Rare Earth Element Adsorption to Clay Minerals: Mechanistic Insights and Implications for Recovery from Secondary Sources.

The energy transition will have significant mineral demands and there is growing interest in recovering critical metals, including rare earth elements (REE), from secondary sources in aqueous and sedimentary environments. However, the role of clays in REE transport and deposition in these settings remains understudied. This work investigated REE adsorption to the clay minerals illite and kaolinite through pH adsorption experiments and extended X-ray absorption fine structure (EXAFS). Clay type, pH, and ionic strength (IS) affected adsorption, with decreased adsorption under acidic pH and elevated IS. Illite had a higher adsorption capacity than kaolinite; however, >95% adsorption was achieved at pH ∼7.5 regardless of IS or clay. These results were used to develop a surface complexation model with the derived binding constants used to predict REE speciation in the presence of competing sorbents. This demonstrated that clays become increasingly important as pH increases, and EXAFS modeling showed that REE can exist as both inner- and outer-sphere complexes. Together, this indicated that clays can be an important control on the transport and enrichment of REE in sedimentary systems. These findings can be applied to identify settings to target for resource extraction or to predict REE transport and fate as a contaminant.

Synergistic mitigation of atrazine-induced oxidative stress on soybeans in black soil using biochar and Paenarthrobacter sp. AT5.

Atrazine, a widely used herbicide in modern agriculture, can lead to soil contamination and adverse effects on specific crops. To address this, we investigated the efficacy of biochar loaded with Paenarthrobacter sp. AT5 (an atrazine-degrading bacterial strain) in mitigating atrazine's impact on soybeans in black soil. Bacterially loaded biochar (BBC) significantly enhanced atrazine removal rates in both unplanted and planted soil systems. Moreover, BBC application improved soybean biomass, photosynthetic pigments, and antioxidant systems while mitigating alterations in metabolite pathways induced by atrazine exposure. These findings demonstrate the effectiveness of BBC in reducing atrazine-induced oxidative stress on soybeans in black soil, highlighting its potential for sustainable agriculture.

Selective Extraction of Critical Metals from Spent Lithium-Ion Batteries.

Selective and highly efficient extraction technologies for the recovery of critical metals including lithium, nickel, cobalt, and manganese from spent lithium-ion battery (LIB) cathode materials are essential in driving circularity. The tailored deep eutectic solvent (DES) choline chloride-formic acid (ChCl-FA) demonstrated a high selectivity and efficiency in extracting critical metals from mixed cathode materials (LiFePO4:Li(NiCoMn)1/3O2 mass ratio of 1:1) under mild conditions (80 °C, 120 min) with a solid-liquid mass ratio of 1:200. The leaching performance of critical metals could be further enhanced by mechanochemical processing because of particle size reduction, grain refinement, and internal energy storage. Furthermore, mechanochemical reactions effectively inhibited undesirable leaching of nontarget elements (iron and phosphorus), thus promoting the selectivity and leaching efficiency of critical metals. This was achieved through the preoxidation of Fe and the enhanced stability of iron phosphate framework, which significantly increased the separation factor of critical metals to nontarget elements from 56.9 to 1475. The proposed combination of ChCl-FA extraction and the mechanochemical reaction can achieve a highly selective extraction of critical metals from multisource spent LIBs under mild conditions.

Exogenous Electroactive Microbes Regulate Soil Geochemical Properties and Microbial Communities by Enhancing the Reduction and Transformation of Fe(III) Minerals.

Electroactive microbes can conduct extracellular electron transfer and have the potential to be applied as a bioresource to regulate soil geochemical properties and microbial communities. In this study, we incubated Fe-limited and Fe-enriched farmland soil together with electroactive microbes for 30 days; both soils were incubated with electroactive microbes and a common iron mineral, ferrihydrite. Our results indicated that the exogenous electroactive microbes decreased soil pH, total organic carbon (TOC), and total nitrogen (TN) but increased soil conductivity and promoted Fe(III) reduction. The addition of electroactive microbes also changed the soil microbial community from Firmicutes-dominated to Proteobacteria-dominated. Moreover, the total number of detected microbial species in the soil decreased from over 700 to less than 500. Importantly, the coexistence of N-transforming bacteria, Fe(III)-reducing bacteria and methanogens was also observed with the addition of electroactive microbes in Fe-rich soil, indicating the accelerated interspecies electron transfer of functional microflora.

Arbuscular Mycorrhizal Fungi Drive Organo-Mineral Association in Iron Ore Tailings: Unravelling Microstructure at the Submicron Scale by Synchrotron-Based FTIR and STXM-NEXAFS.

Arbuscular mycorrhizal (AM) fungi play an important role in organic matter (OM) stabilization in Fe ore tailings for eco-engineered soil formation. However, little has been understood about the AM fungi-derived organic signature and organo-mineral interactions in situ at the submicron scale. In this study, a compartmentalized cultivation system was used to investigate the role of AM fungi in OM formation and stabilization in tailings. Particularly, microspectroscopic analyses including synchrotron-based transmission Fourier transform infrared (FTIR) and scanning transmission X-ray microspectroscopy combined with near-edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS) were employed to characterize the chemical signatures at the AM fungal-mineral and mineral-OM interfaces at the submicron scale. The results indicated that AM fungal mycelia developed well in the tailings and entangled mineral particles for aggregation. AM fungal colonization enhanced N-rich OM stabilization through organo-mineral association. Bulk spectroscopic analysis together with FTIR mapping revealed that fungi-derived lipids, proteins, and carbohydrates were associated with Fe/Si minerals. Furthermore, STXM-NEXAFS analysis revealed that AM fungi-derived aromatic, aliphatic, and carboxylic/amide compounds were heterogeneously distributed and trapped by Fe(II)/Fe(III)-bearing minerals originating from biotite-like minerals weathering. These findings imply that AM fungi can stimulate mineral weathering and provide organic substances to associate with minerals, contributing to OM stabilization and aggregate formation as key processes for eco-engineered soil formation in tailings.

Persisting Effects in Daphnia magna Following an Acute Exposure to Flowback and Produced Waters from the Montney Formation.

Hydraulic fracturing extracts oil and gas through the injection of water and proppants into subterranean formations. These injected fluids mix with the host rock formation and return to the surface as a complex wastewater containing salts, metals, and organic compounds, termed flowback and produced water (FPW). Previous research indicates that FPW is toxic to Daphnia magna (D. magna), impairing reproduction, molting, and maturation time; however, recovery from FPW has not been extensively studied. Species unable to recover have drastic impacts on populations on the ecological scale; thus, this study sought to understand if recovery from an acute 48 h FPW exposure was possible in the freshwater invertebrate, D. magna by using a combination of physiological and molecular analyses. FPW (0.75%) reduced reproduction by 30% and survivorship to 32% compared to controls. System-level quantitative proteomic analyses demonstrate extensive perturbation of metabolism and protein transport in both 0.25 and 0.75% FPW treatments after a 48 h FPW exposure. Collectively, our data indicate that D. magna are unable to recover from acute 48 h exposures to ≥0.25% FPW, as evidence of toxicity persists for at least 19 days post-exposure. This study highlights the importance of considering persisting effects following FPW remediation when modeling potential spill scenarios.

Environmental impact of metal halide perovskite solar cells and potential mitigation strategies: A critical review.

Metal halide perovskite solar cells (PSCs) have gained extensive attention in the field of solar photovoltaic technology over the past few years. Despite being a remarkable alternative to fossil fuels, solar cells may have detrimental effects on the environment and human health owing to the use of toxic materials during manufacturing. Although modern metal-halide-based PSCs are stable and have encapsulation to prevent the release of potentially toxic materials into the environment, their destruction due to strong winds, hail, snow, landslides, fires, or waste disposal can result in the exposure of these materials to the environment. This may lead to the contamination of soil and groundwater, and uptake of potentially toxic elements by plants, subsequently affecting humans and other living organisms via food chain contamination. Despite worldwide concern, the environmental and ecotoxicological impacts of metal-halide-based PSCs have not been comprehensively surveyed. This review summarizes and critically evaluates the current status of metal-halide-based PSC production and its impact on environmental sustainability, food security, and human health. Furthermore, safe handling and disposal methods for the waste generated from metal-halide-based PSCs are proposed, with a focus on recycling and reuse. Although some studies have suggested that the amount of lead released from metal halide PSCs is far below the maximum permissible levels in most soils, a clear conclusion cannot be reached until real contamination scenarios are assessed under field conditions. Precautions must be taken to minimize environmental contamination throughout the lifecycle of PSCs until nontoxic and similarly performing alternative solar photovoltaic products are developed.

Water footprint of shale gas development in China in the carbon neutral era.

The production of shale gas in China has repercussions for the global energy landscape and carbon neutrality. However, limited and threatened water resources may hinder the expansion of shale-derived natural gas, one of China's most promising development prospects. Coupling historical trends with policy guidance, we project that baseline water stress will intensify in two-thirds of China's provinces in the next decade. By 2035, annual water use for shale gas hydraulic fracturing activities is likely to increase to 16-35 million m3, with 13.8-23.7 million m3 of wastewater produced annually to extract 38-48 billion m3 of gas from ∼4800 shale gas wells. Analysis suggests that this projection is based on previously underestimated geological constraints (e.g., deep continental facies) in shale gas development in China. Nevertheless, forecasts suggest that the water footprint of shale development will become impossible to ignore, particularly in drought-stricken areas, indicating the potential risk of competition for water among shale development, domestic use, food production, and ecological protection. Meanwhile, the annual wastewater management market will increase to $0.2 billion by 2035. Our study suggests a critical need to direct attention to the (shale) energy-water nexus and develop multi-pronged policies to facilitate China's transition to carbon neutrality.

Complex impacts of hydraulic fracturing return fluids on soil microbial community respiration, structure and functional potentials.

The consequences of soils exposed to hydraulic fracturing (HF) return fluid, often collectively termed flowback and produced water (FPW), are poorly understood, even though soils are a common receptor of FPW spills. Here, we investigate the impacts on soil microbiota exposed to FPW collected from the Montney Formation of western Canada. We measured soil respiration, microbial community structure and functional potentials under FPW exposure across a range of concentrations, exposure time and soil types (luvisol and chernozem). We find that soil type governs microbial community response upon FPW exposure. Within each soil, FPW exposure led to reduced biotic soil respiration, and shifted microbial community structure and functional potentials. We detect substantially higher species richness and more unique functional genes in FPW-exposed soils than in FPW-unexposed soils, with metagenome-assembled genomes (e.g. Marinobacter persicus) from luvisol soil exposed to concentrated FPW being most similar to genomes from HF/FPW sites. Our data demonstrate the complex impacts of microbial communities following FPW exposure and highlight the site-specific effects in evaluation of spills and agricultural reuse of FPW on the normal soil functions.

Comparison of the Hydraulic Fracturing Water Cycle in China and North America: A Critical Review.

There is considerable debate about the sustainability of the hydraulic fracturing (HF) water cycle in North America. Recently, this debate has expanded to China, where HF activities continue to grow. Here, we provide a critical review of the HF water cycle in China, including water withdrawal practices and flowback and produced water (FPW) management and their environmental impacts, with a comprehensive comparison to the U.S. and Canada (North America). Water stress in arid regions, as well as water management challenges, FPW contamination of aquatic and soil systems, and induced seismicity are all impacts of the HF water cycle in China, the U.S., and Canada. In light of experience gained in North America, standardized practices for analyzing and reporting FPW chemistry and microbiology in China are needed to inform its efficient and safe treatment, discharge and reuse, and identification of potential contaminants. Additionally, conducting ecotoxicological studies is an essential next step to fully reveal the impacts of accidental FPW releases into aquatic and soil ecosystems in China. From a policy perspective, the development of China's unconventional resources lags behind North America's in terms of overall regulation, especially with regard to water withdrawal, FPW management, and routine monitoring. Our study suggests that common environmental risks exist within the world's two largest HF regions, and practices used in North America may help prevent or mitigate adverse effects in China.

Using CO2 as an Oxidant in the Catalytic Pyrolysis of Peat Moss from the North Polar Region.

As global warming and climate change become perceived as significant, the release of greenhouse gases (GHGs) stored in the earth's polar regions is considered a matter of concern. Here, we focused on exploiting GHGs to address potential global warming challenges in the north polar regions. In particular, we used CO2 as a soft oxidant to recover energy as syngas (CO and H2) and to produce biochars from pyrolysis of peat moss. CO2 expedited homogeneous reaction with volatile matters from peat moss pyrolysis, and the mechanistic CO2 role resulted in the conversion of CO2 and peat moss to CO at ≥530 °C. Steel slag waste was then used as an ex situ catalyst to increase reaction kinetics, addressing the issue of the role of CO2 being limited to ≥530 °C, with the result where substantial H2 and CO formation was achieved at a milder temperature. The porosity of biochars, a solid peat moss pyrolysis product, was modified in the presence of CO2, with a significant improvement in CO2 adsorption capacity compared to those achieved by N2 pyrolysis. Therefore, CO2 has the potential to serve as an initial feedstock in sustainable biomass-to-energy applications and biochar production, mitigating atmospheric carbon concentrations.

Exposure to Hydraulic Fracturing Flowback Water Impairs Mahi-Mahi (Coryphaena hippurus) Cardiomyocyte Contractile Function and Swimming Performance.

Publicly available toxicological studies on wastewaters associated with unconventional oil and gas (UOG) activities in offshore regions are nonexistent. The current study investigated the impact of hydraulic fracturing-generated flowback water (HF-FW) on whole organism swimming performance/respiration and cardiomyocyte contractility dynamics in mahi-mahi (Coryphaena hippurus-hereafter referred to as "mahi"), an organism which inhabits marine ecosystems where offshore hydraulic fracturing activity is intensifying. Following exposure to 2.75% HF-FW for 24 h, mahi displayed significantly reduced critical swimming speeds (Ucrit) and aerobic scopes (reductions of ∼40 and 61%, respectively) compared to control fish. Additionally, cardiomyocyte exposures to the same HF-FW sample at 2% dilutions reduced a multitude of mahi sarcomere contraction properties at various stimulation frequencies compared to all other treatment groups, including an approximate 40% decrease in sarcomere contraction size and a nearly 50% reduction in sarcomere relaxation velocity compared to controls. An approximate 8-fold change in expression of the cardiac contractile regulatory gene cmlc2 was also seen in ventricles from 2.75% HF-FW-exposed mahi. These results collectively identify cardiac function as a target for HF-FW toxicity and provide some of the first published data on UOG toxicity in a marine species.

Effects of excessive impregnation, magnesium content, and pyrolysis temperature on MgO-coated watermelon rind biochar and its lead removal capacity.

MgO-coated watermelon rind biochar (MWRB) is a potentially highly-effective waste-derived material in environmental applications. This research aims to provide valuable insights into the optimization of the production of MWRB for superior environmental performance. It was found that the Mg content of the MWRB could be easily controlled by adjusting the Mg/feedstock mass ratio during excessive impregnation. The BET surface area was found to first increase and then decrease as the Mg content of the MWRB (produced at 600 °C) increased from 1.52% to 10.1%, with an optimal surface area of 293 m2/g observed at 2.51%. Similarly, an optimum pyrolysis temperature of 600 °C was observed in the range of 400-800 °C for a maximum surface area of the MWRB at a fixed Mg/feedstock ratio of 0.48% (resulting in MWRBs with Mg contents of 1.89-2.51%). The Pb removal capacity of the MWRB (produced at 600 °C) increased with increasing Mg content, with a greatest Pb removal capacity of 558 mg/g found for the MWRB with the highest Mg content (10.1%), an improvement of 208% over the 181 mg/g Pb removal capacity of unmodified WRB produced at 600 °C. The Pb removal capacity of the MWRB (produced with 1.89-2.51% Mg) was also discovered to increase from 81.7 mg/g (at 400 °C) to 742 mg/g (at 700 °C), before dropping to 368 mg/g at 800 °C. These findings suggest that the MWRB can be more efficiently utilized in soil and water remediation by optimizing its synthesis conditions.

Potential of asphalt concrete as a source of trace metals.

Asphalt concrete is one of the most important building materials in the modern world, but the leaching potential of metals from this composite material to the environment is poorly understood. In this study, metals leaching from four hot-mix asphalt samples were analyzed: two fresh samples of low-traffic and high-traffic composition and their weathered equivalents collected from roads in the city of Edmonton, Alberta, Canada. A sequential extraction, based on the Community Bureau of Reference method, was applied to study the speciation and potential mobility of metals and metalloids in those samples. Major trace metals identified in all four samples were Mn, P, Ba, Sr, Zn, V, and Ni, with the highest metals concentrations generally found in weathered asphalt concrete. Of the major trace metals, P, Mn, Sr, and Zn were relatively mobile, having large portions of their total concentrations in the exchangeable/acid-soluble and reducible fractions. When considering the most mobile fraction (exchangeable/acid soluble) and using Canada as a model country, up to 180 t P, 440 t Mn, 50 t Ba, 36 t Sr, 11 t Zn, and 0.11-3.2 t of other metals and metalloids (including Cr, Ni, Cu, As, and Pb) could potentially leach from the top layer of Canada's total of paved public roads. To place these amounts into perspective, they were estimated to make up to 22‰ of Canada's annual release numbers into soil, water and air for these same metals and metalloids. However, they are concentrated in a small area around roads and highways, creating the potential for localized soil and groundwater contamination.

Toxicity in aquatic model species exposed to a temporal series of three different flowback and produced water samples collected from a horizontal hydraulically fractured well.

In the present study, we compared the toxicity and associated chemical characterizations of flowback and produced water (FPW) collected from a single horizontal hydraulically fractured well at different time points during FPW production. Since few studies on whole mixture toxicity related to FPW exist, our aims were to determine both overall toxicity of the FPW mixture in a suite of organisms (Daphnia magna, Lumbriculus variegatus, Danio rerio, and Oncorhynchus mykiss) and also determine if toxicity changes depending on variation in FPW chemical properties as a function of time sampled (1.33, 72, and 228 h FPW samples collected immediately post-well production onset were analyzed in current study). FPW chemical composition was determined via quadra-pole inductively coupled plasma - mass spectrometry/mass spectrometry (ICP-MS/MS), full-scan high performance liquid chromatography/Orbitrap mass spectrometry (HPLC/Orbitrap-MS), and gas chromatography-mass spectrometry (GC-MS). We observed that FPW sampled later in the production process contained higher ion and total dissolved solids concentrations, whereas the highest concentrations of dissolved organic compounds were observed in the earliest FPW sample analyzed. Toxicity associated with FPW exposure was deemed to be species-specific to a certain extent, but general trends revealed the earliest FPW sampled contained highest toxic potential. Accordingly, we theorize that although the saline conditions of FPW are the foremost toxicological drivers to freshwater organisms, dissolved organics associated with FPW significantly contribute to the overall toxicity of exposed organisms.

Enhanced irreversible fixation of cesium by wetting and drying cycles in soil.

The retention of radioactive cesium (Cs) in soil is significantly related to the types of clay minerals, while the weathering process affects the irreversible adsorption sites in clay minerals. In this study, the effect of weathering (exposure duration of Cs and repeated wetting and drying cycles) on fractionation of Cs in soils was investigated using fractionation analysis by the sequential extraction. The residual fraction of Cs increased slowly with exposure time but increased rapidly by repeated wetting and drying cycles. XRD analysis shows that a 1.43 nm of interlayer size for vermiculite is shortened to 1.00 nm, i.e., similar to that of illite. The change implies the potential that the structure of expandable clay minerals is transformed to the non-expandable structure by weathering process after Cs retention. Based on the result, the residual fraction of Cs, most stable form of Cs in the soil, reached relatively rapidly to a maximum. However, the process is much slower kinetically in the field because the bench-scale weathering process used in this study is more aggressive. This study implies that Cs fractionations in the soil are converted into a more stable fraction by weathering processes in the soil. Therefore, Cs removal should be conducted as soon as possible after accidental release of Cs in an environmental side.

Mechanisms of the Removal of U(VI) from Aqueous Solution Using Biochar: A Combined Spectroscopic and Modeling Approach.

Biochar has been touted as a promising sorbent for the removal of inorganic contaminants, such as uranium (U), from water. However, the molecular-scale mechanisms of aqueous U(VI) species adsorption to biochar remain poorly understood. In this study, two approaches, grounded in equilibrium thermodynamics, were employed to investigate the U(VI) adsorption mechanisms: (1) batch U(VI) adsorption experiments coupled to surface complexation modeling (SCM) and (2) isothermal titration calorimetry (ITC), supported by synchrotron-based X-ray absorption spectroscopy (XAS) analyses. The biochars tested have considerable proton buffering capacity and most strongly adsorb U(VI) between approximately pH 4 and 6. FT-IR and XPS studies, along with XAS analyses, show that U(VI) adsorption occurs primarily at the proton-active carboxyl (-COOH) and phenolic hydroxyl (-OH) functional groups on the biochar surface. The SCM approach is able to predict U(VI) adsorption behavior across a wide range of pH and at varying initial U(VI) and biochar concentrations, and U adsorption is strongly influenced by aqueous U(VI) speciation. Supporting ITC measurements indicate that the calculated enthalpies of protonation reactions of the studied biochar, as well as the adsorption of U(VI), are consistent with anionic oxygen ligands and are indicative of both inner- and outer-sphere complexation. Our results provide new insights into the modes of U(VI) adsorption by biochar and more generally improve our understanding of its potential to remove radionuclides from contaminated waters.

Thermodynamic Analysis of Nickel(II) and Zinc(II) Adsorption to Biochar.

While numerous studies have investigated metal uptake from solution by biochar, few of these have developed a mechanistic understanding of the adsorption reactions that occur at the biochar surface. In this study, we explore a combined modeling and spectroscopic approach for the first time to describe the molecular level adsorption of Ni(II) and Zn(II) to five types of biochar. Following thorough characterization, potentiometric titrations were carried out to measure the proton (H+) reactivity of each biochar, and the data was used to develop protonation models. Surface complexation modeling (SCM) supported by synchrotron-based extended X-ray absorption fine structure (EXAFS) was then used to gain insights into the molecular scale metal-biochar surface reactions. The SCM approach was combined with isothermal titration calorimetry (ITC) data to determine the thermodynamic driving forces of metal adsorption. Our results show that the reactivity of biochar toward Ni(II) and Zn(II) directly relates to the site densities of biochar. EXAFS along with FT-IR analyses, suggest that Ni(II) and Zn(II) adsorption occurred primarily through proton-active carboxyl (-COOH) and hydroxyl (-OH) functional groups on the biochar surface. SCM-ITC analyses revealed that the enthalpies of protonation are exothermic and Ni(II) and Zn(II) complexes with biochar surface are slightly exothermic to slightly endothermic. The results obtained from these combined approaches contribute to the better understanding of molecular scale metal adsorption onto the biochar surface, and will facilitate the further development of thermodynamics-based, predictive approaches to biochar removal of metals from contaminated water.

Effects on Biotransformation, Oxidative Stress, and Endocrine Disruption in Rainbow Trout (Oncorhynchus mykiss) Exposed to Hydraulic Fracturing Flowback and Produced Water.

The effects of hydraulic fracturing (HF) flowback and produced water (HF-FPW), a complex saline mixture of injected HF fluids and deep formation water that return to the surface, was examined in rainbow trout (Oncorhynchus mykiss). Exposure to HF-FPWs resulted in significant induction of ethoxyresorufin-O-deethylase (EROD) activity in both liver and gill tissues. Increased lipid peroxidation via oxidative stress was also detected by thiobarbituric acid reactive substances (TBARS) assay. The mRNA expressions of a battery of genes related to biotransformation, oxidative stress, and endocrine disruption were also measured using quantitative real-time polymerase chain reaction (Q-RT-PCR). The increased expression of cyp1a (2.49 ± 0.28-fold), udpgt (2.01 ± 0.31-fold), sod (1.67 ± 0.09-fold), and gpx (1.58 ± 0.10-fold) in raw sample exposure group (7.5%) indicated elevated metabolic enzyme activity, likely through the aryl hydrocarbon receptor pathway, and generation of reactive oxygen species. In addition, the elevated vtg and era2 expression demonstrated endocrine disrupting potential exerted by HF-FPW in rainbow trout. The overall results suggested HF-FPW could cause significant adverse effects on fish, and the organic contents might play the major role in its toxicity. Future studies are needed to help fully determine the toxic mechanism(s) of HF-FPW on freshwater fish, and aid in establishing monitoring, treatment, and remediation protocols for HF-FPW.