Degradation Pathways Of Atrazine Research Articles

Biochar modification accelerates soil atrazine biodegradation by altering bacterial communities, degradation-related genes and metabolic pathways

Atrazine is one of the most used herbicides, posing non-neglectable threats to ecosystem and human health. This work studied the performance and mechanisms of surface-modified biochar in accelerating atrazine biodegradation by exploring the changes in atrazine metabolites, bacterial communities and atrazine degradation-related genes. Among different types of biochar, nano-hydroxyapatite modified biochar achieved the highest degradation efficiency (85.13 %), mainly attributing to the increasing pH, soil organic matter, soil humus, and some enriched indigenous bacterial families of Bradyrhizobiaceae, Rhodospirillaceae, Methylophilaceae, Micrococcaceae, and Xanthobacteraceae. The abundance of 4 key atrazine degradation-related genes (atzA, atzB, atzC and triA) increased after biochar amendment, boosting both dechlorination and dealkylation pathways in atrazine metabolism. Our findings evidenced that biochar amendment could accelerate atrazine biodegradation by altering soil physicochemical properties, microbial composition and atrazine degradation pathways, providing clues for improving atrazine biodegradation performance at contaminated sites.

Impact of superabsorbent hydrogels on microbial community and atrazine fate in soils by 14C-labeling techniques

The accumulation of atrazine in soils can create environmental challenges, potentially posing risks to human health. Superabsorbent hydrogel (SH)-based formulations offer an eco-friendly approach to accelerate herbicide degradation. However, the impact of SHs on soil microbial community structure, and thus on the fate of atrazine, remains uncertain. In this study, a radioactive tracer was employed to investigate the influence of SHs on microbial communities and atrazine transformation in soils. The results revealed that the mineralization of atrazine in active soils was considerably greater than that in sterilized soils. Atrazine degradation proceeded rapidly under SH treatment, indicating the potential of SH to accelerate atrazine degradation. Furthermore, SH addition did not alter the atrazine degradation pathway in soils, which included dealkylation, dechlorination and hydroxylation. The relative abundance of dominant microbial population was influenced by the presence of SHs in the soil. Additionally, SH application led to an increased relative abundance of Lysobacter, suggesting its potential involvement in atrazine degradation. These findings reveal the significance of soil microorganisms and SH in atrazine degradation, offering crucial insights for the development of effective strategies for atrazine remediation and environmental sustainability.

The influence of vermicompost on atrazine microbial degradation performance and pathway in black soil, Northeast China

The atrazine (ATR) is extensively used in dryland crops like corn and sorghum in black soil region of Northeast China, posing ecological risks due to toxic metabolites. Vermicompost are known for soil organic pollution remediation but their role in pesticide degradation in black soil remains understudied. The influence of vermicompost on the microbial degradation pathway of atrazine was assessed in this study. Although vermicompost didn't significantly boost atrazine removal, they notably aided in primary metabolite degradation, hydroxyatrazine (HYA), deisopropylatrazine (DIA), and deethylatrazine (DEA), reducing their content by 38.67 %. They also altered the soil microbial community structure, favoring atrazine-degrading bacteria like Proteobacteria, Firmicutes, and Actinobacteria. Five secondary degradation products were identified in vermicompost treatments. Atrazine degradation occurred via dechlorination, dealkylation, and deamination pathways mainly by Nocardioidacea, Streptomycetaceae, Bacillaceae, Sphingomonadaceae, Comamonadaceae and Nitrososphaeraceae. pH and available nitrogen (AN) influenced microbial community structure and atrazine degradation, correlating with vermicompost application rates. Future black soil remediation should optimize application rates based on atrazine content and soil properties.

Degradation of atrazine by ionizing radiation coupled with persulfate oxidation: Mechanism, pathway and toxicity assessment

The ubiquitous existence of atrazine (ATZ) in aquatic environments has aroused intense concerns, regarding its potential harmful effects on human health and ecology safety. Ionizing radiation has now drawn increasing attention in wastewater treatment. However, its unsatisfactory mineralization performance has significantly hindered the practical applications. Herein, the gamma radiation combined with persulfate oxidation (gamma/PS) system has been innovatively engineered to facilitate the removal of ATZ. Results showed that ATZ (10 mg/L) can be completely removed by gamma radiation with 1.0 kGy dose, and the pseudo-first-order kinetic model provided an good fit for the degradation. Gamma radiation can effectively remove ATZ with initial concentrations ranging from 5–20 mg/L, over a broad pH range (3.2–10.5), with the co-existence of inorganic anions (including CO32-, NO3-, and SO42-) and humic acid, and in actual waters (tap water and surface water). Degradation pathways of ATZ were proposed according to density functional theory (DFT) calculation and LC-MS analysis, including alkylic-hydroxylation, alkylic-oxidation, and dechlorination-hydroxylation. Moreover, gamma radiation was promising to reduce the toxicity of ATZ. Compared with the gamma radiation alone process, the gamma/PS system exhibited satisfactory ATZ removal performance. The k value rose by 4.78 times when PS (1 mM) was added, and TOC removal efficiency increased from 6.48 % to 34.53 % when PS was 4 mM. •OH and SO4•- participated in ATZ degradation, with •OH dominating. These results demonstrated that gamma/PS is a potential approach to degrade ATZ.

Tailored anthraquinone-based covalent organic frameworks boosted atrazine degradation through peroxymonosulfate activation driven by visible light

Atrazine (ATZ), a wildly used s-triazine herbicide to avoid grassy insects and weeds, causes biological and environmental issues due to its prolonged existence and various toxic properties. Peroxymonosulfate (PMS) photoactivation-based advanced oxidation processes (AOPs) meet the challenges of sustainable energy and environmental concerns, and thus are promising challenging for ATZ degradation. However, preparing photocatalysts to realize efficient ATZ degradation remains challenging. Here, we prepared the highly efficient visible-light photocatalyst with abundant anthraquinone groups, i.e. TpDQ-COF, which was employed to activate PMS for fast and efficient ATZ degradation. ATZ degradation in the TpDQ-COF/PMS system reached 0.127 min−1 under visible light (VL), which is ca. 17.9 times that of TpDA-COF without anthraquinone. It implies that anthraquinone units served as pivotal active sites for facilitating photoelectron separation and migration, which triggered ROS generation towards highly effective ATZ degradation. In addition, the radical-quenching and Electron Paramagnetic Resonance (EPR) experiments proved that •OH, •SO4- and 1O2 played pivotal roles in ATZ degradation under TpDQ-COF/PMS/VL system. The ATZ degradation pathways included dealkylation, dechlorination-hydroxylation, alkylic-hydroxylation, and alkylic-oxidation, which were confirmed by intermediates and density functional theory (DFT) analysis. Overall, TpDQ-COF showcased its excellent practical utility in the removal of organic pollutants in contaminated water.

Constructing a CeFeO3/LaFeO3/ZnIn2S4 double Z-scheme heterojunction for photocatalytic atrazine degradation under visible light irradiation

The limited light absorption range and rapid recombination of interfacial charges were deemed to be the main restriction of the photocatalysts for atrazine (ATZ) degradation, and the construction of Z-scheme heterojunction was an effective strategy. Herein, a CeFeO3/LaFeO3/ZnIn2S4 (CFO/LFO/ZIS) double Z-scheme ternary heterojunction photocatalyst was fabricated by the in-situ precipitation and hydrothermal method. The photocatalytic ATZ degradation efficiency of optimized heterojunction reached 52% within 175 min under visible light irradiation, which was 3.1, 3.7 and 1.7 times higher than that of CFO, LFO and ZIS, respectively. The enhanced photocatalytic activity was due to the excellent light capture capacity and improved photogenerated charge separation in CFO/LFO/ZIS double Z-scheme heterojunction photocatalyst. Meanwhile, some environmental factors on the influence of photocatalytic ATZ degradation performance were systematically investigated. Quenching experiments confirmed that ·OH, h+ and 1O2 were the main active species during the photocatalytic ATZ degradation process. The possible photogenerated charge separation route was proposed via the analysis of the IEF effects between CFO, LFO and ZIS. Finaly, the possible ATZ degradation pathway was deduced by LC-MS measurement and toxicity assessment of the intermediates were also evaluated by the Toxicity Estimation Software Tool (TEST). This work not only provided a potential magnetic recyclable ferrate based double Z-scheme heterojunction photocatalyst for enhancing photogenerated charge separation and light absorption, but also evaluated the intermediate toxicity and related environmental factors on the activity of photocatalyst, which was facilitating the practical application for the degradation of ATZ.

Ruthenium decorated nickel-iron layered double hydroxides (NiFe-LDH) for promoting peroxymonosulfate activation and atrazine degradation

With the extensive use of atrazine (ATZ), its potential hazards to ecological environment and human health have raised public concerns. This study reports the effective degradation of ATZ via advanced oxidation processes (AOPs) using peroxymonosulfate (PMS) activated by heterogeneous catalysts of Ru loaded NiFe-LDH blossom nanosheets (Ru/NiFe-LDH). During AOPs, the highly dispersed Ru sites as the main catalytic centers and the NiFe-LDH substrate synergistically stimulated PMS to efficiently produce reactive oxygen species to oxidize ATZ. Under optimal conditions, the degradation activity of ATZ by 5.8Ru/NiFe-LDH/PMS system reached 100% within 90 min. Additionally, it also exhibited good environmental applicability. Besides, electron paramagnetic resonance along with quenching experiments illustrated the production of 1O2, O2• −, •OH, SO4• − and surface-bond radicals during the degradation, where 1O2, •OH and surface-bond radicals were further identified as the dominant oxygen species for the oxidation. The ATZ degradation pathway was determined using the liquid chromatography-mass spectrometry to discern the intermediate products, e.g., dealkylation, alkylic-hydroxylation and dechlororination-hydroxylation processes. This work holds a potential application value for the removal of atrazine and other pollutants.

Biodegradation of atrazine and nicosulfuron by Streptomyces nigra LM01: Performance, degradative pathway, and possible genes involved

Microbial herbicide degradation is an efficient bioremediation method. In this study, a strain of Streptomyces nigra, LM01, which efficiently degrades atrazine and nicosulfuron, was isolated from a corn field using a direct isolation method. The degradation effects of the identified strain on two herbicides were investigated and optimized using an artificial neural network. The maximum degradation rates of S. nigra LM01 were 58.09 % and 42.97 % for atrazine and nicosulfuron, respectively. The degradation rate of atrazine in the soil reached 67.94 % when the concentration was 108 CFU/g after 5 d and was less effective than that of nicosulfuron. Whole genome sequencing of strain LM01 helped elucidate the possible degradation pathways of atrazine and nicosulfuron. The protein sequences of strain LM01 were aligned with the sequences of the degraded proteins of the two herbicides by using the National Center for Biotechnology Information platform. The sequence (GE005358, GE001556, GE004212, GE005218, GE004846, GE002487) with the highest query cover was retained and docked with the small-molecule ligands of the herbicides. The results revealed a binding energy of − 6.23 kcal/mol between GE005358 and the atrazine ligand and − 6.66 kcal/mol between GE002487 and the nicosulfuron ligand.

Degradation of Atrazine by an Anaerobic Microbial Consortium Enriched from Soil of an Herbicide-Manufacturing Plant.

Atrazine is an important herbicide that has been widely used for weed control in recent decades. However, with the extensive use of atrazine, its residue seriously pollutes the environment. Therefore, the microbial degradation and detoxification of atrazine have received extensive attention. To date, the aerobic degradation pathway of atrazine has been well studied; however, little is known about its anaerobic degradation in the environment. In this study, an anaerobic microbial consortium capable of efficiently degrading atrazine was enriched from soil collected from an herbicide-manufacturing plant. Six metabolites including hydroxyatrazine, deethylatrazine, N-isopropylammelide, deisopropylatrazine, cyanuric acid, and the novel metabolite 4-ethylamino-6-isopropylamino-1,3,5-triazine (EIPAT) were identified, and two putative anaerobic degradation pathways of atrazine were proposed: a hydrolytic dechlorination pathway is similar to that seen in aerobic degradation, and a novel pathway initiated by reductive dechlorination. During enrichment, Denitratisoma, Thiobacillus, Rhodocyclaceae_unclassified, Azospirillum, and Anaerolinea abundances significantly increased, dominating the enriched consortium, indicating that they may be involved in atrazine degradation. These findings provide valuable evidence for elucidating the anaerobic catabolism of atrazine and facilitating anaerobic remediation of residual atrazine pollution.

Interplay of xenobiotic-degrading and antibiotic-resistant microorganisms among the microbiome found in the air, handrail, and floor of the subway station

Investigating the quality of the subway environment, especially regarding antibiotic resistance genes (ARGs) and xenobiotics, conveys ecological and health impacts. In this study, compositions and relations of microorganisms harboring ARGs and xenobiotic degradation and metabolism genes (XDGs) in the Sukhumvit subway station (MRT-SKV) in Bangkok was assessed by analyzing the taxonomic and genetic diversity of the microbiome in the air and on the surfaces of floor and handrail. The major bacteria in the MRT-SKV (including Moraxella, which was abundant in the bioaerosol and handrail samples, and Staphylococcus, which was abundant in the bioaerosol samples) were found to contain both ARGs and XDGs. The co-abundance correlation network revealed notable relationships among bacteria harboring antibiotic resistance genes (ARGs) and xenobiotic degradation genes (XDGs). Significant associations were observed between ARGs linked to glycopeptide and fluoroquinolone resistance and genes associated with benzoate, styrene, and atrazine degradation pathways, as well as between ARGs related to cephamycin, cephalosporin, and MLS resistance and XDGs associated with the cytochrome P450-dependent drug metabolism pathway. These correlations suggested that selective pressure exerted by certain xenobiotics and antibiotics can simultaneously affect both ARGs and XDGs in the environment and should favor correlations and co-survival among ARG- and XDG-containing bacteria in the environments. The correlations may occur via shared mechanisms of resistance to both xenobiotics and antibiotics. Finally, different correlation pairs were seen in different niches (air, handrail, floor) of the subway environment or different geolocations. Thus, the relationship between ARG and XDG pairs most likely depends on the unique characteristics of the niches and on the prominent types of xenobiotics and antibiotics in the subway environment. The results indicated that interactions and connections between microbial communities can impact how they function. These microorganisms can have profound effects on accumulation of xenobiotics and ARGs in the MRT-SKV.

Amino acid promoted oxidation of atrazine by Fe3O4/persulfate

In the present study, we demonstrated that the presence of cysteine could remarkably enhance the degradation of atrazine by Fe3O4/persulfate system. The results of electron paramagnetic resonance (EPR) spectra confirmed the combination of cysteine and Fe3O4 exhibited much higher activity on activation of persulfate to generate more SO4•- and •OH than Fe3O4 alone. At pH of 3.0, SO4•- and •OH contributed to about 58.2 % and 41.8 % of atrazine removal respectively, while •OH gradually dominated the oxidation of atrazine from neutral condition to alkaline condition. The co-existing Cl− and HCO3− could quench SO4•-, resulting in the inhibition of atrazine degradation. The presence of low natural organic matters (NOM) concentration (0–2 mg L−1) could enhance the atrazine removal, and high concentration (>5 mg L−1) of NOM restrained the atrazine degradation. During the Cysteine/Fe3O4/Persulfate process, cysteine served as a complexing reagent and reductant. Through acidolysis and complexation, Fe3O4 could release dissolved and surface bound Fe2+, both of which contributed to the activation of persulfate together. Meanwhile, cysteine was not rapidly consumed due to a regeneration process, which was beneficial for maintaining Fe2+/Fe3+ cycle and constantly accelerating the activation of persulfate for atrazine degradation. The reused Fe3O4 and cysteine in the Cysteine/Fe3O4/Persulfate process exhibited high stability for the atrazine degradation after three cycles. The degradation pathway of atrazine included alkylic-oxidation, dealkylation, dechlorination-hydroxylation processes. The present study indicates the novel Cysteine/Fe3O4/Persulfate process might be a high potential for treatment of organic polluted water.

Physiological and transcriptomic changes drive robust responses in Paenarthrobacter sp. AT5 to co-exposure of sulfamethoxazole and atrazine

Agricultural waterways are often contaminated with herbicide and antibiotic residues due to the widespread use of these chemicals in modern agriculture. The search for resistant bacterial strains that can adapt to and degrade these mixed contaminants is essential for effective in situ bioremediation. Herein, by integrating chemical and transcriptomic analyses, we shed light on mechanisms through which Paenarthrobacter sp. AT5, a well-known atrazine-degrading bacterial strain, can adapt to sulfamethoxazole (SMX) while degrading atrazine. When exposed to SMX and/or atrazine, strain AT5 increased the production of extracellular polymeric substances and reactive oxygen species, as well as the rate of activity of antioxidant enzymes. Atrazine and SMX, either alone or combined, increased the expression of genes involved in antioxidant responses, multidrug resistance, DNA repair, and membrane transport of lipopolysaccharides. Unlike atrazine alone, co-exposure with SMX reduced the expression of genes encoding enzymes involved in the lower part of the atrazine degradation pathway. Overall, these findings emphasize the complexity of bacterial adaptation to mixed herbicide and antibiotic residues and highlight the potential of strain AT5 in bioremediation efforts.

Enhanced generation of oxysulfur radicals by the BiOBr/Montmorillonite activated sulfite system: Performance and mechanism

The easily synthesized, cost-effective, and stable photocatalysts for sulfite activation are always required for the enhancement of organic contaminants degradation. Herein, the facile coprecipitation synthesis of Bismuth oxybromide (BiOBr)/Montmorillonite (MMT) was reported, which could activate sulfite (SO32−/HSO3−) under sunlight and accelerate the catalytic performance more effectively than pristine BiOBr. After adding sulfite to the photocatalysis system, the photodegradation efficiency of atrazine (ATZ) achieved 73.7% ± 1.5% after 5 min and 94.4% ± 1.6% after 30 min of sunlight irradiation with BiOBr/MMT. The BiOBr/MMT-sulfite system also presented remarkable photocatalytic performance to eliminate various contaminants, including ciprofloxacin, sulfadiazine, tetracycline, and carbamazepine. The various features of the photocatalyst materials were studied, including their surface morphology, structure, optical properties, and composition. The results illustrated that by adding MMT, the bandgap of the pristine BiOBr was reduced and the surface area was increased, which led to an increased ability to adsorb materials. Results of various influence factors showed this enhanced system had satisfactory and stable removal performance of ATZ in the pH range of 3.0–6.5, but HPO42− had a strong negative effect on the system performance. Oxysulfur radicals (SO5·- and SO4·-), h+, and 1O2 were discovered as the prevailing active species in the BiOBr/MMT-sulfite system. The proposed degradation mechanism of this photocatalyst-enhanced system revealed that sulfite adsorption on the surface of the photocatalyst played a vital role during the initial phase, and the degradation pathway of ATZ was discussed. This study provides a new synthesis strategy of a photocatalyst for sulfite activation and expands the potential uses of Bi-based photocatalysts in degrading difficult-to-remove organic pollutants.

Evaluation of basalt powder as a natural heterogeneous catalyst in photo-Fenton like treatment of atrazine

Basalt powder was employed to degrade atrazine (ATZ) under ultra-violet (UV-C) and visible light (vis) irradiation. The characterization of clay catalyst samples was confirmed the presence of ferrous oxide responsible of the heterogeneous photo-Fenton like reactions. Initial tests, using an ATZ concentration of 20 mg L−1 and raw basalt (B-R) form, validated the photo-Fenton like process as the most efficient. The optimal conditions were identified to be: an initial pH of approximately 6, basalt sintered at 600 °C (B-600) with dosage of 0.5 g L−1 under UV-C and 0.75 g L−1 under vis, and initial H2O2 concentration of 1.6 mM. Consequently, ATZ removal (initially at 5 mg L−1) was measured at 96.0% and 55.8% under UV-C and vis light, respectively, after 180 min of irradiation, with reusability of three cycles. The efficiency of the photo-Fenton process was further investigated by monitoring the toxicity bioassays of growth bacteria inhibition and phytotoxicity of the treated solutions. The results indicated that, under both UV and Vis irradiation, even with high ATZ removal efficiency, the toxicity of the process effluent is less than the initial sample. The initial degradation products were determined by high performance liquid chromatography (HPLC), and ATZ degradation pathway in the photo-Fenton like system was proposed, in which the reaction is primarily initiated by alkylic oxidation. Finally, the reaction’s inhibition upon addition of isopropanol and chloroform as scavengers emphasized the significant role of hydroxyl radicals over superoxide in the oxidation of ATZ.

Degradation pathways of atrazine by electrochemical oxidation at different current densities: Identifications from compound-specific isotope analysis and DFT calculation

Current density was the key factor that impacted pollutant degradation by electrochemical oxidation, and reaction contributions at various current densities were non-negligible for the cost-effective treatments of organic pollutants. This research introduced compound specific isotope analysis (CSIA) into atrazine (ATZ) degradation by boron doped diamond (BDD) with current density of 2.5–20 mA/cm2, in order to provide “in-situ” and “fingerprint” analysis of reaction contributions with changed current densities. As results, the increased current density displayed a positive impact on ATZ removal. The ɅC/H values (correlations of Δδ13C and Δδ2H) were 24.58, 9.18 and 8.74 when current densities were 20, 4, and 2.5 mA/cm2, with ·OH contribution of 93.5%, 77.2% and 80.35%, respectively. While DET process favored lower current density with contribution rates up to ∼20%. What's more interesting, though the carbon and hydrogen isotope enrichment factors (εC and εH) were fluctuate, the ɅC/H linearly increased accompanied with applied current densities. Therefore, increasing current density was effective due to the larger ·OH contribution even though side reactions may occur. DFT calculations proved the increase of C–Cl bond length and the delocalization of Cl atom, confirming dechlorination reaction mainly occurred in the direct electron transfer process. While ·OH radical mainly attack the C–N bond on the side chain, which was more benefit to the fast decomposition of ATZ molecule and intermediates. It was forceful to discuss pollutant degradation mechanism by combining CSIA and DFT calculations. Target bond cleavage (i.e., dehalogenation reaction) can be conducted by changing reaction conditions like current density due to the significantly different isotope fractionation and bond cleavage.

Enhanced degradation of herbicides in groundwater using sulfur-containing reductants and spinel zinc ferrite activated persulfate

A challenge to successfully implementing an injection-based remedial treatment in aquifers is to ensure that the oxidative reaction is efficient and lasts long enough to contact the contaminated plume. Our objective was to determine the efficacy of zinc ferrite nanocomposites (ZnFe2O4) and sulfur-containing reductants (SCR) (i.e., dithionite; DTN and bisulfite; BS) to co-activate persulfate (S2O82−; PS) and treat herbicide-contaminated water. We also evaluated the ecotoxicity of the treated water. While both SCRs delivered excellent PS activation in a 1:0.4 ratio (PS:SCR), the reaction was relatively short-lived. By including ZnFe2O4 in the PS/BS or PS/DTN activations, herbicide degradation rates dramatically increased by factors of 2.5 to 11.3. This was due to the SO4− and OH reactive radical species that formed. Radical scavenging experiments and ZnFe2O4 XPS spectra results revealed that SO4− was the dominant reactive species that originated from S(IV)/PS activation in solution and from the Fe(II)/PS activation that occurred on the ZnFe2O4 surface. Based on liquid chromatography mass spectrometry (LC–MS), atrazine and alachlor degradation pathways are proposed that involve both dehydration and hydroxylation. In 1-D column experiments, five different treatment scenarios were run using 14C-labeled and unlabeled atrazine, and 3H2O to quantify changes in breakthrough curves. Our results confirmed that ZnFe2O4 successfully prolonged the PS oxidative treatment despite the SCR being completely dissociated. Toxicity testing showed treated 14C-atrazine was more biodegradable than the parent compound in soil microcosms. Post-treatment water (25 %, v/v) also had less impact on both Zea Mays L. and Vigna radiata L. seedling growth, but more impact on root anatomies, while ≤4 % of the treated water started to exert cytotoxicity (<80 % viability) on ELT3 cell lines. Overall, the findings confirm that ZnFe2O4/SCR/PS reaction is efficient and relatively longer lasting in treating herbicide-contaminated groundwater.

Remediation of atrazine-contaminated soil in a fluidized-bed DBD plasma reactor

In this study, an innovative approach combining dielectric barrier discharge (DBD) plasma and fluidized-bed techniques is proposed and employed to remediate atrazine (ATZ) contaminated soil. Compared with traditional fixed-bed plasma soil remediation system, the fluidized-bed DBD plasma soil remediation system ensures sufficient and uniform contact between the chemically reactive species and the fluidized soil particles, thereby improving the migration and infiltration of reactive species in the soil layer and achieving high-efficiency remediation of contaminated soil. The optimum removal efficiency of 91.2% and energy efficiency of 0.342 mg/kJ were achieved, respectively, after only 6 min fluidized-bed DBD plasma treatment, which were 35.5% and 38.9% higher than those in a fixed-bed DBD plasma system. The primary organic intermediates after fluidized-bed DBD plasma treatment were identified, and the toxicological evaluation of intermediates was performed. Additionally, possible degradation pathways of ATZ in the fluidized-bed DBD plasma reactor were proposed. This system may offer an ideal approach to facilitate mass transfer between chemically reactive species and contaminants on the surface of soil particles, which is expected to achieve efficient, rapid, and continuous treatment of actual contaminated soil.

Remediation of atrazine contaminated soil by microwave activated persulfate system: Performance, mechanism and DFT calculation

Effective remediation of pesticide-contaminated sites is challenging due to high concentrations of pollutants with complete habitat destruction. Herein, microwave (MW)-activated persulfate (PS) system was proposed for remediation of organochlorine pesticide contaminated soil with atrazine (ATZ) as representation. The results revealed that the MW/PS system could achieve 97.9% of ATZ (50 mg/kg) degradation after treatment of 60 min, superior to that by conventional heat-activated PS. And more excellent degradation performance was identified in relatively higher microwave temperature (80 °C) with appropriate PS concentration (24 mmol/L), MW power (400 W) and water-soil ratio (1:1). Moreover, the MW/PS system possessed high tolerance to co-existing substances including Cl−, HCO3− and H2PO4−, and appropriate organic substance content favored ATZ degradation in soil. Reactive oxygen species consisting of SO4•−, OH•, O2•− and 1O2 contributed to ATZ decomposition, among which O2∙− played a principal role. The ATZ degradation pathway was then elucidated by combination of HPLC/MS spectra and DFT calculations, and ATZ overall toxicity was effectively alleviated in MW/PS system in term of toxicity assessment. Additionally, the MW/PS system presented high-performance degradation on such organochlorine pesticides as trichloro ethylene, tetrachloride, hexachlorobenzene and chlordane, suggesting great potentials of this system for remediation of organochlorine pesticides contaminated sites.

Degradation of atrazine in river sediment by dielectric barrier discharge plasma (DBDP) combined with a persulfate (PS) oxidation system: response surface methodology, degradation mechanisms, and pathways.

Single degradation systems based on dielectric barrier discharge plasma (DBDP) or persulfate (PS) oxidation cannot achieve the desired goals (high degradation efficiency, high mineralization rate, and low product toxicity) of degrading atrazine (ATZ) in river sediment. In this study, DBDP was combined with a PS oxidation system (DBDP/PS synergistic system) to degrade ATZ in river sediment. A Box-Behnken design (BBD) including five factors (discharge voltage, air flow, initial concentration, oxidizer dose, and activator dose) and three levels (- 1, 0, and 1) was established to test a mathematical model by response surface methodology (RSM). The results confirmed that the degradation efficiency of ATZ in river sediment was 96.5% in the DBDP/PS synergistic system after 10min of degradation. The experimental total organic carbon (TOC) removal efficiency results indicated that 85.3% of ATZ is mineralized into CO2, H2O, and NH4+, which effectively reduces the possible biological toxicity of the intermediate products. Active species (sulfate (SO4•-), hydroxy (•OH), and superoxide (•O2-) radicals) were found to exert positive effects in the DBDP/PS synergistic system and illustrated the degradation mechanism of ATZ. The ATZ degradation pathway, composed of 7 main intermediates, was clarified by Fourier transform infrared spectroscopy (FTIR) and gas chromatography-mass spectrometry (GC-MS). This study indicates that the DBDP/PS synergistic system is a highly efficient, environmentally friendly, novel method for the remediation of river sediment containing ATZ pollution.

Characterization and novel pathway of atrazine catabolism by Agrobacterium rhizogenes AT13 and its potential for environmental bioremediation

Agrobacterium rhizogenes AT13, a novel bacterial strain that was isolated from contaminated soil, could utilize atrazine as the sole nitrogen, thereby degrading it. Optimization of the degradation reaction using a Box–Behnken design resulted in 99.94% atrazine degradation at pH 8.57, with an inoculum size of 3.10 × 109 CFU/mL and a concentration of 50 mg/L atrazine. Ultra-high performance liquid chromatography-electrospray ionization-high resolution mass spectrometry (UPLC-ESI-HRMS), liquid chromatography tandem mass spectrometry (LC-MS/MS) and high performance liquid chromatography (HPLC) analyses identified and quantified six reported metabolites and a novel metabolite (2-hydroxypropazine) from atrazine degradation by AT13. On the basis of these metabolites, we propose an atrazine degradation pathway that includes dichlorination, hydroxylation, deamination, dealkylation and methylation reactions. The toxicity of the degradation products was evaluated by Toxicity Estimation Software Tool (T.E.S.T). Bioaugmentation of atrazine-polluted soils/water with strain AT13 significantly improved the atrazine removal rate. Thus, AT13 has potential applications in bioremediation.