Identification and quantification of mineral precipitation in Fe0 filings from a column study

Thermogravimetric analysis (TGA) combined with X-ray diffraction (XRD) was used to identify mineral phases and determine corrosion rates of granular iron samples from a 2-yr field column study. Similar to other studies, goethite, magnetite, aragonite, and calcite were found to be the major precipitated minerals, with Fe2(OH)2CO3 and green rust as minor phases. Based on TGA-mass spectrometry (MS) analysis, Fe0 corrodes at rates of 0.5-6.1 mmol kg(-1) d(-1) in the high NO3- (up to 13.5 mM) groundwater; this rate is significantly higher than previously reported. Porosity reduction was 40.6%-45.1% for the inlet sand/Fe0 interface and 7.4%-25.6% for effluent samples of two test columns. Normalized for treatment volumes, porosity loss values are consistent with studies that use high levels of SO4(2-) but are higher than those using low levels of corrosive species. Aqueous mass balance calculations yield corrosion rates similar to the TGA-MS method, providing an alternative to coring and mineralogical analysis. A severely corroded iron sample from the column simulating a 17-yr treatment throughput showed >75% porosity loss. Extensive porosity loss due to high levels of corrosive species in groundwater will have significant impact on long-term performance of permeable reactive barriers.