Hydrothermal Treatment of Biomass Feedstocks for Sustainable Production of Chemicals, Fuels, and Materials: Progress and Perspectives.

Hydrothermal process is an emerging technology that contributes to sustainable production of biomass-derived chemicals, fuels, and materials. This technology uses hot compressed water to convert various biomass feedstocks including recalcitrant organic compounds in biowastes into desired solid, liquid, and gaseous products. In recent years, considerable progress has been made in the hydrothermal conversion of lignocellulosic as well as nonlignocellulosic biomass to value-added products and bioenergy to fulfill the principles of circular economy. However, it is important to assess hydrothermal processes in terms of their capabilities and limitations from different sustainability aspects so that further advances can be made toward improvement of their technical maturity and commercialization potential. The key aims of this comprehensive review are to (a) explain the inherent properties of biomass feedstocks and physio-chemical characteristics of their bioproducts, (b) elucidate related transformation pathways, (c) clarify the role of hydrothermal process for biomass conversion, (d) evaluate the capability of hydrothermal treatment coupled with other technologies for producing novel chemicals, fuels and materials, (e) explore different sustainability assessments of hydrothermal processes for potential large-scale applications, and (f) offer our perspectives to facilitate the transition from a primarily petro-based to an alternative biobased society in the context of changing climate.

Recycling of spent lithium-ion batteries for a sustainable future: recent advancements.

Lithium-ion batteries (LIBs) are widely used as power storage systems in electronic devices and electric vehicles (EVs). Recycling of spent LIBs is of utmost importance from various perspectives including recovery of valuable metals (mostly Co and Li) and mitigation of environmental pollution. Recycling methods such as direct recycling, pyrometallurgy, hydrometallurgy, bio-hydrometallurgy (bioleaching) and electrometallurgy are generally used to resynthesise LIBs. These methods have their own benefits and drawbacks. This manuscript provides a critical review of recent advances in the recycling of spent LIBs, including the development of recycling processes, identification of the products obtained from recycling, and the effects of recycling methods on environmental burdens. Insights into chemical reactions, thermodynamics, kinetics, and the influence of operating parameters of each recycling technology are provided. The sustainability of recycling technologies (e.g., life cycle assessment and life cycle cost analysis) is critically evaluated. Finally, the existing challenges and future prospects are presented for further development of sustainable, highly efficient, and environmentally benign recycling of spent LIBs to contribute to the circular economy.

Characteristics of airborne particles in stone quarrying areas: Human exposure assessment and mitigation.

This investigation aims to assess the levels of human exposure to airborne particulate matter (PM) in various locations of a natural stone quarry for the first time based on simultaneous measurements of both PM mass and number concentrations (PMC and PNC). A quarry located in Danang city, Vietnam, considered to be a "hotspot" of air pollution in the city, was selected for detailed investigations. Both PMC and PNC were found to be significantly higher (1.2-6.0 times) within the quarry compared to surrounding areas. Mechanical activities during mining, notably crushing, screening, hauling, and loading stones, contributed to increased emissions of PM in the coarser mode (1-10 µm) compared to the accumulation mode (0.1-1 µm) and thus increased deposition of PM1-10 in the human upper respiratory tract. In contrast, combustion activities, especially the diesel engine exhaust from various machines and vehicles used in the quarry, resulted in increased emissions of small particles in the accumulation mode that dominated the PNC and in their deposition in the lower respiratory tract. Simultaneous measurements of PNC and PMC revealed that the PM counts were strongly associated with PM deposition in the alveolar region (accounting for ≈ 76% of total PNC of particles less than 10 µm, N10), while the PM mass concentration was a better indicator of the deposition of PM in the head airway region (≈92% of total PMC of PM10). Overall, this study demonstrates the significance of measuring both PNC and PMC to assess PM exposure levels, regional respiratory doses, and potential health effects associated with human exposure to PM generated from stone quarrying activities. The novelty of this work is the integration of real-time mass and number concentrations of PM over the size range from 20 nm to 10 µm to provide insights into respiratory deposited doses of size-fractionated PM among quarry workers.

CO2 uptake by activated hydrochar derived from orange peel (Citrus reticulata): Influence of carbonization temperature.

In this study, activated hydrochar was prepared from orange peel (OP) waste using KOH for the first time for potential environmental applications. The influence of hydrothermal carbonization temperature (180 °C, 200 °C, and 220 °C) on the CO2 adsorption capacity of OP-derived activated hydrochar (OP-180, OP-200, and OP-220) was investigated. Scanning electron microscope (SEM) images revealed that the activated OP hydrochar has high microporosity, a desired attribute for effective adsorption. The yield and the oxygen content of the hydrochar decreased with the increasing process temperature whereas the carbon content showed an increase. Fourier-transform infrared spectroscopy showed the presence of various functional groups including ketone, aldehydes, esters, and carboxyl in the hydrochar. CO2 adsorption isotherm was determined for all hydrochar samples. At 25 °C and 1 bar, OP-220 showed the highest CO2 uptake at 3.045 mmol/g. The use of OP waste for CO2 adsorption applications contributes to carbon neutrality and a circular economy.

Biological nitrogen removal from stormwater in bioretention cells: a critical review.

Excess nitrogen in stormwater degrades surface water quality via eutrophication and related processes. Bioretention has been recognized as a highly effective low-impact development (LID) technology for the management of high runoff volumes and reduction of nitrogen (N) pollutants through various mechanisms. This paper provides a comprehensive and critical review of recent developments on the biological N removal processes occurring in bioretention systems. The key plant- and microbe-mediated N transformation processes include assimilation (N uptake by plants and microbes), nitrification, denitrification, and anammox (anaerobic ammonia oxidation), but denitrification is the major pathway of permanent N removal. Overall, both laboratory- and field-scale bioretention systems have demonstrated promising N removal performance (TN: >70%). The phyla Bacteroidetes and Proteobacteria are the most abundant microbial communities found to be enriched in biofilter media. Furthermore, the denitrifying communities contain several functional genes (e.g., nirK/nirS, and nosZ), and their concentrations increase near the surface of media depth. The N removal effectiveness of bioretention systems is largely impacted by the hydraulics and environmental factors. When a bioretention system operates at: low hydraulic/N loading rate, containing a saturation zone, vegetated with native plants, having deeper and multilayer biofilter media with warm climate temperature and wet storm events periods, the N removal efficiency can be high. This review highlights shortcomings and current knowledge gaps in the area of total nitrogen removal using bioretention systems, as well as identifies future research directions on this topic.

Greenhouse Gas Emission Mitigation Pathways for Urban Passenger Land Transport under Ambitious Climate Targets.

Urban passenger land transport is an important source of greenhouse gas (GHG) emissions globally, but it is challenging to mitigate these emissions as this sector interacts with many other economic sectors. We develop the Climate change constrained Urban passenger Transport Integrated Life cycle assessment (CURTAIL) model to outline mitigation pathways of urban passenger land transport that are consistent with ambitious climate targets. CURTAIL uses the transport activity of exogenously defined modal shares to simulate the associated annual vehicle stocks, sales, and life cycle GHG emissions. It estimates GHG emission budgets that are consistent with global warming below 2 and 1.5 °C above preindustrial levels and seeks mitigation strategies to remain within the budgets. We apply it to a case study of Singapore, a city-state. Meeting a 1.5 °C target requires strong commitments in the transport and electricity sectors, such as reducing the motorized passenger activity, accelerating the deployment of public transit and of electrification, and decarbonizing the power generation system. Focusing on one mitigation technology or one mode of transport alone will not be sufficient to meet the target. Our novel model could be applied to any city to provide insights relevant to the design of urban climate change mitigation targets and policies.

Assessment and mitigation of toddlers' personal exposure to black carbon before and during the COVID-19 pandemic: A case study in Singapore.

Black carbon (BC), an important indicator of traffic-related air pollution (TRAP) in urban environments, is receiving increased attention because of its adverse health effects. Personal exposure (PE) of adults to BC has been widely studied, but little is known about the exposure of young children (toddlers) to BC in cities. We carried out a pilot study to investigate the integrated daily PE of toddlers to BC in a city-state with a high population density (Singapore). We studied the impact of urban traffic on the PE of toddlers to BC by comparing and contrasting on-road traffic flow (i.e., volume and composition) in Singapore in 2019 (before the COVID-19 pandemic) and in 2020 (during the COVID-19 pandemic). Our observations indicate that the daily BC exposure levels and inhaled doses increased by about 25% in 2020 (2.9 ± 0.3 µg m-3 and 35.5 µg day-1) compared to that in 2019 (2.3 ± 0.4 µg m-3 and 28.5 µg day-1 for exposure concentration and inhaled dose, respectively). The increased BC levels were associated with the increased traffic volume on both weekdays and weekends in 2020 compared to the same time period in 2019. Specifically, we observed an increase in the number of trucks as well as cars/taxis and motorcycles (private transport) and a decline in the number of buses (public transport) in 2020. The implementation of lockdown measures in 2020 resulted in significant changes in the time, place and duration of PE of toddlers to BC. The recorded daily time-activity patterns indicated that toddlers spent almost all the time in indoor environments during the measurement period in 2020. When we compared different ventilation options (natural ventilation (NV), air conditioning (AC), and portable air cleaner (PAC)) for mitigation of PE to BC in the home environment, we found a significant decrease (>30%) in daily BC exposure levels while using the PAC compared to the NV scenario. Our case study shows that the PE of toddlers to BC is of health concern in indoor environments in 2020 because of the migration of the increased TRAP into naturally ventilated residential homes and more time spent indoors than outdoors. Since toddlers' immune system is weak, technological intervention is necessary to protect their health against inhalation exposure to air pollutants.

Air quality changes in cities during the COVID-19 lockdown: A critical review.

In response to the rapid spread of coronavirus disease-2019 (COVID-19) within and across countries and the need to protect public health, governments worldwide introduced unprecedented measures such as restricted road and air travel and reduced human mobility in 2020. The curtailment of personal travel and economic activity provided a unique opportunity for researchers to assess the interplay between anthropogenic emissions of primary air pollutants, their physical transport, chemical transformation, ultimate fate and potential health impacts. In general, reductions in the atmospheric levels of outdoor air pollutants such as particulate matter (PM), nitrogen dioxide (NO2), carbon monoxide (CO), sulfur dioxide (SO2), and volatile organic compounds (VOCs) were observed in many countries during the lockdowns. However, the levels of ozone (O3), a secondary air pollutant linked to asthma and respiratory ailments, and secondary PM were frequently reported to remain unchanged or even increase. An increase in O3 can enhance the formation of secondary PM2.5, especially secondary organic aerosols, through the atmospheric oxidation of VOCs. Given that the gaseous precursors of O3 (VOCs and NOx) are also involved in the formation of secondary PM2.5, an integrated control strategy should focus on reducing the emission of the common precursors for the co-mitigation of PM2.5 and O3 with an emphasis on their complex photochemical interactions. Compared to outdoor air quality, comprehensive investigations of indoor air quality (IAQ) are relatively sparse. People spend more than 80% of their time indoors with exposure to air pollutants of both outdoor and indoor origins. Consequently, an integrated assessment of exposure to air pollutants in both outdoor and indoor microenvironments is needed for effective urban air quality management and for mitigation of health risk. To provide further insights into air quality, we do a critical review of scientific articles, published from January 2020 to December 2020 across the globe. Finally, we discuss policy implications of our review in the context of global air quality improvement.

Bioretention systems for stormwater management: Recent advances and future prospects.

Bioretention is a popular stormwater management strategy that is often utilized in urban environments to combat water quality and hydrological impacts of stormwater. This goal is achieved by selective designing of a system, which consists of suitable vegetation at the top planted on an engineered media with drainage system and possible underdrain at the bottom. Bibliometric analysis on bioretention studies indicates that most of the original research contributions are derived from a few countries and selected research groups. Hence, most of the bioretention systems installed in diverse geographical locations are based on guidelines from climatically different countries, which often lead to operational failures. The current review critically analyzes recent research findings from the bioretention literature, provides the authors' perspectives on the current state of knowledge, highlights the key knowledge gaps in bioretention research, and points out future research directions to make further advances in the field. Specifically, the role and desired features of bioretention components, the importance of fundamental investigations in laboratory, field-based studies and modeling efforts, the real-time process control of bioretention cells, bioretention system design considerations, and life cycle assessment of full-scale bioretention systems are discussed. The importance of local conditions in guiding bioretention designs in difference climates is emphasized. At the end of the review, current technical challenges are identified and recommendations to overcome them are provided. This comprehensive review not only offers fundamental insights into bioretention technology, but also provides novel ideas to combat issues related to urban runoff and achieve sustainable stormwater management.

Evaluation of the effectiveness of a portable air cleaner in mitigating indoor human exposure to cooking-derived airborne particles.

Gas cooking is an important source of airborne particulate matter (PM) indoors. Exposure to cooking-derived PM can lead to adverse human health impacts on non-smokers, especially in poorly-ventilated residential homes. Most of the previous studies on gas cooking emissions mainly focused on fine particles (PM2.5) with little information on their size-fractionation. Moreover, studies dealing with mitigation of indoor human exposure to cooking-derived PM are currently sparse. Therefore, a systematic study was conducted to investigate the characteristics of PM2.5 and size-fractionated PM derived from five commonly used cooking methods, namely, steaming, boiling, stir-frying, pan-frying and deep-frying in a poorly-ventilated domestic kitchen under controlled experimental conditions. Additionally, an indoor portable air cleaner was employed as a mitigation device to capture cooking-derived PM and improve indoor air quality (IAQ). Results revealed that the oil-based deep-frying cooking released the highest airborne particles which were about 170 folds higher compared to the baseline levels for PM2.5 mass concentrations. The use of the air cleaner showed a statistically significant (p < 0.05) reduction in the indoor PM2.5 levels. Moreover, PM<0.25 (particles with diameter ≤ 250 nm) showed a very high mass concentration (378.2 µg/m3) during deep-frying, raising human health concern. A substantial reduction (~60-85%) in PM<0.25 mass concentrations and their total respiratory deposition doses (RDD) in the human respiratory tract was observed while using the air cleaner during the five cooking methods. Furthermore, morphological characteristics and the relative abundance of trace elements in cooking-derived PM were also investigated. This study provides useful insights into the assessment and mitigation of indoor human exposure to cooking-derived PM.

Effects of Cerium Oxide and Ferrocene Nanoparticles Addition As Fuel-Borne Catalysts on Diesel Engine Particulate Emissions: Environmental and Health Implications.

This study systematically examined the potential impacts of doping CeO2 and Fe(C5H5)2 nanoparticles as fuel-borne catalysts (FBCs) to ultralow sulfur diesel (ULSD) fuel on the physical, chemical and toxicological characteristics of diesel particulate matter (DPM). The FBCs-doped fuels are effective in promoting soot oxidation and reducing the DPM mass emissions, but lead to a significant increase in the total particle counts due to the formation of self-nucleated metallic nanoparticles. Compared to undoped ULSD, the FBCs-doped fuels result in higher concentrations of particle-phase polycyclic aromatic hydrocarbons (PAHs) and n-alkanes, higher fractions of organic carbon (OC) and water-soluble organic carbon (WSOC) in particles, show slight alterations in soot nanostructure, reduce soot ignition temperature and activation energy. Exposure of the human-type II cell alveolar epithelial cells (A549) to DPM derived from FBCs-doped fuels shows a decrease in cell viability and alterations in the global gene expression with a broad range of biochemical pathways. The overall variations in DPM characteristics are mainly caused by the catalytic combustion process, and are related to the type, properties and contents of FBCs used in diesel fuel as well as the engine operating conditions. Environmental and health implications of the study are highlighted.

In situ acidity and pH of size-fractionated aerosols during a recent smoke-haze episode in Southeast Asia.

The characterization of aerosol acidity has received increased attention in recent years due to its influence on atmospheric visibility, climate change and human health. Distribution of water soluble inorganic (WSI) ions in 12 different size fractions of aerosols was investigated under two different atmospheric conditions (smoke-haze and non-haze periods) in 2012 using the Micro-Orifice Uniform Deposit Impactor (MOUDI) and nano-MOUDI for the first time in Singapore. To estimate the in situ acidity ([H(+)]Ins) and in situ aerosol pH (pHIS), the Aerosol Inorganic Model version-IV under deliquescent mode of airborne particles was used at prevailing ambient temperature and relative humidity. The study revealed an increase in the levels of airborne particulate matter (PM) mass and concentrations of WSI ions for all size fractions during the smoke-haze period, which was caused by the trans-boundary transport of biomass burning-impacted air masses from Indonesia. A bimodal distribution was observed for concentrations of SO4(2-), NO3(-), Cl(-), K(+) and Na(+), whereas concentrations of NH4(+), Ca(2+) and Mg(2+) showed a single mode distribution. The concentration of WSI ions in PM1.8 during the smoke-haze period increased by 3.8 (for SO4(2-)) to 10.5 (for K(+)) times more than those observed during the non-haze period. The pHIS were observed to be lower during the smoke-haze period than that during the non-haze period for all size fractions of PM, indicating that atmospheric aerosols were more acidic due to the influence of biomass burning emissions. The particles in the accumulation mode were more acidic than those in the coarse mode.

Comparison of physical and chemical properties of ambient aerosols during the 2009 haze and non-haze periods in Southeast Asia.

Recurrent smoke-haze episodes that occur in Southeast Asia (SEA) are of much concern because of their environmental and health impacts. These haze episodes are mainly caused by uncontrolled biomass and peat burning in Indonesia. Airborne particulate matter (PM) samples were collected in the southwest coast of Singapore from 16 August to 9 November in 2009 to assess the impact of smoke-haze episodes on the air quality due to the long-range transport of biomass and peat burning emissions. The physical and chemical characteristics of PM were investigated during pre-haze, smoke-haze, and post-haze periods. Days with PM2.5 mass concentrations of ≥35 µg m(-3) were considered as smoke-haze events. Using this criterion, out of the total 82 sampling days, nine smoke-haze events were identified. The origin of air masses during smoke-haze episodes was studied on the basis of HYSPLIT backward air trajectory analysis for 4 days. In terms of the physical properties of PM, higher particle surface area concentrations and particle gravimetric mass concentrations were observed during the smoke-haze period, but there was no consistent pattern for particle number concentrations during the haze period as compared to the non-haze period except that there was a significant increase at about 08:00, which could be attributed to the entrainment of PM from aloft after the breakdown of the nocturnal inversion layer. As for the chemical characteristics of PM, among the six key inorganic water-soluble ions (Cl(-), NO3(-), nss-SO4(2-), Na(+), NH4(+), and nss-K(+)) measured in this study, NO3(-), nss-SO4(2-), and NH4(+) showed a significant increase in their concentrations during the smoke-haze period together with nss-K(+). These observations suggest that the increased atmospheric loading of PM with higher surface area and increased concentrations of optically active secondary inorganic aerosols [(NH4)2SO4 or NH4HSO4 and NH4NO3] resulted in the atmospheric visibility reduction in SEA due to the advection of biomass and peat burning emissions.

Effect of oxygenated fuels on physicochemical and toxicological characteristics of diesel particulate emissions.

A systematic study was conducted to make a comparative evaluation of the effects of blending five different oxygenates (diglyme (DGM), palm oil methyl ester (PME), dimethyl carbonate (DMC), diethyl adipate (DEA), and butanol (Bu)) with ultralow sulfur diesel (ULSD) at 2% and 4% oxygen levels on physicochemical and toxicological characteristics of particulate emissions from a nonroad diesel engine. All blended fuels led to an overall decrease in the particulate mass concentration and elemental carbon (EC) emissions, which was strongly associated with the oxygen content in fuels and the specific type of fuels used. In general, the proportion of particulate-bound organic carbon (OC) and water-soluble organic carbon (WSOC) increased while using oxygenated fuel blends. Compared to ULSD, all fuel blends showed different emission factors of particle-phase PAHs and n-alkanes, slight alterations in soot nanostructure, lower soot ignition temperature, and lower activation energy. The total counts of particles (≤ 560 nm diameter) emitted decreased gradually for ULSD blended with DMC, DEA, and Bu, while they increased significantly for other fuel blends. The in vitro toxicity of particulates significantly increased with ULSD blended with DMC and DEA, while it decreased when ULSD was blended with PME, DGM, and Bu.

2013 Southeast Asian smoke haze: fractionation of particulate-bound elements and associated health risk.

Recurring biomass burning-induced smoke haze is a serious regional air pollution problem in Southeast Asia (SEA). The June 2013 haze episode was one of the worst air pollution events in SEA. Size segregated particulate samples (2.5-1.0 µm; 1.0-0.5 µm; 0.5- 0.2 µm; and <0.2 µm) were collected during the June 2013 haze episode. PM2.5 concentrations were elevated (up to 329 µg/m(3)) during the haze episode, compared to those during the nonhaze period (11-21 µg/m(3)). Chemical fractionation of particulate-bound trace elements (B, Ca, K, Fe, Al, Ni, Zn, Mg, Se, Cu, Cr, As, Mn, Pb, Co, and Cd) was done using sequential extraction procedures. There was a 10-fold increase in the concentration of K, an inorganic tracer of biomass burning. A major fraction (>60%) of the elements was present in oxidizable and residual fractions while the bioavailable (exchangeable) fraction accounted for up to 20% for most of the elements except K and Mn. Deposition of inhaled potentially toxic trace elements in various regions of the human respiratory system was estimated using a Multiple-Path Particle Dosimetry model. The particle depositions in the respiratory system tend to be more severe during hazy days than those during nonhazy days. A prolonged exposure to finer particles can thus cause adverse health outcomes during hazy days. Health risk estimates revealed that the excessive lifetime carcinogenic risk to individuals exposed to biomass burning-impacted aerosols (18 ± 1 × 10(-6)) increased significantly (P < 0.05) compared to those who exposed to urban air (12 ± 2 × 10(-6)).

Accumulation of Long-Lived Photogenerated Holes at Indium Single-Atom Catalysts via Two Coordinate Nitrogen Vacancy Defect Engineering for Enhanced Photocatalytic Oxidation.

Visible-light-driven photocatalytic oxidation by photogenerated holes has immense potential for environmental remediation applications. While the electron-mediated photoreduction reactions are often at the spotlight, active holes possess a remarkable oxidation capacity that can degrade recalcitrant organic pollutants, resulting in nontoxic byproducts. However, the random charge transfer and rapid recombination of electron-hole pairs hinder the accumulation of long-lived holes at the reaction center. Herein, a novel method employing defect-engineered indium (In) single-atom photocatalysts with nitrogen vacancy (Nv) defects, dispersed in carbon nitride foam (In-Nv-CNF), is reported to overcome these challenges and make further advances in photocatalysis. This Nv defect-engineered strategy produces a remarkable extension in the lifetime and an increase in the concentration of photogenerated holes in In-Nv-CNF. Consequently, the optimized In-Nv-CNF demonstrates a remarkable 50-fold increase in photo-oxidative degradation rate compared to pristine CN, effectively breaking down two widely used antibiotics (tetracycline and ciprofloxacin) under visible light. The contaminated water treated by In-Nv-CNF is completely nontoxic based on the growth of Escherichia coli. Structural-performance correlations between defect engineering and long-lived hole accumulation in In-Nv-CNF are established and validated through experimental and theoretical agreement. This work has the potential to elevate the efficiency of overall photocatalytic reactions from a hole-centric standpoint.

Elemental Characterization of Ambient Particulate Matter for a Globally Distributed Monitoring Network: Methodology and Implications.

Global ground-level measurements of elements in ambient particulate matter (PM) can provide valuable information to understand the distribution of dust and trace elements, assess health impacts, and investigate emission sources. We use X-ray fluorescence spectroscopy to characterize the elemental composition of PM samples collected from 27 globally distributed sites in the Surface PARTiculate mAtter Network (SPARTAN) over 2019-2023. Consistent protocols are applied to collect all samples and analyze them at one central laboratory, which facilitates comparison across different sites. Multiple quality assurance measures are performed, including applying reference materials that resemble typical PM samples, acceptance testing, and routine quality control. Method detection limits and uncertainties are estimated. Concentrations of dust and trace element oxides (TEO) are determined from the elemental dataset. In addition to sites in arid regions, a moderately high mean dust concentration (6 µg/m3) in PM2.5 is also found in Dhaka (Bangladesh) along with a high average TEO level (6 µg/m3). High carcinogenic risk (>1 cancer case per 100000 adults) from airborne arsenic is observed in Dhaka (Bangladesh), Kanpur (India), and Hanoi (Vietnam). Industries of informal lead-acid battery and e-waste recycling as well as coal-fired brick kilns likely contribute to the elevated trace element concentrations found in Dhaka.

Insights into lipidomic perturbations in zebrafish tissues upon exposure to microcystin-LR and microcystin-RR.

This work represents the first study of its kind that was conducted to evaluate changes in lipid metabolic networks following a balneation exposure of adult zebrafish to MCLR (microcystin-leucine-arginine) and MCRR (microcystin-arginine-arginine) at a sublethal dose (10 µg L(-1)) for a period of 30 days. Following the exposure to MCLR and MCRR, gills, liver, intestine, and brain tissues were harvested for metabolite extraction. Extracted metabolites were detected using qTOF-LC-MS (time-of-flight-liquid chromatography-mass spectrometry). Metabolites were identified using Kegg pathways. The identified metabolites are shown on lipid biochemical maps to demonstrate major perturbations in the metabolic machinery. Results showed that most of the metabolic pathways under the lipid class were affected in different tissues of zebrafish following the exposure to MCLR and MCRR (10 µg L(-1) for 30 days). The kind and flux of metabolic perturbations varied among different tissues of the organs after the exposure to MCLR and MCRR with the tissues of gills being the most affected. Among the various lipid pathways, cholesterol synthesis was affected significantly as observed from the highest number of perturbed metabolites in that pathway. Cholesterol is responsible for synthesis of steroid hormones and bile acids, which have been recognized as endocrine signaling molecules. Disruption in the synthesis of these compounds following MCLR/MCRR exposure suggests that MCs are capable of causing endocrine disruption among aquatic organisms even under sublethal conditions. Apart from cholesterol synthesis, various other metabolic pathways belonging to the class of essential fatty acids and lipid oxidation were also observed to be perturbed following a balneation exposure of zebrafish to MCLR/MCRR.

Recovery of valuable metals from spent lithium-ion batteries using microbial agents for bioleaching: a review.

Spent lithium-ion batteries (LIBs) are increasingly generated due to their widespread use for various energy-related applications. Spent LIBs contain several valuable metals including cobalt (Co) and lithium (Li) whose supply cannot be sustained in the long-term in view of their increased demand. To avoid environmental pollution and recover valuable metals, recycling of spent LIBs is widely explored using different methods. Bioleaching (biohydrometallurgy), an environmentally benign process, is receiving increased attention in recent years since it utilizes suitable microorganisms for selective leaching of Co and Li from spent LIBs and is cost-effective. A comprehensive and critical analysis of recent studies on the performance of various microbial agents for the extraction of Co and Li from the solid matrix of spent LIBs would help for development of novel and practical strategies for effective extraction of precious metals from spent LIBs. Specifically, this review focuses on the current advancements in the application of microbial agents namely bacteria (e.g., Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans) and fungi (e.g., Aspergillus niger) for the recovery of Co and Li from spent LIBs. Both bacterial and fungal leaching are effective for metal dissolution from spent LIBs. Among the two valuable metals, the dissolution rate of Li is higher than Co. The key metabolites which drive the bacterial leaching include sulfuric acid, while citric acid, gluconic acid and oxalic acid are the dominant metabolites in fungal leaching. The bioleaching performance depends on both biotic (microbial agents) and abiotic factors (pH, pulp density, dissolved oxygen level and temperature). The major biochemical mechanisms which contribute to metal dissolution include acidolysis, redoxolysis and complexolysis. In most cases, the shrinking core model is suitable to describe the bioleaching kinetics. Biological-based methods (e.g., bioprecipitation) can be applied for metal recovery from the bioleaching solution. There are several potential operational challenges and knowledge gaps which should be addressed in future studies to scale-up the bioleaching process. Overall, this review is of importance from the perspective of development of highly efficient and sustainable bioleaching processes for optimum resource recovery of Co and Li from spent LIBs, and conservation of natural resources to achieve circular economy.

Insights into interactions of biodegradable and non-biodegradable microplastics with heavy metals.

Biodegradable microplastics (BMPs) are considered to be environmentally friendly compared to non-biodegradable plastics (NMPs). However, BMPs are likely to become toxic during their transport because of the adsorption of pollutants (e.g., heavy metals) onto them. This study investigated the uptake of six heavy metals (Cd2+, Cu2+, Cr3+, Ni2+, Pb2+, and Zn2+) by a common BMPs (polylactic acid (PLA)) and compared their adsorption characteristics to those of three types of NMPs (polyethylene (PE), polypropylene (PP), and polyvinyl chloride (PVC)) for the first time. The order of heavy metal adsorption capacity among the four MPs was PE > PLA > PVC > PP. The findings suggest that BMPs contained more toxic heavy metals than some NMPs. Among the six heavy metals, Cr3+ showed considerably stronger adsorption than other heavy metals in both BMPS and NMPs. The adsorption of heavy metals on MPs can be well explained using the Langmuir isotherm model, while the adsorption kinetic curves showed the best fit to the pseudo-second-order kinetic equation. Desorption experiments revealed that BMPs released a higher percentage of heavy metals (54.6-62.6%) in the acidic environment in a shorter time (~ 6 h) compared to NMPs. Overall, this study provides insights into interactions of BMPs and NMPs with heavy metals and their removal mechanisms in aquatic environment.