Matrix in River Water, Sediments, and Biofilms Mitigates Mercury Toxicity to Medaka (Oryzias Latipes).

Impacts of an environmental matrix on mercury (Hg) bioavailability and toxicity to medaka (Oryzias latipes) were investigated in matrix-free controls and treatments with a stepwise increased environmental matrix of river water, sediments, and biofilms. Generally, river water enhanced but the presence of sediments and biofilms reduced Hg bioavailability to medaka up to 105 times, so that Hgtotal concentrations/amounts among different environmental media cannot mirror Hg availability and toxicity to medaka. On average, 12.9 and 12.4% of Hg in medaka was, respectively, methylated to methylmercury (MeHg) in matrix-free and -containing treatments, indicating no influence of the environmental matrix on Hg methylation in medaka. All oxidative stress, inflammatory injury, and malformation parameters correlated strongly and significantly with Hgtotal and MeHg concentrations in medaka, notably with steeper slopes in matrix-free controls than in matrix-containing treatments, highlighting that the environmental matrix mitigated Hg and MeHg toxicity to medaka. Moreover, oxidative stress was more strongly mitigated than inflammatory injury according to the stronger decreases of the regression line slopes from matrix-free to -containing treatments. Here, we have newly identified that the potential of the environmental matrix to decrease Hg bioavailability and mitigate Hg toxicity to fish together could buffer Hg ecotoxicity in the aquatic environment.

Investigating the diet source influence on freshwater fish mercury bioaccumulation and fatty acids-Experiences from Swedish lakes and Chinese reservoirs.

Dietary uptake is key for transferring potentially toxic contaminants, such as mercury (Hg) and essential dietary nutrients, such as polyunsaturated fatty acids (PUFA), to consumers at higher trophic levels of aquatic food webs. We evaluated the role of diet sources for Hg bioaccumulation and PUFA retention in fish across lake food webs in seven Swedish lakes and two Chinese reservoirs. Fish total Hg (THg) and methyl-Hg (MeHg) differed greatly between the two countries: the Chinese fish contained less than 300 ng g-1 dry weight (d.w.) THg with less than 50% as MeHg, versus the Swedish fishes which contained approximately 2000 ng g-1 d.w. THg and nearly 100% as MeHg. Fatty acids enrichment of linoleic acids (LIN) were more prevalent in the Chinese fishes regardless of size (p < 0.05). Here we examined food web length, fish growth rates, and fatty acids patterns in relation to the quality of fish as a food source for both Hg and FA. Contrary to the expectation that biodilution of Hg throughout the food chain would explain these differences, a more complex picture emerged with high levels of Hg at the base of the food web in the Chinese reservoirs, a decoupling of fatty acid and Hg bioaccumulation, and a major role for both fish stocking and fish feed. It is hoped that this work will provide a nuanced picture of fish quality as a food source in different ecosystems.

Anthropogenic activity and millennial climate variability affect Holocene mercury deposition of an alpine wetland near the largest mercury mine in China.

Mercury (Hg) is a potentially toxic element that can be transported globally through the atmosphere, once deposited in the environment, has strong bioaccumulation and extreme toxicity in food webs, especially in wetland ecosystems. Anthropogenic Hg emissions have enhanced Hg deposition by 3-5 times since the industrial revolution, and the mining and smelting of Hg ore are important emission sources. However, the dynamics in Hg deposition around the largest Hg mine in China before the industrial revolution and their driving forces remain poorly explored. Here we reconstruct the atmospheric Hg depositional fluxes (named here Hg influx (Hginflux)) during the Holocene using a 450-cm alpine wetland sediment core taken from the Jiulongchi wetland, which is only 65 km to the Wanshan Mercury Mine. Our record shows an abrupt rapid increase in Hg concentration since 2500 cal yr BP, suggesting that Hg mining in southwest China may have started before the establishment of the Qin dynasty. Two major Hginflux peaks were found during the periods 10,000-6000 and 6000 - 3800 cal yr BP, with an increase in Hg deposition by a factor of 4-8. These two peaks are also found in other terrestrial archives from several sites across the Northern Hemisphere. We speculate that critical millennial-scale climate changes, i.e., the Holocene Climatic Optimum (HCO) and the Mid-Holocene Transition (MHT), were the potential triggers of these two Hginflux peaks. This study highlights the importance of climatic variability and local Hg mining in controlling atmospheric Hg deposition during the Holocene.

How phytoplankton biomass controls metal(loid) bioaccumulation in size-fractionated plankton in anthropogenic-impacted subtropical lakes: A comprehensive study in the Yangtze River Delta, China.

Phytoplankton biomass can significantly affect metal(loid) bioaccumulation in plankton, but the underlying mechanisms are still controversial. We investigated the bioaccumulation of eight metal(loid)s (As, Co, Cu, Hg, Mn, Pb, Se, and Zn) in three size categories of planktonic organisms - seston (0.7-64 µm), mesozooplankton (200-500 µm), and macrozooplankton (>500 µm) - sampled from six freshwater lakes in two seasons in the Yangtze River Delta, China. Our results highlight phytoplankton biomass is the major driver on metal(loid) bioaccumulation in the studied anthropogenic-impacted subtropical lakes, mainly via affecting site-specific water physiochemical characteristics and plankton communities. However, such impact is highly dependent on chlorophyll a (Chl-a) concentration. The bioaccumulation of metal(loid)s in size-fractionated plankton declined significantly with increasing phytoplankton biomass when Chl-a was below ∼50 µg L-1, mainly owing to the reduced metal(loid) bioavailability and subsequent bioaccumulation at more productive sites (with elevated pH and dissolved organic carbon), rather than algal bloom dilution. To a lesser extent, phytoplankton growth dilution and the smaller body-size of zooplankton at more productive sites also contributed to the lower metal(loid) bioaccumulation. The bioaccumulation of metal(loid)s was enhanced under severe algal bloom conditions (when Chl-a concentration was higher than ∼50 µg L-1). Although the underlying mechanisms still require further investigations, the potential risks of metal(loid) bioaccumulation under severe algal bloom conditions deserve special attention.

[Professor SHAO Jing-ming's clinical experience of fire needling for surgical diseases].

Professor SHAO Jing-ming's clinical experience of fire needling for bone-joint tuberculosis, tuberculous cervical lymphadenitis, ganglion cyst and thyrophyma is summarized. Professor SHAO used fire needling to treat bone-joint tuberculosis. The acupoints included ashi points and nearby acupoints, particularly local opposite acupoints (Neixiyan [EX-LE 4] and Dubi [ST 35], Yinlingquan [SP 9] and Yanglingquan [GB 34], Xuehai [SP 10] and Liangqiu [ST 34]), and for the patients with severe yin-cold syndrome, Yanghe decoction was additionally used. For tuberculous cervical lymphadenitis, fire needling was used at different stages. In the early stage, the nucleus was punctured with fire needling; in the middle stage, the pustule was punctured with fire needling combined with cupping; in the late stage, the fire needling was inserted into the fistula or sinus tract, and the surrounding granulation tissue was treated with horizontal penetrating needling. For ganglion cyst, fire needling combined with centro-square needling was applied. For thyrophyma, the surrounding needling with filiform was used; for simple thyroid mass and thyroid nodule, the surrounding needling with fire needling was used.

[Effect of acupuncture preconditioning combined with PI3K blocker LY294002 on airway inflammation in asthmatic rats].

OBJECTIVE: To observe the effect of acupuncture preconditioning combined with PI3K blocker LY294002 on the expression of PI3K and Akt proteins and genes in the lung tissue and the contents of serum IL-12 and IL-13 in asthmatic rats, so as to explore its preprotective mechanism underlying improving asthma. METHODS: Sixty male Wistar rats were randomly divided into blank control, model, acupuncture pretreatment + blank, acupuncture pretreatment, acupuncture pretreatment + LY294002 and LY294002 groups (n=10 in each group). The asthma model was established by intraperitoneal injection of mixture solution of OVA and Al(OH)3 and followed inhalation of 1%OVA for 30 min, once daily for 7 days. Rats of the blocker groups received inhalation of atomized LY294002 solution for 30 min before inhalation of 1% OVA, and acupuncture was applied to "Feishu"(BL13), "Dazhui"(GV14) and "Fengmen"(BL12) for 20 min, once daily for 7 days before modeling. H.E. staining was used to assess histopathological changes of the lung tissue, and ELISA was used to detect the contents of serum IL-12 and IL-13. The immunoactivity of PI3K and Akt and expression of Akt mRNA of the lung tissue were detected by using immunohistochemistry and fluorescence quantitative real-time PCR, separately. RESULTS: Compared with the blank control group, the content of serum IL-12 was significantly decreased (P<0.01), and the content of serum IL-13, the expression levels of PI3K, Akt protein and Akt mRNA were remarkably increased (P<0.01) in the model group. In comparison with the model group, the content of serum IL-12 in the pretreatment, pretreatment + LY294002 and LY294002 groups was significantly increased (P<0.01, P<0.05), while the content of IL-13 and the expression levels of PI3K, Akt protein and Akt mRNA were considerably decreased (P<0.01, P<0.05) in the acupuncture pretreatment, acupuncture pretreatment+LY294002 and LY294002 groups. The therapeutic effect of acupuncture pretreatment+LY294002 was obviously superior to that of simple acupuncture pretreatment and LY294002 (except PI3K and Akt in the LY294002 group) in up-regulating serum IL-12 level, and in down-regulating serum IL-13, and PI3K and Akt protein levels in the lung tissue (P<0.01). H.E. staining showed severe inflammatory factor infiltration in the bronchus and pulmonary interstitium, and obvious bronchial lumen narrowing with increased exudate in rats of the model group, which was relatively milder in rats of the acupuncture pretreatment, acupuncture pretreatment+LY294002 and LY294002 groups. There were no significant diffe-rences between blank control and pretreatment+blank groups in all of the above indicators （P>0.05）. CONCLUSION: Acupuncture preconditioning can inhibit airway inflammation in asthmatic rats, which may be associated with its functions in down-regulating the levels of pulmonary PI3K and Akt and serum IL-13 and up-regulating the content of serum IL-12. Acupuncture preconditioning combined with LY294002 has the best effect.

Diet influence on mercury bioaccumulation as revealed by polyunsaturated fatty acids in zoobenthos from two contrasting environments: Chinese reservoirs and Swedish lakes.

The bioaccumulation of mercury (Hg) and polyunsaturated fatty acids (PUFA) in zoobenthos varies across aquatic food webs. In this field study, contents of total Hg (THg), methylmercury (MeHg) and PUFA were investigated in zoobenthos of Chinese reservoirs and Swedish lakes, with contrasting environmental characteristics and algal diet sources, which can result in difference of Hg and PUFA in zoobenthos from these two habits. Using PUFA as dietary biomarkers of algae in zoobenthos, we evaluated effects of environmental factors and algal diet sources on the accumulation of THg, MeHg, and the highly required PUFA eicosapentaenoic (EPA, 20: 5n-3) and docosahexaenoic acid (DHA, 22:6n-3) in zoobenthos. Average THg and MeHg in zoobenthos were higher in Chinese reservoirs than Swedish lakes (p < 0.05). Average EPA content of zoobenthos was similar in these two habitats (p > 0.05), yet average DHA content of zoobenthos was higher in Chinese reservoirs than Swedish lakes (p < 0.05). Total Hg and MeHg contents of zoobenthos in Swedish lakes were predicted by environmental factors; e.g., negatively with pH and positively with dissolved organic carbon (DOC) concentrations, yet had no significant relationship with the algal dietary. In Chinese reservoirs, however, no environmental factor correlated well with THg contents in zoobenthos, and only DOC concentrations showed positive correlation with MeHg contents in zoobenthos. Besides, the algal dietary was also positively correlated with MeHg contents in zoobenthos. EPA and DHA contents of zoobenthos in Swedish lakes primarily associated with algal diet. By contrast, in Chinese reservoirs, EPA and DHA contents of zoobenthos were affected by both environmental factors and algal diet.

Use of biochar to reduce mercury accumulation in Oryza sativa L: A trial for sustainable management of historically polluted farmlands.

Mitigating the risk of mercury (Hg) contamination in rice soils using environmental friendly amendments is essential to reducing the probable daily intake (PDI) of MeHg via rice consumption. Here, we examined the impacts of different doses (0% (control), 0.6% and 3%) of rice hull-derived biochar (RHB) and mixture of wheat-rice straw-derived biochar (RWB) on the fractionation, phytoavailability, and uptake of total (THg) and methyl Hg (MeHg) by rice in Hg-polluted soil (THg = 78.3 mg kg-1) collected from Wanshan Hg mining area. Both biochars increased rice biomass up to 119% as compared to control. Application of RHB and RWB significantly (P ≤ 0.05) decreased bioavailable Hg (soluble and exchangeable and specifically-sorbed fractions) concentrations by 55-71% and 67-72%, respectively. The addition of RHB significantly decreased MeHg concentrations in the soil. However, RWB (particularly at 3%) increased significantly MeHg concentrations in the soil as compared to the control and RHB treatments, likely due to the increased abundance of Hg-methylation microorganisms (e.g., Geobacter spp., Nitrospira spp.) in the RWB treatments. Both RHB and RWB significantly decreased MeHg concentrations in the rice grain by 55-85%. We estimated a reduction of the PDI of MeHg from 0.26 µg kg-1 bw d-1of control to below the reference dose (0.1 µg kg-1 bw d-1) of two biochar treatments. Our results highlight the potentiality of RWB and RHB for mitigating MeHg accumulation in rice and reducing PDI of MeHg via rice consumption, which offers a sustainable approach for management of Hg-polluted soils.

Soil and ambient air mercury as an indicator of coal-fired power plant emissions: a case study in North China.

Coal-fired power plants (CFPPs) are an important anthropogenic mercury (Hg) source in China, and it is crucial to understand the environmental impacts of this detrimental element emitted from this source. In the present study, field experiments were conducted for measuring Hg in ambient atmosphere and upland agricultural soils within a radius of 10 km surrounding a large scale coal-fired power plant (1550 MW) in Tangshan, Hebei province. Short-term (20 min) average of gaseous elemental mercury (GEM or Hg0) in ambient air varying from 1.5 to 9.0 ng/m3 and total Hg (THg) in surface agricultural soil (0-20 cm) varying from 9.2 to 43.5 µg/kg at different sites were observed. THg in two soil cores decreased with depth, with concentrations being 2-2.5 times higher in the surface layer than that in the deep layer (50-60 cm), indicating the possibility of the atmospheric input of Hg. Based on the information of the total atmospheric Hg emission since this CFPP's operation in 1970s and the increased THg in nearby soils, it was estimated that about 3.9% discharged Hg has accumulated in the nearby agricultural soils. The low retention rate of the total emitted Hg by soils is a result of high proportion of Hg0 (79.5%) in stack gas emission and potential loss of Hg from soil surface reemission. The positive shifting (~ 0.5‰) of Hg isotopic signature (δ202Hg) from deep soil to surface soil reflected Hg deposition from nearby CFPP emissions that are featured with much heavier Hg isotopic signatures inherited from feed coal (δ202Hg: -0.50‰) and different combustion products (δ202Hg: -0.95 to 3.71‰) compared with that in deep soil layer (δ202Hg: ca -1.50‰). Overall, this study demonstrated that this CFPP has a slight but distinguishable effect on the elevation of ambient GEM and agricultural soil THg in the local environment.

Mercury, microcystins and Omega-3 polyunsaturated fatty acids in farmed fish in eutrophic reservoir: Risk and benefit assessment.

Fish is an important source of nutritional omega-3 (n-3) polyunsaturated fatty acids, but it also readily accumulates toxic mercury (Hg) and microcystins (MC) in eutrophic aquatic systems. In China, farmed fish was widely consumed, and aquaculture has caused pervasive eutrophication of freshwater lakes, resulting in the increasing accumulation of MC in fish tissue. To assess the risk-benefit of consuming farmed fish, 205 fish samples of 10 primary species were collected from the eutrophic Wujiangdu (WJD) Reservoir, SW China. The contents of Hg, microcystin-RR (MC-RR), microcystin-LR (MC-LR), and polyunsaturated fatty acids (PUFA) in fish were analyzed. The results showed that THg and MeHg concentrations in all fish sampls were well below the safety limit (500 ng/g w.w) established by the Standardization Administration of China, with average values of 22.9 ± 22.8 and 6.0 ± 6.6 ng/g wet weight (w.w.), respectively. Average concentrations of MC-RR and MC-LR were 40 ± 80 and 50 ± 80 ng/g w.w., respectively. MC-RR and MC-LR concentrations in fish were significantly higher in silver carp and black carp than in perch and catfish (p < 0.05). In nutritional terms, average concentrations of n-3 PUFA and the eicosapentaenoic (EPA) + docosahexaenoic acids (DHA) of fish were 2.0 ± 2.5 and 1.4 ± 0.5 mg/g w.w., respectively. The risk-benefit assessment suggests that the n-3 PUFA benefits from consuming all farmed fish species in the WJD Reservoir outweigh the adverse effects of MeHg. However, except for perch, most fish species still pose a high MC-LR exposure risk that created a requirement for fish consumption advisories and monitoring. Consequently, more attention should be paid on the health risk of combined exposure to pollutants by aquatic product consumption.

Effect of aquaculture on mercury and polyunsaturated fatty acids in fishes from reservoirs in Southwest China.

Aquaculture can affect the polyunsaturated fatty acids (PUFA) and mercury (Hg) in fish by altering their diet. Here, planktivorous (silver carp and bighead carp), omnivorous and carnivorous fish with different dietary strategies were selected from two reservoirs, one with on-going aquaculture (WJD) and another without aquaculture (HF) in Southwest China. We compared the total mercury (THg), methylmercury (MeHg) contents and PUFA profiles of fish and their potential diets in these two reservoirs. THg and MeHg contents in omnivorous and carnivorous fish were lower from the WJD Reservoir, which is related to the lower THg and MeHg contents in the artificial fish food. THg and MeHg contents in silver carp from the WJD Reservoir were lower than those from the HF Reservoir, while they were similar in bighead carps from the two reservoirs. The Hg variation in planktivorous fish were inconsistent with that in plankton. THg contents in phyto- and zooplankton from the HF Reservoir were higher than those from the WJD Reservoir, yet their MeHg contents were similar. Artificial fish food which contained higher total PUFA eicosapentaenoic (EPA; 20:5n-3) and docosahexaenoic acid (DHA, 22:6n-3), significantly increased the total PUFA and EPA + DHA contents in carnivorous fish, but had less effect on that in omnivorous fish from the WJD Reservoir. Eutrophication caused by aquaculture reduced total PUFA and EPA + DHA contents of plankton in WJD, yet did not reduce those in planktivorous fish. The impacts of aquaculture on Hg and PUFA accumulated in fish were varied among different fish species, and the mechanism needs further exploration.

Anthropogenic influences on mercury in Chinese soil and sediment revealed by relationships with total organic carbon.

Rapid industrialization has led to high levels of mercury (Hg) releases from anthropogenic sources in China. When deposited to terrestrial ecosystems, Hg has a high affinity for natural organic carbon. This means that Hg concentrations will vary naturally as a function of the total organic carbon (TOC) content of different soils and sediment. Thus, Hg to TOC ratios in topsoil and surface sediment provides a useful normalized tracer of the anthropogenic impact on Hg contamination. We compiled literature-documented Hg and total organic carbon (TOC) data for topsoil (n = 957) and surface sediment (n = 1142) in China. Topsoil samples (n = 100) were also collected in this study to broaden the spatial coverage. We found large differences in Hg:TOC ratios among topsoil from background sites, agricultural and urban areas, and mining sites and surface sediment from fluvial, coastal, and marine environments. Specifically, a significant increase in Hg:TOC ratios occurred between soils from background sites (median: Hg:TOC = 21.1; Inter-Quartile Range (IQR): 9.67 to 40.7) and agricultural areas (median: 34.1; IQR: 22.1 to 58.7), urban areas (median: 62.1 ng g-1; IQR: 34.2 to 154) and mining sites (median: 2780; range: 181 to 43500). Urban and mining sites show the largest increase in Hg:TOC ratios, reflecting elevated anthropogenic Hg inputs in these areas. Fluvial sediment showed higher Hg:TOC ratios (median: 197; IQR: 109 to 389) than coastal (median: 88.3; IQR: 46.8 to 168) and marine sediment (median: 89.7; IQR: 53 to 138), indicating decreased anthropogenic Hg input from rivers to coastal and marine regions. Results of our study suggest Hg:TOC ratios are a useful normalized indicator of the influence of anthropogenic Hg releases on Hg enrichment in topsoil and surface sediment.

Research Progress of Mercury Bioaccumulation in the Aquatic Food Chain, China: A Review.

Research on mercury (Hg) in aquatic ecosystems in China has focused mainly on fish, with little research on the base of the food chain and Hg bioaccumulation mechanisms. This paper summarizes research progress pertaining to the characteristics, current status, and trends of Hg accumulation in the aquatic food chain in China, analyzes the effects of human activities on the transmission and accumulation of Hg in aquatic food chains, and assesses their risks to human and ecosystem health. A comparison of fish samples in China between 2000 and 2018 indicates that their total Hg content remains at relatively safe levels. However, because current information is generally insufficient to confirm how anthropogenic activities affect transformation and bioaccumulation in the aqueous environment, Hg isotope studies should be a focus of research on aquatic food webs. Additionally, more attention should be paid to Hg transport and bioaccumulation in the basic food chain by focusing on multi-contaminant joint exposure studies and establishing Hg bio-transport models.

Primary amino acids affect the distribution of methylmercury rather than inorganic mercury among tissues of two farmed-raised fish species.

The distributions of primary amino acids, MeHg and IHg in body tissues of two commonly farm-raised fish species (common carp: Cyprinus carpio; grass carp: Ctenopharyngodon idellus) in Guizhou Province, SW China, were investigated to understand the effects of primary amino acids on MeHg and IHg metabolism in farm-raised fish. The primary amino acids were classified into four groups: (1) essential and polar amino acids; (2) essential and non-polar amino acids; (3) non-essential and polar amino acids; and (4) non-essential and non-polar amino acids. For both fish species, groups (1, 2 and 3) were enriched in muscle and kidney, whereas group (4) was enriched in scale. The two fish species showed low MeHg concentrations (grass carp: 0.5-3.9 ng/g; common carp:1.0-7.4 ng/g) and low MeHg proportions (grass carp: 2-45%; common carp: 6-37%) in their tissues, which are mainly due to the simple food web structures and the fast growth of the farm-raised fish. Positive correlations (r = 0.342 to 0.472; p < 0.01; n = 78) were observed between MeHg and several primary amino acids (cysteine, threonine, phenylalanine, leucine, valine, glutamate serine and tyrosine) in fish tissues, which may be driven by the formation of MeHg-Cys complexes within fish body. However, no significant correlations were observed between IHg and any primary amino acids, indicating the metabolic processes of IHg and MeHg are different. This study advances our understanding that cysteine and its related/derived amino acids may be an important driving force for MeHg distribution and translocation in fish.

Mercury contents in rice and potential health risks across China.

Rice samples were collected at 560 sites in 15 provinces across China in areas without known point mercury (Hg) sources. Total mercury (THg) and methylmercury (MeHg) concentrations were analyzed in these rice samples for risk assessment. Relatively low THg and MeHg concentrations were found in the majority of the white rice samples with an overall mean of 4.74 (1.06-22.7) µg kg-1 and 0.682 (0.03-8.71) µg kg-1, respectively. The means (range of) THg concentration of rice in each geographical region were 5.23 (1.07-19.5) µg kg-1, 5.14 (1.06-17.2) µg kg-1, 4.45 (1.41-17.2) µg kg-1, 4.20 (1.48-19.4) µg kg-1, 3.49 (1.49-10.7) µg kg-1, and 4.53 (1.30-19.4) µg kg-1 in east, centre, south, southwest, northwest and northeast, China, respectively, and the corresponding values for MeHg concentrations were 0.898 (0.127-8.35) µg kg-1, 0.603 (0.207-2.48) µg kg-1, 0.516 (0.032-1.50) µg kg-1, 0.615 (0.050-5.03) µg kg-1, 0.704 (0.148-2.41) µg kg-1 and 0.565 (0.035-8.71) µg kg-1, respectively. Hg contents in rice across China were found to be at background levels. Both the probable daily intakes (PDIs) of inorganic Hg (IHg) and MeHg from rice consumption showed low risks for general population in the investigated regions.

Influence of dissolved organic matter (DOM) characteristics on dissolved mercury (Hg) species composition in sediment porewater of lakes from southwest China.

The origin and composition of dissolved organic matter (DOM) in porewater of lake sediments is intricate and decisive for fate of pollutants including mercury (Hg). While there are many reports on the relationship between dissolved organic carbon concentration (DOC) and mercury (Hg) concentrations in aquatic systems, there are few in which DOM compositional properties, that may better explain the fate of Hg, have been the focus. In this study, porewaters from sediments of three lakes, Caihai Lake (CH), Hongfeng Lake (HF) and Wujiangdu Lake (WJD), all located in southwest China, were selected to test the hypothesis that DOM optical properties control the fate of Hg in aquatic ecosystems. Porewater DOM was extracted and characterized by UV-Vis absorption and fluorescence spectroscopy. A two end-member (autochthonous and allochthonous DOM) mixing model was used to unveil the origin of DOM in porewaters of the three lakes. Our results show a higher input of terrestrial DOM in the pristine lake CH, as compared to lakes HF and WJD lakes, which were both influenced by urban environments and enriched in autochthonous DOM. While the relationships between the concentrations of DOC and the different chemical forms of Hg forms were quite inconsistent, we found important links between specific DOM components and the fate of Hg in the three lakes. In particular, our results suggest that allochthonous, terrestrial DOM inhibits Hg(II) availability for Hg methylating micro-organisms. In contrast, autochthonous DOM seems to have been stimulated MeHg formation, likely by enhancing the activity of microbial communities. Indeed, DOM biodegradation experiments revealed that differences in the microbial activity could explain the variation in the concentration of MeHg. While relationships between concentrations of DOC and Hg vary among different sites and provide little information about Hg cycling, we conclude that the transport and transformation of Hg (e.g. the methylation process) are more strongly linked to DOM chemical composition and reactivity.

Compound specific stable isotope determination of methylmercury in contaminated soil.

Rice is one of the main sources of methylmercury (MeHg) to humans, and soil is the main source of MeHg to rice grains. Determining the Hg isotope composition in environmental samples is a good way of characterizing sources of Hg pollution and investigating environmental processes. We developed a new compound-specific method for determining stable Hg isotopes in MeHg in contaminated soil and sediment. The method involved HNO3 leaching/solvent extraction, chemical ethylation, and separation by gas chromatography with a solenoid valve optimized to enrich MeHg. The method was optimized by using MeHg standard solution, certified reference materials and paddy soil samples. The δ202Hg precision for replicate MeHg isotope analyses was 0.14‰ (2 × standard deviation, n = 11), and no fractionation of Hg stable isotopes was found during the separation processes. The δ202Hg values for MeHg in paddy soils were -1.78‰ to -1.30‰, which were lower than the δ202Hg values for total Hg (-1.32‰ to -0.44‰). The results indicated that methylation (rather than demethylation) was the dominant process in the paddy soils. The method developed in this study can help us to better understand MeHg migration and transformation processes in paddy soil-rice ecosystem.

[Distributions, Sources and Pollution Assessment of Hg in Sediment of Douhe Reservoir in Tangshan City].

Sediment cores from Douhe reservoir in Tangshan City were sampled in August 2013, in order to evaluate the mercury (Hg) pollution degree and its possible sources. Agriculture soils surrounding the Douhe reservoir and sediments from an upstream reservoir (Daheiting) were also collected. Total mercury (THg), methylmercury (MeHg), dissolved mercury in pore water (DHg) and organic matter (OM) in sediment of Douhe reservoir were analyzed, while, only THg in the agriculture soils and upstream reservoir sediments was determined. Finally, the geoaccumulation index method was applied to evaluate the Hg pollution status in soils and reservoir sediments. The results showed that THg content in sediment of Douhe reservoir ranged from 19 to 97 ng·g-1. dw, MeHg (dw) from 0.02 to 1.27 ng·g-1, and the contents of both THg and MeHg were higher in the upper layers than the deeper layers, indicating that Hg in sediments was increasing in recent years by the exogenetic loadings. THg (dw) in soils offshore the Douhe reservoir, which is close to a large coal-fired power plant, averaged at 22 ng·g-1. Among the three sediment cores of Douhe reservoir, the central point had the highest THg, followed by the western site, and the eastern site had the lowest THg. While, THg content (dw) in sediments of Daheiting reservoir was much higher, with a mean of 176 ng·g-1. Combining all the above information, we concluded that Hg in Douhe reservoir was mainly derived from the Daheiting reservoir and the mercury atmospheric deposition from the nearby coal-fired power plant contributed a less content. THg and MeHg in the sediments of Douhe reservoir were positively correlated with OM, indicating that OM in sediments had good ability of adsorbing THg and MeHg, and also played an important role in Hg methylation. The geoaccumulation index (Igeo) showed that the Hg pollution status deceased in this order:central of Daheting, Daba of Daheting, central of Douhe, western of Douhe, eastern of Douhe, soils surrounding Douhe. Central and western sites in Douhe belonged to moderate pollution and the eastern site belonged to slight pollution. While, sediments of Daheiting reservoir, affected by the iron ore mining activities, were in the moderate and strong pollution status.

Mercury methylation in rice paddies and its possible controlling factors in the Hg mining area, Guizhou province, Southwest China.

Understanding mercury (Hg) methylation/demethylation processes and the factors controlling methylmercury (MeHg) production within the rice paddy ecosystem of Hg mining areas is critical to assess the risk of MeHg contamination in rice grain. Two typical Hg-contaminated mining sites, a current-day artisanal site (Gouxi) and an abandoned site (Wukeng), were chosen in this study. We qualified the in situ specific methylation/demethylation rate constants in rice paddy soil during a complete rice-growing season. Our results demonstrate that MeHg levels in rice paddy soil were a function of both methylation and demethylation processes and the net methylation potential in the rice paddy soil reflected the measured MeHg production at any time point. Sulfate stimulating the activity of sulfate-reducing bacteria was a potentially important metabolic pathway for Hg methylation in rice paddies. We suggest that bioavailable Hg derived from new atmospheric deposition appears to be the primary factor regulating net MeHg production in rice paddies.

The impacts of organic matter on the distribution and methylation of mercury in a hydroelectric reservoir in Wujiang River, Southwest China.

To understand the impacts of organic matter on the geochemical processing of Hg in a hydroelectric reservoir, spatial and seasonal distributions of total mercury (THg) and methylmercury (MeHg) in both solid and liquid phases of sediment cores were investigated in the Wujiangdu Reservoir in Guizhou Province, China. Four sampling sites with different intensities of cage aquaculture activities were chosen and were evenly distributed from upstream to downstream of the Wujiangdu Reservoir. Elevated MeHg concentrations and the high percentage of MeHg in solid and liquid phases of the surface sediment demonstrated that the active Hg methylation process occurred downstream of the Wujiangdu Reservoir. In contrast, the absence of obvious peaks for MeHg in sediment from the upper reaches of the Wujiangdu Reservoir, consistent with low levels of organic matter, suggested that production of MeHg was limited. In sediment with high organic matter content, reduction occurred closer to the sediment surface, resulting in maximum MeHg concentration in these layers. The correlation between MeHg and organic carbon implied that organic matter content in the sediment originating from cage aquaculture activities can help to predict MeHg production rates in reservoirs, which could be used to assess possible MeHg contamination in a reservoir ecosystem.