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Kenneth A. Skach

Publications and source records attributed to Kenneth A. Skach.

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Software for analysis of chemical mixtures--composition, occurrence, distribution, and possible toxicity

The composition, occurrence, distribution, and possible toxicity of chemical mixtures in the environment are research concerns of the U.S. Geological Survey and others. The presence of specific chemical mixtures may serve as indicators of natural phenomena or human-caused events. Chemical mixtures may also have ecological, industrial, geochemical, or toxicological effects. Chemical-mixture occurrences vary by analyte composition and concentration. Four related computer programs have been developed by the National Water-Quality Assessment Program of the U.S. Geological Survey for research of chemical-mixture compositions, occurrences, distributions, and possible toxicities. The compositions and occurrences are identified for the user-supplied data, and therefore the resultant counts are constrained by the user’s choices for the selection of chemicals, reporting limits for the analytical methods, spatial coverage, and time span for the data supplied. The distribution of chemical mixtures may be spatial, temporal, and (or) related to some other variable, such as chemical usage. Possible toxicities optionally are estimated from user-supplied benchmark data. The software for the analysis of chemical mixtures described in this report is designed to work with chemical-analysis data files retrieved from the U.S. Geological Survey National Water Information System but can also be used with appropriately formatted data from other sources. Installation and usage of the mixture software are documented. This mixture software was designed to function with minimal changes on a variety of computer-operating systems. To obtain the software described herein and other U.S. Geological Survey software, visit http://water.usgs.gov/software/.

Scientific Investigations Report

Relations between sinkhole density and anthropogenic contaminants in selected carbonate aquifers in the eastern United States

The relation between sinkhole density and water quality was investigated in seven selected carbonate aquifers in the eastern United States. Sinkhole density for these aquifers was grouped into high (>25 sinkholes/100 km 2 ), medium (1–25 sinkholes/100 km 2 ), or low (<1 sinkhole/100 km 2 ) categories using a geographical information system that included four independent databases covering parts of Alabama, Florida, Missouri, Pennsylvania, and Tennessee. Field measurements and concentrations of major ions, nitrate, and selected pesticides in samples from 451 wells and 70 springs were included in the water-quality database. Data were collected as a part of the US Geological Survey (USGS) National Water-Quality Assessment (NAWQA) Program. Areas with high and medium sinkhole density had the greatest well depths and depths to water, the lowest concentrations of total dissolved solids and bicarbonate, the highest concentrations of dissolved oxygen, and the lowest partial pressure of CO 2 compared to areas with low sinkhole density. These chemical indicators are consistent conceptually with a conduit-flow-dominated system in areas with a high density of sinkholes and a diffuse-flow-dominated system in areas with a low density of sinkholes. Higher cave density and spring discharge in Pennsylvania also support the concept that the high sinkhole density areas are dominated by conduit-flow systems. Concentrations of nitrate-N were significantly higher ( p < 0.05) in areas with high and medium sinkhole density than in low sinkhole-density areas; when accounting for the variations in land use near the sampling sites, the high sinkhole-density area still had higher concentrations of nitrate-N than the low sinkhole-density area. Detection frequencies of atrazine, simazine, metolachlor, prometon, and the atrazine degradate deethylatrazine indicated a pattern similar to nitrate; highest pesticide detections were associated with high sinkhole-density areas. These patterns generally persisted when analyzing the detection frequency by land-use groups, particularly for agricultural land-use areas where pesticide use would be expected to be higher and more uniform areally compared to urban and forested areas. Although areas with agricultural land use and a high sinkhole density were most vulnerable (median nitrate-N concentration was 3.7 mg/L, 11% of samples exceeded 10 mg/L, and had the highest frequencies of pesticide detection), areas with agricultural land use and low sinkhole density still were vulnerable to contamination (median nitrate-N concentration was 1.5 mg/L, 8% of samples exceeded 10 mg/L, and had some of the highest frequencies of detections of pesticides). This may be due in part to incomplete or missing data regarding karst features (such as buried sinkholes, low-permeability material in bottom of sinkholes) that do not show up at the scales used for regional mapping and to inconsistent methods among states in karst feature delineation.

Missouri

Factors affecting water quality in selected carbonate aquifers in the United States, 1993-2005

Carbonate aquifers are an important source of water in the United States; however, these aquifers can be particularly susceptible to contamination from the land surface. The U.S. Geological Survey National Water-Quality Assessment (NAWQA) Program collected samples from wells and springs in 12 carbonate aquifers across the country during 1993–2005; water-quality results for 1,042 samples were available to assess the factors affecting ground-water quality. These aquifers represent a wide range of climate, land-use types, degrees of confinement, and other characteristics that were compared and evaluated to assess the effect of those factors on water quality. Differences and similarities among the aquifers were also identified. Samples were analyzed for major ions, radon, nutrients, 47 pesticides, and 54 volatile organic compounds (VOCs). Geochemical analysis helped to identify dominant processes that may contribute to the differences in aquifer susceptibility to anthropogenic contamination. Differences in concentrations of dissolved oxygen and dissolved organic carbon and in ground-water age were directly related to the occurrence of anthropogenic contaminants. Other geochemical indicators, such as mineral saturation indexes and calcium-magnesium molar ratio, were used to infer residence time, an indirect indicator of potential for anthropogenic contamination. Radon exceeded the U.S. Environmental Protection Agency proposed Maximum Contaminant Level (MCL) of 300 picocuries per liter in 423 of 735 wells sampled, of which 309 were drinking-water wells. In general, land use, oxidation-reduction (redox) status, and degree of aquifer confinement were the most important factors affecting the occurrence of anthropogenic contaminants. Although none of these factors individually accounts for all the variation in water quality among the aquifers, a combination of these characteristics accounts for the majority of the variation. Unconfined carbonate aquifers that had high percentages of urban or agricultural land, or a combination of both, had higher concentrations and higher frequency of detections for most of the anthropogenic contaminants than areas with other combinations of land use and degree of aquifer confinement. Redox status is an indicator of more recently recharged water and affects the fate of some contaminants. Median concentrations of nitrate were highest in the Valley and Ridge and Piedmont aquifers and lowest in the Biscayne and Silurian-Devonian/Upper carbonate aquifers. Nitrate concentrations were significantly higher in unconfined aquifers than in confined aquifers and semiconfined/mixed confined aquifers (wells in aquifers with breached confining layers or wells open to both a confined and an unconfined aquifer). Water recharged after 1953 had significantly higher concentrations of nitrate than water recharged prior to 1953. Redox status was also a key factor affecting nitrate concentrations; in recently recharged waters, samples in oxic waters had significantly higher concentrations of nitrate than anoxic waters, regardless of land use in the area around the well. Samples from 54 wells (5 percent) exceeded the U.S. Environmental Protection Agency MCL of 10 mg/L for nitrate in drinking water. Most of the samples exceeding the drinking-water standard (52 samples, or 5 percent) were in domestic supply wells in agricultural areas. The Piedmont and Valley and Ridge aquifers had the largest number of samples (45) exceeding the MCL; in the remaining aquifers only 9 samples had concentrations of nitrate that exceeded the MCL (about 1 percent). None of the water recharged prior to 1953 and only a single sample from a confined aquifer had nitrate concentrations that exceeded 10 mg/L as N. Wells were sampled for a minimum of 47 pesticides. Detection frequencies and comparisons varied depending on the assessment level used. At least 1 of the 47 pesticides was detected at 510 (50 percent) of the 1,027 sites where pesticide data were available using the ‘all detections’ assessment level—that is, including any quantified detection as well as any estimated values where the compound was definitively detected. Multiple pesticides were frequently detected in a sample of water from a site; 34 percent of the samples had two to five pesticides detected in the same sample, and 4 percent of the samples had six or more pesticides detected. Dieldrin was detected at 20 sites, 9 of which were from either domestic or public supply wells, at a concentration above the Health-Based Screening Level (HBSL) of 0.002 µg/L. Diazinon was detected at a concentration greater than the HBSL of 1 µg/L at a single site, which was also a domestic supply well. These are the only samples where a pesticide exceeded a human-health benchmark. The most frequently occurring pesticide compounds were four herbicides—atrazine, simazine, metolachlor, and prometon—and deethylatrazine, a degradate of atrazine. These pesticides typically were detected at concentrations that were less than 10 percent of a human-health benchmark. Of the four frequently occurring pesticides, only samples for atrazine (3 percent) and simazine (0.1 percent) had concentrations that exceeded 10 percent of the human-health benchmark; most of these cases were in agricultural areas. It is important to note, however, that the most frequently occurring pesticide degradate compound—deethylatrazine—has no human-health benchmark. Using a common assessment level of 0.01 µg/L, four of the aquifers—Biscayne, Mississippian, Piedmont, and Valley and Ridge—had at least one of these five compounds detected in more than 30 percent of the wells sampled. These four aquifers, along with the Ordovician, Ozark Plateaus, and Prairie du Chien aquifers were the aquifers or aquifer systems that had concentrations of pesticides that exceeded 10 percent of a human-health benchmark. Water recharged after 1953 had a significantly higher percentage of detections of pesticides than water recharged before 1953, and water from unconfined aquifers had a significantly higher percentage of detections of pesticides than water from confined or semiconfined/mixed confined aquifers. Water from sites in unconfined aquifers, where land use was agricultural or urban, accounted for the vast majority of detections of pesticides. Dissolved oxygen concentration was positively related to pesticide occurrence, which likely reflects the positive association between dissolved oxygen concentration and recently recharged water. Water samples were collected for analysis of VOCs at 793 sites—154 samples were analyzed for 54 VOCs from 1993 through 1995 and 639 samples were analyzed for 86 VOCs from 1996 through 2005. Twenty percent of samples contained one or more VOCs at concentrations greater than or equal to 0.2 µg/L (159 of 793 samples). The aquifers with the highest percentage of samples containing one or more VOCs were the Castle Hayne (about 41 percent of samples) and Biscayne aquifers (34 percent). The most frequently detected VOCs were chloroform, tetrahydrofuran, tetrachloroethene (PCE), toluene, acetone, ethylmethylketone, methyl tert-butyl ether (MTBE), and trichloroethene (TCE). Low-level concentrations of VOCs occurred in a much larger percentage of a subset of the data (the 639 samples analyzed using a low-level analytical method). In these samples, 69 percent of the 639 samples contained 1 or more VOCs, indicating the vulnerability of the carbonate aquifers to low-level VOC contamination. Four VOCs were detected at concentrations exceeding their respective MCLs in five samples, all of which were from drinking-water wells. Vinyl chloride concentrations exceeded the MCL of 2 µg/L in two samples from urban areas in the unconfined Biscayne aquifer. PCE, TCE, and 1,2-dichloropropane each had one sample with a concentration greater than their MCLs of 5 µg/L; these samples were from agricultural and urban areas in the unconfined Mississippian aquifer. Water quality in the 12 carbonate aquifers was highly variable. Most of the samples met drinking-water standards. The occurrence of anthropogenic contaminants was related to contaminant sources but also was affected by degree of aquifer confinement, ground-water age, and redox status. Areas with higher amounts of agricultural or urban land in unconfined aquifers were the most likely to have elevated concentrations of anthropogenic contaminants.

Scientific Investigations Report

Surface-water-quality assessment of the Yakima River basin, Washington: Overview of major findings, 1987-91

Surface-water-quality conditions were assessed in the Yakima River Basin, which drains 6,155 square miles of mostly forested, range, and agricultural land in Washington. The Yakima River Basin is one of the most intensively farmed and irrigated areas in the United States, and is often referred to as the &ldquo;Nation&rsquo;s Fruitbowl.&rdquo; Natural and anthropogenic sources of contaminants and flow regulation control water-quality conditions throughout the basin. This report summarizes the spatial and temporal distribution, sources, and implications of the dissolved oxygen, water temperature, pH, suspended sediment, nutrient, organic compound (pesticide), trace element, fecal indicator bacteria, radionuclide, and aquatic ecology data collected during the 1987&ndash;91 water years. The Yakima River descends from a water surface altitude of 2,449 feet at the foot of Keechelus Dam to 340 feet at its mouth downstream from Horn Rapids Dam near Richland. The basin can be divided into three distinct river reaches on the basis of its physical characteristics. The upper reach, which drains the Kittitas Valley, has a high gradient, with an average streambed slope of 14 feet per mile (ft/mi) over the 74 miles from the foot of Keechelus Dam (river mile [RM] 214.5) to just upstream from Umtanum. The middle reach, which drains the Mid Valley, extends a distance of 33 miles from Umtanum (RM 140.4) to just upstream from Union Gap and also has a high gradient, with an average streambed slope of 11 ft/mi. The lower reach of the Yakima River drains the Lower Valley and has an average streambed slope of 7 ft/mi over the 107 miles from Union Gap (RM 107.2) to the mouth of the Yakima River. These reaches exhibited differences in water-quality conditions related to the differences in geologic sources of contaminants and land use. Compared with the rest of the basin, the Kittitas Valley and headwaters of the Naches River Subbasin had relatively low concentrations and loads of suspended sediment, nutrients, organic compounds, and fecal indicator bacteria. There were very few failures to meet the Washington State dissolved oxygen standard or exceedances of the water temperature and pH standards in this reach. In general, these areas are considered to be areas of lessdegraded water quality in the basin. The preTertiary metamorphic and intrusive rocks of the Cle Elum and Teanaway River Subbasins, however, were found to be significant geologic sources of antimony, arsenic, chromium, copper, mercury, nickel, selenium, and zinc. As a result, the arsenic, chromium, and nickel concentrations measured in the streambed sediment of the Kittitas Valley were 13 to 74 times higher than those measured in the Lower Valley. The Mid and Lower Valleys had similar water-quality conditions, governed by the intensive agricultural and irrigation activities, highly erosive landscapes, and flow regulation. Most of the failures to meet the Washington State standards for dissolved oxygen and exceedances of the standards for water temperature and pH occurred in the Mid and Lower Valleys. Agricultural drains in the Mid and Lower Valleys were found to be significant sources of nutrients, suspended sediment, pesticides, and fecal indicator bacteria. Downstream from the irrigation diversions near Union Gap, summertime streamflow in the Yakima River was drastically reduced to only a few hundred cubic feet per second. In the lower Yakima River, agricultural return flow typically accounts for as much as 80 percent of the main stem summertime flow near the downstream terminus of the basin. Therefore, the water-quality characteristics of the lower Yakima River resemble those of the agricultural drains. The highest fecal bacteria concentrations (35,000 colonies of Escherichia coli per 100 milliliters of water) were measured in the Granger/Sunnyside area, the location of most of the livestock in the basin. The east side area of the Lower Valley (area east of the Yakima River) was the predominant source area for suspended sediment and pesticides in the basin. This area had the largest acreage of irrigated land and generally received the largest application of pesticides. Owing to the highly erosive soils of the area, the suspended sediment load from the east side in June 1989 (320 kilograms per day) was five or more times larger than from any other area, and the loads of several of the more hydrophobic organic compounds were four or more times larger. An ecological assessment of the Yakima River Basin ranked physical, chemical, and biological conditions at impaired (degraded) sites against reference sites in an effort to understand how land use changes physical and chemical site characteristics and how biota respond to these changes. For this assessment, the basin was divided into four natural ecological categories: (1) Cascades ecoregion, (2) Eastern Cascades Slopes and Foothills ecoregion, (3) Columbia Basin ecoregion, and (4) large rivers. Each of these categories has a unique combination of climate and landscape features that produces a distinctive terrestrial vegetation assemblage. In the combined Cascades and Eastern Cascades site group, which had the fewest impaired sites, the metals index was the only physical and chemical index that indicated any impairment. The moderate levels of impairment noted in the invertebrate and algal communities were not, however, associated with metals, and may have been related to the effects of logging, although the intensity of logging was not directly quantified in this study. Sites in the Columbia Basin site group were all moderately or severely impaired with the exception of the two reference sites (Umtanum Creek and Satus Creek below Dry Creek), which showed no physical, chemical, or biological impairment. Three sites were heavily affected by agriculture (Granger Drain, Moxee Drain, and Spring Creek) and were listed as severely impaired by most of the physical, chemical, and biological condition indices. Agriculture was the primary cause of the impairment of biological communities in this site group. The primary physical and chemical indicators of agricultural effects were nutrients, pesticides, dissolved solids, and substrate embeddedness, which all tended to increase with agricultural intensity. The biological effects of agriculture were manifested by a decrease in the abundance and number of native species of fish and invertebrates, a shift in algal communities to species indicative of eutrophic conditions, and higher abundances. There was also an increase in the abundance and number of nonnative fish species due to the prevalence of fish that are largely tolerant of nutrient-rich conditions. Main stem (large river) sites downstream from the city of Yakima exhibited severe impairment of fish communities associated with high levels of pesticides in fish tissues and the presence of external anomalies on fish.

Washington

Surface-water-quality assessment of the Yakima River basin in Washington: Spatial and temporal distribution of trace elements in water, sediment, and aquatic biota, 1987-91

The report describes the distribution of trace elements in sediment, water, and aquatic biota in the Yakima River basin, Washington. Trace elements were determined from streambed sediment, suspended sediment, filtered and unfiltered water samples, aquatic insects, clams, fish livers, and fish fillets between 1987 and 1991. The distribution of trace elements in these media was related to local geology and anthropogenic sources. Additionally, annual and instantaneous loads were estimated for trace elements associated with suspended sediment and trace elements in filtered water samples. Trace elements also were screened against U.S. Environmental Protection Agency guidelines established for the protection of human health and aquatic life.

Washington

Water quality of the lower Columbia River Basin: Analysis of current and historical water-quality data through 1994

The lower Columbia River Basin includes the river basins draining into the Columbia River below Bonneville Dam&mdash;the largest of which is the Willamette River. This report presents the results of a study by the U.S. Geological Survey, done in cooperation with the Lower Columbia River Bi-State Water- Quality Program, to describe the water-quality conditions in the lower Columbia River Basin by interpreting historical data collected and data collected in 1994. Historical water-quality data spanning more than 50 years and comprising more than 200 parameters were collated for interpretation in this report. The U.S. Geological Survey, the Oregon Department of Environmental Quality, and the Washington Department of Ecology collected water-quality data at 10 sites in the lower Columbia River Basin from January to December of 1994. Water-quality constituents measured in 1994 were screened against U.S. Environmental Protection Agency (EPA) and State guidelines. Arsenic, a human carcinogen, was detected in 15 of 16 samples in the lower Columbia River, but was not detected in any of the sampled tributaries. All 15 arsenic detections had concentrations that exceeded both the EPA ambient water-quality criteria for the protection of human health and the EPA human-health advisories for drinking water. Chromium was detected at all four Columbia River sites&mdash;most frequently in the Columbia River at Hayden Island. None of the chromium concentrations detected, however, exceeded water-quality criteria or guidelines. Measurements of suspended trace-element concentrations (trace-element concentrations associated with the suspended-sediment fraction) showed that the suspended form is the dominant transport phase for aluminum, iron, and manganese, whereas the dissolved form is the dominant transport phase for arsenic, barium, chromium, and copper. On the basis of tributary loads during summer low-flow months, sources of suspended silver, nickel, aluminum, and antimony exist in the lower Columbia River Basin, whereas the sources of suspended zinc and arsenic exist outside of the lower basin. Twenty organic compounds were detected of the 47 compounds analyzed for this study. None of the organic compounds measured exceeded EPA&rsquo;s ambient water-quality criteria or drinking-water guidelines. The Willamette River at Portland had the largest number of detections, and all 20 compounds were detected at one time or another at that site. The largest concentrations of the agricultural pesticides, atrazine, metolachlor, and simazine were detected in the Willamette River, where they were detected in 93, 86, 93 percent, respectively, of the samples collected. The highest concentrations of atrazine in the Willamette River were associated with the spring application and fall runoff periods. Both historical and current data showed that the highest water temperatures in the lower Columbia River Basin are present during August. For water years 1977&ndash;81 in the Columbia River at Bradwood (river mile 38.9), 75 percent of the daily mean water temperatures during August exceeded 20 degrees Celsius, a &ldquo;special condition&rdquo; criterion for the State of Washington. The special condition criterion was exceeded at four sites on the lower Columbia River during July and August, 1994&mdash;a period coinciding with season-high air temperatures and low streamflow. Trend tests using data from 1974 to 1994 showed significant (r < 0.05) upward trends for water temperature at the Columbia River at Warrendale and the Willamette River at Portland. Concentrations of dissolved oxygen and total dissolved gas were above saturation levels during high stormflows in the lower Columbia River and the Willamette River during 1994. The high concentrations of total dissolved gas in the Columbia River exceeded Oregon and Washington State standards of 110 percent of saturation and were caused by spilling water at the Columbia River dams. Aquatic life in the lower Columbia River Basin was not subjected to low dissolved-oxygen concentrations. Comparison of dissolved-oxygen concentrations in the Willamette River from 1949&ndash;58 to 1972&ndash;94 showed a significant increase in dissolved-oxygen concentrations during the low-streamflow months of summer. Trend tests showed significant (r < 0.05) downward trends from 1973 to 1994 for three constituents at the Columbia River at Warrendale: phosphorus in unfiltered water, total dissolved solids, and specific conductance. These trends may be a consequence of more conservative agricultural practices in the area upstream from Warrendale.

Oregon

Surface-water-quality assessment of the Yakima River basin in Washington: major-and minor-element data for sediment, water, and aquatic biota, 1987-91

Major- and minor-element concentrations are presented for streambed and suspended sediment, filtered- and unfiltered-water, and aquatic-biota samples collected during 1987-91 from the Yakima River Basin in south-central Washington. The samples were collected as part of the U.S. Geological Survey's National Water-quality Assessment (NAWQA) program which is designed to provide results that are useful in understanding and managing the Nation's water resources. This report includes the sampling approach, field collection and processing techniques, and methods of chemical analysis, as well as a compilation of chemical data, statistical summaries, and quality- control data. These data may be used by scientists and resource managers to describe (1) spatial distribution of selected major and minor elements in sediment, water, and aquatic biota of the Yakima River Basin; (2) temporal variation for element concentrations in filtered water and in suspended sediment at selected sites; (3) suita- bility of surface water for preservation of aquatic life and protection of human health; and (4) major natural and anthropogenic sources of major and minor elements in the Yakima River Basin that affect observed water-quality conditions. Streambed-sediment samples were collected once from 27 sites in the basin during 1987-91. Suspended-sediment and filtered-water samples were collected monthly and during hydrologic events (including snowmelt and winter rainstorms) at seven sites, and filtered-water samples were collected at least once at an additional 37 sites during synoptic samplings. Unfiltered-water samples were collected at seven sites on a quarterly basis during 1987 only. Samples of aquatic plants were collected once in 1989, and aquatic insects, fish, and clams were collected from 34 sites three times during 1989-90.

Washington