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.

Emerging opportunities in management of selenium contamination.

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

Characterizing dissolved Cu and Cd uptake in terms of the biotic ligand and biodynamics using enriched stable isotopes.

The biotic ligand model considers the biological and geochemical complexities that affect metal exposure. It relates toxicity to the fraction of physiological active sites impacted by reactive metal species. The biodynamic model is a complementary construct that predicts bioaccumulation and assumes that toxicity occurs when influx rates exceed rates of loss and detoxification. In this paper we presume that metal influx rates are mechanistically the resulting processes that characterize transmembrane transport. We use enriched stable isotopes to characterize, both in terms of the biotic ligand and biodynamics, dissolved metal uptake by a freshwater snail at water hardness varying up to 180-fold. Upon 24 h exposure, metal uptake was linear over a range encompassing most environmental concentrations; although saturation kinetics were observed at higher concentrations. Cadmium influx rates correlate with changes in the affinity of the biotic ligand, whereas those of Cu correlate with changes in both site affinity and capacity. A relationship between metal influx rate and ligand character asks whether toxicity is the result of accumulation at the biotic ligand or the rate at which metal is transported by that ligand.

Comparison of Selenium bioaccumulation in the clams Corbicula fluminea and Potamocorbula amurensis: a bioenergetic modeling approach.

Selenium uptake from food (assimilation efficiency) and dissolved phase (influx rate) as well as loss kinetics (efflux rate) were compared between two bivalves, Corbicula fluminea and Potamocorbula amurensis. The effects of salinity and temperature on these kinetic parameters for both clam species also were evaluated. The Asiatic clam, C. fluminea, more efficiently assimilated Se associated with algae (66-87%) than Se associated with oxic sediments (20-37%). However, no consistent difference was found between Se assimilation efficiencies from both food types (19-60%) for P. amurensis. The temperature and salinity had a minor influence on the Se assimilation from ingested food. However, the effects of temperature and salinity were more evident in the uptake from dissolved sources. The influx rate of Se(IV) increased by threefold with the increase of temperature from 5 to 21 degrees C for C. fluminea. The increase of salinity from 4 to 20 psu decreased the uptake rate constant (ku) of Se in P. amurensis from 0.011 to 0.005 L/g/h, whereas salinity change (0-8 psu) had a negligible effect on the Se influx rate of C. fluminea. The Se influx rate of P. amurensis decreased by half with the 3.5-fold increase in tissue dry weight. The rate constant of loss was greater for P. amurensis (0.029/d at 8 psu) than for C. fluminea (0.014/d at 0 psu and 0.01/d at 8 psu). A bioenergetic model suggests that dietary uptake is the dominant pathway for Se bioaccumulation in the two clams in San Francisco Bay and that interspecies differences in Se bioaccumulation can be explained by differences in food ingestion rates.

Food web pathway determines how selenium affects aquatic ecosystems: a San Francisco Bay case study.

Chemical contaminants disrupt ecosystems, but specific effects may be under-appreciated when poorly known processes such as uptake mechanisms, uptake via diet, food preferences, and food web dynamics are influential. Here we show that a combination of food web structure and the physiology of trace element accumulation explain why some species in San Francisco Bay are threatened by a relatively low level of selenium contamination and some are not. Bivalves and crustacean zooplankton form the base of two dominant food webs in estuaries. The dominant bivalve Potamocorbula amurensis has a 10-fold slower rate constant of loss for selenium than do common crustaceans such as copepods and the mysid Neomysis mercedis (rate constant of loss, ke = 0.025, 0.155, and 0.25 d(-1), respectively). The result is much higher selenium concentrations in the bivalve than in the crustaceans. Stable isotope analyses show that this difference is propagated up the respective food webs in San Francisco Bay. Several predators of bivalves have tissue concentrations of selenium that exceed thresholds thought to be associated with teratogenesis or reproductive failure (liver Se >15 microg g(-1) dry weight). Deformities typical of selenium-induced teratogenesis were observed in one of these species. Concentrations of selenium in tissues of predators of zooplankton are less than the thresholds. Basic physiological and ecological processes can drive wide differences in exposure and effects among species, but such processes are rarely considered in traditional evaluations of contaminant impacts.

Modeling selenium bioaccumulation through arthropod food webs in San Francisco Bay, California, USA.

Trophic transfer is the main process by which upper trophic level wildlife are exposed to selenium. Transfers through lower levels of a predator's food web thus can be instrumental in determining the threat of selenium in an ecosystem. Little is known about Se transfer through pelagic, zooplankton-based food webs in San Francisco Bay ([SFB], CA, USA), which serve as an energy source for important predators such as striped bass: A dynamic multipathway bioaccumulation model was used to model Se transfer from phytoplankton to pelagic copepods to carnivorous mysids (Neomysis mercedis). Uptake rates of dissolved Se, depuration rates, and assimilation efficiencies (AE) for the model were determined for copepods and mysids in the laboratory. Small (73-250 microm) and large (250-500 microm) herbivorous zooplankton collected from SFB (Oithona/Limnoithona and Acartia sp.) assimilated Se with similar efficiencies (41-52%) from phytoplankton. Mysids assimilated 73% of Se from small herbivorous zooplankton; Se AE was significantly lower (61%) than larger herbivorous zooplankton. Selenium depuration rates were high for both zooplankton and mysids (12-25% d(-1)), especially compared to bivalves (2-3% d(-1)). The model predicted steady state Se concentrations in mysids similar to those observed in the field. The predicted concentration range (1.5-5.4 microg g(-1)) was lower than concentrations of 4.5 to 24 microg g(-1) observed in bivalves from the bay. Differences in efflux between mysids and bivalves were the best explanation for the differences in uptake. The results suggest that the risk of selenium toxicity to predators feeding on N. mercedis would be less than the risk to predators feeding on bivalves. Management of selenium contamination should include food webs analyses to focus on the most important exposure pathways identified for a given watershed.

Increased selenium threat as a result of invasion of the exotic bivalve Potamocorbula amurensis into the San Francisco Bay-Delta.

Following the aggressive invasion of the bivalve, Potamocorbula amurensis, in the San Francisco Bay-Delta in 1986, selenium contamination in the benthic food web increased. Concentrations in this dominant (exotic) bivalve in North Bay were three times higher in 1995-1997 than in earlier studies, and 1990 concentrations in benthic predators (sturgeon and diving ducks) were also higher than in 1986. The contamination was widespread, varied seasonally and was greater in P. amurensis than in co-occurring and transplanted species. Selenium concentrations in the water column of the Bay were enriched relative to the Sacramento River but were not as high as observed in many contaminated aquatic environments. Total Se concentrations in the dissolved phase never exceeded 0.3 microg Se per l in 1995 and 1996; Se concentrations on particulate material ranged from 0.5 to 2.0 microg Se per g dry weight (dw) in the Bay. Nevertheless, concentrations in P. amurensis reached as high as 20 microg Se per g dw in October 1996. The enriched concentrations in bivalves (6-20 microg Se per g dw) were widespread throughout North San Francisco Bay in October 1995 and October 1996. Concentrations varied seasonally from 5 to 20 microg Se per g dw, and were highest during the periods of lowest river inflows and lowest after extended high river inflows. Transplanted bivalves (oysters, mussels or clams) were not effective indicators of either the degree of Se contamination in P. amurensis or the seasonal increases in contamination in the resident benthos. Se is a potent environmental toxin that threatens higher trophic level species because of its reproductive toxicity and efficient food web transfer. Bivalves concentrate selenium effectively because they bioaccumulate the element strongly and lose it slowly; and they are a direct link in the exposure of predaceous benthivore species. Biological invasions of estuaries are increasing worldwide. Changes in ecological structure and function are well known in response to invasions. This study shows that changes in processes such as cycling and effects of contaminants can accompany such invasions.