Celeste A. Journey

Spatial and Seasonal Variability of Dissolved Methylmercury in Two Stream Basins in the Eastern United States

We assessed methylmercury (MeHg) concentrations across multiple ecological scales in the Edisto (South Carolina) and Upper Hudson (New York) River basins. Out-of-channel wetland/floodplain environments were primary sources of filtered MeHg (F-MeHg) to the stream habitat in both systems. Shallow, open-water areas in both basins exhibited low F-MeHg concentrations and decreasing F-MeHg mass flux. Downstream increases in out-of-channel wetlands/floodplains and the absence of impoundments result in high MeHg throughout the Edisto. Despite substantial wetlands coverage and elevated F-MeHg concentrations at the headwater margins, numerous impoundments on primary stream channels favor spatial variability and lower F-MeHg concentrations in the Upper Hudson. The results indicated that, even in geographically, climatically, and ecologically diverse streams, production in wetland/floodplain areas, hydrologic transport to the stream aquatic environment, and conservative/nonconservative attenuation processes in open water areas are fundamental controls on dissolved MeHg concentrations and, by extension, MeHg availability for potential biotic uptake.

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.

Flood hydrology and methylmercury availability in coastal plain rivers.

Mercury (Hg) burdens in top-predator fish differ substantially between adjacent South Carolina Coastal Plain river basins with similar wetlands coverage. In the Congaree River, floodwaters frequently originate in the Blue Ridge and Piedmont regions, where wetlands coverage and surface water dissolved methylmercury (MeHg) concentrations are low. Piedmont-driven flood events can lead to downward hydraulic gradients in the Coastal Plain riparian wetland margins, inhibiting MeHg transport from wetland sediments, and decreasing MeHg availability in the Congaree River habitat. In the adjacent Edisto River basin, floodwaters originate only within Coastal Plain sediments, maintaining upward hydraulic gradients even during flood events, promoting MeHg transport to the water column, and enhancing MeHg availability in the Edisto River habitat. These results indicate that flood hydrodynamics contribute to the variability in Hg vulnerability between Coastal Plain rivers and that comprehensive regional assessment of the relationship between flood hydrodynamics and Hg risk in Coastal Plain streams is warranted.

Shallow groundwater mercury supply in a Coastal Plain stream.

Fluvial methylmercury (MeHg) is attributed to methylation in up-gradient wetland areas. This hypothesis depends on efficient wetland-to-stream hydraulic transport under nonflood and flood conditions. Fluxes of water and dissolved (filtered) mercury (Hg) species (FMeHg and total Hg (FTHg)) were quantified in April and July of 2009 in a reach at McTier Creek, South Carolina to determine the relative importance of tributary surface water and shallow groundwater Hg transport from wetland/floodplain areas to the stream under nonflood conditions. The reach represented less than 6% of upstream main-channel distance and 2% of upstream basin area. Surface-water discharge increased within the reach by approximately 10%. Mean FMeHg and FTHg fluxes increased within the reach by 23–27% and 9–15%, respectively. Mass balances indicated that, under nonflood conditions, the primary supply of water, FMeHg, and FTHg within the reach (excluding upstream surface water influx) was groundwater discharge, rather than tributary transport from wetlands, in-stream MeHg production, or atmospheric Hg deposition. These results illustrate the importance of riparian wetland/floodplain areas as sources of fluvial MeHg and of groundwater Hg transport as a fundamental control on Hg supply to Coastal Plain streams.

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 Akaikes 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.

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.

Environmental Factors that Influence Cyanobacteria and Geosmin Occurrence in Reservoirs

Phytoplankton are small to microscopic, free-floating algae that inhabit the open water of freshwater, estuarine, and saltwater systems. In freshwater lake and reservoirs systems, which are the focus of this chapter, phytoplankton communities commonly consist of assemblages of the major taxonomic groups, including green algae, diatoms, dinoflagellates, and cyano‐ bacteria. Cyanobacteria are a diverse group of single-celled organisms that can exist in a wide range of environments, not just open water, because of their adaptability [1-3]. It is the adaptability of cyanobacteria that enables this group to dominate the phytoplankton com‐ munity and even form nuisance or harmful blooms under certain environmental conditions [3-6]. In fact, cyanobacteria are predicted to adapt favorably to future climate change in freshwater systems compared to other phytoplankton groups because of their tolerance to rising temperatures, enhanced vertical thermal stratification of aquatic ecosystems, and alterations in seasonal and interannual weather patterns [7, 8]. Understanding those environ‐ mental conditions that favor cyanobacterial dominance and bloom formation has been the focus of research throughout the world because of the concomitant production and release of nuisance and toxic cyanobacterial-derived compounds [4-6, 7-10]. However, the complex interaction among the physical, chemical, and biological processes within lakes, reservoirs, and large rivers often makes it difficult to identify primary environmental factors that cause the production and release of these cyanobacterial by-products [9].

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 17β-estradiol) and synthetic (17α-ethinylestradiol) estrogen was significant at all sites. Bed sediment microbial communities in Rocky Mountain National Park also effectively degraded the xenoestrogens bisphenol-A and 4-nonylphenol. The same sediment samples exhibited little potential for aerobic biodegradation of triclocarban, however, illustrating the need to assess a wider range of contaminant compounds. The present studys 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.

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.

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.