Methods for evaluating temporal groundwater quality data and results of decadal-scale changes in chloride, dissolved solids, and nitrate concentrations in groundwater in the United States, 1988-2010

Abstract

Decadal-scale changes in groundwater quality were evaluated by the U.S. Geological Survey National Water-Quality Assessment (NAWQA) Program. Samples of groundwater collected from wells during 1988-2000 - a first sampling event representing the decade ending the 20th century - were compared on a pair-wise basis to samples from the same wells collected during 2001-2010 - a second sampling event representing the decade beginning the 21st century. The data set consists of samples from 1,236 wells in 56 well networks, representing major aquifers and urban and agricultural land-use areas, with analytical results for chloride, dissolved solids, and nitrate. Statistical analysis was done on a network basis rather than by individual wells. Although spanning slightly more or less than a 10-year period, the two-sample comparison between the first and second sampling events is referred to as an analysis of decadal-scale change based on a step-trend analysis. The 22 principal aquifers represented by these 56 networks account for nearly 80 percent of the estimated withdrawals of groundwater used for drinking-water supply in the Nation. Well networks where decadal-scale changes in concentrations were statistically significant were identified using the Wilcoxon-Pratt signed-rank test. For the statistical analysis of chloride, dissolved solids, and nitrate concentrations at the network level, more than half revealed no statistically significant change over the decadal period. However, for networks that had statistically significant changes, increased concentrations outnumbered decreased concentrations by a large margin. Statistically significant increases of chloride concentrations were identified for 43 percent of 56 networks. Dissolved solids concentrations increased significantly in 41 percent of the 54 networks with dissolved solids data, and nitrate concentrations increased significantly in 23 percent of 56 networks. At least one of the three - chloride, dissolved solids, or nitrate - had a statistically significant increase in concentration in 66 percent of the networks. Statistically significant decreases in concentrations were identified in 4 percent of the networks for chloride, 2 percent of the networks for dissolved solids, and 9 percent of the networks for nitrate. A larger percentage of urban land-use networks had statistically significant increases in chloride, dissolved solids, and nitrate concentrations than agricultural land-use networks. In order to assess the magnitude of statistically significant changes, the median of the differences between constituent concentrations from the first full-network sampling event and those from the second full-network sampling event was calculated using the Turnbull method. The largest median decadal increases in chloride concentrations were in networks in the Upper Illinois River Basin (67 mg/L) and in the New England Coastal Basins (34 mg/L), whereas the largest median decadal decrease in chloride concentrations was in the Upper Snake River Basin (1 mg/L). The largest median decadal increases in dissolved solids concentrations were in networks in the Rio Grande Valley (260 mg/L) and the Upper Illinois River Basin (160 mg/L). The largest median decadal decrease in dissolved solids concentrations was in the Apalachicola-Chattahoochee-Flint River Basin (6.0 mg/L). The largest median decadal increases in nitrate as nitrogen (N) concentrations were in networks in the South Platte River Basin (2.0 mg/L as N) and the San Joaquin-Tulare Basins (1.0 mg/L as N). The largest median decadal decrease in nitrate concentrations was in the Santee River Basin and Coastal Drainages (0.63 mg/L). The magnitude of change in networks with statistically significant increases typically was much larger than the magnitude of change in networks with statistically significant decreases. The magnitude of change was greatest for chloride in the urban land-use networks and greatest for dissolved solids and nitrate in the agricultural land-use networks. Analysis of data from all networks combined indicated statistically significant increases for chloride, dissolved solids, and nitrate. Although chloride, dissolved solids, and nitrate concentrations were typically less than the drinking-water standards and guidelines, a statistical test was used to determine whether or not the proportion of samples exceeding the drinking-water standard or guideline changed significantly between the first and second full-network sampling events. The proportion of samples exceeding the U.S. Environmental Protection Agency (USEPA) Secondary Maximum Contaminant Level for dissolved solids (500 milligrams per liter) increased significantly between the first and second full-network sampling events when evaluating all networks combined at the national level. Also, for all networks combined, the proportion of samples exceeding the USEPA Maximum Contaminant Level (MCL) of 10 mg/L as N for nitrate increased significantly. One network in the Delmarva Peninsula had a significant increase in the proportion of samples exceeding the MCL for nitrate. A subset of 261 wells was sampled every other year (biennially) to evaluate decadal-scale changes using a time-series analysis. The analysis of the biennial data set showed that changes were generally similar to the findings from the analysis of decadal-scale change that was based on a step-trend analysis. Because of the small number of wells in a network with biennial data (typically 4-5 wells), the time-series analysis is more useful for understanding water-quality responses to changes in site-specific conditions rather than as an indicator of the change for the entire network.