Unveiling complete natural reductive dechlorination mechanisms of chlorinated ethenes in groundwater: Insights from functional gene analysis.

Monitored natural attenuation (MNA) of chlorinated ethenes (CEs) has proven to be a cost-effective and environment-friendly approach for groundwater remediation. In this study, the complete dechlorination of CEs with formation of ethene under natural conditions, were observed at two CE-contaminated sites, including a pesticide manufacturing facility (PMF) and a fluorochemical plant (FCP), particularly in the deeply weathered bedrock aquifer at the FCP site. Additionally, a higher abundance of CE-degrading bacteria was identified with heightened dechlorination activities at the PMF site, compared to the FCP site. The reductive dehalogenase genes and Dhc 16 S rRNA gene were prevalent at both sites, even in groundwater where no CE dechlorination was observed. vcrA and bvcA was responsible for the complete dechlorination at the PMF and FCP site, respectively, indicating the distinct contributions of functional microbial species at each site. The correlation analyses suggested that Sediminibacterium has the potential to achieve the complete dechlorination at the FCP site. Moreover, the profiles of CE-degrading bacteria suggested that dechlorination occurred under Fe3+/sulfate-reducing and nitrate-reducing conditions at the PMF and FCP site, respectively. Overall these findings provided multi-lines of evidence on the diverse mechanisms of CE-dechlorination under natural conditions, which can provide valuable guidance for MNA strategies implementation.

Mechanisms of benzene and benzo[a]pyrene biodegradation in the individually and mixed contaminated soils.

There is a lack of knowledge on the biodegradation mechanisms of benzene and benzo [a]pyrene (BaP), representative compounds of polycyclic aromatic hydrocarbons (PAHs), and benzene, toluene, ethylbenzene, and xylene (BTEX), under individually and mixed contaminated soils. Therefore, a set of microcosm experiments were conducted to explore the influence of benzene and BaP on biodegradation under individual and mixed contaminated condition, and their subsequent influence on native microbial consortium. The results revealed that the total mass loss of benzene was 56.0% under benzene and BaP mixed contamination, which was less than that of individual benzene contamination (78.3%). On the other hand, the mass loss of BaP was slightly boosted to 17.6% under the condition of benzene mixed contamination with BaP from that of individual BaP contamination (14.4%). The significant differences between the microbial and biocide treatments for both benzene and BaP removal demonstrated that microbial degradation played a crucial role in the mass loss for both contaminants. In addition, the microbial analyses revealed that the contamination of benzene played a major role in the fluctuations of microbial compositions under co-contaminated conditions. Rhodococcus, Nocardioides, Gailla, and norank_c_Gitt-GS-136 performed a major role in benzene biodegradation under individual and mixed contaminated conditions while Rhodococcus, Noviherbaspirillum, and Phenylobacterium were highly involved in BaP biodegradation. Moreover, binary benzene and BaP contamination highly reduced the Rhodococcus abundance, indicating the toxic influence of co-contamination on the functional key genus. Enzymatic activities revealed that catalase, lipase, and dehydrogenase activities proliferated while polyphenol oxidase was reduced with contamination compared to the control treatment. These results provided the fundamental information to facilitate the development of more efficient bioremediation strategies, which can be tailored to specific remediation of different contamination scenarios.

Effects of short and long-term thermal exposure on microbial compositions in soils contaminated with mixed benzene and benzo[a]pyrene: A short communication.

Polycyclic aromatic hydrocarbons (PAHs) and benzene, toluene, ethylbenzene, and xylene (BTEX) are the most persistent and toxic organic contaminants often found co-contaminated in anthropogenic and petrochemical industrial sites. Therefore, an experiment was performed for the safe biodegradation of benzene and benzo[a]pyrene (BaP) through thermally-enhanced biodegradation, and to explore the influence of elevated thermal treatments on microbial diversity and composition. The results revealed that elevated thermal treatments (15 to 45 °C) significantly enhanced the diversity of both bacteria and fungi. The composition analysis revealed that short-term and long-term elevated temperature conditions can directly enhance the specificity of microorganisms that play a crucial role in the biodegradation of benzene and BaP co-contaminated soil. Moreover, the indirect role of elevated temperature conditions on microbial compositions was through the fluctuations of soil properties, especially soil pH, moisture, TOC, potassium, phosphorous, total Fe, Fe(II), and Fe(III). In addition, the correlation analyses revealed that thermal exposure enhances the synergistic association (fungal-fungal, fungal-bacterial, bacterial-bacterial) of microbes to degrade the toxic contaminants and to cope with harsh environmental conditions. These results concluded that the biodegradation of benzene and BaP co-contamination was efficiently enhanced under the thermally-enhanced biodegradation approach and the elevation of temperature can affect the microbial compositions directly via microbial specificity or indirectly by influencing the soil properties.

Thermally enhanced biodegradation of benzo[a]pyrene and benzene co-contaminated soil: Bioavailability and generation of ROS.

In this study, a set of comprehensive experiments were conducted to explore the effects of temperature on the biodegradation, bioavailability, and generation of reactive oxygen species (ROS) by thermally enhanced biodegradation (TEB) under benzene and BaP co-contaminated conditions. The biodegradation rates of benzene increased from 57.4% to 88.7% and 84.9%, and the biodegradation efficiency of BaP was enhanced from 15.8% to 34.6% and 28.6%, when the temperature was raised from the ambient temperature of 15 °C to 45 °C and 30 °C, respectively. In addition, the bioavailability analysis results demonstrated that the water- and butanol-extractable BaP increased with elevated temperatures. High enzymatic activities and PAH-RHDα gene in gram-positive bacteria favored the long-term elevated temperatures (30 and 45 °C) compared to gram-negative bacteria. Moreover, ROS species (O2•- and •OH) generation was detected which were scavenged by the increased superoxide dismutase and catalase activities at elevated temperatures. Soil properties (pH, TOC, moisture, total iron, Fe3+, and Fe2+) were affected by the temperature treatments, revealing that metal-organic-associated reactions occurred during the TEB of benzene-BaP co-contamination. The results concluded that biodegradation of benzene-BaP co-contamination was greatly improved at 45 °C and that microbial activities enhanced the biodegradation under TEB via the increased bioavailability and generation and degradation of ROS.

Mechanisms of biostimulant-enhanced biodegradation of PAHs and BTEX mixed contaminants in soil by native microbial consortium.

Despite the co-occurrence of polycyclic aromatic hydrocarbons (PAHs) and benzene, toluene, ethylbenzene, and xylene (BTEX) in the field, to date, knowledge on the bioremediation of benzene and benzo[a]pyrene (BaP) mixed contaminants is limited. In this study, the mechanisms underlying the biodegradation of benzene and BaP under individual and co-contaminated conditions followed by the enhanced biodegradation using methanol, ethanol, and vegetable oil as biostimulants were investigated. The results demonstrated that the benzene biodegradation was highly reduced under the co-contaminated condition compared to the individual benzene contamination, whereas the BaP biodegradation was slightly enhanced with the co-contamination of benzene. Moreover, biostimulation significantly improved the biodegradation of both contaminants under co-contaminated conditions. A trend of significant reduction in the bioavailable BaP contents was observed in all biostimulant-enhanced groups, implying that the bioavailable BaP was the preferred biodegradable BaP fraction. Furthermore, the enzymatic activity analysis revealed a significant increase in lipase and dehydrogenase (DHA) activities, as well as a reduction in the catalase and polyphenol oxidase, suggesting that the increased hydrolysis of fats and proton transfer, as well as the reduced oxidative stress, contributed to the enhanced benzene and BaP biodegradation in the vegetable oil treatment. In addition, the microbial composition analysis results demonstrated that the enriched functional genera contributed to the increased biodegradation efficiency, and the functional genera in the microbial consortium responded differently to different biostimulants, and competitive growth was observed in the biostimulant-enhanced treatments. In addition, the enrichment of Pseudomonas and Rhodococcus species was noticed during the biostimulation of benzene and BaP co-contamination soil, and was positively correlated with the DHA enzyme activities, indicating that these species encode DHA genes which contributed to the higher biodegradation. In conclusion, multiple lines of evidence were provided to shed light on the mechanisms of biostimulant-enhanced biodegradation of PAHs and BTEX co-contamination with native microbial consortiums.

Effects of ilaprazole on the steady-state pharmacodynamics of clopidogrel in healthy volunteers: An open-label randomized crossover study.

Background: Previous studies have suggested that proton pump inhibitors could impair the antiplatelet effect of clopidogrel. It is uncertain whether ilaprazole affects the antiplatelet effect of clopidogrel. This study aimed to determine the drug-drug interaction between ilaprazole and clopidogrel. Methods: A randomized crossover trial of 40 healthy subjects was performed. Clopidogrel was administered alone or in combination with ilaprazole for 7 days. The maximal platelet aggregation (MPA) to 5 µmol/L adenosine diphosphate was measured by light transmission aggregometry and the platelet reactivity index (PRI) was determined by vasodilator-stimulated phosphoprotein P2Y12 assay. High on-treatment platelet reactivity (HOPR) was defined as a MPA of >40%. The inhibition of platelet aggregation (IPA) and PRI in the two phases were compared between two regimens after the last dosing. Results: IPA was comparable between the two regimens at 0, 10 and 24 h (p > 0.05), but higher at 4 h in the clopidogrel alone regimen compared with that in the combined treatment regimen (75.66 ± 18.44% vs. 70.18 ± 17.67%, p = 0.031). The inhibition of PRI was comparable between the two regimens at 0 and 24 h. There were no significant differences in the area under the time-IPA% curve (AUC) or the incidence of HOPR at all time-points between the two regimens. Conclusion: In healthy subjects, ilaprazole has limited effect on the pharmacodynamics of clopidogrel and it may not be clinically relevant. Clinical Trial Registration: [www.chictr.org.cn], identifier [ChiCTR2000031482].

Thermally enhanced bioremediation: A review of the fundamentals and applications in soil and groundwater remediation.

Thermally enhanced bioremediation (TEB), a new concept proposed in recent years, explores the combination of thermal treatment and bioremediation to address the challenges of the low efficiency and long duration of bioremediation. This study presented a comprehensive review regarding the fundamentals of TEB and its applications in soil and groundwater remediation. The temperature effects on the bioremediation of contaminants were systematically reviewed. The thermal effects on the physical, chemical and biological characteristics of soil, and the corresponding changes of contaminants bioavailability and microbial metabolic activities were summarized. Specifically, the increase in temperature within a suitable range can proliferate enzymes enrichment, extracellular polysaccharides and biosurfactants production, and further enhancing bioremediation. Furthermore, a systematic evaluation of TEB applications by utilizing traditional in situ heating technologies, as well as renewable energy (e.g., stored aquifer thermal energy and solar energy), was provided. Additionally, TEB has been applied as a biological polishing technology post thermal treatment, which can be a cost-effective method to address the contaminants rebounds in groundwater remediation. However, there are still various challenges to be addressed in TEB, and future research perspectives to further improve the basic understanding and applications of TEB for the remediation of contaminated soil and groundwater are presented.

Effects of co-occurrence of PFASs and chlorinated aliphatic hydrocarbons on microbial communities in groundwater: A field study.

The effects of per- and polyfluoroalkyl substances (PFASs) and chlorinated aliphatic hydrocarbons (CAHs) co-contamination on the microbial community in the field have not been studied. In this study, we evaluated the presence of PFASs and CAHs in groundwater collected from a fluorochemical plant (FCP), and carried out Illumina MiSeq sequencing to understand the impact of mixed PFASs and CAHs on the indigenous microbial community. The sum concentrations of 20 PFASs in FCP groundwater ranged from 2.05 to 317.40 µg/L, and the highest PFOA concentration was observed in the deep aquifer (60 m below ground surface), co-contaminated by dense non-aqueous-phase liquid (DNAPL). The existence of PFASs and CAHs co-contamination in groundwater resulted in a considerable decrease in the diversity of microbial communities, while the abundance of metabolisms associated with contaminants biodegradation has increased significantly compared to the background wells. Furthermore, Acinetobacter, Pseudomonas and Arthrobacter were the dominant genera in PFASs and CAHs co-contaminated groundwater. The presence of high concentrations of PFASs and CAHs has been positively associated with the genus of Citreitalea. Finally, geochemical parameters, such as ORP, sulfate and nitrate were the key factors to shape up the structure of the microbial community and sources to rich the abundance of the potential functional bacteria.

Co-occurrence and correlations of PFASs and chlorinated volatile organic compounds (cVOCs) in subsurface in a fluorochemical industrial park: Laboratory and field investigations.

Fluorochemical industrial park (FIP) represents an important source of per- and polyfluoroalkyl substances (PFASs) and chlorinated volatile organic compounds (cVOCs). Exploring the co-occurrence and correlations of PFASs and cVOCs is a key step towards the understanding their distributions in the field. In this study, perfluorooctanoic acid (PFOA) was the dominant compound in groundwater and aquifer solids, and elevated concentrations of short-chain perfluoroalkyl carboxylic acids (PFCAs) and hexafluoropropylene oxide oligomers were also detected in the field, suggesting their wide applications as substitutes for PFOA. Correlation analyses between PFASs and cVOCs suggested that cVOCs had a significant influence on the distribution and composition of PFASs in the field. In addition, the presence of cVOCs in the form of dense non-aqueous-phase organic liquids (DNAPL) affected the distribution and migration of PFASs at various depths, as evidenced by the relatively high PFASs concentrations (204 µg/L) and PFOA abundance (85.4%) in the deep aquifer, likely due to DNAPL-water interfaces sorption or partition into bulk DNAPL. The log Kd values, determined in the laboratory, were found to increase in the presence of DNAPL, especially for PFOA, with more than one time higher than those of perfluorobutanoic acid (PFBA) and hexafluoropropylene oxide dimer acid (HFPO-DA). This conclusion further demonstrated that PFOA had a higher potential to participate into DNAPL, which can migrate with DNAPL to the deep aquifer, supporting the higher abundance of PFOA in the deep aquifer mentioned above. However, the log Kd-field values of PFBA and HFPO-DA in the field were higher than that of PFOA, and no significant correlations (p > 0.05) were found between log Kd-field values and the chain-length of PFCAs at various depths, suggesting that the phenomena observed in the field are a result of composite influencing factors.

Bioremediation of PAHs and heavy metals co-contaminated soils: Challenges and enhancement strategies.

Systemic studies on the bioremediation of co-contaminated PAHs and heavy metals are lacking, and this paper provides an in-depth review on the topic. The released sources and transport of co-contaminated PAHs and heavy metals, including their co-occurrence through formation of cation-π interactions and their adsorption in soil are examined. Moreover, it is investigated that co-contamination of PAHs and heavy metals can drive a synergistic positive influence on bioremediation through enhanced secretion of extracellular polymeric substances (EPSs), production of biosynthetic genes, organic acid and enzymatic proliferation. However, PAHs molecular structure, PAHs-heavy metals bioavailability and their interactive cytotoxic effects on microorganisms can exert a challenging influence on the bioremediation under co-contaminated conditions. The fluctuations in bioavailability for microorganisms are associated with soil properties, chemical coordinative interactions, and biological activities under the co-contaminated PAHs-heavy metals conditions. The interactive cytotoxicity caused by the emergence of co-contaminants includes microbial cell disruption, denaturation of DNA and protein structure, and deregulation of antioxidant biological molecules. Finally, this paper presents the emerging strategies to overcome the bioavailability problems and recommends the use of biostimulation and bioaugmentation along with the microbial immobilization for enhanced bioremediation of PAHs-heavy metals co-contaminated sites. Better knowledge of the bioremediation potential is imperative to improve the use of these approaches for the sustainable and cost-effective remediation of PAHs and heavy metals co-contamination in the near future.

Series of Lanthanide-Mercury Compounds with Three-Dimensional Structures: Rational Preparation, Structures and Properties.

Three novel Ln-Hg complexes [Ln(H2O)2(µ-IA)3Hg3Br6] n (Ln = Pr (1), Nd (2), and Er (3); HIA is isonicotinic acid) are synthesized and characterized. They feature three-dimensional (3-D) motifs. Solid-state UV/vis diffuse reflectance spectroscopy found that their band gaps are 4.91, 4.59, and 2.68 eV. It is found that lanthanide ions could adjust the band structures of semiconductors. Their photoluminescence comes from their characteristic emissions of 1D2 → 3H4 of Pr3+, 7F7/2 → 4S3/2 and 4F3/2 → 4I9/2 of Nd3+, and 4I15/2 → 4F7/2 and 4I15/2 → 4S3/2 of Er3+. The CIE chromaticity coordinate is ( x = 0.5726, y = 0.4206), ( x = 0.7268, y = 0.2732), and ( x = 0.2923, y = 0.4317). Their magnetization susceptibility totally obeys the Curie-Weiss equation with antiferromagnetic performances.