'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.

Water quality constraints H2O2 production in a dual-fiber photocatalytic reactor.

In-situ hydrogen peroxide (H2O2) finds applications in disinfection and oxidation processes. Photoproduction of H2O2 from water and oxygen, avoids reliance upon organic chemicals, and potentially enables smaller-sized or lower-cost reactors than electrochemical methods. In ultrapure water, we previously demonstrated a novel dual-fiber system coupling a light emitting diode (LED) with a metal-organic framework (MOF) catalyst-coated optical fiber (POF-MIL-101(Fe)) and O2-based hollow-membrane fibers and achieved a remarkable H2O2 yield, 308 ± 1.4 mM h-1 catalyst-g-1. To enable H2O2 production anywhere we sought to understand the impacts of common water quality parameters. The production of H2O2 was not affected by added sodium, potassium, hydroxide, sulfate or nitrate ions. There was consistent performance over a wide pH range (4-10), maintaining a high production rate of 232 ± 3.5 mM h-1 catalyst-g-1 even at pH 10, a condition typically unfavorable for H2O2 photoproduction. Chloride ions produced hypochlorous acid, consuming in-situ produced H2O2. Phosphate adsorption on the iron-based MOF catalysts blocked H2O2 production. Inorganic carbon species inhibited H2O2 production due to in-situ formic acid. Encouraging results were obtained using atmospheric water (i.e., condensate), with rates reaching 288 ± 6.1 mM h-1 catalyst-g-1, comparable to ultrapure water. This underscores atmospheric water as a variable alternative, available in nearly all building air conditioning systems or could overcome geographical constraints, particularly in regions where obtaining pure water resources is challenging, offering a cost-effective solution. The dual-fiber reactor using atmospheric water enables high-efficiency H2O2 production anytime and anywhere.

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.

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.

Dechlorination of tetrachloroethylene by palladized iron in the presence of humic acid.

The dechlorination of tetrachloroethylene (PCE) by palladized irons in the presence of humic acid was investigated to understand the feasibility of using Pd/Fe for the in situ remediation of contaminated groundwater. Untreated zerovalent iron (ZVI) was amended with Pd(II) ions to form palladized irons. X-ray photoelectron spectroscopy showed that Pd(II) was completely reduced to metallic Pd on the surface of ZVI. PCE was catalytically dechlorinated via beta-elimination to ethane and ethylene by palladized irons. The carbon mass balances were in the range of 78--98%. The dechlorination followed the pseudo first-order rate equation and the normalized surface reaction rate constant (k(sa)) for PCE dechlorination was 33.47+/-7.21 L/m(2)h in the absence of humic acid. Humic acid competed the reactive sites on the palladized irons with PCE, and thus lowered the dechlorination efficiency and rate of PCE. After 24h of equilibrium between humic acid and palladized irons prior to the injection of PCE, however, the efficiency and rate of PCE dechlorination could increase with increasing concentrations of humic acid. Addition of quinones having low redox potentials including AQDS, lawsone and hydroquinone also enhanced the dechlorination efficiency of PCE after 24h, depicting that humic acids serve as the electron shuttles to effectively transfer electrons and to accelerate the dechlorination efficiency and rate of PCE.