Stable Cd Research Articles

Cd mobilization in mining-impacted soils with different bedrock lithology: Insights from stable Cd isotopes

The environmental risk of Cd in soils strongly depends on the mobilization of Cd in soils. However, limited knowledge exists on the redistribution of exogenic Cd inputs in soils, especially across diverse lithological regions. Herein, we aimed to investigate the fate of Cd in soils from two mining areas with contrasting lithologies (siliceous and calcareous) using stable Cd isotopes. The isotope tracing results confirm that mining activities are the main Cd source in both areas. The positive correlation between δ114/110Cd values and goethite/dolomite content indicates the release of heavy Cd isotopes during the dissolution of exogenetic minerals. Additionally, high contents of exchangeable Cd (11 % to 36 %) and Fe oxide-bound Cd (29 % to 42 %) drive plant pumps to transport heavy Cd isotopes from the deeper to upper horizons of the soils from the siliceous area. In the calcareous area, the total organic carbon content is positively correlated with the Cd concentration and δ114/110Cd value, suggesting potential complexation of Cd with organic matter due to the stabilizing effect of carbonate minerals on soil organic matter. This study highlights the different redistributions of exogenous Cd in soils from diverse lithological regions, emphasizing the need to consider regional lithology when developing soil quality standards for Cd.

Stable Cd(II)-based coordination polymer as a multifunctional fluorescent sensor for ascorbic acid, acetylacetone and nitrofuran antibiotics

The concentrations of hazardous volatile organic compounds (VOCs), pharmaceutical antibiotics and biomolecules in water systems are closely related with public health and ecological security. Thus, the convenient and accurate detection of these harmful items can not only reflect the state of human health but also evaluate the level of homologous contamination in the environment. To this end, a new Cd(II)-CP ({[Cd3L2(bmoe)]·DMF}n) with excellent luminescence properties was designed by employing the semi-rigid tricarboxylic acid 4-(2′,3′-dicarboxylphenoxy) (H3L) and N-donor ligand 1,1′-bis(1H-benzimidazolyl) oxydiethane (bmoe). The as-prepared Cd-CP features the unique uninodal sql topology. Benefiting from its great stability in the aqueous system, Cd-CP serves as a versatile multifunctional fluorescent sensor for different analytes, ascorbic acid (AA), nitrofuran antibiotics nitrofurantoin (NFT) and nitrofurazone (NFZ) and acetylacetone (ACAC). The established methods are characterized with impressive low detection limits, ultrafast response time, high sensitivity, strong anti-interference ability, as well as reliable reproducibility. Experimental and theoretical calculation reveals that the collaborative effects of Förster resonance energy transfer (FRET), inner-filter effect (IFE) and photoinduced electron transfer (PET) are the most probable causes behind the quenching of the CP's fluorescence signal.

Urea reduces the sustainability of soil Cd immobilization by upregulating the expression of AmSTOP1 and AmMATE genes in edible amaranth roots

After cadmium (Cd) immobilization remediation in contaminated farmland soil, which forms of nitrogen fertilizer should be implemented to keep its sustainability? Urea and nitrate were used to compare for their effects on the remobilization of stabilized Cd in the rhizosphere soil of edible amaranth at nitrogen concentrations of 60, 95, and 130 mg kg−1. The results showed that compared to nitrate nitrogen, the Cd content in shoots increased by 76.2%, 65.6%, and 148% after applying three different concentrations of urea, and the total remobilization amount of Cd also increased by 16.0%, 24.9%, and 14.0% respectively. Urea application promotes root secretion of citric acid, malic acid, pyruvate, and γ-aminobutyric acid, crucial in remobilizing stable Cd. The application of urea promoted the expression of genes involved in sucrose transport, glycolysis, the TCA cycle, amino acid secretion, citric acid efflux, and proton efflux. Arabidopsis heterologous expression and yeast one-hybrid assays identify critical roles of AmMATE42 and AmMATE43 in citric acid and fumaric acid efflux, with AmSTOP1 activating their transcription. Inhibition of SIZ1 expression in urea treatment reduce AmSTOP1 SUMOylation, leading to increased expression of AmMATE42 and AmMATE43 and enhanced organic acids efflux. Using edible amaranth as a model vegetable, we discovered that urea is not beneficial to preserving the sustainability of stabilized Cd during the reuse of remediated farmlands contaminated with Cd.

A microporous Cd(II)-MOF for efficient separation of trace SO2 from SO2/CO2/N2 mixture

Trace SO2 removal of flue gas is very important to prevent environmental pollution. Porous Metal-Organic Frameworks (MOFs) possess natural advantages for the mixed gas separation. In the present work, a new microporous Cd(II)-MOF (named HBU-23) has been conveniently synthesized, it possesses a three dimensional (3D) coordination network with trinuclear cluster units. The BET surface area of HBU-23 reaches 384.20 m2/g and the pore size distribution is 6.79 Å. HBU-23 exhibits excellent adsorption ability for SO2, and the saturated adsorption capacity can reach 91.38 cm3/g under ambient condition. More importantly, the compound exhibits higher IAST selectivities for the mixture gases of SO2/CO2 (10 %, 58.9), SO2/N2 (10 %, 2333.5) and SO2/CH4 (10 %, 484.8), which indicate its’ possible applications in the field of flue gas and natural gas desulfurization. Breakthrough experiments further prove that it can be efficiently removal trace SO2 from flue gas, and it can be reused at least three cycles without obvious degradation in separating ability. Furthermore, HBU-23 also shows better separation selectivity of C2H2/CO2 (50 %, 3.0) and CO2/N2 (15 %, 28.4). GCMC simulations and DFT calculations reveal its effective separation property can attribute to the strong interaction and binding energy between HBU-23 and SO2 molecules. The work will contribute to the rational design new MOFs used as gas adsorbents.

Surface-loaded magnesium and phosphorus-modified lignite adsorbents: Efficient adsorption and immobilization for remediation of Cd-contaminated water and soil

Lignite is a resource-rich material with favorable adsorption properties and can be used as an environmentally friendly material for removing heavy metals. In this study, we loaded magnesium and phosphate ions onto the surface of lignite (LM) by using chemical modification to generate modified lignite materials, Mg-LM and P-LM, which were used for the adsorption and immobilization of Cd (II) in polluted water and soil. Characterization analysis showed the introduction of exchangeable Mg ions and enhancement of the pore structure in Mg-LM; the increase in the number of oxygenated functional groups and, exchangeable calcium ions and P content of P-LM may favor the adsorption and immobilization of Cd (II). Cd (II) adsorption on Mg-LM and P-LM was consistent with the pseudo-secondary kinetics and Langmuir isotherm models. The maximum adsorption capacity of Cd (II) on Mg-LM and P-LM was 1033 mg/g and 55 mg/g, respectively. The reduction in the soil DTPA-Cd content (32.9%) was greater under P-LM treatment than under Mg-LM (20.2%) and LM (11.1%) treatments. In addition, successive BCR extractions confirmed that Mg-LM and P-LM promoted the transformation of unstable Cd fractions to stable Cd fractions in the soil. The XRD, FTIR, and XPS results indicated that electrostatic interactions, ion exchange, surface complexation and precipitation might be the main mechanisms involved in the adsorption and immobilization of Cd (II) by Mg-LM and P-LM. Our results suggest that Mg-LM is more suitable than P-LM for the remediation of Cd-contaminated water, and less applicable than in Cd-contaminated soil.

Stable CdII-Based Metal–Organic Framework as a Multiresponsive Luminescent Sensor for Acetylacetone, Salicylaldehyde, and Benzaldehyde with High Sensitivity and Selectivity

Stable Cd^II-Based Metal–Organic Framework as a Multiresponsive Luminescent Sensor for Acetylacetone, Salicylaldehyde, and Benzaldehyde with High Sensitivity and Selectivity

Effects of cultivar, water condition and their interactions on Cd accumulation in rice grains

Using low Cd accumulation cultivars and managing field water regimes are effective measures to mitigate Cd accumulations in rice grains. However, the effect of the cultivar-water condition interaction (CWI) on grain Cd accumulations has largely been ignored. To solve this problem, pot and hydroponic experiments were conducted using 14 rice cultivars and two contrasting water conditions. The results showed that CWI significantly affected Cd concentrations in rice grains and roots, explaining 8.8% and 22.8% of the total variance, respectively. These CWI effects were derived from cultivar-dependent variations in rhizosphere soil properties [Eh, pH and available Cd associated with root radial oxygen loss (ROL)] and root Cd uptake. In this context, cultivar HH61 exhibited low, stable Cd accumulations, owing to its stably lower translocation rate, root Cd uptake ability and available Cd in its rhizosphere than the other cultivars, which was induced by its lower ROL. Root-to-grain Cd translocation rates were vital in determining Cd accumulations in grain of different cultivars but were independent from CWI. These results indicated that CWI could play an important role in Cd accumulation in rice while stable low-Cd cultivar should possess low ROL under flooding and low root-to-grain Cd translocation rate. The results will provide novel theoretical basis for cultivar selection and hence benefit the extensive use of low-accumulation cultivars and public health.

Quantitative transport and immobilization of cadmium in saturated-unsaturated soils with the combined application of biochar and organic fertilizer.

In this study, cadmium (Cd) transport and immobilization on passivators (biochar, organic fertilizer) and soils under saturated-unsaturated conditions were independently analyzed. The results showed that the Cd adsorption capacities of biochar and organic fertilizer were comparable in acidic soils. But in alkaline soils, the Cd adsorption capacity of organic fertilizer was significantly larger than that of biochar. In acidic soils, passivators effectively immobilized Cd, and the total net effects were in the order: combination (44.05-58.13%) > 3% biochar (31.96-46.88%) > 3% organic fertilizer (28.78-41.82%). In alkaline soils, all treatments had negative effects on Cd immobilization. For acidic soils, the immobilization of Cd was mainly attributed to the passivators, and the positive contribution percentages of relatively stable Cd increase by passivators were 81.05-100%, while those by soils were 0-18.95%. For alkaline soils, after the treatments of passivators, although a considerable amount of Cd was immobilized inside the passivator, Cd was activated more inside the soil. Therefore, it is noteworthy that soil conditions must be fully considered when applying biochar and organic fertilizers for Cd remediation.

A Study on the Behavior of Cadmium in the Soil Solution-Plant System by the Lysimeter Method Using the 109Cd Radioactive Tracer.

In soils, cadmium (Cd) and its compounds, originating from industrial activities, differ both in mobility as well as in their ability to permeate the soil solution from naturally occurring cadmium compounds (native Cd). Therefore, the determination of the parameters of cadmium mobility in soils and its accumulation by plants in the soil-soil solution-plant system is very important from both scientific and practical viewpoints. 109Cd was used as a radioactive tracer to study the processes of the transition of Cd into the aqueous phase and its uptake by plants over the course of a vegetative lysimeter experiment. Using sequential extraction according to the Tessier-Förstner procedure and modified BCR schemes, certain patterns were determined in the distribution of Cd/109Cd among their forms in various compounds in the soil, along with the coefficients of the enrichment of native stable Cd with radioactive 109Cd. It was shown that the labile pool of stable Cd compounds (29%) was significantly smaller than that of radioactive 109Cd (69%). The key parameters characterizing the migration capacity of Cd in the soil-soil solution-plant system were determined. It was found that the distribution coefficient of native Cd between the soil and the quasi-equilibrium lysimeter solution exceeded the similar value for the 109Cd radionuclide by 2.2 times, and the concentration coefficients of Cd and 109Cd in the barley roots were 9 times higher than in its vegetative parts. During the experiment, the average removal of Cd (109Cd) from the soil by each barley plant was insignificant: 0.002 (0.004)%. Based on the results of 13C nuclear magnetic resonance (NMR) spectroscopy of a lyophilized sample of the high-molecular-weight dissolved organic matter (HMWDOM) of the soil solution, its components were determined. It transpired that the isolated lyophilized samples of HMWDOM with different molecular weights had an identical structural and functional composition. The selective sorption parameters of the HMWDOM and humic acid (HA) with respect to Cd2+ ions were determined by the isotope dilution method.

Soil addition of MnSO4 reduces wheat Cd accumulation by simultaneously increasing labile Mn and decreasing labile Cd concentrations in calcareous soil: A two-year pot study

Cadmium (Cd) pollution of wheat fields is a serious environmental and health problem that warrants attention. Manganese (Mn)-containing materials are considered effective for inhibiting Cd accumulation in Cd-contaminated acidic soils. However, information on the long-term remediation effects of Mn fertilizers on Cd accumulation in wheat and on the microbial community in calcareous soils remain limited. Here, a two-year pot experiment was conducted to assess the performance of 0.05–0.2% MnSO4 addition in Cd-contaminated calcareous soils (total Cd concentration: 3.65 mg/kg) on Cd accumulation in wheat as well as on the soil bacterial community. The formation of Mn oxides and transformation of exchangeable Cd to stable Cd fractions confirmed that the application of MnSO4 significantly decreased CaCl2-extractable Cd concentrations in soil (0–47.08%). In addition, MnSO4 addition improved the antagonistic effect of Cd and Mn ions in the wheat rhizosphere by increasing the available Mn concentration in the soil (1.04–3.52 times), thereby significantly reducing wheat Cd accumulation by 24.66–54.70%. Notably, the addition of MnSO4 did not affect the richness and diversity (P > 0.05) but altered the composition and function of bacterial communities, especially those involved in metabolism and genetic information processing. Importantly, the effects of MnSO4 on Cd immobilization in soil (10.66–47.08%) and the inhibition of Cd accumulation in wheat (12.13–54.30%) can last for two years after one addition. Furthermore, the maximum decrease in Cd concentration in grains was found in the low-Cd wheat cultivar, with values of 31.39–54.70% and 19.94–54.30% in the first and second years, respectively. Based on the present findings, the combination of MnSO4 with a low-Cd wheat cultivar is effective for the safe utilization of Cd-contaminated calcareous soils.

Graphene oxide modified electrode enhances electricity generation and heavy metal removal in photosynthetic microalgae microbial fuel cells

Improving the power generation performance and pollutant removal of photosynthetic microalgae microbial fuel cells (PMMFCs) is the key to their large-scale application. In this work, microalgae (Chlorella sp. QB-102) were used as a biocatalyst in the cathode, and foam nickel modified by graphene oxide with two degrees of oxidation was used as the electrode. The results showed that the maximum power density of PMMFCs with high oxidation degree graphene oxide modified electrode (NF-GO-H) reached 209.07 mW·m-2, which was 6 times that of PMMFCs with low oxidation degree graphene oxide modified electrode (NF-GO-L), indicating that the use of the NF-GO-H electrode can effectively improve the electrical properties of PMMFCs. Simultaneously, the NF-GO-H electrode can effectively remove Cd(II), with a capacity of 6.039 g·m-2, which is twice that of the NF-GO-L electrode. Moreover, through the synergistic electrochemical action of Chlorella sp. QB-102, a large number of hydroxyl groups can be generated to convert the adsorbed Cd(II) into a more stable Cd(OH)2 precipitate. The results of this work will further expand the application of PMMFCs in power generation and heavy metal removal.

Identifying key processes driving Cd long-term adsorption and immobilization by biochar in soils and evaluating combined aging effects under simulated local climates

To investigate the effects of major environmental processes on biochar aging in field soils, four individual aging processes (dry-wet cycling, freeze-thaw cycling, leaching, and acidification) and a combination treatment including these four individual aging processes were conducted. The effects of five aging treatments on Cd transport between soils and biochar and Cd immobilization by pristine and KMnO4-modified biochars in soils were quantified. The results showed that the percentages of the total net effects of the aging treatments (the percentage sum of the decrease in Cd released into the environment and the increase in relatively stable Cd fractions in the soil) were in the following order: combined aging (−81.79% to −60.66%) < dry-wet cycling (−32.27% to −20.99%) < acidification (−21.93% to −14.46%) < freeze-thaw cycling (−22.69% to −6.91%) < leaching (8.51%–13.76%) for the CK, pristine biochar, and modified biochar treatments. The combined aging treatment had the most negative net effect on Cd immobilization because the effects of the four individual aging treatments superimposed to a certain degree. Modified biochar was more effective for Cd immobilization than pristine biochar under all five aging treatments. These results indicated that dry-wet cycling is a key environmental process among four individual aging processes in this study area, and that leaching is the only process that produces positive outcomes. Therefore, field soil moisture conditions can be adjusted to facilitate Cd immobilization by biochar. Moreover, combined environmental effects rather than individual aging processes should be considered under local climatic conditions when assessing biochar aging in field soils.

A 24-epibrassinolide treatment and intercropping willow with alfalfa increase the efficiency of the phytoremediation of cadmium-contaminated soil

Cadmium contamination in agricultural soils threatens food security and human health, and that has caused widespread concern worldwide. Willow and alfalfa are widely used for the phytoremediation of cadmium (Cd)-contaminated soil, and willow NJU513 is the promising plant for remediating Cd-contaminated soil. In order to discuss the effect of intercropping willow NJU513 with alfalfa on the phytoremediation of Cd-contaminated soil, a pot-culture experiment was conducted in the greenhouse. The result showed that the phytoremediation of Cd-contaminated soil was enhanced by this intercropping because of the 25.90 % increase in the available Cd content. In order to increase the phytoremediation efficiency of Cd in the intercropping treatment, a 24-epibrassinolide (Brs) treatment was designed in the current study. The results showed that the phytoremediation of Cd-contaminated soil by willow and alfalfa improved following a Brs treatment because of the 16.32–74.15 % and 16.91–44.48 % increases in the plant biomass and available Cd content, respectively. Additionally, the extracted Cd by plants in the intercropping treatments with and without Brs was 0.56 and 0.31 mg pot−1, respectively. Transcriptome analyses of willow leaves revealed that Brs up-regulated the expression of genes related to calcium channel activity, calcium and zinc transmembrane transport, photosynthesis, catalase/antioxidant activity, glutathione metabolic processes and detoxification, phagosomes, and vacuoles, and that these upregulated genes promoted plant remediation efficiency and resistance to Cd stress. Brs promoted the phosphate ion transporter activity in willow leaves, which may have enhanced the solubilization of insoluble phosphate minerals by bacterial species (e.g., Vicinamibacterales, Bacillus, and Gaiella) to release Cd, ultimately leading to increased phytoremediation efficiency. In addition, plants with and without Brs treatments induced the bacteria-mediated transformation of available Cd to stable Cd. The study findings may be useful for improving the phytoremediation of Cd-contaminated paddy soil.

Fluorescence sensor based on highly stable Cd(Zn)-coordination polymers for efficient detection of Cr2O72-/Nitrobenzene and recognition mechanism

Two new coordination polymers (CPs), namely, [Zn(GCA)(BDE)]·(H2O) (1) and [Cd(GCA)(TIB)]·(H2O) (2), were designed and synthesized by using H2GCA (Glutaric acid), TIB (1,3,5-tris(1-imidazolyl)benzene), BDE (1-(4-imidazole-1-ylphenyl)imidazole), with Zn2+ or Cd2+ ions under solvothermal or hydrothermal conditions. The two CPs were characterized via infrared spectroscopy, UV–vis spectroscopy, single-crystal diffraction, elemental analysis, thermogravimetric analysis, powder X-ray diffraction, and fluorescence properties. The 3D supramolecular compounds CPs 1–2 is formed by weak interaction hydrogen bonding or π … π stacking. Fluorescence detection results of CPs 1–2 show that they can act as excellent sensors of Cr2O72− and nitrobenzene with a low limit of detection, a high quenching rate and a high quenching constant. The results can be applied to the determination of Cr2O72− and nitrobenzene in water-ethanol system.

First “unsaturated soils” view towards quantitative adsorption and immobilization mechanisms of Cd by biochar in soils during aging

Instead of traditional batch and column experiments with large water-soil ratios, this study investigated the behaviors and mechanisms of Cd adsorption and immobilization by biochar in unsaturated soils, in which the soil moisture conditions were closer to those in the actual field. The transport, transformation, and immobilization of cadmium (Cd) by pristine and KMnO4-modified biochars in unsaturated soils were investigated during a 48-week mild aging process. Biochar acidified with HCl solution was employed to quantify the contributions of mineral and non-mineral components in biochar to Cd adsorption and immobilization in unsaturated soils with a three-layer mesh method. The behaviors and mechanisms of Cd adsorption by biochar in unsaturated soils significantly differed from those in aqueous solutions. The equilibrium times of Cd adsorption by biochar in unsaturated soils (weeks) were much longer than those in aqueous solutions (hours). The percentages of the Cd adsorbed by pristine and modified biochar remained relatively constant relative to the total Cd in unsaturated soils, which accounted for 39.50–49.39 % and 57.35–68.94 %, respectively. The contribution of mineral components to Cd adsorption dominated in both unsaturated soils (45.00–94.09 %) and aqueous solutions (70.73–95.51 %). The process of Cd immobilization in unsaturated soils was that biochar firstly adsorbed the exchangeable Cd from the soil, and then converted it to relatively stable Cd. After aging for 48 weeks, the contributions of non-mineral components to Cd immobilization dominated in unsaturated soil with a low concentration (1.23 mg·kg−1), and the contributions of mineral components to Cd immobilization dominated in unsaturated soil with medium-high concentrations (4.08–51.26 mg·kg−1).

Stable Cd Metal-Organic Framework as a Multiresponsive Luminescent Biosensor for Rapid, Accurate, and Recyclable Detection of Hippuric Acid, Nucleoside Phosphates, and Fe3+ in Urine and Serum.

Detecting biomarkers associated with diseases has significant meaning for early prevention, diagnosis, and treatment of diseases. The development of luminescent biosensors for rapid and accurate detection in real urine and serum is urgently desired for human health monitoring. Herein, a luminescent cadmium metal-organic framework, {[Cd(L)(bpbix)]·x(solv)}n (1), was successfully prepared by using a urea-functionalized dicarboxylate ligand, 5-(3-(pyridin-4-yl)ureido)isophthalic acid (H2L), 4,4'-bis((1H-imidazol-1-yl)methyl)biphenyl (bpbix), and the Cd2+ ion. The structure of 1 presents a 2-fold interpenetrating three-dimensional pillared-layer framework. The complex 1 exhibits good stability in different-pH aqueous solutions and physiological fluids. Strikingly, the complex 1 shows quick response, high sensitivity, good anti-interference performance, and a recyclable ability for simultaneous sensing of hippuric acid (HA), nucleoside phosphates, and Fe3+ in water. More significantly, this sensor can realize the sensitive and accurate detection of HA, nucleoside phosphates, and Fe3+ in real urine and serum and meet the practical detection needs in clinical diagnosis. These results indicate that the complex 1 as a multiresponsive luminescent biosensor possesses great potential for practical detection of HA, nucleoside phosphates, and Fe3+ in biological samples.

Lithologic controls on the mobility of Cd in mining-impacted watersheds revealed by stable Cd isotopes

Cd-rich wastes from open-pit mining can be transported into rivers, which are often followed by deposition in river sediments and/or further transfer into agricultural soils. The lithology of bedrock exerts a huge effect on physicochemical properties (e.g., buffering capacities, metal species, mineral phases, etc.) of the river system, thereby potentially impacting the Cd mobility in watersheds. However, to date, little is known about the microscopic processes (e.g., dissolution, adsorption, and precipitation) controlling the migration of Cd from mines to varied watersheds. This study, therefore, aims to determine the controlling factors on Cd mobilization in two mining-impacted watersheds with contrasting bedrock lithology using both Cd and Pb isotopes. The Pb isotope ratios of sediments and soils in both watersheds fall into a binary mixing model with two isotopically distinct sources, i.e., mining wastes and bedrock. These results indicate that mining activities are the main sources of Cd in sediments and soils. However, the Cd isotope ratios reveal different Cd migration processes between the two watersheds. In the siliceous watershed, the δ114/110Cd values of sediments decrease from -0.116‰ in the upper reach to -0.712‰ in the lower reach, with a concomitant increase in Cd concentration, which may result from Cd adsorption by goethite due to the increased pH. In contrast, in the calcareous watershed, the Cd isotope compositions of sediments (-0.345 to -0.276‰) and the pH of river water are nearly invariable, suggesting that the adsorption and release of Cd in sediments are limited. This may result from the strong pH buffering effect due to the presence of carbonate rocks. This study highlights the different fates of Cd in siliceous and calcareous watersheds and suggests that the development of Cd pollution control policies must consider regional lithology.

Competitive adsorption, immobilization, and desorption risks of Cd, Ni, and Cu in saturated-unsaturated soils by biochar under combined aging

This study investigated saturated-unsaturated soils, which were closer to the actual field conditions than traditional batch and column experiments with large water-soil ratios. The competitive adsorption, immobilization, and desorption of Cd, Ni, and Cu in soils treated with original and KMnO4-modified biochars were investigated under combined aging. Moreover, the employment of a three-layer mesh method enabled the independent analysis of heavy metals on biochar and soil during aging. The results showed that the order of biochar adsorption capacities was Cd > Cu > Ni in tested soils, and competing with Ni and Cu enhanced the Cd adsorption on biochars. Cd desorbed most with the CaCl2 solution while Ni and Cu desorbed most with citric acid. Modified biochar had improved immobilization effects compared to original biochar, and maintained the most stable remediation effects. The maximum variations in the stable Cd fraction during aging were 7.21%, 13.26%, and 14.71% for modified biochar, original biochar, and CK, respectively. However, for Ni and Cu, the biochar application reduced the residual fraction and increased desorption by citric acid. However, the stable fractions of Ni and Cu remained dominant, accounting for 83.28–97.85% and 86.31–98.96%, respectively.

Confirming the Molecular Basis of the Solvent Extraction of Cadmium(II) Using 2-Pyridyl Oximes through a Synthetic Inorganic Chemistry Approach and a Proposal for More Efficient Extractants.

The present work describes the reactions of CdI2 with 2-pyridyl aldoxime (2paoH), 3-pyridyl aldoxime (3paoH), 4-pyridyl aldoxime (4paoH), 2-6-diacetylpyridine dioxime (dapdoH2) and 2,6-pyridyl diamidoxime (LH4). The primary goal was to contribute to understanding the molecular basis of the very good liquid extraction ability of 2-pyridyl ketoximes with long aliphatic chains towards toxic Cd(II) and the inability of their 4-pyridyl isomers for this extraction. Our systematic investigation provided access to coordination complexes [CdI2(2paoH)2] (1), {[CdI2(3paoH)2]}n (2), {[CdI2(4paoH)2]}n (3) and [CdI2(dapdoH2)] (4). The reaction of CdI2 and LH4 in EtOH resulted in a Cd(II)-involving reaction of the bis(amidoxime) and isolation of [CdI2(L’H2)] (5), where L’H2 is the new ligand 2,6-bis(ethoxy)pyridine diimine. A mechanism of this transformation has been proposed. The structures of 1, 2, 3, 4·2EtOH and 5 were determined by single-crystal X-ray crystallography. The complexes have been characterized by FT-IR and FT-Raman spectra in the solid state and the data are discussed in terms of structural features. The stability of the complexes in DMSO was investigated by 1H NMR spectroscopy. Our studies confirm that the excellent extraction ability of 2-pyridyl ketoximes is due to the chelating nature of the extractants leading to thermodynamically stable Cd(II) complexes. The monodentate coordination of 4-pyridyl ketoximes (as confirmed in our model complexes with 4paoH and 3paoH) seems to be responsible for their poor performance as extractants.

Cadmium long-term immobilization by biochar and potential risks in soils with different pH under combined aging

Cd long-term immobilization by biochar and potential risk in soils with different pH were quantified under a combined artificial aging, which simulated five years of aging in the field based on local climate. Two biochars (original and KMnO4-modified) and five soils with different pH were tested, and an improved three-layer mesh method was employed in this study. Five aging cycles were carried out (Cycle 1–Cycle 5), and each aging cycle quantitatively simulated 1 year of natural aging. As the aging time increased, Cd leaching loss in all soils gradually increased from Cycle 1 to Cycle 5; for relatively stable Cd fraction, it decreased firstly and then stabilized in acidic and neutral soils (S1–S4), while it decreased firstly and then increased in alkaline soil (S5). Biochars significantly promoted Cd immobilization in strongly acidic soil (S1) by increasing relatively stable fractions and decreasing leaching loss. For weakly acidic and neutral soils (S2–S4), although biochars still had positive effects, the immobilization effects were weakened to certain extents compared with S1. The percentage of Cd leaching loss decreased by 19.12% in strongly acidic soil (S1) and by 1.12–11.35% in weakly acidic and neutral soils (S2–S4) after modified biochar treatment. For alkaline soil (S5), the application of biochars had negative effects on Cd immobilization by decreasing relatively stable fractions and increasing leaching loss, and posed risks to the environment. For strongly acidic soil (S1) and weakly acidic and neutral soils (S2–S4), the percentages of relatively stable fractions increased from 6.09–19.93% to 24.98–36.70% after modified biochar treatment. However, for alkaline soil, the percentage of relatively stable fractions decreased from 55.27% to 53.93% after biochar treatment. The more acidic the soil, the more effective the Cd immobilization by biochar. Biochars with high pH level are not suitable for the remediation of alkaline Cd contaminated soil.