The relationships between mercury and selenium in plankton and fish from a tropical food web

Background, aim, and scope  Selenium (Se) has been shown to reduce mercury (Hg) bioavailability and trophic transfer in aquatic ecosystems. The study of methylmercury (MeHg) and Se bioaccumulation by plankton is therefore of great significance in order to obtain a better understanding of the estuarine processes concerning Hg and Se accumulation and biomagnification throughout the food web. In the western South Atlantic, few studies have documented trace element and MeHg in fish tissues. No previous study about trace elements and MeHg in plankton has been conducted concerning tropical marine food webs. Se, Hg, and MeHg were determined in two size classes of plankton, microplankton (70–290 μm) and mesoplankton (≥290 μm), and also in muscle tissues and livers of four fish species of different trophic levels (Mugil liza, a planktivorous fish; Bagre spp., an omnivorous fish; Micropogonias furnieri, a benthic carnivorous fish; and Centropomus undecimalis, a pelagic carnivorous fish) from a polluted estuary in the Brazilian Southeast coast, Guanabara Bay. Biological and ecological factors such as body length, feeding habits, and trophic transfer were considered in order to outline the relationships between these two elements. The differences in trace element levels among the different trophic levels were investigated. Materials and methods  Fish were collected from July 2004 to August 2005 at Guanabara Bay. Plankton was collected from six locations within the bay in August 2005. Total mercury (THg) was determined by cold vapor atomic absorption spectrometry (CV-AAS) with sodium borohydride as a reducing agent. MeHg analysis was conducted by digesting samples with an alcoholic potassium hydroxide solution followed by dithizone-toluene extraction. MeHg was then identified and quantified in the toluene layer by gas chromatography with an electron capture detector (GC-ECD). Se was determined by AAS using graphite tube with Pin platform and Zeeman background correction. Results and discussion  Total mercury, MeHg, and Se increased with plankton size class. THg and Se values were below 2.0 and 4.8 μg g⁻¹ dry wt in microplankton and mesoplankton, respectively. A large excess of molar concentrations of Se in relation to THg was observed in both plankton size class and both fish tissues. Plankton presented the lowest concentrations of this element. In fish, the liver showed the highest THg and Se concentrations. THg and Se in muscle were higher in Centropomus undecimalis (3.4 and 25.5 nmol g⁻¹) than in Micropogonias furnieri (2.9 and 15.3 nmol g⁻¹), Bagre spp (1.3 and 3.4 nmol g⁻¹) and Mugil liza (0.3 and 5.1 nmol g⁻¹), respectively. The trophic transfer of THg and Se was observed between trophic levels from prey (considering microplankton and mesoplankton) to top predator (fish). The top predators in this ecosystem, Centropomus undecimalis and Micropogonias furnieri, presented similar MeHg concentrations in muscles and liver. Microplankton presented lower ratios of methylmercury to total mercury concentration (MeHg/THg) (34%) than those found in mesoplankton (69%) and in the muscle of planktivorous fish, Mugil liza (56%). The other fish species presented similar MeHg/THg in muscle tissue (of around 100%). M. liza showed lower MeHg/THg in the liver than C. undecimalis (35%), M. furnieri (31%) and Bagre spp. (22%). Significant positive linear relationships were observed between the molar concentrations of THg and Se in the muscle tissue of M. furnieri and M. liza. These fish species also showed significant inverse linear relationships between hepatic MeHg and Se, suggesting a strong antagonistic effect of Se on MeHg assimilation and accumulation. Conclusions  Differences found among the concentrations THg, MeHg, and Se in microplankton, mesozooplankton, and fishes were probably related to the preferred prey and bioavailability of these elements in the marine environment. The increasing concentration of MeHg and Se at successively higher trophic levels of the food web of Guanabara Bay corresponds to a transfer between trophic levels from the lower trophic level to the top-level predator, suggesting that MeHg and Se were biomagnified throughout the food web. Hg and Se were positively correlated with the fish standard length, suggesting that larger and older fish bioaccumulated more of these trace elements. THg, MeHg, and Se were a function of the plankton size. Recommendations and perspectives  There is a need to assess the role of selenium in mercury accumulation in tropical ecosystems. Without further studies of the speciation of selenium in livers of fishes from this region, the precise role of this element, if any, cannot be verified in positively affecting mercury accumulation. Further studies of this element in the study of marine species should include liver samples containing relatively high concentrations of mercury. A basin-wide survey of selenium in fishes is also recommended.     

Geochemical processes of mercury in Wujiangdu and Dongfeng reservoirs, Guizhou, China

The geochemical processes of mercury in Dongfeng (DF) and Wujiangdu (WJD) reservoirs, which were constructed in 1992 and 1979, respectively in Wujiang River, which is the upper branch of Yangtze River were investigated. One sampling site was chosen upriver of 1 km from the dam for each reservoir. Three sampling campaigns were conducted at these sampling sites in December 2003, April 2004 and July 2004, respectively. The distributions of different mercury species in the water column, sediment, and sediment pore water were studied. We found that the sediment is the net source of both inorganic and MeHg to the water column for both reservoirs. The MeHg diffusion fluxes in WJD reservoir at all sampling campaigns were significantly higher than those in DF reservoir. Our study demonstrated that the high primary productivity in the reservoir produced elevated organic matter content that would favor the methylmercury production in sediment.     

Photodegradation of methylmercury in Jialing River of Chongqing, China

Photodegradation(PD) of methylmercury(MMHg) is a key process of mercury(Hg) cycling i water systems, maintaining MMHg at a low level in water systems. However, we posses little knowledge of this important process in the Jialing River of Chongqing, China. In sit incubation experiments were thus performed to measure temporal patterns and influencin factors of MMHg PD in this river. The results showed that MMHg underwent a ne demethylation process under solar radiation in the water column, which predominantl occurred in surface waters. For surface water, the highest PD rate constants were observed i spring(12 × 10-3± 1.5 × 10~(-3)m~2/E), followed by summer(9.0 × 10~(-3)± 1.2 × 10~(-3)m~2/E), autum(1.4 × 10~(-3)± 0.12 × 10~(-3)m~2/E), and winter(0.78 × 10~(-3)± 0.11 × 10~(-3)m~2/E). UV-A radiatio(320–400 nm), UV-B radiation(280–320 nm), and photosynthetically active radiation(PAR400–700 nm) accounted for 43%–64%, 14%–31%, and 16%–45% of MMHg PD, respectively. PD rat constants varied substantially with the treatments that filtered the river water and amended with chemicals(i.e., Cl-, NO_3~-, dissolved organic matter(DOM), Fe(III)), which reveals tha suspended particulate matter and water components are important factors in affecting the PD process. For the entire water column, the PD rate constant determined for each wavelengt range decreased rapidly with water depth. UV-A, UV-B, and PAR contributed 27%–46%, 6.2%12%, and 42%–65% to the PD process, respectively. PD flux was estimated to be 4.7 μg/(m~2·yea in the study site. Our results are very important to understand the cycling characteristics o MMHg in the Jialing River of Chongqing, China.     

等温气相色谱法测定土壤中甲基汞

样品采用碱消化，室温下在pH＝4．9时进行乙基化反应，氢气为载气，Carbotrap富集有机态汞，等温气相色谱（GC）分离，用冷原子萤光仪（CVAFS）测定。方法检出限20pg。线性范围100～600pg。回收率在95％～105％之间。     

Habitat-specific bioaccumulation of methylmercury in invertebrates of small mid-latitude lakes in North America

We examined habitat-specific bioaccumulation of methylmercury (MeHg) in aquatic food webs by comparing concentrations in pelagic zooplankton to those in littoral macroinvertebrates from 52 mid-latitude lakes in North America. Invertebrate MeHg concentrations were primarily correlated with water pH, and after controlling for this influence, pelagic zooplankton had significantly higher MeHg concentrations than littoral primary consumers but lower MeHg than littoral secondary consumers. Littoral primary consumers and pelagic zooplankton are two dominant prey for fish, and greater MeHg in zooplankton is likely sufficient to increase bioaccumulation in pelagic feeders. Intensive sampling of 8 lakes indicated that habitat-specific bioaccumulation in invertebrates (of similar trophic level) may result from spatial variation in aqueous MeHg concentration or from more efficient uptake of aqueous MeHg into the pelagic food web. Our findings demonstrate that littoral-pelagic differences in MeHg bioaccumulation are widespread in small mid-latitude lakes.     

Low-level maternal methylmercury exposure through rice ingestion and potential implications for offspring health

Fish consumption is considered the primary pathway for MeHg (MeHg) exposure; however, MeHg exposure also occurs through rice ingestion. Rice is grown in an aquatic environment and although documented MeHg concentrations in rice are lower compared to fish tissue, human exposures exceed international guidelines in some regions where rice is a staple food and rice MeHg levels are elevated. Studies concerning human health exposure to MeHg should also include populations where maternal MeHg exposure occurs through ingestion of rice. Rice does not contain long-chain polyunsaturated fatty acids, which are associated with confounding developmental outcomes in offspring. Rice is also a staple food for more than half the world’s population; therefore, it is critical to investigate the potential health risks of maternal ingestion of rice to the developing fetus, the most susceptible population to the deleterious effects of MeHg. Data concerning MeHg in rice are reviewed and micronutrients in rice are discussed.     

Characterization of mercury species in brown and white rice (Oryza sativa L.) grown in water-saving paddies

In China, total Hg (Hg_T) and methylmercury (MeHg) were quantified in rice grain grown in three sites using water-saving rice cultivation methods, and in one Hg-contaminated site, where rice was grown under flooded conditions. Polished white rice concentrations of Hg_T (water-saving: 3.3 ± 1.6 ng/g; flooded: 110 ± 9.2 ng/g) and MeHg (water-saving 1.3 ± 0.56 ng/g; flooded: 12 ± 2.4 ng/g) were positively correlated with root-soil Hg_T and MeHg contents (Hg_T: r² = 0.97, MeHg: r² = 0.87, p < 0.05 for both), which suggested a portion of Hg species in rice grain was derived from the soil, and translocation of Hg species from soil to rice grain was independent of irrigation practices and Hg levels, although other factors may be important. Concentrations of Hg_T and other trace elements were significantly higher in unmilled brown rice (p < 0.05), while MeHg content was similar (p > 0.20), indicating MeHg infiltrated the endosperm (i.e., white rice) more efficiently than inorganic Hg(II).     

Mercury accumulation in marine bivalves: influences of biodynamics and feeding niche

Differences in the accumulation of mercury (Hg) in five species of marine bivalves, including scallops Chlamys nobilis, clams Ruditapes philippinarum, oysters Saccostrea cucullata, green mussels Perna viridis, and black mussels Septifer virgatus, were investigated. The bivalves displayed different patterns of Hg accumulation in terms of the body concentrations of methylmercury (MeHg) and total Hg (THg), as well as the ratio of MeHg to THg. Parameters of the biodynamics of the accumulation of Hg(II) and MeHg could reflect the species-dependent Hg concentrations in the bivalves. With the exception of black mussels, we found a significant relationship between the efflux rates of Hg(II) and the THg concentrations in the bivalves. The interspecific variations in the MeHg to THg ratio were largely controlled by the relative difference between the elimination rates of Hg(II) and MeHg. Stable isotope (δ¹³C) analysis indicated that the five bivalve species had contrasting feeding niches, which may also affect the Hg accumulation.     

Importance of sulfate reducing bacteria in mercury methylation and demethylation in periphyton from Bolivian Amazon region

Sulfate reducing bacteria (SRB) are important mercury methylators in sediments, but information on mercury methylators in other compartments is ambiguous. To investigate SRB involvement in methylation in Amazonian periphyton, the relationship between Hg methylation potential and SRB (Desulfobacteraceae, Desulfobulbaceae and Desulfovibrionaceae) abundance in Eichhornia crassipes and Polygonum densiflorum root associated periphyton was examined. Periphyton subsamples of each macrophyte were amended with electron donors (lactate, acetate and propionate) or inhibitors (molybdate) of sulfate reduction to create differences in SRB subgroup abundance, which was measured by quantitative real-time PCR with primers specific for the 16S rRNA gene. Mercury methylation and demethylation potentials were determined by a stable isotope tracer technique using ²⁰⁰HgCl and CH₃²⁰²HgCl, respectively. Relative abundance of Desulfobacteraceae (<0.01-12.5%) and Desulfovibrionaceae (0.01-6.8%) were both highly variable among samples and subsamples, but a significant linear relationship (p < 0.05) was found between Desulfobacteraceae abundance and net methylmercury formation among treatments of the same macrophyte periphyton and among all P. densiflorum samples, suggesting that Desulfobacteraceae bacteria are the most important mercury methylators among SRB families. Yet, molybdate only partially inhibited mercury methylation potentials, suggesting the involvement of other microorganisms as well. The response of net methylmercury production to the different electron donors and molybdate was highly variable (3-1104 pg g⁻¹ in 12 h) among samples, as was the net formation in control samples (17-164 pg g⁻¹ in 12 h). This demonstrates the importance of community variability and complexity of microbial interactions for the overall methylmercury production in periphyton and their response to external stimulus.     

Patterns of mercury and methylmercury bioaccumulation in fish species downstream of a long-term mercury-contaminated site in the lower Ebro River (NE Spain)

Since the 19th century, large amounts of industrial waste were dumped in a reservoir adjacent to a chlor-alkali plant in the lower Ebro River (NE Spain). Previous toxicological analysis of carp populations inhabiting the surveyed area have shown that the highest biological impact attributable to mercury pollution occurred downstream of the discharge site. However, mercury speciation in fish from this polluted area has not been addressed yet. Thus, in the present study, piscivorous European catfish (Silurus glanis) and non-piscivorous common carp (Cyprinus carpio) were selected, to investigate the bioavailability and bioaccumulation capacities of both total mercury (THg) and methylmercury (MeHg) at the discharge site and downstream points. Multiple Correspondence Analysis (MCA) was applied to reduce the dimensionality of the data set, and Multiple Linear Regression (MLR) models were fitted in order to assess the relationship between both Hg species in fish and different variables of interest. Mercury levels in fish inhabiting the dam at the discharge site were found to be approximately 2-fold higher than those from an upstream site; while mercury pollution progressively increased downstream of the hot spot. In fact, both THg and MeHg levels at the farthest downstream point were 3 times greater than those close to the waste dump. This result clearly indicates downstream transport and increased mercury bioavailability as a function of distance downstream from the contamination source. A number of factors may affect both the downstream transport and increased Hg bioavailability associated with suspended particulate matter (SPM) and dissolved organic carbon (DOC).