Conversion of estriol to estrone: A bacterial strategy for the catabolism of estriol.

Natural estrogens, including estrone (E1), 17ß-estradiol (E2), and estriol (E3), are potentially carcinogenic pollutants commonly found in water and soil environments. Bacterial metabolic pathway of E2 has been studied; however, the catabolic products of E3 have not been discovered thus far. In this study, Novosphingobium sp. ES2-1 was used as the target strain to investigate its catabolic pathway of E3. The metabolites of E3 were identified by high performance liquid chromatography-high resolution mass spectrometry (HPLC-HRMS) combined with stable 13C3-labeling. Strain ES2-1 could almost completely degrade 20 mg∙L-1 of E3 within 72 h under the optimal conditions of 30°C and pH 7.0. When inoculated with strain ES2-1, E3 was initially converted to E1 and then to 4-hydroxyestrone (4-OH-E1), which was then cleaved to HIP (metabolite A6) via the 4, 5-seco pathway or cleaved to the B loop via the 9,10-seco pathway to produce metabolite with a long-chain ketone structure (metabolite B4). Although the ring-opening sequence of the above two metabolic pathways was different, the metabolism of E3 was achieved especially through continuous oxidation reactions. This study reveals that, E3 could be firstly converted to E1 and then to 4-OH-E1, and finally degraded into small molecule metabolites through two alternative pathways, thereby reducing E3 pollution in water and soil environments.

Novel insights into the mechanism of laccase-driven rhizosphere humification for alleviating wheat 17ß-estradiol contamination.

Global-scale crop contamination with environmental estrogens has posed a huge risk to agri-food safety and human health. Laccase is regarded as an unexceptionable biocatalyst for regulating pollution and expediting humification, but the knowledge of estrogen bioremediation and C storage strengthened by laccase-driven rhizosphere humification (LDRH) remains largely unknown. Herein, a greenhouse microcosm was performed to explore the migration and fate of 17ß-estradiol (E2) in water-wheat (Triticum aestivum L.) matrices by LDRH. Compared to the non-added laccase, the pseudo-first-order decay rate constants of E2 in the rhizosphere solution after 10 and 50 µM exposures by LDRH increased from 0.03 and 0.02 h-1 to 0.36 and 0.09 h-1, respectively. Furthermore, LDRH conferred higher yield, polymerizability, O-containing groups, and functional-C signals in the humified precipitates, because it accelerated the formation of highly complex precipitates by radical-controlled continuous polymerization. In particular, not only did LDRH mitigate the phytotoxicity of E2, but it also diminished the metabolic load of E2 in wheat tissues. This was attributed to the rapid attenuation of E2 in the rhizosphere solution during LDRH, which limited E2 uptake and accumulation in each subcellular fraction of the wheat roots and shoots. Although several typical intermediate products such as estrone, estriol, and E2 oligomers were detected in roots, only small-molecule species were found in shoots, evidencing that the polymeric products of E2 were unable to be translocated acropetally due to the vast hydrophobicity and biounavailability. For the first time, our study highlights a novel, eco-friendly, and sustainable candidate for increasing the low-C treatment of organics in rhizosphere microenvironments and alleviating the potential risks of estrogenic contaminants in agroenvironments.

Tetracyclines uptake from irrigation water by vegetables: Accumulation and antimicrobial resistance risks.

Wastewater irrigation may introduce antibiotic residues in the soil-plant systems. This study aimed to investigate the uptake of tetracyclines by spinach and collard greens and assess associated ecological and human health risks. Synthetic wastewater spiked with 1 ppm and 10 ppm of oxytetracycline, doxycycline, and tetracycline was used to grow vegetables in a greenhouse pot experiment. The uptake and accumulation of the tetracyclines were low and residual concentrations in the soil were negligible. All the tetracyclines were detected at concentrations ranging from 1.68 to 51.41 µg/g (spinach) and 1.94-30.95 µg/g (collard greens). The accumulation rate was in a dose-response scenario with a bioconcentration factor of 6.34 mL/kg (spinach) and 2.64 mL/kg (collard greens). Oxytetracycline had the highest accumulation in leaves, followed by doxycycline and tetracycline, and the residual concentrations followed the same order. The highest residual concentration was in soils receiving 10 ppm oxytetracycline. Residual concentrations in the soil were lower than accumulated levels and exerted negligible ecological risks. Tetracyclines accumulation in spinach significantly differed between the vegetables demonstrating a subspecies difference in uptake and accumulation. Ecological risk quotient (RQ) and human health risk quotient (HQ) were below thresholds that would exert toxicity and resistance selection impacts. Although RQs and HQs are low (<0.1), this study shows that the vegetables accumulate tetracyclines from irrigation water, posing plausible human health risks to allergic individuals. Similarly, the ecological risks cannot be ignored because the synergistic and antagonistic effects of sublethal concentrations can perturb ecosystem processes.

Estrogens and xenoestrogen residues in manure-based fertilizers and their potential ecological risks.

Optimal manure treatment aimed at usage as agricultural soil fertilizers is a prerequisite ecological pollution control strategy. In this work, livestock manure-based fertilizers were collected from 71 animal farms across 14 provinces in China. The contamination levels and potential ecotoxicological risks of residual steroid estrogens (SEs): estrone (E1), estriol (E3), 17α-estradiol (17α-E2), 17ß-estradiol (17ß-E2) and xenoestrogen (XE) bisphenol A (BPA), were investigated. The results showed that the occurrence frequencies for SEs and XE ranged from 66.67% to 100%, and the mean concentration varied considerably across the study locations. The total content of SEs and XE in Hebei province was the highest, and swine manure-based fertilizers concentrations were higher than the levels reported in other animal fertilizers. Compared with farm level manure, manure-based fertilizers are processed by composting, and the micropollutants quantities are significantly reduced (mean: 87.65 - 534.02 µg/kg). The total estradiol equivalent quantity (EEQ) that might migrate to the soil was estimated to be 1.23 µg/kg. Based on the estimated application rate of manure, 38% of the fertilizers risk quotients exceeded 0.1, indicating medium to high risks pressure on terrestrial organisms. Nonetheless, the estrogenic risk was lower in manure-based fertilizers than in manure. This study highlights the significance of proper treatment of livestock manure and designing an optimal manure fertilization strategy to mitigate the risks posed by SEs and XEs to the agroecosystems.

Biotransformation of bisphenol A in vivo and in vitro by laccase-producing Trametes hirsuta La-7: Kinetics, products, and mechanisms.

Bisphenol A (BPA) is a ubiquitous endocrine disruptor that poses adverse human health risks. Herein, biotransformation kinetics, products, and mechanisms of BPA undergoing a laccase-producing Trametes hirsuta La-7 metabolism were for the first time reported. Strain La-7 could completely biotransform ≤0.5 mmol·L-1 BPA within 6 d in vivo. Notably, its extracellular crude laccase solution (ECLS) and intracellular homogenized mycelium (HM) only required 6 h to convert 85.71% and 84.24% of 0.5 mmol·L-1 BPA in vitro, respectively. The removal of BPA was noticeably hampered by adding a cytochrome P-450 inhibitor (piperonyl butoxide) in HM, disclosing that cytochrome P-450 monooxygenase participated in BPA oxidation and metabolism. BPA intermediates were elaborately identified by high-resolution mass spectrometry (HRMS) combined with 13C stable isotope ratios (BPA: 13C12-BPA = 0.25: 0.25, molar concentration). Based on the accurate molecular mass, isotope labeling difference, and relative intensity ratio of product peaks, 6 versatile metabolic mechanisms of BPA, including polymerization, hydroxylation, dehydration, bond cleavage, dehydrogenation, and carboxylation in vivo and in vitro, were confirmed. Germination index values revealed that inoculating strain La-7 in a BPA-contaminated medium presented no phytotoxicity to the germinated radish (Raphanus sativus L.) seeds. In vivo, Mg2+, Fe2+, Fe3+, and Mn2+ were conducive to BPA removal, but Cd2+ and Hg2+ significantly obstructed BPA elimination. Additionally, strain La-7 also exhibited high-efficiency metabolic ability toward estrone (E1), 17ß-estradiol (E2), and 17α-ethinylestradiol (EE2), with more than 96.13%, 96.65%, and 100% of E1, E2, and EE2 having been converted, respectively. Our findings provide an environmentally powerful laccase-producing fungus to decontaminate endocrine disruptor-contaminated water matrices by radical polymerization and oxidative decomposition.

Effects and mechanisms of plant growth regulators on horizontal transfer of antibiotic resistance genes through plasmid-mediated conjugation.

A vast number of bacteria occur in both soil and plants, with some of them harboring antibiotic resistance genes (ARGs). When bacteria congregate on the interface of soil particles or on plant root surfaces, these ARGs can be transferred between bacteria via conjugation, leading to the formation of antibiotic-resistant pathogens that threaten human health. Plant growth regulators (PGRs) are widely used in agricultural production, promoting plant growth and increasing crop yields. However, until now, little information has been known about the effects of PGRs on the horizontal gene transfer (HGT) of ARGs. In this study, with Escherichia coli DH5α (carrying RP4 plasmid with TetR, AmpR, KanR) as the donor and E. coli HB101 as the recipient, a series of diparental conjugation experiments were conducted to investigate the effects of indoleacetic acid (IAA), ethel (ETH) and gibberellin (GA3) on HGT of ARGs via plasmid-mediated conjugation. Furthermore, the mechanisms involved were also clarified. The results showed that all three PGRs affected the ARG transfer frequency by inducing the intracellular reactive oxygen species (ROS) formation, changing the cell membrane permeability, and regulating the gene transcription of traA, traL, trfAp, trbBp, kilA, and korA in plasmid RP4. In detail, 50-100 mg⋅L-1 IAA, 20-50 mg⋅L-1 ETH and 1500-2500 mg⋅L-1 GA3 all significantly promoted the ARG conjugation. This study indicated that widespread use of PGRs in agricultural production could affect the HGT of ARGs via plasmid-mediated conjugation, and the application of reasonable concentrations of PGRs could reduce the ARG transmission in both soil environments and plants.

Genotoxicity of organic contaminants in the soil: A review based on bibliometric analysis and methodological progress.

Organic contaminants (OCs) are ubiquitous in the environment, posing severe threats to human health and ecological balance. In particular, OCs and their metabolites could interact with genetic materials to induce genotoxicity, which has attracted considerable attention. In this review, bibliometric analysis was executed to analyze the publications on the genotoxicity of OCs in soil from 1992 to 2021. The result indicated that significant contributions were made by China and the United States in this field and the research hotspots were biological risks, damage mechanisms, and testing methods. Based on this, in this review, we summarized the manifestations and influencing factors of genotoxicity of OCs to soil organisms, the main damage mechanisms, and the most commonly utilized testing methods. OCs can induce genotoxicity and the hierarchical response of soil organisms, which could be influenced by the physicochemical properties of OCs and the properties of soil. Specific mechanisms of genotoxicity can be classified into DNA damage, epigenetic toxicity, and chromosomal aberrations. OCs with different molecular weights lead to genetic material damage by inducing the generation of ROS or forming adducts with DNA, respectively. The micronucleus test and the comet test are the most commonly used testing methods. Moreover, this review also pointed out that future studies should focus on the relationships between bioaccessibilities and genotoxicities, transcriptional regulatory factors, and potential metabolites of OCs to elaborate on the biological risks and mechanisms of genotoxicity from an overall perspective.

Distribution, ecological fate, and risks of steroid estrogens in environmental matrices.

Over the past two decades, steroidal estrogens (SEs) such as 17α-ethylestradiol (EE2), 17ß-estradiol (E2),17α-estradiol (17α-E2), estriol (E3) and estrone (E1) have elicited worldwide attention due to their potentially harmful effects on human health and aquatic organisms even at low concentration ng/L. Natural steroidal estrogens exhibit greater endocrine disruption potency due to their high binding effect on nuclear estrogen receptors (ER). However, less has been explored regarding their associated environmental risks and fate. A comprehensive bibliometric study of the current research status of SEs was conducted using the Web of Science to assess the development trends and current knowledge of SEs in the last two decades, from 2001 to 2021 October. The number of publications has tremendously increased from 2003 to 2021. We summarized the contamination status and the associated ecological risks of SEs in different environmental compartments. The results revealed that SEs are ubiquitous in surface waters and natural SEs are most studied. We further carried out an in-depth evaluation and synthesis of major research hotspots and the dominant SEs in the matrices were E1, 17ß-E2, 17α-E2, E3 and EE2. Nonetheless, investigations of SEs in soils, groundwater, and sediments remain scarce. This study elucidates SEs distribution, toxicological risks, ecological fate and mitigation measures, which will be beneficial for future monitoring, management, and risk assessment. Further studies are recommended to assess the toxicological risks of different SEs in complex environmental matrices to pursue a more precise and holistic quantitative estimation of estrogenic risk.

Ce(â ¢) activates peroxymonosulfate for the degradation of substituted PAHs.

Substituted polycyclic aromatic hydrocarbons (SPAHs) are being intensively investigated, considering their high toxicity. Additionally, the mechanism of the effect of substituents on the removal of SPAHs and the activation of Ce(III) ions on peroxymonosulfate (PMS) have not been explored. Here we evaluated the removal efficiency of SPAHs in the oxidation system constructed by Ce(Ⅲ) ions and PMS, with emphasized the effect of substituents on SPAHs degradation. Ce(Ⅲ) has high catalytic performance for PMS, and the degradation percentage of all pollutants was higher than 92%. The significantly negative correlation between the reaction rate constants of SPAHs and the highest occupied molecular orbital-the lowest unoccupied molecular orbital gap, confirms that substituents lead to the differences in the degradation of SPAHs. The generation of reactive oxygen species (SO4•-, •OH, and 1O2) is based on the electron transfer between Ce(Ⅲ) and PMS, and the contribution of ROS to substituted naphthalene varies due to the role of substituents. The Ce(Ⅳ)/Ce(Ⅲ) cycle accelerates the activation of PMS. Based on the transformation products and condensed Fukui function, the possible degradation pathways are inferred. In addition, inorganic anions and organic matter have little effect on the Ce(Ⅲ)/PMS system, which is a prerequisite for applying this system to real-world waste-water for SPAHs removal. This work demonstrates a new model of the degradation mechanism of SPAHs in the Ce(Ⅲ)/PMS system.

Nitrogen addition enhanced the polycyclic aromatic hydrocarbons dissipation through increasing the abundance of related degrading genes in the soils.

High concentrations of Polycyclic Aromatic Hydrocarbons (PAHs) in the soils cause significant threats to human health. Since nitrogen plays a crucial role in controlling microbial composition and functions in terrestrial ecosystems, bio-stimulation based on nitrogen has been used in PAHs contaminated environments remediation. Recent studies show that microbial community composition and organic pollutants dissipation correlate with nitrogen addition. Here, we investigated the effect of nitrogen addition on the abundance of microbial community, degrading genes, and their relationship to PAHs dissipation. After a 32-day experiment, PAHs residues in nitrogen treatment soil were reduced by 23.23%-34.21%. The application of 80 mg·kg-1 nitrate and ammonium nitrogen resulted in higher PAHs removal efficiency, and the dissipation rate of PAHs was 59.61% and 62.09%, respectively. Nitrogen application could improve the abundance and the diversity of soil microbial community. Degrading genes involved in PAH detoxification were enhanced after nitrogen addition, particularly those encoding ring-hydroxylating and catechol dioxygenases such as nahAc and nidA, thus, accelerating PAH dissipation in the soil. The results will facilitate the development of beneficial microbiome-based remediation strategies and improve agricultural production safety in PAHs-contaminated soils.

Impact of Plastic Particles on the Horizontal Transfer of Antibiotic Resistance Genes to Bacterium: Dependent on Particle Sizes and Antibiotic Resistance Gene Vector Replication Capacities.

Plastic particles impact the propagation of antibiotic resistance genes (ARGs) in environmental media, and their perturbation on the horizontal gene transfer (HGT) of ARGs is recognized as a critical influencing mechanism. However, studies concerning the influence and influencing mechanisms of plastic particles on the HGT of ARGs were limited, particularly for the effect of particle sizes and ARG vector-associated mechanisms. This study explored the impact of polystyrene (PS) particles with sizes of 75, 90, 100, 1000, and 10000 nm on the HGT (via transformation) of ARGs mediated by pUC19, pSTV29, and pBR322 plasmids into Escherichia coli cells. PS particles with sizes ≤100 nm impacted the transformation of ARGs, but large particles (1000 and 10000 nm) showed no obvious effects. Effects of PS particles on the transfer of three plasmids were vastly distinct. For pUC19 with high replication capacities, the transfer was monotonously promoted. However, for pSTV29 and pBR322 with low replication capacities, suppressing effects were observed. This was attributed to two competing mechanisms. The enhancing mechanism was that the direct interaction of PS particles with membrane lipids and the indirect effect associated with bacterial oxidative stress response induced pore formation on the cell membrane and increased membrane permeability, thus enhancing plasmid entrance. The inhibiting mechanism was that PS particles interfered with plasmid replication inside E. coli, thus decreasing the bacterial tranformation. This study deepened our understanding of the environmental dissemination of ARGs in plastic contamination.

Functional group substitutions influence the binding of benzophenone-type UV filters with DNA.

As a class of possible carcinogens, benzophenone-type UV filters (BPs) widely exist in natural environments and organisms. The crucial step of the carcinogenic process induced by cancerous toxins is binding with DNA to form adducts. Here, the binding of 10 typical BPs, i.e., benzophenone (BP1), 2-hydroxyl benzophenone (BP2), 4-hydroxyl benzophenone (BP3), 2,2'-dihydroxyl benzophenone (BP4), 2,4-dihydroxyl benzophenone (BP5), 4,4'-dihydroxyl benzophenone (BP6), 2,4,4'-trihydroxyl benzophenone (BP7), 2,2',4,4'-tetrahydroxyl benzophenone (BP8), 2-hydroxyl-4-methoxyl benzophenone (BP9), and 2,2'-dihydroxyl-4-methoxyl benzophenone (BP10), with DNA was tested via fluorescence quenching experiments. Only hydroxyl group-substituted BPs could bind to DNA by groove binding mode, and the quenching constants were 0.93 × 103-5.89 × 103 L/mol. Substituted BPs were preferentially bound to thymine. Circular dichroism analysis confirmed that BPs could affect DNA base stacking but could not transform its B-form. Based on molecular electrostatic surface potential analyses, molecular dynamics simulations, and energy decomposition calculations, it could be found that the site and number of hydroxyl substitution changed the molecular polarity of BPs, thereby affecting the number and strength of hydrogen bonds between BPs and DNA. The hydroxyl substitution at site 2 was more conducive to binding than at site 4. This study is beneficial in comprehending the carcinogenic mechanisms of BPs.

Nitrogen Regulates the Distribution of Antibiotic Resistance Genes in the Soil-Vegetable System.

The increasing antibiotic resistance genes (ARGs) in fertilizer-amended soils can potentially enter food chains through their transfer in a soil-vegetable system, thus, posing threats to human health. As nitrogen is an essential nutrient in agricultural production, the effect of nitrogen (in the forms NH4 +-N and NO3 --N) on the distribution of ARGs (blaTEM-1, sul1, cmlA, str, and tetO) and a mobile genetic element (MGE; tnpA-4) in a soil-Chinese cabbage system was investigated. Not all the tested genes could transfer from soil to vegetable. For transferable ones (blaTEM-1, sul1, and tnpA-4), nitrogen application influenced their abundances in soil and vegetable but did not impact their distribution patterns (i.e., preference to either leaf or root tissues). For ARGs in soil, effects of nitrogen on their abundances varied over time, and the positive effect of NH4 +-N was more significant than that of NO3 --N. The ARG accumulation to vegetables was affected by nitrogen application, and the nitrogen form was no longer a key influencing factor. In most cases, ARGs were found to prefer being enriched in roots, and nitrogen application may slightly affect their migration from root to leaf. The calculated estimated human intake values indicated that both children and adults could intake 106-107 copies of ARGs per day from Chinese cabbage consumption, and nitrogen application affected ARG intake to varying degrees. These results provided a new understanding of ARG distribution in vegetables under the agronomic measures such as nitrogen application, which may offer knowledge for healthy vegetable cultivation in future.

Enhanced transformation capability towards benzo(a)pyrene by Fe(III)-modified manganese oxides.

Manganese oxides (Mn oxides) are ubiquitous and may coexist with Fe(III) ions in soil environments. In this study, acid birnessite, alkaline birnessite, cryptomelane, pyrolusite, manganite, and their Fe(III)-modified analogues were synthesized and used for benzo(a)pyrene transformation. Fe-modified Mn oxides show a markedly enhanced transformation capability towards benzo(a)pyrene. Specifically, the benzo(a)pyrene transformation rate constants k for Bir-H, Bir-OH, Cry, Pyr, and Man were 0.49, 0.080, 0.0071, 0.0055, and 0.0022 h-1, respectively. After Fe(III) modification, the transformation rate constants were increased to 22, 2.7, 0.25, 0.0072 and 0.0098 h-1, respectively. Fe(III)-modified layered birnessites exhibited better activity than Fe(III)-modified tunnel Mn oxides, which was attributed to their high Fe(III) contents and abundant active free radicals. Fe(III) was found to accept electrons from benzo(a)pyrene, thereby accelerating the benzo(a)pyrene transformation. Moreover, modification with Fe(III) increased the surface adsorbed water and oxygen, and promoted the generation of active free radicals. Finally, the physicochemical and biochemical properties of transformation products showed the environmental benefits of this process. Overall, the results indicate that the occurrence of Fe(III) ions could promote the removal of PAHs in Mn oxides-rich soils, and this study provides a credible understanding of PAH fates in natural soils.

Enhanced PAHs-contaminated site soils remediation by mixed persulfate and calcium peroxide.

Polycyclic aromatic hydrocarbons (PAHs) remain in the site soils after relocated coking plants and oil refineries pose huge constraints to the subsequent land utilization. However, single persulfate (PS) or calcium peroxide (CP) remediation strategies can only inefficiently oxidize some PAHs in soil. This work sought to optimize PS/CP oxidation remediation strategy and verify its practical application effect in soil samples spiked with PAHs. The results showed that the mixed PS/CP oxidation remediation was better than the single oxidants strategies; it had high remediation performance in different particles and pollution loads of PAHs-contaminated soils. Simultaneously, reactive radicals (SO4·- and ·OH) were detected, and one side-product (CaSO4) was characterized. This work optimized the mixed PS/CP system (0.3 mol/L PS, and 8 g/kg CP, together with 0.18 mol/L Fe2+ and 0.11 mol/L C2O42-), and the corresponding Total-PAHs removal rate was 85.41%. Compared to the cost based on benzopyrene (BaP) removal, the study provided a cost-effective mixed PS/CP oxidation remediation technique (1.22 $/ton), widely applicable in soils polluted with various organic contaminants represented such as PAHs.

Up-regulation of ribosomal and carbon metabolism proteins enhanced pyrene biodegradation in fulvic acid-induced biofilm system.

The polycyclic aromatic hydrocarbons (PAHs) that enter the aqueous phase usually coexist with fulvic acid (FA). Therefore, we initiated this investigation to explore the influences of FA on bacterial biofilm formation and its potential to biodegrade pyrene (PYR), using electron microscopic techniques and isobaric tags for relative and absolute quantification (iTRAQ). Our results revealed that FA stimulated biofilm formation and enhanced the biodegradation of PYR. First, FA favored the three-dimensional proliferation of bacteria, with an OD590/OD600 value of up to 14.78, and the extracellular surfaces covered by a layer of biomaterials. Distinctive intracellular morphologies of texture and organization were accompanied by reduced inter-bacterial distances of less than 0.31 µm. The biofilms formed displayed interactions between FA and surficial proteins, as noted by band shifts for the C-O and CO groups. Strikingly, FA triggered the upregulation of 130 proteins that were either operational in biofilm formation or in metabolic adjustments; with the changes supported by the increasing intensity of free amino acids and the newly generated N-O bonds. The results above revealed that the enhanced biodegradation was related to the up-regulation of the proteins functioned for ribosomal and carbon metabolism, and the ultra-structural changes in FA-induced biofilm system.

Ecological and human health risks of manure-borne steroid estrogens: A 20-year global synthesis study.

Estrone (E1), 17α-estradiol (17α-E2), 17ß-estradiol (17ß-E2), and estriol (E3) are persistent in livestock manure and present serious pollution concerns because they can trigger endocrine disruption at part-per-trillion levels. This study conducted a global analysis of estrogen occurrence in manure using all literature data over the past 20 years. Besides, predicted environmental concentration (PEC) in soil and water was estimated using fate models, and risk/harm quotient (RQ/HQ) methods were applied to screen risks on children as well as on sensitive aquatic and soil species. The estradiol equivalent values ranged from 6.6 to 4.78 × 104 ng/g and 12.4 to 9.46 × 104 ng/L in the solid and liquid fraction. The estrogenic potency ranking in both fractions were 17ß-E2> E1>17α-E2>E3. RQs of measured environmental concentration in the liquid fraction pose medium (E3) to high risk (E1, 17α-E2 & 17ß-E2) to fish but are lower than risks posed by xenoestrogens. However, the RQ of PECs on both soil organisms and aquatic species were insignificant (RQ < 0.01), and HQs of contaminated water and soil ingestion were within acceptable limits. Nevertheless, meticulous toxicity studies are still required to confirm (or deny) the findings because endocrine disruption potency from mixtures of these classes of compounds cannot be ignored.

Humidity induces the formation of radicals and enhances photodegradation of chlorinated-PAHs on Fe(III)-montmorillonite.

Chlorinated-PAHs (ClPAHs) are widely detected in the soil surface and atmospheric particles. However, the underlying mechanisms of their photodegradation are not well understood. In the present study, the formation of radicals on ClPAHs-contaminated clay minerals was quantitatively monitored via electron paramagnetic resonance (EPR) spectroscopy, and the impact of relative humidity (RH) was systematically explored. ClPAHs removal (> 75%) was attributed to electron transfer and •OH attack. The degradation easiness of ClPAHs follows: 2-ClNAP >2-ClANT >9-ClPHE >1-ClPYR. Light irradiation significantly improved the generation of reactive oxygen species (ROS, such as •OH and •O2-), and further generate a series of hydroxylated products of ClPAHs. Persistent free radicals (PFRs) were only detected on clay minerals contaminated with 2-ClANT and 1-ClPYR. RH 10-80%, the concentration of •OH and •O2- increased by 1.07 and 62.79 times respectively, which facilitated transformation of PFRs and ClPAHs degradation. The results of quantum chemical calculations indicate that the initial reaction of ClPAHs photodegradation is mediated by the substitution of •OH for chlorine groups. The present work implies that higher humidity may decrease the generation of PFRs on clay minerals and help mitigate the threats of PFRs and ClPAHs to human health.

Formation of environmentally persistent free radicals from photodegradation of triclosan by metal oxides/silica suspensions and particles.

Metal oxides play an essential role in the photocatalysis of contaminants and substantially increase in the environment by the engineering production. However, whether emerging contaminants will be produced during photocatalysis of contaminants remains unclear. Here, triclosan (TCS) photodegradation in metal oxides/silica suspensions and particles, simulated as the states of metal oxides in water and soil environments, were studied. The photodegradation results confirmed that metal oxides exhibited a double-effect. They promoted TCS photodegradation by generating reactive oxidizing species (ROS) in metal oxides/silica suspensions and inhibited the photodegradation by competing with TCS for irradiation in metal oxides/silica particles. In this study, the critical discovery was the formation of emerging contaminants, environmentally persistent free radicals (EPFRs), and EPFRs yields were promoted by metal oxides (Al2O3, ZnO, TiO2). They were more stable in metal oxides than silica, and the half-lives ranged from 6.7 h to 90.9 d. Although CuO did not increase EPFRs yields compared to silica, the half-lives of EPFRs were also longer. In addition, this study found that EPFRs yields were dependent on the metal oxides concentrations. Our results provided a new insight into the negative environmental impacts of metal oxides and improved our understanding of the formation and fate of EPFRs by metal oxides in soil and aquatic environments.

Reducing Phenanthrene Contamination in Trifolium repens L. With Root-Associated Phenanthrene-Degrading Bacterium Diaphorobacter sp. Phe15.

Some root-associated bacteria could degrade polycyclic aromatic hydrocarbons (PAHs) in contaminated soil; however, their dynamic distribution and performance on root surface and in inner plant tissues are still unclear. In this study, greenhouse container experiments were conducted by inoculating the phenanthrene-degrading bacterium Diaphorobacter sp. Phe15, which was isolated from root surfaces of healthy plants contaminated with PAHs, with the white clover (Trifolium repens L.) via root irrigation or seed soaking. The dynamic colonization, distribution, and performance of Phe15 in white clover were investigated. Strain Phe15 could efficiently degrade phenanthrene in shaking flasks and produce IAA and siderophore. After cultivation for 30, 40, and 50 days, it could colonize the root surface of white clover by forming aggregates and enter its inner tissues via root irrigation or seed soaking. The number of strain Phe15 colonized on the white clover root surfaces was the highest, reaching 6.03 Log CFU⋅g-1 FW, followed by that in the roots and the least in the shoots. Colonization of Phe15 significantly reduced the contents of phenanthrene in white clover; the contents of phenanthrene in Phe15-inoculated plants roots and shoots were reduced by 29.92-43.16 and 41.36-51.29%, respectively, compared with the Phe15-free treatment. The Phe15 colonization also significantly enhanced the phenanthrene removal from rhizosphere soil. The colonization and performance of strain Phe15 in white clove inoculated via root inoculation were better than seed soaking. This study provides the technical support and the resource of strains for reducing the plant PAH pollution in PAH-contaminated areas.