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Present Address: Kansas Geological Survey, The University of Kansas, 1930 Constant Ave., Lawrence, KS 66047

ABSTRACT

Petrographic, geochemical, and fluid inclusion analysis of dolomite and calcite cements has been conducted on Mississippian carbonates collected from the surface and subsurface of the southern midcontinent of the United States (Oklahoma, Missouri, Kansas, and Arkansas). Fracture and vug, intergrain, and intragrain porosity are filled with calcite, authigenic quartz, and dolomite cements. Primary limestone porosity is filled partially by early marine and meteoric calcite cements. Equant (blocky) calcite cements were precipitated under seawater or mixed meteoric-seawater conditions in the phreatic zone and in the deep phreatic zone under late (burial) diagenetic conditions. Fracture- and breccia-filling saddle dolomite cements that were observed are late diagenetic and are likely related to the nearby Tri-State Mississippi Valley-type (MVT) mineral district.

Carbon and oxygen isotope values of dolomite cements range from δ18O(VPDB) = −9.5 to −2.7‰ and from δ13C(VPDB) = −4.0 to −0.4‰. Values for calcite cements range from δ18O(VPDB) = −11.6 to −1.9‰ and from δ13C(VPDB) = −12.2 to +4.6‰. These values are consistent with three types of diagenetic fluids: seawater, seawater modified by meteoric water, and evolved basinal water. Analysis of fluid inclusions in late calcite, dolomite, and quartz cements indicates the presence of both dilute and high salinity end-member fluids. Homogenization temperatures (Th) of fluid inclusions range from 57°C to 175°C and salinities range from 0 to 25 equivalent weight % NaCl. Fluid inclusion Th values and salinities are consistent with a saline basinal fluid variably diluted by fluids of meteoric or mixed seawater and meteoric origin. Petroleum inclusions were observed in late diagenetic calcite and dolomite cements.The late diagenetic cements filled porosity retained after early diagenetic cementation indicating that some original porosity in the Mississippian carbonate rocks remained open during petroleum migration. Elevated fluid inclusion Th values over a broad region, not just in the Tri-State Mineral District, imply that the regional thermal maturity of rocks may be higher than believed previously.

This study indicates that the Mississippian carbonate resource play on the southern midcontinent has a very complex diagenetic history, continuing long after early diagenetic cementation. Possibly the most important diagenetic events affecting these rocks occurred during burial and basinal fluid migration through these strata.

INTRODUCTION

Mississippian carbonate rocks on the southern midcontinent of North America comprise an important unconventional petroleum play (Figure 1; Milam, 2013). These rocks also host the world-class Tri-State Mississippi Valley-type (MVT) Zn–Pb district as well as several smaller mineral deposits and sulfide mineral occurrences. The occurrence of MVT mineralization in these Mississippian carbonate rocks suggests that they were affected by pervasive regional basinal fluids associated with sulfide mineralization (Gregg and Shelton, 2012).

Figure 1.

Map of Oklahoma and neighboring states showing the study area (tan rectangle in the east–central portion of the map) and sample localities. Four sampling regions within the study area are shown: “A” cores in Osage County, Oklahoma, “B” surface samples and core in and near the Tri-State MVT mineral district, “C” core and outcrops on and near the Seneca Trough in Delaware, Wagoner, and Mayes counties, northeast Oklahoma, and “D” core and outcrops in McDonald and Stone counties, southwest Missouri and Benton and Boone counties, northwest Arkansas. Petroleum-producing areas and thickness of the Mississippian strata also are shown. Modified from Harris (1987).

Figure 1.

Map of Oklahoma and neighboring states showing the study area (tan rectangle in the east–central portion of the map) and sample localities. Four sampling regions within the study area are shown: “A” cores in Osage County, Oklahoma, “B” surface samples and core in and near the Tri-State MVT mineral district, “C” core and outcrops on and near the Seneca Trough in Delaware, Wagoner, and Mayes counties, northeast Oklahoma, and “D” core and outcrops in McDonald and Stone counties, southwest Missouri and Benton and Boone counties, northwest Arkansas. Petroleum-producing areas and thickness of the Mississippian strata also are shown. Modified from Harris (1987).

This study applies petrography, fluid inclusion microthermometry, and isotope geochemistry to examine the effects of late diagenetic fluids and identify the composition and source(s) of these fluids regionally in Mississippian rocks in the Cherokee and Ozark Platform region (northeastern Oklahoma, northwestern Arkansas, southeastern Kansas, and southwestern Missouri). Of particular interest is the effect of late diagenetic fluids on the evolution of porosity and the thermal history of the region as it relates to petroleum migration.

Geological Background

Mississippian carbonate rocks were deposited in parts of Colorado, Nebraska, Kansas, Oklahoma, Arkansas, Missouri, Iowa, and Illinois across the ancient Burlington shelf (Lane, 1978; Gutschick and Sandberg, 1983). Mississippian rocks in the study area (Figure 1) were deposited in a ramp and shelf system that trended along an approximate northeast–southwest strike and that deepened to the south into the Arkoma basin (Figure 2). This system is bounded by the Ozark uplift on the east and by the Transcontinental Arch (Nemaha uplift) to the north and northwest. Shallower water (shelf) depositional settings occurred in the northern part of the study area and deepened toward the south into the Arkoma Basin (Wilhite et al., 2011).

Figure 2.

Regional map showing Burlington shelf depositional systems during the early Mississippian. The study area is outlined by a red rectangle. Modified from Lane and DeKyser (1980).

Figure 2.

Regional map showing Burlington shelf depositional systems during the early Mississippian. The study area is outlined by a red rectangle. Modified from Lane and DeKyser (1980).

Mississippian strata in the study area are separated into four stages based on lithologic, biostratigraphic, and electric log characteristics (Figure 3). In ascending stratigraphic order, these are: Kinderhookian, Osagean, Meramecian, and Chesterian (Jordan and Rowland, 1959). In northern Oklahoma, Mississippian carbonates are mainly Kinderhookian, Osagean, and Meramecian. In the study area, Kinderhookian units represent a transgressive sequence (Handford, 1989; Shelby, 1986; Mazzullo et al., 2011) that contains the Bachelor, Compton, Northview, and Pierson formations (Unrast, 2012). At the base of the section, the Bachelor Formation comprises a light colored sandstone and greenish shale, which is overlain by the Compton Limestone consisting of thinly bedded mudstones and containing biohermal mud mounds (Anglin, 1966; Huffman, 1958; Unrast, 2012). The Northview Shale is composed of light green, soft limy shale and marl; the Pierson Formation is a gray, thinly bedded, crinoidal wackestone to packstone and also contains individual biohermal mounds as well as mound complexes (Anglin, 1966; Unrast, 2012). Osagean units consist of interbedded light- and dark-colored, dolomitic and argillaceous, cherty limestone (Jordan and Rowland, 1959). Lower Meramecian age rocks cropping out in the Tri-State MVT district are characterized by chert beds (McKnight and Fischer, 1970), whereas in northern Oklahoma, these beds are predominantly limestone (Huffman, 1958). Chesterian rocks are largely absent in northeastern Oklahoma as a result of erosion prior to Pennsylvanian deposition (Jordan and Rowland, 1959).

Figure 3.

Stratigraphic section for the study area, modified from Mazzullo et al. (2013). CHEST = Chesterian; MERA = Meramecian.

Figure 3.

Stratigraphic section for the study area, modified from Mazzullo et al. (2013). CHEST = Chesterian; MERA = Meramecian.

The Mississippian limestone section has been described as an overall 2nd-order sequence made up of a series of higher frequency, 3rd- and 4th-order sequences that occurred in response to eustatic sea-level change. This stratigraphic hierarchy is thought to play a significant role in the quality and vertical heterogeneity of the Mississippian reservoir (LeBlanc, 2014). In the study area, regressive, skeletal (dominantly crinoidal) grainstones exhibit abundant syntaxial cement, which occludes much of the pore space. This cement has been interpreted to be of early diagenetic origin (Morris et al., 2013). Packstones deposited during transgressions typically contain little void-filling cement and display varying degrees of silicification and dissolution, making them better reservoir rocks (Price, 2014). Mazzullo et al. (2009) documented the main diagenetic events in the Cowley Formation in south–central Kansas, including at least three generations of silicification, several periods of porosity-creating dissolution, and minor dolomitization. In the Compton and Pierson formations within the present study area, Morris et al. (2013) recognized early marine radiaxial calcite cementation, meteoric dissolution, and void-filling equant calcite cementation that they attributed to meteoric diagenesis, followed by minor dolomitization (see also Unrast, 2012).

The presence of the Tri-State MVT district (Figure 1) has largely been ignored by petroleum geologists working on the southern midcontinent. This world-class mineral district covers an area of about 5000 km2(1900 mi2) on the western flank of the Ozark Uplift in southwestern Missouri, southeastern Kansas, and northeastern Oklahoma (Hagni and Grawe, 1964; Hagni, 1982). Within the Tri-State MVT district, exposed sedimentary rocks are Mississippian and Pennsylvanian age and subsurface rocks range from Precambrian through Devonian age as determined by drilling (Hagni, 1976). Evidence of sulfide mineralization throughout the Carboniferous strata extends eastward into northern Arkansas and westward into Kansas (Leach et al., 1975; Coveney and Goebel, 1983; Gregg and Shelton, 2012). The ore deposits in the Tri-State MVT district are strata-bound and are hosted almost entirely by the cherty limestones of the Burlington–Keokuk Formation (Figure 3; Hagni, 1982). The most abundant ore and gangue minerals in the district are sphalerite, galena, chalcopyrite, pyrite, marcasite, calcite, dolomite, and quartz (jasperoid; Hagni and Grawe, 1964). Tri-State Zn–Pb mineralization has been linked to petroleum migration across the region (Fowler, 1933; Wei, 1975; Ragan et al, 1996; Gregg and Shelton, 2012). The ores and gangue minerals are believed to have been precipitated by saline basinal fluids emanating from the Arkoma Basin during the Alleghanian–Ouachita orogeny (Late Pennsylvanian to Permian) at temperatures from 50°C to 200°C (Leach, 1994; Appold and Nunn, 2005).

METHODS

Samples used in this study were collected from outcrops and core in Oklahoma, Missouri, Kansas, and Arkansas. Subsurface core was sampled at the Missouri Geological Survey core repository in Rolla, Missouri, the Oklahoma Geological Survey core repository in Norman, Oklahoma, and the Kansas Geological Survey in Lawrence, Kansas. Other core samples used in this study were donated by industry members of the Oklahoma State University Mississippian Consortium.

Petrographic analysis was conducted on 146 thin sections with particular attention given to void-filling dolomite and calcite cements. Cathodoluminescence (CL) petrography was carried out using a CITL MK5-1 cathodoluminescence system mounted on an Olympus-BX51 microscope equipped with 4×, 10×, and 40× long focal distance objective lenses, and a “Q Imaging” 5-megapixel, cooled, low-light, digital camera system.

Carbon and oxygen isotope compositions were determined for dolomite and calcite samples using Thermo-Finnigan Delta Plus gas-source mass spectrometers at the stable isotope laboratories of Oklahoma State University and the University of Missouri. The δ13C and δ18O values (relative to the VPDB standard) have standard errors of less than ±0.05, based on replicate measurements of the NBS-19 calcite reference standard, and have been corrected for reaction with 103% phosphoric acid at 70°C (Rosenbaum and Sheppard, 1986). Ratios of 87Sr/86Sr were determined using a TIMS at the University of Kansas Radiogenic Isotope Laboratory and have errors of ±0.000014  at a 95% confidence interval.

Fluid inclusion microthermometric measurements were made using a Linkam THMSG 600 heating and cooling stage mounted on an Olympus BX41 microscope equipped with 40× and 100× long focal distance objective lenses. Homogenization (Th) and last ice melting (Tm) temperatures have errors of ±1.0°C and ±0.3°C, respectively, based on analysis of synthetic fluid inclusions (Shelton and Orville, 1980). The inclusions analyzed in this study were aqueous, two-phase, primary and secondary inclusions, using the terminology of Roedder (1984). Salinities were calculated from Tm measurements using equations from Bodnar (1992).

RESULTS

Petrography

For the purpose of describing the limestone lithologies and diagenetic features encountered in this study, it is convenient to divide the study area into four regions, A, B, C, and D, as shown in Figure 1.

Region A includes samples from the Tri-State MVT district. They include several core and mine samples from the Joplin area of southwest Missouri including the mines at Neck City (Jasper County), and Granby (Newton County). Samples from the Picher field (a subdistrict of the Tri-State MVT district) of southeastern Kansas and northeastern Oklahoma include mines near Treece and Baxter Springs (Cherokee County), Kansas, and Picher (Ottawa County), Oklahoma. Because mining activity in the Tri-State district ceased in 1967, most of the mine samples were collected from tailings dumps, so accurate locations within mines are unknown. Several samples were donated for this study from private mineral collections and labels indicate only the mine name. All of the mine samples in the Tri-State district likely are from the upper part of the Burlington–Keokuk Formation (Figure 3), which hosted most of the mineralization in this district (Hagni, 1976). Tri-State samples consist of chert breccias cemented by mineralized jasperoid containing dolomite-, calcite-, sphalerite-, and galena-filling open spaces ranging from millimeter to decimeter scale.

In addition to mine samples, one core (PM-21 from Cherokee County, Kansas) was sampled, which penetrated Osagean–Meramecian strata (Figure 3). This core consists of three units in ascending order: (1) chert-free, grain-supported limestone and dolomite overlain by argillaceous, micritic, cherty dolomite; (2) interbedded argillaceous wackestone and brecciated chert; and (3) echinoderm-rich, bioclastic wackestone–packstone (as described by Young, 2010). Replacement dolomite crystals observed in this core have planar-e to -s texture (Sibley and Gregg, 1987) and range in size from approximately 0.05 to 0.1 mm. Solution-enlarged fractures ranging from approximately 1 mm to several centimeters in this core are filled by coarse crystalline (cm size) calcite and saddle dolomite cement.

Two cores from Carterville (Jasper County), Missouri, were sampled from the Burlington–Keokuk Formation. The lithology here is mostly cherty and muddy limestone, with calcite-filled fractures ranging from 1 to 5 mm in width.

Region B samples (Figure 1) are from two cores, the Blackbird 4-33 and the Perryman 2 oil wells, in Osage County, Oklahoma. The rocks encountered in the Blackbird well include 84.7 m (278 ft; 959.21043.9 m [31473425 ft] core interval) of the Reeds Spring Formation (Osage) based on sponge spicule facies (Darwin Boardman, personal communication, 2014). Lithologies sampled in the Blackbird core include argillaceous and siliceous mudstone with scattered fossils and intragrain, vug, and fracture porosity. Intragrain and vug porosity is filled by calcite cement (Figure 4C, D). Fracture porosity includes ptygmatic fractures and solution-widened fractures ranging from 1 to 3 cm (0.41.2 in) and is filled by calcite and quartz cements (Figures 6C, 7). The Perryman 2 core includes 12.7 m (41.7 ft) of chert breccia and partially dolomitized limestone. The exact stratigraphic position of the cored section within the Mississippian is not known. Lithologies in the Perryman 2 core include chert breccia in the upper 6.3 m (20.7 ft) and chert breccia and partly dolomitized lime mudstones dominating the lower 6.4 m (21 ft). No carbonate cements were observed in the Perryman 2 core.

Figure 4.

(A) Skeletal grainstone from the Pierson Formation, Benton County, Arkansas. Bladed calcite cement (b) growing on brachiopod shells and equant (blocky) calcite cement (e) filling remaining porosity. Crossed polarized light (XPL). (B) Cathodoluminescence (CL) photomicrograph of the same field as (A). Note the apparent compositional zoning of the equant calcite cement. (C) Rugose coral, Osage County, Oklahoma, with intragrain porosity filled by bladed and equant calcite cements. Plane polarized light (PPL). (D) CL photomicrograph of the same field as (C) showing compositional zoning in the bladed and equant calcite cements. (E) Crinoid grainstone from the Pierson Formation, Delaware County, Oklahoma. Porosity is largely filled by syntaxial and equant calcite cement. XPL. (F) CL photomicrograph of the same field as (E). Initial syntaxial cement (dark zone 2) extending into banded zones 3 and 4 cement.

Figure 4.

(A) Skeletal grainstone from the Pierson Formation, Benton County, Arkansas. Bladed calcite cement (b) growing on brachiopod shells and equant (blocky) calcite cement (e) filling remaining porosity. Crossed polarized light (XPL). (B) Cathodoluminescence (CL) photomicrograph of the same field as (A). Note the apparent compositional zoning of the equant calcite cement. (C) Rugose coral, Osage County, Oklahoma, with intragrain porosity filled by bladed and equant calcite cements. Plane polarized light (PPL). (D) CL photomicrograph of the same field as (C) showing compositional zoning in the bladed and equant calcite cements. (E) Crinoid grainstone from the Pierson Formation, Delaware County, Oklahoma. Porosity is largely filled by syntaxial and equant calcite cement. XPL. (F) CL photomicrograph of the same field as (E). Initial syntaxial cement (dark zone 2) extending into banded zones 3 and 4 cement.

Region C samples (Figure 1) include outcrop and core samples taken along the Seneca fault system in Mayes, Wagoner, and Delaware counties, Oklahoma. Samples from Mayes County were collected from a quarry near Pryor, Oklahoma and include large fracture- and breccia-filling calcite and dolomite ranging from millimeter to centimeter scale near the top of the Burlington–Keokuk Formation (Figure 3). Core samples from the Hall 2-13 well in Wagoner County, Oklahoma include 15 m (49 ft; 200.5215.6 m [657.8707.3 ft] core interval) of the Fayetteville Formation (Figure 3) and are composed of skeletal packstone containing fractures ranging from 0.5 to 1.0 cm (0.20.4 in) filled by calcite and quartz cement. Samples from Delaware County, Oklahoma were collected from a crinoidal mound in the Pierson Formation along Spavinaw Creek.

Region D (Figure 1) includes outcrops of the Compton, Pierson, and Reeds Spring formations in Benton and Boone counties, Arkansas, and McDonald and Stone counties, Missouri (Figure 3). The sedimentology and petrology of the units in this region were described in detail by Unrast (2012) and Morris et al. (2013). The samples collected are composed of skeletal grainstones and packstones containing porosity-filling calcite and cherty mudstones. We selected samples that preferentially contain fractures and solution-widened fractures ranging in size from 0.5 mm to 1.0 cm (0.20.4 in), filled by calcite cement.

Cement Paragenesis

Radiaxial fibrous and bladed calcite cements were observed in stromatactis-like cavities in Lower Mississippian biohermal mud mounds in southern Missouri and northern Arkansas by Unrast (2013) and Morris et al. (2013). Similar fibrous and bladed calcite cements were observed in grainstones of this study (Figure 4A). Intergrain-filling, bladed calcite cement was observed that nucleated on noncrinoid skeletal fragments in Mississippian grainstones in region “D” of this study (Figure 4A, B). Similar bladed calcite cement was observed as intragrain fillings in rugose corals observed in region “B” (Osage County, Oklahoma; Figure 4C, D). Syntaxial calcite cements typically nucleated on crinoids (Figure 4E, F). Bladed and syntaxial calcites are followed by blocky (equant) calcite cement that typically fills remaining intergrain and intragrain porosity (Figure 4).

Strong compositional zoning was deduced by CL microscopy in all inter- and intragrain calcite cements and vug-filling cements. Unrast (2013) studied the CL cement stratigraphy in Mississippian limestones associated with mud mound build-ups and divided calcite cements into five stages, the first of which consists of nonferroan fibrous to bladed calcite followed by four distinct stages of nonferroan equant calcite. Stage 1 cements are non-CL to mottled CL; stage 2 cements are non-CL; stage 3 cements are bright yellow CL; stage 4 cements are alternating dull orange to brown CL; and stage 5 cements are dull orange-brown CL with no internal zoning (Unrast, 2013). These patterns of CL zonation generally were observed in the study, although some of the stages are absent depending on the sample locality. For instance, intragrain, porosity-filling calcite cement observed in a rugose coral sample from Region B (Figure 1) contains only stages 1, 3, 4, and 5 cement (Figure 4D), whereas intergrain porosity-filling cement from region D contains all of the CL stages (Figure 5).

Figure 5.

(A) Packstone to grainstone with intergrain porosity filled by calcite, McDonald County, Missouri. PPL. (B) CL photomicrograph of the same field as (A) showing four compositional zones (2, 3, 4, and 5) in the equant calcite cement. (C) Grainstone with intragrain porosity filled by calcite, Benton County, Arkansas. Close-up of field shown in Figure 4A, PPL. (D) CL photomicrograph of the same field as (C) showing compositional zoning of the equant calcite cement (zones 1, 2, 3, and 4).

Figure 5.

(A) Packstone to grainstone with intergrain porosity filled by calcite, McDonald County, Missouri. PPL. (B) CL photomicrograph of the same field as (A) showing four compositional zones (2, 3, 4, and 5) in the equant calcite cement. (C) Grainstone with intragrain porosity filled by calcite, Benton County, Arkansas. Close-up of field shown in Figure 4A, PPL. (D) CL photomicrograph of the same field as (C) showing compositional zoning of the equant calcite cement (zones 1, 2, 3, and 4).

Calcite and, infrequently, quartz cement filling fractures, solution-widened channels, and breccias (Figures 6, 7) were observed throughout the study area. Calcite cement-filled ptygmatic fractures in cherty mudstone occur in Region B in Osage County, Oklahoma (Figure 6C). Quartz and calcite cements were observed in fracture porosity from Wagoner County, Oklahoma (Region C, Figure 1), and in fracture, solution-widened channel, and breccia porosity (Figure 7) from Osage County, Oklahoma (Region B, Figure 1).

Figure 6.

(A) Cherty mudstone in the Reeds Spring Formation, Benton County, Arkansas. Solution-widened fracture (channel) porosity is filled by equant calcite cement. PPL. (B) CL photomicrograph of the same field as (A) showing compositional zoning in the equant calcite cement. (C) Cherty mudstone, Osage County Oklahoma, with a ptygmatic fracture filled by equant calcite cement. XPL, composite of nine photomicrographs.

Figure 6.

(A) Cherty mudstone in the Reeds Spring Formation, Benton County, Arkansas. Solution-widened fracture (channel) porosity is filled by equant calcite cement. PPL. (B) CL photomicrograph of the same field as (A) showing compositional zoning in the equant calcite cement. (C) Cherty mudstone, Osage County Oklahoma, with a ptygmatic fracture filled by equant calcite cement. XPL, composite of nine photomicrographs.

Figure 7.

(A) Solution-widened fracture (channel) porosity and unmodified breccia porosity, Osage County, Oklahoma are filled by quartz and equant calcite cement. XPL, composite of 16 photomicrographs. The close-up field is shown by the yellow rectangle. (B) Close-up of a solution-widened fracture, shown in (A), filled by chalcedony quartz (q) and equant calcite (e) cement. XPL. (C) CL photomicrograph of the same field as (B). Quartz cement is non cathodoluminescent and no compositional zoning is apparent in the calcite cement.

Figure 7.

(A) Solution-widened fracture (channel) porosity and unmodified breccia porosity, Osage County, Oklahoma are filled by quartz and equant calcite cement. XPL, composite of 16 photomicrographs. The close-up field is shown by the yellow rectangle. (B) Close-up of a solution-widened fracture, shown in (A), filled by chalcedony quartz (q) and equant calcite (e) cement. XPL. (C) CL photomicrograph of the same field as (B). Quartz cement is non cathodoluminescent and no compositional zoning is apparent in the calcite cement.

The CL characteristics of fracture-filling, equant calcite cement differ among the four regions studied. For example, calcite cement filling fractures in samples from Mayes County, Oklahoma (Region C), and core samples from Jasper County, Missouri (Region A), display yellow CL with no internal zoning. Equant calcite cement that fills solution-widened channels in mine samples from the Tri-State MVT district (Region A) and core samples from Osage County, Oklahoma (Region B), and Benton County, Arkansas (Region D), display alternating bright to dull CL zoning (Figure 6A, B). Authigenic quartz crystals associated with calcite cement filling fractures from Wagoner County, Oklahoma (Region C), and Osage County, Oklahoma (Region B), are non-CL.

Replacement dolomite is uncommon in the study area. Typically, dolomite occurs as scattered rhombic crystals replacing mudstone or carbonate mud matrix in packstone and wackestone (Figure 8A, B). An exception to this observation is the PM-21 core from Cherokee County, Kansas (Region A), which displays both matrix-replacing dolomite and fracture-filling saddle dolomite (Figure 8C, D).

Figure 8.

(A) Replacement dolomite, Mayes County, Oklahoma. PPL. (B) CL photomicrograph of the same field as (A). (C) Dolomitized mudstone with a solution-widened fracture filled by saddle dolomite, Cherokee County, Kansas. PPL. (D) CL photomicrograph of the same field as (C) showing compositional zoning in the dolomite cement. (E) Saddle dolomite cement, Tri-State MVT district, Picher-field, Admiralty Mine (#3 Shaft) Oklahoma. XPL, composite of four photomicrographs. (F) CL photomicrograph of the same field as (E) showing compositional zoning in the dolomite cement.

Figure 8.

(A) Replacement dolomite, Mayes County, Oklahoma. PPL. (B) CL photomicrograph of the same field as (A). (C) Dolomitized mudstone with a solution-widened fracture filled by saddle dolomite, Cherokee County, Kansas. PPL. (D) CL photomicrograph of the same field as (C) showing compositional zoning in the dolomite cement. (E) Saddle dolomite cement, Tri-State MVT district, Picher-field, Admiralty Mine (#3 Shaft) Oklahoma. XPL, composite of four photomicrographs. (F) CL photomicrograph of the same field as (E) showing compositional zoning in the dolomite cement.

Open-space-filling saddle dolomite cement was observed in Mayes County, Oklahoma (Region C, Figure 1) and throughout the Tri-State district (Region A, Figure 1). Figure 8E, F shows an example of saddle dolomite cement from the Picher field, Admiralty mine (#3 Shaft), Oklahoma. The compositional stratigraphy of this dolomite cement, as revealed by CL, is typical of the study area and includes up to four stages of cement growth: bright yellow-orange CL followed by a thin dull gray zone (stage 1); red-orange and thin non-CL zone (stage 2); dark red-orange and thick non-CL (stage 3); orange grading to yellow CL zones (stage 4; Figure 8E, F). It is important to note that all four stages are not always present in all of the dolomite samples studied throughout the district.

Fluid Inclusion Microthermometry

Two-phase, aqueous fluid inclusions (liquid and vapor) were observed in open-space-filling cements throughout the study area. This includes intergrain and intragrain blocky (equant) calcite cement and fracture- and breccia-filling calcite, dolomite, and quartz cements (Figure 9A–D). Measured inclusions range from 2 to 30 micrometers in their longest dimension. Smaller two-phase inclusions were observed in some dolomite cements, but were not measured due to poor optical resolution. Single-phase (liquid only) petroleum inclusions were observed in calcite cements from the Tri-State district (Region A). (These include samples from the Admiralty Mine, Oklahoma, Anna Beaver Mine, Oklahoma, Wood Chuck Mine, Oklahoma, Neck City Mine, Missouri, Treece, Kansas, and one sample without a specific mine location from the Picher Field, Oklahoma.) Single-phase petroleum inclusions also were observed in fracture-filling calcite cements from Osage County, Oklahoma (Region B) and Benton County, Arkansas (Region D). Single- and two-phase (liquid and vapor) petroleum inclusions were observed in fracture- and breccia-filling calcite and dolomite cements from Wagoner and Mayes County, Oklahoma (Region C). Petroleum inclusions observed in this study are characterized by a light blue fluorescence under UV light (Figure 9E, F).

Figure 9.

Photomicrographs of fluid inclusions in cements. (A) Assemblage of primary two-phase inclusions in open-space-filling calcite cement, Tri-State Mineral District, Neck City, Missouri. (B) Secondary inclusions in fracture-filling calcite cement, Mayes County, Oklahoma. (C) Primary inclusions in fracture-filling saddle dolomite cement, Mayes County, Oklahoma. (D) Primary inclusions in solution-widened fracture-filling quartz cement, Osage County, Oklahoma. (E) Assemblage of primary petroleum-bearing inclusions in fracture-filling calcite cement, Wagoner County, Oklahoma. (F) Ultraviolet photomicrograph from the same field as (E) showing light-blue fluorescence of petroleum-bearing inclusions.

Figure 9.

Photomicrographs of fluid inclusions in cements. (A) Assemblage of primary two-phase inclusions in open-space-filling calcite cement, Tri-State Mineral District, Neck City, Missouri. (B) Secondary inclusions in fracture-filling calcite cement, Mayes County, Oklahoma. (C) Primary inclusions in fracture-filling saddle dolomite cement, Mayes County, Oklahoma. (D) Primary inclusions in solution-widened fracture-filling quartz cement, Osage County, Oklahoma. (E) Assemblage of primary petroleum-bearing inclusions in fracture-filling calcite cement, Wagoner County, Oklahoma. (F) Ultraviolet photomicrograph from the same field as (E) showing light-blue fluorescence of petroleum-bearing inclusions.

Values for Th and Tm were obtained for 240 aqueous fluid inclusions (Table 1). Th values for all fluid inclusions measured range from approximately 50 to 175°C and Tm values range from 4.2 to 25.2°C (Table 1). A small population of the low salinity inclusions yielded Tm values above 0°C (Table 1). This likely is caused by metastable, superheated ice that forms due to the failure of a vapor bubble to nucleate on heating (Roedder, 1967). The Th data for these inclusions is reported in Table 1.

Table 1.

Fluid inclusion microthermometric data for carbonate and authigenic quartz cements.

Sample IDLocationAssemblageMineralTh(°C)Tm(°C)Calculated Salinity (wt. % eq. NaCl)
SMD 2100Osage Co., OK (#1)Assemblage 1Calcite970.71.2
  Assemblage 2Calcite1120.50.8
   Calcite1180.50.8
   Calcite1180.50.8
  Assemblage 3Calcite810.10.2
   Calcite1050.10.2
   Calcite841.52.6
   Calcite 0.50.9
  Assemblage 4Calcite872.5 
   Calcite802.5 
   Calcite 0.3 
   Calcite105  
  Assemblage 5Calcite813.0 
  Assemblage 6Calcite1160.7 
SMD 2102Osage Co., OK (#2)Assemblage 1Calcite126−3.76.0
   Calcite1261.83.0
   Calcite1253.86.1
  Assemblage 2Calcite1641.93.2
   Calcite1491.93.2
  Assemblage 3Calcite11521.022.8
   Calcite11819.021.7
   Calcite 19.021.7
   Calcite 15.419.0
   Calcite127  
  Assemblage 4Calcite17317.520.6
   Calcite16815.419.0
  Assemblage 5Calcite8623.024.3
  Assemblage 6Calcite12223.024.3
   Calcite12621.223.1
  Assemblage 7Calcite1352.13.5
  Assemblage 8Quartz12621.623.4
   Quartz13021.623.4
   Quartz10121.623.4
   Quartz13021.623.4
  Assemblage 9Quartz8319.622.1
   Quartz8719.622.1
   Quartz9822.323.9
   Quartz9818.621.4
   Quartz9817.820.8
   Quartz9818.521.3
  Assemblage 10Quartz1222.03.4
   Quartz1232.94.8
   Quartz1191.42.4
   Quartz1131.42.4
  Assemblage 11Quartz1022.33.9
   Quartz1022.03.4
   Quartz1082.33.9
   Quartz1080.40.7
SMD 1002Benton Co., ARAssemblage 1Calcite12011.215.2
  Assemblage 2Calcite13219.021.7
   Calcite13522.624.0
   Calcite 22.624.0
  Assemblage 3Calcite12520.722.8
   Calcite12519.522.0
   Calcite13521.023.0
   Calcite13921.423.3
   Calcite11621.423.3
  Assemblage 4Calcite1492.44.0
   Calcite1382.94.8
   Calcite1472.94.8
  Assemblage 5Calcite1205.07.8
  Assemblage 6Calcite10119.622.1
SMD-P1Mayes Co., OK (#1)Assemblage 1Calcite20018.521.3
  Assemblage 2Calcite880.40.7
  Assemblage 3Calcite 19.622.1
  Assemblage 4Calcite 1.72.9
  Assemblage 5Calcite 1.5 
SMD-P3Mayes Co., OK (#2)Assemblage 1Calcite1128.912.7
   Calcite1143.55.7
  Assemblage 2Calcite1043.65.8
   Calcite1043.15.1
   Calcite1053.15.1
   Calcite1054.26.7
   Calcite1054.26.7
   Calcite1054.26.7
  Assemblage 3Calcite1307.611.2
   Calcite1196.69.9
   Calcite1287.210.7
   Calcite133  
  Assemblage 4Calcite670.7 
   Calcite670.7 
   Calcite670.7 
   Calcite530.7 
  Assemblage 5Calcite972.03.4
   Calcite743.35.4
  Assemblage 6Calcite674.57.2
   Calcite881.72.9
  Assemblage 7Calcite430.71.2
   Calcite740.20.3
   Calcite740.20.3
   Calcite550.20.3
  Assemblage 8Calcite1452.54.1
  Assemblage 9Calcite801.0 
   Calcite701.0 
   Calcite701.0 
   Calcite701.0 
   Calcite701.0 
   Calcite721.0 
   Calcite971.0 
SMD-P5Mayes Co., OK (#3)Assemblage 1Dolomite628.211.9
   Dolomite7513.016.9
   Dolomite6513.016.9
TSNC1-14Tri-State, Neck City, MOAssemblage 1Calcite765.58.5
   Calcite844.47.0
  Assemblage 2Calcite903.35.4
  Assemblage 3Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
  Assemblage 4Calcite594.0 
   Calcite614.0 
   Calcite65  
  Assemblage 5Calcite74  
   Calcite740.7 
  Assemblage 6Calcite860.00.0
   Calcite940.00.0
   Calcite900.00.0
   Calcite90  
   Calcite56  
   Calcite86  
   Calcite980.6 
TSOG2Tri-State, Old Goat Mine, Treece, KSAssemblage 1Calcite89  
JC5McDonald Co., MOAssemblage 1Calcite1291.7 
   Calcite 2.2 
   Calcite 2.2 
   Calcite1400.7 
   Calcite 2.2 
  Assemblage 2Calcite1291.52.6
  Assemblage 3Calcite158  
  Assemblage 4Calcite 0.00.0
  Assemblage 5Calcite11221.823.6
   Calcite9521.823.6
   Calcite8621.823.6
   Calcite11221.823.6
   Calcite 21.823.6
  Assemblage 6Calcite114  
   Calcite114  
   Calcite114  
   Calcite114  
   Calcite114  
TSA-1Tri-State, Admiralty Mine (#1)Assemblage 1Dolomite14224.325.1
  Assemblage 2Dolomite10315.519.0
  Assemblage 3Dolomite13023.224.5
   Dolomite13523.724.8
   Dolomite12822.724.1
   Dolomite13021.823.6
   Dolomite13523.624.7
  Assemblage 4Dolomite12724.025.0
   Dolomite8316.519.8
   Dolomite 23.524.6
   Dolomite 18.521.3
   Dolomite 20.322.6
TSA-4Tri-State, Admiralty Mine (#2)Assemblage 1Dolomite111  
   Dolomite111  
  Assemblage 2Sphalerite107  
TSAB1Tri-State, Anna Beaver Mine, OKAssemblage 1Dolomite10224.425.2
   Dolomite11620.322.6
  Assemblage 2Dolomite11224.225.0
   Dolomite11222.023.7
   Dolomite11217.920.9
   Dolomite10221.423.3
   Dolomite 23.624.7
  Assemblage 3Dolomite1122.44.0
   Dolomite1122.44.0
   Dolomite 3.55.7
  Assemblage 4Dolomite11021.223.2
   Dolomite1072022.4
   Dolomite 25.225.7
   Dolomite 22.924.3
   Dolomite 22.924.3
   Dolomite 2022.4
TSPF1Tri-State, Ottawa Co., OKAssemblage 1Calcite19821.723.5
  Assemblage 2Calcite 6.810.2
TSW-1Tri-State, Wood Chuck Mine, OKAssemblage 1Sphalerite170  
   Sphalerite178  
TSWB-3-3BTri-State, Treece, KSAssemblage 1Dolomite11223.324.5
   Dolomite 16.019.5
  Assemblage 2Dolomite151  
H2-13-663Wagoner Co., OK (#1)Assemblage 1Calcite10918.021.0
   Calcite11316.119.5
  Assemblage 2Calcite114  
   Calcite117  
   Calcite101  
   Calcite101  
   Calcite112  
  Assemblage 3Calcite115  
   Calcite115  
   Calcite115  
  Assemblage 4Calcite870.9 
   Calcite86  
   Calcite986.610.0
  Assemblage 5Calcite857.811.5
   Calcite741.83.0
   Calcite741.83.0
  Assemblage 6Calcite6214.1 
   Calcite6214.1 
  Assemblage 7Calcite151  
  Assemblage 8Calcite83  
   Calcite91  
   Calcite85  
   Calcite99  
   Calcite99  
  Assemblage 9Calcite1102.33.9
   Calcite1102.33.9
   Calcite1102.33.9
H2-13-675Wagoner Co., OK (#2)Assemblage 1Calcite99  
   Calcite10315.318.9
  Assemblage 2Calcite711.6 
  Assemblage 3Calcite61  
   Calcite660.10.2
   Calcite660.10.2
  Assemblage 4Quartz11613.117.0
   Quartz9211.415.4
  Assemblage 5Quartz891.42.4
   Quartz891.42.4
   Quartz891.42.4
   Quartz891.42.4
   Quartz891.42.4
   Quartz941.42.4
  Assemblage 6Quartz1533.45.6
   Quartz1533.45.6
   Quartz1533.45.6
   Quartz1533.45.6
   Quartz1533.45.6
  Assemblage 7Quartz1723.45.6
Sample IDLocationAssemblageMineralTh(°C)Tm(°C)Calculated Salinity (wt. % eq. NaCl)
SMD 2100Osage Co., OK (#1)Assemblage 1Calcite970.71.2
  Assemblage 2Calcite1120.50.8
   Calcite1180.50.8
   Calcite1180.50.8
  Assemblage 3Calcite810.10.2
   Calcite1050.10.2
   Calcite841.52.6
   Calcite 0.50.9
  Assemblage 4Calcite872.5 
   Calcite802.5 
   Calcite 0.3 
   Calcite105  
  Assemblage 5Calcite813.0 
  Assemblage 6Calcite1160.7 
SMD 2102Osage Co., OK (#2)Assemblage 1Calcite126−3.76.0
   Calcite1261.83.0
   Calcite1253.86.1
  Assemblage 2Calcite1641.93.2
   Calcite1491.93.2
  Assemblage 3Calcite11521.022.8
   Calcite11819.021.7
   Calcite 19.021.7
   Calcite 15.419.0
   Calcite127  
  Assemblage 4Calcite17317.520.6
   Calcite16815.419.0
  Assemblage 5Calcite8623.024.3
  Assemblage 6Calcite12223.024.3
   Calcite12621.223.1
  Assemblage 7Calcite1352.13.5
  Assemblage 8Quartz12621.623.4
   Quartz13021.623.4
   Quartz10121.623.4
   Quartz13021.623.4
  Assemblage 9Quartz8319.622.1
   Quartz8719.622.1
   Quartz9822.323.9
   Quartz9818.621.4
   Quartz9817.820.8
   Quartz9818.521.3
  Assemblage 10Quartz1222.03.4
   Quartz1232.94.8
   Quartz1191.42.4
   Quartz1131.42.4
  Assemblage 11Quartz1022.33.9
   Quartz1022.03.4
   Quartz1082.33.9
   Quartz1080.40.7
SMD 1002Benton Co., ARAssemblage 1Calcite12011.215.2
  Assemblage 2Calcite13219.021.7
   Calcite13522.624.0
   Calcite 22.624.0
  Assemblage 3Calcite12520.722.8
   Calcite12519.522.0
   Calcite13521.023.0
   Calcite13921.423.3
   Calcite11621.423.3
  Assemblage 4Calcite1492.44.0
   Calcite1382.94.8
   Calcite1472.94.8
  Assemblage 5Calcite1205.07.8
  Assemblage 6Calcite10119.622.1
SMD-P1Mayes Co., OK (#1)Assemblage 1Calcite20018.521.3
  Assemblage 2Calcite880.40.7
  Assemblage 3Calcite 19.622.1
  Assemblage 4Calcite 1.72.9
  Assemblage 5Calcite 1.5 
SMD-P3Mayes Co., OK (#2)Assemblage 1Calcite1128.912.7
   Calcite1143.55.7
  Assemblage 2Calcite1043.65.8
   Calcite1043.15.1
   Calcite1053.15.1
   Calcite1054.26.7
   Calcite1054.26.7
   Calcite1054.26.7
  Assemblage 3Calcite1307.611.2
   Calcite1196.69.9
   Calcite1287.210.7
   Calcite133  
  Assemblage 4Calcite670.7 
   Calcite670.7 
   Calcite670.7 
   Calcite530.7 
  Assemblage 5Calcite972.03.4
   Calcite743.35.4
  Assemblage 6Calcite674.57.2
   Calcite881.72.9
  Assemblage 7Calcite430.71.2
   Calcite740.20.3
   Calcite740.20.3
   Calcite550.20.3
  Assemblage 8Calcite1452.54.1
  Assemblage 9Calcite801.0 
   Calcite701.0 
   Calcite701.0 
   Calcite701.0 
   Calcite701.0 
   Calcite721.0 
   Calcite971.0 
SMD-P5Mayes Co., OK (#3)Assemblage 1Dolomite628.211.9
   Dolomite7513.016.9
   Dolomite6513.016.9
TSNC1-14Tri-State, Neck City, MOAssemblage 1Calcite765.58.5
   Calcite844.47.0
  Assemblage 2Calcite903.35.4
  Assemblage 3Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
  Assemblage 4Calcite594.0 
   Calcite614.0 
   Calcite65  
  Assemblage 5Calcite74  
   Calcite740.7 
  Assemblage 6Calcite860.00.0
   Calcite940.00.0
   Calcite900.00.0
   Calcite90  
   Calcite56  
   Calcite86  
   Calcite980.6 
TSOG2Tri-State, Old Goat Mine, Treece, KSAssemblage 1Calcite89  
JC5McDonald Co., MOAssemblage 1Calcite1291.7 
   Calcite 2.2 
   Calcite 2.2 
   Calcite1400.7 
   Calcite 2.2 
  Assemblage 2Calcite1291.52.6
  Assemblage 3Calcite158  
  Assemblage 4Calcite 0.00.0
  Assemblage 5Calcite11221.823.6
   Calcite9521.823.6
   Calcite8621.823.6
   Calcite11221.823.6
   Calcite 21.823.6
  Assemblage 6Calcite114  
   Calcite114  
   Calcite114  
   Calcite114  
   Calcite114  
TSA-1Tri-State, Admiralty Mine (#1)Assemblage 1Dolomite14224.325.1
  Assemblage 2Dolomite10315.519.0
  Assemblage 3Dolomite13023.224.5
   Dolomite13523.724.8
   Dolomite12822.724.1
   Dolomite13021.823.6
   Dolomite13523.624.7
  Assemblage 4Dolomite12724.025.0
   Dolomite8316.519.8
   Dolomite 23.524.6
   Dolomite 18.521.3
   Dolomite 20.322.6
TSA-4Tri-State, Admiralty Mine (#2)Assemblage 1Dolomite111  
   Dolomite111  
  Assemblage 2Sphalerite107  
TSAB1Tri-State, Anna Beaver Mine, OKAssemblage 1Dolomite10224.425.2
   Dolomite11620.322.6
  Assemblage 2Dolomite11224.225.0
   Dolomite11222.023.7
   Dolomite11217.920.9
   Dolomite10221.423.3
   Dolomite 23.624.7
  Assemblage 3Dolomite1122.44.0
   Dolomite1122.44.0
   Dolomite 3.55.7
  Assemblage 4Dolomite11021.223.2
   Dolomite1072022.4
   Dolomite 25.225.7
   Dolomite 22.924.3
   Dolomite 22.924.3
   Dolomite 2022.4
TSPF1Tri-State, Ottawa Co., OKAssemblage 1Calcite19821.723.5
  Assemblage 2Calcite 6.810.2
TSW-1Tri-State, Wood Chuck Mine, OKAssemblage 1Sphalerite170  
   Sphalerite178  
TSWB-3-3BTri-State, Treece, KSAssemblage 1Dolomite11223.324.5
   Dolomite 16.019.5
  Assemblage 2Dolomite151  
H2-13-663Wagoner Co., OK (#1)Assemblage 1Calcite10918.021.0
   Calcite11316.119.5
  Assemblage 2Calcite114  
   Calcite117  
   Calcite101  
   Calcite101  
   Calcite112  
  Assemblage 3Calcite115  
   Calcite115  
   Calcite115  
  Assemblage 4Calcite870.9 
   Calcite86  
   Calcite986.610.0
  Assemblage 5Calcite857.811.5
   Calcite741.83.0
   Calcite741.83.0
  Assemblage 6Calcite6214.1 
   Calcite6214.1 
  Assemblage 7Calcite151  
  Assemblage 8Calcite83  
   Calcite91  
   Calcite85  
   Calcite99  
   Calcite99  
  Assemblage 9Calcite1102.33.9
   Calcite1102.33.9
   Calcite1102.33.9
H2-13-675Wagoner Co., OK (#2)Assemblage 1Calcite99  
   Calcite10315.318.9
  Assemblage 2Calcite711.6 
  Assemblage 3Calcite61  
   Calcite660.10.2
   Calcite660.10.2
  Assemblage 4Quartz11613.117.0
   Quartz9211.415.4
  Assemblage 5Quartz891.42.4
   Quartz891.42.4
   Quartz891.42.4
   Quartz891.42.4
   Quartz891.42.4
   Quartz941.42.4
  Assemblage 6Quartz1533.45.6
   Quartz1533.45.6
   Quartz1533.45.6
   Quartz1533.45.6
   Quartz1533.45.6
  Assemblage 7Quartz1723.45.6

Figure 10A displays the fluid inclusion data as salinity, expressed as equivalent weight % NaCl, calculated from measured Tm values (Bodnar, 1992) plotted against Th values for calcite, dolomite, and quartz cements from the study area. Only inclusions for which both Th and Tm values were determined are plotted. These results indicate the presence of both dilute and high salinity end-member fluids (calculated values ranging from 0 to 25 equivalent weight % NaCl). Ranges of Th values are similar for both of these end-member salinity populations.

Figure 10.

(A) Plots of fluid inclusion salinities versus Th values. (B) Fluid inclusion salinities and Th values grouped as assemblages. The number of individual fluid inclusions for which valid Th and Tm values were measured are shown on each data point. Data fields are shown for fluid inclusions measurements made in previous studies in and near the Tri-State MVT district.

Figure 10.

(A) Plots of fluid inclusion salinities versus Th values. (B) Fluid inclusion salinities and Th values grouped as assemblages. The number of individual fluid inclusions for which valid Th and Tm values were measured are shown on each data point. Data fields are shown for fluid inclusions measurements made in previous studies in and near the Tri-State MVT district.

Figure 10B displays the fluid inclusion data with data fields shown from earlier studies in and near the Tri-State Mineral District. The individual fluid inclusions in Figure 10B are grouped on the basis of being observed in the same microscope field, being the same type of inclusion (e.g., primary or secondary) and having almost the same Th and Tm values (thus more than one fluid inclusion group can be identified in a single microscope field). Because the groups of fluid inclusions are in close proximity to one another both spatially and temporally, they are treated here as fluid inclusion assemblages.

Figure 10B shows more clearly the presence of two distinct salinity end members. The fields displaying previously published data (Figure 10B) from in and near the Tri-State Mineral District are consistent with two salinity end members. Data for fluid inclusion assemblages in the four regions of the study area document the presence of the two salinity end members in each region (Figure 11).

Figure 11.

Fluid inclusion assemblages plotted among the four regions in the study area (see Figure 1).

Figure 11.

Fluid inclusion assemblages plotted among the four regions in the study area (see Figure 1).

Isotope Analysis

Carbon and Oxygen Isotopes

Carbon and oxygen isotope analysis was conducted on carbonate samples from all four regions of the study area (Figure 1; Table 2). Calcite mud from region D has δ18O values of −5.6 to −1.4‰ and δ13C values of 1.9 to 4.3‰. Calcitic crinoid debris from regions C and D has δ18O values of −2.5 to −1.3‰ and δ13C values of 2.3 to 4.0‰. These values are similar to those of brachiopods and marine calcite cement from the same areas measured by Morris et al. (2013) (Figure 12).

Table 2.

Stable isotope analyses of carbonate cements and host rocks. Clay-size calcite referred to “calcite mud.”

SampleLocalityMineralogyδ13C‰ (VPDB)δ18O‰ (VPDB)δ18O‰ (VSMOW)
TSAB1Tri-State-Anna Beaver Mine, OKCalcite cement4.7510.9819.60
TSAB1Tri-State-Anna Beaver Mine, OKDolomite–nonplanar1.586.6824.04
TSAB1Tri-State-Anna Beaver Mine, OKDolomite cement1.686.4024.33
TSAB1Tri-State-Anna Beaver Mine, OKDolomite–nonplanar0.985.6125.13
TSW-1Tri-State-Wood Chuck Mine, OKDolomite–nonplanar1.557.1723.53
TSW-2Tri-State-Wood Chuck Mine, OKDolomite–nonplanar2.066.8823.83
TSA-1Tri-State, Admiralty Mine, OKDolomite–nonplanar1.557.0323.67
TSA-2Tri-State, Admiralty Mine, OKDolomite–nonplanar1.687.6123.07
TSA-3Tri-State, Admiralty Mine, OKDolomite cement1.537.7222.96
TSA-4Tri-State, Admiralty Mine, OKDolomite cement1.487.3523.35
TSP-1Tri-State-Premier Mine, OKDolomite cement1.346.1624.57
TSP-2Tri-State-Premier Mine, OKDolomite cement1.867.1723.52
TSOG-1Tri-State, Old Goat Mine, Treece, KSCalcite cement4.3510.2920.31
TSOG-2Tri-State, Old Goat Mine, Treece, KSCalcite cement4.5310.7119.88
SMD1002Benton Co., ARCalcite cement1.768.4522.21
SMD1008McDonald Co., MOCalcite cement2.843.1127.72
SMD2100Osage Co., OKCalcite cement2.584.0426.76
SMD2102Osage Co., OKCalcite cement2.586.2124.52
SMD2103Osage Co., OKCalcite cement0.907.0623.64
SMD3001White Rock Co., MOCalcite cement2.788.8621.78
PM21-608Cherokee Co., KSDolomite cement2.002.6628.18
PM21-608Cherokee Co., KSDolomite–planar0.423.8027.00
PM21-600Cherokee Co., KSSaddle dolomite1.196.2824.44
PM21-614Cherokee Co., KSReplacement dolomite2.025.8324.91
PM21-618Cherokee Co., KSReplacement dolomite2.304.4626.32
A04-1220Jasper Co., MOCalcite cement1.824.4026.38
B50-1-85.5Jasper Co., MOCalcite cement0.799.9320.68
J5.5McDonald Co., MOCalcite crinoid2.261.2629.62
JC2McDonald Co., MOCalcite cement3.183.8426.96
JC2McDonald Co., MOCalcite mud2.664.0426.75
JC4McDonald Co., MOCalcite cement2.905.0625.70
JC4McDonald Co., MOCalcite mud2.524.0626.73
JC5McDonald Co., MOCalcite cement1.948.3022.36
JC5McDonald Co., MOCalcite mud3.013.8626.94
JN2McDonald Co., MOCalcite crinoid3.562.4028.45
JS5McDonald Co., MOCalcite crinoid2.872.1128.74
SW1Stone Co., MOCalcite crinoid3.182.2928.56
SWCU2Stone Co., MOCalcite cement3.696.6424.08
SWCU2Stone Co., MOCalcite cement4.571.9028.96
SWCU4Stone Co., MOCalcite cement3.577.2423.46
SWCU4Stone Co., MOCalcite mud4.291.9128.96
SEP2Delaware Co., OKCalcite crinoid3.391.9028.96
SEP2Delaware Co., OKCalcite cement2.652.9827.85
PAEF2Benton Co., ARCalcite crinoid3.692.4928.36
PAEC5Benton Co., ARCalcite cement1.629.2121.43
PAEC5Benton Co., ARCalcite crinoid3.971.6829.19
PAWCBA2Benton Co., ARCalcite mud1.905.5725.18
PAWC2Benton Co., ARCalcite cement2.444.6626.11
PAWC4Benton Co., ARCalcite crinoid3.512.4328.41
PAWC1Benton Co., ARCalcite mud3.301.4329.44
PAWF1Benton Co., ARCalcite crinoid3.291.8429.02
PAEC4Benton Co., ARCalcite cement1.927.2823.42
PAEC4Benton Co., ARCalcite crinoid3.103.3527.47
H2-13-663AWagoner Co., OKCalcite cement2.039.2421.39
H2-13-663BWagoner Co., OKCalcite cement1.359.8920.73
H2-13-675BWagoner Co., OKCalcite cement1.869.2921.34
H2-13-675AWagoner Co., OKCalcite cement1.829.2521.39
H2-13-678Wagoner Co., OKCalcite cement1.869.3921.24
SMD-P1Mayes Co., OKCalcite cement12.1210.8319.75
SMD-P2Mayes Co., OKCalcite cement11.1211.0319.54
SMD-P3Mayes Co., OKCalcite cement11.8411.4219.15
SMD-P4Mayes Co., OKCalcite cement12.1011.3519.22
SMD-P5-BMayes Co., OKCalcite cement4.3311.5718.99
SMD-P5-AMayes Co., OKDolomite Cement3.989.5021.12
TSNC1-14Neck City, MOCalcite cement3.5011.0419.54
TSWB2-3-BTri-State, Treece, KSDolomite cement1.938.8321.82
TSWB2-3-ATri-State, Treece, KSDolomite cement1.387.7322.95
TSWB2-3A-BTri-State, Treece, KSDolomite cement1.248.0922.58
TSWB2-3A-ATri-State, Treece, KSDolomite cement1.518.8221.82
SampleLocalityMineralogyδ13C‰ (VPDB)δ18O‰ (VPDB)δ18O‰ (VSMOW)
TSAB1Tri-State-Anna Beaver Mine, OKCalcite cement4.7510.9819.60
TSAB1Tri-State-Anna Beaver Mine, OKDolomite–nonplanar1.586.6824.04
TSAB1Tri-State-Anna Beaver Mine, OKDolomite cement1.686.4024.33
TSAB1Tri-State-Anna Beaver Mine, OKDolomite–nonplanar0.985.6125.13
TSW-1Tri-State-Wood Chuck Mine, OKDolomite–nonplanar1.557.1723.53
TSW-2Tri-State-Wood Chuck Mine, OKDolomite–nonplanar2.066.8823.83
TSA-1Tri-State, Admiralty Mine, OKDolomite–nonplanar1.557.0323.67
TSA-2Tri-State, Admiralty Mine, OKDolomite–nonplanar1.687.6123.07
TSA-3Tri-State, Admiralty Mine, OKDolomite cement1.537.7222.96
TSA-4Tri-State, Admiralty Mine, OKDolomite cement1.487.3523.35
TSP-1Tri-State-Premier Mine, OKDolomite cement1.346.1624.57
TSP-2Tri-State-Premier Mine, OKDolomite cement1.867.1723.52
TSOG-1Tri-State, Old Goat Mine, Treece, KSCalcite cement4.3510.2920.31
TSOG-2Tri-State, Old Goat Mine, Treece, KSCalcite cement4.5310.7119.88
SMD1002Benton Co., ARCalcite cement1.768.4522.21
SMD1008McDonald Co., MOCalcite cement2.843.1127.72
SMD2100Osage Co., OKCalcite cement2.584.0426.76
SMD2102Osage Co., OKCalcite cement2.586.2124.52
SMD2103Osage Co., OKCalcite cement0.907.0623.64
SMD3001White Rock Co., MOCalcite cement2.788.8621.78
PM21-608Cherokee Co., KSDolomite cement2.002.6628.18
PM21-608Cherokee Co., KSDolomite–planar0.423.8027.00
PM21-600Cherokee Co., KSSaddle dolomite1.196.2824.44
PM21-614Cherokee Co., KSReplacement dolomite2.025.8324.91
PM21-618Cherokee Co., KSReplacement dolomite2.304.4626.32
A04-1220Jasper Co., MOCalcite cement1.824.4026.38
B50-1-85.5Jasper Co., MOCalcite cement0.799.9320.68
J5.5McDonald Co., MOCalcite crinoid2.261.2629.62
JC2McDonald Co., MOCalcite cement3.183.8426.96
JC2McDonald Co., MOCalcite mud2.664.0426.75
JC4McDonald Co., MOCalcite cement2.905.0625.70
JC4McDonald Co., MOCalcite mud2.524.0626.73
JC5McDonald Co., MOCalcite cement1.948.3022.36
JC5McDonald Co., MOCalcite mud3.013.8626.94
JN2McDonald Co., MOCalcite crinoid3.562.4028.45
JS5McDonald Co., MOCalcite crinoid2.872.1128.74
SW1Stone Co., MOCalcite crinoid3.182.2928.56
SWCU2Stone Co., MOCalcite cement3.696.6424.08
SWCU2Stone Co., MOCalcite cement4.571.9028.96
SWCU4Stone Co., MOCalcite cement3.577.2423.46
SWCU4Stone Co., MOCalcite mud4.291.9128.96
SEP2Delaware Co., OKCalcite crinoid3.391.9028.96
SEP2Delaware Co., OKCalcite cement2.652.9827.85
PAEF2Benton Co., ARCalcite crinoid3.692.4928.36
PAEC5Benton Co., ARCalcite cement1.629.2121.43
PAEC5Benton Co., ARCalcite crinoid3.971.6829.19
PAWCBA2Benton Co., ARCalcite mud1.905.5725.18
PAWC2Benton Co., ARCalcite cement2.444.6626.11
PAWC4Benton Co., ARCalcite crinoid3.512.4328.41
PAWC1Benton Co., ARCalcite mud3.301.4329.44
PAWF1Benton Co., ARCalcite crinoid3.291.8429.02
PAEC4Benton Co., ARCalcite cement1.927.2823.42
PAEC4Benton Co., ARCalcite crinoid3.103.3527.47
H2-13-663AWagoner Co., OKCalcite cement2.039.2421.39
H2-13-663BWagoner Co., OKCalcite cement1.359.8920.73
H2-13-675BWagoner Co., OKCalcite cement1.869.2921.34
H2-13-675AWagoner Co., OKCalcite cement1.829.2521.39
H2-13-678Wagoner Co., OKCalcite cement1.869.3921.24
SMD-P1Mayes Co., OKCalcite cement12.1210.8319.75
SMD-P2Mayes Co., OKCalcite cement11.1211.0319.54
SMD-P3Mayes Co., OKCalcite cement11.8411.4219.15
SMD-P4Mayes Co., OKCalcite cement12.1011.3519.22
SMD-P5-BMayes Co., OKCalcite cement4.3311.5718.99
SMD-P5-AMayes Co., OKDolomite Cement3.989.5021.12
TSNC1-14Neck City, MOCalcite cement3.5011.0419.54
TSWB2-3-BTri-State, Treece, KSDolomite cement1.938.8321.82
TSWB2-3-ATri-State, Treece, KSDolomite cement1.387.7322.95
TSWB2-3A-BTri-State, Treece, KSDolomite cement1.248.0922.58
TSWB2-3A-ATri-State, Treece, KSDolomite cement1.518.8221.82
Figure 12.

Values of δ18O and δ13C (per mil VPDB) for carbonate samples from the study area. The region for calcite in equilibrium with Mississippian seawater (Mii et al., 1999) is shown as well as the regions attributed to fresh phreatic and seawater mixing and late diagenetic calcite. The fields occupied by intermediate- and late-stage calcite cements of Ritter and Goldstein (2012) and equant calcite cements of Morris et al. (2013) are also shown.

Figure 12.

Values of δ18O and δ13C (per mil VPDB) for carbonate samples from the study area. The region for calcite in equilibrium with Mississippian seawater (Mii et al., 1999) is shown as well as the regions attributed to fresh phreatic and seawater mixing and late diagenetic calcite. The fields occupied by intermediate- and late-stage calcite cements of Ritter and Goldstein (2012) and equant calcite cements of Morris et al. (2013) are also shown.

Intergrain and vug-filling calcite cement and fracture- and breccia-filling calcite cement from regions C and D form two clusters of differing δ18O values. The 1st cluster has δ18O values of 5.0 to 1.9 and δ13C values of 1.6 to 4.6‰. The second cluster, which also contains samples from regions A and B, displays δ18O values of 9.9 to 6.3 and δ13C values of 0.8 to 3.7. Morris et al. (2013) obtained values for intergrain equant calcite cements that are similar to the values obtained for the 2nd cluster observed in this study (Figure 12). Equant (blocky) fracture- and breccia-filling calcite cements, from regions A, B, and C, form a grouping with distinct δ18O and δ13C values that range from 11.6 to 6.2 and 12.1 to 2.6, respectively. This group also contains one value for saddle dolomite cement from Mayes County (Figure 12).

Replacement dolomite and saddle dolomite cements in the Tri-State Mineral District (region A) have δ18O and δ13C values of 9.5 to 5.6 and 4.0 to 1.0, respectively. Replacement and saddle dolomite cements from Cherokee County, Kansas (region A) display δ18O and δ13C values ranging from 6.3 to 2.6 and 2.0 to 2.3, respectively.

Strontium Isotopes

Ratios of 87Sr/86Sr for crinoid debris and associated intergrain equant calcite cement from region D are 0.7081 and 0.7085, respectively (Table 3). Fracture-filling calcite cement from all of the regions displays Sr isotope ratio values ranging from 0.7091 to 0.7112. The values for 87Sr/86Sr obtained for intergrain calcite cement and a crinoid grain are 0.7085 and 0.7082, respectively. These ratios and their δ18O values (~ 3 to 2) are consistent with precipitation in equilibrium with the Mississippian seawater (Figure 13, Mii et al., 1999; Bruckschen et al., 1999). The 87Sr/86Sr values for the late diagenetic fracture- and breccia-filling calcite and dolomite cements are more radiogenic, ranging from 0.7091 to 0.7100 and their δ18O values are low, from approximately 11 to 6. One sample of fracture-filling cement in Osage County, Oklahoma has a value of 0.7112 that is anomalously radiogenic, compared to the other values.

Table 3.

Sr isotope and oxygen data () for carbonate components in the study area (see Figure 14).

SampleLocationLithology87Sr/86Srδ18O (VPDB)
TSAB-1-AAnna Beaver Mine, OKBreccia-filling calcite cement0.709810.98
TSAB-1-BAnna Beaver Mine, OKBreccia-filling dolomite cement0.70916.68
SMD2102Osage Co., OKFracture-filling calcite cement0.71126.21
TSNC-1-14Neck City, MOBreccia-filling calcite cement0.709911.04
SMD-P5Mayes Co., OKBreccia-filling dolomite cement0.70929.50
SMD-P1Mayes Co., OKFracture-filling calcite cement0.709710.83
TSA-1Admiralty Mine, OKBreccia-filling dolomite cement0.70937.03
H2-663Wagoner Co., OKFracture-filling calcite cement0.70929.89
JC5McDonald Co., MOFracture-filling calcite cement0.71008.30
SEP2-ADelaware Co., OKCalcite crinoid skeletal grain0.70821.90
SEP2-BDelaware Co., OKIntergrain calcite cement0.70852.98
SampleLocationLithology87Sr/86Srδ18O (VPDB)
TSAB-1-AAnna Beaver Mine, OKBreccia-filling calcite cement0.709810.98
TSAB-1-BAnna Beaver Mine, OKBreccia-filling dolomite cement0.70916.68
SMD2102Osage Co., OKFracture-filling calcite cement0.71126.21
TSNC-1-14Neck City, MOBreccia-filling calcite cement0.709911.04
SMD-P5Mayes Co., OKBreccia-filling dolomite cement0.70929.50
SMD-P1Mayes Co., OKFracture-filling calcite cement0.709710.83
TSA-1Admiralty Mine, OKBreccia-filling dolomite cement0.70937.03
H2-663Wagoner Co., OKFracture-filling calcite cement0.70929.89
JC5McDonald Co., MOFracture-filling calcite cement0.71008.30
SEP2-ADelaware Co., OKCalcite crinoid skeletal grain0.70821.90
SEP2-BDelaware Co., OKIntergrain calcite cement0.70852.98
Figure 13.

Values of 87Sr/86Sr plotted against δ18O values for carbonate samples of the study area. Limestone in equilibrium with Mississippian seawater is shown as the light blue field (Bruckschen et al., 1999; Mii et al., 1999).

Figure 13.

Values of 87Sr/86Sr plotted against δ18O values for carbonate samples of the study area. Limestone in equilibrium with Mississippian seawater is shown as the light blue field (Bruckschen et al., 1999; Mii et al., 1999).

DISCUSSION

Paragenesis

A paragenesis of diagenetic events in the study area is shown in Figure 14. Early diagenesis includes stabilization of high-Mg calcite (and possibly aragonite) skeletal grains and micrite to low-Mg calcite. Early fibrous and bladed calcite cements likely were precipitated initially from seawater (Unrast, 2012, 2013). Values of 87Sr/86Sr and δ18O (Figure 13, Table 3) indicate that these early diagenetic fabrics are in, or near, equilibrium with Mississippian seawater (Mii et al., 1999; Bruckschen et al., 1999). Carbonate cements precipitated from Early Mississippian seawater likely were high-Mg calcite transitioning to aragonite by the Late Mississippian (Lowenstein et al., 2003). Carbon and oxygen isotope values for calcite mud matrix and crinoid grains (Figure 12) are consistent with precipitation from Mississippian seawater (Mii et al., 1999). Stable isotope values for brachiopods and marine calcite cement obtained by Morris et al. (2013) also are consistent with precipitation from Mississippian seawater (Figure 12).

Figure 14.

Paragenetic sequence for diagenetic events in the study area. The dashed lines indicate uncertain timing.

Figure 14.

Paragenetic sequence for diagenetic events in the study area. The dashed lines indicate uncertain timing.

Intragrain, Intergrain, and Vug-Filling Calcite Cements

Unrast (2012, 2013) described five distinct compositional zones, visible with CL, from blocky intergrain and vug-filling calcite cements in the study area (Figure 5). This CL zoning pattern is similar to the 5-zone CL stratigraphy described by Kaufman et al. (1988) for the Burlington–Keokuk Formation in a region extending from the Mississippi Valley of Illinois and Missouri into southwestern Missouri. On the basis of stratigraphy and cross-cutting relationships, they attributed the first three CL zones to mixing of seawater and meteoric water or inundation by meteoric water associated with sea-level falls during the Mississippian.

Ritter and Goldstein (2012) also recognized five major CL zones in intergrain calcite cements in the Burlington–Keokuk in a region extending from east–central Kansas and west–central Missouri to southeastern Kansas and southwestern Missouri. These CL zones are comparable to those of Unrast (2012, 2013) and Kaufman et al. (1988) (Table 4). Carbon and oxygen isotope values for the first three CL zones of Ritter and Goldstein (2012) were interpreted by them to be consistent with precipitation from fresh phreatic and brackish water prior to deep burial. They observed and analyzed one phase (liquid) fluid inclusions that they interpreted to indicate an entrapment temperature below 50°C. Based on one 87Sr/86Sr value (0.7088), which is slightly more radiogenic than Mississippian seawater, Ritter and Goldstein (2012) suggested that this meteoric water interacted with continental-derived argillaceous sediments.

Table 4.

Correlation of cathodoluminescence zones in calcite cements among studies of Mississippian rocks on the midcontinent.

This StudyRitter and Goldstein (2012)Kaufman et al. (1988)
1NL1-NL5II
2ML6-ML7III
3NL7IV
4SL8-NL8V
5SL9VI
This StudyRitter and Goldstein (2012)Kaufman et al. (1988)
1NL1-NL5II
2ML6-ML7III
3NL7IV
4SL8-NL8V
5SL9VI

On the basis of crosscutting relationships with MVT mineralization, Kaufman et al. (1988) assigned an early Permian minimum age for their CL zones 4 and 5, which may correspond in timing with MVT mineralization in the Ozark region (Leach et al. 2001; Gregg and Shelton, 2012). Both Kaufman et al. (1988) and Ritter and Goldstein (2012) suggested that the later CL zones of calcite cements are related to post-Pennsylvanian fluids that may have been associated with either deep circulation of low-temperature meteoric water from the overlying Pennsylvanian strata or warm basinal waters presumably moving up from underlying Cambrian–Ordovician strata.

The δ18O and δ13C values of intergrain, intragrain, and vug-filling calcite cements obtained in this study (Figure 12) range from 8.2 to 1.9 and 1.5 to 4.7, respectively. On the basis of low δ18O values, Morris et al. (2013) interpreted equant intergrain calcite cements to have a meteoric origin. We interpret the equant calcite cements of Morris et al. (2013) to be equivalent to the blocky intergrain calcites of our study. Carbon and oxygen isotope values for the equant calcite cements of Morris et al. (2013) overlap significantly with blocky intergrain cement values of our study (Figure 12) and with carbon and oxygen isotope values obtained by Ritter and Goldstein (2012) for all of the CL stages of calcite cements observed in their study (Figure 12).

The presence of two-phase fluid inclusions in the later stages (CL zones 4 and 5) of intergrain, intragrain, and vug-filling calcite cements (Figure 9A, B) observed in our study indicates that these cements likely precipitated from warm (.50°C) fluids. We therefore reinterpret the low δ18O values of Morris et al. (2013) to indicate precipitation of their equant calcite cement from warm basinal fluids rather than from meteoric waters (Figure 12).

The assignment of CL zone 4 and 5 calcite cements to precipitation from post-Pennsylvanian basinal waters requires that porosity was not totally destroyed during early diagenesis and that considerable porosity remained through the period of petroleum migration. This interpretation also was made by Ritter and Goldstein (2012) for Mississippian rocks north and west of our study area (western Missouri and eastern Kansas). Ritter and Goldstein (2012) believed that an average porosity of 24% remained in the Burlington–Keokuk bioclastic limestones into late stage diagenesis.

Fracture- and Breccia-Filling Calcite Cement

Calcite cement fills fractures and is an open-space breccia filling in all four regions of the study area. Dolomite cements also were observed as a fracture- and breccia-filling in regions A, B, and C (Figure 1). Throughout most of the study area, fracture- and breccia-filling calcite cements display uniformly bright yellow to orange CL. An exception is fracture-filling calcite cement from region D (Benton County, Arkansas) that displays dull to bright CL zonation (Figure 6A, B).

Carbon and oxygen isotope values for fracture- and breccia-filling calcite cements in all four regions of the study area are consistent with precipitation from fluids ranging from Mississippian seawater to basinal water (Figure 12). Low δ13C values for fracture- and breccia-filling calcite cements in the Tri-State Mineral District and in Mayes County, Oklahoma, along the Seneca fault system are consistent with oxidation of organic matter associated with petroleum generation (Figure 12; Machel et al., 1995). These same samples contain petroleum-bearing inclusions (Figure 9E, F).

Significant planar replacement dolomite was observed only in one core from Region A (Cherokee County, Kansas). Slightly lower δ18O values for this dolomite are consistent with dolomitization by meteoric and seawater or, more likely, initial dolomitization by seawater with later resetting of the isotopic composition by recrystallization in the presence of warm basinal water (Figure 12). The presence of fracture-filling saddle dolomite in this core supports this latter hypothesis. Planar replacement dolomite may correspond in timing and have a similar origin as dolomites I & II identified by Banner et al. (1988) and Cander et al. (1988) in the Mississippian Burlington–Keokuk Formation in western Illinois and eastern and central Missouri.

Saddle dolomite cements were observed only in regions A and C of the study area (Figure 1). Hagni and Graw (1964) interpreted saddle dolomite formation in the Tri-State Mineral District (Region A) to be associated with the main stages of sphalerite and galena ore precipitation. Similar CL stratigraphy among saddle dolomites in the Tri-State Mineral District, Cherokee County, Kansas, and along the Seneca fault (Mayes County, Oklahoma) system in Mayes County, Oklahoma (Figure 8) suggest precipitation by the same or similar fluids.

Low δ18O (and δ13C) values (Figure 12) for saddle dolomites are consistent with precipitation from basinal brines, as is their close association with sulfide mineralization in the Tri-State district (Hagni and Grawe, 1964). Saddle dolomite in the study area likely corresponds in timing with dolomite III identified by Cander et al. (1988) in the Mississippian Burlington–Keokuk Formation in western Illinois and eastern and central Missouri, which also is attributed to a late diagenetic origin. The timing of this dolomite may also correspond to the widely dispersed occurrences of saddle dolomite in Mississippian strata elsewhere in the U.S. midcontinent observed by Goldstein and King (2014).

Authigenic quartz cement was observed associated with fracture- and breccia-filling calcite in regions B and C. In region B, quartz cement occurs paragenetically earlier than calcite, whereas in region C it is later. All of the quartz cement examined in this study is non-CL. Possible sources of silica for authigenic quartz in the study area are the cherts, tripolites, and spiculites that are ubiquitous in Mississippian strata in the midcontinent (Mazzullo et al., 2009, 2011). Most of these are thought to be early diagenetic, so the late diagenetic authigenic quartz studied here would represent a remobilization of this silica. Alternatively, silica may have been introduced by basinal fluids originating in the underlying Cambrian–Ordovician section.

Origin and Timing of Late Diagenetic Fluids

Fluid Inclusion Constraints

Fluid inclusion analysis of calcite, dolomite, and quartz cements in the study area indicate precipitation by at least two end-member fluids. Figure 10 shows two distinct clusters of fluid inclusion data: (1) a high salinity fluid and (2) a fluid having moderate salinity to no salinity. Previous studies conducted in the Tri-State district (Ragan, 1996; Young, 2010; Wenz et al., 2012) found similar distributions of high and low salinity values (Figure 10B). Both clusters of fluid inclusion data in Figure 10 have similar Th ranges (approximately 60175°C). Two earlier studies of fluid inclusions in calcite, dolomite, and sphalerite from the Tri-State district (Schmidt, 1962; Wei, 1975) found ranges of Th values similar to those of our study. These studies did not determine Tm values, so salinities are not available for comparison.

The major difference between this study and earlier studies is that this study collected fluid inclusion data for Mississippian-hosted carbonates regionally, whereas previous studies were focused in and near the Tri-State MVT district. Figure 11 indicates that similar distributions of Th values and salinities exist in all four regions of the study area. Taken together with oxygen isotope data, this indicates that the entire Cherokee–Ozark Platform region was affected by the same fluids or fluids of similar temperature and composition during late diagenesis.

Oxygen Isotope Compositions of Cement-Depositing Waters

The δ18O values of carbonate cements are a function of several factors including temperature, the original δ18O value of the cement-depositing fluid, and the extent of fluid–rock interaction along the fluid’s flow paths. To unravel the history of fluids that precipitated the cements, equilibrium δ18Owater  values were calculated. These values may allow us to determine whether the fluids that deposited carbonate cements were in isotopic equilibrium with the local host rock carbonates or instead, reflect nonresident fluids that retained their source-derived oxygen isotope signatures (Shelton et al., 2011). Another possibility is that the δ18Owater values may reflect the presence of both resident and nonresident fluids with the potential of fluid mixing.

Equilibrium δ18Owater values (VSMOW) for fluids that precipitated calcite and dolomite cements were calculated using fractionation equations from O’Neil et al. (1969) for calcite-water and Northrop and Clayton (1966) for dolomite-water (Table 5, Figure 15). Temperatures utilized for the calculations are based on ranges of Th values for fluid inclusions in the carbonate cements. For comparison, the δ18Owater  values in equilibrium with the host limestone were calculated for the same temperatures (O’Neil et al., 1969).

Table 5.

Th values of fluid inclusions, δ18O values of carbonate cements, and calculated δ18O values of waters in equilibrium with these cements and their host rocks at the temperatures shown. The equation used for calcite cements is O’Neil et al. (1969) and that for dolomite cements is Northrop and Clayton (1966). The mean δ18O values (VSMOW) for the host limestone in the study area is 28.2.

SampleLocation and Host CementTh°Cδ18Ocalcite‰ VSMOWδ18Odolomite‰ VSMOWδ18Ocement-depositing water‰ VSMOW
JC5McDonald Co., MO, Calcite87 to 14022.43.9 to 8.9
SMD2100Osage Co., OK #1, Calcite80 to 12026.87.3 to 11.8
SMD2102Osage Co., OK #2, Calcite115, 135, 149, 17324.59.0, 11.0, 11.9, 13.5
TSNC1-14Neck City, MO, Calcite54 to 9819.5−3.2 to 2.3
H2-13-663Wagoner Co., OK #1, Calcite84 to 11821.42.4 to 5.9
H2-13-675Wagoner Co., OK #2, Calcite61 to 7121.4−0.6 to 0.9
SMD1002Benton Co., AR, Calcite116 to 15022.26.7 to 9.6
SMD-P1Mayes Co., OK #1, Calcite8819.81.3
SMD-P3Mayes Co., OK #2, Calcite44, 89, 97, 14519.1−5.5, 0.6, 1.6, 6.1
SMD-P5Mayes Co., OK #3, Dolomite63 to 7521.1−4.9 to −2.9
TSWB2-3Tri-State, Trecee, KS, Dolomite11322.62.6
TSAB1Anna Beaver Mine, OK, Dolomite103 to 11624.33.3 to 4.8
TSA-1Admiralty Mine, OK, Dolomite111, 128, 14223.75.7 to 6.9
SampleLocation and Host CementTh°Cδ18Ocalcite‰ VSMOWδ18Odolomite‰ VSMOWδ18Ocement-depositing water‰ VSMOW
JC5McDonald Co., MO, Calcite87 to 14022.43.9 to 8.9
SMD2100Osage Co., OK #1, Calcite80 to 12026.87.3 to 11.8
SMD2102Osage Co., OK #2, Calcite115, 135, 149, 17324.59.0, 11.0, 11.9, 13.5
TSNC1-14Neck City, MO, Calcite54 to 9819.5−3.2 to 2.3
H2-13-663Wagoner Co., OK #1, Calcite84 to 11821.42.4 to 5.9
H2-13-675Wagoner Co., OK #2, Calcite61 to 7121.4−0.6 to 0.9
SMD1002Benton Co., AR, Calcite116 to 15022.26.7 to 9.6
SMD-P1Mayes Co., OK #1, Calcite8819.81.3
SMD-P3Mayes Co., OK #2, Calcite44, 89, 97, 14519.1−5.5, 0.6, 1.6, 6.1
SMD-P5Mayes Co., OK #3, Dolomite63 to 7521.1−4.9 to −2.9
TSWB2-3Tri-State, Trecee, KS, Dolomite11322.62.6
TSAB1Anna Beaver Mine, OK, Dolomite103 to 11624.33.3 to 4.8
TSA-1Admiralty Mine, OK, Dolomite111, 128, 14223.75.7 to 6.9
Figure 15.

Calculated δ18Owater  values in equilibrium with calcite and dolomite cements and host limestones, using temperature ranges determined from fluid inclusions Th values. Fractionation equations employed are from Friedman and O’Neil (1977) and O’Neil et al. (1969).

Figure 15.

Calculated δ18Owater  values in equilibrium with calcite and dolomite cements and host limestones, using temperature ranges determined from fluid inclusions Th values. Fractionation equations employed are from Friedman and O’Neil (1977) and O’Neil et al. (1969).

Figure 15 shows calculated δ18O values for waters in equilibrium with calcite and dolomite cements from various localities (black and blue lines, respectively) and for waters in equilibrium with host limestones (pink lines). An important observation is that the calculated δ18Owater  values for calcite and dolomite cements vary considerably (from 5 to +12) and do not define a single end-member water. Neither do they show a correspondence between temperature (inferred depth of burial) and δ18Owater  values. This might reflect (1) isotopic differences in the fluid source regions, (2) differences in lithologies encountered along flow paths, or (3) varying water to rock ratios associated with types of fluid flow (i.e., lack of reaction along fault pathways versus extensive reaction during stratigraphically controlled flow).

The δ18Owater  values calculated for both calcite and dolomite cements in all four regions of the study area typically differ substantially from calculated δ18Owater  values in equilibrium with the host limestone. The variation of δ18Owater  values for the carbonate cements compared to those calculated for the host limestone indicates that waters that deposited the cements were not in isotopic equilibrium with the local host rocks (limestone). Their elevated 87Sr/86Sr ratios, compared to those of Mississippian limestones, further supports this interpretation (Figure 13).

Overlapping δ18Owater values for carbonate cement and host limestone observed at Osage County, Oklahoma (region B), indicate that the cement-depositing fluids approached isotopic equilibrium with local carbonate rocks, likely reflecting a large degree of reaction along flow paths at low water/rock ratios. Alternatively, the overlap in values could represent mixing between resident and nonresident fluids, dominated by the resident fluids in equilibrium with the host limestones. The intermediate Th values of different fluid compositions are consistent with variable mixing throughout the region (Figure 15).

Conceptual Model

A regional fluid flow model is shown in Figure 16 in which large volumes of fluid from the underlying aquifer moved up along faults and fractures and mixed with more dilute resident fluids in overlying Mississippian rocks. There is abundant evidence that saline brines, at similar temperatures and salinities to those observed in Mississippian rocks, were ubiquitous in underlying Cambrian and Ordovician strata (Leach et al., 1975; Shelton et al., 1992; Temple, 2016). The likely primary drive for the saline fluids is a regional gravity-driven system postulated as a result of the Ouachita orogeny (Leach, 1994; Appold and Garven, 1999; Gregg and Shelton, 2012). Pulses of saline fluids moved upward along faults and fractures into the overlying Mississippian strata and displaced resident lower salinity fluids. During periods between pulses of saline fluids, the resident fluids reasserted themselves. A similar model was proposed by Shelton et al. (2011) for Mississippian age fracture-related dolomitization and sulfide mineralization on the Isle of Man. An alternative hypothesis, that dilute fluids sourced from overlying strata migrated downward through Mississippian strata, possibly driven by thermal buoyancy, is not as well supported by the data. The overlying Pennsylvanian strata are relatively shale-rich and impermeable. Also, if the overlying strata were the source of the dilute fluid it would be expected that inclusions of these fluids would have displayed lower Th values.

Figure 16.

Conceptual model for late diagenetic fluid flow in the southern midcontinent showing: (A) saline fluids from the underlying Ordovician moving up along faults and fractures and mixing with dilute fluids present in the Mississippian strata and (B) the fluid migration model applied separately to the four regions in the study area.

Figure 16.

Conceptual model for late diagenetic fluid flow in the southern midcontinent showing: (A) saline fluids from the underlying Ordovician moving up along faults and fractures and mixing with dilute fluids present in the Mississippian strata and (B) the fluid migration model applied separately to the four regions in the study area.

High 87Sr/86Sr values of carbonate cements in the Mississippian rocks (Figure 13) suggest interaction of the cement-depositing fluids with continental basement or arkosic sandstone derived from continental basement. Elevated 87Sr/86Sr values also could indicate a continental shale source for fluids, but the underlying Woodford Shale is relatively thin or absent throughout most of the study area. Furthermore, previous fluid inclusion and isotope studies of underlying Cambrian carbonates in the Ozark region indicate that those strata are a potential source of saline brines with high 87Sr/86Sr values derived from interaction with underlying basement rocks (Shelton et al., 1992, 2009). These studies and others (e.g., Gregg, 1985; Gregg and Shelton, 1989; Rowan and Leach, 1989; Bethke and Marshak, 1990; Appold and Garven, 1999; Appold and Nunn, 2005) indicate that regional flow of basinal brines and associated mineralization throughout the Cherokee–Ozark platform region was associated with the Ouachita orogeny and involved flow of fluids through deep Cambrian–Ordovician and basement aquifers.

Goldstein and King (2014), in a study of Cambrian through Mississippian strata in the midcontinent, suggested a three-stage late diagenetic history based on petrographic, fluid inclusion, and isotope data. Their study area is located in southeastern Kansas, partly overlapping with our study area in southwestern Missouri and northeastern Oklahoma. Stage 1 is characterized by authigenic megaquartz and was interpreted to be related to relatively early migration of dilute fluids, prior to regional reflux of Permian brines. This was based on fluid inclusions with relatively low salinities (36 wt. % NaCl). Stage 2 is characterized by the widespread presence of saddle (baroque) dolomite cements containing high-salinity fluid inclusions (1523 wt. % NaCl) and radiogenic Sr isotope values. They attributed this event to advective flow of brines northward out of the Anadarko and Arkoma basins during the Ouachita orogeny. Stage 3 is less well constrained, but is characterized by late-stage calcite cements. A lack of uniformity in stable and radiogenic isotope values in these cements was interpreted to indicate more localized fluid flow events than during stage 2. They hypothesized that stage 3 was related to reactivation of faults during the Laramide orogeny.

In contrast to the conclusions of Goldstein and King (2014), we documented both saline and dilute fluid inclusions in quartz, saddle dolomite, and calcite cements in Mississippian strata throughout the study area (Figure 10). Our diagenetic paragenesis indicates that late-stage calcite and authigenic quartz cements both predate and postdate saddle dolomite cements. Petroleum-rich fluid inclusions were observed in both saddle dolomite and calcite cements. A specific trend of early dilute fluids followed by saline fluids was not observed; rather our data suggest an alternation between the influences of two fluid end members during late diagenesis.

Implications for the Mississippian Petroleum System on the Southern Mid-continent

Data from our study area indicate the regional importance of hydrothermal fluid flow on Mississippian carbonates in the southern midcontinent. Most of the fracture and breccia porosity and much of the intergrain and vug porosity is filled by carbonate cements that are demonstrably late diagenetic. Some of these contain petroleum inclusions (Figure 9) and two-phase aqueous fluid inclusions (Table 1). These observations indicate that cementation occurred during migration of petroleum in the system.

Porosity and permeability in the Mississippian carbonate rocks in the southern midcontinent likely remained relatively high through early seawater and meteoric diagenesis. Ritter and Goldstein (2012) estimated an original mean porosity of 42% for bioclastic grainstones in Osagean–Meramecian rocks in Kansas and Missouri north of and overlapping with our study area. They estimated that original porosity was reduced to a mean porosity of 18% following initial stages of diagenesis. Late-stage cementation reduced much of the rest of this porosity (Ritter and Goldstein, 2012). This study indicates that similar stages of porosity loss due to early and late diagenesis extended southward and eastward into eastern Oklahoma and western Arkansas. This means that Mississippian lithologies maintained relatively high porosity through early seawater and meteoric diagenesis and well into the period of petroleum migration when late diagenetic cements occluded much of the remaining porosity.

Regional flow of warm basinal fluids may also have perturbed the regional thermal gradient in the midcontinent, including the study area, relative to that which could be attributed to burial alone (Newell, 1997). As was suggested by Goldstein and King (2014), this likely impacted the thermal maturity of the region and enhanced the generation of hydrocarbons in the Mississippian carbonates as well as in underlying and overlying source rocks.

Conclusions

Mississippian carbonate rocks in the Cherokee and Ozark platform region were cemented by seawater followed by mixed seawater and meteoric waters during early diagenesis as indicated by petrographic fabrics and carbon, oxygen, and strontium isotope geochemistry. This early cementation partially filled primary intragrain, intergrain, and vug porosity. Remaining primary porosity, as well as late diagenetic fracture and breccia porosity was filled by calcite, dolomite, and quartz cements that were precipitated by evolved basinal fluids as indicated by isotope geochemistry and fluid inclusion microthermometry. Two-phase fluid inclusions display Th values of  50to175°C and salinities of 0to25 equivalent wt. % NaCl.

Analysis of fluid inclusion data indicate that two distinct fluids were present in the study area during late diagenesis: a dilute fluid having salinities ranging from 0 to 10 wt. % NaCl equivalent and a saline fluid with salinities ranging from 15 to 25 wt. % NaCl equivalent. Radiogenic Sr isotope values for fracture- and breccia-filling cements indicate that one of these fluids likely interacted with continental basement. A model is presented where an evolved saline fluid moved up through faults and fractures from underlying Cambrian–Ordovician strata and displaced or mixed with a dilute resident fluid.

Migration of late diagenetic fluids through the study area likely corresponded with the emplacement of sulfides in the Tri-State MVT district. The basinal fluids were accompanied by petroleum migration as indicated by the presence of petroleum inclusions in some of these cements. The regional flow of warm basinal fluids likely increased the geothermal gradient in the region, affecting the thermal maturity of the rocks. Porosity and permeability of the Mississippian carbonate rocks likely remained relatively high prior to and during migration of these fluids.

ACKNOWLEDGMENTS

This study was supported by the Oklahoma State University-Industry Mississippian Consortium and the Boone Pickens School of Geology. We thank all of the companies that supported this Consortium. Also, thanks to the National Association of Black Geoscientists (NABG) for financial support for SM during this study. Thanks are due to Dr. Eliot Atekwana and Dr. Kenneth MacLeod for use of the isotope laboratory facilities at Oklahoma State University and University of Missouri, respectively. Also we would like to thank Morgan Unrast and Cory Godwin for providing some samples from their independent studies of the Mississippian carbonates. Thanks are due to Francis C. Furman who contributed samples from the Tri-State Mineral District for the study. We thank Michael Grammer, Jeffrey White, Gordon MacLeod, and Abbas Seyedolali for their valuable comments and suggestions. Finally, we thank R. D. Hagni and Jeff Lonnee for their concise reviews and G. Michael Grammer for his editorial handling of this manuscript.

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Figures & Tables

Figure 1.

Map of Oklahoma and neighboring states showing the study area (tan rectangle in the east–central portion of the map) and sample localities. Four sampling regions within the study area are shown: “A” cores in Osage County, Oklahoma, “B” surface samples and core in and near the Tri-State MVT mineral district, “C” core and outcrops on and near the Seneca Trough in Delaware, Wagoner, and Mayes counties, northeast Oklahoma, and “D” core and outcrops in McDonald and Stone counties, southwest Missouri and Benton and Boone counties, northwest Arkansas. Petroleum-producing areas and thickness of the Mississippian strata also are shown. Modified from Harris (1987).

Figure 1.

Map of Oklahoma and neighboring states showing the study area (tan rectangle in the east–central portion of the map) and sample localities. Four sampling regions within the study area are shown: “A” cores in Osage County, Oklahoma, “B” surface samples and core in and near the Tri-State MVT mineral district, “C” core and outcrops on and near the Seneca Trough in Delaware, Wagoner, and Mayes counties, northeast Oklahoma, and “D” core and outcrops in McDonald and Stone counties, southwest Missouri and Benton and Boone counties, northwest Arkansas. Petroleum-producing areas and thickness of the Mississippian strata also are shown. Modified from Harris (1987).

Figure 2.

Regional map showing Burlington shelf depositional systems during the early Mississippian. The study area is outlined by a red rectangle. Modified from Lane and DeKyser (1980).

Figure 2.

Regional map showing Burlington shelf depositional systems during the early Mississippian. The study area is outlined by a red rectangle. Modified from Lane and DeKyser (1980).

Figure 3.

Stratigraphic section for the study area, modified from Mazzullo et al. (2013). CHEST = Chesterian; MERA = Meramecian.

Figure 3.

Stratigraphic section for the study area, modified from Mazzullo et al. (2013). CHEST = Chesterian; MERA = Meramecian.

Figure 4.

(A) Skeletal grainstone from the Pierson Formation, Benton County, Arkansas. Bladed calcite cement (b) growing on brachiopod shells and equant (blocky) calcite cement (e) filling remaining porosity. Crossed polarized light (XPL). (B) Cathodoluminescence (CL) photomicrograph of the same field as (A). Note the apparent compositional zoning of the equant calcite cement. (C) Rugose coral, Osage County, Oklahoma, with intragrain porosity filled by bladed and equant calcite cements. Plane polarized light (PPL). (D) CL photomicrograph of the same field as (C) showing compositional zoning in the bladed and equant calcite cements. (E) Crinoid grainstone from the Pierson Formation, Delaware County, Oklahoma. Porosity is largely filled by syntaxial and equant calcite cement. XPL. (F) CL photomicrograph of the same field as (E). Initial syntaxial cement (dark zone 2) extending into banded zones 3 and 4 cement.

Figure 4.

(A) Skeletal grainstone from the Pierson Formation, Benton County, Arkansas. Bladed calcite cement (b) growing on brachiopod shells and equant (blocky) calcite cement (e) filling remaining porosity. Crossed polarized light (XPL). (B) Cathodoluminescence (CL) photomicrograph of the same field as (A). Note the apparent compositional zoning of the equant calcite cement. (C) Rugose coral, Osage County, Oklahoma, with intragrain porosity filled by bladed and equant calcite cements. Plane polarized light (PPL). (D) CL photomicrograph of the same field as (C) showing compositional zoning in the bladed and equant calcite cements. (E) Crinoid grainstone from the Pierson Formation, Delaware County, Oklahoma. Porosity is largely filled by syntaxial and equant calcite cement. XPL. (F) CL photomicrograph of the same field as (E). Initial syntaxial cement (dark zone 2) extending into banded zones 3 and 4 cement.

Figure 5.

(A) Packstone to grainstone with intergrain porosity filled by calcite, McDonald County, Missouri. PPL. (B) CL photomicrograph of the same field as (A) showing four compositional zones (2, 3, 4, and 5) in the equant calcite cement. (C) Grainstone with intragrain porosity filled by calcite, Benton County, Arkansas. Close-up of field shown in Figure 4A, PPL. (D) CL photomicrograph of the same field as (C) showing compositional zoning of the equant calcite cement (zones 1, 2, 3, and 4).

Figure 5.

(A) Packstone to grainstone with intergrain porosity filled by calcite, McDonald County, Missouri. PPL. (B) CL photomicrograph of the same field as (A) showing four compositional zones (2, 3, 4, and 5) in the equant calcite cement. (C) Grainstone with intragrain porosity filled by calcite, Benton County, Arkansas. Close-up of field shown in Figure 4A, PPL. (D) CL photomicrograph of the same field as (C) showing compositional zoning of the equant calcite cement (zones 1, 2, 3, and 4).

Figure 6.

(A) Cherty mudstone in the Reeds Spring Formation, Benton County, Arkansas. Solution-widened fracture (channel) porosity is filled by equant calcite cement. PPL. (B) CL photomicrograph of the same field as (A) showing compositional zoning in the equant calcite cement. (C) Cherty mudstone, Osage County Oklahoma, with a ptygmatic fracture filled by equant calcite cement. XPL, composite of nine photomicrographs.

Figure 6.

(A) Cherty mudstone in the Reeds Spring Formation, Benton County, Arkansas. Solution-widened fracture (channel) porosity is filled by equant calcite cement. PPL. (B) CL photomicrograph of the same field as (A) showing compositional zoning in the equant calcite cement. (C) Cherty mudstone, Osage County Oklahoma, with a ptygmatic fracture filled by equant calcite cement. XPL, composite of nine photomicrographs.

Figure 7.

(A) Solution-widened fracture (channel) porosity and unmodified breccia porosity, Osage County, Oklahoma are filled by quartz and equant calcite cement. XPL, composite of 16 photomicrographs. The close-up field is shown by the yellow rectangle. (B) Close-up of a solution-widened fracture, shown in (A), filled by chalcedony quartz (q) and equant calcite (e) cement. XPL. (C) CL photomicrograph of the same field as (B). Quartz cement is non cathodoluminescent and no compositional zoning is apparent in the calcite cement.

Figure 7.

(A) Solution-widened fracture (channel) porosity and unmodified breccia porosity, Osage County, Oklahoma are filled by quartz and equant calcite cement. XPL, composite of 16 photomicrographs. The close-up field is shown by the yellow rectangle. (B) Close-up of a solution-widened fracture, shown in (A), filled by chalcedony quartz (q) and equant calcite (e) cement. XPL. (C) CL photomicrograph of the same field as (B). Quartz cement is non cathodoluminescent and no compositional zoning is apparent in the calcite cement.

Figure 8.

(A) Replacement dolomite, Mayes County, Oklahoma. PPL. (B) CL photomicrograph of the same field as (A). (C) Dolomitized mudstone with a solution-widened fracture filled by saddle dolomite, Cherokee County, Kansas. PPL. (D) CL photomicrograph of the same field as (C) showing compositional zoning in the dolomite cement. (E) Saddle dolomite cement, Tri-State MVT district, Picher-field, Admiralty Mine (#3 Shaft) Oklahoma. XPL, composite of four photomicrographs. (F) CL photomicrograph of the same field as (E) showing compositional zoning in the dolomite cement.

Figure 8.

(A) Replacement dolomite, Mayes County, Oklahoma. PPL. (B) CL photomicrograph of the same field as (A). (C) Dolomitized mudstone with a solution-widened fracture filled by saddle dolomite, Cherokee County, Kansas. PPL. (D) CL photomicrograph of the same field as (C) showing compositional zoning in the dolomite cement. (E) Saddle dolomite cement, Tri-State MVT district, Picher-field, Admiralty Mine (#3 Shaft) Oklahoma. XPL, composite of four photomicrographs. (F) CL photomicrograph of the same field as (E) showing compositional zoning in the dolomite cement.

Figure 9.

Photomicrographs of fluid inclusions in cements. (A) Assemblage of primary two-phase inclusions in open-space-filling calcite cement, Tri-State Mineral District, Neck City, Missouri. (B) Secondary inclusions in fracture-filling calcite cement, Mayes County, Oklahoma. (C) Primary inclusions in fracture-filling saddle dolomite cement, Mayes County, Oklahoma. (D) Primary inclusions in solution-widened fracture-filling quartz cement, Osage County, Oklahoma. (E) Assemblage of primary petroleum-bearing inclusions in fracture-filling calcite cement, Wagoner County, Oklahoma. (F) Ultraviolet photomicrograph from the same field as (E) showing light-blue fluorescence of petroleum-bearing inclusions.

Figure 9.

Photomicrographs of fluid inclusions in cements. (A) Assemblage of primary two-phase inclusions in open-space-filling calcite cement, Tri-State Mineral District, Neck City, Missouri. (B) Secondary inclusions in fracture-filling calcite cement, Mayes County, Oklahoma. (C) Primary inclusions in fracture-filling saddle dolomite cement, Mayes County, Oklahoma. (D) Primary inclusions in solution-widened fracture-filling quartz cement, Osage County, Oklahoma. (E) Assemblage of primary petroleum-bearing inclusions in fracture-filling calcite cement, Wagoner County, Oklahoma. (F) Ultraviolet photomicrograph from the same field as (E) showing light-blue fluorescence of petroleum-bearing inclusions.

Figure 10.

(A) Plots of fluid inclusion salinities versus Th values. (B) Fluid inclusion salinities and Th values grouped as assemblages. The number of individual fluid inclusions for which valid Th and Tm values were measured are shown on each data point. Data fields are shown for fluid inclusions measurements made in previous studies in and near the Tri-State MVT district.

Figure 10.

(A) Plots of fluid inclusion salinities versus Th values. (B) Fluid inclusion salinities and Th values grouped as assemblages. The number of individual fluid inclusions for which valid Th and Tm values were measured are shown on each data point. Data fields are shown for fluid inclusions measurements made in previous studies in and near the Tri-State MVT district.

Figure 11.

Fluid inclusion assemblages plotted among the four regions in the study area (see Figure 1).

Figure 11.

Fluid inclusion assemblages plotted among the four regions in the study area (see Figure 1).

Figure 12.

Values of δ18O and δ13C (per mil VPDB) for carbonate samples from the study area. The region for calcite in equilibrium with Mississippian seawater (Mii et al., 1999) is shown as well as the regions attributed to fresh phreatic and seawater mixing and late diagenetic calcite. The fields occupied by intermediate- and late-stage calcite cements of Ritter and Goldstein (2012) and equant calcite cements of Morris et al. (2013) are also shown.

Figure 12.

Values of δ18O and δ13C (per mil VPDB) for carbonate samples from the study area. The region for calcite in equilibrium with Mississippian seawater (Mii et al., 1999) is shown as well as the regions attributed to fresh phreatic and seawater mixing and late diagenetic calcite. The fields occupied by intermediate- and late-stage calcite cements of Ritter and Goldstein (2012) and equant calcite cements of Morris et al. (2013) are also shown.

Figure 13.

Values of 87Sr/86Sr plotted against δ18O values for carbonate samples of the study area. Limestone in equilibrium with Mississippian seawater is shown as the light blue field (Bruckschen et al., 1999; Mii et al., 1999).

Figure 13.

Values of 87Sr/86Sr plotted against δ18O values for carbonate samples of the study area. Limestone in equilibrium with Mississippian seawater is shown as the light blue field (Bruckschen et al., 1999; Mii et al., 1999).

Figure 14.

Paragenetic sequence for diagenetic events in the study area. The dashed lines indicate uncertain timing.

Figure 14.

Paragenetic sequence for diagenetic events in the study area. The dashed lines indicate uncertain timing.

Figure 15.

Calculated δ18Owater  values in equilibrium with calcite and dolomite cements and host limestones, using temperature ranges determined from fluid inclusions Th values. Fractionation equations employed are from Friedman and O’Neil (1977) and O’Neil et al. (1969).

Figure 15.

Calculated δ18Owater  values in equilibrium with calcite and dolomite cements and host limestones, using temperature ranges determined from fluid inclusions Th values. Fractionation equations employed are from Friedman and O’Neil (1977) and O’Neil et al. (1969).

Figure 16.

Conceptual model for late diagenetic fluid flow in the southern midcontinent showing: (A) saline fluids from the underlying Ordovician moving up along faults and fractures and mixing with dilute fluids present in the Mississippian strata and (B) the fluid migration model applied separately to the four regions in the study area.

Figure 16.

Conceptual model for late diagenetic fluid flow in the southern midcontinent showing: (A) saline fluids from the underlying Ordovician moving up along faults and fractures and mixing with dilute fluids present in the Mississippian strata and (B) the fluid migration model applied separately to the four regions in the study area.

Table 1.

Fluid inclusion microthermometric data for carbonate and authigenic quartz cements.

Sample IDLocationAssemblageMineralTh(°C)Tm(°C)Calculated Salinity (wt. % eq. NaCl)
SMD 2100Osage Co., OK (#1)Assemblage 1Calcite970.71.2
  Assemblage 2Calcite1120.50.8
   Calcite1180.50.8
   Calcite1180.50.8
  Assemblage 3Calcite810.10.2
   Calcite1050.10.2
   Calcite841.52.6
   Calcite 0.50.9
  Assemblage 4Calcite872.5 
   Calcite802.5 
   Calcite 0.3 
   Calcite105  
  Assemblage 5Calcite813.0 
  Assemblage 6Calcite1160.7 
SMD 2102Osage Co., OK (#2)Assemblage 1Calcite126−3.76.0
   Calcite1261.83.0
   Calcite1253.86.1
  Assemblage 2Calcite1641.93.2
   Calcite1491.93.2
  Assemblage 3Calcite11521.022.8
   Calcite11819.021.7
   Calcite 19.021.7
   Calcite 15.419.0
   Calcite127  
  Assemblage 4Calcite17317.520.6
   Calcite16815.419.0
  Assemblage 5Calcite8623.024.3
  Assemblage 6Calcite12223.024.3
   Calcite12621.223.1
  Assemblage 7Calcite1352.13.5
  Assemblage 8Quartz12621.623.4
   Quartz13021.623.4
   Quartz10121.623.4
   Quartz13021.623.4
  Assemblage 9Quartz8319.622.1
   Quartz8719.622.1
   Quartz9822.323.9
   Quartz9818.621.4
   Quartz9817.820.8
   Quartz9818.521.3
  Assemblage 10Quartz1222.03.4
   Quartz1232.94.8
   Quartz1191.42.4
   Quartz1131.42.4
  Assemblage 11Quartz1022.33.9
   Quartz1022.03.4
   Quartz1082.33.9
   Quartz1080.40.7
SMD 1002Benton Co., ARAssemblage 1Calcite12011.215.2
  Assemblage 2Calcite13219.021.7
   Calcite13522.624.0
   Calcite 22.624.0
  Assemblage 3Calcite12520.722.8
   Calcite12519.522.0
   Calcite13521.023.0
   Calcite13921.423.3
   Calcite11621.423.3
  Assemblage 4Calcite1492.44.0
   Calcite1382.94.8
   Calcite1472.94.8
  Assemblage 5Calcite1205.07.8
  Assemblage 6Calcite10119.622.1
SMD-P1Mayes Co., OK (#1)Assemblage 1Calcite20018.521.3
  Assemblage 2Calcite880.40.7
  Assemblage 3Calcite 19.622.1
  Assemblage 4Calcite 1.72.9
  Assemblage 5Calcite 1.5 
SMD-P3Mayes Co., OK (#2)Assemblage 1Calcite1128.912.7
   Calcite1143.55.7
  Assemblage 2Calcite1043.65.8
   Calcite1043.15.1
   Calcite1053.15.1
   Calcite1054.26.7
   Calcite1054.26.7
   Calcite1054.26.7
  Assemblage 3Calcite1307.611.2
   Calcite1196.69.9
   Calcite1287.210.7
   Calcite133  
  Assemblage 4Calcite670.7 
   Calcite670.7 
   Calcite670.7 
   Calcite530.7 
  Assemblage 5Calcite972.03.4
   Calcite743.35.4
  Assemblage 6Calcite674.57.2
   Calcite881.72.9
  Assemblage 7Calcite430.71.2
   Calcite740.20.3
   Calcite740.20.3
   Calcite550.20.3
  Assemblage 8Calcite1452.54.1
  Assemblage 9Calcite801.0 
   Calcite701.0 
   Calcite701.0 
   Calcite701.0 
   Calcite701.0 
   Calcite721.0 
   Calcite971.0 
SMD-P5Mayes Co., OK (#3)Assemblage 1Dolomite628.211.9
   Dolomite7513.016.9
   Dolomite6513.016.9
TSNC1-14Tri-State, Neck City, MOAssemblage 1Calcite765.58.5
   Calcite844.47.0
  Assemblage 2Calcite903.35.4
  Assemblage 3Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
  Assemblage 4Calcite594.0 
   Calcite614.0 
   Calcite65  
  Assemblage 5Calcite74  
   Calcite740.7 
  Assemblage 6Calcite860.00.0
   Calcite940.00.0
   Calcite900.00.0
   Calcite90  
   Calcite56  
   Calcite86  
   Calcite980.6 
TSOG2Tri-State, Old Goat Mine, Treece, KSAssemblage 1Calcite89  
JC5McDonald Co., MOAssemblage 1Calcite1291.7 
   Calcite 2.2 
   Calcite 2.2 
   Calcite1400.7 
   Calcite 2.2 
  Assemblage 2Calcite1291.52.6
  Assemblage 3Calcite158  
  Assemblage 4Calcite 0.00.0
  Assemblage 5Calcite11221.823.6
   Calcite9521.823.6
   Calcite8621.823.6
   Calcite11221.823.6
   Calcite 21.823.6
  Assemblage 6Calcite114  
   Calcite114  
   Calcite114  
   Calcite114  
   Calcite114  
TSA-1Tri-State, Admiralty Mine (#1)Assemblage 1Dolomite14224.325.1
  Assemblage 2Dolomite10315.519.0
  Assemblage 3Dolomite13023.224.5
   Dolomite13523.724.8
   Dolomite12822.724.1
   Dolomite13021.823.6
   Dolomite13523.624.7
  Assemblage 4Dolomite12724.025.0
   Dolomite8316.519.8
   Dolomite 23.524.6
   Dolomite 18.521.3
   Dolomite 20.322.6
TSA-4Tri-State, Admiralty Mine (#2)Assemblage 1Dolomite111  
   Dolomite111  
  Assemblage 2Sphalerite107  
TSAB1Tri-State, Anna Beaver Mine, OKAssemblage 1Dolomite10224.425.2
   Dolomite11620.322.6
  Assemblage 2Dolomite11224.225.0
   Dolomite11222.023.7
   Dolomite11217.920.9
   Dolomite10221.423.3
   Dolomite 23.624.7
  Assemblage 3Dolomite1122.44.0
   Dolomite1122.44.0
   Dolomite 3.55.7
  Assemblage 4Dolomite11021.223.2
   Dolomite1072022.4
   Dolomite 25.225.7
   Dolomite 22.924.3
   Dolomite 22.924.3
   Dolomite 2022.4
TSPF1Tri-State, Ottawa Co., OKAssemblage 1Calcite19821.723.5
  Assemblage 2Calcite 6.810.2
TSW-1Tri-State, Wood Chuck Mine, OKAssemblage 1Sphalerite170  
   Sphalerite178  
TSWB-3-3BTri-State, Treece, KSAssemblage 1Dolomite11223.324.5
   Dolomite 16.019.5
  Assemblage 2Dolomite151  
H2-13-663Wagoner Co., OK (#1)Assemblage 1Calcite10918.021.0
   Calcite11316.119.5
  Assemblage 2Calcite114  
   Calcite117  
   Calcite101  
   Calcite101  
   Calcite112  
  Assemblage 3Calcite115  
   Calcite115  
   Calcite115  
  Assemblage 4Calcite870.9 
   Calcite86  
   Calcite986.610.0
  Assemblage 5Calcite857.811.5
   Calcite741.83.0
   Calcite741.83.0
  Assemblage 6Calcite6214.1 
   Calcite6214.1 
  Assemblage 7Calcite151  
  Assemblage 8Calcite83  
   Calcite91  
   Calcite85  
   Calcite99  
   Calcite99  
  Assemblage 9Calcite1102.33.9
   Calcite1102.33.9
   Calcite1102.33.9
H2-13-675Wagoner Co., OK (#2)Assemblage 1Calcite99  
   Calcite10315.318.9
  Assemblage 2Calcite711.6 
  Assemblage 3Calcite61  
   Calcite660.10.2
   Calcite660.10.2
  Assemblage 4Quartz11613.117.0
   Quartz9211.415.4
  Assemblage 5Quartz891.42.4
   Quartz891.42.4
   Quartz891.42.4
   Quartz891.42.4
   Quartz891.42.4
   Quartz941.42.4
  Assemblage 6Quartz1533.45.6
   Quartz1533.45.6
   Quartz1533.45.6
   Quartz1533.45.6
   Quartz1533.45.6
  Assemblage 7Quartz1723.45.6
Sample IDLocationAssemblageMineralTh(°C)Tm(°C)Calculated Salinity (wt. % eq. NaCl)
SMD 2100Osage Co., OK (#1)Assemblage 1Calcite970.71.2
  Assemblage 2Calcite1120.50.8
   Calcite1180.50.8
   Calcite1180.50.8
  Assemblage 3Calcite810.10.2
   Calcite1050.10.2
   Calcite841.52.6
   Calcite 0.50.9
  Assemblage 4Calcite872.5 
   Calcite802.5 
   Calcite 0.3 
   Calcite105  
  Assemblage 5Calcite813.0 
  Assemblage 6Calcite1160.7 
SMD 2102Osage Co., OK (#2)Assemblage 1Calcite126−3.76.0
   Calcite1261.83.0
   Calcite1253.86.1
  Assemblage 2Calcite1641.93.2
   Calcite1491.93.2
  Assemblage 3Calcite11521.022.8
   Calcite11819.021.7
   Calcite 19.021.7
   Calcite 15.419.0
   Calcite127  
  Assemblage 4Calcite17317.520.6
   Calcite16815.419.0
  Assemblage 5Calcite8623.024.3
  Assemblage 6Calcite12223.024.3
   Calcite12621.223.1
  Assemblage 7Calcite1352.13.5
  Assemblage 8Quartz12621.623.4
   Quartz13021.623.4
   Quartz10121.623.4
   Quartz13021.623.4
  Assemblage 9Quartz8319.622.1
   Quartz8719.622.1
   Quartz9822.323.9
   Quartz9818.621.4
   Quartz9817.820.8
   Quartz9818.521.3
  Assemblage 10Quartz1222.03.4
   Quartz1232.94.8
   Quartz1191.42.4
   Quartz1131.42.4
  Assemblage 11Quartz1022.33.9
   Quartz1022.03.4
   Quartz1082.33.9
   Quartz1080.40.7
SMD 1002Benton Co., ARAssemblage 1Calcite12011.215.2
  Assemblage 2Calcite13219.021.7
   Calcite13522.624.0
   Calcite 22.624.0
  Assemblage 3Calcite12520.722.8
   Calcite12519.522.0
   Calcite13521.023.0
   Calcite13921.423.3
   Calcite11621.423.3
  Assemblage 4Calcite1492.44.0
   Calcite1382.94.8
   Calcite1472.94.8
  Assemblage 5Calcite1205.07.8
  Assemblage 6Calcite10119.622.1
SMD-P1Mayes Co., OK (#1)Assemblage 1Calcite20018.521.3
  Assemblage 2Calcite880.40.7
  Assemblage 3Calcite 19.622.1
  Assemblage 4Calcite 1.72.9
  Assemblage 5Calcite 1.5 
SMD-P3Mayes Co., OK (#2)Assemblage 1Calcite1128.912.7
   Calcite1143.55.7
  Assemblage 2Calcite1043.65.8
   Calcite1043.15.1
   Calcite1053.15.1
   Calcite1054.26.7
   Calcite1054.26.7
   Calcite1054.26.7
  Assemblage 3Calcite1307.611.2
   Calcite1196.69.9
   Calcite1287.210.7
   Calcite133  
  Assemblage 4Calcite670.7 
   Calcite670.7 
   Calcite670.7 
   Calcite530.7 
  Assemblage 5Calcite972.03.4
   Calcite743.35.4
  Assemblage 6Calcite674.57.2
   Calcite881.72.9
  Assemblage 7Calcite430.71.2
   Calcite740.20.3
   Calcite740.20.3
   Calcite550.20.3
  Assemblage 8Calcite1452.54.1
  Assemblage 9Calcite801.0 
   Calcite701.0 
   Calcite701.0 
   Calcite701.0 
   Calcite701.0 
   Calcite721.0 
   Calcite971.0 
SMD-P5Mayes Co., OK (#3)Assemblage 1Dolomite628.211.9
   Dolomite7513.016.9
   Dolomite6513.016.9
TSNC1-14Tri-State, Neck City, MOAssemblage 1Calcite765.58.5
   Calcite844.47.0
  Assemblage 2Calcite903.35.4
  Assemblage 3Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
   Calcite544.2 
  Assemblage 4Calcite594.0 
   Calcite614.0 
   Calcite65  
  Assemblage 5Calcite74  
   Calcite740.7 
  Assemblage 6Calcite860.00.0
   Calcite940.00.0
   Calcite900.00.0
   Calcite90  
   Calcite56  
   Calcite86  
   Calcite980.6 
TSOG2Tri-State, Old Goat Mine, Treece, KSAssemblage 1Calcite89  
JC5McDonald Co., MOAssemblage 1Calcite1291.7 
   Calcite 2.2 
   Calcite 2.2 
   Calcite1400.7 
   Calcite 2.2 
  Assemblage 2Calcite1291.52.6
  Assemblage 3Calcite158  
  Assemblage 4Calcite 0.00.0
  Assemblage 5Calcite11221.823.6
   Calcite9521.823.6
   Calcite8621.823.6
   Calcite11221.823.6
   Calcite 21.823.6
  Assemblage 6Calcite114  
   Calcite114  
   Calcite114  
   Calcite114  
   Calcite114  
TSA-1Tri-State, Admiralty Mine (#1)Assemblage 1Dolomite14224.325.1
  Assemblage 2Dolomite10315.519.0
  Assemblage 3Dolomite13023.224.5
   Dolomite13523.724.8
   Dolomite12822.724.1
   Dolomite13021.823.6
   Dolomite13523.624.7
  Assemblage 4Dolomite12724.025.0
   Dolomite8316.519.8
   Dolomite 23.524.6
   Dolomite 18.521.3
   Dolomite 20.322.6
TSA-4Tri-State, Admiralty Mine (#2)Assemblage 1Dolomite111  
   Dolomite111  
  Assemblage 2Sphalerite107  
TSAB1Tri-State, Anna Beaver Mine, OKAssemblage 1Dolomite10224.425.2
   Dolomite11620.322.6
  Assemblage 2Dolomite11224.225.0
   Dolomite11222.023.7
   Dolomite11217.920.9
   Dolomite10221.423.3
   Dolomite 23.624.7
  Assemblage 3Dolomite1122.44.0
   Dolomite1122.44.0
   Dolomite 3.55.7
  Assemblage 4Dolomite11021.223.2
   Dolomite1072022.4
   Dolomite 25.225.7
   Dolomite 22.924.3
   Dolomite 22.924.3
   Dolomite 2022.4
TSPF1Tri-State, Ottawa Co., OKAssemblage 1Calcite19821.723.5
  Assemblage 2Calcite 6.810.2
TSW-1Tri-State, Wood Chuck Mine, OKAssemblage 1Sphalerite170  
   Sphalerite178  
TSWB-3-3BTri-State, Treece, KSAssemblage 1Dolomite11223.324.5
   Dolomite 16.019.5
  Assemblage 2Dolomite151  
H2-13-663Wagoner Co., OK (#1)Assemblage 1Calcite10918.021.0
   Calcite11316.119.5
  Assemblage 2Calcite114  
   Calcite117  
   Calcite101  
   Calcite101  
   Calcite112  
  Assemblage 3Calcite115  
   Calcite115  
   Calcite115  
  Assemblage 4Calcite870.9 
   Calcite86  
   Calcite986.610.0
  Assemblage 5Calcite857.811.5
   Calcite741.83.0
   Calcite741.83.0
  Assemblage 6Calcite6214.1 
   Calcite6214.1 
  Assemblage 7Calcite151  
  Assemblage 8Calcite83  
   Calcite91  
   Calcite85  
   Calcite99  
   Calcite99  
  Assemblage 9Calcite1102.33.9
   Calcite1102.33.9
   Calcite1102.33.9
H2-13-675Wagoner Co., OK (#2)Assemblage 1Calcite99  
   Calcite10315.318.9
  Assemblage 2Calcite711.6 
  Assemblage 3Calcite61  
   Calcite660.10.2
   Calcite660.10.2
  Assemblage 4Quartz11613.117.0
   Quartz9211.415.4
  Assemblage 5Quartz891.42.4
   Quartz891.42.4
   Quartz891.42.4
   Quartz891.42.4
   Quartz891.42.4
   Quartz941.42.4
  Assemblage 6Quartz1533.45.6
   Quartz1533.45.6
   Quartz1533.45.6
   Quartz1533.45.6
   Quartz1533.45.6
  Assemblage 7Quartz1723.45.6
Table 2.

Stable isotope analyses of carbonate cements and host rocks. Clay-size calcite referred to “calcite mud.”

SampleLocalityMineralogyδ13C‰ (VPDB)δ18O‰ (VPDB)δ18O‰ (VSMOW)
TSAB1Tri-State-Anna Beaver Mine, OKCalcite cement4.7510.9819.60
TSAB1Tri-State-Anna Beaver Mine, OKDolomite–nonplanar1.586.6824.04
TSAB1Tri-State-Anna Beaver Mine, OKDolomite cement1.686.4024.33
TSAB1Tri-State-Anna Beaver Mine, OKDolomite–nonplanar0.985.6125.13
TSW-1Tri-State-Wood Chuck Mine, OKDolomite–nonplanar1.557.1723.53
TSW-2Tri-State-Wood Chuck Mine, OKDolomite–nonplanar2.066.8823.83
TSA-1Tri-State, Admiralty Mine, OKDolomite–nonplanar1.557.0323.67
TSA-2Tri-State, Admiralty Mine, OKDolomite–nonplanar1.687.6123.07
TSA-3Tri-State, Admiralty Mine, OKDolomite cement1.537.7222.96
TSA-4Tri-State, Admiralty Mine, OKDolomite cement1.487.3523.35
TSP-1Tri-State-Premier Mine, OKDolomite cement1.346.1624.57
TSP-2Tri-State-Premier Mine, OKDolomite cement1.867.1723.52
TSOG-1Tri-State, Old Goat Mine, Treece, KSCalcite cement4.3510.2920.31
TSOG-2Tri-State, Old Goat Mine, Treece, KSCalcite cement4.5310.7119.88
SMD1002Benton Co., ARCalcite cement1.768.4522.21
SMD1008McDonald Co., MOCalcite cement2.843.1127.72
SMD2100Osage Co., OKCalcite cement2.584.0426.76
SMD2102Osage Co., OKCalcite cement2.586.2124.52
SMD2103Osage Co., OKCalcite cement0.907.0623.64
SMD3001White Rock Co., MOCalcite cement2.788.8621.78
PM21-608Cherokee Co., KSDolomite cement2.002.6628.18
PM21-608Cherokee Co., KSDolomite–planar0.423.8027.00
PM21-600Cherokee Co., KSSaddle dolomite1.196.2824.44
PM21-614Cherokee Co., KSReplacement dolomite2.025.8324.91
PM21-618Cherokee Co., KSReplacement dolomite2.304.4626.32
A04-1220Jasper Co., MOCalcite cement1.824.4026.38
B50-1-85.5Jasper Co., MOCalcite cement0.799.9320.68
J5.5McDonald Co., MOCalcite crinoid2.261.2629.62
JC2McDonald Co., MOCalcite cement3.183.8426.96
JC2McDonald Co., MOCalcite mud2.664.0426.75
JC4McDonald Co., MOCalcite cement2.905.0625.70
JC4McDonald Co., MOCalcite mud2.524.0626.73
JC5McDonald Co., MOCalcite cement1.948.3022.36
JC5McDonald Co., MOCalcite mud3.013.8626.94
JN2McDonald Co., MOCalcite crinoid3.562.4028.45
JS5McDonald Co., MOCalcite crinoid2.872.1128.74
SW1Stone Co., MOCalcite crinoid3.182.2928.56
SWCU2Stone Co., MOCalcite cement3.696.6424.08
SWCU2Stone Co., MOCalcite cement4.571.9028.96
SWCU4Stone Co., MOCalcite cement3.577.2423.46
SWCU4Stone Co., MOCalcite mud4.291.9128.96
SEP2Delaware Co., OKCalcite crinoid3.391.9028.96
SEP2Delaware Co., OKCalcite cement2.652.9827.85
PAEF2Benton Co., ARCalcite crinoid3.692.4928.36
PAEC5Benton Co., ARCalcite cement1.629.2121.43
PAEC5Benton Co., ARCalcite crinoid3.971.6829.19
PAWCBA2Benton Co., ARCalcite mud1.905.5725.18
PAWC2Benton Co., ARCalcite cement2.444.6626.11
PAWC4Benton Co., ARCalcite crinoid3.512.4328.41
PAWC1Benton Co., ARCalcite mud3.301.4329.44
PAWF1Benton Co., ARCalcite crinoid3.291.8429.02
PAEC4Benton Co., ARCalcite cement1.927.2823.42
PAEC4Benton Co., ARCalcite crinoid3.103.3527.47
H2-13-663AWagoner Co., OKCalcite cement2.039.2421.39
H2-13-663BWagoner Co., OKCalcite cement1.359.8920.73
H2-13-675BWagoner Co., OKCalcite cement1.869.2921.34
H2-13-675AWagoner Co., OKCalcite cement1.829.2521.39
H2-13-678Wagoner Co., OKCalcite cement1.869.3921.24
SMD-P1Mayes Co., OKCalcite cement12.1210.8319.75
SMD-P2Mayes Co., OKCalcite cement11.1211.0319.54
SMD-P3Mayes Co., OKCalcite cement11.8411.4219.15
SMD-P4Mayes Co., OKCalcite cement12.1011.3519.22
SMD-P5-BMayes Co., OKCalcite cement4.3311.5718.99
SMD-P5-AMayes Co., OKDolomite Cement3.989.5021.12
TSNC1-14Neck City, MOCalcite cement3.5011.0419.54
TSWB2-3-BTri-State, Treece, KSDolomite cement1.938.8321.82
TSWB2-3-ATri-State, Treece, KSDolomite cement1.387.7322.95
TSWB2-3A-BTri-State, Treece, KSDolomite cement1.248.0922.58
TSWB2-3A-ATri-State, Treece, KSDolomite cement1.518.8221.82
SampleLocalityMineralogyδ13C‰ (VPDB)δ18O‰ (VPDB)δ18O‰ (VSMOW)
TSAB1Tri-State-Anna Beaver Mine, OKCalcite cement4.7510.9819.60
TSAB1Tri-State-Anna Beaver Mine, OKDolomite–nonplanar1.586.6824.04
TSAB1Tri-State-Anna Beaver Mine, OKDolomite cement1.686.4024.33
TSAB1Tri-State-Anna Beaver Mine, OKDolomite–nonplanar0.985.6125.13
TSW-1Tri-State-Wood Chuck Mine, OKDolomite–nonplanar1.557.1723.53
TSW-2Tri-State-Wood Chuck Mine, OKDolomite–nonplanar2.066.8823.83
TSA-1Tri-State, Admiralty Mine, OKDolomite–nonplanar1.557.0323.67
TSA-2Tri-State, Admiralty Mine, OKDolomite–nonplanar1.687.6123.07
TSA-3Tri-State, Admiralty Mine, OKDolomite cement1.537.7222.96
TSA-4Tri-State, Admiralty Mine, OKDolomite cement1.487.3523.35
TSP-1Tri-State-Premier Mine, OKDolomite cement1.346.1624.57
TSP-2Tri-State-Premier Mine, OKDolomite cement1.867.1723.52
TSOG-1Tri-State, Old Goat Mine, Treece, KSCalcite cement4.3510.2920.31
TSOG-2Tri-State, Old Goat Mine, Treece, KSCalcite cement4.5310.7119.88
SMD1002Benton Co., ARCalcite cement1.768.4522.21
SMD1008McDonald Co., MOCalcite cement2.843.1127.72
SMD2100Osage Co., OKCalcite cement2.584.0426.76
SMD2102Osage Co., OKCalcite cement2.586.2124.52
SMD2103Osage Co., OKCalcite cement0.907.0623.64
SMD3001White Rock Co., MOCalcite cement2.788.8621.78
PM21-608Cherokee Co., KSDolomite cement2.002.6628.18
PM21-608Cherokee Co., KSDolomite–planar0.423.8027.00
PM21-600Cherokee Co., KSSaddle dolomite1.196.2824.44
PM21-614Cherokee Co., KSReplacement dolomite2.025.8324.91
PM21-618Cherokee Co., KSReplacement dolomite2.304.4626.32
A04-1220Jasper Co., MOCalcite cement1.824.4026.38
B50-1-85.5Jasper Co., MOCalcite cement0.799.9320.68
J5.5McDonald Co., MOCalcite crinoid2.261.2629.62
JC2McDonald Co., MOCalcite cement3.183.8426.96
JC2McDonald Co., MOCalcite mud2.664.0426.75
JC4McDonald Co., MOCalcite cement2.905.0625.70
JC4McDonald Co., MOCalcite mud2.524.0626.73
JC5McDonald Co., MOCalcite cement1.948.3022.36
JC5McDonald Co., MOCalcite mud3.013.8626.94
JN2McDonald Co., MOCalcite crinoid3.562.4028.45
JS5McDonald Co., MOCalcite crinoid2.872.1128.74
SW1Stone Co., MOCalcite crinoid3.182.2928.56
SWCU2Stone Co., MOCalcite cement3.696.6424.08
SWCU2Stone Co., MOCalcite cement4.571.9028.96
SWCU4Stone Co., MOCalcite cement3.577.2423.46
SWCU4Stone Co., MOCalcite mud4.291.9128.96
SEP2Delaware Co., OKCalcite crinoid3.391.9028.96
SEP2Delaware Co., OKCalcite cement2.652.9827.85
PAEF2Benton Co., ARCalcite crinoid3.692.4928.36
PAEC5Benton Co., ARCalcite cement1.629.2121.43
PAEC5Benton Co., ARCalcite crinoid3.971.6829.19
PAWCBA2Benton Co., ARCalcite mud1.905.5725.18
PAWC2Benton Co., ARCalcite cement2.444.6626.11
PAWC4Benton Co., ARCalcite crinoid3.512.4328.41
PAWC1Benton Co., ARCalcite mud3.301.4329.44
PAWF1Benton Co., ARCalcite crinoid3.291.8429.02
PAEC4Benton Co., ARCalcite cement1.927.2823.42
PAEC4Benton Co., ARCalcite crinoid3.103.3527.47
H2-13-663AWagoner Co., OKCalcite cement2.039.2421.39
H2-13-663BWagoner Co., OKCalcite cement1.359.8920.73
H2-13-675BWagoner Co., OKCalcite cement1.869.2921.34
H2-13-675AWagoner Co., OKCalcite cement1.829.2521.39
H2-13-678Wagoner Co., OKCalcite cement1.869.3921.24
SMD-P1Mayes Co., OKCalcite cement12.1210.8319.75
SMD-P2Mayes Co., OKCalcite cement11.1211.0319.54
SMD-P3Mayes Co., OKCalcite cement11.8411.4219.15
SMD-P4Mayes Co., OKCalcite cement12.1011.3519.22
SMD-P5-BMayes Co., OKCalcite cement4.3311.5718.99
SMD-P5-AMayes Co., OKDolomite Cement3.989.5021.12
TSNC1-14Neck City, MOCalcite cement3.5011.0419.54
TSWB2-3-BTri-State, Treece, KSDolomite cement1.938.8321.82
TSWB2-3-ATri-State, Treece, KSDolomite cement1.387.7322.95
TSWB2-3A-BTri-State, Treece, KSDolomite cement1.248.0922.58
TSWB2-3A-ATri-State, Treece, KSDolomite cement1.518.8221.82
Table 3.

Sr isotope and oxygen data () for carbonate components in the study area (see Figure 14).

SampleLocationLithology87Sr/86Srδ18O (VPDB)
TSAB-1-AAnna Beaver Mine, OKBreccia-filling calcite cement0.709810.98
TSAB-1-BAnna Beaver Mine, OKBreccia-filling dolomite cement0.70916.68
SMD2102Osage Co., OKFracture-filling calcite cement0.71126.21
TSNC-1-14Neck City, MOBreccia-filling calcite cement0.709911.04
SMD-P5Mayes Co., OKBreccia-filling dolomite cement0.70929.50
SMD-P1Mayes Co., OKFracture-filling calcite cement0.709710.83
TSA-1Admiralty Mine, OKBreccia-filling dolomite cement0.70937.03
H2-663Wagoner Co., OKFracture-filling calcite cement0.70929.89
JC5McDonald Co., MOFracture-filling calcite cement0.71008.30
SEP2-ADelaware Co., OKCalcite crinoid skeletal grain0.70821.90
SEP2-BDelaware Co., OKIntergrain calcite cement0.70852.98
SampleLocationLithology87Sr/86Srδ18O (VPDB)
TSAB-1-AAnna Beaver Mine, OKBreccia-filling calcite cement0.709810.98
TSAB-1-BAnna Beaver Mine, OKBreccia-filling dolomite cement0.70916.68
SMD2102Osage Co., OKFracture-filling calcite cement0.71126.21
TSNC-1-14Neck City, MOBreccia-filling calcite cement0.709911.04
SMD-P5Mayes Co., OKBreccia-filling dolomite cement0.70929.50
SMD-P1Mayes Co., OKFracture-filling calcite cement0.709710.83
TSA-1Admiralty Mine, OKBreccia-filling dolomite cement0.70937.03
H2-663Wagoner Co., OKFracture-filling calcite cement0.70929.89
JC5McDonald Co., MOFracture-filling calcite cement0.71008.30
SEP2-ADelaware Co., OKCalcite crinoid skeletal grain0.70821.90
SEP2-BDelaware Co., OKIntergrain calcite cement0.70852.98
Table 4.

Correlation of cathodoluminescence zones in calcite cements among studies of Mississippian rocks on the midcontinent.

This StudyRitter and Goldstein (2012)Kaufman et al. (1988)
1NL1-NL5II
2ML6-ML7III
3NL7IV
4SL8-NL8V
5SL9VI
This StudyRitter and Goldstein (2012)Kaufman et al. (1988)
1NL1-NL5II
2ML6-ML7III
3NL7IV
4SL8-NL8V
5SL9VI
Table 5.

Th values of fluid inclusions, δ18O values of carbonate cements, and calculated δ18O values of waters in equilibrium with these cements and their host rocks at the temperatures shown. The equation used for calcite cements is O’Neil et al. (1969) and that for dolomite cements is Northrop and Clayton (1966). The mean δ18O values (VSMOW) for the host limestone in the study area is 28.2.

SampleLocation and Host CementTh°Cδ18Ocalcite‰ VSMOWδ18Odolomite‰ VSMOWδ18Ocement-depositing water‰ VSMOW
JC5McDonald Co., MO, Calcite87 to 14022.43.9 to 8.9
SMD2100Osage Co., OK #1, Calcite80 to 12026.87.3 to 11.8
SMD2102Osage Co., OK #2, Calcite115, 135, 149, 17324.59.0, 11.0, 11.9, 13.5
TSNC1-14Neck City, MO, Calcite54 to 9819.5−3.2 to 2.3
H2-13-663Wagoner Co., OK #1, Calcite84 to 11821.42.4 to 5.9
H2-13-675Wagoner Co., OK #2, Calcite61 to 7121.4−0.6 to 0.9
SMD1002Benton Co., AR, Calcite116 to 15022.26.7 to 9.6
SMD-P1Mayes Co., OK #1, Calcite8819.81.3
SMD-P3Mayes Co., OK #2, Calcite44, 89, 97, 14519.1−5.5, 0.6, 1.6, 6.1
SMD-P5Mayes Co., OK #3, Dolomite63 to 7521.1−4.9 to −2.9
TSWB2-3Tri-State, Trecee, KS, Dolomite11322.62.6
TSAB1Anna Beaver Mine, OK, Dolomite103 to 11624.33.3 to 4.8
TSA-1Admiralty Mine, OK, Dolomite111, 128, 14223.75.7 to 6.9
SampleLocation and Host CementTh°Cδ18Ocalcite‰ VSMOWδ18Odolomite‰ VSMOWδ18Ocement-depositing water‰ VSMOW
JC5McDonald Co., MO, Calcite87 to 14022.43.9 to 8.9
SMD2100Osage Co., OK #1, Calcite80 to 12026.87.3 to 11.8
SMD2102Osage Co., OK #2, Calcite115, 135, 149, 17324.59.0, 11.0, 11.9, 13.5
TSNC1-14Neck City, MO, Calcite54 to 9819.5−3.2 to 2.3
H2-13-663Wagoner Co., OK #1, Calcite84 to 11821.42.4 to 5.9
H2-13-675Wagoner Co., OK #2, Calcite61 to 7121.4−0.6 to 0.9
SMD1002Benton Co., AR, Calcite116 to 15022.26.7 to 9.6
SMD-P1Mayes Co., OK #1, Calcite8819.81.3
SMD-P3Mayes Co., OK #2, Calcite44, 89, 97, 14519.1−5.5, 0.6, 1.6, 6.1
SMD-P5Mayes Co., OK #3, Dolomite63 to 7521.1−4.9 to −2.9
TSWB2-3Tri-State, Trecee, KS, Dolomite11322.62.6
TSAB1Anna Beaver Mine, OK, Dolomite103 to 11624.33.3 to 4.8
TSA-1Admiralty Mine, OK, Dolomite111, 128, 14223.75.7 to 6.9

Contents

GeoRef

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