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Fipronil is a broad-spectrum phenyl-pyrazole insecticide that is widely used in agriculture. However, in the environment, its residues are toxic to aquatic animals, crustaceans, bees, termites, rabbits, lizards, and humans, and it has been classified as a C carcinogen. Due to its residual environmental hazards, various effective approaches, such as adsorption, ozone oxidation, catalyst coupling, inorganic plasma degradation, and microbial degradation, have been developed. Biodegradation is deemed to be the most effective and environmentally friendly method, and several pure cultures of bacteria and fungi capable of degrading fipronil have been isolated and identified, including Streptomyces rochei, Paracoccus sp., Bacillus firmus, Bacillus thuringiensis, Bacillus spp., Stenotrophomonas acidaminiphila, and Aspergillus glaucus. The metabolic reactions of fipronil degradation appear to be the same in different bacteria and are mainly oxidation, reduction, photolysis, and hydrolysis. However, the enzymes and genes responsible for the degradation are somewhat different. The ligninolytic enzyme MnP, the cytochrome P450 enzyme, and esterase play key roles in different strains of bacteria and fungal. Many unanswered questions exist regarding the environmental fate and degradation mechanisms of this pesticide. The genes and enzymes responsible for biodegradation remain largely unexplained, and biomolecular techniques need to be applied in order to gain a comprehensive understanding of these issues. In this review, we summarize the literature on the degradation of fipronil, focusing on biodegradation pathways and identifying the main knowledge gaps that currently exist in order to inform future research. KEY POINTS: • Biodegradation is a powerful tool for the removal of fipronil. • Oxidation, reduction, photolysis, and hydrolysis play key roles in the degradation of fipronil. • Possible biochemical pathways of fipronil in the environment are described.

The herbicide butachlor has been used in huge quantities worldwide, affecting various environmental systems. Butachlor residues have been detected in soil, water, and organisms, and have been shown to be toxic to these non-target organisms. This paper briefly summarizes the toxic effects of butachlor on aquatic and terrestrial animals, including humans, and proposes the necessity of its removal from the environment. Due to long-term exposure, some animals, plants, and microorganisms have developed resistance toward butachlor, indicating that the toxicity of this herbicide can be reduced. Furthermore, we can consider removing butachlor residues from the environment by using such butachlor-resistant organisms. In particular, microbial degradation methods have attracted much attention, with about 30 kinds of butachlor-degrading microorganisms have been found, such as Fusarium solani, Novosphingobium chloroacetimidivorans, Chaetomium globosum, Pseudomonas putida, Sphingomonas chloroacetimidivorans, and Rhodococcus sp. The metabolites and degradation pathways of butachlor have been investigated. In addition, enzymes associated with butachlor degradation have been identified, including CndC1 (ferredoxin), Red1 (reductase), FdX1 (ferredoxin), FdX2 (ferredoxin), Dbo (debutoxylase), and catechol 1,2 dioxygenase. However, few reviews have focused on the microbial degradation and molecular mechanisms of butachlor. This review explores the biochemical pathways and molecular mechanisms of butachlor biodegradation in depth in order to provide new ideas for repairing butachlor-contaminated environments. KEY POINTS: • Biodegradation is a powerful tool for the removal of butachlor. • Dechlorination plays a key role in the degradation of butachlor. • Possible biochemical pathways of butachlor in the environment are described.

Tetramethrin is a pyrethroid insecticide that is commonly used worldwide. The toxicity of this insecticide into the living system is an important concern. In this study, a novel tetramethrin-degrading bacterial strain named A16 was isolated from the activated sludge and identified as Gordonia cholesterolivorans. Strain A16 exhibited superior tetramethrin degradation activity, and utilized tetramethrin as the sole carbon source for growth in a mineral salt medium (MSM). High-performance liquid chromatography (HPLC) analysis revealed that the A16 strain was able to completely degrade 25 mg·L−1 of tetramethrin after 9 days of incubation. Strain A16 effectively degraded tetramethrin at temperature 20–40 °C, pH 5–9, and initial tetramethrin 25–800 mg·L−1. The maximum specific degradation rate (qmax), half-saturation constant (Ks), and inhibition constant (Ki) were determined to be 0.4561 day−1, 7.3 mg·L−1, and 75.2 mg·L−1, respectively. The Box–Behnken design was used to optimize degradation conditions, and maximum degradation was observed at pH 8.5 and a temperature of 38 °C. Five intermediate metabolites were identified after analyzing the degradation products through gas chromatography–mass spectrometry (GC-MS), which suggested that tetramethrin could be degraded first by cleavage of its carboxylester bond, followed by degradation of the five-carbon ring and its subsequent metabolism. This is the first report of a metabolic pathway of tetramethrin in a microorganism. Furthermore, bioaugmentation of tetramethrin-contaminated soils (50 mg·kg−1) with strain A16 (1.0 × 107 cells g−1 of soil) significantly accelerated the degradation rate of tetramethrin, and 74.1% and 82.9% of tetramethrin was removed from sterile and non-sterile soils within 11 days, respectively. The strain A16 was also capable of efficiently degrading a broad spectrum of synthetic pyrethroids including D-cyphenothrin, chlorempenthrin, prallethrin, and allethrin, with a degradation efficiency of 68.3%, 60.7%, 91.6%, and 94.7%, respectively, after being cultured under the same conditions for 11 days. The results of the present study confirmed the bioremediation potential of strain A16 from a contaminated environment.

The microbial degradation of acephate in pure cultures has been thoroughly explored, but synergistic metabolism at the community level has rarely been investigated. Here, we report a novel microbial consortium, ZQ01, capable of effectively degrading acephate and its toxic product methamidophos, which can use acephate as a source of carbon, phosphorus and nitrogen. The degradation conditions with consortium ZQ01 were optimized using response surface methodology at a temperature of 34.1°C, a pH of 8.9, and an inoculum size of 2.4×108 CFU·mL-1, with 89.5% of 200 mg·L-1 acephate degradation observed within 32 h. According to the main products methamidophos, acetamide and acetic acid, a novel degradation pathway for acephate was proposed to include hydrolysis and oxidation as the main pathways of acephate degradation. Moreover, the bioaugmentation of acephate-contaminated soils with consortium ZQ01 significantly enhanced the removal rate of acephate. The results of the present work demonstrate the potential of microbial consortium ZQ01 to degrade acephate in water and soil environments, with a different and complementary acephate degradation pathway.

As members of the organochlorine group of insecticides, aldrin and dieldrin are effective at protecting agriculture from insect pests. However, because of excessive use and a long half-life, they have contributed to the major pollution of the water/soil environments. Aldrin and dieldrin have been reported to be highly toxic to humans and other non-target organisms, and so their use has gradually been banned worldwide. Various methods have been tried to remove them from the environment, including xenon lamps, combustion, ion conversion, and microbial degradation. Microbial degradation is considered the most promising treatment method because of its advantages of economy, environmental protection, and convenience. To date, a few aldrin/dieldrin-degrading microorganisms have been isolated and identified, including Pseudomonas fluorescens, Trichoderma viride, Pleurotus ostreatus, Mucor racemosus, Burkholderia sp., Cupriavidus sp., Pseudonocardia sp., and a community of anaerobic microorganisms. Many aldrin/dieldrin resistance genes have been identified from insects and microorganisms, such as Rdl, bph, HCo-LGC-38, S2-RDLA302S, CSRDL1A, CSRDL2S, HaRdl-1, and HaRdl-2. Aldrin degradation includes three pathways: the oxidation pathway, the reduction pathway, and the hydroxylation pathway, with dieldrin as a major metabolite. Degradation of dieldrin includes four pathways: oxidation, reduction, hydroxylation, and hydrolysis, with 9-hydroxydieldrin and dihydroxydieldrin as major products. Many studies have investigated the toxicity and degradation of aldrin/dieldrin. However, few reviews have focused on the microbial degradation and biochemical mechanisms of aldrin/dieldrin. In this review paper, the microbial degradation and degradation mechanisms of aldrin/dieldrin are summarized in order to provide a theoretical and practical basis for the bioremediation of aldrin/dieldrin-polluted environment.

Heavy metal toxicity has become a pressing ecological problem that affects the ecosystems through bioaccumulation, representing a serious public health hazard. Many conventional strategies have been developed and applied to decontaminate and restore metal-contaminated areas. However, these conventional approaches are not very suitable and environmentally safe for heavy metal remediation because of their high operational costs, high energy requirements, post-waste disposal problems, and secondary pollutant generation. Thus, biosurfactant-based bioremediation of heavy metals is a sustainable and promising approach because of its biodegradation capability, economic effectiveness, and ecofriendly nature. Pseudomonas sp., Bacillus sp., Citrobacter freundii, and Candida tropicalis have been isolated as potential sources of biosurfactants and produce compounds such as surfactin, rhamnolipids, and sophorolipids. Owing to the severity of heavy metal pollution in certain parts of the environment, biosurfactants have garnered great interest and attention as an emerging multi-functional technology of the new century for successful removal of heavy metal pollutants. The present study describes the role of biosurfactants in the bioremediation of heavy metals from contaminated environments. Moreover, the interaction mechanism underlying biosurfactant-metal complexation and metal remediation are discussed. Based on the review of the literature, further research is warranted to elucidate the mechanistic roles and explore the structural characterization and gene regulation of biosurfactants to improve their productivity and expand their applicability in bioremediation.

Chlorpyrifos is extensively used worldwide as an insecticide to control various insect pests. Long-term and irregular applications of chlorpyrifos have resulted in large-scale soil, groundwater, sediment, and air pollution. Numerous studies have shown that chlorpyrifos and its major intermediate metabolite 3,5,6-trichloropyridinol (TCP) accumulate in non-target organisms through biomagnification and have a strong toxic effect on non-target organisms, including human beings. Bioremediation based on microbial metabolism is considered an eco-friendly and efficient strategy to remove chlorpyrifos residues. To date, a variety of bacterial and fungal species have been isolated and characterized for the biodegradation of chlorpyrifos and TCP. The metabolites and degradation pathways of chlorpyrifos have been investigated. In addition, the chlorpyrifos-degrading enzymes and functional genes in microbes have been reported. Hydrolases can catalyze the first step in ester-bond hydrolysis, and this initial regulatory metabolic reaction plays a key role in the degradation of chlorpyrifos. Previous studies have shown that the active site of hydrolase contains serine residues, which can initiate a catalytic reaction by nucleophilic attack on the P-atom of chlorpyrifos. However, few reviews have focused on the microbial degradation and catalytic mechanisms of chlorpyrifos. Therefore, this review discusses the deep understanding of chlorpyrifos degradation mechanisms with microbial strains, metabolic pathways, catalytic mechanisms, and their genetic basis in bioremediation.

Pyrethroid insecticides are widely used to manage crop and household pests. The extensive use of pyrethroids leads to pesticide resistance in insects and negatively affects human health. Microbial degradation of pyrethroids is an emerging method to minimize their off-target toxic effects on the environment. The main aim of this research work to compare the biomagnification of pyrethroids in different living systems in environment. This study performed a detailed analysis of pyrethroid biodegradation and toxicity using an in silico approach. Pyrethroid biodegradation was studied using a systems biology-based approach that correlated human, insect and microbial systems to achieve a comprehensive view of total environmental pyrethroid biomagnification and bioremediation. The topology of the pyrethroid model was determined using the hub nodes in cytoscape that improved the understanding of pyrethroid biodegradation and environmental losses. The results of the simulated model were used for the real-time analysis of metabolites, genes, RNA and enzymes in bacteria, insect and human cells. The model predicted the pyrethroid biochemistry and physiology in three living systems. The findings of this study elucidated the systems biology-based analysis of the effects of pyrethroids on bacterial, insect and human systems.

Persistent use of the insecticide D-cyphenothrin has resulted in heavy environmental contamination and public concern. However, microbial degradation of D-cyphenothrin has never been investigated and the mechanism remains unknown. During this study, for the first time, an efficient D-cyphenothrin-degrading bacterial strain Staphylococcus succinus HLJ-10 was identified. Response surface methodology was successfully employed by using Box-Behnken design to optimize the culture conditions. At optimized conditions, over 90% degradation of D-cyphenothrin (50 mg&middot, L&minus, 1) was achieved in a mineral salt medium within 7 d. Kinetics analysis revealed that its half-life was reduced by 61.2 d, in comparison with the uninoculated control. Eight intermediate metabolites were detected in the biodegradation pathway of D-cyphenothrin including cis-D-cyphenothrin, trans-D-cyphenothrin, 3-phenoxybenzaldehyde, &alpha, hydroxy-3-phenoxy-benzeneacetonitrile, trans-2,2-dimethyl-3-propenyl-cyclopropanol, 2,2-dimethyl-3-propenyl-cyclopropionic acid, trans-2,2-dimethyl-3-propenyl-cyclopropionaldehyde, and 1,2-benzenedicarboxylic acid, dipropyl ester. This is the first report about the degradation of D-cyphenothrin through cleavage of carboxylester linkage and diaryl bond. In addition to degradation of D-cyphenothrin, strain HLJ-10 effectively degraded a wide range of synthetic pyrethroids including permethrin, tetramethrin, bifenthrin, allethrin, and chlorempenthrin, which are also widely used insecticides with environmental contamination problems. Bioaugmentation of D-cyphenothrin-contaminated soils with strain HLJ-10 substantially enhanced its degradation and over 72% of D-phenothrin was removed from soils within 40 d. These findings unveil the biochemical basis of a highly efficient D-cyphenothrin-degrading bacterial isolate and provide potent agents for eliminating environmental residues of pyrethroids.

Carbofuran is one of the most toxic broad-spectrum and systemic N-methyl carbamate pesticide, which is extensively applied as insecticide, nematicide and acaricide for agricultural, domestic and industrial purposes. It is extremely lethal to mammals, birds, fish and wildlife due to its anticholinesterase activity, which inhibits acetyl-cholinesterase and butyrylcholinesterse activity. In humans, carbofuran is associated with endocrine disrupting activity, reproductive disorders, cytotoxic and genotoxic abnormalities. Therefore, cleanup of carbofuran-contaminated environments is of utmost concern and urgently needs an adequate, advanced and effective remedial technology. Microbial technology (bacterial, fugal and algal species) is a very potent, pragmatic and ecofriendly approach for the removal of carbofuran. Microbial enzymes and their catabolic genes exhibit an exceptional potential for bioremediation strategies. To understand the specific mechanism of carbofuran degradation and involvement of carbofuran hydrolase enzymes and genes, highly efficient genomic approaches are required to provide reliable information and unfold metabolic pathways. This review briefly discusses the carbofuran toxicity and its toxicological impact into the environment, in-depth understanding of carbofuran degradation mechanism with microbial strains, metabolic pathways, molecular mechanisms and genetic basis involved in degradation.

Carbamate compounds are commonly applied in agricultural sectors as alternative options to the recalcitrant organochlorine pesticides due to their easier breakdown and less persistent nature. However, the large-scale use of carbamates also leads to toxic environmental residues, causing severe toxicity in various living systems. The toxic effects of carbamates are due to their inhibitor activity against the acetylchlolinesterase enzyme. This enzyme is crucial for neurotransmission signaling in living beings. Hence, from the environmental point of view, the elimination of carbamates is a worldwide concern and priority. Microbial technology can be deliberated as a potential tool that can work efficiently and as an ecofriendly option for the dissipation of carbamate insecticides from contaminated environments by improving biodegradation processes via metabolic activities of microorganisms. A variety of bacterial and fungal species have been isolated and characterized and are capable of degrading a broad range of carbamates in soil and water environments. In addition, microbial carbamate hydrolase genes (mcd, cehA, cahA, cfdJ, and mcbA) were strongly implicated in the evolution of new metabolic functions and carbamate hydrolase enzymes. However, the accurate localization and appropriate functions of carbamate hydrolase enzymes/genes are very limited. To explore the information on the degradation routes of carbamates and promote the application of biodegradation, a study of molecular techniques is required to unlock insights regarding the degradation specific genes and enzymes. Hence, this review discusses the deep understanding of carbamate degradation mechanisms with microbial strains, metabolic pathways, molecular mechanisms, and their genetic basis in degradation.

Dichlorvos (O,O-dimethyl O-(2,2-dichlorovinyl)phosphate, DDVP) is a widely acknowledged broad-spectrum organophosphorus insecticide and acaracide. This pesticide has been used for more than four decades and is still in strong demand in many developing countries. Extensive application of DDVP in agriculture has caused severe hazardous impacts on living systems. The International Agency for Research on Cancer of the World Health Organization considered DDVP among the list of 2B carcinogens, which means a certain extent of cancer risk. Hence, removing DDVP from the environment has attracted worldwide attention. Many studies have tested the removal of DDVP using different kinds of physicochemical methods including gas phase surface discharge plasma, physical adsorption, hydrodynamic cavitation, and nanoparticles. Compared to physicochemical methods, microbial degradation is regarded as an environmentally friendly approach to solve several environmental issues caused by pesticides. Till now, several DDVP-degrading microbes have been isolated and reported, including but not limited to Cunninghamella, Fusarium, Talaromyces, Aspergillus, Penicillium, Ochrobium, Pseudomonas, Bacillus, and Trichoderma. Moreover, the possible degradation pathways of DDVP and the transformation of several metabolites have been fully explored. In addition, there are a few studies on DDVP-degrading enzymes and the corresponding genes in microorganisms. However, further research relevant to molecular biology and genetics are still needed to explore the bioremediation of DDVP. This review summarizes the latest development in DDVP degradation and provides reasonable and scientific advice for pesticide removal in contaminated environments.

Perfluoroalkyl acids (PFAAs) are widely used in industrial production and daily life because of their unique physicochemical properties, such as their hydrophobicity, oleophobicity, surface activity, and thermal stability. Perfluorosulfonic acids (PFSAs) and perfluorocarboxylic acids (PFCAs) are the most studied PFAAs due to their global occurrence. PFAAs are environmentally persistent, toxic, and the long-chain homologs are also bioaccumulative. Exposure to PFAAs may arise directly from emission or indirectly via the environmental release and degradation of PFAA precursors. Precursors themselves or their conversion intermediates can present deleterious effects, including hepatotoxicity, reproductive toxicity, developmental toxicity, and genetic toxicity. Therefore, exposure to PFAA precursors constitutes a potential hazard for environmental contamination. In order to comprehensively evaluate the environmental fate and effects of PFAA precursors and their connection with PFSAs and PFCAs, we review environmental biodegradability studies carried out with microbial strains, activated sludge, plants, and earthworms over the past decade. In particular, we review perfluorooctyl-sulfonamide-based precursors, including perfluroooctane sulfonamide (FOSA) and its N-ethyl derivative (EtFOSA), N-ethyl perfluorooctane sulfonamido ethanol (EtFOSE), and EtFOSE-based phosphate diester (DiSAmPAP). Fluorotelomerization-based precursors are also reviewed, including fluorotelomer alcohols (FTOH), fluorotelomer sulfonates (FTSA), and a suite of their transformation products. Though limited information is currently available on zwitterionic PFAS precursors, a preliminary review of data available for 6:2 fluorotelomer sulfonamide betaine (FTAB) was also conducted. Furthermore, we update and refine the recent knowledge on biotransformation strategies with a focus on metabolic pathways and mechanisms involved in the biotransformation of PFAA precursors. The biotransformation of PFAA precursors mainly involves the cleavage of carbon-fluorine (C-F) bonds and the degradation of non-fluorinated functional groups via oxidation, dealkylation, and defluorination to form shorter-chained PFAAs. Based on the existing research, the current problems and future research directions on the biotransformation of PFAA precursors are proposed.