Polycyclic aromatic hydrocarbons (PAHs), abundant in mixed contaminant sites, often coexist with heavy metals. The fate and remediation of PAHs depend heavily on the sorption and desorption behavior of these contaminants. The sorption behavior can in turn be highly affected by certain soil components and properties, such as soil organic matter (SOM) and the presence of heavy metals. Through review of the literature focused on research from 2006 to 2018, this paper discusses interactions, challenges, influencing factors and potential synergies in sorption/desorption of mixed PAHs and heavy metal contamination of soil. The presence of either natural organic matter or heavy metals can enhance the sorption capability of fine soil, retarding the PAHs in the solid matrix. The co-existence of SOM and heavy metals has been reported to have synergistic effect on PAHs sorption. Enhanced and surfactant desorption of PAHs are also affected by the presence of both SOM and metals. Remediation techniques for PAHs removal from soil, such as soil washing, soil flushing and electrokinetics, can be affected by the presence of SOM and heavy metals. More detailed studies on the simultaneous effects of soil components and properties on the sorption/desorption of PAHs are needed to enhance the effectiveness of PAHs remediation technologies.

Accumulation of potentially toxic elements (PTEs) in agricultural soils has become an increasingly global issue driven by industrialization. A credible knowledge of their distribution and diverse sources in soils is essential to developing effective measures of identifying accumulation of PTEs in rural and periurban environments. However, the assessment of PTE pollution levels and discrimination of anthropogenic and natural sources remain a serious challenge. In China, most studies are focused on highly industrialized and/or urbanized regions, while limited attention has been given to agricultural areas where diffuse source contamination prevails. Therefore, a large dataset of 5207 surface soil samples (1 × 1 km) and 1311 subsoil samples (2 × 2 km) were collected from an agriculturally dominated region in eastern China. Soil total concentrations of As, Cd, Cr, Cu, Hg, Ni, Pb and Zn were analyzed along with additional edaphic variables relevant to PTE accumulation in soils (e.g., pH, SOC). Concentrations of Cr, Ni, Pb and Zn for all sites were lower than those of the risk-screening values. However, elevated concentrations of Cd and Hg observed in surface soils were associated with anthropogenic activities. Land use pattern had a significant impact on the spatial variation of PTEs. Elevated levels of Cd were uniquely associated with high phosphorus and soil organic matter (SOM) contents, and elevated Hg was associated with coal-fired power plants and historical application of fertilizer and Hg-containing pesticides. The data presented herein indicated that geogenic process likely caused a net depletion of As, Cr, Cu, Ni, Pb and Zn in topsoil, despite surface deposition from anthropogenic sources. The result of this study revealed that using subsoil concentrations of PTEs to establish background or reference concentrations might lead to an erroneous assessment of pollution levels in surface soils.

Chromium (Cr) is a toxic element among which hexavalent chromium [Cr(VI)] is more toxic than trivalent chromium [Cr(III)]. Chromium can be reduced or oxidized in soil because soil is a complex medium and various soil components affect redox reaction of Cr in soil. Therefore, Cr speciation in hydroponics and soil was compared and Cr uptake and speciation by lettuce grown in the media were evaluated. Higher phytotoxicity was found in Cr(III) spiked soil than in Cr(VI) spiked soil, while Cr toxicity was higher in Cr(VI) treated hydroponics than Cr(III) treated hydroponics. Chromium was mainly accumulated in lettuce roots as Cr(III), and more Cr was translocated from roots to shoots grown in Cr(VI) treated hydroponics than Cr(III) treated hydroponics. Accumulation of Cr in roots grown in Cr(III) treated nutrient solution reduced Fe, K, Ca, Mg, and P uptake in lettuce. Chromium valence state was Cr(III) in lettuce leaves and roots grown in both Cr(III) and Cr(VI) treated hydroponics and soil. Chromium speciation in hydroponically grown lettuce roots was Cr(III) coordinated with 6 oxygens in the first shell and 2 or 4 carbons in the second shell as analyzed by X-ray absorption spectroscopy (XAS), which was similar to chromium acetate. The valence state of Cr in Cr(III) and Cr(VI) treated nutrient solution was not changed, while Cr(VI) was reduced to Cr(III) in Cr(VI) spiked soil by soil organic matter. Spiking of Cr(III) induced reduction of Mn in soil, which resulted in an increase of bioavailable Mn concentration in the Cr(III) spiked soil. Therefore, the increased phytotoxic effect for lettuce in Cr(III) spiked soil can be attributed to the reduction of Mn and subsequent release of Mn(II). For Cr(III) contaminated soil, Mn speciation should be considered, and bioavailable Mn concentration should be monitored although Cr existed as Cr(III) in soil.

Environmental complexity leads to differences in the spatial distribution of heavy metal pollution in soil and rice. Such spatial differences will seriously affect the safety of planted rice and can impact regional management and control. How to scientifically reveal these spatial differences is an urgent problem. In this study, the spatial mismatch relationship between Cd pollution in soil and rice grains (brown rice) was first explored by the interpolation method. To further reveal the causes of these, the specific recognition rules of the spatial relationship of Cd pollution were extracted based on a decision tree model, and the results were mapped. The results revealed a spatial mismatch in Cd pollution between the soil and rice grains in the study area, and the main results are as follows: (i) slight soil pollution and safe rice accounted for 68.88% of the area; (ii) slight soil pollution and serious rice pollution accounted for 13.39% of the area and (iii) safe soil and serious rice pollution accounted for 11.63% of the area. In addition, 11 recognition rules of Cd spatial pollution relationship between soil and rice were proposed, and the main environmental factors were determined: SOM (soil organic matter), Dis-residence (distance from residential area), soil pH and LAI (leaf area index). The average accuracy of rule recognition was 75.90%. The study reveals the spatial mismatch of heavy metal pollution in soil and crops, providing decision-making references for the spatial accurate identification and targeted prevention of heavy metal pollution spaces.

This study describes the development of a sequential extraction procedure for the evaluation of metal nanoparticle mobility and bioaccessibility in soils. The procedure, that was developed using gold nanoparticles (AuNPs) as model species, relies on the fractionation of nanoparticles by sequentially dissolving soil matrix components (carbonates, metal oxides, organic matter and mineral phases) in order to release the entrapped nanoparticle species in the extract solution. By summing up the concentration of AuNPs recovered in each fraction it was found that 93.5% of the spiked AuNP concentration could be recovered which satisfactorily represents the nominal AuNP concentration in the soil. The efficiency of the procedure was found to depend on several procedural artifacts related to the separation of AuNPs from soil colloids and the reactivity of the extraction reagents with AuNPs and their precursor metal ions. Based on the results obtained a protocol for the speciation of the AuNPs and Au ions in the soil sample was also developed. The results of the study show that both AuNPs and Au ions are mainly associated with soil organic matter, which significantly reduces their mobility, while a small amount (<10%) is associated with metal oxides which are more mobile and potentially bioaccessible. The developed procedure provides a springboard for further development of sequential extraction procedures of metal nanoparticles in soils that could be used to assess both the exposure and release of metal nanoparticles and their precursor metal ions in the environment (as total extractable concentration) as well as provide evidence regarding their bioaccessibility and potential bioavailability by determining the concentration of nanoparticles in each specific soil fraction.

A high-resolution soil sampling has been applied to two forest podzols (ACB-I and ACB-II) from SW Europe in order to investigate the soil components and processes influencing the content, accumulation and vertical distribution of Hg. Total Hg contents (THg) were 28.0 and 23.6 μg kg⁻¹ in A horizons of ACB-I and ACB-II, then they strongly decreased in the E horizons and peaked in the Bhs horizons of both soils (55.3 and 63.0 μg kg⁻¹). THg decreased again in BwC horizons to 17.0 and 39.8 μg kg⁻¹. The Bhs horizons accounted for 46 and 38% of the total Hg stored (ACB-I and ACB-II, respectively). Principal component analysis (PCA) and principal components regression (PCR), i.e. using the extracted components as predictors, allowed to distinguish the soil components that accounted for Hg accumulation in each horizon. The obtained model accurately predicted accumulated Hg (R² = 0.845) through four principal components (PCs). In A horizons, Hg distribution was controlled by fresh soil organic matter (PC4), whereas in E horizons the negative values of all PCs were consistent with the absence of components able to retain Hg and the corresponding very low THg concentrations. Maximum THg contents in Bhs horizons coincided with the highest peaks of reactive Fe and Al compounds (PC1 and PC2) and secondary crystalline minerals (PC3) in both soils. The THg distribution in the deepest horizons (Bw and BwC) seemed to be influenced by other pedogenetic processes than those operating in the upper part of the profile (A, E and Bhs horizons). Our findings confirm the importance of soils in the global Hg cycling, as they exhibit significant Hg pools in horizons below the uppermost O and A horizons, preventing its mobilization to other environmental compartments.

Heavy metal contamination in protected-field vegetable production has aroused widespread concern and manure is considered to be one of the contamination sources. Little is known about its long-term effects on heavy metal pollution in uncontaminated soils. A 15-year protected-field vegetable production experiment was carried out with three manure treatments (chicken manure: cattle manure = 3:1) with high (HMAR), medium (MMAR) and low (LMAR) application rates to evaluate the long-term risks of heavy metal pollution. It was found that continuous and high manure application rates significantly increased the total concentrations of soil Cd, Zn, Cr, and Cu rather than Pb, Ni or As. The high application rate of manure also increased soil available heavy metals although the soil organic matter was increased as well. Though total soil Cd under the HMAR exceeded the threshold of national soil standard, Cd content in tomato and fennel still complied with the food safety requirements of vegetables. Generally, the accumulation rates of soil Zn, Cu, and Cr with 1 t⋅ha⁻¹ of manure application in three treatments were ranked by HMAR < MMAR < LMAR. Based on the results of the ratio of heavy metal accumulation risk (RAR), Zn, Cu, and Cr under HMAR and Cd and Zn under MMAR would exceed their soil threshold values within 100 years and RAR could be a useful indicator for monitoring the long-term risk of soil heavy metal pollution. Recommended manure application rates to guarantee a 100-year period of clean production were 44, 74, and 63 t⋅ha⁻¹⋅yr⁻¹ for Zn, Cu, and Cr, respectively. Measurements should be taken to minimize the risk of heavy metals (Cd, Zn, Cr, and Cu) pollution sourced from manure to ensure food safety and ‘cleaner’ protected-field vegetable production.

The accurate assessment of soil selenium (Se) bioavailability is crucial for Se biofortification in Se-deficient areas and risk assessment in selenosis areas. However, a universally accepted approach to evaluate Se bioavailability in soil is currently lacking. This research investigated Se bioavailability in six soils treated with selenite (Se(IV)) or selenate (Se(VI)) by comparing diffusive gradients in thin-films (DGT) technique and chemical extraction methods through pot experiments. A bioindicator method was used to evaluate Se concentrations in pak choi and compare the results with the Se concentration measured by other methods. Results showed that chemical extraction methods presented different extraction efficiencies for available Se over a range of soil types, and the same extraction method had various extraction efficiencies for different Se species in the same soil. DGT measured Se concentrations (CDGT−Se) for Se(VI) treatment were 2.3–34.1 times of those for Se(IV) treatment. KH2PO4–K2HPO4 and AB-DTPA extractable Se could predict the bioavailability of soil Se, but they were disturbed by soil properties. HAc extraction was unsuitable for evaluating Se bioavailability in different Se(IV)-treated soils. By contrast, DGT technique was preferable for predicting plant uptake of Se(IV) over chemical extraction methods. Although DGT technique was independent of soil properties, KH2PO4–K2HPO4 extraction provided the best fitting regression equation for Se(VI) when it was dependent on soil organic matter. Thus, KH2PO4–K2HPO4 extraction may be preferred to assess Se(VI) bioavailability in different soil types on a large scale.

Rapeseed (Brassica napus L.) is a winter oil crop and biodiesel resource that has been widely cultivated in the southern part of China. Applying rapeseed residue (RSD) to summer rice fields is a common agricultural practice under rice−rapeseed double cropping systems. However, in Cd−contaminated paddy fields, the influence mechanisms of this agricultural practice on the migration and distribution of Cd fractions in soil are not clear. Therefore, a field experiment was carried out to analyse the changes in soil pH, organic matter (OM), microbial biomass carbon (MBC) and nitrogen (MBN), enzyme activity (urease (UA), acid phosphatase (ACP), and dehydrogenase (DH)), Cd distribution fractions, and Cd concentration in rice tissues after RSD application. The results showed that RSD treatment significantly increased the soil OM and MBC concentrations and UA, ACP, and DH activities, decreased the soil acetic acid−extractable fraction of Cd (ACI–Cd), and increased the reducible fraction of Cd (Red–Cd). The formation of stable organic complexes and chelates upon application of RSD is a result of the high affinity of Cd for soil OM. The activities of soil ACP, DH and MBC can well reflect Cd ecotoxicity in soil, particularly the DH activity. In addition, RSD application was helpful in inducing iron plaque formation. The “barrier” effect of iron plaque resulted in reduced Cd accumulation in different tissues of rice. The health risk of rice consumption also decreased as a result of RSD application; it decreased by 0.89–30.0% and 24.1–51.7% in the two tested fields. Overall, the application of RSD was increased soil OM, microbial biomass, and enzyme activity, and these changes was instrumental in reduce the risk of cadmium pollution in rice fields.

The aim of this study was to elucidate the effects of apricot shell-derived biochar (ASB) and apple tree-derived biochar (ATB) on soil properties, plant growth, microbial communities, enzymatic activities, and Zn and Cd fractionation and phytoavailability in mining soils. Smelter soil contaminated by Zn (1860.0 mg kg⁻¹) and Cd (39.9 mg kg⁻¹) was collected from Fengxian, China, treated with different doses (0 (control), 1, 2.5, 5, and 10% w/w) of both biochars and cultivated by Brassica juncea in a greenhouse pot experiment. The acid-soluble, reducible, oxidizable, and residual fraction and plant tissue concentrations of Zn and Cd were determined. Biochar addition improved plant growth (22.6–29.4%), soil pH (up to 0.94 units), and soil organic matter (up to 4-fold) compared to the control. The ASB and ATB, particularly ATB, reduced the acid-soluble (21–26% for Zn and 15–35% for Cd) and the reducible (9–36% for Zn and 11–19% for Cd) fractions of Zn and Cd and altered these fractions in the organic and residual fractions. Therefore, the biochars decreased the metal concentrations in the roots (36–41% for Zn and 33–37% for Cd) and shoots (25–31% for Zn and 20–29% for Cd), which might be due to the increase in pH, biochar liming effects, and metal sorption by the biochar. The biochars impact on the bacterial community composition was selective. The ASB and ATB decreased the activities of soil β-glucosidase, dehydrogenase, and alkaline phosphatase while increasing the urease activity. The biochars, particularly ATB, can be considered as effective soil amendments for reducing the phytotoxicity of Zn and Cd in contaminated soils, improving plant growth, enhancing the abundance of specific bacterial groups and increasing urease activity; however, more attention should be paid to their negative effects on the activities of β-glucosidase, dehydrogenase, and alkaline phosphatase.