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Pesticides in surface waters: distribution, trends, and governing factors

Pesticde use in agriculture and non-agriculture settings has increased dramatically over the last several decades. Concern about adverse effects on the environment and human health has spurred an enormous amount of research into their environmental behavior and fate. Pesticides in Surface Waters presents a comprehensive summary of this research. This book evaluates published studies that focus on measuring pesticide concentration. The studies chosen include peer reviewed scientific literature, government reports, laboratory studies, and those using microcosms and artificial streams and ponds. The authors used this information to develop their overview of pesticide contamination of surface waters. The exhaustive compilation of data along with the fundamental science make this book essential for those involved in pesticide use, environmental protection, water quality, and human or ecological risk assessment. Pesticides in Surface Waters covers the results of actual studies, sources of pesticides to surface water, fate and transport, and environmental significance. Hundreds of data-packed tables, maps, charts, and drawings illustrate the key points, making research and application easy and cost effective.

Book↗

Environmental presence and persistence of pharmaceuticals: An overview

Emerging contaminants (ECs) in the environment – that is, chemicals with domestic, municipal, industrial, or agricultural sources that are not commonly monitored but may have the potential for adverse environmental effects – is a rapidly growing field of research. The use of “emerging” is not intended to infer that the presence of these compounds in the environment is new. These chemicals have been released into the environment as long as they have been in production or, in the case of hormones and other endogenous compounds, since the rise of animal life. What is emerging is the interest by the scientific and lay communities in the presence of these chemicals in the environment, the analytical capabilities required for detection, and the subtle effects that very small concentrations of these chemicals appear to have on aquatic biota. In December 2006, Environmental Science & Technology devoted an entire special issue (volume 40, number 23) to the topic of ECs, illustrating the increased interest in the subject. Within the EGs, one particular class that has seen a substantial increase in research over the past 10 years is pharmaceuticals and personal-care products (PPCPs). This increased research interest can be demonstrated by several means, including requests for proposals from funding agencies, but the clearest indication of a focused effort to understand the introduction, transformation, and potential health and environmental effects of PPCPs and ECs, in general, is the number of published reports. This increase can be shown by examining six environmental journals that regularly publish PPCP-related papers – Chemosphere , Environmental Science & Technology , Environmental Toxicology and Chemistry , Science of the Total Environment , Water Research , and Water Science and Technology . In 1998 there were 22 papers published on pharmaceuticals, antibiotics, or drugs in these 6 journals; by 2006, this number increased sixfold to 132 papers (Figure 1.1). This growth can be attributed to a number of factors. The presence of pharmaceuticals in surface-water samples from Europe and the United States was documented in several sentinel papers. These ground-breaking works encouraged other scientists to examine the rivers, streams, lakes, and reservoirs in their regions for such chemicals. In addition, the intense public attention paid to news reports on the environmental detections of these chemicals and possible effects of aquatic life has made this issue visible to the wastewater-treatment, drinking-water treatment, and regulatory communities. This has driven the funding bodies associated with these communities to fund studies or request proposals that address the presence, fate, and effects of PPCPs in aquatic systems. The release of the first comprehensive reconnaissance of pharmaceuticals and other wastewater contaminants in the United States provides an example of the intense media interest in this topic. Within 6 days on online publication of this study, 72 newspapers across the United States had published articles describing the results, either locally written or based on international media syndicate reports. There also was substantial concurrent coverage by local and national radio and television outlets, including the Cable News Network, ABC World News Tonight , and National Public Radio. A substantial fraction of these news stories may be attributable to press releases and media briefings prior to publication. However, the interest by television and print journalists in reporting the results of a peer-reviewed journal article to the general public was motivated by the recognition that describing the presence of PPCPs in water supplies would be of interest to the public. To better convey the results of the study published by Koplin et al. to the public, a separate general-interest fact sheet was published to summarize the important points of the study. Because PPCPs are commonly and widely used by individuals, there is likely a preexisting, personal identification with these compounds that does not occur for the wide range of other organic and inorganic contaminants whose presence in the environment has previously been described. This greater public “name recognition” makes itself known through the media to the regulatory and technical community and has prompted interest in sponsoring research that defines the composition and concentrations of PPCPs in potential sources and their fate and effects following relase into the environment. Independent of the drivers that potentially fuel the interest in studies of PPCPs, it is clear that PPCP research has grown beyond surface-water studies to examine issues such as: • Presence in other matrices, such as groundwater, landfill leachates, sediments, and biosolids. • Environmental transport and fate in surface water, groundwater, and soils amended with reclaimed water or biosolids. • PPCP source elucidation, such as wastewater treatment plant (WWTP) effluents, confined animal feeding operations (CAFOs), and aquaculture. • Removal during wastewater and drinking-water treatment. • Effects on aquatic ecosystems, terrestrial ecosystems, and human health. The chapters in this book provide an extensive examination of current environmental pharmaceutical research and are divided into three sections: “Occurrence and Analysis of Pharmaceuticals in the Environment,” “Environment Fate and Transformations of Veterinary Pharmaceuticals,” and “treatment of Pharmaceuticals in Drinking Water and Wastewater.” The purpose of this introductory overview chapter is to outline current (2004-2006) knowledge about the presence and concentration of PPCPs as described in the published literature. Previous reviews should be consulted for discussions on pre-2004 publications. Those reviews will provide the reader with a comprehensive introduction to the topic of PPCPs in the environment. This chapter describes the sources of PPCPs and other organic contaminants often associated with human wastewater into the environment, the range of concentrations present in various environmental compartments, and the potential routes of removal/sequestration. An overview of the sources and fate of veterinary pharmaceuticals will be discussed in Chapter 5, “Fate and Transport of Veterinary Medicines in the Soil Environment.”

Book chapter↗

Understanding the hydrologic impacts of wastewater treatment plant discharge to shallow groundwater: Before and after plant shutdown

Effluent-impacted surface water has the potential to transport not only water, but wastewater-derived contaminants to shallow groundwater systems. To better understand the effects of effluent discharge on in-stream and near-stream hydrologic conditions in wastewater-impacted systems, water-level changes were monitored in hyporheic-zone and shallow-groundwater piezometers in a reach of Fourmile Creek adjacent to and downstream of the Ankeny (Iowa, USA) wastewater treatment plant (WWTP). Water-level changes were monitored from approximately 1.5 months before to 0.5 months after WWTP closure. Diurnal patterns in WWTP discharge were closely mirrored in stream and shallow-groundwater levels immediately upstream and up to 3 km downstream of the outfall, indicating that such discharge was the primary control on water levels before shutdown. The hydrologic response to WWTP shutdown was immediately observed throughout the study reach, verifying the far-reaching hydraulic connectivity and associated contaminant transport risk. The movement of WWTP effluent into alluvial aquifers has implications for potential WWTP-derived contamination of shallow groundwater far removed from the WWTP outfall.

Iowa↗

Landfill leachate contributes per-/poly-fluoroalkyl substances (PFAS) and pharmaceuticals to municipal wastewater

Widespread disposal of landfill leachate to municipal sewer infrastructure in the United States calls for an improved understanding of the relative organic-chemical contributions to the wastewater treatment plant (WWTP) waste stream and associated surface-water discharge to receptors in the environment. Landfill leachate, WWTP influent, and WWTP effluent samples were collected from three landfill-WWTP systems and compared with analogous influent and effluent samples from two WWTPs that did not receive leachate. Samples were analyzed for 73 per-/poly-fluoroalkyl substances (PFAS), 109 pharmaceuticals, and 21 hormones and related compounds. PFAS were detected more frequently in leachate (92%) than in influent (55%). Total PFAS concentrations in leachate (93,100 ng/L) were more than ten times higher than in influent (6,950 ng/L), and effluent samples (3,730 ng/L). Concentrations of bisphenol A; the nonprescription pharmaceuticals cotinine, lidocaine, nicotine; and the prescription pharmaceuticals amphetamine, carisoprodol, pentoxifylline, and thiabendazole were an order of magnitude higher in landfill leachate than WWTP influent. Leachate load contributions for PFAS (0.78 to 31 g/d), bisphenol A (0.97 to 8.3 g/d), and nonprescription (2.0 to 3.1 g/d) and prescription (0.48 to 2.5 g/d) pharmaceuticals to WWTP influent were generally low (<10 g/d) for most compounds because of high influent-to-leachate volumetric ratios (0.983). No clear differences in concentrations were apparent between effluents from WWTPs receiving landfill leachate and those that did not receive landfill leachate.

Environmental Science: Water Research & Technology↗

Improving gas-derived parameterization of groundwater using free phase gas measurements

Dissolved atmogenic gasses in groundwater provide significant information about recharge conditions, flowpath, and age. Free phase gas in aquifers is largely ignored in these analyses and there is a lack of quantitative analysis for gas flux mechanisms. Many related fields encountering multiphase flow acknowledge that the presence of bubbles allows for the rapid exsolution of dissolved gasses and volatile compounds through diffusive and polar forces. By measuring the mass flow of the exsolved gas at a spring, coupled with compositional analysis in the free and dissolved phases, we show that not incorporating the effects of the free gas phase of bubbling springs introduces error in the estimation of total gas quantities, particularly light noble gasses. This can significantly affect the corresponding estimation of noble gas temperature (NGT) and apparent age. We examine the transport of free and dissolved gas from the recharge zone, using water level variation data, to the discharge location where the gases are measured. This technique of using the free gas phase for assessing aquifer dynamics will improve groundwater conceptual models, particularly in karstic aquifers where rapid fluctuations in the water table facilitate the development of excess air, generating multiphase spring discharge.

Environmental Science: Water Research & Technology↗

Modeling risk dynamics of contaminants of emerging concern in a temperate-region wastewater effluent-dominated stream

Wastewater effluent-dominated streams are becoming increasingly common worldwide, including in temperate regions, with potential impacts on ecological systems and drinking water sources. We recently quantified the occurrence/spatiotemporal dynamics of pharmaceutical mixtures in a representative temperate-region wastewater effluent-dominated stream (Muddy Creek, Iowa) under baseflow conditions and characterized relevant fate processes. Herein, we quantified the ecological risk quotients (RQs) of 19 effluent-derived contaminants of emerging concern (CECs; including: 14 pharmaceuticals, 2 industrial chemicals, and 3 neonicotinoid insecticides) and 1 run-off-derived compound (atrazine) in the stream under baseflow conditions, and estimated the probabilistic risks of effluent-derived CECs under all-flow conditions ( i.e. , including runoff events) using stochastic risk modeling. We determined that 11 out of 20 CECs pose medium-to-high risks to local ecological systems ( i.e. , algae, invertebrates, fish) based on literature-derived acute effects under measured baseflow conditions. Stochastic risk modeling indicated decreased, but still problematic, risk of effluent-derived CECs ( i.e. , RQ ≥ 0.1) under all-flow conditions when runoff events were included. Dilution of effluent-derived chemicals from storm flows thus only minimally decreased risk to aquatic biota in the effluent-dominated stream. We also modeled in-stream transport. Thirteen out of 14 pharmaceuticals persisted along the stream reach (median attenuation rate constant k < 0.1 h −1 ) and entered the Iowa River at elevated concentrations. Predicted and measured concentrations in the drinking water treatment plant were below the human health benchmarks. This study demonstrates the application of probabilistic risk assessments for effluent-derived CECs in a representative effluent-dominated stream under variable flow conditions (when measurements are less practical) and provides an enhanced prediction tool transferable to other effluent-dominated systems.

Iowa↗

Predicted aquatic exposure effects from a national urban stormwater study

A multi-agency study of 438 organic and 62 inorganic chemicals measured in urban stormwater during 50 total runoff events at 21 sites across the United States demonstrated that stormwater discharges can generate localized, aquatic exposures to extensive contaminant mixtures, including organics suspected to cause adverse aquatic-health effects. The aggregated risks to multiple aquatic trophic levels (fish, invertebrates, plants) of the stormwater mixture exposures, which were documented in the national study, were explored herein by calculating cumulative ratios of organic-contaminant in vitro exposure–activity cutoffs (∑ EAR ) and health-benchmark-weighted cumulative toxicity quotients (∑ TQ ). Both risk assessment approaches indicated substantial (moderate to high) risk for acute adverse effects to aquatic organisms across multiple trophic levels (fish, macroinvertebrates, non-vascular/vascular plants) at or near stormwater discharge points across the United States. The results are interpreted as potential orders of magnitude underestimates of actual aquatic risk in stormwater control wetlands or in the immediate vicinity of such discharges to surface-water receptors, because the 438 organic-compound analytical space assessed in this study is orders of magnitude less than the 350 000 parent compounds estimated to be in current commercial use globally and the incalculable chemical-space of potential metabolites and degradates.

Environmental Science: Water Research and Technolo↗

Exposures and potential health implications of contaminant mixtures in linked source water, finished drinking water, and tapwater from public-supply drinking water systems in Minneapolis/St. Paul area, USA

Continued improvements in drinking-water quality characterization and treatment/distribution infrastructure are required to address the expanding number of documented environmental contaminants. To better understand the variability in contaminant exposures from the drinking water resource (surface and groundwater), through the distribution process, to the point-of-use (tapwater), in 2019 a synoptic assessment of broad chemical exposures was conducted in system-specific source waters, finished drinking water and service-area tapwater from 10 drinking water treatment facilities in the greater Minneapolis/St. Paul area of Minnesota, United States. Source water, finished water (collected pre-distribution in the treatment facility), and tapwater samples were analyzed for 465 unique organic compounds, 34 inorganic constituents, and 3 field parameters as well as in vitro estrogen, androgen, and glucocorticoid bioactivities. Mixtures of organic and inorganic contaminants were prevalent in source water, finished water, and tapwater samples, indicating the continued need for broad assessments of mixed contaminant exposures to characterize potential drinking-water human health outcomes. Contaminant concentrations were similar among drinking water sources and no exceedances of Environmental Protection Agency maximum contaminant level(s) (MCL) were observed in any treated sample (finished water or tapwater) in this study. No treated sample contained estrogenic, androgenic, or glucocorticoid activity at concentrations that may cause adverse human health effects. However, there were multiple exceedances of non-enforceable MCL goal(s) (MCLG), and other health advisories combined with frequent exceedances of benchmark-based hazard indices in both finished water and tapwater samples. These results indicate that exposure to contaminant mixtures is a potential public health concern underscoring our continued efforts to assess contaminant mixture exposures at the drinking-water point of consumption using a broad analytical scope.

Minnesota↗

Comparing contaminants of emerging concern and microbial signatures of wastewater treated by membrane bioreactor and oxidation ditch methods

Membrane bioreactors (MBRs) are an attractive option for upgrades to aging wastewater treatment infrastructure across the United States (U.S.) because they have a relatively small footprint and can handle various wastewater loading conditions. However, little is known regarding the efficiency with which MBRs can reduce contaminants of emerging concern (CECs) and microbial loads, or how they influence the microbiome of wastewater effluent. In 2022, we collected nine paired samples of primary treated effluent (PRI), secondary effluent treated by oxidation ditches (OXI), and secondary effluent treated by MBR from a facility in Minnesota, U.S. Samples were analyzed for CECs including 4 alkylphenol ethoxylates, 6 bisphenol analogues, 20 hormones, 110 pharmaceuticals, and 82 pesticides as well as heterotrophic bacteria counts (HPC) and microbiome communities. Except for pesticides, total sample concentrations of CEC classes in OXI and MBR effluents were similar and lower compared to PRI ( p < 0.01). Pesticide concentrations were similar among all treatments. HPC was lower in MBR, compared to OXI, in 67% of samples. Despite limited differences in CEC signatures, differences in the microbiome between the two secondary treatments were observed. OXI showed more distinct differences in bacterial operational taxonomic unit (OTU) presence from PRI, compared to MBR. Relations between some contaminant groups ( e.g. , pharmaceuticals, bisphenols) and effluent microbiomes were observed, though most correlated with PRI effluent. Results from our study indicate that MBR is as effective as OXI at producing high-quality effluent and offers a viable alternative to conventional secondary treatment methods. This full-scale study provides data that helps fill knowledge gaps related to MBR performance outside of lab or benchtop experiments and direct comparison to OXI treatment.

Environmental Science: Water Research & Technology↗

Tapwater-contaminant mixtures and risk in a biofuel-facility impacted private-well community

We assessed private-well drinking water (DW) at the point of use ( i.e. , tapwater, TW) within a rural Nebraska community around a state-closed biofuel facility, which used pesticide-treated corn seed as feedstock for ethanol production. Organic (485), inorganic (34), and microbial (13) analytes were assessed at 15 locations in June 2022, to evaluate the relative contribution of facility-consistent pesticides (seed-treatment fungicides and insecticides) to overall TW-contaminant exposures and predicted human-health risks. Thirty-three organics (12 pesticides) and 28 inorganics were detected, the former including the fungicide sedaxane, insecticide chlorantraniliprole, and multiple neonicotinoid insecticides/degradates, all consistent with seed treatment and respective biofuel-facility waste. Assessment of pesticides only at extant point-of-use (POU) treatment taps at three sites demonstrated complete elimination of all TW-pesticide detections. Based on detection of maximum pesticide concentrations in a home located downstream along a creek capturing facility runoff, pesticides only were assessed in January 2023 again at this home and at three adjacent locations, confirming results at the former and documenting decreasing TW-pesticide concentrations, including neonicotinoids, with increasing distance from the creek. Human-health DW benchmarks are not available for many detected pesticides, including the detected fungicide and insecticides, but precautionary screening levels were exceeded frequently due to multiple inorganics. The results indicate that exposures to multiple (median: 4.5; range: 1–7) co-occurring TW contaminants of potential human-health concern are common, warranting consideration of point-of-entry or POU treatment(s) throughout the community to reduce or eliminate unrecognized exposures to TW contaminants, including facility-associated pesticides in down-gradient locations. More broadly, results emphasize the importance of continued characterization of private-TW exposures, employing a environmentally informative analytical scope, to identify and mitigate risks of unrecognized exposures in private-well-dependent rural communities.

Nebraska↗

Continuing progress toward a national assessment of water availability and use

Executive Summary The Omnibus Public Land Management Act of 2009 (Public Law 111—11) was passed into law on March 30, 2009. Subtitle F, also known as the SECURE Water Act, calls for the establishment of a “national water availability and use assessment program” within the U.S. Geological Survey (USGS). The USGS issued the first report on the program in 2013. Program progress over the period 2013–17 is reported herein to fulfill the requirement to inform Congress on implementation of the national water availability and use assessment program, also referred to as the USGS National Water Census (the Water Census). Much work has been accomplished during 2013–17 on producing water budgets for the nation, a goal USGS outlined in its first report on program progress to Congress. The USGS has completed three geographic focus area studies and has begun three others. Work has advanced on nationwide efforts in streamflow analysis, groundwater assessment and research, evapotranspiration studies, water use, environmental water science, and drought science. The USGS works with Federal and non-Federal agencies, universities, and other organizations to ensure that the information can be aggregated with other types of water-availability and socioeconomic information, such as data on food and energy production. The USGS has also made great strides in measures for delivering data and information on the Water Census to stakeholders and the public. Much work remains to be accomplished for the Nation to have a comprehensive, ongoing Water Census. In this report, the USGS lays out activities to be accomplished in the next 5 years (2017–22), based upon current funding levels. These include selecting new focus area studies, conducting hydrologic modeling to complete water budgets for the conterminous United States, expanding groundwater modeling efforts, mapping a national classification system for environmental water science, and developing an inventory of interbasin water transfers. All of these steps are necessary in order for the Water Census to achieve the goals outlined by Congress in the SECURE Water Act.

Circular↗

Partnership of Environmental Education and Research-A compilation of student research, 1999-2008

The U.S. Geological Survey (USGS) Tennessee Water Science Center and the College of Engineering and Technology at Tennessee State University developed a Partnership in Environmental Education and Research (PEER) to support environmental research at TSU and to expand the environmental research capabilities of the USGS in Tennessee. The PEER program is driven by the research needs to better define the occurrence, fate, and transport of contaminants in groundwater and surface water. Research in the PEER program has primarily focused on the transport and remediation of organic contamination in karst settings. Research conducted through the program has also expanded to a variety of media and settings. Research areas include contaminant occurrence and transport, natural and enhanced bioremediation, geochemical conditions in karst aquifers, mathematical modeling for contaminant transport and degradation, new methods to evaluate groundwater contamination, the resuspension of bacteria from sediment in streams, the use of bioluminescence and chemiluminescence to identify the presence of contaminants, and contaminant remediation in wetlands. The PEER program has increased research and education opportunities for students in the College of Engineering, Technology, and Computer Science and has provided students with experience in presenting the results of their research. Students in the program have participated in state, regional, national and international conferences with more than 140 presentations since 1998 and more than 40 student awards. The PEER program also supports TSU outreach activities and efforts to increase minority participation in environmental and earth science programs at the undergraduate and graduate levels. TSU students and USGS staff participate in the TSU summer programs for elementary and high school students to promote earth sciences. The 2007 summer camps included more than 130 students from 20 different States and Washington DC.

Tennessee↗

Environmental impacts of petroleum production--Initial results from the Osage-Skiatook Petroleum Environmental Research Sites, Osage County, Oklahoma

Exploration for and production of petroleum have caused major detrimental impacts to soils, surface and ground waters, and the local ecosystems in the United States. These impacts arise primarily from the improper disposal of large volumes of saline water produced with oil and gas, from accidental hydrocarbon and produced water releases, and from abandoned oil wells that were not correctly sealed. It is important to understand the long-term and short-term effects of produced water and hydrocarbon releases from these sites in order to develop risk-based remediation plans. Remediation is particularly needed in aging and depleted fields where land use is changing from petroleum production to residential, agricultural or recreational uses. About 20 scientists from the USGS and other governmental agencies and academia are involved in a multidisciplinary investigation to study the transport, fate, and natural attenuation of inorganic salts, trace metals, organic compounds and radionuclides present in produced water, and their impacts at the Osage-Skiatook Petroleum Environmental Research (OSPER) "A" and "B" sites, located on the Osage Reservation in Osage County, Oklahoma. Stakeholders in the project include the Osage Nation, which holds the mineral rights, the Bureau of Indian Affairs with trust responsibility, and the Army Corps of Engineers, which owns the surface rights at these sites and manages adjacent Skiatook Lake. The 4250-hectare Skiatook Lake provides drinking water to local Tulsa suburban communities and a rural water district, and offers recreational fishing and boating opportunities to tens of thousands of visitors each year. Approximately 1.5 and 1.0 hectare of land at the OSPER "A" (depleted Lester lease) and "B" (active Branstetter lease) sites, respectively, are affected by salt scarring, tree kills, soil salinization and brine and petroleum contamination due to the leakage of produced water and associated hydrocarbons from brine pits and accidental releases from active and inactive pipes and tank batteries. The leases are typical of many depleted and aging petroleum fields in Osage County, which ranks among the top oil and gas producing counties in Oklahoma with about 39,000 wells. Oil and gas production has occurred in Osage county for over one hundred years, but current production is mainly from stripper wells (averaging ~2.8 bbl/d oil and >30 bbl/d brine) that are shallow, mostly 300-700 m in depth, and produce from several sandstones of Pennsylvanian age. Results to date show that the produced water source is a Na-Ca-Cl brine (~150,000 mg/L total dissolved solids), with relatively high concentrations of Mg, Sr, and NH4, but low SO4 and H2S. With the exception of Fe and Mn, the concentrations of trace metals are low. Results also show that some and, eventually, the bulk, of inorganic salts and some dissolved organic species in the released brine from both sites will reach Skiatook Lake. Results at the "A" site show that the salts have essentially been removed from the sandy soil which formed in a surficial layer of eolian sand, but degraded and weathered oil persists on the surface of old oil and brine pits, close to sites of old tanks, on old channels that carried oil from tanks to the oil pits and other impacted areas. Results also show a plume of high salinity water (5,000-30,600 mg/L TDS) is present at intermediate depths that extend from below the old oil and brine pits to Skiatook Lake. No liquid petroleum was found in the contaminated groundwater, but soluble petroleum byproducts, including organic acid anions and other volatile organic compounds (VOCs) are present. Results to date clearly show that significant amounts of salts from produced-water releases and petroleum hydrocarbons still remain in the soils and rocks of the impacted area after more than 60 years of natural attenuation. At the "B" site significant amounts of produced water from the two active brine pits percolate into the surficial rocks and flow towards the Skiatook Reservoir; but only minor amounts of liquid petroleum leave the brine pits and reach the Skiatook Reservoir. At both sites, results show that the chemical composition of released brines is modified further by sorption, mineral precipitation/dissolution, transpiration, volatilization and bacterially mediated oxidation/reduction reactions.

Oklahoma↗

Assessment of existing groundwater quality data in the Green-Duwamish watershed, Washington

The United States Geological Survey (USGS) provided technical support to the Washington Department of Ecology (Ecology) in their assessment of the role groundwater plays in contributing pollutant loading to the Green-Duwamish River near Seattle, Washington. Ecology is developing watershed hydrology models of the Green-Duwamish watershed, and need to assign realistic contaminant concentrations to the various Hydrologic Response Units represented in their models. The USGS compiled existing groundwater quality data in the Green-Duwamish watershed, and this report summarizes results and interpretation of the dataset, including identifying data gaps and needs for further research and monitoring. The sources of existing data were the USGS’s National Water Information System, Ecology’s Environmental Information Management System, and a compilation of several studies by Leidos, a scientific research company. The water-quality parameters of interest included polychlorinated biphenyl (PCB) Aroclors and congeners, phthalates, carcinogenic polycyclic aromatic hydrocarbons (cPAHs), arsenic, copper, and zinc. Results were grouped into the four subwatersheds delineated in Ecology’s hydrology models: Duwamish, Lower Green, Soos, and Upper Green. Results from the Duwamish subwatershed were further sub-divided by the USGS into the Lower Duwamish, containing land adjacent to the Lower Duwamish Waterway Superfund site, and the Upper Duwamish, containing the remaining area of the Duwamish subwatershed. Groundwater quality data in the Lower Duwamish were treated separately because there is known contamination in this area. The availability of water quality data varied by subwatershed as follows: phthalate data was only available within the Duwamish, PCB data was available within the Duwamish and Lower Green, cPAH data was available within the Duwamish, Lower Green, and Soos, and data for arsenic, copper, and zinc were available within all four subwatersheds. More than 99 percent of the available data was within the Duwamish subwatershed, identifying a need for additional monitoring of groundwater quality in the other subwatersheds.

Washington↗

Water-sediment controversy in setting environmental standards for selenium

A substantial amount of laboratory and field research on selenium effects to biota has been accomplished since the national water quality criterion was published for selenium in 1987. Many articles have documented adverse effects on biota at concentrations below the current chronic criterion of 5 μg/L. This commentary will present information to support a national water quality criterion for selenium of 2 μg/L, based on a wide array of support from federal, state, university, and international sources. Recently, two articles have argued for a sediment-based criterion and presented a model for deriving site-specific criteria. In one example, they calculate a criterion of 31 μg/L for a stream with a low sediment selenium toxicity threshold and low site-specific sediment total organic carbon content, which is substantially higher than the national criterion of 5 μg/L. Their basic premise for proposing a sediment-based method has been critically reviewed and problems in their approach are discussed.

Ecotoxicology and Environmental Safety↗

The potential effects of sodium bicarbonate, a major constituent from coalbed natural gas production, on aquatic life

The production water from coalbed natural gas (CBNG) extraction contains many constituents. The U.S. Environmental Protection Agency has established aquatic life criteria for some of these constituents, and it is therefore possible to evaluate their risk to aquatic life. However, of the major ions associated with produced waters, chloride is the only one with an established aquatic life criterion (U.S. Environmental Protection Agency, 1988). The focus of this research was NaHCO 3 , a compound that is a major constituent of coalbed natural gas produced waters in the Tongue and Powder River Basins. This project included laboratory experiments, field in situ experiments, a field mixing zone study, and a fishery presence/absence assessment. Though this investigation focuses on the Tongue and Powder River Basins, the information is applicable to other watersheds where sodium bicarbonate is a principle component of product water either from CBNG or from traditional or unconventional oil and gas development. These data can also be used to separate effects of saline discharges from those potentially posed by other constituents. Finally, this research effort and the additional collaboration with USGS Water Resources and Mapping, Bureau of Land Management, US Environmental Protection Agency, State of Montana, State of Wyoming, Montana State University, University of Wyoming, and others as part of a Powder River Aquatic Task Group, can be used as a model for successful approaches to studying landscapes with energy development. The laboratory acute toxicity experiments were completed with a suite of organisms, including 7 species of fish, 5 species of invertebrates, and 1 amphibian species. Experiments performed on these multiple species resulted in LC50s that ranged from 1,120 to greater than (>) 8,000 milligrams sodium bicarbonate per liter (mg NaHCO 3 /L) (also defined as 769 to >8,000 milligrams bicarbonate per liter (mg HCO 3 -/L) or total alkalinity expressed as 608 to >4,181 milligrams calcium carbonate per liter (mg CaCO 3 /L)) that varied across species and lifestage within a species. The age at which fish were exposed to NaHCO 3 significantly affected the severity of toxic responses for some organisms. The chronic toxicity of NaHCO 3 was defined in experiments that lasted from 7&mdash;60 days post-hatch. For these experiments, sublethal effects such as growth and reproduction, in addition to significant reductions in survival were included in the final determination of effects. Chronic toxicity was observed at concentrations that ranged from 450 to 800mg NaHCO 3 /L (also defined as 430 to 657 mg HCO 3 -/L or total alkalinity expressed as 354 to 539 mg CaCO 3 /L) and the specific concentration depended on the sensitivity of the four species of invertebrates and fish exposed. Sublethal investigations during chronic studies revealed percent decrease in the activity of sodium-potassium adenosine triphosphatase (Na/K ATPase, an enzyme involved in ionoregulation) and the age of the fish at the onset of the decrease may affect the ability of fathead minnow to survive exposures to NaHCO 3 . A database of toxicity evaluations of NaHCO 3 on aquatic life has been constructed. Using these data, sample acute and chronic criteria of 459 and 381 mg NaHCO 3 /L, respectively, can be calculated for the protection of aquatic life. The final derivation and implementation of such criteria is, of course, left to the discretion of the concerned management agencies. A combination of in situ experiments, static-renewal experiments performed simultaneously with in situ experiments, and static renewal experiments performed with site water in the laboratory, demonstrated that untreated coalbed natural gas (CBNG) product water from the Tongue and Powder River Basins reduces survival of fathead minnow and pallid sturgeon. More precisely, the survival of early-lifestage fathead minnow, especially those less than 6-days post hatch (dph), likely is reduced significantly in the field when concentrations of NaHCO 3 rise above 1,500 mg/L. However, age was not a factor for pallid sturgeon and they were sensitive to product water regardless of age. Treatment with the Higgins Loop&trade; technology and dilution of untreated water increased survival in the laboratory. Both of these situations reduced ammonia in addition to the concentrations of NaHCO 3 . These experiments addressed the acute toxicity of effluent waters being added to the main stem rivers, but did not address issues related to the volumes of water that may be added to the watershed. Mixing zones of the three outfalls studied ranged from approximately 800&mdash;1,200 m below the confluence and the areas within these mixing zones with acutely lethal concentrations of NaHCO 3 (as defined by the presence of concentrated dye) are limited. The areas with concentrations of NaHCO 3 more than the concentrations likely to cause significant mortality, and more than the calculated sample water-quality criteria in the Tongue and Powder River Basins appear to be limited to tributaries and parts of mixing zones with considerable additions of untreated effluent.

Montana;Wyoming↗

Assessing environmental drivers of denitrification in restored riverine floodplains

Restoration of impaired floodplains is an increasingly prevalent strategy for alleviating water quality concerns and reducing downstream flooding at watershed scales. Floodplains temporarily store water and slow flow velocity to promote sedimentation during overbank flooding and remove inorganic nitrogen from floodwater and groundwater via denitrification. Evaluating the impacts of different restoration strategies on denitrification can inform more strategic investments into floodplain modifications that improve water quality outcomes. Our research investigates how denitrification rates in floodplains respond to environmental factors that are actionable from an engineering perspective through design and water resources management. We seasonally measured soil denitrification enzyme activity and various environmental characteristics in 4 floodplains with different restoration design and management approaches at the confluence of the Wabash and Tippecanoe Rivers in Indiana, United States. Our results showed that denitrification rates in an agricultural floodplain were significantly lower than in restored floodplains with native vegetation. Certain soil conditions characteristic of floodplain wetlands were associated with higher denitrification, particularly elevated total nitrogen, moisture, silt, and organic matter contents. Vegetation species composition was correlated with denitrification rates. This link may reflect the direct effects of vegetation on soil conditions, such as supplying labile organic carbon, or indirect effects, such as vegetation acting as an indicator of hydrologic regime and land use. Denitrification seasonally varied, peaking in winter when nitrate supply from rivers draining agricultural watersheds in the region is also high. Substrate limitation of soil denitrification enzyme activity was most significant during the summer when overbank flooding, which replenishes soil nitrogen stocks, rarely occurs. Our findings indicate that denitrification capacity will likely be maximized in riverine floodplains that are restored as wetlands with diverse native vegetation and enhanced hydrologic connectivity. Such restoration activities promote higher denitrification rates via elevated moisture, fine sediment deposition, and soil organic matter.

Tippecanoe River, Wabash River↗