Cd Species Research Articles

Utilization of Straw Resources May Affect the Speciation of Cd and Its Solubility in Cd-Contaminated Paddy Soil

Rice-wheat rotation has long been the most typical cropping system along the mid-lower reaches of the Yangtse River in China, and the full amount returning of wheat straw before rice season is widely practiced in the rotation system. However, massive incorporation of fresh wheat straw may activate Cd in the soil solid phase and cause more labile Cd entering soil solution in Cd-contaminated soil during the flooded rice season. An incubation experiment was conducted under flooded conditions to investigate the solubility and speciation of Cd and its variation and driving factors with an ongoing decomposition phase in simulated Cd-contaminated paddy soil treated with wheat straw addition. The results indicated that wheat straw addition enhanced Cd solubility, and soluble Cd concentration increased with the ongoing decomposition phase. The observed significant positive correlation (r = 0.648, p < 0.01, n = 77) between soluble Cd concentration and DOC content in soil leachate was gradually strengthened with ongoing decomposition. Wheat straw addition decreased the exchangeable fraction of Cd and increased the residual fraction during the first 5 days of decomposition, while the exchangeable Cd increased and the residual Cd decreased after 10 days of decomposition. The exchangeable Cd increased and the residual Cd decreased gradually with ongoing decomposition. Correlation analysis showed that the exchangeable and residual fractions were sensitive to DOC content. Nitrogen fertilizer input further activated Cd by promoting wheat straw decomposition. In summary, wheat straw addition would activate Cd by increasing Cd solubility and promoting the translation from immobile fraction to labile fraction in Cd-contaminated paddy soil under flooded conditions.

Solution chemistry mechanisms of exogenous silicon influencing the speciation and bioavailability of cadmium in alkaline paddy soil

The mechanism of silicon (Si) influencing cadmium (Cd) speciation and bioavailability in alkaline paddy soil solution remains unclear. Therefore, this study sought to elucidate the effect of Si on Cd by combining chemical analysis and rice pot experiments. In this work, the effects of Na2SiO3 alkalinity and the differences in Na+ were eliminated in all treatments, and the Cd speciation in soil solutions was determined in-situ using a Field-Donnan membrane technology (DMT) cell. Additionally, rice yields and the Cd content in various parts of the rice plant were studied. The results showed that Si application significantly increased rice biomass by 32% (P < 0.05) while significantly reduced the Cd content in brown rice by 52% (P < 0.01) and the free Cd2+ concentration in the soil solution. Further analysis of the interaction of Si and Cd using Fourier transform-infrared spectroscopy (FT-IR), Raman, and X-ray photoelectron spectroscopy (XPS) indicated that a Si-Cd complex was formed by Cd and Si-O groups. In summary, Si changed the chemical speciation of Cd in the alkaline soil solution and formed a water-soluble Si-Cd complex that the rice could not absorb, consequently reducing Cd bioavailability.

Speciation Characteristics and Risk Assessment of Soil Heavy Metals from Puding Karst Critical Zone, Guizhou Province

The Community Bureau of Reference (BCR) sequential extraction method was used to analyze the distribution and chemical fractions of soil heavy metals (i.e., Cd, Cr, Zn, Fe, Ni, and Mn) under different land uses from the Puding karst critical zone, and the bioavailability and potential ecological risk of these heavy metals were evaluated. The results showed that the Fe, Zn, Cr, and Ni mainly were mainly concentrated in residual fractions and not likely to be absorbed by organisms, whereas the available fractions of Cd and Mn were in higher concentration, which retained strong potential migration and bioavailability. The richer organic matter in Puding soil might have promoted the transformation of oxidizable speciation of Fe, Ni, Cr, and Cd. The oxidizable forms of Fe, Mn, and Ni tended to accumulate in macro-aggregate soil. The risk assessment of RAC and RSP showed that the Puding karst soil was at slight ecological risk, and most heavy metals (except Cd) were at low risk to the ecological environment. Among the five land use types, the environmental risk of Cd in cropland and abandoned farmland was higher, which was mainly related to the input of Cd caused by fertilization, spraying pesticides, and other agricultural activities.

Impact of Pyrolysis Temperature and Application Amount of Sewage Sludge Biochar on the Speciation and Bioavailability of Cd and Pb in Paddy Soil

Impact of Pyrolysis Temperature and Application Amount of Sewage Sludge Biochar on the Speciation and Bioavailability of Cd and Pb in Paddy Soil

Cadmium accumulation regulated by a rice heavy-metal importer is harmful for host plant and leaf bacteria

IntroductionCadmium (Cd), one of the major toxic heavy metals, causes severe deleterious effects on all living organisms from prokaryotes to eukaryotes. Cadmium deposition affects bacterial diversity and bacterial population in soil. Cadmium accumulation in plants is mainly controlled by transporters and the resulting Cd enrichment gives rise to phytotoxicity. ObjectiveThis study aimed to mine transporters that control Cd import or accumulation in rice and uncover the underlying mechanisms that how accumulated Cd poses risks to host plant and leaf bacteria. MethodsRNA-seq analysis, histochemical assays, and elemental quantification were carried out to reveal the biological roles of OsABCG43 for Cd import. Pathogen inoculation, IC50 value, and bacterial virulence assays were conducted to disclose the effects of Cd on leaf bacteria. ResultsOsABCG43 is characterized as a Cd importer controlling Cd accumulation in rice. OsABCG43 was induced under Cd stress and specifically expressed in the vasculature of leaves and roots. Overexpression of OsABCG43 caused Cd accumulation which inhibits photosynthesis and development and alters the antioxidant system, resulting in phytotoxicity. Moreover, overexpression of OsABCG43 resulted in retarded plant growth and enhanced rice sensitivity to Cd stress. Numerous differentially expressed genes were identified via RNA-seq analysis between the OsABCG43-overexpressing plants and wild type, which functioned in Cd or reactive oxygen species (ROS) homeostasis. In addition, OsABCG43 transcripts were induced by leaf bacteria Xanthomonas oryzae pv. oryzicola (Xoc) and X. oryzae pv. oryzae (Xoo). The enriched Cd directly impaired the formation of virulence factors for the leaf bacteria, preventing colonization or proliferation of Xoc or Xoo in rice leaves. ConclusionThis work reveals that OsABCG43 is expressed specifically in the vascular and plasma membrane-localized OsABCG43 functions as a Cd importer. OsABCG43-mediated import of Cd is harmful for both rice and the corresponding leaf bacteria.

Marked changes in biochar's ability to directly immobilize Cd in soil with aging: implication for biochar remediation of Cd-contaminated soil.

To investigate the change in biochar's ability to directly immobilize Cd in soil, a successive wheat cultivation experiment was conducted. Three biochars with different Cd adsorption mechanisms were added to the soils, and a mesh bag was used to separate the soil particles (> 1μm) from the biochar. The results showed that the ash contents and anionic contents (CO32- and PO43-) of the biochar decreased with the cultivation time, while the oxygen-containing functional group content and CEC of the biochar increased. As a result, the Cd concentration on biochar decreased, by 68.9% for WBC300, while unstable Cd species (acid soluble and reducible fraction of Cd) on biochar increased with successive cultivation, increasing from 3 to 17% for WBC300 in FS. Correspondingly, the ability of biochar to inhibit Cd accumulation in wheat decreased. The results of this study illustrated that the ability of biochar to directly immobilize Cd in soil is not permanent; it gradually decreases with aging in soil. The adsorption mechanism of Cd on biochar changed from precipitation to complexation, and ion exchange processes could be the main reason.

Mechanistic and modeling insights into the immobilization of Cd and organic carbon during abiotic transformation of ferrihydrite induced by Fe(II)

Iron (Fe) oxides and fulvic acid (FA) are the key components affecting the fate of cadmium (Cd) in soil. The presence of FA influences Fe mineral transformation, and FA may complicate phase transformation and dynamic behavior of Cd. How varying Fe minerals and FA affect Cd immobilization during the ferrihydrite transformation induced by various Fe(II) concentrations, however, is still lack of quantitative understanding. In this study, we built a model for Cd species quantification during phase transformation based on mechanistic insights obtained from batch experiments. Spectroscopic analysis showed that Fe(II) concentrations affected secondary Fe minerals formation under the condition of co-existence of Cd and FA, and ultimately changed the distribution of Cd and FA. Microscopic analysis revealed that besides surface adsorption, part of Cd was sequestrated by magnetite, whereas FA was able to diffuse into lepidocrocite defects. The model revealed that adsorbed Cd was mainly controlled by FA and ferrihydrite, and direct complexation of Cd by FA had a strong impact on the continuous change in Cd at lower Fe(II) concentration. The results contribute to an in-depth understanding of the mobility of Cd in the environment and provide a method for quantifying the dynamic behavior of heavy metals in multi-reactant systems.

Simultaneous measurements of Cr, Cd, Hg and Pb species in ng L−1 levels by interfacing high performance liquid chromatography and inductively coupled plasma mass spectrometry

Toxicity, mobility, bioavailability and biofunctions of chromium, cadmium, mercury and lead are heavily dependent upon their specific chemical forms, leading to a high demand to metal speciation analysis rather than total quantification. Simultaneous speciation analysis of multiple metal(loid)s is attractive to a large sample capacity containing unstable analytes due to its economic and environmental advantages over the conventional single elemental strategies. In this work, an analytical method integrating online solid phase extraction into high performance liquid chromatography interfaced with inductively coupled plasma mass spectrometry (ICP-MS) to simultaneously preconcentrate and quantify Cr, Cd, Hg and Pb forms in pg L−1 levels in water was developed. Cr(III + VI), Cd(II), Hg(II), Pb(II), methylmercury (MeHg), ethylmercury (EtHg), and trimethyl (TML) and triethyl lead (TEL) were captured by the C18 adsorbent (equilibrated with 10 mL of 1.0 mM 2-hydroxyethanethiol at 10 mL min−1) and eluted by mobile phase (5.0 mM Cys at pH 2.0), then completely separated on the C18 column within 8.0 min and eventually determined by ICP-MS. Low limits of detection (0.001–0.007 ng L−1) and quantification (0.003–0.023 ng L−1), good relative standard deviations (<4%) and high enrichment factors (827–2656 folds) were obtained with good linearities. Three reference materials of total cadmium (GBW08602), total mercury (GBW08603) and total lead (GBW08601) in water were analyzed by the developed method to validate the accuracy with good agreement with certified values and satisfactory recoveries (92–100%). This method was proved feasible by the determination of Cr, Cd, Hg and Pb compounds in drinking water, river water, pond water and tap water.

Exploration of Cd transformations in Cd spiked and EDTA-chelated soil for phytoextraction by Brassica species.

The study of soil cadmium (Cd) fractionation has become the need of the hour due to phytoextraction of Cd heavy metal by indigenous Brassica species of northwest India. The present study was conducted to explore the Cd speciation in soils treated with Cd (0, 5.0, 10.0, 20.0, 40.0, and 80.0mgkg-1 soil) and synthetic chelate ethylene diamine tetraacetic acid (EDTA-0, 1.0 and 2.0gkg-1 soil) planted under three Brassica species (Brassica juncea L., Brassica campestris L., and Brassica napus L). The studied Cd fractions viz. exchangeable and water-soluble (EX + WS), carbonate (CARB), organic matter (OM), Mn oxide (MnOX), amorphous Fe oxide (AFeOX), crystalline Fe oxide (CFeOX), and residual (RES) differed in their Cd content in soils under three investigated Brassica species. Among all plantations, B. juncea reduced the highest soil Cd content of EX + WS form which reflected its bioavailability. The Cd supplementation significantly enhanced the Cd concentration in all Cd forms with EX + WS Cd form exhibiting higher increase even at low Cd level (5.0mgkg-1), whereas the EDTA addition did not influence Cd fractions. The application of EDTA @ 1.0gkg-1 soil proved beneficial as it enhanced the metal mobility for plant extraction. All species positively significantly correlated (r = 0.648** to 0.747**) with all Cd fractions but except B. juncea all confronted reduction in their total biomass. In nutshell, it suggested that Brassica species having large plant biomass could be considered as a potential candidate for phytoremediation.

Cotransport of nano-hydroxyapatite and different Cd(II) forms influenced by fulvic acid and montmorillonite colloids

Soil colloids can affect the cotransport of nanoparticles and pollutants. In this study, the influencing mechanisms of organic fulvic acid (FA) and inorganic montmorillonite colloid (MONT) on the cotransport of nHAP and Cd(II) were investigated. Column experiments combined with Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, attachment efficiency calculation and two-site kinetic retention model were applied to study the mechanisms. Results showed that the co-existence of FA or MONT made the transport of nHAP improved by 58–75% and 33–59%, respectively. Both of them could improve the stability of nHAP particles and enhance electrostatic repulsion between nHAP particles and sand. Retention of nHAP in the sand was mainly caused by secondary energy minimum and physical straining. The co-existence of FA or MONT changed the amount of adsorbed species of Cd(II) and decreased the retardation effect of nHAP on Cd(II) transport. With increasing FA concentration, soluble FA·Cd and suspended nHAP·FA·Cd complexes in the system increased. Transport of soluble Cd(II) and total Cd(II) were strengthened due to the concentration effect of FA and the improved stability of nHAP particles. With increasing MONT concentration, the amount of soluble Cd(II) decreased, but that of colloidal Cd(II) (nHAP·Cd and MONT·Cd) increased. Due to the stronger effect of colloidal Cd(II) change than that of the soluble Cd(II) change, the transport of total Cd(II) was improved by 34–57%. The findings of this study can help to understand the fate of nanoparticles and Cd(II) in natural water and soil.

Enhanced Electrokinetic Remediation of Cadmium (Cd)-Contaminated Soil with Interval Power Breaking

This study compared electrokinetic (EK) remediation with and without interval power breaking in the removal of total and plant available cadmium (Cd) in the soil. Two laboratory experiments, i.e. EK remediation with interval power breaking (24–12 h power-on-off cycles) and conventional EK remediation (continuous power supply), with the same accumulated time (192 h) of power supply, were conducted to remove soil Cd. After the EK remediation with interval power breaking, the total Cd removal efficiency in the soil rose to 38%, in comparison to 28% after the conventional EK remediation. As for the plant available Cd, the removal efficiency was enhanced from 52 to 63%. Additionally, the electric current during the EK remediation and electric conductivity after the EK remediation were higher in the soil treated by interval power breaking, which indicated an enhanced desorption and/or migration of charged species. It further meant that the higher removal efficiency of soil Cd by interval power breaking could be related to the enhanced desorption and/or migration of Cd species. This study indicated that both conventional EK remediation and EK remediation with interval power breaking were effective methods to remove soil Cd but EK remediation with interval power breaking was more efficient.

Co-high-efficiency washing agents for simultaneous removal of Cd, Pb and As from smelting soil with risk assessment

Soil washing is considered a highly efficient technology due to its higher removal rate of multiple heavy metals from contaminated soil. However, previous studies on Cd, Pb and As washing agents for soils with complex contaminations did not consider the differences in As and Cd/Pb properties, resulting in the lack of effective washing compounds and washing conditions for soils with complex contaminations. Moreover, most traditional washing agents can cause secondary pollution. In this study, HEDTA and lactic acid (LA) treatments resulted in a higher Cd and Pb removal, while 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) was more effective in As removal. Most importantly, a new washing strategy was proposed with a new combined high-efficiency washing agents consisting of HEDP + LA + FeCl3 with a ratio of 6:3:1. Considering washing efficiency and consumption under optimal washing conditions, i.e. the soil/liquid (S/L) ratio of 1:20 and washing time of 48 h, the rates of Cd, Pb and As removal were 79.93%, 69.84% and 61.55%, respectively. In addition, washing process could influence the speciation of heavy metals, especially oxidizable and residual Cd and Pb fractions, as well as reducible As fraction. The washing process using the new washing agent can significantly reduce the pollution level and health risk of Cd, Pb and As contamination. The results of this study can provide an efficient washing agent for the remediation of heavy metal-contaminated soils at smelting sites, which will help protect human health.

Effect of application mode (capping and amendment) on the control of cadmium release from sediment by apatite/calcite mixture and its phosphorus release risk.

In this research, the influence of application mode (capping and amendment) on the control of cadmium (Cd) liberation from sediment by apatite/calcite mixture and its phosphorus release risk were investigated. The results showed that calcite addition had a limited effect on the speciation of Cd in sediment, but apatite addition had a significant impact on the fractionation of Cd in sediment. Apatite amendment could effectively immobilize the most readily mobilized Cd by transferring the acid-soluble fraction to the reducible and residual fractions. Apatite addition also could effectively reduce the concentration of toxicity characteristic leaching procedure (TCLP)-leachable Cd in sediment, and apatite had a much higher reduction efficiency of TCLP-leachable Cd than calcite. Apatite/calcite mixture capping could reduce the risk of Cd liberation from sediment into the overlying water, and the controlling efficiency of apatite/calcite mixture capping was higher than that of apatite/calcite mixture amendment. The effect of apatite/calcite mixture addition on the concentration of reactive soluble phosphorus (SRP) in the overlying water was limited. The introduction of calcite into the apatite capping layer could lower the risk of phosphorus release from apatite to the overlying water as compared to single apatite capping. However, the apatite/calcite mixture capping layer still had a relatively high risk of phosphorus liberation into the overlying water. Results of this work suggest that apatite/calcite mixture has a high potential to be used as a capping material to control Cd release from sediment from the perspective of controlling efficiency and application convenience.

Effect of rice straw biochar on three different levels of Cd-contaminated soils: Cd availability, soil properties, and microbial communities

Biochar can be effective in immobilizing soil cadmium (Cd), but the difference in its immobilization mechanisms for different levels of Cd-contaminated soils was overlooked. In this study, rice straw biochar (BC) was added to three Cd-contaminated soils following 180 days of incubation, in the process of which the dynamic changes of Cd speciation, soil properties and microbial community diversity were determined. BC could significantly reduce the ratio of acid-soluble in the three soils, especially in light and medium Cd-contaminated soils by more than 20%. The addition of biochar could significantly increase the soil pH, soil organic matter, cation exchange capacity, and the activities of catalase, but decrease the richness and diversity of bacterial communities in all soils. The associations between microbial communities were inhibited in light and medium Cd-contaminated soils, but promoted in heavy Cd-contaminated soils. Furthermore, the main pathway of BC effect on soil Cd availability was also analyzed by partial least squares model (PLS-PM), which indicated that BC indirectly reduced Cd availability mainly by regulating the microbial community in light Cd-contaminated soil, whereas BC directly reduced Cd availability primarily by its own adsorption in medium and heavy Cd-contaminated soils. This research deepened understanding of the mechanisms of stabilization of Cd by biochar for agricultural soils.

Vertical Distributions and Bioavailabilities of Heavy Metals in Soil in An-Tea Plantations in Qimen County, China

Heavy metals mainly enter tea from the soil. In this study, stratified soil samples were collected, at a depth of 0–60 cm, using a soil drill in An-tea plantations. Speciation of As, Cd, Cr, Cu, Ni, Pb, and Zn was determined using the European Community Bureau of Reference sequential extraction method, and the heavy metal concentrations in the extracts were determined by inductively coupled plasma−mass spectrometry. Compared with other soil layers, the mean Cd, Cu, Pb, and Zn concentrations were highest in the 0–20 cm layer, the Ni concentrations were highest in the 20–40 cm layer, and the As and Cr concentrations were highest in the 40–60 cm layer. The mean contributions of the non-residual fractions, including the acid-soluble, reducible, and oxidizable fractions, to the total concentrations were higher than those of the residual fraction for Cr, Cu, and Ni at all depths in soil from a flat area, as well as for Cd and Zn at all depths in soil from a sloping area. The contributions of non-residual fractions to the total As and Pb concentrations were higher than those of the residual fraction in soil from a depth of 0–20 cm from the flat area and soil from a depth of 20–60 cm from the sloping area. The total heavy metal concentrations correlated well with the acid-soluble fraction and reducible fraction concentrations in soil from 0–40 cm.

Effects of pH variations caused by redox reactions and pH buffering capacity on Cd(II) speciation in paddy soils during submerging/draining alternation

Incubation experiments were conducted to investigate the influencing factors of pH variation in different paddy soils during submerging/draining alternation and the relationship between pH buffering capacity (pHBC) and Cd speciation in ten paddy soils developed from different parent materials (including 8 acid paddy soils and 2 alkaline paddy soils). The soil pHBC and the changes in soil pH, Eh, Fe2+, Mn2+, SO42- and Cd speciation were determined. The results showed that there was a significant positive correlation between cation exchange capacity (CEC) and pHBC of these paddy soils, indicating that soil CEC is a key factor affecting the pHBC of paddy soils. The contribution of Fe(III) oxide reduction to H+ consumption is far greater than the reduction of Mn(IV)/Mn(III) oxides and SO42- during the submerging. For example, the contribution of the reduction of manganese oxides, SO42- and iron oxides to H+ consumption in the paddy soils from Anthrosol at 15 d submerging was 1.2%, 11.6% and 87.2%, respectively. This confirms that the reduction of Fe(III) oxides plays a leading role in increasing soil pH. Importantly, we noticed that during submerging, soil pH was increased and resulted in the content of available Cd in soils being reduced. This was due to the transformation of Cd to less active forms. Also, there was a significant positive correlation between the change rate of available Cd, the percentage of acid extractable Cd and pH variation. This suggests that the variation in soil pH was responsible for the transformation of Cd speciation. In addition, the change rate of available Cd and the percentage of acid extractable Cd concentration were significantly negatively correlated with soil pHBC. The soil with higher pHBC experienced less pH change, and thus the change rate of available Cd and the percentage of acid extractable Cd concentration were less for the soil. The results of this study can provide a basis for the remediation of Cd-contaminated acidic paddy soils.

Remediation of Cd (II) ions in aqueous and soil phases using novel porous cellulose/chitosan composite spheres loaded with zero-valent iron nanoparticles

Novel porous cellulose/chitosan composite spheres loaded with nanoscale zero-valent iron (nZVI/PCSs) were fabricated for the removal of Cd (II) from aqueous solution and the remediation of Cd species in contaminated soil. The green-based nZVI/PCSs exhibited the improved dispersion and antioxidability of nZVI compared to the pristine one. The results from SEM/EDS suggested that the Fe (0) took part in the adsorption of the Cd (II) ions; whereas XPS analysis revealed that Fe (0) and amino groups in nZVI/PCSs played crucial roles in Cd (II) removal via the effects of precipitation or chelation. The results of the experiments in aqueous solution and model fitting showed that the adsorption of Cd (II) induced by nZVI/PCSs was better described by Langmuir isotherm and the maximum adsorption capacity reached up to 110.3 mg/g. The soil remediation tests demonstrated that nZVI/PCSs could significantly enhance cadmium immobilization, enabling the conversion of most exchangeable Cd species to FeMn oxides and organic matters in contaminated soil after the remediation. Overall, nZVI/PCSs have great potential as an excellent adsorbent with cost-effectiveness in Cd (II) removal from the aqueous solution and the remediation of Cd species in contaminated soil phases.

A diatomite-template self-sacrificing route for Mg-chlorite and its adsorption behavior towards Pb(II)/Cd(II)

Heavy metal pollution has caused worldwide attention due to its toxicity to people's health. It's necessary to design and synthesize adsorbents with excellent adsorption performance in low cost. In this work, diatomite is adopted as a self-sacrificing template for the synthesis of adsorbent Mg-chlorite. The three-dimensional (3D) hierarchical porous Mg-chlorite perfectly inherits structure characters from diatomite and exhibits a high specific surface area of 337 m2/g. The maximum adsorption capacities of Mg-chlorite towards Pb(II) and Cd(II) reach 961 mg/g and 506 mg/g, respectively, higher than that of the referenced adsorbents. The Pb(II), Cd(II) adsorption onto Mg-chlorite is a monolayer exothermic process. Chemisorption mainly controls the adsorption rate, in which mass transfer exerts greater influence than intra-particle-diffusion. Electrostatic attraction, chemisorption and co-precipitation are involved in the adsorption process, and co-precipitation mainly contributes to the excellent adsorption performance according to XRD, FT-IR and XPS analysis. This study provides a novel diatomite-template self-sacrificing method in the synthesis of 3D hierarchical porous magnesium silicate. The excellent adsorption performance for Pb(II) and Cd(II) species makes the low cost Mg-chlorite a great potential in the application of practical environment remediation.

Humic acids restrict the transformation and the stabilization of Cd by iron (hydr)oxides

Iron (hydr)oxides and their association with organic matter significantly affect the mobility of heavy metals in natural soils and sediments. However, the behavior of cadmium (Cd) during crystalline iron (hydr)oxide formation in the presence of humic acid (HA) is still unknown. In this study, the speciation of Cd in iron (hydr)oxide-HA coprecipitates were studied by extraction, surface complexation model (SCM) calculation and characterization of the composites during the aging. The results showed that aging promoted the stabilization of ~30–50% of the added Cd ions with minerals in the binary iron (hydr)oxide systems. The reduction of Cd occurred earlier than hematite formation, indicating that the aggregation of amorphous iron (hydr)oxide led to the initial immobilization of Cd. The presence of HA restricted the crystallization of iron (hydr)oxide by the formation of tight mineral nanoparticle-HA aggregates, while there were negligible changes in the speciation of Cd and Fe during aging at high HA concentrations. Therefore, HA promoted the adsorption of Cd onto amorphous iron (hydr)oxide but limited the partition of Cd to mineral aggregates. The knowledge about the role of HA in iron (hydr)oxide transformation and Cd speciation is of great significance for the prediction of heavy metal behavior in soils and sediments.

Potential environmental risk of natural particulate cadmium and zinc in sphalerite- and smithsonite-spiked soils

Cadmium (Cd)-bearing sphalerite and smithsonite ore particles are ubiquitous in soils near metal-mining areas. Previous studies indicate that smithsonite is more readily dissolved in acidic waters and soils than sphalerite but the mobility of Cd and zinc (Zn) derived from these ores in soils is unknown. Using microcosm incubation experiments and microscopic and spectroscopic analysis, we found that the mobility of Cd and Zn derived from smithsonite is higher than from sphalerite. The mobilization rates of Cd (16.6%) and Zn (13.7%) released from smithsonite in soils after 30-day incubation experiments were higher than those from sphalerite (Cd, ~ 1.42%; Zn, ~ 0.75%). Moreover, the percentages of Cd2+ and Zn2+ in soil pore water showed a dynamic increase in smithsonite-spiked treatments but a decrease in sphalerite-spiked treatments. HRTEM-EDX-SAED analysis further indicates the occurrence of dynamic transformation of amorphous Cd and Zn species in soil pore water to crystalline ZnS and iron oxides in sphalerite-spiked soil but crystalline ZnCO3 nanoparticles were dynamically transformed to amorphous metal-bearing species in smithsonite-spiked soil. The opposite transformation trends in pore water of Zn ore-spiked soils provide new insights into the Cd environmental risks in soils affected by Zn mining.