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FORENSIC SCIENCEToxicology and Drugs

Chapter 9 – Drugs

“Having sniffed the dead man’s lips, I detected a slightly sour smell, and I came to the conclusion that he had

poison forced upon him.”

– Sherlock Holmes, in Sir Arthur Conan Doyle’s “A Study in Scarlet”

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TOXICOLOGYTYPES:

• Environmental--air, water, soil

• Consumer--foods, cosmetics, drugs

• Medical, clinical, forensic

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Forensic Toxicology Postmortem--medical examiner or coroner Criminal--motor vehicle accidents (MVA),

assault, etc. Workplace drug testing Sports--human and animal

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Why do Toxicology?Toxicology can:

• Be a cause of death

• Contribute to death

• Cause impairment

• Explain behavior

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OUR STUDY

Drugs Poisons

Basically, toxicology involves the separation, detection, identification and measurement of the drug and/or poison.

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Testing

PDR’s--Physician’s Desk Reference Field Tests--presumptive tests Lab Tests--conclusive tests

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Physician Desk Reference PDR – a physician’s desk reference is used to

identify manufactured pills, tablets and capsules. It is updated each year. This can sometimes be a quick and easier identifier of the legally made drugs that may be found at a scene. The reference book gives a picture of the drug, whether it is a prescription, over the counter, or a controlled substance; as well as, more detailed information about the drug.

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PDR’s

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Drugs and Crime Definition – a natural or synthetic substance

designed to affect the subject psychologically or physiologically.

“Controlled substances” – drugs that are restricted by law

Controlled Substances Act – enacted in 1970 lists illegal drugs, their category and their penalty for possession, sale or use.

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Controlled Substances Act

Schedule I – high potential for abuse; no currently acceptable medical use in the U.S.; a lack of accepted safety for use under medical supervision

Schedule II – high potential for abuse; a currently accepted medical use with severe restrictions; abuse may lead to severe psychological or physical dependence

Schedule III – lower potential for abuse than the drugs in I or II; a currently accepted medical use in treatment in the U.S.; abuse may lead to moderate physical dependence or high psychological dependence

Schedule IV – low potential for abuse relative to drugs in III; a currently accepted medical use in treatment in the U.S.; abuse may lead to limited physical dependence or psychological dependence relative to drugs in III

Schedule V – low potential for abuse relative to drugs in IV; currently accepted medical use in treatment in the U.S.; abuse may lead to limited physical dependence or psychological dependence relative to drugs in IV

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Analysis of Drugs

Controlled Substances Act

• Schedule I--heroin, LSD

• Schedule II--morphine, methadone

• Schedule III--barbiturates, amphetamines

• Schedule IV--other stimulates and depressants

• Schedule V--codeine

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DRUG IDENTIFICATIONScreening tests or

presumptive tests Color tests Ultraviolet (UV) Visible Microcrystalline test--a

reagent is added that produces a crystalline precipitate which are unique for certain drugs.

Confirmation tests Chromatography Spectrophotometry Mass spectrometry

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Presumptive Color Tests

Marquis--turns purple in the presence of most opium derivatives and orange-brown with amphetamines

Dillie-Koppanyi--turns violet-blue in the presence of barbiturates

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Presumptive Color Tests Duquenois-Levine--turns a purple color in

the presence of marijuana Van Urk--turns a blue-purple in the

presence of LSD Scott test--color test for cocaine

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Confirmation TestsChromatography

Techniques for separating mixtures into their component compounds

Includes two phases--one mobile and one stationary that flow past one another

As the mixture separates it interacts with the two phases.

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Human Componentsfor Drug Analysis

Blood

Urine

Hair

Gastric Contents

Bile

Liver tissue

Brain tissue

Kidney tissue

Spleen tissue

Vitreous Humor of the

Eye

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Types of Chromatography Paper Thin Layer Gas Pyrolysis Gas High Pressure Liquid (HPLC)

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Paper Chromatography

Stationary phase--paper

Mobile phase--a liquid solvent

Capillary action moves the mobile phase through the stationary phase

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Thin Layer Chromatography Stationary phase--a

thin layer of coating on a sheet of plastic or glass (usually aluminum or silica)

Mobile phase--a liquid solvent

from www.lbp.police.uk

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Retention Factor (Rf)

This is a number that represents how far a compound travels in a particular solvent

It is determined by measuring the distance the compound traveled and dividing it by the distance the solvent traveled.

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Retention Factor (Rf)

If the Rf value for an unknown compound is close to or the same as that for the known compound, the two compounds are most likely similar or identical (a match)

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Gas Chromatography

Stationary phase--a solid or very syrupy liquid lines a tube or column

Mobile phase--an inert gas like nitrogen or helium

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GC Analysis Shows a peak that is proportional to the

quantity of the substance present Uses retention time instead of Rf for the

quantitative analysis

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Gas ChromatographyPhases Stationary – a solid or

very syrupy liquid lines a tube or column

Mobile – an inert gas like nitrogen or helium

Analysis Shows a peak that is

proportional to the quantity of the substance present

Uses retention time instead of Rf for the quantitative analysis

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Retention Time Time between the sample being injected

and when it exits the column reaching the detector.

Tm is the time taken for the mobile phase to pass through the column

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Pyrolysis Gas Chromatography

Used when a sample does not readily dissolve in a solvent

If heating this sample decomposes it into gaseous products, these products can be analyzed by CGC

A pyrogram is the visual representation of the results

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High Pressure LiquidChromatography

Stationary phase--fine solid particles Mobile phase--a liquid solvent

A solvent is pumped through the column as a sample is injected into it. The sample, as it moves, is slowed to differing degrees, depending on its interaction with the stationary phase. Different components of the sample mixture are, therefore, separated.

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SpectrophotometrySpectroscopy – the interaction of electromagnetic

radiation with matter

Spectrophotometer – An instrument used to measure and record the absorption spectrum of a chemical substance

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SpectrophotometryComponents

• A radiation source• A frequency selector• A sample holder• A detector to convert electromagnetic radiation into an electrical

signal • A recorder to produce a record of the signal

Types• Ultraviolet• Visible• Infrared

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Infrared Spectometry

Material absorbs energy in the near-IR region of the electromagnetic spectrum

Compare the IR light beam before and after passing through a transparent sample

Result – an absorption spectrum Gives a unique view of the substance – like a fingerprint

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Mass Spectrometry

Gas chromatography has one major drawback--it does not give a specific identification. By teaming a gas chromatograph with a mass spectrometer, this is accomplished.

The mixture is separated first in a gas chromatograph. The GC column is directly attached to the mass spectrometer where a beam of electrons is shot through the sample molecules.

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MS (cont.)

The electrons cause the molecules to lose electrons and become positively charged. These are unstable and decompose into many smaller fragments. These fragments pass through an electric or magnetic field and are separated according to their masses.

NO TWO SUBSTANCES PRODUCE THE SAME FRAGMENTATION PATTERN.

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Example of a GS/MS

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Human Analysisfor Drugs

Blood

Urine

Vitreous

Bile

Liver tissue

Brain tissue

Kidney tissue

Spleen tissue

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“If all those buried in our cemeteries who were poisoned could raise their hands, we would probably be shocked by the numbers. --John Trestrail

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POISONERS in HISTORY Olympias—a famous Greek poisoner Locusta—personal poisoner of Emperor Nero Lucretia Borgia—father was Pope Alexander VI Madame Giulia Toffana—committed over 600 successful

poisonings, including two Popes. Hieronyma Spara—formed a society to teach women how

to murder their husbands Madame de Brinvilliers and Catherine Deshayes—French

poisoners.

AND many others through modern times.

Symptoms of VariousTypes of Poisoning

Type of Poison Symptom/Evidence• Caustic Poison (lye) Characteristic burns around the lips

and mouth of the victim

• Carbon Monoxide Red or pink patches on the chest and thighs. Unusually brighter red lividity

• Sulfuric acid Black vomit

• Hydrochloric acid Greenish-brown vomit

• Nitric acid Yellow vomit

• Phosphorous Coffee brown vomit. Onion or garlic odor

• Cyanide Burnt almond odor

• Arsenic, Mercury Pronounced diarrhea

• Methyl (wood) or Nausea and vomiting,

Isopropyl (rubbing) alcohol unconsciousness, possibly blindness

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Points to Know about aPoison

Form Common color Characteristic odor Solubility Taste Common sources Lethal dose Mechanism Possible methods of

administration Time interval of onset of

symptoms.

Symptoms resulting from an acute exposure

Symptoms resulting from chronic exposure

Disease states mimicked by poisoning

Notes relating to the victim Specimens from victim Analytical detection methods Known toxic levels Notes pertinent to analysis of

poison List of cases in which poison

was used

from “Criminal Poisoning” by John Trestrail

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Evidence

ClassPresumptive or screening tests can be used to

determine that it is a drug.

IndividualChromatography, especially in conjunction with

mass spectrometry, will specifically identify a drug or poison and its components.

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People of Historical Significance

Arthur Jeffrey Dempster was born in Canada, but studied and received his PhD from the University of Chicago. He began teaching physics there in 1916. In 1918, Dempster developed the first modern mass spectrometer. His version was over 100 times more accurate than previous ones developed, and established the basic theory and design of mass spectrometers that is still used to this day.

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People of Historical Significance

Francis William Aston was a British physicist who won the Nobel Prize in Chemistry for his work in the invention of the mass spectrometer. He used a method of electromagnetic focusing to invent the mass spectrograph. This allowed him to identify no fewer than 212 of the 287 naturally occurring isotopes.