Comparative evaluation and prioritization of key influences on biodegradation of 2,2',4,4'-tetrabrominated diphenyl ether by bacterial isolate B. xenovorans LB400.

Polybrominated diphenyl ethers (PBDEs) are a class of persistent organic pollutants being widely distributed and harmful to human health and wildlife, and the development of sustainable rehabilitation strategies including microbial degradation is of great concern. Although the increasing number of bacteria, especially the broad-spectrum and potent aerobes have been isolated for the efficient removal of PBDEs, the external influences and the corresponding influential mechanism on biodegradation are not fully understood yet. Given the wide-spectrum biodegradability of aerobic bacterial isolate, B. xenovorans LB400 for PBDEs, the dual impacts of many pivotal factors including pH, temperature, presence of dissolved organic matter (DOM) and cadmium ion etc. were comprehensively revealed on biodegradation of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47). Due to the structural resemblance and stimulation of specific enzyme activity in bacteria, the biphenyl as substrates showed the greater capacity than non-aromatic compounds in improving biodegradation. The individual adaptation to neutrality and cultivation at about 30 °C was beneficial for biodegradation since the bacterial cellular viability and enzyme activity was mostly preserved. Although it was possibly good for the induction of hormesis and favorable to enhance the permeability or bioavailability of pollutant, the exceeding increase of Cd2+ or DOM may not give the profitable increase of biodegradation yet for the detrimental effect. For biodegradation, the mechanistic relationship that took account of the integrative correlation with the influential factors was artfully developed using partial least square (PLS) regression technique. Relative to the most significant influence of culture time and initial concentration of BDE-47, the larger relevance of other factors primarily marked as pH and DOM was consecutively shown after the quantitative prioritization. This may not only help understand the influential mechanism but provide a prioritizing regulation strategy for biodegradation of BDE-47. The PLS-derived relationship was validated with the certain predictability in biodegradation, and could be used as an alternative to accelerate a priori evaluation of suitability or improve the feasibility of such bacteria in remediation of PBDEs in the environment.

Study on active response of superoxide dismutase and relevant binding interaction with bioaccumulated phthalates and key metabolites in Eisenia fetida.

Phthalic acid esters (PAEs) are a group of widespread persistent organic pollutants in the environment. Though the harmful effect of PAEs including activity inhibition of superoxide dismutase (SOD) to arouse oxidative stress were well documented, the deep insights into mechanisms that are relevant with SOD activity are still lacking. By 7d-cultivation of Eisenia fetida in artificially-polluted soil, the different active responses of SOD in earthworm were shown to PAE congeners. Despite the less bioaccumulation and bioavailability, the di-butyl phthalate (DBP) etc. structurally coupled with longer ester-chains appeared more effective to trigger the up-regulation and then the slight decline of SOD activity. Given the remarkable biotransformation especially for short-chain PAEs, the SOD activity response in earthworm should be regarded as joint effect with their metabolites, e.g. monophthalates (MAEs) and phthalic acid (PA). The in vitro SOD activity was shown with the obvious inhibition of 21.31% by DBP, 88.93% by MBP, and 58.57% by PA respectively when the concentrations were elevated up to 0.03 mM. The SOD activity inhibition confirmed the molecular binding with pollutants as an essential event besides the biological regulation for activity. The binding interaction was thermodynamically exothermic, spontaneous and strengthened primarily by Van der Waals force and hydrogen bonds, and was spectrally diagnosed with the conformational changes including diminution of α-helix content and spatial reorientation of fluorophore tryptophan. As coherently illustrated with the larger fluorescence quenching constants (3.65*104-4.47*104/mol) than DBP, the metabolites should be the priority concern due to stronger activity inhibition and toxicological risks.

Does Biochar Induce Similar Successions of Microbial Community Structures Among Different Soils?

In this study, the responses of soil bacterial communities to biochar amendment in different soils were investigated. Biochar amendment had not significantly changed the bacterial richness and diversity in black soil, fluvo-aquic soil and red soil, but shifted all the soil bacterial community structures. Biochar amendment mainly increased the growth of low-abundance bacteria in fluvo-aquic soil and that of high-abundance bacteria in red soil. The most abundant bacterial phylum in black soil and fluvo-aquic soil, Proteobacteria, increased after biochar addition, while Chloroflexi, the most abundant phylum in red soil, decreased after biochar addition. Some bacterial phyla responded consistently to biochar amendment. However, many more bacterial phyla responded differently to biochar amendment in different soils, especially those phyla present at low abundances. Therefore, our study confirmed that the responses of soil bacterial communities to the same biochar were specific to both soil type and bacterial phylum.

Optimization of Sample Pretreatment based on Graphene Oxide Dispersed Acid Silica Gel for Determination of Polybrominated Diphenyl Ethers in Vegetables near an E-waste Recycling Plant.

Polybrominated diphenyl ethers (PBDEs) derived from e-waste dismantling, tend to easily bioaccumulate in vegetables. In this study, an optimized sample pretreatment method based on graphene oxide (GO) dispersed acid silica gel was used to determine PBDEs levels in vegetables. The recovery efficiency of the optimized method ranged between 90.3%-107.5% with the detection limit (LOD) being within 0.17-1.8 ng g-1. Vegetable samples were grown nearby an e-waste recycling plant in Nanjing, China, and analyzed using the optimized method. The concentrations of ΣPBDEs in the samples ranged from 12.1 to 20.1 ng g-1. This study developed an optimized sample pretreatment method to determine PBDEs in vegetables nearby e-waste contaminated sites and provides insights on the potential risks derived from e-waste dismantling to the surrounding environment.

Evaluation of soil washing process with carboxymethyl-ß-cyclodextrin and carboxymethyl chitosan for recovery of PAHs/heavy metals/fluorine from metallurgic plant site.

Polycyclic aromatic hydrocarbons (PAHs)/heavy metals/fluorine (F) mixed-contaminated sites caused by abandoned metallurgic plants are receiving wide attention. To address the associated environmental problems, this study was initiated to investigate the feasibility of using carboxymethyl-ß-cyclodextrin (CMCD) and carboxymethyl chitosan (CMC) solution to enhance ex situ soil washing for extracting mixed contaminants. Further, Tenax extraction method was combined with a first-three-compartment model to evaluate the environmental risk of residual PAHs in washed soil. In addition, the redistribution of heavy metals/F after decontamination was also estimated using a sequential extraction procedure. Three successive washing cycles using 50 g/L CMCD and 5 g/L CMC solution were effective to remove 94.3% of total PAHs, 93.2% of Pb, 85.8% of Cd, 93.4% of Cr, 83.2% of Ni and 97.3% of F simultaneously. After the 3rd washing, the residual PAHs mainly existed as very slowly desorbing fractions, which were in the form of well-aged, well-sequestered compounds; while the remaining Pb, Cd, Cr, Ni and F mainly existed as Fe-Mn oxide and residual fractions, which were always present in stable mineral forms or bound to non-labile soil fractions. Therefore, this combined cleanup strategy proved to be effective and environmentally friendly.

Congener-specificity, dioxygenation dependency and association with enzyme binding for biodegradation of polybrominated diphenyl ethers by typical aerobic bacteria: Experimental and theoretical studies.

Polybrominated diphenyl ethers (PBDEs) are a group of organic pollutants that have attracted much concerns of scientific community over the ubiquitous distribution, chemical persistence and toxicological risks in the environment. Though a great number of aerobic bacteria have been isolated for the rapid removal of PBDEs, the knowledge about biodegradation characteristics and mechanism is less provided yet. Herein, the congener-specificity of aerobic biodegradation of PBDEs by typical bacteria, i.e. B. xenovorans LB400 was identified with the different biodegradation kinetics, of which the changes were largely hinged on the bromination pattern. The more bromination isomerically at ortho-sites other than meta-sites or the single bromination at one of aromatic rings might always exert the positive effect. The biodegradation of PBDEs should be thermodynamically constrained to some extent because the calculated Gibbs free energy changes of initial dioxygenation by quantum chemical method increased with the increase of bromination. Within the transition state theory, the high correlativity between the apparent biodegradation rates and Gibbs free energy changes implied the predominance and rate-limiting character of initial dioxygenation, while the regioselectivity of dioxygenation at the ortho/meta-sites was also manifested for the more negative charge population. The molecular binding with the active domain of dioxygenase BphA1 in aerobe was firstly investigated using docking approach. As significantly illustrated with the positive relationship, the higher binding affinity with BphA1 should probably signify the more rapid biodegradation. Besides the edge-on π-π stacking of PBDEs with F227 or Y277 and π-cation formulation with histidines (H233, H239) in BphA1, the reticular hydrophobic contacts appeared as the major force to underpin the high binding affinity and rapid biodegradation of PBDEs. Overall, the experimental and theoretical results would not only help understand the aerobic biodegradation mechanism, but facilitate enhancing applicability or strategy development of engineering bacteria for bioremediation of PBDEs in the environment.

New insights into persulfate decomposition by soil minerals: radical and non-radical pathways.

Persulfate (PS)-based in situ chemical oxidation (ISCO) has been widely used for pollutant remediation in soil and groundwater. However, the underlying mechanism of interactions between mineral and PS was not fully explored. In this study, several soil model minerals including goethite, hematite, magnetite, pyrolusite, kaolin, montmorillonite, and nontronite were selected to investigate their potential effects on PS decomposition and free radical evolution. It was found the decomposition efficiency of PS by these minerals varied significantly, and both the radical and non-radical decomposition processes were included. Pyrolusite has the highest reactivity for PS decomposition. However, PS decomposition is prone to form SO42- through non-radical pathway, and thus, the amounts of free radicals (e.g., •OH and SO4•-) produced are relatively limited. However, PS mainly decomposed to produce free radicals in the presence of goethite and hematite. In the presence of magnetite, kaolin, montmorillonite, and nontronite, PS both decomposed to produce SO42- and free radicals. Furthermore, the radical process exhibited the high degradation performance for model pollutant such as phenol with relatively high utilization efficiency of PS, while non-radical decomposition has limited contribution to phenol degradation with extremely low utilization efficiency of PS. This study deepened the understanding of interactions between PS and minerals during the PS-based ISCO in soil remediation.

Extracellular polymeric substances enhanced mass transfer of polycyclic aromatic hydrocarbons in the two-liquid-phase system for biodegradation.

The objective was to elucidate the role of extracellular polymeric substances (EPS) in biodegradation of polycyclic aromatic hydrocarbons in two-liquid-phase system (TLPs). Therefore, biodegradation of phenanthrene (PHE) was conducted in a typical TLPs--silicone oil-water--with PHE-degrading bacteria capable of producing EPS, Sphingobium sp. PHE3 and Micrococcus sp. PHE9. The results showed that the presence of both strains enhanced mass transfer of PHE from silicone oil to water, and that biodegradation of PHE mainly occurred at the interfaces. The ratios of tightly bound (TB) proteins to TB polysaccharides kept almost constant, whereas the ratios of loosely bound (LB) proteins to LB polysaccharides increased during the biodegradation. Furthermore, polysaccharides led to increased PHE solubility in the bulk water, which resulted in an increased PHE mass transfer. Both LB-EPS and TB-EPS (proteins and polysaccharides) correlated with PHE mass transfer in silicone oil, indicating that both proteins and polysaccharides favored bacterial uptake of PHE at the interfaces. It could be concluded that EPS could facilitate microbial degradation of PHE in the TLPs.

Mechanistic insight into hydroxylation of 2,2',4,4'-tetrabromodiphenyl ether during biodegradation by typical aerobic bacteria: Experimental and computational studies.

Polybrominated diphenyl ethers (PBDEs) are a group of persistent pollutants in the environment. Though aerobic biodegradation of PBDEs have been extensively studied, the involved hydroxylation mechanism decisive for whole biotransformation is not clear yet. During the effective biodegradation of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) by B. xenovorans LB400, the depletion of endogenous ∙OH by scavenger could bring about the significant decrease of biodegradation efficiency whereas ·O2- was nearly not influential. Given the importance of ∙OH in hydroxylation, the reaction mechanisms along major pathways of electrophilic addition and hydrogen abstraction were theoretically examined by density functional theory (DFT). For the less demand of activation energy, the relative preference of electrophilic addition was shown at aromatic C3-site. When the secondary reaction was considered after addition at C4-site, the barrierless association of ∙OH at C3-site and deprotonation by H2O was validated as the energetically-favorable pathway that may cause dihydroxylation of BDE-47 into 3,4-dihydroxyl-BDE-17. The electrophilic addition followed by seconary barrierless trans-association of ∙OH and then dehydration seemed favorable for monohydroxylation as regards energetic barrier merely up to 194.01 kJ mol-1, while the hydrogen abstraction by ∙OH from C5-site was more privileged actually. The theoretical insights would help well understand the hydroxylation mechanism of PBDEs by aerobes.

Correlations between soil metabolomics and bacterial community structures in the pepper rhizosphere under plastic greenhouse cultivation.

Microbial communities in the plant rhizosphere are critical drivers of soil organic matter conversion and thus affect plant growth, especially under plastic greenhouse vegetable cultivation (PGVC). By high-throughput sequencing and soil metabolomics, we investigated the differential structures and functions of the soil bacterial community in pepper rhizosphere and bulk soils under PGVC. It was found that the soil properties, including the total dissolved organic carbon content, did not show significant differences between the rhizosphere and bulk soil. However, the soil metabolite profiles and the soil bacterial community structures changed in pepper rhizosphere. Eleven differential metabolites were detected between rhizosphere and bulk soils, including organic acids and sugars, which were positively or negatively correlated with the relative abundances of the differential bacteria. Pathway enrichment analysis indicated that the most differentially expressed metabolic pathway was starch and sucrose metabolism, and the main functional genes participating in this pathway were predicted to be downregulated in rhizosphere soil. This study linked the differential soil microbe and soil metabolite profiles in the pepper rhizosphere under PGVC and provided new insights into plant-microbe interactions in soil.

Insights into the mechanisms underlying efficient Rhizodegradation of PAHs in biochar-amended soil: From microbial communities to soil metabolomics.

The combined effects of biochar amendment and the rhizosphere on the soil metabolic microbiome during the remediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soil remain unknown. In this study, we attempted to characterize a PAH degradation network by coupling the direct PAH degradation with soil carbon cycling. From microbial community structure and functions to metabolic pathways, we revealed the modulation strategies by which biochar and the rhizosphere benefited PAH degradation in soil. Firstly, some PAH degraders were enriched by biochar and the rhizosphere, and their combination promoted the cooperation among these PAH degraders. Simultaneously, under the combined effects of biochar and the rhizosphere, the functional genes participating in upstream PAH degradation were greatly upregulated. Secondly, there were strong co-occurrences between soil microbial community members and metabolites, in particular, some PAH degraders and the metabolites, such as PAH degradation products or common carbon resources, were highlighted in the networks. It shows that the overall downstream carbon metabolism of PAH degradation was also greatly upregulated by the combined effects of biochar and plant roots, showing good survival of the soil microbiome and contributing to PAH biodegradation. Taken together, both soil carbon metabolism and direct contaminant biodegradation are likely to be modulated by the combined effects of biochar and plant roots, jointly benefitting to PAH degradation by soil microbiome. Our study is the first to link PAH degradation with native carbon metabolism by coupling sequencing and soil metabolomics technology, providing new insights into a systematic understanding of PAH degradation by indigenous soil microbiome and their networks.

Theoretical investigation of AhR binding property with relevant structural requirements for AhR-mediated toxicity of polybrominated diphenyl ethers.

Polybrominated diphenyl ethers (PBDEs) are more frequently suspected with the induction of toxicity via signal transduction pathway of cytosolic aryl hydrocarbon receptor (AhR), the initial binding to which is assumed to be an essential prerequisite during the ligand-dependent activation. However, the AhR binding property and associated toxicity of PBDEs is yet to be clearly known for lacking insights into the structural requirements at molecular level. To understand the AhR binding property of PBDEs, the ligand binding domain (LBD) of AhR was simulatively developed on homologous protein after basic validation of geometrical rationality and the binding interaction profile was visually described using molecular docking approach. For AhR binding, the offset or edge-on π-π stackings with aromatic motifs including Phe289, Phe345 and His285 were shown to be structurally required whereas the electrostatic attraction validated for AhR binding to dioxins might be less effective for 2,2',3,4,4'-pentabromodiphenyl ether (BDE-85). Besides the demands of less steric hindrance from alanines and weak formulation of hydrogen bonds, the dispersion force through large contact and polarization of S-π electrons seemed to be impactful when BDE-85 were closer to Cys327, Met334 or Met342. With theoretical computation of AhR binding energies, the more significant correlativity with bioassays was derived especially for the lowly/moderately brominated congeners, and could be used to predict the AhR binding affinity on certain degree. The informative results would thus not only help well understand the molecular basis of AhR-mediated toxicity but give an approach for accelerative evaluation of AhR binding and toxicity of PBDEs.

Can biochar and oxalic acid alleviate the toxicity stress caused by polycyclic aromatic hydrocarbons in soil microbial communities?

It remains unclear whether biochar amendment can mediate changes in soil microbial communities caused by organic contaminants in the rhizosphere. In this study, phenanthrene-contaminated soil was amended with biochar and oxalic acid (OA) alone or in combination and incubated for 21 days. Phospholipid fatty acids (PLFAs) and high-throughput sequencing were used to evaluate shifts in bacterial and fungal community structure. Phenanthrene stress led to significant shifts in both soil bacterial and fungal community structure, in particularly, 82% of microbial phyla decreased in abundance. Biochar and/or OA improved the phenanthrene-polluted soil by positively mediating shifts in soil microbial communities stressed by phenanthrene. Specifically, biochar and/or OA led to the survival of certain microbial taxa that were inhibited by phenanthrene stress. In addition, many functional microbial individuals and genes participating in polycyclic aromatic hydrocarbon (PAH) degradation were positively stimulated by high phenanthrene stress and further stimulated by the simultaneous application of biochar and OA. Based on these findings, tandem biochar and rhizoremediation may be a feasible strategy for relieving PAH toxicity to soil microbial communities.

Green conversion of crop residues into porous carbons and their application to efficiently remove polycyclic aromatic hydrocarbons from water: Sorption kinetics, isotherms and mechanism.

In this study, rape straw- and corn cob-derived porous carbons (PCs) were fabricated by hydrothermal treatment (250 °C, 4 h) and subsequent activation (850 °C, 1 h) using a non-corrosive agent, potassium bicarbonate. The PCs exhibited a very large specific surface area (1069-1281 cm2 g-1), high pore volume (0.55-0.72 cm3 g-1), wide pore size distribution (from micropores to macropores), high hydrophobicity, and partly graphitized structure. These properties contributed to highly efficient performance for the sorption of polycyclic aromatic hydrocarbons (PAHs), with maximum sorption capacities of 592.97, 480.27, and 692.27 mg g-1 towards naphthalene, acenaphthene, and phenanthrene, respectively. A three-step sorption process with pore filling, hydrophobic effects, and π-π stacking interactions on the heterogeneous surface is a possible mechanism for the sorption of PAHs onto PCs. This study presents an environmentally friendly strategy for the reuse of crop residues in the field of organic micropollutant-contaminated water treatment.

Meso-/microporous carbon as an adsorbent for enhanced performance in solid-phase microextraction of chlorobenzenes.

There is urgent demand for the design of advanced coating materials for solid-phase microextraction (SPME) for water quality monitoring and assessment because of the global occurrence of chlorobenzenes (CBs). In this study, we proposed a dual-order activation method in which potassium hydroxide is used to modify pre-activated calcium citrate to synthesize a highly developed meso-/microporous carbon (MMC). The as-obtained MMC presented well-developed porosity with a super-high specific surface area (2638.09 m2 g-1), abundant meso-/micropores (0.5-10 nm), high hydrophobicity, excellent thermal stability (>720 °C), and a partly graphitized structure. As a coating material for headspace-SPME, the MMC-coated fiber exhibited outstanding extraction capability for CBs (up to 48.5 times higher than that of commercial fibers), which may be attributed to multiple interactions between the MMC and the pollutants, including size selectivity, micropore filling, π-π stacking and hydrophobicity. Finally, a satisfactory method using an MMC-coated fiber coupled with gas chromatography and electron capture detection was developed with good linearity (1-1000 ng L-1, R2 > 0.9982), high enrichment efficiencies (enrichment factors, 861-7819), low limits of detection (0.003-0.072 ng L-1), excellent repeatability (0.7-5.3%) and reproducibility (1.7-5.1%), and outstanding recoveries (90.18-103.02%) when applied to determine trace CBs in real water samples. These results suggest that MMC is a promising coating material for the SPME of CBs.

Reducing plant uptake of a brominated contaminant (2,2',4,4'­tetrabrominated diphenyl ether) by incorporation of maize straw into horticultural soil.

Application of crop residues is a conventional practice that contributes to crop production through nutrient returns and other benefits to soil health: driving soil physicochemical and biological functions. However, little is known about the impacts of straw residue incorporation on the bioavailability of organic pollutants and associated changes in microbial community structure in contaminated soils. In this study, maize straw was added to a soil contaminated with a model polybrominated diphenyl ether (BDE-47). A pot experiment was conducted and planted with carrot (Daucus carota L.). We found that straw addition greatly reduced the bioavailability of BDE-47, changed the bacterial community structure and affected a range of soil physiochemical properties. Moreover, the amount of BDE-47 that had accumulated in carrot roots and aboveground tissues was significantly reduced. This study may therefore describe an effective agronomic strategy to reduce the bioavailability of polybrominated diphenyl ethers (PBDEs) in a soil used to grow high value vegetable crops. This strategy draws on traditional wisdom and shows promise as a practical method to support horticultural production systems, remediate soils, and help to ensure food safety.

Polycyclic aromatic hydrocarbons in soils in the vicinity of Nanjing, China.

The occurrence and distribution of polycyclic aromatic hydrocarbons (PAHs) in vegetable soils from five vegetable fields (including: Liuhe, Xixia, Pukou, Jianye and Yuhua districts) in Nanjing outskirt were investigated with high performance liquid chromatography (HPLC) equipped with fluorescence detector. The total concentrations of 15 priority PAHs in 126 soil samples ranged from 21.91 to 533.84ng g(-1) dry weight, and the sum of seven carcinogenic PAHs concentrations varied from 1.48 to 236.19ng g(-1) dry weight. Statistical analysis of the PAHs concentrations showed that the highest PAHs concentration was observed in Liuhe, and the lowest PAHs concentrations were found in Xixia among the five districts. The ratios of fluoranthene to sum of fluoranthene and pyrene concentrations (Flt/(Flt+Pyr)) were more than 0.5 in 99% of vegetable soil samples, showing that the PAHs in soils were generally derived from straw and coal combustion sources. The results from principal component analysis (PCA) further indicated that extensive combustion activities affected the PAHs distribution in Nanjing vegetable soils.

Dicofol application resulted in high DDTs residue in cotton fields from northern Jiangsu province, China.

Dicofol with high impurity of DDT compounds is still widely used in agricultural practice such as cotton cultivation and becomes an important source of DDT pollution in China. In this study, investigations on the DDT residues in cotton fields from northern Jiangsu province, China were conducted. The results showed that DDTs in cotton soil were much higher than other mode of land use. The DDTs levels ranged from 4.2 to 678.6 ngg(-1), with a mean concentration of 190.4 ngg(-1), of which the most abundant compounds were p,p'-DDE (mean of 129.38 ngg(-1)), p,p'-DDT (mean of 26.57 ngg(-1)) and o,p'-DDT (mean of 16.92 ngg(-1)). The concentrations of o,p'-DDT and o,p'-DDE were significantly higher (p<0.05) in topsoil (0-10 cm) than in subsoil (10-20 cm), while other DDT compounds were not. Source apportionment showed that dicofol-type DDT accounted for up to 80% of the DDTs residue. All the results indicated that dicofol applications resulted in serious DDT pollution in cotton fields. Our work provided implications for reasons why there was no apparent decrease of DDT level in China.

Facile synthesis of hierarchical porous carbon from crude biomass for high-performance solid-phase microextraction.

Porous materials have great prospective applications for solid-phase microextraction (SPME) technology because of their large specific surface area and pore volume. In this study, a hierarchical porous carbon (HPC) was synthesized by simple hydrothermal reaction and potassium hydroxide (KOH) activation of crude biomass and found to be an efficient adsorbent for SPME of organic pollutants. Results show that the as-prepared HPC has a partly graphitic amorphous-like structure with ultrahigh specific surface area (2551 m2/g), high pore volume (1.53 cm3/g), good pore size distribution (PSD) (mesopore/micropore ratio of 68%), and great thermal stability (>450 °C). When we utilized it as SPME fiber coating, the extraction capacities for chlorobenzenes (CBs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and phthalates (PAEs) were, respectively, 1.13-39.46, 2.40-7.78, 1.34-36.02, and 1.50-1.83 times higher than those of a commercial polydimethylsiloxane (PDMS) fiber. Under the optimized extraction conditions, an analytical method for CBs with low detection limits (0.01-0.24 ng/L), good repeatability (1.00%-4.93% for intra-day, 1.11%-6.94% for inter-day), and great reproducibility (1.48%-8.91%, n = 3) was developed. Moreover, we evaluated the practicality of the developed method for environmental water sample and obtained satisfactory recoveries (86.21%-104.34%). The findings provide a novel and promising HPC from crude biomass using a low-cost and facile synthetic route for SPME applications.

Long-Term Plastic Greenhouse Cultivation Changes Soil Microbial Community Structures: A Case Study.

Plastic greenhouse vegetable cultivation (PGVC) has been widely developed around the world and has resulted in great changes in soil properties and potential contamination by phthalate esters (PAEs). Using high-throughput sequencing, this study investigated the succession and potential factors impacting soil microbial community structures over 20 years of PGVC. The results showed that the pH of soils under PGVC were significantly lower, while the nutrient contents of soils were higher, relative to those of open field soil. The residue concentrations of PAEs in soil under PGVC increased with increasing periods of PGVC. The fungal community diversity, rather than the bacterial community diversity, was significantly reduced in soils under PGVC. However, both the soil bacterial and fungal community structures were changed by long-term PGVC. Among the tested soil physicochemical properties, soil pH and clay were the top two factors affecting the soil bacterial community, while pH and phosphorus (P) mainly affected the soil fungal community structures. No relationship between the changes of microbial communities and PAE residues in soil was observed. This study indicates that the soil acidification and nutrient accumulation under PGVC mainly shifted the changes of soil microbial community structures, which could occur after only 5 years of PGVC.