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External quality-assurance results for the National Atmospheric Deposition Program/National Trends Network, 1995-96

Water-Resources Investigations Report 99-4072

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Abstract

The U.S. Geological Survey operated four external quality-assurance programs for the National Atmospheric Deposition Program/National Trends Network (NADP/NTN) in 1995 and 1996: the intersite-comparison program, the blind-audit program, the interlaboratory- comparison program, and the collocated-sampler program. The intersite-comparison program assessed the precision and bias of pH and specific-conductance determinations made by NADP/NTN site operators. The analytical bias introduced during routine handling, processing, and shipping of wet-deposition samples and precision of analyte values was estimated using a blind-audit program. An interlaboratory-comparison program was used to evaluate differences between analytical results and to estimate the analytical precision of five North American laboratories that routinely analyzed wet deposition. A collocated-sampler program estimated the precision of the overall precipitation collection and analysis system from initial sample collection through final storage of the data. Results of two intersite-comparison studies completed in 1995 indicated 94.6 and 94.4 percent of the onsite pH determinations met the NADP/NTN accuracy goals, whereas 97.2 and 98.3 percent of the specific-conductance determinations were within the established limits. The percentages of onsite determinations that met the accuracy goals in 1996 were slightly less for both pH and specific-conductance than in 1995. In 1996, 93.2 and 87.5 percent of onsite pH determinations met the accuracy goals, whereas the percentage of onsite specific-conductance measurements that met the goals was 93.9 and 94.9 percent.The blind audit program utilizes a paired sample design to evaluate the effects of routine sample handling, processing and shipping on the chemistry of weekly precipitation samples. The portion of the blind audit sample subject to all of the normal onsite handling and processing steps of a regular weekly precipitation sample is referred to as the bucket portion, whereas the portion receiving only minimal handling is referred to as the bottle portion. Throughout the report, the term positive bias in regard to blind-audit results indicates that the bucket portion had a higher concentration than the bottle portion. The paired t-test of 1995 blind-audit data indicated that routine sample handling, processing, and shipping introduced a very small positive bias (a=0.05) for hydrogen ion and specific conductance and a slight negative bias (a =0.05) for ammonium and sodium. In 1995, the median paired differences between the bucket and bottle portions ranged from -0.02 milligram per liter for both ammonium and nitrate to +0.002 milligram per liter for calcium. Although the paired t-test indicated a very small positive bias for hydrogen ion, the median paired difference between the bucket and bottle portions was 0.00 microequivalents per liter, whereas for specific conductance, the median paired difference between the bucket and bottle portions was 0.200 microsiemens per centimeter in 1995. The paired t-test of blind-audit results in 1996 indicated statistically significant bias for 6 of the 10 analytes. Only chloride, nitrate, hydrogen ion, and specific conductance were not biased in 1996. However, the magnitude of the bias in 1996 was very small and only of limited importance from the viewpoint of an analytical chemist or data user. The median paired differences between the bucket and bottle portions ranged from -0.02 milligram per liter for both ammonium and chloride to +0.006 milligram per liter for calcium. For hydrogen ion, the median paired difference between the bucket and bottle portions was -0.357 microequivalent per liter; for specific conductance, the median paired difference between the bucket and bottle portions was 0.00 microsiemens per centimeter in 1996. Surface-chemistry effects due to different amounts of precipitation contacting the sample collection and shipping container surfac

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, 1995-96
Series title:
Water-Resources Investigations Report
Series number:
99-4072
Edition:
-
Year Published:
1999
Language:
ENGLISH
Publisher:
U.S. Dept. of the Interior, U.S. Geological Survey : Information Services [distributor],
Description:
vi, 69 p. :ill. (some col.), col. map ;28 cm.