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Low-molecular-weight organic acids may significantly influence the mobility of metal in environment, but the kinetics are not fully understood and have not been quantified. In this study, the thermodynamic and kinetic effects of citric acid (CA) on the adsorption of Cd(II) and Ni(II) on goethite were investigated using batch-adsorption and stirred-flow experiments. A charge distribution and multisite complexation model (CD-MUSIC) and a thermodynamically based multi-rate kinetic model were employed to describe the adsorption behaviors. Two ternary surface complexes, (≡FeO) 2 CitMe and (≡FeOH) 2 MeCit 2- , were involved in the adsorption. In addition, CA differed in its effects on Cd(II) and Ni(II) adsorption, enhancing Cd(II) adsorption but inhibiting Ni(II) adsorption at high levels. Kinetically, in the presence of CA, the adsorption of Cd(II) was faster than that of Ni(II). Increasing CA concentration led to faster Cd(II) adsorption, but resulted in the dissolution of the adsorbed Ni(II), possibly due to the much higher complexation constants of Ni-CA than of Cd-CA in aqueous phase. This finding implied that, in the rhizosphere, high level of CA may lead to more dissolution of Ni(II) than Cd(II); while in acidic ferrosol, CA may alleviate Cd(II) mobility and toxicity. The proposed mechanistic model sheds light on ion partition in the soil environment and may improve predictions thereof., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

An accurate model to predict Cd accumulation in crops based on soil properties would facilitate evaluations of soil quality and the potential risk posed by metals. However, given the heterogeneity of soil, such models are difficult to establish on large regional scales. This study for the first time examined the applicability of a multi-surface speciation model (MSM) in predicting Cd accumulation in wheat at a regional field scale, based on 140 soil-wheat paired samples collected from a 205-km 2 field. The MSM resulted in a better correlation between Cd accumulation in wheat grain (R 2 = 0.75) and roots (R 2 = 0.74) than obtained with chemical extraction methods (total Cd in soil, 0.01 M CaCl 2 , and 0.43 M HNO 3 ). In addition, while the performance of the MSM was comparable to that of a traditional multiple regression model, a parameter-fitting process was not required. The predictive ability of the MSM was further used to assess and predict the soil Cd risk and to develop a soil Cd sensitivity map to better localize areas of greatest sensitivity to Cd contamination. The results showed that the MSM can serve as a useful tool for regional soil risk assessments and thus in the development of soil protection measures., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Arsenic (As) and cadmium (Cd) are common soil pollutants whose opposing geochemical behaviors must be taken into account in the development of cost-effective, environmentally friendly remediation strategies. In this study, a pot experiment with lettuce and a field experiment with wheat were performed to examine the impacts of zeolite, biochar, MnO 2 , zero-valent iron (ZVI) individually and in binary combinations thereof on As-Cd pollution. The results of the pot experiment showed that biochar, MnO 2 and ZVI had good passivation effects on As and Cd when provided individually, but the effects of a combination of 0.2% ZVI/0.5% biochar or 0.2% MnO 2 /0.5% ZVI were even better. These amendments were further investigated in a field experiment, which confirmed the positive effect of 0.2% MnO 2 /0.5% ZVI. Therefore, ZVI/biochar and MnO 2 /ZVI mixtures may offer effective solutions to the remediation of farmland soil contaminated with both As and Cd.

The activity of e-waste recycling often causes the combined pollution of tetrabromobisphenol A (TBBPA) and cadmium (Cd) in soils. In this study, the effects of their co-existence on each other's fate, further reflecting the bioavailability, were analyzed in the presence of two ecologically different earthworm species, endogeic Metaphire guillelmi and epigeic Eisenia fetida. Mineralization of 14 C-TBBPA combined with 10 mg Cd kg -1 was suppressed by the presence of M. guillelmi, whereas a facilitating effect was produced by the combination of 1 mg Cd kg -1 in the soil-E. fetida system after a 14-day exposure. The uptake of 14 C-TBBPA by M. guillelmi (17% of initial amount) and by E. fetida (10%) dominantly contributed to significant (P < 0.05) decrease of extractable (more bioavailable) 14 C residues in soils both with and without Cd spiked, while the mineralization of 14 C-TBBPA in the soils was negligible (<0.4%). Meanwhile the amendments of the two earthworm species exerted different impact on 14 C distribution in bound residues. In general, co-exposure to Cd did not significantly (P > 0.05) influence the accumulation and metabolism of TBBPA in the earthworms. Both earthworms accumulated only ~7% of Cd in soil, however, the bioavailable Cd determined by the diffusive gradients in thin films technique declined by ~46% in the presence of M. guillelmi, and a much smaller decrease was determined in the presence of E. fetida. Amendment of TBBPA at environmental levels did not alter the accumulation and subcellular distribution of Cd in both earthworms unless that at high doses. The results highlighted the importance of considering the difference of the earthworm species and the interaction of pollutants in soil-risk assessments of such combined contamination. CAPSULE: M. guillelmi displayed greater effect on the fate of TBBPA and Cd co-existed in soils than E. fetida, while the accumulation, metabolism, or distribution of the two pollutants in earthworms did not significantly alter due to interactions between the two pollutants., (Copyright © 2018. Published by Elsevier B.V.)

Cadmium (Cd) and tetrabromobisphenol A (TBBPA) are two ubiquitous pollutants in soils and are often found together at electronic waste recycling sites. In this study, their toxicity as well as the accumulation and subcellular partitioning of Cd were determined in two ecologically different earthworms Eisenia fetida and Metaphire guillelmi exposed for 14 days to Cd (1 mg kg -1 ) and TBBPA (10, 50, 100, and 500 mg kg -1 ) alone and in combination. In general, Cd-TBBPA co-exposure resulted in synergistic effects in terms of acute toxicity, growth inhibition, histopathological changes in body walls, and oxidative stress responses to earthworms, moreover, M. guillelmi showed higher sensitivity than E. fetida. Principal component analysis showed that the two earthworm species differed in their biomarker expression patterns. In addition, Cd accumulation was significantly (P < 0.01) reduced in E. fetida co-exposed to TBBPA but significantly (P < 0.05 and 0.01) enhanced in M. guillelmi. The difference in bioaccumulation between the two earthworm species may be made by their different exposure routes despite the decrease of Cd bioavailability (assessed by the diffusive gradients in thin films technique) in the soils. High doses of TBBPA also altered the subcellular distribution of Cd in the earthworms. These findings demonstrate the need to include more ecologically relevant earthworm species, represented in this study by M. guillelmi, in soil risk assessments of Cd and TBBPA co-exposure., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Metal partitioning in soils is a key process controlling metal bioavailability and mobility and is greatly influenced by the solid/liquid ratio. However, metal partitioning is difficult to describe either by a simple partition coefficient or by isotherm adsorption equations. This study investigated the solubility of Ni(II) and Cd(II) in 19 soils as a function of three extraction reagents (water, 0.01 M NaNO 3 , and 0.01 M CaCl 2 ), five solid/liquid ratios (5-400 g/L) and field condition extracted by Rhizon samplers. Thermodynamically based multi-surface models (MSMs) that included generic parameters were used to describe metal partitioning under the studied conditions. The results showed that Ni/Cd solubility depended on the soil type, extraction reagent, and solid/liquid ratio. Soil major background cations (especially Ca 2+ , Mg 2+ , Fe 3+ and Al 3+ ) had a significant effect on the model's prediction ability. The MSM was able to predict the extractable metal in 0.01 M CaCl 2 in various soils at different solid/liquid ratios when soil background cations were included in the calculation; without the background cations, the model was able to predict metal partitioning only at solid/liquid ratios of <100 g/L. In addition, the model failed to predict water-extracted and 0.01 M-NaNO 3 -extracted Ni/Cd if background cations were not included, but could reasonably do so if they were included. More importantly, after the background cations were included, MSMs relatively well predicted the Ni/Cd content in soil pore water under 80% field capacity conditions with water as the solution matrix., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The prediction of metal bioavailability in soils is critical to metal risk assessments and the amount of dissolved metal in soils is a key factor determining bioavailability. Because the recently developed geochemical multi-surface models (MSMs) offer a promising tool for the determination of metal partitioning in soils, in this study, a MSM based on generic parameters was used to assess the bioavailability of Cd in wheat (Triticum aestivum L.) growing in 12 soils with a wide range of properties. The amount of MSM-calculated dissolved Cd correlated strongly with the amount of Cd uptake by wheat (R 2 =0.873 for roots and R 2 =0.837 for shoots), and the model's performance was better than that of chemical extraction methods (0.01M CaCl 2 , 0.43M HNO 3 and soil total Cd). The reactive fraction of soil organic matter, the soil/solution ratio, and the inclusion/exclusion of background cations influenced the calculation results. The best calculation condition was optimized. The application of the MSM was also examined in 84 wheat-soil samples from the field. The amount of Cd in wheat seeds had a stronger correlation with the amount of MSM-predicted Cd than with the amount of Cd obtained using chemical extraction methods. Our results suggested that MSM-calculated Cd is an effective indicator of the bioavailability of Cd in soils and demonstrated the utility of the method as a tool to assess the risk of Cd contamination in soils., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This work sets out to investigate biological responses of Eisenia fetida to Cd, based on the bioavailable rather than total concentration of Cd, in soils. E. fetida was cultured for 14d in three selected Chinese soils amended with 0.1-40mgkg -1 Cd. Potentially bioavailable concentrations of Cd were measured in soil solution, in extractions using CaCl 2 and HAc solutions, and using the technique of diffusive gradients in thin-films (DGT). Antioxidant system responses in E. fetida to Cd were measured as biological endpoints. Biological responses were more highly correlated with Cd concentrations evaluated using bioavailable methods than with total concentrations. Cd concentration measured using DGT and CaCl 2 extraction provided the narrowest ranges of lowest observed effect concentration (LOEC) values based on biological responses, indicating the potential use of these measurements in management of soil quality and setting soil remediation standards. The LOEC values obtained from 15 field soils contaminated by Cd were similar to those from the three Cd-amended soils and suggested that DGT in particular can be a good tool to predict stress responses of E. fetida to Cd in soils. The study shows the potential of combining biological response and DGT measurements in risk assessment., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Soil toxicological tests are commonly performed using Eisenia fetida as the standard earthworm species, but it is tolerant to a wide range of pollutants. Therefore, the inclusion of susceptible species is crucial for the accurate estimation of soil contamination. In this study, we examined the sensitivity to soil cadmium (Cd) of anecic Metaphire guillelmi and epigeic E. fetida by measuring multiple indexes of oxidative stress. Using subcellular partitioning analysis, we further elucidated the inherent mechanism underlying the species-specific sensitivity of the two earthworm species. Among the battery of biochemical indexes, reactive oxygen species and protein carbonyl groups served as sensitive biomarkers. According to their respective response thresholds, M. guillelmi was more sensitive than E. fetida and they differed in their dose-response relationships. In E. fetida, the activities of three antioxidant enzymes, superoxide dismutase (SOD), catalase (CAT) and glutathione S-transferase (GST), exhibited a hormesis-like U-shaped dose-response relationship, while in M. guillelmi SOD, glutathione peroxidase (an analogue of CAT) and GST showed an inverted U-shaped relationship. The concentrations of Cd in the subcellular fractions and whole body of the earthworms well fit (R 2 >0.9) a saturation model versus bioavailable Cd concentrations determined by the diffusive gradients in thin films technique. Despite the lower accumulation capacity of M. guillelmi, the Cd-binding capacity (C max ) of its subcellular heat-stable protein fraction, the so-called biologically detoxified metal pool, was 2.7 times lower than that of E. fetida, whereas the Cd binding affinity (logK) of its heat-denatured protein fraction, i.e. the metal-sensitive fraction, was 3.0 times higher, which accounted for the high susceptibility of M. guillelmi to soil Cd. Our results suggest that because of their sensitivity, as exemplified by M. guillelmi, native earthworm species should be taken into account in soil risk assessments to avoid underestimation of the toxicity of various pollutants., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Co-contamination of antibiotic and heavy metals commonly occurs in the environment. Tetracycline (TC), a common antibiotic, can behave as an efficient organic ligand to complex with cations. In this paper, the joint toxicity of TC with two commonly existing metals, copper(II) and cadmium(II), towards a luminescent bacteria, Vibrio fischeri, are investigated. Results showed that coexistence of TC and Cu(II) showed a significant antagonistic effect, while TC and Cd(II) showed a synergistic effect. The aqueous speciation of TC with two metal cations was calculated using a chemical equilibrium software Visual MINTEQ and results indicated that a strong complexation exist between TC and Cu(II), while much weaker interaction between TC and Cd(II). Traditional joint toxicity prediction model based on independent action failed to predict the combined toxicity of TC with metals. A new method based on speciation calculation was used to evaluate the joint toxicity of ligands and cations. It is assumed that the metal-ligand complexes are non-toxic to V. fischeri and the joint toxicity is determined by the sum of toxic unit of free metal-ions and free organic ligands. It explained the joint toxicity of the mixed systems reasonably well. Meanwhile, citric acid (CA) and fulvic acid (FA) were also introduced in this study to provide a benchmark comparison with TC. Results showed it is also valid for mixed systems of CA and FA with metals except for the Cd-CA mixture.

Abstract: Illite samples from Fithian, IL were purified and saturated with Na+ ions. The acid–base surface chemistry of the Na-saturated illite was studied by potentiometric titration experiments with 0.1, 0.01, and 0.001 M NaNO3 solutions as the background electrolyte. Results showed that the titration curves obtained at different ionic strengths did not intersect in the studied pH range. The adsorption of Cd(II), Cu(II), Ni(II), Pb(II), and Zn(II) onto illite was investigated as a function of pH and ionic strength by batch adsorption experiments. Two distinct mechanisms of metal adsorption were found from the experimental results: nonspecific ion-exchange reactions at lower pH values on the basal surfaces and ‘frayed edges’ and specific adsorption at higher pH values on the mineral edges. Ionic strength had a greater effect on the ion-exchange reactions. The binding constants for the five heavy metals onto illite were determined using the least-square fitting computer program FITEQL. Linear free energy relationships were found between the surface binding constants and the first hydrolysis constants of the metals. [Copyright &y& Elsevier]

The adsorption and desorption behaviors of Cd(II) and Pb(II) on goethite have important effects on the mobility and bioavailability of these compounds in soils. However, while the respective adsorption isotherms have been extensively investigated, the kinetic process has often been overlooked. Thus, in batch adsorption and stirred-flow experiments this study investigated the thermodynamic and kinetic behaviors of Cd(II) and Pb(II) on goethite as a function of the pH and the loading concentration. CD-MUSIC and integrated kinetic models were proposed to predict metal adsorption behavior, after careful consideration of the surface properties and site heterogeneity of goethite. The results showed that both the surface species and the binding ability of the two metals differed. While Cd(II) formed two corner-sharing species, (≡FeOH) 2 Cd+ and (≡FeOH) 2 CdOH, Pb(II) formed two weak corner-sharing species, (≡FeOH a) 2 Pb+ and (≡FeOH a) 2 PbOH, and one strong edge-sharing species, (≡FeOH b) 2 Pb+. Optimized binding constants (log K) and desorption rate coefficients (k d i) were calculated to quantify the contribution of each surface species to equilibrium adsorption and time-dependent adsorption/desorption under various conditions. Compared with Cd(II), the adsorption of Pb(II) on goethite has two kinds of reaction processes with different affinities, which was attributed to the site heterogeneity of goethite. The proposed model has the potential to be applied to various chemical conditions and goethite samples. Unlabelled Image • A CD-MUSIC-based kinetic model was proposed to reproduce the adsorption/desorption of Cd(II) and Pb(II) on goethite. • The model with limited parameters can predict the adsorption isotherms and kinetics under different conditions. • Compared with Cd(II), the kinetics of Pb(II) adsorbed on goethite have a stronger connection with site heterogeneity. [ABSTRACT FROM AUTHOR]