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The study explored the Sb toxicity by investigating the impacts of 10% and 20% effective concentrations (EC10 and EC20, respectively) of Sb on the inhibition of barley root elongation in 21 Chinese soils with a wide range of physicochemical properties after aging for 3 months. The results demonstrated that various soil properties profoundly influenced the Sb toxicity which was ranged from 201-2506 mg Sb kg -1 to 323-2973 mg Sb kg -1 under EC10 and EC20, respectively. Soil sand fraction was a significant soil factor responsible for elevating Sb bioavailability. The bioavailable Sb concentration accounted for 2.08%-11.94% of total Sb content in all 21 soil samples and the decreased Sb bioavailability in this study was attributed to soil properties including soil clay fraction, amorphous and crystalloid iron, and oxides of manganese and aluminum. The findings would contribute in developing Sb toxicity threshold for establishing standard for Sb regulation in crop production.

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.)

Arsenic (As) and antimony (Sb) are considered as priority environmental pollutants and their accumulation in crop plants particularly in rice has posed a great health risk. This study endeavored to investigate As and Sb contents in paired soil-rice samples obtained from Xikuangshan, the world largest active Sb mining region, situated in China, and to investigate As speciation and location in rice grains. The soil and rice samples were analyzed by coupling the wet chemistry, laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS), synchrotron-based micro X-ray fluorescence mapping (μ-XRF) and micro X-ray absorption near-edge structure (μ-XANES) spectroscopy. The results of field survey indicated that the paddy soil in the region was co-polluted by Sb (5.91-322.35 mg kg -1 ) and As (0.01-57.21 mg kg -1 ). Despite the higher Sb concentration in the soil, rice accumulated more As than Sb indicating the higher phytoavailability of As. Dimethylarsinic acid (DMA) was the predominant species (>60% on average) in the rice grains while the percentage of inorganic As species was 19%-63%. The μ-XRF mapping of the grain section revealed that the most of As was distributed and concentrated in rice husk, bran and embryo. Sb was distributed similarly to As but was not in the endosperm of rice grain based on LA-ICP-MS. The present results deepened our understanding of the As/Sb co-pollution and their association with the agricultural-product safety in the vicinity of Sb mining area., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Di- n-butyl phthalate (DBP) is a prevalent pollutant in agricultural soils due to use of plastic film. This study focused on sorption mechanism, kinetics, and isotherms of DBP to six paddy soil particle-size fractions (i.e., coarse sand, fine sand, coarse silt, fine silt, clay, and humic acid fractions). DBP sorption involved in both boundary layer diffusion and intraparticle diffusion, following pseudo-second-order kinetics. DBP sorption was a spontaneous physical process, which fit the Freundlich model. Hydrophobic and ionic interaction relevant to the organic matter content, cation exchange capacity, surface area, and pore volume of soil fractions played key roles in DBP sorption. DBP was strongly adsorbed to humic acid and the sorption was reversely associated with soil particle sizes. DBP may exhibit higher mobility and bioavailability in a soil-crop system at lower temperature (15 °C), due to the lower log K oc values.

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.)

Perfluorooctanesulfonate (PFOS) is a toxic and persistent organic pollutant that can be widely detected in agricultural soils. In this study, two lettuce cultivars with low PFOS accumulation were screened out to reduce the exposure of PFOS to the human body via vegetable consumption. The screened low-PFOS cultivars may help to ensure food safety, despite planting in highly PFOS-polluted soils (1.0 mg/kg), due to their high tolerance to PFOS and 4.4-5.7 times lower shoot PFOS concentration than the high-PFOS cultivars. Protein content and protein-mediated transpiration played key roles in regulating PFOS accumulation in the lettuce cultivars tested. Lower protein content, lower stomatal conductance, and lower transpiration rate resulted in low PFOS accumulation. This study reveals the mechanism of forming low-PFOS accumulation of lettuce cultivars at physiological and biochemical levels and lays a foundation for developing a cost-effective and safe approach to grow vegetables in PFOS-polluted soils.

Sorption of perfluorooctanoic acid (PFOA), a toxic and persistent organic pollutant, by various size fractions of an agricultural soil at environmentally relevant concentrations was evaluated. PFOA sorption to all fractions involved both film diffusion and intraparticle diffusion with the rate-limiting step by the latter. PFOA isotherm data fitted a linear model. Organic matter (OM), cation exchange capacity, pore volume, and the Brunauer-Emmett-Teller area played key roles in PFOA sorption. The sorption capacity followed the order of humic acid > clay (0.15-4.4 mm) > fine silt (1.9-39.8 mm) > coarse silt (17.3-79.4 mm) > fine sand (45.7-316.2 mm) > coarse sand (120-724.4 mm), opposite to their contributions to overall PFOA sorption due to the influence of their percentage weight in the original soil. Percentage OM content was the dominant factor controlling the fraction contributions to overall PFOA sorption, demonstrating influence of the hydrophobic force on sorption. PFOA should be highly mobile and bioavailable in soil-crop systems due to the low log K oc values.

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.)

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.)

Global warming has obtained increasing attentions due to its multiple impacts on agro-ecosystem. However, limited efforts had been devoted to reveal the temporal variability of metal speciation and phytotoxicity of heavy metal-polluted soils affected by elevated temperature under the global warming scenario. In this study, effects of elevated temperature (15 °C, 25 °C, and 35 °C) on the physicochemical properties, microbial metabolic activities, and phytotoxicity of three Cu-polluted soils were investigated by a laboratory incubation study. Soil physicochemical properties were observed to be significantly altered by elevated temperature with the degree of temperature effect varying in soil types and incubation time. The Biolog and enzymatic tests demonstrated that soil microbial activities were mainly controlled and decreased with increasing incubation temperature. Moreover, plant assays confirmed that the phytotoxicity and Cu uptake by wheat roots were highly dependent on soil types but less affected by incubation temperature. Overall, the findings in this study have highlighted the importance of soil types to better understand the temperature-dependent alternation of soil properties, Cu speciation and bioavailability, as well as phytotoxicity of Cu-polluted soils under global warming scenario. The present study also suggests the necessary of investigating effects of soil types on the transport and accumulation of toxic elements in soil-crop systems under global warming scenario., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Phosphate compounds and related materials are effective amendments for immobilization of heavy metals in contaminated soils. A greenhouse pot experiment with ryegrass (Lolium perenne) as the test plant was conducted to explore the impact of nanoparticle hydroxyapatite (HAP) on the immobilization and bioavailability of Cu and Zn in a heavy metal-polluted soil. The addition of nanoparticle HAP significantly decreased the uptake of Cu and Zn by ryegrass. As a result, the biomass of ryegrass increased as the rate of nanoparticle HAP increased. The toxicity characteristic leaching procedure (TCLP) and physiologically based extraction test (PBET) results of the treatments showed that the leachable and bioaccessible concentrations of Cu and Zn were significantly reduced after the soil stabilized with nanoparticle HAP. The XRD pattern of nanoparticle HAP was not changed by the presence of Cu and Zn, which suggests that Cu and Zn were immobilized by the formation of solid amorphous phosphate. Nanoparticle HAP was an effective material to immobilize heavy metals in contaminated soils.

Heavy metal stress in culture media is always rhizotoxic. Our study aims to investigate the role of negative potential (ψ 0 ) at root cell membrane surface (CMs) on modeling Zn 2+ toxicity to wheat seedling roots and to examine the effects of different nitrogen forms (NH 4 + and NO 3 - ) on ψ 0 and Zn rhizotoxicity. Solution culture experiments were conducted to measure the root elongation and Zn accumulation under Zn 2+ exposure. The role of two nitrogen forms in affecting Zn 2+ toxicity was compared, giving particular consideration to ψ 0 and Zn 2+ activities at CMs ({Zn 2+ } 0 ). Results showed that NH 4 + alleviates Zn 2+ rhizotoxicity and NO 3 - increases Zn 2+ rhizotoxicity. In modeling the rhizotoxicity, root length correlated better with {Zn 2+ } 0 than {Zn 2+ } b , and the predictive accuracy (r 2 ) of NH 4 + treatment increased from 0.748 to 0.917 when incorporation of {Zn 2+ } 0 and {Ca 2+ } 0 into analysis. Oppositely, ψ 0 played a limited role in modeling Zn 2+ rhizotoxicity and bioavailability in NO 3 - treated medium (r 2  = 0.609). Moreover, higher concentration of Zn in roots was found in NO 3 - treatment, compared with the NH 4 + treatment. ψ 0 rather than the rhizotoxicity data correlated better with Zn accumulation especially in the NO 3 - treatment (r 2  > 0.7), which meant the electrical driving force at CMs playing a dominant role in modeling the metal accumulation. In conclusion, the alleviatory role of NH 4 + on Zn toxicity and uptake was well explained and modeled by electrostatic effects at CMs. Though our data do not explore mechanisms for the NO 3 - -Zn 2+ interactions, we propose that ψ 0 worked better in affecting the driving force for root Zn uptake, than influencing metal bioavailability at CMs.

Contaminants zinc (Zn) and arsenate (As) often coexist in soils. However, little is known concerning the impacts of coexisting As on Zn adsorption and precipitation on soil minerals. In the present study, adsorption and precipitation of Zn on γ-alumina in the absence and presence of arsenate was investigated employing batch experiments and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Results indicated that Zn formed edge-sharing tetrahedral surface complexes at pH 5.5 and Zn-Al LDH-like (layered double hydroxide) precipitates at pH 7.0 on the surface of γ-alumina. The presence of arsenate significantly enhanced Zn sorption densities, and remarkably changed its bonding environment. At pH 5.5, SR-XRD (Synchrotron Radiation-based X-ray Diffraction) and EXAFS showed that koettigite-like precipitate were formed in the cosorption of Zn and As on γ-alumina regardless of the addition sequence of As and Zn. At pH 7.0, when Zn was preequilibrated with γ-alumina prior to the As introduction, mixed Zn-Al LDH-like and amorphous adamite-like precipitates formed. However, when Zn and As were added simultaneously, only amorphous adamite-like precipitate was observed. Zn inner-sphere complexes and surface ternary complexes γ-alumina-As-Zn were the main outcome when As was preequilibrated firstly. Zn-arsenate precipitates could significantly decrease the concentration of Zn in aqueous solution and decrease the bioavailability and mobilization of Zn in soils., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

In the present study, the effects of low-molecular-weight organic acids (LMWOAs) on the toxicity of cadmium (Cd) to Eisenia fetida were investigated in a simulated soil solution. The LMWOAs protected E. fetida from Cd toxicity, as indicated by the increased median lethal concentration (LC50) values and the increased activity of superoxide dismutase. In addition, Cd concentrations in E. fetida decreased dramatically in the presence of LMWOAs. These results were likely because of the complexation between Cd and LMWOAs, which decreased the bioavailability and consequential toxicity of Cd to E. fetida. Notably, LMWOAs reduced Cd toxicity in decreasing order (ethylenediamine tetraacetic acid [EDTA] > citric acid > oxalic acid > malic acid > acetic acid), which was consistent with the decreasing complexation constants between LMWOAs and Cd. These results advance our understanding of the interactions between Cd and LMWOAs in soil. Environ Toxicol Chem 2017;36:1005-1011. © 2016 SETAC., (© 2016 SETAC.)

Elevated roxarsone (ROX) concentrations in soils, caused by land application of ROX-bearing poultry litter, mandate investigation of ROX sorption onto soils. Equilibrium and kinetic studies of ROX sorption onto five soils were carried out to explore the relationship between sorption parameters and soil properties, and to reveal the effects of coexisting humic acid (HA), P(V), As(V), and As(III) on ROX transport. Experimental results indicated that ROX sorption reached equilibrium within 24 h, with pseudo-second order rate constants of 5.74-5.26 × 10(2) g/(mg h); film and intra-particle diffusion were the rate-limiting processes. ROX sorption to soils involved partitioning and adsorption phenomena; however, their relative contributions varied for different soils. The maximum ROX sorption varied with soil type, ranging from 0.59 to 4.12 mg/g. Results from correlation analysis and multiple linear regressions revealed that the maximum sorption capacities, partition coefficients, and desorption percentages were correlated with soil properties, especially iron content, total organic carbon, and dissolved organic carbon. ROX sorption to soils was affected more by soil pH than the initial pH of ROX-containing solutions. Carboxylic and amide functional groups were determined to be responsible for ROX sorption to soils. ROX sorption capacities decreased in the presence of HA, P(V), As(V), and As(III), indicating that ROX mobility in soils was facilitated by dissolved organic matter (DOM) and competing anions., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The fate and transport of roxarsone (ROX), a widely used organoarsenic feed additive, in soil is significantly influenced by the ubiquitous presence of soil-derived dissolved organic matter (DOM). In this study, fluorescence quenching titration and two-dimensional correlation spectroscopy (2D-COS) were employed to study ROX binding to DOM. Binding mechanisms were revealed by fluorescence lifetime measurement and Fourier transform infrared spectroscopy (FTIR). Humic- and protein-like fluorophores were identified in the excitation-emission matrix and synchronous fluorescence spectra of DOM. The conditional stability constant (log KC) for ROX binding to DOM was found to be 5.06, indicating that ROX was strongly bound to DOM. The binding order of ROX to DOM fluorophores revealed by 2D-COS followed the sequence of protein-like fluorophore ≈ the longer wavelength excited humic-like (L-humic-like) fluorophore > the shorter wavelength excited humic-like (S-humic-like) fluorophore. 2D-COS resolved issues with peak overlapping and allowed further exploration of the interaction between ROX and DOM. Results of fluorescence lifetime and FTIR spectra demonstrated that ROX interacted with DOM through the hydroxyl, amide II, carboxyl, aliphatic CH, and NO2 groups, yielding stable DOM-ROX complexes. The strong interaction between ROX and DOM implies that DOM plays an important role in the environmental fate of ROX in soil., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Global warming has received growing attentions about its potential threats to human in recent, however little is known about its effects on transfer of heavy metals in agro-ecosystem, especially for Cd in rice. Pot experiments were conducted to evaluate Cd/Cu translocation in a contaminated soil-rice system under Free Air Temperature Increase (FATI). The results showed that warming gradually decreased soil porewater pH and increased water-soluble Cd/Cu concentration, reduced formation of iron plaque on root surface, and thus significantly increased total uptake of Cd/Cu by rice. Subsequently, warming significantly promoted Cd translocation from root to shoot, and increased Cd distribution percentage in shoot, while Cu was not significantly affected. Enhanced Cd uptake and translocation synergistically resulted in higher rice grain contamination with increasing concentration from 0.27 to 0.65 and 0.14-0.40 mg kg(-1) for Indica and Japonica rice, respectively. However increase of Cu in brown grain was only attributed to its uptake enhancement under warming. Our study provides a new understanding about the food production insecurity of heavy metal contaminated soil under the future global warming., (Copyright © 2016. Published by Elsevier Ltd.)

Soil organic matter (SOM) is the major factor affecting sequestration of heavy metals in soil. The mean free binding energy and the mean free adsorption energy and speciation of Zn in soil, as affected by SOM, were determined by employing Wien effect measurements. The presence of SOM markedly decreased the Zn binding energy in soils in the following order: Top (5.86 kJ mol(-1)) < Bottom (8.66 kJ mol(-1)) < Top OM-free (9.44 kJ mol(-1)) ≈ Bottom OM-free (9.50 kJ mol(-1)). The SOM also significantly decreased the adsorption energy of Zn on black soil particles by reducing nonspecific adsorption of Zn on their surfaces. The speciation of Zn in soils was elucidated by extended X-ray absorption fine structure spectroscopy and microfocus X-ray fluorescence. The results obtained by linear combination fitting of EXAFS spectra revealed that the main forms of Zn in soil were outer-sphere Zn, Zn-illite, Zn-kaolinite, and HA-Zn. As the SOM content increased, the proportion of HA-Zn among the total immobilized Zn increased, and the proportion of nonspecific adsorbed Zn decreased. The present results implied that SOM is an important controlling factor for the environmental behavior of Zn in soils.

The effects of Fe(II) on the sorption and precipitation of Sb(V) on soils and goethite were investigated using batch experiments and X-ray photoelectron spectroscopy (XPS) in this study. The sorption capacity of Sb(V) were much higher in anoxic soil than oxic soil. Typically, dissolved Fe(II) concentration in anoxic soils decreased significantly with increasing Sb(V), which may be suggestive of Fe-Sb precipitation. The elevated concentrations of Fe(II) (1 mM) enhanced the sorption capacity of Sb(V) on goethite significantly. However, synchrotron radiation X-ray diffraction showed no new characteristic peak, indicating that this Fe-Sb precipitate might be poor crystallinity or amorphous. Moreover, Sb(III) was detected in anoxic soil, and the reduction of Sb(V) to Sb (III) improved the sorption capacity of Sb in anoxic soil because of the low solubility and migration of Sb(III). Nevertheless, Fe-Sb co-precipitation and Sb(V) reduction to Sb(III) might contribute simultaneously to the increased sorption capacity of Sb(V) on anoxic soils. This research could improve our current understanding of soil Sb chemistry in paddy and wetland soils., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The mechanisms underlying Cd trophic transfer along the soil-lettuce-snail food chain were investigated. The fate of Cd within cells, revealed by assessment of Cd chemical forms and of subcellular partitioning, differed between the two examined lettuce species that we examined (L. longifolia and L. crispa). The species-specific internal Cd fate not only influenced Cd burdens in lettuce, with higher Cd levels in L. crispa, but also affected Cd transfer efficiency to the consumer snail (Achatina fulica). Especially, the incorporation of Cd chemical forms (Cd in the inorganic, water-soluble and pectates and protein-integrated forms) in lettuce could best explain Cd trophic transfer, when compared to dietary Cd levels alone and/or subcellular Cd partitioning. Trophically available metal on the subcellular partitioning base failed to shed light on Cd transfer in this study. After 28-d of exposure, most Cd was trapped in the viscera of Achatina fulica, and cadmium bio-magnification was noted in the snails, as the transfer factor of lettuce-to-snail soft tissue was larger than one. This study provides a first step to apply a chemical speciation approach to dictate the trophic bioavailability of Cd through the soil-plant-snail system, which might be an important pre-requisite for mechanistic understanding of metal trophic transfer., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The acute and subacute toxicities of cadmium (Cd) to earthworm Eisenia fetida in the presence and absence of glyphosate were studied. Although Cd is highly toxic to E. fetida, the presence of glyphosate markedly reduced the acute toxicity of Cd to earthworm; both the mortality rate of the earthworms and the accumulation of Cd decreased with the increase of the glyphosate/Cd molar ratio. The subcellular distribution of Cd in E. fetida tissues showed that internal Cd was dominant in the intact cells fraction and the heat-stable proteins fraction. The presence of glyphosate reduced the concentration of Cd in all fractions, especially the intact cells. During a longer period of exposure, the weight loss of earthworm and the total Cd absorption was alleviated by glyphosate. Thus, the herbicide glyphosate can reduce the toxicity and bioavailability of Cd in the soil ecosystems at both short- and long-term exposures., (© 2014 SETAC.)

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.)

Goethite widely exists in soils and sediments, and plays a very important role in the environmental fate of toxic metal(loid)s. In the present study, photo-induced oxidation of antimonite [Sb(III)] on goethite was investigated with kinetic measurements and X-ray photoelectron spectroscopy (XPS) techniques. Effects of environmental factors including solution pH, the content of goethite as well as humic acid on the photo-induced oxidation of antimonite were tested. The results indicated that no oxidation of antimonite occurred in goethite suspension in the dark, but significant amounts of antimonite were transformed to antimonate when the suspension was exposed to light. Ferrous ions were found in the solution during the antimonite oxidation process, and its concentration decreased with increasing solution pH, which strongly affected the oxidation rate of antimonite. The initial solution pH has great impact on Sb oxidation. After 2h illumination, the highest oxidation rate was found at pH 3, while the initial oxidation rate was even higher at pH 9. In conclusion, the antimonite can be adsorbed and oxidized on goethite irradiated with light, which will greatly reduce its environmental risk., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Glyphosate (GPS) and copper (Cu) are common pollutants in soils, and commonly co-exist. Due to the chemical structure of GPS, it can form complexes of heavy metals and interface their bioavailability in soil environment. In order to explore the interactions between GPS and Cu, subacute toxicity tests of Cu and GPS on soil invertebrate earthworms (Eisenia fetida) were conducted. The relative weight loss and whole-worm metal burdens increased significantly with the increasing exposure concentration of Cu, while the toxicity of GPS was insignificant. The joint toxicity data showed that the relative weight loss and the uptake of Cu, as well as the superoxide dismutase, catalase and malondialdehyde activities, were significantly alleviated in the present of GPS, which indicated that GPS could reduce the toxicity and bioavailability of Cu in the soil because of its strong chelating effects., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Coupling with triolein-embedded cellulose acetate membrane (TECAM) technique, hydroxypropyl β-cyclodextrins (HPCD) extraction method, and the greenhouse pot experiments, the influences of biochars on polychlorinated biphenyls (PCBs) bioavailability in soil to plant (Brassica chinensis L. and Daucus carota) were investigated. Addition of 2% biochars to soils significantly reduced the uptake of PCBs in plant, especially for di-, tri- and tetra-chlorobiphenyls. PCBs concentrations in the roots of B. chinensis and D. carota were reduced for 61.5-93.7%, and 12.7-62.4%, respectively in the presence of biochars. The kinetic study showed that in the soils amended with/without biochars, PCBs concentrations accumulated in TECAM, as well as in the HPCD extraction solution, followed significant linear relationships with those in plant roots. Application of biochars to soil is a potentially promising method to reduce PCBs bioavailability whereas TECAM technique can be a useful tool to predict the bioavailability of PCBs in soil., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Electrokinetic (EK) remediation has potential to simultaneously remove heavy metals and organic compounds from soil, but the removal percent of these pollutants is very low in general if no enhancing treatment is applied. This study developed a new enhanced-EK remediation technology to decontaminate a heavy metal-organic compound co-contaminated soil by applying different oxidants and pH control. A red soil was used as a model clayed soil, and was spiked with pyrene and Cu at about 500 mg kg(-1) for both to simulate real situation. Bench-scale EK experiments were performed using four oxidants (H(2)O(2), NaClO, KMnO(4), and Na(2)S(2)O(8)) and controlling electrolyte pH at 3.5 or 10. After the treatments with 1.0 V cm(-1) of voltage gradient for 335 h, soil pH, electrical conductivity, and the concentrations and chemical fractionations of soil pyrene and Cu were analyzed. The results showed that there was significant migration of pyrene and Cu from the soil, and the removal percent of soil pyrene and Cu varied in the range of 30-52% and 8-94%, respectively. Low pH favoured the migration of soil Cu, while KMnO(4) was the best one for the degradation of pyrene among the tested oxidants, although it unfortunately prevented the migration of soil Cu by forming Cu oxide. Application of Na(2)S(2)O(8) and to control the catholyte pH at 3.5 were found to be the best operation conditions for decontaminating the Cu-pyrene co-contaminated soil., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Glyphosate (GPS) is a wildly-used pesticide throughout the world. It affects metal behaviors in soil-water system as its functional groups such as amine, carboxylate and phosphonate can react with metal ions to form metal complexes. The reaction will result in the decreasing of heavy metal bioavailability. A laboratory experiment was conducted to investigate the interactions between GPS and copper (Cu) on the acute toxicity of soil invertebrate earthworm (Eisenia fetida), which was exposed to aqueous solutions for 48 h with different mixing concentrations of Cu and GPS (technical-grade Gly acid). The mortality rates, Cu uptake by earthworm, and some biomarkers such as superoxide dismutase (SOD) activity, glutathione (GSH) content, and acetylcholinesterase (AchE) activity were measured. The mortality rates and whole-worm metal burdens increased significantly with the increasing Cu concentration in solution. However, toxicity of GPS to earthworms was not observed in this study. Furthermore, the presence of GPS could significantly reduce the acute toxicity of Cu to earthworms. The mortality rates decreased sharply and the uptake of Cu was nearly halted in the presence of GPS. In addition, the SOD activity, GSH content, and AchE activity almost declined to the levels of the control. These results demonstrate that GPS could control the toxicity as well as the bioavailability of heavy metals in soil solutions where both GPS and heavy metals often coexist.

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.)

The effect of different soil types (red soil,yellow-brown soil and black soil) on the electrokinetic (EK)-oxidation remediation of heavy metals-organic pollutant contaminated soil was studied in laboratory-scale experiments. Copper and pyrene were chosen as model pollutant, and 12% H2O2, 10% hydroxypropyl-beta-cyclodextrin and 0.01 mol x L(-1) NaNO3 solution were added into the anode and cathode cell. The applied voltage was 1 V x cm(-1). After 15 days of EK remediation, the removal rate of pyrene and copper in red soil, yellow-brown soil and black soil were 38.5%, 46.8%, 51.3% for pyrene and 85.0%, 22.6%, 24.1% for Cu, respectively. The high pH of black soil produced high electroosmotic flow and increased the exposure of oxidants and pollutants, meanwhile the low clay content was also conducive to the desorption of pyrene. The low pH and organic matter of red soil affected the chemical species distribution of Cu and increased its removal rate. It is concluded that soil pH, clay content and heavy metal speciation in soil are the dominant factors affecting the migration and removal efficiency of pollutants.

Assessing environmental risks of metal contamination in soils is a complex task because the biologically effective concentrations of metals in soils vary widely with soil properties. The factors influencing the toxic effect of nickel (Ni) on root growth of barley (Hordeum vulgare) were re-evaluated using published data from both soil and hydroponic cultures. The electrical potential (ψ(0) (o) ) and ion activities ({I(z) }(0) (o) ) at the outer surfaces of root-cell plasma membranes (PMs) were computed as the basis of the re-evaluation. The reanalyses demonstrated that root growth was related to: the Ni(2+) activity at the PM surface, ({Ni(2+) }(0) (o) ); calcium (Ca) deficiency (related to {Ca(2+) }(0) (o) ); osmotic effects; and modification of intrinsic Ni(2+) toxicity by magnesium (Mg(2+) ; this appeared to exert an intrinsic (specific) ameliorating effect on intrinsic Ni(2+) toxicity). Electrostatic toxicity models (ETM) were developed to relate root growth to these factors (R(2)  > 0.751). Based on the ETM developed in soil culture and a Ni(2+) solid-solution partitioning model, critical metal concentrations in soils linked to a biological effect were well predicted for 16 European soils with a wide range of properties, indicating the potential utility of ETM in risk assessment of metals in terrestrial ecosystems., (© 2011 The Authors. New Phytologist © 2011 New Phytologist Trust.)

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.)

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.

The aim of this study was to investigate the detailed metal speciation/fractionations of a Cu contaminated soil before and after electrokinetic remediation as well as their relationships with the soil microbial and enzyme activities. Significant changes in the exchangeable and adsorbed-Cu fractionations occurred after electrokinetic treatment, while labile soil Cu in the solution had a tendency to decrease from the anode to the cathode, and the soil free Cu(2+) ions were mainly accumulated in the sections close to the cathode. The results of regression analyses revealed that both the soil Cu speciation in solution phase and the Cu fractionations in solid phase could play important roles in the changes of the soil microbial and enzyme activities. Our findings suggest that the bioavailability of soil heavy metals and their ecotoxicological effects on the soil biota before and after electroremediation can be better understood in terms of their chemical speciation and fractionations.

Remediation programmes are considered to be complete when human risk-based criteria are met. However, these targets are often unsatisfied with the ecological parameters that may be important with regard to future soil use. Five soil subsamples, collecting along a pilot-scale soil column after electrokinetic treatment, were studied, from which about 42.0%-93.3% soil Cu had been successfully removed. A series of biological assays including soil microbial biomass carbon, basal soil respiration, soil urease activity, earthworm assays, and seed assays were used to evaluate their ecological risks. The results showed that the bioassay data from the treatment variants did not supposedly reflecting the decreased soil Cu concentrations after the electrokinetic treatment, but were highly correlated with some soil physicochemical characteristics. It suggests that bioassays are necessary to assess the ecotoxicity of soil after electrokinetic treatment.

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.

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.

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.

A pilot-scale experiment for electrokinetic treatment of 700 kg of copper contaminated red soil was conducted using a constant voltage of 80 V. Dynamic removal percentages of Cu from the soil and energy consumption during the treatment were evaluated together with changes of soil pH, electrical conductivity and soil microbial functional diversity before and after the electrokinetic treatment. The results indicate that 76% of Cu was successfully removed from the soil after 140 d of treatment when lactic acid was used as enhancing reagent for adjusting the catholyte pH and dissolving soil Cu by complexation, and the pilot-scale electrokinetic experiment consumed electric energy of 224 kW h t-1 soil. The post-treatment soil pH values decreased about 0.1-1.6 units compared with the initial value (pH 4.8), and soil electrical conductivities in most of soil sections also significantly decreased. Soil microbial functional diversity varied after the electrokinetic treatment, particularly the increase of substrate richness index, which is possibly due to the stimulation of lactic acid that was introduced into the soil column during the experiment.

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.

To determine the environmental free metal ion activity was a recent hot issue. A method to measure low-level free cupric ion activity in soil solution extracted with 0.01 mol/L KNO3 was developed by using cupric ion-selective electrode (ISE) and calibrating with Cu-buffer solution. Three copper buffers including iminodiacetic acid (IDA), ethylenediamine (EN), and glycine (Gly) were compared for calibrating the Cu-ISE curves in the range of free cupric ions (pCu2+) 7-13. The Cu-EN buffer showed the best electrode response and thus was applied as the calibration buffer. The pCu2+ of 39 contaminated agricultural soils around a copper mine was measured, ranging from 5.03 to 9.20. Most Cu in the soil solutions was found to be complexed with dissolved soil organic matters, averaging 98.1%. The proportion of free Cu2+ ions in the soil solutions decreased with the increasing of solution pH. Soluble Cu and free Cu2+ ions concentrations were analyzed by multiple linear regressions to evaluate the effects of soil properties on metal levels and speciation. The results showed that soil solution pH was the most significant factor influencing pCu2+ (with R2 value of 0.76), while not important for the soluble Cu concentration.

Electrokinetics is an innovative technique for treating heavy metals contaminated soil, especially low pH soils such as the Chinese red soil (Udic Ferrisols). In this paper, a Cu-Zn contaminated red soil is treated by electrokinetics. When the Cu-Zn contaminated red soil was treated without control of catholyte pH during the electrokinetic treatment, the soil pH in the soil sections near cathode after the experiment was high above 6, which resulted in accumulation of large amounts of Cu and Zn in the soil sections with such high pH values. Compared to soil Cu, soil Zn was more efficiently removed from the soil by a controlled electrokinetic method. Application of lactic acid as catholyte pH conditioning solution caused an efficient removal of Cu and Zn from the soil. Increasing the electrolyte strength (salt concentration) of the conditioning solution further increased Cu removal, but did not cause a significant improvement for soil Zn. Soil Cu and Zn fractions after the electrokinetic treatments were analyzed using sequential extraction method, which indicated that Cu and Zn precipitation in the soil section closest to the cathode in the treatments without catholyte pH control limited their removal from the soil column. When the catholyte pH was controlled by lactic acid and CaCl(2), the soil Cu and Zn removal percentage after 554 h running reached 63% and 65%, respectively. Moreover, both the residual soil Cu and Zn concentrations were lower than 100 mg kg(-1), which is adequate and meets the requirement of the Chinese soil environmental quality standards.

Effect of electrokinetic treatment on copper partitioning and distribution in mine tailings were studied. In particular the effects of catholyte enhancement by HAc-NaAc, HCl, HAc-NaAc+EDTA and lactic acid+NaOH were evaluated. The results show that conditioning the catholyte plays a very important role in improving Cu removal. When HAc-NaAc is used in the catholyte, the removal percentage of total Cu from the mine tailings sample reached 12.3% under 40 V in 15 days of treatment. The removal percentage of Cu increased to 31.2% when EDTA was used together with HAc-NaAc in the catholyte. At the same time, increasing the applied voltage and treatment time result in an increase in the Cu removal from the mine tailings. Compared with HAc-NaAc (pH=3.52), the use of lactic acid+NaOH (pH=3.15) in the catholyte resulted in better performance in Cu removal from the mine tailings. HCl treatment resulted in removal of about 17.5% of Cu from the mine tailings; however, it resulted in production of significant amounts of toxic chlorine gas. Copper partitioning in the mine tailings was analyzed before and after the electrokinetic treatments. The analysis was conducted using 0.25 mol/l MgCl2 and 0.5 mol/l HCl as extractants, consequently, to assess the mobility of Cu after treatment. The results showed that lowering the pH of the mine tailings increased the exchangeable Cu fraction (or the portion extracted by MgCl2). Accordingly, further acidification results in an increased mobility of Cu and increase in the environmental risk of mine tailings.

The effect of enhancement reagents on the efficiency of electrokinetic remediation of Cu contaminated red soil is evaluated. The enhancement agents were a mix of organic acids, including lactic acid+NaOH, HAc-NaAc and HAc-NaAc+EDTA. The soil was prepared to an initial Cu concentration of 438 mgkg(-1) by incubating the soil with CuSO4 solution in a flooded condition for 1 month. Sequential extraction showed that Cu was partitioned in the soil as follows: 195 mgkg(-1) as water soluble and exchangeable, 71 mgkg(-1) as carbonate bound and 105 mgkg(-1) as Fe and Mn oxides. The results indicate that neutralizing the catholyte pH maintains a lower soil pH compared to that without electrokinetic treatment. The electric currents varied depending upon the conditioning solutions and increased with an increasing applied voltage potential. The electroosmotic flow rate changed significantly when different conditioning enhancing reagents were used. It was observed that lactic acid+NaOH treatments resulted in higher soil electric conductivities than HAc-NaAc and HAc-NaAc+EDTA treatments. Ultimately, enhancement by lactic acid+NaOH resulted in highest removal efficiency (81% Cu removal) from the red soil. The presence of EDTA did not enhance Cu removal efficiencies from the red soil, because EDTA complexed with Cu to form negatively charge complexes, which slowly migrated toward the anode chamber retarding Cu2+ transport towards the cathode.

The electrokinetic removal of chromium and copper from contaminated soils by adding lactic acid in cathode chamber as an enhancing reagent was evaluated. Two sets of duplicate experiments with chromium contaminated kaolinite and with a silty soil sampled from a superfund site in California of USA and polluted by Cr and Cu, were carried out in a constant current mode. Changes of soil water content and soil pH before and after the electrokinetic experiments, and variations of voltage drop and electroosmosis flow during the treatments were examined. The results indicated that Cr, spiked as Cr( VI ) in the kaolinite, was accumulated mainly in the anode chamber, and some of Cr and metal hydroxides precipitated in the soil sections in contact with the cathode, which significantly increased electrical energy consumption. Treatment of the soil collected from the site showed accumulation of large amounts of Cr and Cu in the anode chamber while none was detected in the cathode one. The results suggested that the two metals either complexed with the injected lactic acid at the cathode or existed as negatively charged complex, and electromigrated toward the anode under a voltage gradient.

This report examined electrochemical remediation of copper contaminated kaolinite by controlling electrolytes' pH for both of anolyte and catholyte simultaneously. Results showed that electrokinetic process and remediation efficiency varied obviously when different buffer systems, including citric acid (test 1 ) nitric acid + EDTA (test 2) and nitric acid (test 3), were used to control catholyte pH and Na2CO3 was used at the same time to control all anolyte one. It was found that under such pH condition soil's pH in soil column kept at 3.0-7.0 successfully, and correspondingly no copper precipitation and decrease of soil electroconductivity appeared, which are usually observed in electrokinetic process due to OH- introduction into soil column by electrochemical reaction occurred in cathode. Electroosmosis flow rates were almost equal for these three tests, indicating that these buffers did not affect Zeta-potential of kaolinite within the examined duration. More acid and basic solution was added into electrokinetic cell when nitric acid was used as buffer than when nitric acid + EDTA and then citric acid were used. Due to introduction of large amounts of ions into soil column, significant higher current was observed for test 3 than other two. Analysis of copper speciation and total quantity in kaolinite indicated that 22.5%, 23.74% and 55.65% Cu were removed from kaolinite for test 1, test 2 and test 3 respectively after only 10 days' electrokinetic remediation.

Speciation and fractionation of heavy metals in soil subsamples experimentally loaded with Pb, Cd, Cu and Zn in orthogonal design was investigated by sequential extraction, and operationally defined as water-soluble and exchangeable(SE), weakly specific adsorbed(WSA), Fe and Mn oxides-bound(OX) and organic-bound(ORG). The results showed that fractions of heavy metals in the soil subsamples depended on their speciation. About 90% of Cd and 75% of Zn existed in soil subsamples in the SE fraction. Lead and Cu existed in soil subsamples as SE, WSA and OX fractions simultaneously, although SE was still the major fraction. Organic-bound heavy metals were not clearly apparent in all the soil subsamples. The concentration of some heavy metal fractions in soil subsamples showed the good correlation with ionic impulsion of soil, especially for the SE fraction. Continuous saturation of soil subsamples with 0.20 mol/L NH4Cl, which is the first step for determination of the negative surface charge of soil by the ion retention method, resulted in desorption of certain heavy metals from the soil. It was found that the percentage desorption of heavy metals from soil subsamples depended greatly on pH, the composition and original heavy metal content of the soil subsamples. However, most of the heavy metals in the soil subsamples were still be retained after multiple saturation. Compared with the parent soil, the negative surface charge of soil subsamples loaded with heavy metals did not show difference significantly from that of the parent one by statistical analysis. Heavy metals existed in the soil subsamples mainly as exchangeable and precipitated simultaneously.