Jelena Radjenović

Electrochemical processes have been extensively investigated for the removal of a range of organic and inorganic contaminants. The great majority of these studies were conducted using nitrate-, perchlorate-, sulfate-, and chloride-based electrolyte solutions. In actual treatment applications, organic and inorganic constituents may have substantial effects on the performance of electrochemical treatment. In particular, the outcome of electrochemical oxidation will depend on the concentration of chloride and bromide. Formation of chlorate, perchlorate, chlorinated, and brominated organics may compromise the quality of the treated effluent. A critical review of recent research identifies future opportunities and research needed to overcome major challenges that currently limit the application of electrochemical water treatment systems for industrial and municipal water and wastewater treatment. Given the increasing interest in decentralized wastewater treatment, applications of electrolytic systems for treatment of domestic wastewater, greywater, and source-separated urine are also included. To support future adoption of electrochemical treatment, new approaches are needed to minimize the formation of toxic byproducts and the loss of efficiency caused by mass transfer limitations and undesired side reactions. Prior to realizing these improvements, recognition of the situations where these limitations pose potential health risks is a necessary step in the design and operation of electrochemical treatment systems.

Much attention has recently been devoted to the life and behaviour of pharmaceuticals in the water cycle. In this study the behaviour of several pharmaceutical products in different therapeutic categories (analgesics and anti-inflammatory drugs, lipid regulators, antibiotics, etc.) was monitored during treatment of wastewater in a laboratory-scale membrane bioreactor (MBR). The results were compared with removal in a conventional activated-sludge (CAS) process in a wastewater-treatment facility. The performance of an MBR was monitored for approximately two months to investigate the long-term operational stability of the system and possible effects of solids retention time on the efficiency of removal of target compounds. Pharmaceuticals were, in general, removed to a greater extent by the MBR integrated system than during the CAS process. For most of the compounds investigated the performance of MBR treatment was better (removal rates >80%) and effluent concentrations of, e.g., diclofenac, ketoprofen, ranitidine, gemfibrozil, bezafibrate, pravastatin, and ofloxacin were steadier than for the conventional system. Occasionally removal efficiency was very similar, and high, for both treatments (e.g. for ibuprofen, naproxen, acetaminophen, paroxetine, and hydrochlorothiazide). The antiepileptic drug carbamazepine was the most persistent pharmaceutical and it passed through both the MBR and CAS systems untransformed. Because there was no washout of biomass from the reactor, high-quality effluent in terms of chemical oxygen demand (COD), ammonium content (N-NH(4)), total suspended solids (TSS), and total organic carbon (TOC) was obtained.

Solutions of sulfate have often been used as background electrolytes in the electrochemical degradation of contaminants and have been generally considered inert even when high-oxidation-power anodes such as boron-doped diamond (BDD) were employed. This study examines the role of sulfate by comparing electro-oxidation rates for seven persistent organic contaminants at BDD anodes in sulfate and inert nitrate anolytes. Sulfate yielded electro-oxidation rates 10-15 times higher for all target contaminants compared to the rates of nitrate anolyte. This electrochemical activation of sulfate was also observed at concentrations as low as 1.6 mM, which is relevant for many wastewaters. Electrolysis of diatrizoate in the presence of specific radical quenchers (tert-butanol and methanol) had a similar effect on electro-oxidation rates, illustrating a possible role of the hydroxyl radical ((•)OH) in the anodic formation of sulfate radical (SO4(•-)) species. The addition of 0.55 mM persulfate increased the electro-oxidation rate of diatrizoate in nitrate from 0.94 to 9.97 h(-1), suggesting a nonradical activation of persulfate. Overall findings indicate the formation of strong sulfate-derived oxidant species at BDD anodes when polarized at high potentials. This may have positive implications in the electro-oxidation of wastewaters containing sulfate. For example, the energy required for the 10-fold removal of diatrizoate was decreased from 45.6 to 2.44 kWh m(-3) by switching from nitrate to sulfate anolyte.