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Mercury in fishes from 21 national parks in the Western United States: inter- and intra-park variation in concentrations and ecological risk

Mercury (Hg) is a global contaminant and human activities have increased atmospheric Hg concentrations 3- to 5-fold during the past 150 years. This increased release into the atmosphere has resulted in elevated loadings to aquatic habitats where biogeochemical processes promote the microbial conversion of inorganic Hg to methylmercury, the bioavailable form of Hg. The physicochemical properties of Hg and its complex environmental cycle have resulted in some of the most remote and protected areas of the world becoming contaminated with Hg concentrations that threaten ecosystem and human health. The national park network in the United States is comprised of some of the most pristine and sensitive wilderness in North America. There is concern that via global distribution, Hg contamination could threaten the ecological integrity of aquatic communities in the parks and the wildlife that depends on them. In this study, we examined Hg concentrations in non-migratory freshwater fish in 86 sites across 21 national parks in the Western United States. We report Hg concentrations of more than 1,400 fish collected in waters extending over a 4,000 kilometer distance, from Alaska to the arid Southwest. Across all parks, sites, and species, fish total Hg (THg) concentrations ranged from 9.9 to 1,109 nanograms per gram wet weight (ng/g ww) with a mean of 77.7 ng/g ww. We found substantial variation in fish THg concentrations among and within parks, suggesting that patterns of Hg risk are driven by processes occurring at a combination of scales. Additionally, variation (up to 20-fold) in site-specific fish THg concentrations within individual parks suggests that more intensive sampling in some parks will be required to effectively characterize Hg contamination in western national parks. Across all fish sampled, only 5 percent had THg concentrations exceeding a benchmark (200 ng/g ww) associated with toxic responses within the fish themselves. However, Hg concentrations in 35 percent of fish sampled were above a benchmark for risk to highly sensitive avian consumers (90 ng/g ww), and THg concentrations in 68 percent of fish sampled were above exposure levels recommended by the Great Lakes Advisory Group (50 ng/g ww) for unlimited consumption by humans. Of the fish assessed for risk to human consumers (that is, species that are large enough to be consumed by recreational or subsistence anglers), only one individual fish from Yosemite National Park had a muscle Hg concentration exceeding the benchmark (950 ng/g ww) at which no human consumption is advised. Zion, Capital Reef, Wrangell-St. Elias, and Lake Clark National Parks all contained sites in which most fish exceeded benchmarks for the protection of human and wildlife health. This finding is particularly concerning in Zion and Capitol Reef National Parks because the fish from these parks were speckled dace, a small, invertebrate-feeding species, yet their Hg concentrations were as high or higher than those in the largest, long-lived predatory species, such as lake trout. Future targeted research and monitoring across park habitats would help identify patterns of Hg distribution across the landscape and facilitate management decisions aimed at reducing the ecological risk posed by Hg contamination in sensitive ecosystems protected by the National Park Service.

Alaska;Arizona;California;Colorado;Idaho;Montana;N↗

USGS Tampa Bay Pilot Study

Many of the nation's estuaries have been environmentally stressed since the turn of the 20th century and will continue to be impacted in the future. Tampa Bay, one the Gulf of Mexico's largest estuaries, exemplifies the threats that our estuaries face (EPA Report 2001, Tampa Bay Estuary Program-Comprehensive Conservation and Management Plan (TBEP-CCMP)). More than 2 million people live in the Tampa Bay watershed, and the population constitutes to grow. Demand for freshwater resources, conversion of undeveloped areas to resident and industrial uses, increases in storm-water runoff, and increased air pollution from urban and industrial sources are some of the known human activities that impact Tampa Bay. Beginning on 2001, additional anthropogenic modifications began in Tampa Bat including construction of an underwater gas pipeline and a desalinization plant, expansion of existing ports, and increased freshwater withdrawal from three major tributaries to the bay. In January of 2001, the Tampa Bay Estuary Program (TBEP) and its partners identifies a critical need for participation from the U.S. Geological Survey (USGS) in providing multidisciplinary expertise and a regional-scale, integrated science approach to address complex scientific research issue and critical scientific information gaps that are necessary for continued restoration and preservation of Tampa Bay. Tampa Bay stakeholders identified several critical science gaps for which USGS expertise was needed (Yates et al. 2001). These critical science gaps fall under four topical categories (or system components): 1) water and sediment quality, 2) hydrodynamics, 3) geology and geomorphology, and 4) ecosystem structure and function. Scientists and resource managers participating in Tampa Bay studies recognize that it is no longer sufficient to simply examine each of these estuarine system components individually, Rather, the interrelation among system components must be understood to develop conceptual and predictive modeling tools for effective ecosystem adaptive management. As a multidisciplinary organization, the USGS possesses the capability of developing and coordinating an integrated science strategy for estuarine research founded on partnerships and collaborative efforts, multidisciplinary teams of scientists, and integrated field work, data analysis and interpretation, and product development. The primary role of the USGS in Tamps Bay research was defined with our partners based upon this capability to address estuarine issues using an integrated science approach with a regional perspective and within a national context to complement the numerous ongoing scien efforts by state and local agencies that address local issues within Tamp Bay. Six primary components of the USGS Tamp Bay Study address critical gaps within each of the the four estuarine system components and focus on: 1.) Examining how natural and man-made physical changes affect ecosystem health through mapping and modeling. 2.) Identifying sources and quality of groundwater, surface water, and sediment, 3.) Identifying sources and quality of groundwater, surface water, and sediment, 4.) Assessing the natural and man-made changes affecting wetland health and restoration, 5.) Identifying and measuring the impact of urbanization on seafloor habitats, Providing a web-based digital information management system of information for scientists and the public, including a system that supports the work of those officials who must make decisions that affect the state of the bay. The Tampa Bay Study is in its sixth year and will continue through September 2007. This paper presents a non-inclusive summary of key findings associated with the six primary project components listed above. Component 4 (above) is described in detail in the following chapter 13. More information on the Tampa Bay Study is available from our on-line digital information system for the Tampa Bay Study at http://gulfsci.usgs.gov.

Florida↗

Escherichia coli at Ohio bathing beaches—Distribution, sources, wastewater indicators, and predictive modeling

Results of studies during the recreational seasons of 2000 and 2001 strengthen the science that supports monitoring of our Nation's beaches. Water and sediment samples were collected and analyzed for concentrations of Escherichia coli ( E. coli ). Ancillary water-quality and environmental data were collected or compiled to determine their relation to E. coli concentrations. Data were collected at three Lake Erie urban beaches (Edgewater, Villa Angela, and Huntington), two Lake Erie beaches in a less populated area (Mentor Headlands and Fairport Harbor), and one inland-lake beach (Mosquito Lake). The distribution of E. coli in water and sediments within the bathing area, outside the bathing area, and near the swash zone was investigated at the three Lake Erie urban beaches and at Mosquito Lake. (The swash zone is the zone that is alternately covered and exposed by waves.) Lake-bottom sediments from outside the bathing area were not significant deposition areas for E. coli . In contrast, interstitial water and subsurface sediments from near the swash zone were enriched with E. coli . For example, E. coli concentrations were as high as 100,000 colonies per 100 milliliters in some interstitial waters. Although there are no standards for E. coli in swash-zone materials, the high concentrations found at some locations warrant concern for public health. Studies were done at Mosquito Lake to identify sources of fecal contamination to the lake and bathing beach. Escherichia coli concentrations decreased with distance from a suspected source of fecal contamination that is north of the beach but increased at the bathing beach. This evidence indicated that elevated E. coli concentrations at the bathing beach are of local origin rather than from transport of bacteria from sites to the north. Samples collected from the three Lake Erie urban beaches and Mosquito Lake were analyzed to determine whether wastewater indicators could be used as surrogates for E. coli at bathing beaches. None of the concentrations of wastewater indicators of fecal contamination, including 3b-coprostanol and cholesterol, were significantly correlated (a=0.05) to concentrations of E. coli . Concentrations of the two compounds that were significantly correlated to E. coli were components of coal tar and asphalt, which are not necessarily indicative of fecal contamination. Data were collected to build on an earlier 1997 study to develop and test multiple-linear-regression models to predict E. coli concentrations using water-quality and environmental variables as explanatory variables. The probability of exceeding the single-sample bathing-water standard for E. coli (235 colonies per 100 milliliters) was used as the model output variable. Threshold probabilities for each model were established. Computed probabilities that are less than a threshold probability indicate that bacterial water quality is most likely acceptable. Computed probabilities equal to or above the threshold probability indicate that the water quality is most likely not acceptable and that a water-quality advisory may be needed. Models were developed at each beach, whenever possible, using combinations of 1997, 2000, and (or) 2001 data. The models developed and tested in this study were shown to be beach specific; that is, different explanatory variables were used to predict the probability of exceeding the standard at each beach. At Mentor Headlands and Fairport Harbor, models were not developed because water quality was generally good. At the three Lake Erie urban beaches, models were developed with variable lists that included the number of birds on the beach at the time of sampling, lake-current direction, wave height, turbidity, streamflow of a nearby river, and rainfall. The models for Huntington explained a larger percentage of the variability in E. coli concentrations than the models for Edgewater and Villa Angela. At Mosquito Lake, a model based on 2000 and 2001 data contained the explanatory variables rainfall, number of dry days preceding a rainfall, date, wind direction, wind speed, and turbidity. Additional research could include testing the threshold probabilities assigned for these models in subsequent years and comparing the models’ ability to predict recreational water quality to results from the current method—using antecedent E. coli concentrations. Each year the model is tested, new data can be added and model variables can be recalculated to determine whether the predictive ability improves with additional data.

Ohio↗

Land application of biosolid, livestock, and drilling wastes to US farmland: A potential pathway for the redistribution of contaminants in the environment

In the United States (U.S.), waste byproducts generated from the treatment of municipal waste (biosolids), production of livestock (livestock waste), and drilling of oil and gas wells (drilling waste) are commonly applied to agricultural lands. Although this can be a cost-effective reuse/disposal practice, there is limited research on the potential for contaminant exposures and effects on ecosystems, wildlife, and human health from such land applications. In this study, we conducted extensive chemical, microbial, and toxicity analyses of biosolid, livestock, and drilling wastes just prior to land application on agricultural lands at 34 sites across the U.S. Twenty-two analytical methods were used to determine potential contaminant exposures profiles for 452 organic and 114 inorganic chemicals, nine microbial groups, estrogenicity, and cytotoxicity. Analytical results document unique and substantial chemical, microbial, and toxicity profiles for these land-applied wastes. Of the three waste byproducts, biosolids contained the greatest concentrations of household chemicals, pesticides, pharmaceuticals, per-/polyfluoroalkyl substances, calcium, and phosphorus. Livestock waste contained the greatest concentrations of total and leachable dissolved organic carbon, biogenic hormones, mycotoxins, plant estrogens, total inorganic nitrogen, and potassium. Drilling waste contained the greatest concentrations of BTEX compounds (benzene, toluene, ethylbenzene, and xylenes), polycyclic aromatic hydrocarbons, rare-earth elements, barium, strontium, and uranium–thorium series radioisotopes. Biosolid and livestock wastes had greater culturable heterotrophic bacteria, halophilic bacteria, Escherichia coli ( E. coli ), enterococci, and staphylococci concentrations, and greater microbial diversity than drilling waste. Bioassay analyses indicated that exposure to contaminants in livestock wastes and biosolids could result in estrogenic effects, whereas exposure to contaminants in drilling waste could result in cytotoxic effects. Our study documents that current reuse/disposal practices for biosolid, livestock, and drilling wastes on agricultural lands could provide a potential pathway for the redistribution of unique and complex contaminant mixtures into the environment that have bioactive, endocrine disrupting, and carcinogenic characteristics. Results of this study provide a snapshot of chemical compositions and concentrations that can be used to inform the development of best-management practices to help maximize beneficial reuse of these wastes and minimize risk to the environment and human health.

Environmental Science: Processes & Impacts↗

Exploring the exceptional performance of a deep learning stream temperature model and the value of streamflow data

Stream water temperature ( T s ) is a variable of critical importance for aquatic ecosystem health. T s is strongly affected by groundwater-surface water interactions which can be learned from streamflow records, but previously such information was challenging to effectively absorb with process-based models due to parameter equifinality. Based on the long short-term memory (LSTM) deep learning architecture, we developed a basin-centric lumped daily mean T s model, which was trained over 118 data-rich basins with no major dams in the conterminous United States, and showed strong results. At a national scale, we obtained a median root-mean-square error of 0.69°C, Nash–Sutcliffe model efficiency coefficient of 0.985, and correlation of 0.994, which are marked improvements over previous values reported in literature. The addition of streamflow observations as a model input strongly elevated the performance of this model. In the absence of measured streamflow, we showed that a two-stage model could be used, where simulated streamflow from a pre-trained LSTM model ( Q sim ) still benefited the T s model even though no new information was brought directly into the inputs of the T s model. The model indirectly used information learned from streamflow observations provided during the training of Q sim , potentially to improve internal representation of physically meaningful variables. Our results indicate that strong relationships exist between basin-averaged forcing variables, catchment attributes, and T s that can be simulated by a single model trained by data on the continental scale.

Environmental Research Letters↗

Occurrence of cyanazine compounds in groundwater: Degradates more prevalent than the parent compound

A recently developed analytical method using liquid chromatography/mass spectrometry was used to investigate the occurrence of cyanazine and its degradates cyanazine acid (CAC), cyanazine amide (CAM), deethylcyanazine (DEC), and deethylcyanazine acid (DCAC) in groundwater. This research represents some of the earliest data on the occurrence of cyanazine degradates in groundwater. Although cyanazine was infrequently detected in the 64 wells across Iowa sampled in 1999, cyanazine degradates were commonly found during this study. The most frequently detected cyanazine compound was DCAC (32.8%) followed by CAC (29.7%), CAM (17.2%), DEC (3.1%), and cyanazine (3.1%). The frequency of detection for cyanazine or one or more of its degradates (CYTOT) was more than 12-fold over that of cyanazine alone (39.1% for CYTOT versus 3.1% for cyanazine). Of the total measured concentration of cyanazine, only 0.2% was derived from its parent compound - with DCAC (74.1%) and CAC (18.4%) comprising 92.5% of this total. Thus, although DCAC and CAC had similar frequencies of detection, DCAC was generally present in higher concentrations. No concentrations of cyanazine compounds for this study exceeded water-quality criteria for the protection of human health. Only cyanazine, however, has such a criteria established. Nevertheless, because these cyanazine degradates are still chlorinated, they may have similar toxicity as their parent compound - similar to what has been found with the chlorinated degradates of atrazine. Thus, the results of this study documented that data on the degradates for cyanazine are critical for understanding its fate and transport in the hydrologic system. Furthermore, the prevalence of the chlorinated degradates of cyanazine found in groundwater suggests that to accurately determine the overall effect on human health and the environment from cyanazine its degradates should also be considered. In addition, because CYTOT was found in 57.6% of the samples collected from alluvial aquifers, about 2-5 times more frequently than the other major aquifer types (glacial drift, bedrock/karst, bedrock/nonkarst) under investigation, this finding has long-term implications for the occurrence of CYTOT in streams. It is anticipated that low-level concentrations of CYTOT will continue to be detected in streams for years after the use of cyanazine has terminated (scheduled for the year 2000 in the United States), primarily through its movement from groundwater into streams during base-flow conditions.

Iowa↗

Perspectives on equitable co-production workshop report

The co-production of knowledge is increasingly recognized as an approach to conducting research intended to achieve a societal impact. In this study, we used a broad definition of co-production, defining it as “a process that brings together diverse groups to iteratively create new knowledge and practices (1).” However, co-production has been defined and conceptualized in a variety of ways (2,3), across multiple domains, including public administration, conservation, health, education, and climate change. Theoretical definitions have been introduced by scholars like Jasanoff (4) and Ostrom (5), but definitions can also be grounded in practice (6). For example, unique definitions of co-production have been advanced for work with Arctic Indigenous Peoples (7), in the context of resource management (8), and for a specific program (9). Other similar processes of engagement, such as community-based participatory research (10), action research (11), civic science (12), community science (13), and post-normal science (14) may have overlap with the concept of co-production and have been used to describe similar processes of collaboration. These distinctions and varying definitions have been discussed extensively elsewhere (see Mach et al. 2020, Wyborn et al. 2019). In the context of co-production, power plays a crucial role in shaping interactions and outcomes. Some scholars and practitioners explicitly consider power dynamics as a central element in their definitions of co-production, recognizing how power imbalances can affect participation, decision-making, and the distribution of benefits. Others, however, might not emphasize power as prominently, focusing more on the collaborative aspects without explicitly addressing the underlying power structures. This leads to divergent objectives and priorities among projects claiming to be co-produced (2,3, 6). Chambers and colleagues (2) discussed how co-production projects in the context of sustainability usually emphasize one or more of six different goals, including: researching solutions, empowering voices, brokering power, reframing power, navigating differences, and reframing agency. Because power dynamics are inherent in co-production (15), equity dimensions should be considered in these definitions and conceptualizations. Yet, in the context of government or academically led climate change research and programs, equity is a relatively new focus, even among programs that have been engaging a co-production approach for decades (9). Alternatively, in some recent work the concept of equity in co-production is explicit, but it has only been considered in a limited context (7). Here, we present a discussion about co-production that is informed by research, practice, and community perspectives across partnerships from a range of regions and topics. We are specifically interested in how different actors in these projects think about equity and work towards more equitable approaches in the context of their co-production work. This understanding is needed, as the federal government has increasingly focused on co-production approaches in the design of their programs and funding calls, and most recently the Biden administration has called on federal agencies to more intentionally center equity for underserved groups of people in their work (16). Furthermore, with the Biden administration’s focus on environmental and climate justice, the opportunity for researchers and their societal partners to engage in co-production is expanding. Numerous programs within federal agencies have embraced a co-production approach, such as the National Oceanic and Atmospheric Administration (NOAA) Climate Adaptation Partnerships (CAP; formerly called the Regional Integrated Sciences and Assessments or RISA program) (9,17), Department of the Interior (DOI) Climate Adaptation Science Centers (CASCs)(18), and the US Department of Agriculture (USDA) Climate Hubs. However, the actual implementation of co-production processes varies significantly (1,19), with multiple implications for the design of equitable partnerships. Researchers, their partners, and funders have frequently cited many tensions and challenges in the successful implementation of co-production, including higher resource demands and few systemic structures for support (20). Practically implementing co-production, especially with people who have been underrepresented in or historically excluded from research activities, must consider fairness and the accessibility of co-production processes. While co-production is often cited as important for environmental governance, issues like power and equity are infrequently addressed (15). To explore this topic, we identified and studied three projects that centered on equity in co-production from three federal climate programs (CASC, CAP, USDA Climate Hubs) in three different regions of the U.S. (Alaska, Northeast, Southeast). We aimed to identify consensus or divergence in perspectives related to equitable co-production processes to elevate effective practices and link co-production research and practice. Findings from interviews and a survey (explained further in Akerlof et al., 2023) informed a twoday hybrid workshop involving participants from the three case studies, as well as individuals representing research, governmental, non-governmental, and community organizations across the United States. Participants also included scholars of co-production, program coordinators, and people who participated in co-production projects on behalf of their communities. Several boundary spanners, those practitioners who work at the intersection of the production and use of science (21,22), also attended the workshop. The goals of the workshop were to discuss and build on what was learned from the three case studies, discuss the three distinct perspectives on equitable co-production that emerged from the pre-workshop research, and draft a framework for equitable co-production processes. During the workshop, participants considered the three perspectives on equitable co-production, defining equitable co-production for each and discussing the practical implications of each, including barriers and priorities for overcoming them. We aimed to address the question: How can federal climate programs support equitable co-production processes?

Report↗

Carbon and ecohydrological priorities in managing woody encroachment: UAV perspective 63 years after a control treatment

Woody encroachment, including both woody species expansion and density increase, is a globally observed phenomenon that deteriorates arid and semi-arid rangeland health, biodiversity, and ecosystem services. Mechanical and chemical control treatments are commonly performed to reduce woody cover and restore ecohydrologic function. While the immediate impacts of woody control treatments are well documented in short-term studies, treatment impacts at decadal scales are not commonly studied. Using a controlled herbicide treatment from 1954 in the Sierra Ancha Experimental Forest in central Arizona, USA, we quantify woody encroachment and associated aboveground carbon accumulation in treated and untreated watersheds. Woody encroachment and aboveground carbon are estimated using high resolution multispectral images and photogrammetric data from a fixed-wing unmanned aerial vehicle (UAV). We then combine the contemporary UAV image-derived estimates with historical records from immediately before and after the treatment to consider long-term trends in woody vegetation cover, aboveground carbon, water yield, and sedimentation. Our results indicate that the treatment has had a lasting impact. More than six decades later, woody cover in two treated watersheds are still significantly lower compared to two control watersheds, even though woody cover increased in all four drainages. Aboveground woody carbon in the treated watersheds is approximately one half that accumulated in the control watersheds. The historical records indicate that herbicide treatment also increased water yield and reduced annual sedimentation. Given the sustained reduction in woody cover and aboveground woody biomass in treated watersheds, we infer that the herbicide treatment has had similarly long lasting impacts on ecohydrological function. Land managers can consider legacy impacts from control treatments to better balance carbon and ecohydrological consequences of woody encroachment and treatment activities.

Environmental Research Letters↗

Grassy–herbaceous land moderates regional climate effects on honey bee colonies in the Northcentral US

The lack of seasonally sustained floral resources (i.e. pollen and nectar) is considered a primary global threat to pollinator health. However, the ability to predict the abundance of flowering resources for pollinators based upon climate, weather, and land cover is difficult due to insufficient monitoring over adequate spatial and temporal scales. Here we use spatiotemporally distributed honey bee hive scales that continuously measure hive weights as a standardized method to assess nectar intake. We analyze late summer colony weight gain as the response variable in a random forest regression model to determine the importance of climate, weather, and land cover on honey bee colony productivity. Our random forest model predicted resource acquisition by honey bee colonies with 71% accuracy, highlighting the detrimental effects of warm, wet regions in the Northcentral United States on nectar intake, as well as the detrimental effect of years with high growing degree day accumulation. Our model also predicted that grassy–herbaceous natural land had a positive effect on the summer nectar flow and that large areas of natural grassy–herbaceous land around apiaries can moderate the detrimental effects of warm, wet climates. These patterns characterize multi-scale ecological processes that constrain the quantity and quality of pollinator nutritional resources. That is, broad climate conditions constrain regional floral communities, while land use and weather act to further modify the quantity and quality of pollinator nutritional resources. Observing such broad-scale trends demonstrates the potential for utilizing hive scales to monitor the effects of climate change on landscape-level floral resources for pollinators. The interaction of climate and land use also present an opportunity to manage for climate-resilient landscapes that support pollinators through abundant floral resources under climate change.

Michigan, Minnesota, North Dakota, Ohio, Pennsylva↗

Environmental fate and effects of the lampricide bayluscide: a review

Bayluscide is an additive to TFM that increases the effectiveness of TFM as a lampricide. A review of the literature was undertaken to determine the environmental fate and effects of Bayluscide. Niclosamide (2', 5-dichloro-4'-nitrosalicylanilide), the active ingredient of Bayluscide, degrades rapidly in natural water and sediment systems, however, the rate of degradation is very slow in autoclaved samples. This difference suggests that degradation under laboratory conditions is dependent on microbial activity and hydrolysis plays a minor role in degradation of niclosamide. The major degradation product of niclosamide has been reported to be aminoniclosamide (2',5-dichloro-4'-aminosalicylanilide), which represented more than 50% of the residues extractable from sediments. Significantly more of the chemical is adsorbed to sediments with higher organic content and at lower pH's. The mobility of niclosamide in soil can be characterized as slight to medium; the estimated leaching distance would range from 0 to > 25 cm depending on the soil type and pH. The active ingredient of Bayluscide (niclosamide) is decomposed by ultra-violet light depending on the intensity and duration of the exposure. The uptake of residues by most invertebrates exposed to super(14)C-niclosamide is fairly rapid and equilibrium is reached within 24 h. About 90% of the accumulated residues were lost within 48 h after the organisms were transferred to clean flowing water. As with invertebrates, fish rapidly accumulate and eliminate residues of niclosamide. Three distinct residues were isolated from the extracts of edible fillet tissue; parent niclosamide, the glucuronide conjugate of niclosamide, and the sulfate ester of niclosamide. Aquatic plants and agricultural crops do not appear to be adversely affected at concentrations of Bayluscide used for lamprey or snail control. Mayflies (Hexagenia sp.). tend to be susceptible to TFM, but are relatively resistant to the effects of exposure to Bayluscide. Bayluscide was originally developed as a molluscicide to eliminate snails. Therefore, it is not surprising that mollusks are extremely sensitive to Bayluscide. Oral, dermal, and ocular administration of Bayluscide to mammals resulted in no clinical signs of systemic toxicity. Tests of the chronic effects of Bayluscide indicated that it is not mutagenic or carcinogenic. Bayluscide is not persistent in the environment; it breaks down in natural water and sediment systems through hydrolysis, photolysis, and microbial degradation. Given the limited use and tight control maintained by the U.S. Fish and Wildlife Service during applications of lampricides, Bayluscide presents minimal risk to human health and safety of the environment.

Journal of Great Lakes Research↗

Microbial source tracking (MST) in Chattahoochee River National Recreation Area: Seasonal and precipitation trends in MST marker concentrations, and associations with E. coli levels, pathogenic marker presence, and land use

Escherichia coli levels in recreational waters are often used to predict when fecal-associated pathogen levels are a human health risk. The reach of the Chattahoochee River that flows through the Chattahoochee River National Recreation Area (CRNRA), located in the Atlanta-metropolitan area, is a popular recreation area that frequently exceeds the U.S. Environmental Protection Agency beach action value (BAV) for E. coli . A BacteriALERT program has been implemented to provide real-time E. coli estimates in the reach and notify the public of potentially harmful levels of fecal-associated pathogens as indicated by surrogate models based on real-time turbidity measurements from continuous water quality monitoring stations. However, E. coli does not provide information about the sources of fecal contamination and its accuracy as a human health indicator is questionable when sources of contamination are non-human. The objectives of our study were to investigate, within the Park and surrounding watersheds, seasonal and precipitation-related patterns in microbial source tracking marker concentrations of possible sources (human, dog, and ruminant), assess correlations between source contamination levels and culturable E. coli levels, determine which sources best explained model-based E. coli estimates above the BAV and detection of esp2 (a marker for the esp gene associated with pathogenic strains of Enterococcus faecium and Enterococcus faecalis) , and investigate associations between source contamination levels and land use features. Three BacteriALERT sites on the Chattahoochee River were sampled six times per season in the winter and summer from December 2015 through September 2017, and 11 additional stream sites (synoptic sites) from the CRNRA watershed were sampled once per season. Samples were screened with microbial source tracking (MST) quantitative PCR (qPCR) markers for humans (HF183 Taqman), dogs (DogBact), and ruminants (Rum2Bac), the esp2 qPCR marker, and culturable E. coli. At the BacteriALERT sites, HF183 Taqman concentrations were higher under wet conditions DogBact concentrations were greater in the winter and under wet conditions, and Rum2Bac concentrations were comparatively low throughout the study with no difference across seasons or precipitation conditions. Concentrations of HF183 Taqman, DogBact, and Rum2Bac were positively correlated with culturable E. coli concentrations; however, DogBact had the largest R 2 value among the three markers, and the forward stepwise regression indicated it was the best predictor of culturable E. coli concentrations at the BacteriALERT sites. Recursive partitioning indicated that BAV exceedances of model-based E. coli estimates were best explained by DogBact concentrations ≥3 gene copies per mL (CN/mL). Detections of esp2 at BacteriALERT sites were best explained by DogBact concentrations ≥11 CN/mL, while detections of esp2 at synoptic sites were best explained by HF183 Taqman ≥29 CN/mL. At the synoptic sites, HF183 Taqman levels were associated with wastewater treatment plant density. However, this relationship was driven primarily by a single site, suggesting possible conveyance issues in that catchment. esp2 detections at synoptic sites were positively associated with development within a 2-km radius and negatively associated with development within the catchment, suggesting multiple sources of esp2 in the watershed. DogBact and Rum2Bac were not associated with the land use features included in our analyses. Implications for Park management include: 1) fecal contamination levels were highest during wet conditions and in the off season when fewer visitors are expected to be participating in water-based recreation, 2) dogs are likely contributors to fecal contamination in the CRNRA and may be sources of pathogenic bacteria indicating further investigation of the origins of this contamination may be warranted as would be research to understand the human health risks from exposure to dog fecal contamination, and 3) high levels of the human marker at one site in the CRNRA watershed suggests more extensive monitoring in that catchment may locate the origin of human fecal contamination detected during this study.

Georgia↗

Determination of human-health pharmaceuticals in filtered water by chemically modified styrene-divinylbenzene resin-based solid-phase extraction and high-performance liquid chromatography/Mass Spectrometry

In 1999, the Methods Research and Development Program of the U.S. Geological Survey National Water Quality Laboratory began the process of developing a method designed to identify and quantify human-health pharmaceuticals in four filtered water-sample types: reagent water, ground water, surface water minimally affected by human contributions, and surface water that contains a substantial fraction of treated wastewater. Compounds derived from human pharmaceutical and personal-care product use, which enter the environment through wastewater discharge, are a newly emerging area of concern; this method was intended to fulfill the need for a highly sensitive and highly selective means to identify and quantify 14 commonly used human pharmaceuticals in filtered-water samples. The concentrations of 12 pharmaceuticals are reported without qualification; the concentrations of two pharmaceuticals are reported as estimates because long-term reagent-spike sample recoveries fall below acceptance criteria for reporting concentrations without qualification. The method uses a chemically modified styrene-divinylbenzene resin-based solid-phase extraction (SPE) cartridge for analyte isolation and concentration. For analyte detection and quantitation, an instrumental method was developed that used a high-performance liquid chromatography/mass spectrometry (HPLC/MS) system to separate the pharmaceuticals of interest from each other and coextracted material. Immediately following separation, the pharmaceuticals are ionized by electrospray ionization operated in the positive mode, and the positive ions produced are detected, identified, and quantified using a quadrupole mass spectrometer. In this method, 1-liter water samples are first filtered, either in the field or in the laboratory, using a 0.7-micrometer (μm) nominal pore size glass-fiber filter to remove suspended solids. The filtered samples then are passed through cleaned and conditioned SPE cartridges at a rate of about 15 milliliters per minute. Excess water is eliminated from the cartridge sorbent bed by passing air through the cartridges, and the analytes retained on the SPE bed are eluted from the cartridge sequentially, first with methanol, followed by acidified methanol, and combined in collection tubes. This sample extract then is reduced from about 10 milliliters (mL) to about 0.1 mL (or 100 microliters) under a stream of purified nitrogen gas with the collection tubes in a heated (40°C) water bath. The reduced extracts then are fortified with an internal standard solution (when using internal standard quantitation), brought to a final volume of 1 mL with an aqueous ammonium formate buffer solution, and filtered through a 0.2-μm Teflon syringe filter as they are transferred into vials for instrumental analysis. Instrumental analysis by the HPLC/MS procedure permits determination of individual pharmaceutical concentrations from 0.005 to 1.0 microgram per liter, based on the lowest and the highest calibration standards routinely used. The reporting levels for this method are compound dependent, and have been experimentally determined based on the precision of quantitation of compounds from eight fortified organic-free water samples in single-operator experiments. The method detection limits and interim reporting levels for the compounds determined by this method were calculated from recoveries of the pharmaceuticals from reagent-water samples amended at 0.05 microgram per liter, and ranged between 0.0069 and 0.0142 microgram per liter, and 0.015 and 0.10 microgram per liter, respectively. Concentrations for 12 compounds are reported without qualification, and for two compounds are reported as qualified estimates. After initial development, the method was applied to more than 1,800 surface-, ground-, and wastewater samples from 2002 to 2005 and documented in a number of published studies. This research application of the method provided the opportunity to collect a large data set of ambient environmental concentrations and also permitted the collection of an extensive set of reagent blanks and spike quality-control (QC) samples. This multiple-year set of QC samples enabled further evaluation of method performance under multiple operator and multiple instrument conditions typical of routine laboratory operation. These results are an important part of the entire data set contained in this report because they document method performance over an extended time. Because sample matrix can substantially affect method performance, inclusion of environmental matrix-spike samples is required as a routine component of study plan quality control. Method performance has been measured by long-term tracking of observed recoveries from fortified organic-free water samples processed with environmental samples (laboratory reagent spikes), as well as by observed recoveries from multiple fortified environmental water samples. The fortified environmental samples included surface water, wastewater effluent-dominated surface water, and ground water, fortified at two environmentally relevant concentrations and corrected for ambient environmental concentrations. Because the responses of individual pharmaceuticals vary as a function of proton affinity, the ionization efficiency, and thus relative response, of each pharmaceutical, the quality-control surrogate compounds, and the quantitation internal standard can be suppressed or enhanced by the presence of the sample matrix. As a result, several quality-control sample types are required to properly interpret the ambient environmental concentrations of pharmaceuticals in aqueous samples. The quality-control sample types and results include laboratory reagent spikes and laboratory reagent blanks to provide insight into the performance of the method in the absence of a sample matrix, and matrix-spike recovery samples and replicate environmental samples, collected from representative sample matrix types within the aquatic system under study.

Techniques and Methods↗

Assessment of the potential for in-plume sulphur dioxide gas-ash interactions to influence the respiratory toxicity of volcanic ash

Background Volcanic plumes are complex environments composed of gases and ash particles, where chemical and physical processes occur at different temperature and compositional regimes. Commonly, soluble sulphate- and chloride-bearing salts are formed on ash as gases interact with ash surfaces. Exposure to respirable volcanic ash following an eruption is potentially a significant health concern. The impact of such gas-ash interactions on ash toxicity is wholly un-investigated. Here, we study, for the first time, whether the interaction of volcanic particles with sulphur dioxide (SO 2 ) gas, and the resulting presence of sulphate salt deposits on particle surfaces, influences toxicity to the respiratory system, using an advanced in vitro approach. Methods To emplace surface sulphate salts on particles, via replication of the physicochemical reactions that occur between pristine ash surfaces and volcanic gas, analogue substrates (powdered synthetic volcanic glass and natural pumice) were exposed to SO 2 at 500 °C, in a novel Advanced Gas-Ash Reactor, resulting in salt-laden particles. The solubility of surface salt deposits was then assessed by leaching in water and geochemical modelling. A human multicellular lung model was exposed to aerosolised salt-laden and pristine (salt-free) particles, and incubated for 24 h. Cell cultures were subsequently assessed for biological endpoints, including cytotoxicity (lactate dehydrogenase release), oxidative stress (oxidative stress-related gene expression; heme oxygenase 1 and NAD(P)H dehydrogenase [quinone] 1) and its (pro-)inflammatory response (tumour necrosis factor α, interleukin 8 and interleukin 1β at gene and protein levels). Results In the lung cell model no significant effects were observed between the pristine and SO 2 -exposed particles, indicating that the surface salt deposits, and the underlying alterations to the substrate, do not cause acute adverse effects in vitro . Based on the leachate data, the majority of the sulphate salts from the ash surfaces are likely to dissolve in the lungs prior to cellular uptake. Conclusions The findings of this study indicate that interaction of volcanic ash with SO 2 during ash generation and transport does not significantly affect the respiratory toxicity of volcanic ash in vitro . Therefore, sulphate salts are unlikely a dominant factor controlling variability in in vitro toxicity assessments observed during previous eruption response efforts.

Environmental Research↗

Sources and characteristics of organic matter in the Clackamas River, Oregon, related to the formation of disinfection by-products in treated drinking water

This study characterized the amount and quality of organic matter in the Clackamas River, Oregon, to gain an understanding of sources that contribute to the formation of chlorinated and brominated disinfection by-products (DBPs), focusing on regulated DBPs in treated drinking water from two direct-filtration treatment plants that together serve approximately 100,000 customers. The central hypothesis guiding this study was that natural organic matter leaching out of the forested watershed, in-stream growth of benthic algae, and phytoplankton blooms in the reservoirs contribute different and varying proportions of organic carbon to the river. Differences in the amount and composition of carbon derived from each source affects the types and concentrations of DBP precursors entering the treatment plants and, as a result, yield varying DBP concentrations and species in finished water. The two classes of DBPs analyzed in this study-trihalomethanes (THMs) and haloacetic acids (HAAs)-form from precursors within the dissolved and particulate pools of organic matter present in source water. The five principal objectives of the study were to (1) describe the seasonal quantity and character of organic matter in the Clackamas River; (2) relate the amount and composition of organic matter to the formation of DBPs; (3) evaluate sources of DBP precursors in the watershed; (4) assess the use of optical measurements, including in-situ fluorescence, for estimating dissolved organic carbon (DOC) concentrations and DBP formation; and (5) assess the removal of DBP precursors during treatment by conducting treatability "jar-test" experiments at one of the treatment plants. Data collection consisted of (1) monthly sampling of source and finished water at two drinking-water treatment plants; (2) event-based sampling in the mainstem, tributaries, and North Fork Reservoir; and (3) in-situ continuous monitoring of fluorescent dissolved organic matter (FDOM), turbidity, chlorophyll- a , and other constituents to continuously track source-water conditions in near real-time. Treatability tests were conducted during the four event-based surveys to determine the effectiveness of coagulant and powdered activated carbon (PAC) on the removal of DBP precursors. Sample analyses included DOC, total particulate carbon (TPC), total and dissolved nutrients, absorbance and fluorescence spectroscopy, and, for regulated DBPs, concentrations of THMs and HAAs in finished water and laboratory-based THM and HAA formation potentials (THMFP and HAAFP, respectively) for source water and selected locations throughout the watershed. The results of this study may not be typical given the record and near record amounts of precipitation that occurred during spring that produced streamflow much higher than average in 2010-11. Although there were algal blooms, lower concentrations of chlorophyll- a were observed in the water column during the study period compared to historical data. Concentrations of DBPs in finished (treated) water averaged 0.024 milligrams per liter (mg/L) for THMs and 0.022 mg/L for HAAs; maximum values were about 0.040 mg/L for both classes of DBPs. Although DBP concentrations were somewhat higher within the distribution system, none of the samples collected for this study or for the quarterly compliance monitoring by the water utilities exceeded levels permissible under existing U.S. Environmental Protection Agency (USEPA) regulations: 0.080 mg/L for THMs and 0.060 mg/L for HAAs. DOC concentrations were generally low in the Clackamas River, typically about 1.0-1.5 mg/L. Concentrations in the mainstem occasionally increased to nearly 2.5 mg/L during storms; DOC concentrations in tributaries were sometimes much higher (up to 7.8 mg/L). The continuous in-situ FDOM measurements indicated sharp rises in DOC concentrations in the mainstem following rainfall events; concentrations were relatively stable during summer base flow. Even though the first autumn storm mobilized appreciable quantities of carbon, higher concentrations of DBPs in finished water were observed 3-weeks later, after the ground was saturated from additional rainfall. The majority of the DOC in the lower Clackamas River appears to originate from the upper basin, suggesting terrestrial carbon was commonly the dominant source. Lower-basin tributaries typically contained the highest concentrations of DOC and DBP precursors and contributed substantially to the overall loads in the mainstem during storms. During low-flow periods, tributaries were not major sources of DOC or DBP precursors to the Clackamas River. Although the dissolved fraction of organic carbon contributed the majority of DBP precursors, at times the particulate fraction (inorganic sediment and organic particles including detritus and algal material) contributed a substantial fraction of DBP precursors. Considering just the main-stem sites, on average, 10 percent of THMFP and 32 percent of HAAFP were attributed to particulate carbon. This finding suggests water-treatment methods that remove particles prior to chlorination would reduce finished-water DBP concentrations to some degree. Overall, concentrations of THM and HAA precursors were closely linked to DOC concentrations; laboratory DBP formation potentials (DBPFPs) clearly showed that THMFP and HAAFP were greatest in the downstream tributaries that contained elevated carbon concentrations. However, carbon-normalized "specific" formation potentials for THMs and HAAs (STHMFP and SHAAFP, respectively) revealed changes in carbon character over time that affected the two types of DBP classes differently. HAA precursors were elevated in waters containing aromatic-rich soil-derived material arising from forested areas. In contrast, THM precursors were associated with carbon having a lower aromatic content; highest STHMFP occurred in autumn 2011 in the mainstem from North Fork Reservoir downstream to LO DWTP. This pattern suggests the potential for a link between THM precursors and algal-derived carbon. The highest STHMFP value was measured within North Fork Reservoir, indicating reservoir derived carbon may be important for this class of DBPs. Weak correlations between STHMFP and SHAAFP emphasize that precursor sources for these types of DBPs may be different. This highlights not only that different locations within the watershed produce carbon with different reactivity (specific DBPFP), but also that different management approaches for each class of DBP precursors could be required for control. Treatability tests conducted on source water during four basin-wide surveys demonstrated that an average of about 40 percent of DOC can be removed by coagulation. While the decrease in THMFP following coagulation was similar to DOC, the decrease in HAAFP was much greater (approximately 70 percent), indicating coagulation is particularly effective at removing HAA precursors'likely because of the aromatic nature of the carbon associated with HAA precursors. Several findings from this study have direct implications for managing drinking-water resources and for providing useful information that may help improve treatment-plant operations. For example, the use of in-situ fluorometers that measure FDOM provided an excellent proxy for DOC concentration in this system and revealed short-term, rapid changes in DOC concentration during storm events. In addition, the strong correlation between FDOM values measured in-situ and HAA5 concentrations in finished water may permit estimation of continuous HAA concentrations, as was done here. As part of this study, multiple in-situ FDOM sensors were deployed continuously and in real-time to characterize the composition of dissolved organic matter. Although the initial results were promising, additional research and engineering developments will be needed to demonstrate the full utility of these sensors for this purpose. In conclusion, although DBPFPs were strongly correlated to DOC concentration, some DBPs formed from particulate carbon, including terrestrial leaf material and algal material such as planktonic species of blue-green algae and sloughed filaments, stalks, and cells of benthic algae. Different precursor sources in the watershed were evident from the data, suggesting specific actions may be available to address some of these sources. In-situ measurements of FDOM proved to be an excellent proxy for DOC concentration as well as HAA formation during treatment, which suggests further development and refinement of these sensors have the potential to provide real-time information about complex watershed processes to operators at the drinking-water treatment plants. Follow-up studies could examine the relative roles that terrestrial and algal sources have on the DBP precursor pool to better understand how watershed-management activities may be affecting the transport of these compounds to Clackamas River drinking-water intakes. Given the low concentrations of algae in the water column during this study, additional surveys during more typical river conditions could provide a more complete understanding of how algae contribute DBP precursors. Further development of FDOM-sensor technology can improve our understanding of carbon dynamics in the river and how concentrations may be trending over time. This study was conducted in collaboration with Clackamas River Water and the City of Lake Oswego water utilities. Other research partners included Oregon Health and Science University in Hillsboro, Oregon, Alexin Laboratory in Tigard, Oregon, U.S. Geological Survey National Research Program Laboratory in Denver, Colorado, and the U.S. Geological Survey Water Science Centers in Portland, Oregon, and Sacramento, California. This project was supported with funding from Clackamas River Water, City of Lake Oswego, the U.S. Geological Survey, and the Water Research Foundation.

Oregon↗