API 4155-1971 Rapid Methods of Analysis for Trace Quantities of Polynuclear Aromatic Hydrocarbons and Phenols in Automobile Exhaust@ Gasoline@ and Crankcase Oil - Final Report
"INTRODUCTION The initial and most important objective in the CAPE-12-68 Project was to develop a rapid method to measure BaA and BaP in tar recovered from automobile exhaust@ in gasoline@ and in crankcase oil. In selecting an approach@ we were in position to learn from fifteen years of experience in the assay of petroleum fractions for PNA's. Our choice of technique was based on a recent method which was developed at Esso Research and Engineering to measure several PNA compounds in coke oven effluents (1). Based on combined use of gas chromatography and ultraviolet absorption spectrophotometry@ the new method (GC/UV) appeared to be more advantageous compared with the other most promising approach in which thin layer chromatography would provide the final fraction(s) for each PNA measurement. This approach was in agreement with a conclusion reached earlier in 1967 by McKee and McMahon (2). They surveyed existing methods for analyzing PNA and concluded that ""gas chromatography appears to show the greatest promise of providing a rapid yet reliable and accurate method to determine a number of PNA compounds."" The coke oven effluent method was extensively modified in achieving a satisfactory procedure for the CAPE-12-68 project. Another objective of CAPE-12-68 was to provide a means of measuring all of the PNA's in a sample. Some of the promising approaches included: ultraviolet absorption spectrophotometry@ summation of GC peaks@ and low voltage mass spectrometry. The mass spectrometric capability offered the best potential for comprehensiveness and specificity. The value of low voltage ionization measurements was first demonstrated by Field and Hastings (3). They showed that olefins and aromatic hydrocarbons can be selectively measured in the presence of other compounds. This capability arises from the fact that ionization potentials of olefins and aromatics are one or two volts lower than those of aliphatic and cycloparaffins. By using a low ionization potential@ selective ionization occurs. This principle has been extensively used in the petroleum industry to analyze complex hydrocarbon mixtures. In achieving another objective of CAPE-12@ a method was developed to measure individual phenols at the ppm level. This development was based primarily on the use of an extraction procedure evaluated by Hoffman and Wynder (4) to prepare a sample for analysis by capillary gas chromatography (5@ 6). (1) T. D. Searl@ F. J. Cassidy@ W. H. King@ Jr.@ R. A. Brown@ Anal. Chem. 42@ 954 (1970). (2) H. P. McKee@ W. A. McMahon@ Technical Report No. 1@ Project No. 21-2139@ Committee for Air and Water Conservation@ American Petroleum Institute. (3) F. H. Field@ S. H. Hastings@ Anal. Chem. 28@ 1248 (1956). (4) Dietrich Hoffman@ Ernest L. Wynder@ Beitrage zur Tobakforschung 3@ 101 (196l). (5) Jan Hrivnak@ J. Chroma tog. Sci.8@ 602 (1970). (6) D. S. Payn@ Chemistry Industry@ 1090 (August 20@ 1960)."
API 4155-1971 history
1971API 4155-1971 Rapid Methods of Analysis for Trace Quantities of Polynuclear Aromatic Hydrocarbons and Phenols in Automobile Exhaust@ Gasoline@ and Crankcase Oil - Final Report