William Battaglin, Kelly Smalling, Paul Bradley, and Tim Reilly: all at USGSWith 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

• 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?

USGS is focusing on occurrence, fate, transport, and environmental effects

USGS is mandated to conduct research for DOI Agencies

• NPS “Partnership” programs:Toxics ProgramUSGS-NPS Water Quality

Partnership ProgramNPS providing logistical supportEPA also is partnering with NPS so

we have all 3 working together in some placesAlso partnered with State during

2013 flood

USGS CECs Research

• 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?

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

“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

• 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

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:

• 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

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 fishFish with elevated Vitellogenin

Human Transport:

• 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

• 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:

• 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

• 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

• 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

• 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

• water analyses only for these compounds

• Many drugs detected (26 of 33)

• Frequently below Lab Reporting level, but frequently greater than 0.1 mg/L

• 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 mg/L was not expected

• 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

• 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

USGS Water-Quality Sampling After 2013 Flood

8 major tributaries 6 South Platte main stem sites Inorganics, nutrients, metals, wastewater compounds,

volatile organic compounds, pharmaceuticals, E. Coli Water and Sediment samples

USGS Water-Quality Sampling After 2013 Flood

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

• 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

Questions?

Results IV - Colorado• Samples from near Great Sand Dunes NP• In Water - 4 compounds detected

• Imazalil (0.21 mg/L) , AMPA (0.05 mg/L), EPTC (0.04 mg/L), azoxystrobin (0.009 mg/L)

• In Sediment - 6 compounds detected• Tebuconazole (130 mg/kg), pyraclostrobin (87.4

mg/kg), bifenthrin (4.3 mg/kg), fenhexamide (1.3 mg/kg), prometryn (3.4 mg/kg), p,p’DDE (0.8 mg/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)