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Prenatal exposure to polychlorinated biphenyls (PCBs) has been well researched, but studies covering all 209 congeners are limited. Recent literature suggests a shift in the dominant congeners and increasing levels of unintentionally-produced PCBs (UP-PCBs) in environmental samples in China. To investigate the exposure levels and profiles of PCBs in pregnant women and newborns, as well as the characteristics of transplacental transfer, we measured 209 PCBs in 80 pairs of maternal serum (MS) and cord serum (CS) from Hangzhou and Mianyang, China. The levels of ∑PCBs of participants in this study were lower than those in developed countries and followed the order of (ng/g lw): Hangzhou-MS (148) > Hangzhou-CS (107) > Mianyang-MS (63.8) > Mianyang-CS (57.9). UP-PCBs (mainly PCB-11) contributed around 50% of ∑PCBs in serum, which is consistent with the environmental samples. Environmental burden and dietary intake may account for the differences in the exposure levels, while the historical production and release may have impacted the homologue profiles. Prenatal exposure to PCB-126 was associated with increased birth weight (n = 80, adjusted β = 0.270, p = 0.030). The body burden of dioxin-like PCBs of newborns in Hangzhou was 82.4 pg TEQ/kg bw, suggesting certain health risks under WHO tolerable daily intake of 1-4 pg TEQ/kg bw. Log 10 K OW was negatively correlated with log 10 -transformed transplacental transfer efficiency (R 2  = 0.36, p < 0.001), serving its importance for PCBs' transplacental transfer. This study is the first to investigate maternal and fetal exposure to PCBs in China based on their levels, congener and homologue profiles, and potential adverse effects. Our findings help to provide insights into the processes and factors influencing the transplacental transfer of PCBs., 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.)

Contamination of drinking water by carcinogen arsenic (As) is of worldwide concern as its exposure poses potential threat to human health. As such, it is important to understand the mechanisms associated with As-induced toxicity to humans. The Nrf2/Keap1 signal pathway is one of the most important defense mechanisms in cells to counter oxidative stress; however, limited information is available regarding its role in countering As-induced stress in model animal mouse. In this study, we assessed the responses of Nrf2/keap1 pathway in mice after chronic exposure to As at environmentally-relevant concentrations of 10-200 μg L -1 for 30 days via drinking water. Our results indicate that chronic As exposure had limited effect on mouse growth. However, As induced oxidative stress to mice as indicated by increased content of malondialdehyde (MDA; 52-90%), an index of lipid peroxidation. Further, arsenic exposure reduced the activity of superoxide dismutase (SOD; 14-18%), an indication of reduced anti-oxidative activity. Besides, arsenic exposure increased MnSOD mRNA transcription by 25-66%, and decreased the mRNA transcriptions of Cu/ZnSOD by 72-83% and metallothionein by 16-75%, a cysteine-rich protein involved in metal detoxification. To counter arsenic toxicity, the expression of transcription factor for Nrf2 and Keap1 was increased by 2.8-8.9 and 0.2-8.1 fold in mice. To effectively reduce As-induced oxidative stress, the Nrf2/Keap1 transcription factor upregulated several downstream anti-oxidative genes, including heme oxygenase-1 (0.9-2.5 fold), glutamate-cysteine ligase catalytic subunit (0.6-1.7 fold), and NADH quinone dehydrogenase 1 (2.1-4.8 fold). This study shows the importance of Nrf2/Keap1 signaling pathway and associated anti-oxidative enzymes in countering As-toxicity in mice, possibly having implication for human health., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

E-wastes release toxic metals including Cd, Cu, Ni, Pb and Zn into nearby soils during dismantling process. However, their adverse effects and the associated mechanisms on human intestinal epithelium are poorly understood. In this study, their toxic effects on human colonic epithelial cells Caco-2 and the underlying mechanisms were assessed basing on three soils from Wenling e-waste dismantling site. Since soil-extractable metals are more available for gastrointestinal absorption, we used phosphate buffer saline solution to extract metals at solid to liquid ratio of 1:2. Among metals, total Cd and Ni exceeded the risk screening values in three soils, being 3.8-8.8 and 42.4-155 mg/kg. Furthermore, high extractable-metals at 5.9, 1.9, and 0.87 mg/kg Cd (20-67%) and 4.6, 6.4, and 12.4 mg/kg Ni (3.6-29%) were observed for Soil-1, -2 and -3, respectively. All three extracts triggered cytotoxicity, with Soil-2 showing the strongest inhibition of cell viability. Higher production of reactive oxygen species and stronger inhibition of antioxidant enzymes SOD1 and CAT were observed in Soil-2 and -3. Upregulation of proinflammatory mediators (IL-1β, IL-8 and TNF-α) and apoptosis-regulatory genes (GADD45α, Caspase-3, and Caspase-8) were observed. Our data suggest that soil extracts induced cytotoxicity, oxidative damage, inflammatory response, and cell apoptosis in Caco-2 cells, indicating soil ingestion from e-waste dismantling site may adversely impact human health., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

In this study, a two-step functionalizing strategy by combining co-condensation with grafting procedures was employed to synthesize well-ordered Amino- and Thiol-Bifunctionalized SBA-15 (ATBS) mesoporous silica. Its physicochemical properties, performance, and mechanisms in immobilization of toxic metals Pb and Cd in water and soil were investigated. After bi-functionalization, X-ray diffractometer, transmission electron microscope, and N 2 adsorption-desorption measurements confirmed that the ATBS maintained a highly-ordered mesoporous structure, large surface area and pore volume. The elemental analysis, Fourier transform infrared spectroscopy and X-ray Photoelectron Spectroscopy (XPS) evidenced the successful incorporation of amine and thiol groups into ATBS. These structure and functional characteristics of ATBS benefited Pb and Cd sorption. Sorption isotherms of Pb and Cd were better fit with Sips and Redlich-Peterson models. Sorption kinetics suggested that Pb sorption was mainly regulated by chemical reactions, whereas both diffusion process and chemical reactions were rate-regulating steps in Cd sorption. ATBS showed the maximum sorption capacities for Pb and Cd at 120 and 38 mg g -1 , respectively. The sorption mechanisms revealed by XPS measurements suggested that Cd sorption was mainly attributed to thiol groups while Pb was efficiently bond to both thiol and amino groups. High and stable sorption efficiencies were attained in the pH range of 4-6, with a higher affinity towards Pb than Cd. Furthermore, its ability to immobilize Pb and Cd in soils was examined with an incubation experiment, which showed that ATBS reduced 30-56% of MgCl 2 -extractable Pb and Cd in a contaminated soil. The synthesized sorbent via the two-step functionalizing strategy shows high sorption efficiency towards Pb and Cd, and thus it has potential application in remediating Pb and Cd contaminated water and soils., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

To understand how Cd in different fractions contributes to Cd bioaccessibility by in vitro assays, Cd bioaccessibility in 12 contaminated soils was determined by four assays (UBM, SBRC, IVG, and PBET) and correlated with different Cd fractions based on a sequential extraction scheme. The Cd bioaccessibility in the gastric phase (GP) was high (35-107%, averaging at 77%), implicating high risk to human health, while it decreased to 19-88% averaging at 47% in the intestinal phased (IP). From the GP to IP, the reduction of extractable Cd (0.45-48 mg kg -1 ) and Fe (118-3884 mg kg -1 ) showed significant correlation (R = 0.54-0.74) via UBM, SBRC, and IVG, suggesting co-precipitation with Fe and/or sorption onto Fe oxides maybe responsible for decrease in Cd bioaccessibility. Although Cd bioaccessibility varied among assays, their results show some consistency based on their correlation in the GP (R = 0.56-0.90) and IP (0.34-0.73, excluding UBM-IP and PBET-IP). Sequential extraction data show that Cd was primarily associated with the exchangeable fraction (E1; 7.05-72.9%, averaging 39.4%). The carbonate (C2; 6.86-44.8%, 21.9%) and Fe/Mn oxides fraction (F3; 12.5-53.6%, 28.2%) were similar, while organic (O4; 0.62-25.0%, 7.91%) and residual fraction (R5; 0.22-8.54%, 2.62%) were the lowest. Significant correlation (R = 0.59-0.88) between the first two fractions (E1+C2) and bioaccessible Cd suggest they were the main sources of bioaccessible Cd in those contaminated soils., (Copyright © 2021. Published by Elsevier Ltd.)

Seasonal changes in chemical compositions and source apportionment of PM 2.5 during clear and hazy days help to develop effective control policy, but limited information is available in megacity Nanjing. In this study, 102 PM 2.5 samples were collected during clear and hazy days from 4 seasons in 2014-2015. Their chemical compositions (organic and elemental carbon, 8 water-soluble ions, and 22 inorganic elements) were determined, which were used for PM 2.5 source apportionment using the PMF model. The mean PM 2.5 concentration was lower during clear days than hazy days (42 vs. 122 μg m -3 ), so were mean concentrations of metals (0.48 vs. 0.82 ng m -3 for Co and 2.0 vs. 2.4 μg m -3 for Na), water soluble ions (0.10 vs. 0.16 μg m -3 for Mg 2+ and 12 vs. 23 μg m -3 for SO 4 2- ), and carbon species (3.2 vs. 5.4 μg m -3 for elemetal C and 20 vs. 35 μg m -3 for organic C). Based on the PMF model, five main sources of PM 2.5 were identified including secondary aerosols (31%), coal combustion (27%), road & construction dust (26%), oil combustion (8.5%), and iron & steel industry (5.1%) for all samples. The PM 2.5 concentrations from the 5 sources were 0.01-46.5, averaging 9.8 μg m -3 during clear days (PM 2.5  < 75 μg m -3 ), which increased to 1.83-60.1, averaging 18 μg m -3 during hazy days. However, based on their contributions to PM 2.5 , only secondary aerosols increased during hazy days compared to clear days in all seasons (11 vs. 42%), indicating its dominant contribution to haze in Nanjing. For different seasons, road & construction dust was a major contributor to PM 2.5  in the summer, while oil combustion (4.86 vs.16.8%) contributed more in spring. However, coal combustion became the main source of PM 2.5 during the summer (44-85%) due to the pollution controls for the Youth Olympic Games. Our results suggest that secondary aerosols play an important role in haze formation and season-dependent pollution measures should be implemented for effective control of air pollution., Competing Interests: Declaration of competing interest There is no conflict of interest from all authors., (Published by Elsevier Ltd.)

Novel brominated flame retardants (NBFRs) have been widely used and frequently detected in various environmental matrices. In this study, 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB), bis-(2-ethylhexyl) tetrabromophthalate (TBPH) and their metabolites (namely 2,3,4,5-tetra-bromo benzoic acid (TBBA) and mono(2-ethylhexyl) tetrabromophthalate (TBMEHP)) were exposed to human umbilical vein endothelial cells (HUVECs). Metabolites can induce stronger cytotoxicity than parent compounds with EC50 at 47.3 (TBBA), 8.6 μg/ml (TBMEHP) vs > 200 μg/mL for parent compounds. Gene expression of platelet endothelial cell adhesion molecule-1, the gene associated with blood platelet kinetics, was significantly induced under TBBA and TBMEHP exposure. The in vivo test was consistent with gene expression result that the number of platelets in mouse blood was significantly increased after gavaged with 0.8 μg/mL TBBA and TBMEHP. In addition, TBB or TBPH were exposed to mice via gavage, and higher concentrations of TBBA (4 h, 60.8 ± 12.9 ng/mL, 8 h, 69.4 ± 2.24 ng/mL) in mouse blood were found than those of TBMEHP (4 h, 17.2 ± 4.01 ng/mL, 8 h, 12.8 ± 3.20 ng/mL), indicating that TBB was more readily in vivo metabolized than TBPH. The in vivo metabolism of TBB and TBPH and the stronger toxicity of their metabolites underscore the potential risk through NBFR exposure and the importance of understanding NBFR metabolism process., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Soil contamination by heavy metals is widespread. Heavy metals of concern include As, Cd, Cu, Cr, Mn, Ni, Pb, and Zn. Hyperaccumulating plants are efficient in accumulating metals, which have potential to remediate metal-contaminated soils. Species of closely-related hyperaccumulating plants have been used to screen their ability in metal accumulation. However, there is limited evidence to show that closely-related plant species have similar ability in metal accumulation. Using a global database of 664 hyperaccumulating plants, we constructed a phylogeny of hyperaccumulating plants of As, Cd, Cu, Cr, Mn, Ni, Pb, and Zn. We evaluated the phylogenetic randomness of plants hyperaccumulating different metals by comparing the minimum number of trait-state changes across the phylogenetic tree to a null model. Based on the D value, we evaluated whether closely-related plants tend to accumulate similar metals. Based on the Blomberg's K and Pagel's λ, we tested whether closely-related plants have similar ability in metal accumulation. Excluding Cd and Pb, closely-related plant species tend to accumulate similar metal, however, its ability cannot be predicted based on phylogenetic relations except Ni. Therefore, we concluded that focusing on species of closely-related hyperaccumulating plants can help to screen new hyperaccumulators although their ability could be different., Competing Interests: Declaration of competing interest The authors declare no competing financial interests., (Published by Elsevier Ltd.)

Arsenic (As) and cadmium (Cd) are ubiquitous in the environment and they are both toxic to humans. When present in soils, they can enter food chain, thereby threatening human health. Water spinach (Ipomoea aquatica) is an important leafy vegetable, which is widely consumed in Asian countries. However, it is efficient in taking up As and Cd from soils and accumulating them in the edible parts. Therefore, it is of significance to reduce its As and Cd content, especially in contaminated soil. In this study, pot experiments were conducted to investigate the ability of As-hyperaccumulator Pteris vittata in reducing As and Cd uptake by water spinach under different phosphorus treatments. P. vittata was grown for 60 d in a contaminated-soil amended with P fertilizer (+P) or phosphate rock (+PR), followed by water spinach cultivation for another 30 d. Plant biomass, As and Cd contents in plants and soils, and soil pH were analyzed. We found that, P. vittata coupled with PR decreased the As concentration in water spinach shoots by 42%, probably due to As uptake by P. vittata. Moreover, P. vittata decreased the Cd accumulation in water spinach by 24-44%, probably due to pH increase of 0.47-0.61 after P. vittata cultivation. Taking together, the results showed that P. vittata coupled with PR decreased the As and Cd content in water spinach, which is of significance for improving food safety and protecting human health., (Published by Elsevier Ltd.)

Phosphorus (P) is a critical element affecting eutrophication in aquatic ecosystems. Its availability is closely related to calcium (Ca) in calcareous soils and sediments, but their relations are unclear. In this study, the spatial and temporal changes in P and Ca fractionation and distribution in a karst farmland-wetland ecosystem were investigated. The results showed that total P concentrations were 1.25-3.19 g kg -1 , with higher concentrations in paddy soil than in sediment. Total Ca concentrations were 3.93-10.2 g kg -1 , with higher Ca being accumulated in sediments than in soils. The P fractionations varied seasonally, with Ca-bound P being dominant. The moderately-stable Fe/Al-bound P showed temporal variation, while Ca was dominant in acid-soluble fraction, both probably playing an important role in controlling P availability. Correlation analysis showed seasonal relation between Ca and P distribution in soil/sediment. This study suggests that P migration from farmland to wetland may be a major source for P accumulation in sediments in a karst farmland-wetland system., (Published by Elsevier Ltd.)

Arsenate (AsV) reduction in bacteria is essential to alleviate their arsenic (As) toxicity. We isolated a Bacillus strain PVR-YHB1-1 from the roots of As-hyperaccumulator Pteris vittata. The strain was efficient in reducing AsV to arsenite (AsIII), but the associated mechanisms were unclear. Here, we investigated its As resistance and reduction behaviors and associated genes at genome level. Results showed that the strain tolerated up to 20 mM AsV. When grown in 1 mM AsV, 96% AsV was reduced to AsIII in 48 h, with its AsV reduction ability being positively correlated to bacterial biomass. Two ars operons arsRacr3arsCDA and arsRKacr3arsC for As metabolisms were identified based on draft genome sequencing and gene annotations. Our data suggested that both operons might have attributed to efficient As resistance and AsV reduction in PVR-YHB1-1, providing clues to better understand As transformation in bacteria and their roles in As transformation in the environment., (Published by Elsevier Ltd.)

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous organic contaminants, which are found in soils throughout the U.S. The objective of this study was to determine the background concentrations, distributions, and sources of 16 USEPA priority PAHs in two urban soils. A total of 114 soil samples were collected from two large cities in Florida: Orlando and Tampa. The results showed that soils were dominated by high molecular weight PAHs in both cities. The average ∑16-PAHs in Orlando and Tampa soils were 3227 and 4562 μg kg -1 , respectively. The averages of 7 carcinogenic PAHs based on the benzo[a]pyrene-equivalent (BaP-EQ) concentrations in the two cities were 452 and 802 μg kg -1 . BaP-EQ concentrations in 60-62% of samples were higher than the Florida Soil Cleanup Target Level (FSCTL) for residential soils at 100 μg kg -1 and 20-25% of samples were higher than FSCTL for industrial soils at 700 μg kg -1 . Based on molecular diagnostic ratios and PMF modeling, major sources of soil PAHs in both cities were similar, mainly from pyrogenic sources including vehicle emissions, and biomass and coal combustion. Based on ArcGIS mapping, PAH concentrations in soils near business districts and high traffic roads were higher. Thus, it is important to consider background PAH concentrations in urban soils when considering soil remediation., (Published by Elsevier Ltd.)

Cyanobacterial blooms as a global environmental issue are of public health concern. In this study, we investigated the spatial (10 sites) and temporal (June, August and October) variations in: 1) their biomass based on chlorophyll-a (chl-a) concentration, 2) their toxic genotype based on gene copy ratio of mcyJ to cpcBA, and 3) their cpcBA genotype composition of Microcystis during cyanobacterial bloom in Lake Taihu. While spatial-temporal variations were found in chl-a and mcyJ/cpcBA ratio, only spatial variation was observed in cpcBA genotype composition. Samples from northwestern part had a higher chl-a, but mcyJ/cpcBA ratio didn't vary among the sites. High chl-a was observed in August, while mcyJ/cpcBA ratio and genotypic richness increased with time. The spatial variations in chl-a and mcyJ/cpcBA ratio and temporal variation in cpcBA genotype were correlated negatively with dissolved N and positively with dissolved P. Spatial distribution of Microcystis biomass was positively correlated with nitrite and P excluding October, but no correlation was found for spatial distribution of mcyJ/cpcBA ratio and cpcBA genotype. Spatial distribution of toxic and cpcBA genotypes may result from horizontal transport of Microcystis colonies, while spatial variation in Microcystis biomass was probably controlled by both nutrient-mediated growth and horizontal transport of Microcystis. The temporal variation in Microcystis biomass, toxic genotype and cpcBA genotype composition were related to nutrient levels, but cause-and-effect relationships require further study., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The ability of As-hyperaccumulator Pteris vittata to remove As from two contaminated soils (CCA from an As-treated wood facility and DVA from a cattle-dipping vat) over 5 years was investigated for the first time. The goal was to evaluate P. vittata's ability to continuously remove As during 10 harvests and identify how soil As was affected by P. vittata under P-sufficient (P-fertilizer) and P-limiting (phosphate rock) conditions. Sequential extraction was used to determine changes in metal distribution among different soil fractions. The high frond biomass production occurred on the 9th (62.1-63.9 and 35.6-63.5 g plant -1 ) and 10th harvest (58.6-60.7 and 51.9-57.1 g plant -1 ) for CCA and DVB soils, though frond As concentration decreased. Soil arsenic removal averaged 7-10% per harvest during the 1-6th harvests and was reduced to 0-3% during the 7-10th harvests for DVA and CCA soils. Arsenic from all fractions, excluding the residual fraction, was affected by plant uptake. The largest reduction occurred in the amorphous fraction of CCA-soil at 64-66% (61.2-61.5 to 20.8-21.8 mg kg -1 ) and in the crystalline fraction of DVA-soil at 50-86% (2.18-4.35 to 0.61-1.10 mg kg -1 ). Soil As concentrations were reduced by 37-47% from 26.7 to 129 to 15.6-16.8 and 68.9-70.1 mg kg -1 for the DVA and CCA soils, respectively. Our data indicated that P. vittata efficiently solubilized non-labile As under P-limiting conditions without impacting its As depletion., (Published by Elsevier Ltd.)

Heavy metal pollution in aquatic system is of concern due its ecologic risk. In this study, we investigated the distribution, fractionation and plant uptake of heavy metals (As, Cd, Cr, Co, Cu, Ni, Pb and Zn) in a riparian wetland impacted by mining activities in Yunnan, southwest China. The results showed that excluding Cr, metal contents in sediment were higher than the background values, especially for As, which was 100-fold higher. While Cd showed high levels in the acid-soluble fraction with high availability, As, Cr, Cu, Ni and Pb mainly existed in the residual fraction with low availability. Two native aquatic plants including Phragmites australis (common reed) and Typha orientalis (bullrush) showed different uptake ability. T. orientalis accumulated more As, while P. australis accumulated more other metals. Based on geoaccumulation index (I geo ), As, Cd and Zn were more contaminated (I geo > 3), followed by Cu, Pb and Co (I geo <3), with Cr and Ni being slightly polluted (I geo <1). According to risk assessment code, Cd showed high availability, followed by Zn and Co, with As exhibiting the lowest. The data suggested that both total and bioavailable metals should be considered for risk assessment of metal pollution in a wetland., (Published by Elsevier Ltd.)

It is known that arsenic (As) promotes growth of As-hyperaccumulator Pteris vittata (PV), however, the associated mechanisms are unclear. Here we examined As-induced nutrient uptake in P. vittata and their potential role to enhance plant growth in sterile agar by excluding microbial effects. As-hyperaccumulator P. multifida (PM) and non-hyperaccumulator P. ensiformis (PE) belonging to the Pteris genus were used as comparisons. The results showed that, after 40 d of growth, As induced biomass increase in hyperaccumulators PV and PM by 5.2-9.4 fold whereas it caused 63% decline in PE. The data suggested that As played a beneficial role in promoting hyperaccumulator growth. In addition, hyperaccumulators PV and PM accumulated 7.5-13, 1.4-3.6, and 1.8-4.4 fold more As, Fe, and P than the non-hyperaccumulator PE. In addition, nutrient contents such as K and Zn were also increased while Ca, Mg, and Mn decreased or unaffected under As treatment. This study demonstrated that As promoted growth in hyperaccumulators and enhanced Fe, P, K, and Zn uptake. Different plant growth responses to As among hyperaccumulators PV and PM and non-hyperaccumulator PE may help to better understand why hyperaccumulators grow better under As-stress., (Published by Elsevier Ltd.)

Proper disposal of As-hyperaccumulator Pteris vittata biomass (Chinese brake fern) enhances its application in phytoremediation. The goal of this study was to optimize As removal from P. vittata (PV) biomass by testing different particle sizes, extractants, extraction times and solid-to-liquid ratios. PV biomass was extracted using different extractants followed by different Mg-salts to recover soluble As via precipitation. Water-soluble As in PV biomass varied from 6.8% to 61% of total As depending on extraction time, with 99% of As being arsenate (AsV). Extraction with 2.1% HCl, 2.1% H 3 PO 4 , 1 M NaOH and 50% ethanol recovered 81, 78, 47 and 14% of As from PV biomass. A follow-up extraction using HCl recovered 27-32% with ethanol recovering only 5%. Though ethanol showed the lowest extractable As, residual As in the biomass was also the lowest. Among the extractants, 35% ethanol was the best to remove As from PV biomass. Approximately 90% As was removed from PV biomass using particle size <1 mm at solid:liquid ratio 1:50 and pH 6 for 2 h. Adding MgCl 2 at As:Mg ratio of 1:400 with pH 9.5 was effective to precipitate soluble As, resulting in 98% removal. Effective removal of As from PV biomass prior to disposal helps make phytoremediation more feasible., (Published by Elsevier Ltd.)

Cancerous human liver cell line has been used to test the hepatic toxicity of indoor dust, showing its organic extract decreases cell viability. However, little is known about its impact on normal human liver cell line. In the present study, we compared the cellular responses between carcinoma cell line (HepG2) and normal cell line (HL-7702) after exposing to 10-640 μg/100 μL organic dust extract for 24 h. The dust extract caused cytotoxicity, oxidative damage, inflammatory response and loss of mitochondrial transmembrane potential (MMP) in both cells. The inhibition of cell viability in HL-7702 cells was stronger than that in HepG2 cells, with HL-7702 cells having lower LC 50 . Higher production of oxidative stress, more loss of MMP and stronger suppression of antioxidant enzymes mRNA level occurred in HepG2 cells, while mRNA expression and hepcidin secretion were enhanced in HL-7702 cells at 40/100 μL, indicating the dust extract probably perturbed their liver Fe homeostasis. Our data showed considerable differences in cellular responses between normal and cancerous cell lines. To obtain accurate data, normal hepatocytes should be employed as they better match with the in vivo tissue than cancerous cell lines., (Published by Elsevier Ltd.)

In this study, bioavailability of polychlorinated biphenyls (PCBs) in soil samples aged for various time intervals (7 days, 1 and 5 months) was assessed by in vivo tests using mice. The in vivo bioavailability of PCBs in soil ranged from 45% (PCB180 in soil aging for 5 month) to 119% (PCB52 in soil aging for 1 month), indicating that not all PCBs was available for absorption after ingestion of soil samples. The bioaccessibility was assessed using both physiologically-based extraction test (PBET) and Tenax improved PBET (TI-PBET). Acceptable in vivo-in vitro correlation (r 2  = 0.70 and slope = 1.30 ± 0.20) was observed for TI-PBET, not for PBET. Due to dominant role played by Tenax and bile, the TI-PBET was further simplified to Tenax and Tenax-bile extraction methods. However, poor in vivo-in vitro correlation (r 2  = 0.14 and 0.05) was observed for the two simplified methods, which may be attributed to the combined effect between sorption sink and components in PBET. Therefore, in order to simply TI-PBET or standardize in vitro methods, it is highly necessary to explore the mechanism about the interaction between in vitro method components and sorption sink, or to screen key factors for bioaccessibility results in the future studies., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

In this study, the effects of biochar derived from rice-straw (biochar) and iron-impregnated biochar (Fe-biochar) on Cd and As mobility in rice rhizosphere and transfer from soil to rice were investigated with different application rates. 1-3% biochar reduced porewater Cd in rhizosphere but elevated soluble As, resulting in 49-68% and 26-49% reduction in the root and grain Cd, with a simultaneous increase in root As. Unlike biochar, 0.5% Fe-biochar decreased porewater As throughout rice growth, resulting in reduced root As, which, however, increased Cd uptake by root. Biochar-induced soil As mobilization was probably through competitive desorption and Fe-biochar-induced soil Cd mobilization was probably via soil acidification. The results suggested that biochar and Fe-biochar was effective in reducing Cd and As uptake by rice, respectively, so they may be used as emergency measures to cope with single Cd or As contamination in paddy soils., (Copyright © 2017. Published by Elsevier Ltd.)

Arsenic contamination in drinking water is a worldwide issue, posing threat to human health. Arsenic is an endocrine system disruptor, however, limited information is available regarding its long-term effects on thyroid endocrine system at low exposure. In this study, we assessed the thyroid toxicity of arsenate (AsV) and arsenite (AsIII) at 10-100 μg L -1 in juvenile mice after 8-week of exposure via drinking water. After 1-2 week, AsV and AsIII had little influence on thyroxine (T4) level (56.3-64.7 μg L -1 ) in mouse blood compared to control mice at 57.3-60.7 μg L -1 . However, after 4-8 weeks, 10 μg L -1 AsIII or AsV increased T4 levels to 83.8-88.8 μg L -1 compared to control treatment at 77.2-80.0 μg L -1 , while 100 μg L -1 AsV or AsIII decreased T4 levels except for 100 μg L -1 AsIII for 8 weeks. Based on transmission electron microscopy, exposure to 100 μg L -1 AsIII or AsV for 8 weeks caused thyroid gland damage. In addition, exposure to AsV or AsIII at 10 or 100 μg L -1 impacted gene transcription of hypothalamic-pituitary-thyroid axis including thyroid stimulating hormone and iodothyronine deiodinases. Our data demonstrated that exposing to low levels of AsIII or AsV disrupted T4 homeostasis, influenced the related gene transcription and damaged the thyroid glands in juvenile mice., (Published by Elsevier Ltd.)

Arsenic (As)-resistant bacteria are abundant in the rhizosphere and tissues of As-hyperaccumulator Pteris vittata. However, little is known about their roles in As transformation and As uptake in P. vittata. In this study, the impacts of P. vittata tissue extracts with or without surface sterilization on As transformation in solutions containing 100 μg L -1 AsIII or AsV were investigated. After 48 h incubation, the sterilized and unsterilized root extracts resulted in 45% and 73% oxidation of AsIII, indicating a role of both rhizobacteria and endobacteria. In contrast, AsV reduction was only found in rhizome and frond extracts at 3.7-24% of AsV. A total of 37 strains were isolated from the tissue extracts, which are classified into 18 species based on morphology and 16S rRNA. Phylogenic analysis showed that ∼44% isolates were Firmicutes and others were Proteobacteria except for one strain belonging to Bacteroidetes. While most endobacteria were Firmicutes, most rhizobacteria were Proteobacteria. All isolated bacteria belonged to AsV reducers except for an As-sensitive strain and one AsIII- oxidizer PVR-YHB6-1. Since As transformation was not observed in solutions after filtrating or boiling, we concluded that both rhizobacteria and endobacteria were involved in As transformation in the rhizosphere and tissues of P. vittata., (Published by Elsevier Ltd.)

The monitoring of oxyanions in waters, presents significant challenges due to their relatively low concentrations, and a characteristically changeable/unstable/reactive geochemistry with high spatial and temporal turnover. This results in a very heterogeneous pattern of mobility and bioavailability, which is difficult to capture reliably and in a cost effective manner. The diffusive gradients in thin-films (DGT) technique is a popular analytical tool for testing water quality, primarily because it provides a time-integrated measurement. However, to date, the most widely used DGT configuration for oxyanion sampling, the slurry ferrihydrite binding layer (SF-DGT) has only been fully characterized for phosphate. Confirmatory testing of the functional range of ionic strengths, pH, deployment times and ionic competition effects, that the SF-DGT's operates within has not been carried out, but is addressed in this study for V V , As V , Sb V , and Mo VI . In this study SF-DGT Sb V measurements functioned over the largest range of conditions (ionic strength, 0.1-500 mM; pH 3.86-9.90), while ionic strengths above 100 and 500 mM were found to be problematic for As V and Mo VI , respectively. Low pH (below 4) caused inferences with V V , conversely As V and Mo VI determination faltered/deviated from predicted responses in pH conditions of ∼9. SF-DGT measurements adequately predicted up to weeklong averaged in situ metal oxyanion concentrations in a freshwater river. This study concludes that the SF-DGT configuration is highly suitable for pollution monitoring applications in freshwater systems for key oxyanion species., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

We investigated the effects of arsenate (AsV) and fluoride (F) on each other's uptake in an As-sensitive plant Pteris ensiformis. Plants were exposed to 1) 0.1 × Hoagland solution control, 2) 3.75 mg L -1 As and 1.9, 3.8, or 7.6 mg L -1 F, or 3) 1 mg L -1 F and 3.75 mg L -1 or 7.5 mg L -1 As for 7 d in hydroponics. P. ensiformis accumulated 14.7-32.6 mg kg -1 As at 3.75 mg L -1 AsV, and 99-145 mg kg -1 F at 1 mg L -1 F. Our study revealed that AsV and F increased each other's uptake when co-present. At 1.9 mg L -1 , F increased frond As uptake from 14.7 to 40.3 mg kg -1 , while 7.5 mg L -1 As increased frond F uptake from 99 to 371 mg kg -1 . Although, AsV was the predominant As species in all tissues, F enhanced AsIII levels in the rhizomes and fronds, while the reverse was observed in the roots. Increasing As concentrations also enhanced TBARS and H 2 O 2 in tissues, indicating oxidative stress. However, F alleviated As stress by lowering their levels in the fronds. Frond and root membrane leakage were also evident due to As or F exposure. The results may facilitate better understanding of the mechanisms underlying the co-uptake of As and F in plants. However, the mechanisms of how they enhance each other's uptake in P. ensiformis need further investigation., (Published by Elsevier Ltd.)

Biochar produced by thermal decomposition of biomass under oxygen-limited conditions has received increasing attention as a cost-effective sorbent to treat metal-contaminated waters. However, there is a lack of information on the roles of different sorption mechanisms for different metals and recent development of biochar modification to enhance metal sorption capacity, which is critical for biochar field application. This review summarizes the characteristics of biochar (e.g., surface area, porosity, pH, surface charge, functional groups, and mineral components) and main mechanisms governing sorption of As, Cr, Cd, Pb, and Hg by biochar. Biochar properties vary considerably with feedstock material and pyrolysis temperature, with high temperature producing biochars with higher surface area, porosity, pH, and mineral contents, but less functional groups. Different mechanisms dominate sorption of As (complexation and electrostatic interactions), Cr (electrostatic interactions, reduction, and complexation), Cd and Pb (complexation, cation exchange, and precipitation), and Hg (complexation and reduction). Besides sorption mechanisms, recent advance in modifying biochar by loading with minerals, reductants, organic functional groups, and nanoparticles, and activation with alkali solution to enhance metal sorption capacity is discussed. Future research needs for field application of biochar include competitive sorption mechanisms of co-existing metals, biochar reuse, and cost reduction of biochar production., (Published by Elsevier Ltd.)

Leaching of inorganic arsenic (As) from chromated copper arsenate (CCA)-treated wood may elevate soil As levels. Thus, an environmental concern arises regarding As accumulation in vegetables grown in these soils. In this study, a greenhouse experiment was conducted to investigate the ability of As-hyperaccumulator P. vittata and organic amendments in reducing As uptake by lettuce (Lactuca sativa) from a soil contaminated from CCA-treated wood (63.9 mg kg -1 As). P. vittata was grown for 150 d in a CCA-contaminated soil amended with biochar, activated carbon or coffee grounds at 1%, followed by lettuce for another 55 d. After harvest, plant biomass and As concentrations in plant and soil were determined. The presence of P. vittata reduced As content in lettuce by 21% from 27.3 to 21.5 mg kg -1 while amendment further reduced As in lettuce by 5.6-18%, with activated C being most effective. Our data showed that both P. vittata and organic amendments were effective in reducing As concentration in lettuce. Though no health-based standard for As in vegetables exists in USA, care should be taken when growing lettuce in contaminated soils. Our data showed that application of organic amendments with P. vittata reduced As hazards in CCA-contaminated soils., (Published by Elsevier Ltd.)

Cleanup goals for sites contaminated with persistent organic pollutants (POPs) are often established based on total contaminant concentrations. However, mounting evidence suggests that understanding contaminant bioavailability in soils is necessary for accurate assessment of contaminant exposure to humans via oral ingestion pathway. Animal-based in vivo tests have been used to assess contaminant bioavailability in soils; however, due to ethical issues and cost, it is desirable to use in vitro assays as alternatives. Various in vitro methods have been developed, which simulate human gastrointestinal (GI) tract using different digestion fluids. These methods can be used to predict POP bioavailability in soils, foods, and indoor dust after showing good correlation with in vivo animal data. Here, five common in vitro methods are evaluated and compared using PAHs and PBDEs as an example of traditional and emerging POPs. Their applications and limitations are discussed while focusing on method improvements and future challenges to predict POP bioavailability in different matrices. The discussions should shed light for future research to accurately assess human exposure to POPs via oral ingestion pathway., (Published by Elsevier Ltd.)

The effect of aging on the bioaccessibility of As and Pb in three soils spiked with As (40 or 400 mg kg(-1)), Pb (150 or 1500 mg kg(-1)) or As + Pb (40 mg kg(-1) As and 150 mg kg(-1) Pb) were investigated using the physiologically based extraction test (PBET). Prolonged aging in soils resulted in a decrease in As/Pb bioaccessibility, especially within the first month. After 76 weeks, As/Pb bioaccessibility in soils decreased to a stable level, with 48-84% and 8-34% for bioaccessible As and Pb respectively in the intestinal phase, illustrating that As in spiked soils was much more bioaccessible than Pb. Correlation analysis between sequential extraction data and PBET results showed that the non-specifically sorbed As contributed the most to bioaccessible As, while Pb bound with carbonates and exchangeable fractions were the source for bioaccessible Pb. For future work, minerals containing As and/or Pb instead of their soluble salts can be added to uncontaminated soils to better simulate the natural aging processes., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Incidental ingestion of indoor dust is an important pathway for human exposure to organophosphorus flame retardants (OPFRs) and phthalate esters (PAEs). However, little is known about their bioaccessibility in indoor dust. In this study, indoor dust samples were collected from houses, offices, public microenvironments (PMEs), and university dorms, and physiologically based extraction test (PBET) was used to measure the bioaccessibility of OPFRs and PAEs in these dust samples. Total concentrations of OPFRs in dust samples ranged from 0.01 to 63.2 μg g(-1), with significantly lower concentrations in dorm dust (median = 0.30 μg g(-1)) than those in houses (3.12), offices (5.94), and PMEs (11.6). Total PAEs ranged from 5.49 to 2161 μg g(-1) with significantly lower concentrations in dorm dust (379 μg g(-1)) than those in the other three types of dust (767, 515, and 731 μg g(-1)). When subject to PBET, the bioaccessibility of OPFRs ranged from 8.18% (triphenyl phosphate) to 54.5% (Tris(2-chloroisopropyl) phosphate) for OPFRs, and from 1.21% (di-2-ethylhexyl phthalate, DEHP) to 81.1% (dimethyl phthalate) for PAEs. Estimated exposure doses for adults and infants to OPFRs via dust ingestion were much lower than the reference doses (RfD), but intake dose of DEHP for infants was higher than the RfD of 20 μg kg(-1) d(-1). However, the DEHP intake dose did not exceed the RfD after incorporating bioaccessibility into risk assessment. Our data indicated the importance of considering contaminant bioaccessibility during risk assessment of indoor dust., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Phosphate rock (PR) has been shown to promote plant growth and arsenic (As) uptake by As-hyperaccumulator Pteris vittata (PV). However, little is known about its behaviors in agricultural soils. In this study, impact of 50 mg kg(-1) As and/or 1.5% PR amendment on plant As accumulation and growth was investigated by growing PV for 90 d in three agricultural soils. While As amendment significantly increased plant As uptake and substantially promoted PV growth, the opposite was observed with PR amendment. Arsenic amendment increased plant frond As from 16.9-265 to 961-6017 mg kg(-1),whereas PR amendment lowered frond As to 10.2-216 mg kg(-1). The As-induced plant growth stimulation was 69-71%. While PR amendment increased plant Ca and P uptake, As amendment showed opposite results. The PV biomass was highly correlated with plant As at r = 0.82, but with weak correlations with plant Ca or P at r < 0.30. This study confirmed that 1) As significantly promoted PV growth, probably independent of Ca or P uptake, 2) PR amendment didn't enhance plant growth or As uptake by PV in agricultural soils with adequate available P, and 3) PV effluxed arsenite (AsIII) growing in agricultural soils., (Published by Elsevier Ltd.)

We investigated the effects of chromate (CrVI) and sulfate on their uptake and translocation in As-hyperaccumulator Pteris vittata. Plants were exposed to 1) 0.1 mM CrVI and 0, 0.25, 1.25 or 2.5 mM sulfate or 2) 0.25 mM sulfate and 0, 0.5, 2.5 or 5.0 mM CrVI for 1 d in hydroponics. P. vittata accumulated 26 and 1261 mg kg(-1) Cr in the fronds and roots at CrVI0.1, and 2197 and 1589 mg kg(-1) S in the fronds and roots at S0.25. Increasing sulfate concentrations increased Cr root concentrations by 16-66% and helped CrVI reduction to CrIII whereas increasing CrVI concentrations increased frond sulfate concentrations by 3-27%. Increasing sulfate concentrations enhanced TBARS concentrations in the biomass, indicating oxidative stress caused lipid peroxidation in plant cell membranes. However, addition of 0.25-2.5 mM sulfate alleviated CrVI's toxic effects and decreased TBARS from 23.5 to 9.46-12.3 μmol g(-1) FW. Though CrVI was supplied, 78-96% of CrIII was in the biomass, indicating efficient CrVI reduction to CrIII by P. vittata. The data indicated the amazing ability of P. vittata in Cr uptake at 289 mg kg(-1) h(-1) with little translocation to the fronds. These results indicated that P. vittata had potential in Cr phytoremediation in contaminated sites but further studies are needed to evaluate this potential. The facts that CrVI and sulfate helped each other in uptake by P. vittata suggest that CrVI was not competing with sulfate uptake in P. vittata. However, the mechanisms of how sulfate and CrVI enhance each other's accumulation in P. vittata need further investigation., (Published by Elsevier Ltd.)

The ability of As-resistant endophytic bacteria in As transformation and plant growth promotion was determined. The endophytes were isolated from As-hyperaccumulator Pteris vittata (PV) after growing for 60 d in a soil containing 200 mg kg(-1) arsenate (AsV). They were isolated in presence of 10 mM AsV from PV roots, stems, and leaflets, representing 4 phyla and 17 genera. All endophytes showed at least one plant growth promoting characteristics including IAA synthesis, siderophore production and P solubilization. The root endophytes had higher P solubilization ability than the leaflet (60.0 vs. 18.3 mg L(-1)). In presence of 10 mM AsV, 6 endophytes had greater growth than the control, suggesting As-stimulated growth. Furthermore, root endophytes were more resistant to AsV while the leaflet endophytes were more tolerant to arsenite (AsIII), which corresponded to the dominant As species in PV tissues. Bacterial As resistance was positively correlated to their ability in AsV reduction but not AsIII oxidation. The roles of those endophytes in promoting plant growth and As resistance in P. vittata warrant further investigation., (Published by Elsevier Ltd.)

Bacteria-mediated arsenic (As) transformation and their impacts on As and P uptake and plant growth in As-hyperaccumulator Pteris vittata (PV) were investigated under sterile condition. All As-resistant bacteria (9 endophytic and 6 rhizospheric) were As-reducers except one As-oxidizer. After growing two months in media with 37.5 mg kg(-1) AsV, As concentrations in the fronds and roots were 3655-5389 (89-91% AsIII) and 971-1467 mg kg(-1) (41-73% AsIII), corresponding to 22-52% decrease in the As in the media. Bacterial inoculation enhanced As and P uptake by up to 47 and 69%, and PV growth by 20-74%, which may be related to elevated As and P in plants (r = 0.88-0.97, p < 0.05). Though AsV was supplied, 95% of the As in the bacteria-free media was AsIII, suggesting efficient efflux of AsIII by PV roots (120 µg g(-1) root fw). This was supported by the fact that no AsV was detected in media inoculated with As-reducers while 95% of AsV was detected with As-oxidizer. Our data showed that, under As-stress, PV reduced As toxicity by efficient AsIII efflux into media and AsIII translocation to the fronds, and bacteria benefited PV growth probably via enhanced As and P uptake., (Published by Elsevier Ltd.)

Arsenite (AsIII) efflux is an important mechanism for arsenic (As) detoxification in plants. Low AsIII efflux has been observed in As-hyperaccumulator Pteris vittata, which may contribute to its highly efficient As translocation and accumulation; however, the results may be compromised by microbial AsIII oxidation, relatively low As concentration in the medium and short-term As exposure. Here, sterile P. vittata sporophytes were cultivated in sterile medium containing 10, 200 and 500 µM arsenate (AsV) for 28 d. Arsenite efflux to the growth medium and As speciation in P. vittata was investigated. Low AsIII efflux at 12% of AsV uptake was observed at 10 µM AsV, but high AsIII efflux (36-76%) was observed at 200 and 500 µM AsV, with 1987-2397 mg kg(-1) As being accumulated in the fronds. This is the first report to show efficient AsIII efflux in P. vittata. This study showed that P. vittata may use high AsIII efflux to cope with As toxicity under high As exposure, which may be necessary to sustain growth while accumulating As., (Published by Elsevier Ltd.)

The relationship between bacterial ability in arsenic transformation, siderophore production, and P uptake was investigated using six arsenic-resistant bacteria isolated from the rhizosphere of arsenic-hyperaccumulator Pteris vittata. Bacterial strains of PG5 and 12 were better arsenite (AsIII) oxidizers (31-46 vs. 6.2-21% of 1 mM AsIII) whereas PG 6, 9, 10 and 16 were better arsenate (AsV) reducers (58-95 vs. 7.5-46% of 1 mM AsV). Increase in AsV concentration from 0 to 1 mM induced 3.0-8.4 times more P uptake by bacteria but increase in P concentration from 0.1 to 1 mM reduced AsV uptake by 17-71%, indicating that P and AsV were taken up by P transporters. Bacteria producing more siderophores (PG5 and 12; >73 μM equiv) showed greater AsIII oxidation and AsIII resistance than those producing less siderophore (PG 6, 9, 10 and 16; <23 μM equiv). This observation was further supported by results obtained from mutants of Pseudomonas fluorescens impaired in siderophore production, as they were 23-25% less tolerant to AsIII than the wild-type. Arsenic-resistant bacteria increased their arsenic tolerance by retaining less arsenic in cells via efficient AsIII oxidation and AsV reduction, which were impacted by P uptake and siderophore production., (Published by Elsevier Ltd.)

Phosphorus is an essential nutrient, which is limited in most soils. The P solubilization and growth enhancement ability of seven arsenic-resistant bacteria (ARB), which were isolated from arsenic hyperaccumulator Pteris vittata, was investigated. Siderophore-producing ARB (PG4, 5, 6, 9, 10, 12 and 16) were effective in solubilizing P from inorganic minerals FePO4 and phosphate rock, and organic phytate. To reduce bacterial P uptake we used filter-sterilized Hoagland medium containing siderophores or phytase produced by PG12 or PG6 to grow tomato plants supplied with FePO4 or phytate. To confirm that siderophores were responsible for P release, we compared the mutants of siderophore-producing bacterium Pseudomonas fluorescens Pf5 (PchA) impaired in siderophore production with the wild type and test strains. After 7d of growth, mutant PchA solubilized 10-times less P than strain PG12, which increased tomato root biomass by 1.7 times. For phytate solubilization by PG6, tomato shoot biomass increased by 44% than control bacterium Pseudomonas chlororaphis. P solubilization by ARB from P. vittata may be useful in enhancing plant growth and nutrition in other crop plants., (Published by Elsevier Ltd.)

Rice can take up and translocate more As and Hg than other cereal crops. A hydroponic experiment was conducted to investigate their interactive effects on their uptake and toxicity in rice seedling after exposing to As(III) (0.1, 0.5 or 2.5 mg L−1) and Hg (0.05, 0.25 or 1.25 mg L−1) for 14 d. Rice was much more effective in taking up Hg than As and sequestered both in the roots. As and Hg reached 339 and 433 mg kg−1 in the roots, and 48.5 and 16.1 mg kg−1 in the shoots at As2.5 + Hg1.25. Though Hg inhibited As uptake and translocation, it enhanced As(III) toxicity to rice seedling. However, As inhibited Hg uptake at Hg0.05, but the opposite was observed at Hg0.25 and Hg1.25. Arsenite (54–100%) and inorganic Hg (100%) were the predominant form in the plant based on speciation analysis via HPLC–ICP–MS. Malondialdehyde in the roots and shoots increased with increasing As and Hg concentrations, with the highest being 54 μmol g−1 at As0.5 + Hg1.25 in the roots. Root cell structural damage and organelles number reduction with increasing As and Hg concentration were observed based on TEM. As and Hg transformation and toxicity can help to understand the metabolic mechanisms of As and Hg in rice plant when co-present.

We isolated and characterized As-resistant endophytic bacteria (AEB) from two arsenic hyperaccumulators. Their plant growth promoting traits and the relation between As tolerance and transformation were evaluated. A total of 41 and 33 AEB were isolated from Pteris vittata (PV) and Pteris multifida (PM) respectively. PV AEB represented 2genera while PM AEB comprised of 12 genera, with Bacillus sp. being the most dominant bacteria from both plants. All AEB had limited ability in solubilizing P and producing indole acetic acid (IAA) and siderophore. All isolates tolerated 10mM arsenate (As(V)), with PV isolates being more tolerant to As(V) and PM more tolerant to arsenite (As(III)). Bacterial arsenic tolerance was related to their ability in As(III) oxidation and As(V) reduction as well as their ability to retain As in the biomass to a varying extent. Though AEB showed limited plant growth promoting traits, they were important in arsenic tolerance and speciation in plants., (Published by Elsevier Ltd.)

The characteristics and mechanisms of Pb sorption by biochars produced from sugarcane bagasse at 250, 400, 500, and 600 °C were examined. The Pb sorption isotherms, kinetics and desorption were investigated. All biochars were effective in Pb sorption and were well described by Langmuir isotherm model and pseudo-second-order kinetic model. The maximum sorption capacity decreased from 21 to 6.1 mg g(-1) as temperature increased from 250 to 600 °C. The Pb sorption was rapid initially, probably controlled by cation exchange and complexation and then slowed down, which might be due to intraparticle diffusions. FTIR data and kinetic models suggested that oxygen functional groups were probably responsible for the high Pb sorption onto low temperature biochars (250 and 400 °C) whereas intraparticle diffusion was mainly responsible for low Pb sorption onto high temperature biochars (500 and 600 °C). Decreased phosphorus concentration indicated that P-induced Pb precipitation was also responsible for Pb sorption. Pyrolysis temperature significantly affected biochar properties and played an important role in Pb sorption capacity and mechanisms by biochars., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The two dimensional, small-scale, distribution of labile trace metals was investigated in a sandy loam soil historically treated with sewage sludge. After deployment of two DGT (diffusive gradients in thin-films) probes, their 1.8×15 cm windows were sliced into 5×5 mm and 5×8 mm rectangles to provide three vertical profiles with 5mm resolution. Both sets of profiles showed sharp maxima of Mn, Cd, Co, Cu, Ni and Zn, which varied systematically, both vertically and horizontally. The observed mobilisation of metals was highly localised, as each measurement corresponded to a volume of soil as little as 25-40 μL. Regression analysis indicated mobilisation of Cd, Co, Cu, Ni and Zn were strongly linked to mobilisation of Mn, while there was a strong linkage between Pb and Fe mobilisation. Localised reductive dissolution of Mn oxides or a localised lowering of pH were considered as possible mechanisms., (Copyright © 2012 Elsevier Ltd. All rights reserved.)