Distribution and bioavailability of mercury in size-fractioned atmospheric particles around an ultra-low emission power plant in Southwest China.

Ultra-low emission (ULE) technology retrofits significantly impact the particulate-bound mercury (Hg) emissions from coal-fired power plants (CFPPs); however, the distribution and bioavailability of Hg in size-fractioned particulate matter (PM) around the ULE-retrofitted CFPPs are less understood. Here, total Hg and its chemical speciation in TSP (total suspended particles), PM10 (aerodynamic particle diameter ≤ 10 µm) and PM2.5 (aerodynamic particle diameter ≤ 2.5 µm) around a ULE-retrofitted CFPP in Guizhou Province were quantified. Atmospheric PM2.5 concentration was higher around this ULE-retrofitted CFPP than that in the intra-regional urban cities, and it had higher mass Hg concentration than other size-fractioned PM. Total Hg concentrations in PM had multifarious sources including CFPP, vehicle exhaust and biomass combustion, while they were significantly higher in autumn and winter than those in other seasons (P < 0.05). Regardless of particulate size, atmospheric PM-bound Hg had lower residual fractions (< 21%) while higher HCl-soluble fractions (> 40%). Mass concentrations of exchangeable, HCl-soluble, elemental, and residual Hg in PM2.5 were higher than those in other size-fractioned PM, and were markedly elevated in autumn and winter (P < 0.05). In PM2.5, HCl-soluble Hg presented a significantly positive relationship with elemental Hg (P < 0.05), while residual Hg showed the significantly positive relationships with HCl-soluble Hg and elemental Hg (P < 0.01). Overall, these results suggested that atmospheric PM-bound Hg around the ULE-retrofitted CFPP tends to accumulate in finer PM, and has higher bioavailable fractions, while has potential transformation between chemical speciation.

Application potential of biofertilizer-assisted Pennisetum giganteum in safe utilization of mercury-contaminated paddy fields.

High mercury (Hg) bioaccumulation in crops such as rice in Hg-contaminated areas presents a potential health hazard to humans and wildlife. To develop a safe alternative technique, bacillus-inoculated biofertilizer, citric acid, earthworms, and selenium-modified activated clay were compared for their ability to regulate Hg bioaccumulation in Pennisetum giganteum (P. giganteum). This biofertilizer significantly increased Bacillus sp. abundance in the soil by 157.12%, resulting in the removal of 27.52% of water-soluble Hg fractions through volatilization and adsorption mechanisms. The variation in bioavailable Hg in the soil significantly reduced the total Hg concentration in P. giganteum young leaves, old leaves, stems, and roots of P. giganteum by 74.14%, 48.08%, 93.72%, and 50.91%, respectively (p < 0.05), which is lower than the Chinese feed safety standard (100 ng g-1). The biofertilizer inhibitory potential was highly consistent with that of the selenium-modified activated clay. Biofertilizers significantly reduced the methylmercury concentration in various P. giganteum tissues (p < 0.05), whereas selenium-modified activated clay failed to achieve a comparable effect. This biofertilizer-assisted planting pattern can achieve an economic income quadruple that of the rice planting pattern in the Hg-contaminated paddy fields. Because of its significant environmental and financial applications, the biofertilizer-assisted planting pattern is expected to replace Hg-contaminated paddy fields.

Effects of Composted Agricultural Organic Materials on Mercury Methylation in Paddy Soil and Mercury Enrichment in Rice.

Many studies have shown that returning fresh straw to the field can promote mercury accumulation in crops; therefore, it is necessary to find an appropriate way to use agricultural organic materials in mercury-contaminated farmlands. In this study, pot experiments were conducted to study the effects of composted agricultural organic materials on mercury bioaccumulation in the paddy field ecosystem by adding fresh rice straw (RS), composted rice straw (CRS), cow dung (CD) and composted cow dung (CCD) to the soils. Compared with RS and CD, the CRS and CCD amendments reduced dissolved organic matter (DOM) contents in soil, but increased the aromaticity and small molecule proportion of DOM, and also increased the tartaric acid contents in soil, as well as the methylation and release of mercury in soil. However, the increased available mercury and methylmercury in the soils in the CRS and CCD treatments were not effectively absorbed by rice plants. Overall, compared with fresh organic materials, composted organic materials amendments could reduce mercury accumulation in rice to a certain extent.

Distribution and Release of Mercury Regulated by the Decomposition of a Pioneer Habitat-Adapted Plant in the Water-Level-Fluctuating Zone of the Three Gorges Reservoir.

Pioneer habitat-adapted bermudagrass is prevalent in the water-level-fluctuating zone of the Three Gorges Reservoir area. This study was performed to explore the response characteristics of dissolved organic matter (DOM) qualities to bermudagrass decomposition and their regulation in the distribution and release of mercury (Hg) and methylmercury (MeHg) in the soil-water system. Compared to the control, the bermudagrass decomposition resulted in a great increase in the protein-like components in the water in the initial stages (p < 0.01), but it also greatly reduced the humification degree of water DOM (p < 0.01). However, it accelerated the consumption of protein-like components, the humification rate, and the synthesis of humic-like DOM in the water over time. This changing pattern of the DOM qualities resulted in an initial elevation and a subsequent great decrease in the dissolved Hg and MeHg concentrations in the pore water, which ultimately reduced their release levels into the overlying water by 26.50% and 54.42%, respectively, compared to the control. Our results indicate the potential inhibitory effects of short-term bermudagrass decomposition caused by flooding and how decomposition affects the release of total Hg and MeHg by shaping the DOM qualities, and they have implications for similar aquatic systems in which herbaceous plants are frequently decomposed after submergence.

Remediation of Mercury-Polluted Farmland Soils: A Review.

Mercury (Hg) bioaccumulation in Hg-polluted farmlands poses high health risk for humans and wildlife, and remediation work is urgently needed. Here, we first summarize some specific findings related to the environmental process of Hg in Hg-polluted farmlands, and distinguish the main achievements and deficiencies of available remediation strategies in recent studies. Results demonstrate that farmland is a sensitive area with vibrant Hg biogeochemistry. Current remediation methods are relatively hysteretic whether in mechanism understanding or field application, and deficient for large-scale Hg-polluted farmlands in view of safety, efficiency, sustainability, and cost-effectiveness. New perspectives including environment-friendly functional materials, assisted phytoremediation and agronomic regulations are worthy of further study as their key roles in reducing Hg exposure risk and protecting agricultural sustainability.

Effects of fulvic acid and humic acid from different sources on Hg methylation in soil and accumulation in rice.

Humus is often used as an organic modifier to reduce the bioaccumulation of heavy metals in plants, but the effects of different humus components from different sources on the fate of mercury (Hg) in paddy fields are still unclear. Here, fulvic acid (FA) and humic acid (HA) extracted from composted straw (CS), composted cow dung (CCD), peat soil (PM) and lignite coal (LC) were used to understand their effects on the methylation and bioaccumulation of Hg in paddy soil by pot experiments. Amendments of both FA and HA largely increased the abundance of Hg-methylating microbes and low-molecular-weight organic matters (e.g, cysteine) in paddy soil. They were also found to change the aromaticity, molecular size and Chromophoric DOM concentration of DOM, and resulted in heterogeneous effects on migration and transformation of Hg. All the FA-amended treatments increased the mobility and methylation of Hg in soil and its absorption in roots. Nevertheless, FA from different sources have heterogeneous effects on transport of Hg between rice tissues. FA-CCD and FA-PM promoted the translocation of MeHg from roots to rice grains by 32.95% and 41.12%, while FA-CS and FA-LC significantly inhibited the translocation of inorganic Hg (IHg) by 52.65% and 66.06% and of MeHg by 46.65% and 36.23%, respectively. In contrast, all HA-amended treatments reduced the mobility of soil Hg, but promoted Hg methylation in soil. Among which, HA-CCD and HA-PM promoted the translocation of MeHg in rice tissues by 88.95% and 64.10%, while its accumulation in rice grains by 28.43% and 28.69%, respectively. In general, the application of some FA and HA as organic modifiers to reduce Hg bioaccumulation in rice is not feasible.

Mercury Bioaccumulation in Freshwater Snails as Influenced by Soil Composition.

Soil properties largely control the fate of mercury (Hg), including the synthesis of neurovirulent methylmercury (MeHg). Here, the freshwater snail (Cipangopaludina cahayensis), a snail species commonly bred in flooded farmland, was used in a test of biotoxicity exposure to explore the effects of soil components on Hg bioavailability. The results show that snails incubated on the surface of slightly Hg-polluted flooded soil (2.0 mg/kg) have MeHg concentrations of 7.9 ± 1.5 mg/kg, which greatly exceed the limit of contaminants in food in China (0.5 mg/kg). The addition of ferrous disulfide can significantly increase the MeHg concentrations in soils while reducing the concentrations of total Hg (THg) and MeHg levels in snails by 59.1% and 64.3%, respectively. Peat-derived fulvic acid has the capacity to reduce the MeHg concentrations in soils and snails by 23.8% and 33.2%, respectively, whereas it increases the dissolved Hg levels in overlying water by 104.3%. Moreover, Fe-Mn oxides and humic acid can consistently reduce THg and MeHg concentrations in snails. Overall, freshwater snails bred in Hg-polluted areas may suffer from a high risk of Hg exposure, and importantly, some soil components such as ferrous disulfide and humic acid have strong inhibitory effects on Hg bioaccumulation in snails.

Modified clay mineral: A method for the remediation of the mercury-polluted paddy soil.

Rice is easy to accumulate mercury (Hg), especially methylmercury (MeHg) with high toxicity, and this leads to a serious health risk for residents in some Hg-polluted areas of Asia. Thus, there is an urgent need to find soil remediation techniques that can both guarantee agricultural production and protect human health in these Hg-contaminated areas. In this study, montmorillonite (Mont) and medical stone (Med) were modified by a thiol-based material (-SH) and by chitosan to obtain modified clay mineral adsorbents. Pot experiments were then performed to explore their ability to reduce the levels of Hg and MeHg in rice and their reduction mechanisms. Compared with unmodified clay minerals, modified clay minerals had better Hg reduction efficiencies in rice. The amendment of SH-modified Med (Med-SH) had the highest THg and MeHg reduction efficiencies in rice, reaching up to 78% and 81%, respectively, and brought the THg concentration in the rice below China's health guidelines for rice (20 ng g-1). Not only did amendment of the SH-modified clay minerals reduce the exchangeable and specially adsorbed Hg in the soil, as did the other amendments, but they also significantly reduced the amount of oxide-bound Hg and MeHg in the soil, and greatly enhanced the retention of Hg and MeHg in soil, thus significantly reduced the concentration of Hg and MeHg in rice.

A Review of Studies on the Biogeochemical Behaviors of Mercury in the Three Gorges Reservoir, China.

The Three Gorges Reservoir (TGR) is a relatively large reservoir, and its water level management actions produce a widespread water level fluctuation zone (WLFZ), which has characteristics of both terrestrial and aquatic ecosystems. Here, an integrated overview of current knowledge on Hg behaviors in the TGR, especially the WLFZ, as well as exposure risk to local residents was presented. Hg levels in the TGR were comparable with other natural aquatic systems. WLFZ in the TGR was confirmed to be an environment favorable for Hg methylation by enhancing microbial activity, promoting sulfur cycling and increasing the level of low-molecular-weight organic matters. However, elevated fish Hg concentrations did not follow the impoundment of TGR, indicating no obvious reservoir effect, while it is still noteworthy that frequently consuming fish is likely to be a methylmercury (MeHg) exposure pathway for specific populations e.g. fishermen around the TGR.

Effects of soil properties on production and bioaccumulation of methylmercury in rice paddies at a mercury mining area, China.

Rice paddy soil is recognized as the hotspot of mercury (Hg) methylation, which is mainly a biotic process mediated by many abiotic factors. In this study, effects of key soil properties on the production and bioaccumulation of Hg and methylmercury (MeHg) in Hg-contaminated rice paddies were investigated. Rice and soil samples were collected from the active Hg smelting site and abandoned Hg mining sites (a total of 124 paddy fields) in the Wanshan Mercury Mine, China. Total Hg (THg) and MeHg in soils and rice grains, together with sulfur (S), selenium (Se), organic matter (OM), nitrogen (N), phosphorus (P), mineral compositions (e.g., SiO2, Al2O3 and Fe2O3) and pH in soils were quantified. The results showed that long-term Hg mining activities had resulted in THg and MeHg contaminations in soil-rice system. The newly-deposited atmospheric Hg was more readily methylated relative to the native Hg already in soils, which could be responsible for the elevated MeHg levels in soils and rice grains around the active artificial Hg smelting site. The MeHg concentrations in soils and rice grains showed a significantly negative relationship with soil N/Hg, S/Hg and OM/Hg ratio possibly due to the formation of low-bioavailability Hg-S(N)-OM complexes in rhizosphere. The Hg-Se antagonism undoubtedly occurred in soil-rice system, while its role in bioaccumulation of MeHg in the MeHg-contaminated rice paddies was minor. However, other soil properties showed less influence on the production and bioaccumulation of MeHg in rice paddies located at the Wanshan Mercury Mine zone.

Investigating the role of poly-γ-glutamic acid in Pennisetum giganteum phytoextraction of mercury-contaminated soil.

Farmland mercury (Hg) pollution poses a significant threat to human health, but there is a lack of highly efficient phytoextraction for its remediation at present. This study investigates the impact of poly-γ-glutamic acid (γ-PGA) on the phytoextraction capabilities of Pennisetum giganteum (P. giganteum) in Hg-contaminated soil. Our research indicates that amending γ-PGA to soil markedly enhances the assimilation of soil Hg by P. giganteum and transformation of Hg within itself, with observed increases in Hg concentrations in roots, stems, and leaves by 1.1, 4.3, and 18.9 times, respectively, compared to the control. This enhancement is attributed to that γ-PGA can facilitate the hydrophilic and bioavailable of soil Hg. Besides, γ-PGA can stimulate the abundance of Hg-resistance bacteria Proteobacteria in the rhizosphere of P. giganteum, thus increasing the mobility and uptake of soil Hg by P. giganteum roots. Moreover, the hydrophilic nature of Hg-γ-PGA complexes supports their transport via the apoplastic pathway, across the epidermis, and through the Casparian strip, eventually leading to immobilization in the mesophyll tissues. This study provides novel insights into the mechanisms of Hg phytoextraction, demonstrating that γ-PGA significantly enhances the effectiveness of P. giganteum in Hg uptake and translocation. The findings suggest a promising approach for the remediation of Hg-contaminated soil, offering a sustainable and efficient strategy for environmental management and health risk mitigation.

Selenium-phosphorus modified biochar reduces mercury methylation and bioavailability in agricultural soil.

Biochar is a frequently employed for solidifying and stabilizing mercury (Hg) contamination in soil. However, it often results in an elevated presence of soil methylmercury (MeHg), which introduces new environmental risks. Consequently, there is a necessity for developing a safer modified biochar for use in Hg-contaminated soil. This study employed sodium selenite (at a safe dosage for soil) and hydroxyapatite to modify straw biochar (BC) based on the interaction between selenium (Se) and phosphorus (P). This process led to the formation of Se-modified biochar (Se-BC), P-modified biochar (P-BC), and Se and P co-modified biochar (Se-P-BC). Additionally, solvent adsorption experiments and pot experiments (BC/soil mass ratio: 0.5 %) were conducted to investigate the impacts of these soil amendments on soil Hg methylation and bioavailability. Se and P co-modification substantially increased the surface area, pore volume, and Hg adsorption capacity of BC. BC treatment increased the simulated gastric acid-soluble Hg, organo-chelated Hg, and MeHg in the soil. Conversely, Se-P-BC significantly reduced these forms of Hg in the soil, indicating that Se-P-BC can transform soil Hg into less bioavailable states. Among the different biochar treatments, Se-P-BC exhibited the most pronounced reductions in soil MeHg, total Hg, and MeHg in water spinach, achieving reductions of 63 %, 71 %, and 70 %, respectively. The co-modification of Se and P displayed a synergistic reduction effect in managing soil Hg pollution, which is associated with the increase of available Se in the soil due to phosphorus addition. The significantly reduced dissolved organic carbon and the abnormally high SO42- concentration in the soil of Se-P-BC treatment also inhibited Hg methylation and bioavailability in the soil. In summary, Se-P-BC substantially increased reduction percentage in plant Hg content while mitigating the risk of secondary pollution arising from elevated soil MeHg.

Suppression of mercury methylation in soil and methylmercury accumulation in rice by dissolved organic matter derived from sulfur-rich rape straw.

Straw amendment significantly enhances mercury (Hg) methylation and subsequent methylmercury (MeHg) bioaccumulation in Hg-contaminated paddy fields by releasing dissolved organic matter (DOM). This study comprehensively investigates the regulatory mechanisms of DOM and its different molecular weights derived from sulfur-rich rape straw (RaDOM) and composted rape straw (CRaDOM) applied in the rice-filling stage on soil MeHg production and subsequent bioaccumulation in rice grains. The results indicated that the amendment of RaDOM and CRaDOM significantly reduced soil MeHg content by 42.40-62.42%. This reduction can be attributed to several factors, including the suppression of Hg-methylating bacteria in soil, the supply of sulfate from RaDOM and CRaDOM, and the increase in the humification, molecular weight, and humic-like fractions of soil DOM. Additionally, adding RaDOM increased the MeHg bioaccumulation factor in roots by 27.55% while inhibiting MeHg transportation by 12.24% and ultimately reducing MeHg content in grains by 21.24% compared to the control group. Similarly, CRaDOM enhanced MeHg accumulation by 25.19%, suppressed MeHg transportation by 39.65%, and reduced MeHg levels in the grains by 27.94%. The assimilation of sulfate derived from RaDOM and CRaDOM into glutathione may be responsible for the increased retention of MeHg in the roots. Over the three days, there was a significant decrease in soil MeHg content as the molecular weight of RaDOM increased; conversely, altering the molecular weight of CRaDOM demonstrated an inverse trend. However, this pattern was not observed after 12 days. Applying sulfur-rich rape DOM can help mitigate MeHg accumulation in paddy fields by regulating the quality of soil DOM, sulfur cycling, and Hg-methylating bacteria.

The Effects of Different Soil Component Couplings on the Methylation and Bioavailability of Mercury in Soil.

Soil composition can influence the chemical forms and bioavailability of soil mercury (Hg). However, previous studies have predominantly focused on the influence of individual components on the biogeochemical behavior of soil Hg, while the influence of various component interactions among several individual factors remain unclear. In this study, artificial soil was prepared by precisely regulating its components, and a controlled potted experiment was conducted to investigate the influence of various organic and inorganic constituents, as well as different soil textures resulting from their coupling, on soil Hg methylation and its bioavailability. Our findings show that inorganic components in the soils primarily exhibit adsorption and fixation effects on Hg, thereby reducing the accumulation of total mercury (THg) and methylmercury (MeHg) in plants. It is noteworthy that iron sulfide simultaneously resulted in an increase in soil MeHg concentration (277%). Concentrations of THg and MeHg in soil with peat were lower in rice but greater in spinach. A correlation analysis indicated that the size of soil particles was a crucial factor affecting the accumulation of Hg in plants. Consequently, even though fulvic acid activated soil Hg, it significantly increased the proportion of soil particles smaller than 100.8 µm, thus inhibiting the accumulation of Hg in plants, particularly reducing the concentration of THg (93%) and MeHg (85%) in water spinach. These results demonstrate that the interaction of organic and inorganic components can influence the biogeochemical behavior of soil Hg not only through their chemical properties, but also by altering the soil texture.

Elevated methylmercury production in mercury-contaminated paddy soil resulted from the favorable dissolved organic matter variation created by algal decomposition.

Algae-derived organic matter (AOM) may considerably regulate methylmercury (MeHg) production and accumulation in the paddy fields by changing the soil-dissolved OM (SDOM) properties. In this study, a 25-day microcosm experiment was performed to compare the responding mechanisms of MeHg production in the Hg-contaminated paddy soil-water system to the input of algae-, rice-, and rape-derived OMs. Results showed that algal decomposition could release much more cysteine and sulfate than crop straws. Compared with crop straw-derived OMs, AOM input greatly increased the dissolved organic carbon concentrations in soil but resulted in a greater decrease in tryptophan-like fractions while accelerated the formation of high-molecular-weight fractions in soil DOM. Moreover, AOM input significantly increased MeHg concentrations in the pore water by 19.43%-3427.66% and 52.81%-5846.57% compared to rape- and rice-derived OMs, respectively (P < 0.05). And, a similar MeHg changing pattern was also observed in the overlying water (10-25 d) and the soil solid-phase particles (15-25 d) (P < 0.05). Correlation analysis revealed that MeHg concentrations in the AOM-added soil-water system had significantly negative and positive relationships with the tryptophan-like C4 fraction and molecular weight (E2/E3 ratio) of soil DOM, respectively (P < 0.01). These findings suggest that AOM has a higher capacity than crop straw-derived OMs to promote MeHg production and accumulation in the Hg-contaminated paddy soils by creating a favorable soil DOM variation and providing more microbial electron donors and receptors.

Mercury and methylmercury in Hg-contaminated paddy soil and their uptake in rice as regulated by DOM from different agricultural sources.

In this study, from the perspectives of structural and compositional variations of soil-dissolved organic matter (DOM), we explored the effects of agricultural DOM inputs on methylmercury (MeHg) accumulation in the soil and mercury (Hg) bioaccumulation in rice grains. Pot experiments with the addition of DOMs from maize straw (MaS), rape straw (RaS), rice straw (RiS), composted rice straw (CRiS), cow dung (CD), and composted cow dung (CCD) were then conducted. Results showed that, relative to the control, the DOM amendment from each agricultural source elevated MeHg concentrations in the soil, with an increase of 18-227%, but only parts of DOMs elevated total dissolved Hg (DHg) and MeHg (DMeHg) concentrations in pore water. Among all DOM species, RiS, CRiS, and CCD significantly increased total Hg (THg) and MeHg contents in rice grains by 34-64% and 32-118%, respectively. Compared with RiS, THg and MeHg contents in rice grains in the CRiS treatment decreased slightly, which was consistent with the distributions of DHg and DMeHg concentrations in pore water and the aromaticity variation of soil DOM. In contrast, the CCD input significantly enhanced the enrichment of THg and MeHg in rice grains relative to CD because it significantly reduced the humification of soil DOM at all rice-growing stages while increasing the low-molecular-weight fractions in soil DOM. The THg and MeHg contents in the rice grains were significantly lower treated by RaS than those by MaS and RiS, which may be related to the higher sulfur-containing compounds such as sulfate and cysteine in rape straw or its DOM solution. Overall, DOM amendment from different agricultural sources resulted in significantly discriminative effects on the MeHg accumulation in soil and Hg enrichment in rice in the Hg-contaminated paddy field by shaping soil DOM properties.

Selenium/sulfur-modified montmorillonite materials mitigate mercury pollution in farmland.

Selenium (Se) amendment could reduce mercury (Hg) bioaccumulation in crops, but sometimes it could cause excessive Se accumulation in crops and potential Se exposure risks for humans. In this study, we designed and synthesized selenium and sulfur-modified montmorillonite materials (Se/S-Mont) to effectively reduce mercury levels and avoid excessive Se enrichment in plants. The results of pot experiments (1 g Se/S-Mont/100 g soil) and field microplot trials (0.3 g Se/S-Mont/100 g soil, 8 t/ha) showed that Se/S-Mont amendments significantly reduced the Hg concentrations in water spinach and hybrid Pennisetum by 28-68% and 57%-92% (P < 0.05), respectively, while they did not lead to excessive Se bioaccumulation in the plants. Se/S-Mont was more efficient in mitigating soil Hg pollution than adding raw materials (e.g., NaSeO3) and their combinations, and they significantly reduced the available Se fraction in the soil and the Se levels in the plants (P < 0.05). The potential mechanisms revealed by X-ray absorption near-edge spectra (XANES) and pot experiments were the adsorption and slow release of Hg, S, and Se by Se/S-Mont, the high affinity between Hg and Se, competition between Se and S, and the formation of stable complexes containing Se-S-Hg. The Se/S-Mont immobilizer was easy to prepare and required the application of small amounts, and the remediation effect was relatively stable and exhibited few negative effects; therefore, the approach showed high environmental and economic potentials.

Distribution of Mercury and Methylmercury in Farmland Soils Affected by Manganese Mining and Smelting Activities.

Manganese (Mn)-related activities would affect the mercury (Hg) cycling in farmlands, whereas this was not well understood. Here, one of the largest Mn ores in China was selected to study the effects of Mn-related activities on the accumulation and distribution of total Hg (THg) and methylmercury (MeHg) in farmland soils. The soil THg concentrations in the mining area were 0.56 ± 0.45, 0.56 ± 0.45, 0.53 ± 0.44, and 0.50 ± 0.46 mg kg−1 in the 0−10, 10−20, 20−30, and 30−40 cm layers, respectively, while they were increased to 0.75 ± 0.75, 0.72 ± 0.60, 0.62 ± 0.46, and 0.52 ± 0.38 mg kg−1 in the smelting area. Similarly, the soil MeHg concentrations in the smelting area were also elevated by 1.04−1.34 times as compared to those in the mining area. Concentrations of THg (0.59 ± 0.50 mg kg−1) and MeHg (0.64 ± 0.82 µg kg−1) in soils were higher than the regional background value but lower than in vicinal Hg-mining areas, while they were largely elevated at the intersection of two rivers in the smelting area. Significant positive Mn-THg relationship (p < 0.01) and negative Mn-MeHg relationship (p < 0.01) favored the conclusion that soil Mn could promote Hg accumulation while inhibiting MeHg production. Approximately 70% of soil Hg was distributed in the residual phase, and the environmental hazard was not elevated according to a geochemical model. Overall, mining and smelting activities of Mn ores have resulted in obvious and distinct effects on the accumulation and methylation of Hg in farmland soils, but the environmental hazards are currently manageable.

Fulvic acid: A key factor governing mercury bioavailability in a polluted plateau wetland.

Fulvic acids (FAs) are known to regulate the fate of mercury (Hg) in sediments, but the key effects of their properties are still unclear. In this study, field investigations and simulation experiments were conducted in a heavy metal-polluted wetland to identify FA characteristics and their association with the production and bioaccumulation of methylmercury (MeHg). Compared to permanently inundated areas (PIA), seasonally inundated areas (SIAs) had lower total Hg levels in sediments, whereas higher MeHg levels in sediments (0.20 ± 0.09 ng g-1 vs. 0.55 ± 0.31 ng g-1) and benthos (0.25 ± 0.22 ng g-1 vs. 1.62 ± 1.78 ng g-1). Meanwhile, the THg and MeHg concentrations in the same macrophyte species between PIA and SIA also followed a similar rule with benthos. FA-bound Hg in the sediment was significantly correlated with MeHg in the sediment (p < 0.01), as well as THg and MeHg in benthos (p < 0.05), indicating that FAs have the capacity to promote MeHg production and bioaccumulation. Moreover, the FAs in the sediments of the SIA had lower fractions and alkyl C/O-alkyl C ratios, but higher molecular weights and THg/MeHg concentrations than those in the PIA, indicating that FAs in SIA have increased bioavailability and enhanced competition for Hg, favoring significantly elevated FA-bound Hg levels. Biological exposure testing further demonstrated that FAs extracted from SIA had a greater ability to increase the production and bioaccumulation of MeHg than those extracted from PIA. Overall, these results highlight that the molecular composition and sources of FAs, excluding their concentrations, are one of important factors responsible for the obvious spatial heterogeneity of MeHg in sediments and aquatic organisms in the wetland.

Ecological risks of heavy metals as influenced by water-level fluctuations in a polluted plateau wetland, southwest China.

The Caohai wetland, one of karst plateau wetlands in southwest China, is given more attention due to the serious heavy metal (HM) pollution from artisanal zinc smelting activities. A natural hydrological change has caused this wetland to form a water-level fluctuating zone. This raises a question of whether such an area has elevated HM risks to the aquatic environment, and it was explored by a field investigation and biological exposure experiment. The results showed that Caohai sediment properties were significantly altered by water-level fluctuation, and the permanently inundated sediment had obviously higher organic matter (SOM) concentrations (32.62 ± 9.37%), humification levels (ratio of C to H, 6.81 ± 0.97), and Fe oxide fractions (12.29 ± 3.17%) than seasonally inundated sediment (4.94 ± 2.25%, 1.33 ± 0.75, and 8.72 ± 1.87%, respectively). These significantly enhanced the competition and retention, resulting in the increased accumulation, whereas reduced bioavailability of HMs. In comparison, the mean bioaccumulation capacity of Zn, Pb and Cd by wild benthos at the seasonally inundated area respectively increased by 2, 11 and 20 times higher than that at the permanently inundated area, which was further verified in the biological incubation experiment. Our results suggest that hydraulic fluctuation can greatly shape the sediment properties to increase the ecological risks of HMs to organisms.