Nickel-Catalyzed Alkene Isomerization to Access Bench-Stable Enamines and Their [3 + 2] Annulation.

Enamines are difficult to prepare on the bench due to their instability, which results in side reactions, decompositions, poor yields, etc. Herein, we developed a simple and effective method for making bench-stable enamines using a very low amount of nickel catalyst loading. The deuterium exchange, competitive reaction, and radical clock experiment have all been found to favor the ionic mechanism of this alkene isomerization. Scale-up and [3 + 2] annulation reaction of enamines with activated cyclopropane to deliver cyclopentane derivatives have shown the value of this method in organic synthesis.

How far have we explored fungi to fight cancer?

The use of fungal cultures have been well documented in human history. Although its used in healthcare, like penicillin and statins, have saved countless of lives, but there is still no fungal products that are specifically indicated for cancers. Research into fungal-derived materials to curb cancers in the recent decades have made a considerable progress in terms of drug delivery vehicles, anticancer active ingredients and cancer immunotherapy. Various parts of the organisms have successfully been exploited to achieve specific tasks. Apart from the identification of novel anticancer compound from fungi, its native capsular structure can also be used as drug cargo to achieve higher oral bioavailability. This review summarises the anticancer potential of fungal-derived materials, highlighting the role of capsular polysaccharides, proteins, and other structures in variety of innovative utilities to fit the current pharmaceutical technology. Many bioactive compounds isolated from fungi have also been formulated into nanoparticles to achieve greater anticancer activity. The progress of fungal compounds and their analogues in clinical trials is also highlighted. In addition, the potential of various fungal species to be developed for anticancer immunotherapy are also discussed.

Valorization of dragon fruit waste to value-added bioproducts and formulations: A review.

Owing to the increasing worldwide population explosion, managing waste generated from the food sector has become a cross-cutting issue globally, leading to environmental, economic, and social issues. Circular economy-inspired waste valorization approaches have been increasing steadily, generating new business opportunities developing valuable bioproducts using food waste, especially fruit wastes, that may have several applications in energy-food-pharma sectors. Dragon fruit waste is one such waste resource, which is rich in several value-added chemicals and oils, and can be a renewable resource to produce several value-added compounds of potential applications in different industries. Pretreatment and extraction processes in biorefineries are important strategies for recovering value-added biomolecules. There are different methods of valorization, including green extractions and biological conversion approaches. However, microbe-based conversion is one of the advanced technologies for valorizing dragon fruit waste into bioethanol, bioactive products, pharmaceuticals, and other valued products by reusing or recycling them. This state-of-the-art review briefly overviews the dragon fruit waste management strategies and advanced eco-friendly and cost-effective valorization technologies. Furthermore, various applications of different valuable bioactive components obtained from dragon fruit waste have been critically discussed concerning various industrial sectors. Several industrial sectors, such as food, pharmaceuticals, and biofuels, have been critically reviewed in detail.

Advances in the fabrication, modification, and performance of biochar, red mud, calcium oxide, and bentonite catalysts in waste-to-fuel conversion.

Various catalysts are being used in fuel production from biomass and polymeric waste for the obtention of an alternative energy source with both environmental friendliness and economic viability. Biochar, red mud bentonite, and calcium oxide have been shown to play a pertinent role as catalysts in waste-to-fuel conversion processes, such as transesterification and pyrolysis. In this line of thought, this paper has provided a compendium of the fabrication and modification technologies of bentonite, red mud calcium oxide, and biochar, together with their various performances in their application in the waste-to-fuel processes. Additionally, an overview of the structural and chemical attributes of these components is discussed regarding their efficiency. Ultimately, research trends and future points of focus are evaluated, and it is observed that techno-economic optimization of catalyst synthetic routes and investigation of new catalytic formulations, such as biochar and red mud-based nanocatalysts, are potential prospects. This report also offers future research directions that are anticipated to contribute to the development of sustainable green fuel generation systems.

A review on control and abatement of soil pollution by heavy metals: Emphasis on artificial intelligence in recovery of contaminated soil.

"Save Soil Save Earth" is not just a catchphrase; it is a necessity to protect soil ecosystem from the unwanted and unregulated level of xenobiotic contamination. Numerous challenges such as type, lifespan, nature of pollutants and high cost of treatment has been associated with the treatment or remediation of contaminated soil, whether it be either on-site or off-site. Due to the food chain, the health of non-target soil species as well as human health were impacted by soil contaminants, both organic and inorganic. In this review, the use of microbial omics approaches and artificial intelligence or machine learning has been comprehensively explored with recent advancements in order to identify the sources, characterize, quantify, and mitigate soil pollutants from the environment for increased sustainability. This will generate novel insights into methods for soil remediation that will reduce the time and expense of soil treatment.

Rice husk biochar - A novel engineered bio-based material for transforming groundwater-mediated fluoride cycling in natural environments.

Biochar, a promising carbon-rich and carbon-negative material, can control water pollution, harness the synergy of sustainable development goals, and achieve circular economy. This study examined the performance feasibility of treating fluoride-contaminated surface and groundwater using raw and modified biochar synthesized from agricultural waste rice husk as problem-fixing renewable carbon-neutral material. Physicochemical characterizations of raw/modified biochars were investigated using FESEM-EDAX, FTIR, XRD, BET, CHSN, VSM, pHpzc, Zeta potential, and particle size analysis were analyzed to identify the surface morphology, functional groups, structural, and electrokinetic behavior. In fluoride (F-) cycling, performance feasibility was tested at various governing factors, contact time (0-120 min), initial F- levels (10-50 mg L-1), biochar dose (0.1-0.5 g L-1), pH (2-9), salt strengths (0-50 mM), temperatures (301-328 K), and various co-occurring ions. Results revealed that activated magnetic biochar (AMB) possessed higher adsorption capacity than raw biochar (RB) and activated biochar (AB) at pH 7. The results indicated that maximum F- removal (98.13%) was achieved using AMB at pH 7 for 10 mg L-1. Electrostatic attraction, ion exchange, pore fillings, and surface complexation govern F- removal mechanisms. Pseudo-second-order and Freundlich were the best fit kinetic and isotherm for F- sorption, respectively. Increased biochar dose drives an increase in active sites due to F- level gradient and mass transfer between biochar-fluoride interactions, which reported maximum mass transfer for AMB than RB and AB. Fluoride adsorption using AMB could be described through chemisorption processes at room temperature (301 K), though endothermic sorption follows the physisorption process. Fluoride removal efficiency reduced, from 67.70% to 53.23%, with increased salt concentrations from 0 to 50 mM NaCl solutions, respectively, due to increased hydrodynamic diameter. Biochar was used to treat natural fluoride-contaminated surface and groundwater in real-world problem-solving measures, showed removal efficiency of 91.20% and 95.61%, respectively, for 10 mg L-1 F- contamination, and has been performed multiple times after systematic adsorption-desorption experiments. Lastly, techno-economic analysis was analyzed for biochar synthesis and F- treatment performance costs. Overall, our results revealed worth output and concluded with recommendations for future research on F- adsorption using biochar.

Recent advancements in antimony (Sb) removal from water and wastewater by carbon-based materials: a systematic review.

Antimony (Sb) has been classified as a high-priority contaminant in the environment. Sb contamination resulting from the use of antimony-containing compounds in industry necessitates the development of efficient methods to remove it from water and wastewater. Adsorption is a highly efficient and reliable method for pollutants removal owing to its availability, recyclability, and low cost. Recently, carbonaceous materials and their applications for the removal of Sb from the aqueous matrices have received special attention worldwide. Herein, this review systematically summarizes the occurrence and exposure of Sb in the environment and on human health, respectively. Different carbon-based adsorbents have been classified for the adsorptive removal of Sb and their adsorption characteristics have been delineated. Recent development in the adsorption performance of the adsorbent materials for improving the Sb removal from the aqueous medium has been outlined. Further, to develop an understanding of the effect of different parameters like pH, competitive ions, and dissolved ions for Sb adsorption and subsequent removal have been discussed. A retrospective analysis of literature was conducted to present the adsorption behavior and underlying mechanisms involved in the removal of Sb using various adsorbents. Moreover, this study has identified emerging research gaps and emphasized the need for developing modified/engineered carbonaceous adsorbents to enhance Sb adsorption from various aqueous matrices.

Sustainable microalgal biomass production in food industry wastewater for low-cost biorefinery products: a review.

Microalgae are recognized as cell factories enriched with biochemicals suitable as feedstock for bio-energy, food, feed, pharmaceuticals, and nutraceuticals applications. The industrial application of microalgae is challenging due to hurdles associated with mass cultivation and biomass recovery. The scale-up production of microalgal biomass in freshwater is not a sustainable solution due to the projected increase of freshwater demands in the coming years. Microalgae cultivation in wastewater is encouraged in recent years for sustainable bioeconomy from biorefinery processes. Wastewater from the food industry is a less-toxic growth medium for microalgal biomass production. Traditional wastewater treatment and management processes are expensive; hence it is highly relevant to use low-cost wastewater treatment processes with revenue generation through different products. Microalgae are accepted as potential biocatalysts for the bioremediation of wastewater. Microalgae based purification of wastewater technology could be a universal alternative solution for the recovery of resources from wastewater for low-cost biomass feedstock for industry. This review highlights the importance of microalgal biomass production in food processing wastewater, their characteristics, and different microalgal cultivation methods, followed by nutrient absorption mechanisms. Towards the end of the review, different microalgae biomass harvesting processes with biorefinery products, and void gaps that tend to hinder the biomass production with future perspectives will be intended. Thus, the review could claim to be valuable for sustainable microalgae biomass production for eco-friendly bioproduct conversions.

Production of microalgae with high lipid content and their potential as sources of nutraceuticals.

In the current global scenario, the world is under a serious dilemma due to the increasing human population, industrialization, and urbanization. The ever-increasing need for fuels and increasing nutritional problems have made a serious concern on the demand for nutrients and renewable and eco-friendly fuel sources. Currently, the use of fossil fuels is creating ecological and economic problems. Microalgae have been considered as a promising candidate for high-value metabolites and alternative renewable energy sources. Microalgae offer several advantages such as rapid growth rate, efficient land utilization, carbon dioxide sequestration, ability to cultivate in wastewater, and most importantly, they do not participate in the food crop versus energy crop dilemma or debate. An efficient microalgal biorefinery system for the production of lipids and subsequent byproduct for nutraceutical applications could well satisfy the need. But, the current microalgal cultivation systems for the production of lipids and nutraceuticals do not offer techno-economic feasibility together with energy and environmental sustainability. This review article has its main focus on the production of lipids and nutraceuticals from microalgae, covering the current strategies used for lipid production and the major high-value metabolites from microalgae and their nutraceutical importance. This review also provides insights on the future strategies for enhanced microalgal lipid production and subsequent utilization of microalgal biomass.

Integrated approaches to mitigate threats from emerging potentially toxic elements: A way forward for sustainable environmental management.

Potentially toxic elements (PTEs) such as toxic metal (loid)s and other emerging hazardous contaminants, exist in the environment and poses a serious threat. A large amount of wastewater containing PTEs such as cadmium, chromium, copper, nickel, arsenic, lead, zinc, etc. Release from industries during production process. Besides these, chemical-based fertilizers used in soils during crop production have become one of the crucial sources of PTEs. Various techniques are being employed for the mitigation of PTEs like chemical precipitation, ion exchange, coagulation, activated carbon, adsorption, membrane filtration, and bioremediation. Among these mitigation strategies, biological processes such as bioremediation, phytoremediation etc. Are extensively used, as they are economic have high-efficiency rate and are eco-friendly. This review intends to provide information on PTEs contamination through various sources; along with the toxicity of metal (loid)s with respect to their patterns of transmission and risks in the changing environment. Various remediation methods for the management of these pollutants along with their techno-economic perspective are also summarized in this review.

Carbon-based catalyst for environmental bioremediation and sustainability: Updates and perspectives on techno-economics and life cycle assessment.

Global rise in the generation of waste has caused an enormous environmental concern and waste management problem. The untreated carbon rich waste serves as a breeding ground for pathogens and thus strategies for production of carbon rich biochar from waste by employing different thermochemical routes namely hydrothermal carbonization, hydrothermal liquefaction and pyrolysis has been of interest by researchers globally. Biochar has been globally produced due to its diverse applications from environmental bioremediation to energy storage. Also, several factors affect the production of biochar including feedstock/biomass type, moisture content, heating rate, and temperature. Recently the application of biochar has increased tremendously owing to the cost effectiveness and eco-friendly nature. Thus this communication summarized and highlights the preferred feedstock for optimized biochar yield along with the factor influencing the production. This review provides a close view on biochar activation approaches and synthesis techniques. The application of biochar in environmental remediation, composting, as a catalyst, and in energy storage has been reviewed. These informative findings were supported with an overview of lifecycle and techno-economical assessments in the production of these carbon based catalysts. Integrated closed loop approaches towards biochar generation with lesser/zero landfill waste for safeguarding the environment has also been discussed. Lastly the research gaps were identified and the future perspectives have been elucidated.

Green route for recycling of low-cost waste resources for the biosynthesis of nanoparticles (NPs) and nanomaterials (NMs)-A review.

Nowadays, nanoparticles (NPs) and nanomaterials (NMs) are used extensively in various streams such as medical science, solar energy, drug delivery, water treatment, and detection of persistent pollutants. Intensive synthesis of NPs/NMs carried out via physico-chemical technologies is deteriorating the environment globally. Therefore, an urgent need to adopt cost-effective and green technologies to synthesize NPs/NMs by recycling of secondary waste resources is highly required. Environmental wastes such as metallurgical slag, electronics (e-waste), and acid mine drainage (AMD) are rich sources of metals to produce NPs. This concept can remediate the environment on the one hand and the other hand, it can provide a future roadmap for economic benefits at industrial scale operations. The waste-derived NPs will reduce the industrial consumption of limited primary resources. In this review article, green emerging technologies involving lignocellulosic waste to synthesize the NPs from the waste streams and the role of potential microorganisms such as microalgae, fungi, yeast, bacteria for the synthesis of NPs have been discussed. A critical insight is also given on use of recycling technologies and the incorporation of NMs in the membrane bioreactors (MBRs) to improve membrane functioning and process performance. Finally, this study aims to mitigate various persisting scientific and technological challenges for the safe disposal and recycling of organic and inorganic waste for future use in the circular economy.

Bioremediation of Endocrine Disrupting Chemicals- Advancements and Challenges.

Endocrine Disrupting Chemicals (EDCs), major group of recalcitrant compounds, poses a serious threat to the health and future of millions of human beings, and other flora and fauna for years to come. A close analysis of various xenobiotics undermines the fact that EDC is structurally diverse chemical compounds generated as a part of anthropogenic advancements as well as part of their degradation. Regardless of such structural diversity, EDC is common in their ultimate drastic effect of impeding the proper functioning of the endocrinal system, basic physiologic systems, resulting in deregulated growth, malformations, and cancerous outcomes in animals as well as humans. The current review outlines an overview of various EDCs, their toxic effects on the ecosystem and its inhabitants. Conventional remediation methods such as physico-chemical methods and enzymatic approaches have been put into action as some form of mitigation measures. However, the last decade has seen the hunt for newer technologies and methodologies at an accelerated pace. Genetically engineered microbial degradation, gene editing strategies, metabolic and protein engineering, and in-silico predictive approaches - modern day's additions to our armamentarium in combating the EDCs are addressed. These additions have greater acceptance socially with lesser dissonance owing to reduced toxic by-products, lower health trepidations, better degradation, and ultimately the prevention of bioaccumulation. The positive impact of such new approaches on controlling the menace of EDCs has been outlaid. This review will shed light on sources of EDCs, their impact, significance, and the different remediation and bioremediation approaches, with a special emphasis on the recent trends and perspectives in using sustainable approaches for bioremediation of EDCs. Strict regulations to prevent the release of estrogenic chemicals to the ecosystem, adoption of combinatorial methods to remove EDC and prevalent use of bioremediation techniques should be followed in all future endeavors to combat EDC pollution. Moreover, the proper development, growth and functioning of future living forms relies on their non-exposure to EDCs, thus remediation of such chemicals present even in nano-concentrations should be addressed gravely.

Multi-omics approaches for remediation of bisphenol A: Toxicity, risk analysis, road blocks and research perspectives.

In this "plastic era" with the increased use of plastic in day today's life the accumulation of its degraded products like microplastics or plastic additives such as Bisphenol A(BPA) is also increasing. BPA is an endocrine-disrupting chemical used as a plasticizing agent in clear plastic, building materials, coatings, and epoxy resin. Several enzymes including laccases and lipases have been studied for the reduction of BPA toxicity. Over the decades of encountering these toxicants, microorganisms have evolved to degrade different classes of plastic additives. Since the degradation of BPA is a long process thus meta-omics approaches have been employed to identify the active microbiota and microbial dynamics involved in the mitigation of BPA. It is also necessary to investigate the impact of processing activities on transit of BPA in food items and to limit its entrance in food world. This review summarizes a comprehensive overview on BPA sources, toxicity, bio-based mitigation approaches along with a deeper understanding of multi-omics approaches for its reduction and risk analysis. Knowledge gaps and opportunities have been comprehensively compiled that would aid the state-of-the-art information in the available literature for the researchers to further address this issue.

Development & validation of scales to assess stigma related to COVID-19 in India.

Background & objectives: COVID-19 pandemic has triggered social stigma towards individuals affected and their families. This study describes the process undertaken for the development and validation of scales to assess stigmatizing attitudes and experiences among COVID-19 and non-COVID-19 participants from the community. Methods: COVID-19 Stigma Scale and Community COVID-19 Stigma Scale constituting 13 and six items, respectively, were developed based on review of literature and news reports, expert committee evaluation and participants' interviews through telephone for a multicentric study in India. For content validity, 61 (30 COVID-19-recovered and 31 non-COVID-19 participants from the community) were recruited. Test-retest reliability of the scales was assessed among 99 participants (41 COVID-19 recovered and 58 non-COVID-19). Participants were administered the scale at two-time points after a gap of 7-12 days. Cronbach's alpha, overall percentage agreement and kappa statistics were used to assess internal consistency and test-retest reliability. Results: Items in the scales were relevant and comprehensible. Both the scales had Cronbach's α above 0.6 indicating moderate-to-good internal consistency. Test-retest reliability assessed using kappa statistics indicated that for the COVID-19 Stigma Scale, seven items had a moderate agreement (0.4-0.6). For the Community COVID-19 Stigma Scale, four items had a moderate agreement. Interpretation & conclusions: Validity and reliability of the two stigma scales indicated that the scales were comprehensible and had moderate internal consistency. These scales could be used to assess COVID-19 stigma and help in the development of appropriate stigma reduction interventions for COVID-19 infected, and mitigation of stigmatizing attitudes in the community.

Bioprocess development of 2, 3-butanediol production using agro-industrial residues.

The valorization of agricultural and industrial wastes for fuel and chemical production benefits environmental sustainability. 2, 3-Butanediol (2,3-BDO) is a value-added platform chemical covering many industrial applications. Since the global market is increasing drastically, production rates have to increase. In order to replace the current petroleum-based 2,3-BDO production, renewable feedstock's ability has been studied for the past few decades. This study aims to find an improved bioprocess for producing 2,3-BDO from agricultural and industrial residues, consequently resulting in a low CO2 emission bioprocess. For this, screening of 13 different biomass samples for hydrolyzable sugars has been done. Alkali pretreatment has been performed with the processed biomass and enzyme hydrolysis performed using commercial cellulase. Among all biomass hydrolysate oat hull and spruce bark biomass could produce the maximum amount of total reducing sugars. Later oat hull and spruce bark biomass with maximum hydrolyzable sugars have been selected for submerged fermentation studies using Enterobacter cloacae SG1. After fermentation, 37.59 and 26.74 g/L of 2,3-BDO was obtained with oat hull and spruce bark biomass, respectively. The compositional analysis of each step of biomass processing has been performed and changes in each component have been evaluated. The compositional analysis has revealed that biomass composition has changed significantly after pretreatment and hydrolysis leading to a remarkable release of sugars which can be utilized by bacteria for 2,3-BDO production. The results have been found to be promising, showing the potential of waste biomass residues as a low-cost raw material for 2,3-BDO production and thus a new lead in an efficient waste management approach for less CO2 emission.

Draft genome of the glucose tolerant ß-glucosidase producing rare Aspergillus unguis reveals complete cellulolytic machinery with multiple beta-glucosidase genes.

Draft genome sequence of the glucose tolerant beta glucosidase (GT-BGL) producing rare fungus Aspergillus unguis NII 08,123 was generated through Next Generation Sequencing (NGS). The genome size of the fungus was estimated to be 37.1 Mb. A total of 3116 contigs were assembled using SPades, and 15,161 proteins were predicted using AUGUSTUS 3.1. Among them, 13,850 proteins were annotated using UniProt. Distribution of CAZyme genes specifically those encoding lignocellulose degrading enzymes were analyzed and compared with those from the industrial cellulase producer Trichoderma reesei in view of the huge differences in detectable enzyme activities between the fungi, despite the ability of A. unguis to grow on lignocellulose as sole carbon source. Full length gene sequence of the inducible GT-BGL could be identified through tracing back from peptide mass fingerprint. A total of 403 CAZymes were predicted from the genome, which includes 232 glycoside hydrolases (GHs), 12 carbohydrate esterases (CEs), 109 glycosyl transferases (GTs), 15 polysaccharide lyases (PLs), and 35 genes with auxiliary activities (AAs). The high level of zinc finger motif containing transcription factors could possibly hint a tight regulation of the cellulolytic machinery, which may also explain the low cellulase activities even when a complete repertoire of cellulase degrading enzyme genes are present in the fungus.

A critical review on various feedstocks as sustainable substrates for biosurfactants production: a way towards cleaner production.

The quest for a chemical surfactant substitute has been fuelled by increased environmental awareness. The benefits that biosurfactants present like biodegradability, and biocompatibility over their chemical and synthetic counterparts has contributed immensely to their popularity and use in various industries such as petrochemicals, mining, metallurgy, agrochemicals, fertilizers, beverages, cosmetics, etc. With the growing demand for biosurfactants, researchers are looking for low-cost waste materials to use them as substrates, which will lower the manufacturing costs while providing waste management services as an add-on benefit. The use of low-cost substrates will significantly reduce the cost of producing biosurfactants. This paper discusses the use of various feedstocks in the production of biosurfactants, which not only reduces the cost of waste treatment but also provides an opportunity to profit from the sale of the biosurfactant. Furthermore, it includes state-of-the-art information about employing municipal solid waste as a sustainable feedstock for biosurfactant production, which has not been simultaneously covered in many published literatures on biosurfactant production from different feedstocks. It also addresses the myriad of other issues associated with the processing of biosurfactants, as well as the methods used to address these issues and perspectives, which will move society towards cleaner production.

Prevalence and hazardous impact of pharmaceutical and personal care products and antibiotics in environment: A review on emerging contaminants.

Antibiotic resistance is a global health emergency linked to unrestrained use of pharmaceutical and personal care products (PPCPs) as prophylactic agent and therapeutic purposes across various industries. Occurrence of pharmaceuticals are identified in ground water, surface water, soils, and wastewater treatment plants (WWTPs) in ng/L to µg/L concentration range. The prevalence of organic compounds including antimicrobial agents, hormones, antibiotics, preservatives, disinfectants, synthetic musks etc. in environment have posed serious health concerns. The aim of this review is to elucidate the major sources accountable for emergence of antibiotic resistance. For this purpose, variety of introductory sources and fate of PPCPs in aquatic environment including human and veterinary wastes, aquaculture and agriculture related wastes, and other anthropogenic activities have been discussed. Furthermore, genetic and enzymatic factors responsible for transfer and appearance of antibiotic resistance genes are presented. Ecotoxicity of PPCPs has been studied in environment in order to present risk imposed to human and ecological health. As per published literature reports, the removal of antibiotics and related traces being difficult, couples the possibility of emergence of antibiotic resistance and hence sustainability in global water resources. Therefore, research on environmental behavior and control strategies should be conducted along with assessing their chronic toxicity to identify potential human and ecological risks.

Cleaner technologies to combat heavy metal toxicity.

Heavy metals frequently occur as silent poisons present in our daily diet, the environment we live and the products we use, leaving us victims to various associated drastic health and ecological bad effects even in meagre quantities. The prevalence of heavy metals can be traced from children's toys, electronic goods, industrial effluents, pesticide preparation, and even in drinking water in some instances; necessitating methods to remediate them. The current review discusses the various physicochemical and biological methods employed to tackle the problem of heavy metal pollution. Apart from the conventional methods following the principles of adsorption, precipitation, coagulation, and various separation techniques, the advancements made in the directions of biological heavy metal detoxification using microbes, plants, algae have been critically analyzed to identify the specific utility of different agents for specific heavy metal removal. The review paper is a nutshell of different heavy metal remediation strategies, their merits, demerits, and modifications done to alleviate process of heavy metal pollution.