Robert B. Perkins

Date of Award

Spring 7-22-2013

Document Type


Degree Name

Master of Science (M.S.) in Geology



Physical Description

1 online resource (xi, 142 pages)


Volcanic ash -- Composition -- Environmental aspects, Volcanic tuff -- Composition -- Environmental aspects, Arsenic -- Environmental aspects, Groundwater -- Pollution




Volcanic rocks typically have only low to moderate arsenic concentrations, none-the-less, elevated levels of arsenic in ground waters have been associated with pyroclastic and volcaniclastic rocks and sediments in many parts of the world. The potential for arsenic leaching from these deposits is particularly problematic as they often comprise important water-bearing units in volcanic terrains. However, the role that chemical and mineralogical variations play in controlling the occurrence and mobility of arsenic from pyroclastic rocks is largely unexplored.

This study uses chemical and X-ray diffraction data to characterize and classify 49 samples of ash-flow tuffs, and 11 samples of tuffaceous sediments. The samples exhibit a range of devitrification and chemical weathering. Total and partial digestion, and water extractions of samples are used to determine the total, environmentally available, and readily leachable fractions of arsenic present in all tuff samples. Leaching experiments were also performed with buffered solutions to determine the influence of elevated pH levels on arsenic mobility.

The 49 tuff samples have a mean arsenic content of 7.5 mg kg-1, a geometric mean arsenic content of 4.8 mg kg-1, a median arsenic content of 5.2 mg kg-1, and a maximum arsenic concentration of 81 mg kg-1. The mean and median values are 2.8 - 4.4x the average crustal abundance of 1.7 mg kg-1 (Wedepohl, 1995), and consistent with previously reported values for volcanic glasses and felsic volcanic rocks (Onishi and Sandell, 1955; Wedepohl, 1995), although the maximum arsenic content is higher than previously reported (e.g., Casentini et al., 2010; Fiantis et al., 2010; Nobel et al., 2004). In addition, the arsenic concentrations of tuffs were found to be highly heterogenous, both between and within individual units, and in some cases, individual outcrops.

Results of whole rock and leachate analyses indicate that there is no significant difference in the total arsenic content of tuffs as a result of devitrification or weathering, but both devitrified and weathered tuffs contain higher levels of environmentally available arsenic than unweathered glassy tuffs. Glassy tuffs did not produce any readily leachable arsenic, while individual devitrified and weathered tuffs both generated aqueous concentrations that exceeded regulatory limits after 18 hours. Leaching of weathered tuffs produced higher levels of arsenic at high (~9-11) pH than in tests conducted at circum-neutral pH. Devitrified and glassy tuffs showed no increase in leachable arsenic with increasing pH.

The results of this study indicate that devitrification and weathering processes determine the host phases, degree of adsorption, and overall mobility of arsenic from ash-flow tuffs. Tuffs that have undergone different types of alteration are likely to have different host phases of arsenic, and different mechanisms that mobilize arsenic into the environment. Potential host phases and mobility mechanisms are discussed, and a conceptual model of arsenic behavior in ash-flow tuffs is proposed.

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