15L DtYALLw ”D "’2 EL‘sLi‘u-Aieé ' «N. .L- “S m3 L‘C’Li CALL": L.) V9. 1133‘.» 2613:.(3NESEUL‘C‘? T" 3: ElLliQ C}: L LLJIL’LPL‘LL ‘-.- MILES")? {“36 W é‘LEZ? ‘: ELLL" :. “$2331.: ‘~ 1m '2'?!“ Tiwefs‘ ’M De}, we 3;"? {LL :3. [LLLCHEGALL L. .m‘“ UPL‘L'T".$I’E’Y ’9‘ l p | ' Leamd FL Harm v. ,. 2%? LIBRARY Michigan State University PLACE IN RETURN BOX to remove this checkout from your record. TO AVOID FINES return on or before date due. MAY BE RECALLED with earlier due date if requested. DATE DUE DATE DUE DATE DUE 6/01 c:/CIRC/DaIeDue.p65-p. 15 A DETAILED CHEMICAL ANALYSIS FOR CALCIUM AND MAGNESIUM OF THE SUN OIL COMPANY, PETERSON-HOWARD WELL #1 CORE SAMPLE By David F. Hamil A THESIS Submitted to the College of Science and Arts Michigan State University of Agriculture and Applied Science in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Department of Geology «12: ACKNOWLEDGEMENTS The writer wishes to express his sincere thanks to Dr. C. E. Prouty, of the Department of Geology, Michigan State University, for his many suggestions for the improvement of this report and under whose general guidance the study was made. He also wishes to give grateful acknowledgement to Dr. B. T. Sandefur and Dr. H. B. Stonehouse, who are also members of the Guidance Committee, and other members of the EEpartment of Geology, Michigan State University, for their help in checking the manuscript. The Sun Oil Company furnished the well core used in this analysis; their cooperation is greatly appreciated. For special permission to use the Michigan State Highway Department‘s facilities for crushing the samples. the writer expresses his sincere thanks. ii ABSTRACT A DETAILED CHEMICAL ANALYSIS FOR CALCIUM AND MAGNESIUM OF THE SUN OIL COMPANY, PETERSON-HOWARD WELL #1 CORE SAMPLE by David F. Hamil The use of calcium/magnesium.ratio studies has recently he- come important to oil exploration in Michigan. Oil and gas pro- duction and showings in Ordovician limestone are almost entirely limited to the areas where the Trenton-Black River sequence is dolomite and limestone or entirely dolomite. Tinklepaugh (1957) has suggested a correlation between epigenetic dolomitization and structure in the Michigan basin with the highest degree of dolo- mitization attained on the anticlinal crests. These may be the loci of oil reservoirs. Several studies have been made on the lateral variation of the calcium/magnesium ratio within certain formations in an attempt to delineate anticlincal crests but little has been done to show how much of the calcium/magnesium variation is strati— graphic. By determining the vertical calcium/magnesium variation in several wells, it is hoped that stramigraphic dolomite may be separated from epigenetic dolomite. This, then, is the first part of a study which it is hoped will some day carry to its iii logical conclusion. Implicit in this detailed study is the nature of the dolo- mitization in the high magnesium zones. _ Careful chemical analyses of core samples from the Sun Oil Company, Peterson-Howard well #1 were made to determine the rela- tive percentages of calcium.and magnesium present. The method employed is based on the Versenate method, which quickly gives the calcium/magnesium ratio of samples. iv CONTENTS INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . GENERAL STRATIGRAPHY . . . . . . . . . . . . . . . . . . . Overlying Formations . . . . . . . . . . . . . . . . Trenton-Black River Sequence . . . . . . . . . . . Glenwood Formation. . . . . . . . . . . . . . . . . . St. Peter Sandstone . . . . . . . . . . . . . . . . Prairie du Chien. . . . . . . . . . . . . . . . . . . ANALYTICAL TECHNIQUES. . . . . . . . . . . . . . . . . . . Method of Obtaining Samples . . . . . . . . . . . . . Preparation and Digestion of the Samples . . . . . . Mass Analysis Techniques . . . . . . . . . . . . . CLASSIFICATION OF LIMESTONES AND DOLOMITES ON THE BASIS OF cat/w RA'I‘IO . C O O O O O O O O O 0 C O O O O O C 0 O O O NATURE OF THE DOLOMITIZATION . . . . . . . . . . . . . . CONCLIJSIONS . O O O O O O O O O O O O C O O O O O O O O I BIBLIOGRAPHY . . . . . . . . . . . . . . . . . . . . . . . Page IO 10 ll 12 l6 19 20 3Ll- TABLES TABLE . Page I. Individual Sample Analysis Results Compared with Lithologic Description . . . . . . . . . . . 22 II. Results of TeSt for Insolubles . . . . . . . . . . 33 vi FIGURE FIGURES Page Map Location of the Peterson-Howard well No. l . . . 3 Minerological Section of the Cambrian and Ordovician Systems of Michigan . . . . . . . . . . . 9 Portion of Gamma Ray-Neutron Log of the Peterson- Howard Well No. 1 Compared with the Ca/Mg Ratios . . 32 vii INTRODUCTION The use of calcium/magnesium ratio studies has recently be- come an important method of oil exploration in Michigan. Oil and gas production and showings in the Ordovician limestone are usually limited to the areas where the Trenton-Black River sequence is dolomite and limestone, or entirely dolomite. Normally, the limestone apparently has little effective pore space capable of containing oil or water. Yet, fortunately, when dolomitization has occurred, the Trenton-Black River is often found to be an ex- tremely porous and permeable dolomite. Tinklepaugh (1957) has suggested a correlation between epigenetic dolomitization and structure in the Michigan basin with the highest degree of dolo- mitization attained on the anticlincal crests. These crests being the loci of oil reservoirs. In some localities the dolomific zones are not directly re- lated to folded structure, but extend in narrow, straight bands often less than one-quarter of a mile in width and sometimes several miles in length. Such zones are generally thought to be controlled by faulting, and the porosity of these zones is also attributed to epigenetic dolomitization. The Albion-Scipio field is thought by many to be of this nature. Several studies have been made on the lateral variation of the calcium/magnesium ratio within certain formations in an attempt to locate other "Albion-Scipio" structures. Little, how- ever, has been done to show how much of the calcium/magnesium ratio variation is stratigraphic. By determining the vertical variation of the calcium/magnesium.ratio of several wells, it is hoped that the stratigraphic horizons may be separated from those areas which are epigenetic in nature. Unfortunately, however, due to the detailed nature of the study, analyses of more than one well would be beyond the scope of this thesis. This then is the first part of a study which it is hoped future students will someday carry to its logical conclusion. The Sun Oil Company, Peterson-Howard Well #1 core is particu- larly well suited for the purpose of this study because it lies outside the Albion-Scipio trend. It is therefore more likely to represent the section in its original state, that is, without being affected by epigenetic dolomitization. The Sun Oil Company, Peterson-Howard Well #1 is located in Pulaski wanship, Jackson County, Michigan (Section 17, T. h S., R. 3 w., N.W., N.E., s.w.). The location of the well is shown on the map on the following page. Structurally the Peterson- Howard Well #1 is located just to the southwest of the Albion- Scipio trend. The samples taken represent each combined two-foot interval of the Trenton-Black River section contained in the well core now in the possession of Michigan State University. The interval sampled lies between thO and h3lh feet. The top of the Trenton was intersected at 3711 feet, but coring was not started until thO feet. The Glenwood interval starts at h3lh feet. MAP LOCATION OF THE PETERSON-HOWARD WELL NO.| ' FIGURE: 1’ “‘ f 5 Mia] - PETERSON -HOWAHID ,5 WELL. N0.| Implicit in this detailed study is the nature of the dolo- mitization in the high magnesium zones. This work was closely coordinated with a detailed lithographic and petrographic description of the same core made by Kirschke (1961). GENERAL STRATIGRAPHY The following description of the general stratigraphy is based largely on publications of George v. Cohee (19u7; l9u8). Overlying Formations The overlying formatioasof the Trenton-Black River are of Upper Ordovician age and attain a maximum thickness of 800 feet in the southeastern part of the state. The strata are largely gray and dark gray shale with minor amounts of dolomite and limestone. In southeastern Michigan, Upper Ordovician rocks can be divided into the Utica, Lorraine, and Queenston shales in ascending order. Trenton-Black River The Trenton and underlying Black River rocks generally consist of brown and gray crystalline limestone and dolomite which occur in different proportions in different areas. Dolomite pre- dominates in eastern Wisconsin, northeastern Illinois, and north- western Indiana. Along the Kankakee and Findlay arches and around the margin of the Michigan Basin they are dolomite and limestone mixed. In much of the central part of the Michigan Basin and east of the Findlay arch in eastern Ohio and west of the LaSalle anti- cline in Illinois they are mostly limestone. The occurrence of dolomite along the major anticlinal axes indicates a possible secondary origin for the dolomite which may be in part related to folding. The base of the Trenton limestone has been generally de- termined in southwestern Ontario by a very argillaceous limestone and shale section about #00 feet below the top of the Trenton limestone. The shale and argillaceous limestone is a lithologic unit which can be readily recognized in the subsurface. From southwestern Ontario the Trenton—Black River boundary can be traced into Michigan and can be determined with little difficulty westward across the state except in Berrien County, where the Trenton and Black-River rocks are largely dolomite. The base of the Trenton in the Peterson-Howard Well #1 is shown distinctly at #102 feet on the radioactive log (Fig. l). The Trenton lime- stone is from 203 to #79 feet thick in the area. The Black River limestone in the Southern Peninsula is 150 to 517 feet thick and consists of light brown_and gray, fossiliferous, dense to crystalline limestone and dolomite, quite similar to the overlying Trenton. The basal part of the Black River limestone may consist of fine-grained dark gray to black argillaceous limestone or of limestone and shale. Some chert fragments have been found in the top of the Black River in local areas. The Black River strata overlap Lower Ordovician, Cambrian, and Precambrian rocks along the southern margin of the Michigan Basin from southeastern Michigan to Ontario. The Trenton and Black River rocks are thickest in eastern Michigan and in the adjoining part of Ontario where they attain a maximum thickness of 985 feet. Their regional thickening in the Chatham sag in Kent County, Ontario, suggests that this was a structurally low area which served as the first connection between the Michigan basin and the seas on the east in Black River time. The Trenton and Black River rocks thin over the Kankakee arch through northern Indiana and they thin slightly at the northern end of the Findlay arch in Essex County, Ontario. There is also some thlnnlng on the Cincinnatl arch. Clenwooa The Glenwood formation 18 shale at its type locality in Glenwood Township, Winneshiek County, Iowa, and is here underlain by St. Peter sandstone. In southeastern Michigan, northeastern Indiana and Ohio, shale has been found in wells below the Black River limestone. This shale is sandy, green, brown, or gray and in places pyritic. It is 5 to 30 feet or more thick. In places quartz grains are abundant in the shale, particularly at the con- tact with the underlying dolomite. The quartz grains were prdbably derived from the erosion of older formations and were concentrated locally. The lithologic character of these rocks is very similar to that of the Glenwood formation, although it may not be the exact time equivalent of the Glenwood further west. St. Peter The St. Peter sandstone of Lower Ordovician age is present in Wisconsin, Illinois, western Indiana and western Michigan. Although it is generally absent in eastern Michigan, the Northern Peninsula of Michigan, eastern Indiana, and northwestern Ohio, some wells have penetrated a thin sandstone underlying Middle Ordovician rocks which probably is the/time equivalent of the St. Peter. The St. Peter is absent in the Peterson-Howard well. Prairie du Chien In Michigan, the St. Peter rests on the eroded surface of the Prairie du Chien, in most places, the Oneota formation. The Prairie du Chien is a buff, sandy and cherty dolomite. It contains small amounts of green to green-gray shale in places. Oolitic chert and pyrite are common with iron oxides, glauconite, and gypsum less common. Cohee (l9h8) describes the Oneota dolomite of southwestern Michigan as lighologically similar to the Oneota of Illinois. The Prairie du Chien was evidently eroded to a surface of high relief, and in some places completely removed. In general, the Prairie du Chien is absent in southeastern Michigan. The upper 77 feet of the Prairie du Chien was cored in the Peterson- Howard well. KICHIGAN szquouwo Queenston RICHMOND Big Hill Stonington C INC I I'U-IAT IAN EAISVILLE : figgggtne EDEN Collingwood Trenton .. T . l, m TRENTOI‘I P k P.‘ IMOEIAMXIAH LLACI; RIVER GEtg-EWOOéver CHAZYAN St. Peter Northern Peninsula Southern Peninsula ___J CANADIAN Shakopee PRAIRIE New Richmond s:e«u ZD>FHflUi , Jordan S >§E§E§$fiiLodi T. LAU St. Lawrence C LAKE Franconia R _ c O SUPERIOR Dresbach I . Xi HUNISING Eau Claire I . A. Mt. Simon N JACOBSVILLE Jacobsville Generalized Section of the Cambrian and Ordovician Systems of Michigan after Horowitz (1961) ANALYTICAL TECHNIQUES Method of Obtaining Samples For the purpose of this disseration, it was desirable to take a channel sample of the entire length of the Trenton-Black River interval. This was done with the aid of a diamond rock saw. The interval selected for each sample was two feet, as this has been shown by Bones (1955) to be about an optimum interval for chemical analysis of carbonate rocks. A relatively thin sample slice was made since for the chemical analysis,only a l-gram sample of each 2-foot interval was used. Each sample was labeled and placed in a sample bag. The samples were then pulverized by means of a Denver jaw crusher. It was found that there were still some fragments (less than hO% of the whole) which would not pass through the micro-sample splitter. The sample was then placed on a reciprocating shaker and sieved for the fines. The size of the sieve used was a A17 mm— Tyler sieve. It was felt that the smaller the fragment size of the sample, the more representative it would be of the 2-foot interval. Each sample was then divided on a micro-sample splitter until approximately 8 to 10 grams remained, and were placed in vials ready to be prepared and digested for chemical analysis. 10 Preparation and Digestion of the Samples 1. Samples were washed and dried. As a ratio was the desired result in this study, it was not necessary to remove small flakes of shale and other relatively inert substances. If exact percentages of calcium and magnesium were desired, all foreign substances would have had to be removed. 2. A l-OOO gram (approximately, if a ratio is desired) sample was placed into a 250 milliliter beaker and 10 milliliters of per- chloric acid was added- 3- The solution was gently heated until it became colorless, and then evaporated to dryness. After complete evaporation, the sample was cooled- h- The cooled residue was dissolved by adding 3 milliliters of 1:1 hydrochloric acid and 10 milliliters of water- The solution {was then filtered and diluted to 250 milliliters with water- It was essential that distilled water he used for all aqueous solutions, and that all equipment be washed thoroughly with distilled water.1 l Tb determine the effect of common tap water or unclean apparatus on the results, an analysis was made using 10 ml; of tap water in place of the digested rock sample. The tap water analysis showed that a positive error of h-6% CaO and 1-0% MgO would result if tap water were used instead of distilled water- This error approaches a maximum of 20%- ll Mass Analysis Techniques The following is a description of R. L. Jodry's (195A) adaptation of the basic method of analysis specifically for magnesium/calcium ratio determination. The preliminary work on this method was done by K. L. Cheng, T. Kurtz, and R. H. Bray (1952). Although the Mass Analysis Technique is presented as a magnesium/calcium ratio, the writer found it more useful to use a calcium/magnesium ratio. Therefore, in using the technique described below, it was necessary to invert the formula before computing the ratio. The desired calcium/magnesium.ratio may be expressed as follows: A x 25 x l.h x B x 100 00a = 1,000 oMg A(At.Wt.Mg) _ "(At’m'Caj X 25 x 1.66 x (D B) 1,000 X 100 = 1.4 x B At.Wt. (At.Wt.U§) x 1.66 x (D - B) Where A is milligrams of calcium per milliliter of versenate solution. Where B is milliliters of versenate solution used in titration, with Murexide as indicator. Where D is milliliters of versenate solution used in titration, with F 2hl as indicator. 12 l3 This may be expressed as (C x B)/(D - B) where, (At-Wt Ms) C _ (AtW M) 166 _ tit Where Efiifi E) is 0.607 In its simplest form, the formula for determining the calcium/magnesium ratio for a sample may be expressed as follows: percent Ca _ 1.39 B percent Mg — D - B This basic formula permits the ratio computation without the use of a specific weight of sample (l.OOO gram in the original formula) and without standardizing the versenate solution for either magnesium or calcium.1 It is desirable to use approximately 1 gram of clean sample and a versenate solution near the strength described only because these proportions give optimum reaction without waste of reagents. However, in this study exact sample weights were recorded and the versenate solution was standardized. To analyze a number of samples, it is best first to prepare and weight all samples. Samples may be digested in groups as large as evaporation facilities will permit. Perchloric acid fumes are extremely dangerous, and evaporation must be done with proper ventilation. After evaporation, samples can be kept in their beakers for an indefinite period in a dry place. Many samples, lVersenate solution. Dissolve h grams of the disodium salt of (ethylenedinitrilo) tetraacetic acid in 1 liter of water. lb usually eight to twelve, may be conveniently handled and redissolved at one time. It is desirable to use two or more 250-milliliter calibrated flasks for preparing the sample. The dissolved sample may be filtered directly into the calibrated flasks, and by using two or more, filtering may continue while the preceding sample is "made up" and titrated. A lO-milliliter graduated pipette is used to take the aliquot for analysis. To determine calcium, a quantity of the potassium hydroxide solution is mixed with 20 times its volume of water.2 Twenty milli- liters of this solution and indicator powder are added to the aliquot before titration.3 A graduated 50-milliliter burette is best for titration. The end point of the titration for calcium is reached when the color of the solution changes from pink to violet. Tb determine magnesium, the buffer solution,h water and potassium cyanide5 may be combined in the ratio of 26 parts water, 3 parts buffer, and 1 part potassium cyanide. Thirty milliliters 2 Potassium.hydroxide. Use a 20-percent aqueous solution. 3 Calcium indicator powder. Mix thoroughly #0 grams of powdered potassium sulfate and 0.2 gram of Murexide. A Buffer solution. Dissolve 60 grams of ammonium chloride in approximately 200 milliliters of water; add 570 milliliters of concentrated ammonium hydroxide, and dilute to 1 liter with water. 5 Potassium cyanide. Prepare a lO-percent aqueous solution. 15 of this solution and 8 drops of F 2hl indicator6 are added to the aliquot before titration. The end point of the titration for magnesium is reached when the color of the solution changes from wine-red to clear blue. 6 F 2l+l indicator. Dissolve 0.15 gram of Eriochrome Black T (F 2&1) and 0.5 gram of sodium borate in 25 milliliters of methanol. Classification of Limestones and Dolomites on the Basis of Ca/Mg Ratio The classification used here is that of G- V- Chilingar (1957). Magnesium dolomite 1-0 - 1.5 Dolomite 1.5 - 1.7 Slightly calcareous dolomite 1.7 - 2-0 Calcareous dolomite 2-0 - 3-5 Highly dolomitic limestone 3.5 - 16.0 Dolomitic limestone 16.0 - 60.0 Slightly dolomitic limestone 60-0 - 105-0 Calcitic limestone Greater than 105-0 This cLassification is on the basis of Ca/Mg ratios, with some of the divisions determined by the mode of formation. The following is Chilingar's (1957) explanation of the basis of his subdivision. 1. Magnesian dolomites (Ca/Mg = l-l-5)- A pure dolomite has a ratio of lo6h8zl; however, some dolomites contain an exceSs of MgCO3, due to formation at elevated temperatures. Some hydrothermal dolomites can be placed in this group- 2. Calcareous dolomites (Ca/Mg = 1.7-3-5). The upper limit of calcareous dolomites was chosen because the Ca/Mg ratio of 3ohh:l is the lowest ratio known in the skeletal structure of organisms. Many dolomites fall in this group. They could result from an excess precipitation of calcite over dolomite, or incomplete dolomitization- l6 l7 3. Highly dolomitic limestones (Ca/Mg = 3.5-16). Numerous limestones which are composed almost entirely of skeletal and pro- tective structures of organisms have Ca/Mg ratios which exceed 16.1. However, the skeletal structures can have Ca/Mg ratios as low as 3.hhzl. Secondary dolomitization (diagenetic and epigenetic) is probably also very important in their origin. A. Dolomitic limestones (Ca/Mg = 16460). The majority of dolomitic limestones of this class have their origin in the accumulation of protective and skeletal structures of organisms. Fine grained limestone paste present in these limestones is either of chemical origin or has resulted from comminutation of skeletal structures of organisms. Partial diagenetic and epigenetic dolo- mitization is also possible. 5. Slightly dolomitic limestones (Ca/Mg = 60-105). The upper limit of Ca/Mg ratio of slightly dolomitic limestones is taken as 105. The reason for the selection of this figure is the fact that Ca/Mg ratio of 105.2 is the highest known ratio for calcitic or- ganisms (oysters). These limestones are also probably the result of accumulation of skeletal strcutures of organisms. The fine grained limestone paste of slightly dolomitic limestones is often of chemical origin. 6. Calcitic limestones (Ca/Mg > 105). The calcitic lime- stones could result from accumulations of skeletons of aragonitic organisms, from direct chemical precipitation, or from subsequent loss of MgCO3. Calcitic organisms have made considerable contri- l8 bution to some limestones of this group. The high over-all Ca/Mg ratio of these limestones, therefore, is pr0bably due to the low magnesium content of the cementing limestone paste, precipitated directly out of sea water. NATURE OF THE DOLOMITIZATION The distribution of the dolomite throughout the core was well shown by the ferrocyanide staining done by Kirschke (1961). For the most part, the dolomite is concentrated in the dark car- bonaceous bands and layers which occur in varying frequency through- out the section. In several horizons the carbonaceous material takes on a mottled appearance. There were also two distinct horizons in which dolomite was the main constituent. They varied in thickness from 1 to 3 inches to approximately one foot. In addition, dolomite crystals were generally scattered throughout the section in varying abundance. Fe++ occurs as an "impurity" in dolomite rather than associated calcite. This reacts with ferrocyanide to stain the rock blue. It was not know whether the blue stain in the banded zones might not be due to the Fe++ in the clay constituent. Therefore, the insolubles were separated from.the carbonates, and treated with ferrocyanide. Since this stain test was negative, the writer feels that the carbonate in the banded zones is largely dolomite. Additionally it indicates that dolomite, not clay, yields the positive test observed in the core. Insolubles were examined from three different areas for comparison: (1) a distinct dolomite band, (2) a typical car- bonaceous band, and (3) a limestone area immediately above the capbonaceous band. The insolubles from the carbonaceous band were separated to determine the ratio of silt to clay. The results are shown in Table II- 19 CONCLUSIONS Although it is impossible at this time to draw any definite conclusions as to whether any of the high magnesium zones are stratigraphic, several of these zones merit notice. The most important of these zones lies between A232 and A258 feet. The second most important of these zones occurs between 4291 and #311 feet. While several other zones have a high magnesium content, the two mentioned above are more likely to have a stratigraphic origin due to the consistently high magnesium content, through a large thickness. It will, of course, take similar studies of other wells to show which, if any, of these zones are stratigraphic. It is interesting to note that in plotting the calcium/ magnesium ratios alongside the neutron log, the general pattern shows striking similarities even though the factors measured were different. Even greater similarities might be expected if sampled at a smaller interval. If this concept is valid, it might be possible to estimate calcium/magnesium ratios in relatively pure carbonate rocks. Such a procedure would cut out the time required for a calcium/magnesium ratio analysis and offer a much more handy tool for exploration. The distribution of dolomite throughout the core appears to have three modes of occurrence. The majority of the dolomite appears to be concentrated in the carbonaceous bands. Although it is difficult to estimate the percentage, the second most im- portant concentration of dolomite seems to be in the dolomite 2O 21 crystals scattered throughout the core. Third, and relatively unimportant, there are a small number of bands in which dolomite is the main constituent. 22 TABLE I Individual Sample Analysis Results Compared with Lithologic Depth uloo-hlo2 A102—h10u h10h-A106 A106-u108 A108-ullo h110-h112 A112—ullu h11h-A116 A116-u118 All8-u12o A120-u122 h122-A12u ul2h-hl26 A126—u128 A128ehl30 A130-u132 h132-Al3u A13u—A136 h136-h138 A138—A1u0 h1h0-hlh2 Percent Ca Description A7.l2 h5.01 h6.33 h6.73 A7-53 A2.6A A775 A7.lu u7.02 A7.66 A8.uu h6.95 A7.32 h7.u9 h8.53 h7.38 A6.97 A6.95 A7.27 A5.66 A6.38 Percent Mg 2 1 O .31 .8h ~79 .26 .A3 .68 .85 .2A .28 .33 .A5 .20 .07 .60 .23 .81 .01 .85 .92 .22 .16 Ca/Mg 20 2h 58. 179 110 25 21 20 20 33 21 22 29 39 26 23 25 21. Ratio .398 .u62 6A5 .731 ~535 ~383 .811 .0h5 .623 .h55 .407 .3A1 .860 .681 .u55 .180 .368 .uu7 2A. 1A. 618 180 A71 Classification Dolomitic Dolomitic Dolomitic Slightly dolomitic ls. Slightly dolomitic ls. Highly dolomitic ls. Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Highly dolomitic ls. Dolomitic limestone limestone limestone limestone limestone limestone limestone limestone limestone limestone limestone limestone limestone limestone limestone limestone limestone 23 Lithologic Description thO-h107.2 Ls, lt brn & gry brn, crpxl & dns, w/ num scat carb bnd. A107.2—u111 Ls, 1t gry brn (taffy col), w/ v few carb ptg, crpxl. Alll-hll2 Ls, lt brn, scat clusters of cal and/or dol xls. h112-hl26 Ls, gry & brn gry, crpxl & dns, w/ hum scat clusters of cal and/ or dol xls vf & tt cmt in ls mtx, num carb bnds cont thru section. ul26-hlh2.9 Ls, 1t brn, (taffy col), same as abv, but s1 more carb bnd at base. 2A Depth A1u2—Aluu AlhA—h1u6 Alu6-Alh8 A1u8-Al50 A150-u152 A152-ul5u ul5u-hl56 A156-u158 A158-A160 A160-h162 h162-A16A Al6u—u166 Al66-Al68 A168-u170 Al7o—u172 ul72-ul7u ui7u-u176 ul7o-t178 A178—u180 Al80-Al82 A182—ul8u A18A-hl86 Percent Ca TABLE I (continued) Percent Mg A6.90 46.15 A9.2l h5.12 A7.6u A5.20 u5.26 A5.7u A6.36 h6.60 A6.50 A6.81 A7.8A h7.86 Au.ou AA.06 A7.5u 36-95 h5.68 h6.u3 1+5 .95 A8.52 1.8u 2.18 2.5M 1-75 2.78 3.5A 3.01 1.98 2.91 2.91 2.16 2.0M 2.03 3.86 3.63 2.09 7-A5 2.51 1.70 1.07 Ca/Mg 25 21.. 22 17. 27. 16 l2 l5 23 16 15 23 23 ll 12 22 18. 27. A2. 35- Ratio .A88 517 .573 76A 220 ~259 .785 .196 .u21 .01A .978 21. 671 1,51 -579 .u09 .138 .7A6 A. 960 197 309 9AA 9A1 Classification Dolomitic limestone Dolomitic limestone Dolomitic limestone Dolomitic limestone Dolomitic limestone Dolomitic limestone Highly dolomitic ls. Highly dolomitic ls. Dolomitic limestone Dolomitic limestone Highly dolomitic ls. Dolomitic limestone Dolomitic limestone Dolomitic lime stone Highly dolomitic ls. Highly dolomitic 1s. Dolomitic limestone Highly dolomitic ls. Dolomitic limestone Dolomitic limestone Dolomitic limestone Dolomitic limestone 25 Lithologic Description A1A2.9—A1A3.6 Ls, 1t brn gry, crpxl, v abnt clusters of cal and/or dol xls. A1A3.6-A1A5.6 Ls, gry & brn gry & brn, crpxl & dns, v tt w/ evidence of carb filled vert & hztl frac, section v mot w/ carb mat. AlA5.6-Al75.6 Ls, gry, dns, w/ general birdseye & bnd aprs due to carb mat, v tt, becoming crpxl at pts, w/ small clusters of cal xls. A175.5—A186.5 Ls, gry taffy col, crpxl w/ num 5 clusters of cal or dol xls, v hd & v tt, w/ some carb bnd at A178, A181, & A183. 26 Depth A186-A188 Al88-Al90 A190—A192 A192—A19A Al9A-Al96 A196—A198 Al98-A200 A200-A202 A202—A20A A20A—A206 A206-A208 A208—A210 A210-A212 A2l2-A21A A2lA-A2l6 A216-A2l8 A2l8-A220 A220-A222 A222-A22u A22A-A226 A226-A228 A228—A230 A230-A232 TABLE I (continued) Percent Ca A5.90 45.87 A7.23 A5.38 A3.05 A3-37 AA.66 A3.A2 A2.87 A5.30 A6.98 A8.23 A6.82 A8.75 A8.16 A8.82 A9.0A A8.6A A8.8A A9-55 A9.30 A9-53 AA.l7 Percent Mg 2 3 .33 .Al ~39 .66 .71 -35 .29 .1A .00 .99 ~37 .68 .52 -37 .71 -57 .Al .Al .2A .20 .17 .22 .OO Ca/Mg Ratio 19.700 13.A52 19.80A 17.062 11.60A 12.965 13-595 10.501 10.717 15.176 19.823 28.708 30.803 35-714 28.166 31-193 3A.780 3A.A9A 39-545 A1.295 ;; A2.1A0 A0.768 11.0A2 Classification Dolomitic limestone Highly dolomitic ls. Dolomitic limestone Dolomitic limestone Highly dolomitic Highly dolomitic Highly dolomitic Highly dolomitic Highly dolomitic Highly dolomitic ls. ls. ls. ls. ls. ls. Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic _Dolomitic Dolomitic limestone limestone limestone limestone limestone limestone limestone limestone limestone limestone limestone Dolomitic limestone Highly dolomitic ls. 27 Lithologic Description A186.5-A19A.3 Ls, gry & some brn gry, dns & crpxl w/ some cal or dol xls in s clusters, considerable carb bnd. Al9A.3-A205 Ls, dk gry & dk brn gry, dns & crpxl at pts, w/ widespread carb bnd in thn str & strg, gives a somewhat mot aprs to core, v tt. h205-u227 Ls, dk gry & dk gry brn, dns & crpxl at pts, widespread carb bnd in thn str & strg. Core loses its mot aprs. Cgl at pts, A205.7; A208.5; A216.5; A219.9. All abt 0.1 ft thk. A227-A228.A Ls, dk brn, crpxl, scat strg of Cal or dol, vert carb filled frac v 1t1 carb bnd. A228.A-A2A8.65 Ls, dk gry to dk brn gry, dns w/ carb bnd thru in bnds from A228.A-A238.5, and thn 28 Depth A232—u23u A23A-A236 A236-A238 A238—A2A0 A2A0—A2A2 A2A2—A2AA A2AA-A2A6 A2A6—A2A8 A2A8-A250 A250—A252 A252-A25A A25A-A256 A256-A258 A258-A260 A260-A262 A262-A26A A26A-u266 A266-A268 A268-A270 u270-A272 A272-A27A A27A-A276 A276—u278 A278—A280 TABLE I (continued) Percent Ca 38.33 38.51 39.82 A0.60 AA.62 AA.06 AA.81 AA.67 A3.26 Al.9A AA.02 A6.37 A7.A5 A8.01 A6.76 A6.95 A5-59 A5.02 A6.03 A5.05 A5.A8 A5.03 A3.51 A3.02 Percent Mg 9 9 8 1:— .6A .30 .27 .60 -53 .20 .61 .82 .89 .68 .13 .09 -39 .52 .7A .A5 .AA .A3 .32 .61 .85 .ll .19 .Al Ca/Mg Ratio 3-978 n.1u3 A.818 5-350 9.858 8.A7A 9.721 9-277 7.3AA 6.28A 8.581 15.007 19.855 31.690 26.873 32.382 31.766 31.A8A 35.00A 27.981 2A.65l 21.392 19.866 17.851 Classification Highly Highly Highly Highly .Highly Highly Highly Highly Highly Highly dolomitic dolomitic dolomitic dolomitic dolomitic dolomitic dolomitic dolomitic dolomitic dolomitic 1s. ls. 1s. 1s. ls. ls. ls. ls. ls. ls. 29 Lithologic Description Highly dolomitic Highly dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic Dolomitic limestone limestone limestone limestone limestone limestone limestone limestone limestone limestone limestone limestone ls. ls. strg. A238.5-A2A8.65, some evidence of styl ptg at A235.5, cht nod .15 ft dia at A230.A, v tt, dk brn crpxl from A228.A-u230. A2u8.65-A292.1 Ls. dk gry & dk brn gry, dns & crpxl w/ thn bnd of carb mat scat thru section, also w/ l to 3 in thk strg of m to f x1 ls scat thru section. This x1 is has rd sd gr & shell frag & has pea sz vugs at A280.5. Styl ptg at A292.1 TABLE I (continued) Depth Percent Ca Percent Mg Ca/Mg Ratio 4280—4282 41.15 2.65 15.558 4282-4284 43.16 1.86 23.204 4284-4286 45.62 2.28 20.009 4286-4288 45.31 3.59 12.662 4288—4290 47.71 2.30 20.786 4290—4292 43.83 5.57 7.868 4292—4293 34.76 13.06 2.661 4293—4297 No Sample 4297-4298 45.59 4.15 10.986 4298-4300 41.35 7.51 5.506 4300-4302 46.57 2.68 17.375 4302-4304 38.49 8.14 4.731 430454306 35.36 11.55 3.062 4306-4308 37.17 9.90 3.754 4308-4310 34.40 10.37 3.318 4310-4312 39.89 1.34 29.771 4312-4314 40.36 1.41 28.628 31 Classification Lithologic Description Highly dolomitic ls. Dolomitic limestone Dolomitic limestone Highly dolomitic ls. Dolomitic limestone Highly dolomitic ls. Calcareous dolomite A292.l-A293.0 Ls, brn dns & brn dns tt dol, intbd w/ thn strg of carb mat, also a few 1 to 3 in strg of x1 is w/ rd sd gr. one golf ball sz vug at 4295.4 w/ cly like lmy-brn x1 dol from A292.l to 4292.5 w/ some wh x1 dol filling. 4293-4297 No Sample Highly dolomitic ls. 4297-4298.8 Ls, brn, vvfx, clean dns. Highly dolomitic ls. 4298.8-4299.4 Ibl, brn, vfx. 4299.4-4300 Ls, vvfx, v dns. Dolomitic limestone A300-A303 Ls, brn & gry brn, generally cln, few thn dk carb ptg, Highly dolomitic 1s. v dns. 4303—4304.6 Dol, brn & gry brn, f to m x1. Calcareous dolomite A3OA.6-A305.5 Ls, brn, vvfx Highly dolomitic 1s. 4305.5-4306.6 Dol, brn, f to m xl. A306.6-A307.8 Ls, brn, vvfx, clean, dns. Calcareous dolomite A307.8-A309 Dol, brn, m xl. A309-A31A Ls, brn to gry, vvfx to Dolomitic limestone crpxl w/ many blk highly bit shy ptg, (from paper thn to 5 in thk), Dolomitic limestone dns. Fl! how (Basso? (\l °\qu %>\\.6.U I). 63o. 3.53 “00.3980 H .02 Hawk ©830m1s0mampom 93 .Ho m3 QOHPSonnmm gamma .Ho soapaom 83mm misc i \. LJu—l >\ > < >< VHF“, siE NN «if (f? \\Jr> / \< ¢ \ , / r\ e ___£ £ 00:... OONV Don? TABLE II Results of Test for Insolubles Dolomite Band Carbonaceous Band Limestone Area Total Rock 11.30 gm 9.70 gm 8.19 gm Insolubles 1.01 gm 2.41 gm 0.50 gm Carbonates 10.29 gm 7.39 gm 7.69 gm Total Insolubles from Carbonaceous band 1.30 gm Clay fraction 0.77 gm Silt fraction 0.53 gm Ratio of Silt to Clay 0.688 33 BIBLIOGRAPHY Cheng, K. L., T. Kurtz, and R. H. Bray, 1952, Determination of Calcium and Magnesium, and Iron in Limestone: Analytical Chemistry, v. 2A, no. 10, p. 16AO. Chillingar, C. V., 1957, Classification of Limestones and Dolomites on Basis of Ca/Mg Ratio: Jour. Sed. Pet., v. 27, no. 2, p 0 187-189 0 Cohee, G. V., 1947, Cambrian and Ordovician Rocks in Recent wells in Southeastern Michigan: A.A.P.G. Bull., v. 31, no. 2, , 19A8, Cambrian and Ordovician Rocks in the Michigan Basin and Adjoining Areas: A.A.P.G. Bull., v. 32, no. 8. Horowitz, Martin, 1961, The St. Peter-Glenwood Prdblem in Michigan: M.S. Thesis, Michigan State University. Jodry, R. L., 1954, A Rapid Method for Determining the Magnesium/ Calcium Ratios of well Samples, and its Use as an Aid in Predicting Structure and Secondary Porosity in Calcareous Formations: Thesis, Michigan State University. Kirschke, W. H., 1961, A Petrographic Analysis of the Peterson- Howard Well #1 core, Pulaski wanship, Jackson County, Michigan: M.S. Thesis, Michigan State University. Krumbein, W. C., and F. J. Pettijohn, 1938, Manual of Sedimentary Petrography , Appleton-Century, New York. Rones, Merris, 1957, A Litho-stratigraphic, Petrographic and Chemical Investigation of the Lower Middle Ordovician Carbonate Rocks in Central Pennsylvania: Thesis, Pennsylvania State University. Reig, L. E., 1958, A Petrographic and X-Ray Study of the Dolomite Distribution in Certain Cambro-Ordovician Limestones of Central and South Central Pennsylvania: Ph.D. Thesis, Graduate School of the University of Pittsburgh. Tinklepaugh, B. M., 1957, A Chemical Statistical and Structural Analysis of Secondary Dolomitization in the Rogers City- Dundee Formation of the Central Michigan Basin: Ph.D. Thesis, Michigan State University. 34 $200M u: c:3 0. ”a, «a» yr.“ W- i -_ «Ms. “ --— ‘mdfi-ww-_- _- ' "‘ 1W1 1111111111111W| HI 11 I11 El 31293 01747 7823