Bioavailability Of Heavy Metals In Soil Research Articles

Preparation and characterization of high-ash coal slime-based soil amendment as well as investigations of its adsorption performance and mechanisms towards heavy metals in soil

In this study, high-ash coal slime-based mineral soil amendment (MSA) was prepared via the hydrothermal method using high-ash coal slime as raw material, supplemented with activator calcium oxide and additive KOH solution. After hydrothermal treatment at 230 °C for 5 h, the original crystalline phase (quartz and kaolinite) of the high-ash slime was completely transformed into hydrotalcite zeolite, tobermorite, and silicate of potassium aluminosilicate, which has the largest specific surface area. The adsorption of Pb2+ and Cd2+ was adherent to the kinetic equation of secondary adsorption and Freundlich models, and the removal of Pb2+ and Cd2+ reached up to 362.58 mg g−1 and 64.67 mg g−1. The successive releases of SiO2 and CaO from MSA conformed to the Elovich equation, whereas the releases of SiO2 in Cd-containing environments and CaO in Pb- and Cd-containing environments more closely conformed to the power function; the releases of K2O all conformed to the first-order kinetic equation. The presence of Pb2+ and Cd2+ in the environment promotes the release of potassium and calcium elements with MSA's ion-exchange ability, and attenuates the release of silicon elements. Combining Pb2+ and Cd2+ with silicon resulted in the intolerant precipitation of 3PbO·2SiO2 and Cd2SiO4. The mineral precipitation mechanism is the most important mechanism of MSA in immobilizing heavy metals, accounting for 72.7%–80.5% of the total adsorption. Further contaminated soil immobilization experiments also showed that the application of MSA significantly reduced the bioavailability of soil heavy metals. When the MSA addition amount was 1.6%, the residual state increased by 63.58%. In conclusion, preparing MSA may effectively utilize coal-based solid waste with high added value.

Effects of freeze-thaw action on in vivo and in vitro bioavailability of arsenic in soils from derelict industrial sites

Arsenic is a metalloid with carcinogenic properties and has been classified as a Category I carcinogen by the International Agency for Research on Cancer (IARC). Freeze-thaw processes affect the migration and transformation of soil heavy metals, as well as adsorption/desorption and redox reactions. However, there is limited research directly addressing the impact of freeze-thaw processes on the bioavailability of soil heavy metals. In this study, we focused on As and selected As-contaminated soil samples from three types of legacy sites in heavy industrial areas. Under controlled freeze-thaw experimental conditions, we utilized both in vivo and in vitro bioavailability measurement methods to investigate whether and how freeze-thaw processes affect the bioavailability of soil As. The results of this study showed that freeze-thaw processes reduced soil pH (P < 0.05), CEC, SOM, and particle size, with decreases of 0.33, 1.2 cmol/kg, 5.2 g/kg, and 54 µm, respectively. It also increased weight specific surface area (BET) (P < 0.05), with an increase of 300 m2/kg. Freeze-thaw processes increased the proportions of exchangeable (P < 0.05), carbonate-bound, and iron-manganese oxide-bound As (P < 0.05), but reduced the proportions of organic-bound and residual As (P < 0.05). Freeze-thaw processes significantly increased the relative bioavailability and bioaccessibility of As, with increases of 32 ± 9.6% and 13 ± 0.23%, respectively. Soil pH, SOM, BET and electronic conductivity (EC) were identified as factors which could contribute to the increased bioavailability of As due to freeze-thaw processes. These results provide new insights and evidence for refining the assessment of human health risks associated with heavy metal contamination in polluted soils.

Sulfur fertilization and water management ensure phytoremediation coupled with argo-production by mediating rhizosphere microbiota in the Oryza sativa L.-Sedum alfredii Hance rotation system

Sulfur (S) fertilizers, water management and crop rotation are important agronomic practices, related to soil heavy metal bioavailability. However, the mechanisms of microbial interactions remain unclear. Herein, we investigated how S fertilizers (S0 and Na2SO4) and water management affected plant growth, soil cadmium (Cd) bioavailability, and rhizospheric bacterial communities in the Oryza sativa L. (rice)-Sedum alfredii Hance (S. alfredii) rotation system through 16S rRNA gene sequencing and ICP-MS analysis. During rice cultivation, continuous flooding (CF) was better than alternating wetting and drying (AWD). CF treatment decreased soil Cd bioavailability by the promotion of insoluble metal sulfide production and soil pH, thus lowering Cd accumulation in grains. S application recruited more S-reducing bacteria in the rhizosphere of rice, whilst Pseudomonas promoted metal sulfide production and rice growth. During S. alfredii cultivation, S fertilizer recruited S-oxidizing and metal-activating bacteria in the rhizosphere. Thiobacillus may oxidize metal sulfides and enhance Cd and S absorption into S. alfredii. Notably, S oxidation decreased soil pH and elevated Cd content, thereby promoting S. alfredii growth and Cd absorption. These findings showed rhizosphere bacteria were involved in Cd uptake and accumulation in the rice-S. alfredii rotation system, thus providing useful information for phytoremediation coupled with argo-production.

Amended compost alleviated the stress of heavy metals to pakchoi plants and affected the distribution of heavy metals in soil-plant system

With the development of the social economy, soil heavy metal pollution has become a common worldwide issue. Therefore, the remediation of soil heavy metal pollution is imminent. This study aimed to investigate the effect of amended compost on reducing heavy metal bioavailability in soil and relieving heavy metals stress on plants under Cu and Zn stress in a pot experiment. To model the restoration of heavy metal-polluted farming soil, conventional compost (CKw), activated carbon compost (ACw), modified biochar compost (BCw) and rhamnolipid compost (RLw) were utilized. The results showed that the application of amended compost could promote the growth and quality of pakchoi and enhance the stress ability of malondialdehyde and antioxidant enzymes to heavy metals. The distribution of Cu and Zn in different subcellular parts of pakchoi was also affected. The application of amended compost significantly reduced the heavy metals content in the shoot of pakchoi, among which the content of Cu and Zn in the shoot of pakchoi in RLw was significantly decreased by 57.29% and 60.07%, respectively. Our results can provide a new understanding for efficient remediation of contaminated farmland soil by multiple heavy metals.

New insight into the geochemical mechanism and behavior of heavy metals in soil and dust fall of a typical copper smelter

The desorption mechanism of heavy metals (HMs) in soil around the mining region are complex and affected by multiple pollution sources, including sewage discharge and atmospheric deposition. Meanwhile, pollution sources would change soil physical and chemical properties (mineralogy and organic matter), thus affecting the bioavailability of HMs. This study aimed to investigate the pollution source of HMs (Cd, Co, Cu, Cr, Mn, Ni, Pb, and Zn) in soil near mining, and further evaluate influence mechanism of dust fall on HMs pollution in soil by desorption dynamics processes and pH-dependence leaching test. Result presented that dust fall is the primary pollution source to HMs accumulation in soil. Additionally, the result of mineralogical analysis in dust fall revealed that quartz, kaolinite, calcite, chalcopyrite, and magnetite are the major mineralogical phases by XRD and SEM-EDS. Meanwhile, the abundance of kaolinite and calcite in dust fall is higher than in soil, which is the primary reason of higher acid-base buffer capacity of dust fall. Correspondingly, the weakened or disappeared of hydroxyl after the adding acid extraction (0–0.4 mmol· g−1) demonstrated that hydroxyl is the main participants of HMs absorption in soil and dust fall. These combined findings suggested that atmospheric deposition not only increases the pollution loading of HMs in soil, but also changes the mineral phase composition of soil, which would increase the adsorption capacity and bioavailability of HMs in soil. This is very remarkable that heavy metals in soil influenced by dust fall pollution could be released preferentially when soil pH is changed. The present results of this study would provide efficient and scientific targeted strategies for pollution control of HMs in soil near mining areas.

Earthworm-mediated nitrification and gut digestive processes facilitate the remobilization of biochar-immobilized heavy metals

Earthworms and biochar tend to have opposite effects on heavy metal bioavailability in soil. However, the influence and controlling process of earthworms on the immobilisation effect of biochar remain poorly understood. Through the co-cultivation of earthworms with rice-husk biochar and sludge biochar in heavy metal-contaminated soil and desorption experiments involving simulated earthworm gut, we explored the factors that earthworms influence the heavy metal immobilisation ability of biochar. Our results showed that rice-husk biochar and sludge biochar effectively immobilized heavy metals in soil, whereas earthworm activity mobilised heavy metals in biochar-treated soil, which weakens the immobilisation of biochar. The soil pH reduction effect of earthworms by increasing the abundance of soil ammonia-oxidising bacteria to promote soil nitrification is an important mechanism through which earthworms mobilise heavy metals; however, this process did not occur within 10 days of incubation. Nitrification inhibitors effectively inhibit the mobilisation of heavy metals in soil by earthworms. In addition, the bioavailability of heavy metals in earthworm casts was significantly higher than those in the surrounding soil and earthworm-free soil. Moreover, simulated earthworm gut fluid promoted the re-release of heavy metals from the soil and biochar particles. These results suggest that the gut digestion of earthworms is another important mechanism by which earthworms mobilise soil heavy metals and weaken the immobilisation of biochar. Therefore, earthworms weakened the immobilisation effect of biochar mainly by promoting nitrification to reduce soil pH and through gut digestion.

Polyethylene and poly (butyleneadipate-co-terephthalate)-based biodegradable microplastics modulate the bioavailability and speciation of Cd and As in soil: Insights into transformation mechanisms

Microplastics (MPs) that enter the soil can alter the physicochemical and biochemical properties of soil and affect speciation of heavy metals (HMs), thereby perturbing the bioavailability of HMs. However, the mechanisms underlying these effects are not understood. Therefore, we investigated the effects of MPs from poly (butyleneadipate-co-terephthalate)-based biodegradable mulch (BM) and polyethylene mulch (PM) in Cd- or As-contaminated soil on soil properties and speciation of HMs. MPs were characterised using Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The addition of MPs reduced the bioavailability of HMs in soil and promoted the transformation of HMs into inert fractions. The mechanisms underlying the reduction of the bioavailability of HMs in soils could be as follows: (1) the entry of MPs into the soil changed its properties, which reduced the bioavailability of HMs; (2) FTIR and XPS analyses revealed that the hydroxyl and carboxyl groups and benzene ring present on the surface of aged MPs stabilized complexes (As(V)-O) with As(V) may have directly reduced the bioavailability of As(V) in soil; (3) aged BM exposed more amounts and types of reactive functional groups and was more effective in stabilising soil HMs than PM. Overall, this study provides new insights regarding the complexation mechanisms of soil HMs by MPs from different plastic mulch sources.

Characteristics and DGT Based Bioavailability of Cadmium in the Soil-Crop Systems from the East Edge of the Dongting Lake, China.

Contamination of heavy metals (including the cadmium, Cd) in agricultural soils has become an increased issue, posing a threat to the crop safety and human health. In order to evaluate the contamination characteristics and bioavailability of Cd in the soil−crop systems from the East edge of the Dongting Lake, four kinds of agricultural products for typical crops (rice, peanut, sweet potato, and corn) and corresponding rhizosphere soils were collected and analyzed for the Cd concentrations. The technique of diffusive gradients in thin-films (DGT) was applied to evaluate the Cd bioavailability in the rhizosphere soils. Concentrations of Cd ranged from 0.04 to 2.95 mg/kg (average 0.24 mg/kg) with 73.9% sites above the background levels, especially for paddy soils. Cd concentrations in the agricultural products ranged from 0.01 to 2.19 mg/kg (average 0.18 mg/kg), with Cd enrichment observed in the peanut samples. No obvious correlations (R2 < 0.25) were observed between the Cd concentrations in the agricultural products and total Cd concentrations in the rhizosphere soils, this indicated that the total Cd concentrations in the soils cannot predict the concentrations in the agricultural products of crops. While the DGT measured Cd concentrations showed good correlations (R2 = 0.64−0.90) with the concentrations in the most agricultural products of crops, which may be used to evaluate the safety of the soil and further safety of the agricultural products of crops. Overall, DGT showed a good potential for prediction of heavy metal bioavailability in soil since the DGT technique can simulate the sustained supply of heavy metals from solid to liquid in the soils.

A bibliometric analysis and assessment of priorities for heavy metal bioavailability research and risk management in contaminated land.

Risk assessment has been recognized as an important tool for evaluating heavy metal pollution and providing risk-based information for decision makers. In order to accurately assess the risk of heavy metals in contaminated soil to human health, it is necessary to conduct bioavailability studies on heavy metals in soil. Bioavailability of heavy metals in soils and the implications for risk assessment and land management/remediation has evolved over the decades and now has considerable practical and economic implications internationally. This article aims to explore its evolution by undertaking a bibliometric analysis of the research fields which have addressed heavy metal bioavailability in soils, with a focus on the risk assessment of contaminated land and human exposure to soil-borne metals. Bibliometric analysis techniques are applied to monitor and assess the changing research literature on the bioavailability of heavy metals in contaminated soils. Over 5000 articles were found for the period 1979-2020. The purpose was not to perform an exhaustive literature review, but to draw out trends and patterns in the literature, and to make observations on past and current priorities. Key words were extracted from the analysis and the roles of different countries in driving the research literature identified. Three phases in literature/subject development were identified. Between 1979 and 2000 (initial phase, 213 articles), studies used extraction procedures and solubility studies to investigate the roles of soil properties on metal form/speciation and focused on bioavailability to (crop) plants in agricultural soils. Between 2001 and 2010 (slow development phase, 1105 articles), attention switched to metals introduced in soil amendments and wastes, metal impacts on soil microbial processes, and incorporating bioavailability in risk assessment. More rigorous techniques were being used, such as the diffusive gradients in thin films technique, to better understand kinetic and metal speciation in soils and the quantitative relationship to bioavailability. By 2011-2020 (rapid development phase, 3137 articles), research was being conducted in many countries (site specific, often industrially contaminated and urban sites), with a focus shift to health risk assessment, remediation, and bioavailability to various ecological receptors (e.g., humans and animals), with the development of many methods of bioavailability (e.g., simulated gastrointestinal tract enzymolysis methods). Some priorities for research on soil heavy metal bioavailability are identified.

Does freeze-thaw action affect the extractability and bioavailability of Pb and As in contaminated soils?

As global warming intensifies, there will be increased uncertainty as to the environmental behavior and risks from heavy metals in industrial/legacy contaminated sites in permafrost regions. Bioavailability has been increasingly used for human health risk assessment of heavy metals in contaminated soils. Soil heavy metal bioavailability depends on soil physicochemical properties, and freeze-thaw affects soil physical, chemical and biological processes. However it is not clear whether freeze-thaw has an effect on the bioavailability of soil heavy metals. In this study, soils contaminated with Pb and As were collected from 10 industrial sites in northeast China. Extractability and bioavailability of soil Pb and As were determined by the Tessier sequential extraction method and four in vitro gastron-intestinal simulation methods under control and freeze-thaw treatments. The aims were: to compare the results of extraction and bioavailability from laboratory experiments which artificially simulate freeze-thaw conditions against control soils; to explore the correlation between bioavailability of Pb/As and soil properties. Freeze-thaw significantly decreased soil pH, and increased the soil weight surface area. Freeze-thaw decreased the percentage in the residual fraction, and increased the percentage of Pb and As in the exchangeable fraction, carbonate-bound fraction, Fe-Mn oxides-bound fraction and organic-bound fraction, relative to control soils. Freeze-thaw significantly increased Pb and As bioavailability compared to the controls. Pb and As released in the gastric phase of the four methods was significantly higher than that in the intestinal phase. Further analysis of correlations between Pb and As bioavailability and soil properties indicated that total concentrations of Al, Fe and Mn, particle size, and weight surface area significantly correlated to Pb and As bioavailability. Overall, this study demonstrated that freeze-thaw did influence the bioavailability of soil heavy metals. It suggests the freeze-thaw action should be comprehensively considered in the human risk assessment of soil pollutants in permafrost regions.

The immobilization, plant uptake and translocation of cadmium in a soil-pakchoi (Brassica chinensis L.) system amended with various sugarcane bagasse-based materials

Many organic materials have been used to decrease heavy-metal bioavailability in soil via in-situ remediation due to its high efficiency and easy operation; meanwhile, cheap materials have also been pursued to decrease the cost of remediation. Agricultural wastes exhibit their potential in remediation materials due to their low cost; however, raw agricultural wastes have a low ability to immobilize heavy metals in soil. Attempts have been made to modify agricultural wastes to improve the efficiency of heavy-metal passivation. In this study, novel agricultural waste-based materials, raw sugarcane bagasse (SB), citric acid modified (SSB) and citric-acid/Fe3O4 modified (MSB) sugarcane bagasse at 0.5% and 1% addition rates, were compared for their effectiveness in soil Cd passivation and Cd accumulations in pakchoi plants in a 30-day pot experiment. The addition of SB did not decrease soil bioavailable Cd effectively and slightly decreased Cd accumulation in plant roots and leaves. In comparison, SSB and MSB exhibited a great potential to decrease the transformation, translocation and accumulation of Cd with the decrease being greater at 1% than 0.5% rate in the soil-pakchoi system. For example, the addition of SSB and MSB at 0.5% decreased the concentration of Cd in leaves by 10%, and 16%, and at 1% decreased the concentration by 25% and 30%, respectively. High pH and abundant functional groups of three amendments played important roles in Cd immobilization. The enhanced microbial activities might also contribute to Cd passivation. However, plant growth was decreased in the amended treatments except SSB at 0.5% rate. The results suggest that citric-acid-modified sugarcane bagasse at addition rate of 0.5% has a potential to immobilize Cd in soil and decrease Cd accumulation in edible part of pakchoi effectively without decreasing vegetable growth.

The mechanistic investigation of geochemical fractionation, bioavailability and release kinetic of heavy metals in contaminated soil of a typical copper-smelter

Identifying the bioavailability and release-desorption mechanism of heavy metals (HMs) in soil is critical to understand the release risk of HMs. Simultaneously, the mechanistic investigation of affecting the bioavailability of HMs in soil is necessary, such as the grain-size distribution and soil mineralogy. Herein, the bioavailability of HMs (Cu, Cd, Ni, Pb, and Zn) in different area soils near a typical copper-smelter was evaluated by the sequential extraction technique (BCR), diffusive gradients in thin-films (DGT), and DGT-induced fluxes in sediments (DIFS) model. Results showed that the HMs proportion of the residual fraction in all soils was the highest. The average bioavailability concentration (CDGT) of Cu and Cd in industrial soil was the highest, with 45.12 μg· L−1 and 9.06 μg· L−1. The result of DIFS model revealed that the decreased order of the mean value of desorption rate constant (K-1) was Cd > Zn > Ni > Cu > Pb, 5.91 × 10−5, 4.96 × 10−5, 2.89 × 10−5, 9.64 × 10−6, and 8.69 × 10−6, respectively. According to the spatial distribution of release potential (R-value), the release potential of labile-Cu in agricultural soil was the highest, which was mainly attributed to fertilizer application in farmland. Simultaneously, the reduced hydroxyl was also related to the agricultural activities, resulting in the weakened adsorption capacity of HMs by soil. Redundancy analysis (RDA) results showed that the bioavailability of Cd, Ni, and Zn was mainly driven by soil pH, while the bioavailability of Cu and Pb was primarily driven by dissolved organic carbon (DOC). Meanwhile, carbonate minerals had a positive correlation with the bioavailability of Cd, Ni, and Zn, which could promote the release of HMs in mining soil as chemical weathering progresses. In conclusion, this study provides a structured method which can be used as a standard approach for similar scenarios to determine the geochemical fractionation, bioavailability, and release kinetics of heavy metals in soils.

Effects on the complexation of heavy metals onto biochar-derived WEOM extracted from low-temperature pyrolysis

Biochar-derived water-extractable organic matter (WEOM) was obtained under low-temperature pyrolysis (300 °C) using corncob as raw material. WEOM may affect the mobility and bioavailability of soil heavy metals (HMs) through complexation when biochar was used for soil HM remediation. Herein, the characteristics of complexation between HMs (Cr(III) and Cu(II)) and biochar-derived WEOM were investigated by using spectroscopic techniques in conjunction with parallel factor (PARAFAC) analysis and two-dimensional correlation spectroscopy (2D–COS). Six components were identified by PARAFAC modeling, in which protein-, fulvic- and humic-like components accounted for 48.86%, 25.63% and 25.51%, respectively. A nonlinear model was employed to determine the conditional stability constant (KM) and total ligand concentration (CL) of WEOM-HM complexes. The log KM values were in the range of 4.02–5.04 for WEOM-Cr(III) and 4.04–6.58 for WEOM-Cu(II). The 2D–COS in conjunction with log-transformed synchronous fluorescence spectroscopy (SFS) suggested that WEOM components were preferentially complexed with HMs in the following order: 433/270, 433/335, 496/270, 496/335, 370/335, 433/402, 496/402, 335/290, 402/290 for Cr(III), and 290/280, 390/280, 433/280, 496/280, 433/335, 496/335, 390/335, 433/420, 496/402, 335/290, 316/290 for Cu(II). The results of 2D–FTIR–COS suggested a preferential bonding of Cr(III) to the C–N group of alkyl, and Cu(II) to the CO group of alcohols, ethers and esters. Meanwhile, the CO group of ethers and the CN group of alkyl indicated preferential susceptibilities for the addition of Cr(III) and Cu(II) at different concentrations. In addition, protein-like components had remarkably higher total ligand concentration (CL) than fulvic- or humic-like components.

Fraction distribution and bioavailability of soil heavy metals under different planting patterns in mangrove restoration wetlands in Jinjiang, Fujian, China

The mangrove restoration wetland project in Jinjiang Estuary, Fujian Province, was started in April 2014, and the wetland was restored using vegetation restoration technology. Prior to restoration, the area was a mix of Spartina alterniflora beaches, muddy beaches, and abandoned quarries, which were not environmentally robust. Six species of mangrove plants were used in the wetland, including Kandelia obovata, Aegiceras corniculatum, Avicennia marina, Acanthus ilicifolius, Bruguiera gymnorhiza, and Rhizophora stylosa. The plants were planted according to three mixed patterns and three planting densities. Finally, the whole wetland was divided into 27 plots, and three plant-free control areas were set up in the area close to the vegetation area. In this study, 30 topsoil samples were collected (April 2019), fraction concentrations of heavy metals (Cu, Cr, Zn, and Pb), and their bioavailability and spatial distributions were determined, and the relationships between their fractions and planting patterns were analyzed. The results showed that among the nine planting patterns, the pattern “A-K-C, 0.5×0.5 m” was the most different from the other models, and the fraction of most heavy metals obtained the lowest value of soil metal content in this model. The secondary-phase fraction (SPF) of heavy metals, including acid-soluble, reducible, and oxidizable fractions, is considered to be a direct and potentially hazardous fraction to organisms. In this study, Cu, Zn, and Pb had the greatest SPFs among all the metals (35.29, 33.45, and 51.58%, respectively). Compared with the relevant results before restoration, it was found in after five years of mangrove restoration, the SPF of Cu, Cr, Zn and Pb decreased by 41.31, 22.89, 27.06, and 22.13%, respectively, indicating that the direct and potential toxicity of these four elements to the environment decreased. The risk of heavy metal release decreased from medium and high pollution levels to low pollution levels or even no pollution levels. For most metals, the fraction distributions were controlled by clay, silt, pH, and soil organic matter. The research methods and results can provide a theoretical and scientific basis for further study of wetland vegetation, and in addition, aid in selecting feasible restoration methods for further wetland restoration.

Study on the complexation of heavy metals onto biogas slurry DOM using two-dimensional correlation spectroscopy combined with the log-transformed synchronous fluorescence spectroscopy.

The fluorescent components of dissolved organic matter (DOM) in biogas slurry can react with heavy metals (HMs) and affect the migration, transformation, toxicity, and bioavailability of HMs in soil. Fluorescence quenching titration combined with two-dimensional correlation spectroscopy (2D-COS) can reveal the binding mechanism between HMs and different fluorescent components of biogas slurry DOM. The logarithmic-transformed (log-transformed) 2D-COS can be used to decrease the difference in the fluorescence intensity between low-intensity and high-intensity fluorophores that provides a better insight into the binding mechanism between biogas slurry DOM and HMs. Synchronous maps suggest that protein-like substances are more susceptive to the variation of the concentration of metal ions than fulvic-like substances. Asynchronous maps show that the preferential bonding of Cu(II) and Cr(III) to humic-like substances can be found in the biogas slurry DOM, as well as Fe(III) and Pb(II) to protein-like materials. DOM-Cu(II) may lead to an increasing risk of the migration of Cu(II) from soil to water environment due to the low log K values in the range from 2.93 to 3.46. Protein-like substances can also increase the environmental risk of HMs when these low-stable complexes occur migration and transformation. The potential environmental risk of protein-like with HMs follows the order: Pb(II) > Cu(II) > Cr(III). Here we demonstrate that the log-transformed 2D-COS can also identify fluorescence components at longer wavelength with relatively low content and reveals their preferential binding sequence and the number of binding sites. The study on the complexation between biogas slurry DOM and HMs provides a scientific basis for the environmental chemical behavior of HMs after the application of biogas slurry in agricultural soils.

Decrease in bioavailability of soil heavy metals caused by the presence of microplastics varies across aggregate levels

Microplastics can alter the physicochemical and biogeochemical processes in soil, but whether these alterations have further the effects on the transformation of soil heavy metal speciation, and if so, whether these effects vary across soil aggregate levels remain unknown. Herein, long-term soil culture experiments and soil fractionation are combined to investigate the effects of microplastics on chemical speciation of Cu, Cr, and Ni with different particle-size soil aggregates. Results show that microplastics in soil decrease the exchangeable, carbonate-bound, and Fe-Mn oxide-bound fractions of metals but increase their organic-bound fractions via direct adsorption and indirect effects on the soil microenvironment conditions. The findings suggest that microplastics can promote the transformation of heavy metal speciation from bioavailable to organic bound. Such promotion exerts notable differences across soil aggregate levels. The transformation of soil heavy metal speciation is greater in larger aggregates than in smaller aggregates in the early incubation period with microplastics but shows the opposite trend in the later incubation period. Therefore, this process is more sensitive to long-term microplastic pollution in smaller aggregates than in larger aggregates, most likely owing to the lag in the influence of microplastics on metal speciation transformation in the smaller aggregates.

Effects of sodium sulfide application on the growth of Robinia pseudoacacia, heavy metal immobilization, and soil microbial activity in Pb-Zn polluted soil.

Sodium sulfide (Na2S) is usually used as an amendment in industrial sewage treatment. To evaluate the effects of Na2S on the growth of Robinia pseudoacacia (black locust), heavy metal immobilization, and soil microbial activity, the R. pseudoacacia biomass and nutrient content and the soil heavy metal bioavailability, enzyme activity, and arbuscular mycorrhizal (AM) fungal community were measured by a single-factor pot experiment. The Pb-Zn-contaminated soil was collected from a Pb-Zn mine that had been remediated by R. pseudoacacia for five years. Three pollution levels (unpolluted, mildly polluted, and severely polluted) were evaluated by the pollution load index. Na2S application increased the shoot biomass under severe and mild contamination. In soil, Na2S application decreased the bioavailable Pb and Zn contents under severe and mild contamination, which resulted in a decrease in the Pb and Zn content in R. pseudoacacia. However, Na2S application did not affect the total Pb content per plant and enhanced the total Zn content per plant because of the higher biomass of the plants under Na2S application. Increased phosphatase activity and increased available phosphorous content may promote the uptake of phosphorus in R. pseudoacacia. Moreover, Na2S application is beneficial to the diversity of AM fungi under mild and severe pollution. Overall, Na2S application has great potential for enhancing soil heavy metal immobilization, enhancing soil microbial activity, and improving the growth of R. pseudoacacia in polluted soils. Therefore, Na2S is suitable for use in Pb-Zn remediation to ameliorate environmental heavy metal pollution.

Influencing pathways of soil microbial attributes on accumulation of heavy metals in brassica (Brassica campestris L. ssp.chinensis var.utilis Tsen et Lee) leaves

Microbial attributes have a great impact on soil heavy metal bioavailability, yet their influencing pathway on heavy metal accumulation in crop plants remains elusive. This study was aimed to analyze the influencing pathways of microbial attributes, including microbial biomass C and N (MBC and MBN), basal soil respiration (BSR) along with the activities of catalase, urease, and sucrase, on heavy metals (i.e., Cd, Cr, Cu, Ni, Pb, and Zn) accumulation by brassica leaves. Based upon a field investigation close to electroplating factory outlets, 45 pairs of soil and brassica samples were analyzed in the laboratory. Concentrations of heavy metals in brassica leaves declined with sampling distances downstream from the outlets. Redundancy analysis indicated that bioavailable concentrations of Cr, Cu, Ni, and MBC along with catalase activity were the major variables influencing heavy metal accumulation in brassica leaves and accounted for 83% of the accumulation. MBC and catalase activity accounted for 17% of the heavy metal accumulation in brassica leaves. Stepwise regression indicated that catalase activity, MBC, and BSR significantly affected heavy metal accumulation in brassica leaves. Based on structural equation modeling, the pathway coefficient of microbial activities-brassica heavy metals and the pathway coefficient of microbial biomass-brassica heavy metals are 0.122 (P < 0.05), suggesting that these microbial attributes (i.e. MBC along with catalase activities and SBR) could affect heavy metal accumulation in brassica leaves directly. The pathway coefficients of microbial activities-bioavailable heavy metals-brassica heavy metals and microbial biomass-bioavailable heavy metals-brassica heavy metal were −0.541 (P < 0.001) and 0.453 (P < 0.001), respectively, indicating that increase of microbial activities inhibited heavy metal accumulation while increase of microbial biomass promoted heavy metal accumulation, in brassica leaves. These results suggested that heavy metal bioavailability played a mediating role in the influencing pathways of soil microbial attributes on heavy metals in brassica leaves.

Synergistic effects of biochar and processed fly ash on bioavailability, transformation and accumulation of heavy metals by maize (Zea mays L.) in coal-mining contaminated soil

In the paper, hydrothermally (HT) treated, sulfuric acid (H2SO4), and hydrochloric acid (HCl) washed fly ashes (FA) were used to examine the applied effects with and without biochar (BC) on the bioavailability of heavy metals (HMs) and growth of maize (Zea mays L.) plants in coal-mining contaminated soil. Addition of BC in combination with these processed fly ashes (PFA) significantly increased the soil pH, EC, and soil organic carbon (SOC). Individual application of BC and PFA increased the available contents of Mg, Mn, and Fe, while the combination of BC and PFA significantly decreased the bioavailability of HMs in soil compared to control. The BC + HT-FA and BC + H2SO4-FA were most efficient treatments followed by BC + HCl-FA in promoting plant growth parameters (i.e., fresh and dry biomass, root and shoot lengths), reduction in the uptake of HMs and increase in the uptake of macronutrients. The results established that the combined application of BC and PFA synergistically increased HMs immobilization and maize biomass yields. The lowest transfer rate (TR), bioconcentration factor (BCF), and translocation factor (TF) for Cr, Co, Ni, Cu, Zn, Cd, and Pb were detected in BC + HT-FA, followed by BC + H2SO4-FA and BC + HCl-FA treatments after 60 days of maize crop harvesting. It could be suggested that using BC along with PFA as a soil stabilizer may be a promising source to immobilize HMs in a coal-mining contaminated soil.

Red soil amelioration and heavy metal immobilization by a multi-element mineral amendment: Performance and mechanisms

This field study aims to identify the performance and mechanisms of red soil amelioration and heavy metal immobilization by a multi-element mineral amendment (MMA) mainly containing a mixture of zeolites (laumontite and gismondine), montmorillonite, gehlenite, grossular and calcium silicate powder. The results indicated that the acidity of red soil was neutralized, and the soil EC, CEC, and content of montmorillonite and illite were increased after application of MMA, improving the soil fertility as well as the ability of heavy metals immobilization. The high amounts and reactivity of dissolved and colloidal Fe provided by the ferralsol (red soil) combined with the abundant available Si, Ca, Mg, Na and K supplied by MMA, readily destabilizes kaolinite and facilitates the formation of 2:1 type clay minerals. Meanwhile, the application of MMA was effective in reducing the bioavailability of soil heavy metals due to the activated mineralogical compositions of MMA as well as the increase of pH and 2:1 type clay minerals in the soil, which significantly decreased the up-taking and accumulation of Cd, Pb, Cr and Hg in lettuce tissues (p < 0.05). Compared with the untreated soil, the plant height, the total yield and content of vitamin C in the edible parts of lettuce in MMA-treated soil was increased by 7.6%, 23.6%, and 12.8%, respectively. These results showed that MMA could be a promising amendment for red soil amelioration and heavy metal immobilization.