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NATIONAL MONITORING PROTOCOL FOR PERSISTENT ORGANIC POLLUTANTS (POPS) AND OTHER PRIORITY CHEMICALS IN THE AMBIENT

ENVIRONMENT (AIR, WATER AND SOIL)

UNITED NATIONS DEVELOPMENT PROGRAMME

«UNDP»

REQUEST FOR PROPOSAL: REF: RFP/UNDPKEN/004/2019

CONSULTANCY SERVICES TO ALIGN THE DRAFT KENYAN SOUND CHEMICALS POLICY AND DRAFT CHEMICAL REGULATIONS TO CHEMICAL

MULTILATERAL ENVIRONMENTAL AGREEMENTS (MEAS) AND THE

STRATEGIC APPROACH TO INTERNATIONAL CHEMICALS MANAGEMENT (SAICM), DEVELOP A NATIONAL MONITORING PROTOCOL FOR

PERSISTENT ORGANIC POLLUTANTS AND DEVELOP A POLLUTANT RELEASE AND TRANSFER REGISTER (PRTR)

29TH JANUARY, 2021

Compiled by:

McKay & Company Advocates, McKay Chambers, 215 David Osieli Road, Off Rhapta Road

Westlands P.O. Box 29884-00100

Nairobi

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PREFACE

This protocol provides guidance towards systematic monitoring of ambient air, water and soil to provide comparable national data. Chapters 1 presents the scope of the monitoring protocol, national context and objectives. Chapter 2 outlines the methodology applied in its development and the objectives of the protocol.

Chapters 3 provides a detailed national capacity assessment. Chapter 4 provides key principle features for national monitoring protocol including list of chemicals, sampling sites.

Chapter 5 discusses sampling and sample preparation for air media. Chapter 6 discusses sampling and sample preparation for water media. Chapter 7 discusses soil sampling and sample preparation.

Chapter 8 discusses the analytical methods for different sample matrices providing the overall framework for analytical criteria. Chapter 9 discusses quality control and quality assurances. Chapter 10 provides a data management framework. Chapter 11 outlines the piloting of the national monitoring protocol Chapter 12 provides conclusion and recommendations, while Chapter 13 provides the framework for review of the protocol.

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ACKNOWLEDGMENT

McKay & Company Advocates would like to acknowledge the contribution of the government agencies and the private sector towards the development of this national monitoring protocol.

This monitoring protocol marks an important step towards strengthening chemicals management in the country. A monitoring protocol is a key environmental management tool for comprehensive assessment of hazardous chemicals substances into air, water and soil. It also provides guidance for collection of comparable data on chemical substances in the ambient environment from monitoring activities which is important to assess exposure to human and environment.

This protocol was developed through the financial support provided by the Global Environment Facility (GEF) project under the project on Sound Chemicals Management Mainstreaming and Unintentionally Produced Persistent Organic Pollutants (UPOPs) reduction in Kenya.

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EXECUTIVE SUMMARY

Chemical monitoring is a requirement embedded is several national legislative frameworks addressing air, water and soil management in the country with the goal to protect human health and environment from adverse health effects associated with hazardous chemicals. In addition, Kenya is party to several multilateral environment agreements, such as the Stockholm Convention, the Basel Convention, the Rotterdam Conventions and the Minamata Convention that call for prudent management of chemicals across the entire life cycle. Monitoring is a key step in chemicals management life cycle and involves long-term, standardised, observation, evaluation and reporting of the environment to determine the status and trends overtime. Air, water and soil are key resources that must be monitored to ascertain their quality since they directly affect the quality of life and food we eat.

The Constitution of Kenya 2010, the Kenya Vision 2030, the Draft Chemicals Regulations 2019 under the Environmental Management and Coordination Act, No. 8 of 1999 (EMCA) and the Water Act, No. 43 of 2016 are among the key national instruments that have provisions that demand prudent environmental management to protect human health and environment. Articles 69 and 70 of the Constitution encourage public participation in the management, protection and conservation of the environment and establishment of systems for environmental impact assessment, environmental audit and monitoring of the environment, and utilization of the information collected to develop measures to eliminate processes and activities that are likely to endanger human health and the environment.

Kenya’s Vision 2030 aims to transform Kenya into a newly industrializing, middle-income country providing a high quality of life to all its citizens by the year 2030 in a clean and secure environment. The vision is further amplified in the Big Four Agenda of the current government which aims to strengthen the national Manufacturing, Health, Agriculture and Housing sectors. The goal aims at revamping industries and manufacturing sectors in Kenya to contribute significantly to national development.

The need for consistent monitoring of chemicals in the country is anchored on the fact that chemicals are used in most economic development activities hence emissions to air, water and soil need to be well managed to protect human health and environment. For instance manufacturing and agricultural activities in the country use diverse categories of chemicals such as pesticides, flame retardants, and a wide range chemicals that may fall under emerging pollutants whose releases into environment must be monitored. In addition municipal, agricultural and medical solid waste treatment by combustion at low temperatures or open burning are associated with releases of UPOPs that need to be monitored and controlled to protect human health and environment.

Kenya is also a gateway for international trade to many Eastern and Central African countries such as Uganda, Rwanda, Burundi and Democratic Republic of Congo, and provides a transit route for international cargo transport, part of which involves chemicals, that require risk preparedness, monitoring and pollution control measures to be put in place while the cargo is in transit within the national boundaries. Hence a robust chemicals monitoring programme is required to provide a comprehensive assessment of pollutants released into air, water and soil at both national and county levels.

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This monitoring protocol was developed through review of the existing legislative frameworks and mandates, stakeholder consultation on existing chemicals monitoring capacities and capacity needs assessment, and alignment with international monitoring programmes particularly the Global Monitoring Plan. The main form of engagement of the key national stakeholders in chemicals management involved administration of structured questionnaires and field visits, and the data collected was assessed and incorporated into the monitoring protocol. The institutions included National Environment Management Authority (NEMA), The Water Resources Authority, Kenya Plant Health Inspectorate Services, the Government Chemist Department, Pest Control Products Board, Kenya Bureau of Standards, Kenya Meteorological Department, Kenya Medical Research Institute, Kenya Revenue Authority, and public and private universities within the country. The national chemicals monitoring protocol provides overall guidance to ensure consistency and comparability in monitoring activities of persistent organic pollutants (POPs) and other priority chemicals in the country.

The selection of chemicals to be considered in the national monitoring programme is based on the chemicals listed in the national legislative framework, standards, the chemicals Multilateral Environment Agreements (MEAs) that Kenya is party to and the priority chemicals to Kenya. The chemicals listed for monitoring include POPs (pesticides, PCBs, PBDEs, PFOS, Polychlorinated naphthalenes, Short Chain Chlorinated paraffins, and salts and dioxins and furans), heavy metals (Hg, Pb, Cd, As) & fluoride in water, SOx, NOx, PM10, PM2.5, HCl, CO, PAHs, greenhouse gases and industrial chemicals.

The benefits of the national chemicals monitoring protocol include:

i) Provides guidance to ensure cost-effective approach in providing scientifically sound environmental monitoring data.

ii) Creates consistency in analytical parameters and chemical testing methods thus enhancing comparability of monitoring data.

iii) Ensures long-term sustainability of monitoring activities and development of representative data at national, regional and county levels.

iv) Allows targeted phased enhancement of monitoring capacities of counties to participate in national and regional pollution monitoring.

v) Allows assessment of performance of the environmental legislations in environmental protection.

vi) Provides a framework for collaboration among national and county institutions in environmental monitoring and management.

vii) Identifies pollution sources for mitigation measures to be taken and ensure compliance to the laid down levels of pollution in the national legislation and international frameworks.

The national institutions have basic analytical instruments for analysis of pesticides, polychlorinated biphenyls, poly-brominated diethyl ethers in water, air, soil and in products. However, majority lacking experience in environmental media sampling, analysis and data handling relating to POPs. No national institution has adequate analytical capacity and experience in analysis of dioxins and furans in environmental media.

The national institutions with analytical instrumentation necessary for analysis of pesticides include Kenya Plant Health Inspectorate Services (KEPHIS), Water Resources Authority, the Government Chemist Department, Pests Control Product Board (PCPB), Kenya Bureau of Standards (KEBS), Universities and the SGS private laboratory. The University of Nairobi

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participates in the international Global Monitoring Plan and coordinates POPs monitoring in the country with long-term monitoring sites at Mt. Kenya, Kabete, Chiromo and Industrial are for air, and Sabaki River mouth for water. In addition, the University department of public health, pharmacology and toxicology coordinates the mother’s milk monitoring in Kenya under the UNEP/WHO programme.

The Water Resources Authority is the national institution charged under the Water Act, No. 43 of 2016 with conducting regular water monitoring and geo-referencing of water resources. NEMA is charged with monitoring the air quality and industrial discharges into air, water and soil under the EMCA, draft Chemical Regulations, 2019. Hence, the two are obliged to coordinate monitoring of chemicals in water, air and soil to ensure coordinated, long-term, sustainable chemicals monitoring in the three media. Other national institutions charged with specialised monitoring activities are KEPHIS, PCPB, KEBS, Kenya Fisheries and Marine Research Institute (KEMFRI), Kenya Meteorology Department (KMD), Kenya Forestry Research Institute (KEFRI) and the Division of Occupational health and safety (DOSH) and Universities for driving research and training.

The cost of POPs analysis is depended on the class of POPs. Analytical cost of POP pesticides range from USD 150-350, indicator PCBs (USD 150-350), PBDEs (USD 300-450), dioxins/furans (USD 500-900), dioxin like PCBs (USD 300-350) and PFOS (USD 250-350). It is critical to note that the cost of managing environmental disease burden associated with hazardous chemicals is much higher than the cost of environmental monitoring that enables taking early precautions to control ill health effects.

Several academic institutions in the country are engaged in training and capacity building for chemicals management. It is underscored that to implement the national monitoring programme requires robust training in elements of POPs and other chemicals monitoring, and includes theoretical and hands-on training on sampling, analysis and data management. In view of these requirements, institutions with experience in POPs monitoring are recommended to provide the necessary training modules. From the analysis of the existing capacities and experience of the institutions in POPs monitoring identified the University of Nairobi, Department of Chemistry having the necessary experience for air, water and soil monitoring. The second institution is the Jomo Kenyatta University of Agriculture and Technology for general training on GC/MS and LC/MS. However, it is noteworthy that in the long term additional universities and research institutions at regional level will require systematic capacity enhancement to expand capacity building activities at county and regional levels. These include Maseno University and Masinde Muliro University of Science and Technology for the Western Region, Egerton and Moi Universities for the Rift Valley region, Technical University of Mombasa and Pwani University for Mombasa and coast region, and Technical University of Kenya, Kenyatta University and multimedia university of Kenya for Nairobi and Central region.

Implementation of the national chemicals monitoring programme for air, water and soil in the country will require the following considerations:

i) Endorsement of the analytical parameters and sampling sites for air, water and soil monitoring for the monitoring network.

ii) Establishment of the monitoring network of institutions to work with NEMA and WRA in implementing of the monitoring activities including sampling, sample analysis and data management.

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iii) Enhancing monitoring infrastructure in the country including sampling equipment, analytical equipment, computer hardware and software for data archiving, storage and visualisation tools for data dissemination.

iv) Training staff of WRA and NEMA and other participating institutions to effectively implement chemical monitoring activities including sampling and analytical methods for air, water and soil for the POPs and other priority chemicals.

v) Establishing the national and county coordination teams to guide the implementation of the national monitoring protocol and monitoring activities.

vi) Establishing a peer review team to ensure consistence and quality in data collection, analysis, reporting and dissemination.

vii) Initial piloting of the national monitoring programme to fine tune the logistical arrangements and assessment of the proposed monitoring sites, parameters, methodologies and further capacity enhancement needs.

viii) National institutions should include POPs in the list of chemical substances they monitor on regular basis in water and air. Dioxins and furans can be excluded from water monitoring since they are least soluble in water.

ix) Provision of adequate financial resources for monitoring in institutional budgetary allocation to ensure continuity of monitoring activities at national and county levels.

x) Institutions participating in the monitoring and laboratory sample analysis should implement internal quality control and also continually participate in the inter-laboratory proficiency studies as part of the external QA/QC protocol to ascertain the quality of data produced.

In conclusion the monitoring protocol is an important environmental management tool to guide monitoring activities to provide comparable data on diffuse sources of chemicals into the environment. Together with the Pollutants Release and Transfer Register (PRTR) and exposure assessment, they contribute to a comprehensive picture of the status of chemicals pollution and potential impacts on to human health and ecosystems, and assessment of the performance of the national environmental management legislation and regulatory measures.

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ABBREVIATIONS

AMC Annual maintenance contract AQC Analytical Quality Control BC Basel Convention BOD Biological oxygen demand CAS Chemical Abstract Service CIP Census of Industrial Product COD Chemical oxygen demand CoGs Council of Governors DO Dissolved Oxygen DOSH Division of Occupational Safety and Health EAC East Africa Community GDP Gross Domestic Product GEF Global Environment Facility GMP Global Monitoring Plan GoK Government of Kenya ISIC International Standard of Industrial Classification ISO International Standards Organisation KAM Kenya Association of Manufacturers KEFRI Kenya Fisheries Research Institute KEMRI Kenya Medical Research Institute KIRDI Kenya Industry Research and Development Institute KMC Kenya Meat Commission KNBS Kenya National Bureau of Statistics KNH Kenyatta National Hospital KRA Kenya Revenue Authority LCL Lower control limit LWL Lower warning limit MC Minamata Convention MEA Multilateral Environment Agreement MEFR Ministry of Environment and Forestry Resources MOH Ministry of Health MOWSI Ministry of Water & sanitation and irrigation MSDS Material safety data sheet NCT National Coordination Team NEMA National Environment Management Authority NIP National Implementation Plan OCP Organochlorine Pesticide OECD Organisation for Economic Co-operation and Development PAH Polycyclic aromatic hydrocarbon PBDE Polybrominated Diethyl Ether PCB Polychlorinated Biphenyl PCC Public Complaints Committee PCDD Polychlorinated Dibenzo p-Dioxin PCDF Polychlorinated Dibenzo Furans PCN Polychlorinated Naphthalene PCPB Pest Control Products Board PFOS Perfluorooctane sulfonic acid PIC Prior Informed Consent POP Persistent Organic Pollutant

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PRTR Pollutant Release and Transfer Register RPD Relative Percent Difference SAICM Strategic Approach International Chemicals Management SC Stockholm Convention SCCP Short Chain Chlorinated Paraffin SME Small and Medium Size Enterprise SOP Standard operating procedure TPH Total petroleum hydrocarbons TSS Total suspended solids UCL Upper control limit UNCED United Nations Conference on Environment and Development UNEP United Nations Environment Program UPOP Unintentionally Produced Persistent Organic Pollutant UWL Upper warning limit WHO Word Health Organisation WRA Water Resources Authority

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TABLE OF CONTENTS

PREFACE .......................................................................................................................................................... II

ACKNOWLEDGMENT .......................................................................................................................................III

EXECUTIVE SUMMARY ................................................................................................................................... IV

ABBREVIATIONS .......................................................................................................................................... VIII

LIST OF TABLES ............................................................................................................................................. XV

LIST OF FIGURES .......................................................................................................................................... XVII

1. INTRODUCTION ............................................................................................................................................ 1

1.1 SCOPE AND APPLICATION .................................................................................................................................... 1 1.2 THE GOAL OF THE CHEMICALS MONITORING PROTOCOL ............................................................................................. 1 1.3 BENEFITS OF A NATIONAL MONITORING PROTOCOL ................................................................................................. 2 1.4 NEED FOR CONSISTENT MONITORING OF POPS AND OTHER HAZARDOUS CHEMICALS ...................................................... 2 1.5 NATIONAL CONTEXT........................................................................................................................................... 3

5.1.1 Political administrative units ................................................................................................................ 3 1.5.2 Physical features of interest to chemicals monitoring ......................................................................... 3 1.5.3 Socio-economic Activities ..................................................................................................................... 5

1.6 OVERVIEW OF SELECTED POLLUTANTS IN AMBIENT ENVIRONMENT IN KENYA ................................................................. 5

2. METHODOLOGY FOLLOWED IN DEVELOPING THE NATIONAL MONITORING PROTOCOL ........................... 11

2.1 DESK REVIEW ................................................................................................................................................. 11 2.2 CAPACITY NEEDS ASSESSMENT FOR ANALYSIS OF POPS AND OTHER CHEMICALS ........................................................... 11 2.3 SITE SELECTION, SAMPLE MATRICES AND ANALYTICAL PARAMETERS ........................................................................... 11 2.4 STAKEHOLDER WORKSHOP ................................................................................................................................ 11

3. NATIONAL CAPACITY ASSESSMENT ............................................................................................................ 13

3.1 LEGAL FRAMEWORK FOR ENVIRONMENTAL MONITORING ........................................................................................ 13 3.1.1 The Kenyan constitution ..................................................................................................................... 13 3.1.2 The Environmental Management and Coordination Act (EMCA), 1999 and its amendments, .......... 13 3.1.3 EMCA (Toxic and Hazardous Chemicals and Materials Management) Regulations, 2019 ................ 13 3.1.4 Environmental Management and Co-Ordination (Water Quality) Regulations, 2006 ....................... 14 3.1.5 The Environmental Management and Co-Ordination (Air Quality) Regulations, 2014 ...................... 14 3.1.6 Water Act 2016 .................................................................................................................................. 14 3.1.7 National sustainable waste management bill 2018 ........................................................................... 15

3.2 GLOBAL FRAMEWORKS ON ENVIRONMENTAL MONITORING...................................................................................... 16 3.3.1 Global Monitoring Plan (GMP) ........................................................................................................... 17 3.3.2 Regional seas program ....................................................................................................................... 17

3.3 NATIONAL INSTITUTIONAL FRAMEWORKS AND MANDATES ON ENVIRONMENTAL MANAGEMENT ..................................... 17 3.3.1 National Environmental Authority (NEMA) ........................................................................................ 17 3.3.2 Water Resource Authority (WRA) ....................................................................................................... 17 3.3.3 Kenya Bureau of Standards (KEBS) ..................................................................................................... 18 3.3.4 Government Chemist .......................................................................................................................... 18 3.3.5 Directorate of occupational safety and health services (DOSHS) ....................................................... 18 3.3.6 Kenya Plant Health and Inspectorate Services (KEPHIS) .................................................................... 18 3.3.7 The Pests Control Product Board (PCPB) ............................................................................................ 18 3.3.8 Kenya marine and fisheries research institute (KMFRI)...................................................................... 18 3.3.9 Universities ......................................................................................................................................... 19

3.4 INSTITUTION ANALYTICAL CAPACITIES .................................................................................................................. 19 3.5 EXISTING MONITORING PROGRAMMES WHERE KENYA PARTICIPATES ......................................................................... 25

3.5.1 The Global Monitoring Plan ............................................................................................................... 25

4. ENVIRONMENTAL MONITORING AND ANALYTICAL PARAMETERS ............................................................. 30

4.1 THE OBJECTIVES OF CHEMICALS MONITORING PROGRAMME .................................................................................... 31

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4.2 COST EFFICIENCY AND SOCIOECONOMIC PRINCIPLES ............................................................................................... 31 4.3 GENERALS PRINCIPLES FOR SELECTION OF CHEMICAL MONITORING PARAMETERS .......................................................... 32 4.4 ANALYTICAL PARAMETERS ................................................................................................................................. 32 4.5 RECOMMENDED POPS FOR NATIONAL MONITORING ............................................................................................ 33 4.6 GEOGRAPHICAL SCALE OF MONITORING SITES ....................................................................................................... 37 4.7 MONITORING FREQUENCY ................................................................................................................................ 37 4.8 CHOOSING RELEVANT INDICATORS ...................................................................................................................... 37 4.9 SAMPLING METHODS AND STATISTICAL DESIGN ...................................................................................................... 38 4.10 ENVIRONMENTAL MONITORING TARGETS ........................................................................................................... 39 4.11 QUALITY ASSURANCE AND QUALITY CONTROL .................................................................................................... 39 4.12 DATA ASSESSMENT........................................................................................................................................ 40 4.13 DATA AND INFORMATION SHARING ................................................................................................................... 41 4.14 RESOURCES NECESSARY FOR MONITORING ......................................................................................................... 41

5. AIR SAMPLING AND SAMPLE PREPARATION .............................................................................................. 42

5.1 AIR SAMPLING SITE CONSIDERATION .................................................................................................................... 42 5.2 SPATIAL REPRESENTATIVENESS ........................................................................................................................... 42 5.3 SITE CLASSIFICATION ........................................................................................................................................ 43 5.4 SITING CONSIDERATIONS ................................................................................................................................... 44 5.5 CHARACTERISTIC TRAVEL DISTANCES (CTDS, KM) FOR AIR AND WATER ....................................................................... 45 5.6 AIR SAMPLING AND SAMPLE HANDLING................................................................................................................ 46 5.7 ACTIVE AIR SAMPLING ...................................................................................................................................... 46 5.8 SAMPLING BREAKTHROUGH ............................................................................................................................... 47 5.9 FIELD BLANKS SHOULD BE TAKEN REGULARLY. ....................................................................................................... 47 5.10 ABSORBENTS ARE PRE-CLEANED PRIOR TO SAMPLING............................................................................................ 48 5.11 PASSIVE SAMPLING ........................................................................................................................................ 48

6. WATER SAMPLING AND SAMPLE PREPARATION ........................................................................................ 51

6.1 GENERALS CONSIDERATION OF WATER QUALITY ..................................................................................................... 51 i) Temperature ............................................................................................................................................ 51 ii) Specific Electrical Conductivity (EC25 or SC25) ........................................................................................ 51 iii) pH ........................................................................................................................................................... 52 iv) Dissolved Oxygen (Concentration and % Saturation) ............................................................................. 52 v) Lake Level ................................................................................................................................................ 53 vi) Water Clarity .......................................................................................................................................... 53 vii) Major Ions ............................................................................................................................................. 53 viii) Dissolved Silica (SiO2) ............................................................................................................................ 54 ix) Dissolved Organic Carbon (DOC) ............................................................................................................ 54 x) Nutrients (Total Phosphorus [TP], Total Nitrogen [TN], Nitrate+Nitrite-N .............................................. 54 xi) Chlorophyll-a .......................................................................................................................................... 54

6.2 OBJECTIVES OF WATER QUALITY MONITORING ....................................................................................................... 55 6.3 WATER QUALITY SAMPLING GUIDANCE ................................................................................................................ 55

6.3.1 Site selection ...................................................................................................................................... 55 6.3.2 Sampling frequency ............................................................................................................................ 56 6.3.3 General water sampling design .......................................................................................................... 57 6.3.4 Types of Samples ................................................................................................................................ 57 6.3.5 Water Sampling equipment ............................................................................................................... 58 6.3.6 Sample Containers and Cleaning Procedures ..................................................................................... 62 6.3.7 Sampling surface water for physical and chemical analyses ............................................................. 64 6.3.8 Sampling frequency and parameters ................................................................................................. 65 Table 6. 3 Proposed water sampling sites for POPs monitoring in water ................................................... 65 6.3.9 Preparation for Fieldwork .................................................................................................................. 66 6.3.10 Checklist for field sampling .............................................................................................................. 67 6.3.11Site - Recording Field Information ..................................................................................................... 68 6.3.12 Guidelines during sampling .............................................................................................................. 69 6.3.13 Surface water Sampling ................................................................................................................... 69 6.3.14 Sample Labelling .............................................................................................................................. 71

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6.3.15 Measurement of Field Parameters ................................................................................................... 72 6.3.16 Sample packing and transportation ................................................................................................. 72 6.3.17 Shipping Samples to Contract Laboratory ........................................................................................ 73 6.3.18 Equipment Cleaning and Storage ..................................................................................................... 73 6.3.19 Field Data Entry and Management .................................................................................................. 73 6.3.20 End of Field Season Procedures ........................................................................................................ 74 6.3.21 Reception of samples by the laboratory ........................................................................................... 74 6.3.22 Safety during field work ................................................................................................................... 74

6.4 LABORATORY ANALYSIS FOR PHYSICAL-CHEMICAL PARAMETERS ................................................................................ 74 6.5 DATA VALIDATION ........................................................................................................................................... 76

i) Absolute checking/Data entry .................................................................................................................. 76 ii) General checks: ....................................................................................................................................... 77 iii) Conditional Checks ................................................................................................................................. 77

6.6 DATA ANALYSIS AND PRESENTATION .................................................................................................................... 77 6.7 DATA INTERPRETATION .................................................................................................................................... 78

7. SOIL SAMPLING PROCEDURES .................................................................................................................... 79

7.1 SOIL SAMPLING .............................................................................................................................................. 79 7.2 SOIL SAMPLING PRECAUTIONS ............................................................................................................................ 79 7.3 SPECIAL PRECAUTIONS FOR TRACE CONTAMINANT SOIL SAMPLING ........................................................................... 79 7.4 SAMPLE HOMOGENIZATION .............................................................................................................................. 80 7.5 SAMPLES FOR VOC ANALYSIS ARE NOT HOMOGENIZED. .......................................................................................... 80 7.6 DRESSING SOIL SURFACES ................................................................................................................................. 81 7.7 SOIL SAMPLES FOR VOLATILE ORGANIC COMPOUNDS (VOC) ANALYSIS ..................................................................... 81 7.8 SOIL SAMPLING .............................................................................................................................................. 81

7.8.1 Equipment .......................................................................................................................................... 81 7.8.2 Sampling Methodology - Low Concentrations (<200 µg/kg) .............................................................. 81 7.8.4 Sampling Methodology - High Concentrations (>200 µg/kg) ............................................................. 82 7.8.5 Special Techniques and Considerations .............................................................................................. 82

7.9 METHODS FOR COLLECTING SOIL SAMPLES............................................................................................................ 83 7.10 SOIL SAMPLING SITES AND FREQUENCY .............................................................................................................. 85 7.11 QUALITY CONTROL ........................................................................................................................................ 85 7.12 RECORDS ..................................................................................................................................................... 85

8. ANALYTICAL METHODS FOR POPS ............................................................................................................. 86

8.1 GENERAL CONSIDERATION FOR TRACE ANALYSIS .................................................................................................... 86 8.1.1 Apparatus and instruments ................................................................................................................ 86 8.1.2 Laboratory .......................................................................................................................................... 86 8.1.3 Analytical standards and reference materials.................................................................................... 87 8.1.4 Selection / development of analytical methods ................................................................................. 87 8.1.5 Accuracy and precision ....................................................................................................................... 88

8.2 QUALITY CONTROL SYSTEM ............................................................................................................................... 88 8.3 DOCUMENTING ANALYTICAL METHODS ................................................................................................................ 89 8.4 RECEIVING AND STORAGE OF SAMPLES................................................................................................................. 89 8.5 TAKING SUB-SAMPLES ...................................................................................................................................... 89 8.6 SAMPLE PREPARATION ..................................................................................................................................... 90 8.7 MEASUREMENT .............................................................................................................................................. 90 8.8 MAKING CALIBRATION CURVES ........................................................................................................................... 90 8.9 MONITORING AND INSPECTION .......................................................................................................................... 90

8.8.1 Limit of Detection ............................................................................................................................... 91 8.8.2 Limit of Determination ....................................................................................................................... 91

8.10 RECOMMENDED POPS ANALYTICAL METHODS UNDER GMP ................................................................................. 91 8.11 ESTIMATED INVESTMENT FOR POPS ANALYSIS .................................................................................................... 92

9. QUALITY ASSURANCE AND QUALITY CONTROL REQUIREMENTS ................................................................ 94

9.1 QUALITY ASSURANCE ....................................................................................................................................... 94 9.2 PERSONNEL REQUIREMENTS AND TRAINING ......................................................................................................... 94

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ii) Assistant Project Manager ...................................................................................................................... 95 iii) Field Personnel (Field Crew Member/Leader) ........................................................................................ 95 A. Data Manager ................................................................................................................................... 96 B. Crew Qualifications ............................................................................................................................ 96

9.3 TRAINING MATERIALS ....................................................................................................................................... 96 9.4 OPERATIONAL REQUIREMENTS .......................................................................................................................... 97 9.5 ANALYTICAL QUALITY CONTROL ......................................................................................................................... 97

9.5.1 Intra-laboratory programme studies ................................................................................................. 97 ii) Field Procedures ...................................................................................................................................... 99 iii) Laboratory Procedures ........................................................................................................................... 99 9.5.2 Inter-Laboratory AQC ......................................................................................................................... 99

9.6 GUIDELINES ON MANAGEMENT ASPECTS .............................................................................................................. 99

10. DATA MANAGEMENT ............................................................................................................................. 101

10.1 DATA ENTRY, VERIFICATION, AND EDITING ....................................................................................................... 101 10.2 DATA ARCHIVAL PROCEDURES ....................................................................................................................... 101 10.3 QUALITY ASSURANCE AND QUALITY CONTROL PERTAINING TO DATA ENTRY AND MANAGEMENT ............................... 102 10.4 ROUTINE DATA SUMMARIES ......................................................................................................................... 102

11. IMPLEMENTING THE MONITORING PROTOCOL ..................................................................................... 103

11.1 PILOT MONITORING NETWORK ....................................................................................................................... 103 11.2 BASELINE MONITORING ................................................................................................................................ 103 11.3 PROPOSED INITIAL ANALYTICAL LABORATORIES FOR POPS MONITORING ............................................................... 108 11.4 DATA HANDLING ......................................................................................................................................... 108 11.5 REPORTING AND PUBLISHING ......................................................................................................................... 109 11.6 PROGRAMME REVIEW .................................................................................................................................. 109

11.5.1 Data collection ............................................................................................................................... 109 11.5.2 Data analysis and use..................................................................................................................... 109

11.7 REPORTING FORMAT .................................................................................................................................... 109 11.8 TRAINING AND CAPACITY BUILDING INSTITUTIONS .............................................................................................. 110

12 CONCLUSION AND RECOMMENDATIONS ................................................................................................ 112

12.1 CONCLUSION .............................................................................................................................................. 112 12.2 RECOMMENDATIONS: .................................................................................................................................. 112

13 PROTOCOL REVISION .............................................................................................................................. 114

REFERENCES ................................................................................................................................................. 115

GAW. 2020. CHEMICALS AND PHYSICAL PROCESSES THAT CONTROL COMPOSITION OF CHEMICALS IN THE ATMOSPHERE. ACCESS

AT: HTTPS://COMMUNITY.WMO.INT/ACTIVITY-AREAS/GAW ........................................................................................ 115

APPENDIX 1 ................................................................................................................................................. 119

LABORATORY REPORTING DATA SHEETS .................................................................................................................. 119

APPENDIX 2 ................................................................................................................................................. 122

QUESTIONNAIRE FOR LABORATORY CAPACITY ASSESSMENT ......................................................................................... 122

APPENDIX 3 ................................................................................................................................................. 129

METHODOLOGY OF PASSIVE AIR SAMPLING OF POPS IN AMBIENT AIR ............................................................................ 129

APPENDIX 4 ................................................................................................................................................. 135

TRAINING MATERIALS FOR POPS ANALYSIS ............................................................................................................. 135

APPENDIX 5 ................................................................................................................................................. 144

WATER AND AIR QUALITY STANDARDS ................................................................................................................... 144

APPENDIX 6 ................................................................................................................................................. 148

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WORKSHOP PARTICIPANTS ................................................................................................................................... 148

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LIST OF TABLES

Table 3.1 Analytical capacities in research, monitoring and regulatory institutions .............. 20

Table 3.2 Laboratory operational assessment ....................................................................... 20

Table 3.3 Methods used of extraction for POPs in different matrices ................................... 23

Table 3.4 Estimated cost of analysis for different POPs groups and other pollutants ............ 24

Table 3.5 Existing Monitoring activities .............................................................................. 29

Table 4.1 Types of Chemical monitoring ............................................................................. 30

Table 4.2 POPs Analytical parameters ................................................................................. 32

Table 4.3 Initial POPs compounds .................................................................................... 34

Table 4.4 POPs listed at COP-4 and 5............................................................................... 35

Table 4.5 Quick measureable indicators of environmental change ....................................... 37

Table 4.6. Identified monitoring sites for baseline survey .................................................... 38

Table 5.1 Representation of spatial scale of air masses ........................................................ 43

Table 5.2 Characteristic travel distances (CTDs, km) for air and water ................................ 45

Table 5. 3 Proposed air monitoring sites and frequency ....................................................... 50

Table 6.1 Water sampling designs for lakes and Rivers ....................................................... 57

Table 6.2 General guidelines on sample containers. ............................................................. 63

Table 6.4. Example range of analytical methods, method detection limits (MDLs), containers, preservation methods, and holding times. ............................................................................ 75

Table 7.1 Methods for soil sampling ................................................................................... 83

Table 7.2 Soil monitoring sites for POPs monitoring in soil ................................................ 85

Table 8. 1 Recommended analytical methods for POPs compounds .................................... 91

Table 8.2 Estimated cost for investment in POPs analysis laboratory and consumables. ...... 92

Table 10.1 Summary of QA/QC procedures pertaining to data management. ..................... 102

Table 11.1 Proposed monitoring framework for POPs in ambient air................................. 104

Table 11.2 Proposed monitoring framework for POPs in ambient water ............................ 105

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Table 11.3 Proposed monitoring framework for POPs in ambient water ............................ 106

Table A1.1 Laboratory reporting sheet for water data ........................................................ 119

Table A1.2. Laboratory reporting sheet for soil data .......................................................... 120

Table A1.3. Laboratory reporting sheet for air data ........................................................... 121

Table A1 Domestic Water quality standards ...................................................................... 144

Table A2. List of Priority Air Pollutants ........................................................................ 145

Table A3 Air quality standards .......................................................................................... 146

Table A4 List of participants to Monitoring Protocol workshops ....................................... 148

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LIST OF FIGURES

Figure 1.1 Main water catchments in Kenya .......................................................................... 4

Figure 1.2 Concentration of ∑p,p’-DDT3 in ambient air of Mt. Kenya from 2008-2018. ....... 6

Figure 1.3 Comparison of ∑DDT6 levels in ambient air (PAS, ng filter-1) ............................ 7

Figure 1.4 ∑HCH4 (sum of α, β, γ, δ-HCH) in the ambient air (PAS, ng filter-1) .................... 7

Figure 1.5 HCB levels in the ambient air (PAS, ng filter-1) .................................................... 8

Figure 1.6 ∑PCB7 levels (Sum 7 indicator PCB congeners) in the ambient air (PAS, ngfilter-

1) ........................................................................................................................................... 9

Figure 1.7 ∑PCB7 levels (7 Indicator PCB congeners) in soil (ng g-1) .................................... 9

Figure 1.8 HCB levels in soil (ng g-1) .................................................................................. 10

Figure 2.1 Photo of stakeholders during validation workshop .............................................. 12

Figure 3.1 Photo of Passive samplers for POPs at Kabete Site ............................................. 26

Figure.3.2 Overview of GAW monitoring Programme. ....................................................... 27

Figure 3.3 shows a photo of GAW sampling site located on Mt. Kenya. .............................. 28

Figure 3.4 Atmospheric Deposition measurements station ................................................... 28

Figure 4.1 Overall framework of environmental effect on ecosystem and health .................. 31

Figure 4.2 Geographical scale of monitoring ....................................................................... 37

Figure 5.1 High Volume Air samplers Low Volume samplers ............................................ 46

Figure 5.2 Schematic of PUF disk passive air sampler ......................................................... 49

Figure 6.1 Dissolved oxygen sampler .................................................................................. 58

Figure 6.2 Depth sampler .................................................................................................... 59

Figure 6.3 Depth sampler suitable for moderate depths ....................................................... 60

Figure 6.4 Multi-purpose sampler........................................................................................ 61

Figure 6.5 Sampling surface water ...................................................................................... 62

Figure 6.6 Lowering a weighted bottle into a well ............................................................... 71

Figure 6.7 Field sample storage box .................................................................................... 73

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1. INTRODUCTION

1.1 Scope and application

Chemical monitoring is a requirement embedded in several national legal frameworks addressing air, water and soil management in the country to protect human health and environment. In addition, Kenya is party to several multilateral environmental agreements, such as the Stockholm, the Basel and the Rotterdam Conventions, that call for prudent management of chemicals across the entire life cycle. Monitoring is a key step in chemicals management life cycle and involves long-term, standardised, observation, evaluation and reporting of the environment to determine the status and trends overtime. Air, water and soil are key resources that must be monitored to ascertain their quality since they directly affect the quality of life and food.

Water is one of the most essential commodities for day-to-day life, and plays a crucial role in national socio-economic development. While the total amount of water in the world is constant and ‘is said to be’ adequate to meet all the demands of mankind, its quality and distribution over different regions is uneven and this contributes to the problems of availability and suitability. It is therefore imperative to develop, use and manage the scarce water resources as rationally and efficiently as possible. In order to execute this task, accurate and adequate information must be made available about the extent of chemical pollution in the environment under the constantly changing human pressures and natural forces.

Air pollution has attracted global attention due to the complex mixture of pollutants inhaled and associated ill health effects. Air pollution has both acute and chronic effects on human health, affecting a number of different systems and organs. It ranges from minor upper respiratory irritation to chronic respiratory and heart disease, lung cancer, acute respiratory infections in children and chronic bronchitis in adults, aggravating pre-existing heart and lung disease, or asthmatic attacks (WHO, 2018 & 2009; Miller, 2020; Teresa et al., 2007; Pope et al., 2018). In addition, short- and long-term exposures have also been linked with premature mortality and reduced life expectancy.

1.2 The goal of the chemicals monitoring protocol

The primary purpose of the monitoring protocol is to provide guidance to entities involved in environmental monitoring of air, water and soil to obtain comparable and quality monitoring data that can guide policy decisions. The guidelines provided in this protocol are intended to enhance better coordination in chemicals monitoring activities and analyses of air, water and soil to allow establishment of trends for assessments national source-receptor relationships, and environmental quality impacts.

This protocol provides the minimum requirement for institutions and networks collecting ambient environmental data in support of the Kenya wide environmental pollution monitoring and assessment of compliance with regulatory standards. Adoption of common protocol across the country ensures that data collected by institutions and networks in different jurisdictions are comparable, and can be analysed as a consistent dataset which allows policy decision making and maximum returns from resources invested.

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1.3 Benefits of a national Monitoring Protocol

i) Ensures cost-effective approach to provide scientifically sound environmental monitoring data.

ii) Creates consistency in environmental monitoring activities which include sampling and testing methods and enhances comparability of monitoring data;

iii) Ensures long-term sustainability of monitoring activities and contributes towards achieving national coverage representative data at national, regional and county levels;

iv) Allows phased enhancement of counties and regions to participate in national arrangements for producing comparable monitoring data.

v) Allows assessment of performance of the environmental legislations in minimising or eliminating environmental pollution.

vi) Provides a framework for collaboration among national institutions in environmental monitoring and management of chemicals;

vii) Identifies pollution sources for mitigation measures to be taken in time and avoid crisis and adverse effects of hazardous chemicals on human health and environment;

viii) Allows evaluation of compliance of industry and entities involved in waste management to the laid down maximum pollution levels in the national legislative frameworks.

1.4 Need for consistent monitoring of POPs and other hazardous chemicals

The need for consistent monitoring of chemicals in the country is anchored on the fact that chemicals are used in most economic development activities hence emissions to air, water and soil need to be well managed to protect human health and environment. For instance manufacturing and agricultural activities in the country use diverse categories of chemicals such as pesticides, flame retardants, and a wide range chemicals that may fall under emerging pollutants whose releases into environment must be monitored. In addition municipal, agricultural and medical solid waste treatment by combustion at low temperatures or open burning are associated with releases of Unintentionally Produced Persistent Organic Pollutants (UPOPs) that need to be monitored and controlled to protect human health and environment.

Kenya is also a gateway for international trade to many Eastern and Central African countries such as Uganda, Rwanda, Burundi and Democratic Republic of Congo, and provides a transit route for international cargo transport, part of which involve chemicals, that require risk preparedness, monitoring and pollution control measures to be put in place while the cargo is in transit within the national boundaries. In addition, the Kenyan economy is predominantly driven by agricultural sector whose produce have to meet international standards for export market for tea, coffee, flowers and vegetables etc., as well as the safety standards for domestic market to protect human health. Consequently, a robust chemicals monitoring programme is required to provide a comprehensive assessment of pollutants released into air, water and soil at both national and county levels.

The chemicals of concern in the environment those listed under the national legislations and international conventions such as the Stockholm Convention on persistent organic pollutants, the Rotterdam Convention, the Basel Convention, Minamata Convention among others. Persistent organic pollutants include dioxins and furans, polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenly ethers (PBDEs), Per- and polyfluoroalkyl substances (PFAS), polychlorinated naphthalenes (PCNs), Short Chain

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chlorinated paraffins (SCCPs). Other groups of chemicals of concern in the environment include general pesticides, carbon monoxide (CO), sulfur dioxide (SO2), nitrogen oxides (NOx), volatile organic compounds (VOCs), ozone (O3), heavy metals such as mercury, lead, cadmium, arsenic, chromium, copper, manganese, zinc and gold, and particulate matter (PM2.5 and PM10). The actual mixtures of pollutants differ in their chemical composition, reaction properties, emission, time of disintegration and ability to diffuse in long or short distances.

Chemical pollution is associated with adverse health effects which include cancer, birth defects, reproductive health effects, immunosuppression, respiratory system malfunction, endocrine disruption (Omar et al., 2018; Carpenter, 2011; Christensen et al., 2005; Wu et al., 2008) and negative effects on environment. The ill health burden and diseases associated with hazardous chemicals pollution is much higher than the cost associated with environmental monitoring and sound chemicals management, hence the need to institute robust monitoring of chemicals.

1.5 National context

5.1.1 Political administrative units

The republic of Kenya is located on the eastern part of the continent of Africa between longitudes 34 °E to 42 °E and latitudes 5.5 °N to 5 °S. It neighbours Uganda to the west, Tanzania to the south, Ethiopia to the north, Sudan in the north-west and Somalia to the east. The Indian Ocean is to the south-east and serves the country as an important outlet and means of international maritime contact. Kenya total surface area is about 582,646 km2, of which 11,230 km2 (1.9 %) is covered by water and 571,416 km2 is dry land.

Kenya political administrative structure consists of the national government and the devolved government units made up of 47 counties. National population is estimated at 47 million people according to the 2019 census. The population distribution is uneven from an average of 230 persons per km2 in high population areas to an average of 3 persons per km2 in arid areas. Fast urbanization is influenced by both natural growth and rural-urban migration, has put a lot of strain on the environmental capacity of Kenyan cities to provide adequate housing, hygiene and sanitary services. The growth depicted by these figures will influence solid waste generation and other impacts on environment. It is expected that within the next 20 years, majority of the Kenyan population will be living in urban areas. Such increased urbanization trends will in turn pose further socio-economic, environmental and institutional challenges for Kenyan urban areas.

1.5.2 Physical features of interest to chemicals monitoring

Two-thirds of the country dry land is either semi-desert or desert. National land stretches from sea level in the East with the altitude changing gradually through the coastal belt and plains, the dry intermediate low belt to what is known as the Kenya Highlands within which the Great Rift Valley bisects the Kenya Highlands into East and West. The highest point is about 5,200 Metres at the peak of the snow-capped Mount Kenya located within the central highlands. The main physical features include Mt. Kenya and Aberdare ranges in the central highlands, Mt. Elgon in the western highlands bordering Uganda. Lewis glacier, located on Mt. Kenya, is one of few locations in Africa with glaciers. The tropical Lewis Glacier retreated by more than 800 m (2,625 ft) between 1893 and 2004 and lost almost 16 litres of

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water equivalent to thickness between 1979 and 19961; a phenomenon being associated with global warming.

The major freshwater lakes are L. Victoria to the west and L. Naivasha which is located with the Rift Valley region. Others lakes include L. Nakuru, L. Turkana, L. Bogoria, L. Elementaita, L.Baringo and L. Natron, located within the Rift Valley.

The major rivers within the country include the Tana and the Athi run from Mt. Kenya and the Aberdare ranges to the south to drain into the Indian Ocean. Ewaso Ng’iro river, a major river in the Northeastern Province rises from the Aberdare ranges and flows into the drier areas in the north-eastern parts where it becomes seasonal. Rivers Nyando, Nzoia, Migori, Mara, Sio and Yala run westwards from the western highlands emptying into Lake Victoria (Figure 1.1).

Figure 1.1 Main water catchments in Kenya

The Equator divides the country into almost two equal parts. The country enjoys a tropical climate, with the coastal region being hot and humid, temperate inland and very dry in the north and northeast parts of the country. Kenya generally experiences two seasonal rainfall peaks (bimodal) in most places; short rains during October and December, and long rains from March to May. However, some areas in western and central parts of the Rift Valley experience a tri-modal rainfall pattern. The January to February period is generally dry over most parts of the country. The annual rainfall ranges, from less than 250 mm in the northern,

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eastern and south-eastern parts to over 2,000 mm in the central highlands, western highlands and the Lake Basin. The rainfall is sometimes heavy around April to May. The hot and humid climatic conditions experienced in different parts of the country influence the fate, transport and distribution of chemicals into air, water and soil environment.

1.5.3 Socio-economic Activities

Generally, Kenya settlements are confined to places where water can be found and wildlife occupies the greater part of the country. The greater part of the more arable area of the republic is situated in the wetter south-western area, although there is a narrow strip of the land along the Indian Ocean coast that is also arable. The Kenya communities have different culture and traditions influenced by the extent of economic development in their native geographical locations. For example, some communities are predominantly farmers while others are pastoralists, fishermen, and traders. These diverse communities have over many years used environmental resources in various ways, including keeping livestock, sometimes resulting in adverse anthropogenic outcomes. In addition, releases of hazardous chemicals into environment without proper control measures will have long-term negative effects on the socioeconomic activities of the communities, and can disrupt their livelihoods if the situation is unchecked through monitoring.

1.6 Overview of selected pollutants in ambient environment in Kenya

Environmental management and matters relating to chemicals pollution are a propriety to national resources management in the country due to negative impacts that pollution causes to human health and wildlife. Critical areas associated with releases of hazardous chemicals into the environment include:

i) Uncontrolled combustion of solid wastes from urban centres and municipal waste dumpsites.

ii) Medical waste management particularly incineration at lower temperatures than regulatory guidelines;

iii) Traffic related sources of SOx, NOx, CO, particulate matters and other hydrocarbons into the atmosphere;

iv) Releases of hazardous chemicals from contaminated soils in obsolete chemical storage sites and dumpsites which also act as secondary sources of pollutants;

v) Emissions of hazardous chemicals from industrial facilities and manufacturing process by products;

vi) Chemicals releases from construction, demolition and renovation sites into the environment;

vii) Runoff from hydrocarbons and heavy metals from road construction sites and road markings;

viii) Indoor and outdoor fuel combustion activities particularly biomass combustion. ix) Poor disposal of electronic wastes and house hold goods associated with heavy metals

and industrial POPs. x) Runoff of pesticides and fertilizers from agricultural farms into water resources; xi) Mining related emissions of hydrocarbons and heavy metals into environmental media

such as air, water and soil.

Limited research and monitoring activities in the country have revealed environmental contamination from a wide range of sources in both remote and impacted sites. Figure 1.2

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below shows the levels of ∑p,p’-DDT3 in ambient air in Mt. Kenya site which is considered one of the most remote site in Kenya.

Figure 1.2 Concentration of ∑p,p’-DDT3 in ambient air of Mt. Kenya from 2008-2018.

The results suggest a gradual decease in ∑p,p’-DDT3 concentrations from 2008 to 2018 in the atmospheric environment of Mt. Kenya. However, one notable difference in concentration can be observed for non-remote sites such as Dandora, Industrial area and Kitengela site which showed much higher levels as illustrated in Figure 1.3 (UNEP, 2009). The sites in urban areas showed much more elevated concentrations compared to remote areas suggesting potential revolatilization of DDT from contaminated soils and obsolete pesticides dumped in the municipal waste dumpsites.

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Figure 1.3 Comparison of ∑DDT6 levels in ambient air (PAS, ng filter-1)

The comparison of sum ∑DDT6 (sum of o,p’- and p,p’-DDT, DDE, DDD) in ambient air in Kabete, Industrial area, Dandora, Kitengela and Mt. Kenya (which is considered a remote site) are illustrated in Figure 1.3 below. The results showed that Kitengela site registered the highest concentration of ∑DDT6 compared to the other four sites. The high concentration of the ∑DDT6 could be attributed to obsolete pesticides that had been stored at the site and evaporations from the contaminated soil. The combined concentrations of the measured levels January-June 2008 per site showed Kitengela site as the most significant source of ∑DDT6 in ambient air.

The highest levels of ∑HCH4 (sum of α, β, γ, δ-HCH) was measured in ambient air at Kitengela site compared to the rest of the sites Figure 1.4.

Figure 1.4 ∑HCH4 (sum of α, β, γ, δ-HCH) in the ambient air (PAS, ng filter-1)

Hexachlorobenzene (HCB) in air

Compared to DDTs and HCHs, the hexachlorobenzene (HCB) was relatively prevalent in all sites, though at lower levels. The leading concentrations were observed at Dandora, industrials area and kitengela sites Figure 1.5 (UNEP, 2009).

Polychlorinated biphenyls (PCBs) in air

The concentration of ∑PCB7 (sum of PCBs 28, 52, 101, 138, 153, 180, 118) in ambient air was highest in industrial area and Dandora sites compared to Kabete, Kitengela and Mt. Kenya as illustrated in Figure 1.6 below (UNEP, 2009). No significant levels of ∑PCB7 were measured at the Mt. Kenya and Kabete sites suggesting that the levels measured at Dandora,

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Industrial area and Kitengela could be mainly associated with local activities within these localities.

Figure 1.5 HCB levels in the ambient air (PAS, ng filter-1)

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Figure 1.6 ∑PCB7 levels (Sum 7 indicator PCB congeners) in the ambient air (PAS, ngfilter-1)

Polychlorinated biphenyls (PCBs) in soil

The ∑PCB7 in soil was highest in soils from Dandora and Industrial area sites. Low levels were observed in Kitengela soil while Kabete and Mt. Kenya were the lowest. The results suggest that industrial emissions and combustion of the broad mixtures of solid wastes disposed at Dandora dumpsite could be the leading contributors of the PCBs in the soils (Figure 1.7) (UNEP, 2009).

Figure 1.7 ∑PCB7 levels (7 Indicator PCB congeners) in soil (ng g-1)

Hexachlorobenzene (HCB) in soil

For the HCB levels in soil, Dandora, Kitengela and industrial areas recorded the highest concentrations compared to Kabete and Mt. Kenya as shown in Figure 1.8 (UNEP, 2009). The levels detected in soils from these impacted sites could be attributed to contaminations from obsolete chemicals and also minor contributions associated with combustion activities for Dandora and Industrial area sites.

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Figure 1.8 HCB levels in soil (ng g-1)

Chemical monitoring is an important environmental management tool used to provide critical information on the state of pollution, identification of sources, critical pathways and groups and determination of trends in levels of hazardous chemicals in the country. The overall goal in of chemicals monitoring is to protect human health and the environment by managing the risks posed by production, use, import and export of chemicals and reducing or preventing the release of U-POPs and toxic compounds originating from the unsafe management of wastes. The critical sectors namely health care waste and municipal waste were identified, in updated Kenya National Implementation Plan (NIP) for the Stockholm Convention 2014-2019, as among the highest priorities in UPOPs generation in the country (GoK, 2014).

The NIP 2014-2019 also identified lack of national POPs monitoring programme as one of the impediments to implementing sound chemicals management in the country. A systematic analysis of POPs residues in water and air from the national hot spots was recommended as a national priority in POPs management. In addition, building the national capacity in terms human and analytical capacity to support analysis of POPs, and provision of the required spare parts and consumables to support POPs monitoring and research activities was also recommended (GoK, 2014).

Instituting long-term monitoring helps to identify and track hazardous chemicals pollution in environmental media and provide direction for sectors to implement targeted mitigation measures such promoting 3R (Reduce, Reuse, Recycle) economy in waste streams are necessary to enhance upstream collection, material recovery, promoting atom economy in industrial processes, and provides opportunities cooperation with domestic industries to prevent the release of U-POPs and toxic substances.

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2. METHODOLOGY FOLLOWED IN DEVELOPING THE

NATIONAL MONITORING PROTOCOL

2.1 Desk Review

This included a desk review of the international and national legal framework for development of the national POPs monitoring protocol. This included review of the scientific and technical information necessary to provide high quality nationally representative POPs monitoring and other chemicals of national priority. The review also looked at the existing national and international legal framework that supports the development of chemicals monitoring protocol.

2.2 Capacity needs assessment for analysis of POPs and other chemicals

This involved structured questionnaires (Appendix 2) and field visits to the key institutions to determine the existing human capacities, analytical & technical capacities, applied methodologies, and the existing framework for POPs monitoring and funding. This is critical in integrating the existing institutional capacities in implementing the monitoring protocol, establishing a national monitoring network and building the necessary capacities and training for implanting monitoring activities.

2.3 Site selection, sample matrices and analytical parameters

This included site selection included stakeholder engagement to critically evaluate and select priority sites in Mombasa, Nairobi, Nakuru and Kisumu Counties that can form the basis for initial monitoring. The sites characteristics cover potential emissions from municipal dump sites, industrial areas, medical incineration, residential site and the control site. A reconnaissance survey to selected sites for air, water and soil monitoring will be necessary to document the baseline information and geo-referring to allow digitalization of all the sites when the monitoring activities are initiated. This information will be applied during digital presentation of the monitoring data to enhance information sharing and visualization by the regulators, policy makers and other national stakeholders.

2.4 Stakeholder workshop

This included stakeholder consultative meeting and workshop to discuss the objectives of a national protocol for chemicals monitoring in air, water and soil. Identification of the national priority sample types to be monitored, selection of monitoring sites for air, water and soil matrices. Selection of the national monitoring sites, sampling and analytical methods, sampling frequency and analytical chemicals parameters was conducted with reference to other international frameworks such as the Global Monitoring Plan under the Stockholm Convention (UNEP, 2018). The stakeholders also considered climatic and weather conditions experienced in the country, availability of the meteorological data to inform sampling frequencies as well as the local site dynamics and historical background of pollution incidences. The final monitoring protocol was presented to the stakeholders for validation on 16th November 2020. Figure 2.1 shows a photograph of stakeholders during a stakeholder validation workshop of the monitoring protocol. The list of all stakeholders that participated in the workshops in provided in Appendix Table A6.1.

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Figure 2.1 Photo of stakeholders during validation workshop

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3. NATIONAL CAPACITY ASSESSMENT

The national capacity assessment was categorised into three levels: the assessment of legal instruments and international instruments that Kenya is party to that address chemicals monitoring, institutional frameworks and mandates on chemicals monitoring, and existing analytical and technical capacities of the institutions to monitor chemicals.

3.1 Legal framework for environmental monitoring

3.1.1 The Kenyan constitution

Article 42 of the Constitution of Kenya provides every citizen the right to a clean and healthy environment, which includes the right— (a) to have environment protected for the benefit of present and future generations through legislative and other measures.

3.1.2 The Environmental Management and Coordination Act (EMCA), No. 8 of 1999 and its amendments,

EMCA is the overall framework law on environmental management and conservation. It established NEMA among institutions charged with mandates at different levels of environmental management. EMCA provides for environmental protection through; environmental impact assessment, environmental audit and monitoring, environmental restoration conservation orders, and easements.

3.1.3 EMCA (Toxic and Hazardous Chemicals and Materials Management) Regulations, 2019

According to the draft EMCA Toxic and Hazardous Chemicals and Materials Management Regulations of 2019; Regulation 44 addresses elements of monitoring and impact assessment which include:

(1) Lead Agencies shall monitor and assess the hazards, exposure, risks and impacts of toxic and hazardous chemicals and materials to human health and the environment throughout their life cycle.

(2) Lead agencies shall;

a) Promote research, capacity building and develop strategies for sound management of toxic and hazardous chemicals and materials.

b) Encourage information sharing on technical and economically available toxic and hazardous free products and processes, best available technologies and best environmental practices.

c) Monitor emissions and releases of toxic and hazardous industrial chemicals and materials.

d) Reduce and/or eliminate the impacts of toxic and hazardous chemicals and materials to human health and environment.

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e) Monitor contaminants of emerging concern in environmental and biological media to determine their toxicity and hazards, and risks to human health and environment.

3.1.4 Environmental Management and Co-Ordination (Water Quality) Regulations, 2006

Regulation 14 (1) of these Regulations compels every person who generates and discharges effluent into the environment under a licence issued under EMCA to carry out effluent discharge quality and quantity monitoring in accordance with methods and procedures of sampling and analysis prescribed by NEMA, and to submit quarterly records of such monitoring to NEMA or its designated representative. Regulation 14 (2) requires such discharge monitoring record to be in the prescribed form as set out in Sixth Schedule to the Regulations.

The regulation also provides the water quality standard Appendix Table A5.1.

3.1.5 The Environmental Management and Co-Ordination (Air Quality) Regulations, 2014

Under regulation 52 (1) of these Regulations, a person, owner or operator of a facility listed under the fourth schedule is required to ensure that measurement of emissions and occupational exposure levels are carried out in accordance with the methods of test set out in the Eleventh Schedule. Regulation 52 (2) requires the analysis of all measurements in paragraph (1) above to be carried out by laboratories designated by NEMA. Under regulation 53, NEMA in consultation with the relevant lead agencies may carry out all measurements of ambient air quality levels in accordance with the methods of test set out in the Eleventh Schedule. Regulation 54 requires measurements of visible air pollutants to be conducted in accordance with the relevant method of measurement set out under the Eleventh Schedule or in accordance with any method approved by NEMA. Regulation 55 (1) stipulates that the procedure for measuring vehicular exhaust emissions shall be in accordance with the relevant methods of test and analysis stipulated under the Eleventh Schedule or any other method approved by NEMA. The list of priority pollutants and air quality standards are given in Appendix Table A5.2 and A5.3, respectively.

3.1.6 Water Act, No. 43 of 2016

The Water Act, 2016 provides the overall legal framework on water resources management in the country and establishes the key institutions responsible for different levels of water management. According to Section 5 of the Water Act, 2016, ownership of every water resources in the country is vested in and held by the national government in trust of the people of Kenya. Section 11 of the Act established the WRA, which is charged with functions (Section 12) and mandates through section 13 (2) b) to collect, analyze and disseminate information on water resources; (c) monitor compliance by water users with the conditions of permits and the requirements of the Act; (d) issue permits for inter-basin water

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transfer; and (e) delegate regulatory functions to the basin water to basin water resource committees provided for under section 25 of the Act.

3.1.7 National Sustainable Waste Management Bill, 2018

PART VII – Monitoring and Compliance Monitoring and Evaluation.

Section 20 (1) stipulates that NEMA, in collaboration with county governments, shall regularly monitor and review the performance of private entities and counties in carrying out their duties under this Act.

Section 20 (2), NEMA shall develop regulations governing the nature and procedure for reporting on performance by private entities,

Regulation 20 (3) provides that notwithstanding other provisions in the Bill, NEMA may, by notice in the Gazette require a private entity that is subject to The National Sustainable Waste Management Bill, 2018 to, at any time, prepare reports on the status of its performance of the waste management duties and prescribe the period for reporting;

1.1.8 The Occupational Safety and Health Act, 2007

Section 24 (5) requires that in order to develop needed information regarding potentially toxic substances or harmful physical agents, the director, may with the approval of the Minister, regulations requiring employers to measure, record, and make reports on the exposure of employees to substances or physical agents which may endanger the health or safety of employees and may by such regulations, establish such programmes of medical examinations and tests as may beneficiary for determining the incidence of occupational illnesses and the susceptibility of employees to such illness.

Section 24 (6) requires the Director to establish a safety and health institute to be known as the Occupational Safety and Health Institute to undertake research into all aspects of safety and health and to conduct safety and health skills training for occupational safety and health officers and other persons.

Medical surveillance.

Section103 (1), where the Minister is satisfied that—

a) cases of illness have occurred which he has reason to believe may be due to the nature of the process or other conditions of work;

b) by reason of changes in any process or in the substances used in any process or, by reason of the introduction of any new process or new substance for use in a process, there may be risk of injury to the health of a worker engaged in the process;

c) there may be risk of injury to the health of workers from any substance or material brought to the industries to be used or handled therein or from any change in the conditions in the industries, he may make regulations requiring such reasonable arrangements as may be specified in the regulations to be made for the medical surveillance and medical examination, not including medical treatment of a preventive character, of the persons or any class of persons employed.

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3.2 Global frameworks on environmental monitoring

Kenya is party to several multilateral environment agreements and frameworks that promote sound chemicals management including the Stockholm Convention on Persistent Organic Pollutants, The Rotterdam Convention on Prior and Informed Consent, the Basel Convention on trans-boundary movement of wastes, the Minamata Convention on Mercury, the Vienna Convention on Ozone Depleting Chemicals and Health and Environment Strategic alliance (HESA) among others. The Strategic Approach to International Chemicals Management requires countries to follow life cycle approach and put in place inter-sectoral mechanisms in addressing management of Chemicals in the environment.

The global environmental monitoring protocols are mainly coordinated by UNEP. The following are international documents that govern the monitoring of environmental pollutants:

The Stockholm Convention Article 11 of the convention encourages parties, including Kenya as a party, within their capabilities, to undertake appropriate research, development, monitoring and cooperation pertaining to persistent organic pollutants, their alternatives and candidate POPs. The activities include:

i) Sources and releases into the environment ii) Presence, levels and trends in humans and the environment iii) Environmental transport, fate and transformation iv) Effects on human health and the environment v) Socio-economic and cultural impacts; vi) Release reduction and/or elimination; and 13 vii) Harmonized methodologies for making inventories of generating sources and

analytical techniques for the measurement of releases

2. In undertaking action under paragraph 1, Kenya is encouraged to: a) Support and further develop, as appropriate, international programmes, networks and

organizations aimed at defining, conducting, assessing and financing research, data collection and monitoring, taking into account the need to minimize duplication of effort;

b) Support national and international efforts to strengthen national scientific and technical research capabilities, particularly in developing countries and countries with economies in transition, and to promote access to, and the exchange of, data and analyses;

c) Take into account the concerns and needs, particularly in the field of financial and technical resources, of developing countries and countries with economies in transition and cooperate in improving their capability to participate in the efforts referred to in sub-paragraphs (a) and (b);

d) Undertake research work geared towards alleviating the effects of persistent organic pollutants on reproductive health;

e) Make the results of their research, development and monitoring activities referred to in this paragraph accessible to the public on a timely and regular basis; and

f) Encourage and/or undertake cooperation with regard to storage and maintenance of information generated from research, development and monitoring.

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3.3.1 Global Monitoring Plan (GMP)

Article 16 of the Stockholm convention on effective evaluation established the basis of the GMP aimed at providing comparable environmental monitoring the UN regions. The GMP is focused on providing comparable monitoring data for the core matrices namely air, mothers’ milk/human blood and water (UNEP, 2018). Other matrices of national interest such as soil, sediment and fish and others are occasionally reported but are not monitored on regular basis and also not collected from hot spot areas.

3.3.2 Regional seas program

The programme was established in 1974 and included 140 coastal states focusing on elimination of consequences of environmental degradation and protection of marine environment.

3.3.3 Global plan of action (GPA)

It was established in 1995 with core mandate of monitoring marine environment from land based activities.

3.3.4 MARPOL international convention

This was established in 1973 is mandated to prevent marine pollution from ships due to oil spillage, sewerage, noxious substances garbage and harmful substances carried by ships.

6) Health and Environment Strategic alliance (HESA)

During the third inter-ministerial conference on Health and environment held in Libreville, Gabon in 2018 one of the topics discussed was the need for improved monitoring and evaluation systems to assess activities and impact of the implementation of actions.

3.3 National institutional frameworks and mandates on environmental management

3.3.1 National Environmental Authority (NEMA)

The National Environment Management Authority was established under Environmental Management and Coordination Act (EMCA), 1999 as the principal instrument of government charged with the implementation of all policies relating to the environment, and to exercise general supervision and coordination over all matters relating to the environment. In consultation with the lead agencies, NEMA is empowered to develop regulations, prescribe measures and standards and, issue guidelines for the management and conservation of natural resources and the environment. NEMA is also responsible to undertake and coordinate research, investigation and surveys, collect, collate and disseminate information on the findings of such research, investigations or surveys.

3.3.2 Water Resource Authority (WRA)

Under the Water ACT 2016, WRA is the responsible Authority collects all information on water resources, analyses, stores and disseminates it. This information is critical for water

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allocation, water resources investment decision making and modelling to enact scenarios to better understand the impact of climate change in future.

3.3.3 Kenya Bureau of Standards (KEBS)

KEBS is mandated by the Standards Act, Chapter 496 of the Laws of Kenya to provide comprehensive standards development, metrology, conformity assessment, training and certification services. With the re-establishment of the East African Community (EAC) and Common Market for Eastern and Southern Africa (COMESA), KEBS activities include participation in the development and implementation of SMCA activities at the regional level where it participates in the harmonization of standards, measurements and conformity assessment regimes for regional integration. It also provides testing of locally manufactured and imported commodities with a view to determining whether such commodities comply with the provisions of the Act or any other law dealing with standards of quality or description.

3.3.4 Government Chemist

The government Chemist Department is mandated to test all chemical samples on behalf of the government for the purpose of verifying the contents and quantities.

3.3.5 Directorate of occupational safety and health services (DOSHS)

The mandate of the Directorate is to ensure compliance with the provisions of the Occupational safety and health Act 2007 and promote safety and health of workers. The mission of the Directorate is to promote a safe and health workplace by implementing effective systems for the prevention of Occupational diseases, ill health accidents and damage to property in order to reduce the cost of production and improve productivity in all sectors of our economic activities. Among others, the core functions DOSHS include monitoring of workplace pollutants for purposes of their control.

3.3.6 Kenya Plant Health and Inspectorate Services (KEPHIS)

KEPHIS is the organisation mandated to monitor the presence and levels of pollutants in plants that are imported into and exported out of the country.

3.3.7 The Pests Control Product Board (PCPB)

The Pest Control Products Board is a Statutory organization of Kenya Government established under an Act of parliament, the Pest Control Products Act, Cap 346, Laws of Kenya of 1982 to regulate the importation and exportation, manufacture, distribution and exportation, manufacture, distribution and use of pest control products. PCPB is mandated to monitor quality of pesticides within the distribution chain and regulate volumes of importation of pesticides regulated under international conventions e.g. Rotterdam, Basel and Stockholm Conventions.

3.3.8 Kenya marine and fisheries research institute (KMFRI)

Kenya Marine and Fisheries Research Institute is a State Corporation established in 1979 by the Science and Technology Act, Cap 250 of the Laws of Kenya, which has since been repealed by the Science, Technology and Innovation Act No. 28 of 2013. Under section 56,

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fourth schedule, KMFRI is mandated to undertake research in marine and freshwater fisheries, aquaculture, environmental and ecological studies, and marine research including chemical and physical oceanography, in order to provide scientific data and information for sustainable development of the Blue Economy.

3.3.9 Universities

The universities are mandated under the Universities Act 2012 to conduct research and training of personnel for the country. Several research activities in environment related field contribute towards monitoring data on priority chemicals in all the three media.

3.4 Institution Analytical capacities

A summary of analytical capacities and estimated cost of analysis for different groups of POPs in the national institutions is provided in Tables 3.1-3.4. The assessment revealed that there are many national regulatory and academic institutions that have analytical instruments and can contribute towards the implementation of the chemicals monitoring programme. The key analytical instruments in the institutions include gas chromatograph coupled to mass selective detector (GC/MS), gas chromatograph coupled to electron capture detector (GC-ECD) and liquid chromatograph coupled to a mass selective detector (LC/MS) for POPs analysis and Atomic absorption spectrometer (AAS), Inductively Coupled plasma mass spectrometer (ICPMS) and X-ray Fluorescence (XRF) for heavy metals analysis (Table 3.1).

Institutions in the country operate under different legislative frameworks that guide their mandates. Hence whereas they may have analytical capacity for POPs analysis, they may not necessarily conduct these tests if they do not fall under the institutions core mandate. Consequently, proper coordination and institutional arrangements need to be established to enables these institutions to contribute towards national chemicals monitoring activities. In addition, several institutions whose core mandates involve monitoring of hazardous chemicals in air, water and soil do not have adequate technical and human capacities to carry out sampling and analysis of POPs in these media.

Table 3.2 below shows an overview of the technical and analytical capacities of selected laboratories in the country as captured in the laboratory operational capacity assessment questionnaire. Beside the availability of the analytical instruments, other aspects assessed included the laboratory personnel and qualification, staff training, analytical methods applied, sample matrices analysed, analytical parameters, QA&QC among other technical issues.

Table 3.3 shows the key analytical methods used in extraction of POPs from different media. Methods differ from one laboratory to the other. QuEChERS and liquid/liquid extractions are the main methods for liquid media, while Soxhlet is widely employed for extraction of POPs in solid samples. Table 3.4 summarises the estimated cost of analysis for different POPs groups, varying from KSh. 15,000 to KSh. 30,000 per sample for OCPs and PCBs, and from KSh. 500 to KSh. 2000 per parameter for heavy metals analysis.

Some of the impediments experienced in routine analysis include lack of adequate funding, limited training activities, difficulties to access spare parts, lack of analytical standards, irregular supply of laboratory consumables, and lack of equipment and sampling tools for air matrices. These limitations should be considered while building technical and human resource capacity to ensure that staff are adequately trained and equipped with the necessary competency and hands on experience to carry out the POPs analysis.

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Table 3.1 Analytical capacities in research, monitoring and regulatory institutions

Region Institution Available equipment OCPs PCBs PBDEs Dioxins/ Furans

PFAS

1 Western Kenya

Masinde Muliro University of Science and Technology

GC-ECD, GC-MS √ √ √ x x

2 Nyanza Maseno University GC-ECD √ √ x x x LVEMP GC-ECD, HPLC √ √ x x x 3 Rift Valley Egerton University GC-ECD √ √ x x x Moi University GC-ECD, GC-MS √ √ x x x 4 Nairobi University of Nairobi GC-ECD, GC-MS, XRF,

LCMS √ √ √ x x

PCPB HPLC, GC-ECD √ √ x x x KEBS GC-ECD, GC-MS, HPLC √ √ √ x x KRA GC-ECD, HPLC, GC-MS √ √ √ x x Gov Chemist Dept. GC-ECD, HPLC, GC-MS √ √ √ x x KEPHIS GC-ECD, HRGC-MS, HPLC √ √ √ √ x WRA GC-MS, GC, AAS √ √ √ x x Vet Lab GC-MS, LCMS, ICPMS, √ √ √ x x 5 Central JKUAT GC-MS, LCMS √ √ √ x x Kenyatta University LC-MS, HPLC √ √ x x x 6 Coast KMFRI GC-ECD √ √ x x x SGS (Private) GC-ECD, GC-MS, GC-

OMS, HPLC, FTRIS √ √ √ √ x

Table 3.2 Laboratory operational assessment

Organisation Kenya Plant Health Inspectorate Service

Central Water Testing Laboratories (WRA)

Chemistry Department University of Nairobi

Government Chemists Department

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(KEPHIS) Address 49592-00100,

NAIROBI, KENYA

P.O. BOX 45250-00100

P. O. Box 30197 – 00100, Nairobi

P. O. Box 20753 - 00202 Nairobi

Email kephisinfor@kephis.org

Centralwatertestinglabs@gmail.com

dept-chem@uonbi.ac.ke

gchemist@interior.go.ke

Website https://www.kephis.org/

https://wra.go.ke/

https://chemistry.uonbi.ac.ke/

www.govchemists.go.ke

Main activity of the laboratory Pesticide residues and mycotoxins in agricultural produce.

Water& wastewater

Research and training

Foods, drugs, water, waste-waters, leachets and sediments

Main source of funding Fees & Gov funding

Research projects

Fees & Gov funding

Number of samplers of POPs & other chemicals analysed /year 91 4000 2,000 614 Does the Laboratory have QA/QC Yes Yes Yes Yes Does laboratory use standard or Own in house method yes Yes Yes Yes Does the laboratory apply blank tests Yes Yes Yes Yes Does the laboratory carry out recovery tests Yes No Yes Yes Does the laboratory carry out performance tests of instrument? Yes Yes Yes Yes Does the laboratory use certified reference materials Yes Yes Yes Yes Does the laboratory participate in inter-laboratory proficient studies

Yes Yes Yes Yes

Does the laboratory use written instructions and methods Yes Yes Yes Yes Does the laboratory apply routine documentation Yes Yes Yes Yes Commission projects? Yes Not clear Yes Yes Does the laboratory have register of equipment? Yes Yes Yes Yes Does laboratory have register of samples? Yes Yes Yes Yes Does laboratory have register of analytical work done? Yes Yes Yes Yes

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Are analytical issues documents? Yes Yes Yes Yes Is there reporting and data storage systems? Yes Yes Yes Yes Does laboratory have operational costs? Yes Not clear Yes Yes Are there validation and performance reports? Yes Yes Yes Yes How are documents filed? Reports Yes Yes Yes Is there a LIMS? In progress Yes No No Is the laboratory space shared with other activities? No Yes No No Is there protection from external disturbance? Yes Yes Yes No Is the space adequate? Yes Yes Yes Yes Are there hoods? Yes Need

improvement Yes Yes

Are materials free from contaminants? - Yes Yes Yes Is there sample storage facilities? Yes Yes Yes Yes Is there chemical storage facilities? Yes Yes Yes Yes Is the laboratory safety regulation protocol? Yes Yes Yes Yes Is access to the laboratory regulated? Yes Yes Yes Yes Is there framework waste management? Yes Yes Yes Yes Is the personnel familiar with QA&QC Yes Not adequate Yes Yes Is there routine training of the personnel? Yes No No No Is there specific qualification requirement for the personnel? Yes Yes Yes Yes Is there documentation of the qualification of the personnel? Yes Yes Yes Yes Is the personnel adequate? Yes No No No Is there equipment for POPs analysis? Yes Yes Yes Yes Is there clean-up equipment for POPs? Yes Yes Yes Yes Equipment GC/MS

LC/MS ICP/MS AAS ICPOES

GC/MS AAS GFAAS

Yes GC/MS, GC/ECD AAS

Are there plans to buy new equipment for POPs analysis Yes Yes Yes Yes Is there route servicing of equipment? Yes Yes Yes Yes

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Does the laboratory experience difficulties with supply of spare parts?

Yes Yes Yes Yes

Is there urgent need for spare parts? No Yes Yes No Scope for POPs analysis methods Food Yes All media Yes Scope for POPs parameters analysed POPs in food Yes OCPs, PCBs,

PBDEs Yes

Frequency of training in the last 2 years 20% Vary Once 4 times Number and qualifications of personnel 26 technical Not clear 5 PhD, 2 MSc. Yes Matrices cover Plant, soil,

sediment, animal tissue

Yes Soil, water, air, fish, sediments, vegetables,

Sediments, liquids, biota

POPs and other chemicals analysed OCPs, PCBs, Furans

No OCP, PCB, PBDEs, PAHs, Pesticides, Metals, nutrients

Pesticides

Does the laboratory participate in monitoring activities? No No Yes No Does laboratory have any monitoring stations/sites? No 550 sites/water Yes No

Table 3.3 Methods used of extraction for POPs in different matrices

Analytes Kenya Plant Health Inspectorate Service (KEPHIS)

Central Water Testing Laboratories (WRA)

Chemistry Department University of Nairobi

Government Chemists Department

Abiotic – ambient air - - - Soxhlet - Stake emission - - Abiotic - water OCPs, PCBs QuEChERS

(Liquid-liquid) - L/L L/L

Abiotic – other: soil, sediments, food stuff,

OCPs, PCBs QuEChERS ( - Soxhlet -

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Biota - human milk - - Soxhlet - Biota – other: Fish, vegetables OCPs, PCBs Organic phase - Soxhlet -

Table 3.4 Estimated cost of analysis for different POPs groups and other pollutants

Matrix Parameter Kenya Plant Health Inspectorate Service (KEPHIS)

Central Water Testing Laboratories (WRA)

Chemistry Department University of Nairobi

Government Chemists Department

Abiotic– ambient air OCPs, PCBs - - 20,000/sample - -Stake emission - - - - Abiotic – Surface water OCPs, PCBs 21,500/sample 15,000-

30,000/sample 20,000/sample 1,500/parameter/

sample Abiotic – other: soil, sediments, food stuff,

OCPs, PCBs 21,500 - 20,000/sample -

Biota - human milk OCPs, PCBs - - 20,000/sample - Biota – other: Fish, vegetables OCPs, PCBs 21,500 - 20,000/sample - Abiotic – Surface water Metals 2000/Element 700/parameter/sam

ple 500-2000/ parameter /sample

The indicated cost is in Kenya Shillings (1 USD ≈ KSh. 100)

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Qualification of at least a bachelor degree in Chemistry or preferably analytical discipline will be necessary to for the analyst to understand the technical concepts in the POPs analysis. It was noted that several institutions such as WRA, although they have recently acquired the GC-MS/ECD/FPD that adequate to analyse OCPs, PCBs and PBDEs, they may not have adequate experience in POPs analysis and should be included in regular POPs analysis training to build the needed competency in this field. Therefore, further training is necessary for the analysts to acquire more skills to exploit all the capabilities of the instrument. Provision of laboratory consumable in terms of chemicals and reagents, internal & external standards, sample preparation materials equipment and spare parts are also missing or not adequate in several laboratories. Hence there is a need to provide a dedicated budget to ensure sustainable supply of laboratory consumables to overcome the challenge.

3.5 Existing Monitoring programmes where Kenya participates

As of December 2020, Kenya did not have a nationally driven chemicals monitoring programme for hazardous chemicals such as POPs and other chemicals in hot spot sites with an established consistent sampling and reporting framework. However, the country has participated in international monitoring programmes focussing on remote sites. This section provides an overview of the monitoring programmes and research activities focusing on chemicals monitoring in the country.

3.5.1 The Global Monitoring Plan

The objective of the POPs Global Monitoring Plan Provide a harmonized organizational framework for the collection of comparable monitoring data on the presence of the POPs listed in Annexes A, B and C of the Convention in order to identify trends in levels over time as well as to provide information on their regional and global environmental transport. GMP focuses on monitoring POPs levels in core matrices namely ambient air, mothers’ milk/human blood, and water from remote sites. Kenya participates in the Global monitoring plan. The monitoring site for ambient air Mt. Kenya and Kabete and Chiromo. The site for water is Sabaki River mouth and Athi River for Sabaki River mouth for PFOS monitoring. Data from the sites is reported through the Africa POPs monitoring report. Table 3.2 gives a summary of the existing monitoring sites in the country and analytical parameters covered.

The chemicals covered under the GMP sampling sites in ambient air include POPs pesticides, PCBs, PBDEs, Dioxins/furans and PFOS. In addition to ambient air and water sampling, Kenya has participated in two rounds of sampling of mothers’ milk survey. The sampling activities are coordinated by the University of Nairobi. Figure 3.1 shows a photo of sampling Kabete sampling site.

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Figure 3.1 Photo of Passive samplers for POPs at Kabete Site

3.5.2 Global Atmosphere Watch (GAW)

GAW is a programme of the world meteorological organisation (WMO) which focuses on building global understanding of atmospheric composition, its change, and interactions between the atmosphere, the oceans and the biosphere, variability and trends in atmospheric composition and related physical parameters, and assessment of related consequences at global scale. It provides scientific information for national and international policymakers, supports international conventions on stratospheric ozone depletions and monitors climate change and long-range trans-boundary air pollution.

Kenya hosts one of the GAW monitoring site on Mt. Kenya GAW station. Changes in Earth's atmospheric composition are a serious cause of concern for humanity as they impact weather and climate, human and ecosystem health, water supply and quality, agricultural production, and many socio-economic sectors. The areas of study include:

i) climate change associated with increasing amounts of greenhouse gases, especially

carbon dioxide; ii) the ozone hole associated which is associated with depletion of the protective

stratospheric ozone layer due to chlorofluorocarbons (CFCs) and halons increasing ultraviolet radiation, which in turn increases incidences of skin cancer and other diseases;

iii) urban air pollution, especially fine particles that affect human health.

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Figure 3.2 below shows the overview of GAW Chemicals monitoring network activities (GAW, 2020).

(Source: GAW, 2020)

Figure.3.2 Overview of GAW monitoring Programme.

Figure 3.3 shows a photo of GAW sampling site located on Mt. Kenya.

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Figure 3.3 shows a photo of GAW sampling site located on Mt. Kenya.

Equatorial Africa Deposition Network (EADN)

The goal of atmospheric deposition measurements is to quantify the nutrient deposition in the African great lakes, understand the underlying mechanisms leading the eutrophication within the African lakes and propose solution to improve land use practices and protect the African international waters. EADN project has established the first state of the art atmospheric deposition monitoring stations in the Sub-Sahara Africa region. The Stations are currently operational, one in Rusinga Island in Lake Victoria, the Second superstation is in Senga Bay in Malawi and represents the Southern region, and the third Station is located in Lamto in Ivory Coast representing the deposition of nutrients in West African countries capturing the data for the wet Savana. A sample sites under the monitoring project is shown in Figure 3.4 below.

Figure 3.4 Atmospheric Deposition measurements station

The main chemical parameters monitored include nutrients consisting of anions (sulphates, nitrates, phosphates, chlorides, fluorides, nitrites) and cations (potassium, calcium, sodium, magnesium). The EADN network central laboratory at the University of Nairobi participates in the GAW/WMO inter-laboratory proficiency studies as part of the external quality control. The summary of existing international and national programmes on chemicals monitoring is shown in Table 3.5 below.

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Table 3.5 Existing Monitoring activities

Institution Programme Sites GPS Locations

Altitude Matrix

Parameters analysed Monitoring Period

Scope

Department of Chemistry, UON

MONET Africa POPs Monitoring

Mt. Kenya 0°3′S, 37°18′E Air OCPs, PCBs, PBDEs, Dioxins/Furans, PFOS,

2008 to date International

Department of Chemistry, UON

MONET Africa POPs Monitoring

Chiromo Campus

36°57'511'' E 01o 26' 694 S

1506 m Air OCPs, PCBs, PBDEs, Dioxins/Furans, PFOS,

2017-2018 International

Department of Chemistry, UON

UNEP/GEF POPs Monitoring

Kabete 36° 44' 33" E 1° 14' 58" S

1841 m Air OCPs, PCBs, PBDEs, Dioxins/Furans, PFOS,

2017-2018 International

Department of Chemistry, UON

UNEP/GEF POPs Monitoring

Sabaki River Mouth

40°07’50.0 E, 03°09’41.0 S

0 m Water PFOS 2017-2018 International

Kenya Meteorology Department

Global Atmospheric Watch (GAW)

Mt. Kenya 0°3′S, 37°18′E 3897 m Air Ozone, greenhouse gases 1993-to date International

Department of Chemistry, UON

Equatorial Deposition Network

Rusinga Island

00, 24.147 S 34, 08.866 E

1160 m Air Nutrients (N, P) 2017-2019 International

Ministry of Environment & Forestry

LVEMP Lake Victoria Catchment

Variant Variant Water Nutrients National National

KEMFRI National Indian Ocean

Variant 0 m Water Metals, pesticides - National

NEMA Mobile emissions Mobile emissions

Variant Variant Air PM, SOX, NOX, - National

PCPB National Pesticide Variant variant Pesticides

Pesticides - National

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4. ENVIRONMENTAL MONITORING AND ANALYTICAL

PARAMETERS

Environmental management constitute three main steps which include 1) measurement and observation to describe both the current state of the environment and any changes occurring; 2) evaluation and analysis of environmental data to determine extent and impact of the changes and associated risks; 3) developing warning systems based on predetermined standards to alert the society to change. Environmental monitoring addresses the first activity by implementing scientifically planned measurement and observations and also partly includes the second action of evaluation of data collected to formulate policy decisions.

Environmental monitoring constitutes a series of measurements of defined variables for a specified purpose following a predetermined schedule in time. Depending on the technique, monitoring can be categorised into process monitoring, emission monitoring, ambient monitoring, exposure monitoring, and biological monitoring as summarised in Table 4.1. Monitoring schemes may differ greatly in their extent in space and time-from a small area around an emission source, a continuous measurement to global monitoring programmes. Relevant sampling and analytical techniques are selected depending on the nature of analytes such as organic and inorganic pollutants.

Table 4.1 Types of Chemical monitoring

Type of monitoring

Level of assessment Consequence

1 Process monitoring

Used to measure pollutants sources e.g. to test control technologies applied before hazardous chemicals are released to the environment.

Control Technology

2 Emission monitoring

Used to measure pollutant emissions to determine the output of ecologically active compounds related to specific processes or process parameters.

Control strategies

3 Environmental monitoring

Measure pollutants ambient concentrations of in environment such as air, water soil.

Legislation/regulations

4 Exposure monitoring

Measure pollutant impacts on health or ecological systems and socioeconomic activities. Measure chemical exposure assessment method involving the analysis of blood, urine, hair or exhaled breath samples from workers, for a hazardous substance or its metabolites (breakdown products in the body). It can be used as part of an overall strategy for controlling hazardous chemicals within the workplace, by reducing uncertainty in relation to the effectiveness of control measures in place (e.g. engineering control measures or PPE) and by monitoring work practices.

Legislation/regulations

Environmental monitoring is one of the main tools of environmental management and assessment together with emissions inventories and exposure assessment Figure 4.1. These tools contribute to Sound Chemicals management and life cycles assessment by detecting

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releases and accumulation of hazardous chemicals in the environmental media. Environmental monitoring brings to understanding the health of the environment in relation to the socio-economic activities within the country. In addition, it allows usage of cost-efficient methods and identifying possibilities for maximizing the cost-efficiency of the monitoring activities as key to ensuring sustainability of implementation. This protocol takes note of the existing monitoring programmes and seeks to integrate and extend the monitoring and assessment needs to build on existing capacities.

Figure 4.1 Overall framework of environmental effect on ecosystem and health

4.1 The objectives of Chemicals monitoring programme

i) To provide information about the substances being emitted to the environment, their quantities and sources;

ii) To determine the distribution and transformation of chemicals in the environment; iii) To determine changes in environmental conditions with time; iv) To provide a sound basis for the development of standards, regulations, and other

legal requirements relating to the protection of human health and the environment; v) To determine how well regulatory measures are being met; vi) To provide harmonised information about the monitoring techniques; vii) To provide scientific data that guides the development of appropriate environmental

pollution management strategies on county by county basis; viii) To ensure reliable and inter-comparative monitoring data across the country.

4.2 Cost efficiency and socioeconomic principles

To ensure cost efficiency and socioeconomic benefits in monitoring activities the following principles are considered:

i) prioritization of the most significant risks and to respond to assessment/management needs, taking into consideration the common indicators;

ii) Consider scientific credibility, practical monitoring and data requirements and policy/social relevance of criteria and indicators for measures / pressures as they directly link back to the management element;

iii) Promoting innovative and efficient ways of doing the monitoring;

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iv) Encouraging cooperation as a potential cost-efficient execution of the monitoring programmes to contribute to cost-efficiency by offering data relevant to national and regional uses in support of ecosystem management;

v) Build on existing monitoring activities such as existing monitoring stations, actions carried out and on the use of existing resources by improving the efficiency and coverage of existing programmes.

vi) Encourage monitoring by industry of the environmental effects of their activities through Environmental Impact Assessments and Annual Environmental Audits.

4.3 Generals principles for selection of chemical monitoring parameters

Selection process for chemicals to be monitored is influenced by the monitoring objectives and include:

i) Cause high risk to human health and/or environment; ii) Have the potential to exhibit changes in excess of limits of detection; iii) Be directly related to a testable hypothesis; iv) Be known or measurable above natural variability or background levels; v) Give information from which management decisions can be made; vi) Be able to sustain the monitoring activity; vii) Be able to be sampled within logistical and time constraints; viii) Be measurable on samples that can be transported without deterioration or be

measurable on-site in the field; ix) Be amenable to quality assurance procedures including demonstrable precision,

accuracy and reproducibility. x) Be measurable by cost effective, simple and standard procedures (if the procedures

are non-standard inter-calibrations are essential); xi) Be strongly related by what is believed to be a causal link to a particular activity or

process; xii) Be a direct measure of change in a value of concern; xiii) Permit generalisations about causative agents; xiv) Be definable in terms of limits beyond which changes are judged to be deleterious; xv) Be measurable without conflicting with scientific activities.

4.4 Analytical parameters

Selection of analytical parameter is an important component of the monitoring programme. The analytical parameters proposed in this monitoring protocol are based on the priority list of chemicals that are in different national regulations and international frameworks that Kenya is party to. Table 4.2 shows POPs compounds provided under the Stockholm Convention.

Table 4.2 POPs Analytical parameters

POP Acronym Parent compound1 Initial 12 POPs Aldrin Single compound Chlordane 2 isomers Dichlorodiphenyltrichloroethane DDT 2 isomers Dieldrin Single compound

1Theoretical number of congeners or structural isomers within this chemicals’ group

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POP Acronym Parent compound1 Endrin Single compound Hexachlorobenzene HCB Single compound Heptachlor Single compound Mirex Single compound Polychlorinated biphenyls PCB 209 congeners Polychlorinated dibenzo-p-dioxins PCDD 75 congeners Polychlorinated dibenzofurans PCDF 135 congeners Toxaphene Technical mixtures of chlorinated bornanes

and chlorinated camphenes (about 16,000 congeners or isomers)

POPs listed at COP-4 Chlordecone Single compound alpha-Hexachlorocyclohexane a-HCH Single compound; isomer to b-HCH and g-

HCH beta-Hexachlorocyclohexane b-HCH Single compound; isomer to a-HCH and g-

HCH Lindane, gamma-Hexachlorocyclohexane

g-HCH Single compound; isomer to a-HCH and b-HCH

Hexabromobiphenyl HBB 42 isomers in one homolog group Pentachlorobenzene PeCBz Single compound Tetrabromodiphenyl ether and pentabromodiphenyl ether (commercial pentabromodiphenyl ether)

c-penta BDE

Two homolog groups: 42 tetrabrominated isomers 46 pentabrominated isomers

Hexabromodiphenyl ether and heptabromodiphenyl ether (commercial octabromodiphenyl ether)

c-octa BDE

Two homolog groups: 42 hexabrominated isomers 24 heptabrominated isomers

Perfluorooctane sulfonic acid PFOS Single anionic compound with one linear (L-PFOS) and many branched isomers

POPs listed at COP-5 Endosulfan Single compound; mixture of stereoisomers POPs listed at COP-6

4.5 Recommended POPs for National Monitoring

The list of POPs chemicals is broad and complex and collaborative effort is needed among the laboratory to handle analysed depending on available capacities. To achieve comparability to GMP, the list of POPs to be monitored will be limited to those recommended under the GMP guidance document. Hence the list of individual POP compounds to be monitored will be adapted and updated according to the POPs analytes recommended in the GMP guidance document (UNEP, 2020). The summary of the compounds under GMP is shown in Tables 4. 3-4.4 below.

Due to national interest to monitor pollutions in the three major environmental media namely soil, water and air. The analytical matrices water and soil have been all included in the Table for POPs monitoring.

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Table 4.3 Initial POPs compounds

Compounds to be Monitored

Initial POPs Air Human Milk Soil Water

Aldrin Aldrin Aldrin Aldrin Aldrin

Chlordane cis- and trans-chlordane; and cis- and trans-nonachlor, oxychlordane

cis- and trans-chlordane; and cis- and trans-nonachlor, oxychlordane

cis- and trans-chlordane; and cis- and trans-nonachlor, oxychlordane

cis- and trans-chlordane; and cis- and trans-nonachlor, oxychlordane

DDT 4,4’-DDT, 2,4’-DDT and 4,4’-DDE, 2,4’-DDE, 4,4’-DDD, 2,4’-DDD

4,4’-DDT, 2,4’-DDT and 4,4’-DDE, 2,4’-DDE, 4,4’-DDD, 2,4’-DDD

4,4’-DDT, 2,4’-DDT and 4,4’-DDE, 2,4’-DDE, 4,4’-DDD, 2,4’-DDD

4,4’-DDT, 2,4’-DDT and 4,4’-DDE, 2,4’-DDE, 4,4’-DDD, 2,4’-DDD

Dieldrin Dieldrin Dieldrin Dieldrin Dieldrin

Endrin Endrin Endrin Endrin Endrin

HCB HCB HCB HCB HCB

Heptachlor Heptachlor and heptachlorepoxide

Heptachlor and heptachlorepoxide

Heptachlor and heptachlorepoxide

Heptachlor and heptachlorepoxide

Mirex Mirex Mirex Mirex Mirex

PCB ΣPCB6 (6 congeners): 28, 52, 101, 138, 153, and 180

ΣPCB6 (6 congeners): 28, 52, 101, 138, 153, and 180

ΣPCB6 (6 congeners): 28, 52, 101, 138, 153, and 180

ΣPCB6 (6 congeners): 28, 52, 101, 138, 153, and 180

PCB with TEFs* (12 congeners): 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, and 189

PCB with TEFs* (12 congeners): 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, and 189

PCB with TEFs* (12 congeners): 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, and 189

PCB with TEFs* (12 congeners): 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, and 189

PCDD/PCDF 2,3,7,8-substituted PCD/PCDF (17 congeners)

2,3,7,8-substituted PCD/PCDF (17 congeners)

2,3,7,8-substituted PCD/PCDF (17 congeners)

Toxaphene Congeners P26, P50, P62 Congeners P26, P50, P62 Congeners P26, P50, P62

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Table 4.4 POPs listed at COP-4 and 5

POPs listed at COP-4

Air Human Milk Human Blood Water

Chlordecone Chlordecone Chlordecone Chlordecone Chlordecone

-HCH -HCH -HCH -HCH -HCH

-HCH -HCH -HCH -HCH -HCH

-HCH -HCH -HCH -HCH -HCH

Hexabromobiphenyl PBB 153 PBB 153 PBB 153 PBB 153

Pentachlorobenzene PeCBz PeCBz PeCBz PeCBz

c-penta BDE BDE 47, 99, 153, 154, 175/183 (co-eluting) Optional: BDE 17, 28, 100

BDE 47, 99, 153, 154, 175/183 (co-eluting) Optional: BDE 100

BDE 47, 99, 153, 154, 175/183 (co-eluting) Optional: BDE 100

BDE 47, 99, 153, 154, 175/183 (co-eluting) Optional: BDE 100

c-octa BDE

PFOS PFOS, NMeFOSA, NEtFOSA, NMeFOSE, NEtFOSE (linear and sum of PFOS)

PFOS (linear and sum of PFOS)

PFOS (linear and sum of PFOS)

PFOS (linear and sum of PFOS)

POPs listed at COP-5

Endosulfan α-, β-endosulfan; and endosulfan sulfate

α-, β-endosulfan; and endosulfan sulfate

α-, β-endosulfan; and endosulfan sulfate

POPs listed at COP-6

HBCD -HBCD, -HBCD, -HBCD

-HBCD, -HBCD, -HBCD

-HBCD, -HBCD, -HBCD

-HBCD, -HBCD, -HBCD

Candidate POPs under review (status 2014)

Air Human Milk Human Blood Water

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Polychlorinated naphthalenes (di-, tri-, tetra-, penta-, hexa-, hepta-, and octachlorinated naphthalenes)

TBD TBD TBD TBD

Dicofol TBD TBD TBD TBD

HCBD TBD TBD TBD TBD

PCP and its salts and esters TBD TBD TBD TBD

SCCP (C10-C13) alkanes TBD TBD TBD TBD

Hexabromocyclododecane HBCD 3 structural isomers

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4.6 Geographical scale of monitoring sites

The geographic scale of monitoring for the assessment of contaminants and their effects depends on the specific conditions of an area that influence the background concentration of contaminants at national, regional and county levels Figure 4.2. The risk based approach should be used in order to follow a screening procedure to decide the sites to be assessed and monitored more frequently. The areas where greater pollution pressure occurs could be divided into smaller areas for assessment purposes and could be monitored more frequently than remote and non-affected sites or media.

Figure 4.2 Geographical scale of monitoring

4.7 Monitoring frequency

Monitoring frequencies is determined by the purpose of the sampling effort and range from shorter time scales for seasonally variable input, to large time scales. For trend determination the timescales are influenced by the ability to detect trends, considering the variability in the whole analytical process and the number of replicates. It is possible to decrease the monitoring frequency in cases where established time series show concentrations well below levels of concern, and without any upward trend over a number of years. The recommended monitoring frequencies for air, water and soil are provided under respective matrices in Chapters 5, 6 and 7, respectively.

4.8 Choosing relevant indicators

An indicator is defined as: signs or symptoms of changes due to numerous influencing factors. It is important that the chosen indicators can be readily measured and are achievable within the available resources. Examples of widely applied measurable indicators for changes in different environmental segments are listed in the Table 4.5 below.

Table 4.5 Quick measureable indicators of environmental change

Environmental media Quick measurable indicators Air quality SO2, particulates

Soil quality Erosion (e.g. footpaths), metals, TPH, PAH

Sea water quality TSS, DO, BOD, COD, pH, conductivity

Fresh water quality TSS, DO, BOD, COD, pH, conductivity

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Snow and ice quality Metals, TPH, particulates

Vegetation quality Spatial extent, metals

Wildlife health Population size, breeding success

Fuel handling Amount consumed, number of spills, size and location of spills

Aircraft/vehicle operations

Distance travelled, number of landings, fuel consumed

Solid and liquid waste Waste types (including hazard), volume / weight

Waste water TSS, DO, BOD, COD, pH, conductivity, faecal coliforms, volume

Field activities Number of person days in field, location of field camps

Introduced organisms Species, distribution, population size

EIA/permit compliance Number of breaches recorded

4.9 Sampling methods and statistical design

The goal of sampling is to collect samples that are representative of the matrix under investigation. When collecting samples, one must follow predetermined sampling procedures and methods which have been chosen consideration the sampling site, the number of samples to be collected, and timing of the sampling to meet the purpose of the monitoring survey for the media being investigated.

The basic tenets that need to be followed for the statistical design of monitoring programmes include:

1) A clear question. The thought process include: question > hypothesis > indicators >

parameters > model > statistics and tests of hypothesis > interpretation. 2) Controls. These should be both spatial and temporal where appropriate. 3) A balanced design, e.g. the same number of replicate samples at each time and place. 4) Replicates randomly allocated. 5) Conduct preliminary sampling or pilot study in order to do the following (6 – 9): 6) Assess the sampling methods to ensure they are efficient and do not introduce bias

into the study. Adequate quality assurance must be applied from initial sample collection, through transport to the laboratory, and during the analysis.

7) Estimate the error variability and necessary sampling effort to achieve the desired power.

8) Determine natural environmental patterns to be incorporated into the study design (e.g. stratification).

9) If statistical analysis assumptions are not satisfied, then transform variable before analysis, use non-parametric methods or use simulation or randomisation methods.

10) Prior agreement on how to handle sensitive data.

In 2017, the workshop of key stakeholders held at Kyaka hotel in Machakos identified monitoring sites for baseline survey of POPs in air, water and soil are shown in Table 4.6.

Table 4.6. Identified monitoring sites for baseline survey

Air Water Soil Nairobi Dandora Fourteen falls Dandora

Kikuyu*Steel industry Ngong River(Njiru) Nairobi River (Njiru) Mbagathi River (Downstream EPZ)

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Kitengela*/sheep and goats project

Kitengela/sheep and goats project

ECCL* (Stone Athi)

ECCL old area* ECCL old area*

Babandogo*

Ngong Hills –baseline (Mwai) Athi River industries(Mwai)

KNH

Mombass Kibarani Kibarani Kibarani

Coast RH Sabaki Estuary Mwakinunge

Mazeras Mkurumzi River/Downstram TIOMIN

Bamburi

Nakuru Gioto dumpsite Final effluent into Lake Nakuru

Gioto dumpsite

Nakuru CBD Lake Naivasha/town side Naivasha farming area

Nakuru RH Lake Naivasha/flower side

Nakuru farming area

River Njoro

Kisumu Nyalenda /LVEMP Lake Victoria Nyalenda/LVEMP

Kachoki dumpsite Kisati Kachoki

KEMRI incinerator Nyando River

Kisumu referal hospital R. Nzoia/Webuye R. Nzoia/Midway R. Nzoia/Mouth

Webuye

4.10 Environmental monitoring targets

Good monitoring programme should set high levels management targets for environmental protection and management. Good environmental status is the priority for setting the high-level goal that the need to achieve. These include: Ecologically diverse and dynamic systems which are clean, healthy and productive; Sustainable use of environmental resources: ensure ecosystems which function fully

and maintain their resilience to human-induced environmental change; Protection of species and habitats; Prevention of human-induced decline in biodiversity; Diverse biological components which function in balance; Hydro-morphological, physical and chemical properties of the ecosystems, including

those properties which result from human activities, which support the ecosystems; Anthropogenic inputs of substances and energy, including noise, do not cause

pollution effects.

4.11 Quality Assurance and Quality Control

The accuracy and comparability of the data collected is a key requirement for status assessment and description and for the assessment of anthropogenic influences and required measures. Quality assurance (QA) and quality control (QC) measures ensure that monitoring results of stated quality are obtained across the country. QA/QC should provide confidence in

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the whole analytical process, from sampling to reporting, for all monitoring parameters, from monitoring at national, sub-regional as well as at Regional scale.

Monitoring should provide data, which are representative of the location and time of sampling. For temporal trend monitoring in particular, it is important to perform reliable and reproducible high-quality analyses over decades. Therefore, such analyses require well-documented procedures and experienced analysts. Whereas QA/QC seems to be limited to methods and technical specifications, it is important for the whole monitoring chain: from defining targets to achieve, related indicators and parameters in order to determine the monitoring requirements to designing and performing the monitoring programme in order to collect and assess the monitoring data. The monitoring data should enable meaningful assessment of status in time and space.

Generally, this begins with an assessment of the existing monitoring programme, an iterative process to allow further modification and revision of the monitoring programme. Exchange of best practices, inter-calibration and harmonisation activities enhance the process and highlight any deficiencies and inadequacies. This will result in comparable monitoring approaches based on commonly agreed monitoring principles.

QA and QC also apply to data storage and exchange. This includes common data management standards and technical and semantic interoperability between data management systems.

Cooperate in carrying out monitoring activities and submission of the resulting data Comply with quality assurance prescriptions and participate in inter calibration

exercises. Use and develop jointly other duly validated scientific assessment tools, such as

modeling, remote sensing and progressive risk assessment strategies. Promote joint research which is considered necessary to assess the quality of the

environment, and to increase knowledge of the relationship between inputs, concentration and effects.

Take into account scientific progress which is considered to be useful for such assessment purposes and which has been made elsewhere.

Implement collaborative monitoring and assessment-related research, draw up codes of practice for the guidance of participants to approve the presentation and interpretation of their results.

Carry out assessments taking into account the results of relevant monitoring and research and the data relating to inputs of substances or energy into the maritime area which are provided.

Seek the advice or services of competent national organizations and competent bodies with a view to incorporating the latest results of scientific research.

Cooperate with competent national organizations and other competent international organizations in carrying out quality status assessments.

4.12 Data Assessment

When undertaking assessments there is a need to:

1) Consider data over as long a period as possible, so as to help understand changes in the data, including natural variability as well as anthropogenic influences relevant for setting baseline values;

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2) Use the latest available data from monitoring programmes in the assessment to ensure the assessments reflect the most recent situation;

3) Update all data used in the assessment regularly every i.e. 2-6 years’ period; 4) Use data from the same time period when considering combinations of data; 5) Compare the most recent assessment period with the previous year assessment period

in order to report progress in achieving targets. Key outputs of assessment of the monitoring data should focus, but not limited, to information relating to: 1) Areas of concern identified on the basis of the review of the existing information and 2) Areas of known past and/or present release of chemical contaminants. 3) Areas where risk warrants coverage such as oil and gas activity, dredging, mining,

dumping. 4) Sites representative in monitoring of other land and atmospheric sources. 5) Reference sites for reference values and background concentrations. 6) Representative sensitive pollution sites/areas at national and sub-regional scale. 7) Sites or areas of potential particular concern.

4.13 Data and information sharing

The goal of environmental monitoring is to provide scientific data necessary to guide policy decisions and land use practices. The following are principles that ensure that data are handled in a consistent and transparent manner, as follows:

1) Open access to data, meta data and services as much as appropriate; 2) recognize and respect the national and institutional policies and legislation and the

and intellectual property; 3) Minimum time delay and free of charge or no more than cost of reproduction; 4) the use, re-use and re-combination of data from different sources in different

frameworks and media than those for which they were originally commissioned; 5) Protect the integrity, transparency, and traceability in environmental data, analysis

and forecasts.

4.14 Resources necessary for monitoring

Sufficient resources are instrumental to the success of the monitoring programme. Required resources may include:

1) A dedicated budget for the monitoring programme; 2) A programme manager to oversee the implementation of the monitoring programme; 3) The availability of expert scientists to take responsibility for sample collection and

analysis; 4) Specialist equipment, including field, laboratory and data management equipment; 5) The availability of trained staff to assist with sample collection and analysis, or data

handling and reporting; 6) Collaborative opportunities with other national operators and/or researchers.

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5. AIR SAMPLING AND SAMPLE PREPARATION

5.1 Air sampling site consideration

The selection of sites to meet the network objectives is based on the requirements for distribution, location, separation and spatial scale of representation. Site selection criteria can be divided into those relating to urban and rural monitoring networks. Rural monitoring networks include background and regional transport sites that may also comprise chemical species and gaseous precursors, and special studies sites.

Along with addressing the overall monitoring objectives, the site selection process needs to take the following practical factors into consideration:

1) reliable electric power source 2) accessibility throughout the year 3) security of the site from unauthorized access and vandalism 4) specifications for sampling shelter and inlet probe installation 5) possible interference from local sources and plume dispersion effects

Additionally, quality requirements in terms of equipment, transportation, standardization, and traceability are indispensable. It is important that all sampling procedures are agreed upon and documented before starting a sampling campaign. The analyte, matrix, sampling site, time or frequency, and conditions should be determined depending on the objective of the sampling. Although it may be too expensive to get full accreditation for sampling, Quality Assurance and Quality Control (QA/QC) procedures for sampling should be put in place.

The sampling site is selected to provide the most representative air quality information to a given population. When a small number of monitoring stations are planned for a community or reporting area, subjective methods are often employed such as: the selection of one site each in industrial, commercial and residential neighbourhoods.

Separation distances between stations are dependent on population density of the area. Stations are deployed to give the most accurate measurements representing the air quality of the area. Usually this is in the order of 6 to 8 kilometres for urban locales. Such spatial scales and separation distances are more applicable to gaseous and very fine particulate matter, which are often relatively homogeneously distributed and spatially dispersed within air sheds, than some other parameters.

5.2 Spatial Representativeness

To achieve the different goals of representativeness of the sampling sites, the monitoring stations are identified by both geographical and physical location. Physical location is defined by the concept of spatial scale of representativeness and is described in terms of the physical dimensions of the air parcel nearest to a monitoring station throughout which actual pollutant concentrations are reasonably uniform (Table 5.1). The goal in siting stations is to match the spatial scale represented by the sample of monitored media with the spatial scale most appropriate for the monitoring objective of the station. According the USEPA, there are six

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categories of spatial scales of representativeness defined for monitoring station siting purposes.

Table 5.1 Representation of spatial scale of air masses

Category of spatial scale Volume of air Volume of concentration Micro-scale Several meters to 0.1 km

Middle scale Several city blocks ranging from 0.1 km to 0.5 km

Neighbourhood scale An extended area of the city with relatively similar land use characteristics extending from 0.5 km to 4 km range

Urban scale Entire metropolitan area ranging from 4 km to 50 km

Regional Scale Usually rural area with homogeneous geography from 10s to 1000s km

Global scale Represent concentrations characterising a nation or the globe as a whole

5.3 Site Classification

To address the broad application of data, four categories of monitoring stations can be identified:

1) Community reporting requirements 2) Regional transport/background 3) Chemical speciation/precursor 4) Special studies

A) Community Reporting Stations

Population or community-oriented monitoring sites are used to determine the representative area-wide public exposure levels of pollutants. These stations measure pollutants for comparison with standard requirements for air quality and should be located in residential, commercial, industrial or other areas where people spend significant amounts of time. Neighbourhood or urban scale stations are typically appropriate for this objective.

Measurement at neighbourhood or urban spatial scales are appropriate when sub-regional conditions for the dimensional area are reasonably homogeneous to particulate concentrations, land-use and land-surface characteristics. Concentrations within communities might be expected to occur near major emission sources, hence levels measured close to individual sources may not necessarily represent concentrations to which the majority of the community population is exposed.

Selection of monitoring sites requires careful consideration in order to account for both collective community and other source contributions to the measured levels. Properly sited community-oriented measurements should facilitate the development of control strategies to reduce broader community-wide exposure to air pollutants.

B) Regional Transport/Background Stations

Regional transport/background monitoring sites are used to determine the upwind concentration of air pollutants communities that may be significantly influenced by pollution from trans-boundary source regions or high background levels.

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C) Chemical Speciation/Precursor Stations

The goals of chemical speciation/precursor monitoring sites are to:

assess trends in PM mass components and gaseous precursor concentrations; identify specific source contributions in the air-sheds; track the effectiveness of control strategies; provide input to air quality models and analyses; improve PM and ozone sampling and monitoring strategies; provide information for health impact studies. measure overall progress of air pollution control programs.

D) Special Study Stations

Special study sites are where intensive monitoring is done across a wide range of atmospheric constituents to further develop the science and technology. These sites contribute additional information that could strengthen policy development and program management of pollutants.

Special Studies sites can encompass a wide variety of measurement programs and might focus on characterizing emission sources and transformation products, validating model outputs, improving or inter comparing measurement methods, or understanding health and environmental impacts.

Spatial representativeness of Special Studies sites vary depending on specific issues being investigated, and sites may not necessarily be community-oriented. Vehicle traffic emissions, including exhaust components and re-suspended road dust, can represent an important and sometimes predominant local source in large urban areas. This can affect both the magnitude and variability of urban air pollutant levels, particularly near high traffic routes.

5.4 Siting considerations

Positioning and installation of samplers should follow standard operating procedures for air sampling program. A detailed description of all selected sites should be provided. More general criteria are given here:

Regional representation: A location free of local influences of POPs and other

pollution sources such that air sampled is representative of a much larger region around the site.

Minimal meso-scale meteorological circulation influences: Free of strong systematic diurnal variations in local circulation imposed by topography (e.g. up-slope/ down-slope mountain winds; coastal land breeze/lake breeze circulation).

Long term stability: In many aspects including infrastructure, institutional commitment, land development in the surrounding area.

Ancillary measurements: For the super-sites, other atmospheric composition measurements and meteorological wind speed, temperature and humidity and a measure of boundary layer stability. For the passive sites, meteorological wind speed, temperature and humidity.

Appropriate infrastructure and utilities: Electrical power (for pumped samplers), accessibility, buildings, platforms, towers and roads, with care to avoid sources of potential contamination.

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Passive sampling sites should also take advantage of the freedom to deploy samplers well away from infrastructure (buildings, roads) and human activity which could be potential sources of POPs contamination.

5.5 Characteristic travel distances (CTDs, km) for air and water

POPs are semivolatile compounds with high environmental persistence and bio-accumulate in biota. Understanding of POPs concentrations and trends at a particular site may be obtained through an evaluation of national and regional scale transport pathways. To do this, an understanding of local (meso-scale) as well as large (synoptic) scale air transport pathways to the site is required. This is achieved through local meteorological measurements to characterize meso-scale influences as well as use of Lagrangian or Eulerian transport models to reconstruct the large scale transport pathways to the site. It is also important that for water-soluble POPs, oceanic and riverine transport and air-water exchange be considered, especially for sites located on coastlines.

Table 5.2 shows documented characteristic travel distances (CTDs, km) for air and water and transport efficiencies (%) for selected POPs based on physical-chemical properties (Wegman et al., 2009). POPs are ranked highest to lowest in terms of the CTDs for air and calculations are performed at 25 oC). Calculations performed using OECD Tool*

Table 5.2 Characteristic travel distances (CTDs, km) for air and water ______________________________________________________

Chemical CTD in air, km CTD in water, km TE% (emission to air) Hexachlorobenzene 230 000 700 2500 Hexachlorobutadiene (HCBD)1 160 000 100 50 Pentachlorobenzene 120 000 200 50 OctabrominatedDiphenyl ethers 22 000 360 10 PCB-180 (hepta homolog) 17 000 340 91 α-HCH 7800 830 54 PCB-28 (tri homolog) 5100 190 2.2 Pentachloroanisole (PCA)2 4300 220 5.2 γ-HCH 4200 220 19 BDE-99 3700 540 15 DDT 3600 490 10 β-HCH 3100 430 3.7 Hexabromobiphenyl 3000 540 13 BDE-209 2900 120 13 Toxaphene 2800 1600 7.9 Short-chain chlorinated paraffins1 1800 230 0.78 2378-TCDD 1600 130 0.58 Dieldrin 1100 580 0.89 chlordanes 1100 300 0.46 chlordecone 710 1700 3.2 Aldrin 60 130 0.00018 PFOS** 10 63 000 0.049 _____________________________________________________________________________

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TE – transfer efficiency for emissions to air; HCH – hexachlorocyclohexane; PCB-polychlorinated biphenyl; DDT – dichlorodiphenyltrichloroethane; TCDD – tetrachlorodibenzodioxin; PFOS – perfluorooctane sulfonate. The resulting CTDs indicate that with the exception of PFOS and aldrin, most of the listed POPs are “flyers” and the atmospheric transport pathway is important. POPs for which the water transport pathway is significant (the “swimmers”) include: PFOS, chlordecone and toxaphene.

Active air samplers typically include a pre-filter for capturing particles. This filter can then be extracted and analysed separately. The breakthrough of fine particles through the filter

5.6 Air sampling and sample handling

Air sampling requires the following capacities:

i) active and passive air samplers, ii) trained station personnel to operate and maintain the high-volume samplers, iii) meticulous preparation of clean sampling media in the laboratories performing the

extraction procedures and chemical analysis. iv) validated of sampling methods and QA/QC procedures from existing air monitoring

programmes for POPs, v) Efforts to avoid and minimize sample contamination

Two widely deployed methods of air sampling are active and passive sampling. Fine spatial resolution measurements of atmospheric contaminants are expensive especially at for developing countries like Kenya.

5.7 Active air sampling

Samples of a high volume and low volume samplers are shown in Figure 5.1.

Figure 5.1 High Volume Air samplers Low Volume samplers

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Global networks that employ high volume air samplers to measure atmospheric POPs employ sampling heads with size-selective inlets for collecting particles below some cut-off size threshold, typically particles smaller than 10 micrometres diameter. These groups recommend the technique of separating particles from gases using the combination of glass fibre filters in series with two gas absorbents. The nature of the type of absorbents used need to be matched to the needs of the regional monitoring programme and target analytes such as PUF, XAD, XAD-PUF, activated carbon fell. Several possibilities exist which are favoured for long term measurements and should be selected by experienced experts planning a regional study: For the particle-phase,

a glass or quartz fibre filter is typically employed. Teflon filters are not recommended

due to contamination issues with PFOS and related compounds. For the gas-phase,

Two PUF plugs recognizing that some volatile chemicals (e.g. chlorobenzenes) will

not be trapped efficiently. In this case, keep sample times short (e.g. especially during warm periods);

XAD resin or PUF/XAD combination (generally extracting and analyzing both media together);

PUF followed by active carbon fibre felt disks. Two absorbents are necessary to check periodically for breakthrough losses and to avoid substantive losses for some relatively volatile compounds (e.g. HCB), especially in warmer climates. The addition of higher-capacity sorbents such as XAD and active carbon, as described above helps to improve capture efficiency of the more volatile and/or polar compounds. However, it should be noted that higher capacity sorbents may also lead to higher blanks and are more difficult to fully extract/ and clean. The need for low blanks should be balanced against the need for sorptive capacity of the sampling matrix.

5.8 Sampling breakthrough

Recommendations for dealing with air sampling breakthrough are presented in Bidleman et al. (2018). Samples could be taken intermittently (e.g. approximately once every week or every 2 weeks) or continuously (weekly integrated) with care taken to minimise analyte breakthrough. Breakthrough can be minimized by using a higher capacity sorbent for the gas-phase collection or a reduced air sample volume. Breakthrough is reduced at cold ambient air temperatures when the sorptive capacity of the sampling matrix is increased. As a rule of thumb, the sorptive capacity of the sampling matrix (e.g. PUF plug) will increase by a factor of about 3 for every 10 oC decrease in air temperature.

5.9 Field blanks should be taken regularly.

Field blanks are treated in the same manner as samples including placement in the sampler housing, except no air is drawn through them. In some cases air is drawn through the field blank but only for a very short period of time (e.g. seconds to minutes). The method detection limit (MDL) is often based on the levels of target analytes in blanks, rather than by the sensitivity of the analytical instrument.

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5.10 Absorbents are pre-cleaned prior to sampling.

Filters are usually pre-treated by baking at high temperatures. Samples should be put into the sampling head using environment and handling practices that are free of contamination and volatilization losses. Many POPs are semi-volatile and may evaporate from sampling media if they are warmed appreciably above ambient temperatures. After sampling, samples and field blanks are extracted in the appropriate solvent (e.g. hexane and dichloromethane are common). Although Soxhlet extraction is a commonly used extraction method, other extraction techniques such as accelerated solvent extraction, microwave extraction and sonnication are also used, depending on the target compounds. Extracts are concentrated prior to analysis and it is a common practice to archive some portion. This allows samples to be re-analyzed years later when analytical techniques may have improved and there is new information (such as on additional POPs) to be gained.

5.11 Passive sampling

Passive air samplers (PASs) are alternative cost-effective complementary monitoring tools deployed in ambient air sampling. Due to cost effectiveness PAS can be deployed in high numbers, at sites away from sources of electricity, and in locations where the costs and logistics of active sampler deployments can be difficult. To yield volumetric air concentration data the sampling rate (SR) or the volume of air that is effectively stripped of the contaminant of concern per unit of time is derived by done either calibration experiments that deploy the PAS concurrently with reliable active sampling techniques or theoretically based on an understanding of the processes controlling mass transfer from atmosphere to PAS sorbent. Sampling of POPs using PAS has veen evaluated through several studies (Herkert et al., 2018; Kalina et al, 2017, Holt et al, 2017, Bohlin et al., 2014; Harner et al., 2014). Figure 5.2 shows a schematic diagram of passive sampling devices (UNEP, 2018).

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Figure 5.2 Schematic of PUF disk passive air sampler

The most common conceptual model of uptake in PASs assumes a stagnant air layer or air-side boundary layer (ASBL) around the sorbent, through which contaminant transfer occurs solely by molecular diffusion (Shoeib and Harner, 2002). Hence wind decreases the thickness of the ASBL, which in turn increases the sampling rate. Temperature has the potential to affect SR in two ways: changing the rate of gas phase diffusion of the contaminant due to the temperature dependence of molecular diffusion coefficients and (ii) shifting the partitioning equilibria between the sorbent and the gas phase.

Relative humidity (RH) may also affect SRs by influencing the sorptive properties of certain sorbents for target analytes. Other factors that may affect the sorption of contaminants to PAS sorbents include passivation of sorbents interfering compounds blocking sorbent uptake sites or stripping analytes through reaction), degradation of the sorbent over time, and uptake of the contaminant to the sampler housing or diffusive barrier.

There are several centralized passive air sampling networks contributing internally consistent, regional-scale and global-scale information on POPs to the global monitoring plan and targeting new priority chemicals in air. As a result of their low cost and simplicity the adoption of passive air sampling for addressing data gaps and for assessing spatial trends and long-range transport of POPs has accelerated greatly since the first GMP report. Passive sampling principle (Ji-wong et al., 2019) is based on diffusion process to collect gaseous pollutants as expressed by the Fick’s Law.

………………. Equation 1

Where by J the mass transported (J, unit = mass.time-1length-2) is proportional to a diffusion Coefficient (D, unit = length2.time-1) and a concentration gradient over a distance (dC/dx, unit = mass.length-3length-1).

The flux is a product of a concentration gradient, dC and a mass transfer coefficient, k (unit = length.time-1) as shown in equation (1). Where L represents the diffusion layer length (unit = length), and is theoretically or empirically estimated. For accurate determination of the concentration using a passive sampler, the initial section is applied where the sorbed amount linearly increases. Analyte concentration is calculated as shown in Equation (2).

…… Equation 2

The sampling rate (SR) is estimated by the product of k and the area at which diffusion occurs, which is dependent on the characteristics of the pollutant and the design of the sampler (Ji-wong et al., 2019). During calibration, experimental sampling rate SR is determined using the concentration measured by an active sampler as shown in equation (3).

…….Equation 3

Detailed procedure for field sample preparation is summarised in Appendix 3. A sample of analytical metadata capture form for air media is shown in Appendix Table A1.3.

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Table 5. 3 Proposed air monitoring sites and frequency

Region Air sampling sites Sampling type Monitoring Frequency Nairobi Dandora PUF Quarterly

Kikuyu*Steel industry PUF Quarterly Kitengela*/sheep and goats project

PUF Quarterly

ECCL* (Stone Athi) PUF Quarterly ECCL old area* PUF Quarterly Babandogo* PUF Quarterly

Ngong Hills –baseline. PUF Quarterly Athi River industries PUF Quarterly

KNH PUF Quarterly Kabete PUF Quarterly

Chiromo Campus PUF& Active Quarterly Mombasa Kibarani PUF Quarterly

Coast RH PUF Quarterly Mazeras PUF Quarterly Bamburi PUF Quarterly

Nakuru Gioto dumpsite PUF Quarterly

Nakuru Industrial area PUF Quarterly Nakuru RH PUF Quarterly

Kisumu Nyalenda /LVEMP PUF Quarterly Kachoki dumpsite PUF Quarterly

KEMRI incinerator PUF Quarterly Kisumu referral hospital PUF Quarterly

Control Site

Mt. Kenya PUF Quarterly

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6. WATER SAMPLING AND SAMPLE PREPARATION

6.1 Generals consideration of water quality

The water resources are prone to contamination from diverse sources such as atmospheric deposition, urban and agricultural runoff, industrial wastewater discharges and seepage from septic systems, recreational use, and other anthropogenic impacts. The national mandates relating to water quality monitoring are stipulated under the water act 2016 and the Water Resources Regulations 2019 subsection 61. Whereas quality of most inland lakes and rivers is relatively good at the source, conditions can change considerably as these rivers traverse agricultural, municipal and industrial regimes. Hence it is important to detect change as early as possible, in order to maximize the potential for effective management actions. The national lakes and rivers are extensively used by riparian communities for fishing, boating, swimming, and other recreational activities. Preservation of lake water quality and quantity is of utmost importance to the national water resource authority managers, researchers, and the general public, monitoring basic water quality ranked among the highly.

Water quality parameters can be divided into basic limnolgical parameters and industrials based parameters such as organic and inorganic based pollutants from industrials activities. The regular basic water quality parameters temperature, pH, specific conductance, dissolved oxygen, and flow/water level, Secchi depth or transparency tube depth. Secchi depth or transparency is ranked highest among potential vital signs for aquatic systems although less diagnostic. Inputs of excess nutrients, invasion and spread of exotic species, contaminants from atmospheric fallout and surface runoff, and how these stressors affect the chemical and biological functions of lakes or rivers are key issues of concern in water resources management. Water quality monitoring provides data for understanding changes in lakes or rivers over time.

i) Temperature

Water temperature influences activity, growth, distribution, and survival of aquatic biota. Biota such as fish, insects, zooplankton, phytoplankton, and other aquatic organisms all have preferred temperature ranges for optimal health and reproduction. Temperature also important influences of water chemistry and physical processes, such as evaporation, oxygen (and other gas) diffusion rates, chemical reaction rates, particle settling velocities (via viscosity), and the stability of thermal stratification. Through its effect on water density it structures deeper lakes into distinct layers with profound physical and chemical differences creating diversity habitats for organisms (Wetzel, 2001).

ii) Specific Electrical Conductivity (EC25 or SC25)

Electrical conductivity is a measure of the capacity of water to conduct an electrical current. Specific conductivity (also called EC25 or SC25) is the ‘raw’ conductivity normalized to unit length and cross-section at 25 °C. This normalization eliminates its temperature dependent variability and makes it a good estimator and surrogate measure of the concentration of total dissolved ions in the water. SC25 is controlled by geological type in the watershed, which determines the chemistry of the watershed soil and ultimately the lake. The size of the

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watershed relative to the area of the lake also affects SC25, with a larger ratio indicating that relatively more water drains into the lake because of a larger catchment area and has more contact with soil before reaching the lake. Increased SC25 may indicate a sources of pollutants, such as wastewater from sewage treatment plants or on-site septic systems, urban runoff from roads (especially road salt), agricultural runoff, and atmospheric deposition. Increased conductivity from runoff into soft waters can be a major stressor to salmonids, shoreline and near-shore plants, and other aquatic organisms. Conductivity is an important indicator of polluted runoff that may contain excess nutrients, organic matter, pathogenic microbes, heavy metals, and organic contaminants. SC25 increases naturally due to evaporative salt concentration and respiration, which increases bicarbonate and carbonate concentrations. It is also an excellent ‘tracer’ of water masses in the lake, as well as tributary and groundwater inflows.

iii) pH

The pH value is the negative logarithm of the hydrogen ion (H+) activity in the water. It is the alkalinity or acid-neutralizing capacity (ANC,) which is a measure of the buffering capacity of the water. The pH of water determines the solubility and biological availability of chemical constituents such as nutrients (phosphorus, nitrogen, and carbon) and heavy metals (lead, copper, cadmium, etc.). pH is used to set water quality criteria for lakes and streams because of its potential impacts to the life cycle stages of aquatic macro-invertebrates and certain salmonids that can be adversely affected when pH levels are above 9.0 or below 6.5 (Stednick and Gilbert, 1998). The mobility of many metals is also enhanced by low pH and can be important in assessing mining impacts. Estimating the toxicity of ammonia, aluminum, and some other contaminants requires accurate pH values. Daily and seasonal variability in pH is associated with natural changes in biological photosynthesis and respiration, as well as inputs from runoff and atmospheric deposition (Schindler, 1988; Schindler et al. 1985). When nutrient pollution results in higher algal and plant growth (e.g., from increased temperature or excess nutrients), pH levels may increase, as allowed by the buffering capacity of the lake. Although these small changes in pH are not likely to have a direct impact on aquatic life, they greatly influence the availability and solubility of all chemical forms in the lake and may aggravate nutrient problems.

iv) Dissolved Oxygen (Concentration and % Saturation)

Dissolved oxygen (DO) is a measure of the amount of oxygen in solution. Oxygen solubility is controlled largely by water temperature and the partial pressure of oxygen within gasses in contact with the solution. Its concentration in any stratum of water is determined by the net difference between its sources and its sinks. Oxygen transfer from the atmosphere to the water and from one depth to another depends on its diffusion rate, which is highest in the upper, turbulent wind-mixed layer (epilimnion) and very low in the hypolimnion. The largest source of O2 is the atmosphere, but phytoplankton and macrophyte photosynthesis produce O2 during daylight hours and tributaries can contribute significant DO to specific layers of water. The major sink for DO is respiration by animals, plants, and microbes, occurring throughout the day. Because photosynthesis is light dependent, and surface mixing is largely dependent on wind energy and morphometry (in the sense of wave height and fetch), DO levels can vary throughout the day, season, and with depth. Temperature controls the potential O2 saturation, although water can supersaturate from high turbulence (e.g., waterfalls) or photosynthesis from algal blooms in hypereutrophic lakes.

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A DO level > 1 mg/L is generally accepted as a chronic minimum for most aquatic animals; 5 mg/L is a chronic minimum for the maintenance and survival of most aquatic organisms and is a common regulatory criterion for supporting a cold water fishery. As water becomes warmer it can hold less DO. If the water becomes too warm, even if 100% saturated, O2 levels may be suboptimal for many fish species.

v) Lake Level

It is important in defining the spatial extent of littoral zones. These shallow water areas provide critical habitat for many aquatic organisms and are nursery areas for both planktivorous and piscivorous fish at various stages of their life cycles. Accurate volumetric estimates, hydrologic budgets, heat budgets and mass balance budgets for chemical compounds and oxygen also require accurate lake levels. Fluctuations in lake level are also important in terms of near-shore development, wetland conservation and function (Mitsch and Gosselink, 2000) and nutrient and mercury cycling (Christensen et al. 2004).

vi) Water Clarity

Is a measure of water clarity (Secchi depth and/or transparency tube depth) has fundamental importance to aquatic ecology. Light penetration, for which water clarity is a surrogate, is an important regulator of rate of primary production and plant species composition, including the balance between phytoplankton and macrophyte production in shallow lakes (Moss et al., 1996). Water clarity provides a visual measurement that relates directly to the aesthetic perceptions of the general public. Secchi depth can also be an effective indicator of non-algal suspended sediment loading from agricultural and urban runoff and from shoreline erosion (Swift et al., 2006; Holdren et al., 2001; Preisendorfer, 1986). Secchi depth transparency has a long history of use in lake monitoring programs as an excellent indicator of trends in phytoplankton biomass (e.g., WOW, 2005; Goldman 1988).

vii) Major Ions

Includes cations - calcium (Ca2+), magnesium (Mg2+), sodium (Na+ ), and potassium (K+ )

anions - SO42-, Chloride (Cl-), and alkalinity (CaCO3). The chemical composition of a lake is

a function of land use, climate, and basin geology. Each lake has an ion balance of the three major anions and four major cations (Table 1). The ionic concentrations influence the lake’s ability to assimilate pollutants (e.g., acidification) and maintain nutrients in solution. For example, calcium carbonate (CaCO3) in the form known as marl can precipitate phosphate from the water, thereby removing this important nutrient from the water. High Ca2+

and Mg2+

directly reduce the bio-availability and toxicity of many heavy metals, and indirectly affect mercury cycling (Horne and Goldman, 1994; Driscoll et al., 1994 & 1995).

Bicarbonate and carbonate ions, which are estimated by alkalinity, dominate the major anions. Alkalinity directly estimates the majority of the buffering capacity of the water and is used to estimate sensitivity to acid precipitation. Sulfate concentrations provide a measure of the potential accumulation of sulfur due to acidic deposition of SOx compounds and are important for assessing acid deposition effects. Sulfate is also a critical parameter for understanding and modeling mercury cycling because sulfate-reducing bacteria in anoxic environments are the primary source of methyl mercury, the major fraction involved in the bioaccumulation of mercury in food webs (Driscoll et al. 1994). Chloride (Cl-

) is a particularly good indicator of wastewater plumes as well as inputs and accumulation of road salt. It may be used as a tracer, as it moves through soil without significant absorption or

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adsorption. The concentration of the major ions and their relative ratios influence the species of organisms that can best survive in a lake, in addition to affecting many important chemical reactions that occur in the water. Zebra mussels (Dreissenapolymorpha), for example, require levels of calcium typically higher than those found in Lake Superior water, though this exotic species has invaded several inland lakes at SLBE. Humans can have profound influences on the characteristics of lake chemistry, including ion concentrations. Modification of natural shoreline vegetation and increasing the amount of impervious surfaces surrounding a lake cause increased runoff, which can carry chloride and potassium from the use of road salt.

viii) Dissolved Silica (SiO2)

Silica is considered an essential micro-nutrient for microorganisms and diatom algae. These organisms use silica to form shells and other protective structures. Diatoms are capable of using large amounts of silica, and may be growth-limited when silica is in short supply.

ix) Dissolved Organic Carbon (DOC)

Dissolved organic carbon (DOC) is usually the largest fraction of organic material in the open waters of lakes. (Exceptions generally involve hypereutrophic lakes with intense blooms of algae or an abundance of aquatic plants that die off in the fall.) It is derived primarily from decomposing material in the watershed that is leached into stream and groundwater inputs and washed in from wetlands with abundant sphagnum mosses (Wetzel, 2001; Schindler and Curtis, 1997). Typically, a lesser amount is contributed by algae, both from extracellular leakage and via decomposition; concentrations may be high following intense algae blooms. DOC plays important roles in freshwater ecosystems , including 1) affecting acid-base chemistry and metal cycling (e.g. copper, mercury, aluminum), and potential toxicity; 2) acting as a source of energy and nutrients to the microbial food chain, thereby influencing nutrient availability; 3) attenuating UV-B radiation; 4) attenuating PAR (photosynthetically active radiation) and thereby regulating primary production; and 5) influencing the heat budget of the lake by absorbing sunlight (Gergel et al., 1999; Schindler and Curtis, 1997). Anthropogenic stressors, such as global warming, ozone losses, acidification, and intensive logging are cause for concern as they may be altering the concentration and distribution of DOC, resulting in adverse effects on lakes.

x) Nutrients (Total Phosphorus [TP], Total Nitrogen [TN], Nitrate+Nitrite-N

[NO3+NO2-N], and Ammonium-N [NH4-N])

Nitrogen and phosphorus are the two most influential nutrients in terms of regulating phytoplankton and aquatic macrophyte growth. Excessive inputs of nutrients can lead to excessive algal growth and eutrophication. Significant amounts of available nitrogen may be deposited during rainfall events (wet deposition) and through the less obvious deposition of aerosols and dust particles (dry deposition). Nitrogen and phosphorus in dry fallout and wet precipitation may come from dust, fine soil particles, and fertilizer from agricultural fields.

xi) Chlorophyll-a

The concentration of chlorophyll-a, the primary photosynthetic pigment in all green plants including phytoplankton, is a nearly universally accepted measure of algal biomass in the open waters of lakes (Wetzel, 2001; Wetzel and Likens, 2000). However, it may also be important to examine the algal community microscopically on occasion, because the mix of

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species can influence chlorophyll-a concentration, as different algal groups have different proportions of chlorophyll-a versus other pigments. Hence, chlorophyll-a is not always an accurate measure of biomass, and the mix of species may influence lake management decisions. Chlorophyll-a concentrations are expected to be dynamic, reflecting changes in algal abundance through the ice-free growing season. Consistent and directional trends in chlorophyll-a concentrations are good indicators of change in a lake’s trophic status.

6.2 Objectives of water quality monitoring

The overall goal of monitoring water quality is to contribute to an understanding of the health of aquatic ecosystems and provide insights on likely water resources issues in the country.

Specific objective 1. Rational planning of water pollution control strategies; 2. Identification of the nature and magnitude of water pollution control required; 3. Evaluation effectiveness of water pollution control efforts already in existence; 4. Identification of the state and trends in water quality, both in terms of concentrations

and effects; 5. Identification of the mass flow of contaminants in surface water and effluents; 6. Guide formulation of the water quality standards and permit requirements; 7. Testing of compliance with water quality standards and classifications for waters and

effluents; 8. Establishment of early warning and detection of water pollution.

6.3 Water quality sampling guidance

6.3.1 Site selection

i) Selection of the sampling sites is to be based on the existing human and industrial activities along the rivers. In general, the sites should cover the upstream, midstream and downstream. The following factors should be considered as general criteria for selecting appropriate sampling sites:

ii) A reference station should be located up-stream of all possible discharge points to aid in determining the degree of man induced pollution, and the damage that is caused to aquatic life. The reference station serves to assess the situation with respect to background water quality and biological aspects, which may vary locally and regionally.

iii) Drinking water intake points, bathing ghats, irrigation canal off-take points should be considered for monitoring.

iv) Sampling stations should be located upstream and downstream of significant pollution outfalls like city sewage drains and industrial effluent outfalls.

v) All samples must be representative, which means that the determinants in the sample must have the same value as the water body at the place and time of sampling. In order to achieve this it is important that the sample is collected from well-mixed zone.

vi) Additional downstream stations are necessary to assess the extent of the influence of an outfall, and locate the point of recovery.

vii) In large rivers where mixing is poor and incomplete, the effluent may tend to follow one bank. Stations on both sides downstream are useful to make an estimate of the extent of the mixing zone.

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viii) In large rivers a balance has to be found between the selection of a few stations giving poor coverage, and the selection of more stations having different substrates and dissimilar fauna, which cannot be compared spatially.

ix) In order to enable comparisons among sampling stations, it is essential that all stations be sampled approximately at the same time. Not more than two weeks should elapse between the sampling of the first and last station in a river.

x) Sites for biological sampling should match with sites for chemical sampling. xi) Biological sampling stations need to be selected with proper attention to

representative habitats (kind of substrate, depth and flow). All sampling stations in a certain river should preferably be ecologically similar. To increase biological and chemical comparability, they should have similar substrate (sediments, water), depth, presence of rifles and pools, stream width, flow velocity, bank cover, human disturbances, etc.

xii) The conventional location of macro-invertebrate sampling stations in rivers arises not only from an assumed uniformity of substrate and fauna, but also from the ease with which it may be sampled by means of hand nets and stone lifting or kicking, and from the ease of access.

xiii) For the estimation of the oxygen exchange rate of the river, a measurement of cross section is required. Any station should be typical with respect to the cross section of the river.

xiv) The sampling team normally has to carry an appreciable burden of sampling gear and water samples, and the distance they can walk is limited. Easily accessible sites should be selected. The site should also be accessible under all conditions of weather and river flow. Accessibility is therefore an important consideration.

xv) With respect to preservation, samples are taken to perform analysis on three types of parameters: for some parameters, such as heavy metals, the samples need not be preserved. For other parameters, samples can be preserved by cold storage or by the addition of certain preservatives. However, the samples for analysis of parameters like BOD and bacterial counts cannot be preserved and need to reach the laboratory shortly after taking the sample.

xvi) The collection of samples can be hazardous at some locations in bad weather (such as high flow). Such sampling sites can better be avoided.

xvii) There are many disturbing influences in the rivers, especially cattle wading, melon farming, fishing, sand recovery, etc. These disturbances can drastically influence chemical processes and the nature of the biological community. Dams and barrages provide a different kind of habitat. Such sampling sites should be avoided.

xviii) Availability of sampling facilities such as bridges, boats, and possibilities for wading are important criteria in the selection of sampling sites.

xix) As much as possible, the stations should be sited near regular gauging stations (RGS) where river flow (discharge) can be determined, especially when pollution load has to be estimated.

6.3.2 Sampling frequency

A trade-off exists between the number of lakes and rivers to be sampled within a given year and the number of repeat visits made within a year. Variability of water quality characteristics within a season is often high and may be comparable to the variability between years for some parameters, even for pristine lakes with no apparent long-term trends.

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6.3.3 General water sampling design

The general water sampling schemes are summarised in Table 6.1.

Table 6.1 Water sampling designs for lakes and Rivers

Random Stratified Systematic Non random

Water source (Lake or river)

Sampled lakes or rivers are chosen randomly from geographical area

Randomly selected from each geographical region or based on other classification e.g. Recreational, beneficial type, drainage type

Sample every lake or river along a transect, using a randomly chosen transect starting point

Choose lake or river based on convenience, access, proximity or interest

Site Randomly chosen from the lake or river area

Randomly chosen from within the region lakes or rivers

Sample at equidistant points along the transect of the lake or river

Sample at the dam, over the deepest part of the lake or river, or other location based on interest

Depth Randomly chosen

Randomly chosen with each depth region

Sample at preset intervals starting with randomly chosen depth

Sample at the surface, at preset interval surface to bottom or at discrete depth for particular interest

Date Randomly chosen

Randomly chosen with each season, month and limnological period

Sample every two weeks starting with a randomly chosen data

Sample on a chosen day for a reasons of convenience

Time Randomly chosen

Randomly chosen with each day period i.e. Morning, afternoon, evening etc.

Sample every two hour starting with randomly chosen time

Sample times based on convenience

6.3.4 Types of Samples

Different types of samples can be collected depending on the sampling procedure used. These include:

i) Grab sample (spot - or catch samples) One sample is taken at a given location and time. In case of a flowing river, they are usually taken from the middle of the main stream of the flowing water and in the middle of the water column. Sampling intervals are to be chosen on the basis of the expected frequency with which changes occur.

ii) Composite samples A mixture of spot samples collected at the same sampling site at different times. This method of collection reduces the analytical effort, because variations are averaged out in one analysis. It is a useful technique when daily variations occur and seasonal variations are the objective of the programme.

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iii) Integrated samples Samples are collected at the same location but, due to horizontal or vertical variation in the composition of the river or in water flow or lake, they come from different points in the cross-section that are regarded with a different relative importance.

6.3.5 Water Sampling equipment

Several different types of sampler are available, many of them designed for specific purposes. The three types described here are those that are most useful for a general water sampling programme.

i) Dissolved oxygen sampler

A dissolved oxygen sampler is a metal tube about 10 cm in diameter and 30 cm in length, sealed at one end and with a removable cap at the other. A bracket is located inside the tube in such a way that a 300-mL BOD bottle can be placed in the bracket with the top of the bottle 2 - 3 cm below the top of the sampler. The sampler cap has a tube extending from its underside down into the BOD bottle when the cap is in place. The upper end of this tube is open and flush with the outside face of the sampler top. A second tube in the sampler cap is flush with the inside face and extends upwards for about 8 - 10 cm. This second tube is sometimes incorporated into the frame to which the lowering rope is fastened. Figure 6.1 shows a typical dissolved oxygen sampler (WMO, 1988).

Figure 6.1 Dissolved oxygen sampler

When the sampler is used, a BOD bottle is placed in the bracket, the sampler cap is fitted in place, and a lowering rope is fastened to the sampler which is then lowered vertically to the depth from which the sample is to be taken. Air in the sampler flows out through the highest tube and, consequently, water enters the BOD bottle through the lower tube. The volume of

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the sampler is about five times the volume of the bottle, therefore the incoming water flushes out the bottle at least four times and the water that finally remains in the bottle will have had no contact with the air that was originally in the sampler. Provided that the sampler is lowered quickly to the desired sampling depth, the sample obtained should be representative, in terms of its dissolved oxygen content. If a sample needs to be taken from great depth, inflow to the sampler can be prevented with a cork or similar device that can be removed when the desired depth is reached.

As the sampler is returned to the surface, the cap is removed and a ground-glass stopper is placed in the (ground-glass) neck of the BOD bottle before it is taken out of the sampler. The water remaining in the sampler can be used for other analyses but it must be remembered that this will be water that flowed into the sampler between the surface and the depth at which the dissolved oxygen sample was taken. Moreover, its volume will be only about 1.5 litres, which may not be enough for all of the intended analyses.

ii) Depth sampler

The depth sampler, which is sometimes called a grab sampler, is designed in such a way that it can retrieve a sample from any predetermined depth. A typical depth sampler is shown in Figure 6.2.

Figure 6.2 Depth sampler

It consists of a tube, approximately 10 cm in diameter and 30 cm in length, fastened to a frame along which it can slide. The frame has projections at each end so that the tube cannot slide off. The ends of the tube are covered by spring-loaded flaps, which can be held in the fully open position by latches. The latches can be released by applying a small amount of pressure to a lever. To accomplish this, a weight (called a “messenger”) is dropped down the

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lowering rope, the latch is tripped and the ends of the tube close. When the sampler is in use, the end flaps are latched into the open position. As the sampler is lowered to the required depth with the lowering rope, water passes through the open ends so that, at any depth, the water in the sampler is the water from that depth.

When the desired depth is reached, the messenger weight is dropped down the rope, the latch is tripped and the end flaps close. The sampler is brought to the surface and its contents are transferred to a sample bottle. A sample obtained in this way can be used for all chemical analyses except dissolved oxygen. A simpler and less expensive model of depth sampler, suitable for moderate depths (< 30 m) is illustrated in Figure 6.3.

Figure 6.3 Depth sampler suitable for moderate depths

iii) Multi-purpose sampler

A multi-purpose sampler, also called a sampling iron, is most frequently used for taking samples in flowing streams or rivers. It consists of a weighted platform equipped with clampsor similar means of holding a sample bottle, a rudder to maintain its position in the flowing water, and rings at the top and bottom to which lowering ropes can be attached as shown in Figure 6.4 (WMO, 1988).

One end of the rope may be attached to the top ring and a friction release device, connected between the rope and the bottom ring, holds the bottle in an inverted position during lowering. An alternative arrangement is to use two ropes, one fastened to the lower ring and one to the upper. Both arrangements permit the collection of samples from a deep location by allowing the sampler to be lowered in an inverted position and then restored to the upright position when the required depth is reached.

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The multi-purpose sampler is very easy to use for sampling near the surface. The sampler is immersed in the water and allowed to fill up. For samples from greater depths, it must be lowered in the inverted position and then, when the desired depth is reached, righted either by a sharp tug on the rope (for the one-rope configuration) or by transferring restraint to the rope connected to the upper ring. Although some water may enter the sampler during its descent, this type of sampler has the advantage that the sample does not need to be transferred to another container for shipment because it can remain in the container in which it was collected. Samples taken with the multi- purpose sampler cannot be used for dissolved oxygen determination.

Figure 6.4 Multi-purpose sampler

If the water is flowing, the open mouth of the bottle should point upstream as shown in Figure 6.5.

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Figure 6.5 Sampling surface water

When samples are taken for chemical and physical analysis from rivers and lakes, it is often sufficient merely to immerse an open-mouthed vessel, such as a bucket, below the water surface. The contents can then be poured into an appropriate set of sample bottles. Alternatively, the sample bottle can be immersed in the water and allowed to fill up. Care should be taken to avoid the entry of water from the surface since this will often contain very fine floating material that cannot be easily seen

6.3.6 Sample Containers and Cleaning Procedures

Containers for the transportation of samples are best provided by the laboratory to ensure that large enough samples are obtained for the planned analyses and that sample bottles have been properly prepared, including the addition of stabilizing preservatives when necessary. It is essential to have enough containers to hold the samples collected during a sampling expedition.

The sample containers should be used only for water samples and never for the storage of chemicals or other liquids. Glass containers are commonly used and are appropriate for samples for many analyses, but plastic containers are preferred for samples intended for certain chemical analyses or for biota or sediments. Plastic has the obvious advantage that it is less likely to break than glass.

Sample containers must be scrupulously clean so that they do not contaminate the samples placed in them. The cleaning of samplers, sampling bottles and other lab-ware, that come into contact with the sample, is essentially a task for the analytical chemical laboratory. Depending on the parameter, different cleaning procedures can be applied. General guidelines are summarized below and Table 6.2.

i) Heavy metals soaking with: - 1:1 diluted Nitric acid for 1 week is needed, followed

by: - three times washing with double distilled water. ii) Bottles for trace chlorinated organic compounds, like pesticides, should be cleaned

with the high purity solvent used for extraction. iii) Samples for the general physical-chemical characterization allow less vigorous

methods. Thorough cleaning with water to remove particulates and two times rinsing with distilled water will usually be sufficient.

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iv) Organisms that are to be preserved in alcohol or formalin should be stored in glass bottles. The samples for chemical analysis follow the selection and cleaning procedures for the water and sediment compartments and use wide mouth bottles facilitate the entry of the organisms.

v) All bottles should arrive at the sampling site in a fully cleaned state, protected from accidental contamination.

vi) The last cleaning step is in most cases rinsing 2-3 times with the water to be sampled. This cleaning should be done, one bottle at the time, at the sampling point and both bottle and cap should be cleaned: fill the bottle (1/3), put on the cap, shake and empty. Repeat this procedure 2 times.

vii) Teflon containers can also be used to replace either the recommended polyethylene or glass containers

viii) Chromic acid - 35 ml saturated Na2Cr2O7 per litre reagent grade conc. H2SO4 ix) Special grade acetone - pesticide grade when GC analysis to be performed, UV grade

for LC analysis x) Chromic acid should not be used when the sample will be analysed for chromium xi) Ultrapure distilled water is obtained by passing distilled water through a Corning

model AG-11 all-glass distillation unit or equivalent and then through a Millipore Super Q Ultrapure Water System containing a pre-filter cartridge, activated carbon cartridge and a mixed bed deionisation cartridge.

Table 6.2 General guidelines on sample containers.

Variable(s) to be analysed Sample container Washing procedure Organochlorinated pesticides and PCBs, Organophosphorus

1,000 ml glass (amber) with teflon-lined cap

Rinse three times with tap water, once with chromic acid, three times with organic-free water, twice with washing acetone, once with special grade acetone, twice with pesticide grade hexane and dry (uncapped) in a hot air oven at 360 °C

Pentachlorophenol, Phenolics, Phenoxy acid herbicides

1,000 ml glass (amber) with teflon-lined cap

Rinse three times with tap water, once with chromic acid, three times with organic-free water, twice with washing acetone, once with special grade acetone, twice with pesticide grade hexane and dry (uncapped) in a hot air oven at 360 °C for at least 1 h

Aluminium, Antimony, Barium, Beryllium, Cadmium, Chromium, Cobalt, Copper, Iron, Lead, Lithium, Manganese, Molybdenum, Nickel, Selenium, Strontium, Vanadium, Zinc

500-1,000 ml polyethylene (depending upon number of metals to be determined)

Rinse three times with tap water, once with chromic acid, three times with tap water, once with 1:1 nitric acid and then three times with ultrapure distilled water in that order.

Silver 250 ml polyethylene (amber)

Rinse three times with tap water, once with chromic acid, three times with tap water, once with 1:1 nitric acid and then three times with ultrapure distilled Water in that order.

Mercury 100 mL glass (Sovirel)

Rinse three times with tap water, once with chromic acid, three times with tap water, once with 1:1 nitric acid and then three times with ultrapure distilled Water in that

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order.

Acidity, Alkalinity, Arsenic, Calcium, Chloride, Colour, Fluoride, Hardness, Magnesium, Non- filterable residue, pH, Potassium, Sodium, Specific conductance, Sulphate, Turbidity

1,000 ml polyethylene

Rinse three times with tap water, once with chromic acid, three times with tap water, once with 1:1 nitric acid and then three times with distilled water in that order.

Carbon, total organic Nitrogen: ammonia Nitrogen: nitrate, nitrite Nitrogen: total

250 ml polyethylene Rinse three times with tap water, once with chromic acid, three times with tap water, and three times with distilled water, in that order.

Phosphorus, total 50 ml glass (Sovirel)

Rinse three times with tap water, once with chromic acid, three times with tap water, and three times with distilled water, in that order.

6.3.7 Sampling surface water for physical and chemical analyses

Samples for physical and chemical analyses, the minimum sample size varies widely depending on the range of variables to be considered and the analytical methods to be employed, but it is commonly between 1 and 5 litres. The following general guidelines can be applied to the collection of water samples (to be analysed for physical or chemical variables) from rivers and streams, lakes or reservoirs and groundwater.

i) Before collecting any sample, make sure that you are at the right place. This can be determined by the description of the station, from the position of landmarks and, in lakes, by checking the depth. If samples must be taken from a boat, a sampling station may be marked by placing a buoy at the desired location; otherwise it is necessary to identify the sampling station by the intersection of lines between landmarks on the shore.

ii) Do not include large, non-homogeneous pieces of detritus, such as leaves, in the sample.

iii) Avoid touching and disturbing the bottom of a water body when taking a depth sample because this will cause particles to become suspended.

iv) To remove larger material pass the water sample through a sieve and collect it in a bottle for transport.

v) Sampling depth is measured from the water surface to the middle of the sampler. vi) Samples taken to describe the vertical profile should be taken in a sequence that starts

at the surface and finishes at the bottom. When taking the sample at the maximum depth it is important to ensure that the bottom of the sampler is at least 1 m above the bottom.

vii) Do not lower a depth sampler too rapidly. Let it remain at the required depth for about 15 seconds before releasing the messenger (or whatever other device closes the sampler). The lowering rope should be vertical at the time of sampling. In flowing water, however, this will not be possible and the additional lowering necessary to reach the required depth should be calculated.

viii) A bottle that is to be used for transport or storage of the sample should be rinsed three times with portions of the sample before being filled. This does not apply, however, if the storage/transport bottle already contains a preservative chemical.

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ix) The temperature of the sample should be measured and recorded immediately after the sample is taken.

x) The sample to be used for dissolved oxygen determination should be prepared immediately after the temperature is measured. If an electronic technique is being used, a portion of the sample is carefully poured into a beaker for measurement.

xi) If the Winkler method is being used, the chemical reagents are added to the bottle in accordance with the directions for DO method.

xii) Separate portions of the sample should be set aside for pH and conductivity determinations. The same portion must not be used for both determinations because of the possibility of potassium chloride diffusing from the pH probe.

xiii) At any time that the sample bottles are not closed, their tops must be kept in a clean place.

xiv) A small air space should be left in the sample bottle to allow the sample to be mixed before analysis.

xv) All measurements taken in the field must be recorded in the field notebook before leaving the sampling station.

xvi) All supporting information should be recorded in the field notebook before leaving the sampling station. Such conditions as the ambient air temperature, the weather, the presence of dead fish floating in the water or of oil slicks, growth of algae, or any unusual sights or smells should be noted, to help when interpreting analytical results.

xvii) Samples should be transferred to sample bottles immediately after collection if they are to be transported. If analysis is to be carried out in the field, it should be started as soon as possible.

Samples for bacteriological analysis

1) Most of the guidelines for sampling for physical and chemical analyses apply equally to the collection of samples for bacteriological analyses. Additional considerations are:

2) Samples for bacteriological analyses should be taken in a sterile sampling cup and should be obtained before samples for other analyses.

3) Care must be exercised to prevent contamination of the inside of the sampling cup and sampling containers by touching with the fingers or any non-sterile tools or other objects.

4) Bottles in which samples for bacteriological analyses are to be collected (or transported) should be reserved exclusively for that purpose.

6.3.8 Sampling frequency and parameters

On routine basis, a combination of general parameters, nutrients, oxygen consuming substances and major ions should be analyzed at all stations. Depending upon the industrial activities and anticipated in the upstream of the sampling station other parameters like micro-pollutants, pesticides or other site specific variables may be included at lower frequency. At minimum the sampling frequency should cover at least of the four seasons experienced in Kenya per year. The proposed sampling sites for POPs monitoring are shown in Table 6.3 below. The sites were selected based on previous history of potential contamination and sensitivity of the ecological system.

Table 6. 3 Proposed water sampling sites for POPs monitoring in water

Region Water Sample type Sampling frequency Nairobi Fourteen falls Bulk/composite Quarterly

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Ngong River(Njiru) Nairobi River (Njiru) Mbagathi River (Downstream EPZ) Kikuyu springs

Bulk/composite Quarterly

Mombasa Kibarani Bulk/composite Quarterly

Sabaki Estuary Bulk/composite Quarterly

Mkurumzi River/Downstram TIOMIN

Bulk/composite Quarterly

Nakuru Final effluent into Lake Nakuru Bulk/composite Quarterly

Lake Naivasha/town side Bulk/composite Quarterly

Lake Naivasha/flower side Bulk/composite Quarterly

River Njoro Bulk/composite Quarterly

Kisumu Lake Victoria Bulk/composite Quarterly

Kisati Bulk/composite Quarterly

Nyando River Bulk/composite Quarterly

R. Nzoia/Webuye R. Nzoia/Midway R. Nzoia/Mouth

Bulk/composite Quarterly

6.3.9 Preparation for Fieldwork

i) Following is the sequence of activities during any given field day: ii) Review the checklist of field gear. iii) Create a new field form for each monitoring station, printed on waterproof paper. iv) Sample bottles, field and trip blanks and labels should be prepared in advance and

placed in a cooler. v) Conduct daily calibration of appropriate meters and probes. vi) Inspect motorized field vehicles at the beginning of every field day, including all

safety and directional lights, oil, gasoline, and tire air pressure levels. vii) Drive to boat landing. Load boat with sampling gear, launch boat, and navigate to

monitoring site. Set up a clean work space on the boat for sampling. viii) Refer to description of monitoring station location, directions, and photo to verify

correct location. Verify coordinates on GPS unit. ix) Measure field water quality variables and conduct sampling per SOP. x) Collect water sample from the highest nutrient depth last, which is usually the bottom

sample. xi) Be sure that all samples are correctly labelled and preserved on ice. xii) Navigate to bench-marker and measure water level relative to marker, per SOP. xiii) Verify that the field form is completely filled out, and initial the form. xiv) If sampling from more than one monitoring station in a day, go back to step 7.

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xv) Upon return to shore, inspect boat, trailer, and all equipment that has come into contact with the water for invasive species. Follow procedures for decontamination of equipment per SOP.

6.3.10 Checklist for field sampling

i) Paperwork

Date and time Itinerary. Inventory details of sampling stations; maps List of samples required at each sampling station. List of stations where water level readings are to be recorded.

ii) Co-ordination

Local co-ordination to ensure access to sites on restricted or private land. Institutional co-ordination for travel arrangements or sample transport. Notify laboratories of expected date and time of sample arrival. Check any available sources of information on local weather conditions and

feasibility of Travel.

iii) For sampling

Sample bottles, preservatives, labels and marker pens Field and trip blanks Sample storage/transit containers and ice packs Filtering apparatus (if required) Samplers/sampling equipment Rubber boots, waders, etc. Standard operating procedures for sampling Spares of all above items if possible and when appropriate

iv) For documentation

Pens/wax crayons Sample labels Field notebook Report forms

v) For on-site testing

List of analyses to be performed on site Check stocks of consumables (including distilled water, pH buffers, standards and

blanks); replenish and refresh as appropriate Check and calibrate meters (pH, conductivity, dissolved oxygen, turbidity,

thermometers) Other testing equipment according to local practice Standard operating procedures and equipment manuals Spares (e.g. batteries)

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vi) Safety

First-aid kit Personal protective equipment. Fire extinguisher (if appropriate)

Vii) Transport

Does assigned vehicle have sufficient capacity for personnel, supplies and equipment? Is vehicle road-worthy? Check battery, lubrication, coolant, windshield washer Is there sufficient fuel for the trip, either in the tank, in fuel cans, or available en route? Is the spare tyre inflated, is there a jack, wheel wrench and tool kit?

viii) Double-check

When was equipment last calibrated? Itinerary against travel details on inventory Accessories for equipment and meters (including cables, chargers and spare batteries)

6.3.11Site - Recording Field Information

The following information should be documented based on the observations to help in interpreting water quality information for the site:

1) Water appearance. General observations on water may include color, unusual amount of suspended matter, debris, or foam.

2) Weather. Recent meteorological events that may have impacted water quality include heavy rains, cold front, lack of precipitation, or heavy precipitation.

3) Biological activity. Excessive macrophyte, phytoplankton, or periphyton growth. The observation of water color and excessive algal growth is important in explaining high chlorophyll-a values. Fish, birds, or spawning fish etc.

4) Unusual odors. Examples include hydrogen sulfide, mustiness, sewage, petroleum, chemicals, or chlorine.

5) Watershed or in-lake activities. Shoreline, inlet stream, or drainage-basin activities or events such as bridge construction, shoreline mowing, new construction, high densities of fast moving boats or personal water craft close to shore.

6) Other things related to water quality and lake/river uses. If the water quality conditions are exceptionally poor, note that standards are not met in the observations (for example, dissolved oxygen is below minimum criteria). Uses may include swimming, wading, boating, fishing, irrigation pumps, or navigation. This type of information may be used in evaluating standards compliance.

While at each monitoring site, the information recorded on field data sheets should include:

i) Date ii) Time of arrival iii) Site name and identification code. iv) Sample date, time, and depth. v) The amount of sample collected. vi) Mode of preservation during transportation vii) Whether duplicate samples for quality control were collected.

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viii) Any additional notes or observations pertinent to this sample or location for this sampling period.

ix) Names of field team members x) GPS coordinates, to verify location xi) Current weather (air temperature, wind speed and direction, wave height) and relevant

notes about recent weather (storms or drought) xii) Observations of water quality conditions xiii) Description of any photographs taken xiv) Multiprobe (model), calibration date, and field measurements of core suite variables xv) List of samples collected and collection times for advanced suite variables or quality

assurance samples and method of collection (e.g., integrating tube or grab) xvi) Whether any samples were not collected, and reason xvii) Water level and /or discharge measurement xviii) Any other required meta-data for data entry xix) Time of departure xx) Date analyzed

6.3.12 Guidelines during sampling

The following general guidelines will be followed during sampling:

i) Wear the appropriate PPEs ii) Rinse the sample container three times with the sample before it is filled. iii) Leave a small air space in the bottle to allow mixing of sample at the time of analysis. iv) Label the sample container properly, preferably by attaching an appropriately

inscribed tag or label. The sample code and the sampling date should be clearly marked on the sample container or the tag.

v) Complete the sample identification form for each sample. The sample identification form should be filled for each sampling occasion at a monitoring station. Note that if more than one bottle is filled at a site, this is to be registered on the same form sample identification forms should all be kept in a master file at the laboratory where the sample is analysed.

6.3.13 Surface water Sampling

i) Samples will be collected from well-mixed section of the river (main stream) 30 cm below the water surface using a weighted bottle or DO sampler.

ii) Samples from reservoir sites will be collected from the outgoing canal, power channel or water intake structure, in case water is pumped. When there is no discharge in the canal, sample will be collected from the upstream side of the regulator structure, directly from the reservoir.

iii) DO is determined in a sample collected in a DO bottle using a DO sampler. The DO in the sample must be fixed immediately after collection, using chemical reagents. DO concentration can then be determined either in the field or later, in a level I or level II laboratory.

I) Collecting surface water

i) Open the sterilised bottle and carefully remove the cap and protective cover from the bottle, taking care to prevent entry of dust that may contaminate the sample.

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ii) Fill the bottle. Hold the bottle near its bottom and submerge it to a depth of about 20 cm, with the mouth facing slightly downwards.

iii) If there is a current, the bottle mouth should face towards the current. iv) Turn the bottle upright to fill it. v) Replace the bottle cap.

II) Collection of tap water

i) Clean the tap. Remove any attachments that may cause splashing from the tap. These attachments are a frequent source of contamination that may influence the perceived quality of the water supply. Use a clean cloth to wipe the outlet and to remove any dirt.

ii) Open the tap. Turn on the tap to maximum flow and let the water run for 1-2 minutes. Turn off the tap. Note: Some people omit the next two steps and take the samples at this stage, in which case the tap should not be adjusted or turned off, but left to run at maximum flow.

iii) Sterilize the tap for 1 minute with a flame (from a gas burner, cigarette lighter or an alcohol-soaked cotton wool swab).

iv) Open the tap before sampling. Carefully turn on the tap and allow water to flow at medium rate for 1 - 2 minutes. Do not adjust the flow after it has been set.

v) Fill the bottle. Carefully remove the cap and protective cover from the bottle, taking care to prevent entry of dust that may contaminate the sample. Hold the bottle immediately under the water jet to fill it. A small air space should be left to allow mixing before analysis. Replace the bottle cap.

III) Collection of dug well water and similar sources

In most of the cases groundwater samples are obtained from existing drilled wells, dug (shallow) wells or springs. Occasionally, during the course of a hydro-geological survey, test wells may be drilled and these can be used for monitoring purposes. The easiest case is to use an existing well or spring as a groundwater quality monitoring station. If the groundwater source is a flowing spring or a well equipped with a pump, the sample can be obtained at the point of discharge. The water should flow for several minutes before sampling until it has reached constant conductivity or temperature in order to avoid any water resident in the system’s piping being taken as a sample (the piping material may have contaminated the water).

Samples for dissolved oxygen analysis should be taken by inserting one end of a plastic tube into the discharge pipe and the other end into a sample bottle. The water should be allowed to flow into the bottle for sufficient time to displace the contents of the bottle at least three times. Care should be taken to ensure that no air bubbles are introduced to the sample while the bottle is being filled, since this could alter the dissolved oxygen concentration.

Special care must be taken when sampling from springs that do not have an overflow and from shallow wells without pumps. The sampling container must not be allowed to touch the bottom of the well or spring catchment since this would cause settled particles to become re-suspended and to contaminate the sample. Sometimes, a spring catchment is higher than the surrounding ground and this permits water to be siphoned into the sample bottle. If this is done, water should be allowed to run through the hose for 2 - 3 minutes to rinse it thoroughly before the sample is collected. Siphoned samples are suitable for dissolved oxygen determination provided that the sample bottle is allowed to overflow a volume of at least three times its capacity.

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The depth within an aquifer from which a sample of water is collected from a well is determined by the location of the well screen and cannot be varied by the collector, because water enters a well at the level of the screen. Similarly, water enters a spring through fissures in the rock. Consequently, a groundwater sample can only be obtained as a grab sample. The greatest danger of getting a non-representative sample occurs when insufficient water has been pumped before the sample is collected and that the sample obtained is representative of the well rather than of the aquifer.

i) Prepare the bottle. With a length of string, attach a weight to the sterilised sample bottle.

ii) Attach the bottle to the string. Take a 20 m length of string, rolled around a stick, and tie it to the bottle string and open the bottle (Figure 6.6).

Figure 6.6 Lowering a weighted bottle into a well

iii) Lower the bottle. Lower the weighted bottle into the well, unwinding the string slowly. Do not allow the bottle to touch the sides of the well.

iv) Fill the bottle. Immerse the bottle completely in the water and continue to lower it to some distance below the surface. Do not allow the bottle to touch the bottom of the well or disturb any sediment.

v) Raise the bottle. Once the bottle is judged to be full, bring it up by rewinding the string around the stick. If the bottle is completely full, discard a little water to provide an air space.

vi) Cap the bottle.

6.3.14 Sample Labelling

Label the sample container properly, preferably by attaching an appropriately inscribed tag or label. Alternatively, the bottle can be labelled directly with a water-proof marker. Information on the sample container or the tag should include:

i) sample code number (identifying location) ii) date and time of sampling iii) source and type of sample iv) pre-treatment or preservation carried out on the sample

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v) any special notes for the analyst vi) sampler’s name

6.3.15 Measurement of Field Parameters

Field measurements must be collected from an undisturbed area, and multiprobe instruments must be allowed to stabilize. Take a replicate reading for every 10 readings; values should agree within 10% or the acceptance criteria, whichever is larger.

6.3.16 Sample packing and transportation

The sample collection process should be co-ordinated with the laboratory so that the analysts know how many samples will be arriving, the approximate time of arrival and the analyses that are to be carried out, so that appropriate quantities of reagent chemicals can be prepared. If sample bottles are provided by the laboratory, this ensures that they are of adequate volume and have been properly prepared with added chemical preservatives where necessary.

Verify that each sample bottle has got an identification label on which the following information is legibly and indelibly written:

i) Name of the study. ii) Sample station identification and/or number. iii) Sampling depth. iv) Date and time of sampling. v) Name of the individual who collected the sample. vi) Brief details of weather and any unusual conditions prevailing at the time of sampling. vii) Record of any stabilising preservative treatment. viii) Results of any measurements completed in the field

Sample bottles should be placed in a box for transport to the laboratory. Sturdy, insulated wooden or plastic boxes will protect samples from sunlight, prevent the breakage of sample bottles, and should allow a temperature of 4 °C to be attained and maintained during transport. Figure 6.7 shows a suitable transport box. Rapid cooling of samples for BOD and/or microbiological analyses requires that the transport box should contain cold water in addition to ice or an “ice pack”.

i) The use of a solid coolant alone is inadequate because heat transfer and sample

cooling are too slow. Bottles containing samples for bacteriological analysis should ideally be placed in clear plastic bags to protect them from external contamination.

ii) If the delay between sample collection and bacteriological analysis will be less than 2 hours, samples should simply be kept in a cool, dark place.

iii) When more than 2 hours will elapse, samples should be chilled rapidly to about 4 °C by placing them in a cold water/ice mixture (see above) in an insulated container, where they should remain during shipment.

iv) If the time between collection and analysis exceeds 6 hours, the report of the analysis should include information on the conditions and duration of sample transport.

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Figure 6.7 Field sample storage box

6.3.17 Shipping Samples to Contract Laboratory

i) Prior to shipping samples, notify the laboratory of how many samples of what type and when to expect shipment.

ii) Ensure that laboratory personnel will be available to receive the shipment. iii) Check that the sample bottles are correctly labeled according to the protocols of the

contract laboratory and that caps are securely tightened. iv) Complete the analytical services request and chain-of-custody forms provided by the

Laboratory. v) Pack samples carefully in the shipping container according to laboratory protocols, to

prevent bottle breakage, shipping container leakage, and sample degradation.

6.3.18 Equipment Cleaning and Storage

i) Clean all sample collection and storage containers and lab-ware in a 0.1N HCl acid bath followed by deionized water rinses.

ii) Monitoring equipment should be cleaned and packed for storage. iii) Keep equipment and supplies properly organized and labeled so they can easily be

inventoried using the checklists.

6.3.19 Field Data Entry and Management

i) Download or enter field and laboratory data into appropriate spreadsheets and databases as soon as possible to minimize error.

ii) Refer to the instrument manufacturer’s instruction manual for details on downloading data from field data loggers.

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6.3.20 End of Field Season Procedures

i) When sensor probes are to be stored for extended periods of time, thoroughly clean sensors, remove batteries, and store the sonde according to specific instructions in the manufacturer’s manual.

ii) Store calibration standards and electrolyte solutions in a temperature controlled environment.

iii) Ensure that containers are dated upon receipt and upon opening; observe expiration dates.

6.3.21 Reception of samples by the laboratory

A member of the laboratory staff to sign for the receipt of samples and to make the following checks at the same time:

i) All of the necessary details are recorded on the labels of sample bottles. ii) The samples are contained in appropriate bottles. iii) Samples have arrived in time for subsequent analysis to provide a reliable picture of

water quality at the time of sampling. iv) Samples have been treated with any necessary preservatives. v) Samples have been stored at appropriate temperatures, maintained throughout

transport.

Samples should be logged into the laboratory system as soon as they arrive and transferred to a refrigerator at about 4 °C. If someone other than laboratory staff is to receive the samples, they should be instructed to transfer them directly to a refrigerator, noting the time and the condition of the samples, and then inform laboratory staff accordingly.

Where sample storage times and/or conditions have been such as to make it unlikely that analyses will yield reliable results, laboratory staff should decline to accept the affected samples. Supervisory staff should lend their support to the decision to reject samples on this basis.

6.3.22 Safety during field work

Suitable protective equipment, such as rubber gloves, should be provided and its use by staff strongly encouraged. Field staff should be trained to recognise and deal with as many as possible of the hazards they are likely to encounter. As a minimum, training should include water safety and first-aid. If monitoring staff is new to the site seek, guidance from the community on the safety of the site. Sites with wild animals need to be approached with lots of care. Security personnel might be required for sites with unwelcoming communities.

A basic first-aid kit should be carried at all times, and should not be left in the transport vehicle if the staff are obliged to move any significant distance from it.

6.4 Laboratory analysis for physical-chemical parameters

The laboratory analysis is to be performed by the laboratory staff within stipulated time and precision. Table 6.4 shows the recommended methods for analysis of Physical-chemical parameters in water. It is observed that many laboratories have their own procedures traditionally being followed. Not only that they also use different units to present the results and sometimes many digits after decimal. This create unnecessary problem in integrating the

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results. In order to make the procedures uniform and also presentation methods uniform a guideline is prepared. The analytical methods are prescribed for each parameter along with measurement unit and significant figure.

Table 6.4. Example range of analytical methods, method detection limits (MDLs), containers, preservation methods, and holding times.

Analyte Analytical technique

Method

Det. Limit

Vol (mL)

Filter

Preservation

Sample Bottle Note 2

Hold Time

Alkalinity

Titrimetry Spec. auto Titrimetry

310.1 EPA-ERL 310.2 EPA-NERL NFM USGS-OWQ

10 mg/L 10 mg/L 0.01 mg/L

4 oC 4 oC non

14 days 14 days Non

Calcium

ICP Titrimetry FAA

3120B APHA 215.2 EPA-NERL I-3152 USGS-NWQL

10 µg/L 0.5 mg/L 0.1 mg/L

250 mL

Note 3 Note 3 Note 3

pH<2 HNO3 4 oC pH<2 HNO3

P or G P

6 mons 6 mons 180 days

Chloride

ICP Titrimetry FAA

300.0 EPA-NERL 325.2 EPA-NERL 4500-Cl APHA

0.02 mg/L 0.1 mg/l 0.15 mg/L

100 mL

4 oC 4 oC 4 oC

P or G P or G

28 days 28 days 28 days

Chlorophyll-a

Spect. 10200 APHA 2 ug/L < 1 L Note 4 Freeze filter

P 30 days

DOC Spect. Spect.

415.3 EPA 0-1122-92 USGS

0.018 mg/L 0.1 mg/L

125 Note 3 pH<4 H2SO4 4oC

G AG

28 days

K ICP FAA

3120B APHA 3111B APHA

0.3 mg/L 5 ug/L

Note 3 Note 3

pH<2 HNO3 pH<2 HNO3

P or G P or G

6 mos 6 mos

Mg ICP FAA

3120B APHA 3111B APHA

20 ug/L 5 ug/L

Note 3 Note 3

pH<2 HNO3 pH<2 HNO3

P or G P or G

6 mos 6 mos

Na ICP FAA

3120B APHA 3111B APHA

30 mg/L 2ug/L

Note 3 Note 3

pH<2 HNO3 pH<2 HNO3

P or G P or G

6 mos 6 mos

NH4-N Selective elec. Colorimetry

4500-NH3E 350.2 EPA-

0.08 mg/L 0.08 mg/L

4oC/ pH 2, 0 oC

24h/28d

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Titrimetry IC

NERL 4500-NH3 APHA

5 mg/L pH<4 H2SO4 4oC/ pH2,0oC

28 day 24h/28d

SiO2 ICP Spect. FIA-Spect.

3120B APHA 4500- SiO2 D APHA 4500- SiO2 F APHA

20 ug/L 0.04 mg/L 0.78 ug/L

Note 3 Note 3 Note 3

pH<2 HNO3 No, 4oC No, 4oC

P or G G G

6 mos 28 days 28 days

SO42- IC CIE-UV Spect.

4110C APHA D6508 ASTM 37512 EPA-NERL

75 ug/L 0.1 mg/L 0.5 mg/L

Note 3 Note 3 Note 3

pH<4 H2SO4 pH<4 H2SO4 pH<4 H2SO4

P or G P or G

ASAP 28 days

TP Spect. Alkaline P ICP

I-2606 USGS-NWQL USGS 2003 200.7 EPA-NERL

0.001 mg/L 0.01 mg/L 60 ug/L

125 mL 120 mL

Note 5 MgCl 4oC 4oC /H2SO4 pH<2 HNO3

Brow n P P

30 days 48 h/30d 6 mons

TN Alkaline P Titrimetry Combustion

USGS 2003 4500-N 440.0 EPA-NERL

0.03 mg/L 0-100 mg/L 0.1 mg/L

4oC/H2SO4 4oC Filter

AG

48 h/30d 7 days 100 day

Note 1. CIE-UV= capillary ion electrophoresis with UV detection, FAA = flame atomic absorption, FIA = flow injection analysis, IC= ion chromatography, ICP = inductively coupled plasma, Spec. auto = spectroscopy with auto-analyzer Note 2. P = plastic (polypropylene), G=glass, AG=amber glass Note 3.0.45µm membrane filter. Pre-filter for dissolved portion analysis. Note 4.0.45µm glass fiber filter. Note 5. (Patton and Kryskalla, 2003). Guidance on the methods for POPs analysis are summarised in Chapter 8 on analytical methods for POPs recommended under the GMP on persistent organic pollutants (UNEP, 2020). The methods should be updated regularly as the guidance document is updated.

6.5 Data validation

i) Absolute checking/Data entry

i) Checking if data is within the detection limits of a particular method ii) Checking if the data is within the expected ranges for a parameter iii) Checking if there are too many (or too few) significant digits reported iv) Checking if data are physically or scientifically possible (general checks)

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v) Checking correlation of parameters (Some conditional checks like BOD/COD relation, TC/FC relation)

vi) Checking the correlation between EC and TDS vii) Checking cation/anion balance viii) Total coliforms must be greater than faecal coliforms ix) Total iron must be greater than dissolved iron x) Total phosphorus must be greater than dissolved (ortho-)phosphorus

ii) General checks:

i) Total solids ≥ Total dissolved solids ii) Total solids ≥ Total settleable solids iii) COD > BOD iv) Total Coli ≥ Faecal Coli v) Total Iron ≥ Fe+2, Fe+3 vi) Total P ≥ PO4

-3 vii) EC (µS/cm) ≥ TDS (mg/l) viii) Total oxidized nitrogen ≥ Nitrate, nitrite ix) Total oxidized nitrogen = Nitrate + nitrite x) Total hardness = Ca hardness + Mg hardness

iii) Conditional Checks

When there are known correlations between one or more water quality parameters these can be used. Some of the well-known correlations between parameters are:

i) Total dissolved solids and specific conductance ii) pH and carbonate species iii) pH and free metal concentrations iv) Dissolved oxygen and nitrate v) If pH <8.3 then Carbonate = 0 vi) If DO = 0, then nitrate = 0 vii) If DO >0, then nitrate > 0 viii) If DO > 7mg/L, then ferrous ions = 0 ix) If nitrite >0, then ferrous ions = 0 x) If ferrous ions >0, then nitrite = 0

6.6 Data analysis and presentation

Data should be subjected to some simple statistical analysis to summarise the data; to transform them to aid understanding or to compare them with a water quality standard that is couched in statistical terms. These include annual mean, standard deviation, trend, seasonal changes or a percentile for certain parameters. The data can also be summarized in form of index. Statistical analysis like parametric correlation, seasonal fluctuations, seasonal trends over a period of time are also common. The data after analysis can be presented in different format. For a river usually river profiles are commonly presented. For groundwater contours are plotted over a geographical area.

Graphical Presentation formats:

i) Time Series Graphs

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ii) Histograms iii) Pie Charts iv) Profile Plots (river profiles) v) Geographical Plots (contours)

6.7 Data Interpretation

Data interpretation involves understanding on the water chemistry, biology and hydrology. Normally data is analysed and interpreted in terms of chemical quality, quality fluctuations, and their possible effect on different uses and ecosystem. A comparison is made with predefined criteria or standards set for protection of different uses. The quality fluctuation should be explained in view of possible sources of pollution and their fates in aquatic environment and their effects. A sample of analytical metadata capture form for water media is shown in Appendix Table A1.1.

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7. SOIL SAMPLING PROCEDURES

7.1 Soil Sampling

The method and procedure for obtaining soil samples vary according to the purpose of sampling. Soils vary from place to place hence efforts should be made to take the samples in such a way that it is fully representative of the field. Normally one to ten gram of soil is used for each chemical determination and represents as accurately as possible the entire surface 0-22 cm of soil, weighing about 2 million kg/ha.

The procedures contained in this section are to be used by field personnel when collecting and handling soil samples in the field. In case the field personnel determine that any of the procedures described in this section are inappropriate, inadequate or impractical and that another procedure must be used to obtain a soil sample, the variant procedure should be documented in the field logbook and subsequent investigation report, along with a description of the circumstances requiring its use.

7.2 Soil sampling precautions

The following precautions should be considered when collecting soil samples:

i) Special care must be taken not to contaminate samples. This includes storing samples in a secure location to preclude conditions which could alter the properties of the sample.

ii) Samples shall be custody sealed during long-term storage or shipment. iii) Collected samples are in the custody of the sampler or sample custodian until the

samples are relinquished to another party. iv) If samples are transported by the sampler, they will remain under his/her custody or

be secured until they are relinquished. v) Shipped samples shall conform to national soil requirements for research. vi) Documentation of field sampling is done in a bound logbook. vii) Chain-of-custody documents shall be filled out and remain with the samples until

custody is relinquished. viii) All shipping documents, such as air bills, bills of lading, etc., shall be retained by the

project leader in the project files. ix) Sampling in landscaped areas: Cuttings should be placed on plastic sheeting and

returned to the borehole upon completion of the sample collection. x) Any ‘turf plug’ generated during the sampling process should be returned to the

borehole. xi) Sampling in non-landscaped areas: Return any unused sample material back to the

auger, drill or push hole from which the sample was collected.

7.3 Special Precautions for Trace Contaminant Soil Sampling

i) A clean pair of new, non-powdered, disposable gloves will be worn each time different sample is collected and the gloves should be donned immediately prior to sampling.

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ii) The gloves should not come in contact with the media being sampled and should be changed any time during sample collection when their cleanliness is compromised.

iii) Sample containers with samples suspected of containing high concentrations of contaminants shall be handled and stored separately.

iv) All background samples shall be segregated from obvious high-concentration or waste samples.

v) Sample collection activities shall proceed progressively from the least suspected contaminated area to the most suspected contaminated area.

vi) Samples of waste or highly-contaminated media must not be placed in the same ice chest as environmental (i.e., containing low contaminant levels) or background samples.

vii) If possible, one member of the field sampling team should take all the notes and photographs, fill out tags, etc., while the other member(s) collect the samples.

viii) Samplers must use new, verified/certified-clean disposable or non-disposable equipment cleaned according to procedures contained in the Operating Procedure for Field Equipment Cleaning and Decontamination for collection of samples for trace metals or organic compound analyses.

7.4 Sample Homogenization

i) If sub-sampling of the primary sample is to be performed in the laboratory, transfer the entire primary sample directly into an appropriate, labelled sample container(s). Proceed to step 4.

ii) If sub-sampling the primary sample in the field or compositing multiple primary samples in the field, place the sample into a glass or stainless steel homogenization container and mix thoroughly. Each aliquot of a composite sample should be of the same approximate volume.

iii) All soil samples must be thoroughly mixed to ensure that the sample is as representative as possible of the sample media.

7.5 Samples for VOC analysis are not homogenized.

The most common method of mixing is referred to as quartering. The quartering procedure should be performed as follows:

i) The material in the sample pan should be divided into quarters and each quarter

should be mixed individually. ii) Two quarters should then be mixed to form halves. iii) The two halves should be mixed to form a homogenous matrix. iv) This procedure should be repeated several times until the sample is adequately mixed.

If round bowls are used for sample mixing, adequate mixing is achieved by stirring the material in a circular fashion, reversing direction, and occasionally turning the material over.

v) Place the sample into an appropriate, labelled container(s) by using the alternate shoveling method and secure the cap(s) tightly.

vi) The alternate shoveling method involves placing a spoonful of soil in each container in sequence and repeating until the containers are full or the sample volume has been exhausted.

vii) Threads on the container and lid should be cleaned to ensure a tight seal when closed.

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7.6 Dressing Soil Surfaces

Any time a vertical or near vertical surface is sampled, such as achieved when shovels or similar devices are used for subsurface sampling, the surface should be dressed (scraped) to remove smeared soil. This is necessary to minimize the effects of contaminant migration interferences due to smearing of material from other levels.

7.7 Soil Samples for Volatile Organic Compounds (VOC) Analysis

Samples to be analyzed for VOC should be collected in a manner that minimizes disturbance of the sample. The sample for VOC analysis should be collected directly from the auger bucket (preferred) or from minimally disturbed material immediately after an auger bucket is emptied into the pan. The sample shall be containerized by filling an En Core® Sampler or other Method 5035 compatible container.

7.8 Soil Sampling

The specific sampling containers and sampling tools required will depend upon the detection levels and intended data use. Once this information has been established, selection of the appropriate sampling procedure and preservation method best applicable to the investigation can be made.

7.8.1 Equipment

Once the soil has been obtained, the En Core® Sampler, syringes, stainless steel spatula, standard 2- oz. soil VOC container, or pre-prepared 40 mL vials may be used/required for sub-sampling.

The specific sample containers and the sampling tools required will depend upon the data quality objectives established for the site or sampling investigation. The various sub-sampling methods are described below.

7.8.2 Sampling Methodology - Low Concentrations (<200 µg/kg)

When the total VOC concentration in the soil is expected to be less than 200 µg/kg, the samples may be collected directly with the En Core® Sampler or syringe. If using the syringes, the sample must be placed in the sample container (40 mL vial) immediately to reduce volatilization losses. The 40 mL vials should contain 10 mL of organic-free water for an un-preserved sample or approximately 10 mL of organic-free water and a preservative. It is recommended that the 40 mL vials be prepared and weighed by the laboratory (commercial sources are available which supply preserved and tared vials). When sampling directly with the En Core® Sampler, the vial must be immediately capped and locked.

A soil sample for VOC analysis may also be collected with conventional sampling equipment. A sample collected in this fashion must either be placed in the final sample container (En Core® Sampler or 40 mL pre-prepared vial) immediately or the sample may be immediately placed into an intermediate sample container with no head space. If an intermediate container (usually 2-oz. soil jar) is used, the sample must be transferred to the final sample container (En Core® Sampler or 40 mL pre-prepared vial) as soon as possible, not to exceed 30 minutes.

Soil samples may be prepared for shipping and analysis as follows:

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i) En Core® Sampler - the sample shall be capped, locked, and secured in the original foil bag.

ii) All foil bags containing En Core® samplers are then placed in a plastic bag and sealed with custody tape, if required.

iii) Syringe - Add about 3.7 cc (approximately 5 grams) of sample material to 40-mL pre-prepared containers. Secure the containers in a plastic bag.

iv) Do not use a custody seal on the container; place the custody seal on the plastic bag. Note: When using the syringes, it is important that no air is allowed to become trapped behind the sample prior to extrusion, as this will adversely affect the sample.

v) Stainless Steel Laboratory Spatulas - Add between 4.5 and 5.5 grams (approximate) of sample material to 40 mL containers. Secure the containers in a plastic bag.

vi) Do not use a custody seal on the container; place the custody seal on the plastic bag.

7.8.4 Sampling Methodology - High Concentrations (>200 µg/kg)

Based upon the data quality objectives and the detection level requirements, this high level method may also be used. Specifically, the sample may be packed into a glass container with a screw cap and septum seal. The sample container must be filled quickly and completely to eliminate head space. Soils\sediments containing high total VOC concentrations may also be collected as described in Section 3.2.2, Sampling Methodology - Low Concentrations, and preserved using 10 mL methanol.

7.8.5 Special Techniques and Considerations

i) Effervescence

If low concentration samples effervesce (rapidly form bubbles) from contact with the acid preservative, then either a test for effervescence must be performed prior to sampling, or the investigators must be prepared to collect each sample both preserved or un-preserved, as needed, or all samples must be collected unpreserved.

To check for effervescence, collect a test sample and add to a pre-preserved vial. If preservation (acidification) of the sample results in effervescence then preservation by acidification is not acceptable, and the sample must be collected un-preserved.

If effervescence occurs and only pre-preserved sample vials are available, the preservative solution may be placed into an appropriate hazardous waste container and the vials triple rinsed with organic free water. An appropriate amount of organic free water, equal to the amount of preservative solution, should be placed into the vial. The sample may then be collected as an un-preserved sample. The amount of organic free water placed into the vials will have to be accurately measured.

ii) Sample size

While this method is an improvement over earlier ones, field investigators must be aware of an inherent limitation. Because of the extremely small sample size and the lack of sample mixing, sample representativeness for VOCs may be reduced compared to samples with larger volumes collected for other constituents. The sampling design and objectives of the investigation should take this into consideration.

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iii) Holding times

Holding time for an un-preserved VOC soil/sediment sample on ice is 48 hours. Hence arrangement should be made to ship the soil/sediment VOC samples to the laboratory by overnight delivery the day they are collected so the laboratory may preserve and/or analyze the sample within 48 hours of collection.

iv) Percent solids

Samplers must ensure that the laboratory has sufficient material to determine percent solids in the VOC soil/sediment sample to correct the analytical results to dry weight. If other analyses requiring percent solids determination are being performed upon the sample, these results may be used. If not, a separate sample (minimum of 2 oz.) for percent solids determination will be required. The sample collected for percent solids may also be used by the laboratory to check for preservative compatibility.

v) Safety

Methanol is a toxic and flammable liquid. Therefore, methanol must be handled with all required safety precautions related to toxic and flammable liquids. Inhalation of methanol vapours must be avoided. Vials should be opened and closed quickly during the sample preservation procedure. Methanol must be handled in a ventilated area. Use protective gloves and gas mask when handling the methanol vials. Store methanol away from sources of ignition such as extreme heat or open flames. The vials of methanol should be stored in a cooler with ice at all times.

vi) Shipping

i) Methanol and sodium bisulphate are considered dangerous goods, therefore shipment of samples preserved with these materials by common carrier is regulated.

ii) Regulations must be followed when shipping methanol and sodium bisulphate. Consult regulatory framework or the carrier for additional information.

iii) Shipment of the quantities of methanol and sodium bisulphate used for sample preservation falls under the exemption for small quantities.

7.9 Methods for collecting soil samples

Table 7.1 gives a summary of soil sampling methods.

Table 7.1 Methods for soil sampling

Soil sampling Method

Observations

Manual Soil Sampling Methods

Used primarily to collect surface and shallow subsurface soil samples. Surface soils are generally classified as soils between the ground surface and

6 to 12 inches below ground surface. The most common interval is 0 to 6 inches; however, the data quality

objectives of the investigation may dictate another interval, such as 0 to 3 inches for risk assessment purposes.

The shallow subsurface interval may be considered to extend from approximately 12 inches below ground surface to a site-specific depth at which sample collection using manual collection methods becomes

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impractical. i) Spoons

Stainless steel spoons may be used for surface soil sampling to depths of approximately 6 inches below ground surface where conditions are generally soft and non-indurated, and there is no problematic vegetative layer to penetrate.

ii) Hand Augers

Hand augers may be used to advance boreholes and collect soil samples in the surface and shallow subsurface intervals.

Typically, 4-inch stainless steel auger buckets with cutting heads are used. The bucket is advanced by simultaneously pushing and turning using an

attached handle with extensions (if needed). Surface Soil Sampling

When conducting surface soil sampling with hand augers, the auger buckets may be used with a handle alone or with a handle and extensions.

The bucket is advanced to the appropriate depth and the contents are transferred to the homogenization container for processing.

Subsurface Soil Sampling

Hand augers are the most common equipment used to collect shallow subsurface soil samples. Auger holes are advanced one bucket at a time until the sample depth is achieved.

The practical depth of investigation using a hand auger depends upon the soil properties and depth of investigation. In sand, augering is usually easily performed, but the depth of collection is limited to the depth at which the sand begins to flow or collapse.

Direct Push Soil Sampling Methods

Used primarily to collect shallow and deep subsurface soil samples Has three methods and all sampling tools involve the collection and retrieval

of the soil sample within a thin-walled liner. Large Bore® Soil Sampler Macro-Core® Soil Sampler Dual Tube Soil Sampling System

Split Spoon/Drill Rig Methods

Used primarily to collect shallow and deep subsurface soil samples. All split spoon samplers, regardless of size, are basically split cylindrical barrels that are threaded on each end.

The leading end is held together with a bevelled threaded collar that functions as a cutting shoe.

The other end is held together with a threaded collar that serves as the sub used to attach the spoon to the string of drill rod.

Two methods: smaller diameter standard split spoon, driven with the drill rig safety hammer, and the larger diameter continuous split spoon, advanced inside and slightly ahead of the lead auger during hollow stem auger drilling.

Shelby Tube/Thin-Walled Sampling Methods

Also called thin-walled push tubes or Acker thin-walled samplers, are used to collect subsurface soil samples in cohesive soils and clays during drilling activities.

Backhoe Sampling Method

Used in the collection of surface and shallow subsurface soil samples. The trenches created by excavation with a backhoe offer the capability of

collecting samples from very specific intervals and allow visual correlation with vertically and horizontally adjacent material.

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7.10 Soil sampling sites and frequency

Proposed soil monitoring sites and frequency are shown in Table 7.2 below. The sites were selected based on previous history of potential contamination that need to be managed in environmentally sound manner.

Table 7.2 Soil monitoring sites for POPs monitoring in soil

Region Soil Sample type Sampling frequency

Nairobi Dandora Bulk/composite Annually

Kitengela/sheep and goats project

Bulk/composite Annually

ECCL old area* Bulk/composite Annually

Mombasa Kibarani Bulk/composite Annually

Mwakinunge Bulk/composite Annually

Nakuru Gioto dumpsite Bulk/composite Annually

Naivasha farming area Bulk/composite Annually

Nakuru farming area Bulk/composite Annually

Kisumu Nyalenda/LVEMP Bulk/composite Annually

Kachoki Bulk/composite Annually

Webuye Bulk/composite Annually

7.11 Quality Control

A control sample should be collected from an area not affected by the possible contaminants of concern and submitted with the other samples. This control sample should be collected as close to the sampled area as possible and from the same soil type.

Equipment blanks should be collected if equipment is field cleaned and re-used on-site or if necessary to document that low-level contaminants were not introduced by sampling tools.

7.12 Records

Field notes, recorded in a bound field logbook, as well as chain-of-custody documentation will be generated following Operating Procedure for Logbooks and the Operating Procedure for Sample and Evidence Management. A sample of analytical metadata capture form for soil media is shown in Appendix Table A1.2.

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8. ANALYTICAL METHODS FOR POPS

8.1 General consideration for trace analysis

POPs levels in environmental samples are generally low and constitute trace chemical analysis require special attention in order to obtain reliable results. These include requirements for the ideal laboratory, apparatus, analytical methods, and routine analysis work. As analytical technology improves, sensitivities are improved and the amount which can be detected becomes smaller. Hence analysts are required to pay attention to such matters as contamination or leakage at the time of trace measurement, since the accuracy of data becomes unreliable and errors in the data can be large. It is necessary to make effort to maintain low and constant blank values, and important to prevent contamination.

8.1.1 Apparatus and instruments

All apparatus and instruments used for POPs analysis should be located and maintained separately from equipment used for general analysis. If that is not possible, some management strategies to prevent the risk of contamination when apparatus and instruments are shared, have to be adopted.

8.1.2 Laboratory

The laboratory and associated equipment should be designed to allow analysts to work easily. The materials from which the laboratory is built may affect the analytical results. Building materials should be resistant to corrosion caused by the chemicals being used. Indoor temperature may have an effect on the physical measurement conducted in the laboratory. For example the volume of volumetric glassware is determined at a certain temperature. There are some operations effected by temperature such as extraction with ether, or degradation of target compounds during sample separation. Change of ambient temperature affects the character of chromatographic columns and other instruments. When experiments are conducted at specific, non-ambient temperatures, the temperature should be measured and a record maintained.

Analysts To obtain good results for trace analysis, staff must always consider the details of their work, which aspects should be paid particular attention, what aspects specifically affect results. Good results rely on the experience and cautiousness of the analysts. To obtain consistent results, staff must take pride in their work. The analyst must thoroughly understand the analysis and related matters, and be able to scientifically answer questions about their analytical results. The analyst must understand well specific analyses, and be able to evaluate the “suitability for purpose” of the adopted method. Staff must understand the basic principles of the analytical operations and the necessity of quality control systems. If any member of staff has little experience in these matters then the whole process should be closely supervised by an experienced person. An inexperienced staff

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member should not be allowed to report on his own responsibility until he obtains sufficient analytical skill under the supervision of the experienced person. All staff have to be familiar with the operation of general experimental apparatus such as balances, volumetric apparatus, and know both how to use such equipment and the error generated in their use. Staff must undertake training seminars and programs related to analytical methods and their work.

8.1.3 Analytical standards and reference materials

The term ‘analytical standard’ is used here to mean compounds and solutions which are used for making calibration curves or used for instrument checks. Use commercial standards should come with appropriate purity notes and quality control warranties. Purchase the best standards possible.

Certified reference materials designated for use in the preparation of calibration curves are recommended if they are available. If it is not possible to purchase standards whose concentration or compositions are known, prepare your own analytical standards, then determine the concentrations according to designated methods.

8.1.4 Selection / development of analytical methods

Cautious selection and development of analytical methods is crucial to obtain reliable results. The following summary shows, in order of importance, which methods might be applied for most purposes: i) Official analytical methods being simultaneously compared and unified at multiple

institutions at a very high technical level. ii) Analytical methods whose adequacy has been confirmed at more than two institutions

or which are recommended by specialist committees. iii) Analytical methods have been developed by institution itself and whose adequacy has

been confirmed. Original methods from the literature, books or various manuals.

One should use the largest quantity of sample possible given the limits of sample size and analytical constraints. This is especially important when target compounds are not evenly distributed in the sample matrix. Large amount of samples contain more target compounds, there are less contamination effects, and decreased operational losses. The most important technical points for choosing analytical methods are:

i) How much analytical accuracy is necessary? Does the chosen method satisfy this

requirement? ii) Are measurement results within the range of the calibration curve used? iii) Is the detection limit of the chosen analytical method lower than the expected

concentration of the constituent in the sample? iv) Are there any interferences in the samples? Was a spike recovery test done using

actual samples (spiked amount is equivalent to the amount in the sample)? v) Are instruments, reagents, and apparatus ready for analysis? Were staff appropriately

trained to operate the analytical methods? vi) According to historical data for the selected analytical method, did results of inter-

laboratory analysis or the repeatability reported by each institute agree well? How

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much difference is there between standard deviations of repeatability test within the same samples and that of one test operated on the whole process?

8.1.5 Accuracy and precision

a) Accuracy and precision have to be checked through the whole analytical process. Precision can be checked by analysing standards. If standards are not available, precision can be confirmed by comparing the data being collected with that from another analytical method whose principles are different and whose reliability has been confirmed. Accuracy has to be checked not only at the last determination step, but throughout the whole process. Accuracy can be checked by analysing multiple, homogeneous samples which contain multiple target compounds. Precision may also be checked by analysing spiked samples. Inclination (systematic error) can be checked by analysing samples of known composition such as standards or determining recovery of spiked samples.

8.2 Quality control system

It is necessary to establish internal quality control systems which are clearly regulated, in order to monitor performance of instruments, reliability of calibration curves and dispersion or inclination through the whole analytical procedure. This can be checked by regularly analysing compounds which are close to the composition of the samples.

Systematic internal quality control has to be conducted as a part of normal quality control in order to investigate every day or batch analytical conditions. Prepare a manual which clearly explains the procedures. The nature of quality control system depend on the importance and character of analysis, the frequency of analysis, batch size, automation capacity, difficulty of the analytical method and reliability. Confirmation of analytical results by quality control should be done for each batch. If the check samples are outside prescribed limits, abandon the results of all samples after the last check samples which give a normal result. Then conduct appropriate improvement before re-analysis of samples. Samples for quality control (QC) have to be typical samples, stable, and in a sufficient amount to be used for long periods. During the study period, whether the analytical methods fits in a prescribed range can be checked by plotting analytical values of QC samples on a normal chart. The amount of QC that has to be conducted depends on the nature of the study, but must be sufficient to prove the reliability of the analytical data. For example, it is normal to analyse one QC sample after every 20 samples. For complicated analyses, analysis of 30 % of samples as QC samples is not uncommon, sometimes more than 50 % is necessary. If the analysis is rarely conducted, analysis character tests have to be undertaken each time the method is used. This includes analysis of standards (reference materials) whose concentration are known, double analysis, and recovery tests. If the analysis is conducted more often, systematic QC using control charts and check samples has to be undertaken. Essentially, quality control plans have to include the following:

i) Regular checks for contamination. ii) Regular recovery tests using analyte concentrations similar to that in the samples to

evaluate analytical method operation. Use the same matrix as sample for recovery test.

iii) Analysis of check samples for each group of sample.

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8.3 Documenting analytical methods

The analytical methods and all routine operating procedures have to be documented. The document should contain information detailing the collection and nature of samples, details of the analytical procedure, detection limits, and methods for calculating analyte concentrations. Also it has to be clear who is responsible for the analytical methods and who has authority to change the method.

The document should be stored for a pre-determined period of time, and if some changes and improvements happen, the changes have to be made obvious in the documentation. Written methods include: analytical methods, standard analytical methods, standard operation procedure, business order, protocol etc.

8.4 Receiving and storage of samples

A reliable system for the registration and record of samples in the laboratory must be established. Samples which are brought in and the requested form of analysis should be compared and checked. Make records of any damage, or abnormality of the sample containers and the samples at the time they are received. Record the dates and the time the samples are received.

Open sample packages carefully, in a safe place and with the appropriate level of safety precautions, and in a place which has no, or minimal, risk of contamination. Mark the sample with unique numbers (codes) which can be used from the moment of sample receipt, through the analysis to the reporting of the results.

Analyse unstable samples immediately. If this is not possible, or treat and store the sample in a manner which prevents sample decomposition or change. There are several things to remember when storing and preserving samples. Although light affects only certain kind of compounds, shielding is generally necessary. To prevent evaporation of volatile compounds, it is necessary to pay special attention to temperature, exposure to sunlight, and the integrity of container seals.

The stability of samples, standards, and standard solutions is a function of standing time at each step of the analytical procedure. Samples must be stored in appropriate containers under appropriate conditions which prevent cross contamination with other samples, do not allow decomposition by external factors such as light and heat, and preserve the sample. High concentration standards and samples should be stored separately from calibration curve standards because of the possibility of contamination.

8.5 Taking sub-samples

Check visually if the samples contain objects which have to be removed. If there is any doubt about homogeneity of samples, mix the sample thoroughly. When not all of the sample is used for analysis, take representative sub-samples. Be careful of contamination and chemical changes of target compounds or sample matrices when separating samples.

When sub-samples are taken from inhomogeneous samples, special care is necessary. It may be possible to determine from exceptional data which component of the samples has to be chosen. However, most of the time samples have to be homogenised evenly.

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8.6 Sample preparation

Make sure that extraction or dissolution conditions (temperature etc.) do not cause decomposition or decrease of concentration of target compounds in the sample. Reduce interferences and contamination. Pay attention not to spill sample solutions or cause any loss by adsorption and desorption.

8.7 Measurement

Describe the operation of analytical instruments clearly, so there is no chance of any misunderstanding. Conduct regular maintenance of instruments at appropriate intervals. Mention anything which may affect instrument sensitivity. One must operate the instruments within the limits of the range of the calibration curve or optimum operating range. Check reproducibility for sample measurement beforehand.

Describe in detail in written analytical methods the making of calibration curves, the frequency of measurement of blanks, standards and check samples. Write down details of the operating range of instruments. Conduct work according to such outlines of operations e.g. for steps such as set up of instruments, judgement of ability, operating conditions and operations.

Describe in detail the possibility of interference and appropriate adjustment methods. Adjustments are done by using solutions which contain known concentrations of both target compounds and other compounds whose concentrations are the same as samples.

8.8 Making calibration curves

Measure standards repeatedly at designated intervals to make instrument calibration curves and to adjust results for changes in instrument sensitivity during measurement. Measure reagent blank as necessary in order to check if there is any residual contamination after standard measurement. Measurement of standards is also used to check if the reproducibility of results is within an acceptable range.

8.9 Monitoring and inspection

i) Using confirmed analytical methods does not always guaranteed reliable analytical results. To decrease the chance of causing errors, all analytical procedures should be conducted using a system which guarantees the quality of the analytical results. Quality assurance in trace analysis requires analysts to maintain a control chart. The control chart is useful for error detection and error correction, but it cannot prevent errors which arise at the beginning. Hence a quality assurance system must be instituted to prevent errors. Error elimination increases the quality and efficiency of analytical process.

ii) At regular intervals, internal and external inspections have to be conducted to ensure that the quality assurance program is working appropriately.

iii) Institutions participating in monitoring should participate in confirmation tests or inter-laboratory studies as a quality control on their analytical results. Such tests make direct comparisons of in-house results with results for the same samples obtained by other institutions. If possible, when conducting such tests, add check samples into routine analysis so the analysts can conduct the analysis under the normal, working conditions.

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8.8.1 Limit of Detection

The limit of detection of an analytical method is the least amount of a target analyte in sample which can be detected. The limit of detection is not the smallest amount of analyte for which the true value can be determined. Detection limits of the concentration CL, or amount qL, are calculated from the value of the least amount of analyte which can be detected, XL, accompanied by a certain uncertainty. XL is calculated by the following formula. XL=XbL+kSbL XbL is average value of the blank, and SbL is standard deviation of the blank, k is a coefficient which is determined by necessary confidence limits. Detection limits which are generally used are 3SbL or three times the S/N ratio.

8.8.2 Limit of Determination

The limit of determination of an analytical method is the smallest amount of target compounds in a sample which can be measured for a given uncertainty. It is also Limit of Quantitation, and it is calculated as 10 times the S/N ratio.

8.10 Recommended POPs analytical methods under GMP

Analytical methods selected for environmental contaminants are influenced by physical-chemical properties of the compounds. This section provides guidance on the recommended analytical capabilities for different groups of chemicals provided under the ongoing international programmes and the requirements for the instrumental analysis of POPs including PFOS related compounds Table 8.1 (UNEP, 2018).

Table 8. 1 Recommended analytical methods for POPs compounds

Instrumentation level

Equipment Infrastructure needs Chemicals

5 Sample extraction and clean-up systems (manually or automated), LC-MS/MS)

Nitrogen/air conditioning/consistent power/high operational costs/personnel specifically trained to operate and troubleshoot complicated instrumentation

PFOS and other anionic PFAS HBCD (sum and isomers)

3 Basic sample ex-traction and clean-up equipment, capillary GC-ECD, GC/MS

Nitrogen/air conditioning/power/ personnel specifically trained to operate and troubleshoot equipment problems

PBB, most PCB and all OCPs except toxaphene

2a Sample extraction and clean-up equip-ment, capillary GC-LRMS – electron ionization mode

Helium/air conditioning/ consistent power/ personnel specifically trained to operate and trouble-shoot equipment problems

PBB, most PCB and all OCPs; Also perfluoro-sulfamido alcohols in positive chemical ionization mode

2b Sample extraction and clean-up equipment, capillary GC-LRMS –

Methane or other moderating gas/air conditioning/ consistent power/ personnel specifically trained to operate and trouble-shoot equipment

PBDE and PBB, as well as toxaphene and other highly chlorinated (≥4 Cl) OCPs HBCD as a

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Adapted from GMP guidance document (UNEP, 2018)

GC-ECD – gas chromatography/electron capture detection GC-LRMS – gas chromatography/low resolution mass spectrometry GC-HRMS – gas chromatography/high resolution mass spectrometry LC-MS/MS – high performance liquid chromatography/tandem mass spectrometry PY – Person-year

Although it is very difficult to estimate operational costs according to instrumentation level, providing some orientation on investment costs as well as on consumables according to best knowledge of the experts and assuming operation of an average routine laboratory:

More detailed information can be taken from the UNEP POPs Laboratory Databank where many laboratories have provided costing information for analysis to third parties.

8.11 Estimated Investment for POPs analysis

The estimated investment for POPs analysis has been conducted under the GMP and summarised as shown in the Table 8.2 below (UNEP, 2018). The estimated cost for POPs analysis under international programmes are summarised in the table. The costs are meant to guide parties interested in developing national monitoring programmes and laboratory capacities for POPs analysis. At national levels the costs for analysis can be lowered particularly for government funded laboratories where the costs are subsidised.

Table 8.2 Estimated cost for investment in POPs analysis laboratory and consumables.

USD Instrumentation - Analytical laboratory GC-ECD with autosampler Investment 40,000 GC-LRMS with autosampler Investment 140,000 GC-HRMS with autosampler Investment 700,000 LC-MS/MS with autosampler Investment 200,000 Air samplers USD Low-volume sampler per piece 10,000 Passive air sampler per piece 150 Grab water sampling bottle with cap (500 mL) per piece 5 Consumables Quartz filter plus PUF plugs per set Pre-cleaned PUF plugs/disks per disk 20 Analysis to third parties (cost per sample) Preferred

method USD

PCDD/PCDF HRGC-HRMS 900 dl-PCB (when in addition to PCDD/Fs) HRGC-HRMS 350 TEQ (total) HRGC-HRMS 1,150

negative chemical ionization mode

problems sum

1 Sample extraction and clean-up equipment, capillary GC-HRMS

Helium/air conditioning/ consistent power/high operational costs /personnel specifically trained to operate and troubleshoot complicated instrumentation

PCDD/PCDF, all PCB, all OCPs, PBB, all PBDE HBCD as a sum

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POPs pesticides+indicator PCB+ endosulfan (without toxaphene)

HRGC-HRMS, HRGC-LRMS, HRGC-ECD

700

Toxaphene HRGC-LRMS, HRGC-HRMS

350

PBDE+PBB153+HBCD screen HRGC-LRMS, HRGC-HRMS

450

HBCD isomers (LC) LC-MS/MS 350 PFOS (air, blood) LC-MS/MS 350 PFOS (water) 250 Materials and consumables USD HRGC columns (60 m) per piece 880 Native pesticides standard mix per unit 200 Labelled LRMS pesticides standard mix (calibration, clean-up, syringe)

per set 5,200

Labelled indicator PCB standard mix (calibration, clean-up, syringe) per set 1,500 Labelled LRMS PCDD/PCDF standard mix (EPA 8280, calibration, clean-up, syringe)

per set 4,200

Labelled HRMS PCDD/PCDF standard mix (EPA 1613, calibration, clean-up, syringe)

per set 2,820

Labelled HRMS dl-PCB standard mix (WHO-TEF mix, calibration, clean-up, syringe)

per set 2,100

Labelled MS PBDE standard mix (calibration, clean-up, syringe) per set Labelled MS PFOS standard mix (calibration, clean-up, syringe) per set

Adapted from GMP guidance document (UNEP, 2018)

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9. QUALITY ASSURANCE AND QUALITY CONTROL

REQUIREMENTS

9.1 Quality Assurance

The QA programme for a laboratory or a group of laboratories should contain a set of operating principles, written down and agreed upon by the organisation, delineating specific functions and responsibilities of each person involved and the chain of command. The key quality aspects of the monitoring programme include:

i) Sample control and documentation: Procedures regarding sample collection, labelling, preservation, transport, preparation of its derivatives, where required, and the chain-of custody.

ii) Standard analytical procedures: Procedures giving detailed analytical method for the analysis of each parameter giving results of acceptable accuracy.

iii) Analyst qualifications: Qualifications and training requirements of the analysts must be specified. The number of repetitive analyses required to obtain result of acceptable accuracy also depends on the experience of the analyst.

iv) Equipment maintenance: For each instrument, a strict preventive maintenance programme should be followed. It will reduce instrument malfunctions, maintain calibration and reduce downtime. Corrective actions to be taken in case of malfunctions should be specified.

v) Calibration procedures: In analysis where an instrument has to be calibrated, the procedure for preparing a standard curve must be specified, e.g., the minimum number of different dilutions of a standard to be used, method detection limit (MDL), range of calibration, and verification of the standard curve during routine analyses, etc.

vi) Data reduction, validation and reporting: Data obtained from analytical procedures, where required, must be corrected for sample size, extraction efficiency, instrument efficiency, and background value. The correction factors as well as validation procedures should be specified. Results should be reported in standard units.

9.2 Personnel Requirements and Training

i) Project Manager -roles and responsibilities 1) Coordinate field schedules and availability of supplies with field personnel 2) Develop a training program for field personnel 3) Develop, document, and oversee the implementation of standard procedures for field

data collection and data handling 4) Coordinate logistics with park staff 5) Develop QA/QC measures for the project, supervise staff training, and conduct

quality assurance checks of field sampling techniques at least once, mid-season, with each field crew

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6) Contract with an analytical laboratory for analysis of water samples, ensure lab results meet program needs (e.g., QA/QC procedures, meaningful minimum detection limits for dilute waters, adequate reproducibility of replicate samples)

7) Supervise or perform data entry, verification, and validation 8) Summarize data and analyze data, prepare reports 9) Serve as the main point of contact concerning data content The project manager will also work closely with the data manager in the following capacities:

1) Complete monitoring project documentation (describing who, what, where, when,

why and how of the monitoring) 2) Develop data verification and validation measures for quality assurance 3) Ensure staff are trained in the use of database software and quality assurance

procedures. 4) Coordinate changes to the field data forms and the user interface for the project

database. 5) Identify sensitive information that requires special consideration prior to distribution. 6) Manage the archival process to ensure regular archival of project documentation,

original field data, databases, reports and summaries, and other products from the project.

7) Define how project data will be transformed from raw data into meaningful information and create data summary procedures to automate and standardize this process

8) Establish meaningful liaisons with state counterparts to promote sharing of data on a timely basis.

ii) Assistant Project Manager

This person is largely responsible for implementing the monitoring protocol for water quality on large rivers, but will also have duties related to inland lakes. Specific responsibilities include:

1) Assist with coordination of field schedules and supplies 2) Assist with training field personnel 3) Coordinate logistics with park staff 4) Help ensure all aspects of QA/QC are met 5) Perform data entry, verification, and validation 6) Train other staff in the use of database software 7) Assist with data analysis and report writing

iii) Field Personnel (Field Crew Member/Leader)

The role of field personnel is to conduct all field work related to the monitoring project. Field personnel will include both a crew leader and a crew member. The crew leader is responsible for contacting the parks prior to each sampling event to ensure logistical requirements will be met. Responsibilities for both crew member and crew leader include the following:

1) Complete all training for field sampling, sample handling, and boat operation 2) Complete all phases of field season preparation 3) Collect data and samples according to developed protocols 4) Pack and ship samples to analytical laboratory

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5) Maintain accurate field and office notes 6) Ensure that all QA/QC procedures are implemented 7) Maintain and calibrate equipment according to protocols and manufacturers’

directions. 8) Communicate progress and accomplishments with the project manager during and

after sampling at each park unit, and report any deviations from sampling protocols. 9) Download, enter, and verify data into databases as required 10) Maintain documentation of important details of each field data collection period,

including explanations of all deviations from standard procedures. 11) Maintain hard copies of data forms and send original data forms to archive on a

regular basis. 12) Represent the Network in a professional manner, assist in maintaining positive

communication among the Network, park staff, and the public.

A. Data Manager

The data management aspect of the monitoring effort is the shared responsibility of the data collectors first, then the project manager, and finally the network data manager.

• Field personnel are responsible for data collection, data entry, data verification, and validation.

• The data manager is responsible for data archiving, data security, dissemination, and database design.

• The data manager, in collaboration with the project manager, also develops data entry forms and other database features (as part of quality assurance) and automates report generation.

B. Crew Qualifications

i) The crew leader must have a bachelor’s or advanced degree in biology, chemistry, or other related physical or biological science.

ii) Field experience is mandatory and laboratory experience is preferred. iii) Prior leadership experience and good decision-making skills are highly desirable, as is

experience with boats, motors, and canoes. iv) Crew members should have a background in biology, chemistry, or other related

physical or biological science, although an undergraduate degree is not required. v) Prior field experience, including that with boats, motors, and canoes, is highly

desirable and laboratory experience is preferred. vi) All crew members must be physically fit, able to work long hours in inclement

weather, and able to carry heavy loads. Sampling at some parks will involve camping for several days at a time and portaging between lakes.

9.3 Training materials

Prior to data collection, field personnel must become familiar with the use, calibration, and maintenance of all meters, probes and equipment planned for use in monitoring.

A combination of classroom and field training will be required prior to each field season. Personnel who were previously trained for this monitoring project will participate in a review of all methods and techniques. Specific details of the training procedures include:

i) Basic limnological concepts and field sampling techniques

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ii) Review of all SOPs iii) Calibration, operation, and maintenance of all field and laboratory meters and probes

used in the project iv) Methods for sample collection v) Methods for cleaning equipment vi) Methods for handling and preserving samples vii) Completion of field data forms, sample labels, chain of custody forms, analytical

service request forms viii) Data entry into data management system ix) Completion of field and calibration logbooks x) Use of GPS equipment xi) Lake/ river specific training requirements (e.g., boat operation, navigation, radios) xii) Specific training (e.g. computer use, credit card, travel etc.)

9.4 Operational Requirements

i) Annual Workload and Field Schedule

The annual workload and schedule for the monitoring of water quality in inland lakes must be viewed within the context of the other planned water quality monitoring activities. We prepared the estimated workload and schedule for monitoring of inland lakes and large rivers together, but anticipate additional related protocols in the future (e.g., wadeable streams). As these additional protocols become part of the GLKN monitoring program, the workloads are likely to change.

ii) Facility and Equipment Needs

• At the field crew will need a facility with a sink and counter-top space where they can calibrate instruments, clean and store equipment, and process samples.

• They will also need a refrigerator and freezer for storing samples prior to shipment to an analytical laboratory, and secure space for storing a boat, motor and gasoline, canoe, and other field equipment.

• Availability of needed space varies across park units, but all park units with inland lake resources can meet the basic necessities.

9.5 Analytical Quality Control

This includes both within-laboratory AQC and inter-laboratory AQC.

9.5.1 Intra-laboratory programme studies

These include recovery of known additions to evaluate matrix effect and suitability of analytical method; analysis of reagent blanks to monitor purity of chemicals and reagent water; analysis of sample blanks to evaluate sample preservation, storage and transportation; analysis of duplicates to asses method precision; and analysis of individual samples or sets of samples to obtain mean values from same control standard to check random error. All these Analytical Quality Control (AQC) exercises are internal mechanisms for checking performance and protecting laboratory work from errors that may creep in. These control checks results in only about 5 percent extra work.

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i) Shewhart Control Chart

Shewhart control chart is most widely used form of control charts. In its simplest form, results of individual measurements made on a control sample are plotted on a chart in a time series. The control sample is analyzed in the same way as the routine samples at fixed time intervals, once or twice every week, or after 20 to 50 routine samples.

The chart is constructed from 20 or more replicate analysis results of a control or standard samples. Two lines are inserted on the chart at 2 standard deviations above and below the mean value called upper and lower warning limits, UWL and LWL, respectively.

Figure 9.1 Shewhart Control Chart

If the method is under control, approximately 4.5% of results may be expected to fall outside these lines. This type of chart provides a check on both random and systematic error gauged from the spread of results and their displacement, respectively. Standard Methods lists the following actions that may be taken based on analysis results in comparison to the standard deviation.

Control limit: If one measurement exceeds the limits, repeat the analysis immediately. If the repeated analysis result is within the upper and lower control limits UCL and LCL, continue analyses; if it exceeds the action limits again, discontinue analyses and correct the problem.

Warning limit: If two out of three successive points exceeds the limits, analyse another sample. If the next point is within the UWL and LWL, continue analyses; if the next point exceeds the warning limits, discontinue analyses and correct the problem.

Standard deviation: If four out of five successive points exceed one standard deviation, or are in increasing or decreasing order, analyse another sample. If the next point is less than one standard deviation away from the mean, or changes the order, continue analyses; otherwise discontinue analyses and correct the problem.

Central line: If six successive points are on one side of the mean line, analyse another sample. If the next point changes the side continue the analyses; otherwise discontinue analyses and correct the problem.

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Precision: The most important parameter to evaluate in the results is the precision. Numerical values of standard deviations of low concentration solutions are usually smaller than those of solutions with higher concentrations. Therefore, the coefficient of variation, should be used to evaluate precision. This is particularly useful when comparing results of analysis for samples having different concentrations.

The use of the data determines the required precision. Detection of trends may require more precise results in order to actually detect small changes with time than checking water for use, say for irrigation.

Warning and control limits should be recalculated periodically. Especially when new techniques are introduced, the precision improves when experience is gained with the technique. A good time for recalculating the control and warning limits is at the time when the control chart is full and a new graph has to be created anyway. At this point, use the 20 most recent data on the old chart for construction of LCL, LWL, average, UWL and UCL.

ii) Field Procedures

Site visits, instrument calibrations and program audits are all important elements of an effective QA system. Requirements are dependent on the sampling methods employed and resources available, but each element must be present in an effective QA program.

iii) Laboratory Procedures

Traceable standards, precision checks and inter-laboratory comparisons are all important elements of an effective QA system. Requirements are somewhat dependent on the sampling methods employed and resources available, but each element must be present in an effective QA program.

9.5.2 Inter-Laboratory AQC

Helps to test for possible bias in measurements in a laboratory. To provide direct evidence of comparability of results among laboratories in the monitoring programme. Some related objectives and benefits are listed below:

i) To assess the status of analytical facilities and capabilities of participating laboratories.

ii) To identify the serious constraints (random & systematic) in the working environment of laboratories.

iii) To provide necessary assistance to the concerned laboratories to overcome the short comings in the analytical capabilities.

iv) To promote the scientific and analytical competence of the concerned laboratories to the level of excellence for better output.

v) To enhance the internal and external quality control of the concerned laboratories inter-laboratory AQC should form the routine part of monitoring programme. Such exercises will give more confidence on results.

9.6 Guidelines on management aspects

Following important aspects are included:

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i) Before planning for environmental monitoring programme ensure that adequate resources are available as prescribed.

ii) Ensure that everybody who is involved in monitoring is fully aware of the objectives, procedures, time schedule, quality assurance and importance of this programme.

iii) Ensure that people are motivated and working with full interest. iv) Ensure that accountability of everybody is fixed. v) Ensure that there is enough communication among all the groups involved in

monitoring. vi) All the field data collected should be properly transferred to the laboratory people. vii) Data should be transferred as soon as acquired through electronic mean. viii) Adequate funds are available with the field staff and laboratory people to take care of

emergency measures. ix) Private transport facility should be available to the sampling team. x) There should be annual maintenance contract (AMC) for the repair and maintenance

of laboratory equipment/instruments. xi) There should be regular AQC exercises both internal and external and the results of

these exercises are available to anybody.

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10. DATA MANAGEMENT

Metadata allows potential data users to evaluate the quality and usefulness of the data used on an understanding of the complete process under which it was collected and maintained. Hence all protocol documentation, including standard operating procedures (SOPs), is part of a dataset’s metadata. Data validation, flagging and meta-data are all important elements of an effective quality system. Requirements are dependent on the sampling methods employed and resources available, but each element must be present in an effective QA program. Accordingly:

Copies of field information on waterproof paper should be kept in two types of 3-ring binders: a project binder and a site binder.

The project binder should contain reference information relevant to general field sampling procedures with tabs identifying each procedure for easy access during field work, including QA/QC reminders, copies of all SOPs relating to safety, decontamination, sample collection and processing, copies of equipment instructions and troubleshooting, calibration logs, extra field forms, material safety data sheets (MSDSs) for field supplies that contain hazardous chemicals or materials, and analytical service request and chain-of-custody forms.

Site binders should contain reference information specific to each sampling station, including a complete description of and directions to the monitoring site, location coordinates, maps, and photos, copies of previous field forms, and data tables summarizing all previous measurements of field variables and analytical laboratory

10.1 Data Entry, Verification, and Editing

There are three general classes of environmental quality data collected.

i) The first is field observations and measurements that are recorded on data sheets in the field.

ii) The second class of data is the results of testing performed by contract analytical laboratories.

iii) The last class of environmental quality data is digital data that have been collected by multiprobe sondes and other field data loggers.

10.2 Data Archival Procedures

Data archiving serves two primary functions:

i) It provides a source to retrieve a copy of any dataset when the primary dataset is lost or destroyed, and

ii) It provides a data record that is an essential part of the QA/QC process.

At least two complete copies of dataset are required, including digital replicas (scanned versions) of hard copy data sheets. Digital field data that are entered directly into a field computer or collected from a data logger will be backed up to a second medium at the earliest possibility. The data files on field computers and loggers must not be erased until the integrity of these data files are verified on the duplicate storage medium.

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10.3 Quality Assurance and Quality Control Pertaining to Data Entry and Management

Quality assurance and quality control procedures are crucial during every step of data entry and data management. Details of such QA/QC regarding data management are summarized below in Table 10.1.

Table 10.1 Summary of QA/QC procedures pertaining to data management.

Procedure Description Instrument calibration logs

Each instrument must have a logbook.

Field forms Field forms are the only written record of field measurements. Place copies in site binders and keep originals on file indefinitely.

Estimating precision

The precision measurement is calculated using the Relative Percent Difference (RPD) between duplicate sample results per analyte. Precision estimates should be performed within 7 days of receipt of laboratory results.

Electronic data entry

Approximately 10% of electronic data entries should be spot checked for errors on a random basis. If errors are found, another 10% are spot checked.

Data archiving

Sampling data and associated records are archived in box files and numbered consecutively by year, project, and station number.

Data validation Data validation is the process that determines whether quality control objectives for data collection were met.

Data validation reports

Data validation reports provide a narrative that discusses any deviations from QA/QC procedures and the impacts of those deviations.

Data verification Data verification demonstrates that a data set will qualify as credible data. Data verification reports

Data verification reports document the results of the data verification procedure.

Data qualification codes

Data must be fully qualified before upload.

10.4 Routine Data Summaries

This involves brief characterizations of the data from site be performed following each sampling year after all QA/QC procedures have been completed. For each water quality variable, these descriptive statistics will include mean, median, maximum, and minimum values by lake; and these same values with the addition of skew, kurtosis, and measures of variability (e.g., coefficient of variation, standard error, 95% confidence intervals). In addition to these descriptive statistics, analytical approaches may also include estimation of inter-annual change, graphic approaches (e.g., comparison of mean and variability in a parameter in the current year versus past years), and occasionally qualitative analysis. Modeling, correlational analyses, and various parametric and non-parametric analyses.

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11. IMPLEMENTING THE MONITORING PROTOCOL

11.1 Pilot monitoring network

A pilot study is necessary to test the effectiveness of the indicators and parameters chosen. This involves taking a small set of samples for analysis to test both sampling and laboratory methodologies.

11.2 Baseline monitoring

It will be important to collect baseline data in circumstances where, for example, very little is known about the site to be monitored, or in those cases when some degree of impact is expected. Collection of baseline data may take some time or even over a full annual cycle. As such adequate time may need to be factored into the monitoring programme to ensure that sufficient baseline data can be collected.

The summary tables below show the proposed implementation framework for ambient air, water and soil monitoring sites, sampling frequency, sampling methods and coordinating institutions.

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Table 11.1 Proposed monitoring framework for POPs in ambient air

Air Sampling type

Monitoring Frequency

Analytical parameters Participating Institutions

Nairobi Dandora PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others Kikuyu*Steel industry PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others Kitengela*/sheep and

goats project PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others

ECCL* (Stone Athi) PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others ECCL old area* PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others Babandogo* PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others Ngong Hills –baseline. PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others

Athi River industries PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others KNH PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others Kabete PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans University of Nairobi Chiromo Campus PUF&

Active Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans University of Nairobi

Mombasa Kibarani PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others Coast RH PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others

Mazeras PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others Bamburi PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others Nakuru Gioto dumpsite PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others Nakuru Industrial area PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others Nakuru RH PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others Kisumu Nyalenda /LVEMP PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others Kachoki dumpsite PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others KEMRI incinerator PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others Kisumu referal hospital PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others Control Site

Mt. Kenya PUF Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others

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Table 11.2 Proposed monitoring framework for POPs in ambient water

Water Type of water sampling

Monitoring Frequency

Analytical parameters Participating institution

Nairobi Fourteen falls Bulk/Composite Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, WRA (coordinate) + others

Ngong River (Njiru)

Bulk/Composite Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, WRA (coordinate) + others

Nairobi River (Njiru)

Bulk/Composite Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, WRA (coordinate) + others

Mbagathi River Bulk/Composite Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, WRA (coordinate) + others Downstream EPZ Bulk/Composite Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, WRA (coordinate) + others

Control Kikuyu Bulk/Composite WRA (coordinate) + others

Mombasa Kibarani Bulk/Composite Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, WRA (coordinate) + others

Sabaki Estuary Bulk/Composite Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, WRA (coordinate) + others

Mkurumzi River/Downstram

Bulk/Composite Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, WRA (coordinate) + others

TIOMIN Bulk/Composite Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, WRA (coordinate) + others

Mwakilinge Bulk/Composite Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, WRA (coordinate) + others

Nakuru Final effluent into Lake Nakuru

Bulk/Composite Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, WRA (coordinate) + others

Lake Naivasha/town side

Bulk/Composite Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, WRA (coordinate) + others

Lake Naivasha/flower side

Bulk/Composite Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, WRA (coordinate) + others

River Njoro Bulk/Composite Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, WRA (coordinate) + others

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Kisumu Lake Victoria Bulk/Composite Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, WRA (coordinate) + others

Kisati Bulk/Composite Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, WRA (coordinate) + others

Nyando River Bulk/Composite Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, WRA (coordinate) + others

R. Nzoia/Webuye Bulk/Composite Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, WRA (coordinate) + others

R. Nzoia/Midway Bulk/Composite Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, WRA (coordinate) + others

R. Nzoia/Mouth Bulk/Composite Quarterly OCPs, PCBs, PBDEs, PCN, SCCP, WRA (coordinate) + others

Table 11.3 Proposed monitoring framework for POPs in ambient water

Soil Sample

type

Monitoring

Frequency

Analytical parameters Participating Institution

Nairobi Dandora Composite Annually OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others

Kitengela/sheep and goats

project

Composite Annually OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others

ECCL old area* Composite Annually OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others

Juja/Roysambu KPLC site Composite Annually OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others

Mombass Kibarani Composite Annually OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others

Mwakinunge Composite Annually OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others

Nakuru Gioto dumpsite Composite Annually OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others

Naivasha farming area Composite Annually OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others

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Nakuru farming area Composite Annually OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others

Kisumu Nyalenda/LVEMP Composite Annually OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others

Kachoki Composite Annually OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others

Webuye Composite Annually OCPs, PCBs, PBDEs, PCN, SCCP, Dioxins/Furans NEMA (coordinate) + others

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11.3 Proposed Initial Analytical Laboratories for POPs Monitoring

In the initial phase of the monitoring activities, limited number of laboratories should be contacted to provide the analytical services based on their areas of competency. The coordinating agencies should contact the analytical laboratories to express their consent and logistical and financial needs. Some of the recommended laboratories are list in the list below.

Institution Available equipment OCPs PCBs PBDEs Dioxins/ Furans

PFAS

KEPHIS GC-ECD, HRGC-MS, HPLC, LC/MS

√ √ √ x x

Nairobi University

GC-ECD, GC-MS, LC/MS √ √ √ x x

PCPB HPLC, GC-ECD √ √ x x x

KEBS GC-ECD, GC-MS, HPLC √ √ √ x x

KRA GC-ECD, HPLC, GC-MS √ √ √ x x

Gov Chemist Dept.

GC-ECD, HPLC, GC-MS, ICPMS

√ √ √ x x

WRA GC-MS, GC, AAS √ √ √ x x

Vet Lab GC-MS, LCMS, ICPMS, √ √ √ x x

JKUAT

GC-MS, LCMS

√ √ x x x

SGS (Private) GC-ECD, GC-MS, GC-OMS, HPLC, FTRIS

√ √ √ x x

11.4 Data handling

The data addresses the collection, storage and analysis of the monitoring data. The data collected through the monitoring programme must be analysed in order to assess whether the monitoring goals are being achieved.

Data handling involves a several operations which include data accumulation, processing, transfer, publishing and storage. Each operation has several steps and functions need to be monitored to ensure accuracy. The data handling systems must include several measurement items that must be designed with inherent flexibility to allow addition of historical data.

Relevant experts and scientists should be consulted in interpreting the data. It will be useful to establish a small group of relevant experts/scientists with responsibility for assessing and reporting on the monitoring information.

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11.5 Reporting and publishing

There should an annual report prepared to present the monitoring data on an annual basis to enable evaluation of the state of the environment. In addition, publishing in operational and environmental journals or peer-reviewed scientific journals should be encouraged.

11.6 Programme review

Individual national programmes should periodically review any proposed monitoring programme, the results of such reviews shared amongst national operators. It is recommended that review and critical evaluation focus on each of three phases of the monitoring activity: data collection, data analysis and use of the results in management decisions.

11.5.1 Data collection

The sampling process should be reviewed to ensure that:

i) The original design of sampling location, frequency, replication and measured variables is being followed consistently. If costs, operational difficulties, changing technologies, etc. are limiting the intended design, appropriate changes must be put in place;

ii) The quality of the data is as originally specified. iii) Once analysis has begun, data collection should also be reviewed to ensure that the

design is adequate and that the collected information is meeting the objectives of the monitoring programme.

iv) It is also worth remembering that changes in the objectives/testable hypotheses may be required as new insights, or new activities, and/or technologies occur.

11.5.2 Data analysis and use

Data collection and analyses are intended to provide decision-makers with sound scientific information from which environmental management decisions are made. Therefore, programme review should consider:

i) If the data and the results of the monitoring are providing managers with the information that was envisaged in the original designs. If not adjustments must be made;

ii) Whether management’s use of the data has resulted in a measurable decrease in human impact.

11.7 Reporting format

Both annual summaries and reports that include detailed analyses on trends should follow the format of a typical peer-reviewed journal article. The following outline is a good example of the type of report to be produced.

Title page (Title, Author (s), Participating Institutions, and Date)

Table of contents page

Executive summary page (abstract)

1.0 Introduction

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1.1 Background

1.2 Justification for Study

1.3 Objectives

2.0 Methods

2. 1 Study area(s)

2.2 Field method(s)

2.3 Analytical method(s)

3.0 Results

4.0 Discussion

5.0 Management implications

6.0 Acknowledgements

7.0 Literature cited (If Any)

8.0 Tables

9.0 Figures

10.0 Appendices (If Any)

11.8 Training and capacity building institutions

The institutional capacity assessment of the key institutions involved in POPs monitoring revealed several strengths and weaknesses. The strengths include availability of basic instruments for Analysis of simple POPs such as pesticides, PCBs and PBDEs; existence of legal frameworks, mandates and identified institutions to carry out chemicals monitoring in air, water and soil; existence of personnel established in each institution; Initial chemicals analysis are going on in different institutions. The weaknesses include: lack of harmonised sampling programmes and methods; inadequate financial resources to buy consumables such as standards, spare-parts and reagents; lack of regular training in analysis of POPs and other chemicals; weak QA&QC frameworks; absence of high resolution instruments for dioxins and furans analysis; no consistent POPs monitoring programme for hot spots; and in adequate staff. In view of these weaknesses capacity building and training is a priority in order to implement a successful POPs and other chemicals monitoring at national level.

Several academic institutions in the country are engaged in training and capacity building for chemicals management. It is underscored that to implement of the national monitoring programme requires robust training in elements of POPs and other chemicals monitoring. Training should include both theoretical and hands training on sampling, analysis and data management. In view of these requirement institutions with experience in POPs monitoring are recommended to provide the necessary training modules.

Analysis of the existing capacities and experience of the institutions in POPs monitoring in the country showed that the University of Nairobi, Chemistry of Department has been involved in training on POPs monitoring in the country for over 10 years. The institution is also coordinating POPs monitoring in Africa and leads the national monitoring activities at Mt. Kenya, Kabete, Chiromo for ambient air, Athiriver and Sabaki for surface water, while mother’s milk sampling in Kenya is conducted by the Department of Public health, pharmacology and Toxicology. The Department of Chemistry has established monitoring

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sites at industrial area, Dandora and Kitengela and the data has been presented in the national and regional reports. Since the institution is already applying the international protocols under the Global Monitoring Plan and UNEP/GEF project it is best equipped to transfer the knowledge and skill gained from international programmes to build capacity for local institutions participating in POPs and other chemicals monitoring.

The second institution is the Jomo Kenyatta University of Agriculture and Technology for general training on GC/MS and LC/MS. The university offers regular training on GC/MS and LC/MS to regional institutions under the support of the Pan Africa Chemistry Network (PACN) support by the Royal Society of Chemistry (RSC). The institutions participating in the monitoring networks are strongly encouraged to participate in these training.

However, it is noteworthy that long term sustainability of training should be encouraged. Consequently, additional universities and research institutions at regional level will need systematic capacity enhancement to expand capacity building activities at county and regional levels. These include Maseno University and Masinde Muliro University of Science and Technology for the Western Region, Egerton, Moi, Eldoret, Bomet, Kisii and Kabianga Universities for the Rift Valley region, Technical University of Mombasa and Pwani University for Mombasa and coast region, Machakos, South Eastern, Embu and Meru universitie for the eastern region, and Technical University of Kenya, Kenyatta, Karatina, Kirinyaga, Murang’a and Dedani Kimathi and multimedia university of Kenya for Nairobi and Central regions.

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12 CONCLUSION AND RECOMMENDATIONS

12.1 Conclusion

1) Kenya has national and international legal and regulatory framework to implement the monitoring protocol.

2) The laboratories and monitoring institutions in the country apply different methods for sampling and analysis of pollutants.

3) There already exists some monitoring sites for all the media in Kenya but do not sufficiently cover the list of POPs pollutants.

4) The existing national capacities are not adequate for analysis of dioxins and furans in environmental media hence need to use UNEP Toolkit while targeted capacity building is carried out for analysis of dioxins and furans in the country.

5) The existing sites in national and international monitoring programmes that can be incorporated in the national monitoring programme to build on and broaden existing capacities.

6) Most laboratories in the country do not conduct analysis of POPs parameters and their incorporation in the monitoring programme will promote capacity building.

7) Regular training will be necessary to build capacity for sampling, sample analysis and reporting of the monitoring data.

8) There is no coordination among different monitoring institution to enhance networking and comparability of the data.

9) Most national institutions are not adequately funded to support robust POPs and other chemicals monitoring programme.

12.2 Recommendations:

1) In the implementation of the monitoring protocol, the ministry should start small before gradually going nationwide. The ministry should fund monitoring laboratories to include more pops testing according the institutions equipment capabilities.

2) There is need to harmonise the testing methods and standards so as to meet the international best practice to which Kenya is signatory.

3) The government should set aside more resources to increase capacity for monitoring of pollutants in collaboration with international bodies as it is stipulated in the Stockholm convention.

4) The ministry of environment should liaise with the Ministry of education to identify the best institutions from the list provided and develop curriculum for training and certification of the Environmental monitors.

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5) All monitoring institutions should be linked to form a network to avoid duplication of monitoring activities and ensure data sharing is possible.

6) The government should work with non-governmental and private institutions like Kenya Association of Manufacturers to either fund or establish monitoring sites to monitor pollutants from the industry or other diffuse sources.

7) There is need to establish a coordination and networking mechanism to ensure synergy and production of comparable monitoring data.

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13 PROTOCOL REVISION

The field of ambient air monitoring is complex, and technology is evolving rapidly. Although this Monitoring Protocol identifies national standards wherever possible, these standards may need to be supplemented from time to time with new or revised guidelines. This will also take into consideration the protocols and conventions that Kenya is signatory to. It is proposed that this protocol should be updated after the piloting phase and thereafter regularly at least after 5 years or as deemed appropriate.

Protocol Revision History Log Previous Version #

Revision date

Author

Changes made

Reason for change

New Version #

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APPENDIX 1

Laboratory Reporting Data Sheets

Table A1.1 Laboratory reporting sheet for water data

SITE SAMPLING ATTRIBUTES MEASUREMENT

Required field

Required field

Required field

Required field

Required field if Region <> International waters

Required field

Required field

Required field

Required field

Required field

Required field

Required field

Required field if Minimum = 0

Required field

Text Numeric

Numeric

Code list

Code list Code list

Code list

Code list

Code list

Code list

Integer text YYYY-MM-DD

text YYYY-MM-DD

Code list

Numeric

Numeric Numeric

Code list

Code list

Numeric

Numeric

Text

Site name

Latitude

Longitude

Region/

County

Country Water type

Sea Site

type

Potential

source

Monitoring netwo

rk

Year Start of

sampling

End of

sampling

Sampling

type water

Depth (m)

Temperature

(deg. of C)

Salinity

(PSU)

Parameter

Analytical

method

LOQ Value Laboratory

Surface seawater - ocean

Bulk e.g. PFOS (pg/l)

e.g GC-HRMS

e.g. 100

e.g. UON-Chem

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Table A1.2. Laboratory reporting sheet for soil data

SITE SAMPLING ATTRIBUTES MEASUREMENT

Required field

Required field

Required field

Required field

Required field

Required field

Required field

Required field

Required field

Required field for passive sampling

Required field

Required field

Required field if Value = 0

Required field

Text Numeric

Numeric

Code list

Code list

Code list

Code list

Code list

Integer text YYYY-MM-DD

text YYYY-MM-DD

Code list

Code list

Code list

Text Code list Code list

Numeric

Numeric

Text

Site name

Latitude

Longitude

Region/

County

Country

Site type

Potential sourc

e

Monitoring netwo

rk

Year Start of sampling

End of sampling

Sampling type

air

Sampling type air

passive

Recalculation

Recalculation descrip

tion

Parameter Analytical

method

LOQ

Value Laboratory

Kenya e.g. Agric

e.g. PCB 153 (pg/kg)

e.g. GC-MS

e.g. 0.5

0 e.g. UON-Chem

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Table A1.3. Laboratory reporting sheet for air data

SITE SAMPLING ATTRIBUTES MEASUREMENT

Required field

Required field

Required field

Required field

Required field

Required field

Required field

Required field

Required field

Required field for passive sampling

Required field

Required field

Required field if Value = 0

Required field

Text Numeric

Numeric

Code list

Code list

Code list

Code list

Code list

Integer text YYYY-MM-DD

text YYYY-MM-DD

Code list Code list

Code list

Text Code list Code list

Numeric

Numeric

Text

Site name

Latitude

Longitude

Region/

County

Country

Site type

Potential source

Monitoring netwo

rk

Year Start of sampling

End of sampling

Sampling type air

Samplin

g type air

passive

Recalculation

Recalculation descrip

tion

Analytical Parameter

Analytical

method

LOQ

Value Laboratory

Kenya e.g. Agric

e.g. national

e.g. 2020

e.g. Active or passive

e.g. PCB 153 (pg/m3)

e.g. GC-MS

e.g. 0.5

e.g. UON-Chem

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APPENDIX 2

Questionnaire for laboratory Capacity Assessment

Kenya is party to many international agreements on chemicals and wastes that address risks posed by chemicals and chemical waste to human health and the environment. It is necessary then to regularly monitor the chemicals of concern present in both indoor and outdoor environment as well as in products and food. The Ministry of Environment and Forestry resources is leading development of a national monitoring protocol for toxic chemicals of priority to human health and the environment present in air, water, products and soil. The chemicals currently being focused on are those listed by World Health Organization as 10 priority chemicals and those listed in the conventions that Kenya is party or signatory to. These include persistent Organic Pollutants (POPS) and unintentionally produced POPs (UPOPS) which include (pesticides, industrial chemicals, and toxic wastes. This exercise is being done under a UNDP/GEH/GOK project on mainstreaming chemicals management. The protocol is being done by MacKay Advocates under a consultancy managed by UNDP and the Ministry.

This capacity assessment questionnaire is to facilitate updating the existing national and county capacities and streamlining the institutional participation in National monitoring framework for chemicals and protocol for monitoring specific pollutants. The ultimate objective is that in future, at least 50% of laboratory analyses in research and monitoring institutions monitor hazardous chemicals and wastes on a cost recovery basis. The activity will result in 70% of universities nationwide include issues of hazardous chemicals and wastes, participate in chemicals risks assessment and participate in implementation of national policies and legislation on Chemicals. (Please submit your responses as soon as possible before 26th August 2020 for consideration)

1. General

Name of Institution:

Address of Institution

Name of Laboratory (if applicable)

Location (GPS)

E-mail:

Phone:

Web Page:

Contact person:

2. Technical part - Existing capacity to analyse POPs and other chemicals 2.1 Description of the Laboratory: 2.1.1 Name and address of the institution hosting the Laboratory ………………………………………………………………………………………………………………………………………………………… 2.1.2 Main activity of the Laboratory/Mandates ………………………………………………………………………………………………… ……………………………………………………… 2.1.3 Economic resources/main incomes of the institution/laboratory ………………………………………………………………………………………………… ……………………………………………………… 2.1.4 Present role in relation to the Stockholm Convention on POPs, other MEAs or regional agreements and monitoring activities ………………………………………………………………………………………………………………………………………………………… 2.1.5 Analytical work in collaboration with other laboratories

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………………………………………………………………………………………………………………………………………………………… 2.1.6 Any needs or follow-up from this self-assessment? ………………………………………………………………………………………………………………………………………………………… 2.2. Analytical quality issues 2.2.1 Which matrices and POPs are analysed in the Laboratory and with which separation/detection system? Please use the following abbreviations and the table below and expand as appropriate. For the groups of POPs: Organochlorine pesticides – OCPs

Polychlorinated biphenyls – PCB; polybrominated flame retardants – BFR dioxin-like POPs (PCDD, PCDF, dl-PCB) - dl-POPs; perfluorinated alkylated chemicals – PFAS

Other chemicals: Pesticides, Industrial Chemicals, metals, ODS, Hg Extraction methods: C = Supercritical fluid (SFE) D = Dilution F = Solid phase (SPE)

L = Liquid/liquid M = Microwave P = Pressurized fluid (PFE) S = Soxhlet U = Ultrasonic WD= wet digestion

Separation: Capillary gas chromatographic column (please specify length, type) - HRGC Liquid chromatographic column (please specify) – HPLC or UPLC

Detector ECD LRMS MS/MS TOF MS HRMS FID TCD

AAS ICP/MS XRAF UV/VIS Diode Array others (specify)

Matrix type Chemical Analyses covered

Extraction methods

Separation Detector Estimate Cost of

analysis/Group of chemicals

(Ksh.) Abiotic

Abiotic – ambient air

-Stake emission Abiotic - water

Abiotic – other: soil, sediments,

food stuff,

Biota Biota - human

milk

Biota – other: Fish, vegetables

2.2.2 Please provide approximate number of samples analysed per class of POPs or other chemicals in 2019 ………………………………………………………………………………………………………………………………………………………… 2.2.3 Is there any quality system in the Laboratory if so, which? Who is responsible? ………………………………………………………………………………………………………………………………………………………… 2.2.4 Does the Laboratory use standardised methods or own validated methods? (Please specify) ………………………………………………………………………………………………………………………………………………………… 2.2.5 Does the Laboratory apply blank tests? (Please specify)

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………………………………………………………………………………………………………………………………………………………… 2.2.6 Does the Laboratory carry out recovery tests? (Please specify) ………………………………………………………………………………………………………………………………………………………… 2.2.7 Does the laboratory carry out performance tests of the equipment? (Please specify) ………………………………………………………………………………………………………………………………………………………… 2.2.8 Does the Laboratory use certified reference materials or laboratory reference materials? (Please specify) ………………………………………………………………………………………………………………………………………………………… 2.2.9 Does the Laboratory take part in inter-laboratory studies? ………………………………………………………………………………………………………………………………………………………… 2.2.10 Are there written method descriptions and instructions? Please describe location, accessibility, updating procedures. ………………………………………………………………………………………………………………………………………………………… 2.2.11 How has the laboratory validated its methods? (Please specify) ………………………………………………………………………………………………………………………………………………………… 2.3 Documentation 2.3.1 Laboratory routines & documentation of: 2.3.2 Commissions and projects ………………………………………………………………………………………………………………………………………………………… 2.3.2 Sampling equipment and procedures used ………………………………………………………………………………………………………………………………………………………… 2.3.2 Registration and equipment for storage of samples ………………………………………………………………………………………………………………………………………………………… 2.3.4 Analytical methods and extraction & clean up equipment used ………………………………………………………………………………………………………………………………………………………… 2.3.5 Analytical work/activities ………………………………………………………………………………………………………………………………………………………… 2.3.6 Analytical Instrumental issues documented ………………………………………………………………………………………………………………………………………………………… 2.3.7 Result reports and data storage systems in place ………………………………………………………………………………………………………………………………………………………… 2.3.8 Operational costs for group analyses ………………………………………………………………………………………………………………………………………………………… 2.3.9 Validation and performance results

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………………………………………………………………………………………………………………………………………………………… 2.3.10 How are these documents filed? ………………………………………………………………………………………………………………………………………………………… 2.3.11Is there a laboratory information management system (LIMS)? ………………………………………………………………………………………………………………………………………………………… 2.4 Laboratory space/premises 2.4.1 Is the Laboratory (space) use shared with another activity? ………………………………………………………………………………………………………………………………………………………… 2.4.2 Is the laboratory free from external disturbances such as temperature, humidity, vibrations, energy supply, etc.? ………………………………………………………………………………………………………………………………………………………… 2.4.3 Is the laboratory space adequate for organic or metal trace analyses? 2.4.5 Hoods ………………………………………………………………………………………………………………………………………………………… 2.4.6 Materials free of contaminants ………………………………………………………………………………………………………………………………………………………… 2.4.7 Sample storage facilities ………………………………………………………………………………………………………………………………………………………… 2.4.8 Chemicals’ storage facilities ………………………………………………………………………………………………………………………………………………………… 2.4.9 Laboratory safety regulations protocols ………………………………………………………………………………………………………………………………………………………… 2.4.10 Is the access to the laboratory regulated? ………………………………………………………………………………………………………………………………………………………… 2.4.11 Is there framework for waste in the laboratory? Please specify. ………………………………………………………………………………………………………………………………………………………… 2.5 Laboratory personnel 2.5.1 Is the personnel familiar with QA/QC? ………………………………………………………………………………………………………………………………………………………… 2.5.2 Are there routines for training the personnel? ………………………………………………………………………………………………………………………………………………………… 2.5.3 Are there specific qualification requirements for the personnel? ………………………………………………………………………………………………………………………………………………………… 2.5.4 Are there job descriptions for the personnel?

126

………………………………………………………………………………………………………………………………………………………… 2.5.5 Is there documentation on the qualifications of the personnel? ………………………………………………………………………………………………………………………………………………………… 2.5.6 Are the personnel resources sufficient? ………………………………………………………………………………………………………………………………………………………… 2.6 Equipment 2.6.1 Is there extraction equipment for POPs or other chemical analyses (Please specify): ………………………………………………………………………………………………………………………………………………………… 2.6.2 Is there clean-up equipment for POPs or other chemical analyses? (Please specify) ………………………………………………………………………………………………………………………………………………………… 2.6.3 Which equipment (please modify where necessary) are used for POPs or other chemical analysis: ………………………………………………………………………………………………………………………………………………………… 2.6.4 HRGC/ECD [instrument/model] for analysis of: ………………………………………………………………………………………………………………………………………………………… 2.6.5 HRGC/MS [instrument/model] for analysis of: ………………………………………………………………………………………………………………………………………………………… 2.6.6 HRGC/HRMS [instrument/model] for analysis of: ………………………………………………………………………………………………………………………………………………………… 2.6.7 LC-MS/MS [instrument/model] for analysis of: ………………………………………………………………………………………………………………………………………………………… 2.6.8 ICP/MS [instrument/model] for analysis of: ………………………………………………………………………………………………………………………………………………………… 2.6.9 XRF [instrument/model] for analysis of: ………………………………………………………………………………………………………………………………………………………… 2.6.10 AAS [instrument/model] for analysis of: ………………………………………………………………………………………………………………………………………………………… 2.6.11 UV/VIS [instrument/model] for analysis of: ………………………………………………………………………………………………………………………………………………………… 2.6.12 OTHORS Please specify [instrument/model] for analysis of: ………………………………………………………………………………………………………………………………………………………… 2.6.13 How is the technical service of the instruments organized? …………………………………………………………………………………………………………………………………………………………

127

2.6.14 Are there plans to buy new equipment for POPs analyses? Or is there an urgent need for some equipment? ………………………………………………………………………………………………………………………………………………………… 2.7 Spares 2.7.1 Do you experience difficulties with supply of spare parts? ………………………………………………………………………………………………………………………………………………………… 2.7.2 Is there an urgent need of some spare parts? ………………………………………………………………………………………………………………………………………………………… 2.8 Methods/procedures used for POPs and other chemical analysis ………………………………………………………………………………………………………………………………………………………… 2.9 Additional Comments on 2.1-2.7 …………………………………………………………………………………………………………………………………………………………

3. Technical part - Capacity building/training needs 3.1 Frequency of Laboratory trainings attended last 2 years ………………………………………………………………………………………………………………………………………………………… 3.2 Number/qualification of persons to be trained ………………………………………………………………………………………………………………………………………………………… 3.3 Matrices/sample types ………………………………………………………………………………………………………………………………………………………… 3.4 POPs and other chemicals analysed ………………………………………………………………………………………………………………………………………………………… 3.5 Narrative ………………………………………………………………………………………………………………………………………………………… 4. PARTICIPATION IN CHEMICAL MONITORING ACTIVITIES. 4.1 Does Your Institution Currently Participate in Any Chemical Monitoring Activities on Air, Water, Soil? ………………………………………………………………………………………………………………………………………………………… 4.2 Do you have current monitoring sites that your institution is involved in? Indicate as appropriate. Water sites

GPS Locations and altitude

Air sampling sites

GPS Locations and altitude

Soil sampling sites

GPS Locations and altitude

Other media sampling sites

GPS Locations and altitude

128

[Please provide any additional information you feel necessary on how your institution or laboratory can participate in national chemical monitoring programme and activities] …………………………………………………………………………………………………………………………………………………………

129

APPENDIX 3

Methodology of passive air sampling of POPs in ambient air

The proposed air sampling procedure for passive air sampling in the national monitoring programme is based on the MONET Africa POPs monitoring programme and the UNEP/GEF projects implemented in Africa region. This ensures comparability of the sampling activities in the country to those conducted under the international monitoring framework under the Global Monitoring Plan under the Stockholm Convention on persistent organic pollutants. The protocols for MONET Africa and UNEP/GEF project are already being followed at the sampling stations in Mt. Kenya, Kabete and Chiromo campus, hence rolling out the sample will allow alignment and comparability of procedures to international guidelines. The detailed procedure adapted from the MONET Africa is provided in the text below.

1 Principle of method Low sensitivity to accidental short-time changes in the concentration of pollutants is a basic characteristic of passive samplers. They provide information about the long-term contamination of the studied environmental compartment (for example air). The air streams freely around a filter, membrane or other medium (sorbent), which captures pollutants during the period of passive air sampling. It is possible to use polyurethane foam (PUF) for persistent organic pollutant (POPs) sampling. The relationship between the amount of POPs captured on PUF filter and their concentrations

130

in sampled air has not been mathematically fully described yet. Due to this reason only empirical estimated information (for example based on parallel active and passive measurements) is available for results interpretation. Passive air sampling is a cheap screening method for a comparison of contamination on various sites or for verification of information obtained by active samplers [1-3]. 2 Material 2.1 Sampler (description, maintenance) Passive air sampling device consists of two stainless steel bowls attached to the common axes to form a protective chamber for the polyurethane foam filter. The filter is attached to the same rod and it is sheltered against the wet and dry atmospheric deposition, wind and UV light [4]. Exposure times between four and twelve weeks enable determination of many compounds from the POPs group. Average sampling rate was estimated to be 7 m3 /day which roughly corresponds to 200 m3 of air sampled during four weeks of deployment.

Scheme of the passive air sampling device List of the parts positioned on the axis (from the top): - hanging hook – to hang the sampler - nut and safety-nut – to fix the upper bowl

131

- pad - upper bowl (diameter 30 cm) placed up side down – it protects the filter from the rainwater and solar radiation, stabilizes a stream of air around the filter

- pad - nut – to fasten the upper bowl - distance tube (longer) – to fix the filter position below upper bowl - pad - PUF filter equipped with the metal insert (15 mm length tube prepared in the lab)

132

133

pad

134

- distance tube (shorter one) – to fix the filter position above lower bowl - nut – to fix the distance tubes before mounting the lower bowl - pad - lower bowl (diameter 24 cm) placed the bottom down – it protects the filter against the rain water and stabilizes stream of air around the filter (condensed water is drained through four holes in the bottom of the bowl)

- pad - nut and safety-nut – to fix of position of lower bowl

135

APPENDIX 4

Training Materials for POPs Analysis

1.0 SCOPE AND APPLICATION

The method is used to determine the concentrations of various organochlorine pesticides and the seven UNEP indicator PCBs in extracts from solids and liquid matrices, using capillary columns with electron capture detectors (ECD) and GC/MS.

2.0 INTRODUCTION

This document summarises the hands on training of laboratory personnel on analysis of pesticide residues offered at the Department of Chemistry, University of Nairobi, Kenya. The trainers will demonstrate how to analyse pesticide side residues in different matrices following the standard operating procedure for pesticide residue analysis followed at the Department of Chemistry.

3.0 OBJECTIVE OF THE PROTOCOL

The aim of the protocol is to enhance capacity to generate comparable data for residue analysis such as OCPs and PCBs. Among the OCPs to be analysed will include p,p'-DDT, p,p'-DDD, p,p'-DDE, HCB, aldrin, dieldrin, endrin, heptachlor, hexachlorobenzene, and a, ß, y-HCH. Attention will be paid to sampling, sample handling, sample storage, extraction, clean-up of samples, gas chromatography, reporting and various aspects of quality assurance and quality control (QA/QC) such as method validation, blanks, calibration, internal standards, reference materials, limit of detection, limit of quantification, etc.

4.0 SYNOPSIS OF THE ANALYTICAL PROTOCOL FOR PCB/OCP ANALYSIS

Grind the sample in a mortar with Na2SO4, transfer the powder to a Soxhlet thimble, and leave it for a drying period of 3 hours. Prepare sufficient alumina with 8% water and let it equilibrate overnight.

Start Soxhlet (16 hours with hexane:acetone 3:1 v/v). Include one blank, one internal reference material (IRM) and one recovery standard. In case an internal standard method is followed, an internal standard (CB112 or 103) should be added to all samples and blank, and neither the external recovery standard nor CB29 should be used.

Add 1 ml of keeper (iso-octane) and evaporate extract to approx. 1 ml on rotary evaporator.

Transfer quantitatively to an alumina column, or take an aliquot after diluting and adjusting the Soxhlet extract to a certain volume (50 or 100 ml n-pentane). Prepare alumina columns in n-hexane. Elute over Al2O3 (15 g, 8%), use 60 ml hexane for PCBs only, use 170 ml to include the OCPs.

Evaporate eluate to 1 ml with rotary evaporator and under nitrogen. Transfer to measuring cilinder of 10 ml.

136

Remove sulphur with copper rod or powder.

Prepare silica columns in iso-octane and fractionate over silica (1.8 g, 1.5%), fraction 1: 14 ml iso-octane (collect last 11 ml), fraction 2: 10 ml iso-octane:di-ethylether (85:15, v/v). Fraction 1 contains all PCBs and some OCPs (HCB, p,p’-DDE), rest of OCPs in fraction 2. Both fractions are collected in 10 ml graduated cylinders.

Carry out a test injection and determine the concentration or dilution factor. Concentrate or dilute both fractions in a graduated cylinder after adding the syringe standard (CB 112/198 or 155).

Treat solutions with sulphuric acid and quantitatively transfer top layer into autosampler vials.

Prepare dilutions from the PCB/OCP stock solutions to prepare a multi-level calibration curve.

Inject an iso-octane solution one time into the GC with the normal temperature programme for PCB/OCP analysis and subsequently start the injections of the samples and standards. Ensure that all integration parameters are opimised and the integration/calculation programme is active.

Measure samples on GC-ECD and GC/MS.

5.0 MATERIALS NEEDED

5.1. Glassware

5.1.1 Separatory funnel— 2-L, with Teflon stopcock.

5.1.2 Drying column—Chromatographic column, approximately 250 mm long x 19 mm ID, with coarse frit filter disc.

5.1.3 Concentrator tube, Kuderna-Danish— 10-mL, graduated. Calibration must be checked at the volumes employed in the test. Ground glass stopper is used to prevent evaporation of extracts.

5.1.4 Evaporative flask, Kuderna-Danish—500- mL or equivalent

5.1.5 Vials—10 to 15-mL, amber glass, with Teflon-lined screw cap.

5.2 Boiling chips-Approximately 10/40 mesh. Heat to 400°C for 30 minutes or Soxhlet extract with methylene chloride.

5.3 Water bath—Heated, with concentric ring cover, capable of temperature control (±2°C). The bath should be used in a hood.

5.4 Balance—Analytical, capable of accurately weighing 0.0001 g.

5.5 Gas chromatograph—An analytical system complete with gas chromatograph suitable for on-column injection and all required accessories including syringes, analytical columns, gases, detector, and strip-chart recorder. A data system is recommended for measuring peak areas.

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5.6.1 Column 1—1.8 m long x 4 mm ID glass, packed with 1.5% SP-2250/1.95% SP-2401 on Supelcoport (100/120 mesh) or equivalent. This column was used to develop the method performance statements in Section 14. Guidelines for the use of alternate column packings are provided in Section 12.1.

5.6.2 Column 2—1.8 m long x 4 mm ID glass, packed with 3% OV-1 on Supelcoport (100/120 mesh) or equivalent.

5.6.3 Detector—Electron capture detector. This detector has proven effective in the analysis of wastewaters for the parameters listed in the scope (Section 1.1), and was used to develop the method performance statements in Section 14.

Guidelines for the use of alternate detectors are provided in Section 12.1.

6.0 DETAILED ANALYTICAL PROTOCOL

6.1 Preparation of drying agent

Prepare Na2SO4 (approx. 3 g Na2SO4 per ±1g sample) by ‘baking out’ for 16 hours at 400 °C to remove contaminants.

6.2 Drying and activating column materials

Dry aluminum oxide, Al2O3 (15 g per sample) and silica, SiO2 (1.8 g per sample) overnight at 200 °C to make them 100% active (remove all water).

Deactivate Al2O3 and SiO2 with water: Al2O3 (8%, w/w) and SiO2 (1.5%, w/w). Add 16 ml of HPLC grade water to 184 g of activated Al2O3 in a 250 ml Erlenmeyer and shake, by hand, until all lumps are gone. Put the Erlenmeyer on a shaking table for half an hour. Follow the same procedure for SiO2, but add 1.5 ml of HPLC water to 98.5 g of SiO2. After deactivation, leave this overnight to condition. Always test the performance of Al2O3 and SiO2 before use with real samples.

6.3 Testing Al2O3 column material

Take the appropriate column (with frit), and put a layer of 1 cm of baked-out Na2SO4 on top of the frit, then add 15 g of Al2O3 and on top of this, followed by another 1 cm of baked-out Na2SO4. When adding Al2O3, it is important to tick the side of the column in order to allow the Al2O3 to settle in the column.

Condition the Al2O3 column with 15 ml of hexane (or pentane if water chiller is available). After this has eluted completely, transfer 1 ml of a standard solution containing analytes of interest to the column. Collect the eluate in a round-bottomed flask (500 ml).

After this has eluted, elute the column with 170 ml of hexane (or pentane) if PCBs and OCPs are to be analysed. This is the first fraction. For the second fraction, elute with an extra 30 ml but collect this in a separate round-bottomed flask.

The fractions are evaporated separately with the rotary evaporator. Add 2 ml of isooctane to the round-bottomed flask, and evaporate to ca. 3 ml. Transfer the extract to a tube and rinse the flask 3 times with 1 ml of hexane (or pentane). Evaporate the extract to 1 ml with a gentle stream of nitrogen. The extract is now in isooctane and ready for injection in the GC.

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A maximum of 2% of the total of the added PCBs and OCPs is allowed in the second fraction. Two exceptions: if you only are measuring PCBs then 60 ml of hexane is enough. If you want delta-HCH and beta-endosulfan (especially the latter) you should elute with 500 ml of pentane.

6.4 Testing SiO2 column material

In the fume hood, take the appropriate column for the SiO2 and plug it with silanised glass wool. Add 1.8 g of 1.5% SiO2 and put 1 cm of baked-out Na2SO4 on top. When adding SiO2, it is important to tick the side of the column in order to allow the SiO2 to settle in the column.

Condition the column with 4 ml of isooctane. After this has eluted, add 1 ml of a mixture of the PCBs and OCPs that are to be analysed. After this has eluted, elute with 14 ml of isooctane (Fraction 1). Next, elute with 10 ml of isooctane:diethylether (85:15 v/v) and collect this fraction separately (fraction 2). Next elute with 5 ml of isooctane:diethylether (85:15 v/v) and collect this separately as well (Fraction 3).

Evaporate the 3 fractions to 1 ml each under a gentle stream of nitrogen. All the extracts are in isooctane after evaporation and ready to be analysed. Identification is done on the basis of retention time.

In fraction 1, we expect PCBs and some OCPs. In fraction 2, no more than 2% of the PCBs should be present (on the basis of peak height). The OCPs will be divided over the 2 fractions. In fraction 3, no more than 2% of the OCPs found in fraction 2 should be present. (This is a check of the elution volume.)

Some OCPs (e.g. HCB) will be found exclusively in the first fraction. Other OCPs (e.g. dieldrin) will be found exclusively in the second fraction. Other OCPs (e.g. pp-DDT) will be present in both the 1st and 2nd fractions and therefore must be quantified in both fractions separately and summed after quantification. Now that the tests have been done, we proceed with the extraction.

6.5 Extraction of solid samples

If a dried sample is to be analysed, transfer it directly to the Soxhlet apparatus. If a wet sample (e.g. fish tissue) is to be analysed, place the homogenized wet sample in mortar. For each gram of wet sample add 3 g of baked-out Na2SO4. Grind this with the pestle to a homogeneous powder. Cover it (aluminum foil) and leave it overnight to dry further.

Transfer the dry sample to the Soxhlet thimble and add 100 µl of 1 ppm PCB103 (or 112) solution as an internal standard2 . Add 175 ml of pentane:dichloromethane (1:1, v/v) or hexane:acetone (3:1, v/v) to the flask (100 ml). A glass boiling rod should be added to allow smooth boiling. Allow the extraction to proceed for at least 16 hours (overnight).

Add 2 ml of isooctane as a keeper and evaporate the extract with the rotary evaporator to 3 ml. Transfer the extract to a tube and rinse the flask 3 times with 1 ml of pentane:DCM (or hexane:acetone). Evaporate under a gentle stream of nitrogen to 1 ml.

2 Please note that at this point a choice can be made for two systems: external standard or internal standard approach; in the following text the internal standard method is described; the external standard method would start here with a recovery standard solution of PCBs and OCPs to be taken through the entire procedure; the CB 103 or 112 is only added as a syringe standard after fractionation and before concentration, to correct for errors during concentration and injection. CB29 can be added to all samples and external (recovery) standard to check if something has gone wrong during the extraction and/or clean up. C29 is only used in a qualitative way and not for calculation.

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6.6 Extraction of liquid samples

Mark the water meniscus on the side of the sample bottle for later determination of sample volume. Pour the entire sample into a 2 L separatory funnel. Add 60 mL of methylene chloride to the sample bottle, seal, and shake 30 seconds to rinse the inner surface. Transfer the solvent to the separatory funnel and extract the sample by shaking the funnel for two minutes with periodic venting to release excess pressure. Allow the organic layer to separate from the water phase for a minimum of 10 minutes. If the emulsion interface between layers is more than one-third the volume of the solvent layer, the analyst must employ mechanical techniques to complete the phase separation. The optimum technique depends upon the sample, but may include stirring, filtration of the emulsion through glass wool, centrifugation, or other physical methods. Collect the methylene chloride extract in a 250 mL Erlenmeyer flask.

Add a second 60 mL volume of methylene chloride to the sample bottle and repeat the extraction procedure a second and third times, combining the extracts into 250 ml Erlenmeyer flask.

Assemble a Kuderna-Danish (K-D) or equivalent concentrator by attaching a 10 mL concentrator tube to a 500 mL evaporative flask. Other concentration devices or techniques may be used in place of the K-D concentrator if the requirements of Section 8.2 are met. Pour the combined extract through a solvent-rinsed drying column containing about 10 cm of anhydrous sodium sulfate, and collect the extract in the K-D concentrator. Rinse the Erlenmeyer flask and column with 20-30 mL of methylene chloride to complete the quantitative transfer.

Add one or two clean boiling chips to the evaporative flask and attach a three-ball Snyder column. Prewet the Snyder column by adding about 1 mL of methylene chloride to the top. Place on a hot water bath (60-65°C) so that the concentrator tube is partially immersed in the hot water, and the entire lower rounded surface of the flask is bathed with hot vapor. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 15-20 minutes. At the proper rate of distillation the balls of the column will actively chatter but the chambers will not flood with condensed solvent. When the apparent volume of liquid reaches 1 mL, remove the K-D apparatus and allow it to drain and cool for at least 10 minutes.

Increase the temperature of the hot water bath to about 60°C. Momentarily remove the Snyder column, add 50 mL of hexane and a new boiling chip, and reattach the Snyder column. For concentration of the extract, use hexane to pre-wet the column. The elapsed time of concentration should be 5-10 minutes.

Remove the Snyder column and rinse the flask and its lower joint into the concentrator tube with 1-2 mL of hexane. A 5 mL syringe is recommended for this operation. Stopper the concentrator tube and store refrigerated if further processing will not be performed immediately. If the extract will be stored longer than two days, it should be transferred to a Teflon-sealed screw-cap vial. If the sample extract requires no further clean-up, proceed with gas chromatographic analysis. If the sample requires further clean-up.

Determine the original sample volume by refilling the sample bottle to the mark and transferring the liquid to a 1000 mL graduated cylinder. Record the sample volume to the nearest 5 mL.

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6.7 Clean up with Al2O3

As for the test of the cleanup materials, take the appropriate column (with frit), and put a layer of 1 cm of baked-out Na2SO4 on top of the frit, 15 g of Al2O3 on top of that, followed by 1 cm of baked-out Na2SO4 again. When adding Al2O3, it is important to tick the side of the column in order to allow the Al2O3 to settle in the column. Condition the column with 15 ml of pentane (or hexane if pentane is unavailable).

When this has eluted completely, transfer the Soxhlet extract of the sample to column, on the top layer of Na2SO4 in the column and collect the eluate in a 250 ml round-bottomed flask. Rinse the Soxhlet extract test tube with 1 ml of pentane (or hexane) and transfer it to the top layer of Na2SO4 as soon as the sample extract has eluted. Repeat the rinse with 1 ml pentane another 4 times for best results. (Avoid allowing the column to dry out completely.) After the last elution, elute with another 165 ml of pentane (or hexane).

Add 2 ml of isooctane to the round-bottomed flask with the resulting eluate and evaporate to ca. 3 ml. Transfer the extract to a tube and rinse the flask 3 times with 1 ml of pentane (or hexane). Evaporate the extract to 1 ml with a gentle stream of nitrogen. The extract is ready for fractionation, with the exception of sediment samples (see note below).

NB: If you have a sediment sample, sulfur must be removed at this point, before fractionation. This is done by addition of activated copper powder. The copper powder has to be activated on the same day as it is used for this step. Shake the copper powder needed for that day with concentrated HCl that has been diluted factor 3 with demineralized water. Then centrifuge for 1 minute, 300 rpm, to separate the powder from the liquid. Discard the liquid and add an amount of clean methanol. Shake again and centrifuge again. Repeat the latter step another 2 times. Dry the copper powder with a gentle stream of nitrogen. When dry, it is ready to be used, but keep it well sealed until use because the air will oxidize the Cu very rapidly. Add the copper powder stepwise and in very small amounts to the sediment extract. When sulfur is present, the copper powder will turn black (oxidation). Repeat the copper powder addition until this reaction no longer occurs.

6.8 Fractionation

As for the SiO2 test, take the appropriate column for the SiO2 and plug it with silanised glass wool, in the fume hood. Add 1.8 g of 1.5% SiO2 and put 1 cm of baked-out Na2SO4 on top. When adding SiO2, it is important to tick the side of the column in order to allow the SiO2 to settle in the column.

Condition the column with 4 ml of isooctane. After this has eluted, add the sample extract and collect the eluate in a test tube (e.g. in a 15 ml tube). Rinse the sample extract test tube with 1 ml isooctane and transfer this to the column after elution of the sample extract. Repeat this rinsing step 2 more times. Next, elute with 11 ml of isooctane. Collect all the eluate in the same tube.

When all isooctane has eluted add 10 ml of isooctane:diethylether (85:15) and collect the eluate in a separate test tube.

Evaporate both extracts to 1 ml under a gentle stream of nitrogen. Add per ml of extract 200 µl of 1 ppm PCB198 solution as an injection check standard. These extracts are now ready for analysis by GC-ECD.

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7.0 PREPARATION OF THE CALIBRATION CURVE

The calibration curve will be prepared from the stock solution containing the PCB/OCPs. The curve will consist of 6 levels which are obtained by different dilutions from the stock solution. Serial dilution should be avoided. These solutions will be prepared directly into autosampler vials. The concentrations are calculated by exactly weighing all stock solution additions and iso-octane.

8.0 PERFORMING A TEST INJECTION

Make sure that the correct method is loaded in Chem station (or other integration/calculation program) and perform a test injection with the level 1 standard. Compare the response of all compounds to the response of the same level injected in the multi-level calibration of the last sequence. If both are comparable you can start the new sequence. Otherwise, try to determine what is causing the problem. Resolve this and perform a new test injection. If the deviation is more than 5%, you should prepare a new calibration curve.

9.0 GC CONDITIONS

The procedure is designed for measuring the extracts on a GC equipped with an ECD detector. The settings below are optimized for an Agilent 6890 GC with a split/splitless injector.

Oven program:

Initial temperature: 90 °C

Initial time: 2 min

Ramp 1: 15 °C/min

Final temp 1: 190 °C

Final time 1: 15 min

Ramp 2: 1 °C/min

Final temp 2: 240 °C

Final time 2: 0 min

Ramp 3: 3 °C/min

Final temp 3: 275 °C

Final time 3: 25 min

Total run time: 110.33 min

Injector settings:

Mode: Pulsed splitless

Initial temp: 250 °C

Pressure: 1.441 bar

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Pulse pressure: 4.5 bar

Pulse time: 1.5 min

Purge flow: 55.4 ml/min

Purge time: 1.4 min

Total flow: 63.5 ml/min

Column:

SGE BPX-5 (60 m x 0.22 mm x 0.25 µm)

SGE BPX-5 (30 m x 0.22 mm x 0.25 µm)

SGE BPX-35 (50 m x 0.22 mm x 0.25 µm)

Detector settings:

For ECD detector at 300 °C in “constant makeup flow” mode (30 ml/min of N2; this may differ per type of ECD).

10.0 INJECTIONS

If all samples are ready to be analyzed a sequence can be made. The order in which the samples are measured is as follows: First a solvent blank run (iso-octane) followed by the most diluted standard from the calibration curve and the mid-calibration curve standard. Then the blank sample(s), the reference sample(s), the real samples and the other calibration curve standards are injected at random. The last injection should be the mid-calibration curve standard again.

11.0 INTEGRATION AND INTERPRETATION OF CHROMATOGRAMS AND CALCULATIONS

Check first if the system has been stable over the entire analysis by doing an overlay of the middle point of the calibration curve and all the re-injections of this point during the sequence. All chromatograms should have the same responses for all peaks within a margin of 5%.

Construct a calibration curve for all compounds with Chemstation and check the linearity of the system for all compounds.

Calculate the blank and reference sample(s) that are measured in this sequence and check if the blanks are OK. Calculate for the reference sample(s) the concentrations in the sample and check if the outcome fits in the Shewart (QC) chart of the reference material. Also check the recovery of the whole procedure by calculating the amount of PCB103 (or 112) that is found and compare that to what had been added in the beginning. If all these calculations are OK you can calculate all samples from the sequence.

The detection limits can be calculated by reviewing the noise in the chromatograms next to the place where a compound should elute. The detection limit can be set as three times this noise divided by the response of this compound in the lowest calibration point multiplied by the concentration of this point (in ng injected). All compounds found with concentrations

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below this limit are reported as “< detection limit”. The LOQ (limit of quantification) is calculated in the same way, using ten times the noise level).

12.0 RE-INJECTIONS

If some of the compounds in the samples are to high to fit in the calibration curve, they can be re-injected after being diluted.

13.0 REPORTING

Finally, all data should be reported and be checked by a second technician, prior to being reported to the customer.

14.0 DECLARATION

This method is based on the analytical methodology applied at the University of Nairobi.

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APPENDIX 5

Water and Air Quality Standards

Table A5.1 Domestic Water quality standards

First schedule Second schedule

Quality standards for sources of domestic water

Water quality monitoring for sources of domestic water

Parameter Guide Value (max allowable) Guide value (max allowable) pH 6.5 – 8.5 6.5 -8.5 Suspended solids 30 (mg/L) 30 (mg/L) Nitrate-NO3 10 (mg/L) 10 (mg/L) Ammonia –NH3 0.5 (mg/L) 0.5 (mg/L)

Nitrite –NO2 3 (mg/L) 3 (mg/L) Total Dissolved Solids 1200 (mg/L) 1200 (mg/L) Scientific name (E.coli) Nil/100 ml Nil/100 ml Fluoride 1.5 (mg/L) 1.5 (mg/L) Phenols Nil (mg/L) Nil (mg/L) Arsenic 0.01 (mg/L) 0.01 (mg/L) Cadmium 0.01 (mg/L) 0.01 (mg/L) Lead 0.05 (mg/L) 0.05 (mg/L) Selenium 0.01 (mg/L) 0.01 (mg/L)

Copper 0.05 (mg/L) 0.05 (mg/L) Zinc 1.5 (mg/L) 1.5 (mg/L) Alkyl benzyl sulphonates 0.5 (mg/L) 0.5 (mg/L) Permanganate value (PV) 1.0 (mg/L) 1.0 (mg/L)

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Table A5.2 List of Priority Air Pollutants

Part I: General Source Pollutants 1) Particulate matter (Dust, black smoke, smog, aerosols); 2) Sulphur oxides (SOx); 3) Nitogen oxides (NOx); 4) Carbon monoxide (CO) 5) Carbon dioxide (CO2); 6) Hallocarbons (HC); 7) Volatile organic Compounds (VOCs); 8) Hydrogen Sulphide (H2S); 9) Hydrogen Chloride (HCl); 10) Lead and its compounds; 11) Mercury vapour (Hg) 12) Ozone (O3); 13) Dioxins and furans (PCDD and PCDF). Part II: Mobile Source Pollutants 1) Hydrocarbons (HCs) 2) VolatileorganicCompounds(VOC); 3) Sulphur dioxide (SO*) 4) Nitogen oxides (NO*) 5) Particulates (PM) 6) Carbon Monoxide (CO) Part III Greenhouse gases(GHG) 1) Carbon dioxide (CO2); 2) Methane (CH4); 3) Nirous oxides (N2O); 4) Hydrofluorocarbons(HCFCs); 5) Perfluorocarbons (PFCs); and 6) Sulphurhexafluoride (SF5).

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Table A5.3 Air quality standards

Chemical Industrial area

Residential, Rural and other areas

Controlled areas

1 Sulphur oxides (SOx); Annual Average

80 µg/M3 60 µg/M3 15 µg/M3

24 hour 125 µg/M3 80 µg/M3 30 µg/M3 Annual

Average 0.019 ppm/50

µg/M3

Month 24 hour 0.048 ppm/125

µg/M3

1 hour Instant peak 500 µg/M3

Instant peak (10 min)

0.191 ppm

2 Oxides of Nitogen (NOx); Annual Average

80 µg/M3 60 µg/M3 15 µg/M3

24 hour 150 µg/M3 80 µg/M3 30 µg/M3

8 hour Annual

Average 0.2 ppm

Month 0.3 ppm 24 hour 0.4 ppm 1 hour 0.8 ppm Instant peak 1.4 ppm 3 NitrogenDioxide (NO2) Annual

Average 150 µg/M3 0.05 ppm

Month 0.08 ppm 24 hour 100 µg/M3 0.1 ppm 1 hour 0.2 ppm Instant peak 0.5 ppm

4 Suspended particulate matter (SPM)

Annual Average

360 µg/M3 140 µg/M3 70 µg/M3

24 hour 500 µg/M3 200 µg/M3 100 µg/M3 5 Respirable Particulate

Matter (<l0pm) (RPM)

70 µg/M3 50 µg/M3 50 µg/M3

150 µg/NM3

100 µg/NM3 75 µg/NM3

6 PM2.5

7 Lead (Pb) 8 Carbon Monoxide (co)

carbon Dioxide (co,)

9 Hydrogen Sulphide

10 Non-methane hydrocarbons

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instant Peak 700 ppb 11 Total VOC 24 hours 600 µg/M3 12 Ozone 1 hour 200 µg/M3 0.12 µg/M3 8 hour (instant

Peak) 120 µg/M3 1.25 µg/M3

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APPENDIX 6

Workshop Participants

Table A6.1 List of participants to Monitoring Protocol workshops

1 Mercy Kimani MENR Email

2 JoramNjuguna Water Resources Management Authority

joramknjuguna@gmail.com

3 Richard Sikuku AAU rickuku55@gmail.com 4 Vincent Madadi University of Nairobi vmadadi@uonbia.co.ke 5 Emily Okworo Government Chemist eokworo@yahoo.com 6 Patricia Musau Water Resources Authority musaupat@gmail.com 7 Mary Mwangi Department of Social Health

Safety Mwmwangi16@gmail.com

8 Margaret Waturu Water Resources Authority mwaturu@yahoo.com 9 Nancy Narasha MENR narasham@gmail.com 10 Francis Kihumba MENR kihumbafr@yahoo 11 Mayiani Saino MENR mayiani@live.com 12 Tampushi Leonard MENR tampushi@gmail.com 13 Philip Abuor SGS Philip.Abuor@SGS.com

14 Meshack Ledama MENR ledamameshack@gmail.com 15 Muitungi Mwai NEMA mmwai@nema.go.ke 16 Onesmus Mwaniki KEPHIS omwaniki@kephis.org 17 Nicholas

Mwikwabe KEMRI nmwikwabe@kemri.org

18 Hezron Onyangore Government Chemist honyangore@gmail.com 19 James Kioko KEBS kiokom@live.com 20 John Mumbo NEMA jmumbo@nema.go.ke 21 Tom Makori Galaxy paints tomakori@yahoo.com 22 Peter Oiboo Mckay Advocates oiboo@mckayadvocates.com 24 Charles Kyengo Mckay Advocates ckyengo@mckayadvocates.com 25 William Munyoki Government Chemist wmunyoki@yahoo.com 26 Joseph Nzomoi Mckay Advocates jnzomoi@gmail.com 27 David Sarinke Mckay Advocates sarinke@mckayadvocates.com 28 Washington

Ayiemba UNDP washington.ayiemba@undp.org

29 Caro wamai Government Chemist carowamai@yahoo.com, 30 Fred Nyongesa Water Resources Management

Authority fnyongesa05@yahoo.com

31 Gitu Leonard JKUAT gitumleo@gmail.com