Biodegradation Of Herbicides Research Articles

Efficient Biodegradation of Multiple Aryloxyphenoxypropionate Herbicides by Corynebacterium sp. Z-1 and the Proposed Degradation Mechanism.

Esterases are crucial for aryloxyphenoxypropionate herbicide (AOPP) biodegradation. However, the underlying molecular mechanisms of AOPP biodegradation by esterases are poorly understood. In the current work, Corynebacterium sp. Z-1 was isolated and found to degrade multiple AOPPs, including quizalofop-p-ethyl (QPE), haloxyfop-p-methyl (HPM), fenoxaprop-p-ethyl (FPE), cyhalofop-butyl (CYB), and clodinafop-propargyl (CFP). A novel esterase, QfeH, which catalyzes the cleavage of ester bonds in AOPPs to form AOPP acids, was identified from strain Z-1. The catalytic activities of QfeH toward AOPPs decreased in the following order: CFP > FPE > CYB > QPE > HPM. Molecular docking, computational analyses, and site-directed mutagenesis indicated the catalytic mechanisms of QfeH-mediated degradation of different AOPPs. Notably, the key residue S159 is essential for the activity of QfeH. Moreover, V222Y, T227M, T227A, A271R, and M275K mutants, exhibiting 2.9-5.0 times greater activity than QfeH, were constructed. This study facilitates the mechanistic understanding of AOPPs bioremediation by esterases.

Cations impact the biodegradation of iodosulfuron-methyl herbicidal ionic liquids by fungi

ABSTRACT In the framework of this study, six fungal isolates which demonstrated a high capability for biodegrading iodosulphuron-methyl sodium as well as herbicidal ionic liquids based on this herbicide were isolated from different soil samples. The isolates were identified based on the ITS region, whereas biodegradation residues were determined based on LC-MS/MS. Depending on the isolate, the half-lives values of the biodegraded herbicide or herbicidal ionic liquid ranged significantly from just 1.25 days to more than 40 days. The research findings unveiled that the structure of cations is a central limiting factor affecting fungal growth and herbicide transformation in case of ionic liquids. The length of the alkyl chain has been identified as the primary driver of herbicide toxicity, emphasizing the importance of structural factors in herbicide design. In cases when dodecyl(2-hydroxyethyl)dimethyl cation was used, its biodegradation ranged from 0 to approx. 20% and the biodegradability of the iodosulfuron-methyl was notably limited for the majority of the studied isolates. This knowledge provides guidance for development and selection of herbicides with reduced environmental impact. This study highlights the ecological importance of soil fungi, their potential role in herbicide biodegradation, the influence of cations on fungal growth and herbicide transformation, and the structural factors governing herbicide toxicity. Further research in these areas may lead to more efficient and environmentally friendly approaches to herbicide management.

Performance evaluation of Trichoderma reseei in tolerance and biodegradation of diuron herbicide in agar plate, liquid culture and solid-state fermentation.

The present study evaluated the performance of the fungus Trichoderma reesei to tolerate and biodegrade the herbicide diuron in its agrochemical presentation in agar plates, liquid culture, and solid-state fermentation. The tolerance of T. reesei to diuron was characterized through a non-competitive inhibition model of the fungal radial growth on the PDA agar plate and growth in liquid culture with glucose and ammonium nitrate, showing a higher tolerance to diuron on the PDA agar plate (inhibition constant 98.63 mg L-1) than in liquid culture (inhibition constant 39.4 mg L-1). Diuron biodegradation by T. reesei was characterized through model inhibition by the substrate on agar plate and liquid culture. In liquid culture, the fungus biotransformed diuron into 3,4-dichloroaniline using the amide group from the diuron structure as a carbon and nitrogen source, yielding 0.154mg of biomass per mg of diuron. A mixture of barley straw and agrolite was used as the support and substrate for solid-state fermentation. The diuron removal percentage in solid-state fermentation was fitted by non-multiple linear regression to a parabolic surface response model and reached the higher removal (97.26%) with a specific aeration rate of 1.0 vkgm and inoculum of 2.6 × 108 spores g-1. The diuron removal in solid-state fermentation by sorption on barley straw and agrolite was discarded compared to the removal magnitude of the biosorption and biodegradation mechanisms of Trichoderma reesei. The findings in this work about the tolerance and capability of Trichoderma reesei to remove diuron in liquid and solid culture media demonstrate the potential of the fungus to be implemented in bioremediation technologies of herbicide-polluted sites.

Examining the Role of Material Science in Atrazine Herbicide Biodegradation by Pseudomonas putida MTCC 2252

Atrazine is a chlorinated herbicide of the triazine class. It is used to prevent pre-emergence broadleaf weeds in crops such as maize (corn), soybean and sugarcane and on turf, such as golf courses and residential lawns. Atrazine's primary manufacturer is Syngenta and it is one of the most widely used herbicides in the United States, Canadian, and Australian agriculture. The bacteria used for the bio degradation of Atrazine is Pseudomonas putida. In this study, we report the biodegradation of Atrazine at high initial concentrations. The biodegradation of this Atrazine was investigated using Pseudomonas putida. For Pseudomonas putida optimization parameters like Contact time, Ph, Initial concentration, Temperature, Inoculum volume, Carbon source, Nitrogen source

Adaptation of the metolachlor-degrading fungus Trichoderma harzianum to the simultaneous presence of low-density polyethylene (LDPE) microplastics

Although it is known that microplastics (MPs) in soils cause a threat to this complex environment, the actual effects of MPs on soil microorganisms and their catabolic activities, particularly with the biodegradation of herbicides, remain unclear. Hence, the objective of this study was to investigate the effects of a simultaneous presence of metolachlor and low-density polyethylene (LDPE) microplastics on growth inhibition and adaptive responses of Trichoderma harzianum in soil microcosms. Using ergosterol content as an indicator of fungal biomass, it was observed that MPs alone had a marginal inhibitory effect on the growth of the fungus, whereas MET exhibited a dose-dependent inhibitory effect on T. harzianum. However, the presence of MPs did not influence the fungal transforming activity toward the herbicide. Conversely, analysis of lipid profiles in the presence of MPs and herbicides revealed a reduction in the overall fluidity of phospholipid fatty acids, primarily attributed to an increase in lysophospholipids. The activities of six extracellular enzymes in the soil, measured using methylumbelliferone-linked substrates, were significantly enhanced in the presence of MET. These findings contribute to a broader understanding of the alterations in fungal activity in soil resulting from the influence of MPs and MET.

Investigation of the Persistence, Toxicological Effects, and Ecological Issues of S-Triazine Herbicides and Their Biodegradation Using Emerging Technologies: A Review.

S-triazines are a group of herbicides that are extensively applied to control broadleaf weeds and grasses in agricultural production. They are mainly taken up through plant roots and are transformed by xylem tissues throughout the plant system. They are highly persistent and have a long half-life in the environment. Due to imprudent use, their toxic residues have enormously increased in the last few years and are frequently detected in food commodities, which causes chronic diseases in humans and mammals. However, for the safety of the environment and the diversity of living organisms, the removal of s-triazine herbicides has received widespread attention. In this review, the degradation of s-triazine herbicides and their intermediates by indigenous microbial species, genes, enzymes, plants, and nanoparticles are systematically investigated. The hydrolytic degradation of substituents on the s-triazine ring is catalyzed by enzymes from the amidohydrolase superfamily and yields cyanuric acid as an intermediate. Cyanuric acid is further metabolized into ammonia and carbon dioxide. Microbial-free cells efficiently degrade s-triazine herbicides in laboratory as well as field trials. Additionally, the combinatorial approach of nanomaterials with indigenous microbes has vast potential and considered sustainable for removing toxic residues in the agroecosystem. Due to their smaller size and unique properties, they are equally distributed in sediments, soil, water bodies, and even small crevices. Finally, this paper highlights the implementation of bioinformatics and molecular tools, which provide a myriad of new methods to monitor the biodegradation of s-triazine herbicides and help to identify the diverse number of microbial communities that actively participate in the biodegradation process.

Monitoring Biodegradation of Gramonol Herbicide by Streptomyces scabies

Monitoring Biodegradation of Gramonol Herbicide by Streptomyces scabies

BIODEGRADATION OF GLYPHOSATE CONTAINING HERBICIDE BY SOIL FUNGI

Ten fungal isolates were isolated from two herbicide-contaminated soil farms obtained from Amoyo and the University of Ilorin environment in Kwara State after enrichment with mineral salt medium (MSM) supplemented with glyphosate-containing herbicide. The growth of fungal isolates was efficiently stimulated by the organophosphorus herbicide. Fungi isolated were subjected to screening by varying the herbicide concentrations from 0.1 to 3%, which is prepared with MSM. This screening showed that all the fungal isolates had the ability to act in the biodegradation process. However, varying degradative potentials were observed, as some had heavy growth while others had only slight or no growth as the concentrations of the herbicide increased. The ten fungal isolates were characterized and identified as Aspergillus niger, Penicillum spinulosum, Aspergillus terrus, Aspergillus flavus, Fusarium oxysporum, Mucor spp., Aspergillus oryzae, Aspergillus tamari, Rhizopus stolonifer, and Trichoderma koningii, and these were reduced to six after screening with 3% concentration of the herbicide. Four isolates (A. niger, F. oxysporum, Mucor spp., and A. flavus) were selected based on their growth ability on the medium during screening and were used in the biodegradation study. However, there is an increase in fungal dry weights ranging from 8.60 to 18% for 12 days. This shows that these fungi can be employed in the biodegradation of herbicides since they are potentially effective species and are environmentally safer alternative to protect the soil from the contamination of glyphosate-containing herbicide residues.

Isolation and characterization of indigenous bacterial assemblage for biodegradation of persistent herbicides in the soil.

Extensive pesticides (herbicides) use is negatively disturbing the environment and humans. Pesticide bioremediation with eco-friendly techniques bears prime importance. This study aimed to isolate and characterize three different herbicides (metribuzin, clodinafop- propargyl, MCPA (2-methyl, 4 chlorophenoxyacetic acids) and Bromoxynil) degrading bacterial strains from agricultural fields of Punjab University, Pakistan. Among the 12 bacterial isolates, 5 were metribuzin degrading, 3 were clodinafop propargyl degrading and, 4 were MCPA and Bromoxynil degrading bacteria. Morphological, microscopic, and molecular characterization revealed that the majority of these bacterial strains were gram-negative and belonged to Bacillus and Pseudomonas genera. The isolates A6, B3, and C1 were subjected to respective herbicide degradation and the data was confirmed through GC-MS analysis. The effect of herbicide concentrations, pH, and temperature on bacterial growth was determined at OD600. The strain A6 degraded 14.8% metribuzin out of the provided concentration of 50 ppm by following the deamination pathway. While the isolates B3 and C1 degraded 23.2% and 33.9% clodinafop, MCPA and bromo-xynil, respectively, at a spiking concentration of 50ppm. The clodinafop, MCPA and Bromoxynil were metabolized into less toxic products i.e., dicarboxylic acids and 2-methyl phenol respectively, and metabolized via decarboxylation and dehalogenation mechanism. The present study evaluates the herbicides degrading bacterial strains that could potentially be used for bioremediation of agricultural contaminated sites.

Insights into the metabolic pathways and biodegradation mechanisms of chloroacetamide herbicides

Chloroacetamide herbicides are widely used around the world due to their high efficiency, resulting in increasing levels of their residues in the environment. Residual chloroacetamides and their metabolites have been frequently detected in soil, water and organisms and shown to have toxic effects on non-target organisms, posing a serious threat to the ecosystem. As such, rapid and efficient techniques that eliminate chloroacetamide residues from the ecosystem are urgently needed. Degradation of these herbicides in the environment mainly occurs through microbial metabolism. Microbial strains such as Acinetobacter baumannii DT, Bacillus altitudinis A16, Pseudomonas aeruginosa JD115, Sphingobium baderi DE-13, Catellibacterium caeni DCA-1, Stenotrophomonas acidaminiphila JS-1, Klebsiella variicola B2, and Paecilomyces marquandii can effectively degrade chloroacetamide herbicides. The degradation pathway of chloroacetamide herbicides in aerobic bacteria is mainly initiated by an N/C-dealkylation reaction, followed by aromatic ring hydroxylation and cleavage processes, whereas dechlorination is the initial reaction in anaerobic bacteria. The molecular mechanisms associated with bacterial degradation of chloroacetamide herbicides have been explored, with amidase, hydrolase, reductase, ferredoxin and cytochrome P450 oxygenase currently known to play a pivotal role in the catabolic pathways of chloroacetamides. The fungal pathway for the degradation of these herbicides is more complex with more diversified products, and the degradation enzymes and genes involved remain to be discovered. However, there are few reviews specifically summarizing the microbial degrading species and biochemical mechanisms of chloroacetamide herbicides. Here, we briefly summarize the latest progress resulting from research on microbial strain resources and enzymes involved in degradation of these herbicides and their corresponding genes. Furthermore, we explore the biochemical pathways and molecular mechanisms for biodegradation of chloroacetamide herbicides in depth, thereby providing a reference for further research on the bioremediation of such herbicides.

2,4-D versus 2,4-D based ionic liquids: Effect of cation on herbicide biodegradation, tfdA genes abundance and microbiome changes during soil bioaugmentation.

The commercial formulations of herbicides rely on surfactants which increase the efficiency of active substance. Herbicidal ionic liquids (ILs), in which cationic surfactants are combined with herbicidal anions, allow for additives’ reduction and ensure very good herbicide performance with lower doses. We aimed to test the impact of synthetic and natural cations on biological degradation of 2,4-dichlorophenoxyacetic acid (2,4-D). Although primary biodegradation was high, the mineralization in agricultural soil indicated incomplete conversion of ILs to CO2. Even the introduction of naturally-derived cations resulted in an increase in the herbicide’s half-lives – from 32 days for [Na][2,4-D] to 120 days for [Chol][2,4-D] and 300 days for the synthetic tetramethylammonium derivative [TMA][2,4-D]. Bioaugmentation with 2,4-D-degrading strains improves the herbicides’ degradation, which was reflected by higher abundance of tfdA genes. Microbial community analysis confirmed that hydrophobic cationic surfactants, even those based on natural compounds, played a negative role on microbial biodiversity. Our study provides a valuable indication for further research related to the production of a new generation of environmentally friendly compounds. Moreover, the results shed a new light on the ionic liquids as independent mixtures of ions in the environment, as opposed to treating them as new type of environmental pollutants.

Changes in fatty acid composition as a response to glyphosate toxicity in Pseudomonas fluorescens

Excessive use of herbicides decreases soil biodiversity and fertility. The literature on the xenobiotic response by microorganisms is focused on herbicide biodegradation as a selective event. Non-degradation systems independent of selection could allow the survival of tolerant bacteria in contaminated environments, impacting xenobiotic turnover and, consequently, bioremediation strategies. However, it is uncertain whether the response based on these systems requires selective pressure to be effective. The objective here was to analyze non-degradation phenotypes, enzymatic and structural response systems, of Pseudomonas fluorescens CMA-55 strain, already investigated the production pattern of quorum sensing molecules in response to glyphosate, not present at the isolation site. One mode of response was associated with decrease in membrane permeability and effective antioxidative response for 0–2.30 mM glyphosate, at the mid-log growing phase, with higher activities of Mn-SOD, KatA, and KatB, and presence of fatty acids as nonadecylic acid, margaric and lauric acid. The second response system was characterized by lower antioxidative enzymes activity, presence of KatC isoform, and pelargonic, capric, myristic, stearic, palmitoleic and palmitic acid as principal fatty acids, allowing the strain to face stressful conditions in 9.20–11.50 mM glyphosate at the stationary phase. Therefore, the bacterial strain could modify the fatty acid composition and the permeability of membranes in two response modes according to the herbicide concentration, even glyphosate was not previously selective for P. fluorescens, featuring a generalist system based on physiological plasticity.

Enantioselectivity and mechanisms of chiral herbicide biodegradation in hydroponic systems

This study demonstrates the enantioselective removal dynamics and mechanisms of the chiral herbicide metolachlor in a hydroponic system of Phragmites australis. It presents the first work to elucidate plant-microbial driven enantioselective degradation processes of chiral chemicals. The results showed a degradation efficiency of up to 95.07 ± 2.81% in the hydroponic system driven by a notably high degradation rate constant of 0.086 d−1. P. australis was demonstrated to rapidly increase the contribution of biodegradation pathways in the hydroponic system to 82.21 ± 4.81% within 4 d with an enantiomeric fraction (EF) drop to 0.26 ± 0.02 to favour the enantioselective degradation of S-Metolachlor (kS-Metolachlor = 0.568 d−1 and kR-Metolachlor = 0.147 d−1). Comparatively, the biodegradation pathways in the control constituted less than 25%, with an EF value of circa 0.5. However, the enantioselective biodegradation pathways exhibited complete reversal after about 4 d to favour R-Metolachlor. Plants promoted the degradation of R-Metolachlor, evidenced by an increase in EF to 0.59 ± 0.03. Nonetheless, metolachlor showed an inhibitory effect on plants reflected by the reduction of plant growth rate, chlorophyll content, and electron transport rate to −7.85 ± 1.52%, 1.33 ± 0.43 mg g−1, 4.03 ± 1.33 μmol (m2 s)−1, respectively. However, rhizosphere microorganisms aided plants to catalyze excessive reactive oxygen species production by the antioxidant enzymes to protect plants from oxidative damage and restore their physiological activities. High-throughput analysis of microbial communities demonstrated the enrichment of Massilia (40.63%) and Pseudomonas (8.16%) in the initial stage to promote the rapid degradation of S-Metolachlor. By contrast, the proliferation of Brevundimonas (32.29%) and Pseudarthrobacter (11.03%) in the terminal stage was closely associated with the degradation of R-Metolachlor. Moreover, as symbiotic bacteria of plants, these bacteria aided plants protection from reactive oxygen damages and promoted the recovery of plant metabolic functions and photosynthesis. Overall, these results demonstrate biodegradation mediated by plant-microbe mechanisms as the main driver for the enantioselective degradation of metolachlor in hydroponic systems.

Characterizing the Microbial Consortium L1 Capable of Efficiently Degrading Chlorimuron-Ethyl via Metagenome Combining 16S rDNA Sequencing.

Excessive application of the herbicide chlorimuron-ethyl (CE) severely harms subsequent crops and poses severe risks to environmental health. Therefore, methods for efficiently decreasing and eliminating CE residues are urgently needed. Microbial consortia show potential for bioremediation due to their strong metabolic complementarity and synthesis. In this study, a microbial consortium entitled L1 was enriched from soil contaminated with CE by a “top-down” synthetic biology strategy. The consortium could degrade 98.04% of 100 mg L−1 CE within 6 days. We characterized it from the samples at four time points during the degradation process and a sample without degradation activity via metagenome and 16S rDNA sequencing. The results revealed 39 genera in consortium L1, among which Methyloversatilis (34.31%), Starkeya (28.60%), and Pseudoxanthomonas (7.01%) showed relatively high abundances. Temporal succession and the loss of degradability did not alter the diversity and community composition of L1 but changed the community structure. Taxon-functional contribution analysis predicted that glutathione transferase [EC 2.5.1.18], urease [EC 3.5.1.5], and allophanate hydrolase [EC 3.5.1.54] are relevant for the degradation of CE and that Methyloversatilis, Pseudoxanthomonas, Methylopila, Hyphomicrobium, Stenotrophomonas, and Sphingomonas were the main degrading genera. The degradation pathway of CE by L1 may involve cleavage of the CE carbamide bridge to produce 2-amino-4-chloro-6-methoxypyrimidine and ethyl o-sulfonamide benzoate. The results of network analysis indicated close interactions, cross-feeding, and co-metabolic relationships between strains in the consortium, and most of the above six degrading genera were keystone taxa in the network. Additionally, the degradation of CE by L1 required not only “functional bacteria” with degradation capacity but also “auxiliary bacteria” without degradation capacity but that indirectly facilitate/inhibit the degradation process; however, the abundance of “auxiliary bacteria” should be controlled in an appropriate range. These findings improve the understanding of the synergistic effects of degrading bacterial consortia, which will provide insight for isolating degrading bacterial resources and constructing artificial efficient bacterial consortia. Furthermore, our results provide a new route for pollution control and biodegradation of sulfonylurea herbicides.

Bioremediation of a trifluralin contaminated soil using bioaugmentation with novel isolated bacterial strains and cyclodextrin

Trifluralin (TFL) is a highly persistent with a strong adsorption capacity on soil particles herbicide. This study was to isolate microbial consortia and bacterial strains from a soil with a historical application of pesticides to evaluate their potential to degrade TFL in soil. Different bioremediation techniques were considered for increasing the effectiveness of TFL degradation in soil. These techniques consisted of: i) biostimulation, using a nutrients solution (NS); ii) bioaugmentation, using a natural microbial consortium (NMC), seven individual bacterial strains isolated from NMC, and an artificial bacterial consortium formed by the seven TFL-degrading bacterial strains (ABC); iii) bioavailability enhancement, using a biodegradable compound, a randomly methylated cyclodextrin, RAMEB.Biostimulation using NS leads up to 34 % of soil TFL biodegraded after 100 d. When the contaminated soil was inoculated with NMC or ABC consortia, TFL loss increased up to 62 % and 74 %, respectively, with DT50 values (required time for the pollutant concentration to decline to half of its initial value) of 5.9 and 11 d. In the case of soil inoculation with the isolated individual bacterial strains, the extent of TFL biodegradation ranged widely from 2.3 % to 55 %. The most efficient bacterial strain was Arthrobacter aurescens CTFL7 which had not been previously described in the literature as a TFL-degrading bacterium. Bioaugmentation with CTFL7 bacterium was also tested in the presence of RAMEB, provoking a drastic increase in herbicide biodegradation up to 88 %, achieving a DT50 of only 19 d. Cyclodextrins had never been tested before for enhancement of TFL biodegradation.An ecotoxicity assay was performed to confirm that the proposed bioremediation techniques were also capable to reduce toxicity. A Microtox® test showed that after application A. aurescens CTF7 and A. aurescens CTF7 + RAMEB, the TFL-contaminated soil, which initially presented acute toxicity, became non-toxic at the end of the biodegradation experiments.

Biodegradation of Herbicide by the Immobilized Microbial Consortium SMC1 in Continuous Packed-Bed Biofilm Reactor

The present study aimed to investigate the treatment of butachlor and other commonly used herbicides by the synthetically formulated microbial consortium SMC1 immobilized on the ceramic raschig rings in a packed-bed bioreactor (PBBR). The PBBR was operated in continuous mode at various flow rates over a period of 70 days to determine the effect of hydraulic retention time (HRT) and initial butachlor concentration on the removal efficiency and elimination capability of the bioreactor. It was observed that the overall operation of the bioreactor changes from being controlled by the mass transfer limitations to the controlled bio-reaction , thus proposing the range of 270–325 mg/L/d to be the optimum operating range for the efficient removal of butachlor by the PBBR. The bioreactor can reduce up to 90% of the initial chemical oxygen demand (COD) value while treating the mixture of herbicides. The operating parameters were optimized using response surface methodology where the feed flow rate of 2.9 ml/min, initial herbicide concentration of 454.63 mg/L, and concentration of an additional nitrogen source at 1.41 g/L was found to yield maximal COD reduction. To date, a continuous study in the field of butachlor biodegradation is yet to be reported. Hence, the study could be used as a model to design a better herbicide biotreatment technology.

Changed degradation behavior of pesticides when present in mixtures

Soil microorganisms are indispensable for a healthy soil environment, where the fate of pesticides is contingent on microbial activity. Conversely, soil ecosystems can be distorted by all kinds of variables, such as agrochemicals. These crop protection products have been universally in use for decades in agriculture. In modern crop cultivation, fungicides are increasingly applied because of their high and broad effectivity on plant pathogens. While their use can enhance harvest yields, fungicides, particularly broad-spectrum ones, are responsible for the alteration of the soil microflora. Furthermore, successive and combined application of pesticides is an agronomic routine, which aggravates the concurrent existence of synthetic chemicals in the soil and marine environments. Mutual interactions of such different molecules, or their effects on soil life, can negatively impact the dissipation of biodegradable pesticides from the ecosystems. The direct effects of individual agrochemicals on microbial soil parameters, as well as agronomic efficiency and interactions of mixtures have been thoroughly studied over the past 80 years. The indirect impacts of mixtures on soil and aquatic ecosystems, however, may be overlooked. Moreover, the current regulatory risk assessment of agrochemicals is based on fate investigations of individual substances to derive predicted environmental concentrations, which does not reflect real agricultural scenarios and needs to be updated. In this article, we summarized the results from our own experiments and previous studies, demonstrating that the degradation of pesticides is impacted by the co-existence of fungicides by their effects on microbial and enzymatic activities in soil. • Pesticide mixtures are typical for the agricultural practice and residues may accumulate in soil. • Fungicides can enhance crop yields, but they affect the soil microflora. • Fungicides can adversely impact the biodegradation of herbicides in soil. • Regulatory environmental risk assessment should consider pesticide mixtures.

Anaerobic biodegradation and detoxification of chloroacetamide herbicides by a novel Proteiniclasticum sediminis BAD-10T

Chloroacetamide herbicides (CAAHs) are important herbicides that were widely used to control agricultural weeds. However, their mass applications have seriously contaminated environment, and they are toxic to living beings. CAAHs are easy to enter anoxic environments such as subsoil, wetland sediment, and groundwater, where CAAHs are mainly degraded by anaerobic organisms. To date, there are no research on the anaerobic degradation of CAAHs by pure isolate and toxicity of anaerobic metabolites of CAAHs. In this study, the anaerobic degradation kinetics and metabolites of CAAHs by an anaerobic isolate BAD-10T and the toxicity of anaerobic metabolites were studied. Isolate BAD-10T could degrade alachlor, acetochlor, propisochlor, butachlor, pretilachlor and metolachlor with the degradation kinetics fitting the pseudo-first-order kinetics equation. The degradation rates of CAAHs were significantly affected by the length of N-alkoxyalkyl groups, the shorter the N-alkoxyalkyl groups, the higher the degradation rates. Four metabolites 2-ethyl-6-methyl-N-(ethoxymethyl)-acetanilide (EMEMA), N-(2-methyl-6-ethylphenyl)-acetamide (MEPA), N-2-ethylphenyl acetamide and 2-ethyl-N-carboxyl aniline were identified during acetochlor degradation, and an anaerobic catabolic pathway of acetochlor was proposed. The toxicity of EMEMA and EMPA for zebrafish, Arabidopsis and Chlorella ellipsoidea were obviously lower than that of acetochlor, indicating that the anaerobic degradation of acetochlor by isolate BAD-10T is a detoxification process. The work reveals the anaerobic degradation kinetics and catabolic pathway of CAAHs and highlights a potential application of Proteiniclasticum sediminis BAD-10T for bioremediation of CAAHs residue-contaminated environment.

Rapid degradation of the sulfonylurea herbicide–chlorimuron-ethyl by three novel strains of fungi

Chlorimuron-ethyl is a sulfonylurea herbicide with broad-spectrum weed control characteristics, low utilization rate, relatively high persistence in the soil. Chlorimuron-ethyl has been widely used world-over, and strategies for its removal have attracted increasing attention. Microbial degradation is considered the most acceptable dissipation method. We obtained the best biodegradation conditions using response surface methodology. Through the cleavage of the sulfonylurea bridge, we proposed a metabolic route for chlorimuron-ethyl degradation. Under these conditions (pH 6, 30 °C), Irpex lacteus could degrade 72.40% of the initially supplemented 40 mg L−1 chlorimuron-ethyl within 7 days. The half-life of chlorimuron-ethyl after inoculation was fairly short (4.696 days). The biodegradation rate of chlorimuron-ethyl by Irpex lacteus was 56.1%, which was higher than that of Phlebia sp. (50.8%) and Funalia trogii (25.4%). The pH value has an impact on the free state of the substrate molecule and the dissociation state of the enzyme molecule. The biodegradation rate was the highest (58.5%) at a pH value of 6. When the temperature was 30 °C, 56.3% of chlorimuron-ethyl was eliminated. As the temperature increased, the biodegradation rate of chlorimuron-ethyl by white-rot fungi decreased. Based on the results of LC–MS analysis, a metabolic route for chlorimuron-ethyl biodegradation was proposed. The fragment at m/z 161 (2-amino-4-chloro-6-methoxypyrimidine) originates from the cleavage of the C-N bond of the sulfonylurea bridge, while generating ethyl 2-sulfamoyl benzoate. The fragment at m/z 202 (2-sulfamoyl benzoic acid) corresponds to the ethyl group lost from ethyl 2-sulfamoyl benzoate. Due to the different secreted enzymes, there was a gap between the three strains in the degradation efficiency of chlorimuron-ethyl. The degradation rate of the herbicide by Phlebia sp. was the highest (61.7%), while by Irpex lacteus was the lowest (42.7%). Three white-rot fungi could degrade chlorimuron-ethyl in malt extract. LC–MS analysis indicated that the cleavage of sulfonylurea bridge through Irpex lacteus mediated the degradation of chlorimuron-ethyl. And, inoculation with white-rot fungi enhanced chlorimuron-ethyl degradation in aseptic soil samples. This is the principal report revealing that white-rot fungi can evacuate sulfonylurea herbicides, demonstrating that white-rot fungi will give novel ideas into the biodegradation of herbicides.

Biodegradation of Herbicides by a Plant Nonheme Iron Dioxygenase: Mechanism and Selectivity of Substrate Analogues

AbstractAryloxyalkanoate dioxygenases are unique herbicide biodegrading nonheme iron enzymes found in plants and hence, from environmental and agricultural point of view they are important and valuable. However, they often are substrate specific and little is known on the details of the mechanism and the substrate scope. To this end, we created enzyme models and calculate the mechanism for 2,4‐dichlorophenoxyacetic acid biodegradation and 2‐methyl substituted analogues by density functional theory. The work shows that the substrate binding is tight and positions the aliphatic group close to the metal center to enable a chemoselective reaction mechanism to form the C2‐hydroxy products, whereas the aromatic hydroxylation barriers are well higher in energy. Subsequently, we investigated the metabolism of R‐ and S‐methyl substituted inhibitors and show that these do not react as efficiently as 2,4‐dichlorophenoxyacetic acid substrate due to stereochemical clashes in the active site and particularly for the R‐isomer give high rebound barriers.