RESUMEN
Per- and polyfluoroalkyl substances (PFAS), particularly the perfluorinated ones, are recalcitrant to biodegradation. By integrating an enrichment culture of reductive defluorination with biocompatible electrodes for the electrochemical process, a deeper defluorination of a C6-perfluorinated unsaturated PFAS was achieved compared to the biological or electrochemical system alone. Two synergies in the bioelectrochemical system were identified: i) The in-series microbial-electrochemical defluorination and ii) the electrochemically enabled microbial defluorination of intermediates. These synergies at the material-microbe interfaces surpassed the limitation of microbial defluorination and further turned the biotransformation end products into less fluorinated products, which could be less toxic and more biodegradable in the environment. This material-microbe hybrid system brings opportunities in the bioremediation of PFAS driven by renewable electricity and warrants future research on mechanistic understanding of defluorinating and electroactive microorganisms at the material-microbe interface for system optimizations.
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Biodegradación Ambiental , Anaerobiosis , Halogenación , Electrodos/microbiología , Fluorocarburos/metabolismo , Fluorocarburos/química , Técnicas Electroquímicas/métodos , Bacterias/metabolismoRESUMEN
The acetogen Acetobacterium woodii couples caffeate reduction with ferredoxin reduction and NADH oxidation via electron bifurcation, providing additional reduced ferredoxin for energy conservation and cell synthesis. Caffeate is first activated by an acyl-CoA synthetase (CarB), which ligates CoA to caffeate at the expense of ATP. After caffeoyl-CoA is reduced to hydrocaffeoyl-CoA, the CoA moiety in hydrocaffeoyl-CoA could be recycled for caffeoyl-CoA synthesis by an ATP-independent CoA transferase (CarA) to save energy. However, given that CarA and CarB are co-expressed, it was not well understood how ATP could be saved when both two competitive pathways of caffeate activation are present. Here, we reported a dual feedback inhibition of the CarB-mediated caffeate activation by the intermediate hydrocaffeoyl-CoA and the end-product hydrocaffeate. As the product of CarA, hydrocaffeate inhibited CarB-mediated caffeate activation by serving as another substrate of CarB with hydrocaffeoyl-CoA produced. It effectively competed with caffeate even at a concentration much lower than caffeate. Hydrocaffeoyl-CoA formed in this process can also inhibit CarB-mediated caffeate activation. Thus, the dual feedback inhibition of CarB, together with the faster kinetics of CarA, makes the ATP-independent CarA-mediated CoA loop the major route for caffeoyl-CoA synthesis, further saving ATP in the caffeate-dependent electron-bifurcating pathway. A genetic architecture similar to carABC has been found in other anaerobic bacteria, suggesting that the feedback inhibition of acyl-CoA ligases could be a widely employed strategy for ATP conservation in those pathways requiring substrate activation by CoA. IMPORTANCE: This study reports a dual feedback inhibition of caffeoyl-CoA synthetase by two downstream products, hydrocaffeate and hydrocaffeoyl-CoA. It elucidates how such dual feedback inhibition suppresses ATP-dependent caffeoyl-CoA synthesis, hence making the ATP-independent route the main pathway of caffeate activation. This newly discovered mechanism contributes to our current understanding of ATP conservation during the caffeate-dependent electron-bifurcating pathway in the ecologically important acetogen Acetobacterium woodii. Bioinformatic mining of microbial genomes revealed contiguous genes homologous to carABC within the genomes of other anaerobes from various environments, suggesting this mechanism may be widely used in other CoA-dependent electron-bifurcating pathways.
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Hydrogen-tuned 185 nm vacuum ultraviolet (VUV/H2) photolysis is an emerging technology to destroy per- and polyfluoroalkyl substance (PFAS) in brine. This study discovered the promotive effects of two major brine anions, i.e., chloride and sulfate in VUV/H2 photolysis on the hydrated electron (eaq-) generation and perfluorocarboxylates (PFCAs) destruction and established a kinetics model to elucidate the promotive effects on the steady-state concentration of eaq- ([eaq-]ss). Results showed that VUV/H2 achieved near-complete defluorination of perfluorooctanoic acid (PFOA) in the presence of up to 1000 mM chloride or sulfate at pH 12. The defluorination rate constant (kdeF) of PFOA peaked with a chloride concentration at 100 mM and with a sulfate concentration at 500 mM. The promotive effects of chloride and sulfate were attributed to an enhanced generation of eaq- via their direct VUV photolysis and conversion of additionally generated hydroxyl radical to eaq- by H2, which was supported by a linear correlation between the predicted [eaq-]ss and experimentally observed kdeF. The kdeF value increased from pH 9 to 12, which was attributed to the speciation of the H·/eaq- pair. Furthermore, the VUV system achieved >95% defluorination and ≥99% parent compound degradation of a concentrated PFCAs mixture in a synthetic brine, without generating any toxic perchlorate or chlorate.
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Cloruros , Fluorocarburos , Hidrógeno , Fotólisis , Sulfatos , Rayos Ultravioleta , Cinética , Fluorocarburos/química , Sulfatos/química , Hidrógeno/química , Cloruros/química , Sales (Química)/química , Contaminantes Químicos del Agua/química , CaprilatosRESUMEN
The total oxidizable precursor (TOP) assay has been extensively used for detecting PFAS pollutants that do not have analytical standards. It uses hydroxyl radicals (HOâ¢) from the heat activation of persulfate under alkaline pH to convert H-containing precursors to perfluoroalkyl carboxylates (PFCAs) for target analysis. However, the current TOP assay oxidation method does not apply to emerging PFAS because (i) many structures do not contain C-H bonds for HO⢠attack and (ii) the transformation products are not necessarily PFCAs. In this study, we explored the use of classic acidic persulfate digestion, which generates sulfate radicals (SO4-â¢), to extend the capability of the TOP assay. We examined the oxidation of Nafion-related ether sulfonates that contain C-H or -COO-, characterized the oxidation products, and quantified the F atom balance. The SO4-⢠oxidation greatly expanded the scope of oxidizable precursors. The transformation was initiated by decarboxylation, followed by various spontaneous steps, such as HF elimination and ester hydrolysis. We further compared the oxidation of legacy fluorotelomers using SO4-⢠versus HOâ¢. The results suggest novel product distribution patterns, depending on the functional group and oxidant dose. The general trends and strategies were also validated by analyzing a mixture of 100000- or 10000-fold diluted aqueous film-forming foam (containing various fluorotelomer surfactants and organics) and a spiked Nafion precursor. Therefore, (1) the combined use of SO4-⢠and HO⢠oxidation, (2) the expanded list of standard chemicals, and (3) further elucidation of SO4-⢠oxidation mechanisms will provide more critical information to probe emerging PFAS pollutants.
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Contaminantes Ambientales , Polímeros de Fluorocarbono , Fluorocarburos , Contaminantes Químicos del Agua , Éter , Fluorocarburos/análisis , Contaminantes Químicos del Agua/análisis , Ácidos Carboxílicos , Éteres , Alcanosulfonatos , Éteres de Etila , Digestión , Estrés OxidativoRESUMEN
Graphitic carbon nitride (g-C3N4) nanomaterials hold great promise in diverse applications; however, their stability in engineering systems and transformation in nature are largely underexplored. We evaluated the stability, aging, and environmental impact of g-C3N4 nanosheets under the attack of free chlorine and reactive chlorine species (RCS), a widely used oxidant/disinfectant and a class of ubiquitous radical species, respectively. g-C3N4 nanosheets were slowly oxidized by free chlorine even at a high concentration of 200-1200 mg L-1, but they decomposed rapidly when ClO· and/or Cl2â¢- were the key oxidants. Though Cl2â¢- and ClO· are considered weaker oxidants in previous studies due to their lower reduction potentials and slower reaction kinetics than ·OH and Cl·, our study highlighted that their electrophilic attack efficacy on g-C3N4 nanosheets was on par with ·OH and much higher than Cl·. A trace level of covalently bonded Cl (0.28-0.55 at%) was introduced to g-C3N4 nanosheets after free chlorine and RCS oxidation. Our study elucidates the environmental fate and transformation of g-C3N4 nanosheets, particularly under the oxidation of chlorine-containing species, and it also provides guidelines for designing reactive, robust, and safe nanomaterials for engineering applications.
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Grafito , Nanoestructuras , Cloro , Oxidantes , ClorurosRESUMEN
Superoxide and other reactive oxygen species (ROS) shape microbial communities and drive the transformation of metals and inorganic/organic matter. Taxonomically diverse bacteria and phytoplankton produce extracellular superoxide during laboratory cultivation. Understanding the physiological reasons for extracellular superoxide production by aerobes in the environment is a crucial question yet not fully solved. Here, we showed that iron-starving Arthrobacter sp. QXT-31 (A. QXT-31) secreted a type of siderophore [deferoxamine (DFO)], which provoked extracellular superoxide production by A. QXT-31 during carbon sources-level fluctuation. Several other siderophores also demonstrated similar effects to A. QXT-31. RNA-Seq data hinted that DFO stripped iron from iron-bearing proteins in electron transfer chain (ETC) of metabolically active A. QXT-31, resulting in electron leakage from the electron-rich (resulting from carbon sources metabolism by A. QXT-31) ETC and superoxide production. Considering that most aerobes secrete siderophore(s) and undergo carbon sources-level fluctuation, the superoxide-generation pathway is likely a common pathway by which aerobes produce extracellular superoxide in the environment, thus influencing the microbial community and cycling of elements. Our results pointed that the ubiquitous siderophore might be the potential driving force for the microbial generation of superoxide and other ROS and revealed the important role of iron physiology in microbial ROS generation.
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Arthrobacter , Sideróforos , Arthrobacter/genética , Arthrobacter/metabolismo , Carbono/metabolismo , Hierro/metabolismo , Sideróforos/metabolismo , Superóxidos/metabolismoRESUMEN
The recently discovered microbial reductive defluorination of two C6 branched and unsaturated fluorinated carboxylic acids (FCAs) provided valuable insights into the environmental fate of per- and polyfluoroalkyl substances (PFASs) and potential bioremediation strategies. However, a systematic investigation is needed to further demonstrate the role of CâC double bonds in the biodegradability of unsaturated PFASs. Here, we examined the structure-biodegradability relationships of 13 FCAs, including nine commercially available unsaturated FCAs and four structurally similar saturated ones, in an anaerobic defluorinating enrichment and an activated sludge community. The anaerobic and aerobic transformation/defluorination pathways were elucidated. The results showed that under anaerobic conditions, the α,ß-unsaturation is crucial for FCA biotransformation via reductive defluorination and/or hydrogenation pathways. With sp2 C-F bonds being substituted by C-H bonds, the reductive defluorination became less favorable than hydrogenation. Moreover, for the first time, we reported enhanced degradability and defluorination capability of specific unsaturated FCA structures with trifluoromethyl (-CF3) branches at the α/ß-carbon. Such FCA structures can undergo anaerobic abiotic defluorination in the presence of reducing agents and significant aerobic microbial defluorination. Given the diverse applications and emerging concerns of fluorochemicals, this work not only advances the fundamental understanding of the fate of unsaturated PFASs in natural and engineered environments but also may provide insights into the design of readily degradable fluorinated alternatives to existing PFAS compounds.
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Ácidos Carboxílicos , Fluorocarburos , Anaerobiosis , Biodegradación Ambiental , Fluorocarburos/química , Aguas del AlcantarilladoRESUMEN
The addition of iodide (I-) in the UV/sulfite system (UV/S) significantly accelerated the reductive degradation of perfluorosulfonates (PFSAs, CnF2n+1SO3-) and perfluorocarboxylates (PFCAs, CnF2n+1COO-). Using the highly recalcitrant perfluorobutane sulfonate (C4F9SO3-) as a probe, we optimized the UV/sulfite + iodide system (UV/S + I) to degrade n = 1-7 PFCAs and n = 4, 6, 8 PFSAs. In general, the kinetics of per- and polyfluoroalkyl substance (PFAS) decay, defluorination, and transformation product formations in UV/S + I were up to three times faster than those in UV/S. Both systems achieve a similar maximum defluorination. The enhanced reaction rates and optimized photoreactor settings lowered the EE/O for PFCA degradation below 1.5 kW h m-3. The relatively high quantum yield of eaq- from I- made the availability of hydrated electrons (eaq-) in UV/S + I and UV/I two times greater than that in UV/S. Meanwhile, the rapid scavenging of reactive iodine species by SO32- made the lifetime of eaq- in UV/S + I eight times longer than that in UV/I. The addition of I- also substantially enhanced SO32- utilization in treating concentrated PFAS. The optimized UV/S + I system achieved >99.7% removal of most PFSAs and PFCAs and >90% overall defluorination in a synthetic solution of concentrated PFAS mixtures and NaCl. We extended the discussion over molecular transformation mechanisms, development of PFAS degradation technologies, and the fate of iodine species.
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Fluorocarburos , Yodo , Contaminantes Químicos del Agua , Fluorocarburos/análisis , Yoduros , Sulfitos , Rayos Ultravioleta , Contaminantes Químicos del Agua/análisisRESUMEN
Omega-hydroperfluorocarboxylates (ω-HPFCAs, HCF2-(CF2)n-1-COO-) are commercially available in bulk quantities and have been applied in agrochemicals, fluoropolymer production, and semiconductor coating. In this study, we used kinetic measurements, theoretical calculations, model compound experiments, and transformation product analyses to reveal novel mechanistic insights into the reductive and oxidative transformation of ω-HPFCAs. Like perfluorocarboxylates (PFCAs, CF3-(CF2)n-1-COO-), the direct linkage between HCnF2n- and -COO- enables facile degradation under UV/sulfite treatment. To our surprise, the presence of the H atom on the remote carbon makes ω-HPFCAs more susceptible than PFCAs to decarboxylation (i.e., yielding shorter-chain ω-HPFCAs) and less susceptible to hydrodefluorination (i.e., H/F exchange). Like fluorotelomer carboxylates (FTCAs, CnF2n+1-CH2CH2-COO-), the C-H bond in HCF2-(CF2)n-1-COO- allows hydroxyl radical oxidation and limited defluorination. While FTCAs yielded PFCAs in all chain lengths, ω-HPFCAs only yielded -OOC-(CF2)n-1-COO- (major) and -OOC-(CF2)n-2-COO- (minor) due to the unfavorable ß-fragmentation pathway that shortens the fluoroalkyl chain. We also compared two treatment sequences-UV/sulfite followed by heat/persulfate and the reverse-toward complete defluorination of ω-HPFCAs. The findings will benefit the treatment and monitoring of H-containing per- and polyfluoroalkyl substance (PFAS) pollutants as well as the design of future fluorochemicals.
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Contaminantes Ambientales , Fluorocarburos , Ácidos Carboxílicos , Radical Hidroxilo , Oxidación-ReducciónRESUMEN
The UV-sulfite reductive treatment using hydrated electrons (eaq-) is a promising technology for destroying perfluorocarboxylates (PFCAs, CnF2n+1COO-) in any chain length. However, the C-H bonds formed in the transformation products strengthen the residual C-F bonds and thus prevent complete defluorination. Reductive treatments of fluorotelomer carboxylates (FTCAs, CnF2n+1-CH2CH2-COO-) and sulfonates (FTSAs, CnF2n+1-CH2CH2-SO3-) are also sluggish because the ethylene linker separates the fluoroalkyl chain from the end functional group. In this work, we used oxidation (Ox) with hydroxyl radicals (HOâ¢) to convert FTCAs and FTSAs to a mixture of PFCAs. This process also cleaved 35-95% of C-F bonds depending on the fluoroalkyl chain length. We probed the stoichiometry and mechanism for the oxidative defluorination of fluorotelomers. The subsequent reduction (Red) with UV-sulfite achieved deep defluorination of the PFCA mixture for up to 90%. The following use of HO⢠to oxidize the H-rich residues led to the cleavage of the remaining C-F bonds. We examined the efficacy of integrated oxidative and reductive treatment of n = 1-8 PFCAs, n = 4,6,8 perfluorosulfonates (PFSAs, CnF2n+1-SO3-), n = 1-8 FTCAs, and n = 4,6,8 FTSAs. A majority of structures yielded near-quantitative overall defluorination (97-103%), except for n = 7,8 fluorotelomers (85-89%), n = 4 PFSA (94%), and n = 4 FTSA (93%). The results show the feasibility of complete defluorination of legacy PFAS pollutants and will advance both remediation technology design and water sample analysis.
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Contaminantes Ambientales , Fluorocarburos , Contaminantes Químicos del Agua , Alcanosulfonatos , Ácidos Carboxílicos , Oxidación-ReducciónRESUMEN
Wastewater treatment plant (WWTP) upgrades can reduce both nutrient and micropollutant emissions into receiving rivers, thus modifying the composition and function of biological communities. However, how microbial communities vary and whether they can be restored to levels found in less-polluted rivers remains uncertain. Aquatic biofilms are sensitive to environmental change and respond rapidly to bottom-up pressure. Thus, we used 12 flumes configured in three experimental treatments to mimic the dynamic processes of biofilm microbial communities occurring in a wastewater-receiving river following WWTP upgrade, with rivers containing two levels of nutrients and micropollutants used as references. We compared the biofilm microbial biomass, carbon source utilization, and community composition among the three "blocks". Results showed that the metabolic patterns of the carbon sources and composition of the biofilm bacterial communities in the flumes mimicking a receiving river with WWTP upgrade recovered over time to those mimicking a less-disturbed river. The restoration of potential carboxylic acid-consuming denitrifying bacteria (i.e., Zoogloea, Comamonas, Dechloromonas, and Acinetobacter) likely played a significant role in this process. Combining quantitative analysis of the denitrification genes nirS and nosZ, we confirmed that the denitrification function of the river biofilms recovered after WWTP upgrade, consistent with our previous field investigation.
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Ríos , Purificación del Agua , Bacterias/genética , Biopelículas , Aguas Residuales/análisisRESUMEN
Antibiotic resistance is one of the most challenging issues in public health. Antibiotics have been increasingly used not only for humans and animals but also for crop protection as pesticides. Thus, antibiotics often coexist with pesticides in some environments. To investigate the effects of the co-occurring, nonantibiotic pesticides on the development of antibiotic resistance, we conducted long-term exposure experiments using an Escherichia coli K-12 model strain. The results reveal that (1) the exposure to pesticides (in mg/L) alone led to the emergence of mutants with significantly higher resistance to streptomycin; (2) the exposure to pesticides (in µg/L) together with a subinhibitory level (in high µg/L) of ampicillin synergistically stimulated the selection of ampicillin resistance and the cross-resistance to other antibiotics (i.e., ciprofloxacin, chloramphenicol, and tetracycline). Distinct and diversified genetic mutations emerged in the resistant mutants selected from the coexposure to both pesticides and ampicillin. The genetic mutations likely caused a holistic transcriptional regulation (e.g., biofilm formation, oxidative stress defense) when grown under antibiotic stress and led to increased antibiotic resistance. Together, these findings provide important fundamental insights into the development of antibiotic resistance and the resistance mechanisms under environmentally relevant conditions where antibiotics and nonantibiotic micropollutants coexist.
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Escherichia coli K12 , Plaguicidas , Animales , Antibacterianos/farmacología , Farmacorresistencia Bacteriana/genética , Farmacorresistencia Microbiana/genética , Escherichia coli/genética , Humanos , Pruebas de Sensibilidad Microbiana , Plaguicidas/toxicidadRESUMEN
This study explores structure-reactivity relationships for the degradation of emerging perfluoroalkyl ether carboxylic acid (PFECA) pollutants with ultraviolet-generated hydrated electrons (eaq-). The rate and extent of PFECA degradation depend on both the branching extent and the chain length of oxygen-segregated fluoroalkyl moieties. Kinetic measurements, theoretical calculations, and transformation product analyses provide a comprehensive understanding of the PFECA degradation mechanisms and pathways. In comparison to traditional full-carbon-chain perfluorocarboxylic acids, the distinct degradation behavior of PFECAs is attributed to their ether structures. The ether oxygen atoms increase the bond dissociation energy of the C-F bonds on the adjacent -CF2- moieties. This impact reduces the formation of H/F-exchanged polyfluorinated products that are recalcitrant to reductive defluorination. Instead, the cleavage of ether C-O bonds generates unstable perfluoroalcohols and thus promotes deep defluorination of short fluoroalkyl moieties. In comparison to linear PFECAs, branched PFECAs have a higher tendency of H/F exchange on the tertiary carbon and thus lower percentages of defluorination. These findings provide mechanistic insights for an improved design and efficient degradation of fluorochemicals.
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Ácidos Carboxílicos , Fluorocarburos , Electrones , Éter , ÉteresRESUMEN
The C-F bond is one of the strongest single bonds in nature. Although microbial reductive dehalogenation is well known for the other organohalides, no microbial reductive defluorination has been documented for perfluorinated compounds except for a single, nonreproducible study on trifluoroacetate. Here, we report on C-F bond cleavage in two C6 per- and polyfluorinated compounds via reductive defluorination by an organohalide-respiring microbial community. The reductive defluorination was demonstrated by the release of F- and the formation of the corresponding product when lactate was the electron donor, and the fluorinated compound was the sole electron acceptor. The major dechlorinating species in the seed culture, Dehalococcoides, were not responsible for the defluorination as no growth of Dehalococcoides or active expression of Dehalococcoides-reductive dehalogenases was observed. It suggests that minor phylogenetic groups in the community might be responsible for the reductive defluorination. These findings expand our fundamental knowledge of microbial reductive dehalogenation and warrant further studies on the enrichment, identification, and isolation of responsible microorganisms and enzymes. Given the wide use and emerging concerns of fluorinated organics (e.g., per- and polyfluoroalkyl substances), particularly the perfluorinated ones, the discovery of microbial defluorination under common anaerobic conditions may provide valuable insights into the environmental fate and potential bioremediation strategies of these notorious contaminants.
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Chloroflexi , Biodegradación Ambiental , FilogeniaRESUMEN
The recently discovered complete ammonia-oxidizing (comammox) bacteria occur in various environments, including wastewater treatment plants. To better understand their role in micropollutant biotransformation in comparison with ammonia-oxidizing bacteria (AOB) and ammonia-oxidizing archaea (AOA), we investigated the biotransformation capability of Nitrospira inopinata (the only comammox isolate) for 17 micropollutants. Asulam, fenhexamid, mianserin, and ranitidine were biotransformed by N. inopinata, Nitrososphaera gargensis (AOA), and Nitrosomonas nitrosa Nm90 (AOB). More distinctively, carbendazim, a benzimidazole fungicide, was exclusively biotransformed by N. inopinata. The biotransformation of carbendazim only occurred when N. inopinata was supplied with ammonia but not nitrite as the energy source. The exclusive biotransformation of carbendazim by N. inopinata was likely enabled by an enhanced substrate promiscuity of its unique AMO and its much higher substrate (for ammonia) affinity compared with the other two ammonia oxidizers. One major plausible transformation product (TP) of carbendazim is a hydroxylated form at the aromatic ring, which is consistent with the function of AMO. These findings provide fundamental knowledge on the micropollutant degradation potential of a comammox bacterium to better understand the fate of micropollutants in nitrifying environments.
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Nitrificación , Microbiología del Suelo , Amoníaco , Archaea , Bacterias , Biotransformación , Oxidación-Reducción , FilogeniaRESUMEN
This study investigates critical structure-reactivity relationships within 34 representative per- and polyfluoroalkyl substances (PFASs) undergoing defluorination with UV-generated hydrated electrons. While C nF2 n+1-COO- with variable fluoroalkyl chain lengths ( n = 2 to 10) exhibited a similar rate and extent of parent compound decay and defluorination, the reactions of telomeric C nF2 n+1-CH2CH2-COO- and C nF2 n+1-SO3- showed an apparent dependence on the length of the fluoroalkyl chain. Cross comparison of experimental results, including different rates of decay and defluorination of specific PFAS categories, the incomplete defluorination from most PFAS structures, and the surprising 100% defluorination from CF3COO-, leads to the elucidation of new mechanistic insights into PFAS degradation. Theoretical calculations on the C-F bond dissociation energies (BDEs) of all PFAS structures reveal strong relationships among (i) the rate and extent of decay and defluorination, (ii) head functional groups, (iii) fluoroalkyl chain length, and (iv) the position and number of C-F bonds with low BDEs. These relationships are further supported by the spontaneous cleavage of specific bonds during calculated geometry optimization of PFAS structures bearing one extra electron, and by the product analyses with high-resolution mass spectrometry. Multiple reaction pathways, including H/F exchange, dissociation of terminal functional groups, and decarboxylation-triggered HF elimination and hydrolysis, result in the formation of variable defluorination products. The selectivity and ease of C-F bond cleavage highly depends on molecular structures. These findings provide critical information for developing PFAS treatment processes and technologies to destruct a wide scope of PFAS pollutants and for designing fluorochemical formulations to avoid releasing recalcitrant PFASs into the environment.
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Contaminantes Ambientales , Fluorocarburos , Electrones , Espectrometría de MasasRESUMEN
Functional differentiation and metabolite exchange enable microbial consortia to perform complex metabolic tasks and efficiently cycle the nutrients. Inspired by the cooperative relationships in environmental microbial consortia, synthetic microbial consortia have great promise for studying the microbial interactions in nature and more importantly for various engineering applications. However, challenges coexist with promises, and the potential of consortium-based technologies is far from being fully harnessed. Thorough understanding of the underlying molecular mechanisms of microbial interactions is greatly needed for the rational design and optimization of defined consortia. These knowledge gaps could be potentially filled with the assistance of the ongoing revolution in systems biology and synthetic biology tools. As current fundamental and technical obstacles down the road being removed, we would expect new avenues with synthetic microbial consortia playing important roles in biological and environmental engineering processes such as bioproduction of desired chemicals and fuels, as well as biodegradation of persistent contaminants.
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Consorcios Microbianos , Animales , Biodegradación Ambiental , Humanos , Interacciones Microbianas , Biología Sintética , Biología de SistemasRESUMEN
Biotransformation of various micropollutants (MPs) has been found to be positively correlated with nitrification in activated sludge communities. To further elucidate the roles played by ammonia-oxidizing bacteria (AOB) and nitrite-oxidizing bacteria (NOB), we investigated the biotransformation capabilities of an NOB pure culture ( Nitrobacter sp.) and an AOB ( Nitrosomonas europaea)/NOB ( Nitrobacter sp.) coculture for 15 MPs, whose biotransformation was reported previously to be associated with nitrification. The NOB pure culture did not biotransform any investigated MP, whereas the AOB/NOB coculture was capable of biotransforming six MPs (i.e., asulam, bezafibrate, fenhexamid, furosemide, indomethacin, and rufinamide). Transformation products (TPs) were identified, and tentative structures were proposed. Inhibition studies with octyne, an ammonia monooxygenase (AMO) inhibitor, suggested that AMO was the responsible enzyme for MP transformation that occurred cometabolically. For the first time, hydroxylamine, a key intermediate of all aerobic ammonia oxidizers, was found to react with several MPs at concentrations typically occurring in AOB batch cultures. All of these MPs were also biotransformed by the AOB/NOB coculture. Moreover, the same asulam TPs were detected in both biotransformation and hydroxylamine-treated abiotic transformation experiments, whereas rufinamide TPs formed from biological transformation were not detected during hydroxylamine-mediated abiotic transformation, which was consistent with the inability of rufinamide abiotic transformation by hydroxylamine. Thus, in addition to cometabolism likely carried out by AMO, an abiotic transformation route indirectly mediated by AMO might also contribute to MP biotransformation by AOB.
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Amoníaco , Nitritos , Reactores Biológicos , Biotransformación , Técnicas de Cocultivo , Hidroxilamina , Hidroxilaminas , Oxidación-Reducción , OxidorreductasasRESUMEN
For many polar organic micropollutants, biotransformation by activated sludge microorganisms is a major removal process during wastewater treatment. However, our current understanding of how wastewater treatment operations influence microbial communities and their micropollutant biotransformation potential is limited, leaving major parts of observed variability in biotransformation rates across treatment facilities unexplained. Here, we present biotransformation rate constants for 42 micropollutants belonging to different chemical classes along a gradient of solids retention time (SRT). The geometric mean of biomass-normalized first-order rate constants shows a clear increase between 3 and 15 d SRT by 160% and 87%, respectively, in two experiments. However, individual micropollutants show a variety of trends. Rate constants of oxidative biotransformation reactions mostly increased with SRT. Yet, nitrifying activity could be excluded as primary driver. For substances undergoing other than oxidative reactions, i.e., mostly substitution-type reactions, more diverse dependencies on SRT were observed. Most remarkably, characteristic trends were observed for groups of substances undergoing similar types of initial transformation reaction, suggesting that shared enzymes or enzyme systems that are conjointly regulated catalyze biotransformation reactions within such groups. These findings open up opportunities for correlating rate constants with measures of enzyme abundance such as genes or gene products, which in turn should help to identify enzymes associated with the respective biotransformation reactions.
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Contaminantes Químicos del Agua , Biotransformación , Oxidación-Reducción , Aguas del Alcantarillado , Eliminación de Residuos Líquidos , Aguas ResidualesRESUMEN
The aim of this study is to obtain a systems-level understanding of the interactions between Dehalococcoides and corrinoid-supplying microorganisms by analyzing community structures and functional compositions, activities, and dynamics in trichloroethene (TCE)-dechlorinating enrichments. Metagenomes and metatranscriptomes of the dechlorinating enrichments with and without exogenous cobalamin were compared. Seven putative draft genomes were binned from the metagenomes. At an early stage (2 days), more transcripts of genes in the Veillonellaceae bin-genome were detected in the metatranscriptome of the enrichment without exogenous cobalamin than in the one with the addition of cobalamin. Among these genes, sporulation-related genes exhibited the highest differential expression when cobalamin was not added, suggesting a possible release route of corrinoids from corrinoid producers. Other differentially expressed genes include those involved in energy conservation and nutrient transport (including cobalt transport). The most highly expressed corrinoid de novo biosynthesis pathway was also assigned to the Veillonellaceae bin-genome. Targeted quantitative PCR (qPCR) analyses confirmed higher transcript abundances of those corrinoid biosynthesis genes in the enrichment without exogenous cobalamin than in the enrichment with cobalamin. Furthermore, the corrinoid salvaging and modification pathway of Dehalococcoides was upregulated in response to the cobalamin stress. This study provides important insights into the microbial interactions and roles played by members of dechlorinating communities under cobalamin-limited conditions.IMPORTANCE The key chloroethene-dechlorinating bacterium Dehalococcoides mccartyi is a cobalamin auxotroph, thus acquiring corrinoids from other community members. Therefore, it is important to investigate the microbe-microbe interactions between Dehalococcoides and the corrinoid-providing microorganisms in a community. This study provides systems-level information, i.e., taxonomic and functional compositions and dynamics of the supportive microorganisms in dechlorinating communities under different cobalamin conditions. The findings shed light on the important roles of Veillonellaceae species in the communities compared to other coexisting community members in producing and providing corrinoids for Dehalococcoides species under cobalamin-limited conditions.