Redox-mediated changes in the release dynamics of lead and bacterial community composition in a biochar amended soil contaminated with metal halide perovskite solar panel waste.

This study explored the redox-mediated changes in a lead (Pb) contaminated soil (900 mg/kg) due to the addition of solar cell powder (SC) and investigated the impact of biochar derived from soft wood pellet (SWP) and oil seed rape straw (OSR) (5% w/w) on Pb immobilization using an automated biogeochemical microcosm system. The redox potential (Eh) of the untreated (control; SC) and biochar treated soils (SC + SWP and SC + OSR) ranged from -151 mV to +493 mV. In SC, the dissolved Pb concentrations were higher under oxic (up to 2.29 mg L-1) conditions than reducing (0.13 mg L-1) conditions. The addition of SWP and OSR to soil immobilized Pb, decreased dissolved concentration, which could be possibly due to the increase of pH, co-precipitation of Pb with FeMn (hydro)oxides and pyromorphite, and complexation with biochar surface functional groups. The ability and efficiency of OSR for Pb immobilization were higher than SWP, owing to the higher pH and density of surface functional groups of OSR than SWP. Biochar enhanced the relative abundance of Proteobacteria irrespective of Eh changes, while the relative abundance of Bacterioidota increased under oxidizing conditions. Overall, we found that both OSR and SWP immobilized Pb in solar panel waste contaminated soil under both oxidizing and reducing redox conditions which may mitigate the potential risk of Pb contamination.

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.

Adsorption of antibiotics onto low-grade charcoal in the presence of organic matter: Batch and column tests.

Antibiotics contaminate diverse ecosystems and threaten human health. In ecosystems including water, sediment, and soil, the amount of antibiotics present is tiny compared to the amount of natural organic matter. However, most studies have ignored the co-presence of natural organic matter in the adsorption of target antibiotics. In this study, we quantitatively evaluated the effect of co-presenting natural organic matter on the adsorption of sulfamethazine (SMZ) through batch and column experiments using low-grade charcoal, an industrial by-product. SMZ was used as a model antibiotic compound and humic acid (HA) was used to represent natural organic matter. The co-presence of 2000 mg/L HA (400 times the concentration of SMZ) lowered the adsorption rate of SMZ from 0.023 g/mg·min to 0.007 g/mg·min, and the maximum adsorption capacity from 39.8 mg/g to 15.6 mg/g. HA blocked the charcoal's pores and covered its surface adsorption sites, which dramatically lowered its capacity to adsorb SMZ. Similar results were obtained in the flow-through column experiments, where the co-presence of natural organic matter shortened the lifetime of the charcoal. As a result, the co-presence of a relatively high concentration of natural organic matter can inhibit the adsorption of SMZ and likely other antibiotic compounds, and thus the presence of natural organic matter should be accounted for in the design of adsorption processes to treat antibiotics in water.

Improved energy recovery from yard waste by water-starved hydrothermal treatment: Effects of process water and pressure.

This study investigated the feasibility of a high-loading process with less water consumption for the valorization of wet biomass waste through hydrothermal carbonization (HTC) with and without N2 pressurization from the views of water saving, carbon utilization, and energy recovery. The results revealed that reducing the liquid-to-solid ratio from 10 to 2.5 significantly improved carbon storage in hydrochar due to preferential carbon sequestration as the solid phase (59.9%) instead of being lost in the liquid phase (∼10%). The pressurized HTC process resulted in a higher stability hydrochar through the devolatilization of secondary char that was less stable, yet resulted in âˆ¼10% 15% more carbon transformation to the gas phase. A cost-benefit analysis further demonstrated the potential of the high-loading HTC process for enhancing energy recovery while minimizing energy consumption during hydrochar production from high-moisture yard waste.

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.

Spatial and temporal variation in toxicity and inorganic composition of hydraulic fracturing flowback and produced water.

Hydraulic fracturing for oil and gas extraction produces large volumes of wastewater, termed flowback and produced water (FPW), that are highly saline and contain a variety of organic and inorganic contaminants. In the present study, FPW samples from ten hydraulically fractured wells, across two geologic formations were collected at various timepoints. Samples were analyzed to determine spatial and temporal variation in their inorganic composition. Results indicate that FPW composition varied both between formations and within a single formation, with large compositional changes occurring over short distances. Temporally, all wells showed a time-dependent increase in inorganic elements, with total dissolved solids increasing by up to 200,000 mg/L over time, primarily due to elements associated with salinity (Cl, Na, Ca, Mg, K). Toxicological analysis of a subset of the FPW samples showed median lethal concentrations (LC50) of FPW to the aquatic invertebrate Daphnia magna were highly variable, with the LC50 values ranging from 1.16% to 13.7% FPW. Acute toxicity of FPW significantly correlated with salinity, indicating salinity is a primary driver of FPW toxicity, however organic components also contributed to toxicity. This study provides insight into spatiotemporal variability of FPW composition and illustrates the difficulty in predicting aquatic risk associated with FPW.

Machine learning based prediction and experimental validation of arsenite and arsenate sorption on biochars.

Arsenic (As) contamination in water is a significant environmental concern with profound implications for human health. Accurate prediction of the adsorption capacity of arsenite [As(III)] and arsenate [As(V)] on biochar is vital for the reclamation and recycling of polluted water resources. However, comprehending the intricate mechanisms that govern arsenic accumulation on biochar remains a formidable challenge. Data from the literature on As adsorption to biochar was compiled and fed into machine learning (ML) based modelling algorithms, including AdaBoost, LGBoost, and XGBoost, in order to build models to predict the adsorption efficiency of As(III) and As(V) to biochar, based on the compositional and structural properties. The XGBoost model showed superior accuracy and performance for prediction of As adsorption efficiency (for As(III): coefficient of determination (R2) = 0.93 and root mean square error (RMSE) = 1.29; for As(V), R2 = 0.99, RMSE = 0.62). The initial concentrations of As(III) and As(V) as well as the dosage of the adsorbent were the most significant factors influencing adsorption, explaining 48 % and 66 % of the variability for As(III) and As(V), respectively. The structural properties and composition of the biochar explained 12 % and 40 %, respectively, of the variability of As(III) adsorption, and 13 % and 21 % of that of As(V). The XGBoost models were validated using experimental data. R2 values were 0.9 and 0.84, and RMSE values 6.5 and 8.90 for As(III) and As(V), respectively. The ML approach can be a valuable tool for improving the treatment of inorganic As in aqueous environments as it can help estimate the optimal adsorption conditions of As in biochar-amended water, and serve as an early warning for As-contaminated water.

Deciphering the dual role of bacterial communities in stabilizing rhizosphere priming effect under intra-annual change of growing seasons.

The rhizosphere priming effect (RPE) is a widely observed phenomenon affecting carbon (C) turnover in plant-soil systems. While multiple cropping and seasonal changes can have significant impacts on RPE, the mechanisms driving these processes are complex and not yet fully understood. Here, we planted maize in paddy soil during two growing seasons having substantial temperature differences [May-August (warm season, 26.6 °C) and September-November (cool season, 23.1 °C)] within the same calendar year in southern China to examine how seasonal changes affect RPEs and soil C. We identified sources of C emissions by quantifying the natural abundance of 13C and determined microbial metabolic limitations or efficiency and functional genes related to C cycling using an enzyme-based biogeochemical equilibrium model and high-throughput quantitative PCR-based chip technology, respectively. Results showed that microbial metabolism was mainly limited by phosphorus in the warm season, but by C in the cool season, resulting in positive RPEs in both growing seasons, but no significant differences (9.02 vs. 6.27 mg C kg-1 soil day-1). The RPE intensity remained stable as temperature increased (warm season compared to a cool season), which can be largely explained by the simultaneous increase in the abundance of functional genes related to both C degradation and fixation. Our study highlights the simultaneous response and adaptation of microbial communities to seasonal changes and hence contributes to an understanding and prediction of microbially mediated soil C turnover under multiple cropping systems.

Extractability and phytotoxicity of heavy metals and essential elements from plastics in soil solutions and root exudates.

Plastic waste is increasing and is a serious environmental problem. Among the threats associated with plastics is the release of contaminants into the environment. This study aimed to evaluate the efficiency of metals release from plastics (low-density polyethylene (LDPE), polyethylene terephthalate (PET), and polypropylene (PP)) as affected by different soil solution types, artificial root exudates, and distilled water. The extent of metal release varied depending on the type of solution and plastic used. Metals were leached most effectively from plastics in soil solutions, followed by root exudates, and least effectively by distilled water. LDPE released the highest concentrations of Cu and Na into solution, PP released the greatest amount of Fe, and PET released the most Cr. The efficiencies of Mg and Zn release from the plastics (PP and PET) varied by solution type. Among the plastics studied, LDPE exhibited the strongest ability to adsorb metals, such as Fe, Cr, Mg, and Zn from soil solutions. The amount of metal released from the plastics was also dependent on pH, dissolved organic carbon (DOC) concentrations, and the electrical conductivity (EC) of the solutions. Moreover, plastic extracts were found to have negative effects on germination and growth in Lepidium sativum.

Uranium surface processes with sandstone and volcanic rocks in acidic and alkaline solutions.

Understanding the behaviour of uranium waste, for disposal purposes, is crucial due to the correlation between pH values and the disposal of distinct types of waste, with low level waste typically associated with acidic pH values, and higher and intermediate level waste commonly related to alkaline pH values. We studied the adsorption of U(VI) on sandstone and volcanic rock surfaces at pH 5.5 and 11.5 in aqueous solutions with and without bicarbonate (2 mM HCO3-) using XAS and FTIR. In the sandstone system, U(VI) adsorbs as a bidentate complex to Si at pH 5.5 without bicarbonate and as uranyl carbonate species with bicarbonate. At pH 11.5 without bicarbonate, U(VI) adsorbs as monodentate complexes to Si and precipitates as uranophane. With bicarbonate at pH 11.5, U(VI) precipitated as a Na-clarkeite mineral or remained as a uranyl carbonate surface species. In the volcanic rock system, U(VI) adsorbed to Si as an outer sphere complex at pH 5.5, regardless of the presence of bicarbonate. At pH 11.5 without bicarbonate, U(VI) adsorbed as a monodentate complex to one Si atom and precipitated as a Na-clarkeite mineral. With bicarbonate at pH 11.5, U(VI) sorbed as a bidentate carbonate complex to one Si atom. These results provide insight into the behaviour of U(VI) in heterogeneous, real-world systems related to the disposal of radioactive waste.

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.

Mitigation of arsenic release by calcium peroxide (CaO2) and rice straw biochar in paddy soil.

Biochar has a great potential in the stabilization of soil heavy metals; however, the application can actually enhance the mobility of Arsenic (As) in soil. Here, a biochar-coupled calcium peroxide system was proposed to control the increase in As mobility caused by biochar amendment in paddy soil environment. The capability of rice straw biochar pyrolyzed at 500 °C (RB) and CaO2 to control As mobility was evaluated by incubation for 91 days. CaO2 encapsulation was performed for pH control of CaO2, and As mobility was evaluated using a mixture of RB + CaO2 powder (CaO2-p), and RB + CaO2 bead (CaO2-b), respectively. The control soil solely and RB alone were included for comparison. The combination of RB with CaO2 exhibited remarkable performance in controlling As mobility in soil, and As mobility decreased by 40.2% (RB + CaO2-p) and 58.9% (RB + CaO2-b) compared to RB alone. The result was due to high dissolved oxygen (6 mg L-1 in RB + CaO2-p and RB + CaO2-b) and calcium concentrations (296.3 mg L-1 in RB + CaO2-b); oxygen (O2) and Ca2+ derived from CaO2 is able to prevent the reductive dissolution and chelate-promoted dissolution of As bound to iron (Fe) oxide by biochar. This study revealed that the simultaneous application of CaO2 and biochar could be a promising way to mitigate the environmental risk of As.

Copper toxicity does not affect low tide emersion tolerance of Mytilus galloprovincialis.

Intertidal mussels are well adapted to withstand emersion from water during low tide, but they may be intermittently exposed to waterborne toxicants such as copper, which targets physiological processes including metabolism, ammonia excretion, and osmoregulation. To determine if copper exposure damages intertidal organisms' ability to tolerate tidal emersion, Mediterranean mussels (Mytilus galloprovincialis) were exposed to copper for 96 h followed by 6 h of emersion. Oxygen uptake increased after copper exposure which suggests that copper accumulation caused moderate stress in the mussels, but ammonia excretion and anaerobic metabolism were unaffected by mixed copper and emersion exposures. Shell composition analyses indicate that cycles of copper exposure and tidal emersion may affect bivalve shell growth, but copper deposition into shells may decrease the metal's overall toxicity. Results suggest that copper does not damage M. galloprovincialis's tolerance to tidal emersion, and insight is provided into the mussel's ability to overcome mixed stressor exposures.

Copper exposure does not alter the ability of intertidal sea cucumber Cucumaria miniata to tolerate emersion during low tide.

Intertidal animals experience cycles of tidal emersion from water and are vulnerable to copper (Cu) exposure due to anthropogenic toxicant input into marine waters. Both emersion and Cu toxicity can cause damage to physiological processes like aerobic metabolism, ammonia excretion, and osmoregulation, but the interactions of the combination of these two stressors on marine invertebrates are understudied. Mixed effects of 96 h of low and high Cu exposure (20 and 200 µg/L) followed by 6 h of tidal emersion were evaluated on the intertidal sea cucumber Cucumaria miniata. The respiratory tree accumulated the highest concentrations of Cu, followed by the introvert retractor muscle, body wall, and coelomic fluid. Emersion affected accumulation of Cu, perhaps by inhibiting excretion. 200 µg/L of Cu increased lactate production in the respiratory tree, indicative of damaged aerobic metabolism. Cu diminished ammonia excretion, but emersion increased oxygen uptake and ammonia excretion upon re-immersion. The combination of the two stressors did not have any interactive effects on metabolism or ammonia excretion. Neither Cu exposure nor emersion altered ion (sodium, potassium, calcium, magnesium) content of the coelomic fluid. Overall, results of this study suggest that Cu exposure does not alter C. miniata's high tolerance to emersion, and some potential strategies that this species uses to overcome environmental stress are illuminated.

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.

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.

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.

Latent impacts on juvenile rainbow trout (Oncorhynchus mykiss) cardio-respiratory function and swimming performance following embryonic exposures to hydraulic fracturing flowback and produced water.

Technologies associated with hydraulic fracturing continue to be prevalent in many regions worldwide. As a result, the production of flowback and produced water (FPW) - a wastewater generated once pressure is released from subterranean wellbores - continues to rise in regions experiencing fracturing activities, while waste management strategies attempt to mitigate compounding burdens of increased FPW production. The heightened production of FPW increases the potential for release to the environment. However, relatively few studies have directly investigated how ecosystems and organisms may be latently affected long after exposures occur. The current study examines rainbow trout exposed in ovo at select critical cardiac developmental time points to differing dilutions and lengths of time (acute versus chronic) to determine how FPW-mediated exposure in ovo may alter later cardiac function and development. After exposure, we allowed fish to grow for ∼ 8 months post-fertilization and measured fish swimming performance, aerobic scope, and cardiac structure of juvenile trout. Acute 48 h embryonic 5% FPW exposure at either 3 days post-fertilization (dpf) or 10 dpf significantly reduced later swimming performance and aerobic scope in juvenile trout. In ovo exposure to 2.5% FPW at 3 dpf yielded significant decreases in these metrics as well, while exposing trout to 2.5% FPW at 10 dpf did not induce as significant effects. Morphometric analyses of heart muscle tissue in all treatments decreased compact myocardium thickness. Chronic 1% FPW in ovo exposure for 28 days induced similar reductions in swimming performance, aerobic scope, and decreased compact myocardium thickness as acute exposures. Overall, our results demonstrate that FPW exposure during egg development ultimately results in persistently impaired heart morphology and resulting physiological (swimming) performance.