Uranium Biogeochemistry in the Rhizosphere of a Contaminated Wetland.

The objective of this study was to determine if U sediment concentrations in a U-contaminated wetland located within the Savannah River Site, South Carolina, were greater in the rhizosphere than in the nonrhizosphere. U concentrations were as much as 1100% greater in the rhizosphere than in the nonrhizosphere fractions; however and importantly, not all paired samples followed this trend. Iron (but not C, N, or S) concentrations were significantly enriched in the rhizosphere. XAS analyses showed that in both sediment fractions, U existed as UO22+ coordinated with iron(III)-oxides and organic matter. A key difference between the two sediment fractions was that a larger proportion of U was adsorbed to Fe(III)-oxides, not organic matter, in the rhizosphere, where significantly greater total Fe concentrations and greater proportions of ferrihydrite and goethite existed. Based on 16S rRNA analyses, most bacterial sequences in both paired samples were heterotrophs, and population differences were consistent with the generally more oxidizing conditions in the rhizosphere. Finally, U was very strongly bound to the whole (unfractionated) sediments, with an average desorption Kd value (Usediment/Uaqueous) of 3972 ± 1370 (mg-U/kg)/(mg-U/L). Together, these results indicate that the rhizosphere can greatly enrich U especially in wetland areas, where roots promote the formation of reactive Fe(III)-oxides.

Mineralogical transformation of arsenic at different copper smelting workshops: The impact on arsenic bioaccessibility.

Soil arsenic (As) contamination associated with the demolition of smelting plants has received increasing attention. Soil As can source from different industrial processes, and also participate in soil weathering, making its speciation rather complex. This study combined the usage of chemical sequential extraction and advanced spectroscopic techniques, e.g., time of flight secondary ion mass spectrometry (ToF-SIMS), to investigate the mineralogical transformation of soil As at different processing sites from a typical copper smelting plant in China. Results showed that the stability of arsenic species decreased following the processes of storage, smelting, and flue gas treatment. Arsenic in the warehouse area was incorporated into pyrite (FeS2) as well as its secondary minerals such as jarosite (KFe3(SO4)2(OH)6). At the smelting area, a large proportion of As was adsorbed by iron oxides from smelting slags, while some As existed in stable forms like orpiment (As2S3). At the acid-making area, more than half of As was adsorbed on amorphous iron oxides, and some were adsorbed on the flue gas desulfurization gypsum. More importantly, over 86% of the As belonged to non-specifically and specifically adsorbed fractions was found to be bioaccessible, highlighting the gypsum-adsorbed As one of the most hazardous species in smelting plant soils. Our findings indicated the importance of iron oxides in As retention and suggested the potential health risk of gypsum-adsorbed As. Such detailed knowledge of As speciation and bioaccessibility is vital for the management and remediation of As-contaminated soils in smelting plants.

The environmental impact of heavy metals in sediments of main valleys in the eastern side of Mosul City, Iraq.

Analyzing the geochemical changes in stream sediments can reveal important surface processes on Earth, like weathering, transportation, and cation exchange. The study area is located on the eastern side of Mosul, where valleys named Al-Rashediya, Al-Kharrazi, Al-Khosar, Al-Danffilli, and Al-Shor flow towards the Tigris River. These valleys' sediments contain diverse components like clay minerals, organic matter, iron oxides, carbonates, and heavy metals (H.M.s), either as part of these substances or adsorbed onto them. In this study, 36 sediment samples were gathered from these valleys. They underwent chemical analysis through X-ray fluorescence to ascertain their chemical constituents of major oxides. To understand the distribution of H.M.s in these sediments, correlation coefficient analysis and factor analysis were utilized. The study employed the geoaccumulation index (Igeo) and enrichment factor (E.F.) to evaluate sediment contamination. The results of Igeo ranged from Cr = 0.24 to 1.83, Ni = -0.92 to 0.77, Cu = -2.41 to 0.05, Zn = -1.83 to 0.89, Pb = -1.54 to 0.36, and As = -2.84 to 0.80. These findings suggest that the valley sediments are generally in the range of deficiency to minimal enrichment and moderate enrichment. However, Al-Danffilli Valley shows strong contamination levels for Cu, Zn, and Pb. The E.F. values for Cr = 3.63-12.50, Ni = 1.95-4.19, Cu = 0.69-12.36, Zn = 1.08-16.19, Pb = 1.25-62.16, and As = 0.60-1.79 indicate levels ranging from deficiency to minimal and moderate enrichment. Al-Danffilli Valley, in particular, was identified as ranging from moderate to extremely high enrichment, attributed to its location near industrial areas and its tributaries.

The Cd immobilization mechanisms in paddy soil through ureolysis-based microbial induced carbonate precipitation: Emphasis on the coexisting cations and metatranscriptome analysis.

Microbial induced carbonate precipitation (MICP) can immobilize metals and reduce their bioavailability. However, little is known about the immobilization mechanism of Cd in the presence of soil cations and the triggered gene expression and metabolic pathways in paddy soil. Thus, microcosmic experiments were conducted to study the fractionation transformation of Cd and metatranscriptome analysis. Results showed that bioavailable Cd decreased from 0.62 to 0.29 mg/kg after 330 d due to the MICP immobilization. This was ascribed to the increase in carbonate bound, Fe-Mn oxides bound, and residual Cd. The underlying immobilization mechanisms could be attributed to the formation of insoluble Cd-containing precipitates, the complexation and lattice substitution with carbonate and Fe, Mn and Al (hydr)oxides, and the adsorption on functional group on extracellular polymers of cell. During the MICP immobilization process, up-regulated differential expression urease genes were significantly enriched in the paddy soil, corresponding to the arginine biosynthesis, purine metabolism and atrazine degradation. The metabolic pathway of bacterial chemotaxis, flagellum assembly, and peptidoglycan biosynthesis and the expression of cadA gene related to Cd excretion enhanced Cd resistance of soil microbiome. Therefore, this study provided new insights into the immobilization mechanisms of Cd in paddy soils through ureolysis-based MICP process.

Determination and prediction of micro scale rare earth element geochemical associations in mine drainage treatment wastes.

Acid mine drainage (AMD) has been proposed as a novel source of rare earth elements (REE), a group of elements that includes critical metals for clean energy and modern technologies. REE are sequestered in the Fe-Al-Mn-rich precipitates produced during the treatment of AMD. These AMD solids are typically managed as waste but could be a REE source. Here, results from AMD solids characterization and geochemical modeling are presented to determine the minerals/solid phases that are enriched in REE and identify the mechanism(s) of REE attenuation. AMD solids collected from limestone-based AMD treatment systems were subjected to sequential extraction and synchrotron microprobe analyses to characterize the binding nature of the REE. The results of these analyses indicated REEs were mainly associated with Al or Mn phases. Only selected REE (Gd, Dy) were associated with Fe phases, which were less abundant than Al and Mn phases in analyzed samples. The sequential extractions demonstrated that acidic and/or reducing extractions effectively mobilize REE from the AMD solids evaluated. The observed element associations in solids are consistent with geochemical model results that indicate dissolved REE can be effectively attenuated by adsorption on freshly precipitated Fe, Al, and Mn oxides/hydroxides. The model, which simulates dissolution of CaCO3 and the precipitation of Fe, Al, and Mn oxides with increased pH, accurately predicts the pH dependent accumulation of dissolved REE with Al, Mn, and Fe oxides/hydroxides in the studied AMD treatment systems. The methods and results presented here can be used to identify conditions favorable for accumulation of REE-enriched AMD solids and possible passive or active treatment(s) to extract REE from AMD. This information can be used to design AMD treatment systems for the recovery of REE and is an opportunity to transform the challenges of addressing polluted mine drainage into an environmental and economic asset.

Selective Synergistic Catalytic Elimination of NOx and CH3SH via Engineering Deep Oxidation Sites against Toxic Byproducts Formation.

NOx and CH3SH as two typical air pollutants widely coexist in various energy and industrial processes; hence, it is urgent to develop highly efficient catalysts to synergistically eliminate NOx and CH3SH. However, the catalytic system for synergistically eliminating NOx and CH3SH is seldom investigated to date. Meanwhile, the deactivation effects of CH3SH on catalysts and the formation mechanism of toxic byproducts emitted from the synergistic catalytic elimination reaction are still vague. Herein, selective synergistic catalytic elimination (SSCE) of NOx and CH3SH via engineering deep oxidation sites over Cu-modified Nb-Fe composite oxides supported on TiO2 catalyst against toxic CO and HCN byproducts formation has been originally demonstrated. Various spectroscopic and microscopic characterizations demonstrate that the sufficient chemisorbed oxygen species induced by the persistent electron transfer from Nb-Fe composite oxides to copper oxides can deeply oxidize HCOOH to CO2 for avoiding highly toxic byproducts formation. This work is of significance in designing superior catalysts employed in more complex working conditions and sheds light on the progress in the SSCE of NOx and sulfur-containing volatile organic compounds.

Size-dependent distribution of metal(loid)s in recent marine sediments of the Adriatic sea.

This paper investigates occurrence of metal(loid)s, and size-dependent changes in their concentration in recent marine sediments from coastal and open-sea environments in the eastern Adriatic. Size fractionation of sediments was performed after removal of organic matter (OM), and the individual fractions, comprising particles below 8 µm, 4 µm, 2 µm, 1 µm and 0.45 µm, were analysed using HR ICP-MS. The concentrations of most elements increased with decreasing particle size, as a result of accumulation of clay minerals and Fe and Mn (oxyhydr)oxides. A decrease in concentrations was observed for Ba, Sr, Ti and U, due to lowering of the carbonate content and presence in the coarse-grained and heavy mineral fraction. The highest element concentrations were determined in the fraction comprising particles below 1 µm. Occasionally, depending on the sedimentological environment and/or the element in question, the peak concentrations occurred in the <2 µm or <0.45 µm fraction. The lowest size-dependent enrichment was observed for elements associated with aluminosilicates (Al, Be, Cs, Co, Fe, K, Li, Rb). A different size-dependent behaviour of the elements was observed between deep-sea areas and shallow environments under greater coastal influence, mainly due to differences in sediment sorting, and between the northern and central vs. southern Adriatic due to the different catchment geologies. The Fe and Mn (oxyhydr)oxides, abundant in the deep-sea sediments, played an important role in the geochemical cycle of As, Cd, Co, Mo, Sb and V.

A novel hydrangea-like magnetic composite Fe3O4@MnO2@ZIF-67 for efficient selective adsorption of Pd(II) from metallurgical wastewater.

The selective adsorption of palladium from wastewater is a feasible solution to solving palladium pollution and resource scarcity. Because traditional solvent extraction methods often involve the use of considerable amounts of organic solvents, research is focused on investigating adsorption techniques that can selectively remove palladium from wastewater. In this paper, the magnetic composite Fe3O4@MnO2@ZIF-67 was synthesized and its performance for the adsorption of Pd(II) in acidic water was investigated. Fe3O4@MnO2@ZIF-67 was characterized by various analytical methods such as TEM, SEM, EDS, BET, XRD, FTIR, zeta potential analysis, VSM, and TGA. The effects of palladium ion concentration, contact time, pH, and temperature on adsorption were evaluated. The kinetics were shown to follow the pseudo-second-order kinetic model and Elovich model, and the rate-limiting step was chemisorption. Thermodynamic studies showed that increasing the temperature promoted the adsorption of Pd(II), and the maximum uptake capacity of Fe3O4@MnO2@ZIF-67 for Pd(II) was 531.91 mg g-1. Interestingly, Fe3O4@MnO2@ZIF-67 exhibited superior selectivity for Pd(II) in the presence of Ir(IV), Pt(IV), and Rh(III). The adsorbent can be used repeatedly for selective adsorption of palladium. Even at the fifth cycle, the uptake rate of Pd(II) remained as high as 83.1%, and it showed a favorable adsorption capacity and selectivity for Pd(II) in real metallurgical wastewater. The adsorption mechanism was analyzed by SEM, FTIR, XRD, XPS, and DFT calculations, which indicated that electrostatic interactions and coordination with nitrogen-containing groups were involved. Fe3O4@MnO2@ZIF-67 is a promising adsorbent for the efficient adsorption and selective separation of palladium ions.

Arsenic pollution, geochemical fractions, and leaching characteristics in soil samples from four contaminated sites in the Beijiang River Basin, South China.

To remediate historically polluted sites before their land-use changes, it is essential to understand the concentration distribution, geochemical fraction, and migratory behavior of As in soil with varied particle sizes for the use of a sieving procedure. This study investigated the amount and percentage of As in soil with different particle sizes (0.25, 0.25-1, and 1-2 mm) as well as its toxicity characteristic in leaching procedure at four previously contaminated sites in the Beijiang River Basin, South China. The results showed that the total As concentration in the collected soils ranged from 70.1 to 402.8 mg/kg, and only a few percent of soil particle samples had As contents below the local risk threshold value of 60 mg/kg. The amorphous hydrous oxide bound, crystalline hydrous oxide bound, and residual fractions (F3-F5) of the geochemical fraction of As in soil of polluted sites accounted for 82.2-95.7% of the total As distribution. However, the concentration of As in non-specifically bound fractions increased with the mass ratio of soil with coarse particle sizes due to the negative correlation of Fe-bearing minerals concentration with the mass ratio of soil with coarse particle size. According to redundancy analysis, soil with coarse particle sizes and non-specifically bound As were mostly responsible for the As concentration in the leachate. These findings confirmed that a sieving process was not suitable for the remediation of soil As at four historically contaminated sites in the Beijiang River Basin due to the high concentration of As in soil and non-negligible environmental risk of labile extractable As in soil with coarse particle size.

Predicting the removal efficiency of pharmaceutical and personal care products using heated metal oxides as adsorbents based on their physicochemical characteristics.

Pharmaceutical and personal care products (PPCPs) are emerging pollutants that are commonly found in the environment and exist predominantly in nondegradable forms. Several attempts have been made to remove PPCPs via conventional wastewater treatment processes; however, these processes have limitations, such as high costs and insufficient removal efficiencies. Adsorption is a promising alternative for removing PPCPs because it is inexpensive, highly reusable, and easy to operate. Therefore, this study aims to determine the contributing characteristics that can be used to predict the adsorption behaviour of PPCPs based on their physicochemical properties, with heated metal oxide adsorbents (HMOAs). HAOP (heated aluminium oxide particles) and HIOP (heated iron oxide particles) with particle sizes below 38 µm were used. Results from the Brunauer-Emmett-Teller (BET) analysis show that HIOP has higher surface area and smaller pore size (113.7 ± 26.3 m2/g and 5.4 ± 1.8 nm) than HAOP (14.5 ± 0.6 m2/g and 18.6 ± 3.1 nm), which suggest that HIOP would show superior adsorption rates compared to HAOP. The adsorption mechanism is identified based on three major physicochemical properties of PPCPs: molecular weight (M.W.), octanol-water partition coefficient (log Kow), and acid dissociation constant (pKa). The results suggest that the most dominant factor that contributes to the adsorption of PPCPs on to HMOAs is the M.W., where the larger the molecular size, the better the adsorption efficiency. The tests conducted with varying log Kow values revealed that the hydrophilicity of the adsorbent influences the adsorption performance. It was found that HIOP exhibits better removal efficiencies with hydrophilic PPCPs (up to 83%) than with hydrophobic PPCPs (48%), while HAOP exhibits better removal efficiencies with hydrophobic PPCPs (86%) than with hydrophilic PPCPs, with less than 10% removal. Unlike the M.W. and pKa values, the log Kow does not exhibit any visible trend. Therefore, the adsorption behaviour can be predicted with the M.W. and pKa values of the PPCPs, when HAOP and HIOP are used as adsorbents.

Development of ZnO-GO-NiO membrane for removal of lead and cadmium heavy metal ions from wastewater.

The presence of heavy metal (HM) ions, such as lead, cadmium, and chromium in industrial wastewater discharge are major contaminants that pose a risk to human health. These HMs should separate from the wastewater to ensure the reuse of the discharged water in the process and mitigate their environmental impacts. The distinctive mechanical properties of 2D graphene oxide (GO), and the antifouling characteristics of metal oxides (ZnO/NiO) nanoparticles combined to produce composites supporting special features for wastewater treatment. This study employed solution casting and phase inversion methods to synthesize PSF-based GO, ZnO-GO, and ZnO-GO-NiO mixed matrix membranes and the effects of variation in composition on the removal of lead (Pb2+) and cadmium (Cd2+) ion was examined. Several characterization techniques including X-ray diffraction analysis, scanning electron microscopy, energy dispersive X-ray, and Fourier transform infrared spectroscopy were applied to analyze the synthesized NPs and MMMs. The composite membranes were also analyzed in terms of their porosity, permeability, hydrophilicity, surface roughness, zeta potential, thermal stability, mechanical strength, and flux regeneration at various transmembrane pressures (2-3 kgcm-2), and pH value (5.5). The highest adsorption capacities were measured to be 308.16 mg g-1 and 354.80 mg g-1 for Pb (II) and Cd (II), respectively, for membrane (M4_A) having 0.3 wt% of ZnO-GO-NiO nanocomposite, at 200 mg L-1 of feed concentration and 1.60 mL min-1 of permeate flux. The Pb (II) and Cd (II) adsorption breakthrough curves were created, and the results of the experiment were compared with the data of the Thomas model.

Alleviation of chromium stress in plants using metal and metal oxide nanoparticles.

Chromium (Cr), one of the hazardous pollutants, exists predominantly as Cr(VI) and Cr(III) in the environment. Cr(VI) is more toxic than Cr(III) due to its high mobility and solubility. Elevated levels of Cr in agricultural soil due to various anthropogenic activities cause Cr accumulation in plants, resulting in a significant reduction in plant yield and quality due to Cr-induced physiological, biochemical and molecular alterations. It can infiltrate the food chain through crop plants and cause harmful effects in humans via biomagnification. Cr(VI) is linked to cancer in humans. Therefore, mitigation strategies are required to remediate Cr-polluted soils and limit its accumulation in plants for safe food production. Recent research on metal and metal oxide nanoparticles (NPs) has shown that they can effectively reduce Cr accumulation and phytotoxicity. The effects of these NPs are influenced by their type and dose, exposure method, plant species and experimental settings. In this review, we present an up-to-date compilation and comprehensive analysis of the existing literature regarding the process of uptake and distribution of Cr and impact and potential mechanisms of metal and metal oxide nanoparticles led mitigation of Cr-induced stress in plants. We have also discussed recent developments, existing research gaps and future research directions in the field of Cr stress mitigation by NPs in plants. Overall, this review can provide valuable insights in reducing Cr accumulation and toxicity using metal and metal oxide nanoparticles, thereby promoting safe and sustainable cultivation of food and phytostabilization of Cr-polluted soil.

Pedological data for the study of soils developed over a limestone bed in a humid tropical environment.

Lithological characteristics interact with other factors of soil formation to define soil genesis. This becomes more interesting as data on the mineral and elemental oxide components of soils developed from limestone are rarely available in the humid tropical environment. The present study investigated the elemental oxide content, forms of sesquioxides, and clay mineral species in some limestone soils. Soil samples were obtained from three (3) crestal soil profile pits and analyzed for elemental content by the use of an X-ray fluorescence spectrometer, and sesquioxide forms by inductively coupled plasma-mass spectrometer. Analyses were done in triplicates. The mineralogy of the clay fraction was determined on the A, B, and C horizon samples using an X-ray diffraction technique. The occurrence of SiO2 (203-277 g/kg), Al2O3 (65-105 g/kg), and Fe2O3 (14-95 g/kg) in substantial amounts over MnO2, ZrO2, and TiO2 with negligible quantities of CaO suggested comparatively more developed soils in the Agoi Ibami and Mfamosing tropical rainforests. Crystalline form of Fe was dominant over amorphous form, with indications of the co-migration of dithionite Fe with clay to the B horizons of the soils. Quartz, kaolinite, montmorillonite, and chlorite-vermiculite-montmorillonite interlayered minerals dominated the clay mineralogy of the studied soils. Mineral transformation places the soils at the transitory stage from the intermediate to the complete stage of soil development. The expanding clay minerals are most likely to increase plant nutrient adsorption and soil fertility status to accommodate the cultivation of a wider range of crops.

Molecular characteristics of natural organic matter in the groundwater system with geogenic iodine contamination in the Datong Basin, Northern China.

Natural organic matter (NOM) plays an important role in the iodine mobilization in the groundwater system. In this study, the groundwater and sediments from iodine affected aquifers in the Datong Basin were collected to perform chemistry analysis and molecular characteristics of NOM by Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR-MS). Total iodine concentrations in groundwater and sediments ranged from 1.97 to 926.1 µg/L and 0.001-2.86 µg/g, respectively. A positive correlation was observed between DOC/NOM and groundwater/sediment iodine. FT-ICR-MS results showed that the DOM in the high-iodine groundwater system is characterized by less aliphatic and more aromatic compounds with higher NOSC, indicating the features of more unsaturated larger molecule structures and more bioavailability. Aromatic compounds could be the main carriers of sediment iodine and were easily absorbed on amorphous iron oxides to form the NOM-Fe-I complex. More aliphatic compounds, especially those containing N/S, experienced a higher degree of biodegradation, which further mediated the reductive dissolution of amorphous iron oxides and the transformation of iodine species, thereby causing the release of iodine into groundwater. The findings of this study provide some new insights into the mechanisms of high-iodine groundwater.

Rare earth elements in soil around coal mining and utilization: Contamination, characteristics, and effect of soil physicochemical properties.

REEs are emerging contaminants, and soils nearby coal and coal ash with high REEs composition are vulnerable to REEs contamination. Besides, coal industry can alter surrounding soil characteristics. However, there is information paucity about REEs contamination and geochemical behaviors along with soil characteristics around coal industrial areas, which are essential for understanding their toxicity and mobilization. The study was conducted in soils surrounding Kriel coal-fired power plant (KCM) and Greenside coal mining in Witbank (GSCM), South Africa. Multivariate statistical analysis, pollution and fractionation indices, and BCR sequential extraction were applied. The ∑REEs in the soils were compared to ∑REEs abundance in the upper earth's crust (UEC), and slightly higher ∑REEs was found in KCM but slightly lower in GSCM. Generally, LREEs are abundant. The soil REEs were normalized using the Post-Archean Australian Shale (PAAS) and Eu and Gd in KCM and Gd in GSCM were >1. Contamination assessment revealed that the soils are slightly to moderately contaminated by REEs. ∑REEs in KCM was significantly correlated with soil particle sizes of 2.00-50.00 µm, Al2O3, Fe2O3, and MnO, while with 2.00-3.00 µm and Al2O3 in GSCM. Fractionation characteristics showed a positive Ce anomaly, with positive linear regressions with Fe2O3 and MnO. In contrast, a negative Eu anomaly was found with positive linear regressions with Al, Ca, and Mg-oxides. Oxidizable fractioned REEs accounted for 32.33% of the ∑REEs in GSCM and 35.85% in KCM, and their high EF suggests enrichment that could be due to coal mining and utilization. Most soil physicochemical properties appear to be negatively correlated with the exchangeable REEs. Overall, the soils are contaminated by REEs and the REEs characteristics are considerably influenced by major elements oxide, U, and Th contents. Therefore, more attention should be paid to REEs contamination and impacts around coal mining and utilization.

Carbon sequestration in paddy soils: Contribution and mechanisms of mineral-associated SOC formation.

In this work, comparative study of paddy and upland soils were carried out to unravel mechanisms of enhanced soil organic carbon (SOC) sequestration in paddy soils using fractionation methods, 13C NMR and Nano-SIMS analysis, as well as organic layer thickness calculations (Core-Shell model). The results showed that although there is a strong increase in particulate SOC in paddy soils compared to that in the upland soils, the increase in mineral-associated SOC is more important, explaining 60-75% of SOC increase in the paddy soils. In the wet and dry alternate cycles of paddy soil, iron (hydr)oxides adsorb relatively small and soluble organic molecules (fulvic acid-like), promote catalytic oxidation and polymerization, thus accelerating formation of larger organic molecules. Upon reductive iron dissolution, these molecules are released and incorporated into existing less soluble organic compounds (humic acid or humin-like), which are coagulated and associated with clay minerals, becoming part of the mineral-associated SOC. The functioning of this "iron wheel" process stimulates accumulation of relatively young SOC into mineral-associated organic carbon pool, and reduces the difference in chemical structure between oxides-bound and clay-bound SOC. Further, the faster turnover of oxides and soil aggregates in paddy soil also facilities interaction between SOC and minerals. The formation of mineral-associated SOC may delay degradation of organic matter during both wet and dry period in the paddy field, therefore enhancing carbon sequestration in paddy soils.

Remediation performance of As-contaminated water and soil using a novel Fe-Mn bimetallic (oxyhydr)oxide coated on natural magnetite.

It is challenging to separate the materials for treating arsenic contamination of soil and water from systems. The natural magnetite covered with Fe-Mn bimetallic (oxyhydr)oxide (Fe-Mn MSM) was effectively created in this study, and its potential use in removing As from water and soil was investigated. Batch adsorption studies showed that the As(V) adsorption on Fe-Mn MSM could achieve equilibrium after 120 min when the initial As(V) concentration was 39.85 mg/L. The calculated maximum adsorption of Fe-Mn MSM for As(V) was 17.94 mg/g at 20 °C. The mechanism of As(V) adsorption was confirmed to be a combination of ligand exchange and electrostatic attraction by the outcomes of FTIR analysis, SEM, and batch adsorption tests. Fe-Mn MSM can also be a successful amendment for cleaning up As-polluted soil. The 5% Fe-Mn MSM treatment group had the lowest exchangeable fraction of As (EX-As) concentration, 0.039 mg/kg (8.3% of initial EX-As), after 40 days. Magnetic separation could be used to quickly and completely recover the used Fe-Mn MSM from the soil. EX-As was present in higher concentrations on Fe-Mn MSM than that of the original soil. As a result, this work offers a strategy that may be put into practice to cheaply remove As from soil and water while also encouraging the reuse of natural magnetite.

Release characteristics of heavy metals from electrolytic manganese residue under varying environmental factors.

High levels of manganese (Mn) and other heavy metals from electrolytic manganese residue (EMR) stockpiled would be released into the environment under natural conditions. A batch-leaching test was carried out to investigate the release characteristics of heavy metals from EMR with different storage times under simulated environmental conditions such as acid rain with different pH (3.0, 4.5, 5.6, and 7.0) at contact times of 1, 2, 4, 6, and 12 h; liquid to solid ratio (L/S) (5:1, 10:1, 20:1, and 30:1); and temperature (15, 25, 35, and 45 °C). The results showed that low pH (3.0 and 4.5) and high temperature (35 and 45 °C) could significantly promote heavy metal leaching from EMRs and increasing the L/S ratio above 20:1 mL/g significantly decreased heavy metal leachate concentrations due to dilution effect. Cr, Mn, and Pb concentrations in leachate increased almost continuously throughout the leaching process, while Zn decreased slightly at the 12th hour. Meanwhile, heavy metal concentrations in EMR1 (fresh EMR) were higher than in EMR2 (out stockpiled for more than 3 months). The concentrations of Mn, Pb, and Zn in leachates from EMRs at pH 3.0 and 4.5 leaching far exceeded the allowable maximum discharge concentrations for pollutants of the integrated wastewater discharge standard in China (GB8978-1996) by 57.5-59.0, 1.3-4.3, and 1.1-1.8 and 53.5-56.0, 3.04-7.25, and 1.0-1.91 times, respectively. Additionally, the Mn concentrations from both EMR leachates at pH 7.0 were above the national safe emission threshold. The morphological structure of EMRs changed after leaching, and XRD analysis showed the disappearance of MnO2, SiO2, FeS2, and CaSO4. The XPS revealed that Cr, Mn, Pb, and Zn existed as Cr3+, MnO, PbSO4, and ZnSiO3, respectively, after leaching. The study concluded that Mn, Pb, and Zn from EMRS leached by acid rain might pose a high potential environmental risk. Therefore, developing appropriate disposal techniques for EMR is necessary to prevent heavy metal pollution.

Biochar and nano-ferric oxide synergistically alleviate cadmium toxicity of muskmelon.

Cadmium is toxic to plants. The accumulation of cadmium in edible plants such as muskmelon may affect the safe production of crops and result in human health problem. Thus effective measures are urgently needed for soil remediation. This work aims to investigate the effects of nano-ferric oxide and biochar alone or mixture on muskmelon under cadmium stress. The results of growth and physiological indexes showed that compared with the application of cadmium alone, the composite treatment (biochar and nano-ferric oxide) decreased malondialdehyde content by 59.12% and ascorbate peroxidase activity increased by 276.6%. Their addition can increase the stress resistance of plants. The results of soil analysis and cadmium content determination in plants showed that the composite treatment was beneficial to reduce the cadmium content in various parts of muskmelon. In the presence of high concentration of cadmium, the Target Hazard Quotient value of peel and flesh of muskmelon in the composite treatment was less than 1, which means the edible risk was greatly reduced. Furthermore, the addition of composite treatment increased the content of effective components; the contents of polyphenols, flavonoids, and saponins in the flesh of the compound treatment were increased by 99.73%, 143.07%, and 18.78% compared with the cadmium treatment. The results provide a technical reference for the further application of biochar combined with nano-ferric oxide in the field of soil heavy metal remediation, and provide a theoretical basis for further research on reducing the toxicity of cadmium to plants and improving the edible quality of crops.

Efficient utilization of biogenic manganese oxides in bioaugmentation columns for remediation of thallium(I) contaminated groundwater.

Little attention has been paid to the in situ-generated biogenic manganese oxides (BMnOx) for practical implementation in continuous groundwater remediation systems. The enrichment effects of manganese oxidizing bacteria (MOB) in bioaugmentation columns and the in situ-generated BMnOx for continuous thallium(I) (Tl(I)) removal from groundwater were investigated. Results indicated that Pseudomonas Putida MnB1 (strain MnB1) attached on the groundwater sediments (GS) can achieve a maximum of 97.37 % Mn(II) oxidation and generate 29.6 mg/L BMnOx, which was superior than that of traditional quartz sand (QS). The in situ-generated BMnOx in MOB_GS column effectively removed 10-100 µg/L Tl(I) under the interference of high concentrations of Fe(II) and Mn(II) in groundwater. Distinctive microbial enrichment effects occurred in the bioaugmentation columns under the competition of indigenous microbes in groundwater. The release of Mn(II) from the BMnOx inhibited with the decrease in Tl(I) removal efficiency. XAFS analysis revealed Tl(I) was effectively adsorbed by BMnOx and Mn-O octahedra with Tl-O tetrahedral coordination existed in BMnOx. This study provides an in-depth understanding of the in situ-generated BMnOx for the Tl(I) removal and contributes to the application of BMnOx in groundwater remediation.