U.S. Department of the Interior

U.S. Geological Survey

Scientific Investigations Report 2009–5032

Selected Metals in Sediments and Streams in the Oklahoma 

Part of the Tri-State Mining District, 2000–2006
On the cover: Photograph of chat piles in the Tri-State mining district in Picher, Oklahoma. 

Photograph taken by William Andrews, U.S. Geological Survey. (Photograph taken by William 

J. Andrews on June 1, 2006.)
Selected Metals in Sediments and Streams 

in the Oklahoma Part of the Tri-State 

Mining District, 2000–2006

By William J. Andrews, Mark F. Becker, Shana L. Mashburn, and S. Jerrod Smith

Scientific Investigations Report 2009–5032

U.S. Department of the Interior

U.S. Geological Survey
U.S. Department of the Interior

KEN SALAZAR, Secretary

U.S. Geological Survey

Suzette M. Kimball, Acting Director

U.S. Geological Survey, Reston, Virginia: 2009

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Suggested citation:

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 

2009–5-032, 36 p.
iii

Contents

Abstract...........................................................................................................................................................1

Introduction.....................................................................................................................................................1

Purpose and Scope .............................................................................................................................4

Acknowledgments................................................................................................................................6

Methods...........................................................................................................................................................6

Lakebed, Floodplain, and Streambed Sediment Collection and Analyses..................................6

Water-Quality Sampling and Analyses..............................................................................................7

Quality Assurance and Quality Control ...........................................................................................12

Data Analysis.......................................................................................................................................12

Selected Metals in Streambed Sediments..............................................................................................12

Lakebed Sediments ............................................................................................................................14

Floodplain Sediments.........................................................................................................................14

Streambed Sediments........................................................................................................................14

Aluminum.....................................................................................................................................14

Cadmium......................................................................................................................................14

Iron................................................................................................................................................18

Lead..............................................................................................................................................18

Manganese.................................................................................................................................18

Zinc...............................................................................................................................................18

Selected Metals in Streams.......................................................................................................................20

Aqueous Concentrations and Streamflow .....................................................................................20

Aluminum.....................................................................................................................................20

Cadmium......................................................................................................................................20

Iron................................................................................................................................................27

Lead..............................................................................................................................................28

Manganese.................................................................................................................................29

Zinc...............................................................................................................................................29

Total Metal Loads................................................................................................................................30

Aluminum.....................................................................................................................................30

Cadmium......................................................................................................................................30

Iron................................................................................................................................................31

Lead..............................................................................................................................................31

Manganese.................................................................................................................................31

Zinc...............................................................................................................................................31

Summary........................................................................................................................................................31

References Cited..........................................................................................................................................33
iv

Figures

1. Map showing location of mining areas in the Tri-State mining district of Oklahoma, 

Kansas, and Missouri...................................................................................................................3

2. Photographs of (A) a tailings pile near Picher, Oklahoma, (B) millpond tailings near 

Douthat, Oklahoma, (C) iron-hydroxide-stained water along a ditch draining to Tar 

Creek near Douthat, Oklahoma, and (D) deposits of soft, flocculated botryoidal 

goethite and other iron oxide and hydroxide minerals on the streambed of Tar Creek 

near Douthat, Oklahoma..............................................................................................................4

3. Map showing location of water-quality and sediment sample collection sites in the 

Oklahoma part of the Tri-State mining district, 2000–2006.....................................................5

4. Aerial photograph of location of sites sampled for sediments in the upstream part of 

Grand Lake O’ the Cherokees, April 2002 and April 2004. ......................................................8

5. Photographs of measurement and processing of sediment cores collected in the 

upstream end of Grand Lake O’ the Cherokees in April 2004. ...............................................8

6. Map showing locations of sediment cores collected on the floodplain of Tar Creek 

south of the 22nd Street Bridge in Miami, Oklahoma, on June 16, 2004..............................9

7. Boxplots of relative percent differences for concentrations of (A) selected metals in 

streambed sediment, and (B) water duplicate samples collected in the Oklahoma part 

of the Tri-State mining district, 2000–06..................................................................................13

8. Bar graphs of selected metals concentrations in streambed samples collected 

at sites in the upstream end of Grand Lake O’ the Cherokees, April 2002 and

April 2004......................................................................................................................................15

9. Cross-sectional diagrams showing distributions of concentrations of (A) aluminum, 

(B) cadmium, (C) iron, (D) lead, (E) manganese, and (F) zinc in sediment cores 

collected in a transect 165 feet south of the 22nd Street Bridge at Tar Creek at Miami, 

Oklahoma, on June 16, 2004......................................................................................................16

10–11. Boxplots showing:

10. Ranges of concentrations of selected metals in streambed sediment samples 

from six stream sites in the Oklahoma part of the Tri-State mining district,2004–06. .....17

11. Ranges of concentrations of dissolved oxygen and of pH in water-quality samples 

from 18 stream sites in the Oklahoma part of the Tri-State mining district 2004–06. ......19

 12–18. Graphs showing:

12. Ranges in concentrations of total and dissolved aluminum (A), and graphs of total 

concentrations of aluminum in surface-water samples compared to discharge (B,C) 

for samples collected at sites in the Oklahoma part of the Tri-State mining district, 

2000–06. ........................................................................................................................................21

13. Ranges in concentrations of total and dissolved cadmium (A), and graphs of total 

concentrations of cadmium in surface-water samples compared to discharge (B,C) 

for samples collected at sites in the Oklahoma part of the Tri-State mining district, 

2000–06. ........................................................................................................................................22

14. Ranges in concentrations of total and dissolved iron (A), and graphs of total 

concentrations of iron in surface-water samples compared to discharge (B,C) 

for samples collected at sites in the Oklahoma part of the Tri-State mining district, 

2000–06. ........................................................................................................................................23

15, Ranges in concentrations of total and dissolved lead (A), and graphs of total 

concentrations of lead in surface-water samples compared to discharge (B,C) for 

samples collected at sites in the Oklahoma part of the Tri-State mining district, 

2000–06. ........................................................................................................................................24

16. Ranges in concentrations of total and dissolved manganese (A), and graphs of total 
v

concentrations of manganese in surface-water samples compared to discharge 

(B,C) for samples collected at sites in the Oklahoma part of the Tri-State mining 

district, 2000–06...........................................................................................................................25

17. Ranges in concentrations of total and dissolved zinc (A), and graphs of total 

concentrations of zinc in surface-water samples compared to discharge (B,C) 

for samples collected at sites in the Oklahoma part of the Tri-State mining 

district, 2000–06...........................................................................................................................26

18. Ranges of loads of total aluminum, cadmium, iron, lead, manganese, and zinc 

in surface-water samples collected at sites in the Oklahoma part of the Tri-State

 mining district, 2000–06.............................................................................................................32

Tables

1. Concentrations of selected metals in a tailings sample from the Kennoyer North 

pile and two millpond tailings samples collected near Cardin, Oklahoma in 2004. ...........2

2. U.S. Geological Survey investigations in the Oklahoma portion of the Tri-State 

mining district, 2000-06. ...............................................................................................................6

3. Lakebed sediment sampling sites in the upstream end of Grand Lake O’ the 

Cherokees (April 2002 and April 2004).......................................................................................7

4. Locations and depths of floodplain sediment cores collected along a transect near 

Tar Creek at the 22nd Street Bridge at Miami, Oklahoma gaging station 

on June 16, 2004..........................................................................................................................10

5. Stream sites sampled for water quality and streambed sediment in the 

Oklahoma part of the Tri-State mining district, 2000-06. ......................................................11

6. Regression equations used to estimate streamflow at time of water-quality 

sampling at selected stream sites in the Oklahoma part of the Tri-State mining 

district, 2000–06...........................................................................................................................12

7. Mined areas compared to basin areas for selected basins in the Oklahoma part 

of the Tri-State mining district. .................................................................................................27
vi

Conversion Factors and Datums

Multiply By To obtain

Length

inch (in.) 2.54 centimeter (cm)

foot (ft) 0.3048 meter (m)

mile (mi) 1.609 kilometer (km)

Area

square mile (mi2) 2.590 square kilometer (km2) 

Volume

gallon (gal) 3.785 liter (L) 

cubic foot (ft3) 0.02832 cubic meter (m3) 

cubic yard (yd3) 0.7646 cubic meter (m3) 

Flow rate

cubic foot per second (ft3/s) 0.02832 cubic meter per second (m3/s)

Mass

pound (lb) 0.4536 kilogram (kg) 

ton, short (2,000 lb) 0.9072 megagram (Mg) 

Vertical coordinate information is referenced to the National Geodetic Vertical Datum of 1929 

(NGVD 29).

Horizontal coordinate information is referenced to the North American Datum of 1983 (NAD 83).

Concentrations of chemical constituents in sediment are given in milligrams per kilogram 

(mg/Kg equivalent to parts per million) and in water in micrograms per liter (μg/L, equivalent to 

parts per billion).

Minimum reporting level (MRL)—Smallest measured concentration of a constituent that may be 

reliable reported by using a given method (Timme, 1995).
vii
Selected Metals in Sediments and Streams in the 

Oklahoma Part of the Tri-State Mining District, 2000–2006

By William J. Andrews, Mark F. Becker, Shana L. Mashburn, and S. Jerrod Smith

Abstract

The abandoned Tri-State mining district includes 1,188 

square miles in northeastern Oklahoma, southeastern Kansas, 

and southwestern Missouri. The most productive part of the 

Tri-State mining district was the 40-square mile part in Oklahoma, commonly referred to as “the Picher mining district” in 

north-central Ottawa County, Oklahoma. The Oklahoma part 

of the Tri-State mining district was a primary producing area 

of lead and zinc in the United States during the first half of the 

20th century. Sulfide minerals of cadmium, iron, lead, and zinc 

that remained in flooded underground mine workings and in 

mine tailings on the land surface oxidized and dissolved with 

time, forming a variety of oxide, hydroxide, and hydroxycarbonate metallic minerals on the land surface and in streams 

that drain the district. Metals in water and sediments in 

streams draining the mining district can potentially impair the 

habitat and health of many forms of aquatic and terrestrial life.

Lakebed, streambed and floodplain sediments and/or 

stream water were sampled at 30 sites in the Oklahoma part 

of the Tri-State mining district by the U.S. Geological Survey 

and the Oklahoma Department of Environmental Quality from 

2000 to 2006 in cooperation with the U.S. Environmental Protection Agency, and the Quapaw and Seneca-Cayuga Tribes 

of Oklahoma. Aluminum and iron concentrations of several 

thousand milligrams per kilogram were measured in sediments 

collected from the upstream end of Grand Lake O’ the Cherokees. Manganese and zinc concentrations in those sediments 

were several hundred milligrams per kilogram. Lead and cadmium concentrations in those sediments were about 10 percent 

and 0.1 percent of zinc concentrations, respectively. Sediment 

cores collected in a transect across the floodplain of Tar Creek 

near Miami, Oklahoma, in 2004 had similar or greater concentrations of those metals than sediment cores collected at the 

upstream end of Grand Lake O’ the Cherokees. The greatest 

concentrations of cadmium, iron, lead, and zinc were detected 

in sediments beneath an intermittent tributary to Tar Creek, a 

slough which drains mined areas near Commerce, Oklahoma.

In surface water, aluminum and iron concentrations were 

greatest in the Neosho River, perhaps a result of runoff from 

areas underlain by shales. The greatest aqueous concentrations of cadmium, lead, manganese, and zinc were measured 

in water from Tar Creek, the primary small stream draining the Picher mining district with the largest proportion of 

mined area. Water from the Spring River had greater zinc 

concentrations than water from the Neosho River, perhaps as 

a result of a greater proportion of mined area in the Spring 

River Basin. Dissolved metals concentrations were generally much less than total metals concentrations, except for 

manganese and zinc at sites on Tar Creek, where seepage of 

ground water from the mine workings, saturated mine tailings, 

and/or metalliferous streambed sediments may be sources of 

these dissolved metals. Iron and lead concentrations generally 

decreased with increasing streamflow in upstream reaches of 

Tar Creek, indicating dilution of metals-rich ground water by 

runoff. Farther downstream in Tar Creek, and in the Neosho 

and Spring Rivers, metals concentrations tended to increase 

with increasing streamflow, indicating that most metals in 

these parts of these streams were associated with runoff and 

re-suspension of metals precipitated as oxide, hydroxide, and 

hydroxycarbonate minerals on land surface and streambeds.

Estimated total aluminum, cadmium, iron, manganese, 

and zinc loads generally were greatest in water from the Neosho and Spring Rivers, primarily because of comparatively 

large streamflows in those rivers. Slight increases in metal 

loads in the downstream directions on those rivers indicated 

contributions of metals from inflows of small tributaries such 

as Tar Creek and from runoff.

Introduction

The abandoned Tri-State mining district (fig. 1), an 

1,188-square-mile area in northeast Oklahoma, southeast 

Kansas, and southwest Missouri, was the most productive 

site of lead and zinc mining in the U.S. from the late 1830s to 

the 1970s, producing about 1.7 million tons of lead and 8.8 

million tons of zinc (Gibson, 1972; Gibson, 1982; State of 

Oklahoma, 2000a; Robertson, 2006). Ore production in the 

mining district was active from the late 1800s until the mid1970s. Production reached a peak by 1925 with 387,000 tons 

of recoverable zinc and 101,000 tons of recoverable lead being 

produced. The mines maintained moderate production levels 

until the 1950s when yields began to decline. 
2 Selected Metals in Sediments and Streams in the Oklahoma Part of Tri-State Mining District, 2000–2006

Parts of the mining district, included in the initial 1983 

National Priority list of Superfund sites by the U.S. Environmental Protection Agency, are plagued by some of the most 

severe or widespread environmental degradation of any of 

the tens of thousands of abandoned mining sites in the United 

States (Ferderer, 1996; State of Oklahoma, 2000a; Robertson, 

2006). One of the most productive parts of the Tri-State mining district (fig. 1) was the Picher mining district, a 40-squaremile area in north-central Ottawa County, Oklahoma. This 

area comprises most of the mined land in the Tri-State mining 

district, now the Tar Creek Superfund site, and is referred to as 

“the mining district” in this report.

When mining stopped in the mining district in the 1970s, 

as much as 165–300 million tons of mine tailings (waste rock, 

locally known as “chat”), some of which had been reprocessed 

one or more times to recover metals, were distributed in piles 

and ground cover (fig. 2, State of Oklahoma, 2000a). The U.S. 

Army Corps of Engineers, in 2000, estimated that 60 million 

cubic yards or 75 million tons of chat remained in the mining district (State of Oklahoma, 2000a). Ponds near many of 

the chat piles, filled with silt- and clay-sized by-products of 

the gravity-separation process, are referred to in this report 

as millpond tailings (fig. 2). Tailings in the mining district 

contain concentrations of tens to tens of thousands of milligrams per kilogram (mg/Kg) of metals, including aluminum, 

cadmium, iron, lead, manganese, and zinc, with the greatest concentrations of metals being associated with the finest 

particles (table 1, Datin and Cates, 2002; Schaider and others, 

2007). Those fine particles with the greatest metals concentrations comprise the particles most susceptible to erosion 

(transport) by wind and water. Seeps from the flooded underground mine workings, and leachate and runoff from tailings 

discharge metals, in varying degrees, to local streams. After 

anoxic water rich in dissolved, reduced ferrous (Fe+2) iron 

seeps from the underground mines to the land surface, iron is 

oxidized, precipitating as deposits of amorphous orange iron 

oxide and hydroxide minerals (fig. 2). Other metals such as 

lead and zinc, also gradually dissolve from sulfide minerals in 

the mine workings and in tailings on the land surface, oxidizing to form a variety of oxide, hydroxide, and hydroxycarbonate minerals that precipitate on the land surface and in local 

streambeds (Hem, 1992; Morel and Hering, 1993; American 

Water Works Association Research Foundation, 1996; Carroll 

and others, 1998; O’Day and others, 1998; Schaider and others, 2007). Several metals, including lead and zinc, also can be 

adsorbed onto clay minerals and iron and manganese oxides 

on the land surface and in streams (Drever, 1988; Hem, 1992), 

making many metals subject to transport in land-surface runoff 

and re-suspension from streambed sediments during high 

streamflows.

Table 1. Concentrations of selected metals in a tailings sample from the Kennoyer North pile and two 

millpond tailings samples collected near Cardin, Oklahoma in 2004.

[Analyses by digestion and ICP-MS, U.S. Geological Research Laboratory, Denver, Colorado, written commun., Stephen J. 

Sutley, 2005]

Metal

Kennoyer North pile tailings Mean of two millpond 

tailings samples, metal 

concentration, in milligrams 

per kilogram

Unsieved concentration, 

in milligrams per kilogram

Sieved concentration (particles than 2 millimeters

 in diameter), in milligrams 

per kilogram

Aluminum 1,700 4,100 20,300

Cadmium 12.9 31.2 119

Iron 1,690 4,080 16,900

Lead 369 890 9,180

Manganese 13.8 33.2 158

Zinc 3,630 8,750 22,300
Introduction 3

Figure 1. Location of mining areas in the Tri-State mining district of Oklahoma, Kansas, and Missouri.

44

44

44

96

71

69

66

166

166

71B

69 71

60

KANSAS MISSOURI

OKLAHOMA Study area

EXPLANATION

Approximate extent of mined

area (modified from Brichta, 1960)

Spring River Basin

Neosho River Basin

Tar Creek Basin (in Neosho River

Basin)

94°50' 94°40' 94°30' 94°20'

37°10'

37°00'

36°50'

0 5 10 MILES

0 10 KILOMETERS

Stippville Lawton

Sherwin Carl Junction Carthage

Webb

City Columbus

CHEROKEE

COUNTY

Atlas Neutral

Joplin Galena

Riverton

JASPER COUNTY

NEWTON COUNTY

Melrose Baxter Springs

KANSAS Treece Diamond

Picher

Cardin

Quapaw Commerce

OTTAWA

COUNTY

OKLAHOMA

MISSOURI

Neosho

Miami

Seneca

Roads by Geographic Data Technology, Inc. Copyright 1984–1998.

Albers Equal Area projection

North American Datum 1983

5

Area shown in figure 3
4 Selected Metals in Sediments and Streams in the Oklahoma Part of Tri-State Mining District, 2000–2006

Figure 2. Photographs of (A) a tailings pile near Picher, 

Oklahoma, (B) millpond tailings near Douthat, Oklahoma, (C) 

iron-hydroxide-stained water along a ditch draining to Tar Creek 

near Douthat, Oklahoma, and (D) deposits of soft, flocculated 

botryoidal goethite and other iron oxide and hydroxide minerals on 

the streambed of Tar Creek near Douthat, Oklahoma, (photographs 

A, B, and D by William J. Andrews, U.S. Geological Survey; 

photograph B by R.W. Nairn, University of Oklahoma).

Most of the mining in this mining district took place 

below the water table, necessitating continuous pumping of 

ground water to prevent flooding of the workings. Water from 

dewatering operations was discharged to local streams. More 

than 13 million gallons of water were pumped from the mines 

during production in the 1930s to 1940s (Reed and others, 

1955, p. 53–54), but no information is available regarding 

metals concentrations in water discharged to local streams during mining. Prior to cessation of mining in the 1970s, dewatering operations ended and the mine workings refilled with 

ground water. After the mines filled with ground water, seeps 

of acidic water with large concentrations of metals started 

to flow from abandoned mine shafts, vent holes, dewatering 

wells, and collapsed areas in late 1979 (State of Oklahoma, 

2002). Exacerbating the problem, parts of Tar and Lytle 

Creeks (fig. 3) flowed into collapses, increasing the flow of 

water through the mine workings. Fate and transport of metals 

from leachate and discharges from the flooded mine workings are poorly understood, particularly for the period prior to 

1980.

Purpose and Scope 

The purpose of this report is to summarize concentrations and/or loads of selected metals in samples of: (a) lakebed 

sediments, (b) floodplain sediments, (c) streambed sediments, 

and (d) surface-water samples collected from 2000 through 

2006 at 30 sites in the mining district. Metals-concentration 

data from those samples were collected during several studies 

completed by the U.S. Geological Survey (USGS) and the 

Oklahoma Department of Environmental Quality (DEQ) in 

cooperation with: the Quapaw Tribe of Oklahoma (streamwater quality study in 2000), the Seneca-Cayuga Tribe of 

Oklahoma (lakebed sediment study in 2002 and 2004), the 

Oklahoma Department of Environmental Quality (floodplain 

sediment study in 2004, and streambed sediments and streamwater study from 2004–2006), and investigation of metals in 

ground-water seepage compared to runoff in upstream parts 

of Tar and Lytle Creeks (Cope and others, 2008). This report 

also describes metals loads transported by streams draining the 

mining district. Unpublished data from most of these studies 

D

C

B

A
Introduction 5

Figure 3. Location of water-quality and sediment sample collection sites in the Oklahoma part of the Tri-State mining district, 

2000–2006.

Hydrography, roads, and cities from

Oklahoma Water Resources Board,

Albers Equal Area Conic Projection,

North American Datum 1983

Miami

Peoria

Cardin

Quapaw

Picher

Fairland

Wyandotte

Douthat

Afton

Twin

Bridges

Commerce

U.S. Highway 69

State Highway 125

State Highway 10

Will Rogers Turnpike

Spring River

Grand Lake O'

 the Cherokees

Neosho River

Neosho Riv er

Tar

Creek

Creek

Elm

Creek Lytle

Creek

Beaver

OKLAHOMA

KANSAS

07185000

07185090

07185095

07188000

0

0 5 KILOMETERS

5 MILES

#

#

#

Tailings sampling location

Surface-water and dredge sample, ungaged site

Surface-water and dredge sample, gaged site and identifier

Surface-water, dredge, and sediment core sample, ungaged site

Surface-water, dredge, and sediment core sample, gaged site and identifier

Grand Lake O' the Cherokees sandbar sediment core sample

Tar Creek floodplain sediment core sample

Surface-water-quality sample, ungaged site

#

07185095#

07188000

EXPLANATION

37°00'

36°55'

36°50'

36°45'

94°55' 94°50' 94°45' 94°40'

Area enlarged in figure 4

#

#

#

#

#

#

#

#

#

#

## #

##

#

#

#
6 Selected Metals in Sediments and Streams in the Oklahoma Part of Tri-State Mining District, 2000–2006

are available in the USGS-National Water Information System 

database (http://waterdata.usgs.gov/nwis).

Acknowledgments

The author would like to thank all DEQ and USGS staff 

who collected data summarized in this report. Gratitude is 

extended to Tim Kresse, Michael Kleeshulte, Kim Winton, 

Stan Paxton, Lyn Osburn, and Keith Lucey for their helpful 

reviews of the report. 

Methods

Several recent studies have been done by the USGS and 

DEQ in and downstream from the mining district (table 2). 

Those studies were done in cooperation with several State and 

Federal agencies and Native American Tribes. Sampling sites 

(fig. 3) extended from the mining district downstream into the 

upper parts of Grand Lake O’ the Cherokees.

Lakebed, Floodplain, and Streambed Sediment 

Collection and Analyses

Two lakebed sediment samples were collected by 

clamshell dredge (USGS sampler BM–54) from two sites in 

the upstream end of Grand Lake O’ the Cherokees in April 

2002 and April 2004 (table 2 and fig. 3) by using methods 

described in Radtke (1997). Sediment cores were collected at 

five additional sites on an exposed sandbar during the second 

sampling in April 2004 (fig. 3) by using a stainless steel corebarrel with a 2-inch polycarbonate core liner pushed to depths 

as much as 2 feet below the sandbar surface (table 3). The 

liner-encased core samples were removed from the core barrel, 

capped, and refrigerated (figs. 4 and 5). Core sub-sampling 

methods were followed to ensure minimal cross contamination at different sample depths. Core liners were cut open, 

with core material more than 0.4 inch from the edges being 

composited (fig. 5). Sediment samples collected in April 2002 

and April 2004 were analyzed for concentrations of selected 

metals by the USGS National Water-Quality Laboratory in 

Lakewood, Colorado, (NWQL), by using microwave-assisted 

acid digestion (U.S. Environmental Protection Agency Method 

3051A–revision 1) (U.S. Environmental Protection Agency, 

1998) followed by metals analyses by inductively-coupled 

plasma-mass spectrometry, by using methods described in 

Garbarino and Struzeski (1998). Sediment samples were 

not segregated by particle-size distribution for the studies 

summarized in this report. Metals in tailings in the mining 

district tend to be most concentrated in the smallest particles, 

facilitating erosion and transport of metals by air and water 

(Datin and Cates, 2002; Schaider and others, 2007). USGS 

staff collected 12 sediment cores in a transect across the 

floodplain perpendicular to Tar Creek, the principle stream 

draining the mining district, about 165 feet south of the USGS 

gaging station (number 07185095) at the 22nd Street Bridge 

at Miami, Oklahoma, on June 16, 2004 (figs. 3, 5, and 6), to 

characterize concentrations of metals in sediments. Those core 

samples were obtained by using direct-push technology that 

Table 2. U.S. Geological Survey investigations in the Oklahoma part of the Tri-State mining district, 2000-06.

Cooperator Years Data-collection activity

Quapaw Tribe of Oklahoma 2000

Collect surface-water samples six times at five stream sites to investigate concentrations of total metals and other constituents (summary 

at http://ok.water.usgs.gov/quapaw/).

Seneca-Cayuga Tribe 

of Oklahoma

2002,

2004

Obtain and analyze lake sediment for metals from the upstream end of 

Grand Lake O’ the Cherokees

Oklahoma Department 

of Environmental Quality 2004

Obtain sediment cores in a transect across Tar Creek floodplain in 

Miami, Oklahoma

Have sediment samples analyzed for metals

Oklahoma Department

of Environmental Quality 2004–06

Collect surface-water samples at high flows and sediments for metals 

analysis

Oklahoma Department of Environmental Quality staff collected 

water-quality samples at base flows.

U.S. Environmental

Protection Agency 2005

Collect surface-water samples in Tar and Lytle Creeks to analyze for 

flux of leachate from chat piles and mine discharge entering Tar 

Creek (Cope and others, 2008)
Methods 7

produced cores of 1.5-inch diameter and as much as 3.5 feet in 

length (table 4 and fig. 6). Direct-push coring was completed 

to refusal (inability to further penetrate sediments). Similar 

processing and analyses methods were used for these sediment 

cores as were used for samples collected in hand cores on the 

sandbar in the upstream end of Grand Lake O’ the Cherokees 

in April 2004.

USGS and DEQ staff also periodically collected a total 

of 85 streambed sediment samples from 8 sites in conjunction with the collection of water-quality samples in the mining 

district from 2004–2006. Those sediment samples were collected from the same locations during each sampling period by 

using decontaminated plastic spoons and bowls. No sieving, 

nor any other sediment-size-separation techniques, was done 

with these samples prior to digestion and analysis. Those sediment samples were analyzed by the USGS NWQL for metals 

concentrations by using microwave-assisted acid digestion 

(U.S. Environmental Protection Agency, 1998) and analysis 

of digestate fluids by inductively coupled plasma-optical 

emission spectrometry and inductively coupled plasma-mass 

spectrometry (Garbarino and Struzeski, 1998).

Water-Quality Sampling and Analyses

Streamflow measurements were made coincident with 

collection of about half of the surface-water-quality samples, 

those samples collected at high-flow conditions. Streamflow 

measurements associated with those samples were made by 

using either acoustic Doppler velocity (ADV) instruments, 

Doppler profilers (ADCP), or with Price AA or pygmy current 

meters in accordance with protocols described in Rantz and 

others (1982) and Oberg and others (2005). Sampling times 

and stream discharge measurements were not recorded in conjunction with collection of surface-water-quality samples at 

low- flow conditions. As a result, three approaches, described 

in tables 5 and 6, were used to discard water-quality data or to 

estimate stream discharge at the times of collection of those 

samples.

Surface-water-quality samples were collected and water 

properties such as pH, temperature, turbidity, and dissolved 

oxygen concentrations were collected and measured according to protocols described by Wilde and others (1998a and b). 

Water samples collected from 2000 through 2003 were analyzed by the NWQL for concentrations of total and dissolved 

metals (aluminum, cadmium, iron, lead, manganese, and zinc) 

by inductively coupled plasma (ICP) method (Faires, 1993). 

Table 3. Lakebed sediment sampling sites in the upstream end of Grand Lake O’ the Cherokees (April 2002 and April 2004).

[NAD, North American Datum, sites listed from upstream to downstream]

Site name

USGS site 

identification 

number

Latitude, and 

longitude, in decimal 

degrees

Latitude and 

longitude 

datum

Streambed 

sediment 

collection 

depths,

in inches below 

streambed surface

Grand Lake O’ the 

Cherokees near Wyandotte, 

Oklahoma (Wyandotte)

364532094460801 N36.759,

W–094.769 NAD27 0–0.25 (in 2002)0–2.00 (in 2004)

Grand Lake O’ the 

Cherokees Sediment #1 364520094453101 N36.759,W–094.759 NAD83 0–36

Grand Lake O’ the 

Cherokees Sediment #2 364512094451501 N36.754,W–094.753 NAD83 0–36

Grand Lake O’ the Cherokees 

Sediment #3 364514094451401 N36.754,W–094.754 NAD83 0–36

Grand Lake O’ the 

Cherokees Sediment #4 364514094451401 N36.754,W–094.754 NAD83 0–36

Grand Lake O’ the 

Cherokees Sediment #5 364459094443801 N36.750,W–094.744 NAD83 0–36

Grand Lake O’ the Cherokees near 

Fairland, Oklahoma 

(Fairland)

364344094442001 N36.729,

W–094.739 NAD27 0–0.25 (in 2002)0–2.00 (in 2004)
8 Selected Metals in Sediments and Streams in the Oklahoma Part of Tri-State Mining District, 2000–2006

Figure 4. Location of sites sampled for sediments in the upstream part of Grand Lake O’ the Cherokees, April 2002 and April 2004.

Figure 5. Measurement and processing of sediment cores collected in the upstream end of Grand Lake O’ the Cherokees in April 2004.

Site sampled for streambed sediment

# and site identifier

Near

Fairland,

Okla.

94°47’ 94°46’ 94°45’ 94°44’ 94°43’

36°45’

36°46’

36°44’

0 0.5 1 KILOMETER

0 0.5 1 MILE

Aerial photo mosaic from

U.S. Department of Agriculture (2003)

Universal Transverse Mercator,

Zone 15N Projection

North American Datum 1983

#

##

#

#

#

#

Near

Fairland,

Okla.

Near

Wyandotte,

Okla. #1

#3 #2

#4

#5

GRAND LAKE O’ THE CHEROKEES
Methods 9

Figure 6. Locations of sediment cores collected on the floodplain of Tar Creek south of the 22nd Street Bridge in Miami, Oklahoma, on 

June 16, 2004.

Aerial photography from U.S. Department of Agriculture (2006)

Streams and waterbodies from National Hydrography Dataset

Universal Transverse Mercator Zone 15 North projection

North American Datum 1983

22nd Street

E–7

W–4W–3W–2W–1

W–6

E–1

E–5

W–7

E–2

E–3

E–4

300 METERS

0 150 300 FEET

0 150

!.!. !. !. !. !.!.!.!.!.!.!.

!.

EXPLANATION

Sediment core

Tar Creek

Unnamed

Tar Creek

intermittent

tributary

Tar Creek at 22nd St. Bridge

at Miami, Oklahoma gaging station

#

94°52'20" 94°52'00"

00"

'40"

36°54'

36°53
10 Selected Metals in Sediments and Streams in the Oklahoma Part of Tri-State Mining District, 2000–2006

Table 4. Locations and depths of floodplain sediment cores collected along a transect near 

Tar Creek at the 22nd Street Bridge at Miami, Oklahoma gaging station on June 16, 2004.

[all latitudes and longitudes are referenced to the North American Datum 83 geographic datum]

Site identifier

U.S. Geological 

Survey site 

identification number

Site latitudes and 

longitudes, in decimal 

degrees

Ranges of depths 

of core 

subsamples, in feet 

below land surface

E1 365357094520402 N36.89921,

W–094.86786

0–0.20,

0.20–1.50,

1.50–3.00

E2 365357094520401 N36.89922,

W–094.86773

0–0.15,

0.15–1.10,

1.10–2.90

E3 365357094520302 N36.89924,

W–094.86760

0–0.10,

0.10–0.80,

0.80–2.70

E4 365357094520301 N36.89926,

W–094.86745

0–0.10,

0.10–1.00,

1.00–2.10

E5 365357094520201 N36.89929,

W–094.86727

0–0.10,

0.10–1.60,

1.60–2.60

E7 365357094520403 N36.89923,

W–094.86790 0–1.00

W1 365358094520901 N36.89933,

W–094.86919

0–0.15,

0.15–1.50,

1.50–2.60

W2 365358094521002 N36.89930,

W–094.86941

0–0.20,

0.20–1.40,

1.40–3.50

W3 365358094521101 N36.89930,

W–094.86982

0–0.20,

0.20–1.20,

1.20–3.40

W4 365357094521201 N36.89929,

W–094.87000

0–0.15,

0.15–1.00,

1.00–3.00

W6 365357094520501 N36.89927,

W–094.86803

0–0.90,

0.90–1.35

W7 365357094520701 N36.89930,

W–094.86869

0–0.90,

0.90–1.70
Methods 11

Table 5. Stream sites sampled for water quality and streambed sediment in the Oklahoma part of the Tri-State mining 

district, 2000-06.

[sites listed in downstream order; NAD, North American Datum; under low-flow sample data included column, 1 indicates streamflow measurements made for all samples collected, 2 indicates data not included in report, as streamflows could not be reliably estimated; 3 indicates mean 

daily streamflow at gage used to estimate streamflow at time of sampling, 4 indicates streamflows at low-flow conditions were estimated by 

linear regressions between mean daily streamflows at upstream gaging stations at Spring River near Quapaw, Oklahoma or Neosho River near 

Commerce Oklahoma gages and streamflows measured at higher-flow conditions at sampling times for those sites; 5 indicates that streamflow 

measurements could not be made due to backwater (no-flow) conditions]

Site name

U.S. Geological 

Survey site 

identification 

number

Latitude, and 

longitude, 

in decimal 

degrees

Latitude 

and 

longitude 

datum

Sampled for 

streambed 

sediment

Low-flow 

sample data 

included

Neosho River near Commerce, Oklahoma 07185000 N36.929,

W–094.957 NAD83 Yes 3

Neosho River near Wyandotte, Oklahoma 07185190 N36.797,

W–094.754 NAD83 Yes 4

Elm Creek at Commerce, Oklahoma 071850850 N36.944,

W–094.905 NAD83 No 1

Lytle Creek at State Line Road 

near Picher, Oklahoma 071850840 N36.999,W–094.801 NAD83 No 1

Lytle Creek near Cardin, Oklahoma 071850870 N36.962,

W–094.846 NAD83 No 2

Tar Creek Tributary at Western Chat Pile 

at Cardin, Oklahoma 071850818 N36.978,W–094.852 NAD83 No 1

Tar Creek near Cardin, Oklahoma 071850825 N36.963,

W–094.846 NAD83 No 1

Tar Creek above Douthat Bridge 

near Cardin, Oklahoma 071850875 N36.959,W–094.845 NAD83 No 2

Tar Creek near Picher, Oklahoma 07185088 N36.958,

W–094.846 NAD83 No 2

Tar Creek near Commerce, Oklahoma 07185090 N36.944,

W–094.853 NAD83 Yes 3

Tar Creek at 22nd Street Bridge at Miami, 

Oklahoma 07185095 N36.900,W–094.868 NAD83 Yes 3

Spring River above Devils Hollow 

near Quapaw, Oklahoma 07187995 N36.961,W–094.721 NAD83 No 1

Spring River near Quapaw, Oklahoma 07188000 N36.934,

W–094.747 NAD83 Yes 3

Spring River near Wyandotte, Oklahoma 07188180 N36.801,

W–094.753 NAD83 Yes 4

Beaver Creek near Quapaw, Oklahoma 07188005 N36.934,

W–094.754 NAD83 No 1

Beaver Creek above Spring River 

near Quapaw, Oklahoma 07880070 N36.932,W–094.751 NAD83 No 1

Grand Lake O’ the Cherokees 

near Wyandotte, Oklahoma 364532094460801 N36.759,W–094.769 NAD27 Yes 5

Grand Lake O’ the Cherokees 

near Fairland, Oklahoma 364344094442001 N36.729,W–094.739 NAD27 Yes 5
12 Selected Metals in Sediments and Streams in the Oklahoma Part of Tri-State Mining District, 2000–2006

Surface-water-quality samples collected from 2004 through 

2006 were block digested and analyzed by inductivelycoupled plasma-atomic emission spectrometry with Thermo 

Jerrell Ash Trace ICP Analyzer at the DEQ Laboratory in 

Oklahoma City, Oklahoma, by using methods described in 

U.S. Environmental Protection Agency (EPA) Method 200.7 

(Martin and others, 1994).

Quality Assurance and Quality Control

Several quality-assurance samples were collected and 

analyzed to investigate the possibility of equipment contamination and natural sample variability. The 216 field waterquality samples were accompanied by 19 field blanks (8.8 percent frequency), 28 field duplicates (13.0 percent frequency), 

and 7 equipment blanks (3.2 percent frequency). Total zinc 

was detected in one blank at a concentration of 25 micrograms 

per liter (μg/L), which was greater than the minimum reporting level of 5 μg/L. Total and dissolved zinc were detected at 

concentrations of 7 μg/L in one equipment blank. No blank 

samples were collected for the 89 streambed-sediment samples 

collected in conjunction with water-quality sampling or with 

the sediment cores collected on the sand bar at the upstream 

end of Grand Lake O’ the Cherokees and in the floodplain of 

Tar Creek at Miami, Oklahoma. However, 13 duplicate sediment samples were collected in conjunction with those 

89 samples (14.6 percent collection frequency).

Relative percent differences for metals concentrations 

in streambed-sediment samples typically were 20 percent 

or more (fig. 7). Relative percent differences between fieldduplicate water-quality samples generally were less than 10 

percent, indicating good consistency of water-quality and 

other sampling variables at the times of sampling (fig. 7). 

Greater relative percent differences for sediment samples than 

for water samples probably were a result of greater heterogeneity of metals content of streambed sediments than in the 

well-mixed stream water.

Data Analysis

Metals concentration, streamflow, and metals-load data 

were graphed by using S-Plus, version 7.0, statistical software 

(Insightful Corporation, 2005). Censored data concentrations were estimated by substitution of values of half of the 

minimum reporting levels for evaluating relations between 

concentrations and streamflow. The maximum likelihood estimation (MLE) method (Cohen, 1959) was used for constructing boxplots of concentrations and estimating metals loads in 

censored data sets.

Selected Metals in Streambed 

Sediments

The primary metals associated with sulfide ores in the 

mines were cadmium, iron, lead, and zinc (McKnight and Fischer, 1970). Concentrations of those metals, and of aluminum 

and manganese, range from the tens to tens of thousands of 

milligrams per kilogram in local tailings, which are sources of 

part of the metals in local streams (table 1, Datin and Cates, 

2002; Schaider and others, 2007). Sediments were sampled in 

different settings in and downstream from the mining district 

to determine how metals may have been transported from mining areas to adjoining streams.

Lakebed Sediments

Grand Lake O’ the Cherokees (fig. 3) ultimately receives 

the surface-water drainage from the mining district. Sampling 

of sediments at two sites in the Neosho River in the upstream 

end of Grand Lake O’ the Cherokees in April 2002 and April 

2004 (table 3, figs. 3 and 4) indicated that concentrations of 

zinc, the primary metal mined in the district, range from about 

400 to 600 mg/Kg; whereas lead concentrations were less than 

50 mg/Kg (fig. 8a).

Table 6. Regression equations used to estimate streamflow at time of water-quality sampling at selected stream sites in the 

Oklahoma portion of the Tri-State mining district, 2000–06.

Upstream station with 

known mean daily 

streamflow

Station with estimated 

streamflow at time

of sampling

Regression equation r

2

 correlation 

coefficient

Spring River near 

Quapaw, Oklahoma

Spring River near 

Wyandotte, Oklahoma Estimated streamflow=(0.691*known upstream flow)1.039 0.976

Neosho River near 

Commerce, Oklahoma

Neosho River near 

Wyandotte, Oklahoma Estimated streamflow=(0.591*known upstreamflow)1.057 0.915
Selected Metals in Streambed Sediments 13

Figure 7. Relative percent differences for concentrations of (A) selected metals in streambed sediment, and (B) water duplicate 

samples collected in the Oklahoma part of the Tri-State mining district, 2000–06.

ALUMINUM

CADMIUM

IRONLEAD

MANGANESE

ZINC

DISSOLVED ALUMINUM

TOTAL ALUMINUM

DISSOLVED CADMIUM

TOTAL CADMIUM

DISSOLVED IRON

TOTAL IRON

DISSOLVED LEAD

TOTAL LEAD

DISSOLVED MANGANESE

TOTAL MANGANESE

DISSOLVED ZINC

TOTAL ZINC

METAL

0

20

40

60

80

100

0

20

40

60

80

100

RELATIVE DIFFERENCE, IN PERCENTAGE

x

x

o

o

x

o

o

o

o

o

o

o

o

xx

o

o x

x

o

x

o

x x

x

x

xx

x

x

o oo

16 18 17 21 18 18 16 17 23 22 18 20

12 11 13 13 13 13

17 Number of values

EXPLANATION

x

x

o

o

Upper adjacent

75th percentile

Median

25th percentile

Lower adjacent

Lower outside

Lower detached

Upper detached

Upper outside

A

B
14 Selected Metals in Sediments and Streams in the Oklahoma Part of Tri-State Mining District, 2000–2006

Sampling of five sites on a mid-channel sand bar for additional metals in April 2004 (table 3, figs. 3 and 4) indicated 

that sediment samples in the upstream end of the lake can contain several thousand milligrams per kilogram of aluminum 

and iron, and several hundred milligrams per kilogram of manganese and zinc (figs. 8b and 8c). Lead concentrations were 

about 10 percent of the concentrations of zinc and cadmium 

concentrations were about 0.1 percent of zinc concentrations, 

which is consistent with ratios of those metals in tailings in the 

district (table 1, Datin and Cates, 2002; Schaider and others, 

2007). No clear trends were detected in total cadmium, lead, 

and zinc concentrations in the sediments in downstream direction (north to south, sites 1 to 5, figs. 4 and 8) on that sand bar.

Floodplain Sediments

A transect of sediment cores collected across the floodplain of Tar Creek near Miami, Oklahoma, in 2004 were 

similar to or greater than concentrations of those metals in the 

upstream end of Grand Lake O’ the Cherokees. Concentrations of cadmium, lead, and zinc in sediment samples from a 

transect of cores collected on June 16, 2004, on the floodplain 

of Tar Creek about 165 feet south of the 22nd Street Bridge in 

Miami, Oklahoma, (figs. 3, 6, and 9) generally were greatest 

at cores W6 and W7 (fig. 9) that correspond to the location of 

a slough, which is the channel of an intermittent creek flowing 

from mined areas in Commerce, Oklahoma, southeastward 

toward Miami, Oklahoma. Metals concentrations in sediments 

near that slough were similar or greater than were reported 

for streambed sediment at nearby sites on Tar Creek in the 

mid-1980s (Parkhurst and others, 1988) and were similar to 

concentrations of cadmium, iron, lead and zinc in tailings 

(fig. 8, table 1, Datin and Cates, 2002; Schaider and others, 

2007). Sediment-size analyses were not done on those samples, but visual observation of the cores indicated interbedded 

fine sands, silty sands, and silty clays (fig. 5). The slough area 

near the center of the transect tended to have finer sediments 

than the cores collected on the western and eastern end of the 

transect (Caleb Cope, U.S. Geological Survey, written commun., 2004), with finer sediments commonly being associated 

with greater metals concentrations in tailings in the mining 

district (table 1).

Large concentrations of aluminum and manganese may 

be indigenous to local soils in the forms of clay minerals and 

manganese oxide concretions. Concentrations of these two 

metals had different patterns than the other metals in the cores 

(fig. 9). The greatest concentrations of aluminum were in samples from the westernmost core (W-4) and core E-4, east of 

Tar Creek (fig. 9). The greatest concentrations of manganese 

were 1.5 to 2.0 feet below land surface in the cores closest to 

Tar Creek (fig. 9). Concentrations of both of these metals were 

greater in these cores than in local tailings 

(fig. 9, table 1, Datin and Cates, 2002; Schaider and others, 

2007). General increases in aluminum and manganese with 

depth (fig. 9) may be a result of leaching of these metals from 

shallow soil layers and/or to greater concentrations of these 

metals in less-weathered subsoils and shales with depth.

Streambed Sediments

Streambed sediments collected from Tar Creek at the 

22nd Street Bridge in Miami, Oklahoma, gaging station from 

2004 through 2006 had similar ranges of metals concentrations as those ranges recorded in the sediment cores collected 

in the floodplain of Tar Creek on June 16, 2004 (figs. 9 and 

10). The greatest metal concentrations in local sediments may 

be associated with tailings and ground water seeping from the 

mines, but also may have sources in the mineral components 

of local soils and bedrock, such as aluminum (associated with 

clays), and iron and manganese (associated with oxidized soils 

or local shales) (Hem, 1992, p. 73; Drever, 1988, p. 342).

Aluminum

Aluminum concentrations in streambed sediments 

increased in the downstream direction on the Neosho River, 

Tar Creek, and the Spring River, possibly because of runoff of 

aluminum in clays in local soils and tailings (fig. 10 and

table 1). The greatest aluminum concentrations generally were 

in streambed sediments at the two sampled sites on the Neosho 

River (fig. 10), the drainage basin of which is largely underlain 

by Krebs Group shales of Mississippian age (McKnight and 

Fischer, 1970), a probable source of clay minerals containing 

aluminum.

Cadmium

Cadmium was not detected in streambed sediments at the 

Neosho River near the Wyandotte, Oklahoma, site. Sorption 

to iron oxide and hydroxide in upstream sediments, small concentrations of cadmium in tailings (table 1), or the high propensity of cadmium to dissolve, rather than precipitate (Carroll 

and others, 1998; O’Day and others, 1998; Morel and Hering, 

1993, p. 355), may account for the lack of detectable cadmium 

in streambed sediments several miles downstream from the 

mining district. Cadmium concentrations decreased in the 

downstream direction in Tar Creek (fig. 10). Those concentration decreases were probably a result of some combination of 

dilution of cadmium with other sediments, dissolution and/or 

flushing of cadmium into the water column, or sequestration 

of cadmium in upstream sediments. Greater cadmium concentrations in streambed sediments in the downstream direction, 

such as those concentrations in the Spring River, may be a 

result of flushing of older, more cadmium-enriched sediments 

downstream or inputs of additional sources of cadmium-containing sediments between the sites near Quapaw and Wyandotte, Oklahoma (fig. 10).
Selected Metals in Streambed Sediments 15

Streambed sediment samples collected in the upstream end

of Grand Lake O’ the Cherokees, April 2002 and April 2004

Streambed sediment samples collected on a sandbar in the

upstream end of Grand Lake O’ the Cherokees, April 8, 2004

Streambed sediment samples collected on a sandbar in the

upstream end of Grand Lake O’ the Cherokees, April 8, 2004

0

0

100

200

300

400

500

600

650

0

200

400

600

700

2,000

4,000

6,000

8,000

11,000

10,000

METAL CONCENTRATIONS, IN MILLIGRAMS PER KILOGRAM

#1 #2 #5

SITE

SITE

#1 #2 #5

SITE AND YEAR

FAIRLAND,

2002

WYANDOTTE,

2002

FAIRLAND,

2004

WYANDOTTE,

2004

#3 #4

#3 #4

EXPLANATION

Zinc

Lead

Nickel

Manganese

Iron

Aluminum

EXPLANATION

Zinc

Lead

Cadmium

EXPLANATION

Zinc

Lead

Cadmium

A

C

B Figure 8. Selected metals 

concentrations in streambed 

samples collected at sites in the 

upstream end of Grand Lake O’ the 

Cherokees, April 2002 and April 

2004.
16 Selected Metals in Sediments and Streams in the Oklahoma Part of Tri-State Mining District, 2000–2006

Line of equal value—Intervals variable

Sample location and value in milligrams per kilogram— < , less than

Sample identifier 

EXPLANATION

1,000

E5

490

-2.5

-2.0

-1.5

-1.0

-0.5

0

-2.5

-2.0

-1.5

-1.0

-0.5

0

-2.5

-2.0

-1.5

-1.0

-0.5

0

MEAN CORE DEPTH, IN FEET BELOW LAND SURFACE

600 300 0 300 600 300 0 300

DISTANCE FROM CENTER OF STREAM CHANNEL, IN FEET

Vertical exaggeration=115

W4

W3

W2

W1

W7 (Slough)

W6

E7E1

E2

E3

E4

E5

F. Zinc

Tar Creek

200 200

200

100

100

297

141

39

154

38

38

184

89

39

9,260

75

29

3,410

6,280

4,400

858

194

203

58

40

36

38

33

24

17

121

310315 146

111

180

223

E. Manganese

Tar Creek

1,000

800

800

600

400

1,200

400

400

600

600

400

600

400

701

416

286

1,220

514

502 603

545

352

332

297

187

389

202

559

490

367

343

363

504

423

463

453

462

379

638

482

593

182

817

154

186

W4

W3

W2

W1

W7 (Slough)

W6

E7E1

E2

E3

E4

E5

D. Lead

Tar Creek

100

300

700

200

500

300

100

200

400

600

200

300

400

45

11

27

13

10

36

20

10

49

13

11

306

729

264

30

24

29

14

<10

19

13

13

12

9

19

46 45 24

20 29

30

23 W4

W3

W2

W1

W7 (Slough)

W6

E7E1

E2

E3

E4

E5

C. Iron

Tar Creek

20,000

20,000

30,000

40,000

50,000

12,700

14,500

15,100

13,200

14,200

14,300

14,100

19,400

12,700

14,800

11,300

12,300

13,600

14,300

14,900

17,300

18,400

15,900

16,900

27,000

16,100

17,800

19,200

58,600

13,400

47,600

16,300

10,40012,500

14,100 12,800

11,600

W4

W3

W2

W1

W7 (Slough)

W6

E7E1

E2

E3

E4

E5

B. Cadmium

Tar Creek

1

1

10

20

30

40

2

<1

21

48

24

2

1

1

<1

<1

<1

<1

2 1

1

<1

<1

<1

<1

<1

<1

<1 <1

2

<1

<1

<1

<1

<1

2

<1

<1W4

W3

W2

W1

W7 (Slough)

W6

E7E1

E2

E3

E4

E5

A. Aluminum

Tar Creek

20,000

10,000

10,000

20,000

15,000

15,000

15,000

15,000

15,000

20,000

7,570

16,400

18,300

14,900

9,840

10,000

16,100

7,060

7,060

16,400

9,260

11,800

17,100

9,370

17,300

14,100

18,700

13,700

10,300

13,500

19,000

21,500

19,600

10,400

11,900

12,100

6,250

11,200

11,500

10,000 11,100

20,900

W4

W3

W2

W1

W7 (Slough)

W6

E7E1

E2

E3

E4

E5

Figure 9. Cross-sectional diagrams showing distributions of concentrations of (A) aluminum, (B) cadmium, (C) iron, (D) lead, (E) 

manganese, and (F) zinc in sediment cores collected in a transect 165 feet south of the 22nd Street Bridge at Tar Creek at Miami, 

Oklahoma, on June 16, 2004.
Selected Metals in Streambed Sediments 17

Aluminum

Cadmium Iron

Lead Manganese Zinc

11 17 9 15 16 18

3 0 3 6 6 9 2 2 15 18 9 16 11 17 1 1

9 15 16 11 17 18 2 2 15 18 9 16 11 17 1 1 15 18 9 16 11 17 2 2

xx

x

x

x

o

oo oo

x

x x

x

x

x

oo oo

x x

x

x

x

x

o

x

oo x

oo o

o

100

1,000

10,000

100,000

50

10

51

0.5

5,0001,000

50,00010,000

500,000100,000

500100

5010

51

10

5

100

1,000

10,000

5010

500100

5,000

1,000

10,000

METAL CONCENTRATION, IN MIILGRAMS PER KILOGRAM

30 Number of values

EXPLANATION

Schematic boxpl

o

xx

o

Upper detachedUpper outsideUpper adjacent75th percentileMedian

25th percentile

Lower adjacentLower outside Lower detached

DOT

ot

GRAND LAKE O’ THE CHEROKEES NEAR WYANDOTTE

GRAND LAKE O’ THE CHEROKEES NEAR FAIRLAND

NEOSHO RIVER

NEAR COMMERCE

NEOSHO RIVER

NEAR WYANDOTTE

NEAR COMMERCE

TAR CREEK AT 22ND STREET BRIDGE

SPRING RIVER

NEAR QUAPAW

SPRING RIVER

TAR CREEK

NEAR WYANDOTTE

NEOSHO RIVER

NEAR COMMERCE

NEOSHO RIVER

NEAR WYANDOTTE

NEAR COMMERCE

TAR CREEK AT 22ND STREET BRIDGE

SPRING RIVER

NEAR QUAPAW

SPRING RIVER

TAR CREEK

NEAR WYANDOTTE

GRAND LAKE O’ THE CHEROKEES NEAR WYANDOTTE

GRAND LAKE O’ THE CHEROKEES NEAR FAIRLAND

NEOSHO RIVER

NEAR COMMERCE

NEOSHO RIVER

NEAR WYANDOTTE

NEAR COMMERCE

TAR CREEK AT 22ND STREET BRIDGE

SPRING RIVER

NEAR QUAPAW

SPRING RIVER

TAR CREEK

NEAR WYANDOTTE

GRAND LAKE O’ THE CHEROKEES NEAR WYAN TE

GRAND LAKE O’ THE CHEROKEES NEAR FAIRLAND

NEOSHO RIVER

NEAR COMMERCE

NEOSHO RIVER

NEAR WYANDOTTE

NEAR COMMERCE

TAR CREEK AT 22ND STREET BRIDGE

SPRING RIVER

NEAR QUAPAW

SPRING RIVER

TAR CREEK

NEAR WYANDOTTE

GRAND LAKE O’ THE CHEROKEES NEAR WYANDOTTE

GRAND LAKE O’ THE CHEROKEES NEAR FAIRLAND

NEOSHO RIVER

NEAR COMMERCE

NEOSHO RIVER

NEAR WYANDOTTE

NEAR COMMERCE

TAR CREEK AT 22ND STREET BRIDGE

SPRING RIVER

NEAR QUAPAW

SPRING RIVER

TAR CREEK

NEAR WYANDOTTE

GRAND LAKE O’ THE CHEROKEES NEAR WYANDOTTE

GRAND LAKE O’ THE CHEROKEES NEAR FAIRLAND

NEOSHO RIVER

NEAR COMMERCE

NEOSHO RIVER

NEAR WYANDOTTE

NEAR COMMERCE

TAR CREEK AT 22ND STREET BRIDGE

SPRING RIVER

NEAR QUAPAW

SPRING RIVER

TAR CREEK

NEAR WYANDOTTE

MINIMUM REPORTING LEVEL= 1

MINIMUM REPORTING LEVEL=10

Figure 10. Ranges of concentrations of selected metals in streambed sediment samples from six stream sites in the Oklahoma part of the Tri-State mining district,2004–06.
18 Selected Metals in Sediments and Streams in the Oklahoma Part of Tri-State Mining District, 2000–2006

Iron

Iron, which tends to precipitate as oxide and hydroxide 

minerals in the alkaline and oxidizing conditions of local 

streams (fig. 11, Elder, 1988, p. 11 and 15), generally occurred 

in the greatest concentrations of the analyzed metals in 

streambed sediments (figs. 2 and 10, Morel and Hering, 1993, 

p. 267–271; Hem, 1992, p. 79-80; Drever, 1988, p. 297; and 

Stumm and Morgan, 1981, p. 241). Although oxidation of tens 

of thousands of micrograms per liter of iron likely happens 

rapidly, producing acid in addition to the acid produced by sulfide dissolution in the mine workings (equation 1), abundant 

carbonate minerals such as calcite and dolomite in local rocks 

buffer those acids (equation 2), and bring pH of ground water 

in the mines and local surface water up to circum-neutral values of 6 or more (DeHay, 2003; DeHay and others, 2004; and 

fig. 11). Real-time monitors, recording water-quality data at 

15-minute intervals, at the Tar Creek at Commerce, Oklahoma, 

Tar Creek at 22nd Street Bridge in Miami, Oklahoma, and 

the Beaver Creek near Quapaw, Oklahoma, sites from 2004 

to 2006 obtained similar ranges of pH and dissolved oxygen 

concentrations (fig. 11).

2 Fe+2 (dissolved) + 2 H2O + O2 → 2 FeOOH (solid goethite) + 2 H+ (1)

CaCO3

 (solid calcite) + H+ → Ca+2 (dissolved) + HCO -

3 (dissolved 

bicarbonate) (2)

Iron concentrations in sediments increased in the downstream direction for the two sites sampled on the Neosho River 

and Tar Creek, but decreased in the downstream direction 

between the two sites sampled on the Spring River 

(fig. 10). Increased iron concentration in streambed sediments 

in the downstream direction in the Neosho River and Tar 

Creek may be a result of a combination of runoff and seepage 

from tailings and/or the mine workings, and runoff of ferruginous soil particles from sources in the downstream direction. 

Decreased iron concentration in streambed sediments in the 

downstream direction at the two Spring River sites may be 

a result of flushing of soft flocculated iron particles farther 

downstream or to trapping of ferruginous minerals in parts of 

the river upstream from the site near Wyandotte, Oklahoma. 

In addition to being the dominant precipitated metal in local 

streams, ferric oxyhydroxide surfaces also can adsorb other 

metals, with greater absorption taking place at higher pH 

(Hem, 1992, p. 78; Drever, 1988, p. 343).

Lead

Lead concentrations are likely to be much greater in 

streambed sediments than in water because lead has: (a) small 

solubility constants in sulfide and hydroxycarbonate minerals, 

(b) tendency to precipitate with manganese oxide, and 

(c) tendency to adsorb to organic and inorganic sediment 

surfaces (American Water Works Research Association 

Foundation, 1996, p. 140; Morel and Herring, 1993, p. 524; 

Hem, 1992, p. 143; Drever, 1988, p. 344; Stumm and Morgan, 

1981, p. 243 and 245). Lead was detected in concentrations 

about only one order of magnitude (10 times) greater than 

cadmium in streambed sediments, despite being found in 

concentrations 30-100 times greater than cadmium in tailings 

(table 1 and fig. 10). The relative scarcity of lead compared 

to cadmium in local streambed sediments may be a result 

of adsorption of lead to mobile organic and clay particles in 

stream water that have been flushed downstream, or to seepage 

of dissolved cadmium from oxidizing sphalerite (ZnS) in local 

mine workings. The relative similarity of lead concentrations 

in streambed sediments at the sampled sites (fig. 10) indicated 

a mechanism such as adsorption of lead to and transport on 

organic and inorganic sediment particles that resulted in even 

distribution in streambed sediments.

Manganese

Manganese can substitute for iron, magnesium, or calcium in silicate minerals and participates in reactions similar 

to reactions of iron in similar redox conditions, but manganese 

is slightly less likely to oxidize and precipitate than iron and 

has extremely high adsorption capacities for heavy metals 

(Morel and Hering, 1993, p. 243-244, Hem, 1992, 

p. 85, Drever, 1988, p. 342). Similar to iron, manganese concentrations increased in the downstream direction for the sites 

sampled on the Neosho River and Tar Creek, and decreased 

in the downstream direction for the two sites sampled on the 

Spring River (fig. 10).

Zinc

Concentrations of zinc, the metal extracted in the greatest amounts from this mining district, were at least an order 

of magnitude or more greater than lead concentrations and 

50 times or more greater than cadmium concentrations in the 

streambed-sediment samples (fig. 10). After zinc dissolves 

from sphalerite in the mine workings and in tailings, zinc combines with oxygen, hydroxide, and carbonate to form a variety 

of precipitating minerals and is sequestered with iron oxyhydroxide minerals on the land surface and in local streams 

(Carroll and others, 1998; O’Day and others, 1998). Similar to 

iron, zinc concentrations in streambed sediments increased in 

the downstream direction in the Neosho River and Tar Creek, 

indicating input and/or flushing of zinc downstream along 

those stream segments, and decreased in the downstream 

direction between the two sites on the Spring River, indicating 

upstream sequestration and/or flushing of zinc-rich sediments 

farther downstream (fig. 10).
Selected Metals in Streambed Sediments 19

NEOSHO RIVER NEAR COMMERCE

NEOSHO RIVER NEAR WYANDOTTE

TAR CREEK NEAR COMMERCE

 TAR CREEK AT 22ND STREET BRIDGE

GRAND LAKE O’ THE CHEROKEES NEAR WYANDOTTE

GRAND LAKE O’ THE CHEROKEES NEAR FAIRLAND

SPRING RIVER NEAR WYANDOTTE

BEAVER CREEK NEAR QUAPAW

BEAVER CREEK ABOVE SPRING RIVER NEAR QUAPAW

SPRING RIVER NEAR QUAPAW

TAR CREEK NEAR PICHER

TAR CREEK ABOVE DOUTHAT BRIDGE NEAR CARDIN

TAR CREEK NEAR CARDIN

TAR CREEK TRIBUTARY AT WESTERN CHAT PILE

ELM CREEK AT COMMERCE

LYTLE CREEK NEAR CARDIN

LYTLE CREEK AT STATE LINE ROAD NEAR PICHER

SPRING RIVER ABOVE DEVILS HOLLOW NEAR QUAPAW

SITE

DISSOLVED OXYGEN CONCENTRA TION,

IN MILLIGRAMS PER LITER

0

5

10

15

20

25

PH, IN STANDARD UNTIS

5.5

6.0

6.5

7.0

7.5

8.0

8.5

9.0

9.5

10 10 1 1 8 1 7 7 7 20 20 7 17 11 6 7 2 2

10 10 1 1 8 1 7 7 7 20 20 7 17 11 6 7 2 2

x

x

o

o

30 Number of values

EXPLANATION

Schematic boxplot

Upper adjacent

75th percentile

Median

25th percentile

Lower adjacent

Lower outside 

Lower detached

Upper detached

Upper outside

x

x

o

o

30 Number of values

EXPLANATION

Schematic boxplot

Upper adjacent

75th percentile

Median

25th percentile

Lower adjacent

Lower outside 

Lower detached

Upper detached

Upper outside

o o

o

x

x

x

x

x

x

x o

o

o o o

x

o

o

o

x

Figure 11. Ranges of concentrations of dissolved oxygen and of pH in water-quality samples from 18 stream sites in the Oklahoma 

part of the Tri-State mining district 2004–06.
20 Selected Metals in Sediments and Streams in the Oklahoma Part of Tri-State Mining District, 2000–2006

Selected Metals in Streams

Aqueous Concentrations and Streamflow

In the alkaline and well-oxidized conditions of local 

streams, many of the analyzed metals precipitate into low-solubility oxide, oxyhydroxide, and oxycarbonate minerals. Such 

conditions also facilitate adsorption of metals onto surfaces 

of abundant clay minerals, and onto complexes of iron and 

manganese oxyhydroxides which are abundant in local stream 

channels (fig. 2C and D). Because of the propensity of metals 

to precipitate as many different minerals or be sorbed to other 

minerals, total metals concentrations in these streams typically 

were less than metals concentrations in streambed sediments 

by factors ranging from hundreds to thousands 

(figs. 10, 12–17).

During base flow, metals in stream water in the mining 

district are likely to come primarily from two sources: 

(1) seepage of metals in ground water (from flooded abandoned underground mine workings and locally perched water 

tables) discharging to streams; and (2) leaching of metals from 

streambed sediments, and tailings. Runoff during wet periods 

may wash metals-rich sediments into local streams, increase 

leaching from tailings, and re-suspend metals in metalliferous 

streambed sediments.

Aluminum

Water samples collected from the two sites on the Neosho 

River (Neosho River near Commerce, Oklahoma; and Neosho River near Wyandotte, Oklahoma) had the greatest total 

aluminum concentrations of the sampled sites (fig. 12). Much 

of the Neosho River drains areas underlain by Krebs Group 

shales of Mississippian age (McKnight and Fischer, 1970). 

Similar concentrations of aluminum in water samples collected at the Neosho River near Commerce, Oklahoma, site, 

upstream from most of the mined areas, and at the Neosho 

River near Wyandotte, Oklahoma, site, downstream from most 

of the mined area, support the concept that little of the total 

aluminum in water in that river is associated with the mined 

area, despite the fact that tailings in the mining district contained from about 2,000 to 20,000 mg/Kg of aluminum (table 

1). Total aluminum concentrations for two of the sites on the 

Spring River (Spring River near Quapaw, Oklahoma; and 

Spring River near Wyandotte, Oklahoma) were about an order 

of magnitude (10 times) less than in water samples collected 

at the two Neosho River sites (fig. 12A), possibly because a 

much greater proportion of the Spring River Basin is underlain by limestones of the Mississippian age Boone Formation, 

rather than by aluminum-rich shales (McKnight and Fischer, 

1970). Water samples collected from Tar Creek generally had 

smaller concentrations of total aluminum than water samples 

collected from the Neosho and Spring Rivers (fig. 12A). Tar 

Creek has a much smaller drainage area than those rivers and 

much smaller streamflows capable of transporting clays, but 

a greater proportion of mined lands in the basin (table 7). If 

tailings were the primary source of aluminum to surface water 

in the mining district, then total aluminum concentrations 

should have been greater in Tar Creek than in the rivers. Total 

aluminum concentrations were similar between upstream and 

downstream stations on the Neosho River and Tar Creek, but 

increased slightly in the downstream direction on the Spring 

River (fig. 12A).

Total aluminum concentrations generally increased with 

streamflow at stations on the Neosho and Spring Rivers and 

on Tar Creek (figs. 12B and C). Such consistent increases in 

aluminum with increasing streamflow at those sites further 

support the concept that particulate aluminum is likely to be 

predominantly from runoff and/or re-suspension of clayey, 

aluminum-rich streambed sediments at higher flows, rather 

than an indicator of the effects of mining on surface-water 

quality.

All filtered (dissolved) water samples contained less 

than the minimum reporting level 300 μg/L for aluminum. 

A smaller minimum reporting level for dissolved aluminum 

probably would have produced fewer censored data for 

samples from these sites.

Cadmium

Cadmium is a trace metal substituting in the structure 

of the zinc sulfide mineral sphalerite (Hem, 1992), but may 

be more likely to remain in solution than zinc on weathering 

of sphalerite. Tailings in this mining district contained ratios 

of cadmium:lead:zinc of about 1:10:100 (table 1, Datin and 

Cates, 2002; Schaider and others, 2007). Cadmium, like many 

other metals, can be adsorbed by manganese oxides, clays, and 

organic matter (Hem, 1992, p. 142; Drever, 1988, p. 352–382) 

that may impede or facilitate transport in water, depending on 

the nature of the particles to which cadmium is adsorbed and 

local streamflow and streambed characteristics.

Cadmium in water, particularly in drinking water, poses 

a threat to the health of humans and a variety of other terrestrial and aquatic organisms. Excessive intake of cadmium 

by humans has been associated with health-degrading conditions such as lung damage, kidney disease, bone degradation, and irritation of the digestive tract (Agency for Toxic 

Substances and Disease Registry, 1999a). Cadmium also has 

been determined to be “reasonably anticipated to be carcinogenic” (Agency for Toxic Substances and Disease Registry, 

1999a). Akesson and others (2005) reported that damage may 

be sustained by human kidneys from exposure to cadmium 

at concentrations previously assumed to be safe. According 

to World Health Organization (1996), rates of absorption and 

retention of cadmium are greater in children, with cadmium 

progressively accumulating in the kidneys with age.

Most total and dissolved cadmium concentrations were 

less than the DEQ laboratory minimum reporting level of 

5 μg/L (fig. 13A). Water samples analyzed for projects completed prior to 2004 by the USGS were analyzed at the USGS 
Selected Metals in Streams 21

NEOSHO RIVER NEAR COMMERCE

NEOSHO RIVER NEAR WYANDOTTE

TAR CREEK NEAR COMMERCE

 TAR CREEK AT 22ND STREET BRIDGE

GRAND LAKE O’ THE CHEROKEES NEAR WYANDOTTE

GRAND LAKE O’ THE CHEROKEES NEAR FAIRLAND

SPRING RIVER NEAR WYANDOTTE

BEAVER CREEK NEAR QUAPAW

BEAVER CREEK ABOVE SPRING RIVER NEAR QUAPAW

SPRING RIVER NEAR QUAPAW

TAR CREEK NEAR PICHER

TAR CREEK ABOVE DOUTHAT BRIDGE NEAR CARDIN

TAR CREEK NEAR CARDIN

TAR CREEK TRIBUTARY AT WESTERN CHAT PILE

ELM CREEK AT COMMERCE

LYTLE CREEK NEAR CARDIN

LYTLE CREEK AT STATE LINE ROAD NEAR PICHER

SPRING RIVER ABOVE DEVILS HOLLOW NEAR QUAPAW

SITE

TOTAL AND DISSOLVED ALUMINUM

CONCENTRATIONS, IN MILLIGRAMS

PER KILOGRAM

10

1

100

1,000

10,000

100,000

TOTAL ALUMINUM CONCENTRATION, IN MICROGRAMS PER LITER

MINIMUM REPORTING LEVEL=300

o

o

x

x

x

o x

o

o

o

10 100 1,000 10,000

100

EXPLANATION

Tar Creek near Commerce, Okla.

(Al)=83.9(Q)0.449, r2

=0.817

Tar Creek at 22nd Street Bridge

(Al)=80.6(Q)0.479, r2

=0.823

1,000

1

DOWNSTREAM

[Non-detects of less than 300 micrograms

per liter are estimated as 150 micrograms

per liter]

10,000

STREAM DISCHARGE, IN CUBIC FEET PER SECOND

EXPLANATION

Neosho River near Commerce, Okla.

(Fe)=93.0Q0.488, r2

=0.708

(Fe)=67.6(Q)0.538, r2=0.762

100

1,000

10,000

10 1,000 10,000 50,000

(Fe)=0.149(Q)+15.3, r

2

=1.00

(Fe)=3.10(Q)0.771, r2=0.616

(Fe)=0.172(Q)+1890, r2=0.426

50,000

100

Neosho River near Wyandotte, Okla.

Spring River near Wyandotte, Okla.

Spring River near Quapaw, Okla.

Spring River above Devils Hollow, Okla.

STREAM DISCHARGE, IN CUBIC FEET PER SECOND

[Non-detects of less than 300 micrograms

per liter are estimated as 150 micrograms

per liter. Shading is lighter in the

downstream direction.]

x

x

o

o

Dissolved

Total

30 Number of values

EXPLANATION

Schematic boxplot

Upper adjacent

75th percentile

Median

25th percentile

Lower adjacent

Lower outside 

Lower detached

Upper detached

Upper outside

22 21 23 0 0 0 0 0 0 0 0 0 0 0 0 0 0 27 25 28 27 2 0 23 22 23 25 22 2 0 2 0 1 0 1 0

A

B

C

Figure 12. Ranges in concentrations of total and dissolved aluminum (A), and graphs of total concentrations of aluminum in surfacewater samples compared to discharge (B,C) for samples collected at sites in the Oklahoma part of the Tri-State mining district, 2000–06.
22 Selected Metals in Sediments and Streams in the Oklahoma Part of Tri-State Mining District, 2000–2006 TOTAL AND DISSOLVED CADMIUM CONCENTRATIONS, IN MICROGRAMS PER LITER TOTAL CADMIUM CONCENTRATION, IN MICROGRAMS PER LITER

NEOSHO RIVER NEAR COMMERCE

NEOSHO RIVER NEAR WYANDOTTE

TAR CREEK NEAR COMMERCE

 TAR CREEK AT 22ND STREET BRIDGE

GRAND LAKE O’ THE CHEROKEES NEAR WYANDOTTE

GRAND LAKE O’ THE CHEROKEES NEAR FAIRLAND

SPRING RIVER NEAR WYANDOTTE

BEAVER CREEK NEAR QUAPAW

BEAVER CREEK ABOVE SPRING RIVER NEAR QUAPAW

SPRING RIVER NEAR QUAPAW

TAR CREEK NEAR PICHER

TAR CREEK ABOVE DOUTHAT BRIDGE NEAR CARDIN

TAR CREEK NEAR CARDIN

TAR CREEK TRIBUTARY AT WESTERN CHAT PILE

ELM CREEK AT COMMERCE

LYTLE CREEK NEAR CARDIN

LYTLE CREEK AT STATE LINE ROAD NEAR PICHER

SPRING RIVER ABOVE DEVILS HOLLOW NEAR QUAPAW

SITE

0.05

1

0.1

100

10

o

o o

o

x

x

x

o

x

o

o o

o o

x

x

10 10 17 13 17 14 16 11 10 11 9 9 1 1 1 1 8 8 7 7 7 7 7 7 7 1 6 0 7 1 2 0 2 0 1 1

MINIMUM

REPORTING

LEVEL=5

x

x

o

o

Dissolved

Total

30 Number of values

EXPLANATION

Schematic boxplot

Upper adjacent

75th percentile

Median

25th percentile

Lower adjacent

Lower outside 

Lower detached

Upper detached

Upper outside

[Adjusted maximum likelihood estimation

used to estimate censored values. Some of

these sites had samples collected for total and

dissolved cadmium on different dates]

Tar Creek near Cardin, Okla.

Tar Creek near Commerce, Okla.

Tar Creek near Picher, Okla.

Tar Creek above Douthat Bridge

Tar Creek at 22nd Street Bridge at Miami, Okla.

Tar Creek tributary near western chat pile

[Non-detects of less than 10 and less than 1 micrograms

per liter are estimated as 5 and 0.5 micrograms

per liter, respectively.]

(Zn)=4.73ln(Q)+24.0, r2

=0.535

(Pb)=16.3Q0.399, r2

=0.764

(Pb)=37.8(Q)-0.310, r2

=0.973

(Zn)=8.68(Q)-0.030, r2

=0.043

(Zn)=2.49(Q)0.0930, r2

=0.215

10 100 1,000 10,000

0.1

1

100

0.001 0.01 10.1

DOWNSTREAM UPSTREAM

10

STREAM DISCHARGE, IN CUBIC FEET PER SECOND

EXPLANATION

0.5

100

10 100 1,000 50,000

0.05

10,000

5

50

STREAM DISCHARGE, IN CUBIC FEET PER SECOND

EXPLANATION

Neosho River near Commerce, Okla.

Neosho River near Wyandotte, Okla.

Spring River near Wyandotte, Okla.

Spring River near Quapaw, Okla.

Spring River above Devils Hollow, Okla.

[Non-detects of less than 10 and less than 1 micrograms

per liter are estimated as 5 and 0.5 micrograms

per liter, respectively. Shading is lighter in the

downstream direction.]

All (Cd) less than 5 micrograms per liter

All (Cd) less than 5 micrograms per liter

(Cd)=0.0001(Q)+0.242, r

2

=0.896

(Cd)=0.474ln(Q)-1.66, r2

=0.334

(Mn)=0.00004(Q)+2.33, r2

=0.408

B

C

A

Figure 13. Ranges in concentrations of total and dissolved cadmium (A), and graphs of total concentrations of cadmium in surfacewater samples compared to discharge (B,C) for samples collected at sites in the Oklahoma part of the Tri-State mining district, 2000–06.
Selected Metals in Streams 23

TOTAL IRON CONCENTRATION, IN MICROGRAMS PER LITER

A

B

C

x

x x

x

x

o

o

NEOSHO RIVER NEAR COMMERCE

NEOSHO RIVER NEAR WYANDOTTE

TAR CREEK NEAR COMMERCE

 TAR CREEK AT 22ND STREET BRIDGE

GRAND LAKE O’ THE CHEROKEES NEAR WYANDOTTE

GRAND LAKE O’ THE CHEROKEES NEAR FAIRLAND

SPRING RIVER NEAR WYANDOTTE

BEAVER CREEK NEAR QUAPAW

BEAVER CREEK ABOVE SPRING RIVER NEAR QUAPAW

SPRING RIVER NEAR QUAPAW

TAR CREEK NEAR PICHER

TAR CREEK ABOVE DOUTHAT BRIDGE NEAR CARDIN

TAR CREEK NEAR CARDIN

TAR CREEK TRIBUTARY AT WESTERN CHAT PILE

ELM CREEK AT COMMERCE

LYTLE CREEK NEAR CARDIN

LYTLE CREEK AT STATE LINE ROAD NEAR PICHER

SPRING RIVER ABOVE DEVILS HOLLOW NEAR QUAPAW

SITE

MINIMUM

REPORTING

LEVEL=20

22

22

21

23

1 31

26

32

26

29

23

22

23

1 1 1 1 8 8 1 7 7 7 7 7 7 6 1 6 6 1 1 1 00 0

TOTAL AND DISSOLVED IRON

CONCENTRATIONS, IN MICROGRAMS

PER LITER

10

100

1,000

10,000

100,000

1

0.1

Dissolved

Total

[Adjusted maximum likelihood estimation

used to estimate censored values. Some of

these sites had samples collected for total and

dissolved iron on different dates]

x

x

o

o

30 Number of values

EXPLANATION

Schematic boxplot

Upper adjacent

75th percentile

Median

25th percentile

Lower adjacent

Lower outside 

Lower detached

Upper detached

Upper outside

100

1,000

10,000

10 1,000 10,000 50,000

10

50,000

100

STREAM DISCHARGE, IN CUBIC FEET PER SECOND

EXPLANATION

Neosho River near Commerce, Okla.

Neosho River near Wyandotte, Okla.

Spring River near Wyandotte, Okla.

Spring River near Quapaw, Okla.

Spring River above Devils Hollow, Okla.

[Shading is lighter in the

downstream direction.]

(Fe)=77.0Q0.484, r

2

=0.707

(Fe)=0.188(Q)+126, r

2

=0.971

(Fe)=4.13(Q)0.695, r2

=0.470

(Fe)=0.142(Q)+1560, r2

=0.448

(Fe)=61.8(Q)0.524, r

2

=0.749

STREAM DISCHARGE, IN CUBIC FEET PER SECOND

10 100 1,000 10,000

100

10,000

0.001 0.01 10.1

1,000

50,000

Tar Creek near Cardin, Okla.

Tar Creek near Commerce, Okla.

Tar Creek near Picher, Okla.

Tar Creek above Douthat Bridge

Tar Creek at 22nd Street Bridge at Miami, Okla.

Tar Creek tributary near western chat pile

(Zn)=53400e-0.560(Q), r2

=0.993

(Pb)=781e-4.28(Q), r2

=0.643

(Pb)=40.8(Q)+530, r2

=0.0208

(Zn)=1430ln(Q)+3220, r2

=0.661

(Zn)=832(Q)0.336, r2

=0.842

DOWNSTREAM UPSTREAM

EXPLANATION

Figure 14. Ranges in concentrations of total and dissolved iron (A), and graphs of total concentrations of iron in surface-water 

samples compared to discharge (B,C) for samples collected at sites in the Oklahoma part of the Tri-State mining district, 2000–06.
24 Selected Metals in Sediments and Streams in the Oklahoma Part of Tri-State Mining District, 2000–2006 TOTAL LEAD CONCENTRATION, IN MICROGRAMS PER LITER

A

B

C

NEOSHO RIVER NEAR COMMERCE

NEOSHO RIVER NEAR WYANDOTTE

TAR CREEK NEAR COMMERCE

 TAR CREEK AT 22ND STREET BRIDGE

GRAND LAKE O’ THE CHEROKEES NEAR WYANDOTTE

GRAND LAKE O’ THE CHEROKEES NEAR FAIRLAND

SPRING RIVER NEAR WYANDOTTE

BEAVER CREEK NEAR QUAPAW

BEAVER CREEK ABOVE SPRING RIVER NEAR QUAPAW

SPRING RIVER NEAR QUAPAW

TAR CREEK NEAR PICHER

TAR CREEK ABOVE DOUTHAT BRIDGE NEAR CARDIN

TAR CREEK NEAR CARDIN

TAR CREEK TRIBUTARY AT WESTERN CHAT PILE

ELM CREEK AT COMMERCE

LYTLE CREEK NEAR CARDIN

LYTLE CREEK AT STATE LINE ROAD NEAR PICHER

SPRING RIVER ABOVE DEVILS HOLLOW NEAR QUAPAW

SITE

100

1

0.1

1,000

10

0.01

TOTAL AND DISSOLVED LEAD

CONCENTRATIONS, IN MICROGRAMS

PER LITER

o

o o

o

x

x

x

o

o

MINIMUM

REPORTING

LEVEL=10

18

22

18

22

28

26

26

26

25

23

22

23

1 1 1 1 18 8 1 7 7 7 7 7 7 7 1 6 0 7 1 2 0 2 0

x

x

o

o

Dissolved

Total

30 Number of values

EXPLANATION

Schematic boxplot

Upper adjacent

75th percentile

Median

25th percentile

Lower adjacent

Lower outside 

Lower detached

Upper detached

Upper outside

[Adjusted maximum likelihood estimation

used to estimate censored values. Some of

these sites had samples collected for total and

dissolved lead on different dates]

10

100

10 100 1,000 50,000

1

10,000

STREAM DISCHARGE, IN CUBIC FEET PER SECOND

EXPLANATION

Neosho River near Commerce, Okla.

Neosho River near Wyandotte, Okla.

Spring River near Wyandotte, Okla.

Spring River near Quapaw, Okla.

Spring River above Devils Hollow, Okla.

[Non-detects of less than 10 and less than 1 micrograms

per liter are estimated as 5 and 0.5 micrograms

per liter, respectively. Shading is lighter in the

downstream direction.]

All (Pb) less than 10 micrograms per liter

(Pb)=3.57(Q)0.055, r2

=0.113 (only 2 detections)

(Pb)=0.003(Q)+0.549, r

2

=0.988

(Pb)=0.0001(Q)+5.71, r2

=0.539

(Pb)=0.514(Q)0.340, r2

=0.400

10 100 1,000 10,000

0.1

1

100

1,000

0.001 0.01 10.1

10

STREAM DISCHARGE, IN CUBIC FEET PER SECOND

Tar Creek near Cardin, Okla.

Tar Creek near Commerce, Okla.

Tar Creek near Picher, Okla.

Tar Creek above Douthat Bridge

Tar Creek at 22nd Street Bridge at Miami, Okla.

Tar Creek tributary near western chat pile

[Non-detects of less than 10 and less than 1 micrograms

per liter are estimated as 5 and 0.5 micrograms

per liter, respectively.]

(Pb)=3.62(Q)+0.985, r2

=0.756

(Pb)=13.0e-5.59(Q), r2

=0.125

(Pb)=3.94(Q)+7.46, r2

=0.211

(Pb)=2.04(Q)0.550+5120, r2

=0.608

(Pb)=2.75(Q)0.372, r2

=0.718

DOWNSTREAM UPSTREAM

EXPLANATION

Figure 15, Ranges in concentrations of total and dissolved lead (A), and graphs of total concentrations of lead in surface-water 

samples compared to discharge (B,C) for samples collected at sites in the Oklahoma part of the Tri-State mining district, 2000–06.
Selected Metals in Streams 25

TOTAL MANGANESE CONCENTRATION, IN MICROGRAMS PER LITER

A

B

C

x x

x

x

o

o

o

o

o

o

100

1,000

1,500

100 1,000 10,000 50,000

10

EXPLANATION

Neosho River near Commerce, Okla.

Neosho River near Wyandotte, Okla.

Spring River near Wyandotte, Okla.

Spring River near Quapaw, Okla.

Spring River above Devils Hollow, Okla.

[Shading is lighter in the

downstream direction.]

(Mn)=0.010(Q)+67.4, r

2

=1

(Mn)=68.7ln(Q)-341, r2

=0.424

(Mn)=0.004(Q)+177, r2

=0.151

(Mn)=27.0Q0.244, r2

=0.458

(Mn)=178(e)0.00003Q, r2

=0.353

STREAM DISCHARGE, IN CUBIC FEET PER SECOND

100

1,000

2,000

1 10 100 1,000 10,000

Tar Creek near Commerce, Okla.

Tar Creek at 22nd Street Bridge at Miami, Okla.

(Mn)=1310(Q)-0.180, r2

=0.729

(Mn)=935(Q)-0.140, r2

=0.669

DOWNSTREAM

EXPLANATION

MINIMUM REPORTING LEVEL=5

22

22

21

22

27

25

28

26

25

23

22

22

0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0 2 2 1 1 000 0

x

x

o

o

Dissolved

Total

30 Number of values

EXPLANATION

Schematic boxplot

Upper adjacent

75th percentile

Median

25th percentile

Lower adjacent

Lower outside 

Lower detached

Upper detached

Upper outside

[Adjusted maximum likelihood estimation

used to estimate censored values. Some of

these sites had samples collected for total and

dissolved lead on different dates]

NEOSHO RIVER NEAR COMMERCE

NEOSHO RIVER NEAR WYANDOTTE

TAR CREEK NEAR COMMERCE

 TAR CREEK AT 22ND STREET BRIDGE

GRAND LAKE O’ THE CHEROKEES NEAR WYANDOTTE

GRAND LAKE O’ THE CHEROKEES NEAR FAIRLAND

SPRING RIVER NEAR WYANDOTTE

BEAVER CREEK NEAR QUAPAW

BEAVER CREEK ABOVE SPRING RIVER NEAR QUAPAW

SPRING RIVER NEAR QUAPAW

TAR CREEK NEAR PICHER

TAR CREEK ABOVE DOUTHAT BRIDGE NEAR CARDIN

TAR CREEK NEAR CARDIN

TAR CREEK TRIBUTARY AT WESTERN CHAT PILE

ELM CREEK AT COMMERCE

LYTLE CREEK NEAR CARDIN

LYTLE CREEK AT STATE LINE ROAD NEAR PICHER

SPRING RIVER ABOVE DEVILS HOLLOW NEAR QUAPAW

SITE

TOTAL AND DISSOLVED MANGANESE

CONCENTRATIONS, IN MICROGRAMS

PER LITER

1

10

100

1,000

10,000

0.1

STREAM DISCHARGE, IN CUBIC FEET PER SECOND

Figure 16. Ranges in concentrations of total and dissolved manganese (A), and graphs of total concentrations of manganese in 

surface-water samples compared to discharge (B,C) for samples collected at sites in the Oklahoma part of the Tri-State mining district

2000–06.

, 
26 Selected Metals in Sediments and Streams in the Oklahoma Part of Tri-State Mining District, 2000–2006 TOTAL ZINC CONCENTRATION, IN MICROGRAMS PER LITER

A

B

C

10 100 1,000 10,000

100

1,000

10,000

70,000

0.001 0.01 10.1

STREAM DISCHARGE, IN CUBIC FEET PER SECOND

Tar Creek near Cardin, Okla.

Tar Creek near Commerce, Okla.

Tar Creek near Picher, Okla.

Tar Creek above Douthat Bridge

Tar Creek at 22nd Street Bridge at Miami, Okla.

Tar Creek tributary near western chat pile

[Non-detects of less than 10 and less than 1 micrograms

per liter are estimated as 5 and 0.5 micrograms

per liter, respectively.]

(Zn)=5,080e0.844(Q), r2

=0.993

(Zn)=15,600e0.824(Q), r2

=0.979

(Zn)=6,620(Q)0.214, r2

=0.770

(Zn)=383ln(Q)+5120, r2

=0.632

(Zn)=2,610(Q)-1.00, r2

=0.101

DOWNSTREAM UPSTREAM

EXPLANATION

10

10 100 1,000 10,000 50,000

100

1,000

1

10,000

STREAM DISCHARGE, IN CUBIC FEET PER SECOND

EXPLANATION

Neosho River near Commerce, Okla.

Neosho River near Wyandotte, Okla.

Spring River near Wyandotte, Okla.

Spring River near Quapaw, Okla.

Spring River above Devils Hollow, Okla.

[Non-detects of less than 5 micrograms

per liter are estimated as 2.5 micrograms

per liter. Shading is lighter in the

downstream direction.]

(Zn)=0.004(Q)+18.0, r2

=0.458

(Pb)=0.056(Q)+48.9, r

2

=0.998

(Zn)=0.010(Q)+119, r2

=0.487

(Zn)=10.4(Q)0.340, r2

=0.451

(Zn)=12.1(Q)0.00006, r2

=0.283

NEOSHO RIVER NEAR COMMERCE

NEOSHO RIVER NEAR WYANDOTTE

TAR CREEK NEAR COMMERCE

 TAR CREEK AT 22ND STREET BRIDGE

GRAND LAKE O’ THE CHEROKEES NEAR WYANDOTTE

GRAND LAKE O’ THE CHEROKEES NEAR FAIRLAND

SPRING RIVER NEAR WYANDOTTE

BEAVER CREEK NEAR QUAPAW

BEAVER CREEK ABOVE SPRING RIVER NEAR QUAPAW

SPRING RIVER NEAR QUAPAW

TAR CREEK NEAR PICHER

TAR CREEK ABOVE DOUTHAT BRIDGE NEAR CARDIN

TAR CREEK NEAR CARDIN

TAR CREEK TRIBUTARY AT WESTERN CHAT PILE

ELM CREEK AT COMMERCE

LYTLE CREEK NEAR CARDIN

LYTLE CREEK AT STATE LINE ROAD NEAR PICHER

SPRING RIVER ABOVE DEVILS HOLLOW NEAR QUAPAW

SITE

TOTAL AND DISSOLVED ZINC

CONCENTRATIONS, IN MICROGRAMS

PER LITER

10

1

100

1,000

10,000

100,000

0.1

0.01

o o o

o

o

o

o oo

x x

x

x xx x x

x x

x

x

o

o

Dissolved

Total

30 Number of values

EXPLANATION

Schematic boxplot

Upper adjacent

75th percentile

Median

25th percentile

Lower adjacent

Lower outside 

Lower detached

Upper detached

Upper outside

[Adjusted maximum likelihood estimation

used to estimate censored values. Some of

these sites had samples collected for total and

dissolved lead on different dates]

21

22

21

22

7 7

28

26

28

26

25

22

22

23

1 1 1 1 8 8 1 1 7 7 7 7 13 2 0 13 202 0

MINIMUM REPORTING LEVEL=5

Figure 17. Ranges in concentrations of total and dissolved zinc (A), and graphs of total concentrations of zinc in surface-water 

samples compared to discharge (B,C) for samples collected at sites in the Oklahoma part of the Tri-State mining district, 2000–06.
Selected Metals in Streams 27

National Water Quality Laboratory, which used methods having minimum reporting levels for cadmium as small as 0.05 

μg/L. The largest cadmium concentrations, from 50 to 100 

μg/L, were detected in water samples collected from upstream 

parts of Tar Creek (fig. 13A), where Cope and others (2008) 

estimated that nearly 70 percent of the cadmium in the creek 

was from leachate from tailings and about 25 percent was 

from outflow from the flooded underground mines. Similar 

total and dissolved concentrations of cadmium indicate that 

most cadmium is in the dissolved phase, or in very small 

suspended particles less than 0.45 microns in diameter (the 

typical effective pore size of field water-quality filters). Predominance of cadmium in the dissolved phase in local streams 

from the dissolution of sphalerite in the mining district was 

described previously by Carroll and others (1998) and O’Day 

and others (1998). All water samples from the upstream end 

of Tar Creek, in the center of the mining district, had cadmium 

concentrations greater than the 0.898 and 0.863 μg/L freshwater aquatic life Criteria Maximum Concentration (CMC) and 

Criteria Chronic Concentration (CCC) (at 300 milligrams per 

liter (mg/L) hardness as calcium carbonate), respectively (U.S. 

Environmental Protection Agency, 2006), indicating potential 

toxic effects to aquatic life in the creek from cadmium.

Cadmium concentrations in water samples collected from 

the Spring River above Devils Hollow site generally increased 

with streamflow (fig. 13B), indicating that runoff or resuspension of streambed sediments may be the primary sources of 

cadmium in water at that site. Relations of cadmium concentrations to streamflow in Tar Creek were varying, decreasing with greater streamflows at the Tar Creek above Douthat 

Bridge site, but increasing with streamflow at the upstream site 

near Cardin, Oklahoma, and the downstream site near Picher, 

Oklahoma.

Iron

Most iron in local streams is probably initially discharged 

in the ferrous form (Fe+2) from anoxic waters in mine outflows 

containing tens of thousands of micrograms per liter of iron, 

as described in Cope and others (2008), DeHay (2003), and 

DeHay and others (2004). When those waters discharge at the 

land surface, bacterially mediated precipitation of iron oxides 

and hydroxides happens almost immediately in aerobic stream 

water, creating thick deposits of soft, flocculated botryoidal 

goethite and other iron oxide and hydroxide minerals that 

impair aquatic habitat and are subject to re-suspension and 

washing downstream during high flows (fig. 2C and 2D).

Although iron is more likely to be an indicator of runoff 

or seepage from the mined area than aluminum as a result of 

substantial amounts of pyrite, marcasite, and other iron minerals in the mines (McKnight and Fischer, 1970) and in tailings 

(table 1), patterns of relative ranges in iron concentrations at 

the sampled sites were similar to ranges of aluminum (figs. 

12A and 14A). Aluminum and iron concentrations in local tailings were similar (table 1), though aluminum concentrations 

generally have been reported to be much less in the flooded 

underground mine workings (DeHay, 2003; DeHay and others, 

2004). 

The greatest concentrations of total iron generally were 

measured at the Neosho River sites (fig. 14). Comparatively 

large concentrations of total iron in water from the Neosho 

River sites, which have lesser proportions of mined area than 

most of the other sampled sites (table 7), may be a result of 

natural runoff of ferruginous soils developed on shales in that 

basin. Dissolved iron concentrations were about equal to total 

iron concentrations at the Tar Creek near Picher, Oklahoma 

site (fig. 14A), which is downstream from several mine seeps, 

indicating that most of the iron in water at that site is dissolved 

in the reduced ferrous form, similar to ground water in the 

underground mine workings or perhaps seeping out of anoxic 

zones in iron-rich streambed sediments. Decreases in concentrations of total iron and increases in proportions of total iron 

to dissolved iron downstream from that site are probably a 

result of precipitation of iron into a variety of ferric (Fe+3) iron 

oxide and hydroxide minerals on streambeds and banks 

(fig. 2). Total iron concentrations in Tar Creek in the 

Table 7. Mined areas compared to basin areas for selected basins in the Oklahoma part of the Tri-State mining 

district.

[areas in square miles, mined areas estimated from Brichta, 1960]

Basin Mined area in basin Basin area Proportion of mined area 

to basin area

Neosho River above Twin 

Bridges 20.9 6,130 0.341

Tar Creek at 22nd Street Bridge 

in Miami, Okla. 18.0 44.7 40.2

Spring River above Twin Bridges 49.1 2,590 1.90
28 Selected Metals in Sediments and Streams in the Oklahoma Part of Tri-State Mining District, 2000–2006

mid-1980s commonly exceeded 100,000 μg/L (Parkhurst, 

1987); therefore, iron concentrations have decreased since that 

time.

Similar to aluminum, total iron concentrations increased 

with streamflow at sites on the Neosho and Spring Rivers 

(figs. 12B and C and 14B and C), probably a result of a combination of runoff of these metals in particles eroded from soils 

and tailings, and re-suspension of fine streambed particles 

containing these metals during high streamflows. Conversely, 

at several of the upstream sites on Tar Creek sampled after a 

storm in August 2005, decreases in total iron concentrations 

with increasing streamflow occurred (Cope and others, 2008), 

indicating the seepage of ground water from the mine workings was diluted by storm runoff and that ground-water seepage from the mines may be the predominant source of iron in 

upstream parts of the creek under most flow conditions 

(fig. 13C).

Lead

Lead has comparatively low solubility in aquatic systems 

because of a propensity to precipitate as oxide, carbonate, and 

sulfide minerals and to be adsorbed to oxides and hydroxides 

of iron and manganese, phosphate, clays, and organic particles 

(Drever, 1988, p. 342–344; Hem, 1992, p. 143; Morel and 

Hering, 1993, p. 521–525; Carroll and others, 1998; O’Day 

and others, 1998). Lead in drinking water and food poses substantial threats to the health of humans and other organisms. 

Lead has been known for 3,000 years to be a potent, bioaccumulative neurotoxin that can cause permanent mental, emotional, and physical impairments (North Dakota Department 

of Health, 2004; Karmaus and others, 2005; Lanphear and 

others, 2005). Consumption of lead by pregnant women has 

been associated with premature births, smaller birth weights, 

decreased mental ability in infants, and spontaneous abortion 

(Gray, 2004). Lead accumulates in central nervous system 

tissues of children at greater rates than in adults, partially 

because of greater uptake of many elements for growth and 

incomplete development of the blood-brain barrier in children 

(World Health Organization, 1996; New South Wales Environmental Protection Agency, 2003). Consumption of lead by 

children has been implicated in impaired development, lower 

IQs, shortened attention spans/hyperactivity, and progressive 

mental deterioration (loss of motor skills, severe aggressive 

behavior disorders, and convulsive disorder) (Gray, 2004). 

Effects of lead consumption on adults may include: decreased 

reaction time, decreased memory, weakness in fingers, wrists, 

and ankles; anemia, weakness, palsy, lassitude, insomnia, 

facial pallor, weight loss, anorexia, malnutrition, constipation, 

nausea, abdominal pain, vomiting, increased blood pressure 

in men, kidney damage, and damage to male reproductive 

systems (Agency for Toxic Substances and Disease Registry, 

1999b; Gray, 2004). The compounds lead acetate and lead 

phosphate are believed to be likely carcinogens for humans 

(Agency for Toxic Substances and Disease Registry, 1999b).

Total lead concentrations in local tailings ranged from 

hundreds to thousands of milligrams per kilogram (table 1, 

Datin and Cates, 2002; Schaider and others, 2007), but lead 

concentrations have been reported to be less than 1,000 μg/L 

in ground water in the mine workings (DeHay, 2003; DeHay 

and others, 2004). Cope and others (2008) estimated that in the 

upper reaches of Tar Creek, leachate from tailings accounted 

for almost 70 percent of lead in water, with seepage from 

mines contributing almost 

30 percent of the lead in the Creek.

Because most lead concentrations in the water samples 

were censored, greater uncertainty exists regarding relations 

between lead concentrations and streamflow than for most 

of the other metals. For the two sites on the Neosho River, 

no water samples had lead concentrations greater than the 

minimum reporting level of 10 μg/L at the upstream site near 

Commerce, Oklahoma, and only 2 of 22 samples had detectable lead concentrations (but only slightly greater than the 

minimum reporting level of 10 μg/L) at the downstream site 

near Wyandotte, Oklahoma (fig. 15A). The greatest concentrations of lead were measured at the Tar Creek near Commerce, 

Oklahoma, station, but only 12 of 28 samples collected at that 

site contained lead at concentrations greater than the 10 μg/L 

minimum reporting level, with most total lead concentrations 

in water from that site being less than 100 μg/L (fig. 15A). 

Water samples collected during August 2005 to investigate 

the roles of storm runoff and ground-water seepage in metals 

transport had lead concentrations greater than the minimum 

reporting level for sites on the upstream part of Tar Creek, but 

a smaller minimum reporting level (1 μg/L) was associated 

with those samples (Cope and others, 2008). Most water samples collected from the Spring River and Beaver Creek had 

lead concentrations less than 10 μg/L (fig. 15A), consistent 

with the low solubility of lead in water (Hem, 1992, p. 143). 

Because of the potential toxic effects of lead to aquatic 

biota, the EPA has established Criterion Continuous and Criterion Maximum Concentrations (CCC and CMC) for lead in 

freshwater aquatic systems for protection of aquatic life of 2.2 

and 140 μg/L, respectively, at a hardness of 300 milligrams 

per liter (mg/L) as calcium carbonate (U.S. Environmental 

Protection Agency, 2006). A few samples collected from sites 

on Tar Creek exceeded the CCC and CMC criteria. Water 

samples collected from the Spring River and Beaver Creek 

periodically exceeded the CMC and many of the samples 

exceeded the CCC for lead at that hardness, indicating potential threats to aquatic biota from lead in those streams. Because 

of concern over potential lead contamination of fish in rivers 

draining the mining district in Oklahoma, the DEQ sampled 

fish and in those streams, reporting that fillets from fish caught 

in ponds in the Tar Creek Superfund Site and the Neosho and 

Spring Rivers are safe to eat at rates as much as six 8-ounce 

meals per month, but that whole-uneviscerated and wholeeviscerated parts of all fish from those streams should not be 

consumed (Oklahoma Department of Environmental Quality, 

2003). Beyer and others (2004) reported that several species 

of songbirds and waterfowl sampled from the mining district 
Selected Metals in Streams 29

had increased lead concentrations in tissues compared to birds 

sampled at a reference site, and that exposure of songbirds 

to lead was comparable with that of birds observed at other 

sites severely contaminated with lead. Several birds sampled 

by Beyer and others (2004) had lead concentrations in tissues 

that have been associated with impaired biological functions 

and external signs of poisoning. In the late 1990s, as much as 

40 percent of children in some areas of the mining district had 

elevated (greater than 10 milligrams per deciliter) blood-lead 

levels (State of Oklahoma, 2000b).

Total lead concentrations at the upstream site on the 

Neosho River (near Commerce, Oklahoma) were all less than 

the minimum reporting level, therefore no relation between 

streamflow and lead concentration could be determined at 

that site. At the downstream sampling site (Neosho River near 

Wyandotte, Oklahoma), the only measurable total lead concentrations were measured during high-flow periods, indicating some potential for transport of lead into the lake from the 

Neosho River as a result of runoff from the land surface or resuspension of lead-containing particles in streambed sediments 

(fig. 14B). At the upstream Tar Creek near Cardin, Oklahoma, 

site, a negative trend of total lead concentration with increasing streamflow may indicate that ground-water seepage is 

a prominent source of lead. Sites on Tar Creek downstream 

from the Tar Creek near Cardin, Oklahoma, site had total 

lead detections and concentrations generally increasing with 

streamflow (fig. 15C), indicating that storm runoff may be 

increasing lead concentrations at those sites by washing leadbearing particles from the land surface and/or re-suspending 

lead-bearing particles in streambed sediments.

Manganese

 Manganese and iron tend to have similar chemistry, 

with particles of oxide and hydroxide minerals of both metals adsorbing other metals (Hem, 1992, p. 85). Manganese 

concentrations were about 1 percent of iron concentrations in 

tailings samples collected in the mining district (table 1). Dissolved manganese concentrations reported in DeHay (2003) 

and DeHay and others (2004) ranged from less than 1 μg/L to 

about 1,500 μg/L, or about 1 to 10 percent of iron dissolved in 

ground water in the flooded underground mine workings.

Total manganese concentrations in water samples collected at the two sites on the Neosho River ranged from less 

than 100 to about 1,000 μg/L; whereas, water samples from 

Tar Creek had total manganese concentrations ranging from 

about 400 to 1,500 μg/L, and water samples from the Spring 

River had total manganese concentrations ranging from about 

70 to 600 μg/L (fig. 16A).

Dissolved manganese concentrations generally were an 

order of magnitude less than total manganese concentrations in 

water samples collected at sites on the Neosho and Spring Rivers (fig. 16A), indicating the importance of transport of particulate manganese in those large streams. For the two sites on 

Tar Creek sampled for manganese, similar ranges in total and 

dissolved manganese concentrations indicated predominance 

of the dissolved phase of manganese under most flow conditions. Similarity of total and dissolved manganese concentrations at those sites may have been a result of the predominance 

of ground-water seepage as a source of that metal in that 

smaller stream and/or to smaller reservoirs of metal-rich sediments in the streambed. Most total manganese concentrations 

in Tar Creek in the mid-1980s exceeded 

1,500 μg/L (Parkhurst, 1987), therefore, manganese concentrations have decreased slightly.

Total manganese concentration generally increased with 

streamflow for sites sampled on the Neosho and Spring Rivers, which indicates that storm runoff and/or resuspension of 

manganese-containing particles from the streambeds of those 

rivers were prominent sources of manganese in those streams 

(fig. 16B). Total manganese concentrations decreasing with 

increasing streamflow (fig. 16C) at the two downstream sites 

sampled for manganese on Tar Creek (near Commerce, Oklahoma, and at 22nd Street Bridge at Miami, Oklahoma) and 

similarities of total and dissolved manganese concentrations in 

stream water at those sites compared to manganese concentrations in the mine workings (DeHay, 2003; DeHay and others, 

2004) indicated that ground-water seepage was the predominant source of manganese at those sites.

Zinc

Zinc was the primary metal mined from the mining 

district and remains in concentrations of tens of thousands 

of milligrams per kilogram in fine millpond-tailing particles 

(table 1, Datin and Cates, 2002; Schaider and others, 2007) 

and in thousands to tens of thousands of micrograms per liter 

in ground water in the underground mine workings (DeHay, 

2003; DeHay and others, 2004). After the mineral sphalerite 

dissolves and seeps out of the mine workings, zinc ions tend to 

oxidize, forming comparatively insoluble zinc oxides (such as 

zincite, ZnO), hydroxides (such as Zn(OH)2), zinc hydroxycarbonate minerals (such as hydrozincite, Zn(OH)6

(CO3)2), and 

complexes with iron hydroxide minerals, particularly in wellbuffered carbonate systems common in this and other Mississippi Valley-type deposits (Hem, 1992, p. 142; Morel and 

Hering, 1993, p. 553-556; American Water Works Association 

Research Foundation, 1996; Carroll and others, 1998; O’Day 

and others, 1998; Paradis and others, 2006; and oral commun., 

Dr. Paul L. Younger, Newcastle University (U.K.), oral commun., 2006).

Although zinc is not perceived to have the same potential 

as cadmium and lead to impair the health of humans or wildlife, short-term (acute) consumption of excessive quantities 

of zinc by humans has been associated with nausea, vomiting, diarrhea, fever, and lethargy (World Health Organization, 

1996; Agency for Toxic Substances and Disease Registry, 

2003). Longer-term exposure to elevated zinc concentrations 

interferes with copper absorption, can cause anemia, alters 

serum lipid (blood cholesterol) ratios, and alters some types 

of immune response in humans (World Health Organization, 

1996; Agency for Toxic Substances and Disease Registry, 
30 Selected Metals in Sediments and Streams in the Oklahoma Part of Tri-State Mining District, 2000–2006

2003). Beyer and others (2004) reported that waterfowl 

sampled from the mining district showed signs of pancreatitis 

associated with zinc poisoning. Carpenter and others (2004) 

reported the death of a Free-flying Trumpeter Swan recovered 

near Picher, Oklahoma, the post-mortem analyses indicated 

elevated zinc concentrations in the pancreas, liver, and kidneys 

and resultant damages to pancreatic and renal tissues.

Total zinc was measured at concentrations ranging 

from about 5 to 300 μg/L in water samples collected at the 

two sites on the Neosho River (fig. 17A). The greatest total 

and dissolved zinc concentrations were generally detected 

in small streams draining the mining district (Lytle and Tar 

Creeks). Total zinc concentrations in those streams generally 

ranged from 2,000 to 20,000 μg/L (fig. 17A) that substantially 

exceeded the 423 and 426 μg/L CCC and CMC water-quality 

criteria (at a hardness of 300 mg/L as calcium carbonate) for 

zinc set by the EPA for protection of aquatic biota in freshwater systems (U.S. Environmental Protection Agency, 2006). 

Total zinc concentrations for three sites sampled on the Spring 

River ranged from about 50 to 500 μg/L (fig. 17A).

Most dissolved zinc concentrations at the two sampled 

sites on the Neosho River were less than the minimum reporting level of 5 μg/L and were about an order of magnitude less 

than total zinc concentrations at those sites (fig. 17A). As with 

manganese, ranges of total and dissolved zinc concentrations 

at sites sampled on Lytle and Tar Creeks were similar, indicating predominance of dissolved zinc in those small streams, 

perhaps from ground-water seepage or leaching from metalliferous streambed sediments and tailings, as described in Cope 

and others (2008). Similar to the Neosho River, dissolved zinc 

concentrations were about an order of magnitude less than 

total zinc concentrations at the sites sampled on the Spring 

River, indicating predominance of particulate zinc in those rivers. Larger zinc concentrations in the Spring River relative to 

the Neosho River may be a result of a larger proportion of the 

drainage basin of the Spring River being mined (figs. 1 and 3, 

table 7). In the mid-1980s, zinc concentrations at sites on the 

downstream reach of Tar Creek exceeded 20,000 μg/L and in 

the upstream reach exceeded 100,000 μg/L (Parkhurst, 1987), 

indicating notable decreases of zinc concentrations with time 

in Tar Creek.

Similar to lead, total zinc concentrations at upstream sites 

on Tar Creek, in the center of the mining district, increased 

with streamflow (figs. 15C and 17C), indicating that runoff 

tended to wash zinc-rich particles from the land surface 

and/or resuspend zinc-rich particles in streambed sediments. 

Total zinc concentrations generally decreased with streamflow 

at the two Tar Creek sites downstream from the mined areas 

(fig. 17C) indicating that runoff, perhaps from areas downstream from the mined areas, may have diluted zinc concentrations and that ground-water seepage may have been the 

primary source of zinc in water at those sites. Total zinc concentrations at sites on the Neosho and Spring Rivers increased 

with streamflow, indicating that runoff from the land surface 

or resuspension of zinc-containing streambed sediments were 

influential factors controlling zinc concentrations in Neosho 

and Spring Rivers.

Total Metal Loads

Total loads indicate the flux or mass per unit of time for 

a substance flowing past a given point in a stream channel, 

including suspended and dissolved substances (total). Total 

metal loads can be related to geologic settings and disruptions 

to those settings caused by activities such as mining. The total 

load of a particular substance increasing in the downstream 

direction indicates incremental inputs of a substance along 

the course of a stream. Consistent total loads of a substance 

at the beginning and end of a stream segment indicate lack of 

contribution or balance between runoff/seepage and sedimentation of a substance in a particular stream reach. Total loads 

estimated in this section at base flows are similar in range to 

total load estimates described for streams at base flow in the 

mining district by Oklahoma Department of Environmental 

Quality (2008).

Aluminum

The Neosho River flows through areas underlain by 

shales that may contribute large amounts of aluminum in the 

form of clay minerals to that river. The comparatively large 

concentrations and streamflow of the Neosho River combined 

to produce the largest loads of total aluminum of the stream 

sites sampled near the mining district (fig. 18), with median 

loads of about 100,000 kilograms (100 tonnes) of aluminum 

per day. Similar ranges in total aluminum loads at the Neosho 

River station upstream from most historic mining locations 

(near Commerce, Oklahoma) and the Neosho River station 

downstream from most of the historic mining activity (near 

Wyandotte, Oklahoma, fig. 18) indicate that tailings and seepage from the mine workings probably contribute little aluminum to the Neosho River, as described for total aluminum 

concentrations in water. Only two sites on Tar Creek were 

sampled for total aluminum and the large minimum reporting 

level (300 μg/L) caused most of the data from those sites (18 

of 25 samples for near Commerce, Oklahoma, and 16 of 28 

samples for 22nd Street Bridge in Miami, Oklahoma) to be 

censored (non-detects). Much of the area draining to Tar Creek 

is underlain by Krebs Group shales (McKnight and Fischer, 

1970), but about one-third of that basin is covered with tailings 

piles, which are dominated by crushed particles of limestones, 

dolomites, and cherts from the underlying Boone Formation. 

Aluminum loads at these Spring River sites were generally 

one to two orders of magnitude (10 to 100 times) less than aluminum loads from the Neosho River sites, perhaps a result of 

a smaller proportion of the Spring River Basin being underlain 

by shales containing aluminum-rich clay minerals.
Summary 31

Cadmium

Estimated total cadmium loads are less certain than loads 

estimated for other metals in this report because most of the 

cadmium concentrations in water samples were censored 

(figs. 13 and 18). Increases in estimated cadmium loads from 

upstream reaches of Tar Creek (near Cardin, Oklahoma) to the 

downstream reach (at the 22nd Street Bridge in Miami, Oklahoma) indicated contributions of cadmium in the downstream 

direction, probably from a combination of mine seepage, 

runoff of tailings, and re-suspension of cadmium-bearing sediments during high flows.

Iron

Total iron loads, which can come from erosion and 

seepage from erosion of shales, local soils, tailings, and mine 

workings, were similar to total aluminum loads at the sampled 

sites (fig. 18). Additional sites, however, were sampled for 

iron. Total iron loads in Tar Creek increased by several orders 

of magnitude in the downstream direction, indicating contributions from mine seeps, runoff, dissolution of streambed 

sediments, and/or resuspension of abundant ferruginous sediments in the downstream direction. Iron loads at sites sampled 

in Lytle and Beaver Creeks, which also drain parts of mined 

areas, were similar to the iron loads in the upstream reaches of 

Tar Creek (fig. 18).

Lead

All concentrations, and thus loads, of total lead were 

less than the minimum reporting level at the two sites on the 

Neosho River, indicating that small quantities of lead were 

transported by that River, despite comparatively large streamflows at those sites. A smaller minimum reporting level of 

1 μg/L for samples collected at upstream sites on Tar Creek 

in August 2005, rather than the 10 μg/L level that applied to 

other samples, caused there to be no censored lead data for 

those sites. Much greater proportions of censored data for the 

downstream sites (16 of 26 samples from near Commerce, 

Oklahoma, and 16 of 25 samples for 22nd Street Bridge in 

Miami, Oklahoma) contributed to less certainty about total 

lead loads at the downstream sites. Despite those differences in 

censoring of data, total lead loads increased in the downstream 

direction, indicating contributions from ground-water seepage, runoff, and/or dissolution and resuspension of streambed 

sediments along the course of Tar Creek. As with Tar Creek, a 

smaller minimum reporting level of 1 μg/L applied to samples 

collected at Spring River above Devils Hollow near Quapaw, 

Oklahoma, site, provides more reliable estimates of total lead 

loads. Apparent lesser total lead loads at the downstream sites 

near Quapaw, Oklahoma, and near Wyandotte, Oklahoma, 

may be a result of greater proportions of censored total lead 

data (17 of 24 and 16 of 21 samples, respectively) at those two 

sites on the Spring River (fig. 18).

Manganese

Unlike lead, total manganese had no censored data, but 

fewer sites were sampled for manganese. Manganese is commonly associated with iron, and has similar chemical behavior, 

but generally is found in smaller concentrations than iron. 

Although the manganese sulfide mineral alabandite (MnS) 

was not reported in the mining district (McKnight and Fischer, 

1970), that or other manganese minerals may be present in 

trace amounts with abundant iron minerals in the mines and 

manganese commonly is associated with iron in soils in the 

forms of oxide and hydroxide minerals (Hem, 1992, p. 86). 

As with total iron, the ranges of total manganese loads were 

similar in the Neosho River at the upstream (near Commerce, 

Oklahoma) and downstream (near Wyandotte, Oklahoma) 

reaches, indicating little effect of the mined area on total 

manganese loads (fig. 18). Ranges of total manganese loads at 

the Tar Creek near Commerce, Oklahoma, and at 22nd Street 

Bridge in Miami, Oklahoma, were similar (fig. 18), as was 

the case with iron loads. Ranges of total manganese loads at 

the Spring River near Quapaw, Oklahoma, and near Wyandotte, Oklahoma, sites were intermediate between those in the 

Neosho River and Tar Creek (fig. 18), also similar to total iron. 

Those intermediate total manganese loads may be a result of 

a greater proportion of the Spring River Basin having been 

mined than the Neosho River Basin, but a smaller proportion 

of the Spring River Basin being affected by mining than the 

Tar Creek Basin (table 7).

Zinc

Total zinc concentrations were substantially less in water 

samples collected at the sites on the Neosho and Spring Rivers than at the sites sampled on Lytle and Tar Creeks (fig. 

17). However, streamflows of the Neosho and Spring Rivers commonly are in the tens of thousands of cubic feet per 

second, contributing to the comparatively large total zinc loads 

ranging from tens to several thousand kilograms per day. A 

slight increase in total zinc loads at the Neosho River near 

Wyandotte, Oklahoma, site compared to the upstream site 

near Commerce, Oklahoma, (fig. 18) may have been caused 

by inputs of zinc from tributary streams flowing through the 

mined area, particularly Tar Creek. Total zinc and total lead 

loads increased in the downstream direction along Tar Creek 

(fig. 18), indicating inputs of zinc from ground-water seepage, 

runoff, and/or dissolution and re-suspension of zinc- and leadcontaining streambed sediments. 

Summary

The Oklahoma part of the Tri-State mining district, also 

known as the Picher mining district, is an abandoned lead and 

zinc mining district in Ottawa County, northeastern Oklahoma. 

During the first half of the 20th century, the district was a 
32 Selected Metals in Sediments and Streams in the Oklahoma Part of Tri-State Mining District, 2000–2006 1,000 100,000 10,000,00010

x

x

0.1

0.001

0.00001

0.0000001

0.000000001

o

o

o

o

o

o

Aluminum 0 18/2516/28 0/2 4/25 2/22 0/2 0/210/22 0 0 0 00 0 0/2

0/8 16/2616/25 0/6 17/2416/21 0/6 16/16 18/18 0/1 0/1 0/1 0/70/7 0/7 0/7

0/8 0/17 7/16 4/6 13/16 9/10 5/5 9/910/10 0/1 0/1 0/1 0/70/7 0/7 5/5 0/8 0/31 0/32 0/5 1/29 0/22 0/6 0/210/22 0/1 0/1 0/1 0/70/7 0/7 0/6

0/0 0/27 0/28 0/2 0/25 0/22 0/2 0/210/22 0/0 0/0 0/0 0/00/0 0/0 0/2

0/8 0/28 0/28 0/5 0/250/22 0/2 0/211/21 0/1 0/1 0/1 0/70/7 0/7 0/6

o

xxo

1/30 Number of censored values/

number of total values

EXPLANATION

Schematic boxplot

Upper detachedUpper outsideUpper adjacent75th percentileMedian

25th percentile

Lower adjacentLower outside Lower detached

[Adjusted maximum likelihood estimation

used to estimate censored values]

Largest censored value

Smallest censored value

100

1,000

10,000

10

1

0.1

0.001

0.0001

0.00001

0.0000001

x

0.01

0.000001

Cadmium

x x x

x

Lead

100

1,000

10,000

10

1

0.1

0.01

0.001

0.0001

0.00001

0.000001

0.0000001

NEOSHO RIVER NEAR COMMERCE

NEOSHO RIVER NEAR WYANDOTTE

TAR CREEK NEAR COMMERCE

 TAR CREEK AT 22ND STREET BRIDGE

SPRING RIVER NEAR WYANDOTTE

BEAVER CREEK NEAR QUAPAW

SPRING RIVER NEAR QUAPAW

BEAVER CREEK ABOVE SPRING RIVER NEAR QUAPAW

TAR CREEK NEAR PICHER

TAR CREEK ABOVE DOUTHAT BRIDGE NEAR CARDIN

TAR CREEK NEAR CARDIN

TAR CREEK TRIBUTARY AT WESTERN CHAT PILE

ELM CREEK AT COMMERCE

LYTLE CREEK NEAR CARDIN

LYTLE CREEK AT STATE LINE ROAD NEAR PICHER

SPRING RIVER ABOVE DEVILS HOLLOW NEAR QUAPAW

SITE

1,000,000

10,000,000

100,000,000

10,000

1,000

100

10

1

0.1

0.01

100,000

o

x

x

0.001

0.0001

Iron

NEOSHO RIVER NEAR COMMERCE

NEOSHO RIVER NEAR WYANDOTTE

TAR CREEK NEAR COMMERCE

 TAR CREEK AT 22ND STREET BRIDGE

SPRING RIVER NEAR WYANDOTTE

BEAVER CREEK NEAR QUAPAW

SPRING RIVER NEAR QUAPAW

BEAVER CREEK ABOVE SPRING RIVER NEAR QUAPAW

TAR CREEK NEAR PICHER

TAR CREEK ABOVE DOUTHAT BRIDGE NEAR CARDIN

TAR CREEK NEAR CARDIN

TAR CREEK TRIBUTARY AT WESTERN CHAT PILE

ELM CREEK AT COMMERCE

LYTLE CREEK NEAR CARDIN

LYTLE CREEK AT STATE LINE ROAD NEAR PICHER

SPRING RIVER ABOVE DEVILS HOLLOW NEAR QUAPAW

SITE

10,000

100,000

1,000

100

10

1

x

o

o

o o o

o

Manganese

10,000

100,000

100

10

1

0.1

1,000

0.01

x x

x

x

o

o o

o

oo

o

o

o

o o

o

o

Zinc

NEOSHO RIVER NEAR COMMERCE

NEOSHO RIVER NEAR WYANDOTTE

TAR CREEK NEAR COMMERCE

 TAR CREEK AT 22ND STREET BRIDGE

SPRING RIVER NEAR WYANDOTTE

BEAVER CREEK NEAR QUAPAW

SPRING RIVER NEAR QUAPAW

BEAVER CREEK ABOVE SPRING RIVER NEAR QUAPAW

TAR CREEK NEAR PICHER

TAR CREEK ABOVE DOUTHAT BRIDGE NEAR CARDIN

TAR CREEK NEAR CARDIN

TAR CREEK TRIBUTARY AT WESTERN CHAT PILE

ELM CREEK AT COMMERCE

LYTLE CREEK NEAR CARDIN

LYTLE CREEK AT STATE LINE ROAD NEAR PICHER

SPRING RIVER ABOVE DEVILS HOLLOW NEAR QUAPAW

0.001

SITE

Figure 18. Ranges of loads of total aluminum, cadmium, iron, lead, manganese, and zinc in surface-water samples collected at sites in the Oklahoma part of the Tri-State miningdistrict, 2000–06.
Summary 33

primary producer of lead and zinc in the United States. Those

two metals are common in sulfide minerals of the Mississippian-age Boone Formation, which is composed primarily of 

limestones and dolomitic limestones. Ore production in the 

district was active from the late 1800s until the mid-1970s. 

Production reached a peak by 1925 with 387,000 tons of 

recoverable zinc and 101,000 tons of recoverable lead being 

produced. The mines maintained moderate production levels 

until the 1950s when yields began to decline. 

Sulfide minerals of iron, lead, and zinc can gradually 

oxidize and dissolve in underground mine workings, and in 

tailings on the land surface in the mining district. A variety 

of low-solubility oxide, hydroxide, and hydroxycarbonate 

metallic minerals form as dissolved metals seeping from the 

mine workings and tailings oxidize further and combine with 

abundant dissolving carbonate minerals.

Tens of millions of tons of gravel- to sand-sized mine 

tailings known as “chat” remain in the mining district. Ponds 

of silt- and clay-sized by-products of the gravity separation 

process, referred to as millpond tailings, commonly lie adjacent to chat piles. Fine particles (<2 millimeters in diameter) 

in millpond tailings in the district contain tens to hundreds of 

thousands of milligrams per kilogram of aluminum, iron, and

zinc, with concentrations of other trace metals such as lead 

and cadmium ranging from tens to hundreds of milligrams 

per kilogram. Seepage from tailings and from flooded underground mine workings supply both water and metals to base 

flow of local streams.

Lakebed, streambed, and floodplain sediments and/or 

stream water were sampled at a total of 30 sites by the U.S. 

Geological Survey and the Oklahoma Department of Environmental Quality from 2000 to 2006 in cooperation with the

U.S. Environmental Protection Agency, and the Quapaw and 

Seneca-Cayuga Tribes of Oklahoma. Aluminum and iron wer

measured in concentrations of several thousand milligrams 

per kilogram in sediments in the upstream end of Grand Lake

O’ the Cherokees, with manganese and zinc concentrations 

being several hundred milligrams per kilogram. Concentrations of lead were about 10 percent of zinc concentrations an

with cadmium concentrations were about 0.1 percent of zinc 

concentrations. A transect of sediment cores collected across 

the floodplain of Tar Creek near Miami, Oklahoma, in 2004 

were similar to or greater than concentrations of those metals

in the upstream end of Grand Lake O’ the Cherokees, with th

greatest concentrations of cadmium, iron, lead, and zinc bein

found beneath a tributary draining abandoned mined areas 

near Commerce, Oklahoma.

Concentrations of aluminum and iron were greatest in 

the Neosho River in surface-water samples collected in the 

Oklahoma part of the Tri-State mining district from 2000 to 

2006, perhaps a result of runoff from areas overlain by shales

The greatest concentrations of cadmium, lead, manganese, 

and zinc were measured in Tar Creek. The Spring River had 

greater concentrations of zinc than the Neosho River, perhaps

a result of a greater proportion of mined area in the Spring 

River Basin. Dissolved metals concentrations were generally 

e 

d 

e 

g 

. 

much less than total metals concentrations, except for manganese and zinc at sites on Tar Creek, where ground-water 

seepage or seepage from metalliferous streambed sediments 

may be the primary sources of those metals. Concentrations 

of total aluminum generally increased with streamflows at 

all sites, probably caused by runoff and re-suspension of 

aluminum-rich clay particles during high flows. Total cadmium concentrations increased with streamflow at the Spring 

River sites and at Tar Creek near Cardin, Oklahoma, and near 

Picher, Oklahoma, sites, but decreased with streamflow at 

other sites on Tar Creek, indicating predominance of base flow 

(ground-water seepage) as a cadmium source at some sites, 

and runoff and/or re-suspension of cadmium being prominent sources of cadmium in water at other sites on Tar Creek. 

Total iron concentrations generally increased with greater 

streamflows for sites on the Neosho and Spring Rivers, but 

not for upstream sites on Tar Creek, where seepage of metals from ground-water or streambed sediments may be the 

predominant sources of iron at most flow conditions. With the 

majority of lead concentrations at most sites being censored, 

there is greater uncertainty regarding relations between lead 

concentrations and streamflow. Total manganese concentrations generally increased with streamflow in the Neosho and 

Spring Rivers, indicating possible enrichment by runoff and/

or re-suspension of metalliferous streambed sediments during 

higher streamflows. Decreases in manganese concentrations 

with increasing streamflow at the downstream sites on Tar 

Creek indicate dilution of manganese seeping from groundwater during higher streamflows. General increases in total 

zinc concentrations with higher streamflows in the Neosho and 

Spring Rivers and in upstream parts of Tar Creek indicate that 

the primary sources of total zinc concentrations at those sites 

were likely to be runoff and/or re-suspension of metalliferous 

streambed sediments. Decrease in total zinc concentrations 

with increasing streamflow at downstream sites on Tar Creek 

may indicate predominance of ground-water seepage as a 

source of zinc at those sites, with higher streamflows diluting 

zinc concentrations.

Loads (masses flowing past a given point on a stream 

per unit of time) of total aluminum, iron, manganese, and zinc 

generally were greatest at the sampled sites on the Neosho and 

Spring Rivers, in part a result of streamflows that regularly 

exceeded 10,000 cubic feet per second at those sites. Slight 

increases in loads in the downstream directions on those rivers 

indicated contributions of metals from inflows of small tributaries like Tar Creek and from runoff. Increasing loads of cadmium, lead and zinc in the downstream direction in Tar Creek 

indicated gains in metal flows in the downstream direction, 

possibly caused by combinations of ground-water seepage, 

seepage from streambed sediments, and runoff and resuspension of metalliferous streambed sediments at higher flows.
34 Selected Metals in Sediments and Streams in the Oklahoma Part of Tri-State Mining District, 2000–2006

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