__ E:g_:g::i_____:__:_2:13::3 . w .r . u. z. ,3 '- "4 ’5 4 “voov‘d-l a '- -¢.-\. .B.fi - wk. - V I . ‘ ' ' fHESIS. ,- A I .\ I This is to certify that the thesis entitled .. “A Rapid method for the Correlation of Fine-grained " 1. Sediments With the Aid of the Spectograph, As Applied to the IDe'von.’La.n-IVJ.ssisslppian Sequence in Clare County ' Michigan'l presented by David Stanley Paige has been accepted towards fulfillment of the requirements for / 1.9M/éA—«fi Major professorV A RAPID METHOD FOR THE GOREIATION OF FINE GRAINED SEDIMENTS WITH THE AID OF THE SPECTIDGRAPH AS APPLIED TO THE MISSISSIPPIAN—DEVONIAN SEQUENCE III CLARE COUNTY, MICHIGAN A RWID 2411:1301) F023 l‘ziE COULAZ‘IUN 0F It‘ll-,8 filth- w 5‘ D1718 WITH TH": All) OF TEE} 8.- EC"? SLG‘W’ f AS N7P'IJIYZD '30 mg}; :91 313133113} IMl-DWJO: IAN 83:33:03 m cum comm. HICZiIGAN David 8. P313. ABS’EE'tCT Because 01’ the rugid lateral changes taking place in the type of sediments being de;.-oeited at any particular time in different parts of the basin. mbsoguont correlation of these dogtosits from subsurface 60-11110! is sometimes very difficult. Consequently. (my method develo,od thich night facilitate this correlation is of worms value to the petroleum geologist. The writer describes a method «relayed which utilizes the egectrogreyh for the analysis of the relative ooqiosition of the soluble yortions of sediments. The smlos are treated Iith hydrochloric acid and the resulting solution is introduced to a flat neg-Luvs electrode with an sysdro'gper. ”The who are then tired and the sgeetra are recorded on congenial out shoot film for econow. The individual spectra are then sliced lengthwise and ogrlicod tagethsr to tom 3 loop. This long is then introduced into a sgeciol densitonntsr designed by the writer for this work. The whee-giant ratios of the shunts to be plotted with degth are used as a. basis for correlation. A RAPID NETHOD FOR THE CORRELATION OF FINE GRAINED SEDIMENTS WITH THE AID OF THE SPECTROGRAPH AS APPLIED TO THE MISSISSIPPIAN-DEVONIAN SEQIIENCE IN CLARE COUNTY . MICHIGAN BY DAVID STANLEY PAIGE A THESIS Submitted to the Graduate School of Michigan State College of Agriculture and Applied Science in partial fulfillment of the requirements for the degree of MASTER 03‘ SC IENCE Department of Geology 1952 THESIS /o-'V~§L—fip ACKNOWLEDGEMENTS After the original conception of the possibilities for the research outlined in this paper, all further work was done in collaboration with Mr. John H. Hefner. Without Mr. Hefner's long hours of diligent work it would have been impossible to complete the project in the time available. The writer would like to express his gratitude to Dr. S. G. Bergquist for his genuine interest in the develOpment of the research and for making the resources of the department available for the construction of the densitometer. The writer is also indepted to Dru B. T. Sandefur for correcting the manuscript, and to the Michigan Geological Survey for the samples which were used. 7.8657 8 LIST OF ILLUSTRATIONS . . . . INTRODUCTION . . . . . . . . Statement of the problem Section analyzed . . . . Area studied . . . . . . Analysis of shales . . . CONTENT Basic departures from accepted technique spectrographic RESUME 0F SPECTBDGRAPHIC THEORY . . . . . . Emission of spectral energy Recording of relative intensity values EQHIPMENT.......¢......... CONSTRUCTION OF DENSITOMETER. Reason for need. Essentials of design . . Description of instrument. Cost of parts. . . . . . DEVELOPMENT OF TECHNIQPE. . . Sampling . . . . . . . . Preparation of samples . Preparation of electrodes. Loading of electrodes . Cost of analysis PWWE O O O O O O O O O O 10 11 12 12 12 13 14 14 14 14 15 15 16 16 DENSITY TO RELATIVE DATA . . . . . . . Well number 1 . Well number 2 . Well number 8 . CUEWES SHOWING CHANGES WITH DEPTH INTENSITY OF THE RELATIVE RATIO OF BARR“ To MGNESIUMO 0 e e e e e e e o e e o 0 e 0 O INTERPRETATION OF RESULTS . . . . .'. . . . . . . . . . CONCLUSION Page 19 20 21 25 29 31 32 Figure ILLUSTRATIONS Index map showing location of wells . . . . . Positive print of typical series of exposures showing lines used for analysis . . . . . . . Density-relative intensity curve of the .mulsione e e e e e e e e e e e e e e e e e e DCRBitomCtere e e e e e e e e e e e e e e e e LOading Of €1.Ctr°d°8 o e e e e e e e e e e e vi Page . 11 . 12 . 16 INTRODUCTION In recent years much emphasis has been placed on the study of depositional environments as related to facies changes. The dependence of the sedimentary rock type on the tectonic events occurring concurrently with deposition has been well illustrated by Spieker (1949). The similarity of the lithology of geographi- cally separated beds of different ages having similar tectonic and environmental histories was the subject of a study by Pettijohn (1943). The emergence of these principles has clarified basic prob- lems inherent in attempting correlations over any appreciable distance. It becomes increasingly clear that extensions of litho- logic correlation across tectonic and environmental boundaries are subject to considerable question. The situation is further com- plicated by the transgression and regression of environmental zones with time. Thus a certain rock type, as determined by the physical factors controlling its deposition, is layed down at different times in different places. The dangers of using such a "key" horizon in determining the time-stratigraphic height of a formation were first pointed out by Lee (1915). The prdblem becomes even more complex in areas of possible faulting. Interfingering of facies accompanied by relative movement along fault planes makes the correlation between two points on relatively close wells subject to considerable uncerb tainty. To date, the most successful method for time-stratigraphic correlation has been paleontological. Geophysical methods depend largely on the physical characteristics of the strata.penetrated, and are therefore subject to the same limitations as are lithologic correlations. 'Even paleontological methods are greatly restricted in many areas by the lack of species superior to their environment. In the light of these facts, it seems evident to the writer that any method developed which.could circumvent these limitations, would have a definite place in stratigraphic studies. One of the newer approaches to this type of problem is by the use of geochemistry. If there are any conditions which are constant over the entire basin of deposition they might be reflected in some way by the chemical composition of the sedi- ments.> Probably the most laterally uniform of the environmental factors controlling sedimentation is the composition of the basin water in which the deposition takes place. There has been considerb able hepeful theorizing in the past few years on the possibility of conducting "trace element“ analysis as a possible means of correlation. It has been hypothesized that at certain times in the geologic past some rather rare elements could.have been present in the water for short periods. If this were true, the mere pres- ence of one of these elements in a stratum would have a very posi- tive correlative value. However, to the best of the writer's knowledge, no phenomenon so restricted in time has been noted. Either such.conditions have never prevailed, or there have been no methods as yet developed that would.pick out the important horizons. Continuing in this general line of research the writer scanned available data on the composition of present day basins to try to determine any qualitative difference which might be present. It was hoped that by following such a line of reasoning some clue might be found as to what elements one should look for in ancient sediments. This approach.proved futile, however, and the conclup sion was reached that any further work done along this line would have to be quantitative. It was decided that the most sensible way to quantitatively analyze large numbers of samples would be spectrographicalLy. The inherent speed of the spectrograph.coupled with the fact that the records of the analyses are permanently retained on the film, made the instrument extremely applicable to the type of work to be undertaken. Statemegt of the pzoblem - At this point the problem re- solved itself into essentially two parts. The first was to de- velop a spectrOgraphic technique which was rapid, and yet which retained sufficient accuracy so that the results could be inter- preted. The second phase of the problem consisted of develOping an interpretative procedure, and determining whether or not any relationship, such as was outlined in the preceding paragraphs did exist. Section gpalyzed.- Because of the scope of the problem it was decided to limit the sampling to one type of sediment. The lack of any really usable methods other than the gamma and neutron logs for the correlation of shales indicated a special need for research on argillaceous sediments. However, it should be empha- sized that future work need not be limited to any particular facies insofar as the overall principles are concerned. The MississippianpDevonian sequence was selected for study. It consists of some fifteen hundred feet of shales (Goldwater, Sunbury, Ellsworth, and.Antrim formations), with.minor beds of intertonguing sandstone (BereaéBedford facies). The present correlation of these beds is mainly litholOgic. The top of the Sunbury formation (black shale) is probabLy the most distinctive horizon. The electric log is also used to more accurately place the top of this bed. The gamma ray log shows a high.gamma reading in the Antrim shale. These beds were chosen not because of any peculiar problem of correlation, but rather for the purpose of developing a technique for their analysis that might find use in any further work along this line. ,Area studied - Wells selected from Grant and Sheridan Town- ships, Clare County, Michigan, were chosen for this study. However, as a similar problem was being conducted concurrently in Ogemaw County, three wells from this area were included in the final chart. The location of, and the data pertaining to these wells may be found on the following page. Analysis of shales - In itself, the process of unraveling the depositional history of shales presents many difficulties. It was realized at the beginning that argillaceous sediments Nmmm . . . . n mom . . . . m ”38 . . . . a .02 washed .oz So: .3550 eumao dummy m. mmbma . . . . m mmnma . . . . a .02 uuaem .oz .333 $300 sweemo <1. —_-_‘ 24L —l——- ___- would.probably be the most inconsistent of any type of facies which might have been.picked. The dependence of shales upon an immediate source for depositional material, and the rapid lateral lithologic changes due to this dependence long has been a major drawback in their correlation. The great amount of compaction which the shale undergoes along with "slumping“ in place and "gliding" along pro-existing slopes is bound to mask somewhat the original relationship of the beds. The concept of analyzing the sediments for those constitu- ents whose deposition might have been controlled by the composi- tion of the basinal water becomes slightly more complex in argillaceous rocks. In an attempt to eliminate the extraneous influence of the "dumping" of sediments from a nearby source it was decided to obtain what might be known as the "solubles" of shales for analysis. It was hOped that these would consist of the normal salts which were being deposited contemporaneously in all parts of the basin, and which should differ from those being layed down in other parts only in relative amounts. After preliminary qualitative and quantitative spectrographic analysis of samples which had been treated with hydrochloric acid it was found that this was true and the work was continued along this line. Basic departures from accepted spectrqgraphic technigu - During the course of the research several rather radical depar- tures from accepted spectrOgraphic technique were made. It is deemed preper to mention the more important here. The first, and probably most essential of these changes is in the method of computing the results from the readings obtained from line density determinations. In most spectrOgraphic work it is necessary to determine the absolute percentage of an impurity or other minor constituent within some substance. To do this, known samples must be run and the results plotted on what is known as a "working curve" for the element in question. A separate curve must be plotted for each element analyzed. The unknown sample is then run, and the percentage of the constituent in question is obtained by interpolation from the curve. Other re- finements, such as the addition of “internal” or "external" stand- ards also are necessary in many cases. Rather than attempt to follow these tedious methods of analysis the writer decided to work entirely with relative ratios of the elements to be analyzed. This may be done by picking an arbitrary line from each element, and utilizing the variations of intensity of these lines. It should be evident from the foregoing that the entire interh pretation will be based on relative changes of composition. In a recent work by Sloss and Cooke (1946) the absolute percentages of the minor constituents of limestones were computed and then plotted by means of bargraphs or histograms. Every element was then plotted with a different scale so as to make the range of varia- tions for each element, as shown on the graph, equal. If each of these bars is now measured with the same rule, without regard for original scale, and the ratios of these measurements calculated, the results would be comparable to what may be obtained by using the ratios of arbitrary lines. In other words, it is simply a matter of changing the scale. Furthermore, it seems to the writer that the absolute amounts of the minor constituents of sedimentary rocks have no meaning emept as they are related to one another. That is to say the deposition of the major constituents of sedi- mentary rocks is so affected by extraneous factors not related to the composition of the water that the amount of minor constituents per cubic foot will have no usable relationship to the volume of the major rock forming materials. The other changes are, very briefly, the positioning of cut sheet film in the plate holder so as to include previously picked lines (figure 2), Figure 2. Positive print of typical series of exposures showing lines used for analysis. and the construction of a densitometer especially designed to speed the reading of the line densities. These will be discussed at greater length in later pages. RESUME OF SPECTRDGRAPHIC THEORY There will be no attempt in this paper to fully cover the theory underlying the use of the spectrograph. However, a few of the principles upon which the methods developed in this work are based should be briefly mentioned. Further information may be obtained from any of the many books available on the subject. Two excellent works used as reference by the writer are those by Brode (1945) and.Ahrens (1950). Emi§§ion of specgral energy - When substances are burned at high.temperatures, the electrons present in the shells of the constituent atoms are affected in such a manner that they move to higher “energy levels". 'Each type of atom has its own number of levels, and each level has its own characteristic "state" of energy. These energized electrons are unstable in their new environments, and tend to return to their respective "ground states". In a manner of speaking, they have a choice as to how they may do so. For example, if an electron has been moved three levels above its ground state, it may return by any of four paths. It may travel by way of the first level, the second level, or via both of the inter— mediate levels. As the electron makes each "jump“ it gives off a definite amount of energy in the form of radiation. The nature of the jump determines the amount of energy released.per electron, per step. In turn, this unit amount of energy determines the frequency at which these light rays will be propogated. The number of electrons making each jump conforms to the laws of statistical probability. This accounts for the fact that every element has a number of lines of differing intensities. It should be evident at this point that any particular line of a specified element should vary in intensity directly as the amount of the parent atoms present in the sample. It is this direct relationship that is utilized in the preposed method. _3ecordigg of relative intensiyy values - When the radiations resulting from the burning of a sample are passed through a fine slit and directed onto a suitable dispersing agent, such as a system of prisms, or a grating, the rays are differentially refracted. The amount of refraction of each ray is dependent upon its fre- quency, and hence the position of the image of the slit that is produced by each characteristic dump of an atom will have a fixed position upon any plane of reference. By placing a photOgraphic plate in the focal plane of the instrument, a record of the relative intensity of each line may be obtained. 'Unfortunately, the response of the film emulsion to variations in intensity alters somewhat the ideal relationship outlined above. For the most part, however, while working within the limits of line density set by the particup lar type of film being used, the slaps of the intensity--line density curve is constant. Thus, with proper selection of the exposed films to be used for measurement of line intensities, the characteristic curve of the emulsion should not have to be taken into account. However, to utilize the maximum number of exposures an empirical relative intensity-density curve was constructed. To facilitate the interpolation of this curve, a reference chart was made up, 10 (see page 19) , giving the relative intensity values for line densities from one to one hundred. An approximation to the density-relative intensity curve used is shown in Figure 3. 100 10 100 Figure 3. Density-relative intensity curve of the emulsion. EQUIPMENT A. Cenco grating spectrograph equipped with a replica grating was the instrument used in this work. The source of excitation was a D.C. are, and the pictures were taken on Ansco Isopan cut sheet film. The densitometer used was designed and built by the writer. Electrodes were shaped from 2" lengths cut from National Carbon Co. standard spectrographic carbons. Electrode and bottle holders were constructed from strips of soft wood. Standard sampling bottles as used by the Michigan Geological Survey were used for the cuttings. Chemically pure lZN hydrochloric acid was diluted to Q1 with dis- tilled water. A separating funnel was used totintroduce the acid to the samples. CONSTRUCTION OF THE DENSITOMETER fieagon for need - The primary reason for the construction of the densitometer was the non-availability of any instrument equipped to handle celluloid film. In addition, however, the writer felt that the process of line density determination could be considerably speeded by the adeption of a few basic changes in densitometer design. Figure 4e Densitometer Essential. g of <1“ng - The densitometer was designed to simulate the operation of a movie projector. It handled continup ous strip film made up of individual spectra, spliced end to end. It consists of a light source, a condensing lens, a film track system, a slit lined in aluminum, and a sensitive light meter. 12 Qgggription of instrument - The standard about which the densitometer is constructed is an eight millimeter movie projector from which the light box, motor, and lens system have been removed. A small aluminum chassis, approximately 2” x 6" x 10”, is fastened to this base. The light source, which was a part of the projector, is mounted on the top of the chassis in such manner that the light is directed downward. The film track proper, being that part of the original pro— jector through which the film.passed on the way to the lens system, is mounted horizontally in the chassis so that its long axis is in line with the path of the film. A narrow slit was lined in a strip of thin aluminum which in turn was glued to the film track. Before gluing, the slit was so oriented that it was directly over the rectangular "picture frame“ contained in the track. When the film is moved over the track the lines are successively superposed on the slit. The light, passing through the condensing lens, the film, and the slit, is thus modulated by the density of the line which happens to be coincident with the slit. The amount of light reaching the slit is controlled by a "wedge—diaphragm" mounted directly under the light source. The circular film is kept taut by a spring arrangement built into the film track system. The film may be slowly moved through.the machine by turning a small knob which is geared to a pulley around which the film is wrapped. The modulated light, after leaving the slit, passes through. a short tube, at the bottom of which.a mirror is mounted. The light is deflected at right angles by this mirror so that it falls 13 on the light sensitive element of the light meter. This element conveniently plugs into a circular hole cut in the side of the chassis. Cost of parts - Excluding the cost of the light meter, and of the miscellaneous pulleys, nuts, and.bolts which were obtained from the department of GeolOgy, the entire cost of the parts used in the final design of the densitometer was about ten dollars. DEVELOPMENT OF TECHNIQUE .An integral part of the study was the development of the technique. .A brief discussion of each of the significant points will be included here. .A step by step summary of the entire procedure will be listed on later pages. ,§ag2ligg - .Samples were obtained from regular well cuttings such as stored by the Michigan G6010gical Survey. Approximately one gram of sample was poured into a standard sampling bottle for each interval (usually 10'). Due to the aforementioned nature of the work, it was deemed unneccessary to attempt any extreme caution on this point. Care was exercised, however, not to include too much material which did not seem to be characteristic of the sample as a whole. The amount of solubles derived from a particular sample will depend as much on such.factors as permeability, surface area, solubility, etc., as on the weight. This concept adds importance to the principle of using the ratios of the elements as a basis for correlation. Preparation of samples - The bottles containing the cuttings 14 were placed in the specially constructed bottle holders and onto a hot plate. They were then filled with.6N hydrochloric acid. The hot plate was turned on to hasten the action of the acid. The samples were simmered until they were sufficiently broken up to insure adequate solution. They were then removed from the hot plate and allowed to settle so that the solution was free of insoluble constituents. Preparatiog of electrodes - Preliminary quantitative work indicated that the standard type of'spectrographic carbon was suf- ficiently free of the elements to be measured that any further expense was unwarranted. .After considerable experimentation with different types of cavities it was decided that flat tapped elec— trodes were the most suitable for work with solutions. The posi- tive electrodes were sharpened slightly to partially control "arc wandering". .A small hand pencil sharpener proved ideal for this purpose. JBoth the positives and the negatives were levelled and polished at each end with emery cloth. ‘When they had been fired once it was merely necessary to invert them to provide another usable end. There are, therefore, two effective electrodes for one 2" length of rod. Loadipg of electrodes - The electrodes were inserted in the electrode holders and placed in a drying oven. .A drop of the sample was introduced to the tap of the negative electrode by means of an eyedroPper (Figure 5). The heat of the oven soon evaporated the liquid, leaving the sample impregnated in, and baked on the top of, the electrode. The eyedropper was then 15 rinsed with distilled water in preparation for the next sample. It is important to leave the electrodes in the oven until Just before they are to be fired. The dried salt takes on water readily and the difficulty of maintaining an even arc is greatly increased. Figure 5. Loading of electrodes Cost of agalysig - With laboratory labor figured at a dollar and a half an hour, the cost, per sample of this type of analysis, is under 25¢. PROCEDURE 1. Place approximately one gram of sample in each sample bottle. 2. Place bottles in holders and onto hot plate. Fill with acid. 16 3. 4. 5. 6. 7. 8. 9. 10. ll. 12. 13. Turn on hot plate, allow samples to simmer. Remove samples, allow insoluble material to precipitate. Load electrodes with eyedropper and dry in oven. Remove just before firing. Place electrodes (one positive ane one negative) in holders on spectrograph. Adjust height of electrodes so that the center of the elect- rode gap coincides with the height of the center of the slit on the spectrOgraph. I Close switch. Lower upper electrode to meet the bottom elect- rode and immediately raise, thus arcing the gap. Raise upper electrode to optimum height for prOper arcing (approximately one half inch). Open shutter on spectrograph for approximately four seconds. (Time will vary with type of film, amount of sample, etc.) Repeat for the seven exposures available on one film. Develop film in dark as follows: Two and one half minutes in Kodak D-19 develOper, agitating continuously, 30 seconds in running water wash, and approximately 10 minutes in acid fix. Allow to wash in water for convenient length of time, and dry. Cut film along each spectrum by running razor blade along straight edge on the side opposite the emulsion. Film will now break with bending. Splice film as follows: Scrape off emulsion from one end of the first film, being especially careful to scrape the very end. Roughen the other side of the second film. Apply regu- lar splicing cement and press films together for a short period 17 14. 15. 16. 17. of time. Repeat for the seven films. Notch ends of the completed strip of seven films so that they may be fitted to- gether as a loop. Insert film in densitometer and fasten the ends together. Tighten film on track'by releasing spring. Line up starting line (approximately one centimeter ahead of the Mg - 5184 line) with the edge of the film track. Set calibrated dial to starting point. Rotate film thromgh machine until dial indicates that the starting position has been reached. Turn on light and adjust wedge for a background reading of 100 on the meter. Proceed to read pertinent lines by moving film through.den- sitometer until dial indicates that the line to be read is about to be superposed on the slit. Obtain null reading. Record readings. Refer to relative intensity chart (page 19) for the corres- ponding relative intensities. Perform indicated.calculations, and.plot curves. 18 1. 2. 3. 4. 5. 6. 7. 8. 9. 1o. 11. 12. 13. 14. 15. 16. 17. 18. 19. 585 570 555 540 525 500 490 482 475 470 460 451 439 433 416 409 401 21. 22. 23. 24. 25. 26. 27. 28. 30. 31. 32. 33. 34. 39. 397 392 388 384 382 379 375 370 360 337 334 330 46. 47. 49 . 50. 51 . 52. 53. 54. 55. 57. 58. 59. 60. 826 323 321 306 304 300 297 292 290 289 287 19 ENSI'I'Y T0 RELATIVE INTENSITY 68. 69. 70. 71. 72. 73. 77. 78. 79. 80. CHART 279 N 77 m x] U! 272 270 268 266 264 262 260 254 249 247 227 81. 82. 83. 84. 85. 86. 87. 88. 89. 94. 95. 96. 225 220 217 213 208 204 199 194 185 180 175 170 165 160 155 150 DATA The data contained on the following pages was obtained by use of the procedure outlined above. Only the readings for the samples from the three wells in Clare County are included. For the sake of brevity, only those values actually used in the computations are listed. The first column (page 21) gives the code number of the sample; the second and third are the direct density readings as recorded. The fourth and fifth.are the values of relative intensity as read from the relative intensity chart."| The sixth column is twice the relative intensity of the magnesium.line plus the relative intensity of the barium line. The last column is the ratio of the relative intensity of the barium line to this sum. * This chart was used for well number 3 in Clare County, and for all three wells in Ogemaw County. The first two wells in Clare County had been run before subsequent improvements in densitometer design (insertion of wedge-diaphragm and the development of a more satisfactory slit) had made the simplified scheme possible. Previous to this time it had been necessary to substract the line reading from a background reading and to use this value for the interpolation of the relative intensity. DENSITY READINGS AND RELATIVE INTENSITY VALUES WELL NO. 1 (PERMIT #9904) GRANT TOWNSHIP, CLARE COUNTY, MICHIGAN Density Relative Intensities day]: Mg .52 his 3.9 21M 138- .B_a. £- 21“ A- 1 43 66 321 241 883 273 2 69 - . 262 - - .- 3 57 75 287 245 819 299 4 46 37 312 337 961 350 5 13 23 297 277 871 318 6 68 80 264 227 755 300 7 75 63 245 275 765 360 8 57 51 287 300 874 348 9 43 53 321 295 937 315 10 50 62 304 277 885 313 11 48 69 309 262 880 297 12 76 37 241 337 819 413 13 61 62 279 277 835 332 14 49 54 306 272 884 296 15 39 26 235 - - - 16 22 14 275 184 734 251 17 47 49 311 306 928 330 18 48 48 309 309 927 334 19 42 42 323 323 969 334 20 40 46 330 312 972 321 21 40 37 309 337 955 353 22 46 59 312 283 907 312 23 47 53 311 295 917 322 24 32 36 353 340 1046 325 25 33 30 351 360 1062 342 26 .. .. - _ - .. 27 61 53 279 295 853 346 28 52 53 - - - - 29 54 73 292 249 833 299 30 38 49 334 306 974 315 31 29 46 365 312 1042 299 32 29 32 365 353 1083 325 33 31 41 357 326 1040 313 84 33 32 351 353 1055 335 35 27 40 375 330 1080 306 36 44 58 319 285 923 309 37 39 56 332 289 953 304 38 36 58 304 285 965 295 39 45 51 316 304 936 325 40 37 32 241 256 738 347 41 25 10 375 309 1059 293 42 48 50 309 304 922 329 43 52 61 297 279 873 320 44 81 65 225 270 720 375 45 63 ‘ 31 275 357 907 393 27 686882882888888 Well No. 1 (continued) Density .45 .82 57 42 4O 4O 50 51 43 43 58 57 58 6O 58 59 76 74 64 53 58 51 49 47 46 43 83 67 71 39 81 72 27 17 47 4O 34 18 55 44 49 58 34 20 52 53 68 61 61 55 34 34 36 42 4O 49 5O 63 45 59 36 4O 58 65 62 58 57 48 39 52 51 47 62 60 36 36 49 56 42 42 47 54 58 60 60 54 64 57 53 58 71 33 61 35 69 48 Relative Intensities 22 287 304 323 285 285 283 241 272 285 306 313 217 256 225 290 311 290 256 297 264 279 349 340 330 304 316 340 285 277 287 332 300 277 306 323 311 285 280 277 295 256 279 262 ‘§§ 323 300 321 287 280 285 274 295 300 311 321 266 332 254 316 330 283 319 285 287 295 279 290 349 323 306 275 283 330 270 285 309 297 311 280 289 323 292 280 292 287 285 351 399 2xM 897 908 967 857 850 853 729 839 870 923 947 700 844 704 896 952 773 899 897 799 889 807 848 1047 1003 966 883 915 1010 840 839 883 961 911 834 1020 901 969 914 850 852 841 875 863 903 833 B 360 333 331 333 335 329 332 339 352 345 337 339 380 394 361 352 347 366 355 318 359 332 346 342 333 322 316 311 310 327 321 3.11 No. 1 (continued) Density Relative Intensities m 112 8.4 118 Jade“: 13.4.5.4;th Ba B-43 54 56 292 289 873 331 44 64 55 272 290 764 380 45 47 65 311 270 892 303 46 47 87 311 199 821 242 47 50 72 304 254 862 294 48 75 69 245 262 752 348 49 39 46 332 313 977 321 50 35 22 345 392 1082 362 c- 1 56 65 289 270 848 319 2 39 52 332 297 961 309 3 46 58 313 285 911 313 4 34 46 349 313 1011 309 5 43 65 321 270 912 296 6 72 82 254 220 728 302 7 56 60 289 280 858 326 8 70 75 260 245 765 320 9 .. .. - .. .. - 10 49 64 306 272 884 308 11 4o 71 330 256 916 279 12 47 66 311 268 890 301 13 44 82 319 220 858 257 14 40 48 330 309 969 319 15 49 60 306 280 892 314 16 52 67 297 266 860 310 17 36 52 340 297 977 304 18 40 80 330 227 887 256 19 44 71 319 256 894 286 20 44 67 319 266 904 295 21 40 51 330 300 960 313 22 45 63 316 275 907 303 23 51 64 300 272 872 312 24 54 86 289 204 782 261 25 42 68 323 264 910 290 26 42 76 323 241 887 272 27 37 71 337 256 930 275 28 42 84 323 213 859 248 29 39 71 332 256 920 278 30 45 73 316 249 881 282 31 44 87 319 199 837 238 32 29 69 365 262 992 264 33 15 16 439 433 1311 330 34 62 54 277 292 846 345 35 47 43 311 321 943 340 36 66 53 268 295 831 355 37 34 59 349 283 981 288 38 69 52 262 297 821 362 23 flmu 0-39 1588138 Well N0. 1 (continued) Density Mg ;§a 66 50 77 69 65 80 11 16 51 47 54 65 Relative Intensities .Mg 268 238 326 470 300 292 gg, (Zng)lBa 304 840 260 736 227 879 433 1373 311 911 270 854 gg;§.(253g):8a 362 353 258 315 342 316 DENSITY READINGS AND RELATIVE INTENSITY VALUES 5.44212 consummated)!” 6&888888888388888838888 WELL N0. 2 (PERMIT #866) GRANT TOWNSHIP, CLARE COUNTY, MICHIGAN Density r4854. 33 63 22 9 21 20 38 45 23 25 19 15 15 6 26 44 13 10 36 25 10 13 25 23 13 15 22 19 48 41 24 32 19 21 15 23 12 19 25 27 34 22 39 49 16 45 31 28 13 28 29 37 3O 13 18 6 29 47 29 24 48 63 37 41 27 31 46 64 42 49 14 22 ll 10 l4 16 11 22 12 9 12 ll 23 31 10 20 9 14 12 18 Relative Intensities pg Ba (2x15g)B§ pg; 277 170 724 326 334 988 283 285 752 266 247 781 295 290 882 309 319 937 319 340 978 292 254 838 387 292 866 272 275 819 304 295 903 292 297 881 289 285 863 297 306 900 241 262 743 283 275 841 300 295 895 292 277 861 312 295 919 287 280 854 275 300 850 269 241 779 316 247 879 283 289 855 319 283 921 285 269 839 283 323 889 312 323 947 287 245 822 287 295 869 241 175 657 270 262 802 290 283 863 247 170 764 249 227 726 311 290 912 319 321 949 312 309 935 316 289 921 323 332 978 319 321 959 292 277 861 323 297 943 323 311 957 323 309 955 25 322 310 282 338 310 310 364 341 299 340 266 327 328 223 312 318 338 331 314 339 335 322 315 325 323 Well N0. 2 (continued) Density 145 13.9 15 14 2 4O 46 63 15 23 9 21 16 17 16 20 14 25 10 15 21 23 8 12 13 21 20 29 21 7 33 59 10 22 28 49 ll 25 15 23 19 22 12 21 43 62 25 35 19 48 24 4O 18 25 52 64 22 36 27 33 9 13 14 27 16 27 36 36 3O 41 15 31 16 27 17 21 14 26 16 24 32 40 ll 20 10 18 14 31 ll 22 13 25 71 56 Relative Intensities 15.5 292 321 238 306 326 285 304 309 319 292 232 319 304 300 272 323 279 319 311 311 312 254 269 280 295 312 232 304 300 297 323 316 287 323 321 312 312 311 277 323 297 316 297 321 304 8a ( 21Mg) Ba 295 879 256 898 160 636 287 899 295 947 283 853 292 900 283 901 306 944 289 873 312 958 297 935 283 891 337 937 180 724 292 938 254 812 285 923 290 912 304 926 290 914 175 683 241 779 185 745 262 852 295 919 175 629 272 880 287 887 289 883 209 935 289 921 264 838 285 931 292 934 304 928 285 909 290 912 260 814 300 946 280 874 277 916 275 869 270 912 208 816 L 316 Ba w I omqmmsuww888888£88 8988888588828888888 Well N0. 2 (continued) Density 1425.4 11 13 12 21 12 39 14 31 14 4O 16 49 11 35 22 55 13 32 12 40 12 3O 19 43 11 27 11 36 11 38 16 4O 13 38 14 46 12 44 7 27 7 5 20 57 9 35 9 42 8 24 9 40 7 22 7 25 7 21 6 14 15 44 11 46 10 45 2O 60 7 29 16 35 10 39 15 46 9 39 10 36 9 25 17 32 17 27 12 44 10 25 32 55 14 35 Relative Intensities 35 323 297 319 319 316 311 321 297 309 306 297 300 300 304 295 319 316 312 297 312 326 285 321 309 316 319 323 326 321 319 292 312 312 283 319 297 311 297 311 306 300 297 295 306 300 266 297 g. 319 279 256 279 256 227 266 208 266 232 260 245 266 245 227 265 260 235 213 269 332 100 262 225 279 245 287 283 249 297 217 225 225 100 269 256 241 217 238 245 266 266 275 225 269 180 249 23M 965 873 894 917 888 849 908 802 884 844 854 845 866 853 817 902 892 859 807 893 984 670 904 843 911 883 933 935 891 935 801 849 849 666 907 850 863 811 860 857 866 860 865 837 869 712 843 Ba —a (2§§g218§ 330 320 287 304 288 268 293 260 301 274 304 290 307 287 278 293 292 274 264 302 290 267 278 307 303 279 318 271 265 265 297 302 279 267 277 307 309 318 269 310 253 296 2&2 0-39 £88158 Well N0. 2 (continued) Density M £2 14 29 20 38 23 25 24 31 18 39 ll 32 Relative Intensities 7% 301 290 290 279 290 306 fig. (23gg)28a 272 874 249 829 287 867 264 822 241 821 260 872 ;§§.§ (2ng)Ba 312 301 331 321 294 298 DENSITY READINGS AND RELATIVE INTENSITY VALUES WELL N0. 3 (PERMIT #8352) SHERIDAN TOWNSHIP, CLARE COUNTY, MICHIGAN Density Relative Intensities m1: 114 3.4 .42 .114 13.912124 52:- 246 A- 1 11 5 470 526 1465 357 2 18 31 416 357 1189 300 3 6 37 510 337 3157 249 4 7 17 500 425 1425 298 5 2 21 570 397 1537 259 6 3 16 555 433 1543 279 '7 15 56 439 289 1167 247 8 .. .. - .. - .. 9 5 5 525 525 1575 332 10 6% 54 505 292 1302 223 11 5 15 525 439 1489 301 12 26 71 379 256 1014 254 13 83,; 35 486 345 1317 285 14 11 46 470 313 1253 250 15 31 75 357 245 959 256 16 40 70 330 260 920 283 17 16 53 433 295 1161 253 18 5 16 525 433 1483 291 19 6 21 510 397 1417 281 20 7% 27 495 375 1365 275 21 6 33 510 351 1371 255 22 6 21 510 397 1417 281 23 11 47 470 311 1251 249 24 18 45 416 316 1148 275 25 18 8 416 490 1322 370 26 5 25 525 382 1432 267 27 6 33 510 351 1371 256 28 2 28 570 370 1510 245 29 22 52 392 297 1081 274 30 6 22 510 293 1412 271 31 6 12 510 460 1480 310 32 5 43 525 321 1371 234 33 8 24 490 384 1364 280 34 12 57 460 287 1207 236 35 4 30 540 360 1440 249 36 3 59 555 283 1393 203 37 3 21 555 397 1507 263 38 10 34 475 349 1299 267 39 5 13 525 451 1501 330 40 3%,- 7 555 500 1610 322 41 22 22 392 392 1176 336 42 8 17 490 425 1405 302 43 5 26 525 379 1429 265 44 30 85 360 208 928 222 45 16 42 433 323 1189 271 29 Well N0. 3 (continued) Density Relative Intensities §am21§ pg pg, pg 33 2x11 Ba __t_9._ .3 2x121 A-46 20 59 401 283 1085 261 47 6 20 510 401 1421 282 48 5 30 525 360 1410 255 49 2 30 270 360 1500 240 50 5 23 525 388 1438 270 51 6 24 510 384 1404 273 52 7 17 500 425 1425 298 53 17 30 425 360 1210 298 54 4 19 540 409 1489 274 55 7 39 500 332 1333 249 56 6 51 510 300 1320 227 57 4 27 540 375 1455 258 58 8 52 490 297 1277 233 59 6 34 510 349 1369 255 60 7 29 500 365 1365 267 61 11 55 470 290 1230 236 62 14 48 442 309 1193 269 63 8 68 490 264 1244 212 64 7 49 500 306 1306 234 65 10 44 475 319 1269 251 66 10 74 275 247 1197 206 67 10 37 475 337 1287 262 68 11 40 470 330 1270 260 69 11% 39 465 332 1262 263 70 5 24 525 384 1434 268 71 .. _ .. .. .. .. 72 10 36 475 392 340 263 73 5 26 525 379 1429 265 74 13 32 451 353 1255 282 75 13 26 451 379 1281 296 76 14 36 442 340 1224 277 77 11 65 470 270 1210 223 78 6 13 510 451 1471 306 79 8 43 490 321 1301 247 80 37 87 337 199 873 228 81 7 30 500 360 1360 264 82 5 — 525 - 1050 - v . . . _ 1.-.“- v - . 41...-.. 4 . . e . . . 31m 5253 , n _ . . gm 2.52 . - INTERPRETATION OF THE RESULTS The interpretation of the data obtained by the methods outlined in the preceding paragraphs has presented as many prob- lems as has its procurement. Readings were taken on lines of the elements magnesium, strontium, barium, calcium, and iron. Various combinations of these substances were plotted in an attempt of find any relationship which.might be present. Certain ratios seemed to work better in some wells than they did in others. Because of the limited time available, the calcium and iron lines were not used further. The reasons for discarding these parb ticular lines is spectrographic in nature as they both fall in a zone of high.cyan0gen background. Various methods, such as the lowering of the current through the electrodes were tried to cut down the background. Although.considerab1e success was realized in this attempt, the lines were still not as usable as were those of magnesium, strontium, and barium. In areas of close sampling it was noted that the plotted points almost invariably gave good control on some sort of a curve. The conclusion was reached that the method, as developed for the analysis of the samples was giving good results. The essence of the problem at this stage of the research consisted in finding what relationships, if any, could be used for correlative purposes. ' During the time devoted to experimenting with the calculations it was evident that barium was taking part in a major trend which roughly separated the Goldwater shale from the underlying forma~ tions. To try to more fully understand the relationships of the 32 elements in regard to this trend, curves of strontium over barium, and strontium over magnesium were plotted. It was noted at this time that the highs in the strontium over barium curve were gener- ally coincident with lows in the strontium over magnesium curve. It was further observed that the high in the strontium over barium curve was of approximately twice the magnitude of the low in the strontium over magnesium curve. In order to obtain as constant a denominator as possible for the final ratio it was decided to add the relative intensity of the barium line to twice the relap tive intensity of the magnesium line. It is admitted that this step is extremely empirical, and that the writer is not at all certain that the results are improved by its use. However, due to the nature of the work, it is doubtful that any relationship is destroyed because of its ad0ption. It may be seen, by referring to the plot of the relative ratio of barium to magnesium (page 31) that the previously mentioned trend separating the Cdldwater shale from the deeper formations is quite prominent. .A "base level“ (shown as a double line) has been arbitrarily drawn through each curve so as to better illustrate this relationship. The fact that this level varies from well to well introduces interesting possibilities having to do with determining water depth at the time of deposi- tion. In every oase the wells that were appreciably down dip had a lower barium level than did the higher ones. According to Rankama and Sahama (1949), barium is associated with near shore facies. It is a natural continuation of this line of reasoning to hypothesize that the Goldwater shale is a predominately shallow 33 water facies. while the underlying shales are deeper. It may be reasoned further that the cnange from deep water to shallow water facies in the early'Mississippian.period might possibly accompany relative uplift of the Michigan basin. However, there is not enough data assembled at this time to make any such positive statement. CONCLUSIONS It is concluded that the method presented in this paper has merit, and is worthy of further research. Several recommendations might be made here to facilitate any such further work. The first of these would be the use of a spark source for firing the samples. The ease of firing and timing with this type of excitation would greatly increase the number of usable films, and would reduce any possible error within the source caused by selective volatilizap tion of the constituent materials. The second recommendation would have to do with the use of a slower type of fill for greater exposure latitude. .Although the film used in this work gave satisfactory results, it is thought that a better type may be available. Final emphasis should be placed on the possibilities of extending the technique develOped herein to other types of sedi- mentary rocks. It seems to the writer that the spectrOgraphic analysis of all types of sediments will some day yield a good deal of information that will be useful in the realms of strati- graphy and sedimentation. 34 BIBLIOGRAPHY Bookg Ahrens, L. H. (1950). ectrochemic- si . Press, Inc., Cambridge. Addison—Wesley Brode, w. 3. (1945). Chemical spectroscgpy. (2d Ed.) John Wiley and Sons, N. Y. alleles Lee, Willis T. (1915). Relation of the Cretaceous formations of the Rocky Mountains in Colorado and New Mexico. 5:, §, Geog" §urvey Professional]I Paper 95, pp. 27-58. Pettijobn, Francis J. (1943). Archean sedimentation. Geo oc W“ Vol. 54, No. 7, pp. 925-972. Spec trochemical sample Sloss, L. L. and Cooke, S. 3.. B. (1946). Pe eo ., Vol. 30, logging of limestones. Am A o No. 11, pp. 1888-1898. Spieker, Edmund M. (1949). Sedimentary facies and associated diastrophism in the Upper Cretaceous of central and eastern Utah, in Longwell, C. 3.. Chm., Sedimentary facies in geologic history (symposium): geol, §ocI Am. Mom, 59, pp. 55-81. (llllllllilllllllllilllllllllllllll O 4 6 6 2 4 1 3 0 3 9 2 1 3 lllllllllllllllllillllllllill