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One hundred and eighty-six soil samples from Northwest Oregon were tested for arsenic content. The highest values measured were 13.9 ppm in the A horizon (site C4) and 20.4 ppm in the B horizon (Site P4). Arsenic was not detected in 28 A horizon samples and 23 B horizon samples. Data are grouped based on the age and rock type of underlying bedrock. Lithologic groups with six or more data points were compared statistically to ascertain if groups are distinct. Analysis of Variance (ANOVA) multiple comparison tests indicate that the arsenic content of the Marine Sediments and Sedimentary Rocks group samples is distinguishable from the Quaternary Basalts group in the A horizon and all other groups in the B horizon. Kruskal-Wallis multiple comparison tests indicate that the arsenic content of the Marine Sediments and Sedimentary Rocks group is distinguishable from the Quaternary Basalts, Quaternary/ Tertiary Sediments and Sedimentary Rocks and Volcanic Sediments groups in both the A and B soil horizons. The ANOVA and Kruskal-Wallis tests compared A and B horizon data by lithologic group. The ANOVA shows the Marine Sediments and Sedimentary Rocks group in the A horizon is distinct from the Quaternary Basalts in the A and B horizon. The Kruskal-Wallis test yielded the same result. Per the ANOVA, the Marine Sediments and Sedimentary Rocks in the B horizon are distinct from all other tested groups. The Kruskal-Wallis test shows the Marine Sediments and Sedimentary Rocks group in the B horizon as distinct from the Quaternary Basalts, Quaternary/ Tertiary Sediments, and Volcanic Sediments groups in the A and B horizon. A K-means cluster analysis was used to group all available data independent of underlying bedrock. Three, four, and five group analyses were conducted, and the results of these tests were compared to the data grouped by underlying rock type. No correlation between the groups resulting from the K-means cluster analysis and groups based on underlying lithology was found. This analysis supports the creation of a map distinguishing arsenic content in the soils above Marine Sediments and Sedimentary Rocks group units from arsenic content in all other tested lithologic groups. The mean and standard deviations of these groups (in ppm) are: A horizon: Marine Sediments (6.09 ±2.66); other groups (3.10 ±3.19); B horizon: Marine Sediments (10.26 ±4.65); other groups (3.13, ±2.52). This analysis indicates that geologic context must be taken into account when determining background levels of naturally occurring arsenic in soils.

This study examines the natural background concentrations of arsenic in the soils of southwest Oregon, using new samples in addition to data collected from previous theses (Khandoker, 1997 and Douglas, 1999). The original 213 samples were run by ICP-AES with a reporting limit of 20 ppm, and only three samples had detected values. The original samples were tested again (2013) at a lower reporting limit of 0.2 ppm by ICP-MS, as were 42 new samples (2013), to better ascertain the natural levels of arsenic in undisturbed soils. The aim is to add to the existing DEQ data set, which has been used to establish new regulatory levels based on natural levels in the environment that are both safer and more economically viable than the former risk-based remediation levels (DEQ, 2013). The maximum and mean concentrations, respectively, for each province (with high formation map unit) are 85.4 and 21.99 ppm for South Willamette Valley (Tfee), 45.4 and 5.42 ppm for the Klamath Mountains (Jub), 11.9 and 2.76 ppm for the Cascade Range (Tbaa), 10.6 and 5.15 ppm for the Coast Range (Ty), 2.32 and 1.29 ppm for the Basin and Range (Qba) and 1.5 and 1.20 ppm for the High Lava Plains (Tmv). In addition, the distribution and variance of arsenic in the A and B soil horizons is assessed in this study by comparing deviation at a single site, and also by comparing A and B horizons of 119 PSU sites. One of 18 new sites sampled for this study (distinguished with the HH prefix), site HH11, was randomly chosen to evaluate differences at a single location. Site HH11 is an Inceptisol soil above volcanic rock (KJdv map unit) located at 275 meters elevation in Douglas County within the Klamath province. Five samples were taken from the A and from the B horizons at site HH11. The means and standard deviations were 3.74 ± 0.44 for the A horizon and 4.53 ± 0.39 for the B horizon. The consistency and low deviation within each horizon indicate that a single sample within a horizon is a good representative of that horizon and supports the field methodology used in this study of taking only one sample in the A horizon and one sample in the B horizon. Wilcoxon Rank-Sum test determined that A and B horizons for the 119 sites that had data for both the A and B horizons were not statistically different (p-value 0.76). Arsenic concentration is not associated with a particular horizon for these sites. However, differentiation between soil horizons increases with age (Birkeland, 1999), as does accumulation of the iron oxides and sulfide minerals on clay surfaces (McLaren et al., 2006) which concentrate in the B horizon. These associations warrant further study to see how they relate to arsenic level, soil development and age in Oregon soils. Lastly, this study statistically examines six potentially important environmental predictors of naturally occurring arsenic in southwestern Oregon: site elevation, geomorphic province, mapped rock type and age, and sample soil order and color (redness). A Classification and Regression Tree Model (CART) determined soil order, elevation and rock type to be of significant importance in determining arsenic concentrations in the natural environment. According to the regression tree, arsenic concentrations are greater within Alfisol and Ultisol/Alfisol and Vertisol soil orders, at lower elevations below 1,207 meters, and within soils from sedimentary, mixed volcanic/sedimentary and unconsolidated rock types.

Volcanic tuffs and tuffaceous sediments are frequently associated with elevated As groundwater concentrations even though their bulk As contents (~ 5 mg kg-1; Savoie, 2013) are only marginally greater than the average crustal abundance of 4.8 mg g-1 (Rudnick & Gao, 2003). Thus, As mobilization must be facilitated by conditions particular to these rocks. Alkaline desorption, anionic competition, reactive glass dissolution, and reductive dissolution of iron oxides are proposed processes of As release from volcanic rocks. Geogenic As contamination of groundwater in the southern Willamette Valley in western Oregon has been well-documented since the early 1960s, and previous studies have identified the Little Butte Volcanics Series and Fisher and Eugene Formations as the source of As contamination. This study examines 19 samples from 10 units of ash flow tuffs and tuffaceous sediments within the Fisher Formation and Little Butte Volcanics Series, representing a range of weathering and devitrification, to determine conditions of mobilization and mineralogical constraints that control As release into solution. Leachate studies were conducted over a range of pH from 7 to 11, phosphate concentrations from 10 μM to 100 mM, and in time series from 4 to 196 hours. Results demonstrate that silicic volcanic tuffs are capable of mobilizing As in concentrations above regulatory limits at pH conditions produced naturally by the tuffs (pH 8-9) or with moderate concentrations of P (10-100 μM). Alteration products, e.g. zeolites and clays, appear to be the primary host phases for mobile As. Samples that do not contain these alteration products tend to produce concentrations of As well below regulatory limits and often below the instrument detection limits of this study. The type of alteration may influence As mobilization: tuffs containing more clays tend to mobilize As through surficial desorption, and tuffs containing more zeolites tend to mobilize As by dissolution or formation of colloids. Additionally, one volcaniclastic sample demonstrates that extremely elevated concentrations of As, up to 1000 μg/L are possible as a result of oxidative dissolution of As-bearing sulfide phases.

This project examines arsenic in plants growing near closed or reclaimed gold mines located in the traditional territories of two Yukon First Nations. A total of 238 soil and plant samples (comprising 9 different species) were collected from Mt. Nansen, Arctic Gold and Silver, and Venus Mine tailing properties. At each property, samples were collected near the suspected point source of contamination, approximately 1 -3 km away, and from background sites. Species were chosen for their ethnobotanical significance to the Little Salmon/Carmacks and the Carcross/Tagish First Nations, based on interviews with Elders and other knowledgeable people. Total and inorganic arsenic concentrations were determined using ICP-MS and AAS instrumentation, and organic arsenic concentrations were calculated from the difference. Uptake of arsenic by plants was low compared to soil arsenic concentrations. In both plants and soil, the arsenic form was predominantly inorganic. Concentrations in berries at all three sites were low or undetectable, and are therefore considered safe to eat under Health Canada tolerable daily intake guidelines for inorganic arsenic. At Mt. Nansen, the lichen "caribou moss" (Cetraria/Cladina spp.), Bolete mushrooms (Leccinum spp.), and the medicinal shrubs willow (Salix spp.) and Labrador tea (Ledum groenlandicum/L. decumbens spp.) had high mean arsenic concentrations around point sources or at sites up to 1.5 km away. These localized high concentrations will not likely affect foraging animals, given their constant movement. However, Carmacks residents could avoid gathering all species with elevated arsenic around the Mt. Nansen mining property until reclamation is complete.

This project examines arsenic in plants growing near closed or reclaimed gold mines located in the traditional territories of two Yukon First Nations. A total of 238 soil and plant samples (comprising 9 different species) were collected from Mt. Nansen, Arctic Gold and Silver, and Venus Mine tailing properties. At each property, samples were collected near the suspected point source of contamination, approximately 1 -3 km away, and from background sites. Species were chosen for their ethnobotanical significance to the Little Salmon/Carmacks and the Carcross/Tagish First Nations, based on interviews with Elders and other knowledgeable people. Total and inorganic arsenic concentrations were determined using ICP-MS and AAS instrumentation, and organic arsenic concentrations were calculated from the difference. Uptake of arsenic by plants was low compared to soil arsenic concentrations. In both plants and soil, the arsenic form was predominantly inorganic. Concentrations in berries at all three sites were low or undetectable, and are therefore considered safe to eat under Health Canada tolerable daily intake guidelines for inorganic arsenic. At Mt. Nansen, the lichen "caribou moss" (Cetraria/Cladina spp.), Bolete mushrooms (Leccinum spp.), and the medicinal shrubs willow (Salix spp.) and Labrador tea (Ledum groenlandicum/L. decumbens spp.) had high mean arsenic concentrations around point sources or at sites up to 1.5 km away. These localized high concentrations will not likely affect foraging animals, given their constant movement. However, Carmacks residents could avoid gathering all species with elevated arsenic around the Mt. Nansen mining property until reclamation is complete. / Arts, Faculty of / Geography, Department of / Graduate