The long term vertical and horizontal mobility of mercury (Hg) in soils of agricultural areas of a historically contaminated Italian National Relevance Site (SIN Brescia-Caffaro) was investigated. The contamination resulted from the continuous discharge of Hg in irrigation waters by an industrial plant (Caffaro S.p.A), equipped with a mercury-cell chlor-alkali process. The contamination levels with depth ranged from about 20 mg/kg dry weight (d.w.) of soil in the top (plow) layer to less than 0.1 mg/kg d.w. at 1 m depth. The concentrations varied also spatially, up to one order of magnitude within the same field and showing a decreasing trend from the Hg source (i.e., irrigation ditches). The concentration profiles and gradients measured were explained considering Hg loading, soil properties, such as the texture, organic carbon content, pH and cation exchange capacity. A Selective Sequential Extraction (SSE) was also applied on soil samples from an ad hoc greenhouse experiment to investigate the role of different plant species in influencing Hg speciation in soils. Although most of the extracted Hg was included in scarcely mobile or immobile forms, some plant species (i.e., alfalfa) showed to importantly increase the soluble and exchangeable fractions with respect to the unplanted control soils, thus affecting mobility and potential bioavailability of Hg.

Heavy metal contamination has been threatening the health of human beings. To decrease the bio-toxicity of heavy metals, a thiol-functionalized nano-silica (SiO₂-SH) was adopted to remediate the soil contaminated by lead (Pb), cadmium (Cd) and copper (Cu). The remediation effect of SiO₂-SH on contaminated soils was investigated by the uptake of the heavy metals into lettuce and pakchoi in pot experiment. The bio-toxicity of the SiO₂-SH was evaluated, and its immobilization mechanisms were proposed by the fraction distribution of Cd, Pb and Cu. It was found that the SiO₂-SH can significantly reduce the uptake of Cd, Pb, Cu into pakchoi by 92.02%, 68.03%, 76.34% and into lettuce by 89.81%, 43.41%, 5.76%, respectively. The chemical species analyses of Cd, Pb, Cu indicate SiO₂-SH can transform the heavy metal in acid soluble states into reducible fraction and oxidizable fraction, thereby inhibiting the extraction of heavy metals into soil solution. The concentrations of microbial biomass carbon, organic matter, and cation exchange capacity of the soil increased while the soil bulk density decreased after remediation. Those changes demonstrate that SiO₂-SH not only has no bio-toxic impact on the soil environment but also improves the soil environment, which proves the prepared SiO₂-SH is environmental-friendly. The SiO₂-SH could be a promising amendment for heavy metal contaminated soils.

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.

Heavy metals contamination in agricultural soil has become a worldwide problem, and soil characteristics modulate metal availability in soils. Four field experiments were conducted simultaneously to evaluate concentration and distribution of cadmium (Cd) and lead (Pb) in 39 oilseed rape cultivars at four agricultural locations with different contamination levels of Cd and Pb, as well as the influence of soil characteristics together with soil total and bioavailable Cd and Pb concentration on metal transfer from soil to oilseed rape. Shoot concentrations of Cd and Pb in oilseed rape cultivars ranged from 0.09 to 3.18 and from 0.01 to 10.5 mg kg⁻¹ across four sites. For most cultivars, Cd concentration in root or shoot were higher than pod and lowest in seed, while the highest Pb concentration was observed in root followed by shoot and seed. Stepwise multiple linear regression analysis allows for a better estimation of Cd and Pb concentration in oilseed rape while taking soil properties into consideration. The results demonstrated that Cd and Pb concentration in oilseed rape were correlated with soil organic matter (OM), cation exchange capacity (CEC), available phosphorus (AP), available potassium (AK), sand, soil total and available Cd and Pb concentration, and R² varied from 0.993 to 0.999 (P < 0.05). The Cd and Pb levels found in oilseed rape indicated its phytoextraction potential for Cd and Pb co-contaminated agricultural soils in winter without stopping agricultural activities.

In China, the cadmium (Cd) levels in paddy fields have increased, which has led to the excessive uptake of Cd into rice grains. In this study, we determined the physicochemical properties of soil samples, including the pH, soil organic matter (SOM) content, cation exchange capacity (CEC), and total Cd content (Cdsoil) in order to establish a quadratic discriminant analysis (QDA) model for assessing the risk of Cd in rice and to calculate its prior probability. Decision tree and logistic regression models were also established for comparison. The results showed that the accuracy rate was 74% with QDA, which was significantly higher than that obtained using the decision tree (67%) and logistic regression (68%) models. The correlation coefficients between the soil pH and the other three factors (CEC, SOM, and Cdsoil) were higher in the inaccurate set than the accurate set, whereas the correlation coefficients were smaller in the inaccurate set than the accurate set.

In situ remediation technology applied aims to not only decrease cadmium (Cd) and arsenic (As) uptake by rice but also improve soil health and rice quality in contaminated paddy soils. Here the effects of a combined amendment, consisting of limestone, iron powder, silicon fertilizer, and calcium-magnesium-phosphate fertilizer, with three application rates (0, 450, and 900 g m⁻²) on soil health, rice root system, and brown rice quality were compared in moderately versus highly Cd and As co-contaminated paddy fields. After the amendment application, soil pH, cation exchange capacity, four kinds of soil enzyme activities increased (sucrase, urease, acid phosphatase, and catalase), and concentrations of leached Cd/As decreased, as measured by the DTPA (diethylene triamine pentaacetic acid) and TCLP (toxicity characteristic leaching procedure). Changes in the above soil indicators promoted soil health. In both fields, the dithionite-citrate-bicarbonate (DCB)-Fe and DCB-Mn concentration in iron plaque increased and root length became longer. Changes in the above root system indicators reduced the root system's absorption of Cd and As but increased that of nutrients. Under 900 g m⁻² treatment, the Cd concentration in brown rice of two sites decreased by 55.8% and 28.9%, likewise inorganic As (iAs) decreased by 50.0% and 21.1%, whereas essential amino acids increased by 20.4% and 20.0%, respectively. Furthermore, the Cd and iAs concentrations in brown rice were <0.2 mg kg⁻¹ (maximum contaminant level of Cd and iAs in the Chinese National Food Safety Standards GB2762-2017 for brown rice) under the 900 g m⁻² in the moderately contaminated field. These results suggest the combined amendment can improve soil health and brown rice quality in the moderately and highly Cd- and As-co-contaminated paddy soils, offering potential eco-friendly and efficient remediation material for applications in such polluted paddy soils.

The bioavailability of chromium (Cr) in soils is highly dependent on Cr fractions and soil physicochemical properties, but it is still unclear how the Cr fractions change in different soils. In this study, phytotoxicity to wheat root elongation was evaluated in different soils across China, and the kinetics of the biogeochemical processes of the added Cr(VI) were examined. After 105 days of soil Cr(VI) spiking, the added Cr(VI) causing 10% inhibition (EC₁₀) of wheat root elongation varied greatly in soils (0.92–151.12 mg kg⁻¹). The results of correlation analysis between EC₁₀ and soil properties showed that the toxicity of Cr was affected by pH, organic matter (OM), clay, cation exchange capacity (CEC), and amorphous Fe oxides. Moreover, the correlation analysis showed that wheat root elongation was more sensitive to extracted Cr(VI) than Cr(III) after 105 days of incubation. A kinetic model was established to evaluate the redox and aging-activating reactions of Cr(VI)/(III) over 105 days. The correlation analysis between the soil properties and rate constants of the model showed that the pH, clay, and amorphous Fe/Al oxides might be the key factors controlling the aging and reduction processes of Cr(VI), and the OM and CEC might greatly affect the aging process of Cr(III). This modeling study is helpful in understanding which soil properties control the transformation and toxicity of Cr in soils.

Acidification in variable charge soils is on the rise due to increased acid deposition and use of nitrogenous fertilizers. The associated low pH and cation exchange capacity make the soils prone to depleted base cations and increased levels of Al³⁺. Consequently, Al toxicity to plants and soil infertility decrease crop yield. This study was designed to investigate the effect of Pseudomonas fluorescens on the acidification of two Ultisols. The simulated acidification experiment demonstrated that the pH of bacteria-treated soil was higher than that of control under similar conditions, suggesting that the adhered bacteria inhibited soil acidification. This observation was attributed to the association of organic anions (RCOO⁻ or RO⁻) on bacteria with H⁺ to form neutral molecules (RCOOH or ROH) and reducing the activity of H⁺ in solution. The bacteria also inhibited the increase in soil soluble Al and exchangeable Al during soil acidification. The adhesion of bacteria on the soils increased soil effective cation exchange capacity (ECEC) and exchangeable base cations at each pH compared to control. The release of exchangeable base cations from bacteria-treated soil, and the decrease in soil ECEC and exchangeable base cations with decreasing pH confirmed that protonation of organic anions on adhered bacteria was mainly responsible for the inhibition of soil acidification. The change of zeta potential of the bacteria with pH and the ART-FTIR analysis at various pH provided more evidence for this mechanism. Therefore, the bacteria in variable charge soils played an important role in retarding soil acidification.

Despite common knowledge that the metal content adsorbed by fine particles is relatively higher compared to coarser particles, the reasons for this phenomenon have gained little research attention. The research study discussed in the paper investigated the variations in metal content for different particle sizes of solids associated with pollutant build-up on urban road surfaces. Data analysis confirmed that parameters favourable for metal adsorption to solids such as specific surface area, organic carbon content, effective cation exchange capacity and clay forming minerals content decrease with the increase in particle size. Furthermore, the mineralogical composition of solids was found to be the governing factor influencing the specific surface area and effective cation exchange capacity. There is high quartz content in particles >150 μm compared to particles <150 μm. As particle size reduces below 150 μm, the clay forming minerals content increases, providing favourable physical and chemical properties that influence adsorption.

Soil washing using a strong chelating agent is a common practice for restoring contaminated soils, but significant soil fertility degradation and high operation costs are the major disadvantages. Washing soil with a dissolved organic matter (DOM) solution has been identified as a method that can moderate the loss of nutrients in the soil and enhance metal removal. The DOM solutions were extracted from waste sludge obtained from a local whisky distillery. Single chelating washing and chelate-DOM washing were carried out using ethylenediaminetetraacetic acid (EDTA), citric acid, and DOM solutions to remediate highly Cu-contaminated soil. Two-phase washing using 0.34 M citric acid and then 1500 mg L−1 DOM solution (pH 8.5) was found to be most favorable for the soil. With this treatment, 91% Cu was removed from the topsoil; the organic matter, cation exchange capacity, plant-available nitrogen, and available phosphate content increased by 28.1%, 103%, 17.7%, and 422%, respectively.