Forensic Chemistry
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Forensic chemistry is the application of
chemistry Chemistry is the science, scientific study of the properties and behavior of matter. It is a natural science that covers the Chemical element, elements that make up matter to the chemical compound, compounds made of atoms, molecules and ions ...
and its subfield,
forensic toxicology Forensic toxicology is the use of toxicology and disciplines such as analytical chemistry, pharmacology and clinical chemistry to aid medical or legal investigation of death, poisoning, and drug use. The primary concern for forensic toxicology is ...
, in a legal setting. A forensic chemist can assist in the identification of unknown materials found at a
crime scene A crime scene is any location that may be associated with a committed crime. Crime scenes contain physical evidence that is pertinent to a criminal investigation. This evidence is collected by crime scene investigators (CSI) and law enforcement ...
. Specialists in this field have a wide array of methods and instruments to help identify unknown substances. These include
high-performance liquid chromatography High-performance liquid chromatography (HPLC), formerly referred to as high-pressure liquid chromatography, is a technique in analytical chemistry used to separate, identify, and quantify each component in a mixture. It relies on pumps to pa ...
,
gas chromatography-mass spectrometry Gas is one of the four fundamental states of matter (the others being solid, liquid, and plasma). A pure gas may be made up of individual atoms (e.g. a noble gas like neon), elemental molecules made from one type of atom (e.g. oxygen), or com ...
,
atomic absorption spectroscopy Atomic absorption spectroscopy (AAS) and atomic emission spectroscopy (AES) is a spectroanalytical procedure for the quantitative determination of chemical elemlight) by free atoms in the gaseous state. Atomic absorption spectroscopy is based o ...
,
Fourier transform infrared spectroscopy Fourier-transform infrared spectroscopy (FTIR) is a technique used to obtain an infrared spectrum of absorption or emission of a solid, liquid, or gas. An FTIR spectrometer simultaneously collects high-resolution spectral data over a wide spectr ...
, and
thin layer chromatography Thin-layer chromatography (TLC) is a chromatography technique used to separate non-volatile mixtures. Thin-layer chromatography is performed on a sheet of an inert substrate such as glass, plastic, or aluminium foil, which is coated with a t ...
. The range of different methods is important due to the destructive nature of some instruments and the number of possible unknown substances that can be found at a scene. Forensic chemists prefer using nondestructive methods first, to preserve evidence and to determine which destructive methods will produce the best results. Along with other forensic specialists, forensic chemists commonly testify in court as
expert witness An expert witness, particularly in common law countries such as the United Kingdom, Australia, and the United States, is a person whose opinion by virtue of education, training, certification, skills or experience, is accepted by the judge as ...
es regarding their findings. Forensic chemists follow a set of standards that have been proposed by various agencies and governing bodies, including the Scientific Working Group on the Analysis of Seized Drugs. In addition to the
standard operating procedure A standard operating procedure (SOP) is a set of step-by-step instructions compiled by an organization to help workers carry out routine operations. SOPs aim to achieve efficiency, quality output, and uniformity of performance, while reducing misc ...
s proposed by the group, specific agencies have their own standards regarding the
quality assurance Quality assurance (QA) is the term used in both manufacturing and service industries to describe the systematic efforts taken to ensure that the product(s) delivered to customer(s) meet with the contractual and other agreed upon performance, design ...
and
quality control Quality control (QC) is a process by which entities review the quality of all factors involved in production. ISO 9000 defines quality control as "a part of quality management focused on fulfilling quality requirements". This approach places ...
of their results and their instruments. To ensure the accuracy of what they are reporting, forensic chemists routinely check and verify that their instruments are working correctly and are still able to detect and measure various quantities of different substances.


Role in investigations

Forensic chemists' analysis can provide leads for investigators, and they can confirm or refute their suspicions. The identification of the various substances found at the scene can tell investigators what to look for during their search. During
fire investigation Fire investigation, sometimes referred to as origin and cause investigation, is the analysis of fire-related incidents. After firefighters extinguish a fire, an investigation is launched to determine the origin and cause of the fire or explosion ...
s, forensic chemists can determine if an
accelerant Accelerants are substances that can bond, mix or disturb another substance and cause an increase in the speed of a natural, or artificial chemical process. Accelerants play a major role in chemistry—most chemical reactions can be hastened with an ...
such as
gasoline Gasoline (; ) or petrol (; ) (see ) is a transparent, petroleum-derived flammable liquid that is used primarily as a fuel in most spark-ignited internal combustion engines (also known as petrol engines). It consists mostly of organic co ...
or
kerosene Kerosene, paraffin, or lamp oil is a combustible hydrocarbon liquid which is derived from petroleum. It is widely used as a fuel in aviation as well as households. Its name derives from el, κηρός (''keros'') meaning "wax", and was regi ...
was used; if so, this suggests that the fire was intentionally set. Forensic chemists can also narrow down the suspect list to people who would have access to the substance used in a crime. For example, in explosive investigations, the identification of
RDX RDX (abbreviation of "Research Department eXplosive") or hexogen, among other names, is an organic compound with the formula (O2N2CH2)3. It is a white solid without smell or taste, widely used as an explosive. Chemically, it is classified as a ...
or C-4 would indicate a military connection as those substances are military grade explosives. On the other hand, the identification of
TNT Trinitrotoluene (), more commonly known as TNT, more specifically 2,4,6-trinitrotoluene, and by its preferred IUPAC name 2-methyl-1,3,5-trinitrobenzene, is a chemical compound with the formula C6H2(NO2)3CH3. TNT is occasionally used as a reagen ...
would create a wider suspect list, since it is used by demolition companies as well as in the military. During poisoning investigations, the detection of specific poisons can give detectives an idea of what to look for when they are interviewing potential suspects. For example, an investigation that involves
ricin Ricin ( ) is a lectin (a carbohydrate-binding protein) and a highly potent toxin produced in the seeds of the castor oil plant, ''Ricinus communis''. The median lethal dose (LD50) of ricin for mice is around 22 micrograms per kilogram of body ...
would tell investigators to look for ricin's precursors, the seeds of the
castor oil plant ''Ricinus communis'', the castor bean or castor oil plant, is a species of perennial flowering plant in the spurge family, Euphorbiaceae. It is the sole species in the monotypic genus, ''Ricinus'', and subtribe, Ricininae. The evolution of cas ...
. Forensic chemists also help to confirm or refute investigators' suspicions in drug or alcohol cases. The instruments used by forensic chemists can detect minute quantities, and accurate measurement can be important in crimes such as
driving under the influence Driving under the influence (DUI)—also called driving while impaired, impaired driving, driving while intoxicated (DWI), drunk driving, operating while intoxicated (OWI), operating under the influence (OUI), operating vehicle under the infl ...
as there are specific
blood alcohol content Blood alcohol content (BAC), also called blood alcohol concentration or blood alcohol level, is a measurement of alcohol intoxication used for legal or medical purposes; it is expressed as mass of alcohol per volume or mass of blood. For exampl ...
cutoffs where penalties begin or increase. In suspected
overdose A drug overdose (overdose or OD) is the ingestion or application of a drug or other substance in quantities much greater than are recommended.
cases, the quantity of the drug found in the person's system can confirm or rule out overdose as the cause of death.


History


Early history

Throughout history, a variety of poisons have been used to commit murder, including
arsenic Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. Arsenic is a metalloid. It has various allotropes, but ...
, nightshade, hemlock,
strychnine Strychnine (, , US chiefly ) is a highly toxic, colorless, bitter, crystalline alkaloid used as a pesticide, particularly for killing small vertebrates such as birds and rodents. Strychnine, when inhaled, swallowed, or absorbed through the eye ...
, and
curare Curare ( /kʊˈrɑːri/ or /kjʊˈrɑːri/; ''koo-rah-ree'' or ''kyoo-rah-ree'') is a common name for various alkaloid arrow poisons originating from plant extracts. Used as a paralyzing agent by indigenous peoples in Central and South ...
. Until the early 19th century, there were no methods to accurately determine if a particular chemical was present, and poisoners were rarely punished for their crimes. In 1836, one of the first major contributions to forensic chemistry was introduced by British chemist James Marsh. He created the
Marsh test The Marsh test is a highly sensitive method in the detection of arsenic, especially useful in the field of forensic toxicology when arsenic was used as a poison. It was developed by the chemist James Marsh and first published in 1836. The metho ...
for arsenic detection, which was subsequently used successfully in a murder trial. It was also during this time that forensic toxicology began to be recognized as a distinct field.
Mathieu Orfila Mathieu Joseph Bonaventure Orfila (Catalan: ''Mateu Josep Bonaventura Orfila i Rotger'') (24 April 1787 – 12 March 1853) was a Spanish toxicologist and chemist, the founder of the science of toxicology. Role in forensic toxicology If th ...
, the "father of toxicology", made great advancements to the field during the early 19th century. A pioneer in the development of forensic microscopy, Orfila contributed to the advancement of this method for the detection of blood and semen. Orfila was also the first chemist to successfully classify different chemicals into categories such as
corrosive A corrosive substance is one that will damage or destroy other substances with which it comes into contact by means of a chemical reaction. Etymology The word ''corrosive'' is derived from the Latin verb ''corrodere'', which means ''to gnaw'', ...
s,
narcotic The term narcotic (, from ancient Greek ναρκῶ ''narkō'', "to make numb") originally referred medically to any psychoactive compound with numbing or paralyzing properties. In the United States, it has since become associated with opiates ...
s, and
astringent An astringent (sometimes called adstringent) is a chemical that shrinks or constricts body tissues. The word derives from the Latin ''adstringere'', which means "to bind fast". Calamine lotion, witch hazel, and yerba mansa, a Californian plant ...
s. The next advancement in the detection of poisons came in 1850 when a valid method for detecting vegetable
alkaloid Alkaloids are a class of basic, naturally occurring organic compounds that contain at least one nitrogen atom. This group also includes some related compounds with neutral and even weakly acidic properties. Some synthetic compounds of similar ...
s in human tissue was created by chemist
Jean Stas Jean Servais Stas (21 August 1813 – 13 December 1891) was a Belgian analytical chemist who co-discovered the atomic weight of carbon. Life and work Stas was born in Leuven and trained initially as a physician. He later switched to chemistr ...
. Stas's method was quickly adopted and used successfully in court to convict Count Hippolyte Visart de Bocarmé of murdering his brother-in-law by
nicotine Nicotine is a natural product, naturally produced alkaloid in the nightshade family of plants (most predominantly in tobacco and ''Duboisia hopwoodii'') and is widely used recreational drug use, recreationally as a stimulant and anxiolytic. As ...
poisoning. Stas was able to successfully isolate the alkaloid from the organs of the victim. Stas's protocol was subsequently altered to incorporate tests for
caffeine Caffeine is a central nervous system (CNS) stimulant of the methylxanthine class. It is mainly used recreationally as a cognitive enhancer, increasing alertness and attentional performance. Caffeine acts by blocking binding of adenosine t ...
,
quinine Quinine is a medication used to treat malaria and babesiosis. This includes the treatment of malaria due to ''Plasmodium falciparum'' that is resistant to chloroquine when artesunate is not available. While sometimes used for nocturnal leg cr ...
,
morphine Morphine is a strong opiate that is found naturally in opium, a dark brown resin in poppies (''Papaver somniferum''). It is mainly used as a analgesic, pain medication, and is also commonly used recreational drug, recreationally, or to make ...
, strychnine,
atropine Atropine is a tropane alkaloid and anticholinergic medication used to treat certain types of nerve agent and pesticide poisonings as well as some types of slow heart rate, and to decrease saliva production during surgery. It is typically given i ...
, and
opium Opium (or poppy tears, scientific name: ''Lachryma papaveris'') is dried latex obtained from the seed capsules of the opium poppy ''Papaver somniferum''. Approximately 12 percent of opium is made up of the analgesic alkaloid morphine, which i ...
. The wide range of instrumentation for forensic chemical analysis also began to be developed during this time period. The early 19th century saw the invention of the
spectroscope An optical spectrometer (spectrophotometer, spectrograph or spectroscope) is an instrument used to measure properties of light over a specific portion of the electromagnetic spectrum, typically used in spectroscopic analysis to identify mate ...
by
Joseph von Fraunhofer Joseph Ritter von Fraunhofer (; ; 6 March 1787 – 7 June 1826) was a German physicist and optical lens manufacturer. He made optical glass, an achromatic telescope, and objective lenses. He also invented the spectroscope and developed diffract ...
. In 1859, chemist
Robert Bunsen Robert Wilhelm Eberhard Bunsen (; 30 March 1811 – 16 August 1899) was a German chemist. He investigated emission spectra of heated elements, and discovered caesium (in 1860) and rubidium (in 1861) with the physicist Gustav Kirchhoff. The Bu ...
and physicist
Gustav Kirchhoff Gustav Robert Kirchhoff (; 12 March 1824 – 17 October 1887) was a German physicist who contributed to the fundamental understanding of electrical circuits, spectroscopy, and the emission of black-body radiation by heated objects. He coine ...
expanded on Fraunhofer's invention. Their experiments with spectroscopy showed that specific substances created a unique
spectrum A spectrum (plural ''spectra'' or ''spectrums'') is a condition that is not limited to a specific set of values but can vary, without gaps, across a continuum. The word was first used scientifically in optics to describe the rainbow of colors i ...
when exposed to specific wavelengths of light. Using spectroscopy, the two scientists were able to identify substances based on their spectrum, providing a method of identification for unknown materials. In 1906 botanist
Mikhail Tsvet Mikhail Semyonovich Tsvet (Михаил Семёнович Цвет, also spelled Tsvett, Tswett, Tswet, Zwet, and Cvet; 14 May 1872 – 26 June 1919) was a Russian-Italian botanist who invented chromatography. His last name is Russian for "colo ...
invented
paper chromatography Paper chromatography is an analytical method used to separate coloured chemicals or substances. It is now primarily used as a teaching tool, having been replaced in the laboratory by other chromatography methods such as thin-layer chromatography ...
, an early predecessor to thin layer chromatography, and used it to separate and examine the plant proteins that make up
chlorophyll Chlorophyll (also chlorophyl) is any of several related green pigments found in cyanobacteria and in the chloroplasts of algae and plants. Its name is derived from the Greek words , ("pale green") and , ("leaf"). Chlorophyll allow plants to a ...
. The ability to separate mixtures into their individual components allows forensic chemists to examine the parts of an unknown material against a database of known products. By matching the
retention factor In chromatography, the retardation factor (''R'') is the fraction of an analyte An analyte, component (in clinical chemistry), or chemical species is a substance or chemical constituent that is of interest in an analytical procedure. The purest ...
s for the separated components with known values, materials can be identified.


Modernization

Modern forensic chemists rely on numerous instruments to identify unknown materials found at a crime scene. The 20th century saw many advancements in technology that allowed chemists to detect smaller amounts of material more accurately. The first major advancement in this century came during the 1930s with the invention of a spectrometer that could measure the signal produced with infrared (IR) light. Early IR spectrometers used a
monochromator A monochromator is an optical device that transmits a mechanically selectable narrow band of wavelengths of light or other radiation chosen from a wider range of wavelengths available at the input. The name is from the Greek roots ''mono-'', "s ...
and could only measure light absorption in a very narrow wavelength band. It was not until the coupling of an
interferometer Interferometry is a technique which uses the ''interference'' of superimposed waves to extract information. Interferometry typically uses electromagnetic waves and is an important investigative technique in the fields of astronomy, fiber op ...
with an IR spectrometer in 1949 by Peter Fellgett that the complete infrared spectrum could be measured at once. Fellgett also used the
Fourier transform A Fourier transform (FT) is a mathematical transform that decomposes functions into frequency components, which are represented by the output of the transform as a function of frequency. Most commonly functions of time or space are transformed, ...
, a mathematical method that can break down a signal into its individual frequencies, to make sense of the enormous amount of data received from the complete infrared analysis of a material. Since then,
Fourier transform infrared spectroscopy Fourier-transform infrared spectroscopy (FTIR) is a technique used to obtain an infrared spectrum of absorption or emission of a solid, liquid, or gas. An FTIR spectrometer simultaneously collects high-resolution spectral data over a wide spectr ...
(FTIR) instruments have become critical in the forensic analysis of unknown material because they are nondestructive and extremely quick to use. Spectroscopy was further advanced in 1955 with the invention of the modern atomic absorption (AA) spectrophotometer by Alan Walsh. AA analysis can detect specific elements that make up a sample along with their concentrations, allowing for the easy detection of heavy metals such as arsenic and
cadmium Cadmium is a chemical element with the symbol Cd and atomic number 48. This soft, silvery-white metal is chemically similar to the two other stable metals in group 12, zinc and mercury. Like zinc, it demonstrates oxidation state +2 in most of ...
. Advancements in the field of chromatography arrived in 1953 with the invention of the
gas chromatograph Gas chromatography (GC) is a common type of chromatography used in analytical chemistry for separating and analyzing compounds that can be vaporized without decomposition. Typical uses of GC include testing the purity of a particular substance, ...
by Anthony T. James and
Archer John Porter Martin Archer John Porter Martin (1 March 1910 – 28 July 2002) was a British chemist who shared the 1952 Nobel Prize in Chemistry for the invention of partition chromatography with Richard Synge. Early life Martin's father was a GP. Martin was e ...
, allowing for the separation of volatile liquid mixtures with components which have similar boiling points. Nonvolatile liquid mixtures could be separated with
liquid chromatography In chemical analysis, chromatography is a laboratory technique for the separation of a mixture into its components. The mixture is dissolved in a fluid solvent (gas or liquid) called the ''mobile phase'', which carries it through a system (a ...
, but substances with similar retention times could not be resolved until the invention of high-performance liquid chromatography (HPLC) by Csaba Horváth in 1970. Modern HPLC instruments are capable of detecting and resolving substances whose concentrations are as low as
parts per trillion In science and engineering, the parts-per notation is a set of pseudo-units to describe small values of miscellaneous dimensionless quantities, e.g. mole fraction or mass fraction. Since these fractions are quantity-per-quantity measures, they ...
. One of the most important advancements in forensic chemistry came in 1955 with the invention of
gas chromatography-mass spectrometry Gas is one of the four fundamental states of matter (the others being solid, liquid, and plasma). A pure gas may be made up of individual atoms (e.g. a noble gas like neon), elemental molecules made from one type of atom (e.g. oxygen), or com ...
(GC-MS) by
Fred McLafferty Fred Warren McLafferty (May 11, 1923 − December 26, 2021) was an American chemist known for his work in mass spectrometry. He is best known for the McLafferty rearrangement reaction that was observed with mass spectrometry. With Roland Gohl ...
and Roland Gohlke. The coupling of a gas chromatograph with a mass spectrometer allowed for the identification of a wide range of substances. GC-MS analysis is widely considered the "gold standard" for forensic analysis due to its sensitivity and versatility along with its ability to quantify the amount of substance present. The increase in the sensitivity of instrumentation has advanced to the point that minute impurities within compounds can be detected potentially allowing investigators to trace chemicals to a specific batch and lot from a manufacturer.


Methods

Forensic chemists rely on a multitude of instruments to identify unknown substances found at a scene. Different methods can be used to determine the identity of the same substance, and it is up to the examiner to determine which method will produce the best results. Factors that forensic chemists might consider when performing an examination are the length of time a specific instrument will take to examine a substance and the destructive nature of that instrument. They prefer using nondestructive methods first, to preserve the evidence for further examination. Nondestructive techniques can also be used to narrow down the possibilities, making it more likely that the correct method will be used the first time when a destructive method is used.


Spectroscopy

The two main standalone spectroscopy techniques for forensic chemistry are FTIR and AA spectroscopy. FTIR is a nondestructive process that uses
infrared light Infrared (IR), sometimes called infrared light, is electromagnetic radiation (EMR) with wavelengths longer than those of visible light. It is therefore invisible to the human eye. IR is generally understood to encompass wavelengths from arou ...
to identify a substance. The
attenuated total reflectance Attenuated total reflection (ATR) is a sampling technique used in conjunction with infrared spectroscopy which enables samples to be examined directly in the solid or liquid state without further preparation. ATR uses a property of total inter ...
sampling technique eliminates the need for substances to be prepared before analysis. The combination of nondestructiveness and zero preparation makes ATR FTIR analysis a quick and easy first step in the analysis of unknown substances. To facilitate the positive identification of the substance, FTIR instruments are loaded with databases that can be searched for known spectra that match the unknown's spectra. FTIR analysis of mixtures, while not impossible, presents specific difficulties due to the cumulative nature of the response. When analyzing an unknown that contains more than one substance, the resulting spectra will be a combination of the individual spectra of each component. While common mixtures have known spectra on file, novel mixtures can be difficult to resolve, making FTIR an unacceptable means of identification. However, the instrument can be used to determine the general chemical structures present, allowing forensic chemists to determine the best method for analysis with other instruments. For example, a methoxy group will result in a peak between 3,030 and 2,950
wavenumber In the physical sciences, the wavenumber (also wave number or repetency) is the ''spatial frequency'' of a wave, measured in cycles per unit distance (ordinary wavenumber) or radians per unit distance (angular wavenumber). It is analogous to temp ...
s (cm−1). Atomic absorption spectroscopy (AAS) is a destructive technique that is able to determine the elements that make up the analyzed sample. AAS performs this analysis by subjecting the sample to an extremely high heat source, breaking the atomic bonds of the substance, leaving free atoms. Radiation in the form of light is then passed through the sample forcing the atoms to jump to a higher energy state. Forensic chemists can test for each element by using a corresponding wavelength of light that forces that element's atoms to a higher energy state during the analysis. For this reason, and due to the destructive nature of this method, AAS is generally used as a confirmatory technique after preliminary tests have indicated the presence of a specific element in the sample. The concentration of the element in the sample is proportional to the amount of light absorbed when compared to a blank sample. AAS is useful in cases of suspected
heavy metal poisoning A toxic heavy metal is any relatively dense metal or metalloid that is noted for its potential toxicity, especially in environmental contexts. The term has particular application to cadmium, mercury and lead, all of which appear in the World H ...
such as with
arsenic Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. Arsenic is a metalloid. It has various allotropes, but ...
,
lead Lead is a chemical element with the symbol Pb (from the Latin ) and atomic number 82. It is a heavy metal that is denser than most common materials. Lead is soft and malleable, and also has a relatively low melting point. When freshly cu ...
,
mercury Mercury commonly refers to: * Mercury (planet), the nearest planet to the Sun * Mercury (element), a metallic chemical element with the symbol Hg * Mercury (mythology), a Roman god Mercury or The Mercury may also refer to: Companies * Merc ...
, and
cadmium Cadmium is a chemical element with the symbol Cd and atomic number 48. This soft, silvery-white metal is chemically similar to the two other stable metals in group 12, zinc and mercury. Like zinc, it demonstrates oxidation state +2 in most of ...
. The concentration of the substance in the sample can indicate whether heavy metals were the cause of death.


Chromatography

Spectroscopy techniques are useful when the sample being tested is pure, or a very common mixture. When an unknown mixture is being analyzed it must be broken down into its individual parts. Chromatography techniques can be used to break apart mixtures into their components allowing for each part to be analyzed separately. Thin layer chromatography (TLC) is a quick alternative to more complex chromatography methods. TLC can be used to analyze inks and dyes by extracting the individual components. This can be used to investigate notes or fibers left at the scene since each company's product is slightly different and those differences can be seen with TLC. The only limiting factor with TLC analysis is the necessity for the components to be
soluble In chemistry, solubility is the ability of a substance, the solute, to form a solution with another substance, the solvent. Insolubility is the opposite property, the inability of the solute to form such a solution. The extent of the solubil ...
in whatever solution is used to carry the components up the analysis plate. This solution is called the
mobile phase In analytical and organic chemistry, elution is the process of extracting one material from another by washing with a solvent; as in washing of loaded ion-exchange resins to remove captured ions. In a liquid chromatography experiment, for exa ...
. The forensic chemist can compare unknowns with known standards by looking at the distance each component travelled. This distance, when compared to the starting point, is known as the retention factor (Rf) for each extracted component. If each Rf value matches a known sample, that is an indication of the unknown's identity. High-performance liquid chromatography can be used to extract individual components from a mixture dissolved in a
solution Solution may refer to: * Solution (chemistry), a mixture where one substance is dissolved in another * Solution (equation), in mathematics ** Numerical solution, in numerical analysis, approximate solutions within specified error bounds * Soluti ...
. HPLC is used for nonvolatile mixtures that would not be suitable for gas chromatography. This is useful in drug analysis where the pharmaceutical is a combination drug since the components would separate, or elute, at different times allowing for the verification of each component. The eluates from the HPLC column are then fed into various
detectors A sensor is a device that produces an output signal for the purpose of sensing a physical phenomenon. In the broadest definition, a sensor is a device, module, machine, or subsystem that detects events or changes in its environment and sends ...
that produce a peak on a graph relative to its concentration as it elutes off the column. The most common type of detector is an ultraviolet-visible spectrometer as the most common item of interest tested with HPLC, pharmaceuticals, have UV absorbance. Gas chromatography (GC) performs the same function as liquid chromatography, but it is used for volatile mixtures. In forensic chemistry, the most common GC instruments use mass spectrometry as their detector. GC-MS can be used in investigations of arson, poisoning, and explosions to determine exactly what was used. In theory, GC-MS instruments can detect substances whose concentrations are in the
femtogram To help compare different Order of magnitude, orders of magnitude, the following lists describe various mass levels between 10−59 kilogram, kg and 1052 kg. The least massive thing listed here is a graviton, and the most massive thing ...
() range. However, in practice, due to
signal-to-noise ratio Signal-to-noise ratio (SNR or S/N) is a measure used in science and engineering that compares the level of a desired signal to the level of background noise. SNR is defined as the ratio of signal power to the noise power, often expressed in deci ...
s and other limiting factors, such as the age of the individual parts of the instrument, the practical
detection limit The limit of detection (LOD or LoD) is the lowest signal, or the lowest corresponding quantity to be determined (or extracted) from the signal, that can be observed with a sufficient degree of confidence or statistical significance. However, the ...
for GC-MS is in the
picogram To help compare different orders of magnitude, the following lists describe various mass levels between 10−59  kg and 1052 kg. The least massive thing listed here is a graviton, and the most massive thing is the observable universe. ...
() range. GC-MS is also capable of quantifying the substances it detects; chemists can use this information to determine the effect the substance would have on an individual. GC-MS instruments need around 1,000 times more of the substance to quantify the amount than they need simply to detect it; the limit of quantification is typically in the
nanogram To help compare different orders of magnitude, the following lists describe various mass levels between 10−59  kg and 1052 kg. The least massive thing listed here is a graviton, and the most massive thing is the observable universe ...
() range.


Forensic toxicology

Forensic toxicology is the study of the
pharmacodynamics Pharmacodynamics (PD) is the study of the biochemical and physiologic effects of drugs (especially pharmaceutical drugs). The effects can include those manifested within animals (including humans), microorganisms, or combinations of organisms (fo ...
, or what a substance does to the body, and
pharmacokinetics Pharmacokinetics (from Ancient Greek ''pharmakon'' "drug" and ''kinetikos'' "moving, putting in motion"; see chemical kinetics), sometimes abbreviated as PK, is a branch of pharmacology dedicated to determining the fate of substances administered ...
, or what the body does to the substance. To accurately determine the effect a particular drug has on the human body, forensic toxicologists must be aware of various levels of
drug tolerance Drug tolerance or drug insensitivity is a pharmacological concept describing subjects' reduced reaction to a drug following its repeated use. Increasing its dosage may re-amplify the drug's effects; however, this may accelerate tolerance, further ...
that an individual can build up as well as the
therapeutic index The therapeutic index (TI; also referred to as therapeutic ratio) is a quantitative measurement of the relative safety of a drug. It is a comparison of the amount of a therapeutic agent that causes the therapeutic effect to the amount that causes ...
for various pharmaceuticals. Toxicologists are tasked with determining whether any toxin found in a body was the cause of or contributed to an incident, or whether it was at too low a level to have had an effect. While the determination of the specific toxin can be time-consuming due to the number of different substances that can cause injury or death, certain clues can narrow down the possibilities. For example,
carbon monoxide poisoning Carbon monoxide poisoning typically occurs from breathing in carbon monoxide (CO) at excessive levels. Symptoms are often described as "flu-like" and commonly include headache, dizziness, weakness, vomiting, chest pain, and confusion. Large e ...
would result in bright red blood while death from
hydrogen sulfide Hydrogen sulfide is a chemical compound with the formula . It is a colorless chalcogen-hydride gas, and is poisonous, corrosive, and flammable, with trace amounts in ambient atmosphere having a characteristic foul odor of rotten eggs. The unde ...
poisoning would cause the brain to have a green hue. Toxicologists are also aware of the different
metabolite In biochemistry, a metabolite is an intermediate or end product of metabolism. The term is usually used for small molecules. Metabolites have various functions, including fuel, structure, signaling, stimulatory and inhibitory effects on enzymes, c ...
s that a specific drug could break down into inside the body. For example, a toxicologist can confirm that a person took
heroin Heroin, also known as diacetylmorphine and diamorphine among other names, is a potent opioid mainly used as a recreational drug for its euphoric effects. Medical grade diamorphine is used as a pure hydrochloride salt. Various white and brow ...
by the presence in a sample of
6-monoacetylmorphine 6-Monoacetylmorphine (6-MAM, 6-acetylmorphine, or 6-AM) is one of three active metabolites of heroin (diacetylmorphine), the others being morphine and the much less active 3-monoacetylmorphine (3-MAM). Pharmacology 6-MAM occurs as a metabolite o ...
, which only comes from the breakdown of heroin. The constant creation of new drugs, both legal and illicit, forces toxicologists to keep themselves apprised of new research and methods to test for these novel substances. The stream of new formulations means that a negative test result does not necessarily rule out drugs. To avoid detection, illicit drug manufacturers frequently change the chemicals' structure slightly. These compounds are often not detected by routine toxicology tests and can be masked by the presence of a known compound in the same sample. As new compounds are discovered, known spectra are determined and entered into the databases that can be downloaded and used as reference standards. Laboratories also tend to keep in-house databases for the substances they find locally.


Standards

Guidelines have been set up by various governing bodies regarding the standards that are followed by practicing forensic scientists. For forensic chemists, the international
Scientific Working Group Since the early 1990s, American and International forensic science laboratories and practitioners have collaborated in Scientific Working Groups (SWGs) to improve discipline practices and build consensus standards. In 2014, the SWGs are being ...
for the Analysis of Seized Drugs (SWGDRUG) presents recommendations for the quality assurance and quality control of tested materials. In the identification of unknown samples, protocols have been grouped into three categories based on the probability for false positives. Instruments and protocols in category A are considered the best for uniquely identifying an unknown material, followed by categories B and then C. To ensure the accuracy of identifications SWGDRUG recommends that multiple tests using different instruments be performed on each sample, and that one category A technique and at least one other technique be used. If a category A technique is not available, or the forensic chemist decides not to use one, SWGDRUG recommends that at least three techniques be used, two of which must be from category B. Combination instruments, such as GC-MS, are considered two separate tests as long as the results are compared to known values individually For example, the GC elution times would be compared to known values along with the MS spectra. If both of those match a known substance, no further tests are needed. Standards and controls are necessary in the quality control of the various instruments used to test samples. Due to the nature of their work in the legal system, chemists must ensure that their instruments are working accurately. To do this, known controls are tested consecutively with unknown samples. By comparing the readouts of the controls with their known profiles the instrument can be confirmed to have been working properly at the time the unknowns were tested. Standards are also used to determine the instrument's limit of detection and limit of quantification for various common substances. Calculated quantities must be above the limit of detection to be confirmed as present and above the limit of quantification to be quantified. If the value is below the limit the value is not considered reliable.


Testimony

The standardized procedures for testimony by forensic chemists are provided by the various agencies that employ the scientists as well as SWGDRUG. Forensic chemists are ethically bound to present testimony in a neutral manner and to be open to reconsidering their statements if new information is found. Chemists should also limit their testimony to areas they have been qualified in regardless of questions during
direct Direct may refer to: Mathematics * Directed set, in order theory * Direct limit of (pre), sheaves * Direct sum of modules, a construction in abstract algebra which combines several vector spaces Computing * Direct access (disambiguation), a ...
or
cross-examination In law, cross-examination is the interrogation of a witness called by one's opponent. It is preceded by direct examination (in Ireland, the United Kingdom, Australia, Canada, South Africa, India and Pakistan known as examination-in-chief) and m ...
. Individuals called to testify must be able to relay scientific information and processes in a manner that lay individuals can understand. By being qualified as an expert, chemists are allowed to give their opinions on the evidence as opposed to just stating the facts. This can lead to competing opinions from experts hired by the opposing side. Ethical guidelines for forensic chemists require that testimony be given in an objective manner, regardless of what side the expert is testifying for. Forensic experts that are called to testify are expected to work with the lawyer who issued the summons and to assist in their understanding of the material they will be asking questions about.


Education

Forensic chemistry positions require a bachelor's degree or similar in a natural or physical science, as well as laboratory experience in
general A general officer is an Officer (armed forces), officer of highest military ranks, high rank in the army, armies, and in some nations' air forces, space forces, and marines or naval infantry. In some usages the term "general officer" refers t ...
, organic, and analytical chemistry. Once in the position, individuals are trained in protocols performed at that specific lab until they proven compotent to perform all experiments without supervision. Practicing chemists in the field are expected to complete continuing education to maintain their proficiency.


References

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Chemistry Chemistry is the science, scientific study of the properties and behavior of matter. It is a natural science that covers the Chemical element, elements that make up matter to the chemical compound, compounds made of atoms, molecules and ions ...