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。     

Mercury in surface waters of a macrotidal urban estuary (River Adour, south-west France)

Surface waters were collected in the River Adour estuary (south-western France) during different sampling periods from 1998 to 2001 in order to investigate the phase distribution and speciation of methylmercury (MeHg⁺). Although a high variability is observed, significant higher average concentrations of total MeHg⁺ (dissolved and particulate) are measured during the warm seasons, at 4.40±8.18 pM and 3.90±1.87 pM for July 1998 and September 1999, compared with the winter seasons, with concentrations at 0.99±2.85 pM and 1.00±1.75 pM for February 1998 and February 2001, respectively (one-tailed t-test, P=0.01). The seasonal variations are explained with enhanced bacterial activity during summer and sedimentation/resuspension phenomena. Additionally, signi-ficant longitudinal variations of the MeHg⁺ concentrations are observed. The highest levels in both dissolved and particulate fractions are found within the downstream urban estuarine area. This can be explained by the high methylation potential of the sediments, but direct anthropogenic inputs of MeHg⁺ from specific discharge points cannot be neglected. Biogeochemical factors like phytoplankton biomass and salinity also show a relationship with MeHg⁺ partitioning in the surface waters of the Adour estuary.     

Differentiated emission control strategy based on comprehensive evaluation of multi-media pollution: Case of mercury emission control

In order to comprehensively evaluate the environmental impact of multi-media mercury pollution under differentiated emission control strategies in China, a literature review and case studies were carried out. Increased human exposure to methylmercury was assessed through the dietary intake of residents in areas surrounding a typical coal-fired power plant and a zinc(Zn) smelter, located either on acid soil with paddy growth in southern China, or on alkaline soil with wheat growth in northern Chi...     

Influence of dissolved organic matter on methylmercury transformation during aerobic composting of municipal sewage sludge under different C/N ratios

Current knowledge about the transformation of total mercury and methylmercury (MeHg) in aerobic composting process is limited. In this study, the composition and transformation of mercury and dissovled organic matter (DOM) in aerobic composting process of municipal sewage sludge were were comprehensively characterized, and the differences among the three C/N ratio (20, 26 and 30) were investigated. The main form of mercury in C/N 20 and 26 was organo-chelated Hg (F3, 46%-60%); while the main form of mercury in C/N 30 was mercuric sulfide (F5, 64%-70%). The main component of DOM in C/N 20 and 26 were tyrosine-like substance (C1, 53%-76%) while the main fractions in C/N 30 were tyrosine-like substance (C1, 28%-37%) and fulvic-like substance (C2, 17%-39%). The mercury and DOM varied significantly during the 9 days composting process. Compared to C/N 20 and 26, C/N 30 produced the less MeHg after aerobic composting process, with values of 658% (C/N 20), 1400% (C/N 26) and 139% (C/N 30) of the initial, respectively. Meanwhile, C/N 30 produced the best compost showed greater degree of DOM molecular condensation and humification. Hg fraction had been altered by DOM, as indicated by a significant correlation between mercury species and DOM components. Notably, C/N 30 should be used as an appropriate C/N ratio to control the methylation processes of mercury and degration of DOM.     

松花江流域渔业生态环境汞污染现状评价

2007～2009年对松花江干流、嫩江下游江段、第二松花江干流水质、底质和鱼类汞含量状况进行了调查研究,并参照渔业水质标准、无公害水产品产地环境要求、无公害水产品安全要求和松花江流域汞的背景值对流域生态环境汞污染进行评价.结果表明:江水中总汞含量0.000010～0.000172 mg/L,符合渔业水质标准要求;第二松...     

DGT富集-乙基化GC-CVAFS测定天然水体中的甲基汞

利用薄膜扩散技术(DGT)原位富集天然水体中的甲基汞,溶剂洗脱后进入水相连行乙基化反应,与气相色谱(GC)联用,冷原子荧光光谱法(CVAFS)测定.实验结果显示,26"(3条件下在超纯水中放置24 h,典型DGT单元的最低检出限为0.014 ng/L;延长放置时闻或者减少扩散层厚度,可以得到更低的检测限.相对标准偏差＜...     

Organochlorines, brominated flame retardants and mercury levels in six seabird species from the Gulf of St. Lawrence (Canada): Relationships with feeding ecology, migration and molt

Concentrations of organochlorines (OCs), brominated flame retardants (BFRs) and mercury (Hg) were measured in eggs of six seabird species breeding in the Gulf of St. Lawrence, Canada. Stable nitrogen (δ¹⁵N) and carbon (δ¹³C) isotopes were used as ecological tracers to measure trophic level and connectivity with benthos, respectively. Concentrations, patterns as well as ecological tracers varied significantly between species. The sum of polychlorinated biphenyls (ΣPCBs) was the most important group measured in all seabird species based on concentration followed generally by the sum of chlorinated pesticides (ΣCPs), the sum of brominated flame retardants (ΣBFRs) and finally total Hg (THg). ΣPCBs, ΣCPs and ΣBFRs increased with trophic level, whereas THg did not. Only ΣBFRs increased with a higher connectivity with the benthos. Seabird species resident to the Great Lakes-St. Lawrence ecosystem showed higher Hg and BFR levels than migratory species. Molt patterns were used to explain variations of contaminant levels.