Estimation of upper centile concentrations using historical atrazine monitoring data from community water systems

A survey sampling approach is presented for estimating upper centiles of aggregate distributions of surface water pesticide measurements obtained from datasets with large sample sizes but variable sampling frequency. It is applied to three atrazine monitoring programs of Community Water Systems (CWS) that used surface water as their drinking water source: the nationwide Safe Drinking Water Act (SDWA) data, the Syngenta Voluntary Monitoring Program (VMP), and the Atrazine Monitoring Program (AMP).The VMP/AMP CWS were selected on the basis of atrazine monitoring history (CWS having at least one annual average concentration from SDWA ≥ 1.6 ppb atrazine since 1997 in the AMP). Estimates of the raw water 95th, 99th, and 99.9th centile atrazine concentrations for the VMP/AMP CWS are 4.82, 11.85, and 34.00 ppb, respectively. The corresponding estimates are lower for the finished drinking water samples, with estimates of 2.75, 7.94, and 22.66 ppb, respectively. Finished water centile estimates for the VMP/AMP CWS using only the SDWA data for these sites are consistent with the results. Estimates are provided for the April through July period and for CWS based on surface water source type (static, flowing, or mixed). Requisite sample sizes are determined using statistical tolerance limits, relative SE, and the Woodruff interval sample size criterion. These analyses provide 99.9% confidence that the existing data include the 99.9th centile atrazine concentration for CWS raw and finished water in the Midwest atrazine high-use areas and in the nationwide SDWA dataset. The general validity of this approach is established by a simulation that shows estimates to be close to target quantities for weights based on sampling probabilities or time intervals between samples. Recommendations are given for suitable effective sample sizes to reliably determine interval estimates.