Changes in chemical occurrence, concentration, and bioactivity in the Colorado River before and after replacement of the Moab, Utah wastewater treatment plant.

Long-term (2010-19) water-quality monitoring on the Colorado River downstream from Moab Utah indicated the persistent presence of Bioactive Chemicals (BC), such as pesticides and pharmaceuticals. This stream reach near Canyonlands National Park provides critical habitat for federally endangered species. The Moab wastewater treatment plant (WWTP) outfall discharges to the Colorado River and is the nearest potential point-source to this reach. The original WWTP was replaced in 2018. In 2016-19, a study was completed to determine if the new plant reduced BC input to the Colorado River at, and downstream from, the outfall. Water samples were collected before and after the plant replacement at sites upstream and downstream from the outfall. Samples were analyzed for as many as 243 pesticides, 109 pharmaceuticals, 20 hormones, 51 wastewater indicator chemicals, 20 metals, and 8 nutrients. BC concentrations, hazard quotients (HQs), and exposure activity ratios (EARs) were used to identify and prioritize contaminants for their potential to have adverse biological effects on the health of native and endangered wildlife. There were 22 BC with HQs >1, mostly metals and hormones; and 23 BC with EARs >0.1, mostly hormones and pharmaceuticals. Most high HQs or EARs were associated with samples collected at the WWTP outfall site prior to its replacement. Discharge from the new plant had reduced concentrations of nutrients, hormones, pharmaceuticals, and other BC. For example, all 16 of the hormones detected at the WWTP outfall site had maximum concentrations in samples collected prior to the WWTP replacement. The WWTP replacement had less effect on instream concentrations of metals and pesticides, BC whose sources are less directly tied to domestic wastewater. Study results indicate that improved WWTP technology can create substantial reductions in concentrations of non-regulated BC such as pharmaceuticals, in addition to regulated contaminants such as nutrients.

Density declines, richness increases, and composition shifts in stream macroinvertebrates.

Documenting trends of stream macroinvertebrate biodiversity is challenging because biomonitoring often has limited spatial, temporal, and taxonomic scopes. We analyzed biodiversity and composition of assemblages of >500 genera, spanning 27 years, and 6131 stream sites across forested, grassland, urban, and agricultural land uses throughout the United States. In this dataset, macroinvertebrate density declined by 11% and richness increased by 12.2%, and insect density and richness declined by 23.3 and 6.8%, respectively, over 27 years. In addition, differences in richness and composition between urban and agricultural versus forested and grassland streams have increased over time. Urban and agricultural streams lost the few disturbance-sensitive taxa they once had and gained disturbance-tolerant taxa. These results suggest that current efforts to protect and restore streams are not sufficient to mitigate anthropogenic effects.

Effects-Based Monitoring of Bioactive Chemicals Discharged to the Colorado River before and after a Municipal Wastewater Treatment Plant Replacement.

Monitoring of the Colorado River near the Moab, Utah, wastewater treatment plant (WWTP) outflow has detected pharmaceuticals, hormones, and estrogen-receptor (ER)-, glucocorticoid receptor (GR)-, and peroxisome proliferator-activated receptor-gamma (PPARγ)-mediated biological activities. The aim of the present multi-year study was to assess effects of a WWTP replacement on bioactive chemical (BC) concentrations. Water samples were collected bimonthly, pre- and post-replacement, at 11 sites along the Colorado River upstream and downstream of the WWTP and analyzed for in vitro bioactivities (e.g., agonism of ER, GR, and PPARγ) and BC concentrations; fathead minnows were cage deployed pre- and post-replacement at sites with varying proximities to the WWTP. Before the WWTP replacement, in vitro ER (24 ng 17ß-estradiol equivalents/L)-, GR (60 ng dexamethasone equivalents/L)-, and PPARγ-mediated activities were detected at the WWTP outflow but diminished downstream. In March 2018, the WWTP effluent was acutely toxic to the fish, likely due to elevated ammonia concentrations. Following the WWTP replacement, ER, GR, and PPARγ bioactivities were reduced by approximately 60-79%, no toxicity was observed in caged fish, and there were marked decreases in concentrations of many BCs. Results suggest that replacement of the Moab WWTP achieved a significant reduction in BC concentrations to the Colorado River.

Evaluating the potential role of bioactive chemicals on the distribution of invasive Asian carp upstream and downstream from river mile 278 in the Illinois waterway.

Two non-native carp species have invaded the Illinois Waterway and are a threat to Great Lakes ecosystems. Poor water quality in the upper Illinois Waterway may be a factor contributing to the stalling of the carp population front near river mile 278. In 2015, the U.S. Geological Survey collected 4 sets of water samples from two sites upstream and 4 sites downstream from river mile 278, and one tributary. Each sample was analyzed for up to 649 unique constituents of which 287 were detected including 96 pesticides, 62 pharmaceuticals, 39 wastewater indicator chemicals, 29 metals, 19 volatile organic compounds (VOCs), 6 disinfection by-products (DBPs), 5 hormones, and 5 carboxylic acids. Potential for bioactivity was estimated by comparing chemical concentrations to aquatic life or human health criteria and to in-vitro bioactivity screening results in the U.S Environmental Protection Agency ToxCast™ database. The resulting hazard quotients and exposure-activity ratios (EARs) are toxicity indexes that can be used to rank potential bioactivity of individual chemicals and chemical mixtures. This analysis indicates that several bioactive chemicals (BCs) including: carbendazim, 2,4-D, metolachlor, terbuthylazine, and acetochlor (pesticides); 1,4-dioxane (VOC); metformin, diphenhydramine, sulfamethoxazole, tramadol, fexofenadine, and the anti-depressants (pharmaceuticals); bisphenol A, 4-nonylphenol, galaxolide, 4-tert-octylphenol (wastewater indicator chemical); lead and boron (metals); and estrone (hormone) all occur in the upper Illinois Waterway at concentrations that produce elevated EARs values and may be adversely affecting carp reproduction and health. The clear differences in water quality upstream and downstream from river mile 278 with higher contaminant concentrations and potential bioactivity upstream could represent a barrier to carp range expansion.

Exposure and potential effects of pesticides and pharmaceuticals in protected streams of the US National park Service southeast region.

Globally, protected areas offer refugia for a broad range of taxa including threatened and endangered species. In the United States (US), the National Park Service (NPS) manages public lands to preserve biodiversity, but increasing park visitation and development of surrounding landscapes increase exposure to and effects from bioactive contaminants. The risk (exposure and hazard) to NPS protected-stream ecosystems within the highly urbanized southeast region (SER) from bioactive contaminants was assessed in five systems based on 334 pesticide and pharmaceutical analytes in water and 119 pesticides in sediment. Contaminant mixtures were common across all sampled systems, with approximately 24% of the unique analytes (80/334) detected at least once and 15% (49/334) detected in half of the surface-water samples. Pharmaceuticals were observed more frequently than pesticides, consistent with riparian buffers and concomitant spatial separation from non-point pesticide sources in four of the systems. To extrapolate exposure data to biological effects space, site-specific cumulative exposure-activity ratios (ΣEAR) were calculated for detected surface-water contaminants with available ToxCast data; common exceedances of a 0.001 ΣEAR effects-screening threshold raise concerns for molecular toxicity and possible, sub-lethal effects to non-target, aquatic vertebrates. The results illustrate the need for continued management of protected resources to reduce contaminant exposure and preserve habitat quality, including prioritization of conservation practices (riparian buffers) near stream corridors and increased engagement with upstream/up-gradient property owners and municipal wastewater facilities.

Pharmaceuticals, hormones, pesticides, and other bioactive contaminants in water, sediment, and tissue from Rocky Mountain National Park, 2012-2013.

Pharmaceuticals, hormones, pesticides, and other bioactive contaminants (BCs) are commonly detected in surface water and bed sediment in urban and suburban areas, but these contaminants are understudied in remote locations. In Rocky Mountain National Park (RMNP), Colorado, USA, BCs may threaten the reproductive success and survival of native aquatic species, benthic communities, and pelagic food webs. In 2012-2013, 67 water, 57 sediment, 63 fish, 10 frog, and 12 quality-control samples (8 water and 4 sediment) were collected from 20 sites in RMNP. Samples were analyzed for 369 parameters including 149 pharmaceuticals, 22 hormones, 137 pesticides, and 61 other chemicals or conditions to provide a representative assessment of BC occurrence within RMNP. Results indicate that BCs were detected in water and/or sediment from both remote and more accessible locations in RMNP. The most commonly detected BCs in water were caffeine, camphor, para-cresol, and DEET; and the most commonly detected BCs in sediment were indole, 3-methyl-1H-indole, para-cresol, and 2,6-dimethyl-naphthalene. Some detected contaminants, including carbaryl, caffeine, and oxycodone, are clearly attributable to direct local human input, whereas others may be transported into the park atmospherically (e.g., atrazine) or have local natural sources (e.g., para-cresol). One or more pharmaceuticals were detected in at least 1 sample from 15 of 20 sites. Most of the 29 detected pharmaceuticals are excreted primarily in human urine, not feces. Elevated net estrogenicity was observed in 18% of water samples, and elevated vitellogenin in blood was observed in 12% of male trout, both evidence of potential endocrine disruption. Hormone concentrations in sediment tended to be greater than concentrations in water. Most BCs were observed at concentrations below those not expected to pose adverse effects to aquatic life. Results indicate that even in remote locations aquatic wildlife can be exposed to pharmaceuticals, hormones, pesticides, and other bioactive contaminants.

Bioactive contaminants of emerging concern in National Park waters of the northern Colorado Plateau, USA.

Pharmaceuticals and personal care products (PPCPs), wastewater indicators (WWIs), and pesticides (herein, Contaminants of Emerging Concern [CECs]) have been documented in surface waters throughout the world and have associated risks to aquatic life. While much research has focused on temperate and urbanized watersheds, less is known about CEC presence in semi-arid landscapes, where water availability is limited and populations are low. CEC presence in water and sediment is reported for 21 sites in eight U.S. national parks in the northern Colorado Plateau region. From 2012 to 2016, at least one PPCP and/or WWI was detected at most sites on over half of sampling visits, indicating that CECs are not uncommon even in isolated areas. CEC detections were generally fewer and at lower concentrations than in urbanized or agricultural watersheds. Consistent with studies from other U.S. regions, the most frequently detected CECs in this study include DEET, caffeine, organophosphorus flame retardants, and bisphenol A in water and fecal indicators and polycyclic aromatic hydrocarbons in sediment. Maximum concentrations in this study were generally below available water quality benchmarks, sediment quality guidelines, and risk assessment thresholds associated with vertebrates. Additional work is needed to assess the potential activity of hormones, which had high reporting limits in our study, and potential bioactivity of environmental concentrations for invertebrates, microbial communities, and algae. Potential sources of CEC contamination include upstream wastewater effluent discharges and National Park Service invasive-plant-control herbicide applications. CEC occurrence patterns and similarities between continuous and isolated flow locations suggest that direct contamination from individual visitors may also occur. While our data indicate there is little aquatic health risk associated with CECs at our sites, our results demonstrate the ubiquity of CECs on the landscape and a continued need for public outreach concerning resource-use ethics and the potential effects of upstream development.

Effects of an Extreme Flood on Trace Elements in River Water-From Urban Stream to Major River Basin.

Major floods adversely affect water quality through surface runoff, groundwater discharge, and damage to municipal water infrastructure. Despite their importance, it can be difficult to assess the effects of floods on streamwater chemistry because of challenges collecting samples and the absence of baseline data. This study documents water quality during the September 2013 extreme flood in the South Platte River, Colorado, USA. Weekly time-series water samples were collected from 3 urban source waters (municipal tap water, streamwater, and wastewater treatment facility effluent) under normal-flow and flood conditions. In addition, water samples were collected during the flood at 5 locations along the South Platte River and from 7 tributaries along the Colorado Front Range. Samples were analyzed for 54 major and trace elements. Specific chemical tracers, representing different natural and anthropogenic sources and geochemical behaviors, were used to compare streamwater composition before and during the flood. The results differentiate hydrological processes that affected water quality: (1) in the upper watershed, runoff diluted most dissolved constituents, (2) in the urban corridor and lower watershed, runoff mobilized soluble constituents accumulated on the landscape and contributed to stream loading, and (3) flood-induced groundwater discharge mobilized soluble constituents stored in the vadose zone.

Widespread legacy brine contamination from oil production reduces survival of chorus frog larvae.

Advances in drilling techniques have facilitated a rapid increase in hydrocarbon extraction from energy shales, including the Williston Basin in central North America. This area overlaps with the Prairie Pothole Region, a region densely populated with wetlands that provide numerous ecosystem services. Historical (legacy) disposal practices often released saline co-produced waters (brines) with high chloride concentrations, affecting wetland water quality directly or persisting in sediments. Despite the potential threat of brine contamination to aquatic habitats, there has been little research into its ecological effects. We capitalized on a gradient of legacy brine-contaminated wetlands in northeast Montana to conduct laboratory experiments to assess variation in survival of larval Boreal Chorus Frogs (Pseudacris maculata) reared on sediments from 3 local wetlands and a control source. To help provide environmental context for the experiment, we also measured chloride concentrations in 6 brine-contaminated wetlands in our study area, including the 2 contaminated sites used for sediment exposures. Survival of frog larvae during 46- and 55-day experiments differed by up to 88% among sediment sources (Site Model) and was negatively correlated with potential chloride exposure (Chloride Model). Five of the 6 contaminated wetlands exceeded the U.S. EPA acute benchmark for chloride in freshwater (860 mg/L) and all exceeded the chronic benchmark (230 mg/L). However, the Wetland Site model explained more variation in survival than the Chloride Model, suggesting that chloride concentration alone does not fully reflect the threat of contamination to aquatic species. Because the profiles of brine-contaminated sediments are complex, further surveys and experiments are needed across a broad range of conditions, especially where restoration or remediation actions have reduced brine-contamination. Information provided by this study can help quantify potential ecological threats and help land managers prioritize conservation strategies as part of responsible and sustainable energy development.

A pesticide paradox: fungicides indirectly increase fungal infections.

There are many examples where the use of chemicals have had profound unintended consequences, such as fertilizers reducing crop yields (paradox of enrichment) and insecticides increasing insect pests (by reducing natural biocontrol). Recently, the application of agrochemicals, such as agricultural disinfectants and fungicides, has been explored as an approach to curb the pathogenic fungus, Batrachochytrium dendrobatidis (Bd), which is associated with worldwide amphibian declines. However, the long-term, net effects of early-life exposure to these chemicals on amphibian disease risk have not been thoroughly investigated. Using a combination of laboratory experiments and analysis of data from the literature, we explored the effects of fungicide exposure on Bd infections in two frog species. Extremely low concentrations of the fungicides azoxystrobin, chlorothalonil, and mancozeb were directly toxic to Bd in culture. However, estimated environmental concentrations of the fungicides did not reduce Bd on Cuban tree frog (Osteopilus septentrionalis) tadpoles exposed simultaneously to any of these fungicides and Bd, and fungicide exposure actually increased Bd-induced mortality. Additionally, exposure to any of these fungicides as tadpoles resulted in higher Bd abundance and greater Bd-induced mortality when challenged with Bd post-metamorphosis, an average of 71 d after their last fungicide exposure. Analysis of data from the literature revealed that previous exposure to the fungicide itraconazole, which is commonly used to clear Bd infections, made the critically endangered booroolong frog (Litoria booroolongensis) more susceptible to Bd. Finally, a field survey revealed that Bd prevalence was positively associated with concentrations of fungicides in ponds. Although fungicides show promise for controlling Bd, these results suggest that, if fungicides do not completely eliminate Bd or if Bd recolonizes, exposure to fungicides has the potential to do more harm than good. To ensure that fungicide applications have the intended consequence of curbing amphibian declines, researchers must identify which fungicides do not compromise the pathogen resistance mechanisms of amphibians.

Widespread occurrence and potential for biodegradation of bioactive contaminants in Congaree National Park, USA.

Organic contaminants with designed molecular bioactivity, such as pesticides and pharmaceuticals, originate from human and agricultural sources, occur frequently in surface waters, and threaten the structure and function of aquatic and terrestrial ecosystems. Congaree National Park in South Carolina (USA) is a vulnerable park unit due to its location downstream of multiple urban and agricultural contaminant sources and its hydrologic setting, being composed almost entirely of floodplain and aquatic environments. Seventy-two water and sediment samples were collected from 16 sites in Congaree National Park during 2013 to 2015, and analyzed for 199 and 81 targeted organic contaminants, respectively. More than half of these water and sediment analytes were not detected or potentially had natural sources. Pharmaceutical contaminants were detected (49 total) frequently in water throughout Congaree National Park, with higher detection frequencies and concentrations at Congaree and Wateree River sites, downstream from major urban areas. Forty-seven organic wastewater indicator chemicals were detected in water, and 36 were detected in sediment, of which approximately half are distinctly anthropogenic. Endogenous sterols and hormones, which may originate from humans or wildlife, were detected in water and sediment samples throughout Congaree National Park, but synthetic hormones were detected only once, suggesting a comparatively low risk of adverse impacts. Assessment of the biodegradation potentials of 8 14 C-radiolabeled model contaminants indicated poor potentials for some contaminants, particularly under anaerobic sediments conditions. Environ Toxicol Chem 2017;36:3045-3056. Published 2017 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

Effects of Backpacker Use, Pack Stock Trail Use, and Pack Stock Grazing on Water-Quality Indicators, Including Nutrients, E. coli, Hormones, and Pharmaceuticals, in Yosemite National Park, USA.

We investigated how visitor-use affects water quality in wilderness in Yosemite National Park. During the summers of 2012-2014, we collected and analyzed surface-water samples for water-quality indicators, including fecal indicator bacteria Escherichia coli, nutrients (nitrogen, phosphorus, carbon), suspended sediment concentration, pharmaceuticals, and hormones. Samples were collected upstream and downstream from different types of visitor use at weekly to biweekly intervals and during summer storms. We conducted a park-wide synoptic sampling campaign during summer 2014, and sampled upstream and downstream from meadows to evaluate the mitigating effect of meadows on water quality. At pack stock stream crossings, Escherichia coli concentrations were greater downstream from crossings than upstream (median downstream increase in Escherichia coli of three colony forming units 100 mL-1), with the greatest increases occurring during storms (median downstream increase in Escherichia coli of 32 CFU 100 mL-1). At backpacker use sites, hormones, and pharmaceuticals (e.g., insect repellent) were detected at downstream sites, and Escherichia coli concentrations were greater at downstream sites (median downstream increase in Escherichia coli of 1 CFU 100 mL-1). Differences in water quality downstream vs. upstream from meadows grazed by pack stock were not detectable for most water-quality indicators, however, Escherichia coli concentrations decreased downstream, suggesting entrapment and die-off of fecal indicator bacteria in meadows. Our results indicate that under current-use levels pack stock trail use and backpacker use are associated with detectable, but relatively minor, effects on water quality, which are most pronounced during storms.

Aerobic biodegradation potential of endocrine-disrupting chemicals in surface-water sediment at Rocky Mountain National Park, USA.

Endocrine-disrupting chemicals (EDCs) in surface water and bed sediment threaten the structure and function of aquatic ecosystems. In natural, remote, and protected surface-water environments where contaminant releases are sporadic, contaminant biodegradation is a fundamental driver of exposure concentration, timing, duration, and, thus, EDC ecological risk. Anthropogenic contaminants, including known and suspected EDCs, were detected in surface water and sediment collected from 2 streams and 2 lakes in Rocky Mountain National Park (Colorado, USA). The potential for aerobic EDC biodegradation was assessed in collected sediments using 6 (14) C-radiolabeled model compounds. Aerobic microbial mineralization of natural (estrone and 17ß-estradiol) and synthetic (17α-ethinylestradiol) estrogen was significant at all sites. Bed sediment microbial communities in Rocky Mountain National Park also effectively degraded the xenoestrogens bisphenol-A and 4-nonylphenol. The same sediment samples exhibited little potential for aerobic biodegradation of triclocarban, however, illustrating the need to assess a wider range of contaminant compounds. The present study's results support recent concerns over the widespread environmental occurrence of carbanalide antibacterials, like triclocarban and triclosan, and suggest that backcountry use of products containing these compounds should be discouraged.

Pesticide concentrations in frog tissue and wetland habitats in a landscape dominated by agriculture.

Habitat loss and exposure to pesticides are likely primary factors contributing to amphibian decline in agricultural landscapes. Conservation efforts have attempted to restore wetlands lost through landscape modifications to reduce contaminant loads in surface waters and providing quality habitat to wildlife. The benefits of this increased wetland area, perhaps especially for amphibians, may be negated if habitat quality is insufficient to support persistent populations. We examined the presence of pesticides and nutrients in water and sediment as indicators of habitat quality and assessed the bioaccumulation of pesticides in the tissue of two native amphibian species Pseudacris maculata (chorus frogs) and Lithobates pipiens (leopard frogs) at six wetlands (3 restored and 3 reference) in Iowa, USA. Restored wetlands are positioned on the landscape to receive subsurface tile drainage water while reference wetlands receive water from overland run-off and shallow groundwater sources. Concentrations of the pesticides frequently detected in water and sediment samples were not different between wetland types. The median concentration of atrazine in surface water was 0.2 µg/L. Reproductive abnormalities in leopard frogs have been observed in other studies at these concentrations. Nutrient concentrations were higher in the restored wetlands but lower than concentrations thought lethal to frogs. Complex mixtures of pesticides including up to 8 fungicides, some previously unreported in tissue, were detected with concentrations ranging from 0.08 to 1,500 µg/kg wet weight. No significant differences in pesticide concentrations were observed between species, although concentrations tended to be higher in leopard frogs compared to chorus frogs, possibly because of differences in life histories. Our results provide information on habitat quality in restored wetlands that will assist state and federal agencies, landowners, and resource managers in identifying and implementing conservation and management actions for these and similar wetlands in agriculturally dominated landscapes.

The occurrence of glyphosate, atrazine, and other pesticides in vernal pools and adjacent streams in Washington, DC, Maryland, Iowa, and Wyoming, 2005-2006.

Vernal pools are sensitive environments that provide critical habitat for many species, including amphibians. These small water bodies are not always protected by pesticide label requirements for no-spray buffer zones, and the occurrence of pesticides in them is poorly documented. In this study, we investigated the occurrence of glyphosate, its primary degradation product aminomethylphosphonic acid, and additional pesticides in vernal pools and adjacent flowing waters. Most sampling sites were chosen to be in areas where glyphosate was being used either in production agriculture or for nonindigenous plant control. The four site locations were in otherwise protected areas (e.g., in a National Park). When possible, water samples were collected both before and after glyphosate application in 2005 and 2006. Twenty-eight pesticides or pesticide degradation products were detected in the study, and as many as 11 were identified in individual samples. Atrazine was detected most frequently and concentrations exceeded the freshwater aquatic life standard of 1.8 micrograms per liter (microg/l) in samples from Rands Ditch and Browns Ditch in DeSoto National Wildlife Refuge. Glyphosate was measured at the highest concentration (328 microg/l) in a sample from Riley Spring Pond in Rock Creek National Park. This concentration exceeded the freshwater aquatic life standard for glyphosate of 65 microg/l. Aminomethylphosphonic acid, triclopyr, and nicosulfuron also were detected at concentrations greater than 3.0 microg/l.