|Abstract:||The U.S. Geological Survey, in cooperation with the U.S. Department of Energy, collects surface water and groundwater samples at and near the Idaho National Laboratory as part of a routine, site-wide, water-quality monitoring program. Quality-control samples are collected as part of the program to ensure and document the quality of environmental data. From 1996 to 2001, quality-control samples consisting of 204 replicates and 27 blanks were collected at sampling sites. Paired measurements from replicates were used to calculate variability (as reproducibility and reliability) from sample collection and analysis of radiochemical, chemical, and organic constituents. Measurements from field and equipment blanks were used to estimate the potential contamination bias of constituents. The reproducibility of measurements of constituents was calculated from paired measurements as the normalized absolute difference (NAD) or the relative standard deviation (RSD). The NADs and RSDs, as well as paired measurements with censored or estimated concentrations for which NADs and RSDs were not calculated, were compared to specified criteria to determine if the paired measurements had acceptable reproducibility. If the percentage of paired measurements with acceptable reproducibility for a constituent was greater than or equal to 90 percent, then the reproducibility for that constituent was considered acceptable. The percentage of paired measurements with acceptable reproducibility was greater than or equal to 90 percent for all constituents except orthophosphate (89 percent), zinc (80 percent), hexavalent chromium (53 percent), and total organic carbon (TOC; 38 percent). The low reproducibility for orthophosphate and zinc was attributed to calculation of RSDs for replicates with low concentrations of these constituents. The low reproducibility for hexavalent chromium and TOC was attributed to the inability to preserve hexavalent chromium in water samples and high variability with the analytical method for TOC. The reliability of measurements of constituents was estimated from pooled RSDs that were calculated for discrete concentration ranges for each constituent. Pooled RSDs of 15 to 33 percent were calculated for low concentrations of gross-beta radioactivity, strontium-90, ammonia, nitrite, orthophosphate, nickel, selenium, zinc, tetrachloroethene, and toluene. Lower pooled RSDs of 0 to 12 percent were calculated for all other concentration ranges of these constituents, and for all other constituents, except for one concentration range for gross-beta radioactivity, chloride, and nitrate + nitrite; two concentration ranges for hexavalent chromium; and TOC. Pooled RSDs for the 50 to 60 picocuries per liter concentration range of gross-beta radioactivity (reported as cesium-137) and the 10 to 60 milligrams per liter (mg/L) concentration range of nitrate + nitrite (reported as nitrogen [N]) were 17 percent. Chloride had a pooled RSD of 14 percent for the 20 to less than 60 mg/L concentration range. High pooled RSDs of 40 and 51 percent were calculated for two concentration ranges for hexavalent chromium and of 60 percent for TOC. Measurements from (1) field blanks were used to estimate the potential bias associated with environmental samples from sample collection and analysis, (2) equipment blanks were used to estimate the potential bias from cross contamination of samples collected from wells where portable sampling equipment was used, and (3) a source-solution blank was used to verify that the deionized water source-solution was free of the constituents of interest. If more than one measurement was available, the bias was estimated using order statistics and the binomial probability distribution. The source-solution blank had a detectable concentration of hexavalent chromium of 2 micrograms per liter. If this bias was from a source other than the source solution, then about 84 percent of the 117 hexavalent chromium measurements from environmental samples could have a bias of 10 percent or more. Of the 14 field blanks that were collected, only chloride (0.2 milligrams per liter) and ammonia (0.03 milligrams per liter as nitrogen), in one blank each, had detectable concentrations. With an estimated confidencelevel of 95 percent, at least 80 percent of the 1,987 chloride concentrations measured from all environmental samples had a potential bias of less than 8 percent. The ammonia bias, which may have occurred at the analytical laboratory, could produce a potential bias of 5-100 percent in eight potentially affected ammonia measurements. Of the 11 equipment blanks that were collected, chloride was detected in 4 of these blanks, sodium in 3 blanks, and sulfate and hexavalent chromium were each detected in 1 blank. The concentration of hexavalent chromium in the equipment blank was the same concentration as in the source-solution blank collected on the same day, which indicates that the hexavalent chromium in the equipment blank is probably from a source other than the portable sampling equipment, such as the sample bottles or the source-solution water itself. The potential bias for chloride, sodium, and sulfate measurements was estimated for environmental samples that were collected using portable sampling equipment. For chloride, it was estimated with 93 percent confidence that at least 80 percent of the measurements had a bias of less than 18 percent. For sodium and sulfate, it was estimated with 91 percent confidence that at least 70 percent of the measurements had a bias of less than 12 and 5 percent, respectively.