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Imidacloprid in United States rivers, 2013–2022: Persistent presence and emerging chronic hazard

Imidacloprid, a neonicotinoid insecticide, is used for agricultural and nonagricultural purposes and is toxic to nontarget organisms at low concentrations in aquatic ecosystems. A total of 12,547 water samples were collected from 2013 to 2022 from 77 rivers across the United States (U.S.) and were analyzed to evaluate detections and temporal trends in imidacloprid concentrations. Imidacloprid was detected in 44% of all samples, and the mean concentration, adjusted for nondetect samples, of 24.9 ng/L (median = 11.9 ng/L) was more than twice the chronic benchmark for freshwater invertebrates (10 ng/L). This potential hazard to aquatic life was persistent, with 44% of the sites having a median concentration exceeding the chronic benchmark. Half of the sites ( n = 38) had increasing trends, including large river sites along the Mississippi River. The mean increase was 10.6 ng/L over the past decade, while only six sites indicated decreasing trends. The estimated total loading of imidacloprid delivered to the Gulf of America from 2013 to 2022 was 129,489 kg (142.7 U.S. ton). The extensive presence of imidacloprid in U.S. waterways, the high percentage of sites with trends of increasing concentrations, and the prevalence of concentrations exceeding chronic benchmarks suggest widespread persistent risks to ecosystem health.

Environmental Science & Technology↗

Spatiotemporal patterns of mercury accumulation in lake sediments of western North America

For the Western North America Mercury Synthesis, we compiled mercury records from 165 dated sediment cores from 138 natural lakes across western North America. Lake sediments are accepted as faithful recorders of historical mercury accumulation rates, and regional and sub-regional temporal and spatial trends were analyzed with descriptive and inferential statistics. Mercury accumulation rates in sediments have increased, on average, four times (4×) from 1850 to 2000 and continue to increase by approximately 0.2 μg/m 2 per year. Lakes with the greatest increases were influenced by the Flin Flon smelter, followed by lakes directly affected by mining and wastewater discharges. Of lakes not directly affected by point sources, there is a clear separation in mercury accumulation rates between lakes with no/little watershed development and lakes with extensive watershed development for agricultural and/or residential purposes. Lakes in the latter group exhibited a sharp increase in mercury accumulation rates with human settlement, stabilizing after 1950 at five times (5×) 1850 rates. Mercury accumulation rates in lakes with no/little watershed development were controlled primarily by relative watershed size prior to 1850, and since have exhibited modest increases (in absolute terms and compared to that described above) associated with (regional and global) industrialization. A sub-regional analysis highlighted that in the ecoregion Northwestern Forest Mountains, <1% of mercury deposited to watersheds is delivered to lakes. Research is warranted to understand whether mountainous watersheds act as permanent sinks for mercury or if export of “legacy” mercury (deposited in years past) will delay recovery when/if emissions reductions are achieved.

Alaska, Alberta, Arizona, British Columbia, Califo↗

Identification of groundwater nitrate contamination from explosives used in road construction: Isotopic, chemical, and hydrologic evidence

Explosives used in construction have been implicated as sources of NO 3 &ndash; contamination in groundwater, but direct forensic evidence is limited. Identification of blasting-related NO 3 &ndash; can be complicated by other NO 3 &ndash; sources, including agriculture and wastewater disposal, and by hydrogeologic factors affecting NO 3 &ndash; transport and stability. Here we describe a study that used hydrogeology, chemistry, stable isotopes, and mass balance calculations to evaluate groundwater NO 3 &ndash; sources and transport in areas surrounding a highway construction site with documented blasting in New Hampshire. Results indicate various groundwater responses to contamination: (1) rapid breakthrough and flushing of synthetic NO 3 &ndash; (low &delta; 15 N, high &delta; 18 O) from dissolution of unexploded NH 4 NO 3 blasting agents in oxic groundwater; (2) delayed and reduced breakthrough of synthetic NO 3 &ndash; subjected to partial denitrification (high &delta; 15 N, high &delta; 18 O); (3) relatively persistent concentrations of blasting-related biogenic NO 3 &ndash; derived from nitrification of NH 4 + (low &delta; 15 N, low &delta; 18 O); and (4) stable but spatially variable biogenic NO 3 &ndash; concentrations, consistent with recharge from septic systems (high &delta; 15 N, low &delta; 18 O), variably affected by denitrification. Source characteristics of denitrified samples were reconstructed from dissolved-gas data (Ar, N 2 ) and isotopic fractionation trends associated with denitrification (&Delta;&delta; 15 N/&Delta;&delta; 18 O &asymp; 1.31). Methods and data from this study are expected to be applicable in studies of other aquifers affected by explosives used in construction.

Environmental Science & Technology↗

Groundwater discharges as a source of phytoestrogens and other agriculturally derived contaminants to streams

Groundwater discharge zones in streams are important habitats for aquatic organisms. The use of discharge zones for thermal refuge and spawning by fish and other biota renders them susceptible to potential focused discharge of groundwater contamination. Currently, there is a paucity of information about discharge zones as a potential exposure pathway of chemicals to stream ecosystems. Using thermal mapping technologies to locate groundwater discharges, shallow groundwater and surface water from three rivers in the Chesapeake Bay Watershed, USA were analyzed for phytoestrogens, pesticides and their degradates, steroid hormones, sterols and bisphenol A. A Bayesian censored regression model was used to compare groundwater and surface water chemical concentrations. The most frequently detected chemicals in both ground and surface water were the phytoestrogens genistein (79%) and formononetin (55%), the herbicides metolachlor (50%) and atrazine (74%), and the sterol cholesterol (88%). There was evidence suggesting groundwater discharge zones could be a unique exposure pathway of chemicals to surface water systems, in our case, metolachlor sulfonic acid (posterior mean concentration = 150 ng/L in groundwater and 4.6 ng/L in surface water). Our study also demonstrated heterogeneity of chemical concentration in groundwater discharge zones within a stream for the phytoestrogen formononetin, the herbicides metolachlor and atrazine, and cholesterol. Results support the hypothesis that discharge zones are an important source of exposure of phytoestrogens and herbicides to aquatic organisms. To manage critical resources within the Chesapeake Bay Watershed, more work is needed to characterize exposure in discharge zones more broadly across time and space.

Delaware, Maryland, New Jersey, New York, Pennsylv↗

Land cover changes associated with recent energy development in the Williston Basin; Northern Great Plains, USA

The Williston Basin in the Northern Great Plains has experienced rapid energy development since 2000. To evaluate the land cover changes resulting from recent (2000 &ndash; 2015) development, the area and previous land cover of all well pads (pads) constructed during this time was determined, the amount of disturbed and reclaimed land adjacent to pads was estimated, land cover changes were analyzed over time for three different well types, and the effects from future development were predicted. The previous land cover of the 12,990 ha converted to pads was predominately agricultural (49.5%) or prairie (47.4%) with lesser amounts of developed (2.3%), aquatic (0.5%), and forest (0.4%). Additionally, 12,121 ha have likely been disturbed and reclaimed. The area required per gas well remained constant through time while the land required per oil well increased initially and then decreased as development first shifted from conventional to unconventional drilling and then to multi-bore pads. For non-oil-and- gas wells (i.e. stratigraphic test wells, water wells, injection wells, etc.), the area per well increased through time likely due to increased produced water disposal requirements. Future land cover change is expected to be 2.7 times greater than recent development with much of the development occurring in five counties in the core Bakken development area. Direct land cover change and disturbance from recent and expected development are predicted to affect 0.4% of the landscape across the basin; however, in the core Bakken development area, 2.3% of the landscape will be affected including 2.1% of the remaining grassland. Although future development will result in significant land cover change, evolving industry practices and proactive siting decisions, such as development along energy corridors and placing pads in areas previously altered by human activity, have the potential to reduce the ecological effects of future energy development in the Williston Basin.

Williston Basin↗

Occurrence of neonicotinoid insecticides in finished drinking water and fate during drinking water treatment

Neonicotinoid insecticides are widespread in surface waters across the agriculturally-intensive Midwestern US. We report for the first time the presence of three neonicotinoids in finished drinking water and demonstrate their general persistence during conventional water treatment. Periodic tap water grab samples were collected at the University of Iowa over seven weeks in 2016 (May-July) after maize/soy planting. Clothianidin, imidacloprid, and thiamethoxam were ubiquitously detected in finished water samples and ranged from 0.24-57.3 ng/L. Samples collected along the University of Iowa treatment train indicate no apparent removal of clothianidin and imidacloprid, with modest thiamethoxam removal (~50%). In contrast, the concentrations of all neonicotinoids were substantially lower in the Iowa City treatment facility finished water using granular activated carbon (GAC) filtration. Batch experiments investigated potential losses. Thiamethoxam losses are due to base-catalyzed hydrolysis at high pH conditions during lime softening. GAC rapidly and nearly completely removed all three neonicotinoids. Clothianidin is susceptible to reaction with free chlorine and may undergo at least partial transformation during chlorination. Our work provides new insights into the persistence of neonicotinoids and their potential for transformation during water treatment and distribution, while also identifying GAC as an effective management tool to lower neonicotinoid concentrations in finished drinking water.

Environmental Science & Technology Letters↗

An assessment of the effects of cell size on AGNPS modeling of watershed runoff

This study investigates the changes in simulated watershed runoff from the Agricultural NonPoint Source (AGNPS) pollution model as a function of model input cell size resolution for eight different cell sizes (30 m, 60 m, 120 m, 210 m, 240 m, 480 m, 960 m, and 1920 m) for the Little River Watershed (Georgia, USA). Overland cell runoff (area-weighted cell runoff), total runoff volume, clustering statistics, and hot spot patterns were examined for the different cell sizes and trends identified. Total runoff volumes decreased with increasing cell size. Using data sets of 210-m cell size or smaller in conjunction with a representative watershed boundary allows one to model the runoff volumes within 0.2 percent accuracy. The runoff clustering statistics decrease with increasing cell size; a cell size of 960 m or smaller is necessary to indicate significant high-runoff clustering. Runoff hot spot areas have a decreasing trend with increasing cell size; a cell size of 240 m or smaller is required to detect important hot spots. Conclusions regarding cell size effects on runoff estimation cannot be applied to local watershed areas due to the inconsistent changes of runoff volume with cell size; but, optimal cells sizes for clustering and hot spot analyses are applicable to local watershed areas due to the consistent trends.

Cartography and Geographic Information Science↗

Data resources for the Wyoming Landscape Conservation Initiative (WLCI) Integrated Assessment (IA)

The data contained in this report were compiled, modified, and analyzed for the Wyoming Landscape Conservation Initiative (WLCI) Integrated Assessment (IA). The WLCI is a long-term science based effort to assess and enhance aquatic and terrestrial habitats at a landscape scale in southwest Wyoming while facilitating responsible energy development through local collaboration and partnerships. The IA is an integrated synthesis and analysis of WLCI resource values based on best available data and information collected from multiple agencies and organizations. It is a support tool for landscape-scale conservation planning and evaluation, and a data and analysis resource that can be used for addressing specific management questions. The IA analysis was conducted using a Geographic Information System in a raster (that is, a grid) environment using a cell size of 30 meters. To facilitate the interpretation of the data in a regional context, mean values were summarized and displayed at the subwatershed unit (WLCI subwatersheds were subset from the National Hydrography Dataset, Hydrologic Unit Code 12/Level 6). A dynamic mapping platform, accessed via the WLCI webpage at http://www.wlci.gov is used to display the mapped information, and to access underlying resource values that were combined to produce the final mapped results. The raster data used in the IA are provided here for use by interested parties to conduct additional analyses and can be accessed via the WLCI webpage. This series contains 74 spatial data sets: WLCI subwatersheds (vector) and 73 geotiffs (raster) that are segregated into the major categories of Multicriteria Index (including Resource Index and Condition), Change Agents, and Future Change. The Total Multicriteria Index is composed of the Aquatic Multicriteria Index and the Terrestrial Multicriteria Index. The Aquatic Multicriteria Index is composed of the Aquatic Resource Index and the Aquatic Condition. The Aquatic Resource Index is composed of the following components: Groundwater, Special Management Areas, and Priority Areas. The Aquatic Condition is composed of the following components: Focal Species, Species of Concern, Focal Ecosystems, and Proper Functioning Condition. The Terrestrial Multicriteria Index is composed of the Terrestrial Resource Index and the Terrestrial Condition. The Terrestrial Resource Index is composed of the following components: Special Management Areas, Agriculture, and Priority Areas. The Terrestrial Condition is composed of the following components: Focal Species, Big Game, Species of Concern, Rare Plants, and Focal Ecosystems. The Change Agents are composed the following components: Roads, Energy, Mines, and Urban. The Future Change is composed of the following components: Oil-Gas-Coal, Wind, Minerals, Climate-Temperature, Invasive Species, and Urban.

Wyoming↗

Reach-scale stream restoration in agricultural streams of southern Minnesota alters structural and functional responses of macroinvertebrates

Recent studies suggest that stream restoration at the reach scale may not increase stream biodiversity, raising concerns about the utility of this conservation practice. We examined whether reach-scale restoration in disturbed agricultural streams was associated with changes in macroinvertebrate community structure (total macroinvertebrate taxon richness, total macroinvertebrate density, Ephemeroptera, Plecoptera, Trichoptera [EPT] taxon richness, % abundance of EPT taxa) or secondary production (macroinvertebrate biomass over time). We collected macroinvertebrate samples over the course of 1 y from restored and unrestored reaches of 3 streams in southern Minnesota and used generalized least-square (GLS) models to assess whether measures of community structure were related to reach type, stream site, or sampling month. After accounting for effects of stream site and time, we found no significant difference in total taxon richness or % abundance of EPT taxa between restored and unrestored reaches. However, the number of EPT taxa and macroinvertebrate density were significantly higher in restored than in unrestored reaches. We compared secondary production estimates among study reaches based on 95 th -percentile confidence intervals generated via bootstrapping. In each study stream, secondary production was significantly (2–3×) higher in the restored than in the unrestored reach. Higher productivity in the restored reaches was largely a result of the disproportionate success of a few dominant, tolerant taxa. Our findings suggest that reach-scale restoration may have ecological effects that are not detected by measures of total taxon richness alone.

Freshwater Science↗

Widespread use of the nitrification inhibitor nitrapyrin: Assessing benefits and costs to agriculture, ecosystems, and environmental health

Agricultural production and associated applications of nitrogen (N) fertilizers have increased dramatically in the last century, and current projections to 2050 show that demands will continue to increase as the human population grows. Applied in both organic and inorganic fertilizer forms, N is an essential nutrient in crop productivity. Increased fertilizer applications, however, create the potential for more N loss before plant uptake. One strategy for minimizing N loss is the use of enhanced efficiency fertilizers, fortified with a nitrification inhibitor, such as nitrapyrin. In soils and water, nitrapyrin inhibits the activity of ammonia monooxygenase, a microbial enzyme that catalyzes the first step of nitrification from ammonium to nitrite. Potential benefits of using nitrification inhibitors range from reduced nitrate leaching and nitrous oxide emissions to increased crop yield. The extent of these benefits, however, depends on environmental conditions and management practices. Thus, such benefits are not always realized. Additionally, nitrapyrin has been shown to transport off-field, and it is unknown what effects environmental nitrapyrin could have on nontarget organisms and the ecological nitrogen cycle. Here, we review the agronomic and environmental benefits and costs of nitrapyrin use and present a series of research questions and considerations to be addressed with future nitrification inhibitor research.

Environmental Science and Technology↗

Applying the ecology of aquatic–terrestrial linkages to freshwater and riparian management

Global stressors such as climate change, invasive species, urbanization, agricultural practices, and pollution can alter aquatic resource subsidies to terrestrial consumers. The effects of these stressors on timing, quality, and quantity of aquatic subsidies, such as adult aquatic insects, to birds, herpetofauna, and mammals, have large implications for wildlife management (Baxter et al. 2004 , Saunders and Fausch 2007 , Walters et al. 2008 , Sullivan and Rodewald 2012 , Morrissey et al. 2015 , Kraus et al. 2016 , Larsen et al. 2016 , Sullivan et al. 2019 ). For example, insect-mediated contaminant transport from polluted rivers expose song bird nestlings and other protected birds to potentially toxic levels of persistent organic contaminants and pharmaceuticals (Walters et al. 2010 , Richmond et al. 2018 ). Recent declines in aquatic insect production caused by pollution and changes in land use have been tied to global declines in terrestrial insectivores such as birds and bats (Hallmann et al. 2014 , Morrissey et al. 2015 , Raby et al. 2018 ). These natural-resource impacts from aquatic–terrestrial exposure and loss of resource subsidies are leading to changes in monitoring protocols and how management agencies evaluate the effectiveness of corrective remedies (Muehlbauer et al. 2019 ). For researchers interested in the application of resource subsidy research, a logical next step is to help practitioners anticipate effects of global stressors on aquatic-terrestrial linkages and incorporate these principles into decision making.

Freshwater Science↗

Occurrence, distribution and transport of pesticides into the Salton Sea Basin, California, 2001-2002

The Salton Sea is a hypersaline lake located in southeastern California. Concerns over the ecological impacts of sediment quality and potential human exposure to dust emissions from exposed lakebed sediments resulting from anticipated shrinking of shoreline led to a study of pesticide distribution and transport within the Salton Sea Basin, California, in 2001-2002. Three sampling stations-upriver, river mouth, and offshore-were established along each of the three major rivers that discharge into the Salton Sea. Large-volume water samples were collected for analysis of pesticides in water and suspended sediments at the nine sampling stations. Samples of the bottom sediment were also collected at each site for pesticide analysis. Sampling occurred in October 2001, March-April 2002, and October 2002, coinciding with the regional fall and spring peaks in pesticide use in the heavily agricultural watershed. Fourteen current-use pesticides were detected in water and the majority of dissolved concentrations ranged from the limits of detection to 151 ng/l. Diazinon, EPTC and malathion were detected at much higher concentrations (940-3,830 ng/l) at the New and Alamo River upriver and near-shore stations. Concentrations of carbaryl, dacthal, diazinon, and EPTC were higher in the two fall sampling periods, whereas concentrations of atrazine, carbofuran, and trifluralin were higher during the spring, which matched seasonal use patterns of these pesticides. Current-use pesticides were also detected on suspended and bed sediments in concentrations ranging from detection limits to 106 ng/g. Chlorpyrifos, dacthal, EPTC, trifluralin, and DDE were the most frequently detected pesticides on sediments from all three rivers. The number of detections and concentrations of suspended sediment-associated pesticides were often similar for the river upriver and near-shore sites, consistent with downstream transport of pesticides via suspended sediment. While detectable suspended sediment pesticide concentrations were more sporadic than detected aqueous concentrations, seasonal trends were similar to those for dissolved concentrations. Generally, the pesticides detected on suspended sediments were the same as those on the bed sediments, and concentrations were similar, especially at the Alamo River upriver site. With a few exceptions, pesticides were not detected in suspended or bed sediments from the off-shore sites. The partitioning of pesticides between water and sediment was not predictable from solely the physical-chemical properties of individual pesticide compounds, but appear to be a complicated function of the quantity of pesticide applied in the watershed, residence time of sediments in the water, and compound solubility and hydrophobicity. Sediment concentrations of most pesticides were found to be 100-1,000 times lower than the low-effects levels determined in human health risk assessment studies. However, maximum concentrations of chlorpyrifos on suspended sediments were approximately half the low-effects level, suggesting the need for further sediment characterization of lake sediments proximate to riverine inputs. ?? 2008 Springer Science+Business Media B.V.

Hydrobiologia↗

Influence of land use and region on glyphosate and aminomethylphosphonic acid in streams in the USA

Glyphosate is the most widely used herbicide in the United States for agricultural and non-agricultural weed control. Many studies demonstrate possible effects of glyphosate and its degradate AMPA on human and ecological health. Although glyphosate is thought to have limited mobility in soil, it is found year-round in many rivers and streams throughout the world in both agricultural and developed environments. It is vitally important to continue to increase the knowledge base of glyphosate use, distribution, transport, and impacts on human health and the environment. Here we show that glyphosate and AMPA are found in nearly all of 70 streams throughout the United States at concentrations far below human health or ecological benchmarks, with less occurrence in the Northeast and that undeveloped land, classified as such by land use near the sampling station, has lower concentrations compared to other types of land. Results also show that sites with large watersheds tend to have more AMPA than glyphosate and the opposite is true for small watersheds. Travel times and opportunity for glyphosate to degrade to AMPA and for reservoirs of AMPA to grow are greater in large watersheds. Factors that promoted quick movement of glyphosate to streams, such as subsurface tile or storm drains, sewers, overland flow from developed landscapes, and arid landscapes were associated with sites that had greater concentrations of glyphosate compared to AMPA. These results contribute contemporary information and generalized interpretations adding to the knowledge base of the fate of glyphosate on a national scale and provide a springboard for further exploration of technical processes controlling transport to streams.

Science of the Total Environment↗

Assessing microplastics, per- and polyfluoroalkyl substances (PFAS), and other contaminants of global concern in wadable agricultural streams

Microplastics, per- and polyfluoroalkyl substances (PFAS), antibiotic resistance genes (ARGs), pharmaceuticals and personal care products (PPCPs), and pesticides may lead to unintended environmental contamination through many pathways in multiple matrices. This statewide, multi-matrix study of contaminants of global concern (CGCs) in agricultural streams across Iowa (United States) is the first to examine multiple CGCs in water, bed sediment, and fish to understand their occurrence in small streams located in regions of intense agriculture activity. Iowa plays a pivotal role in agriculture, with more than 85% of Iowa’s landscape devoted to agriculture making it an ideal location for determining the prevalence of CGCs to provide critical baseline exposure data. Fifteen sites were sampled across a range of predominant land uses (e.g., poultry, swine); all sites had detections of microplastics in all matrices. Concentrations of PFAS varied but were detected in water and sediment; all fish had detections of perfluorooctanesulfonate (PFOS), a type of PFAS. More than 50% of water and bed sediment samples had detections of ARGs. The most frequently detected PPCP was metformin. No sites had a cumulative exposure activity ratio greater than 1.0 for chemical exposures; 13 sites were above the 0.001 precautionary threshold. Toxicity quotients calculated using Aquatic Life Benchmarks were below the 0.1 moderate risk threshold for chemical exposures for all but one site. For fish, all sites exceeded the moderate and high-risk thresholds proposed for microplastic particles for food dilution (both chronic and acute exposures) and all sites exceeded the microplastic moderate threshold proposed for chronic tissue translocation, and two sites exceeded the threshold for acute tissue translocation.

Iowa↗

Trace element residues in bluegills and common carp from the lower San Joaquin River, California, and its tributaries

Whole-body samples of bluegills (Lepomis macrochirus) and common carp (Cyprinus carpio) from the San Joaquin River and two tributaries (Merced River and Salt Slough) were analyzed to determine if the concentrations of any of nine elements were elevated as a result of exposure of the fish to agricultural subsurface (tile) drainage water. Highest concentrations (μg/g dry weight) detected were as follows (first number in each pair applies to bluegills and the second to carp): arsenic (As), 0.97 and 1.5; boron (B), 14 and 20; cadmium (Cd), 0.14 and 0.27; chromium (Cr), 2.7 and 2.2; mercury (hg), 3.3 and 2.9; molybdenum (Mo), 2.8 and 3.6; nickel (Ni), 0.87 and 2.2; lead (Pb), 0.26 and 2.3; and selenium (Se), 3.2 and 5.5. The lowest concentrations were below the levels of detection, except for Hg (0.15 in bluegills and 0.12 in carp) and Se (0.43 and 0.56). As judged by comparisons with data from the National Contaminant Biomonitoring Program and other published surveys, the concentrations of B, Hg, Mo, and Se were moderately elevated in fish from several sites in the San Joaquin Valley. However, only the Se concentrations were positively correlated with water quality variables (e.g., total alkalinity, conductivity, and turbidity) known to be influenced by irrigation return flows. Historical data from one site (Salt Slough), where trace elements in whole fish have been measured since 1969, indicated that Se concentrations increased more than twofold between 1973 and 1977, but thereafter remained near 3.0 μg g−1 (dry weight basis), presumably due to the continuing practice of disposing seleniferous tile drainage water into the most convenient stream channel.

California↗

Declines in reproductive condition of male largemouth bass (Micropterus salmoides) following seasonal exposure to estrogenic endocrine-disrupting compounds

Reproductive abnormalities, that could lead to possible effects at the population level, have been observed in wild fish throughout the United States, with high prevalence in largemouth bass (LMB; Micropterus salmoides ) and smallmouth bass ( Micropterus dolomieu ). Estrone (E1) and atrazine (ATR) are common environmental contaminants often associated with agricultural land use. 17alpha-ethinylestradiol (EE2) is a contaminant associated with wastewater treatment effluent, and a representative, well-studied estrogen commonly used for fish toxicity testing. Our objective was to assess whether early gonad recrudescence in adult fish was a period of sensitivity for alterations in reproductive condition and function. Adult male LMB were exposed from post-spawning to early gonad recrudescence to either a mixture of E1 (47.9 ng/L) + ATR (5.4 µg/L), or EE2 (2.4 ng/L) in outdoor experimental ponds. Gonad samples were collected from fish just prior to the start of exposure (July), at the end of the exposure period (December), the following spring just prior to spawning (April), and post spawning (May). Gonadosomatic index (GSI) was significantly reduced in E1 + ATR-exposed and EE2-exposed males compared to control at every post-exposure time point. Reduced sperm count and sperm motility were observed in the mixture treatment (E1 + ATR) compared to the control. Sperm motility was also reduced in the EE2 treatment. These data together indicate that estrogenic endocrine-disrupting compounds can lessen the reproductive condition of adult male LMB, and that effects of exposure during early gonad recrudescence can persist at least through the subsequent spawning cycle.

International Journal of Molecular Sciences↗

Decreased glutathione S-transferase expression and activity and altered sex steroids in Lake Apopka brown bullheads (Ameriurus nebulosus)

A number of freshwater lakes and reclaimed agricultural sites in Central Florida have been the receiving waters for agrochemical and municipal runoff. One of these sites, Lake Apopka, is also a eutrophic system that has been the focus of several case studies reporting altered reproductive activity linked to bioaccumulation of persistent organochlorine chemicals in aquatic species. The present study was initiated to determine if brown bullheads (Ameriurus nebulosus) from the north marsh of Lake Apopka (Lake Apopka Marsh) exhibit an altered capacity to detoxify environmental chemicals through hepatic glutathione S-transferase (GST)-mediated conjugation as compared with bullheads from a nearby reference site (Lake Woodruff). We also compared plasma sex hormone concentrations (testosterone, 17-?? estradiol, and 11 keto-testosterone) in bullheads from the two sites. Female bullheads from Lake Apopka had 40% lower initial rate GST conjugative activity toward 1-chloro-2,4-dinitrobenzene (CDNB), 50% lower activity towards p-nitrobutyl chloride (NBC), 33% lower activity toward ethacrynic acid (ECA), and 43% lower activity toward ??5-androstene-3,17-dione (??5-ADI), as compared with female bullheads from Lake Woodruff. Enzyme kinetic analyses demonstrated that female bullheads from Lake Apopka had lower GST-catalyzed CDNB clearance than did female Lake Woodruff bullheads. Western blotting studies of bullhead liver cytosolic proteins demonstrated that the reduced GST catalytic activities in female Lake Apopka bullheads were accompanied by lower expression of hepatic GST protein. No site differences were observed with respect to GST activities or GST protein expression in male bullheads. Female Lake Apopka bullheads also had elevated concentrations of plasma androgens (testosterone and 11-ketotestosterone) as compared with females from Lake Woodruff. In contrast, male Lake Apopka bullheads had elevated levels of plasma estrogen but similar levels of androgens as compared with male bullheads from Lake Woodruff. Collectively, our studies indicate the presence of reduced GST protein expression, reduced GST conjugative capacity and altered sex steroid homeostasis in female bullheads from a contaminated field site in Central Florida. The implications of these physiological alterations in terms of pollutant biotransformation and reproduction are discussed. ?? 2001 Elsevier Science B.V. All rights reserved.

Aquatic Toxicology↗

Assessing the toxicity and teratogenicity of pond water in north-central Minnesota to amphibians

Background Incidence of amphibian deformities have increased in recent years, especially in the northern region of the United States. While many factors have been proposed as being responsible for generating deformities (e.g., contaminants, ultraviolet radiation [UV], parasites), no single cause has been definitively established. Methods To determine whether waterborne chemicals are responsible for amphibian deformities in ponds in north-central Minnesota, we deployed semipermeable membrane devices (SPMDs) in an imparted and a reference site to accumulate lipophilic contaminants. We then exposed native tadpoles (northern leopard frogs; Rana pipiens ) to the SPMD extracts combined with two agricultural pesticides (atrazine, carbaryl) at two levels of UV radiation. Results and Discussion UV radiation alone caused a slight increase in hatching success and tadpole growth rate. Deformity rate among hatchlings was high following exposure to SPMD extracts from the reference site in the absence of UV, suggesting that chemicals present at this site are broken down by UV to less harmful forms, or become less bioavailable. Conversely, impacted site SPMD extracts caused hatchling deformities only in the presence of UV, suggesting that UV potentiates the teratogenicity of the compounds present there. Impacted site SPMD extracts significantly increased the number of bony triangles among metamorphs, a common deformity observed at this site. The incidence of skin webbings increased significantly with SPMD extracts from both sites as well as with our pesticide control containing atrazine and carbaryl alone. Conclusions Higher deformity rates among tadpoles reared in the presence of UV radiation and SPMD extracts from sites where deformities are common indicates a chemical compound (or compounds) in the water at this site may be causing the deformities. Recommendations and Outlook It is important to examine the effects of chemical stressors in the presence of other natural stressors (e.g., UV radiation) to gain a better understanding of how multiple stressors work to impact amphibians and amphibian populations.

Environmental Science and Pollution Research↗