Electrochemical Advanced Oxidation of Perfluorooctanoic Acid: Mechanisms and Process Optimization with Kinetic Modeling.

Electrochemical advanced oxidation processes (EAOPs) are promising technologies for perfluorooctanoic acid (PFOA) degradation, but the mechanisms and preferred pathways for PFOA mineralization remain unknown. Herein, we proposed a plausible primary pathway for electrochemical PFOA mineralization using density functional theory (DFT) simulations and experiments. We neglected the unique effects of the anode surface and treated anodes as electron sinks only to acquire a general pathway. This was the essential first step toward fully revealing the primary pathway applicable to all anodes. Systematically exploring the roles of valence band holes (h+), hydroxyl radicals (HO•), and H2O, we found that h+, whose contribution was previously underestimated, dominated PFOA mineralization. Notably, the primary pathway did not generate short-chain perfluoroalkyl carboxylic acids (PFCAs), which were previously thought to be the main degradation intermediates, but generated other polyfluorinated alkyl substances (PFASs) that were rapidly degraded upon formation. Also, we developed a simplified kinetic model, which considered all of the main processes (mass transfer with electromigration included, surface adsorption/desorption, and oxidation on the anode surface), to simulate PFOA degradation in EAOPs. Our model can predict PFOA concentration profiles under various current densities, initial PFOA concentrations, and flow velocities.

Discrepancies in N2O emissions between household waste and its food waste and non-food waste components during the predisposal stage.

Nitrous oxide (N2O) is a greenhouse gas (GHG) and an ozone-depleting substance. Municipal solid waste (MSW) management and treatment activities are some of the sources of GHG emissions. However, the biogenic GHG emissions during the predisposal stage of MSW management, during which waste is transferred to garbage cans and then transported to disposal sites, have received little attention. In this study, household waste was divided into food and non-food waste, and the effects of these types of waste and different oxygen concentrations (21%, 10%, and 1%) on N2O emissions were investigated. A15N-labeled isotope experiment was conducted over three days to determine the contributions of nitrification and denitrification to N2O emissions. The results showed that the N2O fluxes first increased and then decreased during the three-day tests at different O2 concentrations. The maximum N2O flux of 1469.59 ± 1004.32 µg N·kg-1 wet waste·h-1 occurred during the predisposal of food waste at an O2 concentration of 21%, with the total N2O emissions reaching 20.26 ± 10.87 mg N·kg-1 wet waste, which exceeds the emissions from some waste disposal processes, such as composting and landfills. The N2O emissions decreased in the following order: food waste > household waste > non-food waste. For food waste, the peak value and total amount of N2O emissions decreased significantly as the O2 concentration decreased. In contrast, the N2O emissions from non-food waste increased as the O2 concentration decreased. Denitrification was the predominant biogenic source of N2O emissions; it accounted for over 60% of N2O production in all treatments. Nitrification also played an important role in N2O emissions during the early predisposal stage.

The transformation of dissolved organic matter and formation of halogenated by-products during electrochemical advanced oxidation pretreatment for shale gas produced water.

Electrochemical advanced oxidation processes (EAOPs) have shown great potential for the treatment of shale gas produced water (SGPW). In this study, we investigated the transformation of dissolved organic matter (DOM) during EAOPs of SGPW and the formation of toxic halogenated by-products at various current densities, using fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry. We found that the priority of DOM removal was terrestrial humic-like > microbial humic-like > protein-like substances. Non-Halogenated organic compounds (non-HOCs) and HOCs were predominantly CHO, and CHOCl/CHOBr compounds in EAOP-treated SGPW, respectively. As applied current density and treatment time increased, the production of oxyhalides increased, with chlorate > bromate > perchlorate. Meanwhile, most DOM was mineralized, resulting in residual products with higher modified aromaticity index (AImod) and nominal oxidation state of carbon (NOSC). The resistants had lower mass-to-charge ratio (m/z), AImod, NOSC, and double bond equivalent minus oxygen per carbon ((DBE-O)/C). The dominant reactions were the addition of tri-oxygen and deallyl. Bromine addition dominated the reactions of halogenating addition, while chlorine addition took second place. Furthermore, the acute toxicity of SGPW was positively correlated with inorganic halogenated by-products. This study contributes to the understanding and improvement of EAOPs for the treatment of SGPW.

Generation, toxicity, and reduction of chlorinated byproducts: Overcome bottlenecks of electrochemical advanced oxidation technology to treat high chloride wastewater.

Electrochemical advanced oxidation process (EAOP) is recommended for high-strength refractory organics wastewater treatment, but the accompanying chlorinated byproduct generation becomes a bottleneck that limits the application of this technology to actual wastewater. In this study, we applied EAOP (0.4-40 mA cm-2) to treat ultrafiltration effluent of an actual landfill leachate, and quantitatively assessed the toxicities of the dominant chlorinated byproducts in EAOP-treated effluent. Considering both toxic effect and dose, it followed the order: active chlorine > chlorate > perchlorate > organochlorines. The toxic active chlorine could spontaneously decompose by settling. And secondary bioreactor originally serving for denitrification could be used to reduce perchlorate and chlorate. The effects of residual active chlorine and extra carbon addition on simultaneous denitrification, perchlorate, and chlorate reduction were investigated. It seemed that 20 mg of active chlorine was an acceptable level to bioactivity, and sufficient electron donors favored the removal of chlorate and perchlorate. Pseudomonas was identified as an active chlorine tolerant chlorate-reducing bacteria. And Thauera was responsible for perchlorate reduction under the conditions of sufficient carbon source supply. Our results confirmed that the perchlorate and chlorate concentrations in the effluent below their health advisory levels were achievable, solving the issue of toxic chlorinated byproduct generation during EAOP. This study provided a solution to realistic application of EAOP to treat high chloride wastewater.

Identification of key water parameters and microbiological compositions triggering intensive N2O emissions during landfill leachate treatment process.

Landfill leachate treatment processes tend to emit more N2O compared to domestic wastewater treatment. This discrepancy may be ascribed to leachate water characteristics such as high refractory COD, ammonium (NH4+) content, and salinity. In this work, the leachate influent was varied to examine the N2O emission scenarios. NH4+-N, COD, and Cl- concentrations ranged between 1000-2500, 1000-10,000, and 500-3000 mg L-1, respectively. Simultaneously, we attempted to combine statistical analysis with high-throughput sequencing to understand the microbial mechanism with regards to N2O emission. Results show that the strong N2O emissions occur in the nitrifying tank due to the intensive aeration. The system receiving the lowest COD shows the maximum N2O emission factor of 42.7% of the removed nitrogen. Both redundancy analysis and a structural equation model verify that insufficient degradable organics are the key water parameter triggering intensive N2O emission within the designed influent limits. Furthermore, two essential but non-abundant functional bacteria, Flavobacterium (acting as a denitrifier) and Nitrosomonas (acting as a nitrifier), are identified as the core functional species that dramatically influence N2O emissions. An increase in influent COD promotes the proliferation of Flavobacterium and inhibits Nitrosomonas, which in turn reduce N2O release. Meanwhile, two keystone species of Castellaniella and Saprospiraceae unclassified are recognized. They may supply a suitable niche and integrity of the microbial community for N-cycle functional bacteria. These findings reveal the essential role of non-abundant species in microbial community, and expand the current understanding of microbial interactions underlying N2O dynamics in leachate treatment systems.

Characterization of dissolved organic matter during the O3-based advanced oxidation of mature landfill leachate with and without biological pre-treatment and operating cost analysis.

In this study, the organic matter in an O3-based advanced oxidation process (AOP) for treating raw leachate (RL) and bio-treated leachate (BTL) was characterized. The optimal conditions for COD removal in RL and BTL treatment were as follows: initial pH of 6.0 and H2O2 dosage of 9 mL 30% H2O2 L-1 leachate, and initial pH of 12 without H2O2 addition, respectively. H2O2 addition had little influence on COD removal in the BTL treatment as sufficient hydroxyl radicals may not be produced at extremely high pH levels. The differences in the alkalinity between RL and BTL caused differences in the optimum pH of the AOPs. Overall, the initial pH more affected COD removal than the H2O2 dosage. O3-based AOP converted organics with high molecular weight fractions into low ones. Meanwhile, it preferentially degraded hydrophobic substances over hydrophilic substances. The organic matter in the BTL contained more refractory and hydrophobic fractions; therefore, higher COD removal was achieved in the treatment of RL. The organics in the treatment of RL and BTL were identified by excitation-emission matrix spectroscopy combined with parallel factor analysis, and their degradation decreased in the following order: terrestrial humic-like > microbial humic-like > combination of tryptophan and humic-like components. O3-based AOP significantly enhanced biodegradability. According to the economic analysis results, as an intermediate treatment, O3-based AOP is a cost-effective strategy of ensuring that leachate effluent meets the discharge standards, with the lowest operating cost of $4.62 m-3. This study provides a reference for the application of O3-based AOP in full-scale landfill leachate treatment.

[Fermentations of xylose and arabinose by Kluyveromyces marxianus].

Kluyveromyces marxianus, as unconventional yeast, attracts more and more attention in the biofuel fermentation. Although this sort of yeasts can ferment pentose sugars, the fermentation capacity differs largely. Xylose and arabinose fermentation by three K. marxianus strains (K. m 9009, K. m 1911 and K. m 1727) were compared at different temperatures. The results showed that the fermentation performance of the three strains had significant difference under different fermentation temperatures. Especially, the sugar consumption rate and alcohol yield of K. m 9009 and K. m 1727 at 40 ℃ were better than 30 ℃. This results fully reflect the fermentation advantages of K. marxianus yeast under high-temperature. On this basis, five genes (XR, XDH, XK, AR and LAD) coding key metabolic enzymes in three different yeasts were amplified by PCR, and the sequence were compared by Clustalx 2.1. The results showed that the amino acid sequences coding key enzymes have similarity of over 98% with the reference sequences reported in the literature. Furthermore, the difference of amino acid was not at the key site of its enzyme, so the differences between three stains were not caused by the gene level, but by transcribed or translation regulation level. By real-time PCR experiment, we determined the gene expression levels of four key enzymes (XR, XDH, XK and ADH) in the xylose metabolism pathway of K. m 1727 and K. m 1911 at different fermentation time points. The results showed that, for thermotolerant yeast K. m 1727, the low expression level of XDH and XK genes was the main factors leading to accumulation of xylitol. In addition, according to the pathway of Zygosaccharomyces bailii, which have been reported in NCBI and KEGG, the xylose and arabinose metabolic pathways of K. marxianus were identified, which laid foundation for further improving the pentose fermentation ability by metabolic engineering.

Enhanced fermentative performance under stresses of multiple lignocellulose-derived inhibitors by overexpression of a typical 2-Cys peroxiredoxin from Kluyveromyces marxianus.

BACKGROUND: Bioethanol from lignocellulosic materials is of great significance to the production of renewable fuels due to its wide sources. However, multiple inhibitors generated from pretreatments represent great challenges for its industrial-scale fermentation. Despite the complex toxicity mechanisms, lignocellulose-derived inhibitors have been reported to be related to the levels of intracellular reactive oxygen species (ROS), which makes oxidoreductase a potential target for the enhancement of the tolerance of yeasts to these inhibitors. RESULTS: A typical 2-Cys peroxiredoxin from Kluyveromyces marxianus Y179 (KmTPX1) was identified, and its overexpression was achieved in Saccharomyces cerevisiae 280. Strain TPX1 with overexpressed KmTPX1 gene showed an enhanced tolerance to oxidative stresses. Serial dilution assay indicated that KmTPX1 gene contributed to a better cellular growth behavior, when the cells were exposed to multiple lignocellulose-derived inhibitors, such as formic acid, acetic acid, furfural, ethanol, and salt. In particular, KmTPX1 expression also possessed enhanced tolerance to a mixture of formic acid, acetic acid, and furfural (FAF) with a shorter lag period. The maximum glucose consumption rate and ethanol generation rate in KmTPX1-expressing strain were significantly improved, compared with the control. The mechanism of improved tolerance to FAF depends on the lower level of intracellular ROS for cell survival under stress. CONCLUSION: A new functional gene KmTPX1 from K. marxianus is firstly associated with the enhanced tolerance to multiple lignocellulose-derived inhibitors in S. cerevisiae. We provided a possible detoxification mechanism of the KmTPX1 for further theoretical research; meanwhile, we provided a powerful potential for application of the KmTPX1 overexpressing strain in ethanol production from lignocellulosic materials.