Transformation process and phytotoxicity of sulfamethoxazole and N4-acetyl-sulfamethoxazole in rice.

Sulfonamide antibiotics, extensively used in human and veterinary therapy, accumulate in agroecosystem soils through livestock manure and sewage irrigation. However, the interaction between sulfonamides and rice plants remains unclear. This study investigated the transformation behavior and toxicity of sulfamethoxazole (SMX) and its main metabolite, N4-acetyl-sulfamethoxazole (NASMX) in rice. SMX and NASMX were rapidly taken up by roots and translocated acropetally. NASMX showed higher accumulating capacity, with NASMX concentrations up to 20.36 ± 1.98 µg/g (roots) and 5.62 ± 1.17 µg/g (shoots), and with SMX concentrations up to 15.97 ± 2.53 µg/g (roots) and 3.22 ± 0.789 µg/g (shoots). A total of 18 intermediate transformation products of SMX were identified by nontarget screening using Orbitrap-HRMS, revealing pathways such as deamination, hydroxylation, acetylation, formylation, and glycosylation. Notably, NASMX transformed back into SMX in rice, a novel finding. Transcriptomic analysis highlights the involvements of cytochrome P450 (CYP450), acetyltransferase (ACEs) and glycosyltransferases (GTs) in these biotransformation pathways. Moreover, exposure to SMX and NASMX disrupts TCA cycle, amino acid, linoleic acid, nucleotide metabolism, and phenylpropanoid biosynthesis pathways of rice, with NASMX exerting a stronger impact on metabolic networks. These findings elucidate the sulfonamides' metabolism, phytotoxicity mechanisms, and contribute to assessing food safety and human exposure risk amid antibiotic pollution.

Aerobic Microbial Transformation of Fluorinated Liquid Crystal Monomer: New Pathways and Mechanism.

Fluorinated liquid crystal monomers (FLCMs) have been suggested as emerging contaminants, raising global concern due to their frequent occurrence, potential toxic effects, and endurance capacity in the environment. However, the environmental fate of the FLCMs remains unknown. To fill this knowledge gap, we investigated the aerobic microbial transformation mechanisms of an important FLCM, 4-[difluoro(3,4,5-trifluorophenoxy)methyl]-3, 5-difluoro-4'-propylbiphenyl (DTMDPB), using an enrichment culture termed as BG1. Our findings revealed that 67.5 ± 2.1% of the initially added DTMDPB was transformed in 10 days under optimal conditions. A total of 14 microbial transformation products obtained due to a series of reactions (e.g., reductive defluorination, ether bond cleavage, demethylation, oxidative hydroxylation and aromatic ring opening, sulfonation, glucuronidation, O-methylation, and thiolation) were identified. Consortium BG1 harbored essential genes that could transform DTMDPB, such as dehalogenation-related genes [e.g., glutathione S-transferase gene (GST), 2-haloacid dehalogenase gene (2-HAD), nrdB, nuoC, and nuoD]; hydroxylating-related genes hcaC, ubiH, and COQ7; aromatic ring opening-related genes ligB and catE; and methyltransferase genes ubiE and ubiG. Two DTMDPB-degrading strains were isolated, which are affiliated with the genus Sphingopyxis and Agromyces. This study provides a novel insight into the microbial transformation of FLCMs. The findings of this study have important implications for the development of bioremediation strategies aimed at addressing sites contaminated with FLCMs.

Translocation and metabolism of tricresyl phosphate in rice and microbiome system: Isomer-specific processes and overlooked metabolites.

Tricresyl phosphate (TCP) is extensively used organophosphorus flame retardants and plasticizers that posed risks to organisms and human beings. In this study, the translocation and biotransformation behavior of isomers tri-p-cresyl phosphate (TpCP), tri-m-cresyl phosphate (TmCP), and tri-o-cresyl phosphate (ToCP) in rice and rhizosphere microbiome was explored by hydroponic exposure. TpCP and TmCP were found more liable to be translocated acropetally, compared with ToCP, although they have same molecular weight and similar Kow. Rhizosphere microbiome named microbial consortium GY could reduce the uptake of TpCP, TmCP, and ToCP in rice tissues, and promote rice growth. New metabolites were successfully identified in rice and microbiome, including hydrolysis, hydroxylated, methylated, demethylated, methoxylated, and glucuronide- products. The methylation, demethylation, methoxylation, and glycosylation pathways of TCP isomers were observed for the first time in organisms. What is more important is that the demethylation of TCPs could be an important and overlooked source of triphenyl phosphate (TPHP), which broke the traditional understanding of the only manmade source of toxic TPHP in the environment. Active members of the microbial consortium GY during degradation were revealed and metagenomic analysis indicated that most of active populations contained TCP-degrading genes. It is noteworthy that the strains and function genes in microbial consortium GY that responsible for TCP isomers' transformation were different. These results can improve our understanding of the translocation and transformation of organic pollutant isomers in plants and rhizosphere microbiome.

Biotransformation of Organophosphate Esters by Rice and Rhizosphere Microbiome: Multiple Metabolic Pathways, Mechanism, and Toxicity Assessment.

The biotransformation behavior and toxicity of organophosphate esters (OPEs) in rice and rhizosphere microbiomes were comprehensively studied by hydroponic experiments. OPEs with lower hydrophobicity were liable to be translocated acropetally, and rhizosphere microbiome could reduce the uptake and translocation of OPEs in rice tissues. New metabolites were successfully identified in rice and rhizosphere microbiome, including hydrolysis, hydroxylated, methylated, and glutathione-, glucuronide-, and sulfate-conjugated products. Rhizobacteria and plants could cooperate to form a complex ecological interaction web for OPE elimination. Furthermore, active members of the rhizosphere microbiome during OPE degradation were revealed and the metagenomic analysis indicated that most of these active populations contained OPE-degrading genes. The results of metabolomics analyses for phytotoxicity assessment implied that several key function metabolic pathways of the rice plant were found perturbed by metabolites, such as diphenyl phosphate and monophenyl phosphate. In addition, the involved metabolism mechanisms, such as the carbohydrate metabolism, amino acid metabolism and synthesis, and nucleotide metabolism in Escherichia coli, were significantly altered after exposure to the products mixture of OPEs generated by rhizosphere microbiome. This work for the first time gives a comprehensive understanding of the entire metabolism of OPEs in plants and associated microbiome, and provides support for the ongoing risk assessment of emerging contaminants and, most critically, their transformation products.

The novel chitosan-amphoteric starch dual flocculants for enhanced removal of Microcystis aeruginosa and algal organic matter.

A novel flocculation strategy for simultaneously removing Microcystis aeruginosa and algal organic matter (AOM) was proposed using chitosan-amphoteric starch (C-A) dual flocculants in an efficient, cost-effective and ecologically friendly way, providing new insights for harmful algal blooms (HABs) control. A dual-functional starch-based flocculant, amphoteric starch (AS) with high anion degree of substitution (DSA) and cation degree of substitution (DSC), was prepared using a cationic moiety of 3-chloro-2-hydroxypropyltrimethylammonium chloride (CTA) coupled with an anion moiety of chloroacetic acid onto the backbone of starch simultaneously. In combination of the results of FTIR, XPS, 1H NMR, 13C NMR, GPC, EA, TGA and SEM, it was evidenced that the successfully synthesized AS with excellent structural characteristics contributed to the enhanced flocculation of M. aeruginosa. Furthermore, the novel C-A dual flocculants could achieve not only the removal of >99.3 % of M. aeruginosa, but also the efficacious flocculation of algal organic matter (AOM) at optimal concentration of (0.8:24) mg/L, within a wide pH range of 3-11. The analysis of zeta potential and cellular morphology revealed that the dual effects of both enhanced charge neutralization and notable netting-bridging played a vital role in efficient M. aeruginosa removal.

Renewable biochar derived from mixed sewage sludge and pine sawdust for carbon dioxide capture.

Carbon dioxide (CO2) is the main anthropogenic greenhouse gas contributing to global warming. In this study, a series of KOH-modified biochars derived from feedstock mixtures (i.e., S3W7 biomass consisting of 70% pine sawdust and 30% sewage sludge; S5W5 biomass consisting of 50% pine sawdust and 50% sewage sludge) at different temperature (i.e., 600-800 °C) were prepared for evaluating CO2 adsorption performance. The KOH-activated biochars prepared with S3W7 biomass displayed larger surface areas and micropore volumes compared to those of S5W5 biochars. In particular, the highest CO2 adsorption capacity (177.1 mg/g) was observed on S3W7 biomass at 700 °C (S3W7-700K), due to the largest surface area (2623 m2/g) and the highest micropore volume (0.68 cm3/g). Furthermore, surface functional groups, hydrophobicity, and aromaticity of biochar and presence of hetero atoms (N) also were actively involved in CO2 adsorption of biochar. In addition, in situ DRIFTS analysis advanced current understanding for the chemical sorption mechanisms by identifying the transformation composites of CO2 on biochars, and characterizing the weakly adsorbed and newly formed mineral species (e.g., carbonates) during the CO2 sorption process. This study may provide an insight into the research of CO2 capture by identifying physical and chemical adsorption, and expand the effective utilization of natural biomass-based biochar for mitigation greenhouse gas emission.

Biodegradation of tricresyl phosphates isomers by a novel microbial consortium and the toxicity evaluation of its major products.

A novel microbial consortium ZY1 capable of degrading tricresyl phosphates (TCPs) was isolated, it could quickly degrade 100% of 1 mg/L tri-o-cresyl phosphate (ToCP), tri-p-cresyl phosphate (TpCP) and tri-m-cresyl phosphate (TmCP) within 36, 24 and 12 h separately and intracellular enzymes occupied the dominated role in TCPs biodegradation. Additionally, triphenyl phosphate (TPHP), 2-ethylhexyl diphenyl phosphate (EHDPP), bisphenol-A bis (diphenyl phosphate) (BDP), tris (2-chloroethyl) phosphate (TCEP) and tris (1-chloro-2-propyl) phosphate (TCPP) could also be degraded by ZY1 and the aryl-phosphates was easier to be degraded. The TCPs reduction observed in freshwater and seawater indicated that high salinity might weak the degradability of ZY1. The detected degradation products suggested that TCPs was mainly metabolized though the hydrolysis and hydroxylation. Sequencing analysis presented that the degradation of TCPs relied on the cooperation between sphingobacterium, variovorax and flavobacterium. The cytochrome P450/NADPH-cytochrome P450 reductase and phosphatase were speculated might involve in TCPs degradation. Finally, toxicity evaluation study found that the toxicity of the diesters products was lower than their parent compound based on the generation of the intracellular reactive oxygen (ROS) and the apoptosis rate of A549 cell. Taken together, this research provided a new insight for the bioremediation of TCPs in actual environment.

Dehalococcoides-Containing Enrichment Cultures Transform Two Chlorinated Organophosphate Esters.

Although chlorinated organophosphate esters (Cl-OPEs) have been reported to be ubiquitously distributed in various anoxic environments, little information is available on their fate under anoxic conditions. In this study, we report two Dehalococcoides-containing enrichment cultures that transformed 3.88 ± 0.22 µmol tris(2-chloroethyl) phosphate (TCEP) and 2.61 ± 0.02 µmol tris(1-chloro-2-propyl) phosphate (TCPP) within 10 days. Based on the identification of the transformed products and deuteration experiments, we inferred that TCEP may be transformed to generate bis(2-chloroethyl) phosphate and ethene via one-electron transfer (radical mechanism), followed by C-O bond cleavage. Ethene was subsequently reduced to ethane. Similarly, TCPP was transformed to form bis(1-chloro-2-propyl) phosphate and propene. 16S rRNA gene amplicon sequencing and quantitative polymerase chain reaction analysis revealed that Dehalococcoides was the predominant contributor to the transformation of TCEP and TCPP. Two draft genomes of Dehalococcoides assembled from the metagenomes of the TCEP- and TCPP-transforming enrichment cultures contained 14 and 15 putative reductive dehalogenase (rdh) genes, respectively. Most of these rdh genes were actively transcribed, suggesting that they might contribute to the transformation of TCEP and TCPP. Taken together, this study provides insights into the role of Dehalococcoides during the transformation of representative Cl-OPEs.

Transformation of sulfamethoxazole by sulfidated nanoscale zerovalent iron activated persulfate: Mechanism and risk assessment using environmental metabolomics.

The threat caused by the misuse of antibiotics to ecology and human health has been aroused an extensive attention. Developing cost-effective techniques for removing antibiotics needs to put on the agenda. In current research, the degradation mechanism of sulfamethoxazole (SMX) by sulfidated nanoscale zerovalent iron (S-nZVI) driven persulfate, together with the potential risk of intermediates were studied. The degradation of SMX followed a pseudo-first order kinetics reaction with kobs at 0.1176 min-1. Both SO4•- and •OH were responsible for the degradation of SMX, and SO4•- was the predominant free radical. XPS analysis demonstrated that reduced sulfide species promoted the conversion of Fe (III) to Fe (II), resulting in the higher transformation rate of SMX. Six intermediates products were generated through hydroxylation, dehydration condensation, nucleophilic reaction, and hydrolysis. The risk of intermediates products is subsequently assessed using E. coli as a model microorganism. After E.coli exposure to intermediates for 24 h, the upmetabolism of carbohydrate, nucleotide, citrate acid cycle and downmetabolism of glutathione, sphingolipid, galactose by metabolomics analysis identified that SMX was effectively detoxified by oxidation treatment. These findings not only clarified the superiority of S-nZVI/persulfate, but also generated a novel insight into the security of advanced oxidation processes.

Reductive degradation of chlorinated organophosphate esters by nanoscale zerovalent iron/cetyltrimethylammonium bromide composites: Reactivity, mechanism and new pathways.

Chlorinated organophosphate esters (Cl-OPEs), e.g., tris(2-chloroethyl) phosphate (TCEP), tris(2-chloro-2-propyl) phosphate (TCPP) and tris(1,3-dichloro-2-propyl) phosphate (TDCPP), are widely used as additive flame retardants in commercial and building products. They have potential persistent organic pollutant properties and are frequently detected in various waters, especially in wastewaters. Nanoscale zerovalent iron (nZVI)-based method is an efficient reductive technology for treating waters polluted by halogenated organic pollutants (HOCs). Cetyltrimethylammonium bromide (CTAB) is a ubiquitous surfactant in wastewaters and can favorably affect the interaction between HOCs and nZVI. However, its effect on the Cl-OPEs removal by nZVI-based materials still remains unknown. Herein, the adsorption and degradation efficiencies of Cl-OPEs by nZVI and sulfidated nZVI (S-nZVI) in the presence or absence of CTAB were quantified based on the decreasing concentrations of Cl-OPEs in reaction systems. Our results showed that TDCPP and TCPP were adsorbed onto the nZVI or S-nZVI surface and subsequently degraded. In contrast, TCEP was just adsorbed onto the particle surface without further degradation. The addition of CTAB significantly enhanced the hydrophobic adsorption between Cl-OPEs and nZVI or S-nZVI, leading to increased degradation of Cl-OPEs (especially TCEP). CTAB adsorption isotherms indicated that S-nZVI had a higher adsorption capacity for CTAB than nZVI. The S-nZVI/CTAB composite exhibited a better performance than nZVI/CTAB composite. When S-nZVI was combined with 100.0 mg L-1 CTAB, 100% of TDCPP, TCPP and TCEP was degraded within 3 hours, 5 and 14 days, respectively. As the concentration of CTAB was increased up to 335.0 mg L-1, TCEP could be completely degraded within 3 days by S-nZVI. Five degradation products of TCEP were identified, of which O,O-di-(2-chloroethyl) O-ethyl phosphate (DCEEP) and ethane were reported for the first time. We propose that TCEP is dechlorinated by nZVI or S-nZVI through the electron attack at the ethyl-chlorine group to form bis(2-chloroethyl) phosphate, DCEEP, chloride, ethene and ethane, representing previously unknown degradation pathways.

Enhanced tetrabromobisphenol A debromination by nanoscale zero valent iron particles sulfidated with S0 dissolved in ethanol.

Modification of nanoscale zero-valent iron (nZVI) with reducing sulfur compounds has proven to improve the reactivity of nZVI towards recalcitrant halogenated organic contaminants. In this study, we develop a novel method for the preparation of sulfidated nZVI (S-nZVI) with S0 (a low cost and available reducing sulfur agent) dissolved in ethanol under mild conditions and apply it for the transformation of tetrabromobisphenol A (TBBPA), a potential persistent organic pollutant. Surface analysis shows that S0 dissolved in ethanol has been successfully doped into nZVI via a reaction with Fe0 to form a relatively homogeneous layer of FeS/FeS2 on the nZVI surface. The H2 production test and the electrochemical analysis show that the FeS/FeS2 layer not only slows the H2 evolution reaction but also enhances the electron transfer. Debromination kinetics indicate that the resulting S-nZVI with a S/Fe ratio of 0.015-0.05 possesses higher debromination activity for TBBPA and its debromination products (i.e., tri-BBPA, di-BBPA, mono-BBPA and BPA) in comparison with nZVI. Among them, S-nZVI at a S/Fe of 0.025 (S-nZVIS-0.025) has the greatest debromination rate constant (kobs) of 1.19 ± 0.071 h-1 for TBBPA. It debrominates TBBPA at a faster rate than other conventional S-nZVI made from Na2S and Na2S2O4 and has been successfully applied in the treatment of TBBPA-spiked environmental water samples (including river water, groundwater, and tap water). The results suggest that the modification of nZVI with S0 dissolved in ethanol is a simple, safe, inexpensive, and effective sulfidation technique, which can be applied for the large-scale production of S-nZVI for treating contaminated water.

Enhanced reactivity of iron monosulfide towards reductive transformation of tris(2-chloroethyl) phosphate in the presence of cetyltrimethylammonium bromide.

Tris(2-chloroethyl) phosphate (TCEP) is a widely found emerging pollutant due to its heavy usage as a flame retardant. It is chemically stable and is very difficult to removal from water. The goal of this study was to explore whether iron monosulfide (FeS) can be used for reductive transformation of TCEP as FeS can react with a variety of halogenated organic contaminants. We used batch reactor systems to quantify the transformation reactions in the absence and presence of cetyltrimethylammonium bromide (CTAB, a common surfactant in aquatic environments). The results showed that, in the presence of CTAB (100 mg L-1), FeS exhibited much greater reactivity towards TCEP as 93% of initial TCEP had been transformed within 14 d of reaction. In the absence of CTAB, it required 710 d of reaction to achieve 97.3% reduction of initial TCEP. The enhancement of CTAB on TCEP transformation rate could be due to the facts that CTAB could stabilize FeS suspension against aggregation, protect FeS from rapid oxidation, and increase surface adsorption of TCEP on FeS. XPS analysis showed that both Fe(II) and S(-II) species on the FeS surface were involved in the reductive transformation of TCEP. Analysis of transformation products revealed that TCEP was reductively transformed into bis(2-chloroethyl) phosphate (BCEP), Cl- and C2H4. These findings showed that FeS may play an important role in the reductive transformation of TCEP when TCEP coexisting with CTAB in aquatic environments.

Compound-specific carbon isotope analysis for mechanistic characterization of debromination of decabrominated diphenyl ether.

RATIONALE: Decabrominated diphenyl ether (BDE-209) is a notorious persistent organic pollutant widely found in the environment. Developing a compound-specific isotope analysis (CSIA) method is much needed in order to trace its transport and degradation processes and to evaluate the effectiveness of the remediation of BDE-209 in the environment. However, the conventional CSIA method, i.e. gas chromatography (GC) combustion isotope ratio mass spectrometry, is not appropriate for BDE-209 because of its high thermal instability and incomplete combustion. METHODS: We developed a high-performance liquid chromatography (HPLC) method for the separation and purification of BDE-209 that prevents its thermal reactivity as occurred in prior GC-based methods. The δ13 C value of the purified BDE-209 was determined using offline elemental analyzer isotope ratio mass spectrometry (EA/IRMS). This two-step method was applied to determine the δ13 C values of BDE-209 in two commercial samples and to characterize carbon isotope fractionation associated with the debromination of BDE-209 via nanoscale zero-valent iron. RESULTS: The mean values of daily δ13 C analyses of six replicates of a BDE-209 standard varied from -27.66‰ to -27.92‰, with a standard deviation ranging from 0.07‰ to 0.16‰, indicating a good reproducibility of EA/IRMS. The EA/IRMS analysis of the purified BDE-209 standard indicated no obvious isotope fractionation during the sample purification. The impurity content in commercial BDE-209 samples may contribute additional variation of the δ13 C values of BDE-209. The δ13 C values of BDE-209 gradually changed from -27.47 ± 0.37‰ to -24.59 ± 0.19‰ when 74% of the BDE-209 standard was degraded within 36 h. The estimated carbon isotope enrichment factor was -1.72 ± 0.18‰. CONCLUSIONS: The two-step method based on HPLC and EA/IRMS avoids the thermal instability of BDE-209 in the traditional CSIA method. It offers a novel approach for elucidating the degradation mechanisms of BDE-209 in the environment and for source identification in contaminated sites.

New insights into the anaerobic microbial degradation of decabrominated diphenyl ether (BDE-209) in coastal marine sediments.

Severe contamination of decabrominated diphenyl ether (BDE-209, an emerging persistent organic pollutant) in coastal marine sediments has posed a serious threat to the marine ecosystems. Anaerobic microbial degradation can affect the toxicity and environmental fate of BDE-209 in anoxic marine sediments. However, little is known about the anaerobic microbial degradation of BDE-209 in anoxic marine/coastal sediments. In this study, the anaerobic degradation of BDE-209 in microcosms containing coastal marine sediments from a contaminated bay located in Southern China was investigated. It was observed that over 70% of the BDE-209 (5 µmol) added to the anaerobic sediment microcosms disappeared after 90-day of incubation. Thirty-five debrominated products (tetra- to nonaBDEs) were identified by GC-MS. Remarkably, a majority of these products (i.e. 20 products, including BDE-52, -92, -101, -102, -103, -133, -144, -146, -150, -161, -171, -172, -175, -177, -178, -180, -182, -188, -193, -199) have not been previously reported in the literature on the anaerobic microbial degradation of BDE-209 in sediments. There was no preferential debromination among ortho-, meta-, and para-bromines on BDE-209 and higher-brominated diphenyl ethers were the predominant debromination products. High-throughput sequencing revealed that the relative abundances of 9 microbial genera in the sediment microcosms increased as the anaerobic degradation of BDE-209 progressed, indicating their involvements in the degradation process. Taken together, our findings provided new insights into the anaerobic microbial degradation of BDE-209 in anoxic marine sediments.

Diastereoisomer-Specific Biotransformation of Hexabromocyclododecanes by a Mixed Culture Containing Dehalococcoides mccartyi Strain 195.

Hexabromocyclododecane (HBCD) stereoisomers may exhibit substantial differences in physicochemical, biological, and toxicological properties. However, there remains a lack of knowledge about stereoisomer-specific toxicity, metabolism, and environmental fate of HBCD. In this study, the biotransformation of (±)α-, (±)ß-, and (±)γ-HBCD contained in technical HBCD by a mixed culture containing the organohalide-respiring bacterium Dehalococcoides mccartyi strain 195 was investigated. Results showed that the mixed culture was able to efficiently biotransform the technical HBCD mixture, with 75% of the initial HBCD (∼12 µM) in the growth medium being removed within 42 days. Based on the metabolites analysis, HBCD might be sequentially debrominated via dibromo elimination reaction to form tetrabromocyclododecene, dibromocyclododecadiene, and 1,5,9-cyclododecatriene. The biotransformation of the technical HBCD was likely diastereoisomer-specific. The transformation rates of α-, ß-, and γ-HBCD were in the following order: α-HBCD > ß-HBCD > γ-HBCD. The enantiomer fractions of (±)α-, (±)ß-, and (±)γ-HBCD were maintained at about 0.5 during the 28 days of incubation, indicating a lack of enantioselective biotransformation of these diastereoisomers. Additionally, the amendment of another halogenated substrate tetrachloroethene (PCE), which supports the growth of strain 195, had a negligible impact on the transformation patterns of HBCD diastereoisomers and enantiomers. This study provided new insights into the stereoisomer-specific transformation patterns of HBCD by anaerobic microbes and has important implications for microbial remediation of anoxic environments contaminated by HBCD using the mixed culture containing Dehalococcoides.

Solvent effects on quantitative analysis of brominated flame retardants with Soxhlet extraction.

Reliable quantifications of brominated flame retardants (BFRs) not only ensure compliance with laws and regulations on the use of BFRs in commercial products, but also is key for accurate risk assessments of BFRs. Acetone is a common solvent widely used in the analytical procedure of BFRs, but our recent study found that acetone can react with some BFRs. It is highly likely that such reactions can negatively affect the quantifications of BFRs in environmental samples. In this study, the effects of acetone on the extraction yields of three representative BFRs [i.e., decabrominated diphenyl ether (decaBDE), hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA)] were evaluated in the Soxhlet extraction (SE) system. The results showed that acetone-based SE procedure had no measureable effect for the recovery efficiencies of decaBDE but could substantially lower the extraction yields for both TBBPA and HBCD. After 24 h of extraction, the recovery efficiencies of TBBPA and HBCD by SE were 93 and 78% with acetone, 47 and 70% with 3:1 acetone:n-hexane, and 82 and 94% with 1:1 acetone:n-hexane, respectively. After 72 h of extraction, the extraction efficiencies of TBBPA and HBCD decreased to 68 and 55% with acetone, 0 and 5% with 3:1 acetone/n-hexane mixtures, and 0 and 13% with 1:1 acetone/n-hexane mixtures, respectively. The study suggested that the use of acetone alone or acetone-based mixtures should be restricted in the quantitative analysis of HBCD and TBBPA. We further evaluated nine alternative solvents for the extraction of the three BFRs. The result showed that diethyl ether might be reactive with HBCD and may not be considered as the alternative to acetone used solvents for the extraction of HBCD.

Abiotic transformation of hexabromocyclododecane by sulfidated nanoscale zerovalent iron: Kinetics, mechanism and influencing factors.

Recent studies showed that sulfidated nanoscale zerovalent iron (S-nZVI) is a better reducing agent than nanoscale zerovalen iron (nZVI) alone for reductive dechlorination of several organic solvents such as trichloroethylene (TCE) due to the catalytic role of iron sulfide (FeS). We measured the rates of transformation of hexabromocyclododecane (HBCD) by S-nZVI and compared them to those by FeS, nZVI, and reduced sulfur species. The results showed that: i) HBCD (20 mg L-1) was almost completely transformed by S-nZVI (0.5 g L-1) within 12 h; ii) the reaction with ß-HBCD was much faster than with α- and γ-HBCD, suggesting the diastereoisomeric selectivity for the reaction by S-nZVI; and iii) the reaction with S-nZVI was 1.4-9.3 times faster than with FeS, S2- and nZVI, respectively. The study further showed that the HBCD reaction by S-nZVI was likely endothermic, with the optimal solution pH of 5.0, and could be slowed in the presence of Ca2+, Mg2+, NO3-, HCO3- and Cl-, and by increasing ionic strength, solvent content and initial HBCD concentration, or decreasing the S-nZVI dosage. GC-MS analysis showed that tetrabromocyclododecene and dibromocyclododecadiene were the products. XPS spectra indicated that both Fe(II) and S(-II) on the S-nZVI surface were oxidized during the reaction, suggesting that FeS might act as both catalyst and reactant. The study not only demonstrated the superiority of S-nZVI over other well-known reactive reagents, but also provided insight to the mechanisms of the reaction.

Engineered jadomycin analogues with altered sugar moieties revealing JadS as a substrate flexible O-glycosyltransferase.

Glycosyltransferases (GTs)-mediated glycodiversification studies have drawn significant attention recently, with the goal of generating bioactive compounds with improved pharmacological properties by diversifying the appended sugars. The key to achieving glycodiversification is to identify natural and/or engineered flexible GTs capable of acting upon a broad range of substrates. Here, we report the use of a combinatorial biosynthetic approach to probe the substrate flexibility of JadS, the GT in jadomycin biosynthesis, towards different non-native NDP-sugar substrates, enabling us to identify six jadomycin B analogues with different sugar moieties. Further structural engineering by precursor-directed biosynthesis allowed us to obtain 11 new jadomycin analogues. Our results for the first time show that JadS is a flexible O-GT that can utilize both L- and D- sugars as donor substrates, and tolerate structural changes at the C2, C4 and C6 positions of the sugar moiety. JadS may be further exploited to generate novel glycosylated jadomycin molecules in future glycodiversification studies.