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This study investigated the effects of soil water content on Cd immobilization and uptake by leek with the combined application of biochar and organic fertilizer using mechanism experiment and pot experiment. Mechanism experiment was conducted with the three-layer mesh method, which can reveal the individual mechanisms and contributions of biochar and soil to Cd immobilization. The results of mechanism experiment showed that the Cd adsorption amount by biochar was very little at low soil water content (θw = 20%, w/w), and both of Cd adsorption amount and rate significantly increased at higher θw (40% and 60%). The Cd immobilization by biochar at higher θw (40% and 60%) was significantly better than that at low θw (20%) in soils because F1 (percentages of exchangeable Cd) decreased with increasing moisture. For example, the F1 percentages were 58.27%, 40.67%, and 38.46% in the soil at 4.40 mg·kg-1 under M20, M40, and M60 (θw = 20%, 40%, 60%) at day 120, respectively. The results of pot experiment showed that the Cd in leek leaves and roots continuously accumulated with planting time in each batch, and biochar and organic fertilizer treatments significantly reduced the Cd enrichment in leek. Combined treatment of biochar and organic fertilizer (BO) is superior to biochar treatments (BC) and CK for Cd immobilization in soil. For example, the percentages of F1 under the treatments of CK, BC, and BO were 64.43%, 49.13%, and 43.67% at 75% field water capacity treatment, respectively. For the same treatment, with increasing water contents, the better the Cd was immobilized in the soil and the greater the leek biomass. However, the total uptake of Cd by leek were increased by promoting crop growth under water content conditions.

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Many experiments showed that exogenous ligands could enhance cadmium (Cd) phytoextraction efficiency in soils. Previous studies suggested that the dissociation and the apoplastic uptake of Cd complex could not fully explain the increase of root Cd uptake. Two hypotheses are evaluated to explain enhanced Cd uptake in the presence of ligand: i) enhanced apoplastic uptake of complex due to reduced apoplastic resistance and ii) complex internalization by membrane transporters. RESULTS: show that the ligand affinity for Cd is a key characteristic determining the potential mechanism for enhanced Cd uptake. When low molecular weight organic acids are applied, the complex dissociation could generally be fast (> 10-3.3 s-1) and result in the increased Cd uptake. When hydrophilic aminopolycarboxylic acids (APCAs) are applied in experiments without water or temperature stresses to the plant, the root water uptake flux could very likely be high (> 10-7.8 dm s-1), and the strong apoplastic complex uptake could enhance the root Cd uptake. When lipophilic APCAs are applied, the strong internalization of the complex by membrane transporters could result in the increased Cd uptake if the maximum internalization rate is high (> 10-12 mol dm-2 s-1). However, the complex internalization by membrane transporters must be experimentally confirmed.

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This study investigated the competitive adsorption and immobilization of cadmium (Cd), nickel (Ni), and copper (Cu) by biochar in unsaturated soils under single-, binary-, and ternary-metal systems. The results showed that the immobilization effects by the soil itself were in the order of Cu > Ni > Cd, and the adsorption capacities of freshly contaminated heavy metals by biochar were in the order of Cd > Ni > Cu in unsaturated soils. The adsorption and immobilization of Cd by biochars in soils was weakened by competition more in the ternary-metal system than that in the binary-metal system; the competition with Cu caused a more significant weakening effect than that with Ni. For Cd and Ni, nonmineral mechanisms preferentially adsorbed and immobilized Cd and Ni compared to mineral mechanisms, but the contributions of the mineral mechanisms to the adsorption gradually increased and became dominant with increasing concentrations (at average percentages of 62.59%-83.30% and 41.38%-74.29%, respectively). However, for Cu, the contributions of the nonmineral mechanisms to Cu adsorption were always dominant (average percentages of 60.92%-74.87%) and gradually increased with increasing concentrations. This study highlighted that the types of heavy metals and coexistence should be focused when remediating heavy metal contamination in soils.

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In this study, cadmium (Cd) transport and immobilization on passivators (biochar, organic fertilizer) and soils under saturated-unsaturated conditions were independently analyzed. The results showed that the Cd adsorption capacities of biochar and organic fertilizer were comparable in acidic soils. But in alkaline soils, the Cd adsorption capacity of organic fertilizer was significantly larger than that of biochar. In acidic soils, passivators effectively immobilized Cd, and the total net effects were in the order: combination (44.05-58.13%) > 3% biochar (31.96-46.88%) > 3% organic fertilizer (28.78-41.82%). In alkaline soils, all treatments had negative effects on Cd immobilization. For acidic soils, the immobilization of Cd was mainly attributed to the passivators, and the positive contribution percentages of relatively stable Cd increase by passivators were 81.05-100%, while those by soils were 0-18.95%. For alkaline soils, after the treatments of passivators, although a considerable amount of Cd was immobilized inside the passivator, Cd was activated more inside the soil. Therefore, it is noteworthy that soil conditions must be fully considered when applying biochar and organic fertilizers for Cd remediation.

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In this study, original and two KMnO4-modified rice straw biochars (pre- and postmodification) were prepared, which were all pyrolysed at 400 °C. Premodified biochar had the largest Cd adsorption capacity, strongest acid and solute buffering capacity, which benefited from the increase of carbonate content, specific surface area, and the emergence of Mn(II) and MnOx through modification. Original and premodified biochars were then conducted four types of aging process by an improved three-layer mesh method, namely, aging without soil and co-aging with acid (pH = 5.00), neutral (pH = 7.00), and alkaline (pH = 8.30) soils. The adsorption capacities of modified biochar were always larger than those of original biochar after aging processes. After four aging processes, Cd(II) adsorption capacities were basically in the order of aged biochar without soil > biochar co-aged with alkaline soil > biochar co-aged with neutral soil > biochar co-aged with acid soil, and KMnO4-modified biochar was always better than original biochar after co-aging with soils. The dominant adsorption mechanism of original and premodified biochars (fresh and aged) for Cd(II) was all the precipitation and adsorption with minerals (accounted for 58.55 ~ 85.55%). In this study, we highlighted that biochar remediation for Cd should be evaluated by co-aging with soil instead of aging without soil participation.

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Instead of traditional batch and column experiments with large water-soil ratios, this study investigated the behaviors and mechanisms of Cd adsorption and immobilization by biochar in unsaturated soils, in which the soil moisture conditions were closer to those in the actual field. The transport, transformation, and immobilization of cadmium (Cd) by pristine and KMnO4-modified biochars in unsaturated soils were investigated during a 48-week mild aging process. Biochar acidified with HCl solution was employed to quantify the contributions of mineral and non-mineral components in biochar to Cd adsorption and immobilization in unsaturated soils with a three-layer mesh method. The behaviors and mechanisms of Cd adsorption by biochar in unsaturated soils significantly differed from those in aqueous solutions. The equilibrium times of Cd adsorption by biochar in unsaturated soils (weeks) were much longer than those in aqueous solutions (hours). The percentages of the Cd adsorbed by pristine and modified biochar remained relatively constant relative to the total Cd in unsaturated soils, which accounted for 39.50-49.39 % and 57.35-68.94 %, respectively. The contribution of mineral components to Cd adsorption dominated in both unsaturated soils (45.00-94.09 %) and aqueous solutions (70.73-95.51 %). The process of Cd immobilization in unsaturated soils was that biochar firstly adsorbed the exchangeable Cd from the soil, and then converted it to relatively stable Cd. After aging for 48 weeks, the contributions of non-mineral components to Cd immobilization dominated in unsaturated soil with a low concentration (1.23 mg·kg-1), and the contributions of mineral components to Cd immobilization dominated in unsaturated soil with medium-high concentrations (4.08-51.26 mg·kg-1).

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This study investigated saturated-unsaturated soils, which were closer to the actual field conditions than traditional batch and column experiments with large water-soil ratios. The competitive adsorption, immobilization, and desorption of Cd, Ni, and Cu in soils treated with original and KMnO4-modified biochars were investigated under combined aging. Moreover, the employment of a three-layer mesh method enabled the independent analysis of heavy metals on biochar and soil during aging. The results showed that the order of biochar adsorption capacities was Cd > Cu > Ni in tested soils, and competing with Ni and Cu enhanced the Cd adsorption on biochars. Cd desorbed most with the CaCl2 solution while Ni and Cu desorbed most with citric acid. Modified biochar had improved immobilization effects compared to original biochar, and maintained the most stable remediation effects. The maximum variations in the stable Cd fraction during aging were 7.21%, 13.26%, and 14.71% for modified biochar, original biochar, and CK, respectively. However, for Ni and Cu, the biochar application reduced the residual fraction and increased desorption by citric acid. However, the stable fractions of Ni and Cu remained dominant, accounting for 83.28-97.85% and 86.31-98.96%, respectively.

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Cd long-term immobilization by biochar and potential risk in soils with different pH were quantified under a combined artificial aging, which simulated five years of aging in the field based on local climate. Two biochars (original and KMnO4-modified) and five soils with different pH were tested, and an improved three-layer mesh method was employed in this study. Five aging cycles were carried out (Cycle 1-Cycle 5), and each aging cycle quantitatively simulated 1 year of natural aging. As the aging time increased, Cd leaching loss in all soils gradually increased from Cycle 1 to Cycle 5; for relatively stable Cd fraction, it decreased firstly and then stabilized in acidic and neutral soils (S1-S4), while it decreased firstly and then increased in alkaline soil (S5). Biochars significantly promoted Cd immobilization in strongly acidic soil (S1) by increasing relatively stable fractions and decreasing leaching loss. For weakly acidic and neutral soils (S2-S4), although biochars still had positive effects, the immobilization effects were weakened to certain extents compared with S1. The percentage of Cd leaching loss decreased by 19.12% in strongly acidic soil (S1) and by 1.12-11.35% in weakly acidic and neutral soils (S2-S4) after modified biochar treatment. For alkaline soil (S5), the application of biochars had negative effects on Cd immobilization by decreasing relatively stable fractions and increasing leaching loss, and posed risks to the environment. For strongly acidic soil (S1) and weakly acidic and neutral soils (S2-S4), the percentages of relatively stable fractions increased from 6.09-19.93% to 24.98-36.70% after modified biochar treatment. However, for alkaline soil, the percentage of relatively stable fractions decreased from 55.27% to 53.93% after biochar treatment. The more acidic the soil, the more effective the Cd immobilization by biochar. Biochars with high pH level are not suitable for the remediation of alkaline Cd contaminated soil.

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To investigate the effects of competitive adsorption with Ni(II) and Cu(II) on the adsorption of Cd(II) by modified biochar co-aged with acidic soil, four biochars were employed in this study, namely original biochar, KMnO4-modified biochar and two aged biochars which co-aged with an acidic soil using above biochars under freeze-thaw cycling and dry-wet cycling for 54 days simulating 6 years of natural aging. The results showed that biochar adsorption capacities of three heavy metal ions were in the order of Cd(II) > Cu(II) > Ni(II) in the single system while Cu(II) > Cd(II) > Ni(II) in binary and ternary systems. Modification improved biochar adsorption capacity of Cd(II), but competitive adsorption with Ni(II) and Cu(II) weakened the improvement of modification on adsorption performance of modified biochar in binary and ternary systems. The QMBC/QBC of Cd(II) (QMBC and QBC are the adsorption capacities of heavy metals by modified and original biochars) decreased from 231.57% (single system) to 216.67%∼219.41% (binary system) and further decreased to 207.74% (ternary system). Co-aging with soil weakened the adsorption capacities of biochars for Cd(II), even worse, competition aggravated this negative effect of co-aging. The QAMBC/QMBC of Cd(II) (QAMBC is the adsorption capacities of heavy metals by aged modified biochar) decreased from 65.41% (single system) to 14.43%∼19.46% (binary and ternary systems). Therefore, the impact of competition should be fully considered when evaluating Cd long-term remediation effects of modified biochar in Cd polluted soils accompanied with other heavy metals.

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We quantified the transport and transformation of Cd in historically contaminated soil (OS) and artificially contaminated soil (NS), treated with 3% (w/w) rice straw biochar prepared at 400 °C (BC400) and 700 °C (BC700) under combined dry-wet and freeze-thaw cycles for 72 days simulating the natural aging process of 8 years. An improved three-layer mesh experiment was developed to simulate the natural situation in field. The result showed that the total Cd concentration increased in the biochar but decreased in the soil, suggesting that Cd was transported from the soil into the biochar during the aging process. The total Cd concentration in BC400 treated with both soils was higher than that in BC700 treated with both soils, however, BC700 displayed stronger ability on immobilizing Cd than BC400 because the Tessier exchangeable Cd fraction in BC700 treated both soils was lower than that in BC400 treated with both soils. The average Tessier exchangeable Cd fraction in the soil and biochar decreased in all treatments during the aging process, indicating that Cd tended to be more stable in the soil for a long term. The result also showed that biochar could immobilizate Cd by decreasing the Tessier exchangeable Cd fraction of soil and biochar, and the quantitative contributions of biochar and soil to Cd immobilization were different in OS and NS treated with BC400 and BC700. The biochar contribution to the reduction in Tessier exchangeable Cd fraction accounted for 40-85% in NS treated with BC400 and 54-82% in NS treated with BC700. However, in OS treated with biochar, the biochar contribution accounted for nearly 100%, and soil had almost no contribution. In summary, OS did not contribute to Cd immobilization, while NS contributed nearly 50% to Cd immobilization, and BC700 was more effective in immobilizing Cd than BC400.

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The desorption rate is an important factor determining cadmium (Cd) ecotoxicity and pollution remediation in soils. The pedotransfer functions (PTFs) of desorption rate coefficients of fresh Cd in soils have been developed in literature. We hypothesized that the aging of Cd pollution would alter Cd desorption process. Taking historically polluted soils as the object, this study aimed at testing the hypothesis and developing new PTFs of desorption rate coefficients for historical Cd. 15 d batch extraction experiments and 13 kinetic models were employed to define Cd desorption rate coefficients in 27 historically polluted soil samples. Compared with fresh Cd, the desorption rate coefficients of historical Cd were lower, and the break time of biphasic desorption processes was retarded to 3 d (4320 min). Different with the usual models for fresh Cd desorption (e.g. parabolic diffusion and two constant rate models), the best models to mimic the historical Cd desorption processes were the pseudo first order, logarithmic, Elovich, and simple Elovich models. The rate-limiting step controlling Cd desorption was changed from the intraparticle diffusion to the interface reaction with aging of pollution. New PTFs of desorption rate coefficients of historical Cd were established (R2 ≥ 0.71). Cd desorption rate coefficients increased with organic matter and clay contents, but decreased with oxalate extractable Fe content, solution pH, cation exchange capacity, and silt content. The key soil properties influencing desorption rate coefficients were not altered by the aging of pollution. The developed PTFs could guide us to adjusting the ecotoxicity and pollution remediation of Cd in historically polluted field soils.

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To improve the reliability of methods to trace surface water pollutants in river basins, hydrological and water quality processes in the Fuxi River Basin were continuously monitored from 2013 to 2015, and the main pollution sources in the watershed and δ15N as well as δ18O in the rivers were measured simultaneously. The Soil and Water Assessment Tool (SWAT) model was used to simulate the NH4+ and NO3- migration processes in the hydrological processes of the land surface and rivers. On this basis, the processes of mixing, transformation, and fractionation of δ15N and δ18O in NO3- were coupled, and the simulation methods of δ15N and δ18O in the rivers were developed. The results showed that δ15N and δ18O in the rivers were mainly affected by the pollution sources in the river basin and the variation in runoff conditions during different hydrological periods. The contribution of the mixing process of different isotopes to the isotope abundance was 82.74%. The contribution of isotope fractionation in the process of nitrogen conversion was 16.26%. The influence of NH4+ and NO3- concentration deviation from the SWAT simulation on the simulation errors of δ15N and δ18O was 10.44%. The δ18O simulation errors were 18.72% larger than those of δ15N because of the higher variation range of δ18O in rainfall and the complexity of δ18O. The systematic errors and deviations of the simulated δ15N and δ18O results using the proposed method were less than 10% and 15%, respectively. The simulation method of δ15N and δ18O in the river basin has a clear physical meaning, which provides a useful approach for tracing nitrogen sources in rivers.

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Human populations are threatened by chronic exposure to the Cd accumulated in foods after being taken up from soils by crops. To decide whether and to what extent it is necessary to reduce the Cd content in cultivated soils, one needs to understand and predict its evolution. We therefore simulated the Cd mass balance in the soils under annual crops in France and in its 22 regions for the next century, following six scenarios of agricultural practices or regulatory conditions. If current cultivation practices are maintained, the average Cd content would increase by about 15% after a century, due to the input of Cd with P fertilizer applications. This represents around 85% of the soil Cd inputs and is nearly twice the Cd output caused by leaching and crop offtake. These results conflict with those recently obtained at the European level, due to three factors: the higher rate of P application in France than in Europe, a higher Cd content in the P fertilizers applied in France and a lower Cd leaching in French soils. Strict application of the good practices for P fertilization would stabilize the future soil Cd content at its present level. Assuming the current excessive P fertilization, the enforcement of a regulation limiting Cd content in the P fertilizers, as proposed by the European Union, would lead to a lesser increase in soil Cd, by 1.6% to 3.9% after a century. The combination of P fertilization good practices and Cd content limitation in P fertilizers would lead to a decrease in soil Cd content of between 3.0% to 5.2%. Organic agriculture would lead to an evolution of soil Cd content similar to that of conventional agriculture applying good practices. The accuracy of the mass balances could be ameliorated by a better assessment of Cd leaching.

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The dissociation of metal complexes in the soil solution can increase the availability of metals for root uptake. When it is accounted for in models of bioavailability of soil metals, the number of partial differential equations (PDEs) increases and the computation time to numerically solve these equations may be problematic when a large number of simulations are required, for example for sensitivity analyses or when considering root architecture. This work presents analytical solutions for the set of PDEs describing the bioavailability of soil metals including the kinetics of complexation for three scenarios where the metal complex in solution was fully inert, fully labile, or partially labile. The analytical solutions are only valid i) at steady-state when the PDEs become ordinary differential equations, the transient phase being not covered, ii) when diffusion is the major mechanism of transport and therefore, when convection is negligible, iii) when there is no between-root competition. The formulation of the analytical solutions is for cylindrical geometry but the solutions rely on the spread of the depletion profile around the root, which was modelled assuming a planar geometry. The analytical solutions were evaluated by comparison with the corresponding PDEs for cadmium in the case of the French agricultural soils. Provided that convection was much lower than diffusion (Péclet's number<0.02), the cumulative uptakes calculated from the analytic solutions were in very good agreement with those calculated from the PDEs, even in the case of a partially labile complex. The analytic solutions can be used instead of the PDEs to predict root uptake of metals. The analytic solutions were also used to build an indicator of the contribution of a complex to the uptake of the metal by roots, which can be helpful to predict the effect of soluble organic matter on the bioavailability of soil metals.

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The aim of this study was to investigate the influence of chemical leaching on permeability and Cd removal from fine-grained polluted soils. Column leaching experiments were conducted using two types of soils (i.e., artificially Cd-polluted loam and historically polluted silty loam). Chemical agents of CaCl2, FeCl3, citric acid, EDTA, rhamnolipid, and deionized water were used to leach Cd from the soils. Results showed that organic agents reduced permeability of both soils, and FeCl3 reduced permeability of loam soil, compared with inorganic agents and deionized water. Entrapment and deposition of colloids generated from the organic agents and FeCl3 treatments reduced the soil permeability. The peak Cd effluence from the artificially polluted loam columns was retarded. For the artificially polluted soils treated with EDTA and the historically polluted soils with FeCl3, Cd precipitates were observed at the bottom after chemical leaching. When Cd was associated with large colloid particles, the reduction of soil permeability caused Cd accumulation in deeper soil. In addition, the slow process of disintegration of soil clay during chemical leaching might result in the retardation of peak Cd effluence. These results suggest the need for caution when using chemical-leaching agents for Cd removal in fine-grained soils.

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The objective of this study was to investigate the influence of large-scale phosphate mining (PM) on hydrology and water quality in the Huangbai River basin, China. Rainfall and runoff data were used to analyze hydrological changes of the basin before (from 1978 to 2002) and during (from 2003 to 2014) the PM period. From 2009 to 2014, flow rate and concentrations of ammonia nitrogen (NH4(+)), nitrate (NO3(-)), fluoride (F(-)), suspended solids (SS), total nitrogen (TN), soluble phosphorus (SP), and total phosphorus (TP) were measured at the outfalls of PM as well as at outlets of sub-basins with and without PM practices. Results showed that the PM activities generally reduced runoff (i.e., the runoff coefficient and runoff peak). The sequential Mann Kendall test revealed a decrease trend of runoff during wet seasons after 2008 in the PM regions. For a mining scale of one unit of PM productivity (i.e., 10(8)kg phosphate ore per year or 2.74×10(5) kg d(-1)), TN, SS, and TP of 0.633, 1.46 to 5.22, and 0.218 to 0.554 kg d(-1) were generated, respectively. The NH4(+) and TN loads in the sub-basins with PM were significantly higher than these in the sub-basins without PM; however, the NH4(+) and TN loads that discharged into rivers from the background non-point sources discharged were less in the sub-basins with PM than those without PM. The result was attributed to the reduction of runoff volume by PM. The annual mean concentrations of TN in reservoir water increased with the scales of PM, whereas the mean concentrations of SP were low. Nevertheless, the SP concentrations in the reservoirs greatly increased after 2012, mainly related to the dissolution of apatite in the sediment. The information from this study should improve the understanding of changes in hydrology and water quality in regions with large-scale PM.

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Phytoextraction is a potential method for cleaning Cd-polluted soils. Ligand addition to soil is expected to enhance Cd phytoextraction. However, experimental results show that this addition has contradictory effects on plant Cd uptake. A mechanistic model simulating the reaction kinetics (adsorption on solid phase, complexation in solution), transport (convection, diffusion) and root absorption (symplastic, apoplastic) of Cd and its complexes in soil was developed. This was used to calculate plant Cd uptake with and without ligand addition in a great number of combinations of soil, ligand and plant characteristics, varying the parameters within defined domains. Ligand addition generally strongly reduced hydrated Cd (Cd(2+)) concentration in soil solution through Cd complexation. Dissociation of Cd complex ([Formula: see text]) could not compensate for this reduction, which greatly lowered Cd(2+) symplastic uptake by roots. The apoplastic uptake of [Formula: see text] was not sufficient to compensate for the decrease in symplastic uptake. This explained why in the majority of the cases, ligand addition resulted in the reduction of the simulated Cd phytoextraction. A few results showed an enhanced phytoextraction in very particular conditions (strong plant transpiration with high apoplastic Cd uptake capacity), but this enhancement was very limited, making chelant-enhanced phytoextraction poorly efficient for Cd.

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