Arsenic Release from Chlorine Promoted Oxidation of Pyrite in the St. Peter Sandstone Aquifer, Eastern Wisconsin

High arsenic concentrations (>100 ppb) have been measured in wells completed in the Ordovician St. Peter sandstone aquifer of eastern Wisconsin. The primary source of arsenic is As-bearing sulfide minerals within the aquifer. There is concern that periodic disinfection of wells by chlorination may facilitate arsenic release to groundwater by increasing the rate of sulfide mineral oxidation. Current guidance from the Wisconsin Department of Natural Resources recommends a "low-dose" treatment of 20% of the chlorine strength and 10% of the of the contact time of chlorine treatments used in non-arsenic impacted wells for well disinfection and biofilm removal. In order to provide information pertaining to WDNR's recommendations, St. Peter sulfide minerals were reacted with a range of chlorine "shock-treatments" similar to those occurring in wells. This study focuses on abiotic processes that mobilize arsenic from the solid phase during controlled exposure to chlorinated solutions. Thin sections were made from aquifer material collected at Leonard's Michael quarry, located in Winnebago County, Wisconsin. Bulk arsenic content of this material was measured as 674 ppm. Quantitative EPMA analysis shows As zoning in pyrite grains with concentrations up to 1 wt. % As. After mineral characterization, the thin sections were exposed to solutions of 60 mg/L "free chlorine," 1200 mg/L "free chlorine," and nanopure water (control) at pH 7.0 and pH 8.5 for 24 hours. Thin sections were then analyzed to measure changes in the pyrite surfaces. For solution experiments, aquifer material was crushed to between 250 μm and 355 μm mesh sizes (S.A. ~ 50 cm2/g – 60 cm2/g, Foust et al. 1980) and reacted under the same conditions as the thin sections in a batch reactor. Solution samples were collected periodically during the 24 hour exposure and analyzed for arsenic, iron, and sulfate ion. Pyrite oxidation is shown to dramatically increase with increasing chlorine concentrations as shown by measurements of released sulfate ion, used here as the reaction progress variable. EPMA maps also reveal complete oxidation of pyrite cements to Fe-oxyhydroxides at 1200 mg/L "free chlorine" and pH 7.0. This behavior does not occur at lower concentrations or higher pH. Arsenic release to solution does not appear to be directly correlated to increasing chlorine concentrations, but is governed by Fe-oxyhydroxide nucleation, which inhibits the release of dissolved arsenic at higher concentrations of chlorine.

Name thesis:degree_name

Master of Science

Level thesis:degree_level

masters

Discipline thesis:degree_discipline

Geosciences

Department dc:contributor.department

Geosciences

Grantor dc:publisher

Virginia Tech

Year dc:date.issued

2008

Author dc:creator

• West, Nicole Renee

Chair dc:contributor.committeechair

• Schreiber, Madeline E.

Committee members dc:contributor.committeemember

• Rimstidt, J. Donald
• Chermak, John A.

• Arsenic
• Pyrite
• Chlorination
• St. Peter Sandstone
• Fox River Valley

Statement dc:rights

• In Copyright

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Dc Identifier Other

etd-05092008-165817

OAI identifier oai:identifier

oai:vtechworks.lib.vt.edu:10919/32451