[Determination of 24 elements migration in Yixing clay pottery by inductively coupled plasma mass spectrometry].

OBJECTIVE: To establish an analytical method for determining the migration of 24 elements in Yixing clay pottery in 4% acetic acid simulated solution by inductively coupled plasma mass spectrometry. METHODS: Four types of Yixing clay pottery, including Yixing clay teapot, Yixing clay kettle, Yixing clay pot, and Yixing clay electric stew pot, were immersed in 4% acetic acid as a food simulant for testing. The migration amount of 24 elements in the migration solution was determined using inductively coupled plasma mass spectrometry. RESULTS: Lithium, magnesium, aluminum, iron, and barium elements with a mass concentration of 1000 µg/L; Lead, cadmium, total arsenic, chromium, nickel, copper, vanadium, manganese, antimony, tin, zinc, cobalt, molybdenum, silver, beryllium, thallium, titanium, and strontium elements within 100 µg/L there was a linear relationship within, the r value was between 0.998 739 and 0.999 989. Total mercury at 5.0 µg/L, there was a linear relationship within, the r value of 0.995 056. The detection limit of the elements measured by this method was between 0.5 and 45.0 µg/L, the recovery rate was 80.6%-108.9%, and the relative standard deviation was 1.0%-4.8%(n=6). A total of 32 samples of four types of Yixing clay pottery sold on the market, including teapots, boiling kettles, casseroles, and electric stewing pots, were tested. It was found that the migration of 16 elements, including beryllium, titanium, chromium, nickel, cobalt, zinc, silver, cadmium, antimony, total mercury, thallium, tin, copper, total arsenic, molybdenum, and lead, were lower than the quantitative limit. The element with the highest migration volume teapot was aluminum, magnesium, and barium; The kettle was aluminum and magnesium; Casserole was aluminum, magnesium, and lithium; The electric stew pot was aluminum. CONCLUSION: This method is easy to operate and has high accuracy, providing an effective and feasible detection method for the determination and evaluation of element migration in Yixing clay pottery.

Arsenic and mercury exposure in different insect trophic guilds from mercury mining areas in Mexico.

The exposure to arsenic and mercury in various insect trophic guilds from two mercury mining sites in Mexico was assessed. The two study sites were La Laja (LL) and La Soledad (LS) mines. Additionally, a reference site (LSR) was evaluated for LS. The terrestrial ecosystem was studied at LL, whereas both the terrestrial ecosystem and a stream called El Cedral (EC) were assessed at LS. The study sites are situated in the Biosphere Reserve Sierra Gorda (BRSG). Mercury vapor concentrations were measured with a portable analyzer, and concentrations of arsenic and mercury in environmental and biological samples were determined through atomic absorption spectrophotometry. Both pollutants were detected in all terrestrial ecosystem components (soil, air, leaves, flowers, and insects) from the two mines. The insect trophic guilds exposed included pollinivores, rhizophages, predators, coprophages, and necrophages. In LS, insects accumulated arsenic at levels 29 to 80 times higher than those found in specimens from LSR, and 10 to 46 times higher than those from LL. Similarly, mercury exposure in LS was 13 to 62 times higher than LSR, and 15 to 54 times higher than in LL. The analysis of insect exposure routes indicated potential exposure through air, soil, leaves, flowers, animal prey, carrion, and excrement. Water and sediment from EC exhibited high levels of arsenic and mercury compared to reference values, and predatory aquatic insects were exposed to both pollutants. In conclusion, insects from mercury mining sites in the BRSG are at risk.

Essential and non-essential element concentrations in human milk samples and the assessment of infants' exposure.

As the data concerning element concentrations in human milk (HM) samples and their intake by infants are lacking in Poland, the present study aimed to explore this issue. The material consisted of HM samples obtained from 30 exclusively breastfeeding mothers during 4-6 weeks postpartum. Additionally, to identify the factors that may potentially affect HM composition, information regarding maternal data (anthropometry, body composition, and diet) was also collected. Maternal diet was assessed with two methods-a food frequency questionnaire and 3-day dietary records. In total, 18 essential and non-essential elements were determined. For the elements analysis, we used inductively coupled plasma quadrupole mass spectrometry. Most of the elements (n = 11, 61%) were detected in all HM samples. In all HM samples tin concentration was higher (5.67 ± 2.39 µg/L) than the usual range reported by the World Health Organization (~ 1.0 µg/L). HM cadmium content was positively associated with maternal salty snacks intake (r = 0.502, p = 0.005), arsenic with whole-grain products intake (r = 0.37, p = 0.043), and mercury concentration with fruits and seeds/nuts consumption (r = 0.424, p = 0.042 and r = 0.378, p = 0.039, respectively). Higher HM lead concentration was predicted by maternal age (95% CI [0.94-0.97]), intake of fish (95% CI [1.01-1.03]), and vegetables (95% CI [1.02-1.06]). The highest infants' intake was observed for copper (35.24 ± 12.48) and the lowest for arsenic (0.076 ± 0.102). Infants' exposure to lead was associated with maternal frequency consumption of canned fish (p = 0.0045). There is a need to perform further research on this topic to maximize the benefits of breastfeeding by minimizing maternal and infant exposure to potentially toxic elements.

Heavy metal association with chronic kidney disease of unknown cause in central India-results from a case-control study.

BACKGROUND: Chronic Kidney Disease of unknown cause (CKDu) a disease of exclusion, and remains unexplained in various parts of the world, including India. Previous studies have reported mixed findings about the role of heavy metals or agrochemicals in CKDu. These studies compared CKDu with healthy controls but lacked subjects with CKD as controls. The purpose of this study was to test the hypothesis whether heavy metals, i.e. Arsenic (As), Cadmium (Cd), Lead (Pb), and Chromium (Cr) are associated with CKDu, in central India. METHODS: The study was conducted in a case-control manner at a tertiary care hospital. CKDu cases (n = 60) were compared with CKD (n = 62) and healthy subjects (n = 54). Blood and urine levels of As, Cd, Pb, and Cr were measured by Inductively Coupled Plasma- Optical Emission Spectrometry. Pesticide use, painkillers, smoking, and alcohol addiction were also evaluated. The median blood and urine metal levels were compared among the groups by the Kruskal-Wallis rank sum test. RESULTS: CKDu had significantly higher pesticide and surface water usage as a source of drinking water. Blood As levels (median, IQR) were significantly higher in CKDu 91.97 (1.3-132.7) µg/L compared to CKD 4.5 (0.0-58.8) µg/L and healthy subjects 39.01 (4.8-67.4) µg/L (p < 0.001) On multinominal regression age and sex adjusted blood As was independently associated with CKDu[ OR 1.013 (95%CI 1.003-1.024) P < .05].Blood and urinary Cd, Pb, and Cr were higher in CKD compared to CKDu (p > .05). Urinary Cd, Pb and Cr were undetectable in healthy subjects and were significantly higher in CKDu and CKD compared to healthy subjects (P = < 0.001). There was a significant correlation of Cd, Pb and Cr in blood and urine with each other in CKDu and CKD subjects as compared to healthy subjects. Surface water use also associated with CKDu [OR 3.178 (95%CI 1.029-9.818) p < .05). CONCLUSION: The study showed an independent association of age and sex adjusted blood As with CKDu in this Indian cohort. Subjects with renal dysfunction (CKDu and CKD) were found to have significantly higher metal burden of Pb, Cd, As, and Cr as compared to healthy controls. CKDu subjects had significantly higher pesticide and surface water usage, which may be the source of differential As exposure in these subjects.

Histidine tag modified magnetic beads for analysis of arsenic binding proteins.

BACKGROUND: Many proteins with thiol groups can bind with trivalent arsenic which are termed as arsenic binding proteins, thus change their physiological functions. Therefore, it is vital to analyze the arsenic binding proteins in cells. The Pull-Down strategy based on biotinylated phenylarsenic acid (Bio-PAO(III)) probes is an effective way for analysis of arsenic binding proteins. In this strategy, streptavidin magnetic beads (SA-MBs) was applied to capture the arsenic binding proteins conjugating with Bio-PAO(III) probe. However, strong interaction between SA and biotin makes the elution of arsenic binding proteins not easy. RESULTS: We developed a novel affinity separation strategy to address the challenge of eluting arsenic binding proteins, a key issue with the existing Bio-PAO(III) Pull-Down method. By employing magnetic beads modified with Nα-Bis(carboxymethyl)-l-lysine (NTA-Lys), polyhistidine-tag (His6-Tag), and SA (MB-NTA(Ni)-His6-SA), we established a more efficient purification process. This innovative approach enables selective capture of arsenic binding proteins in HepG2 cells labeled by Bio-PAO(III) probes, facilitating gentle digestion by trypsin for precise identification through capillary high performance liquid chromatography (Cap HPLC)-electrospray ionization (ESI)-tandem mass spectrometry (MS/MS). What is more, the magnetic beads can be regenerated by using imidazole as the eluent, and the obtained MB-NTA(Ni) can be reloaded with His6-SA for next use. Our method successfully identified 41 arsenic binding proteins, including those involved in cytoskeletal structure, heat shock response, transcriptional regulation, DNA damage repair, redox state regulation, mitochondrial dehydrogenase function, and protein synthesis and structure. SIGNIFICANCE: This work contributes to a more comprehensive understanding of the toxic mechanisms of arsenic, potentially providing valuable insights for the prevention or treatment of arsenic-related diseases.

Toxicological profile and potential health concerns through metals and trace elements exposure in brick kiln workers from Lahore, Pakistan.

This study examined levels of lead (Pb), cadmium (Cd), chromium (Cr), copper (Cu), mercury (Hg), and arsenic (As) in blood, hair, and nails of 18 brick kiln workers from three brick kiln units located around a metropolitan city, Lahore, Pakistan. All the trace elements except Hg and As were detected in the studied matrices of Brick kiln workers. In general, brick kiln workers reflect the highest concentration of Pb, followed by Cd, Cr, and Cu. Of the pollutants analyzed, Pb has the highest mean (min-max) concentrations at 0.35 (0.09-0.65) in blood (µg/mL), 0.34 (0.14-0.71) in hairs (µg/g), and 0.44 (0.32-0.59) in nails (µg/g) of brick kiln workers. Following Pb, the trend was Cd 0.17 (0.10-0.24), Cu 0.11(0.03-0.27), and Cr 0.07 (0.04-0.08) in blood (µg/mL), followed by Cr 0.11(0.05-0.20), Cd 0.09 (0.03-0.13), and Cu 0.08 (0.04-0.16) in hairs (µg/g) and Cu 0.16 (0.05-0.36), Cd 0.13 (0.11-0.17), and Cr 0.10 (0.05-0.14) in nails (µg/g) respectively. Relatively higher concentrations of metals and other trace elements in blood depicts recent dietary exposure. The difference of trace elements except Pb was non-significant (P > 0.05) among studied matrices of workers as well as between Zigzag and traditional exhaust-based brick kilns. The concentrations of Pb, Cd and Cr in blood of brick kilns workers are higher than the values reported to cause health problems in human populations. It is concluded that chronic exposure to metals and other trace elements may pose some serious health risks to brick kiln workers which needs to be addressed immediately to avoid future worst-case scenarios.

Pro-vegetarian dietary patterns and essential and heavy metal exposure in children of 4-5-years from the INfancia y medio Ambiente cohort (INMA).

Dietary patterns provide a comprehensive assessment of food consumption, including essential nutrients and potential exposure to environmental contaminants. While pro-vegetarian (PVG) dietary patterns have shown health benefits in adults, their effects on children are less well studied. This study aims to explore the association between children's adherence to the most common PVG dietary patterns and their exposure to metals, assessed through urine concentration. In our study, we included a population of 723 children aged 4-5-years from the INfancia y Medio Ambiente (INMA) cohort in Spain. We calculated three predefined PVG dietary patterns, namely general (gPVG), healthful (hPVG), and unhealthful (uPVG), using dietary information collected through a validated Food Frequency Questionnaire. Urinary concentrations of various essential and heavy metals (Co, Cu, Zn, Se, Mo, Pb, and Cd) were measured using mass spectrometry. Additionally, urinary arsenic speciation, including arsenobetaine (AsB), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), and inorganic arsenic (iAs), was measured. The sum of urinary MMA and iAs was used to assess iAs exposure. We estimated primary (PMI) and secondary iAs methylation (SMI) indices. To explore the association between PVG dietary patterns in quintiles and metal exposure, we utilized multiple-adjusted linear regression models and the quantile g-computation approach. Compared with the lowest quintile, participants in the highest quintile of gPVG showed a 22.7% lower urinary Co (95% confidence interval (CI): -38.7; -1.98) and a 12.6% lower Se (95%CI: -22.9; -1.00) concentrations. Second quintile of adherence to hPVG was associated with a 51.7% lower urinary iAs + MMA concentrations (95%CI: -74.3; -8.61). Second quintile of adherence to an uPVG was associated with a 13.6% lower Se levels (95%CI: -22.9; -2.95) while the third quintile to this pattern was associated with 17.5% lower Mo concentrations (95%CI: -29.5; -2.95). The fourth quintile of adherence to gPVG was associated with a 68.5% higher PMI and a 53.7% lower SMI. Our study showed that adherence to a gPVG dietary pattern in childhood may modestly reduce the intakes of some essential metals such as Co and Se. Further investigations are warranted to explore any potential health implications.

Applications of engineered biochar in remediation of heavy metal(loid)s pollution from wastewater: Current perspectives toward sustainable development goals.

Environmental pollution of heavy metal(loid)s (HMs) caused adverse impacts, has become one of the emerging concerns and challenges worldwide. Metal(loid)s can pose significant threats to living organisms even when present in trace levels within environmental matrices. Extended exposure to these substances can lead to adverse health consequences in humans. Removing HM-contaminated water and moving toward sustainable development goals (SDGs) is critical. In this mission, biochar has recently gained attention in the environmental sector as a green and alternative material for wastewater removal. This work provides a comprehensive analysis of the remediation of typical HMs by biochars, associated with an understanding of remediation mechanisms, and gives practical solutions for ecologically sustainable. Applying engineered biochar in various fields, especially with nanoscale biochar-aided wastewater treatment approaches, can eliminate hazardous metal(loid) contaminants, highlighting an environmentally friendly and low-cost method. Surface modification of engineered biochar with nanomaterials is a potential strategy that positively influences its sorption capacity to remove contaminants. The research findings highlighted the biochars' ability to adsorb HM ions based on increased specific surface area (SSA), heightened porosity, and forming inner-sphere complexes with oxygen-rich groups. Utilizing biochar modification emerged as a viable approach for addressing lead (Pb), cadmium (Cd), arsenic (As), mercury (Hg), and chromium (Cr) pollution in aqueous environments. Most biochars investigated demonstrated a removal efficiency >90 % (Cd, As, Hg) and can reach an impressive 99 % (Pb and Cr). Furthermore, biochar and advanced engineered applications are also considered alternative solutions based on the circular economy.

Arsenic-enhanced plant growth in As-hyperaccumulator Pteris vittata: Metabolomic investigations and molecular mechanisms.

The first-known As-hyperaccumulator Pteris vittata is efficient in As uptake and translocation, which can be used for phytoremediation of As-contaminated soils. However, the underlying mechanisms of As-enhanced plant growth are unknown. We used untargeted metabolomics to investigate the potential metabolites and associated metabolic pathways regulating As-enhanced plant growth in P. vittata. After 60 days of growth in an MS-agar medium containing 15 mg kg-1 As, P. vittata biomass was 33-34 % greater than the no-As control. Similarly, the As contents in P. vittata roots and fronds were 272 and 1300 mg kg-1, considerably greater than the no-As control. Univariate and multivariate analyses based on electrospray ionization indicate that As exposure changed the expression of 1604 and 1248 metabolites in positive and negative modes. By comparing with the no-As control, As exposure significantly changed the expression of 14 metabolites including abscisic acid, d-glucose, raffinose, stachyose, chitobiose, xylitol, gibberellic acids, castasterone, citric acid, riboflavin-5-phosphate, ubiquinone, ubiquinol, UDP-glucose, and GDP-glucose. These metabolites are involved in phytohormone synthesis, energy metabolism, and sugar metabolism and may all potentially contribute to regulating As-enhanced plant growth in P. vittata. Our data provide clues to understanding the metabolic regulations of As-enhanced plant growth in P. vittata, which helps to enhance its phytoremediation efficiency of As-contaminated soils.

Soil Microbiomes and their Arsenic Functional Genes in Chronically High-Arsenic Contaminated Soils.

Microbial arsenic transformations play essential roles in controlling pollution and ameliorating risk. This study combined high-throughput sequencing and PCR-based approaches targeting both the 16 S rRNA and arsenic functional genes to investigate the temporal and spatial dynamics of the soil microbiomes impacted by high arsenic contamination (9.13 to 911.88 mg/kg) and to investigate the diversity and abundance of arsenic functional genes in soils influenced by an arsenic gradient. The results showed that the soil microbiomes were relatively consistent and mainly composed of Actinobacteria (uncultured Gaiellales and an unknown_67 - 14 bacterium), Proteobacteria, Firmicutes (particularly, Bacillus), Chloroflexi, and Acidobacteria (unknown_Subgroup_6). Although a range of arsenic functional genes (e.g., arsM, arsC, arrA, and aioA) were identified by shotgun metagenomics, only the arsM gene was detected by the PCR-based method. The relative abundance of the arsM gene accounted for 0.20%-1.57% of the total microbial abundance. Combining all analyses, arsenic methylation mediated by the arsM gene was proposed to be a key process involved in the arsenic biogeochemical cycle and mitigation of arsenic toxicity. This study advances our knowledge about arsenic mechanisms over the long-term in highly contaminated soils.

Assessment of the stabilization effect of ferrous sulfate for arsenic-contaminated soils based on chemical extraction methods and in vitro methods: Methodological differences and linkages.

Stabilization of arsenic-contaminated soils with ferrous sulfate has been reported in many studies, but there are few stabilization effects assessments simultaneously combined chemical extraction methods and in vitro methods, and further explored the corresponding alternative relationships. In this study, ferrous sulfate was added at FeAs molar ratio of 0, 5, 10 and 20 to stabilize As in 10 As spiked soils. Stabilization effects were assessed by 6 chemical extraction methods (toxicity characteristic leaching procedures (TCLP), HCl, diethylenetriamine pentaacetic acid (DTPA), CaCl2, CH3COONH4, (NH4)2SO4), and 4 in vitro methods (physiologically based extraction test (PBET), in vitro gastrointestinal method (IVG), Solubility Bioaccessibility Research Consortium (SBRC) method, and the Unified Bioaccessibility Research Group of Europe method (UBM)). The results showed that the HCl method provides the most conservative assessment results in non-calcareous soils, and in alkaline calcareous soils, (NH4)2SO4 method provides a more conservative assessment. In vitro methods provided significantly higher As concentrations than chemical extraction methods. The components of the simulated digestion solution as well as the parameters may have contributed to this result. The small intestinal phase of PBET and SBRC method produced the highest and lowest ranges of As concentrations, and in the range of 127-462 mg/kg and 68-222 mg/kg when the FeAs molar ratio was 5. So the small intestinal phase of PBET method may provide the most conservative assessment results, while the same phase of SBRC may underestimate the human health risks of As in stabilized soil by 51 %(at a FeAs molar ratio of 5). Spearman correlation analysis indicated that the small intestinal phase of PBET method correlated best with HCl method (correlation coefficient: 0.71). This study provides ideas for the assessment of stabilization efforts to ensure that stabilization meets ecological needs while also being less harmful to humans.

Characterization and childhood exposure assessment of toxic heavy metals in household dust under true living conditions from 10 China cities.

Health hazards caused by metal exposure in household dust are concerning environmental health problems. Exposure to toxic metals in household dust imposes unclear but solid health risks, especially for children. In this multicenter cross-sectional study, a total of 250 household dust samples were collected from ten stratified cities in China (Panjin, Shijiazhuang, Qingdao, Lanzhou, Luoyang, Ningbo, Xi'an, Wuxi, Mianyang, Shenzhen) between April 2018 and March 2019. Questionnaire was conducted to gather information on individuals' living environment and health status in real-life situations. Multivariate logistic regression and principal component analysis were conducted to identify risk factors and determine the sources of metals in household dust. The median concentration of five metals in household dust from 10 cities ranged from 0.03 to 73.18 µg/g. Among the five heavy metals, only chromium in household dust of Mianyang was observed significantly both higher in the cold season and from the downwind households. Mercury, cadmium, and chromium were higher in the third-tier cities, with levels of 0.08, 0.30 and 97.28 µg/g, respectively. There were two sources with a contribution rate of 38.3 % and 25.8 %, respectively. Potential risk factors for increased metal concentration include long residence time, close to the motorway, decoration within five years, and purchase of new furniture within one year. Under both moderate and high exposure scenarios, chromium showed the highest level of exposure with 6.77 × 10-4 and 2.28 × 10-3 mg·kg-1·d-1, and arsenic imposed the highest lifetime carcinogenic risk at 1.67 × 10-4 and 3.17 × 10-4, respectively. The finding highlighted the priority to minimize childhood exposure of arsenic from household dust.

Inhibiting effects of humic acid on iron flocculation hindered As removal by electro-flocculation on air cathode iron anode.

Activated carbon air cathode combined with iron anode oxidation-flocculation synergistic Arsenic (As) removal was a new groundwater purification technology with low energy consumption and high efficiency for groundwater with high As concentration. The presence of organic matter such as humic acid (HA) had ambiguous effects on formation of organic colloids in the system. The effects of the particle size distribution characteristics of these colloids on the formation characteristics of flocs and the efficiency of As purification was not clear. In this work, we used five different pore size alumina filter membranes to separate mixed phase solutions and studied the corresponding changes in iron and arsenic concentrations in the presence and absence of humic acid conditions. In the presence of HA, the arsenic concentration of < 0.05 µm particle size components was 1.01, 1.28, 3.07, 7.69, 2.85 and 1.24 times of that in the absence of HA. At the same time, the arsenic content in 0.05-0.1 µm and 0.1-0.45 µm particle size components was also higher than that in the system without HA, which revealed that the presence of HA hindered the flocculation behavior of As distribution to higher particle sizes in the early stage of the reaction. The presence of HA affected the flocculation rate of iron flocs from small to large particle size fractions and it had limited effect on the behavior of large-size flocs in adsorption of As. These results provide a theoretical basis for targeted, rapid, and low consumption synergistic removal of arsenic and organic compounds in high arsenic groundwater.

Can arsenic bioavailability be predicted in soils using in vitro gastro-intestinal simulation?

Many gastrointestinal simulation methods have been used to predict bioavailability, but the suitability of different methods for the same metal(loid)s varies widely, which inevitably affects the accuracy of human health risk assessment. Arsenic is a common and important contaminant in many contaminated land situations. It can be readily absorbed and has teratogenic and mutagenic toxicity. Therefore, in this study, four the most commonly used in vitro simulation methods (the Physiologically Based Extraction Test (PBET), In Vitro Gastrointestinal Method (IVG), Soluble Bioavailability Research Consortium (SBRC), the Unified BARGE Method (UBM)) were tested against an in vivo animal live model, to evaluate their effectiveness for the prediction of soil As bioavailability in 10 industrially contaminated soils. The soil As relative bioavailability (RBA) varied between 15% and 68% in the different soils. As bioaccessibility differed between the 4 gastro-intestinal simulation methods. Gastric phase of UBM (UBMG) predicted As relative bioavailability the best of the 4 assays (R2 = 0.81). This study provides theoretical and technical support to refine human health risk assessment of As in soils from urban industrial legacy contaminated sites.

Cumulative effect of arsenic on the number of mouse offspring and the female reproductive hormones in mice.

In this study, we evaluated the cumulative effects of arsenic (III) oxide on the number of mouse offspring over three consecutive generations and monitored changes in levels of the reproductive hormones, oestradiol and progesterone in female mice during the dioestrus phase of the cycle. The control group received water from the mains. In two experimental groups, mice were given drinking water containing dissolved arsenic (III) oxide at concentrations of 10.6 mg L-1 and 106 mg L-1, respectively. These concentrations represent the values converted from a human model to an animal model (mice) thus correspond to the arsenic content of the groundwater in the southern part of the Pannonian Basin, in the province of Vojvodina, in the Banat region, in particular in the town of Zrenjanin. The average number of newborn mice in both experimental groups decreased for three consecutive generations. The total arsenic content of day-old mice did not show significant differences between the experimental groups. Arsenic (III) oxide affected the reproductive hormone levels of female mice at both concentrations.

[Effect of Silica Fertilizer(Husk Ash) to Improve Soil Quality and Reduce Cd and As Accumulation in Rice].

A rice pot experiment was conducted to identify the effect of silica fertilizer prepared from husk ash on the soil bioavailability of cadmium (Cd) and arsenic (As), enzyme activities, microbial community structure, and heavy metal content in brown rice at different growth stages. The results showed that the application of 0.1%-1.0% silica fertilizer-husk ash increased the pH value of soil by 0.04-0.24 units and the content of soil available silicon by 44.2%-97.5%. It also decreased the content of available Cd and available As by 16.2%-21.4% and 16.0%-24.9%, respectively. With the increase in application amount, the soil enzyme activities increased at all growth stages, and the sucrase activity and the dehydrogenase activity significantly increased by 6.3%-145.7% and 6.7%-224.1%, respectively. The analysis of the soil microbial community composition structure at mature stages showed that the application of silica fertilizer-husk ash had no effect on microbial α-diversity, but it had a significant effect on microbial ß-diversity and then promoted microbial growth and maintained the stability of the community structure. With the increase in application amount, the contents of Cd in brown rice decreased by 29.3%-89.7%, and the contents of total As and inorganic As in brown rice decreased by 7.8%-42.3% and 17.2%-44.5%, respectively. Under the application of 0.5% and 1.0% silica fertilizer-husk ash, the Cd contents in brown rice were lower than 0.2 mg·kg-1, and the inorganic As contents in brown rice were lower than 0.35 mg·kg-1. In conclusion, the silica fertilizer-husk ash can improve soil quality and reduce the contents of Cd and As in brown rice, and it is eco-friendly and can be used to remedy the paddy soil contaminated with Cd and As.

[Health Risk Assessment for an Arsenic-contaminated Site Based on Monte Carlo Simulation and Parameters Optimization].

Risk assessment is a critical part of risk management for contaminated sites. However， in the specific management practice of As-contaminated sites， it is difficult to obtain realistic health risks for contaminated sites based on the total amount of pollutants and determined values of the model， thus preventing the control requirements of later remediation to be met. An increasing number of studies have recently been conducting risk assessments by considering bioavailability， modification parameters， and combined probabilistic models. To improve the accuracy of risk assessment results， taking a large As-contaminated site as a case， 432 sampling sites were set up and collected at different depths to analyze the level and distribution characteristics of As pollution， and probabilistic risk assessment was conducted with the modification of model parameters through literature research and Monte Carlo simulation. Then， the impact of traditional methods and probabilistic methods on health risk assessment was explored in comparison. The results indicated that ω（As） in the top soil of the study area ranged from 2.70-97.0 mg·kg-1， with a spatial variation coefficient of 0.61 and weaker spatial continuity. The carcinogenic risk and hazard index obtained by the traditional risk assessment method were 2.12E-4 and 8.36， respectively， which obviously overestimated the actual risk level and were not conductive to the refined management of As-contaminated sites. Combined with modification of model parameters and probabilistic risk assessment， the non-carcinogenic risk for adults and children was found to be at an acceptable level， and the carcinogenic risk was reduced by nearly an order of magnitude compared to that in the conventional method. Considering the relative biological effectiveness （RBA） of As， the 95% quantile of the total carcinogenic risk was 1.24E-5， a reduction of up to 36.41% compared to the uncorrected corresponding risk value of 1.95E-5. The carcinogenic risk of soil As for adults and children in the study area exceeded acceptable risk levels 1E-6， with oral ingestion of soil being the primary route of exposure. In addition， the results of the sensitivity analysis of the parameters showed that As concentration， daily oral ingestion rate of soils， and exposure duration of children had relatively larger effects for health risks. This work will provide a methodological and theoretical basis for achieving accurate risk assessment of As-contaminated sites and provide concepts for refined risk management.

Investigation of the protective effect of chitosan against arsenic-induced nephrotoxicity and oxidative damage in rat kidney tissue.

Arsenic is an important metalloid that can cause poisoning in humans and domestic animals. Exposure to arsenic causes cell damage, increasing the production of reactive oxygen species. Chitosan is a biopolymer obtained by deacetylation of chitin with antioxidant and metal ion chelating properties. In this study, the protective effect of chitosan on arsenic-induced nephrotoxicity and oxidative damage was investigated. 32 male Wistar-albino rats were divided into 4 groups of 8 rats each as control group (C), chitosan group (CS group), arsenic group (AS group), and arsenic+chitosan group (AS+CS group). The C group was given distilled water by oral gavage, the AS group was given 100 ppm/day Na-arsenite ad libitum with drinking water, the CS group was given 200 mg/kg/day chitosan dissolved in saline by oral gavage, the AS+CS group was given 100 ppm/day Na-arsenite ad libitum with drinking water and 200 mg/kg/day chitosan dissolved in saline by oral gavage for 30 days. At the end of the 30-day experimental period, 90 mg/kg ketamine was administered intraperitoneally to all rats, and blood samples and kidney tissues were collected. Urea, uric acid, creatinine, P, Mg, K, Ca, Na, Cystatin C (CYS-C), Neutrophil Gelatinase Associated Lipocalin (NGAL) and Kidney Injury Molecule 1 (KIM-1) levels were measured in serum samples. Malondialdehyde (MDA), Glutathione (GSH), Catalase (CAT) and Superoxide dismutase (SOD) levels in the supernatant obtained from kidney tissue were analyzed by ELISA method. Compared with AS group, uric acid and creatinine levels of the AS+CS group were significantly decreased (p<0.001), urea, KIM-1, CYS-C, NGAL, and MDA levels were numerically decreased and CAT, GSH, and SOD levels were numerically increased (p>0.05). In conclusion, based on both biochemical and histopathological-immunohistochemical- immunofluorescence findings, it can be concluded that chitosan attenuates kidney injury and protects the kidney.

An exploratory study on the association of multiple metals in serum with preeclampsia.

Background: Individual metal levels are potential risk factors for the development of preeclampsia (PE). However, understanding of relationship between multiple metals and PE remains elusive. Purpose: The purpose of this study was to explore whether eight metals [zinc (Zn), manganese (Mn), copper (Cu), nickel (Ni), lead (Pb), arsenic (As), cadmium (Cd), and mercury (Hg)] in serum had a certain relationship with PE. Methods: A study was conducted in Dongguan, China. The concentrations of metals in maternal serum were assessed using inductively coupled plasma mass spectrometry (ICP-MS). Data on various factors were collected through a face-to-face interview and hospital electronic medical records. The unconditional logistic regression model, principal component analysis (PCA) and Bayesian Kernel Machine Regression (BKMR) were applied in our study. Results: The logistic regression model revealed that the elevated levels of Cu, Pb, and Hg were associated with an increased risk of PE. According to PCA, principal component 1 (PC1) was predominated by Hg, Pb, Mn, Ni, Cu, and As, and PC1 was associated with an increased risk of PE, while PC2 was predominated by Cd and Zn. The results of BKMR indicated a significant positive cumulative effect of serum metals on PE risk, with Ni and Cu exhibiting a significant positive effect. Moreover, BKMR results also revealed the nonlinear effects of Ni and Cd. Conclusion: The investigation suggests a potential positive cumulative impact of serum metals on the occurrence of PE, with a particular emphasis on Cu as a potential risk factor for the onset and exacerbation of PE. These findings offer valuable insights for guiding future studies on this concern.

Deep resource utilization of hazardous arsenic-alkali slag: Thermodynamic analysis, mechanism investigation and process optimization.

The best solution to address environmental pollution caused by arsenic-containing hazardous waste is to prepare high-purity elemental arsenic from such waste. The key to this approach lies in the efficient separation of arsenic from various impurities. This paper presents a viable solution for producing high-purity elemental arsenic from arsenic-alkali slag, and the keylies in utilizing the selective precipitation of magnesium ammonium arsenate (MgNH4AsO4) to achieve efficient separation of arsenic from alkali, antimony, and other impurities. Thermodynamic analysis and hydrometallurgical condition experiments indicate that in complex alkaline arsenic-containing solutions, over 90% of arsenic components can selectively precipitate in the form of MgNH4AsO4. The content of arsenic in the resulting precipitate reaches approximately 30%, while the content of antimony is below 0.1%. This achieves efficient enrichment of arsenic and preliminary separation of impurities in complex arsenic-alkali slag. Thermodynamic analysis and pyrometallurgical condition experiments demonstrate that the precipitate of MgNH4AsO4 can be reduced to elemental arsenic with an arsenic content reaching 99.85%, and an antimony content as low as 0.05%. This achieves a profound separation of arsenic from impurities. Based on the research presented in this paper, a production line was established that enables the deep resource utilization of arsenic-alkali slag.