Forensic Analysis of Fire Samples Flashcards
How are fire scene residues analysed?
- Common accelerants are volatile liquids which evaporate quickly.
- Portable hydrocarbon detectors
- Organic vapours affect the electrical conductivity of semi-conductor detectors. Not susbtance specific.
- Trained dogs are also used
How does a photo-ionisation detector work?
- This uses photons in UV range to break down molecules into positively charged ions.
- The gas becomes electrically charged and the ions produce a current. This gives an instantaneous reading with DL down to PPB. Data is automatically logged.
- This is a portable detector, for use at fire scene. Used when searching through large amounts of clothing for residues of ignitable liquids.
What are the three classes of samples obtained at the fire scene?
- Fire sample: a sample from as near as possible to the seat of fire, tested for presence of accelerant.
- Comparative control sample - same material as fire sample taken from elsewhere in the room and thus uncontaminated with accelerant.
- Negative control samples - tools and empty containers of the same type used in the sampling process.
- Samples from suspect (if there is one).
How should fire residues be packaged?
- Airtight and retain volatile long-chain hydrocarbons and aromatic molecules such as toluene and xylene
- Dual-bagging in nylon (inner) and polypropylene (outer). Closed by swan neck seal with cable tag.
- Glass jars can be used with a metal lid and must withstand vapour pressure of volatile liquids.
How is a swan neck seal made?
- The bag should be sealed when no more than 75% full
- The neck is twisted firmly and is then doubled over.
- Hold the twist firmly and pass the seal over the neck of the bag.
- Tighten seal manually to create an effective seal.
- Accurate labelling of all samples is essential
- Good record keeping is essential to ensure continuity of evidence.
What samples should be obtained in the laboratory?
- A positive control is obtained with a volatile flammable liquid on it. This is packaged in same manner as fire scene sample
- Usually analysed at end of analytical sequence to reduce risk of contamination.
- Additional negative control samples should be obtained from within the analysis laboratory, to guard against accelerant traces arising from contamination of laboratory equipment.
What is passive headspace analysis?
- In passive headspace analysis, the vapour in the sealed container is exposed to activated charcoal, a chemical adsorbant, where it is trapped for later analysis.
- Temperature is between 60-80oC
- Time = 2 hours
What is dynamic headspace analysis?
- The vapour is drawn from the sample through an adsorbent using a flow of carrier gas such as dry nitrogen.
- This method was developed from methods used for environmental monitoring of ultra-trace quantities.
- The adsorbent is activated charcoal or TENAXTM - a porous polymer which traps organic volatiles but has a low affinity for water.
- DL as low as 1 microlitre of accelerant.
- Applicable to wide range of accelerants, inc alcohols/ketones.
How is gas chromatography implemented after headspace analysis?
- The samples containing volatile solutes are injected into a high temperature port and are vaporised.
- The sample is carried into a separating column by a stream of inert gas.
- GC column separates solutes by adsorption on an active column material.
- Each solute has its own characteristic retention time depending on the setup of the experiment.
How does a flame-ionising detector detect the separated components in the gas column?
- The gas stream carrying the separated components passes through a detector, which responds to the solute molecules
- A flame ionisation detector (FID) uses a small hydrogen-oxygen flame to burn sample solutes as they emerge from the column.
- A high voltage is applied across electrodes close to the flame. Most carbon-containing compounds produce charged molecular fragments when burnt. These fragment ions allow an electrical current to flow between the electrodes.
What are the limitations/advantages of using GC for fire residue analysis?
- Not many ions produced by functional groups so GC detects solute molecules by their hydrocarbon skeleton. It is not selective for the class of compound
- Method is more sensitive to heavier hydrocarbons which produce a higher yield of ions. This is not very important in ID, since compounds have already been separated by the column, but it does affect quantitative analysis.
What information can be obtained from interpretation of GC?
- Retention time depends primarily on molecular mass
- It depends secondarily on structure of molecule
- For samples with a broad boiling point range, programmed temperature increase of the column is used.
- Recognition of chromatographic patterns of common flammable liquids.
- Recognition of mixtures.
- Weathering of samples due to ageing at scene and heating.
What GC pattern is typical of distillate fuels?
- The spread of components with different numbers of carbon atoms (resembling Gaussian distribution is characteristic of distillate fuels.
- This allows these fuels to be distinguished from mixtures of unrelated single substances that might be present in a sample, such as pyrolysis products.
What is typical of weathered samples on the Gas Chromatogram?
- The most volatile components are missing from fire samples as they have evapourated before samples could be collected.
- The most volatile components have a lower molecular mass, among compounds of the same type.
- This does not necessarily apply if low molecular mass oxygenate additives are being compared with higher molecular mass hydrocarbons e.g.
What other substances may be present in the GC?
- Combustion/pyrolysis of carpets, polymers, adhesives, wood products and clothing
- Fire retardents e.g. brominated hydrocarbons (remove free radicals, preventing combustion)
- Surfactants and fire suppression agents from foams:
- Phos-Chek WD 881 foaming agent contains long-chain sulfonated alkenes, alcohols and limonene (interferes with GC analysis of accelerants. Also in perfumes etc.)
- F500 - long aliphatic acids, alcohols and ethers.