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External quality-assurance results for the National Atmospheric Deposition Program/National Trends Network, 1997-99

Water-Resources Investigations Report 2003-4027

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Abstract

Five external quality-assurance programs were operated by the U.S. Geological Survey for the National Atmospheric Deposition Program/ National Trends Network (NADP/NTN) during 1997 through 1999: the intersite-comparison program, the blind-audit program, the field- audit program, the interlaboratory-comparison program, and the collocated-sampler program. The intersite-comparison program assesses the accuracy of pH and specific-conductance determinations made by NADP/NTN site operators. In two 1997 intersite-comparison studies, 83.7 and 85.8 percent of the pH determinations met the NADP/NTN accuracy goals, whereas 97.3 and 92.4 percent of the specific-conductance determinations met the NADP/NTN accuracy goals. The percentage of pH and specific-conductance determinations that met the accuracy goals in 1998 were, for the most part, higher than in 1997. In two 1998 studies, 90.9 and 90.3 percent of the pH determinations met the accuracy goals compared to 94.7 and 96.0 percent of the specific- conductance measurements meeting the accuracy goals. In one 1999 intersite-comparison study, 89.5 percent and 99.4 percent of pH and specific- conductance determinations, respectively, met the NADP/NTN accuracy goals. The blind-audit program evaluates the effects of routine sample handling, processing, and shipping on the analytical bias and precision of weekly precipitation samples. A portion of the blind-audit sample subject to the normal onsite handling and processing of a weekly precipitation sample is referred to as the bucket portion, whereas the portion receiving only minimal handling is referred to as the bottle portion. Positive bias in regard to blind-audit results indicates that the bucket portion has a higher concentration than the bottle portion. The paired t-test for the 1997 through 1999 blind- audit data indicates that routine sample handling, processing, and shipping introduced a positive bias (a=0.05) for calcium and chloride and a negative bias (cz=0.05) for hydrogen ion. During 1997 through 1999, the median paired differences between the bucket and bottle portions ranged from 0.00 milligram per liter for nitrate and ammonium to +0.010 milligram per liter for both chloride and sulfate. The median paired difference between the bucket and bottle portions for hydrogen ion was -1.086 microequivalents per liter, whereas for specific conductance, the median paired difference between the bucket and bottle portions was -0.200 microsiemen per centimeter during 1997 through 1999. Surface-chemistry effects due to variable amounts of precipitation contacting prewashed sample-collection and shipping-container surfaces were studied in the blind-audit program by using three different sample volumes. The sample- collection and shipping containers used for the blind-audit study were obtained from the site operator's supply and could have been used for precipitation samples. Results of a Kruskal-Wallis analysis of variance test of the relation between paired blind-audit sample differences in units of concentration and sample volume were statistically significant for magnesium, chloride, sulfate, and hydrogen ion during 1997 through 1999. Before 1994, at least 5 of the 10 analytes displayed a statistically significant difference between paired blind-audit differences in units of concentration and sample volume, supporting the premise that chemical reactions between the 13-liter bucket shipping container (primarily the butadiene o-ring lid of the shipping container) and the sample, which resulted in an increasing loss of hydrogen ion with increasing volume, have been eliminated by the new l-liter bottle sample- shipping protocol. The field-audit program measures the effects of field exposure, handling, and processing on the chemistry of NADP/NTN precipitation samples. In the field-audit program, the site operator is instructed to process and submit a quality- control sample following a standard 7-day, Tuesday-to-Tuesday sampling period with no

Additional Publication Details

Publication type:
Report
Publication Subtype:
USGS Numbered Series
Title:
External quality-assurance results for the National Atmospheric Deposition Program/National Trends Network, 1997-99
Series title:
Water-Resources Investigations Report
Series number:
2003-4027
Edition:
-
Year Published:
2003
Language:
ENGLISH
Description:
vi, 75 p. : ill. (some col.), col. map ; 28 cm.