Degradation Of Phthalate Esters Research Articles

Phthalate ester (PAEs) accumulation in wheat tissues and dynamic changes of rhizosphere microorganisms in the field with plastic-film residue

Phthalates acid esters (PAEs) have accumulated in soil and crops like wheat as a result of the widespread usage of plastic films. It is yet unclear, nevertheless, how these dynamic variations in PAE accumulation in wheat tissues relate to rhizosphere bacteria in the field. In this work, a field root-bag experiment was conducted to examine the changes of PAEs accumulation in the rhizosphere soil and wheat tissues under film residue conditions at four different growth stages of wheat, and to clarify the roles played by the microbial community in the alterations. Results showed that the plastic film residues significantly increased the concentrations of PAEs in soils, wheat roots, straw and grains. The maximum ΣPAEs concentration in soils and different wheat tissues appeared at the maturity, with the ΣPAEs concentration of 1.57 mg kg−1, 4.77 mg kg−1, 5.21 mg kg−1, 1.81 mg kg−1 for rhizosphere soils, wheat roots, straw and grains, respectively. The plastic film residues significantly changed the functions and components of the bacterial community, increased the stochastic processes of the bacterial community assembly, and reduced the complexity and stability of the bacterial network. In addition, the present study identified some bacteria associated with plastic film residues and PAEs degradation in key-stone taxa, and their relative abundances were positive related to the ΣPAEs concentration in soils. The PAEs content and key-stone taxa in rhizosphere soil play a crucial role in the formation of rhizosphere soil bacterial communities. This field study provides valuable information for better understanding the role of microorganisms in the complex system consisting of film residue, soil and crops.

Reutilization of scrap tyre for the enhanced removal of phthalate esters from water: immobilization performance, interaction mechanisms, and application

Waste scrap tyre as microbial immobilization matrix enhanced degradation of phthalate esters (PAEs), di (2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DBP), and diethyl phthalate (DEP). The hybrid (physical adsorption and microbial immobilization) degradation process performance of scrap tyres was examined for the PAEs degradation. The scrap tyre was shown with competitive adsorption capacity toward PAEs, influenced by pH, temperature, dosage of adsorbent (scrap tyre), and concentration of PAE. The primary adsorption mechanism for tyres toward PAEs was considered hydrophobic. The immobilization of previously isolated Bacillus sp. MY156 on tyre surface significantly enhanced PAEs degradation as well as bacterial growth. The enzymatic activity results implied immobilization promoted dehydrogenase activity and decreased esterase activity. The cell surface response during PAEs degradation, in terms of morphological observation, FTIR and XRD analyses, and extracellular polymeric substance (EPS) release, was further assessed to better understand the interactions between microorganisms and tyre surface. Waste scrap tyres could be a promising potential candidate to be reused for sustainable environmental management, including contaminants removal.

Enhanced degradation of phthalate esters (PAEs) by biochar-sodium alginate immobilised Rhodococcus sp. KLW-1

ABSTRACT In this study, a new strain of bacteria, named Rhodococcus sp. KLW-1, was isolated from farmland soil contaminated by plastic mulch for more than 30 years. To improve the application performance of free bacteria and find more ways to use waste biochar, KLW-1 was immobilised on waste biochar by sodium alginate embedding method to prepare immobilised pellet. Response Surface Method (RSM) predicted that under optimal conditions (3% sodium alginate, 2% biochar and 4% CaCl2), di (2-ethylhexyl) phthalate (DEHP) degradation efficiency of 90.48% can be achieved. Under the adverse environmental conditions of pH 5 and 9, immobilisation increased the degradation efficiency of 100 mg/L DEHP by 16.42% and 11.48% respectively, and under the high-stress condition of 500 mg/L DEHP concentration, immobilisation increased the degradation efficiency from 71.52% to 91.56%, making the immobilised pellets have strong stability and impact load resistance to environmental stress. In addition, immobilisation also enhanced the degradation efficiency of several phthalate esters (PAEs) widely existing in the environment. After four cycles of utilisation, the immobilised particles maintained stable degradation efficiency for different PAEs. Therefore, immobilised pellets have great application potential for the remediation of the actual environment.

Complete genome sequence of Acinetobacter indicus and identification of the hydrolases provides direct insights into phthalate ester degradation.

The online version contains supplementary material available at 10.1007/s10068-023-01334-w.

Plasticizer phthalate esters degradation with a laccase from Trametes versicolor: effects of TEMPO used as a mediator and estrogenic activity removal.

Phthalate esters (PAEs) are toxic and persistent chemicals that are ubiquitous in the environment and have attracted worldwide attention due to their threats to the environment and human health. Dimethyl phthalate (DMP) is a relatively simple structure and one of the most observed PAEs in the environment. This study investigated the degradation of the DMP using Trametes versicolor laccase and its laccase-mediator systems. The degradation effect of laccase alone on DMP was poor, while the laccase-mediator systems can effectively enhance the degradation efficiency. Within 24h, 45% of DMP (25mg/L) was degraded in the presence of 0.8 U/mL laccase and 0.053mM 2, 2, 6, 6-tetramethylpiperidine-1-oxyl (TEMPO). A certain concentration (1mM) of metal ions Al3+, Cu2+ or Ca2+ can positively promote DMP degradation with the laccase-TEMPO system. Moreover, the structure of PAEs also had a great influence on the degradation efficiency. Higher degradation efficiencies were observed when incubating PAEs with short alkyl side chains by the laccase-TEMPO system compared to that with long alkyl side chains. Additionally, the branched-chain PAEs had a better degradation effect than the straight-chain. The estrogenic activity of the DMP solution after reaction was much smaller than that of the original solution. Finally, transformation products ortho-hydroxylated DMP and phthalic acid were identified by GC-MS and the possible degradation pathway was proposed. This study verifies the feasibility of the laccase-TEMPO system to degrade PAEs and provides a reference for exploring more potential value of laccase.

Humic Substance Photosensitized Degradation of Phthalate Esters Characterized by 2H and 13C Isotope Fractionation.

The photosensitized transformation of organic chemicals is an important degradation mechanism in natural surface waters, aerosols, and water films on surfaces. Dissolved organic matter including humic-like substances (HS), acting as photosensitizers that participate in electron transfer reactions, can generate a variety of reactive species, such as OH radicals and excited triplet-state HS (3HS*), which promote the degradation of organic compounds. We use phthalate esters, which are important contaminants found in wastewaters, landfills, soils, rivers, lakes, groundwaters, and mine tailings. We use phthalate esters as probes to study the reactivity of HS irradiated with artificial sunlight. Phthalate esters with different side-chain lengths were used as probes for elucidation of reaction mechanisms using 2H and 13C isotope fractionation. Reference experiments with the artificial photosensitizers 4,5,6,7-tetrachloro-2',4',5',7'-tetraiodofluorescein (Rose Bengal), 3-methoxy-acetophenone (3-MAP), and 4-methoxybenzaldehyde (4-MBA) yielded characteristic fractionation factors (-4 ± 1, -4 ± 2, and -4 ± 1‰ for 2H; 0.7 ± 0.2, 1.0 ± 0.4, and 0.8 ± 0.2‰ for 13C), allowing interpretation of reaction mechanisms of humic substances with phthalate esters. The correlation of 2H and 13C fractions can be used diagnostically to determine photosensitized reactions in the environment and to differentiate among biodegradation, hydrolysis, and photosensitized HS reaction.

The occurrence, fate, toxicity, and biodegradation of phthalate esters: An overview.

Phthalate esters (PAEs) are a class of emerging xenobiotic compounds that are extensively used as plasticizers. In recent times, there has been an increasing concern over the risk of this pervasive pollution exposure causing endocrine disruption and carcinogenicity in humans and animals. The widespread use of PAEs in home and industrial applications has resulted in their discharge in aquatic bodies via leaching, volatilization, and precipitation. In this overview, the current state of PAE pollution, its potential origins, its fate, as well as its effects on the aquatic environment are discussed. A state-of-the-art review of several studies in the literature that focus on the biological degradation of PAEs is included in this study. The paper aims to provide a comprehensive view of current research on PAEs in the environment, highlighting its fate and alleviated risks on the aquatic biotas, their challenges, future prospects, and the need for good management and policies for its remediation. PRACTITIONER POINTS: Occurrence of phthalate esters was summarized in various environmental matrices along with its serious ecotoxicological implications on biota. Wastewater is the prime source of PAEs contamination. Lack of species-specific effects on biota due to dose, exposure route, and susceptibility. The predominant route to mineralization in PAEs is biodegradation. A critical analysis of worldwide PAE production and consumption identifies the necessity for global PAE production, consumption, and release policies.

The content of PAEs in field soils caused by the residual film has a periodical peak

The wide use of plastic film mulch has led to the release of phthalate esters (PAEs), which seriously threatens the soil environment and the safety of crop production. However, it is unknown whether there is a maximum threshold of soil PAEs accumulation induced by plastic film residue, and the dynamic changes of soil PAEs under field conditions are still unclear. To address these issues, a field experiment was conducted to investigate the temporal fluctuations of soil PAEs content and the response of microbial community structure in the field with plastic film residue. Results showed that the content of soil PAEs fluctuated during an observation period of one year, had a periodical peak in winter and summer, and was exacerbated by the increase in the aging degree and residual amount of plastic films. The PAEs content in soil with black films was higher than the US soil allowable criteria. High-throughput sequencing analysis showed that the addition of residual film significantly increased the alpha diversity of bacterial communities, changed the structure of bacterial community, and generated significant disturbances in bacterial function. Besides, the residual film recruited more microbiota related to plastic film and PAEs degradation. Results of the present study provide insight into the dynamic variation of soil PAEs caused by plastic film residue in one year, which is important to help evaluate the pollution risk of PAEs on soils and crops caused by residual plastic film.

Microbial community structure and potential function associated with poly-3-hydroxybutyrate biopolymer-boosted activation of peroxymonosulfate for waste-activated sludge decontamination

Excess waste-activated sludge (WAS) is a major biosolid management problem due to its biohazardous and recalcitrant content of phthalate esters (PAEs). This study aimed to assess the combined use of biopolymer, poly-3-hydroxybutyrate and peroxymonosulfate to degrade PAEs and decontaminate WAS. Poly-3-hydroxybutyrate was biosynthesized by Cupriavidus sp. L7L. The combined poly-3-hydroxybutyrate and peroxymonosulfate process removed 86 % of PAEs from WAS in 12 h. The carbonyl groups of poly-3-hydroxybutyrate were conducive to peroxymonosulfate activation leading to PAE degradation followed the radical pathway and surface-mediated electron transfer. Poly-3-hydroxybutyrate and peroxymonosulfate also enriched the PAE-biodegrading microbes in WAS. The microbial population and the functional composition in response to peroxymonosultate treatment was identified, with the genus Sulfurisoma being the most abundant. This synergistic treatment, i.e., advanced oxidation process, was augmented by highly promising microbial polyesters, exhibited important implications for WAS pretreatment toward circular bioeconomy that encompasses carbon–neutral biorefinery and mitigate pollution.

Fate of phthalate esters in landfill leachate under subcritical and supercritical conditions and determination of transformation products

The hypothesis of this study is that the complex organic load of landfill leachate could be reduced by supercritical water oxidation (SCWO) in a single stage, but this operation could lead to the formation of some undesired by-products of phthalate esters (PAEs). In this context, the fate of selected PAEs, butyl benzyl phthalate (BBP), di-2-ethylhexyl phthalate (DEHP) and di-n-octyl phthalate (DNOP), was investigated during the oxidation of leachate under subcritical and supercritical conditions. Experiments were conducted at various temperatures (250–500 °C), pressures (10–35 MPa), residence times (2–18 min) and dimensionless oxidant doses (DOD: 0.2–2.3). The SCWO process decreased the leachate’s chemical oxygen demand (COD) from 34,400 mg/L to 1,120 mg/L (97%). Removal efficiencies of DEHP and DNOP with longer chains were higher than BBP. The DEHP, DNOP and BBP compounds were removed in the range of −35 to 100%, −18 to 92%, and 28 to 36%, respectively, by the SCWO process. Many non-target PAEs were qualitatively detected in the raw leachate apart from the selected PAEs. Besides, 97% of total PAEs including both target and non-target PAEs was mineralized at 15 MPa, 300 °C and 5 min. Although PAEs were highly mineralized during SCWO of the leachate, aldehyde, ester, amide and amine-based phthalic substances were frequently detected as by-products. These by-products have transformed into higher molecular weight by-products with binding reactions as a result of complex SCWO process chemistry. It has also been determined that some non-target PAEs such as 1,2-benzenedicarboxylic acid bis(2-methylpropyl)ester and bis(2-ethylhexyl) isophthalate can transform to the DEHP. Therefore, the suggested pathway in this study for PAEs degradation during the SCWO of the leachate includes substitution and binding reactions as well as an oxidation reaction.

Carboxylesterase and lipase-catalyzed degradation of phthalate esters in soil and water: Congener structure selectivity and specificity

Phthalate esters (PAEs) are ubiquitous in agricultural soil and crops because of the widespread application of plastic films containing PAEs. The enzymes play critical roles in the elimination of pollutants from environmental matrices. In an attempt to evaluate the effect of enzymes on the degradation of various PAEs, this study investigated the enzyme-catalyzed reaction kinetics of seven selected PAE congeners in water and soil. Carboxylesterase and lipase catalyzed the transformation of PAEs to monoalkyl phthalate esters and phthalic acid with the half-life ranges of 4.78–126.03 h. PAEs with long-alkyl-chain were more recalcitrant to carboxylesterase and lipase-catalyzed degradation, and PAEs with short alkyl chains were relatively easier to be degraded by the two enzymes. The results indicate that the alkyl chain length had a profound effect on the enzyme-catalyzed degradation of PAEs. The reaction rates and half-lives were significantly correlated with the log Kow value ( p < 0.01), which was dominated by the molecular structure. The results obtained in this work are expected to well guide the application of carboxylesterase and lipase in the remediation of waterbody contaminated by various PAEs. With respect to soil, they can be well used in the remediation, exposure, and risk assessment of paddy soil. However, the application of the results in the remediation of other soils might lead to the risk of a low removal ratio. • PAEs can be readily degraded by carboxylesterase and lipase. • The degradation rates of PAEs are relatively higher in water than in soil. • The degradation rates of PAEs are congener structure associated. • The removal ratio of PAEs related to soil properties.

Combination of a Highly Efficient Biological System and Visible-Light Photocatalysis Pretreatment System for the Removal of Phthalate Esters from Wastewater

To save energy and increase treatment efficiency, a visible-light photocatalysis system was coupled with a biological treatment system for the continuous removal of phthalate esters (PAEs) from synthetic wastewater. Di-(2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DBP), and dimethyl phthalate (DMP) were treated using an iodine-doped TiO2 photocatalyst, and the reactions followed first-order kinetics (similar to ultraviolet TiO2 photocatalysis) to produce phthalic acid as an intermediate product. The effects of various operating factors, such as PAE concentrations, pH, light intensity, retention time (RT), and the coexistence of PAEs, on individual PAE removal were investigated. DEHP-degrading bacteria were isolated from DEHP-contaminated soil, purified through serial dilution, and then identified through DNA sequencing. The results indicated that the optimal operating conditions for PAE removal with a visible-light photoreactor were a pH of 5, a temperature of 30 °C, a light intensity of 300 W, and an RT of 5.5 min. DEHP, which contains long and branched chains, was more difficult to degrade than DMP, which contains short alkyl side chains. Pseudomonas sp. was the most dominant bacteria in the DEHP-contaminated soil and was inoculated in a packed bed reactor (PBR) for complete PAE degradation. The effluent containing PAEs was pretreated using the visible-light photoreactor under a short RT. This treatment resulted in the effluent becoming biodegradable, and PAEs could be completely removed from the treated effluent by using the PBR. The coupled photobiological system achieved removal efficiencies of 99.6%, 99.9%, and 100% for DEHP, DBP, and DMP, respectively, during the continuous treatment. The results of this study indicate that the developed coupled system is an effective, energy-saving, and cost-efficient tool for treating wastewater containing PAEs.

Synergistic effect of ferrous ion-activated hydrogen peroxide and persulfate on the degradation of phthalates in aquatic environments by non-target analysis

Oxidative degradation of most recalcitrant organics in the wastewater by exciting the oxidative potential and high efficacy of economic and environmental compatible oxidants is currently an extensively studied field of research. In this study, an efficient phthalate esters (PAEs) degradation method utilizing dual oxidants persulfate (PS) and hydrogen peroxide in the presence of ferrous ions was developed with high removal efficiency, small oxidant dosage and wide pH range. Compared with the degradation efficiency of single systems including Fe2+/ H2O2 (40 %), PS (24 %) and Fe2+/PS (49 %) for dimethyl phthalate (DMP) degradation, the combining PS and H2O2 activated by Fe2+ is more effective, with the removal efficiency of 95 %. The synergistic effect of PS and H2O2 in the Fe2+-containing system on PAEs degradation was reflected by the degradation products determined by non-target analysis of various oxidation processes. The results showed that the degradation of DMP in two single oxidant systems was dominated by aromatic compounds via dealkylation, hydroxyl addition and decarboxylation, while DMP in the PS/H2O2/FeSO4 system was mainly deeply oxidized to aliphatic molecules through further dearomatization, which was vulnerable for the mineralization of DMP to CO2 and H2O. In addition, the EPR technique combined with DMPO captured SO4•− and •OH signals in the presence of the same Fe2+ and oxidant dosage, revealing that a higher intensity of ·OH and SO4•− generated in the combined oxidative process resulted in a high removal of DMP. This work lays the groundwork for recalcitrant organics removal to apply synergistic activation mode in the AOPs system.

Effects of fertilizer application on phthalate ester pollution and the soil microbial community in plastic-shed soil on long-term fertilizer experiment

Due to the use of agricultural film, the pollution of phthalate esters (PAEs) in plastic-shed soils has attracted increasing attention. In this study, we used watermelon as a planting system and investigated the effects of organic fertilizer and chemical fertilizer application on the degradation of PAEs by evaluating soil nutrients and soil bacterial communities in plastic-shed soil. The dibutyl phthalate (DBP) concentration in the organic fertilizer soil was only 58.2% in the zero-fertilization control (CK) soil, but the concentrations of monohexyl phthalate (MEHP) and mono-n-butyl ester (MBP), the metabolites of PAEs, were found to be higher. The concentration of MBP is ten times that of DBP. The results showed that fertilization, especially the application of organic fertilizers, had a significant effect on the degradation of PAEs. There were specific biomarkers in different fertilization treatments. Among the microbiome community, Planifilum had the highest relative abundance in the organic fertilizer (OF) soil, and the highest proportion of Thermodesulfovibrionia was detected in the chemical fertilizer (CF) soil. These biomarkers were significantly correlated with PAEs and their metabolites. The relative abundance of Thermomonosporaceae was significantly positively correlated with DBP. Planifilum and Thermaerobacter, which significantly increased in organic fertilizer soil, showed a significant negative correlation with DBP and a significant positive correlation with MBP. The relative abundances of Planifilum and Geobacillus were elevated in the OF soil and may be able to co-metabolize soil nitrogen and PAEs. PAEs and their metabolites in soils had significant effects on soil microbes, as did the soil nutrients including available phosphorus (AP), alkali-hydrolysable nitrogen (Alkali-N), and organic matter (OM). Our research provides scientific support for the use of fertilizers to reduce PAE contamination but also warns of the potential risks of PAE metabolites.

Analysis of the performance of the efficient di-(2-ethylhexyl) phthalate-degrading bacterium Rhodococcus pyridinovorans DNHP-S2 and associated catabolic pathways

The widespread use of plastic has led to the global occurrence of phthalate esters (PAEs) pollution. PAEs can be effectively removed from polluted environments by microbe-mediated degradation. Di-(2-ethylhexyl) phthalate (DEHP) has the highest residual concentration in agricultural soil-contaminated areas compared to other PAEs in most of China. The Rhodococcus pyridinovorans DNHP-S2 microbial isolate identified was found to efficiently degrade DEHP. Within a 72 h period, the bacteria were able to degrade 52.47% and 99.75% of 500 mg L−1 DEHP at 10 °C and 35 °C, respectively. Dimethyl phthalate (DMP) was first identified as an intermediate metabolite of DEHP, which is different from the previously reported DEHP catabolic pathway. Genomic sequencing of DNHP-S2 identified benzoate 1,2-dioxygenase and catechol 2,3/1,2-dioxygenase as potential mediators of DEHP degradation, consistent with the existence of two downstream metabolic pathways governing DEHP degradation. Three targets DEHP metabolism-related enzymes were found to be DEHP-inducible at the mRNA level, and DNHP-S2 was able to mediate the complete degradation of DEHP at lower temperatures, as confirmed via RT-qPCR. DNHP-S2 was also found to readily break down other PAEs including DMP, di-n-butyl phthalate (DBP), di-n-octyl phthalate (DnOP), and n-butyl benzyl phthalate (BBP). Together, these results thus highlight DNHP-S2 as a bacterial strain with great promise as a tool for the remediation of PAE pollution. In addition to providing new germplasm and genetic resources for use in the context of PAE degradation, these results also offer new insight into the potential mechanisms whereby PAEs undergo catabolic degradation, making them well-suited for use in PAE-contaminated environments.

Engineering Transcription Factor XylS for Sensing Phthalic Acid and Terephthalic Acid: An Application for Enzyme Evolution.

Poly(ethylene terephthalate) (PET) and phthalate esters (PAEs) are used extensively as plastics and plasticizers. Enzymatic degradation of PET and PAEs has drawn great attention in recent years; however, evolution of PET- and PAE-degrading enzymes is still a big challenge, partly because of the lack of an effective screening method to detect phthalic acid (PA) and terephthalic acid (TPA), which are the main hydrolysis products of PAEs and PET. Here, by directed evolution of a promiscuous transcription factor, XylS from Pseudomonas putida, we created two novel variants, XylS-K38R-L224Q and XylS-W88C-L224Q, that are able to bind PA and TPA and activate the downstream expression of a fluorescent reporter protein. Based on these elements, whole-cell biosensors were constructed, which enabled the fluorimetric detection of as little as 10 μM PA or TPA. A PAE hydrolase, GoEst15, was preliminarily engineered using this new biosensor, yielding a mutant GoEst15-V3 whose activity toward dibutyl phthalate (DBP) and p-nitrophenyl butyrate was enhanced 2.0- and 2.5-fold, respectively. It was shown that 96.5% DBP (5 mM) was degraded by GoEst15-V3 in 60 min, while the wild-type enzyme degraded only 55% DBP. This study provides an effective screening tool for directed evolution of PAE-/PET-degrading enzymes.

Insights into photocatalytic degradation of phthalate esters over MSnO3 perovskites (M = Mg, Ca): Experiments and density functional theory

In this study, the physicochemical and photocatalytic properties of two kinds of stannate perovskite oxides (MgSnO3 and CaSnO3) were investigated under simulated sunlight, where dimethyl phthalate (DMP) and diethyl phthalate (DEP) were selected as the probe pollutants. The results of photochemical characterization showed that MgSnO3 perovskite exhibited better photocatalytic performance than CaSnO3 perovskite. MgSnO3 perovskite could effectively degrade 75% of DMP and 79% of DEP through pseudo-first-order reaction kinetics, which remained good in pH 3.0 to 9.0. Quenching experiments and electron paramagnetic resonance (EPR) characterization indicated that photogenerated holes (h+), superoxide (O2−), and hydroxyl radicals (OH) worked in the photo-degradation, while O2− played the most important role. Furthermore, intermediates identification and density functional theory (DFT) calculations were used to explore the degradation mechanism. For both DMP and DEP, the reactive oxygen species (ROS, including O2− and OH) were responsible for the hydroxylation of benzene ring and the breaking of the aliphatic chain, while h+ was prone to break the aliphatic chain. This work is expected to provide new insights on the photocatalytic mechanism of stannate perovskites for environmental remediation.

Characterization of microbial communities and functions in shale gas wastewaters and sludge: Implications for pretreatment

As hydraulic fracturing (HF) practices keep expanding in China, a comparative understanding of biological characteristics of flowback and produced waters (FPW) and sludge in impoundments for FPW reserve will help propose appropriate treatment strategies. Therefore, in this study, the microbial communities and functions in impoundments that collected wastewaters from dozens of wells were characterized. The results showed that microbial richness and diversity were significantly increased in sludge compared with those in FPW. The vast majority of microorganisms found in FPW and sludge are organic degraders, providing the possibility of using these indigenous microorganisms to biodegrade organic compounds. Our laboratory findings first show that wastewater pretreatment using these microorganisms was effective, and organic compounds in FPW from different shale formations were removed by 35–68% within 72 h in a wide temperature range (8 – 30 ℃). Meanwhile, highly toxic compounds such as phthalate esters (PAEs), polycyclic aromatic hydrocarbons (PAHs), and petroleum hydrocarbons were effectively eliminated in reactors. The main microorganisms, key functional genes, and putative pathways for alkanes, PAHs, and PAEs degradation were also identified.

Brønsted-acid sites promoted degradation of phthalate esters over MnO2: Mineralization enhancement and aquatic toxicity assessment

Advanced oxidation processes (AOPs) are important technologies for aqueous organics removal. Despite organic pollutants can be degraded via AOPs generally, high mineralization of them is hard to achieve. Herein, we synthesized a manganese oxide nanomaterial (H2-OMS-2) with abundant Brønsted-acid sites via ion-exchange of cryptomelane-type MnO2 (OMS-2), and tested its catalytic performance for the degradation of phthalate esters via peroxymonosulfate (PMS) activation. About 99% of dimethyl phthalate (DMP) at a concentration of 20 mg/L could be degraded within 90 min and 82% of it could be mineralized within 180 min over 0.6 g/L of catalyst and 1.8 g/L of PMS. The catalyst could activate PMS to generate SO4−˙ and ·OH as the dominant reactive oxygen species to reach complete degradation of DMP. Especially, the higher TOC removal rate was obtained due to the rich Brønsted-acid sites and surface oxygen vacancies on the catalyst. Kinetics and mechanism study showed that MnII/MnIII might work as the active sites during the catalytic process with a lower reaction energy barrier of 55.61 kJ/mol. Furthermore, the catalyst could be reused for many times through the regeneration of the catalytic ability. The degradation and TOC removal efficiencies were still above 98% and 65% after seven consecutive cycles, respectively. Finally, H2-OMS-2-catalyzed AOPs significantly reduced the organismal developmental toxicity of the DMP wastewater through the investigation of zebrafish model system. The present work, for the first time, provides an idea for promoting the oxidative degradation and mineralization efficiencies of aqueous organic pollutants by surface acid-modification on the catalysts.

Biodegradation of phthalate esters by Pantoea dispersa BJQ0007 isolated from Baijiu

Baijiu is a famous Chinese alcoholic beverage and is produced by the co-fermentation of microorganisms with grains as the raw materials. Phthalate esters (PAEs) are toxic chemicals and frequently detected in Baijiu. Identification of microorganisms that could degrade PAEs was recognized as a possible way to solve the contamination. Pantoea spp. are one kind of dominant microorganisms for manufacturing Baijiu. Here, Pantoea dispersa BJQ0007 was isolated from Baijiu fermentation starter and showed the ability in degrading dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, and di-(2-ethylhexyl) phthalate, with di-(2-ethylhexyl) phthalate as the preferred substrate. The whole genome was sequenced with a chromosome of 4,325,134 bp and three plasmids. The metabolic pathway of PAE degradation is proposed with an uncommon metabolic step by converting phthalate monoester to benzoate ester based on metabolic intermediate analysis and genome annotation. Two enzymes responsible for ester bond hydrolysis of PAEs were identified and belonged to enzyme families IV and not defined, respectively. The results revealed PAE degradation of Pantoea species and would promote the safety control of Baijiu products by offering bacterial and enzymatic resources.