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William Battaglin, Kelly Smalling, Paul Bradley, and Tim Reilly: all at USGS With help from: lots of others Supported by: USGS-NPS Partnership, USGS Toxics.

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Presentation on theme: "William Battaglin, Kelly Smalling, Paul Bradley, and Tim Reilly: all at USGS With help from: lots of others Supported by: USGS-NPS Partnership, USGS Toxics."— Presentation transcript:

1 William Battaglin, Kelly Smalling, Paul Bradley, and Tim Reilly: all at USGS With help from: lots of others Supported by: USGS-NPS Partnership, USGS Toxics Program, and USGS Amphibian Research and Monitoring Initiative From Rocky Mountain High to Below LoDo: Hormones, Pesticides, Endocrine Disrupters, and other CECs in Remote and not-so- Remote Colorado Locations

2 Contaminants of Emerging Concern Typically unregulated man-made compounds Pesticides, personal care products, prescription drugs, non-prescription drugs, industrial chemicals, household chemicals, natural hormones, synthetic hormones, PAHs, flame retardants, nanomaterials, … Over 60 million commercially available chemicals Over 300,000 inventoried or regulated chemicals Not all bad – many improve quality of life Using our newest and best and really expensive methods we can quantify about 300 CECs in water or sediment New methods may eventually allow for “total screening” What are CECs?

3 USGS is focusing on occurrence, fate, transport, and environmental effects USGS is mandated to conduct research for DOI Agencies NPS “Partnership” programs:  Toxics Program  USGS-NPS Water Quality Partnership Program  NPS providing logistical support  EPA also is partnering with NPS so we have all 3 working together in some places  Also partnered with State during 2013 flood USGS CECs Research

4 Pharmaceuticals and CECs can include: Drugs, personal care products, pesticides, industrial chemicals, metals Hormones are naturally released by animals (including humans) and plants. Some hormones used by humans, stock, and pets in various drugs A fraction of CECs and hormones used or “released” ends up in nearby water or sediment Pharmaceuticals, CECs, Hormones can: persist for months or years affect wildlife at very low concentrations alter ecosystems at low concentrations move far from their point-of-deposition Why worry about drugs, hormones, or CECs in Colorado’s Streams and Lakes?

5 Why worry about very low concentrations of some contaminants? Affect wildlife at very low concentrations Is the Paracelsian presumption that “the dose makes the poison” wrong? For EDC’s and hormones the answer - “yes” U-shaped, n-shaped, Jet Star-shaped Review by Vandenberg et al., 2012 states “non-monotonic responses and low-dose effects are remarkably common in studies of natural hormones and EDCs” Same study states that “the timing of exposure is profoundly important to detect low-dose effects of EDCs” Mixtures – Silva de Assis, 2013 – Fluoxetine + EE2

6 “Scope of Contaminants of Emerging Concern in National Parks” (Landewe, NPS/NRPC/NRR-2008/032)  CEC impacts:  “Probably” widespread  Severity increasing w/ growth  Service-Wide Ecological Risk Assessment:  Identify vulnerable park areas  Define CEC occurrence/sources  Define CEC degradation  Inform future decisions on source reduction or removal

7 Not a big surprise when we find pesticides in agricultural areas Nor is it a unusual to find CECs and hormones and other “WWTP indicators” in urban waters Do these chemicals occur in more remote locations? Or is remote just a matter of perspective? Science Questions I

8 What contaminants CECs are wildlife exposed to in remote and less remote aquatic habitats? Were do these contaminants occur in these setting In water, sediment, and tissue What are the likely sources and transport mechanisms Is atmospheric transport the only way for contaminants to reach remote locations ? Humans, stock, pets, wildlife, and dust, moths (just ask) Science Questions II:

9 Goolsby and others – herbicides in precipitation in Midwest Plenty of atrazine, alachlor, metolachlor in Iowa rain Background sites “far from study area” Isle Royale NP, MI Rocky MT NP, CO Glacier NP, MT Denali NP, AK Transport on dust (really very fine dirt) Atmospheric Transport - I

10 National Parks are “remote” by modern standards, not “untraveled” Rocky Mtn NP gets over 3 million visitors a year, 500+ camping sites, 250+ backcountry sites, pack animal tours, 800+ elk Some evidence of human impacts on water/sediment Some evidence of hormonally active water or sediment Transgender fish Fish with elevated Vitellogenin Human Transport:

11 Sampled water and sediment In a few cases fish/frog tissue Water and sediment analyzed for: Hormones WWTP indicators compounds Pharmaceuticals (water) Detection levels in nanograms per liter for water and micrograms per kilogram for sediment Water - ~150 in 2012, ~200 in 2013 Sediment -~75 both years Also Total Estero, nutrients, ions Histology, Vitellogenin Monitoring Methods

12 16 sites on streams or ponds in Rocky Mountain NP Some front-country, some back-country 3 sites in Denver below numerous WWTP outfalls Study Sites:

13 Water is very clean Only 1 wetlands with SC over 100, median of all sample = 20 54 chemicals detected (~25% of ones looked for) 14 chemical detected in more than 10% of samples Cholesterol in 73% of samples >15,000 ng/L – high in lakes Caffeine in 61%, >750 ng/L Camphor in 43%, 73 ng/L Beta-Sitosterol in 25%, 119 ng/L Lidocaine in 36%, > 1000 ng/L DEET in 36%, 80 ng/L P –Cresol in 33%, 56 ng/L Isophorone in 27%, 21 ng/L ROMO Results I - Water

14 Sediment is less clean 45 chemicals detected (60% of those looked for) 23 chemical detected in more than 10% of samples, 7 in more than 50% Indole in 98% of samples 3-Methyl-1H-indole in 96% P –Cresol in 95% Beta-Sitosterol in 95% Cholesterol in 86% Beta-Stigmastanol in 71% 2,6-Dimethylnaphthalene in 66% 4-Androstene 46% Camphor 42% Phenol 40% D-limonene 40% ROMO Results 2 - Sediment

15 Explain the graph Bill! Natural plant sterols most common Concentrations higher in sediment than water More natural than synthetic Frequently in both water and sediment 17-alpha should be with 17-beta

16 Natural sterols most common Concentrations higher in sediment More natural than synthetic In both water and sediment About the same as Urban! Most likely not coming from atmospheric deposition

17 water analyses only for these compounds Many drugs detected (26 of 33) Frequently below Lab Reporting level, but frequently greater than 0.1  g/L

18 Not nearly as many drugs detected (6 of 33) Frequently below Lab Reporting level Still detections of any of these compounds at more than 0.1  g/L was not expected

19 Just first ½ of list here Lots of detections in water (26 of 34) Less in sediment (9 of 34) Perhaps due to higher RL Several known EDCs like bisphenol A

20 Fewer detections in water (14 of 34) Less frequent detections above the RL More in sediment (16 of 34) More frequent detections above the RL Several that were not observed in urban setting like camphor Some higher concentrations

21  8 major tributaries  6 South Platte main stem sites  Inorganics, nutrients, metals, wastewater compounds, volatile organic compounds, pharmaceuticals, E. Coli  Water and Sediment samples

22  E. coli (Standard is 200)  7 sites at or exceeded standard with South Boulder Creek at 4,350  6 sites below standard (and 1 lab error) with St Vrain at 4.3  Pharmaceuticals (110 compounds)  Boulder Creek – acetaminophen, caffeine, acyclovir, metformin, nicotine, fexofenadine, piperonyl butoxide, 1,7-dimethylxanthine  Caffeine at 261 ng/L, acyclovir at 97 ng/L  St Vrain River - – acetaminophen, caffeine, carbamazepine, cotinine, lidocaine, acyclovir, metformin, methocaramol, fexofenadine, piperonyl butoxide, tramadol, metoprolol, methyl-1h benzotriazole, desvenlafaxine  Caffeine at 168 ng/L, acyclovir at 72 ng/L, metformin at 78 ng/L  S. Platte in Commerce City – 1,7-dimethylxanthine, acetaminophen, atrazine, buproprion, cotinine, desvenlfaxine, fexofenadine, fluconazole, lidocaine,  Caffeine 210 ng/L, acyclovir 89 ng/L, metformin 222 ng/L, benzotrazole 1240 ng/L, nicotine 12.3 ng/L, oxycodone 10.7 ng/L ng/L, venlafaxine 36.9 ng/L

23 Water and sediment from both urban and more remote locations can contain a complex mixture of hormones, drugs, WWTP indicators, and other CECs Sediments can contain substantial quantities of hormones and WWTP indicators Could be source to water in some cases Atmospheric transport could be transport mechanism for some contaminants in both settings Human inputs from WWTPs most likely source in urban waters “More direct” human and wildlife inputs are likely source in more remote locations Conclusions

24 Questions?

25 Results IV - Colorado Samples from near Great Sand Dunes NP In Water - 4 compounds detected Imazalil (0.21  g/L), AMPA (0.05  g/L), EPTC (0.04  g/L), azoxystrobin (0.009  g/L) In Sediment - 6 compounds detected Tebuconazole (130  g/kg), pyraclostrobin (87.4  g/kg), bifenthrin (4.3  g/kg), fenhexamide (1.3  g/kg), prometryn (3.4  g/kg), p,p’DDE (0.8  g/kg) In Frog Tissue – 8 compounds detected p,p,’DDE (0.711 ppt), simazine (0.337 ppt), myclobutinal (0.272 ppt), pyraclostrobin (0.066 ppt), methoprene (0.066 ppt), bifenthrin (0.064 ppt), malathion (0.064 ppt), 3,4,DCA (0.021 ppt)

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