Appendix K: Data Validation (QA/QC) - Department of Defence...Appendix K: Data Validation (QA/QC) Introduction This data validation appendix summarises the DQOs, established for the

Appendix K: Data Validation (QA/QC)

Introduction

This data validation appendix summarises the DQOs, established for the current DSI and then assesses the reliability of the fieldwork procedures and laboratory analytical results using the data quality indicators (DQIs).

Data Quality Objectives

To define the purpose, type, quantity and quality of data required for the current DSI of RAAF Base Tindal, the seven step data quality objectives (DQOs) approach, as described in the NEPM 2013, was adopted.

The seven step DQO process is a systematic approach to obtaining reliable and adequate data in making risk-based decisions. The seven steps of the DQO process for the DSI are briefly summarised below:

Table K1: Summary of data quality objectives

Quality objectives

1. State the Problem

PFAS contamination sources have been identified at RAAF Base Tindal. Previous investigations have identified contaminated soil and groundwater in the vicinity of known source areas. Other potential source areas have had limited (if any) assessment for PFAS contaminant nature and extent. A comprehensive investigation of soils, waters and sediments is proposed through 2017.

The extent of PFAS contamination in groundwater and associated impact in surface water off-Base is not previously well understood. Given the tropical climate of the Tindal/Katherine area, surface water flows and groundwater recharge rates will have a strong seasonal variation.

In order to forecast the future impact of residual contamination, and inform contaminant management strategies, some modelling of contaminant transport behaviour will be required. The modelling will be undertaken following the analysis of data collected during the 2018 wet season.

2. Identify the goal of the study

The purpose of the broader investigation is to understand the nature and extent of PFAS contamination as a result of Defence activities.

The purpose of the DSI is to provide sufficient information on the sources of contamination, the contaminant transport conditions, the migration pathways and the current extent of contamination to enable a robust site model to be developed.

The conceptual site model will inform human health and/or ecological risk assessment, and guide effective management strategies.

3. Identify information inputs

Site history relating use of PFAS contaminant materials, to identify product types and locations where contamination may be emanating from (source areas).

Existing data relevant to PFAS in soil, waters and sediment, to confirm the presence of source areas, indicate the potential extent of contamination, and identify gaps in reliable data.

Surface water and groundwater flow regimes, to develop the conceptual site model about the potential migration pathways of contamination from source areas towards human and ecological receptors.

Location and types of human and environmental receptors, to guide selection of relevant screening criteria to reflect plausible exposure routes.

4. Define the boundary of the study

Quality objectives

Based on the potential for contaminated surface water or shallow groundwater to migrate west north-west towards Katherine River, the broad study area includes land and waterways on RAAF Base Tindal and the area between the Base and Katherine River (Figure 2). An approximate buffer of 200 m across the western side of Katherine River has been included.

5. Develop a decision rule

Primary environmental samples will be collected and analysed by the laboratories for the full suite of PFAS compounds.

Soil samples

Relative concentrations and leaching analysis provides information about potential ongoing sources of contamination to surface water and groundwater.

Absolute concentrations describe direct exposure potential where people, plants or animals may be in contact with soil and allow an assessment of risk.

Sediment samples

Relative concentrations and leaching analysis provides information about potential ongoing sources of contamination to surface water through leaching, and indications of historic migration of contamination to drains and waterways.

Relative concentrations and leaching analysis allows for correlation of PFAS concentrations in sediments with biota uptake of PFAS.

Absolute concentrations describe direct exposure potential where people, plants or animals may be in contact with sediments and allow an assessment of risk.

Groundwater samples

Relative concentrations identify sources of contamination and preferential pathways of migration to other areas of the Base, or off-Base. Relative concentrations are also used to calibrate contaminant transport models which can be used to predict future behaviour.

Comparison of groundwater concentrations and surface water concentration informs the understanding of interaction between surface water and groundwater.

Absolute concentrations (and model predictions) at the point of use, or groundwater discharge zoned, describe the exposure where direct contact between water and people, plants or animals may occur, which allows an assessment of risk.

Surface water samples

Relative concentrations identify where residual sources are creating an impact and describe preferential pathways of migration to other areas of the Base, or off-Base.

Absolute concentrations describe the exposure where direct contact between water and people, plants or animals may occur, which allows an assessment of risk.

Absolute concentrations can also be related to biota test results to inform an understanding of bioaccumulation, which then relates to assessment of associated human health or ecological risk.

PFOS, PFHxS and PFOA concentrations will be compared against screening levels relevant to the potential beneficial uses of land or water to identify potential complete pathways and potentially unacceptable risks.

The relative concentrations of all (analysed) PFAS compounds in soil and groundwater samples will be used to characterise the source areas, define the lateral and vertical extent and identify complete exposure pathways.

Residual source mass, leachability of the source and measurements of contaminant mass flux will be used to assess the contribution that each identified source area is making to adverse impact on beneficial uses.

6. Specify performance of acceptance criteria

The assessment as a whole (including consideration of previous assessments) must reliably characterise the sources of contamination from the Base and described the risk that the contamination may pose to human or

Quality objectives

ecological receptors. In order to achieve that, there must be multiple lines of evidence to support location of source areas; the characterisation of the nature and extent of the residual source and associated surface water or ground water impact; the significance of the risk that that contamination currently poses to relevant receptors; and predictions of future impacts.

Analytical data quality indicators are described in Section 8.

7. Develop a plan for obtaining the data

The methodology and rationale for obtaining relevant data for the DSI is described in the DSI SAQP.

Data Quality Indicators

An assessment of the reliability of field procedures and laboratory analytical results outlined through the DQOs has been undertaking using the DQIs of precision, accuracy, representativeness, completeness and comparability. A brief outline of the DQIs is presented below.

Precision – All Coffey field staff to implement Coffey standard operating procedures (SOPs) appropriate for the task being undertaken. All laboratories used to undertake analysis are NATA accredited for the analytes being tested for. An appropriate number of intra-laboratory and inter-laboratory replicate samples were collected and analysed and are within the acceptable limits of 1 in 20.

Accuracy – All Coffey staff to follow the appropriate SOPs for the tasks being undertaken. Trip blanks and equipment rinsate blank samples collected and results of which are to be satisfactory. All laboratories used are to be NATA accredited and the use of NATA endorsed methods, including appropriate method blanks, laboratory control samples, laboratory spikes and duplicates, and the results of which satisfy the defined criteria of acceptability.

Representativeness – A sufficient number of samples are to be collected and analysed from each media to adequately achieve the overall DSI objectives.

Completeness – All Coffey staff to follow Coffey SOPs appropriate to the task being performed, along with the appropriate documentation. All identified areas of environmental concern to be assessed with chemical analysis for relevant chemicals of potential concern from targeted and systematic sampling locations. All samples to be under proper custody between the field and laboratory. The data obtained from the laboratory is considered relevant and usable.

Comparability – All Coffey staff to follow the appropriate SOPs for the task being undertaken and complete all sampling documentation. All analyte holding times to be complied with and samples properly and adequately preserved. All laboratory analysis to use the correct methods, along with appropriate limits of reporting (LORs).

The DQIs for the field works and laboratory analysis were established in the SAQP. The established acceptance limits are presented in Table K2.

Table K2 – Field works quality control criteria

Item Comments

Intra-laboratory

duplicates

Inter-laboratory duplicates (triplicates)

Intra-laboratory field duplicates were collected at a minimum frequency of one sample per

twenty samples collected (5%). The analytical results of the primary sample and

duplicate/triplicate samples will be compared to assess the precision of the sampling

protocol and to provide an indication of variation in the sample source.

Item Comments

Repeatability will be assessed by calculating the relative percentage difference (RPD)

between the primary and duplicate results. Where the RPD is greater than 30%, the

potential causes of variability has been reviewed.

Trip blanks Trip blanks are a check on sample contamination originating from containers, sample

transport, shipping and site conditions. The trip blank will be prepared in a clean

environment (office or warehouse) and remain with the sample containers during sampling

and during the return trip to the laboratory. At no time during these procedures will the

blanks be opened. Upon return to the laboratory the blank will be analysed, if needed, as

any other field sample. As PFAS is not volatile, a reduced blank frequency is considered

appropriate and a single trip blank per sample batch will be transported and analysed.

Detectable concentrations of PFAS in a trip blank sample will trigger review of sample

container types, transport procedures and UHP water quality. The concentration and

compound detected will be considered in reviewing the potential impact of transport related

cross-contamination of the assessment data quality.

Rinsate blanks Rinsate samples will be prepared in the field using empty bottles and the distilled

water/potable water used for the cleaning of non-disposable sampling equipment. These

samples will be a check of field decontamination procedures. A rinsate sample will be

collected and analysed for each day of field work, where non-disposable sampling

equipment has been used.

Detectable concentrations of PFAS in a rinsate blank sample will trigger review of

decontamination procedures, equipment materials, sample container types and UHP water

quality. The concentration and compound detected will be considered in reviewing the

potential impact of transport related cross-contamination of the assessment data quality.

Sample Analysis All sample analyses to be conducted using NATA certified laboratories which will implement a quality control plan in accordance with NEPM (1999).

Holding times Maximum acceptable sample holding times:

Soil: 14 days for organic analyses (including PFAS) and 6 months for inorganic analyses (28 days for mercury).

Groundwater/surface water: 14 days for organic analyses (including PFAS) and 6 months for inorganic analyses (28 days for mercury).

Laboratory detection limits

All laboratory detection limits to be less than the site investigation criteria.

Laboratory Blanks

Laboratory blanks to be analysed at a rate of 1 in 20, with a minimum of one analysed per batch.

Concentration of analytes to be less than the laboratory detection limits.

Laboratory Duplicates

Laboratory duplicates to be analysed at a rate of 1 in 20, with a minimum of one analysed per batch. RPDs to be less than 30%.

Laboratory Control Samples (LCS)

LCSs to be analysed at a rate of 1 in 20, with a minimum of one analysed per analytical batch.

Control limits: 50 to 150 % acceptable recovery

Matrix spikes Matrix spike duplicate prepared by dividing a field sample into two aliquots, then spiking each with identical concentrations of the analytes at a rate of 1 in 20.

Matrix spike control limits:

50–150 % acceptable recovery. Lower recoveries may be acceptable for OCPs, OPPs, PCBs and phenols and will be assessed according to USEPA protocols.

Item Comments

Matrix spike duplicates:

RPDs <50%

Field Quality Assurance and Quality Control (QAQC)

Field Quality Assurance Procedures

Field quality assurance involves all the planned actions, procedures, checks and decisions which have been made and undertaken through quality control measures to ensure the representativeness and integrity of collected samples is that of the true conditions.

Sample Collection

All Coffey environmental scientists/engineers were suitably qualified, trained and experienced for the sample collection undertaken. Sampling of each matrix was undertaken with reference to the Coffey standard operating procedures (SOPs).

Sampling Methodology

The adopted sampling methods for each media (soil, sediments, groundwater and surface water) is presented in the DSI SAQP.

All samples were collected using a new disposable nitrile glove. Each sample was collected in a laboratory supplied jar or bottle appropriate to the analysis required.

All groundwater samples were collected using disposable bladders and tubing or disposable hydro sleeves.

Each sample was labelled using a unique sample identifier, project reference and date of sample collection, as directed by Defence and documented in the DSI SAQP (754-MELEN199420-R03).

Sample Transport and Preservation

To maintain sample integrity, all samples were placed into laboratory prepared containers suitable for PFAS and other non-PFAS analysis. Samples were immediately placed into an insulated ice chest containing ice, for storage and transportation to the Eurofins and ALS laboratories.

All samples were placed into lip-lock bags according to analysis, separating samples requiring PFAS analysis and samples requiring non-PFAS analysis.

All samples were sent to the laboratories under chain of custody (CoC) documentation.

Field Equipment Calibration

All equipment was calibrated before being used to collect data. All equipment was calibrated in accordance with the manufacturers’ specifications.

Field Duplicates

In order to assess analyte concentration variability between samples collected from the same point and the repeatability of the laboratory analysis procedures, both duplicate (intra-laboratory) and triplicate (inter-laboratory) samples have been collected at a ratio of 1:20 (1 per 20 primary samples).

During soil and sediment investigation phases, the duplicate and triplicate samples were collected from a larger than normal portion of soil from the same depth and then split evenly between sampling containers. Due to limited volumes within the Hydrasleeve used during groundwater sampling, duplicates and triplicates were split between different sampling points and depths.

Variability and repeatability will be assessed by calculating the relative percentage difference (RPD) between the primary sample and the duplicate/triplicate results. The calculated RPDs between the primary and duplicate samples has been compared to the acceptance criteria of <30%. Where the RPD is greater than 30%, the potential causes of variability has been reviewed.

An overview of the PFAS quality control sampling is provided in Table K3.

Table K3 – PFAS quality control sample overview

Sample type Primary

samples

Primary

laboratory

duplicate

samples

Secondary

laboratory

duplicate

(triplicate)

samples

Rate Blanks

Rinsate Trip

Soil and sediment 370 30 23 1 in 7 44 6

Groundwater 306 23 16 1 in 8 43 24

Surface water 100 14 8 1 in 5 9 4

All of the calculated RPDs between primary and duplicate and primary and triplicate samples were within the acceptable criteria (<30%), with the exception of those listed in Table K4, below.

Where an individual compound has reported an elevated RPD above the criteria the corresponding sum of results has also reported elevated RPDs. However in the summary table below only the individual compound has been reported and discussed.

Table K4 – RPD Results outside Acceptable Criteria

Date Batch Analyte Primary sample (Eurofins) Result Duplicate sample (Eurofins)

Result Batch Triplicate sample (ALS)

Result RPD

Soil and sediment

7/07/2017 553958 Aluminium 0990_BH103_0.2_1 12,000 0990_QCBH104_1 3,800 - - - 104

Arsenic 11 3.4 - - - 106

Chromium 40 17 - - - 81

Copper 19 5.5 - - - 110

Iron 41,000 13,000 - - - 104

Lead 24 48 - - - 67

Nickel 16 6.3 - - - 87

Zinc 45 16 - - - 95

11/07/2017 554258 Chromium 0990_BH114_0.0_170711 50 0990_QCBH110_170711 35 - - - 35

12/07/2017 554681 PFDS 0990_BH117_0.0_170712 180 0990_QCBH114_170712 65 - - - 94

PFOSA 100 47 - - - 72

PFOS 180 900 - - - 133

12/07/2017 554681 PFDS 0990_BH117_0.0_170712 180 - - EB1715147 0990QCBH114A_170712 95.7 61

PFOSA 100 - - 6.8 69

PFOS 180 - - 267 39

12/07/2017 554681 PFDS 0990_SS131_170712 270 0990_QCBH115_170712 13 - - - 182

PFOS 3,800 78 - - - 192

12/07/2017 554681 Arsenic 0990_SS131_170712 2 0990_QCBH115_170712 3.2 - - - 46

Manganese 270 2,400 - - - 160

Nickel 16 23 - - - 36

12/07/2017 554681 10:2 FTS 0990_SS131_170712 0.029 - - EB1714679 0990_QCBH115_170712 0.0006 192

8:2 FTS 110 - - 3.4 188

PFOA 16 - - 4 120



Result RPD

PFBS 12 - - 2.2 138

PFHxS 65 - - 10.9 143

PFHxA 18 - - 4 127

PFOS 3,800 - - 405 161

PFPeA 9.5 - - 1.3 152

12/07/2017 554681 PFHxS 0990_SS122_170712 11 0990_QCBH116_170712 32 - - - 98

PFOS 98 310 - - - 104

Cadmium 1 0.7 - - - 35

12/07/2017 554681 PFHxS 0990_SS122_170712 11 - - EB1715147 0990QCBH116A_170712 6.2 56

Aluminium 9,000 - - 5,300 52

Cadmium 1 - - 2 67

Chromium 150 - - 47 105

Copper 39 - - 28 33

Iron 86,000 - - 25,800 108

Zinc 160 - - 285 56

17/07/2017 555513 PFOS 0990_BH137_0.4_170718 9.8 0990_QCBH123_170718 6.7 - - - 38

17/07/2017 555513 PFOS 0990_BH137_0.4_170718 9.8 - - EM1710316 0990_QCBH123A_170718 5.3 60

29/07/2017 557381 Manganese 0990_SS146_0.0_170729 1,200 0990_QCSS139_170729 340 - - - 112

29/07/2017 557381 Chromium 0990_SS146_0.0_170729 31 - - EB1716434 0990_QCSS139A_170729 18 53

Copper 12 - - 8 40

Lead 18 - - 12 40

Nickel 16 - - 7 78

Zinc 18 - - 12 40

29/07/2017 557381 Aluminium 0990_SS146_0.0_170729 15,000 - - EM1710450 0990_QCSS139A_170729 8,150 59

Chromium 31 - - 21 38

Lead 18 - - 12 40

Manganese 1,200 - - 327 114



Result RPD

Nickel 16 - - 8 67

Zinc 18 - - 5 113

7/08/2017 558305 Lead 0990_MW133_0.0_170807 44 0990_QCMW155_170807 30 - - - 38

Manganese 1,000 540 - - - 60

7/08/2017 558305 Aluminium 0990_MW133_0.0_170807 27,000 - - EM1710785 0990_QCMW156_170807 27,000 96

Arsenic 10 - - 5 67

Chromium 56 - - 36 43

Copper 25 - - 16 44

Iron 45,000 - - 31,500 35

Lead 44 - - 21 71

Manganese 1,000 - - 454 75

Nickel 24 - - 12 67

Zinc 20 - - 8 86

10/08/2017 561326 Aluminium 0990_BH166_1.5_170810 1,900 0990_QCBH147_170810 1,200 - - - 45

Iron 16,000 5,800 - - - 94

Manganese 25 12 - - - 70

10/08/2017 561326 PFOS 0990_BH166_1.5_170810 35 - - EM1711973 0990_QCBH147A_170810 14.3 84

Aluminium 1,900 - - 960 66

Chromium 37 - - 22 51

Iron 16,000 - - 4,530 112

Manganese 25 - - 16 44

11/08/2017 559638 PFOS 0990_BH180_0.2_170811 44 - - EM1711301 0990_QCBH160A_170811 29.8 38

Aluminium 27,000 - - 12,600 73

Arsenic 11 - - 8 32

Nickel 25 - - 14 56

Zinc 12 - - 6 67

15/08/2017 559790 Aluminium 0990_SS166_170815 11,000 - - EM1711374 0990_QCSS180A_170815 4,690 80



Result RPD

Zinc 7.2 - - 5 36

16/08/2017 559790 PFOS 0990_MW126_0.0_170816 8 - - EM1711303 0990_QCMW181A_170816 4.1 64

Iron 9,000 - - 6,420 33

18/08/2017 559812 Arsenic 0990_MW129_0.1_170818 2.9 0990_QCMW184_170818 5.7 - - - 65

Chromium 25 47 - - - 61

Lead 5.9 9.3 - - - 45

19/08/2017 559812 PFOA 0990_MW128_0.0_170819 6.4 0990_QCMW175_170819 11 - - - 53

PFBS 21 39 - - - 60

PFPeS 17 32 - - - 61

PFHxS 160 320 - - - 67

PFHxA 20 38 - - - 62

PFOS 23 34 - - - 39

Arsenic 4.9 6.7 - - - 31

Zinc 45 13 - - - 110

19/08/2017 559812 PFOA 0990_MW128_0.0_170819 6.4 - - EM1711367 0990_QCMW175A_170819 2.3 94

PFBS 21 - - 4.6 128

PFPeS 17 - - 4.3 119

PFHxS 160 - - 15 166

PFHxA 20 - - 2.9 149

PFOS 23 - - 5.4 124

19/08/2017 559812 Chromium 0990_MW128_0.0_170819 41 - - EM1711367 0990_QCMW175A_170819 30 31

Copper 14 - - 10 33

Lead 20 - - 12 50

Zinc 45 - - 11 121

24/08/2017 560594 PFHxS 0990_BH195_2.0_170824 8.4 - - EM1711653 0990_QCBH199A_170824 2 123

PFOS 120 - - 25.3 130

Aluminium 13,000 - - 7,420 55



Result RPD

Arsenic 18 - - 12 40

Chromium 58 - - 34 52

Lead 39 - - 26 40

Nickel 19 - - 13 38

Zinc 46 - - 31 39

5/9/2017 563114 Arsenic 0990_BH199_0.3_170905 5.4 0990_QCBH220_170905 11 - - - 68

Manganese 200 140 - - - 35

5/09/2017 563114 Iron 0990_BH199_0.3_170905 32,000 - - EM1712586 0990_QCBH220A_170905 22,100 37

29/09/2017 566040 Chromium 0990_SS205_170929 100 0990_QCSS306_170929 66 - - - 41

29/09/2017 566040 Aluminium 0990_SS205_170929 9,000 - - EM1713612 0990_QCSS307_170929 5,490 48

Chromium 100 - - 48 70

Copper 18 - - 11 48

Iron 49,000 - - 28,400 53

Manganese 230 - - 346 40

Zinc 26 - - 18 36

Groundwater and surface water

28/04/2017 544592 PFPeS 0990_070MW01_170428 0.05 - - EB1709001 0990_QC3GW_170428 0.08 46

PFHxS 0.18 - - 0.25 33

PFOS 0.07 - - 0.12 53

28/04/2017 544592 PFOS 0990_054MW02_170428 0.05 - - EB1709001 0990_QC4GW_170428 0.08 46

29/04/2017 544592 PFOA 0990_NT0064MW11_170429 0.52 - - EB1709001 0990_QC7GW_170429 0.37 34

30/04/2017 544592 /

544553

PFPeA 0990_SW060_170430 0.03 0990_QC11SW_170430 0.02 - - - 40

Barium 0.02 0.03 - - - 40

1/05/2017 544592 PFOS 0990_SW51_17/05/01 1.5 0990_QC15SW_17/05/01 1.1 - - - 31

1/05/2017 544592 PFHpS 0990_SW28_17/05/01 0.02 - - EB1709001 0990_QC17SW_170501 0.03 40

PFHxS 0.41 - - 0.56 31

2/05/2017 544814 PFOA 0990_076MW01_170502 0.02 0990_QC19GW_170502 0.05 - - - 86



Result RPD

PFPeS 0.19 0.26 - - - 31

PFHpS 0.05 0.09 - - - 57

PFHxS 1.2 1.7 - - - 34

PFHxA 0.12 0.24 - - - 67

PFOS 0.21 0.41 - - - 65

PFPeA 0.03 0.06 - - - 67

2/05/2017 544814 PFOA 0990_RN002890_170502 0.02 0990_QC21_GW_170502 0.03 - - - 40

11/05/2017 546509 PFOA 0990_RN022475_170511 0.02 - - EB1710163 QC25_GW_170511 0.01 67

10/07/2017 554258 PFHxS 0990_SW129_170710 0.03 0990_QCSW108A_170710 0.02 - - - 40

23/07/2017 555721 6:2 FTS 0990_064MW03_170723 87 - - EB1715506 0990_QCMW134_170723 57.2 41

PFPeA 81 - - 112 32

14/08/2017 559648 Magnesium 0990_PB021_170814-1 41 0990_QCPB171_170814 58 - - - 34

22/08/2017 560143 8:2 FTS 0990_SW161_170822 0.003 0990_QCSS195_170822 0.013 - - - 125

PFOA 0.002 0.007 - - - 111

PFNA 0.001 0.006 - - - 143

PFOS 0.0096 0.037 - - - 118

22/08/2017 560143 PFOS 0990_SW161_170822 0.0096 - - EM1711498 0990_QCSW195A_170822 0.0064 40

24/08/2017 560551 PFOA 0990_TR004_170824 0.01 0990_QCTR202_170824 0.02 - - - 67

25/08/2017 560909 PFPeS 0990_RN020118_170825 0.03 - - EM1711784 0990_QCRN188A_170825 0.02 40

PFOS 0.22 - - 0.15 38

31/08/2017 567120 PFOA 0990_SW162_170831 0.04 - - EB1721129 0990_QCSW214A_17083 0.02 67

PFBS 0.06 - - 0.14 80

PFHxS 0.48 - - 0.71 39

PFOS 1.4 - - 0.95 38

11/09/2017 562852 PFBS 0990_RN025768_170911 0.04 0990_QCPB226_170911 0.06 - - - 40

PFPeS 0.11 0.06 - - - 59

PFHxS 0.23 0.35 - - - 41



Result RPD

PFOS 0.31 0.54 - - - 54

11/09/2017 562852 PFBS 0990_RN025768_170911 0.04 - - EM1712474 0990_QCPB226A_170911 0.06 40

PFPeS 0.11 - - 0.07 44

PFHpS 0.03 - - 0.02 40

PFHxS 0.23 - - 0.39 52

PFOS 0.31 - - 0.45 37

14/09/2017 563665 PFHxS 0990_MW142A_170914 0.04 - - EM1712768 0990_QCGW245_170914 0.02 67

15/09/2017 563889 PFPeS 0990_MW137A_170915 0.02 0990_QCGW248_170915 0.03 - - - 40

20/09/2017 564886 PFOS 0990_SW161_170920 0.003 - - EM1713184 0990_QCSW263_170920 0.0045 40

21/09/2017 564886 PFBS 0990_MW139_170921 0.06 - - EM1713184 0990_QCMW266_170921 0.099 49

PFHpA 0.014 - - 0.0092 41

21/09/2017 564886 PFHxA 0990_MW139_170921 0.096 - - EM1713184 0990_QCMW266_170921 0.0687 33

PFOS 1.0 - - 0.498 67

PFPeA 0.022 - - 0.0116 62

21/09/2017 564886 PFOS 0990_MW135_170922 0.03 0990_QCMW269_170922 0.02 - - - 40

23/09/2017 565191 PFHpA 0990_MW111_170923 0.05 - - EM1713367 0990_QCMW277_170923 0.07 33

24/09/2017 565191 PFOA 0990_064MW12_170924 150 0990_QCMW279_170924 230 - - - 42

PFBA 71 51 - - - 33

PFHxS 260 400 - - - 42

PFOS 110 500 - - - 128

25/09/2017 565353 PFPeA 0990_064MW02_170925 150 0990_QCMW282_170925 290 - - - 64

25/09/2017 565353 8:2 FTS 0990_064MW01_170925 0.03 0990_QCMW283_170925 0.07 - - - 80

28/09/2017 565894 PFOA 0990_SW175_170928 0.03 0990_QCSW298_170928 0.02 - - - 40

PFOS 0.3 0.12 - - - 86

Where RPDs have exceeded the acceptable criteria an investigation was undertaken to determine the likely cause of the variation, and whether the variability will affect the reliability of the data.

The investigation included a review of the laboratory batch QC, a review of the lithology encountered when collection of sample was undertaken, and correspondence with the laboratory.

After an investigation of the sample pairs that were outside the acceptance criteria of <30%, it was determined that a majority of the exceedances could be attributed to one of the following explanations.

When low analyte concentrations are reported in the primary sample and the corresponding duplicate or triplicate sample, these have exaggerated the calculated RPD with respect to small total concentration differences. The calculated RPD values are not considered to affect the integrity of the results as both results remain well below nominated criteria. This has been observed in batches

When the reported concentrations for both the primary sample and duplicate/triplicate sample are above the nominated criteria, or where there are no criteria, the reported concentrations indicate the presence of contamination. The calculated RPD values are not considered to affect the integrity of the results, as the samples indicate the presence of impact.

Due to the heterogeneity of soils, results in soils can exhibit a wide variation in results, exaggerating RPDs. The calculated RPD values are not considered to affect the integrity of the results as the highest concentration has been adopted (as a conservative measure) as the representative sample.

Rinsate Blanks

To confirm that the decontamination processes of re-usable pieces of sampling equipment is adequate and not causing cross-contamination of chemicals of potential concern into the sampled medium, a rinsate blank has been collected. The rinsate blank is collected after the decontamination of a piece of equipment used for collection of samples (hand auger, nitrile gloves, and surface water sampling pole and cup, and oil-water interface probe). A separate rinsate blank has been collected for each piece of equipment used to sample each separate medium per day.

All samples reported concentrations below the laboratory limit of reporting or where above the laboratory LOR but below the adopted screening limits, with the exception of the following.

Table K5 – Rinsate results above the laboratory limit of reporting

Date Batch Analyte Sample ID Result

(µg/L)

11/07/2017 554304 PFOS 0990_QCSW109_170710 0.01

14/07/2017 554677 PFOS 0990_QCBH120_170714 0.02

17/07/2017 555513 PFOS 0990_QCBH125_170717 0.03

31/07/2017 557381 PFOS 0990_QCSS141_170731 0.03

2/08/2017 558305 PFOS 0990_QCMW142_170801 0.08

20/09/2017 564886 4:2 FTS 0990_QCSW264_170920 0.002

PFDS 0.003

PFHxA 0.002

PFOS 0.003

21/09/2017 564886 PFDS 0990_QCSW265_170921 0.004

PFHxA 0.002

PFOS 0.003

PFDS 0.002


(µg/L)

PFHxA 0.001

29/09/2017 566040 Alkalinity (total) as CaCO3 0990_QCSS305_170929 350

Chloride 20

Calcium 68

Magnesium 40

Potassium 2.4

Sodium 6.4

Trip Blanks

To be confident that cross contamination between samples is not occurring during the storage of samples on-site and then during transport to the laboratories, a trip blank is placed into each esky and analysed for the chemicals of concern.

All trip blank samples reported concentrations below the laboratory LOR, with the exception of the following.

Table K6 – Trip blank results above laboratory limit of reporting


(µg/L)

11/09/2017 562857 8:2 FTS 0990_QCPB225_170911 0.04

11/09/2017 562857 PFOS 0990_QCPB225_170911 0.17

14/09/2017 563665 PFHxS 0990_QCGW247_170914 0.01

21/09/2017 564886 6:2 FTS 0990_QCMW268_170921 0.005

4:2FTS 0.001

PFDS 0.002

PFHxS 0.006

PFOS 0.002

24/09/2017 565191 PFOA 0990_QCMW278_170924 0.04

PFBS 0.02

PFPeS 0.03

PFHpS 0.04

PFHpA 0.02

PFHxS 0.14

PFHxA 0.06

PFOS 0.16

PFPeA 0.02

Laboratory Quality Assurance Quality Control

Laboratories

Eurofins (primary laboratory) and ALS (secondary laboratory) are NATA accredited laboratory for all the analytes requiring analysis.

Holding Times

To maintain the sample integrity and reliability of results, to most closely reflect the conditions at the time of sample collection, samples were delivered to the laboratory within the recommended holding times. Holding times are specific to the types of analytes be analysed and laboratory methods.

After a review of the laboratory sample receipt documentation, all samples were received in the laboratory within the recommended holding times, with the exception of those in Table K7 below.

Table K7 – Samples received at the laboratory outside of recommended holding times

Laboratory Batch Number

Date Analyte Lab Sample Id. Days outside holding time

EB1718647 20170821 Moisture 0990_QCSS193A_20170821

9

EM1711299 20170810 Dissolved Major Cations

0990_QCPB159A_20170810

8

EM1711302 20170814 Dissolved Major Cations

0990_QCPB171A_20170814

4

As these analytes are not COPCs, this is not considered the have impacted the outcome of the investigation.

Analytical Methods

The primary laboratory analytical methods are summarised in Table K8 below:

Table K8 – Laboratory analytical methods

Analytes Analytical Method ^ Limit of Reporting

Soil/Sediments

Standard minimum PFAS suite – 22 compounds** In-house Method based on US EPA Method 537 Version 1.1

5 µg/kg

Total Organic Carbon (TOC), pH, Conductivity (EC) APHA 5310, APHA 4500 pH, NEPM Schedules B3, APHA 2510, NEPM Schedule B3

0.1% C, 0.1 pH, 10 uS/cm

Exchangeable Cations and Cation Exchange Capacity (CEC), Clay content, Particle size distribution (PSD)

Rayment & Lyons 15B1-B3 0.05 meq/100g

Neutral ASLP and analysis for standard PFAS suite AS 4439.3 -

Metals (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Zn) USEPA 6010, 6020 0.1 (Hg) – 20 Fe) mg/kg

Total Recoverable Hydrocarbons/Benzene, Toluene, Ethylbenzene, Xylenes, Naphthalene

NEPM Schedule B3 20/50/100/100 mg/kg, 0.1 mg/kg

Volatile and semi-volatile organic compounds (including chlorinated compounds)

USEPA 8260, USEPA 8270, NEPM Schedule B3

0.5 – 5 mg/kg

Organochlorine Pesticides (OCP), Organophosphate pesticides (OPP), and Phenoxy Acid Herbicides


0.05 – 2.0 mg/kg

Polycyclic Aromatic Hydrocarbons USEPA 8270, 8100, NEPM Schedule B3

0.5 mg/kg

1,4-Dioxane SW-846 8270C 333 µg/kg

Asbestos/Presence, includes presence absence for free fibres)

AS 4964-2004 -

Water

Standard minimum PFAS suite – 22 compounds** In-house Method based on US EPA Method 537 Version 1.1

0.01 – 0.05 µg/L

Total Oxidisable Precursors (TOP) Houtz et al

1,4-Dioxane SW-846 8270C 5 µg/L

Field Filtered Metals (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Zn)

USEPA 6010, 6020 0.001 (Hg) – 0.5 (Fe) mg/L

Total Recoverable Hydrocarbons/Benzene, Toluene, Ethylbenzene, Xylenes, Naphthalene

NEPM Schedule B3 0.02/0.05/0.1/0.1, 0.001 mg/L

Volatile and semi-volatile organic compounds (including chlorinated compounds)


0.001 – 0.1 mg/L

Ca, Mg, Na, K, Cl, SO4, Alkalinity USEPA 6010, APHA 4500-Cl, APHA 4500-SO4, CO3

0.5 – 20 mg/L

Total Organic Carbon (TOC), Nutrient Suite (Total nitrogen, TKN, NOx, NO2, NO3, NH3)

APHA 5310, APHA 4500 5 mg/L, 0.02 – 0.2 mg/L

^ NATA certified or equivalent

*Analysis to be carried out by Eurofins│Lancaster Laboratories Environmental in the USA. ISO17025 accredited.

**28 analytes will be tested via the primary laboratory (Eurofins). In-house method based on USEPA Method 537 Version 1.1 (LC/MS-MS)

**28 analytes will be tested via the secondary laboratory (ALS). In-house method (EP231PFC) LC/MS-MS (NATA certified)

Laboratory (Method) Blanks

The method blank allows assessment for potential method bias for a relevant analytes. A method blank is the component of the analytical signal from each analytical method that is from laboratory equipment (reagents, glassware and analytical instruments etc.). The method blank is determined by the laboratories through running solvents and reagents in exactly the same manner as the samples.

At least one method blank should be run per 20 samples analysed, with a minimum of one method blank per sample batch.

A review of the laboratory reports showed all method blank results were below the laboratory LOR.

Laboratory Duplicates

To provide an estimate of the analysis method precision and duplicate sample heterogeneity, a sample from the same batch is duplicated and analysed for a targeted analyte.

A review of the laboratory reports showed that there were sufficient duplicates run to satisfy the required frequency. The review also showed that all RPDs between the laboratory primary and duplicate samples were within the laboratory DQI, with the exception of those in Table K9.

Table K9 – Laboratory duplicate RPD exceedances

Laboratory Batch

Number

Date Analyte Lab Sample ID.

RPD Laboratory qualifying code

Soil/sediment

554258-S 20170710 Aldrin M17-JI18322 100 Q15

555149-S 20170711 Nickel M17-JI23194 41 Q15

558047_L 20170711 8:2 FTS B17-Au12523 35 Q15

554681-S 20170712 TRH C15-C28 S17-JI18244 34 Q15

554681-S 20170712 TRH C29- C36 S17-JI18244 37 Q15

554681-S 20170712 TRH >C16-C34 S17-JI18244 34 Q15

557977-L 20170712 8:2 FTS B17-Au12523 35 Q15

554677-S 20170714 Cadmium M17-JI2246 77 Q15

556894-S 20170718 o-Xylene M17-Au01489 37 Q15

556468-W 20170720 Copper M17-JI33015 34 Q15

558617-S 20170808-09 Zinc M17-Au17493 35 Q15

558617_W 20170808-09 Nickel M17-Au2100 42 Q15

556894-S 20170810 o-Xylene M17-Au01489 37 Q15

558914-S 20170811 Arsenic M17-Au19858 34 Q15

558914-S 20170811 Chromium M17-Au19928 34 Q15

559638-S 20170811 TRH C15-C28 M17-Au22963 75 Q15

559638-S 20170811 TRH C29-C36 M17-Au22963 44 Q15

559638-S 20170811 TRH >16-C34 M17-Au22963 71 Q15

559638-S 20170811 TRH >34-C40 M17-Au22963 60 Q15

557381-S 20170818 Bis(2-ethylhexyl)phthalate

M17-Au07078 100 Q15

EM1711367_0_QCI

20170819 Acenaphthylene EM1711437-002 41.9 -

EM1711367_0_QCI

20170819 Sum of PAHs EM1711437-002 40.4 -

Laboratory Batch

Number


RPD Laboratory qualifying code

562180-S 20170831 Total Organic Carbon M17-Se07440 46 Q15

563696-S 20170911 Arsenic M17-Se20791 39 Q15

563696-S 20170911 Chromium M17-Se20791 49 Q15

557381-S 20170729 Bis(2-ethylhexyl)phthalate

M17-Au07078 100 Q15

Groundwater

559812-W-V4

20170818 PFTriDA M17-Au26495 200 No explanation code

559812-W-V4

20170818 PFTeDA M17-Au26495 200 No explanation code

559812-W-V4

20170818 N-MeFOSE M17-Au26495 200 No explanation code

Leachate

557977-L 20170821 8:2 FTS B17-Au12523 35 Q15

Surface Water

554258-S 20170728 Aldrin M17JI16322 100 Q15

554468-S 20170731 TRH C15-C28 S17-JI18244 34 Q15

554468-S 20170731 TRH C29-C36 S17-JI18244 37 Q15

554468-S 20170731 TRH >C16-C34 S17-JI18244 34 Q15

558305-S 20170802 Diethyl phthalate M17-Au14102 31 Q15

Vertical Delineation (Groundwater)

561846-W 20170901 TRH C29-C36 S17-Se05678 38 Q15

Laboratory Control Sample

Laboratory control samples are prepared in the laboratory and comprise either a known analyte concentration within a proven matrix or a control matrix spiked with analytes representative of the target analyte. The laboratory control sample percent recovery is reported along with the primary sample data to assess method accuracy for all targeted analytes.

Laboratory control samples are required to be processed per 20 samples analysed, with a minimum of one laboratory control sample run per batch of samples.

A review of the laboratory reports showed that the required frequency of laboratory control sample were run and that the percent recoveries were within the acceptable (50-150%) range as per the laboratory DQI, with the exception of those in Table K10.

Table K10 – Laboratory control spike exceedances

Laboratory Batch

Number


Result Laboratory qualifying code

Soil

EB1714679_0_QCI

20170713 1.2.4-Trichlorobenzene QC-1009629-002 60.3 Less than lower control limit (63-108%)

EM1711301_0_QCI

20170811 N-Ntirosomethylethyla QC-1073020-001 130 Recovery greater than control limit (70-120%)

EM1711301_0_QCI

20170811 Methapyrilene QC-1073020-001 92.7 Recovery greater than control limit (10-40%)

Laboratory Batch

Number


Result Laboratory qualifying code

EM1711301_0_QCI

20170811 1-Naphthylamine QC-1073020-001 27.0 Recovery less than control limit (40-120%)

EM1711301_0_QCI

20170811 Hexachlorobenzene (HCB)

QC-1073020-001 111 Recovery greater than control limit (50-101%)

EM1711301_0_QCI

20170811 3.3’-Dichlorobenzidine QC-1073020-001 131 Recovery greater than the control limit (70-130%)

EM1711367_0_QCI

20170819 Methapyrilene QC-1080090-001 122 Recovery greater than control limit (10-40%)

EM1711367_0_QCI

20170819 1-Naphthylamine QC-1080090-001 26.3 Recovery less than lower control (40-120%)

Groundwater

559790-S 20170814 2.4-Dinitrophenol - 0.00 Fail

Matrix Spikes

A matrix spike is undertaken to document the effect of the matrix on the performance of the method used. The matrix spike is the addition of a known analyte concentration to the target matrix prior to extraction or digestion. If a poor percentage recovery of a matrix spike is reported below the expected analytical method performance, the laboratory should investigate the likely cause. If, after investigation, the poor matrix spike remains and is reported to the client, an explanation documenting the limitations of the method for recovery of the target analyte from that particular matrix needs to be provided. If the laboratory control sample recovery is acceptable for the same analyte, this may indicate that it is the matrix causing the poor recovery and not the method.

A review of the laboratory reports showed that laboratory matrix spike percent recoveries were within the acceptable limits, with the exception of those presented in Table K11.

Table K11 – Matrix spike exceedances


Date Analyte Lab Sample ID. % Recovery

Laboratory qualifying code

Soil

553969-S-V2 20170704 Chromium M17-JI13946 144 Q08

553969-S-V2 20170704 Manganese M17-JI13946 143 Q08

553969-S-V2 20170704 Zinc M17-JI13946 54 Q08

EM1709217_)_QCI

20170707 Manganese EM1709226-002 Not determined

MS recovery not determined as background levels greater than or equal to 4x spike level

554677-S 20170714 Nickel M17-JI23575 59 Q08

556894-S 20170718 Manganese M17-Au02958 181 Q08

556468-S 20170720 Manganese M17-JI36955 165 Q08

556468-W 20170720 Nickel M17-JI33015 71 Q08

558617-S 20170808-09 1.4-Dioxane M17-Au17505 23 Q08

558617-S 20170808-09 Chromium M17-Au17509 68 Q08

558617-S 20170808-09 Copper M17-Au17509 132 Q08

558617-S 20170808-09 Zinc M17-Au17509 182 Q08

561326-S 20170810 2.4-D M17-Au36056 int Q09




561326-S 20170810 Actril (loxynil) M17-Au36056 int Q09

561326-S 20170810 Dichloprop M17-Au36056 int Q09

561326-S 20170810 MCPA M17-Au36056 int Q09

561326-S 20170810 MCPB M17-Au36056 int Q09

556894-S 20170810 Manganese M17-Au02958 181 Q08

558914-S 20170811 1.4-Dioxane M17-Au17505 23 Q08

559638-S 20170811 1.4-Dioxane M17-Au17505 23 Q08 (same as 558914-S)

EM1711374_0_QCI


MS recovery not determined as background level greater or equal to 4x spike level

EM1711303_0_QCI



557381-S 20170818 Chromium M17-Au07169 134 Q08

557381-S 20170818 Copper M17-Au07169 128 Q08

EM1711367_0_QCI

20170819 Acenaphthene EM1711437-001 Not determined


EM1711367_0_QCI

20170819 pyrene EM1711437-001 Not determined


563114-S 20170905 Manganese M17-Se16018 127 Q08

563114-S 20170905 Manganese M17-Se16028 136 Q08

563696-S 20170811 Chromium M17-Se20368 30 Q08

Groundwater

554304-S 20170711 N-EtFOSE B17-JI16761 154 Q08

557381-S 20170721 Chromium M17-Au07169 134 Q08

557381-S 20170721 Copper M17-Au07169 128 Q08

EM1710450_0_QCI

20170721 Manganese EM1710262-147 Not Determined


560441-S-V4 20170724 8:2 FTS M17-Se16726 188 Q08

Groundwater

559790-S 20170814 2.4-Dinitrrophenol M17-Au29074 0.00 Fail (no code)

560551-W 20170824 Calcium M17-Au24021 138 Q08

562852-W 20170911 Calcium M17-Se11244 144 Q08

562852-W 20170911 Magnesium M17-Se11244 133 Q08

562852-W-V2

20170911 Calcium M17-Se11244 144 Q08

562852-W-V2

20170911 Magnesium M17-Se11244 133 Q08

560522-W 20170808 Calcium M17-Au24021 138 Q08

560575-W 20170810 Magnesium M17-Au27410 139 Q08

559812-S 20170817 Benzo(g.h.i)pyrene M17-Au26601 65 Q08

559812-W-V3

20170817 Calcium M17-Au27410 152 Q08

559812-W-V3

20170817 Magnesium M17-Au27410 139 Q08




562295-W 20170904 chloride M17-Se09301 58 Q08

562295-W 20170904 Calcium M17-Se14463 151 Q08

562295-W 20170904 Magnesium M17-Se14463 150 Q08

562295-W 20170904 Sodium M17-Se14463 138 Q08

562587-W-V3

20170911 Calcium M17-Se11244 144 Q08

562587-W-V3

20170911 Magnesium M17-Se11244 133 Q08

Surface Water

554681-S 20170731 Manganese B17-JI20225 145 Q08

554681-S 20170731 Zinc B17-JI20225 139 Q08

553958-W 20170731 N-MeFOSE M17-JI13881 163 Q08

558305-W 20170802 Calcium M17-Au14798 133 Q08

558305-W 20170802 Sodium M17-Au19100 132 Q08

558305-W 20170802 Zinc M17-Au14320 55 Q08

EM1711498_0_QCI

20170822 6:2 FTS EB1717577-002 Not determined

MS recovery not determined, background level greater than or equal to 4x spike level

Vertical Delineation (Groundwater)

562774-W-V2

20170907 Iron M17-Se12885 64 Q08

562774-W-V2

20170907 Sodium M17-Se14463 138 Q08

Surrogate Spikes

Surrogate spikes are a means of the laboratory checking that no gross errors have taken place throughout the analysis procedure, causing losses of the target analytes. The laboratory undertakes surrogate spikes by adding a known quantity of compounds with similar properties and behaviour to the target compounds, but which are not expected to be found in field samples.

Surrogate spikes are only appropriate for organic analysis and are added to all samples being analysed prior to the extraction process. A percent recovery is calculated for each surrogate, providing the analytical method accuracy of extraction of the target analytes from samples.

A review of the laboratory reports have shown that all the surrogate recoveries were within the acceptable DQI of 50 to 150% for phenols and 20 to 130% for PFAS. Therefore all the sample recoveries reported from the laboratories are considered to have acceptable accuracy.

Documents

Appendix K: Data Validation (QA/QC) - Department of Defence...Appendix K: Data Validation (QA/QC) Introduction This data validation appendix summarises the DQOs, established for the