sample="quota" bates="1000779683" isource="pm" decade="1980" class="ui" date="19800423" Charge Number: Various Program Title: Spectroscopy and Chromatography Program Leader: D. C. Watson Period Covered: March 23 - April 23, 1980 I. TOBACCO AND FILLER A. Bright/Burley Ratios - Competitive Brands B. Mixing Cylinder Test - Residual Ethanol II. SMOKE A. TDL - Puff Profiling III. ADDITIVES A. Off-odor - WS-14 B. Methoprene - Method Development C. Trinity - Preblend D. Method Development - WS-14 IV. CHEMOMETRICS A. Headspace - Tobacco Volatiles B. SPSS - Discriminant Analysis V. OTHER A. CO - Laser Perforator B. Model 283B Perkin-Elmer Infrared C. NMR - Lab Air Handling Modification D. Volatile Sweep - Disposable Cambridge Pad Holders E. Headspace - Method Improvement F. GC/MS G. TPM/H20 Nicotine/Tar - Instrument Installation H. Routine and Semi-Routine I. Completion Reports J. Method Development K. Significant Memos I. TOBACCO AND FILLER A. Quantification of bright and burley content of ET in selected competitor's brands was completed. The data also indicated (except for PM brands using DBC blend) the general use of thin grades in expansion processes. A summary of the data is shown below. B. Residual ethanol levels were determined in filler just prior to, and at the exit of, the final mixing cylinder at the Manufacturing Center. The data are summarized below on an "as received" basis. The deviation is shown at 2 for N=12. II. SMOKE A. A high efficiency vacuum pump is being installed to allow puff-by-puff analyses using the 100 meter gas cell with the TDL. Four different smoking assembly designs have been evaluated for application to the unit. Since dead volume in the system affects the puff profile shape, any system used must be characterized so that valid comparisons can be made between different cigarette types. III. ADDITIVES A. An off-odor in a shipment of WS-14 was characterized using head-space analyses. The chromatograms showed considerable qualitative and quantitative differences between the volatiles collected from a control versus the "constrained" sample. The off-odor note was especially evident in the collected volatiles of the sample. No further characterization (i.e. gc/ms) was done. B. A draft of the method for the determination of methoprene in tobacco (µg/g level) has been written. This method along with procedures for Assay of KABATR and technical grade methoprene and a list of all recommended instruments is being transmitted to QA personnel at our stemmerys. C. Trinity Preblend I is being compared on a lot-to-lot basis for conformity to laboratory batches using (gc)2. Preblend I components will be quantitated and the method for quantitation will be transmitted to QA personnel at the M/C. D. A method was developed for the determination of WS-14. Copies of the procedure (Analytical Methods Manuel, E-55) were provided to QA personnel. IV. CHEMOMETRICS A. The headspace collection and gc analysis has been completed for the 12 Trinity model's filler (6 x 85 mm and 6 x 100 mm). The chromatograms have been collated and are ready for application of chemometric techniques. Data will be generated for Cambridge to allow an over-all comparison of the headspace filler volatiles of: Kent III, Cambridge, Carlton (1 mg) and Carlton 100's. B. Data from the 17 samples previously studied (filler head space) were used with the SPSS discriminant program. Discriminant functions were calculated that led to 100% correct classification of the 3 brands, Carlton Box (1 mg), Carlton 100's, and Kent III. When one of the 17 sample runs was omitted from the training set and used as a training set of one, however, the results were less than convincing. IV. OTHER A. Infrared analyses showed no increase in CO levels in the vacuum exhaust (Hauni-Apollo Laser Cabinet) as compared to room air. B. The Model 283B Perkin-Elmer Infrared Spectrometer and data station was installed. Formal operator training will follow a period of familiarization with this microprocessor controlled instrument and its dedicated data system. C. Both NMR spectrometers were functional following a 3-week down-time. This was necessary for installation of the additional air handling capacity needed for optimum operation of their associated computer systems. The back-log of NMR experiments and requests that occurred during the down-time is being reduced. D. Volatile sweeps of the disposable Cambridge filter holders showed a loss of about 0.2 mg/holder of a phthalate. This amount is not enough to account for the approximately 1.5 mg/holder observed in experiments by A. Kallianos. E. Refinements being made to tighten control of collection and analyses of head space volatiles include addition or appropriate internal standards. F. The Varian Mat Statos 3308 printer/plotter was installed as a part of the Varian 200S GC/MS/Data System. G. A system for the automated determination of TPM, H2O, nicotine, and tar was installed in PM facilities in Buenos Aires, Argentina. A similar, but up-dated, system will be set-up in the Maracay, Venezuela labs during May and a 5th such unit is scheduled for Quito, Ecuador. H. Routine and Semi-Routine Analyses included: 1. Purity scans of alternate sources of TA. 2. Cation content of various suppliers lots of WS-14 3. Cation content and level in Tipping papers. 4. Pyrolytic products of materials proposed for use in our manufacturing facilities. 5. Spectral/Structure correlations of synthesized samples (IR and NMR). 6. Acetic acid, volatile fatty acids (C2-C5), and sugars content as a function of tobacco storage and of bruising. 7. Formic and acetic acids, phenol, and catechol in TPM in ageing studies. 8. Volatile fatty acids in CEL and finished sheet as a function of denitration processes. 9. Residual air in liquid CO2 storage tanks. 10. Humectants, organic acids, plastilizers, and specific flavors in tobacco, filler, sheet, paper, and filters. I. Completion Report, Bennie W. Good, Milton E. Parrish, & D. R. Douglas, "Volatile Phase Profiling of Mainstream Smoke," April 17, 1980, ACC. No. 80-097. J. Methods Development "WS-14 in Cigarettes, Filler, and Smoke", Analytical Division Methods Manual #E-55, Mary B. Buckner, J. R. Atkinson, and D. C. Watson K. Significant Memos 1. L. C. Smith to Mr. Donald Keel, "Comparison of WS-14 Flavor Samples", April 1, 1980. 2. Tom Hill and Dot Clark to Mr. E. B. Stultz, "Sampling Laser Perforator Exhaust System", April 3, 1980. 3. Gunars Vilcins and Gary Forrest to Manuel Bourlas, "Atmospheric NO2 Study", April 16, 1980. 4. C. S. Kroustalis to Mr. A. Kallianos, "Final Mixing Cylinder Test for Ethanol - M/C", March 25, 1980. 5. R. C. Esperdy to Andy Kallianos, "Headspace Analysis of Disposable Cambridge Filter Holders", March 27, 1980.