Cold Plasma for Green Advanced Reduction/Oxidation Processes (AROPs) of Organic Pollutants in Water.

Cold plasma is gaining increasing attention as a novel tool to activate energy demanding chemical processes, including advanced reduction/oxidation processes (AROPs) of organic pollutants in water. The very complex milieu generated by discharges at the water/plasma interface comprises photons, strong oxidants and strong reductants which can be exploited for achieving the degradation of most any kind of pollutants. Despite the complexity of these systems, the powerful arsenal of mechanistic tools and chemical probes of physical organic chemists can be usefully applied to understand and develop plasma chemistry. Specifically, the added value of air plasma generated by in situ discharge with respect to ozonation (ex situ discharge) is demonstrated using phenol and various phenol derivatives and mechanistic evidence for the prevailing role of hydroxyl radicals in the initial attack is presented. On the reduction front, the impressive performance of cold plasma in inducing the degradation of recalcitrant perfluoroalkyl substances, which do not react with OH radicals but are attacked by electrons, is reported and discussed. The widely different reactivities of perfluorooctanoic acid (PFOA) and of perfluorobutanoic acid (PFBA) underline the crucial role played in these processes by the interface between plasma and solution and the surfactant properties of the treated pollutants.

Atmospheric plasma-based approaches for the degradation of dimethyl phthalate (DMP) in water.

Cold plasma based treatment of contaminated water is becoming a promising novel green remediation option. This study assessed the performance of two different cold plasma reactors, using, respectively, a self-pulsing discharge (SPD) and a multipin corona discharge (MCD), in the degradation of dimethyl phthalate (DMP), a persistent and ubiquitous pollutant of the aquatic environment. The process kinetics and energy efficiency, as well as the main plasma generated reactive species were determined under various operating conditions concerning the plasma feed gas and flowrate, the voltage polarity, the input power, the DMP initial concentration, the liquid conductivity, and the aqueous matrix used to prepare DMP solutions for these experiments. The MCD reactor, operated with air as plasma feed gas and negative voltage polarity, gave the best results in terms of rate and energy efficiency. Moreover, variations in plasma input power and in the liquid conductivity have limited effect on DMP degradation rate, making this reactor suitable for treating liquids with a range of initial conductivities The effects of DMP initial concentration on its rate of degradation and on the process energy efficiency were also investigated. Differences in the efficiency of production and distribution of plasma generated reactive species, notably •OH and H2O2, observed for the two tested reactors are discussed in terms of different extension of the plasma/liquid interface and diffusion into the bulk solution. It is proposed that among the reactive species, •OH foremost, and O3 to a lesser extent, play a pivotal role in DMP degradation, while the contribution of H2O2 appears to be limited. The rate of DMP degradation was not drastically different in Milli-Q water and in tap water, a positive outcome in view of practical applications of the technology. The lower rate observed in tap than in Milli-Q water is attributed to the presence of bicarbonate and carbonate, which are known scavengers of hydroxyl radicals.

Exploring dynamic membrane as an alternative for conventional membrane for the treatment of old landfill leachate.

This study compares the performance of a lab-scale pre-anoxic and post-aerobic submerged dynamic membrane bioreactor (DMBR) with similar studies on conventional membrane bioreactors (MBRs) for the treatment of old landfill leachate (LFL) while presenting a strategy to achieve stable DMBR operation. The results suggested that DMBR performed similar, or in some cases, better than MBRs. Like conventional MBRs treating LFL, DMBR can also accommodate large variations in operating parameters including influent feed composition and loading rates and thus, it can guarantee long term stable bioreactor operation (total nitrogen removal up to 98%) with acceptable effluent quality (Turbidity < 10 NTU). The results also demonstrated that gradual increment in influent LFL concentration was found to be effective for a stable DMBR operation however, it significantly deteriorated dynamic membrane (DM) filtration performance (p < 10E-7), resulting in higher fouling rate and deteriorated effluent quality. Nonetheless, poor DM performance and higher fouling rate were effectively controlled by using lower mesh porosity (52 µm instead of 200 µm) and increase in DM effective filtration area.

Assessment of dynamic membrane filtration for biological treatment of old landfill leachate.

This study investigated the behaviour of dynamic membrane (DM) filtration for the treatment of stabilised landfill leachate in a bench-scale pre-anoxic and aerobic submerged dynamic membrane bioreactor (DMBR). Four meshes with different openings (10, 52, 85 and 200 µm) were tested to support the development of DM. Differences were observed among the meshes in supporting the development of the cake layer constituting the DM. The treatment of landfill leachate had an impact on sludge characteristics resulting in deteriorated filtration performance of the DM. Effluent turbidity was often higher than 100 NTU for larger mesh pore size (85 and 200 µm). Low effluent turbidity was achieved with meshes with 10 and 52 µm (13 ±â€¯2 and 26 ±â€¯4 NTU, respectively) although at membrane fluxes lower than 10 L m- 2 h-1. The bioreactor exhibited a moderate organics removal of 50-60% and an ammonia oxidation between 80 and 90%. Incomplete nitrification was observed due to increased concentrations of free ammonia and free nitrous acid, with nitrite effluent concentrations up to 1062 mgNO2--N L-1. Due to the large presence of refractory organic matter in landfill leachate, denitrification was limited resulting in a total nitrogen removal of approximately 20%.

Products, reactive species and mechanisms of PFOA degradation in a self-pulsing discharge (SPD) plasma reactor.

Non-thermal plasma is a promising tool for novel technologies to treat water contaminated by recalcitrant pollutants. We report here on products, reactive species and mechanisms of the efficient degradation of perfluorooctanoic acid (PFOA) achieved with a self-pulsing discharge developed previously in our lab. Air or argon were used as plasma feed gas, ultrapure or tap water as aqueous medium. Identified organic intermediate products arise from chain-shortening and defluorination reactions, the latter achieving not only C-F to C-H exchange (hydro-de-fluorination), as reported in the literature, but also C-F to C-OH exchange (hydroxy-de-fluorination). In contrast with chain-shortening, yielding lower homologues of PFOA via selective cleavage of the C-C bond at the carboxylate group, defluorination occurs at various sites of the alkyl chain giving mixtures of different isomeric products. Plasma generated reactive species were investigated under all experimental conditions tested, using specific chemical probes and optical emission spectroscopy. Cross-analysis of the results revealed a striking direct correlation of energy efficiency for PFOA degradation and for production of plasma electrons. In contrast, no correlation was observed for emission bands of either Ar+ or OH radical. These results indicate a prevalent role of plasma electrons in initiating PFOA degradation using self-pulsing discharge plasma above the liquid.

Highly efficient degradation of PFAS and other surfactants in water with atmospheric RAdial plasma (RAP) discharge.

Atmospheric plasma offers a viable approach to new water remediation technologies, best suited for the degradation of persistent organic pollutants such as PFAS, per- and polyfluoroalkyl substances. This paper reports on the remarkable performance of a novel RAdial Plasma (RAP) discharge reactor in treating water contaminated with PFAS surfactants, notably the ubiquitous perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). RAP proved to be versatile and robust, performing very well over a wide range of pollutants concentrations. Thus, PFOA degradation was most satisfactory with regard to all critical indicators, kinetics (≥99% PFOA conversion in less than 2.5 min and 30 min in solutions with initial concentrations of 41 µg/L and 41 mg/L, respectively), byproducts, and energy efficiency (G50 greater than 2000 mg/kWh for 41 µg/L - 4.1 mg/L PFOA initial concentrations). Likewise for PFOS as well as for Triton X-100, a common fluorine-free non-ionic surfactant tested to explore the scope of applicability of RAP to the degradation of surfactants in general. The results obtained with RAP compare most favourably with those reported for state-of-art plasma systems in similar experiments. RAP's excellent performance is attributed to the dense network of radial discharges it generates, randomly spread over the entire exposed surface of the liquid thus establishing an extended highly reactive plasma-liquid interface with both strongly reducing and oxidizing species. Mechanistic insight is offered based on the observed degradation products and on available literature data on the surfactants properties and on their plasma induced degradation investigated in previous studies.

Anaerobic self-forming dynamic membrane bioreactors (AnSFDMBRs) for wastewater treatment - Recent advances, process optimization and perspectives.

Recently, anaerobic self-forming dynamic membrane bioreactors (AnSFDMBRs) have attracted increasing attention, and are considered as an alternative to conventional anaerobic membrane bioreactors (AnMBRs). The key advantages of AnSFDMBRs include high flux, low propensity towards fouling, and low capital and operational costs. Although there have been several reviews on AnMBRs, very few reviews on AnSFDMBR system. Previous AnSFDMBR studies have focused on lab-scale to investigate the long-term flux, methods to improve performance and the associated mechanisms. Microbial analysis showed that the phyla namely Proteobacteria, Bacteroidetes and Firmicutes are dominant in both bulk sludge and cake biofilm, but their abundance is low in biocake. This review critically examines the fundamentals of AnSFDMBRs, operational conditions, process optimization and applications. Moreover, the current knowledge gaps (e.g., dynamic membrane module optimization, membrane surface modification and functional microbes enrichment) that should be studied in future to design an efficient AnSFDMBR system for treatment of diverse wastewaters.

Dynamic membrane bioreactor (DMBR) for the treatment of landfill leachate; bioreactor's performance and metagenomic insights into microbial community evolution.

The use of dynamic membranes as a low-cost alternative for conventional membrane for the treatment of landfill leachate (LFL) was investigated in this study. For this purpose a lab-scale, submerged pre-anoxic and post-aerobic bioreactor configuration was used with nylon mesh as dynamic membrane support. The study was conducted at ambient temperature and LFL was fed to the bioreactor in gradually increasing concentration mixed with tap water (from 20% to 100%). The results of this study demonstrated that lower mesh pore size of 52 µm achieved better results in terms of solid-liquid separation performance (turbidity <10 NTU) of the formed dynamic membrane layer as compared to 200 and 85 µm meshes while treating LFL. Consistently high NH4+-N conversion efficiency of more than 98% was achieved under all nitrogen loading conditions, showing effectiveness of the formed dynamic membrane in retaining slow growing nitrifying species. Total nitrogen removal reached more than 90% however, the denitrification activity showed a fluctuating profile and found to be inhibited by elevated concentrations of free nitrous acid and NO2--N at low pH values inside the anoxic bioreactor. A detailed metagenomic analysis allowed a taxonomic investigation over time and revealed the potential biochemical pathways involved in NH4+-N conversion. This study led to the identification of a dynamic system in which nitrite concentration is determined by the contribution of NH4+ oxidizers (Nitrosomonas), and by a competition between nitrite oxidizers (Nitrospira and Nitrobacter) and reducers (Thauera).

Application of anaerobic dynamic membrane bioreactor (AnDMBR) for the successful enrichment of Anammox bacteria using mixed anaerobic and aerobic seed sludge.

This study investigated a novel bioreactor configuration coupled with a side-stream dynamic membrane (DM) for Anammox enrichment as an alternative for conventional membrane. Bioreactor was fed with synthetic feed and seeded with a mix of anaerobic and aerobic sludge. In situ mechanical cleaning was employed for DM cleaning. DM development and performance was analysed over two polyamide-nylon meshes (200 and 52 µm). Solid-liquid separation of 52 µm mesh outperformed 200 µm with an average effluent turbidity of 2.4 ±â€¯0.1 NTU. The system was operated at a maximum nitrogen loading rate of 696 mg-N L-1 d-1 and achieved a maximum nitrogen removal rate of 611.6 mg-N L-1 d-1. At steady state, the average ammonium, nitrite and total nitrogen removal efficiencies were 87 ±â€¯0.6%, 98.5 ±â€¯0.15% and 87.5 ±â€¯0.56% respectively. Digital realtime PCRSequence analysis showed that Planctomycetales belonging to ascertained Anammox-specific genera progressively increased their presence in the reactor consistently with its nitrogen removal performance.