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USGS2010

Methylmercury cycling, bioaccumulation, and export from agricultural and non-agricultural wetlands in the Yolo Bypass

This 18-month field study addresses the seasonal and spatial patterns and processes controlling methylmercury (MeHg) production, bioaccumulation, and export from natural and agricultural wetlands of the Yolo Bypass Wildlife Area (YBWA). The data were collected in conjuntion with a Proposition 40 grant from the State Water Resources Control Board in support of the development of Best Management Practices (BMP's) for reducing MeHg loading from agricultural lands in the wetland-dominated Yolo Bypass to the Sacramento-San Joaquin River Delta. The four managemenr-based questions addressed in this study were: 1. Is there a different among agricultural and managfed wetland types in terms of Me Hg dynamic (production, degradation, bioaccumulation, or export)? 2. Does water residence time influence MeHg dynamics? 3. Does the application of sulfate-based fertilizer impact MeHg production rates? 4. Does the presence (or absence) of vegetation influence MeHg production rates? Measurements of MeHg concentrations in sediment, water, and biota (plants, invertebrates, and fish) were made to assess management-level patterns in five wetland types, which included three type of shallowly-flooded agricultural wetlands (white rice, wild rice, and fallow) and two types of managed wetlands (permanently and seasonally flooded). To strengthen our understanding of the processes underlying the seasonal and spatial patterns of MeHg cycling, additional exploratory factors were measured including ancillary sediment and water quality parameters, stable isotope fractionation (oxygen, sulfur, carbon, and nitrogen), photodemethylation rates, and daily-integrated hydrologic budgets. Samples and field data were collected from May 2007 to July 2008, and nearly all sample analyses were completed by September 2008 as per the Quality Assurance Program Plan (QAPP) requirements. Although wetland type was a major factor that drove the study design, within-field hydrology also proved to be an important factor controlling aqueous MeHg and total mercury (THg) concentrations and export. Overall, agricultural wetlands exhibited higher MeHg concentrations in overlying water, sediment, and biota than did managed seasonal and permanent wetlands. This appears to be partly due to higher rates of sediment in microbial production of MeHg on agricultural wetlands during the fall through spring period. Both sulfate- and iron-reducing bacteria have been implicated in the MeHg production process, and both were demonstrably active in all wetlands studied; however, sulfate-reducing bacteria were not stimulated by the addition of sulfate-based fertilizer to agricultural wetlands, suggesting that easily-degraded (labile) organic matter, rather than sulfate, was limiting their activity in these field types. The data suggest that agriculturally-managed soils promoted MeHg production through 1) enhanced microbial activity via higher temperatures and larger pools of labile carbon, and 2) enhanced pools of microbially available inorganic divalent mercury (Hg(II)) resulting from a decrease in reduced-sulfur, solid-phase minerals under oxic or only mildly reducing conditions. MeHg mass balances were assessed by comparing filed-specific MeHg loads for inlets vs. outlet flows. The overall mass balance for MeHg in surface water during the summer irrigation period (June - September 2007) indicated little to no net MeHg export from the six agricultural wetlands taken as a whole. Of the six agricultural wetlands, there was net overall MeHg export from two fields (one fallow and one white rice) during August, and from four of the six fields (one fallow, one white rice, and two wild rice) during September) Over the entire summer irrigation period, two of the fields (one fallow and one wild rive) showed net MeHg export, and the other four fields showed wither net import or no significant change. Rates of measured photomethylation and exchange between sediment and water pools suggest that both processes may be responsible for the lack of MeHg export. Despite significant differences during winter months between fields in surface water concentrations of MeHg, MeHg loads were not calculated in mid-winter because flood waters had overtopped field boundaries and field fidelity could not be established. During the summer 2007 irrigation season, surface water out-flows from agricultural wetlands were 9%-36% of inlet flows, and evaporation rates explained most of this water loss, with infiltration likely accounting for the remainder. Unfiltered aqueous MeHg concentrations increased from <1 ng L -1 in source waters to up to 10 ng L -1 in agricultural wetland drains during the summer irrigation period. Increases in solute concentration caused by evapoconcentration were estimated by determining concentration factors (outflow/inflow) for chloride (a conservative dissolved constituent) and by measuring oxygen isotope ratios ( 18 O/ 16 O, expressed as δ 18 O) in water. Increases in MeHg concentration from inflows-to-outflows exceeded those caused by evapoconcentration on several fields during the summer irrigation season. This was especially true when initial surface water MeHg concentrations were low, as seen in the southern block of fields receiving irrigation water directly from the Toe Drain. The northern block of fields received irrigation water from Greens Lake, which included Toe Drain water plus recirculated drain water from other agricultural fields within the Yolo Bypass and west of the Yolo Bypass; as such, the northern fields showed a smaller percentage increase in MeHg concentration because initial MeHg concentrations in surface water inflows were greater than in inputs to the southern fields. Mercury concentrations in fish were greater in agricultural wetlands white rice and wild rice) than in the two permanently flooded wetlands. Additionally, Hg concentrations in biota showed a general increase from inlets to outlets withing agricultural wetlands, but not within permanent wetlands. This was particular evident in white rice fields where caged western mosquitofish at the outlets had Hg concentrations that were more than 4 times higher than in caged fish held at the inlets. Similar spatial patterns in Hg bioaccumulation in agricultural and permanent wetlands were seen for wild populations of western mosquitofish and Mississippi silversides. In contrast to fish, invertebrates, such as water-boatman (Corixidae) and back swimmers (Notonectidae), had greater Hg concentrations in permanent wetlands than in tempoarirly flooded agricultural wetlands, Fish THg concentrations were weakly correlated with water MeHg,a and not correlated with sediment MeHg. In contrast, invertebrate MeHg concentrations were more strongly correlated with sediment MeHg than with water MeHg concentrations. These results illustrate the complexity of MeHg bioaccumulation through food webs and indicate the importance of simultaneously using multiple biosentinels when monitoring MeHg production and bioaccumulation. Despite high sediment production rates and water concentrations in agricultural wetlands, MeHg export was physically limited by hydrologic export for all wetlands studied. We suggest that load reduction is maximized by limiting water throughout, but that on-site biota exposure is maximized by this loner water residence time. While field-specific hydrologic loads could not be fully quantified during flood conditions in February 2008, we suggest that the primary period of MeHg export from Yolo Bypass Wildlife Area is during those winter flooding periods when overall microbial activity and MeHg production in agricultural soils is fueled by the decomposition of rice straw, and when hydrologic flowthrough is maximal. Local stakeholders participated in two workshops related to this study, demonstrating an interest in understanding factors controlling MeHg production, export, and bioaccumulation. The results of this field study show that permanently flooded, naturally vegetated wetlands are unlikely to a large source of MeHg production within the YBWA, in contrast with agriculturally-managed wetlands. MeHg loading to Toe Drain waters of the Yolo Bypass may be reduced by lowering rated of hydrologic export from agricultural wetlands during the growing season and especially during rice harvest, However, under these water-holding conditions, biota living within agricultural wetlands may thus be exposed to higher MeHg concentrations in surface water, As observed in this study, rapid bioacculumaltion over a 2-month period led to MeHg concentrations in invertebrates and fish more than 6 and 11 times higher, respectively, than proposed TMDL target values to protect wildlife (0.03 ppm ww). The results of this field study, together with the information from YBWA stakeholders, provide a more definitive understanding of how MeHg cycling and bioaccumulation respond to habitat differences and specific management practices. These results directly address 4 core components of CBDA's Mercury Strategy for the Bay-Delta Ecosystem (Wiener et al., 2003a): a) Quantification and evaluation of THg and MeHg sources, b) Quantification of effects of ecosystem restoration on MeHg exposure, c) Assessment of ecological risk, and d) Identification and testing of potential management approaches for reducing MeHg contamination. In addition, the quantitative results reported here assess the effect of current land use practices in the Yolo Bypass MeHg production, bioaccumulation and export, and provide process-based advice towards achieving current goals of the RWQCB-CVR's Sacramento -- San Joaquin Delta Estuary TMDL for Methyl & Total Mercury (Wood et al., 2010b). Further work is necessary to evaluate biotic exposure in the Yolo Bypass Wildlife Area at higher trophic levels (e.g. birds), to quantify winter hydrologic flux of MeHg to the larger Delta ecosystem, and to evaluate rice straw management options to limit labile carbon supplies to surface sediment during winter months. In summary, agricultural management of rice fields -- specifically the periodic flooding and production of easily degraded organic matter -- promotes the production of MeHg beyond rates seen in naturally vegetated wetlands, whether seasonally or permanently flooded., The exported load from MeHg from these agricultural wetlands may be controlled by limiting hydrologic export from fields to enhance on-site MeHg removal processes, but the tradeoff is that this impoundement increases Me Hg exposure to resident organisms.

California↗

USGS2002

Possible sources of nitrate in ground water at swine licensed-managed feeding operations in Oklahoma, 2001

Samples collected and analyzed by the Oklahoma Department of Agriculture, Food, and Forestry from 1999 to 2001 determined that nitrate exceeded the U.S. Environmental Protection Agency maximum contaminant level for public drinking-water supplies of 10 milligrams per liter as nitrogen in 79 monitoring wells at 35 swine licensed-managed feeding operations (LMFO) in Oklahoma. The LMFOs are located in rural agricultural settings where long-term agriculture has potentially affected the ground-water quality in some areas. Land use prior to the construction of the LMFOs was assessed to evaluate the types of agricultural land use within a 500-meter radius of the sampled wells. Chemical and microbiological techniques were used to determine the possible sources of nitrate in water sampled from 10 wastewater lagoons and 79 wells. Samples were analyzed for dissolved major ions, dissolved trace elements, dissolved nutrients, nitrogen isotope ratios of nitrate and ammonia, wastewater organic compounds, and fecal coliform bacteria. Bacteria ribotyping analysis was done on selected samples to identify possible specific animal sources. A decision process was developed to identify the possible sources of nitrate. First, nitrogen isotope ratios were used to define sources as animal, mixed animal and fertilizer, or fertilizer. Second, wastewater organic compound detections, nitrogen-isotope ratios, fecal coliform bacteria detections, and ribotyping were used to refine the identification of possible sources as LFMO waste, fertilizer, or unidentified animal or mixtures of these sources. Additional evidence provided by ribotyping and wastewater organic compound data can, in some cases, specifically indicate the animal source. Detections of three or more wastewater organic compounds that are indicators of animal sources and detections of fecal coliform bacteria provided additional evidence of an animal source. LMFO waste was designated as a possible source of nitrate in water from 10 wells. The source of waste in water from five of those wells was determined through ribotyping, and the source of waste in water from the remaining five wells was determined by detections of three or more animal-waste compounds in the well samples. LMFO waste in the water from wells with unidentified animal source of nitrate does not indicate that LMFO waste was not the source, but indicated that multiple animal sources, including LMFO waste, may be the source of the nitrate.

Water-Resources Investigations Report↗

USGS2017

Mercury contamination and stable isotopes reveal variability in foraging ecology of generalist California gulls

Environmental contaminants are a concern for animal health, but contaminant exposure can also be used as a tracer of foraging ecology. In particular, mercury (Hg) concentrations are highly variable among aquatic and terrestrial food webs as a result of habitat- and site-specific biogeochemical processes that produce the bioaccumulative form, methylmercury (MeHg). We used stable isotopes and total Hg (THg) concentrations of a generalist consumer, the California gull ( Larus californicus ), to examine foraging ecology and illustrate the utility of using Hg contamination as an ecological tracer under certain conditions. We identified four main foraging clusters of gulls during pre-breeding and breeding, using a traditional approach based on light stable isotopes. The foraging cluster with the highest δ 15 N and δ 34 S values in gulls (cluster 4) had mean blood THg concentrations 614% (pre-breeding) and 250% (breeding) higher than gulls with the lowest isotope values (cluster 1). Using a traditional approach of stable-isotope mixing models, we showed that breeding birds with a higher proportion of garbage in their diet (cluster 2: 63–82% garbage) corresponded to lower THg concentrations and lower δ 15 N and δ 34 S values. In contrast, gull clusters with higher THg concentrations, which were more enriched in 15 N and 34 S isotopes, consumed a higher proportion of more natural, estuarine prey. δ 34 S values, which change markedly across the terrestrial to marine habitat gradient, were positively correlated with blood THg concentrations in gulls. The linkage we observed between stable isotopes and THg concentrations suggests that Hg contamination can be used as an additional tool for understanding animal foraging across coastal habitat gradients.

Ecological Indicators↗

USGS2026

Mercury biomagnification across food webs with varying non-native fish presence: Implications for native fish conservation in the upper Colorado River Basin

Environmental contaminants and non-native species introductions negatively affect aquatic ecosystem conservation. Mercury (Hg) accumulates within food webs where it can biomagnify to toxic concentrations, which can be affected by altered trophic relationships from non-native species. This study examined Hg concentrations (n samples = 655) and stable carbon and nitrogen isotope ( n = 746) compositions in native ( n = 313) and non-native ( n = 342) species among four river subbasins (Gunnison, Lower Green, Colorado-Dolores, and White-Yampa), in the Upper Colorado River Basin (UCRB) during 2016 and 2017 to inform the potential combined effects of Hg exposure and non-native species interactions on native fishes of conservation concern. We assessed Hg biomagnification at the fish assemblage level, compared concentrations to risk thresholds for fish and human health, and evaluated niche overlap among trophic levels across subbasins. The generalist-invertivores feeding guild had the lowest Hg concentrations (0.001–0.191 μg g −1 wet weight), and no individuals exceeded the U.S. Environmental Protection Agency aquatic life criterion (0.225 μg g −1 ). Piscivores had the highest concentrations (0.008–1.840 μg g −1 ), and 74% of individuals exceeded the criterion. Biomagnification across trophic levels was observed throughout the UCRB, yet varied by subbasin, with higher magnification factors in the Lower Green and White-Yampa subbasins which also had the highest proportion of non-native species. Stable isotope compositions revealed niche overlap among native and non-native species. Additionally, trophic position varied within species among the subbasins. The proliferation of non-native species has likely reshaped food webs and may have intensified the potential threat Hg poses to native fish recovery and conservation. This study documented increased Hg concentrations relative to past assessments, suggesting that continued monitoring could assist in evaluating trends in Hg accumulation. Particularly studies that focus on sources entering the food web, vectors for accumulation, and competitive interactions among native and non-native species.

Colorado, Utah, Wyoming↗

USGS1981

Biochemistry and metabolism of lake trout: laboratory and field studies on the effects of contaminants

To evaluate the effects of ambient and higher concentrations of PCB's (Aroclor 1254) and DDE in food and water on fry of lake trout ( Salvelinus namaycush ) from Lake Michigan, I measured several biochemical indicators of stress in exposed and unexposed (control) fry. No differences between treatments were observed in oxygen consumption rates or lactate concentrations of unexercised fry, but apparent differences in specific swimming speed and lactate response in fry that swam to exhaustion suggested that exposed fry had lower stamina. Observed differences between biochemical profiles of 1-day-old sac fry reared from eggs originating from lake trout collected off Saugatuck and those originating from eggs of brood stock at the Marquette (Michigan) hatchery may have been caused by organochlorine contamination or by genetic and dietary differences between the parental stocks. Activity of the enzyme allantoinase was measured in juvenile and adult lake trout as an indicator of sublethal effects of Great Lakes contaminants. The 50% inhibition of allantoinase in vitro occurred at 6.0 mg/L Cu++, 6.7 mg/L Cd++, 34 mg/L Hg++, and 52 mg/L Pb++. Allantoinase was not affected by in vitro exposure to PCB's up to 7 μg/g, or DDE or DDT up to 10 μg/g; however, in vivo exposure resulting in 2.6 μg/g PCB's in the whole fish activated allantoinase slightly (10% significance level). Allantoinase activity was negatively correlated with total length for fish from Lake Michigan but not for fish from Lake Superior or from laboratory stocks. Mercury, PCB's, and DDT, possibly acting in combination with each other and with additional contaminants, may be the cause of the negative correlation of allantoinase activity with size in Lake Michigan lake trout.

Book chapter↗

USGS2022

Assessing per- and polyfluoroalkyl substances (PFAS) in sediments and fishes in a large, urbanized estuary and the potential human health implications

The primary source of chronic exposures to per- and polyfluoroalkyl substances (PFASs) in humans is through the ingestion of contaminated foods and drinking water, with fish and other seafood being a major contributor. Nevertheless, there is scant literature on the dietary exposure to PFASs for the general United States (U.S.) population. The Tampa Bay (Florida, USA) region has the highest population density in the State and communities and their attendant support services are arrayed in an urban to semi-rural continuum from the head of the Bay to the ocean mouth. Tampa Bay supports productive recreational and commercial fisheries, providing a diverse community of species. A variety of potential PFAS sources surround Tampa Bay including airports, industry, wastewater treatment plants, fire-fighting training areas and military installations. The objective of this study is to quantify PFASs in sediment and fishes collected from Tampa Bay to further estimate human health risks from dietary exposures. Sediment ( n = 17) and fish (24 species, n = 140) were collected throughout Tampa Bay in 2020 and 2021 and analyzed for 25 PFAS compounds. Concentrations of PFASs in sediments and edible tissues of fish ranged from 36.8 to 2,990 ng kg -1 (dry weight) and 307 to 33,600 ng kg -1 (wet weight), respectively. Generally, levels were highest in Old Tampa Bay and decreased south towards the Gulf of Mexico. Profiles in both matrices were generally dominated by perfluorooctane sulfonic acid (PFOS) with variations by location. Estimated human health risks from the consumption of contaminated fish collected in Tampa Bay exceeded concentration thresholds for minimum risk levels (MRLs) and tolerable weekly intake (TWIs) values for adults and youths. Additionally, concentrations of PFOS in edible fish tissues of several recreationally important species collected in Tampa Bay exceeded consumption guideline levels established by several governmental agencies. In the current context, the elevated levels of PFAS in Tampa Bay and the exceedances of available thresholds for potential human health risks are a cause for concern and justify a more intensive examination especially for more heavily utilized species, particularly those used in subsistence-level fishing, which, as elsewhere may be significantly under documented.

Florida↗

USGS1986

DDE, DDT + dieldrin: Residues in American kestrels and relations to reproduction

Captive American kestrels (Falco sparverius) given long-term dietary dosages of DDT and dieldrin in combination, at low and high rates, were compared with controls to determine the effects of the toxicants on reproductive success and eggshell thickness. Additional kestrels were dosed with DDE to determine its effect on shell thickness. Tissues of birds that died or were sacrificed, and eggs, were analyzed for DDE, DDD, DDT, and dieldrin. Eight paired birds, mostly males, given a high dosage of DDT + dieldrin died of dieldrin poisoning. Three periods of heavy mortality involving only dosed birds, which occurred in summer 1966, fall 1967, and spring 1968, followed temperature declines and other stress factors. Organochlorine concentrations in tissues of sacrificed birds and eggs in all units of the DDT + dieldrin study were significantly different among treatments. Residue concentrations in tissues of birds on high dosage of DDT + dieldrin were about 3 times higher than those on low dosage, a difference similar to the relative magnitude of the dose rates. Concentrations of some toxicants, especially DDE, were significantly higher in tissues of males than females, although these differences were difficult to interpret because males generally were sacrificed later than females. Concentrations in tissues and eggs of dosed yearlings, placed on clean food 7 to 9 weeks before pairing, were often significantly lower than in those yearlings that remained on dosage. Concentrations of each toxicant were usually highly correlated (r > 0.85) among tissues, especially for DDE and dieldrin. Organochlorine concentrations in brains and eggs could be predicted from concentrations in carcasses. DDE and dieldrin concentrations in eggs were about one-half those in carcasses, DDD about one-seventh, and DDT 1.5 to 2 times higher in eggs than carcasses. Eggshells of DDT + dieldrin-dosed kestrels were 6-23% thinner than eggshells of corresponding controls in different groups and years. Organochlorine concentrations in eggs and tissues of females were poorly correlated with shell thickness. Of the four toxicants in eggs, DDE was significantly and most closely correlated with fledging success. Interpretation of direct comparisons between our DDT + dieldrin studies and most current field situations are difficult because contaminant profiles in our birds are unlike those in most field samples.

Fish and Wildlife Technical Report↗

USGS2013

Mercury bioaccumulation in fishes from subalpine lakes of the Wallowa-Whitman National Forest, northeastern Oregon and western Idaho

Mercury (Hg) is a globally distributed pollutant that poses considerable risks to human and wildlife health. Over the past 150 years since the advent of the industrial revolution, approximately 80 percent of global emissions have come from anthropogenic sources, largely fossil fuel combustion. As a result, atmospheric deposition of Hg has increased by up to 4-fold above pre-industrial times. Because of their isolation, remote high-elevation lakes represent unique environments for evaluating the bioaccumulation of atmospherically deposited Hg through freshwater food webs, as well as for evaluating the relative importance of Hg loading versus landscape influences on Hg bioaccumulation. The increase in Hg deposition to these systems over the past century, coupled with their limited exposure to direct anthropogenic disturbance make them useful indicators for estimating how changes in Hg emissions may propagate to changes in Hg bioaccumulation and ecological risk. In this study, we evaluated Hg concentrations in fishes of high-elevation, sub-alpine lakes in the Wallowa-Whitman National Forest in northeastern Oregon and western Idaho. Our goals were to (1) assess the magnitude of Hg contamination in small-catchment lakes to evaluate the risk of atmospheric Hg to human and wildlife health, (2) quantify the spatial variability in fish Hg concentrations, and (3) determine the ecological, limnological, and landscape factors that are best correlated with fish total mercury (THg) concentrations in these systems. Across the 28 study lakes, mean THg concentrations of resident salmonid fishes varied as much as 18-fold among lakes. Importantly, our top statistical model explained 87 percent of the variability in fish THg concentrations among lakes with four key landscape and limnological variables— catchment conifer density (basal area of conifers within a lake’s catchment), lake surface area, aqueous dissolved sulfate, and dissolved organic carbon. The basal area of conifers within a lake’s catchment was by far the most important variable explaining fish THg concentrations, with an increase in THg concentrations of more than 400 percent across the forest density spectrum. Across all study lakes, fish THg concentrations ranged from 0.004 to 0.438 milligrams per kilogram wet weight (mg/kg ww). Only a single individual fish sample exceeded the U.S. Environmental Protection Agency’s (USEPA) human health tissue residue criteria of 0.3 mg/kg ww. However, 54 percent of fish (N=177) exceeded the more stringent tissue residue criteria (0.04 mg/kg ww) adopted by the Oregon Department of Environmental Quality to better protect subsistence fishers. Additionally, 2 and 10 percent of fish exceeded levels associated with reduced common loon reproduction and behavior, respectively. Whereas 25 and 68 percent of fish sampled exceeded concentrations deemed protective of mink and kingfisher, respectively. These results suggest that THg concentrations may be present in these lakes at levels associated with ecological risk. It is important to note however, that accurate inference on potential impairment cannot be made within the context of this study design and further research is needed to better quantify these risks.

Oregon;Idaho↗

USGS2010

The quality of our nation's waters: Nutrients in the nation's streams and groundwater, 1992-2004

National Findings and Their Implications Although the use of artificial fertilizer has supported increasing food production to meet the needs of a growing population, increases in nutrient loadings from agricultural and, to a lesser extent, urban sources have resulted in nutrient concentrations in many streams and parts of aquifers that exceed standards for protection of human health and (or) aquatic life, often by large margins. Do NAWQA findings substantiate national concerns for aquatic and human health? National Water-Quality Assessment (NAWQA) findings indicate that nutrient concentrations in streams and groundwater in basins with significant agricultural or urban development are substantially greater than naturally occurring or “background” levels. For example, median concentrations of total nitrogen and phosphorus in agricultural streams are about 6 times greater than background levels. Findings also indicate that concentrations in streams routinely were 2 to 10 times greater than regional nutrient criteria recommended by the U.S. Environmental Protection Agency (USEPA) to protect aquatic life. Such large differences in magnitude suggest that significant reductions in sources of nutrients, as well as greater use of land management strategies to reduce the transport of nutrients to streams, are needed to meet recommended criteria for streams draining areas with significant agricultural and urban development. Nitrate concentrations above the Federal drinking-water standard—or Maximum Contaminant Level (MCL)—of 10 milligrams per liter (mg/L, as nitrogen) are relatively uncommon in samples from streams used for drinking water or from relatively deep aquifers; the MCL is exceeded, however, in more than 20 percent of shallow (less than 100 feet below the water table) domestic wells in agricultural areas. This finding raises concerns for human health in rural agricultural areas where shallow groundwater is used for domestic supply and may warn of future contamination of deeper groundwater pumped from public‑supply wells. Are levels of nutrients in water increasing or decreasing? A decadal assessment of trends in concentrations of nitrogen and phosphorus from about 1993 to 2003 shows minimal changes in those concentrations in the majority of studied streams across the Nation, and more upward than downward trends in concentrations at sites with changes. These findings underscore the need for reductions in nutrient inputs or management strategies that would reduce transport of nutrients to streams. Upward trends were evident among all land uses, including those only minimally affected by agricultural and (or) urban development, which suggests that additional protection of some of our Nation’s most pristine streams warrants consideration. The median of nitrate concentrations in groundwater from 495 wells also increased significantly from 3.2 to 3.4 mg/L (6 percent) during about the same period, and the proportion of wells with concentrations of nitrate greater than the MCL increased from 16 to 21 percent. Nitrate concentrations in water in deep aquifers are likely to increase during the next decade as shallow groundwater with elevated concentrations moves downward. The potential for future contamination of the deep aquifers requires attention because these aquifers commonly are used for public water supply, and because restoration of groundwater is costly and difficult. Long-term and consistent monitoring of nutrients, improved accounting of nutrient sources, and improved tracking and modeling of climatic and landscape changes will be essential for distinguishing trends in nutrient concentrations, understanding the causes of those trends, and accurately tracking the effectiveness of strategies implemented to manage nutrients.

Circular↗

USGS1993

1993 Annual Report: San Francisco estuary regional monitoring program for trace substances

This first annual report of the San Francisco Estuary Regional Monitoring Program contains the results of monitoring measurements made in 1993. Measurements of conventional water quality parameters and trace contaminant concentrations were made at 16 stations throughout the Estuary three times during the year: the wet period (March), during declining Delta outflow (May), and during the dry period (September). Water toxicity tests were conducted at 8 of those stations. Measurements of sediment quality and contaminant concentrations were made at the same 16 stations during the wet and dry sampling periods. Sediment toxicity was measured at 8 of those stations. Transplanted, bagged bivalve bioaccumulation and condition was measured at 11 stations during the wet and dry sampling periods. Water Monitoring. Total or near-total (dissolved + particulate, see text) arsenic, cadmium, selenium, and dissolved (0.45 µm filtered) arsenic, cadmium, copper, nickel, silver, and zinc in water were highest in the South Bay. In general, dissolved metals in water were usually lowest in the Central Bay due to ocean influences. Near-total nickel and total mercury in water were highest in the northern estuary (San Pablo and Suisun Bays). Dissolved chromium and lead were highest at the Sacramento and San Joaquin River confluence stations. Six of the ten dissolved trace metals were highest in March during high runoff. Dissolved and total arsenic, selenium, and near-total cadmium were highest in September. Concentrations of trace organic contaminants are reported for the March sampling period. Total PAHs and PCBs were highest in the South Bay, but PCBs were also high in the Napa River. Dissolved PAHs were highest in the Central Bay, and dissolved PCBs were highest in the Napa River. Total and dissolved pesticides were highest in the Sacramento River and in the Extreme South Bay. Concentrations of trace elements in water (except selenium) were usually closely related with other environmental parameters. Total or near-total metals concentrations in water were most often associated with the amount of particulate material (TSS) in the water. Dissolved concentrations were usually associated with salinity or dissolved organic carbon (DOC) content. Dissolved PAHs were well correlated with TSS, but dissolved and total trace organic contaminants were poorly correlated with other water parameters. Based on deviations from conservative mixing of fresh and salt water, three different patterns of possible sources of metals were identified in 1993. For dissolved chromium and lead, rivers and local runoff appeared to be important sources. For dissolved arsenic, cadmium, copper, and nickel year-round inputs from the South Bay appeared to be important sources. Dissolved mercury, selenium, and zinc were associated with local runoff in the South Bay during the wet period. Dissolved silver did not fit any of these patterns. Although most contaminant concentrations were below water quality objectives, several trace contaminants were above the objectives at some stations. Comparisons to water quality objectives are used as a guide for evaluation of contaminant concentrations, but there are some differences in the way the RMP data are measured and that prescribed for regulatory purposes (see text). Concentrations of 5 metals in water were above EPA or Regional Basin Plan water quality objectives at six stations (see Table 30). Most of these elevated levels occurred at the northern estuary stations. Total PCB concentrations were above EPA human health objectives at all RMP stations. The pesticides chlordane, dieldrin, and DDTs were above the EPA objectives at several RMP stations, particularly at the northern-most, and river confluence stations. Although some of the contaminant concentrations were above water quality objectives, water toxicity tests (96 hour algal growth and 48 hour bivalve larval development tests) did not indicate toxicity (sometimes inconclusive) associated with the water samples collected at any of the RMP stations in 1993. Exposure to Bay San Francisco Estuary Regional Monitoring Program Regional Monitoring Program 1993 Report ii water actually enhanced algal growth at most stations. In addition to the Estuary-wide sampling, the Sacramento and San Joaquin Rivers were sampled upstream from their confluence. Stations in each river were sampled six times over a 6 week period of high flows. In the Sacramento River, seven of the ten dissolved metals measured had concentrations lower than those measured at the river confluence stations. Some metals concentrations in the San Joaquin River were higher, and some were lower than concentrations from the river confluence station. Metals concentrations in the Sacramento River were poorly related to river flow because the station at Rio Vista is under considerable tidal influence. In the San Joaquin River, flows were inversely related to 7 of 10 total metals concentrations. Sediment Monitoring. Concentrations of silver, mercury, and lead in sediment were highest in the South Bay. However, concentrations of most trace metals in sediments were highest in the northern estuary at stations with the finest (silt, clay) sediments. The northern estuary stations with the coarsest (sand, shell) sediments generally had the lowest metals concentrations. There were differences in concentrations of cadmium, lead, and selenium in sediments between the sampling periods, but no consistent trend as to which sampling period had higher values. In September, PAHs and PCBs in sediments were highest in the Central Bay, but pesticides in sediments were highest in the northern estuary and Extreme South Bay. NOAA’s Median Effects Ranges (ERM) for sediments were used as a guide for evaluation of sediment contaminant concentrations. Nickel was the only trace contaminant in sediment above the ERM guidelines, and it was high at all RMP stations. These high levels are probably due to natural, geologic sources. Although sediment contaminant concentrations were below ERMs, sediment toxicity tests (10 day amphipod mortality, and 48 hour bivalve larval development in elutriates) indicated toxicity at all stations tested. Sediment factors that could have caused the toxicity were not investigated. Bivalve Bioaccumulation. Mussels, oysters, and freshwater clams were transplanted to the RMP stations to evaluate bioaccumulation of trace substances. Trace metals were bioaccumulated at nearly all RMP stations. However, arsenic, lead, and mercury did not appear to bioaccumulate. There was generally more bioaccumulation during the dry season than during the wet season. In September, PAHs, PCBs, and pesticides accumulated in all samples. Bioaccumulation of PAHs and pesticides was generally highest at the river confluence stations, and the Napa River. PCBs accumulated most at Redwood Creek. There were substantial differences in the degree of bioaccumulation among the species. Oysters appeared to accumulate higher concentrations of trace metals than the other species, especially copper, which may be a natural phenomenon. There are no established tissue contaminant standards for trace metal and organic contaminants. Therefore, comparisons to Median International Standards (MIS) for human consumption, or U.S. Food and Drug Administration (USFDA) action levels for trace organics are used to evaluate the bioaccumulation results. Concentrations of selenium were higher than MIS guidelines at all stations during the wet season. Other trace metal concentrations were higher than MIS guidelines at various stations during one or the other sampling period. However, none of the bivalves contained concentrations above the USFDA or National Academy of Sciences (NAS) guidelines for trace organic contaminants. The transplanted bivalves survived well at all stations except in the Napa River where less than 35% survived during both sampling seasons. Measures of bivalve condition (dry weight, shell volume) indicated that bivalves deployed in the Central Bay grew significantly, but those at most other stations actually lost weight. Whether these differences were due to natural causes such as salinity or food supply, or to contamination, was not determined. Pilot Studies. Two pilot monitoring studies were conducted in 1993. A pilot study of Estuary hydrography and phytoplankton was conducted by scientists from the U.S. Summary Geological Survey in Menlo Park and U.C. Davis. Water column profiles at up to 37 stations were monitored along a transect of the Estuary run monthly between the South Bay and the Delta. The primary objective of this study was to define physical (salinity, temperature, suspended particulate matter, and light penetration), chemical (dissolved oxygen) and biological (chlorophyll a) characteristics of Estuary water that may influence other chemical and biological reactions. A second objective was to investigate planktonic indicators of ecosystem structure and function. The data collected in 1993 showed the extent and duration of the spring phytoplankton bloom in the South Bay, other localized blooms in the northern estuary, the stratification and mixing associated with the entrapment zone in the northern estuary, and mixing in the Estuary resulting from the high rainfall in 1993. Knowledge of the duration and extent of these natural features of the Estuary provide context for interpretation of the RMP contaminant data collected only 3 times per year. Another pilot study of suspended sediment transport processes was conducted by the USGS in Sacramento. This study used continuous recording sensors at Point San Pablo and the Bay Bridge to measure the amount of suspended sediment in the water at mid-depth and near the bottom, as well as tide height. The objectives of this study were to estimate which factors determine suspended solids concentrations in the Central Bay and to collect time series of suspended solids that are appropriate for continuous monitoring of suspended solids and for calibration and validation of numerical models. The investigators determined that spring tides accounted for most of the variation in suspended solids concentrations at the stations monitored, not runoff from the Sacramento or San Joaquin Rivers, or semidiurnal and diurnal tides. Comparisons were also made between measurements made by the continuous recordings and the RMP samples collected during the regular monitoring cruises. The different ways of measuring TSS were generally comparable, however only 3 measurements per year as made by the RMP could not provide the information of TSS variation actually occurring in the Estuary. This information is important because as shown by the RMP data, total contaminant concentrations in Estuary water is largely dependent on the TSS in the water. This implies that the RMP measurements alone cannot determine accurately the range of contaminant concentrations without better characterizing the dynamics of TSS. The RMP Pilot Studies are important to the developing RMP because they will help put RMP measurements into the perspective of Estuary processes and mechanisms at other time scales. The studies can relate those processes to the RMP measurements and will facilitate revision of sampling design and interpretation. Summaries of other monitoring activities pertinent to regional monitoring are also included in the Report: a description of the Regional Board’s Bay Protection Studies, the Sacramento Coordinated Monitoring Program, and a wetlands monitoring plan are included.

California↗

USGS2023

Selenium hazards in the Salton Sea environment—Summary of current knowledge to inform future wetland management

Quaternary marine and continental shales in the western United States are sources of selenium that can be loaded into the aquatic environment through mining, agricultural, and energy production processes. The mobilization of selenium from shales through agricultural irrigation has been recognized since the 1930s; however, discovery of deformities in birds and other wildlife using agricultural habitats during the 1980s spurred studies to determine the extent and effects of the contamination. Through these early studies, researchers determined that biota in the Salton Sea drainage basin was at risk from legacy selenium contamination in the Colorado River watershed. The Salton Sea and its surrounding managed and unmanaged wetlands provide vital inland habitat and trophic support for diverse assemblages of resident and migratory wildlife, and understanding regional selenium hazards for these trust species is a priority for many Federal and State agencies. The modern Salton Sea is a shallow, landlocked saline lake in Riverside and Imperial Counties (not shown) of California that is sustained by irrigation return and perennial river inflow. Changes in water transfer agreements under the 2003 Quantification Settlement Agreement (QSA) have resulted in reduced irrigation flow, declining lake levels, and the evolution of unmanaged wetlands in areas where drains and rivers no longer reach the Salton Sea. These wetlands provide additional habitat for some species of concern, but their potential to increase selenium hazards for trust species is largely unknown. From the 1980s to 2020, efforts to document selenium contamination and effects throughout the region have resulted in a considerable amount of selenium data from the Salton Sea and its surrounding drainage basin; however, no long-term (greater than 20 years), consistent sampling program has been established, and all data have been collected by different entities using a variety of protocols and analytical techniques. This lack of coordination has been previously documented in regional management plans and has led to difficulty in reliably assessing selenium hazards in the Salton Sea environment. This report provides a summary of the available disparate selenium information collected from water, sediment, and biota in the Salton Sea region since the 1980s and to identify data gaps that need to be filled to understand the potential effects of selenium on species of concern, including federally endangered desert pupfish ( Cyprinodon macularius ) and Yuma Ridgway’s Rail ( Rallus obsoletus yumanensis; formerly Yuma Clapper Rail, Rallus longirostris yumanensis ). Available data from the Salton Sea drainage basin show that water from the Colorado River has the lowest selenium concentration of all surface water sources. All other surface water flowing into the Salton Sea has elevated selenium concentrations due to evaporation and evapotranspiration that occurs in agricultural fields and associated water delivery infrastructure or leaching of selenium from irrigated farmland soils. The Salton Sea has lower selenium concentrations because of various biogeochemical processes that recycle selenium into the sediment or volatilize it to the atmosphere; however, these mechanisms are not well defined, and it is not clear if selenium cycling will change in response to possible changes in the oxidation state of the Salton Sea bottom waters as water levels decline. Agricultural drains have the highest average selenium concentrations, but few drains have been sampled since changes in irrigation practices have occurred (due to the 2003 QSA). Groundwater selenium concentrations are variable; some wells south of the Salton Sea have selenium concentrations as high as 300 micrograms per liter (µg/L), whereas selenium concentrations are below detection in other wells. Groundwater and surface-water geothermal discharge zones around the margins of the Salton Sea and in unmanaged wetlands have not been studied in detail, and published selenium measurements are not available for these surface features. Selenium concentrations in the sediment of the Salton Sea drainage basin are highest in wetland particulate organic matter and the Salton Sea lakebed, indicating that removal of selenium from the water to the sediment has been a primary mechanism for keeping selenium concentrations low in the water column. Sediment selenium concentrations in wetlands are lower than in the Salton Sea but higher than inflowing drains and rivers, indicating the lentic wetland sites also may be important sinks for selenium because of biogeochemical processes. Sediment selenium data have not been collected in agricultural drains since changes in irrigation practices occurred (due to the 2003 QSA), and it is unknown if selenium sequestration from the water column has changed in these systems. We divided biological data into broad taxonomic categories, including primary producers, invertebrates, herpetofauna, mammals, fishes, and birds to facilitate evaluation of selenium concentrations and spatiotemporal trends observed in the Salton Sea. Overall, selenium concentrations were substantially greater in algae samples compared to all vascular plant samples combined. Median selenium concentrations in several invertebrate taxa (Chironomidae, Formicidae, Corixidae, Corbiculidae and Nereididae, and Decapoda) exceeded the maximum suggested dietary threshold of 3.0–4.0 micrograms per gram (µg/g) dry weight (dw) for predators consuming invertebrates in aquatic food webs. The greatest number of samples were collected from fish, and selenium distributions among species and locations showed that the range for most samples was lower than the U.S. Environmental Protection Agency selenium criterion for aquatic life (8.5 µg/g dw whole body, 11.3 µg/g dw fillets). The median selenium concentrations for whole body fish were below the selenium criterion in most locations, except for bairdiella ( Bairdiella icistia ) from the Salton Sea and irrigation drains, a few individual tilapia spp. (family Cichlidae, including genera Tilapia, Oreochromis , and their hybrids) from the river and river outlets, and several western mosquitofish ( Gambusia affinis ) and sailfin molly ( Poecilia latipinna ) from irrigation drain outlets. For avian samples combined among years and locations, median selenium concentrations in livers from all families except waders and Ibis (family Threskiornithidae) were higher than levels expected to cause selenium toxicosis (10–20 µg/g dw), and all median egg concentrations were above or near 6.0 μg/g dw, which is a conservative threshold value for reproductive impairment. Most knowledge gaps we identified for water, sediment, and biota were interrelated, and the use of integrated approaches to address knowledge gaps can provide greater insight into the drivers behind selenium hazards. Integrated water, sediment, and biota studies could help identify cost-effective management solutions that serve multiple purposes. A comprehensive analysis of the hydrology, biogeochemistry, and food-web processes in wetlands and other habitats can inform predictive models to identify drivers of selenium bioavailability, uptake from the environment and subsequent trophic transfer, ultimately forming the basis for experimental habitat management manipulations to minimize selenium hazards to wildlife. Furthermore, a comprehensive, long-term sampling and analytical laboratory plan would enable comparison of data among different entities that are sampling at the Salton Sea. Such efforts are well suited to help fill knowledge gaps that preclude understanding of selenium hazards and future management options for biota using Salton Sea habitats, including newly formed wetlands throughout the region. All data compiled for this report are available in two U.S. Geological Survey data releases: Groover and others (2022) for water and sediment samples and De La Cruz and others (2022) for biological samples. The data releases include all publicly available data for selenium concentrations in water, sediment, and biological samples collected in and around the Salton Sea, including the Coachella and Imperial Valleys. The data releases also include previously unpublished data.

California↗

USGS2012

Bioaccumulation and toxicity of selenium during a life-cycle exposure with desert pupfish (Cyprinodon macularius)

Populations of desert pupfish ( Cyprinodon macularius ; pupfish), a federally-listed endangered species, inhabit irrigation drains in the Imperial Valley agricultural area of southern California. These drains have varying degrees of selenium (Se) contamination of water, sediment, and aquatic biota. Published Se toxicity studies suggest that these levels of Se contamination may pose risk of chronic toxicity to Se-sensitive fish, but until recently there have been no studies of the chronic toxicity of Se to desert pupfish. A life-cycle Se exposure with pupfish was conducted to estimate dietary and tissue thresholds for toxic effects of Se on all life stages. The dietary exposure was based on live oligochaete worms ( Lumbriculus variegatus ) dosed with Se by a laboratory food chain based on selenized yeast. Oligochaetes readily accumulated Se from mixtures of selenized and control yeasts. The protocol for dosing oligochaetes for pupfish feeding studies included long-term (at least 28 days) feeding of a low-ration of yeast mixtures to large batches of oligochaetes. Oligochaetes were dosed at five Se levels in a 50-percent dilution series. Pupfish were simultaneously fed Se-dosed oligochaetes and exposed to a series of Se concentrations in water (consisting of 85 percent selenate and 15 percent selenite) to produce exposures that were consistent with Se concentrations and speciation in pupfish habitats. The nutritional characteristics of oligochaete diets were consistent across the range of oligochaete Se concentrations tested. The life-cycle exposure started with laboratory-cultured juvenile pupfish that were exposed to Se through sexual maturation and reproduction (150 days; F0 exposure). The Se exposure continued with eggs, larvae, and juveniles produced by Se-exposed parents (79 days; F1 exposure). Selenium exposure (water and diets), Se bioaccumulation (whole-body and eggs), and toxicity endpoints (juvenile and adult survival and growth; egg production and hatching success, larval survival and deformities) were documented throughout the life-cycle study. Selenium concentrations in water (as much as 52 micrograms per liter [μg/L]) and diets (as much as 53 micrograms per gram [μg/g], on a dry weight basis) bracketed concentrations reported in pupfish habitats. Juvenile F0 pupfish rapidly accumulated Se and bioaccumulation models indicated that pupfish had reached more than 97 percent of maximum whole-body Se concentrations by the time they reached reproductive maturity. Adult pupfish accumulated whole-body Se concentrations that averaged about 40 percent of those in the oligochaete diets. Selenium concentrations in eggs and F1 juveniles were similar to or slightly greater than Se concentrations in F0 adults. Juvenile F0 pupfish contained selenomethionine fractions (62–71 percent of whole-body Se) greater than the average reported for wild pupfish from the Imperial Valley (53 percent). Selenium exposure had minimal effects on survival or growth of juvenile and adult pupfish. There was evidence of toxic effects on pupfish in the highest Se treatment (Se–5), including reduced growth of F0 and F1 juvenile pupfish (17–21 percent less than controls) on some sampling dates. These growth reductions did not persist to subsequent sampling dates, but reduced growth of F1 pupfish in the Se–5 treatment was associated with reduced survival (12 percent less than controls). Egg production was greatest in the controls and decreased with increasing Se exposure, reaching a minimum (51 percent less than controls) in the Se–4 treatment, but egg production was reduced by only 24 percent in the Se–5 treatment, a lesser reduction than in other Se treatments except Se–1. There was no statistically significant overall effect of Se treatment on mean pupfish egg production, reflecting large variation among replicates and among sampling dates. However, comparisons of daily mean egg production for 23 sampling dates indicated that egg production in each of 5 Se treatments was significantly less than controls on multiple (3–7) sampling dates, but no mean for any Se treatment was significantly greater than controls on any date. Significant reductions in daily egg production occurred mainly during the middle of the study and egg production increased in several Se treatments during the final 2 weeks of the study. These results suggest that pupfish egg production, although a highly variable endpoint, was adversely affected by elevated Se exposure. Neither egg hatching success nor survival of F1 larvae indicated clear evidence of Se toxicity. Egg hatching success did not differ significantly among treatments, with means ranging from 84–91 percent. The frequency of morphological deformities (primarily spinal deformities) was greater in larvae 10 days post-fertilization (dpf) from a preliminary reproduction study than in older larvae (14 dpf) from the main reproduction study. The frequency of larval deformities was generally greater in Se treatments than controls, but mean frequencies did not differ significantly among treatments. Survival of F1 larvae to 21 dpf was not reduced significantly by parental Se exposure, but the Se–5 treatment had the lowest larval survival (84 percent), and lowest combined egg hatching and larval survival (76 percent). Results of the Se treatments indicate that pupfish were insensitive to Se toxicity through most of their life cycle. Consistent toxic effects on survival and growth of juvenile and adult pupfish (defined as at least 10 percent reduction compared to controls) occurred only in treatment Se–5, which had a mean dietary Se concentration of 52 μg/g and a mean pupfish whole-body Se concentration of 27 μg/g. These apparent toxicity thresholds for growth and survival rank among the least sensitive chronic Se toxicity values reported for nonreproductive endpoints in freshwater fish. Comparisons of these thresholds to surveys of Se concentrations in the Imperial Valley suggest that risks of Se toxicity are low in pupfish habitats. The dietary threshold was about twice as high as the greatest mean Se concentrations reported in midge larvae from seven sites in the Imperial Valley. Whole-body thresholds were greater than mean whole-body Se concentrations reported for field-collected pupfish from three sites and for the sailfin molly (Poecilia latipinna), a potential bioaccumulation surrogate for pupfish, from seven sites. Reduced egg production, although highly variable, was the most sensitive response of pupfish to Se exposure. Toxic effects on egg production (reductions of 24–51 percent relative to controls) occurred in the four highest Se treatments, corresponding to reproductive toxicity thresholds of 7.3 μg/g for Se in diet, 3.4 μg/g in pupfish (whole body), and 4.4 μg/g in pupfish eggs. These thresholds are substantially lower than published Se toxicity values for reproductive effects in other freshwater fish (for example, 17–24 μg/g in eggs). Reduced egg production has not been reported as a sensitive endpoint in Se toxicity studies, although abnormal ovarian development has been reported in Se-exposed fish, and reduced egg production has been reported as a sensitive response of other Cyprinodon pupfish to other environmental stressors. Selenium concentrations in tissues of pupfish, mollies, and diet items from Imperial Valley sites frequently exceeded concentrations associated with reduced pupfish egg production in the laboratory study. Reduced egg production may limit the ability of pupfish populations to persist and recover in Se-contaminated habitats in the Imperial Valley and elsewhere in their limited range. However, these apparent risks of Se toxicity are not supported by recent surveys of desert pupfish populations in the Imperial Valley. These surveys indicated that desert pupfish made up a small, but variable, component of fish communities in Imperial Valley habitats, including sites with increased levels of Se exposure, and that pupfish distribution and population density indicated no clear relationships with Se concentrations in diets or fish tissues. Additional studies could determine the role of egg production in the maintenance and recovery of desert pupfish populations in Se-contaminated habitats.

Scientific Investigations Report↗

USGS2008

Davis Pond freshwater prediversion biomonitoring study: freshwater fisheries and eagles

In January 2001, the construction of the Davis Pond freshwater diversion structure was completed by the U.S. Army Corps of Engineers. The diversion of freshwater from the Mississippi River is intended to mitigate saltwater intrusion from the Gulf of Mexico and to lessen the concomitant loss of wetland areas. In addition to the freshwater inflow, Barataria Bay basin would receive nutrients, increased flows of sediments, and water-borne and sediment-bound compounds. The purpose of this biomonitoring study was, therefore, to serve as a baseline for prediversion concentrations of selected contaminants in bald eagle ( Haliaeetus leucocephalus ) nestlings (hereafter referred to as eaglets), representative freshwater fish, and bivalves. Samples were collected from January through June 2001. Two similarly designed postdiversion studies, as described in the biological monitoring program, are planned. Active bald eagle nests targeted for sampling eaglet blood (n = 6) were generally located southwest and south of the diversion structure. The designated sites for aquatic animal sampling were at Lake Salvador, at Lake Cataouatche, at Bayou Couba, and along the Mississippi River. Aquatic animals representative of eagle prey were collected. Fish were from three different trophic levels and have varying feeding strategies and life histories. These included herbivorous striped mullet ( Mugil cephalus ), omnivorous blue catfish ( Ictalurus furcatus ), and carnivorous largemouth bass ( Micropterus salmoides ). Three individuals per species were collected at each of the four sampling sites. Freshwater Atlantic rangia clams ( Rangia cuneata ) were collected at the downstream marsh sites, and zebra mussels ( Dreissena spp.) were collected on the Mississippi River. The U.S. Geological Survey (USGS) Biomonitoring of Environmental Status and Trends (BEST) protocols served as guides for fish sampling and health assessments. Fish are useful for monitoring aquatic ecosystems because they accumulate pesticides and other contaminants. Biomarker data on individual fish, generated at the USGS National Wetlands Research Center (Lafayette, La.), included percent white blood cells in whole blood, spleen weight to body weight ratio, liver weight to body weight ratio, condition factor, splenic macrophage aggregates, and liver microsomal 7-ethoxyresorufin-o-deethylase (EROD) activity. Fish age was estimated by comparing total lengths with values from the same species in the Southeast United States as determined from the literature. Contaminant analyses were coordinated by the U.S. Fish and Wildlife Service (USFWS) Analytical Control Facility (Laurel, Md.), where residues of organochlorine (OC) pesticides, total polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), aliphatic hydrocarbons (AHs), and trace elements were determined. The organic contaminant data were generated at the Mississippi State University Chemical Lab (Mississippi State, Miss.), and the inorganic contaminant data were generated by the Texas A&M University Geochemical and Environmental Research Group (College Station, Tex.). Statistical tests were performed to assess relationships among contaminants, fish age, fish species, and collection sites. Trends in interspecific differences among fish in concentrations of contaminants were noted. Striped mullet (hereafter mullet) frequently displayed the highest chemical concentrations. Levels of contaminants were generally higher in samples obtained from the Mississippi River than in those collected from the diversion area and were higher in mussels and clams (hereafter bivalves) than in fish. Because the Mississippi River sampling site for mullet and largemouth bass was downriver of the structure and south of New Orleans and the catfish site was upriver, the downriver data may not be directly reflective of the results from the receiving waters at the Davis Pond structure. Compared to the Caernarvon freshwater prediversion study in 1990 that assessed possible influx of contaminants with the freshwater diversion, contaminant levels in fishes and bivalves in this study were generally lower, yet three nontoxic inorganic elements in Davis Pond fish samples exhibited ranges of concentrations that were more than two times higher than did those from Caernarvon. Levels in bivalves were different between diversions but about equal in the numbers of trace elements showing high levels per location. Contaminant values were compared to those listed in various literature and agency sources, both regional and national, including the National Contaminant Biomonitoring Program (NCBP), in which the 85th percentile and above represents what is considered to be an elevated contaminant concentration and cause for concern. Generally, bivalves were at the high end of their ranges for both organic and inorganic contaminants. In this study, OCs were detectable in 67 percent of fish from the Mississippi River site, ranging from 0.15 to 1.09 μg/g wet weight (ww) or fresh weight (fw), and in 11 percent of the fish from the marsh sites, ranging from 0.06 to 0.612 μg/g ww. Bivalves from the Mississippi River had OC levels of 0.096 μg/g ww, whereas none were detectable in bivalves at the marsh sites. In this study, p,p ’-dichlorodiphenyldichloroethylene ( p,p’ -DDE) (a biodegradation product of DDT [dichlorodiphenyl trichloroethane]) and total PCBs were the most frequently detected OCs and were primarily from the Mississippi River. For total OC content, using adjusted least squares means, some significant interactions were noted between fish species and sites. PAHs were detected in aquatic animals at all sites (range of 0.017–17.534 μg/g ww), as were AHs (range of 0.423–4.549 μg/g ww); the highest levels of PAHs and AHs were found in bivalves from the Mississippi River. When analysis of variance (α = 0.05) was performed with data from aquatic animals, there were only two significant relationships between PAHs, AHs, and OCs between species, site, and age or the interaction among these variables. There was an interaction between fish species and n-decane (an AH) in that mullet and largemouth bass had significantly higher levels than did catfish ( P = 0.0175). When general linear means were used to investigate associations of inorganic contaminants among fish species, site, and age or any interactions among these variables, no significant results were noted for arsenic, cadmium, lead, beryllium, boron, molybdenum, or nickel. The range of mercury in fish in this study was 0.04–0.14 μg/g ww (0.14– 0.48 μg/g dry weight [dw]), with the most elevated levels detected in predatory largemouth bass at the sampling point farthest downstream from the structure and within the marsh area. Mercury was positively correlated with fish age ( P = 0.0152), where levels were estimated to increase 0.0253 parts per million (ppm) dw per year. In the Mississippi River, catfish showed significantly higher levels of mercury than did mullet or largemouth bass ( P = 0.00167). Among fish species, mullet displayed the highest levels in fish of aluminum, barium, manganese, and iron, all considered to have low toxicity in hydrologic systems. An interaction between fish and site was seen with aluminum ( P = 0.0031), where concentrations in mullet were significantly higher in the Mississippi River than at the other sites, as was also seen with barium ( P = 0.0009), chromium ( P = <0.0001), manganese ( P = 0.0004), strontium ( P = 0.0074), vanadium ( P = 0.0156), and zinc ( P = 0.0059). For iron ( P = 0.0.0001), mullet and largemouth bass at both the Mississippi River and Lake Salvador showed higher levels than did catfish, and these two species showed higher levels at two of the four sites. An interaction between fish and site was also seen with chromium ( P = <0.0001) in that concentrations in mullet were significantly higher in the Mississippi River than at the other sites, as was also seen with strontium ( P = 0.0074), vanadium ( P = 0.0156), and zinc ( P = 0.0059), metals for which deleterious effects have been demonstrated in other ecosystems. The NCBP program lists the 85th percentile for zinc at 34.2 μg/g fw (117.9 μg/g dw). In the Davis Pond prediversion biomonitoring study (hereafter the current study), one fish (MUL31RIVER, fish ID 8) showed values higher than that (125.4 μg/g dw or 37.54 μg/g ww), and the Mississippi River bivalve sample (MUSSRIVER) had a value of 140 μg/g dw (41.2 μg/g ww). In the current study, approximately 86 percent of the fish had measurable selenium levels, yet none reached the 85th percentile. The 85th percentile for selenium from the NCBP was 0.73 μg/g ww. Significantly higher levels of selenium were seen in mullet than in largemouth bass and catfish ( P = 0.0023). The NCBP 85th percentile for lead is 0.22 μg/g ww (0.76 μg/g dw). In the current study, the range of concentrations of lead was as much as 18.3 ppm dw (MUL31RIVER, fish ID 8), with the three most elevated values (range of 3.46–5.31 μg/g ww) coming from mullet from the Mississippi River. Biomarker data are measurable and directly reflect the condition of the animal, and measuring more than one biomarker in an individual increases confidence in health assessments. In the current study, biomarkers included macrophage aggregates (MAs), liver (hepatosomatic index [HSI]) and spleen (splenosomatic index [SSI]) weight to body weight ratios, percent white blood cells (WBCs) in whole blood, and condition factor. Few significant differences were noted with any of the biomarkers between sites, and there were no relationships between species and sites. For improved use of biomarker assessments, an increase in fish sample size would be useful for postdiversion sampling, as would comparisons of fish of the same sex and reproductive condition. During the current study, success for eagle nests in the diversion area and reference sites was similar as determined by numbers of nestlings fledged. When temperatures were below average during winter 2000, nests in both regions similarly failed. At each nest, the primary evidence of food items was small mammals. Eaglets (n = 6) generally appeared healthy, and whole blood concentrations of organic contaminants exceeded detection limits with three incidences of p,p’ -DDE (0.002–0.006 μg/L ww) and one incidence of oxychlordane (0.002 μg/L ww). The levels of p,p’ -DDE were well below those that have been inversely correlated with productivity and success rates of nesting bald eagles on a regional scale. The low values found in the whole blood samples for OC pesticides and PCBs were even lower when corrected for plasma volume. Aluminum values were 3.66 and 5.75 μg/L in two samples, zinc ranged from 5.21 to 6.77 μg/L ww in six samples, and silicon ranged from 1.7 to 4.6 μg/L in four samples. Selenium was detectable in each bird with the range at 0.332–0.566 μg/L ww, and strontium ranged from 0.0581 to 0.0975 μg/L ww. Mercury was detectable in blood samples from each bird and ranged from 0.0254 to 0.0845 μg/L ww, whereas lead was detectable in four samples and ranged from 0.0042 to 0.0136 μg/L ww. Although no detectable levels of total PCBs were found (also correlated with decreased reproductive productivity), 70 percent of the aquatic animals from the Mississippi River contained total PCBs (range 0.13–0.79 μg/L), whereas only about 7 percent of the aquatic animals sampled from the marsh area contained PCBs. Suggestions for postdiversion sampling include lowering the analytical detection limit for some metals, sampling aquatic animals over the course of a single season, obtaining a higher sample number of mature fish of one species (for example, blue catfish) within a range of total lengths for biomarker analyses, obtaining otoliths for estimating fish ages, assessing dioxins in eaglet blood, examining triazines in water, and obtaining all Mississippi River fish samples as close to the Davis Pond structure intake as possible. Because contaminants found in blood of eaglets reflect their prey species and because of the contaminant levels found in fish in the current study, eaglets may not be consuming primarily these species; therefore, obtaining juvenile nutria ( Myocastor coypus ) or turtle species for contaminant analyses might be considered, as well as collecting greater blood volume and using plasma to measure OCs and PCBs. Data obtained postdiversion will be compared with prediversion data to monitor changes.

Louisiana↗