2018 G STATUS REPORT · TCE concentration of 6.6 µg/L slightly less than the historical high concentration of 7.1 µg/L in a sample collected on February 20, 2008. The Schofield

2018 GROUNDWATER STATUS REPORT

GROUNDWATER PROTECTION PROGRAM

SAFE DRINKING WATER BRANCH

HAWAIÌ DEPARTMENT OF HEALTH

OCTOBER 21, 2019

GW106.2018GroundwaterStatusReport.Final.20191021.docx Page 2 of 44

ACRONYMS BTC Break Through Curve HBWS Honolulu Board of Water Supply CEC Contaminant of Emerging Concern CTC Carbon Tetrachloride CWB Clean Water Branch DBCP 1,2-Dibromo-3-Chloropropane or Dibromochloropropane DOA Hawaiì Department of Agriculture DOH Hawaiì Department of Health EDB Ethylene Dibromide EHASB Environmental Health Analytical Services Branch EPA Environmental Protection Agency EPO Environmental Planning Office GWPP Groundwater Protection Program HAR Hawaiì Administrative Rules HEER Hazard Evaluation and Emergency Response Office HPP Hawaiian Paradise Park HSPA Hawaiì Sugar Planters’ Association LC-MS Liquid Chromatography-Mass Spectroscopy LWRF Lahaina Wastewater Reclamation Facility MCL Maximum Contaminant Level MDL Method Detection Level MEK Methyl-ethyl Ketone MRL Method Reporting Limit OEQC Office of Environmental Quality Control OSDS Onsite Sewage Disposal System PCE Perchloroetylene PPCP Pharmaceuticals and Personal Care Products PWS Public Water System SDWA Safe Drinking Water Act SLD State Laboratories Division RUP Restricted Use Pesticides SDWB Safe Drinking Water Branch SLD State Laboratories Division TACP Technical Advisory Committee on Pesticides TCE Trichloroethylene TCP Trichloropropane UH University of Hawaiì UV Ultraviolet WQA Water Quality Analyzer WRMC Water Resources Monitoring Committee


TABLE OF CONTENTS

Acronyms ........................................................................................................................ 2 Hawaiì DOH Groundwater Protection Strategy .............................................................. 5 History of Groundwater Monitoring in Hawaiì (1979-2011) ............................................. 6

Detection of Contaminants in Hawaiì’s Groundwater .................................................. 6 Atrazine and Degradation By-Products .................................................................... 6 Other Detected Contaminants: ................................................................................. 8

Development of a Groundwater Monitoring Program (1984-2011) ................................ 10 Act 275, Session Laws of Hawaiì (SLH) 1984 ........................................................... 10 Act 127, SLH 1985 ..................................................................................................... 11 Act 220, SLH 1986 ..................................................................................................... 12 Groundwater Contamination Maps (2011) ................................................................. 15

Recent Monitoring Projects (2011-2017) ....................................................................... 15 Lahaina Groundwater Tracer Study - Appendix C ..................................................... 18

Project Description ................................................................................................. 18 Excerpt from Full Report Executive Summary ........................................................ 18 Future Use of Project Results ................................................................................. 19

Hawaiian Paradise Park Shallow Groundwater Quality Monitoring - Appendix D ...... 19 Project Description ................................................................................................. 19 Conclusions ............................................................................................................ 19 Future Work ............................................................................................................ 20

PPCP Leachability Model Monitoring Project - Appendix E ....................................... 20 Historical Detections and Drinking Water Monitoring (Groundwater Systems/Sources) - Appendix F ............................................................................................................... 21

Summary of Goal Completion ................................................................................. 21 Data Use and Archiving .......................................................................................... 21 Future Use of Project Results ................................................................................. 21 Project Description ................................................................................................. 21 1,2,3-Trichlolopropane (TCP) Results .................................................................... 22 1,2-Dibromo-3-Chloropropane (DBCP) .................................................................. 22 Trichloroethylene (TCE).......................................................................................... 22 Dieldrin ................................................................................................................... 23 Atrazine .................................................................................................................. 23 Other Contaminant Results .................................................................................... 23

Atrazine/Degradation By-Product Monitoring – Appendix G ...................................... 23 2015-2017 Atrazine/Degradation By Products in Groundwater Monitoring Data Summary and Recommendations .......................................................................... 24 Recommendations .................................................................................................. 25

Pharmaceutical and Personal Care Products (PPCP) Monitoring - Appendix H ........ 25 Why are PPCPs a Potential Water Quality Issue? .................................................. 25

Pesticides in Groundwater Monitoring Program (Development) ................................ 27 Groundwater Data Management ................................................................................... 28


Groundwater Contamination Viewer (Maps) ................................................................. 28 Groundwater Status ...................................................................................................... 29

Historical Groundwater Detections (prior to 2011) ..................................................... 29 Summary of recent Historical Groundwater Detections Monitoring (2011-2018) ....... 30

1,2,3-Trichlolopropane (TCP) Results .................................................................... 31 1,2-Dibromo-3-Chloropropane (DBCP) .................................................................. 31 Trichloroethylene (TCE).......................................................................................... 31 Dieldrin ................................................................................................................... 31 Atrazine .................................................................................................................. 32 Other Contaminant Results .................................................................................... 33

Summary of recent Groundwater Monitoring Studies (2011-2018) ............................... 38 Current Groundwater Monitoring ................................................................................... 39 Future Monitoring of Contaminants of Concern ............................................................. 39

Why Groundwater Quality Monitoring is Necessary ................................................... 39 Pesticides in Groundwater Monitoring Program Implementation ............................... 40 PPCP Monitoring of Water Resources and Use ......................................................... 42

Further Actions .............................................................................................................. 43 Additional Monitoring Needs and Resources ............................................................. 43 Criteria for areas where reuse wastewater should not be used ................................. 43 Potential need for Program changes .......................................................................... 44 Historical Detections and Drinking Water Monitoring ................................................. 44


HAWAIÌ DOH GROUNDWATER PROTECTION STRATEGY The mission of the Groundwater Protection Program is to safeguard groundwater quality and public health by protecting Hawaiì’s groundwater from contamination. In June 2017, the Hawaiì Department of Health (DOH) Groundwater Protection Strategy was finalized. See full strategy in Appendix A. Goal 1: Monitor and assess groundwater quality. ►Objective 3: Every four years, generate a Groundwater Status Report which

provides a review, analysis, and summary of groundwater monitoring data to understand contamination threats and sources of contamination. The report shall include a list of proposed future monitoring of contaminants of concern with rationale and priorities based on severity of public health impacts.

Goal 2: Identify and prioritize groundwater contamination threats. ►Objective 1: Recognize that groundwater quality monitoring since the 1990’s has

shown that the priority threats to groundwater quality as determined by DOH and review of data are as follows:

Priority Threats to Groundwater Quality – 2017 Onsite sewage disposal systems/cesspools/injection wells Large scale use of recycled water Large fuel storage facilities Increasing nitrate concentrations Agricultural chemicals

►Objective 2: Identify future threats to groundwater quality and prioritize for Goal 1 or Goal 3 follow-up.

Goal 3: Mitigate priority contamination threats and prevent contamination. ►Objective 1: Coordinate protection efforts with other branches/offices/agencies. ►Objective 2: Coordinate use of funding sources to support the HIGWPS: Safe

Drinking Water Branch (GW106/DWSRF 15%/DWSRF Fees). ►Objective 3: Coordinate the regulatory framework used by each

branch/office/agency to protect groundwater from the prioritized contamination threats (e.g., Code of Federal Regulations, Hawaiì Revised Statutes, Hawaiì Administrative Rules, EPA Guidelines and online tools).

This report will provide an overview of the history of groundwater contamination and monitoring in Hawaiì, summarize recently completed monitoring projects, and identify proposed future monitoring of potential contaminants of concern. Monitoring reports from 2011 to present are included in the Appendices.


HISTORY OF GROUNDWATER MONITORING IN HAWAIÌ (1979-2011)

DETECTION OF CONTAMINANTS IN HAWAIÌ’S GROUNDWATER Ethylene Dibromide (EDB), 1,2-Dibromo-3-Chloropropane (DBCP), and 1,2,3-Trichloropropane (TCP)

Starting in 1979, the Hawaiì State DOH initiated testing for Dibromochloropropane (DBCP) on four (4) of the islands at 16 sites, selected because of their proximity to pineapple fields. No DBCP was detected at these sites, though subsequent testing of water from another site (the Maui High School Well) revealed the presence of DBCP (Water Resources Research Center, 1985). Contamination of well water on O’ahu was first detected in April 1980 in Well No. 2703-01 near which a major spill of Ethylene Dibromide (EDB) had occurred three (3) years earlier. At the time of the spill, testing of the same well had revealed no detectable contamination with EDB. Starting in late 1982, extensive monitoring of wells supplying drinking water on O’ahu was started by the Honolulu Board of Water Supply (HBWS), and low levels of these chemicals, and subsequently a related chemical (1,2,3-trichloropropane), were identified in water samples taken from wells to the north of Honolulu in the pineapple-growing regions.

Although the precise source of the chemicals has not been determined, it is likely that the some of the EDB and DBCP used as soil fumigants leached from the treated soils into the groundwater and subsequently moved with the groundwater towards the wells. The HBWS, the DOH, and the Office of Environmental Quality Control (OEQC) were concerned that the presence of these chemicals in the water may present an unacceptable risk to the health of consumers. In the absence of federal or state regulations governing permissible levels of these chemicals in drinking water, and in view of the increasing dilemma brought about by improvements in chemical analytical techniques which enable lower and lower concentrations of contaminants to be detected, the HBWS, the DOH, and the OEQC sought expert opinion on the significance of these findings and on the most appropriate course of action.

Atrazine and Degradation By-Products

Discovery and Early Detections of Atrazine

Prior to 1993, atrazine was not routinely monitored in drinking water. The Hawaiì Sugar Planters’ Association (HSPA) was the first to identify atrazine in groundwater and voluntarily established a monitoring program in Hawaiì. At the time there was no Maximum Contaminant Level (MCL) and the health advisory level was 25 ppb. In 1983, HSPA alerted the DOH about detectable levels of atrazine found in Kunia and Waipahu on O’ahu. Subsequent groundwater sampling by HSPA in the early 1980s in areas of high agricultural use found about 40% of the sources had detectable levels of atrazine. In 1986, elevated levels were found in Pepeekeo Spring and Kihalani Spring on the


Hāmākua Coast of Hawaii Island which measured 4.1 and 2.3 ppb, respectively. The monitoring found that areas of high rainfall together with permeable soils were more susceptible to atrazine groundwater contamination. Throughout the 1980s and 1990s, HSPA has been an active participant in monitoring and evaluating atrazine trends in Hawaiì’s groundwater. Also, in partial fulfillment of EPA’s re-registration requirements for atrazine, the manufacturer, Ciba-Geigy agreed to conduct groundwater monitoring in 19 states that represented the major atrazine use areas in the country. Hawaiì’s component of The Ciba Crop Protection Groundwater Monitoring Study for Atrazine and its Major Degradation Products in the United States began in 1992 and included active participation from the DOA and HSPA. During the early 1990s, numerous sugar companies were still in operation and actively using atrazine. The purpose of the study was to assess the presence of atrazine and its degradation products in groundwater in areas of high atrazine use. The focus of the study was on drinking water supplies, particularly those with hydrogeologic features that increased vulnerability to contamination, but also evaluated shallow irrigation wells, and wells at different depths to better understand how and where atrazine may occur. Safe Drinking Water Program Atrazine Data

Since 1993, the Safe Drinking Water Branch (SDWB) has routinely sampled community drinking water systems. The most current water quality results by water system show all detectable levels of atrazine in the state water supply are well below the MCL of 3.0 ppb. Between 1993 and 1995, DOH tested community drinking water systems every three (3) months for atrazine. Water systems that did not detect atrazine could reduce the sample frequency for atrazine to once every three (3) years, or twice within a one (1) year period every three (3) years depending on the system population. Water systems that had detectable levels of atrazine were required to sample quarterly and could reduce sampling to annual if the concentration of atrazine was reliably and consistently less than the MCL. There are currently 129 active (CWS and NTNC) systems serving a population of 1,502,575. The remainder of the population is served by transient public water systems and by non-public water systems which include individual well, stream, or rainwater catchment sources. Since 1993, no public water system tested in Hawaii has exceeded the MCL for atrazine. Irrigation Wells Atrazine Data

State and federal law do not require routine pesticide monitoring of irrigation wells. In Hawaii, no ongoing monitoring of these wells is in place, and current water quality data are not available for pesticides in irrigation wells. However, the research conducted by Ciba-Geigy and HSPA provide a useful snapshot of historic impacts of sugarcane


herbicide use on groundwater. Irrigation wells in areas of active sugarcane cultivation were evaluated as part of the 1992-1994 Ciba-Geigy study. Eight (8) out of fourteen (14) irrigation wells sampled on Oahu had detections of atrazine or a degradation by-product. An earlier study by HSPA reported data collected by agricultural operators between 1983 and 1986 from eight (8) irrigation wells in the ‘Ewa Plain, Waipahu and Waialua on O’ahu. However, only one (1) of these samples from an irrigation well in Waialua, had a detection of atrazine (0.6 ppb). Detection limits ranged from 0.5 to 1.0 ppb, and the sampling may have missed lower concentrations consistent with those found in the Ciba-Geigy study. On Maui, 12 irrigation wells were sampled with detections in six (6) wells ranging from 0.13 ppb to 0.3 ppb atrazine and 0.12 to 0.63 ppb atrazine degradation by-products. The highest detection was at a well depth of 380 ft. On Kauai, there were no detections of atrazine or its degradation by-products in any of four (4) irrigation wells sampled during the Ciba-Geigy study period. The SDWB dataset included one (1) additional irrigation well sampled on Kauai at Barking Sands. A single sample was taken in 1988 with a reported detection of 3.5 ppb. However, the original datasheet or other information regarding the sampling is not available. The depth and status of the well is unknown and the well was not re-sampled. Historical Detection of Atrazine/Degradation By-Products in Hawaiì’s Groundwater Resources

Based on the Groundwater Contamination Maps from 2011, the following table shows the number of sample locations with Atrazine and Degradation By-Products detected in groundwater, by island.

ISLAND Atrazine Desethyl Atrazine

Desisopropyl Atrazine

Desethyl, Desisopropyl Atrazine

Kauai 3 0 0 0 O’ahu 13 13 3 3 Maui 5 6 0 1 Hawaiì 32 18 3 2

Other Detected Contaminants:

Dieldrin/Chlordane

In 1995, regulatory drinking water testing has found and confirmed the presence of trace levels of chlordane dieldrin in some of the Honolulu Board of Water Supply wells. Samples from HBWS wells were analyzed from January through December 1995. The analysis was conducted by Montgomery-Watson Laboratories in Pasadena, California using test methods approved by the Environmental Protection Agency. Chlordane is currently regulated by the Environmental Protection Agency. Levels detected did not exceed the maximum contaminant limit (MCL) of 2.0 ppb established for drinking water.


Dieldrin is an insecticide that was widely used from the 1950s to the 1970s in agriculture, for termite treatment and the control of disease vectors such as mosquitos. In Hawaiì, dieldrin was first registered for use in 1976 as a restricted use pesticide primarily for subsurface soil treatment of termites. It was also used on various fruits, vegetables, turf and ornamentals. Most uses for dieldrin were banned in 1974 except to control termites. In 1987, EPA banned all uses. Dieldrin is no longer produced in or imported into the United States. EPA does not regulate dieldrin in drinking water. However, California adopted a dieldrin action level of 0.05 ppb. Based on California’s action level, HBWS discontinued the use of Jonathan Springs Well (0.06 ppb) as a precautionary measure. Levels detected in other wells do not warrant a health concern at this time. The HBWS and the Department of Health continue to monitor chlordane and dieldrin levels in drinking water sources.

Bromacil

In 1988, the Department of Health’s groundwater monitoring program detected a trace level (1.3 ppb) of the herbicide bromacil in the Waiehu Well on Maui. The level detected was far below the Lifetime Health Advisory Level set by the Environmental Protection Agency. This was the first time that this compound has been found in groundwater in the state. Bromacil is registered for use on pineapple and citrus fruits.

Hexazinone

The herbicide hexazinone (sold under the trade name “Velpar” by the DuPont Company) was used by the sugar industry to control weeds in sugar cane fields. Its use has a very short history dating back to the late 1980s when it was first registered for use on crops for human consumption. It also had an experimental use approval on pineapple which expired in 1983. During the mid-1980s the Hawaiì Sugar Planters’ Association (HSPA) began detecting hexazinone at its various monitoring sites. In 1987, HSPA submitted a report to the Board of Agriculture indicating the presence of hexazinone in spring waters along the Hāmākua Coast at levels ranging from 0.05 to 0.7 ppb. The presence of hexazinone in the Hāmākua area is probably due to its relatively high solubility in water combined with high rainfall, highly permeable soil, and the shallow water table in the area. It was recommended that the use of hexazinone in vulnerable areas be re-evaluated and continued to be monitored.


Other Contaminants

In the mid-1980’s, other contaminants such as trichloroethylene (TCE), perchloroethylene (PCE), carbon tetrachloride (CTC) were also being detected in groundwater/drinking water sources. These contaminants are industrial-based solvents and were believed to have been generated by the military as well as by such operations as paint stripping, degreasing, and dry cleaning (just to name a few). DEVELOPMENT OF A GROUNDWATER MONITORING PROGRAM (1984-2011)

ACT 275, SESSION LAWS OF HAWAIÌ (SLH) 1984 Groundwater protection became an issue of public concern in Hawaiì with the detection of pesticides used by the pineapple and sugar industries in the early 1980s. As a result of contamination being detected in Hawaiì’s drinking water, the Hawaiì State Legislature passed Act 275, SLH 1984. This Act placed the responsibility for coordinating all affected agencies involved in the prevention, monitoring, and mitigation of groundwater contamination with the OEQC. To accomplish this, the OEQC shall coordinate systematic monitoring by the Department of Health and Honolulu Board of Water Supply of all aquifers and surface water sources, regardless of whether they are used as drinking water sources, for locally suspected pesticides and chemical by-products. Monitoring priority would be given to potable aquifers and surface water resources. Findings from a review of existing groundwater monitoring activities in Hawaiì revealed that:

• Groundwater quality monitoring was conducted by more than a dozen independent county, state, federal and private institutions;

• Monitoring activities were specifically tailored to suit the special informational needs of the funding agency, limiting activities mostly to drinking water wells and organic contaminants;

• Limited value in determining the origin of groundwater contamination from discrete (point) sources of pollution.

Technical Problems

• Present groundwater monitoring system was not designed to demonstrate cause and effect relationship between pollution sources and changes in water quality. (Drinking water wells located away from pollution sources.)

• Depth and thickness of the aquifer was another problem in determining pollutant impact on groundwater. (Drinking water wells are designed to produce sufficient


quantities of water and optimize water quality within the column, generally casing off the top of the water table.) Without site-specific monitoring, the magnitude and extent of potential groundwater contamination can only be subject to speculation and modeling based on factors such as geology, contaminant characteristics, and quality of underlying water bodies.

Concerns

• Unclear regulatory roles; • Limited analytical resources; • Limited risk assessment resources; • Groundwater monitoring limited to reactive, rather than proactive role; and • Monitoring uncoordinated between State agencies and private industries.

ACT 127, SLH 1985 The Hawaiì State Legislature passed Act 127, SLH 1985 which amended Act 275, SLH 1984. This Act authorized OEQC to review, evaluate, and make recommendations to agencies involved in groundwater contamination. The Act specifically tasked the OEQC to:

Coordinate the development of a systematic approach to monitoring by the department of health and board of water supply of all aquifers and surface water sources, regardless of whether they are used as drinking water sources, for locally suspected pesticides and chemical by-products. Monitoring priority would be given to potable aquifers and surface water drinking resources.

As a result of Act 127, SLH 1985, a Water Resources Monitoring Committee (an ad hoc subcommittee of the Technical Advisory Committee on Pesticides (TACP)) was formed. Agencies participating on the Water Resources Monitoring Committee included: DOA - Pesticides Branch, DOH – Hazardous Waste & Safe Drinking Water Programs, OEQC, and HBWS. The tasks of the Water Resources Monitoring Committee were to:

• Survey all groundwater monitoring activities in Hawaiì; • Begin the design of an interim systematic groundwater monitoring strategy; • Interim strategy to develop an approach for screening groundwater for

compounds most likely to be present due to environmental contamination; and • List of 39 Pesticides and Chemical Parameters that should be monitoring (from

an original list of 42 parameters).


Criteria for selecting the following list of 39 chemical parameters that should be monitored in groundwater were:

• Use of chemical in Hawaiì, • Record as a groundwater contaminant, • Chemical properties (AF & RF values), • Cost and reliability of analysis, and • Toxicological properties.

1. Acetone 2. Aldicarb 3. Ametryn 4. Atrazine 5. Benzene 6. Bromacil 7. Carbofuran 8. Carbon Tetrachloride 9. Total Chlordane 10. 2,4-D 11. Dalapon 12. 1,3-Dibromochloropropane

(DBCP) 13. 1,2-Dichloropropane (1,2-D) 14. Cis/Trans 1,3- Dichloropropene

(1,3-D) 15. Difolatan 16. Diuron 17. Endosulfan 18. Ethylene Dibromide (EDB) 19. Glyphosate

20. Heptachlor 21. Heptachlor Epoxide 22. Hexazinone 23. Methomyl 24. Methyl Bromide 25. Methyl Ethyl Ketone (MEK) 26. Ketone (MIBK) 27. Mevinphos 28. Nemacur 29. Oxamyl 30. Paraquat 31. Pentachlorophenol 32. Perchloroethylene (PCE) 33. Simazine 34. Toluene 35. 1,1,1-Trichloroethane 36. 1,1,2-Trichloroethane 37. Trichloropropane (TCP) 38. Trichloroethylene 39. Xylene

ACT 220, SLH 1986 In 1986, the Hawaiì State Legislature found that the establishment of a Groundwater Protection Program was a matter of compelling state interest to protect and preserve the health of the people of Hawaiì. Act 220, SLH 1986 provided resources to the DOH for the creation of a Groundwater Protection Program. The Program was to:

• implement groundwater strategy developed by the WRMC; and • initiate baseline groundwater monitoring.


Tasks for the Interim Groundwater Monitoring Strategy: • Select Preliminary Target Compounds to Monitor. • Collect Chemodynamic, Analytical, and Cost Data. • Select Monitoring Sites and Prioritize Target Compounds. • Select Sampling, Analytical, Quality Assurance and Reporting Protocols. • Select and Contract Laboratories to Analyze Samples. • Collect Samples for Analyses. • Compile Results of Analyses. • Report and Publish Results. • Update WRRC Database. • Analyze Monitoring Strategy.

Implementing the Interim Groundwater Monitoring Strategy:

• Sampling began in 1987. • Well Selection Criteria: groundwater use, land use, presence of groundwater

contamination in surrounding area, and geological location. Sample Collection:

• 1987 – 12 wells • 1988 – 29 wells • 1989 – 20 wells/13 confirmation samples

Initial Report completed in 1991. Positives reported on Groundwater Contamination

Maps. Groundwater Monitoring transferred from EPO to SDWB. Additional monitoring conducted for Hexazinone and MEK. Due to budget cuts and staff layoffs, funding for the groundwater monitoring program was eliminated. From 1989 to 2011, the primary source of groundwater monitoring data was the Drinking Water Compliance Monitoring Program. The Safe Drinking Water Monitoring Requirements (1986 and 1996 SDWAA) required drinking water sources to be monitored for the following Volatile Organic Chemicals and Synthetic Organic Chemicals:


Volatile Organic Chemicals (VOCs) Benzene Carbon Tetrachloride Chlorobenzene o-Dichlorobenzene p-Dichlorobenzene 1,2-Dichloroethane 1,1-Dichloroethylene cis-1,2-Dichloroethylene trans-1,2-Dichloroethylene Dichloromethane 1,2-Dichloropropane (DCP) Ethylbenzene Styrene Tetrachloroethylene Toluene 1,1,1-Trichlroethane 1,1,2-Trichloroethane 1,2,4-Trichlorobenzene Trichloroethylene Vinyl Chloride Xylenes (total)

Synthetic Organic Chemicals (SOCs)

2,4-D Alachlor Aldicarb Aldicarb Sulfone Aldicarb Sulfoxide Atrazine Benzo(a)Pyrene Carbofuran Chlordane Dalapon Dibromochloropropane (DBCP) Di(2-ethylhexyl)adipate Di(2-ethylhexyl)phthalate Dieldrin Dinoseb Diquat Dioxin (2,3,7,8-TCDD) Endothall Endrin Ethylene Dibromide (EDB) Glyphosate Heptachlor Heptachlor epoxide Hexachlorobenzene Hexachlorocyclopentadiene Lindane Methoxychlor Oxamyl (Vydate) Pentachlorophenol Picloram Polychlorinated biphenyls (PCBs) 2,4,5-TP (Silvex) Simazine Toxaphene 1,2,3-Trichloropropane


From 1989 to 2011, the Groundwater Protection Program focused its effort on:

• Worked with the DOA and the University of Hawaiì on the Comprehensive Leaching Risk Assessment System (CLERS) Model for pesticides, drinking water contaminants and pharmaceutical and personal care products (PPCPs).

• Prepared an EPA-approved wellhead protection program. • Prepared an EPA-approved source water assessment and protection program

plan and conducted assessments for over 450 drinking water wells/sources; and • Created a Wellhead Protection – Financial Assistance Program to provide

funding to PWS for the development and implementation of protection activities. GROUNDWATER CONTAMINATION MAPS (2011) The Groundwater Contamination Maps for the State of Hawaiì were first published in August 1989. However, the maps were not published between 1999-2001 and 2006-2011 due to resource limitations. These 2011 Maps include historical monitoring data generated since the first publication unless subsequent monitoring data shows no detection at which time the contaminant was removed from the report. See Appendix B for the 2011 Groundwater Contamination Maps for O’ahu, Kauai, Maui, and Hawaiì Islands. RECENT MONITORING PROJECTS (2011-2017)

A Comprehensive Water Quality Monitoring Strategy for the State of Hawaiì, Version 2.0, 9/22/2010 identified that recent layoffs and reduction-in-force caused major changes in drinking water monitoring. The DOH lost four (4) positions on four (4) islands from the monitoring program of the SDWB. As a result, the branch scaled back its compliance monitoring and transitioned that monitoring work to the public water systems (PWS), who must monitor their respective water sources. Beginning in 2011, the SDWB provided sampling training to the PWS. Staff continues to interact with the PWS to ensure a smooth transaction in sample handling and logistics and continues to manage the analytical results. The Hawaiì Groundwater Protection Program under the Federal Groundwater (GW 106) Program Grant shifted its focus from planning to monitoring activities. The monitoring activities include the collection of data on the quality of groundwater sources which will be used as the basis for developing groundwater protection policies and guidelines. Prior to the implementation of any groundwater monitoring projects, the Groundwater Protection Program was required to prepare an EPA-approved Quality Assurance Program Plan and a Groundwater/Drinking Water Quality Monitoring Projects Plan.


The Groundwater Protection Program envisioned a Groundwater Quality Monitoring Program consisting of a systematic approach to monitoring groundwater resources based on criteria developed as part of Hawaiì’s Comprehensive Water Quality Monitoring Strategy for the State of Hawaiì, Version 2.0, 9/22/2010. The following identifies the monitoring program’s objectives and requirements. There are several instances where groundwater quality monitoring was performed: • Collection of basic groundwater quality data for use in assessing ambient

groundwater quality; • Collection of groundwater quality data to confirm drinking water monitoring

detections of contaminants and historical data; • Collection of groundwater quality data to assist SDWB drinking water monitoring in

defining the actual extent of detected groundwater contaminants; • Collect ambient groundwater quality data in areas where limited or no monitoring

has been conducted; • Collect groundwater quality data to assess water quality in areas of concern due to

possible contamination sources; and • Assist special projects with groundwater quality monitoring activities. Identified potential impacts to groundwater quality from various activities, included:

• Agricultural activities: sediments nutrients (fertilizers) toxic chemicals (pesticides)

• Wastewater disposal systems (cesspools, septic systems, other Onsite Sewage Disposal System [OSDS]) pathogens nutrients toxic chemicals (PPCPs)

• Use of Alternative Water Sources (Reuse Wastewater) toxic chemicals (PPCPs)

Some of the groundwater monitoring projects identified included:

• Ambient monitoring of groundwater quality for drinking water sources that are currently not being used but are identified as potential Underground Sources of Drinking Water (USDW). This data may be used by public water systems to identify new drinking water sources as well as evaluate the water quality and the effectiveness of the system’s water protection efforts.

• Groundwater surveillance monitoring. This will allow problematic contaminants associated with specific sources of contamination to be monitored in groundwater


that are drinking water sources or potential drinking water sources, including new and emerging contaminants.

• Other monitoring activities that were being developed include the detection of new and emerging contaminants. The monitoring program will explore numerous non-drinking water regulated contaminants and work with the Environmental Health Analytical Services Branch (EHASB), State Laboratories Division (SLD) to expand analytical capabilities capable of detecting new and emerging chemical compounds.

• Working with the Hawaiì DOA-Pesticides Branch which regulates the licensing and use of pesticides in the state. Potential groundwater contamination is one of the criteria used in the pesticide licensing process. The DOA currently does not have adequate resources to monitor the impact of pesticides on groundwater. Through collaboration and data sharing, SDWB will be able to implement a monitoring program to evaluate areas where specific pesticides may be used.

• Work with other programs within the Environmental Health Administration including: o Wastewater Branch (WWB): water quality data of reused/recycled/reclaimed

water. o Clean Water Branch (CWB)/WWB: water quality of groundwater sources

near OSDS, in watershed and impaired water bodies. o CWB: water quality data related to the interaction of ground and surface

waters. • Microbial testing of shallow groundwater wells at Hawaiian Paradise Park (HPP).

Over the last decade, a significant number of private wells have been developed in the HPP area which is predominantly on cesspools and septic systems. This project will assess the water quality of shallow groundwater wells in that area for microbes, nutrients, personal care products and pharmaceuticals as it relates to OSDS. In addition to providing data on groundwater quality, data useful to the WWB could be generated which would assist in the banning and upgrading of cesspools.

Groundwater Quality and Related Projects conducted and/or completed include the following:

• Lahaina Tracer Study • Hawaiian Paradise Park Shallow Groundwater Quality Monitoring Study • PPCP Leachability Model Monitoring Project • Historical Detections and Drinking Water Monitoring (Groundwater Sources) • Atrazine and Degradation By-Products Monitoring • Pharmaceutical and Personal Care Products (PPCP) Monitoring • Pesticides in Groundwater Monitoring Program (Development)

See the reports for these projects in the respective appendices as listed in the section title.


LAHAINA GROUNDWATER TRACER STUDY - APPENDIX C Project Description

This project was initiated as joint effort between DOH, U.S. EPA, U.S. Army Corp of Engineers, and the University of Hawaiì – Department of Geology and Geophysics. The goal of the study was to use a groundwater tracer test to investigate whether treated wastewater injected at the Lahaina Wastewater Reclamation Facility (LWRF) was likely seeping into surface waters near the shoreline fronting the Kā’anapali resort area of Maui, Hawaiì.

On July 28, 2011, about 340 pounds of Fluorescein dye were added to the injectate stream of Wells 3 and 4 at the LWRF. The dye was detected 84 days later at a submarine spring group referred to as the North Seep Group (NSG). About three (3) weeks later the dye was detected at a group of submarine springs about 150 yards south of the NSG. The southern set of submarine springs is referred to as the South Seep Group (SSG). Field work for the Lahaina Groundwater Tracer Study officially ended on December 31, 2012. At the end of the field work, the Break Through Curve (BTC) was sufficiently developed to extrapolate the future dye concentrations to point where the dye could no longer be detected by laboratory instruments. However, it is desirable to confirm the extrapolated portion of the BTC with actual measurements of the dye concentration. DOH CWB started monthly nutrient seep sampling in January 2012 and continued this sampling through December 2014. CWB provided SDWB with dye samples as part of their monthly sampling. These samples have been analyzed for Fluorescein and the results are compared to the extrapolated portion of the BTC.

Excerpt from Full Report Executive Summary

In sum, our results conclusively demonstrate that a hydrogeologic connection exists between LWRF Injection Wells 3 and 4 and the nearby coastal waters of West Maui. Eighty-four days following injection, FLT tracer dye introduced to these wells began to emerge from very nearshore seafloor along North Kā’anapali Beach, approximately 0.85 km (0.5 miles) to the southwest of the LWRF. As proposed by Hunt and Rosa (2009), our results substantiate the conclusion that due to geologic controls that include a hydraulic barrier created by valley fills to the northwest, the main wastewater effluent plume from the LWRF travels obliquely towards the southwest. An estimated 64 percent of the Well 3&4 effluent follows this route and discharges at coast. The peak concentration of the FLT dye occurred 9 to 10 months following injection, with an average transit time of approximately 15 months. Since the treated wastewater plume is broad, the injectate travel time takes from about three months to arrive, to over an estimated four years for the draining trailing edge fully to exit the coast. During this time, there is a significant loss of nitrogen due to extensive denitrification and other suboxic to anoxic microbial degradation processes fueled by a sustained supply of organic matter transport within the effluent plume. The release of dissolved phosphorus, on the other hand, is relatively enriched. The treated wastewater discharges from the seafloor mixed


with other marine and fresh waters predominantly as diffuse flow (>90%), but also through a patchwork of hundreds of very small (ca. 5 cm2) submarine springs. This central discharge area occurs as two adjacent clusters of diffuse flow and springs with a combined total seafloor area of 2,300 m2. The emerging waters appear well mixed in the nearshore zone and, being relatively warm and brackish, spread over an area visible by thermal infrared imagining that covers an ocean surface area more than 167 acres in size. The lateral distribution of the FLT tracer dye agrees well with the lateral limits of the ES-4 anomalously warm ocean surface water plume detected by air. These conclusions drawn from both the Interim Report and this Final Report are summarized and discussed below.

Future Use of Project Results

The project results are currently being used to evaluate whether or not NPDES permits should be required for underground injection that directly impacts CWA regulated waters. The long duration of tracking tracer test breakthrough curves generated by the Lahaina Groundwater Tracer Study can be used in research projects to better understand the transport solutes in Hawaiì’s groundwater.

HAWAIIAN PARADISE PARK SHALLOW GROUNDWATER QUALITY MONITORING - APPENDIX D Project Description

This project measured water quality of shallow groundwater wells (less than 150 deep) in the HPP Subdivision on the Island of Hawaiì. The HPP Subdivision is completely reliant on OSDS for the disposal of wastewater. Since there is no centralized domestic water sources located in the area, >250 subdivision residents may be using wells that may be contaminated with OSDS pollutants. This project analyzed for microbial and basic water/wastewater contaminants. Conclusions

The high rate of bacteria detections (of the 31 wells sampled, 16 were positive for total coliforms (52%) and 7 were positive for e. coli (23%)) showed that the large concentrations of OSDS are having a detrimental impact on the drinking water quality of the groundwater. This impact can pose a health risk to the consumers of domestic well water if the ultraviolet treatment systems are not used. Again, it must be stressed that the survival time for the indicator bacteria monitored for by this study is much shorter than that for other pathogens. Thus, the risk of infection from ingesting untreated groundwater is greater than the rate of positive bacteria detections would indicate. This study was not able to correlate any of the chemical species analyzed to any the incidents of bacteria detections. This may be partially due to dilution by upwelling of


groundwater not impacted by OSDS. The lack of the expected trend of increasing concentrations of the wastewater indicators (optical brighteners, nitrate, and phosphate) along the groundwater flow path could have multiple causes such as natural attenuation of the indicators through sorption, transformation, or degradation; or the mixing of OSDS contaminated groundwater with groundwater free of OSDS constituents. But, the low nutrient concentrations do indicate that groundwater discharging along the coastline at HPP should present no greater environmental risk than other groundwater in eastern Hawaiì Island.

The results of this study were presented to the residents of HPP on March 18, 2015. It should be stressed to those residents that get their domestic water from on-site wells that they need an operating filtration and disinfection system.

Future Work

Potential follow-on investigations could include:

• Analyzing samples for PPCPs, • Continuing to investigate the utility of fluorescent scans to screen for wastewater

influence; and • Doing dual analysis to compare the analytical results measured by a field

colorimeter with the analysis performed by a certified laboratory. This exercise will test the utility of the field colorimeter as an analytical tool.

PPCP LEACHABILITY MODEL MONITORING PROJECT - APPENDIX E PPCPs are ubiquitous in domestic sewage as well as in animal waste lagoons, manures, and land application sites. In addition, estrogenic compounds (natural and synthetic) are also found in sewage and waste lagoons. Because of their endocrine disrupting properties, there is public as well as regulatory concern about the presence of these compounds in drinking water sources. The origins of these chemicals are primarily from the discharge of treated wastewater to streams and rivers. In areas where large confined animal feeding operations (CAFOs) exist, many antibiotics and pharmaceutical compounds have also been found in shallow ground waters adjoining lagoons. While many of these PPCPs bind strongly to soils, many others are also extreme leachers. Currently, the database for the leaching behavior of these chemicals, particularly for Hawaiì conditions is scarce. In order to improve the CLERS model for assessing the leaching of PPCPs, the fate and transport data for selected PPCPs in Hawaiì conditions will be needed.

The Department of Health has worked with the University of Hawaiì, Water Resources Research Center to identify selected chemical compounds (illicit, PPCP, and steroids) found in Hawaiì’s wastewater and its leachability in Hawaiì’s soils.


HISTORICAL DETECTIONS AND DRINKING WATER MONITORING (GROUNDWATER SYSTEMS/SOURCES) - APPENDIX F Summary of Goal Completion

A total of 62 wells that have a history of past contamination were sampled. This included samples from 23 well fields (locations with closely spaces such as the Waipahu IV which has four wells within the same compound).

Data Use and Archiving

The report, tables and maps will be archived on the SDWB server. The data from this study will be shared with Hawaiì Department of Agriculture (DOA) and the Hawaiì Agriculture Research Center. Data will be publicly available on the Groundwater Contamination Viewer.

The results of this project will be used to increase surveillance in areas where an increasing trend in contaminant concentrations were identified. The data can also be used by water systems when planning locations for new water sources and planning well head treatment systems.


The areas that show an increasing trend in the contaminant concentrations need further evaluation to determine potential migration paths. A follow on workplan will be developed to track the groundwater contamination trends in those areas that the concentrations are either stable or increasing.

Project Description

All of the major Hawaiian Islands, except Lāna’i, have a history of detections of contaminants regulated under the Safe Drinking Water Act (SDWA). Currently, most samples collected for SDWA compliance are taken after the water had been treated to reflect the water quality that is being consumed. This treatment removes contaminants that are captured by the well and are not reflective of the groundwater quality in the aquifer. This project collected samples prior to treatment from drinking water sources with a history of contamination. For wells with a sufficient number of samples collected, a determination was made as to whether the contamination level was increasing, decreasing, or remaining stable. These trend analyses were only made for wells where contamination was detected during the 2014 sampling events and there were at least two (2) previous detections of the contaminant. There was sufficient data for 1,2,3-Trichlolopropane (TCP), 1,2-Dibromo-3-Chloropropane (DBCP), Trichloroethylene (TCE), and Dieldrin to make determinations regarding trends in contamination levels. The contaminants Carbon Tetrachloride, Chlordane, Heptachlor Epoxide, Tetrachloroethylene (PCE), and Ethylene Dibromide (EDB) were detected in 2014, but there was an insufficient number of historical samples to evaluate trends. Eight (8)


wells were sampled during 2014 for Atrazine, and all concentrations were less than the detection limit.

1,2,3-Trichlolopropane (TCP) Results

Table 1 shows the sampling results for TCP. Samples from 49 wells or well fields were analyzed for TCP either during 2014 or previously. During the 2014 round, samples were collected from 40 wells or well fields. Of the samples collected during 2014, 9 had TCP concentrations greater than the MCL of 0.6 µg/L. The highest TCP concentration was 2.8 µg/L in a sample collected from the Mililani III Wells on May 1, 2013. A sample collected from the nearby Mililani II Wells had a concentration of 2.4 µg/L on March 3, 2008. Prior to 2014, TCP exceeded the MCL at 12 of the wells sampled.

There were a sufficient number of samples to evaluate trends for 30 wells. The TCP concentration in eight wells was either decreasing or stable and decreasing. At 11 of the other wells the TCP concentration was stable, neither increasing nor decreasing with the 2014 concentration only slightly less than the historical concentration. At 11 wells, the TCP concentration was either increasing or stable with 2014 sample concentration being slightly higher than historical concentrations. The area with most consistent increasing trend was Waipahu.

1,2-Dibromo-3-Chloropropane (DBCP)

Table 2 shows the sampling results for DBCP. Thirteen (13) wells have a history of positive DBCP detections. All but one well had DBCP concentrations that exceeded the MCL of 0.04 µg/L. Ten (10) wells were resampled in 2014. The DBCP concentration in nine (9) of the wells exceeded the MCL. The maximum DBCP concentration of 0.27 µg/L were measured at the Mililani I wells. This is only slightly less than the historical high concentration of 0.28 µg/L measured at this well field. There were a sufficient number of sampling events at four (4) of the wells to evaluate the temporal trend. There was no confirmed increasing trend, but the trend at the Mililani I Wells was either stable or slightly increasing. There was a decreasing trend at 2 wells and the trend was stable at another well.

Trichloroethylene (TCE)

Table 3 list the sampling results for TCE. There are five (5) drinking water wells with a history of positive detections for TCE. These wells are all located in the central O’ahu corridor between the Ko’olau and the Wai’anae Mountain Ranges. Four (4) of these wells were resampled during the 2014 sampling events. The MCL of 5 µg/L was exceeded in the sample collected from the Del Monte Kunia 3 Well. This sample had a TCE concentration of 6.6 µg/L slightly less than the historical high concentration of 7.1 µg/L in a sample collected on February 20, 2008. The Schofield Battery of Wells had the highest TCE concentration at 40.6 µg/L in a sample collected on June 18, 2013. The TCE concentration in all other wells was less than the MCL. The Waialua Wells were the only location where a sufficient number of samples were collected to evaluate the


temporal trend of TCE contamination. At these wells the TCE concentration remained stable at about 1 µg/L.

Dieldrin

The Dieldrin sample results are summarized in Table 4. A total of fifteen (15) public drinking water wells or well fields have a history of Dieldren detections. Eleven (11) of these wells were resampled in 2014. The MCL of 0.2 µg/L was not exceeded in any sample collected. The highest concentration in samples collected during the 2014 sampling event was 0.09 µg/L at the Halawa Wells. The highest historical Dieldrin concentration was 0.28 µg/L in a sample collected at the Wilder Well on April 5, 2001. Dieldrin was below the detection limit in two of the samples collected during the 2014 sampling event. There are five (5) locations where a sufficient number of samples were collected to evaluate the temporal trend. All had decreasing trends except for Halawa Wells where the Dieldrin concentration was either stable or slightly increasing.

Atrazine

Table 5 lists the sampling results for Atrazine. There are 23 public drinking water wells or well fields with a history of Atrazine contamination. The majority (13) are on the island of Hawaiì. Five of these wells and four (4) irrigation wells were sampled during the 2014 sampling event. The Atrazine concentration in all of the samples collected in 2014 was less than the detection limit. The MCL of 3 ug/L has been not exceeded in any sample collected. The highest Atrazine concentration in any sample collected was 1.3 ug/L in a sample collected at the Ō`ōkala Well in 1994. Subsequent samples from the Ō`ōkala Well has shown a steady decline in the atrazine concentration to less than 0.3 ug/L in 2016.

Other Contaminant Results

Table 6 lists the results for contaminants where there was only a single location where the concentration was equal to or greater than the reporting limit. The contaminants include: Carbon Tetrachloride, Heptachlor Epoxide, Tetrachloroethylene, and Ethylene Dibromide. The well, highest concentration detected, and current concentration are compared to the MCL. The only contaminant that exceeded the MCL was Ethylene Dibromide in the Maunaolu-Smith Well on Maui. ATRAZINE/DEGRADATION BY-PRODUCT MONITORING – APPENDIX G One of the GWPP’s first monitoring efforts was to conduct Atrazine/Degradation By-Products monitoring of groundwater resources. The GWPP sampled groundwater sources that have reported positive results for atrazine/degradation by-products from 1983 to 2011 and for which no subsequent monitoring has taken place. Samples were also collected from groundwater wells near areas where atrazine was or is currently being used.


Samples were collected by GWPP staff and analyzed by the DOH - State Laboratories Division (SLD). Analysis was conducted using EPA Method 536 – “Determination of Triazine Pesticides and Their Degradates in Drinking Water by Liquid Chromatography Electrospray Ionization Tandem Mass Spectrometry (LC/ESI-MS/MS).” The contaminant detection level for atrazine and its degradation by-products was less than 0.03 ug/l (ppb). 2015-2017 Atrazine/Degradation By Products in Groundwater Monitoring Data Summary and Recommendations

A review of the historical water quality data indicates a direct connection between historical/current applications of atrazine for agricultural uses and subsequent detections in groundwater. Areas expected to be most vulnerable to contamination include those with high rainfall, thin permeable soils, limited weathering of rocks in the unsaturated zone, shallow depths to groundwater, and high rates of atrazine use. Contamination of groundwater by atrazine and its degradation by-products has primarily been detected within or hydraulically down gradient from areas currently or previously used for sugarcane cultivation. Atrazine use in Hawaiì has decreased over the years due to label restrictions and the decline of the sugar industry. Until recently (2016), the largest user in the state was the sugar industry on Maui. With the closure of the last sugar cane plantation, atrazine usage has shifted to sweet corn and seed corn production. Data from the “Atrazine/Degradation By-Products in Groundwater Monitoring Project” conducted by the DOH from 2015-2017 has generally shown a downward trend in the levels of atrazine and its degradation by-products detected in groundwater throughout the state. Several wells with prior detections (at low concentrations below 0.10 ug/l) are now “not detected.” Atrazine and its degradation by-products were detected in several wells that were previously negative or not in existence in 2011 (these wells are located in areas where atrazine was previously or currently used). Many of the historical detections associated with agriculture and irrigation wells were not sampled for this project, as closure of sugar cane operations have made these wells inactive, abandoned, sealed, or not operational. Several wells associated with drinking water

Figure 1. SLD – Analysis Using LC-MS


systems were not sampled, as the wells were not operational at the time of project sampling. Recommendations

After reviewing the groundwater and drinking water data, DOH recommends the following:

• Resample new detections (to confirm that contaminants are present); • Conduct sampling at sources (that were not sampled under this project) which

have been brought back into operation; • Continue sampling in the limited areas where atrazine is still being used

(sampling may be done under a Pesticides in Groundwater Monitoring Project), as it has been shown that there is a connection between the use of atrazine and detection in groundwater; and

• Conduct periodic sampling (possibly once every 5-10 years) of historical detection sites to assess continuing contamination trends in areas of past atrazine use. As lands in former agriculture and sugar cane cultivation are converted to housing developments or other uses, groundwater quality in these areas should be monitored to ensure that the quality of water meets the increased demands for drinking water resources.

These recommendations are based on the Hawaiì Groundwater Protection Strategy:

• Goal 1 - Objectives 1 and 3 • Goal 2 - Objective 2 • Goal 3 - Objective 1 (HEER and DOA)

PHARMACEUTICAL AND PERSONAL CARE PRODUCTS (PPCP) MONITORING - APPENDIX H Why are PPCPs a Potential Water Quality Issue?

Alternative Water Sources - Water Reuse

The DOH Wastewater Branch has refined its data collection methods to more accurately measure the amount of recycled water being used. As such, the reuse amount for 2015 onward is based on operator reports rather than estimations. Operator reports provide more accurate figures because they account for declines in use due to rainy periods, off-spec water, and equipment malfunctions. In 2015, 16.3 million gallons per day (MGD) were supplied for reuse. In 2016, 17.2 MGD were supplied.

The combination of growing population and limited drinking water resources is reducing the availability and quality of our drinking water supplies. In addition, we continue to experience problems as a result of the disposal of wastewater. Wastewater management practices that protect, conserve, and fully utilize water resources are vital


to Hawaiì. Increasing the safe use of recycled water can greatly assist in meeting the State’s water requirements, enhance the environment, and benefit public health by preserving resources upon which public health protection is based. DOH has long been an advocate for water reuse as long as it does not compromise public health and our valuable water resources. Promoting the use of recycled water is one of the DOH’s high priority goals.

Water reuse has moderately increased in Hawaiì over the past several years. There are now 39 wastewater treatment facilities that produce recycled water. Of these 39 facilities, 11 are R-1 facilities, which produce the highest quality recycled water, while the remaining facilities produce R-2 and R-3 water.

In January 2016, the DOH WWB revised the Reuse Guidelines and separated it into two volumes. Volume 1: Recycled Water Facilities addresses technical requirements to be met for various qualities of recycled water, and requirements to construct or modify a wastewater reclamation facility. Volume II: Recycled Water Projects covers the application process to use recycled water for various purposes and establishes best management practices that apply to the end user. See http://health.hawaii.gov/wastewater/home/reuse/.

In order to assess potential impacts on groundwater quality, the Groundwater Protection Program studied the quality of groundwater, wastewater and reuse water to evaluate the quality of these waters and assess the potential impact of the use of reclaimed wastewater on groundwater, surface water, and drinking water. The project analyzed these waters for a comprehensive and wide variety of emerging contaminants, including endocrine disrupting chemicals, pharmaceuticals, and trace elements.

For this project we selected four (4) WWTP/WWRF facilities to conduct raw wastewater (influent) sampling. These four (4) facilities were selected since previous monitoring of PPCPs by the GWPP were conducted at these sites. A total of 10 R-1 effluent, one (1) R-2 effluent and one (1) RO Quality effluent water sources statewide were also selected for sampling.

Areas where there is a high density of OSDS may also be of concern due to the method of treatment and disposal from these systems. The potential of contaminant leaching from OSDS is quite possible.

http://health.hawaii.gov/wastewater/home/reuse/


Determine Receptors of Reuse Water: Groundwater Of primary concern is the impact on groundwater resources. The reuse of treated wastewater and the areas with a high density of OSDS may result in the potential of leaching of PPCPs into the groundwater. For this project, samples were collected from several groundwater wells in Upcountry Maui (to coincide with another water quality project) in an area where there is a high density of OSDS and elevated levels of nitrate in the groundwater. A sample was also collected on O’ahu at a groundwater well being investigated for rising nitrate levels.

PESTICIDES IN GROUNDWATER MONITORING PROGRAM (DEVELOPMENT) (PHASE I/II Planning Only)

SAMPLING PROJECT: Pesticides in Groundwater Monitoring (Development)

PROJECT PERIOD: 6/1/2017 - 6/30/2018

PROJECT LOCATION: Statewide

SAMPLING LOCATION(S): Groundwater Wells in Areas where contamination by Phase I pesticides may occur. Based on discussions with DOA-Pesticides and HEER. As well as pesticide use records and use potential.

SAMPLING FREQUENCIES: Monitoring Program Development/Planning

ANALYTICAL PARAMETER(S): Drinking Water Contaminants that are also identified by the DOA as Pesticides of Groundwater Concern.

The State Drinking Water Program monitors drinking water contaminants at public water systems. The Pesticides in Groundwater Monitoring (Phase I) will monitor drinking water contaminants (identified as pesticides of groundwater concern) in areas where these pesticides may have been used throughout the State. The SDWB is working with the DOA and HEER Office to identify sampling locations. This monitoring project will sample and analyze groundwater wells (that are not regularly monitored) for drinking water contaminants/pesticides of groundwater concerns. See “Pesticides in Groundwater Monitoring Program Implementation” on page 40 for the table of active ingredients (pesticides) that have been determined (by DOA) to be pesticides of groundwater concerns.


GROUNDWATER DATA MANAGEMENT GROUNDWATER CONTAMINATION VIEWER1 (MAPS) The Groundwater Contamination Viewer has eliminated the tedious nature of developing yearly updated maps by using new GIS software, as the maps are now more easily updated and are made more readily available to the public. The Groundwater Contamination Viewer for the State of Hawaiì represent current information available to the DOH and are based on monitoring data for public drinking water wells, select non-drinking water wells (such as irrigation and industrial wells), and fresh water springs. Besides generating its own data, the DOH accepts data from other testing agencies such as the University of Hawaiì, DOA, Hawaiì Department of Land and Natural Resources and the U.S. Geological Survey.

These maps identify organic contaminants that have been detected by the DOH and other agencies and have been confirmed through repeat testing in drinking water wells, select non-potable wells, and fresh water springs throughout the state. Organic contaminants are generally a measure of human impact on the environment, since they rarely occur naturally. Contaminants include herbicides, pesticides, industrial solvents, fuels and other sources that are applied, spilled, leaked, or disposed of into the ground. Groundwater contamination is an especially significant concern in Hawaiì since nearly all of Hawaiì’s drinking water comes from groundwater sources.

The intent of the Groundwater Contamination Viewer is to identify only those wells with detectable levels of groundwater contamination. This is done by reporting the actual groundwater contamination, or the quality of the water directly out of the ground prior to any treatment to remove contaminants. Naturally occurring contaminants are not included in these reports. Not all contaminated wells are listed due to a lack of confirmed data and reporting, or because they have not yet been tested. Levels of groundwater contamination may fluctuate for a number of reasons, including actual diminishing or increasing levels of contamination, chemical breakdown of contaminants, variability in sampling and analytical methods, the effects of pumping rates, and other factors. Groundwater sources previously reported as contaminated, but later test negative for contaminants are no longer included in this report. Some data are extremely outdated due of the inaccessibility of the source, or lack of resources to perform resampling.

The Groundwater Contamination Viewer shows that groundwater contamination continues to occur in Hawaiì. Our knowledge base concerning chemicals continues to grow about the contamination potential of many chemicals, their behavior as they travel down the soil column, their degradation or lack of degradation, the mechanisms that serve to promote or restrict groundwater contamination, and much more. Today, many 1 Groundwater Contamination Viewer is available at: https://eha-cloud.doh.hawaii.gov/sdwb/#!/viewer

https://eha-cloud.doh.hawaii.gov/sdwb/#!/viewer


activities strive to prevent groundwater contamination through regulation and clean-up requirements. Unfortunately, contamination which was initiated years ago, and prior to these activities, may just now be showing up in our groundwater. Further, the use of new and innovative chemicals will continue to challenge our groundwater protection efforts. Therefore, the ability of these maps to be more regularly updated is important in order to ensure the health and safety of Hawaiì residents.

GROUNDWATER STATUS

HISTORICAL GROUNDWATER DETECTIONS (PRIOR TO 2011) Beginning in 1979, Groundwater has been monitored for various contaminants associated with its use in Hawaii. During these initial monitoring efforts, the following contaminants have been detected in Hawaii’s groundwater:

CONTAMINANT KAUAI OAHU MAUI HAWAII Alachlor 1 Ametryn 1 2 1 Atrazine and Degradation By-Products

3 15 7 32

Bromacil 1 Carbon Tetrachloride 4 Chlordane 5 1,2-Dibromo-3-Chloropropane (DBCP)

14 7

p-Dichlorobenzene 1


CONTAMINANT KAUAI OAHU MAUI HAWAII Dichloropropane 1 Dieldrin 25 1 Diuron 3 Ethylene Dibromide (EDB) 3 5 Heptachlor epoxide 1 Hexazinone 7 Lindane 1 Perchloroethylene (PCE) 1 Simazine 1 5 Trichloroethylene (TCE) 17 Trichloropropane (TCP) 4 63 11

SUMMARY OF RECENT HISTORICAL GROUNDWATER DETECTIONS MONITORING (2011-2018)

CONTAMINANT KAUAI OAHU MAUI HAWAII Alachlor Ametryn Atrazine and Degradation By-Products

4 1 10 10

Bromacil Carbon Tetrachloride 1 Chlordane 1 1,2-Dibromo-3-Chloropropane (DBCP)

7 6

p-Dichlorobenzene Dichloropropane Dieldrin 14 1 Diuron Ethylene Dibromide (EDB) 1 Heptachlor epoxide 1 Hexazinone Lindane Perchloroethylene (PCE) 1 Simazine Trichloroethylene (TCE) 5 Trichloropropane (TCP) 5 20 9

Number Represents How Many Wells were sampled and detected with contaminant.

RED Well Closed

YELLOW Contaminant Not Sampled

BLUE Sampled with No Detections

orWell not Sampled (non-DW source or well Inactive)



Of the samples collected during 2014, 9 had TCP concentrations greater than the MCL of 0.6 ug/L. The highest TCP concentration was 2.8 ug/L in a sample collected from the Mililani III Wells on May 1, 2013. A sample collected from the nearby Mililani II Wells had a concentration of 2.4 ug/L on March 3, 2008. Prior to 2014, TCP exceeded the MCL at 12 of the wells sampled. There were a sufficient number of samples to evaluate trends for 30 wells. The TCP concentration in eight wells was either decreasing or stable and decreasing. At 11 of the other wells the TCP concentration was stable, neither increasing nor decreasing with the 2014 concentration be only slightly less than the historical concentration. At 11 wells, the TCP concentration was either increasing or stable with 2014 sample concentration being slightly higher than historical concentrations. The area with most consistent increasing trend was Waipahu. 1,2-Dibromo-3-Chloropropane (DBCP)

Thirteen wells have a history of positive DBCP detections. All but one well had DBCP concentrations that exceeded the MCL of 0.04 ug/L. Ten wells were resampled in 2014. The DBCP concentration in 9 of the wells exceeded the MCL. The maximum DBCP concentration of 0.27 ug/L was measured at the Mililani I wells. This is only slightly less than the historical high concentration of 0.28 ug/L measured at this well field. There were a sufficient number of sampling events at 4 of the wells to evaluate the temporal trend. There was no confirmed increasing trend, but the trend at the Mililani I Wells was either stable or slightly increasing. There was a decreasing trend at 2 wells and the trend was stable at another well.


There are 5 drinking water wells with a history of positive detections for TCE. These wells are all located in the central Oahu corridor between the Koolau and the Waianae Mountain Ranges. Four of these wells were resampled during the 2014 sampling events. The MCL of 5 ug/L was exceeded in the sample collected from the Del Monte Kunia 3 Well. This sample had a TCE concentration of 6.6 ug/L slightly less than the historical high concentration of 7.1 ug/L in sample collected on February 20, 2008. The Schofield Battery of Wells had the highest TCE concentration at 40.6 ug/L in a sample collected on June 18, 2013. The TCE concentration in all other wells was less than the MCL. The Waialua Wells were the only location where a sufficient number of samples were collect to evaluation the temporal trend of TCE contamination. At these wells the TCE concentration stable at about 1 ug/L. Dieldrin

A total of 15 public drinking water wells or well fields have a history of Dieldrin detections. 11 of these wells were resampled in 2014. The MCL of 0.2 ug/L was not exceeded in any sample collected. The highest concentration in samples collected during the 2014 sampling event was 0.09 ug/L at the Halawa Wells. The highest historical Dieldrin concentration was 0.28 ug/L in a sample collected at the Wilder Well


in April 2001. Dieldrin was below the detection limit in two of samples collected during the 2014 sampling event. There are 5 locations where a sufficient number of samples were collected to evaluate the temporal trend. All had decreasing trends except for Halawa Wells where the Dieldrin concentration was either stable or slightly increasing.

Atrazine

Prior to 1993, atrazine was not routinely monitored in drinking water. The HSPA was the first to identify atrazine in groundwater and voluntarily established a monitoring program in Hawaii. At the time there was no MCL and the health advisory level was 25 ppb. In 1983, HSPA alerted the DOH about detectable levels of atrazine found in Kunia and Waipahu on Oahu. Subsequent groundwater sampling by HSPA in the early 1980s in areas of high agricultural use found about 40% of the sources had detectable levels of atrazine. In 1986, elevated levels were found in Pepeekeo Spring and Kihalani Spring on the Hamakua Coast of Hawaii Island which measured 4.1 and 2.3 ppb, respectively. The monitoring found that areas of high rainfall together with permeable soils were more susceptible to atrazine groundwater contamination. Throughout the 1980s and 1990s, HSPA has been an active participant in monitoring and evaluating atrazine trends in Hawaii’s groundwater. There are 23 public drinking water wells or well fields with a history of Atrazine contamination. The majority (13) are on the island of Hawaii. Five of these wells and 4 irrigation wells were sampled during the 2014 sampling event. The Atrazine concentration in all of the samples collected in 2014 was less than the detection limit. The MCL of 3 ug/L has been not exceeded in any sample collected. The highest Atrazine concentration in any sample collected was 1.3 ug/L in a sample collected at the Ō`ōkala Well in 1994.

In 2015-2017, the Groundwater Protection Program conducted an Atrazine/Degradation By-Products Monitoring Study. Data from the “Atrazine/Degradation By-Products in Groundwater Monitoring Project” generally shown a downward trend in the levels of atrazine and its degradation by-products detected in Data from the “Atrazine/Degradation By-Products in Groundwater Monitoring Project” conducted by the DOH from 2015-2017 has generally shown a downward trend in the levels of atrazine and its degradation by-products detected in groundwater throughout the state. Several wells with prior detections (at low concentrations below 0.10 ug/l) are now “not detected.” Atrazine and its degradation by-products were detected in several wells that were previously negative or not in existence in 2011 (these wells are located in areas where atrazine was previously or currently used). Many of the historical detections associated with agriculture and irrigation wells were not sampled for this project, as closure of sugar cane operations have made these wells inactive, abandoned, sealed, or not operational. Several wells associated with drinking water systems were not sampled, as the wells were not operational at the time of project sampling.



Other contaminants where there was only a single location or only a few locations where the concentration was equal to or greater than the reporting limit. The contaminants include: Alachlor, Carbon Tetrachloride, Heptachlor Epoxide, Tetrachloroethylene, and Ethylene Dibromide. The well, highest concentration detected, and current concentration are compared to the MCL. The only contaminant that exceeded the MCL was Ethylene Dibromide in the Maunaolu-Smith Well on Maui. The detection of Alachlor one well (Waimanalo Well) on Oahu has resulted in the well-being inactivated and is currently not being used as a source of drinking water. Other non-drinking water monitoring of groundwater have detected contaminants such as bromacil, hexazinone, trichloroethylene, diuron, and simazine.

PPCPs found in Raw Influent Wastewater In 2014, as part of the “Development of an enhanced groundwater vulnerability tool in Hawaii for pharmaceuticals” Project, samples were collected from four (4) Wastewater Reclamation Facilities or Treatment Plants (one on Kauai, two on Oahu and one on Maui). For each of the facilities/plants, a single (1) round of samples were collected. Analytes Found in raw wastewater influent samples were:

1,7‐Dimethylxanthine (4) Acetaminophen (3) Caffeine (4) Carbamazpine (2) Cotinine (4) d‐Amphetamine (3) Diphenhydramine (2) Gemfibrozil (4) Methamphetamine (4) Morphine (2) Sulfadiazine (3) Sulfamethoxazole (4) Thiabendazole (2) Ibuprofen (4) Naproxen (4) Triclosan (4) Warfarin (3) 4‐Androstenedione (1) α‐Estradiol (1) Androstanedienedione (1) Androsterone (1) α‐Trenbolone (1) β‐Trenbolone (1) Epitestosterone (1) Estriol (1) Estrone(1) Progesterone (1) Testolactone (1) Testosterone (3)

In 2017, as part of the “Assessing the Presence and Potential Impacts of Pharmaceuticals and Personal Care Products (PPCPs) on Groundwater and Drinking Water - Preliminary Findings: Project, samples were collected from four (4) Wastewater Reclamation Facilities or Treatment Plants (one on Kauai, two on Oahu and one on Maui). For each of the facilities/plants, two (2) rounds of samples were collected.


Analytes Found in all raw wastewater influent samples were: 1,7‐Dimethylxanthine Acetaminophen Caffeine Cotinine DEET Theophylline Acesulfame‐K Ibuprofen Naproxen Propylparaben Sucralose

Analytes Found in > 75% of raw wastewater influent samples or at least once (1) at each WWRF/WWTP:

Amoxicillin (semi‐quantitative) Andorostenedione Atenolol Cimetidine Diazepam Lidocaine Meprobamate Quinoline Sulfamethoxazole TCEP Testosterone Theobromine Trimethoprim Gemfibrozil Methylparaben Triclosan

PPCPs found in Raw Influent Wastewater and Treated Reuse Effluent Water Raw Influent Wastewater and Treated Reuse Effluent Water samples collected from the four (4) Wastewater Reclamation Facilities or Treatment Plants (one on Kauai, two on Oahu and one on Maui). For each of the facilities/plants, two (2) rounds of samples were collected.

SCHOFIELD (Analytes found in 100% of samples from WWRF/WWTP) 1,7-Dimethylxanthine Acetaminophen Amoxicillin Caffeine DEET 4-nonylphenol Sucralose

SCHOFIELD (Analytes found in 75% of samples from WWRF/WWTP)

Atenolol Cotinine Lidocaine Meprobamate Sulfadiazine Sulfamethoxazole TCEP Theophylline Tromeyhoprim Acesulfame‐K Gemfibrozil Propylparaben

WAHIAWA (Analytes found in 100% of samples from WWRF/WWTP)

1,7‐Dimethylxanthine Acetaminophen Amoxicillin Atenolol Caffeine Cotinine DEET Lidocaine Lopressor Theophylline Acesulfame‐K Sucralose


WAHIAWA (Analytes found in 75% of samples from WWRF/WWTP) Albuterol Andorostenedione DACT Diltiazem Diuron Meprobamate Sulfamethoxazole TCEP Theobromine 4‐nonylphenol Gemfibrozil Ibuprofen

WAIMEA (Analytes found in 100% of samples from WWRF/WWTP)

1,7‐Dimethylxanthine Atenolol Caffeine Cotinine DEET Diltiazem Sulfamethoxazole Theobromide Acesulfame‐K Gemfibrozil Naproxen Sucralose Triclocarban


Acetaminophen Amoxicillin Diuron Lidocaine Lopressor Meprobamate Quinoline TCEP TCPP Trimethoprim Ibuprofen Triclosan

PUKALANI (Analytes found in 100% of samples from WWRF/WWTP)

1,7‐Dimethylxanthine Acetaminophen Caffeine Cotinine Lidocaine Lopressor Meprobamate Theobromine Acesulfame‐K


Amoxicillin Carisoprodol Diuron Primidone Sulfamethoxazole TCEP Theophyllne 4‐nonylphenol Gemfibrozil Ibuprofen Iohexal Propylparaben Sucralose

PPCPs found in Treated Reuse Effluent Water In 2014, as part of the “Development of an enhanced groundwater vulnerability tool in Hawaii for pharmaceuticals” Project, treated reuse effluent samples were collected from four (4) Wastewater Reclamation Facilities or Treatment Plants (one on Kauai, two on Oahu and one on Maui). For each of the facilities/plants, a single (1) round of samples were collected. Analytes Found in treated reuse effluent samples were:

1,7‐Dimethylxanthine (4) Acetaminophen (1) Caffeine (3) Carbamazpine (3) Cotinine (2) d‐Amphetamine (0) Diphenhydramine (4) Gemfibrozil (4)


Methamphetamine (2) Morphine (0) Sulfadiazine (2) Sulfamethoxazole (4) Thiabendazole (1) Ibuprofen (1) Naproxen (4) Triclosan (1) Warfarin (2) 4‐Androstenedione (1) α‐Estradiol (1) Androstanedienedione (1) Androsterone (0) α‐Trenbolone (1) β‐Trenbolone (1) Epitestosterone (1) Estriol (1) Estrone (1) Progesterone (1) Testolactone (1) Testosterone (2)

In 2017, as part of the “Assessing the Presence and Potential Impacts of Pharmaceuticals and Personal Care Products (PPCPs) on Groundwater and Drinking Water - Preliminary Findings: Project, samples were collected from a total of 10 R-1 effluent, one (1) R-2 effluent and one (1) Reverse Osmosis (RO) Quality effluent water sources statewide were also selected for sampling. Two (2) rounds of sampling was conducted at each source. ANALYTES (found at all treated wastewater sources sampled)

Sucralose ANALYTES (found at all treated wastewater sources sampled, except Honouliuli RO)

1,7‐Dimethylxanthine Acetaminophen Caffeine Cotinine Lidocaine TCEP TCPP Theophylline Acesulfame‐K

ANALYTES (found at a significant number of treated wastewater sources sampled)

Amoxicillin Atenolol Carbanazepine Carisoprodol DACT DEET Dilantin Diltiazem Diuron Erythromycin Lopressor Meclofenamic Acid Meprobamate Primidone Quinodone Sulfamethoxazole TDCPP Theobromine Trimethoprim 4‐nonylphenol Gemfibrozil

OTHER ANALYTES OF INTEREST (found in multiple treated wastewater sources)

Albuterol Ketorolac 4‐tert‐octylphenol BPA Diclofenac Estrone Ibuprofen Iohexal Iopromide Naproxen Salicylic Acid Triclocarban Triclosan


Data Observations

(1) Some analytes were found in the raw wastewater influent but not in the treated effluent – possibility that analyses are treated/removed by the wastewater treatment process.

(2) Some analytes were found in the treated effluent but not in the raw wastewater influent – there is a possibility that those analytes were masked by the chromatographic peaks of other analytes (of high concentration) but detected in the treated effluent after treatment/removal of the higher concentration analytes.

(3) RO appears to be an effective method of removing PPCPs from wastewater as the first-round sample did not detect any analytes and the second-round sample only detected three (3) analytes. This is compared with the R-1 water from the same treatment facility that showed the detection of 58 analytes.

Data Issues Are there other factors that may have impacted the monitoring project and do these factors affect the presence and levels of PPCPs in raw wastewater influent and treated wastewater effluent? Possible concerns may be associated with wastewater flow/time of sampling (more flow may equate to more dilution or possibly increase analyte levels), treatment processes (how does the process affect the treatment/removal of the


analyte), or possibly population demographics (differing population factors such as age, race, health issues, others may affect the type and quantities of PPCPs that would be used in a particular geographical area). PPCPs found in Groundwater in Areas with high density of OSDS Samples were collected from several groundwater wells in Upcountry Maui (to coincide with another water quality project) in an area where there is a high density of OSDS and elevated levels of nitrate in the groundwater. A sample was also collected on Oahu at a groundwater well being investigated for rising nitrate levels. Several analytes were detected in the three samples:

Pukalani Amoxicillin, Chloridazon, Sulfamethoxazole, Sulfathiazole, 4-nonylphenol, and Acesulfame-K

Omaopio-Esty Amoxicillin, Bromacil, Chloridazon, Sulfathiazole, and 4-nonylphenol Kipapa Acres Cimetidine, DACT (Diamino-chloro-triazine), and Sucralose

Data Observations

(1) The presence of Acesulfame-K and Sucralose may be a good indication of contaminant leaching from OSDS to groundwater. Throughout the project, these two (2) analytes were detected at high concentrations in most of the samples collected.

(2) Amoxicillin, Chloridazon, Sulfathiazole, and 4-nonylphenol were detected in two (2) of the wells sampled.

Throughout the project, these analytes were also detected in most of the samples collected. Data Issue While these detections may be a possible indication of the leaching of contaminants in areas where there are high densities of OSDS or elevated nitrate levels, only one (1) sample from each well was collected. It would be wise to collect a follow-up sample to confirm the findings of the initial sample.

SUMMARY OF RECENT GROUNDWATER MONITORING STUDIES (2011-2018) The reports generated by the Groundwater Program’s monitoring efforts have been valuable in various environmental issues that currently impact the State of Hawaii. They include:

(1) Interconnection of Groundwater and Surface Water (Lahaina Tracer Study) that is currently being used in the lawsuit on whether the discharge from the LWRF should be regulated by the Clean Water Act (County of Maui, Hawaii v. Hawaii Wildlife Fund, et. al; Supreme Court Docket No. 18-260; Issue: Whether the Clean Water Act requires a permit when pollutants originate from a point source


but are conveyed to navigable waters by a nonpoint source, such as groundwater.).

(2) Impacts of cesspools/OSDS/Wastewater on Water Resources (Hawaiian Paradise Park Shallow Groundwater Quality Monitoring, PPCPs Monitoring-Preliminary Findings) has been used in support of efforts to ban the construction of new cesspools and require the elimination or upgrading of all cesspools by the year 2050 (Act 125, SLH 2017).

CURRENT GROUNDWATER MONITORING There are currently no routine groundwater monitoring projects being conducted.

Current drinking water monitoring is now done at entry points to the distribution system (EPD) and may not indicate the actual contaminant levels located in the groundwater source(s).

FUTURE MONITORING OF CONTAMINANTS OF CONCERN

WHY GROUNDWATER QUALITY MONITORING IS NECESSARY Groundwater quality monitoring is essential for assessing contaminants and suitability for use. It is also an important tool when generating data for water management. The objectives of a groundwater quality monitoring program must be clearly defined at the outset, to provide adequate data and information for the intended application. Groundwater monitoring is important to:

(1) Develop an understanding of the regional and long-term groundwater quality and characteristics which will allow for optimal management of groundwater resources;

(2) Identify potential human impacts and emerging problems; (3) Identify and monitor major pollutant sources, including their locations and the

movement of pollutant in the groundwater; (4) Determine compliance with standards and regulations; (5) Identify trends over time; (6) Help direct pollution control efforts to where they are most needed; (7) Assess the effectiveness of pollution control measures; (8) Determine the quality of groundwater, particularly with respect to its possible

use as a drinking water source; and (9) Understand the recharge areas, recharge mechanisms and recharge rates,

as well as the aquifer’s hydraulic properties.


The Hawaiì Groundwater Protection Strategy has identified and prioritized groundwater contamination threats since the 1990s. These threats identified below will be further studied and evaluated as part of the State’s Groundwater Quality Monitoring Program.

Priority Threats to Groundwater Quality – 2017 On-site sewage disposal systems/cesspools/injection wells Large scale use of recycled water Large fuel storage facilities Increasing nitrate concentrations Agricultural chemicals

PESTICIDES IN GROUNDWATER MONITORING PROGRAM IMPLEMENTATION The Groundwater Protection Program is continuing its partnership with the DOA – Pesticides Branch to manage potential impacts of selected pesticides on groundwater resources. The DOA is responsible for the review and licensing eligibility of new pesticides products in the State of Hawaiì. Through its Pesticides in Water Program Workplan, DOA’s primary objectives are to initiate regulatory actions such as use restrictions; cancellation or registration denial (if it is determined that unreasonable risks are or will result from a pesticide’s use; and develop a program to identify pesticides which could potentially leach to groundwater. All new outdoor use products containing a new chemical: Requires the submission of environmental fate data and undergoes an initial review process which considers Federal Register status; chemical properties, method of application and expected use. Groundwater Review for New Chemicals is a three-tiered approach with (1) Internal Review – review chemical properties, determination of total acreage and the method of application; (2) Leaching Model – analysis of chemical properties and Hawaiian soils data to determine if the pesticide is “likely” or “unlikely” to leach to groundwater; and (3) Full groundwater review (if score is 45 or more) – Submit for full review and seek comments on classification. (options are: 1) do not license, 2) Annual Use Permit, or 3) licensed as restricted.) If score is 45 or less – license without groundwater review. What about pesticide products that are already licensed? Products that have already been licensed must undergo a mechanism for the evaluation of the licensed product. The process includes environmental monitoring, collaboration with other agencies and re-evaluation of the registered use.


The Groundwater Protection Program has developed a partnership with the DOA – Pesticides Branch to implement a Pesticides in Groundwater Monitoring Program. The table includes the active ingredients (pesticides) that has been determined (by DOA) to be pesticides of groundwater concerns. The active ingredients were further identified whether they were monitored by drinking water and if there are appropriate methods for analysis.

PESTICIDES IN GROUNDWATER MONITORING PROGRAM

ACTIVE INGREDIENT

REGULATORY STATUS

GROUNDWATER ADVISORY

RESTRICTED USE PESTICIDE

(RUP) DRINKING

WATER MCL/HA

EPA

METHOD MONITORING

PHASE 2,4-D Yes No Yes 515.3 1 Acetochlor Yes No 535 3 Alachlor Yes Yes Yes 508.1

507 1

Aldicarb Under cancellation

Yes Yes Yes 531.1 1

Atrazine Yes Yes Yes 508.1 507

1

Bentazon Yes No 515.3 2 Bromacil Yes Yes(S) 507 2 Carbofuran Cancelled Yes Yes Yes 531.1 1 Chlorothalonil Yes No 508.1 2 Clopralid Yes No 3 Dacthal (DCPA) Undergoing

cancellation Yes No 515.3 2

DBCP Cancelled N/A Yes 504.1 1 Dimethenamid Yes No 3 Hexazinone Yes Yes(S) 507 2 Imidacloprid Yes No 3 Metalaxyl Yes No 3 Metsulfuron methyl No No 3 Metolachlor Yes Yes Unreg 508.1

507 1

Metribuzin Yes No Unreg 508.1 507

1

Norflurazon Yes No 507 2 Picloram Yes Yes Yes 515.3 1 Simazine Yes Yes(S) Yes 508.1

507 1

Tebuthiuron Yes No 507 2 Terbacil Yes No 507 2 Thiamethoxam Yes No 3 Triclopyr Yes No 3 Fludioxonil Yes No 3 Fluopicolide No No 3 Imazaquin Yes No 3 Chlorantraniliprole Yes Yes 3 Quinclorac Not licensed in

HI Yes Yes 3

Cyantraniliprole Pending full GW review

Yes N/A 3

Penflufen Yes No 3


PHASE I: PESTICIDES ON EXISTING DRINKING WATER MONITORING LIST

2,4-D Metolachlor Alachlor Metribuzin Atrazine/Metabolites Picloram DBCP Simazine

PHASE 2: PESTICIDES ON EXISTING DRINKING WATER ANALYTICAL

METHODS

Bentazon Hexazinone Bromacil Norflurazon Chlorothalonil Tebuthiuron Dacthal Terbacil

PHASE 3: PESTICIDES REQUIRING APPROVED ANALYTICAL METHODS

Acetochlor Metsulfuron methyl Chlorantraniliprole Clopralid Triclopyr Quinclorac Dimethenamid Fludioxonil Cyantraniliprole Imidacloprid Fluopicolide Penflufen Metalaxyl Imazaquin

The Groundwater Protection Program has worked with the EHASB, SLD on developing capabilities for the Pesticides in Groundwater Monitoring Program. Phase I identifies pesticides currently monitored in drinking water and Phase II identifies pesticides that can be analyzed using existing methods used in Phase I. The implementation of Phase I & II Monitoring of the Pesticides in Groundwater Monitoring Program is expected to begin in Fall 2019. PPCP MONITORING OF WATER RESOURCES AND USE The State of Hawaiì is interested/involved in the use of reclaimed wastewater as an alternative water source. While the quality of reclaimed wastewater may meet the Hawaiì State Water Quality Standards (WQS), HAR, Chapter 11-54, and be free of drinking water contaminants, as listed in HAR, Chapter 11-20, there remains a concern regarding other contaminants. While there are guidelines on the use and quality of reclaimed wastewater (R-1/R-2), very little is known about other potential Contaminant of Emerging Concern (CEC), such as PPCPs in wastewater and reclaimed wastewater.


PPCPs have recently emerged as CECs due to their potential impact on water quality and aquatic life. Will proposed uses of reclaimed wastewater for irrigation, dust suppression and other uses on land overlying impact underlaying aquifers and groundwater resources? While the potential impact of the use of reclaimed wastewater on water resources is a primary concern, PPCPs may originate and enter the environment through other mechanisms that may impact the State’s water resources. As most PPCPs are eliminated via human excretion and the disposal of unused PPCPs has been through the wastewater disposal system, sampling at WWRF/WWTP would provide the best indication of what PPCPs may be in the environment. As the State continues to grow and the demand for water increases, the generation of treated wastewater for reuse and application (for irrigation and other uses) provides another alternative water source. The application of reuse water on land above potable groundwater resources is a concern due the possible leaching of PPCPs and other CEC. FURTHER ACTIONS

ADDITIONAL MONITORING NEEDS AND RESOURCES (1) Conduct follow-up sampling to confirm the results of the PPCPs detections in

raw/treated wastewater and as a constant over time. (2) Conduct sampling to detect PPCPs in groundwater sources that may be impacted

by reuse water or discharges from WWTP or OSDS. At the present time, the GWPP is working with the SLD to develop analytical capabilities to monitor for indicator/marker compounds (including caffeine and selected artificial sweeteners).

(3) Utilize the data to develop and implement a PPCPs in Water Monitoring Program focusing on PPCPs and indicators that were detected in the raw influent and the R-1 effluent). GWPP will be working with the SLD to identify PPCPs and begin the development of capabilities to conduct analyses of the selected PPCPs.

The data gathered through these monitoring efforts will allow us to better manage the use of reuse water and protect our groundwater resources. Data may be used in the following:

CRITERIA FOR AREAS WHERE REUSE WASTEWATER SHOULD NOT BE USED

(1) Conduct leaching model studies of identified/selected PPCPs to determine leachability of detected PPCPs to groundwater.


(2) Assessment of monitoring results to determine the impacts of using R-1, R-2, or R-3 Reuse water over our drinking water/groundwater resources.

POTENTIAL NEED FOR PROGRAM CHANGES

(1) Reuse Guidelines for Emerging Contaminants: Are levels and types of PPCP analytes a public health concern? Do we need guidelines or standards for these contaminants? Do we need additional treatment/controls of PPCPs and the reuse wastewater effluent (Best management practices/Mitigation Measures/ Contaminant reduction/Pollution technology/Others) to improve the reuse wastewater quality?

(2) Reuse wastewater effluent/groundwater monitoring: Do we need to monitor our reuse water and pollution sources to protect our groundwater resources?

(3) Public Education/Outreach: The reuse of treated wastewater is an area in which the public may not be aware of and therefore may be a concern. Not being educated/informed of the value and need associated with reused water (Where will it be used? How will it be used? Is it safe to use? How do we ensure public health/safety?) will lead to uncertainty and concern. How do we present this issue to the public?

HISTORICAL DETECTIONS AND DRINKING WATER MONITORING The goal and objectives for continued monitoring of historical detections is to provide updated monitoring data on status of historical contaminants detected in groundwater.

There are over 60 wells that have a history of past contamination. The results of this monitoring will be used to increase surveillance in areas where an increasing trend in contaminant concentrations were identified. The data can also be used by water systems when planning locations for new water sources and planning well head treatment systems.

Areas that show an increasing trend in the contaminant concentrations may need further evaluation to determine potential migration paths. Follow-up monitoring may be implemented to track the groundwater contamination trends in those areas where the concentrations are either stable or increasing.

Atrazine and its Degradation By-Products will be of significant interest since the pesticide is still in use (although significantly reduced) and contamination is still being detected in groundwater. Due to its presence in drinking water the following other contaminants that will continued to be monitored includes DBCP, EDB, TCP, TCE, Chlordane, and Dieldrin.

APPENDIX A - DOH GROUNDWATER PROTECTION STRATEGY

APPENDIX B - GROUNDWATER CONTAMINATION MAPS (2011) Kauai

Oahu

Maui

Hawaii

APPENDIX C - LAHAINA TRACER STUDY, UNDATED (6 PAGES)

Full Report:

Lahaina Groundwater Tracer Study; Lahaina, Maui, Hawaiì: Final Report, dated June 2013 (503 pages)

https://archive.epa.gov/region9/water/archive/web/pdf/lahaina-gw-tracer-study-final-report-june-2013.pdf

2nd Joint Government Water Conference presentation at Kahului, Maui on August 13, 2014

The Lahaina Groundwater Tracer Study: Project Overview and Update (32 pages)

https://health.hawaii.gov/sdwb/files/2014/09/SessionB-02.Lahaina-Groundwater-Tracer-Study_8-13-14.pdf





1

LAHAINA TRACER STUDY

Project Goals

Determine whether or not the Lahaina Wastewater Treatment Facility injected effluent

discharges near the Kaanapali shoreline and validate the portion of the tracer breakthrough curve

that was extrapolated in Craig et al. (2013).

Summary of Goal Completion

The additional 22 months of tracer test sampling and analysis that has occurred since the

cessation of field work for the Lahaina Groundwater Tracer Study in December 2012 shows that

the actual dye concentration approximately tracks the concentrations that were estimated. There

is some divergent where the expected concentrations are slightly less than that measured.


Data will be archived on the HDOH-SDWB server. Data will also be made available to HDOH

Clean Water Branch and the University of Hawaii research partners.


The long duration of tracking tracer test breakthrough curves generated by the Lahaina

Groundwater Tracer Study can be used in research projects to better understand the transport

solutes in Hawaii groundwater.

Project Description

This project was initiated as joint effort between HDOH, U.S. EPA, U.S. Army Corp of

Engineers, and the University of Hawaii – Department of Geology and Geophysics. The goal of

the study was to use a groundwater tracer test to investigate whether or not treated wastewater

injected at the Lahaina Wastewater Reclamation Facility near the shoreline fronting the

Kaanapali resort area of Maui, Hawaii. Figure 1 shows the location of the Lahaina Wastewater

Reclamation Facility, the injection wells, the major seep groups, and the model tracer dye plume.

On July 28, 2011, about 340 lbs of Fluorescein dye were added to the injectate stream of Wells 3

and 4 at the LWRF. The dye was detected 84 days later at a submarine spring group referred to

as the North Seep Group (NSG). About three weeks later the dye was detected at a group of

submarine springs about 150 yards south of the NSG. The southern set of submarine springs is

referred to as the South Seep Group (SSG). Field work for the Lahaina Groundwater Tracer

Study officially ended on December 31, 2012. At the end of the field work, the BTC was

sufficiently developed to extrapolate the future dye concentrations to point where the dye could

no longer be detected by laboratory instruments. However, it is desirable to confirm the

extrapolated portion of the BTC with actual measurements of the dye concentration. HDOH

Clean Water Branch started monthly nutrient seep sampling in January, 2012 and will continue

2

this sampling through December, 2014. Clean Water Branch has been providing SDWB with

dye samples as part of their monthly sampling. These samples have been analyzed for

Fluorescein and the results are compared to extrapolated portion of the BTC.

Tracer Dye Breakthrough Curves

The dye concentrations at the submarine springs have not been documented for more than 3

years. This study is the most successful tracer test done in Hawaii and has the added benefit of

having the longest BTC record. Figure 2 shows the BTC for the NSG, while Figure 3 shows the

BTC for the SSG. In each figure the elapsed time from dye addition to critical points in BTC are

shown by blue-vertical dashed lines. The critical points include; the time to first detection, time

to the peak dye concentration, the average travel time, and time for the dye concentration to

decay to less instrument detection limits. The “mean transit time” stated in Craig et al. (2013) is

replace by “average time of travel”. Field (2002) defined “mean transit time” as the centroid of

mass of the BTC. Reviewers of the report found this term difficult to understand and has been

replaced by “average time of travel”. Average time of travel is defined as the time it takes 50

percent of the cumulative dye mass to discharge from the submarine spring. The average time of

travel for the NSG is a little less than a year, and a little more than a year for the SSG. It is

expected that the dye concentration will remain greater than the instrument detection limit

through 2017 for the NSG and through 2016 for the SSG.

As described above, the purpose of this phase of the Lahaina Groundwater Tracer Study was to

validate the extrapolated portion of the BTC. In the BTC calculations described in Craig et al.

(2013) the portion of the curve past December 2012 was extrapolated using data from the peak

concentration through the December 2012. As Figures 2 and 3 show, the BTC extends well

beyond the official end of field work for this project. Visual inspection of the BTC graphs show

that the dye concentration in those samples collected after December fall very close to the

extrapolated line. To further investigate any deviation, the percent difference between the dye

concentrations predicted and that measured is plotted on the right-hand Y axis of Figures 2 and

3. The graphs show an increasing difference between the predicted and actual concentrations,

with the actual concentrations being greater than that predicted. This is not unexpected given

that the BTC was projected years into the future based on a few months of data. However, the

small absolute difference the predicted and measured concentrations show that percent recovery

calculations of Craig et al. (2013) are still valid. While the percent difference line for the NSG is

noisy from about January 2013 through about October 2013, the corresponding line for the SSG

show near steady increasing percent difference. The differences between the sampling methods

at the two seep groups could account for the difference. The NSG is in a sandy area right at the

shoreline. During the first year of the study, permanently sampling piezometers were

consistently lost due to the shifting sands. Rather than permanently install a sampling

piezometer at the NSG a temporary piezometer is driven into the sand for each sampling event

then retrieved at the end of sampling. This will cause the sampling location to vary slightly from

3

one sampling event to another. The sampling piezometers for the SSG are permanently installed

and only re-located if one becomes clogged or otherwise unusable.

The comparison between the predicted versus measured dye concentrations are useful for

evaluating whether or not there has been any changes in the groundwater flow field that

discharges to the seep groups. Figures 4 and 5 show the concentrations of total nitrogen and total

phosphorus measured by the CWB at the seep groups. The total nitrogen concentration started

increasing from a 0.15 mg/L baseline in March 2013. The total nitrogen concentration peaked at

about 5 to 6 mg/L in February 2014, and has now settled to a new baseline of about 3 mg/L. The

close absolute agreement between the predict and measured dye concentrations and the lack of

significant deviation from the increasing percent difference line for the SSG indicate that

groundwater flow field for SSG remains as it has been for duration of the BTC. The possible

conclusion is that the increase in total nitrogen is due some change at the LWRF or a change is

chemical processes that occur between injection and the discharge of the treated wastewater at

the SSG. With the exception of concentration spike in December 2013, the total phosphorus

concentration shows little variability further indicating no change in the groundwater flow field.

Drawing similar conclusions from the NSG data are more difficult due to the variability in the

percent difference line.

Possible future uses of this data include using numerical models to investigate the processes that

result in the long trailing edge of the BTC. It is important to understand this and the implications

for contaminant transport in groundwater through Hawaii basalts.

References

Glenn, C.R., Whittier, R.B., Dailer, M.L., Dulaiova, H., El-Kadi, A.I., Fackrell, J., Kelly, J.L.,

Waters, C.A., and J. Sevadjian, 2013. Lahaina Groundwater Tracer Study – Lahaina,

Maui, Hawaii, Final Report, prepared for the State of Hawaii Department of Health, the

U.S. Environmental Protection Agency, and the U.S. Army Engineer Research and

Development Center

Field, M.S., 2002, The QTRACER2 Program for tracer-breakthrough curve analysis for tracer

tests in karst and other hydrologic systems, EPA/600/R-02/001, U.S. Environmental

Protection Agency.

4

Figure 1. A map of the Kaanapali area showing the modeled tracer dye plume and the location

of the major seep groups and injection wells.

5

Figure 2. The BTC for the NSG showing the actual dye concentration, the extrapolated curve,

and the percent difference between the actual and measured dye concentrations.

Figure 3. The BTC for the SSG showing the actual dye concentration, the extrapolated curve,

and the percent difference between the actual and measured dye concentrations.

6

Figure 4. The average total nitrogen concentration in the discharge from the NSG and SSG.

Error bars show the maximum and minimum concentrations measured at each sampling event.

Figure 5. The average total phosphorous concentration in the discharge from the NSG and SSG.

Error bars show the maximum and minimum concentrations measured at each sampling event.

APPENDIX D - SHALLOW GROUNDWATER QUALITY MONITORING, UNDATED (6 PAGES)

1

SHALLOW GROUNDWATER QUALITY MONITORING

Project Description

Measure the water quality of shallow groundwater wells (less than 150 deep) in the Hawaiian Paradise Park (HPP) Subdivision on the Island of Hawaii. The HPP Subdivision is completely reliant on on-site sewage disposal systems (OSDS) for the disposal of wastewater. This project analyzed for microbial and basic water/wastewater contaminants.

Project Goals

Determine the quality of the shallow groundwater and the impact of OSDS on the water quality. Assess methods of screening water for OSDS contamination.


A total of 18 wells were sampled. Wastewater contamination screening methods assessed included:

• Basic water quality parameters (temperature, pH, specific electrical conductivity [SEC], dissolved oxygen content, and oxidation/reduction potential [ORP]);

• Presences of Total Coliform and Escherichia coli bacteria; • Presences of optical brightener compounds; • Colorimeter analysis for nitrate, phosphate, and sulfate; and • Spectrophotometry.


This report, tables and maps will be archived on the SDWB server. The data from this study will be shared with HDOH Clean Water and Wastewater Branches. The results of the study will be also presented to the Hawaiian Paradise Park Homeowners Association. The participating homeowners in HPP will also be given a project report with data specific to their well.


The project results can be used by the HDOH branches in assessing wastewater processes, in the development of OSDS requirements, in evaluating water samples for wastewater impact.

Project Description

There are estimated to be in excess of 110,000 on-site sewage disposal (OSDS) systems in the State of Hawaii that discharge approximately 70 million gallon per day (mgd) of wastewater effluent. Whittier and El-Kadi) (2009 and 2014) estimated the number, location, and effluent discharge from OSDS. These studies identified where any adverse impacts from OSDS would theoretically occur. However, field studies are needed to investigate whether or not adverse

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impacts are actually occurring. These impact could include contamination of drinking water with pathogens and increased nutrient loading to surface and coastal waters. Figure 1 shows the density in units per square mile of OSDS in east Hawaii Island. The EPA considers OSDS densities greater than 40 units per square mile as posing a high risk of groundwater contamination. The OSDS density in Hawaiian Paradise Park exceeds 100 units per square mile.

Hawaiian Paradise Park is an optimum location for a field investigation of the health and environmental risk posed by OSDS. In this community there are approximately 4,300 OSDS. HPP lacks both sewer and municipal water service. Wastewater disposal is done through OSDS, primarily cesspools. Having no municipal water service, the domestic water needs of HPP are met by rainwater collection, transporting water in (either bottled or collected in jugs), or by domestic wells. There are a proximately 250 domestic wells in HPP. This provides excellent coverage of the area to evaluate the quality of groundwater beneath HPP. The domestic wells packages commonly include an ultra-violet (UV) disinfection system to kill any pathogens that might be captured by the well. However, it is common for the UV system to be turned off.

Sample Collection

Samples were collected at the wellhead whenever possible. Water was diverted into a purge bucket and a minimum of 20 gallons of water was purged from the well prior to collecting a sample. When the well purge was complete water quality measurements were taken. Samples were then collected in a 250 ml HPDE white bottles. Each sample container was rinsed with the sample water and emptied just prior to the sample collection. The bottle was then filled to the shoulder and placed in a cooler for transport to Hilo HDOH office where the colorimetric analysis was performed.

Field Parameter Measurements

The field parameters were measured with a YSI ProPlus Water Quality Analyzer (WQA). Measurements of temperature, pH, specific electrical conductivity, and dissolved oxygen were taken after the well purge and just before the sample collection. To take the field measurements the discharge tubing from well was connected to the flow-through cell of the WQA. The well discharge rate was decreased so that there was no pressure build-up in the flow-through cell that would bias the dissolved oxygen readings high. The water was allowed to discharge through flow cell for at least two-minutes to allow pH and dissolved oxygen to stabilize.

Colorimeter Measurements

Nitrate, phosphate, and sulfate analysis were done with a Hach DR-890 colorimeter. The nitrate concentration was measured by cadmium reduction using the Hach Method 8192. The reactive phosphorus (orthophosphate) was measured using the Hach Ascorbic Acid Method 8048. The sulfate concentration was measured using the Hach barium reaction Method 8051. Phosphate is

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the form of phosphorus that is stable in oxic waters. The sulfate concentration was measure by reaction of the sulfate ion with barium using Hach Method 8051.

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Fluorometric Measurements

Wastewater contains many fluorescent compounds such as optical brighteners and organic acids. Optical brighteners are used in laundry detergent to enhance the colors of items being washed. A Turner Designs AquaFluor Handheld Fluorimeter was used to analyze samples for the presence of optical brighteners. Using the AquaFluor optical brightener optical package, samples were screened for fluorescence emitted at a wavelength of 440 nanometers (nm) when excited by a light beam with a wavelength of 380 nm.

Other compounds include fluvic and humic acids associated with organic matter are also fluorescent. Performing a three dimensional scan (excitation wavelength, emission wavelength, and emission intensity) produces a detailed fluorescence signature of a water sample. Three dimensional fluorescence scans of the HPP samples were done using Aligent Carey Eclipse G98001 Spectrophotometer. The results were compared to scans of diluted wastewater, and nearly pristine groundwater.

RESULTS

Water Quality Parameters

The groundwater beneath HPP is generally cool and well oxygenated. Table 1 summarizes the water quality measurements taken from the wells sampled at HPP. The specific electrical conductivity (SEC) (Figure 2) is low in wells furthest from the coast, but the SEC increases as the distance to the coast decreases. Mixing with seawater increases the SEC from 110 µs/cm at the upgradient well near the inland extent of HPP to 3,400 µs/cm in the well closest to the shoreline. An SEC of 3,400 µs/cm is equivalent to a salinity of 2 parts per thousand or about 6 percent seawater. However, there wells located near the shoreline indicated by the yellow symbols that have a low SEC compared to adjacent wells indicating fresher than expected water.

The well oxygenated nature of the aquifer (dissolved oxygen concentrations near the saturate concentration of about 9 mg/L) indicates that nitrogen and phosphorus would be present in their oxidized forms of nitrate and phosphate respectively. No spatial trend in temperature or pH was found.

Nitrate and Phosphate

Nitrate and phosphorus can be indicators of wastewater influence. Nitrogen is enriched in wastewater. When the groundwater is oxic, nitrogen will occur as nitrate. However, nitrate is not unique to wastewater. Other common sources include fertilizer leaching and decay of organic matter. Concentrations of nitrate that are elevated above background with no other agricultural source could indicate a wastewater source.

Like nitrate, phosphorus is enriched in wastewater but is not unique to this source. When evaluating the linkage between the phosphate content of the groundwater, the potential for

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agricultural leachate must be taken into account. The sorption of phosphate to the aquifer matrix is greater than that of nitrate, thus a natural reduction in the phosphate should occur along the groundwater flow path.

Sulfate is enriched in wastewater, but is also enriched in seawater compared to freshwater. Thus when evaluating sulfate as a wastewater indicator in a coastal environment, the contribution from seawater must be taken into account. This can be done by correlating the sulfate concentration with SEC.

A wastewater influence on groundwater would be indicated by an increasing concentration in one of more of these parameters along the groundwater flow path. Since nearly all groundwater that is not captured by wells flows into the ocean, the groundwater flow path is expected to be from the interior of the island to the ocean. Along the seaward flow path the concentration of the wastewater indicators should increase since OSDS will continually be adding contaminants to the groundwater.

The large amount of groundwater that flows beneath HPP will significantly dilute the concentrations of nitrogen and phosphorus that are leached from the OSDS. Figure 3 is a map of east Hawaii Island showing the modeled groundwater nitrogen concentration resulting OSDS leachate. Even with high density of OSDS the simulated groundwater nitrogen does not exceed 1 mg/L. By contrast the simulated groundwater nitrogen concentration from OSDS near the smaller community of Leilani Estates is significantly higher due to a lower amount of groundwater flow in the vicinity of Leilani Estates. Figures 4 and 5 show the concentrations nitrate and phosphate respectively measured in wells at HPP. The highest nitrate concentration was measured in a shoreline spring at the southeast corner of HPP. The next highest nitrate concentration was in a sample collected well upgradient from the shoreline (shown by the red symbol near the highway). This well serves a plant nursery and the higher nitrate concentration may be fertilizer leaching. However, the concentration is still lower than that of most Hawaii groundwater. The actual concentration of nitrate is lower than that modeled and does not show the expected increasing trend along the flow groundwater flow path to the ocean. A contributing factor to the lower than expected nitrate concentration could be that the actual OSDS effluent is lower than that assumed Whittier and El-Kadi (2014). The OSDS study assumed an OSDS discharge rate of 200 gallons per day per bedroom. The houses in HPP are generally large with many bedrooms. However, in many cases retired persons occupy these houses leaving some the bedrooms unused. Also Whittier and El-Kadi assumed that there is no natural remediation of the effluent once is leaves the zone of treatment. Undoubtedly some natural processes will modify the effluent nutrient concentration as it migrates down to the water table and is transported seaward by the flow of groundwater. Finally, groundwater flow is complex and unexpected contributions of groundwater not impacted by OSDS could occur.

Phosphate like nitrate showed no pattern of increasing concentration along the assumed groundwater flow paths. The highest phosphate concentration was measured in the most

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upgradient well. Other high phosphate concentrations occurred in a cluster of wells near the mid-point of the northwest boundary of HPP. A group of wells near the coast had relatively low concentrations of phosphate.

Bacteria Sampling Results

There was a high rate of bacteria detections in the samples collected from HPP. Figure 6 shows that location of the wells sampled, whether or not bacteria was detected, and the estimated water table elevation. Table 2 summarizes the bacteria sampling results by sampling campaigns. Sampling was done at HPP in 2010 and 2011. The current sampling all occurred in 2014. Table 2 also shows the incidents of bacteria detections when the data from both sampling campaigns are merged.

During 2014, 46 samples were analyzed for the presence of Total Coliform (TC) bacteria. If the sample tested positive for TC, the sample was then tested for the presence of Escherichia coli (EC) bacteria. Twenty-one samples tested positive for TC and 3 samples tested positive for EC. Wells that tested positive for the presence of bacteria were usually sampled multiple times. The number of wells sampled was 18, of which 7 tested positive for TC and 3 tested positive for EC. The presence of TC could indicate groundwater contamination by OSDS effluent, but TC is not unique to wastewater as other organic rich water can contain this bacteria. However, TC is generally not present of groundwater not contaminated by surface water or wastewater. The presence of EC is a more specific indicator of OSDS effluent, but the survival of the EC bacteria appears to be shorter than that of some other species of coliform bacteria.

HDOH conducted bacteria sampling during the years 2010 and 2011. During this campaign a total of 23 samples were collected from 19 different wells. Twelve of the samples tested positive for TC and 7 tested positive for EC. When the results from both sampling events are combined, at total of 69 samples from 31 different wells were tested for coliform bacteria. Fifty-two percent of the wells tested positive for TC in at least one of samples collected and 23 percent of the wells tested positive for EC. Coliform bacteria can survive about 3 days outside of human body (Crockett, 2007). The presence of these bacteria in a well sample strongly suggest a short travel time from OSDS discharge to the well intake. It was observed during this sampling the rate of bacteria detection increased after heavy rain storms such as tropical storm Iselle. More troubling is that pathogens such as salmonella can have survival times much greater that of Coliform bacteria.

As described above groundwater anomalies were observed such as zones of fresher than expected water near the coast, and no apparent increase in nitrate and phosphate concentration along the assumed groundwater flow path. To better define the groundwater flow direction the water table elevations measured during the well installations was contoured as shown in Figure 6. This is a generalized method to define the water table elevation since the water level in each well was only measured at the time it was drilled. Thus the water table elevations used for this

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analysis consists one-time measurements that occurred over a period of years. In spite of this constraint, significant variations in the water table are evident. Of particular interest is an area with an elevated water elevation about 1 mile southwest of the coastline embayment. The wells in this area tested negative for the presences of bacteria. This area also has a lower than expected SEC. The combined observations indicate that fresher water may be upwelling in that area and mitigating the impact of the OSDS effluent.

Fluorescence Study

The results of the fluorescence study are inconclusive. The average value of the optical brightener analysis for the samples collected from HPP was 0.3 ppb, less than the optical brightener fluorescence of the background sample. There were no independent indicators of wastewater influence such as a correlation between fluorescence and detections of Coliform bacteria. The concentrations of both nitrate and phosphate in the high fluorescence samples were near the average for HPP. The nitrate concentration was 0.2 mg/L phosphate concentration of 0.5 mg/L compared to the average values of 0.4 and 0.2 mg/L for nitrate and phosphate respectively.

HDOH is still working to develop a protocol for evaluating the full fluorescence scans of the water samples.

CONCLUSIONS

The high rate of bacteria detections show that the large concentrations of OSDS are having a detrimental impact on the drinking water quality of the groundwater. This impact can pose a health risk to the consumers of domestic well water if the ultraviolet treatment systems are not used. Again it must be stressed that the survival time for the indicator bacteria monitored for by this study is much shorter than that for other pathogens. Thus the risk of infection from ingesting untreated groundwater is greater than the rate of positive bacteria detections would indicate. This study was not able to correlate any of the chemical species analyzed for to any the incidents of bacteria detections. This may be partially due dilution by upwelling of groundwater not impacted by OSDS. The lack of the expected trend increasing concentrations of the wastewater indicators (optical brighteners, nitrate, and phosphate) along the groundwater flow path could have multiple causes such as natural attenuation of the indicators through sorption, transformation, or degradation; or the mixing of OSDS contaminated groundwater with groundwater free of OSDS constituents. But the low nutrient concentrations do indicate that groundwater discharging along the coastline at HPP should present no greater environmental risk than other groundwater in eastern Hawaii Island.

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FUTURE WORK

The results of this study need to be presented to the residents of HPP. It should be stressed to those residents that get their domestic water from on-site wells that they need an operating filtration and disinfection system. Potential follow-on investigations could include:

• Analyzing samples for pharmaceutical and personal care products, • Continuing to investigate the utility of fluorescent scans to screen for wastewater

influence; and • Doing dual analysis to compare the analytical results measured by a field colorimeter

with the analysis performed by a certified laboratory. This exercise will test the utility of the field colorimeter as an analytical tool.

References

Crockett, C. S. 2007. The Role of Wastewater Treatment in Protecting Water Supplies Against Emerging Pathogens. Water Environmental Research, 79(3), 221-232.

Whittier, R. B., and A. I. El-Kadi. 2009. Human and Environmental Risk Ranking of Onsite Sewage Disposal Systems—Final. Prepared for the Hawaii Dept. of Health by University of Hawaii at Manoa, Dept. of Geology and Geophysics.

Whittier, R. B., and A. I. El-Kadi. 2014. Human and Environmental Risk Ranking of Onsite Sewage Disposal Systems for the Hawaiian Islands of Kauai, Molokai, Maui, and Hawaii. Prepared for the Hawaii Dept. of Health by University of Hawaii at Manoa, Dept. of Geology and Geophysics.

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Table 1. A summary of the water quality parameter measurements at HPP

Temp DO Spec.

Cond. pH Opt.

Brightener NO3 PO4 SO4

(oC) (mg/L) (µs/cm) (unitless) (ppb) (mg/L) (mg/L) (mg/L) Minimum 20.0 6.0 107.5 6.9 0.0 0.1 0.1 < 1 Average 21.9 7.9 595.0 7.3 0.3 0.2 0.4 22.7 Maximum 24.1 10.5 3390.0 7.9 1.1 0.4 1.1 132.0 Standard Deviation

0.9 .9

616.0 0.2 0.3 0.1 0.1 29.0

Background 19.2 9.3 114 7.9 0.41 0.04 0.5 < 1 oC – degrees Centigrade mg/L – milligrams per liter ppb – parts per billion µs/cm – micro Siemens per centimeter NA – Not Analyzed

Table 2. A summary of the bacteria detections in the well samples collected at HPP

2014 2010-11 All No. of Samples 46 23 69 N. of Positive for TC 21 12 33 No. of Positive for EC 3 4 7 No. of Wells Sampled 18 19 31 No. of Wells Positive for TC 7 12 16 No. of Wells Positive for EC 3 4 7 Percent Wells Positive for TC 39% 63% 52% Percent Wells Positive for TC 17% 21% 23%

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Figure 1. A map of the OSDS density in east Hawaii Island. The EPA considers OSDS densities greater than 40 units per square mile as having a high risk of groundwater contamination.

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Figure 2. A map of the specific conductivity (SEC) measured in the wells at HPP. Increasing specific conductivity indicates increased mixing with seawater.

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Figure 3. A map of the modeled groundwater nitrogen concentration resulting OSDS leachate

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Figure 4. A map of the nitrate concentration in Hawaiian Paradise Park

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Figure 5. A map of the phosphate concentrations in Hawaiian Paradise Park

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Figure 6. A map of the bacteria sampling results overlaid on the estimated water table elevations.

APPENDIX E - PPCP LEACHABILITY MODEL MONITORING REPORT

Draft Final Report

Development of an enhanced groundwater vulnerability tool in Hawaii for pharmaceuticals, dated December 2014 (55 pages)

Additional Appendix VIII

Metadata for the major attribute tables in the new CLERS tool for pharmaceuticals

Appendix VIII. Metadata for the major attribute tables in the new CLERS tool for pharmaceuticals.

Table VIII-1. Attribute tables for classification and recharge in the major islands of Hawaii implemented in the new CLERS tool.

Classification Parameters Types Description Units

1 FID Object ID A feature ID - 2 Shape Geometry A geometry for a feature - 3 AREASYMBOL String A five character string (postal code and soil survey area) - 4 SPATIALVER Double A serial version of the spatial data for soil survey area - 5 MUSYM String An abbreviation for the map unit - 6 MUKEY String A map unit key - 7 BD Double Bulk density (BD) kg/m3 8 S2BD Double Variance of BD kg/m3 9 SBD Double Standard deviation of BD kg/m3

10 OC Double Organic carbon content (OC) - 11 S2OC Double Variance of OC - 12 SOC Double Standard deviation of OC - 13 FC Double Water content at field capacity (FC) - 14 S2FC Double Variance of FC - 15 SFC Double Standard deviation of FC - 16 RECHARGERA Double Groundwater recharge m/d 17 PD Double Particle density (PD) kg/m3 18 S2PD Double Variance of PD kg/m3 19 SPD Double Standard deviation of PD kg/m3 20 MAP String MUSYM is presented when AFR has value - 21 CVAFRLEACH Double Total uncertainty of AFR for leacher - 22 CVAFRNONL Double Total uncertainty of AFR for non-leacher - 23 CVDEPTH Double Uncertainty of compliance depth - 24 CVWATFLUX Double Uncertainty of groundwater recharge - 25 CVTHALF Double Uncertainty of half-life - 26 CVFIELDCAP Double Uncertainty of FC - 27 RF Double Retardation factor (RF) - 28 AFRVALUE Double Revised attenuation factor (AFR) - 29 CVRF Double Uncertainty of RF - 30 CVAFR Double Total uncertainty of AFR - 31 AFRCLASS String Classification scheme - 32 Area_km2 Double Area of a polygon km2

Recharge 1 FID Object ID A feature ID - 2 Shape Geometry A geometry for a feature - 3 ID Short A polygon ID - 4 RECHARGERA Double Groundwater recharge m/d

Development of an enhanced groundwater vulnerability tool in Hawaii for pharmaceuticals

Chittaranjan Ray Matteo D'Alessio

Seo Jin Ki

PREPARED FOR

Safe Drinking Water Branch Environmental Health Administration

Hawaii Department of Health 919 Ala Moana Blvd., Room 308

Honolulu, HI 96814-4920

Contract No. ASO LOG 14-164 Project Period: April 1, 2014 ‒ December, 2014

Principal Investigator: Chittaranjan Ray

Research Scientists: Matteo D'Alessio and Seo Jin Ki

Department of Civil and Environmental Engineering University of Hawaii at Manoa

2540 Dole Street, 383 Holmes Hall Honolulu, HI 96822

December 2014

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Executive Summary

Groundwater resources in Hawaii are subject to contamination due to the intrinsic aquifer vulnerability by leaching from land surface. The Hawaii Department of Health (HDOH), which is responsible for protecting statewide drinking water sources, has been establishing appropriate water quality management plans to meet state water quality standards. One of various efforts that have been made by the HDOH is the redevelopment of a Comprehensive Leaching Risk Assessment System (CLERS) that quickly assesses the leaching potential of conventional and emerging contaminants. The CLERS tool is used in Tier One screening? for chemical leaching evaluation procedure that a particular chemical (being applied) shows low, moderate, and high groundwater vulnerability at different areas in Hawaii. The tool incorporates a few input parameters (i.e., soil, chemical, and recharge properties) that are readily available in its screening algorithm, which is continuously updated by the HDOH from pesticides (in the first stage) through volatile organic compounds (in the second stage) to now pharmaceuticals (in the third stage).

There is growing concern for leaching of pharmaceutical compounds as conventional wastewater treatment plants do not remove these chemicals from the effluent and sludge “significantly” and “cost-effectively”. So, a reliable assessment tool that can delineate groundwater vulnerability to pharmaceuticals needs to be developed to provide adequate information to the public as well as to state health authorities in a timely manner. However, as information for determining contaminant behavior in soils rarely exists in the literature, experimental research on sorption, degradation and leaching is conducted to construct an appropriate chemical database for these pharmaceuticals. Interestingly, the leaching tool implementing this new database shows good agreement with a numerical model of HYDRUS-1D that describes the complex movement of chemicals under local conditions, except for few soils in Big Island. Therefore, the new leaching tool can be applied to address statewide groundwater vulnerability to pharmaceuticals, in addition to volatile and non-volatile pesticides. The tool now comes with the latest Python code so that it is operated and managed properly in the recent ArcGIS program (version 10.0 or higher). The aggregate leaching for pharmaceuticals can be also evaluated with the leaching map (assessed by the new CLERS tool) and extra layers (i.e., SWAP and PCA layers) provided and updated regularly by the HDOH.

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Project Background

Pharmaceuticals have recently received considerable attention due to their occurrence in the Nation's streams, groundwaters, and drinking water supplies (Kolpin et al. 2002, Anderson et al. 2004, Kinney et al. 2006, Domenech et al. 2011, Fram and Belitz 2011). Many pharmaceuticals are known to be not effectively removed by conventional wastewater treatment. So, a variety of pharmaceuticals including their metabolites are easily distributed into the environment through various pathways such as discharge (or reuse) of treated wastewater, excretion by humans and animals through septic tanks and cesspools, and runoff from land-applied manure (Anderson et al. 2004, Domenech et al. 2011). Although detected at low concentrations, pharmaceutical compounds are found to be relatively persistent in the environment, and adversely affect the health of humans and aquatic organisms (Domenech et al. 2011). What is worse, the mass emission to the environment is difficult to quantify due to a multitude of sources from both point and diffuse sources. Therefore, more research is needed to better understand environmental fate and transport of pharmaceuticals as well as to quantify their risks to humans and aquatic ecosystems. The US EPA currently put pharmaceuticals into the Contaminant Candidate List 3 to be considered for regulated regulation under the Safe Drinking Water Act (SDWA).

There are continuous efforts by the Hawaii Department of Health (HDOH) to strengthen the Comprehensive Leaching Risk Assessment System (CLERS) model, in particular groundwater vulnerability analysis for volatile chemicals in the second stage. The CLEARS model assesses the leaching potential of land-applied chemicals based on soil, chemical, recharge properties (Stenemo et al. 2007, Dusek et al. 2011). The model is used by the Hawaii Department of Agriculture (HDOA) for registration and approval of new pesticides in the state (Stenemo et al. 2007, Dusek et al. 2011). The earlier pesticide leaching tool (see Stenemo et al., 2007) is being modified to account for the loss by volatilization, allowing new volatile chemicals to be assessed. To account for the reduced leaching by volatilization loss, the previous tool is expanded to include additional terms, liquid-vapor partitioning for the retardation factor (RF) and vapor loss at the soil surface for the attenuation factor (AF), respectively. The new leaching model is also implementing various geospatial layers for regional vulnerability maps so that all contamination activities and their associated risks can be determined simultaneously. These additional layers, obtained from the Source Water Assessment Program (SWAP) of HDOH, include the capture zones around public supply wells and potential contaminating activities (PCAs) score within the capture zones, as outlined in Whittier et al. (2010).

As concern grows on the possible impacts of pharmaceuticals, a reliable and valid assessment for groundwater vulnerability needs to be provided for federal and state agencies as well as local public. This will be consistent with the goals of the Safe Drinking Water Act including those of CLEARS model to regulate chemicals that have potential occurrence in groundwater. It also continues to help the Underground Injection Control (UIC) program (by the HDOH) as well as registration and approval processes of new pharmaceuticals for agricultural procedures in the future (by the HDOA). In this project, a Commented [RBW1]: Do you mean agricultural procedures or

something similar? HDOA does not regulate pharmaceuticals.

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new CLERS tool is, therefore, developed that can delineate the groundwater vulnerability to pharmaceuticals, in addition to pesticides. This is because the screening algorithm for pharmaceuticals and pesticides is slightly different from that of volatile compounds which requires additional parameters for chemical leaching assessment. The new CLERS tool developed in the third phase shares soil and recharge properties updated in the second stage, but comes with the latest Python code which is freely available in the recent ArcGIS program (version 10.0 or higher).

Project Objectives

The project was undertaken with the following objectives:

1) Collect important chemical characteristics of pharmaceuticals from appropriate databases including software programs,

2) Develop an emission inventory for wastewater treatment facilities to quantify their impact on surrounding areas,

3) Conduct laboratory experiments to evaluate the sorption, degradation and leaching behavior of pharmaceuticals in the selected soils in Hawaii,

4) Compare the accuracy between CLERS and a numerical model to determine the suitability of the existing CLERS model for vulnerability analysis of pharmaceuticals, and

5) Implement the leachability of pharmaceutical compounds tool in GIS to maps and to prioritize areas vulnerable areas with SWAP and PCA layers which are generated by HDOH to groundwater contamination.

Individual Project Tasks

Task 1: Updating physico-chemical properties for pharmaceuticals

A total of 16 pharmaceutical compounds (see Table 1) were selected for evaluation based on their detection frequency in the national and international waters (Luo et al., 2014; Meffe and de Bustamante, 2014; Fatta-Kassinos et al., 2011; Benotti et al., 2009; Focazio et al., 2008; Verliefde et al., 2007; Kolpin et al., 2002; Ternes, 1998) as well as statewide groundwater and wastewater monitoring program. Since information on the fate of pharmaceuticals in the environment was rare, an Estimation Program Interface Suited (EPIWEB 4.1) developed by the US Environmental Protection Agency (http://www.epa.gov/opptintr/exposure/pubs/episuite.htm) appropriate database was consulted for determining physico-chemical parameters with their toxicological profiles. Literature was also reviewed to provide a more reliable estimate of the chemical properties. A “data gap” was also partially filled with supported by laboratory batch

Commented [RBW2]: Could you specify the database and how it was used?

Commented [RBW3]: Do you mean “resolved” or “filled”?

http://www.epa.gov/opptintr/exposure/pubs/episuite.htm

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sorption and degradation experiments as proposed in this project. Physico-chemical properties of each chemical are also provided in Appendix A.1.

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Table 1. A list of 16 pharmaceutical compounds investigated during batch sorption and degradation experiments and their chemical formula and structure.

Pharmaceuticals Class Chemical Formulaa

Chemical structureb

1,7 Dimethylxanthine Illicit C7H8N4O2

Acetaminophen Illicit C8H9NO2

Caffeine Illicit C8H10N4O2

Cotinine Illicit C10H12N2O

Diphenhydramine Illicit C7H8N4O2

Methamphetamine Illicit C10H15N

Trimethoprim Illicit C14H13N4O3

http://en.wikipedia.org/wiki/Carbon

http://en.wikipedia.org/wiki/Hydrogen

http://en.wikipedia.org/wiki/Nitrogen

http://en.wikipedia.org/wiki/Oxygen






















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Table 1 (continued)


Chemical structureb

17-b Estradiol Steroid C18H24O2

b-Trenbolone Steroid C18H22O2

Estriol Steroid C18H24O3

Estrone Steroid C18H22O2

Testosterone Steroid C19H28O2

Gemfibrozil PPCPs C15H22O3

Ibuprofen PPCPs C13H18O2






















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Table 1 (continued)


Chemical structureb

Naproxen PPCPs C14H14O3

Triclosan PPCPs C12H7Cl3O2

a Chemical formula has been obtained using EPIWEB 4.1. b Chemical structure was obtained from Sigma-Aldrich at www.sigmaaldrich.com/catalog/search. Task 2: Determining flow and loading from wastewater treatment facilities

Estimation of mass loading and flow from wastewater treatment plants plays an important role in assessing regional groundwater vulnerability, as the majority of pharmaceuticals stems from these facilities (Standley et al. 2008). Excretion by patients, seepage from landfills and septic systems, and runoff from animal wastes and land-applied manure are also important for determining their transport (Anderson et al. 2004, Domenech et al. 2011). However, these primary routes to the environment are not considered here for rapid and simple screening analysis. Conventional treatment plants typically show low removal efficiency for many pharmaceuticals. However, the actual removal performance is highly specific to the types of treatment as well as the compounds. Four wastewater treatment plants (Wahiawa and Schofield on Oahu, Pukalani on Maui, and Waimea on Kauai) were selected during this study (see Table 2).

Raw water (influent to the treatment plant) and recycled water (tertiary treated effluent used for agricultural purposes) were collected for determining the occurrence of pharmaceuticals in the effluent samples, as well as the removal achieved within each treatment plant. Grab and composite samples were collected at the four wastewater treatment facilities. Within one day, the wastewater samples were filtered through Oasis HLB solid phase extraction cartridges (200 mg, 6cc, Waters) and the samples were sent to the Water Sciences Laboratory at the University of Nebraska for analysis of the compounds. A detailed description of the analytical methods used to investigate the occurrence of pharmaceutical compounds in the wastewater samples is given in Appendix A.2. Three methods were developed to identify three classes of pharmaceutical compounds (illicit pharmaceuticals, pharmaceutical and personal care products, and steroids) (Appendix A.2). The term “illicit” was used for illicit (i.e., methamphetamine), life-style (i.e., caffeine,







http://www.sigmaaldrich.com/catalog/search

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cotinine), and analgesic (i.e., 1,7 Dimethylxanthine) compounds. The results of the preliminary investigation (see Table 3, Appendix III) were used to select the 16 pharmaceuticals used during the study and their starting concentrations. Detailed information regarding the occurrence of pharmaceuticals and the removals obtained at the different wastewater treatments plants are given in Appendix A.3.

Table 2. Locations of the four selected wastewater facilities.

Locations (islands) Sample types GPS (latitude; longitude)

Schofield Wastewater Reclamation Facility (Oahu)

Raw (21.476521; -158.043204) R1 (recycled) (21.475894; -158.044270)

Wahiawa Wastewater Treatment Facility (Oahu)

Raw (21.492006; -158.038862) R1 (recycled) (21.491096; - 158.038862)

Pukalani Wastewater Treatment Facility (Maui)

Raw (20.829949; -156.354044) R1 (recycled) (20.830042; -156.354244)

Waimea Wastewater Reclamation Facility (Kauai)

Raw (21.493275; -158.034562) R1 (recycled) (21.492913; -158.034593)

Task 3: Experimental research on sorption, degradation and leaching

Little is known about the persistence and fate of pharmaceutical compounds in soils (Williams and McLain 2012), specifically those in Hawaii. Research has been generally conducted on surface waters, to a lesser extent in ground waters. Many studies continue to determine the occurrence and distribution of pharmaceuticals against other types of organic micro-pollutants such as pesticides, volatile organic compounds and hormones. Laboratory batch and column studies can help not only investigate the behavior of pharmaceuticals in soils, but also provide site specific parameters required to run the simulation models. As experimental data obtained from temperate soils are also different from those of tropical soils, sorption, degradation and leaching studies of pharmaceuticals was conducted using selected Hawaiian soils where wastewater recharge was most likely to occur. Eight sampling locations, representing eight different soil types, were identified across four Hawaiian Islands (Table 4). Soil samples were collected at three depths: 0-30cm, 30-60cm, and 60-90cm. Additional information are given in Appendix 4.

The experimental approach employed was very similar to earlier work of Shuai et al. (2012) that characterizes adsorption and degradation of fipronil in Hawaiian soils under funding from the Hawaii Department of Agriculture. The processes controlling the pharmaceutical concentration in the subsurface was initially evaluated from laboratory experiments and then from model simulations. Detailed information regarding the sample preparation and the experimental design are provided in Appendix 4, while Appendix 5

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provides information regarding the analytical methods used to identify the selected pharmaceutical compounds.

The University of Hawaii did not have adequate facilities and technical expertise for the analysis of the pharmaceutical compounds and their degradation products at concentrations that are environmentally relevant (parts per trillion levels). As a result, the primarily analytical work and the degradation and sorption experiments were subcontracted to the Water Sciences Laboratory at the University of Nebraska. The same laboratory analyzed wastewater samples for the presence of residual pharmaceuticals.

Table 3. Occurrence of pharmaceutical compounds at the selected wastewater treatment plants.

Illicit pharmaceuticals Pharmaceutical and Personal care products (PPCPs)

Steroids

Raw water 1,7-Dimethylxanthine (4) Gemfibrozil (4) 4-Androstenedione (3) Acetaminophen (3) Ibuprofen (4) a-Estradiol (2) Caffeine (4) Naproxen (4) Androstanedienedione (2) Carbamazepine (3) Triclosan (4) Androsterone (1) Cotinine (4) Warfarin (3) a-Trenbolone (2) d-Amphetamine (3) b-Trenbolone (2) Diphenhydramine (3) Epitestosterone (2) Methamphetamine (4) Estriol (3) Morphine (2) Estrone (2) Sulfadiazine (3) Progesterone (2) Sulfamethoxazole (4) Testolactone (2) Thiabendazole (2) Testosterone (3) Recycled water 1,7-Dimethylxanthine (4) Gemfibrozil (4) Testosterone (2) Acetaminophen (1) Ibuprofen (1) Caffeine (3) Naproxen (4) Carbamazepine (3) Triclosan (1) Cotinine (2) Warfarin (2) Diphenhydramine (3) Methamphetamine (2) Sulfadiazine (2) Sulfamethoxazole (4)

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Thiabendazole (1) ( ): number of wastewater treatment plants.

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Table 4. Soil type and locations of the different soil samples used during the study.

Soil types Locations (islands) GPS (latitude; longitude)

Oxisol Poamoho (Oahu) (21.544165; -158.087780) Mollisol Waimanalo (Oahu) (21.333913;-157.711669) Vertisol Alou Farms (Oahu) (21.357986; -158.042327) Ultisol East Maui Watershed (Maui) (20.841393; -156.294875) Andisols Kula (Maui) (20.756267; -156.318585) Entisol Waimea (Kauai) (22.010874; -159.768656) Histosol Waiakea (Big Island) (19.642476; -155.081108) Inceptisol Mealani (Big Island) (20.035398; -155.608280)

Task 4: Inter-model comparison between CLERS and HDRUS-1D

As described in the previous sections, soil and wastewater samples were collected across the major islands of Hawaii to characterize the fate and transport of various pharmaceuticals in different soils. Figure 1 shows sampling locations for soil and wastewater samples in the four islands of Hawaii which are used for inter-model comparison between CLERS and HDRUS-1D models. The meteorological data in Hawaii distributed for Exposure Assessment Modeling from the US EPA are used as input to the numerical model of HYDRUS-1D (see Weather Bureau Army Navy (WBAN) number in the figure). Before running the CLRES tool, the soil database is also recompiled from 0.5 m to 0.9 m, which is illustrated in Figure 2. As can be seen in the figure, the soil properties at 0.9 m depth in particular areas are lowershow lower values than those of 0.5 m depth (see black arrows), although most areas still show the same characteristics. Specifically, this is more apparent in the parameter of organic carbon content than the water content. More detailed information on parameters, schematic diagram, and associated screening indices implemented in the CLERS tool is also documented in Ki and Ray (2014 and 2015) as well as the previous report of the new CLERS tool for volatile organic compounds (VOCs) (Ray and Ki, 2014).

Among 16 pharmaceutical compounds, we selected estrone, cotinine, and methamphetamine as test chemicals for the inter-model comparison between two models (see Table VI-1 in Appendix VI). This is because the three chemicals are mainly classified as leacher (i.e., unlikely), non-leacher (i.e., likely), and intermediate leaching (i.e., uncertain or likely) in all the islands of Hawaii in the CLERS tool (see Figure 3). The properties of 8 different soils used for inter-model comparison are given in Table VI-2 in Appendix VI. Soil hydraulic parameters for running the HYDRUS-1D model are estimated from Rosetta Lite

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program using this basic soil information with particle size fractions. The HYDRUS-1D model was initially run under transient condition using the last two years of weather data for different islands, and was then switched to steady-state condition using constant water flux at the surface for another one year. Different recharge rates for individual soils were used as constant fluxes and (1 mmol of) each pharmaceutical was spilled or applied on the soil surface for the first day. The dispersivity and diffusion coefficient were set to 15 cm and 1 cm2/day for the simulation. The soil profile consisted of one single layer that was assumed to be homogeneous at 1 m soil depth. In particular, the 1 m soil profile (that was slightly larger than 0.9 m applied for the new CLERS tool) was selected to avoid the bottom boundary effect. We believe that there is no significant difference in the leaching behavior of test pharmaceuticals between these two depths (i.e., 0.9 m and 1 m) in HYDRUS-1D as high attenuation occurs in the upper 0.5 m of the soil or less top soil.

Figure 4 shows the results of a comparison between the new CLERS tool (Figure 4a) and HYDRUS-1D (Figure 4b) when assessing the leaching potential of three pharmaceuticals in 8 different soils. As shown in Figure 4a, leaching behavior of test pharmaceuticals are clearly classified by the new CLERS tool. The high and low revised attenuation factor (AFR) values indicate chemicals as leacher and non-leacher, respectively (Stenemo et al. 2007, Ki and Ray 2014 and 2015). The chemical that shows intermediate leaching is classified as uncertain or likely depending on soil and recharge properties in different areas. Note that the value of AFR should be reserved reversed due to the double logarithmic screening algorithm; high AFR indicates non-leacher and vice versa. On the other hand, concentration of a chemical should be high in the HYDRUS-1D if it is less attenuated and remains in the soil profile. As can be seen in Figure 4b, the HYDRUS-1D also correctly classifies chemicals that show high leaching, non-low leaching, and intermediate leaching, except for soils in Hawaii (i.e., BI2 and BI1). We cannot clearly explain the different leaching behaviors of these chemicals in Hawaiian soils. However, this is probably attributed to inaccurate estimation of soil hydraulic properties resulting from low bulk density in these two soils (see Table VI-2 in Appendix VI). From these results, the new CLERS tool shows sufficient accuracy in ranking the relative leachability of a compound compared to a known leaching chemical and a non-leaching chemical under the given conditions in Hawaii. Thus, it can be still used to address groundwater vulnerability to contamination of pharmaceuticals, in addition to pesticides and VOCs.

Commented [RBW4]: Maybe something like “occurs in the upper 0.XX m of the soil”?

Commented [RBW5]: Could a report or paper that describes the criteria for leacher vs. non-leacher be added as an appendix or at least a reference cited?

Commented [RBW6]: This is very unclear.

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Figure 1. Soil and wastewater sampling locations along with weather monitoring locations across the major islands of Hawaii.

Figure 2. Updated soil database at a depth from 0.5 m (a and c) to 0.9 m (b and d) in Maui Island. FC and OC indicate the water content at field capacity (– or m3/m3) and the fractional organic carbon content (–or m3/m3), respectively.

Formatted: Superscript

Formatted: Superscript

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Figure 3. Leaching potential of three pharmaceutical compounds (i.e., estrone, cotinine, and methamphetamine) on Maui Island assessed from the new CLERS tool.

Figure 4. A comparison of (a) the new CLERS tool (0.9 m depth) and (b) HYDRUS-1D (1 m depth) when assessing the leaching potential of three pharmaceutical compounds in 8 different soils (see Table VI-2 for soil abbreviations).

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Task 5: Aggregate Leachability Potential of Pharmaceuticals with SWAP and PCA layers

The overall leaching potential of pharmaceuticals can be further investigated with SWAP and PCA layers to associate the leaching potential of pharmaceuticals with their contamination activities. This enables users to highlight hotspot areas for groundwater protection as well as to determine proper regulatory actions around these areas. These layers have been prepared from a parallel project in the HDOH that are were developed for protecting public water supplies of the state (Whittier et al., 2010). They include information of public supply wells, their capture zones (i.e., contaminants can travel over different years), and various contaminating activities around drinking water sources. Figures 5 and 6 illustrate how the user can evaluate aggregate leaching for different chemicals with these two types of layers. When the leaching potential of methamphetamine is evaluated as an example, most areas on Molokai and Hawaii Islands are classified as “uncertain” (see yellow color). However, there are still some areas in both islands that exhibit high groundwater vulnerability to methamphetamine (see red color). SWAP and PCA layers are separately added to the leaching map of methamphetamine for Molokai (Figure 5) and Hawaii Islands (Figure 6), respectively, which allows the users to justify the overall risk rating at particular areas. Monitoring waiver that reduces regular sample frequency is requested if both the groundwater vulnerability to a particular chemical and contamination activities are low. Otherwise, monitoring will likely continue until more data may be needed to support this request. Note that the HDOH has also developed other geospatial layers (i.e., areas with wastewater reuse and onsite sewage disposal systems) across the major islands of Hawaii. Detailed information about geoprocessing operations on these data sets (i.e., map overlay) is described in Appendix VII.

Summary and Conclusions

In this project, the new CLERS tool was developed to delineate groundwater vulnerability to contamination with pharmaceuticals on the major islands of Hawaii. Soil and wastewater samples were collected for the four islands of Hawaii (i.e., Kauai, Oahu, Maui, and Hawaii Islands) and were used for experimental research on sorption, degradation and leaching. From these experiments, an appropriate chemical database was constructed to properly estimate the leaching potential of pharmaceuticals using the new CLERS tool (see Built-in chemical database.txt or Built-in chemical database.py). Input parameters for the HYDRUS-1D model were also obtained from the laboratory experiments. The results of inter-model comparison between the CLERS and HDRUS-1D showed that the CLERS tool correctly

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assessed the relative leachability of pharmaceuticals in various soils in Hawaii. Surprisingly,

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Figure 5. The overall leaching potential of a particular pharmaceutical (i.e., methamphetamine) on Molokai Island with SWAP layers, capture zones for different travel-times (i.e., b, c, and d).

Figure 6. The overall leaching potential of a particular pharmaceutical (i.e., methamphetamine) on Molokai Island with PCA layers, hospital and cesspool..

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there was disagreement in the leaching prediction between the CLERS and HDRUS-1D for the sampled soils in Big Island, which was probably attributed to inaccurate estimation of the unsaturated soil hydraulic properties. So, we recommend further work on characterizing the soil hydraulic characteristics for these soils in more detail. The aggregate leaching for pharmaceuticals in particular areas was evaluated with the leaching map (assessed by the CLERS tool) and extra layers (i.e., SWAP and PCA layers) provided and updated regularly by the HDOH. This will help determine if the DOH will be pursuing sampling of a particular pharmaceutical at any specific areas. Finally, the source code of the new CLERS tool for pharmaceuticals is now converted successfully from Visual Basic to Python which is freely provided with the recent ArcGIS 10.0 or higher.

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References

Anderson, P.D., D'Aco, V.J., Shanahan, P., Chapra, S.C., Buzby, M.E., Cunningham, V.L., Duplessie, B.M., Hayes, E.P., Mastrocco, F.J., Parke, N.J., Rader, J.C., Samuelian, J.H. and Schwab, B.W. (2004) Screening analysis of human pharmaceutical compounds in US surface waters. Environmental Science & Technology 38(3), 838-849.

Benotti MJ, Trenholm RA, Vanderford BJ, Holady JC, Stanford BD, Snyder SA, Pharmaceuticals and endocrine disrupting compounds in US drinking water. Environ. Sci. Technol. 2009; 43 (3): 597–603.

Domenech, X., Ribera, M. and Peral, J. (2011) Assessment of Pharmaceuticals Fate in a Model Environment. Water Air and Soil Pollution 218(1-4), 413-422.

Dusek, J., Dohnal, M., Vogel, T., Ray, C. (2011) Field leaching of pesticides at five test sites in Hawaii: modeling flow and transport. Pest Management Science 67(12), 1571–1582.

Fatta-Kassinos D, Meric S, Nikolaou A, Pharmaceutical residues in environmental waters and wastewater: Current state of knowledge and future research, Analytical and Bioanalytical Chemistry 2011; 399 (1): 251–275.

Focazio MJ, Kolpin DW, Barnes KK, Furlong ET, Meyer MT, Zaugg SD, Barber LB, Thurman ME, A national reconnaissance for pharmaceuticals and other organic wastewater contaminants in the United States – II) Untreated drinking water sources. Sci. Total Environ. 2008; 402 (2-3): 201–216.

Fram, M.S. and Belitz, K. (2011) Occurrence and concentrations of pharmaceutical compounds in groundwater used for public drinking-water supply in California. Science of the Total Environment 409(18), 3409-3417.

http://www.epa.gov/opptintr/exposure/pubs/episuite.htm Accessed on January 3, 2015

Ki, S.J. and Ray, C. (2014) Application of a regional screening index for chemical leaching to groundwater vulnerability analysis in the national level. In: Jones, R.L., Shamim, M., Jackson, S.H. (Eds.), Describing the Behavior and Effects of Pesticides in Urban and Agricultural Settings. American Chemical Society, Washington, DC, pp 275-286.

Ki, S.J. and Ray, C. (2015) A regional screening tool to evaluate the leaching potential of volatile and non-volatile pesticides. Journal of Hydrology. DOI: 10.1016/j.jhydrol.2014.12.024.

Kinney, C.A., Furlong, E.T., Werner, S.L. and Cahill, J.D. (2006) Presence and distribution of wastewater-derived pharmaceuticals in soil irrigated with reclaimed water. Environmental Toxicology and Chemistry 25(2), 317-326.

Kolpin, D.W., Furlong, E.T., Meyer, M.T., Thurman, E.M., Zaugg, S.D., Barber, L.B. and Buxton, H.T. (2002) Pharmaceuticals, hormones, and other organic wastewater

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contaminants in US streams, 1999-2000: A national reconnaissance. Environmental Science & Technology 36(6), 1202-1211.

Luo Y, Guo W, Ngo HH, Nghiem LD, Hai FI, Zhang J, Liang S, Wang XC, A review on the occurrence of micropollutants in the aquatic environment and their fate and removal during wastewater treatment. Sci. Total Environ. 2014; 473–474: 619–641.

Meffe R, de Bustamante R, Emerging organic contaminants in surface water and groundwater: A first overview of the situation in Italy. Sci. Total Environ. 2014; 481 (1): 280–295.

Ray, C. and Ki, S.J. (2014) Modeling to support monitoring waiver for selected wells in Hawaii. Hawaii Department of Health, Safe Drinking Water Branch, Honolulu, HI, 27 pp.

Shuai, X.F., Chen, J.Y. and Ray, C. (2012) Adsorption, transport and degradation of fipronil termiticide in three Hawaii soils. Pest Management Science 68(5), 731-739.

Šimůnek, J., van Genuchten, M.T. (2008) Modeling nonequilibrium flow and transport processes using HYDRUS. Vadose Zone Journal 7(2), 782–797.

Standley, L.J., Rudel, R.A., Swartz, C.H., Attfield, K.R., Christian, J., Erickson, M. and Brody, J.G. (2008) Wastewater-Contaminated Groundwater as a Source of Endogenous Hormones and Pharmaceuticals to Surface Water Ecosystems. Environmental Toxicology and Chemistry 27(12), 2457-2468.

Stenemo, F., Ray, C., Yost, R., Matsuda, S. (2007) A screening tool for vulnerability assessment of pesticide leaching to groundwater for the islands of Hawaii, USA. Pest Management Science 63(4), 404–411.

Ternes TA, Occurrence of drugs in Germany sewage treatment plants and rivers. Water Res. 1998, 32 (11): 3245–3260.

Verliefde A, Cornelissen E, Amy G, van der Bruggen B, van Dijk H, Priority organic miropollutants in water sources in Flanders and the Netherlands and assessment of removal possibilities with nanofiltration. Environ. Pollut. 2007; 146: 281–289.

Whittier, R.B., Rotzoll, K., Dhal, S., El-Kadi, A.I., Ray, C., Chang, D. (2010) Groundwater source assessment program for the state of Hawaii, USA: methodology and example application. Hydrogeology Journal 18(3), 711–723.

Williams, C.F. and McLain, J.E.T. (2012) Soil Persistence and Fate of Carbamazepine, Lincomycin, Caffeine, and Ibuprofen from Wastewater Reuse. Journal of Environmental Quality 41(5), 1473-1480.

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Appendix I. List of 16 pharmaceutical compounds selected in this project.

Table I-1. List of 16 pharmaceutical compounds investigated during batch sorption and degradation experiments and their physico-chemical propertiesapropertiesa .

Contaminants Class CAS Number

MW (g mol-

1)

Log Kow

Water Solubility

(mg L-1, 25 ºC)

VP (mm Hg,

25 ºC) Usage

Henrys Law Constant (atm m3 mol-1, 25

ºC) 1,7 Dimethylxanthine Illicit 611-59-6 180.16 -0.39 4.15E+03 8.21E-09 CNS stimulant 1.75E-12

Acetaminophen Illicit 103-90-2 151.16 0.27 3.04E+04 1.94E-06 Analgesic, antipyretic 6.42E-013

Caffeine Illicit 58-08-2 194.19 0.16 2.63E+03 7.33E-09 CNS stimulant 3.58E-11 Cotinine Illicit 486-56-6 176.22 0.34 9.99E+05 3.81E-04 CNS stimulant 3.33E-12 Diphenhydramine (DPH) Illicit 58-73-1 255.36 3.11 3.63E+02 5.80E-06 Antihistamine 3.70E-09 Methamphetamine Illicit 537-46-2 149.23 2.22 1.32E+04 4.48E-03 Psychostimulant 2.37E-06

Trimethoprim Illicit 738-70-5 290.32 0.73 2.33E+03 7.52E-09 Bacteriostatic antibiotic 2.39E-14

17b- Estradiol (E2) Steroid 50-28-2 272.38 3.94 8.20E+01 1.99E-09 Estrogen 3.64E-11 b-Trenbolone Steroid 10161-33-8 270.37 2.65 3.24E+02 1.86E-08 Steroid 1.90E-09 Estriol (E3) Steroid 50-27-1 288.38 2.81 4.41E+02 0.37E-12 Estrogen 1.33E-12 Estrone (E1) Steroid 53-16-7 270.37 3.43 1.47E+02 5.09E-03 Estrogen 3.80E-10 Testosterone Steroid 58-22-0 288.42 3.27 6.78E+01 1.71E-08 Steroid hormone 3.53E-09 Gemfibrozil PPCPs 25812-30-0 250.33 4.77 4.96E+00 3.05E-05 Lipid regulator 1.19E-08

Ibuprofen PPCPs 15687-27-1 206.29 3.79 4.10E+01 1.86E-04 Nonsteroidal anti-inflammatory drug 1.52E-07

Naproxen PPCPs 22204-53-1 230.26 3.10 1.45E+02 1.27E-06 Nonsteroidal anti-inflammatory drug 3.39E-10

Triclosan PPCPs 3380-34-5 289.54 4.66 4.62E+00 4.65E-06 Antibacterial, antifungal 4.99E-09

a Acronym: CAS number = Chemical Abstracts Service number, MW = Molecular Weight, Log K0W = octanol-water coefficient, VP = vapor pressure, and CNS stimulant = central nervous system. Physico-chemical properties have been estimated using EPIWEB 4.1.

Formatted

Formatted Table

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Appendix II. Identification of illicit pharmaceuticals, personal care products and steroids in wastewater extracts by solid-phase extraction (SPE) and high pressure liquid chromatography/tandem mass spectrometry (HPLC/MS/MS).

Raw water and recycled water collected from four different wastewater treatment plants (Wahiawa and Schofield on Oahu, Pukalani on Maui, and Waimea on Kauai) across the Hawaiian Islands were analyzed. Triplicates were used during this preliminary investigation.

Preparation of the samples was completed at the University of Hawaii – Department of Civil and Environmental Engineering, while the chemical analyses were performed at the Water Sciences Laboratory – University of Nebraska.

Solid-phase extraction (SPE) is a procedure for extracting organic compounds from larger volumes of water and injecting a portion of the extract onto an HPLC column for analysis. The method has been developed and validated on a triple-quadrupole mass spectrometer at the Water Sciences Laboratory – University of Nebraska.

One hundred milliliters (mL) of wastewater was weighed into a 100-mL bottle and extracted through an HLB solid-phase extraction cartridge (200 mg, 6 cc, Waters). Prior to load the samples, each cartridge was pre-conditioned with 6 mL acetone, followed by 6 mL of methanol and 6 mL of deionized water.

After loading the samples, cartridges were eluted sequentially with 5 mL 0.1% formic acid in methanol and 3 mL of acetone using a VisiprepTM DL elution manifold cover. All samples were spiked with 100 mL of internal standard spike solution of illicit pharmaceuticals, personal care products, and steroids. After elution, samples were concentrated by blowing down to dryness under a stream of dry nitrogen gas the samples and re-constituted by adding methanol and deionized water. A different water methanol ratio (80:20 for illicit pharmaceuticals, pharmaceuticals and personal care products, 50:50 for steroids) was adopted to re-constitute the samples. The water and methanol mixture was subject to vortex for approximately 10 seconds and transferred using glass disposable pipet into an HPLC vial equipped with a silanized glass insert. Prior to run the samples, each HPLC vial was centrifuged at 2000 rpm for approximately 10 minutes. Additional information regarding the HPLC column and gradient and Quattro-Micro mass spectrometer specifications used during the analysis of illicit pharmaceuticals, pharmaceuticals and personal care products, and steroids in the wastewater samples are given in Tables II.1−4.

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Table II-1. HPLC columns and Quattro-Micro mass spectrometer specifications used during the analysis of illicit pharmaceuticals, pharmaceuticals and personal care products, and steroids in the wastewater samples.

Analytical specifications Illicit pharmaceuticals

Pharmaceutical and Personal care products (PPCPs)

Steroids

High-Performance Liquid Chromatography specification

Column model HyPURITY C18 HPLC column HyPURITY C18 HPLC column BetaBasic C18 reverse phase HPLC column

Column size 250 mm x 2.1 mm ID, 5 µm particle size

250 mm x 2.1 mm ID, 5 µm particle size 250x2 mm

Temperature 50°C 50°C 50°C Flow rate 0.20 ml/min 0.20 ml/min 0.30 ml/min

Mobile phases

A: 0.5 g/L Ammonium formate in 97% Methanol and 3% DDI H2O; B: .5 g/L Ammonium formate in 97% DDI H2O and 3% Methanol

A: 0.002% v/v formic acid in Methanol; B: 0.002% v/v formic acid in DDI H2O

A: 0.15% formic acid in methanol/water (97:3); B: 0.15% formic acid in water/methanol (97:3)

Gradient

0%A, hold until 3.0 min, then step to 60%A followed by linear gradient to reach 95%A at 12.0 min, hold 6 min, then immediately back to initial conditions (0%A), hold for 8 min

0%A, hold until 3.0 min, then step to 60%A followed by linear gradient to reach 95%A at 12.0 min, hold 6 min, then immediately back to initial conditions (0%A), hold for 8 min

Dopant Toluene Total run time 26 minutes 26 minutes 30 minutes Quattro-Micro mass spectrometer specification

Ionization Source/mode

ESI (electrospray ionization)positive/negative ion modes

ESI (electrospray ionization) source in positive/negative ion modes

APPI (atmospheric pressure photoelectron ionization) positive ion mode

Formatted: Right: 0.75"

Formatted Table

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Post column addition 20% toluene in methanol at a flow rate of 0.02 mL/min

Table II-1 (continued)



Steroids

Collision gas Argon at 4.0x10-3 torr Argon at 4.0x10-3 torr Argon at 4.2x10-3 torr Desolvation gas N2 at 600 L/hr N2 at 600 L/hr N2 at 200 L/hr Cone gas N2 at 30 L/hr N2 at 30 L/hr N2 at 30 L/hr Source temperature 125°C 125°C 135°C Desolvation temperature 450°C 450°C -

Probe temperature - - 450°C Capillary 4/3 kV 4/3 kV Repeller 1 kV Extractor 3/2 V 3/2 V 3 V RF Lens 0.1/0.2 V 0.1/0.2 V 0 V LM Resolution 1: 13 1: 13 1: 13 HM Resolution 1: 13 1: 13 1: 13 Ion Energy 1: 0.8/0.5 V 1: 0.8/0.5 V 1: 0.8 V LM Resolution 2: 13 2: 13 2: 13 HM Resolution 2: 13 2: 13 2: 13 Ion Energy 2: 1.5/2.0 V 2: 1.5/2.0 V 2: 1.5 V Multiplier 650 eV 650 eV 750 eV Entrance -5 V -5 V -5 V Exit 1 V 1 V 1 V
























































































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Compound CAS number Formula MW (g mol-1)

Parent Ion

(m/z)

Product Ion

(m/z)

Cone Voltage

(V)

Collision Energy

(eV)

Retention time

(min) Phenazone Gemfibrozil Trimethoprim

60-80-0 25812-30-0

738-70-5

C11H12N2O C15H22O3

C14H18N4O3

188.23 250.33 290.32

188.95 248.95 291.20

147 121

230.2

40 30 40

20 18 25

11.25 17.52 9.70

* Internal Standard

Table II-3. Cone voltages, collision energies, and other details pertaining to standards and analytes used during the method developed for pharmaceuticals and personal care products (PPCPs).


Parent Ion

(m/z)

Product Ion

(m/z)

Cone Voltage

(V)

Collision Energy

(eV)

Retention time

(min) Caffeine 13C3*

13C-Atrazine**

13C-DEA*

Gemfibrozil Ibuprofen Naproxen Triclosan

- - - 25812-30-0 15687-27-1 22204-53-1 3380-34-5

13C3C5H10N4O2

13CC7H14ClN5 13CC5H10ClN5 C15H22O3

C13H18O2

C14H14O3

C112H7Cl3O2

197.18 215.68 187.63 250.33 206.29 230.26 289.54

198 219.1 191.05 248.95 205 229 287

139.95 177.05 148.95 121 161 170 35

37 33 33 27 18 17 20

19 17 17 18 9 19 13

10.94 13.59 11.94 17.27 16.27 14.27 17.35

* Internal Standard ** Surrogate















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Table II-4. Cone voltages, collision energies, and other details pertaining to standards and analytes used during the method developed for steroids.


Parent Ion (m/z)

Product Ion (m/z)

Cone Voltage (V)

Collision Energy (eV)

11-Ketotestosterone 53187-98-7 C19H26O3 302.408 303 120.9 30 22 17α-Hydroxyprogesterone 68-96-2 C21H30O3 330.46 331 96.85 30 25 4-Androstenedione 63-05-8 C19H26O2 286.4 287 96.85 30 20 Androstenedienedione (Androstadienedione)

897-06-3 C19H24O2 284.39 285 120.9 20 25

Androsterone 53-41-8 C19H30O2 290.44 273 255.1 25 14 Caffeine 58-08-2 C8H10N4O2 194.19 195 137.95 34 18 Epitestosterone 481-30-1 C19H28O2 288.42 289 108.9 32 26 α-Estradiol 57-91-0 C18H24O2 272.38 255 159 24 20 β-Estradiol 50-28-2 C18H24O2 272.38 255 159 24 20 β-Estradiol-13C6* ---------- 13C6C12H24O2 278.38 261 159 24 20 Estriol 50-27-1 C18H24O3 288.38 288 146 22 22 Estrone 53-16-7 C18H22O2 270.366 271 132.9 24 20 Ethinylestradiol 57-63-6 C20H24O2 296.403 279 132.9 20 18 Melengestrol Acetate 2919-66-6 C25H32O4 396.52 397 337.1 24 14 α-Methyltestosterone** 58-18-4 C20H30O2 302.451 303.05 96.85 32 24 Progesterone 57-83-0 C21H30O2 314.46 315.05 96.85 30 20 Testosterone 58-22-0 C19H28O2 288.42 289.05 96.85 32 24 Testosterone-d5* ---------- C19H23D5O2 293.42 294.05 99.85 32 24 α-Trenbolone 80657-17-6 C18H22O2 270.37 271 253.05 32 20 β-Trenbolone 10161-33-8 C18H22O2 270.37 271 253.05 32 20 α-Zearalanol 26538-44-3 C18H26O5 322.4 305 189.0 28 20 β-Zearalanol 42422-68-4 C18H26O5 322.4 305 189.0 28 20 α-Zearalenol 36455-72-8 C18H24O5 320.3 303 285 24 12 β-Zearalenol 71030-11-0 C18H24O5 320.3 303 285 24 12

* Internal Standard; ** Surrogate











































































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Appendix III. Occurrence of pharmaceutical compounds at the four wastewater treatment plants investigated.

Table III-1. List of pharmaceutical compounds investigated at four wastewater treatment plants using solid-phase extraction (SPE) and high liquid pressure chromatography/tandem mass spectrometry (HPLC/MS/MS).

Illicit pharmaceuticals Pharmaceutical and Personal care products (PPCPs)

Steroids

Raw water 1,7-Dimethylxanthine Gemfibrozil 17α-Hydroxyprogesterone Acetaminophen Ibuprofen 4-Androstenedione Caffeine Naproxen α-Estradiol Carbamazepine Triclosan Androstanedienedione Cotinine Warfarin Androsterone d-Amphetamine α-Trenbolone Diphenhydramine α-Zearalanol Methamphetamine α- Zearalenol Morphine β-Estradiol Sulfadiazine β-Trenbolone Sulfamethoxazole β-Zearalanol Thiabendazole β- Zearalenol Epitestosterone Estriol Estrone Ethynyl Estradiol Melengesterol Acetate Progesterone Testolactone Testosterone

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Figure III-2. Pharmaceutical and personal care products (PPCPs) detected at the four wastewater treatment plants investigated.

0

20

40

60

80

100

120

Gemfibrozil Ibuprofen Naproxen Triclosan Warfarin

Conc

entr

atio

n (n

g/m

L)

SCHOFIELD Raw Avg

SCHOFIELD R1 Avg

MAUI RAW

MAUI R1

KAUAI RAW

KAUAI R1

WAHIAWA RAW

WAHIAWA R1

Formatted: Left

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Table III-2. Illicit (ng/mL) detected at the four wastewater treatment plants investigated. Sample size: 100 gr. Concentrations of Cemitidine, MDA, MDMA, Phenazone, Sulfadimethoxine, Sulfamethazine were below the analytical detection limits.

Sample ID 1,7-

Dim

ethy

lxan

thin

e

Acet

amin

ophe

n

Caffe

ine

Carb

amaz

apin

e

Coti

nine

d-Am

phet

amin

e

Dip

henh

ydra

min

e

Gem

fibro

zil

Met

ham

phet

amin

e

Mor

phin

e

Sulfa

diaz

ine

Sulfa

met

hoxa

zole

Thia

bend

azol

e

Schofield Raw Avg 38.1 38.8 27.3 0.1 14.0 n.a. 12.4 0.7 0.4 0.1 n.a. 0.2 n.a. Schofield R1 Avg 0.2 n.a. n.a. 0.1 n.a. n.a. 0.9 n.a. n.a. n.a. n.a. 0.1 n.a. Maui Raw 32.6 25.3 63.8 n.a. 7.7 0.1 n.a. 6.2 1.2 0.5 1.4 0.1 0.1 Maui R1 0.2 n.a. 0.1 0.1 n.a. n.a. 0.1 n.a. n.a. n.a. 0.2 0.1 n.a. Kauai Raw 7.1 n.a. 16.2 0.1 8.9 0.9 7.3 1.7 3.6 n.a. 0.1 0.4 n.a. Kauai R1 0.4 0.2 0.1 n.a. 0.2 n.a. 0.3 n.a. 0.3 n.a. n.a. 0.1 n.a. Wahiawa Raw 23.8 31.0 30.6 n.a. 6.9 0.3 n.a. 3.5 4.8 n.a. 0.3 0.3 0.1 Wahiawa R1 0.2 n.a. 0.1 0.3 0.2 n.a. 3.6 0.1 0.1 n.a. 0.2 0.2 0.1

n.a. = Not applicable. Analyte concentrations were below the analytical detection limits.

Formatted Table

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Table III-3. Pharmaceutical and personal care products, PPCPs, (ng/mL) detected at the four wastewater treatment plants investigated. Sample size: 100 gr.

Sample_ID

Gem

fibro

zil

Ibup

rofe

n

Nap

roxe

n

Tric

losa

n

War

fari

n

Schofield Raw Avg 1.170 96.519 45.386 0.179 n.a. Schofield R1 Avg 0.012 n.a. 0.049 n.a. n.a. Maui Raw 6.994 40.742 30.505 2.523 0.209 Maui R1 0.018 0.038 0.035 0.183 n.a. Kauai Raw 3.568 16.433 15.544 1.701 0.093 Kauai R1 0.044 n.a. 0.103 n.a. 0.026 Wahiawa Raw 5.639 28.930 33.967 2.378 0.130 Wahiawa R1 0.206 n.a. 0.014 n.a. 0.034

n.a. = Not applicable. Analyte concentrations were below the analytical detection limits.

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Table III-4. Steroids (ng/mL) detected at four wastewater treatment plants investigated. Sample size: 100 gr. Concentrations of 17α-Hydroxyprogesterone, α−Zearalanol, α-Zearalenol, β-Zearalanol, β-Zearalenol, 17β-Estradiol, Ethynyl Estradiol, Melengesterol Acetate were below the analytical detection limits.

Sample_ID

4-An

dros

tene

dion

e

α-E

stra

diol

Andr

osta

nedi

ened

ione

Andr

oste

rone

α-T

renb

olon

e

β-Tr

enbo

lone

Epit

esto

ster

one

Estr

iol

Estr

one

Prog

este

rone

Test

olac

tone

Test

oste

rone

Schofield Raw Avg n.a. n.a. n.a. n.a. n.a. n.a. n.a. 2.161 n.a. n.a. n.a. 0.002

Schofield R1 Avg n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a.

Maui Raw 0.139 0.065 0.274 0.768 0.473 0.758 0.028 n.a. 0.388 0.018 0.318 0.028 Maui R1 n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. Kauai Raw n.a. n.a. n.a. n.a. n.a. n.a. n.a. 0.389 n.a. n.a. n.a. n.a. Kauai R1 n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. 0.004 Wahiawa Raw n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. 0.002

Wahiawa R1 0.147 0.072 0.180 n.a. 0.609 1.522 0.052 0.455 0.700 0.019 0.213 0.038 n.a. = Not applicable. Analyte concentrations were below the analytical detection limits.

Formatted Table

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Table III-25. Removal (%) of illicit pharmaceuticals, pharmaceutical and personal care products (PPCPs) and steroids detected at the four wastewater treatment plants investigated.

Compounds Wastewater Treatment Plants Schofield Maui Kauai Wahiawa

Illicit 1,7-Dimethylxanthine 99.42 99.38 93.98 99.12 Acetaminophen 100 100 n.a. 100 Caffeine 99.84 99.87 99.14 99.83 Carbamazapine n.a.0 0n.a. 53.94 0n.a. Cotinine 99.75 99.48 97.49 97.71 d-Amphetamine n.a. 88.84 99.16 96.65 Diphenhydramine 92.91 n.a. 96.16 n.a. Gemfibrozil 98.94 100 97.19 97.89 Methamphetamine 93.79 99.32 91.31 97.51 Morphine 88.10 100 n.a. n.a. Sulfadiazine n.a. 88.27 78.19 34.08 Sulfamethoxazole 61.40 8.74 86.09 35.45 Thiabendazole 0n.a. 69.34 17.65 10.23 PPCPs Gemfibrozil 98.94 99.75 98.76 96.34 Ibuprofen 100.00 99.91 100.00 100.00 Naproxen 99.89 99.89 99.33 99.96 Triclosan 100.00 92.74 100.00 100.00 Warfarin n.a. 100.00 71.87 73.95 4-Androstenedione n.a. 100 n.a. 100 IllicitSteroid α-Estradiol n.a. 100 n.a. 100 Androstanedienedione n.a. 100 n.a. 100 Androsterone n.a. 100 n.a. n.a.

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Table III-5 (continued) Compounds Wastewater Treatment Plants Schofield Maui Kauai Wahiawa α-Trenbolone n.a. 100 n.a. 100 β-Trenbolone n.a. 100 n.a. 100 Epitestosterone n.a. 100 n.a. 100 Estriol 100 n.a 100 100 Estrone n.a. 100 n.a. 100 Progesterone n.a. 100 n.a. 100 Testolactone n.a. 100 n.a. 100 Testosterone 100 100 n.a. 95.04

n.a. = Not applicable. Analyte concentrations in raw and recycled waters were 0below the analytical detection limits.

Formatted: Left

Formatted: Font: Italic

Formatted Table

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Appendix IV. Materials and Methods

1. Collection and storage

An approximately 1.5m x 1m area was identified within each sampling location. The identified area was scraped using shovels or pickaxepeakaxe, if needed, to remove possible vegetation and smeared soil. Disturbed and undisturbed soil samples were collected from the four corners of the identified area at three different depths (0-30cm, 30-60cm, and 60-90cm), representing surface and deep subsurface soils samples using a hand auger and a soil core sampler, respectively.

Disturbed soil samples were used during the degradation and the sorption studies as well as to estimate soil properties. Undisturbed soil samples were used to estimate the bulk density of the soils.

A 4-inches stainless steel auger bucket with cutting heads was used. The auger bucket was carefully cleaned prior to start the sampling. The bucket was advanced by simultaneously pushing and turning using the attached handle. Auger holes were advanced one bucket at a time until the sample depth was achieved. Samples were placed into clean, labeled Ziploc bags, stored in coolers containing ice packs during the transport from the sampling location to the laboratory, where the soils samples were stored at 4ºC.

Undisturbed soil cores were extracted using a soil core sampler (Soilmoisture, CA). A core (5.7cm diameter) was held in a brass cylinder, placed in a metal stainless steel cutter cast. A drop hammer was used to advance the sampler into the soil until the top edge of the cuter reached the final depth. After that, the core sample was carefully removed, the ends of the core were trimmed, and the cores were capped and stored in coolers containing ice packs until they were properly stored in the laboratory.

2. Experimental design

Batch studies were conducted to estimate the behavior of selected compounds in the environment. Degradation studies and adsorption isotherms were determined. Half-life and sorption coefficients were estimated. Batch studies were conducted according to the Fate, Transport and Transformation Test Guidelines (OPPTS 835.1220 Sediment and Soil Adsorption/Desorption Isotherm, EPA, 1998).

Batch experiments were conducted using sieved soil less than or equal to 2 mm (sieve: no. 10). Deionized water fortified with calcium chloride (0.01 M CaCl2) was used as aqueous matrix. Glass vials wrapped with aluminum foil were used throughout the study to

Commented [RBW7]: Pickaxe?

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minimize i) adsorption of the selected compounds to the wall of the vials and ii) photodegration of the selected compounds.

In order to obtain a representative sample, a known amount of soils was mixed and homogenized using a combination of a sieving riffler (see Figure IV-1a) followed by a rotary micro riffler (see Figure IV-1b). The amount of soil contained into each glass tubes located in the micro riffler was transferred into 40 mL glass vials and used during the batch degradation and sorption experiments.

a. b.

Figure IV-1. Sieving riffler (a, left) and rotary micro riffler (b, right) used to prepare the soil samples used during the degradtion and sorption experiments.

A screening test was conducted prior to the sorption study to identify the correct soil to water ratio, the proper equilibration time and to verify the adsorption of selected chemical, the stability of the compounds and possible analytical interference. Soil to water ratio was performed by settle on a few fixed ratios, for which the percentage adsorbed should be above 20%, preferably >50%, while particular attention should be taken to keep the test substance concentration in the aqueous phase high enough to be measured accurately. Various amounts of soil (0.2, 1, 2, 5 gr) were added to a fixed amount of water (10 mL) in order to achieve 1:50, 1:10, 1:5, and 1:2 soil to water ratio, mixed for 16 hours in presence using a stainless steel mixing box (Figure IV-2) of a fixed concentration (1 mg L-1) of each compound. Blanks including the soil with only 0.01 M CaCl2 solution (no compounds were added) and compounds with only 0.01 M CaCl2 solution (no soil) were analyzed. After

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agitation, the soil-water suspension was centrifuged, and a clear solution was obtained. The clean solution was analyzed. Due to the different soil properties, different soil:water ratios were selected. A 1:10 ratio was selected for Poamoho, and Waimanalo, a 1:2 ratio was selected for Kauai, while a 1: 5 was selected for the remaining soils.

The selected soil:water ratios were used to estimate the equilibration time for the three class of compounds. 4, 18, and 24 hours were used in the presence of steroids, pharmaceuticals and personal care products, and illicit pharmaceuticals, respectively.

According to the results of the soil:water ratio and the equilibration time, sorption and isotherms were calculated to predict the mobility in soil/water system. Known amounts of soil samples were placed in 40 mL glass vials, wrapped with aluminum foil to prevent possible photodegradation. Samples were mixed using a stainless steel mixing box (see Figure IV-2). After agitation, the soil-water suspension was centrifuged, and a clear solution was obtained. The clean solution was analyzed. Different models, linear, Langmuir, and Freundlich isotherms, were used to fit the results of the sorption-desorption study.

However, results obtained using the linear model were implemented into our model simulation.

Figure IV-2. Stainless stealsteel mixing box used during the sorption study.

Degradation of selected pharmaceutical compounds was performed by placing a fixed amount of soil (5gr) into a 40 mL glass vial wrapped with aluminum foil to prevent

Commented [RBW8]: A little more detail on the soil:water ratio criteria, why it is important, and how it was determined would be useful

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photodegradation. 10 mL of stock solution was added into each vial. 5 different sampling times (1, 7, 14, 28, and 56 days) were used during this study. Commented [RBW9]: A table of results would be very useful.

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Appendix V. Identification of illicit pharmaceuticals, personal care products and steroids in solid samples extracts by by microwave-assisted solvent extraction (MASE) and high pressure liquid chromatography/tandem mass spectrometry (HPLC/MS/MS).

Extraction of selected pharmaceutical compounds from soil samples after degradation experiments were at the Water Sciences Laboratory – University of Nebraska.

The microwave-assisted solvent method (MASE) is a procedure for extracting water insoluble or slightly water soluble organic compounds from soils, clays, sediments, sludges, and solid wastes. This method was originally developed and validated for analysis of trace levels (< 100 ng/g) of steroid hormones and related compounds using a commercially-available laboratory microwave. In order to conduct this study, the MASE method was implemented and validated for illicit pharmaceuticals and pharmaceutical and personal care products. The procedure uses microwave energy to produce elevated temperature and pressure conditions in a closed vessel containing the sample and organic solvent(s) to achieve analyte recoveries equivalent to those from a traditional extraction. The benefits of this method are enhanced extraction times, low solvent consumption and improved extraction efficiencies.

Soil samples used during the degradation study were carefully transferred into 40mL MASE Teflon vessels. In order to investigate the degradation of illicit pharmaceuticals and pharmaceuticals and personal care products 7 mL of acetonitrile with 100 mM Ammonium Hydroxide were added into each MASE Teflon vessel, while 6 mL of methanol were used during the investigation of steroids. After vortexing vigorously for 30 seconds each MASE Teflon vessel, they were placed inside the microwave and an appropriate loading cycle (see Table 1) was selected. When the cycle was complete, the vessels were cooled to room temperature and the extracts were decanted into 40 mL Falcon tubes. The MASE Teflon vessels were refilled with 7 mL of acetonitrile with 100 mM Ammonium Hydroxide or 6 mL of methanol according to the compounds, shaked with a vortex for 5 minutes and the extracts were decanted in the 40 mL Falcon tubes. Each tube was centrifuged at 3000 rpm for 10 minutes. The extracts were transferred to the a 100 mL glass tube and 1.4 mL 10mM formic acid was added prior to reduce the amounts of solvents to approximately 1 mL under nitrogen gas using Rapid Wap. After that deionized water was added to achieve a total volume of 100 mL and the SPE procedure (see Appendix A1) was applied. The Rapid Wap was not used during the analysis of steroids compounds.

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Table V-1. Solvents and analytical specifications related to the MASE method used during the study.



Steroids

Solvent 7 mL Acetonitrile with 100 mM NH4OH

7 mL Acetonitrile with 100 mM NH4OH

6 mL Acetonitrile with 100 mM NH4OH

Power (W) 400 400 400

Ramping time 10 mintutes 10 mintutes 15 mintutes

Temperature 80ºC 80ºC 90ºC

Holding time 10 minutes 10 minutes 5 minutes

Cooling time 5 minutes 5 minutes 5 minutes

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Appendix VI. Test pharmaceutical compounds and soils used for inter-model comparison of the new CLERS tool with HYDRUS-1D.

Table VI-1. Representative chemical properties of three pharmaceutical compounds selected for inter-model comparison between CLERS and HDRUS-1D models. a

Chemicals Koc (m3/kg) T1/2 (d) Kd (m3/kg) Mean SD Mean SD Mean SD Estrone 2.087 3.462 3.209 1.450 0.045 0.064 Cotinine 0.091 0.088 25.818 19.112 0.002 0.001 Methamphetamine 0.654 0.845 14.346 10.098 0.014 0.016

a Acronym: SD = standard deviation.

Table VI-2. Representative soil properties at 0.9 m soil depth used for inter-model comparison between CLERS and HDRUS-1D models a.

Islands Soilsb MUSYM MUKEY ρb fOC θFC

(kg/m3) (‒) (‒)

Oahu AF1 KyA 468441 1,250 0.017 0.336

Oahu W1 WnB 468519 1,150 0.017 0.357

Oahu P1 WaB 468511 1,330 0.020 0.383

Maui M2 KxaD 468296 550 0.111 0.196

Maui M1 MfC 468310 1,048 0.064 0.354

Kauai K1 JfB 467825 1,482 0.004 0.089

Hawaii BI2 HoC 1883069 500c 0.067 0.236

Hawaii BI1 MaA 1883115 500c 0.150 0.264 a Acronym: MUSYM = map unit symbol and MUKEY = map unit key. MUSYM and MUKEY are unique soil codes assigned to describe soil series in SSURGO database. b Soils: AF1 = Aloun Farms, W1 = UH Waimanalo UH Waimanalo Ag Station, P1 = UH Poamoho Ag Station, M2 = UH Kula Ag Station, M1 = UH Haleakala Ag Station, K1 = Kauai Ag Development corporation, BI2 = UH Waiakea Ag Station, and BI1 = UH Mealani Ag Station. c The bulk density of the soils is adjusted to 500 (kg/m3) due to the lower bound in Rosetta Lite program to estimate soil hydraulic parameters.

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Appendix VII. User manual of the new CLERS tool for pharmaceuticals.

Note that you have to install ArcGIS 10.1 for Desktop on your desktop to open the new CLERS tool for pharmaceuticals. This is because the program developer have mainly developed and tested this tool in the recent version of ArcGIS program. Python 2.7 comes with the ArcGIS 10.1.

Step 1: Extract the “CLERS Tool Ver2.zip” file in the directory under "C:\”. You can unzip it in other folder you wish, but in this case, you have to also change the certain paths of scripts in Layer Update Script_OSDS.py and Layer Update Script_R1.py (see the figure in Step 2).

Step 2: Then, you can see 7 folders and other python scripts (a file extension of py) in that directory (see the figure blow). Each folder includes geospatial data such as soil map, recharge map, and other maps (i.e., OSDS_density, R1, SWAP_Layers, and PCA_Layers) related to contamination activities for each island. GIS data in 7_Merge folder are used to update the symbols of newly added layers consistently for all islands.

The user can open python scripts in different modes, 1) built-in window under ArcMap or 2) default Python editor: Integrated Development Environment (IDLE) (see the figure blow).

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(Built-in window under ArcMap)

(A default Python editor)

Step 3: Open CLERS_V3.mxd file. This will launch ArcMap (see the figure blow).

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Step 5: Click the “Python window” button in the Menu Bar Icons to run geoprocessing commands and scripts (as shown in built-in window at Step 2). This will launch the Python window (see the figure blow).

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Step 6: If you do a right-click on the Python window, you will see another pop-up menus, as shown below. Here, you can load python scripts (a file extension of py) that are introduced at Step 2.

To develop the vulnerability map for a particular compound of interest, you have to firstly open (or load) Built-in chemical database.py using a default Python editor (as shown below). Here, we include chemical properties of pharmaceuticals as well as pesticides.

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Please only copy chemical properties of a compound of your interest in parenthesis (Ctrl+C). Next, load the CLERS Script.py using the built-in Python window (as shown below).

Then, paste the chemical properties of your interest into ChemPr in the CLERS Script.py (Ctrl+V). You may have to scroll up to the top of the Python screen to see this code (see the figure below).

The picture can't be displayed.

Commented [RBW10]: This is a bit unclear.

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Once you change the chemical properties you are interested in, press “Enter” button. That’s it. Close the built-in Python window. Then, groundwater vulnerability map will be shown as in Step 3. Re-test other chemicals as much as you wish.

Please note that you have to change certain scripts for data frame depending on the islands you choose or activate in the table of contents (see the figure below).


Formatted: Font: +Headings (Cambria), 12 pt

Commented [RBW11]: What is meant here is not clear. Do you have change scripts for each dataframe? If so, which scripts?

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Step 7: Please add a layer of interest (OSDS Density) for the selected data frame (e.g., Oahu) using “Add data” button (see the figure below).



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In this case, we select “oahu_osds_density.shp” island in the 3_OSDS_density folder, and then press “Add” button.

Open Python window in ArcMap and load “Layer Update Script_OSDS.py”. Then, make necessary changes for data frame index (e.g., 0 for Oahu) and layer name (e.g., oahu_osds_density) in the script code and then press “Enter” button. This will automatically update the layer symbology which is consistent across all islands. The script codes should



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be changed to data frame index (e.g., 1 for Maui) and layer name (e.g., maui_osds_density) on the island of Maui, and so on.

Step 8: The same is applied to the 4_R1_water folder. Here, we select “R1_water_oahu.shp” to add a layer of interest (R1_water) in the selected data frame (e.g., Oahu).



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Then, click “Enter” button after you load Layer Update Script_R1.py in the Python window. As shown in updating the layer of OSDS Density, modify data frame index (e.g., 0 for Oahu) and layer name (e.g., R1_water_oahu), and so on. This will make the polygons with light blue color and 30% of transparency (see the figure below).



APPENDIX F - HISTORICAL CONTAMINANT SAMPLING, UNDATED (18 PAGES)

1

HISTORICAL CONTAMINANT SAMPLING

Project Goals

The goal of this project was to provide updated monitoring data on detected historical

contaminants found in groundwater.


A total of 62 wells that have a history of past contamination were sampled. This included

samples from 23 well fields (locations with closely spaces such as the Waiaphu IV which has

four wells within the same compound).


The report, tables and maps will be archived on the SDWB server. The data from this study will

be shared with Hawaii Department of Agriculture and the Hawaii Agriculture Research Center.

Data will be publically available on the Groundwater Contamination Viewer.

The results of this project will be used to increase surveillance in areas where an increasing trend

in contaminant concentrations were identified. The data can also be used by water systems when

planning locations for new water sources and planning well head treatment systems.


The areas that show an increasing trend in the contaminant concentrations need further

evaluation to determine potential migration paths. A follow on workplan will be developed to

track the groundwater contamination trends in those areas that the concentrations are either

stable or increasing.

Project Description

Hawaii has on all of the major islands except Lanai with a history of detections of contaminants

regulated under the Safe Drinking Water Act (SDWA). Currently, most samples collected for

SDWA compliance are taken after the water had been treated to reflect what the water quality

that is being consumed. This treatment removes contaminants that are captured by the well and

are not reflected of the groundwater quality in the aquifer. This project collected samples prior

to treatment from drinking water sources with a history of contamination. For wells with a

sufficient number of samples collected, a determination was made as to whether the

contamination level was increasing, decreasing, or remaining stable. These trend analysis were

only made for wells where contamination was detected during the 2014 sampling events and

there were at least 2 previous detections of the contaminant. There were sufficient data for 1,2,3-

Trichlolopropane (TCP), 1,2-Dibromo-3-Chloropropane (DBCP), Trichloroethylene (TCE), and

Dieldrin to make determinations regarding trends in contamination levels. The contaminants

Carbon Tetrachloride, Chlordane, Heptachlor Epoxide, Tetrachloroethylene (PCE), and Ethylene

2

DiBromide (EDB) were detected in 2014 but there are an insufficient number of historical

samples to evaluate trends. Eight wells were sampled during 2014 for Atrazine, all

concentrations were less than the detection limit.

Tables 1 through 6 summarize the results of the sampling. Temporal trends in concentration

were commented on if there were three or more positive detections of the contaminant. A

sampling event is defined as any sample collected from a well or from well field where more

than three months had elapsed from any previous sample. Concentrations that exceed the

Maximum Contaminant Limit (MCL) are shown in bold red.


Table 1 shows the sampling results for TCP. Samples from 49 wells or well fields were analyzed

for TCP either during 2014 or previously. During the 2014 round, samples were collected from

40 wells or well fields. Of the samples collected during 2014, 9 had TCP concentrations greater

than the MCL of 0.6 g/L. The highest TCP concentration was 2.8 g/L in a sample collected

from the Mililani III Wells on May, 1, 2013. A sample collected from the nearby Mililani II

Wells had a concentration of 2.4 g/L on March 3, 2008. Prior to 2014, TCP exceeded the MCL

at 12 of the wells sampled.

There were a sufficient number of samples to evaluate trends for 30 wells. The TCP

concentration in eight wells was either decreasing or stable and decreasing. At 11 of the other

wells the TCP concentration was stable, neither increasing nor decreasing with the 2014

concentration be only slightly less than the historical concentration. At 11 wells, the TCP

concentration was either increasing or stable with 2014 sample concentration being slightly

higher than historical concentrations. The area with most consistent increasing trend was

Waipahu.

1,2-Dibromo-3-Chloropropane (DBCP)

Table 2 shows the sampling results for DBCP. Thirteen wells have a history of positive DBCP

detections. All but one well had DBCP concentrations that exceeded the MCL of 0.04 g/L.

Ten wells were resampled in 2014. The DBCP concentration in 9 of the wells exceeded the

MCL. The maximum DBCP concentration of 0.27 g/L was measured at the Mililani I wells.

This is only slightly less than the historical high concentration of 0.28 g/L measured at this well

field. There were a sufficient number of sampling events at 4 of the wells to evaluate the

temporal trend. There was no confirmed increasing trend, but the trend at the Mililani I Wells

was either stable or slightly increasing. There was a decreasing trend at 2 wells and the trend

was stable at another well.

3


Table 3 list the sampling results for TCE. There are 5 drinking water wells with a history of

positive detections for TCE. These wells are all located in the central Oahu corridor between the

Koolau and the Waianae Mountain Ranges. Four of these wells were resampled during the 2014

sampling events. The MCL of 5 g/L was exceeded in the sample collected from the Del Monte

Kunia 3 Well. This sample had a TCE concentration of 6.6 g/L slightly less than the historical

high concentration of 7.1 g/L in sample collected on February 20, 2008. The Schofield Battery

of Wells had the highest TCE concentration at 40.6 g/L in a sample collected on June 18, 2013.

The TCE concentration in all other wells was less than the MCL. The Waialua Wells were the

only location where a sufficient number of samples were collect to evaluation the temporal trend

of TCE contamination. At these wells the TCE concentration stable at about 1 g/L.

Dieldrin

The Dieldrin sample results are summarized in Table 4. A total of 15 public drinking water

wells or well fields have a history of Dieldren detections. Eleven of these wells were resampled

in 2014. The MCL of 0.2 g/L was not exceeded in any sample collected. The highest

concentration in samples collected during the 2014 sampling event was 0.09 g/L at the Halawa

Wells. The highest historical Dieldrin concentration was 0.2 g/L in a sample collected at the

Kapalama Wells on December 21, 2011. The Dieldrin concentration measured at this well

during the 2014 sampling event was 0.02 g/L. Dieldrin was below the detection limit in two of

samples collected during the 2014 sampling event. There are 5 locations where a sufficient

number of samples were collected to evaluate the temporal trend. All had decreasing trends

except for Halawa Wells where the Dieldrin concentration was either stable or slightly

increasing.

Atrazine

Table 5 lists the sampling results for Atrazine. There are 23 public drinking water wells or well

fields with a history of Atrazine contamination. The majority (13) are on the island of Hawaii.

Five of these wells and 4 irrigation wells were sampled during the 2014 sampling event. The

Atrazine concentration in all of the samples collected in 2014 was less than the detection limit.

The MCL of 3 mg/L has been not exceeded in any sample collected. The highest Atrazine

concentration in any sample collected was 0.69 mg/L in a sample collected at the Ookala Well

on August 13, 2002.

4


Table 6 lists the results for contaminants where there was only a single location where the

concentration was equal to or greater than the reporting limit. The contaminants include: Carbon

Tetrachloride, Heptachlor Epoxide, Tetrachloroethylene, and Ethylene Dibromide. The well,

highest concentration detected, and current concentration are compared to the MCL. The only

contaminant that exceeded the MCL was Ethylene Dibromide in the Maunaolu-Smith Well on

Maui.

5

Table 1. 1,2,3-Trichloropropane (TCP) Sample Results (page 1 of 3)

Island Water

System

ID

Well or Well

Field

Well ID Sampling

Events

Trend Minimum Maximum Date of

Maximum

Current MCL

(ppb) (ppb)

(ppb) (ppb)

Kauai 400-030 Puhi Well 4 5824-04 2 NA 0.05 0.06 4/8/08 0.05 0.6

Kauai 400-039 Wailua

Homestead

Well A

0421-01 2 NA 0.04 0.06 11/28/12 0.05 0.6

Kauai 400-064 Hanamaulu

Wells

0124-01 3 Increasing 0.05 0.10 9/10/14 0.10 0.6

Kauai 434-010 Lawai Well I 5530-01 1 NA ---- 0.04 2/23/08 ---- 0.6

Kauai 434-502 Piwai Well 2 5629-01 1 NA ---- ---- 9/10/14 0.11 0.6

Maui 204-003 Kapalua Well

1

5938-01 1 NA ---- 0.04 1/23/13 ---- 0.6

Maui 205-001 Kaanapali

Well P4

5739-01 2 NA 0.29 0.36 4/8/13 0.29 0.6


Well P5

5738-01 2 NA 0.43 0.51 4/8/13 0.43 0.6


Well P6

5739-02 2 NA 0.60 0.84 5/19/08 0.60 0.6


Well P-5A

5739-04 2 NA 0.13 0.29 12/13/11 0.13 0.6

Maui 213-003 Haiku Well 5419-01 2 NA 0.15 0.16 9/10/14 0.16 0.6

Maui 214-001 Napili D 5838-03 1 NA ---- 0.09 11/30/05 ---- 0.6

NA – not applicable ---- no sample collected in 2014 or only one historical sample

6

Table 1. (Continued) 1,2,3-Trichloropropane (TCP) Sampling Results (page 2 of 3)

Island Water

System

ID

Well or Well

Field

Well ID Sampling

Events


Maximum

Current MCL

(ppb) (ppb)

(ppb) (ppb)

Maui 214-008 Napili C 5838-04 2 NA 0.04 0.05 1/12/09 0.04 0.6

Maui 254-001 Maunaolu-

Smith Well

5320-02 2 NA 0.53 0.61 10/7/14 0.61 0.6

Oahu 303-002 Del Monte 3

Well

2803-05 2 NA 0.12 0.23 2/20/08 0.12 0.6

Oahu 303-003 Del Monte

Kunia Well 4

2803-07 2 NA 0.21 0.22 7/21/14 0.22 0.6

Oahu 304-001 Hawaii

Country Club

Well

2603-01 2 NA 0.57 0.59 12/18/13 0.57 0.6

Oahu 331-105 Pearl City

Shaft

2458-01 2 NA 0.05 0.05 NA 0.05 0.6

Oahu 332-002 Haleiwa Wells 3405-04 2 NA 0.59 0.77 8/12/08 0.59 0.6

Oahu 332-004 Waialua Wells 3405-02 3 increasing 0.60 0.73 7/10/14 0.73 0.6

Oahu 333-006 Wahiawa II

Wells

2902-02 3 stable 0.11 0.13 7/31/08 0.11 0.6

Oahu 334-006 Wapio

Heights I

Wells

2459-01 3 Stable or

increasing

0.24 0.34 7/23/14 0.28 0.6

Oahu 334-007 Waipio

Heights II

Wells

2500-01 2 NA 0.24 0.68 7/23/14 0.68 0.6

Oahu 334-010 Waipio

Heights III

Wells

2659-02 3 increasing 0.34 0.53 7/23/14 0.44 0.6


7

Table 1. (Continued) 1,2,3-Trichloropropane (TCP) Sampling Results (page 3 of 3)

Island Water

System

ID

Well or Well

Field

Well ID Sampling

Events


Maximum

Current MCL

(ppb) (ppb)

(ppb) (ppb)

Oahu 335-006 Hoaeae Wells 2301-05 3 stable 0.35 0.74 5/9/08 0.44 0.6

Oahu 335-014 Kunia I Wells 2302-04 4 decreasing 0.90 1.11 5/9/08 0.88 0.6

Oahu 335-035 Waipahu I

Wells

2400-03 5 increasing 0.44 0.54 8/21/14 0.53 0.6

Oahu 335-066 Waipahu II

Wells

2400-07 2 NA 0.67 0.87 8/21/14 0.85 0.6

Oahu 335-068 Kunia II Wells 2402-08 3 Increasing 1.02 1.48 9/9/14 1.46 0.6

Oahu 335-109 Kunia III

Wells

2401-05 2 NA 0.21 0.32 9/9/14 0.31 0.6

Oahu 335-116 Waipahu IV

Wells

2301-47 2 NA 0.24 0.65 8/21/14 0.55 0.6

Oahu 335-122 Waipahu II

Wells

2400-12 1 NA ---- 0.79 5/1/14 ---- 0.6

Oahu 367-010 Mililani I

Wells

2800-04 4 stable or

decreasing

2.80 4.01 5/1/13 2.80 0.6

Oahu 367-012 Mililani II

Wells

2859-06 2 NA 2.13 2.39 3/3/08 ---- 0.6

Oahu 367-013 Mililani III

Wells

2600-07 3 stable 1.09 2.80 5/1/13 1.96 0.6


8

Table 2. 1,2-Dibromo-3-Chloropropane (DBCP) Sampling Results

Island Water

System

ID

Well or Well

Field

Well ID Sampling

Events


Maximum

Current MCL

(ppb) (ppb)

(ppb) (ppb)


Well P4

5739-01 1 NA ---- 0.04 10/11/10 ---- 0.04


Well P6

5739-02 2 decreasing 0.12 0.2 5/19/08 0.12 0.04


Well P-5A

5739-04 2 NA 0.13 0.29 12/13/11 0.13 0.04

Maui 213-003 Haiku Well 5419-01 2 NA 0.18 0.18 NA 0.18 0.04

Maui 214-006 Napili A 5838-03 2 NA 0.13 0.13 9/23/14 0.13 0.04

Maui 254-001 Napili C 5320-02 2 NA ND 0.02 3/9/07 ND 0.04

Oahu 304-001 Maunaolu-

Smith Well

2603-01 2 NA 0.12 0.12 NA 0.12 0.04

Oahu 332-002 Hawaii

County Club

Well

3405-04 2 NA 0.12 0.12 7/21/14 0.12 0.04

Oahu 334-009 Waipio

Heights III

Wells

2659-01 3 decreasing 0.04 0.06 5/3/06 0.04 0.04

Oahu 335-015 Kunia II Wells 2402-01 2 NA 0.04 0.04 4/12/01 ---- 0.04

Oahu 367-010 Mililani I

Wells

2800-04 4 Stable or

increasing

0.14 0.28 5/1/13 0.27 0.04

Oahu 367-012 Mililani II

Wells

2859-06 2 NA 0.12 0.18 3/3/08 ---- 0.04

Oahu 367-013 Mililani III

Wells

2600-07 3 stable 0.05 0.16 5/1/13 0.13 0.04


9

Table 3. Trichloroethylene (TCE) Sampling Results

Island Water

System

ID

Well or Well

Field

Well ID Sampling

Events


Maximum

Current MCL

(ppb) (ppb)

(ppb) (ppb)

Oahu 345-013 Scholfield

Wells

2901-01 2 NA 19.4 40.6 6/18/13 ---- 5


Kunia 3 Well

2803-05 2 NA 6.6 7.1 2/20/08 6.60 5


Kunia 4 Well

2803-07 2 NA 2 3 2/20/08 2.00 5

Oahu 332-004 Waialua Wells 3405-02 3 stable 0.9 1 7/10/14 1.00 5

Oahu 332-002 Haleiwa Wells 3405-04 2 NA 0.5 0.7 9/22/14 0.70 5


10

Table 4. Dieldrin Sampling Results (page 1 of 2)

Island Water

System

ID

Well or Well

Field

Well ID Samples Trend Minimum Maximum Date of

Maximum

Current MCL

(ppb) (ppb)

(ppb) (ppb)

Oahu 331-005 Aina Koa

Wells

1746-01 2 stable 0.02 0.02 7/21/09 0.02 0.2

Oahu 331-039 Kaimuki

Pumping

Station

1748-01 3 decreasing 0.02 0.03 5/12/09 0.02 0.2

Oahu 331-144 Wilder Wells 1849-01 2 decreasing 0.01 0.03 7/7/15/09 0.01 0.2

Oahu 331-085 Manoa II

Wells

1948-01 1 NA ---- 0.01 6/29/09 ---- 0.2

Oahu 331-057 Kalihi

Pumping

Station

1952-

HS/LS

2 decreasing 0.01 0.02 8/26/09 0.01 0.2

Oahu 331-055 Kalihi Shaft 2052-01 2 decreasing ND 0.01 7/12/04 ND 0.2

Oahu 331-158 Kapalama

Wells

2052-01 3 decreasing 0.02 0.20 12/21/11 0.02 0.2

Oahu 331-087 Moanalua

Wells

2153-11 3 decreasing ND 0.01 4/8/08 ND 0.2

Oahu 360-003 Halawa Shaft

(Navy)

2255-32 2 stable or

decreasing

0.02 0.03 9/20/06 0.02 0.2

Oahu 331-023 Halawa Wells 2255-39 3 stable or

increasing

0.03 0.15 11/4/13 0.09 0.2


11

Table 4. (Continued) Dieldrin Sampling Results (page 2 of 2)

Island Water

System

ID

Well or Well

Field

Well ID Samples Trend Minimum Maximum Date of

Maximum

Current MCL

(ppb) (ppb)

(ppb) (ppb)

Oahu 335-005 Hoaeae Wells 2301-36 3 decreasing 0.02 0.04 10/2/07 0.02 0.2

Oahu 331-004 Aiea Wells 2355-04 2 decreasing 0.01 0.04 7/15/09 0.02 0.2

Oahu 331-031 Kaamilo Wells 2356-01 1 NA ---- 0.011 4/1/08 ---- 0.2

Oahu 331-099 Pearl City

Wells

2458-01 2 decreasing ND 0.012 6/27/05 ---- 0.2

Hawaii 106-004 Kulaimano

Deep Well

5006-01 1 NA ---- 0.011 9/11/02 ---- 0.2


12

Table 5. Atrazine Sampling Results (page 1 of 3)

Island Water

System

ID

Well

ID

Well or Well

Field

Well Use Historical

Conc.

Historical

Year

2014

Conc.

MCL

(ppb) (ppb) (ppb)

Maui NA

Kihei 3 Irrigation

9/23/2014 ND 3

Maui NA

Paia 16 Irrigation

9/23/2014 ND 3

Maui NA

Puunene 19 Irrigation

9/23/2014 ND 3

Maui NA

Puunene 6 Irrigation

9/23/2014 ND 3

Hawaii 102-

002

5814-

01

Laupahoehoe

Wells P-1

Public Drinking

Water

0.08 10/23/06 NS 3

Hawaii 102-

003

5814-

02

laupahoehoe

Wells P-2

Public Drinking

Water

0.06 2/28/07 NS 3

Hawaii 104-

002

6017-

05

Ookala Well Public Drinking

Water

0.69 8/13/02 NS 3

Hawaii 106-

004

5006-

01

Kulaimano

Deep Well

Public Drinking

Water

0.66 9/11/02 NS 3

Hawaii 109-

002

1229-

01

Pahala Well 1 Public Drinking

Water

0.08 2/26/07 NS 3

Hawaii 110-

001

2487-

01

Kalapana

Wells 1

Public Drinking

Water

0.054 9/11/02 NS 3

Hawaii 110-

002

2487-

02

Kalapana

Wells 2

Public Drinking

Water

0.05 9/16/02 NS 3

Hawaii 111-

002

2986-

01

Pahoa Wells 1 Public Drinking

Water

0.057 8/27/02 NS 3


13

Table 5. (Continued) Atrazine Sampling Results (page 2 of 3)

Island Water

System

ID

Well

ID

Well or Well

Field

Well Use Historical

Conc.

Historical

Year

2014

Conc.

MCL

(ppb) (ppb) (ppb)

Hawaii 114-

001

0831-

02

Ninole A Public Drinking

Water

0.07 3/27/07 NS 3

Hawaii 114-

002

0831-

03

Ninole B Public Drinking

Water

0.07 3/27/07 NS 3

Hawaii 115-

003

3900-

02

Maunaloa

Mac Nut

Well 2

Public Drinking

Water

0.09 3/12/08 NS 3

Hawaii 154-

004

5307-

01

Hakalau Well Public Drinking

Water

0.34 3/27/07 NS 3

Hawaii 161-

003

6528-

01

Haina Well Public Drinking

Water

0.47 8/28/02 NS 3

Kauai 400-

004

5923-

04

Kilohana C Public Drinking

Water

0.081 11/24/03 Offline 3

Kauai 400-

005

5923-

06

Kilohana G Public Drinking

Water

0.081 5/23/01 Offline 3

Maui 258-

001

5129-

01

Consolidated

Baseyard

Well 1

Public Drinking

Water

0.068 11/12/08 ND 3


14

Table 5. (Continued) Atrazine Sampling Results (page 3 of 3)

Island Water

System

ID

Well

ID

Well or Well

Field

Well Use Historical

Conc.

Historical

Year

2014

Conc.

MCL

(ppb) (ppb) (ppb)

Oahu 335-004 2301-

37

Hoaeae P-3 Public Drinking

Water

0.076 4/14/05 ND 3

Oahu 335-005 2301-

36

Hoaeae P-4 Public Drinking

Water

0.068 4/13/05 ND 3

Oahu 335-011 2302-

01

Kunia I P-1 Public Drinking

Water

0.052 3/19/03 ND 3

Oahu 335-012 2302-

02


Water

0.057 3/20/03 Offline 3

Oahu 335-014 2302-

04


Water

0.05 3/15/05 Offline 3

Oahu 355-001 2103-

03

Barbers

Point Shaft

Public Drinking

Water

0.1 5/22/13 NS 3

Oahu 360-003 2255-

32

Navy

Halawa Shaft

Public Drinking

Water

0.012 4/21/04 Offline 3


15

Table 6. Sampling Results for Carbon Tetrachloride, Chlordane, Heptachlor Epoxide, Tetrachloroethylene, and Ethylene Dibromide

Well ID Well or Well Field Contaminant Historical

Concentration

Historical

Year

2014

Concentration

MCL

(ppb)

(ppb) (ppb)

2803-05 Del Monte Kunia 3 Carbon Tetrachloride 1.40 2008 1.30 5

2255-38 Halawa Wells Chlordane 0.48 2013 0.53 2

2255-38 Halawa Wells Heptachlor Epoxide 0.03 2013 0.03 0.2

2902-02 Wahiawa II Wells Tetrachloroethylene 1.10 2009 1.00 5

5320-02 Maunaolu-Smith Well Ethylene Dibromide 0.08 2013 0.08 0.04

16

Figure 1. Locations of positive contaminant detections on Kauai and the TCP sampling

results

17

Figure 2. Locations of positive contaminant detections on Oahu and the TCP sampling

results

18

Figure 3. Locations of positive contaminant detections on Maui and the TCP sampling

results

APPENDIX G - 2015-2017ATRAZINE/DEGRADATION BY-PRODUCTS IN GROUNDWATER MONITORING PROJECT, DATED DECEMBER 29, 2017 (18 PAGES)

Seto, Joanna L

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PAGE 1 OF 17

ACRONYMS CFR Code of Federal Regulations CWS Community Water System EPA Environmental Protection Agency FIFRA Federal Insecticide, Fungicide, Rodenticide Act GWPP Groundwater Protection Program HAR Hawaii Administrative Rules HARC Hawaii Agricultural Research Center HC&S Hawaiian Commercial & Sugar HiDOA Hawaii Department of Agriculture HiDOH Hawaii Department of Health HRS Hawaii Revised Statutes HSPA Hawaii Sugar Planters Association LC-MS Liquid Chromatograph-Mass Spectrometer MCL Maximum Contaminant Level ND Not Detected NQ Not Quantifiable NTNC Non-Transient, Non-Community OSCO Oahu Sugar Company PBRC Pacific Biomedical Research Center SDWA Safe Drinking Water Act SDWB Safe Drinking Water Branch SLD State Laboratories Division

PAGE 2 OF 17

2015-2017

ATRAZINE/DEGRADATION BY-PRODUCTSIN GROUNDWATER MONITORING PROJECT

Table of Contents ACRONYMS ................................................................................................................................................................ 1

WHAT IS ATRAZINE? ................................................................................................................................................... 3

ATRAZINE USE IN HAWAII .......................................................................................................................................... 3

Sugarcane ............................................................................................................................................................... 3

Seed Corn ............................................................................................................................................................... 4

Recent Uses 2010‐2012 ......................................................................................................................................... 4

ATRAZINE FATE AND TRANSPORT .............................................................................................................................. 4

Degradation By‐Products ....................................................................................................................................... 5

Environmental Transport Mechanisms .................................................................................................................. 5

Leaching to Groundwater ...................................................................................................................................... 6

REGULATORY HISTORY FOR ATRAZINE IN GROUNDWATER ...................................................................................... 6

HiDOA Pesticide Regulations for Protection of Groundwater ............................................................................... 6

Safe Drinking Water Act ......................................................................................................................................... 7

HAWAII GROUNDWATER DATA– ATRAZINE AND DEGRADATION BY‐PRODUCTS ..................................................... 8

Discovery and Early Detections of Atrazine ........................................................................................................... 8

Safe Drinking Water Program Data ........................................................................................................................ 8

Groundwater Data from Irrigation Wells ............................................................................................................... 9

Historical Detection of Atrazine/9Degradation By‐Products in Hawaii’s Groundwater Resources ...................... 9

STATE GROUNDWATER PROTECTION PROGRAM .................................................................................................... 10

2015‐2017 ATRAZINE/DEGRADATION BY‐PRODUCTS11IN GROUNDWATER MONITORING DATA ......................... 11

ISLAND OF HAWAII ............................................................................................................................................... 11

ISLAND OF KAUAI ................................................................................................................................................. 12

ISLAND OF MAUI .................................................................................................................................................. 13

ISLAND OF OAHU ................................................................................................................................................. 15

SUMMARY AND RECOMMENDATIONS .................................................................................................................... 16

Table of Figures Figure 1. Atrazine Use in Hawaii (1964‐2012) .............................................................................................. 3

Figure 2. AAtrex Nine‐0 – (Based on 2010‐2012 sales records).Most purchased atrazine product in

Hawaii. .......................................................................................................................................... 4

Figure 3. Atrazine and Its Degradation By‐Products .................................................................................... 5

Figure 4. Dissipation Pathways of Applied Pesticide ................................................................................... 5

Figure 5. Sampling at HC&S well on Maui .................................................................................................. 10

Figure 6. SLD – Analysis Using LC‐MS ......................................................................................................... 11

Figure 7. Hawaii Groundwater Protection Strategy, June 2017 ................................................................ 17

PAGE 3 OF 17

Figure 1. Atrazine Use in Hawaii (1964‐2012)

WHAT IS ATRAZINE? Atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) which has been registered in the United States since 1958 is a pre- or post-emergence herbicide used for weed control. Atrazine is one of the most widely used herbicides in the United States where approximately 76.5 million pounds of atrazine active ingredient are used domestically each year (Environmental Protection Agency [EPA], 2003). About seventy-five percent (75%) of all field corn and sugarcane grown are treated with atrazine.

ATRAZINE USE IN HAWAII Records from various sources (including the Hawaii Department of Agriculture (HiDOA), Hawaii Sugar Planters Association (HSPA), Pacific Biomedical Research Center (PBRC), and the Hawaii Agriculture Research Center (HARC)indicate that the earliest use of Atrazine in Hawaii was in 1964.

Records indicate that atrazine usage declined from a high of about just over 400,000 pounds active ingredient per year in 1964 to about 75,000 pounds active ingredient in 2012. The sugar industry was, until recently, the largest user of atrazine in

Hawaii. In the past, atrazine was also used on pineapple, vegetable crops, corn and along highways, but at much lower levels than sugarcane. The drop in atrazine usage over time reflects the decline of sugarcane cultivation, cancellation of some uses and more restrictive label application rates. With the closure in 2016 of Hawaiian Commercial & Sugar (HC&S) on Maui (the last remaining sugar cane operation in Hawaii), the major usage of atrazine is now corn.

Sugarcane Weeds were a major concern for Hawaii sugarcane and cause more economic loss than all other pests combined. Thus, herbicides account for almost all of the pesticides used by sugarcane growers in Hawaii. The application rates of soil applied herbicides are higher in Hawaii compared to the U.S. mainland because tropical soils have high iron oxide content and a large adsorptive surface area. The average growth period for a crop of sugar cane ranged from 22 to 26 months so only a portion of the total acreage in sugar cane was harvested each year. In the mid-1930’s, a high of

PAGE 4 OF 17

140,000 acres were harvested. In 2016, the last sugar cane plantation with 34,300 total acres and representing 15,100 harvestable acres per year ceased operations.

Seed Corn Atrazine applications to corn are most often applied directly to soil as a pre-emergent herbicide. In Hawaii, corn is harvested approximately 110 days after planting. The seed corn growers in Hawaii grow three (3) crops per year, but they are not planted within the same field each year due to concerns about cross contamination with different genetic varieties of corn and crop rotation to control insect pests and maintain the soil fertility. The total amount of atrazine allowed is 2.5 pounds of active ingredient per acre for a calendar year. According to the label, the total amount of atrazine applied may not exceed 2.0 pounds of active ingredient in a single application or 2.5 pounds (pre- and post-emergence combined) of active ingredient per acre per calendar year.

Recent Uses 2010‐2012 As of 2012, 20 atrazine products were registered in Hawaii. From 2010 to 2012, seven (7) of these atrazine products were used in Hawaii. All of the atrazine used in Hawaii is for agriculture. Seed corn, sugarcane, sweet corn and macadamia nuts were the only crops recently using atrazine in Hawaii. The average atrazine sales in the State of Hawaii for 2010-2012 are 80,912 pounds of active ingredient per year. About 94% of the atrazine sold in Hawaii was used for weed control on sugarcane. A very small fraction, 44 pounds per year is used in macadamia orchards, and 326 pounds in sweet corn production. Seed corn production accounts for 6% of the total atrazine used statewide, at an average of 4,771 pounds per year.

ATRAZINE FATE AND TRANSPORT When properly usedpesticides protect crop quality while reducing impacts from weeds and/or insect pests. However, as a result of a pesticide’s chemical characteristics, toxicity, application practices and local environmental conditions at the site of application, pesticides can have impacts on non-target species. These range from unsafe exposures to farm workers or applicators who do not follow the label instructions, to inadvertent damage to crops and offsite movement of pesticides from runoff, erosion, volatilization, spray drift or migration to groundwater.

Figure 2. AAtrex Nine‐0 – (Based on 2010‐2012 sales records).Most purchased atrazine product in Hawaii.

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AGE 5 OF 17

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PAGE 6 OF 17

previously treated with this herbicide resulting in reduced efficiency has been shown in Hawaii and other locations. Predicting the long-term behavior of atrazine in soil is challenging because of the complex interaction of these different dynamic processes on degradation of pesticides. Leaching to Groundwater In Hawaii, leaching to groundwater is a key pathway that has the potential to introduce atrazine and other soluble chemicals into drinking water supplies, into streams through groundwater recharge and eventually to near shore marine waters. Atrazine that remains in the soil can dissolve into infiltrating rainwater and be carried down over time to groundwater aquifers. Within coastal zones, atrazine can leach into shallow groundwater and seep into bays, streams and near shore water. Like surface runoff, heavy rain events on bare soils treated with atrazine are likely to result in increased losses to groundwater. In groundwater, both atrazine and its major breakdown products have long half lives because they are resistant to degradation.

REGULATORY HISTORY FOR ATRAZINE IN GROUNDWATER Pesticide use is regulated by both the EPA and the State of Hawaii through existing authorities under the Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA);Hawaii Pesticide Law (Chapter 149A, Hawaii Revised Statutes [HRS]); and Hawaii Administrative Rules (HAR) Title 4- Department of Agriculture, Subtitle 6 - Division of Plant Industry, Chapter 66 - Pesticides. Federal law requires that before selling or distributing a pesticide in the United States, a person or company must obtain registration or license from EPA. Under federal law, EPA's Office of Pesticide Programs is responsible for evaluating the human health and environmental risk and ensuring the safety of pesticides when properly applied. To make such determinations, EPA requires more than a 100 different scientific studies and tests from the producer of the pesticide.

HiDOA Pesticide Regulations for Protection of Groundwater HiDOA has several statutes and rules that apply to groundwater protection. They are listed below:

HRS§149A-14 - Refusal, Cancellation, or suspension of the license. Provides authority to refuse or cancel a pesticide should the proposed use meet certain criteria.

HRS§149A-32.5 - Cancellation or suspension of pesticide uses.Provides authority to

suspend, cancel or restrict the use of pesticides / pesticide uses if unreasonable adverse effects could result from that use.

HAR §4-66-32.1 - Evaluation of pesticide uses. This section refers to unreasonable

adverse effects for products/chemicals already being used. Of particular interest in this section is where it states that, “[t]he head shall evaluate a licensed pesticide when unreasonable adverse effects to humans or the environment have been documented and associated with the use of that pesticide.” The circumstances include public health hazard, pesticides in drinking water that are present at levels that equal or exceed 20% of the federal or state health standards or advisory, pesticides residues in food or feed that are present at levels exceeding established tolerances and several other criteria. Evaluation of the pesticide could ultimately result in no change, restriction of a use, refusal to renew a license, or cancellation or suspension of the license.

PAGE 7 OF 17

HAR §4-66-34 - Applications for licensing pesticides and for approval of non-

chemical pest control devices. Section (5) states "[i]f requested by the head, the applicant for a pesticide shall provide the complete formula of the pesticide including active and inert ingredients and a description of tests and the results thereof on which claims are based, including efficacy, residue, safety and other supporting data that shows the pesticide shall perform its intended function without unreasonable adverse effects.

For new active ingredients, HiDOA requests environmental fate information to determine leachability of the chemical in Hawaii soils. The potential to leach is investigated in a phased approach. If a pesticide is shown “likely to leach,” a full groundwater review is required. In this case, full groundwater data is requested from the company, based on 40 CFR §158.290. After data are received, the information is forwarded on to the Water Resources Research Center at the University of Hawaii for reviewby a hydrologist. This review will look at specific environmental fate characteristics, the use pattern in all available products containing that active ingredient, Hawaii conditions, to determine the likelihood of leaching. At the end of this review, a determination is made to license products containing that chemical, require state restriction, or deny licensing.

Safe Drinking Water Act HiDOH has been authorized by EPA to administer requirements of the Safe Drinking Water Act (SDWA) in Hawaii. Hawaii’s authority is found in HRS Chapter 340E. Hawaii’s requirements for public water systems are found in HAR, Title 11, Chapter 20, entitled “Rules Relating to Public Water Systems.” State and federal drinking water regulations require that drinking water systems be routinely tested for a large number of chemical and biological contaminants. Required testing includes 23 pesticides, including atrazine, for which the EPA has established standards known as maximum contaminant levels (MCLs). The MCL for atrazine was set at 3.0 micrograms per liter (μg/l) or parts per billion (ppb). The SDWA does not require testing for breakdown products of these pesticides. Hawaii’s requirements include all federal drinking water standards as well as Hawaii standards. These standards apply to all public water systems which are systems that serve 25 or more persons per day at least 60 days per year or have 15 or more service connections. Monitoring requirements for atrazine and the other contaminants were assigned to two (2) types of public water systems known as “community” systems (CWS) which are systems that serve residential populations and “non-transient non-community” systems (NTNC) which are systems that serve non-residential but constant populations such as working places. A third type of system “transient non-community” systems,which are systems which serve a transient population, were not required to sample for these contaminants due to the limited exposure of the service population. Because of groundwater concerns, EPA established anMCL of 3.0ppb in the early 1990s. Also, in the early 1990s, the producers of the pesticide voluntarily instituted some risk reduction measures because of concerns about surface water and groundwater contamination. One of the measures was to classify atrazine as a restricted use pesticide. Other measures of interest to

PAGE 8 OF 17

Hawaii crops include reducing application rates for corn, deletion of all uses for vegetation control on non-cropland, requiring that post-emergence application be made to corn before it reaches 12 inches in height, deleting pineapple use, and requiring setbacks from wells and surface water. In 2003, as part of the atrazine re-registration process, EPA made further changes to the atrazine label to minimize impacts to drinking water, reduce worker exposures and require surface and groundwater monitoring by the registrant in areas shown to be impacted with atrazine above EPA’s level of concern.

HAWAII GROUNDWATER DATA– ATRAZINE AND DEGRADATION BY‐

PRODUCTS Discovery and Early Detections of Atrazine Prior to 1993, atrazine was not routinely monitored in drinking water. The HSPA was the first to identify atrazine in groundwater and voluntarily established a monitoring program in Hawaii. At the time there was no MCL and the health advisory level was 25 ppb. In 1983, HSPA alerted the HiDOH about detectable levels of atrazine found in Kunia and Waipahu on Oahu. Subsequent groundwater sampling by HSPA in the early 1980s in areas of high agricultural use found about 40% of the sources had detectable levels of atrazine. In 1986, elevated levels were found in Pepeekeo Spring and Kihalani Spring on the Hamakua Coast of Hawaii Island which measured 4.1 and 2.3 ppb, respectively. The monitoring found that areas of high rainfall together with permeable soils were more susceptible to atrazine groundwater contamination. Throughout the 1980s and 1990s, HSPA has been an active participant in monitoring and evaluating atrazine trends in Hawaii’s groundwater. Also, in partial fulfillment of EPA’s re-registration requirements for atrazine, the manufacturer, Ciba-Geigy agreed to conduct groundwater monitoring in 19 states that represented the major atrazine use areas in the country. Hawaii’s component of The Ciba Crop Protection Groundwater Monitoring Study for Atrazine and its Major Degradation Products in the United Statesbegan in 1992 and included active participation from the HiDOA and HSPA. During the early 1990s, numerous sugar companies were still in operation and actively using atrazine. The purpose of the study was to assess the presence of atrazine and its degradation products in groundwater in areas of high atrazine use. The focus of the study was on drinking water supplies, particularly those with hydrogeologic features that increased vulnerability to contamination, but also evaluated shallow irrigation wells, and wells at different depths to better understand how and where atrazine may occur.

Safe Drinking Water Program Data Since 1993, the Safe Drinking Water Branch (SDWB) has routinely sampled community drinking water systems. The most current water quality results by water system show all detectable levels of atrazine in the state water supply are well below the MCL of 3.0 ppb. Between 1993 and 1995, HiDOH tested community drinking water systems every three (3) months for atrazine. Water systems that did not detect atrazine could reduce the sample frequency for atrazine to once every three (3) years, or twice within a one (1) year period every three (3) years depending on the system population. Water systems that had detectable levels of atrazine were required to sample quarterly and could reduce sampling to annual if the concentration of atrazine was reliably and consistently less than the MCL.

PAGE 9 OF 17

There are currently 129 active (CWS and NTNC) systems serving a population of 1,502,575. The remainder of the population is served by transient public water systems and by non-public water systems which include individual well, stream, or rainwater catchment sources. Since 1993, no public water system tested in Hawaii has exceeded the MCL for atrazine.

Groundwater Data from Irrigation Wells State and federal law do not require routine pesticide monitoring of irrigation wells. In Hawaii, no ongoing monitoring of these wells is in place, and current water quality data are not available for pesticides in irrigation wells. However, the research conducted by Ciba-Geigy and HSPA provide a useful snapshot of historic impacts of sugarcane herbicide use on groundwater.Irrigation wells in areas of active sugarcane cultivation were evaluated as part of the 1992-1994 Ciba-Geigystudy. Eight (8) out of 14 irrigation wells sampled on Oahu had detections of atrazine or a degradation by-product. An earlier study by HSPA reported data collected by agricultural operators between 1983 and 1986 from eight (8) irrigation wells in the Ewa Plain, Waipahu and Waialua on Oahu. However, only one (1) of these samples from an irrigation well in Waialua, had a detection of atrazine (0.6 ppb). Detection limits ranged from 0.5 to 1.0 ppb, and the sampling may have missed lower concentrations consistent with those found in the Ciba-Geigystudy. On Maui, 12irrigation wells were sampled with detections in six (6)wells ranging from 0.13 ppb to 0.3 ppb atrazine and 0.12 to 0.63 ppb atrazine degradation by-products. The highest detection was at a well depth of 380 ft. On Kauai, there were no detections of atrazine or its degradation by-products in any of four (4) irrigation wells sampled during the Ciba-Geigystudy period. The SDWB dataset includes one (1) additional irrigation well sampled on Kauai at Barking Sands. A single sample was taken in 1988 with a reported detection of 3.5 ppb, however, the original datasheet or other information regarding the sampling is not available. The depth and status of the well is unknown and the well was not re-sampled.

Historical Detection of Atrazine/Degradation By‐Products in Hawaii’s Groundwater

Resources Based on the latest Groundwater Contamination Maps from 2011, the following table show the number of sample locations with Atrazine and Degradation By-Products detected in groundwater, by island.

ISLAND Atrazine Desethyl Atrazine

Desisopropyl Atrazine

Desethyl, Desisopropyl Atrazine

Kauai 3 0 0 0 Oahu 13 13 3 3 Maui 5 6 0 1 Hawaii 32 18 3 2

PAGE 10 OF 17

Figure 5. Sampling at HC&S well on Maui

STATE GROUNDWATER PROTECTION PROGRAM

Hawaii’s Groundwater Protection Program (GWPP) is a non-regulatory program whose goal is to protect human health and sensitive ecosystems by protecting groundwater resources. Its focus is on water quality assessment and on developing pollution prevention and protection measures. While originally developed as a planning and coordinative activity, the GWPP has recognized the need for developing its own groundwater monitoring program for contaminants of interest or concern. Recently, the program acquired analytical equipment, a liquid chromatograph-mass spectrometer (LC-MS), to analyze for a wide variety of contaminants and is currently developing methods and capacity at the State Laboratory. The June 2017 Hawaii Groundwater Protection Strategy1 is a coordinated effort within the HiDOH “to safeguard groundwater quality and public health by protecting Hawaii’s groundwater from contamination” using multiple branch and office resources and funds

(in parantheses). The Hawaii Department of Health Coordinating Branches/Offices include: SDWB (GW106/DWSRF 15%), Wastewater Branch (CWSRF), Clean Water Branch (SW106),Solid & Hazardous Waste Branch (SHWB), and Hazard Evaluation and Emergency Response Office (HEER). This report is a result of Goal 1 - Monitor and assess groundwater quality and Goal 2 - Identify and prioritize groundwater contamination threats for the recognized 2017 priority threat of “Agricultural chemicals.” The GWPP can improve the State’s knowledge of the current groundwater condition in two (2) major ways. First, with its flexibility to sample both drinking water and non-drinking water groundwater sources, HiDOH will be able to confirm, track trends and better define areas of the state impacted by contaminants such as atrazine and its degradation by-products. Second, groundwater sampling can be expanded beyond the list of contaminants required for drinking water testing. It will enable the State to sample for new contaminants of emerging concern such as new pesticides, pharmaceuticals, degradation by-products and other contaminants not regulated by drinking water rules. One of the GWPP’s first monitoring efforts was to conduct Atrazine/Degradation By-Products monitoring of groundwater resources. The GWPP will sample groundwater sources that have reported positive results for atrazine/degradation by-products from 1983to2011 and for which no subsequent monitoring has taken place.Samples were also collected from groundwater wells near areas where atrazine was or is currently being used. 1The Hawaii Groundwater Protection Strategy, June 2017, may be found at the end of this report.

PAGE 11 OF 17

Figure 6. SLD – Analysis Using LC‐MS

Samples were collected by GWPP staff and analyzed by the HiDOH - State Laboratories Division (SLD). Analysis was conducted using EPA Method 536 – “Determination of TriazinePesticides and Their Degradates in Drinking Water by Liquid Chromatography Electrospray Ionization Tandem Mass Spectrometry (LC/ESI-MS/MS).”The contaminant detection level for atrazine and its degradation by-products was less than 0.03ug/l (ppb).

2015‐2017 ATRAZINE/DEGRADATION BY‐PRODUCTSIN GROUNDWATER

MONITORING DATA

ISLAND OF HAWAII

SAMPLE POINT SAMPLE

DATE ATRAZINE

ATRAZINE, Desethyl

ATRAZINE, Desisopropyl-

ATRAZINE, Desethyl,

Desisopropyl-

Ninole (Punaluu) A&B 12/14/2015 0.06(0.061) 0.09(0.13) ND ND

Pahoa Wells 1&2 12/14/2015 ND (0.057) ND ND ND

Keauohana (Kalapama) 1&2

12/14/2015 ND (0.054) ND ND ND

Naalehu Well 12/14/2015 ND (0.061) ND ND ND

Hakalau Well &Iki Spring 12/15/2015 0.10(0.34) 0.38(0.046) ND ND

Pahala Well 1&2 12/15/2015 0.09(0.14) 0.09 ND ND

Kulaimano Well A 12/15/2015 0.24(0.66) 0.10(0.13) ND ND

Kaieie Spring 12/15/2015 0.23(0.23) 0.28(0.52) ND ND

Chaves Spring 12/15/2015 0.13(0.13) 0.06(0.14) ND ND

OokalaWell 12/15/2015 0.30(0.58) 0.49(0.93) ND ND

Laupahoehoe Wells P1&P2

12/15/2015 0.05(0.1) 0.06(0.17) ND ND

Maunaloa Mac Nut Well 2

2/9/2016 ND (0.09) ND ND ND

Paauilo Well 2/10/2016 0.47(0.55) 1.04(1.14) 0.04(0.05) 0.04(0.05)

HakalauIki Spring 2/9/2016 ND(0.23) ND ND ND

Hawaii Beef Producer (DBA Big Island Meat)

2/10/2016 0.34(0.21) 0.37(0.39) ND ND

PAGE 12 OF 17

SAMPLE POINT SAMPLE

DATE ATRAZINE

ATRAZINE, Desethyl

ATRAZINE, Desisopropyl-

ATRAZINE, Desethyl,

Desisopropyl-

HELCo Keaau Well 2/9/2016 ND (0.26) ND ND ND

(x.xx) – Indicate previous positive detection results, based on Groundwater Contamination Maps (2011). (BOLD) – Indicate new positive result. Atrazine and/or its degradation by-products have been previously detected in the following groundwater sources:

SAMPLE POINT CONTAMINANTS DETECTED Waiuliuli Spring Atrazine, Desethyl- (2) Haina Well Atrazine, Desethyl- (2) Paauilo Shaft Atrazine (1) Ookala Shaft Atrazine, Desethyl-, Desisopropyl-, Desethyl-Desisopropyl (#) Kaiaakea Spring Atrazine, Desethyl- (2) Maukaloa Spring Atrazine, Desethyl-, Desisopropyl-(3) Pepeekeo Sugar Mauka Atrazine, Desethyl- (2) Papaikou Deep Well Atrazine (1) Punaluu TH-2 Atrazine, Desethyl- (2) Manowaiopae Spring Atrazine (1)

These groundwater sources were not sampled under this project, due to the source being inactive, abandoned/sealed, or not operational at the time of sampling.

ISLAND OF KAUAI

SAMPLE POINT SAMPLE

DATE ATRAZINE

ATRAZINE- Desethyl

ATRAZINE- Desisopropyl

ATRAZINE-Desethyl-

Desisopropyl

Kilohana A 2/29/2016 ND ND ND ND

Kilohana B 2/29/2016 ND ND ND ND

Kilohana I 2/29/2016 ND ND ND ND

Puhi Well 3 2/29/2016 ND ND ND ND

Puhi Well 4 2/29/2016 ND ND ND ND

Puhi Well 5A 2/29/2016 ND ND ND ND

Puhi Well 5B 2/29/2016 ND ND ND ND

Garlinghouse Tunnel

2/29/2016 ND ND ND ND

Kapilimao Well 4/11/2016 ND ND ND ND

Waimea Deep Well A

4/11/2016 ND 0.06 ND ND

Waimea Deep Well B

4/11/2016 ND 0.04 ND ND

Paua Valley Well 4/11/2016 ND 0.03 ND ND

Waipao Valley Well B

4/11/2016 ND ND ND ND

PAGE 13 OF 17

SAMPLE POINT SAMPLE

DATE ATRAZINE

ATRAZINE- Desethyl


ATRAZINE-Desethyl-

Desisopropyl

Koloa Well D 4/11/2016 ND ND ND ND

Koloa Well F 4/11/2016 ND ND ND ND

Hanapepe Well #4 4/11/2016 ND ND ND ND

Hanamaulu Well 4 3/9/2017 ND ND ND ND

Kalepa Well 3/9/2017 ND 0.03 ND ND

Nonou 9-1C 3/9/2017 ND ND ND ND

Nonou 9-1B 3/9/2017 ND ND ND ND

Anahola Wells 1,2,3

3/9/2017 ND ND ND ND

Kaulaula Well 4/11/2017 ND ND ND ND

Mana Shaft 4/11/2017 ND ND ND ND


SAMPLE POINT CONTAMINANTS DETECTED Barking Sands Atrazine (1) Kilohana C Atrazine (1) Kilohana G Atrazine (1)

These groundwater sources were not sampled under this project, due to the source being inactive, abandoned/sealed, or not operational at the time of sampling. The drinking water supply at the Gay & Robinson plantation in Olokele was sampled from 1993 to 2011, with a single detection (0.081 ppb) in 2008, the last year of the sugar operation there.The operator declined a request to collect samples at this source.

ISLAND OF MAUI

SAMPLE POINT SAMPLE

DATE ATRAZINE

ATRAZINE- Desethyl


ATRAZINE-Desethyl-

Desisopropyl

HCS – Puunene Pump 6

6/8/2016 0.05(0.08) 0.06(0.1) ND ND

HCS – Puunene Pump 7A

6/8/2016 0.03 0.11(0.09) ND ND

HCS – Kihei Well 1

6/8/2016 0.07(0.12) 0.14(0.24) ND ND (0.07)

HCS – Puunene Pump 9

6/8/2016 0.03 0.04(0.06) ND ND

HCS – Paia 17 6/8/2016 0.06(0.23) 0.10 ND ND

Olowalu Shaft 10/19/2016 ND ND ND ND

PAGE 14 OF 17

SAMPLE POINT SAMPLE

DATE ATRAZINE

ATRAZINE- Desethyl


ATRAZINE-Desethyl-

Desisopropyl

OlowaluElua Well 10/19/2016 ND ND ND ND

Kaanapali Well P4

10/19/2016 ND ND ND ND

Kaanapali Well P5

10/19/2016 ND ND ND ND

Kaanapali Well P6

10/19/2016 ND ND ND ND

Maui Highlands Well 1

4/25/2017 ND ND ND ND

Maui Highlands Well 2

4/25/2017 ND ND ND ND

Consolidated Baseyard Well No.1

4/25/2017 ND ND ND ND

Consolidated Baseyard Well No. 2

4/25/2017 ND 0.05 ND ND

Hamakuapoko Well 1

5/25/2017 ND 0.04 ND ND

Hamakuapoko Well 2

5/25/2017 ND 0.04 ND ND

Pookela Well 5/25/2017 ND ND ND ND

Kaupakulua Well 7/17/2017 ND ND ND ND

Haiku Well 7/17/2017 ND ND ND ND

W. Kuiaha Meadows Well

7/18/2017 ND ND ND ND

Maunaolu-Smith Well

7/18/2017 ND ND ND ND

Omaopio-Esty Well

7/18/2017 ND ND ND ND

Pukalani Golf Course Well

7/19/2017 ND ND ND ND

Launiupoko Well No. 3

8/24/2017 ND ND ND ND

Waiale Well 1 8/24/2017 ND 0.03 ND ND

Waiale Well 2 8/24/2017 ND 0.04 ND ND


SAMPLE POINT CONTAMINANTS DETECTED Kihei Well 3 Atrazine, Desethyl- (2) Paia 16 Atrazine, Desethyl- (2)

PAGE 15 OF 17

SAMPLE POINT SAMPLE

DATE ATRAZINE

ATRAZINE- Desethyl


ATRAZINE-Desethyl-

Desisopropyl

These groundwater sources were not sampled under this project, due to the source being inactive, abandoned/sealed, or not operational at the time of sampling

ISLAND OF OAHU

SAMPLE POINT SAMPLE

DATE ATRAZINE

ATRAZINE- Desethyl


ATRAZINE-Desethyl-

Desisopropyl

Kipapa Acres Well

6/6/2016 ND ND ND ND

Hoaeae Well P-4 11/16/2016 0.04 ND(“Estimated”NQ<0.05)

ND ND

Kunia Wells I (P-2)

11/16/2016 ND ND(0.09) ND ND

Kunia Wells I (P-4)

11/16/2016 ND(0.05) ND ND ND


SAMPLE POINT CONTAMINANTS DETECTED Haleiwa Battery Atrazine (1) Wailua Battery P-2 Atrazine, Desethyl- (2) Kunia Battery Atrazine, Desethyl- (2) OSCO Ewa Pump 15 Atrazine, Desethyl- (2) OSCO Ewa Pump 3 Atrazine, Desethyl- (2) OSCO Ewa Pump 5 Atrazine, Desethyl- (2) OSCO Ewa Pump 7A Atrazine, Desethyl- (2) OSCO Ewa Pump 10 Atrazine, Desethyl- (2) OSCO Ewa Pump 24 Atrazine, Desethyl-, Desisopropyl-, Desethyl-Desisopropyl(4) OSCO Ewa Pump 20 Atrazine, Desethyl-, Desisopropyl-, Desethyl-Desisopropyl(4) OSCO Ewa Pump 21 Atrazine, Desethyl-, Desisopropyl-, Desethyl-Desisopropyl(4) Barbers Point Shaft Atrazine, Desethyl- (2)

These groundwater sources were not sampled under this project, due to the source being inactive, abandoned/sealed, or not operational at the time of sampling.

PAGE 16 OF 17

SUMMARY AND RECOMMENDATIONS A review of the historical water quality data indicates a direct connection between historical/current applications of atrazine for agricultural uses and subsequent detections in groundwater.Areas expected to be most vulnerable to contamination include those with high rainfall, thin permeable soils, limited weathering of rocks in the unsaturated zone, shallow depths to groundwater, and a high rates of atrazine use. Contamination of groundwater by atrazine and its degradation by-products has primarily been detected within or hydraulically down gradient from areas currently or previously used for sugarcane cultivation. Atrazine use in Hawaii has decreased over the years due to label restrictions and the decline of the sugar industry. Until recently (2016), the largest user in the state was the sugar industry on Maui. With the closure of the last sugar cane plantation, atrazine usage has shifted to sweet corn and seed corn production. Data from the “Atrazine/Degradation By-Products in Groundwater Monitoring Project” conducted by the HiDOH from 2015-2017 has generally shown a downward trend in the levels of atrazine and its degradation by-products detected in groundwater throughout the state. Several wells with prior detections (at low concentrations below 0.10ug/l) are now “not detected.” Atrazine and its degradation by-products were detected in several wells that were previously negative or not in existence in 2011 (these wells are located in areas where atrazine was previously or currently used). Many of the historical detections associated with agriculture and irrigation wells were not sampled for this project, as closure of sugar cane operations have made these wells inactive, abandoned, sealed, or not operational. Several wells associated with drinking water systems were not sampled, as the wells were not operational at the time of project sampling. After reviewing thegroundwater and drinking water data, HiDOH recommends the following:

Resample new detections (to confirm that contaminants are present); Conduct sampling at sources (that were not sampled under this project) which have

been brought backinto operation; Continuesampling in the limited areas where atrazine is still being used (sampling may

be done under a Pesticides in Groundwater Monitoring Project), as it has been shown that there is a connection between the use of atrazine and detection in groundwater; and

Conduct periodic sampling (possibly once every 5-10 years) of historical detection sites to assesscontinuing contamination trends in areas of past atrazine use. As lands in former agriculture and sugar cane cultivation are converted to housing developments or other uses, groundwater quality in these areas should be monitored to ensure that the quality of water meets the increased demands for drinking water resources.

These recommendations are based on the Hawaii Groundwater Protection Strategy:

Goal 1 - Objectives 1 and 3 Goal 2 - Objective 2 Goal 3 - Objective 1 (HEER and HiDOA)

PAGE 17 OF 17

Figure 7. Hawaii Groundwater Protection Strategy, June 2017

APPENDIX H - ASSESSING THE PRESENCE AND POTENTIAL IMPACTS OF PHARMACEUTICAL AND PERSONAL CARE PRODUCTS (PPCPS) ON GROUNDWATER AND DRINKING WATER: PRELIMINARY FINDINGS, DATED DECEMBER 29, 2017 (90 PAGES)

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Page 3 of 91

Acronyms

CEC Contaminant of Emerging Concern

CWB Clean Water Branch

DOH Department of Health

LC‐MS‐MS Liquid Chromatography‐Mass Spectroscopy‐Mass Spectroscopy

MDL Method Detection Level

MGD Million Gallons per Day

MRL Method Reporting Level

OSDS On‐site Sewage Disposal System

PPCP Pharmaceuticals and Personal Care Products

RO Reverse Osmosis

SDWB Safe Drinking Water Branch

WQS Water Quality Standards

WWB Wastewater Branch

WWRF Wastewater Reclamation Facility

WWTP Wastewater Treatment Plant

Page 4 of 91

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Page 5 of 91

Assessing the Presence and Potential Impacts of

Pharmaceuticals and Personal Care Products (PPCPs)

on Groundwater and Drinking Water

Acronyms ...................................................................................................................................................... 3

Introduction .................................................................................................................................................. 7

Why are PPCPs a Potential Water Quality Issue? ......................................................................................... 8

Alternative Water Sources ‐ Water Reuse ................................................................................................ 8

Potential Contamination Sources ‐ On‐site Wastewater Disposal Systems (OSDS) ~ Cesspools and

Septic Systems .......................................................................................................................................... 9

Fate and Transport of PPCPs in the Environment ....................................................................................... 11

Receptors of Contamination from PPCPs Sources ...................................................................................... 12

What Contaminants are We Looking for? .................................................................................................. 12

LC‐MS‐MS ENDOCRINE DISRUPTORS (POSITIVE MODE – SPE) ............................................................... 13

LC‐MS‐MS ENDOCRINE DISRUPTORS (NEGATIVE MODE – SPE) ............................................................. 13

Where and Why are we Looking for these Contaminants? ........................................................................ 14

Determine Sampling locations/sites: WWRF/WWTP/OSDS Areas ........................................................ 14

Determine Receptors of Reuse Water: Groundwater ........................................................................... 14

Summary of Sample Results ....................................................................................................................... 15

PPCPs found in Raw Influent Wastewater .............................................................................................. 15

PPCPs found in Raw Influent Wastewater and Treated Reuse Effluent Water ...................................... 17

PPCPs found in Treated Reuse Effluent Water ....................................................................................... 26

PPCPs found in Groundwater in Areas with high density of OSDS ......................................................... 29

Summary ..................................................................................................................................................... 31

RAW WASTEWATER INFLUENT ............................................................................................................... 31

RAW WASTEWATER INFLUENT and TREATED REUSE EFFLUENT WATER FROM SELECTED

WWRF/WWTP ......................................................................................................................................... 32

TREATED REUSE EFFLUENT WATER FROM SELECTED REUSE WATER FACILITIES ................................... 33

Data Observations ................................................................................................................................... 34

Data Issues .............................................................................................................................................. 34

GROUNDWATER IN AREAS WITH HIGH DENSITY OF OSDS or ELEVATED NITRATE LEVELS .................... 34

Page 6 of 91

Further Action(s) ......................................................................................................................................... 35

Additional Monitoring Needs and Resources:Source: ............................................................................ 35

Criteria for areas where reuse wastewater should not be used: ........................................................... 35

Potential need for Program changes: ..................................................................................................... 35

APPENDIX A ‐ PPCPs ~ Analytes Sampling and Reporting Information ...................................................... 36

APPENDIX B ‐ Monitoring Results ................................................................................................................. 0

Page 7 of 91

Introduction The State of Hawaii is interested/involved in the use of reclaimed wastewater as an alternative water

source. While the quality of reclaimed wastewater may meet the Hawaii State Water Quality Standards

(WQS), Hawaii Administrative Rules (HAR), Chapter 11‐54, and be free of drinking water contaminants,

as listed in HAR, Chapter 11‐20, there remains a concern regarding other contaminants. While there are

guidelines on the use and quality of reclaimed wastewater (R1/R2), very little is known about other

potential contaminants of concern (CEC), such as pharmaceuticals and personal care products (PPCPs) in

wastewater and reclaimed wastewater.

PPCPs have recently emerged as CECs due to their potential impact om water quality and aquatic life.

Will proposed uses of reclaimed wastewater for irrigation, dust suppression and other uses on land

overlying impact underlaying aquifers and groundwater resources?

While the potential impact of the use of reclaimed wastewater on water resources is a primary concern,

PPCPs may originate and enter the environment through other mechanisms that may impact the State’s

water resources.

Waste disposal through On‐site Disposal Systems (OSDS), land disposal of sewage biosolids, veterinary

use of antibiotics and other drugsmay also be other potential contamination sources for PPCPs to enter

our water resources.

Source: U.s. Environmental Protection Agency, Office of Research Development (March 2006)

Page 8 of 91

Why are PPCPs a Potential Water Quality Issue? Alternative Water Sources ‐ Water Reuse The DOH Wastewater Branch has refined its data collection methods to more accurately measure the

amount of recycled water being used. As such, the reuse amount for 2015 onward is based on operator

reports rather than estimations. Operator reports provide more accurate figures because they account

for declines in use due to rainy periods, off‐spec water, and equipment malfunctions. In 2015, 16.3

million gallons per day (MGD) were supplied for reuse. In 2016, 17.2 MGD were supplied.

The combination of growing population and limited drinking water resources is reducing the availability

and quality of our drinking water supplies. In addition, we continue to experience problems as a result

of the disposal of wastewater. Wastewater management practices that protect, conserve, and fully

utilize water resources are vital to Hawaii. Increasing the safe use of recycled water can greatly assist in

meeting the State’s water requirements, enhance the environment, and benefit public health by

preserving resources upon which public health protection is based. DOH has long been an advocate for

water reuse as long as it does not compromise public health and our valuable water resources. Promoting

the use of recycled water is one of the DOH’s high priority goals.

Water reuse has moderately increased

in Hawaii over the past several years.

There are now 39 wastewater

treatment facilities that produce

recycled water. Of these 39 facilities,

11 are R‐1 facilities, which produce the

highest quality recycled water, while

the remaining facilities produce R‐2

and R‐3 water.

In January 2016, the DOH Wastewater

Branch (WWB) revised the Reuse

Guidelines and separated it into two

volumes. Volume 1: Recycled Water

Facilities addresses technical

requirements to be met for various qualities of recycled water, and requirements to construct or modify a

wastewater reclamation facility. Volume II: Recycled Water Projects covers the application process to use

recycled water for various purposes and establishes best management practices that apply to the end

user. See http://health.hawaii.gov/wastewater/home/reuse/.

In order to assess potential impacts on groundwater quality, the Groundwater Protection Program will

study the quality of groundwater, wastewater and reuse water to evaluate the quality of these waters and

assess the potential impact of the use of reclaimed wastewater on groundwater, surface water, and

drinking water. The project will analyze these waters for a comprehensive and wide variety of emerging

contaminants, including endocrine disrupting chemicals, pharmaceuticals, and trace elements.

Page 9 of 91

Wastewater from a leaking cesspool

Potential Contamination Sources ‐ On‐site Wastewater Disposal Systems

(OSDS) ~ Cesspools and Septic Systems Wastewater treatment facilities and septic systems

treat wastewater before discharging it to the

environment, but cesspools do not. Cesspools are

little more than holes in the ground, an outmoded

15th century technology that discharges raw,

untreated human waste directly into the ground,

where it can spread and contaminate groundwater,

drinking water sources, streams, and the ocean by

releasing disease‐causing pathogens and other

contaminants including PPCPs. In order to protect

public health, new cesspools in Hawaii are currently

prohibited, and existing cesspools should be gradually phased out through mandatory connection to a

centralized wastewater collection system or upgrading to a septic system.

A septic system should contain and treat wastewater before disposal. A septic system allows solids to

settle in a tank where anaerobic organisms slowly digest organic solids and allow liquids to flow into a

shallow absorption bed. A proper soil bed has a biologically active area in the first three feet of the soil

layer where oxygen can support microorganism activity that neutralizes pathogens. The studies indicate

that soil treatment is very effective in removing bacteria (fecal coliform was only 13 colony forming units

(cfu) per 100 milliliters (mL) in leachate after soil treatment, versus 1,000,000 cfu/mL for cesspools).

Septic systems with soil treatment also greatly reduce the amount of nitrogen and phosphorus

compared to cesspools.

Page 10 of 91

In contrast, when waste is delivered directly into subsoil that is too coarse or lacks oxygen, as usually

happens with cesspools, biological activity to treat wastewater cannot be supported. Coarse, porous

soil conditions and fractured lava or lava tubes are a problem particularly on the island of Hawaiì (Big

Island), where the majority of the cesspools in the State are located. Porous rock cannot effectively

filter wastewater, but instead allows easy flow within tubes and caves. Other potential contamination

arises from cesspools along the coast in close proximity to the ocean and/or groundwater table.

Hawaiì is the last state in the US to prohibit the construction of new cesspools. There are currently

approximately 88,000 cesspools in the State—nearly 50,000 located on the Big Island, almost 14,000 on

Kauaì, over 12,000 on Maui, over 11,000 on Oàhu, and over 1,400 on Molokaì. Each year an

additional 800 new cesspools were approved for construction. See

http://health.hawaii.gov/wastewater/cesspools/.On December 18, 2017, as required by Act 125 of

2017, the DOH filed a report with the Legislature identifying 14 priority areas of the state where

cesspool upgrades are critically needed to protect public health and the environment. The report

indicates about 43,000 cesspools – half of Hawai‘i’s total 88,000 cesspools – are located in the 14

priority areas: Upcountry Maui; Kahalu‘u, Diamond Head, Waimanalo, Waialua and Ewa on O‘ahu;

Kapoho, Kea‘au, Puako, Hilo Bay and Kailua/Kona coastal areas on Hawai‘i Island; and Kapa‘a/Wailua,

Poipu/Koloa, and Hanalei Bay on Kauai. See the Cesspool Report at

https://health.hawaii.gov/opppd/files/2017/12/Act‐125‐HB1244‐HD1‐SD3‐CD1‐29th‐Legislature‐

Cesspool‐Report.pdf.

Hawaiì's cesspools release approximately 53 million gallons of untreated domestic wastewater into the

ground each day. Untreated wastewater contains pathogens such as bacteria, protozoa, and viruses

that can cause gastroenteritis, Hepatitis A, conjunctivitis, leptospirosis, salmonellosis, and cholera.

Pharmaceuticals in wastewater, including disruptive hormones, also may adversely affect human health

and aquatic organisms. Hawaiì's cesspools also release as much as 23,700 pounds of nitrogen and

nearly 6,000 pounds of phosphorus into the ground each day, which can stimulate undesirable algae

growth, degrade water quality, and impact coral reefs. Health risks from cesspool chemical

contamination include methemoglobinemia (or blue baby syndrome), when elevated nitrogen levels

interfere with the transport of oxygen in the blood stream of young children.

Studies performed for DOH have designated “receptors of concern” as sensitive ecosystems that can

potentially be adversely affected by cesspool effluent, or areas where potential human contact with

cesspool contaminated waters may occur. These studies considered three receptors of concern: (1)

drinking water sources; (2) streams and watersheds; and (3) coastal waters. Setback zones were

delineated around each receptor of concern based on either a fixed distance or a groundwater time of

travel to the receptor of concern. The purpose of these studies was to identify the cesspools and other

individual wastewater treatment systems that have the potential for adverse receptor of concern

impact. The presence of a cesspool within a receptor of concern’s setback zone is considered to have

the potential for a negative impact.

Cesspool effluent can also negatively impact drinking water wells by introducing biological and chemical

contamination into a well’s intake. Two setbacks were delineated for public drinking water wells based

on the groundwater travel time to the well intake. A two‐year time‐of‐travel setback for drinking water

wells identifies those cesspools that have the potential to introduce chemical and biological

contamination into a well. It is assumed that pathogens will not survive longer than 2 years, but

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Page 12 of 91

Receptors of Contamination from PPCPs Sources

Groundwater

Surface Water

Drinking Water

Food Crops

Land Applications

What Contaminants are We Looking for?

The Project Goal/Objective is to evaluate raw wastewater and reclaimed wastewater (R‐1/R‐2) for

identified pharmaceuticals and personal care products (PPCPs). The identified analytes detected would

then be used to develop a monitoring program to evaluate the impact of PPCPs on water quality and the

environment.

Samples were collected by Safe Drinking Water Branch staff using non‐plastic sampling equipment. Each

sample consist of 2 – 40ml amber glass vials with 80ul of 32g/l NaOmadine and 5mg AA.

Eurofins Eaton Analytical was contracted to perform sample analysis via LC‐MS‐MS methods for the

following list of analytes at the listed Method Reporting Level (MRL)/Method Detection Level (MDL).

Page 13 of 91

LC‐MS‐MS ENDOCRINE DISRUPTORS (POSITIVE MODE – SPE) 1,7‐Dimethylxanthine Acetaminophen Albuterol

Amoxicillin (semi‐quantitative) Andorostenedione Atenolol

Atrazine Bezafibrate Bromacil

Caffeine Carbadox Carbamazepine

Carisoprodol Chloridazon Chlorotoluron

Cimetidine Ciprofloxacin ‐ Cipro Cotinine

Cyanazine DACT DEA

DEET Dehydronifedipine DIA

Diazepam Dilantin Diltiazem

Diuron Erythromycin Flumeqine

Fluoxetine Isoproturon Ketoprofen

Ketorolac Lidocaine Lincomycin

Linuron Lopressor Meclofenamic Acid

Meprobamate Metazachlor Metolachlor

Nifedipine Norethisterone Oxolinic acid

Pentoxifylline Phenazone Primidone

Progesterone Propazine Quinoline

Simazine Sulfachloropyridazine Sulfadiazine

Sulfadimethoxine Sulfamerazine Sulfamethazine

Sulfamethizole Sulfamethoxazole Sulfathiazole

TCEP TCPP TDCPP

Testosterone Theobromine Theophylline

Trimethoprim

LC‐MS‐MS ENDOCRINE DISRUPTORS (NEGATIVE MODE – SPE) 2,4‐D 4‐nonylphenol ‐ semi quantitative 4‐tert‐octylphenol

Acesulfame‐K Bendroflumethiazide BPA

Butalbital Butylparaben Chloramphenicol

Clofibric Acid Diclofenac Estradiol

Estrone Ethinyl Estradiol ‐ 17 alha Ethylparaben

Gemfibrozil Ibuprofen Iohexal

Iopromide Isobutylparaben Lipitor (Atorvastain)

Methylparaben Naproxen Propylparaben

Salicylic Acid Sucralose Triclocarban

Triclosan Warfarin

A listing of the analytes with sample collection information (method, sample container, preservative,

holding time) and reporting information (MDL, MRL, units, % Recovery) may be found in Appendix A.

Page 14 of 91

Where and Why are we Looking for these

Contaminants?

Determine Sampling locations/sites: WWRF/WWTP/OSDS Areas As most PPCPs are eliminated via human excretion and the disposal of unused PPCPs has been through the

wastewater disposal system, sampling at WWRF/WWTP would provide the best indication of what PPCPs

may be in the environment. As the State continues to grow and the demand for water increases, the

generation of treated wastewater for reuse and application (for irrigation and other uses) provides

another alternative water source. The application of reuse water on land

above potable groundwater resources is a concern due the possible leaching

of PPCPs and other contaminants of emerging concern (CEC). For this

project we selected four (4) WWTP/WWRF facilities to conduct raw

wastewater (influent) sampling. These four (4) facilities were selected

since previous monitoring of PPCPs by the GWPP was conducted at these

sites. A total of ten (10) R‐1 effluent, one (1) R‐2 effluent and one (1) RO

Quality effluent water sources statewide were also selected for sampling.

Areas where there is a high density of OSDS may also be of concern due to

the method of treatment and disposal from these systems. The potential of

contaminant leaching from OSDS is quite possible.

Determine Receptors of Reuse Water: Groundwater Of primary concern is the impact on groundwater resources. The reuse of treated wastewater and the

areas with a high density of OSDS may results in the potential leaching of PPCPs into the groundwater. For

this project, samples were collected from several groundwater wells in Upcountry Maui (to coincide

with another water quality project) in an area where there is a high density of OSDS and elevated levels

of nitrate in the groundwater. A sample was also collected on Oahu at a groundwater well being

investigated for rising nitrate levels.

Wastewater Reclamation Facilities or Wastewater Treatment Plants

RAW Influent Wastewater

Schofield WWTP (Oahu) Wahiawa WWTP (Oahu)

Pukalani WWTP (Maui) Waimea WWTP (Kauai)

R‐1 Grade/Quality Reuse Water

Schofield WWTP (Oahu) Wahiawa WWTP (Oahu)

Honouliuli WWRF (Oahu) Laie WWTP (Oahu)

Lihue WWTP (Kauai) Poipu WWTP (Kauai)

Grove Farm Lihue‐Puhi WWTP (Kauai) Pukalani WWTP (Maui)

Lahaina WWTP (Maui) Waikoloa (Hawaii)

Kihei WWTP (Maui)

R‐2 Grade/Quality Reuse Water RO Quality Effluent Water

Waimea WWTP (Kauai) Honouliuli WWRF (Oahu)

Page 15 of 91

Groundwater

Pukalani Golf Course Well (Maui) Omaopio‐Esty Well (Maui)

Kipapa Acres Well (Oahu)

Summary of Sample Results

PPCPs found in Raw Influent Wastewater Samples were collected from four (4) Wastewater Reclamation Facilities or Treatment Plants (one on

Kauai, two on Oahu and one on Maui). For each of the facilities/plants, two (2) rounds of samples were

collected.

LC‐MS‐MS ENDOCRINE DISRUPTORS (POSITIVE MODE – SPE) ANALYTE Schofield Wahiawa Waimea Pukalani

1,7‐Dimethylxanthine XO XO XO XO

Acetaminophen XO XO XO XO

Albuterol X O

Amoxicillin (semi‐quantitative) XO XO O XO

Andorostenedione XO XO O O

Atenolol O XO XO XO

Atrazine

Bezafibrate O O

Bromacil

Caffeine XO XO XO XO

Carbadox X

Carbamazepine

Carisoprodol X O

Chloridazon

Chlorotoluron

Cimetidine O O O O

Ciprofloxacin ‐ Cipro O

Cotinine XO XO XO XO

Cyanazine O O O

DACT O

DEA

DEET XO XO XO XO

Dehydronifedipine

DIA

Diazepam

Dilantin

Diltiazem XO XO XO

Diuron O O O

Erythromycin

Flumeqine

Fluoxetine

Isoproturon

Ketoprofen

Ketorolac X

Lidocaine O XO O XO

Lincomycin O O

Linuron

Lopressor XO O XO

Page 16 of 91

ANALYTE Schofield Wahiawa Waimea Pukalani

Meclofenamic Acid O O

Meprobamate O O X XO

Metazachlor

Metolachlor

Nifedipine X

Norethisterone

Oxolinic acid

Pentoxifylline O

Phenazone

Primidone X O

Progesterone O O O

Propazine

Quinoline O O XO XO

Simazine

Sulfachloropyridazine

Sulfadiazine XO O O

Sulfadimethoxine O

Sulfamerazine

Sulfamethazine O

Sulfamethizole

Sulfamethoxazole XO O XO XO

Sulfathiazole

TCEP O O X O

TCPP O

TDCPP

Testosterone O O O O

Theobromine XO X XO XO

Theophylline XO XO XO XO

Trimethoprim XO O O XO

NOTES: X = 1

STRound Sample

O= 2ND Round Sample

LC‐MS‐MS ENDOCRINE DISRUPTORS (NEGATIVE MODE – SPE) ANALYTE Schofield Wahiawa Waimea Pukalani

2,4‐D

4‐nonylphenol ‐ semi quantitative XO O O

4‐tert‐octylphenol

Acesulfame‐K XO XO XO XO

Bendroflumethiazide

BPA X

Butalbital O XO XO

Butylparaben

Chloramphenicol

Clofibric Acid

Diclofenac O

Estradiol O

Estrone O

Ethinyl Estradiol ‐ 17 alha X X X

Ethylparaben O O X

Gemfibrozil O XO XO XO

Ibuprofen XO XO XO XO

Iohexal X XO

Iopromide O

Isobutylparaben

Lipitor (Atorvastain) O

Methylparaben O O XO XO

Page 17 of 91

ANALYTE Schofield Wahiawa Waimea Pukalani Naproxen XO XO XO XO

Propylparaben XO XO XO XO

Salicylic Acid O O

Sucralose XO XO XO XO

Triclocarban O XO O

Triclosan XO X XO O

Warfarin

NOTES: X = 1

ST Round Sample

O = 2ND Round Sample

Analytes Found in all raw wastewater influent samples were: 1,7‐Dimethylxanthine Acetaminophen

Caffeine Cotinine

DEET Theophylline

Acesulfame‐K Ibuprofen

Naproxen Propylparaben

Sucralose

Analytes Found in > 75% of raw wastewater influent samples or at least once (1) at

each WWRF/WWTP: Amoxicillin (semi‐quantitative) Andorostenedione

Atenolol Cimetidine

Diazepam Lidocaine

Meprobamate Quinoline

Sulfamethoxazole TCEP

Testosterone Theobromine

Trimethoprim Gemfibrozil

Methylparaben Triclosan

PPCPs found in Raw Influent Wastewater and Treated Reuse Effluent

Water Raw Influent Wastewater and Treated Reuse Effluent Water samples collected from the four (4)

Wastewater Reclamation Facilities or Treatment Plants (one on Kauai, two on Oahu and one on Maui). For

each of the facilities/plants, two (2) rounds of samples were collected.

SCHOFIELD

LC‐MS‐MS ENDOCRINE DISRUPTORS (POSITIVE MODE – SPE)

ANALYTE Raw Influent

Round 1

R‐1 Effluent

Round 1

Raw Influent

Round 2

R‐1 Effluent

Round 2

1,7‐Dimethylxanthine X X O O

Acetaminophen X X O O

Albuterol

Amoxicillin (semi‐quantitative) X X O O

Andorostenedione X O

Atenolol X O O

Atrazine

Bezafibrate X O

Bromacil

Caffeine X X O O

Page 18 of 91


Round 1

R‐1 Effluent

Round 1

Raw Influent

Round 2

R‐1 Effluent

Round 2

Carbadox O

Carbamazepine X

Carisoprodol

Chloridazon

Chlorotoluron

Cimetidine O O

Ciprofloxacin ‐ Cipro

Cotinine X X O

Cyanazine

DACT O

DEA

DEET X X O O

Dehydronifedipine

DIA

Diazepam

Dilantin O

Diltiazem X

Diuron

Erythromycin

Flumeqine

Fluoxetine

Isoproturon

Ketoprofen

Ketorolac X O

Lidocaine X O O

Lincomycin O

Linuron

Lopressor X

Meclofenamic Acid

Meprobamate X O O

Metazachlor

Metolachlor

Nifedipine

Norethisterone

Oxolinic acid

Pentoxifylline

Phenazone

Primidone X O

Progesterone X O

Propazine

Quinoline X O

Simazine


Sulfadiazine X O O

Sulfadimethoxine

Sulfamerazine

Sulfamethazine X O

Sulfamethizole

Sulfamethoxazole X X O

Sulfathiazole

TCEP X O O

TCPP X O

TDCPP X

Testosterone O

Theobromine X O

Theophylline X X O

Page 19 of 91


Round 1

R‐1 Effluent

Round 1

Raw Influent

Round 2

R‐1 Effluent

Round 2

Trimethoprim X X O

LC‐MS‐MS ENDOCRINE DISRUPTORS (NEGATIVE MODE – SPE)


Round 1 R‐1 Effluent

Round 1 Raw Influent


Round 2 2,4‐D

4‐nonylphenol ‐ semi quantitative X X O O


Acesulfame‐K X X O

Bendroflumethiazide

BPA O

Butalbital O

Butylparaben

Chloramphenicol

Clofibric Acid

Diclofenac

Estradiol O

Estrone O

Ethinyl Estradiol ‐ 17 alha X

Ethylparaben O

Gemfibrozil X O O

Ibuprofen X O

Iohexal X

Iopromide

Isobutylparaben

Lipitor (Atorvastain)

Methylparaben O

Naproxen X O

Propylparaben X O O

Salicylic Acid O O

Sucralose X X O O

Triclocarban O

Triclosan X O

Warfarin

SCHOFIELD (Analytes found in 100% of samples from WWRF/WWTP) 1,7-Dimethylxanthine Acetaminophen Amoxicillin

Caffeine DEET 4-nonylphenol

Sucralose


Atenolol Cotinine Lidocaine

Meprobamate Sulfadiazine Sulfamethoxazole

TCEP Theophyllne Tromeyhoprim

Acesulfame‐K Gemfibrozil Propylparaben

WAHIAWA

Page 20 of 91



Round 1

R‐1 Effluent

Round 1

Raw Influent

Round 2

R‐1 Effluent

Round 2



Albuterol X X O

Amoxicillin (semi‐quantitative) X X O O

Andorostenedione X O O

Atenolol X X O O

Atrazine

Bezafibrate

Bromacil

Caffeine X X O O

Carbadox O

Carbamazepine X O

Carisoprodol X O

Chloridazon

Chlorotoluron

Cimetidine O O


Cotinine X X O O

Cyanazine O

DACT X O O

DEA

DEET X X O O

Dehydronifedipine X

DIA

Diazepam

Dilantin O

Diltiazem X X O

Diuron X O O

Erythromycin

Flumeqine

Fluoxetine

Isoproturon

Ketoprofen

Ketorolac O

Lidocaine X X O O

Lincomycin O O

Linuron

Lopressor X X O O

Meclofenamic Acid

Meprobamate X O O

Metazachlor

Metolachlor

Nifedipine X

Norethisterone

Oxolinic acid

Pentoxifylline O

Phenazone

Primidone X O

Progesterone

Propazine

Quinoline X O

Simazine


Sulfadiazine O O

Sulfadimethoxine

Page 21 of 91


Round 1

R‐1 Effluent

Round 1

Raw Influent

Round 2

R‐1 Effluent

Round 2

Sulfamerazine

Sulfamethazine O O

Sulfamethizole O

Sulfamethoxazole X O O

Sulfathiazole

TCEP X O O

TCPP X O

TDCPP

Testosterone O

Theobromine X X O

Theophylline X X O O

Trimethoprim X O



Round 1

R‐1 Effluent

Round 1

Raw Influent

Round 2

R‐1 Effluent

Round 2

2,4‐D

4‐nonylphenol ‐ semi quantitative X O O


Acesulfame‐K X X O O

Bendroflumethiazide

BPA O

Butalbital X

Butylparaben

Chloramphenicol

Clofibric Acid

Diclofenac O

Estradiol

Estrone

Ethinyl Estradiol ‐ 17 alha

Ethylparaben O

Gemfibrozil X X O

Ibuprofen X X O

Iohexal X

Iopromide

Isobutylparaben


Methylparaben O

Naproxen X O

Propylparaben X O

Salicylic Acid O

Sucralose X X O O

Triclocarban O

Triclosan X

Warfarin


1,7‐Dimethylxanthine Acetaminophen Amoxicillin

Atenolol Caffeine Cotinine

DEET Lidocaine Lopressor

Theophylline Acesulfame‐K Sucralose

Page 22 of 91


Albuterol Andorostenedione DACT

Diltiazem Diuron Meprobamate

Sulfamethoxazole TCEP Theobromine

4‐nonylphenol Gemfibrozil Ibuprofen

WAIMEA



Round 1

R‐1 Effluent

Round 1

Raw Influent

Round 2

R‐1 Effluent

Round 2


Acetaminophen X X O

Albuterol X O

Amoxicillin (semi‐quantitative) X O O

Andorostenedione O O

Atenolol X X O O

Atrazine O

Bezafibrate O

Bromacil

Caffeine X X O O

Carbadox X

Carbamazepine

Carisoprodol X O

Chloridazon O

Chlorotoluron

Cimetidine O O


Cotinine X X O O

Cyanazine O

DACT O

DEA

DEET X X O O

Dehydronifedipine

DIA

Diazepam

Dilantin X O

Diltiazem X X O O

Diuron X O O

Erythromycin O

Flumeqine

Fluoxetine

Isoproturon

Ketoprofen

Ketorolac

Lidocaine X O O

Lincomycin

Linuron

Lopressor X O O

Meclofenamic Acid O O

Meprobamate X X O

Metazachlor

Metolachlor

Nifedipine

Norethisterone

Page 23 of 91


Round 1

R‐1 Effluent

Round 1

Raw Influent

Round 2

R‐1 Effluent

Round 2

Oxolinic acid

Pentoxifylline

Phenazone

Primidone X

Progesterone O

Propazine

Quinoline X X O

Simazine O


Sulfadiazine

Sulfadimethoxine

Sulfamerazine

Sulfamethazine

Sulfamethizole

Sulfamethoxazole X X O O

Sulfathiazole

TCEP X X O

TCPP X O O

TDCPP X

Testosterone O

Theobromine X X O O

Theophylline X X O

Trimethoprim X O O






Round 2 2,4‐D O

4‐nonylphenol ‐ semi quantitative X



Bendroflumethiazide

BPA

Butalbital X O

Butylparaben

Chloramphenicol

Clofibric Acid O

Diclofenac O

Estradiol O

Estrone O

Ethinyl Estradiol ‐ 17 alha X

Ethylparaben

Gemfibrozil X X O O

Ibuprofen X O O

Iohexal X O

Iopromide O O

Isobutylparaben


Methylparaben X O

Naproxen X X O O

Propylparaben X O

Salicylic Acid

Sucralose X X O O

Triclocarban X X O O

Triclosan X O O

Warfarin

Page 24 of 91


1,7‐Dimethylxanthine Atenolol Caffeine

Cotinine DEET Diltiazem

Sulfamethoxazole Theobromide Acesulfame‐K

Gemfibrozil Naproxen Sucralose

Triclocarban


Acetaminophen Amoxicillin Diuron

Lidocaine Lopressor Meprobamat

Quinoline TCEP TCPP

Trimethoprim Ibuprofen Triclosan

PUKALANI



Round 1

R‐1 Effluent

Round 1

Raw Influent

Round 2

R‐1 Effluent

Round 2



Albuterol O

Amoxicillin (semi‐quantitative) X X O

Andorostenedione O

Atenolol X O

Atrazine

Bezafibrate O

Bromacil

Caffeine X X O O

Carbadox O

Carbamazepine X O

Carisoprodol X O O

Chloridazon

Chlorotoluron

Cimetidine O O


Cotinine X X O O

Cyanazine O

DACT O

DEA

DEET X O

Dehydronifedipine X

DIA

Diazepam

Dilantin X O

Diltiazem X O

Diuron X O O

Erythromycin

Flumeqine

Fluoxetine

Page 25 of 91


Round 1

R‐1 Effluent

Round 1

Raw Influent

Round 2

R‐1 Effluent

Round 2

Isoproturon

Ketoprofen

Ketorolac X

Lidocaine X X O O

Lincomycin

Linuron

Lopressor X X O O

Meclofenamic Acid O

Meprobamate X X O O

Metazachlor

Metolachlor

Nifedipine

Norethisterone O

Oxolinic acid

Pentoxifylline O

Phenazone

Primidone X O O

Progesterone O

Propazine

Quinoline X O

Simazine


Sulfadiazine O

Sulfadimethoxine O

Sulfamerazine

Sulfamethazine

Sulfamethizole

Sulfamethoxazole X O O

Sulfathiazole O

TCEP X O O

TCPP X O

TDCPP O

Testosterone O

Theobromine X X O O

Theophylline X O O

Trimethoprim X O






Round 2 2,4‐D

4‐nonylphenol ‐ semi quantitative X O O



Bendroflumethiazide

BPA X

Butalbital X O

Butylparaben

Chloramphenicol

Clofibric Acid

Diclofenac O

Estradiol

Estrone O

Ethinyl Estradiol ‐ 17 alha X X O

Ethylparaben X

Gemfibrozil X O O

Page 26 of 91





Round 2 Ibuprofen X O O

Iohexal X O

Iopromide O

Isobutylparaben

Lipitor (Atorvastain) O

Methylparaben X O

Naproxen X O

Propylparaben X O O

Salicylic Acid

Sucralose X O O

Triclocarban X O

Triclosan O

Warfarin

PUKALANI(Analytes found in 100% of samples from WWRF/WWTP)

1,7‐Dimethylxanthine Acetaminophen Caffeine

Cotinine Lidocaine Lopressor

Meprobamate Theobromine Acesulfame‐K


Amoxicillin Carisoprodol Diuron

Primidone Sulfamethoxazole TCEP

Theophyllne 4‐nonylphenol Gemfibrozil

Ibuprofen Iohexal Propylparaben

Sucralose

PPCPs found in Treated Reuse Effluent Water A total of ten (10) R‐1 effluent, one (1) R‐2 effluent and one (1) RO Quality effluent water sources

statewide were also selected for sampling. Two (2) rounds of sampling was conducted at each source.


ANALYTE

SC

HO

FIE

LD

WA

HIA

WA

LA

IE

HO

NO

UL

IUL

I RO

HO

NO

UL

IUL

I R-1

LIH

UE

WA

IME

A

PO

IPU

GR

OV

E F

RM

PU

KA

LA

NI

LA

HA

INA

KIH

EI

WA

IKO

LO

A

1,7‐Dimethylxanthine XO XO XO XO XO XO XO X XO XO XO XO

Acetaminophen XO XO XO XO XO X XO X XO XO XO XO

Albuterol XO X O XO XO

Amoxicillin (semi‐quantitative) XO XO XO XO XO XO XO X X XO

Andorostenedione O O O O O

Atenolol XO XO XO XO XO XO XO O XO XO

Atrazine O

Bezafibrate X O

Bromacil

Page 27 of 91

ANALYTE

SC

HO

FIE

LD

WA

HIA

WA

LA

IE

HO

NO

UL

IUL

I RO

HO

NO

UL

IUL

I R-1

LIH

UE

WA

IME

A

PO

IPU

GR

OV

E F

RM

PU

KA

LA

NI

LA

HA

INA

KIH

EI

WA

IKO

LO

A

Caffeine XO XO X XO XO XO XO X XO XO X XO

Carbadox O O O O O O O

Carbamazepine X XO O XO X XO XO XO XO

Carisoprodol XO XO XO O O O XO O O O

Chloridazon O O O XO

Chlorotoluron

Cimetidine O O O O O O O O O O O


Cotinine X XO X XO XO XO XO X XO XO XO XO

Cyanazine

DACT O XO XO O XO O O O O O O

DEA XO

DEET XO XO XO XO XO XO XO XO XO XO XO

Dehydronifedipine X XO X X

DIA

Diazepam

Dilantin O O XO O XO XO XO X XO

Diltiazem X XO XO XO XO XO XO X O

Diuron XO X XO XO XO O XO XO XO XO

Erythromycin X XO XO O XO XO

Flumeqine

Fluoxetine O

Isoproturon

Ketoprofen

Ketorolac XO O XO O O O

Lidocaine XO XO XO XO XO XO XO X XO XO X XO

Lincomycin O O

Linuron

Lopressor X XO X XO XO XO X XO XO XO XO

Meclofenamic Acid O XO XO O O X XO XO

Meprobamate XO XO XO XO XO XO XO XO XO XO XO

Metazachlor

Metolachlor

Nifedipine

Norethisterone X O

Oxolinic acid

Pentoxifylline O X

Phenazone

Primidone X XO XO XO X X XO XO XO XO

Progesterone X

Propazine

Quinoline X X X XO XO X XO XO X X

Simazine O


Sulfadiazine O O O O O

Sulfadimethoxine O

Sulfamerazine

Sulfamethazine XO O O O O

Sulfamethizole O XO

Sulfamethoxazole XX XO O XO XO XO O O O XO O

Sulfathiazole O O O

Page 28 of 91

ANALYTE

SC

HO

FIE

LD

WA

HIA

WA

LA

IE

HO

NO

UL

IUL

I RO

HO

NO

UL

IUL

I R-1

LIH

UE

WA

IME

A

PO

IPU

GR

OV

E F

RM

PU

KA

LA

NI

LA

HA

INA

KIH

EI

WA

IKO

LO

A

TCEP XO XO XO XO XO XO XO XO XO XO XO XO

TCPP XO XO XO XO XO XO XO XO XO XO XO XO

TDCPP X X XO XO XO X O XO XO X

Testosterone

Theobromine XO O XO XO XO XO X XO XO XO O

Theophylline X XO XO XO XO X XO X O O X X

Trimethoprim X XO XO O XO XO O X

NOTES: X = 1

ST Round Sample



ANALYTE

SC

HO

FIE

LD

WA

HIA

WA

LA

IE

HO

NO

UL

IUL

I RO

HO

NO

UL

IUL

I R-1

LIH

UE

WA

IME

A

PO

IPU

GR

OV

E F

RM

PU

KA

LA

NI

LA

HA

INA

KIH

EI

WA

IKO

LO

A

2,4‐D XO XO O

4‐nonylphenol ‐ semi quantitative XO XO XO X XO X XO XO XO X O

4‐tert‐octylphenol XO XO XO O

Acesulfame‐K XO XO XO XO XO XO XO XO XO XO X XO

Bendroflumethiazide X

BPA O O XO O X XO XO X

Butalbital X O X XO

Butylparaben

Chloramphenicol

Clofibric Acid X O O XO

Diclofenac O XO XO O O X O

Estradiol O O X

Estrone O O XO O XO O O

Ethinyl Estradiol ‐ 17 alha O X

Ethylparaben

Gemfibrozil XO X XO XO XO XO XO X O XO X

Ibuprofen X O XO XO O

Iohexal X XO XO XO X X

Iopromide XO X O XO XO O

Isobutylparaben

Lipitor (Atorvastain) X X

Methylparaben X

Naproxen XO XO XO X X

Propylparaben O O O

Salicylic Acid O XO O XO X XO

Sucralose XO XO XO O XO XO XO XO XO O X X XO

Triclocarban O XO XO XO O X XO

Triclosan XO XO O XO X O

Warfarin O O

NOTES: X = 1

ST Round Sample


Page 29 of 91

ANALYTES (found at all treated wastewater sources sampled) Sucralose

ANALYTES (found at all treated wastewater sources sampled, except Honouliuli RO) 1,7‐Dimethylxanthine Acetaminophen Caffeine

Cotinine Lidocaine TCEP

TCPP Theophylline Acesulfame‐K

ANALYTES (found at a significant number of treated wastewater sources sampled) Amoxicillin Atenolol Carbanazepine

Carisoprodol DACT DEET

Dilantin Diltiazem Diuron

Erythromycin Lopressor Meclofenamic Acid

Meprobamate Primidone Quinodone

Sulfamethoxazole TDCPP Theobromine

Trimethoprim 4‐nonylphenol Gemfibrozil

OTHER ANALYTES OF INTEREST(found in multiple treated wastewater sources) Albuterol Ketorolac 4‐tert‐octylphenol

BPA Diclofenac Estrone

Ibuprofen Iohexal Iopromide

Naproxen Salicylic Acid Triclocarban

Triclosan

PPCPs found in Groundwater in Areas with high density of OSDS Samples were collected from several groundwater wells in Upcountry Maui (to coincide with another

water quality project) in an area where there is a high density of OSDS and elevated levels of nitrate in the

groundwater. A sample was also collected on Oahu at a groundwater well being investigated for rising

nitrate levels.

LC‐MS‐MS ENDOCRINE DISRUPTORS (POSITIVE MODE – SPE) ANALYTE Pukalani GC Omaopio‐Esty Kipapa Acres

1,7‐Dimethylxanthine

Acetaminophen

Albuterol

Amoxicillin (semi‐quantitative) 300 ng/L 72 ng/L

Andorostenedione

Atenolol

Atrazine

Bezafibrate

Bromacil 13 ng/L

Caffeine

Carbadox

Carbamazepine

Carisoprodol

Chloridazon 13 ng/L 11 ng/L

Page 30 of 91

ANALYTE Pukalani GC Omaopio‐Esty Kipapa Acres

Chlorotoluron

Cimetidine 8.8 ng/L


Cotinine

Cyanazine

DACT 32 ng/L

DEA

DEET

Dehydronifedipine

DIA

Diazepam

Dilantin

Diltiazem

Diuron

Erythromycin

Flumeqine

Fluoxetine

Isoproturon

Ketoprofen

Ketorolac

Lidocaine

Lincomycin

Linuron

Lopressor

Meclofenamic Acid

Meprobamate

Metazachlor

Metolachlor

Nifedipine

Norethisterone

Oxolinic acid

Pentoxifylline

Phenazone

Primidone

Progesterone

Propazine

Quinoline

Simazine


Sulfadiazine

Sulfadimethoxine

Sulfamerazine

Sulfamethazine

Sulfamethizole

Sulfamethoxazole 11 ng/L

Sulfathiazole 30 ng/L 6.2 ng/L

TCEP

TCPP

TDCPP

Testosterone

Theobromine

Theophylline

Trimethoprim

LC‐MS‐MS ENDOCRINE DISRUPTORS (NEGATIVE MODE – SPE) ANALYTE Pukalani GC Omaopio‐Esty Kipapa Acres

2,4‐D

Page 31 of 91

ANALYTE Pukalani GC Omaopio‐Esty Kipapa Acres 4‐nonylphenol ‐ semi quantitative 460 ng/L 460 ng/L


Acesulfame‐K 30 ng/L

Bendroflumethiazide

BPA

Butalbital

Butylparaben

Chloramphenicol

Clofibric Acid

Diclofenac

Estradiol

Estrone

Ethinyl Estradiol ‐ 17 alha

Ethylparaben

Gemfibrozil

Ibuprofen

Iohexal

Iopromide

Isobutylparaben


Methylparaben

Naproxen

Propylparaben

Salicylic Acid

Sucralose 190 ng/L

Triclocarban

Triclosan

Warfarin

Several analytes were detected in the three samples: Pukalani: Amoxicillin, Chloridazon, Sulfamethoxazole, Sulfathiazole, 4-nonylphenol, and

Acesulfame-K Omaopio-Esty: Amoxicillin, Bromacil, Chloridazon, Sulfathiazole, and 4-nonylphenol Kipapa Acres: Cimetidine, DACT (Diamino-chloro-triazine), and Sucralose

Summary

The following is a Summary of the Positive Results from the PPCPs Sampling.

RAW WASTEWATER INFLUENT

Analytes Found in all raw wastewater influent samples were: 1,7‐Dimethylxanthine Acetaminophen

Caffeine Cotinine

DEET Theophylline

Acesulfame‐K Ibuprofen

Naproxen Propylparaben

Sucralose

Analytes Found in > 75% of raw wastewater influent samples or at least once (1) at

each WWRF/WWTP: Amoxicillin (semi‐quantitative) Andorostenedione

Page 32 of 91

Atenolol Cimetidine

Diazepam Lidocaine

Meprobamate Quinoline

Sulfamethoxazole TCEP

Testosterone Theobromine

Trimethoprim Gemfibrozil

Methylparaben Triclosan

RAW WASTEWATER INFLUENT and TREATED REUSE EFFLUENT WATER

FROM SELECTED WWRF/WWTP

SCHOFIELD (Analytes found in 100% of samples from WWRF/WWTP) 1,7-Dimethylxanthine Acetaminophen Amoxicillin Caffeine DEET 4-nonylphenol Sucralose


Atenolol Cotinine Lidocaine

Meprobamate Sulfadiazine Sulfamethoxazole

TCEP Theophyllne Tromeyhoprim

Acesulfame‐K Gemfibrozil Propylparaben


1,7‐Dimethylxanthine Acetaminophen Amoxicillin

Atenolol Caffeine Cotinine

DEET Lidocaine Lopressor

Theophylline Acesulfame‐K Sucralose


Albuterol Andorostenedione DACT

Diltiazem Diuron Meprobamate

Sulfamethoxazole TCEP Theobromine

4‐nonylphenol Gemfibrozil Ibuprofen


1,7‐Dimethylxanthine Atenolol Caffeine

Cotinine DEET Diltiazem

Sulfamethoxazole Theobromide Acesulfame‐K

Gemfibrozil Naproxen Sucralose

Triclocarban


Acetaminophen Amoxicillin Diuron

Lidocaine Lopressor Meprobamat

Quinoline TCEP TCPP

Page 33 of 91

Trimethoprim Ibuprofen Triclosan


1,7‐Dimethylxanthine Acetaminophen Caffeine

Cotinine Lidocaine Lopressor

Meprobamate Theobromine Acesulfame‐K


Amoxicillin Carisoprodol Diuron

Primidone Sulfamethoxazole TCEP

Theophyllne 4‐nonylphenol Gemfibrozil

Ibuprofen Iohexal Propylparaben

Sucralose

TREATED REUSE EFFLUENT WATER FROM SELECTED REUSE WATER

FACILITIES

ANALYTES (found at all treated wastewater sources sampled) Sucralose

ANALYTES (found at all treated wastewater sources sampled, except Honouliuli RO) 1,7‐Dimethylxanthine Acetaminophen Caffeine

Cotinine Lidocaine TCEP

TCPP Theophylline Acesulfame‐K

ANALYTES (found at a significant number of treated wastewater sources sampled) Amoxicillin Atenolol Carbanazepine

Carisoprodol DACT DEET

Dilantin Diltiazem Diuron

Erythromycin Lopressor Meclofenamic Acid

Meprobamate Primidone Quinodone

Sulfamethoxazole TDCPP Theobromine

Trimethoprim 4‐nonylphenol Gemfibrozil

OTHER ANALYTES OF INTEREST (found in multiple treated wastewater sources) Albuterol Ketorolac 4‐tert‐octylphenol

BPA Diclofenac Estrone

Ibuprofen Iohexal Iopromide

Naproxen Salicylic Acid Triclocarban

Triclosan

The data for this project was the result of two rounds of samples collected from four (4) WWRF/WWTP

(raw wastewater influent) and thirteen (13) facilities that treate wastewater (1 ‐ RO, 11 ‐ R‐1, and 1 – R‐2).

Page 34 of 91

Data Observations (1) Some analytes were found in the raw wastewater influent but not in the treated effluent –

possibility that analyses are treated/removed by the wastewater treatment process. (2) Some analytes were found in the treated effluent but not in the raw wastewater influent – there is

a possibility that those analytes were masked by the chromatographic peaks of other analytes (of high concentration) but detected in the treated effluent after treatment/removal of the higher concentration analytes.

(3) Reverse osmosis appears to be an effective method of removing PPCPs from wastewater as the first round sample did not detect any analytes and the second round sample only detected three (3) analytes. This is compared with the R-1 water from the same treatment facility that showed the detection of fifty-eight(58) analytes.

Data Issues Are there other factors that may have impacted the monitoring project and do these factors affect the

presence and levels of PPCPs in raw wastewater influent and treated wastewater effluent? Possible

concerns may be associated with wastewater flow/time of sampling (more flow may equate to more

dilution or possibly increase analyte levels), treatment processes (how does the process affect the

treatment/removal of the analyte), or possibly population demographics (differing population factors such

as age, race, health issues, others may affect the type and quantities of PPCPs that would be used in a

particular geographical area).

GROUNDWATER IN AREAS WITH HIGH DENSITY OF OSDS or ELEVATED

NITRATE LEVELS Samples were collected from several groundwater wells in Upcountry Maui (to coincide with another

water quality project) in an area where there is a high density of OSDS and elevated levels of nitrate in the

groundwater. A sample was also collected on Oahu at a groundwater well being investigated for rising

nitrate levels.

Several contamination analytes were detected in the three samples: Pukalani: Amoxicillin, Chloridazon, Sulfamethoxazole, Sulfathiazole, 4-nonylphenol, and

Acesulfame-K Omaopio-Esty: Amoxicillin, Bromacil, Chloridazon, Sulfathiazole, and 4-nonylphenol Kipapa Acres: Cimetidine, DACT (Diamino-chloro-triazine), and Sucralose

Data Observations (1) The presence of Acesulfame-K and Sucralose may be a good indication of contaminant leaching

from OSDS to groundwater. Throughout the project, these two (2) analytes were detected at high concentrations in most of the samples collected.

(2) Amoxicillin, Chloridazon, Sulfathiazole, and 4-nonylphenol were detected in two (2) of the wells sampled. Throughout the project, these analytes were also detected in most of the samples collected.

Data Issue While these detections may be a possible indication of the leaching of contaminants in areas where there are high densities of OSDS or elevated nitrate levels, only one (1) sample from each well was collected. It would be wise to collect a follow-up sample to confirm the findings of the initial sample.

Page 35 of 91

Further Action(s) Additional Monitoring Needs and Resources:

(1) Conduct follow‐up sampling to confirm the results of the PPCPs detections in Groundwater.

(2) Utilize the data to develop and implement a PPCPs in Water Monitoring Program focusing on

PPCPs and indicators that were detected in the raw influent and the R‐1 effluent). GWPP will be

working with the SLD to identify PPCPs and begin the development of capabilities to conduct

analyses of the selected PPCPs.

Criteria for areas where reuse wastewater should not be used: (1) Conduct leaching model studies of identified/selected PPCPs to determine leachability to

groundwater.

(2) Assessment of monitoring results to determine the impacts of using Reuse (R‐1) water over our

drinking water/groundwater resources).

Potential need for Program changes: (1) Reuse Guidelines for Emerging Contaminants: Are levels and types of PPCP analytes a public

health concern? Do we need guidelines or standards for these contaminants? Do we need

additional treatment/controls of PPCPs and the reuse wastewater effluent (Best management

practices/Mitigation measures/Contaminant reduction/Pollution technology/Others) to improve

the reuse wastewater quality?

(2) Reuse wastewater effluent/groundwater monitoring: Do we need to monitor our reuse water

and water sources to protect our water resources?

(3) Public Education/Outreach: The reuse of treated wastewater is an area in which the public may

not be aware of and therefore may be a concern. Not being educated/informed of the value and

need associated with reused water (Where will it be used? How will it be used? Is it safe to use?

How do ensure public health/safety) will lead to uncertainty and concern. How do we present

this issue to the public?

Page 36 of 91

APPENDIX A ‐ PPCPs ~ Analytes Sampling and

Reporting Information

#DX_ABI_EDC_PLUS

Date: 01/24/2014

ANALYTE MRL UNITS CAS #LCS

RANGE

MS

RANGEMETHOD MDLCONTAINER &

PRESERVATIVES

HOLDING

TIME

2,4-D 5 ng/L 94-75-760 - 140 60 - 1404.98LC-MS-MS 40ml amber glass vial

80ul 32g/l NaOmadine + 5mg AA28 DAY

4-nonylphenol - semi quantitative 100 ng/L 25154-52-360 - 140 60 - 14050LC-MS-MS 40ml amber glass vial


4-tert-octylphenol 50 ng/L 140-66-960 - 140 60 - 1406.90LC-MS-MS 40ml amber glass vial


Acesulfame-K 20 ng/L 55589-62-360 - 140 60 - 14020LC-MS-MS 40ml amber glass vial


Bendroflumethiazide 5 ng/L 73-48-360 - 140 60 - 1404.37LC-MS-MS 40ml amber glass vial


BPA 10 ng/L 80-05-760 - 140 60 - 1407.17LC-MS-MS 40ml amber glass vial


Butalbital 5 ng/L 77-26-960 - 140 60 - 1402.90LC-MS-MS 40ml amber glass vial


Butylparben 5 ng/L 94-26-860 - 140 60 - 1403.27LC-MS-MS 40ml amber glass vial


Chloramphenicol 10 ng/L 56-75-760 - 140 60 - 1403.10LC-MS-MS 40ml amber glass vial


Clofibric Acid 5 ng/L 882-09-760 - 140 60 - 1405LC-MS-MS 40ml amber glass vial


Diclofenac 5 ng/L 15307-86-560 - 140 60 - 1403.30LC-MS-MS 40ml amber glass vial


Estradiol 5 ng/L 50-28-260 - 140 60 - 1404.41LC-MS-MS 40ml amber glass vial


Estrone 5 ng/L 53-16-760 - 140 60 - 1403.90LC-MS-MS 40ml amber glass vial


Ethinyl Estradiol - 17 alpha 5 ng/L 77538-56-860 - 140 60 - 1403.32LC-MS-MS 40ml amber glass vial


Ethylparaben 20 ng/L 120-47-860 - 140 60 - 14011.4LC-MS-MS 40ml amber glass vial


Gemfibrozil 5 ng/L 25812-30-060 - 140 60 - 1402.47LC-MS-MS 40ml amber glass vial


Ibuprofen 10 ng/L 15687-27-160 - 140 60 - 1408.63LC-MS-MS 40ml amber glass vial


Iohexal 10 ng/L 66108-95-060 - 140 50 - 1507.74LC-MS-MS 40ml amber glass vial


Iopromide 5 ng/L 73334-07-360 - 140 50 - 1501.59LC-MS-MS 40ml amber glass vial


Isobutylparaben 5 ng/L 4247-02-360 - 140 60 - 1404.21LC-MS-MS 40ml amber glass vial


Page 1 of 5


RANGE

MS


PRESERVATIVES

HOLDING

TIME

Lipitor (Atorvastain) 100 ng/L 60 - 140 60 - 140LC-MS-MS 40ml amber glass vial


Methylparaben 20 ng/L 99-76-360 - 140 60 - 14011.4LC-MS-MS 40ml amber glass vial


Naproxen 10 ng/L 22204-53-160 - 140 60 - 1408.51LC-MS-MS 40ml amber glass vial


Propylparaben 5 ng/L 94-13-360 - 140 60 - 1402.94LC-MS-MS 40ml amber glass vial


Salicylic Acid 100 ng/L 69-72-760 - 140 60 - 140LC-MS-MS 40ml amber glass vial


Sucralose 100 ng/L 56038-13-260 - 140 60 - 14042.2LC-MS-MS 40ml amber glass vial


Triclocarban 5 ng/L 10-20-2160 - 140 60 - 140LC-MS-MS 40ml amber glass vial


Triclosan 10 ng/L 3380-34-560 - 140 60 - 1406.32LC-MS-MS 40ml amber glass vial


Warfarin 5 ng/L 81-81-260 - 140 60 - 1404.06LC-MS-MS 40ml amber glass vial


1,7-Dimethylxanthine 10 ng/L 611-59-660 - 140 60 - 1403.35LC-MS-MS 40ml amber glass vial


Acetaminophen 5 ng/L 103-90-260 - 140 60 - 1403.01LC-MS-MS 40ml amber glass vial


Albuterol 5 ng/L 18559-94-960 - 140 60 - 1402.45LC-MS-MS 40ml amber glass vial


Amoxicillin (semi-quantitative) 20 ng/L 26787-78-060 - 140 60 - 1406.39LC-MS-MS 40ml amber glass vial


Andorostenedione 5 ng/L 63-05-860 - 140 60 - 1401.71LC-MS-MS 40ml amber glass vial


Atenolol 5 ng/L 29122-68-760 - 140 60 - 1403.88LC-MS-MS 40ml amber glass vial


Atrazine 5 ng/L 1912-24-960 - 140 60 - 1402.34LC-MS-MS 40ml amber glass vial


Azithromycin 20 ng/L 83905-01-560 - 140 60 - 14010LC-MS-MS 40ml amber glass vial


Bezafibrate 5 ng/L 41859-67-060 - 140 60 - 1403.51LC-MS-MS 40ml amber glass vial


Bromacil 5 ng/L 314-40-960 - 140 60 - 1403.245LC-MS-MS 40ml amber glass vial


Caffeine 5 ng/L 58-08-270 - 130 60 - 1404.31LC-MS-MS 40ml amber glass vial


Carbadox 5 ng/L 6804-07-560 - 140 60 - 1404.19LC-MS-MS 40ml amber glass vial


Carbamazepine 5 ng/L 298-46-460 - 140 60 - 1401.21LC-MS-MS 40ml amber glass vial


Page 2 of 5


RANGE

MS


PRESERVATIVES

HOLDING

TIME

Carisoprodol 5 ng/L 78-44-460 - 140 60 - 1401.19LC-MS-MS 40ml amber glass vial


Chloridazon 5 ng/L 1698-60-860 - 140 60 - 1401.57LC-MS-MS 40ml amber glass vial


Chlorotoluron 5 ng/L 155-45-48960 - 140 60 - 1400.892LC-MS-MS 40ml amber glass vial


Cimetidine 5 ng/L 51481-61-960 - 140 60 - 1402.71LC-MS-MS 40ml amber glass vial


Ciprofloxacin - Cipro 100 ng/L 40 - 160 40 - 16020LC-MS-MS 40ml amber glass vial


Cotinine 10 ng/L 486-56-660 - 140 60 - 1404.85LC-MS-MS 40ml amber glass vial


Cyanazine 5 ng/L 21725-46-260 - 140 60 - 1401.68LC-MS-MS 40ml amber glass vial


DACT 5 ng/L 3397-62-460 - 140 60 - 1403.92LC-MS-MS 40ml amber glass vial


DEA 5 ng/L 6190-65-460 - 140 60 - 1401.48LC-MS-MS 40ml amber glass vial


DEET 10 ng/L 134-62-370 - 130 60 - 1401.08LC-MS-MS 40ml amber glass vial


Dehydronifedipine 5 ng/L 67035-22-760 - 140 60 - 1401.35LC-MS-MS 40ml amber glass vial


DIA 5 ng/L 1007-28-960 - 140 60 - 1402.45LC-MS-MS 40ml amber glass vial


Diazepam 5 ng/L 15307-86-560 - 140 60 - 1402.06LC-MS-MS 40ml amber glass vial


Dilantin 20 ng/L 57-41-060 - 140 60 - 14012.6LC-MS-MS 40ml amber glass vial


Diltiazem 5 ng/L 42399-41-760 - 140 60 - 1403LC-MS-MS 40ml amber glass vial


Diuron 5 ng/L 330-54-160 - 140 60 - 1401.80LC-MS-MS 40ml amber glass vial


Erythromycin 10 ng/L 114-07-860 - 140 60 - 1404.03LC-MS-MS 40ml amber glass vial


Flumeqine 10 ng/L 42835-25-660 - 140 60 - 1407.10LC-MS-MS 40ml amber glass vial


Fluoxetine 10 ng/L 54910-89-360 - 140 60 - 14010LC-MS-MS 40ml amber glass vial


Isoproturon 100 ng/L 341-23-59660 - 140 60 - 14012.3LC-MS-MS 40ml amber glass vial


Ketoprofen 5 ng/L 22071-15-460 - 140 60 - 1402.59LC-MS-MS 40ml amber glass vial


Ketorolac 5 ng/L 74103-06-360 - 140 60 - 1402.07LC-MS-MS 40ml amber glass vial


Page 3 of 5


RANGE

MS


PRESERVATIVES

HOLDING

TIME

Lidocaine 5 ng/L 137-58-660 - 140 60 - 1401.11LC-MS-MS 40ml amber glass vial


Lincomycin 10 ng/L 154-21-260 - 140 60 - 1401.68LC-MS-MS 40ml amber glass vial


Linuron 5 ng/L 330-55-260 - 140 60 - 1402.84LC-MS-MS 40ml amber glass vial


Lopressor 20 ng/L 51384-51-160 - 140 60 - 1405.14LC-MS-MS 40ml amber glass vial


Meclofenamic Acid 5 ng/L 644-62-260 - 140 60 - 1404.66LC-MS-MS 40ml amber glass vial


Meprobamate 5 ng/L 57-53-460 - 140 60 - 1402.03LC-MS-MS 40ml amber glass vial


Metazachlor 5 ng/L 67129-08-260 - 140 60 - 1401.27LC-MS-MS 40ml amber glass vial


Metolachlor 5 ng/L 51218-45-260 - 140 60 - 140LC-MS-MS 40ml amber glass vial


Nifedipine 20 ng/L 21829-25-460 - 140 60 - 14012.4LC-MS-MS 40ml amber glass vial


Norethisterone 5 ng/L 68-22-460 - 140 60 - 1402.26LC-MS-MS 40ml amber glass vial


Oxolinic acid 10 ng/L 14698-29-460 - 140 60 - 1402.46LC-MS-MS 40ml amber glass vial


Pentoxifylline 5 ng/L 6493-05-660 - 140 60 - 1401.53LC-MS-MS 40ml amber glass vial


Phenazone 5 ng/L 60-80-060 - 140 60 - 1405LC-MS-MS 40ml amber glass vial


Primidone 5 ng/L 125-33-760 - 140 60 - 1404.77LC-MS-MS 40ml amber glass vial


Progesterone 5 ng/L 57-83-060 - 140 60 - 1402.94LC-MS-MS 40ml amber glass vial


Propazine 5 ng/L 139-40-260 - 140 60 - 1401.81LC-MS-MS 40ml amber glass vial


Quinoline 5 ng/L 91-22-560 - 140 60 - 1402.5LC-MS-MS 40ml amber glass vial


Simazine 5 ng/L 122-34-960 - 140 60 - 1401.23LC-MS-MS 40ml amber glass vial


Sulfachloropyridazine 5 ng/L 80-32-060 - 140 60 - 1402.09LC-MS-MS 40ml amber glass vial


Sulfadiazine 5 ng/L 68-35-960 - 140 60 - 1403.94LC-MS-MS 40ml amber glass vial


Sulfadimethoxine 5 ng/L 122-11-260 - 140 60 - 1401.60LC-MS-MS 40ml amber glass vial


Sulfamerazine 5 ng/L 127-79-760 - 140 60 - 1404.58LC-MS-MS 40ml amber glass vial


Page 4 of 5


RANGE

MS


PRESERVATIVES

HOLDING

TIME

Sulfamethazine 5 ng/L 57-68-160 - 140 60 - 1401.46LC-MS-MS 40ml amber glass vial


Sulfamethizole 5 ng/L 144-82-160 - 140 60 - 1403.15LC-MS-MS 40ml amber glass vial


Sulfamethoxazole 5 ng/L 723-46-670 - 130 60 - 1402.82LC-MS-MS 40ml amber glass vial


Sulfathiazole 5 ng/L 72-14-060 - 140 60 - 1402.36LC-MS-MS 40ml amber glass vial


TCEP 10 ng/L 51805-45-960 - 140 60 - 1403.18LC-MS-MS 40ml amber glass vial


TCPP 100 ng/L 13674-87-840 - 160 40 - 16020LC-MS-MS 40ml amber glass vial


TDCPP 100 ng/L 13674-87-840 - 160 40 - 16020LC-MS-MS 40ml amber glass vial


Testosterone 5 ng/L 58-22-060 - 140 60 - 1402.5LC-MS-MS 40ml amber glass vial


Theobromine 10 ng/L 83-67-060 - 140 60 - 1403.17LC-MS-MS 40ml amber glass vial


Theophylline 20 ng/L 58-55-960 - 140 60 - 1404.76LC-MS-MS 40ml amber glass vial


Trimethoprim 5 ng/L 738-70-560 - 140 60 - 1401.81LC-MS-MS 40ml amber glass vial


Page 5 of 5

Page 43 of 91

APPENDIX B ‐ Monitoring Results

(Copies of positive results sheets only)

Documents

2018 G STATUS REPORT · TCE concentration of 6.6 µg/L slightly less than the historical high concentration of 7.1 µg/L in a sample collected on February 20, 2008. The Schofield