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The diffusive gradient in thin films technique (DGT), with a resin gel based on Lewatit® FO 36 was used for the first time to predict arsenic (As) bioavailability in soils collected in different environmental contexts. The predicted bioavailability, determined by fluxes to DGT, was compared with the bioavailability and bioaccumulation in the plants (Calendula officinalis), where a strong correlation was observed (r = 0.8857 (C E /C roots ) and r = 0.9208 (C E /C shoots ); p < 0.05; n > 40). Arsenic, predominantly accumulated in the roots of plants from all soil samples, reached concentrations up to 507.8 mg kg -1 . To better understand the As distribution within the various soil-bearing phases, sequential extraction procedures were performed and revealed low mobility and availability of As, particularly in A and R soil samples, where As pollution is primarily caused by anthropogenic activities such as mining and industrial activities. The obtained results show that Calendula officinalis plants can be grown on soils contaminated by arsenic, while the low translocation factors indicate that accumulate arsenic predominantly in the root system., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Biodegradable plastics (BPs) are regarded as ecomaterials and are emerging as a substitute for traditional non-degradable plastics. However, the information on the interaction between biodegradable microplastics (BMPs) and cadmium (Cd) in agricultural soil is still limited. Here, lettuce plants were cultured in BMPs (polylactic acid (PLA) MPs and poly(butylene-adipate-co-terephthalate) (PBAT) MPs) and Cd co-polluted soil for 35 days. The results show that diffusive gradient in thin films technique (DGT) but not diethylenetriaminepentaacetic acid (DTPA) extraction method greatly improved the prediction reliability of Cd bioavailability in non-rhizosphere soil treated with BMPs (R 2  = 0.902). BMPs increased the Cd bioavailability in non-rhizosphere soil indirectly by decreasing soil pH, cation exchange capacity (CEC), and dissolved organic carbon (DOC), rather than by directly adsorbing Cd on their surface. PLA MPs incubated in rhizosphere soil showed more considerable degradation with extremely obvious cavities and the fracture of ester functional groups on their surface than PBAT MPs. BMPs could provide ecological niches to colonize and induce microorganisms associated with BMPs' degradation to occupy a more dominant position. In addition, Cd only affected the composition and function of microbial communities in soil but not on BMPs. However, co-exposure to BMPs and Cd significantly reduced the degrees of co-occurrence network of fungal communities on PLA MPs and PBAT MPs by 37.7% and 26.7%, respectively, compared to single exposure to BMPs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Naturally selenium (Se)-rich soils often contain elevated cadmium (Cd) levels, complicating safe production of Se-enriched rice. This study employed diffusive gradients in thin-films (DGT) and DGT-induced fluxes in soils (DIFS) model to determine Se and Cd bioavailability in paddy soils. We investigated desorption kinetics and accumulation patterns in rice using paired rhizosphere and grain samples from 65 field sites in Guangxi, China, encompassing Se-enriched karst and non-karst soils. Despite greater total Se and Cd contents in karst soils, their elevated pH, along with greater soil organic matter and total Fe, Mn, and Ca contents, constrained Se and Cd bioavailability, resulting in similar accumulation levels in rice grains from both soil categories. DIFS-derived kinetic data revealed that Se was replenished 75.4 times faster than Cd, but Cd had an 83.2 times larger labile pool, leading to a stronger overall Cd resupply capacity. DGT-based labile Se:Cd molar ratios showed that rice Cd content declined sharply as the ratio increased from 0.7 to 4.0, stabilizing at its lowest level when exceeding 20. Moreover, DGT measurements demonstrated stronger correlations with grain Se and Cd concentrations compared to traditional methods. Our findings highlight the effectiveness of DGT and kinetic analyses in determining Se and Cd bioavailability in high-background paddy soils, offering insights for balancing Se fortification and Cd risk mitigation in rice production., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The marine toxins of the Okadaic acid (OA) group are natural compounds produced by dinoflagellates that enters the food chain by accumulating in seafood. They are responsible for Diarrhetic Shellfish Poisoning (DSP) events in humans over the world and therefore are also jointly named as Diarrhetic Shellfish Toxins (DSTs). The main objective of this study was to evaluate symptoms, toxicity, absorption, distribution, and elimination of OA, Dinophysistoxin-1 (DTX1), and Dinophysistoxin-2 (DTX2) at the sublethal dose of 90 μg toxin/kg bw administered through voluntary feeding to mice. The toxin comparison highlighted that OA and DTX1 induced more severe and specific symptoms such as diarrhea. After oral ingestion toxins were distributed through the entire organism being detected in liver, kidney, stomach, small and large intestine. Predominant excretion of the toxins was observed in feces, with OA exhibiting fast elimination, while DTX2 was showing prolonged excretion. The passage and accumulation of toxins in gastrointestinal organs instigated macroscopic damage in the stomach, small and large intestine that could persist up to 120 h. These findings highlight the importance of pharmacokinetic of sublethal doses of DSTs administered by voluntary feeding in their toxicity and their implication for public health., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Due to the bioavailability and movement of antimony in trophic web, the overexploitation of antimony mine resulted in antimony contamination that harmed the ecology nearby, raising concerns for public health. Whereas, most researches focused on the removal of antimony in the aqueous instead of the immobilization of antimony in the soil. Herein, the immobilized performance of biochar (BC) loaded with nano zero-valent iron (nZVI-BC) on antimony in the soil near the smelting area was researched through pot experiments for the first time, and its stabilization mechanism on antimony was investigated by valent state variation of antimony. The results demonstrated that BC restricted the cation exchange capacity and catalase activity in the soil, while nZVI-BC had a favorable and negative impact on two variables, respectively. The nZVI-BC showed more stable immobilization capacity on antimony over time than BC, whose exchangeable speciation only marginally rose (2%-6%), although the exchangeable speciation of antimony fell both from 15% to 2% after adding the BC and nZVI-BC, The electron attraction force between nZVI-BC and antimony was also intensified owing to the oxidation-reduction process, which was considered as the stabilizing principle of nZVI-BC on antimony in soil. Furthermore, the decreased bioaccumulation factor for the perennial ryegrass (0.46-0.21) and Galinsoga parviflora Cav. (0.26-0.17) stated that the BC effectively mitigated the bioaccumulation risk of antimony., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Interactions between polycyclic aromatic hydrocarbons (PAHs) and titanium dioxide (TiO 2 ) nanoparticles (NPs) can produce unforeseen photoproducts in the aqueous phase. Both PAHs and TiO 2 -NPs are well-studied and highly persistent environmental pollutants, but the consequences of PAH-TiO 2 -NP interactions are rarely explored. We investigated PAH photoproduct formation over time for benzo[a]pyrene (BaP), fluoranthene (FLT), and pyrene (PYR) in the presence of ultraviolet A (UVA) using a combination of analytical and computational methods including, identification of PAH photoproducts, assessment of expression profiles for gene indicators of PAH metabolism, and computational evaluation of the reaction mechanisms through which certain photoproducts might be formed. Chemical analyses identified diverse photoproducts, but all PAHs shared a primary photoproduct, 9,10-phenanthraquinone (9,10-PQ), regardless of TiO 2 -NP presence. The computed reaction mechanisms revealed the roles photodissociation and singlet oxygen chemistry likely play in PAH mediated photochemical processes that result in the congruent production of 9,10-PQ within this study. Our investigation of PAH photoproduct formation has provided substantial evidence of the many, diverse and congruent, photoproducts formed from physicochemically distinct PAHs and how TiO 2 -NPs influence bioavailability and time-related formation of PAH photoproducts., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The use of Sargassum spp., a brown invasive algae, for the production of biochars (BCs) or activated carbons (ACs) and their efficiency to sequestrate chlordecone (CLD) in soil has been recently suggested. The objective of this study was to assess the potential of microwave prepared Sargasso biochar (BCS) amendment in Andosol on the bioavailability of chlordecone in laying hens and piglets, when exposed to this matrix. The efficiency of BCS was compared to a commercial activated carbon, DARCO® (ACD), used as a positive control and to an unamended soil. Samples of CLD-contaminated Andosol were amended with 2% of each carbonaceous matrix and let maturing for 3 months. Thereafter, adequate doses of soil were administered into the laying hens and piglets diets every day during the exposure phase, to simulate involuntary soil ingestion which may happen in practical conditions when animals are reared outside. Finally, bioavailability tests were carried out on target tissue (liver, muscle, adipose tissues and egg yolk). The results showed that the highest reduction of CLD bioavailability was obtained with ACD in both animal species. For laying hens, ACD showed reductions of around 60% (liver: 59%, muscle: 57% and egg yolk: 56%) whereas the BCS showed reduction of around 30% (liver: 31%, muscle: 26% and egg yolk: 30%) compared to the unamended soil. For piglets, only the liver showed interpretable results with reduction of 65% with ACD and 41% with BCS. Overall, BCS is efficient reducing CLD availability but in a lower extend than ACD. This discrepancy may be explained by the variations of physico-chemical characteristics that exist between the two matrices, resulting, from the additional activation phase for DARCO®. Therefore, to improve the efficiency of BCS it would be interesting to move towards DARCO® characteristics by determining out the optimal microwave pyrolysis parameters., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The two trace elements cobalt (Co) and nickel (Ni) are widely distributed in the environment due to the increasing industrial application, for example in lithium-ion batteries. Both metals are known to cause detrimental health impacts to humans when overexposed and both are supposed to be a risk factor for various diseases. The individual toxicity of Co and Ni has been partially investigated, however the underlying mechanisms, as well as the interactions of both remain unknown. In this study, we focused on the treatment of liver carcinoma (HepG2) and astrocytoma (CCF-STTG1) cells as a model for the target sites of these two metals. We investigated their effects in single and combined exposure on cell survival, cell death mechanisms, bioavailability, and the induction of oxidative stress. The combination of CoCl 2 and NiCl 2 resulted in higher Co levels with subsequent decreased amount of Ni compared to the individual treatment. Only CoCl 2 and the combination of both metals led to RONS induction and increased GSSG formation, while apoptosis and necrosis seem to be involved in the cell death mechanisms of both CoCl 2 and NiCl 2 . Collectively, this study demonstrates cell-type specific toxicity, with HepG2 representing the more sensitive cell line. Importantly, combined exposure to CoCl 2 and NiCl 2 is more toxic than single exposure, which may originate partly from the respective cellular Co and Ni content. Our data imply that the major mechanism of joint toxicity is associated with oxidative stress. More studies are needed to assess toxicity after combined exposure to elements such as Co and Ni to advance an improved hazard prediction for less artificial and more real-life exposure scenarios., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Current human health risk assessments of soil arsenic (As) contamination rarely consider bioaccessibility (IVBA), which may overestimate the health risks of soil As. The IVBA of As (As-IVBA) may differ among various soil types. This investigation of As-IVBA focused As from geological origin in a typical subtropical soil, lateritic red soil, and its risk control values. The study used the SBRC gastric phase in vitro digestion method and As speciation sequential extraction based upon phosphorus speciation extraction method. Two construction land sites (CH and HD sites) in the Pearl River Delta region were surveyed. The results revealed a high content of residual As (including scorodite, mansfieldite, orpiment, realgar, and aluminum arsenite) in the lateritic red soils at both sites (CH: 84.9%, HD: 91.7%). The content of adsorbed aluminum arsenate (CH: 3.24%, HD: 0.228%), adsorbed ferrum arsenate (CH: 8.55%, HD: 5.01%), and calcium arsenate (CH: 7.33%, HD: 3.01%) were found to be low. The bioaccessible As content was significantly positively correlated with the As content in adsorbed aluminum arsenate, adsorbed ferrum arsenate, and calcium arsenate. A small portion of these sequential extractable As speciation could be absorbed by the human body (CH: 14.9%, HD: 3.16%), posing a certain health risk. Adsorbed aluminum arsenate had the highest IVBA, followed by calcium arsenate, and adsorbed ferrum arsenate had the lowest IVBA. The aforementioned speciation characteristics of As from geological origin in lateritic red soil contributed to its lower IVBA compared to other soils. The oxidation state of As did not significantly affect As-IVBA. Based on As-IVBA, the carcinogenic and non-carcinogenic risks of soil As in the CH and HD sites decreased greatly in human health risk assessment. The results suggest that As-IVBA in lateritic red soil should be considered when assessing human health risks on construction land., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Microorganisms play an important role in heavy metal bioremediation and soil fertility. The effects of soil inoculation with Pseudomonas sp. W112 on Cd accumulation in wheat were investigated by analyzing the transport, subcellular distribution and speciation of Cd in the soil and plants. Pseudomonas sp. W112 application significantly decreased Cd content in the roots, internode and grains by 10.2%, 29.5% and 33.0%, respectively, and decreased Cd transfer from the basal nodes to internodes by 63.5%. Treatment with strain W112 decreased the inorganic and water-soluble Cd content in the roots and increased the proportion of residual Cd in both the roots and basal nodes. At the subcellular level, the Cd content in the root cell wall and basal node cytosol increased by 19.6% and 61.8%, respectively, indicating that strain W112 improved the ability of the root cell wall and basal node cytosol to fix Cd. In the rhizosphere soil, strain W112 effectively colonized and significantly decreased the exchangeable Cd, carbonate-bound Cd and iron-manganese oxide-bound Cd content by 43.5%, 27.3% and 17.6%, respectively, while it increased the proportion of residual Cd by up to 65.2%. Moreover, a 3.1% and 23.5% increase in the pH and inorganic nitrogen content in the rhizosphere soil, respectively, was recorded. Similarly, soil bacterial community sequencing revealed that inoculating with strain W112 increased the abundance of Pseudomonas, Thauera and Azoarcus, which are associated with inorganic nitrogen metabolism, and decreased that of Acidobacteria, which is indicative of soil alkalinization. Hence, root application of Pseudomonas sp. W112 improved soil nitrogen availability and inhibited Cd accumulation in the wheat grains in a two-stage process: by reducing the Cd availability in the rhizosphere soil and by improving Cd interception and fixation in the wheat roots and basal nodes. Pseudomonas sp. W112 may be a suitable bioremediation agent for restoring Cd-contaminated wheat fields., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The bioavailability of contaminants in aquatic environments was highly related with the existing forms (soluble or adsorbed) and properties of dissolved organic matters (DOMs). In this study, the molecular weight (MWs)-dependent effects of DOMs on the adsorption and bioavailability of sulfadiazine were explored. Colloid ZnO and Al 2 O 3 were employed as the representative colloidal particles, and algae-derived organic matter (AOM) and humic acid (HA) were selected as typical autochthonous and allochthonous DOMs. The ultrafiltration procedure was applied to divide the bulk DOMs into high MW (HMW-, 1 kDã0.45 μm) and low MW (LMW-, <1 kDa) fractions. Results showed that HMW-DOM contained more aromatic and protein-like substances as compared to the LMW counterparts. In addition, presence of AOM promoted sulfadiazine adsorption capabilities by 1.19-4.54 folds and mitigated the inhibition ratio by 0.56-0.78 folds, whereas those of HA inhibited sulfadiazine adsorption by 0.27-0.84 folds and enhanced the biotoxicity by 1.21-1.45 folds. Regardless of different DOM types, HMW-fraction exhibited highest effects on sulfadiazine adsorption and bioavailability, followed by the bulk- and LMW-fractions. Two-dimensional correlation spectroscopy showed that sulfadiazine was adsorbed on colloidal surfaces prior to AOM, and the subsequent adsorption of AOM can provide additional sites for sulfadiazine adsorption, which decreased the concentrations of aqueous sulfadiazine as well as the biotoxicity to Microcystis aeruginosa (M. aeruginosa). The HA, however, was preferentially adsorbed on colloidal surfaces, which hindered the subsequent sulfadiazine adsorption and resulted in a high sulfadiazine abundance in aqueous solution as well as the enhanced biotoxicity to M. aeruginosa. This study highlighted the importance of the types and MWs of DOMs in influencing the behaviors and ecological effects of aquatic contaminants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Regulating nitrogen source composition is efficient approach to accelerate the spent mushroom substrate (SMS) composting process. However, currently, most traditional composting study only focuses on total C/N ratio of initial composting material. Rarely research concerns the effect of carbon or nitrogen components at different degradable level and their corresponding decomposed-substances on humification process. This study deciphers and compares the mechanism of mixed manure-N sources on SMS humification from bioavailability and molecular perspective. Two different biodegradable manure-N sources, cattle manure (CM) and Hainan chicken manure (CH), were added into the SMS composting with the different CM:CH ratio of 1:0, 3:1, 1:1, 1:3, and 0:1, respectively. The physicochemical properties and humic substances were determined to evaluate the compost quality. Coupling analysis of spectroscopy, fluorescence, and humic intermediate precursors were conducted to characterizing molecular formation process of humic acid (HA). The results indicated that regulating the carbon-nitrogen nutrient biodegradability of composting material by adding mixed nitrogen sources is an effective strategy to accelerate the SMS humification process. The C1H3 (CM:CH ratio of 1:3) and CH treatments obtained great physicochemical properties and the highest growth rate of HA (31.96% and 27.02%, respectively). The rapid reaction of polysaccharide, ketone, quinone, and amide in DOM (LCP1) might be the key for the fast humification in C1H3 and CH. The polyphenol, reducing sugar and amino acid originated from the labile-carbon-proportion I (LCP1) and recalcitrant-carbon-proportion (RCP), labile-carbon-proportion II (LCP2) and RCP, and labile-nitrogen-proportion I (LNP1), respectively, were the main driving intermediate precursors for the formation of HA. This study deciphers the SMS humification mechanism at molecular level and provides a strategy in accelerating-regulating the composting process. which will be beneficial for enhancing the disposing efficiency of SMS, producing high-quality organic fertilizer, and even popularizing to the similar types of organic waste in practical field., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Among endocrine disruption, interference with the thyroid hormone (TH) regulation is of increasing concern. Respective compounds encode through their structural features both the potential for TH disruption, and the bioavailability mitigating the toxicological effect. The aim of this study is to provide a substructure-based screening-level QSAR (quantitative structure-activity relationship) that discriminates bioavailable TH disruptors from not bioavailable counterparts, covering both direct and indirect (retinoid- and AhR-mediated) modes of action. The QSAR has been derived from literature data for 1642 compounds, and takes into account Lipinski's rule-of-five and the brain/blood partition coefficient K brain/blood . For its validation, an external test set of 145 substances has been used. For 1787 compounds meeting the model application domain, the model yields only one false negative. The discussion addresses the mechanistic meaning of the bioavailability triggers molecular weight, H-bond donor and acceptor, hydrophobicity (log K ow ), and the physicochemical properties underlying log K brain/blood . The model may serve as bioavailability-screening step within a decision support system for the predictive assessment of chemicals regarding their potential to disrupt thyroid hormone function in a direct or indirect manner., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Stratigraphic lithology strongly influences the spatial heterogeneity of soil available selenium (ASe), however, it is often neglected in regional simulation. Therefore, taking the Jiangjin District, where the soil is richer in selenium (Se), as the research area, the changes of soil ASe at different spatial scales have been simulated by combining Geodetector and three popular models (Multiple linear regression (MLR), Random forest (RF) and BP neural network (BPN)). The results showed that modelling with 'Formation' as the spatial scale could reduce the influence of stratum lithology difference on the spatial heterogeneity of soil ASe and improve the model's prediction accuracy. Compared with the MLR (R 2  = 0.52, root mean squares error (RMSE) = 13.217 μg kg -1 ) and BPN (R 2  = 0.55, RMSE = 13.79 μg kg -1 ), the RF (R 2  = 0.67, RMSE = 10.85 μg kg -1 ) exhibited higher R 2 and smaller RMSE, and the simulation effect of soil ASe is the best in the Middle Jurassic Shaximiao Formation (J 2 s). The outcomes of variable importance analysis revealed that soil total selenium (TSe) and soil organic matter (SOM) were the imperative factors for predicting ASe. The scenario simulation prediction showed that in the next 40 years, due to the combined influence of SOM and pH, the content of ASe in soil developed in the J 2 s would decrease from 40.8 μg kg -1 to 37.8 μg kg -1 , a 7.8 percent drop. The main areas of soil ASe loss were in the western farming areas. The ASe content in dry land and paddy fields decreased by 12.0% and 4.9%, respectively. Therefore, long-term agricultural production activities would lead to soil ASe loss. The present results could provide a new scheme for the simulation and prediction of regional soil ASe, which is helpful for scientific planning, utilization of selenium-rich soil resources, and development of regional agricultural economy., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Due to its large specific surface area and great hydrophobicity, microplastics can adsorb polycyclic aromatic hydrocarbons (PAHs), affecting the bioavailability and the toxicity of PAHs to plants. This study aimed to evaluate the effects of D550 and D250 (with diameters of 550 μm and 250 μm) microplastics on phenanthrene (PHE) removal from soil and PHE accumulation in maize (Zea mays L.). Moreover, the effects of microplastics on rhizosphere microbial community of maize grown in PHE-contaminated soil would also be determined. The results showed that D550 and D250 microplastics decreased the removal of PHE from soil by 6.5% and 2.7% and significantly reduced the accumulation of PHE in maize leaves by 64.9% and 88.5%. Interestingly, D550 microplastics promoted the growth of maize and enhanced the activities of soil protease and alkaline phosphatase, while D250 microplastics significantly inhibited the growth of maize and decreased the activities of soil invertase, alkaline phosphatase and catalase, in comparison with PHE treatment. In addition, microplastics changed the rhizosphere soil microbial community and reduced the relative abundance of PAHs degrading bacteria (Pseudomonas, Massilia, Proteobacteria), which might further inhibit the removal of PHE from soil. This study provided a new perspective for evaluating the role of microplastics on the bioavailability of PHE to plants and revealing the combined toxicity of microplastics and PHE to soil microcosm and plant growth., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The aim of this study was to assess the bioavailability of epoxiconazole (EPO) and difenoconazole (DIF) in rice plants by evaluating their uptake, translocation, and accumulation. The results showed that the concentration of DIF in the roots was approximately three times higher than EPO, and both accumulated mainly in the roots. In addition, EPO continued to be transported from stems to leaves, causing a rise in its concentration in leaves. Contrastingly, only a minimal amount of DIF was transported to the leaves. This phenomenon is mainly governed by their differing octanol-water partition coefficient. The effects of dissolved organic carbon (DOC) on the accumulation of EPO and DIF in the roots were similar to those of the freely dissolved concentration measured by OECAMs. The concentrations of EPO and DIF in the roots and OECAMs consistently decreased with increasing DOC levels. Furthermore, a significant linear relationship was observed between the EPO and DIF concentrations in root and OECAMs. We also confirmed the accuracy and usefulness of the OECAMs method in predicting the bioavailability of EPO and DIF in rice roots. Therefore, OECAMs show good potential for use as a passive sampler to evaluate the bioavailability of EPO and DIF., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Exposure to heavy metal(loid)s (HM) through contaminated food chains poses significant health risks to humans. While soil amendments are known to reduce HM bioavailability, their effects on bioaccessibility and health risks in soil-pakchoi-human systems remain unclear. To address this knowledge gap, we conducted a greenhouse pot experiment coupling soil immobilization with bioaccessibility-based health risk assessment for Cd and As exposure from pakchoi consumption. Four amendments (attapulgite, shell powder, nanoscale zero-valent iron, and biochar) were applied to soil, resulting in changes to soil characteristics (pH and organic matter), plant dry weight, and exchangeable fractions of As and Cd. Among the tested amendments, biochar exhibited the highest effectiveness in reducing the risk of Cd and As exposure from pakchoi consumption. The bioaccessibility-based health risk assessment revealed that the application of 5% biochar resulted in the lowest hazard index, significantly decreasing it from 1.36 to 0.33 in contaminated soil. Furthermore, the structural equation model demonstrated that pH played a critical role in influencing remediation efficiency, impacting the exposure of the human body to Cd and As. In conclusion, our study offers a new perspective on mitigating exposure risks of soil HM and promoting safe crop production. The results underscore the importance of considering bioaccessibility in health risk assessment and highlight the potential of biochar as a promising amendment for reducing Cd and As exposure from pakchoi consumption., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Straw amendment is a prevalent agricultural practice worldwide, which can reduce air pollution and improve soil fertility. However, the impact of aging straw amendment on the bioavailability of mercury (Hg) and methylmercury (MeHg) in paddy soil remains unclear. To investigate this, incubation experiments were conducted using the diffusive gradient in thin-film technique. Results showed that amendments of dry-wet aging (DRS), photochemical aging (LRS), and freeze-thaw aging rice straw (FRS) reduced the bioavailable MeHg in paddy soil by 2.2-27.6%, 13.5-69.8%, and 23.5-86.1%, respectively, compared to fresh rice straw (RS) amendment. This result could be due to changes in soil properties such as soil pH and overlying water Fe and Mn as well as microbial abundance (including Clostridiaceae, Firmicutes, and Actinobacteriota). Simultaneously, The LRS and FRS amendments reduced bioavailable Hg in paddy soil by 20.0-40.8% and 17.1-48.6%, respectively, while DRS increased the bioavailable Hg by 15.8-120.0%. This could be attributed to changes in soil oxidation-reduction potential and overlying water SO 4 2- content. Additionally, the results of sand culture experiments showed that the concentrations of Hg uptake by rice seedlings were 97.1-118.2%, 28.1-35.6%, and 198.0-217.1% higher in dissolved organic matter (DOM) derived from DRS, LRS, and FRS than RS, indicating that aging straw leached DOM may promote the Hg bioavailable when straw amendment. This result could be due to lower molecular weight and higher CO functional group content. These results provide new insight into how aging straw amendment affects the bioavailability of Hg and MeHg in paddy soil under different climates., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The mechanisms of toxicity of engineered nanomaterials (ENMs) to the early life stages of freshwater fish, and the relative hazard compared to dissolved metals, is only partially understood. In the present study, zebrafish (Danio rerio) embryos were exposed to lethal concentrations of silver nitrate (AgNO 3 ) or silver (Ag) ENMs (primary size 42.5 ± 10.2 nm). The 96 h-LC 50 for AgNO 3 was 32.8 ± 0.72 μg Ag L -1 (mean ± 95% CI) compared to 6.5 ± 0.4 mg L -1 of the whole material for Ag ENMs; with the ENMs being orders of magnitude less toxic than the metal salt. The EC 50 for hatching success was 30.5 ± 1.4 μg Ag L -1 and 6.04 ± 0.4 mg L -1 for AgNO 3 and Ag ENMs, respectively. Further sub-lethal exposures were performed with the estimated LC 10 concentrations for both AgNO 3 or Ag ENMs over 96 h, where about 3.7% of the total Ag as AgNO 3 was internalised, as measured by Ag accumulation in the dechorionated embryos. However, for the ENM exposures, nearly all (99.8%) of the total Ag was associated with chorion; indicating the chorion as an effective barrier to protect the embryo in the short term. Calcium (Ca 2+ ) and sodium (Na + ) depletion was induced in embryos by both forms of Ag, but hyponatremia was more pronounced in the nano form. Total glutathione (tGSH) levels declined in embryos exposed to both Ag forms, but a superior depletion occurred with the nano form. Nevertheless, oxidative stress was mild as superoxide dismutase (SOD) activity stayed uniform and the sodium pump (Na + /K + -ATPase) activity had no appreciable inhibition compared to the control. In conclusion, AgNO 3 was more toxic to the early life stage zebrafish than the Ag ENMs, still differences were found in the exposure and toxic mechanisms of both Ag forms., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Pyrolysis of calcium-rich feedstock (e.g., poultry manure) generates semi-crystalline and crystalline phosphorus (P) species, compromising its short-term availability to plants. However, enriching poultry manure with magnesium (Mg) before pyrolysis may improve the ability of biochar to supply P. This study investigated how increasing the Mg/Ca ratio and pyrolysis temperature of poultry manure affected its P availability and speciation. Mg enrichment by ∼2.1% increased P availability (extracted using 2% citric and formic acid) by 20% in Mg-biochar at pyrolysis temperatures up to 600 °C. Linear combination fitting of P K-edge XANES of biochar, and Mg/Ca stoichiometry, indicate that P species, mainly Ca-P and Mg-P, are altered after pyrolysis. At 300 °C, adding Mg as magnesium hydroxide [Mg(OH) 2 ] created MgNH 4 PO 4 (18%) and Mg 3 (PO 4 ) 2 .8H 2 O (23%) in the biochar, while without addition of Mg Ca 3 (PO 4 ) 2 (11%) predominated, both differing only for pyrophosphate, 33 and 16%, respectively. Similarly, the P L 2,3 edge XANES data of biochar made with Mg were indicative of either MgHPO 4 .3H 2 O or Mg 3 (PO 4 ) 2 .8H 2 O, in comparison to CaHPO 4 .2H 2 O or Ca 3 (PO 4 ) 2 without Mg. More importantly, hydroxyapatite [Ca 5 (PO 4 ) 3 (OH)] was not identified with Mg additions, while it was abundant in biochars produced without Mg both at 600 (12%) and 700 °C (32%). The presence of Mg formed Mg-P minerals that could enhance P mobility in soil more than Ca-P, and may have resulted in greater P availability in Mg-enriched biochars. Thus, a relatively low Mg enrichment can be an approach for designing and optimize biochar as a P fertilizer from P-rich excreta, with the potential to improve P availability and contribute to the sustainable use of organic residues., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The effects of the independent and combined addition strategies of sepiolite and palygorskite on humification and heavy metals (HMs) during chicken manure composting were evaluated. Results showed that clay mineral addition showed a favorable effect on composting, prolonged the duration of the thermophilic phase (5-9 d) and improved the TN content (14%-38%) compared to CK. Independent strategy enhanced the humification degree in equal measures with the combined strategy. Carbon nuclear magnetic resonance spectroscopy ( 13 C NMR) and fourier transform infrared spectroscopy (FTIR) confirmed that aromatic carbon species increased by 31%-33% during composting process. Excitation-emission matrix (EEM) fluorescence spectroscopy showed that humic acid-like compounds increased by 12%-15%. In addition, the maximum passivation rate of Cr, Mn, Cu, Zn, As, Cd, Pb and Ni were 51.35%, 35.98%, 30.39%, 32.46%, -87.02%, 36.61% and 27.62%, respectively. The independent addition of palygorskite exhibits the most potent effects for most HMs. Pearson correlation analysis indicated that pH and aromatic carbon were the key determinants of the HMs passivation. This study provided preliminary evidence and perspective of the application of clay minerals on the humification and safety of composting., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The photochemical behavior of dissolved organic matter (DOM) in surface water and its effect on Hg(II) photoreduction has been extensively studied, but the contribution of DOM in paddy water to Hg(II) photoreduction is largely unknown. Herein, the effect of DOM from biochar (BC DOM ), rice straw (RS DOM ), and chicken manure (CM DOM ) on Hg(II) photoreduction were examined. The comparable reduction efficiency of Hg(II) suggested that DOM-like fraction (62.3-63.7%) contributes more than suspended particulate matter-like fraction (17.7-23.4%) and bacteria-like fraction (13.0-20.0%) in paddy water. Under irradiation, the typical DOM significantly promoted Hg(II) photoreduction, and the reduction efficiency of BC DOM (65.5 ± 2.1%) was higher than that of CM DOM (48.3 ± 2.6%) and RS DOM (32.8 ± 2.4%) in 6 h. The quenching and kinetics experiments showed that superoxide anion (O 2 •- ) was the main reactive species for Hg(II) photoreduction. Fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry revealed that DOM with a higher degree of lignin/carboxy-rich acyclic molecules, condensed aromatics structures, and phenolic compounds could promote the formation of O 2 •- . These findings highlight the importance of DOM in Hg(II) photoreduction and provide new ideas for regulating Hg cycling and bioavailability in paddy environments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Bioavailability is recognized as a useful technical standard for risk assessment and pollution rehabilitation. However, knowledge on the bioavailability of polycyclic aromatic hydrocarbons (PAHs) in contaminated site soils is still limited, especially concerning the influential mechanism. With an abundance of soil collections from nine industrial areas in China, the bioavailabilities, as conceptually defined as bioconcentration factors (BCFs) of PAHs were analyzed using biomimetic extraction of hydroxypropyl-β-cyclodextrin (HPCD). Apart from the total content of PAHs varying with the different pyrogenic sources, the BCFs were greatly dependent on the soil physicochemical properties from the spatial scale and inversely proportional to the number of rings. Pearson correlation analysis indicated a weak relationship between bioavailability and the soil dissolved organic matter (DOM), pH and particle size. To incorporate the soil physicochemical properties and structural characteristics of PAHs determined by density functional theory (DFT), the optimum model for bioavailability was developed for BCFs by partial least square (PLS) analysis. The PLS-derived model was shown to be predictive within the applicability domain (AD). The structural characteristics, e.g., molecular polarizability and frontier orbital energy level that favor the soil adsorption of PAH isomers via dispersion interactions, and electron exchanges were indicated to be more impactful on bioavailability than soil environmental factors. However, soil factors should not be neglected, because the pH, DOM, etc. were significantly influential. It makes sense that the higher DOM causes greater bioavailability via increasing the free-dissolved fractions of PAHs. Interestingly, the effect of pH on bioavailability was spectrally validated by excitation-emission matrix (EEM) fluorescence, showing that the interaction between DOM and pyrene strengthened the fluorescence quenching of chromophores with the decline in pH., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Amino antioxidants (AAOs), a suite of emerging organic contaminants, have been widely used in numerous industrial and commercial products to inhibit oxidation and corrosion. Recently, their environmental ubiquity, health risks, bioaccumulative and toxic potential have led to mounting public concern. This review summarizes the current state of knowledge on the production and usage, environmental occurrence, bioavailability, human exposure, and aquatic toxicity of representative AAOs, and provides suggestions for future research directions. Previous studies have revealed widespread distribution of many AAOs in various environmental matrixes, including air, water, sediment, dust, and biota. In addition to parent compounds, their degradation products, such as 2-anilino-5-(1,3-dimethylbutylamino)-1,4-benzoquinone (6PPD-Q) and 4-nitrodiphenylamine (4-NO 2 -DPA), have also been detected at high levels in multiple compartments. Dust ingestion and air inhalation are the two most well-investigated routes for human exposure to AAOs and their transformation products, while studies on other pathways (e.g., skin contact and dietary intake) still remain extremely limited. Moreover, AAO burdens in human tissue have been poorly documented. Toxicological data have shown that a few AAOs may cause teratogenic, developmental, reproductive, endocrinic, neuronic, and genetic toxicity to aquatic organisms, and the toxic capacities of degradation products differ from their precursors. Future studies should focus on elucidating AAO exposure for humans and associated health risks. Additionally, more attention should be given to AAO transformation products (particularly those quinoid derivatives possessing substantial affinity with DNA) and to the effects of complex mixtures of these chemicals., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Virgin microplastics (MPs) would undergo aging process when entering environment, the adsorption capability of pollutants onto MPs may change during the aging process. To better understand the influence of aged polyethylene microplastics (PE-MP) on the bioavailability of three heavy metals (Zn, Pb, and Cd) in soil, hydrogen peroxide exposure (3% H 2 O 2 ) and ultraviolet irradiation methods were employed to simulate the aging process. After aging process, different amount (0.1%, 1%, 10%) of PE-MP (pristine or aged) was added into soil to assess the ability of soil (containing PE-MP) adsorbing heavy metal. Moreover, different amount (0.01%, 0.1%, 1%) of PE-MP (pristine or aged) was added into soil to cultivate the earthworms to assess the impact of PE-MP on bioavailability of three heavy metals. Results indicated that the aged and virgin PE-MP had similar capability to adsorb heavy metal, the adsorption ability of Zn 2+ , Pb 2+ , and Cd 2+ to pristine PE-MP were 2.42, 7.47, and 7.76 mg/g, respectively. The concentration of Zn or Pb in earthworms in treatments of metal +1% PE-MP was slightly higher than that in single metal (Zn or Pb) treatment, moreover, the concentration of Cd in earthworms in treatment of Cd + 1% PE-MP was significantly (p < 0.05) higher than that in single Cd treatment, exhibiting that 1% of PE-MP enhanced the bioavailability of heavy metals in soil. However, heavy metal concentrations in earthworms in treatments of metal + pristine PE-MP showed insignificant (p > 0.05) difference with those in treatments of metal + aged PE-MP, indicating that the aging process in this study did not change the environmental influence of PE-MP on heavy metals bioavailability. Superoxide dismutase activity, reactive oxygen species level, malondialdehyde content, and related gene expression in earthworms showed that PE-MP and heavy metals would bring toxic synergy to earthworms, therefore, the influence of MPs should be comprehensively considered when determining the environmental risk of heavy metals in soil., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier Ltd.)