Theresa S. Presser

Biogeochemical cycling of selenium in the San Joaquin Valley, California, USA

Subsurface agricultural drainage waters from western San Joaquin Valley, California, were found to contain elevated concentrations of the element selenium in the form of selenate. In 1978, these drainage waters began to replace previous input to Kesterson Reservoir, a pond system within Kesterson National Wildlife Refuge; this substitution was completed by 1982. In the 1983 nesting season, unusual rates of deformity and death in embryos and hatchlings of wild aquatic birds (up to 64% of eared grebe and American coot nests) occurred at the refuge and were attributed to selenium toxicosis. Features necessary for contamination to have taken place included geologic setting, climate, soil type, availability of imported irrigation water, type of irrigation, and the unique chemical properties of selenium. The mechanisms of biogeochemical cycling raise questions about other ecosystems and human exposure.

Bioaccumulation of selenium from natural geologic sources in western states and its potential consequences

Ecological impacts of water-quality problems have developed in the western United States resulting from the disposal of seleniferous agricultural wastewater in wetland areas. Overt effects of selenium toxicosis occurred at five areas where deformities of wild aquatic birds were similar to those first observed at Kesterson National Wildlife Refuge in the west-central San Joaquin Valley of California. These areas are: Tulare Lake Bed Area, California, Middle Green River Basin, Utah, Kendrick Reclamation Project Area, Wyoming, Sun River Basin, Montana, and Stillwater Wildlife Management Area, Nevada. Potential for ecological damage is indicated at six more sites in Oregon, Colorado, the Colorado/Kansas border, and South Dakota out of 16 areas in 11 states where biological tissue data were collected. This conclusion is based on the fact that selenium bioaccumulated in bird livers to median levels that had exceeded or were in the range associated with adverse reproductive effects. Selenium concentrations in samples of fish and bird eggs support these conclusions at a majority of these areas. Reason for concern is also given for the lower Colorado River Valley, although this is not exclusively a conclusion from these reconnaissance data. Biogeochemical conditions and the extent of selenium contamination of water, bottom sediment, and biota from which this assessment was made are given here. In a companion paper, the biogeochemical pathway postulated for selenium contamination to take place from natural geologic sources to aquatic wildlife is defined.

Ecological assessment of selenium in the aquatic environment.

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 Background and Need for Workshop . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7 Workshop Purpose and Goals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 Participation and Format . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 Workgroup Findings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 Workgroup 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 Problem formulation: Context for selenium risk assessment . . . . . . . . . . . . . . . . . . . . . 9 Selenium is a global problem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 Case studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 Conceptual model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 How to investigate a potential selenium problem . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 Recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 Workgroup 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 Environmental partitioning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 Workgroup 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 Bioaccumulation and trophic transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 Workgroup 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 Selenium toxicity to aquatic organisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 Workgroup 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 Risk characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 Importance of problem formulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 Risk characterization: Unique challenges concerning selenium . . . . . . . . . . . . . . . . . . 26 Risk management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 Uncertainties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29 Overall Workshop Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29 Appendix: SETAC Pellston Workshop Participants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 List of Figures Figure 1 Conceptual model depicting Se dynamics and transfer in aquatic ecosystems . . . . . . . . . . . . .11 Figure 2 Hierarchy of effects across levels of biological organization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12 Figure 3 Potential sources of Se to aquatic systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .15 Figure 4 Selenium species associated with major processes in aquatic systems . . . . . . . . . . . . . . . . . . . . . . . . . . .16 Figure 5 Partitioning of Se among environmental compartments in a typical aquatic system. . . .16 Figure 6 Selenium enrichment and trophic transfer in aquatic food webs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .19 Figure 7 Selenium accumulation in different species of algae, invertebrates, and fish . . . . . . . . . . . . . . . .20 Figure 8 Conceptual pathway of Se transfer in aquatic ecosystems and relative certainty with which Se concentrations in environmental compartments can be assessed in making accurate characterizations of risk . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .28 List of Tables Table 1 Assessment endpoints and measures of exposure and effect for aquatic and aquaticlinked organisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .14 Table 2 Uncertainties and recommendations for future research pertaining to toxicity of Se species . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .24 Ecological Assessment of Selenium in the Aquatic Environment 4

The Kesterson effect

Hypothesized to be derived from Cretaceous marine sedimentary rocks, selenium contamination of the Kesterson National Wildlife Refuge is traced through irrigation drainage to the source bedrock of the California Coast Ranges. This biogeochemical pathway of selenium is defined here as the “Kesterson effect.” At the refuge ponds, this effect culminated in 1983 in a 64% rate of deformity and death of embryos and hatchlings of wild aquatic birds. From the previous companion paper on irrigation drainage, the Kesterson effect has been implicated in nine of 11 reconnaissance areas studied in the western United States. Deformities have resulted in at least five of these sites. Climatic, geologic, hydrologic, and soil conditions in these reconnaissance areas are similar to those in the area surrounding Kesterson National Wildlife Refuge in the west-central San Joaquin Valley of California. In California, selenium, as selenate, was ultimately found weathered with sulfur from marine sources in soluble sodium and magnesium sulfate salts, which are concentrated by evaporation on farmland soils. The Se, mobilized by irrigation drainage, is bioaccumulated to toxic levels in refuge wetland ponds that are located mainly in hydrologically closed basins and thus act as concentrating disposal points. The depositional environment of the ponds may be similar to that of the nutrient-rich continental shelf edge and slope in which Cretaceous, Eocene, and Miocene sediments found to be seleniferous in the California Coast Ranges were deposited. Bioaccumulation may be therefore a primary mechanism of selenium enrichment in ancient sediments in addition to that of the formerly suggested Cretaceous volcanic pathway.

Emerging Opportunities in Management of Selenium Contamination1

Integrating the chemistry of selenium with its biology and ecotoxicology gives indications on how to regulate its environmental levels.

A methodology for ecosystem‐scale modeling of selenium

The main route of exposure for selenium (Se) is dietary, yet regulations lack biologically based protocols for evaluations of risk. We propose here an ecosystem-scale model that conceptualizes and quantifies the variables that determine how Se is processed from water through diet to predators. This approach uses biogeochemical and physiological factors from laboratory and field studies and considers loading, speciation, transformation to particulate material, bioavailability, bioaccumulation in invertebrates, and trophic transfer to predators. Validation of the model is through data sets from 29 historic and recent field case studies of Se-exposed sites. The model links Se concentrations across media (water, particulate, tissue of different food web species). It can be used to forecast toxicity under different management or regulatory proposals or as a methodology for translating a fish-tissue (or other predator tissue) Se concentration guideline to a dissolved Se concentration. The model illustrates some critical aspects of implementing a tissue criterion: 1) the choice of fish species determines the food web through which Se should be modeled, 2) the choice of food web is critical because the particulate material to prey kinetics of bioaccumulation differs widely among invertebrates, 3) the characterization of the type and phase of particulate material is important to quantifying Se exposure to prey through the base of the food web, and 4) the metric describing partitioning between particulate material and dissolved Se concentrations allows determination of a site-specific dissolved Se concentration that would be responsible for that fish body burden in the specific environment. The linked approach illustrates that environmentally safe dissolved Se concentrations will differ among ecosystems depending on the ecological pathways and biogeochemical conditions in that system. Uncertainties and model sensitivities can be directly illustrated by varying exposure scenarios based on site-specific knowledge. The model can also be used to facilitate site-specific regulation and to present generic comparisons to illustrate limitations imposed by ecosystem setting and inhabitants. Used optimally, the model provides a tool for framing a site-specific ecological problem or occurrence of Se exposure, quantify exposure within that ecosystem, and narrow uncertainties about how to protect it by understanding the specifics of the underlying system ecology, biogeochemistry, and hydrology.

Excess nitrogen in selected thermal and mineral springs of the Cascade Range in northern California, Oregon, and Washington: sedimentary or volcanic in origin?

Abstract Anomalous N2/Ar values occur in many thermal springs and mineral springs, some volcanic fumaroles, and at least one acid-sulfate spring of the Cascade Range. Our data show that N2/Ar values are as high as 300 in gas from some of the hot springs, as high as 1650 in gas from some of the mineral springs, and as high as 2400 in gas from the acid-sulfate spring on Mt. Shasta. In contrast, gas discharging from hot springs that contain nitrogen and argon solely of atmospheric origin typically exhibits N2/Ar values of 40–80, depending on the spring temperature. If the excess nitrogen in the thermal and mineral springs is of sedimentary origin then the geothermal potential of the area must be small, but if the nitrogen is of volcanic origin then the geothermal potential must be very large. End-member excess nitrogen (δ15N) is +5.3‰ for the thermal waters of the Oregon Cascades but is only about +1‰ for fumaroles on Mt. Hood and the acid-sulfate spring on Mt. Shasta. Dissolved nitrogen concentrations are highest for thermal springs associated with aquifers between 120 and 140°C. Chloride is the major anion in most of the nitrogen-rich springs of the Cascade Range, and N2/Ar values generally increase as chloride concentrations increase. Chloride and excess nitrogen in the thermal waters of the Oregon Cascades probably originate in an early Tertiary marine formation that has been buried by the late Tertiary and Quaternary lava flows of the High Cascades. The widespread distribution of excess nitrogen that has been generated in low to moderate-temperature sedimentary environments is further proof of the restricted geothermal potential of the Cascade Range.

Removal of selenium from contaminated agricultural drainage water by nanofiltration membranes

Abstract Seleniferous agricultural drainage wastewater has become a new major source of pollution in the world. In the USA, large areas of farmland in 17 western states, generate contaminated salinized drainage with Se concentrations much higher than 5 μg/I, the US Environmental Protection Agency water-quality criterion for the protection of aquatic life; Se values locally reach 4200 wg/1 in western San Joaquin Valley, California. Wetland habitats receiving this drainage have generally shown Se toxicosis in aquatic birds causing high rates of embryonic deformity and mortality, or have indicated potential ecological damage. Results of our laboratory flow experiments indicate that nanofiltration, the latest membrane separation technology, can selectively remove > 95% of Se and other multivalent anions from > 90% of highly contaminated water from the San Joaquin Valley, California. Such membranes yield greater water output and require lower pressures and less pretreatment, and therefore, are more cost effective than traditional reverse osmosis membranes. Nanofiltration membranes offer a potential breakthrough for the management of Se contaminated wastes not only from agricultural drainage, but from other sources also.

In search of earthquake-related hydrologic and chemical changes along Hayward Fault

Flow and chemical measurements have been made about once a month, and more frequently when required, since 1976 at two springs in Alum Rock Park in eastern San Jose, California, and since 1980 at two shallow wells in eastern Oakland in search of earthquake-related changes. All sites are on or near the Hayward Fault and are about 55 km apart. Temperature, electric conductivity, and water level or flow rate were measured in situ with portable instruments. Water samples were collected for later chemical and isotopic analyses in the laboratory. The measured flow rate at one of the springs showed a long-term decrease of about 40% since 1987, when a multi-year drought began in California. It also showed several increases that lasted a few days to a few months with amplitudes of 2.4 to 8.6 times the standard deviations above the background rate. Five of these increases were recorded shortly after nearby earthquakes of magnitude 5.0 or larger, and may have resulted from unclogging of the flow path and increase of permeability caused by strong seismic shaking. Two other flow increases were possibly induced by exceptionally heavy rainfalls. The water in both wells showed seasonal temperature and chemical variations, largely in response to rainfall. In 1980 the water also showed some clear chemical changes unrelated to rainfall that lasted a few months; these changes were followed by a magnitude 4 earthquake 37 km away. The chemical composition at one of the wells and at the springs also showed some longer-term variations that were not correlated with rainfall but possibly correlated with the five earthquakes mentioned above. These correlations suggest a common tectonic origin for the earthquakes and the anomalies. The last variation at the affected well occurred abruptly in 1989, shortly before a magnitude 5.0 earthquake 54 km away.

Geochemical evidence for Se mobilization by the weathering of pyritic shale, San Joaquin Valley, California, U.S.A.

Abstract Acidic (pH 4) seeps issue from the weathered Upper Cretaceous-Paleocene marine sedimentary shales of the Moreno Formation in the semi-arid Coast Ranges of California. The chemistry of the acidic solutions is believed to be evidence of current reactions ultimately yielding hydrous sodium and magnesium sulfate salts, e.g. mirabilite and bloedite, from the oxidation of primary pyrite. The selenate form of Se is concentrated in these soluble salts, which act as temporary geological sinks. Theoretically, the open lattice structures of these hydrous minerals could incorporate the selenate (SeO 4 −2 ) anion in the sulfate (SO 4 −2 ) space. When coupled with a semi-arid to arid climate, fractional crystallization and evaporative concentration can occur creating a sodium-sulfate fluid that exceeds the U.S. Environmental Protection Agency limit of 1000 μg l −1 for a toxic Se waste. The oxidative alkaline conditions necessary to ensure the concentration of soluble selenate are provided in the accompanying marine sandstones of the Panoche and Lodo Formations and the eugeosynclinal Franciscan assemblage. Runoff and extensive mass wasting in the area reflect these processes and provide the mechanisms which transport Se to the farmlands of the west-central San Joaquin Valley. Subsurface drainage from these soils consequently transports Se to refuge areas in amounts elevated to cause a threat to wildlife.