Structure of Fe(III) precipitates generated by Fe(0) electrocoagulation in the presence of groundwater ions
Abstract
Electrocoagulation (EC) using Fe(0) electrodes is an inexpensive and efficient technology capable of removing a variety of contaminants from water supplies. Because of its ease of use and modest electricity and Fe(0) requirements, EC has potential as an arsenic-removal technology for rural South Asia, where millions drink groundwater contaminated by arsenic. In EC, a small external voltage applied to a sacrificial Fe(0) anode in contact with an electrolyte (e.g. pumped groundwater containing arsenic) promotes the oxidative dissolution of Fe ions, which polymerize and create reactive hydrous ferric oxides (HFO) in-situ with a high affinity for binding contaminants. The chemical composition of the electrolyte influences EC performance. For example, major inorganic ions present in groundwater (e.g. Ca, Mg, P, As(V), Si) alter the pathway by which FeO6 oligomers polymerize to form crystalline Fe (oxyhydr)oxide minerals. Because the precipitate structure largely determines properties that govern the efficiency of EC systems (e.g. precipitate reactivity and colloidal stability), it is essential to understand the individual and interdependent structural effects of common groundwater ions. In this work, we integrate Fe K-edge EXAFS spectroscopy with the Pair Distribution Function (PDF) technique to create a detailed description of EC precipitate structure as a function of electrolyte chemistry. EC precipitate samples were generated in a range of individual and combined concentrations of Ca, Mg, P, As(V), and Si, encompassing most of the typical levels found in natural groundwater. Combining complementary EXAFS and PDF techniques with batch uptake experiments and general chemical reasoning, we obtain structural representations of EC precipitates that are inaccessible with any single characterization technique. Our results indicate that the presence of As(V), P, and Si oxyanions promote the formation of nanoscale material bearing similar, but not identical, intermediate-ranged atomic pair correlations as 2-line ferrihydrite (2LFH), rather than lepidocrocite (Lp) which is generated in an NaCl electrolyte. However, when Ca or Mg is added to oxyanion electrolytes, Fe-Fe polymerization and particle size both tend to increase and a Lp-like material with characteristic Fe-O and Fe-Fe pair correlations is once again favored. The presence of either Ca or Mg also enhances the removal P, As(V), and to a lesser extent, Si per mass of Fe. The analysis from EXAFS and PDF spectra provide new insights into the polyhedral connectivity of nanoscale oxyanion-bearing HFO formed under a wide range of chemical conditions, improving predictions of EC performance in the field and allowing for knowledge-based improvements in the design of future EC systems. Our PDF data also show that the most disordered EC precipitate samples (formed at high oxyanion/Fe ratios) all share a similar "backbone" of 3-4 peaks beyond the first 4 Å, regardless of the oxyanion present during synthesis. Using 2LFH as a reference, we index all atomic pair correlations throughout the coherently scattering structure of our disordered samples.
- Publication:
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AGU Fall Meeting Abstracts
- Pub Date:
- December 2012
- Bibcode:
- 2012AGUFM.B53D0694V
- Keywords:
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- 0496 BIOGEOSCIENCES / Water quality;
- 1042 GEOCHEMISTRY / Mineral and crystal chemistry;
- 1806 HYDROLOGY / Chemistry of fresh water