Assessing leached TOC, nutrients and phenols from peatland soils after lab-simulated wildfires: Implications to source water protection.

Pollutant leaching from wildfire-impacted peatland soils (peat) is well-known, but often underestimated when considering boreal ecosystem source water protection and when treating source waters to provide clean drinking water. Burning peat impacts its physical properties and chemical composition, yet the consequences of these transformations to source water quality through pollutant leaching has not been studied in detail. We combusted near-surface boreal peat under simulated peat smoldering conditions at two temperatures (250 °C and 300 °C) and quantified the concentrations of the leached carbon, nutrients and phenols from 5 g peat L-1 reverse osmosis (RO) water suspensions over a 2-day leaching period. For the conditions studied, measured water quality parameters exceeded US surface water guidelines and even exceeded EU and Canadian wastewater/sewer discharge limits including chemical oxygen demand (COD) (125 mg/L), total nitrogen (TN) (15 mg/L), and total phosphorus (TP) (2 mg/L). Phenols were close to or higher than the suggested water supply standard established by US EPA (1 mg/L). Leached carbon, nitrogen and phosphorus mainly came from the organic fraction of peats. Heating peats to 250 °C promoted the leaching of carbon-related pollutants, whereas heating to 300 °C enhanced the leaching of nutrients. Post-heated peats leached higher loads of pollutants in water than pre-heated peats, suggesting that fire-damaged boreal peats may be a critical but underappreciated source of water pollution. A simplified Partial Least Squares (PLS) model based on other easily measured parameters provided a simple method for determining the extent of COD and phenolic pollution in bulk water, relevant for water and wastewater treatment plants. Conclusions from this lab study indicate the need for field measurements of aquatic pollutants downstream of peatland watersheds post-fire as well as increased monitoring and treatment of potable water sources for leachable micropollutants in fire-dominated forested peatlands.

Mixed metal oxide anodes used for the electrochemical degradation of a real mixed industrial wastewater.

Mixed industrial wastewaters are often highly contaminated with heavy metals and organic pollutants. Treating these mixed wastewaters requires many stagewise unit operations. Our work investigates using an electrochemical oxidation-in-situ coagulation (ECO-IC) process as a pre-treatment step toward the efficient treatment of real mixed industrial wastewater rich with heavy metals and organic contaminants. The process degraded organic contaminants in the wastewater via anodic electrochemical oxidation. Simultaneously, heavy metals were precipitated in the solution by coagulants (iron hydroxides) formed in-situ by cathode-generated hydroxyl ions reacting with the significant amounts of dissolved iron in the wastewater. IrO2-RuO2 mixed metal oxide anodes were identified as the best electrodes for organic compound degradation demonstrating 97% degradation of methyl orange (MO) as a model compound within 15 min. These anodes were used to treat real industrial wastewater produced from the industrial cleaning of train tanker cars transporting industrial solvents. The electrochemical treatment experiments resulted in a treated solution with a lower heavy metal content, achieving 96% reduction in Fe and 30% reduction in As content. Only moderate decreases in organic content were observed up to a maximum of 13% reduction in total organic carbon after 1 h of treatment. Electrochemical treatment of the mixed industrial wastewater produced greater effective diameter of the suspended particles and distinct sediment, liquid, and suspended foam phases that could be easily separated for further treatment. ECO-IC shows promise as an efficient and chemical-free method to coagulate heavy metals in real industrial wastewaters and could be an effective pre-treatment in their separation.

Simultaneous Dechlorination and Advanced Oxidation Using Electrically Conductive Carbon Nanotube Membranes.

Electrically conductive membranes have shown significant promise in combining conventional separations with in situ contaminant oxidation, but little has been done to consider chlorine removal. This study demonstrates the simultaneous chlorine removal and oxidation of organic compounds during filtration using an electrochemically assisted electrically conductive carbon nanotube (CNT) membrane. As much as 80% of chlorine was removed in the feed by CNT membranes at the initial phase of continuous filtration. The efficacy of these CNT membranes toward chlorine removal was dependent on the mass of CNTs within the membranes and the applied pressure to the membranes, indicating the central role of available CNT active sites and sufficient reaction time. Furthermore, the removal mechanism of chlorine by CNTs was revealed by studying the degradation of benzoic acid and cyclic voltammetry on the membrane surface. Reactive oxidants were generated by the reductive decomposition of chlorine through the catalytic interaction with CNTs. Subsequently, electrical potentials were applied to the CNT membrane surfaces during the filtration of chlorinated feed waters. The simultaneous decomposition of chlorine and oxidation of benzoic acid were significantly enhanced by applying a cathodic current to CNT membranes enabling continuous dechlorination. The cathodic current applied to CNT membranes is believed to regenerate CNT membranes by providing electrons for the reductive decomposition of chlorine. In situ chemical-free dechlorination coupled with membrane filtration offers great opportunity to reducing the environmental impact of desalination, while maximizing the lifetime of reverse osmosis membranes and demonstrating greener approaches available to industrial water treatment.

CNT-sorbents for heavy metals: Electrochemical regeneration and closed-loop recycling.

Heavy metal contamination of aquatic environments is a major concern. Carbon nanotubes (CNTs) are among the most effective adsorbents for heavy metal removal due. However, their high cost and their uncertain environmental impact necessitates a closed-loop process through sorbent regeneration and recycling for practical application. Our work demonstrates heavy metal adsorption by carboxylic acid-functionalized single-walled/double-walled carbon nanotubes (f-SW/DWCNTs) and their regeneration using electric fields. We follow a multi-step process: 1) copper in an aqueous solution is adsorbed onto the surface of f-SW/DWCNTs, 2) the copper-saturated f-SW/DWCNTs are filtered onto a microfiltration (MF) membrane, 3) the f-SW/DWCNT coated membrane is used as an anode in an electrochemical cell, 4) an applied electric field desorbs the metals from the CNTs into a concentrated waste, and 5) the CNTs are separated from the membrane, re-dispersed and reused in copper-contaminated water for successive adsorption. With an applied positive electric potential, we achieved ∼90 % desorption of Cu from f-SW/DWCNTs. We hypothesize that the electric field generated at the anode causes electrostatic repulsion between the anode and the electrostatically adsorbed heavy metal ions. The effect of applied voltages, electrode spacing and electrolyte conductivity on the desorption of Cu from CNTs was also investigated.

Defect engineering in 1D Ti-W oxide nanotube arrays and their correlated photoelectrochemical performance.

Understanding the nature of interfacial defects of materials is a critical undertaking for the design of high-performance hybrid electrodes for photocatalysis applications. Theoretical and computational endeavors to achieve this have touched boundaries far ahead of their experimental counterparts. However, to achieve any industrial benefit out of such studies, experimental validation needs to be systematically undertaken. In this sense, we present herein experimental insights into the synergistic relationship between the lattice position and oxidation state of tungsten ions inside a TiO2 lattice, and the respective nature of the created defect states. Consequently, a roadmap to tune the defect states in anodically-fabricated, ultrathin-walled W-doped TiO2 nanotubes is proposed. Annealing the nanotubes in different gas streams enabled the engineering of defects in such structures, as confirmed by XRD and XPS measurements. While annealing under hydrogen stream resulted in the formation of abundant Wn+ (n < 6) ions at the interstitial sites of the TiO2 lattice, oxygen- and air-annealing induced W6+ ions at substitutional sites. EIS and Mott-Schottky analyses indicated the formation of deep-natured trap states in the hydrogen-annealed samples, and predominantly shallow donating defect states in the oxygen- and air-annealed samples. Consequently, the photocatalytic performance of the latter was significantly higher than those of the hydrogen-annealed counterparts. Upon increasing the W content, photoelectrochemical performance deteriorated due to the formation of WO3 crystallites that hindered charge transfer through the photoanode, as evident from the structural and chemical characterization. To this end, this study validates the previous theoretical predictions on the detrimental effect of interstitial W ions. In addition, it sheds light on the importance of defect states and their nature for tuning the photoelectrochemical performance of the investigated materials.