Occurrence, distribution, and volume of metals-contaminated sediment of selected streams draining the Tri-State Mining District, Missouri, Oklahoma, and Kansas, 2011–12
<p>Lead and zinc were mined in the Tri-State Mining District (TSMD) of southwest Missouri, northeast Oklahoma, and southeast Kansas for more than 100 years.…
Public-domain full text preserved in the Mountain Man Mining Library. Original source: pubs.usgs.gov.
Prepared in cooperation with the U.S. Fish and Wildlife Service Occurrence, Distribution, and Volume of MetalsContaminated Sediment of Selected Streams Draining the Tri-State Mining District, Missouri, Oklahoma, and Kansas, 2011-12 Scientific Investigations Report 2016-5144 U.S. Department of the Interior U.S. Geological Survey
Cover. Miners in the Beaver Mine near Cardin, Oklahoma, around 1930. Photograph courtesy of Leona Atwood.
Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams Draining the Tri-State Mining District, Missouri, Oklahoma, and Kansas, 2011-12 By D. Charlie Smith Prepared in cooperation with the U.S. Fish and Wildlife Service Scientific Investigations Report 2016-5144 U.S. Department of the Interior U.S. Geological Survey
U.S. Department of the Interior SALLY JEWELL, Secretary U.S. Geological Survey Suzette M. Kimball, Director U.S. Geological Survey, Reston, Virginia: 2016 For more information on the USGS—the Federal source for science about the Earth, its natural and living resources, natural hazards, and the environment—visit ://www.usgs.gov or call 1-888-ASK-USGS. For an overview of USGS information products, including maps, imagery, and publications, visit ://store.usgs.gov. Any use of trade, firm, or product names is for descriptive purposes only and does not imply endorsement by the U.S. Government. Although this information product, for the most part, is in the public domain, it also may contain copyrighted materials as noted in the text. Permission to reproduce copyrighted items must be secured from the copyright owner. Suggested citation: Smith, D.C., 2016, Occurrence, distribution, and volume of metals-contaminated sediment of selected streams drain ing the Tri-State Mining District, Missouri, Oklahoma, and Kansas, 2011-12: U.S. Geological Survey Scientific Investi gations Report 2016-5144, 86 p., ://dx.doi.org/10.3133/sir20165144. ISSN 2328-0328 (online)
Contents Abstract 1 Introduction 2 Description of Study Area and Mining History 2 Purpose and Scope 2 Previous Investigations 4 Methodology 6 Site Selection 6 Sample Collection 7 Stream Channel 7 Flood Plain 15 Sample Processing and Analysis 15 Stream Channel 20 Flood Plain 21 Laboratory Confirmation Samples 21 Estimation of the Volume of Contaminated Gravel Bar Deposits 22 Quality Control and Quality Assurance 23 Data Analysis Methods 23 Standard Reference Material 25 Blanks 29 Replicate X-Ray Fluorescence Analyses 29 Laboratory Confirmation Samples 29 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment 33 Center Creek 33 Site Selection and Description 33 Depth and Concentration of Metals in Channel Sediments 33 Estimated Volume of Channel Sediment Contaminated by Mine Waste 37 Depth and Concentration of Metals in Flood-Plain Sediments 37 Turkey Creek 41 Site Selection and Description 41 Depth and Concentration of Metals in Channel Sediments 47 Estimated Volume of Channel Sediment Contaminated by Mine Waste 47 Depth and Concentration of Metals in Flood-Plain Sediments 47 Shoal Creek 50 Site Selection and Description 50 Depth and Concentration of Metals in Channel Sediments 50 Estimated Volume of Channel Sediment Contaminated by Mine Waste 55 Depth and Concentration of Metals in Flood-Plain Sediments 55 Tar Creek 55 Site Selection and Description 55 Depth and Concentration of Metals in Channel Sediments 58 Estimated Volume of Channel Sediment Contaminated by Mine Waste 58 Depth and Concentration of Metals in Flood-Plain Sediments 58
Spring River 62 Site Selection and Description 62 Depth and Concentration of Metals in Channel Sediments 62 Summary and Conclusions 64 References Cited 68 Figures
1. Map showing study sites in the Tri-State Mining District in Missouri, Oklahoma, and Kansas 3
2. Photograph showing freeze-core sampler with attached frozen sediment sample immediately after recovery and the freeze-core sampler with scale 13
3. Photograph showing liquid carbon dioxide injection tube inserted into the hollow driving rods during the injection of liquid CO2 14
4. Photograph showing removal of the rods and sample by hand using a fence-post puller 15
5. Photograph showing flood-plain core that has been prepared for analysis with the x-ray fluorescence instrument 21
6. Graphs showing relations of percent difference between mean concentration by x-ray fluorescence with the most-probable-value concentrations of cadmium, lead, and zinc in standard reference materials 28
7. Graphs showing relations between concentrations of cadmium, lead, and zinc in laboratory subsamples determined by x-ray fluorescence and laboratory methods, and between concentrations determined by x-ray fluorescence in original and split subsamples 31
8. Graphs showing comparison of relative percent difference between laboratory results for cadmium, lead, and zinc in the split samples, and the x-ray fluorescence results for either the original samples or the split sample before its submittal to the laboratory for stream channel sediment, Tri-State Mining District 32
9. Aerial photographs from 2013 and 1938 showing location of cores, samples, and tile probe soundings for sites C1 and C2 of intensive study on Center Creek, Missouri, 2011-12 34
10. Aerial photographs from 2013 and 1938 for site C3 and from 2013 and 1961 for site C4 showing location of cores, samples, and tile probe soundings on Center Creek, Missouri, 2011-12 35
11. Aerial photographs from 2013 and 1961 showing location of cores, samples, and tile probe soundings for sites C5 and C6 on Center Creek, Missouri, 2011-12 36
12. Boxplots showing frequency distributions of the concentrations of cadmium, lead, and zinc at specific sites in order from downstream to upstream 38
13. Graphs showing vertical concentration profiles for lead in the less than 2-millimeter size fraction of gravel bar-sediment samples scanned by x-ray fluorescence, Center Creek, Missouri, 2011-12 39
14. Graphs showing vertical concentration profiles for zinc in the less than 2-millimeter size fraction of gravel bar-sediment samples scanned by x-ray fluorescence, Center Creek, Missouri, 2011-12 40
15. Graphs showing vertical profiles by flood-plain core and sample location of lead concentrations analyzed by x-ray fluorescence in Center Creek, Turkey Creek, Shoal Creek, and Tar Creek, 2011-12 42
16. Graphs showing vertical profiles by flood-plain core and sample location of zinc concentrations analyzed by x-ray fluorescence in Center Creek, Turkey Creek, Shoal Creek, and Tar Creek, 2011-12 43
17. Aerial photographs from 2013 and 1938 showing location of bed-sediment cores, samples, and tile probe soundings for sites TC1, TC2, and TC3 in Turkey Creek, Missouri, 2012 44
18. Aerial photographs from 2013 and 1938 showing location of bed-sediment cores, samples, and tile probe soundings for sites TC4 and TC5 in Turkey Creek, Missouri, 2012 45
19. Aerial photographs from 2013 and 1961 showing location of bed-sediment cores, samples, and tile probe soundings for sites TC6 and TC7 in Turkey Creek, Missouri, 2012 46
20. Graphs showing vertical profiles by core and sample location of lead concentrations in the less than 2-millimeter size fraction of gravel bar-sediment samples analyzed by x-ray fluorescence in Turkey Creek, Missouri, 2012 48
21. Graphs showing vertical profiles by core and sample location of zinc concentrations in the less than 2-millimeter size fraction of gravel bar-sediment samples analyzed by x-ray fluorescence in Turkey Creek, Missouri, 2012 49
22. Aerial photographs from 2013 and 1958 showing location of bed-sediment cores and sample locations for sites SFP1 and S1 in Shoal Creek, Missouri, 2012 51
23. Aerial photographs from 2013 and 1938 showing location of bed-sediment cores and sample locations for sites S2 and SFP2 in Shoal Creek, Missouri, 2012 52
24. Aerial photographs from 2013 and 1938 for sites S3 and S4, and from 2013 and 1958 for site S5 showing location of cores, samples, and tile probes in Shoal Creek, Missouri, 2012 53
25. Graphs showing vertical profiles by core and sample location of lead concentrations in the less than 2-millimeter size fraction of stream channel samples analyzed by x-ray fluorescence in Shoal Creek, Missouri, 2012 54
26. Graphs showing vertical profiles by core and sample location of zinc concentrations in the less than 2-millimeter size fraction of stream channel samples analyzed by x-ray fluorescence in Shoal Creek, Missouri, 2012 56
27. Aerial photographs from 2013 and 1958 showing location of sediment cores, samples, and tile probe soundings for sites TR7, TR6, TR5, TRFP2, TR4, TR3, TR2, and TR1 on Tar Creek, Oklahoma, 2011 57
28. Aerial photographs from 2013 and 1958 showing location of sediment cores, samples, and tile probe soundings for sites TR12, TR11, TRFP1, TR10, TR9, and TR8 on Tar Creek, Oklahoma, 2011 59
29. Graphs showing vertical profiles by core and sample location of lead concentrations in the less than 2-millimeter size fraction of stream channel samples analyzed by x-ray fluorescence in Tar Creek, Oklahoma, 2011 60
30. Vertical profiles by core and sample location of zinc concentrations in the less than 2-millimeter size fraction of stream channel samples analyzed by x-ray fluorescence in Tar Creek, Oklahoma, 2011 61
31. Aerial photographs from 2013 and 1958 showing location of sediment cores and samples for sites SR1 and SR2 on Spring River, Kansas, 2012 63
32. Graphs showing vertical profiles by core and sample location of lead and zinc concentrations in the less than 2-millimeter size fraction of gravel bar-sediment samples analyzed by x-ray fluorescence, Spring River, Kansas, 2012 64
Tables
1. Sediment core and sample locations, depth of water from the surface and maximum sample depth at each location, maximum depth of sediment exceeding the consensus probable effects concentration and the Tri-State Mining District specific probable effects concentration, and the percent depth of sediment exceeding the general probable effects concentration and the Tri-State Mining District specific probable effects concentration for Center Creek, Turkey Creek, Shoal Creek, Tar Creek, and Spring River in the Tri-State Mining District, 2011-12 8
2. Flood-plain core and sample locations, maximum depth or core at each location, maximum depth of core exceeding the consensus probable effects concentration and the Tri-State Mining District-specific probable effects concentration, and the percent depth of core exceeding the general probable effects concentration and the Tri-State Mining District specific probable effects concentration for the flood plains of Center Creek, Turkey Creek, Shoal Creek, and Tar Creek in the Tri-State Mining District, 2011-12 12
3. Tile probe locations, depth of water from the surface, and maximum depth of refusal at each location for Center Creek, Turkey Creek, Shoal Creek, and Tar Creek in the Tri-State Mining District, 2011-12 16
4. Mean maximum proportional depth of sediment exceeding the consensus probable effects concentrations and the Tri-State Mining District specific probable effects concentrations, and mean total depth of boreholes and tile probes for each site, Center Creek, Turkey Creek, Shoal Creek, Tar Creek, and Spring River in the Tri-State Mining District, 2011-12 24
5. Digitized gravel bar area, creek or river total drainage area, hydrologic unit code, mean thickness of sediments exceeding the consensus probable effects concentrations and the Tri-State Mining District specific probable effects concentration, and estimated total volume of sediment with concentrations of lead or zinc that exceed the consensus probable effects concentration and the Tri-State Mining District specific probable effects concentration for Center Creek, Turkey Creek, Shoal Creek, and Tar Creek in the in the Tri-State Mining District, 2011-12 26
6. Results of analyses of standard reference materials by the x-ray fluorescence unit 27
7. Statistical summary of triplicate and septuplet x-ray fluorescence scans of intact flood-plain cores in the Tri-State Lead and Zinc Mining District, 2011-12 30
8. Concentrations of select trace element measured by two methods, with two sample preparation types, in the less than 2-millimeter size fractions of stream channel sediment samples 72
Conversion Factors U.S. customary units to International System of Units Multiply By To obtain Length inch (in.) centimeter (cm) inch (in.) millimeter (mm) foot (ft) meter (m) mile (mi) kilometer (km) Area acre 4,047 square meter (m2) acre hectare (ha) acre square hectometer (hm2) acre square kilometer (km2) square foot (ft2) square centimeter (cm2) square foot (ft2) square meter (m2) square mile (mi2) hectare (ha) square mile (mi2) square kilometer (km2) Volume cubic yard (yd3) cubic meter (m3) Mass ounce, avoirdupois (oz) gram (g) pound, avoirdupois (lb) kilogram (kg)
International System of Units to U.S. customary units Multiply By To obtain Length centimeter (cm) inch (in.) millimeter (mm) inch (in.) meter (m) foot (ft) kilometer (km) mile (mi) Area square meter (m2) 0.0002471 acre hectare (ha) acre square hectometer (hm2) acre square kilometer (km2) acre square centimeter (cm2) square foot (ft2) square meter (m2) square foot (ft2) square hectometer (hm2) section (640 acres or 1 square mile) hectare (ha) square mile (mi2) square kilometer (km2) square mile (mi2) Volume cubic meter (m3) cubic yard (yd3) Mass gram (g) ounce, avoirdupois (oz) kilogram (kg) pound avoirdupois (lb) Datum Horizontal coordinate information is referenced to the North American Datum of 1983 (NAD 83).
Abbreviations ALA-D enzyme-aminolevulinic acid dehydratase CMERSC Central Mineral and Environmental Resources Science Center COC chain of custody CPEC consensus probable effects concentration DQO data quality objective ICP-AES inductively coupled plasma-atomic emission spectrometry ICP-MS inductively coupled plasma-mass spectrometry LOD limit of detection MPV most probable value MVT Mississippi Valley-Type (metals) NIST National Institute of Standards and Technology NRCS Natural Resources Conservation Service PEC probable effects concentration RCRA Resource Conservation and Recovery Act RPD relative percent difference RSD relative standard deviation SLERA screening level ecological risk assessment SRM standard reference material SSURGO Soil Survey Geographic Database TPEC Tri-State Mining District specific probable effects concentration TSMD Tri-State Mining District USFWS U.S. Fish and Wildlife Service USGS U.S. Geological Survey XRF x-ray fluorescence
Occurrence, Distribution, and Volume of MetalsContaminated Sediment of Selected Streams Draining the Tri-State Mining District, Missouri, Oklahoma, and Kansas, 2011-12 By D. Charlie Smith Abstract Lead and zinc were mined in the Tri-State Mining District (TSMD) of southwest Missouri, northeast Oklahoma, and southeast Kansas for more than 100 years. The effects of mining on the landscape are still evident, nearly 50 years after the last mine ceased operation. The legacies of min ing are the mine waste and discharge of groundwater from underground mines. The mine-waste piles and underground mines are continuous sources of trace metals (primarily lead, zinc, and cadmium) to the streams that drain the TSMD. Many previous studies characterized the horizontal extent of minewaste contamination in streams but little information exists on the depth of mine-waste contamination in these streams. Characterizing the vertical extent of contamination is difficult because of the large amount of coarse-grained material, rang ing from coarse gravel to boulders, within channel sediment. The U.S. Geological Survey, in cooperation with U.S. Fish and Wildlife service, collected channel-sediment samples at depth for subsequent analyses that would allow attainment of the following goals: (1) determination of the relation between concentration and depth for lead, zinc and cadmium in chan nel sediments and flood-plain sediments, and (2) determina tion of the volume of gravel-bar sediment from the surface to the maximum depth with concentrations of these metals that exceeded sediment-quality guidelines. For the purpose of this report, volume of gravel-bar sediment is considered to be distributed in two forms, gravel bars and the wetted channel, and this study focused on gravel bars. Concentrations of lead, zinc, and cadmium in samples were compared to the con sensus probable effects concentration (CPEC) and Tri-State Mining District specific probable effects concentration (TPEC) sediment-quality guidelines. During the study, more than 700 sediment samples were collected from borings at multiple sites, including gravel bars and flood plains, along Center Creek, Turkey Creek, Shoal Creek, Tar Creek, and Spring River in order to character ize the vertical extent of mine waste in select streams in the TSMD. The largest concentrations of lead, zinc, and cadmium in gravel bar-sediment samples generally were detected in Turkey Creek and Tar Creek and the smallest concentrations were detected in Shoal Creek followed by the Spring River. Gravel bar-sediment samples from Turkey Creek exceeded the CPEC for cadmium (minimum of 70 percent of samples), lead (94 percent), and zinc (99 percent) at a slightly higher frequency than similar samples from Tar Creek (69 percent, 88 percent, and 96 percent, respectively). Gravel bar-sediment samples from Turkey Creek also contained the largest concen trations of cadmium (174 milligrams per kilogram [mg/kg]) and lead (7,520 mg/kg) detected; however, the largest zinc concentration (46,600 mg/kg) was detected in a gravel barsediment sample from Tar Creek. In contrast, none of the 65 gravel bar-sediment samples from Shoal Creek contained cadmium above the x-ray fluorescence reporting level of 12 mg/kg, and lead and zinc exceeded the CPEC in only 12 percent and 74 percent of samples, respectively. In most cases, concentrations of lead and zinc above the CPEC or TPEC were present at the maximum depth of boring, which indicated that nearly the entire thickness of sediment in the stream has been contaminated by mine wastes. Approximately 284,000 cubic yards of channel sediment from land surface to the maximum depth that exceeded the CPEC and approxi mately 236,000 cubic yards of channel sediment from land surface to the maximum depth that exceeded the TPEC were estimated along 37.6 of the 55.1 miles of Center Creek, Tur key Creek, Shoal Creek, and Tar Creek examined in this study. Mine-waste contamination reported along additional reaches of these streams is beyond the scope of this study. Flood-plain cores collected in the TSMD generally only had exceedances of the CPEC and TPEC for lead and zinc in the top 1 or 2 feet of soil with a few exceptions, such as cores in low areas near the stream or cores in areas disturbed by past mining.
2 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Introduction The Tri-State Mining District (TSMD) covers about 2,500 square miles (mi2) in southwest Missouri, northeast Oklahoma, and southeast Kansas (fig. 1) and has a rich his tory of lead and zinc mining beginning in the early 1800s and continuing through the mid-1900s. Most of the ore deposits were in Jasper and Newton Counties in Missouri, Ottawa County in Oklahoma, and Cherokee County in Kansas. More than 100 years of mining in the area has left a legacy of metalcontaminated mine-waste areas, contaminated soils and stream sediment, and contaminated groundwater in the region (Chris tension, 1995; Barks, 1977; Feder and others, 1969). Although a large amount of previous work has been done to characterize the spatial extent of surficial streambed sedi ments contaminated by mine waste in the TSMD (Pope, 2005; Juracek, 2009 and 2013; Andrews and others, 2009; MacDon ald and others, 2010), little information is available on the depth or thickness of contaminated sediments in the streams. Based on surficial streambed-sediment samples compiled from various sources, maps by McDonald and others (2010) show that approximately 49 miles (mi) of Center Creek, Turkey Creek, Shoal Creek, and Tar Creek have streambed sediments that have moderate to high risk for toxicity to benthic inverte brates, as do sediments in the entire reach of the Spring River downstream from the mouth of Center Creek. Information on the depth of contamination is important to the U.S. Fish and Wildlife Service (USFWS) and other natural resource agen cies entrusted with assessing damage to the ecosystem and evaluating restoration alternatives in the TSMD. Determin ing the depth of metal contamination is difficult in saturated streambed sediment because of the wide range of grain size of the sediments (silt and sand interspersed with coarse gravels and large cobbles) that are difficult to sample with traditional methods that are generally used to collect sands, silts, and clays. The USFWS requested assistance from the U.S. Geo logical Survey (USGS) to provide information on the depth of mine-waste contaminated sediments in selected streams in the TSMD. The USGS set the goals of (1) determination of the relation between concentration and depth for lead and zinc in channel sediments and flood-plain sediments, and (2) deter mination of the volume of channel sediments from the surface to the maximum depth with concentrations of lead and zinc that exceeded sediment-quality guidelines. Similar to previous studies, the extent of mine-waste contamination was deter mined using concentrations of Mississippi Valley-Type (MVT) metals, which include lead and zinc (Leach and others, 2010). Description of Study Area and Mining History The TSMD covers an area of about 2,500 mi2 and spans three States (fig. 1). Lead and zinc ore are present in Mississippian-age rocks that are exposed at the surface in Missouri and buried by up to several hundred feet of younger (Pennsylvanian-age) rocks in the Oklahoma and Kansas parts of the TSMD. Surface and near-surface deposits of lead ore were mined and smelted as early as 1820, but commercial mining of lead ore did not begin until about 1850 near Joplin, Missouri (Pope, 2005). Although zinc ore was about five times more common than lead ore, little zinc was produced from the district during the early years because of the difficulty in smelting zinc and the low price for the concentrate (Gibson, 1972). The lack of heavy machinery in the early years lim ited most mining to the shallow near-surface deposits in the Missouri part of the district. In the 1870s, the availability of railroads and steam machinery resulted in rapid expansion to other areas of the district, and by 1876, mines were opened at Galena, Kansas. In Oklahoma and Kansas, mine shafts as much as 480 feet (ft) deep allowed mining by the room and pillar method. The water from the deep underground mines was pumped into nearby streams to dewater the mine. Mining in the TSMD peaked in about 1920, after which most mining in Missouri ceased. Production from Kansas and Oklahoma gradually declined after World War II, with the last mine clos ing in 1970. Ore was crushed during the milling process to extract the ore minerals. Waste rock from the milling process either was stored locally in large piles that often washed into nearby streams or was sold for use as agricultural lime, road aggre gate, roof aggregate, or base rock for roads and railroads. The size to which the ore was crushed during milling decreased as milling methods improved and ranged from "chat" (medium to coarse sand) in the early years to silt-size material with the introduction of the floatation process around 1920. Purpose and Scope The purpose of this report is to present results of a USGS study to assess the depth of mine-waste contaminated sedi ments along selected reaches of streams along Center Creek, Turkey Creek, Shoal Creek, and Tar Creek (fig. 1) and two locations along the Spring River in the TSMD. In 2011, 22 stream channel cores and 13 flood-plain cores were collected in gravel bars, wetted channels, and the adjacent flood plain along a 7.4-mi stretch of Tar Creek in northeastern Oklahoma. In late 2011 and 2012, 24 stream channel cores and 7 floodplain cores were collected in gravel bars, wetted channels, and the adjacent flood plain along a 11.1-mi stretch of Center Creek, 23 stream channel cores and 6 flood-plain cores were collected along a 10.1-mi stretch of Turkey Creek, 12 stream channel cores and 8 flood-plain cores were collected along an 9-mi stretch of Shoal Creek, and 5 stream channel cores were collected in 2 gravel bars on Spring River in southeastern Kan sas and southwestern Missouri. For the purpose of this report, volume of gravel-bar sediment is considered to be distributed in two forms, gravel bars and the wetted channel, and this study focused on gravel bars.
Introduction 3 ! ! ! ! ! ! ! ! Miami Galena Neosho Joplin Commerce Carthage Baxter Springs Picher Spring River Shoal Creek Lost Creek Center Creek Tar Creek Neosho River Turkey Creek Spring River Empire Lake KANSAS MISSOURI OKLAHOMA 94°20' 94°30' 94°40' 94°50' 37°20' 37°10' 37°00' 36°50' Designated waste area from Damage Assessment Plan for Jasper and Newton Counties, Missouri, 2009 20 MILES 20 KILOMETERS EXPLANATION Designated waste area Study site and identifier Stream study reach for volume estimate TC1 TC2 TC3 TC4 TC5 TC6 TC7 SFP1 S1 SFP2 S4 S2 S5 S3 TR8, 9, 10, 11, 12, TRFP2 TR1, 2, 3, 4, 5, 6, 7, TRFP1 SR1 SR2 MISSOURI KANSAS OKLAHOMA Tri-State Mining District Base from National Hydrologic dataset, 2011, 1:100,000 U.S. Geological Survey digital data, 2011, 1:100,000 North American Datum 1983 JASPER COUNTY BARTON COUNTY CHEROKEE COUNTY CRAWFORD COUNTY CHEROKEE COUNTY CRAWFORD COUNTY OTTAWA COUNTY NEWTON COUNTY MCDONALD COUNTY JASPER COUNTY BARTON COUNTY Figure 1. Study sites in the Tri-State Mining District in Missouri, Oklahoma, and Kansas.
4 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Previous Investigations Previous studies have sought to determine the lasting effects of more than 100 years of mining in the TSMD. Pope (2005) points out that hundreds of books, reports, articles, pamphlets, circulars, and abstracts have been written about the TSMD. This highlights the vast amount of work and research that has been done that ranges from geologic aspects to the environmental effects of the mining. Some of the earliest research examined the geologic nature of TSMD. Schmidt and Leonhard (1874) give one of the earliest accounts of the TSMD and describe in great detail the ore, geological condi tions, and the mining activities at the time. The TSMD is an MVT deposit that was first characterized by Bastin (1939). MVT deposits are sulfide mineral deposits and are generally dominated by zinc (sphalerite) and lead (galena) ores that are hosted in carbonate rocks. They also may contain silver and copper, which can be mined for profit. Other MVT-related metals include arsenic, barium, cadmium, nickel, and cobalt (Leach and others, 2010). These types of deposits are found throughout the world, but the largest and most stud ied deposits are in North America. Many large MVT deposits are found in the drainage basin of the Mississippi River in the central United States and include those found in the Viburnum Trend and the Old Lead Belt in southeast Missouri, the Upper Mississippi Valley District in Illinois, Wisconsin, and Iowa, and in northern Arkansas, and central Tennessee. One of the earliest studies on the environmental effects of mining in the district was done by Bailey (1911), who col lected surface-water samples from the Spring River and select tributaries that drain the TSMD. A water sample collected from a tributary of Spring River just north of Galena, Kans., had a zinc concentration of 732 milligrams per liter (mg/L). Bailey (1911) also sampled water directly from select mine discharge and storage ponds. Concentrations of zinc in those samples ranged from 677 mg/L to 1,852 mg/L. Barks (1977) determined that mine-waste runoff and mine-water discharge were contributing to high concentrations of zinc and lead in Center Creek and Turkey Creek. Barks (1977) determined that groundwater from abandoned lead and zinc mines had a mean zinc concentration of 9.4 mg/L, but was limited to the immediate mine area and had little effect on the deep aquifer. The mean dissolved zinc concentration in runoff from mine-waste areas was 16 mg/L but was as large as 200 mg/L in one summer runoff sample that also had a lead concentration of 0.4 mg/L and cadmium concentration of 1.4 mg/L. Barks (1977) also determined that mine-water discharge had increased the dissolved zinc concentrations in receiving streams from a background concentration of 0.04 mg/L to about 0.5 mg/L during low-flow conditions and that the higher concentrations were sustained during high-flow conditions by runoff from mine-waste piles. The deposition of mine waste in the streambed increased concentrations of lead and zinc in the bed material from background concentrations of 20 milligrams per kilogram (mg/kg) to 450 mg/kg for lead and from 100 mg/kg to 2,500 mg/kg for zinc (Barks, 1977). Barks (1977) estimated that the runoff from mine-waste piles contributed to a 25-fold increase in concentrations of lead and zinc in the stream bed sediments. Exposure to contaminants in an aquatic environment can cause adverse effects on the health of various aquatic spe cies, and the contaminant concentrations at which adverse effects can occur vary widely and depend on exposure time, species, life stage, and many other factors. In an effort to establish a guideline for aquatic exposure to various con taminants, sediment toxicity tests, commonly using Hyalella azteca (a freshwater amphipod), are done to determine acute and chronic exposures to contaminants (Wang and others, 2004). The results of toxicity tests are used to obtain the probable effects concentration (PEC) values for the various contaminants, above which adverse effects are more likely. MacDonald and others (2000) developed consensus-based PEC values (referred to as consensus probable effects concen tration [CPEC] values in this report) for some trace metals that were based on several published sediment-quality guidelines obtained from observed effects that elevated concentrations of mining related metals had on aquatic wildlife. CPEC values were determined to be 33 mg/kg for arsenic, 4.98 mg/kg for cadmium, 111 mg/kg for chromium, 149 mg/kg for copper, 128 mg/kg for lead, 48.6 mg/kg for nickel, and 459 mg/kg for zinc (MacDonald and others, 2000). Ingersoll and oth ers (2009), using sediments from the TSMD, developed PEC values for cadmium, lead, and zinc concentrations that were predicted to reduce the survival rate of Hyalella azteca by 10 percent relative to reference sediments that were natural background concentrations and not enriched from mineral ized areas. The Tri-State specific PEC (referred to as Tri-State Mining District specific probable effects concentration [TPEC] in this report) values of Ingersoll and others (2009) were deter mined to be 11.1 mg/kg for cadmium, 150 mg/kg for lead, and 2,083 mg/kg for zinc. The TPECs were developed using sedi ment samples collected from the Grand Lake O' the Cherokees (Grand Lake) in Oklahoma. The TSMD lies in the watersheds of the Spring River and the Neosho River. The Spring River flows into the Neosho River upstream from Grand Lake. The TSMD encompasses streams with varying levels of lead- and zinc-mining effects. For this reason, the CPEC or TPEC may not be an appropriate metric in all parts of the TSMD. In this report the general term PEC is used to represent both the CPEC and TPEC. Pope (2005) studied surficial sediments from the Spring River and Tar Creek watersheds in Kansas and determined that the sediments were particularly enriched in cadmium, lead, and zinc compared to other trace elements. The median concentrations for cadmium, lead, and zinc were 13, 180, and 1,800 mg/kg, respectively. Pope (2005) determined that the maximum concentrations of cadmium, lead, and zinc were several hundred times higher than the minimum values for those respective metals, whereas the majority of maxi mum concentrations of other trace metals were less than 10 times the minimum value. Pope (2005) determined that samples in most mine-affected individual watersheds had
Introduction 5 concentrations of cadmium, lead, and zinc that exceeded their respective CPEC. Concentrations exceeded the CPEC in 64 percent of cadmium samples, 56 percent of lead samples, and 75 percent of zinc samples. Schmitt and others (2005) collected 74 fish, representing 6 different species, from 6 different sites on the Spring and Neosho Rivers in northeast Oklahoma in the TSMD. These six sites had varying degrees of mining influence, including non-mined reference sites. Schmitt and others (2005) analyzed the blood from each fish for cadmium, lead, zinc, iron, hemo globin, and the activity of the enzyme δ-aminolevulinic acid dehydratase (ALA-D), which is involved in heme synthesis and is inhibited by lead. Fish from the sites that were most heavily affected by mining had elevated cadmium, lead, and zinc concentrations in their blood and generally exhibited a decrease in activity of ALA-D. Enzyme activity was greatest in fish from the reference sites. Schmitt and others (2005) also determined a negative correlation between lead concentrations and ALA-D activity in most species collected for the study. Their results indicated that lead was bioavailable and active biochemically in the Spring/Neosho River system. Spring River flows through Empire Lake in Kansas, which traps much of the river's sediment load. Juracek (2006) collected cores of bottom sediments from Empire Lake to determine the history of sediment deposition in the lake—a history that reflects the land use changes in the TSMD. Jura cek (2006) was able to identify pre-1954 and post-1954 layers of sediment based on the activity of cesium-137. The overall concentrations of metals in sediments decreased as sediments got younger and have leveled off since 1954. Despite the concentrations remaining constant, cadmium concentrations exceeded the CPEC by 440 to 640 percent, lead by 40 to 80 percent, and zinc by 580 to 970 percent in the most recently deposited (2005) sediments. The total volume and mass of sediment in Empire Lake was estimated to be 44 million cubic feet (about 1.6 million cubic yards) and 2,400 million pounds, respectively. Juracek (2006) also estimated the total mass of cadmium (78,000 pounds), lead (650,000 pounds), and zinc (12 million pounds) in sediment contained within Empire Lake. Sediment is deposited in Empire Lake dur ing low-inflow periods; however, the ability of the reservoir to act as a sediment trap may have decreased over time and during periods of high-inflow most sediment may be trans ported through the reservoir and deposited farther downstream (Juracek, 2006). Angelo and others (2007) studied mussels in the Spring River and determined that the number of species downstream from the heavily mined areas in the TSMD was considerably less than the number of species upstream from the mining areas. This decrease in species richness also corresponded to elevated concentrations of cadmium, lead, and zinc in the water, sediment, and tissue samples. Tar Creek, a tributary to the Neosho River, drains the historically most productive mining area of the TSMD near Picher, Oklahoma (Andrews and others, 2009). Andrews and others (2009) collected lakebed, streambed, and flood-plain sediments and (or) stream water samples at 30 sites in the Spring and Neosho River Basins and the Grand Lake O' the Cherokees from 2000 to 2006. Of all the water samples col lected from the study, samples from Tar Creek had the highest concentrations of cadmium, lead, manganese, and zinc. Tar Creek also had the highest concentrations of cadmium, iron, lead, manganese, and zinc in streambed-sediment samples col lected for the study. Juracek and Becker (2009) collected cores from five locations in the Grand Lake O' the Cherokees to look at trends in the deposition of lead, zinc, cadmium, and other selected constituents. Concentrations of cadmium and lead in the core samples were typically less than the CPEC (MacDonald and others, 2000). Concentrations were also less than the TPECs (Ingersoll and others, 2009) of 11.1 mg/kg for cadmium and 150 mg/ kg for lead. In contrast, zinc concentrations typically exceeded the CPEC of 459 mg/kg but were less than the TPEC of 2,083 mg/kg. Using the activity of cesium-137, Juracek and Becker (2009) were able to identify layers of sediment depos ited earlier than 1954 and noticed an initial spike in concentra tions of lead and zinc after 1964 and then a general decrease in concentrations in the depositional material beginning in the 1980s. McDonald and others (2010) conducted an advanced screening level ecological risk assessment (SLERA) of aquatic habitats in streams within and draining the TSMD. The SLERA consisted of a screening level ecological risk assessment to aquatic organisms and a detailed ecological risk assessment to benthic invertebrates to provide risk manag ers with additional information for identifying contaminant sources in streams, evaluating candidate source control mea sures, and assessing other risk management options. Of the 1,162 sampling sites, 566 (49 percent) posed moderate or high risks to benthic invertebrate communities from contaminants of potential concern (COPCs) in the TSMD. The primary COPCs identified in sediment were metals, polycyclic aro matic hydrocarbons (PAHs), and butyl benzyl phthalate. Most sediment samples that posed moderate to high risk to benthic invertebrates were identified along about the lower 20 mi of Center Creek, the lower 18 mi of Turkey Creek, the lower 20 mi of Shoal Creek, and the lower 8-10 mi of Tar Creek. Sediments with moderate risk to benthic invertebrates also were present along most of the Spring River from its mouth at the Neosho River upstream to at least the mouth of Center Creek. The effect of past mining activities is not limited to aquatic animals. Van der Merwe and others (2011) determined that migratory Canada geese (branta canadensis) collected in the TSMD had elevated concentrations of lead and zinc in their tissue. In their study, four to eight apparently healthy Canada geese, primarily young of the year goslings and adults, were collected from four sites with known mine-waste con tamination and one reference site with no known contamina tion and were examined for metal poisoning. The geese from the mine-waste contaminated sites showed decreased activity of ALA-D that corresponded with elevated lead concentrations
6 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District in tissue samples. Geese at one of the contaminated sites also demonstrated signs of zinc poisoning in the form of fibrosis and vacuolization of the pancreas, which also corresponded with elevated pancreatic zinc concentrations. Juracek (2013) expanded upon his 2009 study by focus ing on the presence of mining related lead and zinc in the flood plains of the Spring River and its tributaries in Cherokee County, Kans. Juracek (2013) identified the flood plain using USGS 1:24,000-scale topographic quadrangle maps. The 2013 study indicated that surficial soils in the Spring River flood plain generally had lead and zinc concentrations that were less than the CPECs, and the concentrations that exceeded the CPECs were restricted to the flood plain of tributary streams. Concentrations that exceeded the CPEC or the TPEC were generally within the upper 2 ft of soil, or more frequently within the upper 6 inches (in.) of soil. Concentrations of lead and zinc in the surficial soil samples in the Spring River flood plain tended to decrease with increasing distance downstream and with increasing distance from the channel—the largest concentrations were generally present near the stream chan nel. Surficial soils in tributaries with very little mined areas had concentrations of lead and zinc that were substantially less than the CPEC and TPEC. Tributaries with extensive leadand zinc-mined areas had concentrations of lead and zinc in surficial soils that frequently or typically exceeded the CPEC and TPEC. Methodology The large area of the TSMD required an array of methods for collecting samples from the stream channels along selected stream reaches and adjacent flood plains. The initial approach was to identify a representative reach along each stream that would be studied, and this selected reach would include several geomorphic channel units such as riffle, run, and pool. Several possible study sites along each stream were identified, but during an initial field reconnaissance of the area, land owner permission to access was not granted at most proposed study sites. Alternative study sites were selected that often were shorter in length and contained fewer geomorphic chan nel features. In an effort to provide more spatial data on depth of mine-waste contaminated sediments along each stream, additional study locations focusing on gravel bars were added along each stream. Collection of channel sediments focused primarily on gravel bars, and the thickness of sediments was determined using various coring techniques and a tile probe. Site Selection Five streams in the TSMD were selected for study: Center Creek, Turkey Creek, Shoal Creek, Tar Creek, and the Spring River. These streams were selected because they drain mined areas, are spatially distributed across the TSMD, and have a range of drainage areas—Turkey Creek (46 mi2), Tar Creek (53 mi2), Shoal Creek (251 mi2), and Center Creek (300 mi2). The Spring River has a drainage area of about 2,422 mi2 at the downstream-most sampling site near Baxter Springs, Kans., but the overall drainage area at its mouth at the Grand Lake O' the Cherokees is 2,590 mi2. Study reaches, flood plains, and gravel bar sites were identified using Natural Resources Conservation Service (NRCS [1938]), U.S. Department of Agriculture (2010), and Earth™ (2011) aerial imagery and NRCS Soil Survey Geographic Database [SSURGO (NRCS, 2003)] maps. After possible study reaches (overall length of stream that was studied) and sites (sections of the stream consisting of 1 or 2 gravel bars and [or] an adjacent flood plain) were chosen, the corresponding flood plain was identified using SSURGO maps by identifying soils that were classified as "frequently flooded," where the probability of flooding in any year is greater than 50 percent, or "occasionally flooded," where the probability of flooding in any year is 5 to 50 percent (Natural Resources Conservation Service, 2003). Flood-plain sites along Spring River and its tributaries selected by Jura cek (2010) were also located in soils that were classified as "frequently flooded" or "occasionally flooded," indicating that both methods were comparable. Once these sites were identi fied, landowner permission to access the gravel bars and flood plains was pursued. Site identifiers were chosen for locations on the streams that had 1 to 2 gravel bars in proximity to one another. In the case of Center Creek and Turkey Creek, the flood-plain samples were near site C2 (Center Creek) and sites TC2 and TC3 (Turkey Creek; fig. 1). The site identifiers used the first letter of the stream and the number of its order from downstream in relation to other sites on the stream. Two letters from the stream name were used in case the first letters of the two stream names were identical. For example, site C2 is on Center Creek and it is the second upstream site from the mouth of Center Creek. Site TR1 is the first upstream site on Tar Creek from the mouth. Site identifiers with "FP" in the identifier indicated flood-plain cores with the exception of Center Creek and Turkey Creek, which were both intensive study areas and the flood-plain transects were part of the gravel bar transects. For example, site C2 contained gravel bar-sediment samples and flood-plain samples. Flood-plain samples were collected from several cores located along one or two transects approximately perpendicular to the stream either on one side of the stream or on both sides depending on the flood-plain location and accessibility. Transects were used to describe the linear placement of core holes across the flood plain and gravel bar used to characterize the metal concentra tions spatially both at depth and horizontally across the flood plain from the lowest elevation near the stream channel to its highest elevation based on flooding frequency. Additional cores were collected in locations that were not along the floodplain transects but were at features of interest, such as old channels or low-lying areas, that could be areas of preferential deposition. These additional flood-plain samples were given the prefix "FB" to indicate a possibly biased flood-plain bor ing. Because the Spring River flood plain had already been
Methodology 7 sampled by Juracek (2013), no flood-plain cores were col lected from the Spring River flood plain. Two stream sites, one on the lower part of the reach of Center Creek and one on the lower part of the reach of Turkey Creek, were selected for more intensive study. These were sites C1 and C2 on Center Creek and sites TC1, TC2, and TC3 on Turkey Creek (fig. 1). A greater number of cores within the channel and on the adjacent flood plain were collected at these intensive sites compared to other sites along the streams. Also, additional gravel bars were sampled upstream from these two intensive study sites to provide further information on the spatial variability of metal concentrations within the stream channel. Because of difficulty obtaining access, intensive study sites were not located along Tar Creek, Shoal Creek, or Spring River. A complete list of channel-sediment sample and flood-plain sample locations can be found in tables 1 and 2, respectively. Sample Collection This section presents the details of the sampling methods used to collect both channel-sediment samples and flood-plain sediment samples. A detailed field log was made for each flood plain and channel sediment core and sample by a hydrologist during the sample collection. The general sedimentological description of sample, method description, general remarks, and core recovery was noted on each log. Each log also included a detailed field sketch of the gravel bar, wetted chan nel, and (or) flood plain. A chain of custody (COC) was filled out for every flood-plain core and channel-sediment sample collected. The COC noted the general handling procedures, location, and persons in custody of the samples as they were transported from the field to the USGS Rolla, Mo., office or USFWS office for handheld x-ray fluorescence (XRF) analysis by USFWS personnel. Stream Channel Gravel bar-sediment samples required different methods based on cohesion, depth, and grain-size distribution of the sediments. Shallow samples on gravel bars (<2 ft deep and above the water surface) were collected using a shovel and a small hand scoop. A hole was typically dug to the target depth with a shovel. The disturbed sediment on the sides of the hole was carefully cleared away to expose the undisturbed sedi ment. A plastic hand scoop was then used to scoop up a sam ple of undisturbed sediment from the all exposed 1-ft intervals. Care was taken to avoid sampling near areas that could contain float from shallower depths. The channel-sediment sample was then placed directly in double plastic bags that were marked with the date, time, depth interval, and coring location identi fier. The plastic scoop was rinsed with deionized water after each use to prevent cross contamination between the samples. Gravel bars with a surface 3 to 6 ft above the water level of the stream were typically excavated to the maximum depth above the saturation zone with a tractor-mounted bucket if the gravel bar was accessible by heavy equipment, and then samples were collected as described above. If the gravel bar was not accessible by heavy equipment, then samples from above the water surface were collected by digging a hole with a shovel as described above. A traditional method for sediment sampling is to collect core samples using a heavy walled sampler such as the splitspoon sampler or the piston sampler (Coduto, 1999). Loose, saturated sediment may fall from these samplers as they are removed from the subsurface (Murphy and Herkelrath, 1996). Further difficulties are encountered when sampling in coarsegrained sediments. Because of its high friction, sand and fine gravel can create a plug within the sampler during collection, which can prevent material from completely feeding into the sampler. Granular material larger than the opening of the sam pler can block the opening and prevent sediment from feeding into to tube (Zapico and others, 1987). Zapico and others (1987) used a piston sampler to collect saturated cohesionless sands and gravels to depths up to approximately 110 ft and reported a mean recovery rate of 88 percent. The researchers suspected that the presence of cobble-sized material may have been responsible for the reduced recovery rate. Because of the great volume of coarse-grained material found in streams of the TSMD, this study used a combination of traditional and experimental methods to obtain gravel bar-sediment samples. Most of the gravel bar-sediment samples were collected by using the freeze-core method (Smith and Barr, USGS, writ ten commun., 2015; Smith, 2013; Smith and Elmore, 2013) with a truck- or tractor-mounted Geoprobe™ direct-push soil probe to mechanically force the freeze-core sampler into the subsurface and retrieve it. Many of the gravel bars in the TSMD are fine grained material mixed with cobble and boul der-size material, which can cause poor core recovery with traditional core methods. The saturated sediment in TSMD streams has little or no cohesion and can quickly fall from the traditional sampler as it is removed from the subsurface. A freeze-core bit was fabricated at the USGS Missouri Water Science Center (fig. 2) and has been successfully used to collect vertical profiles of sediments from other mine-waste contaminated streams (Smith and Barr, USGS, written com mun., 2015). Early designs used by Lisle and Eads (1991) recommended a simple hand-driven hollow rod to freeze sedi ments in gravels used by salmon spawning. The design used for the TSMD study was a 1-ft long freeze-core sampler fabri cated from Geoprobe™ 1.25-in. drive rods with ½-in. verti cal steel fins along the outside, which has a gross diameter of 2.25 in. (fig. 2). Large material is pushed aside by the sampler as it is driven to the desired depth. Fine grain material is then frozen alongside the sampler between the fins. The fins also protect the frozen sample from scraping against large mate rial as the rods are pulled from the subsurface. Performance and quality assurance testing of the freeze-core sampler were discussed in Smith (2013) and Smith and Elmore (2013). The freeze-core sampler was attached to a 4-ft section of hollow drive rod and driven into the sediment mechanically
8 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Table 1. Sediment core and sample locations, depth of water from the surface and maximum sample depth at each location, maximum depth of sediment exceeding the consensus probable effects concentration and the Tri-State Mining District specific probable effects concentration, and the percent depth of sediment exceeding the general probable effects concentration and the Tri-State Mining District specific probable effects concentration for Center Creek, Turkey Creek, Shoal Creek, Tar Creek, and Spring River in the Tri-State Mining District, 2011-12. [DDMMSS, degrees, minutes, seconds; mm/dd/yyyy, month, day, year; , hours, minutes; ft, foot; CPEC, probable effects concentration (MacDonald and others, 2000); TPEC, Tri-State Mining Disctrict specific probable effects concentration (Ingersoll and others, 2009); GB, gravel bar; —, no data; WC, wetted channel; all coordinates are referenced in the World Geodetic System 1984] Coring or sample identifier Latitude (DDMMSS) Longitude (DDMMSS) Date (mm/dd/yyyy) Time () Gravel bar or wetted channel Site identifier Depth of water below the surface at coring or sample location (ft) Maximum sediment deptha (ft) Maximum depth of sediment exceeding the CPEC (ft) Maximum depth of sediment exceeding the TPEC (ft) Percent depth of sediment exceeding the CPEC Percent depth of sediment exceeding the TPEC Center Creek CTR-CH-1 11/02/2011 GB CTR-CH-2 11/02/2011 GB CTR-CH-3 11/02/2011 GB CTR-CH-4 11/03/2012 GB CTR-GB-1 11/03/2011 — GB CTR-WC-1 11/02/2012 WC CTR-WC-2 11/02/2012 WC CTR-CH-5 11/04/2011 GB CTR-CH-6 11/04/2011 GB CTR-CH-7 11/04/2011 GB CTR-WC-3 11/04/2011 WC CTR-WC-4 11/04/2011 WC CC-A-HD1 05/12/2012 GB CC-A-HD2 05/12/2012 GB CC-D-HD1 06/07/2012 GB CC-D-HD2 06/07/2012 GB CC-D-WC1 06/07/2012 GB CC-C-HD1 06/05/2012 GB CC-C-HD2 06/05/2012 — GB CC-C-WC1 06/07/2012 GB CC-B-HD1 05/15/2012 GB CC-B-HD2 05/15/2012 GB CC-B-HS1 05/15/2012 — GB CC-B-HS2 05/15/2012 — GB
Methodology 9 Table 1. Sediment core and sample locations, depth of water from the surface and maximum sample depth at each location, maximum depth of sediment exceeding the consensus probable effects concentration and the Tri-State Mining District specific probable effects concentration, and the percent depth of sediment exceeding the general probable effects concentration and the Tri-State Mining District specific probable effects concentration for Center Creek, Turkey Creek, Shoal Creek, Tar Creek, and Spring River in the Tri-State Mining District, 2011-12.—Continued [DDMMSS, degrees, minutes, seconds; mm/dd/yyyy, month, day, year; , hours, minutes; ft, foot; CPEC, probable effects concentration (MacDonald and others, 2000); TPEC, Tri-State Mining Disctrict specific probable effects concentration (Ingersoll and others, 2009); GB, gravel bar; —, no data; WC, wetted channel; all coordinates are referenced in the World Geodetic System 1984] Coring or sample identifier Latitude (DDMMSS) Longitude (DDMMSS) Date (mm/dd/yyyy) Time () Gravel bar or wetted channel Site identifier Depth of water below the surface at coring or sample location (ft) Maximum sediment deptha (ft) Maximum depth of sediment exceeding the CPEC (ft) Maximum depth of sediment exceeding the TPEC (ft) Percent depth of sediment exceeding the CPEC Percent depth of sediment exceeding the TPEC Turkey Creek TKC-CH-5 06/21/2012 GB TC1 TKC-CH-5P 06/20/2015 GB TC1 TKC-CH-6 06/21/2012 GB TC1 TKC-CH-7 06/20/2012 GB TC1 TKC-WC-3 06/21/2012 WC TC1 TKC-CH-4 06/20/2012 GB TC2 TKC-CH-1 06/19/2012 GB TC3 TKC-CH-2 06/19/2012 GB TC3 TKC-CH-3 06/19/2012 GB TC3 TKC-WC-1 06/19/2012 WC TC3 TC-D-HD1 06/06/2012 GB TC4 TC-D-HD2 06/06/2012 GB TC4 TC-B-HD1 05/16/2012 GB TC6 TC-B-HD2 05/16/2012 GB TC6 TC-C-HD1 05/16/2012 GB TC6 TC-C-HD2 05/16/2012 GB TC6 TC-C-HS1 05/16/2012 GB TC6 TC-E-HD1 06/06/2012 GB TC5 TC-E-HD2 06/06/2012 GB TC5 TC-E-HD3 06/06/2012 GB TC5 TC-E-WC1 06/07/2012 WC TC5 TC-A-HD1 05/15/2012 GB TC7 TC-A-HD2 05/15/2012 GB TC7
10 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Table 1. Sediment core and sample locations, depth of water from the surface and maximum sample depth at each location, maximum depth of sediment exceeding the consensus probable effects concentration and the Tri-State Mining District specific probable effects concentration, and the percent depth of sediment exceeding the general probable effects concentration and the Tri-State Mining District specific probable effects concentration for Center Creek, Turkey Creek, Shoal Creek, Tar Creek, and Spring River in the Tri-State Mining District, 2011-12.—Continued [DDMMSS, degrees, minutes, seconds; mm/dd/yyyy, month, day, year; , hours, minutes; ft, foot; CPEC, probable effects concentration (MacDonald and others, 2000); TPEC, Tri-State Mining Disctrict specific probable effects concentration (Ingersoll and others, 2009); GB, gravel bar; —, no data; WC, wetted channel; all coordinates are referenced in the World Geodetic System 1984] Coring or sample identifier Latitude (DDMMSS) Longitude (DDMMSS) Date (mm/dd/yyyy) Time () Gravel bar or wetted channel Site identifier Depth of water below the surface at coring or sample location (ft) Maximum sediment deptha (ft) Maximum depth of sediment exceeding the CPEC (ft) Maximum depth of sediment exceeding the TPEC (ft) Percent depth of sediment exceeding the CPEC Percent depth of sediment exceeding the TPEC Shoal Creek SH-CH-11 07/09/2012 GB S1 SH-WC-3 07/09/2012 WC S1 SH-CH-8 07/30/2012 GB S2 SH-CH-9 07/30/2012 GB S2 SH-CH-7 07/11/2012 GB S3 SH-CH-5 07/12/2012 GB S3 SH-WC-2 07/12/2012 WC S3 SH-CH-1 07/31/2012 GB S4 SH-CH-2 07/31/2012 GB S4 SH-WC-1 07/12/2012 WC S4 SC-A-HD1 05/17/2012 GB S5 SC-A-HD2 05/17/2012 GB S5 Tar Creek TAR-12-HC1 07/28/2011 WC TR1 TAR-11-HC1 07/27/2011 GB TR2 TAR-TR-11 07/14/2011 GB TR2 TAR-TR-5 07/13/2011 GB TR3 TAR-4-HC1 07/28/2011 GB TR4 TAR-TR-4 07/13/2011 GB TR4 TAR-3-HP1 07/28/2011 GB TR5 TAR-TR-3 07/13/2011 GB TR5 TAR-TR-3A 07/12/2011 GB TR5 TAR-TR-2 07/13/2011 GB TR6
Methodology 11 Table 1. Sediment core and sample locations, depth of water from the surface and maximum sample depth at each location, maximum depth of sediment exceeding the consensus probable effects concentration and the Tri-State Mining District specific probable effects concentration, and the percent depth of sediment exceeding the general probable effects concentration and the Tri-State Mining District specific probable effects concentration for Center Creek, Turkey Creek, Shoal Creek, Tar Creek, and Spring River in the Tri-State Mining District, 2011-12.—Continued [DDMMSS, degrees, minutes, seconds; mm/dd/yyyy, month, day, year; , hours, minutes; ft, foot; CPEC, probable effects concentration (MacDonald and others, 2000); TPEC, Tri-State Mining Disctrict specific probable effects concentration (Ingersoll and others, 2009); GB, gravel bar; —, no data; WC, wetted channel; all coordinates are referenced in the World Geodetic System 1984] Coring or sample identifier Latitude (DDMMSS) Longitude (DDMMSS) Date (mm/dd/yyyy) Time () Gravel bar or wetted channel Site identifier Depth of water below the surface at coring or sample location (ft) Maximum sediment deptha (ft) Maximum depth of sediment exceeding the CPEC (ft) Maximum depth of sediment exceeding the TPEC (ft) Percent depth of sediment exceeding the CPEC Percent depth of sediment exceeding the TPEC Tar Creek—Continued TAR-TR-1 07/13/2011 GB TR7 TAR-TR-10b 07/14/2011 GB TR8 TAR-6-VC1 07/27/2011 GB TR9 TAR-TR-6b 07/14/2011 GB TR9 TAR-TR-7b 07/14/2011 GB TR10 TAR-9-PT1 07/27/2011 GB TR11 TAR-9-VC1 07/27/2011 GB TR11 TAR-9-VC1A 07/27/2011 GB TR11 TAR-BAR-1 08/10/2011 GB TR11 TAR-TR-9b 07/14/2011 GB TR11 TAR-8-VC1 07/27/2011 GB TR12 TAR-TR-8b 07/14/2011 GB TR12 Spring River SR-CH-1 08/01/2012 GB SR1 SR-CH-2 08/01/2012 GB SR1 SR-CH-3 08/01/2012 GB SR1 SR-CH-4 08/02/2012 GB SR2 SR-CH-5 08/02/2012 GB SR2 aThe maximum depth of recovery, which is equal to the refusal of the sampler. bThe maximum depth of the core or sample and the maximum depth differ due to the collection of shallow core or samples paired with tile probe sounding to determine the maximum depth at these locations.
12 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Table 2. Flood-plain core and sample locations, maximum depth or core at each location, maximum depth of core exceeding the consensus probable effects concentration and the Tri-State Mining District-specific probable effects concentration, and the percent depth of core exceeding the general probable effects concentration and the Tri-State Mining District specific probable effects concentration for the flood plains of Center Creek, Turkey Creek, Shoal Creek, and Tar Creek in the Tri-State Mining District, 2011-12. [DDMMSS, degrees, minutes, seconds; mm/dd/yyyy, month, day, year; , hours, minutes; ft,foot; CPEC, concensus probable effects concentration (Mac Donald and others, 2000); TPEC, Tri-State Mining Disctrict specific probable effects concentration (Ingersoll and others, 2009); —, no data; all coordinates are referenced in the World Geodetic System 1984] Coring or sample identifier Latitude (DDMMSS) Longitude (DDMMSS) Date (mm/dd/yyyy) Time () Site identifier Maximum depth of core (ft) Maximum depth of core exceeding the CPEC (ft) Maximum depth of core exceeding the TPEC (ft) Percent depth of core exceeding the CPEC Percent depth of core exceeding the TPEC Center Creek CTR-FB-1 11/05/2011 CTR-FB-2 11/05/2011 CTR-FP-1 11/08/2011 CTR-FP-2 11/08/2011 CTR-FP-3 11/08/2011 CTR-FP-4 11/01/2011 CTR-FP-5 11/01/2011 — Turkey Creek TKC-FB-1 06/18/2012 TC3 TKC-FB-2 06/19/2012 TC1 TKC-FP-1 06/18/2012 TC2 TKC-FP-2 06/18/2012 TC2 TKC-FP-3 06/18/2012 TC2 TKC-FP-4 06/19/2012 TC3 Shoal Creek SH-FB-1 07/10/2012 S4 SH-FB-2 07/10/2012 SFP2 SH-FB-3 07/10/2012 SFP2 SH-FB-4 07/31/2012 S4 SH-FP-1 07/10/2012 SFP1 SH-FP-2 07/10/2012 SFP1 SH-FP-3 07/10/2012 SFP1 SH-FP-4 07/10/2012 SFP1 Tar Creek TAR-FB-1 08/09/2011 TRFP2 TAR-FB-2 08/09/2011 TRFP2 TAR-FB-3 08/09/2011 TRFP2 TAR-FB-4 08/10/2011 TR11 TAR-FP1-1 08/09/2011 TRFP1 TAR-FP1-2 08/09/2011 TRFP1 TAR-FP1-3 08/09/2011 TRFP1 TAR-FP1-4 08/09/2011 TRFP1 TAR-FP2-1 08/09/2011 TRFP2 TAR-FP2-2 08/09/2011 TRFP2
Methodology 13 Table 2. Flood-plain core and sample locations, maximum depth or core at each location, maximum depth of core exceeding the consensus probable effects concentration and the Tri-State Mining District-specific probable effects concentration, and the percent depth of core exceeding the general probable effects concentration and the Tri-State Mining District specific probable effects concentration for the flood plains of Center Creek, Turkey Creek, Shoal Creek, and Tar Creek in the Tri-State Mining District, 2011-12.— Continued [DDMMSS, degrees, minutes, seconds; mm/dd/yyyy, month, day, year; , hours, minutes; ft,foot; CPEC, concensus probable effects concentration (Mac Donald and others, 2000); TPEC, Tri-State Mining Disctrict specific probable effects concentration (Ingersoll and others, 2009); —, no data; all coordinates are referenced in the World Geodetic System 1984] Coring or sample identifier Latitude (DDMMSS) Longitude (DDMMSS) Date (mm/dd/yyyy) Time () Site identifier Maximum depth of core (ft) Maximum depth of core exceeding the CPEC (ft) Maximum depth of core exceeding the TPEC (ft) Percent depth of core exceeding the CPEC Percent depth of core exceeding the TPEC Tar Creek—Continued TAR-FP2-3 08/09/2011 TRFP2 TAR-FP2-4 08/09/2011 TRFP2 TAR-FP2-5 08/09/2011 TRFP2 Figure 2. Freeze-core sampler with attached frozen sediment sample immediately after recovery and the freeze-core sampler with scale (Smith and Elmore, 2013).
14 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District by the Geoprobe™ hammer or by hand using a 15-pound (lb) fence-post driver at locations not accessible to heavy equip ment. Once the sampler was driven to the required depth, 0.125-in. stainless steel tubing was inserted into the driving rods until the opening of the tubing was even with the cen ter of the freeze-core sampler. The tubing was attached to a tank of liquid carbon dioxide (CO2). The tank had an internal siphon tube that draws liquid from the bottom of the tank, ensuring that liquid CO2 was released and not gaseous CO2. This was also accomplished using a tank without a siphon tube by inverting the tank. It was important to release the liquid CO2 near the center of the sampler because the evaporation of the liquid was instantaneous. The endothermic reaction absorbed heat energy, which cooled the sampler and the sur rounding saturated sediment. Liquid CO2 was injected into the sampler for 0.5-4 minutes (min) (fig. 3). The injection of CO2 was either continuous or divided up into two to three pulses with 15- to 30-second breaks. The length of time that CO2 was injected was varied based on conditions in the field and sample recovery of previous samples. The rods and sampler were removed mechanically by the Geoprobe™ or by hand using a fence-post puller (fig. 4). Once the frozen sample was removed, it was quickly rinsed with deionized water to remove loose particles that may have attached from shallower depths while the sampler was pulled upward. This rinse left a frozen core that was a representative channel-sediment sample at the depth that it was frozen. The sampler with frozen sediment was placed over a steel pan (fig. 2) and the frozen sediment was scraped into the pan with a plastic scraping tool. If needed, any remain ing attached sediment was then melted by rinsing into the pan using deionized water. The sample was then placed in double plastic bags and labeled with the date, time, depth interval, and core identification. Tar Creek lacked the cobble and boulder sized material present at the other streams and the freeze-core method often was not necessary. Shallow samples (<2 ft deep and above the water surface) were collected using a shovel and a small hand scoop similar to the other streams. Deeper channelsediment samples were collected using the vibra-core method as described by Lanesky and others (1979) to collect continu ous cores from the surface to bedrock. The vibra-core method involved vibrating a 4-in. aluminum tube into the sediment with an attached concrete mixer. Aluminum alloys generally contain trace amounts of copper, magnesium, manganese, silicon, tin, and zinc. These amounts are generally percent. The sample for analysis was taken from about a 2-in. diameter core in the center of the aluminum tube to reduce the prob ability of contamination of the sample. The vibra-core method tended to work well for sampling at Tar Creek because the sediment thickness was generally a few feet or less. Once the cores were removed from the subsurface, the excess core tube was cut off using a reciprocating saw and the ends covered in plastic and sealed with tape. The core was marked with the date, time, depth interval, core identification, and orientation. The last method used for gravel-bar sediment was a steel Geo probe™ core barrel sampler with plastic liner, typically used for collecting flood-plain samples (described in methodology subsection, "Flood plain"), was hammered into the gravel-bar sediment in gravel bars with an intermediate sediment thick ness of 1 to 2 ft. dioxide (CO Figure 3. Liquid carbon 2) injection tube inserted into the hollow driving rods during the injection of liquid CO2.
Methodology 15 Figure 4. Removal of the rods and sample by hand using a fence-post puller. The depth of refusal at each borehole (traditional core, freeze core, or vibra core) location was recorded. Refusal was assumed to be the lower vertical extent of the channel sedi ments. A tile probe was also used to verify the depth of refusal at the borehole locations as well as at other locations within the channel to provide additional information on the thickness distribution of channel sediments. The height of the gravel bar deposits above the water level of the stream at each borehole location and tile probe location was determined by measur ing the depth to water that was visible in the borehole or by measuring the height with a hand level and surveyor's rod. A complete list of tile probe locations can be found in table 3. Flood Plain Flood-plain cores were collected using a truck-mounted Geoprobe™ direct-push soil sampling unit. Traditional cor ing used a 4-ft long, 2.25-in. outside diameter core barrel to collect a 1.125-in. diameter core. After collection of each 4-ft increment, the sampler was mechanically removed from the soil. It was opened to retrieve the soil core that was inside of a clear plastic sleeve that prevented contact with the steel core barrel. Once a core was retrieved, it was measured to determine the percent recovery, which is computed by divid ing the length of recovered core by the length of the run. Plastic caps were placed on both ends of the plastic sleeve and secured with tape. The plastic sleeve was labeled with the date, time, depth interval, core identification, and orientation. A measurement was made in the open hole to verify the depth between runs and ensure that the hole did not collapse. An insert was used in the drive shoe of the core barrel to prevent soil from entering until the core barrel reached the previous sampling depth in the event that the hole collapsed. Measuring the depth of the hole ensured that the sample was representa tive of the target depth. This process was repeated after each run until the sampler met refusal. Sample Processing and Analysis The following describes the handling and processing procedures including the storage, sieving, and XRF analysis of more than 700 stream and flood-plain samples collected during this study. An XRF instrument was used to analyze all samples for the concentration of arsenic, cadmium, barium, cobalt, copper, manganese, nickel, lead, and zinc. The 2007 Thermo Niton™ XL3t 600 XRF instrument was owned by the USFWS and analyses were conducted by USFWS personnel at the USFWS office in Columbia, Missouri and the USGS office in Rolla, Missouri. The XRF instrument analyzed concentra tions for these nine MVT-related metals; however, the primary metals of concern for the project were cadmium, lead, and zinc. The XRF analysis was conducted following the U.S. Environmental Protection Agency Method 6200 (EPA, 2007) which can be used in the determination of elemental concen trations in soils and must be used with confirmatory analysis using other techniques.
16 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Table 3. Tile probe locations, depth of water from the surface, and maximum depth of refusal at each location for Center Creek, Turkey Creek, Shoal Creek, and Tar Creek in the Tri-State Mining District, 2011-12. [DDMMSS, degrees, minutes, seconds; mm/dd/yyyy, month, day, year; ft, foot; GB, gravel bar; WC, wetted channel; --, no data] Tile probe identifier Latitude (DDMMSS) Longitude (DDMMSS) Date (mm/dd/yyyy) Site identifier Gravel bar or wetted channel Depth of water below the surface (ft) Maximum depth of refusal (ft) Center Creek CC-A-TP-1 5/14/2012 GB CC-B-TP-1 5/15/2012 GB CC-B-TP-2 5/15/2012 GB CC-B-TP-3 5/15/2012 GB CC-C-WC-TP-1 6/5/2012 WC CC-C-WC-TP-2 6/5/2012 WC CC-D-TP-1 6/7/2012 GB CC-D-WC-TP-2 6/7/2012 WC CRT-GP-1 11/3/2011 GB CRT-GP-10 11/3/2011 GB CRT-GP-11 11/3/2011 GB CRT-GP-2 11/3/2011 GB CRT-GP-3 11/3/2011 GB CRT-GP-4 11/3/2011 GB CRT-GP-5 11/3/2011 GB CRT-GP-6 11/3/2011 GB CRT-GP-7 11/3/2011 GB CRT-GP-8 11/3/2011 GB CRT-GP-9 11/3/2011 GB CTR-GP-13 11/4/2011 GB CTR-GP-14 11/4/2011 GB CTR-TP-1 11/3/2011 GB CTR-TP-2 11/3/2011 GB Turkey Creek TC-A-TP-1 5/15/2012 TC7 GB TC-A-TP-2 5/15/2012 TC7 GB TC-A-TP-3 5/15/2012 TC7 GB TC-B-TP-1 5/16/2012 TC6 GB TC-B-TP-2 5/16/2012 TC6 GB TC-B-TP-3 5/16/2012 TC6 GB TC-B-TP-4 5/16/2012 TC6 GB TC-D-WC-TP-1 6/6/2012 TC4 WC TC-D-WC-TP-2 6/6/2012 TC4 WC TC-E-TP-2 6/6/2012 TC5 GB TC-E-WC-TP-1 6/6/2012 TC5 WC TKC-TP-1 6/19/2012 TC3 GB TKC-TP-2 6/19/2012 TC3 GB TKC-TP-3 6/19/2012 TC3 GB TKC-TP-4 6/20/2012 TC1 WC
Methodology 17 Table 3. Tile probe locations, depth of water from the surface, and maximum depth of refusal at each location for Center Creek, Turkey Creek, Shoal Creek, and Tar Creek in the Tri-State Mining District, 2011-12.—Continued [DDMMSS, degrees, minutes, seconds; mm/dd/yyyy, month, day, year; ft, foot; GB, gravel bar; WC, wetted channel; --, no data] Tile probe identifier Latitude (DDMMSS) Longitude (DDMMSS) Date (mm/dd/yyyy) Site identifier Gravel bar or wetted channel Depth of water below the surface (ft) Maximum depth of refusal (ft) Shoal Creek SC-A-TP-1 5/17/2012 S5 GB SC-A-TP-2 5/17/2012 S5 GB SC-A-TP-3 5/17/2012 S5 GB SC-A-TP-4 5/17/2012 S5 GB SH-WC-TP-1 7/12/2012 S4 WC Tar Creek TAR-TP-7-0 7/14/2011 TR10 WC TAR-TP-7-1 7/14/2011 TR10 WC TAR-TP-7-2 7/14/2011 TR10 WC TAR-TP-7-3 7/14/2011 TR10 WC TAR-TP-7-4 7/14/2011 TR10 WC TAR-TP-7-5 7/14/2011 TR10 WC TAR-TP-7-6 7/14/2011 TR10 WC TAR-TP-7-7 7/14/2011 TR10 GB TAR-TP-9-1 7/14/2011 TR11 GB TAR-TP-9-2 7/14/2011 TR11 GB TAR-TP-9-3 7/14/2011 TR11 GB TAR-TP-9-4 7/14/2011 TR11 GB TAR-TP-9-5 7/14/2011 TR11 WC TAR-TP-9-6 7/14/2011 TR11 WC TAR-TP-9-7 7/14/2011 TR11 WC TAR-TP-9-8 7/14/2011 TR11 WC TAR-TP-9-9 7/14/2011 TR11 WC TAR-TP-8-0 7/14/2011 TR12 GB TAR-TP-8-1 7/14/2011 TR12 GB TAR-TP-8-10 7/14/2011 TR12 GB TAR-TP-8-11 7/14/2011 TR12 GB TAR-TP-8-12 7/14/2011 TR12 GB TAR-TP-8-2 7/14/2011 TR12 GB TAR-TP-8-3 7/14/2011 TR12 WC TAR-TP-8-4 7/14/2011 TR12 WC TAR-TP-8-5 7/14/2011 TR12 WC TAR-TP-8-6 7/14/2011 TR12 GB TAR-TP-8-7 7/14/2011 TR12 GB TAR-TP-8-8 7/14/2011 TR12 GB TAR-TP-8-9 7/14/2011 TR12 GB TAR-TP-11-1 7/14/2011 TR2 WC TAR-TP-11-10 7/14/2011 TR2 WC TAR-TP-11-11 7/14/2011 TR2 WC
18 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Table 3. Tile probe locations, depth of water from the surface, and maximum depth of refusal at each location for Center Creek, Turkey Creek, Shoal Creek, and Tar Creek in the Tri-State Mining District, 2011-12.—Continued [DDMMSS, degrees, minutes, seconds; mm/dd/yyyy, month, day, year; ft, foot; GB, gravel bar; WC, wetted channel; --, no data] Tile probe identifier Latitude (DDMMSS) Longitude (DDMMSS) Date (mm/dd/yyyy) Site identifier Gravel bar or wetted channel Depth of water below the surface (ft) Maximum depth of refusal (ft) Tar Creek—Continued TAR-TP-11-12 7/14/2011 TR2 WC TAR-TP-11-13 7/14/2011 TR2 WC TAR-TP-11-14 7/14/2011 TR2 WC TAR-TP-11-15 7/14/2011 TR2 WC TAR-TP-11-2 7/14/2011 TR2 WC TAR-TP-11-3 7/14/2011 TR2 WC TAR-TP-11-4 7/14/2011 TR2 WC TAR-TP-11-5 7/14/2011 TR2 WC TAR-TP-11-6 7/14/2011 TR2 WC TAR-TP-11-7 7/14/2011 TR2 WC TAR-TP-11-8 7/14/2011 TR2 WC TAR-TP-11-9 7/14/2011 TR2 WC TAR-TP-5-0 7/13/2011 TR3 GB TAR-TP-5-1 7/13/2011 TR3 WC TAR-TP-5-10 7/13/2011 TR3 WC TAR-TP-5-11 7/13/2011 TR3 WC TAR-TP-5-12 7/13/2011 TR3 WC TAR-TP-5-13 7/13/2011 TR3 WC TAR-TP-5-14 7/13/2011 TR3 WC TAR-TP-5-15 7/13/2011 TR3 WC TAR-TP-5-16 7/13/2011 TR3 WC TAR-TP-5-2 7/13/2011 TR3 WC TAR-TP-5-3 7/13/2011 TR3 WC TAR-TP-5-4 7/13/2011 TR3 WC TAR-TP-5-5 7/13/2011 TR3 WC TAR-TP-5-6 7/13/2011 TR3 WC TAR-TP-5-7 7/13/2011 TR3 WC TAR-TP-5-8 7/13/2011 TR3 WC TAR-TP-5-9 7/13/2011 TR3 WC TAR-TP-4-0 7/13/2011 TR4 GB TAR-TP-4-1 7/13/2011 TR4 GB TAR-TP-4-10 7/13/2011 TR4 WC TAR-TP-4-11 7/13/2011 TR4 WC TAR-TP-4-12 7/13/2011 TR4 WC TAR-TP-4-2 7/13/2011 TR4 GB TAR-TP-4-3 7/13/2011 TR4 GB TAR-TP-4-4 7/13/2011 TR4 WC TAR-TP-4-5 7/13/2011 TR4 WC TAR-TP-4-6 7/13/2011 TR4 WC
Methodology 19 Table 3. Tile probe locations, depth of water from the surface, and maximum depth of refusal at each location for Center Creek, Turkey Creek, Shoal Creek, and Tar Creek in the Tri-State Mining District, 2011-12.—Continued [DDMMSS, degrees, minutes, seconds; mm/dd/yyyy, month, day, year; ft, foot; GB, gravel bar; WC, wetted channel; --, no data] Tile probe identifier Latitude (DDMMSS) Longitude (DDMMSS) Date (mm/dd/yyyy) Site identifier Gravel bar or wetted channel Depth of water below the surface (ft) Maximum depth of refusal (ft) Tar Creek—Continued TAR-TP-4-7 7/13/2011 TR4 WC TAR-TP-4-8 7/13/2011 TR4 WC TAR-TP-4-9 7/13/2011 TR4 WC TAR-TP-3-0 7/13/2011 TR5 GB TAR-TP-3-1 7/13/2011 TR5 GB TAR-TP-3-2 7/13/2011 TR5 WC TAR-TP-3-3 7/13/2011 TR5 WC TAR-TP-3-4 7/13/2011 TR5 WC TAR-TP-3-5 7/13/2011 TR5 WC TAR-TP-3-6 7/13/2011 TR5 WC TAR-TP-3-7 7/13/2011 TR5 GB TAR-TP-2-1 7/13/2011 TR6 WC TAR-TP-2-10 7/13/2011 TR6 WC TAR-TP-2-11 7/13/2011 TR6 WC TAR-TP-2-12 7/13/2011 TR6 WC TAR-TP-2-13 7/13/2011 TR6 WC TAR-TP-2-14 7/13/2011 TR6 WC TAR-TP-2-15 7/13/2011 TR6 WC TAR-TP-2-2 7/13/2011 TR6 GB TAR-TP-2-3 7/13/2011 TR6 GB TAR-TP-2-4 7/13/2011 TR6 GB TAR-TP-2-5 7/13/2011 TR6 GB TAR-TP-2-6 7/13/2011 TR6 WC TAR-TP-2-7 7/13/2011 TR6 WC TAR-TP-2-8 7/13/2011 TR6 WC TAR-TP-2-9 7/13/2011 TR6 WC TAR-TP-1-1 7/13/2011 TR7 WC TAR-TP-1-10 7/13/2011 TR7 WC TAR-TP-1-11 7/13/2011 TR7 WC TAR-TP-1-12 7/13/2011 TR7 WC TAR-TP-1-13 7/13/2011 TR7 WC TAR-TP-1-14 7/13/2011 TR7 WC TAR-TP-1-15 7/13/2011 TR7 WC TAR-TP-1-16 7/13/2011 TR7 WC TAR-TP-1-17 7/13/2011 TR7 WC TAR-TP-1-18 7/13/2011 TR7 WC TAR-TP-1-19 7/13/2011 TR7 WC TAR-TP-1-2 7/13/2011 TR7 WC TAR-TP-1-3 7/13/2011 TR7 WC
20 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Table 3. Tile probe locations, depth of water from the surface, and maximum depth of refusal at each location for Center Creek, Turkey Creek, Shoal Creek, and Tar Creek in the Tri-State Mining District, 2011-12.—Continued [DDMMSS, degrees, minutes, seconds; mm/dd/yyyy, month, day, year; ft, foot; GB, gravel bar; WC, wetted channel; --, no data] Tile probe identifier Latitude (DDMMSS) Longitude (DDMMSS) Date (mm/dd/yyyy) Site identifier Gravel bar or wetted channel Depth of water below the surface (ft) Maximum depth of refusal (ft) Tar Creek—Continued TAR-TP-1-4 7/13/2011 TR7 WC TAR-TP-1-5 7/13/2011 TR7 WC TAR-TP-1-6 7/13/2011 TR7 WC TAR-TP-1-7 7/13/2011 TR7 WC TAR-TP-1-8 7/13/2011 TR7 WC TAR-TP-1-9 7/13/2011 TR7 WC TAR-TP-10-0 7/14/2011 TR8 GB TAR-TP-10-1 7/14/2011 TR8 GB TAR-TP-10-10 7/14/2011 TR8 GB TAR-TP-10-2 7/14/2011 TR8 GB TAR-TP-10-3 7/14/2011 TR8 WC TAR-TP-10-4 7/14/2011 TR8 WC TAR-TP-10-5 7/14/2011 TR8 WC TAR-TP-10-6 7/14/2011 TR8 WC TAR-TP-10-7 7/14/2011 TR8 WC TAR-TP-10-8 7/14/2011 TR8 WC TAR-TP-10-9 7/14/2011 TR8 GB TAR-TP-6-0 7/14/2011 TR9 WC TAR-TP-6-1 7/14/2011 TR9 WC TAR-TP-6-2 7/14/2011 TR9 WC TAR-TP-6-3 7/14/2011 TR9 WC TAR-TP-6-4 7/14/2011 TR9 GB TAR-TP-6-5 7/14/2011 TR9 GB TAR-TP-6-6 7/14/2011 TR9 GB TAR-TP-6-7 7/14/2011 TR9 GB Stream Channel After collection, channel-sediment samples were allowed to air dry for several days at the USGS office in Rolla, Mo. Once the samples were dry, they were disaggregated using a stainless steel mortar and pestle. Stainless steel is an iron, chromium, and nickel alloy that may be a source of contami nation into the sample for these three elements; however, nickel varied in a manner consistent with other metal con tamination derived from the sediment, whereas contamination from the probe would tend not to vary from sample to sample. In addition, sediment sampled using other hardware also contained these elements. Vibra-core samples were opened to expose the sediment and allowed to air dry. Samples were collected from the vibra-core tube by scooping the sediment from each 1-ft interval using a plastic scoop, placed in plastic bags, and weighed. The weights were generally greater than 200 grams (g), and these samples did not require disaggrega tion. All samples were then sieved using a single 2-millime ter (mm) mesh-size stainless steel sieve (U.S. Number 10). This divided the sample into two size fractions, mm and mm. The two fractions were placed in separate plastic bags, labeled, and weighed. The <2-mm size fraction of each sample was analyzed three times using the XRF instrument. Before each individual scan, the bag was thoroughly mixed to ensure a representative scan. Each analysis was 60 seconds in dura tion, which was sufficient time to determine concentrations of the MVT-related metals (arsenic, cadmium, barium, cobalt, copper, manganese, nickel, lead, and zinc). The arithmetic mean of the three individual analyses was reported as the con centration in the sample for each constituent.
Methodology 21 Flood Plain The plastic sleeves containing flood-plain cores were cut lengthwise in the laboratory with a special core cutting knife to expose an area of the core about 1 in. wide. The outside of the core is typically disturbed during the coring process as it slides against the steel cutting head and into the core barrel. A steel knife was then used to remove a 0.25-in. thick section to expose the undisturbed core (fig. 5). This created a flat surface for the XRF that was relatively undisturbed and would be representative of the metal concentrations at that location. The core recovery was measured and the depths were marked to guide the XRF analysis. Then the core was cut into 2-ft lengths and placed in core boxes to air dry. Metal concentrations were determined using an XRF placed on the flat surface of the core previously exposed with the knife. Each 1-ft section of core was generally analyzed three times by USFWS using the XRF at the USGS office in Rolla, Mo. The original protocol was to collect XRF measurements using a 60-second analysis at three equally spaced intervals within each foot of the core and then compute the mean of these three measurements. For example, the mean of measurements at 0.25, 0.50, and 0.75 ft would represent the metal concentrations in the 0- to 1-ft depth inter val and was assigned the mean depth of 0.50 ft. After several days of XRF analysis, it was determined that metal concentra tions in flood-plain cores tended to be largest in the upper few feet then decreased to much smaller concentrations through out most of the lower sections of the cores. To expedite the analyses of hundreds of feet of core, three analyses were made each foot for the upper 3 to 5 feet of each core, and at depths greater than 5 ft, a single analysis was first done at the even foot mark. As long as the single analysis at the even foot mark indicated relatively low concentrations of zinc (less than about one-half the CPEC), analysis proceeded at 1-ft intervals down the core. If, for example, the single analysis indicated a zinc concentration greater than one-half the CPEC at 6 ft, then three analyses at the 6.25-, 6.50-, and 6.75-ft intervals were done and the mean calculated to represent the metals concentrations in the 6- to 7-ft intervals. Such a mean concentration was reported for the assigned mean depth of 6.5 ft. Additional measures were taken during the analysis of the 379 core sections to expedite the results for the floodplain cores. A 60-second analysis using the XRF is required to determine the concentrations for arsenic, cadmium, barium, cobalt, copper, manganese, nickel, lead, and zinc. A 30-second analysis can be used determine the concentrations of the same metals with the exception of cadmium and barium. During the analysis of the flood-plain cores, the analysis time was reduced from 60 seconds to 30 seconds for 211 core sections (samples). Laboratory Confirmation Samples Eighty-five stream channel and flood-plain sediment samples were split and submitted for laboratory analysis to evaluate the accuracy of the concentrations obtained by the XRF instrument which is required when using EPA method 6200 (EPA, 2007). Samples sent to the laboratory were selected to ensure spatial coverage of each stream segment and to represent a range of lead and zinc concentrations. Of the 355 stream channel samples, 76 were sent for laboratory confirma tion. Nine samples from the 34 flood-plain borings (379 total samples) were selected for laboratory confirmation. Most of the flood-plain samples selected were within the top few feet of the boreholes where the XRF detected larger concentrations of lead and zinc. Figure 5. Flood-plain core that has been prepared for analysis with the x-ray fluorescence instrument.
22 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Laboratory splits from the <2-mm size fraction of stream channel samples that had been previously prepared and analyzed by the XRF were prepared by removing 3 to 5 g of sample from the original sample using a plastic spatula and placing it in a separate bag. Before the split sample was collected, the sample bag was mixed by turning the sample bag over 10 to 15 times then opening the bag and passing the spatula though the entire thickness of the mixed sample. Only one to three passes through the original sample were required to obtain the split sample. The laboratory confirmatory samples for the flood-plain core samples required additional processing because the origi nal XRF analyses were made on the intact core. The 1-ft inter val selected for laboratory confirmation was removed from the plastic liner, disaggregated and sieved using a 2-mm stainless steel sieve, and the material finer than 2 mm was weighed before placing in a plastic bag. The laboratory confirmatory samples were then split from the bagged material in the same manner as described above for stream channel samples. Before submitting the split samples to the laboratory, each split sam ple (stream channel or flood-plain core) was analyzed again using the XRF to provide a more direct comparison between the XRF and laboratory analytical results. Split samples were shipped to the USGS Central Mineral and Environmental Resources Science Center (CMERSC) laboratory in Denver, Colorado. The laboratory analyzed the split samples using inductively coupled plasma-atomic emission spectrometry (ICP-AES) and inductively coupled plasma-mass spectrometry (ICP-MS) methods on samples that were completely digested (Taggart, 2002). The laboratory reported concentrations for 43 constituents, 9 of which were also analyzed by XRF for this study. Concentration of metals in a sample detected through laboratory analysis through the complete digestion of the sam ple does not completely reflect the typical digestion process in aquatic organisms or the true bioavailability of the metals found in the sediment. The strength of stomach acids tend to vary based on diet. Beasley and others (2015) have shown that stomach acid pH lowers with the risk of food-borne pathogen exposure. Scavengers tend to have lower stomach pH than carnivores, and carnivores tend to have lower stomach acid pH than herbivores. Lower stomach acid pH can result in greater metal bioavailability by increasing metal solubility (Luoma, 1989). Beasley and others (2015) reported scavenger birds with stomach acid pH ranging from 1.1 to 1.7. There are also many other factors that affect the bioavailability of metals, including metal concentrations, solute metal speciation, metal concentration in food, metal partitioning among ligands within food, influence of other cations, temperature, and redox poten tial (Louma, 1983). Estimation of the Volume of Contaminated Gravel Bar Deposits Sullivan and others (1987) indicate that most of the readily available sediment is found in gravel bars for large to moderate streams and characterization of gravel-bar sediments in this study focused on gravel bars with some additional samples collected from the wetted channel. Estimates of the volume of contaminated gravel bar deposits were computed relative to two benchmarks of contamination (that is, for both PEC values [CPEC and TPEC]) because of the importance of such information to the USFWS and other natural resource agencies of the TSMD for assessing damage to the ecosystem and evaluating restoration alternatives. The maximum depth of contamination was determined as the maximum depth where either the lead or zinc concentration exceeded the respective PEC values. The data files showing maximum sample depth at each location are listed in the Stream channel sediment sam ples dataset (Smith, 2016). Cadmium concentrations were not used to determine contaminated sediment depths because the limit of detection (LOD) for cadmium from the XRF analysis (12 mg/kg) was larger than the cadmium PECs: CPEC (4.98 mg/kg) and TPEC (11.1 mg/kg). Thus, no sample analyzed by XRF could be determined with certainty from any depth to have a cadmium concentration below either PEC value. Occasionally, the concentration of lead or zinc would exceed either the CPEC or the TPEC at one depth, but not exceed either at the next depth (or several subsequent depths), and then would exceed again at an even greater depth. For example, the concentration of lead exceeds both the CPEC and the TPEC at 4-5 ft. The concentration of lead then does not exceed either the CPEC or the TPEC at 5-8 ft but then does exceed the CPEC and the TPEC at 8-9ft. The maximum depth of contamination was reported as the deepest CPEC or TPEC exceedance in this case 9 ft, and it was assumed that the distance between the land surface and the maximum contami nated depth represented the depth of excavation required to remediate the contaminated sediment, despite the fact that part or all of the sediment above may not actually have been classi fied as contaminated per the CPEC or TPEC. Two measures were required to estimate the volume of contaminated sediment in Center Creek, Turkey Creek, Shoal Creek, and Tar Creek in the reaches studied: (1) the depth of contaminated sediment in the study reach and (2) the areal extent of contaminated sediment in the study reach. Estimates of the volume of contaminated sediment along the Spring River could not be made because of the small number of loca tions sampled. To determine the depth of contaminated sedi ment in the study reach, a six-step procedure was used: D1. Determine the maximum depth for each borehole that exceeded either the CPEC or the TPEC, or both, for lead and zinc (Smith, 2016; Stream channel sediment samples; table 1) D2. Express the maximum depth (from D1 above) of con tamination (relative to each PEC type) as a proportion
Quality Control and Quality Assurance 23 of the investigation depth in each borehole (maximum contaminated sediment depth in core divided by total depth represented by recovered core), expressed as a percentage. The investigation sample depth at each location is listed in the Flood-plain cores dataset (Smith, 2016). D3. Determine the mean depth of the sediment at each indi vidual site (mean value of borehole refusal depths and tile probe refusal depths for each site; table 4) D4. Determine the mean maximum proportional depth of contamination for each site (compute the mean of D2 above), expressed as a percentage, for the CPEC and TPEC (table 4) D5. Determine the mean maximum depth of sediment ex ceeding the CPEC or TPEC for each site (multiply mean maximum proportional depth of contamination [from D4 above] by the mean depth of sediment in each gravel bar [from D3 above]) (table 4) D6. Determine the overall mean of the site-mean depths of contaminated sediment for each study site (tables 4 and 5, mean value for stream) To determine the areal extent of contaminated sedi ment sampled in the study reach, a two-step procedure was followed: A1. Determine the planimetric area of each gravel bar within the studied reach. EarthTM aerial george ferenced orthophotography from 2012 (Center Creek, Turkey Creek, and Shoal Creek) and 2015 (Tar Creek) was used to identify and delineate the gravel bars that were digitized at the nominal scale of 1:2000 into a geographic information system (GIS). Comparison of more recent aerial photographs to 1930s aerial photo graphs also was done to identify persistent bars, areas of stream channel migration, and bars that were partially vegetated on the more recent photographs. For example, a gravel bar may experience recent growth of vegeta tion, which can hide the overall size of the bar. This can be identified using older aerial photography. A2. Determine the total area of contaminated sediment by summing the areas of each individual gravel bar for the selected study reach of each stream (fig. 1). There were sites located outside of the reaches selected for the estimation of the volume of contaminated sediment (site C6 in Center Creek and site S5 in Shoal Creek; fig. 1). These sites had distances of 7.5 mi (Center Creek) and 10 mi (Shoal Creek between these sites and the closest downstream site so volume estimates were not calcu lated for these reaches. The volume of contaminated gravel bar sediment along the sampled reaches of Center Creek, Turkey Creek, Shoal Creek, and Tar Creek was estimated by multiplying the total areal extent of gravel bars along each studied reach by the mean maximum depth of contaminated sediment in gravel bars along that studied reach that exceeded the CPEC or the TPEC (D6 times A2 above; table 4). Estimated volumes of sediment in gravel bars in the study reaches exceeding the CPEC and TPEC presented in this report should be considered minimum volumes because they are only based on lead and zinc concentrations in the sampled gravel bars. Because the XRF LOD was greater than the PECs for some other constituents, particularly cadmium and nickel concentrations, other constituents could have exceeded the PECs, which could potentially have changed the maxi mum depths of contaminated sediment that were determined from the lead and zinc concentrations. In addition, there are many other gravel bars within the study reaches that were not sampled, in addition to sediment beneath other channel fea tures such as in pools and riffles, which were not sufficiently characterized. Finally, the estimated volume of contaminated sediment is only for the 37.6 mi of selected reaches along Center Creek, Turkey Creek, Shoal Creek, and Tar Creek that were examined in this study. The total length of these streams that are contaminated by mine waste is approximately 49 mi (MacDonald and others, 2010). Quality Control and Quality Assurance To efficiently analyze the large number of samples col lected (357 stream channel samples [Smith, 2016; Stream channel sediment samples]; 379 flood-plain samples [Smith, 2016; Flood-plain cores]) in this study, all samples were analyzed using the XRF. Although samples were collected during 2011 to 2012, samples were analyzed during five periods between October 2012 and June 2014 as samples were processed and the XRF operated by the USFWS became avail able. Several quality control and quality assurance procedures were implemented to ensure the quality of the data acquired using the XRF. A series of standards and blanks were ana lyzed at the beginning, end, and several times throughout the day when environmental samples were analyzed. In addition to standards, triplicate and septuplet analyses of the selected flood-plain cores were done during the analysis. These were replicate analyses (3 or 7) at the same location in the core without moving the XRF instrument. Analyzing the same loca tion of the core multiple times determines the variability in precision of the XRF on samples that are often more heteroge neous in both grain size and metals distribution than prepared standards. In addition, split samples from 85 channel sediment and flood-plain samples were analyzed by the XRF instrument and also analyzed by the CMERSC laboratory to allow com parison of the XRF results to the laboratory results. Data Analysis Methods Data analysis was completed using a combination of graphical methods and basic statistics to interpret and to better
24 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Table 4. Mean maximum proportional depth of sediment exceeding the consensus probable effects concentrations and the Tri-State Mining District specific probable effects concentrations, and mean total depth of boreholes and tile probes for each site, Center Creek, Turkey Creek, Shoal Creek, Tar Creek, and Spring River in the Tri-State Mining District, 2011-12. [CPEC, consensus probable effects concentration (MacDonald and others, 2000); TPEC, Tri-State Mining District specific probable effects concentration (Inger soll and others, 2009); ft, foot; --, not applicable] Site identifier Maximum proportional depth exceeding the CPEC Maximum proportional depth exceeding the TPEC Average total depth of coring and tile probes from site (ft) Average depth of sediment exceeding the CPEC (ft) Average depth of sediment exceeding the TPEC (ft) Center Creek Mean, excluding gravel bar C6 Turkey Creek TC1 TC2 TC3 TC4 TC5 TC6 TC7 Mean Shoal Creek S1 S2 S3 S4 S5 Mean, excluding gravel bar S5 Tar Creek TR1 TR2 TR3 TR4 TR5 TR6 TR7 TR8 TR9 TR10 TR11
Quality Control and Quality Assurance 25 Table 4. Mean maximum proportional depth of sediment exceeding the consensus probable effects concentrations and the Tri-State Mining District specific probable effects concentrations, and mean total depth of boreholes and tile probes for each site, Center Creek, Turkey Creek, Shoal Creek, Tar Creek, and Spring River in the Tri-State Mining District, 2011-12.—Continued [CPEC, consensus probable effects concentration (MacDonald and others, 2000); TPEC, Tri-State Mining District specific probable effects concentration (Inger soll and others, 2009); ft, foot; --, not applicable] Site identifier Maximum proportional depth exceeding the CPEC Maximum proportional depth exceeding the TPEC Average total depth of coring and tile probes from site (ft) Average depth of sediment exceeding the CPEC (ft) Average depth of sediment exceeding the TPEC (ft) Tar Creek —Continued TR12 Mean Spring River SR1 SR2 Mean understand the data. Graphical examination included bar graphs, scatterplots, and boxplots. Basic statistics given in this report include the number of cases, means, standard devia tions, lower and upper 95th percentiles, and RSDs. Medians and upper and lower quartiles were displayed graphically in boxplots. Left censored data were common in the XRF results due to the high LOD of the XRF compared to laboratory results. The mean was calculated from the results of three individual scans using the XRF for each sample. Constituents for a sam ple that were below the LOD for the XRF for all three scans were reported as the LOD value. The LOD for the constituents of interest in this report are 11 mg/kg for arsenic, 12 mg/kg for cadmium, 100 mg/kg for barium, 260 mg/kg for cobalt, 35 mg/kg for copper, 85 mg/kg for manganese, 65 m/kg for nickel, 13 mg/kg for lead, and 25 mg/kg for zinc. If one or two of the three scans were below the LOD then that particular LOD value would be used to calculate the mean. For example, the mean of three individual scans of a sediment sample with reported copper concentrations of 38 mg/kg, 34 mg/kg, and LOD" (less than the LOD) would be the mean of 38, 35, and 35 mg/kg. Means that were less than their respective LOD were reported as less than their respective LOD using the less than sign. For, example a sample with three individual scans that reported all concentrations less than the LOD, the reported concentration in the tables would be <35 mg/kg. Concentra tions below the LOD were not used to calculate RPDs and were not used in any scatterplots. The LOD values were used only in the bar charts showing the vertical concentration of lead and zinc and in the creation of boxplots because the distribution shown by boxplots is better represented by using the reported values and concentrations below the LOD. The distribution of data would be skewed if LODs were not used. Standard Reference Material Standards included National Institute of Standards and Technology (NIST) high standard [standard reference mate rial (SRM) 2710a Montana I Soil], NIST medium standard (SRM 2711a Montana I Soil), NCS DC 73308 standard, and the U.S. Environmental Protection Agency Resource Conser vation and Recovery Act (RCRA) standard. Standards were used to ensure the instrument was within daily calibration requirements and to assess the general accuracy and precision of the XRF measurements on known materials. The overall mean concentration, standard deviation, upper and lower 95th percentiles, and percent difference were calculated for six MVT-related metals measured by XRF in each standard and compared to the standard's most probable value (MPV; table 6). Accuracy of the XRF allowed a percent difference within 30 percent of the standard's MPV concentration of target elements to be the data quality objective (DQO) for this project. The precision of the XRF measurements was assessed by calculating the relative standard deviation (RSD) of XRF mea surements for each of the standards. The RSD was calculated for target elements in each standard by dividing the standard deviation of the XRF results by the mean XRF result for each standard. The DQO for the precision of XRF measurements for this study was that the RSD would be <20 percent for all target elements measured in the standard materials. The stan dards were also used to ensure that the XRF was calibrated properly on a daily basis before and during the analysis of environmental samples. The concentrations of the measured target elements were to be within plus or minus 20 percent of the standard's MPV or the instrument would be recalibrated. Mean concentrations of arsenic, lead, manganese, and zinc from more than 30 analyses of standard reference materi als by the XRF attained the accuracy goal of being within
26 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Table 5. Digitized gravel bar area, creek or river total drainage area, hydrologic unit code, mean thickness of sediments exceeding the consensus probable effects concentrations and the Tri-State Mining District specific probable effects concentration, and estimated total volume of sediment with concentrations of lead or zinc that exceed the consensus probable effects concentration and the Tri-State Mining District specific probable effects concentration for Center Creek, Turkey Creek, Shoal Creek, and Tar Creek in the in the Tri-State Mining District, 2011-12. [ft2, square foot; mi, mile; mi2, square mile; USGS, U.S. Geological Survey; CPEC, consensus probable effects concentration (MacDonald and others, 2000); ft, foot; TPEC, Tri-State Mining District specific probable effects concentration (Ingersoll and others, 2009); yd3, cubic yard; --, data not calculated] Creek or river name Area of all digitized gravel bars along reach from mouth to most upstream site used in volume estimate (ft2) Area of all digitized gravel bars along reach from mouth to most upstream site used in volume estimate (acre) Length of stream used for volume estimated (mi) Length of stream studied (mi) Drainage area (mi2) USGS hydrologic unit code Average maximum depth to sediment exceeding the CPEC (ft) Average maximum depth to sediment exceeding the TPEC (ft) Minimum volume of sediment exceeding CPEC that could be excavated (yd3) Minimum volume of sediment exceeding TPEC that could be excavated (yd3) Center Creek 916,000 1107020706 136,000 115,000 Turkey Creek 632,000 110702070901 115,000 108,000 Shoal Creek 146,000 1107020708 24,000 4,000 Tar Creek 230,000 110702060106 9,000 9,000 Spring River 2,590 Total 1,924,000 284,000 236,000 aThe farthest upstream site used in the volume estimate was not the farthest upstream site in the length of the studied stream due to stretches of stream (Center Creek and Shoal Creek) with little or no data. bThe length of the stream used in the volume estimate was shorter than the overall length of the stream studied due to stretches of stream (Center Creek and Shoal Creek) with little or no data. cThe overall length of the studied stream reach from the farthest upstream site to its mouth at the Spring River (Center Creek, Turkey Creek, and Shoal Creek) or Neosho River (Tar Creek).
Quality Control and Quality Assurance 27 Table 6. Results of analyses of standard reference materials by the x-ray fluorescence unit. [mg/kg; milligram per kilogram; n, sample size; XRF, x-ray fluorescence; LCL, lower 95-percent confidence limit; UCL, upper 95-percent confidence limit; RSD, relative standard deviation; NIST, National Institute of Standards and Technology; NCS, NCS Testing Technology Co., Ltd.; less than; --, not calcu lated; RCRA, Resource Conservation and Recovery Act; shaded value indicates value outside project goal of mean XRF value more than 30 percent different from standard or precision as measured by RSD of less than 20 percent; analysis was conducted using an x-ray fluorescence instrument owned and operated by the U.S. Fish and Wildlife Service personnel following the U.S. Environmental Protection Agency Method 6200 (EPA, 2007) at the U.S. Fish and Wildlife Service office] Constituent Standard most probable value (mg/kg) n Number of left censored values XRF mean (mg/kg) XRF standard deviation (mg/kg) (mg/kg) UCL (mg/kg) Percent difference between XRF mean and standard (mg/kg) RSD (percent) Overall average RSDb (percent) NIST high standard Arsenic Barium Cadmium Lead 5,532 5,430 5,358 5,502 Manganese 10,100 9,887 9,678 10,096 Zinc 6,952 6,885 6,781 6,988 NIST medium standard Arsenic Barium Cadmium Lead 1,162 1,111 1,097 1,126 Manganese Zinc NCS DC 73308 standard Arsenic Barium Cadmium Lead Manganese 1,010 Zinc RCRA standard Arsenic Barium Cadmium Lead Manganese Zinc aNumber of samples with result less than the XRF limit of detection (LOD). bAverage relative percent difference (RPD) of all four check standards where the RPD for each standard is the XRF standard deviation divided by the average value reported by the XRF.
28 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District 30 percent of the MPV for all standards (table 6). The mean RSD for these four metals averaged over the several stan dards was <15 percent and within the DQO for precision of 20 percent; however, individual RSD values for arsenic in the NIST medium standard (23.0 percent), barium in the NCS DC 73308 standard (41.4 percent), cadmium in the NIST high standard (21.0 percent), and lead in the NCS DC 77308 standard (22.8 percent) were slightly larger than the DQO for precision (table 6). The XRF results for lead, manganese, and zinc tended to be biased slightly low compared to the standard MPVs (table 6). The bias generally increased with decreasing concentration in the standards (fig. 6; table 6). Results for lead concentrations were most accurate with the percent difference of the XRF mean from the MPV in the standards ranging from -13.7 to -1.8 percent, followed by zinc (-15.1 to -1.0 percent), and manganese (-28.5 to -2.1 percent). For arsenic, the pat tern was somewhat different, as the bias of the XRF mean concentration was of similar magnitude for the two standards with minimum and maximum MPVs (associated biases of -15.8 to 15.3 percent, respectively), and a much smaller bias (-0.5 percent) for the NIST medium standard. The standard MPV in relation to the upper and lower 95th percentile is also an indicator of non-zero bias. MPVs that are higher than the upper 95th percentile indicate a positive bias (XRF results that are higher than the laboratory results), whereas MPVs that are lower than the lower 95th percentile indicate a negative bias (XRF results that are lower than the laboratory results). All standard MPVs fell below the upper 95th percentile with the exception of all cadmium MPVs and the arsenic MPV for the NIST high standard. All standard MPVs fell below the lower 95th percentile with the exception of all cadmium MPVs and the arsenic and zinc MPVs for the NIST high standard. No time trends were noted in XRF results of standards based on qualitative inspection of the data. Based on analysis of the standards, concentrations of barium and cadmium reported by the XRF are less accurate than those reported for arsenic, lead, manganese, and zinc. The mean cadmium concentrations reported by the XRF in the NIST high standard exceeded the 30-percent accuracy goal for the project and the NCS DC 73308 standard was below the LOD for XRF; however, these were for the standards with the smallest MPV values (table 6). The mean cadmium concentra tion of 29 mg/kg reported by the XRF for the NIST high stan dard was about 33 percent larger than the MPV of 21.8 mg/kg. The mean measured cadmium concentrations in the NIST medium standard (MPV of 41.7 mg/kg) and RCRA standard (MPV of 500 mg/kg) were within 11 percent of the MPVs indi cating the XRF can reliably determine cadmium concentrations in the 41.7 to 500 mg/kg range in environmental samples but the XRF could attain the reliability levels corresponding to the project DQOs in concentrations less than about 41 mg/kg. The mean barium concentration of 190 mg/kg reported by the XRF for the NCS DC 77308 standard was more than 350 percent larger than the MPV of 42 mg/kg, and the 41.4 percent RSD for barium in this standard was the poorest precision result for the XRF among the target elements (table 6). The mean barium concentrations reported by the XRF in the NIST medium and NIST high standards (MPVs of 726 and 707 mg/kg, respectively) were more reliable, within 18 percent of MPVs; moreover, the associated RSDs were <10 percent, whereas the mean barium concentrations reported by the XRF in the NCS DC 73308 standard (MPV of 42 mg/kg) were greater than 350 percent and did not attain the reliability levels corresponding to the project DQOs. Environmental samples were not excluded based on the range of concentrations and the corresponding XRF reliability for reporting a specific constituent's concentration at those ranges. The statistics calculated on the standard reference mate rial is important for stakeholders when interpreting the data. A. Cadmium B. Lead C. Zinc 1,000 1,000 Most probable value Percent difference between x-ray fluorescence mean and the most probable value Probable effects concentration, 4.98 for cadmium, 128 for lead, and 459 milligrams per kilogram for zinc Tri-Satate Mining District probable effects concentration, 11.1 for cadmium, 150 for lead, and 2,083 milligrams per kilogram for zinc Trend line EXPLANATION Figure 6. Relations of percent difference between mean concentration by x-ray fluorescence with the most-probable-value concentrations of A, cadmium; B, lead; and C, zinc in standard reference materials.
Quality Control and Quality Assurance 29 Blanks A total of 45 silica sand blanks were analyzed during XRF analysis of environmental samples for the project. The XRF did not report concentrations in these samples of arsenic, lead, or manganese above the XRF LOD for these metals of 11 mg/kg, 13 mg/kg, and 85 mg/kg, respectively. The XRF did report a zinc concentration (17.3 mg/kg) in one sample that was below its LOD of 25 mg/kg for zinc. The XRF reported cadmium concentrations (14.8 to 18.7 mg/kg) greater than its LOD of 12 mg/kg in 6 of 43 blank samples. This indicates that the XRF does tend to have a positive bias in the reported cad mium concentrations compared to the standard's MPV, which can also be seen in the analysis of the standards (table 6). The LOD for the non-target metals cobalt (260 mg/kg) and nickel (65 mg/kg) were relatively large compared to other metals reported by the XRF, and the XRF did not report concentra tions of these constituents. Replicate X-Ray Fluorescence Analyses Because flood-plain core samples were analyzed intact and not disaggregated, examination of the precision of the XRF results on these samples was done using 24 sets of tripli cate (19) or septuplet (5) analyses of flood-plain core samples. These were replicate analyses (3 or 7) at the same location of the core without moving the XRF instrument. Metal concen trations should be similar for each replicate analysis, limited by the precision of the XRF instrument, when analyzing the same location of the core. The mean, standard deviation, and RSD were calculated for each set of analyses. The project DQO for precision of the XRF used with flood-plain sediment was to attain an RSD of <30 percent of the calculated mean measured concentration for groups of triplicate and septuplet analyses. Results of the triplicate and septuplet replicate analy ses indicate that the XRF results for intact flood-plain core generally were less than or near the DQO of 30 percent for the RSD. Metals with mean RSDs <30 percent were arsenic (27), barium (6), lead (25), and zinc (16; table 7). Manganese gener ally exceeded the DQO for precision with a mean RSD of 34.3 percent. Fourteen out of 24 samples were not scanned with the required length of time for measuring the concentration of barium. Standard deviations and RSDs were not calcu lated for samples with no measured values for barium and for samples that were below the LOD. Another measure of preci sion is the standard deviation of the replicate analyses. The mean standard deviation for arsenic was 10 mg/kg, barium was 28 mg/kg, lead was 28 mg/kg, and zinc was 33 mg/kg (table 7), and all were relatively low compared to manganese (204 mg/kg). The trimmed mean standard deviation for lead the outlier of 495 mg/kg (table 7) was 7.1 mg/kg, which indi cates very high precision for lead. There was very little data to examine the precision for cobalt, copper, and nickel because of their low concentrations in the samples. Laboratory Confirmation Samples The results of the XRF instrument's analysis of 85 split samples (76 stream channel samples and 9 flood-plain samples) collected during this study were compared to the CMERSC laboratory results as a quality check on the accuracy of the XRF results and to determine the comparability of XRF to laboratory results The laboratory results are listed in the Laboratory confirmation data (Smith, 2016). The split samples were analyzed by the XRF before submission to the CMERSC laboratory to provide a direct comparison between the XRF values and the laboratory values of the same sample. This provided three datasets for comparison: the results of the XRF instrument's analysis of the original sample, the results of XRF instrument's analysis of the split sample for the labora tory, and the laboratory results of the split sample. Overall, the XRF results from analysis of the original sample for the target elements lead and zinc compared favor ably to laboratory results, with linear regression coefficient of determination 0.87 for lead and 0.78 for zinc (fig. 7D and 7G). The results for the target element cadmium were less favorable with a coefficient of determination of 0.15 (fig. 7A) and the residuals are strongly biased towards one side of the line and no inferences should be made using the cadmium regression model. The XRF results of the original sample compared more favorably to the XRF results of the subsample with linear regression correlation coefficients of 0.84 for lead, 0.80 for zinc, and 0.76 for cadmium (fig. 7F, 7I, and 7C), indicating that compositing 1 to 3 subsamples to prepare the split sample was adequate for representativeness of the laboratory split samples. Concentrations of arsenic, cobalt, copper, and nickel in the split samples were generally below the LOD of the XRF instrument. To compare the results between analytical methods, the relative percent difference (RPD) was computed as the absolute value of the difference between the two values being compared divided by the mean of the two values being compared, expressed as a percentage. In the computation of the RPD values, the LOD level was substituted for samples where the value determined by the XRF was less than the LOD. Comparisons were made using (1) the RPD between the XRF result for the original sample and the laboratory result for the split sample (RPD-1), and (2) the RPD between the XRF result for the split sample and the laboratory result for the same split sample (RPD-2; table 8 at the back of this report). For the three metals of most concern for this study, the mean RPD values for lead (22-23 percent) was less than the project DQO for accuracy of 30 percent, and the mean RPD values for cadmium and zinc (58-67 percent and 38-39 percent, respec tively) exceeded the project DQO (table 8). Excluding samples where the cadmium concentration reported by the laboratory was less than the LOD of the XRF, there is a tendency for the RPD-1 and RPD-2 values for cadmium, lead, and zinc to increase with increasing concen tration reported by the laboratory (fig. 8). The cause for this trend is not known but could be related to heterogeneity in the
30 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Table 7. Statistical summary of triplicate and septuplet x-ray fluorescence scans of intact flood-plain cores in the Tri-State Lead and Zinc Mining District, 2011-12. [ft, foot; less than; --, not calculated (samples were not scanned for sufficient time for the detection of constituent); cells with gray shading exceeded the project goal of 30 percent for relative standard devia tion; all concentrations are in milligrams per kilogram; analysis was conducted using an x-ray fluorescence instrument owned and operated by the U.S. Fish and Wildlife Service personnel following the U.S. Enviornmental Protection Agency Method 6200 (EPA, 2007) at the U.S. Fish and Wildlife Service office] Coring or sample identifier Depth (ft) Number of replicate measure ments Arithmetic mean Standard deviation Relative standard deviation Arsenic Barium Lead Manganese Zinc Arsenic Barium Lead Manganese Zinc Arsenic Barium Lead Manganese Zinc CTR-FB-2 CTR-FP-1 1,520 CTR-FP-2 CTR-FP-3 CTR-FP-3 2,798 CTR-FP-4 CTR-FP-5 TKC-FB-1 TKC-FB-2 TKC-FB-2 TKC-FP-1 TKC-FP-2 TKC-FP-3 SH-FB-2 SH-FB-3 SH-FP-1 SH-FP-4 TAR-FB1 3,083 1,497 TAR-FB4 TAR-FP1-2 TAR-FP2-1 TAR-FP2-2 TAR-FP2-3a TAR-FP2-4 Averages Trimmed mean 7.1b Number of values summarized aMaterial identified as slough by the onsite hydrologist, indicating that the material likely fell from a shallower depth and is not representative of the soil at the 11-ft depth. bAverage standard deviation of lead excluding the value 495.3.
Quality Control and Quality Assurance 31 Logarithm of concentration in the original sample reported by the x-ray fluorescence analysis, in milligrams per kilogram (table 8) Logarithm of concentration in the laboratory subsample reported by the x-ray fluorescence analysis, in milligrams per kilogram (table 8) EXPLANATION Prediction line 0.95-confidence interval Lead Zinc Logarithm of concentration in sample reported by the laboratory, in milligrams per kilogram (table 8) Concentration in the original samples reported by the x-ray fluorescence, in milligrams per kilogram R² 0.90 y 1.01x + 0.057 n 83 R² 0.84 y 0.998x + 0.002 n 83 R² 0.78 y 0.896x + 0.506 n 85 R² 0.92 y 1.06x - 0.042 n 83 R² 0.80 y 0.975x + 0.082 n 83 E F G H Cadmium R² 0.52 y 1.02x + 0.197 R² 0.15 y 0.695x + 0.527 n 42 R² 0.76 y 1.11x - 0.142 n 34 n 44 A B R²= 0.87 y 0.916x + 0.274 n 85 D Figure 7. Relations between concentrations of A-C, cadmium; D-F, lead; G-I, zinc in laboratory subsamples determined by x-ray fluorescence and laboratory methods, and between concentrations determined by x-ray fluorescence in original and split subsamples.
32 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District EXPLANATION Consensus probable effects concentration Tri-State Mining District specific probable effects concentration Trend line Relative percent difference between laboratory results for the split sample and the x-ray fluorescence results for the original sample Concentration reported by the laboratory, in milligrams per kilograms Relative percent difference between laboratory results for the split sample and the x-ray fluorescence results for the laboratory subsample D 1,000 10,000 1,000 10,000 Lead Lead E F 1,000 10,000 1,000 10,000 Zinc Zinc A B 1,000 1,000 Cadmium Cadmium Figure 8. Comparison of relative percent difference between laboratory results for A-B, cadmium; C-D, lead; and E-F, zinc in the split samples, and the x-ray fluorescence results for either the original samples (A, C, and E ) or the split sample before its submittal to the laboratory (B, D, and F ) for stream channel sediment, Tri-State Mining District.
Occurrence, Distribution, and Volume of Metals-Contaminated Sediment 33 distribution of metals in the samples or in sample grain size. It is possible that larger concentrations of metals may reflect the effect of a proportionately smaller number of very metal-rich grains (perhaps grains consisting of mostly ore minerals) that are not evenly distributed throughout the sample; however, sample-preparation differences also could explain the observed upward trend in RPD between XRF and laboratory results as concentrations increase. The laboratory completely digested a thoroughly homogenized fraction of the split sample submit ted to the laboratory, whereas the XRF method measured only three small locations within the entire subsample. Occurrence, Distribution, and Volume of Metals-Contaminated Sediment This section presents the data from the XRF analysis of the sediments collected in the Spring River and four tributaries draining mined areas in the TSMD. Data from the XRF field measurements were also used to estimate the total volume of sediment deposited in selected sampled reaches (fig. 1) of the stream channel with concentrations of lead or zinc greater than the CPEC and TPEC sediment-quality guidelines. The estimated volume of contaminated sediments is based on sedi ments in gravel bars because insufficient data was obtained to characterize sediment volumes beneath other channel features such as pools. Center Creek Center Creek has a drainage area of 300 mi2 at its conflu ence with Spring River and is approximately 66.0 mi in length from the headwaters to the mouth. Approximately 18.6 mi of the lower part of the creek were studied and the lower 11.1 mi were used in the estimation of the volume of contaminated sediment (table 5). Site Selection and Description The Center Creek study reach consisted of an area of intensive study (gravel bar sites C1, C2, and nearby flood plain; fig. 9) and four upstream supplementary gravel bar sites (C3, C4, C5, C6; figs. 10 and 11). The intensive study on Cen ter Creek was done over a 1-week period in November 2011. Samples also were collected on four supplemental gravel bars during 2 weeks of drilling in the summer of 2012. In total, samples were collected from 24 channel locations and 7 floodplain locations in the Center Creek study reach. The intensive study area was just west of Highway JJ, north of Joplin, Mo. (fig. 9). Gravel bar-sediment samples were centered on two gravel bars at sites C1 and C2 (fig. 9). Five cores (CTR-CH-5, CTR-CH-6, CTR-CH-7, CTR-WC-3, and CTR-WC-4) were on or near the gravel bar at site C2 near the flood-plain transect CTR-CTR'. The wetted channel (WC) cores were located adjacent to the gravel bar. The cores (CTRCH-1, CTR-CH-2, CTR-CH-3, CTR-CH-4, CTR-WC-1, and CTR-WC-2) were at site C1 on and near a gravel bar on the left bank about 1,500 ft downstream from the flood-plain transect CTR-CTR' at site C2. Core CTR-GB-1 was a hand scoop from a small gravel bar on the right bank of the stream. A transect (CTR-CTR') of five cores (CTR-FP-1, CTR-FP-2, CTR-FP-3, CTR-FP-4, and CTR-FP-5) were drilled across the flood plain with three on the north side of the creek and two on the south. Two flood-plain bias cores (CTR-FB-1 and CTR-FB-2), located on features of interest, were drilled off the flood-plain transect CTR-CTR' line. The flood-plain borehole CTR-FB-1 was 1,300 ft west of CTR-FP-4. The flood-plain borehole CTR-FB-2 was on the inside of a creek meander. The locations of CTR-FB-1 and CTR-FB-2 were selected because of an apparent lower elevation within the flood plain, which may be subject to greater frequency of flooding. Four additional gravel bars farther upstream were selected for sampling. The gravel bar at site C3 with two core locations (CC-A-HD1 and CC-A-HD2) was located about 1,000 ft downstream from the Highway 171 bridge (fig. 10). The gravel bar at site C4 had three core locations (CC-DHD1, CC-D-HD2, and CC-D-WC-1) and was located about 1.7 river mi upstream from site C3. Gravel bar at site C5 had three cores (CC-C-HD1, CC-C-HD2, and CC-C-WC1; fig. 11) and was located 700 ft downstream from the Highway O bridge (not shown). The gravel bar at site C6 had two core locations (CC-B-HD1 and CC-B-HD2) and two hand scoop sample locations (CC-B-HS1 and CC-B-HS2). It was the far thest upstream site on Center Creek and was located directly downstream from the Highway 175 bridge east of Joplin, Mo. (fig. 11). Depth and Concentration of Metals in Channel Sediments A total of 89 gravel bar-sediment samples from 24 loca tions were collected from gravel bar deposits along the lower 18.6 miles of Center Creek. The maximum sample depth was 9.5 ft below the gravel bar surface. Most of the gravel bar-sed iment samples from Center Creek exceeded the CPEC and the TPEC for lead or zinc for sites C1, C2, C3, C4, and C5. About 45 percent of these had detections of cadmium greater than the LOD for the XRF. Because the CPEC (4.98 mg/kg) and TPEC (11.1 mg/kg) for cadmium is less than the LOD (12 mg/kg), the frequency of cadmium exceeding the PEC's is at least 45 percent. Site C6 is upstream from most of the historic min ing activity in the Center Creek basin, and none of the samples from this site had concentrations of lead, or zinc that exceeded the CPEC or TPEC or concentrations of cadmium that exceeded the LOD. Overall, median concentrations of lead and zinc increased dramatically from upstream site C6 to site C5, peaked at sites C4 and C3, and decreased downstream through sites C2 and C1; however, lead and zinc median concentra tions at site C1 remained enriched significantly above their
34 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District CTR-FP-5 CTR-FP-4 CTR-FP-3 CTR-FP-2 CTR-FP-1 CTR-FB-2 CTR-FB-1 CTR-FB-1 CTR-WC-4 CTR-WC-3 CTR-WC-2 CTR-WC-1 CTR-GB-1 CTR-CH-7 CTR-CH-6 CTR-CH-4 CTR-CH-3 CTR-CH-2 CTR-CH-1 CTR-CH-1 CTR-CH-5 94°34'50" 94°35'00" 94°35'10" 94°35'20" 94°35'30" 37°09'50" 37°09'40" 37°09'30" CTR-FP-5 CTR-FP-4 CTR-FP-3 CTR-FP-2 CTR-FP-1 CTR-FB-2 CTR-FB-1 CTR-WC-4 CTR-WC-3 CTR-WC-2 CTR-WC-1 CTR-GB-1 CTR-CH-7 CTR-CH-6 CTR-CH-4 CTR-CH-3 CTR-CH-2 CTR-CH-1 CTR CTR' CTR CTR' CTR-CH-5 37°09'50" 37°09'40" 37°09'30" 500 FEET 500 METERS Frequently to occasionally flooded soil Flood-plain transect Direction of flow Site identifier EXPLANATION Tile probe sounding Flood-plain core or sample and identifier Channel core or sample and identifier Possible mine shaft Possible mine shaft Possible mine dump Possible mine dump Abandoned channel Abandoned channel Flooded soils from Natural Resources Conservation Service (NRCS) digital data, 2003 Base from National Agriculture Imagery Program (NAIP) U.S. Department of Agriculture, 2013 (top); Natural Resources Conservation Service (NRCS) aerial photography, 1938 (bottom) Geographic coordinate system, North American Datum 1983 Center Creek Center Creek HIGHWAY JJ A. 2013 B. 1938 CTR CTR' HIGHWAY JJ Figure 9. Aerial photographs from A, 2013 and B, 1938 showing location of cores, samples, and tile probe soundings for sites C1 and C2 of intensive study on Center Creek, Missouri, 2011-12.
Occurrence, Distribution, and Volume of Metals-Contaminated Sediment 35 CC-A-HD1 CC-A-HD1 CC-A-HD2 94°32'15" 94°32'20" 94°32'25" 37°10'10" 37°10'05" 37°10'00" 37°09'55" CC-D-HD1 CC-D-HD2 CC-D-WC1 94°30'45" 94°30'50" 94°30'55" 94°31'00" 37°10'15" 37°10'10" 37°10'05" 37°10'00" CC-A-HD1 CC-A-HD2 94°32'15" 94°32'20" 94°32'25" CC-D-HD1 CC-D-HD2 CC-D-WC1 94°30'45" 94°30'50" 94°30'55" 94°31'00" 400 FEET 400 METERS Center Creek Center Creek Center Creek Center Creek Direction of flow Site identifier EXPLANATION Tile probe sounding Channel core or sample and identifier A. 2013 D. 1961 B. 1938 Base from National Agriculture Imagery Program (NAIP), U.S. Department of Agriculture, 2013 (left images); Natural Resources Conservation Service (NRCS) aerial photography, 1938 (top right); U.S. Geological Survey aerial photography, 1961 (bottom right) Geographic coordinate system, North American Datum 1983 HIGHWAY 171 HIGHWAY 171 Figure 10. Aerial photographs from A, 2013 and B, 1938 for site C3 and from C, 2013 and D, 1961 for site C4 showing location of cores, samples, and tile probe soundings on Center Creek, Missouri, 2011-12.
36 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District CC-C-HD1 CC-C-HD2 CC-C-WC1 94°27'20" 94°27'25" 94°27'30" 94°27'35" 37°10'35" 37°10'30" 37°10'25" 37°10'20" CC-C-HD1 CC-B-HD1 CC-B-HD2 CC-B-HS1 CC-B-HS2 94°22'50" 94°22'55" 94°23'00" 94°23'05" 37°07'50" 37°07'45" 37°07'40" CC-C-HD1 CC-C-HD2 CC-C-WC1 94°27'20" 94°27'25" 94°27'30" 94°27'35" CC-B-HD1 CC-B-HD2 CC-B-HS1 CC-B-HS2 94°22'50" 94°22'55" 94°23'00" 94°23'05" 400 FEET 400 METERS A. 2013 A. 2013 B. 1961 B. 1961 Direction of flow Site identifier EXPLANATION Tile probe sounding Channel core or sample and identifier Base from National Agriculture Imagery Program (NAIP), U.S. Department of Agriculture, 2013 (left images); U.S. Geological Survey aerial photography, 1961 (right images) Geographic coordinate system, North American Datum 1983 HIGHWAY 175 HIGHWAY 175 Shoal Creek Shoal Creek Shoal Creek Shoal Creek Figure 11. Aerial photographs from A, 2013 and B, 1961 showing location of cores, samples, and tile probe soundings for sites C5 and C6 on Center Creek, Missouri, 2011-12.
Occurrence, Distribution, and Volume of Metals-Contaminated Sediment 37 levels at upstream site C6 (fig. 12). Although no samples from site C6 had XRF-detectable cadmium concentrations, con centrations of cadmium followed a similar but more subdued pattern. Laboratory results from four samples from site C6 had detectable concentrations of lead, zinc, and cadmium all below the respective CPECs. Very few gravel bar-sediment samples from Center Creek exceeded the CPEC for other metals (one exceedance for arsenic and six exceedances for nickel), although exceedances for nickel may be underrepresented because the CPEC is less than the XRF LOD of 65 mg/kg. Lead concentrations ranged from 14.0 mg/kg to 1,880 mg/kg (Smith, 2016; Stream channel sediment samples) in the <2-mm size fraction of the 89 channel-sediment samples from Center Creek and exceeded the CPEC in 60 samples (67 percent). The largest lead concentration was at site C1 in borehole CTR-CH-3 at a depth of 4 to 5 ft below surface. Hereinafter, all depths in the body of this report will be ref erenced to the local land surface. The deepest sample with a lead concentration (177 mg/kg) greater than the CPEC was at site C1 in borehole CTR-CH-2 at a depth of 6.5 to 7.5 ft (fig. 13). Of the 80 samples from sites C1-C5, 60 had lead con centrations greater than the CPEC and 57 were greater than the TPEC. Excluding upstream site C6, concentrations of lead in the upper 5 ft of most cores exceeded the CPEC or TPEC for one or more depth intervals (fig. 13), and in a few cases, concentrations tended to increase with depth. As examples of the latter, see results in figure 13 for CTR-CH-3, CC-A-HD2, and CC-C-HD1. Zinc concentrations in the <2-mm size fraction in channel-sediment samples from Center Creek ranged from 201 mg/kg to 25,200 mg/kg exceeding the CPEC in 76 samples (85 percent). The largest zinc concentration was in borehole CC-A-HD1 at a depth of 3 to 4 ft (Smith, 2016; Stream channel sediment samples). The deepest sample with a zinc concentration (1,100 mg/kg) greater than the CPEC was at site C1 at a depth of 8.5 to 9.5 ft in borehole CTRCH-2 (fig. 14), the same borehole that had the deepest lead concentration greater than the CPEC (fig. 13). The deepest sample with a zinc concentration (3,470 mg/kg) greater than the TPEC was at site C1 in borehole CTR-CH-1 at a depth of 6 to 7 ft. Because the zinc TPEC is more than 4 times larger than the CPEC, the frequency of samples from sites C1 to C5 with zinc exceeding the TPEC is smaller (53 of 80, or 66 per cent) than the frequency of samples exceeding the CPEC (76 of 80, or 95 percent). Perhaps more importantly, the depth of contamination is greatly dependent on which PEC (CPEC or TPEC) value is used. Of the 56 samples from sites C1 to C5 collected from depths ft, 55 samples (98 percent) exceeded the CPEC and 45 samples (80 percent) exceeded the TPEC; however, of the 24 samples collected from depths greater than 4 ft, 21 of 24 (88 percent) exceeded the CPEC, whereas only 8 (33 percent) exceeded the TPEC. Cadmium concentrations in the <2-mm size fraction in stream channel sediments were detected above the 12 mg/kg LOD in 34 samples (38 percent) and the maximum concentration was 171 mg/kg (Smith, 2016; Stream channel sediment samples). The median concentrations (fig. 12) tended to increase down stream from no detection at site C6 to a peak at site C3 and then decreased to site C1, which is nearest to the confluence with Spring River. Gravel bars at sites C3, C4, and C5 had detectable cadmium concentrations that exceeded the CPEC and TPEC in 24 out of 27 samples. The farthest downstream sites (C1 and C2) had fewer cadmium concentrations that exceeded the CPEC and LOD (10 out of 53 samples). Estimated Volume of Channel Sediment Contaminated by Mine Waste The total volume of sediment deposited in gravel bars along the lower 11.1 mi of Center Creek from site C1 to site C5 was estimated on the basis of the mean maximum sediment depths with concentrations of lead and zinc that exceeded the CPEC and the TPEC. Site C5 was chosen as the farthest upstream extent of known sediment contamination because no lead or zinc concentrations exceeding their respective CPEC or TPEC values were upstream from site C5. Site C6 was approximately 7.5 mi upstream from site C5. The mean thickness of sediment that would need excavation based on the CPEC for Center Creek was 4.0 ft, and the mean thickness of sediment that would need excavation based on the TPEC was 3.4 ft (table 5). The total area of studied gravel bars for Center Creek was 916,000 square feet (ft2; 21.0 acres; table 5). The estimated minimum volume of sediment in gravel bars that would need excavation based on the CPEC along Center Creek from the mouth to site C5 was 136,000 cubic yards (yd3), and the estimated minimum volume of gravel bar sedi ment exceeding the TPEC was 115,000 yd3 (table 5). These estimates are considered minimum volumes because they were only based on the visible gravel bars and do not include sediment beneath the wetted channel in other features such as pools, and presumably some of these deposits are negatively affected by mine-waste contaminated sediment but were not sufficiently characterized to be included in the volume estimate. Depth and Concentration of Metals in FloodPlain Sediments A total of 84 samples were collected from 7 locations on the Center Creek flood plain at sites C1 and C2 within the intensive study. Four of the seven boreholes had at least one depth interval where lead or zinc exceeded the CPEC or TPEC. Intervals that exceeded the lead or zinc CPEC and TPEC were generally ft deep with occasional detections greater than the CPEC at deeper intervals. Because of time limitations, concentrations of cadmium or barium were not analyzed in many core intervals. For the intervals that were analyzed, 15 out of 23 had concentrations of cadmium greater than the LOD, CPEC, and TPEC, 3 of which were greater than 2 times the LOD. Core samples from borehole CTR-FB-2 had cadmium concentrations analyzed at every sampled interval,
38 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District LEAD 1,000 1,000 1,000 TC1 TC2 TC3 TC4 TC5 TC6 TC7 S1 S2 S3 S4 S5 S6 SR1 n=38 SR2 TR1 n 42 n=17 n=13 n=1 ZINC 1,000 10,000 1,000 10,000 1,000 1,000 1,000 10,000 n 42 n=17 n=13 n=1 TC1 TC2 TC3 TC4 TC5 TC6 TC7 TR1 SR1 n=38 SR2 S1 S2 S3 S4 S5 S6 Concentration in samples reported by the x-ray fluorescence, in milligrams per kilogram Gravel bar sites in order from downstream to upstream CADMIUM n 42 n=17 TC1 TC2 TC3 TC4 TC5 TC6 TC7 TR1 n=1 SR1 n=38 SR2 Upper adjacent (within 1.5 times IQR) 75th percentile Median 25th percentile Interquartile range (IQR) Upper detached (greater than 3.0 times IQR) Upper outside (1.5 to 3 times IQR) Lower adjacent (within 1.5 times IQR) Lower detached (greater than 3.0 times IQR) Upper outside (1.5 to 3 times IQR) IQR is the interquartile range EXPLANATION Spring River Turkey Creek Center Creek Shoal Creek Tar Creek Figure 12. Frequency distributions of the concentrations of cadmium, lead, and zinc at specific sites in order from downstream to upstream.
Occurrence, Distribution, and Volume of Metals-Contaminated Sediment 39 1,000 Concentration of lead in sediment samples, in milligrams per kilogram Midpoint of each sample interval below the local water surface, in feet 1,000 1,000 1,000 1,000 CC-A-HD1 CC-A-HD2 CC-B-HD1 CC-B-HD2 CC-B-HS1 CC-B-HS2 CC-C-HD1 CC-C-HD2 CC-C-WC1 CC-D-HD1 CC-D-HD2 CC-D-WC1 CTR-CH-1 CTR-CH-2 CTR-CH-3 CTR-CH-4 CTR-CH-5 CTR-CH-6 CTR-CH-7 CTR-GB-1 CTR-WC-1 CTR-WC-2 CTR-WC-3 CTR-WC-4 [Core and site identifiers are explained in table 1] Sample concentration Probable effects concentration, 128 milligrams per kilogram Tri-State Mining District specific probable effects concentration, 150 milligrams per kilogram EXPLANATION Figure 13. Vertical concentration profiles for lead in the less than 2-millimeter size fraction of gravel bar-sediment samples scanned by x-ray fluorescence, Center Creek, Missouri, 2011-12.
40 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Concentration of zinc in sediment samples, in milligrams per kilogram Midpoint of each sample interval below the local water surface, in feet 1,000 10,000 1,000 10,000 1,000 10,000 1,000 10,000 1,000 10,000 [Core and site identifiers are explained in table 1] Sample concentration Probable effects concentration, 459 milligrams per kilogram Tri-State Mining District specific probable effects concentration, 2,083 milligrams per kilogram EXPLANATION CC-A-HD1 CC-A-HD2 CC-B-HD1 CC-B-HD2 CC-B-HS1 CC-B-HS2 CC-C-HD1 CC-C-HD2 CC-C-WC1 CC-D-HD1 CC-D-HD2 CC-D-WC1 CTR-CH-1 CTR-CH-2 CTR-CH-3 CTR-CH-4 CTR-CH-5 CTR-CH-6 CTR-CH-7 CTR-GB-1 CTR-WC-1 CTR-WC-2 CTR-WC-3 CTR-WC-4 Figure 14. Vertical concentration profiles for zinc in the less than 2-millimeter size fraction of gravel bar-sediment samples scanned by x-ray fluorescence, Center Creek, Missouri, 2011-12.
Occurrence, Distribution, and Volume of Metals-Contaminated Sediment 41 and concentrations exceeded the CPEC and TPEC in every interval shallower than 7 ft and at the 8 to 9 ft interval (Smith, 2016; Flood-plain cores) but had no exceedances of the CPEC or TPEC for lead or zinc. Of 84 samples on the Center Creek flood plain, 14 had concentrations of lead greater than the CPEC (13 greater than the TPEC) and 25 had concentrations of zinc greater than the CPEC (10 greater than the TPEC [Smith, 2016; Flood-plain cores]). Three of the seven boreholes (CTR-FB-2, CTR-FP-4, and CTR-FP-5) had no samples with lead or zinc concentra tions greater than the CPEC, and borehole CTR-FP-3 had lead and zinc exceed their CPEC values in only the 0 to 1 ft interval (figs. 15 and 16). One borehole, CTR-FP-1, had lead concentrations generally exceeding the CPEC value in inter vals ft deep and zinc concentrations exceeding the CPEC in intervals <11 ft deep. From the 1938 aerial photograph (fig. 9B), borehole CTR-FP-1 was within or very near an old stream channel draining what appears to be a possible minewaste dump and mine shaft. Borehole CTR-FP-2 was farther from the old stream channel, and lead and zinc contamination levels greater than the CPEC values were limited to intervals ft deep (figs. 15 and 16). In deeper intervals of most floodplain boreholes, lead concentrations generally were between 20 and 50 mg/kg, and zinc concentrations were more variable ranging from <25 mg/kg to about 175 mg/kg. The concentrations of lead and zinc in deeper core intervals are similar to background concentrations estimated by Pope (2005) of 20 mg/kg for lead and 100 mg/kg for zinc except for an anomalous zinc concentration (33,700 mg/kg) at the bottom of borehole CTR-FP-2. This anomalous zinc sam ple also had the largest cadmium concentration (183 mg/kg) detected in any flood-plain sample or streambed-sediment sample from this study (Smith, 2016; Flood-plain cores), but visual inspection of the core indicated the presence of the zinc ore mineral, sphalerite, which is known to contain abundant quantities of cadmium (Jolly and Van Heyl, 1968). Changes in the geologic character of the core at depth, and the abrupt increases in concentrations at the bottom of the core, lead to the interpretation that the anomalous concentrations of zinc and cadmium in the sample from 15 to 16 ft depth are most likely derived from naturally occurring minerals in weathered bedrock and not the result of mine contamination. Turkey Creek Turkey Creek has a drainage area of 46 mi2 at its conflu ence with Spring River and is approximately 20.8 mi in length from the headwaters to the mouth. Approximately 10.1 mi of the lower part of the creek was studied and used in the estima tion of the volume of contaminated sediment (table 5). Site Selection and Description Turkey Creek gravel bar-sediment samples and floodplain samples were collected during a period of 3 weeks in the summer of 2012. The Turkey Creek study reach consisted of an area of intensive study (TC1, TC2, and TC3; fig. 17) and four upstream supplemental gravel bar sites (TC4, TC5, TC6, and TC7 [the farthest upstream]; figs. 18, 19). The intensive study area was west of Joplin (fig. 1). Twenty-three gravel bar locations and six flood-plain locations were cored along Turkey Creek. Transect TC-TC' with five cores spanning gravel bar sites TC2 and TC3 (TKC-FP-1, TKC-FP-2, TKCFP-3, TKC-FB-1, and TKC-FP-4) were drilled across the flood plain with four on the north side of the creek and one on the south (fig. 17). There were three gravel bar coring locations along transect TC-TC' at gravel bar site TC3: two on the dry part of the gravel bar (TKC-CH-2 and TKC-CH-3) and one in the wetted channel (TKC-WC-1). One gravel bar borehole at gravel bar site TC3 (TKC-CH-1) was located a short distance out of the transect line but on the same gravel bar (fig. 17). Additional cores were collected in the intensive study area downstream from transect TC-TC'. Another core at gravel bar site TC2 (TKC-CH-4) was located about 600 ft downstream from the transect line on the north side of the creek. Another flood-plain borehole at gravel bar site TC1 (TKC-FB-2) was drilled south of the creek and about 1,000 ft downstream from transect TC-TC'. Four additional gravel bar-sediment sample locations at site TC1 were on gravel bars <1,500 ft downstream from transect TC-TC', near an over flow channel that exists north of the main channel of Turkey Creek (fig. 17). The overflow channel branches off of the main channel and rejoins it less than half a mile downstream. At the time of sampling, the overflow channel contained only small pools of standing water and was choked with sand and gravel, especially at the upstream end. Flow through the overflow channel likely only occurs during periods of high flow in Turkey Creek, which makes it a likely depositional area for sediment transported during storm events. Four cores were drilled in and between the overflow and main channels. At site TC1, one core (TKC-CH-7) was drilled on a gravel bar and one core (TKC-WC-3) was drilled in the adjacent submerged part of the gravel bar in the overflow channel (fig. 17). At site TC1, hand sample TKC-CH-5P and core TKC-CH-5 were on opposite sides of the main channel. At site TC1, hand samples were collected from TKC-CH-5P from 0 to 2 ft on a gravel bar on the opposite side of the stream from coring location TKCCH-5. At site TC1, core TKC-CH-6 was drilled between the main channel and overflow channel (fig. 17). Thirteen locations were sampled at five supplemental gravel bars upstream from the intensive study site. Site TC4 had two cores (TC-D-HD1 and TC-D-HD2) and was located about 1,000 ft downstream from the bridge at North Black Cat Road (fig. 18). Site TC5 had three cores (TC-E-HD1, TC-E-HD2, and TC-E-WC1), and was located about 3,000 ft upstream from the bridge at site TC4. At site TC5, core TCE-WC1 was in the wetted channel while the remaining cores were drilled on the gravel bar itself (fig. 18). Site TC6 had two adjacent gravel bars (fig. 19) and was located about 3 mi upstream from the site TC5. The upstream gravel bar at site TC6 had a single core (TC-B-HD1). Coring was attempted in
42 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District 1,000 1,000 1,000 1,000 1,000 1,000 SH-FB-1 SH-FB-2 SH-FB-3 SH-FB-4 SH-FP1 SH-FP-2 TAR-FB-1 TAR-FB-2 TAR-FB-3 TAR-FB-4 TAR-FP1-1 TAR-FP1-2 TAR-FP1-3 TAR-FP1-4 TAR-FP2-1 TAR-FP2-2 TAR-FP2-3 TAR-FP2-4 TAR-FP2-5 TKC-FP-4 CTR TKC SH TAR Center Creek Turkey Creek Shoal Creek Tar Creek CTR-FB-1 CTR-FB-2 CTR-FP-1 CTR-FP-2 CTR-FP-3 CTR-FP-4 CTR-FP-5 TKC-FB-1 TKC-FB-2 TKC-FP-1 TKC-FP-2 TKC-FP-3 SH-FP-3 SH-FP-4 Concentration of lead in flood-plain cores and samples, in milligrams per kilogram Midpoint of each sample interval below land surface, in feet [Core and site identifiers are explained in table 2] Sample concentration Probable effects concentration, 128 milligrams per kilogram Tri-State Mining District specific probable effects concentration, 150 milligrams per kilogram EXPLANATION Figure 15. Vertical profiles by flood-plain core and sample location of lead concentrations analyzed by x-ray fluorescence in Center Creek, Turkey Creek, Shoal Creek, and Tar Creek, 2011-12.
Occurrence, Distribution, and Volume of Metals-Contaminated Sediment 43 [Core and site identifiers are explained in table 2]
Sample concentration Probable effects concentration, 459 milligrams per kilogram Tri-State Mining District specific probable effects concentration, 2,083 milligrams per kilogram EXPLANATION Midpoint of each sample interval below land surface, in feet Concentration of zinc in flood-plain cores and samples, in milligrams per kilogram 1,000 1,000 1,000 1,000 1,000 1,000 SH-FB-1 SH-FB-2 SH-FB-3 SH-FB-4 SH-FP1 SH-FP-2 TAR-FB-1 TAR-FB-2 TAR-FB-3 TAR-FB-4 TAR-FP1-1 TAR-FP1-2 TAR-FP1-3 TAR-FP1-4 TAR-FP2-1 TAR-FP2-2 TAR-FP2-3 TAR-FP2-4 TAR-FP2-5 TKC-FP-4 CTR-FB-1 CTR-FB-2 CTR-FP-1 CTR-FP-2 CTR-FP-3 CTR-FP-4 CTR-FP-5 TKC-FB-1 TKC-FB-2 TKC-FP-1 TKC-FP-2 TKC-FP-3 SH-FP-3 SH-FP-4 CTR TKC SH TAR Center Creek Turkey Creek Shoal Creek Tar Creek Figure 16. Vertical profiles by flood-plain core and sample location of zinc concentrations analyzed by x-ray fluorescence in Center Creek, Turkey Creek, Shoal Creek, and Tar Creek, 2011-12.
44 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District TKC-CH-2 TKC-CH-1 TKC-CH-3 TKC-CH-4 TKC-CH-5 TKC-CH-6 TKC-CH-7 TKC-WC-3 TKC-CH-5P TKC-WC-1 TKC-FB-1 TKC-FB-2 TKC-FP-1 TKC-FP-2 TKC-FP-3 TKC-FP-4 TKC TKC' 94°34'40" 94°34'50" 94°35'00" 94°35'10" 94°35'20" 37°07'20" 37°07'10" TKC TKC' Turkey Creek Turkey Creek 37°07'20" 37°07'10" TKC-FB-1 TKC-FB-2 TKC-FP-1 TKC-FP-2 TKC-FP-3 TKC-FP-4 TKC-CH-2 TKC-CH-1 TKC-CH-3 TKC-CH-4 TKC-CH-5 TKC-CH-6 TKC-CH-7 TKC-WC-1 TKC-WC-3 TKC-CH-5P 500 FEET 500 METERS TKC-FP-1 TKC-CH-1 TC1 Frequently to occasionally flooded soil Flood-plain transect Direction of flow Site identifier EXPLANATION Tile probe sounding Flood-plain core or sample and identifier Channel core or sample and identifier TKC TKC' Base from National Agriculture Imagery Program (NAIP), U.S. Department of Agriculture, 2013 (top); Natural Resources Conservation Service (NRCS) aerial photography 1938 (bottom) Geographic coordinate system, North American Datum 1983 Overflow channel Overflow channel TC1 TC1 TC2 TC2 TC3 TC3 A. 2013 B. 1938 Flooded soils from Natural Resources Conservation Service (NRCS) digital data, 2003 Figure 17. Aerial photographs from A, 2013 and B, 1938 showing location of bed-sediment cores, samples, and tile probe soundings for sites TC1, TC2, and TC3 in Turkey Creek, Missouri, 2012.
Occurrence, Distribution, and Volume of Metals-Contaminated Sediment 45 TC-D-HD1 TC-D-HD2 94°34'00" 94°34'05" 94°34'10" 94°34'15" 37°07'15" 37°07'10" 37°07'05" 37°07'00" TC-E-HD1 TC-E-HD2 TC-E-WC1 TC-E-HD3 94°33'20" 94°33'25" 94°33'30" 94°33'35" 37°07'05" 37°07'00" 37°06'55" TC-D-HD1 TC-D-HD2 94°34'00" 94°34'05" 94°34'10" 94°34'15" TC-E-HD1 TC-E-HD2 TC-E-WC1 TC-E-HD3 94°33'20" 94°33'25" 94°33'30" 94°33'35" Base from National Agriculture Imagery Program (NAIP), U.S. Department of Agriculture, 2013 (left images); Natural Resources Conservation Service (NRCS) aerial photography, 1938 (right images) Geographic coordinate system, North American Datum 1983 A. 2013 TC4 A. 2013 TC5 B. 1938 TC5 B. 1938 TC4 NORTH BLACK CAT ROAD NORTH BLACK CAT ROAD TC-D-HD1 TC4 Direction of flow Site identifier EXPLANATION Tile probe sounding Channel core or sample and identifier Turkey Creek Turkey Creek Turkey Creek Turkey Creek 400 FEET 400 METERS Figure 18. Aerial photographs from A, 2013 and B, 1938 showing location of bed-sediment cores, samples, and tile probe soundings for sites TC4 and TC5 in Turkey Creek, Missouri, 2012.
46 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District TC-B-HD1 TC-C-HD1 TC-C-HD2 TC-C-HS1 TC-B-HD2 94°30'25" 94°30'30" 94°30'35" 94°30'40" 37°06'35" 37°06'30" 37°06'25" 37°06'20" TC-A-HD1 TC-A-HD2 94°28'35" 94°28'40" 94°28'45" 94°28'50" 37°06'05" 37°06'00" 37°05'55" TC-B-HD1 TC-C-HD1 TC-C-HD2 TC-C-HS1 TC-B-HD2 94°30'25" 94°30'30" 94°30'35" 94°30'40" TC-A-HD1 TC-A-HD2 94°28'35" 94°28'40" 94°28'45" 94°28'50" 400 FEET 400 METERS TC-C-HD1 TC6 Direction of flow Site identifier EXPLANATION Tile probe sounding Channel core or sample and identifier Base from National Agriculture Imagery Program (NAIP), U.S. Department of Agriculture, 2013 (left images); U.S. Geological Survey aerial photography, 1961 (right images) Geographic coordinate system, North American Datum 1983 A. 2013 TC6 A. 2013 TC7 B. 1961 TC7 B. 1961 TC6 NORTH RANGELINE ROAD NORTH RANGELINE ROAD Turkey Creek Turkey Creek Turkey Creek Turkey Creek Figure 19. Aerial photographs from A, 2013 and B, 1961 showing location of bed-sediment cores, samples, and tile probe soundings for sites TC6 and TC7 in Turkey Creek, Missouri, 2012.
Occurrence, Distribution, and Volume of Metals-Contaminated Sediment 47 other parts of the gravel bar with no success. Coring at this location was extremely difficult because of large boulders and broken concrete rubble placed in the creek to control ero sion. The downstream gravel bar at site TC6 had two cores (TC-C-HD1 and TC-C-HD2) and one hand sample location (TC-C-HS1; fig. 19). Site TC7, located near North Rangeline Road, had two cores (TC-A-HD1 and TC-A-HD2) and was the farthest upstream bar sampled on Turkey Creek (fig. 19). Depth and Concentration of Metals in Channel Sediments A total of 100 samples were collected from 23 locations on gravel bar deposits along Turkey Creek. The maximum sample depth was 13 ft, with the thickest channel deposits in the gravel bars at sites TC2 and TC3 (table 5) and thinnest deposits at upstream site TC7 (<2 ft thick). Excluding samples with concentrations below the LOD, median lead concentra tions increased from the most upstream site TC7 to a peak at TC5 and decreased somewhat at the two downstream sites TC1 and TC2 (fig. 12). Median zinc concentrations increased from the most upstream site at TC7 to a peak at TC4 then remained relatively steady to the most downstream site at TC1 (fig. 12). Median cadmium concentrations increased from concentrations below the LOD at the upstream site TC7 to site TC3 and then remained relatively steady to the most down stream site at TC1 (fig. 12). Lead and zinc concentrations in nearly all gravel barsediment samples from Turkey Creek exceeded the CPEC and TPEC often to the maximum depth of the boreholes. Lead con centrations exceeded the CPEC in all but 6 samples (94 per cent) and exceeded the TPEC in all but 11 samples. Zinc concentrations exceeded the CPEC in all but 1 sample (99 percent) and exceeded the TPEC in all but 13 samples. Most samples also had exceedances of both PECs for cadmium (minimum of 70 percent; <12 to 175 mg/kg), although this number of exceedances may be greater because the XRF LOD is greater than the CPEC and TPEC for cadmium. Cadmium concentrations exceeding the CPEC and TPEC were present as deep as 11.5 ft. Few samples exceeded the CPECs for metals other than lead, zinc, and cadmium, although exceedances for nickel may be underrepresented because the CPEC for nickel (48.6 mg/kg) is less than the XRF LOD (65 mg/kg). Lead concentrations in gravel bar-sediment samples from Turkey Creek ranged from 70 mg/kg to 7,520 mg/kg and zinc concentrations ranged from 329 mg/kg to 27,900 mg/kg (Smith, 2016; Stream channel sediment samples). The smallest lead and zinc concentrations generally were from upstream site TC7 where lead and zinc concentrations were less than the TPEC in all four samples from this site. At site TC7, the lead concentration exceeded the CPEC in one sample, and the zinc concentration exceeded the CPEC in all four samples (figs. 20 and 21). All samples collected from sites downstream from TC7 contained lead concentrations greater than the CPEC with the exception of three samples with concentrations <120 mg/kg (at boreholes TKC-CH-4 [0 to 2 ft], TKC-CH-6 [8 ft], and TKC-WC-1 [3.6 to 4.6 ft]). Samples that exceeded the CPEC in Turkey Creek generally exceeded the larger TPEC with the exception of 5 samples: TC-C-HS1 from 0 to 1 ft (129 mg/kg), TC-A-HD2 from 0 to 1 ft (137 mg/kg), TKC-CH-2 from 7.2 to 8.2 ft (140 mg/kg), TKC-CH-3 from 8 to 9 ft (128 mg/kg), and TKC-CH-3 from 9 to 10 ft (138 mg/kg) (Smith, 2016; Stream channel sediment samples; fig. 20). Estimated Volume of Channel Sediment Contaminated by Mine Waste Sediment deposited in gravel bars along the entire 10.1-mi study reach of Turkey Creek had concentrations of lead and zinc that exceeded the CPEC and the TPEC, from the gravel bar at site TC7 to the creek's mouth at the Spring River. The gravel bar at site TC7 was chosen as the farthest upstream extent for the estimated volume of sediment because no data were collected farther upstream from this site. The mean thickness of sediment that would need excavation based on the CPEC for Turkey Creek was 4.9 ft and the mean thickness of sediment that would need excavation based on the TPEC was 4.6 ft (table 5). The total area of studied gravel bars for Turkey Creek was 632,000 ft2 (14.5 acres; table 5). The estimated minimum volume of sediment in gravel bars exceeding the CPEC for the chosen reach of Turkey Creek was 115,000 yd3 and 108,000 yd3 of sediment in gravel bars exceeding the TPEC (table 5). These estimates are considered minimum volumes because they were only based on the visible gravel bars and do not include sediment beneath the wetted channel in other features such as pools, and presumably some of these deposits are negatively affected by mine-waste contaminated sediment but were not sufficiently characterized to be included in the volume estimate. Depth and Concentration of Metals in FloodPlain Sediments A total of 73 samples were collected from six locations on the Turkey Creek flood plain (Smith, 2016; Flood-plain cores). Of these, cadmium concentrations were analyzed in 51 samples (Smith, 2016; Flood-plain cores). Nine of the 73 samples had concentrations of lead greater than the CPEC and 15 had concentrations of zinc greater than the CPEC. Lead concentrations in eight samples and zinc concentrations in five samples exceeded their respective TPECs. The exceedances of the TPEC for lead or zinc were limited to the upper 1 or 2 feet of the cores except for core TKC-FP-2 where concentrations of lead and zinc were less than the CPEC and TPEC in the upper few feet. Concentrations for lead and zinc for core TKCFP-2 gradually increased with depth and lead exceeded the CPEC between 6 and 10 ft (fig. 15). The largest concentrations of lead (789 mg/kg from core TKC-FP-4) and zinc (6,620 mg/kg from core TKC-FP-3) were in the 0 to 1 ft intervals
48 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District TC-A-HD1 TC-A-HD2 TC-B-HD1 TC-B-HD2 TC-C-HD1 TC-C-HD2 TC-C-HS1 TC-D-HD1 TC-D-HD2 TC-E-HD1 TC-E-HD2 TC-E-HD3 TC-E-WC1 TKC-CH-1 TKC-CH-2 TKC-CH-3 TKC-CH-4 TKC-CH-5 TKC-CH-5P TKC-CH-6 TKC-CH-7 TKC-WC-1 TKC-WC-3 TC1 TC2 TC3 TC4 TC5 TC6 TC7 TC5 TC6 1,000 1,000 1,000 1,000 1,000 Concentration of lead in sediment samples, in milligrams per kilogram Midpoint of each sample interval below the local water surface, in feet [Core and site identifiers are explained in table 1] Sample concentration Probable effects concentration, 128 milligrams per kilogram Tri-State Mining District specific probable effects concentration, 150 milligrams per kilogram EXPLANATION Figure 20. Vertical profiles by core and sample location of lead concentrations in the less than 2-millimeter size fraction of gravel bar-sediment samples analyzed by x-ray fluorescence in Turkey Creek, Missouri, 2012.
Occurrence, Distribution, and Volume of Metals-Contaminated Sediment 49 10,000 1,000 10,000 1,000 10,000 1,000 10,000 1,000 10,000 1,000 [Core and site identifiers are explained in table 1] Sample concentration Probable effects concentration, 459 milligrams per kilogram Tri-State Mining District specific probable effects concentration, 2,083 milligrams per kilogram EXPLANATION Concentration of zinc in sediment samples, in milligrams per kilogram Midpoint of each sample interval below the local water surface, in feet TC-A-HD1 TC-A-HD2 TC-B-HD1 TC-B-HD2 TC-C-HD1 TC-C-HD2 TC-C-HS1 TC-D-HD1 TC-D-HD2 TC-E-HD1 TC-E-HD2 TC-E-HD3 TC-E-WC1 TKC-CH-1 TKC-CH-2 TKC-CH-3 TKC-CH-4 TKC-CH-5 TKC-CH-5P TKC-CH-6 TKC-CH-7 TKC-WC-1 TKC-WC-3 TC1 TC4 TC5 TC6 TC7 TC6 TC2 TC3 TC5 Figure 21. Vertical profiles by core and sample location of zinc concentrations in the less than 2-millimeter size fraction of gravel bar-sediment samples analyzed by x-ray fluorescence in Turkey Creek, Missouri, 2012.
50 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District (figs. 15, 16). Borehole TKC-FP-1 was farthest from the creek and lead concentrations in all samples from this core were less than the CPEC, however, zinc concentrations were greater than the CPEC in most samples ft deep. Three cores (TKCFB-1, TKC-FB-2, and TKC-FP-4) had lead concentrations exceed both PECs in the top 1 ft of depth only (fig. 15). Those lead concentrations were 371 mg/kg (TKC-FB-1), 162 mg/kg (TKC-FB-2), and 789 mg/kg (TKC-FP-4). Cadmium concentrations exceeded the CPEC at most depths in flood-plain cores on Turkey Creek. Out of 51 samples from the flood plain that were analyzed for cadmium concentrations, a minimum 44 concentrations exceeded both PECs for cadmium (Smith, 2016; Flood-plain cores). The number of cadmium concentration exceedances may be greater because the LOD (12 mg/kg) is larger than the CPEC (4.98 mg/kg) and TPEC (11.1 mg/kg). Shoal Creek Shoal Creek has a drainage area of 251 mi2 at its conflu ence with Spring River and is approximately 80.2 mi in length from the headwaters to the mouth. Approximately 19 mi of the lower part of the creek was studied and the lower 9 mi was used in the estimation of the volume of contaminated sediment (table 5). Site Selection and Description Shoal Creek gravel bar-sediment samples and flood-plain samples were collected from eight sites during a period of 3 weeks during the summer of 2012. Because of difficulties with permission to access the flood plain in the vicinity of sampled gravel bars, an intensive study area with a number of co-located flood-plain borehole and channel core samples was not possible. Flood-plain boreholes were drilled at two sites (SFP1 and SFP2) with no corresponding gravel bar-sediment samples, and hand samples of flood-plain deposits were obtained from a cut bank and the side wall of an excavation at site S4. The flood-plain transect SH-SH' along Shoal Creek was at the downstream most site (SFP1) about 2.0 mi south of Galena, Kansas (fig. 1). Four boreholes were drilled on the north side of the stream at distances of about 450 ft (SH-FP-1), 900 ft (SH-FP-2), 1,400 ft (SH-FP-3), and 1,900 ft (SH-FP-4) from the stream (fig. 22). Two additional flood-plain boreholes (SH-FB-2 and SH-FB-3) were drilled on the south side of Shoal Creek at site SFP2 (fig. 23) about 5.5 mi upstream from site SFP1. Access to the channel at these two sites was limited to a reach that contained few channel deposits at either site; therefore, no gravel bar-sediment samples were collected at the sites with the flood-plain samples. Gravel bar-sediment samples from Shoal Creek were collected from 12 locations at 5 sites along the lower 19 mi of Shoal Creek (S1, S2, S3, S4, and S5; fig. 1). Sites S1, S2, S3, and S4 were along about a 6-mi reach of Shoal Creek rang ing from about 2.5 mi to about 10.5 mi upstream from Empire Lake. The upstream most site (S5) was about 10 mi upstream from site S4. Site S4 was about 1,000 ft upstream from the Schifferdecker Road Bridge (fig. 24). This site included three channel sediment cores (SH-CH-1, SH-CH-2, and SH-WC1) and two nearby flood-plain sample locations (SH-FB-1 and SH-FB-4). Flood-plain locations SH-FB-1 and SH-FB-4 were samples of soil from the side wall of an excavation made by a gravel mining operation (SH-FB-1) and the side of an inactive cut bank on the north side of the creek (SH-FB-4; fig. 24). Three channel sediment cores were collected about 0.1 mi downstream at site S3 (fig. 24). Core SH-CH-5 was on a gravel bar 400 ft upstream from the Schifferdecker Road Bridge on the north side of the channel. Core SH-WC-2 was also upstream from the bridge but inside the wetted channel. Downstream from the bridge, core SH-CH-7 was collected on the south side of the creek (fig. 24). Site S2 was centered on a gravel bar near the City of Joplin's Shoal Creek Wastewater Plant and had two cores (SH-CH-8 and SH-CH-9; fig. 23). Site S1 was on the south side of Galena, Kans., and included the gravel bar cores SH-CH-11 and SH-WC-3 (fig. 22). Two bore holes (SC-A-HD1 and SC-A-HD2) were drilled on a gravel bar about 10 mi upstream from site S4 at site S5 (fig. 24). Depth and Concentration of Metals in Channel Sediments A total of 65 samples were collected from 12 locations on gravel-bar deposits along Shoal Creek. The maximum sample depth was 11.9 ft. The maximum depth of sediments that had concentrations of lead and zinc that exceeded the respective CPEC for those metals was 7 ft for lead and 9 ft for zinc. Overall, cores from Shoal Creek generally had concentrations of zinc that exceeded the CPEC at many depths, including the upstream site S5 about 19 mi upstream from Empire Lake. Few samples had exceedances of the TPEC for any MVTrelated metals in channel sediments from Shoal Creek. In the <2-mm size fraction of gravel bar-sediment samples from Shoal Creek, lead concentrations ranged from <13 mg/kg to 183 mg/kg (Smith, 2016; Stream channel sedi ment samples). Of the 65 samples, 8 samples (12 percent) had lead concentrations greater than the CPEC and only 4 samples (about 6 percent) had concentrations greater than the TPEC. Five of the eight gravel bar-sediment samples greater than the CPEC for lead and three greater than the TPEC for lead were from site S2 at borehole SH-CH-9 (2 to 7 ft). The other samples were from site S3 from borehole SH-CH-7 from 2 to 3 ft (139 mg/kg), site S2 from borehole SH-CH-8 from 0 to 1 ft (181 mg/kg), and site S1 from borehole SH-CH-11 from 1 to 2 ft (130 mg/kg) (Smith, 2016; Stream channel sediment samples; fig. 25). Zinc concentrations in the <2-mm size fraction in samples ranged from 176 mg/kg to 3,010 mg/kg and cadmium concentrations were <12 mg/kg in all samples (Smith, 2016; Stream channel sediment samples). Almost 74 percent of the samples (48 of 65) had zinc concentrations greater than
Occurrence, Distribution, and Volume of Metals-Contaminated Sediment 51 SH-FP-1 SH-FP-2 SH-FP-3 SH-FP-4 94°38'40" 94°38'45" 94°38'50" 94°38'55" 94°39'00" 37°02'50" 37°02'45" 37°02'40" 37°02'35" 37°02'30" SH-CH-11 SH-WC-3 94°38'15" 94°38'20" 94°38'25" 94°38'30" 94°38'35" 37°02'40" 37°02'35" 37°02'30" 37°02'25" 37°02'20" SH-FP-1 SH-FP-2 SH-FP-3 SH-FP-4 SH SH' SH SH' 94°38'40" 94°38'45" 94°38'50" 94°38'55" 94°39'00" SH-CH-11 SH-WC-3 94°38'15" 94°38'20" 94°38'25" 94°38'30" 94°38'35" 400 FEET 400 METERS SH-FP-1 SH-CH-1 S1 Frequently to occasionally flooded soil Flood-plain transect Direction of flow Site identifier EXPLANATION Flood-plain core or sample and identifier Channel core or sample and identifier SH SH' Flooded soils from Natural Resources Conservation Service (NRCS) digital data, 2003 Base from National Agriculture Imagery Program (NAIP), U.S. Department of Agriculture, 2013 (left images); U.S. Geological Survey aerial photography, 1958 (right images) Geographic coordinate system, North American Datum 1983 A. 2013 SFP1 A. 2013 S1 B. 1958 S1 B. 1958 SFP1 Shoal Creek Shoal Creek Shoal Creek Shoal Creek Figure 22. Aerial photographs from A, 2013 and B, 1958 showing location of bed-sediment cores and sample locations for sites SFP1 and S1 in Shoal Creek, Missouri, 2012.
52 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District SH-CH-8 SH-CH-9 94°35'20" 94°35'25" 94°35'30" 94°35'35" 37°02'10" 37°02'05" 37°02'00" SH-FB-2 SH-FB-3 94°34'25" 94°34'30" 94°34'35" 94°34'40" 37°02'25" 37°02'20" 37°02'15" 37°02'10" SH-CH-8 SH-CH-9 94°35'20" 94°35'25" 94°35'30" 94°35'35" SH-FB-2 SH-FB-3 94°34'25" 94°34'30" 94°34'35" 94°34'40" A. 2013 S2 A. 2013 SFP2 B. 1938 SFP2 B. 1938 S2 Shoal Creek Wastewater Treatment Plant Shoal Creek Shoal Creek Shoal Creek Shoal Creek SH-FB-2 SH-CH-9 S2 Frequently to occasionally flooded soil Direction of flow Site identifier EXPLANATION Flood-plain core or sample and identifier Channel core or sample and identifier Flooded soils from Natural Resources Conservation Service (NRCS) digital data, 2003 Base from National Agriculture Imagery Program (NAIP), U.S. Department of Agriculture, 2013 (left images); Natural Resources Conservation Service (NRCS) aerial photography, 1938 (right images) Geographic coordinate system, North American Datum 1983 400 FEET 400 METERS Figure 23. Aerial photographs from A, 2013 and B, 1938 showing location of bed-sediment cores and sample locations for sites S2 and SFP2 in Shoal Creek, Missouri, 2012.
Occurrence, Distribution, and Volume of Metals-Contaminated Sediment 53 SH-CH-1 SH-CH-2 SH-CH-5 SH-CH-7 SH-WC-1 SH-WC-2 SH-FB-4 SH-FB-1 94°33'10" 94°33'15" 94°33'20" 94°33'25" 94°33'30" 37°02'15" 37°02'10" 37°02'05" 37°02'00" SC-A-HD1 SC-A-HD2 94°26'15" 94°26'20" 94°26'25" 94°26'30" 36°59'10" 36°59'05" 36°59'00" 36°58'55" 36°58'50" SH-CH-1 SH-CH-2 SH-CH-5 SH-CH-7 SH-WC-1 SH-WC-2 SH-FB-4 SH-FB-1 94°33'1 94°33'15" 94°33'20" 94°33'25" 94°33'30" SC-A-HD1 SC-A-HD2 94°26'15" 94°26'20" 94°26'25" 94°26'30" 400 FEET 400 METERS Base from National Agriculture Imagery Program (NAIP), U.S. Department of Agriculture, 2013 (left images); Natural Resources Conservation Service (NRCS) aerial photography, 1938 (top right); U.S. Geological Survey aerial photography, 1958 (bottom right) Geographic coordinate system, North American Datum 1983 SH-FB-1 SH-CH-1 S3 Frequently to occasionally flooded soil Direction of flow Site identifier EXPLANATION Tile probe sounding Flood-plain core or sample and identifier Channel core or sample and identifier Flooded soils from Natural Resources Conservation Service (NRCS) digital data, 2003 SCHIFFERDECKER ROAD A. 2013 D. 1958 S5 S5 S4 S3 S4 B. 1938 S3 Shoal Creek Shoal Creek Shoal Creek Shoal Creek Figure 24. Aerial photographs from A, 2013 and B, 1938 for sites S3 and S4, and from C, 2013 and D, 1958 for site S5 showing location of cores, samples, and tile probes in Shoal Creek, Missouri, 2012.
54 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District [Core and site identifiers are explained in table 1] Sample concentration Probable effects concentration, 128 milligrams per kilogram Tri-State Mining District specific probable effects concentration, 150 milligrams per kilogram EXPLANATION S1 S2 S3 S4 S4 S5 SC-A-HD1 SC-A-HD2 SH-CH-1 SH-CH-11 SH-CH-2 SH-CH-5 SH-CH-7 SH-CH-8 SH-CH-9 SH-WC-1 SH-WC-2 SH-WC-3 Midpoint of each sample interval below local water surface, in feet Concentration of lead in sediment samples, in milligrams per kilogram Figure 25. Vertical profiles by core and sample location of lead concentrations in the less than 2-millimeter size fraction of stream channel samples analyzed by x-ray fluorescence in Shoal Creek, Missouri, 2012.
Occurrence, Distribution, and Volume of Metals-Contaminated Sediment 55 the CPEC, but only one sample had a concentration greater than the TPEC (borehole SH-CH-8 at depth interval 0 to 1 ft (Smith, 2016; Stream channel sediment samples). This sample was collected at the same site (S2) where all four samples exceeding the lead TPEC were found. The wastewater plant outfall has created a large pool (fig. 23), which may act as a trap and allow fine material to collect at this site. Concentra tions of zinc that exceeded the CPEC generally extended several feet to as much as 9 ft below the surface of the channel sediment (Smith, 2016; Stream channel sediment samples; fig. 26). Concentrations of zinc in 9 of the 15 samples from site S5 were greater than the CPEC with the maximum of 996 mg/kg in samples from ft deep (Smith, 2016; Stream channel sediment samples). None of the stream channel sedi ments contained detectable concentrations of cadmium, and only four samples contained concentrations of nickel greater than the LOD of 65 mg/kg. Estimated Volume of Channel Sediment Contaminated by Mine Waste The volume of contaminated sediment within sampled gravel bars was estimated for the 9-mi reach of Shoal Creek from site S4 to the upper end of the south arm of Empire Lake (fig. 1). Although channel sediments at site S5 contained zinc concentrations greater than the CPEC, the absence of data along the nearly 10-mi reach between this site and the next downstream site (S4) precluded the estimation of contami nated sediment volume along this reach. The mean thickness of sediment along the lower, 9-mi reach of Shoal Creek that would need excavation based on the CPEC was 4.5 ft, and the mean thickness of sediment that would need excavation based on the TPEC was 0.8 ft (table 5). The total area of studied gravel bars for Shoal Creek was 146,000 ft2 (3.4 acres; table 5). Using the mean thickness of contaminated sedi ment and a total area of sampled gravel bars along this reach of 146,000 ft2, the estimated minimum volume of contami nated sediment in gravel bars exceeding the CPEC is about 24,000 yd3 (table 5). The estimated minimum volume of sedi ment in gravel bars exceeding the TPEC is smaller at about 4,000 yd3 (table 5). These estimates are considered minimum volumes because they were only based on the visible gravel bars and do not include sediment beneath the wetted channel in other features such as pools, and presumably some of these deposits are negatively affected by mine-waste contaminated sediment but were not sufficiently characterized to be included in the volume estimate. Depth and Concentration of Metals in FloodPlain Sediments A total of 80 flood-plain samples were collected from 8 locations along the Shoal Creek flood plain (Smith, 2016; Flood-plain cores). Lead concentrations greater than the CPEC were present in 5 of the 80 (about 6 percent) flood-plain samples from Shoal Creek. Zinc concentrations exceeded the CPEC in 11 samples (about 14 percent). Flood-plain cores sampled along Shoal Creek tended to have concentrations of lead and zinc below the CPEC and TPEC, even in the upper 2 ft of depth; however, the samples from borehole SH-FB-4 had lead or zinc concentrations that exceeded the CPEC and TPEC to depths greater than 8 ft (Smith, 2016; Flood-plain cores; figs. 15, 16). All 5 of the CPEC exceedances by lead concentration and 9 of the 11 CPEC exceedances by zinc were from this single location. Samples at this location were col lected from a cut bank on the north side of Shoal Creek at site S4 (fig. 24). It is possible that the stream channel at this loca tion has migrated southward leaving a thick metal-rich deposit of recently (post mining) deposited sediment but comparison of the 1938 and 2013 imagery the migration of what would be defined as the thalweg is not definitive (fig. 24). The area also has active gravel mining and other disturbances such as maintenance of the nearby gravel road for access to the gravel bar or erosion control may have occurred since 1938, and this material may have been reworked at some point as well. This would mean that nearby metal-rich surficial material could have been filled and graded in this area, which could create an anthropogenic sediment profile that is not representative of the natural deposition of sediment from the nearby stream. Tar Creek Tar Creek has a drainage area of 53 mi2 at its confluence with the Neosho River and is approximately 19.3 mi in length from the headwaters to the mouth. Approximately 7.4 mi of the creek was studied and was used in the estimation of the volume of contaminated sediment (table 5). Site Selection and Description Tar Creek gravel bar-sediment samples and flood-plain samples were collected during a period of 3 weeks in the summer of 2012. The Tar Creek study reach consisted of multiple sites including 22 stream channel cores and 13 floodplain cores collected in gravel bars, wetted channels, and the adjacent flood plain. One of the more intensively studied sites (TR4) was located just east of Miami, Oklahoma. Transect TR2-TR2' with five cores at site TRFP2 (TAR-FP2-1, TARFP2-2, TAR-FP2-3, TAR-FP2-4, and TAR-FP2-5) were drilled across the flood plain (figs. 1 and 27). Three additional floodplain cores (TAR-FB-1, TAR-FB-2, and TAR-FB-3) were located off transect TR2-TR2'. Cores TAR-FB-2 and TARFB-3 were in what may have been an older channel of the creek. Core TAR-FB-1 was in an area to contrast the locations of cores TAR-FB-2 and TAR-FB-3 and was located slightly upstream from the other cores and farther away from the stream (1,500 ft). Near flood-plain transect TR2-TR2' were six stream channel cores (site TR4); two cores (TAR-TR-4 and TAR-4-HC1) were on a gravel bar downstream from the flood-plain transect TR2-TR2' and four cores (TAR-BAR-1,
56 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District [Core and site identifiers are explained in table 1]
Sample concentration Probable effects concentration, 459 milligrams per kilogram Tri-State Mining District specific probable effects concentration, 2,083 milligrams per kilogram EXPLANATION Midpoint of each sample interval below the local water surface, in feet Concentration of zinc in sediment samples, in milligrams per kilogram 1,000 1,000 1,000 1,000 SC-A-HD1 SC-A-HD2 SH-CH-1 SH-CH-11 SH-CH-2 SH-CH-5 SH-CH-7 SH-CH-8 SH-CH-9 SH-WC-1 SH-WC-2 SH-WC-3 S1 S2 S3 S4 S4 S5 Figure 26. Vertical profiles by core and sample location of zinc concentrations in the less than 2-millimeter size fraction of stream channel samples analyzed by x-ray fluorescence in Shoal Creek, Missouri, 2012.
Occurrence, Distribution, and Volume of Metals-Contaminated Sediment 57 TAR-12-HC1 TAR-3-HP1 TAR-4-HC1 TAR-11-HC1 TAR-TR-1 TAR-TR-11 TAR-TR-2 TAR-TR-3 TAR-TR-4 TAR-TR-5 TAR-FB-1 TAR-FB-2 TAR-FB-3 TAR-FP2-1 TAR-FP2-2 TAR-FP2-3 TAR-FP2-4 TAR-FP2-5 TR2 TR2' TAR-TR-3A 94°51'50" 94°52'00" 94°52'10" 94°52'20" 36°55'10" 36°55'00" 36°54'50" 36°54'40" 36°54'30" 36°54'20" 36°54'10" 500 FEET 500 METERS TAR-12-HC1 TAR-3-HP1 TAR-4-HC1 TAR-11-HC1 TAR-TR-1 TAR-TR-11 TAR-TR-2 TAR-TR-3 TAR-TR-4 TAR-TR-5 TAR-FB-1 TAR-FB-2 TAR-FB-3 TAR-FP2-1 TAR-FP2-3 TAR-FP2-2 TAR-FP2-4 TAR-FP2-5 TAR-TR-3A TR2 TR2' 94°51'50" 94°52'0" 94°52'10" 94°52'20" Base from National Agriculture Imagery Program (NAIP), U.S. Department of Agriculture, 2013 (left); U.S. Geological Survey aerial photography, 1958 (right) Geographic coordinate system, North American Datum 1983 Flooded soils from Natural Resources Conservation Service (NRCS) digital data, 2003 TR7 TR7 TR1 TR1 TR2 TR2 TR3 TR3 TR4 TR5 TR5 TRFP2 TRFP2 TR6 TR6 TR4 Abandoned channel Abandoned channel A. 2013 B. 1958 Tar Creek Tar Creek TAR-FB-1 TAR-TR-1 TR1 Frequently to occasionally flooded soil Flood-plain transect Direction of flow Site identifier—Yellow represents a flood-plain site EXPLANATION Tile probe sounding Flood-plain core or sample and identifier Channel core or sample and identifier TR2 TR2' Figure 27. Aerial photographs from A, 2013 and B, 1958 showing location of sediment cores, samples, and tile probe soundings for sites TR7, TR6, TR5, TRFP2, TR4, TR3, TR2, and TR1 on Tar Creek, Oklahoma, 2011.
58 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District TAR-3-HP1, TAR-TR-3, and TAR-TR-3A were on a gravel bar upstream from the flood-plain transect TR2-TR2'. Within about 0.5 mi of site TR4 were six additional core and sample locations at five different sites. Sites TR7 (TAR-TR-1) and TR6 (TAR-TR-2) are upstream and sites TR3 (TAR-TR-5), TR2 (TAR-11-HC1 and TAR-TR-11), and TR1 (TAR-12-HC1) are downstream sites (fig. 27). Another area, east of Commerce, Okla., and about 2 mi upstream from the flood-plain transect TR1-TR1' at site TRFP1, had 6 sites with 11 gravel bar-sediment samples and sample locations and 5 flood-plain cores. Those sites (fig. 28), in order from upstream to downstream, are TR12 (TAR-8-VC1 and TAR-TR-8), TR11 (TAR-FB-4, TAR-9-PT1, TAR-9-VC1, TAR-9-VC1A, and TAR-TR-9), TRFP1 (TAR-FP1-1, TARFP1-2, TAR-FP1-3, and TAR-FP1-4), TR10 (TAR-TR-7), TR9 (TAR-TR-6 and TAR-6-VC1), and TR8 (TAR-TR-10). Depth and Concentration of Metals in Channel Sediments A total of 51 samples were collected on gravel bar depos its along Tar Creek. The maximum sample depth was 6.6 ft. Overall, concentrations of lead and zinc generally exceeded the CPEC in cores from the surface to the top of bedrock that was generally ft deep and in some cases ft deep. Lead and zinc concentrations generally also exceeded the TPEC from the surface to the maximum depth. Lead concentra tions, in the <2-mm size fraction in these samples, ranged from a single non-detection (<13 mg/kg) to 2,540 mg/kg (Smith, 2016; Stream channel sediment samples). Out of the 51 gravel bar-sediment samples, all but 6 (88 percent) had lead concentrations greater than the CPEC and the TPEC. All samples collected in Tar Creek that exceeded the CPEC for lead also exceeded the TPEC (Smith, 2016; Stream channel sediment samples; fig. 29). Zinc concentrations, in the <2-mm size fraction in these samples, ranged from 63.0 mg/kg to 46,600 mg/kg (Smith, 2016; Stream channel sediment sam ples). Out of the 51 stream channel samples, all but 2 (96 per cent) had zinc concentrations that exceeded the CPEC, and all but 5 had concentrations that exceeded the TPEC (Smith, 2016; Stream channel sediment samples; fig. 30). Cadmium concentrations, in the <2-mm size fraction in these cores, ranged from non-detection (<12 mg/kg) to 131 mg/kg (Smith, 2016; Stream channel sediment samples). Of 51 stream channel samples, 35 had detectable cadmium (69 percent) and exceeded the CPEC and TPEC. Cadmium concentrations exceeded the CPEC and TPEC in samples from multiple depths. The number of cadmium concentration exceedances may be greater because the LOD (12 mg/kg) is larger than the CPEC (4.98 mg/kg) and TPEC (11.1 mg/kg). Of the 51 samples, 31 (61 percent) had concentrations of nickel that exceeded the CPEC (48.6 mg/kg). There is no TPEC for nickel. Exceedances of the CPEC for nickel gener ally extended several feet below the surface and were pres ent as deep as 6.6 ft (sample TAR-9-VC1A). Nickel CPEC exceedance frequencies may be underreported because the LOD (65 mg/kg) is larger than the CPEC (48.6 mg/kg). Estimated Volume of Channel Sediment Contaminated by Mine Waste The total volume of sediment in Tar Creek gravel bar deposits that had concentrations of lead and zinc that exceeded the CPEC and the TPEC was estimated using data collected in this study. The estimated volume was computed for the 7.4-mi Tar Creek reach from about 800 ft upstream from site TR12 to the creek's confluence at the Neosho River. Although large mine-waste piles and past mining areas are upstream from the site chosen as the farthest upstream extent of the contaminated sediment-volume analysis, no data were collected upstream from the TR12 location. The mean thickness of sediment that exceeded the CPEC and the TPEC for Tar Creek was 1.1 ft (table 5). The total area of studied gravel bars for Tar Creek was 230,000 ft2 (5.3 acres; table 5). The estimated mini mum volume of sediment in sampled gravel bars exceeding the CPEC and TPEC for the chosen reach of Tar Creek was 9,000 yd3 (table 5). These estimates are considered minimum volumes because they were only based on the visible gravel bars and do not include sediment beneath the wetted channel in other features such as pools, and presumably some of these deposits are negatively affected by mine-waste contaminated sediment but were not sufficiently characterized to be included in the volume estimate. Depth and Concentration of Metals in FloodPlain Sediments A total of 142 samples were collected from 13 locations along the Tar Creek flood plain (Smith, 2016; Flood-plain cores). Concentrations of lead and zinc in flood-plain samples from Tar Creek generally exceeded the CPEC and the TPEC in the upper 1 or 2 ft of soil, and the concentrations were generally greater than concentrations in samples deeper than 2 or 3 ft by an order of magnitude or more. Lead and zinc concentrations in flood-plain samples seemed to decrease with distance from the creek. The 7 cores located within 450 ft of the creek had lead and zinc concentrations that exceeded the CPEC and the TPEC, whereas the 6 cores at distances greater than 450 ft from the creek had no exceedances. Lead concen trations in 11 of 142 analyzed flood-plain core sections from Tar Creek exceeded the CPEC and the TPEC. Concentrations of zinc exceeded the CPEC in 21 flood-plain core sections and exceeded the TPEC in 9 flood-plain core sections. Cadmium concentrations exceeded the CPEC and the TPEC in 25 of 33 flood-plain core sections where cadmium was analyzed. Site TRFP1 (figs. 1, 28) was east of Commerce, Okla. This site had four cores (in order from nearest to the creek to the farthest): TAR-FP1-1, TAR-FP1-2, TAR-FP1-3, and TAR-FP1-4 (fig. 28). The lead concentration in samples from TAR-FP1-1 exceeded the CPEC and TPEC at depths ft
Occurrence, Distribution, and Volume of Metals-Contaminated Sediment 59 TAR-6-VC1 TAR-8-VC1 TAR-9-PT1 TAR-9-VC1 TAR-9-VC1A TAR-BAR-1 TAR-TR-10 TAR-TR-6 TAR-TR-7 TAR-TR-8 TAR-TR-9 TAR-FB-4 TAR-FP1-1 TAR-FP1-2 TAR-FP1-3 TAR-FP1-4 94°51'10" 94°51'20" 94°51'30" 36°56'30" 36°56'20" 36°56'10" 36°56'00" TAR-6-VC1 TAR-8-VC1 TAR-9-PT1 TAR-9-VC1 TAR-9-VC1A TAR-BAR-1 TAR-TR-10 TAR-TR-6 TAR-TR-7 TAR-TR-8 TAR-TR-9 TAR-FB-4 TAR-FP1-1 TAR-FP1-2 TAR-FP1-3 TAR-FP1-4 94°51'10" 94°51'20" 94°51'30" TR12 TR11 TR10 TRFP1 TR9 TR8 TR12 TR11 TR10 TRFP1 TR9 TR8 A. 2013 B. 1958 Base from National Agriculture Imagery Program (NAIP), U.S. Department of Agriculture, 2013 (left); U.S. Geological Survey aerial photography, 1958 (right) Geographic coordinate system, North American Datum 1983 TAR-FB-4 TAR-TR-8 TR8 Frequently to occasionally flooded soil Flood-plain transect Direction of flow Site identifier EXPLANATION Tile probe sounding Flood-plain core or sample and identifier Channel core or sample and identifier TR1 TR1' Tar Creek Tar Creek TR1 TR1' TR1' TR1 400 FEET 400 METERS Flooded soils from Natural Resources Conservation Service (NRCS) digital data, 2003 Figure 28. Aerial photographs from A, 2013 and B, 1958 showing location of sediment cores, samples, and tile probe soundings for sites TR12, TR11, TRFP1, TR10, TR9, and TR8 on Tar Creek, Oklahoma, 2011.
60 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Midpoint of each sample interval below the local water surface, in feet Concentration of lead in sediment samples, in milligrams per kilogram TAR-11-HC1 TAR-12-HC1 TAR-3-HP1 TAR-4-HC1 TAR-6-VC1 TAR-8-VC1 TAR-9-PT1 TAR-9-VC1 TAR-9-VC1A TAR-BAR-1 TAR-TR-1 TAR-TR-10 TAR-TR-11 TAR-TR-2 TAR-TR-3 TAR-TR-3A TAR-TR-4 TAR-TR-5 TAR-TR-6 TAR-TR-7 TAR-TR-8 TAR-TR-9 1,000 1,000 1,000 1,000 1,000 TR1 TR3 TR2 TR4 TR5 TR6 TR7 TR4 TR8 TR9 TR10 TR11 TR12 [Core and site identifiers are explained in table 1] Sample concentration Probable effects concentration, 128 milligrams per kilogram Tri-State Mining District specific probable effects concentration, 150 milligrams per kilogram EXPLANATION Figure 29. Vertical profiles by core and sample location of lead concentrations in the less than 2-millimeter size fraction of stream channel samples analyzed by x-ray fluorescence in Tar Creek, Oklahoma, 2011.
Occurrence, Distribution, and Volume of Metals-Contaminated Sediment 61 1,000 10,000 1,000 10,000 1,000 10,000 1,000 10,000 1,000 10,000 TAR-11-HC1 TAR-12-HC1 TAR-3-HP1 TAR-4-HC1 TAR-6-VC1 TAR-8-VC1 TAR-9-PT1 TAR-9-VC1 TAR-9-VC1A TAR-BAR-1 TAR-TR-1 TAR-TR-10 TAR-TR-11 TAR-TR-2 TAR-TR-3 TAR-TR-3A TAR-TR-4 TAR-TR-5 TAR-TR-6 TAR-TR-7 TAR-TR-8 TAR-TR-9 TR1 TR3 TR2 TR4 TR5 TR6 TR7 TR4 TR8 TR9 TR10 TR11 TR12 [Core and site identifiers are explained in table 1]
Sample concentration Probable effects concentration, 459 milligrams per kilogram Tri-State Mining District specific probable effects concentration, 2,083 milligrams per kilogram EXPLANATION Midpoint of each sample interval below the local water surface, in feet Concentration of zinc in sediment samples, in milligrams per kilogram Figure 30. Vertical profiles by core and sample location of zinc concentrations in the less than 2-millimeter size fraction of stream channel samples analyzed by x-ray fluorescence in Tar Creek, Oklahoma, 2011.
62 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District and depths between 4 and 5 ft with the greatest concentra tions in the top 2 ft (1,120 mg/kg in the interval 0 to 1 ft and 2,190 mg/kg in the interval 1 to 2 ft). The largest zinc concentrations were also in the top 2 ft (10,700 mg/kg in the interval 0 to 1 ft and 11,900 mg/kg in the interval 1 to 2 ft). Zinc concentration in core TAR-FP1-1 exceeded the CPEC for all samples from depths ft but only exceeded the TPEC for depths ft and the depth interval between 4 and 5 ft. Lead and zinc concentrations in samples from depths ft in cores TAR-FP1-2 and TAR-FP1-3 exceeded the CPEC and TPEC, except for zinc concentrations in TAR-FP1-3, which only exceeded the CPEC. The lead and zinc concentrations generally decreased with depth in core TAR-FP1-4, as they did generally for all flood-plain cores, but concentrations in core TAR-FP1-4 did not exceed the PECs. Site TR11 was about 1,300 ft upstream from site TRFP1 and had a single floodplain core (TAR-FB-4). Core TAR-FB-4 was within 100 ft of the creek, and lead concentrations exceeded the CPEC and the TPEC only in the sample from 0 to 1 ft (220 mg/kg), whereas the zinc concentration in that sample exceeded only the CPEC (1,810 mg/kg) (Smith, 2016; Flood-plain cores; fig. 16). Site TRFP2 (fig. 27) is the downstream flood-plain site. A total of eight flood-plain cores were drilled at this location. Cores TAR-FB-1, TAR-FP2-2, TAR-FP2-3, TAR-FP2-4, and TAR-FP2-5 were located more than 450 ft from the creek and none of the 54 samples from these cores had concentrations of lead or zinc that exceeded the respective CPEC or TPEC (Smith, 2016; Flood-plain cores; figs. 15, 16). TAR-FP2-1 was <300 ft from the creek, and the lead concentration at 0-1 ft below soil surface (190 mg/kg) exceeded the CPEC and TPEC, whereas the zinc concentration in that depth interval (795 mg/kg) exceeded the CPEC only. Cores TAR-FB-2 and TAR-FB-3 were the nearest to the creek (<300 ft) and had concentrations at various depths that exceeded the CPEC or both PECs for lead and zinc. Concentrations of lead and zinc in core TAR-FB-2 exceeded the CPEC and TPEC for all samples from depths ft, whereas for zinc concentrations also exceeded the CPEC for all samples from depths 3-6 ft. Lead concentrations from samples ft deep from TAR-FB-2 were 1 to 2 orders of magnitude greater than concentrations from samples deeper than 3 ft, and zinc concentrations from samples ft deep averaged more than 1 order of magnitude greater than concentrations from samples deeper than 6 ft. Concentrations in samples from core TAR-FB-3 exceeded the CPEC for lead at depths ft and for zinc at depths ft and in the 9 to 10 ft depth interval. The lead and zinc concentra tions in core TAR-FB-3 exceeded the TPEC only for the sam ple from depth 0-1 ft. Like core TAR-FB-2, concentrations of lead and zinc less than the CPEC were generally more than 1 order of magnitude less than the concentrations that exceeded the CPEC (Smith, 2016; Flood-plain cores; figs. 15, 16). Spring River The Spring River has a drainage area of 2,590 mi2 where it enters the Grand Lake O' the Cherokees and is approxi mately 133.6 mi in length. The Spring River was heavily affected by lead and zinc mining in the TSMD because the Spring River and many of its tributary streams received sedi ment loads including waste material derived from mining activities. Site Selection and Description Spring River gravel bar-sediment samples were collected during a 1-week period in the summer of 2012. Juracek (2013) completed a study on the flood plain located adjacent to the downstream gravel bar site sampled in this study so the Spring River flood plain was not sampled during this study. Estimates of the volume of contaminated sediment along the Spring River were also not made because of the small number of loca tions sampled. The Spring River study reach consisted of two sites (SR1 and SR2; fig. 31) where five gravel bar cores were collected. Three cores (SR-CH-1, SR-CH-2, and SR-CH-3) were drilled at site SR1 just north of Baxter Springs, Kans. (figs. 1, 31). Two cores (SR-CH-4 and SR-CH-5) were drilled at site SR2 near the mouth of Turkey Creek, north of Galena, Kans. (figs. 2, 31). Depth and Concentration of Metals in Channel Sediments A total of 52 samples were collected from 5 locations on gravel bar deposits along the Spring River (Smith, 2016; Stream channel sediment samples). The maximum depth sampled was 19.1 ft. Lead concentrations ranged from 14 to 390 mg/kg and exceeded the CPEC in 7 samples (14 per cent). Zinc concentrations ranged from 225 to 5,020 mg/ kg exceeding the CPEC in 46 (89 percent) of the samples. Lead concentrations in gravel bar-sediment samples at the site downstream from Empire Lake (SR1) were generally less than concentrations in samples collected at the upstream site (SR2). Lead concentrations in the <2-mm size fraction from all 38 samples from the downstream site (SR1) were <105 mg/kg, which was less than the CPEC; however, zinc concentrations exceeded the CPEC in 32 of these samples. Lead concentrations at the upstream site (SR2) were larger, exceeding the CPEC and TPEC in 7 of the 14 samples with the largest concentration of 390 mg/kg detected in a samples from 1 to 2 ft deep (Smith, 2016; Stream channel sediment samples). Zinc exceeded the CPEC in all 14 samples from the upstream site and exceeded the TPEC in 7 samples from site SR2. Lead and zinc concentrations in core SR-CH-4 from upstream site SR2 exceeded the respective CPEC and TPEC in all samples from depths up to 5 ft (Smith, 2016;
Occurrence, Distribution, and Volume of Metals-Contaminated Sediment 63 SR-CH-1 SR-CH-2 SR-CH-3 94°43'30" 94°43'35" 94°43'40" 94°43'45" 37°03'45" 37°03'40" 37°03'35" 37°03'30" 37°03'25" SR-CH-1 SR-CH-4 SR-CH-5 94°37'25" 94°37'30" 94°37'35" 94°37'40" 94°37'45" 37°08'00" 37°07'55" 37°07'50" 37°07'45" 37°07'40" SR-CH-1 SR-CH-2 SR-CH-3 94°43'30" 94°43'35" 94°43'40" 94°43'45" SR-CH-4 SR-CH-5 94°37'25" 94°37'30" 94°37'35" 94°37'40" 94°37'45" Turkey Creek Turkey Creek Spring River Spring River Spring River Spring River 400 FEET 400 METERS A. 2013 SR1 A. 2013 SR2 B. 1958 SR2 B. 1958 SR1 SR1 Direction of flow Site identifier Channel core or sample and identifier EXPLANATION Flooded soils from Natural Resources Conservation Service (NRCS) digital data, 2003 Base from National Agriculture Imagery Program (NAIP), U.S. Department of Agriculture, 2013 (left images); U.S. Geological Survey aerial photography, 1958 (right images) Geographic coordinate system, North American Datum 1983 Figure 31. Aerial photographs from A, 2013 and B, 1958 showing location of sediment cores and samples for sites SR1 and SR2 on Spring River, Kansas, 2012.
64 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Stream channel sediment samples; fig. 32). Lead and zinc concentrations in core SR-CH-5 from site SR2 exceeded the respective CPEC and TPEC in both samples from depths ft. Cadmium was detected in 7 of the 52 (14 percent) sam ples at a maximum concentration of 22 mg/kg. The detected cadmium concentrations in samples exceeded the CPEC and TPEC at site SR2 near the mouth of Turkey Creek. Cadmium concentrations in samples from core SR-CH-4 exceeded both PECs at depths ft, and cadmium concentrations in samples from core SR-CH-5 exceeded both PECs for depths ft. The number of cadmium concentration exceedances may be greater because the LOD (12 mg/kg) is larger than the CPEC (4.98 mg/kg) and TPEC (11.1 mg/kg). Nickel concentrations in samples from Spring River also had several exceedances of the CPEC at one or more depths in each of four cores. The CPEC for nickel is less than the LOD (65 mg/kg) for nickel, so the frequency of nickel concentra tion exceedances of PECs may be underreported. Ten of the 52 samples (19 percent) had measured exceedances of the CPEC. Summary and Conclusions The Tri-State Mining District (TSMD) covers about 2,500 square miles (mi2) in southwest Missouri, northeast Oklahoma, and southeast Kansas and has a rich history of lead and zinc mining beginning in the early 1800s and continued through the mid-1900s. Most of the ore deposits were in Jas per and Newton Counties in Missouri, Ottawa County in Okla homa, and Cherokee County in Kansas. More than 100 years of mining in the area has left a legacy of metal-contaminated mine-waste areas, contaminated soils and stream sediment, and contaminated groundwater in the region. Although previous work has been done to characterize the spatial extent of surficial streambed sediments contami nated by mine waste in the TSMD, little information is avail able on the depth or thickness of contaminated sediments in the streams. Based on surficial streambed-sediment samples compiled from various sources, it is estimated that approxi mately 49 miles of Center Creek, Turkey Creek, Shoal Creek, Concentration of lead in sediment samples, in milligrams per kilogram Concentration of zinc in sediment samples, in milligrams per kilogram Midpoint of each sample interval below the local water surface, in feet 1,000 1,000 1,000 1,000 1,000 [Core and site identifiers are explained in table 1]
Sample concentration Probable effects concentration, 128 milligrams per kilogram for lead and 459 milligrams per kilogram for zinc Tri-State Mining District specific probable effects concentration, 150 milligrams per kilogram for lead and 2,083 milligrams per kilogram for zinc EXPLANATION SR1 SR1 SR2 SR2 SR-CH-1 SR-CH-2 SR-CH-3 SR-CH-4 SR-CH-5 SR-CH-1 SR-CH-2 SR-CH-3 SR-CH-4 SR-CH-5 Figure 32. Vertical profiles by core and sample location of lead and zinc concentrations in the less than 2-millimeter size fraction of gravel bar-sediment samples analyzed by x-ray fluorescence, Spring River, Kansas, 2012.
Summary and Conclusions 65 and Tar Creek have streambed sediments that have a moderate to high risk for toxicity to benthic invertebrates, as do sedi ments in the entire reach of the Spring River downstream from the mouth of Center Creek. Information on the depth of con tamination is important to the U.S. Fish and Wildlife Service (USFWS) and other natural resource agencies entrusted with assessing damage to the ecosystem and evaluating restoration alternatives in the TSMD. Determining the depth of metal con tamination is difficult in saturated streambed sediment because of the wide range of grain size of the sediments (silt and sand interspersed with coarse gravels and large cobbles) that are difficult to sample with traditional methods that are generally used to collect sands, silts, and clays. The USFWS requested assistance from the U.S. Geological Survey to provide infor mation on the depth of mine-waste contaminated sediments in selected streams in the TSMD. The U.S. Geological Survey set the goals of (1) determination of the relation between concen tration and depth for lead, zinc, and cadmium in channel sedi ments and flood-plain sediments, and (2) determination of the volume of channel sediment from the surface to the maximum depth with concentrations of lead, zinc, and cadmium that exceeded sediment-quality guidelines. The large area of the TSMD required an array of methods for collecting samples from the stream channels along selected stream reaches and adjacent flood plains. The initial approach was to identify a representative reach along each stream that would be studied and this selected reach would include several geomorphic channel units, such as riffle, run, and pool. Sev eral possible study sites along each stream were identified, but during an initial field reconnaissance of the area, landowner permission to access was not granted at most proposed study sites. Alternative study sites were selected that often were shorter in length and contained fewer geomorphic channel features. In an effort to provide more spatial data on depth of mine-waste contaminated sediments along each stream, additional study locations focusing on gravel bars were added along each stream. Collection of channel sediments focused primarily on gravel bars, and the thickness of sediments was determined using various coring techniques and a tile probe. Five streams in the TSMD were selected for study: Center Creek, Turkey Creek, Shoal Creek, Tar Creek, and the Spring River. These streams were selected because they drain mined areas, are spatially distributed across the TSMD, and have a range of drainage areas—Turkey Creek (46 mi2), Tar Creek (53 mi2), Shoal Creek (251 mi2), and Center Creek (300 mi2). The Spring River has a drainage area of about 2,422 mi2 from the downstream-most sampling site near Baxter Springs, Kansas, but the overall drainage area from its mouth at the Grand Lake O' the Cherokees is 2,590 mi2. Volume of gravel-bar sediment is considered to be dis tributed in two forms, gravel bars and the wetted channel, and this study focused on gravel bars. Most of the readily available sediment is found in gravel bars for large to moderate streams and characterization of gravel-bar sediments in this study focused on gravel bars with some additional samples collected in adjacent areas. Estimates of the volume of contaminated gravel bar deposits were computed relative to two benchmarks of contamination—that is, for both probable effects concentra tion (PEC) values (consensus PEC [CPEC] and Tri-State Min ing District specific PEC [TPEC])—because of the importance of such information to the USFWS and other natural resource agencies of the TSMD for assessing damage to the ecosystem and evaluating restoration alternatives. The maximum depth of contamination was determined as the maximum depth where either the lead or zinc concentration exceeded the respec tive PEC values. Cadmium concentrations were not used to determine contaminated sediment depths because the limit of detection (LOD) for cadmium from the x-ray fluorescence (XRF) analysis (12 milligrams per kilogram [mg/kg]) was larger than the cadmium PECs: CPEC (4.98 mg/kg) and TPEC (11.1 mg/kg). Thus, no sample analyzed by XRF could be determined with certainty from any depth to have a cadmium concentration below either PEC value. To efficiently analyze the large number of samples collected (357 stream channel samples and 379 flood-plain samples) in this study, all samples were analyzed using the XRF. Several quality control and quality assurance procedures were implemented to ensure the quality of the data acquired using the XRF. A series of standards and blanks were ana lyzed at the beginning, end, and several times throughout the day when environmental samples were analyzed. In addition to standards, triplicate and septuplet analyses of the selected flood-plain cores were done during the analysis. During the study, more than 700 sediment samples were collected from borings at multiple sites along Center Creek, Turkey Creek, Shoal Creek, Tar Creek, and Spring River in order to characterize the vertical extent of mine waste in select streams in the TSMD. The largest concentrations of lead, zinc, and cadmium in gravel bar-sediment samples generally were detected in Turkey Creek and Tar Creek and the small est concentrations were detected in Shoal Creek followed by the Spring River. Gravel bar-sediment samples from Turkey Creek exceeded the CPEC for cadmium (minimum of 70 per cent of samples), lead (94 percent), and zinc (99 percent) at a slightly higher frequency than similar samples from Tar Creek (69 percent, 88 percent, and 96 percent, respectively). Gravel bar-sediment samples from Turkey Creek also contained the largest concentrations of cadmium (174 milligrams per kilogram [mg/kg]) and lead (7,520 mg/kg) detected; however, the largest zinc concentration (46,600 mg/kg) was detected in a gravel bar-sediment sample from Tar Creek. In contrast, none of the 65 streambed-sediment samples from Shoal Creek contained cadmium above the x-ray fluorescence reporting level of 12 mg/kg, and lead and zinc exceeded the CPEC in only 12 percent and 74 percent of samples, respectively. In most cases, concentrations of lead and zinc above the CPEC or TPEC were present at the maximum depth of boring, which indicated that nearly the entire thickness of sediment in the stream has been contaminated by mine wastes. Approximately 284,000 cubic yards of channel sediment from land surface to the maximum depth that exceeded the CPEC and approxi mately 236,000 cubic yards of channel sediment from land
66 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District surface to the maximum depth that exceeded the TPEC were estimated along 37.6 of the 55.1 miles of Center Creek, Tur key Creek, Shoal Creek, and Tar Creek examined in this study. Mine-waste contamination reported along additional reaches of these streams is beyond the scope of this study. Flood-plain cores collected in the TSMD generally only had exceedances of the CPEC and TPEC for lead and zinc in the top 1 or 2 feet of soil with a few exceptions, such as cores in low areas near the stream or cores in areas disturbed by past mining. A total of 89 gravel bar-sediment samples from 24 loca tions were collected from gravel bar deposits along the lower 18.6 miles of Center Creek. The maximum sample depth was 9.5 ft below the gravel bar surface. Most of the gravel barsediment samples from Center Creek exceeded the CPEC and the TPEC for lead or zinc at five (C1, C2, C3, C4, and C5) of the six sites along this stream. Site C6 is upstream from most of the historic mining activity in the Center Creek basin, and none of the samples from this site had concentrations of lead, or zinc that exceeded the CPEC or TPEC or concentrations of cadmium that exceeded the LOD. Overall, median concentra tions of lead and zinc increased dramatically from upstream site C6 to site C5, peaked at sites C4 and C3, and decreased downstream through sites C2 and C1; however, lead and zinc median concentrations at site C1 remained enriched signifi cantly above levels at upstream site C6. Lead concentrations ranged from 14.0 mg/kg to 1,880 mg/kg in the <2-millimeter (mm) size fraction of the 89 channel-sediment samples from Center Creek and exceeded the CPEC in 60 samples (67 per cent). Zinc concentrations in the <2-mm size fraction in channel-sediment samples from Center Creek ranged from 201 mg/kg to 25,200 mg/kg exceeding the CPEC in 76 samples (85 percent). Cadmium concentrations in the <2-mm size fraction in stream channel sediments were detected above the 12 mg/kg LOD in 34 samples (38 percent) and the maximum concentration was 171 mg/kg. Very few gravel bar-sediment samples from Center Creek exceeded the CPEC for other metals. The total area of studied gravel bars for Center Creek was 916,000 square feet (ft2; 21.0 acres). The estimated minimum volume of sediment in gravel bars that would need excava tion based on the CPEC along Center Creek from the mouth to site C5 was 136,000 cubic yards (yd3), and the estimated minimum volume of gravel bar sediment exceeding the TPEC was 115,000 yd3. These estimates are considered minimum volumes because they were only based on the visible gravel bars and do not include sediment beneath the wetted channel in other features such as pools, and presumably some of these deposits are negatively affected by mine-waste contaminated sediment but were not sufficiently characterized to be included in the volume estimate. A total of 84 samples were collected from 7 locations on the Center Creek flood plain at sites C1 and C2 within the intensive study area. Four of the seven boreholes had at least one depth interval where lead or zinc exceeded the CPEC or TPEC. Intervals that exceeded the lead or zinc CPEC and TPEC were generally ft deep with occasional detections greater than the CPEC at deeper intervals. Because of time limitations, concentrations of cadmium or barium were not analyzed in many core intervals. For the intervals that were analyzed, 15 out of 23 had concentrations of cadmium greater than the LOD, CPEC, and TPEC. Core samples from borehole CTR-FB-2 had cadmium concentrations analyzed at every sampled interval, and concentrations exceeded the CPEC and TPEC in every interval shallower than 7 ft and at the 8 to 9 ft interval but had no exceedances of the CPEC or TPEC for lead or zinc. A total of 100 samples were collected from 23 locations on gravel bar deposits along Turkey Creek. The maximum sample depth was 13 ft, with the thickest channel deposits in the gravel bars at sites TC2 and TC3 and thinnest deposits at upstream site TC7 (<2 ft thick). Excluding samples with concentrations below the LOD, median lead concentrations increased from the most upstream site TC7 to a peak at site TC5 and decreased somewhat at the two downstream sites TC1 and TC2. Median zinc concentrations increased from the most upstream site at TC7 to a peak at TC4 then remained relatively steady to the most downstream site at TC1. Median cadmium concentrations increased from concentrations below the LOD at the upstream site TC7 to site TC3 and then remained relatively steady to the most downstream site at TC1. Lead and zinc concentrations in nearly all gravel barsediment samples from Turkey Creek exceeded the CPEC and TPEC often to the maximum depth of the boreholes. Lead concentrations exceeded the CPEC in all but 6 samples and exceeded the TPEC in all but 11 samples. Zinc concentra tions exceeded the CPEC in all but 1 sample and exceeded the TPEC in all but 13 samples. Most samples also had exceed ances of both PECs for cadmium (minimum of 70 percent; <12 to 174 mg/kg), although this number of exceedances may be greater because the XRF LOD is greater than the CPEC and TPEC for cadmium. Lead concentrations in gravel bar-sedi ment samples from Turkey Creek ranged from 70.0 mg/kg to 7,520 mg/kg and zinc concentrations ranged from 329 mg/kg to 27,900 mg/kg. The total area of studied gravel bars for Tur key Creek was 632,000 ft2. The estimated minimum volume of sediment in gravel bars exceeding the CPEC for the chosen reach of Turkey Creek was 115,000 yd3 and 108,000 yd3 of sediment in gravel bars exceeding the TPEC. A total of 73 samples were collected from six locations on the Turkey Creek flood plain. Of these, cadmium concen trations were analyzed in 51 samples. Nine of the 73 samples had concentrations of lead greater than the CPEC and 15 had concentrations of zinc greater than the CPEC. Lead concentra tions in eight samples and zinc concentrations in five samples exceeded their respective TPECs. The exceedances of the TPEC for lead or zinc were limited to the upper 1 or 2 feet of the cores except for core TKC-FP-2 where concentrations of lead and zinc were less than the CPEC and TPEC in the upper few feet. Concentrations for lead and zinc for core TKC-FP-2 gradually increased with depth and lead exceeded the CPEC between 6 and 10 ft.
Summary and Conclusions 67 A total of 65 samples were collected from 12 locations on gravel bar deposits along Shoal Creek. The maximum sample depth was 11.9 ft. The maximum depth of sediments that had concentrations of lead and zinc that exceeded the respective CPEC for those metals was 7 ft for lead and 9 ft for zinc. Overall, cores from Shoal Creek generally had concentrations of zinc that exceeded the CPEC at many depths, including the upstream site S5 about 19 miles upstream from Empire Lake. In channel sediments from Shoal Creek, few samples had exceedances of the TPEC for any Mississippi ValleyType related metals. In the <2-mm size fraction of gravel bar-sediment samples from Shoal Creek, lead concentrations ranged from <13 mg/kg to 183 mg/kg. Out of the 65 samples, 8 samples (12 percent) had lead concentrations greater than the CPEC and only 4 samples (about 6 percent) had concen trations greater than the TPEC. Zinc concentrations in the <2-mm size fraction in samples ranged from 176 mg/kg to 3,010 mg/kg and cadmium concentrations were <12 mg/kg in all samples. Almost 74 percent of the samples (48 of 65) had zinc concentrations greater than the CPEC, but only one sample had a concentration greater than the TPEC (borehole SH-CH-8 at depth interval 0 to 1 ft). The total area of studied gravel bars for Shoal Creek was 146,000 ft2 (3.4 acres). Using the mean thickness of contaminated sediment and a total area of sampled gravel bars along this reach of 146,000 ft2, the esti mated minimum volume of contaminated sediment in gravel bars exceeding the CPEC is about 24,000 yd3. The estimated minimum volume of sediment in gravel bars exceeding the TPEC is smaller at about 4,000 yd3. A total of 80 flood-plain samples were collected from 8 locations along the Shoal Creek flood plain. Lead concen trations greater than the CPEC were present in 5 of the 80 (about 6 percent) flood-plain samples from Shoal Creek. Zinc concentrations exceeded the CPEC in 11 samples (about 14 percent). Flood-plain cores sampled along Shoal Creek tended to have concentrations of lead and zinc below the CPEC and TPEC, even in the upper 2 ft of depth. A total of 51 samples were collected on gravel bar depos its along Tar Creek. The maximum sample depth was 6.6 ft. Overall, concentrations of lead and zinc generally exceeded the CPEC in cores from the surface to the top of bedrock that was generally ft deep and in some cases ft deep. Lead and zinc concentrations generally also exceeded the TPEC from the surface to the maximum depth. Lead concentrations, in the <2-mm size fraction in these samples, ranged from a single non-detection (<13 mg/kg) to 2,540 mg/kg. Out of the 51 gravel bar-sediment samples, all but 6 had lead concen trations greater than the CPEC and the TPEC. All samples collected in Tar Creek that exceeded the CPEC for lead also exceeded the TPEC. Zinc concentrations, in the <2-mm size fraction in these samples, ranged from 63.0 mg/kg to 46,600 mg/kg. Out of the 51 stream channel samples, all but 2 had zinc concentrations that exceeded the CPEC, and all but 5 had concentrations that exceeded the TPEC. Cadmium concentrations, in the <2-mm size fraction in these cores, ranged from non-detection to 131 mg/kg. Out of 51 stream channel samples, 35 had detectable cadmium (69 percent) and exceeded the CPEC and TPEC. Out of the 51 samples, 31 (61 percent) had concentrations of nickel that exceeded the CPEC (48.6 mg/kg). There is no TPEC for nickel. Exceedances of the CPEC for nickel generally extended several feet below the surface and were present as deep as 6.6 ft. The total area of studied gravel bars for Tar Creek was 230,000 ft2 (5.3 acres). The estimated minimum volume of sediment in sampled gravel bars exceeding the CPEC and TPEC for the chosen reach of Tar Creek was 9,000 yd3. These estimates are consid ered minimum volumes because they were only based on the visible gravel bars. A total of 142 samples were collected from 13 locations along the Tar Creek flood plain. Concentrations of lead and zinc in flood-plain samples from Tar Creek generally exceeded the CPEC and the TPEC in the upper 1 or 2 ft of soil, and the concentrations were generally greater than concentrations in samples deeper than 2 or 3 ft by an order of magnitude or more. Lead and zinc concentrations in flood-plain samples seemed to decrease with distance from the creek. The 7 cores located within 450 ft of the creek had lead and zinc concen trations that exceeded the CPEC and the TPEC, whereas the 6 cores located at distances greater than 450 ft from the creek had no exceedances. Lead concentrations in 11 of 142 analyzed flood-plain core sections from Tar Creek exceeded the CPEC and the TPEC. Concentrations of zinc exceeded the CPEC in 21 flood-plain core sections and exceeded the TPEC in 9 flood-plain core sections. Cadmium concentrations exceeded the CPEC and the TPEC in 25 of 33 flood-plain core sections where cadmium was analyzed. A total of 52 samples were collected from 5 loca tions on gravel bar deposits along the Spring River. The maximum depth sampled was 19.1 ft. Lead concentrations ranged from 14.0 to 390 mg/kg and exceeded the CPEC in 7 samples (14 percent). Zinc concentrations ranged from 225 to 5,020 mg/kg exceeding the CPEC in 46 (89 percent) of the samples. Lead concentrations in gravel bar-sediment samples at the site downstream from Empire Lake (SR1) were generally less than concentrations in samples collected at the upstream site (SR2). Lead concentrations in the <2-mm size fraction from all 38 samples from the downstream site (SR1) were <105 mg/kg, which was less than the CPEC; however, zinc concentrations exceeded the CPEC in 32 of these samples. Cadmium was detected in 7 of the 52 (14 per cent) samples at a maximum concentration of 22 mg/kg. The detected cadmium concentrations in samples exceeded the CPEC and TPEC at site SR2 near the mouth of Turkey Creek.
68 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District References Cited Andrews, W.J., Becker, M.F., Mashburn, S.L., and Smith, S.J., 2009, Selected metals in sediments and streams in the Oklahoma part of the Tri-State mining district, 2000-2006: U.S. Geological Survey Scientific Investigations Report 2009-5032, 36 p. Angelo, R.T., Cringan, M.S., Chamberlain, D.L., Stahl, A.J., Haslouer, S.G., and Goodrich, C.A., 2007, Residual effects of lead and zinc mining on freshwater mussels in the Spring River Basin (Kansas, Missouri, and Oklahoma, USA): Sci ence of the Total Environment, v. 384, p. 467-496. Bailey, E.H.S., 1911, Preliminary report on stream pollution by mine waters in southeastern Kansas, in Parker, H.N., Quality of the water supplies of Kansas: U.S. Geological Survey Water-Supply Paper 273, p. 349-361. Barks, J.H., 1977, Effects of abandoned lead and zinc mines and mine-waste piles on water quality in the Joplin area, Missouri: U.S. Geological Survey Water-Resources Investi gations 77-75, 49 p. Bastin, E.S., 1939, Theories of formation of ore deposits: Scientific American, v. 49, no. 6, p. 538-547. Beasley, D.E., Koltz, A.M., Lambert, J.E., Fierer, N., and Dunn, R.R., 2015, The evolution of stomach acidity and its relevance to the human microbiome: PLoS ONE, v. 10, no. 7, 12 p. Christenson, S., 1995, Contamination of wells completed in the Roubidoux aquifer by abandoned zinc and lead mines, Ottawa County, Oklahoma: U.S. Geological Survey WaterResources Investigation Report 95-4150, 65 p. Coduto, D.P., 1999, Geotechnical engineering—Principles and practices: Upper Saddle River, New Jersey, Prentice Hall, 759 p. Feder, G.L., Skelton, J., Jeffery, H.G., and Harvey, E.J., 1969, Water resources of the Joplin area, Missouri: Missouri Divi sion of Geology and Land Survey Water Resources Report 24, 97 p. [Also available at ://www.dnr.mo.gov/pubs/ WR24.pdf.] Gibson, A.M., 1972, Wilderness bonanza—The Tri-State Dis trict of Missouri, Kansas, and Oklahoma: Norman, Okla homa, University of Oklahoma Press, 362 p. Earth™, 2011, Aerial imagery, Aerial imagery of Jasper and Newton Counties, Missouri, Cherokee County, Kansas, and Ottawa County, Oklahoma. Ingersoll, C.G., Ivey, C.D., Brumbaugh, W.G., Besser, J.M., and Kemble, N.E., 2009, Toxicity assessment of sediments from the Grand Lake O' the Cherokees with the amphipod Hyalella azteca: U.S. Geological Survey Administrative Report CERC-8335-FY09-20-01, 97 p., accessed December 2009 at ://www.fws.gov/southwest/es/oklahoma/docu ments/contaminants/ingersoll%20et%20al.%20grand%20 lake%20sediment%20toxicity%20report%20text%20 final%20august%2027%202009.pdf. Jolly, J.L., and Van Heyl, A., 1968, Mercury and other trace elements in sphalerite and wallrocks from central Kentucky, Tennessee, and Appalachian Zinc Districts: U.S. Geological Survey Bulletin 1252-F, 40 p. Juracek, K.E., 2006, Sedimentation and occurrence and trends of selected chemical constituents in bottom sediment, Empire Lake, Cherokee County, Kansas, 1905-2005: U.S. Geological Survey Scientific Investigations Report 2006- 5307, 79 p. Juracek, K.E., 2013, Occurrence and variability of miningrelated lead and zinc in the Spring River flood plain and tributary flood plains, Cherokee County, Kansas, 2009-11: U.S. Geological Survey Scientific Investigations Report 2013-5028, 70 p. Juracek, K.E., and Becker, M.F., 2009, Occurrence and trends of selected chemical constituents in bottom sediment, Grand Lake O' the Cherokees, northeast Oklahoma, 1940-2008: U.S. Geological Survey Scientific Investigations Report 2009-5258, 28 p. Lanesky, D.E., Logan, B.W., Brown, R.G., and Hine, A.C., 1979, A new approach to portable vibracoring underwater and on land: Journal of Sedimentary Petrology, v. 49, p. 654-657. Leach, D.L., Taylor, R.D., Fey, D.L., Diehl, S.F., and Saltus, R.W., 2010, A deposit model for Mississippi Valley-Type lead-zinc ores, chap. A of Mineral deposit models for resource assessment: U.S. Geological Survey Scientific Investigations Report 2010-5070-A, 52 p. Lisle, T.E., and Eads, R.E., 1991, Methods to measure sedi mentation of spawning gravels: U.S. Department of Agri culture, Forest Service, Pacific Southwest Research Station Research Note PSW-411, 7 p. Luoma, S.N., 1983, Bioavailability of trace metals to aquatic organisms—A review: The Science of the Total Environ ment, v. 28, p. 1-22. Luoma, S. N., 1989, Can we determine the biological avail ability of sediment-bound trace elements?: Hydrobiologia, v. 176, no. 1, p. 379-396.
References Cited 69 MacDonald, D.D., Ingersoll, C.G., and Berger, T.A., 2000, Development and evaluation of consensus-based sediment quality guidelines for freshwater ecosystems: Archives of Environmental Contamination and Toxicology, v. 39, p. 20-31. MacDonald, D.D., Ingersoll, C.G., Crawford, Meara, Pren cipe, Heather, Besser, J.M., Brumbaugh, W.G., Kemble, Nile, May, T.W., Ivey, C.D., Meneghetti, Melissa, Sinclair, Jesse, and O'Hare, Margaret, 2010, Advanced ScreeningLevel Ecological Risk Assessment (SLERA) for aquatic habitats within the Tri-State Mining District, Oklahoma, Kansas, and Missouri: Nanaimo, British Columbia, Mac Donald Environmental Sciences Ltd., [variously paged]. Merwe, D. van der, Carpenter, J.W., Nietfeld, J.C., and Miesner, J.F., 2011, Adverse health effects in Canada geese (Branta Canadensis) associated with waste from zinc and lead mines in the Tri-State Mining District (Kansas, Okla homa, and Missouri, USA): Journal of Wildlife Diseases, v. 47, no. 3, p. 650-660. Murphy, F., and Herkelrath, W.N., 1996, A sample-freezing drive shoe for a wire-line piston core sampler: Groundwater Monitoring and Remediation, v. 16, no. 3, p. 86-90. Natural Resources Conservation Service, 2003, Soil survey of Jasper and Newton Counties, Missouri, Cherokee County, Kansas, and Ottawa County, Oklahoma: accessed Novem ber 2015 at ://websoilsurvey.sc.egov.usda.gov/App/Web SoilSurvey.aspx. Natural Resources Conservation Service, 1938, Aerial imagery of Jasper and Newton Counties, Missouri. Pope, L.M., 2005, Assessment of contaminated streambed sediment in the Kansas part of the historic Tri-State Lead and Zinc Mining District, Cherokee County, 2004: U.S. Geological Survey Scientific Investigations Report 2005- 5251, 61 p. Schmidt, A., and Leonhard, A., 1874, The lead and zinc regions of south-west Missouri, in Broadhead, G.C., ed., Report of the Geological Survey of the State of Mis souri including field work of 1873-1874: Jefferson City, Missouri, Bureau of Geology and Mines, p. 381-502, accessed June 7, 2005, at ://archive.org/details/ aet7172.0001.001.umich.edu. Schmitt, C.J., Whyte, J.J., Brumbaugh, W.G, and Tillitt, D.E., 2005, Biochemical effects of lead, zinc, and cadmium from mining on fish in the Tri-States District of northeastern Oklahoma, USA: Environmental Toxicology and Chemistry, v. 24, no. 6, p. 1483-1495. Smith, D., 2013, A modification of freeze-core technology for collecting granular fluvial sediment sample: Rolla, Mo., Missouri University of Science and Technology, Master's thesis, 60 p. Smith, D., and Elmore, A.C., 2013, A modification of freezecore technology for collecting granular fluvial sediment samples: Environmental Earth Sciences, v. 71, no. 9, p. 4149-4156. Smith, D.C, 2016, Metals and other constituent concentra tions in metals-contaminated sediment of selected streams draining the Tri-State Mining District, Missouri, Oklahoma, and Kansas, 2011-12: U.S. Geological Survey data release, accessed November 2016, at ://dx.doi.org/10.5066/ F7CZ359X. Sullivan, K., Lisle, T.E., Dolloff, C.A., Grant, G.E. and Reid, L.M., 1987. Stream channels—The link between forests and fishes, in Salo, E.O. and Cundy, T.W., eds., Streamside management—Forestry and fishery interactions: Seattle, Washington, University of Washington, Institute of Forest Resources, no. 57, p. 39-97. Taggart, J.E., 2002, Analytical methods for chemical analysis of geologic and other materials, U.S. Geological Survey: U.S. Geological Survey Open-File Report 02-223 U.S. Department of Agriculture, 2010, Aerial imagery of Jasper and Newton Counties, Missouri, Cherokee County, Kansas, and Ottawa County, Oklahoma. U.S. Environmental Protection Agency, 2007, Method 6200, Field portable x-ray fluorescence spectrometry for the deter mination of elemental concentrations in soil and sediment: Washington, D.C., U.S. Environmental Protection Agency, 32 p. ://www.epa.gov/sites/production/files/2015-12/ documents/6200.pdf. U.S. Geological Survey, 2011, National hydrography dataset: U.S. Geological Survey, accessed November 15, 2014, at ://nhd.usgs.gov/. Wang, F., Goulet, R.R., and Chapman, P.M., 2004, Testing sediment biological effects with the freshwater amphipod Hyalella azteca—The gap between laboratory and nature: Chemosphere, v. 57, no. 11, p. 1713-1724. Zapico, M.M., Vales, S., and Cherry, J.A., 1987, A wireline piston core barrel for sampling cohesionless sand and gravel below the water table: Ground Water Monitoring Review, v. 7, no. 3, p. 74-82.
Table 8 71 Table 8
72 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Table 8. Concentrations of select trace element measured by two methods, with two sample preparation types, in the less than 2-millimeter size fractions of stream channel sediment samples. [XRF, analysis was conducted using an x-ray fluorescence instrument owned and operated by U.S. Fish and Wildlife Service personnel following U.S. Environmental Protection Agency Method 6200 (EPA, 2007) at the U.S. Fish and Wildlife Service office; LAB, analysis was conducted by the U.S. Geological Survey Central Mineral and Environmental Resources Science Center laboratory in Denver, Colorado, using inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry methods described in Taggart (2002); RPD, relative percent difference; less than; --, not calculated; shaded value indicates RPD greater than 30 percent] Core location Depth below land surface (foot) Arsenic Barium Cadmium Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b XRF XRF LAB XRF XRF LAB XRF XRF LAB Center Creek CC-A-HD1 2-3 <11 <12 CC-A-HD2 3-4 <11 CC-B-HD1 0-1 <11 <12 <12 CC-B-HD2 1-2 <11 <12 <12 CC-B-HS1 1-2 <11 <12 <12 CC-B-HS2 0-1 <11 <11 <12 <12 CC-C-HD1 1-2 <11 CC-C-HD2 0-1 <11 CC-C-WC1 0-0.5 <11 <11 CC-D-HD1 3-3.5 <11 <11 CC-D-HD2 3-4 <11 CC-D-WC1 0.2-0.5 <11 <11 CTR-CH-1 7-8 <11 <11 <12 <12 CTR-CH-2 3-4 <11 <12 CTR-CH-3 3-4 <11 <11 CTR-CH-4 6-7 <12 <12 CTR-CH-4 <11 <11 CTR-CH-5 4.5-5.5 <11 <12 CTR-CH-6 0.5-1 <11 <11 <12 CTR-CH-7 0-1 <11 <11 CTR-FB-1 1-2 <11 <11 CTR-FB-2 5-6 <11 <11 <12 CTR-GB-1 0-0.2 <11 <11 CTR-WC-1 5.5-6.5 <11 <12 <12 CTR-WC-2 1-2 <11 <11 <12 <12 CTR-WC-2 2-3 <11 <12 <12 CTR-WC-4 0-0.2 <11 <12 <12
Table 8 73 Table 8. Concentrations of select trace element measured by two methods, with two sample preparation types, in the less than 2-millimeter size fractions of stream channel sediment samples.—Continued [XRF, analysis was conducted using an x-ray fluorescence instrument owned and operated by U.S. Fish and Wildlife Service personnel following U.S. Environmental Protection Agency Method 6200 (EPA, 2007) at the U.S. Fish and Wildlife Service office; LAB, analysis was conducted by the U.S. Geological Survey Central Mineral and Environmental Resources Science Center laboratory in Denver, Colorado, using inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry methods described in Taggart (2002); RPD, relative percent difference; less than; --, not calculated; shaded value indicates RPD greater than 30 percent] Core location Depth below land surface (foot) Colbalt Copper Lead Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b XRF XRF LAB XRF XRF LAB XRF XRF LAB Center Creek—Continued CC-A-HD1 2-3 <35 <35 CC-A-HD2 3-4 <35 1,020 1,010 CC-B-HD1 0-1 <35 <35 CC-B-HD2 1-2 <35 <35 CC-B-HS1 1-2 <35 <35 CC-B-HS2 0-1 <35 <35 CC-C-HD1 1-2 <35 CC-C-HD2 0-1 <35 <35 CC-C-WC1 0-0.5 <35 <35 CC-D-HD1 3-3.5 <35 CC-D-HD2 3-4 <35 <35 CC-D-WC1 0.2-0.5 <35 <35 CTR-CH-1 7-8 <35 <35 CTR-CH-2 3-4 <35 <35 CTR-CH-3 3-4 1,180 CTR-CH-4 6-7 CTR-CH-4 0-1 <35 <35 CTR-CH-5 4.5-5.5 <35 <35 CTR-CH-6 0.5-1 <35 <35 CTR-CH-7 0-1 <35 <35 CTR-FB-1 1-2 1,240 1,280 CTR-FB-2 5-6 <35 <35 CTR-GB-1 0-0.2 <35 <35 CTR-WC-1 5.5-6.5 <35 <35 CTR-WC-2 1-2 <35 <35 CTR-WC-2 2-3 <35 <35 CTR-WC-4 0-0.2 <35 <35
74 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Table 8. Concentrations of select trace element measured by two methods, with two sample preparation types, in the less than 2-millimeter size fractions of stream channel sediment samples.—Continued [XRF, analysis was conducted using an x-ray fluorescence instrument owned and operated by U.S. Fish and Wildlife Service personnel following U.S. Environmental Protection Agency Method 6200 (EPA, 2007) at the U.S. Fish and Wildlife Service office; LAB, analysis was conducted by the U.S. Geological Survey Central Mineral and Environmental Resources Science Center laboratory in Denver, Colorado, using inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry methods described in Taggart (2002); RPD, relative percent difference; less than; --, not calculated; shaded value indicates RPD greater than 30 percent] Core location Depth below land surface (foot) Manganese Nickel Zinc Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b XRF XRF LAB XRF XRF LAB XRF XRF LAB Center Creek—Continued CC-A-HD1 2-3 <65 <65 6,160 4,100 4,880 CC-A-HD2 3-4 <65 <65 17,800 17,900 21,300 CC-B-HD1 0-1 <65 <65 CC-B-HD2 1-2 <65 <65 CC-B-HS1 1-2 <65 <65 CC-B-HS2 0-1 1,150 <65 <65 CC-C-HD1 1-2 <65 <65 3,590 1,970 4,360 CC-C-HD2 0-1 <65 <65 4,140 3,090 10,300 CC-C-WC1 0-0.5 <65 <65 3,190 3,170 8,410 CC-D-HD1 3-3.5 <65 <65 4,140 3,960 9,980 CC-D-HD2 3-4 <65 <65 8,320 5,320 5,550 CC-D-WC1 0.2-0.5 1,110 1,070 <65 <65 5,860 6,160 7,090 CTR-CH-1 7-8 7,460 6,950 9,340 <65 CTR-CH-2 3-4 1,103 <65 <65 1,300 1,210 2,110 CTR-CH-3 3-4 <65 10,100 9,950 10,400 CTR-CH-4 6-7 3,670 4,380 3,130 <65 <65 CTR-CH-4 0-1 1,000 <65 <65 3,800 3,430 4,000 CTR-CH-5 4.5-5.5 1,260 1,230 <65 4,230 5,090 7,270 CTR-CH-6 0.5-1 <65 <65 2,670 3,040 4,380 CTR-CH-7 0-1 <65 <65 3,980 3,590 4,540 CTR-FB-1 1-2 <65 <65 6,830 7,770 8,870 CTR-FB-2 5-6 <65 <65 CTR-GB-1 0-0.2 <65 <65 4,260 3,560 5,150 CTR-WC-1 5.5-6.5 <65 <65 1,410 1,410 1,610 CTR-WC-2 1-2 1,040 <65 <65 1,830 1,680 1,790 CTR-WC-2 2-3 <65 <65 1,200 1,110 1,290 CTR-WC-4 0-0.2 <65 <65 2,300 2,720 4,550
Table 8 75 Table 8. Concentrations of select trace element measured by two methods, with two sample preparation types, in the less than 2-millimeter size fractions of stream channel sediment samples.—Continued [XRF, analysis was conducted using an x-ray fluorescence instrument owned and operated by U.S. Fish and Wildlife Service personnel following U.S. Environmental Protection Agency Method 6200 (EPA, 2007) at the U.S. Fish and Wildlife Service office; LAB, analysis was conducted by the U.S. Geological Survey Central Mineral and Environmental Resources Science Center laboratory in Denver, Colorado, using inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry methods described in Taggart (2002); RPD, relative percent difference; less than; --, not calculated; shaded value indicates RPD greater than 30 percent] Core location Depth below land surface (foot) Arsenic Barium Cadmium Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b XRF XRF LAB XRF XRF LAB XRF XRF LAB Turkey Creek TC-A-HD1 1-1.3 <11 <11 <12 <12 TC-A-HD2 1-1.8 <11 <11 <12 <12 TC-B-HD1 1-2 <11 <11 <12 TC-B-HD2 0-1 <11 <11 <12 TC-C-HD1 2-3 <11 <12 TC-C-HD2 <11 <11 <12 TC-C-HS1 0-1 <11 <12 <12 TC-D-HD1 7.5-8.5 TC-D-HD2 3-4 <11 <11 TC-E-HD1 1-2 <11 TC-E-HD2 3.5-4.5 <11 <11 TC-E-HD3 0-1 <11 <11 TC-E-WC1 0-0.7 <11 <11 TKC-CH-1 4-5 <11 TKC-CH-2 1-2 <11 TKC-CH-3 9-10 <11 <11 <12 <12 TKC-CH-4 10-11 TKC-CH-5 2-3 <11 <11 <12 TKC-CH-5P 1-2 <11 <11 TKC-CH-6 8-8.5 <11 <11 TKC-CH-7 1-2 TKC-CH-7 4-4.5 <11 <11 TKC-FP-1 0-1 <11 <11 TKC-FP-3 0-1 <11 <11 TKC-WC-1 3.6-4.6 <11 <12 <12 TKC-WC-3 2-3 <11
76 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Table 8. Concentrations of select trace element measured by two methods, with two sample preparation types, in the less than 2-millimeter size fractions of stream channel sediment samples.—Continued [XRF, analysis was conducted using an x-ray fluorescence instrument owned and operated by U.S. Fish and Wildlife Service personnel following U.S. Environmental Protection Agency Method 6200 (EPA, 2007) at the U.S. Fish and Wildlife Service office; LAB, analysis was conducted by the U.S. Geological Survey Central Mineral and Environmental Resources Science Center laboratory in Denver, Colorado, using inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry methods described in Taggart (2002); RPD, relative percent difference; less than; --, not calculated; shaded value indicates RPD greater than 30 percent] Core location Depth below land surface (foot) Colbalt Copper Lead Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b XRF XRF LAB XRF XRF LAB XRF XRF LAB Turkey Creek—Continued TC-A-HD1 1-1.3 <35 <35 TC-A-HD2 1-1.8 <35 <35 TC-B-HD1 1-2 <35 1,320 TC-B-HD2 0-1 <35 TC-C-HD1 2-3 TC-C-HD2 2-3 <35 <35 1,880 TC-C-HS1 0-1 <35 <35 TC-D-HD1 7.5-8.5 1,100 1,070 TC-D-HD2 3-4 <35 <35 TC-E-HD1 1-2 <35 <35 TC-E-HD2 3.5-4.5 <35 <35 1,160 TC-E-HD3 0-1 <35 <35 TC-E-WC1 0-0.7 <35 <35 TKC-CH-1 4-5 <35 2,970 2,260 4,320 TKC-CH-2 1-2 <35 TKC-CH-3 9-10 <35 <35 TKC-CH-4 10-11 <35 TKC-CH-5 2-3 TKC-CH-5P 1-2 <35 TKC-CH-6 8-8.5 <35 <35 TKC-CH-7 1-2 <35 TKC-CH-7 4-4.5 <35 <35 TKC-FP-1 0-1 <35 TKC-FP-3 0-1 <35 TKC-WC-1 3.6-4.6 <35 TKC-WC-3 2-3 <35 <35 7,520 7,500 7,050
Table 8 77 Table 8. Concentrations of select trace element measured by two methods, with two sample preparation types, in the less than 2-millimeter size fractions of stream channel sediment samples.—Continued [XRF, analysis was conducted using an x-ray fluorescence instrument owned and operated by U.S. Fish and Wildlife Service personnel following U.S. Environmental Protection Agency Method 6200 (EPA, 2007) at the U.S. Fish and Wildlife Service office; LAB, analysis was conducted by the U.S. Geological Survey Central Mineral and Environmental Resources Science Center laboratory in Denver, Colorado, using inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry methods described in Taggart (2002); RPD, relative percent difference; less than; --, not calculated; shaded value indicates RPD greater than 30 percent] Core location Depth below land surface (foot) Manganese Nickel Zinc Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b XRF XRF LAB XRF XRF LAB XRF XRF LAB Turkey Creek—Continued TC-A-HD1 1-1.3 <65 <65 1,930 2,460 TC-A-HD2 1-1.8 <65 <65 1,830 1,210 2,310 TC-B-HD1 1-2 1,430 1,260 1,020 <65 <65 2,670 2,610 9,290 TC-B-HD2 0-1 1,040 1,270 1,050 <65 2,970 2,620 3,060 TC-C-HD1 2-3 <65 <65 3,590 2,240 3,520 TC-C-HD2 2-3 1,440 <65 <65 1,710 2,010 2,720 TC-C-HS1 0-1 1,350 <65 <65 1,450 3,680 TC-D-HD1 7.5-8.5 <65 13,100 8,630 20,000 TC-D-HD2 3-4 <65 <65 11,600 7,270 15,300 TC-E-HD1 1-2 <65 <65 3,510 4,530 13,200 TC-E-HD2 3.5-4.5 <65 <65 7,960 7,880 20,900 TC-E-HD3 0-1 <65 <65 6,470 5,380 8,800 TC-E-WC1 0-0.7 <65 <65 8,960 3,260 1,310 TKC-CH-1 4-5 <65 27,900 21,900 42,100 TKC-CH-2 1-2 <65 <65 11,700 6,480 20,200 TKC-CH-3 9-10 <65 <65 3,120 3,940 3,930 TKC-CH-4 10-11 <65 <65 4,590 4,060 5,620 TKC-CH-5 2-3 3,740 4,400 11,600 TKC-CH-5P 1-2 <65 <65 6,080 7,210 9,800 TKC-CH-6 8-8.5 <65 <65 4,880 4,640 5,220 TKC-CH-7 1-2 <65 8,930 12,100 TKC-CH-7 4-4.5 <65 <65 7,460 5,460 15,000 TKC-FP-1 0-1 <65 <65 5,750 8,050 9,270 TKC-FP-3 0-1 <65 <65 6,620 8,170 9,880 TKC-WC-1 3.6-4.6 1,240 1,290 1,230 <65 <65 TKC-WC-3 2-3 <65 9,560 9,140 8,970
78 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Table 8. Concentrations of select trace element measured by two methods, with two sample preparation types, in the less than 2-millimeter size fractions of stream channel sediment samples.—Continued [XRF, analysis was conducted using an x-ray fluorescence instrument owned and operated by U.S. Fish and Wildlife Service personnel following U.S. Environmental Protection Agency Method 6200 (EPA, 2007) at the U.S. Fish and Wildlife Service office; LAB, analysis was conducted by the U.S. Geological Survey Central Mineral and Environmental Resources Science Center laboratory in Denver, Colorado, using inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry methods described in Taggart (2002); RPD, relative percent difference; less than; --, not calculated; shaded value indicates RPD greater than 30 percent] Core location Depth below land surface (foot) Arsenic Barium Cadmium Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b XRF XRF LAB XRF XRF LAB XRF XRF LAB Shoal Creek SC-A-HD1 2.5-3.5 <11 <11 <12 <12 SC-A-HD2 1-2 <11 <11 <12 <12 SH-CH-1 3-4 <11 <12 <12 SH-CH-11 3-4 <11 <11 <12 <12 SH-CH-5 0-1 <11 <11 <12 <12 SH-CH-7 2-3 <11 <12 <12 SH-CH-8 4-5 <11 <11 <12 <12 SH-CH-9 2-3 <11 <11 <12 <12 SH-FB-2 1-2 <11 <11 <12 SH-FB-3 0-1 <11 <12 SH-FB-4 7-8 <11 <11 <12 <12 SH-WC-1 2-2.8 <11 <11 <12 <12 SH-WC-2 1-2 <11 <11 <12 <12 SH-WC-3 3-4 <11 <12 <12 Tar Creek TAR-FB-3 0-1 <11 <11 TAR-FP1-3 4-5 <11 <11 TAR-TR-1 0-0.3 TAR-TR-2 0-0.2 TAR-TR-3 0-0.7 <12 TAR-TR-3A 1-2 TAR-TR-4 0-1 <11 <11 <12 <12 TAR-TR-5 0-0.5 <11 <12 <12 TAR-TR-6 0-1 <11 TAR-TR-7 0-1 <11 <11 <12 TAR-TR-8 0-1 TAR-TR-9 0-1 <12
Table 8 79 Table 8. Concentrations of select trace element measured by two methods, with two sample preparation types, in the less than 2-millimeter size fractions of stream channel sediment samples.—Continued [XRF, analysis was conducted using an x-ray fluorescence instrument owned and operated by U.S. Fish and Wildlife Service personnel following U.S. Environmental Protection Agency Method 6200 (EPA, 2007) at the U.S. Fish and Wildlife Service office; LAB, analysis was conducted by the U.S. Geological Survey Central Mineral and Environmental Resources Science Center laboratory in Denver, Colorado, using inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry methods described in Taggart (2002); RPD, relative percent difference; less than; --, not calculated; shaded value indicates RPD greater than 30 percent] Core location Depth below land surface (foot) Colbalt Copper Lead Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b XRF XRF LAB XRF XRF LAB XRF XRF LAB Shoal Creek—Continued SC-A-HD1 2.5-3.5 <35 <35 SC-A-HD2 1-2 <35 SH-CH-1 3-4 <35 <35 SH-CH-11 3-4 <35 SH-CH-5 0-1 <35 <35 SH-CH-7 2-3 <35 <35 SH-CH-8 4-5 <35 <35 SH-CH-9 2-3 <35 <35 SH-FB-2 1-2 <35 <35 SH-FB-3 0-1 <35 <35 SH-FB-4 7-8 <35 SH-WC-1 2-2.8 <35 <35 SH-WC-2 1-2 <35 <35 SH-WC-3 3-4 <35 <35 Tar Creek—Continued TAR-FB-3 0-1 TAR-FP1-3 4-5 <35 TAR-TR-1 0-0.3 <35 TAR-TR-2 0-0.2 <35 TAR-TR-3 0-0.7 <35 <35 TAR-TR-3A 1-2 <35 <35 TAR-TR-4 0-1 <35 <35 TAR-TR-5 0-0.5 <35 <35 TAR-TR-6 0-1 <35 <35 TAR-TR-7 0-1 <35 <35 TAR-TR-8 0-1 <35 <35 TAR-TR-9 0-1 <35 <35
80 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Table 8. Concentrations of select trace element measured by two methods, with two sample preparation types, in the less than 2-millimeter size fractions of stream channel sediment samples.—Continued [XRF, analysis was conducted using an x-ray fluorescence instrument owned and operated by U.S. Fish and Wildlife Service personnel following U.S. Environmental Protection Agency Method 6200 (EPA, 2007) at the U.S. Fish and Wildlife Service office; LAB, analysis was conducted by the U.S. Geological Survey Central Mineral and Environmental Resources Science Center laboratory in Denver, Colorado, using inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry methods described in Taggart (2002); RPD, relative percent difference; less than; --, not calculated; shaded value indicates RPD greater than 30 percent] Core location Depth below land surface (foot) Manganese Nickel Zinc Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b XRF XRF LAB XRF XRF LAB XRF XRF LAB Shoal Creek—Continued SC-A-HD1 2.5-3.5 <65 <65 SC-A-HD2 1-2 <65 <65 SH-CH-1 3-4 <65 1,020 SH-CH-11 3-4 <65 <65 1,030 1,020 SH-CH-5 0-1 <65 <65 SH-CH-7 2-3 <65 <65 SH-CH-8 4-5 <65 <65 SH-CH-9 2-3 <65 <65 1,850 1,360 2,110 SH-FB-2 1-2 <65 <65 SH-FB-3 0-1 <65 <65 SH-FB-4 7-8 <65 <65 1,740 1,690 1,920 SH-WC-1 2-2.8 <65 SH-WC-2 1-2 <65 <65 1,080 SH-WC-3 3-4 <65 <65 Tar Creek—Continued TAR-FB-3 0-1 <65 <65 4,430 6,130 6,100 TAR-FP1-3 4-5 <65 <65 3,630 3,680 TAR-TR-1 0-0.3 6,970 7,490 8,010 TAR-TR-2 0-0.2 5,220 4,230 7,990 TAR-TR-3 0-0.7 1,190 2,410 5,040 5,970 7,100 TAR-TR-3A 1-2 3,150 3,870 6,740 TAR-TR-4 0-1 <65 2,730 2,550 5,910 TAR-TR-5 0-0.5 <65 <65 TAR-TR-6 0-1 1,020 2,280 3,230 4,980 11,300 TAR-TR-7 0-1 2,300 2,270 3,860 3,690 7,740 TAR-TR-8 0-1 4,120 3,750 7,070 TAR-TR-9 0-1 <85 2,280 4,450 6,010
Table 8 81 Table 8. Concentrations of select trace element measured by two methods, with two sample preparation types, in the less than 2-millimeter size fractions of stream channel sediment samples.—Continued [XRF, analysis was conducted using an x-ray fluorescence instrument owned and operated by U.S. Fish and Wildlife Service personnel following U.S. Environmental Protection Agency Method 6200 (EPA, 2007) at the U.S. Fish and Wildlife Service office; LAB, analysis was conducted by the U.S. Geological Survey Central Mineral and Environmental Resources Science Center laboratory in Denver, Colorado, using inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry methods described in Taggart (2002); RPD, relative percent difference; less than; --, not calculated; shaded value indicates RPD greater than 30 percent] Core location Depth below land surface (foot) Arsenic Barium Cadmium Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b XRF XRF LAB XRF XRF LAB XRF XRF LAB Spring River SR-CH-1 5-6 <11 <11 <12 <12 SR-CH-2 9-10 <11 <12 SR-CH-3 2-3 <11 <11 <12 <12 SR-CH-4 3-4 <11 <11 SR-CH-5 4-5 <11 <12 SR-CH-5 6-7 <11 <11 <12 <12
82 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Table 8. Concentrations of select trace element measured by two methods, with two sample preparation types, in the less than 2-millimeter size fractions of stream channel sediment samples.—Continued [XRF, analysis was conducted using an x-ray fluorescence instrument owned and operated by U.S. Fish and Wildlife Service personnel following U.S. Environmental Protection Agency Method 6200 (EPA, 2007) at the U.S. Fish and Wildlife Service office; LAB, analysis was conducted by the U.S. Geological Survey Central Mineral and Environmental Resources Science Center laboratory in Denver, Colorado, using inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry methods described in Taggart (2002); RPD, relative percent difference; less than; --, not calculated; shaded value indicates RPD greater than 30 percent] Core location Depth below land surface (foot) Colbalt Copper Lead Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b XRF XRF LAB XRF XRF LAB XRF XRF LAB Spring River—Continued SR-CH-1 5-6 <35 <35 SR-CH-2 9-10 <35 <35 SR-CH-3 2-3 <35 <35 SR-CH-4 3-4 <35 <35 SR-CH-5 4-5 <35 SR-CH-5 6-7 <35 <35
Table 8 83 Table 8. Concentrations of select trace element measured by two methods, with two sample preparation types, in the less than 2-millimeter size fractions of stream channel sediment samples.—Continued [XRF, analysis was conducted using an x-ray fluorescence instrument owned and operated by U.S. Fish and Wildlife Service personnel following U.S. Environmental Protection Agency Method 6200 (EPA, 2007) at the U.S. Fish and Wildlife Service office; LAB, analysis was conducted by the U.S. Geological Survey Central Mineral and Environmental Resources Science Center laboratory in Denver, Colorado, using inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry methods described in Taggart (2002); RPD, relative percent difference; less than; --, not calculated; shaded value indicates RPD greater than 30 percent] Core location Depth below land surface (foot) Manganese Nickel Zinc Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b XRF XRF LAB XRF XRF LAB XRF XRF LAB Spring River—Continued SR-CH-1 5-6 7,030 4,360 2,050 <65 SR-CH-2 9-10 <65 <65 1,120 1,130 1,170 SR-CH-3 2-3 <65 <65 SR-CH-4 3-4 <65 <65 5,020 3,780 7,160 SR-CH-5 4-5 <65 1,070 1,570 SR-CH-5 6-7 <65 <65
84 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Table 8. Concentrations of select trace element measured by two methods, with two sample preparation types, in the less than 2-millimeter size fractions of stream channel sediment samples.—Continued [XRF, analysis was conducted using an x-ray fluorescence instrument owned and operated by U.S. Fish and Wildlife Service personnel following U.S. Environmental Protection Agency Method 6200 (EPA, 2007) at the U.S. Fish and Wildlife Service office; LAB, analysis was conducted by the U.S. Geological Survey Central Mineral and Environmental Resources Science Center laboratory in Denver, Colorado, using inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry methods described in Taggart (2002); RPD, relative percent difference; less than; --, not calculated; shaded value indicates RPD greater than 30 percent] Core location Depth below land surface (foot) Arsenic Barium Cadmium Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b XRF XRF LAB XRF XRF LAB XRF XRF LAB Average RPD Number of cases Maximum value Minimum value <11 <11 <12 <12
Table 8 85 Table 8. Concentrations of select trace element measured by two methods, with two sample preparation types, in the less than 2-millimeter size fractions of stream channel sediment samples.—Continued [XRF, analysis was conducted using an x-ray fluorescence instrument owned and operated by U.S. Fish and Wildlife Service personnel following U.S. Environmental Protection Agency Method 6200 (EPA, 2007) at the U.S. Fish and Wildlife Service office; LAB, analysis was conducted by the U.S. Geological Survey Central Mineral and Environmental Resources Science Center laboratory in Denver, Colorado, using inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry methods described in Taggart (2002); RPD, relative percent difference; less than; --, not calculated; shaded value indicates RPD greater than 30 percent] Core location Depth below land surface (foot) Cobalt Copper Lead Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b XRF XRF LAB XRF XRF LAB XRF XRF LAB Average relative percent difference—Continued Number of cases—Continued Maximum value—Continued 7,520 7,500 7,050 Minimum value—Continued <35 <35
86 Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District Table 8. Concentrations of select trace element measured by two methods, with two sample preparation types, in the less than 2-millimeter size fractions of stream channel sediment samples.—Continued [XRF, analysis was conducted using an x-ray fluorescence instrument owned and operated by U.S. Fish and Wildlife Service personnel following U.S. Environmental Protection Agency Method 6200 (EPA, 2007) at the U.S. Fish and Wildlife Service office; LAB, analysis was conducted by the U.S. Geological Survey Central Mineral and Environmental Resources Science Center laboratory in Denver, Colorado, using inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry methods described in Taggart (2002); RPD, relative percent difference; less than; --, not calculated; shaded value indicates RPD greater than 30 percent] Core location Depth below land surface (foot) Manganese Nickel Zinc Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b Original sample Split sample RPD-1a RPD-2b XRF XRF LAB XRF XRF LAB XRF XRF LAB Average relative percent difference—Continued Number of cases—Continued Maximum value—Continued 7,460 6,950 9,340 27,900 21,900 42,100 Minimum value—Continued <65 <65 aRPD between XRF results from analysis of the original sample and split sample sent for laboratory analysis. bRPD between XRF scan of split sample sent for laboratory chemical analysis and split sample sent for laboratory analysis.
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Smith—Occurrence, Distribution, and Volume of Metals-Contaminated Sediment of Selected Streams, Tri-State Mining District—SIR 2016-5144 ISSN 2328-0328 (online) ://dx.doi.org/10.3133/sir20165144