Temporal variability in TiO2 engineered particle concentrations in rural Edisto River.

Titanium dioxide (TiO2) is widely used in engineered particles including engineered nanomaterial (ENM) and pigments, yet its occurrence, concentrations, temporal variability, and fate in natural environmental systems are poorly understood. For three years, we monitored TiO2 concentrations in a rural river basin (Edisto River, < 1% urban land cover) in South Carolina, United States. The total concentrations of Ti, Nb, Al, Fe, Ce, and La in the Edisto River trended higher during spring/summer compared to autumn/winter. Upward trending Ti/Nb ratio in the spring/summer compared to near-background autumn/winter ratios of 255.7 ± 8.9 indicated agricultural preparation and growing-season-related increases in TiO2 engineered particles. In contrast, downward trending of the Ti/Al and Ti/Fe ratios in the spring and summer compared to the near-background autumn/winter ratios of 0.05 indicated greater mobilization of Fe and Al, relative to Ti during spring/summer. Surface-water concentrations of TiO2 engineered particles varied between 0 and 128.7 ± 3.9 µg TiO2 L-1. Increases in TiO2 concentrations over the spring/summer were associated with increases in phosphorus, orthophosphate, nitrate, ammonia, anthropogenic gadolinium, water temperature, suspended sediments, organic carbon, and alkalinity, and with decreases in dissolved oxygen. The association between these contaminants together with the timing of the increases in their concentrations is consistent with diffuse wastewater sources, such as reuse application overspray, biosolids fertilization, leaking sewers, or septic tanks, as the driver of instream concentrations; however, other diffuse sources cannot be ruled out. The findings of this study indicate spatially-distributed (non-point source) releases can result in high concentrations of TiO2 engineered particles, which may pose higher risks to rural stream aquatic ecosystems during the agricultural season. The results illustrate the importance of monitoring seasonal variations in engineered particles concentrations in surface waters for a more representative assessment of ecosystem risk.

Multi-region assessment of chemical mixture exposures and predicted cumulative effects in USA wadeable urban/agriculture-gradient streams.

Chemical-contaminant mixtures are widely reported in large stream reaches in urban/agriculture-developed watersheds, but mixture compositions and aggregate biological effects are less well understood in corresponding smaller headwaters, which comprise most of stream length, riparian connectivity, and spatial biodiversity. During 2014-2017, the U.S. Geological Survey (USGS) measured 389 unique organic analytes (pharmaceutical, pesticide, organic wastewater indicators) in 305 headwater streams within four contiguous United States (US) regions. Potential aquatic biological effects were evaluated for estimated maximum and median exposure conditions using multiple lines of evidence, including occurrence/concentrations of designed-bioactive pesticides and pharmaceuticals and cumulative risk screening based on vertebrate-centric ToxCast™ exposure-response data and on invertebrate and nonvascular plant aquatic life benchmarks. Mixed-contaminant exposures were ubiquitous and varied, with 78% (304) of analytes detected at least once and cumulative maximum concentrations up to more than 156,000 ng/L. Designed bioactives represented 83% of detected analytes. Contaminant summary metrics correlated strong-positive (rho (ρ): 0.569-0.719) to multiple watershed-development metrics, only weak-positive to point-source discharges (ρ: 0.225-353), and moderate- to strong-negative with multiple instream invertebrate metrics (ρ: -0.373 to -0.652). Risk screening indicated common exposures with high probability of vertebrate-centric molecular effects and of acute toxicity to invertebrates, respectively. The results confirm exposures to broad and diverse contaminant mixtures and provide convincing multiple lines of evidence that chemical contaminants contribute substantially to adverse multi-stressor effects in headwater-stream communities.

Reconnaissance of cumulative risk of pesticides and pharmaceuticals in Great Smoky Mountains National Park streams.

The United States (US) National Park Service (NPS) manages protected public lands to preserve biodiversity. Exposure to and effects of bioactive organic contaminants in NPS streams are challenges for resource managers. Recent assessment of pesticides and pharmaceuticals in protected-streams within the urbanized NPS Southeast Region (SER) indicated the importance of fluvial inflows from external sources as drivers of aquatic contaminant-mixture exposures. Great Smoky Mountains National Park (GRSM), lies within SER, has the highest biodiversity and annual visitation of NPS parks, but, in contrast to the previously studied systems, straddles a high-elevation hydrologic divide; this setting limits fluvial-inflows of contaminants but potentially increases visitation-driven contaminant deliveries. We leveraged the unique characteristics of GRSM to test further the importance of fluvial contaminant inflows as drivers of protected-stream exposures and to inform the relative importance of potential additional contaminant transport mechanisms, by comparing the estimated risks of 328 pesticides and pharmaceuticals in water at 16 GRSM stream locations to those estimated previously in SER streams. Extensive mixtures (31 compounds) were only observed in an atypical reach on the boundary of GRSM downstream of a wastewater discharge, while limited mixtures (2-5 compounds) were observed in one stream with elevated visitation pressure (recreational "tube floating"). The insecticide, imidacloprid, used to eradicate hemlock woolly adelgid, was detected in 8 (50%) streams. Infrequent exceedances of a cumulative ToxCast-based, exposure-activity ratio (ΣEAR) 0.001 screening-level of concern suggested limited risk to non-target, aquatic vertebrates, whereas exceedances of a cumulative benchmark-based, invertebrate toxicity quotient (ΣTQ) 0.1 screening level at 8 locations indicated generally high risk to invertebrates. The results are consistent with the importance of fluvial transport from extra-park sources as a driver of bioactive-contaminant mixture exposures in protected streams and illustrate the potential additional risks from visitation-driven and tactical-use-pesticides.

Mixed organic and inorganic tapwater exposures and potential effects in greater Chicago area, USA.

Safe drinking water at the point of use (tapwater, TW) is a public-health priority. TW exposures and potential human-health concerns of 540 organics and 35 inorganics were assessed in 45 Chicago-area United States (US) homes in 2017. No US Environmental Protection Agency (EPA) enforceable Maximum Contaminant Level(s) (MCL) were exceeded in any residential or water treatment plant (WTP) pre-distribution TW sample. Ninety percent (90%) of organic analytes were not detected in treated TW, emphasizing the high quality of the Lake Michigan drinking-water source and the efficacy of the drinking-water treatment and monitoring. Sixteen (16) organics were detected in >25% of TW samples, with about 50 detected at least once. Low-level TW exposures to unregulated disinfection byproducts (DBP) of emerging concern, per/polyfluoroalkyl substances (PFAS), and three pesticides were ubiquitous. Common exceedances of non-enforceable EPA MCL Goal(s) (MCLG) of zero for arsenic [As], lead [Pb], uranium [U], bromodichloromethane, and tribromomethane suggest potential human-health concerns and emphasize the continuing need for improved understanding of cumulative effects of low-concentration mixtures on vulnerable sub-populations. Because DBP dominated TW organics, residential-TW concentrations are potentially predictable with expanded pre-distribution DBP monitoring. However, several TW chemicals, notably Pb and several infrequently detected organic compounds, were not readily explained by pre-distribution samples, illustrating the need for continued broad inorganic/organic TW characterization to support consumer assessment of acceptable risk and point-of-use treatment options.

Multi-region assessment of pharmaceutical exposures and predicted effects in USA wadeable urban-gradient streams.

Human-use pharmaceuticals in urban streams link aquatic-ecosystem health to human health. Pharmaceutical mixtures have been widely reported in larger streams due to historical emphasis on wastewater-treatment plant (WWTP) sources, with limited investigation of pharmaceutical exposures and potential effects in smaller headwater streams. In 2014-2017, the United States Geological Survey measured 111 pharmaceutical compounds in 308 headwater streams (261 urban-gradient sites sampled 3-5 times, 47 putative low-impact sites sampled once) in 4 regions across the US. Simultaneous exposures to multiple pharmaceutical compounds (pharmaceutical mixtures) were observed in 91% of streams (248 urban-gradient, 32 low-impact), with 88 analytes detected across all sites and cumulative maximum concentrations up to 36,142 ng/L per site. Cumulative detections and concentrations correlated to urban land use and presence/absence of permitted WWTP discharges, but pharmaceutical mixtures also were common in the 75% of sampled streams without WWTP. Cumulative exposure-activity ratios (EAR) indicated widespread transient exposures with high probability of molecular effects to vertebrates. Considering the potential individual and interactive effects of the detected pharmaceuticals and the recognized analytical underestimation of the pharmaceutical-contaminant (unassessed parent compounds, metabolites, degradates) space, these results demonstrate a nation-wide environmental concern and the need for watershed-scale mitigation of in-stream pharmaceutical contamination.

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

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

Mixed-chemical exposure and predicted effects potential in wadeable southeastern USA streams.

Complex chemical mixtures have been widely reported in larger streams but relatively little work has been done to characterize them and assess their potential effects in headwater streams. In 2014, the United States Geological Survey (USGS) sampled 54 Piedmont streams over ten weeks and measured 475 unique organic compounds using five analytical methods. Maximum and median exposure conditions were evaluated in relation to watershed characteristics and for potential biological effects using multiple lines of evidence. Results demonstrate that mixed-contaminant exposures are ubiquitous and varied in sampled headwater streams. Approximately 56% (264) of the 475 compounds were detected at least once across all sites. Cumulative maximum concentrations ranged 1,922-162,346ngL-1 per site. Chemical occurrence significantly correlated to urban land use but was not related to presence/absence of wastewater treatment facility discharges. Designed bioactive chemicals represent about 2/3rd of chemicals detected, notably pharmaceuticals and pesticides, qualitative evidence for possible adverse biological effects. Comparative Toxicogenomics Database chemical-gene associations applied to maximum exposure conditions indicate >12,000 and 2,900 potential gene targets were predicted at least once across all sites for fish and invertebrates, respectively. Analysis of cumulative exposure-activity ratios provided additional evidence that, at a minimum, transient exposures with high probability of molecular effects to vertebrates were common. Finally, cumulative detections and concentrations correlated inversely with invertebrate metrics from in-stream surveys. The results demonstrate widespread instream exposure to extensive contaminant mixtures and compelling multiple lines of evidence for adverse effects on aquatic communities.

Reconnaissance of Mixed Organic and Inorganic Chemicals in Private and Public Supply Tapwaters at Selected Residential and Workplace Sites in the United States.

Safe drinking water at the point-of-use (tapwater, TW) is a United States public health priority. Multiple lines of evidence were used to evaluate potential human health concerns of 482 organics and 19 inorganics in TW from 13 (7 public supply, 6 private well self-supply) home and 12 (public supply) workplace locations in 11 states. Only uranium (61.9 µg L-1, private well) exceeded a National Primary Drinking Water Regulation maximum contaminant level (MCL: 30 µg L-1). Lead was detected in 23 samples (MCL goal: zero). Seventy-five organics were detected at least once, with median detections of 5 and 17 compounds in self-supply and public supply samples, respectively (corresponding maxima: 12 and 29). Disinfection byproducts predominated in public supply samples, comprising 21% of all detected and 6 of the 10 most frequently detected. Chemicals designed to be bioactive (26 pesticides, 10 pharmaceuticals) comprised 48% of detected organics. Site-specific cumulative exposure-activity ratios (∑EAR) were calculated for the 36 detected organics with ToxCast data. Because these detections are fractional indicators of a largely uncharacterized contaminant space, ∑EAR in excess of 0.001 and 0.01 in 74 and 26% of public supply samples, respectively, provide an argument for prioritized assessment of cumulative effects to vulnerable populations from trace-level TW exposures.

Nutrient enrichment in wadeable urban streams in the Piedmont Ecoregion of the Southeastern United States.

The U.S. Geological Survey (USGS) Southeastern Stream Quality Assessment (SESQA) collected weekly samples for nitrogen and phosphorus in 76 wadeable streams in the urbanized Piedmont Ecoregion of the Southeastern United States, during April-June 2014. Total nitrogen (TN) concentrations in excess of U.S. Environmental Protection Agency (EPA) guidelines and statistically greater than at reference locations indicated nitrogen-nutrient enrichment in streams draining poultry confined animal feeding operations (CAFO) or urban centers. Nitrate plus nitrite (NO3 + NO2) dominated TN species in urban/CAFO-influenced streams. Streams that drained poultry CAFO and Washington DC had statistically higher NO3 + NO2 concentrations than streams draining Atlanta, Charlotte, Greenville, or Raleigh. In contrast, total phosphorus (TP) concentrations in Atlanta and Washington DC streams statistically were comparable to and lower than, respectively, reference stream concentrations. Over 50% of TP concentrations in Greenville, Charlotte, Raleigh and CAFO-influenced streams exceeded the EPA guideline and reference-location mean concentrations, indicating phosphorus-nutrient enrichment. Urban land use, permitted point sources, and soil infiltration metrics best predicted TN exceedances. Elevated TN and NO3 + NO2 concentrations in urban streams during low flow were consistent with reduced in-stream dilution of point-source or groundwater contributions. Urban land use, permitted point sources, and surface runoff metrics best predicted TP exceedances. Elevated TP in CAFO and urban streams during high flow were consistent with non-point sources and particulate transport.

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

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

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

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

Expanded Target-Chemical Analysis Reveals Extensive Mixed-Organic-Contaminant Exposure in U.S. Streams.

Surface water from 38 streams nationwide was assessed using 14 target-organic methods (719 compounds). Designed-bioactive anthropogenic contaminants (biocides, pharmaceuticals) comprised 57% of 406 organics detected at least once. The 10 most-frequently detected anthropogenic-organics included eight pesticides (desulfinylfipronil, AMPA, chlorpyrifos, dieldrin, metolachlor, atrazine, CIAT, glyphosate) and two pharmaceuticals (caffeine, metformin) with detection frequencies ranging 66-84% of all sites. Detected contaminant concentrations varied from less than 1 ng L-1 to greater than 10 µg L-1, with 77 and 278 having median detected concentrations greater than 100 ng L-1 and 10 ng L-1, respectively. Cumulative detections and concentrations ranged 4-161 compounds (median 70) and 8.5-102 847 ng L-1, respectively, and correlated significantly with wastewater discharge, watershed development, and toxic release inventory metrics. Log10 concentrations of widely monitored HHCB, triclosan, and carbamazepine explained 71-82% of the variability in the total number of compounds detected (linear regression; p-values: < 0.001-0.012), providing a statistical inference tool for unmonitored contaminants. Due to multiple modes of action, high bioactivity, biorecalcitrance, and direct environment application (pesticides), designed-bioactive organics (median 41 per site at µg L-1 cumulative concentrations) in developed watersheds present aquatic health concerns, given their acknowledged potential for sublethal effects to sensitive species and lifecycle stages at low ng L-1.

Pre/post-closure assessment of groundwater pharmaceutical fate in a wastewater-facility-impacted stream reach.

Pharmaceutical contamination of contiguous groundwater is a substantial concern in wastewater-impacted streams, due to ubiquity in effluent, high aqueous mobility, designed bioactivity, and to effluent-driven hydraulic gradients. Wastewater treatment facility (WWTF) closures are rare environmental remediation events; offering unique insights into contaminant persistence, long-term wastewater impacts, and ecosystem recovery processes. The USGS conducted a combined pre/post-closure groundwater assessment adjacent to an effluent-impacted reach of Fourmile Creek, Ankeny, Iowa, USA. Higher surface-water concentrations, consistent surface-water to groundwater concentration gradients, and sustained groundwater detections tens of meters from the stream bank demonstrated the importance of WWTF effluent as the source of groundwater pharmaceuticals as well as the persistence of these contaminants under effluent-driven, pre-closure conditions. The number of analytes (110 total) detected in surface water decreased from 69 prior to closure down to 8 in the first post-closure sampling event approximately 30 d later, with a corresponding 2 order of magnitude decrease in the cumulative concentration of detected analytes. Post-closure cumulative concentrations of detected analytes were approximately 5 times higher in proximal groundwater than in surface water. About 40% of the 21 contaminants detected in a downstream groundwater transect immediately before WWTF closure exhibited rapid attenuation with estimated half-lives on the order of a few days; however, a comparable number exhibited no consistent attenuation during the year-long post-closure assessment. The results demonstrate the potential for effluent-impacted shallow groundwater systems to accumulate pharmaceutical contaminants and serve as long-term residual sources, further increasing the risk of adverse ecological effects in groundwater and the near-stream ecosystem.

Spatial and temporal variation in microcystin occurrence in wadeable streams in the southeastern United States.

Despite historical observations of potential microcystin-producing cyanobacteria (including Leptolyngbya, Phormidium, Pseudoanabaena, and Anabaena species) in 74% of headwater streams in Alabama, Georgia, South Carolina, and North Carolina (USA) from 1993 to 2011, fluvial cyanotoxin occurrence has not been systematically assessed in the southeastern United States. To begin to address this data gap, a spatial reconnaissance of fluvial microcystin concentrations was conducted in 75 wadeable streams in the Piedmont region (southeastern USA) during June 2014. Microcystins were detected using enzyme-linked immunosorbent assay (limit = 0.10 µg/L) in 39% of the streams with mean, median, and maximum detected concentrations of 0.29 µg/L, 0.11 µg/L, and 3.2 µg/L, respectively. Significant (α = 0.05) correlations were observed between June 2014 microcystin concentrations and stream flow, total nitrogen to total phosphorus ratio, and water temperature; but each of these factors explained 38% or less of the variability in fluvial microcystins across the region. Temporal microcystin variability was assessed monthly through October 2014 in 5 of the streams where microcystins were observed in June and in 1 reference location; microcystins were repeatedly detected in all but the reference stream. Although microcystin concentrations in the present study did not exceed World Health Organization recreational guidance thresholds, their widespread occurrence demonstrates the need for further investigation of possible in-stream environmental health effects as well as potential impacts on downstream lakes and reservoirs. Environ Toxicol Chem 2016;35:2281-2287. Published 2016 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.

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

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

Optimizing fish sampling for fish-mercury bioaccumulation factors.

Fish Bioaccumulation Factors (BAFs; ratios of mercury (Hg) in fish (Hgfish) and water (Hgwater)) are used to develop total maximum daily load and water quality criteria for Hg-impaired waters. Both applications require representative Hgfish estimates and, thus, are sensitive to sampling and data-treatment methods. Data collected by fixed protocol from 11 streams in 5 states distributed across the US were used to assess the effects of Hgfish normalization/standardization methods and fish-sample numbers on BAF estimates. Fish length, followed by weight, was most correlated to adult top-predator Hgfish. Site-specific BAFs based on length-normalized and standardized Hgfish estimates demonstrated up to 50% less variability than those based on non-normalized Hgfish. Permutation analysis indicated that length-normalized and standardized Hgfish estimates based on at least 8 trout or 5 bass resulted in mean Hgfish coefficients of variation less than 20%. These results are intended to support regulatory mercury monitoring and load-reduction program improvements.

Optimizing stream water mercury sampling for calculation of fish bioaccumulation factors.

Mercury (Hg) bioaccumulation factors (BAFs) for game fishes are widely employed for monitoring, assessment, and regulatory purposes. Mercury BAFs are calculated as the fish Hg concentration (Hg(fish)) divided by the water Hg concentration (Hg(water)) and, consequently, are sensitive to sampling and analysis artifacts for fish and water. We evaluated the influence of water sample timing, filtration, and mercury species on the modeled relation between game fish and water mercury concentrations across 11 streams and rivers in five states in order to identify optimum Hg(water) sampling approaches. Each model included fish trophic position, to account for a wide range of species collected among sites, and flow-weighted Hg(water) estimates. Models were evaluated for parsimony, using Akaike's Information Criterion. Better models included filtered water methylmercury (FMeHg) or unfiltered water methylmercury (UMeHg), whereas filtered total mercury did not meet parsimony requirements. Models including mean annual FMeHg were superior to those with mean FMeHg calculated over shorter time periods throughout the year. FMeHg models including metrics of high concentrations (80th percentile and above) observed during the year performed better, in general. These higher concentrations occurred most often during the growing season at all sites. Streamflow was significantly related to the probability of achieving higher concentrations during the growing season at six sites, but the direction of influence varied among sites. These findings indicate that streamwater Hg collection can be optimized by evaluating site-specific FMeHg-UMeHg relations, intra-annual temporal variation in their concentrations, and streamflow-Hg dynamics.

Assessing the relative bioavailability of DOC in regional groundwater systems.

It has been hypothesized that the degree to which a hyperbolic relationship exists between concentrations of dissolved organic carbon (DOC) and dissolved oxygen (DO) in groundwater may indicate the relative bioavailability of DOC. This hypothesis was examined for 73 different regional aquifers of the United States using 7745 analyses of groundwater compiled by the National Water Assessment (NAWQA) program of the U.S. Geological Survey. The relative reaction quotient (RRQ), a measure of the curvature of DOC concentrations plotted versus DO concentrations and regressed to a decaying hyperbolic equation, was used to assess the relative bioavailability of DOC. For the basalt aquifer of Oahu, Hawaii, RRQ values were low (0.0013 mM(-2)), reflecting a nearly random relationship between DOC and DO concentrations. In contrast, on the island of Maui, treated sewage effluent injected into a portion of the basalt aquifer resulted in pronounced hyperbolic DOC-DO behavior and a higher RRQ (142 mM(-2)). RRQ values for the 73 aquifers correlated positively with mean concentrations of ammonia, dissolved iron, and manganese, and correlated negatively with mean pH. This indicates that greater RRQ values are associated with greater concentrations of the final products of microbial reduction reactions. RRQ values and DOC concentrations were negatively correlated with the thickness of the unsaturated zone (UNST) and depth to the top of the screened interval. Finally, RRQ values were positively correlated with mean annual precipitation (MAP), and the highest observed RRQ values were associated with aquifers receiving MAP rates ranging between 900 and 1300 mm/year. These results are uniformly consistent with the hypothesis that the hyperbolic behavior of DOC-DO plots, as quantified by the RRQ metric, can be an indicator of relative DOC bioavailability in groundwater systems.

Intra- and inter-basin mercury comparisons: Importance of basin scale and time-weighted methylmercury estimates.

To assess inter-comparability of fluvial mercury (Hg) observations at substantially different scales, Hg concentrations, yields, and bivariate-relations were evaluated at nested-basin locations in the Edisto River, South Carolina and Hudson River, New York. Differences between scales were observed for filtered methylmercury (FMeHg) in the Edisto (attributed to wetland coverage differences) but not in the Hudson. Total mercury (THg) concentrations and bivariate-relationships did not vary substantially with scale in either basin. Combining results of this and a previously published multi-basin study, fish Hg correlated strongly with sampled water FMeHg concentration (ρ = 0.78; p = 0.003) and annual FMeHg basin yield (ρ = 0.66; p = 0.026). Improved correlation (ρ = 0.88; p < 0.0001) was achieved with time-weighted mean annual FMeHg concentrations estimated from basin-specific LOADEST models and daily streamflow. Results suggest reasonable scalability and inter-comparability for different basin sizes if wetland area or related MeHg-source-area metrics are considered.

Influence of dietary carbon on mercury bioaccumulation in streams of the Adirondack Mountains of New York and the Coastal Plain of South Carolina, USA.

We studied lower food webs in streams of two mercury-sensitive regions to determine whether variations in consumer foraging strategy and resultant dietary carbon signatures accounted for observed within-site and among-site variations in consumer mercury concentration. We collected macroinvertebrates (primary consumers and predators) and selected forage fishes from three sites in the Adirondack Mountains of New York, and three sites in the Coastal Plain of South Carolina, for analysis of mercury (Hg) and stable isotopes of carbon (δ(13)C) and nitrogen (δ(15)N). Among primary consumers, scrapers and filterers had higher MeHg and more depleted δ(13)C than shredders from the same site. Variation in δ(13)C accounted for up to 34 % of within-site variation in MeHg among primary consumers, beyond that explained by δ(15)N, an indicator of trophic position. Consumer δ(13)C accounted for 10 % of the variation in Hg among predatory macroinvertebrates and forage fishes across these six sites, after accounting for environmental aqueous methylmercury (MeHg, 5 % of variation) and base-N adjusted consumer trophic position (Δδ(15)N, 22 % of variation). The δ(13)C spatial pattern within consumer taxa groups corresponded to differences in benthic habitat shading among sites. Consumers from relatively more-shaded sites had more enriched δ(13)C that was more similar to typical detrital δ(13)C, while those from the relatively more-open sites had more depleted δ(13)C. Although we could not clearly attribute these differences strictly to differences in assimilation of carbon from terrestrial or in-channel sources, greater potential for benthic primary production at more open sites might play a role. We found significant variation among consumers within and among sites in carbon source; this may be related to within-site differences in diet and foraging habitat, and to among-site differences in environmental conditions that influence primary production. These observations suggest that different foraging strategies and habitats influence MeHg bioaccumulation in streams, even at relatively small spatial scales. Such influence must be considered when selecting lower trophic level consumers as sentinels of MeHg bioaccumulation for comparison within and among sites.