Date : April 2, 1996 To : Ms . DINAH MYERS Quality Assurance Fm : GUY SPENCE Scientific & Regulatory Affairs MICROANALYSIS OF CONSUMER COMPLAINT SAMPLE 95-148 : DIANE BUOTE, PHILADELPHIA, PA, MORE F120 MENTHOL, "CIGARETTE EXPLODED" OBJECTIVE Ms Buote claimed that when she smoked "1 - 2 cigarettes close to the filter, they 'kinda exploded"' . Examine the returned materials to determine whether any evidence existed that would support her allegation . SUMMARY The materials received for microanalysis consisted of a pack containing six unlighted cigarettes, a butt, and a note to which three small particles had been taped . The blend of the whole cigarettes was examined through the stereomicroscope at 12X . Absolutely nothing resembling explosive or incendiary materials was discovered in them . The butt had no tears or rips which might suggest that an explosion had occurred in it . Analysis of some of the loose blend particles in the pack revealed two laminae specimens which were littered with bright metallic-looking particles . These were prepared and analyzed with the SEm/Enx system . That analysis revealed that they were Mg particles, a very potent incendiary metal when in a finely divided state . It now strongly appears that the cigarette was tampered with by the insertion of incendiary materials rather deep within the rod . EXPERIMENTAL The materials submitted for microanalysis consisted of six unlighted cigarettes, one butt, and a note to which some small particles had been taped . The note read, "I Sh'lpk this was part of what exploded--it stuck to my arm ." The material taped to the note was examined through the stereomicroscope . These ~ .~i specimens included a somewhat circular black particle which measured approximately one w millimeter . This particle was attached to an SEM stub with double-sticky carbon adhesive for .i microanalysis . The untaped side was oriented upward . Also under the tape, there were three ro http://legacy.library.ucsf.edu/tid/zgg11d00/pdf w To : Ms . DINAH MYERS Date : April 2, 1996 Fm : GUY SPENCE smaller orange-amber colored particles . Two of these were likewise attached to the SEM stub for microanalysis . They were similarly oriented on the stub . Preliminary analysis of the butt revealed that it was 39 mm tip-to-tip . It had no tears or rips that would strongly suggest that an explosion had occttrred . The char line was not evenly burned around the rod . The cigarette had been burned to within 3%x mm of the face of the filter plug on one side, but the opposing side had burned to within one mm of the plug . On examination of the charred tip components, including the paper, I observed a light-colored residue on two laminae particles and one stem particle . Although my impression of this substance was that it was paper ash, I prepared the two laminae particles for electron microanalysis . A . INSTRUMENTS, OPERATING CONDITIONS The samples were plated with an ultrathin layer of evaporated carbon prior to their being analyzed with the instruments . The instruments employed for this microanalysis were the AmaaY 1910 FE SEM/Luvtc Isis Eux ANALYZER. For the microanalysis the electron gun was adjusted to 10kV accelerating potential, and the beam was controlled with a 300 µm final aperture and a condenser lens setting of-20 on the panel . All images were acquired with the solid state Backscattered Electron (B86) detector, which detector produced a signal intensity that is directly proportional to the average molecular weight of the target substrate . In order to focus the EDx (specimen characteristic X-Ray) signal to the EDx detector, the specimen stub was tilted 350 toward the detector and placed at a vertical distance of 15 .5 mm below the focal lens of the gun . Selected images were archived on disk, and selected spectra were quantitatively analyzed by computer employing standards generated from a C . M . Taylor Standard block . RESULTS AND DISCUSSION The blend from the six whole cigarettes was examined through the stereomicroscope . The analysis was an effort to discover some anomalous material(s) that might be either explosive or incendiary . None of these materials was found . Thus, these unlighted cigarettes were judged normal . When the prepared materials were imaged with the S6M, it became immediately clear that one of the two laminae specimens was significantly littered with several particles that were nontobacco . That lamina specimen, which I labeled "#1" on the photomicrographs, had several of these foreign particles, but one was quite large compared to the others . An overview of that particular lamina and the debris that was collected on its surface is shown in FIGURE 1 . From the SEm image acquired at 20oX, the brighter particles reveal their average molecular weight with http://legacy.library.ucsf.edu/tid/zgg11d00/pdf Page 2 To : Ms. DINAH MYERS Date : April 2, 1996 Fm: GUY SPENCE respect to the tobacco lamina was higherl by an appreciable factor . The graphics box that was drawn around the large particle was a computer measuring system that indicated particle dimensions of 136 µm x 117 µm2 . FIGURE 2 shows a view of the large metallic-looking particle recorded at 750X with the Stavt . In that particular image, the particle appeared to consist of a compressed ball of material, much of which seemed to be thin platelets . It was, without doubt, not a firmly solid ball of homogeneous material . Another feature that was revealed in this image was that although the material was heavier than tobacco, it also had a few smaller contaminating particles on it . They were revealed by the small white spots seen on its surface . Ftol :Viewoflaminakl,from20oXSrntimage . Brightpanicleson FtG2 :Viewoflargestpanice nlamina,seenlnFw2. Viewfmm surface are nontobacco . 75oX 5eM image . Particle dimensions shown in label . FIGuRE 3 exhibits a further enhancement of the large particle . It was taken from the SEM image collected at 2 .5kX . There, the extend to which the particle was composed of layers of smaller, often platelet-type materials became clearer . Also, the bright particles, previously seen ' The Bss signal is generated by high energy electrons that are essentially gun electrons that bounce off the surface of their target substrate, with little loss of energy . The heavier the average molecular weight of a specific substrate, the more efficient becomes its ability to effect this "electron bounce" . Thus, when two neighboring target areas consist of different substrate materials, the heavier substrate produces a brighter signal because it more efficiently redirects the incident electron beam back to the Bsa detector than does the lighter substrate . 2 In reality, the height measurement was too short, for the 35° tilt caused shortening of the true value . I suspect that the reading was more like the 136 µm horizontal value recorded . http://legacy.library.ucsf.edu/tid/zgg11d00/pdf Page 3 To : Ms . DINAH MYERS Date : April 2, 1996 Fm: GUY SPENCE in FicuitE 2, were seen to be angular crystals . At this location and magnification, an EDX spectrum was collected and quantitatively analyzed . It revealed that the material was a blend of components, with the major components being Ca, Mg, K, Cl, and S . Of course, oxygen was also a major constituent . The results of the quantitative analysis are disclosed in TABLE 1 . Some significant impressions were immediately made when these results were seen . First, much of the data resembled that which would be collected on residue from a firecracker explosion . The exception would be in the constituent Ca, which certainly came from the paper filler . Second, the materials present in this spectrum certainly did not come from a traditional cigarette load detonation. That material is always pure lead, from the reduction of explosive PbN6 . .TA@LB_1 : Quantitative Spectral Analysis from Area Shown in F76uaE 3 . Spectrum label : I30umPartMgKCalmag007Map 1 Elmt Element Atomic Compound Nos . of % % % ions Mg K 10 .80 11 .39 MgO 17 .90 0.24 Si K 0 .58 P K 1 .45 S K 3 .74 Cl K 2 .41 K K 20 .69 1 .24 j . r n an: • i~ . flc 3 : V iew of surface structure of particle shown in Fla 2 . View from 2 .5kX Seet image . Note that the brighter particles on the sW clure indicate that they were of different composition than the basic substructure . They were crystalline whereas the substructure appeared to be compressed platelets . 0 .01 1 .20 P205 3 .31 0.02 2 .99 S03 9 .33 0.06 1 .74 0 .00 0 .04 13 .57 K20 Ca K 29 .22 18 .70 Ca0 31 .12 49 .89 0 Total 100 .00 100 .00 97 .59 ur .." J~r .lll_I ' le~m -- 0 .53 Si02 24 .92 0,28 40 .89 0.39 1 .03 Anion sum 1 .07 • = Q Sigma In order to get information about the arrangement of discreet components in the structure seen in FtGu1tE 3, elemental E D x maps3 were collected over the same area . Figures 4 and 5 show various window combinations of the EDx map from F1GuRE 3 . FIGuRE 4 shows the BSE image and maps for elements Mg, Cl, and K . FIGuRE 5 shows a variant of the map where the upper left quadrant represented a combined map structure of the three elements, S, Cl, and K . By analyzing these map data, it was determined that K, Cl, and S had spatial arrangements that indicated Cl was pure KCI (or perhaps KC1O3, which map structure would be identical), and that S existed in identical space as K, indicating that it was probably K2SO4 . There was no mixing of Mg with ' The generation of an EDX map is accomplished when the beam rasters across the field, producing bright signals (from the charasteristic X-rays) for each element window when that element is detected . Simultaneously, the system produces an SEM image window along with the selected element maps . http://legacy.library.ucsf.edu/tid/zgg11d00/pdf Page 4 Date : April 2, 1996 To : Ms . DINAH MYERS Fm : GUY SPENCE any of the above three elements . If it had reacted in an exothermic reaction, then it was probably in the form of its oxide . FtG 4 : Fox of area shown in FIO 3, from 2 .5kX SeM image. The maps FtG 5 : Another view of the EpX map, this time showing the S show spatial locations of Mg, Cl, and K . Note that laaer two component . The upper left quadrant shows atombination of elements indicate that the crystals are KCI (or KCIO,) . the three elements : S, Cl, and K. Produced in color, it revealed that S was coincident with K (probably KiSUJ . Not shown, combined maps revcaled no mixing of Mg and S . ' In FIGURE 1, shown previously, there was a flake located just above and slightly toward the right of the measurement box . The flake was evaluated at high magnification, both by image and chemistry . FlcuaE 6 shows that flake, from the 2 .5kX SEM image . The line across its body is a computer measurement line, revealing that it was 38 .5 µm in length, which was approximately the length of the flake . The flake was analyzed by Evx. The quantitative analysis of its spectrum, shown in TABLE 2, disclosed that it was 12% Mg (or 20% MgO) . The spectrum also contained an appreciable amount of S, which is a sensitizer to incendiary fuels . Other ingredients that suggested that the material was a residue from an incendiary reaction was Cl and K, which are key ingredients of the oxidizing agent of choice, KClO4 (or occasionally KC103) . Finally, it also contained P . The reference literature suggests that phosphorus sesquisulf de (P4S) is a key ingredient in match incendiary blends . http://legacy.library.ucsf.edu/tid/zgg11d00/pdf Page 5 TABLE 2 : Quantitative Spectral Analysis from Area Shown In FIGURE 6. Spectrum label : k2Flake on IaminalMgKSCICaP Elmt Element Atomic Compound Nos . of % % % ions Mg K 12 .08 12 .84 MgO 20 .03 0.26 Si K 0 .55 0 .51 Si02 1 .18 0.01 P K 1 .36 1 .14 P205 3 .13 0.02 S K 4 .97 4 .00 S03 CI K 3 .97 2 .89 12 .41 0 .00 K K 39.65 26 .20 K20 Ca K 8 .24 5 .31 CaO 0 29.18 47 .11 b 3I1 .'. . .`.ini . ym ! Iq .N AY IN r~llll .m . 4l . FtG 6 : View of Mg-rich flake located on tobacco lamina M a . From the 2 .5kX SEM Image. See EDX quantitative analysis date in TABLE 2 at right . 0.08 0 .06 47 .76 0 .52 11 .53 0 .11 0.94 Total 100 .00 100 .00 96 .03 Mion sun 1 .00 . .Q Sigma Again referring back to F1GURE 1, there was a rather sizable contaminant particle shown to the left and slightly above the horizontal center of the measurement box . That area was analyzed at higher magnification . The particle's morphology is shown in F1GUttE 7, which is a view of the SEM image acquired at 2 .5kX. From the various shades of brightness, it was obvious that more than a single element phase was present in the structure . An Enx map was acquired over the area. Those data are shown in FIGUaE 8 . In the map, the Mg spatial distribution was coincident with the bright branched material from the image, horizontally center downward . From its appearance in 7, the material looked as if it had been deposited in a molten state' in a splatter, and cooled in that configuration. Although the original map collection acquired five elements (Mg, Cl, S, K, Ca) and the BSE image, no more than four of these specific FIGURE elements/image can be copied for insertion into this document at once . Therefore, FIGURE 9 displays another selection of elements from this map group . In it, the identity of the small aggregated group of particles above the Mg deposit was seen to be Ca . Of course, the specific identity was CaCO3, for the particles resemble very strongly those crystals frequently seen in analysis of cigarette paper. The Enx spectrum from that area was analyzed quantitatively . Those data are shown in TABLE 3 . It shows that a significant amount of the materials included incendiary ingredients Mg, Cl, P, S, and K . http://legacy.library.ucsf.edu/tid/zgg11d00/pdf TABLE 3 : Quantitative Spectral Analysis from Area Shown in FICURE 7 . Spectrum label: A30nIam/1 l 2 .5kXOnMgCaKSplash Elmt Element Atomic Compound Nos . of % % a/o ions Mg K 5 .89 6 .23 MgO 9 .77 0 .14 Si K 2 .SON~ W_N kV "t", i', r~ .n ; x: : MA J :- :LNiu Fto 7 : View of mass of a contaminant on lamina R I . View of the 2.5kX Seht image . sec EDx maps in Fta 8 . 0.54 0 .50 5i02 1 .16 0 .01 P K 2 .25 1 .87 P205 5 .16 0 .04 S K 6 .34 5 .08 S03 15.83 0 .11 CI K 3 .45 2 .50 0 .00 0 .05 K K 22 .23 14 .62 K20 26.78 0 .32 Ca K 27 .06 17 .36 CaO 37 .86 0.38 0 32 .24 51 .83 1 .13 Total 100 .00 100 .00 96 .55 Anion sum 1 .19 • ~ Q Sigma In the SEM analysis of the prepared materials, a second lamina section was found having a significant amount of incendiary-type components on it . Its surface was considerably different in appearance from that of lamina#1 . Rather than an array of discreet particles, relatively few in number, this lamina#2 was well covered with contaminant materials . Much of it was discovered by EDx analysis to be CaCO3 (from the paper ash), but in the contaminant blend, the EDx spectra showed a rather significant amount of incendiary-type materials similar to that which was identified in the discreet particles on lamina#1, previously reported . A view of lamina#2 is exhibited in F1ouItE 10, which was taken from the 250X SEM image . An EDX spectral analysis of this area produced quantitative data shown in TABLE 4 . Fto 8 : ImagelFDx map array showing spatial arrangemenlof eiemenis FLO9 : Eox map array ofeiements rmm F1o 7. Note that Ca was Mg, S, and CI . Note that bright, larger materials toward bottom coincident in space with the aggregate of small erystais situated of image were principally Mg deposits, above the Mg branched material . http://legacy.library.ucsf.edu/tid/zgg11d00/pdf To : Ms . DINAH MYERS Date : April 2, 1996 Fm : GUY SPENCE TABLE ¢ : Quantitative Spectral Analysis from Area Shown In FtoUnE 10 . Spectrum label : SpecLaminaq2NoLgPart Wi MgEtc Elmt Element Atomic Compound Nos . of % % % ions Mg K 3 .85 4 .20 MgO 6 .39 0.09 Si K 0.99 0 .93 Si02 2,11 0.02 P K 1 .63 1 .39 P205 3 .74 0.03 S K 3 .62 2.99 503 9 .03 0 .06 CI K 2 .44 1 .83 0.00 0 .04 K K 15 .52 10 .51 K20 18 .70 0 .22 Ca K 41 .16 27 .20 CaO 57 .59 0 .58 0 30 .79 50.96 1 .08 Total 100 .00 100,00 97.56 FIG 10 : View or250X SEM image, IaminaN2 . Anion sum 1 .12 ~ =Q Sigma The specimens that were taped to the note were examined with the SEm/Eox . They had some Mg materials on them, but the bulk of litter that was found on them was NaCI . Its significance is unconnected to the incendiary problem at this time . GUY SPENCE Cc : Dr . COOPER REES http://legacy.library.ucsf.edu/tid/zgg11d00/pdf Page 8
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