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Pollutant fate and spatio-temporal variability in the choptank river estuary: Factors influencing water quality

Restoration of the Chesapeake Bay, the largest estuary in the United States, is a national priority. Documentation of progress of this restoration effort is needed. A study was conducted to examine water quality in the Choptank River estuary, a tributary of the Chesapeake Bay that since 1998 has been classified as impaired waters under the Federal Clean Water Act. Multiple water quality parameters (salinity, temperature, dissolved oxygen, chlorophyll a) and analyte concentrations (nutrients, herbicide and herbicide degradation products, arsenic, and copper) were measured at seven sampling stations in the Choptank River estuary. Samples were collected under base flow conditions in the basin on thirteen dates between March 2005 and April 2008. As commonly observed, results indicate that agriculture is a primary source of nitrate in the estuary and that both agriculture and wastewater treatment plants are important sources of phosphorus. Concentrations of copper in the lower estuary consistently exceeded both chronic and acute water quality criteria, possibly due to use of copper in antifouling boat paint. Concentrations of copper in the upstream watersheds were low, indicating that agriculture is not a significant source of copper loading to the estuary. Concentrations of herbicides (atrazine, simazine, and metolachlor) peaked during early-summer, indicating a rapid surface-transport delivery pathway from agricultural areas, while their degradation products (CIAT, CEAT, MESA, and MOA) appeared to be delivered via groundwater transport. Some in-river processing of CEAT occurred, whereas MESA was conservative. Observed concentrations of herbicide residues did not approach established levels of concern for aquatic organisms. Results of this study highlight the importance of continued implementation of best management practices to improve water quality in the estuary. This work provides a baseline against which to compare future changes in water quality and may be used to design future monitoring programs needed to assess restoration strategy efficacy.

Science of the Total Environment↗

Linking non-culturable (qPCR) and culturable enterococci densities with hydrometeorological conditions

Quantitative polymerase chain reaction (qPCR) measurement of enterococci has been proposed as a rapid technique for assessment of beach water quality, but the response of qPCR results to environmental conditions has not been fully explored. Culture-based E. coli and enterococci have been used in empirical predictive models to characterize their responses to environmental conditions and to increase monitoring frequency and efficiency. This approach has been attempted with qPCR results only in few studies. During the summer of 2006, water samples were collected from two southern Lake Michigan beaches and the nearby river outfall (Burns Ditch) and were analyzed for enterococci by culture-based and non-culture-based (i.e., qPCR) methods, as well as culture-based E. coli . Culturable enterococci densities (log CFU/100 ml) for the beaches were significantly correlated with enterococci qPCR cell equivalents (CE) ( R = 0.650, P < 0.0001, N = 32). Enterococci CE and CFU densities were highest in Burns Ditch relative to the beach sites; however, only CFUs were significantly higher ( P < 0.0001). Culturable enterococci densities at Burns Ditch and the beaches were significantly correlated ( R = 0.565, P < 0.0001, N = 32). Culturable E. coli and enterococci densities were significantly correlated ( R = 0.682, P < 0.0001, N = 32). Regression analyses suggested that enterococci CFU could be predicted by lake turbidity, Burns Ditch discharge, and wind direction (adjusted R 2 = 0.608); enterococci CE was best predicted by Burns Ditch discharge and log-transformed lake turbidity × wave height (adjusted R 2 = 0.40). In summary, our results show that analytically, the qPCR method compares well to the non-culture-based method for measuring enterococci densities in beach water and that both these approaches can be predicted by hydrometeorological conditions. Selected predictors and model results highlight the differences between the environmental responses of the two method endpoints and the potentially high variance in qPCR results

Lake Michigan↗

Anthropogenic tracers, endocrine disrupting chemicals, and endocrine disruption in Minnesota lakes

Concentrations of endocrine disrupting chemicals and endocrine disruption in fish were determined in 11 lakes across Minnesota that represent a range of trophic conditions and land uses (urban, agricultural, residential, and forested) and in which wastewater treatment plant discharges were absent. Water, sediment, and passive polar organic integrative samplers (POCIS) were analyzed for steroidal hormones, alkylphenols, bisphenol A, and other organic and inorganic molecular tracers to evaluate potential non-point source inputs into the lakes. Resident fish from the lakes were collected, and caged male fathead minnows were deployed to evaluate endocrine disruption, as indicated by the biological endpoints of plasma vitellogenin and gonadal histology. Endocrine disrupting chemicals, including bisphenol A, 17β-estradiol, estrone, and 4-nonylphenol were detected in 90% of the lakes at part per trillion concentrations. Endocrine disruption was observed in caged fathead minnows and resident fish in 90% of the lakes. The widespread but variable occurrence of anthropogenic chemicals in the lakes and endocrine disruption in fish indicates that potential sources are diverse, not limited to wastewater treatment plant discharges, and not entirely predictable based on trophic status and land use.

Minnesota↗

Multivariate analysis of the geochemistry and mineralogy of soils along two continental-scale transects in North America

Soils collected in 2004 along two North American continental-scale transects were subjected to geochemical and mineralogical analyses. In previous interpretations of these analyses, data were expressed in weight percent and parts per million, and thus were subject to the effect of the constant-sum phenomenon. In a new approach to the data, this effect was removed by using centered log-ratio transformations to 'open' the mineralogical and geochemical arrays. Multivariate analyses, including principal component and linear discriminant analyses, of the centered log-ratio data reveal the effects of soil-forming processes, including soil parent material, weathering, and soil age, at the continental-scale of the data arrays that were not readily apparent in the more conventionally presented data. Linear discriminant analysis of the data arrays indicates that the majority of the soil samples collected along the transects can be more successfully classified with Level 1 ecological regional-scale classification by the soil geochemistry than soil mineralogy. A primary objective of this study is to discover and describe, in a parsimonious way, geochemical processes that are both independent and inter-dependent and manifested through compositional data including estimates of the elements and corresponding mineralogy. ?? 2010.

Science of the Total Environment↗

Removal of inorganic mercury and methylmercury from surface waters following coagulation of dissolved organic matter with metal-based salts

The presence of inorganic mercury (IHg) and methylmercury (MeHg) in surface waters is a health concern worldwide. This study assessed the removal potential use of metal-based coagulants as a means to remove both dissolved IHg and MeHg from natural waters and provides information regarding the importance of Hg associations with the dissolved organic matter (DOM) fraction and metal hydroxides. Previous research indicated coagulants were not effective at removing Hg from solution; however these studies used high concentrations of Hg and did not reflect naturally occurring concentrations of Hg. In this study, water collected from an agricultural drain in the Sacramento-San Joaquin Delta was filtered to isolate the dissolved organic matter (DOM) fraction. The DOM was then treated with a range of coagulant doses to determine the efficacy of removing all forms of Hg from solution. Three industrial-grade coagulants were tested: ferric chloride, ferric sulfate, and polyaluminum chloride. Coagulation removed up to 85% of DOM from solution. In the absence of DOM, all three coagulants released IHg into solution, however in the presence of DOM the coagulants removed up to 97% of IHg and 80% of MeHg. Results suggest that the removal of Hg is mediated by DOM-coagulant interactions. There was a preferential association of IHg with the more aromatic, higher molecular weight fraction of DOM but no such relationship was found for MeHg. This study offers new fundamental insights regarding large-scale removal of Hg at environmentally relevant regarding large-scale removal of Hg at environmentally relevant concentrations.

Science of the Total Environment↗

Sulfate threshold target to control methylmercury levels in wetland ecosystems

Sulfate contamination has a significant environmental implication through the stimulation of toxic hydrogen sulfide and methylmercury (MeHg) production. High levels of MeHg are a serious problem in many wetland ecosystems worldwide. In the Florida Everglades, it has been demonstrated that increasing MeHg occurrence is due to a sulfate contamination problem. A promising strategy of lowering the MeHg occurrence is to reduce the amount of sulfate entering the ecosystem. High surface water sulfate concentrations in the Everglades are mainly due to discharges from the Everglades Agricultural Area (EAA) canals. Water and total sulfur mass balances indicated that total sulfur released by soil oxidation, Lake Okeechobee and agricultural application were the major sources contributing 49,169, 35,217 and 11,775mtonsyear-1, respectively. Total sulfur loads from groundwater, levees, and atmospheric deposition contributed to a lesser extent: 4055; 5858 and 4229mtonsyear-1, respectively. Total sulfur leaving the EAA into Water Conservation Areas (WCAs) through canal discharge was estimated at 116,360mtonsyear-1, and total sulfur removed by sugarcane harvest accounted for 23,182mtonsyear-1. Furthermore, a rise in the mineral content and pH of the EAA soil over time, suggested that the current rates of sulfur application would increase as the buffer capacity of the soil increases. Therefore, a site specific numeric criterion for sulfate of 1mgL-1 was recommended for the protection of the Everglades; above this level, mercury methylation is enhanced. In parallel, sulfide concentrations in the EAA exceeded the 2??gL-1 criterion for surface water already established by the U.S. Environmental Protection Agency (EPA). ?? 2011 Elsevier B.V.

Science of the Total Environment↗

Relating nutrient and herbicide fate with landscape features and characteristics of 15 subwatersheds in the Choptank River watershed

Excess nutrients and agrochemicals from non-point sources contribute to water quality impairment in the Chesapeake Bay watershed and their loading rates are related to land use, agricultural practices, hydrology, and pollutant fate and transport processes. In this study, monthly baseflow stream samples from 15 agricultural subwatersheds of the Choptank River in Maryland USA (2005 to 2007) were characterized for nutrients, herbicides, and herbicide transformation products. High-resolution digital maps of land use and forested wetlands were derived from remote sensing imagery. Examination of landscape metrics and water quality data, partitioned according to hydrogeomorphic class, provided insight into the fate, delivery, and transport mechanisms associated with agricultural pollutants. Mean Nitrate-N concentrations (4.9 mg/L) were correlated positively with percent agriculture (R 2 = 0.56) and negatively with percent forest (R 2 = 0.60). Concentrations were greater ( p = 0.0001) in the well-drained upland (WDU) hydrogeomorphic region than in poorly drained upland (PDU), reflecting increased denitrification and reduced agricultural land use intensity in the PDU landscape due to the prevalence of hydric soils. Atrazine and metolachlor concentrations (mean 0.29 &mu;g/L and 0.19 &mu;g/L) were also greater ( p = 0.0001) in WDU subwatersheds than in PDU subwatersheds. Springtime herbicide concentrations exhibited a strong, positive correlation (R 2 = 0.90) with percent forest in the WDU subwatersheds but not in the PDU subwatersheds. In addition, forested riparian stream buffers in the WDU were more prevalent than in the PDU where forested patches are typically not located near streams, suggesting an alternative delivery mechanism whereby volatilized herbicides are captured by the riparian forest canopy and subsequently washed off during rainfall. Orthophosphate, CIAT (6-chloro- N -(1-methylethyl)-1,3,5-triazine-2,4-diamine), CEAT (6-chloro- N -ethyl-1,3,5-triazine-2,4-diamine), and MESA (2-[(2-ethyl-6-methylphenyl) (2-methoxy-1-methylethyl)amino]-2-oxoethanesulfonic acid) were also analyzed. These findings will assist efforts in targeting implementation of conservation practices to the most environmentally-critical areas within watersheds to achieve water quality improvements in a cost-effective manner.

Delaware, Maryland↗

Occurrence and concentrations of pharmaceutical compounds in groundwater used for public drinking-water supply in California

Pharmaceutical compounds were detected at low concentrations in 2.3% of 1231 samples of groundwater (median depth to top of screened interval in wells = 61 m) used for public drinking-water supply in California. Samples were collected statewide for the California State Water Resources Control Board's Groundwater Ambient Monitoring and Assessment (GAMA) Program. Of 14 pharmaceutical compounds analyzed, 7 were detected at concentrations greater than or equal to method detection limits: acetaminophen (used as an analgesic, detection frequency 0.32%, maximum concentration 1.89 μg/L), caffeine (stimulant, 0.24%, 0.29 μg/L), carbamazepine (mood stabilizer, 1.5%, 0.42 μg/L), codeine (opioid analgesic, 0.16%, 0.214 μg/L), p -xanthine (caffeine metabolite, 0.08%, 0.12 μg/L), sulfamethoxazole (antibiotic, 0.41%, 0.17 μg/L), and trimethoprim (antibiotic, 0.08%, 0.018 μg/L). Detection frequencies of pesticides (33%), volatile organic compounds not including trihalomethanes (23%), and trihalomethanes (28%) in the same 1231 samples were significantly higher. Median detected concentration of pharmaceutical compounds was similar to those of volatile organic compounds, and higher than that of pesticides. Pharmaceutical compounds were detected in 3.3% of the 855 samples containing modern groundwater (tritium activity > 0.2 TU). Pharmaceutical detections were significantly positively correlated with detections of urban-use herbicides and insecticides, detections of volatile organic compounds, and percentage of urban land use around wells. Groundwater from the Los Angeles metropolitan area had higher detection frequencies of pharmaceuticals and other anthropogenic compounds than groundwater from other areas of the state with similar proportions of urban land use. The higher detection frequencies may reflect that groundwater flow systems in Los Angeles area basins are dominated by engineered recharge and intensive groundwater pumping.

California↗

Water- and sediment-quality effects on Pimephales promelas spawning vary along an agriculture-to-urban land-use gradient

Many streams in the U.S. are “impaired” due to anthropogenic influence. For watershed managers to achieve practical understanding of these impairments, a multitude of factors must be considered, including point and nonpoint-source influence on water quality. A spawning assay was developed in this study to evaluate water- and sediment-quality effects that influenced Pimephales promelas (fathead minnow) egg production over a gradient of urban and agricultural land use in 27 small watersheds in Eastern Wisconsin. Six pairs of reproducing fathead minnows were contained in separate mesh cartridges within one larger flow-through chamber. Water- and sediment quality were sampled for an array of parameters. Egg production was monitored for each pair providing an assessment of spawning success throughout the 21-day test periods. Incidences of low dissolved oxygen (DO) in many of these streams negatively impacted spawning success. Nine of 27 streams experienced DO less than 3.1 mg/L and 15 streams experienced DO less than 4.8 mg/L. Low DO was observed in urban and agricultural watersheds, but the upper threshold of minimum DO decreased with increasing urban development. An increase in specific conductance was related to a decrease in spawning success. In previous studies for streams in this region, specific conductance had a linear relation with chloride, suggesting the possibility that chloride could be a factor in egg production. Egg production was lower at sites with substantial urban development, but sites with low egg production were not limited to urban sites. Degradation of water- and sediment-quality parameters with increasing urban development is indicated for multiple parameters while patterns were not detected for others. Results from this study indicate that DO must be a high priority watershed management consideration for this region, specific conductance should be investigated further to determine the mechanism of the relation with egg production, and water- and sediment-quality degrade in relation to urban influence.

Science of the Total Environment↗

Tumor prevalence and biomarkers of genotoxicity in brown bullhead (Ameiurus nebulosus) in Chesapeake Bay tributaries

We surveyed four Chesapeake Bay tributaries for skin and liver tumors in brown bullhead ( Ameiurus nebulosus ). We focused on the South River, where the highest skin tumor prevalence (53%) in the Bay watershed had been reported. The objectives were to 1) compare tumor prevalence with nearby rivers (Severn and Rhode) and a more remote river (Choptank); 2) investigate associations between tumor prevalence and polynuclear aromatic hydrocarbons (PAHs) and alkylating agents; and 3) statistically analyze Chesapeake Bay bullhead tumor data from 1992 through 2008. All four South River collections exhibited high skin tumor prevalence (19% to 58%), whereas skin tumor prevalence was 2%, 10%, and 52% in the three Severn collections; 0% and 2% in the Choptank collections; and 5.6% in the Rhode collection. Liver tumor prevalence was 0% to 6% in all but one South River collection (20%) and 0% to 6% in the three other rivers. In a subset of samples, PAH-like biliary metabolites and 32 P-DNA adducts were used as biomarkers of exposure and response to polycyclic aromatic compounds (PACs). Adducts from alkylating agents were detected as O6-methyl-2′-deoxyguanosine (O6Me-dG) and O6-ethyl-2′-deoxyguanosine (O6Et-dG) modified DNA. Bullheads from the contaminated Anacostia River were used as a positive control for DNA adducts. 32 P-DNA adduct concentrations were significantly higher in Anacostia bullhead livers compared with the other rivers. We identified alkyl DNA adducts in bullhead livers from the South and Anacostia, but not the Choptank. Neither the PAH-like bile metabolite data, sediment PAH data, nor the DNA adduct data suggest an association between liver or skin tumor prevalence and exposure to PACs or alkylating agents in the South, Choptank, Severn, or Rhode rivers. Logistic regression analysis of the Chesapeake Bay database revealed that sex and length were significant covariates for liver tumors and length was a significant covariate for skin tumors.

Chesapeake Bay watershed, South River↗

Effects of watershed densities of animal feeding operations on nutrient concentrations and estrogenic activity in agricultural streams

Application of manures from animal feeding operations (AFOs) as fertilizer on agricultural land can introduce nutrients and hormones (e.g. estrogens) to streams. A landscape-scale study was conducted in the Shenandoah River watershed (Virginia, USA) in order to assess the relationship between densities of AFOs in watersheds of agricultural streams and in-stream nutrient concentrations and estrogenic activity. The effect of wastewater treatment plants (WWTPs) on nutrients and estrogenic activity was also evaluated. During periods of high and low flow, dissolved inorganic nitrogen (DIN) and orthophosphate (PO4-P) concentrations were analyzed and estrogens/estrogenic compounds were extracted and quantified as17β-estradiol equivalents (E2Eq) using a bioluminescent yeast estrogen screen. Estrogenic activity was measurable in the majority of collected samples, and 20% had E2Eq concentrations > 1 ng/L. Relatively high concentrations of DIN (> 1000 μg/L) were also frequently detected. During all sampling periods, there were strong relationships between watershed densities of AFOs and in-stream concentrations of DIN (R2 = 0.56–0.81) and E2Eq (R2 = 0.39–0.75). Relationships between watershed densities of AFOs and PO4-P were weaker, but were also significant (R2 = 0.27–0.57). When combined with the effect of watershed AFO density, streams receiving WWTP effluent had higher concentrations of PO4-P than streams without WWTP discharges, and PO4-P was the only analyte with a consistent relationship to WWTPs. The results of this study suggest that as the watershed density of AFOs increases, there is a proportional increase in the potential for nonpoint source pollution of agricultural streams and their receiving waters by nutrients, particularly DIN, and compounds that can cause endocrine disruption in aquatic organisms.

Science of the Total Environment↗

Concentration, distribution, and translocation of mercury and methylmercury in mine-waste, sediment, soil, water, and fish collected near the Abbadia San Salvatore mercury mine, Monte Amiata district, Italy

The distribution and translocation of mercury (Hg) was studied in the Paglia River ecosystem, located downstream from the inactive Abbadia San Salvatore mine (ASSM). The ASSM is part of the Monte Amiata Hg district, Southern Tuscany, Italy, which was one of the world’s largest Hg districts. Concentrations of Hg and methyl-Hg were determined in mine-waste calcine (retorted ore), sediment, water, soil, and freshwater fish collected from the ASSM and the downstream Paglia River. Concentrations of Hg in calcine samples ranged from 25 to 1500 μg/g, all of which exceeded the industrial soil contamination level for Hg of 5 μg/g used in Italy. Stream and lake sediment samples collected downstream from the ASSM ranged in Hg concentration from 0.26 to 15 μg/g, of which more than 50% exceeded the probable effect concentration for Hg of 1.06 μg/g, the concentration above which harmful effects are likely to be observed in sediment-dwelling organisms. Stream and lake sediment methyl-Hg concentrations showed a significant correlation with TOC indicating considerable methylation and potential bioavailability of Hg. Stream water contained Hg as high as 1400 ng/L, but only one water sample exceeded the 1000 ng/L drinking water Hg standard used in Italy. Concentrations of Hg were elevated in freshwater fish muscle samples and ranged from 0.16 to 1.2 μg/g (wet weight), averaged 0.84 μg/g, and 96% of these exceeded the 0.3 μg/g (methyl-Hg, wet weight) USEPA fish muscle standard recommended to protect human health. Analysis of fish muscle for methyl-Hg confirmed that > 90% of the Hg in these fish is methyl-Hg. Such highly elevated Hg concentrations in fish indicated active methylation, significant bioavailability, and uptake of Hg by fish in the Paglia River ecosystem. Methyl-Hg is highly toxic and the high Hg concentrations in these fish represent a potential pathway of Hg to the human food chain.

Monte Amiata↗

The population structure of Escherichia coli isolated from subtropical and temperate soils

While genotypically-distinct naturalized Escherichia coli strains have been shown to occur in riparian soils of Lake Michigan and Lake Superior watersheds, comparative analyses of E. coli populations in diverse soils across a range of geographic and climatic conditions have not been investigated. The main objectives of this study were to: (a) examine the population structure and genetic relatedness of E. coli isolates collected from different soil types on a tropical island (Hawaii), and (b) determine if E. coli populations from Hawaii and temperate soils (Indiana, Minnesota) shared similar genotypes that may be reflective of biome-related soil conditions. DNA fingerprint and multivariate statistical analyses were used to examine the population structure and genotypic characteristics of the E. coli isolates. About 33% (98 of 293) of the E. coli from different soil types and locations on the island of Oahu, Hawaii, had unique DNA fingerprints, indicating that these bacteria were relatively diverse; the Shannon diversity index for the population was 4.03. Nearly 60% (171 of 293) of the E. coli isolates from Hawaii clustered into two major groups and the rest, with two or more isolates, fell into one of 22 smaller groups, or individual lineages. Multivariate analysis of variance of 89, 21, and 106 unique E. coli DNA fingerprints for Hawaii, Indiana, and Minnesota soils, respectively, showed that isolates formed tight cohesive groups, clustering mainly by location. However, there were several instances of clonal isolates being shared between geographically different locations. Thus, while nearly identical E. coli strains were shared between disparate climatologically- and geographically-distinct locations, a vast majority of the soil E. coli strains were genotypically diverse and were likely derived from separate lineages. This supports the hypothesis that these bacteria are not unique and multiple genotypes can readily adapt to become part of the soil autochthonous microflora.

Hawai'i, Indiana, Minnesota↗

Concentration of organic contaminants in fish and their biological effects in a wastewater-dominated urban stream

Data are presented on the concentrations of alkylphenol and alkylphenol ethoxylates (APEs) and persistent organic compounds in largemouth bass collected from a waste-water dominated stream in downtown Chicago. The fish residue concentrations of APEs are compared to concentrations of the APEs in the water that were collected at weekly intervals over two months bracketing the fall (2006) and a spring (2007) fish collection. The concentrations of APEs were significantly higher in the spring-collected fish (5.42 μg/g) versus the fall (0.99 μg/g) tand these differences were shared by differences in the water concentrations (spring — 11.47 versus fall — 3.44 μg/L). The differences in water concentration were negatively correlated with water temperatures observed over the two sampling times. Fish residue concentrations of persistent organic compounds (PCBs, PBDEs, toxaphene, and many legacy pesticides including the DDT family) did not vary from fall to spring. Some of these residue concentrations were comparable to the highest NPE (nonylphenol ethoxylate) homologue concentrations, e.g. NP1EO was 3.5 μg/g in the bass for the spring, the PBDE-congener 47 and p,p′-DDE averaged 1.0 μg/g and 0.5 μg/g, respectively, over both seasons. All the other persistent single-analyte concentrations were lower. Biological endpoints for endocrine effects measured in the same fish showed that there was an apparent positive correlation for physiological effects based on increased vitellogenin levels in males versus concentration of NPEs; however there were no observable histological differences in fall versus spring fish samples.

Science of the Total Environment↗

Zinc isotope investigation of surface and pore waters in a mountain watershed impacted by acid rock drainage

The pollution of natural waters with metals derived from the oxidation of sulfide minerals like pyrite is a global environmental problem. However, the metal loading pathways and transport mechanisms associated with acid rock drainage reactions are often difficult to characterize using bulk chemical data alone. In this study, we evaluated the use of zinc (Zn) isotopes to complement traditional geochemical tools in the investigation of contaminated waters at the former Waldorf mining site in the Rocky Mountains, Colorado, U.S.A. Geochemical signatures and statistical analysis helped in identifying two primary metal loading pathways at the Waldorf site. The first was characterized by a circumneutral pH, high alkalinity, and high Zn/Cd ratios. The second was characterized by acidic pHs and low Zn/Cd ratios. Zinc isotope signatures in surface water samples collected across the site were remarkably similar (the δ 66 Zn, relative to JMC 3-0749-L, for most samples ranged from 0.20 to 0.30‰ ± 0.09‰ 2σ). This probably suggests that the ultimate source of Zn is consistent across the Waldorf site, regardless of the metal loading pathway. The δ 66 Zn of pore water samples collected within a nearby metal-impacted wetland area, however, were more variable, ranging from 0.20 to 0.80‰ ± 0.09‰ 2σ. Here the Zn isotopes seemed to reflect differences in groundwater flow pathways. However, a host of secondary processes might also have impacted Zn isotopes, including adsorption of Zn onto soil components, complexation of Zn with dissolved organic matter, uptake of Zn into plants, and the precipitation of Zn during the formation of reduced sulfur species. Zinc isotope analysis proved useful in this study; however, the utility of this isotopic tool would improve considerably with the addition of a comprehensive experimental foundation for interpreting the complex isotopic relationships found in soil pore waters.

Colorado↗

Assessing time-integrated dissolved concentrations and predicting toxicity of metals during diel cycling in streams

Evaluating water quality and the health of aquatic organisms is challenging in systems with systematic diel (24 hour) or less predictable runoff-induced changes in water composition. To advance our understanding of how to evaluate environmental health in these dynamic systems, field studies of diel cycling were conducted in two streams (Silver Bow Creek and High Ore Creek) affected by historical mining activities in southwestern Montana. A combination of sampling and modeling tools were used to assess the toxicity of metals in these systems. Diffusive Gradients in Thin Films (DGT) samplers were deployed at multiple time intervals during diel sampling to confirm that DGT integrates time-varying concentrations of dissolved metals. Thermodynamic speciation calculations using site specific water compositions, including time-integrated dissolved metal concentrations determined from DGT, and a competitive, multiple-metal biotic ligand model incorporated into the Windemere Humic Aqueous Model Version 6.0 (WHAM VI) were used to determine the chemical speciation of dissolved metals and biotic ligands. The model results were combined with previously collected toxicity data on cutthroat trout to derive a relationship that predicts the relative survivability of these fish at a given site. This integrative approach may prove useful for assessing water quality and toxicity of metals to aquatic organisms in dynamic systems and evaluating whether potential changes in environmental health of aquatic systems are due to anthropogenic activities or natural variability.

Science of the Total Environment↗

Potential pollutant sources in a Choptank River (USA) subwatershed and the influence of land use and watershed characteristics

Row-crop and poultry production have been implicated as sources of water pollution along the Choptank River, an estuary and tributary of the Chesapeake Bay. This study examined the effects of land use, subwatershed characteristics, and climatic conditions on the water quality parameters of a subwatershed in the Choptank River watershed. The catchments within the subwatershed were defined using advanced remotely-sensed data and current geographic information system processing techniques. Water and sediment samples were collected in May&ndash;October 2009 and April&ndash;June 2010 under mostly baseflow conditions and analyzed for select bacteria, nitrate-N, ammonium-N, total arsenic, total phosphorus (TP), orthophosphate (ortho-P), and particle-phase phosphorus (PP); n = 96 for all analytes except for arsenic, n = 136, and for bacteria, n = 89 (aqueous) and 62 (sediment). Detections of Enterococci and Escherichia coli concentrations were ubiquitous in this subwatershed and showed no correlation to location or land use, however larger bacterial counts were observed shortly after precipitation. Nitrate-N concentrations were not correlated with agricultural lands, which may reflect the small change in percent agriculture and/or the similarity of agronomic practices and crops produced between catchments. Concentration data suggested that ammonia emission and possible deposition to surface waters occurred and that these processes may be influenced by local agronomic practices and climatic conditions. The negative correlation of PP and arsenic concentrations with percent forest was explained by the stronger signal of the head waters and overland flow of particulate phase analytes versus dissolved phase inputs from groundwater. Service roadways at some poultry production facilities were found to redirect runoff from the facilities to neighboring catchment areas, which affected water quality parameters. Results suggest that in this subwatershed, catchments with poultry production facilities are possible sources for arsenic and PP as compared to catchment areas where these facilities were not present.

Choptank River↗

Point sources of emerging contaminants along the Colorado River Basin: Source water for the arid Southwestern United States

Emerging contaminants (ECs) (e.g., pharmaceuticals, illicit drugs, personal care products) have been detected in waters across the United States. The objective of this study was to evaluate point sources of ECs along the Colorado River, from the headwaters in Colorado to the Gulf of California. At selected locations in the Colorado River Basin (sites in Colorado, Utah, Nevada, Arizona, and California), waste stream tributaries and receiving surface waters were sampled using either grab sampling or polar organic chemical integrative samplers (POCIS). The grab samples were extracted using solid-phase cartridge extraction (SPE), and the POCIS sorbents were transferred into empty SPEs and eluted with methanol. All extracts were prepared for, and analyzed by, liquid chromatography–electrospray-ion trap mass spectrometry (LC–ESI-ITMS). Log D OW values were calculated for all ECs in the study and compared to the empirical data collected. POCIS extracts were screened for the presence of estrogenic chemicals using the yeast estrogen screen (YES) assay. Extracts from the 2008 POCIS deployment in the Las Vegas Wash showed the second highest estrogenicity response. In the grab samples, azithromycin (an antibiotic) was detected in all but one urban waste stream, with concentrations ranging from 30 ng/L to 2800 ng/L. Concentration levels of azithromycin, methamphetamine and pseudoephedrine showed temporal variation from the Tucson WWTP. Those ECs that were detected in the main surface water channels (those that are diverted for urban use and irrigation along the Colorado River) were in the region of the limit-of-detection (e.g., 10 ng/L), but most were below detection limits.

Arizona;California;Colorado;Nevada;New Mexico;Utah↗