Huan Zhong

Controls of dissolved organic matter and chloride on mercury uptake by a marine diatom.

The effects of natural dissolved organic carbon (DOC) from different origins (estuarine, coastal, and diatom decomposed) and chloride (Cl) on the uptake of inorganic mercury [Hg(II)] and methylated mercury (MeHg) by the marine diatom Thalassiosira pseudonana was investigated using radiotracer techniques. We first developed a new method to remove the surface adsorbed mercury and quantified the intracellular mercury uptake by the diatoms. The dominant mercury species (DOC or chloride complexes, based on the mercury speciation phase diagrams) was controlled by the concentrations of DOC and Cl(-), which could explain the effects of DOC and Cl(-) on mercury uptake. DOC complexes dominated Hg(II)s speciation and reduced its uptake in most seawater examined. DOC complexes dominated MeHgs speciation only at relatively high DOC levels (>100 muM), but it could affect MeHg uptake even when MeHg-Cl complexes dominated. In a mercury-DOC complex dominated system, both the origin and quantity of DOC greatly influenced mercury uptake by the diatoms. Although DOC generally inhibited the uptake of Hg(II) or MeHg, DOC resulting from diatom decomposition enhanced Hg(II) uptake. Under conditions dominated by chloride complexation, neutral mercury chloride species (HgCl(2) or MeHgCl) may control the uptake.

Copper uptake kinetics and regulation in a marine fish after waterborne copper acclimation

The uptake kinetics and regulation of copper in a marine predatory fish, the black sea bream Acanthopagrus schlegeli after acclimation to waterborne Cu were examined, using radiotracer techniques. The dissolved Cu uptake followed a linear pattern during the time of exposure, and the calculated uptake rate constant was 6.24 L kg(-1) day(-1). The efflux rate constant was 0.091 day(-1) following dietary uptake of Cu, and the dietary assimilation efficiency (AE) of Cu varied between 1.7% and 10.9% after the fish were fed with three types of prey (oysters, clams and brine shrimp). After the fish were acclimated at a nominal concentration of 50 microg Cu L(-1) for 14 days, the Cu uptake rate and efflux rate constant did not change significantly, but the Cu body concentrations and metallothionein (MT) concentrations in fish tissues increased significantly. Subcellular Cu distributions were also modified. Significant MT induction was observed in response to increased Cu tissue concentrations, indicating that MT rather than the uptake kinetics may play a primary role in Cu regulation during waterborne Cu acclimation in this marine fish. Moreover, the high Cu efflux may also be important in Cu regulation during long-term exposure. Our modeling calculations indicated that dietary uptake was likely to be the main route for Cu bioaccumulation in the fish, and the relative contribution of waterborne and dietary uptake depended on the bioconcentration factor (BCF) of the prey and ingestion rate of fish.

Influences of aging on the bioavailability of sediment‐bound Cd and Zn to deposit‐feeding sipunculans and soldier crabs

The radiotracer technique was used to assess the influences of sediment-metal contact time or aging (up to two years) on the bioavailability and geochemical speciation of Cd and Zn in sediments. Bioavailability was quantified by measuring the assimilation efficiency of metals in two deposit-feeding invertebrates (sipunculans and soldier crabs) and the extraction by the sipunculans gut juices. Sediment aging generally did not significantly affect the Cd speciation in the sediments, Cd assimilation, and Cd extraction. In contrast, sediment aging significantly affected the Zn distribution in different geochemical phases and the Zn bioavailability. With increasing aging, the Zn distributed in the carbonate phase decreased, whereas that in the reducible phase increased. Accordingly, the Zn gut-juice extraction decreased significantly. Two years of aging were not sufficient for Zn to be associated with the organic and residual phases. A significant positive correlation was found between Cd gut-juice extraction and assimilation efficiency. Gut-juice extraction of Cd and Zn generally increased with metal distribution in the exchangeable and carbonate phases but decreased with that in the reducible phase. Our results suggest that different metals are influenced by sediment aging differently and that geochemical speciation analysis is useful in studying the bioavailability of sediment-bound metals. This study may have implications for designing sediment toxicity tests using spiking techniques and for understanding the fates of anthropogenically derived metals in sediments.

Methylmercury extraction from artificial sediments by the gut juice of the sipunculan, Sipunculus nudus†

Artificially prepared sediments were used to investigate their binding with methylmercury (MeHg). The bioavailability of sediment-bound MeHg then was quantified by measuring the extraction by gut juice of the sipunculan Sipunculus nudus, as well as by different free amino acids and bovine serum albumin (BSA). Methylmercury distribution in different molecular weight- size fractions of gut juice also was determined using an ultrafiltration methodology. Organic and clay content were the two most important sediment components in MeHg partitioning, but most of the sediment-bound MeHg was complexed by organic matter (fulvic acid > humic acid) in sediments. Treatment with humic or fulvic acid generally increased the amount of bioavailable MeHg. Cysteine was more important than other amino acids in MeHg extraction. Proteins (especially >100 kDa fraction) in gut juice rather than free amino acids were the main agents in gut juice that extracted MeHg from sediments. Most extracted MeHg from artificial sediments was associated with the >100 kDa fraction (probably proteins) of gut juice but not with organic matter from sediments (humic acid and fulvic acid). Our results suggested that competition among different agents in gut juice (especially the large molecular-weight proteins) and the organic content of the sediments controlled the bioavailability of sediment-bound MeHg.

Mechanistic understanding of MeHg-Se antagonism in soil-rice systems: the key role of antagonism in soil.

Methylmercury (MeHg) accumulation in rice has great implications for human health. Here, effects of selenium (Se) on MeHg availability to rice are explored by growing rice under soil or foliar fertilization with Se. Results indicate that soil amendment with Se could reduce MeHg levels in soil and grain (maximally 73%). In contrast, foliar fertilization with Se enhanced plant Se levels (3–12 folds) without affecting grain MeHg concentrations. This evidence, along with the distinct distribution of MeHg and Se within the plant, demonstrate for the first time that Se-induced reduction in soil MeHg levels (i.e., MeHg-Se antagonism in soil) rather than MeHg-Se interactions within the plant might be the key process triggering the decreased grain MeHg levels under Se amendment. The reduction in soil MeHg concentrations could be mainly attributed to the formation of Hg-Se complexes (detected by TEM-EDX and XANES) and thus reduced microbial MeHg production. Moreover, selenite and selenate were equally effective in reducing soil MeHg concentrations, possibly because of rapid changes in Se speciation. The dominant role of Se-induced reduction in soil MeHg levels, which has been largely underestimated previously, together with the possible mechanisms advance our mechanistic understanding about MeHg dynamics in soil-rice systems.

Inorganic mercury binding with different sulfur species in anoxic sediments and their gut juice extractions.

To investigate the roles of different sulfur (S) species in controlling the partitioning and bioavailability of inorganic mercury (Hg) in anoxic sediments, we examined the differential binding of Hg with three key S species in anoxic sediment (mackinawite [FeS], pyrite [FeS2], and S(2-)) and then quantified their extraction by the gut juice of deposit-feeding sipunculans Sipunculus nudus. A sequential extraction method was simultaneously used to distinguish Hg sorption with different sediment components. All three S-containing sediment components could lead to a high binding of Hg in sediments, but most Hg was sorbed with FeS or FeS2 instead of formation of Hg sulfide despite the presence of S(2-) or humic acid. The gut juice extraction was relatively low and constant whenever FeS and FeS2 were in the sediment, indicating that both FeS and FeS2 controlled the Hg gut juice extraction and thus bioavailability. Mercury sorbed with FeS2 had higher gut juice extraction than that with FeS, while Hg sulfide was not extracted, strongly suggesting that Hg sorbed with FeS2 was more bioavailable than that with other S species. Mercury sorbed with FeS had very low bioavailability to sipunculans at a low Hg:S ratio in the sediment but was more bioavailable with increasing Hg:S ratio up to a maximum (approximately 1:10, mole based). The present study showed that different S species (FeS, FeS2) and Hg:S ratios significantly affected the binding and bioavailability of Hg in anoxic sediments.

The role of sorption and bacteria in mercury partitioning and bioavailability in artificial sediments

This study compared the relative importance of three types of sorption (organic matter-particle, mercury-organic matter and mercury-particle) in controlling the overall mercury partitioning and bioavailability in sediments. We found that all three types of sorption were important for both inorganic mercury (Hg) and methylated mercury (MeHg). Mercury-particle sorption was more important than mercury-fulvic acid (FA) sorption in increasing the mercury concentrations with increasing aging. Bioavailability (quantified by gut juice extraction from sipunculans) was mainly controlled by mercury-particle sorption, while FA-particle and mercury-FA sorption were not as important, especially for MeHg. Bacterial activity also increased the partitioning of Hg or MeHg in the sediments and was further facilitated by the presence of organic matter. The bioavailability of Hg or MeHg from sediments was only slightly influenced by bacterial activity. This study highlights the importance of sorption from various sources (especially mercury-particle sorption) as well as bacteria in controlling the partitioning and bioavailability of Hg or MeHg in sediments.

Uptake of Dissolved Organic Carbon-Complexed 65Cu by the Green Mussel Perna viridis

Stable Cu isotope ((65)Cu) was complexed with various representative dissolved organic carbon (DOC) types, including coastal seawater DOC, fulvic acid (FA), cyanobacteria spirulina (SP) DOC, histidine (His), cysteine (Cys), and lipophilic diethyl dithiocarbamate (DDC) at different concentrations. The uptake of these dissolved Cu species by the coastal green mussel Perna viridis was quantified for the first time. Copper complexed with different DOC types were taken up in some measure by mussels, depending on the DOC types. However, complexation generally reduced Cu uptake as compared to that of inorganic Cu species, and DOC type-specific negative relationships were found between DOC levels and Cu uptake. Strong Cu binding sites (including His and organic sulfur functional groups) within DOC appeared to control the inhibitory effects of DOC on Cu uptake, possibly due to the competitive binding of Cu between the dissolved phase and biological membranes. Therefore, differences in strong Cu binding site levels may explain the differences in bioavailability of Cu complexed with different types of DOC. At the same time, the variations in Cu-DOC uptake may also be partly attributed to the absorption of Cu-DOC complexes, especially for the small Cu-DOC complexes (e.g., Cu-Cys, Cu-His, or Cu-DDC). Our study highlights the importance of considering the specificity of Cu-DOC complexes when assessing biological exposure to dissolved Cu in natural waters, especially during events, such as phytoplankton bloom periods, that could modify DOC composition and concentrations.