Chemical and physical examination of the chert-free portions of the Keokuk Limestone (Mississippian) in Cherokee County, Kansas, showed it to be a high purity (mean 98.31% CaCO3), low silica (mean 0.24%), low iron (mean 0.12%) limestone of commercial quality. It is estimated that about 1 1/4 million tons of the high-calcium limestone are present. Analyses of the limestone are included. Loss on ignition rate was shown to increase when the samples were calcined under a nitrogen atmosphere

Waugh , Truman C.

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اکMINNOFSITYNOV281966LIBRARYAnalyses of High -Calcium Chert -FreeBeds in the Keokuk Limestone ,Cherokee County , Kansas Winchell[tbraryofGeologByTruman C. WaughSTATEGEOLOGICALSURVEYOF 1889KANSAS STATEGLOGICALSURVEYKANSASTHE UNIVERSITY OF KANSASLAWRENCE , KANSAS 1966BULLETIN 180 , PART 2STATE OF KANSAS William H. Avery , GovernorBOARD OF REGENTS .Henry A. BubbCharles N. CushingJohn F. EberhardtRay EvansClement H. HallArthur H. Cromb , ChairmanDwight D. KlingerLawrence D. MorganEldon SloanMax Bickford , Executive OfficerMINERAL INDUSTRIES COUNCILHoward Carey , Jr.Simeon S.ClarkeCharles S.CookLee H. CornellO. S.FentBeatrice L. JacquartGeorge K.Mackie , Jr.Robert F. Walters , ChairmanGeorge E.Nettles , Jr.Clifford W. StoneW. L. StrykerBenjamin O.WeaverSTATE GEOLOGICAL SURVEY OF KANSASW.Clarke Wescoe , M.D. , Chancellor of The University and ex officio Director of the SurveyFrank C. Foley , Ph.D. , State Geologist and DirectorWilliam W.Hambleton , Ph.D. , Associate State Geologist and Associate DirectorRaymond C.Moore , Ph.D. , Sc.D. , Principal Geologist EmeritusJohn M.Jewett , Ph.D. , Senior Geologist EmeritusNorman Plummer , A.B. , Senior CeramistLila M.Watkins , SecretaryADMINISTRATIVE SERVICES SECTIONEDITORIAL DIVISIONEdwin D.Goebel , M.S. , ChiefDoris E.Nodine Zeller , Ph.D. , HeadGrace E. Muilenburg , B.S. , HeadBeth Clark Kolars , HeadPUBLIC INFORMATION DIVISIONILLUSTRATIONS DIVISIONENVIRONMENTAL GEOLOGY SECTION Paul L. Hilpman , M.S. , ChiefGEOCHEMISTRY SECTION Ernest E. Angino , Ph.D. , ChiefGEOLOGIC RESEARCH SECTION Daniel F. Merriam , Ph.D. , ChiefMINERAL RESOURCESSECTIONPRODUCT DEVELOPMENT DIVISIONRonald G. Hardy , B.S. , ChiefMaynard P.Bauleke , Ph.D. , HeadAllison L. Hornbaker , M.S. , HeadRonald G.Hardy , B.S. , HeadINDUSTRIAL MINERALS DIVISIONECONOMIC ANALYSIS DIVISIONOPERATIONS RESEARCH SECTION Owen T. Spitz , B.S. , ChiefDouglas L. Beene , B.S. , Acting HeadOIL AND GAS DIVISIONWATER RESOURCESSECTION Robert J. Dingman , B.S. , ChiefGROUND-WATER RESOURCESCOOPERATIVE STUDIES WITH THE UNITED STATES GEOLOGICAL SURVEYRobert J. Dingman , B.S. , District GeologistW.L. Adkison , B.S. , Geologist in ChargeD.L. Kennedy , Regional EngincerMINERAL FUELSTOPOGRAPHYBRANCH OFFICESWELL SAMPLE LIBRARY , 4150 Monroe Street , Wichita R.L. Dilts , B.S. , Geologist in ChargeSOUTHWESTKANSAS FIELD OFFICE , 1111 Kansas Plaza ,Garden City R.C.Prill , Ph.D. , In ChargeNORTHWEST KANSAS PROJECT OFFICE , 465 North Austin Avenue ,Colby E.D.Jenkins , B.S. , Engineer in Charge1989STATE GEOLOGICALSURVEY BULLETIN 180 , PART 2KANSASAnalyses of High -Calcium Chert -FreeBeds in the Keokuk Limestone ,Cherokee County , KansasBy Truman C. WaughPrinted by authority of the State of KansasDistributed from LawrenceUNIVERSITY OF KANSAS PUBLICATIONSNOVEMBER 1966CONTENTSPAGE PAGEAbstract 3ILLUSTRATIONSFIGURE1. Map showing sample locations , CherokeeCounty , Kansas .2. Rate of loss of weight on ignition curves forchert -free samples from the Keokuk Limestone and for analytical - grade calcium carbonate.Introduction 33AcknowledgmentsSampling Procedure 3 7Sample Preparation 4 TABLESDiscussion 6 PAGEConclusions 7TABLE1. Chemical composition of high -calcium chertfree beds in the Keokuk Limestone , CherokeeCounty , Kansas .References 7 5TRUMAN C. WAUGHAnalyses of High -Calcium Chert -FreeBeds in the Keokuk Limestone ,Cherokee County, KansasABSTRACT SAMPLING PROCEDUREChemical and physical examination of the chert -free Nine spot samples were taken from an outportions of the Keokuk Limestone (Mississippian ) inCherokee County , Kansas , showed it to be a high puritycrop of the chert -free beds in the Keokuk Lime(mean 98.31 % CaCO3 ), low silica (mean 0.24% ), low stone along a northeastward flowing creek ( Fig .iron (mean 0.12% ) limestone of commercial quality . 1 ) :It is esumated that about 194 million tons of the highcalcium limestone are present. Analyses of the limestone KGS SampleNumberLocationare included . Loss on ignition rate was shown to increase 65146 SE SE SE Sec. 35, T 34 S, R 25 Ewhen the samples were calcined under a nitrogen atmos 65147 dophere. 65148 do65149 do65150 doINTRODUCTION 65151 do65152 doMississippian rocks are found at the surface 65153 NW NW NW Sec. 1, T 35 S, R 25 Ein Kansas only in a small area of less than two 65154 SE NW NW Sec. 2, T 35 S, R 25 Etownships in Cherokee County in extreme south Samples 65146 through 65152 were taken at aeastern Kansas ( Fig . 1) . Here the Keokuk vertical spacing of 4 to 5 feet along the outcrop .Limestone of Osagian age is a bluish -gray to These samples were found to have an excepgray , sometimes buff, medium- to coarse-grained, tionally high calcium carbonate content of 97 tofossiliferous limestone ranging from 10 to 100 99 percent ( Table 1 ) .feet in thickness . Fossiliferous chert is irregu In order to assure good sample representationlarly distributed throughout the Keokuk . Within the Keokuk chert - free beds occur , ranging inand to provide a check of the chemical composition of the spot samples 10 channel samples werethickness from 10 to 50 feet.collected . Of these 10 samples, five were takenAnalyses of chert - free strata in the Keokuk at each of two locations . The first location wasLimestone have shown that the calcium cara bluff cut by a small unnamed northward -Howbonate content is as high as 97 to 98 percent(Runnels, 1951; Runnels andSchleicher, 1956 ) . ingcreek through oneofthechert -free beds( Fig . 1 ) :An extension of these studies seemed warrantedbecause ofconsiderable interest in both the occur- KGSSampleNumber661rence and use of high -calcium limestone . Nine NE NE NE Sec . 2, T 35 S , R 25 E662 dospot samples and eight channel samples were 663 docollected for analysis . 664 dodoACKNOWLEDGMENTSAn exposed portion 28.2 feet thick was sampled .W. E. Hill , Jr., and A.L. Hornbaker aided The first 5 - foot channel sample ( 661 ) was takenin sample location and collection . George Shimer vertically beginning at the top of a chert -bearingmade some ofthe chemical analyses . limestone in the Keokuk lying approximately 2aLocation6654 Kansas Geol . Survey Bull . 180, Pt. 2 , 1966Locationfeet above the creek bed . Four 5.8 -foot channel An additional 5 - foot channel sample (6610 ) wassamples (662-665 ) were taken above it . taken on the outside of the underground quarry .The second sample collection site was an Channel sampling was done according to theunderground quarry ( Fig . 1) : procedure used by Galle ( 1964 ).KGS SampleNumber666 SW SW SW Sec. 25, T 34 S, R 25 E SAMPLE PREPARATION667 do668 do The samples were prepared foranalysis by669 do crushing in a mechanical jaw crusher , followed6610 dobyquartering and splitting until a sample size ofFour 5 -foot channel samples were taken in the approximately 100 g was obtained . They wereunderground quarry , one ( 666) in the chert- further ground bymortar and pestle until eachbearing limestone and three (667-669 ) above it . sample passed a 60-mesh screen (250 m ) . TheM.-K.-Y.R.R.RIVERST335T345K.26JASPERCOUNTYSPRINGK. 26 U.S. 66 GalenaK.C.S.RY.ST.L.- S.F. RYST.L.-S.F.RY. KetuaShoa? MISSOURIQuarry !U.S.66COUNTYCreekK.26Bluff T345T355U.S. 166Fakat NEWTONU.S.166BaxterSpringsOTTAWA COUNTYK.O.&G.RYR24ER25E OKLAHOMAR25EFIGURE 1. —Map showing sample locations , Cherokee County , Kansas . ( Based upon General Highway Map , Cherokee County , Kansas , 1963 ed. )Waugh - High -Calcium Chert -Free Beds, Keokuk Limestone , Cherokee County , KansasTable1.- Chemicalcompositionofhigh- calciumchert- freebedsintheKeokukLimestone, CherokeeCounty, Kansas.KGSsamplenumberSiogMgoTio,A1,0,Fe,ogСаоSPOSO,NaoMgCO,( Calc.)Caco,( Calc.)K,0LOI550LOL550/1000TOTAL0.3065146651476514865149651506515165152651536515466166266366454.9655.2655.3855.3355.3955.1755.1355.2654.8355.1355.2554.9755.0255.1244.04*55.0554.8854.5353.28*54.790.260.370.390.380.290.190.320.250.330.410.420.210.370.170.280.300.340.430.280.2198.0998.6398.8498.7598.8698.4798.4098.6397.8698.4098.6198.1198.2098.3878.6098.2597.9597.3395.0997.790.570.340.210.080.320.360.500.330.540.340.080.210.520.170.610.690.801.991.171.040.300.170.160.270.100.220.190.140.510.100.130.330.170.2319.83*0.360.290.422.44*0.270.120.040.030.060.020.050.03Nil0.120.090.110.150.110.090.060.030.040.050.120.070.150.110.100.130.140.120.120.100.150.080.080.160.110.140.130.130.130.130.180.100.020.020.040.030.010.020.010.030.04NilNilNilNil0.010.050.040.050.050.050.04TRTRTRTRTR TRTRTRTR 0.01TRTRTRTR 0.020.010.010.010.020.01TRNilTRTRTRTR NilTRTRTR TRTRTRTR0.050.010.020.050.01TRTR NilNil0.01Nil<0.010.01Nil<0.010.010.020.020.010.010.010.010.020.01TR 0.01TR TRTRTR TRTRTR TRTR NilTRTRTRTR 0.030.050.080.080.150.150.010.010.010.010.010.010.010.010.01NilTRTRTRTR 0.010.010.020.020.020.020.140.180.250.170.240.200.170.320.310.330.430.250.350.250.400.460.440.510.3343.4343.5543.5743.4643.6443.4943.5243.5443.3143.4443.4043.2543.4543.3534.83*43.5543.4743.3942.3943.5799,5599.6799.8699.9299.7799.5199.5399.5099.6299.5799.7299.5099.4899.4699.5899.9499.7999.6099.4599.56665666*6676686696610*52137+Mean0.3198.310.540.07.020.3043.4155.080.230.240.110.120.03S • Samples666and6610exceededthelimitsofthreestandarddeviationsandwereexcludedinthecalculationsforCaOandSio+KGSsample52137( NESec.26,T34S,R25E)describedbyRunnelsandSchleicher, 1956, rerunandincludedforpurposesofcomparison.6 Kansas Geol . Survey Bull . 180, Pt. 2 , 1966asieved samples were rolled and blended until As part of the study of physical properties ofthoroughly mixed . They were then split to ap- the chert -free limestone in the Keokuk , loss ofproximately 20 g foranalysis . Chemical analyses weight on ignition (LOI ) was determined under)were carried out as described by Hill , et al . three different atmospheric conditions : in carbon( 1961 ) . dioxide , in air , and in nitrogen . A setofthreesamples ( 663 , 665 , and 667 ) was chosen for theDISCUSSION LOI study . These were heated and held at 50 ° CSamples 661 thru 6610 were assumed to forintervals of1 hour , cooled , and weighed .be most representative owing to the channel The temperature range was from 500-1000 ° C .sampling technique used . The standard devia- The resulting percent loss of weight on ignitiontion ofthe CaO in these samples was determined was summed and graphed against temperature( Table 1 ) . Similarly , using the CaO values of( Fig . 2 ) .the spot samples ( 65146-65154 ) , a second stand Curve A ( Fig . 2 ) represents the rate of LOIard deviation was calculated and found to beofthe chert - free samples of Keokuk Limestoneessentially the same as that ofthe channelwhere the samples were heated in a muffle fursamples . A Student t test supports the assumpnace in closed platinum crucibles . In this systemtion that allthesamples were from the same the convection volume was reduced to thatpopulation .Since the CaO values ofthe spot samplesbounded bythe sides and lid ofthe platinumcrucible and the surface ofthe sample ( no morewere within one standard deviation of the Caovalues forthe channel samples , a more inclusive than 17cc ) . Since there would have been littlestandard deviation was calculated using the dilution ofthe carbon dioxide ( CO2 ) evolvedvalues of CaO forspot and channel samples , ex with air , the sample was essentially in a CO . ,cluding samples 666 and 6610. The accepted enriched atmosphere — themost favorable condiformula used for staard deviation was : tion forrecarbonation and the poorest for rapidevolution ofgas and subsequent loss of weight .Σ ( ( X – X ) 2 Curve B represents a setof samples heatedS = + without lids in a closed muffle furnace in an air- 1CO . , atmosphere . There was a marked increasewhere : in the rate ofCO2 evolution . The volume whichS = standard deviation , previously was restricted to the platinum cruciX = sample determination , blewas in this case expanded to include theX = mean of sample determinations , volume ofa proportionate part ofthe inside ofn = number of determinations . the muffle furnace . This procedure allowed amore rapid loss of CO2 and a consequent inThe standard deviation for these samples was crease in the rate of weight loss .found to be 0.23 for CaO . The mean Ca ( ) con- Curve C represents the results obtained whentent was 55.08 , which is equivalent to 98.31 per- a constant flow of nitrogen (N2 ) was passedcent CaCO3 . Values from 54.85 to 55.31 percent through the muffle furnace and over a set ofCao encompassed alldata within one standard samples in uncovered platinum crucibles . Thisdeviation . technique gave thegreatest CO , evolution rate .In order to obtain a representative figure for Sweeping the surface of the limestone with N.thetwo most common impurities , thestandard rapidly removes the CO. , and prevents recarbonadeviation was also figured for silica ( SiO2 ) and tion as noted by Boynton ( 1966 , p . 140 ) . Rateiron ( Fe , O3) . The mean value forSiO2 was ofloss on ignition ofanalytical -grade calcium0.24 percent , with a standard deviation of0.11 . carbonate is shown for purposes of comparison .The low silica value of the chert - free beds in the These data clearly indicate that if maximumKeokuk Limestone suggests their possible use loss of weight on ignition is desired at any givenin many industrial processes ( e.g. , as blast fur- temperature forany given time increment ( herenace flux ) . 1 hour ) then consideration of the use of N. , orIn determining the standard deviation for some other inert sweeping gas is indicated . FurFe2O3 , samples 666 and 6610 were included ther investigation ofthe effects ofan N , atmos( Table 1 ) . The mean was 0.12 percent , and the phere on therate of weight loss ofthe limestonestandard deviation 0.03 . The other constituents seems warranted . Additional study will be necesofthis limestone make upless than 0.5percent sary before the mechanics acting to produce( Table 1 ) and were not treated statistically . these effects are fully known .>nWaugh - High - Calcium Chert- FreeBeds , Keokuk Limestone , Cherokee County , Kansas 71000900ААB800B   11700600KEOKUK LIMESTONE ANALYTICAL - GRADE COCO350010 20 30TH40 0 10WEIGHT LOSS, PERCENT20 30 40 50FIGURE 2. -Rate of loss of weight on ignition curves for high -calcium chert - free samples from the Keokuk Limestone and for analytical -grade calcium carbonate . A , CO2 - enriched atmosphere ; B , C0 , -air ; C , N. Loss on ignitionrate increased progressively from A to B to C.CONCLUSIONSThe Keokuk Limestone in Cherokee Countyin southeastern Kansas is a limestone of unusually high calcium content . The amounts ofchert - free limestone available in this part of theKeokuk Limestone are estimated to be oftheorder of1-1/ 4 million tons based upon a 20 -footthickness ( personal communication , AllisonHornbaker , 1966 ) . Approximately 20 acres areavailable foropen pitquarry operation . Exploratory drilling will be necessary in order tooutline the areal extent of high quality limestone . The chert - free limestone studied here iswithin 4 miles of rail transportation available inthe north part ofGalena ( Fig . 1 ) . It is 6 milesfrom Baxter Springs , Kansas , and 13 miles fromJoplin , Missouri .REFERENCESBOYNTON , R.S. , 1966 , Chemistry and Technology ofLime and Limestone : 520 p . , Interscience Publishers , John Wiley& Sons , N.Y.GALLE , O.K. , 1964 , Comparison of chemical analyses based upon two sampling procedures and two sample preparation methods : Trans . Kansas Acad . Sci . , v . 67 , no. 1 , p . 100-110 .Hill , W. E. , JR . , Waugh , W. N. , Galle , O. K. , and Runnels , R. T. , 1961 , Methods of chemical analysis for carbonate and silicate rocks : Kansas Geol . Surv . Bull . 152 , pt. 1 , p . 1-30 .MOORE , R.C., 1928 , Early Mississippian formations in Missouri : Missouri Bur . Geol . and Mines , v . 21 , 2d. ser. , p .1-283 .FRYE , J. C. , JEWETT , J. M., LEE , Wallace , and O'CONNOR , H.G. , 1951 , The Kansas Rock Column : Kansas Geol . Surv . Bull . 89 , 132 p .RUNNELS , R.T. , 1951 , Some high -calcium limestones in Kansas : Kansas Geol . Surv . Bull . 90 , pt. 5 , p . 77-104 .and SCHLEICHER , J. A. , 1956 , Chemical compositions ofEastern Kansas Limestones : Kansas Geol . Surv .Bull . 119, pt. 3 , p . 81-103

Analyses of High-Calcium Chert-Free Beds in the Keokuk Limestone, Cherokee County, Kansas

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Analyses of High-Calcium Chert-Free Beds in the Keokuk Limestone, Cherokee County, Kansas

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