Rapid and sustained resolution in generalized pustular psoriasis with IL-17A inhibitors required high adherence: a 96-week analysis in a real-life setting.

BACKGROUND: Generalized pustular psoriasis (GPP) is a rare, potentially life-threatening skin disease often requiring long-term therapy. We aimed to evaluate the use of Interleukin (IL)-17A inhibitors (secukinumab and ixekizumab) in GPP patients over 96 weeks. METHODS: We retrospectively analyzed a case series of 18 patients with GPP who received secukinumab (n = 13) and ixekizumab (n = 5) therapy with a 96-week follow-up period. The primary effectiveness analysis included determining the percentage of patients who achieved ≥90% or 100% improvement in the Generalized Pustular Psoriasis Area and Severity Index (GPPASI) score. Adherence was captured using the medication possession ratio (MPR). RESULTS: Using the as-observed (AO) method, 87% and 67% of patients treated with secukinumab or ixekizumab achieved GPPASI 90 and 100 responses, respectively. At Week 96, the mean GPPASI improvements from baseline GPPASI were 96.3% (95% CI: 0.91-1.01) using the AO method. After Week 48, 14 patients tapered (n = 8) or terminated (n = 6) the treatment. High-adherence therapy (MPR ≥ 80%) was significantly superior to the low-adherence group in the rate of patients achieving a GPPASI 100 response (AO, 100% vs. 38%, P < 0.05). By Week 96, 5 (27.8%) patients had new GPP flares, and 4 (80%) were in the low-adherence group. No new safety signals occurred. CONCLUSION: IL-17A inhibitors led to effective and sustained improvement in GPP patients, and high-adherence therapy had long-term positive effects on skin clearance. Given its relapsing nature, improving compliance is beneficial for long-term clinical management.

Antimony and arsenic migration in a heterogeneous subsurface at an abandoned antimony smelter under rainfall.

While antimony (Sb) and arsenic (As) co-contamination in subsurface soil systems due to the legacy of Sb smelting wastes has been documented, the role of inherent heterogeneity on pollutant migration is largely overlooked. Herein this study investigated Sb and As migration in a slag impacted, vertically stratified subsurface at an abandoned Sb smelter. A 2-dimensional flume was assembled as a lab-scale analogue of the site and subject to rainfall and stop-rain events. Reactive transport modeling was then performed by matching the experimental observations to verify the key factors and processes controlling pollutant migration. Results showed that rainfall caused Sb and As release from the shallow slag layer and promoted their downward movement. Nevertheless, the less permeable deeper layers limited physical flow and transport, which led to Sb and As accumulation at the interface. The re-adsorption of Sb and As onto iron oxides in the deeper, more acidic layers further retarded their migration. Because of the large difference between Sb and As concentrations, Sb re-adsorption was much less effective, which led to higher mobility. Our findings overall highlight the necessity of understanding the degree and impacts of physicochemical heterogeneity for risk exposure assessment and remediation of abandoned Sb smelting sites.

Occlusion-Aware Transformer With Second-Order Attention for Person Re-Identification.

Person re-identification (ReID) typically encounters varying degrees of occlusion in real-world scenarios. While previous methods have addressed this using handcrafted partitions or external cues, they often compromise semantic information or increase network complexity. In this paper, we propose a new method from a novel perspective, termed as OAT. Specifically, we first use a Transformer backbone with multiple class tokens for diverse pedestrian feature learning. Given that the self-attention mechanism in the Transformer solely focuses on low-level feature correlations, neglecting higher-order relations among different body parts or regions. Thus, we propose the Second-Order Attention (SOA) module to capture more comprehensive features. To address computational efficiency, we further derive approximation formulations for implementing second-order attention. Observing that the importance of semantics associated with different class tokens varies due to the uncertainty of the location and size of occlusion, we propose the Entropy Guided Fusion (EGF) module for multiple class tokens. By conducting uncertainty analysis on each class token, higher weights are assigned to those with lower information entropy, while lower weights are assigned to class tokens with higher entropy. The dynamic weight adjustment can mitigate the impact of occlusion-induced uncertainty on feature learning, thereby facilitating the acquisition of discriminative class token representations. Extensive experiments have been conducted on occluded and holistic person re-identification datasets, which demonstrate the effectiveness of our proposed method.

Comparison between super-responders and non-super-responders in psoriasis under adalimumab treatment: a real-life cohort study on the effectiveness and drug survival over one-year.

BACKGROUND: Data on the characteristics and treatment outcomes of super-responders and non-super-responders in psoriasis under adalimumab treatment are limited. METHODS: A retrospective analysis from psoriatic patients treated with adalimumab was compared to characterize super-responders vs non-super-responders' groups, identify factors associated with super response, and assess treatment outcomes after switching. RESULTS: 15 out of 70 (21.4%) patients were categorized as super-responder. The proportion of patients achieving a PASI 100 response was significantly higher in super-responders than non-super-responders at weeks 12, 24, and 52. Female sex and Charlson Co-morbidity Index were significantly associated with super-responders. A high level of high-density lipoprotein was independently associated with PASI 90 response at weeks 24 and 52. Additionally, nearly 35%-43% of non-super-responders switching to interleukin-17A (IL-17A) inhibitors may achieve a PASI 100 response at week 12. In contrast, all super-responders switching to IL-17A inhibitors achieved a PASI 100 response at week 4. CONCLUSIONS: Super-responders treated with adalimumab have a higher rate of being female and fewer comorbidities. And super-responders have better PASI responses than non-super-responders, whether the patients were treated with adalimumab or switched to IL-17A inhibitors.

Modeling spatial trends and exchange fluxes of contaminants in agricultural soil under pollution prevention measures.

Modeling the long-term trends of contaminants in topsoil under controlled measures is critical for sustainable agricultural environmental management. Traditional mass balance equations cannot predict spatial variation and exchange flux of regional soil contaminants for it lacks a method of assigning input-output parameters to each simulated cell. To overcome this limitation, we allocate the estimated source contribution flux to the spatial grid cell in the regional chemical mass balance by integrated positive matrix factorization (P-RCMB) with historical trends quantification. Focusing on Cd and As, which are elements with elevated risks of food intake and volatilization/infiltration, the model is applied to 30 ha of agricultural land near the enterprise. Predictions indicate an additional 13.5% of the soil is contaminated, and approximately 2.57 ha may accrue after 100 years at the site, with an uncertainty range of 0.98-5.3 ha. Clean water irrigation (CWI) reduces contamination expansion by approximately 42%, including approximately 4813 g ha-1 yr-1 net As infiltration, playing a dominant role in preventing the formation of severely contaminated soil. Stop straw return, green fertilizers use, and reduced atmospheric deposition control the exchange flux of Cd (114.9 g ha-1 yr-1) in moderate/slight contamination areas. For the different contaminants' cumulative trends in dryland and paddy fields, achieving a net cumulative flux close to zero in marginally contaminated areas presents a viable approach to optimize current emission standards. if trade-off straw removal and additional fertilizer inputs, a straw return rate of approximately 40% in Cd-contaminated soil will yield overall benefits. This model contributes valuable insights and tools for policymaking in contaminated land sustainable utilization and emission standard optimization.

The effect of biogeochemical redox oscillations on arsenic release from legacy mine tailings.

Exposed and un-remediated metal(loid)-bearing mine tailings are susceptible to wind and water erosion that disperses toxic elements into the surrounding environment. Compost-assisted phytostabilization has been successfully applied to legacy tailings as an inexpensive, eco-friendly, and sustainable landscape rehabilitation that provides vegetative cover and subsurface scaffolding to inhibit offsite transport of contaminant laden particles. The possibility of augmented metal(loid) mobility from subsurface redox reactions driven by irrigation and organic amendments is known and arsenic (As) is of particular concern because of its high affinity for adsorption to reducible ferric (oxyhydr)oxide surface sites. However, the biogeochemical transformation of As in mine tailings during multiple redox oscillations has not yet been addressed. In the present study, a redox-stat reactor was used to control oscillations between 7 d oxic and 7 d anoxic half-cycles over a three-month period in mine tailings with and without amendment of compost-derived organic matter (OM) solution. Aqueous and solid phase analyses during and after redox oscillations by mass spectrometry and synchrotron X-ray absorption spectroscopy revealed that soluble OM addition stimulated pyrite oxidation, which resulted in accelerated acidification and increased aqueous sulfate activity. Soluble OM in the reactor solution significantly increased mobilization of As under anoxic half-cycles primarily through reductive dissolution of ferrihydrite. Microbially-mediated As reduction was also observed in compost treatments, which increased partitioning to the aqueous phase due to the lower affinity of As(III) for complexation on ferric surface sites, e.g. ferrihydrite. Oxic half-cycles showed As repartitioned to the solid phase concurrent with precipitation of ferrihydrite and jarosite. Multiple redox oscillations increased the crystallinity of Fe minerals in the Treatment reactors with compost solution due to the reductive dissolution of ferrihydrite and precipitation of jarosite. The release of As from tailings gradually decreased after repeated redox oscillations. The high sulfate, ferrous iron, and hydronium activity promoted the precipitation of jarosite, which sequestered arsenic. Our results indicated that redox oscillations under compost-assisted phytostabilization can promote As release that diminishes over time, which should inform remediation assessment and environmental risk assessment of mine site compost-assisted phytostabilization.

Fluorescence biosensor for ultrasensitive detection of the available lead based on target biorecognition-induced DNA cyclic assembly.

A fluorescence biosensor was developed for the ultrasensitive detection of the available lead in soil samples by coupling with DNAzyme and hairpin DNA cyclic assembly. The biorecognition between lead and 8-17 DNAzyme will cleave the substrate strands (DNA2) and release the trigger DNA (T), which can be used to initiate the DNA assembly reactions among the hairpins (H1, H2, and H3). The formed Y-shaped sensing scaffold (H1-H2-H3) contains active Mg2+-DNAyzmes at three directions. In the presence of Mg2+, the BHQ and FAM modified H4 will be cleaved by the Mg2+-DNAyzme to generate a high fluorescence signal for lead monitoring. The linear range of the fluorescence biosensor is from 1 pM to 100 nM and the detection limit is 0.2 pM. The biosensor also exhibited high selectivity and the nontarget competing heavy metals did not interfere with the detection results. Compare with the traditional method (DTPA+ICP-MS) for the available lead detection, the relative error (Re) is in the range from -8.3 % to 9.5 %. The results indicated that our constructed fluorescence biosensor is robust, accurate, and reliable, and can be applied directly to the detection of the available lead in soil samples without complex extraction steps.

Recycling of phosphate tailings for an efficient hydroxyapatite-based adsorbent to immobilize heavy metal cations.

Hydroxyapatite (HAP) is a promising adsorbent for immobilizing heavy metals in soil and water. However, the preparation and modification of HAP from pure chemicals increases its cost and limits its large-scale practical application. In this study, a hydroxyapatite-based adsorbent (HAPPT) was prepared from phosphate tailing produced in the phosphorus industry to sequester Pb, Cd and Zn from solution. The results showed that HAPPT was composed of HAP and MgO, with a surface area of 27.74 m2/g. The kinetics studies showed that most Pb and Cd were removed from the initial solution in 4 h and the adsorption of Zn increased with increasing contact time. Metals presented higher adsorption capacities at 35 °C than that at 25 °C. The adsorption isotherms showed that HAPPT presented high adsorption capacities for Pb, Cd and Zn in mono-metal solutions. The adsorption capacity of Cd at pH 6 was higher than that at pH 3, but the adsorption for Pb and Zn was similar at both pHs. HAPPT has selectivity for Pb in Pb-Cd-Zn multi-metals solution, and competitive adsorption reduced the adsorption quantity by 53%, 93% and 79% for Pb, Cd and Zn, respectively. The combined results of TEM-EDS, XRD and XPS showed that Pb was immobilized by forming phosphates due to the dissolution of HAP, whereas Cd and Zn were immobilized by forming hydroxide precipitates resulting from the function of MgO in HAPPT. The results of this study provided an efficient adsorbent for the removal of heavy metals in solution and provided a new perspective on the recycling of phosphate tailings in the phosphorus industry.

Magnetic anaerobic granular sludge for sequestration and immobilization of Pb.

The development of magnetic adsorbents with high capacity to capture heavy metals has been the subject of intense research, but the process usually involves costive synthesis steps. Here, we propose a green approach to obtaining a magnetic biohybrid through in situ grown anaerobic granular sludge (AGS) with the help of magnetite, constituting a promising adsorbent for sequestration and immobilization of Pb in aqueous solutions and soils. The resultant magnetite-embedded AGS (M-AGS) was not only capable of promoting methane production but also conducive to Pb adsorption because of the large surface area and abundant function groups. The uptake of Pb on M-AGS followed the pseudo-second order, having a maximum adsorption capacity of 197.8 mg gDS-1 at pH 5.0, larger than 159.7, 170.3, and 178.1 mg gDS-1 in relation to AGS, F-AGS (ferrihydrite-mediated), and H-AGS (hematite-mediated), respectively. Mechanistic investigations showed that Pb binding to M-AGS proceeds via surface complexation, mineral precipitation, and lattice replacement, which promotes heavy metal capture and stabilization. This was evident from the increased proportion of structural Pb sequestrated from the aqueous solution and the enhanced percentage of the residual fraction of Pb extracted from the contaminated soils.

Zinc Stable Isotope Fractionation Mechanisms during Adsorption on and Substitution in Iron (Hydr)oxides.

The Zn isotope fingerprint is widely used as a proxy of various environmental geochemical processes, so it is crucial to determine which are the mechanisms responsible for isotopic fractionation. Iron (Fe) (hydr)oxides greatly control the cycling and fate and thus isotope fractionation factors of Zn in terrestrial environments. Here, Zn isotope fractionation and related mechanisms during adsorption on and substitution in three FeOOH polymorphs are explored. Results demonstrate that heavy Zn isotopes are preferentially enriched onto solids, with almost similar isotopic offsets (Δ66/64Znsolid-solution = 0.25-0.36‰) for goethite, lepidocrocite, and feroxyhyte. This is consistent with the same average Zn-O bond lengths for adsorbed Zn on these solids as revealed by Zn K-edge X-ray absorption fine structure spectroscopy. In contrast, at an initial Zn/Fe molar ratio of 0.02, incorporation of Zn into goethite and lepidocrocite by substituting for lattice Fe preferentially sequesters light Zn isotopes with Δ66/64Znsubstituted-stock solution of -1.52 ± 0.09‰ and -1.18 ± 0.15‰, while Zn-substituted feroxyhyte (0.06 ± 0.11‰) indicates almost no isotope fractionation. This is closely related to the different crystal nucleation and growth rates during the Zn-doped FeOOH formation processes. These results provide direct experimental evidence of incorporation of isotopically light Zn into Fe (hydr)oxides and improve our understanding of Zn isotope fractionation mechanisms during mineral-solution interface processes.

[Accumulation and Pollution Risks of Heavy Metals in Soils and Agricultural Products from a Typical Black Shale Region with High Geological Background].

Soil polluted by heavy metals (HMs) is an important environmental issue in China, and regional geological background is a vital factor that influences the enrichment of HMs in soils. Previous studies have shown that soils derived from black shales are commonly enriched in HMs and present high potential eco-environmental risks. However, few studies have investigated the HMs in different agricultural products, which inhibit the safe use of land and safe production of food crops in black shale regions. This study investigated the concentrations, pollution risks, and speciation of HMs in soils and agricultural products from a typical black shale region in Chongqing. The results showed that the study soils were enriched in Cd, Cr, Cu, Zn, and Se but not in Pb. Approximately 98.7% of total soils exceeded the risk screening values, and 47.3% of total soils exceeded the risk intervention values. Cd had the highest pollution level and potential ecological risks and was the primary pollutant in soils of the study area. Most of the Cd resided in ion-exchangeable fractions (40.6%), followed by residual fractions (19.1%) and weak organic matter combined fractions (16.6%), whereas Cr, Cu, Pb, Se, and Zn were dominated by residual fractions. Additionally, organic combined fractions contributed to Se and Cu, and Fe-Mn oxide combined fractions contributed to Pb. These results indicated that Cd had higher mobility and availability than those of other metals. The agricultural products presented a weak ability to accumulate HMs. Approximately 18.7% of the collected samples with Cd exceeded the safety limit, but the enrichment factor was relatively low, indicating low pollution risks of the heavy metals. The findings of this study could provide guidelines for safe use of land and safe production of food crops in black shale regions with high geological background.

Ratiometric and visual determination of copper ions with fluorescent nanohybrids of semiconducting polymer nanoparticles and carbon dots.

Developing nanohybrid composition based fluorescent carbon dots (CDs) for ratiometric detection of copper ions is highly appealing. Herein, a ratiometric sensing platform (GCDs@RSPN) for copper ions detection has been developed by loaded green fluorescence carbon dots (GCDs) on the surface of red emission semiconducting polymer nanoparticles (RSPN) through electrostatic adsorption. The GCDs, featuring abundant amino groups, can selectively bind copper ions to induce the photoinduced electron transfer, leading to fluorescence quenching. A good linearity within the range of 0-100 µM is obtained, and the limit of detection (LOD) is 0.577 µM by using obtained GCDs@RSPN as ratiometric probe to detect copper ion. Moreover, the paper-based sensor derived from GCDs@RSPN was successfully applied for the visual detection of Cu2+.

Emission and transformation behaviors of trace elements during combustion of Cd-rich coals from coal combustion related endemic fluorosis areas of Southwest, China.

Long-term combustion of low-quality coal may release hazardous elements into the environment causing serious environmental problems. This phenomenon is particularly prevalent in the Three Gorges Region of Southwest (SW), China. Cadmium (Cd), as well as other harmful elements are found to be highly enriched in coals and supergene environments in this area. In the existing literature, the behavioral issue of emission and transformation of the elevated trace elements during simulated household stove combustion from Cd-rich inferior coal remains unknown. This study investigated the emission of toxic elements, mineral assemblages, and provided technical guidance for reducing pollution by means of optimization combustion tests on inferior coals. The research may improve the understanding of geochemical characteristics from toxic elements emission in coal combustion endemic diseased areas. For this purpose, a series of simulated coal combustion experiments were conducted to reveal the release, mobility, and distribution of elevated elements in Cd-rich coal combustion products. The results showed that Cd, Mo, Cr, Cu, Zn, As, and Sb were significantly enriched in the inferior coals of the study area. Furthermore, large amounts of toxic elements were released as fly ash into the environment during the combustion process. In particular, combustion conditions played an important role in the emission and transformation of elevated elements. For example, higher temperatures promoted the release of Cd, Sb, Zn, and Tl into the environment. Oxygen-deficient combustion was found to liberate more Cd, Sb, and Tl to the atmosphere and generated complex mineral assemblages of lizardite, calcite, dolomite, forsterite, and enstatite. Moreover, toxic elements were found to be absorbed in the fine particle matter of fly ash from the endemic fluorosis area of SW, China. The findings of this work may aid to control the emission of toxic elements from inferior coals and mitigate the effect of toxic elements in the environment to protect human health.

Redistribution and isotope fractionation of endogenous Cd in soil profiles with geogenic Cd enrichment.

The concentration and speciation of endogenous cadmium (Cd) in soil systems derived from parent materials is continuously altered by rock-soil-plant interactions. Previous studies on the distribution of Cd primarily focused on surface soil at regional scale. However, it lacks a novel approach to provide a new perspective on dynamics and redistribution of Cd in soil profile. Therefore, this study tries to establish the linkage between isotope fractionation and environmental processes of Cd in soil profiles with geogenic Cd enrichment based on Cd isotopes. High Cd concentrations were observed in the profile from forest at accumulation zone and the one from farmland at ridge in a rural area, southwest China. Soil erosion and deposition substantially influence the vertical distribution of total Cd in soil from the accumulation zone. Accordingly, distinct Cd isotope compositions were observed in different layers (δ114/110Cd: -0.087 ‰ to -0.066 ‰ vs -0.325 ‰ to -0.056 ‰). Mineral transformation, pedogenesis and biological activities controlled the dynamics and redistribution of Cd. The mobility of Cd increased during weathering processes, with ~40 % to 60 % of Cd residing in exchangeable fraction in the surface layers. Biological activity is a vital factor that drives Cd isotope fractionation in soil, resulting in depletion of heavy Cd isotopes in surface layers of the studied farmland profile. Contrasting fractionation effects were observed in profiles from forest and farmland due to the variance in soil-plant Cd cycling. Our study revealed the processes that control dynamics and redistribution of endogenous Cd in soil profiles, and proved that Cd isotope is a useful tool to investigate the bio-geochemical processes of Cd in soil systems.

Field aging declines the regulatory effects of biochar on cadmium uptake by pepper in the soil.

Biochar application is not only being widely promoted as an ideal strategy to mitigate global climate warming, but it also has the advantage of reducing heavy metal bioavailability and migration in the soil. However, studies on the effects of field aging on biochar to reduce heavy metals from the soil are still limited. The present study aimed to explore the effects and mechanisms of aged biochar added to the soil planted with pepper plants on cadmium (Cd) uptake. To achieve this, un-amended soil (control), soil amended with fresh biochar, and aged biochar (biochar recovered from a long-term field trial after 9 years) were used to investigate the effects of field aging on biochar adsorption efficiency. The results revealed that the amount of Cd in the plant planted in control soil, amended with fresh and aged biochar, accounted for 40 ± 6.10, 17.18 ± 1.19, and 18.68 ± 0.79, respectively. There was a significant difference (P < 0.05) in the amount of Cd that was uptaken by plants among all treatments. However, soil amended with fresh biochar significantly (P < 0.05) decreased the amount of Cd in plants compared with soil amended with aged biochar. This indicates that field aging declines the potential of biochar to lower heavy metal bioavailability and retention in the soil. This study demonstrates that long-term burial lessens the ability of biochar to interact with Cd and suggests that biochar amendment can lower Cd in the soil, depending on the freshness and aging of biochar.

Nickel bioaccessibility in soils with high geochemical background and anthropogenic contamination.

Abnormally high concentrations of metals including nickel (Ni) in soils result from high geochemical background (HB) or anthropogenic contamination (AC). Metal bioaccessibility in AC-soils has been extensively explored, but studies in HB-soils are limited. This study examined the Ni bioaccessibility in basalt and black shale derived HB-soils, with AC-soils and soils without contamination (CT) being used for comparison. Although HB- and AC-soils had similar Ni levels (123 ± 43.0 vs 155 ± 84.7 mg kg-1), their Ni bioaccessibility based on the gastric phase of the Solubility Bioaccessibility Research Consortium (SBRC) in vitro assay was different. Nickel bioaccessibility in HB-soils was 6.42 ± 3.78%, 2-times lower than the CT-soils (12.0 ± 9.71%) and 6-times lower than that in AC-soils (42.6 ± 16.3%). Based on the sequential extraction, a much higher residual Ni fractionation in HB-soils than that in CT- and AC-soils was observed (81.9 ± 9.52% vs 68.6 ± 9.46% and 38.7 ± 16.0%). Further, correlation analysis indicate that the available Ni (exchangeable + carbonate-bound + Fe/Mn hydroxide-bound) was highly correlated with Ni bioaccessibility, which was also related to the organic carbon content in soils. The difference in co-localization between Ni and other elements (Fe, Mn and Ca) from high-resolution NanoSIMS analysis provided additional explanation for Ni bioaccessibility. In short, based on the large difference in Ni bioaccessibility in geochemical background and anthropogenic contaminated soils, it is important to base contamination sources for proper risk assessment of Ni-contaminated soils.

Role of Sp1 in atherosclerosis.

Specificity protein (Sp) is a famous family of transcription factors including Sp1, Sp2 and Sp3. Sp1 is the first one of Sp family proteins to be characterized and cloned in mammalian. It has been proposed that Sp1 acts as a modulator of the expression of target gene through interacting with a series of proteins, especially with transcriptional factors, and thereby contributes to the regulation of diverse biological processes. Notably, growing evidence indicates that Sp1 is involved in the main events in the development of atherosclerosis (AS), such as inflammation, lipid metabolism, plaque stability, vascular smooth muscle cells (VSMCs) proliferation and endothelial dysfunction. This review is designed to provide useful clues to further understanding roles of Sp1 in the pathogenesis of AS, and may be helpful for the design of novel efficacious therapeutics agents targeting Sp1.

Flooding-drainage alternations impact mobilization and isotope fractionation of cadmium in soil-rice systems.

Sequential flooding and draining substantially alter Cd mobilization in paddy fields, primarily due to redox-driven changes in Fe-Mn (hydro)oxides and Cd-sulfides. However, the impacts of carbonates on Cd mobilization during flooding-drainage alternations remain poorly understood. In this study, Cd isotope compositions were analyzed in soils and plants at three growth stages, and the results show a pH-dependent Cd mobilization and isotope fractionation. Sequential extraction shows the Cd mainly binds to the exchangeable fraction and carbonates, and their amounts vary with pH. Exchangeable Cd with light isotopes coprecipitates into carbonates due to increased pH during flooding (tillering and panicle initiation). Whereas in drained soils (maturity), the carbonate-bound Cd releases with decreased pH. Light isotopes are enriched in rice compared with exchangeable Cd, but this enrichment is insignificant at maturity. This difference is mainly caused by the change in Cd isotope composition of exchangeable Cd pool due to carbonate coprecipitation during flooding. Limited isotope fractionation between roots and aboveground tissues is found at tillering, whereas significant isotope fractionation is observed at two other stages, suggesting the nodes might work during Cd translocation between tissues. These findings demonstrate alternating flooding-drainage impacts the mobilization of carbonate-bound Cd and, consequently, isotope fractionation in soil-rice systems.

Adsorption of cadmium on clay-organic associations in different pH solutions: The effect of amphoteric organic matter.

Clay minerals are important soil components and usually coexist with organic matter, forming mineral-organic associations (MOAs), which control the speciation, mobility, and bioavailability of heavy metals. However, the adsorption mechanism of cadmium (Cd) by MOAs is still unclear, especially for the associations of amphotericorganic matter and clay minerals. In this study, 12-aminododecanoic acid (ALA) and montmorillonite (Mt) were chosen to prepare MOAs via intercalation (Mt-ALA composite) and physical mixing (Mt-ALA mixture). Batch experiments were conducted to investigate the adsorption mechanism of Cd(II) by MOAs under different pH values and initial Cd(II) concentrations. The results showed that the Cd(II) adsorption capacities followed as Mt > Mt-ALA mixture > Mt-ALA composite under acidic conditions, Mt-ALA mixture > Mt > Mt-ALA composite under neutral conditions, and Mt-ALA mixture > Mt-ALA composite > Mt under alkaline conditions, suggesting the adsorption behaviors of Cd(II) by MOAs were primarily constrained by the speciation of ALA and solution pH. Under acidic conditions, cationic HALA+ could intercalate into the interlayer of Mt and occupy the adsorption sites, reducing the adsorption capacity of Cd(II). As pH increased to neutral, HALA+ decreased and changed to a zwitterionic state, which caused ALA to release out from the interlayer of Mt-ALA composite or not easily enter into Mt-ALA mixture and promoted Cd(II) adsorption. Under alkaline conditions, the increase of anion ALA- would cause ALA to be mainly adsorbed on the surface of Mt and chelate with Cd(II), enhancing the adsorption of Cd(II). Further analysis by Fourier transform infrared and X-ray photoelectron spectroscopy indicated that the carboxyl and amino groups of ALA both participated in the adsorption of Cd(II). These findings could extend the knowledge on the mobility and fate of Cd in clay-based soils and be used as a basis for understanding the biogeochemical behavior of Cd in the environment.

Enrichment and environmental availability of cadmium in agricultural soils developed on Cd-rich black shale in southwestern China.

The enrichment of cadmium (Cd) in black shale-derived soils is of increasing concern due to its wide occurrence, high Cd concentrations, and potential risks. However, characteristics of enrichment and environmental availability of Cd in these soils are not well understood, which has restricted pollution control and land management. In this study, agricultural soils with elevated Cd concentrations resulting from weathering of Cd-bearing black shale in southwestern China were collected and analyzed. The results showed that Cd could be retained in soils through mechanical inheritance and/or associated with secondary minerals and organic materials. Cd concentrations in soils of the study area ranged between 0.83 and 21.6 mg/kg (average of 5.20 mg/kg), exceeding the risk screening value for agricultural land in China. The heterogeneity of Cd in these soils was highly related to geochemical composition of parent rock and other natural factors. The 0.01 M CaCl2 and 0.05 M EDTA extraction showed that Cd in these soils had high environmental availability and potential risks. Mobile Cd pool (CaCl2 extractable Cd, average: 0.24 mg/kg) accounted for 0.07-38.9% of the total Cd, depending on soil pH. Mobilizable Cd pool (EDTA extractable Cd, average: 2.18 mg/kg) accounted for 22.0-100%. These results showed the significance of geochemical background on enrichment of Cd in soils, documented high environmental availability of Cd in black shale-derived soils, and influence of soil pH.