Pesticide concentrations at all fixed sites ranged often applied to powerline and road rights-of-way, was from 0.001 to 2.0 µg/L (table 4). Ten pesticides—atra- detected at a substantially higher frequency at Copper zine, bromacil, dichlorprop, 2,6-diethylaniline, meto- Creek than at the Nolichucky River or Big Limestone lachlor, metribuzin, simazine, carbaryl, carbofuran, Creek. Detection frequencies for Big Limestone Creek and diazinon—were detected in water samples at con- and the Nolichucky River near Lowland were similar centrations greater than 0.10 µg/L (table 4). In 47 of for atrazine, deethylatrazine, metolachlor, napropam- the 362 water samples collected at the fixed sites, one ide, and carbofuran (fig. 4). The most noticeable dif- or more pesticides were detected at a concentration ference between these two sites was that metribuzin, greater than 0.10 µg/L. Concentrations of atrazine an herbicide used to control a large number of grasses exceeded 0.10 µg/L in 37 samples, and concentrations and broadleaf weeds on a variety of agricultural crops of metolachlor exceeded 0.10 µg/L in 11 samples. (potatoes, soybeans, and winter wheat), was detected Seven water samples had concentrations of one or in 17 percent of the samples at the Nolichucky River more pesticides exceeding 0.50 µg/L, and only four near Lowland but was not detected at Big Limestone samples had concentrations of one or more pesticides Creek. Big Limestone Creek is a tributary to the Noli- that exceeded 1.0 µg/L. chucky River, and both drain the same general agricul- Differences in pesticide occurrence among the turally dominated area; however, the Big Limestone three agricultural sites (Big Limestone Creek, Copper Creek Basin contains a higher percentage of agricul- Creek, and Nolichucky River) were related to the vari- tural land use (both pasture and cropland) than the ety of land uses and pesticide application within each remainder of the Nolichucky River Basin. Agricultural 2 basin. Among the agricultural sites, more pesticides land accounts for only about 39 percent (650 mi ) of (22) were detected in samples from the Nolichucky the drainage upstream of the Nolichucky River site; River near Lowland than from the other agricultural however, most of the area adjacent to or directly sites (fig. 4). Similarly, more pesticides also were upstream from the sampling site is predominantly detected in samples from Big Limestone Creek (17) agricultural. than at Copper Creek (11) probably because of a Detection frequencies of pesticides at the three greater percentage of agricultural land use and a agricultural sites generally characterize pesticide greater variety of crops grown in the Big Limestone detection at all fixed sites; however, some noticeable Creek Basin. Tebuthiuron, a noncropland herbicide differences were observed (fig. 4). At the agricultural

14 Seasonal and Spatial Variability of Pesticides in Streams of the Upper Tennessee River Basin, 1996-99 sites, 27 different pesticides were detected. Detection Comparisons of Detection Frequencies in the frequencies at Big Limestone Creek near Limestone Upper Tennessee River Basin with Detection and the Nolichucky River near Lowland were particu- Frequencies Across the Nation larly high when compared to the detection frequencies at the other fixed sites for the pesticides (atrazine and Pesticide detection frequencies for the UTEN metolachlor), which are commonly used for agricul- were compared to a national summary of pesticide ture in the UTEN. Detection frequencies of pesticides detections compiled by the USGS from NAWQA stud- in water samples at the Nolichucky River site more ies that were completed in 36 of the Nation’s major closely resembled detection frequencies at the other 10 hydrologic basins from 1992 to 1998 and that included fixed sites probably because of a greater degree of analyses of about 2,500 samples collected at 115 fixed mixed land use in the Nolichucky River Basin. Detec- sites. Pesticide detection frequencies in the UTEN tion frequencies of pesticides for Copper Creek, how- were compared to the national averages for stream ever, varied considerably from the other sites, sites with agricultural drainages as well as for sites particularly for some of the more commonly detected with drainages of mixed land use. pesticides such as metolachlor, simazine, and prome- Atrazine, deethylatrazine, tebuthiuron, and ton (fig. 4). Tebuthiuron was detected more frequently napropamide were detected in streams of agricultural at Copper Creek than at the other agricultural sites, drainages in the UTEN more frequently than at agri- perhaps as a result of road construction and weed con- cultural sites included in the national summary of pes- trol on roadway rights-of-way upstream of the sam- ticide detections (fig. 5). Atrazine and deethylatrazine pling site. At Copper Creek, 11 pesticides were were detected in 99 and 98 percent of samples in the detected in 51 samples; however, only 4 pesticides UTEN compared to the national average for agricul- were detected in more than 2 samples (less than 4 per- tural sites of 85 and 69 percent, respectively. Tebuthiu- cent of samples). ron was detected in 62 percent of samples in the Of the 47 pesticides that were analyzed in all UTEN compared to the average of 22 percent for agri- samples (using the GC/MS method), 7 pesticides cultural sites nationwide. The detection frequency for detected at the fixed sites were not detected at any of napropamide in the UTEN slightly exceeded the the sites included in the spatial analysis. Conversely, national average for agricultural indicator sites (6.2 only one pesticide (terbacil) was detected at a spatial- and 5.6 percent, respectively). Pesticides that were analysis site that was not detected in samples collected detected considerably less frequently in the UTEN at the fixed sites. streams than at the nationwide agricultural sites

Pesticides in Streams of the Upper Tennessee River Basin 15 included alachlor, acetochlor, carbofuran, diazinon, the samples collected at UTEN sites had concentra- metolachlor, metribuzin, prometon, and simazine. tions of one or more pesticides that exceeded the Atrazine, deethylatrazine, metolachlor, tebuthiu- chronic aquatic-life criteria (fig. 6), and the exceed- ron, and napropamide were detected more frequently ances were for atrazine, diazinon, carbaryl, and lin- at mixed land-use sites in the UTEN than at mixed dane. land-use sites included in the national summary of Total pesticide concentrations were computed pesticide detections (fig. 5). Atrazine and deethylatra- by summing the concentrations of the detectable pesti- zine were detected in 94 and 95 percent of samples cides (above the MRL) for each sample in order to from mixed land-use sites in the UTEN compared to account for the presence of multiple pesticides. Total the national average for mixed land-use sites of 83 and pesticide concentrations for samples collected at the 68 percent, respectively. For mixed land-use sites, fixed sites in the UTEN ranged from less than metolachlor was detected in 84 percent of samples in 0.001 µg/L at Clear Creek at Lilly Bridge near Lanc- the UTEN compared to 74 percent nationwide; and ing, Tenn., to 3.15 µg/L for a sample with eight pesti- tebuthiuron was detected in 61 percent of samples in cide detections collected at Nolichucky River near the UTEN compared to the average of 34 percent for Lowland, Tenn. The effects of pesticide mixtures on mixed land-use sites nationwide. Detection frequency biota and human health are unknown; however, this is for napropamide in the UTEN slightly exceeded the an area of active research, and the U.S. EPA is consid- national average for mixed land-use sites (fig. 5). ering establishing health standards for combinations of Comparison of detection frequencies at sites with pesticides (U.S. Environmental Protection Agency, mixed land-use drainages in the UTEN with national 1994). averages reveal results similar to the agricultural sites with the exception of metolachlor, which was detected more frequently in the UTEN. SEASONAL AND SPATIAL VARIABILITY OF PESTICIDES IN STREAMS OF THE UPPER TENNESSEE RIVER BASIN Water-Quality Standards Pesticide occurrence and concentrations varied The U.S. EPA has established water-quality seasonally and spatially in the UTEN and were closely standards and guidelines that specify thresholds of associated with land use and time of application. Peak concentrations of certain chemicals that have adverse concentrations of pesticides generally were detected effects on human health, aquatic organisms, and wild- during the spring and immediately following pesticide life. Although the maximum contaminant levels application. However, low levels (concentrations gen- (MCL) and lifetime health advisory levels (HAL) erally less than 0.10 µg/L) of pesticides were detected established by the U.S. EPA (2000) pertain to finished throughout the year at the fixed sites in the UTEN. drinking water supplied by a community water system, Seasonal variability was evident for several pes- values are provided with which ambient concentra- ticides at the 13 fixed sites. Monthly sampling for pes- tions can be compared. MCLs or HALs have been ticides at fixed sites was conducted to characterize the established for 21 of the 31 pesticides and metabolites seasonal variation of pesticides in streams in the detected at sites in the UTEN study (table 4). Aquatic- UTEN. Peak concentrations occurred during the grow- life criteria have been established for the protection of ing season (April through September) for all pesticides aquatic organisms for short-term (acute) and long-term except dichlobenil, trifluralin, and alpha HCH (chronic) exposures. Chronic aquatic-life criteria have (table 4). Differences in pesticide concentrations (and been established for 14 of the 31 pesticides and metab- detection frequencies) between the growing and non- olites detected at sites in the UTEN study (table 4). growing seasons were pronounced for the French Concentrations of pesticides and metabolites Broad River, Middle Fork Holston River, Clinch detected in streams in the UTEN generally were below River, Clear Creek, Big Limestone Creek, and Noli- established water-quality standards and guidelines. chucky River. Although comparisons of median con- Although most of the samples collected in the UTEN centrations between the growing and nongrowing contained detectable concentrations of one or more seasons indicate little change for some sites (Guest pesticides, no concentrations exceeded any human River and Copper Creek), maximum concentrations health standards (MCLs or HALs). Only 2 percent of for most pesticides were detected during the growing

16 Seasonal and Spatial Variability of Pesticides in Streams of the Upper Tennessee River Basin, 1996-99 season, usually during June and July following the were collected during the months of May, June, July, application of agricultural pesticides, at all fixed sites and August. (table 4). Elevated concentrations of several pesticides Data were collected at 61 stream sites to analyze including atrazine, deethylatrazine, metolachlor, the spatial variation of pesticides in 7 major subbasins tebuthiuron, simazine, prometon, and chlorpyrifos and 3 smaller tributaries to the Tennessee River were detected during the growing season at most fixed (fig. 2). Sampling conducted during the late springs sites. and early summers of 1996, 1997, and 1998 was Weekly sampling at the three agricultural sites, focused on low streamflow conditions in agricultural where the upstream drainage areas contained large and mixed land-use settings. A few water samples percentages of agricultural land, revealed that the were collected in urban streams that are influenced by highest pesticide concentrations were detected in late industrial and municipal effluents and urban runoff. In spring and early summer (fig. 7). Peak herbicide con- 1996, data collection was focused in the Clinch, Pow- centrations usually coincided with the first substantial ell, and Emory River Basins; in 1997, in the Noli- storm following agricultural applications in the spring chucky and French Broad River Basins, and in 1998, and declined to near-background levels as concentra- in the Holston River Basin. Because of breaks in the tions were diluted by the increased discharge that sampling schedule as a result of unsuitable hydrologic accompanied the storm. Maximum concentrations of conditions, these data do not portray nearly instanta- herbicides were detected during May and June follow- neous, concurrent water-quality conditions, as would ing the application of herbicides to farm fields and res- have been possible if intensive sampling had been per- idential lawns. Of the 39 samples that contained at formed over a short time period. Instead, greater least one pesticide with a concentration greater than emphasis was given to sampling under consistent 0.1 µg/L at the three agricultural sites, 36 samples streamflow conditions. Because of the offsets in

Seasonal and Spatial Variability of Pesticides in Streams of the Upper Tennessee River Basin 17 18 Seasonal and Spatial Variability of Pesticides in Streams of the Upper Tennessee River Basin, 1996-99 sampling dates, potential for variations of pesticide The spatial-analysis sites sampled in the Emory concentrations exists among sites; therefore, these River Basin are located within the Obed National Wild variations of concentrations can be related to variation and Scenic River system. Two or three pesticides were in timing of sampling relative to pesticide applica- detected at each of the five sites sampled in the Emory tions. River Basin in 1996 (fig. 9). Six pesticides were detected at one additional site that was sampled in In 1996, sampling was conducted at 24 sites pri- 1998. Atrazine and deethylatrazine were detected in marily in the Clinch, Powell, and Emory River Basins all samples, and prometon was detected in half of the to evaluate spatial distribution of pesticides. Twelve samples. Metolachlor and tebuthiuron were detected in pesticides were detected at sites in the Clinch and two samples, and diazinon was detected in one sam- Powell River Basins; the number of pesticides ple. Concentrations of the detected pesticides were detected per sample ranged from one to eight (fig. 8). generally less than 0.10 µg/L. Atrazine was detected most frequently (100 percent) The French Broad River Basin sites were sam- in samples from the Clinch River Basin sites, and pled in the spring and summer of 1997. Sampling tebuthiuron was detected most frequently (100 per- began in April but was discontinued for several weeks cent) in samples from the Powell River Basin sites. because of extremely wet weather and high stream- Concentrations of all detected pesticides were rela- flow conditions; sampling resumed in June and was tively low (less than 0.10 µg/L), with the exception of completed in July. Concentrations for 14 different pes- two tebuthiuron concentrations (0.21 and 0.26 µg/L) ticides—8 herbicides, 5 insecticides, and 1 metabo- in samples from the Powell River Basin. lite—were detected at 20 fixed and spatial-analysis

Seasonal and Spatial Variability of Pesticides in Streams of the Upper Tennessee River Basin 19 sampling sites. The number of pesticide detections per Nolichucky River Basin sites also were sampled sample ranged from none detected at five sites to eight in the summer of 1997. Concentrations for 15 different pesticides detected at three sites (fig. 10). The largest pesticides—10 herbicides, 4 insecticides, and 1 metab- number of detections were from samples in the urban olite—were detected at 10 fixed and spatial-analysis drainages of the Asheville, N.C., area. The only detec- sampling sites. The number of pesticides detected per tion of the herbicide terbacil was at Mud Creek (F5 on site ranged from four to nine. The three fixed sites in fig. 10 and appendix A), which is an urban stream near the basin, Nolichucky River near Lowland, Tenn. Asheville that is influenced by industrial activity. Pes- (site 4), Nolichucky River at Embreeville, Tenn. ticide concentrations were generally lower in the (site 10), and Big Limestone Creek near Limestone, French Broad River Basin than in the other study-unit Tenn. (site 9), were sampled during the same time basins with the exception of prometon, which was period as the spatial-analysis sites. Nine pesticides detected at a concentration of 0.16 µg/L in the French were detected at the Nolichucky River near Lowland, Broad River at Glenn Bridge Road near Arden, N.C. six pesticides were detected at the Nolichucky River at (F7 on fig. 10 and appendix A). Embreeville, and five pesticides were detected at Big

20 Seasonal and Spatial Variability of Pesticides in Streams of the Upper Tennessee River Basin, 1996-99 Limestone Creek in samples from this period (fig. 10). with high turbidity conditions. Concentrations for sev- Atrazine and deethylatrazine were detected in all sam- eral pesticides were elevated for this sample, including ples, and tebuthiuron and metolachlor were detected in atrazine (0.999 µg/L), metolachlor (4.0 µg/L), ace- 8 of the 10 samples. tochlor (0.393 µg/L), diuron (0.30 µg/L), and lindane Eight detections occurred at the only site (Little (0.012 µg/L), which was the only exceedance of an Limestone Creek at Broylesville, Tenn.—site N1) that aquatic-life criterion detected in stream samples from was not sampled during low-flow conditions in 1997. the spatial-analysis sites in the UTEN. The concentra- Little Limestone Creek was sampled several hours tions for metolachlor, diuron, and acetochlor in this after a local thunderstorm during a declining stage sample were also the highest of all 423 samples (fixed

Seasonal and Spatial Variability of Pesticides in Streams of the Upper Tennessee River Basin 21 and spatial-analysis sites) collected in the UTEN which includes parts of Tennessee, North Carolina, (1996-99); the atrazine concentration at Little Lime- Virginia, and Georgia and drains about 21,400 mi2. stone Creek exceeded 99 percent of measured concen- The fixed sites were sampled for pesticides at fixed trations. The only detections of alachlor, acetochlor, intervals and supplemented with storm-flow samples. and lindane at spatial-analysis sites in the French Samples also were collected at 61 additional sites in Broad and Nolichucky River Basins occurred at the the major subbasins of the UTEN during the springs Little Limestone Creek site. These data indicate that and summers of 1996, 1997, and 1998 to assess the pesticide concentrations can vary significantly in spatial variation of pesticides during low flow in streams during storm flows, particularly during the streams. growing season. Pesticides that were detected frequently in In 1998, samples were collected at spatial- streams in the UTEN were generally the pesticides analysis sites and two fixed sites in the Holston River having high estimated use in the basin. A total of 30 Basin. Seven different pesticides—five herbicides, one pesticides were detected in 362 samples collected at insecticide, and one metabolite—were detected in the 13 fixed sites. Herbicides were detected more fre- samples from the 12 sites. The number of pesticide quently than insecticides, which is consistent with the detections per sample ranged from zero at Horse greater use of herbicides in the UTEN. Of the 10 most Creek near Kingsport, Tenn. (site H9, fig. 8), to four at frequently detected pesticides, 8 were herbicides and 1 the North Fork Holston River at Cloud Ford, Tenn. was a metabolite of atrazine. Atrazine, metolachlor, (site H7), and at two sites on Beaver Creek near Bris- and simazine, heavily used herbicides in the UTEN, tol, Tenn./Va. (sites H5 and H6) (fig. 8). Atrazine and were detected frequently in streams in the UTEN. The metolachlor were the two most commonly detected herbicides most frequently detected at concentrations pesticides. Atrazine was detected in 11 samples; at or greater than 0.01 µg/L were atrazine (in 59 per- metolachlor was detected in 7 samples. Pesticides cent of samples), tebuthiuron (41 percent), deethyl- were measured at relatively low concentrations (less atrazine (31 percent), metolachlor (24 percent), than 0.05 µg/L) with no exceedances of human health simazine (17 percent), and prometon (6.4 percent). or aquatic-life criteria. The insecticides most frequently detected at At the 61 stream sites, 20 different pesticides concentrations at or greater than 0.01 µg/L were car- were detected, and at least 1 pesticide was detected in baryl (6.1 percent), diazinon (1.9 percent), carbofuran 89 percent of the samples collected. Median concen- (1.7 percent), and chlorpyrifos (1.1 percent). trations of pesticides for all spatial-analysis samples Pesticide detection frequencies also were asso- equaled the MRL for all pesticides except atrazine and ciated with land use. Generally, the most frequently deethylatrazine. Pesticide concentrations most fre- detected pesticides (atrazine, deethylatrazine, quently exceeding the threshold concentration of metolachlor, and simazine) were those applied to agri- 0.01 µg/L were atrazine (54 percent), tebuthiuron cultural land. Detection frequencies of pesticides var- (41 percent), deethylatrazine (17 percent), metolachlor ied from site to site, reflecting differences in land use (16 percent), simazine (14 percent), and prometon in the upstream drainages. Although Copper Creek (12 percent). Although the detection frequencies were near Gate City, Va., is an intensively agricultural site, lower for most pesticides at the spatial-analysis sam- metolachlor was detected in only 18 percent of the ple sites in comparison to the fixed sites, the same samples from the Copper Creek site. Tebuthiuron and group of pesticides were most frequently detected at prometon, which are most commonly used in noncrop- both sets of sites. Seven pesticides detected at the land areas and on pastureland, also were among the fixed sites were not detected at any of the spatial- most frequently detected herbicides in the UTEN analysis sites. study. Pesticide detection frequencies for the UTEN SUMMARY were compared with the national summary compiled by the USGS from NAWQA studies (1992-98); atra- The USGS conducted an assessment of pesti- zine, deethylatrazine, tebuthiuron, and napropamide cides in streams in the UTEN as part of the National were more frequently detected in the UTEN study than Water-Quality Assessment Program. Thirteen stream in the national summary of pesticide detections for sites were selected as fixed sampling sites to represent streams with agricultural drainages and for streams the diverse land uses, physiographic settings, and draining areas of mixed land use. Atrazine and other drainage-basin characteristics in the UTEN, deethylatrazine were detected in about 99 and

22 Seasonal and Spatial Variability of Pesticides in Streams of the Upper Tennessee River Basin, 1996-99 98 percent of samples, respectively, in the UTEN com- and chlorpyrifos were detected during the growing pared to the national average of about 85 and season at most fixed sites. 69 percent, respectively, for agricultural sites. Tebuthi- Concentrations of pesticides and metabolites in uron was detected in 62 percent of water samples from streams in the UTEN generally were well below estab- agricultural sites in the UTEN as compared to about lished water-quality criteria. Although most of the 22 percent of samples from agricultural sites nation- water samples collected in the UTEN study area con- wide. Pesticides that were detected considerably less tained detectable concentrations of one or more pesti- frequently in the UTEN streams than at the nationwide cides, none of the concentrations exceeded human agricultural sites included alachlor, acetochlor, carbo- health standards. Only 21 of the 31 pesticides furan, diazinon, metolachlor, metribuzin, prometon, and simazine. Comparison of detection frequencies at detected, however, have established MCL or HAL cri- sites with mixed land-use drainages in the UTEN with teria. Of the 14 pesticides detected that have estab- the national averages reveal results similar to the agri- lished criteria for the protection of aquatic life, only cultural sites with the exception of metolachlor, which carbaryl, lindane, diazinon, and atrazine were detected was detected more frequently in the UTEN. at concentrations exceeding the criteria in 7 of the 362 Low concentrations (generally less than samples collected at fixed sites. 0.10 µg/L) of pesticides were detected at all 13 fixed Spatial analysis of pesticide detections and con- sites in the UTEN. Concentrations of individual pesti- centrations in several of the subbasins of the UTEN cides ranged from 0.001 to 2.0 µg/L. Atrazine, bro- indicated that the network of fixed sites in the UTEN macil, dichlorprop, 2,6-diethylaniline, metolachlor, were generally representative of conditions throughout metribuzin, simazine, carbaryl, carbofuran, and diazi- the basin. The most frequently detected pesticides in non were detected in samples at concentrations greater water samples from the spatial-analysis sites were than 0.10 µg/L. In 47 of the 362 samples collected, atrazine, deethylatrazine, metolachlor, tebuthiuron, one or more pesticides were detected in samples at simazine, and prometon. Only 1 of the 61 stream sam- concentrations greater than 0.10 µg/L. Concentrations ples was collected under hydrologic conditions that of atrazine exceeded 0.10 µg/L in 37 samples, and did not represent low flow. This site, Little Limestone concentrations of metolachlor exceeded 0.10 µg/L in Creek at Broylesville, Tenn., was sampled several 11 samples. Seven samples had concentrations of one hours after a major storm. High concentrations of sev- or more pesticides exceeding 0.50 µg/L, and only four eral pesticides were measured at this site, including samples had concentrations of one or more pesticides one exceedance of the aquatic-life criterion for lin- exceeding 1.0 µg/L. dane. Overall, concentrations of pesticides at spatial- Peak pesticide concentrations were detected at analysis sites were lower than at fixed sites in every the agricultural sites in late spring and early summer, subbasin; however, a greater number of detections generally coinciding with pesticide applications and usually occurred at sites that were influenced by urban the first substantial runoff event following pesticide applications. Concentrations of atrazine and meto- or industrial land use. Of the 47 pesticides that were lachlor were elevated more frequently than concentra- analyzed in all samples, 7 pesticides detected at the tions of other pesticides, and most of the elevated fixed sites were not detected at any of the spatial- concentrations were detected at the agricultural sites. analysis sites. Conversely, only one of the pesticides The maximum pesticide concentration of 2 µg/L was (terbacil) detected at a spatial-analysis site was not detected for atrazine at the Nolichucky River near detected in samples collected at the fixed sites. Lowland, Tenn. Agricultural land accounts for only about 39 percent (650 mi2) of the drainage upstream of REFERENCES this site; however, most of the area adjacent to or directly upstream from the sampling site is predomi- Canadian Council of Ministers of the Environment, 1997, nantly agricultural. The maximum concentration Canadian water quality guidelines (rev. ed.): Ottawa, detected for metolachlor was 1.3 µg/L in a sample col- Ontario, Water Quality Guidelines Task Group, Cana- lected at Big Limestone Creek near Limestone, Tenn., dian Council of Resource and Environment Ministers, which has a watershed that consists of about loose-leaf (originally published 1987), 23 appendixes. 83 percent agricultural land. Elevated concentrations Capel, P.D., Nacionales, F.C., and Larson, S.J., 1995, Preci- of several pesticides including atrazine, deethylatra- sion of a splitting device for water samples: U.S. Geo- zine, metolachlor, tebuthiuron, simazine, prometon, logical Survey Open-File Report 95-293, 10 p.

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Geological Survey Open-File Report 95-181, 49 p.

24 Seasonal and Spatial Variability of Pesticides in Streams of the Upper Tennessee River Basin, 1996-99 APPENDIX

0.2 0.0 0.9 0.4 0.1 0.1 0.1 0.2 2.6 1.6 0.5 0.0 0.1 0.1 0.1 0.0 0.2 0.4 0.3 0.2 0.1 Other 1.1 2.8 7.3 7.6 0.6 4.6 3.4 3.6 2.2 4.1 3.2 0.5 0.8 0.6 1.3 1.2 0.9 1.6 10.6 21.8 13.6 Urban 0.7 1.2 0.2 0.2 2.0 0.1 0.0 0.0 0.2 0.4 0.6 2.6 2.0 1.0 2.1 1.1 0.8 8.8 5.8 1.6 3.3 Cropland Land use (percent) 9.0 9.9 46.4 44.6 13.0 13.7 20.4 10.9 10.4 11.3 14.0 33.1 39.9 24.7 30.4 11.0 22.4 48.7 36.9 25.4 33.0 Pasture 49.8 50.6 78.5 78.0 76.9 84.3 86.1 87.0 85.1 82.6 81.7 63.3 57.2 72.9 66.1 86.7 74.9 31.5 35.2 70.8 49.9 Forest 7 9 86 23 87 32 11 25 23 89 44 52 26 62 53 105 223 136 158 329 717 area miles) (square (square Drainage date Sample 6-11-96 6-10-96 5-14-96 5-14-96 5-20-98 6-3-96 6-4-96 6-4-96 5-15-96 6-6-96 6-12-96 5-20-98 5-21-98 6-13-96 7-15-98 7-15-98 7-14-98 7-15-98 7-16-98 7-14-98 7-13-98 USGS station station number 03522000 03523080 03524330 03524500 0352763950 03529050 03529075 03529295 03530150 03530225 03530550 03531518 03531900 03488000 03472150 03472700 03489870 03478400 03478592 03490090 03487595 Powell River Basin (fig. 8) Clinch River Basin (fig. 8) (fig. Basin Clinch River Holston River Basin (fig. 8) Basin (fig. River Holston Gap, Va. s Cave near Lebanon, Va. Lebanon, near s Cave nwood near Hansonville, Va. near Hansonville, nwood n near Kingsport, Tenn. at Penningham USGS station name Blackwood, Va. Blackwood, Sites sampled for spatial analysis of pesticides in the upper Tennessee River Basin, 1996-98—Continued River analysis spatialupperthein of pesticides Tennessee Sites sampled for Sites sampled for spatial analysis of pesticides in the upper Tennessee River Basin, 1996-98 River spatialpesticides analysis of the upper in Tennessee Sites sampled for Little River at U.S. Highway 19 near Wardell, Va. 19 at near Wardell, U.S. Highway Little River Daugherty’ Big Cedar Creek below Va. at Esserville, Guest River Va. at Coeburn, Guest River Tenn. Ford, Ridge near Kyles Creek at Newman Blackwater Va, Esserville, near River Powell Va. at Norton, River Powell at River Powell Va. at Keokee, River Powell North Fork near Dryden, Va. River Powell North Fork River Powell North Fork Branch near Lone Jonesville, Va. Creek below Wallen Tenn. at Greers Chapel, Creek Indian Va. near Saltville, Holston River North Fork Damascus, Va. above River Holston South Fork Va. Damascus, at Mill Vails at Creek Laurel Creek at Big Moccasin Colli CreekBristol, at Va. Beaver Bristol, Tenn. below Avoca near Creek Beaver Tenn. near Cloud Ford, Holston River North Fork Reedy Creek at Gibsontow Site C1 C2 C3 C4 C5 P1 P2 P3 P4 P5 P6 P7 P8 H1 H2 H3 H4 H5 H6 H7 H8 number Appendix A. Appendix A. Appendix month-day-year] as given dates Survey; Geological U.S. [USGS,

Appendix A 27 0.2 0.1 1.5 0.2 0.2 0.3 0.3 1.8 0.2 0.2 1.1 0.9 0.0 0.1 1.2 0.3 0.4 0.3 0.2 0.4 0.2 7.8 1.0 2.9 0.7 2.7 0.4 4.1 2.7 0.4 0.3 4.2 2.4 0.2 0.8 1.2 1.5 0.4 1.9 4.4 4.1 13.0 3.6 4.3 1.4 0.2 1.9 2.9 3.1 7.0 5.4 3.9 4.4 4.3 0.7 1.4 1.0 0.8 1.2 6.3 1.9 3.4 0.3 Land use (percent) 4.6 9.8 4.9 4.9 2.0 7.7 36.4 33.2 16.0 18.5 15.9 21.5 39.5 29.4 24.9 29.8 27.6 32.4 28.0 17.9 15.3 52.0 61.4 78.2 94.3 76.7 80.5 71.0 49.0 60.3 68.2 60.5 64.2 89.3 92.8 91.7 95.4 90.3 48.0 68.0 73.9 80.1 Forest Pasture Cropland Urban Other 44 48 61 81 92 69 43 47 73 82 38 750 192 300 118 107 146 174 518 110 651 area miles) (square (square Drainage date Sample 7-13-98 7-17-98 7-16-98 7-9-96 6-24-96 6-25-96 6-27-96 7-25-96 7-23-96 7-22-96 7-24-96 6-30-98 6-26-96 7-9-97 7-9-97 7-8-97 7-30-97 4-17-97 4-16-97 4-17-97 7-29-97 4-9-97 ies to the Tennessee River (fig. 9) (fig. River Tennessee ies to the USGS station station number 03487521 03491000 03483960 03497450 03498863 03541498 03542495 03538860 03539717 03539735 03539690 03539800 03538580 03439000 0344150700 0344114090 0344602100 0344700000 0344766600 0344776625 0344834200 French Broad River Basin (fig. 10) Basin (fig. River Broad French Holston River Basin (fig. 8)—Continued Basin (fig. River Holston Emory River Basin and other tributar and Basin Emory River ad near Little River, N.C. River, Little ad near on Highway at Brevard, N.C. at Brevard, on Highway near Mills River, N.C. near Mills River, dge near Maryville, Tenn. USGS station name Sites sampled for spatial analysis of pesticides in the upper Tennessee River Basin, 1996-98—Continued River analysis spatialupperthein of pesticides Tennessee Sites sampled for Horse Creek at Smoky Valley Tenn. near Kingsport, Valley Horse Creek at Smoky Big Creek near Rogersville, Tenn. 8) on fig. (not shown Point, Tenn. near Watauga River Watauga Bri at Coulter River Little at Rockford, Tenn. Little River Tenn. Creek near Roddy, Whites City, near Spring Creek Sock mouth of above River Piney Tenn. Tenn. Crossville, near Ford Potters at River Obed near Jones Knob, Tenn. Clear Creek at Norris Ford near Frankfort, Bridge Tenn. Ford Clear Creek at Waltham Tenn. Table, Breakfast Creek at Daddys Devil’s near Tenn. Lancing, Obed River Lancing, Tenn. near River Emory at Rosman, N.C. French River Broad Ro Lake at Cascade River Little at Old Henders River Davidson at Hopper Lane Mills River N.C. Naples, at Mud Creek N.C. CaneatCreekU.S. Fletcher, at 25 near Arden, N.C. Road Glenn Bridge at River French Broad N.C. Creek at Candler, South Hominy Site H9 H10 -- L1 L2 W1 W2 E1 E2 E3 E4 E5 E6 F1 F2 F3 F4 F5 F6 F7 F8 number Appendix A.

28 Seasonal and Spatial Variability of Pesticides in Streams of the Upper Tennessee River Basin, 1996-99 0.2 0.7 0.6 0.0 0.1 0.1 0.0 0.0 0.5 0.0 0.0 0.1 0.2 0.1 0.1 0.1 0.1 0.2 0.3 7.0 7.7 6.0 6.7 0.9 2.6 6.6 0.7 0.3 9.1 2.5 6.5 2.1 4.9 3.6 6.7 5.2 12.3 10.9 1.1 0.6 2.6 6.6 1.1 3.7 3.5 2.2 2.8 0.9 0.5 9.4 7.9 9.7 9.7 1.2 10.9 16.7 11.5 Land use (percent) 8.5 6.8 7.8 18.6 16.6 37.6 14.9 32.2 23.5 20.1 18.8 64.8 68.7 55.7 51.4 63.4 55.6 58.7 11.2 67.8 79.3 73.2 48.0 77.9 57.4 72.1 75.1 71.3 91.6 91.4 15.1 11.9 28.3 38.5 21.8 31.1 23.0 82.1 Forest Pasture Cropland Urban Other 33 34 25 45 58 70 27 14 39 78 39 39 103 130 944 154 262 568 area miles) 1331 (square (square Drainage date Sample 4-16-97 4-15-97 7-30-97 4-8-97 4-9-97 4-10-97 4-8-97 7-8-97 7-31-97 4-22-97 4-21-97 7-1-97 7-16-97 6-25-97 7-17-97 6-24-97 6-25-97 6-24-97 7-10-96 USGS station station number 0344878100 03451000 03451500 0345169000 0345182580 0345195390 0345199400 0345292005 03453500 03454000 0345458780 03465650 03466233 03466698 03466835 03467485 03467300 03468065 03461080 Pigeon River Basin River Pigeon Nolichucky River Basin (fig. 10) Basin (fig. River Nolichucky French Broad River Basin (fig. 10)—Continued Basin (fig. River Broad French USGS station name Sites sampled for spatial analysis of pesticides in the upper Tennessee River Basin, 1996-98—Continued River analysis spatialupperthein of pesticides Tennessee Sites sampled for Hominy Creek near West Asheville, N.C. Asheville, Creek near West Hominy N.C. at Biltmore, River Swannanoa N.C. at Asheville, French River Broad N.C. Creek near Alexander, Newfound N.C. Weaverville, near Road Stock at New Creek Reems N.C. Weaverville, near Creek Flat N.C. Volga, near Sandymush Creek at Marshall, N.C. Ivy River at Marshall, N.C. French River Broad N.C. Big Laurel Creek Stackhouse, near Spring Creek at NC 209 near Hot Springs, N.C. Tenn. at Broylesville, Creek Limestone Little Tenn. Afton, WWTP near at Sinking Creek Tenn. Creek near Warrensburg, Little Chucky Tenn. near Baileyton, Mill near Lick Creek Creek Lick Tenn. City, Silver near Creek Bent Mill, Tenn. at Scoot Creek Lick Tenn. Lowland, near Creek Long near Denton, Tenn. Pigeon River Site F9 F10 F11 F12 F13 F14 F15 F16 F17 F18 F19 N1 N2 N3 N4 N5 N6 N7 PI1 number Appendix A.

Appendix A 29