Chapter 02

Analytical Instruments

Chapter 02· 5 min read

Analytical Instruments

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The forensic laboratory's purpose is to convert physical evidence into legally defensible identifications. Different evidence types call for different instruments; matching the technique to the sample is the analyst's central skill. This chapter covers the instrument families that appear repeatedly in casework: microscopy, spectroscopy, mass spectrometry, X-ray methods, thermal analysis, and capillary electrophoresis.

2.1Microscopy — Choose by Specimen

MicroscopeBest forForensic use
CompoundThin / transparent specimensHair, fibre, pollen identification
Stereo3-D opaque specimens, low magnificationBullets, tool marks, evidence sorting
ComparisonSide-by-side comparisonFirearms ID, tool-mark comparison
Polarised (PLM)Birefringent materialsFibre ID (Δn), asbestos, minerals
FluorescenceFluorophore-labelled samplesStained latent prints, dye-tagged DNA
SEMHigh-magnification surface imagingGSR particles, fingerprint detail, paint cross-sections

The comparison microscope is the workhorse of firearms and tool-mark examination. Two complete stereo columns are joined optically through a beam-splitter bridge that combines the two image-paths. The examiner sees a single eyepiece view divided by a vertical seam: questioned specimen on one side, known on the other. Striations are aligned across the seam by rotating both stages until the patterns are continuous.

eyepieceOPTICAL BRIDGEobjective LQUESTIONEDscene specimenobjective RKNOWNtest specimenQKsplit-field eyepiece view
Fig 2.1Comparison microscope: two stereo columns + optical bridge yield a single split-field view.

2.2The Beer-Lambert Law

The foundational quantitative law in absorption spectroscopy:

Beer-Lambert Law
A = ε × c × l
A = absorbance (dimensionless) · ε = molar absorptivity (L mol⁻¹ cm⁻¹) · c = concentration (mol L⁻¹) · l = path length (cm, typically 1)

The law holds linearly between absorbance ~0.1 and ~1.0:

concentration cabsorbance A0.11.0Linear (0.1–1.0)analyte signal > noise floorSaturationstray-light dominatesnoise floor
Fig 2.2Beer-Lambert linearity. When A > 1.0, dilute the sample and re-measure within the linear region.

When an unknown gives absorbance > 1.0, dilute by a known factor (e.g., 1:10) and re-measure within the linear region. Compute the diluted concentration via Beer-Lambert, then multiply back by the dilution factor.

2.3FTIR — Functional-Group Fingerprinting

Fourier-Transform Infrared spectroscopy identifies organic compounds by their functional-group absorption pattern. Different bonds vibrate at characteristic wavenumbers (cm⁻¹).

Wavenumber (cm⁻¹)Functional groupForensic example
3200–3550O-H stretchAlcohols, water
3300N-H stretchAmines, amides
3050=C-H aromaticBenzene rings
2960–2870C-H aliphaticAlkanes
1715C=O esterPET, esters
1640C=O amideNylon, proteins
1540N-H bend (amide-II)Nylon, peptides
1240C-O-C asymmetricEsters, ethers
720Aromatic out-of-planePara-substituted benzenes

PET fingerprint trio: 1715 + 1240 + 720 cm⁻¹ — diagnostic of polyethylene terephthalate.

Sampling techniques

  • ATR (Attenuated Total Reflectance): solid pressed against diamond / ZnSe / Ge crystal; non-destructive; ~0.5–2 µm penetration. Modern default for forensic chips and films.
  • KBr-pellet transmission: ground sample mixed with KBr powder, pressed into transparent pellet. Gold standard for ground powders but destructive.
  • Direct transmission: thin films / liquids in a cell.

2.4Mass Spectrometry — GC-MS Confirmation

Gas chromatography coupled to mass spectrometry (GC-MS) is the gold-standard confirmatory technique for organic controlled substances.

The GC separates the sample into peaks by volatility on a heated capillary column. Each peak enters the MS where electron-impact ionisation (70 eV is the EI standard) fragments the molecules into characteristic patterns. The mass spectrum is matched against library references (NIST, Wiley, SWGDRUG); a match score above 700 / 1000 is considered strong.

Cocaine EI mass spectrum (schematic)m/z82base10577182303M⁺0100200300Cocaine fingerprintM⁺ 303 + 182 + 82SWGDRUG Cat-A confirmed
Fig 2.3Cocaine mass-spectrum fingerprint (M⁺ 303 + 182 + 82) under electron impact ionisation.

The trio 303 + 182 + 82 is the cocaine fingerprint. Confirmation requires: (1) library mass-spectrum match + (2) co-injected reference retention time match (within ±0.5%). This is Category-A SWGDRUG confirmation, court-admissible.

LC-MS/MS handles polar / thermolabile / non-volatile compounds that GC-MS cannot vaporise: drug glucuronides (e.g., morphine glucuronide MRM 462→286), peptides, proteins. Tandem MS adds a second mass-selection stage for high specificity at picogram detection.

2.5Atomic Spectroscopy Hierarchy

For trace metals in forensic toxicology, the choice of atomic spectroscopy depends on sensitivity and multi-element needs:

TechniqueSensitivityMulti-elementIsotopicCost
ICP-MSppt (10⁻¹² g/mL)YesYesHigh
ICP-AES (OES)ppb–ppmYesNoMedium
Flame AASppbNo (single lamp)NoLow
Flame photometrymg/LNo (alkali only)NoVery low

For forensic GSR identification (ASTM E1588), SEM-EDX gives both morphology (1–5 µm spheroidal particle) and elemental composition (Pb + Sb + Ba simultaneously). Detection limits ~0.1–1 wt% for elements heavier than sodium — sufficient for the primer-residue triad.

2.6X-Ray Methods

XRF — X-ray Fluorescence

Each element has unique inner-shell binding energies, so X-rays emitted when atoms relax after ionisation identify which element produced them. Fe K-α at 6.4 keV, Cu K-α at 8.05 keV, Au L-α at 9.71 keV, Pb L-α at 10.5 keV. Used for GSR, glass discrimination, paint composition, counterfeit metals.

XRD — X-ray Diffraction (Bragg's Law)

Crystalline materials identified by characteristic d-spacings via Bragg's law: nλ = 2d sin θ. Pattern matched against ICDD-PDF reference library (~100 000 entries). Distinguishes polymorphs (cocaine HCl vs free base, NH₄NO₃ phases I-V).

LIBS — Laser-Induced Breakdown Spectroscopy

High-energy pulsed laser creates a microplasma; atomic emission lines identify elements. Portable, near-non-destructive (μm crater), and capable of depth-profiling through paint layers. Standard for handheld field analysis.

Bragg's Law
n λ = 2 d sin θ
n = order (usually 1) · λ = X-ray wavelength (Cu K-α at 1.5418 Å is standard) · d = lattice spacing · θ = ½ of the 2θ peak angle

2.7TLC and HPLC — Chromatographic Separation

Thin-layer chromatography (TLC) is the simplest separation technique. Sample is spotted at the bottom of a silica plate; a mobile phase travels up by capillary action; analytes partition between silica and mobile phase, separating by polarity.

Rf Value
Rf = distance of spot from origin / distance of solvent front from origin
Reproducible on the same plate; primary identifier in TLC. For basic drugs (morphine) on silica: chloroform–methanol–ammonia 90:9:1.

HPLC is the high-pressure liquid version, with detection by UV-Vis or mass spectrometry. Reversed-phase HPLC uses a non-polar C18 stationary phase + polar water-acetonitrile mobile phase. More acetonitrile = shorter retention; more water = longer retention.

2.8Capillary Electrophoresis — STR Profiling

CE has displaced slab-gel electrophoresis for forensic DNA STR profiling. Single-base-pair resolution across the 75–450 bp STR allele range; multi-colour fluorescence detection allowing 20+ STR loci in a single multiplexed PCR + CE run; 96 samples processed per day per multi-capillary instrument (ABI 3500 / 3500xL).

Memory hooks · Chapter 2

Microscope choice: thin transmitted = compound; 3-D opaque = stereo / comparison; birefringent = PLM; surface morphology = SEM. Beer-Lambert: A = εcl. Linear 0.1–1.0; above 1.0 → dilute. FTIR sampling: ATR for solids (modern default); KBr for ground powders. GC-MS confirmation: library + co-injected retention time. Both required. LC-MS/MS: polar / thermolabile / non-volatile. GSR: Pb + Sb + Ba on a 1–5 µm spheroid by SEM-EDX. XRD: Bragg's law nλ = 2d sin θ; match against ICDD-PDF. Rf: spot distance / solvent distance, reproducible on same plate.

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