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Microplastics emerge as a new environmental and human health crisis. Minimal research exists on effects of microplastic ingestion on the oral bioavailability of minerals (Fe, Ca, Cu, Zn, Mn, and Mg) in the gastrointestinal tract via impacting intestinal permeability, mineral transcellular transporters, and gut metabolites. Here, mice were exposed to polyethylene spheres of 30 and 200 μm (PE-30 and PE-200) in diet (2, 20, and 200 μg PE g -1 ) for 35 d to determine the microplastic effects on mineral oral bioavailability. Results showed that for mice fed diet amended with PE-30 and PE-200 at 2-200 μg g -1 , Ca, Cu, Zn, Mn, and Mg concentrations in the small intestine tissue were 43.3-68.8 %, 28.6-52.4 %, 19.3-27.1 %, 12.9-29.9 %, and 10.2-22.4 % lower compared to control mice, suggesting hampered bioavailability of these minerals. In addition, Ca and Mg concentrations in mouse femur were 10.6 % and 11.0 % lower with PE-200 at 200 μg g -1 . In contrast, Fe bioavailability was elevated, as suggested by significantly (p < 0.05) higher Fe concentration in the intestine tissue of mice exposed to PE-200 than control mice (157-180 vs. 115 ± 7.58 μg Fe g -1 ) and significantly (p < 0.05) higher Fe concentrations in liver and kidney with PE-30 and PE-200 at 200 μg g -1 . Following PE-200 exposure at 200 μg g -1 , genes coding for duodenal expression of tight junction proteins (e.g., claudin 4, occludin, zona occludins 1, and cingulin) were significantly up-regulated, possibility weakening intestinal permeability to Ca, Cu, Zn, Mn, and Mg ions. The elevated Fe bioavailability was possibly related to microplastic-induced greater abundances of small peptides in the intestinal tract, which inhibited Fe precipitation and elevated Fe solubility. Results showed that microplastic ingestion may cause Ca, Cu, Zn, Mn, and Mg deficiency but Fe overload via altering intestinal permeability and gut metabolites, posing a threat to human nutrition 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 © 2023 Elsevier B.V. All rights reserved.)

Biochar is a cost-effective and multifunctional carbon material, which can be used to immobilize heavy metal (HM) in soil. To date, the immobilization of different HM by various biochars are well-studied, however, little is known about the release condition of the immobilized HM. As the released HM may bring a threat to the soil environment, it is critical to understand the release pattern of biochar-sorbed HM in soil. Herein, six wheat straw-derived biochars (WBs) pyrolyzed under different temperature and duration time were loaded with zinc(Zn (II)), and the evolution of Zn(II) fractions in soils remediated by WBs over time was investigated by Community Bureau of Reference (BCR) three-step sequential extraction method. The main Zn(II) species sorbed on WBs were the Zn(II) sorbed on the acidic functional groups of WB and that sorbed on WB surface via electrostatic interaction. Generally, Zn(II) sorbed on high-temperature WB was more mobile than that sorbed on low-temperature WB. In the red soil, the soluble and exchangeable Zn(II) (i.e., Zn(II) in Fraction 1) in WB was inclined to transform to organic matter associated-Zn(II) (i.e., Zn(II) in Fraction 3) and residual Zn(II) (i.e., Zn(II) in Fraction 4). In the yellow-brown soil, the soluble and exchangeable Zn(II) in WB was prone to convert into amorphous Fe/Mn oxide associated-Zn(II) (i.e., Zn(II) in Fraction 2) and residual Zn(II). These results imply that Zn(II) sorbed by WB has the risk to be released into the soil environment, and WB produced at low temperature are more suitable to remediate soils with low/neutral pH., Competing Interests: Declaration of competing interest The authors declare that there is no any actual or potential conflict of interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The abnormally high activity of the proteasome system is closely related to the occurrence and development of various tumors. PSMB4 is a non-catalytic subunit for the proteasome assembly. Although the reports from genetic screening have demonstrated it's a driver gene for cell growth in several types of solid tumor, its expression pattern and regulatory mechanisms in malignant diseases are still elusive. Here, we found that PSMB4 is overexpressed in cervical cancer tissues. And knockdown of PSMB4 significantly inhibited cervical cancer cell proliferation. The mechanistic study revealed that FoxM1, a master regulator of cell division, binds directly to the promoter region of PSMB4 and regulates the PSMB4 expression in the mRNA level. In addition, the data analysis from TCGA showed a positive correlation between FxoM1 and PSMB4 in cervical cancer. Furthermore, the loss of functional and rescue experiments confirmed that PSMB4 is required for FoxM1-driven cervical cancer cell proliferation. Collectively, our study explains the phenomenon of dysregulated expression of PSMB4 in cervical cancer tissues and verifies its driver effect on cancer cell proliferation. More importantly, it highlights a FoxM1-PSMB4 axis could be a potential target for the treatment of cervical cancer., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Metal contamination in mining areas, where mining and farming coexist, is of great concern worldwide. Nevertheless, a disconnection exists between those risks to environmental and human health. In this study, an integrated approach was used to connect the environmental and human health risks from metal exposures nearby a Pb-Zn-Ag mine. The field survey showed metal contamination in soils and crop plants as well as variation in soil microbial community in mining region relative to the reference site. Together with non-carcinogenic and carcinogenic risk assessment with a probabilistic approach, Cd and Cr were identified as the priority contaminants. Further, consumption of contaminated food crops was a significant pathway of human exposure. Especially, children were susceptible to metal contamination with non-carcinogenic hazard index (0.45 for soil ingestion and 1.19 for dietary intake) and carcinogenic risk index (3.47 × 10 -4 for soil ingestion and 5.10 × 10 -3 for dietary intake) at the 50th percentile. These findings facilitate the priority actions on mitigation strategies to minimize the environmental and health risks. Also, the potential environmental and human health consequences due to uncontrolled mining in this region serve as a case study for other regions involved in mining activities., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Silver, either in ionic or nanoparticulate form, is widely used in consumer products. However, silver sulfide (Ag 2 S) are more likely to be the form that Ag enters the environment. The retention of silver sulfide nanoparticles (Ag 2 S-NPs) in natural soils is critical for bioavailability and toxicity but remains unclear. Here, we examined the retention of Ag 2 S-NPs in 11 natural soils with varying properties using batch assays. More than 99% of Ag 2 S-NPs were retained in soil solids, irrespective of soil properties. Such high retention of Ag 2 S-NPs, at least partially, explained the distinct differences in phytoavailability performed in soil vs. liquid media in the literature. Nanoparticles containing Ag and S were identified in representative soil solids by high resolution transmission electron microscopy equipped with an energy dispersive X-ray spectrometer. Iron-rich acidic soil had a high dissolution of Ag 2 S-NPs ranging from 47.1% to 61.7% in porewater. In contrast to Ag 2 S-NPs, silver nanoparticles (AgNPs) and Ag + in these soils were less retained (as described by Freundlich model) and the retention was closely associated with soil properties. These findings highlight the unique behaviors of Ag 2 S-NPs in natural soils., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Regorafenib has been approved to treat patients who have HCC progression after sorafenib failure, however, regorafenib also faces the risk of drug resistance and subsequent progression of HCC patients. As LSD1 inhibitors can alleviate acquired resistance to sorafenib, in this context, we are interested to investigate the role of LSD1 in regorafenib treatment. Firstly, over-expressed LSD1 was observed in HCC patients and predicted poor prognosis. However, regorafenib failed to suppress the expression of LSD1 in HCC cells. Thus, we hypothesized that LSD1 inhibition could enhance the anti-HCC activity of regorafenib. As expected, LSD1 knockdown could enhance anti-proliferation effect of regorafenib in HCC cells. LSD1 inhibitor SP2509 could enhance the cytotoxic and apoptotic effects of regorafenib in HCC cells. In addition, clinically used LSD1 inhibitor tranylcypromine also enhanced anti-HCC effect of regorafenib. Furthermore, LSD1 suppressed by SP2590 or tranylcypromine could alleviate the activated p-AKT (ser473) induced by regorafenib in HCC cells. Thus, inhibiting LSD1 might be an attractive target for regorafenib sensitization and clinical HCC therapy, our findings could help to elucidate more effective therapeutic options for HCC patients., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The immobilization behaviors of Zn(II) and Cd(II) by wheat straw (WS) biochars could vary with the soil conditions. In the acidic environment, WS biochars produced at low temperature were more competent than those produced at high temperature on Zn(II) and Cd(II) immobilization; while WS biochars produced at high temperature were more effective than those produced at low temperature in the alkaline environment. The ions in the porewater could compromise the sorption capacities of Zn(II) and Cd(II) by WS biochars in acidic soils, while could enhance them in alkaline soils. For biochars produced at the same temperature, residence time had little effect on their behaviors of Zn(II) and Cd(II) immobilization. Only a small portion of immobilized Zn(II)/Cd(II) could be released from WS biochar in the simulated acid rain. Compared with Zn(II)/Cd(II) adsorbed on the acidic functional groups, Zn(II)/Cd(II) precipitates were more stable in 0.01 M CaCl 2 solution. Most of the Zn(II) and Cd(II) species on biochar could be released in 1 mM citric acid solution. The immobilized Zn(II) and Cd(II) on WS biochar are likely to be released into the soil environment in the long run., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Microbial degradation is considered the most promising method for removing phthalate acid esters (PAEs) from polluted environments; however, a comprehensive genomic understanding of the entire PAE catabolic process is still lacking. In this study, the repertoire of PAE catabolism genes in the metabolically versatile bacterium Rhodococcus sp. 2G was examined using genomic, metabolic, and bioinformatic analyses. A total of 4930 coding genes were identified from the 5.6 Mb genome of the 2G strain, including 337 esterase/hydrolase genes and 48 transferase and decarboxylase genes that were involved in hydrolysing PAEs into phthalate acid (PA) and decarboxylating PA into benzoic acid (BA). One gene cluster (xyl) responsible for transforming BA into catechol and two catechol-catabolism gene clusters controlling the ortho (cat) and meta (xyl &mhp) cleavage pathways were also identified. The proposed PAE catabolism pathway and some key degradation genes were validated by intermediate-utilising tests and real-time quantitative polymerase chain reaction. Our results provide novel insight into the mechanisms of PAE biodegradation at the molecular level and useful information on gene resources for future studies., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The cultivation of crop cultivars with low pollutant accumulation is an important strategy to reduce the potential health risks of food produced from polluted soils. In this study, we identified three loose-leaf lettuce cultivars with low accumulation of perfluorooctanoic acid (PFOA), a highly toxic and persistent organic pollutant. PFOA concentrations in the shoots of low-PFOA cultivars were 3.7-5.5-fold lower than those of high-PFOA cultivars. The identification of low-PFOA cultivars could contribute to ensuring food safety despite cultivation in highly polluted soils (1 mg/kg) based on the tolerable daily PFOA intake (1.5 μg/kg/d). We detected lower desorbing fractions of PFOA in rhizosphere soil, lower bioconcentration factors, and higher distribution in the cell walls and organelles of roots in low-PFOA cultivars, all of which are key factors in limiting PFOA uptake and translocation from soil to shoots, than in high-PFOA cultivars. This study reveals the mechanism of PFOA uptake from soil to crop and lays a foundation for establishing a cost-effective strategy to plant crops in polluted soil and reduce exposure risk due to persistent organic pollutants in crops., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Aniline aerofloat (AAF), a high-toxic organic flotation reagent, is widely used in mineral processing industry. However, little information on its environmental fate is available. AAF sorption to four types of agricultural soils at low concentrations (1-10 mg/L) was investigated using batch experiments. AAF sorption kinetics involved both boundary layer diffusion and intraparticle diffusion, following pseudo-second-order kinetics with equilibrium time within 120 min. Both Langmuir and Freundlich models fitted well the AAF sorption with the former better. Sorption of AAF to soils was a spontaneous and favorable physical sorption that was controlled by ion bridge effect and hydrophobic interaction that was related to van der Waals force and π-π coordination based on FTIR analyses. AAF sorption was remarkably affected by soil constituents, positively correlating with the contents of organic matter and clay. The relatively higher logK oc values (3.53-4.66) of AAF at environmental concentrations (1-5 mg/L) imply that soils are serving as a sink of AAF from beneficiation wastewater, posing great potential risks to environment and human health., (Copyright © 2018 Elsevier Inc. All rights reserved.)

To investigate the mechanism of genotype differences in ciprofloxacin (CIP) accumulation, this study was designed to compare the tolerance and metabolic responses to CIP exposure between low (Cutai) and high (Sijiu) CIP-accumulation cultivars of Brassica parachinensis. Decreases in biomass and chlorophyll content were significantly greater (p < 0.05) and toxicities were more severe within cell ultrastructures of Cutai compared to Sijiu. A sequential growth test also revealed that Sijiu was more tolerant to CIP stress compared to Cutai. Meanwhile, significantly higher (p < 0.05) root parameters and higher areas of the stele and xylem may be responsible for the increased uptake and transport of CIP in Sijiu. Ultra performance liquid chromatography-electrospray ionization tandem mass spectrometry (UPLC-ESI-MS/MS) analysis revealed that CIP was metabolized to three major metabolites by the hydroxylation and breakdown of the piperazinyl substituent in the CIP molecule. The enhanced metabolic transformation of CIP in Sijiu indicated a more efficient capacity to detoxify, which in turn favored an increased accumulation of CIP in this cultivar. Thus, the present study demonstrated that the stronger tolerance and metabolism of Sijiu to CIP were responsible for its high CIP accumulation, suggesting an evolutionary mechanism for adaptation to environmental stress., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Zn deficiency is a critical problem for many crops and human populations worldwide. Soil biochar amendment has recently been promoted as a sustainable agricultural practice. However, its effect on the bioavailability of micronutrients (especially Zn) to crops has not been fully addressed. This study investigated the impact of long-term biochar application in soils on Zn bioavailability to rice and wheat, using field experiments, and batch sorption/desorption experiments, in combination with extended X-ray absorption fine structure spectroscopy (EXAFS). In field soils biochar amendment increased total Zn content, but significantly decreased CaCl 2 -extractable Zn concentrations. Intriguingly, the uptake of Zn to wheat and rice grains was decreased. At high biochar application rates of 124 and 270t/ha the Zn concentrations in wheat grains (36.6 and 37.5mg/kg) reached a deficient level, lower than the recommended concentration of 45mg/kg. The batch experiments showed that biochar application at a cumulative rate of 10.5, 15.8, 31.5, 124, and 270t/ha significantly increased soil pH and soil organic matter (SOM) content, resulting in greater sorption and lower desorption of Zn. The EXAFS results demonstrated that the main forms of sorbed Zn were outer-sphere Zn complexes, Zn-illite, Zn-kaolinite and Zn-OM. The proportion of Zn-OM increased with increasing biochar application rates, suggesting that higher SOM might be more effective in immobilizing Zn and thus decreasing the Zn bioavailability. These results on the microscopic and macroscopic scales improved our understanding of the Zn bioavailability to crops, and raised potential concerns on the Zn deficiency in agricultural soils with long-term biochar application., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Phthalic acid esters (PAEs) are a group of recalcitrant and hazardous organic compounds that pose a great threat to both ecosystem and human beings. A novel endophytic strain YJB3 that could utilize a wide range of PAEs as the sole carbon and energy sources for cell growth was isolated from Canna indica root tissue. It was identified as Bacillus megaterium based on morphological characteristics and 16S rDNA sequence homology analysis. The degradation capability of the strain YJB3 was investigated by incubation in mineral salt medium containing di-n-butyl-phthalate (DBP), one of important PAEs under different environmental conditions, showing 82.5% of the DBP removal in 5days of incubation under the optimum conditions (acetate 1.2g·L -1 , inocula 1.8%, and temperature 34.2°C) achieved by two-step sequential optimization technologies. The DBP metabolites including mono-butyl phthalate (MBP), phthalic acid (PA), protocatechuic acid (PCA), etc. were determined by GC-MS. The PCA catabolic genes responsible for the aromatic ring cleavage of PCA in the strain YJB3 were excavated by whole-genome sequencing. Thus, a degradation pathway of DBP by the strain YJB3 was proposed that MBP was formed, followed by PA, and then the intermediates were further utilized till complete degradation. To our knowledge, this is the first study to show the biodegradation of PAEs using endophyte. The results in the present study suggest that the strain YJB3 is greatly promising to act as a competent inoculum in removal of PAEs in both soils and crops., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Roxarsone (ROX) is transformed to more toxic arsenicals after land application of ROX-containing poultry litter to agricultural soils. To date, no reports have compared ROX degradation in soils with contrasting properties. In this study, the impact of different incubation conditions on ROX degradation was investigated in red (C-Soil) and yellow-brown (H-Soil) soils. The degradation half-lives of extractable ROX in C-Soil and H-Soil were found to be 130-394d and 4-94d, respectively, indicating that the extractable ROX degraded faster in H-Soil. This result stems from the higher organic matter content, more abundant soil microbes, and lower ROX sorption capacity of H-Soil compared to C-Soil. Degradation of extractable ROX in both C-Soil and H-Soil was significantly promoted by soil moisture and exogenous glucose. Exogenous P(V) facilitated degradation of extractable ROX in C-Soil, but limited effects were observed for H-Soil. HPLC-ICP-MS analysis confirmed that ROX and dimethylarsinic acid were the predominant As species in soil extracts from 119-day incubated C-Soil and H-Soil, respectively. Ultimately, minimal transformation of extractable ROX was observed in C-Soil, but the majority of extractable ROX in H-Soil was biologically transformed. The differences in degradation of extractable ROX in C-Soil and H-Soil highlight the key roles of soil properties on the environmental fate of ROX and associated arsenicals. Results from this study inform the need for comprehensive evaluation of the ecological risks in organoarsenical-contaminated soils., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Rhinovirus C (RV-C), a newly identified group of human rhinoviruses (RVs), is associated with exacerbation of severe asthma. The type I interferon (IFN) response induced by this virus and the mechanisms of evasion of IFN-mediated innate immunity for RV-C remain unclear. In this study, we constructed a full-length cDNA clone of RV-C (LZ651) from a clinical sample. IFN-β mRNA and protein levels were not elevated in differentiated Human bronchial epithelial (HBE) cells at the air-liquid interface infected with RV-C, except in the early stage of infection. The ability to attenuate IFN-β activation was ascribed to 3C pro of RV-C, and the 40-His site of 3C pro played an important role. Furthermore, RIG-I was degraded by 3C pro in a caspase-dependent manner and 3C pro cleaved MAVS at 148 Q/A, which inhibited IFN signaling. Taken together, our results demonstrate the mechanism by which RV-C circumvents the production of type I IFN in infected cells., (Copyright © 2017. Published by Elsevier Inc.)

A knowledge gap concerning the potential effects of extracellular polymeric substances (EPS), a common organic material but highly variable in their composition of microbial origin, on the fate and phytotoxicity of silver nanoparticles (AgNP) still remains. A 48-h root elongation toxicity test showed that AgNP toxicity to wheat Triticum aestivum L. was dramatically alleviated by EPS isolated from Pseudomonas putida, as revealed by 7-59% increase in relative root elongation (RRE), 8-99% increase in root weight, 27-32% decrease in malondialdehyde (MDA) content and 11-43% decrease in H2O2 content compared to the treatment with AgNP in the absence of EPS. This was coincident with 7-69% decrease in root Ag concentrations. Our results showed that EPS could protect wheat seedlings from AgNP toxicity by reducing dissolved Ag concentration ([Ag]diss) and by forming AgNP-EPS complex. The FTIR spectra further showed that the amide, carboxyl, and phosphoryl functional groups of EPS were involved in binding with AgNP and/or Ag(+). All these processes worked simultaneously to reduce AgNP bioavailability, and subsequently mitigate AgNP toxicity. These findings highlight the importance of EPS in AgNP biogeochemistry in the terrestrial environment. EPS could be highly useful in developing strategies to counteract the phytotoxicty of metal-based nanoparticles in crops., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Understanding the fate and transport of graphene oxide nanoparticles (GONPs) in the subsurface environments is of crucial importance since they may pose potential risks to the environment and human health. However, little is known about the significance of biofilm on mobility of GONPs in the subsurface. Here we investigated the transport of GONPs in saturated sand coated with Bacillus subtilis (Gram-positive) and Pseudomonas putida (Gram-negative) biofilms, and their secreted extracellular polymeric substances (EPS) under environmentally relevant ionic strengths (1-50mM NaCl) at pH 7.2. Our results showed that irrespective of bacteria type, greater retention of GONPs occurred in biofilm-coated sand compared to clean sand, likely attributed to the increased surface roughness and physical straining. However, EPS showed negligible influence on GONPs transport, which was inconsistent with the findings in the presence of biofilms, while they exhibited comparable ζ-potentials. The different retention phenotype of GONPs in the presence of EPS was induced by hydration effect and steric repulsion. A two-site kinetic retention model well-described the transport of GONPs in porous media covered with different surface coatings, which proves the applicability of mathematical model in predicting nanoparticles' mobility in the subsurface environments, when considering the potential effects of biofilm and EPS., (Copyright © 2015 Elsevier B.V. All rights reserved.)

The geochemical behavior and speciation of arsenic (As) in paddy soils is strongly controlled by soil redox conditions and the sequestration by soil iron oxyhydroxides. Hence, the effects of iron oxide reductive dissolution on the adsorption, transformation and precipitation of As(III) and As(V) in soils were investigated using batch experiments and synchrotron based techniques to gain a deeper understanding at both macroscopic and microscopic scales. The results of batch sorption experiments revealed that the sorption capacity of As(V) on anoxic soil was much higher than that on control soil. Synchrotron based X-ray fluorescence (μ-XRF) mapping studies indicated that As was heterogeneously distributed and was mainly associated with iron in the soil. X-ray absorption near edge structure (XANES), micro-X-ray absorption near edge structure (μ-XANES) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the primary speciation of As in the soil is As(V). These results further suggested that, when As(V) was introduced into the anoxic soil, the rapid coprecipitation of As(V) with ferric/ferrous ion prevented its reduction to As(III), and was the main mechanism controlling the immobilization of As. This research could improve the current understanding of soil As chemistry in paddy and wetland soils., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Increasing attention has been paid to magnetite nanoparticles (MNPs) due to their highly reductive reactivity toward environmental contaminants. However, there is little information related to the generation of reactive oxygen species (ROS) by MNPs, which in fact plays a vital role for the transformation of contaminants. In this paper, the degradation of 2-chlorobiphenyl (2-CB) by MNPs was investigated. The role of ROS generated by MNPs in this process was elucidated. The results demonstrated that hydroxyl radicals (OH) generated by MNPs at low pH could efficiently degrade 2-CB. The mechanism of the formation of OH by MNPs was divided into two steps: (i) the superoxide radical anion (O2(-)) mediated production of hydrogen peroxide (H2O2), and (ii) the reaction of formed H2O2 with Fe(II) dissolved from MNPs to produce OH through Fenton reaction. Comparison of the degradation products of 2-CB by MNPs with MNPs/ethanol and Fenton reagents further supported the involvement of OH in the degradation of 2-CB. The degradation efficiency of 2-CB by MNPs under acidic conditions was higher than that in alkaline solution. These findings provide a new insight into the understanding of reactivity of MNPs for the transformation of 2-CB and possibly other relevant environmental contaminants., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Advanced oxidation processes (AOPs) based on sulfate radical (SO(4)(·-)) have been recently used for soil and groundwater remediation. The presence of chloride ion in natural or wastewater decreases the reactivity of sulfate radical system, but explanations for this behavior were inconsistent, and the mechanisms are poorly understood. Therefore, in this paper we investigated the effect of chloride ion on the degradation of 2,4,4'-CB (PCB28) and biphenyl (BP) by persulfate, based on the produced SO(4)(·-). The results showed that the presence of chloride ion greatly inhibited the transformation of PCB28 and BP. Transformation intermediates of BP were monitored, suggesting that the chloride ion can react with SO(4)(·-) to produce chlorine radical, which reacts with BP to generate chlorinated compounds. To better understand the underlying mechanisms of these processes, a kinetic model was developed for predicting the effect of chloride ion on the types of radical species and their distributions. The results showed that chloride ion could influence the selectivity of radical species and their distribution, and increase the concentration of the sum of radical species. In addition, the second-order rate constants of sulfate radical with PCBs were determined, and quantum-chemical descriptors were introduced to predict the rate constants of other PCBs based on our experimental data., (Copyright © 2012 Elsevier B.V. All rights reserved.)

The accumulation and elimination kinetics for Cd described by one-compartment model were determined in five subcellular fractions of wheat after exposure to 5.0 μM Cd with or without pre-exposure to 0.1 μM Cd or 5.0 μM Zn. The results show that the acclimation of wheat to Cd or Zn generates its resistance to Cd and decreased Cd accumulation in wheat. The acclimation of wheat to Cd or Zn enhanced the accumulation of Cd in the biological detoxified fractions especially the heat-stable fraction and decreased the accumulation of Cd in the metal sensitive fractions especially the heat-denatured proteins over time. Subsequently, the acclimation to Cd or Zn increased the activities of CAT and SOD in root and shoot to different extents compared to the unacclimated wheat. This study for the first time suggests that the acclimation of plant to low-level metal affects the accumulation and the toxicity of metal in plant., (Copyright © 2012 Elsevier Inc. All rights reserved.)

Relative metal-ligand complex stability is predicted by evaluating the relationships between physicochemical properties of metal ions and their experimental biotic and abiotic binding constants, K. Linear regression analysis showed that the softness index (σ(p)) and the covalent index (χ(2)(m) r) were especially useful in model construction for rainbow trout (Oncorhynchus mykiss), fathead minnows (Pimephales promelas) and crustaceansaquatic (Daphnia magna) based on RMSE and F-ratio criterion (F(observed)/F(critical) of ≥4). The absolute value of the log of the first hydrolysis constant |logK(OH)| correlated best with logK values for barley (R(2)=0.74, p=0.02) and earthworm (R(2)=0.82, p=0.01). In contrast, the ionic index Z(2)/r explained most of the variability of logK values for the two clays kaolinite and montmorillonite, while |logK(OH)| was a better predictor of the generic NICA-Donnan parameters for HA and FA (0.67

Phytoremediation is an emerging technology for the remediation of polycyclic aromatic hydrocarbons (PAHs). In this study, pot experiments were conducted to evaluate the efficacy of phytoremediation of phenanthrene and pyrene in a typical low organic matter soil (3.75 g kg(-1)), and the contribution proportions of abiotic losses, microbes, plant roots, and root exudates were ascertained during the PAHs dissipation. The results indicated that contribution of abiotic losses from this soil was high both for phenanthrene (83.4%) and pyrene (57.2%). The contributions of root-exudates-enhanced biodegradation of phenanthrene (15.5%) and pyrene (21.3%) were higher than those of indigenous microbial degradation. The role of root exudates on dissipation of phenanthrene and pyrene was evident in this experiment. By the way, with the increasing of ring numbers in PAHs structures, the root-exudates-enhanced degradation became more and more important. BIOLOG-ECO plate analysis indicated that microbial community structure of the soil receiving root exudates had changed. The removal efficiency and substrate utilization rate in the treatment with plant roots were lower than the treatment only with root exudates, which suggested that possible competition between roots and microbes for nutrients had occurred in a low organic matter soil., (2009. Published by Elsevier B.V.)

Commercial carbon blacks often have low adsorption capacity for metal ions. Surface modification of them by appropriate physical and chemical treatments could improve their absorption capacities, and hence extend their environmental application. A surface-modified nanoscale carbon black was prepared by oxidizing the carbon black with 65% HNO(3). Batch experiments showed that the adsorption quantities of Cu(II) or Cd(II) on this modified carbon black (MCB) were significantly increased compared with those on the parent one, and the maximum adsorption quantities of Cu(II) and Cd(II) on the MCB were 438 and 282 mmol kg(-1), respectively. The desorption percentages of Cu(II) or Cd(II) from the MCB increased with the increasing quantities initially adsorbed. In the binary system of Cu(II) and Cd(II), these two metal ions exhibited competition on the MCB, preferential for Cu(II). It could be concluded that the MCB had very good adsorption properties for the metal ions, and could be applied in the purification of wastewater containing such metal ions.

There is a growing concern on the potential application of a direct current (DC) electric field to soil for removing contaminants, but little is known about its impact on soil enzyme activities. This study investigated the change of enzyme activities of a heavy metal contaminated soil before and after electrokinetic (EK) treatments at lab-scale and the mechanisms of EK treatment to affect soil enzyme activities were explored. After treatments with 1-3 V cm(-1) of voltage gradient for 420 h, soil pH, electrical conductivity (EC), soil organic carbon, dissolved organic carbon (DOC), soil heavy metal concentration and enzyme activities were analyzed. The results showed that the average removal efficiencies of soil copper were about 65% and 83% without and with pH control of catholyte, respectively, and all the removal efficiencies of cadmium were above 90%. The soil invertase and catalase activities increased and the highest invertase activity was as 170 times as the initial one. The activities of soil urease and acidic phosphatase were lower than the initial ones. Bivariate correlation analyses indicated that the soil invertase and acidic phosphatase activities were significantly correlated with soil pH, EC, and DOC at P<0.05, but the soil urease activities had no correlation with the soil properties. On the other hand, the effects of DC electric current on solution invertase and catalase enzyme protein activities indicated that it had negative effect on solution catalase activity and little effect on solution invertase activity. From the change of invertase and catalase activities in soil and solution, the conclusion can be drawn that the dominant effect mechanism is the change of soil properties by EK treatments.

Adsorption kinetics and adsorption isotherms of Cu(II) onto a nanosized hydroxyapatite (HAP) in the absence and presence of different low-molecular-weight organic acids are studied in batch experiments. The results show that the adsorption kinetics of Cu(II) onto the HAP are best described by pseudo-second-order model, and the adsorption isotherms of Cu(II) onto the HAP fit Dubinin-Radushkevich model very well with high correlation coefficient (R(2)=0.97-0.99). The amount adsorbed of Cu(II) onto the HAP at pH 5.5 was much higher than that at pH 4.5. The presence of organic acids significantly decreased the adsorption quantity of Cu(II), clarifying the lower sorption affinities of Cu(II)-organic acid complexes onto the HAP rather than Cu(II) ion. The decreased maximal adsorption quantity of Cu(II) onto the HAP increased with the increasing logarithm of cumulative formation constants of Cu(II) and organic acids. The stronger coordination of organic acid with Cu(II), the more decreased Cu(II) adsorption quantity onto the HAP.

A semi-static solution culture method was used to study the effects of Ca(2+) supply and interaction of Cd-Pb on the subcellular distribution of Cd and Pb in earthworm Eisenia fetida. The subcellular distribution of Cd and Pb was shown to be metal specific. About 80% of the Cd was distributed in the cytosol (fraction G), and only about 20% of total Cd was found in the tissue and cell membrane (fraction E) and the microsomes (fraction F). Nearly 50% of the Pb was rich in the tissue and cell membrane (fraction E). The supply of Ca(2+) ions significantly decreased Cd concentration in the cytosol (fraction G) and the whole tissue of the E. fetida. At the subcellular level, the addition of Pb(2+) ions significantly decreased the Cd percentage associated with fraction G from 83.7% to 58.4% and increased fraction E from 10.7% to 34.0%, respectively.

In this work, chloride, chlorate and perchlorate are fast separated on PDMS microchip and detected via in-channel indirect amperometric detection mode. With PDMS/PDMS microchip treated by oxygen plasma, anions chloride (Cl-), chlorate (ClO3-), and perchlorate (ClO4-) are separated within 35s. Some parameters including buffer salt concentration, buffer pH, separation voltage and detection potential are investigated in detail. The separation conditions using 15 mM (pH 6.12) of 2-(N-morpholino)ethanesulfonic acid (MES)+L-histidine (L-His) as running buffer, -2000 V as separation voltage and 0.7 V as detection potential are optimized. Under this condition, the detection limits of Cl-, ClO3-, and ClO4- are 1.9, 3.6, and 2.8 microM, respectively.

Cosorption of metals with herbicides on minerals affects their mobility and their environmental effect. Batch experiments were conducted to evaluate the interaction between Zn and glyphosate [N-(phosphonomethyl)glycine (GPS; H3L)] with regard to the effect of GPS on Zn adsorption on goethite. The herbicide GPS markedly affected Zn adsorption on goethite when they coexisted in a goethite suspension. When solution pH was not intentionally adjusted, addition of GPS decreased Zn adsorption on goethite, since the equilibrium solution pH was significantly decreased in the presence of GPS and correspondingly the negative surface charges of goethite decreased. Zinc adsorption on goethite in the presence and absence of GPS at different pH of the equilibrium solution was studied in order to know if pH was the only variable for Zn adsorption with coexisting GPS. At lower pH (pH<5), the presence of GPS increased the adsorption of Zn, because Zn adsorbed on the sites of goethite via GPS bridge. However, at higher pH (pH>5), the presence of GPS decreased the adsorption of Zn on goethite, because GPS reacted with solution Zn to form water-soluble complexes that had lower affinity to the goethite surface in comparison with Zn itself. Zeta potential of goethite significantly decreased after adsorption of GPS, suggesting a chemical bond occurred between GPS and the mineral. FTIRs also show that GPS adsorbs on goethite by coordinating through caboxylate group.

Effects of sodium hypochlorite (NaClO), applied as an oxidant in catholyte, and high pH buffer solution on soil Cr removal and the functional diversity of soil microbial community during enhanced electrokinetic treatments of a chromium (Cr) contaminated red soil are evaluated. Using pH control system to maintain high alkalinity of soil together with the use of NaClO increased the electrical conductivities of soil pore liquid and electroosmotic flux compared with the control (Exp-01). The pH control and NaClO improved the removal of Cr(VI) and total Cr from the soil. The highest removal percentages of soil Cr(VI) and total Cr were 96 and 72%, respectively, in Exp-04 when the pH value of the anolyte was controlled at 10 and NaClO was added in the catholyte. The alkaline soil environment and introduction of NaClO in the soil enhanced the desorption of Cr(VI) from the soil and promoted Cr(III) oxidation to mobile Cr(VI), respectively. However, the elevated pH and introduction of NaClO in the soil, which are necessary for improving the removal efficiency of soil Cr, resulted in a significantly adverse impact on the functional diversity of soil microbial community. It suggests that to assess the negative impact of extreme conditions for enhancing the extraction efficiencies of Cr on the soil properties and function is necessary.

In-channel indirect amperometric detection mode for microchip capillary electrophoresis with positive separation electric field is successfully applied to some heavy metal ions. The influences of separation voltage, detection potential, the concentration and pH value of running buffer on the response of the detector have been investigated. An optimized condition of 1200V separation voltage, -0.1V detection potential, 20mM (pH 4.46) running buffer of 2-(N-morpholino)ethanesulfonic acid (MES)+l-histidine (l-His) was selected. The results clearly showed that Pb(2+), Cd(2+), and Cu(2+) were efficiently separated within 80s in a 3.7cm long native separation PDMS/PDMS channel and successfully detected at a single carbon fibre electrode. The theoretical plate numbers of Pb(2+), Cd(2+), and Cu(2+) were 1.2x10(5), 2.5x10(5), and 1.9x10(5)m(-1), respectively. The detection limits for Pb(2+), Cd(2+), and Cu(2+) were 1.3, 3.3 and 7.4muM (S/N=3).

Agricultural application of large amounts of glyphosate [N-(phosphonomethyl)-glycine] may affect soil metal behaviors to some extend, because glyphosate can react with many kinds of metals to form metal complexes. Cosorption of Zn and glyphosate on a Red soil (RS, Udic Ferrosols) and a Wushan soil (WS, Anthrosol) was studied. In comparison with the WS, the RS has less adsorption capacity for Zn and higher for glyphosate. The presence of glyphosate decreased Zn adsorption on the two soils, which are resulted from the decreased equilibrium solution pH caused by the added glyphosate, and also the formation of water-soluble complexes of glyphosate with solution Zn(2+) that had lower affinity to soil surface in comparison with Zn(2+) itself. Such effect is more significant on the RS than on the WS, mainly because of the less adsorption quantity of Zn on the former one. On the contrary, the presence of Zn increased the adsorption quantities of glyphosate on the RS and WS, which is resulted from the decreasing pH value of the equilibrium solution caused by Zn(2+) exchange with H(+) ions of soil surface. Such results suggest that glyphosate in field may increase the mobility and bioavailability of Zn and correspondingly increase its environmental risk.

Solid/solution partition coefficient (Kd) and speciation of soil heavy metals can be used for predicting their environmental risks. The Kd values and solution speciation of soil Cu, Cd and Zn were analyzed in 40 samples of contaminated agricultural soils around Jiuhua copper mine in eastern Nanjing city, China. The Kd ranges (and mean values) for soil Cu, Cd and Zn are 703-7418 (3453), 37.3-3963 (940) and 319-17965 (7244) L kg-1, respectively, showing a large variability both for metals and soils. The results of differential pulse anodic stripping voltammetry (DPASV) indicates that 95.6% solution Cu is bound to dissolved organic ligands. About half of the dissolved Zn is DPASV-labile at pH<6, while 92.1% solution Zn is in the form of organic complexes at pH>6. DPASV-labile Cd is ranged from 22.6 to 98.7% with the mean value of 56.3%. Multiple linear regressions indicate that Kd, the dissolved and DPASV-labile concentrations of Cd and Zn are mostly influenced by the soil solution pH with R2 of 0.50, 0.59 and 0.63, respectively for Cd, and 0.58, 0.72 and 0.64, respectively for Zn. Considering the second parameter of corresponding soil metal, the linear relationships of Kd with pH were improved with R2 of 0.70 and 0.73 for Cd and Zn, respectively. However, the solubility of soil Cu was insensitive to pH. Only SOC shows a weak relationship to the dissolved Cu with R2 of 0.21. As for its Kd, total soil Cu is the most significant factor. But for DPASV-labile Cu, no soil parameters were found to be good predictors.