Enantioselective Phytotoxic Disturbances of Fatty Acids in Arabidopsis thaliana by Dichlorprop.

Plant fatty acids have indispensable physiological functions and nutritional value. However, the overuse of herbicides may cause phytotoxic disturbances of fatty acids in nontarget plants while spraying for weeds. Evidence has shown that the herbicide dichlorprop can inhibit the activity of acetyl-CoA carboxylase (ACCase), a key enzyme involved in fatty acid synthesis. However, the enantioselective phytotoxic effects of dichlorprop enantiomers ((R)-dichlorprop and (S)-dichlorprop) on fatty acids and their related mechanisms remain unclear. To solve this issue, the enantioselective phytotoxicity of dichlorprop in the model plant species Arabidopsis thaliana (A. thaliana) with a focus on fatty acids was evaluated for the first time. The results indicated a significant difference in enantioselectivity and that exposure to (R)-dichlorprop can cause marked fatty acid disturbances in nontarget plant species. Specifically, (R)-dichlorprop decreased the content of three fatty acids by more than 50% by inhibiting the activity of ACCase. In addition, increased malondialdehyde (MDA) and lipid hydroperoxides (LOOHs) contents and membrane permeability reflected herbicide-induced lipid peroxidation, which decreased the unsaturation of fatty acids in membranes and further influenced membrane composition and function. Moreover, an increased level of glutathione peroxidase (GPX) and cytochrome P450 (CYP450) reflected a plant stress-induced response. To summarize, fatty acids represent a new perspective for evaluating the toxicity of chiral pesticides, contributing to a better understanding of the enantioselective phytotoxicity and mechanisms of dichlorprop, and providing evidence for herbicide security and risk assessments.

Fe-N-Graphene Wrapped Al2O3/Pentlandite from Microalgae: High Fenton Catalytic Efficiency from Enhanced Fe3+ Reduction.

Efficient cycling of Fe3+/Fe2+ is a key step for the Fenton reaction. In this exploration, from microalgae, we have prepared a novel Fe-N-graphene wrapped Al2O3/pentlandite composite which showed high Fenton catalytic ability through accelerating of Fe3+ reduction. The catalyst exhibits high activity, good reusability along with stability, and wide adaptation for the organics degradation under neutral pH. High TON and H2O2 utilization efficiency have also reached by this catalyst. Characterization results disclose a unique structure that the layered Fe-N-graphene structure tightly covers on Al2O3/pentlandite particles. Mechanistic evidence suggests that the accelerated Fe3+/Fe2+ redox cycle originates from the enhanced electron transfer by the synergistic effect of Fe, Ni and Al in the catalyst, and it causes the low H2O2 consumption and high •OH generation rate. Moreover, organic radicals formed in the Fenton process also participate in the Fe3+ reduction, and this process may be accelerated by the N doped graphene through a quick electron transfer. These findings stimulate an approach with great potential to further extend the synthetic power and versatility of Fenton catalysis through N doped graphene in catalysts.

Enantioselective Phytotoxicity of Dichlorprop to Arabidopsis thaliana: The Effect of Cytochrome P450 Enzymes and the Role of Fe.

The ecotoxicology effects of chiral herbicides have long been recognized and have drawn increasing attention. The toxic mechanisms of herbicides in plants are involved in production of reactive oxygen species (ROS) and cause damage to target enzymes, but the relationship between these two factors in the enantioselectivity of chiral herbicides has rarely been investigated. Furthermore, even though cytochromes P450 enzymes (CYP450s) have been related to the phytotoxicity of herbicides, their roles in the enantioselectivity of chiral herbicides have yet to be explored. To solve this puzzle, the CYP450s suicide inhibitor 1-aminobenzotriazole (ABT) was added to an exposure system made from dichlorprop (DCPP) enantiomers in the model plant Arabidopsis thaliana. The results indicated that different phytotoxicities of DCPP enantiomers by causing oxidative stress and acetyl-CoA carboxylase (ACCase) damage were observed in the presence and the absence of ABT. The addition of ABT decreased the toxicity of (R)-DCPP but was not significantly affected that of (S)-DCPP, resulting in smaller differences between enantiomers. Furthermore, profound differences were also observed in Fe uptake and distribution, exhibiting different distribution patterns in A. thaliana leaves exposed to DCPP and ABT, which helped bridge the relationship between ROS production and target enzyme ACCase damage through the function of CYP450s. These results offer an opportunity for a more-comprehensive understanding of chiral herbicide action mechanism and provide basic evidence for risk assessments of chiral herbicides in the environment.

Phthalate degradation by glow discharge plasma enhanced with pyrite in aqueous solution.

In order to prevent health risk from potential exposures to phthalates, a glow discharge plasma (GDP) process was applied for phthalate degradation in aqueous solution. The results revealed that the phthalate derivatives 4-hydroxyphthalic acid, 4-methylphthalic acid and 4-tert-butylphthalic anhydride could be degraded efficiently in GDP process (498 V, 0.2 A) with high removal efficiencies of over 99% in 60 minutes. Additionally, pyrite as a promising heterogeneous iron source in the Fenton reaction was found to be favorable for GDP process. The phthalate degradation reaction could be significantly enhanced by the continuous formation of •OH and the inhibition of the quenching reaction in the pyrite Fenton system due to the constant dissolution of Fe(II) from pyrite surface. Meanwhile, the initial pH value showed little impact on the degradation of phthalates and the energy efficiency of GDP system for phthalate degradation ranged between 0.280 × 10-9 and 1.210 × 10-9 mol/J, which is similar to the GDP system with phenol, bisphenol A and methyl tert-butyl ether as the substrates. Further, the X-ray diffraction and scanning electron microscopy with energy dispersive X-ray spectroscopy analyses indicated that the pyrite was relatively stable in GDP system and there was no obvious polymeric compound formed on the catalyst surface. Overall, this GDP process offers high removal efficiency, simple technology, considerable energy efficiency and the applicability to salt-containing phthalate wastewater.

A Petroleum Vapor Intrusion Model Involving Upward Advective Soil Gas Flow Due to Methane Generation.

At petroleum vapor intrusion (PVI) sites at which there is significant methane generation, upward advective soil gas transport may be observed. To evaluate the health and explosion risks that may exist under such scenarios, a one-dimensional analytical model describing these processes is introduced in this study. This new model accounts for both advective and diffusive transport in soil gas and couples this with a piecewise first-order aerobic biodegradation model, limited by oxygen availability. The predicted results from the new model are shown to be in good agreement with the simulation results obtained from a three-dimensional numerical model. These results suggest that this analytical model is suitable for describing cases involving open ground surface beyond the foundation edge, serving as the primary oxygen source. This new analytical model indicates that the major contribution of upward advection to indoor air concentration could be limited to the increase of soil gas entry rate, since the oxygen in soil might already be depleted owing to the associated high methane source vapor concentration.

A novel (S)-6-hydroxynicotine oxidase gene from Shinella sp. strain HZN7.

Nicotine is an important environmental toxicant in tobacco waste. Shinella sp. strain HZN7 can metabolize nicotine into nontoxic compounds via variations of the pyridine and pyrrolidine pathways. However, the catabolic mechanism of this variant pathway at the gene or enzyme level is still unknown. In this study, two 6-hydroxynicotine degradation-deficient mutants, N7-M9 and N7-W3, were generated by transposon mutagenesis. The corresponding mutant genes, designated nctB and tnp2, were cloned and analyzed. The nctB gene encodes a novel flavin adenine dinucleotide-containing (S)-6-hydroxynicotine oxidase that converts (S)-6-hydroxynicotine into 6-hydroxy-N-methylmyosmine and then spontaneously hydrolyzes into 6-hydroxypseudooxynicotine. The deletion and complementation of the nctB gene showed that this enzyme is essential for nicotine or (S)-6-hydroxynicotine degradation. Purified NctB could also convert (S)-nicotine into N-methylmyosmine, which spontaneously hydrolyzed into pseudooxynicotine. The kinetic constants of NctB toward (S)-6-hydroxynicotine (Km = 0.019 mM, kcat = 7.3 s(-1)) and nicotine (Km = 2.03 mM, kcat = 0.396 s(-1)) indicated that (S)-6-hydroxynicotine is the preferred substrate in vivo. NctB showed no activities toward the R enantiomer of nicotine or 6-hydroxynicotine. Strain HZN7 could degrade (R)-nicotine into (R)-6-hydroxynicotine without any further degradation. The tnp2 gene from mutant N7-W3 encodes a putative transposase, and its deletion did not abolish the nicotine degradation activity. This study advances the understanding of the microbial diversity of nicotine biodegradation.

Protection against Cu(II)-induced oxidative stress and toxicity to Chlorella vulgaris by 2,2'-Bipyridine-5,5'-dicarboxylic acid.

In this study, we evaluated the role of 2,2'-bipyridine-5,5'-dicarboxylic acid (Bpy-COOH) in protecting Chlorella vulgaris from the oxidative stress and toxicity induced by Cu(II). Both in vivo and in vitro tests were performed. Different addition orders of Bpy-COOH and Cu(II) were tried in the former, whereas different Bpy-COOH concentrations were used in both experiments. The in vivo experiments showed that the production of reactive oxygen species in C. pyrenoidosa treated by the addition of Bpy-COOH and Cu(II) in three orders were all significantly less than that in cases treated with only Cu(II). In vitro tests indicated that peroxidase-like complexes could be formed between Bpy-COOH and Cu(II). Based on these results, it could be concluded that the use of Bpy-COOH could significantly decrease Cu(II) toxicity to algal cells by forming peroxidase-like complexes.

Regulatory potential of secondary metabolite DIMBOA and baicalein to imazethapyr-induced toxicity in wheat seedlings.

Controlling and mitigating the toxicity of herbicides to non-target plants is of significant importance in reducing ecological risks. The development of green and natural herbicide control technologies has become an urgent necessity. In this paper, how 2,4-dihydroxy-7-methoxy-2H-1,4-benzoxazine-3(4H)-one (DIMBOA) and baicalein alleviated oxidative stress induced by imazethapyr (IM) in wheat seedlings was investigated. We found that DIMBOA and baicalein enhanced the antioxidant enzyme activities in wheat seedlings exposed to IM and reduced the excessive reactive oxygen species due to IM stress by 21.3% and 23.5%, respectively. DIMBOA and baicalein also restored the iron content reduced by IM and effectively mitigated Fe2+ overload by alleviating the response of heme oxygenase 1 to IM stress. The antioxidant and iron homeostatic maintenance properties of DIMBOA and baicalein enhanced the defenses of wheat seedlings against IM stress. Our results highlight the potential implication of secondary metabolites as natural products to modulate herbicide toxicity to non-target plants.

Chiral herbicide imazethapy influences plant-soil feedback on nitrogen metabolism by shaping rhizosphere microorganisms.

Herbicides are known to affect the soil nitrogen cycle by shaping soil microorganisms. However, it is not clear how herbicides regulate diverse transformation processes of soil nitrogen cycling by altering rhizosphere microorganisms, subsequently influencing the feedback to plant nitrogen metabolism. Here, we investigated how imazethapyr (IM) enantiomers drive plant-soil feedback on nitrogen metabolism by altering the rhizosphere microorganisms. The results indicated that (R)- and (S)-IM significantly changed the composition and structure rhizosphere microbiome with enantioselectivity and functional changes in microbial communities were associated with soil nitrogen circulation. The determination of nitrogen-cycling functional genes further supported the above findings. The results revealed that (R)- and (S)-IM could change the abundance of nitrogen-cycling functional genes by changing specific bacteria abundances, such as Bacteroidetes, Proteobacteria, and Acidobacteria, thus resulting in diverse nitrogen transformation processes. The alternation of nitrogen transformation processes indicated (R)-IM exhibited a more notable tendency to form a nitrogen cycling pattern with lower energy cost and higher nitrogen retention than (S)-IM. Sterilization experiments demonstrated changes in soil nitrogen cycling drive plant nitrogen metabolism and rhizosphere microorganisms are responsible for the above process of plant-soil feedback for nitrogen metabolism. Under IM enantiomer treatments, rhizosphere microorganisms might stimulate glutamate synthesis by promoting NH4+ uptake and glutamine-glutamate synthesis cycling in roots, thus contributing to positive feedback, with (R)-IM treatments showing more pronounced positive feedback on nitrogen metabolism than (S)-IM treatments. Our results provide theoretical support for determining the mechanism by which IM enantiomers drive plant-soil nitrogen metabolism by changing the rhizosphere microbial communities.

Dual-Mediated Roles of H+-ATPase in Alleviating the Phytotoxicity of Imazethapyr to Nontarget Wheat.

The regulation solutions and mechanisms of reducing pesticide phytotoxicity to nontarget plants are not well-defined and detailed. Here, we have proposed a new detoxification strategy to control the toxic effects of herbicide imazethapyr (IM) induced in wheat seedlings from the perspective of the plasma membrane (PM) H+-ATPase. We found that the changes in PM H+-ATPase activity have a regulatory effect on the phytotoxic effects induced by IM in plants. Treatment with PM H+-ATPase activators restored the reduced auxin content and photosynthetic efficiency caused by IM, thereby promoting plant growth. Application of a PM H+-ATPase inhibitor further reduced phosphorus content and significantly increased 2,4-dihydroxy-7-methoxy-2H,1,4-benzoxazin-3(4H)one (DIMBOA) and jasmonic acid levels. These effects indicate that auxin and DIMBOA may regulate plant growth trends and detoxification effects mediated by PM H+-ATPase. This work opens a new strategy for regulating herbicide toxicity to nontarget plants from the PM H+-ATPase.

Dynamic changes of fatty acids and (R)-dichlorprop toxicity in Arabidopsis thaliana: correlation, mechanism, and implications.

Plant fatty acids (FAs) are critical components of lipids and play an important role in coping with pollution-induced stress. However, the relationship between the fluctuating changes of FAs and the toxic effects of pollutants is not clear. Here, we analyzed and identified 19 FAs, namely 14 medium and long chain fatty acids (MLCFAs) and 5 very long chain fatty acids (VLCFAs). First, a positive correlation between plant biomass and LCFA content was observed. Changes in unsaturation were inversely related to cell membrane permeability, which serves as an indicator of the toxic effects. In particular, the use of herbicides led to a reduction in total FA content, but caused a significant increase in free fatty acids (FFAs), which facilitate oxidative stress. In addition, supplementation with exogenous FAs, particularly linoleic and alpha-linolenic acids, effectively alleviated the toxic inhibition. (R)-dichlorprop causes abnormal FA metabolism that can be reversed by ferrostatin-1, a ferroptosis inhibitor. Under (R)-dichlorprop exposure, the balance of FA unsaturation in plants is disrupted by inhibition of FA desaturase activity, ultimately leading to ferroptosis and disruption of cell membrane integrity. This study aims to enhance the understanding of the ecotoxic effects of herbicides by examining changes in FAs. The findings will provide a scientific basis for controlling environmental risks associated with hazardous substances.

Plasma Membrane (PM) H+-ATPase Mediates Rhizosphere Acidification and Regulates Herbicide Imazethapyr Toxicity in Wheat.

The plasma membrane (PM) H+-ATPase is crucial for a plant defense system. However, there is currently no consensus on whether the PM H+-ATPase plays a role in alleviating the toxic effects of herbicides on nontarget plants. We found that under the herbicide imazethapyr (IM) exposure, PM H+-ATPase activity in wheat roots increased by approximately 69.53%, leading to rhizosphere acidification. When PM H+-ATPase activity is inhibited, the toxicity of IM significantly increases: When exposed to IM alone, the total Fe content of wheat roots decreased by 29.07%, the relative Fe2+ content increased by 27.75%, and the ROS content increased by 27.74%. When the PM H+-ATPase activity was inhibited, the corresponding data under IM exposure were 37.36%, 215%, and 57.68%, respectively. This work delves into the role of PM H+-ATPase in mediating the detoxification mechanism in plants exposed to herbicides, offering new insights into enhancing crop resistance against herbicides.

Mechanisms Underlying Allelopathic Disturbance of Herbicide Imazethapyr on Wheat and Its Neighboring Ryegrass (Lolium perenne).

As representatives of allelopathy, weeds consistently coexist with crops, exhibiting mutual growth inhibition. At the same time, herbicides are usually employed to control weeds. However, few studies have investigated how herbicides will affect allelopathy between crops and their neighboring weeds. Our findings suggested that allelopathic-induced phenotypic variations in ryegrass were reduced in the presence of the herbicide imazethapyr (IM), consistent with the antioxidant system analysis results. Additionally, IM affected the levels of allelochemical hydroxamic acid (Hx) in both plants. Hydroponic experiments revealed that this impact was due to the accelerated transportation of Hx from wheat to ryegrass, driven by ryegrass-secreted jasmonic acid. This study holds paramount significance for comprehending the effects of herbicides on the allelopathic interactions between nontargeted crops and neighboring weeds, contributing to an enhanced understanding of herbicides on plant species interactions.

Effects of polystyrene microplastic composite with florfenicol on photosynthetic carbon assimilation of rice (Oryza sativa L.) seedlings: Light reactions, carbon reactions, and molecular metabolism.

The effects of co-exposure to antibiotics and microplastics in agricultural systems are still unclear. This study investigated the effects of florfenicol (FF) and polystyrene microplastics (PS-MPs) on photosynthetic carbon assimilation in rice seedlings. Both FF and PS-MPs inhibited photosynthesis, while PS-MPs can alleviate the toxicity of FF. Chlorophyll synthesis genes (HEMA, HEMG, CHLD, CHLG, CHLM, and CAO) were down-regulated, whereas electron transport chain genes (PGR5, PGRL1A, PGRL1B, petH, and ndhH) were up-regulated. FF inhibited linear electron transfer (LET) and activated cyclic electron transfer (CET), which was consistent with the results of the chlorophyll fluorescence parameters. The photosynthetic carbon assimilation pathway was altered, the C3 pathway enzyme Ribulose1,5-bisphosphatecarboxylase/oxygenase (RuBisCO) was affected, C4 enzyme ((phosphoenolpyruvate carboxykinase (PEPCK), pyruvate orthophosphate dikinase (PPDK), malate dehydrogenase (MDH), and phosphoenolpyruvate carboxylase (PEPC))) and related genes were significantly up-regulated, suggesting that the C3 pathway is converted to C4 pathway for self-protection. The key enzymes involved in photorespiration, glycolate oxidase (GO) and catalase (CAT), responded positively, photosynthetic phosphorylation was inhibited, and ATP content and H+-ATPase activity were suppressed, nutrient content (K, P, N, Ca, Mg, Fe, Cu, Zn, Mn, and Ni) significantly affected. Transcriptomic analysis showed that FF and PS-MPs severely affected the photosynthetic capacity of rice seedlings, including photosystem I, photosystem II, non-photochemical quenching coefficients, and photosynthetic electron transport.

Cloning of a novel nicotine oxidase gene from Pseudomonas sp. strain HZN6 whose product nonenantioselectively degrades nicotine to pseudooxynicotine.

Pseudomonas sp. strain HZN6 utilizes nicotine as its sole source of carbon, nitrogen, and energy. However, its catabolic mechanism has not been elucidated. In this study, self-formed adaptor PCR was performed to amplify the upstream sequence of the pseudooxynicotine amine oxidase gene. A 1,437-bp open reading frame (designated nox) was found to encode a nicotine oxidase (NOX) that shows 30% amino acid sequence identity with 6-hydroxy-l-nicotine oxidase from Arthrobacter nicotinovorans. The nox gene was cloned into a broad-host-range cloning vector and transferred into the non-nicotine-degrading bacteria Escherichia coli DH5α (DH-nox) and Pseudomonas putida KT2440 (KT-nox). The transconjugant KT-nox obtained nicotine degradation ability and yielded an equimolar amount of pseudooxynicotine, while DH-nox did not. Reverse transcription-PCR showed that the nox gene is expressed in both DH5α and KT2440, suggesting that additional factors required for nicotine degradation are present in a Pseudomonas strain(s), but not in E. coli. The mutant of strain HZN6 with nox disrupted lost the ability to degrade nicotine, but not pseudooxynicotine. These results suggested that the nox gene is responsible for the first step of nicotine degradation. The (RS)-nicotine degradation results showed that the two enantiomers were degraded at approximately the same rate, indicating that NOX does not show chiral selectivity. Site-directed mutagenesis revealed that both the conserved flavin adenine dinucleotide (FAD)-binding GXGXXG motif and His456 are essential for nicotine degradation activity.

Phytotoxicity alleviation of imazethapyr to non-target plant wheat: active regulation between auxin and DIMBOA.

Effectively controlling target organisms while reducing the adverse effects of pesticides on non-target organisms is a crucial scientific inquiry and challenge in pesticide ecotoxicology research. Here, we studied the alleviation of herbicide (R)-imazethapyr [(R)-IM] to non-target plant wheat by active regulation between auxin and secondary metabolite 2,4-dihydroxy-7-methoxy-2H-1,4-benzoxazine-3(4H)-one (DIMBOA). We found (R)-IM reduced 32.4% auxin content in wheat leaves and induced 40.7% DIMBOA accumulation compared to the control group, which effortlessly disrupted the balance between wheat growth and defense. Transcriptomic results indicated that restoration of the auxin level in plants promoted the up-regulation of growth-related genes and the accumulation of DIMBOA up-regulated the expression of defense-related genes. Auxin and DIMBOA alleviated herbicide stress primarily through effects in the two directions of wheat growth and defense, respectively. Additionally, as a common precursor of auxin and DIMBOA, indole adopted a combined growth and defense strategy in response to (R)-IM toxicity, i.e., restoring growth development and enhancing the defense system. Future regulation of auxin and DIMBOA levels in plants may be possible through appropriate methods, thus regulating the plant growth-defense balance under herbicide stress. Our insight into the interference mechanism of herbicides to the plant growth-defense system will facilitate the design of improved strategies for herbicide detoxification.

Comparative study of the toxicity mechanisms of quinolone antibiotics on soybean seedlings: Insights from molecular docking and transcriptomic analysis.

The ecological effects of quinolone antibiotics (QNs) on non-target organisms have received widespread attention. The toxicological mechanisms of three common QNs, that is, enrofloxacin, levofloxacin, and ciprofloxacin, on soybean seedlings were investigated in this study. Enrofloxacin and levofloxacin caused significant growth inhibition, ultrastructural alterations, photosynthetic suppression, and stimulation of the antioxidant system, with levofloxacin exhibiting the strongest toxic effects. Ciprofloxacin (<1 mg·L-1) did not have a significant effect on the soybean seedlings. As the concentrations of enrofloxacin and levofloxacin increased, antioxidant enzyme activities, malondialdehyde content, and hydrogen peroxide levels also increased. Meanwhile, the chlorophyll content and chlorophyll fluorescence parameters decreased, indicating that the plants underwent oxidative stress and photosynthesis was suppressed. The cellular ultrastructure was also disrupted, which was manifested by swollen chloroplasts, increased starch granules, disintegration of plastoglobules, and mitochondrial degradation. The molecular docking results suggested that the QNs have an affinity for soybean target protein receptors (4TOP, 2IUJ, and 1FHF), with levofloxacin having the highest binding energy (-4.97, -3.08, -3.8, respectively). Transcriptomic analysis has shown that genes were upregulated under the enrofloxacin and levofloxacin treatments were mainly involved in ribosome metabolism and processes to synthesize oxidative stress-related proteins. Downregulated genes in the levofloxacin treatment were primarily enriched in photosynthesis-related pathways, indicating that levofloxacin significantly inhibited gene expression for photosynthesis. Genes expression level by quantitative real-time PCR analysis was consistent with the transcriptomic results. This study confirmed the toxic effect of QNs on soybean seedlings, and provided new insights into the environmental risks of antibiotics.

Polystyrene microplastic attenuated the toxic effects of florfenicol on rice (Oryza sativa L.) seedlings in hydroponics: From the perspective of oxidative response, phototoxicity and molecular metabolism.

Antibiotics and microplastics (MPs) are two emerging pollutants in agroecosystems, however the effects of co-exposure to antibiotics and MPs remain unclear. The toxicity of florfenicol (FF) and polystyrene microplastics (PS-MPs) on rice seedlings was investigated. FF and PS-MPs caused colloidal agglomeration, which changed the environmental behavior of FF. FF inhibited rice growth and altered antioxidant enzyme (superoxide dismutase, peroxidase, and catalase) activities, leading to membrane lipid peroxidation; impaired photosynthetic systems, decreased photosynthetic pigments (Chlorophyll a, Chlorophyll b, and carotene), chlorophyll precursors (Proto IX, Mg-Proto IX, and Pchlide), photosynthetic and respiratory rates. The key photosynthesis related genes (PsaA, PsaB, PsbA, PsbB, PsbC, and PsbD) were significantly down-regulated. The ultrastructure of mesophyll cells was destroyed with chloroplast swelling, membrane surface blurring, irregular thylakoid lamellar structure, and number of peroxisomes increased. PS-MPs mitigated FF toxicity, and the IBR index values showed that 10 mg∙L-1 PS-MPs were more effective. Metabolomic analysis revealed that the abundance of metabolites and metabolic pathways were altered by FF, was greater than the combined "MPs-FF" contamination. The metabolism of amino acids, sugars, and organic acids were severely interfered. Among these, 15 metabolic pathways were significantly altered, with the most significant effects on phenylalanine metabolism and the citric acid cycle (p < 0.05).

Functional identification of two novel genes from Pseudomonas sp. strain HZN6 involved in the catabolism of nicotine.

Nicotine is a natural alkaloid produced by tobacco plants, and the mechanisms of its catabolism by microorganisms are diverse. In the present study, we reported the mutation, cloning, and identification of two novel genes involved in nicotine degradation from the newly isolated Pseudomonas sp. strain HZN6. Transposon mutagenesis identified a HZN6 mutant in which the nicotine-degrading pathway was blocked at pseudooxynicotine. A 3,874-bp DNA fragment flanking the transposon insertion site was obtained through self-formed adaptor PCR. Two open reading frames (designated pao and sap) were analyzed, and the deduced amino acid sequences shared 29% identity with 6-hydroxy-l-nicotine oxidase from Arthrobacter nicotinovorans and 49% identity with an aldehyde dehydrogenase from Bartonella henselae. Both pao and sap were cloned and functionally expressed in recombinant Escherichia coli BL21. The pao gene encoded a novel pseudooxynicotine amine oxidase with noncovalently bound flavin adenine dinucleotide (FAD) and exhibited substrate specificity removing the methylamine from pseudooxynicotine with the formation of 3-succinoylsemialdehyde-pyridine and hydrogen dioxide. The sap gene encoded a NADP(+)-dependent 3-succinoylsemialdehyde-pyridine dehydrogenase that catalyzed the dehydrogenation of 3-succinoylsemialdehyde-pyridine to 3-succinoyl-pyridine. Genetic analyses indicated that the pao gene played an essential role in nicotine or pseudooxynicotine mineralization in strain HZN6, whereas the sap gene did not. This study provides novel insight into the nicotine-degrading mechanism at the genetic level in Pseudomonas spp.

The strong promoting effects of thin layer Al2O3 on FeCu Fenton-like components: Enhanced electron transfer.

The Fe(III)/Fe(II) redox cycle is the main factor limiting the effectiveness of Fe-mediated advanced oxidation processes (AOPs) for the degradation of organic pollutants. In this study, the promoting effects of thin-layer Al2O3 (t-Al2O3) between the frequently used FeCu components and the mesoporous silica support were studied to reduce Fe(III) to promote the activity of the Fenton-like catalyst. After modification by t-Al2O3, the mesoporous silicon-loaded FeCu catalyst removed 97% of Rhodamine B at pH 7, which was superior to the unmodified sample with a removal rate of 62.4% under the same conditions. Morphological characterization and X-ray diffraction patterns indicated that the Fe-Cu/t-Al2O3 active components were highly dispersed. Pyridine infrared spectra suggested that all of the acid sites were Lewis acids, and the t-Al2O3-loaded samples provided moderate/strong Lewis acids. The loading of t-Al2O3 between the FeCu complex and mesoporous silica support facilitated electron transfer during the Fe(III)/Fe(II) redox cycle by enhancing the dispersion of Fe-Cu/t-Al2O3 and the Lewis acidity. The results of this study provide insight into how t-Al2O3 promoted the interactions between the active components and silica support and how it can be used to aid in the selection of suitable wastewater treatment technologies.