Heavy metal pollution near an abandoned mercury-bearing waste recovery enterprise in southwestern China: Spatial distribution and its sources in soil and plants.

The contribution of smelting of nonferrous metals to heavy metals in surface soil have become increasingly important over the past decade. In this study, the distribution of heavy metals around an abandoned mercury-bearing waste recovery enterprise were investigated. Soil (14) and plant (18) samples were collected in the surrounding area. The total concentration of heavy metals and methyl mercury content were measured by ICP-MS and HPLC-ICP-MS. The results show that the average contents of Cd, Cr, Pb, Hg and As in all soil samples are higher than the second-level values of Soil environmental quality-Risk control standard for soil contamination of development land (GB 36600-2018). Hg in the leaves ranged from 0.003 to 0.174 mg kg-1. Besides, the Pearson correlation analysis results indicate that Hg has a different environmental behavior compared to the other heavy metal under certain environmental or geographical conditions. But the mantel test statistical analysis results show that the Cr (P < 0.01), Cu, Pb, and Fe (P < 0.05) in the soil may have similar pollution sources with carbonate-bound mercury and iron-manganese oxide-bound mercury. The Hg concentrations show no correlation among plant leaves and soil, but significantly influenced by the distance and wind direction. These findings suggest that Hg in plant leaves may be derived from the deposition of atmospheric mercury from secondary mercury plant. The results will supplement those for relevant policy making for mercury-bearing waste recovery enterprises to improve urban environmental quality and human health.

Characteristics, source analysis, and health risk assessment of potentially toxic elements pollution in soil of dense molybdenum tailing ponds area in central China.

The issue of potentially toxic elements (PTEs) contamination of regional soil caused by mining activities and tailings accumulation has attracted wide attention all over the world. The East Qinling is one of the three main molybdenum mines in the world, and the concentration of PTEs such as Hg, Pb and Cu in the slag is high. Quantifying the amount of PTEs contamination in soil and identifying potential sources of contamination is vital for soil environmental management. In the present investigation, the pollution levels of 8 PTEs in the Qinling molybdenum tailings intensive area were quantitatively identified. Additionally, an integrated source-risk method was adopted for resource allocation and risk assessment based on the PMF model, the ecological risk, and the health risk assessment model. The mean concentrations of Cu, Ni, Pb, Cd, Cr, Zn, As, and Hg in the 80 topsoil samples ranged from 0.80 to 13.38 times the corresponding background values; notably high levels were observed for Pb and Hg. The source partitioning results showed that PTEs were mainly affected by four pollution sources: natural and agricultural sources, coal-burning sources, combined transport and mining industry sources, and mining and smelting sources. The health risk assessment results revealed that the risks of soil PTEs for adults are acceptable, while the risks for children exceeded the limit values. The obtained results will help policymakers to obtain the sources of PTEs of tailing ponds intensive area. Moreover, it provides priorities for the governance of subsequent pollution sources and ecological restoration.

Life expectancy among older adults with or without frailty in China: multistate modelling of a national longitudinal cohort study.

BACKGROUND: Little is known about life expectancy (LE) with or without frailty. We aimed to estimate the total LE and duration of the state of frailty in China. METHODS: This study included older adults aged 65 years and older from the Chinese Longitudinal Healthy Longevity Study (CLHLS). Frailty status was classified into robust, pre-frailty and frailty based on a cumulative deficit model. Total and specific frailty state LEs at 65 years of age were estimated and stratified by demographic characteristics, behaviours, and psychosocial factors using continuous-time multistate modelling. RESULTS: The total LE of older adults aged 65 years in China was 14.74 years on average (95% CI: 14.52-14.94), of which 4.18 years (95% CI: 4.05-4.30) were robust, 7.46 years (95% CI: 7.31-7.61) pre-frail and 3.10 years (95% CI: 3.01-3.20) frail. Older adults with higher robust LE included men (4.71 years, 95% CI: 4.56-4.88), married older adults (4.41 years, 95% CI: 4.27-4.56), those engaging in physical activity (4.41 years, 95% CI: 4.23-4.59), those consuming fruits daily (4.48 years, 95% CI: 4.22-4.77) and those with high social participation (4.39 years, 95% CI: 4.26-4.53). Increased educational attainment were gradually associated with increased robust LE. CONCLUSIONS: Frailty may lead to a reduced total LE and robust LE of older adults in China. In addition to finding inequalities in total and robust LEs by socioeconomic status, our findings also highlight that healthy behaviours and social participation may ease frailty-related reductions in total and robust LE. Our findings imply that national life-course strategies aimed at frailty screening and psychosocial and behavioural interventions could be important for health aging in China.

Tris-amidoximate uranyl complexes via η2 binding mode coordinated in aqueous solution shown by X-ray absorption spectroscopy and density functional theory methods.

The present study sheds some light on the long-standing debate concerning the coordination properties between uranyl ions and the amidoxime ligand, which is a key ingredient for achieving efficient extraction of uranium. Using X-ray absorption fine structure combined with theoretical simulation methods, the binding mode and bonding nature of a uranyl-amidoxime complex in aqueous solution were determined for the first time. The results show that in a highly concentrated amidoxime solution the preferred binding mode between UO22+ and the amidoxime ligand is η2 coordination with tris-amidoximate species. In such a uranyl-amidoximate complex with η2 binding motif, strong covalent interaction and orbital hybridization between U 5f/6d and (N, O) 2p should be responsible for the excellent binding ability of the amidoximate ligand to uranyl. The study was performed directly in aqueous solution to avoid the possible binding mode differences caused by crystallization of a single-crystal sample. This work also is an example of the simultaneous study of local structure and electronic structure in solution systems using combined diagnostic tools.

Selenium Sequestration in a Cationic Layered Rare Earth Hydroxide: A Combined Batch Experiments and EXAFS Investigation.

Selenium is of great concern owing to its acutely toxic characteristic at elevated dosage and the long-term radiotoxicity of 79Se. The contents of selenium in industrial wastewater, agricultural runoff, and drinking water have to be constrained to a value of 50 µg/L as the maximum concentration limit. We reported here the selenium uptake using a structurally well-defined cationic layered rare earth hydroxide, Y2(OH)5Cl·1.5H2O. The sorption kinetics, isotherms, selectivity, and desorption of selenite and selenate on Y2(OH)5Cl·1.5H2O at pH 7 and 8.5 were systematically investigated using a batch method. The maximum sorption capacities of selenite and selenate are 207 and 124 mg/g, respectively, both representing the new records among those of inorganic sorbents. In the low concentration region, Y2(OH)5Cl·1.5H2O is able to almost completely remove selenium from aqueous solution even in the presence of competitive anions such as NO3-, Cl-, CO32-, SO42-, and HPO42-. The resulting concentration of selenium is below 10 µg/L, well meeting the strictest criterion for the drinking water. The selenate on loaded samples could be desorbed by rinsing with concentrated noncomplexing NaCl solutions whereas complexing ligands have to be employed to elute selenite for the material regeneration. After desorption, Y2(OH)5Cl·1.5H2O could be reused to remove selenate and selenite. In addition, the sorption mechanism was unraveled by the combination of EDS, FT-IR, Raman, PXRD, and EXAFS techniques. Specifically, the selenate ions were exchanged with chloride ions in the interlayer space, forming outer-sphere complexes. In comparison, besides anion exchange mechanism, the selenite ions were directly bound to the Y3+ center in the positively charged layer of [Y2(OH)5(H2O)]+ through strong bidentate binuclear inner-sphere complexation, consistent with the observation of the higher uptake of selenite over selenate. The results presented in this work confirm that the cationic layered rare earth hydroxide is an emerging and promising material for efficient removal of selenite and selenate as well as other anionic environmental pollutants.

Uptake Mechanisms of Eu(III) on Hydroxyapatite: A Potential Permeable Reactive Barrier Backfill Material for Trapping Trivalent Minor Actinides.

The permeable reactive barrier (PRB) technique has attracted an increasing level of attention for the in situ remediation of contaminated groundwater. In this study, the macroscopic uptake behaviors and microscopic speciation of Eu(III) on hydroxyapatite (HAP) were investigated by a combination of theoretical modeling, batch experiments, powder X-ray diffraction (PXRD) fitting, and X-ray absorption spectroscopy (XAS). The underlying removal mechanisms were identified to further assess the application potential of HAP as an effective PRB backfill material. The macroscopic analysis revealed that nearly all dissolved Eu(III) in solution was removed at pH 6.5 within an extremely short reaction time of 5 min. In addition, the thermodynamic calculations, desorption experiments, and PXRD and XAS analyses definitely confirmed the formation of the EuPO4·H2O(s) phase during the process of uptake of dissolved Eu(III) by HAP via the dissolution-precipitation mechanism. A detailed comparison of the present experimental findings and related HAP-metal systems suggests that the relative contribution of precipitation to the total Eu(III) removal increases as the P:Eu ratio decreases. The dosage of HAP-based PRB for the remediation of groundwater polluted by Eu(III) and analogous trivalent actinides [e.g., Am(III) and Cm(III)] should be strictly controlled depending on the dissolved Eu(III) concentration to obtain an optimal P:M (M represents Eu, Am, or Cm) ratio and treatment efficiency.

RBF neural network dynamic sliding mode control based on lambert W function for piezoelectric stick-slip actuator.

This paper presents a novel approach for increasing the precision of high-precision positioning control experiments for a piezoelectric stick-slip actuator system. This is achieved through dynamic sliding mode control with a radial basis function neural network (RBFNN) based on the Lambert W function. The proposed control strategy is divided into two parts: scanning mode control and stepping mode control. For scanning control, a dynamic sliding mode controller was designed to solve the jitter problem in traditional sliding mode control. The introduction of the RBFNN avoids the effects of uncertainty terms and unknown disturbances in the model; reduces the controller gain, which must be adjusted; and improves the robustness of the system to disturbances. The stability of the dynamic sliding mode controller based on the RBFNN was verified through a Lyapunov analysis, and the Lambert W function was introduced to optimize the controller parameters responsible for the time lag in the closed-loop control system. This optimization improved the system's robustness against time delays, which can adversely affect its performance. Simulation and experimental results indicated that the proposed control strategy achieved a positioning control accuracy of <40 nm during the scanning phase and was robust in the presence of a load. In long-distance positioning control experiments, the control strategy achieved a control target of 40 µm while maintaining the positioning control accuracy and reducing the impact of time lag on the system.

Comparison of water-soluble organic matter (WSOM)-containing and WSOM-free biochars for simultaneous sorption of lead and cadmium.

The effects of individual biochar constituents and natural environmental media on the immobilization behaviors and chemical activities of toxic heavy metals are still poorly understood. In this work, the physicochemical properties of raw corn straw (CS) and CS-derived biochar materials as well as their sorption abilities and retention mechanisms for lead (Pb) and cadmium (Cd) were evaluated by combining batch experiments and spectral approaches. According to the spectral analysis results and single variable principle, the setting of biochars after soaking in solution as the control group was suggested when evaluating their retention mechanisms for Pb and Cd. The rising of ionic strength did not apparently affect the immobilization of Pb by biochar prepared at 500 °C (i.e., CB500) and Pb/Cd by water-soluble organic matter (WSOM)-free CB500 (i.e., DCB500), while slightly inhibited the sorption of Cd by CB500. Pb and Cd exhibited a mutual inhibition effect on their sorption trends with a higher sorption preference of Pb. The dominant fixation mechanism of Pb by CB500 and DCB500 was identified to be mineral precipitation. In contrast, the main sorption mechanism of Cd changed from mineral precipitation in the single-metal system to surface complexation in the binary-metal system. The sorption ratios of Pb and Cd on CB500 were comparable to those on DCB500 with the coexistence of mixed natural organic matters (NOM) and ferrihydrite. The current experimental findings suggested that DCB500 was a suitable remediation agent for regulating the migration behaviors of toxic Pb and Cd in acidic and NOM-rich soil and water systems.

ENGEP: advancing spatial transcriptomics with accurate unmeasured gene expression prediction.

Imaging-based spatial transcriptomics techniques provide valuable spatial and gene expression information at single-cell resolution. However, their current capability is restricted to profiling a limited number of genes per sample, resulting in most of the transcriptome remaining unmeasured. To overcome this challenge, we develop ENGEP, an ensemble learning-based tool that predicts unmeasured gene expression in spatial transcriptomics data by using multiple single-cell RNA sequencing datasets as references. ENGEP outperforms current state-of-the-art tools and brings biological insight by accurately predicting unmeasured genes. ENGEP has exceptional efficiency in terms of runtime and memory usage, making it scalable for analyzing large datasets.

Exploratory graph analysis on the Connor-Davidson Resilience Scale (CD-RISC) among older adults in China.

It is important for healthy aging to understand resilience in depth. This study aims to examine the dimensional structure underlying the Connor-Davidson Resilience Scale (CD-RISC) among Chinese older adults. Exploratory Graph Analysis (EGA) was used to evaluate the dimensional structure of CD-RISC in two large samples: training sample (n = 11,493) and cross-validation sample (n = 7662). Then, Confirmatory Factor Analysis (CFA) was used to compare the fit of the theoretical dimensions with the EGA dimensions. Finially, Generalized Linear Model was used to examine the association between resilience scores and self-rated health (SRH) after controlling other covariates in order to evaluate the predictive value of the EGA dimensions. The EGA indicated two demensions(named foresight and self-adjustment) of the 25-item CD-RISC. The CFA comparison found that the two-demension structure of CD-RISC fit significantly better than the theoretical three-demension structure. After controlling for sociodemographic characteristics, generalized linear model showed that the EGA dimensions has better protective value with SRH. Compared with older adults with lowest quartile of foresight, those with second (odds ratio, OR = 0.68, 95% CI = 0.62 ~ 0.75), third (OR = 0.50, 95% CI = 0.45 ~ 0.56) and fourth quartile (OR = 0.42, 95% CI = 0.37 ~ 0.48) of foresight had lower odds ratio of poor SRH. Similarly, older adults with the second (OR = 1.11, 95% CI = 1.01 ~ 1.23) and fourth (OR = 0.79, 95% CI = 0.69 ~ 0.90) quartile of self-adjustment also had lower OR of poor SRH than those with lowest quartile of self-adjustment. These findings show that EGA outperforms the traditional methods, which may be helpful to understand resilience deeply. CD-RISC should be interpreted into two aspects among community-dwelling older adults in China, highlighting the significance of the practical value and cultural context of resilience.

How long were older people expected to live with or without sarcopenia? Multistate modeling of a national cohort study.

Objectives: Sarcopenia is well known to be associated with mortality, but there is a lack of evidence on the estimates of life expectancy (LE) for sarcopenia in China. This study aims to estimate total life expectancy (TLE) and sarcopenia-specific LE in community-dwelling older Chinese adults with and without sarcopenia. Methods: This study included participants aged 60 years and older who enrolled in the cohort in 2011 and 2013 and at least completed one follow-up until 2015 as part of the China Health and Retirement Longitudinal Study (CHARLS). The criteria for defining sarcopenia were based on the guidelines established by the Asian Working Group on Sarcopenia in 2019. TLE and sarcopenia-specific LE were estimated for the total population and subgroups using continuous-time multistate modeling. Results: A total of 6,029 participants (49.2% women) with an average age of 68.4 (SD: 6.56) years were included in the study. The baseline prevalence of sarcopenia and possible sarcopenia was 19.5 and 44.9%, respectively. We observed that sarcopenia stages naturally deteriorated to worse stages (including death, by 24.4%) and returned to better stages (17.1%) during a median follow-up of 3.92 years (IQR: 2.00 ~ 4.00). The average TLE at the age of 60 was 20.9 [95% CI: 20.2-21.5] years (22.1 [95% CI: 19.6-24.6] for non-sarcopenic older adults, 20.9 [95% CI: 19.5-22.3] for possible sarcopenic, and 18.7 [95% CI: 16.4-21.1] for sarcopenic). Men, former and current smokers, and those living in northwest China had less TLE. Sarcopenic older adults, those with lower education, those who are unmarried, those with agriculture hukou, and those living in rural and northwest China were expected to live fewer years with non-sarcopenia. Sarcopenic older people, men, those with agriculture hukou, and those living in rural and southwest China were expected to live more years with sarcopenia. Discussion: The results improved our understanding of the relationship between sarcopenia and life expectancy. We suggested that targeted strategies should be considered in high-risk populations and underdeveloped regions to prevent sarcopenia and improve non-sarcopenic life years for the older population.

Temporal and spatial analysis of anthropogenic mercury and CO2 emissions from municipal solid waste incineration in China: Implications for mercury and climate change mitigation.

The contribution of municipal solid waste incineration (MSWI) to anthropogenic mercury and CO2 emissions have become increasingly important over the past decade. This study developed an inventory of anthropogenic mercury emissions and CO2 emissions during the period of 2014-2020, of MSWI process in China using a bottom-up inventory at the plant level. Overall, national MSWI anthropogenic mercury emissions increased from 2014 to 2020 by province. It was estimated that total 8321.09 kg of anthropogenic mercury emissions from 548 MSWI plants were scattered in 31 provinces of mainland China in 2020. The average intensity of mercury emission in China was 0.06 g·t-1 in 2020, which was much lower than the pre-2010 level. Furthermore, the increased CO2 emission generated by MSWI from 2014 to 2020 is 1.97 times. Anthropogenic mercury emissions and CO2 emissions were concentrated mainly in developed coastal provinces and cities. The general uncertainty of national mercury emissions and CO2 emissions was estimated to be -123% to 323% and -130% to 335%, respectively. Furthermore, future emissions were predicted from 2030 to 2060 based on different scenarios of the independent and collaborative effects of control proposals, the results indicate that the enhancement of advanced air pollution control technologies and effective management of MSWI represent pivotal factors in realizing future reductions in CO2 and mercury emissions. The findings will supplement those for mercury and CO2 emissions, and be useful for relevant policy-making and to improve urban air quality, as well as human health.

Vehicle-Mounted Pavement Health Monitoring System Based on a Spring-Guide-Assisted Triboelectric Sensor.

The present pavement health monitoring is limited by a professional staff patrol. Herein, a vehicle-mounted pavement health monitoring system (VPHMS) based on a spring-guide-assisted triboelectric sensor (S-TES) is proposed, which uses the vibration generated by vehicles passing through uneven pavements to monitor the pavement damage. The VPHMS consists of S-TES, the integration module, and the terminal display module. The designed S-TES has high stability and can achieve a high linear vibration amplitude measurement within 90 mm. Moreover, the integration module is used to process signals and transmit wireless data transmission. The terminal display module is used to receive signals and display the measurement results on the screen. When a vehicle equipped with VPHMS is driven over uneven pavements, the system can accurately monitor the potholes and upheavals on the pavement in real time. This work has significant application value in fields such as pavement health monitoring and intelligent transportation.

Retraction: Sequestration and speciation of Eu(III) on gamma alumina: role of temperature and contact order.

Retraction of 'Sequestration and speciation of Eu(III) on gamma alumina: role of temperature and contact order' by Yawen Cai et al., Environ. Sci.: Processes Impacts, 2015, 17, 1904-1914, https://doi.org/10.1039/C5EM00412H.

Macroscopic and microscopic investigation of Ni(II) sequestration on diatomite by batch, XPS, and EXAFS techniques.

Sequestration of Ni(II) on diatomite as a function of time, pH, and temperature was investigated by batch, XPS, and EXAFS techniques. The ionic strength-dependent sorption at pH < 7.0 was consistent with outer-sphere surface complexation, while the ionic strength-independent sorption at pH = 7.0-8.6 was indicative of inner-sphere surface complexation. EXAFS results indicated that the adsorbed Ni(II) consisted of ∼6 O at R(Ni-O) ≈ 2.05 Å. EXAFS analysis from the second shell suggested that three phenomena occurred at the diatomite/water interface: (1) outer-sphere and/or inner-sphere complexation; (2) dissolution of Si which is the rate limiting step during Ni uptake; and (3) extensive growth of surface (co)precipitates. Under acidic conditions, outer-sphere complexation is the main mechanism controlling Ni uptake, which is in good agreement with the macroscopic results. At contact time of 1 h or 1 day or pH = 7.0-8.0, surface coprecipitates occur concurrently with inner-sphere complexes on diatomite surface, whereas at contact time of 1 month or pH = 10.0, surface (co)precipitates dominate Ni uptake. Furthermore, surface loading increases with temperature increasing, and surface coprecipitates become the dominant mechanism at elevated temperature. The results are important to understand Ni interaction with minerals at the solid-water interface, which is helpful to evaluate the mobility of Ni(II) in the natural environment.

[Regulation Control of a Tribasic Amendment on the Chemical Fractions of Cd and As in Paddy Soil and Their Accumulation in Rice].

A pot experiment was conducted to identify the effect of a tribasic amendment (limestone+diatomite+ferric sulfate, LDF) on chemical fractions of Cd and As in paddy soils and their accumulation in brown rice. LDF was set to seven levels (0, 0.5, 1.0, 2.0, 4.0, 8.0, and 16.0 g·kg-1) based on the quality ratio, and two genotypes of rice were planted (Huanghuazhan and T-you 272). The results show that:① The application of LDF increased the rhizosphere soil pH of two varieties of rice, Huanghuazhan and T-you 272, by 0.01-0.42 and 0.11-0.54, respectively, and decreased the concentrations of EX-Cd by 11.1%-61.1% and 26.5%-52.9%, respectively, and the concentrations of EX-As by 8.2%-60.0% and 5.6%-49.9%, respectively. ② Application of LDF promoted the transformation of soil Cd and As from soluble to insoluble forms. Although the trends of the rhizosphere soils of the two rice varieties were not consistent, the application of LDF could decrease the proportion of EX-Cd and increase the proportion of Fe/Mn-Cd, Org-Cd, and O-Cd, which was accompanied by the reduction of the proportion of EX-As and an increase in the proportion of Ca-As. ③ The concentrations of Cd, As, and Fe in the iron plaque decreased by applying LDF, while the concentration of Mn increased, and the maximum increase of Mn could reach 124.2%. ④ Application of LDF decreased the concentrations of Cd in brown rice of the two varieties of rice by 64.6% and 65.9%, respectively, and decreased that of As by 37.0% and 42.5%, respectively. The effect on the concentrations of inorganic As was not significant. When the application amount of LDF was 2-16 g·kg-1, the concentrations of Cd and inorganic As in T-you 272 brown rice were both under 0.2 mg·kg-1, and when the application amount was 16 g·kg-1, the concentrations of Cd and inorganic As in Huanghuazhan brown rice were both under 0.2 mg·kg-1. In actual agricultural production, the application amount of LDF can be adjusted according to the soil pollution levels and the rice varieties.

Correction to: Competitive sequestration of Ni(II) and Eu(III) on montmorillonite: role of molar Ni:Eu ratios and coexisting oxalate.

In the original publication Fig. 10b was erroneously plotted due to the authors' carelessness and unintentional misoperation.

Mechanisms of U(VI) removal by biochar derived from Ficus microcarpa aerial root: A comparison between raw and modified biochar.

Uranium (U) is a toxic and radioactive element. Excessive amounts of aqueous U(VI) generated from U mining, processing and nuclear industry may result in severe and irreversible damage to the environment. Herein, Ficus microcarpa aerial root (FMAR), a biowaste material, was used to adsorb U(VI) from aqueous solutions for the first time. Potassium permanganate (KMnO4)-modified FMAR biochar was synthesised, characterised and compared with raw (unmodified) biochar with respect to U(VI) adsorption. The results showed that the adsorption capability of the modified FMAR biochar was evidently higher than that of the raw biochar. Multiple characterisation techniques confirmed that the discrepancy was mainly due to the increased content of O-H and formation of irregular sheet-like nanostructure with the ultrafine MnO2 nanoparticles on the biochar surfaces after KMnO4 modification. The abundance of O-H and nanoscale MnO2 notably enhanced the adsorption of U(VI) by means of coordination and Lewis acid-base interaction. The results indicate that KMnO4-modified FMAR biochar has a good potential to serve as an environment-friendly adsorbent for the removal of U(VI) from solution.

Competitive sequestration of Ni(II) and Eu(III) on montmorillonite: role of molar Ni:Eu ratios and coexisting oxalate.

The competitive binding trends of Ni(II) and Eu(III) on montmorillonite in the absence/presence of Na-oxalate are explored by using batch sorption/desorption technique, speciation modeling, and X-ray diffraction (XRD) analysis. With a series of molar Ni:Eu ratios (i.e., 1:1, 5:1, 10:1, 1:5, and 1:10), the coexisting Ni(II) did not affect the sequestration behaviors and immobilization mechanisms of Eu(III). In contrast, the presence of Eu(III) obviously suppressed the sorption percentages of Ni(II) in the acidic pH range. Even though no obvious influence of Eu(III) on the macroscopic binding trends of Ni(II) was observed under alkaline conditions, the fraction of Ni(II) adsorbed by the inner-sphere complexation mechanism decreased and that of Ni(II) precipitation increased with rising molar Ni:Eu ratio. The coexisting Na-oxalate did not influence Eu(III) sorption, while inhibited the sorption of Ni(II). The XRD analysis indicated the potential formation of two Eu-oxalate precipitate phases (i.e., Eu2(C2O4)3·xH2O(s)-1 and Eu2(C2O4)3·xH2O(s)-2) at different pH values (4.0 and 6.5) and Na-oxalate concentrations (ranging from 0.5 to 5.0 mM). Interestingly, the Eu2(C2O4)3·xH2O(s)-2 phase would be transformed into the Eu2(C2O4)3·xH2O(s)-1 solid with the increase of Na-oxalate concentration. The research findings could provide essential data for evaluating the fate of coexistent Eu(III) and Ni(II) in the complicated aquatic environment.

Macroscopic, theoretical simulation and spectroscopic investigation on the immobilization mechanisms of Ni(II) at cryptomelane/water interfaces.

In the present study, the macroscopic sorption behaviors and microscopic immobilization mechanisms of Ni(II) at cryptomelane/water interfaces were explored using the combination of batch sorption technique, desorption procedure, theoretical simulation, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and extended X-ray absorption fine structure (EXAFS) analyses. The good simulation of the pseudo-second-order model on the sorption kinetics data suggests a driving force of chemical sorption rather than mass transport or physical interaction. The sorption trends and uptake mechanisms are obviously related to the solution pH, with cation exchange or outer-sphere surface complexation at an acidic pH of 4.0, inner-sphere surface complexation in both the edge-shared (ES) and double corner-shared (DCS) modes at a neutral pH of 7.0, and precipitation of α-Ni(OH)2(s) phase at a highly alkaline pH of 10.0. The gradual increase of Ni(II) sorption amount with solution temperature rising from 293 K to 333 K is consistent with the increased ratio of the weak DCS configuration. The research findings herein can help us better understand the migration and transformation trends of Ni(II) in the manganese mineral-riched aquatic environment.