Mass Flow and Metabolic Pathway of Nonaeration Greywater Treatment in an Oxygenic Microalgal-Bacterial Biofilm.

A symbiotic microalgal-bacterial biofilm can enable efficient carbon (C) and nitrogen (N) removal during aeration-free wastewater treatment. However, the contributions of microalgae and bacteria to C and N removal remain unexplored. Here, we developed a baffled oxygenic microalgal-bacterial biofilm reactor (MBBfR) for the nonaerated treatment of greywater. A hydraulic retention time (HRT) of 6 h gave the highest biomass concentration and biofilm thickness as well as the maximum removal of chemical oxygen demand (94.8%), linear alkylbenzenesulfonates (LAS, 99.7%), and total nitrogen (97.4%). An HRT of 4 h caused a decline in all of the performance metrics due to LAS biotoxicity. Most of C (92.6%) and N (95.7%) removals were ultimately associated with newly synthesized biomass, with only minor fractions transformed into CO2 (2.2%) and N2 (1.7%) on the function of multifarious-related enzymes in the symbiotic biofilm. Specifically, microalgae photosynthesis contributed to the removal of C and N at 75.3 and 79.0%, respectively, which accounted for 17.3% (C) and 16.7% (N) by bacteria assimilation. Oxygen produced by microalgae favored the efficient organics mineralization and CO2 supply by bacteria. The symbiotic biofilm system achieved stable and efficient removal of C and N during greywater treatment, thus providing a novel technology to achieve low-energy-input wastewater treatment, reuse, and resource recovery.

Co-Removal of Perfluorooctanoic Acid and Nitrate from Water by Coupling Pd Catalysis with Enzymatic Biotransformation.

PFAS (poly- and per-fluorinated alkyl substances) represent a large family of recalcitrant organic compounds that are widely used and pose serious threats to human and ecosystem health. Here, palladium (Pd0)-catalyzed defluorination and microbiological mineralization were combined in a denitrifying H2-based membrane biofilm reactor to remove co-occurring perfluorooctanoic acid (PFOA) and nitrate. The combined process, i.e., Pd-biofilm, enabled continuous removal of ∼4 mmol/L nitrate and ∼1 mg/L PFOA, with 81% defluorination of PFOA. Metagenome analysis identified bacteria likely responsible for biodegradation of partially defluorinated PFOA: Dechloromonas sp. CZR5, Kaistella koreensis, Ochrobacterum anthropic, and Azospira sp. I13. High-performance liquid chromatography-quadrupole time-of-flight mass spectrometry and metagenome analyses revealed that the presence of nitrate promoted microbiological oxidation of partially defluorinated PFOA. Taken together, the results point to PFOA-oxidation pathways that began with PFOA adsorption to Pd0, which enabled catalytic generation of partially or fully defluorinated fatty acids and stepwise oxidation and defluorination by the bacteria. This study documents how combining catalysis and microbiological transformation enables the simultaneous removal of PFOA and nitrate.

Achieving Long-Term Stability of Partial Nitrification and Autotrophic Denitrification in an MABR via Sulfide Dosing.

While partial nitrification (PN) has the potential to reduce energy for aeration, it has proven to be unstable when treating low-strength wastewater. This study introduces an innovative combined strategy incorporating a low rate of oxygen supply, pH control, and sulfide addition to selectively inhibit nitrite-oxidizing bacteria (NOB). This strategy led to a stable PN in a laboratory-scale membrane aerated biofilm reactor (MABR). Over a period of 260 days, the nitrite accumulation ratio exceeded 60% when treating synthetic sewage containing 50 mg NH4+-N/L. Through in situ activity testing and high-throughput sequencing, the combined strategy led to low levels of nitrite-oxidation activity (<5.5 mg N/m2 h), Nitrospira species (relative abundance <1%), and transcription of nitrite-oxidation genes (undetectable). The addition of sulfide led to simultaneous PN and autotrophic denitrification in the single-stage MABR, resulting in over 60% total inorganic nitrogen removal. Sulfur-based autotrophic denitrification consumed nitrite and inhibited NOB conversion of nitrite to nitrate. The combined strategy has potential to be applied in large-scale sewage treatment and deserves further exploration.

Method of H2 Transfer Is Vital for Catalytic Hydrodefluorination of Perfluorooctanoic Acid (PFOA).

The efficient transfer of H2 plays a critical role in catalytic hydrogenation, particularly for the removal of recalcitrant contaminants from water. One of the most persistent contaminants, perfluorooctanoic acid (PFOA), was used to investigate how the method of H2 transfer affected the catalytic hydrodefluorination ability of elemental palladium nanoparticles (Pd0NPs). Pd0NPs were synthesized through an in situ autocatalytic reduction of Pd2+ driven by H2 from the membrane. The Pd0 nanoparticles were directly deposited onto the membrane fibers to form the catalyst film. Direct delivery of H2 to Pd0NPs through the walls of nonporous gas transfer membranes enhanced the hydrodefluorination of PFOA, compared to delivering H2 through the headspace. A higher H2 lumen pressure (20 vs 5 psig) also significantly increased the defluorination rate, although 5 psig H2 flux was sufficient for full reductive defluorination of PFOA. Calculations made using density functional theory (DFT) suggest that subsurface hydrogen delivered directly from the membrane increases and accelerates hydrodefluorination by creating a higher coverage of reactive hydrogen species on the Pd0NP catalyst compared to H2 delivery through the headspace. This study documents the crucial role of the H2 transfer method in the catalytic hydrogenation of PFOA and provides mechanistic insights into how membrane delivery accelerates hydrodefluorination.

Biogenic Palladium Improved Perchlorate Reduction during Nitrate Co-Reduction by Diverting Electron Flow in a Hydrogenotrophic Biofilm.

Microbial reduction of perchlorate (ClO4-) is emerging as a cost-effective strategy for groundwater remediation. However, the effectiveness of perchlorate reduction can be suppressed by the common co-contamination of nitrate (NO3-). We propose a means to overcome the limitation of ClO4- reduction: depositing palladium nanoparticles (Pd0NPs) within the matrix of a hydrogenotrophic biofilm. Two H2-based membrane biofilm reactors (MBfRs) were operated in parallel in long-term continuous and batch modes: one system had only a biofilm (bio-MBfR), while the other incorporated biogenic Pd0NPs in the biofilm matrix (bioPd-MBfR). For long-term co-reduction, bioPd-MBfR had a distinct advantage of oxyanion reduction fluxes, and it particularly alleviated the competitive advantage of NO3- reduction over ClO4- reduction. Batch tests also demonstrated that bioPd-MBfR gave more rapid reduction rates for ClO4- and ClO3- compared to those of bio-MBfR. Both biofilm communities were dominated by bacteria known to be perchlorate and nitrate reducers. Functional-gene abundances reflecting the intracellular electron flow from H2 to NADH to the reductases were supplanted by extracellular electron flow with the addition of Pd0NPs.

Efficient CO2 Conversion through a Novel Dual-Fiber Reactor System.

Carbon dioxide (CO2) can be converted to valuable organic chemicals using light irradiation and photocatalysis. Today, light-energy loss, poor conversion efficiency, and low quantum efficiency (QE) hamper the application of photocatalytic CO2 reduction. To overcome these drawbacks, we developed an efficient photocatalytic reactor platform for producing formic acid (HCOOH) by coating an iron-based metal-organic framework (Fe-MOF) onto side-emitting polymeric optical fibers (POFs) and using hollow-fiber membranes (HFMs) to deliver bubble-free CO2. The photocatalyst, Fe-MOF with amine-group (-NH2) decoration, provided exceptional dissolved inorganic carbon (DIC) absorption. The dual-fiber system gave a CO2-to-HCOOH conversion rate of 116 ± 1.2 mM h-1 g-1, which is ≥18-fold higher than the rates in photocatalytic slurry systems. The 12% QE obtained using the POF was 18-fold greater than the QE obtained by a photocatalytic slurry. The conversion efficiency and product selectivity of CO2-to-HCOOH were up to 22 and 99%, respectively. Due to the dual efficiencies of bubble-free CO2 delivery and the high QE achieved using the POF platform, the dual-fiber system had energy consumption of only 0.60 ± 0.05 kWh mol-1, 3000-fold better than photocatalysis using slurry-based systems. This innovative dual-fiber design enables efficient CO2 valorization without the use of platinum group metals or rare earth elements.

Core taxa, co-occurrence pattern, diversity, and metabolic pathways contributing to robust anaerobic biodegradation of chlorophenol.

It is hard to achieve robustness in anaerobic biodegradation of trichlorophenol (TCP). We hypothesized that specific combinations of environmental factors determine phylogenetic diversity and play important roles in the decomposition and stability of TCP-biodegrading bacteria. The anaerobic bioreactor was operated at 35 °C (H condition) or 30 °C (L condition) and mainly fed with TCP (from 28 µM to 180 µM) and organic material. Metagenome sequencing was combined with 16S rRNA gene amplicon sequencing for the microbial community analysis. The results exhibited that the property of robustness occurred in specific conditions. The corresponding co-occurrence and diversity patterns suggest high collectivization, degree and evenness for robust communities. Two types of core functional taxa were recognized: dechlorinators (unclassified Anaerolineae, Thermanaerothrix and Desulfovibrio) and ring-opening members (unclassified Proteobacteria, Methanosarcina, Methanoperedens, and Rubrobacter). The deterministic process of the expansion of niche of syntrophic bacteria at higher temperatures was confirmed. The reductive and hydrolytic dechlorination mechanisms jointly lead to C-Cl bond cleavage. H ultimately adapted to the stress of high TCP loading, with more abundant ring-opening enzyme (EC 3.1.1.45, ∼55%) and hydrolytic dechlorinase (EC 3.8.1.5, 26.5%) genes than L (∼47%, 10.5%). The functional structure (based on KEGG) in H was highly stable despite the high loading of TCP (up to 60 µM), but not in L. Furthermore, an unknown taxon with multiple functions (dechlorinating and ring-opening) was found based on genetic sequencing; its functional contribution of EC 3.8.1.5 in H (26.5%) was higher than that in L (10.5%), and it possessed a new metabolic pathway for biodegradation of halogenated aromatic compounds. This new finding is supplementary to the robust mechanisms underlying organic chlorine biodegradation, which can be used to support the engineering, regulation, and design of synthetic microbiomes.

'Dark' CO2 fixation in succinate fermentations enabled by direct CO2 delivery via hollow fiber membrane carbonation.

Anaerobic succinate fermentations can achieve high-titer, high-yield performance while fixing CO2 through the reductive branch of the tricarboxylic acid cycle. To provide the needed CO2, conventional media is supplemented with significant (up to 60 g/L) bicarbonate (HCO3-), and/or carbonate (CO32-) salts. However, producing these salts from CO2 and natural ores is thermodynamically unfavorable and, thus, energetically costly, which reduces the overall sustainability of the process. Here, a series of composite hollow fiber membranes (HFMs) were first fabricated, after which comprehensive CO2 mass transfer measurements were performed under cell-free conditions using a novel, constant-pH method. Lumen pressure and total HFM surface area were found to be linearly correlated with the flux and volumetric rate of CO2 delivery, respectively. Novel HFM bioreactors were then constructed and used to comprehensively investigate the effects of modulating the CO2 delivery rate on succinate fermentations by engineered Escherichia coli. Through appropriate tuning of the design and operating conditions, it was ultimately possible to produce up to 64.5 g/L succinate at a glucose yield of 0.68 g/g; performance approaching that of control fermentations with directly added HCO3-/CO32- salts and on par with prior studies. HFMs were further found to demonstrate a high potential for repeated reuse. Overall, HFM-based CO2 delivery represents a viable alternative to the addition of HCO3-/CO32- salts to succinate fermentations, and likely other 'dark' CO2-fixing fermentations.

Microbiological hydrogen (H2 ) thresholds in anaerobic continuous-flow systems: Effects of system characteristics.

Hydrogen (H2 ) concentrations that were associated with microbiological respiratory processes (RPs) such as sulfate reduction and methanogenesis were quantified in continuous-flow systems (CFSs) (e.g., bioreactors, sediments). Gibbs free energy yield (ΔÇ´ ~ 0) of the relevant RP has been proposed to control the observed H2 concentrations, but most of the reported values do not align with the proposed energetic trends. Alternatively, we postulate that system characteristics of each experimental design influence all system components including H2 concentrations. To analyze this proposal, a Monod-based mathematical model was developed and used to design a gas-liquid bioreactor for hydrogenotrophic methanogenesis with Methanobacterium bryantii M.o.H. Gas-to-liquid H2 mass transfer, microbiological H2 consumption, biomass growth, methane formation, and Gibbs free energy yields were evaluated systematically. Combining model predictions and experimental results revealed that an initially large biomass concentration created transients during which biomass consumed [H2 ]L rapidly to the thermodynamic H2 -threshold (≤1 nM) that triggerred the microorganisms to stop H2 oxidation. With no H2 oxidation, continuous gas-to-liquid H2 transfer increased [H2 ]L to a level that signaled the methanogens to resume H2 oxidation. Thus, an oscillatory H2 -concentration profile developed between the thermodynamic H2 -threshold (≤1 nM) and a low [H2 ]L (~10 nM) that relied on the rate of gas-to-liquid H2 -transfer. The transient [H2 ]L values were too low to support biomass synthesis that could balance biomass losses through endogenous oxidation and advection; thus, biomass declined continuously and disappeared. A stable [H2 ]L (1807 nM) emerged as a result of abiotic H2 -balance between gas-to-liquid H2 transfer and H2 removal via advection of liquid-phase.

Reduction of Chromate via Biotic and Abiotic Pathways in the Presence of Three Co-contaminating Electron Acceptors.

Bioreduction of Cr(VI) to Cr(III) is a promising technology for removing Cr(VI), but Cr(VI) reduction alone cannot support microbial growth. This study investigated the reduction of Cr(VI) in the presence of three electron acceptors that typically coexist with Cr(VI): NO3-, SO42-, and Fe(III). All three systems could reduce Cr(VI) to Cr(III), but the fate of Cr, its impacts on reduction of the other acceptors, and its impact on the microbial community differed. Although Cr(VI) was continuously removed in the NO3--reduction systems, batch tests showed that denitrification was inhibited primarily through impeding nitrite reduction. The SO42- and Fe(III) reduction systems reduced Cr(VI) using a combination of biotic and abiotic processes. Across all three systems, the abundance of genera capable of reducing Cr(VI) increased following the introduction of Cr(VI). Conversely, the abundance of genera that cannot reduce or resist Cr(VI) decreased, leading to restructuring of the microbial community. Furthermore, the abundance of sulfide oxidizers and Fe(II) oxidizers substantially increased after the introduction of chromate. This study provides fundamental knowledge about how Cr(VI) bioreduction interacts with bioreductions of three other co-contaminating electron acceptors.

Novel Sulfate Reduction Coupled to Simultaneous Nitrification and Autotrophic Denitrification Process for Removing Nitrogen and Organics from Saline Wastewater.

Highly efficient sulfate reduction coupled to autotrophic denitrification plus nitrification is demonstrated by integrating an anaerobic membrane bioreactor (AnMBR) with a membrane aerated biofilm reactor (MABR). Concurrent chemical oxygen demand (COD) removal and sulfate reduction were accomplished in the AnMBR, while simultaneous nitrification and autotrophic denitrification were carried out in the MABR. Separate operation of the MABR achieved >90% total nitrogen (TN) removal when the N/S ratio was controlled at 0.4 gN/gS. The integrated AnMBR-MABR system efficiently resisted influent variability, realizing >95% COD removal in the AnMBR and >75% TN removal in the MABR when the influent COD/N ratio was above 4 gCOD/gN. Membrane fouling did not happen during ∼170 days of operation. Due to sulfide oxidation, a large amount of elemental sulfur (S0) accumulated in the MABR biofilm, where it served as an electron donor for denitrification. Microbial community analysis indicated that Nitrospira and Thiobacillus played key roles in nitrification and sulfide-driven denitrification, respectively, and that they occurred in different layers of the biofilm. This novel process offers advantages of a small land-area footprint, modular operation, and high efficiency electron-donor and oxygen utilizations, particularly for wastewater with a low COD/N ratio.

Long-Term Continuous Test of H2-Induced Denitrification Catalyzed by Palladium Nanoparticles in a Biofilm Matrix.

Pd0 catalysis and microbially catalyzed reduction of nitrate (NO3--N) were combined as a strategy to increase the kinetics of NO3- reduction and control selectivity to N2 gas versus ammonium (NH4+). Two H2-based membrane biofilm reactors (MBfRs) were tested in continuous mode: one with a biofilm alone (H2-MBfR) and the other with biogenic Pd0 nanoparticles (Pd0NPs) deposited in the biofilm (Pd-H2-MBfR). Solid-state characterizations of Pd0NPs in Pd-H2-MBfR documented that the Pd0NPs were uniformly located along the outer surfaces of the bacteria in the biofilm. Pd-H2-MBfR had a higher rate of NO3- reduction compared to H2-MBfR, especially when the influent NO3- concentration was high (28 mg-N/L versus 14 mg-N/L). Pd-H2-MBfR enriched denitrifiers of Dechloromonas, Azospira, Pseudomonas, and Stenotrophomonas in the microbial community and also increased abundances of genes affiliated with NO3--N reductases, which reflected that the denitrifying bacteria could channel their respiratory electron flow to NO3- reduction to NO2-. N2 selectivity in Pd-H2-MBfR was regulated by the H2/NO3- flux ratio: 100% selectivity to N2 was achieved when the ratio was less than 1.3 e- equiv of H2/e- equiv N, while the selectivity toward NH4+ occurred with larger H2/NO3- flux ratios. Thus, the results with Pd-H2-MBfR revealed two advantages of it over the H2-MBfR: faster kinetics for NO3- removal and controllable selectivity toward N2 versus NH4+. By being able to regulate the H2/NO3- flux ratio, Pd-H2-MBfR has significant implications for improving the efficiency and effectiveness of the NO3- reduction processes, ultimately leading to more environmentally benign wastewater treatment.

Conductive Materials on Biocathodes Altered the Electron-Transfer Paths and Modulated γ-HCH Dechlorination and CH4 Production in Microbial Electrochemical Systems.

Adding conductive materials to the cathode of a microbial electrochemical system (MES) can alter the route of interspecies electron transfer and the kinetics of reduction reactions. We tested reductive dechlorination of γ-hexachlorocyclohexane (γ-HCH), along with CH4 production, in MES systems whose cathodes were coated with conductive magnetite nanoparticles (NaFe), biochar (BC), magnetic biochar (FeBC), or anti-conductive silica biochar (SiBC). Coating with NaFe enriched electroactive microorganisms, boosted electro-bioreduction, and accelerated γ-HCH dechlorination and CH4 production. In contrast, BC only accelerated dechlorination, while FeBC only accelerated methanogenesis, because of their assemblies of functional taxa that selectively transferred electrons to those electron sinks. SiBC, which decreased electro-bioreduction, yielded the highest CH4 production and increased methanogens and the mcrA gene. This study provides a strategy to selectively control the distribution of electrons between reductive dechlorination and methanogenesis by adding conductive or anti-conductive materials to the MES's cathode. If the goal is to maximize dechlorination and minimize methane generation, then BC is the optimal conductive material. If the goal is to accelerate electro-bioreduction, then the best addition is NaFe. If the goal is to increase the rate of methanogenesis, adding anti-conductive SiBC is the best.

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.

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.

Electrochemically Driven Photosynthetic Electron Transport in Cyanobacteria Lacking Photosystem II.

Light-activated photosystem II (PSII) carries out the critical step of splitting water in photosynthesis. However, PSII is susceptible to light-induced damage. Here, results are presented from a novel microbial electro-photosynthetic system (MEPS) that uses redox mediators in conjunction with an electrode to drive electron transport in live Synechocystis (ΔpsbB) cells lacking PSII. MEPS-generated, light-dependent current increased with light intensity up to 2050 µmol photons m-2 s-1, which yielded a delivery rate of 113 µmol electrons h-1 mg-chl-1 and an average current density of 150 A m-2 s-1 mg-chl-1. P700+ re-reduction kinetics demonstrated that initial rates exceeded wildtype PSII-driven electron delivery. The electron delivery occurs ahead of the cytochrome b6f complex to enable both NADPH and ATP production. This work demonstrates an electrochemical system that can drive photosynthetic electron transport, provides a platform for photosynthetic foundational studies, and has the potential for improving photosynthetic performance at high light intensities.

Dissimilatory and Cytoplasmic Antimonate Reductions in a Hydrogen-Based Membrane Biofilm Reactor.

A hydrogen-based membrane biofilm reactor (H2-MBfR) was operated to investigate the bioreduction of antimonate [Sb(V)] in terms of Sb(V) removal, the fate of Sb, and the pathways of reduction metabolism. The MBfR achieved up to 80% Sb(V) removal and an Sb(V) removal flux of 0.55 g/m2·day. Sb(V) was reduced to Sb(III), which mainly formed Sb2O3 precipitates in the biofilm matrix, although some Sb(III) was retained intracellularly. High Sb(V) loading caused stress that deteriorated performance that was not recovered when the high Sb(V) loading was removed. The biofilm community consisted of DSbRB (dissimilatory Sb-reduction bacteria), SbRB (Sb-resistant bacteria), and DIRB (dissimilatory iron-reducing bacteria). Dissimilatory antimonate reduction, mediated by the respiratory arsenate reductase ArrAB, was the main reduction route, but respiratory reduction coexisted with cytoplasmic Sb(V)-reduction mediated by arsenate reductase ArsC. Increasing Sb(V) loading caused stress that led to increases in the expression of arsC gene and intracellular accumulation of Sb(III). By illuminating the roles of the dissimilatory and cytoplasmic Sb(V) reduction mechanism in the biofilms of the H2-MBfR, this study reveals that the Sb(V) loading should be controlled to avoid stress that deteriorates Sb(V) reduction.

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.

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.

Thermodynamic Analysis of Intermediary Metabolic Steps and Nitrous Oxide Production by Ammonium-Oxidizing Bacteria.

Nitrous oxide (N2O) is a greenhouse gas emitted from wastewater treatment, soils, and agriculture largely by ammonium-oxidizing bacteria (AOB). While AOB are characterized by being aerobes that oxidize ammonium (NH4+) to nitrite (NO2-), fundamental studies in microbiology are revealing the importance of metabolic intermediates and reactions that can lead to the production of N2O. These findings about the metabolic pathways for AOB were integrated with thermodynamic electron-equivalents modeling (TEEM) to estimate kinetic and stoichiometric parameters for each of the AOB's nitrogen (N)-oxidation and -reduction reactions. The TEEM analysis shows that hydroxylamine (NH2OH) oxidation to nitroxyl (HNO) is the most energetically efficient means for the AOB to provide electrons for ammonium monooxygenation, while oxidations of HNO to nitric oxide (NO) and NO to NO2- are energetically favorable for respiration and biomass synthesis. The respiratory electron acceptor can be O2 or NO, and both have similar energetics. The TEEM-predicted value for biomass yield, maximum-specific rate of NH4+ utilization, and maximum specific growth rate are consistent with empirical observations. NO reduction to N2O is thermodynamically favorable for respiration and biomass synthesis, but the need for O2 as a reactant in ammonium monooxygenation likely precludes NO reduction to N2O from becoming the major pathway for respiration.