@article {798, title = {Isotopic and molecular fractionation in combustion; three routes to molecular marker validation, including direct molecular {\textquoteright}dating{\textquoteright} (GC/AMS)}, journal = {Atmospheric Environment}, volume = {33}, year = {1999}, note = {208duTimes Cited:38Cited References Count:31}, month = {Aug}, pages = {2789-2806}, abstract = {The identification of unique isotopic, elemental, and molecular markers for sources of combustion aerosol has growing practical importance because of the potential effects of fine particle aerosol on health, visibility and global climate. It is urgent, therefore, that substantial efforts be directed toward the validation of assumptions involving the use of such tracers for source apportionment. We describe here three independent routes toward carbonaceous aerosol molecular marker identification and validation: (1) tracer regression and multivariate statistical techniques applied to field measurements of mixed source, carbonaceous aerosols; (2) a new development in aerosol (14)C metrology: direct, pure compound accelerator mass spectrometry (AMS) by off-line GC/AMS ({\textquoteright}molecular dating{\textquoteright}); and (3) direct observation of isotopic and molecular source emissions during controlled laboratory combustion of specific fuels. Findings from the combined studies include. independent support for benzo(ghi)perylene as a motor vehicle tracer from the first (statistical) and second (direct {\textquoteright}dating{\textquoteright}) studies; a new indication, from the third (controlled combustion) study, of a relation between (13)C isotopic fractionation and PAH molecular fractionation, also linked with fuel and stage of combustion; and quantitative data showing the influence of both fuel type and combustion conditions on the yields of such species as elemental carbon and PAH, reinforcing the importance of exercising caution when applying presumed conservative elemental or organic tracers to fossil or biomass burning field data as in the first study. Published by Elsevier Science Ltd.}, issn = {1352-2310}, doi = {10.1016/S1352-2310(98)00325-2}, author = {Currie, L. A. and Klouda, G. A. and Benner, B. A. and Garrity, K. and Eglinton, T. I.} }