Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

Prepared in cooperation with the Missouri Department of Natural Resources

Scientific Investigations Report 2007–5181

U.S. Department of the Interior U.S. Geological Survey Cover Photographs. Little Sugar Creek near Pineville, Missouri (07188838), September 2004 (inset: November 2004). Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

By Brenda J. Smith, Joseph M. Richards, and John G. Schumacher

Prepared in cooperation with the Missouri Department of Natural Resources

Scientific Investigations Report 2007–5181

U.S. Department of the Interior U.S. Geological Survey U.S. Department of the Interior DIRK KEMPTHORNE, Secretary U.S. Geological Survey Mark D. Myers, Director

U.S. Geological Survey, Reston, Virginia: 2007

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Suggested citation: Smith, B.J., Richards, J.M., and Schumacher, J.G., 2007, Water and streambed-sediment quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06: U.S. Geological Survey Scientific Investigations Report 2007–5181, 53 p. iii

Contents

Abstract...... 1 Introduction...... 1 Background...... 2 Purpose and Scope...... 2 Study Area Description...... 2 Methods of Study...... 8 Sample Collection and Analysis Methods...... 8 Data Analysis Methods...... 9 Water Quality...... 10 Historical Water Quality...... 10 Ambient Water Quality...... 13 Stormwater Water Quality...... 18 Seepage Run Water Quality...... 29 Streambed-Sediment Quality...... 37 Summary...... 50 References Cited...... 51

Figures

1. Map showing location of the Elk River Basin...... 3 2. Box plots showing discharge at the Elk River near Tiff City, 1960 through September 2006...... 5 3. Graphs showing monthly (A) and cumulative (B) departure from normal precipitation at Anderson, Missouri, January 1999 through September 2006...... 6 4. Map showing land use in the Upper Elk River Basin, Missouri and Arkansas...... 7 5–9. Box plots showing— 5. The distribution of selected major ion concentrations in historical water- quality samples within the Upper Elk River Basin...... 11 6. The distribution of nutrient concentrations in historical water-quality samples within the Upper Elk River Basin...... 12 7. Distribution of total phosphorus and nitrate as nitrogen concentrations, by decades, in samples from the Elk River near Tiff City...... 13 8. The distribution of total phosphorus concentrations in samples from the Elk River near Tiff City, 1962–2006...... 14 9. The distribution of nitrate as nitrogen concentrations in samples from the Elk River near Tiff City, 1960–2006...... 15 10. Scatter plot showing the relation between nitrate as nitrogen concentrations and discharge in samples from the Elk River near Tiff City, 1960 to September 2006...... 16 11. Trilinear diagram of major ions in samples from the Upper Elk River Basin, October 2004 through September 2006...... 18 iv

12–13. Box plots showing— 12. The distribution of nutrient concentrations in samples from the Upper Elk River Basin, October 2004 through September 2006...... 19 13. The distribution of monthly nutrient loads in samples from the Upper Elk River Basin, October 2004 through September 2006...... 20 14–15. Graphs showing— 14. Relation of nitrate as nitrogen concentrations in samples from the Upper Elk River Basin to discharge in the Elk River near Tiff City, October 2004 through September 2006...... 21 15. Relation of total phosphorus concentrations in samples from the Upper Elk River Basin to discharge in Little Sugar Creek near Pineville, October 2004 through September 2006...... 22 16–17. Box plots showing— 16. The distribution of nutrient concentrations in stormwater samples in the Upper Elk River Basin, October 2004 through December 2006...... 23 17. The distribution of nutrient loads in stormwater samples in the Upper Elk River Basin, October 2004 through December 2006...... 28 18. Map showing location of seepage run sites and discharge values in the Upper Elk River Basin...... 30 19–22. Bar charts showing— 19. Concentration of nitrate as nitrogen in samples from the seepage run, July 31 through August 3, 2006, in the Upper Elk River Basin...... 34 20. Concentration of total phosphorus in samples from the seepage run, July 31 through August 3, 2006, in the Upper Elk River Basin...... 35 21. Sodium, chloride, and sulfate concentrations in samples from the seepage run, November 2006, in the Upper Elk River Basin...... 39 22. Nutrient concentrations in samples from the seepage run, November 2006, in the Upper Elk River Basin...... 40 23. Maps showing concentrations of leachable nutrients normalized to organic carbon content in streambed-sediment samples in the Upper Elk River Basin, August 2005...... 41 24. Boxplots showing concentrations of selected nutrients in leachate samples normalized to organic carbon content in streambed-sediment samples in the Upper Elk River Basin, August 2005...... 46 25. Maps showing concentrations of selected trace elements normalized to organic carbon content in streambed-sediment samples in the Upper Elk River Basin, August 2005...... 47 26–27. Graphs showing— 26. Relation of selected trace-element concentrations and iron in the less than 63-micrometer size fraction of streambed-sediment samples from the Upper Elk River Basin, August 2005...... 48 27. The trend of cadmium and zinc in streambed-sediment samples in the Upper Elk River Basin, August 2005...... 49 v

Tables

1. Water-quality sampling sites and annual mean discharge within the Upper Elk River Basin, Missouri, 2004–06...... 4 2. Summary statistics for selected physical properties, inorganic constituents, and nutrients in the Upper Elk River Basin, October 2004 through September 2006...... 17 3. Values of physical properties, major ion and nutrient concentrations, and bacteria densities in stormwater samples in the Upper Elk River Basin, October 2004 through December 2006...... 24 4. Values of physical properties, major ion and nutrient concentrations, and bacteria densities in samples from the seepage run, July 31 through August 3, 2006, in the Upper Elk River Basin...... 32 5. Wastewater indicator compounds analyzed and reporting limit for samples collected during the seepage run, July 31–August 3, 2006, in the Upper Elk River Basin...... 36 6. Concentrations of wastewater indicator and pharmaceutical compounds detected in samples from the seepage run, July 31–August 3, 2006, in the Upper Elk River Basin...... 37 7. Values of physical properties, major ion and nutrient concentrations, bacteria densities, and wastewater indicator and pharmaceutical compound concentrations in samples from the seepage run, November 2006, in the Upper Elk River Basin...... 38 8. Nutrient and trace-element concentrations from streambed-sediment samples collected from the Upper Elk River Basin, August 2005...... 42 vi

Conversion Factors and Datum

Multiply By To obtain Length inch (in.) 2.54 centimeter (cm) foot (ft)) 0.3048 meter (m) mile (mi) 1.609 kilometer (km) Area acre 4,047 square meter (m2) square mile (mi2) 2.590 square kilometer (km2) Flow rate cubic foot per second (ft3/s) 0.02832 cubic meter per second (m3/s) Mass ton, short (2,000 lb) 0.9072 megagram (Mg)

Temperature in degrees Celsius (°C) may be converted to degrees Fahrenheit (°F) as follows: °F=(1.8×°C)+32 Temperature in degrees Fahrenheit (°F) may be converted to degrees Celsius (°C) as follows: °C=(°F-32)/1.8 Vertical coordinate information is referenced to the North American Vertical Datum of 1988 (NAVD 88). Horizontal coordinate information is referenced to the North American Datum of 1983 (NAD 83). Altitude, as used in this report, refers to distance above the vertical datum. Specific conductance is given in microsiemens per centimeter at 25 degrees Celsius (μS/cm at 25 °C). Concentrations of chemical constituents in water are given either in milligrams per liter (mg/L) or micrograms per liter (μg/L). Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

By Brenda J. Smith, Joseph M. Richards, and John G. Schumacher

Abstract Base-flow conditions as reflected by the seepage run of the summer of 2006 indicate that 52 percent of the discharge at the Elk River near Tiff City is contributed by Indian Creek. The U.S. Geological Survey, in cooperation with the Missouri Little Sugar Creek contributes 32 percent and Big Sugar Creek Department of Natural Resources, collected water and streambed- 9 percent of the discharge in the Elk River near Tiff City. Only sediment samples in the Upper Elk River Basin in southwestern about 7 percent of the discharge at Tiff City comes from the Missouri and northwestern Arkansas from October 2004 through mainstem of the Elk River. December 2006. The samples were collected to determine the Concentrations of dissolved ammonia plus organic stream-water quality and streambed-sediment quality. nitrogen as nitrogen, dissolved ammonia as nitrogen, dissolved In 1998, the Missouri Department of Natural Resources phosphorus, and dissolved orthophosphorus were detected in included a 21.5-mile river reach of the Elk River on the 303(d) all streambed-sediment leachate samples. list of impaired waters in Missouri as required by Section Concentrations of leachable nutrients in streambed- 303(d) of the Federal Clean Water Act. The Elk River is on the sediment samples generally tended to be slightly larger along 303(d) list for excess nutrient loading. the major forks of the Elk River as compared to tributary The total phosphorus distribution by decade indicates sites, with sites in the upper reaches of the major forks having that the concentrations since 2000 have increased significantly among the largest concentrations. Concentrations of leachable from those in the 1960s, 1980s, and 1990s. The nitrate as nutrients in the major forks generally decreased with increas- nitrogen (nitrate) concentrations also have increased signifi- ing distance downstream. cantly in post-1985 from pre-1985 samples collected at the Elk River near Tiff City. Concentrations have increased significantly since the 1960s. Concentrations in the 1970s and 1980s, though similar, have increased from those in the 1960s, and Introduction the concentrations from the 1990s and 2000s increased still more. Nitrate concentrations significantly increased in samples The Elk River Basin (fig. 1) encompasses about 1,030 that were collected during large discharges (greater than 355 square miles (mi2) in parts of southwestern Missouri, north- cubic feet per second) from the Elk River near Tiff City. western Arkansas, and northeastern Oklahoma (Missouri Nitrate concentrations were largest in Indian Creek. Watershed Information Network, 2006). More than 850 mi2 Several sources of nitrate are present in the basin, including are in Missouri (Missouri Department of Conservation, 2006). poultry facilities in the upper part of the basin, effluent inflow The headwaters of the Elk River are near Pineville, Missouri, from communities of Anderson and Lanagan, land-applied at the confluence of Big Sugar and Little Sugar Creeks. The animal waste, chemical fertilizer, and possible leaking septic Elk River flows westerly into the Grand Lake O’ the Chero- systems. Total phosphorus concentrations were largest in Little kees in northeastern Oklahoma. Much of the basin is within Sugar Creek. The median concentration of total phosphorus McDonald County, Missouri. The rest of the basin is in Barry from samples from Little Sugar Creek near Pineville was and Newton Counties, Missouri, Benton County, Arkansas, almost four times the median concentration in samples from and Ottawa and Delaware Counties, Oklahoma. The largest the Elk River near Tiff City. municipalities partially or completely within the basin are Median concentrations of nutrient species were greater Bentonville and Bella Vista, Arkansas; and Noel, Anderson, in the stormwater samples than the median concentrations in Goodman, and Neosho, Missouri (Missouri Watershed Infor- the ambient samples. Nitrate concentrations in stormwater mation Network, 2006). Smaller communities within the basin samples ranged from 133 to 179 percent of the concentration include Wheaton, Stella, Lanagan, and Pineville, Missouri. in the ambient samples. The total phosphorus concentrations Major tributaries to the Elk River include Big Sugar Creek, in the stormwater samples ranged from about 200 to more than Little Sugar Creek (headwaters in Arkansas), Indian Creek, 600 percent of the concentration in the ambient samples. and Buffalo Creek (Missouri Department of Conservation, 2 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

2006). Two of the more economically important activities in Newton County (9); and Indian Creek in McDonald and New- the Elk River Basin are livestock production and recreational ton Counties (26). activities. In 1997, McDonald, Barry, and Newton Counties Nutrients are essential to plant growth. Aquatic vegeta- were ranked second, third, and fourth in Missouri counties for tion, such as algae, depends on nitrogen and phosphorus the market value of livestock and poultry products with a com- compounds for a nutrient supply, but the availability of other bined value of more than $418,000,000 (Missouri Watershed required elements also may affect growth. Dense growths of Information Network, 2006). Recreational activities within algae, or algal blooms, usually occur when the concentration the Elk River Basin include boating (primarily canoes and of nitrogen or phosphorus increases above normal, ambi- kayaks), swimming, tubing (use of personal flotation device to ent concentrations. During an algal bloom, a lake or stream float downstream on the river), fishing, camping, hiking, and becomes undesirable for recreational use. After an algal bloom hunting. die-off, bacterial decomposition of dead algal cells, which sink to the bottom of the water, results in the depletion of dissolved oxygen. This condition can result in fish kills and Background other negative effects on aquatic life (Davis and Schumacher, 1992). Although nitrogen and phosphorus are essential for The Missouri Department of Natural Resources (MDNR) algal growth, phosphorus availability is considered to be the has designated specific uses for water bodies in the State. Uses limiting factor in many natural waters (Hem, 1985). Nitrate for Big Sugar Creek, Little Sugar Creek, Indian Creek, and concentrations are attributed to drainage from nearby barn- the Elk River are irrigation, livestock and wildlife watering, yards or septic tanks and nitrogen fertilizer use. Phosphorus protection of warm-water aquatic life and human health-fish is a component of sewage effluent and is present in animal consumption, cool-water fishery, whole-body-contact recre- metabolic waste; domestic and industrial effluent probably is a ation, and secondary contact recreation (Missouri Department large source of phosphorus in surface water (Hem, 1985). of Natural Resources, 2005). Whole-body-contact recreation includes public swimming beaches and property where whole- body-contact recreational activities are open to the public. Purpose and Scope Secondary contact recreation includes fishing, wading, com- mercial and recreational boating, and activities in which users The purpose of this report is to present the results of a do not swim or float in the water (Missouri Department of detailed assessment on stream-water quality and streambed- Natural Resources, 2005). sediment quality in the Upper Elk River Basin in southwestern Section 303(d) of the Federal Clean Water Act requires Missouri and northwestern Arkansas. To provide techni- that each State identify those stream segments with docu- cal information needed by the MDNR to assess TMDLs mented pollution problems for which existing pollution for the Elk River and its tributaries, the U.S. Geological controls are not adequate to meet the Statewide water-quality Survey (USGS), in cooperation with the MDNR, collected standards. For these impaired stream segments, States are and analyzed water and streambed-sediment samples in the required to establish total maximum daily loads (TMDLs) Upper Elk River Basin from October 2004 to December 2006. of the identified pollutant. A TMDL specifies the maximum Measurements of physical properties, fecal-indicator bacteria, amount of the identified pollutant allowed to be present in a nutrients, organic wastewater compounds, and pharmaceuti- water body, allocates allowable pollutant loads among sources, cal compounds are discussed. Monthly water-quality samples and provides the basis for attaining or maintaining water- were collected at sites on the Big Sugar Creek, Little Sugar quality standards within the affected water body (Davis and Creek, Indian Creek, and the Elk River from October 2004 Barr, 2006). through September 2006. Streambed-sediment samples were In 1998, the MDNR included a 21.5-mile river reach of collected during the summer of 2005, water-quality samples the Elk River on the 303(d) list of impaired waters in Mis- were collected during low-base flow conditions in the summer souri as required by Section 303(d) of the Federal Clean Water and fall of 2006, and stormwater samples were collected dur- Act. The Elk River is on the 303(d) list for excess nutrient ing selected storms from November 2004 through December loading (Missouri Department of Natural Resources, 1998). 2006. The primary source cited was nonpoint source pollution from livestock production, although both point and nonpoint Study Area Description sources contribute nutrients to the streams. A trend analysis that indicated nutrient accumulation was occurring with time The Elk River Basin is in the Springfield Plateaus physio- and repeated complaints from the public about nuisance algae graphic section of the Ozark Plateaus physiographic province were the basis for the 303(d) listing (Missouri Department (Fenneman, 1938). Rocks in the basin predominantly are of Natural Resources, 2004). Also included on the list (river limestone, shale, and sandstone of Mississippian age (Missouri miles affected) were Big Sugar Creek, McDonald and Barry Watershed Information Network, 2006). Land-surface eleva- Counties (35); Little Sugar Creek, McDonald County (11); tions range from 1,500 feet (ft) in the uplands to about 800 ft North Indian Creek, Newton County (5); South Indian Creek, at the Missouri-Oklahoma state line (Missouri Department of Introduction 3 Arkansas Missouri MILES 10 Seligman Gateway Washburn Garfield Oklahoma KILOMETERS Location Map 10 BARRY 5 94° 5 Wheaton

Avoca

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Indian Big

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City o u N North Indian Creek near Wanda

Stark

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i Little Sugar Creek below Caverna

d # n I

MISSOURI UPPER ELK RIVER BASIN Big ARKANSAS NEWTON Bella Vista Centerton MCDONALD Little Sugar Creek near Pineville # # Big Sugar Creek near Pineville Neosho BENTON ELK RIVER BASIN Goodman Pineville

r e

Anderson v i

# R

Gravette Elk Lanagan Noel Springs Sulphur 94°30’’ Indian Creek near Lanagan

Creek Creek

Patterson

# Elk River near Tiff City Elk River near Tiff

Buffalo

MISSOURI OKLAHOMA

River Elk sampling site and name Water-quality # EXPLANATION Location of the Elk River Basin. Grand Lake Lake Grand DELAWARE OTTAWA O’ the Cherokees

94°45’’ Elk River near Tiff City Elk River near Tiff Figure 1. Base from U.S. Geological Survey digital data, 1:100,000, 1992 Mercator projection Universal Transverse Zone 15 Incorporated boundary of communities from the U.S. Bureau Census, digital data,1:100,000, 2000 36°45’’ 36°30’’ 4 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

Natural Resources, 2004). The slightly rolling hills contain and Atmospheric Administration, 2005). Average monthly numerous karst features (sinkholes, caves, and springs) that precipitation generally is greatest in the spring [April through transport surface water through solution-enlarged joints and June; about 4 to 5 inches per month (in./mo)] and least in the fractures (Imes, 1989). More than 500 explored caves are in late fall and winter (December through January; about 2 to 3 McDonald County (Missouri Watershed Information Network, in./mo; National Oceanic and Atmospheric Administration, 2006). Karst topography greatly affects water quantity and 2004–2006). Monthly precipitation at Anderson from October quality because water and any associated contaminants can 2004 through November 2006 generally was less than normal travel a great distance quickly through joints and fractures. (National Oceanic and Atmospheric Administration, 2004– Although the Elk River Basin encompasses parts of three 2006; fig. 3). states and several counties in those states, the study area for Much of southern Missouri, including that part of the this report focuses on the Upper Elk River Basin and, spe- Upper Elk River Basin in the State, experienced a drought cifically, McDonald County, Missouri. Patterson Creek is a that began in late 1999 (National Drought Mitigation Cen- tributary to Buffalo Creek, but Buffalo Creek flows into the ter, 2007). Monthly and cumulative departure from normal Elk River in Oklahoma, downstream from the sampling site precipitation from January 1999 through September 2006 on the Elk River near Tiff City. Any data collected from these for Anderson, Missouri (National Oceanic and Atmospheric streams will not be discussed in this report. Monthly water- Administration, 1999–2006), are shown in figure 3. In 1999, quality samples from Big Sugar Creek, Little Sugar Creek, there was an excess of precipitation when compared to normal Indian Creek, and the Elk River were collected in McDonald monthly quantities. From 2000 through summer 2002, the County. Although most of the samples from the seepage runs cumulative precipitation fluctuated, but generally ranged from were collected in McDonald County, some were collected in 5 in. less than normal to about 4 in. greater than normal; how- Barry and Newton Counties, Missouri, and Benton County, ever, from summer 2002, cumulative precipitation was less Arkansas. than normal for every month. In March 2006, the cumulative The annual mean discharge of the Elk River near Tiff precipitation was more than 17 in. below normal. City was 822 cubic feet per second (ft3/s) from 1939 through Land use in the Elk River Basin is divided equally October 2005 (Hauck and Harris, 2006). The annual mean dis- between forest and pasture (fig. 4). Historically, land use was charge for water years 2005 (October 2004 through September 60 percent forest, 35 percent woodlands, glades, and savan- 2005) and 2006 (October 2005 through September 2006) for nas, and 5 percent prairie. Currently (2007), much of the land the Elk River and its major tributaries is shown in table 1. The has been converted for use as pasture for cattle and confined annual mean discharge for water year 2006 at each site was animal feeding operations (Missouri Watershed Information less than 30 percent of the annual mean discharge for water Network, 2006). year 2005. Confined animal feeding operations in McDonald County A general trend of declining discharge at the Elk River account for the second largest concentration of poultry in Mis- near Tiff City from 1996 through September 2006 is apparent souri, with an estimated 6 million broilers and other meat-type from the boxplots of the daily mean discharge shown in figure chickens, about 186,000 turkeys, and 157 poultry farms in 2. Also apparent is the decrease in discharge at this location 2002, down from about 7.7 million broilers and other meat- from the decade of the 1990s to the 2000s based on the daily type chickens, 292,000 turkeys, and 161 poultry farms in 1997 mean discharge. (U.S. Department of Agriculture, 2006). Poultry operations The Elk River Basin has a temperate climate, with are located throughout the county, but within the Upper Elk average annual precipitation of 44.6 inches per year (in./ River Basin, most are in the Indian Creek Basin (fig. 4). In yr) from 1999 through 2001 (Missouri Department of McDonald County, 25 poultry operating permits were issued Natural Resources, 1998). In 2005, the annual precipita- by the Missouri Department of Natural Resources (Missouri tion at Anderson was 32.59 inches (in.; National Oceanic Department of Natural Resources, 2007). However, not all

Table 1. Water-quality sampling sites and annual mean discharge within the Upper Elk River Basin, Missouri, 2004–06.

[d, degree; m, minute; s, second; mi2, square mile; ft3/s, cubic feet per second; water year 2005, October 2004 through September 2005; water year 2006, Octo- ber 2005 through September 2006; --, no data available]

Annual mean discharge Site location Site Latitude Longitude Basin size (ft3/s) (fig. 1) number (ddmmss) (dddmmss) (mi2) Date of operation Water year 2005 Water year 2006 Big Sugar Creek near Powell 07188653 363657 0941506 141 May 2000 to present 138 33 Big Sugar Creek near Pineville 07188760 363502 0942223 278 October 2004 to present -- -- Little Sugar Creek below Caverna 07188824 363143 0941715 152 October 2004 to present -- -- Little Sugar Creek near Pineville 07188838 363502 0942223 195 October 2004 to present 219 63 Indian Creek near Lanagan 07188885 363557 0942659 239 May 2000 to present 250 66 Elk River near Tiff City 07189000 363753 0943512 872 October 1939 to present 865 234 Introduction 5

100,000

10,000

1,000

100

1960 1970 1980 1990 2000 2010

100,000 EXPLANATION

Value more than 3.0 times the interquartile range Value within 1.5 and 3.0 times the interquartile range 10,000 90th percentile

DAILY MEAN DISCHARGE, IN CUBIC FEET PER SECOND

1,000 75th percentile (upper quartile) 50th percentile (median) 25th percentile (lower quartile)

100 10th percentile Value within 1.5 and 3.0 times the interquartile range 1960s 1970s 1980s 1990s 2000s Value more than 3.0 times the interquartile range

Figure 2. Discharge at the Elk River near Tiff City, 1960 through September 2006. 6 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

8 A

-2

DEPARTURE FROM NORMAL PRECIPITATION, IN INCHES FROMDEPARTURE NORMAL PRECIPITATION, -4

-6

15 B

-5

-10

CUMULATIVE DEPARTURE FROM NORMAL PRECIPITATION, IN INCHES FROM DEPARTURE NORMALCUMULATIVE PRECIPITATION,

-15

-20 1999 2000 2001 2002 2003 2004 2005 2006 Data from National Oceanic and Atmospheric Administration (1999-2006)

Figure 3. Monthly (A) and cumulative (B) departure from normal precipitation at Anderson, Missouri, January 1999 through September 2006. Introduction 7 " ) " ) " ) " ) " ) " ) " ) " ) " ) " ) " ) " ) " ) " ) " ) " ) BARRY " ) " ) " ) " ) " ) " ) " ) 94° " ) " ) " ) " ) " ) " ) " ) " ) " ) " ) " ) " )

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Goodman r

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Anderson v i 0 0

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MISSOURI " ) " ) ARKANSAS " ) " ) " ) " )

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OKLAHOMA OKLAHOMA

River Elk Grand Lake Lake Grand Land use in the Upper Elk River Basin, Missouri and Arkansas. DELAWARE OTTAWA O’ the Cherokees

EXPLANATION 94°45’’ Land use Forest Pasture Urban Water poultry facility Permitted Figure 4. Base from U.S. Geological Survey digital data, 1:100,000, 1992 Mercator projection Universal Transverse Zone 15 36°45’’ 36°30’’ 8 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06 poultry operations require a permit. An estimated 700 barns streambed-sediment samples collected from October 2004 are in McDonald County; each barn holds about 25,000 broil- through December 2006. ers with 5 to 6 flocks raised per year. Poultry waste is applied directly to the land surface as fertilizer (Lynn Jenkins, Natural Sample Collection and Analysis Methods Resources Conservation Service, oral commun., 2007). In 2004 and 2005, more than 35,000 acres were harvested Monthly water-quality samples were collected from six for hay in McDonald County. From 1986 through 2006, the sites within the Upper Elk River Basin upstream from Tiff number of cattle ranged from 58,900 (1997) to 49,500 (2004 City from October 2004 through September 2006. These sites and 2005) in McDonald County (U.S. Department of Agri- (USGS streamflow-gaging station number is shown in paren- culture, 2006). From 1986 through 2001, there were more theses) included Big Sugar Creek near Powell (07188653), than 40,000 head of swine in McDonald County. The number Big Sugar Creek near Pineville (07188760), Little Sugar Creek of swine decreased dramatically in 2002 and 2003 to less below Caverna (07188824), Little Sugar Creek near Pineville than 15,000 head. No data for swine were available for 2004 (07188838), Indian Creek near Lanagan (07188885), and the through 2006 (U.S. Department of Agriculture, 2006). Elk River near Tiff City (07189000; fig. 1, table 1). Samples The population in McDonald County in 2005 is estimated for nutrient analyses (dissolved ammonia, nitrite, nitrite plus at 22,844, an increase of 35 percent since 1990 (Indiana Busi- nitrate, and orthophosphorus and total ammonia plus organic ness Research Center, 2006). Population estimates for 2005 nitrogen and total phosphorus) were collected according to for selected communities in McDonald County are: Anderson, standard USGS sample collection and processing protocols 1,902; Goodman, 1,233; Lanagan, 453; Noel, 1,515; and Pin- described by Edwards and Glysson (1998) and Wilde and eville, 868 (Missouri Census Data Center, 2006). The popula- others (1999a, 1999b). All chemical analyses were done by tion for Neosho, Missouri (10,505), Bella Vista, Arkansas the USGS National Water Quality Laboratory (NWQL) in (16,582), and Bentonville, Arkansas (21,906), are from 2000 Lakewood, Colorado, according to procedures described in data (City-Data.com, 2007). Benton County, Arkansas, is the Fishman and Friedman (1989) or Fishman (1993). Onsite fastest growing county in Arkansas with a 21 percent popu- measurements of dissolved oxygen, pH, specific conductance, lation increase in the 5 years preceding March 2006 (Greg and water temperature were made at each site according to Hoggatt, written commun., 2007). The 2005 population for procedures described by Wilde and Radtke (1998). Samples Bentonville has increased by 23.6 percent to 27,077 in July were collected and analyzed by the USGS at each site for indi- 2006 (City-Data.com, 2007). cator bacteria [fecal coliform and Escherichia coli (E. coli)] The State of Missouri issues operating permits for sewage using the membrane filtration procedure described in Myers and agricultural processing effluents under the authority of the and Wilde (1997). Individual bacteria samples were collected National Pollution Discharge Elimination System (NPDES). in sterile 500-mL (milliliter) polypropylene bottles by facing Permits have been issued for the following facilities (receiv- the bottle into the stream current and dipping quickly into the ing stream and discharge): city of Anderson (Indian Creek, stream at three to five equally spaced locations in the stream 0.3 ft3/s), city of Lanagan Housing Authority (tributary to cross section. The samples were placed on ice and held a Indian Creek, 0.003 ft3/s), city of Lanagan Housing Authority maximum of 6 hours until processing. Because densities of #2 (Indian Creek, 0.003 ft3/s), city of Noel (Elk River, 0.31 indicator bacteria can be quite variable, generally two sample ft3/s), city of Pineville (Elk River, 0.192 ft3/s), village of Stella volumes ranging from 10 to 100 mL were filtered from indi- (South Indian Creek, 0.053 ft3/s) and two poultry facilities vidual stream samples. Reagent blanks were run twice each (Elk River, 3.6 ft3/s; and Little Sugar Creek, stormwater run- day to check for contamination of equipment and reagents. off) (Missouri Department of Natural Resources, 2007). Little A continuous streamflow-gaging station was installed Sugar Creek also is the receiving stream for effluent from at three of the sites—Big Sugar Creek near Powell (May Bella Vista (0.618 ft3/s). Effluent from Bentonville (5.86 ft3/s) 2000), Little Sugar Creek near Pineville (October 2004), and discharges into Town Branch, which flows into a tributary Indian Creek near Lanagan (May 2000). A long-term gaging of Little Sugar Creek, then into Little Sugar Creek. Effluent station has been operational at the Elk River near Tiff City from Sulphur Springs, Arkansas (0.155 ft3/s), discharges into a since October 1939. Continuous stream-stage (water-surface tributary of the Elk River, then into the Elk River. elevation) data were collected at these sites using a vented sub- mersible pressure transducer. Streamflow measurements were used to establish and maintain the relation between stage and Methods of Study discharge (Rantz and others, 1982). Stormwater samples were obtained at the four gaged sites To assess the water quality of the study area, a network of Big Sugar Creek near Powell, Little Sugar Creek near Pin- of sampling sites throughout the Upper Elk River Basin was eville, Indian Creek near Lanagan, and the Elk River near Tiff established. Water and streambed-sediment samples were col- City using either automatic samplers programmed to collect lected from these sites and analyzed for a variety of physical samples after stage thresholds were exceeded, or by manual properties and chemical constituents during different stream- collection. Stormwater sampling generally was conducted flow conditions. This report includes analyses of water and after 72 hours of no runoff. For several storms, more than one Introduction 9 site was sampled (November 2004, May 2005, April 2006, analyzed with environmental samples to ensure that laboratory and May 2006). Sampling was initiated on the rising limb of contamination was not a concern during analyses. Measurable the storm hydrograph; one or more samples were collected on concentrations in blank water can result from trace quantities the rising limb, a sample was collected at or near the peak of of constituents in the water, as well as residual material in flow, and one or more samples were collected on the falling sample processing or analytical equipment. Most compounds limb. The initial three samples after the sampler was activated were not detected in any blank samples; if detected, the were composited and sent to the NWQL for the analysis of reported concentrations were near the detection limit for these the same constituents as for the monthly samples. The remain- compounds (data on file at the U.S. Geological Survey office, ing samples were analyzed for the nutrients only. Indicator Rolla, Missouri). The blank sample data support the conclu- bacteria densities were determined from at least one sample. sion that equipment cleaning, sample collection, and process- Also, one or more samples for nitrogen isotope analysis were ing procedures provided an inconsequential source of bias to collected at each site. These samples were sent to the USGS environmental samples. Reston Stable Isotope Laboratory in Reston, Virginia. The Replicate samples were collected to determine the vari- nitrate samples were analyzed by bacterial conversion of nitrate ability in sample collection and processing procedures and to to nitrous oxide and subsequent measurement on a continuous examine the effect these variations may have on concentrations flow isotope ratio mass spectrometer (Sigman and others, 2001; determined from environmental samples. Generally, a repli- Casciotti and others, 2002; Coplen and others, 2004). cate sample was collected immediately after an environmental During the summer and fall of 2006, two seepage runs sample using the same equipment and sampling techniques. were conducted in the study area. From July 31 through The environmental and replicate samples were analyzed at August 3, discharge measurements were made at more than the NWQL using identical analytical techniques. Analysis of 70 sites, and water-quality samples were collected at about replicate samples indicated that the laboratory analysis and the 50 sites throughout the Upper Elk River Basin (see ‘Seep- sampling procedure were producing consistent results. Results age Run Water Quality’ section). On November 13 and 14, of the environmental and replicate sample analyses generally the seepage run was repeated at eight of the sites from the were within 5 percent of each other. previous seepage run. Discharge measurements were made in A total of 35 streambed-sediment samples were collected accordance with standard USGS procedures (Rantz and others, from the Upper Elk River Basin in August 2005 to examine 1982). Water-quality samples were analyzed for a similar suite geographic differences in sediment composition (see ‘Stream- of constituents, as were the monthly samples. Samples also bed-Sediment Quality’ section). Samples were collected using were collected for the determination of optical brighteners and a small plastic scoop in areas where fine-grained sediment chlorophyll a. Analysis of these samples was conducted in the accumulated (for example, behind large rocks, woody debris, USGS laboratory in Rolla, Missouri, using a spectrofluoropho- and bridge piers). Several subsamples were collected at each tometer and fluorometer. Selected samples were analyzed for site. Fine-grained sediment was sampled to target material wastewater indicator compounds and pharmaceutical com- that could be mobilized easily during storm flow. Subsamples pounds. Wastewater indicator compounds were determined were composited into two split samples (split A and B) in from filtered samples by continuous liquid-liquid extraction polyethylene containers and transported to the USGS office with methylene chloride and determined by capillary-column in Rolla, Missouri. Sample split A was shipped to the USGS gas chromatography/mass spectrometry using selected-ion Geochemistry Laboratory in Denver, Colorado, for grain-size monitoring (Brown and others, 1999; Kolpin and others, 2002) (percent sand, silt, and clay) and chemical analysis of the at the NWQL. Information in Zaugg and others (2001) pro- less than 63-micrometer (µm) size fraction using Inductively vides details about specific wastewater indicator compounds Coupled Plasma/Mass Spectrometry (ICP/MS). Sample split and their uses. Pharmaceutical compounds were determined B was leached with deionized water in an effort to estimate the from filtered samples by high-performance liquid chroma- quantity of nutrients readily leachable from the sediment. Split tography/electrospray ionization-mass spectrometry analysis B samples were prepared by air drying the sample overnight (Furlong and others, 2000; Kolpin and others, 2002) at the and sieving through a 2-millimeter (mm) mesh stainless steel NWQL. screen. Approximately 22 grams (g) of sieved sediment sam- Quality-assurance samples were collected and analyzed ple were placed into a clean polyethylene bottle with 220 mL to ensure the integrity of the water-quality data. About 10 per- of deionized water. The bottles were shaken for 10 minutes cent of all samples collected were blank or replicate quality- and allowed to settle for 2 hours. After settling, the superna- assurance samples. tant was filtered through a 0.45-µm pore-size filter into clean The adequacy of the field cleaning and sample process- polyethylene bottles and shipped overnight on ice for nutrient ing protocols were evaluated through field equipment blank analysis at the NWQL. samples. Purified water (blank water) was passed through the same equipment used to collect and process water-quality Data Analysis Methods samples and then stored, shipped, and analyzed by NWQL using identical methods that were used for environmental Statistical analyses were conducted by comparing water- samples. A blank sample was prepared by the NWQL and quality characteristics between sites and between ambient and 10 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06 stormwater samples at individual sampling sites. Nonparamet- side-by-side boxplots (Tukey, 1977). A boxplot is a useful tool ric statistical methods were used to analyze data when appro- for visually examining the central tendency and dispersion of priate because water-quality data generally are not normally a group of data or for comparing two or more groups of data. distributed, and the data often contain values less than the To construct a boxplot, the median value is plotted as a hori- method detection limit (censored data). Nonparametric statisti- zontal line, and a box is drawn from the 25th percentile to the cal methods were used because these methods are not unduly 75th percentile. The box length equals the interquartile range affected by extreme data values (outliers) and because ranks of (IQR). Vertical lines are then drawn from the quartiles to two data are used instead of the actual concentrations of the water- “adjacent” values. The upper adjacent value is defined as the quality constituents. A significance level (α) of 0.05 was used largest data point less than or equal to the upper quartile plus for statistical tests for water-quality samples. A significance 1.5 times the IQR (90th percentile). The lower adjacent value level (α) of 0.10 was used for statistical tests for streambed- is the smallest data point greater than or equal to the lower sediment samples. The higher level of 0.10 was used for the quartile minus 1.5 times the IQR (10th percentile). Values more sediment samples because of the lack of reproducibility of extreme in either direction than the adjacent values are plotted the results caused by the inhomogeneity of the samples. The individually. Those values equal to 1.5 to 3.0 times the IQR attained significance level, or probability of error (p-value) are called “outside values” and generally are represented by an from the test, often was much lower and is reported to provide asterisk; those values greater than 3.0 times the IQR are called a quantitative indication of the degree of similarity or differ- “far-out values” and generally are represented by a circle ence between data sets. (Davis and Schumacher, 1992). The nonparametric statistical methods included the For streambed-sediment samples, a linear regression was Kruskal-Wallis test and multiple comparison tests on the data used to analyze the relation between a dependent concentra- ranks (Helsel and Hirsch, 1992). The Kruskal-Wallis test is tion and an independent concentration. Graphs showing the an analysis of variance on the ranks of data that test for dif- relation of streambed-sediment concentrations have the linear ferences in the central tendency, or medians, of two or more trend plotted along with the confidence interval. The confi- groups. When the Kruskal-Wallis test indicated a significant dence interval specifies the range that contains most of the difference at the 0.05 level for water-quality samples and at the streambed-sediment concentrations—for example, the upper 0.10 level for sediment samples, a t-test on the ranks (Tukey’s confidence level of 95 percent and the lower level of 5 percent W) was performed on each paired group to evaluate which were plotted. groups were statistically different from one another. Selected nutrient loads were estimated with the USGS software LOADEST as part of the S-Plus software program (Insightful Corporation, 2005). LOADEST uses time-series Water Quality streamflow data and constituent concentrations to calibrate a regression model that describes constituent loads in terms of Historical Water Quality various functions of streamflow and time (Runkel and others, 2004). A complete discussion of the theory and principles The USGS has collected water-quality data from sev- behind the calibration and estimation methods is presented in eral sites throughout the Upper Elk River Basin (fig. 1). Data Runkel and others (2004). The LOADEST software allows collected before October 2004 have been included in the the user to choose between selecting the general form of the historical data category. Data were collected for Mikes Creek regression from several predefined models and letting the at Powell (07188660) and North Indian Creek near Wanda software automatically select the best-defined model on the (07188855) during 1994 and 1995, Little Sugar Creek at basis of the Akaike Information Criterion (AIC) (Akaike, Caverna (07188820) from 1964 through 1983, and the Elk 1981). The model that the software selected was used for this River near Tiff City from 1960 through 2004. Samples col- study. lected from Little Sugar Creek at Caverna were collected at a The output regression equations have the following gen- site about 2 miles (mi) upstream from the site of the monthly eral form: water-quality sample collection at Little Sugar Creek below Caverna (07188824). 1n(L)=a+b(1nQ)+c(1nQ2)+d[sin(2πT)]+e[cos(2 πT)]+ fT+ gT 2 (1) The following discussion about constituent concentrations and analysis will be limited to the sampling sites at where L is the constituent load, in tons per day; Little Sugar Creek at Caverna and the Elk River near Tiff City Q is the stream discharge, in cubic feet per because of the extremely small sample size at Mikes Creek at second; Powell and North Indian Creek near Wanda. The discussion T is the time, in decimal years, from the also will be confined to the period of overlapping sample col- beginning of the calibration period; and lection (August 1964 through September 1983) at Little Sugar a,b,c,d,e,f,g are regression coefficients. Creek and the Elk River. However, the boxplots in the follow- The distribution of selected physical property values or ing figures will show samples from all sites that have historical constituent concentrations at sampling sites is shown using data. Water Quality 11

Sodium and chloride concentrations in historical small [less than 0.01 milligram per liter (mg/L)]. Total nitro- samples from Little Sugar Creek at Caverna were signifi- gen concentrations were calculated by summing the concentra- cantly larger (p<0.01) than those concentrations from the tions of total ammonia plus organic nitrogen and nitrite plus Elk River near Tiff City (fig. 5). Sulfate concentrations at the nitrate. two sites were similar (p=0.269). The increased concentra- The total nitrogen concentrations within the Upper Elk tions of sodium and chloride at Little Sugar Creek at Caverna River Basin generally were comprised of 80 percent or more possibly indicate effects from wastewater effluent discharged nitrate (fig. 6). Hereinafter, only nitrate concentrations will into the creek. be discussed. The distribution of nutrient species in historical The constituents of concern in the Upper Elk River samples is shown in figure 6. The nitrate concentrations were Basin are nutrients; therefore, the following discussion will statistically larger in samples from Little Sugar Creek at Cav- be limited to analysis of dissolved nitrate as nitrogen (nitrate), erna (p<0.01) than those in samples from the Elk River near total nitrogen, and total phosphorus concentrations. The nitrate Tiff City during the period of overlapping sample collection. concentrations were expressed in several ways: concentrations Total phosphorus concentrations generally were less than of nitrate (not as nitrogen) were multiplied by an appropri- 0.70 mg/L for all sites within the basin (fig. 6). Concentrations ate conversion factor to determine a nitrate concentration as in samples from Little Sugar Creek at Caverna were signifi- nitrogen; concentrations of nitrate as nitrogen were used as is; cantly larger than those in samples from the Elk River near and nitrite plus nitrate concentrations were assumed to equal Tiff City (p<0.01). The median total phosphorus concentration nitrate concentrations because concentrations of nitrite were was 0.20 mg/L in samples from Little Sugar Creek at Caverna.

15 50 235 Sodium Chloride 189 40

10 99 30 262

3 20 5 * * 3 10 3 * 3 * * * * 0 0 Mikes North Little Elk River Mikes North Little Elk River Creek Indian Sugar near Creek Indian Sugar near at Creek Creek Tiff City at Creek Creek Tiff City Powell near at Powell near at Wanda Caverna Wanda Caverna

40 EXPLANATION 186 Sulfate 241 Number of samples Value more than 3.0 times the interquartile range CONCENTRATION, IN MILLIGRAMS PER LITER 30 241 Value within 1.5 and 3.0 times the interquartile range 90th percentile

75th percentile (upper quartile) 50th percentile (median) 10 25th percentile (lower quartile) 3 3 * * 10th percentile 0 Mikes North Little Elk River Value within 1.5 and 3.0 times the interquartile range Creek Indian Sugar near at Creek Creek Tiff City Value more than 3.0 times the interquartile range Powell near at * Data value Wanda Caverna

Figure 5. The distribution of selected major ion concentrations in historical water-quality samples within the Upper Elk River Basin. 12 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

4 5 * 363 * Total nitrogen 242 3 3 Nitrate as nitrogen 179 4 3 * 96 3

1 3 1 3 * * 0 0 Mikes North Little Elk River Mikes North Little Elk River Creek Indian Sugar near Creek Indian Sugar near at Creek Creek Tiff City at Creek Creek Tiff City Powell near at Powell near at Wanda Caverna Wanda Caverna

1.0 EXPLANATION

0.9 Total phosphorus 242 Number of samples 0.8 Value more than 3.0 times the interquartile range CONCENTRATION, IN MILLIGRAMS PER LITER 184 368 0.7 Value within 1.5 and 3.0 times the interquartile range 0.6 90th percentile

0.5

0.4 75th percentile (upper quartile) 0.3 50th percentile (median) 0.2 25th percentile (lower quartile)

0.1 3 3 10th percentile 0 * * Mikes North Little Elk River Value within 1.5 and 3.0 times the interquartile range Creek Indian Sugar near at Creek Creek Tiff City Value more than 3.0 times the interquartile range Powell near at Wanda Caverna * Data value

Figure 6. The distribution of nutrient concentrations in historical water-quality samples within the Upper Elk River Basin.

Discharge and water-quality data from the Elk River With the addition of samples from 2003 through Septem- near Tiff City from 1966 through 2002 were used for a trend ber 2004, the concentrations of total phosphorus in post-1985 analysis by the Missouri Department of Natural Resources as samples from the Elk River near Tiff City also were signifi- a basis for including the Elk River on its 303(d) list. The total cantly larger (p<0.01; fig. 7) than the concentrations in the phosphorus concentrations for 1966 through 1984 were statis- pre-1985 samples. The mean before 1985 was 0.064; after tically different from the concentrations for 1985 through 2002 1985, it was 0.093 mg/L. (p<0.01). The mean total phosphorus concentration before The total phosphorus concentrations have increased in 1985 was 0.064 mg/L and after 1985 was 0.094 mg/L (Mis- historical samples from the Elk River near Tiff City during souri Department of Natural Resources, 2004). Throughout the periods from 1962 through September 2004 (fig. 8). The last Upper Elk River Basin in Missouri, which has about one-third increase occurred from 2000 through 2003. The total phos- of the number of poultry in the entire basin, the yearly average phorus distribution by decade indicates that the concentrations number of poultry increased by 189 percent since 1985 when since 2000 have increased significantly (p<0.01) from those in compared to the number before 1985. The increase is based the 1960s, 1980s, and 1990s (fig. 8). on the yearly averages of 1974, 1978, 1982, 1987, 1992, and Although nitrate concentrations were not referred to in 1997. The number of hogs and cattle declined slightly for the Missouri Department of Natural Resources (2004), these the same period (Missouri Department of Natural Resources, concentrations also have significantly increased in post-1985 2004). samples from pre-1985 samples in the Elk River near Tiff City Water Quality 13

4 87 67 78 1.0 98 Total phosphorus Nitrate as nitrogen

59 77 60 3

67 98 74 0.10 2

1 0.01

CONCENTRATION, IN MILLIGRAMS PER LITER 0 1960s 1970s 1980s 1990s 2000s 1960s 1970s 1980s 1990s 2000s

EXPLANATION

78 Number of samples Within 1.5 and 3.0 times the interquartile range 90th percentile

75th percentile (upper quartile) 50th percentile (median) 25th percentile (lower quartile)

10th percentile Within 1.5 and 3.0 times the interquartile range

Figure 7. Distribution of total phosphorus and nitrate as nitrogen concentrations, by decades, in samples from the Elk River near Tiff City.

(fig. 7). Median nitrate concentrations increased from 0.880 Ambient Water Quality mg/L before 1985 to 1.44 mg/L after 1985. The distribution of nitrate at Elk River near Tiff City Water-quality samples were collected monthly from indicates a slight upward trend with time; however, when the October 2004 through September 2006 from six sites within data are grouped by decade, the trend becomes more apparent the Upper Elk River Basin (fig. 1). These sites were Big Sugar (fig. 9). Concentrations have increased significantly since the Creek near Powell, Big Sugar Creek near Pineville, Little 1960s. Concentrations in the 1970s and 1980s, though similar, Sugar Creek below Caverna, Little Sugar Creek near Pineville, had increased from those in the 1960s, and the concentrations Indian Creek near Lanagan, and the Elk River near Tiff City. from the 1990s and 2000s increased still more. Whenever possible, samples were collected synoptically at Nitrate concentrations significantly (p<0.01) increased these sites, meaning as close in time as possible, with no inter- in samples that were collected during larger discharges from vening rainfall during sample collection. Summary statistics the Elk River near Tiff City as compared to the concentra- for selected physical properties, inorganic constituents, and tions in samples collected during smaller discharges (fig. 10). nutrients are listed in table 2. The discharge used was 355 ft3/s, which was the discharge Stream samples were calcium-bicarbonate type waters that was exceeded 50 percent of the time. Not only are nitrate (fig. 11). The samples plot within a small area near the concentrations increasing as discharge increases, the concen- calcium and bicarbonate vertices. Samples from Little Sugar trations are increasing during the period of sample collec- Creek below Caverna and the Elk River near Tiff City indicate tion. However, nitrate concentrations in samples collected at minor variations that plot along a line trending toward decreas- discharges less than 355 ft3/s decreased from the late 1990s ing calcium and increasing chloride values, indicating possible when discharge began to decrease (fig. 2). The increased mixtures of effluent from wastewater treatment plants. nitrate concentrations possibly can be attributed to runoff from The specific conductance values throughout the upper Elk nonpoint sources. River Basin ranged from 200 to 350 microsiemens per centi- 14 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

1.0

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0 1960 1970 1980 1990 2000 2010

EXPLANATION 87 1.0 98 77 Number of samples Value more than 3.0 times the interquartile range 59 77 60 Value within 1.5 and 3.0 times the interquartile range 90th percentile

CONCENTRATION, IN MILLIGRAMS PER LITER 0.10

75th percentile (upper quartile) 50th percentile (median) 25th percentile (lower quartile) 0.01

10th percentile Value within 1.5 and 3.0 times the interquartile range 1960s 1970s 1980s 1990s 2000s Value more than 3.0 times the interquartile range

Figure 8. The distribution of total phosphorus concentrations in samples from the Elk River near Tiff City, 1962–2006. menter at 25 ºCelsius (µS/cm) at the ambient sampling sites oxygen concentrations are a function of temperature, waste (median values less than 300 µS/cm) except for the sites on loads, and hydraulic properties that affect the rates at which Little Sugar Creek. In the adjoining Shoal Creek Basin, much atmospheric oxygen can be supplied (Davis and Schumacher, of which is in Barry County northeast of the Elk River Basin, 1992). The solubility of oxygen is greater in colder water than specific conductance values generally were less than 350 in warm water (Hem, 1985). No statistical difference existed µS/cm (Schumacher, 2001). The Shoal Creek Basin also has a in the dissolved oxygen concentrations at the sites (p=0.614). large number of livestock production facilities. Effluent inflow appears to have not adversely affected the dis- Stream samples generally had slightly alkaline pH values solved oxygen concentrations at the sampled sites. (7.0 to 8.4) and dissolved oxygen concentrations greater than Fecal indicator bacteria densities in ambient samples 6.0 mg/L. Dissolved oxygen concentrations of less than 5.0 generally increased with increasing discharge. The largest mg/L were measured in Big Sugar Creek near Pineville dur- densities were related to changes in discharge as a result of ing the summer months. The Missouri Department of Natural storms. Missouri has established water-quality criteria for Resources has a minimum dissolved oxygen concentration fecal bacteria in streams that have a designated beneficial use requirement for warm-water fisheries of 5 mg/L. One of the of whole-body-contact recreation. Category A criteria for E. beneficial uses of Big Sugar Creek is warm-water fishery coli is 126 colonies per 100 milliliters (col/100 mL) and for (Missouri Department of Natural Resources, 2005). Dissolved fecal coliform is 200 col/100 mL. Category A includes “public Water Quality 15

* * 2

CONCENTRATION, IN MILLIGRAMS PER LITER

0 1960 1970 1980 1990 2000 2010

EXPLANATION

4 12 78 Number of samples 67 78 Value more than 3.0 times the interquartile range Value within 1.5 and 3.0 times the interquartile range 90th percentile 3 9

98 67 75th percentile (upper quartile) 74 50th percentile (median) 2 6 25th percentile (lower quartile)

10th percentile

1 3 Value within 1.5 and 3.0 times the interquartile range

POPULATION, IN TENS OF THOUSANDS Value more than 3.0 times the interquartile range

CONCENTRATION, IN MILLIGRAMS PER LITER ESTIMATED NUMBER OF POULTRY, IN MILLIONS * Data value Population of McDonald County, Missouri 0 0 (Missouri Census Data Center, 2006) 1960s 1970s 1980s 1990s 2000s Population of Bella Vista, Arkansas (City-Data.com, 2007)

Estimated number of poultry in the Elk River Basin in Missouri (Missouri Department of Natural Resources, 2004; Lynn Jenkins, Natural Resources Conservation Service, oral commun., 2007) Figure 9. The distribution of nitrate as nitrogen concentrations in samples from the Elk River near Tiff City, 1960–2006. swimming beaches and property where whole body contact Creek below Caverna and four times near Pineville (in August recreational activity is open to and accessible by the public 2005, only the E. coli criteria were exceeded); the criteria also through law or written permission of the landowner” (Missouri were exceeded four times in samples from the Elk River near Department of Natural Resources, 2005). The criteria are a Tiff City. No exceedances were noted in samples from Indian monthly geometric mean during the recreation season (April Creek near Lanagan. 1 to October 31) in waters designated for recreation or at any Nitrate concentrations were largest in Indian Creek. Sev- time in losing streams. For ambient samples, fecal coliform eral sources of nitrate are present in the basin, including poul- and E. coli densities exceeded the water-quality criteria in try facilities in the upper part of the basin, effluent inflow from Big Sugar Creek—twice near Powell and three times near communities of Anderson and Lanagan, land applied animal Pineville. The criteria were exceeded two times in Little Sugar waste, chemical fertilizer, and possible leaking septic systems. 16 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

4 Load calculation of the various constituents is important in determining the total quantity of the constituent that passes Discharge less than 355 cubic feet per second a certain point in a given time. The constituent load at the Elk River near Tiff City is determined, in part, by the loads of Discharge greater than 355 cubic feet per second the tributaries of Big Sugar, Little Sugar, and Indian Creeks 3 that flow into the Elk River. Tributary inflow into the Elk River, using only samples where the discharge from the three tributaries was less than the discharge at the Elk River near Tiff City, was comprised of about 21 percent from Big Sugar 2 Creek, 25 percent from Little Sugar Creek, and 29 percent from Indian Creek. Flow from these tributaries accounted for about 75 percent of the flow in the Elk River near Tiff City. Generally at discharges of less than 100 ft3/s, inflow from the three tributaries exceeded the discharge at the Elk River near 1 Tiff City, indicating the presence of losing stream segments in the reach of the Elk River between the confluence of Big and Little Sugar Creeks and the gaging station near Tiff City.

NITRATE AS NITROGEN CONCENTRATION, IN MILLIGRAMS PER LITER In the Upper Elk River Basin, the largest monthly median nitrate load was carried by the Elk River near Tiff City 0 1960 1970 1980 1990 2000 2010 (fig. 13), and the second largest by Indian Creek near Lana- gan, the tributary immediately upstream from the Elk River at Figure 10. Relation between nitrate as nitrogen concentrations Tiff City. The smallest load was from Big Sugar Creek near and discharge in samples from the Elk River near Tiff City, 1960 to Powell, with a corresponding increase downstream. The loads September 2006. increased downstream in the basin. The total phosphorus loads were largest at Little Sugar Creek near Pineville and the Elk River near Tiff City. The median load at Little Sugar Creek Concentrations of nitrate in samples from the upstream sites near Pineville was 0.649 ton per day and at the Elk River near for Big and Little Sugar Creeks were larger than the concen- Tiff City was 0.719 ton per day. trations of nitrate in the downstream sites. Several poultry Based on median monthly nutrient loads calculated from facilities present in the upper reaches of Big Sugar Creek and the ambient samples, Big Sugar Creek near Powell contributes fertilizer applied to lawns and golf courses around Bella Vista, 18 percent of the nitrate load at the Elk River near Tiff City. Arkansas, and effluent from that city possibly could provide Little Sugar Creek near Pineville contributes another 31 per- the larger nitrate concentrations that were detected at Big cent, and Indian Creek near Lanagan contributes 59 percent. Sugar Creek near Powell and Little Sugar Creek below Cav- The total phosphorus load at the Elk River near Tiff City com- erna. The nitrate concentrations in the Elk River were not sig- prises 4 percent from Big Sugar Creek, 90 percent from Little nificantly different from those of Big and Little Sugar Creeks. Sugar Creek, and 29 percent from Indian Creek. If the nutrient Median nitrate concentrations ranged from 0.55 (Big Sugar loads at the Elk River near Tiff City were simply a total of the Creek near Pineville) to 1.7 mg/L (Indian Creek near Lanagan; loads from the major tributaries, they would be much larger table 2; fig. 12). The maximum concentration of 4.6 mg/L was than those determined from the samples. Nutrients are being detected in a sample from Indian Creek near Lanagan. removed in the Elk River by processes that consume them or The total phosphorus concentrations were largest in Little bind them to sediment or through stream losses. For example, Sugar Creek. The median concentration in samples from Little the cumulative nitrate load from the three tributaries to the Elk Sugar Creek below Caverna was more than eight times the River was 108 percent of the load calculated at the Elk River median concentration in samples from the Elk River near Tiff near Tiff City, and the total phosphorus load was more than City; the median concentration from samples from Little Sugar 123 percent of the load calculated in samples from the Elk Creek near Pineville was almost four times the median con- River near Tiff City. centration in samples from the Elk River near Tiff City (table Little Sugar Creek in the vicinity of Caverna is one of 2; fig. 12). Median total phosphorus concentrations in samples two locations in the study area that has substantial historical from the Upper Elk River Basin ranged from 0.02 (Big Sugar data, in addition to the ambient data. Previous data col- Creek near Powell) to 0.265 mg/L (Little Sugar Creek below lection ended in 1983; therefore, more than 20 years have Caverna; table 2; fig. 12). The largest total phosphorus con- passed to the beginning of the sample collection during 2004. centration detected in samples was 0.430 mg/L at Little Sugar The nitrate concentrations from the ambient samples were Creek below Caverna. The site on Little Sugar Creek below significantly larger (p<0.01) than the concentrations in the Caverna is about 3 river miles downstream from the outfall for historical samples. However, the total phosphorus concentra- the wastewater treatment facility that processes wastewater for tions between the different periods were statistically similar. Bella Vista. Therefore, increases in human population and recreational Water Quality 17

.006 .020 .106 .023 .019 .003 .008 .042 .011 .009 .089 .265 .430 .255 .097 .020 .112 .260 .119 .046 .009 .031 .410 .044 .080 .020 .030 .050 .032 .010 Total 24 23 24 24 23 24 (mg/L) phosphorus

.006 .020 .090 .019 .017 .003 .020 .090 .020 .016 .030 .240 .377 .229 .102 .030 .090 .171 .091 .035 .008 .020 .190 .024 .037 .020 .040 .050 .036 .009 23 23 24 24 23 24 (mg/L) Ortho- phosphorus

.002 .008 .008 .007 .002 .001 .008 .008 .007 .002 .004 .008 .021 .008 .004 .002 .008 .016 .007 .003 .002 .008 .008 .007 .002 .003 .008 .011 .007 .002 24 23 24 24 23 24 (mg/L) Nitrite

.41 .91 .10 .55 .81 .79 .44 .59 .08 .75 .06 .06 .82 .94 1.3 3.6 1.5 2.6 1.5 2.8 1.5 1.1 2.8 1.1 1.7 4.6 1.9 1.2 3.4 1.1 24 23 24 24 23 24 (mg/L) nitrate Nitrite +

.04 .04 .03 .01 .01 .04 .04 .04 .01 .01 .04 .10 .04 .02 .01 .04 .04 .04 .01 .01 .04 .09 .24 .01 .04 .04 .03 .01 0.00 1.17 24 23 24 24 22 24 (mg/L) Ammonia

.46 .52 .67 8 5.5 6.3 6.9 6.3 4.9 5.6 6.5 5.6 7.7 4.2 8.2 8.2 3.8 4.2 5.5 4.5 8 8 8 3.2 8 2.0 7 8 2.4 11 16 12 11 10 14 11 (mg/L) Sulfate

.93 .57 8 3.9 6.1 6.9 5.9 8 2.7 5.1 6.3 4.8 1.11 8 6.4 4.3 8 5.9 9.8 3.6 7 6.5 7.3 8.3 7.4 8 5.9 9.8 3.6 11 17 12 16 10 16 10 (mg/L) Chloride

.30 .20 .43 8 2.9 3.3 3.8 3.3 2.3 2.7 3.0 2.7 5.0 9.7 4.2 7.8 8.5 4.0 4.5 5.2 4.6 4.2 7.8 8.5 8 8 4.3 8 3.6 7 8 3.6 16 10 14 14 (mg/L) Sodium

.16 .24 .69 .44 .27 .44 8 1.8 2.2 2.3 2.1 1.3 1.9 2.1 1.8 2.2 3.2 4.2 3.2 2.1 3.0 3.4 3.0 1.6 2.2 2.3 2.1 2.1 3.0 3.4 3.0 8 8 8 7 8 (mg/L) Potassium

.60 .39 .34 .36 .16 .36 8 3.3 4.0 5.2 4.0 8 2.6 3.2 3.8 3.2 8 1.9 2.5 2.9 2.5 8 2.9 3.5 4.1 3.5 7 1.8 2.1 2.3 2.1 8 2.9 3.5 4.1 3.5 (mg/L) Magnesium

Elk River near Tiff City Elk River near Tiff Indian Creek near Lanagan Big Sugar Creek near Powell 2.4 8 2.2 8 2.7 8 5.0 7 3.2 8 5.0 8 Big Sugar Creek near Pineville Little Sugar Creek near Pineville 51 54 59 54 45 49 53 49 52 56 59 55 42 54 58 52 48 52 58 52 42 54 58 52 Little Sugar Creek below Caverna (mg/L) Calcium a .32 a .25 a .23 a .25 a .20 a .30 7 7.6 8.2 7.2 7.6 8.0 7.3 7.8 8.1 7.2 7.7 8.1 7.5 7.8 8.1 7.4 7.9 8.4 pH 24 23 24 24 22 24

24 14.6 23 23.4 24 34.8 24 28.7 22 15.7 24 22.4 280 298 341 300 202 278 307 275 268 349 390 341 258 342 368 328 258 286 319 288 263 316 348 311 (µS/cm) Specific conductance

5 9 8.9 2.0 4.1 9.6 9.3 2.9 6.1 8.4 8.9 1.7 6.4 8.5 9.1 2.0 5.6 9.2 9.5 2.1 4.5 9.9 2.8 24 12.9 23 15.5 24 12.2 24 13.3 21 13.3 24 10.5 16.4 (mg/L) oxygen Dissolved

4.8 7.1 8.5 6.5 5.1 6.6 7.2 6.5 6.1 7.4 6.1 7.9 C) 24 17.9 27.1 17.4 23 18.5 28.8 18.6 24 18.4 26.8 17.3 24 19.6 27.6 18.3 21 18.1 29.9 18.1 24 21.9 31.8 19.8 o ( Water temperature C, degrees Celsius; mg/L, milligrams per liter; µS/cm, microsiemens per centimeter at 25 degrees Celsius; pH, in standard units; concentrations dissolved unless otherwise Celsius; pH, in standard units; concentrations dissolved Celsius; mg/L, milligrams per liter; µS/cm, microsiemens centimeter at 25 degrees C, degrees o 1.1 3.9 /s) 24 40 93 23 28 24 14 42 24 13 42 22 17 46 24 26 99 3 775 161 168 314 769 103 159 801 129 182 700 115 162 325 495 (ft 1,096 2,200 Discharge Summary statistics for selected physical properties, inorganic constituents, and nutrients in the Upper Elk River Basin, Octobe r 2004 through September 2006.

/s, cubic feet per second; Mean pH will not satisfactorily summarize the typical hydrogen ion concentration if the pH values are not normally distributed. ion concentration if the pH values summarize the typical hydrogen Mean pH will not satisfactorily 3 a Number of samples Minimum Median Maximum Mean Standard deviation Number of samples Minimum Median Maximum Mean Standard deviation Number of samples Minimum Median Maximum Mean Standard deviation Number of samples Minimum Median Maximum Mean Standard deviation Number of samples Minimum Median Maximum Mean Standard deviation Number of samples Minimum Median Maximum Mean Standard deviation Table 2. Table [ft indicated] 18 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

80 Calcium plus magnesium

60 EXPLANATION

Sulfate plus chloride 40 Big Sugar Creek near Powell

20 Big Sugar Creek near Pineville Little Sugar Creek below Caverna 20 Little Sugar Creek near Pineville Indian Creek near Lanagan Elk River near Tiff City

20 40

20 Sodium plus potassium 80 60 80

40 60 Sulfate 40 60 80 60

60 80 Magnesium 40 60 40

Bicarbonate 80 plus carbonate

20 80 20

80 60 40 20

20 40 60 80 Calcium Chloride PERCENTAGE OF MILLIEQUVALENTS PER LITER

Figure 11. Trilinear diagram of major ions in samples from the Upper Elk River Basin, October 2004 through September 2006. and agricultural activities seem not to have increased the total storms were sampled at each site (table 3). One of the ambi- phosphorus concentrations at this site. ent samples at Indian Creek was collected the day after storm Nitrate concentrations in the Upper Elk River Basin samples were collected in May 2005 and is included with the tended to increase with increasing discharge (fig. 14). Concen- stormwater samples. trations increased near the beginning of the ambient sample The pH and specific conductance values in stormwater collection in November 2004 and continued to increase samples generally were less than the values in the ambient through January 2005, when they began to rather substantially samples except for the values in stormwater samples collected decrease through the summer, fall, and winter of 2005 along at Little Sugar Creek near Pineville. In those samples, pH val- with a corresponding decrease in discharge. During the sum- ues ranged from 7.9 to 8.2 (table 3), and specific conductance mer of 2006, an increased concentration was detected, and a values ranged from 237 to 351 µS/cm. The pH values in the smaller decrease was detected in September 2006. ambient samples from Little Sugar Creek near Pineville were Total phosphorus concentrations tended to be inversely 8.1 or less, and specific conductance values ranged from 258 related to discharge in the ambient samples (fig. 15). Some of to 368 µS/cm. the largest concentrations at Little Sugar Creek near Pineville Stormwater samples generally had major ion concentra- were in samples collected at some of the smallest discharges, tions that were slightly less than the concentrations in the indicating point sources of the nutrient. Concentrations in ambient samples. However, sulfate concentrations in stormwa- samples from all sites, except for those from Little Sugar ter samples at Little Sugar Creek near Pineville ranged from Creek, were less than 0.11 mg/L. 8.8 to 20.1 mg/L, and concentrations from ambient samples ranged from 4.2 to 11.4 mg/L. Stormwater Water Quality Major ion concentrations at sampling sites on Little Sugar and Indian Creek and the Elk River generally were inversely Stormwater samples were collected at the four sites with related to discharge (table 3). However, potassium concentra- continuous streamflow gaging stations—Big Sugar Creek tions at Indian Creek near Lanagan increased with increasing near Powell, Little Sugar Creek near Pineville, Indian Creek discharge during the storm of May 2005, which indicates a near Lanagan, and the Elk River near Tiff City (fig. 1). Three runoff-derived source for this constituent. Leaching of potas- Water Quality 19

5 23 Nitrate as nitrogen Total nitrogen

4 24 24 24 24

24 24 3 24 24 23 23

0 Powell Pineville Caverna Pineville Indian Elk River Powell Pineville Caverna Pineville Indian Elk River Creek near Creek near Big Sugar Little Sugar near Tiff City Big Sugar Little Sugar near Tiff City Creek Creek Lanagan Creek Creek Lanagan

0.5

Total phosphorus 24 EXPLANATION 0.4

CONCENTRATION, IN MILLIGRAMS PER LITER 23 Number of samples Value more than 3.0 times the interquartile range 0.3 24 Value within 1.5 and 3.0 times the interquartile range 90th percentile

0.2

75th percentile (upper quartile) 24 50th percentile (median) 0.1 23 25th percentile (lower quartile) 23 24

0 10th percentile Powell Pineville Caverna Pineville Indian Elk River Value within 1.5 and 3.0 times the interquartile range Creek near Big Sugar Little Sugar near Tiff City Value more than 3.0 times the interquartile range Creek Creek Lanagan

Figure 12. The distribution of nutrient concentrations in samples from the Upper Elk River Basin, October 2004 through September 2006. sium from soils and organic matter can produce this increase based on the longer than normal hold times. Because fecal with increasing discharge (Hem, 1985). indicator bacteria densities in stormwater samples tend to be In stormwater samples, indicator fecal bacteria densities large, the use of cleaned, but not sterile, bottles should not (fecal coliform and E. coli) generally increased with increas- cause a substantial increase in bacterial density. The bacteria ing discharge. Bacteria densities were greater than 200 col/100 densities for the storm of May 2006 at Little Sugar Creek near mL in all stormwater samples except for one sample from the Pineville and Indian Creek near Lanagan were collected using Elk River near Tiff City (fecal coliform density of less than standard USGS protocol. 100 col/100 mL). Bacteria densities for most samples were Although all sites were not sampled for all storms, nitrate cultured from samples that had been collected by an automatic concentrations generally were largest in samples from Big sampler, and the samples had been stored for varying times in Sugar Creek near Powell—most notably in samples from the polyethylene, unsterilized bottles. This is not standard USGS storms in November 2004 and April 2006 (fig. 16). Concen- protocol for determining bacteria densities, which requires trations of nitrate and total phosphorus tended to be slightly sample analysis within 6 hours of sample collection (Myers larger for the storm of November 2004 as compared to the and Wilde, 2003). Some bacterial die-off would be expected concentrations detected for the other storms. Discharges at 20 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

1,000 100 Nitrate as nitrogen Total phosphorus

10 100

0.10

LOAD, IN TONS PER DAY 1 0.010

0.10 0.001 Big Sugar Little Sugar Indian Elk River Big Sugar Little Sugar Indian Elk River Creek Creek Creek near Creek Creek Creek near near near near Tiff City near near near Tiff City Powell Pineville Lanagan Powell Pineville Lanagan EXPLANATION

Value within 1.5 and 3.0 times the interquartile range 90th percentile

75th percentile (upper quartile) 50th percentile (median) 25th percentile (lower quartile)

10th percentile Value within 1.5 and 3.0 times the interquartile range

Figure 13. The distribution of monthly nutrient loads in samples from the Upper Elk River Basin, October 2004 through September 2006.

Big Sugar Creek near Powell and the Elk River near Tiff City calculated at this site for the storm of November 2004 were were largest for that storm. This storm followed a period of the largest for all storms sampled. Small concentrations of decreased flow from September to November 2004 (discharge nutrients carried in large storm flows can deliver extremely at the Elk River near Tiff City was less than 100 ft3/s for large loads of nutrients. For example, in the storm of Novem- much of this period). The nitrate concentrations in stormwater ber 2004, the nitrate load at Big Sugar Creek near Powell was samples ranged from 133 to 179 percent of the concentration 13 percent and the total phosphorus load was 32 percent of the in the ambient samples. The total phosphorus concentrations load calculated at that site for the entire set of ambient samples in the stormwater samples ranged from about 200 to more than collected from October 2004 through September 2006. Also, 600 percent of the concentration in the ambient samples. the total phosphorus load in the samples from the November Nitrate concentrations in stormwater samples gener- 2004 storm at the Elk River near Tiff City were 26 percent of ally increased with increasing discharge and decreased with the load of the ambient samples. decreasing discharge at Big Sugar Creek near Powell and the Samples were collected for nitrogen isotope analyses Elk River near Tiff City, which may indicate similar sources during two storms. Stable isotopes, including those of nitro- and modes of transport during stormwater runoff. Samples gen, are at or near natural abundance levels and usually are collected from two of the three storms at Indian Creek near reported as delta, a value in parts per thousand (per mil). The Lanagan had decreasing nitrate concentrations with increasing samples were analyzed for the 15N/14N isotope ratio (hereafter discharge. Total phosphorus concentrations at all sites gener- referred to as δ15 N). The nitrogen isotope values in this report ally increased with increasing discharge. are in parts per thousand (per mil) relative to nitrogen in air Nutrient loads for stormwater samples were largest in (Mariotti, 1983). Samples (δ15N analyses in per mil) from Big samples from the Elk River near Tiff City (fig. 17). The loads Sugar (+6.23) and Little Sugar Creeks (+11.21) and the Elk Water Quality 21

5 EXPLANATION 4.5 Nitrate as nitrogen

4 Big Sugar Creek near Powell 3.5 near Pineville

3 Little Sugar Creek below Caverna 2.5 near Pineville

2 Indian Creek near Lanagan Elk River near Tiff City 1.5

CONCENTRATION, IN MILLIGRAMS PER LITER 0.5

0 2/20/2005 4/20/2005 6/20/2005 8/20/2005 2/20/2006 4/20/2006 6/20/2006 8/20/2006 10/20/2004 12/20/2004 10/20/2005 12/20/2005

100,000

Elk River near Tiff City

10,000

1,000

100

DISCHARGE, IN CUBIC FEET PER SECOND 10

1 2/1/2005 4/1/2005 6/1/2005 8/1/2005 2/1/2006 4/1/2006 6/1/2006 8/1/2006 10/1/2004 12/1/2004 10/1/2005 12/1/2005

Figure 14. Relation of nitrate as nitrogen concentrations in samples from the Upper Elk River Basin to discharge in the Elk River near Tiff City, October 2004 through September 2006. 22 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

0.5 EXPLANATION

0.45 Total phosphorous

Big Sugar Creek 0.4 near Powell

0.35 near Pineville Little Sugar Creek 0.3 below Caverna

0.25 near Pineville Indian Creek near Lanagan 0.2 Elk River near Tiff City

0.15

CONCENTRATION, IN MILLIGRAM PER LITER 0.1

0.05

0 2/20/2005 4/20/2005 6/20/2005 8/20/2005 2/20/2006 4/20/2006 6/20/2006 8/20/2006 10/20/2004 12/20/2004 10/20/2005 12/20/2005

10,000

Little Sugar Creek near Pineville

1,000

100

10 DISCHARGE, IN CUBIC FEET PER SECOND

1 2/1/2005 4/1/2005 6/1/2005 8/1/2005 2/1/2006 4/1/2006 6/1/2006 8/1/2006 10/1/2004 12/1/2004 10/1/2005 12/1/2005

Figure 15. Relation of total phosphorus concentrations in samples from the Upper Elk River Basin to discharge in Little Sugar Creek near Pineville, October 2004 through September 2006. Water Quality 23

5 EXPLANATION

Nitrate as nitrogen Value more than 3.0 times the interquartile range Value within 1.5 and 3.0 times the interquartile range 4 90th percentile

3 75th percentile (upper quartile) 50th percentile (median) 25th percentile (lower quartile)

2 10th percentile Value within 1.5 and 3.0 times the interquartile range Value more than 3.0 times the interquartile range 1 Big Sugar Creek near Powell

5 Little Sugar Creek near Pineville Indian Creek near Lanagan Elk River near Tiff City Total nitrogen

CONCENTRATION, IN MILLIGRAMS PER LITER

1.2

Total phosphorus 1.0

0.8

0.6

0.4

0.2

0 November May April May November- 2004 2005 2006 2006 December 2006 STORM

Figure 16. The distribution of nutrient concentrations in stormwater samples in the Upper Elk River Basin, October 2004 through December 2006. 24 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

------6 5.3 7.3 8.8 13.1 20.1 (mg/L) Sulfate

------0.1 <.1 <.1 E.1 E.1 <0.1 (mg/L) Fluoride

------5.25 2.8 4.53 4.6 11.9 13.1 (mg/L) Chloride

------2.97 2.31 2.45 3.22 10 12 (mg/L) Sodium

------2.33 2.07 1.94 3.41 3.06 3.87 (mg/L) Potassium

------4.49 3.17 2.96 3.13 4.16 3.81 (mg/L) Magnesium

------53.1 46.3 50.1 51.1 39.0 55.8 (mg/L) Calcium Big Sugar Creek near Powell Little Sugar Creek near Pineville -- pH 7.8 7.7 7.6 7.6 7.6 7.7 7.5 7.6 7.7 7.7 7.7 7.7 8.1 8.1 8.0 8.0 8.0 8.2 8.0 8.2 7.9 8.0 7.9 7.9 7.9 8.2 8.0 8.0 8.0 7.9 7.9

266 219 195 195 210 263 254 241 250 264 272 277 269 270 260 259 263 320 326 310 291 293 237 251 273 283 351 348 312 270 259 277 (µS/cm) Specific conductance N nitrogen isotope ratio in parts per thousand (per mil)]

14 N/ 15 /s) 3 328 590 360 492 581 472 585 442 260 402 747 794 637 211 381 568 847 800 842 242 439 973 718 N, (ft 1,220 1,140 2,360 1,710 1,460 1,490 1,240 1,310 1,440 15 δ Discharge 021 ; E, estimated; Time 0138 0241 0441 0821 1221 1308 1414 1654 2154 2354 0754 1009 1510 2310 0310 0910 0703 1044 1724 0124 0924 1220 1510 2225 0805 0909 1013 1335 1555 2353 0753 Values of physical properties, major ion and nutrient concentrations, bacteria densities in stormwater samples the Upper Elk River Basin, October 2004 through Values

Escherichia coli Escherichia , Date /s, cubic feet per second; --, no data; <, less than; mg/L, milligrams per liter; µS/cm, microsiemens per centimeter at 25 degrees Celsius; N, nitrogen; P, phosphorus; col/100 mL, colonies per 100 milliliters; Celsius; N, nitrogen; P, /s, cubic feet per second; --, no data; <, less than; mg/L, milligrams liter; µS/cm, microsiemens centimeter at 25 degrees 3 11/1/2004 11/1/2004 11/1/2004 11/1/2004 11/1/2004 11/2/2004 5/24/2005 5/24/2005 5/24/2005 5/24/2005 5/24/2005 5/25/2005 4/29/2006 4/29/2006 4/29/2006 4/30/2006 4/30/2006 4/29/2006 4/29/2006 4/29/2006 4/30/2006 4/30/2006 5/10/2006 5/10/2006 5/10/2006 5/11/2006 11/30/2006 11/30/2006 11/30/2006 11/30/2006 11/30/2006 12/1/2006 Table 3. Table December 2006.—Continued [ft E. coli Water Quality 25

------4.9 4.6 5.5 7.1 6.4 28.3 10.1 10.2 (mg/L) Sulfate

------<.1 <.1 <.1 <.1 E.1 E.1 E0.1 E0.1 (mg/L) Fluoride

------5.14 5.06 3.64 3.73 6.37 5.08 10 10.1 (mg/L) Chloride

------3.01 3.9 2.84 2.33 7.37 5.18 4.03 7.22 (mg/L) Sodium

------2.81 2.04 2.27 2.49 3.21 2.37 2.41 2.87 (mg/L) Potassium

------3.78 1.77 1.43 1.4 3.84 3.09 2.75 2.99 (mg/L) Magnesium

------Elk River near Tiff City Elk River near Tiff 39.9 46 38.1 32.6 51.1 47.4 46.1 49.4 (mg/L) Calcium Indian Creek near Lanagan ------pH 7.8 7.8 7.7 7.6 7.6 7.4 7.6 7.6 7.5 7.5 7.7 7.8 7.8 7.8 7.8 7.9 7.7 7.5 7.6 7.6 7.6 7.6 7.9 7.6 7.7 7.5 7.7 7.7 7.5 7.6

------226 244 201 184 297 209 190 201 228 253 277 270 262 270 277 275 239 239 299 (µS/cm) Specific conductance N nitrogen isotope ratio in parts per thousand (per mil)]

14 N/ 15 /s) 3 326 437 662 613 567 495 888 740 796 N, (ft 1,020 1,520 3,210 1,560 1,670 2,390 1,810 1,850 1,440 4,620 8,180 9,720 6,260 3,830 1,196 1,490 1,730 1,720 1,500 2,962 3,650 2,880 1,305 2,310 2,725 2,985 15 δ Discharge ; E, estimated; Time 0115 0218 0418 1158 2358 1150 1335 1535 2035 0235 1030 1245 1435 1630 2200 0745 0450 0713 1333 2133 0636 1636 1906 2131 0611 0940 2211 0211 0756 1456 1039 1820 0620 1020 1420 Values of physical properties, major ion and nutrient concentrations, bacteria densities in stormwater samples the Upper Elk River Basin, October 2004 through Values a

Escherichia coli Escherichia , Date /s, cubic feet per second; --, no data; <, less than; mg/L, milligrams per liter; µS/cm, microsiemens per centimeter at 25 degrees Celsius; N, nitrogen; P, phosphorus; col/100 mL, colonies per 100 milliliters; Celsius; N, nitrogen; P, /s, cubic feet per second; --, no data; <, less than; mg/L, milligrams liter; µS/cm, microsiemens centimeter at 25 degrees 3 11/1/2004 11/1/2004 11/1/2004 11/1/2004 11/1/2004 5/23/2005 5/23/2005 5/23/2005 5/23/2005 5/24/2005 5/25/2005 5/10/2006 5/10/2006 5/10/2006 5/10/2006 5/11/2006 11/1/2004 11/1/2004 11/1/2004 11/1/2004 11/2/2004 11/2/2004 5/23/2005 5/23/2005 5/24/2005 5/24/2005 5/24/2005 5/25/2005 5/25/2005 5/25/2005 4/29/2006 4/29/2006 4/30/2006 4/30/2006 4/30/2006 Table 3. Table December 2006.—Continued [ft E. coli 26 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

N ------15 6.23 7.09 δ 11.21 (per mil)

------460 5,200 1,400 1,500 8,000 1,900 1,500 1,400 1,500 4,700 2,100 1,200 Fecal 27,000 22,000 coliform (col/100mL) ------

540 300 1,200 1,700 1,500 2,100 1,800 3,900 1,500 1,100 1,500 E. coli E1,600 E7,000 E16,000 (col/100mL)

.490 .280 .530 .340 .128 .176 .141 .078 .080 .069 .060 .038 .049 .057 .066 .060 .230 .210 .220 .171 .260 .270 .180 .161 .133 .192 .223 .340 .550 .330 .231 Total 0.063 (mg/L) phosphorus

- .19 .14 .21 .19 .08 .03 .02 .01 .03 .03 .03 .03 .03 .04 .03 .03 .19 .17 .17 .14 .04 .12 .10 .09 .09 .09 .17 .13 .16 .15 .14 0.05 (mg/L) Orthophos phorus as P

.011 .010 .011 .010 .012 .019 .027 .014 .011 .011 .011 0.008 0.008 0.013 0.011 <.008 <.008 <.008 <.008 <.008 <.008 <.008 <.008 <.008 E.006 E.006 E.004 E.004 E.007 E.006 E.006 E.006 (mg/L) Nitrite as N

1.64 1.56 1.62 2.82 3.52 4.01 1.34 1.16 1.16 1.34 1.36 1.34 1.66 2.02 2.46 2.52 2.72 1.20 1.38 1.52 1.59 1.69 1.31 1.48 1.65 1.68 1.93 2.14 1.75 1.95 2.03 2.14 (mg/L) Nitrite + nitrate as N Big Sugar Creek near Powell Little Sugar Creek near Pineville

.147 .246 .116 .086 .065 .066 <.04 <.04 <.04 <.04 <.04 <.04 <.04 <.04 <.04 <.04 <.04 <.04 <.04 <.04 <.04 <.04 <.04 <.04 <.04 E.02 E.02 E.02 E.02 E.02 as N (mg/L) <0.04 E0.02 Ammonia

.47 .74 .58 .33 .31 .23 .20 .20 .33 .33 .80 .71 .49 .36 .48 .61 .58 0.21 1.7 1.0 2.0 1.0 1.7 1.6 1.7 1.3 1.7 1.5 1.2 1.0 1.9 1.2 as N (mg/L) organic N Ammonia + N nitrogen isotope ratio in parts per thousand (per mil)] 14

N/ 15 ------N, 9.1 9.3 9.5 8.8 15 Silica 13.1 20.1 (mg/L) δ 021 ; E, estimated; Time 0138 0241 0441 0821 1221 1308 1414 1654 2154 2354 0754 1009 1510 2310 0310 0910 0703 1044 1724 0124 0924 1220 1510 2225 0805 0909 1013 1335 1555 2353 0753 Values of physical properties, major ion and nutrient concentrations, bacteria densities in stormwater samples the Upper Elk River Basin, October 2004 through Values

N ------15 7.38 9.30 δ (per mil)

------910 <100 E700 E770 4,100 5,300 3,000 5,000 2,000 1,800 Fecal 25,000 27,000 30,000 E1,300 coliform E13,000 (col/100mL) ------

800 E890 E300 E270 3,000 2,700 7,200 1,000 1,500 1,000 2,000 25,000 E. coli E1,500 E11,000 E10,000 (col/100mL)

.550 .260 .610 .350 .101 .101 .092 .200 .115 .108 .210 .540 .260 .200 .190 .500 .380 .360 .260 .165 .190 .122 .126 .090 .084 .133 .320 .340 .086 .083 .128 .094 .100 Total 1.03 0.135 (mg/L) phosphorus

- .06 .08 .21 .22 .04 .02 .04 .12 .05 .04 .05 .11 .07 .09 .12 .18 .12 .14 .13 .09 .02 .04 .05 .04 .03 .04 .04 .05 .05 .05 0.04 0.10 <.02 <.02 <.02 (mg/L) Orthophos phorus as P

.011 .008 .010 .009 .008 .008 .009 .009 .011 .013 .009 .037 .010 .010 .011 .014 .011 0.021 <.008 E.007 E.006 E.005 E.005 E.004 E.005 E.006 E.006 E.006 E.005 E.007 E.007 E.006 E.007 E.004 E.004 (mg/L) Nitrite as N

1.17 1.08 1.33 1.60 2.48 1.99 2.05 2.06 2.10 2.25 1.97 1.65 1.20 1.78 2.42 2.38 1.41 1.26 1.62 1.87 2.40 2.47 1.38 1.44 1.41 1.44 1.43 1.62 1.31 1.26 1.06 1.30 1.46 1.55 1.64 Elk River near Tiff City Elk River near Tiff (mg/L) Nitrite + Indian Creek near Lanagan nitrate as N

.07 <.04 <.04 <.04 <.04 <.04 <.04 <.04 <.04 <.04 <.04 <.04 <.04 E.02 E.02 E.02 E.02 E.02 E.02 E.02 E.02 E.02 E.02 E.02 E.02 E.02 E.03 E.03 E.03 E.03 E.03 E.04 E.02 as N (mg/L) <0.04 E0.02 Ammonia

.82 .42 .40 .36 .65 .33 .32 .91 .68 .78 .56 .74 .49 .40 .29 .27 .49 .46 .44 .72 .41 .44 1.0 1.6 1.0 2.2 1.2 3.6 1.3 0.31 1.9 1.5 1.3 1.3 1.1 as N (mg/L) organic N Ammonia + N nitrogen isotope ratio in parts per thousand (per mil)] 14

N/ 15 ------N, 5.8 8.8 9.2 <.2 15 Silica 11.1 10.9 11.4 (mg/L) δ 450 713 636 611 940 211 756 620 ; E, estimated; Time 0115 0218 0418 1158 2358 1150 1335 1535 2035 0235 1030 1245 1435 1630 2200 0745 1333 2133 1636 1906 2131 2211 1456 1039 1820 1020 1420 Values of physical properties, major ion and nutrient concentrations, bacteria densities in stormwater samples the Upper Elk River Basin, October 2004 through Values a

Escherichia coli Escherichia , Date /s, cubic feet per second; --, no data; <, less than; mg/L, milligrams per liter; µS/cm, microsiemens per centimeter at 25 degrees Celsius; N, nitrogen; P, phosphorus; col/100 mL, colonies per 100 milliliters; Celsius; N, nitrogen; P, /s, cubic feet per second; --, no data; <, less than; mg/L, milligrams liter; µS/cm, microsiemens centimeter at 25 degrees Ambient sample. 3 a 11/1/2004 11/1/2004 11/1/2004 11/1/2004 11/1/2004 5/23/2005 5/23/2005 5/23/2005 5/23/2005 5/24/2005 5/25/2005 5/10/2006 5/10/2006 5/10/2006 5/10/2006 5/11/2006 11/1/2004 11/1/2004 11/1/2004 11/1/2004 11/2/2004 11/2/2004 5/23/2005 5/23/2005 5/24/2005 5/24/2005 5/24/2005 5/25/2005 5/25/2005 5/25/2005 4/29/2006 4/29/2006 4/30/2006 4/30/2006 4/30/2006 Table 3. Table December 2006.—Continued [ft E. coli 28 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

50 EXPLANATION

Nitrate as nitrogen Value more than 3.0 times the interquartile range Value within 1.5 and 3.0 times the interquartile range 40 90th percentile

75th percentile (upper quartile) 30 50th percentile (median) 25th percentile (lower quartile)

20 10th percentile Value within 1.5 and 3.0 times the interquartile range Value more than 3.0 times the interquartile range

10 Big Sugar Creek near Powell Little Sugar Creek near Pineville Indian Creek near Lanagan Elk River near Tiff City 0

LOAD, IN TONS PER DAY Total phosphorus

0 November May April May November- 2004 2005 2006 2006 December 2006 STORM

Figure 17. The distribution of nutrient loads in stormwater samples in the Upper Elk River Basin, October 2004 through December 2006. Water Quality 29

River near Tiff City (+9.30) were collected on April 29, 2006, Creek, discharge was measured at 1.5 ft3/s (site BK02) and had and samples from Little Sugar (+7.09) and Indian Creeks increased to about 5 ft3/s at the gaging station near Powell (site (+7.38) were collected on May 10, 2006. Chemical fertilizer JS06) and remained stable to Big Sugar Creek at Cyclone (site has a value less than +6 per mil, septic tank effluent has a BK11), even with an input of more that 2 ft3/s from Mikes value of -2 to +3 per mil, human sewage has a value of +1 to Creek (site JS09). A decrease of about 2 ft3/s was measured +11 per mil (Lindsey and Koch, 2004), and animal manure has from Cyclone to below Hambrich Hollow (site BK12). How- a value of about + 5 to +15 per mil (Jeffrey and others, 1997). ever, the measurement at Hambrich Hollow was rated poor. The value from Big Sugar Creek near Powell is in the range of Discharge at the mouth of Big Sugar Creek (site BK 15) had animal manure and human sewage. Because no sewage inflow decreased to 3.6 ft3/s from 4.8 ft3/s at the site above Dog Hol- is permitted for this stream, this δ15N value indicates animal low (site BK13), with an additional 0.21 ft3/s from Dog Hol- sources. The source of the δ15N from Little Sugar Creek with low (site BK14). The streambed was comprised of gravel for a value of +11.21 per mil is in the range of human sewage many of the stream reaches in the Big Sugar Creek Basin. and animal manure. Based on effluent inflow into Little Sugar Discharge in Little Sugar Creek was first measured down- Creek from Bella Vista, Arkansas, and upstream land use, the stream from the lake at Bella Vista, Arkansas (site JR02; 14 value probably is indicative of human and animal sources. The ft3/s). It decreased slightly at Little Sugar Creek above Tanyard δ15N values for May 2006 for Little Sugar and Indian Creeks Creek (site JR74) then increased to 15 ft3/s at Little Sugar were about +7.0 per mil, indicating human or animal sources, Creek at Missouri Road (site JR01). The discharge at this site or a combination. was the largest measured in Little Sugar Creek. Discharge at the mouth of Little Sugar Creek (site JR04) was 13 ft3/s, even after small inputs of less than 1 ft3/s from tributaries to Little Seepage Run Water Quality Sugar Creek. Two tributaries, South Indian Creek (site JS17) and North The Elk River and its tributaries are the primary discharge Indian Creek (site JS19), provided about 7 ft3/s each to the areas for precipitation that percolates through the land surface flow of Indian Creek. At Indian Creek near Erie (site JS23) and recharges the ground water in the study area. A seepage the discharge was 19 ft3/s. The discharge increased slightly at run, a series of stream discharge measurements made along a the mouth of Indian Creek from small inflow from springs and stream reach during a short time to identify where gains and tributaries upstream from the mouth. losses in flow occur, was conducted on these streams. A seep- The discharge measured in the Elk River downstream age run is designed to be made during periods of minimum from the inflow of Big and Little Sugar Creeks (site JR30) was streamflow and minimum daily fluctuations (base flow). Base 16 ft3/s. The discharge from Big Sugar Creek (site BK15; 3.6 flow is sustained by diffuse ground-water and spring inflow, ft3/s) and Little Sugar Creek (site JR04; 13 ft3/s) accounts for not by surface runoff. The flow-rate changes were used to this. Discharge in the Elk River upstream from Indian Creek identify gaining and losing stream reaches throughout the (site BK18) was 15 ft3/s. The inflow from Indian Creek (site basin. Water-quality samples also were collected at selected JR27) was 21 ft3/s, resulting in a discharge of 36 ft3/s in the sites to identify where increases or decreases in constituent Elk River downstream from Indian Creek. The discharge mea- concentrations occurred. sured downstream from Noel (site BK24) was 40 ft3/s, which The USGS conducted a low-flow seepage run on the Elk included additional inflows of almost 1.5 ft3/s. Upstream from River and its tributaries from July 31 to August 3, 2006. Dis- Tiff City (site BK27), the measured discharge was 38 ft3/s, charge was measured at more than 70 sites and water-quality which was a decrease of almost 5 percent from the discharge samples were collected at more than 45 sites (fig. 18). The dis- in the Elk River downstream from Noel. The discharge at Tiff charge at the Elk River near Tiff City on August 3, 2006, was City was 40 ft3/s. 40 ft3/s; the discharge during the time of the seepage run was A few decreases in streamflow were noted, usually from the smallest measured from October 2004 through September one site to another. The decreases were in Big and Little Sugar 2006. The annual mean discharge from October 2005 through Creeks and in the mainstem of the Elk River. In most cases, September 2006 was 234 ft3/s at the Elk River near Tiff City. the decrease was within measurement error (generally less The Upper Elk River Basin was abnormally dry or under a than 8 percent). Because the decreases were small, definitive moderate drought (National Drought Mitigation Center, 2007) losing stream reaches could not be identified. at the time of this seepage run. Another seepage run was con- Base-flow conditions, as reflected by the seepage run, ducted November 13 and 14, 2006, at eight of the sites from indicate that about 52 percent of the discharge at the Elk River the previous seepage run and an additional site. The second near Tiff City is contributed by Indian Creek. Little Sugar seepage run was conducted at a different time and under dif- Creek contributes about 32 percent and Big Sugar Creek con- ferent hydrologic conditions. In November, the discharge at tributes about 9 percent of the discharge in the Elk River near the Elk River near Tiff City was 65 ft3/s. Tiff City. Only about 7 percent of the discharge at Tiff City In the first seepage run, discharge measurements indi- comes from the mainstem of the Elk River. cated that in the Upper Elk River Basin, most of the streams Specific conductance values during the seepage run were gained flow (table 4; fig. 18). In the upper reach of Big Sugar 453 µS/cm or less; the specific conductance generally was 30 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06 MILES 10 KILOMETERS

10 BARRY Creek

5 94° Greasy 5

Creek Creek

1.5

BK02 r

Creek C Creek Trent 0 0

r Brush Mikes a g u 3.8 S BK05

Big Indian k

1.3 e

BK07

e r 0.02 JS01

2.3 C

JS09

4.5

n JS04

i South

0.53 d JS03

n I 5.3 pool JS07 JS14

k 5.7 North 1.8 e JS21 4.8 k

JS12 e

JS06 e

r e Creek C

Creek r

6.6 r

JS19

6.9

u r

Bear 12

JS17 o a Cr

s JR74 g

5.0 13

s Su i BK11

14 JR73 M JR02 94°15’’

Creek g

u Little

n 15 k

S e

C 0.01 r

i JR49

JR01 0.01

d JR47

Elkhorn d I r

a y

12 n a JR34 T

Big 12 JR03 0.70 3.0 JR76 0.46 NEWTON BK12 2.8 JRMM JS25 0.02 JR67 4.8 BK13

MCDONALD

JS23

Cr Bullskin MISSOURI ARKANSAS 3.6 BK15 1.1 0.67 JR82 JR64 0.21 JS28 BK14 BENTON 13

JR04 Creek 16 JR30

Creek

h 19

n JR54 a

r r

B le

21 Creek t

r 0.18

e u JR27 JR62 v a e B B

21 Deer

20 Mill JR06 JR08 15 BK18

ver 94°30’’ i

R 0.75

BK22

k 0.65

l BK21 E 40 BK24 38 BK27

JS29

MISSOURI OKLAHOMA

River Elk EXPLANATION Location of seepage run sites and discharge values in the Upper Elk River Basin. Grand Lake Lake Grand DELAWARE OTTAWA Water-quality sampling site and identifier Water-quality First seepage run (July 31 through August 3, 2006) 2006) Second seepage run ( November Both seepage runs site and identifier Measurement in cubic feet per second Number is discharge, seepage run only) (first

O’ the Cherokees 40 94°45’’ JS29 JR82 BK14 BK22 Figure 18. Base from U.S. Geological Survey digital data, 1:100,000, 1992 Mercator projection Universal Transverse Zone 15 36°45’’ 36°30’’ Water Quality 31 less than 350 µS/cm in Big Sugar Creek and the Elk River and by about 60 percent from the concentration detected in the tributaries. Specific conductance values generally were larger sample from Little Sugar Creek near the mouth (0.097 mg/L). than 350 µS/cm in Little Sugar Creek. Selected wastewater indicator (table 5) and pharmaceuti- Potassium, sodium, chloride, and sulfate concentrations cal compounds were analyzed in samples from six sites during in samples from Little Sugar Creek and tributaries were larger the first seepage run. Six wastewater indicator compounds relative to most of the other samples (table 4). The concentra- were detected—most of the concentrations were estimated or tions in these samples possibly could indicate greater waste- presence verified, but not quantified (table 6). The remaining water effects in this basin. Effluent from municipal wastewater wastewater indicator compounds were detected at less than 1 treatment plants commonly contains increased concentrations microgram per liter (µg/L). Four of the six compounds were of potassium, sodium, chloride, and sulfate, relative to calcium detected in the sample from Little Sugar Creek at Caverna and magnesium (Schumacher, 2001). (site JR34); one compound was detected in the sample from Fecal indicator bacteria densities generally did not exceed Big Sugar Creek at the mouth (site BK15) and the Elk River the Missouri water-quality criteria for whole-body-contact rec- near Tiff City (site JS29). Three pharmaceutical compounds reation from samples collected during the seepage run in July were detected in the first seepage run samples; all detections and August. E. coli densities larger than 126 col/100 mL were were estimated and were in the sample from Little Sugar counted in samples from two tributaries to Little Sugar Creek Creek at Caverna. Compounds included carbamazepine (0.040 (sites JR49 and JRMM) and a tributary to Indian Creek (site µg/L, high blood pressure), diltiazem (0.003 µg/L, urinary JS14). Evidence of cattle was present at the site on Missouri tract infections), and sulfamethoxazole (0.038 µg/L, manic Creek (E. coli of 230 col/100 mL). Fecal coliform densities depression and bipolar disorder). exceeded 200 col/100 mL at four sites—three tributaries to Optical brighteners are added to laundry detergents as Little Sugar Creek (sites JR47, JR49, and JRMM; two had whiteners for cotton and other plant-derived textiles. Detec- large E. coli densities) and a tributary to Indian Creek (site tion of optical brighteners in a water sample is an indicator of JS17) that did not have the large E. coli density. effects from septic systems. Samples were collected at all sites The nitrate concentrations in most samples from the first shown in table 4, and no optical brighteners were detected in seepage run were about 1 mg/L or less (table 4; fig. 19), espe- any of the samples. cially in Big and Little Sugar Creek and their tributaries and in Chlorophyll a is the predominant type of pigment in the mainstem of the Elk River. The exceptions were in samples algae and blue-green algae. Excessive quantities are indica- from Indian Creek and its tributaries, especially in the upper tive of algal blooms. Chlorophyll a concentrations generally reaches of the basin. Concentrations in two of the three springs were less than 10 µg/L in samples (table 4), except for Little sampled in the Indian Creek Basin were the largest detected— Sugar Creek below Bella Vista, Ark. (site JR02; 39.2 µg/L) 4.34 mg/L from Sears Spring (site JS21) and 11.1 mg/L from and Maness Spring (site JR64; 38.8 µg/L). Excessive nutrient the spring at MoArk site 13 (site JR67). Concentrations in the concentrations can stimulate algal growth. Little Sugar Creek upper reaches of the Indian Creek Basin were larger than 2.50 below Bella Vista had the largest total phosphorus concentra- mg/L and decreased downstream from 1.66 mg/L in samples tion detected in the seepage run samples (0.670 mg/L). from Indian Creek near Erie (site JS23) to less than 1.0 mg/L Samples were collected for nitrogen isotope analyses at the mouth of Indian Creek (JR27). Many livestock produc- throughout the upper Elk River Basin in conjunction with tion facilities in the Upper Elk River Basin are in the upper the seepage run. Samples were collected at the mouth of Big reaches of the Indian Creek Basin (fig. 4). Sugar (site BK15), Little Sugar (site JR04), and Indian Creeks Total phosphorus concentrations in the seepage run (site JR27) and the Elk River near Tiff City (site JS29). A samples in the summer of 2006 were less than 0.1 mg/L (table sample also was collected at Little Sugar Creek at Caverna 4; fig. 20) with a few exceptions: 0.128 mg/L from the spring (site JS34). The δ15N values at all sites were greater than +11 at MoArk site 13 (site JR67) and samples from Little Sugar per mil except for the sample from the mouth of Big Sugar Creek and its tributaries. Total phosphorus concentrations were Creek (+8.5 per mil). Values greater than +12 per mil indicate largest in the upper reaches of the Little Sugar Creek Basin the source likely originates from organic nitrogen (human downstream from Bella Vista (site JR02; 0.67 mg/L), with a sewage or animal manure). Manure has a δ15N value of about trend of generally decreasing concentrations to the mouth of + 5 to +15 per mil (Jeffrey and others, 1997), and δ15N value Little Sugar Creek (site JR04; 0.097 mg/L). Tributary inflow of human sewage is + 1 to +11 per mil (Lindsey and Koch, did not contribute to the large total phosphorus concentrations 2004). Chemical fertilizers have a δ15N value of less than +6 detected in the basin, but diluted the concentrations. per mil (Lindsay and Koch, 2004). Water from Little Sugar Nitrate concentrations from the mouth of the three major Creek from both sites and the Elk River near Tiff City prob- tributaries to the Elk River in the study area included 0.223 ably has a component of effluent mixed with animal manure mg/L (Big Sugar Creek), 0.102 mg/L (Little Sugar Creek), and fertilizer from lawns and golf courses. Indian Creek is a 0.648 mg/L (Indian Creek). The nitrate concentration detected receiving stream for effluent from local communities: how- in the sample from the Elk River near Tiff City was 0.295 ever, septic tank effluent generally has a δ15N value of less mg/L. The total phosphorus concentration detected in the sam- than +4 per mil, which indicates the source of the δ15N value ple from the Elk River near Tiff City (0.039 mg/L decreased in Indian Creek likely is animal manure and human sewage. 32 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

------9.06 11.8 12.1 11.1 12.0 11.7 11.5 12.3 11.7 11.3 12.7 11.3 13.2 11.4 12.9 13.4 13.1 12.8 Silica (mg/L)

------6.07 5.09 4.95 5.62 5.84 2.59 4.56 4.73 3.38 4.54 3.58 7.64 3.94 4.38 16.6 12.2 10.8 10.9 (mg/L) Sulfate

------.16 ------<.10 <.10 <.10 <.10 <.10 <.10 <.10 <.10 <.10 <.10 <.10 <.10 <.10 <.10 <.10 E.07 <0.10 (mg/L) Fluoride

------6.14 3.93 4.17 5.07 4.71 7.64 7.77 7.52 7.06 6.98 6.93 7.45 7.63 18.9 13.2 15.7 10.7 21.1 (mg/L) Chloride

------3.63 2.54 2.47 3.45 2.99 5.01 5.77 5.63 4.49 4.65 4.52 9.63 4.85 5.16 6.94 17.1 11.3 14.8 (mg/L) Sodium

------2.36 1.68 1.57 2.18 2.13 4.86 3.7 2.05 2.43 2.4 2.18 2.04 2.36 2.15 2.37 2.49 2.29 5.36 (mg/L) Potassium

N isotope ratio; per mil, parts thousand] ------14 47.2 56.5 58.7 50.5 51.1 58.2 55.4 61.0 67.8 68.9 53.0 58.9 49.6 72.0 52.2 50.8 56.9 45.8 N/ (mg/L) Calcium 15 N, 15 δ 7.6 8.2 7.3 7.4 7.7 7.6 7.8 7.6 7.4 8.8 8.6 8.6 8.6 8.5 8.4 8.3 7.2 8.0 7.7 7.7 7.9 7.8 7.9 8.4 8.1 7.9 8.0 8.0 7.3 7.6 8.0 8.1 7.2 8.0 7.4 8.0 7.6 7.9 8.0 7.7 8.2 7.8 7.5 8.0 8.1 7.6 7.7 pH

317 245 293 289 171 305 281 299 311 284 287 309 337 289 381 376 234 367 387 290 377 398 453 373 347 337 352 342 362 361 315 303 401 210 301 277 395 286 282 287 321 298 343 355 340 331 326 (µS/cm) Specific conductance

22.7 31.5 24.9 26.8 27.2 27.7 29.5 24.4 19.7 28.1 29.8 26.8 27.5 29.0 27.2 30.7 23.9 30.4 26.3 23.8 26.1 27.8 26.4 30.3 30.1 24.6 24.4 27.9 17.5 20.7 27.6 29.8 22.9 28.4 20.0 29.7 20.6 27.0 26.7 27.1 31.2 27.3 26.9 29.9 31.8 28.7 27.9 (°C) Water temperature

/s) .02 .53 .21 .01 .70 .01 .46 .02 .67 .18 .75 .65 3 1.5 3.8 1.3 4.5 4.8 2.3 5.0 3.0 4.8 3.6 1.8 5.3 6.9 5.7 6.6 2.8 1.1 pool 14 12 13 12 15 12 13 19 19 20 21 21 16 15 40 38 40 (ft Discharge 1345 1600 1330 1355 1750 1515 1710 1830 0830 1310 1510 1620 1725 1815 1540 1640 1720 1800 0830 0920 1010 1040 1220 1330 1620 1230 1400 1600 1015 1845 1500 1300 0740 0820 1745 1510 1420 1140 0930 0820 1730 1030 1430 1330 1635 1015 0900 Time ; µg/L, micrograms per liter; K, count outside acceptable range; Date 7/31/2006 7/31/2006 7/31/2006 7/31/2006 7/31/2006 7/31/2006 7/31/2006 7/31/2006 8/1/2006 8/1/2006 8/1/2006 8/1/2006 8/1/2006 8/1/2006 7/31/2006 7/31/2006 7/31/2006 7/31/2006 8/1/2006 8/1/2006 8/1/2006 8/1/2006 8/1/2006 8/1/2006 8/1/2006 8/1/2006 8/1/2006 8/1/2006 8/2/2006 8/1/2006 8/2/2006 8/2/2006 8/3/2006 8/3/2006 8/2/2006 8/2/2006 8/2/2006 8/2/2006 8/2/2006 8/2/2006 8/1/2006 8/2/2006 8/2/2006 8/2/2006 8/2/2006 8/3/2006 8/3/2006 Escherichia coli Escherichia , E. coli Site name Values of physical properties, major ion and nutrient concentrations, bacteria densities in samples from the seepage run, July 31 through August 3, 2006, Values Big Sugar Creek below Greasy Creek Creek below Big Sugar Creek at Mountain Big Sugar Creek at mouth Trent Creek Creek at Trent Big Sugar Creek Trent Creek below Big Sugar Creek near Blackjack Hollow Big Sugar Creek near Powell Big Sugar Creek near mouth Mikes Hayes Hollow Creek above Mikes Creek at Cyclone Big Sugar Hambrich Hollow Creek below Big Sugar Dog Hollow Creek above Big Sugar Dog Hollow Creek at mouth Big Sugar Ark. Bella Vista, Creek below Little Sugar Creek Tanyard Creek above Little Sugar Creek Tanyard Creek Tanyard Creek below Little Sugar Creek at Caverna Little Sugar Gordon Hollow Creek at Missouri Road Little Sugar Missouri Creek 90 Miser Creek at Highway Creek at Skaggs Hollow Little Sugar Creek at mouth Little Sugar South Indian Creek at Stella Stella South Indian Creek below South Indian Creek near mouth Sears Spring near Wanda North Indian Creek near Wanda Elkhorn Creek near mouth Indian Creek near Erie Spring at MoArk site 13 Maness Spring Bullskin Creek near mouth Anderson Indian Creek above Branch at mouth Beaver Indian Creek at Anderson Indian Creek near Lanagan Indian Creek at mouth 71 Highway below Elk River Indian Creek above Elk River Butler Creek at Deer Road Bulter Creek at mouth Noel below Elk River Hollow Lake Honey below Elk River City near Tiff Elk River

Site /s, cubic feet per second; °C, degrees Celsius; µS/cm, microsiemens per centimeter at 25 degrees Celsius; mg/L, milligrams per liter; --, no data; <, less than; E, estimated; N, nitrogen; col/100 Celsius; µS/cm, microsiemens per centimeter at 25 degrees /s, cubic feet per second; °C, degrees 3 (fig. 18) identifier BK02 BK05 JS01 JS03 BK07 JS04 JS06 JS07 JS09 BK11 BK12 BK13 BK14 BK15 JR02 JR74 JR47 JR73 JR34 JR76 JR01 JR49 JRMM JR03 JR04 JS12 JS14 JS17 JS21 JS19 JS25 JS23 JR67 JR64 JS28 JR54 JR62 JR08 JR06 JR27 JR30 BK18 BK22 BK21 BK24 BK27 JS29 Table 4. Table in the Upper Elk River Basin. [ft mL, colonies per 100 milliliters; Water Quality 33

------8.5 15N mil) (per 16.9 14.4 15.4 12.8 δ

.60 .80 .60 .30 -- .90 .70 a 1.1 3.3 2.7 1.2 1.7 2.8 1.3 1.8 2.7 1.4 6.9 1.6 5.1 4.1 1.3 2.5 1.7 1.6 2.2 4.9 6.0 1.2 1.7 2.7 2.0 3.4 1.8 1.7 9.8 4.2 4.4 3.6 3.5 2.5 3.9 2.5 1.6 3.0 39.2 38.8 (µg/L) Chlorophyll

-- -- 21 5K 5K 5K 5K 5K 5K 150 160 140 240 100 115 240 120 240 115 100 35K 20K 10K 35K 20K 15K 35K 80K 25K 55K 25K 45K 10K 50K 20K 10K 90K 40K 45K 75K 75K 30K 95K 20K 35K 75K 560K Fecal coliform (col/100 mL)

-- -- <5 <5 <5 5K 5K 7K 5K 5K 5K 230 175 100 mL) 20K 10K 20K 10K 10K 50K 10K 10K 75K 50K 20K 70K 25K 70K 40K 25K 20K 45K 30K 35K 10K 55K 20K 35K 55K 90K 10K 70K 80K 20K 20K 70K 490K E. coli (col/100

.030 .014 .022 .019 .011 .019 .012 .004 .012 .014 .013 .027 .009 .670 .479 -- .430 .460 .015 .370 .020 .052 .250 .097 .042 .056 .045 .053 .046 .029 .044 .128 .033 .018 .033 .051 .032 .032 .034 .068 .040 .045 .017 .056 .032 .039 Total 0.018 (mg/L) phosphorus

.024 .017 .021 .016 .013 .019 .014 .011 .009 .012 .011 .020 .009 .571 .450 -- .402 .424 .012 .346 .016 .048 .235 .078 .034 .039 .035 .050 .044 .022 .024 .118 .014 .022 .026 .018 .025 .024 .060 .047 .038 .014 .039 .021 .021 0.013 E.006 (mg/L) Ortho- phosphorus

.005 .003 .043 .005 -- .004 .032 .006 .004 .012 .003 .007 .020 .008 .003 .009 .007 .030 .004 .003 .004 .006 .004 .005 .012 .004 0.003 <.002 <.002 <.002 <.002 <.002 <.002 <.002 <.002 <.002 E.001 E.001 E.002 E.002 E.001 E.001 E.002 E.001 E.002 E.001 E.001 (mg/L) Nitrite N isotope ratio; per mil, parts thousand]

N/ 15 1.29 .824 .651 .564 .710 .704 .443 .694 .755 .270 .184 .253 .385 .223 1.09 .627 -- .528 .625 .178 .559 .812 1.1 .118 .102 2.94 3.21 2.58 4.34 4.13 1.99 1.66 11.1 E.030 .978 .949 1.68 .938 .692 .648 .100 .084 .408 E.032 1.03 .522 .295 N, (mg/L) nitrate Nitrite + 15 δ

<0.010 .023 <.010 <.010 E.006 .014 .014 .013 E.006 E.009 .014 E.009 .018 E.007 .168 .020 -- .026 .074 .013 .020 .015 <.010 .016 .011 .020 .024 .019 <.010 .018 .019 .011 .282 .022 <.010 .011 .012 <.010 .022 .010 .014 E.009 <.010 <.010 .042 .019 E.006 (mg/L) Ammonia

.30 .10 .10 .10 .10 .10 .20 .10 .77 .40 -- .30 .30 .10 .30 .20 .20 .22 .20 .20 .30 .30 .10 .20 .60 .50 .10 .10 .10 .20 .10 .20 .20 .10 .10 .30 .20 .20 <.1 <.1 E.06 E.09 E.08 E.07 E.09 E.10 E0.09 (mg/L) organic N Ammonia +

------48.4 53.4 53.4 48.8 49.8 58.9 58.5 52.9 68.2 68.8 53.4 55.3 53.3 70.3 55.5 55.9 57.8 (µg/L) Strontium 1345 1600 1330 1355 1750 1515 1710 1830 0830 1310 1510 1620 1725 1815 1540 1640 1720 1800 0830 0920 1010 1040 1220 1330 1620 1230 1400 1600 1015 1845 1500 1300 0740 0820 1745 1510 1420 1140 0930 0820 1730 1030 1430 1330 1635 1015 0900 Time Date 7/31/2006 7/31/2006 7/31/2006 7/31/2006 7/31/2006 7/31/2006 7/31/2006 7/31/2006 8/1/2006 8/1/2006 8/1/2006 8/1/2006 8/1/2006 8/1/2006 7/31/2006 7/31/2006 7/31/2006 7/31/2006 8/1/2006 8/1/2006 8/1/2006 8/1/2006 8/1/2006 8/1/2006 8/1/2006 8/1/2006 8/1/2006 8/1/2006 8/2/2006 8/1/2006 8/2/2006 8/2/2006 8/3/2006 8/3/2006 8/2/2006 8/2/2006 8/2/2006 8/2/2006 8/2/2006 8/2/2006 8/1/2006 8/2/2006 8/2/2006 8/2/2006 8/2/2006 8/3/2006 8/3/2006 ; µg/L, micrograms per liter; K, count outside acceptable range; Escherichia coli Escherichia , Site name E. coli Values of physical properties, major ion and nutrient concentrations, bacteria densities in samples from the seepage run, July 31 through August 3, 2006, Values Big Sugar Creek below Greasy Creek Creek below Big Sugar Creek at Mountain Big Sugar Creek at mouth Trent Creek Creek at Trent Big Sugar Creek Trent Creek below Big Sugar Creek near Blackjack Hollow Big Sugar Creek near Powell Big Sugar Creek near mouth Mikes Hayes Hollow Creek above Mikes Creek at Cyclone Big Sugar Hambrich Hollow Creek below Big Sugar Dog Hollow Creek above Big Sugar Dog Hollow Creek at mouth Big Sugar Ark. Bella Vista, Creek below Little Sugar Creek Tanyard Creek above Little Sugar Creek Tanyard Creek Tanyard Creek below Little Sugar Creek at Caverna Little Sugar Gordon Hollow Creek at Missouri Road Little Sugar Missouri Creek 90 Miser Creek at Highway Creek at Skaggs Hollow Little Sugar Creek at mouth Little Sugar South Indian Creek at Stella Stella South Indian Creek below South Indian Creek near mouth Sears Spring near Wanda North Indian Creek near Wanda Elkhorn Creek near mouth Indian Creek near Erie Spring at MoArk site 13 Maness Spring Bullskin Creek near mouth Anderson Indian Creek above Branch at mouth Beaver Indian Creek at Anderson Indian Creek near Lanagan Indian Creek at mouth 71 Highway below Elk River Indian Creek above Elk River Butler Creek at Deer Road Bulter Creek at mouth Noel below Elk River Hollow Lake Honey below Elk River City near Tiff Elk River

Site /s, cubic feet per second; °C, degrees Celsius; µS/cm, microsiemens per centimeter at 25 degrees Celsius; mg/L, milligrams per liter; --, no data; <, less than; E, estimated; N, nitrogen; col/100 mL, colo Celsius; µS/cm, microsiemens per centimeter at 25 degrees /s, cubic feet per second; °C, degrees 3 (fig. 18) identifier BK02 BK05 JS01 JS03 BK07 JS04 JS06 JS07 JS09 BK11 BK12 BK13 BK14 BK15 JR02 JR74 JR47 JR73 JR34 JR76 JR01 JR49 JRMM JR03 JR04 JS12 JS14 JS17 JS21 JS19 JS25 JS23 JR67 JR64 JS28 JR54 JR62 JR08 JR06 JR27 JR30 BK18 BK22 BK21 BK24 BK27 JS29 Table 4. Table Upper Elk River Basin.—Continued [ft nies per 100 milliliters;

34 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

near Tiff City Tiff near

o H e

e v

i R

k Noel w

h t o y

E l

u e

o n

m t

o H w

o k

i R l

e l

r r C

r e

e t

r C Elk River and tributaries l

i R u

a k

B i l

d E

h t

o b

m t Highway 71 Highway w

e l a

v k e

i R

Butler Creek at Deer Creek R Creek Deer at Creek Butler k

v E r C

i R a

e i

d l

near Lanagan near

n E

k n I

A t

k r C n

e n o

i r

d e

r C

n n I

A d

n I v

g o

b n

Beaver Branch at mouth at Branch Beaver

11.1 milligrams per liter p

and tributaries k

e S

e s

e r C

n n

i e

d M

n I E

a Bullskin Creek near mouth near Creek Bullskin

mouth

r a

a d

e r C

n Spring at MoArk site 13 site MoArk at Spring

Indian Creek n a

k i

e W

r e

n I a

k h t

e u

e o

r C Elkhorn m

r C

i e

n I

e a

l l e h t

e t

r C

o N n Sears Spring near Wanda near Spring Sears

below Stella below

S t

a k

d k

n I

r C

mouth t

h t

r C

o i

o k

d a

e S i

n I

o H

s r C

h t n I

h t a

u g a

S k

u o k

S e

S t

r C

l t t

Highway 90 Highway t k

L e

a u

k o

r C

e s

i r

w M

l u

o H

r C Miser

n l t t

Missouri Road Missouri t

L a

r k

o e k

e e G

r C

at Caverna at

k r C

e d

g r e e

Little Sugar Creek and tributaries u a e

S r C

. r C e

l t t

r g

T w

y A ,

S o

a t

e a

l t t

k L

a e

l e

T above at mouth at r C

k k

B w a

e e

o g

e e

e o H

r C

g r C

o r

o D

g l t t

u u

S S

r C

e r g

l t t

B i g

L o H u

i e

o H Dog above b l t t

i k

m w

e l

at Cyclone at

r C

a H w

o H

e s

r C

S k

a l

g l e

a H

e e

u B

e w

S o

near mouth near r C

r g k b

a P e

a r

k o a

l e

r C

k i

r C e

e k

i s e

i r C

r C t

n M

Big Sugar Creek and tributaries a

g e r

Nitrate as nitrogen u

r C t

T w

h t

i n

l u

B o H Blackjack near r e o

k m t

e T at

k e

r C

r e

r C

a e

k a

r C

e r g

r C t

e a u S

g g

e i

at Mountain at

u r

r C

k B

i T y

6 5 4 3 2 1 0 s

a i

B r

r C

a CONCENTRATION, IN MILLIGRAMS PER LITER LITER PER MILLIGRAMS IN CONCENTRATION,

g G w

l Concentration of nitrate as nitrogen in samples from the seepage run, July 31 through August 3, 2006, Upper Elk River B asin.

S e

i b

r C

g i B Figure 19.

Water Quality 35

near Tiff City Tiff near

o H e

e v

i R

k Noel w

h t o y

E l

u e

o n

m t

o H w

o k

i R l

e l

r r C

r e

e t

r C Elk River and tributaries l

i R u

a k

B i l

d E

h t

o b

m t Highway 71 Highway w

e l a

v k e

i R

Butler Creek at Deer Creek R Creek Deer at Creek Butler k

v E r C

i R a

e i

d l

near Lanagan near

n E

k n I

A t

k r C n

e n o

i r

d e

r C

n n I

A d

n I v

g o

b n

Beaver Branch at mouth at Branch Beaver

e S

e s

e r C

n n

i e

d M

n I E

a Bullskin Creek near mouth near Creek Bullskin

mouth

e r

Indian Creek and tributaries d

e r C

Spring at MoArk site 13 site MoArk at Spring

k i

e W

r e

n I a

k h t

e u

e o

r C Elkhorn m

r C

i e

n I

e a

l h l e t

e t

r C

o N n Sears Spring near Wanda near Spring Sears

below Stella below

S t

a k

d k

n I

r C

mouth t

h t

r C

o i

o k

d a

e S i

n I

o H

s r C

h t n I

h t a

u g a

S k

u o k

S e

S t

r C

l t t

Highway 90 Highway t k

L e

a u

k o

r C

e s

i r

w M

l u

o H

r C Miser

n l t t

Missouri Road Missouri t

L a

r k

o e k

e e G

r C

at Caverna at

k r C

e d

g r e e

Little Sugar Creek and tributaries u a e

S r C

. r C e

l t t

r g

T w

y A ,

S o

a t

e a

l t t

k L

a e

l e

T above at mouth at r C

k k

B w a

e e

o g

e e

e o H

r C

g r C

o r

o D

g l t t

u u

S S

r C

e r g

l t t

B i g

L o H u

i e

o H Dog above b l t t

m w

e l

at Cyclone at

r C

a H w

o H

e s

r C

S k

g e

a H

e e

v e w

near mouth near S o

o r C

k r g b

P e

r w

e g

a k o

l u

e e

r C

e S

n s

k k

r C e e k

i s

e e

i r C

r C t r k

n M a

Big Sugar Creek and tributaries e

Total phosphorus Total e

g e

r u

r C t

T w

h t n

l u e

r o H Blackjack near e o

k m t

T at

a k

k r C

r e

r C

a e

k a

r C

r e g

r C t

a e u S

e i

at Mountain at

r C

k B

i T y

e s

g e i

. 7 . 6 . 5 . 4 . 3 . 2 . 1 a

0 0 0 0 0 0 0 e r

r C

a CONCENTRATION, IN MILLIGRAMS PER LITER LITER PER MILLIGRAMS IN CONCENTRATION,

G w

u o

l Concentration of total phosphorus in samples from the seepage run, July 31 through August 3, 2006, Upper Elk River Basi n.

S e

g i b

B e

r C

g i B Figure 20. 36 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

Table 5. Wastewater indicator compounds analyzed and reporting limit for samples collected during the seepage run, July 31–August 3, 2006, in the Upper Elk River Basin.

[µg/L, micrograms per liter; AHTN, acetyl hexamethyl tetrahydronaphthalene; DEET, N,N-diethyl-meta-toluamide; HHCB, hexahydrohexamethylcyclopentabenzopyran; bold-faced compounds were detected]

Reporting limit Reporting limit Compound (µg/L) Compound (µg/L) 1-Methylnaphthalene 0.2 Cholesterol 0.8 1,4-Dichlorobenzene .2 Cotinine .8 2-Methylnaphthalene .2 d-Limonene .2 2,6-Dimethylnaphthalene .2 DEET .2 2,2’,4,4’-Tetrabromodiphenyl ether .2 Diazinon .2 3-beta-Coprostanol .8 Dichlorvos .4 3-Methyl-1(H)-indole (Skatole) .2 Diethyl phthalate .2 3-t-butyl-4-hydroxy anisole (BHA) .2 Fluoranthene .2 3,4-Dichlorophenyl isocyanate 2 HHCB .2 4-Cumylphenol .2 Indole .2 4-n-Octylphenol .2 Isoborneol .2 4-Nonylphenol diethoxylates 3.2 Isophorone .2 4-Octylphenol diethoxylates .32 Isopropylbenzene .2 4-Octylphenol monoethoxylates 1 Isoquinoline .2 4-tert-Octylphenol .2 Menthol .2 5-Methyl-1H-benzotriazole 1.6 Metalaxyl .2 9,10-Anthraquinone .2 Methyl salicylate .2 Anthraquinone .2 Metolachlor .2 Acetophenone .2 Naphthalene .2 AHTN .2 Nonylphenol, monoethoxy- (total) 2 Anthracene .2 p-Cresol .2 Atrazine .2 para-Nonylphenol (total) 1.6 Benzo[a]pyrene .2 Phenanthrene .2 Benzophenone .2 Phenol .2 beta-Sitosterol .8 Pentachlorophenol .8 beta-Stigmastanol .8 Prometon .20 Bisphenol A .4 Pyrene .20 bis(2-Ethylhexyl) phthalate 2 Tetrachloroethylene .40 Bromacil .2 Tributyl phosphate .2 Bromoform .2 Triclosan .20 Caffeine .2 Triethyl citrate (ethyl citrate) .20 Camphor .2 Triphenyl phosphate .2 Carbaryl .2 Tris(dichlorisopropyl)phosphate .20 Carbazole .2 Tris(2-butoxyethyl)phosphate .2 Chlorpyrifos .2 Tris(2-chloroethyl)phosphate .2 Streambed-Sediment Quality 37

Discharge values measured during the second seepage

run, November 13–14, 2006 (table 7; fig. 18) generally had

increased from those measured in the first seepage run. The

.038 flow in Big Sugar Creek had more than doubled, had doubled <.024 <.024 <.024 <.024 (µg/L) oxazole <0.024

Sulfameth- in Little Sugar Creek, and had increased more than 30 percent

in the Elk River. Calcium concentrations in samples from the second

.003 seepage run ranged from 52.8 to 69.1 mg/L and were smallest <.022 <.022 <.022 <.022 (µg/L) <0.022 Diltiazem in samples from Big Sugar Creek and the Elk River. Sodium,

chloride, and sulfate concentrations were largest in samples from Little Sugar Creek and the Elk River (fig. 21), possibly

.040 indicating effects from effluent inflow into Little Sugar Creek <.018 <.018 <.018 <.018 epine (µg/L) <0.018

Carbamaz- and the Elk River.

E. coli densities were less than 85 col/100 mL in samples

from the second seepage run; therefore, the Missouri water-

.9 quality criteria for whole-body-contact recreation was not <.2 <.2 <.2 <.2 (µg/L) Tris(2- <0.2 exceeded, although the time of sample collection was after phosphate butoxyethyl) the recreational season. The maximum fecal coliform density

was 260 col/100 mL from Little Sugar Creek at Missouri Road

.4 (site JR01). <.2 <.2 <.2 <.2 (µg/L) <0.2

Diethyl Nitrate concentrations were less than 4.0 mg/L in all phthalate samples from the second seepage run (fig. 22). The largest

concentration was detected in a sample from North Indian <.2 <.2 <.2 <.2 E.2 <0.2 DEET (µg/L) Creek (site JS19), a tributary to Indian Creek. The concen-

tration in the sample from Indian Creek near Lanagan had

M decreased to less than 1.0 mg/L. Nitrate concentrations in <.2 <.2 <.2 <.2 <0.2 (µg/L) samples from Little Sugar Creek ranged from 0.88 (site JR82; Caffeine near the mouth) to 2.60 mg/L (site JR02; below Bella Vista);

these concentrations were larger than those detected in the

prior seepage run—0.102 (at the mouth) to 1.09 mg/L (below <2 <2 <2 <2 <2 E1

(µg/L) Bella Vista). The total phosphorus concentrations in samples hexyl) phthalate

Bis(2-ethyl- from Little Sugar Creek below Bella Vista decreased from

those detected in the first seepage run (0.670 mg/L) to 0.430

M mg/L in November 2006. <.2 <.2 <.2 <.2 <0.2 (µg/L) AHTN Seven pharmaceutical compounds were detected in samples from the second seepage run (table 7). Seven compounds were detected in the sample from Little Sugar Creek at Cav- Time 1815 0830 1620 1745 0820 0900 erna, three from Little Sugar Creek near Pineville (site JR82), two from the Elk River below Noel (site Bk24), and one from Indian Creek near Lanagan (site JR06). All of these sites are

Date located downstream from effluent inflow. No samples were 8/1/2006 8/1/2006 8/1/2006 8/2/2006 8/2/2006 8/3/2006 collected for analysis of wastewater indicator compounds, optical brighteners, chlorophyll a, and nitrogen isotopes.

Streambed-Sediment Quality

Site name Streambed-sediment samples were collected at 35 sites (table 8; fig. 23) throughout the Upper Elk River Basin in August 2005. Analytical and leaching results on individual Big Sugar Creek at mouth Big Sugar Creek at Caverna Little Sugar Creek at mouth Little Sugar Bullskin Creek near mouth Indian Creek at mouth City near Tiff Elk River streambed-sediment samples were grouped to facilitate spatial Concentrations of wastewater indicator and pharmaceutical compounds detected in samples from the seepage run, July 31–August 3, 2006, Upper Elk

and statistical analyses of the data. Data from the samples were grouped to represent the major forks of the Elk River Site (fig. 18)

identifier (Big and Little Sugar Creeks, Indian Creek, and the Elk River) BK15 JR34 JR04 JS28 JR27 JS29 Table 6. Table River Basin. µg/L, micrograms per liter; <, less than; E, estimated; M, HHCB,hexahydrohexamethylcyclopentabenzopyran; N,N-diethyl-meta-toluamide; DEET, tetrahydronaphthalene; [AHTN, acetyl hexamethyl not quantified] but presence verified, or tributaries of the major forks (Big Sugar Creek tributaries, 38 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

5.91 4.59 4.24 ; .048 20.1 17.9 16.9 16.8 12.5 13.2 <.021 <.021 <.021 <.021 <.021 <.021 <.021 (µg/L) (mg/L) 1,7-di- <0.021 Sulfate methyl- xanthine

.21 .15 .13 26 39 20 9K <.10 <.10 <.10 140 260 E.08 E.05 mL) 25K 15K 158K <0.10 Fecal (mg/L) (col/100 Fluoride coliform Escherichia coli Escherichia ,

E. coli 42 25 82 34 9K 2K 5.48 7.34 8.15 mL) 21K 18K 16K 21.5 18.7 16.4 15.1 17.4 19.8 (mg/L) E. coli (col/100 Chloride

.430 .340 .250 .104 .034 .016 .035 2.80 5.41 5.23 0.009 21.4 17.6 15.2 12.8 13.6 15.6 E.02 Total (mg/L) (mg/L) Sodium phosphorus

.337 .316 .244 .087 .029 .007 .018 .010 1.77 5.78 4.71 4.22 3.37 1.92 2.01 4.14 4.39 0.033 <.024 <.024 <.024 <.024 <.024 E.021 E.013 (µg/L) meth- Sulfa- (mg/L) (mg/L) E0.006 Ortho- <0.024 oxazole Potassium phosphorus

54.0 68.6 63.1 62.6 60.1 69.1 58.1 53.7 52.8 .015 .050 .007 .004 .002 Di- <.023 <.023 <.023 <.023 <.023 <.023 <.023 E.011 E.002 E.001 E.002 (µg/L) phen- <0.023 (mg/L) (mg/L) Nitrite <0.002 Calcium hydramine

.88 .82 .98 .93 8.3 7.7 7.5 7.7 7.6 7.8 8.0 8.3 8.1 pH 0.09 2.60 2.06 1.71 3.48 <.022 <.022 <.022 <.022 <.022 <.022 <.022 E.008 (µg/L) <0.022 (mg/L) nitrate Nitrite + Diltiazem

.043 .250 444 378 313 359 364 291 404 391 381 <.028 <.028 <.028 <.028 <.028 <.028 <.028 E.019 <.020 <.020 <.020 <.020 <.020 <.020 (µg/L) (mg/L) <0.028 <0.020 (µS/cm) Specific Cotinine Ammonia conductance

C) .47 .41 .14 .12 .52 .11 .14 o 13.6 15.4 12.2 13.4 11.9 13.1 14.5 13.7 12.8 ( <.10 <.018 <.018 <.018 <.018 <.018 <.018 E.032 E.011 (µg/L) <0.10 Water (mg/L) Carba- <0.018 mazepine organic N Ammonia + temperature

/s) -- -- 3 8.1 4.2 9.25 8.43 7.44 7.22 7.15 9.70 9.37 7.30 17 20 26 26 64 55 (ft <.200 <.200 <.200 <.200 E.157 E.012 E.021 E.008 (µg/L) Silica (mg/L) <0.200 Caffeine Discharge 1330 1440 1110 1230 0930 0950 1500 1610 0800 0950 1330 1500 1610 0800 1440 1110 1230 0930 0950 1330 1500 1610 0800 1440 1110 1230 0930 Time Time Time Date Date Date 11/14/2006 11/13/2006 11/13/2006 11/13/2006 11/14/2006 11/14/2006 11/14/2006 11/14/2006 11/14/2006 11/14/2006 11/13/2006 11/13/2006 11/13/2006 11/14/2006 11/14/2006 11/14/2006 11/14/2006 11/14/2006 11/14/2006 11/13/2006 11/13/2006 11/13/2006 11/14/2006 11/14/2006 11/14/2006 11/14/2006 11/14/2006 Site name Site name Site name Values of physical properties, major ion and nutrient concentrations, bacteria densities, wastewater indicator pharmaceutical compounds in samples Values Big Sugar Creek at mouth Big Sugar Ark. Bella Vista, Creek below Little Sugar Creek at Caverna Little Sugar Creek at Missouri Road Little Sugar Creek near Pineville Little Sugar North Indian Creek near Wanda Indian Creek near Lanagan Noel below Elk River City near Tiff Elk River Creek at mouth Big Sugar Ark. Bella Vista, Creek below Little Sugar Creek at Caverna Little Sugar Creek at Missouri Road Little Sugar Creek near Pineville Little Sugar North Indian Creek near Wanda Indian Creek near Lanagan Noel below Elk River City near Tiff Elk River Creek at mouth Big Sugar Ark. Bella Vista, Creek below Little Sugar Creek at Caverna Little Sugar Creek at Missouri Road Little Sugar Creek near Pineville Little Sugar North Indian Creek near Wanda Indian Creek near Lanagan Noel below Elk River City near Tiff Elk River

Site Site Site /sec, cubic feet per second; ºC, degrees Celsius; µS/cm, microsiemens per centimeter at 25 degrees Celsius; mg/L, milligrams per liter; <, less than, --, no data; N, nitrogen; Celsius; µS/cm, microsiemens per centimeter at 25 degrees /sec, cubic feet per second; ºC, degrees 3 (fig. 18) (fig. 18) (fig. 18) identifier identifier identifier BK15 JR02 JR34 JR01 JR82 JS19 JR06 BK24 JS29 BK15 JR02 JR34 JR01 JR82 JS19 JR06 BK24 JS29 BK15 JR02 JR34 JR01 JR82 JS19 JR06 BK24 JS29 Table 7. Table from the seepage run, November 2006, in Upper Elk River Basin. [ft col/100 mL, colonies per 100 milliliters; µg/L, micrograms liter; E, estimated; K, count outside acceptable range] Streambed-Sediment Quality 39

20 EXPLANATION

15 Sodium

Chloride 10 Sulfate

CONCENTRATION, IN MILLIGRAMS PER LITER CONCENTRATION, 0 Big Sugar Bella Caverna Missouri Pineville North Indian Noel Tiff City Creek Vista Road Indian Creek at mouth Creek near near Little Sugar Creek Wanda Lanagan Elk River

Figure 21. Sodium, chloride, and sulfate concentrations in samples from the seepage run, November 2006, in the Upper Elk River Basin.

Little Sugar Creek tributaries, Indian Creek tributaries, and the statistical analysis. The reporting limit was used for concentra- Elk River tributaries). tions with “less than” values. Concentrations of trace elements and other constituents Concentrations of one or more nutrients were detected in sediments often are normalized to improve the sensitiv- in all sediment leachate samples (table 8). The most fre- ity of methods used to examine trends or patterns in the data quently detected and at the largest concentrations was dis- (Horowitz, 1985; Luoma, 1990; Daskalakis and O’Connor, solved ammonia plus organic nitrogen as nitrogen (hereinafter 1995). Normalization to grain-size or organic carbon content referred to as ammonia plus organic nitrogen), which was are two of the more commonly used factors, in addition to detected in all leachate samples at concentrations ranging aluminum and iron content (Daskalakis and O’Connor, 1995). from 0.80 to 15.0 mg/L. Smaller concentrations of dissolved A Pearson pairwise correlation matrix between four factors ammonia as nitrogen (hereinafter referred to as ammonia) (grain-size, organic carbon, aluminum, and iron content) in were detected in all leachate samples at concentrations rang- streambed-sediment samples and nutrient concentrations in ing from 0.02 to 2.23 mg/L. All leachate samples contained the leachate samples indicated that organic carbon content was detectable concentrations of dissolved phosphorus and dis- most highly correlated with nutrient concentrations (table 8). solved orthophosphorus at concentrations ranging from 0.08 Therefore, nutrient concentrations in leachate samples were to 1.58 mg/L and 0.02 to 1.19 mg/L (table 8). In contrast, only normalized to sediment organic carbon content using the fol- 16 leachate samples contained detectable concentrations of lowing relations: dissolved nitrite plus nitrate as nitrogen (hereinafter referred to as nitrate) at concentrations ranging from 0.03 mg/L to 0.17

Cadj = Cleachate * (100/percent organic carbon content) Step 1 (2) mg/L. Concentrations of dissolved nitrite were detected in only nine samples at concentrations equal to or less than 0.017 mg/L.

Cscaled = Cadj / (maximum Cadj calculated in all samples) Step 2 (3) To minimize variance caused by differences in sediment grain-size or other factors, statistical analysis of the leaching where Cadj is the nutrient concentration in the leaching data was done using normalized (to sediment organic carbon experiment adjusted for organic carbon content) and scaled values. Concentrations of leachable nutri- content; ents normalized to organic carbon content generally tended to

Cleachate is the initial nutrient concentration in the be slightly larger along the major forks of the Elk River com- leachate solution; and pared to tributary sites, with sites in the upper reaches of the

Cscaled is the final leachate concentration normalized major forks having among the largest concentrations (fig. 23). to the maximum value reported for each Normalized concentrations of leachable nutrients in the major constituent in all samples. forks generally decreased with increasing distance down- Normalization concentrations for each individual nutrient stream. The largest normalized leachable nutrients concentra- were then scaled by dividing by the largest Cadj value calcu- tions were from sites along Big Sugar Creek (sites 29 and 35), lated for all samples. This resulted in normalized nutrient Little Sugar Creek (site 5) or Elk River (site 11A). Big Sugar concentrations ranging from 0 to 1.0 that were then used in the Creek near Cyclone (site 29) had the largest normalized leach- 40 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

4 Nitrate as nitrogen

2 LITER

R 1 E P

S M A R G I L

L 0 I M

I 0.5

N Total phosphorus O I T A R

T 0.4 N E C N O C 0.3

0.2

0.1

0 Big Sugar Bella Caverna Missouri Pineville North Indian Noel Tiff City Creek Vista Road Indian Creek at mouth Creek near near Little Sugar Creek Wanda Lanagan Elk River

Figure 22. Nutrient concentrations in samples from the seepage run, November 2006, in the Upper Elk River Basin. able phosphorus and ammonia plus organic nitrogen and the Whereas concentrations of leachable ammonia plus second largest normalized leachable orthophosphorus concen- organic nitrogen and ammonia in the three major forks of the trations (table 8). Little Sugar Creek near Bella Vista (site 5) had Elk River were similar, concentrations of phosphorus and the largest normalized leachable orthophosphorus and second orthophosphorus tended to be larger in Little Sugar Creek largest normalized leachable phosphorus concentrations. The than in the other two major forks (fig. 23). Results of Tukey’s largest normalized leachable ammonia concentration detected pairwise comparison using only data from the three major was from the Elk River near Noel (site 11A). An overall ranking forks of Elk River (Big Sugar Creek, Little Sugar Creek, of sites based on summing the normalized leachable nutrient and Indian Creek) indicated that leachable orthophosphorus concentrations (ammonia plus organic nitrogen, ammonia, phos- concentrations in Little Sugar Creek were significantly larger phorus, and orthophosphorus) indicated that the largest leach- than in Indian Creek (p=0.03), but not significantly larger than able nutrient concentrations were from Big Sugar Creek near concentrations in Big Sugar Creek (p=0.12). Cyclone (site 29), Little Sugar Creek near Bella Vista (site 5), Normalized concentrations of phosphorus and orthophos- and the Elk River near Noel (site 11A). phorus in tributaries to Little Sugar Creek were significantly No significant difference in leachable nutrient concentra- smaller than those from the main stem of Little Sugar Creek tions normalized to organic carbon between the sample groups (p-values of 0.04 and 0.03). No significant differences were (fig. 24) was indicated. The p-values using Tukey’s multiple detected between main stem and tributary sites along Big comparison test were greater than 0.13 for all nutrients, except Sugar Creek, Indian Creek, or the Elk River. The largest nor- for normalized orthophosphorus concentrations, which was malized leachable nutrient concentrations detected in tributary marginally significant at the 10 percent level with a p-value of sites were at site 23A (South Indian Creek near Boulder City) 0.10. The p-value is the probability of erroneously reporting followed by site 1A on Bear Creek near Caverna (tributary a difference when no difference actually exits. Results were of Little Sugar Creek) and site 36 on Otter Creek near Jacket considered significant if p-values were less than 0.10. (tributary of Big Sugar Creek). Streambed-Sediment Quality 41

Dissolved ammonia plus organic nitrogen Dissolved ammonia

21 21 22 22 23A 23A Creek Creek 17 17 19 19 16 18 16 18

Elk 15 Elk 15 Indian Indian Ri 28 Rive ar 28 ver 13 Sugar r 13 Sug 24A 39 24A 14 39 Big 14 Big 34 29 34 29 10 30 10 30 25 9A 33 25 9A 33 8 8 7 26 7 26 11A 11A 37 37 4 27A 4 27A 37A 37A 3 eek 3 reek 35 Cr 35 C 2 1A 2 1A 36 36 6 6

5 5 Su Sugar Creek gar Creek Little Little

Concentration, in milligrams per liter Concentration, in milligrams per liter 0.062 to .0182 0.463 to 0.609 0.015 to 0.211 0.421 to 0.565 0.183 to 0.382 0.610 to 1.000 0.212 to 0.250 0.566 to 1.000 0.383 to 0.462 0.251 to .0420

Dissolved phosphorus Dissolved orthophosphorus

21 21 22 22 23A 23A Creek Creek 17 17 19 19 16 18 16 18

Elk 15 Indian Elk 15 Indian Ri 28 Ri 28 ver 13 Sugar ver 13 Sugar 24A 14 39 Big 24A 14 39 Big 29 34 29 34 10 30 10 30 9A 33 25 9A 33 25 8 7 26 8 7 26 11A 37 11A 37 4 27A 4 27A 37A 37A 3 eek 3 eek 35 Cr 35 Cr 2 1A 2 1A 36 36 6 6

5 5 Sugar Creek Sugar Creek Little Little

Concentration, in milligrams per liter Concentration, in milligrams per liter 0.277 to 0.451 0.094 to 0.214 0.394 to 0.510 0.035 to 0.080 EXPLANATION 0.081 to 0.175 0.215 to 0.289 0.511 to 1.000 0.452 to 1.000 0.290 to 0.393 0.176 to 0.276 9A Identifier (table 8) Tributary site Mainstem site NOTE: Concentrations scaled to maximum value

Figure 23. Concentrations of leachable nutrients normalized to organic carbon content in strambed-sediment samples, in the Upper Elk River Basin, August 2005. 42 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06 4 - .33 .62 .30 .08 .43 .41 .25 .22 .51 .15 .04 .23 .22 .08 .06 .24 .08 .15 .46 .06 .09 .03 .28 .04 .70 .18 .49 .16 .66 .45 .41 .12 .18 0.08 1.00 PO (mg/L) .32 .51 .31 .82 .21 .55 .39 .21 .29 .62 .31 .14 .25 .43 .17 .19 .47 .26 .32 .62 .21 .26 .20 .29 .09 .23 .52 .31 .76 .50 .41 .23 .43 P 0.43 1.00 (mg/L) 3 2 .07 .07 .12 .04 .07 .30 .30 .06 .06 .06 .12 .34 .18 .08 .10 .40 .12 .15 .08 .10 .06 .08 .09 .06 .31 .07 .32 .31 .07 .09 .07 .12 .11 0.10 1.00 NO (mg/L) , dissolved ammonia as , dissolved 3 3 .21 .23 .60 .64 .31 .45 .19 .15 .53 .65 .25 .07 .45 .10 .10 .54 .42 .57 .88 .25 .54 .36 .32 .02 .82 .16 .25 .38 .85 .39 .33 .23 .22 0.47 1.00 NH (mg/L) Normalized to organic carbon .28 .45 .44 .50 .40 .71 .13 .18 .46 .61 .29 .12 .06 .66 .14 .23 .58 .43 .53 .43 .40 .73 .70 .48 .08 .27 .23 .53 .79 .51 .20 .16 .38 0.90 1.00 +org N 3 (mg/L) NH 4 .230 .500 .130 .060 .360 .220 .200 .190 .460 .070 .040 .240 .140 .040 .030 .180 .060 .100 .250 .060 .060 .020 .240 .020 .520 .060 .200 .120 .390 .360 .310 .100 .050 0.04 1.19 PO (mg/L) , chromium; Cs, cesium; Cu, copper; Fe, iron; Ga, gallium; , chromium; Cs, cesium; Cu, copper; Fe, iron; Ga, gallium; .360 .660 .220 .260 .750 .340 .280 .410 .890 .230 .210 .410 .440 .136 .163 .580 .300 .350 .540 .330 .280 .190 .410 .080 .126 .340 .390 .720 .640 .500 .300 .190 P 0.36 1.58 1.20 (mg/L) 2 .006 .005 .017 .009 .004 .004 .004 .005 0.004 <.004 <.004 <.004 <.004 <.004 <.004 <.004 <.004 <.004 <.004 <.004 <.004 <.004 <.004 <.004 <.004 <.004 <.004 <.004 <.004 <.004 <.004 <.004 <.004 <.004 <.004 NO (mg/L) 3 2 .140 .090 .030 .170 .100 .120 .050 .060 .030 .030 .090 .060 .070 .029 .050 .150 <.029 <.029 <.029 <.029 <.029 <.029 <.029 <.029 <.029 <.029 <.029 <.029 <.029 <.029 <.029 <.029 <.029 <.029 , dissolved orthophosphorus as phosphorus; mg/L, milligrams per liter; mg/kg, mil , dissolved NO 4 <0.029 (mg/L) 3 .37 .46 .66 .58 .95 .26 .30 .75 .56 .17 .71 .12 .14 .74 .94 .61 .89 .51 .70 .02 .14 .25 .73 .77 .62 .47 .15 0.61 1.90 1.17 2.23 1.02 1.18 1.52 1.24 NH +org N, dissolved ammonia plus organic nitrogen as nitrogen; NH ammonia plus organic N, dissolved +org 3 (mg/L) .80 9.4 4.0 7.2 3.9 6.1 1.4 3.0 8.2 2.7 2.1 1.3 8.4 1.4 2.5 8.8 6.1 7.2 4.7 7.9 9.7 8.1 8.4 1.9 1.9 8.2 9.4 8.2 3.1 2.7 2.1 12.0 12.0 11.0 15.0 +org N 3 (mg/L) NH UTM Y 4040529 4040533 4043162 4044043 4032446 4037319 4047307 4049394 4048907 4051191 4046389 4054870 4056487 4056921 4062542 4065461 4064906 4065799 4072421 4072928 4071746 4053909 4049014 4047989 4044717 4055111 4053013 4050154 4052624 4052710 4040326 4040111 4045714 4045272 4053011 387587 384534 384739 385113 389709 387683 383207 377140 369084 370325 365912 358142 370663 371024 377044 378551 382279 382858 389106 390734 390619 394338 398189 398092 399219 393219 387719 376730 394338 394286 400721 400726 367909 366702 379070 UTM X 1440 1650 1620 1540 1145 1230 1500 1330 1215 1045 1040 0840 1345 1420 1530 1545 1615 1635 0830 0920 0945 1615 0905 0940 1005 1550 1500 1400 1655 1700 1115 1100 1150 1110 1415 Time , dissolved nitrite as nitrogen; P, dissolved phosphorus; PO dissolved nitrite as nitrogen; P, , dissolved 2 Date 8/30/2005 8/29/2005 8/29/2005 8/29/2005 8/30/2005 8/30/2005 8/29/2005 8/29/2005 8/30/2005 8/30/2005 8/30/2005 8/30/2005 8/29/2005 8/29/2005 8/29/2005 8/29/2005 8/29/2005 8/29/2005 8/30/2005 8/30/2005 8/30/2005 8/29/2005 8/30/2005 8/30/2005 8/30/2005 8/29/2005 8/29/2005 8/29/2005 8/29/2005 8/29/2005 8/30/2005 8/30/2005 8/30/2005 8/30/2005 8/29/2005 Site Name , dissolved nitrite plus nitrate as nitrogen; NO , dissolved 3 2 Bear Creek near Caverna Unnamed creek at Gordon Hollow Jane Creek above Little Sugar Missouri Creek near Jane Ark. Creek near Bella Vista, Little Sugar Ark. Creek near Bella Vista, Tanyard Jane Creek below Little Sugar Creek near Pineville Little Sugar near Mt Shira Elk River Indian Creek near Lanagan near Noel Elk River City near Tiff Elk River Indian Creek near Anderson Br near Anderson Beaver Hollow Rocky Indian Creek below Bullskin Creek near Erie Elkhorn Creek near McNatt Indian Creek near McNatt Indian Creek at Boulder City North Indian Creek near Boulder City South Indian Creek near Boulder City Creek near Powell Mikes Hollow Woodard Creek below Trent Pine Creek Creek below Big Sugar Mountain Creek below Big Sugar Unnamed creek at Kings Valley Creek near Cyclone Big Sugar Creek near Pineville Big Sugar Hollow Unnamed creek at Bentonville Creek near Powell Big Sugar Creek near Jacket Big Sugar Otter Creek near Jacket Mill Creek near Noel Butler Creek near Noel Access Creek at Deep Ford Big Sugar Nutrient and trace-element concentrations from streambed-sediment samples collected the Upper Elk River Basin, August 2005 .

(fig. 23) Identifier 1A 2 3 4 5 6 7 8 9A 10 11A 13 14 15 16 17 18 19 21 22 23A 24A 25 26 27A 28 29 30 33 34 35 36 37A 37 39 Table 8. Table Mecator; Ark., Arkansas; nutrient concentrations are from leachate samples; NH Transverse [UTM, Universal nitrogen; NO ligrams per kilogram; <, less than; Al, aluminum; Ba, barium; Be, beryllium; Bi, bismuth; Ca, calcium; Cd, cadmium; Ce, cerium; Co, cobalt; Cr Sc, scandium; Sr, phosphorus; Pb, lead; Rb, rubidium; Sb, antimony; P, Mo, molybdenum; Na, sodium; Nb, niobium; Ni, nickel; K, potassium; La, lanthanum; Li, lithium; Mg, magnesium; Mn, manganese; yttrium; Zn, zinc] Y, vanadium; titanium; Tl, thallium; U, uranium; V, tantalum; Th, thorium; Ti, strontium; Ta, Streambed-Sediment Quality 43 - 8.9 4.1 6.4 8.3 9.7 7.9 7.4 9.3 6.8 7 9.6 8.5 8.8 9.7 8.7 9.4 9.2 7.2 7.2 5.1 7.8 9.2 9.6 7.5 11 11 18 11 10 15 12 16 10 12 10 Ga (mg/kg) Fe 8,400 17,000 27,000 13,000 25,000 18,000 19,000 42,000 24,000 34,000 16,000 18,000 19,000 19,000 24,000 19,000 19,000 19,000 30,000 26,000 22,000 20,000 30,000 13,000 21,000 25,000 31,000 32,000 18,000 18,000 24,000 23,000 26,000 16,000 19,000 (mg/kg) 15.8 10.9 22 14.5 22.5 15.4 18.3 32 47.2 22.4 17 17.7 19.8 23.2 14.9 13.4 19.8 14.3 14.1 16 13 17.9 26.5 13.2 13.6 18.7 19.9 26.5 17.2 19.7 14.6 17.2 21.6 16.3 15.5 Cu , dissolved ammonia as , dissolved (mg/kg) 3 3.8 1.6 4.5 2.2 4.1 3.1 3.9 8.6 4.7 3.2 3.0 3.8 2.4 2.6 3.3 3.0 3.6 3.1 2.9 2.7 3.1 3.7 7.2 2.7 2.5 4.7 2.0 7.5 3.8 3.0 3.2 3.3 4.9 2.8 4.1 Cs (mg/kg) Cr 60.2 28.3 73.7 36.7 66.0 46.4 55.5 94.8 64.1 45.6 42.4 48.4 47.6 60.8 64.3 45.2 63.8 52.2 66.3 59.3 59.2 44.5 70.6 46.6 55.8 59.2 27.2 76.1 48.8 41.9 66.5 64.4 56.0 36.0 46.2 (mg/kg) 6.1 8.4 8.2 14.3 20.4 22.3 13.1 13.0 24.6 19.6 15.6 13.7 11.4 14.7 14.1 19.4 12.7 12.1 15.6 23.0 21.9 14.6 18.4 25.6 10.3 15.2 23.7 18.9 11.4 12.1 16.3 15.5 16.1 12.5 13.5 Co (mg/kg) , chromium; Cs, cesium; Cu, copper; Fe, iron; Ga, gallium; , chromium; Cs, cesium; Cu, copper; Fe, iron; Ga, gallium; 67.4 29.6 67.6 49.1 85.0 60.6 73.1 94.5 71.4 51.3 56.6 77.9 61.1 58.2 75.3 78.3 82.7 86.0 93.7 88.2 73.7 62.1 79.0 71.4 51.3 90.0 34.4 73.7 77.5 52.0 70.4 71.9 68.8 52.5 68.0 Ce (mg/kg) .46 .66 .22 .83 .58 .50 .78 .54 .47 .79 .78 .74 .47 .40 .79 .98 .73 .56 .44 .90 .61 .56 .40 1.00 1.40 1.20 1.10 1.50 2.60 1.90 2.00 2.40 1.10 1.00 Cd 12.2 (mg/kg) , dissolved orthophosphorus as phosphorus; mg/L, milligrams per liter; mg/kg, mil , dissolved 4 Ca 7,000 6,630 4,090 4,110 4,730 6,340 73,100 22,000 78,000 45,700 25,100 14,700 66,400 13,300 86,900 23,900 26,900 16,200 78,400 11,800 37,800 29,900 42,000 21,100 88,600 15,300 29,200 29,000 29,500 30,600 10,800 187,000 116,000 101,000 181,000 (mg/kg) +org N, dissolved ammonia plus organic nitrogen as nitrogen; NH ammonia plus organic N, dissolved +org 3 .04 .20 .07 .28 .12 .15 .27 .17 .24 .10 .14 .15 .16 .15 .12 .15 .12 .21 .18 .19 .18 .25 .14 .16 .24 .10 .28 .18 .15 .18 .19 .24 .16 .18 0.14 Bi (mg/kg) .65 .84 1.5 2.0 1.0 1.7 1.2 1.5 3.2 2.0 1.4 1.2 1.5 1.2 1.2 1.5 1.2 1.8 1.4 1.8 1.6 1.4 1.4 2.7 1.3 1.2 1.9 2.9 1.6 1.3 1.7 1.7 2.0 1.2 1.6 Be (mg/kg) Ba 291 180 380 292 552 376 368 562 384 372 363 431 374 268 342 382 365 463 357 474 338 349 462 343 313 395 243 467 381 300 320 364 373 289 368 (mg/kg) 5.5 3.0 8.5 4.0 8.4 7.4 4.8 7.1 5.1 4.5 4.8 6.8 6.0 5.3 3.8 4.0 7.6 5.9 6.6 4.1 6.8 8.4 6.4 9.0 8.2 7.8 9.8 5.0 6.0 16 22 10 12 20 12 As (mg/kg) Al 42,000 19,400 51,800 32,700 51,900 41,600 48,300 84,900 53,600 35,100 34,600 47,700 32,500 33,300 44,700 42,800 51,000 40,900 37,000 34,500 39,400 38,900 64,000 31,000 28,800 50,100 20,000 67,000 41,600 33,100 36,600 37,600 49,700 31,800 41,500 (mg/kg) , dissolved nitrite as nitrogen; P, dissolved phosphorus; PO dissolved nitrite as nitrogen; P, , dissolved 2 Date 8/30/2005 8/29/2005 8/29/2005 8/29/2005 8/30/2005 8/30/2005 8/29/2005 8/29/2005 8/30/2005 8/30/2005 8/30/2005 8/30/2005 8/29/2005 8/29/2005 8/29/2005 8/29/2005 8/29/2005 8/29/2005 8/30/2005 8/30/2005 8/30/2005 8/29/2005 8/30/2005 8/30/2005 8/30/2005 8/29/2005 8/29/2005 8/29/2005 8/29/2005 8/29/2005 8/30/2005 8/30/2005 8/30/2005 8/30/2005 8/29/2005 Site Name , dissolved nitrite plus nitrate as nitrogen; NO , dissolved 3 2 Bear Creek near Caverna Unnamed creek at Gordon Hollow Jane Creek above Little Sugar Missouri Creek near Jane Ark. Creek near Bella Vista, Little Sugar Ark. Creek near Bella Vista, Tanyard Jane Creek below Little Sugar Creek near Pineville Little Sugar near Mt Shira Elk River Indian Creek near Lanagan near Noel Elk River City near Tiff Elk River Indian Creek near Anderson Br near Anderson Beaver Hollow Rocky Indian Creek below Bullskin Creek near Erie Elkhorn Creek near McNatt Indian Creek near McNatt Indian Creek at Boulder City North Indian Creek near Boulder City South Indian Creek near Boulder City Creek near Powell Mikes Hollow Woodard Creek below Trent Pine Creek Creek below Big Sugar Mountain Creek below Big Sugar Unnamed creek at Kings Valley Creek near Cyclone Big Sugar Creek near Pineville Big Sugar Hollow Unnamed creek at Bentonville Creek near Powell Big Sugar Creek near Jacket Big Sugar Otter Creek near Jacket Mill Creek near Noel Butler Creek near Noel Access Creek at Deep Ford Big Sugar Nutrient and trace-element concentrations from streambed-sediment samples collected the Upper Elk River Basin, August 2005 .—Continued

(fig. 23) Identifier 1A 2 3 4 5 6 7 8 9A 10 11A 13 14 15 16 17 18 19 21 22 23A 24A 25 26 27A 28 29 30 33 34 35 36 37A 37 39 Table 8. Table Mecator; Ark., Arkansas; nutrient concentrations are from leachate samples; NH Transverse [UTM, Universal nitrogen; NO ligrams per kilogram; <, less than; Al, aluminum; Ba, barium; Be, beryllium; Bi, bismuth; Ca, calcium; Cd, cadmium; Ce, cerium; Co, cobalt; Cr Sc, scandium; Sr, phosphorus; Pb, lead; Rb, rubidium; Sb, antimony; P, Mo, molybdenum; Na, sodium; Nb, niobium; Ni, nickel; K, potassium; La, lanthanum; Li, lithium; Mg, magnesium; Mn, manganese; yttrium; Zn, zinc] Y, vanadium; titanium; Tl, thallium; U, uranium; V, tantalum; Th, thorium; Ti, strontium; Ta, 44 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06 - 8.3 3.6 9.0 4.8 8.9 7.2 8.3 9.7 6.3 6.2 8.2 5.5 5.7 6.9 6.8 8.3 6.9 5.8 5.5 6.4 7.6 5.5 4.9 9.5 3.8 8.2 5.9 6.1 6.4 9.7 5.8 8.4 Sc 16.6 12.8 13.4 (mg/kg) .30 .84 .37 .56 .55 .65 .71 .51 .62 .62 .68 .48 .48 .46 .36 .82 .72 .70 .62 .86 .42 .51 .68 .64 .56 .69 .74 .95 .61 .56 0.54 1.20 1.20 1.30 1.00 Sb (mg/kg) Rb 61.2 28.3 77.7 46.0 69.0 54.2 69.9 81.5 55.3 54.0 71.0 42.8 41.8 54.8 56.0 60.5 57.1 50.7 50.9 53.9 61.4 55.0 42.8 79.6 37.0 74.4 55.5 54.8 60.0 90.5 57.6 73.2 154 120 127 , dissolved ammonia as , dissolved (mg/kg) 3 Pb 20.7 14.9 31.8 16.8 30.3 21.5 23.4 51.8 33.1 34.4 87.7 86.6 85.4 30.8 20.8 26.4 26.4 55.8 50.8 27.8 23.8 34.1 19.0 28.0 37.6 20.4 29.2 22.3 31.0 27.4 26.4 32.4 25.4 20.2 853 (mg/kg) 500 510 370 800 860 980 950 550 800 840 810 410 540 690 800 700 550 620 560 330 850 580 580 520 550 530 800 840 600 560 420 P 1,200 2,500 1,100 1,200 (mg/kg) 44 20 53.7 17.7 33.5 40.2 28.9 42 49.5 38.6 26.1 25.6 34.8 34.2 29.4 19.2 24.6 21.9 28.3 27.1 21.5 43.2 50.4 18.1 27.5 50.9 20.5 40.9 27.3 26.2 26.3 25.8 39.5 25.9 30.9 Ni (mg/kg) , chromium; Cs, cesium; Cu, copper; Fe, iron; Ga, gallium; , chromium; Cs, cesium; Cu, copper; Fe, iron; Ga, gallium; 8.2 4.8 3.8 9.7 7.7 8.6 8.8 8.0 5.3 7.7 4.9 4.8 9.6 5.7 5.0 9.0 6.4 7.3 8.5 12 10 15 10 11 10 13 14 14 15 15 10 12 14 11 15 Nb (mg/kg) 752 773 960 825 Na 1,690 1,510 1,950 1,640 1,570 1,990 1,460 1,310 1,080 1,500 2,670 1,230 1,030 1,180 2,330 1,880 1,980 1,150 1,610 1,500 1,020 1,450 1,940 1,340 2,130 1,450 1,140 1,460 1,370 1,620 1,820 (mg/kg) , dissolved orthophosphorus as phosphorus; mg/L, milligrams per liter; mg/kg, mil , dissolved .94 .50 .59 .69 .30 .32 .25 .20 .96 .88 .76 .76 .81 .92 4 1.5 4 1 1.7 1 1.3 4.1 2.2 4.6 1 1.6 4.1 1.3 1.7 4.8 3.1 1.1 1.3 3.2 1.6 1.1 Mo (mg/kg) +org N, dissolved ammonia plus organic nitrogen as nitrogen; NH ammonia plus organic N, dissolved +org 3 819 707 625 718 822 879 732 988 647 425 601 473 Mn 2,340 5,970 3,430 2,690 2,050 2,250 2,660 1,980 1,530 1,690 1,030 2,750 2,080 2,720 1,320 2,250 1,790 2,500 1,230 1,070 1,340 1,010 1,060 (mg/kg) Mg 5,540 7,150 9,960 3,100 7,760 6,050 4,590 4,120 3,360 2,500 3,140 2,560 2,240 2,960 2,460 1,960 1,850 1,960 4,980 7,520 2,120 2,890 3,870 2,640 8,430 3,140 9,840 1,970 2,010 4,940 5,220 3,400 53,800 40,300 11,300 (mg/kg) Li 24.8 11.5 25.9 17.6 27.2 22.8 26.4 28.1 25 17.3 18.7 25.7 19.5 19.5 26.8 23.4 27.5 24.2 23.4 21.9 24.8 24.1 30.8 20.6 18.2 32.2 12.1 28.4 25.9 20.5 26.1 25.5 28.3 18.7 26.3 (mg/kg) La 40.3 17.7 37.6 25.1 48.2 39.1 40.7 49.3 39 29.8 33.3 43.9 35.3 36.6 44.1 41.8 48.1 46.6 39.8 39.8 37.7 39.6 43.6 40.6 31.8 50.2 22.7 46.7 45.5 31.7 39.8 40.1 39.4 31.1 40.4 (mg/kg) K 6,280 7,140 7,090 8,090 9,780 6,750 7,690 8,020 6,710 6,490 7,600 8,640 11,500 16,900 14,400 13,700 10,400 14,700 37,700 18,500 11,800 11,200 15,100 10,800 10,000 10,700 25,000 10,300 13,200 26,800 13,500 11,400 16,900 11,600 13,100 (mg/kg) , dissolved nitrite as nitrogen; P, dissolved phosphorus; PO dissolved nitrite as nitrogen; P, , dissolved 2 Date 8/30/2005 8/29/2005 8/29/2005 8/29/2005 8/30/2005 8/30/2005 8/29/2005 8/29/2005 8/30/2005 8/30/2005 8/30/2005 8/30/2005 8/29/2005 8/29/2005 8/29/2005 8/29/2005 8/29/2005 8/29/2005 8/30/2005 8/30/2005 8/30/2005 8/29/2005 8/30/2005 8/30/2005 8/30/2005 8/29/2005 8/29/2005 8/29/2005 8/29/2005 8/29/2005 8/30/2005 8/30/2005 8/30/2005 8/30/2005 8/29/2005 Site Name , dissolved nitrite plus nitrate as nitrogen; NO , dissolved 3 2 Bear Creek near Caverna Unnamed creek at Gordon Hollow Jane Creek above Little Sugar Missouri Creek near Jane Ark. Creek near Bella Vista, Little Sugar Ark. Creek near Bella Vista, Tanyard Jane Creek below Little Sugar Creek near Pineville Little Sugar near Mt Shira Elk River Indian Creek near Lanagan near Noel Elk River City near Tiff Elk River Indian Creek near Anderson Br near Anderson Beaver Hollow Rocky Indian Creek below Bullskin Creek near Erie Elkhorn Creek near McNatt Indian Creek near McNatt Indian Creek at Boulder City North Indian Creek near Boulder City South Indian Creek near Boulder City Creek near Powell Mikes Hollow Woodard Creek below Trent Pine Creek Creek below Big Sugar Mountain Creek below Big Sugar Unnamed creek at Kings Valley Creek near Cyclone Big Sugar Creek near Pineville Big Sugar Hollow Unnamed creek at Bentonville Creek near Powell Big Sugar Creek near Jacket Big Sugar Otter Creek near Jacket Mill Creek near Noel Butler Creek near Noel Access Creek at Deep Ford Big Sugar Nutrient and trace-element concentrations from streambed-sediment samples collected the Upper Elk River Basin, August 2005 .—Continued

(fig. 23) Identifier 1A 2 3 4 5 6 7 8 9A 10 11A 13 14 15 16 17 18 19 21 22 23A 24A 25 26 27A 28 29 30 33 34 35 36 37A 37 39 Table 8. Table Mecator; Ark., Arkansas; nutrient concentrations are from leachate samples; NH Transverse [UTM, Universal nitrogen; NO ligrams per kilogram; <, less than; Al, aluminum; Ba, barium; Be, beryllium; Bi, bismuth; Ca, calcium; Cd, cadmium; Ce, cerium; Co, cobalt; Cr Sc, scandium; Sr, phosphorus; Pb, lead; Rb, rubidium; Sb, antimony; P, Mo, molybdenum; Na, sodium; Nb, niobium; Ni, nickel; K, potassium; La, lanthanum; Li, lithium; Mg, magnesium; Mn, manganese; yttrium; Zn, zinc] Y, vanadium; titanium; Tl, thallium; U, uranium; V, tantalum; Th, thorium; Ti, strontium; Ta, Streambed-Sediment Quality 45 54.1 45.2 91.3 98.1 76.7 89.6 89.8 54.8 99.8 97.6 89.3 86.0 95.0 72.9 Zn 105 114 176 101 300 138 152 262 208 488 200 116 196 309 658 113 109 199 118 117 114 (mg/kg) Y 40.6 16.2 31.9 14.5 48.2 36.5 32.0 33.1 29.8 25.1 26.5 35.0 29.4 36.4 34.1 30.6 46.5 33.4 31.3 32.7 30.4 39.8 33.8 33.5 30.6 45.4 21.6 36.7 44.2 27.5 39.2 38.6 34.6 25.6 38.2 (mg/kg) V 63.5 27.4 82.8 43.5 68.9 59.3 64.4 83.6 58.2 50.2 64.9 48.2 53.0 62.4 58.9 61.9 56.1 74.6 66.3 62.7 64.2 49.4 51.6 86.4 35.4 64.3 53.7 64.5 65.6 89.8 50.7 65.3 153 108 124 (mg/kg) U 2.2 1.2 2.8 2.1 2.4 2.2 2.5 5.5 3.0 2.0 2.0 2.5 1.4 1.8 1.6 2.4 2.2 2.0 1.8 2.0 2.1 2.2 3.5 2.5 1.5 2.6 1.4 4.8 2.9 2.2 1.9 2.3 3.4 2.6 2.5 (mg/kg) +org N, dissolved ammonia plus organic ammonia plus organic N, dissolved +org , dissolved nitrite as nitrogen; P, dissolved dissolved nitrite as nitrogen; P, , dissolved 3 2 .20 .59 .40 .54 .50 .57 .57 .68 .40 .57 .40 .40 .50 .50 .51 .50 .50 .50 .50 .56 .94 .40 .40 .71 .69 .58 .50 .50 .51 .80 .55 .60 0.57 1.1 1.1 Tl (mg/kg) Ti 2,400 1,100 2,700 1,900 2,400 2,400 3,100 3,800 2,600 1,900 2,200 3,400 2,000 1,900 2,400 3,000 3,000 2,500 2,200 2,400 2,500 1,900 3,200 2,600 1,600 2,300 1,300 3,000 3,300 2,300 2,300 2,700 2,800 2,100 2,800 (mg/kg) 8.0 3.6 8.2 6.2 8.6 7.2 8.8 8.1 6.0 6.8 9.4 6.7 6.1 9.1 9.7 9.2 9.8 9.5 7.7 9.2 7.1 9.8 4.8 7.7 9.3 9.9 9.9 7.7 9.6 Th 11.4 10.1 10.0 11.4 11.3 10.5 (mg/kg) .23 .63 .23 .74 .48 .49 .52 .60 .45 .58 .31 .20 .42 .32 .24 .30 .51 .28 .59 .20 .77 .27 .33 .30 .41 .90 .67 .46 .56 .58 .83 .43 .76 0.57 1.1 Ta (mg/kg) 62.0 81.7 36.9 54.6 64.5 32.2 45.2 49.0 52.0 59.4 55.8 45.8 51.3 35.7 34.2 38.2 38.3 54.5 29.9 44.7 40.6 39.7 55.8 41.6 45.6 31.5 71.3 44.2 44.8 40.9 36.3 41.1 38.6 42.7 41.6 Sr , dissolved nitrite plus nitrate as nitrogen; NO , dissolved 3 2 (mg/kg) Date 8/30/2005 8/29/2005 8/29/2005 8/29/2005 8/30/2005 8/30/2005 8/29/2005 8/29/2005 8/30/2005 8/30/2005 8/30/2005 8/30/2005 8/29/2005 8/29/2005 8/29/2005 8/29/2005 8/29/2005 8/29/2005 8/30/2005 8/30/2005 8/30/2005 8/29/2005 8/30/2005 8/30/2005 8/30/2005 8/29/2005 8/29/2005 8/29/2005 8/29/2005 8/29/2005 8/30/2005 8/30/2005 8/30/2005 8/30/2005 8/29/2005 Site Name , dissolved ammonia as nitrogen; NO , dissolved 3 , dissolved orthophosphorus as phosphorus; mg/L, milligrams per liter; mg/kg, kilogram; <, less than; Al, aluminum; Ba, , dissolved 4 Bear Creek near Caverna Unnamed creek at Gordon Hollow Jane Creek above Little Sugar Missouri Creek near Jane Ark. Creek near Bella Vista, Little Sugar Ark. Creek near Bella Vista, Tanyard Jane Creek below Little Sugar Creek near Pineville Little Sugar near Mt Shira Elk River Indian Creek near Lanagan near Noel Elk River City near Tiff Elk River Indian Creek near Anderson Br near Anderson Beaver Hollow Rocky Indian Creek below Bullskin Creek near Erie Elkhorn Creek near McNatt Indian Creek near McNatt Indian Creek at Boulder City North Indian Creek near Boulder City South Indian Creek near Boulder City Creek near Powell Mikes Hollow Woodard Creek below Trent Pine Creek Creek below Big Sugar Mountain Creek below Big Sugar Unnamed creek at Kings Valley Creek near Cyclone Big Sugar Creek near Pineville Big Sugar Hollow Unnamed creek at Bentonville Creek near Powell Big Sugar Creek near Jacket Big Sugar Otter Creek near Jacket Mill Creek near Noel Butler Creek near Noel Access Creek at Deep Ford Big Sugar Nutrient and trace-element concentrations from streambed-sediment samples collected the Upper Elk River Basin,

(fig. 23) Identifier 1A 2 3 4 5 6 7 8 9A 10 11A 13 14 15 16 17 18 19 21 22 23A 24A 25 26 27A 28 29 30 33 34 35 36 37A 37 39 Table 8. Table August 2005.—Continued Mecator; Ark., Arkansas; nutrient concentrations are from leachate samples; NH Transverse [UTM, Universal nitrogen as nitrogen; NH phosphorus; PO chromium; Cs, cesium; Cu, copper; Fe, iron; Ga, gallium; barium; Be, beryllium; Bi, bismuth; Ca, calcium; Cd, cadmium; Ce, cerium; Co, cobalt; Cr, phosphorus; Pb, P, Mo, molybdenum; Na, sodium; Nb, niobium; Ni, nickel; K, potassium; La, lanthanum; Li, lithium; Mg, magnesium; Mn, manganese; yttrium; Y, vanadium; titanium; Tl, thallium; U, uranium; V, tantalum; Th, thorium; Ti, strontium; Ta, Sc, scandium; Sr, lead; Rb, rubidium; Sb, antimony; Zn, zinc] 46 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

1.0

0.9 Dissolved ammonia as nitrogen Total ammonia plus organic nitrogen as nitrogen 0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

1.2

Dissolved nitrite plus nitrate as nitrogen Dissolved orthophosphorus as phosphorus 1.0

0.8

0.6

0.4

0.2

lk River 1.2 E Indian Creek Big Sugar Creekittle Sugar Creek Total phosphorus L Elk River tributaries Indian Creek tributaries 1.0 Little Sugar Creek tributaries

NORMALIZED AND SCALED CONCENTRATION IN LEACHATE SAMPLES, IN MILLIGRAMS PER LITER IN LEACHATE NORMALIZED AND SCALED CONCENTRATION EXPLANATION 0.8 Value more than 3.0 times the interquartile range Value within 1.5 and 3.0 times the interquartile range 0.6 90th percentile

0.4

75th percentile (upper quartile) 0.2 50th percentile (median) 25th percentile (lower quartile) 0

Elk River 10th percentile Indian Creek Big Sugar Creekittle Sugar Creek Value within 1.5 and 3.0 times the interquartile range L Elk River tributaries Indian Creek tributaries Value more than 3.0 times the interquartile range Little Sugar Creek tributaries

Figure 24. Concentrations of selected nutrients in leachate samples normalized to organic carbon content in streambed-sediment samples in the Upper Elk River Basin, August 2005. Streambed-Sediment Quality 47

Arsenic Chromium

21 22 21 22 23A 23A Creek Creek 17 17 19 19 16 18 16 18

Elk 15 Indian Elk 15 Indian Ri 28 Ri 28 ver 13 Sugar ver 13 Sugar 14 39 Big 24A 14 39 Big 24A 29 34 29 34 10 30 10 30 9A 33 25 9A 33 25 8 7 26 8 7 26 11A 37 11A 37 4 27A 4 27A 37A 3 eek 37A 3 eek 35 Cr 35 Cr 2 1A 2 1A 36 36 6 6

5 5 Sugar Creek Sugar Creek Little Little

Concentration, in milligrams per kilogram Concentration, in milligrams per kilogram

3.0 to .4.8 7.7 to 9.0 0 to 44.5 59.3 to 64.4 4.9 to 6.0 9.1 to 22.0 44.6 to 48.8 64.5 to 94.8 6.1 to 7.6 48.9 to 59.2

Lead Zinc

21 21 22 22 23A 23A Creek Creek 17 17 19 19 16 18 16 18

Elk 15 Indian Elk 15 Indian Ri 28 Riv 28 ver 13 Sugar er 13 Sugar 14 39 24A 14 39 Big 24A Big 34 29 34 29 10 30 10 30 9A 33 25 9A 33 25 8 7 26 8 7 26 11A 11A 37 37 4 27A 4 27A 37A eek 37A 3 reek 35 Cr 35 C 2 1A 2 1A 36 36 6 6

5 5 S Sugar Creek ugar Creek Little Little

Concentration, in milligrams per kilogram Concentration, in milligrams per kilogram

14.9 to 25.4 55.9 to 87.7 45.2 to 89.6 116.1 to 199 25.5 to 37.6 87.8 to 853 EXPLANATION 89.7 to 101 199.1 to 658 37.7 to 55.8 101.1 to 116 9A Identifier (table 8) Tributary site Mainstem site NOTE: Concentrations scaled to maximum value

Figure 25. Concentrations of selected trace elements normalized to organic carbon content in streambed-sediment samples in the Upper Elk River Basin, August 2005. 48 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

25 14 22 10 12 Arsenic 10 Cadmium 20 29 8 log cadmium = 0.871 log iron - 3.84 log arsenic = 1.28 log iron - 4.65 6 r2 = 0.14 15 r2 = 0.74 p = 0.025 p <0.01 4 15 21 10 34 2 19 16 14

1,000 10 800 50 Copper Lead 9A 600 40 log copper = 0.55 log iron -1.128 2 400 log lead = 1.049 log iron - 3.02 r = 0.34 2 p <0.01 r = 0.21 p = 0.004 30 200

20 13 14 15

10,000 20,000 30,000 40,000 50,000 700 22 IRON CONCENTRATION, IN MILLIGRAMS PER KILOGRAM 600 Zinc 500 15 EXPLANATION 400 log zinc = 0.006 log iron + 26.72 r2 = 0.12 21 95th percentile confidence interval 300 p = 0.004

TRACE-ELEMENT CONCENTRATION IN THE LESS THAN 63-MICROMETER SIZE FRACTION, MILLIGRAMS PER KILOGRAM 13 Linear trend 34 14 16 200 19 5th percentile confidence interval Big Sugar Creek tributaries Big Sugar Creek

100 Little Sugar Creek tributaries Little Sugar Creek

Indian Creek tributaries Indian Creek Elk River tributaries Elk River 10,000 20,000 30,000 40,000 50,000 9A Identifier from table 8 IRON CONCENTRATION, IN MILLIGRAMS PER KILOGRAM

Figure 26. Relation of selected trace-element concentrations and iron in the less than 63-micrometer size fraction of streambed-sediment samples from the Upper Elk River Basin, August 2005. Streambed-Sediment Quality 49

14 12 EXPLANATION 10 Log cadmium = 1.121 log zinc - 2.43 8 r2 = 0.83 95th percentile confidence interval p <0 .01 6 Linear trend

5th percentile confidence interval 4 Big Sugar Creek tributaries Big Sugar Creek 2 Little Sugar Creek tributaries Little Sugar Creek

Indian Creek tributaries Indian Creek Elk River tributaries Elk River CADMIUM CONCENTRATION, IN MILLIGRAMS PER KILOGRAM CADMIUM CONCENTRATION,

100 200 300 400 500 600 700

ZINC CONCENTRATION, IN MILLIGRAMS PER KILOGRAM

Figure 27. The trend of cadmium and zinc in streambed-sediment samples in the Upper Elk River Basin, August 2005.

Concentrations of trace elements in sediments vary anthropogenic contamination, possibly from urban sources widely depending upon the geologic material from which from within Lanagan. Site 22 is along North Indian Creek they are derived. This natural variability complicates deter- about 1 river mile upstream from Boulder City. mining if trace-element concentrations are larger than Samples from two of the five tributary sites (sites 15 naturally occurring background concentrations. However, and 22) and four of the five main stem (sites 14, 16, 19, and many trace elements in sediment are associated with the 21) sampling sites along Indian Creek plot above the general iron-oxides and strong correlations exist between their trend of cadmium and iron (fig. 26). Although above the concentrations and iron (Hem, 1985). This natural positive general trend line, concentrations of cadmium in streambed- relation between trace-element and iron concentrations can sediment samples at all sites were less than 15 mg/kg. be utilized to identify increased trace-element concentrations The larger than expected cadmium concentrations at site from manmade or anthropogenic sources. Mahler (2003) 22 and other sites within the Indian Creek Basin possibly illustrated this relation graphically by showing that sediment are related to geology. The Elk River Basin lies just south samples with naturally occurring trace-element concentra- of the historical Tri-State Lead-Zinc Mining District, and tions plotted along a linear trend. Samples that plotted above some abandoned shallow mine workings are located within the linear trend (larger than expected trace-element concen- the upper part of the North Indian Creek Basin, about 4 mi tration) were suspected of being affected from anthropogenic upstream from site 22. One of the major ore minerals in the sources. district was sphalerite (ZnS), which contains considerable Concentrations of trace elements in streambed-sedi- amounts of cadmium. Concentrations of cadmium in stream- ment samples from the Elk River Basin (fig. 25) generally bed sediments are strongly correlated with zinc, and samples correlated well with iron concentrations (fig. 26), indicat- from Indian Creek and its tributaries have among the largest ing mostly non-anthropogenic (or natural) sources for most cadmium and zinc concentrations (fig. 27). Indian Creek trace elements. Several outliers plotting substantially above sediments have significantly larger cadmium, lead, and zinc the general trends were lead at site 10 and cadmium at site (p<0.01, p=0.06, and 0.02) concentrations than sediments in 22. Site 10 (Indian Creek near Lanagan) is immediately Big Sugar Creek. Concentrations of cadmium in sediments downstream from Lanagan, and the lead concentration of in Indian Creek also were significantly larger than in sedi- 853 milligrams per kilogram (mg/kg) is likely the result of ments from Little Sugar Creek (p<0.01). 50 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

Summary cantly since the 1960s. Concentrations in the 1970s and 1980s, though similar, had increased from those in the 1960s, and the concentrations from the 1990s and 2000s increased still more. The U.S. Geological Survey, in cooperation with the Nitrate concentrations significantly increased in samples Missouri Department of Natural Resources, collected samples that were collected during larger discharges (greater than 355 in the Upper Elk River Basin in southwestern Missouri and cubic feet per second) from the Elk River near Tiff City as northwestern Arkansas from October 2004 through Septem- compared to the concentrations in samples collected during ber 2006 (one set of stormwater samples was collected in late smaller discharges. November and early December 2006) to determine the water Data collected by the U.S. Geological Survey from Octo- quality and streambed-sediment quality. Water-quality samples ber 2004 through December 2006 indicate the following: were collected monthly, during selected storms, and during * Nitrate concentrations were largest in Indian Creek. low-base flow conditions; streambed-sediment samples were Several sources of nitrate are present in the basin, including collected one time. poultry facilities in the upper part of the basin, effluent inflow The Elk River Basin encompasses more than 1,000 from communities of Anderson and Lanagan, land-applied square miles in parts of Missouri, Arkansas, and Oklahoma. animal waste, chemical fertilizer, and possible leaking septic It is in the Springfield Plateaus physiographic section of the systems. Ozark Plateaus physiographic province. The slightly rolling * The total phosphorus concentrations were largest in hills contain numerous karst features (sinkholes, caves, and Little Sugar Creek. The median concentration in samples from springs) that transport surface water through solution-enlarged Little Sugar Creek below Caverna was more than eight times joints and fractures. Land use in the Elk River Basin is equally the median concentration in samples from the Elk River near divided between forest and pasture. Confined animal feeding Tiff City; the median concentration from samples from Little operations in McDonald County account for the second largest Sugar Creek near Pineville was almost four times the median concentration of poultry in Missouri, with an estimated 6 mil- concentration in samples from the Elk River near Tiff City. lion broilers and other meat-type chickens. Poultry operations * In the Upper Elk River Basin, the largest median nitrate are throughout the basin, but tend to be denser in the Indian load was carried by the Elk River near Tiff City. The loads Creek Basin. The population of McDonald County in 2005 is increased downstream in the basin. Little Sugar Creek below estimated to be 22,844, an increase of 35 percent since 1990. Caverna and the Elk River near Tiff City carried the largest In 1998, the Missouri Department of Natural Resources total phosphorus load. included a 21.5-mile river reach of the Elk River on the 303(d) * Nitrate concentrations tended to increase with increas- list of impaired waters in Missouri as required by Section ing discharge. Concentrations increased near the beginning 303(d) of the Federal Clean Water Act. The Elk River is on the of the ambient sample collection in November 2004 and 303(d) list for excess nutrient loading. continued to increase through January 2005, when they began The nitrate as nitrogen (nitrate) concentrations from to rather substantially decrease through the summer, fall, and historical water-quality samples (data collected before October winter of 2005 along with a corresponding decrease in dis- 2004) were similar for sites on Little Sugar Creek and the Elk charge. Runoff from livestock operations or fertilizer applied River. Concentrations of total phosphorus in historical samples to lawns or fields can contribute to the increased nitrate were significantly larger in samples from Little Sugar Creek. concentrations. Total phosphorus concentrations tended to be The distribution of total phosphorus in historical samples inversely related to discharge. Some of the largest concentra- from the Elk River near Tiff City was significantly different tions at Little Sugar Creek near Pineville were in samples for samples before 1985 and after 1985. The pre-1985 mean collected at some of the smallest discharges, indicating point total phosphorus concentration was 0.064 milligram per liter, sources of the nutrient. and the post-1985 mean total phosphorus concentrations * Median concentrations of nutrient species were greater was 0.093 milligram per liter. In the Upper Elk River Basin in the stormwater samples than the median concentrations of in Missouri, the yearly average number of poultry increased the ambient samples. The nitrate concentrations in stormwater by 189 percent since 1985 when compared to the number samples ranged from 133 to 179 percent of the concentration before 1985. The total phosphorus concentrations increased in the ambient samples. The total phosphorus concentrations in samples from the Elk River near Tiff City; the last increase in the stormwater samples ranged from about 200 to more was from 2000 through 2003. The total phosphorus distribu- than 600 percent of the concentration in the ambient samples. tion by decade indicates that the concentrations since 2000 Small concentrations of nutrients carried in large storm flows have increased significantly from those in the 1960s, 1980s, can deliver extremely large loads of nutrients. For example, and 1990s. the total phosphorus load in the samples from the November Nitrate concentrations also have significantly increased in 2004 storm at the Elk River near Tiff City was 26 percent of post-1985 samples compared to pre-1985 samples in the Elk the load of the ambient samples collected from October 2004 River near Tiff City. Median nitrate concentrations increased through September 2006. from 0.880 milligram per liter before 1985 to 1.44 milligram * Nitrogen isotope samples were collected during per liter after 1985. Concentrations have increased signifi- selected storms. The value from Big Sugar Creek near Powell References Cited 51 is in the range of animal manure and human sewage. Because March 8-12, 1999: U.S. Geological Survey Water-Resources no sewage inflow is permitted for this stream, this δ15N values Investigations Report 99–4018B, v. 2, p. 431–436. indicates animal sources. The source of the δ15N from Little Sugar Creek, with a nitrogen isotope value of +11.21 per mil, Casciotti, K.L., Sigman, D.M., Hastings, M., Böhlke, J.K., and is in the range of human sewage and animal manure. Based on Hilkert, A., 2002, Measurement of the oxygen isotopic com- effluent inflow into Little Sugar Creek from Bella Vista, Ark., position of nitrate in seawater and freshwater using the deni- the value probably is indicative of human sources. The δ15N trifier method: Analytical Chemistry, v. 74, p. 4,905–4,912. values for May 2006 for Little Sugar and Indian Creeks were City-Data.com, 2007, Arkansas and Missouri cities: each about +7.0 per mil, indicating human or animal sources, accessed July 2007 at URL http://www.city-data.com/city/ or a combination of both. Arkansas[Missouri].html * Base-flow conditions as reflected by the seepage run of the summer of 2006 indicate that 52 percent of the discharge Coplen, T.B., Böhlke, J.K., and Casciotti, K.L., 2004, Using in the Elk River near Tiff City is contributed by Indian Creek. dual-bacterial denitrification to improve delta-15N deter- Little Sugar Creek contributes 32 percent and Big Sugar Creek minations of nitrates containing mass-independent 17-O: 9 percent of the discharge in the Elk River near Tiff City. Only Rapid Communications in Mass Spectrometry, v. 18, about 7 percent of the discharge at Tiff City comes from the p. 245–250. mainstem of the Elk River. * Nitrate concentrations in two of the three springs Daskalakis, K.D., and O’Connor, T.P., 1995, Normalization sampled in the Indian Creek Basin during the seepage run in and elemental sediment contamination in the coastal United the summer of 2006 were some of the largest detected dur- States: Environmental Science and Technology, v. 29, ing this study—4.34 and 11.1 milligrams per liter. Livestock p. 470–477. production facilities in the Upper Elk River Basin are concen- Davis, J.V., and Barr, M.N., 2006, Assessment of possible trated in the upper reaches of the Indian Creek Basin. Total sources of microbiological contamination in the water phosphorus concentrations were largest in the upper reaches column and streambed sediment of the Jacks Fork, Ozark of the Little Sugar Creek Basin downstream from Bella Vista, National Scenic Riverways, Missouri—Phase III: U.S. Arkansas, with a trend of generally decreasing concentrations Geological Survey Scientific Investigations Report 2006–- to the mouth of Little Sugar Creek. 5161, 32 p. * Concentrations of dissolved ammonia plus organic nitrogen as nitrogen, dissolved ammonia as nitrogen, dissolved Davis, J.V., and Schumacher, J.G., 1992, Water-quality charac- phosphorus, and dissolved orthophosphorus were detected in terization of the Spring River Basin, Southwestern Missouri all sediment leachate samples. and Southeastern Kansas: U.S. Geological Survey Water- * Concentrations of leachable nutrients normalized to Resources Investigations Report 90–4176, 112 p. organic carbon content generally tended to be slightly larger along the major forks of the Elk River as compared concentra- Edwards, T.K., and Glysson, G.D., 1998, Field methods for tions in samples from tributary sites, with sites in the upper measure of fluvial sediment: U.S. Geological Survey Tech- reaches of the major forks having among the largest concentra- niques of Water-Resources Investigations, book 3, chap. C2, tions. Concentrations of leachable nutrients in the major forks 80 p. generally decreased with increasing distance downstream. The Fenneman, N.M., 1938, Physiography of eastern United largest normalized leachable nutrients concentrations were States: New York, McGraw-Hill Book Co., Inc., 689 p. from sites on Big Sugar Creek, Little Sugar Creek, and the Elk River. Concentrations of dissolved phosphorus and dissolved Fishman, M.J., ed., 1993, Methods of analysis by the U.S. orthophosphorus tended to be larger in Little Sugar Creek than Geological Survey National Water Quality Laboratory—De- in samples from other sites. termination of inorganic and organic constituents in water and fluvial sediments: U.S. Geological Survey Open-File Report 93–125, 217 p. References Cited Fishman, M.J., and Friedman, L.C., eds., 1989, Methods for determination of inorganic substances in water and fluvial Akaike, H., 1981, Likelihood of a model and information sediments; U.S. Geological Survey Techniques of Water- criterion: Journal of Econometrics, v. 16. p. 3–14. Resources Investigations, book 5, chap. A1, 545 p. Brown, G.K., Zaugg, S.D., and Barber, L.B., 1999, Wastewa- Furlong, E.T., Cahill, J.D., Werner, S.L., Burkhardt, M.R., ter analysis by gas chromatography/mass spectrometry, in Kolpin, D.W., and Gates, P.M., 2000, High-performance Morganwalp, D.W., and Buxton, H.T., eds,, U.S. Geological liquid chromatography/electrospray ionization-mass Survey Toxic Substances Hydrology Program-Proceedings spectrometric analysis of agricultural and human health of the Technical Meeting, Charleston, South Carolina, pharmaceuticals in samples of ground and surface water, in 52 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

Emerging Issues Conference of the National Ground Water Mariotti, A., 1983, Atmospheric nitrogen is a reliable standard Association, June 7–8, 2000, Minneapolis, Minn., p. 6. for natural 15N abundance measurements: Nature, v. 303, p. 685–687. Hauck, H.S., and Harris, T.E., 2006, Water resources data, Missouri, water year 2005: U.S. Geological Survey Water- Missouri Census Data Center, 2006, Population estimates Data Report MO–05–1, 723 p. (published annually). reports: accessed December 2006 at URL http://mcdc. missouri.edu/pub/data/popests/Curmoest.xls. Helsel, D.R., and Hirsch, R.M., 1992, Statistical methods in water resources: New York, Elsevier Science Publishing Missouri Department of Conservation, 2006, Elk River water- Co., 522 p. shed: accessed November 2006 at URL http://www.mdc. mo.gov/fish/watershed/elk/location. Hem, J.D., 1985, Study and interpretation of the chemical characteristics of natural water: U.S. Geological Survey Missouri Department of Natural Resources, 1998, Section Water-Supply Paper 2254, 3d ed., 263 p. 303(d) waters: accessed December 2006 at URL http:// www.dnr.mo.gov/env/wwp/waterquality/1998_303d_list.pdf. Horowitz, A.J., 1985, A primer on trace metal sediment chemistry: U.S. Geological Survey Water- Supply Paper 2277, Missouri Department of Natural Resources, 2004, Total 57 p. maximum daily load (TMDL) for the Elk River Basin— McDonald, Barry and Newton Counties, Missouri; Benton Imes, J.L., 1989, Analysis of the effect of pumping on ground- County, Arkansas: Jefferson City, Water Pollution Control water flow in the Springfield Plateau and Ozark aquifers Program, 47 p. near Springfield, Missouri: U.S. Geological Survey Water- Resources Investigations Report 89–4079, 63 p. Missouri Department of Natural Resources, 2005, Stream classification and use designations: Rules of Department of Indiana Business Research Center, 2006, USA counties in Natural Resources Division 20—Clean Water Commission profile: STATS Indiana, accessed December 2006 at URL Chapter 7—Water Quality, accessed February 2007 at URL http://www.stats.indiana.edu/uspr/a/us_profile_frame. http://www.sos.mo.gov/adrules/csr/current/10csr/10csr.asp. html?S29?C119. Missouri Department of Natural Resources, 2006, State oper- Insightful Corporation, 2005, S-Plus for Windows—Profes- ating permits: Water Pollution Control Program, accessed sional Developer, version 7: Seattle, Wash. December 2006 at URL http://www.dnr.mo.gov/env/wwp/ Jeffrey, Alan, Kaplan, Isaac, Zhang, Dachun, Lu, Shan-Tan, cafo/index.html. and Nielsen, Jesper, 1997, Identifying the sources of nitrate Missouri Department of Natural Resources, 2007, Final contamination in groundwater, accessed August 2007 at site specific permits, Division of Environmental Quality: URL http://www.dpra.com/File/zymaxstableisotope.pdf. accessed April 2007 at URL http://www.dnr.mo.gov/env/ Kolpin, D.W., Furlong, E.T., Meyer, M.T., Thurman, E.M., wpp/permits/wpcpermits-issued.htm . Zaugg, S.D., Barber, L.B., and Buxton, H.T., 2002, Pharma- Missouri Resource Assessment Partnership, 2005, Missouri ceuticals, hormones, and other organic wastewater contami- land use land cover: accessed February 2007 at URL http:// nants in U.S. streams, 1999-2000: A national reconnais- msdis.missouri.edu/html/Lulc2.html sance: Environmental Science and Technology, v. 36, no. 6, p. 1,202–1,211. Missouri Watershed Information Network, 2006, Elk River Basin: accessed December 2006 at URL http://www. Lindsey, B.D., and Koch, M.L., 2004, Determining sources cerc.usgs.gov/morap/Assets/maps/MoRap_2005_lulc_ of water and contaminants to wells in a carbonate aquifer Mo2005_003.pdf. near Martinsburg, Blair County, Pennsylvania, by use of geochemical indicators, analysis of anthropogenic contami- Myers, D.N., and Wilde, F.D., eds, 1997, National field nants, and simulation of ground-water flow: U.S. Geologi- manual for the collection of water-quality data—Biological cal Survey Scientific Investigations Report 2004–5124, indicators: U.S. Geological Survey Techniques of Water- 46 p. Resources Investigations, book 9, chap. A7, 38 p. Luoma, S.N., 1990, Processes affecting metal concentrations Myers, D.N., and Wilde, F.D., eds,, 2003, Biological indica- in estuarine and coastal marine sediments, in Furness, R.W., tors (3d ed.): U.S. Geological Survey Techniques of Water- and Rainbow, P.S., (eds.), Heavy metals in the marine envi- Resources Investigations, book 9, chap. A7, accessed July ronment, Boca Raton, Fla., CRC Press. 2007 at URL http://water.usgs.gov/owq/FieldManual. Mahler, B.J., 2003, Quality of sediment discharging from the National Drought Mitigation Center, 2007, University of Barton Springs system, Austin, Texas, 2000–2002: U.S. Nebraska-Lincoln, accessed April 2007 at URL http://www. Geological Survey Fact Sheet 089–03, 6 p. drought.unl.edu/dm/archive.html. References Cited 53

National Oceanic and Atmospheric Administration, 1999–- University of Arkansas, 1997, Center for Advanced Spatial 2003, Climatologic data annual summary, Missouri: Technologies: accessed February 2007 at URL http://www. Asheville, North Carolina, National Climatic Center, cast.uark.edu/cast/research/lulc. v. 103–107, no. 13. U.S. Department of Agriculture, 2006, National Agriculture National Oceanic and Atmospheric Administration, 2004– Statistics Service—Quick stats: accessed December 2006 at 2006, Climatologic data monthly, Missouri: Asheville, URL http://www.nass.usda.gov/QuickStats. North Carolina, National Climatic Center, v. 108–110, no. 1–12. Wilde, F.D., and Radtke, D.B., eds., 1998, National field manual for the collection of water-quality data—Field mea- Rantz, S.E., and others, 1982, Measurement and computation surements: U.S. Geological Survey Techniques of Water- of streamflow—Volume 1. Measurement of stage and dis- Resources Investigations, book 9, chap. A6, 238 p. charge: U.S. Geological Survey Water-Supply Paper 2175, 284 p. Wilde, F.D., Radtke, D.B., Gibs, J., and Iwatsubo, R.T., eds., 1999a, National field manual for the collection of water- Runkel, R.L., Crawford, C.G., and Cohn, T.A., 2004, Load quality data—Collection of water samples: U.S. Geological estimator (LOADEST)—A FORTRAN program for esti- Survey Techniques of Water-Resources Investigations, book mating constituent loads in streams and rivers: U.S. Geo- 9, chap. A4, 103 p. logical Survey Techniques and Methods Report 4–A5, 75 p. Wilde, F.D., Radtke, D.B., Gibs, J., and Iwatsubo, R.T., eds., 1999b, National field manual for the collection of water- Schumacher, J.G., 2001, Water quality in the Upper Shoal quality data—Processing of water samples: U.S. Geological Creek Basin, southwestern Missouri, 1999-2000: U.S. Survey Techniques of Water-Resources Investigations, book Geological Survey Water-Resources Investigations Report 9, chap. A5, 128 p. 01–4181, 60 p. Zauug, S.D., Smith, S.G., Schroeder, M.P., Barber, L.B., and Sigman, D.M., Casciotti, K.L., Andreani, M., Barford, C., Burkhardt, M.R., 2001, Methods of analysis by the U.S. Galanter, M., and Böhlke, J.K., 2001, A bacterial method Geological Survey National Water Quality Laboratory— for the nitrogen isotopic analysis of nitrate in seawater and Determination of wastewater compounds by polystyrene freshwater: Analytical Chemistry, v. 73, p. 4,145–4,153. divinylbenzene solid-phase extraction and capillary-column gas chromatography/mass spectrometry: U.S. Geological Tukey, J.W., 1977, Eexploratory data analysis: Reading, Mass., Survey Water-Resources Investigations Report 01–4186, Addison-Wesley, 688 p. p. 37. 54 Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas, 2004–06

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Smith and others—Water and Streambed-Sediment Quality in the Upper Elk River Basin, Missouri and Arkansas—Scientific Investigations Report 2007–5181 Printed on recycled paper