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.

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.

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.

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

The speciation, migration and transport of radionuclides in the environment are significantly influenced by their interactions with the natural minerals and humic substances therein. In view of this, the effect of temperature and contact order on the sorption behaviors of trivalent Eu(iii) in the γ-Al2O3/Eu(iii) and γ-Al2O3/HA/Eu(iii) systems was studied using batch experiments and the extended X-ray absorption fine structure spectroscopy (EXAFS) technique. The endothermic sorption behavior of Eu(iii) in the γ-Al2O3/Eu(iii) systems was induced by the hydrolysis reaction of Eu(iii) in solution and the complexation of Eu(iii) with the γ-Al2O3 surface sites. The endothermic sorption of Eu(iii) in the γ-Al2O3/HA/Eu(iii) systems was attributed to the endothermic binding of HA on γ-Al2O3 and the endothermic complexation between Eu(iii) and HA. EXAFS analysis suggested the formation of type B ternary complexes and their thermodynamic stability improves with rising temperature. The different sorption percentages under various contact orders were closely related to the binding mode of Eu(iii) on the exposed γ-Al2O3 surfaces or the γ-Al2O3/HA colloids. The findings obtained herein are important to evaluate the security of the radioactive waste repository and predict the fate of trivalent actinides (e.g., Am(iii), Cm(iii), Pu(iii), etc.) near the geological repository.

Mutual effects of copper and phosphate on their interaction with γ-Al2O3: combined batch macroscopic experiments with DFT calculations.

The mutual effects of Cu(II) and phosphate on their interaction with γ-Al(2)O(3) are investigated by using batch experiments combined with density functional theory (DFT) calculations. The results of batch experiments show that coexisting phosphate promotes the retention of Cu(II) on γ-Al(2)O(3), whereas phosphate retention is not affected by coexisting Cu(II) at low initial phosphate concentrations (≤ 3.6 mg P/L). Cu-phosphate aqueous complexes control Cu(II) retention through the formation of type B ternary surface complexes (where phosphate bridges γ-Al(2)O(3) and Cu(II)) at pH 5.5. This deduction is further supported by the results of DFT calculations. More specifically, the DFT calculation results indicate that the type B ternary surface complexes prefer to form outer-sphere or monodentate inner-sphere binding mode under our experimental conditions. The enhancement of phosphate retention on γ-Al(2)O(3) in the presence of Cu(II) at high initial phosphate concentrations (>3.6 mg P/L) may be attributed to the formation of 1:2 Cu(II)-phosphate species and/or surface precipitates. Understanding the mutual effects of phosphate and Cu(II) on their mobility and transport in mineral/water environments is more realistic to design effective remediation strategies for reducing their negative impacts on aquatic/terrestrial environments.

The removal of U(VI) from aqueous solution by oxidized multiwalled carbon nanotubes.

Multiwalled carbon nanotubes (MWCNTs) have exhibited high sorption capacity for radionuclides due to the unique hollow structure and large surface area. In this study, surface properties of oxidized MWCNTs were characterized by using XRD, SEM, FTIR and potentiometric acid-base titration. The sorption of U(VI) on oxidized MWCNTs as a function of contact time, U(VI) concentration, pH, ionic strength, humic acid/fulvic acid (HA/FA) and carbonate was investigated by using batch technique. The removal of U(VI) by oxidized MWCNTs was strongly dependent on pH and ionic strength. The presence of HA/FA enhanced U(VI) removal on oxidized MWCNTs at low pH while inhibited U(VI) sorption at high pH. The mechanism of U(VI) sorption on oxidized MWCNTs was assumed to be cation exchange/outer-sphere surface complexation in acidic pH and to form precipitation under circum neutral conditions. The oxidized MWCNTs exhibit higher sorption capacity and stronger chemical affinity than pristine MWCNTs.

Impact of water quality parameters on the sorption of U(VI) onto hematite.

In this study, the sorption of U(VI) from aqueous solution on hematite was studied as a function of various water quality parameters such as contact time, pH, ionic strength, soil humic acid (HA) or fulvic acid (FA), solid content and temperature by using a batch technique. The results demonstrated that the sorption of U(VI) was strongly dependent on ionic strength at pH<6.0, and outer-sphere surface complexation may be the main sorption mechanism. The sorption was independent of ionic strength at pH>6.0 and the sorption was mainly dominated by inner-sphere surface complexation. The presence of HA/FA increases U(VI) sorption at low pH, whereas decreases U(VI) sorption at high pH. The thermodynamic parameters (ΔH°, ΔS°, and ΔG°) were calculated from the temperature dependent sorption isotherms, and the results suggested that U(VI) sorption was a spontaneous and endothermic process. The results might be important for the application of hematite in U(VI) pollution management.