Assessments to determine whether agricultural pesticides are present in ground water are performed by the Commonwealth of Pennsylvania under the aquifer monitoring provisions of the State Pesticides and Ground Water Strategy. Pennsylvania's Department of Agriculture conducts the monitoring and collects samples; the Department of Environmental Protection (PaDEP) Laboratory analyzes the samples to measure pesticide concentration. To evaluate the quality of the measurements of pesticide concentration for a groundwater assessment, a quality-assurance design was developed and applied to a selected assessment area in Pennsylvania. This report describes the quality-assurance design, describes how and where the design was applied, describes procedures used to collect and analyze samples and to evaluate the results, and summarizes the quality assurance results along with the assessment results.

The design was applied in an agricultural area of the Delaware River Basin in Berks, Lebanon, Lehigh, and Northampton Counties to evaluate the bias and variability in laboratory results for pesticides. The design—with random spatial and temporal components—included four data-quality objectives for bias and variability. The spatial design was primary and represented an area comprising 30 sampling cells. A quality-assurance sampling frequency of 20 percent of cells was selected to ensure a sample number of five or more for analysis. Quality-control samples included blanks, spikes, and replicates of laboratory water and spikes, replicates, and 2-lab splits of groundwater. Two analytical laboratories, the PaDEP Laboratory and a U.S. Geological Survey Laboratory, were part of the design. Bias and variability were evaluated by use of data collected from October 1997 through January 1998 for alachlor, atrazine, cyanazine, metolachlor, simazine, pendimethalin, metribuzin, and chlorpyrifos.

Results of analyses of field blanks indicate that collection, processing, transport, and laboratory analysis procedures did not contaminate the samples; there were no false-positive results. Pesticides were detected in water when pesticides were spiked into (added to) samples. There were no false negatives for the eight pesticides in all spiked samples. Negative bias was characteristic of analytical results for the eight pesticides, and bias was generally in excess of 10 percent from the ‘true’ or expected concentration (34 of 39 analyses, or 87 percent of the ground-water results) for pesticide concentrations ranging from 0.31 to 0.51 mg/L (micrograms per liter). The magnitude of the negative bias for the eight pesticides, with the exception of cyanazine, would result in reported concentrations commonly 75-80 percent of the expected concentration in the water sample. The bias for cyanazine was negative and within 10 percent of the expected concentration. A comparison of spiked pesticide-concentration recoveries in laboratory water and ground water indicated no effect of the ground-water matrix, and matrix interference was not a source of the negative bias. Results for the laboratory-water spikes submitted in triplicate showed large variability for recoveries of atrazine, cyanazine, and pendimethalin. The relative standard deviation (RSD) was used as a measure of method variability over the course of the study for laboratory waters at a concentration of 0.4 mg/L. An RSD of about 11 percent (or about ?0.05 mg/L)characterizes the method results for alachlor, chlorpyrifos, metolachlor, metribuzin, and simazine. Atrazine and pendimethalin have RSD values of about 17 and 23 percent, respectively. Cyanazine showed the largest RSD at nearly 51 percent. The pesticides with low variability in laboratory-water spikes also had low variability in ground water.

The assessment results showed that atrazinewas the most commonly detected pesticide in ground water in the assessment area. Atrazine was detected in water from 22 of the 28 wells sampled, and recovery results for atrazine were some of the worst (largest negative bias). Concentrations of the eight pesticides in ground water from wells were generally less than 0.3 µg/L. Only six individual measurements of the concentrations in water from six of the wells were at or above 0.3 µg/L, five for atrazine and one for metolachlor. There were eight additional detections of metolachlor and simazine at concentrations less than 0.1 µg/L. No well water contained more than one pesticide at concentra-tions at or above 0.3 µg/L. Evidence exists, how-ever, for a pattern of co-occurrence of metolachlor and simazine at low concentrations with higher concentrations of atrazine.

Large variability in replicate samples and negative bias for pesticide recovery from spiked samples indicate the need to use data for pesticide recovery in the interpretation of measured pesti-cide concentrations in ground water. Data from samples spiked with known amounts of pesticides were a critical component of a quality-assurance design for the monitoring component of the Pesti-cides and Ground Water Strategy.

Trigger concentrations, the concentrations that require action under the Pesticides and Ground Water Strategy, should be considered maximums for action. This consideration is needed because of the magnitude of negative bias.