Results of quality-control sampling of water, bed sediment, and tissue in the Western Lake Michigan Drainages study unit of the National Water-Quality Assessment Program

This report contains the quality control results of the Western Lake Michigan Drainages study unit of the National Water Quality Assessment Program. Quality control samples were collected in the same manner and contemporaneously with environmental samples during the first highintensity study phase in the unit (1992 through 1995) and amounted to approximately 15 percent of all samples collected. The accuracy and precision of hundreds of chemical analyses of surface and ground-water, bed sediment, and tissue was determined through the collection and analysis of field blanks, field replicates and splits, matrix spikes, and surrogates. Despite the several detections of analytes in the field blanks, the concentrations of most constituents in the environmental samples will likely be an order of magnitude or higher than those in the blanks. However, frequent detections, and high concentrations, of dissolved organic carbon (DOC) in several surface and ground-water blanks are probably significant with respect to commonly measured environmental concentrations, and the environmental data will have to be qualified accordingly. The precision of sampling of water on a percent basis, as determined from replicates and splits, was generally proportional to the concentration of the constituents, with constituents present in relatively high concentrations generally having less sampling variability than those with relatively low concentrations. In general, analytes with relatively high variability between replicates were present at concentrations near the reporting limit or were associated with relatively small absolute concentration differences, or both. Precision of replicates compared to that for splits in bed sediment samples was similar, thus eliminating sampling as a major source of variability in analyte concentrations. In the case the phthalates in bed sediment, contamination in either the field or laboratory could have caused the relatively large variability between replicate samples and between split samples.Variability of analyte concentrations in tissue samples was relatively low, being 29 percent or less for all constituents. Recoveries of most laboratory schedule 2001/2010 pesticide spike compounds in surfacewater samples were reasonably good. Low intrinsic method recovery resulted in relatively low recovery forp,p'-DDE, metribuzin, and propargite. In the case of propargite, decomposition with the environmental sample matrices was also indicated. Recoveries of two compounds, cyanazine and thiobencarb, might have been biased high due to interferences. The one laboratory schedule 2050/2051 field matrix pesticide spike indicated numerous operational problems with this method that biased recoveries either low or high. Recoveries of pesticides from both pesticide schedules in field spikes of ground-water samples generally were similar to those of field matrix spikes of surface- water samples. High maximum recoveries were noted for tebuthiuron, disulfoton, DCPA, and permethrin, which indicates the possible presence of interferents in the matrices for these compounds. Problems in the recoveries of pesticides on schedule 2050/2051 from ground-water samples generally were the same as those for surfacewater samples. Recoveries of VOCs in field matrix spikes were reasonable when consideration was given for the use of the micropipettor that delivered only about 80 percent on average of the nominal mass of spiked analytes. Finally, the recoveries of most surrogate compounds in surface and ground-water samples were reasonable. Problems in sample handling (for example, spillage) were likely not the cause of any of the low recoveries of spiked compounds.