Efficient Recovery of Rare Earth Elements from Acidic Wastewater by a Green ß-CDs-Functionalized Nanosponge.

The recovery of rare earth elements (REEs) from acidic wastewater is crucial to sustainable development, industrial processes, and human health. In this research, ß-cyclodextrin-based nanosponges (ß-CD/PVA-SA NSs) have been proposed as potential adsorbents for europium (Eu), dysprosium (Dy), and gadolinium (Gd) recovery. The nanosponges are synthesized by cross-linking ß-cyclodextrin (ß-CD) functionalized polyvinyl alcohol (PVA) and sodium alginate (SA). Experimental results indicate that ß-CD/PVA-SA NSs exhibit favorable selectivity for Eu, Dy, and Gd, with the maximum adsorption capacity of 222, 217, and 204 mg/g, respectively, in addition to stability and cyclicity. ß-CD/PVA-SA NSs maintain selective adsorption effects towards RE ions that are present in acidic mine drainage (AMD), thereby highlighting their potential for practical applications. Furthermore, density functional theory (DFT) simulations have unveiled the fundamental interactions between the functional groups anchored in ß-CD/PVA-SA NSs and the REEs, providing vital insights into their adsorption mechanism. Hence, the utilization of ß-CD/PVA-SA NSs has the potential to advance initiatives in remediating acidic water pollution and facilitating the sustainable recycling of RE resources.

Acidibrevibacterium fodinaquatile gen. nov., sp. nov., isolated from acidic mine drainage.

A heterotrophic and acidophilic bacterial strain, G45-3T, was isolated from acidic mine drainage sampled in Fujian Province, PR China. Cells of strain G45-3T were Gram-stain-negative, non-spore-forming, non-motile and rod-shaped. Catalase and oxidase activities were positive. Strain G45-3T grew aerobically at 20-45 °C (optimum, 37 °C) and at pH 2.5-5.0 (optimum, pH 4.0). Photosynthetic pigments were not produced. Analysis of 16S rRNA gene sequences showed that strain G45-3T was phylogenetically related to different members of the family Acetobacteraceae, and the sequence identities to Acidisphaera rubrifaciens JCM 10600T, Rhodovastum atsumiense G2-11T and Rhodopila globiformis ATCC 35887T were 95.9 , 95.3 and 95.3 %, respectively. Strain G45-3T contained ubiquinone-10 as its respiratory quinone. The major polar lipids were determined to be diphosphatidylglycerol, phosphatidylglycerol, phosphatidylethanolamine, phosphatidylcholine, an unidentified aminophospholipid and an unidentified aminolipid. The predominant fatty acids were cyclo-C19 : 0ω8c, C18 : 1ω7c, C16 : 0 and C18 : 0. The genome of G45-3T consists of one chromosome (3 907 406 bp) and three plasmids (68 344, 45 771 and 16 090 bp), with an average G+C content of 65.9 mol%. Based on the results of phenotypic and genomic analyses, it is concluded that strain G45-3T represents a novel species of a new genus, for which the name Acidibrevibacterium fodinaquatile gen. nov., sp. nov. is proposed. A. fodinaquatile is nominated as type species and its type strain is G45-3T (=CGMCC 1.16069T=KCTC 62275T).

Streptomyces fodineus sp. nov., an actinobacterium with antifungal activity isolated from mine area soil.

A novel actinobacterial strain producing an antifungal substance was isolated from a sample of acidic mine area soil, and its taxonomic position was evaluated. The novel strain, designated TW1S1T, formed white-grey aerial mycelium and yellow substrate mycelium on oatmeal agar. Growth occurred at 10-45 °C (optimum, 30 °C), pH 4-9 (pH 6-7) and in the presence of up to 8 % (w/v) NaCl. Melanin was produced on peptone-yeast extract-iron agar. Phylogenetic analysis based on its 16S rRNA gene sequence indicated that the novel strain should be assigned to the genus Streptomyces, and the closest species was Streptomyces puniciscabiei S77T with 99.1 % sequence similarity, which was followed by Streptomyces durhamensis NRRL B-3309T (99.0 %), Streptomyces filipinensis NBRC 12860T (98.9 %) and Streptomyces yaanensis Z4T (98.7 %). The chemotaxonomic properties were consistent with those of Streptomyces. ll-Diaminopimelic acid was the diagnostic diamino acid, and alanine, glutamic acid and glycine were present in the peptidoglycan. The cell-wall hydrolysate also contained galactose, glucose, mannose and ribose. The predominant isoprenoid quinones were MK-9(H4) and MK-9(H6), the major polar lipids were phosphatidylglycerol and an unidentified phospholipid, and the main fatty acids were iso-C16 : 0 and anteiso-C15 : 0. However, strain TW1S1T could be distinguished from its neighbouring species by its phenotypic properties. In addition, the genome-based comparison with the closest species indicated that strain TW1S1T should be recognized as a separate species. The phylogenetic, phenotypic and chemotaxonomic as well as genomic evidence supported that TW1S1T represents a novel species of Streptomyces, for which the name Streptomycesfodineus sp. nov. is proposed (type strain, TW1S1T = KCTC 49013T = JCM 32404T).

Experimental research on compressive strength deterioration of coal seam floor sandstone under the action of acidic mine drainage.

In sulphur-coal symbiotic coal seams, after the mining of sulphide iron ore, when the coal resources are mined, the mine water accumulated in the roadway mining area will have a certain impact on the stability of the surrounding rock of the coal seam roadway. Taking the floor sandstone of sulfur coal symbiotic coal seam as the research object, the roof fissure water with pH values of 7.48, 4.81 and 2.62 was used as the experimental solution. 10 experimental schemes were designed to measure the compressive strength of the samples under the action of AMD, and the hydrochemical analysis of AMD was conducted. The pore structures of the samples before and after the action of AMD were analyzed. Based on the hydrochemistry and pore structure, the deterioration mechanism of compressive strength of the coal seam floor sandstone under the action of AMD was explained. The results indicated that the compressive strength of the samples decreased with the increasing action time of AMD. The compressive strength decreased with the increment of the porosity. The concentration of H+ ion in AMD was relatively small. Na2O in albite dissolved and reacted with water, leading to an increase in the concentration of Na+ ion. Soluble substances such as MgCl2 and CaSO4 in the pore structure dissolved, leading to an increase in the concentration of Ca2+ and Mg2+ ions. The dissolution of soluble substances and the physical-chemical reactions between solutions and minerals were the essential causes of the continuous deterioration of the compressive strength of the coal seam floor sandstone. The results of this study can provide a theoretical basis for the deterioration of the mechanical properties of the peripheral rock in the roadway of the sulphur coal seam, and can also provide a certain engineering reference for the sulphur coal seam roadway.

Metal recovery from spent lithium-ion batteries via two-step bioleaching using adapted chemolithotrophs from an acidic mine pit lake.

The demand for lithium-ion batteries (LIBs) has dramatically increased in recent years due to their application in various electronic devices and electric vehicles (EVs). Great amount of LIB waste is generated, most of which ends up in landfills. LIB wastes contain substantial amounts of critical metals (such as Li, Co, Ni, Mn, and Cu) and can therefore serve as valuable secondary sources of these metals. Metal recovery from the black mass (shredded spent LIBs) can be achieved via bioleaching, a microbiology-based technology that is considered to be environmentally friendly, due to its lower costs and energy consumption compared to conventional pyrometallurgy or hydrometallurgy. However, the growth and metabolism of bioleaching microorganisms can be inhibited by dissolved metals. In this study, the indigenous acidophilic chemolithotrophs in a sediment from a highly acidic and metal-contaminated mine pit lake were enriched in a selective medium containing iron, sulfur, or both electron donors. The enriched culture with the highest growth and oxidation rate and the lowest microbial diversity (dominated by Acidithiobacillus and Alicyclobacillus spp. utilizing both electron donors) was then gradually adapted to increasing concentrations of Li+, Co2+, Ni2+, Mn2+, and Cu2+. Finally, up to 100% recovery rates of Li, Co, Ni, Mn, and Al were achieved via two-step bioleaching using the adapted culture, resulting in more effective metal extraction compared to bioleaching with a non-adapted culture and abiotic control.

Mineralogy affects prokaryotic community composition in an acidic metal mine.

The microbial ecology of acidic mine and sulfide cave ecosystems is well characterised with respect to aquatic communities, typically revealing low taxonomic complexity and dominance by a relatively limited number of cosmopolitan acidophilic bacterial and archaeal taxa. Whilst pH, temperature, and geochemistry are recognised drivers of diversity in these ecosystems, the specific question of a possible influence of substratum mineralogy on microbial community composition remains unanswered. Here we address this void, using 81 subterranean mineral samples from a low temperature abandoned, acidic, sulfide ore mine system at Mynydd Parys (Parys Mountain in English), Wales, UK. Four primary and 15 secondary minerals were identified via x-ray diffraction, each sample containing a maximum of five and an average of two minerals. The mineralogy of primary (e.g. pyrite and quartz) and secondary (e.g. melanterite and pisanite) minerals was significantly correlated with prokaryotic community structure at multiple taxonomic levels, implying that the mineralosphere effect reported in less extreme terrestrial environments is also implicated in driving prokaryotic community composition in extremely acidic, base metal-bearing sulfide mineralisation at Mynydd Parys. Twenty phyla were identified, nine of which were abundant (mean relative abundance >1%). While taxa characteristic of acidic mines were detected, for example Leptospirillum (phylum Nitrospirae), Acidithiobacillus (phylum Proteobacteria), Sulfobacillus (phylum Firmicutes) and Ferroplasma (phylum Euryarchaeota), their abundance in individual samples was highly variable. Indeed, in the majority of the 81 samples investigated the abundance of these and other typical acidic mine taxa was low, with 25% of samples devoid of sequences from recognised acidic mine taxa. Most notable amongst the bacterial taxa not previously reported in such environments were the recently cultivated Muribaculaceae family (phylum Bacteroidetes), which often dominated Mynydd Parys samples regardless of their mineralogical content. Our results pose further questions regarding the mechanisms by which taxa not previously reported in such extreme environments appear to survive in Mynydd Parys, opening up research pathways for exploring the biodiversity drivers underlying microbial community composition and function in extremely acidic mine environments.

Genome-resolved metagenomics inferred novel insights into the microbial community, metabolic pathways, and biomining potential of Malanjkhand acidic copper mine tailings.

Mine tailing sites provide profound opportunities to elucidate the microbial mechanisms involved in ecosystem functioning. In the present study, metagenomic analysis of dumping soil and adjacent pond around India's largest copper mine at Malanjkhand has been done. Taxonomic analysis deciphered the abundance of phyla Proteobacteria, Bacteroidetes, Acidobacteria, and Chloroflexi. Genomic signatures of viruses were predicted in the soil metagenome, whereas Archaea and Eukaryotes were noticed in water samples. Mesophilic chemolithotrophs, such as Acidobacteria bacterium, Chloroflexi bacterium, and Verrucomicrobia bacterium, were predominant in soil, whereas, in the water sample, the abundance of Methylobacterium mesophilicum, Pedobacter sp., and Thaumarchaeota archaeon was determined. The functional potential analysis highlighted the abundance of genes related to sulfur, nitrogen, methane, ferrous oxidation, carbon fixation, and carbohydrate metabolisms. The genes for copper, iron, arsenic, mercury, chromium, tellurium, hydrogen peroxide, and selenium resistance were found to be predominant in the metagenomes. Metagenome-assembled genomes (MAGs) were constructed from the sequencing data, indicating novel microbial species genetically related to the phylum predicted through whole genome metagenomics. Phylogenetic analysis, genome annotations, functional potential, and resistome analysis showed the resemblance of assembled novel MAGs with traditional organisms used in bioremediation and biomining applications. Microorganisms harboring adaptive mechanisms, such as detoxification, hydroxyl radical scavenging, and heavy metal resistance, could be the potent benefactions for their utility as bioleaching agents. The genetic information produced in the present investigation provides a foundation for pursuing and understanding the molecular aspects of bioleaching and bioremediation applications.

Immobilization of metal(loid)s from acid mine drainage by biological soil crusts through biomineralization.

Acid mine drainage is harmful to the environment. Bioremediation based on biological soil crusts (BSCs) can be used as a new method to alleviate metal pollution in acid mine drainage. In this study, we found that BSCs can survive in a strongly acidic environment (pH = 3.28) and have a high metal(loid)s accumulation ability. The algae of genera Fragilaria, Klebsormidium, Cymbella, Melosira, Microcystacea, and Planctonema a're the main components of BSCs. These organisms in the BSCs regulated fatty acids and produced acid-resistant enzymes. The bioconcentration factors for As, Cd, Pb, Zn, and Cu were as high as 16,000, 200, 50, 26, and 400, respectively. The concentration of As and Cd in acid mine drainage decreased from 7.1 µg and 350 µg/L to 1.9 µg and 110 µg/L, respectively. In total, 56% of As, 73% of Cd, 88% of Pb, 85% of Zn, and 92% of Cu were present in BSCs as residual or mineral-bound forms. The XRD results (e.g., quarartz and phyllosilicates), SEM results (e.g., phylosilicates and diatom shells) and correlation results show that these metal(loid)s are immobilized by Cymbella (diatoms) during the deposition of silica in the acidic environment. Furthermore, adsorption and co-precipitation are other ways that metal(loid)s could have been bound. These findings provide new insights into the removal of metals (loid) in acidic water.

Strong succession in prokaryotic association networks and community assembly mechanisms in an acid mine drainage-impacted riverine ecosystem.

Acid mine drainage (AMD) serves as an ideal model system for investigating microbial ecology, interaction, and assembly mechanism in natural environments. While previous studies have explored the structure and function of microbial communities in AMD, the succession patterns of microbial association networks and underlying assembly mechanisms during natural attenuation processes remain elusive. Here, we investigated prokaryotic microbial diversity and community assembly along an AMD-impacted river, from the extremely acidic, heavily polluted headwaters to the nearly neutral downstream sites. Microbial diversity was increased along the river, and microbial community composition shifted from acidophile-dominated to freshwater taxa-dominated communities. The complexity and relative modularity of the microbial networks were also increased, indicating greater network stability during succession. Deterministic processes, including abiotic selection of pH and high contents of sulfur and iron, governed community assembly in the headwaters. Although the stochasticity ratio was increased downstream, manganese content, microbial negative cohesion, and relative modularity played important roles in shaping microbial community structure. Overall, this study provides valuable insights into the ecological processes that govern microbial community succession in AMD-impacted riverine ecosystems. These findings have important implications for in-situ remediation of AMD contamination.

Study on the removal of iron (II) and manganese (II) in acidic mine drainage by red mud: Performance and mechanism.

Red mud is an environmental burden during the alumina production process. To mitigate the hazards associated with red mud storage, this study investigated the utilization of alkaline red mud as a treatment agent for acidic mine drainage (AMD) with high concentrations of Fe(II) and Mn(II). This study explored the influence of reaction times, addition amounts of red mud, and pH values on the removal efficiency of Fe (II) and Mn(II) from high-concentration AMD. Various parameters such as suspended solids levels, effluent pH, and zeta potentials were measured to meet discharge standards. The adsorption mechanism of red mud was examined using SEM, XRD, EDX, XPS, and 3D-EEM analysis. Optimal conditions were determined as a reaction time of 2 h, pH value of 5.01 and the addition of 100 g/L red mud, achieving effective removal of Fe(II) (reduced from 1000 to 0.224 mg/L) and Mn (II) (reduced from 20 to 1.03 mg/L). The treated AMD meets discharge standards with reduced suspended matter content of 37.4 mg/L. These findings provided valuable insights for the utilization of red mud waste in engineering applications.

Biochar-templated surface precipitation and inner-sphere complexation effectively removes arsenic from acid mine drainage.

Treatment of aqueous leachate from acid mine tailings with pristine biochar (BC) resulted in the removal of more than 90% of the dissolved arsenic with an attendant rapid and sustained pH buffering from 3 to 4. Pine forest waste BC was transformed to a highly effective adsorbent for arsenic remediation of acid mine drainage (AMD) because the dissolved iron induced "activation" of BC through accumulation of highly reactive ferric hydroxide surface sites. Physicochemical properties of the BC surface, and molecular mechanisms of Fe, S, and As phase transfer, were investigated using a multi-method, micro-scale approach (SEM, XRD, FTIR, XANES, EXAFS, and STXM). Co-located carbon and iron analysis with STXM indicated preferential iron neo-precipitates at carboxylic BC surface sites. Iron and arsenic X-ray spectroscopy showed an initial precipitation of ferrihydrite on BC, with concurrent adsorption/coprecipitation of arsenate. The molecular mechanism of arsenic removal involved bidentate, binuclear inner-sphere complexation of arsenate at the surfaces of pioneering ferric precipitates. Nucleation and crystal growth of ferrihydrite and goethite were observed after 1 h of reaction. The high sulfate activity in AMD promoted schwertmannite precipitation beginning at 6 h of reaction. At reaction times beyond 6 h, goethite and schwertmannite accumulated at the expense of ferrihydrite. Results indicate that the highly functionalized surface of BC acts as a scaffolding for the precipitation and activation of positively charged ferric hydroxy(sulf)oxide surface sites from iron-rich AMD, which then complex oxyanion arsenate, effectively removing it from porewaters. Graphical abstract.

Arsenic in leafy vegetable plants grown on mine water-contaminated soils: Uptake, human health risk and remedial effects of biochar.

Field investigation and microcosm experiment were conducted to examine the uptake of arsenic by vegetable plants grown on the soils contaminated by acidic mine water and evaluate the human health risk from consuming the vegetables. Plant uptake of arsenic was related to the ratio of phosphorus to arsenic in soil solution for the same vegetable species. Bioaccumulation coefficient (BAC) of arsenic was highly variable amongst the different vegetable species with water spinach (white stem) and sweet potato leaf being identified as major vegetable species with high BAC. There was a reasonably good relationship between the gastric phase-bioaccessible arsenic and the gastrointestinal phase-bioaccessible arsenic. Consumption of the vegetables grown in the investigated area poses a significantly potential human health risk with a hazard quotient (HQ) of 2.7. Application of biochar significantly inhibited the uptake of arsenic by the vegetable plant due to protonation of biochar surfaces under acidic conditions, which favoured adsorption of arsenic. The bioaccessibity of arsenic in the edible part of vegetable was also reduced due to biochar application. The HQ of the test vegetable plant (Gynura cusimbua) after soil amendment by biochar was reduced to 2 from 6 for the unamended soil.

From nanofiltration membrane permeances to design projections for the remediation and valorisation of acid mine waters.

Acidic Mine Waters (AMWs) are characterised by high acidity (pH < 3) as H2SO4 and elevated contents of metals (Al, Fe, Cu, Zn), including rare earth elements (REEs). Due to the exhaustion of minable REE containing-minerals, AMWs are increasingly regarded as an alternative source of REEs. Among the different alternatives for the pre-concentration of AMWs required to make the REE extraction possible, nanofiltration (NF) membranes emerge as a promising technology because they not only successfully reject multivalent ions (metals), allowing its concentration in the retentate stream, but also permit the transport of monovalent ones, such as H+ and HSO4-, allowing the recovery of sulphuric acid in the permeate. Despite this potential of NF, there is still a lack of modelling tools for predicting the performance of NF membranes because of its dependence on solution composition, membrane properties and interaction between both. In this study, a prediction tool based on the Solution-Electro-Diffusion model (including the effect of solution composition) was developed and experimentally validated for the application of two polyamide-based NF membranes (NF270 and Desal DL) for the recovery of REEs and H2SO4 from three different synthetic solutions mimicking AMWs (pH 1.0, 60 mg/L REEs and, 25-600 mg/L Al, Cu, Ca and Zn) differing in their Fe concentration (0-2125 mg/L). Metals were effectively rejected (>98%), whereas H2SO4 was transported across the membrane (H+ rejections <30%). The mathematical model was able to predict the performance of both membranes as well as the potential scaling events associated with Fe and Al hydroxides and hydroxy-sulphates.

Performance of organic substrate amended constructed wetland treating acid mine drainage (AMD) of North-Eastern India.

A horizontal subsurface flow constructed wetland (HSSF-CW) was evaluated for the remediation of synthetic acid mine drainage (AMD) using an organic-rich substrate (cow manure and bamboo chips) planted with common cattail. The synthetic AMD simulated the source AMD generated in North Eastern Coalfield of Assam, India. The synthetic AMD was highly acidic (pH < 2.5) and contained heavy metals (Fe, Mn, Al, Co, Ni and Cr) and sulfate (900-1500 mg L-1). HSSF-CW was operated under varying levels of AMD concentration (10, 25, 40, 70 and 100%) during the acclimatization and thereafter continued to operate at full strength AMD at hydraulic retention time of 7 days. After the 6-month experiment, the results suggested the potential application of HSSF-CW due to its ability to raise the pH from 2.1 to 6.4 with the simultaneous removal of metals (except for manganese) and microbial sulfate reduction (44-75%). Metal removal efficiency in the order: chromium (99.7%) > nickel (97.8%) > cobalt (93.7%) > iron (91.6%) > aluminium (59.7%). Toxicity Characteristic Leaching Procedure test (TCLP) study suggested very negligible leachability of chromium for safe disposal. Common cattails exhibited poor bioaccumulation and translocation for all heavy metals except for manganese and cobalt.

Zeolitic tuffs for acid mine drainage (AMD) treatment in Ecuador: breakthrough curves for Mn2+, Cd2+, Cr3+, Zn2+, and Al3.

Zeolitic tuff constitutes a technical and economical feasible alternative to manage acidic waters in initial phases of generation. A study of cation exchange with two zeolitic tuffs from Ecuador and one from Cuba has been conducted using breakthrough curve methodology. Cations Mn2+, Cd2+, Cr3+, Zn2+, and Al3+ have been chosen owing to their presence in underground water in exploration activities (decline development) in Fruta del Norte (Ecuador). Zeolites characterized by X-ray diffraction and thermal stability after heating overnight as heulandites show a similar exchange behavior for the five cations studied. The clinoptilolite sample Tasajeras shows a relevant cation exchange performance expressed in the important increment of spatial time to reach the breakthrough point in comparison with heulandite samples. The maximum length of unused beds was found for Cr3+ and Zn2+ cations showing, therefore, a lower adsorption performance in relation with Mn2+ and Cd2+. A final disposal method of metal-loaded zeolites with cement is proposed.

Multibiomarker toxicity characterization of uranium mine drainages to the fish Carassius auratus.

The release of acidic effluents, naturally enriched in metals and radionuclides, is the main legacy of uranium mines. Generally, metals dissolved by these acidic effluents can cause significant alterations in exposed organisms, with distinct toxicological outcomes. In this study, 72 individuals of the freshwater fish species Carassius auratus were exposed in situ for different periods (8, 16, 24, and 48 h) to water from a pond (treatment pond (TP)) with a chemically treated effluent and a reference pond (PRP), in the vicinity of the Cunha Baixa uranium mine (Portugal). Comparing the water of the two ponds, the PRP pond was characterized by higher pH and oxygen values and lower conductivity and hardness values. Regarding total metal concentrations, among others, magnesium (56,000 µg/L), sodium (17,400 µg/L), zinc (86 µg/L), manganese (6340 µg/L), and uranium (1380 µg/L) concentrations in the TP pond were above the values obtained for the PRP pond. The values of manganese and uranium exceeded the values of quality criteria established for surface waters for cyprinids and for irrigation purposes. After exposure to pond water, significant differences were recorded for several biomarkers: (i) between ponds for acetylcholinesterase (AChE) with higher activities for animals from the PRP and glutathione-S-transferase (GST) activities that were particularly enhanced in animals from the TP pond; (ii) between ponds and exposure periods for lactate dehydrogenase (LDH) activity, since organisms from PRP pond presented always higher values than those from the TP pond, and among these, organisms exposed for the longer period presented a further depression in LDH activity; and (iii) between exposure periods for erythrocyte micronucleus. GSTs and LDH were the most sensitive biomarkers within the timeframe of the in situ assay performed. Despite the alleged efficacy of the chemical treatment (evidenced by a significantly lower pH), some metals persisted in the treated effluent (TP pond), potentially contributing to the induction of oxidative stress or increased conjugation metabolic activity in fish.