Emerging Contaminants: Emerging Contaminants: Organic Chemical Organic Chemical

Occurrences in Raw and Occurrences in Raw and Finished Drinking WaterFinished Drinking Water

Dennis NelsonDennis Nelson

Drinking Water ProgramDrinking Water Program

Public Health DivisionPublic Health Division

Oregon Health AuthorityOregon Health AuthoritySeptember 9, 2008

Emerging ContaminantsEmerging Contaminants Non-regulated chemicals, naturally occurring Non-regulated chemicals, naturally occurring

or synthetic, that have become recognized as or synthetic, that have become recognized as occurring in water resources and may occurring in water resources and may potentially pose a risk to human health or the potentially pose a risk to human health or the environmentenvironment

Improvements in analytical methods has Improvements in analytical methods has increased our ability to detect the occurrence increased our ability to detect the occurrence of chemicals in very minute quantities.of chemicals in very minute quantities.

Very little is known about the health impact of Very little is known about the health impact of these chemicals, but they are widespread, these chemicals, but they are widespread, persistent in the environment and tend to persistent in the environment and tend to bioaccumulate. bioaccumulate.

Effects of a mixture of these chemicals Effects of a mixture of these chemicals unknownunknown

Emerging ContaminantsEmerging Contaminants Over 30,000,000 organic and inorganic Over 30,000,000 organic and inorganic

chemicals have been registeredchemicals have been registered More than 5,000,000 in the last two years aloneMore than 5,000,000 in the last two years alone 13,000,000 are commercially available13,000,000 are commercially available

Pharmaceuticals and Personal Care Products (PPCP)Pharmaceuticals and Personal Care Products (PPCP) PesticidesPesticides Endocrine (hormonal) disrupting chemicalsEndocrine (hormonal) disrupting chemicals Flame RetardantsFlame Retardants Nanoparticles (widely distributed, many different Nanoparticles (widely distributed, many different

uses, smaller than individual cells)uses, smaller than individual cells) Prions – infectious proteins, in waste water, not Prions – infectious proteins, in waste water, not

inactivated by chlorine, cause fatal brain disease in inactivated by chlorine, cause fatal brain disease in animals/humansanimals/humans

Organic Chemicals in Organic Chemicals in Drinking WaterDrinking Water

Pesticide occurrencesPesticide occurrences USGS Open-File 01-456: Pesticides in Selected USGS Open-File 01-456: Pesticides in Selected

Water-Supply Reservoirs and Finished Water, 1999-Water-Supply Reservoirs and Finished Water, 1999-20002000

USGS Scientific Invest Rpt 2008-5027: Pesticide USGS Scientific Invest Rpt 2008-5027: Pesticide Occurrence and Distribution in the Lower Occurrence and Distribution in the Lower Clackamas River Basin, Oregon, 2000-2005Clackamas River Basin, Oregon, 2000-2005

USGS Water-Resources Invest Rpt 97-4268: Distribution USGS Water-Resources Invest Rpt 97-4268: Distribution of Dissolved Pesticides…in the Willamette…Basin, 1996of Dissolved Pesticides…in the Willamette…Basin, 1996

USGS Water-Resources Invest Rpt 97-4082B: Quality of USGS Water-Resources Invest Rpt 97-4082B: Quality of Shallow Groundwater in…the Willamette Basin, 1993-95Shallow Groundwater in…the Willamette Basin, 1993-95

Pharmaceuticals and Personal Care ProductsPharmaceuticals and Personal Care Products AWWA 2005 Webcast: Endocrine Disrupters, AWWA 2005 Webcast: Endocrine Disrupters,

Pharmaceuticals and Personal Care ProductsPharmaceuticals and Personal Care Products http://www.epa.gov/ppcp/http://www.epa.gov/ppcp/

Pesticides in Drinking Pesticides in Drinking WaterWater

Pilot project by USGS and EPA in 1999Pilot project by USGS and EPA in 1999 Samples collected of both raw and Samples collected of both raw and

finished water prior to distribution systemfinished water prior to distribution system Focus was on surface water bodiesFocus was on surface water bodies

Primarily reservoirsPrimarily reservoirs High vulnerability to pesticide activity in High vulnerability to pesticide activity in

reservoirreservoir Tested for 178 pesticides (herbicides and Tested for 178 pesticides (herbicides and

insecticides)insecticides)

Sample Site Sample Site CharacteristicsCharacteristics

States involved: CA, IN, OH, OK, LA, MO, States involved: CA, IN, OH, OK, LA, MO, SC, SD, NY, NC, PA, and TXSC, SD, NY, NC, PA, and TX

Watershed Area: 3,300 to 784,000 miWatershed Area: 3,300 to 784,000 mi22 Landuse: Usually Ag Landuse: Usually Ag andand Forest > Forest Forest > Forest

oror Ag > Urban Ag > Urban Ag generally mixture of pasture and row Ag generally mixture of pasture and row

cropcrop Treatment methods varied, e.g., in Treatment methods varied, e.g., in

chemical additives and type of filtrationchemical additives and type of filtration Sampling quarterly, w/semi-weekly during Sampling quarterly, w/semi-weekly during

high-use time of May to Septemberhigh-use time of May to September

Occurrence DataOccurrence Data Of Of 178178 pesticides/degradation products, pesticides/degradation products, 108108

were detected at least once in raw or were detected at least once in raw or finished waterfinished water

Occurrence data similar to that of the Occurrence data similar to that of the Willamette River and shallow groundwater Willamette River and shallow groundwater studiesstudies

Widely used Widely used herbicidesherbicides, e.g., atrazine, , e.g., atrazine, simazine, etc., were most common: 36 to simazine, etc., were most common: 36 to 96% of raw water samples; 19 to 96% of 96% of raw water samples; 19 to 96% of finished waterfinished water

Most common Most common insecticidesinsecticides in raw water: in raw water: Diazinon and chlorpyrofos at 35% and 5% of Diazinon and chlorpyrofos at 35% and 5% of samples, respectivelysamples, respectively

Raw Water versus Finished Raw Water versus Finished Water (Conventional Water (Conventional

Treatment)Treatment) Raw Water (323)Raw Water (323) Finished Water (228)Finished Water (228)

ChemicalChemical # Detects# Detects %% 9595thth %* %* # Detects# Detects %% 9595th th %*%*

AtrazineAtrazine 311311 96.396.3 0.5160.516 218218 95.695.6 1.401.40

SimazineSimazine 293293 90.790.7 0.0280.028 192192 84.284.2 0.3850.385

MetolachlorMetolachlor 288288 89.289.2 0.0330.033 198198 86.886.8 0.3360.336

PrometonPrometon 241241 74.674.6 0.1380.138 145145 63.663.6 0.0670.067

CyanazineCyanazine 145145 44.944.9 0.0070.007 9696 42.142.1 0.1280.128

DiazinonDiazinon 114114 35.335.3 0.0020.002 00 00 00

AlachlorAlachlor 8787 26.926.9 0.0020.002 5151 22.422.4 0.0270.027

MetribuzinMetribuzin 4747 14.614.6 0.0040.004 00 00 00

DacthalDacthal 1616 5.05.0 0.0020.002 88 3.53.5 <0.004<0.004

TerbacilTerbacil 77 2.22.2 0.0080.008 00 00 00

* ug/L Underlined = Regulated by SDWA

Pesticide Occurrence in Pesticide Occurrence in Clackamas River BasinClackamas River Basin

119 water samples analyzed for 86-198 dissolved 119 water samples analyzed for 86-198 dissolved pesticides (there are 11,000 pesticide products pesticides (there are 11,000 pesticide products registered in Oregon)registered in Oregon)

Pre- and post-treatment samples from one of the Pre- and post-treatment samples from one of the four WTPs along lower riverfour WTPs along lower river

63 pesticide compounds detected63 pesticide compounds detected 33 herbicides33 herbicides 15 insecticides15 insecticides 6 fungicides6 fungicides 9 pesticide degradation products9 pesticide degradation products

Tributary (8) sampling primarily during storm eventsTributary (8) sampling primarily during storm events WTP (1 of 5) sampling at regular intervals: 1 storm WTP (1 of 5) sampling at regular intervals: 1 storm

eventevent

Clackamas River Sample Clackamas River Sample SitesSites

Clackamas Pesticide Clackamas Pesticide Sampling ResultsSampling Results

Pesticides detected in lower basin Pesticides detected in lower basin tributaries and from the main stem of the tributaries and from the main stem of the riverriver

Atrazine, simazine most common in Atrazine, simazine most common in waters tested (50% of samples)waters tested (50% of samples)

Glyphosate, triclopyr, 2,4-D and Glyphosate, triclopyr, 2,4-D and metolachlor also occurmetolachlor also occur

Below human health standards, but Below human health standards, but several exceeded the EPA and DEQ several exceeded the EPA and DEQ aquatic-life benchmarks, e.g., fish and aquatic-life benchmarks, e.g., fish and benthic invertebratesbenthic invertebrates

Clackamas Pesticide Clackamas Pesticide Sampling ResultsSampling Results

Finished water: 60% of samples (9 of 15)Finished water: 60% of samples (9 of 15) 10 herbicides: diuron, simazine10 herbicides: diuron, simazine Also, 1 insecticide, 1 fungicide, 1 insect Also, 1 insecticide, 1 fungicide, 1 insect

repellent, and 2 pesticide degradation repellent, and 2 pesticide degradation productsproducts

0-2 pesticides detected in most finished 0-2 pesticides detected in most finished water samples; 6-9 detected during 2 water samples; 6-9 detected during 2 storm eventsstorm events

All detects below human health All detects below human health standards standards

Sources of PesticidesSources of Pesticides Tributaries drain basins containing nurseries, Tributaries drain basins containing nurseries,

pasture, agricultural, rural and residential landpasture, agricultural, rural and residential land Most of the 51 current-use pesticides have Most of the 51 current-use pesticides have

multiple uses, i.e., are not specific to one land multiple uses, i.e., are not specific to one land useuse 94% used on crops94% used on crops 92% used by nurseries92% used by nurseries 57% lawns and landscaping in urban areas57% lawns and landscaping in urban areas 49% on golf courses49% on golf courses 45% along roads and right-of-ways45% along roads and right-of-ways 7% on forestland7% on forestland

Glyphosate among most common detected Glyphosate among most common detected (roundup, rodeo, accord); household, Ag, Forest(roundup, rodeo, accord); household, Ag, Forest

Newspaper HeadlinesNewspaper HeadlinesMarch 10, 2008March 10, 2008

““Pharmaceuticals Lurking in U.S. Pharmaceuticals Lurking in U.S. Drinking Water”Drinking Water”

““Water Superintendent Does Not Water Superintendent Does Not See A Problem With See A Problem With

Pharmaceuticals in City Water”Pharmaceuticals in City Water”

““Drugs in Your Water?”Drugs in Your Water?”

Associated Press and Associated Press and Related ArticlesRelated Articles

AP survey of 62 large water providers and AP survey of 62 large water providers and independent researchersindependent researchers PPCPs in 24 systems, serving ~41 million peoplePPCPs in 24 systems, serving ~41 million people Antibiotics, anti-convulsants, mood stabilizers and Antibiotics, anti-convulsants, mood stabilizers and

sex hormonessex hormones Detections at very low levels (ppb-ppt)Detections at very low levels (ppb-ppt)

Portland: acetaminophen (tylenol), Portland: acetaminophen (tylenol), ibuprofen, caffeine, and sulfamethoxazxole ibuprofen, caffeine, and sulfamethoxazxole (antibiotic)(antibiotic)

Most detections occur, or are at higher Most detections occur, or are at higher levels, downstream from WWTPslevels, downstream from WWTPs

Pharmaceuticals and Pharmaceuticals and Personal Care Products Personal Care Products

(PPCPs)(PPCPs) Thousands of diverse chemical compounds: used by Thousands of diverse chemical compounds: used by

people, pets, and livestockpeople, pets, and livestock 50,000,000 lbs/annually, half used in agriculture: growth 50,000,000 lbs/annually, half used in agriculture: growth

promotionpromotion Virtually constant loading into the environmentVirtually constant loading into the environment Includes prescription and over-the-counter substancesIncludes prescription and over-the-counter substances

Antibiotics, steroids, synthetic hormonesAntibiotics, steroids, synthetic hormones Therapeutic drugs, herbal remediesTherapeutic drugs, herbal remedies Cosmetics, fragrances, shampoos, sun screen additivesCosmetics, fragrances, shampoos, sun screen additives Veterinary drugsVeterinary drugs Feed additives: nutritional, antibiotics (using subtherapeutic Feed additives: nutritional, antibiotics (using subtherapeutic

levels leads to lower animal care costs in large-scale confined levels leads to lower animal care costs in large-scale confined operations)operations)

Prescription drug use has increased by ~12% since Prescription drug use has increased by ~12% since 20032003

Endocrine DisruptersEndocrine Disrupters Chemicals that interfere Chemicals that interfere

with glands and with glands and hormones that regulate hormones that regulate biological processesbiological processes

Glands communicate Glands communicate with organs in the body with organs in the body by sending hormones by sending hormones through blood vesselsthrough blood vessels

Controls development, Controls development, reproduction, immune reproduction, immune system, organ function, system, organ function, metabolism, mood, etc.metabolism, mood, etc.

Source of PPCPsSource of PPCPs

Agriculture: Feed Agriculture: Feed supplements, supplements, Animal waste, Animal waste,

Veterinary drug use, Veterinary drug use, especially especially antibiotics and antibiotics and steroidssteroids

Municiple sewage Municiple sewage treatment plants treatment plants

Land application of Land application of sludgesludge

PPCPs Not Fully PPCPs Not Fully Metabolized by the BodyMetabolized by the Body

Excreted as active metabolites or parent substances

Pathway between homes and septic or municipal sewage facilities.

Improper Disposal of Improper Disposal of PharmaceuticalsPharmaceuticals

Discarding unused drugs and personal care products down the toilet is a common but poor disposal method.

Disposal of DrugsDisposal of DrugsFederal GuidelinesFederal Guidelines

•Take unused, unneeded, or expired prescription drugs out of their original containers and throw them in the trash.•Mixing prescription drugs with an undesirable substance, such as used coffee grounds or kitty litter, and putting them in impermeable, non-descript containers, such as empty cans or sealable bags, will further ensure the drugs are not diverted.•Flush prescription drugs down the toilet only if the label or accompanying patient information specifically instructs doing so.

Fate and Transport of Fate and Transport of PPPCsPPPCs

How do these chemicals move into How do these chemicals move into groundwater:groundwater:

Generally must travel though Generally must travel though unsaturated zoneunsaturated zone Open spaces not completely filled with Open spaces not completely filled with

waterwater In laboratory column experimentsIn laboratory column experiments

Simulated unsaturated zoneSimulated unsaturated zone Artificial loading of contaminant in Artificial loading of contaminant in

representative solution representative solution

Chemical CharacteristicsChemical Characteristics Research needed, preliminary data onlyResearch needed, preliminary data only Sorption characteristics:Sorption characteristics:

Attachment to “solids”, e.g., organic matterAttachment to “solids”, e.g., organic matter Bind up contaminant in soil, enhance is surface Bind up contaminant in soil, enhance is surface

waterwater Retardation of contaminants (VRetardation of contaminants (Vww/V/Vcc): ):

One study found values from 1.8 to 4.8One study found values from 1.8 to 4.8 Microbial transformation:Microbial transformation:

Biodegradation, e.g., organic compounds => COBiodegradation, e.g., organic compounds => CO22

Persistence (residence time): Length of time Persistence (residence time): Length of time for compound to break down.for compound to break down.

PPCPs: Health EffectsPPCPs: Health Effects Found in very low concentrations (ppb – ppt)Found in very low concentrations (ppb – ppt) Drinking one gallon/day of water containing 1ppb Drinking one gallon/day of water containing 1ppb

of a pharmaceutical would be equivalent to:of a pharmaceutical would be equivalent to: 1 Valium or 1 Ritalin in 3.5 years1 Valium or 1 Ritalin in 3.5 years One Benadryl in 14.5 yearsOne Benadryl in 14.5 years One Children’s Tylenol in 58 yearsOne Children’s Tylenol in 58 years

Concern that long-term exposure may cause subtle Concern that long-term exposure may cause subtle effects that could accumulate over time through effects that could accumulate over time through generationsgenerations

Hormones work in body at very low concentrations Hormones work in body at very low concentrations and affect sexual developmentand affect sexual development

Prevalent use of antibiotics producing “super Prevalent use of antibiotics producing “super bugs”, i.e., resistant to current medicationbugs”, i.e., resistant to current medication

Aquatic Organisms: constant/multi-generational Aquatic Organisms: constant/multi-generational exposureexposure

PPCPs: Health EffectsPPCPs: Health Effects Lack of definitive information regarding long-term Lack of definitive information regarding long-term

health effects. health effects. However:However: Combination of chemicals: One-third of samples in a Combination of chemicals: One-third of samples in a

reconnaissance study in which PPCPs were detected, reconnaissance study in which PPCPs were detected, contained more than 10 individual chemicalscontained more than 10 individual chemicals

Evidence of impact on wildlife, e.g., fish, plankton, in ppt Evidence of impact on wildlife, e.g., fish, plankton, in ppt rangerange

Similar concentrations of pesticides have demonstrated Similar concentrations of pesticides have demonstrated impactimpact

Impact of constant exposure to a mixture of low-level Impact of constant exposure to a mixture of low-level chemicalschemicals

Target vs. non-Target organismsTarget vs. non-Target organisms Detection levelsDetection levels

Research Methods: pptResearch Methods: ppt Drinking Water Methods: ppbDrinking Water Methods: ppb

USGS Reconnaissance USGS Reconnaissance Study 1999-2000: 139 Study 1999-2000: 139

StreamsStreams

Characteristics of BasinsCharacteristics of Basins 24 streams in 19 states (earlier pesticide 24 streams in 19 states (earlier pesticide

occurrence review)occurrence review) 14 streams from basins with intense animal 14 streams from basins with intense animal

productionproduction Hogs (2)Hogs (2) Poultry (6)Poultry (6) Dairy or Beef cattle (4)Dairy or Beef cattle (4) Mixed-animal production (2)Mixed-animal production (2)

9 urban basins: Denver, Dallas, Minneapolis, 9 urban basins: Denver, Dallas, Minneapolis, and Salt Lake Cityand Salt Lake City

One mixed basin: Mississippi River in One mixed basin: Mississippi River in LouisianaLouisiana

PPCPs in 1999-2000 PPCPs in 1999-2000 Reconnaissance StudyReconnaissance Study

Surface Water Surface Water (139)(139)

Groundwater Groundwater (47)(47)

Drinking Drinking WaterWater

(74)(74)

Non-DrugsNon-Drugs 81%81% 15%15% 64%64%

AntibioticsAntibiotics 48%48% 26%26% 26%26%

PharmaceuticalsPharmaceuticals 32%32% 6%6% 23%23%

MetabolitesMetabolites 69%69% 43%43% 19%19%

DEETDEET 74%74% 35%35% 19%19%

CaffeineCaffeine 71%71% 11%11% 54%54%

Treatment EffectivenessTreatment Effectiveness

Major source is from wastewater Major source is from wastewater treatment plant effluent discharged to treatment plant effluent discharged to surface watersurface water

Surface water treatment, study Surface water treatment, study evaluatedevaluated Conventional/Direct filtrationConventional/Direct filtration Slow sandSlow sand Variety of coagulants/conditionersVariety of coagulants/conditioners

Limited ability to remove these Limited ability to remove these chemicalschemicals

Effectiveness of Effectiveness of Conventional TreatmentConventional Treatment

Chemical (Use)Chemical (Use) Raw Water (ng/L)Raw Water (ng/L) % of samples% of samplesfound infound in

Finished Water Finished Water (ng/L)(ng/L)

% of samples% of samplesfound infound in

DEET (1)DEET (1) 10.810.8 100100 10.910.9 94.494.4

TCEP (2)TCEP (2) 21.921.9 94.494.4 9.99.9 88.988.9

Caffeine (3)Caffeine (3) 26.626.6 94.494.4 27.727.7 83.383.3

Ibuprofen (4)Ibuprofen (4) 7.37.3 83.383.3 10.410.4 77.877.8

Atrazine (5)Atrazine (5) 153.8153.8 77.877.8 117.8117.8 72.272.2

Meprobromate (6)Meprobromate (6) 6.86.8 66.766.7 5.75.7 66.766.7

Dilanton (7)Dilanton (7) 4.14.1 88.988.9 3.33.3 61.161.1

Iopromide (8)Iopromide (8) 13.813.8 61.161.1 9.09.0 55.655.6

Carbamazapine (7)Carbamazapine (7) 5.75.7 88.988.9 4.14.1 44.444.4

Gemfibrozil (9)Gemfibrozil (9) 6.16.1 61.161.1 5.25.2 22.222.2

Estrone (10)Estrone (10) 1.41.4 5.65.6 1.21.2 11.111.1

Acetominophen (4)Acetominophen (4) 3.63.6 22.222.2 1.11.1 5.65.6

Ethromycin-H2O (11)Ethromycin-H2O (11) 2.72.7 44.444.4 2.62.6 5.65.6

Sulfamethoxazole (11)Sulfamethoxazole (11) 17.817.8 83.383.3 2.12.1 5.65.6

Naproxen (12)Naproxen (12) 5.65.6 61.161.1 1.01.0 5.65.6

Ranking of Treatment Ranking of Treatment Methods Removal of PPCPsMethods Removal of PPCPs

1.1. Reverse Osmosis (RO)Reverse Osmosis (RO)2.2. NanofiltrationNanofiltration3.3. Advanced Oxidation (AOP)Advanced Oxidation (AOP)4.4. Granular Activated Carbon (GAC)Granular Activated Carbon (GAC)5.5. OzoneOzone6.6. ChlorineChlorine7.7. Micro/UltrafiltrationMicro/Ultrafiltration8.8. UVUV

Responsibility of water Responsibility of water system?system?

SDWA does not require additional sampling for these SDWA does not require additional sampling for these chemicals nor does it require systems to inform their chemicals nor does it require systems to inform their customers of detections of unregulated chemicalscustomers of detections of unregulated chemicals

Drinking Water Program recommends that water Drinking Water Program recommends that water systems do inform customerssystems do inform customers Better to tell them than for them to find out through other Better to tell them than for them to find out through other

routesroutes Absent other information, public will reach its own Absent other information, public will reach its own

conclusionsconclusions Recommendations:Recommendations:

Water meets drinking water standardsWater meets drinking water standards Concentrations are minuteConcentrations are minute Studies are under way, however there is no known human Studies are under way, however there is no known human

health effectshealth effects Customers can choose to install simple carbon filtersCustomers can choose to install simple carbon filters

From Candidate From Candidate Contaminant List (CCL) to Contaminant List (CCL) to

RegulationRegulation SDWA regulates more than 90 SDWA regulates more than 90

contaminantscontaminants EPA must periodically publish a CCL of EPA must periodically publish a CCL of

contaminants to potentially regulatecontaminants to potentially regulate Current list is CCL3: Current list is CCL3:

93 chemicals, 11 microbiological93 chemicals, 11 microbiological EPA evaluated ~7,500 chemicals and microbes EPA evaluated ~7,500 chemicals and microbes

List is evaluated for potential health List is evaluated for potential health impacts and overall benefit of establishing impacts and overall benefit of establishing regulationregulation

Future Regulation by Future Regulation by SDWA?SDWA?

Does the contaminant adversely affect public Does the contaminant adversely affect public health?health? Toxicology Toxicology

Is the contaminant likely to occur in PWSs at a Is the contaminant likely to occur in PWSs at a frequency to pose a threat to public health?frequency to pose a threat to public health? Evidence of environmental impactEvidence of environmental impact MonitoringMonitoring Laboratory analytical capabilities?Laboratory analytical capabilities?

Will regulation of the contaminant provide a Will regulation of the contaminant provide a meaningful opportunity for health risk meaningful opportunity for health risk reduction?reduction?

Regulation in the near future not likelyRegulation in the near future not likely