Electrochemical oxidation of reverse osmosis concentrate on mixed metal oxide (MMO) titanium coated electrodes

Reverse osmosis (RO) membranes have been successfully applied around the world for wastewater reuse applications. However, RO is a physical separation process, and besides the clean water stream (permeate) a reverse osmosis concentrate (ROC) is produced, usually representing 15-25% of the feed water flow and containing the organic and inorganic contaminants at higher concentrations. In this study, electrochemical oxidation was investigated for the treatment of ROC generated during the reclamation of municipal wastewater effluent. Using laboratory-scale two-compartment electrochemical systems, five electrode materials (i.e. titanium coated with IrO₂-Ta₂O₅, RuO₂-IrO₂, Pt-IrO₂, PbO₂, and SnO₂-Sb) were tested as anodes in batch mode experiments, using ROC from an advanced water treatment plant. The best oxidation performance was observed for Ti/Pt-IrO₂ anodes, followed by the Ti/SnO₂-Sb and Ti/PbO₂ anodes. The effectiveness of the treatment appears to correlate with the formation of oxidants such as active chlorine (i.e. Cl₂/HClO/ClO⁻). As a result, electro-generated chlorine led to the abundant formation of harmful by-products such as trihalomethanes (THMs) and haloacetic acids (HAAs), particularly at Ti/SnO₂-Sb and Ti/Pt-IrO₂ anodes. The highest concentration of total HAAs (i.e. 2.7 mg L⁻¹) was measured for the Ti/SnO₂-Sb electrode, after 0.55 Ah L⁻¹ of supplied specific electrical charge. Irrespective of the used material, electrochemical oxidation of ROC needs to be complemented by a polishing treatment to alleviate the release of halogenated by-products.     

Comparison of the removal of hydrophobic trace organic contaminants by forward osmosis and reverse osmosis

We compared the rejection behaviours of three hydrophobic trace organic contaminants, bisphenol A, triclosan and diclofenac, in forward osmosis (FO) and reverse osmosis (RO). Using erythritol, xylose and glucose as inert reference organic solutes and the membrane pore transport model, the mean effective pore size of a commercial cellulose-based FO membrane was estimated to be 0.74 nm. When NaCl was used as the draw solute, at the same water permeate flux of 5.4 L/m² h (or 1.5 μm/s), the adsorption of all three compounds to the membrane in the FO mode was consistently lower than that in the RO mode. Rejection of bisphenol A and diclofenac were higher in the FO mode compared to that in the RO mode. Because the molecular width of triclosan was larger than the estimated mean effective membrane pore size, triclosan was completely rejected by the membrane and negligent difference between the FO and RO modes could be observed. The difference in the separation behaviour of these hydrophobic trace organics in the FO (using NaCl the draw solute) and RO modes could be explained by the phenomenon of retarded forward diffusion of solutes. The reverse salt flux of NaCl hinders the pore diffusion and subsequent adsorption of the trace organic compounds within the membrane. The retarded forward diffusion effect was not observed when MgSO₄ and glucose were used as the draw solutes. The reverse flux of both MgSO₄ and glucose was negligible and thus both adsorption and rejection of BPA in the FO mode were identical to those in the RO mode.     

Advanced treatment of the reverse osmosis concentrate produced during reclamation of municipal wastewater

The work investigated the treatment of the concentrate produced from the reverse osmosis treatment of an MBR effluent. Two conventional chemical processes, coagulation and activated carbon adsorption, and three advanced oxidation processes (electrochemical treatment, photocatalysis and sonolysis) were applied. Coagulation with alum gave dissolved organic carbon (DOC) removals up to 42%, while FeCl(3) achieved higher removals (52%) at lower molar doses. Adsorption with granular activated carbon showed the highest DOC removals up to 91.3% for 5 g/L. The adsorption isotherm was linear with a non-adsorbable organic fraction of around 1.2 mg/L DOC. The three oxidation methods employed, electrolytic oxidation over a boron-doped diamond electrode, UVA/TiO2 photocatalysis and sonolysis at 80 kHz, showed similar behavior: during the first few minutes of treatment there was a moderate removal of DOC followed by further oxidation at a very slow rate. Electrolytic oxidation was capable of removing up to 36% at 17.8A after 30 min of treatment, sonolysis removed up to 34% at 135W after 60 min, while photocatalysis was capable of removing up to 50% at 60 min.     

Effect of ozone exposure on the oxidation of trace organic contaminants in wastewater

Three tertiary-treated wastewater effluents were evaluated to determine the impact of wastewater quality (i.e. effluent organic matter (EfOM), nitrite, and alkalinity) on ozone (O₃) decomposition and subsequent removal of 31 organic contaminants including endocrine disrupting compounds, pharmaceuticals, and personal care products. The O₃ dose was normalized based upon total organic carbon (TOC) and nitrite to allow comparison between the different wastewaters with respect to O₃ decomposition. EfOM with higher molecular weight components underwent greater transformation, which corresponded to increased O₃ decomposition when compared on a TOC basis. Hydroxyl radical (OH) exposure, measured by parachlorobenzoic acid (pCBA), showed that limited OH was available for contaminant destruction during the initial stage of O₃ decomposition (t < 30 s) due to the effect of the scavenging by the water quality. Advanced oxidation using O₃ and hydrogen peroxide did not increase the net production of OH compared to O₃ under the conditions studied. EfOM reactivity impacted the removal of trace contaminants when evaluated based on the O₃:TOC ratio. Trace contaminants with second order reaction rate constants with O₃ (kO3) > 10⁵ M⁻¹ s⁻¹ and OH (k_OH) > 10⁹ M⁻¹ s⁻¹, including carbamazepine, diclofenac, naproxen, sulfamethoxazole, and triclosan, were >95% removed independent of water quality when the O₃ exposure () was measurable (0-0.8 mg min/L). O₃ exposure would be a conservative surrogate to assess the removal of trace contaminants that are fast-reacting with O₃. Removal of contaminants with and k_OH > 10⁹ M⁻¹ s⁻¹, including atrazine, iopromide, diazepam, and ibuprofen, varied when O₃ exposure could not be measured, and appeared to be dependent upon the compound specific k_OH. Atrazine, diazepam, ibuprofen and iopromide provided excellent linear correlation with pCBA (R² > 0.86) making them good indicators of OH availability.     

Characterisation and removal of recalcitrants in reverse osmosis concentrates from water reclamation plants

Water reclamation plants frequently utilise reverse osmosis (RO), generating a concentrated reject stream as a by-product. The concentrate stream contains salts, and dissolved organic compounds, which are recalcitrant to biological treatment, and may have an environmental impact due to colour and embedded nitrogen. In this study, we characterise organic compounds in RO concentrates (ROC) and treated ROC (by coagulation, adsorption, and advanced oxidation) from two full-scale plants, assessing the diversity and treatability of colour and organic compounds containing nitrogen. One of the plants was from a coastal catchment, while the other was inland. Stirred cell membrane fractionation was applied to fractionate the treated ROC, and untreated ROC along with chemical analysis (DOC, DON, COD), colour, and fluorescence excitation-emission matrix (EEM) scans to characterise changes within each fraction. In both streams, the largest fraction contained <1 kDa molecules which were small humic substances, fulvic acids and soluble microbial products (SMPs), as indicated by EEM. Under optimal treatment conditions, alum preferentially removed >10 kDa molecules, with 17-34% of organic compounds as COD. Iron coagulation affected a wider size range, with better removal of organics (41-49% as COD) at the same molar dosage. As with iron, adsorption reduced organics of a broader size range, including organic nitrogen (26-47%). Advanced oxidation (UV/H₂O₂) was superior for complete decolourisation and provided superior organics removal (50-55% as COD).     

Impact of salinity and pH on the UVC/H2O2 treatment of reverse osmosis concentrate produced from municipal wastewater reclamation

While reverse osmosis (RO) technology is playing an increasingly important role in the reclamation of municipal wastewater, safe disposal of the resulting RO concentrate (ROC), which can have high levels of effluent organic pollutants, remains a challenge to the water industry. The potential of UVC/H₂O₂ treatment for degrading the organic pollutants and increasing their biodegradability has been demonstrated in several studies, and in this work the impact of the water quality variables pH, salinity and initial organic concentration on the UVC/H₂O₂ (3 mM) treatment of a municipal ROC was investigated. The reduction in chemical oxygen demand and dissolved organic carbon was markedly faster and greater under acidic conditions, and the treatment performance was apparently not affected by salinity as increasing the ROC salinity 4-fold had only minimal impact on organics reduction. The biodegradability of the ROC (as indicated by biodegradable dissolved organic carbon (BDOC) level) was at least doubled after 2 h UVC/H₂O₂ treatment under various reaction conditions. However, the production of biodegradable intermediates was limited after 30 min treatment, which was associated with the depletion of the conjugated compounds. Overall, more than 80% of the DOC was removed after 2 h UVC/3 mM H₂O₂ treatment followed by biological treatment (BDOC test) for the ROC at pH 4-8.5 and electrical conductivity up to 11.16 mS/cm. However, shorter UV irradiation time gave markedly higher energy efficiency (e.g., EE/O 50 kWh/m³ at 30 min (63% DOC removal) cf. 112 kWh/m³ at 2 h). No toxicity was detected for the treated ROC using Microtox^® tests. Although the trihalomethane formation potential increased after the UVC/H₂O₂ treatment, it was reduced to below that of the raw ROC after the biological treatment.     

Effects of ozone and ozone/peroxide on trace organic contaminants and NDMA in drinking water and water reuse applications

An ozone and ozone/peroxide oxidation process was evaluated at pilot scale for trace organic contaminant (TOrC) mitigation and NDMA formation in both drinking water and water reuse applications. A reverse osmosis (RO) pilot was also evaluated as part of the water reuse treatment train. Ozone/peroxide showed lower electrical energy per order of removal (EEO) values for TOrCs in surface water treatment, but the addition of hydrogen peroxide increased EEO values during wastewater treatment. TOrC oxidation was correlated to changes in UV₂₅₄ absorbance and fluorescence offering a surrogate model for predicting contaminant removal. A decrease in N-nitrosodimethylamine (NDMA) formation potential (after chloramination) was observed after treatment with ozone and ozone/peroxide. However, during spiking experiments with surface water, ozone/peroxide achieved limited destruction of NDMA, while in wastewaters net direct formation of NDMA of 6-33 ng/L was observed after either ozone or ozone/peroxide treatment. Once formed during ozonation, NDMA passed through the subsequent RO membranes, which highlights the significance of the potential for direct NDMA formation during oxidation in reuse applications.     

Evaluation of UV/H2O2 treatment for the oxidation of pharmaceuticals in wastewater

Advanced oxidation treatment using low pressure UV light coupled with hydrogen peroxide (UV/H₂O₂) was evaluated for the oxidation of six pharmaceuticals in three wastewater effluents. The removal of these six pharmaceuticals (meprobamate, carbamazepine, dilantin, atenolol, primidone and trimethoprim) varied between no observed removal and >90%. The role of the water quality (i.e., alkalinity, nitrite, and specifically effluent organic matter (EfOM)) on hydroxyl radical (OH) exposure was evaluated and used to explain the differences in pharmaceutical removal between the three wastewaters. Results indicated that the efficacy of UV/H₂O₂ treatment for the removal of pharmaceuticals from wastewater was a function of not only the concentration of EfOM but also its inherent reactivity towards OH. The removal of pharmaceuticals also correlated with reductions in ultraviolet absorbance at 254 nm (UV₂₅₄), which offers utilities a surrogate to assess pharmaceutical removal efficiency during UV/H₂O₂ treatment.     

Degradation of the antibiotic oxolinic acid by photocatalysis with TiO2 in suspension

In the work presented here, a photocatalytic system using titanium Degussa P-25 in suspension was used to evaluate the degradation of 20 mg L⁻¹ of antibiotic oxolinic acid (OA). The effects of catalyst load (0.2-1.5 g L⁻¹) and pH (7.5-11) were evaluated and optimized using the surface response methodology and the Pareto diagram. In the range of variables studied, low pH values and 1.0 g L⁻¹ of TiO₂ favoured the efficiency of the process. Under optimal conditions the evolution of the substrate, chemical oxygen demand, dissolved organic carbon, toxicity and antimicrobial activity on Escherichia coli cultures were evaluated. The results indicate that, under optimal conditions, after 30 min, the TiO₂ photocatalytic system is able to eliminate both the substrate and the antimicrobial activity, and to reduce the toxicity of the solution by 60%. However, at the same time, ∼53% of both initial DOC and COD remain in solution. Thus, the photocatalytical system is able to transform the target compound into more oxidized by-products without antimicrobial activity and with a low toxicity. The study of OA by-products using liquid chromatography coupled with mass spectrometry, as well as the evaluation of OA degradation in acetonitrile media as solvent or in the presence of isopropanol and iodide suggest that the reaction is initiated by the photo-Kolbe reaction. Adsorption isotherm experiments in the dark indicated that under pH 7.5, adsorption corresponded to the Langmuir adsorption model, indicating the dependence of the reaction on an initial adsorption step.