Temporal correspondence of selenium and mercury, among brine shrimp and water in Great Salt Lake, Utah, USA.

The specific source of high burdens of selenium (Se) and mercury (Hg) in several bird species at Great Salt Lake (GSL) remain unknown. Frequent co-located water and brine shrimp samples were collected during 2016 through 2017 to identify potential correlations of element concentrations among brines and brine shrimp, a keystone species in the GSL. Like many aquatic systems, GSL is characterized by elevated methylmercury (MeHg) in deep waters. However, in contrast to thermally-stratified aquatic systems, biota in the salinity-stratified GSL do not reside in its deep waters, obscuring the presumed relationship between elevated MeHg in biota and in the deep brine. Brine shrimp and water column (shallow and deep, filtered and unfiltered) samples were collected from six sites spanning the South Arm of GSL approximately every other month. Mercury concentrations in brine shrimp (on average 89% of which is MeHg) were correlated only with total mercury in surface filtered water, and displayed little spatial variability, but consistent seasonal trends across the two sampled years. In contrast to Hg, temporal correspondence was observed between Se concentrations in brine shrimp and those in all water samples regardless of filtering and depth, with maxima and minima at higher-than-seasonal frequency. The data suggest a spatially diffuse source of bioavailable mercury to the shallow brine that responds to seasonal influences, for which the underlying deep brine, surficial sediments, and overlying atmosphere were evaluated in terms of potential temporal correspondence to shallow brine and brine shrimp Hg concentrations, as well as potential to mix across the extent of the shallow brine. Bioaccumulation factors were at the low end of those reported for marine systems, and decreased at higher trace element concentrations in water.

Total Mercury and Methylmercury Response in Water, Sediment, and Biota to Destratification of the Great Salt Lake, Utah, United States.

Measurements of chemical and physical parameters made before and after sealing of culverts in the railroad causeway spanning the Great Salt Lake in late 2013 documented dramatic alterations in the system in response to the elimination of flow between the Great Salt Lake's north and south arms. The flow of denser, more-saline water through the culverts from the north arm (Gunnison Bay) to the south arm (Gilbert Bay) previously drove the perennial stratification of the south arm and the existence of oxic shallow brine and anoxic deep brine layers. Closure of the causeway culverts occurred concurrently with a multiyear drought that resulted in a decrease in the lake elevation and a concomitant increase in top-down erosion of the upper surface of the deep brine layer by wind-forced mixing. The combination of these events resulted in the replacement of the formerly stratified water column in the south arm with one that was vertically homogeneous and oxic. Total mercury concentrations in the deep waters of the south arm decreased by approximately 81% and methylmercury concentrations in deep waters decreased by roughly 86% due to destratification. Methylmercury concentrations decreased by 77% in underlying surficial sediment, whereas there was no change observed in total mercury. The dramatic mercury loss from deep waters and methylmercury loss from underlying sediment in response to causeway sealing provides new understanding of the potential role of the deep brine layer in the accumulation and persistence of methylmercury in the Great Salt Lake. Additional mercury measurements in biota appear to contradict the previously implied connection between elevated methylmercury concentrations in the deep brine layer and elevated mercury in avian species reported prior to causeway sealing.

Maternal transfer of inorganic mercury and methylmercury in aquatic and terrestrial arthropods.

The transfer of mercury from females to their offspring plays an important role in mercury accumulation and toxicity during early development. To quantify the transfer of inorganic mercury and methylmercury from female arthropods to their eggs, the authors collected and analyzed brine shrimp (Artemia franciscana), wolf spiders (Alopecosa spp.), and their attached eggs from aquatic and terrestrial ecosystems at the Great Salt Lake, Utah, USA. Essentially all of the mercury in both the female brine shrimp and their eggs was methylmercury (94 ± 17% and 90 ± 21%, respectively). The brine shrimp eggs had methylmercury concentrations that were 84 ± 2% lower than in the females, reflecting the fact that females transferred 45 ± 4% of their total body mass but only 11 ± 3% of their methylmercury burden to their eggs. As a result of this sequestration, the concentration of methylmercury in the female brine shrimp increased by 62 ± 8% during egg formation. The percentage of the total mercury that was methylmercury in female wolf spiders (77 ± 21%) was similar to that in their egg masses (81 ± 19%), indicating similar maternal transfer efficiencies for inorganic mercury and methylmercury in these invertebrates. The concentration of inorganic mercury and methylmercury in the female spiders was the same as in their eggs. These arachnids transferred 48 ± 9% of their total body mass, 55 ± 13% of their inorganic mercury, and 50 ± 9% of their methylmercury to their egg masses. Thus, female wolf spiders do not have the ability to reduce the transfer of methylmercury to their eggs, nor does this process represent an important pathway for the depuration of mercury. The present study demonstrates that although some arthropods have mechanisms to minimize the transfer of methylmercury to their eggs and reduce the potential for mercury toxicity during early development, other arthropods do not.

The tropical African mercury anomaly: lower than expected mercury concentrations in fish and human hair.

Mercury is a neurotoxin and global pollutant, and wetlands and newly flooded areas are known to be sites of enhanced production of monomethylmercury, the form of mercury that is readily biomagnified in aquatic food chains to potentially toxic levels. The Okavango Delta in Botswana, Southern Africa, is the largest inland delta in the world and a wetland ecosystem that experiences dramatic annual flooding of large tracts of seasonal floodplains. The Delta was, therefore, expected to be home to high mercury levels in fish and to be an area where local subsistence fishing communities would be at substantial risk of mercury toxicity from fish consumption. Total mercury concentrations measured in 27 species of fish from the Okavango Delta averaged (mean±s.d., wet weight) 19±19ng g(-1) in non-piscivorous fish, and 59±53ng g(-1) in piscivorous fish. These mercury concentrations are similar to those reported for fish from lakes in other areas of tropical Africa, demonstrating that not all wetlands are sites of elevated mercury concentrations in biota. Even more intriguing is that concentrations of mercury in fish from across tropical Africa are systematically and substantially lower than those typically reported for fish from freshwater ecosystems elsewhere globally. The reasons for this apparent "African mercury anomaly" are unclear, but this finding poses a unique opportunity to improve our understanding of mercury's biogeochemical cycling in the environment. Mercury concentrations measured in human hair collected in subsistence fishing communities in the Okavango Delta were similarly low (0.21±0.22µg g(-1) dry weight) despite high levels of fish consumption, and reflect the low mercury concentrations in the fish here.

Stability of dimethyl mercury in seawater and its conversion to monomethyl mercury.

Dimethyl mercury (DMHg) is commonly detected in the world's oceans, but little is known about the mechanisms responsible for DMHg degradation in natural waters or the products of this degradation. Similarly, the potential for the conversion of DMHg to monomethyl mercury (MMHg) under the acidic conditions commonly used to preserve samples for MMHg analysis has not been fully addressed. We provide evidence suggesting that DMHg in natural seawater is not readily photodegraded by sunlight as previously thought. Other experiments demonstrated that DMHg in seawater is, however, readily decomposed under acidic conditions, with MMHg as the predominant product. This facile conversion of DMHg to MMHg at low pH both necessitates an alternative preservation method to acidification for samples to be analyzed for MMHg when DMHg is present, and requires that data from previous studies of MMHg in seawater employing sample acidification be revisited in instances where appreciable DMHg concentrations were possible.

Mercury concentrations and loads in a large river system tributary to San Francisco Bay, California, U.S.A.

In order to estimate total mercury (HgT) loads entering San Francisco Bay, U.S.A., via the Sacramento-San Joaquin River system, unfiltered water samples were collected between January 2002 and January 2006 during high flow events and analyzed for HgT. Unfiltered HgT concentrations ranged from 3.2 to 75 ng/L and showed a strong correlation (r2 = 0.8, p < 0.001, n=78) to suspended sediment concentrations (SSC). During infrequent large floods, HgT concentrations relative to SSC were approximately twice as high as observed during smaller floods. This difference indicates the transport of more Hg-contaminated particles during high discharge events. Daily HgT loads in the Sacramento-San Joaquin River at Mallard Island ranged from below the limit of detection to 35 kg. Annual HgT loads varied from 61 +/- 22 kg (n=5) in water year (WY) 2002 to 470 +/- 170 kg (n=25) in WY 2006. The data collected will assist in understanding the long-term recovery of San Francisco Bay from Hg contamination and in implementing the Hg total maximum daily load, the long-term cleanup plan for Hg in the Bay.

Dimethylmercury in coastal upwelling waters, Monterey Bay, California.

Depth profiles of dimethylmercury (DMHg) concentration were determined at nearshore to offshore sites in Monterey Bay, California. The onset of spring upwelling in the bay was accompanied by increases in DMHg concentrations. Profiles show DMHg increasing gradually with depth in fall and winter from <0.03 pM at the surface to 0.5 pM at 200 m. During the spring, DMHg concentrations increased between 30 and 100 m, first within Monterey Bay, then offshore. This change was accompanied by an increase in DMHg concentrations in the surface water DMHg between fall/winter (<0.03 pM) and spring (0.06-0.29 pM). Microbial activity associated with the remineralization of sinking organic matter produced by the high primary production in the bay may result in the relatively high DMHg in subsurface water in the bay, which when upwelled may facilitate the incorporation of organomercury into biota. As a result, productive coastal upwelling areas may represent an important source of methylated mercury to surface waters, and thus be an important source of mercury to marine ecosystems.

Mercury in the San Francisco Estuary.

This review presents some of the published and other important literature on mercury contamination in San Francisco Estuary. Studies on human consumption of contaminated sportfish and on detecting ecological impacts of this contamination in wetland areas validate concerns regarding mercury's toxicity in this system. Mining, industrial, and environmental uses of mercury have occurred for more than a century, resulting in its large historic and continuing transport to the estuary. Consequently, there is a widespread distribution in the estuary, but more work is needed to show its relative chemical and biological availability from these sources. The uptake of mercury in the estuary has been shown in phytoplankton, but studies on biomagnification in local food webs have yet to draw a clear path to impairment in sportfish and waterbirds. In light of these concerns of impairment and the need for further information, large restoration activities planned for the estuary will require new technical approaches to solve important management questions, such as the location of key areas of methylmercury production.

Competing ligand exchange-solid phase extraction method for the determination of the complexation of dissolved inorganic mercury (II) in natural waters.

A method employing dual competitive ligand exchange followed by solid phase extraction (CLE-SPE) for characterizing the complexation of inorganic Hg(II) in natural waters is described. This method employs parallel use of two competing ligands: diethyldithiolcarbamate (DEDC), which forms hydrophobic complexes with Hg(II), and thiosalicylic acid (TSA), which forms hydrophilic complexes with Hg(II). Inorganic mercury complexed by natural and competing ligands are separated based on hydrophobicity using C18 solid phase extraction columns. Data modeling allows for the calculation of the concentration and conditional stability constants of natural ligands capable of complexing Hg(II) in both the operationally defined hydrophilic and hydrophobic fractions. The use of multiple ligand concentrations, and thus multiple analytical windows, to characterize different ligand classes within both of these two fractions is described. Studies of the kinetics of the ligand exchange involved, potential for changes in the stability of natural ligands during freezing and thawing, potential breakthrough during solid phase extraction, as well as the method's precision and estimation of error, are presented and discussed. Results from the application of the method to natural freshwaters demonstrated that in the limited samples collected over 99.99% of the ambient inorganic mercury is strongly complexed by ligands with conditional stability constants (K(HgL)(cond), Hg2+) on the order of 10(30), values similar to that of reduced sulfur ligands. At ambient conditions 85-90% of the mercury exists in hydrophobic complexes in these freshwaters, but strong Hg-binding ligands exist in both the hydrophobic and hydrophilic fractions.