Technical Notes - An Investigation of the Use of the Spectrograph for Correlation in Limestone Rock

In many areas where carbonate rocks form important parts of the stratigraphic sequence, stratigraphers have experienced varying degrees of difficulty in differentiating and correlating limestone and dolomite units in both surface and subsurface work. With early Paleozoic rocks of the Mid-Continent, insoluble residues yield a remarkable amount of strati-graphic data and relatively good correlations may be carried over broad distances.' Unfortunately, neither such information nor electric logs and radioactive logs have been particularly helpful in interpreting the limestone sections of the Permian Basin of West Texas. This is because: (1) the variations in the sections may be very slight; (2) no completely satisfactory method of interpretation has been developed; and (3) the measurements themselves are not sensitive enough for small variations. Also, such logs are influenced by the fluid content. Paleontology and micro-paleontology remain the ultimate arbiters. As a routine tool, however, paleontol-ogical examination is slow and tedious. Chemical analysis may be used, but this, too, is extremely slow. Although rocks are not classified according to chemical composition, there is considerable variation with rock types. Correlation by chemical composition has two advantages, first, the characteristics determined are subject to minimum human error and interpretation, and secondly, the lithologic changes are not masked by fluid content as in the case of electric and radioactive logs. Some fossils concentrate certain elements which tentatively might be used to date rock units.' Rapid chemical analysis by spec-trographic means could be used as an adjunct to other means employed in correlation work, or might, in itself, present a suitable method. PURPOSE OF THIS INVESTIGATION Sloss and Cooke' have published data concerning spectrographic analysis of limestone rocks specifically for purposes of direct correlation of a single formation. These authors found satisfactory evidence that differences in percentage of four elements (Mg, Fe, Al, and Sr) in the Mississippian limestones of northern Montana were useful in carrying out correlation of this formation over a distance of approximately 50 miles. It was concluded from the preliminary work that the spectrochemical method offered possibilities of solution of some problems of correlation heretofore not possible. Since the work of Sloss and Cooke' was confined to one particular limestone zone, extension of the use of the method to examine two or more geologic formations would aid materially in the over-all problem of correlation of such rocks. Equipment is now available commercially with which very rapid spectrographic analyses may be made, and hence the problem was to determine whether the variations existing in the minor constituents of limestones were sufficient for use in possible correlation. Qualitative and semi-quantitative investigations were made to determine whether significant changes in the chemical condition occurred. It was a further purpose to investigate the geologic time-boundaries to see whether significant chemical variation could be found corresponding to the paleontological breaks. It was desirable to attempt correlation of a thick section of limestone or dolomite rock and to have as much information as possible on the section. Furthermore, it was felt that examination of formations more difficult to correlate by other means would enhance the value of the method should definite points of correlation be found. Samples were chosen from the Chapman-McFarlin Cogdell No. 25 well in the Cogdell field, Kent County, Tex., and from the General Crude Oil Co., Coleman No. 193-2 well in the Salt Creek field, Kent County, Tex. These fields belong to the famous series of "Canyon" reef fields of West Texas. Cores from the above wells were available from the United States Geological Survey, Austin, Tex. THE SPECTROGRAPHIC METHOD The choice of procedure to be followed in this investigation was based on the anticipated requirements peculiar to the problem. Since the problem was primarily to investigate the possibilities of applying the spec-trograph to problems of correlation in thick carbonate sections, a precise quantitative analysis did not appear necessary. A qualitative analysis to show the possible absence of presence of any element, or a semi-quantitative analysis of the elements present to show the relative changes in magnitude of selected elements was required. Both types of analysis were employed. The two most widely applied methods of semi-quantitative estimates are those of Harvey and of Slavin4,5 though various other procedures have been described.6 while the Harvey method has been modified by Addink,7 this refinement did not seem necessary to the present problem. Essentially, the procedure employed is a variation of the total energy method of Slavin with two exceptions: (1) stressing matrix effect, and (2) using densitometer measurements. As measured by a densito-