Recent advances in clay minerals for groundwater pollution control and remediation.

Clay minerals are abundant on Earth and have been crucial to the advancement of human civilization. The ability of clay minerals to absorb chemicals is frequently utilized to remove hazardous compounds from aquatic environments. Moreover, clay-based adsorbent products are both environmentally acceptable and affordable. This study provides an overview of advances in clay minerals in the field of groundwater remediation and related predictions. The existing literature was examined using data and information aggregation approaches. Keyword clustering analysis of the relevant literature revealed that clay minerals are associated with groundwater utilization and soil pollution remediation. Principal component analysis was used to assess the relationships among clay mineral modification methods, pollutant properties, and the Langmuir adsorption capacity (Qmax). The results demonstrated that pollutant properties affect the Qmax of pollutants adsorbed by clay minerals. Systematic cluster analysis was utilized to classify the collected data and investigate the relationships. The pollution adsorption mechanism of the unique structure of clay minerals was investigated based on the characterization results. Modified clay minerals exhibited changes in surface functional groups, internal structure, and pHpzc. This review provides a summary of recent clay-based materials and their applications in groundwater remediation, as well as discussions of their challenges and future prospects.

Aggregation, retention and transport of γ-MnO2 nanoparticles in water-saturated porous media: Impact on the immobility of thallium.

Nano-scale Mn oxides can act as effective stabilizers for Tl in soil and sediments. Nevertheless, the comprehensive analysis of the capacity of MnO2 to immobilize Tl in such porous media has not been systematically explored. Therefore, this study investigates the impact of γ-MnO2, a model functional nanomaterial for remediation, on the mobility of Tl in a water-saturated quartz sand-packed column. The mechanisms involved are further elucidated based on the adsorption and aggregation kinetics of γ-MnO2. The results indicate that higher ionic strength (IS) and the presence of ion Ca(II) promote the aggregation of γ-MnO2, resulting from the reduced electrostatic repulsion between particles. Conversely, an increase in pH inhibits aggregation due to enhanced interaction energy. γ-MnO2 significantly influences Tl retention and mobility, with a substantial fraction of γ-MnO2-bound Tl transported through the column. This might be attributed to the high affinity of γ-MnO2 for Tl through ion exchange reactions and precipitation at the surface of γ-MnO2. The mobility of Tl in the sand column is influenced by the γ-MnO2 colloids, exhibiting either inhibition or promotion depending on the pH, IS, and cation type of the solution. In solutions with higher IS and Ca(II), the mobility of Tl decreases as γ-MnO2 colloids tend to aggregate, strain, and block, facilitating colloidal Tl retention in porous media. Although higher pH reduces the mobility of individual Tl, it promotes the mobility of γ-MnO2 colloids, facilitating a substantial fraction of colloidal-form Tl. Consequently, the optimal conditions for stabilizing Tl by γ-MnO2 involve either high IS and low pH or the presence of competitive cations (e.g., Ca(II)). These findings provide new insights into Tl immobilization using MnO2- and Mn oxide-based functional materials, offering potential applications in the remediation of Tl contamination in soil and groundwater.

Hydrogeochemical evolution of groundwater impacted by acid mine drainage (AMD) from polymetallic mining areas (South China).

Mining activities have long-term impacts on the groundwater of surrounding areas and deserve in-depth analysis and study. Herein, the geochemical mechanisms of acid mine drainage (AMD)-affected groundwaters were examined, and groundwater quality was assessed through water quality indices. 15 water samples from 7 domestic and 4 groundwater monitoring wells were tested for physical and chemical parameters in 2022, and multivariate statistical analysis was carried out with monitoring data from 21 domestic wells in 2010. The groundwater chemical composition varied from a predominantly Ca-HCO3 type in 2010 to a Ca-SO4 type in 2022. The isotopic values of δ18O and δD indicate that groundwater has not been significantly affected by evaporation. Changes in groundwater sulfate and total dissolved solids (TDS) levels over the twelve-year period confirmed the AMD infiltration impact on groundwater quality. The groundwater chemical properties changed more slowly than those of surface waters affected by AMD based on a cumulative increase in sulfate concentration of 29.94 mg/L. Changes in groundwater quality were investigated, namely, the spatiotemporal distribution of potentially toxic elements (PTEs), including Fe, Mn, Cd, Pb, and As. Mn concentrations in upstream groundwater areas near the mine decreased by 61.8% between 2010 and 2022. Conversely, groundwater in midstream areas had Mn concentrations of 2.25 mg/L and arsenic concentrations of 11.8 µg/L, both exceeding the WHO, 2022 standard. According to multivariate statistical analysis, Mn, Cd, and Pb originated from polymetallic minerals, whereas As was likely derived from the reduction of Fe/Mn hydroxyl oxides. AMD remediation improved contaminated upstream groundwater quality over 12 years, with a 36.8% improvement in WQI values. PTE distribution determined water quality changes; therefore, PTE contamination should be treated in mid- and downstream regions while contaminated groundwater should be treated upstream.

Thallium release from biochar-amended soil to runoff in laboratory experiments.

Biochar has been widely used for trace metal(loid) (TM) immobilisation in contaminated soils. However, studies on the physicochemical mobility of TMs related to biochar application are highly limited, hampering the evaluation of the immobilisation efficiency of biochar. Therefore, after confirming the ability of biochar to decrease soil Tl bioavailability, this study examined the release of Tl in dissolved and particulate forms in surface runoff and leachate from soil mixed with biochar at different dosages and grain sizes under artificially simulated rainfall and irrigation experiments. The rainfall experimental results showed that the dissolved Tl in the surface runoff decreased from 1.30 µg in the control group to 0.75 µg and 0.54 µg in the groups with 3% and 5% biochar application, respectively. With the same dosages (5%), the finer the biochar applied, the higher the immobilisation ability achieved in surface runoff and the lower the Tl amounts in the leachate, indicating that the grain size of biochar can impact Tl mobility in dissolved forms. Comparisons between rainfall and irrigation experiments indicated that raindrops disturb the soil-water surface and enhance Tl diffusion. The mass in particulate form accounted for more than 95% of lateral released Tl in surface runoff. However, biochar application did not decrease the enrichment ratio of Tl in the eroded sediments. Notably, the finest biochar group produced less mass of eroded Tl owing to the low flux of soil erosion, indicating that grain size would indirectly impact sediment-bound Tl lateral mobility. Colloidal particles should be highlighted as they carried a maximum TI of up to 38% in the rainfall leachate. Focusing on the effect of biochar application on Tl chemical- and physical mobility from the soil matrix to runoff, this study contributes the comprehensive understanding of the role of biochar in TM remediation.

Impact of acid mine drainage on groundwater hydrogeochemistry at a pyrite mine (South China): a study using stable isotopes and multivariate statistical analyses.

Combining environmental isotope analysis with principal component analysis can be an effective method to discriminate the inflows and sources of contamination in mining-affected watersheds. This paper presents a field-scale study conducted at an acid mine drainage (AMD)-contaminated site adjacent to a pyrite mine in South China. Samples of surface water and groundwater were collected to investigate transport in the vadose zone using stable isotopes of oxygen (δ18O) and hydrogen (δD) as environmental tracers. Principal component analysis of hydrogeochemical data was used to identify the probable sources of heavy metals in the AMD. The heavy metal pollution index (HPI) was applied to evaluate the pollution status of heavy metals in the groundwater. The groundwater associated with the Datai reservoir was recharged by atmospheric precipitation and surface water. On the side near the AMD pond, the groundwater was significantly affected by the soluble metals produced by pyrite oxidation. The concentrations of some metals (Al, Mn, and Pb) in all of the samples exceed the desirable limits prescribed by the World Health Organization (Guidelines for drinking-water quality, 4th edn. World Health Organization, Geneva, 2011). Among them, the concentration of Al is more than 30,000 times higher than the desirable limits prescribed by the World Health Organization (2011), and the concentration of Mn is more than 3000 times higher. The HPI values based on these heavy metal concentrations were found to be 10-1000 times higher than the critical pollution index value of 100. These findings provide a reference and guidance for research on the migration and evolution of heavy metals in vadose zone water in AMD-contaminated areas.

Removal of Arsenic from Wastewater by Using Nano Fe3O4/Zinc Organic Frameworks.

Efficient removal of arsenic in wastewater is of fundamental importance due to the increasingly severe arsenic pollution. In this study, a new composite adsorbent (Fe3O4@ZIF-8) for As(V) removal from wastewater was synthesized by encapsulating magnetic Fe3O4 nanoparticles into metal organic frameworks. In order to evaluate the feasibility of Fe3O4@ZIF-8 as an adsorbent for As(V) removal, the adsorption properties of Fe3O4@ZIF-8 were systematically explored by studying the effects of dosage, pH, adsorption isotherm, kinetics, and thermodynamics. Additionally, the characterization of Fe3O4@ZIF-8 before and after adsorption was analyzed thoroughly using various tests including SEM-EDS, XPS, BET, XRD, TG, FTIR, and the properties and arsenic removal mechanism of the Fe3O4@ZIF-8 were further studied. The results showed that the Fe3O4@ZIF-8 has a specific surface area of 316 m2/g and has excellent adsorption performance. At 25 °C, the initial concentration of arsenic was 46.916 mg/L, and pH 3 was the optimum condition for the Fe3O4@ZIF-8 to adsorb arsenic. When the dosage of the Fe3O4@ZIF-8 was 0.60 g/L, the adsorption of arsenic by the Fe3O4@ZIF-8 can reach 76 mg/g, and the removal rate can reach 97.20%. The adsorption process of arsenic to the Fe3O4@ZIF-8 can be well described by the Langmuir isotherm model and the second-order kinetic equation. At pH 3 and temperature 298 K, the maximum adsorption capacity of arsenic by the Fe3O4@ZIF-8 was 116.114 mg/g. Through the analysis of thermodynamic parameters, it is proved that the adsorption process of arsenic by the Fe3O4@ZIF-8 is a spontaneous endothermic reaction. The Fe3O4@ZIF-8 has broad prospects for removing As(V) pollution in wastewater, because of its strong adsorption capacity, good water stability, and easy preparation.

A review of water pollution arising from agriculture and mining activities in Central Asia: Facts, causes and effects.

Central Asia is one of many regions worldwide that face severe water shortages; nevertheless, water pollution in this region exacerbates the existing water stress and increases the risk of regional water conflicts. In this study, we perform an extensive literature review, and the data show that water pollution in Central Asia is closely linked to human activities. Within the Asian Gold Belt, water pollution is influenced mainly by mining, and the predominant pollutants are heavy metals and radionuclides. However, in the irrigated areas along the middle and lower reaches of inland rivers (e.g., the Amu Darya and Syr Darya), water pollution is strongly associated with agriculture. Hence, irrigated areas are characterized by high concentrations of ammonia, nitrogen, and phosphorus. In addition, the salinities of rivers and groundwater in the middle and lower reaches of inland rivers generally increase along the flow path due to high rates of evaporation. Soil salinization and frequent salt dust storms in the Aral Sea basin further increase the pollution of surface water bodies. Ultimately, the pollution of surface water and groundwater poses risks to human health and deteriorates the ecological environment. To prevent further water pollution, joint monitoring of the surface water and groundwater quantity and quality throughout Central Asia must be implemented immediately.

Geochemical distribution and speciation of thallium in groundwater impacted by acid mine drainage (Southern China).

Thallium (Tl) commonly occurs in shallow groundwater affected by acid mine drainage (AMD); however, our knowledge of the occurrence of Tl in shallow groundwater is limited. This study observes that the shallow groundwater in an AMD-impacted area in Southern China contains an elevated Tl concentration (22 µg/L) under the oxidizing conditions and a low Tl concentration (<1 µg/L) in the reducing environment. The groundwater Tl concentration is positively correlated with oxidation-reduction potential (Eh) and negatively correlated with Cl content. The modelling results of the Tl species demonstrate that Tl+, TlSO4-, TlCl, and TlNO3 are the main forms of Tl in groundwater. Tl may precipitate as Tl(OH)3 under weakly acidic to alkaline conditions. Drill-core analysis of wells indicates that the Tl content in the vadose zone is equal to the background soil Tl content under oxidizing conditions. However, under artificial reducing conditions, the Tl content at the 3-4 m depth below the groundwater level ranges from 1.6 to 3.5 µg/g. This finding demonstrates that Tl solute in groundwater migrates into the aquifer when redox conditions change. Mn-oxides and illite in the weak permeable aquifer are the key minerals for Tl adsorption; some major sites of illite start to uptake Tl from pH 8.0. This study highlights not only the geochemical distribution of Tl in groundwater but also the influences of changes in redox conditions caused by human activities on Tl enrichment in groundwater. Enhancing our understanding of the aqueous geochemistry of Tl is of significance for the prevention and control of Tl pollution.

Metal accumulations in aquatic organisms and health risks in an acid mine-affected site in South China.

Metal contamination from base metal sulphide mines is a major environmental challenge that poses many ecological and health risks. We examined the metal concentrations in the Dabaoshan mine in South China in water, sediments, and aquatic organisms and their specific characteristics (i.e. size, body tissue, species, and habitat) along the Hengshi and Wengjiang River courses to assess acid mine drainage remediation efforts. Metal concentrations of arsenic, cadmium, chromium, copper, lead, nickel, thallium, and zinc were examined in tissues (i.e. gills, intestines, and muscles) of 17 freshwater species of fish, shrimps, and crabs. Metals in tissues followed the trend: intestines > gills > muscles; nearly all intestine samples exceeded the safe limits of metals analysed in this study. There is a positive correlation between distance from the mine and metal concentrations related to the flow of surface water and the habitat of aquatic organisms. The concentrations of arsenic, copper, and zinc were the highest in aquatic organisms, and the distribution was influenced by physical (distance from mine, currents, and seasonality), chemical (pH and competing ions), and biological (species, habitat, and predator-prey relation) factors. Large demersal fish and benthic fauna had higher concentrations of metals. Bioaccumulation and biomagnification of metals, as well as the high metal pollution index and target hazard quotient (arsenic, cadmium, copper, lead, thallium, and zinc), occurred in bottom feeders (C. aumtus, X. argentea) and fish belonging to higher trophic levels (P. fulvidraco, O. mossambicus). Lead and cadmium indicated the highest level of biomagnification from prey to predator. Health risks exist from the dietary intake of common aquatic species such as tilapia and carp besides crustaceans due to high arsenic, cadmium, lead, and thallium levels. Further reduction of metals is necessary to improve the effects of acid mine drainage in the catchment.

Effects of metal stabilizers on soil hydraulic characteristics and mobility of cadmium.

This study investigated the effect of typical stabilizers on hydraulic properties, immobilization, and leachate characteristics based on the diffusive gradient thin-films technique (DGT) and a leaching experiment. Three types of stabilizers were classified based on various characteristics of soil field capacity (θf), and their immobilization effects were as follows: (i) θf increased and the immobilization of Cd was achieved with nanohydroxyapatite, increasing θf by 19.36% and decreasing the bioavailable Cd by 78.84%; (ii) the increasing θf conversely inhibited cadmium stabilization. Straw biochar averagely promoted θf by 17.39%, while the stabilization was suppressed; (iii) other stabilizers (zeolite, montmorillonite, and sepiolite) had no significant effect on θf and immobilization. It is suggested that stabilization depends on chemical mechanisms and is probably also affected by hydraulic mechanisms. The first types of stabilizers formed precipitates with poor solubility, and the strong affinity of heavy metals to soil particles can account for that the increasing θf had a negligible influence on the dissolution equilibrium of the heavy metals. Attapulgite also belongs to this type. The second and third types of stabilizers primarily adsorbed cadmium through ion exchange, resulting in the relatively easy heavy metal release. Increasing θf facilitated the desorption of heavy metals in the case of the second stabilizer type. However, the inconspicuous change in θf caused by the third stabilizer type had no impact on stabilization. Moreover, Cd leaching was positively correlated with bioavailable Cd and soil permeability. Heavy metal migration induced by colloids less than 90 nm in coarse biochar treatments deserves further research.

Distribution and mobilization of heavy metals at an acid mine drainage affected region in South China, a post-remediation study.

Dabaoshan Mine Site (DMS) is the largest polymetallic mine in South China. The Hengshi River flowing next to DMS receives acid mine wastes leaching from the tailings pond and run-off from a treatment plant, which flows into the Wengjiang River. This study focuses on spatiotemporal distribution and mobilization of As, Cd, Pb, and Zn along the Hengshi River, groundwater, fluvial sediments, and soils, with a focus on As due to its high toxicity and the fact that mining is one of the main sources of contamination. Geochemical analyses (heavy metals, grain-size, X-ray diffraction, organic carbon and sulfur content) followed by geochemical modeling (PHREEQC) and statistical assessment were done to determine the physicochemical characteristics, toxicity risks, and behavior of heavy metals. Near the tailings pond, heavy metal concentrations in surface water were 2-100 times higher than the Chinese surface water standard for agriculture. Although water quality during the dry season has improved since the wastewater treatment plant started, heavy metal concentrations were high during rainy season. In groundwater, heavy metal concentrations were low and pose little risks. Soils along the Hengshi River were disturbed and they did not show any specific trends. The potential ecological risk of heavy metals was ranked as Cd > As > Cu > Pb > Zn in sediments and Cd > Cu > Pb > As > Zn in soils indicating multi-metal contamination and toxicity. As(III) was the predominant species in surface water during the dry season, whereas As(V) dominated during the rainy season. Arsenic levels in most sites exceeded the Chinese soil standard. Although As is assumed to have a moderate ecological risk in sediments and low risk in soils, anthropogenic activities, such as mining and land-use changes contribute to the release of As and other heavy metals and pose a risk for local residents.

Comparative Activation Process of Pb, Cd and Tl Using Chelating Agents from Contaminated Red Soils.

Adding chelating agents is a critical technique of heavy metal activation for enhancing phytoextraction through the formation of soluble metal complexes which will be more readily available for extraction. The preliminary, dynamic, equilibrium activation experiments and speciation analysis of Pb, Cd and Tl in contaminated red soils were used to select six chelates with relatively good activation performance from nine chelates, and the effects of dosage and pH on the heavy metals activation were studied systematically. Results showed that the activation of Pb, Cd and Tl by chelates reached equilibrium within 2 h, and the activation process showed three stages. Under neutral conditions, chelates had better activation performance on Pb- and Cd-contaminated soils. Except for S,S-ethylenediamine disuccinic acid (S,S-EDDS) and citric acid (CA), the maximum equilibrium activation effect (MEAE) of ethylenediaminetetraacetic acid (EDTA), N,N-bis (carboxymethyl) glutamic acid (GLDA), diethylenetriaminepentaacetic acid (DTPA) and aminotriacetic acid (NTA) was over 81%. The MEAE of Tl-contaminated soil was less than 15%. The decreasing order of the dosage of chelating agents corresponding to MEAE for three types of contaminated soils was Pb-, Cd- and Tl-contaminated soil, relating to the forms of heavy metals, the stability constants of metal-chelates and the activation of non-target elements Fe in red soil. Under acidic conditions, the activation efficiencies of chelates decreased to differing degrees in Pb- and Cd-contaminated soils, whereas the activation efficiencies of chelating agents in Tl-contaminated soils were slightly enhanced.

Evaluation method for the measuring comprehensive suitability of chelating agents: a study of the temporal dynamics of heavy metal activation.

The effects of chelating agents on heavy metal activation in Cd- and Pb-contaminated soils were studied through a dynamic activation experiment. An evaluation method for the measuring comprehensive suitability of chelating agent was established by calculating indexes for the degree of activation effect suitability and activated heavy metals' half-life suitability. The following results were obtained: in Cd- and Pb-contaminated soils, heavy metal activation effects reached or approached maximum activating effects within 1 d and subsequently showed different levels of decline in all chelating agent treatment conditions. Declines in activation effects similarly subjected to the law of exponents over time and to the goodness of fit in DTPA, NTA, and GLDA ranged from 0.80 to 0.98. For Cd- and Pb-contaminated soils, chelating agents' levels of comprehensive suitability (H) were recorded as follows: NTA(1.40) > GLDA(1.31) > DTPA(1.14) > EDTA(1.00) > EDDS(0.14) > CA(0.06) and GLDA(1.56) > DTPA(1.48) > EDTA(1.00) > NTA(0.78) > EDDS(0.26) > CA (0.02). GLDA and DTPA are both suitable for Cd and Pb phytoextraction. Moreover, NTA and GLDA are optimal chelating agents for Cd and Pb phytoextraction, respectively.

Distribution, Source and Risk Assessment of Heavy Metal(oid)s in Water, Sediments, and Corbicula Fluminea of Xijiang River, China.

A total of 43 water and sediment samples, and 34 Corbicula fluminea samples were collected in Xijiang River in southern China to determine the spatial distribution and sources of 12 metals/metalloids (V, Co, Cr, Ni, Cu, Mn, Zn, Cd, Pb, As, Sb, and Tl) and to assess the pollution levels and ecological risks of the pollutants. The results showed that the levels of the metals/metalloids (except for Tl) in the river water from almost all of the sampling sites met the Chinese national surface water quality standards. However, the concentrations of the metals/metalloids in the sediments exceeded the background values by a factor of 1.03-56.56 except for V, Co, and Mn, and the contents of Zn, Cd, and Pb in the Corbicula fluminea soft tissue exceeded the limits of the Chinese Category I food Quality Standards. The spatial distribution analysis showed that the concentrations of the contaminants in the lower reaches of Xijiang River were higher than in the upper reaches. The bioaccumulation factor (BAF), biota-sediment accumulation factor (BSF), geo-accumulation index (Igeo), and the potential ecological risk index (RI) were obtained to assess the pollution levels and ecological risks. The results indicated that Cu, Cd, and Zn were the most prone to bio-accumulation in the Corbicula fluminea soft tissue, and the lower reaches showed a much higher pollution level and risk than the upper reaches. The metals/metalloids in the sediments posed serious threat on the aquatic ecosystem, of which Cd, As, and Sb are the most risky contaminants. The results of principal component analysis (PCA) indicated Cr, Ni, Cu, Mn, Cd, Pb, and As in the sediments came from relevant industrial activities, and V and Co originated from natural sources, and Sb from mining activities, Zn and Tl came from industrial activities and mining activities.

Insights into Heavy Metals Leakage in Chelator-Induced Phytoextraction of Pb- and Tl-Contaminated Soil.

Chelators including DTPA (diethylene triamine pentaacetic acid) and oxalic acid were selected for inducing phytoextraction of heavy metals (HMs) from Pb-, Tl-, and Pb-Tl- contaminated soil, in which heavy metals leakage was highly remarkable. Results showed that compared with the control group without chelating agent under planting conditions, the extraction efficiency (i.e., uptake coefficient) of Pb, Tl increased by 86%, 43% from Pb-Tl- contaminated soil in the presence of oxalic acid, and there was no significant change in heavy metal leakage under rainfall conditions. It was the best phytoremediation scheme in this work. Under rainfall conditions, the HMs concentration in the leachate showed a linear decreasing trend. Acid rain promoted the leakage of heavy metals, and the average leached amount of Tl increased by 1.47 times under acid rain conditions. However, for Pb, DTPA was the main influencing factor, followed by acid rain.

Fractional distribution of thallium in paddy soil and its bioavailability to rice.

To investigate the bioavailability of thallium (Tl) in soil and rice in a Tl-contaminated area in Guangdong, China, the topsoil and rice samples were collected from 24 sampling sites and analyzed. Moreover, a modified sequential extraction procedure was applied to determine the different Tl fractions in the soil. The mean pH value of the soil samples was 4.50. The total Tl concentration in the paddy soil was about 4-8 times higher than the Canadian guideline value (1mgkg-1) for agricultural land uses. The mean ecological risk index of Tl was determined to be 483, indicating that potential hazard of the paddy soil was serious. The mean content of Tl in rice was 1.42mgkg-1, which exceeded the German maximum permissible level (0.5mgkg-1) of Tl in foods and feedstuffs by a factor of nearly 3. The hazard quotient value via rice intake was 57.6, indicating a high potential health risk to the local residents. The distribution of various Tl fractions followed the order of easily reducible fraction (40.3%) > acid exchangeable fraction (30.5%) > residual fraction (23.8%) > oxidizable fraction (5.4%). Correlation analyses showed that the easily reducible fraction correlates positively with the soil Fe and Mn contents, whereas the acid exchangeable fraction is significantly correlated with the S content. The soil pH was negatively correlated with the Tl content in both soil and rice. The Tl content in rice was more strongly correlated with the exchangeable fraction than the total Tl content in the soil. Overall, the bioavailability of Tl in more acidic soil is higher, and is strongly dependent on the speciation of Tl, especially the content of acid exchangeable fraction.

Leaching variations of heavy metals in chelator-assisted phytoextraction by Zea mays L. exposed to acid rainfall.

Chelant-enhanced phytoextraction method has been put forward as an effective soil remediation method, whereas the heavy metal leaching could not be ignored. In this study, a cropping-leaching experiment, using soil columns, was applied to study the metal leaching variations during assisted phytoextraction of Cd- and Pb-polluted soils, using seedlings of Zea mays, applying three different chelators (EDTA, EDDS, and rhamnolipid), and artificial rainfall (acid rainfall or normal rainfall). It showed that artificial rainfall, especially artificial acid rain, after chelator application led to the increase of heavy metals in the leaching solution. EDTA increased both Cd and Pb concentrations in the leaching solution, obviously, whereas EDDS and rhamnolipid increased Cd concentration but not Pb. The amount of Cd and Pb decreased as the leaching solution increased, the patterns as well matched LRMs (linear regression models), with R-square (R 2) higher than 90 and 82% for Cd and Pb, respectively. The maximum cumulative Cd and Pb in the leaching solutions were 18.44 and 16.68%, respectively, which was amended by EDTA and acid rainwater (pH 4.5), and followed by EDDS (pH 4.5), EDDS (pH 6.5), rhamnolipid (0.5 g kg-1 soil, pH 4.5), and rhamnolipid (pH 6.5).

Leaching characteristics of EDTA-enhanced phytoextraction of Cd and Pb by Zea mays L. in different particle-size fractions of soil aggregates exposed to artificial rain.

Chelator-assisted phytoextraction is an alternative and effective technique for the remediation of heavy metal-contaminated soils, but the potential for heavy metal leaching needs to be assessed. In the present study, a soil column cultivation-leaching experiment was conducted to investigate the Cd and Pb leaching characteristics during assisted phytoextraction of metal-contaminated soils containing different particle-size soil aggregates. The columns were planted with Zea mays "Zhengdan 958" seedlings and treated with combined applications of EDTA and simulated rainfall (pH 4.5 or 6.5). The results were as follows: (1) The greatest uptake of Cd and Pb by Z. mays was observed after treatment with EDTA (2.5 mmol kg-1 soil) and soil aggregates of <1 mm; uptake decreased as the soil aggregate size increased. (2) Simulated rainfall, especially acid rain (pH 4.5), after EDTA applications led to the increasing metal concentrations in the leachate, and EDTA significantly increased the concentrations of both Cd and Pb in the leachate, especially with soil aggregates of <1 mm; metal leachate concentrations decreased as soil particle sizes increased. (3) Concentrations of Cd and Pb decreased with each continuing leachate collection, and data were fit to linear regression models with coefficients of determination (R 2) above 0.90 and 0.87 for Cd and Pb, respectively. The highest total amounts of Cd (22.12%) and Pb (19.29%) were observed in the leachate of soils treated with EDTA and artificial acid rain (pH 4.5) with soil aggregates of <1 mm. The application of EDTA during phytoextraction method increased the leaching risk in the following order: EDTA2.5-1 (pH 4.5) > EDTA2.5-1 (pH 6.5) > EDTA2.5-2 (pH 4.5) > EDTA2.5-4 (pH 4.5) > EDTA2.5-2 (pH 6.5) > EDTA2.5-4 (pH 6.5).

Risk assessment and vertical distribution of thallium in paddy soils and uptake in rice plants irrigated with acid mine drainage.

The objective of this paper is to assess the influence of irritating paddy fields with acid mine drainage containing thallium (Tl) to rice plant-soil system and potential health risks for local residents. Vertical distribution of Tl, pH, organic matter (OM), and cation exchange capacity (CEC) in 24 paddy soil profiles around Yunfu pyrite mine area was investigated. Rice plant samples were collected from the corresponding soil sampling site. The results showed that Tl concentrations in paddy soils at 0-60 cm depth range from 3.07 to 9.42 mg kg-1, with a mean of 5.74 mg kg-1, which were significantly higher than the background value of soil in China (0.58 mg kg-1). On the whole, Tl contents in paddy soil profiles increased quickly with soil depth from 0 to 30 cm and decreased slowly with soil depth from 30 to 60 cm. The soil Tl content was significant negatively correlated with soil pH. The mean content of Tl in the root, stem, leaf, and rice was 4.36, 1.83, 2.74, and 1.42 mg kg-1, respectively, which exceeded the proposed permissible limits for foods and feedstuffs in Germany. The Tl content in various tissues of the rice plants followed the order root > leaf > stem (rice), which suggested that most Tl taken up by rice plants retained in the root, and a little migrated to the leaf, stem, and rice. Correlation analysis showed that Tl content in root was significant positively correlated with Tl content in leaf and rice. The ranges of hazard quotient (HQ) values were 4.08∼24.50 and 3.84∼22.38 for males and females, respectively. Males have higher health risk than females in the same age group. In childhood age groups (2 to <21 years) and adult age groups (21 to <70 years), the highest health risk level was observed in the 11 to 16 age group and 21 to 50 age group, respectively. The findings indicated that regular irrigation with Tl-bearing acid mine drainage led to considerable contamination of Tl in paddy soil and rice plant. Local government should take various measures to treat Tl contamination, especially the tailings.

Thallium transformation and partitioning during Pb-Zn smelting and environmental implications.

Thallium (Tl) is a toxic and non-essential heavy metal. Raw Pb-Zn ores and solid smelting wastes from a large Pb-Zn smelting plant - a typical thallium (Tl) pollution source in South China, were investigated in terms of Tl distribution and fractionation. A modified IRMM (Institute for Reference Materials and Measurement, Europe) sequential extraction scheme was applied on the samples, in order to uncover the geochemical behavior and transformation of Tl during Pb-Zn smelting and to assess the potential environmental risk of Tl arising from this plant. Results showed that the Pb-Zn ore materials were relatively enriched with Tl (15.1-87.7 mg kg(-1)), while even higher accumulation existed in the electrostatic dust (3280-4050 mg kg(-1)) and acidic waste (13,300 mg kg(-1)). A comparison of Tl concentration and fraction distribution in different samples clearly demonstrated the significant role of the ore roasting in Tl transformation and mobilization, probably as a result of alteration/decomposition of related minerals followed by Tl release and subsequent deposition/co-precipitation on fine surface particles of the electrostatic dust and acidic waste. While only 10-30% of total Tl amounts was associated with the exchangeable/acid-extractable fraction of the Pb-Zn ore materials, up to 90% of total Tl was found in this fraction of the electrostatic dust and acidic waste. Taking into account the mobility and bioavailability of this fraction, these waste forms may pose significant environmental risk.