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Water Purification and Electrochemical Oxidation - Meeting Different Targets with BDD and MMO Anodes

MetadataDetails
Publication Date2022-10-27
JournalEnvironments
AuthorsMonika R. Snowdon, Shasvat Rathod, Azar Fattahi, Abrar Khan, Leslie M. Bragg
InstitutionsUniversity of Waterloo, Harvard University
Citations13
AnalysisFull AI Review Included
  • Core Objective: Comparative assessment of Boron-doped Diamond (BDD) and Mixed-Metal Oxide (MMO) anodes for electrochemical oxidation (EO) of Natural Organic Matter (NOM) in standardized Suwannee River water.
  • Performance Comparison: BDD electrodes demonstrated higher NOM oxidation efficiency and greater consistency across varying pH (6.5 and 8.5) and current densities (10 and 20 mA cm-2) compared to MMO.
  • Optimal BDD Performance: The BDD-SS configuration achieved 40.2% TOC removal and 75.4% COD removal at the highest tested parameters (pH 8.5, 20 mA cm-2).
  • Optimal MMO Performance: MMO-SS achieved the highest overall removal metrics (65.8% TOC, 91.6% COD) but only at the lowest tested parameters (pH 6.5, 10 mA cm-2), showing reduced efficiency at higher pH/current.
  • Cost-Effectiveness: BDD-SS exhibited the lowest Specific Energy Consumption (Esp) at 4.4 x 103 kWh kg COD-1 (20 mA cm-2, pH 8.5), confirming BDD’s superior cost-efficiency under strong operating conditions.
  • Mechanism Insight: BDD’s non-active surface favors the generation of weakly adsorbed hydroxyl radicals (‱OH), leading to effective mineralization and better breakdown of aromatic NOM structures (lower SUVA increase).
  • Conclusion for Engineers: BDD anodes are recommended for surface water pre-treatment, especially where high current densities or fluctuating pH levels are expected, due to their stability and lower long-term energy consumption.
ParameterValueUnitContext
Anode Materials TestedBDD, MMO (Ti-based)N/AComparative EO study
Cathode Materials TestedBDD, Stainless Steel (SS)N/AElectrode configurations
Initial pH Levels Tested6.5, 8.5N/AMimicking natural water alkalinity
Current Densities (i)10, 20mA cm-2Applied operational parameters
Electrode Surface Area10 x 10 x 1mmAll electrodes
Electrolysis Time120minMaximum treatment duration
Initial TOC (pH 8.5)7.03mg L-1Standardized water matrix
Initial COD (Theoretical)21.21mg L-1Calculated ThOD
Initial COD (Measured PeCOD)18mg L-1Measured value (15% lower than ThOD)
Highest TOC Removal65.8%MMO-SS, pH 6.5, 10 mA cm-2
Highest COD Removal91.6%MMO-SS, pH 6.5, 10 mA cm-2
BDD Max COD Removal75.4%BDD-SS, pH 8.5, 20 mA cm-2
Lowest Specific Energy Consumption (Esp)1.5 x 103kWh kg COD-1BDD-SS, pH 8.5, 10 mA cm-2
Lowest Esp (High Current)4.4 x 103kWh kg COD-1BDD-SS, pH 8.5, 20 mA cm-2
BDD COD/TOC Ratio (Best)0.55 ± 0.4N/ABDD-SS, pH 6.5, 20 mA cm-2
MMO COD/TOC Ratio (Best)0.33 ± 0.3N/AMMO-SS, pH 6.5, 10 mA cm-2
  1. Water Matrix Standardization: Synthetic water was prepared using Suwannee River NOM (reference standard) and specific salts (Table 2) to control the initial pH at two extremes (6.5 and 8.5) representative of natural water alkalinity.
  2. Electrode Configuration: Three two-electrode batch systems were tested: BDD anode/BDD cathode (BDD-BDD), BDD anode/Stainless Steel cathode (BDD-SS), and MMO anode/Stainless Steel cathode (MMO-SS).
  3. Electrolysis Operation: 300 mL samples were treated in a batch reactor under constant current densities (10 or 20 mA cm-2) for 120 minutes, with a 30-minute equilibration period prior to treatment.
  4. Particulate Removal: All treated water samples were filtered using a 0.45 ”m polyethersulfone (PES) membrane to remove particulate matter and agglomerates before analysis.
  5. Organic Matter Quantification: NOM degradation was tracked using four surrogate parameters:
    • TOC: Measured via 680 °C combustion catalytic oxidation (Shimadzu TOC-L).
    • COD: Measured via photoelectrochemical oxygen demand (PeCOD© Analyzer).
    • UV254: Measured via fluorescence plate reader to quantify aromatic/unsaturated carbon bonds.
    • SUVA: Calculated by normalizing UV254 by Dissolved Organic Carbon (DOC) to indicate aromaticity changes.
  6. Energy Efficiency Calculation: Specific Energy Consumption (Esp) was determined using the formula: Esp = (103 * U * I * t) / ((COD0 - CODt) * V), where U is the average cell voltage and V is the water volume.
  • Drinking Water Pre-treatment: Utilizing BDD anodes to effectively degrade NOM precursors, thereby minimizing the formation of carcinogenic disinfection by-products (DBPs) like trihalomethanes (THMs) and haloacetic acids (HAAs) during subsequent chlorination.
  • Industrial Wastewater Treatment: Application of BDD EO for the mineralization of recalcitrant organic pollutants (e.g., dyes, pharmaceuticals, landfill leachate) that resist conventional biological or chemical treatments.
  • Water Reclamation and Reuse: Employing BDD systems for robust, high-efficiency removal of complex organic loads in municipal and industrial reuse cycles, ensuring high water quality standards.
  • Advanced Oxidation Processes (AOP): Integration of BDD electrodes into AOP systems where high overpotential and strong hydroxyl radical generation are required for non-selective oxidation of stable organic molecules.
  • Electrode Manufacturing: The study supports the commercial viability of BDD electrodes (fabricated via CVD) as a stable, low-capacitance alternative to traditional MMO anodes, particularly for systems requiring long operational life and resistance to corrosion.
View Original Abstract

The complex composition of natural organic matter (NOM) can affect drinking water treatment processes, leading to perceptible and undesired taste, color and odor, and bacterial growth. Further, current treatments tackling NOM can generate carcinogenic by-products. In contrast, promising substitutes such as electrochemical methods including electrooxidation (EO) have shown safer humic acid and algae degradation, but a formal comparison between EO methods has been lacking. In this study, we compared the Boron-doped diamond (BDD) electrode electrolysis performance for Suwannee River NOM degradation using mixed-metal oxide (MMO) anodes under different pH (6.5 and 8.5) representative of the high and low ranges for acidity and alkalinity in wastewater and applied two different current densities (10 and 20 mA cm−2). BDD anodes were combined with either BDD cathodes or stainless steel (SS) cathodes. To characterize NOM, we used (a) total organic compound (TOC), (b) chemical oxygen demand (COD), (c) specific ultraviolet absorbance (SUVA), and (d) specific energy consumption. We observed that NOM degradation differed upon operative parameters on these two electrodes. BDD electrodes performed better than MMO under stronger current density and higher pH and proved to be more cost-effective. BDD-SS electrodes showed the lowest energy consumption at 4.4 × 103 kWh kg COD−1. while obtaining a TOC removal of 40.2%, COD of 75.4% and SUVA of 3.4 at higher pH and current. On the contrary, MMO produced lower TOC, COD and SUVA at the lower pH. BDD electrodes can be used in surface water as a pre-treatment in combination with some other purification technologies to remove organic contaminants.

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