External quality-assurance results for the National Atmospheric Deposition Program/National Trends Network, 2002-03

Abstract

Six external quality-assurance programs were operated by the U.S. Geological Survey (USGS) External Quality-Assurance (QA) Project for the National Atmospheric Deposition Program/National Trends Network (NADP/NTN) from 2002 through 2003. Each program measured specific components of the overall error inherent in NADP/NTN wet-deposition measurements. The intersite-comparison program assessed the variability and bias of pH and specific conductance determinations made by NADP/NTN site operators twice per year with respect to accuracy goals. The percentage of site operators that met the pH accuracy goals decreased from 92.0 percent in spring 2002 to 86.3 percent in spring 2003. In these same four intersite-comparison studies, the percentage of site operators that met the accuracy goals for specific conductance ranged from 94.4 to 97.5 percent. The blind-audit program and the sample-handling evaluation (SHE) program evaluated the effects of routine sample handling, processing, and shipping on the chemistry of weekly NADP/NTN samples. The blind-audit program data indicated that the variability introduced by sample handling might be environmentally significant to data users for sodium, potassium, chloride, and hydrogen ion concentrations during 2002. In 2003, the blind-audit program was modified and replaced by the SHE program. The SHE program was designed to control the effects of laboratory-analysis variability. The 2003 SHE data had less overall variability than the 2002 blind-audit data. The SHE data indicated that sample handling buffers the pH of the precipitation samples and, in turn, results in slightly lower conductivity. Otherwise, the SHE data provided error estimates that were not environmentally significant to data users. The field-audit program was designed to evaluate the effects of onsite exposure, sample handling, and shipping on the chemistry of NADP/NTN precipitation samples. Field-audit results indicated that exposure of NADP/NTN wet-deposition samples to onsite conditions tended to neutralize the acidity of the samples by less than 1.0 microequivalent per liter. Onsite exposure of the sampling bucket appeared to slightly increase the concentration of most of the analytes but not to an extent that was environmentally significant to NADP data users. An interlaboratory-comparison program was used to estimate the analytical variability and bias of the NADP Central Analytical Laboratory (CAL) during 2002-03. Bias was identified in the CAL data for calcium, magnesium, sodium, potassium, ammonium, chloride, nitrate, sulfate, hydrogen ion, and specific conductance, but the absolute value of the bias was less than analytical minimum detection limits for all constituents except magnesium, nitrate, sulfate, and specific conductance. Control charts showed that CAL results were within statistical control approximately 90 percent of the time. Data for the analysis of ultrapure deionized-water samples indicated that CAL did not have problems with laboratory contamination. During 2002-03, the overall variability of data from the NADP/NTN precipitation-monitoring system was estimated using data from three collocated monitoring sites. Measurement differences of constituent concentration and deposition for paired samples from the collocated samplers were evaluated to compute error terms. The medians of the absolute percentage errors (MAEs) for the paired samples generally were larger for cations (approximately 8 to 50 percent) than for anions (approximately 3 to 33 percent). MAEs were approximately 16 to 30 percent for hydrogen-ion concentration, less than 10 percent for specific conductance, less than 5 percent for sample volume, and less than 8 percent for precipitation depth. The variability attributed to each component of the sample-collection and analysis processes, as estimated by USGS quality-assurance programs, varied among analytes. Laboratory analysis variability accounted for approximately 2 percent of the