Quality of pesticide data for groundwater analyzed for the National Water-Quality Assessment Project, 2013–18

The National Water-Quality Assessment (NAWQA) Project of the U.S. Geological Survey (USGS) submitted nearly 1,900 samples collected from groundwater sites across the United States in 2013–18 for analysis of 225 pesticide compounds (pesticides and pesticide degradates, hereafter referred to as “pesticides”) by USGS National Water Quality Laboratory schedule 2437 (S2437). For the associated NAWQA study of pesticide occurrence and concentration in groundwater, and for other studies using pesticide results determined by S2437, it is necessary to assess the ability of reported results to meet data-quality requirements that will allow study objectives to be achieved. This assessment of the quality of S2437 results reported in 2013–18 examined data from field and laboratory quality-control samples, along with third-party performance assessment samples, to estimate bias and variability and to identify their potential sources, with an emphasis on implications for the interpretation of pesticide data for groundwater. Results indicate that measurements produced by the S2437 method for most pesticides have bias and variability that would be considered acceptable for many interpretative studies, which could therefore use the results without qualification or censoring. However, the reported data for a subset of pesticides have the potential for unacceptable contamination bias, high or low recovery bias, or high variability as a consequence of method performance and (or) nonlaboratory factors that could preclude their use for certain common objectives or could necessitate adjustment or qualification to meet those objectives.

Based on data for laboratory blanks, censoring of some detections for a subset of pesticides reported by the laboratory in environmental samples might be necessary or desirable to avoid an unacceptably high likelihood of a false-positive result caused by laboratory contamination. The 90-percent upper confidence limit for the 95th percentile of laboratory blank concentration equals or exceeds the minimum reported groundwater concentration in at least 1 water year for 28 pesticides. During at least 1 water year, this upper confidence limit exceeds the maximum laboratory detection limit for 17 pesticides and exceeds the maximum laboratory reporting limit for 3 pesticides (ametryn, atrazine, and diazinon). The level of contamination indicated by this upper confidence limit should not substantially affect the suitability of reported environmental concentrations for any compound for comparison with corresponding human-health benchmarks.

Despite being subjected to the same laboratory processes as laboratory blanks, field blanks indicated little evidence of contamination bias. This observation could largely be the consequence of data-reporting practices, which utilize detections in laboratory blanks to censor results in associated field samples (including blanks and environmental samples) when relative concentrations indicate that a result could have a substantial contribution from laboratory contamination. Laboratory censoring appears likely to reduce the risk of false-positive results in environmental samples below the level that laboratory blank results alone would imply.

Whereas data available for third-party blind blank samples analyzed in 2018 indicate that only propoxur had any false-positive results, data for pesticides that were not spiked into blind spike samples analyzed in 2013–18 indicate that the false-positive rates for 31 pesticides exceeded 1 percent when considering only detections reported at concentrations greater than the maximum detection limit. Although about half of these pesticides lack substantial supporting evidence of contamination bias based on laboratory blank or field blank detections, indicating that spiking issues or degradation of parent compounds within the spiked samples might be a contributing factor to some false-positive results, these results indicate the need to closely examine detections reported for some pesticides in environmental samples analyzed during a similar period for possible contributions from contamination bias. Data for blind spike samples that were spiked at concentrations above the maximum reporting limit indicate that false-negative rates for eight pesticides exceed 10 percent; substantial low bias could affect results reported for these pesticides in environmental samples analyzed during a similar period.

Data for laboratory reagent spikes, which measure recovery of pesticides in blank water, show little evidence for unacceptable recovery bias for S2437 pesticides. However, field matrix spikes, which measure recovery of pesticides in environmental matrices, indicate that degradation and (or) matrix effects could result in moderate to substantial low bias for groundwater results for several pesticides. Low bias could cause some reported concentrations to be categorized as being below a benchmark when the actual concentration in groundwater is greater than the benchmark. Occurrence and concentrations in groundwater could be substantially underrepresented for six pesticides with benchmarks (1H-1,2,4-triazole, asulam, bifenthrin, cis-permethrin, fenbutatin oxide, and naled) that have median recoveries between zero and 50 percent in field matrix spikes. Two compounds (didealkylatrazine and 2-hydroxy-6-ethylamino-4-amino-s-triazine) have median recoveries near or greater than 150 percent in field matrix spikes, indicating a substantial high bias. Plots of data for all spike types show clear changes in the typical recovery with time for some pesticides, which would require further examination for evaluation of temporal trends in environmental concentrations.

Data for laboratory reagent spikes indicate that nearly all S2437 pesticides have acceptable variability resulting from random measurement error. Only two compounds (fenbutatin oxide and naled) have F-pseudosigma values greater than 30 percent for recovery, which implies the potential for relatively high variability in reported concentrations and could affect comparison of concentrations to benchmarks and determination of whether concentrations for samples collected at separate locations or times are truly different with a specified level of confidence. Data for third-party blind spike samples show relatively high variability for a greater number of pesticides, although these results likely reflect the influence of degradation and (or) differences in the magnitude and variability of concentrations used for blind spikes relative to laboratory reagent spikes. Detailed analysis of variability using field replicate data is possible for only 12 pesticides on S2437; low variability in analyte detection and concentration is indicated for most of these pesticides in groundwater.