Performance and mechanisms for Cd(II) and As(III) simultaneous adsorption by goethite-loaded montmorillonite in aqueous solution and soil.

A series of goethite-modified montmorillonite (GMt) materials was synthesized for the amelioration of cationic cadmium (Cd) and anionic arsenic (As) complex contaminants in soil and water bodies. The results showed that goethite (Gt) was successfully loaded onto the surface of montmorillonite (Mt), which possessed more functional groups (such as Fe-O, and Fe-OH) and a larger specific surface area. GMt-0.5 (Mt loaded with Gt at a ratio of 0.5:1) showed the highest adsorption capacity for Cd(II) and As(III) with the maximum of 50.61 mg/g and 57.58 mg/g, respectively. The removal rate of Cd(II) was highly pH dependent, while the removal rate of As(III) showed little dependence on pH. The goethite on montmorillonite might contribute to the formation of surface complexes with As(III) and oxidation of As(III) to As(V). In the binary system, both, synergistic and competitive adsorption existed simultaneously. Importantly, in the binary system, the removal of As(III) was more favorable because of the electrostatic interaction, formation of a ternary complex, and co-precipitation. In addition, the amendment of GMt-0.5 significantly reduced the availability of Cd and As in the soil. This study suggests that GMt-0.5 is a promising candidate for the simultaneous immobilization of metal (loid)s in both, aqueous solution and mine soil.

Effect of goethite-loaded montmorillonite on immobilization of metal(loid)s and the micro-ecological soil response in non-ferrous metal smelting areas.

In this work, the immobilization stabilization and mechanism of heavy metal(loid)s by goethite loaded montmorillonite (GMt) were investigated, and the soil microbial response was explored. The simulated acid rain leaching experiment showed that GMt had a higher acid tolerance and the more stable heavy metal(loid)s fixation ability. The soil incubation demonstrated that GMt significantly decreased the available Cd, Zn, Pb and As concentration. Interestingly, higher immobilization of heavy metals was observed by GMt in highly acid leached and acidic soils. The richness and diversity of bacterial communities improved after the addition of GMt. GMt induced the enrichment of the excellent functional bacteria of the phylum Proteobacteria as well as the genus Massilia and Sphingomonas. The main immobilization mechanisms of heavy metal(loid)s by GMt include electrostatic interaction, complexation, precipitation and oxidation. The addition of the GMt also optimizes the soil bacterial community structure, which further facilitates the immobilization of heavy metal(loid)s. Our results confirm that the novel GMt has a promising application in the immobilization and stabilization of heavy metal(loid)s contaminated soils in non-ferrous metal smelting areas.

Dithionite accelerated copper slag heterogeneous-homogeneous coupled Fenton degradation of organic pollutants.

The heterogeneous-homogeneous coupled Fenton (HHCF) processes combine the advantages of rapid reaction and the catalyst reuse, which makes them attractive for wastewater treatment. Nevertheless, the lack of both, cost-effective catalysts and the desirable Fe3+/Fe2+ conversion mediators limit the development of HHCF processes. This study investigates a prospective HHCF process, in which solid waste copper slag (CS) and dithionite (DNT) act as catalyst and mediator of Fe3+/Fe2+ transformation, respectively. DNT enables controlled leaching of iron and a highly efficient homogeneous Fe3+/Fe2+ cycle by dissociating to SO2- • under acidic conditions, leading to the enhanced H2O2 decomposition and •OH generation (from 48 µmol/L to 399 µmol/L) for p-chloroaniline (p-CA) degradation. The removal rate of p-CA in the CS/DNT/H2O2 system increased by 30 times in comparison with the CS/H2O2 system (increased from 1.21 × 10-3 min-1 to 3.61 × 10-2 min-1). Moreover, batch dosing of H2O2 can greatly promote the yield of •OH (from 399 µmol/L to 627 µmol/L), by mitigating the side reactions between H2O2 and SO2- •. This study highlights the importance of the iron cycle regulation for improvement of the Fenton efficiency and develops a cost-effective Fenton system for organic contaminants elimination in wastewater.

Simultaneous removal of typical flotation reagent 8-hydroxyquinoline and Cr(VI) through heterogeneous Fenton-like processes mediated by polydopamine functionalized ATP supported nZVI.

The heavy metal and organic pollution caused by mining activities keep attracting attention, thus an economic and efficient treatment for combined pollution is pressing. In this study, the simultaneous removal performance of typical organic flotation reagent 8-hydroxyquinoline (8-HQ) and Cr(VI) was investigated via heterogeneous Fenton process induced by a novel polydopamine (PDA) functionalized attapulgite supported nano sized zero-valent iron (nZVI) composite (PDA/ATP-nZVI). Batch experiments showed that PDA/ATP-nZVI had better catalytic reactivity and reduction ability than both ATP-nZVI and nZVI. Under acidic condition, 96.0% of 8-HQ was degraded accompanied with the 42.5% of total organic carbon (TOC) decrease, while 95.8% of Cr(VI) removal efficiency was accomplished by PDA/ATP-nZVI. PDA not only served as redox mediator in expediting electron transfer, but also acted as electron donor that accelerated transformation from Fe(III) to both dissolved Fe(II) and surface Fe(II), which resulted in the increased degradation of 8-HQ. The synergic removal behavior between 8-HQ and Cr(VI) was discussed and the reaction mechanism in the persulfate (PS)-PDA/ATP-nZVI system was also explored. This study developed a highly efficient heterogeneous catalyst, and demonstrated that the PS-PDA/ATP-nZVI system had a potential for remediation of mine environment polluted by both heavy metals and organic flotation reagents.

A robust biocatalyst based on laccase immobilized superparamagnetic Fe3O4@SiO2-NH2 nanoparticles and its application for degradation of chlorophenols.

The presence of chlorophenols in water and wastewater is considered a serious environmental issue. To eliminate these micropollutants, biodegradation of chlorophenols using enzyme-nanoparticle conjugated biocatalyst, is proposed as an economical and eco-friendly method. Herein, amino-functionalized superparamagnetic Fe3O4@SiO2-NH2 nanoparticles with core-shell structure were constructed as a promising carrier for immobilization of laccase from Trametes versicolor. Compared with free laccase, Fe3O4@SiO2-NH2-Laccase displayed remarkable outcomes in all major areas such as temperature and storage stabilities, and tolerance to organic solvents and metal ions. The biocatalytic performance and reusability of Fe3O4@SiO2-NH2-Laccase were evaluated for the degradation of 2,4-dichlorophenol (2,4-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP) in repeated cycles. Even after 10 successive reuses, the degradation rate of 2,4-DCP and 2,4,6-TCP were found to be 54.9% and 68.7%, respectively. The influences of solution pH, initial chlorophenol concentration, and temperature on the degradation rate of these two chlorophenols were evaluated. The degradation intermediate products including dimers, trimers, and tetramers of 2,4-DCP and 2,4,6-TCP were identified. Release of chloride ions was observed during the enzymatic degradation of these two chlorophenols. Based on the determination of intermediate products and released chloride ions, the degradation pathway that was involved in dehydrogenation, reactive radical intermediates formation, dechlorination, self-coupling and oligomers/polymers formation was proposed. The toxicity of these two chlorophenols and their intermediates was substantially reduced during the enzymatic degradation. The results of this study might present an alternative clean biotechnology for the remediation of 2,4-DCP and 2,4,6-TCP contaminated water matrices.

Superior elimination of Cr(VI) using polydopamine functionalized attapulgite supported nZVI composite: Behavior and mechanism.

In this study, a polydopamine (PDA) modified attapulgite (ATP) supported nano sized zero-valent iron (nZVI) composite (PDA/ATP-nZVI) was rapidly synthesized under acidic conditions, and employed to alleviate Cr(VI) toxicity from an aqueous solution. Kinetic studies revealed that Cr(VI) adsorption process followed the pseudo-second order model, suggesting chemisorption was the dominant adsorption mechanism. Liu isotherm adsorption model was able to better describe the Cr(VI) adsorption isotherm with the maximum adsorption capacity of 134.05 mg/g. The thermodynamic study demonstrated that the adsorption process occurred spontaneously, accompanied by the increase in entropy and endothermic reaction. Low concentrations of coexisting ions had negligible effects on the removal of Cr(VI), while high concentrations of interfering ions were able to facilitate the removal of Cr(VI). Reactive species test revealed that Fe2+ played a key role in Cr(VI) reduction by PDA/ATP-nZVI. PDA enhanced the elimination of Cr(VI) via donation of electrons to Cr(VI) and acceleration of Fe3+ transformation to Fe2+. Furthermore, PDA was able to effectively inhibit the leaching of iron species and generation of ferric hydroxide sludge. Mechanistic study revealed that 72% of Cr(VI) elimination was attributed to reduction/precipitation, while 28% of Cr(VI) elimination was due to the surface adsorption.

Metal(loid)s diffusion pathway triggers distinct microbiota responses in key regions of typical karst non-ferrous smelting assembly.

Non-ferrous metal(loid)s in region with karst characteristic are highly diffusible, especially by runoff or atmospheric deposition. However, microbiota in response to the diffusing metal(loid)s is still to be understood. In this study, we focused on microbiota across metal(loid)s diffusion pathways around a non-ferrous smelting assembly. The microbial distribution and metal(loid)s-microbial interactions were analysed by 16S rRNA amplicon and multivariate statistical analysis. Although runoff and atmospheric deposition showed similar metal(loid)s diffusion contribution, different microbial compositions were revealed. The microbiota along the runoff transect (region3) was similar to those within the atmospheric deposition transect (region4), which significantly differed from those closer to the smelting assembly (region1 and region2; R2 = 0.3866, p = 0.001). Random forest model indicated the negative impacts of bioavailable metal(loid)s on microbial diversity. Proteobacteria was predominant in region1 while Actinobacteriota dominated in the other regions. Twenty abundant genera were identified in metal(loid)s rich area, such as sulfur metabolizer Sulfurifustis and metal resistant Acinetobacter. Interactions between the geochemical parameters and the dominant taxa indicated that the main drivers were Al, Sb, As and their bioavailable fractions and sulfate. This study provides understandings of microbiota patterns towards different metal(loid)s diffusion pathways around non-ferrous smelting assembly with karst characteristic.

Relationships between microbial activity, enzyme activities and metal(loid) form in NiCu tailings area.

Here we combined microcalorimetry, enzyme activity measurements, and characterization of metal form in order to evaluate the effect of metal(loid)s on the activity of microbial community inhabiting tailings area with high toxic metal(loid)s concentration. Chromium (Cr), nickel (Ni), copper (Cu) and manganese (Mn) were the main pollutants. The exchangeable fractions (bioavailability) of Cu, Ni and Mn were higher in the tailings sample (Site Z), indicating a higher environmental risk. The total heat Qtotal (17,726.87 J/g), peak power Ppeak (541.42 µW/g) and growth rate constant k (0.11 h-1) of Site Z were higher than that of the polluted soil around tailings (Site Y). Such observation may be explained by physiological changes within the microbial community in response to high levels of heavy metal stress, thereby increasing respiration and improving microbial activity. In contrast, enzyme activities and enzyme activities index (GmeA) of Site Z were lower than the Site Y, which is strongly influenced by changes on physical-chemical properties (TN and TOC) and the presence of Cr, Mn, and Ni. Correlation coefficient and principal component analysis (PCA) indicate that GmeA is significantly correlated (p < 0.05 or p < 0.01) with environmental factors (EC, TOC and TN), Mn and Ni concentration, Ni bioavailability, and peak time (Tpeak). Therefore, GmeA represents a potential biological indicator for reporting the pollution degree in tailings area. Our results provide a theoretical basis for the prevention and control of pollution in non-ferrous metal(loid) tailings area.

Microbial community profiles in soils adjacent to mining and smelting areas: Contrasting potentially toxic metals and co-occurrence patterns.

Mining and smelting activities have introduced severe potentially toxic metals (PTMs) contamination into surrounding soil settings. Influences of PTMs on microbial diversity have been widely studied. However, variations of microbial communities, network structures and community functions in different levels of PTMs contaminated soils adjacent to mining and smelting aera are still poorly investigated. In this study, microbial communities of soils around different levels of PTMs contamination were comprehensively studied by 16S rRNA gene amplicons high-throughput sequencing. Microbial interactions and module functions were also exploited to ascertain the discrepancies of PTMs concentration levels on microbial ecological functions. Results indicated that the microbial community composition was significantly distinct attributed to the phylum Protebacteria (p = 0.002) dominating in soil with high level PTMs contents but Actinobacteria (p = 0.002) in low level of PTMs-contaminated soil. Microbial α diversity was not significantly influenced by different levels of PTMs contaminations. Microorganisms proactively responded to PTMs content levels by means of strengthening network complexities and modularities among microbe-microbe interactions. The functions of main network modules were predicted associating membrane transport, amino acid metabolism, energy metabolism and carbohydrate metabolism. The PTMs detoxification and anti-oxidation were significantly strengthened at the high level of PTMs contamination. The present study demonstrated that modification of microbial community by the adaptive adjustment of microbial compositions and strengthening their network complexity and modularity.

Toxic response of the freshwater green algae Chlorella pyrenoidosa to combined effect of flotation reagent butyl xanthate and nickel.

Butyl Xanthate (BX) is a typical flotation reagent used to extract non-ferrous nickel ores, discharged into the surrounding environment of mining areas in large quantities. However, few studies have focused on the toxicity of combined pollution of BX and nickel (Ni) on aquatic plants, especially phytoplankton, the main producer of aquatic ecosystems. The toxicity and potential mechanism of single and combined pollution of BX and Ni at different concentrations (0-20 mg L-1) on typical freshwater algae (Chlorella pyrenoidosa) were studied. BX slightly stimulated the growth of C. pyrenoidosa on the first day, but Ni and Ni/BX mixture significantly inhibited it during incubation. Results showed that the inhibition rate (I) of the pollutants on the growth of C. pyrenoidosa followed the order: Ni/BX mixture > Ni > BX. The 96-h 20% effective inhibitory concentrations (96h-EC20) of Ni and BX on C. pyrenoidosa growth were 3.86 mg L-1 and 19.25 mg L-1, respectively, indicating C. pyrenoidosa was sensitive to pollutants. The content of total soluble protein (TSP) and chlorophyll a (Chl-a) changed significantly, which may be caused by the damage of pollutants to cell structures (cell membranes and chloroplasts). In addition, the I of pollutants on C. pyrenoidosa growth was related to dose, superoxide dismutase (SOD), catalase (CAT) and malondialdehyde (MDA). The increasement of reactive oxygen species (ROS), antioxidant enzymes (SOD and CAT), and MDA content, suggested C. pyrenoidosa suffered from oxidative stress, leading to lipid oxidation. These results will help to understand the toxicity mechanism of pollutants in typical mining areas and assess the environmental risks of pollutants to primary producers in aquatic ecosystems.

Metagenomic exploration of multi-resistance genes linked to microbial attributes in active nonferrous metal(loid) tailings.

Mine tailings sites are considered as a continuous source of discharged metal(loid)s and residual organic flotation reagents. They are extremely toxic environments representing unique ecological niches for microbial communities. Mine tailings as a source of multi-resistance genes have been poorly investigated. Metagenomic analysis for four active nonferrous metal(loid) tailings sites with different environmental parameters was conducted. The abundance of Thiobacillus, able to tolerate acidity and showing iron- and sulfur/sulfide oxidation capacities, was significantly different (p < 0.05) between acid and neutral tailings sites. Correlation analyses showed that Zn, Pb, TP, Cd, and Cu were the main drivers influencing the bacterial compositions. Multi-metal resistance genes (MRGs) and antibiotic resistance genes (ARGs), such as baca and copA, were found to be co-selected by high concentrations of metal(loid)s tailings. The main contributors to different distributions of MRGs were Thiobacillus and Nocardioides genus, while genera with low abundance (<0.1%) were the main contributors for ARGs. Functional metabolic pathways related to Fe-S metabolism, polycyclic aromatic hydrocarbons (PAHs) degradation and acid stress were largely from Altererythrobacter, Lysobacter, and Thiobacillus, respectively. Such information provides new insights on active tailings with highly toxic contaminants. Short-term metal(loid) exposure of microorganism in active nonferrous metal(loid) tailings contribute to the co-occurrence of ARGs and MRGs, and aggravation of tailings acidification. Our results recommend that the management of microorganisms involved in acid tolerance and metal/antibiotic resistance is of key importance for in-suit treatment of the continuous discharge of tailings with multiple metal(loid) contaminants into impoundments.

Combined effects of antimony and sodium diethyldithiocarbamate on soil microbial activity and speciation change of heavy metals. Implications for contaminated lands hazardous material pollution in nonferrous metal mining areas.

The combined effects of antimony (Sb) and sodium diethyldithiocarbamate (DDTC), a common organic flotation reagent, on soil microbial activity and speciation changes of heavy metals were investigated for the first time. The results showed that the exchangeable fraction of Sb was transformed to a stable residual fraction during the incubation period, and the addition of DDTC promoted the transformation compared with single Sb pollution, probably because DDTC can react with heavy metals to form a complex. In addition, the presence of DDTC and Sb inhibited the soil microbial activity to varying degrees. The growth rate constant k of different interaction systems was in the following order on the 28th day: control group ≥ single DDTC pollution > combined pollution > single Sb pollution. A correlation analysis showed that the concentration of exchangeable Sb was the primary factor that affected the toxic reaction under combined pollution conditions, and it significantly affected the characteristics of the soil microorganisms. All the observations provide useful information for a better understanding of the toxic effects and potential risks of combined Sb and DDTC pollution in antimony mining areas.

China's most typical nonferrous organic-metal facilities own specific microbial communities.

The diversity and function of microorganisms have yet to be explored at non-ferrous metal mining facilities (NMMFs), which are the world's largest and potentially most toxic sources of co-existing metal(loid)s and flotation reagents (FRs). The diversity and inferred functions of different bacterial communities inhabiting two types of sites (active and abandoned) in Guangxi province (China) were investigated for the first time. Here we show that the structure and diversity of bacteria correlated with the types of mine sites, metal(loid)s, and FRs concentrations; and best correlated with the combination of pH, Cu, Pb, and Mn. Combined microbial coenobium may play a pivotal role in NMMFs microbial life. Arenimonas, specific in active mine sites and an acidophilic bacterium, carries functions able to cope with the extreme conditions, whereas Latescibacteria specific in abandoned sites can degrade organics. Such a bacterial consortium provides new insights to develop cost-effective remediation strategies of co-contaminated sites that currently remain intractable for bioremediation.

Application of phosphate solubilizing bacteria in immobilization of Pb and Cd in soil.

In the present study, heavy metal (HM)-tolerant phosphate solubilizing bacteria (PSB) were isolated and their performance during the remediation of Pb and Cd in contaminated soil was studied. A total of 16 bacterial strains and one consortium were isolated, and the consortium had the highest phosphate solubilizing ability and HM tolerance. Great variations between the Fourier transform infrared (FTIR) spectra of consortium cells before and after adsorption of Pb2+ and Cd2+ revealed that amide I/amide II bonds and carboxyl on the cell surface were involved in binding of metal ions. High-throughput sequencing technique revealed that the consortium was composed of Enterobacter spp., Bacillus spp., and Lactococcus spp. The consortium was added into contaminated soil, and its potential ability in dissolution of phosphate from Ca3(PO4)2 and subsequent immobilization of HMs was tested. Results showed that when Ca3(PO4)2 was applied at 10.60 mg/g soil, PSB addition significantly increased soil available phosphate content from 12.28 to 17.30 mg/kg, thereby enhancing the immobilization rate of Pb and Cd from 69.95 to 80.76% and from 28.38 to 30.81%, respectively. Microcalorimetric analysis revealed that PSB addition significantly improved soil microbial activity, which was possibly related with the decreased HMs availability and the nutrient effect of the solubilized phosphate. The present study can provide a cost-effective and environmental-friendly strategy to remediate multiple HM-contaminated soils.