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Biochar is widely accepted as a green and effective amendment for remediating heavy metals (HMs) contaminated soil, but its long-term efficiency and safety changes with biochar aging in fields. Currently, some reviews have qualitatively summarized biochar aging methods and mechanisms, aging - induced changes in biochar properties, and often ignored the potential eco-environmental risk during biochar aging process. Therefore, this review systematically summarizes the study methods of biochar aging, quantitatively compares the effects of different biochar aging process on its properties, and discusses the potential eco-environmental risk due to biochar aging in HMs contaminated soil. At present, various artificial aging methods (physical aging, chemical aging and biological aging) rather than natural field aging have been applied to study the changes of biochar's properties. Generally, biochar aging increases specific surface area (SSA), pore volume (PV), surface oxygen-containing functional group (OFGs) and O content, while decreases pH, ash, H, C and N content. Chemical aging method has a greater effect on the properties of biochar than other aging methods. In addition, biochar aging may lead to HMs remobilization and produce new types of pollutants, such as polycyclic aromatic hydrocarbons (PAHs), environmentally persistent free radicals (EPFRs) and colloidal/nano biochar particles, which consequently bring secondary eco-environmental risk. Finally, future research directions are suggested to establish a more accurate assessment method and model on biochar aging behavior and evaluate the environmental safety of aged biochar, in order to promote its wider application for remediating HMs contaminated soil., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

A clear understanding of the allocation of Cd to grains is essential to manage the level of Cd in cereal diets effectively. Yet, debate remains over whether and how the pre-anthesis pools contribute to grain Cd accumulation, resulting in uncertainty regarding the need to control plant Cd uptake during vegetative growth. To this end, rice seedlings were exposed to 111 Cd labeled solution until tillering, transplanted to unlabeled soils, and grown under open-air conditions. The remobilization of Cd derived from pre-anthesis vegetative pools was studied through the fluxes of 111 Cd-enriched label among organs during grain filling. The 111 Cd label was continuously allocated to the grain after anthesis. The lower leaves remobilized the Cd label during the earlier stage of grain development, which was allocated almost equally to the grains and husks + rachis. During the final stage, the Cd label was strongly remobilized from the roots and, less importantly, the internodes, which was strongly allocated to the nodes and, to a less extent, the grains. The results show that the pre-anthesis vegetative pools are an important source of Cd in rice grains. The lower leaves, internodes, and roots are the source organs, whereas the husks + rachis and nodes are the sinks competing with the grain for the remobilized Cd. This study provides insight into understanding the ecophysiological mechanism of Cd remobilization and setting agronomic measures for lowering grain Cd levels., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Microbial co-metabolism is crucial for the efficient biodegradation of polycyclic aromatic hydrocarbons (PAHs); however, their intrinsic mechanisms remain unclear. To explore the co-metabolic degradation of PAHs, root organic acids (ROAs) (phenolic ROAs: caffeic acid [CA] and ferulic acid [FA]; non-phenolic ROAs: oxalic acid [OA]) were exogenously added as co-metabolic substrates under high (HFe) and low (LFe) iron levels in this study. The results demonstrated that more than 90% of PAHs were eliminated from the rhizosphere of Phragmites australis. OA can promote the enrichment of unrelated degrading bacteria and non-specific dioxygenases. FA with a monohydroxy structure can activate hydroxylase; however, it relies on phytosiderophores released by plants (such as OA) to adapt to stress. Therefore, non-specific co-metabolism occurred in these units. The best performance for PAH removal was observed in the HFe-CA unit because: (a) HFe concentrations enriched the Fe-reducing and denitrifying bacteria and promoted the rate-limiting degradation for PAHs as the enzyme cofactor; (b) CA with a dihydroxyl structure enriched the related degrading bacteria, stimulated specific dioxygenase, and activated Fe to concentrate around the rhizosphere simultaneously to perform the specific co-metabolism. Understanding the co-metabolic degradation of PAHs will help improve the efficacy of rhizosphere-mediated remediation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

The exploitation of ion-adsorption rare earth element (REE) deposits has resulted in large quantities of abandoned mine tailings, which pose significant risks to the surrounding environment. However, the natural evolutional patterns at early successional stages and related biogeochemical dynamics (e.g. nutrient and REE cycling) on such mine tailings remains poorly understood. To this end, a chronosequence of REE mine tailings abandoned for up to 15 years was investigated in a post-mining site in south China. Our results showed that biocrusts were the earliest colonizers on these tailings, reaching a peak of 10% of surface coverage after 10 years of abandonment. Later on, after 15 years, the biocrusts began to be replaced by pioneer plants (e.g. Miscanthus sinensis), suggesting a rather rapid succession. This ecological succession was accompanied by obvious changes in soil nutrients and microbial community structure. Compared to bulk soils, both the biocrusts and rhizospheric soils favored an accumulation of nutrients (e.g. P, S, N, C). Notably, the autotrophic bacteria (e.g. Chloroflexi and Cyanobacteria) with C and N fixation abilities were preferentially enriched in biocrusts, while heterotrophic plant growth promoting bacteria (e.g. Pseudoocardiaceae and Acidobacteriales) were mainly present in the rhizosphere. Moreover, the biocrusts showed a remarkably high concentration of REEs (up to 1820 mg kg -1 ), while the rhizospheric soils tended to decrease REE concentrations (~400 mg kg -1 ) in comparison with bulk soils, indicating that the REEs could be redistributed by biological processes. Principal component analysis and mantel tests showed that the concentrations of nutrients and REEs were the most important factors affecting the microbial communities in biocrusts, rhizospheric and bulk soils. In sum, based on the observation of nutrient accumulation and pollutant (i.e. REE) dynamics in the initial successional stages, this work provides a feasible theoretical basis for future restoration practices on REE mine tailings., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

Basalt-derived soils are widespread worldwide. Such soils contain high levels of heavy metals like chromium (Cr), which is a serious environmental concern. However, little is known regarding the enrichment and speciation of Cr during the basalt weathering process. Therefore, two basalt-derived soil profiles (Nitisol and Ferralsol) in the Leizhou Peninsula, south tropical China, were investigated to explore the redistribution and transformation of Cr during basalt weathering. All profiles could be divided into three layers: rocks, saprolites, and soils. The Nitisol and Ferralsol profiles exhibited strong (kaolinization) and extreme (laterization) degrees of weathering, respectively. Results showed that Cr concentrations in the saprolites (234 to 315 mg·kg -1 ) were higher than those in basalt rocks (139 to 159 mg·kg -1 ), indicating that Cr was enriched with the continuous loss of Si and other mobile macro-elements. While high levels of Cr were also enriched in the soils (178 to 430 mg·kg -1 ) accompanied with Fe. However, in the upper soils of the Ferralsol profile, the acidity and organic matter could promote the leaching of Cr. Geochemical fractions and EPMA mapping showed that chromite and olivine were the main Cr-bearing minerals in basalt, but Fe-oxides (e.g., goethite and hematite) contained the highest portion of Cr in weathered saprolites and soils. The availability of Cr in the soil was extremely low due to the high stability of Cr bound to Fe-oxides. However, the decreasing contents of Cr bound to Fe-oxides in the upper soils of the Ferralsol profile indicated that Cr could also be released during Fe leaching. In conclusion, the weathering of basalt can lead to the enrichment of Cr in Fe-(hydro)oxides, which are the main controlling minerals for Cr mobility in basalt-derived soils. Further research is needed to evaluate the effect of Fe-(hydro)oxide formation and dissolution on the release of soil Cr., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The exploitation of ion-adsorption rare earth element (REE) deposits in South China has left large areas of mine tailings. However, limited remediation practices on these tailings have been reported, and how the remediation strategies and economic plants cultivation affect the biogeochemical cycles of nutrients, REEs and Al remains unclear. The aim of the present study was to investigate the effects of the combination of the addition of soil amendment and the root development and activity of a fiber plant ramie (Boehmeria nivea L.) on the availability and distribution of nutrients, as well as of REEs and other potentially toxic elements (e.g. Al) in the soil-plant system. The results showed that the application of organic amendment and ramie planting induced a significant increase in soil pH, total carbon (C), nitrogen (N), and other nutrient (e.g. P and Ca) concentrations, while led to a decrease of 80-90% and 60-90% in soil extractable REE and Al concentrations respectively. Matrices of correlation showed that soil pH, total C, N, and P concentrations were among the most important factors controlling the availability of soil REEs and Al, and root characteristics (e.g. fine root length). The total C, N, P and extractable nutrient concentrations, and electrical conductivity were higher in the rhizosphere soils of ramie than those in the bulk soils. Moreover, more than 60% of the quantity of REE and Al in the whole ramie plant was stored within the thick roots. These results showed that, in addition to amendment, the effects induced by the roots of ramie could further improve soil properties through C input, nutrient mobilization and toxic element stabilization. Our study concludes that ramie planting with organic amendment is a promising phytostabilization strategy for the remediation of REE mine tailings in South China., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The plant Phytolacca americana L. simultaneously hyperaccumulates manganese (Mn) and rare earth elements (REEs), but the underlying mechanisms are largely unknown. In this study, P. americana and the corresponding rhizosphere soil samples were collected from an ion-adsorption REE mine area in China, and the elemental composition and soil properties were analyzed in order to explore the relationship between metal accumulation and soil properties. The results show that P. americana accumulates high concentrations of REEs (up to 1040 mg kg -1 ), Mn (up to 10400 mg kg -1 ) and aluminum (Al) (up to 5960 mg kg -1 ) in leaves. The REE concentrations in leaves were positively correlated with those of Al, Fe and Zn, while light REE concentrations were negatively correlated with P concentrations (p < 0.05). The soil properties explained 81.7%, 72.9% and 67.1% of REEs, Mn and Al accumulated in P. americana, respectively. The variation of REE accumulation in P. americana was primarily explained by plant available P (24.4%), pH (12.9%), TOC (9.4%) and total P (7.7%). The accumulation of Mn was primarily explained by plant available REEs (42.9%) and available Al (13.1%) while Al in P. americana was primarily explained by soil pH (14.4%). This study suggests the potential by regulation of soil properties in improving the efficiency of phytoextraction for REEs by hyperaccumulators., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

In-situ remediation of heavy-metal-contaminated soil in farmland using phytostabilization combined with soil amendments is a low-cost and effective technology for soil pollution remediation. In this study, coconut shell biochar (CB, 0.1% and 0.5%), organic fertilizer (OF, 3.0%), and Fe-Si-Ca material (IS, 3.0%) were used to enhance the phytostabilization effect of ramie ( Boehmeria nivea L.) on Cd and Pb in highly polluted soils collected at Dabaoshan (DB) and Yangshuo (YS) mine sites. Results showed that simultaneous application of CB, OF, and IS amendments (0.1% CB + 3.0% OF + 3.0% IS and 0.5% CB + 3.0% OF + 3.0% IS, DB-T5 and DB-T6) could significantly increase soil pH, reduce the concentrations of CaCl 2 -extractable Cd and Pb, and increase the contents of Ca, P, S, and Si in DB soil. Under these two treatments, the growth of ramie was significantly improved, its photosynthesis was enhanced, and its levels of Cd and Pb were reduced, in comparison with the control (DB-CK). After applying DB-T5 and DB-T6, the concentrations of Cd and Pb in roots were decreased by 97.7-100% and 64.6-77.9%, while in shoots they were decreased by up to 100% and 92.9-100%, respectively. In YS-T4 (0.5% CB + 3.0% OF), the concentrations of Cd and Pb in roots were decreased by 39.5% and 46.0%, and in shoots they were decreased by 44.7% and 88.3%. We posit that phytostabilization using ramie and amendments could reduce the Cd and Pb bioavailability in the soil mainly through rhizosphere immobilization and plant absorption. In summary, this study suggests that the use of tolerant plant ramie and simultaneous application of coconut shell biochar, organic fertilizer, and Fe-Si-Ca materials is an effective stabilization strategy that can reduce Cd and Pb availabilities in soil. Ultimately, this strategy may reduce the exposure risk of crops to heavy metal pollution in farmland.

Nowadays rare earth elements (REEs) are widely applied in high-technology and clean energy products, but their environmental risks are still largely unknown. To estimate the ecological risk of REEs, soil samples were collected from REE mine tailings with and without phytoremediation. The results showed that the tailings had rather low organic matter and high total REE concentrations, up to 808.5 mg/kg. The 10% effective concentration (EC10) of neodymium (Nd) and yttrium (Y) were calculated based on the toxicity tests of seed germination and root growth. For both wheat and mung bean, the EC10 of Nd and Y in soils were in the range of 1053.1-1300.1 mg/kg. The average hazard quotient of mine tailing soil without phytoremediation was higher than that with phytoremediation. All the hazard quotient of Nd and Y were less than 1, indicating that Nd or Y alone was unlikely to cause adverse ecological effects. Given to the coexistence of REEs on mine sites, the ecological risk of REE mixture could be potentially high towards local soil environments, even for soils with phytoremdiation.

Electronic waste or e-waste dismantling activities are known to release metals. However, the human exposure pathways of metals, and their association with oxidative stress in e-waste dismantling areas (EDAs) remain unclear. In this study, our results revealed elevated geometric mean concentrations in vegetables (Cd 0.096 and Pb 0.35 µg/g fw), rice (Cd 0.15, Pb 0.20, and 12.3 µg/g fw), hen eggs (Cd 0.006 and Pb 0.071 µg/g fw), and human urine (Cd 2.12, Pb 4.98, Cu 22.2, and Sb 0.20 ng/mL). Our calculations indicate that rice consumption source accounted for the overwhelming proportion of daily intakes (DIs) of Cd (61-64%), Cu (85-89%), and Zn (75-80%) in children and adults living in EDA; vegetables were the primary contributors to the DIs of Cd (30-32%); and rice (20-29%), vegetables (28-38%), and dust ingestion (26-45%) were all important exposure sources of Pb. Risk assessment predicted that DIs of Cd, Pb, Cu, and Zn via food consumption poses health risks to local residents of EDAs, and the urinary concentrations of analyzed metals were significantly (Pearson correlation coefficient: r = 0.324-0.710; p < 0.01) associated with elevated 8-OHdG, a biomarker of oxidative stress in humans., (Copyright © 2018. Published by Elsevier Inc.)

Hyperaccumulator plants are the material basis for phytoextraction research and for practical applications in decontaminating polluted soils and industrial wastes. China's high biodiversity and substantial mineral resources make it a global hotspot for hyperaccumulator plant species. Intensive screening efforts over the past 20 years by researchers working in China have led to the discovery of many different hyperaccumulators for a range of elements. In this review, we present the state of knowledge on all currently reported hyperaccumulator species from China, including Cardamine hupingshanensis (selenium, Se), Dicranopteris dichotoma (rare earth elements, REEs), Elsholtzia splendens (copper, Cu), Phytolacca americana (manganese, Mn), Pteris vittata (arsenic, As), Sedum alfredii, and Sedum plumbizincicola (cadmium/zinc, Cd/Zn). This review covers aspects of the ecophysiology and molecular biology of tolerance and hyperaccumulation for each element. The major scientific advances resulting from the study of hyperaccumulator plants in China are summarized and synthesized.

Cadmium uptake in rice is believed to be mediated by the Fe transport system. Phyto-available Cd can be changed by Fe fertilization of substrates. This work investigated whether and how Fe fertilization affects mitigation of Cd accumulation in paddy rice. A 90-d soil column experiment was conducted to study the change of Cd and Fe availability in soil after Fe fertilization (ionic and chelated Fe). A low-Cd accumulating cultivar (TY116) and a high-Cd accumulating cultivar (JY841) were grown in two Cd-polluted paddy soils amended with chelated Fe fertilizers. Additionally, both cultivars were grown in hydroponics to compare Fe-related gene expression in EDDHAFe-deficient and EDDHAFe-sufficient roots. The column experiment showed that EDTANa 2 Fe(II) and EDDHAFe(III) fertilization had a better mitigation effect on soil Cd availability compared to FeSO 4 ·7H 2 O. Moreover, the field experiment demonstrated that these two chelated fertilizations could reduce Cd concentrations in brown rice by up to 80%. Iron concentrations in the brown rice were elevated by Fe chelates. Compared to EDDHAFe(III), EDTANa 2 Fe(II) fertilization had a stronger mitigation effect by generating more EDTANa 2 Cd(II) in the soil solution to decrease phyto-available Cd in the soil. While EDDHAFe(III) fertilization could increase soil pH and decrease soil Eh which contributed to decreasing phyto-available Cd in a contaminated soil. In the hydroponic experiment, Fe sufficiency significantly reduced Cd concentrations in above-ground organs. In some cases, the expression of OsIRT1, OsNRAMP1 and OsNRAMP5 was inhibited under Fe sufficiency relative to Fe deficiency conditions. These results suggest that mitigation of rice Cd by Fe chelate fertilization results from a decrease in available Cd in substrates and the inhibition of the expression of several Fe-related genes in the IRT and NRAMP families., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The development of more selective chelators for the washing of heavy metal contaminated soil is desirable in order to avoid excessive dissolution of soil minerals. Speciation and mobility of Cu, Zn, Pb, and Ni in a contaminated soil washed with phenyldiaminetetraacetic acid (PDTA), a derivative of EDTA, were investigated by batch leaching test using a range of soil washing conditions followed by sequential extraction. With appropriate washing conditions, PDTA significantly enhanced extraction of Cu from the contaminated soil. The primary mechanisms of Cu extraction by PDTA were complexation-promoted dissolution of soil Cu and increased dissolution of soil organic matter (SOM). PDTA showed high selectivity for Cu(II) over soil component cations (Ca(II), Mg(II), Fe(III), Mn(II), Al(III)), especially at lower liquid-to-soil ratios under PDTA deficiency, thus avoiding unwanted dissolution of soil minerals during the soil washing process which can degrade soil structure and interfere with future land use. PDTA-enhanced soil washing increased the exchangeable fractions of Cu, Zn, and Pb and decreased their residual fractions, compared to their levels in unwashed soil., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Soil washing is one of the few permanent treatment alternatives for removing metal contaminants. Ethylenediaminetetraacetic acid (EDTA) and its salts can substantially increase heavy metal removal from contaminated soils and have been extensively studied for soil washing. However, EDTA has a poor utilization ratio due to its low selectivity resulting from the competition between soil major cations and trace metal ions for chelation. The present study evaluated the potential for soil washing using EDTA and three of its derivatives: CDTA (trans-1,2-cyclohexanediaminetetraacetic acid), BDTA (benzyldiaminetetraacetic acid), and PDTA (phenyldiaminetetraacetic acid), which contain a cylcohexane ring, a benzyl group, and a phenyl group, respectively. Titration results showed that PDTA had the highest stability constants for Cu(2+) and Ni(2+) and the highest overall selectivity for trace metals over major cations. Equilibrium batch experiments were conducted to evaluate the efficacy of the EDTA derivatives at extracting Cu(2+), Zn(2+), Ni(2+), Pb(2+), Ca(2+), and Fe(3+) from a contaminated soil. At pH 7.0, PDTA extracted 1.5 times more Cu(2+) than did EDTA, but only 75% as much Ca(2+). Although CDTA was a strong chelator of heavy metal ions, its overall selectivity was lower and comparable to that of EDTA. BDTA was the least effective extractant because its stability constants with heavy metals were low. PDTA is potentially a practical washing agent for soils contaminated with trace metals., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Siderophore-producing rhizobacteria (SPR) are a group of plant growth-promoting rhizobacteria, being able to play an important role in assisting the phytoremediation of heavy metals-contaminated soils. Based on the comprehensive analysis of related researches at home and abroad, this paper elaborated the functions of SPR in alleviating the heavy metals stress and toxicity to plants and the mechanisms of SPR in improving the heavy metals bioavailability in soil, and indicated that SPR had good application potential in promoting the plant growth in heavy metals-contaminated soils and reinforcing the heavy metals accumulation in plants. The contradictory phenomena of SPR in increasing or decreasing heavy metals accumulation in plants, which existed in current researches, were also analyzed. Aiming at the deficiencies in current researches, it was suggested that in the future researches, the mechanisms of the interactions between SPR and plants, especially hyperaccumulators, should be further studied, the key factors affecting the heavy metals complexation and mobilization in soil by siderophores should also be further clarified, the effects of siderophores on the heavy metals bioavailability and its subsequent influence on the heavy metals uptake by plants should be comprehensively considered, and the measures for improving the colonization of SPR in heavy metals-contaminated soil should be explored.

A five-year field trial was conducted at the surrounding area of Dabao Mountain Mine to explore the feasibility and availability of using kenaf (Hibiscus cannabinus) , a fiber crop with strong heavy metals tolerance and potential economic value, to reclaim the multi-metal contaminated acidic farmland soil. Different amendments were applied prior to the kenaf planting to evaluate their effects on the soil properties and kenaf growth. After the amendments application, the kenaf could grow well on the heavy metals contaminated soil with the Pb, Zn, Cu, Cd, and As concentrations being 1600, 440, 640, 7. 6, and 850 mg . kg-1, respectively. Among the amendments, dolomite and fly ash had better effects than limestone and organic fertilizer. With the application of dolomite and fly ash, the aboveground dry mass production of kenaf reached 14-15 t . hm-2, which was similar to that on normal soils, and the heavy metal concentrations in the bast fiber and stem of kenaf decreased significantly, as compared with the control. The mass of the bast fiber accounted for 32% -38% of the shoot production, and the extractable heavy metal concentrations in the bast fiber could meet the standard of 'technical specifications of ecological textiles' in China, suggesting that the bast fiber had potential economic value. It was suggested that planting kenaf combining with dolomite/fly ash application could be an effective measure to reclaim the multi-metal contaminated acidic farmland soil.

Understanding the complex biotic and abiotic interactions invoked by the rice root system in oxygen-depleted soil is an important step in screening genotypes for low toxic metal or metalloid accumulation. A hydroponic and a rhizobox experiment have been conducted to explore the effects of varying root oxygen release on chemical changes, As fractionation in rhizosphere soil and Fe plaque formation, As uptake and tolerance by different rice genotypes. The results showed that rice genotypes with higher rates of radial oxygen loss (ROL) and at the bolting stage, tended to have greater effects on rhizosphere Eh, pH, Fe(3+)/Fe(2+) quotients, As fractionation and mobility and also on Fe plaque formation compared to those with lower ROL and at the tillering stage. Genotypes with higher ROL have a strong ability to reduce As accumulation in shoots and increase As tolerance by reducing As mobilization in the rhizosphere and by limiting As translocation., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Cadmium (Cd) uptake and tolerance were investigated among 20 rice cultivars based on a field experiment (1.2 mg Cd kg⁻¹ in soil) and a soil pot trial (control, 100 mg Cd kg⁻¹), and rates of radial oxygen loss (ROL) were measured under a deoxygenated solution. Significant differences were found among the cultivars in: (1) brown rice Cd concentrations (0.11-0.29 mg kg⁻¹) in a field soil, (2) grain Cd tolerance (34-113%) and concentrations (2.1-6.5 mg kg⁻¹) in a pot trial, and (3) rates of ROL (15-31 mmol O₂ kg⁻¹ root d.w. h⁻¹). Target hazard quotients were calculated for the field experiment to assess potential Cd risk. Significant negative relationships were found between rates of ROL and concentrations of Cd in brown rice or straw under field and greenhouse conditions, indicating that rice cultivars with higher rates of ROL had higher capacities for limiting the transfer of Cd to rice and straw., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

The mechanisms of stabilization by silicon-rich amendments of cadmium, zinc, copper and lead in a multi-metal contaminated acidic soil and the mitigation of metal accumulation in rice were investigated in this study. The results from a pot experiment indicated that the application of fly ash (20 and 40gkg(-1)) and steel slag (3 and 6gkg(-1)) increased soil pH from 4.0 to 5.0-6.4, decreased the phytoavailability of heavy metals by at least 60%, and further suppressed metal uptake by rice. Diffusion gradient in thin-film measurement showed the heavy metal diffusion fluxes from soil to solution decreased by greater than 84% after remediation. X-ray diffraction analysis indicated the mobile metals were mainly deposited as their silicates, phosphates and hydroxides in amended treatments. Moreover, it was found metal translocation from stem to leaf was dramatically restrained by adding amendments, which might be due to the increase of silicon concentration and co-precipitation with heavy metals in stem. Finally, a field experiment showed the trace element concentrations in polished rice treated with amendments complied with the food safety standards of China. These results demonstrated fly ash and steel slag could be effective in mitigating heavy metal accumulation in rice grown on multi-metal contaminated acidic soils., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

The Zn/Cd hyperaccumulator Arabis paniculata is able to tolerate high level of Zn and Cd. To clarify the molecular basis of Zn and Cd tolerance, proteomic approaches were applied to identify proteins involved in Zn and Cd stress response in A. paniculata. Plants were exposed to both low and high Zn or Cd levels for 10 d. Proteins of leaves in each treatment were separated by 2-DE (two-dimensional electrophoresis). Nineteen differentially-expressed proteins upon Zn treatments and 18 proteins upon Cd treatments were observed. Seventeen out of 19 of Zn-responsive proteins and 16 out of 18 of Cd-responsive proteins were identified using MALDI-TOF/TOF-MS (matrix-assisted laser desorption/ionization time of flight mass spectrometry). The most of identified proteins were known to function in energy metabolism, xenobiotic/antioxidant defense, cellular metabolism, protein metabolism, suggesting the responses of A. paniculata to Zn and Cd share similar pathway to certain extend. However, the different metal defense was also revealed between Zn and Cd treatment in A. paniculata. These results indicated that A. paniculata against to Zn stress mainly by enhancement of energy metabolism including auxin biosynthesis and protein metabolism to maintain plant growth and correct misfolded proteins. In the case of Cd, plants adopted antioxidative/xenobiotic defense and cellular metabolism to keep cellular redox homeostasis and metal-transportation under Cd stress., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

The adsorption behavior of exogenous thorium on soil was studied to evaluate the contaminated risk on soil. The adsorption capacity, equilibrium time, distribution coefficient and desorption ability were investigated by the experiments of static adsorption. The strong adsorption ability of exogenous thorium on soil samples was observed by high adsorption ratio (> 92%) and low desorption ratio (< 5%) in equilibrium, and the biggest distribution coefficient was over 10(4). The adsorption capacity and equilibrium time were related to soil properties. According to the results of adsorption, Freundlich equation (r > or = 0.9167) and Elovich equation (R2 > or = 0.8980) were primely fit for describing the thermodynamics and kinetics of the adsorption of exogenous thorium on soil samples, respectively, which indicated that the adsorption was belonged to the nonlinear adsorption, and was affected by the diffusion of thorium on soil surface and in mineral interbed. Sequential extraction procedure was employed to evaluate the bound fractions of exogenous thorium adsorbed on soil samples. Based on the extracted results of thorium fractions, exogenous thorium was presented in the labile nonresidual fractions (over 58%) at the low initial concentration (10(-7) - 10(-6) mol x L(-1)), and nonresidual fractions enhanced with the increase of the initial amount, meanwhile more exogenous throium was transferred to the stable residual fractions.

Based on field investigation and laboratory analysis, the speciation and bioavailability of the heavy metals (Cd, Cu, Pb, and Zn) was studied. These metals were tested from 16 soil samples taken from paddy soils irrigated by acid mine drainage in the lower stream of Dabaoshan mine area, Guangdong Province, China. The toxicity characteristic leaching procedure (TCLP) and three-step community bureau of reference (BCR) sequential extraction procedure methods were used to analyse the bioavailability of heavy metals. TCLP is currently recognized as an international method for evaluation of heavy metal pollution in soils. Two methods were compared in bioavailability by stepwise multiple linear regression analysis. Cd was dominated mainly by the acid-extractable and residual fractions, and followed by the order of acid-extractable > residual > oxidisable > reducible. Cu was dominated mainly by the residual fraction, and decreased in the following order: residual > reducible > acid-extractable > oxidisable. Pb was dominantly released in the reducible and residual fractions, they account for 86.54% of the total contents, and decreased in the following order: reducible > residual > acid-extractable > oxidisable. Zn was dominated mainly by the residual fraction, it takes more than 50% of the total contents, and followed by the order of residual > acid-extractable > reducible > oxidisable. The levels of Cd, Cu, Pb and Zn extracted by TCLP were 0.17-0.89, 8.12-70.33, 3.16-90.33 and 10.24-106.85 mg x kg(-1), respectively, and the average concentrations of Cd, Cu, Pb and Zn were 0.41, 36.60, 15.97 and 50.78 mg x kg(-1), respectively. The concentrations of Cd, Cu, Ph and Zn in rice seeds were 0.183-0.947, 3.542-5.997, 0.285-1.532 and 17.54-41.10 mg x kg(-1), respectively. Comparing to the national standards on heavy metals in foods by the Chinese Ministry of Health, the contents of Cu and Zn in rice seeds didn't exceed the upper limit, while the contents of Cd and Pb in rice seeds exceed the upper limit by 87.50% and 81.25%, respectively. Results of the stepwise multiple linear regression analysis revealed that contents of Cd and Zn in seeds of rice were significantly influenced by contents of acid-extractable Cd and Zn, that contents of Cu in seeds of rice were significantly influenced by contents of acid-extractable and oxidisable Cu, and the contents of Pb in seeds of rice were significantly influenced by contents of reducible Pb and organic matter. Contents of four metals in seeds of rice were significantly influenced by contents of metals extracted by TCLP, and the influences of total content, pH and organic matter were not significant. In short, TCLP method was fast, simple and suitable for evaluation of bioavailability of heavy metals in sewage-irrigated paddy soils by acid mine drainage.

Mining activities in the Dabaoshan area in the upper reach of the Hengshihe River have caused severe environmental changes, the waste water of milling and refining drained directly into the Hengshihe River, which contaminated the soils along the river severely. It is shown that Pb, Zn, Cd and Cu have contaminated the soil, the Cd contamination was more severe, and the contaminated level of Pb, Zn reached moderately to strongly polluted. The pH value of river and soil affected directly the heavy metals concentration of total and exchangeable ions, and presented negative pertinences. The levels of Pb, Zn, Cu and Cd in the surface soil of Shangbacun village in the lower reach of the river were found as high as 257.762, 350.235, 5.083 and 186.901 mg x kg(-1) respectively, which were relatively higher than those of the background values of soil 1.03, 1.75, 16.9 and 3.7 times respectively, and the result on the soil profiles showed that the contaminations have infiltrated into lower layer soil, ecological environment was harmed severely.