Sources and human health risks associated with potentially toxic elements (PTEs) in urban dust: A global perspective.

Long-term exposure to urban dust containing potentially toxic elements (PTEs) poses detrimental impacts on human health. However, studies estimating human health risks in urban dusts from a global perspective are scarce. We evaluated data for twelve PTEs in urban dusts across 59 countries from 463 published articles, including their concentrations, input sources, and probabilistic risks to human health. We found that 34.1 and 60.3% of those investigated urban dusts have been heavily contaminated with As and Cd, respectively. The input of PTEs was significantly correlated with economic structure due to emissions of industrial activities and traffic emissions being the major sources. Based on the Monte Carlo simulation, we found that the mean hazard index below the safe threshold (1.0) could still cause non-negligible risks to human health. Arsenic and Cr were the major PTEs threatening human health, and relatively high risk levels were observed in cities in China, Korea, Chile, Malaysia, and Australia. Importantly, our analysis suggested that PTEs threaten the health of approximately 92 million adults and 280 million children worldwide. Overall, our study provides important foundational understanding and guidance for policy decision-making to reduce the potential risks associated with PTE exposure and to promote sustainable development of urban economies.

Field-aged rice hull biochar stimulated the methylation of mercury and altered the microbial community in a paddy soil under controlled redox condition changes.

Mercury (Hg) contaminated paddy soils are hot spots for methylmercury (MeHg) which can enter the food chain via rice plants causing high risks for human health. Biochar can immobilize Hg and reduce plant uptake of MeHg. However, the effects of biochar on the microbial community and Hg (de)methylation under dynamic redox conditions in paddy soils are unclear. Therefore, we determined the microbial community in an Hg contaminated paddy soil non-treated and treated with rice hull biochar under controlled redox conditions (< 0 mV to 600 mV) using a biogeochemical microcosm system. Hg methylation exceeded demethylation in the biochar-treated soil. The aromatic hydrocarbon degraders Phenylobacterium and Novosphingobium provided electron donors stimulating Hg methylation. MeHg demethylation exceeded methylation in the non-treated soil and was associated with lower available organic matter. Actinobacteria were involved in MeHg demethylation and interlinked with nitrifying bacteria and nitrogen-fixing genus Hyphomicrobium. Microbial assemblages seem more important than single species in Hg transformation. For future directions, the demethylation potential of Hyphomicrobium assemblages and other nitrogen-fixing bacteria should be elucidated. Additionally, different organic matter inputs on paddy soils under constant and dynamic redox conditions could unravel the relationship between Hg (de)methylation, microbial carbon utilization and nitrogen cycling.

Almond shell-derived biochar decreased toxic metals bioavailability and uptake by tomato and enhanced the antioxidant system and microbial community.

The effectiveness of almond shell-derived biochar (ASB) in immobilizing soil heavy metals (HMs) and its impact on soil microbial activity and diversity have not been sufficiently studied. Hence, a pot study was carried out to investigate the effectiveness of ASB addition at 2, 4, and 6 % (w/w) on soil biochemical characteristics and the bioavailability of Cd, Cu, Pb, and Zn to tomato (Solanum lycopersicum L.) plants, as compared to the control (contaminated soil without ASB addition). The addition of ASB promoted plant growth (up to two-fold) and restored the damage to the ultrastructure of chloroplast organelles. In addition, ASB mitigated the adverse effects of HMs toxicity by decreasing oxidative damage, regulating the antioxidant system, improving soil physicochemical properties, and enhancing enzymatic activities. At the phylum level, ASB addition enhanced the relative abundance of Actinobacteriota, Acidobacteriota, and Firmicutes while decreasing the relative abundance of Proteobacteria and Bacteroidota. Furthermore, ASB application increased the relative abundance of several fungal taxa (Ascomycota and Mortierellomycota) while reducing the relative abundance of Basidiomycota in the soil. The ASB-induced improvement in soil properties, microbial community, and diversity led to a significant decrease in the DTPA-extractable HMs down to 41.0 %, 51.0 %, 52.0 %, and 35.0 % for Cd, Cu, Pb, and Zn, respectively, as compared to the control. The highest doses of ASB (ASB6) significantly reduced the metals content by 26.0 % for Cd, 78.0 % for Cu, 38.0 % for Pb, and 20.0 % for Zn in the roots, and 72.0 % for Cd, 67.0 % for Cu, 46.0 % for Pb, and 35.0 % for Zn in the shoots, as compared to the control. The structural equation model predicts that soil pH and organic matter are driving factors in reducing the availability and uptake of HMs. ASB could be used as a sustainable trial for remediation of HMs polluted soils and reducing metal content in edible plants.

Soil Geobacteraceae are the key predictors of neurotoxic methylmercury bioaccumulation in rice.

Contamination of rice by the potent neurotoxin methylmercury (MeHg) originates from microbe-mediated Hg methylation in soils. However, the high diversity of Hg methylating microorganisms in soils hinders the prediction of MeHg formation and challenges the mitigation of MeHg bioaccumulation via regulating soil microbiomes. Here we explored the roles of various cropland microbial communities in MeHg formation in the potentials leading to MeHg accumulation in rice and reveal that Geobacteraceae are the key predictors of MeHg bioaccumulation in paddy soil systems. We characterized Hg methylating microorganisms from 67 cropland ecosystems across 3,600 latitudinal kilometres. The simulations of a rice-paddy biogeochemical model show that MeHg accumulation in rice is 1.3-1.7-fold more sensitive to changes in the relative abundance of Geobacteraceae compared to Hg input, which is recognized as the primary parameter in controlling MeHg exposure. These findings open up a window to predict MeHg formation and accumulation in human food webs, enabling more efficient mitigation of risks to human health through regulations of key soil microbiomes.

Exploring the hidden environmental pollution of microplastics derived from bioplastics: A review.

Bioplastics might be an ecofriendly alternative to traditional plastics. However, recent studies have emphasized that even bioplastics can end up becoming micro- and nano-plastics due to their degradation under ambient environmental conditions. Hence, there is an urgent need to assess the hidden environmental pollution caused by bioplastics. However, little is known about the evolutionary trends of bibliographic data, degradation pathways, formation, and toxicity of micro- and nano-scaled bioplastics originating from biodegradable polymers such as polylactic acid, polyhydroxyalkanoates, and starch-based plastics. Therefore, the prime objective of the current review was to investigate evolutionary trends and the latest advancements in the field of micro-bioplastic pollution. Additionally, it aims to confront the limitations of existing research on microplastic pollution derived from the degradation of bioplastic wastes, and to understand what is needed in future research. The literature survey revealed that research focusing on micro- and nano-bioplastics has begun since 2012. This review identifies novel insights into microbioplastics formation through diverse degradation pathways, including photo-oxidation, ozone-induced degradation, mechanochemical degradation, biodegradation, thermal, and catalytic degradation. Critical research gaps are identified, including defining optimal environmental conditions for complete degradation of diverse bioplastics, exploring micro- and nano-bioplastics formation in natural environments, investigating the global occurrence and distribution of these particles in diverse ecosystems, assessing toxic substances released during bioplastics degradation, and bridging the disparity between laboratory studies and real-world applications. By identifying new trends and knowledge gaps, this study lays the groundwork for future investigations and sustainable solutions in the realm of sustainable management of bioplastic wastes.

New Insights into MeHg Accumulation in Rice (Oryza sativa L.): Evidence from Cysteine.

The intake of methylmercury (MeHg)-contaminated rice poses immense health risks to rice consumers. However, the mechanisms of MeHg accumulation in rice plants are not entirely understood. The knowledge that the MeHg-Cysteine complex was dominant in polished rice proposed a hypothesis of co-transportation of MeHg and cysteine inside rice plants. This study was therefore designed to explore the MeHg accumulation processes in rice plants by investigating biogeochemical associations between MeHg and amino acids. Rice plants and underlying soils were collected from different Hg-contaminated sites in the Wanshan Hg mining area. The concentrations of both MeHg and cysteine in polished rice were higher than those in other rice tissues. A significant positive correlation between MeHg and cysteine in rice plants was found, especially in polished rice, indicating a close geochemical association between cysteine and MeHg. The translocation factor (TF) of cysteine showed behavior similar to that of the TF of MeHg, demonstrating that these two chemical species might share a similar transportation mechanism in rice plants. The accumulation of MeHg in rice plants may vary due to differences in the molar ratios of MeHg to cysteine and the presence of specific amino acid transporters. Our results suggest that cysteine plays a vital role in MeHg accumulation and transportation inside rice plants.

Effects of microplastics on soil microorganisms and microbial functions in nutrients and carbon cycling - A review.

The harmful effects of microplastics (MPs) pollution in the soil ecosystem have drawn global attention in recent years. This paper critically reviews the effects of MPs on soil microbial diversity and functions in relation to nutrients and carbon cycling. Reports suggested that both plastisphere (MP-microbe consortium) and MP-contaminated soils had distinct and lower microbial diversity than that of non-contaminated soils. Alteration in soil physicochemical properties and microbial interactions within the plastisphere facilitated the enrichment of plastic-degrading microorganisms, including those involved in carbon (C) and nutrient cycling. MPs conferred a significant increase in the relative abundance of soil nitrogen (N)-fixing and phosphorus (P)-solubilizing bacteria, while decreased the abundance of soil nitrifiers and ammonia oxidisers. Depending on soil types, MPs increased bioavailable N and P contents and nitrous oxide emission in some instances. Furthermore, MPs regulated soil microbial functional activities owing to the combined toxicity of organic and inorganic contaminants derived from MPs and contaminants frequently encountered in the soil environment. However, a thorough understanding of the interactions among soil microorganisms, MPs and other contaminants still needs to develop. Since currently available reports are mostly based on short-term laboratory experiments, field investigations are needed to assess the long-term impact of MPs (at environmentally relevant concentration) on soil microorganisms and their functions under different soil types and agro-climatic conditions.

Hydrogeochemical characteristics, stable isotopes, positive matrix factorization, source apportionment, and health risk of high fluoride groundwater in semiarid region.

Chronic exposure to high fluoride (F-) levels in groundwater causes community fluorosis and non-carcinogenic health concerns in local people. This study described occurrence, dental fluorosis, and origin of high F-groundwater using δ2H and δ18O isotopes at semiarid Gilgit, Pakistan. Therefore, groundwater (n = 85) was collected and analyzed for F- concentrations using ion-chromatography. The lowest F- concentration was 0.4 mg/L and the highest 6.8 mg/L. F- enrichment is linked with higher pH, NaHCO3, NaCl, δ18O, Na+, HCO3-, and depleted Ca+2 aquifers. The depleted δ2H and δ18O values indicated precipitation and higher values represented the evaporation effect. Thermodynamic considerations of fluorite minerals showed undersaturation, revealing that other F-bearing minerals viz. biotite and muscovite were essential in F- enrichment in groundwater. Positive matrix factorization (PMF) and principal component analysis multilinear regression (PCAMLR) models were used to determine four-factor solutions for groundwater contamination. The PMF model results were accurate and reliable compared with those of the PCAMLR model, which compiled the overlapping results. Therefore, 28.3% exceeded the WHO permissible limit of 1.5 mg/L F-. Photomicrographs of granite rocks showed enriched F-bearing minerals that trigger F- in groundwater. The community fluorosis index values were recorded at > 0.6, revealing community fluorosis and unsuitability of groundwater for drinking.

Bromine contamination and risk management in terrestrial and aquatic ecosystems.

Bromine (Br) is widely distributed through the lithosphere and hydrosphere, and its chemistry in the environment is affected by natural processes and anthropogenic activities. While the chemistry of Br in the atmosphere has been comprehensively explored, there has never been an overview of the chemistry of Br in soil and aquatic systems. This review synthesizes current knowledge on the sources, geochemistry, health and environmental threats, remediation approaches, and regulatory guidelines pertaining to Br pollution in terrestrial and aquatic environments. Volcanic eruptions, geothermal streams, and seawater are the major natural sources of Br. In soils and sediments, Br undergoes natural cycling between organic and inorganic forms, with bromination reactions occurring both abiotically and through microbial activity. For organisms, Br is a non-essential element; it is passively taken up by plant roots in the form of the Br- anion. Elevated Br- levels can limit plant growth on coastal soils of arid and semi-arid environments. Br is used in the chemical industry to manufacture pesticides, flame retardants, pharmaceuticals, and other products. Anthropogenic sources of organobromine contaminants in the environment are primarily wastewater treatment, fumigants, and flame retardants. When aqueous Br- reacts with oxidants in water treatment plants, it can generate brominated disinfection by-products (DBPs), and exposure to DBPs is linked to adverse human health effects including increased cancer risk. Br- can be removed from aquatic systems using adsorbents, and amelioration of soils containing excess Br- can be achieved by leaching, adding various amendments, or phytoremediation. Developing cost-effective methods for Br- removal from wastewater would help address the problem of toxic brominated DBPs. Other anthropogenic organobromines, such as polybrominated diphenyl ether (PBDE) flame retardants, are persistent, toxic, and bioaccumulative, posing a challenge in environmental remediation. Future research directives for managing Br pollution sustainably in various environmental settings are suggested here.

Possible hazards from biodegradation of soil plastic mulch: Increases in microplastics and CO2 emissions.

Biodegradable mulches are widely recognized as ecologically friendly substances. However, their degradation percentage upon entering soils may vary based on mulch type and soil microbial activities, raising concerns about potential increases in microplastics (MPs). The effects of using different types of mulch on soil carbon pools and its potential to accelerate their depletion have not yet well understood. Therefore, we conducted an 18-month experiment to investigate mulch biodegradation and its effects on CO2 emissions. The experiment included burying soil with biodegradable mulch made of polylactic acid (PLA) and polybutylene adipate terephthalate (PBAT), and control treatments with traditional mulch (PE) and no mulch (CK). The results indicated that PE did not degrade, and the degradation percentage of PLA and PBAT were 46.2% and 88.1%, and the MPs produced by the degradation were 6.7 × 104 and 37.2 × 104 items/m2, respectively. Biodegradable mulch, particularly PLA, can enhance soil microbial diversity and foster more intricate bacterial communities compared to PE. The CO2 emissions were 0.58, 0.74, 0.99, and 0.86 g C/kg in CK, PE, PLA, , PBAT, respectively. A positive correlation was observed between microbial abundance and diversity with CO2 emissions, while a negative correlation was observed with soil total organic carbon. Biodegradable mulch enhanced the transformation of soil organic C into CO2 by stimulating microbial activity.

Manure derived hydrochar reduced phosphorus loss risk via an alteration of phosphorus fractions and diversified microbial community in rice paddy soil.

Phosphorus (P) loss caused by the irrational use of manure organic fertilizer has become a worldwide environmental problem, which has caused a potential threat to water safety and intensified agricultural non-point source pollution. Hydrothermal carbonization is method with a low-energy consumption and high efficiency to deal with environmental problems. Application of pig manure-derived hydrochar (PMH) to soil exhibited potential of sustainable development compared with the pristine pig manure (PM). However, the effects of PMH on the distribution of P among the fractions/forms and the interaction between microorganisms and P forms and its relevance to the potential loss of P in paddy fields has not been clarified. Therefore, in this study, a soil column experiment was conducted using the untreated soil (control), and the PM, PMH1 (PMH derived at 180 °C), and PMH2 (PMH derived at 260 °C) treated soils (at the dose of 0.05 %) and rice was cultivated to investigate the effects of PM and PMH on the P fractions, mobilization, ad potential loss via the induced changes on soil microbial community after a complete growing season of rice. The trend of P utilization was evaluated by P speciation via continuous extraction and 31P NMR. The addition of PMH reduced the proportion of residual P in soil by 23.8-26.3 %, and increased the proportion of HCl-P and orthophosphate by 116.2-158.6 % and 6.1-6.8 % compared to PM. The abundance of gcd gene developed after the application of PMH2, which enhanced the mobile forms of soil P utilization via secreting gluconic acid. The network diagram analysis concluded that the changes in various P forms were mainly related to Proteobacteria, Bacteroides, Firmicutes and Acidobacteria. The results illustrated that PMH mitigate the potential risk of P loss more than PM by altering P fractions and affecting soil microbial community.

Remediation of neonicotinoid-contaminated soils using peanut shell biochar and composted chicken manure: Transformation mechanisms of geochemical fractions.

Soil remediation techniques are promising approaches to relieve the adverse environmental impacts in soils caused by neonicotinoids application. This study systematically investigated the remediation mechanisms for peanut shell biochar (PSB) and composted chicken manure (CCM) on neonicotinoid-contaminated soils from the perspective of transformation of geochemical fractions by combining a 3-step sequential extraction procedure and non-steady state model. The neonicotinoid geochemical fractions were divided into labile, moderate-adsorbed, stable-adsorbed, bound, and degradable fractions. The PSB and CCM addition stimulated the neonicotinoid transformation in soils from labile fraction to moderate-adsorbed and stable-adsorbed fractions. Compared with unamended soils, the labile fractions decreased from 47.6% ± 11.8% of the initial concentrations to 12.1 ± 9.3% in PSB-amended soils, and 7.1 ± 4.9% in PSB and CCM-amended soils, while the proportions of moderate-adsorbed and stable-adsorbed fractions correspondingly increased by 1.8-2.4 times and 2.3-4.8 times, respectively. A small proportion (<4.8%) in bound fractions suggested there were rather limited bound-residues after 48 days incubation. The PSB stimulated the -NO2-containing neonicotinoid-degraders, which promoted the degradable fractions of corresponding neonicotinoids by 8.2 ± 6.3%. Degradable fraction of neonicotinoids was the dominant fate in soils, which accounted for 58.3 ± 16.7%. The findings made beneficial theoretical supplements and provided valuable empirical evidence for the remediation of neonicotinoid-contaminated soils.

Seed nano-priming with multiple nanoparticles enhanced the growth parameters of lettuce and mitigated cadmium (Cd) bio-toxicity: An advanced technique for remediation of Cd contaminated environments.

Seed nano-priming can be used as an advanced technology for enhancing seed germination, plant growth, and crop productivity; however, the potential role of seed nano-priming in ameliorative cadmium (Cd) bio-toxicity under Cd stress has not yet been sufficiently investigated. Therefore, in this study we investigated the beneficial impacts of seed priming with low (L) and high (H) concentrations of nanoparticles including nSiO2 (50/100 mg L-1), nTiO2 (20/60 mg L-1), nZnO (50/100 mg L-1), nFe3O4 (100/200 mg L-1), nCuO (50/100 mg L-1), and nCeO2 (50/100 mg L-1) on lettuce growth and antioxidant enzyme activities aiming to assess their efficacy for enhancing plant growth and reducing Cd phytotoxicity. The results showed a significant increase in plant growth, biomass production, antioxidant enzyme activities, and photosynthetic efficiency in lettuce treated with nano-primed nSiH + Cd (100 mg L-1), nTiH + Cd (60 mg L-1), and nZnL + Cd (50 mg L-1) under Cd stress. Moreover, nano-priming effectively reduced the accumulation of reactive oxygen species (ROS) and malondialdehyde (MDA) in lettuce shoots. Interestingly, nano-primed nSiH + Cd, nTiH + Cd, and nZnL + Cd demonstrated efficient reduction of Cd uptake, less translocation factor of Cd with high tolerance index, ultimately reducing toxicity by stabilizing the root morphology and superior accumulation of critical nutrients (K, Mg, Ca, Fe, and Zn). Thus, this study provides the first evidence of alleviating Cd toxicity in lettuce by using multiple nanoparticles via priming strategy. The findings highlight the potential of nanoparticles (Si, Zn, and Ti) as stress mitigation agents for improved crop growth and yield in Cd contaminated areas, thereby offering a promising and advanced approach for remediation of Cd contaminated environments.

Catchment land use effect on mercury concentrations in lake sediments: A high-resolution study of Qinghai Lake.

Mercury (Hg) contamination in aquatic environments presents a significant ecological and human health concern. This study explored the relationship between catchment land use and Hg concentrations within Qinghai Lake sediment, the largest lake in China, situated on the Qinghai-Tibet plateau. The study entailed detailed mapping of Hg sediment concentrations and a subsequent environmental risk assessment. Considering the complex nature of the plateau landform and surface vegetation, the study area was delineated at a 100 km radius centered on Qinghai Lake, which was divided into 30 sectors to quantify relationships between land use and the sediment Hg concentration. The results revealed a mean sediment Hg concentration of 29.91 µg/kg, which was elevated above the background level. Kendall's correlation analysis revealed significant but weak associations between sediment Hg concentrations and three land use types: grassland (rangeland and trees) (rs = 0.27, p < 0.05), crops (rs = -0.37, p < 0.05), and bare ground (rs = -0.25, p < 0.1), suggesting that growing areas of grassland correlated with higher Hg levels in the lake sediment, in contrast to bare ground or crops area, which correlated with lower Hg concentrations. Multiple linear regression models also observed weak negative relationships between bare ground and crops with sediment Hg concentration. This research methodology enhances our understanding of the impact of land use on Hg accumulation in lake sediments and underscores the need for integrated watershed management strategies to mitigate Hg pollution in Qinghai Lake.

The distribution, fate, and environmental impacts of food additive nanomaterials in soil and aquatic ecosystems.

Nanomaterials in the food industry are used as food additives, and the main function of these food additives is to improve food qualities including texture, flavor, color, consistency, preservation, and nutrient bioavailability. This review aims to provide an overview of the distribution, fate, and environmental and health impacts of food additive nanomaterials in soil and aquatic ecosystems. Some of the major nanomaterials in food additives include titanium dioxide, silver, gold, silicon dioxide, iron oxide, and zinc oxide. Ingestion of food products containing food additive nanomaterials via dietary intake is considered to be one of the major pathways of human exposure to nanomaterials. Food additive nanomaterials reach the terrestrial and aquatic environments directly through the disposal of food wastes in landfills and the application of food waste-derived soil amendments. A significant amount of ingested food additive nanomaterials (> 90 %) is excreted, and these nanomaterials are not efficiently removed in the wastewater system, thereby reaching the environment indirectly through the disposal of recycled water and sewage sludge in agricultural land. Food additive nanomaterials undergo various transformation and reaction processes, such as adsorption, aggregation-sedimentation, desorption, degradation, dissolution, and bio-mediated reactions in the environment. These processes significantly impact the transport and bioavailability of nanomaterials as well as their behaviour and fate in the environment. These nanomaterials are toxic to soil and aquatic organisms, and reach the food chain through plant uptake and animal transfer. The environmental and health risks of food additive nanomaterials can be overcome by eliminating their emission through recycled water and sewage sludge.

Biochar co-pyrolyzed from peanut shells and maize straw improved soil biochemical properties, rice yield, and reduced cadmium mobilization and accumulation by rice: Biogeochemical investigations.

Biochar is an eco-friendly amendment for the remediation of soils contaminated with cadmium (Cd). However, little attention has been paid to the influence and underlying mechanisms of the co-pyrolyzed biochar on the bioavailability and uptake of Cd in paddy soils. The current study explored the effects of biochar co-pyrolyzed from peanut shells (P) and maize straw (M) at different mixing ratios (1:0, 1:1, 1:2, 1:3, 0:1, 2:1 and 3:1, w/w), on the bacterial community and Cd fractionation in paddy soil, and its uptake by rice plant. Biochar addition, particularly P1M3 (P/M 1:3), significantly elevated soil pH and cation exchange capacity, transferred the mobile Cd to the residual fraction, and reduced Cd availability in the rhizosphere soil. P1M3 application decreased the concentration of Cd in different rice tissues (root, stem, leaf, and grain) by 30.0%- 49.4%, compared to the control. Also, P1M3 enhanced the microbial diversity indices and relative abundance of iron-oxidizing bacteria in the rhizosphere soil. Moreover, P1M3 was more effective in promoting the formation of iron plaque, increasing the Cd sequestration by iron plaque than other treatments. Consequently, the highest yield and lowest Cd accumulation in rice were observed following P1M3 application. This study revealed the feasibility of applying P1M3 for facilitating paddy soils contaminated with Cd.

A hidden demethylation pathway removes mercury from rice plants and mitigates mercury flux to food chains.

Dietary exposure to methylmercury (MeHg) causes irreversible damage to human cognition and is mitigated by photolysis and microbial demethylation of MeHg. Rice (Oryza sativa L.) has been identified as a major dietary source of MeHg. However, it remains unknown what drives the process within plants for MeHg to make its way from soils to rice and the subsequent human dietary exposure to Hg. Here we report a hidden pathway of MeHg demethylation independent of light and microorganisms in rice plants. This natural pathway is driven by reactive oxygen species generated in vivo, rapidly transforming MeHg to inorganic Hg and then eliminating Hg from plants as gaseous Hg°. MeHg concentrations in rice grains would increase by 2.4- to 4.7-fold without this pathway, which equates to intelligence quotient losses of 0.01-0.51 points per newborn in major rice-consuming countries, corresponding to annual economic losses of US$30.7-84.2 billion globally. This discovered pathway effectively removes Hg from human food webs, playing an important role in exposure mitigation and global Hg cycling.

Digestive fluid components affect speciation and bioaccessibility and the subsequent exposure risk of soil chromium from stomach to intestinal phase in in-vitro gastrointestinal digestion.

The simulated in-vitro gastrointestinal method provides a simple way to evaluate the health risk of human body exposed to soil contaminants. Several in-vitro methods have been successfully established for soil As, Pb, and Cd. However, the method development for soil Cr failed up to now, which could be resulted from alteration in the species of Cr (e.g., Cr(VI)/Cr(III)) caused by the gastrointestinal digestion components, ultimately affecting the accessibility of Cr. This study explored the transformation and bioaccessibility of Cr in two Cr-contaminated soils during the physiologically based extraction test. The water-soluble and exchangeable Cr in soil was dissolved in gastrointestinal tract, accompanied with reduction of Cr(VI) into Cr(III), and the reduction occurred after the chemical extraction in two soils rather than during the extraction. Pepsin and organic acids in gastric phase could reduce Cr(VI) into Cr(III) and reduction efficiency were 20.4%- 53.0%, while in intestinal phase, pancreatin and bile salt had little effect on the Cr(VI) reduction, instead, more Cr(VI) was released from soil. In the gastric solution, Cr(VI) was mainly present as HCrO4- and Cr(III) as free Cr3+ ion. In the intestinal phase, Cr(VI) mainly occurred as CrO42- and Cr(III) as Cr(OH)3 (aq). Cr in the soil solid phase was dominated as the precipitates of Cr-Fe oxide, which was hardly extracted. Bioaccessibility of Cr in gastric phase increased as extraction duration increased and decreased in the intestinal phase, the contrary trend was observed for the hazard quotient of Cr in two phases due to Cr(VI)/Cr(III) transformation. This study indicates that the gastrointestinal components could influence the Cr transformation and subsequently affect the Cr bioaccessibility, which would help for a successful establishment of in vitro determination method for soil Cr bioaccessibility.

Temperature-induced changes in DTPA-extractable trace elements: Predicting the potential impact of climate change on the availability of soil elements.

The extraction of trace elements from soil with DTPA is a widely used protocol across laboratories. There is a possible "hidden" discrepancy regarding the results obtained from the extractions, i.e., ambient laboratory temperature and soil properties. In this study, the possible influence of these factors on the extractability of the available forms of Cu, Fe, Pb, Mn, Ni, and Zn, measured with DTPA were studied. Α series of extractions was carried out on a soil sample under normal laboratory temperatures, which fluctuated throughout the year, from 15 to 33.9 °C. In other 144 soil samples, the prevailing physico-chemical properties of soil were evaluated (pH, organic C, clay, CaCO3) that affected the percentage of DTPA extractability relative to the pseudo-total determined content. A strong positive correlation of all metals versus increased ambient temperature was found. Cu had an R2 of 0.897, Fe 0.970, Mn 0.957, Ni 0.938, Pb 0.876, and, Zn 0.922, all highly significant. Extracted Mn exhibited a 6.5-fold increase at the highest temperature of 33.9 οC compared to the lowest. Similar increasing trend was observed for Fe, and Ni, and smaller for Cu, Zn, and Pb. Inherent soil properties affected the percentage of extractability relative to the total content: extractability of Cu, Fe, Mn, and Ni was affected negatively by pH, and the extractability of the studied metals with CaCO3 content. Other soil properties (organic C and clay/sand content) also had an effect, not as pronounced as that of pH and CaCO3. This signifies the necessity of employing standard conditions for routine extractions such as DTPA so that data may be comparable. Also these identified discrepancies may have consequences in the extractability and availability of soil micronutrients and toxic elements regarding climate change. This study aspires to play the role of an initial step towards more robust investigations that would suggest ways of correcting temperature and soil characteristics discrepancies across laboratories.