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  Arsenic in Ground Water of the Willamette Basin, Oregon

GEOCHEMISTRY OF ARSENIC

An understanding of factors controlling the distribution of arsenic in ground water requires a knowledge of arsenic sources and of processes controlling arsenic mobility. To that end, possible sources of arsenic in Willamette Basin ground water are discussed in this section. Processes that have been shown to control arsenic mobility in other natural systems are discussed next. Then, arsenic speciation data collected as part of this project, along with some historical speciation data, are presented. Finally, geochemical data (including the speciation data) and information from existing interpretive reports are used to construct preliminary hypotheses regarding possible geochemical controls over mobilization of arsenic in the Willamette Basin. An understanding of arsenic sources and geochemistry in the basin could help guide future monitoring efforts both in the basin and elsewhere. However, rigorous geochemical investigation of reasonable hypotheses will be required before an adequate understanding of arsenic geochemistry in the Willamette Basin can be said to exist. Thus, this discussion may serve future research.

Sources of Arsenic

Arsenic can be introduced into ground water from anthropogenic and natural sources. Anthropogenic sources may be important in some settings. Because industrial activity tends to be localized, it would be difficult to explain regional patterns of arsenic occurrence in the Willamette Basin by introduction from industrial sources. However, arsenical pesticides such as lead arsenate were historically used in large quantities in agricultural areas of the Willamette Basin (Rinehold and Jenkins, 1993). High-arsenic ground water in bedrock areas of Lane and Linn County tends to occur in nonagricultural areas, so it is unlikely that the observed high concentrations of arsenic in ground water in those areas can be attributed to historical use of arsenical pesticides. However, in contrast to land-use patterns in the bedrock areas of Lane and Linn Counties, land use in alluvial portions of the Tualatin Basin includes a variety of agricultural land uses, and high-arsenic ground water in alluvium in the Tualatin Basin does generally coincide with occurrence of agricultural areas. Closer inspection of the data, however, shows that detections of high concentrations of arsenic in Tualatin Basin ground water generally are near rivers and streams (pl. 1). Ground water near these rivers and streams likely represents ground water near the end of ground-water flowpaths. Occurrence of high concentrations of arsenic in downgradient parts of ground-water flowpaths could result from transport of arsenic from upgradient areas where arsenical pesticides historically had been applied, or from mobilization of naturally occurring arsenic during geochemical evolution as ground water moves along flowpaths. Arsenic is nearly immobile in topsoils, and arsenic in arsenical-pesticide-contaminated topsoil leaches on timescales of decades or more (Aten and others, 1980). Thus, occurrence of high concentrations of arsenic primarily in downgradient areas, and not more uniformly distributed in the Tualatin Basin, is more consistent with a natural source than an anthropogenic source. However, no rigorous ground-water flowpath analysis has been done for arsenic transport in the Tualatin Basin, and instances of leaching of arsenic from sites of historical arsenical use into ground water of the Tualatin Basin cannot be ruled out. Nonetheless, regional patterns of arsenic concentrations in ground water of the Willamette Basin as a whole probably reflect primarily natural sources.

Naturally occurring arsenic commonly is found in 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 (Welch and others, 1988). Sulfide minerals can contain arsenic either as a dominant mineral-forming element or as an impurity; sulfide minerals are found locally in the Western Cascades (U.S. Geological Survey, 1969). Metal oxides and clay minerals are ubiquitous in the Willamette Basin. Organic carbon is widespread in many parts of the Willamette Basin, especially in alluvial deposits. Volcanic glass, commonly a major component of volcanic rocks, also is widely found in Willamette Basin aquifers, although much of the original glass in older volcanic rocks has been devitrified (Peck and others, 1964). Thus, arsenic originally associated with such volcanic glass either will have become associated with devitrification alteration products such as clays and metal oxides, or will have been released into solution and subsequently adsorbed or precipitated elsewhere or flushed from the aquifer. However, volcanic glass is still abundant in the Willamette Basin, and thus may constitute a current source of arsenic. At a minimum, the apparent relationship between rock associations containing silicic volcanic rocks and the occurrence of high concentrations of arsenic in ground water in Lane and Linn Counties described earlier in this report suggests that considerable amounts of arsenic might ultimately have come from volcanic glass. Thus, several sources of naturally occurring arsenic dispersed in aquifer materials can reasonably be postulated. However, examination of these various potential arsenic sources for arsenic availability in the Willamette Basin apparently has never been done.

Review of Geochemical Processes Controlling Arsenic Mobility

Two categories of processes largely control arsenic mobility in aquifers: (1) adsorption and desorption reactions and (2) solid-phase precipitation and dissolution reactions. Attachment of arsenic to an iron oxide surface is an example of an adsorption reaction. The reverse of this reaction, arsenic becoming detached from such a surface, is an example of desorption. Solid-phase precipitation is the formation of a solid phase from components present in aqueous solution. Precipitation of the mineral calcite, from calcium and carbonate present in ground water, is an example of solid-phase precipitation. Dissolution of volcanic glass within an aquifer is an example of solid-phase dissolution.

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.

Adsorption and Desorption Processes

Arsenic is a redox-sensitive element. This means that arsenic may gain or lose electrons in redox reactions. As a result, arsenic may be present in a variety of redox states. Arsenate and arsenite are the two forms of arsenic commonly found in ground water (Masscheleyn and others, 1991). Arsenate generally predominates under oxidizing conditions. Arsenite predominates when conditions become sufficiently reducing. Under the pH conditions of most ground water, arsenate is present as the negatively charged oxyanions H2AsO4- or HAsO42-, whereas arsenite is present as the uncharged species H3AsO30 (Hem, 1985). The strength of adsorption and desorption reactions between these different arsenic species and solid-phase surfaces in aquifers varies, in part, because of these differences in charge. Differences in species charge affect the character of electrostatic interactions between species and surfaces.

Arsenate and arsenite adsorb to surfaces of a variety of aquifer materials, including iron oxides, aluminum oxides, and clay minerals. Adsorption and desorption reactions between arsenate and iron-oxide surfaces are particularly important controlling reactions because iron oxides are widespread in the hydrogeologic environment as coatings on other solids, and because arsenate adsorbs strongly to iron-oxide surfaces in acidic and near-neutral-pH water (Dzombak and Morel, 1990; Waychunas and others, 1993). However, desorption of arsenate from iron-oxide surfaces becomes favored as pH values become alkaline (Fuller and Davis, 1989; Dzombak and Morel, 1990). The pH-dependence of arsenate adsorption to iron-oxide surfaces appears to be related to the change in iron-oxide net surface charge from positive to negative as pH increases above the zero-point-of-charge (pH at which the net surface charge is equal to zero) of about 7.7 for goethite (crystalline iron oxide) (Stumm and Morgan, 1996) or 8.0 for ferrihydrite (amorphous iron oxide) (Dzombak and Morel, 1990). Where pH values are above about 8, the negative net surface charge of iron oxide can repel negatively charged ions such as arsenate.

Iron-oxide surfaces also adsorb arsenite, and both arsenate and arsenite adsorb to aluminum oxides and clay-mineral surfaces. However, these adsorption reactions appear generally to be weaker than is the case for arsenate adsorption to iron-oxide surfaces under typical environmental pH conditions (Manning and Goldberg, 1997). Nevertheless, pH-dependent adsorption and desorption reactions other than those between arsenate and iron-oxide surfaces may be important controls over arsenic mobility in some settings. As is the case for adsorption of arsenate to iron-oxide surfaces, adsorption of arsenite to iron-oxide surfaces tends to decrease as pH increases, at least between the range from pH 6 to pH 9 (Dzombak and Morel, 1990). Unfortunately, arsenate and arsenite adsorption and desorption reactions with other common surfaces are less well characterized, and apparently more complex than is the case for adsorption and desorption reactions with iron-oxide surfaces (Manning and Goldberg, 1997).

As a result of the pH dependence of arsenic adsorption, changes in ground-water pH can promote adsorption or desorption of arsenic. Because solid-phase diagenesis (water-rock interaction) typically consumes H+ (Stumm and Morgan, 1996), the pH of ground water tends to increase with residence time, which, in turn, increases along ground-water flowpaths. Because iron-oxide surfaces can hold large amounts of adsorbed arsenate, geochemical evolution of ground water to high (alkaline) pH can induce desorption of arsenic sufficient to result in exceedances of the USEPA current MCL in some environments (see, for example, Robertson, 1989).

Similarly, redox reactions can control aqueous arsenic concentrations by their effects on arsenic speciation, and hence, arsenic adsorption and desorption. For example, reduction of arsenate to arsenite can promote arsenic mobility because arsenite is generally less strongly adsorbed than is arsenate. Redox reactions involving either aqueous or adsorbed arsenic can affect arsenic mobility (Manning and Goldberg, 1997).

Arsenic adsorption also can be affected by the presence of competing ions. In particular, phosphate and arsenate have similar geochemical behavior, and as such, both compete for sorption sites (Hingston and others, 1971; Livesey and Huang, 1981; Manning and Goldberg, 1996). Oxyanions in addition to phosphate also may compete for sorption sites. For example, Robertson (1989) suggested that correlation of arsenate with oxyanions of molybdenum, selenium, and vanadium in ground water of the Southwestern United States may be evidence for competitive adsorption among those oxyanions.

Finally, structural changes in solid phases at the atomic level also affect arsenic adsorption and desorption. For example, conversion of ferrihydrite to goethite or to other crystalline iron-oxide phases may occur gradually over time (Dzombak and Morel, 1990). Fuller and others (1993) demonstrated that as ferrihydrite crystallizes into goe- thite, the density of arsenic adsorption sites decreases. This decrease in density of adsorption sites can result in desorption of adsorbed arsenic. Structural changes in other solid phases may possibly affect arsenic mobility, too. The role of such solid-phase structural changes on ground-water arsenic concentrations has, however, received little attention to date.

Precipitation and Dissolution Processes

The various solid phases (minerals, amorphous oxides, volcanic glass, organic carbon) of which aquifers are composed exist in a variety of thermodynamic states. At any given time, some aquifer solid phases will be undergoing dissolution, whereas others will be precipitating from solution. Arsenic contained within solid phases, either as a primary structural component of or an impurity in any of a variety of solid phases, is released to ground water when those solid phases dissolve. Similarly, arsenic is removed from ground water when solid phases containing arsenic precipitate from aqueous solution. As an example, because arsenic often coprecipitates with iron oxide (Waychunas and others, 1993), iron oxide may act as an arsenic source (case of dissolution) or a sink (case of precipitation) for ground water. Furthermore, solid-phase dissolution will contribute not only arsenic contained within that phase, but also any arsenic adsorbed to the solid-phase surface. The process of release of adsorbed arsenic as a result of solid-phase dissolution is distinct from the process of desorption from stable solid phases.


 

Table 4. Speciation of arsenic

[Total arsenic concentration is from a separate analysis of a separate sample, and differs from the total of arsenite-plus-arsenate because of sampling and (or) analytical variability. Recovery, total of arsenite-plus-arsenate divided by total arsenic; µg/L, micrograms per liter]
Well location Date Arsenite (percent of total of arsenite-plus-arsenate)
Arsenate (percent of total of arsenite-plus-arsenate)
Arsenite (µg/L)
Arsenate (µg/L)
Total of arsenite-plus-arsenate
(µg/L)
Total arsenic concentration
(µg/L)
Recovery (percent)
01N/03W-04CCC
08/19/97
76
24
61.1
18.9
80.0
97
82
01S/03W-10BCA1
08/19/97
96
4
58.8
2.3
61.1
56
110
02S/02W-11CCD1
08/19/97
94
6
15.3
.9
16.2
19
85
18S/04W-14BBA
08/20/97
>99
<1
1,200
6.1
1,210
1,100
110
19S/03W-31E1
08/20/97
68
32
61.5
29.4
90.9
130
70

The interplay of redox reactions and solid-phase precipitation and dissolution may be particularly important with regard to aqueous arsenic and solid-phase iron oxides and sulfide minerals. High concentrations of arsenic often are associated with iron oxides and sulfide minerals (Thornton, 1996). Iron oxides frequently dissolve under reducing conditions, but often precipitate under oxidizing conditions. Sulfide minerals generally are unstable under oxidizing conditions, but may precipitate under reducing conditions. Thus, as a result of the redox-sensitive nature of iron oxides and sulfide minerals, transfer of large amounts of arsenic between these solid phases and neighboring water may result from redox-facilitated precipitation and dissolution reactions.

Arsenic Speciation in the Willamette Basin

Three samples from alluvial wells in the Tualatin Basin and two from bedrock wells in Lane County were analyzed for four common species of arsenic. Concentrations of the two organic species of arsenic analyzed (monosodium methylarsonate, or CH3AsO3HNa, and sodium dimethylarsinate, or (CH3)2AsO2Na) were below MDLs, so only the data for the two inorganic species are tabulated. These speciation data are given in table 4.

Two additional analyses for arsenic species in ground water from the Willamette Basin were available in the literature. Welch and others (1988) reported arsenite and arsenate concentrations for water from two wells in Lane County. Arsenite represented 7 percent and 62 percent of the total arsenic in these samples (total arsenic concentrations being 25 and 45 µg/L, respectively).

The most striking feature of the data from the two studies is the predominance of arsenite. The predominance of arsenite has both geochemical and toxicological implications. From a geochemical standpoint, the speciation data are of interest because mobility of arsenite differs from that of arsenate (see section "Review of Geochemical Processes Controlling Arsenic Mobility"). From a public-health perspective, the speciation data are interesting because arsenite is more toxic than arsenate in at least some of its effects. In human acute toxicity studies, arsenite has been shown to be more potent than arsenate (U.S. Environmental Protection Agency, 1988). With regard to human chromosome breakage, arsenite is about an order of magnitude more potent than arsenate (U.S. Environmental Protection Agency, 1988). Morrison and others (1989) report that arsenite is 50 times as toxic as arsenate, but do not report the organisms studied. Also, arsenite is more difficult to remove from drinking-water supplies than is arsenate (Gupta and Chen, 1978; Schneiter and Middlebrooks, 1983). However, it would be premature to make generalizations regarding arsenic toxicity in the Willamette Basin based upon such limited speciation data (seven samples). Complicating the matter, in the benchmarks against which drinking water arsenic concentration data commonly are compared--the USEPA current MCL and the WHO provisional guideline--no differentiation is made between arsenite and arsenate. But if the apparent predominance of arsenite in Willamette Basin ground water is confirmed 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.

Geochemistry of Arsenic in the Willamette Basin

Few routine chemical analyses (of major ions and field parameters) are available for high-arsenic ground water from bedrock areas of Lane and Linn Counties. Goldblatt and others (1963) noted that high-arsenic ground water tended to have high pH (>8.0) and high orthophosphate concentrations, although only two routine chemical analyses for high-arsenic ground water were published. Reliable measures of redox conditions were not collected. However, the observation was made during site visits that water from many of the wells in bedrock areas of Lane and Linn Counties that yielded high-arsenic ground water during project sampling also had sulfide odors. The presence of sulfide in water indicates chemically reducing conditions. The observation of sulfide, along with the detection of arsenite (the more reduced of the two major arsenic species) in some ground-water samples, indicates the presence of reducing conditions in some ground water in these areas.

Together, these data suggest that for ground water in bedrock areas of Lane and Linn Counties, one or more of the following controlling factors likely are important in adsorption and desorption reactions that in turn often control arsenic mobility: (1) high pH, (2) presence of competing anions, and (3) occurrence of reducing conditions. The sparse available data do not allow even for speculation about adsorption and desorption reactions related to solid-phase structural changes at the atomic level in ground water of bedrock areas of Lane and Linn Counties. Similarly, evidence is lacking to even begin to develop hypotheses about solid-phase precipitation and dissolution reactions.

Previous investigations of the quality of Tualatin Basin ground water provide some preliminary insight into arsenic geochemistry there. Rounds and others (1994) reported that high phosphorus concentrations (up to 2.9 mg/L [milligrams per liter]) are common in Tualatin Basin ground water. In an analysis of 47 filtered ground-water samples from the Tualatin Basin, Hinkle (1997) reported that the median arsenic concentration in low-dissolved-oxygen samples (dissolved oxygen concentrations < 1.0 mg/L) was greater than the median arsenic concentration in well-oxygenated samples. The difference was statistically significant. Of the 47 samples, the 4 that exceeded the USEPA current MCL not only had low dissolved-oxygen concentrations, but also had high concentrations of orthophosphate (0.36 to 2.0 mg/L) and iron (160 to 1,900 µg/L). However, pH was not unusually high; pH of three of the four high-arsenic samples ranged from 7.5 to 7.6, and was 8.1 for the fourth sample.

These data suggest that for alluvial ground water in 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 or coprecipitated arsenic, may play a role in arsenic mobility in the Tualatin Basin.

Hypotheses about factors affecting arsenic adsorption and desorption reactions should account for arsenic speciation. Limited geochemical data suggest that desorption of arsenic from solid phases may be an important process in ground water both in bedrock areas of Lane and Linn Counties and in alluvium in the Tualatin Basin. Desorption of arsenate from iron oxides commonly results from high pH or the presence of competing ions. Such processes, of course, require the presence of arsenate on solid-phase surfaces. Because redox reactions often are slow and frequently far from equilibrium, it would not be unexpected to find arsenate adsorbed to solid-phase surfaces in chemically reducing environments. It might appear, though, that the predominance of arsenite relative to arsenate in aqueous speciation samples would be inconsistent with a hypothesis of desorption of arsenate from iron-oxide surfaces. However, it may be that arsenate is desorbed from aquifer surfaces and subsequently reduced to arsenite.

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