Double Spike-Standard Addition Technique and Its Application in Measuring Isotopes.

Double spike (DS) method has been extensively used in determining stable isotope ratios of many elements. However, challenges remain in obtaining high-precision isotope data for ultra-trace elements owing to the limitations of instrumental signal-to-noise ratios and the systematics of precision of DS-based measurements. Here, the DS-standard addition (SA) (DSSA) technique is proposed to improve measurements of isotope compositions of ultra-trace elements in natural samples. According to the U-shaped relationship between DS measurement uncertainty and the spike/sample ratio, theoretical equations and an error propagation model (EPM) were constructed comprehensively. In our method, a spiked secondary standard solution with a high, precisely known spike/sample ratio is mixed with samples such that the mixtures have spike/sample ratios within the optimal range. The abundances of the samples relative to the added standards (sample fraction; fspl) and the samples' isotope ratios can then be obtained exactly using a standard DS data reduction routine and the isotope binary mixing model. The accuracy and precision of the DSSA approach were verified by measurements of cadmium and molybdenum isotopes at as low as 5 ng levels. Compared with traditional DS measurements, the sample size for isotope analysis is reduced to 1/6-1/5 of the original with no loss of measurement precision. The optimal mixing range fspl = 0.15-0.5 is recommended. The DSSA method can be extended to isotope measurement of more than 33 elements where the DS method is applicable, especially for the ultra-trace elements such as platinum group and rare earth element isotopes.

Antibiotic Resistance Determinants and Virulence Factors of Hypervirulent and Carbapenem Non-Susceptible Pseudomonas aeruginosa.

BACKGROUND: The aim was to investigate the distribution of antibiotic resistance determinants and virulence factors in a group of carbapenem non-susceptible Pseudomonas aeruginosa (P. aeruginosa). METHODS: From March 2018 to May 2019, a total of 98 P. aeruginosa samples were collected from 6 hospitals in Ningbo and Hangzhou, Zhejiang Province, China. Drug susceptibility tests to 13 antimicrobial agents were conducted. The presence of antibiotic resistance determinants and virulence factors were investigated by PCR, including 39 ß-lactamase genes, 14 aminoglycoside modifying enzyme genes, 10 16SrRNA methylase genes, and 11 virulence genes. Phylogenetics of 98 P. aeruginosa was analyzed by sample cluster analysis (UPGMA). RESULTS: PCR revealed the presence of 7 ß-lactamase genes, 5 aminoglycoside modifying enzymes, 1 16S rRNA methylase gene, and 8 virulence genes in total, at least 2 ß-lactamase genes and 4 virulence genes were positive in every isolate. In addition, regional differences in distributions of resistance and virulence genes remained between 2 cities. Sample cluster analysis showed that the strains had obvious aggregation and were divided into several clusters, strains in the same cluster were isolated from different hospitals, even from different cities. CONCLUSIONS: Carrying resistance genes blaPDC and blaOXA-50 group and virulence genes plcH, aprA, and algD were the important epidemiological characteristics of this group of P. aeruginosa. The present findings provide insights into the mechanisms of hypervirulence as well as resistance to ß-lactams and aminoglycosides. To the best of our knowledge, this is the first report of blaPDC, blaOXA-50, and aph(3')-XV in P. aeruginosa in China.

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.

Microscale Investigation into Selenium Distribution and Speciation in Se-Rich Soils from Enshi, China.

In this study, we investigated the distribution and chemical speciation of Se in Se-rich soil by using micro-focused X-ray absorption near-edge structure (µ-XANES) spectroscopy coupling with X-ray fluorescence (µ-XRF) mapping. The microscale distribution showed that Se is heterogeneously distributed in the soil from seleniferous areas in Enshi, China. Se K-edge µ-XANES analysis suggested that Se is mainly present as Se(IV), organic Se(-II) or Se(0) species in Se-rich agricultural soil. The findings from this study would help improve the understanding of the fate, mobility, bioavailability, and biogeochemical cycling of Se in the seleniferous soil environment.

Opportunistic bacteria use quorum sensing to disturb coral symbiotic communities and mediate the occurrence of coral bleaching.

Coral associated microorganisms, especially some opportunistic pathogens can utilize quorum-sensing (QS) signals to affect population structure and host health. However, direct evidence about the link between coral bleaching and dysbiotic microbiomes under QS regulation was lacking. Here, using 11 opportunistic bacteria and their QS products (AHLs, acyl-homoserine-lactones), we exposed Pocillopora damicornis to three different treatments: test groups (A and B: mixture of AHLs-producing bacteria and cocktail of AHLs signals respectively); control groups (C and D: group A and B with furanone added respectively); and a blank control (group E: only seawater) for 21 days. The results showed that remarkable bleaching phenomenon was observed in groups A and B. The operational taxonomic units-sequencing analysis shown that the bacterial network interactions and communities composition were significantly changed, becoming especially enhanced in the relative abundances of Vibrio, Edwardsiella, Enterobacter, Pseudomonas, and Aeromonas. Interestingly, the control groups (C and D) were found to have a limited influence upon host microbial composition and reduced bleaching susceptibility of P. damicornis. These results indicate bleaching's initiation and progression may be caused by opportunistic bacteria of resident microbes in a process under regulation by AHLs. These findings add a new dimension to our understanding of the complexity of bleaching mechanisms from a chemoecological perspective.

High-Sensitivity Measurement of Cr Isotopes by Double Spike MC-ICP-MS at the 10 ng Level.

High-sensitivity and high-precision (2 SD ≤ 0.06‰) measurement of chromium (Cr) isotopes at the 10 ng level was successfully carried out using double spike multiple-collector inductively couple plasma mass spectrometry (MC-ICP-MS). To enhance the signal sensitivity and stability, the Aridus II desolvating nebulizer system was improved by placing its waste gas trap bottle in an ice chamber (5 °C cold trap). This setup, beyond Cr isotope analysis, can be applied to most heavy metal isotope measurements. The sensitivity of the 52Cr signal is ≥300 V mg-1 L (with a 1011Ω amplifier and a 110 µL min-1 uptake rate), an enhancement of ≥1.5 times compared to the Aridus II without the cold trap. In addition, the relative standard deviation of the 52Cr signal varied ≤4% over 8 h, demonstrating high stability. The δ53Cr values of common geological reference materials determined using 10 ng of Cr are in excellent agreement with results measured at 25 ng and 50 ng and are consistent with previous determinations, validating the accurate and precise Cr isotope ratio measurements. An empirical method is proposed to correct for the residual (after subtraction) effect of Fe interference on δ53Cr determination. This method relies on a linear relationship between the [Fe]/[Cr] and δ53Cr shift within one analytical session. Finally, we report the δ53Cr values of 19 new reference materials, ranging from -0.44‰ to 0.49‰. Among them, GSS-7 (-0.44 ± 0.02‰, 2 SD, n = 5), GSS-4 (0.48 ± 0.02‰, 2 SD, n = 5), and GSD-10 (0.49 ± 0.05‰, 2 SD, n = 5) can be used as candidate reference materials for interlaboratory comparisons to complement existing ones that are mostly isotopically unfractionated from the bulk silicate earth.

High-precision magnesium isotope analysis of geological and environmental reference materials by multiple-collector inductively coupled plasma mass spectrometry.

RATIONALE: High-precision magnesium (Mg) isotopic analysis for geological and environmental reference materials is a prerequisite to ensure data quality before using Mg isotopes to trace geochemical and environmental processes. However, the Mg-isotopic ratios of many commonly used reference materials, especially sediments, have rarely been reported. Furthermore, published values for some commonly used reference materials exhibit a significant inconsistency across laboratories and thus need more data comparison. METHODS: We developed different Mg purification schemes for silicate rocks, high-Ca carbonates and carbonatites, and high-Mn samples because of their significantly different matrices. We then used synthetic solutions to evaluate potential effects on measurement using multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The accuracy and precision of our procedures were assessed by measurement on both synthetic solutions and well-studied geostandards. RESULTS: The three different schemes for routine, high-Ca, and high-Mn samples can remove matrices efficiently with nearly 100% Mg yield. However, the presence of acid molarity and concentration mismatch, matrix elements, and fluctuations in room temperature can significantly affect the precision and accuracy of Mg isotope analysis, and must be avoided. The Mg isotopic ratios of reference materials obtained in this study are identical to the previously published values within ±0.06‰, verifying that our procedures are robust. CONCLUSIONS: This study presented a thorough set of tests for high precision and accuracy of Mg isotope measurements using MC-ICP-MS, which demonstrate reproducibility and accuracy better than 0.05‰ for δ25 Mg values and 0.06‰ for δ26 Mg values. We reported high-quality Mg isotopic data for 16 geological and environmental reference materials to aid the inter-laboratory calibration of Mg isotope measurements in the future.

Neuroanatomical Alterations in Patients with Early Stage of Unilateral Pulsatile Tinnitus: A Voxel-Based Morphometry Study.

During the past several years, the rapid development of neuroimaging techniques has contributed greatly in the noninvasive imaging studies of tinnitus. The aim of the present study was to explore the brain anatomical alterations in patients with right-sided unilateral pulsatile tinnitus (PT) in the early stage of PT symptom using voxel-based morphometry (VBM) analysis. Twenty-four patients with right-sided pulsatile tinnitus and 24 age- and gender-matched normal controls were recruited to this study. Structural image data preprocessing was performed using VBM8 toolbox. Tinnitus Handicap Inventory (THI) score was acquired in the tinnitus group to assess the severity of tinnitus and tinnitus-related distress. Two-sample t-test and Pearson's correlation analysis were used in statistical analysis. Patients with unilateral pulsatile tinnitus had significantly increased gray matter (GM) volume in bilateral superior temporal gyrus compared with the normal controls. However, the left cerebellum posterior lobe, left frontal superior orbital lobe (gyrus rectus), right middle occipital gyrus (MOG), and bilateral putamen showed significantly decreased brain volumes. This was the first study which demonstrated the features of neuroanatomical changes in patients with unilateral PT during their early stages of the symptom.

Docking-based structural splicing and reassembly strategy to develop novel deazapurine derivatives as potent B-RafV600E inhibitors.

The mutation of B-RafV600E is widespread in a variety of human cancers. Its inhibitors vemurafenib and dabrafenib have been launched as drugs for treating unresectable melanoma, demonstrating that B-RafV600E is an ideal drug target. This study focused on developing novel B-RafV600E inhibitors as drug leads against various cancers with B-RafV600E mutation. Using molecular modeling approaches, 200 blockbuster drugs were spliced to generate 283 fragments followed by molecular docking to identify potent fragments. Molecular structures of potential inhibitors of B-RafV600E were then obtained by fragment reassembly followed by docking to predict the bioactivity of the reassembled molecules. The structures with high predicted bioactivity were synthesized, followed by in vitro study to identify potent B-RafV600E inhibitors. A highly potent fragment binding to the hinge area of B-RafV600E was identified via a docking-based structural splicing approach. Using the fragment, 14 novel structures were designed by structural reassembly, two of which were predicted to be as strong as marketed B-RafV600E inhibitors. Biological evaluation revealed that compound 1m is a potent B-RafV600E inhibitor with an IC50 value of 0.05 µmol/L, which was lower than that of vemurafenib (0.13 µmol/L). Moreover, the selectivity of 1m against B-RafWT was enhanced compared with vemurafenib. In addition, 1m exhibits desirable solubility, bioavailability and metabolic stability in in vitro assays. Thus, a highly potent and selective B-RafV600E inhibitor was designed via a docking-based structural splicing and reassembly strategy and was validated by medicinal synthesis and biological evaluation.

Optimization of intra-voxel incoherent motion measurement in diffusion-weighted imaging of breast cancer.

PURPOSE: The purpose of this study was to optimize intra-voxel incoherent motion (IVIM) measurement in diffusion-weighted imaging (DWI) of breast cancer by separating perfusion and diffusion effects through the determination of an optimal threshold b-value, thus benign and cancerous breast tissues can be accurately differentiated using IVIM-derived diffusion and perfusion parameters. MATERIALS AND METHODS: Twenty-eight patients, with biopsy-confirmed breast cancers, were studied with a 3T MRI scanner, using T1-weighted dynamic contrast-enhanced MRI images, and diffusion-weighted images with nine b-values, ranging from 0 to 1000 s/mm². IVIM-derived parameter maps for tissue diffusion coefficients D, perfusion fraction f, and pseudo-diffusion coefficients D* were computed using the segmented fitting method with optimized threshold b-value, and the sum of squared residuals (SSR) were calculated for IVIM-derived parameters in different breast lesions. RESULTS: The IVIM analysis method developed in this work can separate perfusion and diffusion effects with the optimal threshold b-value of 300 s/mm², and the results of diffusion and perfusion parameters from IVIM analysis can be used to differentiate pathological changes in breast tissues. It was found that the averages and standard deviations of the diffusion and perfusion parameters, D, f, D*, are the following, for malignant, benign and normal breast tissues respectively: D (0.813 ± 0.225 × 10-3 mm2 /s, 1.437 ± 0.538 × 10-3 mm2 /s, 1.838 ± 0.213 × 10-3 mm2 /s), f (10.73 ± 3.44%, 7.86 ± 3.70%, 8.92 ± 3.72%), D* (15.23 ± 12.17×10-3 mm²/s, 12.02 ± 3.19 × 10-3 mm2 /s, 12.03 ± 7.21 × 10-3 mm2 /s). CONCLUSION: IVIM-derived diffusion and perfusion parameter maps depend highly on the choice of threshold b-value. Using the methodology developed in this work, and with the optimized threshold b-value, the diffusion and perfusion parameters of breast tissues can be accurately assessed, making IVIM MRI a technique of choice for differential diagnosis of breast cancer.

[Single scrotal-incision orchidopexy without ligation of processus vaginalis for palpable undescended testis].

OBJECTIVE: To determine the feasibility and short-term effect of single scrotal-incision orchidopexy (SSIO) without ligation of the processus vaginalis (PV) in the treatment of palpable undescended testis (PUDT). METHODS: This retrospective study included 109 cases of PUDT (125 sides) and 15 cases of impalpable undescended testis (IUDT). The former underwent SSIO without PV ligation (group A, n = 53) or standard inguinal orchidopexy with PV ligation (group B, n = 56) while the latter received laparoscopic exploration (group C). We analyzed the success rate of SSIO in the management of PUDT, postoperative complications, and incidence rates of hernia and hydrocele, and compared the relevant parameters between groups A and B. RESULTS: The median age of the PUDT patients was 1.4 (0.6－11.0) years. Group A included 24 cases of left PUDT (2 with hydrocele), 20 cases of right PUDT (1 with hydrocele), and 9 cases of bilateral PUDT, the success rate of which was 95.1%. Group B consisted of 27 cases of left PUDT, 22 cases of right PUDT (3 with hernias), and 7 cases of bilateral PUDT. The rate of PV patency in the PUDT patients was 80.8% (101/125). Laparoscopic exploration of the 15 IUDT patients revealed 2 cases of congenital testis absence, 6 cases of testis dysplasia, all treated by surgical removal, 3 cases of staying around the inner ring, descended by inguinal orchidopexy, and the other 4 treated by laparoscopic surgery. The incisions healed well in all cases, with no testicular atrophy, inguinal hernia or hydrocele. CONCLUSIONS: Single scrotal-incision orchidopexy without PV ligation is a safe and feasible procedure for the treatment of palpable undescended testis, which avoids the risk of inguinal hernia or hydrocele.

[Molecular epidemiology study on an acute gastroenteritis outbreak caused by a new GII. 4 norovirus recombinant strain].

OBJECTIVE: To analyze the epidemiological characteristics of an acute gastroenteritis outbreak in a nursing home caused by norovirus (NoV) and the genotype of the pathogen. METHODS: On January 29th 2013, a total of 26 acute gastroenteritis patients infected by norovirus were reported in the nursing home of Jinshan, Shanghai. A questionnaire was used to acquire information of patients involved in the outbreak, 9 stool or anal swab samples were collected from 9 patients without treatment by simple random sampling method, and 4 environmental samples from the surface of doorknobs or toilets were collected. The samples were detected by Real-time PCR for NoV, and positive samples were then amplified by routine RT-PCR. The PCR products were purified, sequenced, and aligned by comparing sequences in GenBank. Phylogenetic trees were constructed by using Clustal X, employing MEGA 5.1 program package. RESULTS: For the 26 patients, 7 were men and 19 were women.8 samples were found NoV positive among the 13 samples when detected by real-time PCR. The sequence alignment showed that the nucleotide sequence homology between Jinshan08 and Jinshan12 strain which obtained sequencing signal was 100%. The phylogenetic analysis revealed that Jinshan08, Jinshan12 and GII.e/NV2634/BCN/Spain/2008 strains in the RdRp region were on the the same branch of evolutionary tree, the confidence level was 99%, and in the N/S region of the Capsid, 2 other strains and Lordsdal strain were in the same branch, the confidence level was 97%. CONCLUSION: It was confirmed that the acute gastroenteritis outbreak was caused by the new GII.4 NoV recombinant.

[Research on serum prostate-specific antigen measurement by characteristic spectral imaging method].

A serum prostate-specific antigen (PSA) measurement method was studied using characteristic spectral imaging method and immunochromatography-based colloidal gold-marked test-strips. An annular light source made of LEDs in the range from 520 to 535 nm irradiated the test-strips sampled by PSA in darkroom, and then the photograph of the test-strip was captured by the CCD industrial camera an d transferred to PC. Th e characteristic value of the test line on t he test-strip wa s acquired bythe Quantitative Testing Software on PC using grey level transformation and image segmentation, and then the relationship between the characteristic value and PSA level could be ascertained by cubic polynomial fitting method. Some experiments were completed by 25 blood samples which were taken from one man with no prostate disease and 24 men with prostate disease, and then the correlation coefficient between the measurement values and the true values equals to 0.924. In addition, when the PSA level in the blood sample is lower than 25 ng.mL-1, the measurement accuracy is higher than that when the PSA level in the blood sample exceeds 25 ng.mL-1. The experimental results proved that the proposed method for serum PSA level measurement is feasible.

Topographic constraints on the distribution of selenium in the supergene environment: A case study at Yutangba, China.

The local topography and leaching conditions significantly affect the spatial distribution of selenium (Se) in the local environment. However, the driving factors controlling Se distribution have not been well addressed. In this paper, taking Yutangba, a village known for human selenosis in China, as an example, we demonstrate how topographic factors influence the spatial distribution of Se in soils and plants. In the scenarios of slope ≤25°, the correlations among slope and soil/extractable/plant Se are significantly negative (P < 0.05), whereas they become weak or unclear when the slope is > 25°, suggesting that 25° of slope is a critical transition boundary. Similar observations were further verified by the soil erosion modulus (SEM) and the surface runoff intensity index (SRI), indicating that Se transport via soil erosion is limited and accounts for 11.2-17% of the soil Se, while surface runoff plays a dominant role in the Se distribution, accounting for 83-88.1%. Soil extractable Se is negatively correlated with SRI (Pearson r = -0.87 at slope < 25°), showing that the migration capacity of Se is higher at steep terrain and controlled by topography through soil erosion and surface runoff. The positive relationship between plant Se and soil/extractable Se demonstrates that topography indirectly influences plant Se through soil Se bioavailability. Abnormally local Se enrichment observed at the elevated steep hillside (>25°) in northwestern Yutangba primarily was resulted from the weathering of Se-rich rocks. These observations confirm that the topographic slope gradient influences the transport and spatial distribution of soil Se, implying that topography should be considered when studying the spatial distribution of soil Se at a regional scale, especially for the Se-poor belt in China.

Ni isotopes provide a glimpse of Earth's pre-late-veneer mantle.

Moderately siderophile (e.g., Ni) and highly siderophile elements (HSEs) in the bulk silicate Earth (BSE) are believed to be partly or near-completely delivered by late accretion after the depletion caused by metallic core formation. However, the extent and rate of remixing of late-accreted materials that equilibrated with Earth's pre-late-veneer mantle have long been debated. Observing evidence of this siderophile element-depleted pre-late-veneer mantle would provide powerful confirmation of this model of early mantle evolution. We find that the mantle source of the ~3.8-billion-year-old (Ga) Narssaq ultramafic cumulates from Southwest Greenland exhibits a subtle 60Ni/58Ni excess of ~0.05 per mil and contains a clear HSE deficiency of ~60% relative to the BSE. The intermediate Ni isotopic composition and HSE abundances of the ~3.8-Ga Narssaq mantle mark a transitional Eoarchean snapshot as the poorly mixed 3.8-Ga mantle containing elements of pre-late-veneer mantle material transitions to modern Earth's mantle.

[Research on serum prostate-specific antigen measurement by characteristic spectral absorption method].

A serum prostate-specific antigen (PSA) measurement method was studied using immunochromatography-based colloidal gold-marked test-strips and characteristic spectral absorption method. Some LEDs in the range from 520 to 535 nm irradiated the test-strips sampled by PSA, and then a photodiode in the range from 520 to 540 nm measured the reflex light at the specific area. Accordingly, the absorbency of the strip could be calculated, then the relationship between PSA level and strip absorbency could be ascertained by linear fit method. The experimental measurement system was calibrated by different PSA standard solutions in this research. As a result, in the range between 5 to 50 ng x mL(-1), the levels of PSA have a linear relationship with the absorbency of test-strips. Some experiments were completed by 21 different PSA standard solutions within that range, and then the correlation coefficient of the results is equal to 0.910, which proves that the proposed method for serum PSA level measurement is feasible.

The structure and assembly mechanisms of plastisphere microbial community in natural marine environment.

The microbial colonization profiles on microplastics (MPs) in marine environments have recently sparked global interest. However, many studies have characterized plastisphere microbiomes without considering the ecological processes that underly microbiome assembly. Here, we carried out a three-timepoint exposure experiment at 1-, 4-, and 8-week and investigated the colonization dynamics for polyethylene, polypropylene, polystyrene, polyvinyl chloride, and acrylonitrile-butadiene-styrene MP pellets in natural coastal water. Using high-throughput sequencing of 16S rRNA, we found diversity and evenness were higher (p < 0.05) in the plastisphere communities than those in seawater, and microorganisms colonizing were co-influenced by environmental factors, polymer types, and exposure duration. Functional potential and co-occurrence network analysis revealed that MP exposure enriched the xenobiotic biodegradation potential and reduced the complexity of the MP microbial network. Simultaneously, null-model analyses indicated that stochastic processes contributed a bigger role than deterministic processes in shaping plastisphere microbial community structure with dispersal limitations contributing to a greater extent to microbial succession trajectories. These results implied the plastic surface had a more important role as a raft onto which microbes attach rather than selectively recruiting plastic-specific microbial colonizers. Our work strengthened the understanding of the ecological mechanisms by which microbial community patterns are controlled during colonization by plastic-associated microbes.

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.

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.

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.