Electrocatalytic Degradation of Phenolic Wastewater Using a Zero-Gap Flow-Through Reactor Coupled with a 3D Ti/RuO2-TiO2@Pt Electrode.

In this study, the performance of a zero-gap flow-through reactor with three-dimensional (3D) porous Ti/RuO2-TiO2@Pt anodes was systematically investigated for the electrocatalytic oxidation of phenolic wastewater, considering phenol and 4-nitrophenol (4-NP) as the target pollutants. The optimum parameters for the electrochemical oxidation of phenol and 4-NP were examined. For phenol degradation, at an initial concentration of 50 mg/L, initial pH of 7, NaCl concentration of 10.0 g/L, current density of 10 mA/cm2, and retention time of 30 min, the degradation efficiency achieved was 95.05%, with an energy consumption of 15.39 kWh/kg; meanwhile, for 4-NP, the degradation efficiency was 98.42% and energy consumption was 19.21 kWh/kg (at an initial concentration of 40 mg/L, initial pH of 3, NaCl concentration of 10.0 g/L, current density of 10 mA/cm2, and retention time of 30 min). The electrocatalytic oxidation of phenol and 4-NP conformed to the pseudo-first-order kinetics model, and the k values were 0.2562 min-1 and 0.1736 min-1, respectively, which are 1.7 and 3.6-times higher than those of a conventional electrolyzer. Liquid chromatography-mass spectrometry (LC-MS) was used to verify the intermediates formed during the degradation of phenol or 4-NP and a possible degradation pathway was provided. The extremely narrow electrode distance and the flow-through configuration of the zero-gap flow-through reactor were thought to be essential for its lower energy consumption and higher mass transfer efficiency. The zero-gap flow-through reactor with a novel 3D porous Ti/RuO2-TiO2@Pt electrode is a superior alternative for the treatment of industrial wastewater.

Efficient and Selective Electrochemical Nitrate Reduction to N2 Using a Flow-Through Zero-Gap Electrochemical Reactor with a Reconstructed Cu(OH)2 Cathode: Insights into the Importance of Inter-Electrode Distance.

Electrochemically converting nitrate, a widely distributed nitrogen contaminant, into harmless N2 is a feasible and environmentally friendly route to close the anthropogenic nitrogen-based cycle. However, it is currently hindered by sluggish kinetics and low N2 selectivity, as well as scarce attention to reactor configuration. Here, we report a flow-through zero-gap electrochemical reactor that shows a high performance of nitrate reduction with 100% conversion and 80.36% selectivity of desired N2 in the chlorine-free system at 100 mg-N·L-1 NO3- while maintaining a rapid reduction kinetics of 0.07676 min-1. More importantly, the mass transport and current utilization efficiency are significantly improved by shortening the inter-electrode distance, especially in the zero-gap electrocatalytic system where the current efficiency reached 50.15% at 5 mA·cm-2. Detailed characterizations demonstrated that during the electroreduction process, partial Cu(OH)2 on the cathode surface was reconstructed into stable Cu/Cu2O as the active phase for efficient nitrate reduction. In situ characterizations revealed that the highly selective *NO to *N conversion and the N-N coupling step played crucial roles during the selective reduction of NO3- to N2 in the zero-gap electrochemical system. In addition, theoretical calculations demonstrated that improving the key intermediate *N coverage could effectively facilitate the N-N coupling step, thereby promoting N2 selectivity. Moreover, the environmental and economic benefits and long-term stability shown by the treatment of real nitrate-containing wastewater make our proposed electrocatalytic system more attractive for practical applications.

Innovative flow-through reaction system for the sustainable production of phenolic monomers from lignocellulose catalyzed by supported Mo2C.

Molybdenum carbide supported on activated carbon (ß-Mo2C/AC) has been tested as catalyst in the reductive catalytic fractionation (RCF) of lignocellulosic biomass both in batch and in Flow-Through (FT) reaction systems. High phenolic monomer yields (34 wt.%) and selectivity to monomers with reduced side alkyl chains (up to 80 wt.%) could be achieved in batch in the presence of hydrogen. FT-RCF were made with no hydrogen feed, thus via transfer hydrogenation from ethanol. Similar selectivity could be attained in FT-RCF using high catalyst/biomass ratios (0.6) and high molybdenum loading (35 wt.%) in the catalyst, although selectivity decreased with lower catalyst/biomass ratios or molybdenum contents. Regardless of these parameters, high delignification of the lignocellulosic biomass and similar monomer yields were observed in the FT mode (13-15 wt.%) while preserving the holocellulose fractions in the delignified pulp. FT-RCF system outperforms the batch reaction mode in the absence of hydrogen, both in terms of activity and selectivity to reduced monomers that is attributed to the two-step non-equilibrium processes and the removal of diffusional limitations that occur in the FT mode. Even though some molybdenum leaching was detected, the catalytic performance could be maintained with negligible loss of activity or selectivity for 15 consecutive runs.

Integrated physicochemical processes to tackle high-COD wastewater from pharmaceutical industry.

Wastewater decontamination in pharmaceuticals is crucial to prevent environmental and health risks from API residues and other contaminants. Advanced oxidation processes (AOPs) combined with cavitational treatments offer effective solutions. Challenges include designing reactors on a large scale and monitoring the effectiveness and synergies of the hybrid technology. In the present work, pilot-scale treatment of a real high COD (485 g/L) pharmaceutical wastewater (PW) was investigated using hydrodynamic cavitation (HC) operated individually at 330 L/h or in combination with oxidants and electrical discharge (ED) with cold plasma (15 kV and 48 kHz). The first approach consisted of PW cavitational treatment alone of 7 L of 1:100 diluted PW at a HC-induced pressure of 60 bar and a flow rate of 330 L/h. However, this strategy did not provide satisfactory results for COD (∼15% less), and only when HC treatment was extended to more than 30 min in a recirculation mode, encouraging results were obtained (∼45% COD reduction). Consequently, a hybrid approach combining HC with ED-cold plasma was chosen to treat this high-COD PW. Aiming to establish an efficient flow-through hybrid process, after optimising all cavitation and electrical discharge parameters (45 bar HC pressure and 10 kHz ED frequency), the best COD abatement of ∼50 % was recorded with a 1:50 diluted PW. However, a subsequent adsorption step over activated carbon was required to achieve an almost quantitative COD reduction (95%+). Our integrated physicochemical process proved to be extremely efficient in treating high-COD industrial wastewater and resulted in a remarkable reduction of the COD value. In addition, the residual surfactants content in the PW were also drastically reduced (98%+) when a small amount of oxidants was added in the hybrid HC/ED treatment.

Degradation of micropollutants in flow-through VUV/UV reactors: Impact of internal diameter and baffle allocation.

Application of VUV/UV process for micropollutants removal in decentralized water supply systems (e.g., rural drinking water treatment) is promising while few researches by far paid attention to the performance of practical flow-through reactors. This study investigated the degradation of atrazine (ATZ), sulfamethoxazole (SMX) and metoprolol (MET) under different hydrodynamic conditions in reactors with varied internal diameters and baffle allocations. Results showed that the target micropollutants could be degraded efficiently in the flow-through VUV/UV reactors following basically the pseudo-first order kinetics (R2 ≥ 0.97). The largest degradation rate constants were found in the D35 reactor and incorporation of baffles in the D50 and D80 reactors accelerated obviously the micrpollutants degradation. The improved performances of the baffled reactors were due mainly to the elevated utilization of HO•, and a new parameter named UEHO (HO• utilization efficiency) was proposed accordingly. The calculated UEHO values of the reactors ranged between 30.2% and 69.2% with the largest found in the D50-5 reactor. This testified the usually insufficient utilization of radicals in flow-through reactors and the effectiveness of baffle implementation. Electrical energy per order (EEO) values of micropollutants degradation in the reactors were in the range of 0.104-0.263 kWh m-3 order-1. The degradation was inhibited significantly by high-concentration nitrate yet the formed nitrite concentration stayed consistently below the drinking water limitation. The acute toxicity of the micropollutant solutions increased first and leveled off afterwards during the VUV/UV treatment, as indicated by the inhibition ratios of luminescence intensity of Vibrio fischeri.

Electrochemical removal of gaseous benzene using a flow-through reactor with efficient and ultra-stable titanium suboxide/titanium-foam anode at ambient temperature.

Catalytic oxidation technology is currently considered as a feasible approach to degrade and mineralize volatile organic compounds (VOCs). However, it is still challenging to realize efficient removal of VOCs through catalytic oxidation at room temperature. In our study, a novel flow-through electrocatalytic reactor was designed, composed of porous solid-electrolyte, gas-permeable titanium sub-oxides/titanium-foam (TiSO/Ti-foam) as anode and platinum coated titanium foam (Pt/Ti-foam) as cathode. This device could oxidize nearly 100% of benzene (10 ppm) to carbon dioxide at a current density of 1.2 mA/cm2 under room temperature. More importantly, the device maintained excellent stability over 1000 h. Mechanism of benzene mineralization was discussed. Hydroxyl radicals generated on the TiSO/Ti-foam anode played a crucial role in the oxidation of benzene. This study provides a promising prototype of the electrochemical air purifier, and may find its application in domestic and industrial air pollution control.

Flow-through heterogeneous electro-Fenton system using a bifunctional FeOCl/carbon cloth/activated carbon fiber cathode for efficient degradation of trimethoprim at neutral pH.

The synthesis of multifunctional cathode with high-efficiency and stable catalytic activity for simultaneously producing and activating H2O2 is an effective way for promoting the performance of heterogeneous electro-Fenton process (HEF). In addition, accelerating mass transfer by adopting a flow-through reactor is also great importance because of its better utilization of catalysts and adequate contact of the contaminant with the oxidants generated on the electrode surface. Herein, a novel flow-through HEF (FHEF) system was designed for the degradation of trimethoprim (TMP) using bifunctional cathode with a sandwich structure FeOCl nanosheets loaded onto carbon cloth (CC) and activated carbon fiber (ACF) (FeOCl/CC/ACF). The cathode exhibited excellent performance in activating H2O2 for the in-situ generation of hydroxyl radicals (•OH). The electron spin resonance (ESR) measurements and radical quenching tests proved that the high production of •OH in the FHEF process was favorable to the high catalytic efficiency. 25 mg L-1 TMP was entirely degraded after 60 min, with the TOC removal of 62.6% (180 min) at pH 6.8, 9.0 mA cm-2, and flux rate 210 mL min-1. Moreover, the degradation rate still could reach 83% (60 min) after 10 cycles without obvious valence and crystal phase changes. Simultaneously, the current utilization rate has also been greatly enhanced, with an average current efficiency of 69.9% and a low energy consumption of 0.28 kWh kg-1. The reasonable degradation pathways for TMP were proposed based on the UPLC-QTOF-MS/MS results. Finally, the results of toxicological simulation showed a declining trend in the toxicity of the samples during TMP degradation. These results claim that the FeOCl/CC/ACF-FHEF system is an efficient and economical technology for the treatment of organic contaminants in effluents.

Performance of a Flow-Through Enzyme Reactor Prepared from a Silica Monolith and an α-Poly(D-Lysine)-Enzyme Conjugate.

Horseradish peroxidase (HRP) is covalently bound in aqueous solution to polycationic α-poly(D-lysine) chains of ≈1000 repeating units length, PDL, via a bis-aryl hydrazone bond (BAH). Under the experimental conditions used, about 15 HRP molecules are bound along the PDL chain. The purified PDL-BAH-HRP conjugate is very stable when stored at micromolar HRP concentration in a pH 7.2 phosphate buffer solution at 4 °C. When a defined volume of such a conjugate solution of desired HRP concentration (i.e., HRP activity) is added to a macro- and mesoporous silica monolith with pore sizes of 20-30 µm as well as below 30 nm, quantitative and stable noncovalent conjugate immobilization is achieved. The HRP-containing monolith can be used as flow-through enzyme reactor for bioanalytical applications at neutral or slightly alkaline pH, as demonstrated for the determination of hydrogen peroxide in diluted honey. The conjugate can be detached from the monolith by simple enzyme reactor washing with an aqueous solution of pH 5.0, enabling reloading with fresh conjugate solution at pH 7.2. Compared to previously investigated polycationic dendronized polymer-enzyme conjugates with approximately the same average polymer chain length, the PDL-BAH-HRP conjugate appears to be equally suitable for HRP immobilization on silica surfaces.

Degradation of micropollutants in flow-through UV/chlorine reactors: Kinetics, mechanism, energy requirement and toxicity evaluation.

The degradation of three micropollutants (i.e., atrazine (ATZ), sulfamethoxazole (SMX) and metoprolol (MET)) was comprehensively investigated in flow-through UV/chlorine reactors. Results showed that the micropollutants degradation fitted well with pseudo-first-order kinetics (R2 > 0.92) with the order of rate constants following SMX > MET > ATZ. The developed steady-state approximation (SSA) model was roughly applicable in flow-through UV/chlorine reactors with the predictions deviated within 44%. UV photolysis here stood as the major degradation pathway for ATZ while the contribution of non-radical processes (UV photolysis and chlorination) to SMX degradation increased as the reactor internal diameter enlarged. The degradation rates were reduced to varying extents with complex water matrices (chloride, bicarbonate and dissolved organic matter (DOM)) where the inhibition from the DOM was most prominent (up to 73.6%). Although reactors with a larger internal diameter resulted in reduced degradation rate constants, the energy requirements were also lowered. The EEO values of micropollutants degradation by UV/chlorine fell mostly within 1.0 kWh m-3 order-1 in deionized water and under different water matrices. The acute toxicity was observed to be higher after UV/chlorine treatment in tap water, but still stayed low in general. This study revealed the different kinetics and mechanisms of micropollutants degradation in flow-through reactors and demonstrated the potential of the UV/chlorine process in terms of low energy consumption and acute toxicity.

Experimental and modeling of tetracycline degradation in water in a flow-through enzymatic monolithic reactor.

In this work, the laccase from Trametes versicolor was immobilized in highly porous silica monoliths (0.6-cm diameter, 0.5-cm length). These monoliths feature a unique homogeneous network of interconnected macropores (20 µm) with mesopores (20 nm) in the skeleton and a high specific surface area (330 m2/g). The enzymatic monoliths were applied to degrade tetracycline (TC) in model aqueous solutions (20 ppm). For this purpose, a tubular flow-through reactor (FTR) configuration with recycling was built. The TC degradation was improved with oxygen saturation, presence of degradation products, and recirculation rate. The TC depletion reaches 50% in the FTR and 90% in a stirred tank reactor (CSTR) using crushed monoliths. These results indicate the importance of maintaining a high co-substrate concentration near active sites. A model coupling mass transfers with a Michaelis-Menten kinetics was applied to simulate the TC degradation in real wastewaters at actual TC concentration (2.8 10-4 ppm). Simulation results show that industrial scale FTR reactor should be suitable to degrade 90% of TC in 5 h at a flow rate of 1 mL/min in a single passage flow configuration. Nevertheless, the process could certainly be further optimized in terms of laccase activity, oxygen supply near active sites, and contact time.

Electrochemical flow-through disinfection reduces antibiotic resistance genes and horizontal transfer risk across bacterial species.

Antibiotic resistant bacteria (ARB) and antibiotic resistance genes (ARGs), as emerging pollutants, are released into environment, increasing the risk of horizontal gene transfer (HGT). However, a limited number of studies quantified the effects of ARB disinfection on the HGT risk. This study investigated the inactivation of E. coli 10667 (sul) and the release and removal of ARGs using an electrochemical flow-through reactor (EFTR). Furthermore, the transfer frequencies and potential mechanisms of HGT after disinfection were explored using non-resistant E. coli GMCC 13373 as the recipient and E. coli DH5α carrying plasmid RP4 as the donor. A threshold of current density (0.25 mA/cm2) was observed to destroy cells and release intracellular ARGs (iARGs) to increase extracellular ARGs (eARGs) concentration. The further increase in the current density to 1 mA/cm2 resulted in the decline of eARGs concentration due to the higher degradation rate of eARGs than the release rate of iARGs. The performance of ARGs degradation and HGT frequency by EFTR were compared with those of conventional disinfection processes, including chlorination and ultraviolet radiation (UV). A higher ARGs degradation (83.46%) was observed by EFTR compared with that under chlorination (10.23%) and UV (27.07%). Accordingly, EFTR reduced the HGT frequency (0.69) of released ARGs into the recipient (Forward transfer), and the value was lower than that by chlorination (2.69) and UV (1.73). Meanwhile, the surviving injured E. coli 10667 (sul) with increased cell permeability was transferred by plasmid RP4 from the donor (Reverse transfer) with a higher frequency of 0.33 by EFTR compared with that under chlorination (0.26) and UV (0.16). In addition, the sul3 gene was the least resistant to EFTR than sul1 and sul2 gene. These findings provide important insights into the mechanism of HGT between the injured E. coli 10667 (sul) and environmental bacteria. EFTR is a promising disinfection technology for preventing the spread of antibiotic resistance.

Electrodeposition of Pb and PbO2 on Graphite Felt in Membraneless Flow-Through Reactor: A Method to Prepare Lightweight Electrode Grids for Lead-Acid Batteries.

One of the possible ways of mitigating the primary lead-acid battery downside-mass- is to replace the heavy lead grids that can add up to half of the total electrode's mass. The grids can be exchanged for a lightweight, chemically inert, and conductive material such as graphite felt. To reduce carbon surface area, Pb/PbO2 can be electrochemically deposited on graphite felt. A flow-through reactor was applied to enhance penetration of adequate coverage of graphite felt fibers. Three types of electrolytes (acetate, nitrate, and methanesulfonate) and two additives (ligninsulfonate and Triton X-100) were tested. The prepared composite electrodes showed greater mechanical strength, up to 5 times lower electrical resistivity, and acted as Pb and PbO2 electrodes in sulfuric acid electrolytes.

Degradation of micropolluants in flow-through VUV/UV/H2O2 reactors: Effects of H2O2 dosage and reactor internal diameter.

The degradation of atrazine (ATZ), sulfamethoxazole (SMX) and metoprolol (MET) in flow-through VUV/UV/H2O2 reactors was investigated with a focus on the effects of H2O2 dosage and reactor internal diameter (ID). Results showed that the micropollutants were degraded efficiently in the flow-through VUV/UV/H2O2 reactors following the pseudo first-order kinetics (R2 > 0.92). However, the steady-state assumption (SSA) kinetic model being vital in batch reactors was found invalid in flow-through reactors where fluid mixing was less sufficient. With the increase of H2O2 dosage, the ATZ removal efficiency remained almost constant while the SMX and MET removal was enhanced to different extents, which could be explained by the different reactivities of the pollutants towards HO•. A larger reactor ID resulted in lower degradation rate constants for all the three pollutants on account of the lower average fluence rate, but the change in energy efficiency was much more complicated. In reality, the electrical energy per order (EEO) of the investigated VUV/UV/H2O2 treatments ranged between 0.14-0.20, 0.07-0.14 and 0.09-0.26 kWh/m3/order for ATZ, SMX and MET, respectively, with the lowest EEO for each pollutant obtained under varied H2O2 dosages and reactor IDs. This study has demonstrated the efficiency of VUV/UV/H2O2 process for micropollutant removal and the inadequacy of the SSA model in flow-through reactors, and elaborated the influential mechanisms of H2O2 dosage and reactor ID on the reactor performances.

Nitrogen dynamic in vitro using sludge of a sewage stabilization pond from Patagonia (Argentina).

A relevant and current aspect of wastewater treatment systems is related to the processes of the nitrogen cycle that results in its elimination in gaseous forms. In the present study, we report the first measurements of nitrate-reducing rate (NRR) at lab-scale, using the flow-through reactor technique with sludge of a sewage stabilization pond system located in Patagonia (Argentina). Sludge was collected from Inlet and Outlet areas, in winter and summer. The sludge was characterized by having high moisture content (>94%) and organic matter concentration greater than 37%. The nitrate reduction experimental dates fitted significantly to the Michaelis-Menten model, allowing the estimation of the parameters that regulate the NR kinetics. The maximum potential nitrate reduction rate (Rmax) showed great variability, registering a maximum of 131.6 µmol-N·gdw-1·h-1 (Outlet-Summer) and a minimum of 4.1 µmol-N·gdw-1·h-1 (Inlet-Winter). The lowest half saturation constant (Km) was recorded in the Inlet sludge during the winter (6.1 mg N-NO3-·L-1), which indicates a greater affinity for nitrate of this bacterial consortium. An unusually high activity of NR was registered, being higher with sludge from the Outlet zone and with summer temperature. In full-scale ponds, the NR activity could explain a relevant part of the nitrogen removal that involves the escape of gaseous forms.

Comprehensive treatment of marine aquaculture wastewater by a cost-effective flow-through electro-oxidation process.

The effective treatment of marine aquaculture wastewater is of great significance to protect marine environment and marine organisms. This study validated the feasibility of the comprehensive removal of NH4+-N, NO2--N, COD and P, as well as disinfection and antibiotics removal from marine aquaculture wastewater by electrochemical oxidation (EO), comparing the performance and energy consumption with that by electro-peroxone (EP) and electro-Fenton (EF) process. Due to the formation of more free chlorine, the removal of NH4+-N and COD was in order of EO â‰« EP > EF. A new flow-through EO reactor was adopted, which was found enhanced the formation rate of free chlorine and degradation rate of pollutants, and thus performed better than that of flow-by reactor and batch reactor. By this flow-through EO process, the removal of NH4+-N and NO2--N could reach >90% and their concentrations after treatment both meet the Water Drainage Standard for Sea Water Mariculture (SC/T 9103-2007). Meanwhile, the process had a good bactericidal performance with a lg(c/c0) of -5.6. At the same time, antibiotics such as sulfadimidine (SMT) and norfloxacin (NOR) could be completely removed. The energy consumption was only 0.054 kWh/g NH4+-N (0.27 kWh/m3), which was far more cost-effective than other oxidative processes. The new flow-through EO process has great practical application prospects for the comprehensive removal of multiple pollutants and sterilization from marine aquaculture wastewater.

Electrochemically mediated nitrate reduction on nanoconfined zerovalent iron: Properties and mechanism.

Selective reduction of nitrate to N2 is attractive but still a difficult challenge in the water treatment field. Herein, we established a flow-through electrochemical system packed with polymeric beads supported nZVI (nZVI@D201) for selective nitrate reduction. Consequently, efficient nitrate reduction in the flow mode was achieved on nZVI@D201 under electrochemical regulation with N2 selectivity of up to 95% for at least 60 h. Otherwise, nZVI was gradually exhausted after 20 h, and the product was mainly the undesired NH4+. Through a series of comparative experiments, we clarified that the enhanced nitrate reduction on nZVI under electrochemical regulation was mainly attributed to electrons (from cathode) and active hydrogen ([H]) rather than the previously speculated H2. Combining the characterizations of nZVI during nitrate reduction by X-ray diffraction and X-ray photoelectron spectrometry, we found that nitrate reduction under electrochemical regulation was mediated by nZVI along with the resultant Fe0@FexOy-Fe(II) structure and was sustained by electrons (from cathode) and [H] via the in situ reduction of Fe(III) back to Fe(II). Meanwhile, the undesirable product NH4+ was efficiently oxidized to N2 by the active chlorine generated on the anode. This study not only clarifies the mechanism of enhanced nitrate reduction on nZVI via electrochemical regulation but also advances the technological coupling of nZVI reduction with electrochemistry.

Nitrate addition stimulates microbial decomposition of organic matter in salt marsh sediments.

Salt marshes sequester carbon at rates more than an order of magnitude greater than their terrestrial counterparts, helping to mitigate climate change. As nitrogen loading to coastal waters continues, primarily in the form of nitrate, it is unclear what effect it will have on carbon storage capacity of these highly productive systems. This uncertainty is largely driven by the dual role nitrate can play in biological processes, where it can serve as a nutrient-stimulating primary production or a thermodynamically favorable electron acceptor fueling heterotrophic metabolism. Here, we used a controlled flow-through reactor experiment to test the role of nitrate as an electron acceptor, and its effect on organic matter decomposition and the associated microbial community in salt marsh sediments. Organic matter decomposition significantly increased in response to nitrate, even at sediment depths typically considered resistant to decomposition. The use of isotope tracers suggests that this pattern was largely driven by stimulated denitrification. Nitrate addition also significantly altered the microbial community and decreased alpha diversity, selecting for taxa belonging to groups known to reduce nitrate and oxidize more complex forms of organic matter. Fourier Transform-Infrared Spectroscopy further supported these results, suggesting that nitrate facilitated decomposition of complex organic matter compounds into more bioavailable forms. Taken together, these results suggest the existence of organic matter pools that only become accessible with nitrate and would otherwise remain stabilized in the sediment. The existence of such pools could have important implications for carbon storage, since greater decomposition rates as N loading increases may result in less overall burial of organic-rich sediment. Given the extent of nitrogen loading along our coastlines, it is imperative that we better understand the resilience of salt marsh systems to nutrient enrichment, especially if we hope to rely on salt marshes, and other blue carbon systems, for long-term carbon storage.

Arsenite and chromate sequestration onto ferrihydrite, siderite and goethite nanostructured minerals: Isotherms from flow-through reactor experiments and XAS measurements.

Sorption isotherms remain a major tool to describe and predict the mobility of pollutants in natural and anthropogenic environments, but they are typically determined by independent batch experiments. In the present study, the sequestration of As(III), Cr(VI) and competitive As(III)-Cr(VI) on/in 6L-ferrihydrite, siderite and goethite nanostructured minerals was reinvestigated using stirred flow-through reactor experiments. Herein, sorption isotherms were particularly determined from breakthrough curves for inert and reactive tracers monitored simultaneously in a single percolation experiment. In complement, X-ray absorption spectroscopy (XAS) was used to identify As sorption sites on 6L-ferrihydrite and goethite. As expected, the minerals have high potential to remove As and Cr from water (siderite = ferrihydrite (about 60 mg/g) > goethite (20 mg/g)). As and Cr sorption isotherms were modelled with a Langmuir model, and with a sigmoidal Hill model in the case of the competitive sorption. XAS measurements have revealed that As(III) was partially oxidized (up to 22%) in the competitive system with chromate oxyanion Cr(VI). As(III) sorbed on ferrihydrite and goethite adopted edge-sharing and corner sharing complex geometries. Nowadays, a new class of adsorbing phases is being developed for wastewater treatment, including engineered nanostructured materials and nanocomposites. The use of flow through reactor experiments as a high throughput method, combined with XAS, should be considered as efficient screening methods to test their sorbing properties on various contaminants.

Understanding possible underlying mechanism in declining germicidal efficiency of UV-LED reactor.

Since ultraviolet light emitting diodes (UV-LEDs) have emerged as an alternative light source for UV disinfection systems, enhancement of reactor performance is a demanding challenge to promote its practical application in water treatment process. This study explored the underlying mechanism of the inefficiency observed in flow-through mode UV disinfection tests to improve the light utilization of UV-LED applications. In particular, the disinfection performance of UV-LED reactors was evaluated using two different flow channel types, reservoir and pathway systems, in order to elucidate the impact of physical circumstances on germicidal efficiency as the light profile was adjusted. Overall, a significant reduction in germicidal efficiency was observed when exposure time was prolonged or a mixing chamber was integrated. Zeta analysis revealed that the repulsion rate between microorganisms decreased with UV fluence transfer, and that change might cause the shielding effect of UV delivery to target microorganisms. In line with the above findings, the reduction in efficiency intensified when opportunities for microbial collision increased. Thus, UV induced microbial aggregation was implicated as being a disinfection hindering factor, exerting its effect through uneven UV illumination. Ultimately, the results refuted the prevailing belief that UV has a cumulative effect. We found that the reservoir system achieved worse performance than the pathway system despite it providing 15 times higher UV fluence: the differences in germicidal efficiency were 1-log, 1.4-log and 1.7-log in the cases of P.aeruginosa, E.coli and S.aureus, respectively.

Steel slag carbonation in a flow-through reactor system: the role of fluid-flux.

Steel production is currently the largest industrial source of atmospheric CO2. As annual steel production continues to grow, the need for effective methods of reducing its carbon footprint increases correspondingly. The carbonation of the calcium-bearing phases in steel slag generated during basic oxygen furnace (BOF) steel production, in particular its major constituent, larnite {Ca2SiO4}, which is a structural analogue of olivine {(MgFe)2SiO4}, the main mineral subjected to natural carbonation in peridotites, offers the potential to offset some of these emissions. However, the controls on the nature and efficiency of steel slag carbonation are yet to be completely understood. Experiments were conducted exposing steel slag grains to a CO2-H2O mixture in both batch and flow-through reactors to investigate the impact of temperature, fluid flux, and reaction gradient on the dissolution and carbonation of steel slag. The results of these experiments show that dissolution and carbonation of BOF steel slag are more efficient in a flow-through reactor than in the batch reactors used in most previous studies. Moreover, they show that fluid flux needs to be optimized in addition to grain size, pressure, and temperature, in order to maximize the efficiency of carbonation. Based on these results, a two-stage reactor consisting of a high and a low fluid-flux chamber is proposed for CO2 sequestration by steel slag carbonation, allowing dissolution of the slag and precipitation of calcium carbonate to occur within a single flow-through system.