Arbuscular Mycorrhizal Fungus Alleviates Charged Nanoplastic Stress in Host Plants via Enhanced Defense-Related Gene Expressions and Hyphal Capture.

Contamination of small-sized plastics is recognized as a factor of global change. Nanoplastics (NPs) can readily enter organisms and pose significant ecological risks. Arbuscular mycorrhizal (AM) fungi are the most ubiquitous and impactful plant symbiotic fungi, regulating essential ecological functions. Here, we first found that an AM fungus, Rhizophagus irregularis, increased lettuce shoot biomass by 25-100% when exposed to positively and negatively charged NPs vs control, although it did not increase that grown without NPs. The stress alleviation was attributed to the upregulation of gene expressions involving phytohormone signaling, cell wall metabolism, and oxidant scavenging. Using a root organ-fungus axenic growth system treated with fluorescence-labeled NPs, we subsequently revealed that the hyphae captured NPs and further delivered them to roots. NPs were observed at the hyphal cell walls, membranes, and spore walls. NPs mediated by the hyphae were localized at the root epidermis, cortex, and stele. Hyphal exudates aggregated positively charged NPs, thereby reducing their uptake due to NP aggregate formation (up to 5000 nm). This work demonstrates the critical roles of AM fungus in regulating NP behaviors and provides a potential strategy for NP risk mitigation in terrestrial ecosystems. Consequent NP-induced ecological impacts due to the affected AM fungi require further attention.

Accurate Prediction of Rat Acute Oral Toxicity and Reference Dose for Thousands of Polycyclic Aromatic Hydrocarbon Derivatives Based on Chemometric QSAR and Machine Learning.

Acute oral toxicity is currently not available for most polycyclic aromatic hydrocarbons (PAHs), especially their derivatives, because it is cost-prohibitive to experimentally determine all of them. Here, quantitative structure-activity relationship (QSAR) models using machine learning (ML) for predicting the toxicity of PAH derivatives were developed, based on oral toxicity data points of 788 individual substances of rats. Both the individual ML algorithm gradient boosting regression trees (GBRT) and the stacking ML algorithm (extreme gradient boosting + GBRT + random forest regression) provided the best prediction results with satisfactory determination coefficients for both cross-validation and the test set. It was found that those PAH derivatives with fewer polar hydrogens, more large-sized atoms, more branches, and lower polarizability have higher toxicity. Software based on the optimal ML-QSAR model was successfully developed to expand the application potential of the developed model, obtaining reliable prediction of pLD50 values and reference doses for 6893 external PAH derivatives. Among these chemicals, 472 were identified as moderately or highly toxic; 10 out of them had clear environment detection or use records. The findings provide valuable insights into the toxicity of PAHs and their derivatives, offering a standard platform for effectively evaluating chemical toxicity using ML-QSAR models.

Development, Evaluation, and Application of Machine Learning Models for Accurate Prediction of Root Uptake of Per- and Polyfluoroalkyl Substances.

Machine learning (ML) models were developed for understanding the root uptake of per- and polyfluoroalkyl substances (PFASs) under complex PFAS-crop-soil interactions. Three hundred root concentration factor (RCF) data points and 26 features associated with PFAS structures, crop properties, soil properties, and cultivation conditions were used for the model development. The optimal ML model, obtained by stratified sampling, Bayesian optimization, and 5-fold cross-validation, was explained by permutation feature importance, individual conditional expectation plot, and 3D interaction plot. The results showed that soil organic carbon contents, pH, chemical logP, soil PFAS concentration, root protein contents, and exposure time greatly affected the root uptake of PFASs with 0.43, 0.25, 0.10, 0.05, 0.05, and 0.05 of relative importance, respectively. Furthermore, these factors presented the key threshold ranges in favor of the PFAS uptake. Carbon-chain length was identified as the critical molecular structure affecting root uptake of PFASs with 0.12 of relative importance, based on the extended connectivity fingerprints. A user-friendly model was established with symbolic regression for accurately predicting RCF values of the PFASs (including branched PFAS isomerides). The present study provides a novel approach for profound insight into the uptake of PFASs by crops under complex PFAS-crop-soil interactions, aiming to ensure food safety and human health.

Mechanism and Association between Microbial Nitrogen Transformation in Rhizosphere and Accumulation of Ciprofloxacin in Choysum (Brassica parachinensis).

Rhizosphere microbiota are an important factor impacting plant uptake of pollutants. However, little is known about how microbial nitrogen (N) transformation in the rhizosphere affects the uptake and accumulation of antibiotics in plants. Here, we determined recruitment of N transformation functional bacteria upon ciprofloxacin (CIP) exposure, by comparing differences in assembly processes of both rhizospheric bacterial communities and N transformation between two choysum (Brassica parachinensis) varieties differing in CIP accumulation. The low accumulation variety (LAV) of CIP recruited more host bacteria (e.g., Nitrospiria and Nitrolancea) carrying nitrification genes (mainly nxrA) but fewer host bacteria carrying denitrification genes, especially narG, relative to the high accumulation variety (HAV) of CIP. The nxrA and narG abundance in the LAV rhizosphere were, respectively, 1.6-7.8 fold higher and 1.4-3.4 fold lower than those in the HAV rhizosphere. Considering that nitrate can decrease CIP uptake into choysum through competing for the proton motive force and energy, such specific bacteria recruitment in LAV favored the production and utilization of nitrate in its rhizosphere, thus limiting its CIP accumulation with 1.6-2.4 fold lower than the HAV. The findings give insight into the mechanism underlying low pollutant accumulation, filling the knowledge gap regarding the profound effects of rhizosphere microflora and N transformation processes on antibiotic accumulation in crops.

Variety-Selective Rhizospheric Activation, Uptake, and Subcellular Distribution of Perfluorooctanesulfonate (PFOS) in Lettuce (Lactuca sativa L.).

Perfluorooctanesulfonate (PFOS) as an accumulative emerging persistent organic pollutant in crops poses severe threats to human health. Lettuce varieties that accumulate a lower amount of PFOS (low-accumulating crop variety, LACV) have been identified, but the regarding mechanisms remain unsolved. Here, rhizospheric activation, uptake, translocation, and compartmentalization of PFOS in LACV were investigated in comparison with those of high-accumulating crop variety (HACV) in terms of rhizospheric forms, transporters, and subcellular distributions of PFOS. The enhanced PFOS desorption from the rhizosphere soils by dissolved organic matter from root exudates was observed with weaker effect in LACV than in HACV. PFOS root uptake was controlled by a transporter-mediated passive process in which low activities of aquaporins and rapid-type anion channels were corrected with low expression levels of PIPs (PIP1-1 and PIP2-2) and ALMTs (ALMT10 and ALMT13) genes in LACV roots. Higher PFOS proportions in root cell walls and trophoplasts caused lower root-to-shoot transport in LACV. The ability to cope with PFOS toxicity to shoot cells was poorer in LACV relative to HACV since PFOS proportions were higher in chloroplasts but lower in vacuoles. Our findings provide novel insights into PFOS accumulation in lettuce and further understanding of multiprocess mechanisms of LACV.

Oxalic Acid in Root Exudates Enhances Accumulation of Perfluorooctanoic Acid in Lettuce.

Perfluorooctanoic acid (PFOA) is bioaccumulative in crops. PFOA bioaccumulation potential varies largely among crop varieties. Root exudates are found to be associated with such variations. Concentrations of low-molecular-weight organic acids (LMWOAs) in root exudates from a PFOA-high-accumulation lettuce variety are observed significantly higher than those from PFOA-low-accumulation lettuce variety (p < 0.05). Root exudates and their LMWOAs components exert great influences on the linear sorption-desorption isotherms of PFOA in soils, thus activating PFOA and enhancing its bioavailability. Among root exudate components, oxalic acid is identified to play a key role in activating PFOA uptake, with >80% attribution. Oxalic acid at rhizospheric concentrations (0.02-0.5 mM) can effectively inhibit PFOA sorption to soils by decreasing hydrophobic force, electrostatic attraction, ligand exchange, and cation-bridge effect. Oxalic acid enhances dissolution of metallic ions, iron/aluminum oxides, and organic matters from soils and forms oxalate-metal complexes, based on nuclear magnetic resonance spectra, ultraviolet spectra, and analyses of metal ions, iron/aluminum organometallic complexes, and dissolved organic carbon. The findings not only reveal the activation process of PFOA in soils by root exudates, particularly oxalic acid at rhizospheric concentrations, but also give an insight into the mechanism of enhancing PFOA accumulation in lettuce varieties.

Dynamics, thermodynamics, and mechanism of perfluorooctane sulfonate (PFOS) sorption to various soil particle-size fractions of paddy soil.

Soil is an important sink for perfluorooctane sulfonate (PFOS) that is a typical persistent organic pollutant with high toxicity. Understanding of PFOS sorption to various particle-size fractions of soil provides an insight into the mobility and bioavailability of PFOS in soil. This study evaluated kinetics, isotherms, and mechanisms of PFOS sorption to six soil particle-size fractions of paddy soil at environmentally relevant concentrations (0.01-1 µg/mL). The used soil particle-size fractions included coarse sand (120.4-724.4 mm), fine sand (45.7-316.2 mm), coarse silt (17.3-79.4 mm), fine silt (1.9-39.8 mm), clay (0.5-4.4 mm), and humic acid fractions (8.2-83.7 mm) labeled as F1~F6, respectively. PFOS sorption followed pseudo-second-order kinetics related to film diffusion and intraparticle diffusion, with speed-limiting phase acted by the latter. PFOS sorption isotherm data followed Freundlich model, with generally convex isotherms in larger size fractions (F1~F3) but concave isotherms in smaller size fractions (F4 and F5) and humic acid fraction (F6). Increasing organic matter content, Brunner-Emmet-Teller surface area, and smaller size fractions were conducive to PFOS sorption. Hydrophobic force, divalent metal ion-bridging effect, ligand exchange, hydrogen bonding, and protein-like interaction played roles in PFOS sorption. But hydrophobic force controlled the PFOS sorption, because its relevant organic matter governed the contribution of the soil fractions to the overall PFOS sorption. The larger size fractions dominated the PFOS sorption to the original soil because of their high mass percentages (~80%). This likely caused greater potential risks of PFOS migration into groundwater and bioaccumulation in crops at higher temperatures and ce values, based on their convex isotherms with an exothermic physical process.

Identification of Differentially Expressed Genes of Rice Under Cadmium Stress Using DDRT-PCR Approach.

Cadmium (Cd) is one of the hazardous environmental pollutants, and it can be harmful to human health through consumption of food-plants capable of bioaccumulating Cd. Therefore, lowering cadmium accumulation in plants is highly desirable. Here, a rice cultivar 'Qisanzhan' was studied using differential display reverse transcription-polymerase chain reaction (DDRT-PCR). Fifty-six differentially expressed genes were found in the root tips of 4-leaf stage rice seedlings exposed to 4 and 12 h of 50 µmol/L Cd(NO3)2 in a nutrient solution using DDRT-PCR. Further validation using semi-quantitative RT-PCR showed that the expression patterns of 16 genes were consistent with those found in DDRT-PCR. These genes encode receptor-like protein kinase, pleiotropic drug resistance protein, aquaporin protein, plasma membrane ATPase, etc. The differentially genes identified here can be used to obtain a better understanding of the molecular mechanisms of Cd absorption and accumulation in plants.

Interface Engineering with MoS2 -Pd Nanoparticles Hybrid Structure for a Low Voltage Resistive Switching Memory.

Metal oxide-based resistive random access memory (RRAM) has attracted a lot of attention for its scalability, temperature robustness, and potential to achieve machine learning. However, a thick oxide layer results in relatively high program voltage while a thin one causes large leakage current and a small window. Owing to these fundamental limitations, by optimizing the oxide layer itself a novel interface engineering idea is proposed to reduce the programming voltage, increase the uniformity and on/off ratio. According to this idea, a molybdenum disulfide (MoS2 )-palladium nanoparticles hybrid structure is used to engineer the oxide/electrode interface of hafnium oxide (HfOx )-based RRAM. Through its interface engineering, the set voltage can be greatly lowered (from -3.5 to -0.8 V) with better uniformity under a relatively thick HfOx layer (≈15 nm), and a 30 times improvement of the memory window can be obtained. Moreover, due to the atomic thickness of MoS2 film and high transmittance of ITO, the proposed RRAM exhibits high transparency in visible light. As the proposed interface-engineering RRAM exhibits good transparency, low SET voltage, and a large resistive switching window, it has huge potential in data storage in transparent circuits and wearable electronics with relatively low supply voltage.

Soil contamination and sources of phthalates and its health risk in China: A review.

Phthalates (PAEs) are extensively used as plasticizers and constitute one of the most frequently detected organic contaminants in the environment. With the deterioration of eco-environment in China during the past three decades, many studies on PAE occurrence in soils and their risk assessments have been conducted which allow us to carry out a fairly comprehensive assessment of soil PAE contamination on a nation-wide scale. This review combines the updated information available associated with PAE current levels, distribution patterns (including urban soil, rural or agricultural soil, seasonal and vertical variations), potential sources, and human health exposure. The levels of PAEs in soils of China are generally at the high end of the global range, and higher than the grade II limits of the Environmental Quality Standard for soil in China. The most abundant compounds, di-n-butyl phthalate (DBP) and di-(2-ethylhexyl) phthalate (DEHP), display obvious spatial distribution in different provinces. It is noted that urbanization and industrialization, application of plastic film (especially plastic film mulching in agricultural soil) and fertilizer are the major sources of PAEs in soil. Uptake of PAEs by crops, and human exposure to PAEs via ingestion of soil and vegetables are reviewed, with scientific gaps highlighted.

Variations in microbial community and di-(2-ethylhexyl) phthalate (DEHP) dissipation in different rhizospheric compartments between low- and high-DEHP accumulating cultivars of rice (Oryza sativa L.).

Di-(2-ethylhexyl) phthalate (DEHP) is a typical endocrine disrupting chemical with relatively high concentrations in agricultural soils of China. Here, a rhizobox experiment was conducted to investigate the variations in microbial community and DEHP dissipation among different soil rhizospheric compartments between low (Fengyousimiao) and high (Peizataifeng) DEHP-accumulating cultivars of rice (Oryza sativa L.) grown in DEHP spiked soil (0, 20, 100 mg/kg). The dissipation rates of DEHP in rhizospheric soils of Peizataifeng were generally significantly higher than those of Fengyousimiao, with the highest removal rate in 0-2 mm rhizosphere. The results of Illumina-HiSeq high-throughput sequencing revealed that both bacterial and fungal diversity and community structure were significantly different in rhizospheric soils of the two cultivars. DEHP dissipation rates in 0-2 mm rhizosphere of Peizataifeng were positively correlated with bacterial and fungal diversity. The relative abundance of DEHP-degrading bacterial genera Acinetobacter, Pseudomonas and Bacillus of Peizataifeng was generally higher than those in the same rhizospheric compartment of Fengyousimiao in DEHP treatments, resulting in different rhizospheric DEHP dissipation. Cultivation of Peizataifeng in agricultural soil is promising to facilitate DEHP dissipation and ensure safety of agricultural products.

Sorption kinetics, isotherms, and mechanism of aniline aerofloat to agricultural soils with various physicochemical properties.

Aniline aerofloat (AAF), a high-toxic organic flotation reagent, is widely used in mineral processing industry. However, little information on its environmental fate is available. AAF sorption to four types of agricultural soils at low concentrations (1-10 mg/L) was investigated using batch experiments. AAF sorption kinetics involved both boundary layer diffusion and intraparticle diffusion, following pseudo-second-order kinetics with equilibrium time within 120 min. Both Langmuir and Freundlich models fitted well the AAF sorption with the former better. Sorption of AAF to soils was a spontaneous and favorable physical sorption that was controlled by ion bridge effect and hydrophobic interaction that was related to van der Waals force and π-π coordination based on FTIR analyses. AAF sorption was remarkably affected by soil constituents, positively correlating with the contents of organic matter and clay. The relatively higher logKoc values (3.53-4.66) of AAF at environmental concentrations (1-5 mg/L) imply that soils are serving as a sink of AAF from beneficiation wastewater, posing great potential risks to environment and human health.

Genotypic variation in the uptake, accumulation, and translocation of di-(2-ethylhexyl) phthalate by twenty cultivars of rice (Oryza sativa L.).

Agricultural soil in China contains high levels of di-(2-ethylhexyl) phthalate (DEHP), especially in paddy-field soil of Guangdong province of China, but the accumulation and translocation of DEHP by rice (Oryza sativa L.) remains unknown. In the present study, twenty rice cultivars were cultivated in paddy soil spiked with DEHP, and variations in DEHP accumulation and translocation among various cultivars were investigated. Our results showed that DEHP concentrations in roots and shoots of different rice cultivars at four growth stages (i.e., ripening, tillering, jointing, and flowering stages) varied greatly from 0.26 to 11.8 mg/kg (dry weight, dw) and 0.40 to 7.58 mg/kg (dw), respectively. No obvious change over time was observed. The greatest variation in DEHP concentrations among the rice cultivars occurred at ripening stage, whereas the lowest variation at flowering stage. During ripening stage, the largest variation in DEHP concentrations among cultivars were observed in stems (varying from 0.35 to 13.2 mg/kg), whereas the least one was observed in roots (ranging from 1.01 to 5.72 mg/kg). Significant differences in DEHP concentrations in the roots, stems, leaves and grains of most rice cultivars were found. The translocation factors of DEHP from roots to stems or stems to leaves were higher than those from shoots to grains. Overall, cultivars Tianfengyou 316, Wuyou 308, and Peizataifeng, which contained low levels of DEHP in grains but high levels in shoots, were ideal cultivars for simultaneous production of safe food and phytoremediation of contaminated soil.

Effects of microplastics on the environmental behaviors of the herbicide atrazine in soil: Dissipation, adsorption, and bioconcentration.

As an emerging contaminant in soil, the impact of microplastics (MPs) on the environmental behavior of other organic pollutants remains uncertain, potentially threatening the sustainability of agricultural production. In this study, the impact of two kinds of MPs on the environmental behaviors of herbicide atrazine in soil-plant system was investigated. The results showed that MPs significantly reduced the half-life 17.69 ∼ 21.86 days of atrazine in the soil, compared to the control group. Meanwhile, the introduction of MPs substantially increased atrazine adsorption. Additionally, MPs substantially enriched the diversity and functionality of soil microbiome, and the soil metabolic activity was stimulated. Regarding the crop growth, the accumulation of atrazine in maize were significantly decreased by approximately 48.4-78.5 % after exposure to MPs. In conclusion, this study reveals the impact of MPs on atrazine's environmental behaviors in soil and highlights their less effect on maize growth, providing valuable insights for managing MPs contamination in sustainable agriculture.

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"Planting conifer and reserving broadleaved tree" is an effective way to restore broad-leaved pine forest of temperate zone in Northeast China. Liberation cutting can promote the growth of Korean pine (Pinus koraiensis) under forest crown and accelerate the succession. However, how liberation cutting intensity affects the growth of Korean pine in secondary forest is still unclear. Taking the "Planting conifer and reserving broadleaved tree" Korean pine forest in Changbai Mountain as the object, we constructed a growth model of diameter at breast height (DBH) and tree height of Korean pine with double dummy variables (liberation cutting intensity and tree classification) to predict the growth of Korean pine plantation under different liberation cutting intensities, i.e. control (no liberation cutting), light-intensity liberation cutting (retaining upper canopy closure 0.6), medium-intensity liberation cutting (0.4), heavy-intensity liberation cutting (0.2) and clear cutting (cutting all upper broadleaf trees) stands. We analyzed the effects of liberation cutting intensities on DBH, tree height, and the ratio of tree height to DBH. The results showed that among six theoretical growth equations, the Gompertz model on the DBH (R2=0.46) and tree height (R2=0.81) was optimal basic model. The R2 of the DBH model was increased to 0.65 and 0.89, respectively, after the single dummy variable and the double dummy variable were introduced into the basic model, while the R2 of the tree height model was increased to 0.84 and 0.94. Therefore, the double dummy variable model was the most suitable for predicting the growth of Korean pine. The growth of DBH of pressed tree increased with the increases of liberation cutting intensity (increase by 145.8%-933.3%) during the whole simulation period (0-80 a). Average and dominant trees showed the same pattern at 42 and 60 a. In the early and middle stages of liberation cutting (20 and 42 a), clear cutting and heavy-intensity liberation cutting had similar effects on the height growth of dominant trees (64.8%-68.5%), average trees (100.0%-144.2%), and pressed trees (138.5%-183.9%). The effects of medium-intensity liberation cutting and light-intensity liberation cutting on the height growth were similar (24.3%-35.1%, 56.0%-92.3%, 84.6%-103.2%). While in the middle and late period (42 and 80 a), height growth of three grade trees increased with the increases of liberation cutting intensity. Under each liberation cutting intensity, the ratio of height to DBH of the dominant, average, and pressed trees increased successively, ranging from 0.50-0.95, 0.64-1.23, and 0.73-4.33, respectively. Only the pressed tree decreased with the increases of liberation cutting intensity at 0-80 a. Therefore, about 40 years after the implementation of liberation cutting, the promoting effect of different liberation cutting intensities on DBH growth was significantly weakened, the promoting effect on tree height growth was significantly enhanced, and the ratio of tree height to diameter began to increase. In order to alleviate forest competition, second liberation cutting should be carried out for light-intensity liberation cutting and medium-intensity liberation cutting stands to further release the growth potential of Korean pine, and thinning management should be carried out in clear cutting and heavy-intensity liberation cutting stands.

Simultaneous biodegradation of polycyclic aromatic hydrocarbons and phthalates by bacterial consortium and its bioremediation for complex polluted soil and sewage sludge.

Simultaneous biodegradation of multiple micropollutantslike polycyclic aromatic hydrocarbons (PAHs) and phthalates (PAEs) by microbial consortia remain unclear. Here, four distinct bacterial consortia capable of degrading PAHs and PAEs were domesticated from sludge and its composts. PAH-degrading consortium HS and PAE-degrading consortium EC2 displayed the highest degradation efficiencies for PAHs (37 %-99 %) and PAEs (98 %-99 %), respectively, being significantly higher than those of individual member strains. Consortia HS and EC2 could simultaneously degrade both PAHs and PAEs. Remarkably, a synthetic consortium Syn by co-culturing consortia HS and EC2 demonstrated proficient simultaneous biodegradation for both PAHs (65 %-98 %) and PAEs (91 %-97 %). These consortia changed their community structure with enriching pollutant-degrading genera and extracellular polymeric substance contents to promote simultaneous biodegradation of multiple pollutants. Moreover, consortium Syn significantly enhanced degradation of both PAHs and PAEs in soil and sludge. This study provides strong candidates for simultaneous bioremediation of complex polluted environments by PAHs and PAEs.

Molecular insights into the catabolism of dibutyl phthalate in Pseudomonas aeruginosa PS1 based on biochemical and multi-omics approaches.

A comprehensive understanding of the molecular mechanisms underlying microbial catabolism of dibutyl phthalate (DBP) is still lacking. Here, we newly isolated a bacterial strain identified as Pseudomonas aeruginosa PS1 with high efficiency of DBP degradation. The degradation ratios of DBP at 100-1000 mg/L by this strain reached 80-99 % within 72 h without a lag phase. A rare DBP-degradation pathway containing two monobutyl phthalate-catabolism steps was proposed based on intermediates identified by HPLC-TOF-MS/MS. In combination with genomic and transcriptomic analyses, we identified 66 key genes involved in DBP biodegradation and revealed the genetic basis for a new complete catabolic pathway from DBP to Succinyl-CoA or Acetyl-CoA in the genus Pseudomonas for the first time. Notably, we found that a series of homologous genes in Pht and Pca clusters were simultaneously activated under DBP exposure and some key intermediate degradation related gene clusters including Pht, Pca, Xyl, Ben, and Cat exhibited a favorable coexisting pattern, which contributed the high-efficient DBP degradation ability and strong adaptability to this strain. Overall, these results broaden the knowledge of the catabolic diversity of DBP in microorganisms and enhance our understanding of the molecular mechanism underlying DBP biodegradation.

Congener-specific fate and impact of microcystins in the soil-earthworm system.

Microcystins (MCs) have a significant influence on aquatic ecosystems, but little is known about their terrestrial fate and impact. Here, we investigated the fate of two MCs (MC-LR and MC-RR) in the soil-earthworm system, with consideration of their congener-specific impact on earthworm health, soil bacteria, and soil metabolome. Although MCs had little acute lethal effect on earthworms, they caused obvious growth inhibition and setae rupture. Relative to MC-RR, MC-LR exhibited higher bioaccumulation and the resulting dermal lesions and deformation of longitudinal muscles. While the incorporation of both MCs into soils stimulated pathogenic bacteria and depressed oxidative stress tolerant bacteria, the response among soil nitrification and glutathione metabolism differed between the two congeners. The dissipation kinetics of MCs obeyed the first-order model. Earthworms stimulated soil N-cycling enzyme activities, increased the abundance of MC-degrading bacteria, and promoted bacterial metabolic functions related to glutathione metabolism, xenobiotics biodegradation, and metabolism of amino acids that comprise MCs, which accelerated the dissipation of MC-LR and MC-RR by 227% and 82%, respectively. These results provide evidence of significant congener differences in the terrestrial fate and impact of MCs, which will enable a better understanding of their role in mediating soil functions and ecosystem services.

Improving key gene expression and di-n-butyl phthalate (DBP) degrading ability in a novel Pseudochrobactrum sp. XF203 by ribosome engineering.

Di-n-butyl phthalate (DBP) is one of the important phthalates detected commonly in soils and crops, posing serious threat to human health. Pseudochrobactrum sp. XF203 (XF203), a new strain related with DBP biodegradation, was first identified from a natural habitat lacking human disturbance. Genomic analysis coupled with gene expression comparison assay revealed this strain harbors the key aromatic ring-cleaving gene catE203 (encoding catechol 2,3-dioxygenase/C23O) involved DBP biodegradation. Following intermediates identification and enzymatic analysis also indicated a C23O dependent DBP lysis pathway in XF203. The gene directed ribosome engineering was operated and to generate a desirable mutant strain XF203R with highest catE203 gene expression level and strong DBP degrading ability. The X203R removed DBP in soil jointly by reassembling bacterial community. These results demonstrate a great value of XF203R for the practical DBP bioremediation application, highlighting the important role of the key gene-directed ribosome engineering in mining multi-pollutants degrading bacteria from natural habitats where various functional genes are well conserved.

Mining flotation reagents: Quantitative and robust analysis of metal-xanthate complexes in water.

Xanthates, common mining flotation reagents, strongly bind thiophilic metals such as copper (Cu), lead (Pb), cadmium (Cd), and zinc (Zn) and consequentially change their bioavailability and mobility upon their discharge into the environment. However, accurate quantification of the metal-xanthate complexes has remained elusive. This study develops a novel and robust method that realizes the accurate quantification of the metal-xanthate complexes resulted from single and multiple reactions of three typical xanthates (ethyl, isopropyl, and butyl xanthates) and four thiophilic metals (Cu, Pb, Cd, and Zn) in water samples. This method uses sulfur (S2-) dissociation, followed by tandem solid phase extraction of C18 + PWAX and subsequent LC-MS/MS analysis. It has a wide linearity range (1-1000 µg/L, R2 ≥ 0.995), low method detection limits (0.002-0.036 µg/L), and good recoveries (70.6-107.0 %) at 0.01-10 mg/L of xanthates. Applications of this method showed ubiquitous occurrence of the metal-xanthate complexes as the primary species in flotation wastewaters, which the concentrations were 4.6-28.9-fold higher than those previously determined. It is the first quantitative method established for the analysis of metal-xanthate complexes in water samples, which is of great importance to comprehensively understand the fate and risks of xanthates in the environment.