A two-stage design enhanced biodegradation of high concentrations of a C16-alkyl quaternary ammonium compound in oxygen-based membrane biofilm reactors.

Quaternary ammonia compounds (QAC), such as hexadecyltrimethyl-ammonium (CTAB), are widely used as disinfectants and in personal-care products. Their use as disinfectants grew during the SARS-CoV-2 (COVID-19) pandemic, leading to increased loads to wastewater treatment systems and the environment. Though low concentrations of CTAB are biodegradable, high concentrations are toxic to bacteria. Sufficient O2 delivery is a key to achieve high CTAB removal, and the O2-based Membrane Biofilm Reactor (O2-MBfR) is a proven means to biodegrade CTAB in a bubble-free, non-foaming manner. A strategy for achieving complete biodegradation of high-concentrations of CTAB is a two-stage O2-MBfR, in which partial CTAB removal in the Lead reactor relieves inhibition in the Lag reactor. Here, more than 98 % removal of 728 mg/L CTAB could be achieved in the two-stage MBfR, and the CTAB-removal rate was 70 % higher than for a one-stage MBfR with the same O2-delivery capacity. CTAB exposure shifted the bacterial community toward Pseudomonas and Stenotrophomonas as the dominant genera. In particular, P. alcaligenes and P. aeruginosa were enriched in the Lag reactor, as they were capable of biodegrading the metabolites of initial CTAB monooxygenation. Metagenomic analysis also revealed that the Lag reactor was enriched in genes for CTAB and metabolite oxygenation, due to reduced CTAB inhibition.

Simultaneous biodegradation kinetics of 1,4-dioxane and ethane.

Biodegradation of 1,4-Dioxane at environmentally relevant concentrations usually requires the addition of a primary electron-donor substrate to sustain biomass growth. Ethane is a promising substrate, since it is available as a degradation product of 1,4-Dioxane's common co-contaminants. This study reports kinetic parameters for ethane biodegradation and co-oxidations of ethane and 1,4-Dioxane. Based on experiments combined with mathematical modeling, we found that ethane promoted 1,4-Dioxane biodegradation when the initial mass ratio of ethane:1,4-Dioxane was < 9:1 mg COD/mg COD, while it inhibited 1,4-Dioxane degradation when the ratio was > 9:1. A model-independent estimator was used for kinetic-parameter estimation, and all parameter values for 1,4-Dioxane were consistent with literature-reported ranges. Estimated parameters support competitive inhibition between ethane as the primary substrate and 1,4-Dioxane as the secondary substrate. The results also support that bacteria that co-oxidize ethane and 1,4-Dioxane had a competitive advantage over bacteria that can use only one of the two substrates. The minimum concentration of ethane to sustain ethane-oxidizing bacteria and ethane and 1,4-Dioxane-co-oxidizing bacteria was 0.09 mg COD/L, which is approximately 20-fold lower than the minimum concentration reported for propane, another common substrate used to promote 1,4-Dioxane biodegradation. The minimum 1,4-Dioxane concentration required to sustain steady-state biomass with 1,4-Dioxane as the sole primary substrate was 1.3 mg COD/L. As 1,4-Dioxane concentrations at most groundwater sites are less than 0.18 mg COD/L, providing ethane as a primary substrate is vital to support biomass growth and consequently enable 1,4-Dioxane bioremediation.

Identifying biodegradation pathways of cetrimonium bromide (CTAB) using metagenome, metatranscriptome, and metabolome tri-omics integration.

Traditional research on biodegradation of emerging organic pollutants involves slow and labor-intensive experimentation. Currently, fast-developing metagenome, metatranscriptome, and metabolome technologies promise to expedite mechanistic research on biodegradation of emerging organic pollutants. Integrating the metagenome, metatranscriptome, and metabolome (i.e., tri-omics) makes it possible to link gene abundance and expression with the biotransformation of the contaminant and the formation of metabolites from this biotransformation. In this study, we used this tri-omics approach to study the biotransformation pathways for cetyltrimethylammonium bromide (CTAB) under aerobic conditions. The tri-omics analysis showed that CTAB undergoes three parallel first-step mono-/di-oxygenations (to the α, ß, and ω-carbons); intermediate metabolites and expressed enzymes were identified for all three pathways, and the ß-carbon mono-/di-oxygenation is a novel pathway; and the genes related to CTAB biodegradation were associated with Pseudomonas spp. Four metabolites - palmitic acid, trimethylamine N-oxide (TMAO), myristic acid, and betaine - were the key identified biodegradation intermediates of CTAB, and they were associated with first-step mono-/di-oxygenations at the α/ß-C. This tri-omics approach with CTAB demonstrates its power for identifying promising paths for future research on the biodegradation of complex organics by microbial communities.

Phenotypic and Transcriptional Responses of Pseudomonas aeruginosa Biofilms to UV-C Irradiation via Side-Emitting Optical Fibers: Implications for Biofouling Control.

Biofilms give rise to a range of issues, spanning from harboring pathogens to accelerating microbial-induced corrosion in pressurized water systems. Introducing germicidal UV-C (200-280 nm) irradiation from light-emitting diodes (LEDs) into flexible side-emitting optical fibers (SEOFs) presents a novel light delivery method to inhibit the accumulation of biofilms on surfaces found in small-diameter tubing or other intricate geometries. This work used surfaces fully submerged in flowing water that contained Pseudomonas aeruginosa, an opportunistic pathogen commonly found in water system biofilms. A SEOF delivered a UV-C gradient to the surface for biofilm inhibition. Biofilm growth over time was monitored in situ using optical conference tomography. Biofilm formation was effectively inhibited when the 275 nm UV-C irradiance was ≥8 µW/cm2. Biofilm samples were collected from several regions on the surface, representing low and high UV-C irradiance. RNA sequencing of these samples revealed that high UV-C irradiance inhibited the expression of functional genes related to energy metabolism, DNA repair, quorum sensing, polysaccharide production, and mobility. However, insufficient sublethal UV-C exposure led to upregulation genes for SOS response and quorum sensing as survival strategies against the UV-C stress. These results underscore the need to maintain minimum UV-C exposure on surfaces to effectively inhibit biofilm formation in water systems.

Co-metabolic biodegradation of chlorinated ethene in an oxygen- and ethane-based membrane biofilm reactor.

Groundwater contamination by chlorinated ethenes is an urgent concern worldwide. One approach for detoxifying chlorinated ethenes is aerobic co-metabilims using ethane (C2H6) as the primary substrate. This study evaluated long-term continuous biodegradation of three chlorinated alkenes in a membrane biofilm reactor (MBfR) that delivered C2H6 and O2 via gas-transfer membranes. During 133 days of continuous operation, removals of dichloroethane (DCE), trichloroethene (TCE), and tetrachloroethene (PCE) were as high as 94 % and with effluent concentrations below 5 µM. In situ batch tests showed that the co-metabolic kinetics were faster with more chlorination. C2H6-oxidizing Comamonadaceae and "others," such as Methylococcaceae, oxidized C2H6 via monooxyenation reactions. The abundant non-ethane monooxygenases, particularly propane monooxygenase, appears to have been responsible for C2H6 aerobic metabolism and co-metabolism of chlorinated ethenes. This work proves that the C2H6 + O2 MBfR is a platform for ex-situ bioremediation of chlorinated ethenes, and the generalized action of the monooxygenases may make it applicable for other chlorinated organic contaminants.

The structure of biodegradable surfactants shaped the microbial community, antimicrobial resistance, and potential for horizontal gene transfer.

While most household surfactants are biodegradable in aerobic conditions, their biodegradability may obscure their environmental risks. The presence of surfactants in a biological treatment process can lead to the proliferation of antimicrobial-resistance genes (ARG) in the biomass. Surfactants can be cationic, anionic, or zwitterionic, and these different classes may have different effects on the proliferation ARG. Cationic hexadecyltrimethyl-ammonium (CTAB), anionic sodium dodecyl sulfate (SDS), and zwitterionic 3-(decyldimethylammonio)-propanesulfonate inner salt (DAPS) were used to represent the three classes of surfactants in domestic household clean-up products. This study focused on the removal of these surfactants by the O2-based Membrane Biofilm Reactor (O2-MBfR) for hotspot scenarios (∼1 mM) and how the three classes of surfactants affected the microbial community's structure and ARG. Given sufficient O2 delivery, the MBfR provided at least 98% surfactant removal. The presence and biodegradation for each surfactant uniquely shaped the biofilms' microbial communities and the presence of ARG. CTAB had by far the strongest impact and the higher ARG abundance. In particular, Pseudomonas and Stenotrophomonas, the two main genera in the biofilm treating CTAB, were highly correlated to the abundance of ARG for efflux pumps and antibiotic inactivation. CTAB also led to more functional genes relevant to the Type-IV secretion system and protection against oxidative stress, which also could encourage horizontal gene transfer. Our findings highlight that the biodegradation of quaternary ammonium surfactants, while beneficial, can pose public health concerns from its ability to promote the proliferation of ARG.

A synergistic platform enables co-oxidation of halogenated organic pollutants without input of organic primary substrate.

While co-oxidation is widely used to biodegrade halogenated organic pollutants (HOPs), a considerable amount of organic primary substrate is required. Adding organic primary substrates increases the operating cost and also leads to extra carbon dioxide release. In this study, we evaluated a two-stage Reduction and Oxidation Synergistic Platform (ROSP), which integrated catalytic reductive dehalogenation with biological co-oxidation for HOPs removal. The ROSP was a combination of an H2-based membrane catalytic-film reactor (H2-MCfR) and an O2-based membrane biofilm reactor (O2-MBfR). 4-chlorophenol (4-CP) was used as a model HOP to evaluate the performance of ROSP. In the MCfR stage, zero-valent palladium nanoparticles (Pd0NPs) catalyzed reductive hydrodechlorination that converted 4-CP to phenol, with a conversion yield over 92%. In the MBfR stage, the phenol was oxidized and used as a primary substrate that supported the co-oxidation of residual 4-CP. Genomic DNA sequencing revealed that phenol produced from 4-CP reduction enriched bacteria having genes for functional enzymes for phenol biodegradation in the biofilm community. In the ROSP, over 99% of 60 mg/L 4-CP was removed and mineralized during continuous operation: Effluent 4-CP and chemical oxygen demand concentrations were below 0.1 and 3 mg/L, respectively. H2 was the only added electron donor to the ROSP, which means no extra carbon dioxide was produced by primary-substrate oxidation.

Coremoval of Energetics and Oxyanions via the In Situ Coupling of Catalytic and Enzymatic Destructions: A Solution to Ammunition Wastewater Treatment.

Ammunition wastewater contains toxic nitrated explosives like RDX and oxyanions like nitrate and perchlorate. Its treatment is challenged by low efficiency due to contaminant recalcitrance and high cost due to multiple processes needed for separately removing different contaminant types. This paper reports a H2-based low-energy strategy featuring the treatment of explosives via catalytic denitration followed by microbial mineralization coupled with oxyanion reduction. After a nitrate- and perchlorate-reducing biofilm incapable of RDX biodegradation was coated with palladium nanoparticles (Pd0NPs), RDX was rapidly denitrated with a specific catalytic activity of 8.7 gcat-1 min-1, while biological reductions of nitrate and perchlorate remained efficient. In the subsequent 30-day continuous test, >99% of RDX, nitrate, and perchlorate were coremoved, and their effluent concentrations were below their respective regulation levels. Detected intermediates and shallow metagenome analysis suggest that the intermediates after Pd-catalytic denitration of RDX ultimately were enzymatically utilized by the nitrate- and perchlorate-reducing bacteria as additional electron donor sources.

Reductive Dehalogenation of Herbicides Catalyzed by Pd0NPs in a H2-Based Membrane Catalyst-Film Reactor.

More food production required to feed humans will require intensive use of herbicides to protect against weeds. The widespread application and persistence of herbicides pose environmental risks for nontarget species. Elemental-palladium nanoparticles (Pd0NPs) are known to catalyze reductive dehalogenation of halogenated organic pollutants. In this study, the reductive conversion of 2,4-dichlorophenoxyacetic acid (2,4-D) was evaluated in a H2-based membrane catalyst-film reactor (H2-MCfR), in which Pd0NPs were in situ-synthesized as the catalyst film and used to activate H2 on the surface of H2-delivery membranes. Batch kinetic experiments showed that 99% of 2,4-D was removed and converted to phenoxyacetic acid (POA) within 90 min with a Pd0 surface loading of 20 mg Pd/m2, achieving a catalyst specific activity of 6.6 ± 0.5 L/g-Pd-min. Continuous operation of the H2-MCfR loaded with 20 mg Pd/m2 sustained >99% removal of 50 µM 2,4-D for 20 days. A higher Pd0 surface loading, 1030 mg Pd/m2, also enabled hydrosaturation and hydrolysis of POA to cyclohexanone and glycolic acid. Density functional theory identified the reaction mechanisms and pathways, which involved reductive hydrodechlorination, hydrosaturation, and hydrolysis. Molecular electrostatic potential calculations and Fukui indices suggested that reductive dehalogenation could increase the bioavailability of herbicides. Furthermore, three other halogenated herbicides─atrazine, dicamba, and bromoxynil─were reductively dehalogenated in the H2-MCfR. This study documents a promising method for the removal and detoxification of halogenated herbicides in aqueous environments.

Hydrodehalogenation of Trichlorofluoromethane over Biogenic Palladium Nanoparticles in Ambient Conditions.

Among a number of persistent chlorofluorocarbons (CFCs, or freons), the emissions of trichlorofluoromethane (CFCl3, CFC-11) have been increasing since 2002. Zero-valent-Pd (Pd0) catalysts are known to hydrodehalogenate CFCs; however, most studies rely on cost-inefficient and eco-unfriendly chemical synthesis of Pd0NPs and harsh reaction conditions. In this study, we synthesized Pd0 nanoparticles (Pd0NPs) using D. vulgaris biomass as the support and evaluated hydrodehalogenation of CFC-11 catalyzed by the biogenic Pd0NPs. The presence of D. vulgaris biomass stabilized and dispersed 3-6 nm Pd0NPs that were highly active. We documented, for the first time, Pd0-catalyzed simultaneous hydrodechlorination and hydrodefluorination of CFC-11 at ambient conditions (room temperature and 1 atm). More than 70% CFC-11 removal was achieved within 15 h with a catalytic activity of 1.5 L/g-Pd/h, dechlorination was 50%, defluorination was 41%, and selectivity to fully dehalogenated methane was >30%. The reaction pathway had a mixture of parallel and sequential hydrodehalogenation. In particular, hydrodefluorination was favored by higher H2 availability and Pd0:CFC-11 ratio. This study offers a promising strategy for efficient and sustainable treatment of freon-contaminated water.

Wastewater treatment for ships experiencing large temperature changes： the activated sludge/membrane-biofilm reactor.

A particular challenge to treatment systems for ship wastewater comes from low and variable temperatures. We evaluated the temperature response (35-15 °C) of a novel biological treatment system involving activated sludge followed by a membrane-biofilm reactor: the activated sludge/membrane-biofilm reactor (AS-ABfMemR). In this study, a pilot-scale AS-ABfMemR achieved over 96% chemical oxygen demand (COD) and 94% total nitrogen (TN) removal from a ship wastewater (550-960 mgCOD·L-1 and 52-77 mgTN·L-1) with a continuous operation with a hydraulic retention time of 12 h at 25 °C. The effluent COD and TN concentrations met IMO discharge standards at temperatures as low as 17 °C, which reduced the energy consumption for wastewater heating. The COD and TN removals of the biofilm stage became important (up to 34% and 35%, respectively) at low temperatures, and this compensated for the deterioration in performance of the aerobic sludge. The genus Azospira dominated in the biofilm's denitrification removal for TN at low temperature. In addition, the buildup of trans-membrane pressure was so slow that backwashing was not needed over the 90 days of continuous operation. These conclusions indicate that the pilot-scale AS-ABfMemR technology is an effective way for real ship sewage treatment under temperature variations.

Palladium (Pd0) Loading-Controlled Catalytic Activity and Selectivity for Chlorophenol Hydrodechlorination and Hydrosaturation.

Reductive catalysis by zero-valent palladium nanoparticles (Pd0NPs) has emerged as an efficient strategy for promoting the detoxification of chlorophenols (CPs) via hydrogenation. Most studies achieved hydrodechlorination of CP to phenol for detoxification, but it requires considerably high energy input and harsh conditions to further hydrosaturate phenol to cyclohexanone (CHN) as the most desired product for resource recovery. This study documented 4-CP hydrodechlorination and hydrosaturation catalyzed by Pd0NPs deposited on H2-transfer membranes in the H2-based membrane catalyst-film reactor, which yielded up to 99% CHN selectivity under ambient conditions. It was further discovered that the Pd0 morphology and size, both determined by Pd0 loading, were the key factors controlling the catalytic activity and selectivity: while sub-nano Pd particles catalyzed only 4-CP hydrodechlorination, Pd0NPs were able to catalyze the subsequent hydrosaturation that requires more Pd0 reactive sites than hydrodechlorination. In addition, better dispersion of Pd0, caused by lower Pd0 loading, yielded higher activity for hydrodechlorination but lower activity for hydrosaturation. During the 15 day continuous tests, the substantial product from 4-CP hydrogenation was constantly phenol (>98%) for 0.2 g-Pd/m2 and CHN (>92%) for 1.0 g-Pd/m2. This study opens the door for selectively manipulating desired products from Pd0-catalyzed CP hydrogenation under ambient conditions.

Reductive destruction of multiple nitrated energetics over palladium nanoparticles in the H2-based membrane catalyst-film reactor (MCfR).

Nitrated energetics are widespread contaminants due to their improper disposal from ammunition facilities. Different classes of nitrated energetics commonly co-exist in ammunition wastewater, but co-removal of the classes has hardly been documented. In this study, we evaluated the catalytic destruction of three types of energetics using palladium (Pd0) nano-catalysts deposited on H2-transfer membranes in membrane catalyst-film reactors (MCfRs). This work documented nitro-reduction of 2,4,6-trinitrotoluene (TNT), as well as, for the first time, denitration of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and pentaerythritol tetranitrate (PETN) over Pd0 at ambient temperature. The catalyst-specific activity was 20- to 90-fold higher than reported for other catalyst systems. Nitrite (NO2-) released from RDX and PETN also was catalytically reduced to dinitrogen gas (N2). Continuous treatment of a synthetic wastewater containing TNT, RDX, and PETN (5 mg/L each) for more than 20 hydraulic retention times yielded removals higher than 96% for all three energetics. Furthermore, the concentrations of NO2- and NH4+ were below the detection limit due to subsequent NO2- reduction with > 99% selectivity to N2. Thus, the MCfR provides a promising strategy for sustainable catalytic removal of co-existing energetics in ammunition wastewater.

Hydrodefluorination of Perfluorooctanoic Acid in the H2-Based Membrane Catalyst-Film Reactor with Platinum Group Metal Nanoparticles: Pathways and Optimal Conditions.

PFAAs (perfluorinated alkyl acids) have become a concern because of their widespread pollution and persistence. A previous study introduced a novel approach for removing and hydrodefluorinating perfluorooctanoic acid (PFOA) using palladium nanoparticles (Pd0NPs) in situ synthesized on H2-gas-transfer membranes. This work focuses on the products, pathways, and optimal catalyst conditions. Kinetic tests tracking PFOA removal, F- release, and hydrodefluorination intermediates documented that PFOA was hydrodefluorinated by a mixture of parallel and stepwise reactions on the Pd0NP surfaces. Slow desorption of defluorination products lowered the catalyst's activity for hydrodefluorination. Of the platinum group metals studied, Pd was overall superior to Pt, Rh, and Ru for hydrodefluorinating PFOA. pH had a strong influence on performance: PFOA was more strongly adsorbed at higher pH, but lower pH promoted defluorination. A membrane catalyst-film reactor (MCfR), containing an optimum loading of 1.2 g/m2 Pd0 for a total Pd amount of 22 mg, removed 3 mg/L PFOA during continuous flow for 90 days, and the removal flux was as high as 4 mg PFOA/m2/d at a steady state. The EPA health advisory level (70 ng/L) also was achieved over the 90 days with the influent PFOA at an environmentally relevant concentration of 500 ng/L. The results document a sustainable catalytic method for the detoxification of PFOA-contaminated water.

Adsorption and Reductive Defluorination of Perfluorooctanoic Acid over Palladium Nanoparticles.

Per- and polyfluoroalkyl substances (PFASs) comprise a group of widespread and recalcitrant contaminants that are attracting increasing concern due to their persistence and adverse health effects. This study evaluated removal of one of the most prevalent PFAS, perfluorooctanoic acid (PFOA), in H2-based membrane catalyst-film reactors (H2-MCfRs) coated with palladium nanoparticles (Pd0NPs). Batch tests documented that Pd0NPs catalyzed hydrodefluorination of PFOA to partially fluorinated and nonfluorinated octanoic acids; the first-order rate constant for PFOA removal was 0.030 h-1, and a maximum defluorination rate was 16 µM/h in our bench-scale MCfR. Continuous-flow tests achieved stable long-term depletion of PFOA to below the EPA health advisory level (70 ng/L) for up to 70 days without catalyst loss or deactivation. Two distinct mechanisms for Pd0-based PFOA removal were identified based on insights from experimental results and density functional theory (DFT) calculations: (1) nonreactive chemisorption of PFOA in a perpendicular orientation on empty metallic surface sites and (2) reactive defluorination promoted by physiosorption of PFOA in a parallel orientation above surface sites populated with activated hydrogen atoms (Hads*). Pd0-based catalytic reduction chemistry and continuous-flow treatment may be broadly applicable to the ambient-temperature destruction of other PFAS compounds.

A Synergistic Platform for Continuous Co-removal of 1,1,1-Trichloroethane, Trichloroethene, and 1,4-Dioxane via Catalytic Dechlorination Followed by Biodegradation.

Groundwater co-contaminated with 1,4-dioxane, 1,1,1-trichloroethane (TCA), and trichloroethene (TCE) is among the most urgent environmental concerns of the U.S. Department of Defense (DoD), U.S. Environmental Protection Agency (EPA), and industries related to chlorinated solvents. Inspired by the pressing need to remove all three contaminants at many sites, we tested a synergistic platform: catalytic reduction of 1,1,1-TCA and TCE to ethane in a H2-based membrane palladium-film reactor (H2-MPfR), followed by aerobic biodegradation of ethane and 1,4-dioxane in an O2-based membrane biofilm reactor (O2-MBfR). During 130 days of continuous operation, 1,1,1-TCA and TCE were 95-98% reductively dechlorinated to ethane in the H2-MPfR, and ethane served as the endogenous primary electron donor for promoting 98.5% aerobic biodegradation of 1,4-dioxane in the O2-MBfR. In addition, the small concentrations of the chlorinated intermediate from the H2-MPfR, dichloroethane (DCA) and monochloroethane (MCA), were fully biodegraded through aerobic biodegradation in the O2-MBfR. The biofilms in the O2-MBfR were enriched in phylotypes closely related to the genera Pseudonocardia known to biodegrade 1,4-dioxane.

H2-Based Membrane Catalyst-Film Reactor (H2-MCfR) Loaded with Palladium for Removing Oxidized Contaminants in Water.

Scalable applications of precious-metal catalysts for water treatment face obstacles in H2-transfer efficiency and catalyst stability during continuous operation. Here, we introduce a H2-based membrane catalyst-film reactor (H2-MCfR), which enables in situ reduction and immobilization of a film of heterogeneous Pd0 catalysts that are stably anchored on the exterior of a nonporous H2-transfer membrane under ambient conditions. In situ immobilization had >95% yield of Pd0 in controllable forms, from isolated single atoms to moderately agglomerated nanoparticles (averaging 3-4 nm). A series of batch tests documented rapid Pd-catalyzed reduction of a wide spectrum of oxyanions (nonmetal and metal) and organics (e.g., industrial raw materials, solvents, refrigerants, and explosives) at room temperature, owing to accurately controlled H2 supply on demand. Reduction kinetics and selectivity were readily controlled through the Pd0 loading on the membranes, H2 pressure, and pH. A 45-day continuous treatment of trichloroethene (TCE)-contaminated water documented removal fluxes up to 120 mg-TCE/m2/d with over 90% selectivity to ethane and minimal (<1.5%) catalyst leaching or deactivation. The results support that the H2-MCfR is a potentially sustainable and reliable catalytic platform for reducing oxidized water contaminants: simple synthesis of an active and versatile catalyst that has long-term stability during continuous operation.

Para-Chlorophenol (4-CP) Removal by a Palladium-Coated Biofilm: Coupling Catalytic Dechlorination and Microbial Mineralization via Denitrification.

Rapid dechlorination and full mineralization of para-chlorophenol (4-CP), a toxic contaminant, are unfulfilled goals in water treatment. Means to achieve both goals stem from the novel concept of coupling catalysis by palladium nanoparticles (PdNPs) with biodegradation in a biofilm. Here, we demonstrate that a synergistic version of the hydrogen (H2)-based membrane biofilm reactor (MBfR) enabled simultaneous removals of 4-CP and cocontaminating nitrate. In situ generation of PdNPs within the MBfR biofilm led to rapid 4-CP reductive dechlorination, with >90% selectivity to more bioavailable cyclohexanone. Then, the biofilm mineralized the cyclohexanone by utilizing it as a supplementary electron donor to accelerate nitrate reduction. Long-term operation of the Pd-MBfR enriched the microbial community in cyclohexanone degraders within Clostridium, Chryseobacterium, and Brachymonas. In addition, the PdNP played an important role in accelerating nitrite reduction; while NO3- reduction to NO2- was entirely accomplished by bacteria, NO2- reduction to N2 was catalyzed by PdNPs and bacterial reductases. This study documents a promising option for efficient and complete remediation of halogenated organics and nitrate by the combined action of PdNP and bacterial catalysis.

Increased expression of antibiotic-resistance genes in biofilm communities upon exposure to cetyltrimethylammonium bromide (CTAB) and other stress conditions.

Quaternary ammonium compounds (QAC, e.g., cetyltrimethylammonium bromide, (CTAB)) are widely used as surfactants and disinfectants. QAC already are commonly found in wastewaters, and their concentration could increase, since QAC are recommended to inactivate the SARS-CoV-2 (COVID-19) virus. Exposure of bacteria to QAC can lead to proliferation of antibiotic resistance genes (ARG). In particular, O2-based membrane biofilm reactors (O2-MBfRs) achieved excellent CTAB biodegradation, but ARG increased in their biofilms. Here, we applied meta-transcriptomic analyses to assess the impacts of CTAB exposure and operating conditions on microbial community's composition and ARG expression in the O2-MBfRs. Two opportunistic pathogens, Pseudomonas aeruginosa and Stenotrophomonas maltophilia, dominated the microbial communities and were associated with the presence of ARG. Operating conditions that imposed stress on the biofilms, i.e., limited supplies of O2 and nitrogen or a high loading of CTAB, led to large increases in ARG expression, particularly for genes conferring antibiotic-target protection. Important within the efflux pumps was the Resistance-Nodulation-Division (RND) family, which may have been active in exporting CTAB from cells. Oxidative stress appeared to be the key factor that triggered ARG proliferation by selecting intrinsically resistant species and accentuating the expression of ARG. Our findings suggest that means to mitigate the spread of ARG, such as shown here in a O2-based membrane biofilm reactor, need to consider the impacts of stressors, including QAC exposure and stressful operating conditions.

Stable dechlorination of Trichloroacetic Acid (TCAA) to acetic acid catalyzed by palladium nanoparticles deposited on H2-transfer membranes.

Trichloroacetic acid (TCAA) is a common disinfection byproduct (DBP) produced during chlorine disinfection. With the outbreak of the Coronavirus Disease 2019 (COVID-19) pandemic, the use of chlorine disinfection has increased, raising the already substantial risks of DBP exposure. While a number of methods are able to remove TCAA, their application for continuous treatment is limited due to their complexity and expensive or hazardous inputs. We investigated a novel system that employs palladium (Pd0) nanoparticles (PdNPs) for catalytic reductive dechlorination of TCAA. H2 was delivered directly to PdNPs in situ coated on the surface of bubble-free hollow-fiber gas-transfer membranes. The H2-based membrane Pd film reactor (H2-MPfR) achieved a high catalyst-specific TCAA reduction rate, 32 L/g-Pd/min, a value similar to the rate of using homogeneously suspended PdNP, but orders of magnitude higher than with other immobilized PdNP systems. In batch tests, over 99% removal of 1 mM TCAA was achieved in 180 min with strong product selectivity (≥ 93%) to acetic acid. During 50 days of continuous operation, over 99% of 1 mg/L influent TCAA was removed, again with acetic acid as the major product (≥ 94%). We identified the reaction pathways and their kinetics for TCAA reductive dechlorination with PdNPs using direct delivery of H2. Sustained continuous TCAA removal, high selectivity to acetic acid, and minimal loss of PdNPs support that the H2-MPfR is a promising catalytic reactor to remove chlorinated DBPs in practice.