Toxic Hydrology Program 

Results of Chemical and Isotopic 

Analyses of Sediment and Water from 

Alluvium of the Canadian River near a 

Closed Municipal Landfill, Norman, 

Oklahoma 

By George N. Breit, Michele L.W. Tuttle, Isabelle M. Cozzarelli, Scott C. Christenson, Jeanne B. Jaeschke, 

David L. Fey, and Cyrus J. Berry 

Open-File Report 2005-1091

U.S. Department of the Interior 

U.S. Geological Survey 

i
U.S. Department of the Interior 

Gale A. Norton, Secretary 

U.S. Geological Survey 

Charles G. Groat, Director 

U.S. Geological Survey, Reston, Virginia 2005 

Revised and reprinted: 2005 

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Cover Photograph of the wall of a shallow trench dug into north the bank of the Canadian River perpendicular to the 

river. Trench is approximately 1 foot deep and shows iron sulfide (black) phases coating the typically red sediment. 

Intensity of black coating increases toward the river.

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copyright owners to reproduce any copyrighted material contained within this report. 

ii
Contents 

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

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

Methods .............................................................................................................................................................................3

Sample Site Selection.....................................................................................................................................................3

Sediment Sampling ........................................................................................................................................................3

Water Sampling .............................................................................................................................................................4

Sediment Analyses.......................................................................................................................................................10

Water Analyses............................................................................................................................................................11

Results..............................................................................................................................................................................11

Sediment Composition.................................................................................................................................................11

Water Composition ......................................................................................................................................................26

Literature Cited ................................................................................................................................................................36

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Figures 

1. Map of freeze-shoe core and shallow sediment sample sites in the Canadian River alluvium.............................2 

2. Lithologic characteristics of sediment recovered by freeze-shoe coring with locations of sediment and 

 pore-water samples..............................................................................................................................................5 

3. Map of locations of water samples collected from the Canadian River, New Mexico, Texas, and Oklahoma......9 

4. Ternary diagram of the relative abundance of sand, silt, and clay in sediment samples collected by 

 freeze-shoe coring of the Canadian River alluvium............................................................................................ 20 

5. Secondary electron micrograph images of pyrite from relatively shallow samples (<2 meters) within the 

 Canadian River alluvium. ................................................................................................................................... 21 

6. Secondary electron and backscatter micrographs of massive pyrite aggregates from sediment 

 samples of the Canadian River alluvium. ........................................................................................................... 22 

7. Secondary electron images of well-formed pyrite crystals from samples of the Canadian River 

 alluvium below depths of 2 meters ..................................................................................................................... 23 

8. Micrographs of barite detected within the Canadian River alluvium. .................................................................. 24 

Tables 

1. Locations and elevations of core sites and sampled wells.............................................................................. 3 

2. Description of sediment samples from the Canadian River alluvium. ............................................................. 6 

3. Time of collection and location of Canadian River water samples.................................................................. 9 

4. Results of particle-size analysis of sediment samples collected by freeze-shoe coring................................. 12 

5. Concentrations of iron extracted from sediment samples by treatment with 1N KCl, 0.5M HCl 

 and Ti3+-EDTA for 24 hours.......................................................................................................................... 25 

6. Content of organic carbon, forms of sulfur, and sulfur isotopic compositions of sediment samples. ........... 27 

7. Chemical composition of pore water withdrawn directly from core of the Canadian River 

 alluvium that was obtained by freeze-shoe coring. ...................................................................................... 29 

8. Composition of ground water collected from wells in the Canadian River alluvium. ...................................... 32 

9. Chemical composition of water samples from the Canadian River................................................................ 34 

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CONVERSION FACTORS AND DATUMS 

Multiply By To obtain 

Length 

centimeter (cm) 0.3937 inch (in.) 

meter (m) 3.281 foot (ft) 

kilometer (km) 0.6214 mile (mi) 

kilometer (km) 0.5400 mile, nautical (nmi) 

liter (L) 33.82 ounce, fluid (fl. oz) 

liter (L) 0.2642 gallon (gal) 

liter (L) 61.02 cubic inch (in3) 

cubic foot per second (ft3/s) 0.0283 cubic meter per second (m3/s) 

gram (g) 0.03527 ounce, avoirdupois (oz) 

kilogram (kg) 2.205 pound avoirdupois (lb) 

Temperature in degrees Celsius (°C) may be converted to degrees Fahrenheit (°F) as follows: 

°F=(1.8×°C)+32 

Vertical coordinate information is referenced to the insert datum name (and abbreviation) here, for instance, 

“North American Vertical Datum of 1988 (NAVD 88)” 

Horizontal coordinate information is referenced to the insert datum name (and abbreviation) here, for 

instance, “North American Datum of 1983 (NAD 83)” 

Altitude, as used in this report, refers to distance above the vertical datum. 

Specific conductance is given in microsiemens per centimeter at 25 degrees Celsius (μS/cm at 25°C). 

Concentrations of chemical constituents in water are given either in milligrams per liter (mg/L) or micrograms 

per liter (μg/L). 

Abbreviated Units 

Chemical concentration and water temperature are given only in metric units. Chemical concentration in 

water is given as milligrams per liter (mg/L) or micrograms per liter (μg/L). Chemical concentrations in solid 

phase samples are given as weight percent (wt.%), parts per million (ppm), millimoles per gram (mmol/g), or 

micromoles per gram (μmol/g). Grain size abundances are listed in volume percent (volume %). Stableisotope ratios are reported relative to internationally agreed upon standards. Deviations from standards are 

expressed in per mil (‰) using the delta (δ) notation. The delta symbol in this report is followed by the 

chemical symbol for the heavier isotope measured during isotopic analysis. 

v
Abbreviated Chemical Symbols 

____________________________________________

Ag Silver 

Al Aluminum 

As Arsenic 

B Boron 

Ba Barium 

Be Beryllium 

Ca Calcium 

Cd Cadmium 

Co Cobalt 

Cr Chromium 

Cs Cesium 

Cu Copper 

Fe Iron 

Fe2+ Ferrous iron 

Fe3+ Ferric iron 

K Potassium 

Li Lithium 

Mg Magnesium 

Mn Manganese 

Mo Molybdenum 

Ni Nickel 

OSO4 Sulfate oxygen 

Pb Lead 

Rb Rubidium 

S Sulfur 

SAV Acid-volatile sulfur 

SDI Disulfide sulfur 

SSO4 Sulfate sulfur 

Sb Antimony 

Se Selenium 

Si Silicon 

Sr Strontium 

Ti Titanium 

U Uranium 

V Vanadium 

Zn Zinc 

vi
Results of Chemical and Isotopic 

Analyses of Sediment and Water from 

Alluvium of the Canadian River near a 

Closed Municipal Landfill, Norman, 

Oklahoma 

By George N. Breit, Michele L.W. Tuttle, Isabelle M. Cozzarelli, Scott C. Christenson, Jeanne B. 

Jaeschke, David L. Fey, and Cyrus J. Berry 

Abstract 

Results of physical and chemical analyses of sediment and water collected near a closed municipal landfill 

at Norman, Oklahoma are presented in this report. Sediment analyses are from 40 samples obtained by freeze-shoe 

coring at 5 sites, and 14 shallow (depth <1.3 m) sediment samples. The sediment was analyzed to determine grain 

size, the abundance of extractable iron species and the abundances and isotopic compositions of forms of sulfur. 

Water samples included pore water from the freeze-shoe core, ground water, and surface water. Pore water from 23 

intervals of the core was collected and analyzed for major and trace dissolved species. Thirteen ground-water 

samples obtained from wells within a few meters of the freeze-shoe core sites and one from the landfill were 

analyzed for major and trace elements as well as the sulfur and oxygen isotope composition of dissolved sulfate. 

Samples of surface water were collected at 10 sites along the Canadian River from New Mexico to central 

Oklahoma. These river-water samples were analyzed for major elements, trace elements, and the isotopic 

composition of dissolved sulfate. 

Introduction 

Thousands of municipal landfills were sited adjacent to rivers prior to the passage of regulations intended 

to restrict the impact of solid wastes and leachates produced by interaction of ground water and surface water with 

those wastes. The U.S. Geological Survey (USGS) Toxic Hydrology Program is supporting the study of a closed 

municipal landfill located on Canadian River alluvium near the city of Norman, Oklahoma, to evaluate the 

environmental impact of one of these waste repositories. The closed Norman municipal landfill operated in varying 

forms from 1922 until 1985 on the north bank of the Canadian River. Initially the wastes were dispersed along the 

banks of the river. Beginning in 1960, the operators excavated trenches to the water table and buried wastes beneath 

15 cm of sand (Schlottmann, 2001). Trenches were abandoned in 1971, and wastes were deposited on lifts of sand 

0.6 meter above the water table. Wastes were buried daily with sand. The landfill was closed in 1985 and covered 

with a low permeability cap leaving two mounds rising about 12 meters above the surrounding land surface 

(Schlottmann, 2001) (fig. 1). 
Figure 1. Map of freeze-shoe core (●) and shallow sediment sample sites (+) near the closed Norman municipal 

landfill. Details of locations and depths are presented in table 1.

Movement of water through the waste produces a leachate recognizable by high specific conductance, 

dissolved organic carbon, iron, methane, ammonium, and boron (Schlottmann, 2001). Processes that attenuate the 

organic contaminants as the leachate moves through the Canadian River alluvium are a primary emphasis of the 

USGS project. A set of processes collectively identified as natural attenuation results in the degradation of organic 

matter through bacterial oxidation of organic components of the leachate. Bacterial oxidation of the organic 

compounds requires the presence of electron acceptors such as dissolved oxygen, nitrate, manganese oxides, ferric 

iron, or sulfate. This report presents data on the abundance of iron and sulfur species in the sediment that will be 

used to gauge the significance of ferric iron and sulfate as electron acceptors. Sediment and pore water collected by 

coring, ground water collected from established wells, shallow alluvial sediment and surface-water samples were 

analyzed. Results show the impact of leachate on the speciation of iron and sulfur in the alluvium downgradient of 

the landfill can be detected. Nonetheless, the effects of the leachate are small relative to the effects of natural 

processes evident in the composition of sediment unaffected by leachate. 

2
Methods 

Sample Site Selection 

The extent of the landfill leachate was described by surface geophysics (Lucius and Bisdorf, 1995) and 

through profiling the electrical conductivity of the ground water (Becker, 2002; Christenson, 1999, USGS written 

commun.). Coupled with existing knowledge of the hydrologic and lithologic characteristics of the Canadian River 

alluvium (Scholl and Christenson, 1998), sites SG40, SG38, SG41, SG88, and SG99 (table 1, fig. 1) were selected to 

represent sediment with varied exposure to landfill leachate. The depth profiles of the specific conductance of water 

at SG40, SG38, SG41, and SG88 using measurements collected in 1995 and 1997 are presented in Becker (2002). 

SG40 and SG38 are intended to represent sediment with sustained exposure to leachate. The specific conductance 

of ground water in the cored interval from site SG41 increased sharply from 1997 to 1999 (1000 to 4000 μS cm-1 at 

some depths; Christenson, 1999, written commun.) and is interpreted to represent advance of the leachate down the 

hydrologic gradient from the landfill toward the Canadian River. Ground water extracted near site SG88 is 

consistent with background water compositions, although sediment samples collected at SG88 had a distinctive odor 

consistent with the presence of leachate. This may indicate some exposure of SG88 sediment to leachate. SG99 is 

approximately 400 meters (m) south of the west landfill cell in an area beyond the extent of the recognized leachate 

plume within the sampled depth range. 

3
Sediment Sampling 

Canadian River alluvium was sampled in May of 2000. At each site, sediment was collected within the 

depth interval of 2 to 6 m. This depth range was selected to sample above the high permeability of coarse sands and 

gravels characteristic of the lower third of the alluvium (Scholl and Christenson, 1998) and to minimize the 

influence of the fluctuating water table to only the uppermost portions of the core (Becker, 2002). Subsurface 

sampling used a freeze-shoe coring device with a hollow-stem auger. The freeze-shoe coring device captures 

sediment and enclosed pore water by freezing the lowest sediment in the core barrel by circulating liquid carbon 

dioxide through the bit (Murphy and Herkelrath, 1996). During the sampling, sediment and enclosed pore water 

were captured in transparent acrylic core liners. The liners were cut into approximately 2-foot lengths subsequent to 

the water sampling described below, sealed with end caps that were taped shut, and transported in “ammo cans” 

purged with nitrogen. The cans containing the core were refrigerated in the microbiology laboratories of Dr. Joseph 

Suflita at the University of Oklahoma, 4 miles from the study site. Shallow sediment samples were collected from 

the active Canadian River (ACRS), the slough, and near the water table by using a hand trowel, shovel, and a 

hollow-stem auger. The shallow sediments were stored in glass vials, plastic containers, and acrylic core liners that 

were frozen on site with dry ice. 

Core liners from the freeze-shoe coring were cut and split using a knife in a glove box filled with nitrogen 

and a small amount of hydrogen. The oxygen-free integrity of the atmosphere within the glove box was ensured 

using a palladium catalyst. Each length of core was described and divided by apparent grain size and color 

variations into separate samples (table 2, fig. 2). Each visually distinct interval was homogenized in a plastic beaker 

and subsampled. A 3-milliliter (mL) detipped syringe was used to transfer an aliquot of sediment into acid-washed 

serum vials for iron speciation analysis. Each vial was wrapped in foil to minimize exposure to light during 

treatment with iron speciation reagents. A 10-mL detipped syringe was used to transfer an aliquot of the sediment 

into amber septa vials. These vials were frozen immediately after removal from the glove box for later speciation of 

the sulfur forms. A separate aliquot was frozen for later freeze drying and examination with the scanning electron 

microscope (SEM). 

Water Sampling 

Water was collected from the cored sediment, existing wells, drive point wells and surface water. Water 

extracted from the cored sediment was withdrawn with a syringe through small holes drilled in the liner. The voids 

produced by the withdrawn water were filled with nitrogen provided through a pressurized cap placed on top of the 

liner. Where sufficient water was recovered, pH, alkalinity, ferrous iron, and ammonium were determined in the 

field. A small aliquot of water was filtered (<0.1 μm) and acidified with nitric acid to a pH < 2 for analysis of 

cations and trace elements. A second filtered aliquot was preserved on ice for analysis of anions. Filtered water 

stored in a baked glass bottle was used for dissolved organic carbon. Unfiltered water also was placed in a tightly 

sealed glass bottle and refrigerated for determination of methane concentration. 

Ground water was recovered with a peristaltic pump from existing wells (MLS38, MLS40, MLS41, 

MLS88, and WLMLF) and from stainless steel drive point wells (SG99-1, SG99-2, and SG99-3). After 

conductivity and pH became constant, the samples were filtered through an inline 0.45 μm filter and stored on ice 

for transport. 

In April of 2002, Water samples along the length of the Canadian River from New Mexico to central 

Oklahoma (fig. 3, table 3) were collected from the river bank in reaches with visible flow. Stagnant pools on the 

margin of the main channel near the landfill also were sampled. Measurements of electrical conductivity, 

temperature, and pH were made directly on the water source using calibrated meters. A beaker or syringe was used 

to collect the water. Water was filtered to <0.2 um for cation and anion analysis with a syringe filter. Cation 

samples were acidified with nitric acid to a pH <2. Raw water samples were collected to recover sulfate for isotopic 

analyses and alkalinity determinations. The raw water and anion samples were transported in an ice-filled cooler. 

4
5

Figure 2. Lithologic characteristics of sediment cored by freeze-shoe coring with locations of sediment and porewater samples. Locations of screened wells within a few meters of the core sites that were sampled to collect ground 

water are indicated in the inset. Detailed descriptions and locations of samples are listed in tables 1 and 2. 
6
7
8
Figure 3. Map of locations of water samples collected from the Canadian River, New Mexico, Texas, and Oklahoma. 

Detailed coordinates are listed in table 3. Bold font and (●) indicate the location of sample sites. Flow rates in the 

Canadian River (cubic feet per second) at the time of sampling are in italics for sample sites and the gauging stations 

at Purcell and Calvin, Oklahoma. Flow rates were obtained from NWIS at (http://waterdata.usgs.gov/nwis/rt). 
Sediment Analyses 

Grain size, mineralogy, iron species, sulfur species and their isotopic composition, and appearance of 

reactants and products were determined on the sediment samples. Sieves and a Malvern Mastersizer S long-bed 

laser-refraction instrument were used to determine the particle-size distribution of splits of the sediment samples. A 

10-gram split of each air-dried sample was first lightly disaggregated with a mortar and pestle, manually sieved to > 

2 mm, 2 mm to 425 μm, and <425 μm fractions. Clay aggregates larger than 425 mm were visually identified and 

disaggregated by hand to <425 μm. The mass of the three sieve fractions was measured to the nearest 0.01 gram. 

Approximately 0.3-gram splits of the <425 μm fraction, prepared with a mechanical splitter, were soaked overnight 

in distilled water amended with sodium hexametaphosphate to enhance particle dispersion. The disaggregation 

treatments were intended to disperse individual mineral particles. Although large intraclasts of mud and silt were 

visually recognized, they are not considered for this analysis. Disaggregation is compatible with the emphasis of 

this study on the reactivity of the sediment, which is more accurately represented by the dispersed particles. The 

density of measured grains were considered to be relatively similar so the weight fraction of the >2 mm and <2mm 

to >425 μm fractions were converted to volume percent to be consistent with the results of the Mastersizer. 

Bulk mineralogy of the sediments was determined by powder X-ray diffraction using a Siemens D500 with 

copper K-alpha radiation scanning at a count rate of 2 seconds per degree 2--theta. Clay mineralogy was determined 

on <2 μm-size separates that were prepared by centrifugation. Oriented mounts of the <2 μm-size separates were 

scanned as air dried, after saturating with ethylene glycol, and subsequent to heating at 550°C for 1 hour. 

Total and organic carbon contents of the sediment were determined on raw and acid-treated aliquots. A 2-

gram split of the sample was combined with 20 mL of 2 N HCl overnight to remove carbonate minerals. The 

suspension of solid and acid was filtered and rinsed thoroughly with distilled water. The total carbon and organic 

carbon contents of the sediment were measured by using a LECO SC-444 combustion furnace. Accuracy and 

precision of the carbon analyses were ± 5% for total carbon and ± 10% for organic carbon. Reported values close 

to the detection limit (0.02 wt.% carbon) were ± 20%. 

A JEOL JSM5800LV scanning electron microscope (SEM) equipped with an Oxford Isis energy dispersive 

X-ray analyzer was used to examine 30 freeze-dried sediment samples. Disaggregated sediment was attached to a 

sticky carbon membrane and lightly coated with carbon and gold prior to examination and analysis. Iron and sulfur 

phases were the focus of the examination. 

Iron speciation procedures were modified slightly from those of Heron and others (1994). Exchangeable 

and dissolved iron were determined by combining one of the sediment samples stored in the 50 mL serum vial with 

40 mL of de-aired 1 N KCl for 24 hours. KCl was used rather than the CaCl2

 of Heron and others (1994) to avoid 

precipitation of CaCO3

 given the high bicarbonate content in ground water contaminated with leachate (Cozzarelli 

and others, 2000). The serum vial was agitated intermittently to suspend the sediment. Following approximately 24 

hours, an aliquot of solution was withdrawn by needle and syringe, and the solution was filtered using a 0.2 μm 

filter. The solution then was analyzed for ferrous and total iron by using the spectrophotometric ferrozine method of 

Stookey (1970) with an ammonium acetate buffer used to maintain pH. A second aliquot of sediment in a separate 

serum vial was combined with 0.5 N HCl and reacted for 24 hours. The serum vial was intermittently shaken to 

suspend the sediment. Upon completion of the extraction, an aliquot of solution was removed by needle and syringe 

and filtered. The filtered solution was analyzed for ferrous iron by the ferrozine method (Stookey, 1970). Total iron 

was determined on a separate aliquot of the solution that was reacted with 2 mL of 1.4 M hydroxylamine 

hydrochloride in 2 N HCl. After 10 minutes, the ammonium acetate buffer and ferrozine solution were added, and 

the concentration of total iron measured colorimetrically. Ferric iron was determined by difference between total 

and ferrous iron. Extraction of the reducible iron phases in the sediment was determined by using a third aliquot of 

the sediment and reacting it with 40 mL of 0.008 M TiCl3

 in 0.05 M EDTA, pH adjusted to 6.5 with HCl. The 

serum vial was shaken intermittently, and the solution was withdrawn after 24 hours. The filtered Ti3+-EDTA 

solution was analyzed for total iron by standard methods of atomic-absorption spectrophotometry. The mass of 

solids was measured on the filtered residue of each extraction. This is considered a reasonable approximation of the 

original dry sample weight for the KCl and Ti3+ extractions. Results of the 0.5 N HCl extractions of mud and 

intraclast samples were corrected for the mass loss because of carbonate mineral dissolution. Mass loss due to 

carbonate minerals in sand samples was insignificant and less than 10 percent in intraclast and silt samples. 

10
The abundances of acid-volatile sulfide (AVS, FeS), acid-soluble sulfate and total reducible-disulfide (DI, 

FeS2

) were determined following the extraction scheme of Tuttle and others (1986). Approximately 10 to 15 grams 

of sediment were transferred from the frozen archive vial under a nitrogen atmosphere into a glass reaction vessel. 

Under flowing nitrogen, the sample was combined with 50 mL of 6 N HCl and 1 gram of stannous chloride and 

heated to evolve H2

S. The stannous chloride was added to reduce ferric iron in the samples that might oxidize 

evolved H2

S (Rice and others, 1993). Minor corrosion of crystallites of FeS2 following treatment of the samples 

with the stannous chloride and HCl was apparent during examination with the SEM. Based on these observations, 

the contribution of FeS2

 to the AVS component of the samples is considered small. The evolved H2S then was 

carried in flowing nitrogen through a reservoir of pH 4 buffer to remove HCl and bubbled through a trap containing 

silver nitrate. The resulting silver sulfide was collected by filtration. After volatization of the AVS, the acid 

solution was separated from the solid by filtration. The solution was reacted with 10 mL of a 10 weight percent 

BaCl2

 solution to precipitate dissolved sulfate as BaSO4. 

The residual solid was placed in a reaction vessel under flowing nitrogen and combined with 1M CrCl2

 in 4 

N HCl with 10 milliliters of ethanol. Chromium (II) reduces pyritic sulfur, which is evolved as H2

S. Evolved H2S 

was carried through the pH 4 buffer and then a silver nitrate solution that precipitated the H2

S as silver sulfide. The 

silver sulfide produced by the disulfide and AVS extractions was analyzed isotopically by direct combustion (Kester 

and others, 2001). Six sediment samples were mixed with acetone to extract elemental sulfur prior to AVS 

extraction. The resulting acetone solution was separated by filtration and treated with CrCl2 to recover the sulfur as 

silver sulfide. The amount of sulfur recovered by this extraction was consistently less than 0.01 ppm and is not 

presented in the summary results. 

Water Analyses 

Major ion, trace element, dissolved organic carbon, and methane concentrations were determined on 

selected water samples in USGS laboratories in Reston, Virginia and Denver, Colorado. Inductively coupled plasma 

atomic emission spectrometry, inductively coupled plasma mass spectrometry and direct current plasma 

spectrometry determined the cation and trace element composition of water samples. Anions were measured with 

ion chromatography. Dissolved organic carbon (DOC) was measured by the method of Qian and Mopper (1996); 

methane was determined by the method described in Baedecker and Cozzarelli (1992). 

Addition of dissolved barium chloride to selected water samples precipitated dissolved sulfate for isotope 

analyses. The pH of the water samples was adjusted between 3 and 4 with addition of HCl to remove dissolved 

carbonate species while minimizing exchange of oxygen bound to sulfate. Resulting BaSO4 was analyzed by direct 

combustion for sulfur and oxygen isotopes (Kester and others, 2001). 

Results 

Sediment Composition 

The alluvium deposited by the Canadian River contains sand, silt, clay, and aggregates of fine-grained 

sediment forming intraclasts (table 2). Most of the samples are red as a result of the transport of hematite pigment 

from Permian and Triassic red beds within the drainage basin. A few samples are distinctly gray consistent with 

post-depositional reductive dissolution of ferric oxides. Sand samples vary from finely laminated to massive. 

Mixtures of silt, fine sand, and clay also tend to be massive. Intraclasts are angular to rounded and 1 to 3 cm in long 

dimension. They commonly form conglomerates that likely formed by bank collapse or during episodes of high 

flow. Sand intercalated with the intraclasts typically is upper medium to coarse with some granules. Results of the 

grain-size analysis on disaggregated sediment are presented in table 4. Sand samples are fine to medium grained 

and moderately to poorly sorted. Intraclast-rich samples generally have the smallest median grain size. Silt samples 

are mixtures of sand, silt, and clay and, according to the classification of Folk (1980), are considered mainly sandy 

silt (fig. 4). Silt and intraclast samples typically are very poorly sorted. Many of the silty samples were identified 

initially as mud during examination in the glove box because of the heavy clay texture. 

11
12
13
 

14
15
16
17
18
19
Figure 4. Ternary diagram of the relative abundance of sand, silt, and clay in samples collected by freeze-shoe 

coring from the alluvium of the Canadian River near Norman, Oklahoma. 

Detrital constituents of the Canadian River alluvium include quartz, plagioclase, potassium feldspar, 

calcite, dolomite, and clay minerals. Silts are differentiated mineralogically from sands by increased abundances of 

clay and calcite. Clay minerals detected include illite-smectite, illite, smectite, kaolinite, and chlorite. Common 

heavy minerals that were identified include magnetite, hematite, sphene, and garnet consistent with the results of 

Pollack (1961). 

Examination of the sediment samples with the SEM identified pyrite, barite and very fine (<0.1 μm) ferric 

oxides as well as the major minerals described above. Pyrite is present in nearly all samples. Pyrite textures include 

framboids formed by anhedral aggregates (fig. 5), framboids with euhedral constituent grains, massive pyrite 

aggregates (fig. 6) and large (>10 μm) crystals, some with spiral overgrowths (fig. 7). Crystallite aggregates that 

form framboids in shallow samples are typically pseudo cubic to subhedral (fig. 5) while deeper samples have well 

formed octahedral faces. Textures of barite are consistent with detrital and authigenic grains (fig. 8). Several of the 

detrital barite grains have delicate textures that are would not have survived transport. The delicate textures are 

attributed to in situ dissolution. Although the sediment is pervasively red, isolated grains of iron oxide responsible 

for the pigment were not resolvable at 0.1 μm. Efforts to isolate red particles on sand grain surfaces consistently 

detected iron-rich clay particles and not the discrete iron oxides expected. The particles of hematite responsible for 

the red color could not be resolved at the resolution of the SEM (<50 nm). 

Table 5 lists the results of the iron analyses. Variations in the abundance of extractable iron are related to 

grain size with muds and mud clasts having greater amounts of leachable iron than sands. Only small amounts of 

exchangable and soluble iron were extracted with 1N KCl in a few silt and intraclast samples. Iron soluble in 0.5 N 

HCl is largely ferrous iron and is approximately 10 times more abundant in silt and intraclast samples than sand 

samples. Ferric iron was determined to be the dominant component of acid extractable iron only in modern river 

sand. Core samples with detectable ferric iron include a few silt samples and all samples from SG99. 

20
Figure 5. Secondary electron micrograph images of pyrite from relatively shallow samples (<2 meters) within the 

Canadian River alluvium. Note the irregular shape and surface of pyrite crystallites forming framboids and other 

aggregates. (A, B, and C) pyrite aggregates in black sand from the slough sediment. (D, E, and F) pyrite aggregates 

associated with clays from a black layer near water table at 5 feet depth in core VCA. 

21
Figure 6. Secondary electron and backscatter micrographs of massive pyrite aggregates from sediment samples of 

the Canadian River alluvium. (A) SG99-02, secondary electron micrograph of pyrite aggregate with poor crystal 

outline may be corroded or possibly reworked with sediment, (B) SG88-02-01, secondary electron micrograph of 

pyrite formed by aggregate of octahedral crystals, (C) SG41-04, secondary electron micrograph of an aggregate of 

octahedral pyrite crystals, (D) backscatter electron micrograph of pyrite (bright field) with quartz and clay, (E) 

secondary electron micrograph, and (F) backscatter electron micrograph of a large grain composed mainly of pyrite. 

22
Figure 7. Secondary electron images of well-formed pyrite crystals from samples of the Canadian River alluvium 

below depths of 2 meters. (A) SG88-02-07, pyrite framboid coated with biophage?, (B) SG99-03, pyrite framboid on 

clay, (C) SG41-04, (D) SG99-03, truncated octahedral pyrite in clay, (E,F) SG88-03-01, coarse pyrite with spiral 

overgrowths formed in vertical open space about 1 mm in diameter crossing red mud. 

23
Figure 8. Micrographs of barite detected within the Canadian River alluvium. Micrographs are obtained with a 

scanning electron microscope. (A) backscatter electron image and (B) secondary electron image of authigenic barite 

growing on woody fragment from SG38-04, (C) secondary electron image of corroded detrital barite VCA, 17 feet 

depth, (D) SG40-06, partially corroded detrital barite grain, (E) secondary electron image of relatively unaltered 

detrital barite from SG-88-07, (F) secondary electron image of partially dissolved barite grain from slough sediment. 

24
25
26

The Ti3+ reductive dissolution of iron oxides in 24 hours was variably effective at dissolution of red ferric 

oxides. Following 24 hours of exposure to the reagent, all pink-red sand samples had visually changed to gray. 

Red-brown silt and intraclast samples, however, remained largely red brown. The color of the Ti3+ solution in 

contact with the mud after 24 hours remained distinctly pink indicating that the Ti3+ had not been consumed. 

Allowing the suspended clay to settle revealed a stratification in which the last settled particles (smallest size 

fraction) were distinctly gray while the coarser fragments were red brown. Solutions were nonetheless extracted and 

analyzed according to the 24-hour reaction time recommended by Heron and others (1994). The Ti3+ and clay 

suspensions were allowed to react for 18 additional months after which time the color of the solution became pale 

yellow for the silt and intraclast samples but remained pink for sand samples. Most of the mud remained red even 

after 18 months, although the portion of gray sediment increased. The incomplete and slow reductive dissolution of 

ferric oxides in the silt and intraclast samples is attributed to a diffusion limited reduction reaction of ferric oxides 

intercalated with clay particles and insufficient Ti3+ to complete the reduction. 

Sulfur is present in the Canadian River alluvium as acid-soluble sulfate, acid-volatile sulfides (FeS), and 

chromium reducible sulfide (FeS2

) (table 6). Gray sediment accumulates 2 to 4 times more sulfur than red-brown 

sediment, with gray mud accumulating more than gray sand. Red sand on the surface contains the least amount of 

sulfur. Samples having the highest concentrations of pyrite and sulfate are intraclasts from uncontaminated core. 

The highest acid-volatile sulfur concentrations are from intraclasts and sands from the uncontaminated core. The 

sulfur isotopic compositions of these phases generally are higher in samples from contaminated core, likely 

reflecting greater reduction of the sulfate reservoir with increased dissolved organic compounds contained in the 

leachate. Silt and intraclast samples contain about twice the amount of sulfate as sands; however, the sulfate from 

the sands has negative sulfur isotopic compositions, suggesting the sulfate extracted from the sand is a product of 

oxidation of bacterially reduced sulfide. 

Water Composition 

The composition of pore water and ground water follow the pattern of compositions outlined in Cozzarelli 

and others (2000) (tables 7 and 8). Concentrations of alkalinity, ammonium, iron, arsenic, barium, boron, calcium, 

chloride, cobalt, DOC, lithium, magnesium, methane, nickel, potassium, rubidium, and selenium decline with 

increasing distance from the landfill. Sulfate is the only constituent that increases as the river is approached. The 

concentrations of ammonium, arsenic, boron, cobalt, and potassium in pore water from SG41 are intermediate to 

values characteristic of highly impacted (SG38 and SG40) and background sites (SG88 and SG99). Other 

parameters such as alkalinity, calcium, iron, magnesium, and strontium are consistent with substantial leachate 

contamination. The intermediate concentrations of several constituents in ground water recovered from SG41 are 

consistent with either leachate of a slightly different composition or the recent increase of the leachate component to 

ground water at SG41 as described by Becker (2002). As the leachate advances through the alluvium, some 

constituents are removed from solution by cation exchange and absorption. The sulfur isotopic composition of the 

ground water and surface water is highly variable. Systematic changes of composition with sulfate abundance, 

however, indicate that bacterial sulfate reduction is an active process in the Canadian River alluvium independent of 

the landfill leachate. 

The Canadian River water composition changes slightly along its course from northeastern New Mexico to 

east-central Oklahoma (table 9). Some of the variations may be related to the three man-made reservoirs located on 

the river prior to its entry into Oklahoma. Specific conductance generally declines downstream reflecting the 

addition of dilute recharge eastward through Oklahoma. The increased recharge is apparent in the increased flow of 

the river (fig. 3). Samples of two small surface depressions containing stagnant water (table 2) near the active 

channel of the Canadian River were also sampled. Water in both the proximal pond (1 m from the active channel, 

02-CR-05) and distal pond (10 m from the active channel, 02-CR-06) have markedly lower specific conductance 

than river water (02-CR-04) (table 9). The lower specific conductance of the ponds is attributed to rainwater 

recharge of the alluvium. 

The sulfur isotope composition of dissolved sulfate in the river is distinctly different between northeastern 

New Mexico and Oklahoma. The supply of sulfate in New Mexico is attributed to the oxidation of biogenic sulfide 

minerals in Cretaceous rock exposed in the drainage basin. In northern Texas and Oklahoma, the principal source of 

sulfate is gypsum exposed in Permian rocks along the drainage.
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