Predictive modeling of methylmercury in rice (Oryza sativa L.) and species-sensitivity-distribution-based derivation of the threshold of soil mercury in karst mountain areas.

The bioavailable mercury (Hg) in the soil is highly active and can affect the formulation of methyl-Hg (MeHg) in soil and its accumulation in rice. Herein, we predicted the concentration of MeHg in rice using bioavailable Hg extracted from soils; additionally, we determined the threshold value of soil Hg in karst mountain areas based on species sensitivity distribution. The bioavailable Hg was extracted using calcium chloride, hydrochloric acid (HCl), diethylenetriaminepentaacetic acid mixture, ammonium acetate, and thioglycolic acid. Results showed that HCl is the best extractant, and the prediction model demonstrated good predictability of the MeHg concentration in rice based on the HCl-extractable Hg, pH, and soil organic matter (SOM) data. Compared with the actual MeHg concentration in rice, approximately 99% of the predicted values (n = 103) were within the 95% prediction range, indicating the good performance of the rice MeHg prediction model based on soil pH, SOM, and bioavailable Hg in karst mountain areas. Based on this MeHg prediction model, the safety threshold of soil Hg was calculated to be 0.0936 mg/kg, which is much lower than the soil pollution risk screening value of agricultural land (0.5 mg/kg), suggesting that a stricter standard should be applied regarding soil Hg in karst mountain areas. This study presents the threshold of soil Hg pollution for rice safety in karst mountain areas, and future studies should target this threshold range.

Using live videography observation and Bayesian isotope mixing model to identify food composition and dietary contribution to inorganic mercury and methylmercury intake by songbird nestlings.

Mercury (Hg) exposure is increasing in terrestrial birds; however, studies on its sources are scarce. In the present study, we elucidated the food composition of green-backed tit nestlings from three urban forest parks (CPL, AHL, and LCG) using live videography observation (LVO). Furthermore, the daily dietary intakes of inorganic Hg (IHg) (MDIIHg) and methylmercury (MeHg) (MDIMeHg) were determined using the Bayesian isotope mixing model (BIMM) to uncover the nestlings' specific dietary Hg contribution. Both LVO and BIMM indicated that Lepidoptera (primarily caterpillar) constituted the primary food source for the nestlings in the three forests, accounting for approximately 60% of their diet in all three forest parks. The estimated MDI of Hg revealed that lepidopterans and spiders primarily contributed to IHg exposure, with a co-contribution ratio of 71.8%-97.7%. Unexpectedly, dietary MeHg was mostly derived from spiders; the highest contribution ratio of 93.6% was recorded at CPL, followed by another peak ratio of 92.9% at LCG. However, the dietary exposure was primarily IHg, accounting for 69.8% (AHL), 62.0% (LCG), and 61.3% (CPL) of the nestlings. Our study findings highlight the importance of dietary IHg transfer in evaluating the effects of Hg in nestlings. LVO, coupled with BIMM, is an effective tool for determining the food compositions of songbird nestlings and estimating the contribution of specific diets.

Aquatic methylmercury is a significant subsidy for terrestrial songbirds: Evidence from the odd mass-independent fractionation of mercury isotopes.

In contrast to aquatic food chains, knowledge of the origins and transfer of mercury (Hg) and methylmercury (MeHg) in terrestrial food chains is relatively limited, especially in songbirds. We collected soil, rice plants, aquatic and terrestrial invertebrates, small wild fish, and resident songbird feathers from an Hg-contaminated rice paddy ecosystem for an analysis of stable Hg isotopes to clarify the sources of Hg and its transfer in songbirds and their prey. Significant mass-dependent fractionation (MDF, δ202Hg), but no mass-independent fractionation (MIF, ∆199Hg) occurred in the trophic transfers in terrestrial food chains. Piscivorous, granivorous, and frugivorous songbirds and aquatic invertebrates were all characterized by elevated Δ199Hg values. The estimated MeHg isotopic compositions obtained using linear fitting and a binary mixing model explained both the terrestrial and aquatic origins of MeHg in the terrestrial food chains. We found that MeHg from aquatic habitats is an important subsidy for terrestrial songbirds, even those that feed mainly on seeds, fruits, or cereals. The results show that MIF of the MeHg isotope is a reliable tool to reveal MeHg sources in songbirds. Because the MeHg isotopic compositions was calculated with a binary mixing model or directly estimated from the high proportions of MeHg, compound-specific isotope analysis of Hg would be more useful for the interpretation of the Hg sources, and is highly recommended for future studies.

Integrated Insights into Source Apportionment and Source-Specific Health Risks of Potential Pollutants in Urban Park Soils on the Karst Plateau, SW China.

Polycyclic aromatic hydrocarbons (PAHs) and heavy metal(loid)s (HMs) pose risks to environmental and human health. Identification of priority control contaminants is important in guiding the management and control of these synchronous pollutants. A total of 247 soil samples were collected from 64 urban parks in the karst plateau city of Guiyang in SW China to determine the concentrations, spatial distributions, and health risks of PAHs and HMs. The results indicate that dibenz(ah)anthracene and benzo(a)pyrene are the main PAHs species of high ecological risk, and Cr, Mn, and Ni pose elevated ecological risk among the HMs. Four sources were identified for PAHs (biomass burning, coke oven, traffic sources, and coal burning) and HMs (traffic sources, coal burning, industrial sources, and natural sources). The non-carcinogenic risk (NCR) and total carcinogenic risk (TCR) of PAHs were all determined to be negligible and at acceptable levels, several orders of magnitude below those of HMs. The NCR and TCR values of HMs were relatively high, especially for children (11.9% of NCR > 1; 79.1% of TCR > 10-4). Coal burning and natural sources make the greatest contributions to the NCR and TCR values from karst park soils in Guiyang. Considering HMs bioavailability, NCR and TCR values were rather low, due to the high residual HM fractions. Integrated insights into source specific ecological and human health risk indicate future directions for management and control of synchronous PAH and HM pollution, particularly for karst plateau areas. Supplementary Information: The online version contains supplementary material available at 10.1007/s12403-023-00534-3.

Terrestrial mercury and methylmercury bioaccumulation and trophic transfer in subtropical urban forest food webs.

As the "lungs of the city", urban forests can improve air quality by absorbing air pollutants, becoming hotspots for mercury (Hg) pollution from anthropogenic activities. However, the bioaccumulation and transfer of Hg in the urban forest food web are unclear. In this study, total mercury (THg) and methylmercury (MeHg) concentrations, as well as the stable isotopes of carbon (δ13C) and nitrogen (δ15N) in organisms with different trophic levels (TLs) were investigated in a mid-subtropical urban forest of the Changpoling Forest Park (CFP) in Guiyang City, Guizhou Province, southwestern China. The results showed that THg and MeHg among all taxa ranged from 5.6 to 1267 ng g-1 and 0.046-692 ng g-1, respectively. MeHg% (% of Hg present as MeHg) at different TLs exhibited a wide range of 5.0-69% on average. Both THg and MeHg increased with the TLs from plants to nestling birds, indicating distinct biomagnification through the food web of grasses/pine needles - grasshoppers/caterpillars/katydids/mantis - spiders/songbird nestlings. The trophic magnification slope (TMS) of THg and MeHg were 0.18 ± 0.05 and 0.37 ± 0.08, respectively, suggesting both of them significantly increase along food webs. These findings improve the understanding of biogeochemical Hg cycles in terrestrial food webs and highlight the impacts of terrestrial MeHg on nestling birds.

Cadmium exposure as a key risk factor for residents in a world large-scale barite mining district, southwestern China.

Cadmium (Cd) contamination is easily generated during the mining and manufacturing of barium (Ba). In this study, concentrations of both Ba and Cd in rice, vegetables, pork, fish, drinking water, and soil samples from an active barite mining district were determined. Daily intakes of Ba and Cd, as well as corresponding health risks, were evaluated. The average total daily exposure doses of Cd were 0.0035 and 0.0012 mg/kg BW/day (geometric mean) in the mining zone (MZ) and the chemical plant zone (PZ), respectively. These values significantly exceed the provisional tolerable monthly intake (25 µg/kg BW/month, equal to 0.00083 mg/kg BW/day). Based on the daily exposure doses, vegetable consumption was the most significant Ba exposure route for residents, contributing around 66.1% of the total exposure. In contrast, rice consumption was the major Cd exposure pathway, accounting for about 85.6% of the total exposure. Although the geometric mean (0.17) and 95th percentile (P95, 0.75) of the total hazard quotient (HQ) for Ba were below the acceptable level (1), suggesting that there were no significant health effects caused by Ba exposure, Cd exposure was associated with significant health risks, with the geometric mean of the HQ (1.7) and the P95 (21) well above the acceptable limit (1), indicating the unacceptable non-carcinogenic risk of Cd exposure. In summary, high Cd exposure risk, rather than Ba, was observed for populations living in a large-scale active Ba mining area.

Multi-pathway mercury health risk assessment, categorization and prioritization in an abandoned mercury mining area: A pilot study for implementation of the Minamata Convention.

This is a systematic study of human health risk assessment (HHRA) and risk categorization for inorganic mercury (IHg) and methylmercury (MeHg) in Hg mining areas. A multi-pathway exposure model coupled with Monte Carlo simulation was constructed for the Wanshan Hg mining area (WSMM), Southwestern China, with consideration of oral ingestion (foodstuffs, water and soil), dermal contact (water and soil), and inhalation (gaseous Hg and particulate Hg). The results show that dietary intake (food and water), gaseous Hg inhalation, oral ingestion of soil particles, dermal contact, and particulate Hg inhalation comprised 88.3-96.3%, 3.49-6.14%, 0.14-5.3%, 0.02%, and <0.01% of total IHg ingestion, respectively. As expected, rice consumption contributed the highest proportion (86.3-92.7%) of MeHg. The study shows that the elevated MeHg exposure risk is the most significant issue in Hg mining areas. In addition, Hg risk categorization and prioritization in the WSMM are established for the first time based on rice-based exposure doses of IHg and MeHg. Target areas for future treatment and/or remediation are characterized according to thresholds of reference dose and provisional tolerable weekly intake for exposure doses, as well as risk screening values and risk control values for contaminated soil. The proposed multi-pathway exposure model is strongly recommended for the HHRA of Hg-contaminated sites worldwide and helps facilitate the implementation of the Minamata Convention on Mercury.

Newly deposited atmospheric mercury in a simulated rice ecosystem in an active mercury mining region: High loading, accumulation, and availability.

Mercury (Hg) mining activities are an important anthropogenic source of atmospheric Hg. The Xunyang Hg mine located in Shaanxi Province is the largest active Hg producing centre in China. To understand the biogeochemical processes of atmospheric Hg through Hg mining activities, six groups of experimental pots were carefully designed to investigate the effect of Hg mining activities on Hg contamination from atmospheric deposition in the local surface soils. Based on the variations of Hg in the soil from the experimental pots, the deposition flux and loading of Hg in the Xunyang Hg mining district were investigated. The results showed that the average concentration of total gaseous mercury (TGM) as high as 193 ±â€¯122 ng m-3 was observed in the ambient air, which was orders of magnitude higher than that in remote areas. The average deposition flux and annual loading of atmospheric Hg were 72 mg m-2 y-1 and 10 t y-1, respectively. The dominant atmospheric Hg deposition is within a distance range of 6.0-12 km from the Hg retorting facility, accounting for approximately 85% of the total Hg loading. After 14 months of exposure, total mercury (THg) concentrations in the soil from the experimental pots increased 0.35-9.5 times, and the highest concentrations of methylmercury (MeHg) (3.7 ±â€¯2.9 µg kg-1) in soil were observed in February. Concentrations as high as 643 µg kg-1 THg and 13 µg kg-1 MeHg in rice were observed in the second experimental year. Elevated concentrations of both THg and MeHg in rice indicated that the newly deposited atmospheric Hg was bioavailable, readily methylated, and taken up by rice, suggesting that the ongoing Hg mining activities cause serious Hg contamination in the soil-rice ecosystem and posed a threat to local residents in the Xunyang Hg mining area.

Characteristics, speciation, and bioavailability of mercury and methylmercury impacted by an abandoned coal gangue in southwestern China.

During coal mining activities, a lot of coal gangue is produced, which usually contains high mercury (Hg) concentrations as well as the acid mine drainage (AMD) generator of pyrite. In the present study, the total mercury (THg) and methylmercury (MeHg) in gangue, water, sediment, paddy soil, and rice samples, collected from abandoned coal mining areas, were analyzed. Results showed that the THg concentrations ranged from 0.37 to 35 mg/kg (11 ± 8.4 mg/kg) and 0.15 to 19 mg/kg (2.0 ± 3.9 mg/kg) in gangue and sediments, respectively. For paddy soils, the THg concentrations and MeHg varied from 0.16 to 0.91 mg/kg and 0.71 to 11 ng/g, respectively. Rice samples exhibited wide concentration ranges of THg (3.0-22 ng/g) and MeHg (0.71-8.9 ng/g). Sequential extraction of Hg revealed that the nitric acid-extractable state Hg (F4) was the dominant Hg species in gangue and sediment, while humic acids state Hg (F3) was the dominant form in paddy soil. Compared with gangue, higher percentages of F3 and the residual state Hg (F5) in both sediment and soil samples implied the transformation of F4 to F3 and F5 during transportation. Soil n-HAs (the difference between the total organic carbon and humic acids) were positively correlated with both THg and MeHg in soil and rice, indicating that n-HAs enhance Hg bioavailability under acidic conditions. Further studies should be conducted to reveal the factors influencing the transformation of different Hg fractions, providing ideas on decreasing the bioavailability of Hg in coal mining areas.

Cadmium contamination in a soil-rice system and the associated health risk: An addressing concern caused by barium mining.

Cadmium (Cd) is associated with barite; however, its biogeochemical characteristics in environments impacted by barium (Ba) mining are not known. Here, we first revealed the characteristics of Cd concentrations, distributions, and chemical forms in the soil-rice system in Ba mining areas. The associated exposure and risk assessments of Cd via rice consumption were also conducted. Elevated levels of Cd with a wide range of 0.054-91 mg/kg were found in paddy soils, approximately 63% of which exceeded the national Grade II value for soil Cd levels in China (0.3 mg/kg). A significant positive correlation between the soil Cd and soil Ba demonstrated that large amounts of Cd were released into the environment from Ba mining. Cadmium accumulated remarkably in the rice grains (0.007-3.5 mg/kg). The chemical forms in the rice plants indicated that most of the Cd was in the pectate/protein fraction (F2, 92% in the grains and 61-71% in the other tissues), followed by the residual fraction (F3, 7.1% in the grains, 27-38% in the other tissues). A minor portion of Cd was in the soluble and aminophenol fraction (F1, 0.44% in the grains, 0.26-1.4% in the other tissues). The positive correlations observed between the grain Cd and F2 in the roots, stems and leaves suggested that Cd in the rice grain was mainly from F2. Similarly, the root F2 was also positively correlated with that in the stems/leaves, indicating the critical role of F2 in Cd2+ migration in rice tissues. The estimated average hazard quotient (2.5) and annual excess lifetime cancer risk (21 × 10-5 a-1) were higher than the safety levels of 1 and 5.0 × 10-5 a-1, respectively, showing that the dietary intake of Cd via rice consumption posed high health risks to residents. Our study demonstrated that more concerns should be paid to Cd contamination in Ba mining areas.

Impacts of selenium supplementation on soil mercury speciation, and inorganic mercury and methylmercury uptake in rice (Oryza sativa L.).

Rice grain is known to accumulate methylmercury (MeHg) and has been confirmed to be the major pathway of MeHg exposure to residents in mercury (Hg) mining areas in China. Selenium (Se) supplementation has been proven to be effective in mitigating the toxicity of Hg. To understand how Se supplementation influences soil Hg speciation, a wide range of Se (0-500 mg/kg) was applied to Hg polluted paddy soils in this study, which decreased MeHg concentration in soil from 2.95 ±â€¯0.36 to 0.69 ±â€¯0.16 µg/kg (or 77%). After Se addition, humic acid state Hg (F4) was transformed into strong-complexed state Hg (F5), indicating that Hg bound up to the non-sulfur functional groups of humic acid (non-RSH) was released and reabsorbed by strong binding Se functional group (F5). As a result, inorganic Hg (IHg) was reduced by >48%, 18%, and 80% in root, stem, and grain, respectively, however, the reduction was not apparent in leaf. Substantial reductions were also found for MeHg in grain and root, but not in stem and leaf. Soil is suggested to be the main source of both MeHg and IHg in rice grain. Such a finding may provide an idea for improving Hg-polluted paddies through controlling soil IHg and MeHg. Further research on the molecular structure of the strong-complexed Hg in F5 should be conducted to elucidate the mechanism of Hg-Se antagonism.

New insights into the chemical forms of extremely high methylmercury in songbird feathers from a contaminated site.

The chemical forms of mercury (Hg), particularly methylmercury (MeHg), in songbird feathers from an abandoned mining region were analyzed via X-ray absorption near-edge structure analysis (XANES). In feathers, proportions of MeHg as total mercury (75.6-100%) quantified by the XANES were directly comparable to the chemical extraction values (74.1-95.9%). Most of MeHg were bound with cysteine (Cys) and reduced glutathione (GSH), whereas inorganic mercury (IHg) was mainly bound with GSH. These results were consistent with those found in fish muscles and human hairs of both fish consumers and occupational Hg exposure populations. Our study suggested that chemical forms and speciation of Hg were highly dependent on the exposure sources and food consumption, respectively. Bird feathers were able to selectively accumulate MeHg due to their special binding ways. However, detailed mechanisms of Hg accumulation in bird feathers remain to be further elucidated.

Health Risk Assessment of Inorganic Mercury and Methylmercury via Rice Consumption in the Urban City of Guiyang, Southwest China.

Rice consumption is the main methylmercury (MeHg) exposure route for residents in mercury (Hg) mining areas. However, there is limited studies on mercury in commercial rice, which has high liquidity and can be directly consumed by urban residents. This study measured the total Hg (THg) and MeHg concentrations in 146 rice samples purchased from the markets in Guiyang city, southwest China, and both the inorganic Hg (IHg) and MeHg estimated daily intakes (EDIs) and hazard quotients (HQs) were calculated according to rice consumption. The THg concentrations in all rice samples (range: 0.97 to 13.10 µg·kg-1; mean: 3.88 µg·kg-1) were lower than the Chinese national standard (20 µg·kg-1). The average MeHg concentration in rice was 1.16 µg·kg-1. The total HQs (THQs) ranged from 0.0106 to 0.1048, with a mean of 0.0462, which was far lower than 1. This result suggests that there were low Hg exposure levels through consumption of commercial rice in residents of Guiyang.

Atmospheric PM2.5-Bound Polycyclic Aromatic Hydrocarbons (PAHs) in Guiyang City, Southwest China: Concentration, Seasonal Variation, Sources and Health Risk Assessment.

The polycyclic aromatic hydrocarbons (PAHs) bound to fine particulate matter (PM2.5) can cause long-term adverse health consequences and are a public concern. A total of 144 PM2.5-bound PAHs samples collected from Guiyang City, a typical plateau montane area in southwest China, from September 2012 to August 2013 were investigated to clarify their concentration, distribution, and potential sources. The health exposure risk also was evaluated. The samplers equipped with 90-mm glass fibre filters were operated at a flow rate of 100 L min-1 for 24 h. The concentrations of the 16 PAHs (US EPA priority) were analysed by using ultra performance liquid chromatography equipped with photo diode array detector. Diagnostic ratios and back-trajectories were performed for the 16 PAHs sources apportionment. The results showed that the 16 PAHs ranged from 2.9 to 231 ng m-3 with an annual average of 41 ± 21 ng m-3. The PAHs concentrations exhibited obvious seasonal variation, with higher levels in winter than in summer. Diagnostic ratios indicated that PAHs mainly originated from the combustion of coal and biomass, followed by the emission of vehicle exhaust. Cluster analyses on back-trajectories illustrated that approximately 34% of the air mass came from abroad, as far as Laos and Vietnam, in summer, whereas more than 90% of the air mass came from domestic sources in winter. The lifetime excess cancer risk from exposure to PAHs was 3.63 × 10-4, approximately 360 times higher than the health guideline (10-6) recommended by the US EPA, reflecting a high risk of cancer.

Chemical characterization and sources of PM2.5 at 12-hr resolution in Guiyang, China.

The increasing emission of primary and gaseous precursors of secondarily formed atmospheric particulate matter due to continuing industrial development and urbanization are leading to an increased public awareness of environmental issues and human health risks in China. As part of a pilot study, 12-hr integrated fine fraction particulate matter (PM2.5) filter samples were collected to chemically characterize and investigate the sources of ambient particulate matter in Guiyang City, Guizhou Province, southwestern China. Results showed that the 12-hr integrated PM2.5 concentrations exhibited a daytime average of 51 ± 22µg·m-3 (mean ± standard deviation) with a range of 17-128µg·m-3 and a nighttime average of 55 ± 32µg·m-33 with a range of 4-186 µg·m-3. The 24-hr integrated PM2.5 concentrations varied from 15 to 157 µg·m-3, with a mean value of 53 ± 25 µg·m-3, which exceeded the 24-hr PM2.5 standard of 35µg·m-3 set by USEPA, but was below the standard of 75µg·m-3, set by China Ministry of Environmental Protection. Energy-dispersive X-ray fluorescence spectrometry (XRF) was applied to determine PM2.5 chemical element concentrations. The order of concentrations of heavy metals in PM2.5 were iron (Fe) > zinc (Zn) > manganese (Mn) > lead (Pb) > arsenic (As) > chromium (Cr). The total concentration of 18 chemical elements was 13 ± 2 µg·m-3, accounting for 25% in PM2.5, which is comparable to other major cities in China, but much higher than cities outside of China.

Barium concentrations and speciation in surface waters collected from an active barium mining area in Guizhou Province, southwestern China.

Barium (Ba) is a toxic element and can cause serious health effects. Humans have experienced increased exposure to Ba due to its intensive usage in industrial areas and daily life. Anthropogenic activities of Ba mining and the manufacture of Ba containing products introduce the element into surrounding areas, posing environmental concerns. Concentrations of total Ba (TBa) and dissolved Ba (DBa) in water samples collected from active Ba mines in Tianzhu, east Guizhou Province, southwestern China were measured to show the regional dispersion of Ba contamination. Aqueous Ba species in water were calculated using the PHREEQC program. The results showed that TBa and DBa concentrations ranged from 6.7 to 483.1 µg/L and from 7.5 to 222.7 µg/L, respectively. TBa concentrations presented a high average value of 126.6 µg/L and greatly exceeded the reported common value of 10 µg/L Ba in surface water set by the Ministry of Environment Protection of China. PHREEQC results indicated that Ba species in water were present as Ba2+, BaSO4, BaHCO3, BaCO3, and BaOH+. The distribution of Ba species in water is controlled by pH and total organic carbon (TOC), and the lower pH (pH < 7) the higher the dissolved fractions. The log K d values (K d , dissolved-particulate distribution coefficients) varied from 2.41 to 6.32. Significant correlations were observed among Ba2+ and K+, Na+, Cl-, NO3-, with Pearson correlation coefficients of 0.425, 0.531, 0.853, 0.612, and 0.329, respectively (p < 0.01). Elevated Ba concentrations in water indicated that the Ba contamination and its distribution pattern in local aquatic ecosystems are derived from Ba mining sites in the Tianzhu area.