Search

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.

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 17β-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.

The National Park Service (NPS) manages hundreds of parks in the United States, and many contain important aquatic ecosystems and/or threatened and endangered aquatic species vulnerable to hydro-climatic change. More effective management of park resources under future hydro-climatic uncertainty requires information on both baseline conditions and the range of projected future conditions. A monthly water balance model was used to assess baseline (1981&ndash, 1999) conditions and a range of projected future hydro-climatic conditions in 374 NPS parks. General circulation model outputs representing 214 future climate simulations were used to drive the model. Projected future changes in air temperature (T), precipitation (p), and runoff (R) are expressed as departures from historical baselines. Climate simulations indicate increasing T by 2030 for all parks with 50th percentile simulations projecting increases of 1.67 &deg, C or more in 50% of parks. Departures in 2030 p indicate a mix of mostly increases and some decreases, with 50th percentile simulations projecting increases in p in more than 70% of parks. Departures in R for 2030 are mostly decreases, with the 50th percentile simulations projecting decreases in R in more than 50% of parks in all seasons except winter. Hence, in many NPS parks, R is projected to decrease even when p is projected to increase because of increasing T in all parks. Projected changes in future hydro-climatic conditions can also be assessed for individual parks, and Rocky Mountain National Park and Congaree National Park are used as examples.

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.

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.

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 17β-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.

Amphibians are declining throughout the United States and worldwide due, partly, to habitat loss. Conservation practices on the landscape restore wetlands to denitrify tile drainage effluent and restore ecosystem services. Understanding how water quality, hydroperiod, predation, and disease affect amphibians in restored wetlands is central to maintaining healthy amphibian populations in the region. We examined the quality of amphibian habitat in restored wetlands relative to reference wetlands by comparing species richness, developmental stress, and adult leopard frog (Lithobates pipiens) survival probabilities to a suite of environmental metrics. Although measured habitat variables differed between restored and reference wetlands, differences appeared to have sub-lethal rather than lethal effects on resident amphibian populations. There were few differences in amphibian species richness and no difference in estimated survival probabilities between wetland types. Restored wetlands had more nitrate and alkaline pH, longer hydroperiods, and were deeper, whereas reference wetlands had more amphibian chytrid fungus zoospores in water samples and resident amphibians exhibited increased developmental stress. Restored and reference wetlands are both important components of the landscape in central Iowa and maintaining a complex of fish-free wetlands with a variety of hydroperiods will likely contribute to the persistence of amphibians in this landscape.

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.

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 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.

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.

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

Glyphosate use in the United States increased from less than 5,000 to more than 80,000 metric tons/yr between 1987 and 2007. Glyphosate is popular due to its ease of use on soybean, cotton, and corn crops that are genetically modified to tolerate it, utility in no-till farming practices, utility in urban areas, and the perception that it has low toxicity and little mobility in the environment. This compilation is the largest and most comprehensive assessment of the environmental occurrence of glyphosate and aminomethylphosphonic acid (AMPA) in the United States conducted to date, summarizing the results of 3,732 water and sediment and 1,018 quality assurance samples collected between 2001 and 2010 from 38 states. Results indicate that glyphosate and AMPA are usually detected together, mobile, and occur widely in the environment. Glyphosate was detected without AMPA in only 2.3% of samples, whereas AMPA was detected without glyphosate in 17.9% of samples. Glyphosate and AMPA were detected frequently in soils and sediment, ditches and drains, precipitation, rivers, and streams; and less frequently in lakes, ponds, and wetlands; soil water; and groundwater. Concentrations of glyphosate were below the levels of concern for humans or wildlife; however, pesticides are often detected in mixtures. Ecosystem effects of chronic low-level exposures to pesticide mixtures are uncertain. The environmental health risk of low-level detections of glyphosate, AMPA, and associated adjuvants and mixtures remain to be determined.

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.

To investigate interactions among disease, pesticides, water quality, and adjacent land cover, we collected samples of water, sediment, and frog tissue from 21 sites in 7 States in the United States (US) representing a variety of amphibian habitats. All samples were analyzed for >90 pesticides and pesticide degradates, and water and frogs were screened for the amphibian chytrid fungus Batrachochytrium dendrobatidis (Bd) using molecular methods. Pesticides and pesticide degradates were detected frequently in frog breeding habitats (water and sediment) as well as in frog tissue. Fungicides occurred more frequently in water, sediment, and tissue than was expected based upon their limited use relative to herbicides or insecticides. Pesticide occurrence in water or sediment was not a strong predictor of occurrence in tissue, but pesticide concentrations in tissue were correlated positively to agricultural and urban land, and negatively to forested land in 2-km buffers around the sites. Bd was detected in water at 45% of sites, and on 34% of swabbed frogs. Bd detections in water were not associated with differences in land use around sites, but sites with detections had colder water. Frogs that tested positive for Bd were associated with sites that had higher total fungicide concentrations in water and sediment, but lower insecticide concentrations in sediments relative to frogs that were Bd negative. Bd concentrations on frog swabs were positively correlated to dissolved organic carbon, and total nitrogen and phosphorus, and negatively correlated to pH and water temperature. Data were collected from a range of locations and amphibian habitats and represent some of the first field-collected information aimed at understanding the interactions between pesticides, land use, and amphibian disease. These interactions are of particular interest to conservation efforts as many amphibians live in altered habitats and may depend on wetlands embedded in these landscapes to survive.

The mountainous areas of Colorado are used for tourism and recreation, and they provide water storage and supply for municipalities, industries, and agriculture. Recent studies suggest that water supply and tourist industries such as skiing are at risk from climate change. In this study, a distributed-parameter watershed model, the Precipitation-Runoff Modeling System (PRMS), is used to identify the potential effects of future climate on hydrologic conditions for two Colorado basins, the East River at Almont and the Yampa River at Steamboat Springs, and at the subbasin scale for two ski areas within those basins. Climate-change input files for PRMS were generated by modifying daily PRMS precipitation and temperature inputs with mean monthly climate-change fields of precipitation and temperature derived from five general circulation model (GCM) simulations using one current and three future carbon emission scenarios. All GCM simulations of mean daily minimum and maximum air temperature for the East and Yampa River basins indicate a relatively steady increase of up to several degrees Celsius from baseline conditions by 2094. GCM simulations of precipitation in the two basins indicate little change or trend in precipitation, but there is a large range associated with these projections. PRMS projections of basin mean daily streamflow vary by scenario but indicate a central tendency toward slight decreases, with a large range associated with these projections. Decreases in water content or changes in the spatial extent of snowpack in the East and Yampa River basins are important because of potential adverse effects on water supply and recreational activities. PRMS projections of each future scenario indicate a central tendency for decreases in basin mean snow-covered area and snowpack water equivalent, with the range in the projected decreases increasing with time. However, when examined on a monthly basis, the projected decreases are most dramatic during fall and spring. Presumably, ski area locations are picked because of a tendency to receive snow and keep snowpack relative to the surrounding area. This effect of ski area location within the basin was examined by comparing projections of March snow-covered area and snowpack water equivalent for the entire basin with more local projections for the portion of the basin that represents the ski area in the PRMS models. These projections indicate a steady decrease in March snow-covered area for the basins but only small changes in March snow-covered area at both ski areas for the three future scenarios until around 2050. After 2050, larger decreases are possible, but there is a large range in the projections of future scenarios. The rates of decrease for snowpack water equivalent and precipitation that falls as snow are similar at the basin and subbasin scale in both basins. Results from this modeling effort show that there is a wide range of possible outcomes for future snowpack conditions in Colorado. The results also highlight the differences between projections for entire basins and projections for local areas or subbasins within those basins.

Fungicides are used to prevent foliar diseases on a wide range of vegetable, field, fruit, and ornamental crops. They are generally more effective as protective rather than curative treatments, and hence tend to be applied before infections take place. Less than 1% of US soybeans were treated with a fungicide in 2002 but by 2006, 4% were treated. Like other pesticides, fungicides can move-off of fields after application and subsequently contaminate surface water, groundwater, and associated sediments. Due to the constant pressure from fungal diseases such as the recent Asian soybean rust outbreak, and the always-present desire to increase crop yields, there is the potential for a significant increase in the amount of fungicides used on US farms. Increased fungicide use could lead to increased environmental concentrations of these compounds. This study documents the occurrence of fungicides in select US streams soon after the first documentation of soybean rust in the US and prior to the corresponding increase in fungicide use to treat this problem. Water samples were collected from 29 streams in 13 states in 2005 and/or 2006, and analyzed for 12 target fungicides. Nine of the 12 fungicides were detected in at least one stream sample and at least one fungicide was detected in 20 of 29 streams. At least one fungicide was detected in 56% of the 103 samples, as many as five fungicides were detected in an individual sample, and mixtures of fungicides were common. Azoxystrobin was detected most frequently (45% of 103 samples) followed by metalaxyl (27%), propiconazole (17%), myclobutanil (9%), and tebuconazole (6%). Fungicide detections ranged from 0.002 to 1.15 μg/L. There was indication of a seasonal pattern to fungicide occurrence, with detections more common and concentrations higher in late summer and early fall than in spring. At a few sites, fungicides were detected in all samples collected suggesting the potential for season-long occurrence in some streams. Fungicide occurrence appears to be related to fungicide use in the associated drainage basins; however, current use information is generally lacking and more detailed occurrence data are needed to accurately quantify such a relation. Maximum concentrations of fungicides were typically one or more orders of magnitude less than current toxicity estimates for freshwater aquatic organisms or humans; however, gaps in current toxicological understandings of the effects of fungicides in the environment limit these interpretations.

Recent national concerns regarding the environmental occurrence of emerging contaminants (ECs) have catalyzed a series of recent studies. Many ECs are released into the environment through discharges from wastewater treatment plants (WWTPs) and other sources. In 2005, the U.S. Geological Survey and the City of Longmont initiated an investigation of selected ECs in a 13.8-km reach of St. Vrain Creek, Colorado. Seven sites were sampled for ECs following a Lagrangian design; sites were located upstream, downstream, and in the outfall of the Longmont WWTP, and at the mouths of two tributaries, Left Hand Creek and Boulder Creek (which is influenced by multiple WWTP outfalls). Samples for 61 ECs in 16 chemical use categories were analyzed and 36 were detected in one or more samples. Of these, 16 have known or suspected endocrine-disrupting potential. At and downstream from the WWTP outfall, detergent metabolites, fire retardants, and steroids were detected at the highest concentrations, which commonly exceeded 1 μg/l in 2005 and 2 μg/l in 2006. Most individual ECs were measured at concentrations less than 2 μg/l. The results indicate that outfalls from WWTPs are the largest but may not be the sole source of ECs in St. Vrain Creek. In 2005, high discharge was associated with fewer EC detections, lower total EC concentrations, and smaller EC loads in St. Vrain Creek and its tributaries as compared with 2006. EC behavior differed by individual compound, and some differences between sites could be attributed to analytical variability or to other factors such as physical or chemical characteristics or distance from contributing sources. Loads of some ECs, such as diethoxynonylphenol, accumulated or attenuated depending on location, discharge, and distance downstream from the WWTP, whereas others, such as bisphenol A, were largely conservative. The extent to which ECs in St. Vrain Creek affect native fish species and macroinvertebrate communities is unknown, but recent studies have shown that fish respond to very low concentrations of ECs, and further study on the fate and transport of these contaminants in the aquatic environment is warranted.

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.

The use of glyphosate has increased rapidly, and there is limited understanding of its environmental fate. The objective of this study was to document the occurrence of glyphosate and the transformation product aminomethylphosphonic acid (AMPA) in Midwestern streams and to compare their occurrence with that of more commonly measured herbicides such as acetochlor, atrazine, and metolachlor. Water samples were collected at sites on 51 streams in nine Midwestern states in 2002 during three runoff events: after the application of pre-emergence herbicides, after the application of post-emergence herbicides, and during harvest season. All samples were analyzed for glyphosate and 20 other herbicides using gas chromatography/mass spectrometry or high performance liquid chromatography/mass spectrometry. The frequency of glyphosate and AMPA detection, range of concentrations in runoff samples, and ratios of AMPA to glyphosate concentrations did not vary throughout the growing season as substantially as for other herbicides like atrazine, probably because of different seasonal use patterns. Glyphosate was detected at or above 0.1 μg/l in 35 percent of pre-emergence, 40 percent of post-emergence, and 31 percent of harvest season samples, with a maximum concentration of 8.7 μg/l. AMPA was detected at or above 0.1 μg/l in 53 percent of pre-emergence, 83 percent of post-emergence, and 73 percent of harvest season samples, with a maximum concentration of 3.6 μg/l. Glyphosate was not detected at a concentration at or above the U.S. Environmental Protection Agency's maximum contamination level (MCL) of 700 μg/l in any sample. Atrazine was detected at or above 0.1 μg/l in 94 percent of pre-emergence, 96 percent of post-emergence, and 57 percent of harvest season samples, with a maximum concentration of 55 μg/l. Atrazine was detected at or above its MCL (3 μg/l) in 57 percent of pre-emergence and 33 percent of post-emergence samples.

Most research to assess amphibian declines has focused on local-scale projects on one or a few species. The Amphibian Research and Monitoring Initiative (ARMI) is a national program in the United States mandated by congressional directive and implemented by the U.S. Department of the Interior (specifically the U.S. Geological Survey, USGS). Program goals are to monitor changes in populations of amphibians across U.S. Department of the Interior lands and to address research questions related to amphibian declines using a hierarchical framework of base-, mid- and apex-level monitoring sites. ARMI is currently monitoring 83 amphibian species (29% of species in the U.S.) at mid- and apex-level areas. We chart the progress of this 5-year-old program and provide an example of mid-level monitoring from 1 of the 7 ARMI regions.

Most herbicides applied to crops are adsorbed by plants or transformed (degraded) in the soil, but small fractions are lost from fields and either move to streams in overland runoff, near surface flow, or subsurface drains, or they infiltrate slowly to ground water. Herbicide transformation products (TPs) can be more or less mobile and more or less toxic in the environment than their source herbicides. To obtain information on the concentrations of selected herbicides and TPs in surface waters of the Midwestern United States, 151 water samples were collected from 71 streams and five reservoir outflows in 1998. These samples were analyzed for 13 herbicides and 10 herbicide TPs. Herbicide TPs were found to occur as frequently or more frequently than source herbicides and at concentrations that were often larger than their source herbicides. Most samples contained a mixture of more than 10 different herbicides or TPs. The ratios of TPs to herbicide concentrations can be used to determine the source of herbicides in streams. Results of a two-component mixing model suggest that on average 90 percent or more of the herbicide mass in Midwestern streams during early summer runoff events originates from the runoff and 10 percent or less comes from increased ground water discharge.

A study was conducted to determine whether NO3– stable isotopes (δ15N and δ18O), at natural abundance levels, could discriminate among NO3– sources from sites with different land uses at the basin scale. Water samples were collected from 24 sites in the Mississippi River Basin from five land-use categories: (1) large river basins (>34 590 km2) draining multiple land uses and smaller basins in which the predominant land use was (2) urban, (3) undeveloped, (4) crops, or (5) crops and livestock. Our data suggest that riverine nitrates from different land uses have overlapping but moderately distinct isotopic signatures. δ18O data were critical in showing abrupt changes in NO3– source with discharge. The isotopic values of large rivers resembled crop sites, sites with livestock tended to have δ15N values characteristic of manure, and urban sites tended to have high δ18O values characteristic of atmospheric nitrate.

Society is becoming increasingly aware of the value of healthy aquatic ecosystems as well as the effects that man’s activities have on those ecosystems. In recent years, many urban and industrial sources of contamination have been reduced or eliminated. The agricultural community also has worked towards reducing off-site movement of agricultural chemicals, but their use in farming is still growing. A small fraction, estimated at

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 1500 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.

Current and historical data show that nitrogen concentrations and flux in the Mississippi River Basin have increased significantly during the past 100 years. Most of the increase observed in the lower Mississippi River has occurred since the early 1970s and is due almost entirely to an increase in nitrate. The current (1980–99) average annual nitrogen (N) flux from the Mississippi Basin to the Gulf of Mexico is about 1 555 500 t year−1, of which about 62% is nitrate-N. The remaining 38% is organic nitrogen and a small amount of ammonium. The current (1980–99) average nitrate flux to the Gulf is almost three times larger than it was during 1955–70. This increased supply of nitrogen to the Gulf is believed to be partly responsible for the increasing size of a large hypoxic zone that develops along the Louisiana–Texas shelf each summer. This zone of oxygen-depleted water has doubled in areal extent since it was first measured in 1985. The increase in annual nitrate flux to the Gulf can be largely explained by three factors: increased fertilizer use, annual variability in precipitation and increased streamflow, and the year-to-year variability in the amount of nitrogen available in the soil-ground water system for leaching to streams. The predominant source areas for the nitrogen transported to the Gulf of Mexico are basins draining southern Minnesota, Iowa, Illinois, Indiana, and Ohio. Basins in this region yield 1801 to 3050 kg N km−2 year−1 to streams, several times the N yield of basins outside this region. Published in 2001 by John Wiley & Sons, Ltd.

An Erratum has been published for this article in Hydrological Processes 16(5) 2002, 1129–1130. Nitrate (NO3) and other nutrients discharged by the Mississippi River are suspected of causing a zone of depleted dissolved oxygen (hypoxic zone) in the Gulf of Mexico each summer. The hypoxic zone may have an adverse affect on aquatic life and commercial fisheries. The amount of NO3 delivered by the Mississippi River to the Gulf of Mexico is well documented, but the relative contributions of different sources of NO3, and the magnitude of subsequent in-stream transformations of NO3, are not well understood. Forty-two water samples collected in 1997 and 1998 at eight stations located either on the Mississippi River or its major tributaries were analysed for NO3, total nitrogen (N), atrazine, chloride concentrations and NO3 stable isotopes (δ15N and δ18O). These data are used to assess the magnitude and nature of in-stream N transformation and to determine if the δ15N and δ18O of NO3 provide information about NO3 sources and transformation processes in a large river system (drainage area 2 900 000 km2) that would otherwise be unavailable using concentration and discharge data alone. Results from 42 samples indicate that the δ15N and δ18O ratios between sites on the Mississippi River and its tributaries are somewhat distinctive, and vary with season and discharge rate. Of particular interest are two nearly Lagrangian sample sets, in which samples from the Mississippi River at St Francisville, LA, are compared with samples collected from the Ohio River at Grand Chain, II, and the Mississippi River at Thebes, IL. In both Lagrangian sets, mass-balance calculations indicate only a small amount of in-stream N loss. The stable isotope data from the samples suggest that in-stream N assimilation and not denitrification accounts for most of the N loss in the lower Mississippi River during the spring and early summer months. Published in 2001 by John Wiley & Sons, Ltd.

Atmospheric deposition of nitrogen has been cited as a major factor in the nitrogen saturation of forests in the north-eastern United States and as a contributor to the eutrophication of coastal waters, including the Gulf of Mexico near the mouth of the Mississippi River. Sources of nitrogen emissions and the resulting spatial patterns of nitrogen deposition within the Mississippi River Basin, however, have not been fully documented. An assessment of atmospheric nitrogen in the Mississippi River Basin was therefore conducted in 1998-1999 to: (1) evaluate the forms in which nitrogen is deposited from the atmosphere; (2) quantify the spatial distribution of atmospheric nitrogen deposition throughout the basin; and (3) relate locations of emission sources to spatial deposition patterns to evaluate atmospheric transport. Deposition data collected through the NADP/NTN (National Atmospheric Deposition Program/National Trends Network) and CASTNet (Clean Air Status and Trends Network) were used for this analysis. NOx Tier 1 emission data by county was obtained for 1992 from the US Environmental Protection Agency (Emissions Trends Viewer CD, 1985-1995, version 1.0, September 1996) and NH3 emissions data was derived from the 1992 Census of Agriculture (US Department of Commerce. Census of Agriculture, US Summary and County Level Data, US Department of Commerce, Bureau of the Census. Geographic Area series, 1995:1b) or the National Agricultural Statistics Service (US Department of Agriculture. National Agricultural Statistics Service Historical Data. Accessed 7/98 at URL, 1998. http://www.usda.gov/nass/pubs/hisdata++ +.htm). The highest rates of wet deposition of NO3- were in the north-eastern part of the basin, downwind of electric utility plants and urban areas, whereas the highest rates of wet deposition of NH4+ were in Iowa, near the center of intensive agricultural activities in the Midwest. The lowest rates of atmospheric nitrogen deposition were on the western (windward) side of the basin, which suggests that most of the nitrogen deposited within the basin is derived from internal sources. Atmospheric transport eastward across the basin boundary is greater for NO3- than NH4+, but a significant amount of NH4+ is likely to be transported out of the basin through the formation of (NH4)2SO4 and NH4NO3 particles--a process that greatly increases the atmospheric residence time of NH4+. This process is also a likely factor in the atmospheric transport of nitrogen from the Midwest to upland forest regions in the North-East, such as the western Adirondack region of New York, where NH4+ constitutes 38% of the total wet deposition of N.

Sulfonylurea (SU), imidazolinone (IMI), and sulfonamide (SA) herbicides are new classes of low-application-rate herbicides increasingly used by farmers. Some of these herbicides affect both weed and crop species at low dosages and must be carefully used. Less is known about the effect of these compounds on non-crop plant species, but a concentration of 100 ng/l in water has been proposed as the threshold for possible plant toxicity for most of these herbicides. Hence, analytical methods must be capable of detecting SUs, IMIs, and SAs at concentrations less than 100 ng/l in ambient water samples. The authors developed a two-cartridge, solid-phase extraction method for isolating 12 SU, 3 IMI, and 1 SA herbicides by using high-performance liquid chromatography/electrospray ionization-mass spectrometry (HPLC/ESI-MS) to identify and quantify these herbicides to 10 ng/l. This method was used to analyze 196 surface- and ground-water samples collected from May to August 1998 throughout the Midwestern United States, and more than 100 quality-assurance and quality-control samples. During the 16 weeks of the study, the HPLC/ESI-MS maintained excellent calibration linearity across the calibration range from 5 to 500 ng/l, with correlation coefficients of 0.9975 or greater. Continuing calibration verification standards at 100-ng/l concentration were analyzed throughout the study, and the average measured concentrations for individual herbicides ranged from 93 to 100 ng/l. Recovery of herbicides from 27 reagent-water samples spiked at 50 and 100 ng/l ranged from 39 to 92%, and averaged 73%. The standard deviation of recoveries ranged from 14 to 26%, and averaged 20%. This variability reflects multiple instruments, operators, and the use of automated and manual sample preparation. Spiked environmental water samples had similar recoveries, although for some herbicides, the sample matrix enhanced recoveries by as much as 200% greater than the spiked concentration. This matrix enhancement was sample- and compound-dependent. Concentrations of herbicides in unspiked duplicate environmental samples were typically within 25% of each other. The results demonstrate the usefulness of HPLC/ESI-MS for determining low-application-rate herbicides at ambient concentrations.

Nitrogen from the Mississippi River Basin is believed to be at least partly responsible for the large zone of oxygen-depleted water that develops in the Gulf of Mexico each summer. Historical data show that concentrations of nitrate in the Mississippi River and some of its tributaries have increased by factors of 2 to more than 5 since the early 1900s. We have used the historical streamflow and concentration data in regression models to estimate the annual flux of nitrogen (N) to the Gulf of Mexico and to determine where the nitrogen originates within the Mississippi Basin. Results show that for 1980–1996 the mean annual total N flux to the Gulf of Mexico was 1 568 000 t/year. The flux was approximately 61% nitrate as N, 37% organic N, and 2% ammonium as N. The flux of nitrate to the Gulf has approximately tripled in the last 30 years with most of the increase occurring between 1970 and 1983. The mean annual N flux has changed little since the early 1980s, but large year-to-year variations in N flux occur because of variations in precipitation. During wet years the N flux can increase by 50% or more due to flushing of nitrate that has accumulated in the soils and unsaturated zones in the basin. The principal source areas of N are basins in southern Minnesota, Iowa, Illinois, Indiana, and Ohio that drain agricultural land. Basins in this region yield 800 to more than 3100 kg total N/km 2 per year to streams, several times the N yield of basins outside this region. Assuming conservative transport of N in the Mississippi River, streams draining Iowa and Illinois contribute on average approximately 35% of the total N discharged by the Mississippi River to the Gulf of Mexico. In years with high precipitation they can contribute a larger percentage.

The environmental occurrence of trace organic compounds such as pharmaceuticals, personal care products, pesticides, and hormones, and their potential adverse effects on aquatic and terrestrial life and on human health is an issue that concerns not only scientists and engineers, but also the general public. Such trace organic compounds are being found with increasing frequency in the environment on a global scale (Halling-Sorensen et al., 1998; Kolpin et al., 2002; Ashton et al., 2004; Moldovan, 2006; Gulkowska et al., 2007). Research has shown that there is a wide variety of sources and pathways for these compounds to enter the environment (Campagnolo et al., 2002; Bound and Voulvoulis, 2005; Clara et al., 2005; Glassmeyer et al., 2005; Lindqvist et al., 2005; Brown et al., 2006; Conn et al., 2006; Larsson et al., 2007; Watkinson et al., 2007). Detection capabilities for organic compounds in the environment continue to be refined and detection levels continue to become ever lower. This has lead to the documented presence of many targeted compounds in water resources around the world including in sources of public drinking water (Wiegel et al., 2004; Focazio et al., 2008). Recent studies have focused on questions concerning contaminant environmental fate and behavior (Loffler et al., 2005), as well as wastewater and drinkingwater-treatment efficacies (Stackelberg et al., 2004; Westerhoff et al., 2005). As the evidence mounts that some of these contaminants can have human or ecological health effects (Smital, 2008) there is a need for both better understanding of their fate in environmental systems and better communication of what the results of scientific investigations mean to the general public.

In many Midwestern rivers, elevated concentrations of herbicides occur during runoff events for 1−3 months following application. The highest or “peak” herbicide concentration often occurs during one of these runoff events. Herbicide concentrations in rivers are affected by a number of factors, including herbicide use patterns within the associated basin. Changing agricultural practices, reductions in recommended and permitted herbicide applications, shifts to new herbicides, and greater environmental awareness in the agricultural community have resulted in changes to herbicide use patterns. In the Midwestern United States, alachlor use was much larger in 1989 than in 1995, while acetochlor was not used in 1989, and commonly used in 1995. Use of atrazine, cyanazine, and metolachlor was about the same in 1989 and 1995. Herbicide concentrations were measured in samples from 53 Midwestern rivers during the first major runoff event that occurred after herbicide application (postapplication) in 1989, 1990, 199...

Water samples collected from rivers in the Mississippi River Basin were analyzed for selected herbicides to evaluate their discharge to the Gulf of Mexico and to identify their predominant source a...

Reservoirs are used to store water for public water supply, flood control, irrigation, recreation, hydropower, and wildlife habitat, but also often store undesirable substances such as herbicides. The outflow from 76 reservoirs in the midwestern USA, was sampled four times in 1992 and four times in 1993. At least one herbicide was detected in 82.6 percent of all samples, and atrazine was detected in 82.1 percent of all samples. Herbicide properties; topography, land use, herbicide use, and soil type in the contributing drainage area; residence time of water in reservoirs; and timing of inflow, release, and rainfall all can affect the concentration of herbicides in reservoirs. A GIS was used to quantify characteristics of land use, agricultural chemical use, climatic conditions, topographic character, and soil type by reservoir drainage basins. Multiple linear and logistic regression equations were used to model mean herbicide concentrations in reservoir outflow as a function of these characteristics. Results demonstrate a strong association between mean herbicide concentrations in reservoir outflow and herbicide use rates within associated drainage basins. Results also demonstrate the importance of including soils and basin hydrologic characteristics in models used to estimate mean herbicide concentrations.

Nitrate in surface water can have adverse effects on aquatic life and, in drinking-water supplies, can be a risk to human health. As part of a regional study, nitrate as N (NO 3 -N) was analyzed in water samples collected from streams throughout 10 Midwestern states during synoptic surveys in 1989, 1990, and 1994. Data from the period immediately following crop planting at 124 sites were analyzed using logistic regression to relate discrete categories of NO 3 -N concentrations to characteristics of the basins upstream from the sites. The NO 3 -N data were divided into three categories representing probable background concentrations ( 10 mg L -1 ). Nitrate-N concentrations were positively correlated to streamflow, upstream area planted in corn (Zea mays L.), and upstream N-fertilizer application rates. Elevated NO 3 -N concentrations were associated with poorly drained soils and were weakly correlated with population density. Nitrate-N and streamflow data collected during 1989 and 1990 were used to calibrate the model, and data collected during 1994 were used for verification. The model correctly estimated NO 3 -N concentration categories for 79% of the samples in the calibration data set and 60% of the samples in the verification data set. The model was used to indicate where NO 3 -N concentrations might be elevated or exceed the NO 3 -N MCL in streams throughout the study area. The potential for elevated NO 3 -N concentrations was predicted to be greatest for streams in Illinois, Indiana, Iowa, and western Ohio.

Agricultural chemicals in surface water may constitute a human health risk or have adverse effects on aquatic life. Recent research on unregulated rivers in the midwestern USA documents that elevated concentrations of herbicides occur for 1–4 months following application in late spring and early summer. In contrast, nitrate concentrations in unregulated rivers are elevated during fall, winter, and spring months. Natural and anthropogenic variables of river drainage basins, such as soil permeability, amount of agricultural chemicals applied, or percentage of land planted in corn, affect agricultural chemical concentration and mass transport in rivers. Presented is an analysis of selected data on agricultural chemicals collected for three regional studies conducted by the US Geological Survey. Statistical techniques such as multiple linear and logistic regression were used to identify natural and anthropogenic variables of drainage basins that have strong relations to agricultural chemical concentrations and mass transport measured in rivers. A geographic information system (GIS) was used to manage and analyze spatial data. Statistical models were developed that estimated the concentration, annual transport, and annual mean concentration of selected agricultural chemicals in midwestern rivers. Multiple linear regression models were not very successful ( R 2 from 0.162 to 0.517) in explaining the variance in observed agricultural chemical concentrations during post-planting runoff. Logistic regression models were somewhat more successful, correctly matching the observed concentration category in 61–80% of observations. Linear and multiple linear regression models were moderately successful ( R 2 from 0.522 to 0.995) in explaining the variance in observed annual transport and annual mean concentration of agricultural chemicals. Explanatory variables that were commonly significant in the regression models include estimates of agricultural chemical use, crop acreage, soil characteristics, and basin topography.

Herbicides were detected in rainfall throughout the midwestern and northeastern United States during late spring and summer of 1990 and 1991. Herbicide concentrations exhibited distinct geographic ...

The effects of 10 sampling strategies on estimates of annual mean concentrations of the herbicides atrazine, alachlor, and cyanazine in selected midwestern rivers were tested. The accuracy of the strategies was computed by comparing time-weighted annual mean herbicide concentrations calculated from water samples collected from 17 locations on midwestern rivers, with simulated annual mean concentrations calculated for each sampling strategy, using Monte Carlo simulations. Monthly sampling was the most accurate strategy tested. The U.S. Environmental Protection Agency requires quarterly sampling for municipalities using surface water as a source of drinking water. Due to the seasonality of herbicide occurrence and transport, quarterly sampling underestimates annual mean herbicide concentrations in over 40% of the simulations. Three of the strategies tested showed that, relative to quarterly sampling, a more accurate representation of annual mean concentrations could be obtained by sampling more frequently during spring and early summer runoff and assuming zero herbicide concentration during late summer and winter months.

The Gunnison River drains a mountainous basin in western Colorado, and is a large contributor of water to the Colorado River. As part of a study to assess water resource sensitivity to alterations in climate in the Gunnison River basin, climatic and hydrologic processes are being modeled. A geographic information system (GIS) is being used in this study as a link between data and modelers - serving as a common data base for project personnel with differing specialties, providing a means to investigate the effects of scale on model results, and providing a framework for the transfer of parameter values among models. Specific applications presented include: (1) developing elevation grids for a precipitation model from digital elevation model (DEM) point-elevation values, and visualizing the effects of grid resolution on model results; (2) using a GIS to facilitate the definition and parameterization of a distributed-parameters, watershed model in multiple basins; and (3) nesting atmospheric and hydrologic models to produce possible scenarios of climate change.

Historically, most environmental occurrence research has focused on the parent compounds of organic contaminants. Research, however, has documented that the environmental transport of chemicals, such as pesticides and emerging contaminants, are substantially underestimated if transformation products are not considered. Although most examples described herein were drawn from research conducted by the U.S. Geological Survey, such results are generally reflective of those found in other parts of the world. Results from a study of 51 streams in the Midwestern United States found that transformation products were seven of the ten most frequently detected pesticide compounds in late spring runoff (after application of pre-emergent herbicides), and nine of the ten most frequently detected compounds in fall season runoff (during and after harvest). In fact, 70% of the total herbicide concentration in water from the Mississippi River Basin was from transformation products. Results from a study of 86 municipal wells in Iowa found the frequency of detection increased from 17%, when pesticide parent compounds were considered, to 53%, when both parents and transformation products were considered. Transformation products were 12 of the 15 most frequently detected compounds for this groundwater study. Although studies on transformation products of synthetic organic compounds other than pesticides are not as common, wastewater treatment plant discharges have repeatedly been shown to contribute such transformation products to streams. In addition, select detergent transformation products have been commonly found in solid waste in the 1000's mg/kg. These findings and many others document that transformation products must be considered to fully assess the potential environmental occurrence of chemical contaminants and their transport and fate in various compartments of the hydrologic system.

Efforts to relate shallow ground-water quality to the land use near a well lead to several statistical difficulties. These include potential uncertainty in land-use categorical data due to misclassification, data closure, distributional skewing, and spatial autocorrelation. Methods of addressing these problems are, respectively, the establishment of limits on minimum buffer radius, the estimation of contrasts, rank-based tests of association, and subsampling to prevent buffer overlap. Relations between the presence of purgeable organic compounds in ground water and land use are used to illustrate these problems and methods.