Forensic chemistry

Forensic chemistry is the application of chemistry to law enforcement or the failure of products or processes.
Many different analytical methods may be used to reveal what chemical changes occurred during an incident,
and so help reconstruct the sequence of events. "Forensic chemistry is unique among chemical sciences in that
its research, practice, and presentation must meet the needs of both the scientific and the legal communities. As
such, forensic chemistry research is applied and derivative by nature and design, and it emphasizes metrology
and validation."
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Methods
"ne useful method is the gas chromatograph#mass spectrometer $%&M'(, which is actually two instruments
that are attached. )he gas chromatograph is essentially a very hot oven holding a hollow coiled column. A drug
sample is diluted in a solvent $e.g., chloroform, methanol( and is in*ected into this column, the solvent will
evaporate very quic+ly leaving the drug to travel through the column. ,ifferent substances are retained in the
column for different amounts of time. )he retention time, as compared to a +nown standard sample using the
same method$same column length-polarity, same flow rate, same temperature program(, can help to provide a
positive identification for the presence of a compound of interest. )he column eluent is then fed into a mass
spectrometer. A mass spectrometer bombards the eluant with electrons, causing it to fragment into ions. )hese
ions are separated by their mass, commonly with the use of a quadrupole mass analyzer or quadrupole ion trap,
and detected by an electron multiplier. )his provides a fragmentation pattern, which functions as a sort of
fingerprint for each compound, and is compared to a reference sample.
Spectroscopy
./ spectrum showing carbonyl absorption due to o0idative degradation of polypropylene
Another instrument used to aide in identification of compounds is the Fourier )ransform infrared
spectrophotometer $F)./(. )he sample is bombarded with infrared radiation. 1olar bonds found in organic
compounds have a natural frequency of vibration similar to the frequency of infrared radiation. 2hen the
frequency of the infrared radiation matches the natural frequency of the bond, the amplitude of the vibration
increases, and the infrared is absorbed. )he output of an infrared spectrophotometer charts the amount of light
absorbed vs. the wavelength, typically with units of percent transmission and wavenumbers$cm
#
(. 3ecause both
the frequency and the intensity of absorption are dependent on the type of bond, a s+illed chemist can determine
the functional groups present by e0amining the infrared spectrum.
As with the %&M' the F)./ spectrum can be compared to that of a +nown sample, thus providing evidence for
the identification of a compound. 'pectroscopy can also help to identify materials used in failed products,
especially polymers, additives and fillers. 'amples can be ta+en by dissolution, or by cutting a thin slice using a
microtome from the specimen under e0amination. 'urfaces can be e0amined using Attenuated total reflectance
spectroscopy, and the method has also been adapted to the optical microscope with infra#red microspectroscopy.
)hermoplastics can be analysed using infra#red spectroscopy, 45 spectroscopy, as 6M/ and 7'7M. Failed
samples can either be dissolved in a suitable solvent and e0amined directly $45, ./ and 6M/ spectroscopy( or
be a thin film cast from solvent or cut using microtomy from the solid product. .nfra#red spectroscopy is
especially useful for assessing o0idation of polymers, such as the polymer degradation caused by faulty
in*ection moulding. )he spectrum shows the characteristic carbonyl group produced by o0idation of
polypropylene, which made the product brittle. .t was a critical part of a crutch, and when it failed, the user fell
and in*ured herself very seriously. )he spectrum was obtained from a thin film cast from a solution of a sample
of the plastic ta+en from the failed forearm crutch.
Sample integrity
Forensic chemists usually perform their analytical wor+ in a sterile laboratory decreasing the ris+ of sample
contamination. .n order to prevent tampering, forensic chemists must +eep trac+ of a chain of custody for each
sample. A chain of custody is a document that stays with the evidence at all times. Among other information,
contains signatures and identification of all the people involved in transport, storage and analysis of the
evidence.
)his ma+es it much more difficult for intentional tampering to occur, it also acts as a detailed record of the
location of the evidence at all times for record +eeping purposes. .t increases the reliability of a forensic
chemist8s wor+ and increases the strength of the evidence in court.
A distinction is made between destructive and non#destructive analytical methods. ,estructive methods involve
ta+ing a sample from the ob*ect of interest, and so in*ures the ob*ect. Most spectroscopic techniques fall into this
category. 3y contrast, a non#destructive method conserves the integrity of the ob*ect, and is generally preferred
by forensic e0aminers. For e0ample, "ptical microscopy cannot in*ure the sample, so it falls in this class.
Examples
1olymers for e0ample, can be attac+ed by aggressive chemicals, and if under load, then crac+s will grow by the
mechanism of stress corrosion crac+ing. 1erhaps the oldest +nown e0ample is the ozone crac+ing of rubbers,
where traces of ozone in the atmosphere attac+ double bonds in the chains of the materials. 7lastomers with
double bonds in their chains include natural rubber, nitrile rubber, and styrene#butadiene rubber. )hey are all
highly susceptible to ozone attac+, and can cause problems li+e car fires $from rubber fuel lines( and tire blow#
outs. 6owadays, anti#ozonants are widely added to these polymers, so the incidence of crac+ing has dropped.
9owever, not all safety#critical rubber products are protected, and, since only ppb of ozone will start attac+,
failures are still occurring.
Another highly reactive gas is chlorine, which will attac+ susceptible polymers such as acetal resin and
polybutylene pipewor+. )here have been many e0amples of such pipes and acetal fittings failing in properties in
the 4'A as a result of chlorine#induced crac+ing. .n essence, the gas attac+s sensitive parts of the chain
molecules $especially secondary, tertiary or allylic carbon atoms(, o0idizing the chains and ultimately causing
chain cleavage. )he root cause is traces of chlorine in the water supply, added for its anti#bacterial action, attac+
occurring even at parts per million traces of the dissolved gas.
Most step#growth polymers can suffer hydrolysis in the presence of water, often a reaction catalysed by acid or
al+ali. 6ylon for e0ample, will degrade and crac+ rapidly if e0posed to strong acids, a phenomenon well +nown
to those who accidentally spill acid onto their shirts or tights. 1olycarbonate is susceptible to al+ali hydrolysis,
the reaction simply depolymerising the material. 1olyesters are prone to degrade when treated with strong acids,
and, in all these cases, care must be ta+en to dry the raw materials for processing at high temperatures to prevent
the problem from occurring.
Many polymers are also attac+ed by 45 radiation at vulnerable points in their chain structures. )hus,
polypropylene suffers severe crac+ing in sunlight unless anti#o0idants are added. )he point of attac+ occurs at
the tertiary carbon atom present in every repeat unit, causing o0idation and finally chain brea+age.
Gas chromatography-mass spectrometry
Gas chromatography-mass spectrometry $GC-MS( is a method that combines the features of gas#liquid
chromatography and mass spectrometry to identify different substances within a test sample. Applications of
%&#M' include drug detection, fire investigation, environmental analysis, e0plosives investigation, and
identification of un+nown samples. %&-M' can also be used in airport security to detect substances in luggage
or on human beings. Additionally, it can identify trace elements in materials that were previously thought to
have disintegrated beyond identification.
)he %&#M' has been widely heralded as a "gold standard" for forensic substance identification because it is
used to perform a specific test. A specific test positively identifies the actual presence of a particular substance
in a given sample. A non-specific test merely indicates that a substance falls into a category of substances.
Although a non#specific test could statistically suggest the identity of the substance, this could lead to false
positive identification.
Instrumentation
)he %&#M' is composed of two ma*or building bloc+s: the gas chromatograph and the mass spectrometer. )he
gas chromatograph utilizes a capillary column which depends on the column8s dimensions $length, diameter,
film thic+ness( as well as the phase properties $e.g. ;< phenyl polysilo0ane(. )he difference in the chemical
properties between different molecules in a mi0ture will separate the molecules as the sample travels the length
of the column. )he molecules ta+e different amounts of time $called the retention time( to come out of $elute
from( the gas chromatograph, and this allows the mass spectrometer downstream to capture, ionize, accelerate,
deflect, and detect the ionized molecules separately. )he mass spectrometer does this by brea+ing each molecule
into ionized fragments and detecting these fragments using their mass to charge ratio.
GC-MS schematic
)hese two components, used together, allow a much finer degree of substance identification than either unit
used separately. .t is not possible to ma+e an accurate identification of a particular molecule by gas
chromatography or mass spectrometry alone. )he mass spectrometry process normally requires a very pure
sample while gas chromatography using a traditional detector $e.g. Flame .onization ,etector( detects multiple
molecules that happen to ta+e the same amount of time to travel through the column $i.e. have the same
retention time( which results in two or more molecules to co#elute. 'ometimes two different molecules can also
have a similar pattern of ionized fragments in a mass spectrometer $mass spectrum(. &ombining the two
processes ma+es it e0tremely unli+ely that two different molecules will behave in the same way in both a gas
chromatograph and a mass spectrometer. )herefore when an identifying mass spectrum appears at a
characteristic retention time in a %&#M' analysis, it typically lends to increased certainty that the analyte of
interest is in the sample.
Purge and Trap GC-MS
For the analysis of volatile compounds a 1urge and )rap $1=)( concentrator system may be used to introduce
samples. )he target analytes are e0tracted and mi0ed with water and introduced into an airtight chamber. An
inert gas such as 6itrogen $6>( is bubbled through the water? this is +nown as purging. )he volatile compounds
move into the headspace above the water and are drawn along a pressure gradient $caused by the introduction of
the purge gas( out of the chamber. )he volatile compounds are drawn along a heated line onto a 8trap8. )he trap
is a column of adsorbent material at ambient temperature that holds the compounds by returning them to the
liquid phase. )he trap is then heated and the sample compounds are introduced to the %&#M' column via a
volatiles interface, which is a split inlet system. 1=) %&#M' is particularly suited to volatile organic
compounds $5"&s( and 3)7@ compounds $aromatic compounds associated with petroleum(.
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Types of Mass Spectrometer Detectors
)he most common type of mass spectrometer $M'( associated with a gas chromatograph $%&( is the quadrupole
mass spectrometer, sometimes referred to by the 9ewlett#1ac+ard $now Agilent( trade name "Mass 'elective
,etector" $M',(. Another relatively common detector is the ion trap mass spectrometer. Additionally one may
find a magnetic sector mass spectrometer, however these particular instruments are e0pensive and bul+y and not
typically found in high#throughput service laboratories. "ther detectors may be encountered such as time of
flight $)"F(, tandem quadrupoles $M'#M'( $see below(, or in the case of an ion trap M'
n
where n indicates the
number mass spectrometry stages.
nalysis
A mass spectrometer is typically utilized in one of two ways: Full 'can or 'elective .on Monitoring $'.M(. )he
typical %&-M' instrument is capable of performing both functions either individually or concomitantly,
depending on the setup of the particular instrument.
Full scan MS
2hen collecting data in the full scan mode, a target range of mass fragments is determined and put into the
instrument8s method. An e0ample of a typical broad range of mass fragments to monitor would be m/z ;B to m/z
CBB. )he determination of what range to use is largely dictated by what one anticipates being in the sample
while being cognizant of the solvent and other possible interferences. A M' should not be set to loo+ for mass
fragments too low or else one may detect air $found as m/z >D due to nitrogen(, carbon dio0ide $m/z CC( or other
possible interferences. Additionally if one is to use a large scan range then sensitivity of the instrument is
decreased due to performing fewer scans per second since each scan will have to detect a wide range of mass
fragments.
Full scan is useful in determining un+nown compounds in a sample. .t provides more information than '.M
when it comes to confirming or resolving compounds in a sample. ,uring instrument method development it
may be common to first analyze test solutions in full scan mode to determine the retention time and the mass
fragment fingerprint before moving to a '.M instrument method.
Selected ion monitoring
.n selected ion monitoring $'.M( certain ion fragments are entered into the instrument method and only those
mass fragments are detected by the mass spectrometer. )he advantages of '.M are that the detection limit is
lower since the instrument is only loo+ing at a small number of fragments $e.g. three fragments( during each
scan. More scans can ta+e place each second. 'ince only a few mass fragments of interest are being monitored,
matri0 interferences are typically lower. )o additionally confirm the li+elihood of a potentially positive result, it
is relatively important to be sure that the ion ratios of the various mass fragments are comparable to a +nown
reference standard.
!edit" Types of Ioni#ation
After the molecules travel the length of the column, pass through the transfer line and enter into the mass
spectrometer they are ionized by various methods with typically only one method being used at any given time.
"nce the sample is fragmented it will then be detected, usually by an electron multiplier diode, which
essentially turns the ionized mass fragment into an electrical signal that is then detected.
)he ionization technique chosen is independent of using Full 'can or '.M.
[edit] Electron Ionization
3y far the most common and perhaps standard form of ionization is electron ionization $7.(. )he molecules
enter into the M' $the source is a quadrupole or the ion trap itself in an ion trap M'( where they are bombarded
with free electrons emitted from a filament, not much unli+e the filament one would find in a standard light
bulb. )he electrons bombard the molecules, causing the molecule to fragment in a characteristic and
reproducible way. )his "hard ionization" technique results in the creation of more fragments of low mass to
charge ratio $m-z( and few, if any, molecules approaching the molecular mass unit. 9ard ionization is
considered by mass spectroscopists as the employ of molecular electron bombardment, whereas "soft
ionization" is charge by molecular collision with an introduced gas. )he molecular fragmentation pattern is
dependant upon the electron energy applied to the system, typically EB e5 $electron 5olts(. )he use of EB e5
facilitates comparison of generated spectra with 6ational .nstitute of 'tandard $6.')#4'A( library of spectra
applying algorithmic matching programs and the use of methods of analysis written by many method
standardization agencies.
] Chemical Ionization
.n chemical ionization a reagent gas, typically methane or ammonia is introduced into the mass spectrometer.
,epending on the technique $positive &. or negative &.( chosen, this reagent gas will interact with the electrons
and analyte and cause a 8soft8 ionization of the molecule of interest. A softer ionization fragments the molecule
to a lower degree than the hard ionization of 7.. "ne of the main benefits of using chemical ionization is that a
mass fragment closely corresponding to the molecular weight of the analyte of interest is produced.
Positive Chemical Ionization
.n 1ositive &hemical .onization $1&.( the reagent gas interacts with the target molecule, most often with a
proton e0change. )his produces the species in relatively high amounts.
Negative Chemical Ionization
.n 6egative &hemical .onization $6&.( the reagent gas decreases the impact of the free electrons on the target
analyte. )his decreased energy typically leaves the fragment in great supply.
This section requires expansion with:
p!ating" The following information is in the process of being updated:"
)he primary goal of instrument analysis is to quantify an amount of substance. )his is done by comparing the
relative concentrations among the atomic masses in the generated spectrum. )wo +inds of analysis are possible,
comparative and original. &omparative analysis essentially compares the given spectrum to a spectrum library
to see if its characteristics are present for some sample in the library. )his is best performed by a computer
because there are a myriad of visual distortions that can ta+e place due to variations in scale. &omputers can
also simultaneously correlate more data $such as the retention times identified by %&(, to more accurately relate
certain data.
Another method of analysis measures the pea+s in relation to one another. .n this method, the tallest pea+ is
assigned BB< of the value, and the other pea+s being assigned proportionate values. All values above A< are
assigned. )he total mass of the un+nown compound is normally indicated by the parent pea+. )he value of this
parent pea+ can be used to fit with a chemical formula containing the various elements which are believed to be
in the compound. )he isotope pattern in the spectrum, which is unique for elements that have many isotopes,
can also be used to identify the various elements present. "nce a chemical formula has been matched to the
spectrum, the molecular structure and bonding can be identified, and must be consistent with the characteristics
recorded by %&-M'. )ypically, this identification done automatically by programs which come with the
instrument, given a list of the elements which could be present in the sample.
A Ffull spectrumG analysis considers all the Fpea+sG within a spectrum. &onversely, selective ion monitoring
$'.M( only monitors selected pea+s associated with a specific substance. )his is done on the assumption that at
a given retention time, a set of ions is characteristic of a certain compound. )his is a fast and efficient analysis,
especially if the analyst has previous information about a sample or is only loo+ing for a few specific
substances. 2hen the amount of information collected about the ions in a given gas chromatographic pea+
decreases, the sensitivity of the analysis increases. 'o, '.M analysis allows for a smaller quantity of a
compound to be detected and measured, but the degree of certainty about the identity of that compound is
reduced.
GC-tandem MS
2hen a second phase of mass fragmentation is added, for e0ample using a second quadrupole in a quadrupole
instrument, it is called tandem M' $M'-M'(. M'-M' can sometimes be used quantitate low levels of target
compounds in the presence of a high sample matri0 bac+ground.
)he first quadrupole $H( is connected with a collision cell $q>( and another quadrupole $HA(. 3oth quadrupoles
can be used in scanning or static mode, depending on the type of M'-M' analysis being performed. )ypes of
analysis include product ion scan, precursor ion scan, 'elected /eaction Monitoring $'/M( $sometimes referred
to as Multiple /eaction Monitoring $M/M(( and 6eutral Ioss 'can. For e0ample: 2hen H is in static mode
$loo+ing at one mass only as in '.M(, and HA is in scanning mode, one obtains a so#called product ion spectrum
$also called "daughter spectrum"(. From this spectrum, one can select a prominent product ion which can be the
product ion for the chosen precursor ion. )he pair is called a "transition" and forms the basis for '/M. '/M is
highly specific and virtually eliminates matri0 bac+ground.
pplications
En$ironmental Monitoring and Cleanup
%&#M' is becoming the tool of choice for trac+ing organic pollutants in the environment. )he cost of %&#M'
equipment has decreased significantly, and the reliability has increased at the same time, which has contributed
to its increased adoption in environmental studies. )here are some compounds for which %&#M' is not
sufficiently sensitive, including certain pesticides and herbicides, but for most organic analysis of environmental
samples, including many ma*or classes of pesticides, it is very sensitive and effective.
Criminal Forensics
%&#M' can analyze the particles from a human body in order to help lin+ a criminal to a crime. )he analysis of
fire debris using %&#M' is well established, and there is even an established American 'ociety for )esting
Materials $A')M( standard for fire debris analysis. %&M'-M' is especially useful here as samples often
contain very comple0 matrices and results, used in court, need to be highly accurate.
%a& Enforcement
%&#M' is increasingly used for detection of illegal narcotics, and may eventually supplant drug#sniffing dogs.
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.t is also commonly used in forensic to0icology to find drugs and-or poisons in biological specimens of
suspects, victims, or the deceased.
Security
A post#'eptember development, e0plosive detection systems have become a part of all 4' airports. )hese
systems run on a host of technologies, many of them based on %&#M'. )here are only three manufacturers
certified by the FAA to provide these systems,
[citation needed!
one of which is )hermo ,etection $formerly
)hermedics(, which produces the 7%.', a %&#M'#based line of e0plosives detectors. )he other two
manufacturers are 3arringer )echnologies, now owned by 'mith8s ,etection 'ystems, and .on )rac+
.nstruments, part of %eneral 7lectric .nfrastructure 'ecurity 'ystems.
Food' (e$erage and Perfume nalysis
Foods and beverages contain numerous aromatic compounds, some naturally present in the raw materials and
some forming during processing. %&#M' is e0tensively used for the analysis of these compounds which include
esters, fatty acids, alcohols, aldehydes, terpenes etc. .t is also used to detect and measure contaminants from
spoilage or adulteration which may be harmful and which is often controlled by governmental agencies, for
e0ample pesticides.
strochemistry
'everal %&#M' have left earth. )wo were brought to Mars by the 5i+ing program.
[C!
5enera and > and
1ioneer 5enus analysed the atmosphere of 5enus with %&#M'.
[;!
)he 9uygens probe of the &assini#9uygens
mission landed one %&#M' on 'aturn8s largest moon, )itan.
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)he material in the comet JE1-&huryumov#
%erasimen+o will be analysed by the /osetta mission with a chiral %&#M' in >BC.
[E!
Medicine
.n combination with isotopic labeling of metabolic compounds, the %&#M' is used for determining metabolic
activity. Most applications are based on the use of
A
& as the labeling and the measurement of
A
&-
>
& ratios with
an isotope ratio mass spectrometer $I)MS(? an M' with a detector designed to measure a few select ions and
return values as ratios.
Mass spectrometry
Mass spectrometry $M'( is an analytical technique that measures the mass#to#charge ratio of charged particles.
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.t is used for determining masses of particles, for determining the elemental composition of a sample or
molecule, and for elucidating the chemical structures of molecules, such as peptides and other chemical
compounds. )he M' principle consists of ionizing chemical compounds to generate charged molecules or
molecule fragments and measurement of their mass#to#charge ratios.
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.n a typical M' procedure:
. A sample is loaded onto the M' instrument, and undergoes vaporization
>. )he components of the sample are ionized by one of a variety of methods $e.g., by impacting them with
an electron beam(, which results in the formation of charged particles $ions(
A. )he ions are separated according to their mass#to#charge ratio in an analyzer by electromagnetic fields
C. )he ions are detected, usually by a quantitative method
;. )he ion signal is processed into mass spectra
M' instruments consist of three modules:
An ion source, which can convert gas phase sample molecules into ions $or, in the case of electrospray
ionization, move ions that e0ist in solution into the gas phase(
A mass analyzer, which sorts the ions by their masses by applying electromagnetic fields
A detector, which measures the value of an indicator quantity and thus provides data for calculating the
abundances of each ion present
)he technique has both qualitative and quantitative uses. )hese include identifying un+nown compounds,
determining the isotopic composition of elements in a molecule, and determining the structure of a compound
by observing its fragmentation. "ther uses include quantifying the amount of a compound in a sample or
studying the fundamentals of gas phase ion chemistry $the chemistry of ions and neutrals in a vacuum(. M' is
now in very common use in analytical laboratories that study physical, chemical, or biological properties of a
great variety of compounds.
Fourier transform spectroscopy
Fourier transform spectroscopy is a measurement technique whereby spectra are collected based on
measurements of the coherence of a radiative source, using time#domain or space#domain measurements of the
electromagnetic radiation or other type of radiation. .t can be applied to a variety of types of spectroscopy
including optical spectroscopy, infrared spectroscopy $F)./, F)#6./'(, nuclear magnetic resonance $6M/(
and magnetic resonance spectroscopic imaging $M/'.(
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, mass spectrometry and electron spin resonance
spectroscopy. )here are several methods for measuring the temporal coherence of the light, including the
continuous wave Michelson or Fourier transform spectrometer and the pulsed Fourier transform spectrograph
$which is more sensitive and has a much shorter sampling time than conventional spectroscopic techniques, but
is only applicable in a laboratory environment(.
)he term Fourier transform spectroscopy reflects the fact that in all these techniques, a Fourier transform is
required to turn the raw data into the actual spectrum.
Measuring an emission spectrum
An e0ample of a spectrum: )he spectrum of light emitted by the blue flame of a butane torch. )he horizontal
a0is is the wavelength of light, and the vertical a0is represents how much light is emitted by the torch at that
wavelength.
"ne of the most basic tas+s in spectroscopy is to characterize the spectrum of a light source: 9ow much light is
emitted at each different wavelength. )he most straightforward way to measure a spectrum is to pass the light
through a monochromator, an instrument that bloc+s all of the light except the light at a certain wavelength $the
un#bloc+ed wavelength is set by a +nob on the monochromator(. )hen the intensity of this remaining $single#
wavelength( light is measured. )he measured intensity directly indicates how much light is emitted at that
wavelength. 3y varying the monochromator8s wavelength setting, the full spectrum can be measured. )his
simple scheme in fact describes how some spectrometers wor+.
Fourier transform spectroscopy is a less intuitive way to get the same information. /ather than allowing only
one wavelength at a time to pass through to the detector, this technique lets through a beam containing many
different wavelengths of light at once, and measures the total beam intensity. 6e0t, the beam is modified to
contain a different combination of wavelengths, giving a second data point. )his process is repeated many
times. Afterwards, a computer ta+es all this data and wor+s bac+wards to infer how much light there is at each
wavelength.
)o be more specific, between the light source and the detector, there is a certain configuration of mirrors that
allows some wavelengths to pass through but bloc+s others $due to wave interference(. )he beam is modified
for each new data point by moving one of the mirrors? this changes the set of wavelengths that can pass through.
As mentioned, computer processing is required to turn the raw data $light intensity for each mirror position( into
the desired result $light intensity for each wavelength(. )he processing required turns out to be a common
algorithm called the Fourier transform $hence the name, "Fourier transform spectroscopy"(. )he raw data is
sometimes called an "interferogram".