AN OVERVIEW OF ORGANIC CONTAMINANTS IN THE CHAMPLAIN BASIN

Transcription

1 AN OVERVIEW OF ORGANIC CONTAMINANTS IN THE CHAMPLAIN BASIN

2 Organic Contaminants of Emerging Concern in the Lake Champlain Basin: A Review of Current Knowledge, Nathaniel Shambaugh natsh@myfairpoint.net December 29, 2016 *Lake Champlain Basin Program Technical Report # Funded by Lake Champlain Basin Program and NEWIPCC

3 ORGANIC CONTAMINANTS OF EMERGING CONCERN (OCECs) ORGANIC: containing carbon, NOT metals or minerals ANTHROPOGENIC: man-made, NOT bacteria, cyanotoxins, etc. AQUEOUS: dissolved in water, NOT bound to sediment EMERGING CONCERN: recently introduced or discovered to be a potential problem, NOT well regulated

4 CONTAMINANT TYPES PHARMACEUTICALS PESTICIDES POLYCYCLIC AROMATIC HYDROCARBONS (PAHs) PERSONAL CARE PRODUCTS ANTIBIOTICS

5 ABLE TO FIND DATA ON: SEWAGE TREATMENT PLANT EFFLUENT Treated waste Untreated waste Combined sewer overflow STORMWATER RUNOFF AGRICULTURAL RUNOFF Surface runoff Tile drain discharge URBAN STREAM RAILROAD PESTICIDE RUNOFF GOLF COURSE PESTICIDE RUNOFF LAMPRICIDE TREATMENT

6 * Looked at Priority (regulated) Pollutants such as: Methylene Chloride, Acetone, Chloroform and other organic solvents. Samples collected in Low ppb detection limits.

7 NPDES EFFLUENT CHARACTERIZATION WHOLE EFFLUENT TOXICITY AND PRIORITY POLLUTANTS LAKE CHAMPLAIN BASIN, VERMONT by Alan Quackenbush Vermont Agency of Natural Resources Department of Environmental Conservation Biomonitoring and Aquatic Studies Unit April 1993 * Looked at Priority (regulated) Pollutants such as: Methylene Chloride, Acetone, Chloroform and other organic solvents. Samples collected in Low ppb detection limits.

8 Concentrations of Selected Pharmaceuticals and Personal Care Products in the Effluents of Twelve Municipal Wastewater Treatment Facilities in Vermont USEPA Region I and Vermont DEC January 30, 2006 *FIRST STUDY TO TARGET EMERGING CONTAMINANTS Samples collected November 2002 Low part per trillion detection limits.

9 COMPOUND HIGHEST CONCENTRATION WWTF TRICLOCARBAN PPB BELLOWS FALLS 17b ESTRADIOL PPB BURLINGTON MAIN ESTRONE PPB SAXTONS RIVER 17a ETHINYLESTRADIOL PPB BELLOWS FALLS BISPHENOL A PPB NORTHFIELD 4-NONYLPHENOL PPB BELLOWS FALLS

10 CONTAMINANTS OF EMERGING CONCERN IN WASTEWATER TREATMENT FACILITY EFFLUENT WITHIN THE WINOOSKI RIVER WATERSHED OF VERMONT Vermont Department of Environmental Conservation *Analyzed for 69 compounds in the Winooski River and 8 treatment facilities. Samples collected in Low part per trillion detection limits.

11 DETECTIONS IN WINOOSKI BASIN WWTF EFFLUENT: 2008 ANTIMICROBLIALS (1) ANTIOXIDENTS (1) DEODERIZERS (1) DISINFECTANTS (1) FIRE RETARDANTS (4) FRAGRANCES (4) PESTICIDES (3) DETERGENT METABOLITES (6) POLYCYCLIC AROMATIC HYDROCARBONS (1) ANIMAL STEROIDS (2) PLASTICIZERS (7) MISCELLANEOUS: CAFFEINE COTININE (NICOTINE METABOLITE) ISOPROPYLBENZENE (HYDROCARBON) METHYL SALICYLATE TETRACHLOROETHENE (chlorinated hydrocarbon) INDOLE 5-METHYL-1H-BENZOTRIAZOLE ESTRONE (sex hormone) FLUOXETINE (antidepressant-prozac) * 40 compounds detected at quantifiable levels.

12 DETECTIONS IN THE WINOOSKI RIVER 2008: CONTAMINANT 5-METHYL-1H-BENZOTRIAZOLE (anticorrosive) 0.23 ppb FLUOXETINE (antidepressant) ppb COTININE (nicotine metabolite) 0.11 ppb DIETHYL PHTHALATE (plasticizer) 0.27 ppb CAFFEINE ppb TRIETHYL CITRATE (plasticizer) ppb MAXIMUM DETECTED

13 WASTEWATER EFFLUENT, COMBINED SEWER OVERFLOWS, AND OTHER SOURCES OF ORGANIC COMPOUNDS TO LAKE CHAMPLAIN P. Phillips and A. Chalmers (USGS) JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION Vol. 45, No. 1 AMERICAN WATER RESOURCES ASSOCIATION February 2009 *Analyzed for 62 PAHs, pesticides, and personal care products. Samples collected in 2006

14 COMPOUNDS DETECTED PESTICIDES 3 PAHs 6 FRAGRANCES and FLAVORS 4 STEROLS 4 DETERGENT DEGRADATES 5 FLAME RETARDANTS 5 MISCELLANEOUS 8 EXAMPLE: Range in CSO Concentration WTTP Effluents Urban-Stream Stormflow PHENANTHRENE (ppb) nd nd

15 Combined Sewer Overflows: An Environmental Source of Hormones and Wastewater Micropollutants By Phillips, P. J., Chalmers, A. T., Gray, J. L, Kolpin, D. W., Foreman, W. T., and Wall, G. R. Environmental Science and Technolnology, 2012, 46 (10), pp *Analyzed for 89 compounds, similar to previous study, plus hormones. Samples collected in 2008

16 Detections of Trace Wastewater Contaminants, Burlington, VT. COMPOUND REPORTING LIMIT (ng/l) PERCENT DETECTION PLANT EFFLUENT CSO Estrogens 17-beta-estradiol Androgens 11-Ketotestosterone Wastewater Micropollutants Triclosan

17 Investigating dynamic sources of pharmaceuticals: Demographic and seasonal use are more important than down-the-drain disposal in wastewater effluent in a University City setting Christine Vatovec, Patrick Phillips, Emily VanWagoner, Tia-Marie Scott, Edward Furlong Science of The Total Environment Volume 572, 1 December 2016, Pages *Analyzed for 109 compounds, primarily pharmaceuticals. Samples collected in 2014 INTERESTING IN THAT LOOKED AT DAILY VARIABILITY, AS WELL AS INFLUENT AND EFFLUENT CONCENTRATIONS.

18 VERMONT AGENCY OF AGRICULTURE SURFACE WATER PESTICIDE MONITORING CORN HERBICIDES AND METABOLITES IN LAKE CHAMPLAIN AND TRIBS IN ASSOCIATION WITH LCBP LONG-TERM MONITORING PROGRAM ONGOING PROJECT FOR 15 YEARS ALSO, (MOSTLY SMALL SCALE) TARGETED PROJECTS: GOLF COURSE RUNOFF RAILROAD RUNOFF LAMPRICIDE TREATMENT OTHERS

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20 VERMONT CORN HERBICIDE SURFACE WATER MONITORING ( ) Lake Champlain & Tribs (collected by VTDEC) Six lake sites & seven tributaries Tribs sampled during storm events >1200 SAMPLES Statewide Agency of Agriculture Sampling Sampling sites throughout Vermont Detailed investigations and targeted sampling possible >400 SAMPLES

21 CORN HERBICIDES LARGEST CROP IN VT: (FIELD) CORN TO FEED DAIRY COWS WEED KILLERS (HERBICIDES) USED ON FIELD CORN ARE THE MOST WIDELY USED PESTICIDES IN VT ATRAZINE and METOLACHLOR MOST WIDELY USED CORN HERBICIDES ATRAZINE and METOLACHLOR RELATIVELY STABLE (long lived) BOTH HAVE BREAKDOWN PRODUCTS WHICH ARE VERY WATER SOLUBLE

22 Lake Champlain Long-term Water Quality and Biological Monitoring Project

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24 SUM OF MAX CONCENTRATIONS (PPB) MAXIMUM RIVER CONCENTRATIONS WINOOSKI LAMOILLE METOLACHLOR ATRAZINE POULTNEY OTTER CREEK MISSISQUOI LITTLE OTTER PIKE

25 SUM OF MAXIMUM CONCENTRATION (PPB) MAXIMUM LAKE SEGMENT CONCENTRATIONS METOLACHLOR ATRAZINE MAIN LAKE MALLETTS BAY ALBURG DIAMOND ISLAND ST. ALBANS BAY MISSISQUOI BAY

26 KG/YR MISSISQUOI BAY LOADING MISSISQUOI PIKE 0 ATRAZINE METOLACHLOR

27 JEWETT BROOK

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29 CORN HERBICIDE HIGHEST CONCENTRATION (ppb) LOCATION ATRAZINE 32.9 JEWETT BROOK ATRAZINE-DESETHYL 2.6 JEWETT BROOK ATRAZINE-DESISO 2.2 JEWETT BROOK HYDROXY ATRAZINE 2.0 JEWETT BROOK METOLACHLOR 12.0 JEWETT BROOK METOLACHLOR ESA 4.1 JEWETT BROOK SIMAZINE 7.9 JEWETT BROOK DIMETHENAMID 2.9 JEWETT BROOK *ALSO VERY HIGH IN PHOSPHORUS AND NITROGEN

30 RAILROAD SAMPLING

31 RAILROAD HERBICIDES SPRAYING PESTICIDES ON ROCKS (BALLAST) SO SOME RUNOFF INEVITABLE PROBLEM SITES IN VERMONT APPEAR TO BE WHERE MULTIPLE TRACKS/SIDINGS

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33 GOLF COURSE SAMPLING: HERBICIDES, FUNGICIDES and INSECTICIDES ANALYZED SAMPLE SITES: GOLF COURSE PONDS GOLF COURSE POND OUTLETS STREAMS ABOVE, WITHIN, AND BELOW GOLF COURSES

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35 GOLF COURSE FUNGICIDES PROBLEMS ARISE WHEN LARGE LATE FALL RAINSTORMS OCCUR AFTER FUNGICIDE APPLICATION AND BEFORE SNOWPACK

36 Lake Champlain Sea Lamprey Control Program Chemical Treatment Summary: Missisquoi River, Vermont 2012 Stephen Smith U.S. Fish and Wildlife Service Lake Champlain Fish and Wildlife Resources Office

37 LAMPRICIDE: 2012 MISSISQUOI BAY TFM DATA VERMONT DEPT. OF HEALTH DRINKING WATER ADVISORY LEVEL: MAXIMUM DETECTED IN DRINKING WATER INPUT: MAXIMUM DETECTED IN FINISHED DRINKING WATER: MAXIMUM DETECTED IN MISSISQUOI BAY: CONCENTRATION DETECTED 12 WEEKS AFTER TREATMENT: 35 PPB 33 PPB < 1PPB 226 PPB 1.4 PPB

38 NEONICOTINOID INSECTICIDES: POSSIBLE ISSUES CONCERNING TOXICITY TO HONEYBEES and OTHER POLLINATORS. Neonicotinoid insecticides used as replacements for pyrethroid insecticides which were used as replacements for organophosphate insecticides

39 Virtually all conventional corn and soy seeds planted in the U.S. are treated with systemic insecticides (neonicotinoids) and fungicides. *Neonicotinoids are VERY water soluble and persistent.

40 A PRELIMINARY INVESTIGATION OF PESTICIDES IN VERMONT POLLEN: 2012 Vermont Agency of Agriculture, Food, and Markets Contact: BEES: PESTICIDES: PESTICIDE ANALYSIS:

41 JEWETT BROOK

42 Neonicotinoid and Corn Herbicide Runoff from Corn Fields in 2015 and SITE IMIDACLOPRID CLOTHIANIDIN THIAMETHOXAM ATRAZINE METOLACHLOR DESETHYL METOLACHLOR NAME ATRAZINE ESA JEWETT BROOK (JEW01) Maximum ppb 2015(2016) Maximum ppb 2015(2016) Maximum ppb 2015(2016) Maximum ppb 2015 Maximum ppb 2015 Maximum ppb 2015 Maximum ppb (0.07) 0.33(0.49) 0.69 (1.07) PIKE RIVER ND ROCK RIVER ND STEVENS ND 0.06(0.44) 0.10(0.23) BROOK TILE #8 0.84(0.10) 0.73(4.17) 0.10 (1.31) (CORN) TILE #9 0.54(1.12) 0.64(0.60) 0.03(ND) (SOY) EPA Aquatic Life Benchmark (ppb) * NEONICS ARE HIGHLY TOXIC NOT ONLY TO POLLINATORS, BUT ALSO TO AQUATIC INSECTS

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44 BIG PICTURE CONCLUSION: 160 ORGANIC CONTAMINANTS WITH QUANTIFIABLE CONCENTRATIONS FOUND IN OUR WATERS!

45 BIG PICTURE CONCLUSION: 160 ORGANIC CONTAMINANTS WITH QUANTIFIABLE CONCENTRATIONS FOUND IN OUR WATERS! SO WHAT???????

46 OCECs IN OUR SURFACE WATERS: NEXT STEP: ARE THEY A PROBLEM FOR OUR AQUATIC PLANTS AND ANIMALS? RISK ASSESSMENT: DETERMINE IF CONCENTRATIONS OF OCECs IN OUR WATERS ARE ACTUALLY OF CONCERN (in progress)

47 ACUTE TOXICITY ACUTE TOXICITY= SHORT-TERM EXPOSURE LIKELY TO LEAD TO IMMEDIATE DEATH OR OTHER EFFECTS EC50 = CONCENTRATION OF A SUBSTANCE CAUSING AN EFFECT ON 50% OF TEST ORGANISMS LC50 = CONCENTRATION OF A SUBSTANCE LETHAL TO 50% OF TEST ORGANISMS

48 ACUTE TOXICITY TESTS:

49 ACUTE RISK QUOTIENT (RQ) = (ACUTE RISK OF TOXICITY TO AT LEAST ONE SPECIES OF PLANT OR ANIMAL) RQ = MAXIMUM DETECTED (in CSO, WWTFE, stream, river, lake) Divided by LOWEST LC50 or EC50 If RQ>1 then should be concerned (i.e. If maximum detected is greater than EC50)

50 EXAMPLE OF RISK ASSESSMENT: CHOLESTEROL vs. ESTRADIOL (Both excreted by people) COMPOUND maximum detected lowest EC50/LC50 RQ CHOLESTEROL 6.8 ppb (CSO) 1121 ppb ESTRADIOL ppb (effluent) ppb 29.5

51 EXAMPLE #2: ATRAZINE (triazine herbicide) vs. CLOTHIANIDIN (neonicotinoid insecticide) (Both are pesticides used on corn) COMPOUND maximum detected lowest EC50/LC50 RQ EPA benchmark # exceeding EC50 ATRAZINE 33.8 ppb (Jewett Brook) ppb * 697** (tile discharge) ppb CLOTHIANIDIN 4.17 ppb (tile discharge) 1.85 ppb ppb (Jewett Brook) 1.85 ppb 0.3 * ATRAZINE AQUATIC LIFE BENCHMARK: 01/19/2017 (SNAPSHOT) = PPB 2/9/2017 (MENTIONED IN USGS 2017) = PPB 11/12/2017 = <1 PPB **Atrazine detection limit varied from 0.1 ppb to 0.02 ppb

52 SO FAR (PRELIMINARY!!!): 160 COMPOUNDS IN DATABASE WITH QUANTIFIABLE CONCENTRATIONS IN OUR WATERS 88 WITH ECOTOX EC50/LC50 DATA 22 COMPOUNDS WITH DETECTIONS ABOVE THE ACUTE LEVEL OF CONCERN CAFFEINE (FROM CSO) PHENANTHRENE (FROM URBAN STREAM) 4-NONYLPHENOL (FROM WWTF EFFLUENT) CHLOROTHALONIL (FROM GOLF COURSE) TFM (FROM LAMPRICIDE APPLICATION) ATRAZINE (FROM FIELD CORN)

53 WHAT S NEXT? COMPLETE THE RISK ASSESSMENT, both acute and chronic DETERMINE DATA GAPS WHICH DATA IS IMPORTANT/RELEVANT? JUST LARGE RIVERS AND LAKES? INCLUDE CSOs AND WWTF EFFLUENT? INCLUDE SMALL STREAMS? INCLUDE DITCHES, TILE DRAINS, ETC.? IS JEWETT BROOK IMPAIRED FOR PESTICIDES?

54 THE NEED TO COORDINATE AND PRIORITIZE WHAT SURFACE WATER ORGANIC CONTAMINANT MONITORING IS OCCURRING IN VERMONT/LAKE CHAMPLAIN BETWEEN VTDEC and VAAFM BETWEEN LCBP and STATE of VERMONT WHEN FUNDING WATER QUALITY RESEARCH/DEMONSTRATION PROJECTS

55 PROPOSAL TO LEGISLATURE: THE NEED FOR A COMPREHENSIVE SURFACE WATER ORGANIC CONTAMINANT MONITORING STRATEGY IN VERMONT Prepared by Nat Shambaugh February 12, 2017

56 THANKS TO: Lake Champlain Basin Program and NEIWPCC USGS UVM VAAFM VTDEC