STATE OF OHIO John J. Gilligan, Governor DEPARTMENT OF NATURAL RESOURCES William B. Nye, Director DIVISION OF GEOLOGICAL SURVEY Horace R. Collins, Chief Report of Investigations No. 86 HIGH-CALCIUM LIMESTONE FACIES OF THE DEVONIAN DUNDEE LIMESTONE , NORTHWESTERN OHIO by Dav id A. Stith Columbus 1972 SCIENTIFIC AND TECHNICAL STAFF OF THE OHIO DIVISION OF GEOLOGICAL SURVEY ADMINISTRATIVE SECTION Horace R. Collins, MS, State Geologist and Division Chief David K. Webb, Jr., PhD, Geologist and Assistant Chief Jean Simmons Brown, MS, Geologist and Editor William J. Buschman, Jr., BS, Administrative Geologist Karen M. Harper, BS, Geologist Pauline Smyth, MS, Geologist Eleanor J. Hyle, Secretary REGIONAL GEOLOGY SECTION Richard A. Struble, PhD, Geologist and Section Head Richard W. Carlton, MS, Geologist Richard M. DeLong, MS, Geologist Norman F. Knapp, MS, Chemist Arthur H. Morch, PhD, Chemical Engineer David A. Stith, MS, Geologist Joel D. Vormelker, MS, Geologist SUBSURFACE GEOLOGY SECTION Adriaan Janssens, PhD, Geologist and Section Head Michael J. Clifford, BS, Geologist Barbera J. Adams, Clerlt.-Typist B. Margalene Crammer, Clerlt. James Wooten, Geologist Aide LAKE ERIE SECTION David K. Webb, Jr., PhD, Geologist and Acting Section Head Lawrence L. Bmidech, BS, Geologist Welter R. Lemke, Boat Captain PUBLICATIONS SECTION Herold J. Flint, Cartographer and Section Head James A. Brown, Cartographer Donald R. Camburn, Cartographer Philip J. Celnar, BFA, Cartographer J een J. Miller, Photocopy Composer STATE OF OHIO John J. Gilligan, Governor DEPARTMENT OF NATURAL RESOURCES William B. Nye, Director DIVISION OF GEOLOGICAL SURVEY Horace R. Collins, Chief Report of Investigations No. 86 HIGH- CALCIUM LIMESTONE FACIES OF THE DEVONIAN DUNDEE LIMESTONE, NORTHWESTERN OHIO by David A. Stith Columbus 1972 GEOLOGY SERVES OHIO ~ CONTENTS Page Page Abstract ................................................. 1 X-ray solid-solution analysis ................... 5 Introduction .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. 1 Results ................................................. 8 Purpose and scope .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. 1 Quantitative X-ray analysis ..................... 8 Geologic setting .. .. .. .. .. ... .. .. .. .. .. .. .. .. .. .. .. .. 1 Chemical analysis ................................. 9 Acknowledgments ................................... 3 X-ray solid-solution analysis ................... 10 Procedure . .. .. 3 Summary ................................................ 10 Sample collection .. .. ... .. .. .. .. .. .. 3 References cited .................................... .. 10 Quantitative X-ray analysis .. .... ...... .. .. .. .. .. 3 Appendix ............................................... 12 Chemical analysis .. .. .. .. .. .. .. .. 4 Sample descriptions ............................... 12 FIGURES 1. Locations of sampling sites ................... 2 3. X-ray calibration curve for dolomite ......... 4 2. X-ray calibration curve for calcite ........... 4 4. X-ray calibration curve for quartz ............ 5 TABLES 1. X-ray instrument settings ...................... 3 by X-ray and chemical analysis ............ 6 2. X-ray diffraction peaks used in quantitative 5. Chemical analysis data ........................ 9 analysis .......................................... 3 6. Limestone standard (G. F. Smith #401), 3. AAS standard solutions ....................... .. 5 analytical results .............................. 9 4. Comparison of calcite, dolomite, and quartz 7. Solid-solution data .............................. 10 111 HIGH-CALCIUM LIMESTONE FACIES OF THE DEVONIAN DUNDEE LIMESTONE, NORTHWESTERN OHIO by David A. Stith ABSTRACT A lithographic limestone facies of the Devonian Dundee Limestone is exposed in two quarries in Paulding County, Ohio, and is present in the subsurface in much of the north- western corner of the state at depths of less than 900 feet. Samples of this facies were collected from one of the quarries and from representative water- and oil-well sample strings. The samples were analyzed for calcite, dolomite, and quartz by X-ray diffraction and for calcium, magnesium, silicon, aluminum, iron, and potassium by atomic absorption spectrophotometry. Results of the analyses show that the facies is a high-calcium limestone. In general, calcite content is greater than 95 percent; MgO is less than 0.5 percent, Si02 is less than 1.0 percent, and Fe20 3 is less than 0.1 percent. INTRODUCTION Geologic setting Purpose and scope The Dundee Limestone of northwestern Ohio is Middle_ Devonian in age. It is underlain by the Detroit High-calcium limestone is a commodity that is be- River Group and overlain by the Traverse Group. coming increasingly scarce. As the demand for pure The Detroit River Group in the study area is undif- limestone increases and the surface supplies are ferentiated. It is sublithographic to finely crystalline worked out, those deposits not now economically at- light- to medium-gray, grayish-brown, and brown dolo- tractive may become minable. mite and sandy dolomite, laminated and pelletal in part. At the present time a lithographic limestone facies The Dundee Limestone can be divided into two of the Dundee Limestone is exposed in two quarries in units. The lower Dundee is sandy sucrosic light-gray Paulding County, Ohio (State mine numbers Pg 1 and and light-brown dolomite and limestone with abundant Pg 2). In a recent report J anssens (1970) showed the chert. The upper Dundee is fossiliferous medium- to distribution and thickness of the facies in the subsur- coarse-grained light-gray, yellowish-gray, and medium- face in Defiance, Williams, and parts of Fulton, Henry, brown limestone. In the study area the basal portion of and Paulding Counties. The isopach lines in figure 1 the upper Dundee is a sublithographic to lithographic are reproduced from figure 7 of his report. The purpose very light-gray, medium-gray, and grayish-brown lime- of the present report is to show the mineralogical and stone, pelletal in part. The outcrop of the lithographic chemical composition of this lithographic facie s as facies is limited to a portion of Paulding County and determined by X-ray diffraction and atomic absorption extreme southeastern Defiance County. The glacial spectrophotometry. overburden in this area is mainly ground moraine and 1 I'-> ----r- --,--- -- 0\ 7 I -- I -- ---,:---,I r-I I I •S-1005 Rs-2037 • ,,,.o I L :u c : A s I • • I I I S·109~--- -~ 111 1 •S-1,21 S-1474 _____l ____ J ____ -f_J _____ _ I I •s-911 I I I I I ---- -- -- -- -· - I I I I I ( fJ -J I ---- I 1 I J -.I':. __I 1 I I I ------- _t.S.:.6J!.. _ 1- 11 -------- I ••s-823 I 51 1 ,i- ----I ----- IL _,- ----'--- 1 I w II L L 11 A M SI I S· I •S-2Q_l7 I I : I ::c I I I I • S· 1 964 I I I C) I ,,() 1 • S-306 I r.,_ I I "' I S-655• · -- I ::c -----,-------1-- ___ ,.. - •S-654 I I --- (J 1 I o..o l I I ,----f l _____ _ "' I I I I > 1 -l r' I /t -- -r-- L._.., I I (") I S-1429 I •S-1934 I I I I I '---t---lI -., I I I I I I I I I I I ~ I L-.rT-__ L I r' --, --- I --,--- I I 1 r---- 1 I J I I 1 ~ I I I I r-- I I 1 CJ') I I D E Fl I .rJ.-, I L-r-J ....; : s-11s5L •s-1055 I 1 I l I", .. ' ' ' -------t-------1-'§:_9~ I I I I ~ 31 lTl : .:::: tE -~--R-:~----""--- ---:- '"1:i f ---;-----r------ > 0 I I1 ~I 0 II II W QII Q IDI II [Tl I I I I I I I I I CJ') 0 ----r- -;;;;; L.._ M-32 I ----- t- ----:- -- --_j_ ----- -i -----i ----- ~ ------ '"1:i I I I I I I I . I ....; r I I I I I I ::c I I I I I I I I lTl I -----8~;~0~9& Pg 1 I I : l : : : 0 ~ I : - ,----:------:----,----- __,___ 0 I I I I I I I I p iA u L I D I N1 G I I I I lTl lTl I I I I 1 I ----! _____ ,_ I I : I S-1474 • Oil well r' ~ I j -- -r------,-- -- M-32 • Water well [Tl --i------t- ---- --1 CJ') MI 1 I I P: U T IN A MI Pg 20 Quarry ....; 1 I I I I I 87·2049 & Near-surface core I I I I I I I ~ I J I I I 87-2048 Ohio Division of Geological [Tl - ' --- I ----'-' - ------r------,- I Survey field sample number t ' --,.I r-I I' T I I ,------r-----1 -20- I 1 1 O If Miles r-- I 1 I I I: I 'lJ U 'Y FIGURE 1.-Locations of sampling sites; isopachs on lithographic limestone facies from J anssens (1970). PROCEDURE 3 lacustrine silt and clay and ranges from I 5 to 70 feet. Quantitative X-ray analysis Maximum depth to the facies is about 900 feet in Wil- liams County. The determination of the mineralogical composition In northwestern Ohio the Traverse Group consists of a rock by X-ray diffraction has become commonplace. of the Silica Formation and the Tenmile Creek Dolo- The methods primarily used determine either the ratio mite_ The Silica Formation, overlying the Dundee, is of the minerals in a rock from the ratio of their diffrac- interbedded fossiliferous grayish-brown limestone and tion intensities or the absolute percentages of minerals shale. The Tenmile Creek Dolomite is fine- to medium- in a rock from the ratios of their diffraction intensities grained light-yellowish-gray dolomite with abundant to that of an internal standard (Azaroff and Buerger, chert. In much of Williams County and the northwestern I958; Cullity, I956; Fisher, I968; Gulbrandsen, I960; part of Defiance County, limestone predominates and Runnells, I970). the Traverse is undifferentiated (Janssens, I970). All of the samples were analyzed by quantitative X-ray diffraction. The internal standard method was Acknowledgments used with reagent-grade CaF 2 (fluorite) as the stand- ard. The rock was ground to less than 85 mesh by hand The author would like to express his appreciation or by a micropulverizer, depending on the amount of to the managements of those quarries contributing sam- sample. Each sample was prepared for X-ray analysis ples to this study. The well sample descriptions were by mixing approximately 0.75 gm of sample with suffi- done by Dr.