Arsenic concentrations exceeding the U.S. Environmental Protection Agency (USEPA) current Maximum Contaminant Level (MCL) of 50 µg/L (micrograms per liter) are widespread in ground water in the Willamette Basin. The Oregon Water Resources Department and the U.S. Geological Survey began a cooperative study in the Willamette Basin in 1996. One goal of this study is to characterize the regional distribution of naturally occurring poor-quality ground water, such as ground water with high concentrations of arsenic. Characterization of the regional distribution of arsenic concentrations in the Willamette Basin will be useful to public health officials, water-resource managers, the medical community, and those using ground water for drinking and cooking.
The spatial distribution of arsenic concentrations in ground water of the Willamette Basin was assessed by combining historical data from 597 sites with data from 131 sites collected for this study. A total of 728 spatially distinct samples thus were available. Additional data also were collected to evaluate temporal variability of arsenic concentrations on a seasonal timescale. Samples were collected quarterly from 17 sites for 1 year for this purpose. Temporal variability was addressed for two reasons: First, characterization of temporal variability allowed evaluation of the acceptability of combining arsenic-concentration data collected during different seasons for determining the spatial distribution of arsenic concentrations. Second, knowledge of temporal variability will benefit well owners and water managers who require guidance on timing for sampling.
During the course of quarterly sampling, arsenic concentrations in water from many wells remained essentially constant, but variations of up to almost a factor of three were observed in other wells. No obvious correlation with season was apparent. Analytical accuracy, as determined from 11 standard reference samples submitted during the course of project work, generally was within ±10 percent, and always ±20 percent. Thus, analytical variability can only explain some of the observed temporal variability. One possible explanation for observed temporal variability in arsenic concentrations is that differences in the amount of pumpage prior to sampling may lead to variations in the amounts of water pumped from different sources (different aquifers or parts of aquifers), and thus, differences in water chemistry.
For a regional assessment of arsenic concentrations in ground water, where arsenic concentrations may vary in space by several orders of magnitude, the relatively smaller temporal variations such as those observed in the quarterly samples are not a significant limitation, and the aggregation of data collected at different times is justified. However, this conclusion may not necessarily apply to all investigations of arsenic concentrations in ground water. For some purposes, site-specific characterization may require characterization of temporal variability. Such characterization may require evaluation over a range of well uses and seasons.
Concentrations of arsenic in the 728 spatially distributed samples ranged from less than 1 to 2,000 µg/L. Concentrations in 58 (8.0 percent) of the samples exceeded the USEPA current MCL.
Regionally, the distribution of arsenic concentrations in ground water of the Willamette Basin appears to be primarily related to aquifer geology. High arsenic concentrations (concentrations exceeding the USEPA current MCL) are widespread in bedrock areas in south-central and eastern Lane County, and Linn County. High concentrations of arsenic also are present in some ground water in the Tualatin Basin (a subbasin in the northwestern part of the Willamette Basin). High arsenic concentrations in Lane and Linn Counties appear to be associated with two regionally extensive associations of rocks, (1) the Fisher and Eugene Formations and correlative rocks, and (2) the undifferentiated tuffaceous sedimentary rocks, tuffs, and basalt. (These rock associations are defined by Walker and MacLeod, 1991. The undifferentiated tuffaceous sedimentary rocks, tuffs, and basalt are approximately equivalent to the Little Butte Volcanic Series of Peck and others, 1964.) At land surface, these two rock associations cover 24 percent of the Willamette Basin. These associations of rocks include extensive volumes of silicic (rhyolitic) volcanic rocks, which are commonly associated with high concentrations of arsenic. High concentrations in the Tualatin Basin are associated with alluvial deposits. At a regional scale, well depth does not appear to be a useful predictor of arsenic concentration in the Willamette Basin. However, depth may be an important parameter on a local scale, particularly where wells of different depth tap aquifers in different geologic units.
Ground waters in bedrock areas in south-central and eastern Lane County, bedrock areas in Linn County, and alluvial areas in the Tualatin Basin may be more likely to yield water high in arsenic than ground water elsewhere in the basin. However, it cannot be assumed that these areas are the only areas in the basin that contain ground water with high concentrations of arsenic. Little or no data exist for many parts of the basin. Even in areas that have been sampled, geohydrologic heterogeneity makes it difficult to formulate meaningful generalizations regarding the likelihood of finding high-arsenic ground water. There is no substitute for actual sampling.
Available information, in combination with an understanding of processes known to promote arsenic mobilization, is sufficient to formulate hypotheses that explain arsenic sources and mobilization in the Willamette Basin. However, available geochemical data and interpretations are sparse. Thus, these hypotheses are preliminary, serving mainly to help direct future geochemical investigation in the Willamette Basin.
Anthropogenic sources of arsenic can be significant in some settings. Arsenical pesticides such as lead arsenate have been used in the basin, and arsenic can be released into the environment from industrial sources. However, regional patterns of arsenic occurrence in Willamette Basin ground water are not consistent with either industrial or agricultural sources of arsenic.
Naturally occurring arsenic commonly is found in a variety of solid phases. Arsenic can be a component of volcanic glass in volcanic rocks of rhyolitic to intermediate composition, adsorbed to and coprecipitated with metal oxides (especially iron oxides), adsorbed to clay-mineral surfaces, and associated with sulfide minerals and organic carbon. Examination of these potential arsenic sources for arsenic availability in the Willamette Basin apparently has never been done.
Two categories of processes largely control arsenic mobility in aquifers: (1) adsorption and desorption reactions and (2) solid-phase precipitation and dissolution reactions. Arsenic adsorption and desorption reactions are influenced by changes in pH, occurrence of redox (reduction/oxidation) reactions, presence of competing anions, and solid-phase structural changes at the atomic level. Solid-phase precipitation and dissolution reactions are controlled by solution chemistry, including pH, redox state, and chemical composition.
Several species of arsenic occur in nature, but arsenate (arsenic V) and arsenite (arsenic III) are the two forms commonly found in ground water. For this study, samples from five domestic wells were analyzed for arsenic species. Two additional analyses for arsenic species in ground water from the Willamette Basin were available in the literature. Arsenite was the predominant species of arsenic in six of these seven samples. The predominance of arsenite has both geochemical and toxicological implications. From a geochemical standpoint, mobility of arsenite differs from that of arsenate. From a public-health perspective, arsenite is more toxic than arsenate, and arsenite also is more difficult to remove from drinking-water supplies than is arsenate. Seven samples do not characterize regional arsenic speciation patterns. However, if the predominance of arsenite in Willamette Basin samples is substantiated by additional speciation work, public health officials and water managers may need to evaluate the scope of the arsenic problem with regard not only to arsenic concentrations, but also to arsenic speciation.
Existing data, including the speciation data, and published interpretations were used to establish preliminary hypotheses for the evolution of high-arsenic ground water in the Willamette Basin. For ground water in bedrock areas of Lane and Linn Counties, existing information suggests that at least some of the following controlling factors likely are important in adsorption and desorption reactions that often control arsenic mobility: (1) high pH, (2) presence of competing anions, and (3) occurrence of reducing conditions. Existing information did not allow for evaluation of the potential importance of adsorption and desorption reactions related to solid-phase structural changes at the atomic level, or solid-phase precipitation and dissolution reactions.
For alluvial ground water of the Tualatin Basin, presence of competing anions and occurrence of reducing conditions may be important controlling factors in arsenic adsorption and desorption reactions. These two factors might be more important than pH controls over arsenic adsorption and desorption. Reducing conditions and high concentrations of dissolved iron also suggest that dissolution of iron oxides, with subsequent release of adsorbed and (or) coprecipitated arsenic, may play a role in arsenic mobility in the Tualatin Basin.
Although the regional distribution of arsenic concentrations in ground water of the Willamette Basin has been evaluated by this study, an understanding of how ground water in parts of the basin evolved to contain high concentrations of arsenic has not yet been developed. Limited geochemical data have allowed establishment of preliminary hypotheses to explain the evolution of high-arsenic ground water. Developing an understanding of arsenic sources and processes responsible for evolution of high concentrations of arsenic, though, will require additional geochemical investigation. In particular, thermodynamic evaluation of ground water chemistry and study of solid phases present in aquifers would facilitate development of an understanding of adsorption and desorption and precipitation and dissolution reactions controlling arsenic mobility in the Willamette Basin. A key benefit of detailed geochemical study of arsenic in ground water of the Willamette Basin would be increased predictability of areas likely to yield ground water with high arsenic concentrations. Such increased predictability would be likely to have transfer value beyond the Willamette Basin.
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U.S. Geological Survey