Chemical Analyses for Selected Minor Elements in Pierre Shale GEOLOGICAL SURVEY PROFESSIONAL PAPER 391-A Chemical Analyses for Selected Minor Elements in Pierre Shale By L. F. RADER and F. S. GRIMALDI ANALYTICAL METHODS IN GEOCHEMICAL INVESTIGATIONS OF THE PIERRE SHALE GEOLOGICAL SURVEY PROFESSIONAL PAPER 391-A UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON : 1961 UNITED STATES DEPARTMENT OF THE INTERIOR STEW ART L. UDALL, Secretary GEOLOGICAL SURVEY Thomas B. Nolan, Director For sale by the Superintendent of Documents, U.S. Government Printing Office Washington 25, D.C. CONTENTS Page Page Abstract--_________________________________________ A-l Methods for the determination of individual Introduction ___-----_-_--_________________-__--__-_ 1 constituents Continued General remarks._________________________ ______ 1 Copper lead, and zinc Continued Laboratories. -._---____-_-______________________ 2 Zinc, dithizone method._____^_______________ A-20 Acknowledgments. ___-_-_-_--______--_-_________ 2 Lead, dithizone method______------_-____-__- 22 Division of work________________________________ 2 Arsenic.___________,__________-_-_--___-__---_- 23 Methods selected and treatment of data ___________ 3 Acid digestion, heteropoly blue method________ 23 Sample preparation _________________________________ 4 Alternative fusion-heteropoly blue method_____ 24 Methods for the determination of individual constituents. 4 Titanium. _____________________________________ 4 Selenium, distillation, visual-estimation method.____ 25 Peroxide method._--_--_-____._____________ 4 Molybdenum and tungsten______-____------_---_- 27 Alternative tiron method, ___________________ 5 Isolation by method 1, alpha-benzoinoxime pre­ Vanadium. _--.---_____-_-___.__________________ 7 cipitation. ___----_-_-_-__--_----_-----_-- 27 Fusion-leach separation method. _____________ 7 Isolation by alternative method 2, alpha-ben­ Alternative cupferron separation method....... 8 zoinoxime extraction ______________________ 28 Chromium, fusion-leach chromate method _ ________ 10 Isolation of molybdenum by alternative method Manganese, persulfate oxidation method.__________ 12 3, cupferron separation.___________________ 29 Cobalt, dithizone-nitroso-R-salt method ___________ 13 Uranium, fluorometric method.________----__-___. 31 Nickel, dimethylglyoxine method _________________ 15 Carbon__-.___.--------------_-----------_----_ 33 Persulfate oxidation.________________________ 15 Carbonate carbon, gasometric determination--- 33 Alternative bromine oxidation._______________ 16 Total carbon, gasometric determiilation _______ 37 Copper, lead, and zinc...-_______________________ 17 Determinations of organic carbon.____________ 38 Isolation by extraction._____________________ 17 Organic matter.________________--__-_____--_-_- 39 Copper._-__-_____--.___--_________________ 18 Dithiuone method ______________________ 18 Summary.._________________-__--__--____---_------ 41 Alternative 2, 2' biquinoline method. _____ 19 Literature cited___________----_-___-___---___--_-_- 44 ILLUSTRATIONS Page Page FIGURE 1. Comparison of titanium determinations of B FIGURE 11. Comparison of selenium determinations of A with those of A, C + D, F, and G______ A-6 with those of B and BI__.__._..__.----- A-26 2. Comparison of vanadium determinations of A 12. Comparison of molybdenum determinations with those of AI, A2, and B____________. 9 of A with those of B______-_-_____-_--- 31 3. Comparison of chromium determinations of B 13. Comparison of uranium determinations of B with those of A, F, and G_______________ 11 with those of BI and A__----_-_-------- 33 4. Comparison of manganese determinations of 14. Apparatus for gasometric determination of A with those of B, C + D, and F________ 13 carbon dioxide- ____________-_--__---_- 34 5. Comparison of cobalt determinations of B with those of A, AI, F, and G...________ 15 15. The relation between the percentage of car­ 6. Comparison of nickel determinations of A bon dioxide in the sample and its volume with those of B and F__________________ 17 at standard conditions._______________ 35 7. Comparison of copper determinations of B 16. Comparison of carbonate carbon determina­ with those of A, AI, A2, A3, and A4_____._ 20 tions of A with those of AI and of C + D_ 36 8. Comparison of zinc determinations of B with 17. Comparison of total carbon exterminations of those of A, AI, and A2__________________ 21 A with those of A2_ _____ A------------- 38 9. Comparison of lead determinations of B with 18. Comparison of organic carbon determinations those of A and AI________._____________ 22 of A with those of Aj___-__-___-__---_- 39 10. Comparison of arsenic determinations of A 19. Comparison of organic-matter determina­ with those of B and B! _________________ 24 tions of E with those of A_______________ 40 in IV CONTENTS TABLES Page Page TABLE 1. Determinations of titanium by different labo­ TABLE 33. Determinations of selenium in hidden splits. _ - A-26 ratories _______________________________ A-7 34. Determinations of selenium in check samples-- 27 2. Determinations of titanium in hidden splits 35. Replicate determinations of molybdenum. __. 31 by three laboratories.___________________ 7 36. Determinations of molybdenum in hidden 3. Determinations of titanium in check samples. 7 splits. _.___-____--__---___--_----.-_ 31 4. Replicate determinations of vanadium ______ 9 37. Determinations of molybdenum in check sam­ 5. Determinations of vanadium in hidden splits. _ 10 ples. _ ____________-_______-_-__----__-_ 31 6. Determinations of vanadium in check sam­ 38. Determinations of uranium by different chem­ ples. _________________________________ 10 ists, one laboratory_____________________ 33 7. Comparision of vanadium recovery by two 39. Determinations of uranium in hidden splits.-. 33 methods when iron content (Fe203) of shale 40. Determinations of uranium in the check sam­ is less than 5 percent___________________ 10 ples. _______-------_---_----_--------_- 33 8. Replicate determinations of chromium____ __ 11 41. Factors for calculating percent of carbon 9. Determinations of chromium in hidden splits. _ 11 dioxide and percent of carbon for various 10. Determinations of chromium in check sam­ sample weights from the volume of carbon ples. __________________________________ 11 dioxide under standard conditions.----..__ 36 11. Determinations of manganese by three labo­ 42. Determinations of carbonate carbon by dif­ ratories _______________________________ 13 ferent methods and laboratories__________ 36 12. Determinations of manganese in hidden 43. Determinations of carbonate carbon in hidden splits _________________________________ 13 splits _________________________________ 36 13. Determinations of manganese in check 44. Determinations of carbonate carbon in check samples _______________________________ 13 samples. _____________________________ 37 14. Replicate determinations of cobalt- ________ 15 45. Replicate determinations of total carbon. _ _ _ 38 15. Determinations of cobalt in hidden splits_-_- 15 46. Determinations of total carbon in hidden 16. Determinations of cobalt in check samples, __ 15 splits. ________________________________ 38 17. Replicate determinations of nickel-_________ 17 47. Determinations of total carbon in check and 18. Determinations of nickel in hidden splits- ____ 17 other samples-_________________________ 38 19. Determinations of nickel in check samples. 17 48. Replicate determinations of organic carbon _ _ 39 20. Replicate determinations of copper_________ 20 49. Determinations of organic carbon in hidden 21. Determinations of copper in hidden splits. 20 splits ________________________________ 39 22. Determinations of copper in check sampleS-__ 20 50. Determinations of organic carbon in check 23. Replicate determinations of zinc____________ 21 samples. _____________--__----__-_-_-_- 39 24. Determinations of zinc in hidden splits.- 21 51. Replicate determinations of organic matter _ _ 40 25. Determinations of zinc in check samples,_ 21 52. Determinations of organic matter in hidden 26. Replicate determinations of lead-___________ 22 splits. _____-___---__------------_--_-- 40 27. Determinations of lead in hidden splits-- 22 53. Determinations of organic matter in check 28. Determinations of lead in check samples.-___ 23 samples,_________-__--_-___---_-______ 41 29. Replicate determinations of arsenic _________ 24 54. Mean element content and standard devia­ 30. Determinations of arsenic in hidden splits____ 24 tions of 10 check samples..-__-____-___-_ 41 31. Determinations of arsenic in check samples. _. 25 55. Summary of the precision and reliability of the 32. Replicate determinations of selenium. ______ 26 determinations for various elements- - _ _ _ . 42 ANALYTICAL METHODS IN GEOCHEMICAL INVESTIGATIONS OF THE PIERRE SHALE CHEMICAL ANALYSES FOR SELECTED MINOR ELEMENTS IN PIERRE SHALE By L. F. RADER and F. S. GRIMALDI ABSTRACT was planned to continue for several years, it was A study of the analytical precision of chemical methods for imperative that the analytical work be uniform and determination of selected minor elements in the Pierre shale is comparable in reliability and precision over the full reported. The detailed procedures for the determination of period of the study not only with reference to the titanium, vanadium, chromium, manganese, cobalt, nickel, analyses made by each laboratory but also with refer­ copper, zinc, lead, arsenic, selenium, molybdenum, tungsten, uranium, carbonate carbon, total carbon, and organic matter