Overview. Emerging Contaminants in Michigan s Water. Emerging Chemical Contaminants. Emerging Chemical Contaminants. Emerging Chemical Contaminants

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1 Overview Emerging Contaminants in Michigan s Water Sheridan Kidd Haack, PhD US Geological Survey Lansing, MI skhaack@usgs.gov Chemical Classes Sources Michigan USGS studies with water and wastewater utilities EMERGING CHEMICAL CONTAMINANTS Emerging Chemical Contaminants Pharmaceuticals (human and veterinary) Intended to be bioactive Do not generally bioaccumulate Not toxic to humans (or intended animals) May have unintended consequences for non-target organisms Fluoxetine/fish Diclofenac/vultures Degradation products may be toxic Acetaminophen forms toxics during chlorination Carbamazepine (antiepileptic) photodegrades to acridine (mutagen) Personal Care Products (chemicals in lotions and potions) Not toxic to humans Not intended to be ingested May have unintended consequences for non-target organisms Emerging Chemical Contaminants Antibiotics (human and veterinary) Some veterinary antibiotics are toxic to humans Concern over antibiotic resistance in bacteria Hormones and steroids (natural and prescribed) Clearly influence reproduction and endocrine function Detergents, disinfectants, fragrances, fumigants, etc. and their by-products Not intended to be consumed Several compounds have endocrine disruption effects (detergent by-products such as nonylphenols, musk fragrances, bisphenol A, triclosan) Emerging Chemical Contaminants Fire-retardants PBDEs found to bioaccumulate Pesticides and herbicides Intended to be bioactive Most current-use do not bioaccumulate Some implicated in endocrine disruption 1

2 Endocrine Disruptive Compounds Occur in many chemical classes Hormones Pesticides (atrazine, diazinon) Industrial (bisphenol A, other plasticizers) i Fragrances (AHTN, HHCB) Detergent by-products (nonyl- and octyl-phenols) Of particular concern because these are active at very low concentrations and influence reproduction and growth Chemical Structure Affects Fate and Function Bioaccumulate or not Endocrine disrupter or not For WWTP: biodegradation or sorption to solids For WTP: susceptibility to chlorine or ozone Few generalities Human Sources A Michigan beach with a storm drain WWTPs CSOs Land application of municipal biosolids or septage Illicit connections to storm or agricultural l drains A Michigan beach Animal Sources Manure contains veterinary pharmaceuticals and cleaning agents MDEQ: image of a septage application violation Sources- Septic Systems Liquid Solid (μg/l) (μg/kg) AHTN (tonalide) ND 18 Triclosan p-nonylphenol Carbamazepine.5 Caffeine 38 Acetaminophen 45 Cotinine 1.7 Kolpin, D.W., 26, Keynote address for Risk Assessment of Pharmaceuticals & Veterinary Medicines in the Environment, Sept , Amsterdam, The Netherlands Sources Antibiotics in Septic Systems (ug/l), n=9 Chlortetracylcine <.1 for all Iso-Chlortetracyline < Iso-Epi-Chlortetracyline < Anhydro-Chlortetracyline <.1 for all Tetracycline <.1-2. Epi-Anhydro-Tetracycline < Epi-Tetracyline < Ofloxacin < Ciprofloxacin Erythromycin <.1.14 Kolpin, D.W., 26, Keynote address for Risk Assessment of Pharmaceuticals & Veterinary Medicines in the Environment, Sept , Amsterdam, The Netherlands 2

3 Septic Systems in Michigan MDEQ, million septic systems in Michigan Up to 1% are failing Sources mg/kg Kinney et al., 26, ES&T, 4, pp , Survey of organic wastewater contaminants in 1 mg/kg biosolids 8 6 destined for land 4 2 application Prescrip. Drugs Steroids Detergent Metab. Fragrances Compound Class Nonprescrip. Fire Disinfectants Drugs Retardants Compound Class Biosolid A Biosolid B Biosolid C Biosolid D Biosolid E Biosolid F Biosolid G A-E are the Class A F & G are the Class B Biosolid A Biosolid B Biosolid C Biosolid D Biosolid E Biosolid F Biosolid G A-E are the Class A PAHs F & G are the Class B Sources Antibiotics found in all swine waste lagoons sampled (N=78): Compound % Med Max μg/l CTET SMTH LINC TET OTET SDIMX TYLO Campagnolo, et al. 22, Science of the Total Environment Meyer, 24, in Kummerer, (ed.) Pharmaceuticals in the Environment, Springer-Verlag. Sources Antibiotics in cattle waste lagoons (ug/l), n=3 Chlortetracylcine <.1.11 Iso-Chlortetracyline Iso-Epi-Chlortetracyline Anhydro-Chlortetracyline <.1 for all Tetracycline <.1.83 Epi-Anhydro-Tetracycline <.1 for all Epi-Tetracyline <.1.47 Erythromycin <.5.14 Sulfamethazine <.5.71 Tylosin.1.28 National Studies USGS Toxic Substances Hydrology Program Emerging Contaminants Project Kolpin, D.W., 26, Keynote address for Risk Assessment of Pharmaceuticals & Veterinary Medicines in the Environment, Sept , Amsterdam, The Netherlands 3

4 Occurrence National Studies Streams (1999-2) Ground Water (2) Sources of Drinking Water (21) Streambed Sediment (22) Surface- and Groundwater Drinking Water Sources ES&T; March 15, 22 v. 36, no. 6, p Focazio et al., 28, Science of the Total Environment, 42, pp What Have We Learned? Present at sub-ppb (ng/l) concentrations in surface and groundwater Present as complex mixtures With other chemicals as well Reflect a wide range of human activities Some compounds mobile and persistent Depend on the media (water, solids, tissue) sampled Michigan Studies Haack, 29, Antibiotic, Pharmaceutical, and Wastewater-Compound Data for Michigan, , USGS report, in press surface water sites for antibiotics 1/5 antibiotics detected at 7/2 sites 11 surface water sites for pharmaceuticals 8/13 pharmaceuticals detected at 7/11 sites Michigan Studies 4 surface water sites for wastewater compounds in filtered water 56/62 compounds; detections at each site Maximum detections on Clinton River (46) and S. Branch River Raisin, both downstream of WWTP (36) Kalamazoo (1-18 compounds), Clinton (9-46), Muskegon (3-16), Saginaw (2-33), Grand (2-3) rivers quarterly for two years Michigan Studies 2 public water supply wells, 8 times each Portland, Ionia County Parchment, Kalamazoo County Detections of -13 compounds Varied by date Some detections of AHTN, HHCB, octylphenol Potential endocrine disruptive compounds 4

5 Michigan Studies Concentrations generally near reporting limit Compounds detected generally similar to those reported by USGS and others nationwide Some compounds detected in field blanks Important to conduct QA/QC and sample carefully Antibiotics and pharmaceuticals, AHTN, HHCB, carbamazepine never in blanks Among the more frequently-detected ompounds Emerging Chemical Contaminants in Michigan Industrial and household chemicals and herbicides are found in both urban and agricultural settings Total concentrations of all chemicals similar Nature of chemicals different in urban and agricultural settings Emerging Chemical patterns Are site-specific Suggest local land use Chemicals occur as complex mixtures from many sources Concentrations are usually quite low Urban Setting Oakland County, MI Pop. 1.2 million 25% urban, 32% suburban 5 headwater watersheds Funded by Oakland County Site-specific patterns Musk fragrances (AHTN/HHCB) only downstream of WWTPs Cholesterol only in one watershed Generally fewer detections on upstream reaches Herbicides Prometon (right-of-way) 3 detections Metolachlor (corn/soybeans) detections DET MET AHTN/HHCB FIRE RETARDANT 2.57 CHOLESTEROL.11 CAFFEINE 2.24 PAH PLASTICIZER 1.2 Total concentration (µg/l) WWTP River Raisin: Up- and downstream of Adrian, MI Concentration (ug/l) Concentration (ug/l) River Raisin Above and Below Adrian Above Adrian Below Adrain PAH PHENOL p-cresol PLAST SOLV River Raisin Above and Below Adrian Above Adrian Below Adrian DET MET AHTN/HHCB FRAG FIRE RET STEROL CAFFEINE Agricultural Setting Site-specific patterns for emerging chemicals Industrial compounds at the most urban site Antibiotics reflect sewage-lagoon and agricultural (?) inputs Pigeon River Taft Drain.34 Bad Axe Creek Pinnebog River Sulfamethoxazole l.2 Sulfadimethoxine/Sulfamethazine 1.2 TOTAL CONCENTRATION DET MET FIRE RETARDANT FRAGRANCE CAFFEINE PAH PLASTICIZER ANTIBIOTIC WWTP CAFO Antibiotic Patterns CONCENTRATION (MI ICROGRAMS PER LITER) General Use Antibiotics Azithromycin Erythromycin Erythromycin-H2O/ Anhydroerythromycin Sulfamethoxazole Trimethoprim Ciprofloxacin Ofloxacin.84 Pigeon River Ciprofloxacin/Ofloxacin 5

6 Antibiotic Patterns Veterinary Antibiotics Influence of Hydrology Galien River CONCENTRATION (M MICROGRAMS PER LITER) Sulfadimethoxine Sulfamethazine Tylosin NUMBER OF DET TECTIONS Low flow High flow Industrial Human Other chemicals wastewater chemicals chemicals Sterols Agricultural herbicides and pesticides Total Upstream/ Downstream of 1 U.S. Cities Difference Only During Low Flow Conditions Sediments Are Also An Issue Percent Detected 8% Water (3) Sediment (36) 6% 4% 2% % Kolpin et al., 24, Science of The Total Environment, v. 328, p Sulfamethoxazole Codeine Cotinine Trimethoprim Dehydronifedipine Diltiazem Acetaminophen Ranitidine Caffeine Diphenhydramine Carbamazapine Cimetidine Metformin Erythromycin Thiabendazole Fluoxetine Gemfibrozil Furlong et al. Miconazole Utility Studies USGS has collaborated with USEPA and with utilities in several states to evaluate water and wastewater treatment processes and effects on chemicals ca New York, North Carolina, Massachusetts, Florida, New Jersey, Colorado, Minnesota USGS has targeted research on selected chemicals in water or wastewater treatment Antibiotics, antidepressants WWTP Study WWTP Settings upstream effluent 1 st downstream 2 nd downstream 2 Background settings ES&T, 25, v. 39, n. 14, p

7 Frequency of Detection (%) WWTP Study Summary Results Upstream Effluent Downstream 1 1. Downstream 2 median DEET galaxolide (HHCB) tonalide (AHTN) tributylphosphate triclosan ncentration (μg/ L) Median Con WWTP Summary Some chemicals were found in 1% of WWTP effluents at concentrations significantly above background Some chemicals are recalcitrant to degradation Carbamazepine Ratios of selected chemicals may indicate proximity to, or distance from, source Chemicals May Indicate Fecal Pollution Haack et al., 29, J. Environmental Quality, 38, pp surface-water samples with <5 E. coli per 1 ml human pharmaceuticals or chemical indicators of wastewater treatment plant effluent in 6 Chemicals present even when microbial standards are met Unlike indicator bacteria, can suggest source Water Treatment Effect on Antibiotics Effective: Calgon WPH powdered activated carbon Reverse osmosis Chlorine and ozone Ineffective: coagulation/flocculation/sedimentation lime/soda ash softening ultraviolet irradiation ion exchange Adams et al., J. Environmental Engineering, 128, pp Chemical Persistence During Drinking-Water Treatment Concentrations of selected compounds in samples of raw (circles), settled (triangles), filtered (squares), and finished (inverted triangles) water from Stackelberg et al., 24, Science of the Total Environment, 329, pp Observations Studies by USGS and others indicate that different chemicals respond to treatment in different ways Benotti et al., 29, ES&T Atrazine poor response to either chlorine or ozone Carbamazepine response to chlorine varies with ph; ozone works well Trimethoprim, both chlorine and ozone work well 7

8 Observations Benotti et al. proposed selected chemicals as indicators of treatment effectiveness For WWTP, biodegradation seems to be more effective than sorption to solids However, degradation products may also be bioactive, or more hazardous Summary As in other states, water in Michigan may contain emerging chemical contaminants Many sources, both human and other, contribute these contaminants to Michigan water Results are usually site-specific suggesting local influences Concentrations are usually low, but Usually complex mixtures of chemicals Indicate multiple sources of contamination Cannot assume only the tested chemicals are present For More Information USGS Emerging Chemicals in the Environment Project (information, bibliography, links) gov/regional/emc/ USGS Publications (searchable; Michigan report will be there after publication) Sheridan K. Haack, , Great Lakes Restoration Initiative Funding Guide 9_r3.pdf Measuring Progress of Toxic Reduction Activities and Preventing New Chemicals from Entering the Great Lakes proposed $7.8 million in grants Musks have been detected in fish in the Detroit River Carbamazepine is persistent into the lakes 8