Arsenic in Ground Water of the Willamette Basin, Oregon


The overall approach used to collect, assemble, and analyze data for this report is described in this section. First, a description of the sources of historical data is given, followed by a description of the sampling design for project data. Approaches used to define the quality of both historical and project data are discussed, as are collection and analytical methods used for project data. Finally, benchmarks for comparison of arsenic-concentration data, and methods for identification of well locations, are described.

Historical Data

Analysis of historical data (arsenic concentrations and site locations, and in most cases, well depths) from regional ground-water investigations was the starting point for evaluation of distribution of arsenic in the Willamette Basin. Some wells were sampled more than once; in these cases, the first-in-time sample was selected. Four sets of historical data used in this report are described below.

Historical data from the USGS National Water Information System (NWIS) database (Maddy and others, 1990) (271 wells). These data were collected between 1971 and 1997 as parts of various USGS projects. Many of these projects were regional in scope, and thus these data cover large areas in the Willamette Basin. In addition to arsenic concentrations, depth data also were retrieved. Data from both unfiltered and filtered samples were found in NWIS. Some of these NWIS data are discussed in the following reports: Frank and Collins, 1978; Gonthier, 1983; Leonard and Collins, 1983; Hinkle, 1997. Project data, although stored in NWIS, are discussed separately (see section "Sampling Design for Project Data").

Data from four USGS studies (Frank, 1973, 1974, 1976; Helm and Leonard, 1977), not entered into NWIS (89 wells). These data, also from regional-scale projects, encompass large areas in the southern part of the basin. The data were collected between 1964 and 1973 by USGS personnel. Well depths were obtained from tables in the reports. Techniques used to process these samples (in particular, filtering or a lack thereof) are not known.

Data from a USGS study in Lane County, not entered into NWIS (171 wells; 1 nonthermal spring). These data were collected during 1962-63, and summarized by Goldblatt and others (1963). Many of these wells withdraw water from the arsenic-rich Fisher Formation (Goldblatt and others, 1963). Arsenic concentrations and well depths were compiled from original project notes from USGS files. Samples were collected and analyzed as unfiltered samples (A.S. Van Denburgh, U.S. Geological Survey, oral commun., 1997).

Data from Linn County Department of Health Services, Environmental Health Program (65 wells). More than 100 wells were sampled for arsenic by the Environmental Health Program in 1987. Most of these wells were located near Sweet Home, an area that received little coverage in the three regional data sets listed above. Drillers' logs were on file with the Environmental Health Program for many of these wells. In 1996, USGS personnel were able to locate 65 homes corresponding to addresses from well drillers' logs for sampled wells. Arsenic concentrations from Environmental Health Program files and well depths from well drillers' logs were matched with the home locations to create a data coverage. Samples were probably collected and analyzed as unfiltered samples.

Sampling Design for Project Data

Project data were collected for several purposes. Ground-water samples were collected to fill gaps in the spatial distribution of the historical data and to illustrate the magnitude of temporal variability in arsenic concentrations. In addition, five ground-water samples were analyzed for arsenic species. Quality-control (QC) data were collected to evaluate the quality of project data, evaluate the quality of historical data (by resampling selected historical sites), and compare results obtained by different processing and analytical methods.

Samples from 125 wells and 6 nonthermal springs were collected during 1996 and 1997 to complement the spatial distribution of historical data. The wells and springs sampled were distributed throughout the lower elevation areas of the Willamette Basin, which are areas of greatest ground-water use. These sites had not previously been sampled for arsenic by the USGS. Some wells were sampled more than once during the course of this project; in these cases, the first-in-time samples were used to define the spatial distribution of arsenic.

To evaluate temporal variability of arsenic concentrations, samples were collected quarterly for 1 year from each of 17 sites. These samples also were collected during 1996 and 1997. A subset (5) of these 17 sites were sampled for arsenic species.

QC samples were used to evaluate the quality of techniques used to collect and analyze project samples. Twelve field equipment blanks, 6 sets of triplicate split samples, and 11 standard reference samples (SRSs) were analyzed over the course of the project. Field equipment blanks allow evaluation of the extent of any sample contamination resulting from sample collection, processing, and analysis. Replicate samples allow evaluation of the reproducibility (precision) of analyses. SRSs facilitate evaluation of analytical accuracy. The USGS SRS program, an interlaboratory testing program, is described in a report by Long and Farrar (1995). Preparation, description, and most probable values (MPVs) of constituents of individual SRSs used in this study are described by U.S. Geological Survey (1990) and Long and Farrar (1991, 1993, 1995). An MPV for an analyte is the median of the concentrations determined by the participating laboratories. Analytical results are reported as percentages of SRS-program MPVs.

Additional quality assurance included resampling 11 historical sites. Comparison between historical arsenic concentrations and concentrations determined upon resampling offers a measure of the reliability of historical data.

Comparisons between filtered and unfiltered samples, and between USGS and USEPA analytical methods, also were made. Characterization of differences in arsenic concentrations among unfiltered and filtered samples helps quantify the effect of sample filtering, and increases the transfer value of the data and interpretations presented in this report. Data from comparison of USGS and USEPA analytical methods facilitate comparison of arsenic concentrations determined by USGS methods with USEPA water-quality criteria.

Project Sample Collection Methods

Project samples from wells and springs used for evaluation of spatial distribution of arsenic were not filtered. Unfiltered samples, in addition to being more economical to collect than samples filtered through 0.45-µm (micrometer) filters, also have the advantage of being more representative of the water being consumed by most well owners. Another justification for collection of unfiltered samples is that many of the historical data, with which project data were combined, were from analyses of unfiltered samples. Furthermore, USEPA and World Health Organization (WHO) guidelines for water quality (see section "Comparisons with Water-Quality Criteria") apply to "finished water." For most project wells, which were primarily domestic wells, "finished water" generally is equivalent to unfiltered water. However, because unfiltered samples may contain more colloids and (or) more sediment entrained during pumping, unfiltered samples are less representative of water actually moving through an aquifer than are 0.45-µm-filtered samples. Thus, the use of unfiltered samples in characterization of ground-water quality represents an approximation. Additional, quantitative discussion on this topic is presented in the section, "Comparison of Processing and Analytical Methods."

Of the 125 project wells used for evaluation of spatial distribution of arsenic, 116 were actively used domestic wells. The remaining 9 wells included 3 public-water-supply wells, 3 industrial wells, 2 irrigation wells, and 1 livestock well. Of these nine wells, those that were not actively used were purged a minimum of three casing volumes prior to sampling to remove standing water from the well. Samples from actively used wells were collected following a minimum purge time of 1 minute. Longer purge times, characteristic of most USGS ground-water-quality work, were deemed unnecessary for actively used wells in this project because these wells experienced a degree of regular purging from the frequent use of the wells. A resulting limitation, however, is that samples from these wells may lose arsenic by way of adsorption to iron casing or precipitation as ground water undergoes geochemical changes while residing in a well bore or casing. Thus, arsenic concentrations in samples from these wells may be biased toward low arsenic concentrations relative to water actually moving through the aquifer. The extent of this possible bias has not been quantified, but because these wells were actively used, this potential bias is likely to be small.

Project samples collected from springs were collected from flowing springs. Fine sediment was present along with the water in several of the springs, so spring samples were filtered through 0.45-µm nominal-pore-size filters.

Project wells sampled for evaluation of temporal variability in arsenic concentrations were actively used wells, sampled using the same methods as for project wells sampled for evaluation of spatial distribution of arsenic.

Project wells sampled for arsenic speciation also were actively used wells. Samples were collected as unfiltered samples following a minimum well purge time of 1 minute. Samples were collected without headspace in brown glass vials, wrapped in aluminum foil (to prevent photooxidation), and shipped on ice to the laboratory.

Eleven wells represented in the historical data set were resampled. All were actively used wells and were sampled using the same methods as for project wells sampled for evaluation of spatial distribution of arsenic.

Samples for comparison between filtered and unfiltered samples, and comparison of USGS and USEPA methods, were collected from a subset of the wells sampled for temporal variability. Each 10-liter sample was split in the field by mechanical agitation into four subsamples. One subsample was filtered through a 0.10-µm nominal-pore-size 47-mm-diameter filter. One subsample was filtered through a 0.45-µm nominal-pore-size 142-mm-diameter filter. Two subsamples were collected as unfiltered samples. For each set of the four subsamples, both of the filtered samples and one of the unfiltered samples were analyzed by USGS methods (see section "Project Analytical Methods"). The other unfiltered sample was analyzed by USEPA methods (see section "Project Analytical Methods").

All arsenic samples, except samples collected for analysis of arsenic species, were field-acidified to below pH 2 with nitric acid. Samples for analysis of arsenic species were not acidified.

Project Analytical Methods

Arsenic analyses were done at the USGS National Water Quality Laboratory (NWQL) in Arvada, Colorado. Most arsenic determinations were done by hydride atomic absorption with a 3-minute sulfuric acid and potassium persulfate digestion (Fishman and Friedman, 1989). This is the standard USGS method, and it is referred to as the "USGS method" in this report. Ten analyses were done by graphite furnace atomic absorption with a 2-hour hydrochloric acid and nitric acid digestion (U.S. Environmental Protection Agency, 1994). This method is referred to as the "USEPA method" in this report. The analytical minimum reporting level (MRL) was 1 µg/L for both methods.

Samples for arsenic speciation were analyzed by the USGS Methods Research and Development Program at the USGS NWQL. Samples were analyzed for two inorganic species, arsenite (arsenic III) and arsenate (arsenic V), and two organic species, monosodium methylarsonate (CH3AsO3HNa) and sodium dimethylarsinate ((CH3)2AsO2Na). Analyses were done by direct injection high-performance liquid chromatography/hydride generation/inductively coupled plasma-mass spectrometry. Method detection limits (MDLs) were 0.2 µg/L (expressed as mass of arsenic per liter). Samples were analyzed within 48 hours of collection.

Comparisons with Water-Quality Criteria

To provide benchmarks against which arsenic-concentration data can be compared, arsenic-concentration data are compared with USEPA and WHO drinking-water standards. Concentrations of arsenic are compared to the USEPA current drinking water MCL for arsenic of 50 µg/L (U.S. Environmental Protection Agency, 1996). The USEPA current MCL is the maximum concentration of a contaminant allowed in a public water system. This MCL is under review (U.S. Environmental Protection Agency, 1996). Bagla and Kaiser (1996) report that the USEPA is considering reducing the current MCL by 90 percent. However, until any such reduction in the MCL occurs, the current MCL remains a logical benchmark for comparison. As an alternative benchmark, concentrations of arsenic also are compared to the WHO provisional guideline of 10 µg/L (World Health Organization, 1996).

Water with an arsenic concentration below the USEPA current MCL or WHO provisional guideline is not necessarily free from health risks. For example, arsenic concentrations may be below the USEPA current MCL and WHO provisional guideline, but still be greater than the USEPA drinking-water Risk-Specific-Dose Health Advisory (RSDHA) of 2 µg/L (U.S. Environmental Protection Agency, 1996). (The RSDHA is defined as the concentration of a contaminant in drinking water that is expected to result in a specified increased risk of cancer. The USEPA RSDHA for arsenic is calculated at the 1-in-10,000 cancer risk level. Consumption of water containing a contaminant at the RSDHA 1-in-10,000 risk level is expected to be associated with the following risk: a 70-kg adult drinking 2 L of such water per day for 70 years faces an increased risk of cancer of approximately 1 in 10,000.) Furthermore, effects of arsenic consumption on human health are not uniform among different people, and no single threshold can be defined as the dividing line between "safe" and "unsafe." Comparison of arsenic data to the USEPA current MCL and WHO provisional guideline are done solely for illustrative purposes; no implication of "safety" or lack thereof is implied.

Methods of Identifying Wells

All wells discussed in this report were assigned well location names corresponding to well locations. Well locations generally were determined when the wells were first visited. Well locations were identified using the Township, Range, and Section method of land subdivision. Two methods are shown on figure 2. Most wells were identified with a system that uses nested groups of the letters A, B, C, and D for section subdivision. Prior to about 1967, wells were identified with an alternative system, using letters A through R (excluding I and O) for section subdivision. To preserve linkage to historical data sources, all wells discussed in this report are referred to by the well location names originally assigned to them. It should be noted, however, that in some cases, the original well location names do not accurately describe the true locations of the wells. To provide accurate locational and identifying information for wells discussed in this report, corrected well locations, and additional identifying information (USGS site identification number and OWRD well log identification number), are listed along with original well locations in the Appendix. Note that in the project data report (Orzol and others, in press), wells are listed by corrected well location names.



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