From Rocky Mountain High to Below LoDo:
Hormones, Pesticides, Endocrine Disrupters,
and other CECs in Remote and not-soRemote Colorado Locations
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
What are CECs?
• 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”
USGS CECs Research
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
Why worry about drugs, hormones, or CECs
in Colorado’s Streams and Lakes?
• 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:
•
•
•
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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 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
Science Questions I
• 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 II:
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)
Atmospheric Transport - I
• 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)
Human Transport:
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
Monitoring Methods
• Sampled water and sediment
• In a few cases fish/frog tissue
• Water and sediment analyzed for:
•
•
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•
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• 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
Study Sites:
• 16 sites on streams or
ponds in Rocky
Mountain NP
• Some front-country,
some back-country
• 3 sites in Denver below
numerous WWTP
outfalls
ROMO Results I - Water
• 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 2 - Sediment
• 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%
• 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
 8 major tributaries
 6 South Platte main stem sites
 Inorganics, nutrients, metals, wastewater compounds, volatile
organic compounds, pharmaceuticals, E. Coli
 Water and Sediment samples
 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


St Vrain River - – acetaminophen, caffeine,
carbamazepine, cotinine, lidocaine, acyclovir,
metformin, methocaramol, fexofenadine, piperonyl
butoxide, tramadol, metoprolol, methyl-1h
benzotriazole, desvenlafaxine


Caffeine at 261 ng/L, acyclovir at 97 ng/L
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
Conclusions
• 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
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)