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T. C. Willoughby

Publications and source records attributed to T. C. Willoughby.

11 recordsLinked to original sources

Quality of wet deposition in the Grand Calumet River watershed, northwestern Indiana, June 30, 1992-August 31, 1993

Northwestern Indiana is one of the most heavily industrialized and largest steel-producing areas in the United States. High temperature processes, such as fossil-fuel combustion and steel production, release contaminants to the atmosphere that may result in wet deposition being a major contributor to major ion and trace-metal loadings in north- western Indiana and Lake Michigan. A wet-deposition collection site was established at the Gary (Indiana) Regional Airport in June 1992 to monitor the chemical quality of wet deposition. Weekly samples were collected at this site from June 30, 1992, through August 31, 1993, and were analyzed for pH, specific conductance, and selected major ions and trace metals. Forty-eight samples collected during the study were of sufficient volumes for some of the determinations to be performed. Median constituent concentrations were determined for samples collected during warm weather and cold weather (November 1 through March 31). Median concentrations were substituted for missing values from samples with insufficient volumes for analysis of all the constituents of interest. Constituent concentrations were converted to weekly loadings. Two values were calculated to provide a range for the weekly loading for samples with measured concentrations of constituents less than the method reporting limit. The minimum weekly loading was computed by substituting zero for the constituent concentration; the maximum weekly loading was computed by substituting the method reporting limit for the concentration. If all of the sample concentrations measured were greater than the method reporting limit, an annual loading value was computed. The annual loadings could be used to assist in estimating the contribution of wet deposition to the total annual constituent loadings in the Grand Calumet River in northwestern Indiana.

Indiana

A quality-assurance assessment for constituents reported by the National Atmospheric Deposition Program and the National Trends Network

A continuing quality-assurance program has been operated by the U.S. Geological Survey to evaluate any bias introduced by routine handling, shipping, and laboratory analyses of wet-deposition samples collected in the National Atmospheric Deposition Program (NADP) and National Trends Network (NTN). Blind-audit samples having a variety of constituent concentrations and values were selected. Only blind-audit samples with constituent concentrations and values less than the 95th-percentile concentration for natural wet-deposition samples were included in the analysis. Of the major ions, there was a significant increase of Ca 2+ , Mg 2+ , Na 2+ , K + , SO 4 2− and Cl −1 in samples handled according to standard protocols and shipped in NADP/NTN sample-collection buckets. For 1979–1987, graphs of smoothed data showing the estimated contamination in blind-audit samples indicate a decrease in the median concentration and ranges of Ca 2+ , Mg 2+ and SO 4 2− contamination of blind-audit samples shipped in sample-collection buckets. Part of the contamination detected in blind-audit samples can be attributed to contact with the sample-collection bucket and lid; however, additional sources also seem to contaminate the blind-audit sample. Apparent decreases in the magnitude and range of sample contamination may be caused by differences in sample-collection bucket- and lid-washing procedures by the NADP/NTN Central Analytical Laboratory. Although the degree of bias is minimal for most constituents, summaries of the NADP/NTN data base may contain overestimates of Ca 2+ , Mg 2+ , Na − , K + and SO 4 2− and Cl − concentrations, and underestimates of H + concentrations.

Atmospheric Environment

Stability of nitrate-ion concentrations in simulated deposition samples used for quality-assurance activities by the U.S. Geological Survey

Three experiments were conducted to determine the stability of nitrate-ion concentrations in simulated deposition samples. In the four experiment-A solutions, nitric acid provided nitrate-ion concentrations ranging from 0.6 to 10.0 mg/L and that had pH values ranging from 3.8 to 5.0. In the five experiment-B solutions, sodium nitrate provided nitrate-ion concentrations ranging from 0.5 to 3.0 mg/L. The pH was adjusted to about 4.5 for each of the solutions by addition of sulfuric acid. In the four experiment-C solutions, nitric acid provided nitrate-ion concentrations ranging from 0.5 to 3.0 mg/L. Major cation and anion concentrations were added to each solution to simulate natural deposition. Aliquots were removed from the 13 original solutions and analyzed by ion chromatography about once a week for 100 days to determine if any changes occurred in nitrate-ion concentrations throughout the study period. No substantial changes were observed in the nitrate-ion concentrations in solutions that had initial concentrations below 4.0 mg/L in experiments A and B, although most of the measured nitrate-ion concentrations for the 100-day study were below the initial concentrations. In experiment C, changes in nitrate-ion concentrations were much more pronounced; the measured nitrate-ion concentrations for the study period were less than the initial concentrations for 62 of the 67 analyses. (USGS)

Water-Resources Investigations Report

Bias and precision of selected analytes reported by the National Atmospheric Deposition Program and National Trends Network, 1984

The U.S. Geological Survey operated a blind audit sample program during 1974 to test the effects of the sample handling and shipping procedures used by the National Atmospheric Deposition Program and National Trends Network on the quality of wet deposition data produced by the combined networks. Blind audit samples, which were dilutions of standard reference water samples, were submitted by network site operators to the central analytical laboratory disguised as actual wet deposition samples. Results from the analyses of blind audit samples were used to calculate estimates of analyte bias associated with all network wet deposition samples analyzed in 1984 and to estimate analyte precision. Concentration differences between double blind samples that were submitted to the central analytical laboratory and separate analyses of aliquots of those blind audit samples that had not undergone network sample handling and shipping were used to calculate analyte masses that apparently were added to each blind audit sample by routine network handling and shipping procedures. These calculated masses indicated statistically significant biases for magnesium, sodium , potassium, chloride, and sulfate. Median calculated masses were 41.4 micrograms (ug) for calcium, 14.9 ug for magnesium, 23.3 ug for sodium, 0.7 ug for potassium, 16.5 ug for chloride and 55.3 ug for sulfate. Analyte precision was estimated using two different sets of replicate measures performed by the central analytical laboratory. Estimated standard deviations were similar to those previously reported. (Author 's abstract)

Water-Resources Investigations Report

Quality-assurance results for field pH and specific-conductance measurements, and for laboratory analysis, National Atmospheric Deposition Program and National Trends Network; January 1980-September 1984

Five intersite comparison studies for the field determination of pH and specific conductance, using simulated-precipitation samples, were conducted by the U.S.G.S. for the National Atmospheric Deposition Program and National Trends Network. These comparisons were performed to estimate the precision of pH and specific conductance determinations made by sampling-site operators. Simulated-precipitation samples were prepared from nitric acid and deionized water. The estimated standard deviation for site-operator determination of pH was 0.25 for pH values ranging from 3.79 to 4.64; the estimated standard deviation for specific conductance was 4.6 microsiemens/cm at 25 C for specific-conductance values ranging from 10.4 to 59.0 microsiemens/cm at 25 C. Performance-audit samples with known analyte concentrations were prepared by the U.S.G.S.and distributed to the National Atmospheric Deposition Program 's Central Analytical Laboratory. The differences between the National Atmospheric Deposition Program and national Trends Network-reported analyte concentrations and known analyte concentrations were calculated, and the bias and precision were determined. For 1983, concentrations of calcium, magnesium, sodium, and chloride were biased at the 99% confidence limit; concentrations of potassium and sulfate were unbiased at the 99% confidence limit. Four analytical laboratories routinely analyzing precipitation were evaluated in their analysis of identical natural- and simulated precipitation samples. Analyte bias for each laboratory was examined using analysis of variance coupled with Duncan 's multiple-range test on data produced by these laboratories, from the analysis of identical simulated-precipitation samples. Analyte precision for each laboratory has been estimated by calculating a pooled variance for each analyte. Interlaboratory comparability results may be used to normalize natural-precipitation chemistry data obtained from two or more of these laboratories. (Author 's abstract)

Water-Resources Investigations Report

Precision and bias of selected analytes reported by the National Atmospheric Deposition Program and National Trends Network, 1983; and January 1980 through September 1984

Blind-audit samples with known analyte concentrations have been prepared by the U.S. Geological Survey and distributed to the National Atmospheric Deposition Program 's Central Analytical Laboratory. The difference between the National Atmospheric Deposition Program and National Trends Network reported analyte concentrations and known analyte concentrations have been calculated, and the bias has been determined. Calcium, magnesium , sodium, and chloride were biased at the 99-percent confidence limit; potassium and sulfate were unbiased at the 99-percent confidence limit, for 1983 results. Relative-percent differences between the measured and known analyte concentration for calcium , magnesium, sodium, potassium, chloride, and sulfate have been calculated for 1983. The median relative percent difference for calcium was 17.0; magnesium was 6.4; sodium was 10.8; potassium was 6.4; chloride was 17.2; and sulfate was -5.3. These relative percent differences should be used to correct the 1983 data before user-analysis of the data. Variances have been calculated for calcium, magnesium, sodium, potassium, chloride, and sulfate determinations. These variances should be applicable to natural-sample analyte concentrations reported by the National Atmospheric Deposition Program and National Trends Network for calendar year 1983. (USGS)

Water-Resources Investigations Report