30th SEMI-ANNUAL SEMINAR (Fall 1967)
CALIFORNIA ASSOCIATION OF CRIMINALISTS
November 2-14, 1967
SAN JOSE, CALIFORNIA
RECENT PROGRESS IN FORENSIC ACTIVATION ANALYSIS
D.E. Bryan, V.P. Guinn, H.R. Lukens, H.L. Schlesinger, and D.M. Settle General Atomic Division of General Dynamics Corporation, San Diego
Although still relatively new, and still largely in the exploratory stage of development, forensic activation analysis is now showing distinct signs of approaching maturity (or at least puberty). These signs are the following:
- Certain kinds of important evidence materials are now being examined in depth, in large-scale studies designed to build up a suitable statistical background for the proper interpretation of the activation analysis results obtained in actual case work (these materials: hair, paint, paper, bullet lead).
- Some kinds of evidence materials previously surveyed by conventional instrumental neutron activation analysis (NAA) are now being re-examined with more advanced or supplementary techniques (these techniques! germanium-detector gamma-ray spectrometry, photonuclear activation analysis, reactor pulsing, and advanced computer data-processing techniques).
- Five appreciably-qualified laboratories now employ high-flux NAA on a regular basis for the examination of evidence specimens in selected criminal cases (these laboratories: the U.S. Treasury Department, the F.B.I., Gulf General Atomic, the Ontario [Canada] Centre of Forensic Sciences, and the Home Office Laboratory in Aldermaston [England]).
- Forensic activation analysis specialists are now themselves expressing concern about the premature use of as-yet not well-supported applications of NAA in actual cage work, the premature introduction of such results in court, and the premature examination of specimens from actual cases by some activation analysis who are as yet completely unversed in the field of forensic activation analysis. About one year ago, an informal international Forensic Activation Analysis Coordinating Group was formed, to help minimize such premature activities, and to help guide the development of the technique. Some progress is being made.
- The growth of the field has reached the point where the holding of the First International Conference on Forensic Activation Analysis, in San Diego about one year ago, was warranted.
- Forensic activation analysts have had sufficient direct contact with professional criminalists to begin to appreciate and under stand many of the problems faced by the criminalist — and many criminalists have begun to acquire a good working knowledge of the possibilities and limitations of forensic activation analysis. Increased liaison is needed, and is developing.
DETERMINATION OF ABO BLOOD GROUPS IN HUMAN HAIR
William J. Chisum and Fred H. Wynbrandt, California State Department of Justice, Sacramento, California
A method was described for the determination of the ABO blood group from a single strand of hair. The method is outlined as follows:
- Cut a length of hair approximately 3/4 inch.
- Wash for 1 minute in methanol, with agitation.
- Crush between 2 polished steel plates at 12,000 psi for 30 Seconds
- Boil in pH 7.4 McIlvaine's buffer for 30 seconds. Pat dry.
- Place 1/4" of hair into depression cells, add 1 drop Antisera (A,B and H).
- Allow to absorb for 24 hours at 4°-6°C.
- Wash thoroughly with ice water. Pat dry.
- Place on micro slide and cover with cover slip.
- Add appropriate 1/14%. cell suspension (A,B,O).
- Place in oven at 52-57°C for 10 minutes (moist chamber).
- Remove, read agglutination every 10 minutes for 1 hour.
Excellent results were obtained on hairs from both sexes of all age groups. Bleaching and dying the hair have no effect on the results; however, weak results were obtained on hairs from women using hair spray frequently.
POISON EXTRACTION AS RELATED TO CELLULAR ULTRASTRUCTURE
Brian P. Parker, School of Criminology, University of California, Berkeley, California
Separation of a toxic organic substance from the tissue matrix is effected by bulk chemical differentiations, making use of solubility characteristics for the organic substance in different environments. The current rapid expansion of knowledge on cellular ultrastructure and function presents an opportunity to examine the separation step in view of the possible, or probable, location of toxic organic substances within living tissue and, consequently, the most effective means of removal. Penetration of the cell membrane by a chemical substance was related to the outer protein, intermediate lipid, and inner protein layers of the membrane. Various models were discussed which attempt to explain the accumulated experimental data. A comparison of techniques used to extract tissue lipids directed at poison recoveries suggests that the extraction procedures are separating the total lipid content from the tissue. The essential solvent action in each case is a breakdown of the protein and phospholipid complex in membranes with subsequent lipid solution. The resulting solution in a complex mixture of small molecules to be separated (purified) for qualitative and quantitative determinations.
PERFORMANCE OF THE DPC INTOXIMETER IN COMBINATION WITH VAPOR PHASE CHROMATOGRAPHIC ANALYSIS OF THE ALCOHOL COLLECTED ON MAGNESIUM PERCHLORATE
Alfred A. Biasotti and Lowell W. Bradford, Laboratory of Criminalistics, Santa Clara County District Attorney's Office, San Jose, California
A method has been developed for the quantitative analysis of small amounts of ethanol (e.g., 50 to 500 micrograms) which are collected on anhydrous magnesium perchlorate. Measured samples of air passed through ethanol-water reference solutions were collected using a piston-cylinder arrangement called the "DPC" INTOXIMETER (Intoximeter Association), which operates on the "Breathalyzer" principle for collecting alveolar air but utilizes a larger sample volume (ca. 250cc) and a different valving system. The vapor samples were then discharged into magnesium perchlorate tubes to collect the ethanol. The ethanol collected was then analyzed by G.L.C. using one to two ml vapor samples taken over a solution of the magnesium perchlorate-ethanol in a measured volume of water containing dioxane as an internal standard.
Experimental data using this method with reference solution indicates a precision capability of ±5% of the ethanol concentration, e.g., 0.20 ±.01%.
X-RAY EVIDENCE IN THE BATTERED CHILD SYNDROME
James S. Vaudagna, M.D., Pediatric Radiologist, San Jose, California
The incidence of child abuse is common but often unrecognized. Child abuse is the second most common cause of death in pediatrics. Beating (including hitting, kicking, pulling, and twisting) is the most common type of abuse, but burning, biting, starvation, suffocation, isolation, and drowning are occasionally encountered. The mortality is estimated to be of the order of 10-20%, with a greater percentage suffering some degree of brain damage. The parent is the most common offender, although abuse by a sibling, baby sitter, or visiting lover is occasionally seen. In instances of child abuse, a detailed medical history is of extreme importance in establishing the factual considerations surrounding the injury. The statements furnished by the parents may not comply with the physical findings as to the time sequence of the injury. Slides were shown illustrating X-Rays of injuries to children resulting from physical abuse.
PRESENTATION OF EVIDENCE IN THE PROSECUTION OF ILLICIT AMPHETAMINE MANUFACTURING CASES
Cecil L. Hider, San Mateo County Sheriff's Department, Redwood City
The four basic proofs involved in court testimony of illicit amphetamine synthesis were discussed. The laboratory role and court testimony in these cases were evaluated. Special emphasis was placed on identification of yield products, precursors and the methods by which amphetamines could be manufactured. Eight methods of illicit amphetamine synthesis encountered in previous cases were discussed in detail. Facilitation of discussion of these cases was enhanced by use of a handout, which illustrated the chemical reactions involved. One additional handout was discussed where the suspect's actual notes and diagrams were utilized.
CONCEPT OF MINIMUM AMOUNT OF MARIJUANA REQUIRED FOR PROSECUTION
Robert L. Webb, Assistant District Attorney, Santa Clara County, San Jose, California
A brief history of the minimum amount of marijuana required for prosecution was presented. Section 11530 of the California Health and Safety Code makes possession of marijuana an offense. The statute does not specify the quantity necessary to sustain a conviction. The consideration arose first in 1936 with regard to traces of morphine in a spoon. The courts at this time declared minute traces to be illegal and sustained a conviction. In 1962 the courts appeared to reverse their original rulings and suggested that 5 mg of an unspecified narcotic may have been less than a usable amount, although the court sustained a conviction on the basis that the defendant presented no evidence at the time of the trial that the amount was insignificant. in P. vs. Leal, 64 Cal 2nd 504 (1966) and People vs. Thomas 246 Cal App. 244 (1966) the courts held that in a prosecution for possession of marijuana or a narcotic, the amount must be sufficient for "consumption or sale." A conviction cannot be based upon possession of minute fragments alone, but the possession of these fragments may be admitted into evidence in the course of the prosecution to prove knowledge of the nature of the material on the part of the defendant.
SOME CONSIDERATIONS REGARDING THE DUQUENOIS TEST FOR MARIJUANA
John I. Thornton and Duayne J. Dillon, Contra Costa County Sheriff's Department, Martinez, California
The chemistry of marijuana was discussed with respect to the structure of the phenolic and terpene constituents of marijuana. The reactivity of the Duquenois reagent was related to the structure of the phenolic moiety, and evidence was presented to suggest that the mechanism of the test is an electrophilic substitution reaction at the ortho- and parapositions to the phenol, with subsequent oxidation to a colored quinone-type material. Evidence was presented that the product of the Duquenois reaction is not an extensively reticulated polycondensate, but is a resole of limited size. Evidence was presented to indicate that the solubility of the colored complex from the Duquenois reaction in chloroform is a function of the long aliphatic chain on the resorcinol portion of the molecule, and that the specific colors formed in the chloroform layer and aqueous layer are a function of the solubility of the constituents and the pH of the solution. Slides were shown of TLC plates illustrating separations of cannabidiol, cannabidiolic acid, cannabinol, delta-1- and delta-6- tetrahydrocannabinol, using straight benzene or hexane: diethyl ether (4:1) as developing solvent on Silica Gel H plates.
EXAMINATION OF MARIJUANA SMOKE FOR CANNABINOL COMPOUNDS
Brian S. Finkle, Laboratory of Criminalistics, Santa Clara County District Attorney's Office, San Jose, California
Gas chromatography was employed to determine whether or not constituents of cannabis sativa resin were detectable in smoke, produced by artificially smoking marijuana cigarettes. It was determined that the quantity of each resin constituent varied greatly between different samples of cannabis plant, but that a typical marijuana cigarette (approximately 250 mg plant) could contain from 5 to 10 micrograms of tetrahydrocannabinol. Four resin constituents were trapped from the Gas Chromatograph, two of which were identified by infrared spectrophotometry as cannabinol and tetrahydrocannabinol. All four trapped fractions gave a blue color, varying somewhat in color and intensity, with Duquenois reagent and acid. The resin constituents were detectable in a petroleum ether extract of the smoke but in very small quantities compared to the amounts in the parent plant material. Smoking three marijuana cigarettes consecutively produced between one and two micrograms of cannabinol, but only a fraction of a microgram of tetrahydrocannabinol.
IDEALIZED MODELS OF STRIATED MARKS (Construction of Dependent Models)
James W. Brackett, Jr., San Mateo County Coroner's Office, Redwood City
A brief review of two previous papers in this field was presented to define the idealized tool mark which is quantized; that is, each striation is some integral distance from each neighbor, and of uniform distribution; that is, having equal numbers of striations of unit space apart, 2x unit space apart, 3x unit apace apart....It was previously established that such an ideal tool nark model is well approximated by suitable use of data from a random number table, and comparisons of such marks revealed regular properties of each class of comparison. An algebraic analysis led to a set of equations consistent with experiments which defined independent comparisons and various kinds of dependent comparisons.
A series of random number comparison experiments showed that there was no effect caused by any phase displacement of two dissimilar sets of like p, but identical sets were affected greatly by small phase displacements in an oscillatory manner, damped to a random non-identical comparison at displacements greater than p2. An algorithm to estimate these effects was found.
This paper presents data from non-identical comparisons of random number models of tool marks to show the effect of deviations from ideality caused by increasing the relative number of one spacing distance at the expense of the remaining distances, while retaining quantitization The results are shown in the table below. For experiments for p=3 the notation 1, 2, 3, indicates an equal number of 1 unit, 2 unit, and 3 unit spacings in comparison, while 2, 3, 2, 3 indicates twice as many two unit spaces as the number of either one or three spaces, etc.
|For all experiments above, p = 3 and N = 2187.
S₁ is number of single matches.
S₂ is number of double consecutive matches.
S₃ is number of triple consecutive matches, etc. p (exp) = (total of matches + non-matches)/matches = 1/probability of match.
* average of 4 separate experiments.
** this experiment and all below are actual.
|Description of Comparison||Non Match||Match||P exp||S₁||S₂||S₃||S₄||S₅||S₆||S₇||S₈||S₉||S₁₀||S₁₁||S₁₂
It may be seen that the effect on the number of matching lines is virtually independent of relative numbers of striae spacings as long as the effect is symmetrical; while dissymmetry causes a large effect. The number and size of runs of consecutive matching lines is shown to be generally a more sensitive indicator of ideality than is the percentage of matches, and reveals violation of the independence criterion.
SOME OBSERVATIONS ON THE REACTION OF NINHYDRIN WITH AMPHETAMINE-LIKE COMPOUNDS
Clifford C. Cromp, Los Angeles County Sheriff's Department, Los Angeles
The reaction of ninhydrin with amphetamine like compounds has been found to produce distinctive colors which are of use in identification of the compound. The colors found by the author differ from some reported in the literature.
- Powdered preparation of suspected drug dissolved in dilute HC1 in test tube, centrifuged and supernatant transferred to another tube. Filter if necessary. Liquid preparations are treated by starting with step 2 below.
- Add solution or liquid preparation made basic with 10% NaOH. Add 1 to 2 ml ether and shake. Allow ether layer to separate.
- Spot on thin layer plate along with suitable known compounds and develop with suitable solvent. Note: Eastman Chromagram Silica Gel sheets and isobutanol, acetic acid, water solvent used by author. This solvent does not appear to be the ideal one so more experimentation on solvents is indicated.
- Spray plate with 2% Ninhydrin in acetone. Allow to dry and place in oven for 5 to 10 minutes at approx. 105°C.
- Observe colors and location of spots.
Table I lists colors developed with six compounds investigated. The colors change with time and all change to brownish-purple after a few minutes to several hours, so observation of the colors as the plates come from the oven after the 5 to 10 minutes is extremely important.
|*Identity of STP (4-Methyl-2, 5-Dimethoxyamphetamine) sample not confirmed.
GAS CHROMATOGRAPHIC IDENTIFICATION OF BARBITURATES USING DERIVATIVES
Paul Leblsh, James W. Brackett, Jr., and David Lewis, San Mateo County Coroner's Office, Redwood City, California
A rapid, simple method was described for chlorinating aliphatic or aromatic unsaturated barbiturates to facilitate separation and identification by gas chromatography. The RRt's of the chlorinated products were reproducible and specific for the barbiturates whose derivatives were formed. Unsaturated barbiturates were thus distinguished from each other and also from saturated barbiturates close in RRt.
Formation of barbiturate derivatives was discussed with a view to achieving extreme sensitivity of detection using an electron capture detector. By formation of suitable derivatives it appears that pico-grain detection is feasible for barbiturates, amphetamine, certain other drugs and their metabolites. For example, whereas the limit of detectability with a hydrogen flame detector for amphetamine and methamphetamine is approximately 5 nanograms, it is possible to detect as little as 5 picograms of the AcCl₃ derivatives of amphetamine and methamphetamine using a Ni₆₃ electron capture detector.
IDENTIFICATION MOTES ON EXTRACTS OF THE LYSERGAMIDE CONTAINING TROPICAL WOOD ROSE
Steven P. McJunkins, San Mateo County Sheriff's Department, Redwood City, California, and John I. Thornton and Duayne J. Dillon, Contra Costa County Sheriff's Department, Martinez, California
The hallucinogenic tropical wood rose, Aroyreia nervosa, whose seeds have been shown to be the richest natural source of lysergemide yet investigated, was described with a brief outline of the botanical features followed by the results of a chemical examination of the seed extracts. Preparation and extraction of the seeds and the subsequent application of the extracts to thin layer plates was described. The color reactions obtained with a spray reagent were illustrated with projected color slides; U.V. spectrophotometric absorption data for the thin layer zones was given as well.
GAS CHROMATOGRAPHIC DETERMINATION OF HEROIN IN SILYLATED ILLICIT HEROIN SAMPLES
Julian O. Grooms and Herman J. Meuron, Alcohol and Tobacco Tax Unit, U.S. Treasury Department, San Francisco, California
Silylation of illicit heroin samples results in greatly superior GC curves. Besides improving peaks of a few alkaloids which can be obtained without silylation (such as heroin or morphine), peaks for adulterants such as lactose and procaine can also be obtained on the some chromatogram. Quinine is masked and starch does not give a peak. Heroin can be detected at the 1% level. For quantitative determination of heroin, an internal standard of 12 mg chinconine sulfate is added to the sample of illicit powder.
Silylating agent la "BSA" [N, 0-bis (trimethylsilyl) acetamide], sold by Pierce Chemical Company, Rockford, Illinois. 25 to 50 mg sample is weighed into a small glass vial and shaken with .5 ml BSA reagent (and cinchonine, if preferred) for 5 min. 2 1 are injected.
The column used is packed with 5% Se 30 on acid washed trimethylchlorosilane treated chronosorb W, 60/80 mesh. The temperature should be constant at around 200-203°C, with N₂ gas flow of 30 ml/min. Flame ionization detector was used.
Note: It has not yet been established that heroin itself is silylated but this does not appear to affect the quantitative results.