NITROGEN ISOTOPE TECHNIQUES
CONTENTS I HOW IT WORKS WHAT ARE STABLE ISOTOPES? NATURAL ABUNDANCE VARIATION OF STABLE ISOTOPES CHEMICALLY IDENTICAL AND YET NOT THE SAME ISOTOPE EFFECTS, MASS DISCRIMINATION AND ISOTOPIC FRACTIONATION PHYSICAL CHEMISTRY BACKGROUND FRACTIONATION FACTOR ??AND ENRICHMENT FACTOR ?? ISOTOPIC FRACTIONATION IN RAYLEIGH PROCESSES ISOTOPIC FRACTIONATION SUMMARY STABLE ISOTOPIC DISTRIBUTION AND ISOTOPIC FRACTIONATION OF LIGHT ELEMENTS IN NATURE HYDROGEN OXYGEN CARBON NITROGEN SULFUR ISOSCAPES STABLE ISOTOPE FORENSICS IN EVERYDAY LIFE “FOOD FORENSICS” AUTHENTICITY AND PROVENANCE OF SINGLE-SEED VEGETABLE OILS AUTHENTICITY AND PROVENANCE OF BEVERAGES CAVEATS AUTHENTICITY AND PROVENANCE OF OTHER PREMIUM PRODUCTS COUNTERFEIT PHARMACEUTICALS ENVIRONMENTAL FORENSICS WILDLIFE FORENSICS ANTI-DOPING CONTROL SUMMARY OF PART I REFERENCES PART I II INSTRUMENTATION, ANALYTICAL TECHNIQUES AND DATA QUALITY MASS SPECTROMETRY VERSUS ISOTOPE RATIO MASS SPECTROMETRY STABILITY, ISOTOPIC LINEARITY AND ISOTOPIC CALIBRATION INSTRUMENTATION FOR STABLE ISOTOPE ANALYSIS DUAL-INLET IRMS SYSTEMS CONTINUOUS-FLOW IRMS SYSTEMS BULK MATERIAL STABLE ISOTOPE ANALYSIS 13C, 15N AND 34S 2H AND 18O COMPOUND-SPECIFIC STABLE ISOTOPE ANALYSIS OF VOLATILE ORGANIC COMPOUNDS COMPOUND-SPECIFIC 13C OR 15N ANALYSIS BY GC/C-IRMS COMPOUND-SPECIFIC 2H OR 18O ANALYSIS BY GC/HTC-IRMS POSITION-SPECIFIC ISOTOPE ANALYSIS COMPOUND-SPECIFIC 13C/15N ANALYSIS OF POLAR, NON-VOLATILE ORGANIC COMPOUNDS BY LC-IRMS COMPOUND-SPECIFIC ISOTOPE ANALYSIS AND FORENSIC COMPOUND IDENTIFICATION QUALITY CONTROL AND QUALITY ASSURANCE IN CONTINUOUS-FLOW ISOTOPE RATIO MASS SPECTROMETRY COMPLIANCE WITH IUPAC GUIDELINES IS A PREREQUISITE NOT A LUXURY THE IDENTICAL TREATMENT PRINCIPLE THE IMPORTANCE OF SCALE NORMALIZATION SCALE NORMALIZATION OF MEASURED ??2H VALUES TO VSMOW SCALE NORMALIZATION OF MEASURED ??13C VALUES TO VPDB SCALE NORMALIZATION OF MEASURED ??18O VALUES TO VSMOW SCALE NORMALIZATION OF MEASURED ??15N VALUES TO AIR SCALE NORMALIZATION OF MEASURED ??34S VALUES TO VCDT POINTS OF NOTE FOR STABLE ISOTOPE ANALYSIS PREPARING FOR ANALYSIS GENERIC CONSIDERATIONS FOR BSIA SCALE NORMALIZATION OF BSIA KEEPING YOUR POWDER DRY ISOBARIC INTERFERENCE IONIZATION QUENCH EFFECT PARTICULAR CONSIDERATIONS FOR BSIA BULK 15N ANALYSIS OF NITRATES BULK 2H ANALYSIS OF NITROGEN-RICH COMPOUNDS TOTAL ??2H VERSUS TRUE ??2H VALUES ORGANIC COMPOUNDS WITH EXCHANGEABLE HYDROGEN AND IMPLICATIONS FOR 2H ABUNDANCE ANALYSIS CHEMICAL AND BIOCHEMICAL CONSIDERATIONS – EXAMPLE: HAIR 2H ANALYSIS OF HUMAN HAIR TWO-POINT EQUILIBRATION WITH WATER AT AMBIENT TEMPERATURE TWO-POINT END-MEMBER COMPARATIVE EQUILIBRATION ON-LINE TWO-POINT END-MEMBER COMPARATIVE STEAM EQUILIBRATION POINTS OF NOTE FOR CSIA SCALE NORMALIZATION OF GC-IRMS ANALYSES ISOTOPE EFFECTS IN GC-IRMS DURING SAMPLE INJECTION THE CHROMATOGRAPHIC ISOTOPE EFFECT IN GC-IRMS DERIVATIZATION OF POLAR COMPOUNDS FOR GC-IRMS COMPOUND-SPECIFIC 2H ANALYSIS OF N- OR CL-RICH COMPOUNDS STATISTICAL ANALYSIS OF STABLE ISOTOPE DATA WITHIN A FORENSIC CONTEXT CHEMOMETRIC ANALYSIS BAYESIAN ANALYSIS QUALITY CONTROL AND QUALITY ASSURANCE IN FORENSIC STABLE ISOTOPE ANALYSIS ACCREDITATION TO ISO WHO ASSESSES THE ASSESSORS? THE FORENSIC ISOTOPE RATIO MASS SPECTROMETRY NETWORK SUMMARY OF PART II II A HOW TO SET UP A LABORATORY FOR CONTINUOUS-FLOW ISOTOPE RATIO MASS SPECTROMETRY PRE-INSTALLATION REQUIREMENTS LABORATORY LOCATION TEMPERATURE CONTROL POWER SUPPLY GAS SUPPLY FORENSIC LABORATORY CONSIDERATIONS FINISHING TOUCHES II B SOURCES OF INTERNATIONAL REFERENCE MATERIALS AND TERTIARY STANDARDS II C SELECTED SAMPLE PREPARATION PROTOCOLS DERIVATIZATION OF AMINO ACIDS FOR COMPOUND SPECIFIC ISOTOPE ANALYSIS BY GC-IRMS ACID DIGEST OF CARBONATE FROM BIO-APATITE FOR 13C AND 18O ANALYSIS PREPARING SILVER PHOSPHATE FROM BIO-APATITE FOR 18O ANALYSIS TWO-POINT WATER EQUILIBRATION PROTOCOL FOR DETERMINATION OF NON-EX ??2H VALUES OF HUMAN HAIR II D INTERNET SOURCES OF GUIDANCE AND POLICY DOCUMENTS REFERENCES PART II III STABLE ISOTOPE FORENSICS: CASE STUDIES AND CURRENT RESEARCH III 1 FORENSIC CONTEXT III 1 1 LEGAL CONTEXT III 2 DISTINGUISHING DRUGS III 2 1 NATURAL AND SEMISYNTHETIC DRUGS III 2 1 1 MARIJUANA III 2 1 2 MORPHINE AND HEROIN III 2 1 3 COCAINE III 2 2 SYNTHETIC DRUGS III 2 2 1 AMPHETAMINES III 2 2 2 METHAMPHETAMINE: SYNTHESIS AND ISOTOPIC SIGNATURE III 2 2 2 1 TWO DIFFERENT SYNTHETIC ROUTES – CLANDESTINE CONDITIONS III 2 2 3 MDMA: SYNTHESIS AND ISOTOPIC SIGNATURE III 2 2 3 1 THREE DIFFERENT SYNTHETIC ROUTES – CONTROLLED CONDITIONS III 2 2 3 2 ONE SYNTHETIC ROUTE – VARIABLE CONDITIONS III 2 3 “LEGAL HIGHS” AND “DESIGNER DRUGS” III 2 3 1 MEPHEDRONE III 2 3 2 PIPERAZINES III 2 4 EXCIPIENTS III 2 5 CONCLUSIONS III 3 ELUCIDATING EXPLOSIVES III 3 1 STABLE ISOTOPE ANALYSIS OF EXPLOSIVES AND PRECURSORS III 3 1 1 AMMONIUM NITRATE (AN) III 3 1 2 HEXAMINE, RDX, C4 AND SEMTEX III 3 1 3 ISOTOPIC PRODUCT/PRECURSOR RELATIONSHIP III 3 1 3 1 RDX AND HMX III 3 1 3 2 HMTD AND TATP III 3 1 4 HYDROGEN PEROXIDE III 3 2 POTENTIAL PITFALLS III 3 3 CONCLUSIONS III 4 MATCHING MATCHSTICKS 13C-BULK ISOTOPE ANALYSIS 18O-BULK ISOTOPE ANALYSIS 2H-BULK ISOTOPE ANALYSIS III 4 4 MATCHING MATCHES FROM FIRE SCENES III 4 5 CONCLUSIONS III 5 PROVENANCING PEOPLE III 5 1 STABLE ISOTOPE ABUNDANCE VARIATION IN HUMAN TISSUE III 5 1 1 HAIR AND NAILS III 5 1 1 1 CHARACTERISTICS OF HAIR III 5 1 1 2 CHARACTERISTICS OF NAILS III 5 1 1 3 DIAGENETIC CHANGES OF KERATIN 2H ISOTOPIC RECORD IN HAIR AND NAIL 18O ISOTOPIC RECORD IN HAIR AND NAIL 13C ISOTOPIC RECORD IN HAIR AND NAIL 15N ISOTOPIC RECORD IN HAIR AND NAIL III 5 1 2 BONE AND TEETH III 5 1 2 1 CHEMICAL COMPOSITION OF BONE AND TEETH III 5 1 2 2 STATIC VERSUS REMODELLING TISSUE COMPARTMENTS III 5 1 2 3 DIAGENETIC CHANGES OF BONE AND TEETH MINERAL III 5 1 2 4 DIAGENETIC CHANGES OF TYPE I COLLAGEN 18O ISOTOPIC RECORD IN CARBONATE AND PHOSPHATE FROM BIO-APATITE 13C ISOTOPIC RECORD IN CARBONATE FROM BIO-APATITE III 5 1 2 7 ISOTOPIC RECORD IN TYPE I COLLAGEN III 5 1 3 TROPHIC LEVEL SHIFT EFFECT ON STABLE ISOTOPE ABUNDANCE VALUES IN HUMAN TISSUE III 5 2 CASE EXAMPLES III 5 2 1 THE SKULL FROM THE SEA III 5 2 2 A HUMAN LIFE RECORDED IN HAIR III 5 2 3 FOUND IN NEWFOUNDLAND III 5 2 4 THE CASE OF “THE SCISSOR SISTERS” III 5 2 5 TOO SHORT A LIFE III 5 2 6 SALTAIR SALLY III 5 2 7 A TALE OF TWO CULTURES III 5 3 CONCLUSIONS AND CAVEATS III 6 STABLE ISOTOPE FORENSICS OF OTHER PHYSICAL EVIDENCE III 6 1 MICROBIAL ISOTOPE FORENSICS III 6 2 TOXINS AND POISONS III 6 3 PAPER, PLASTIC (BAGS) AND PARCEL TAPE III 6 3 1 PAPER III 6 3 2 PLASTIC AND PLASTIC BAGS III 6 3 3 PARCEL TAPE III 6 4 CONCLUSIONS III 7 EVALUATIVE INTERPRETATION OF FORENSIC STABLE ISOTOPE DATA III 7 1 NOT SCALE REFERENCED ??-VALUES III 7 2 UNRESOLVED CONTRADICTORY DATA III 7 2 1 EXAMPLE: “GEOGRAPHIC PROVENANCE OF A MURDER VICTIM” III 7 2 2 EXAMPLE: “MANSLAUGHTER DUE TO NEGLIGENCE” III 7 3 FOREGONE CONCLUSIONS III 7 4 LOGICAL FALLACIES III 7 5 UNTESTED ASSUMPTIONS III 7 6 CONCLUSION III 8 SUMMARY OF PART III III A AN ABRIDGED LIST OF FORENSIC STABLE ISOTOPE LABORATORIES WORLDWIDE REFERENCES PART III