Forensic identification of dyes extracted from textile fibers by liquid chromatography mass spectrometry (LC-MS)

LC-MS is used for the identification of dyes extracted from textile fibers and the utility of the method for forensic trace analysis is demonstrated. The technique is shown to provide a high degree of chemical structural information, making dye identification highly specific in comparison to optical and/or chromatographic methods of dye analysis. A UV-visible absorbance detector, placed in series before the MS detector, facilitates monitoring the elution of dyes in the presence of other non-dye components extracted from colored textile fibers. In this way, dye identification becomes practical, even when a dye standard is not available for comparison. A set of 22 reference dyestuffs and 10 dyes extracted from textile fibers were analyzed to demonstrate the utility of the method. Six of the extracted dyes corresponded to dyes also contained in the set of 22 reference dyestuffs. Reference dyestuffs were not available for four of the extracted dyes. Triethylamine (TEA) was shown to increase the electrospray ionization-mass spectrometry (ESI-MS) response of dyes containing multiple sulfonated groups.     

A laboratory incubation method for determining the rate of microbiological degradation of skeletal muscle tissue in soil

A controlled laboratory experiment is described, in principle and practice, which can be used for the of determination the rate of tissue decomposition in soil. By way of example, an experiment was conducted to determine the effect of temperature (12 degrees, 22 degrees C) on the aerobic decomposition of skeletal muscle tissue (Organic Texel x Suffolk lamb (Ovis aries)) in a sandy loam soil. Measurements of decomposition processes included muscle tissue mass loss, microbial CO2 respiration, and muscle tissue carbon (C) and nitrogen (N). Muscle tissue mass loss at 22 degrees C always was greater than at 12 degrees C (p < 0.001). Microbial respiration was greater in samples incubated at 22 degrees C for the initial 21 days of burial (p < 0.01). All buried muscle tissue samples demonstrated changes in C and N content at the end of the experiment. A significant correlation (p < 0.001) was demonstrated between the loss of muscle tissue-derived C (Ct) and microbially-respired C (Cm) demonstrating CO2 respiration may be used to predict mass loss and hence biodegradation. In this experiment Q10 (12 degrees C-22 degrees C) = 2.0. This method is recommended as a useful tool in determing the effect of environmental variables on the rate of decomposition of various tissues and associated materials.     

Oxycodone intoxication in an infant: accidental or intentional exposure?

A case is presented of a 10 month old male who went into cardiac arrest at a local store. The infant subsequently expired and was autopsied at the Office of the Chief Medical Examiner, State of Maryland. The only remarkable finding was the detection of oxycodone in the postmortem specimens; the blood and liver oxycodone concentrations were 0.6 mg/L and 1.6 mg/kg, respectively. Oxycodone was identified and quantitated by gas chromatography-nitrogen-phosphorus detection and confirmed by full scan electron ionization gas chromatography-mass spectrometry. The medical examiner ruled that the cause of death was oxycodone intoxication, and the manner of death was homicide. The key toxicologic question in this case was whether or not it was reasonable for the infant to be exposed to oxycodone exclusively through breast milk or through an alternate source. It was concluded that, at best, there were serious concerns about the likelihood of drug exposure through consumption of breast milk.     

Analysis of nitrite in adulterated urine samples by capillary electrophoresis

A simple method for analyzing nitrite in urine has been developed to confirm and quantify the amount of nitrite in potentially adulterated urine samples. The method involved separation of nitrite by capillary electrophoresis and direct UV detection at 214 nm. Separation was performed using a bare fused silica capillary and a 25 mM phosphate run buffer at a pH of 7.5. Sample preparation consisted of diluting the urine samples 1:20 with run buffer and internal standard, and centrifuging for 5 min at 2500 rpm. The sample was hydrodynamically injected, then separated using -25 kV with the column maintained at 35 degrees C. The method had upper and lower limits of linearity of 1500 and 80 microg/mL nitrite, respectively, and a limit of detection of 20 microg/mL. The method was evaluated using the National Committee for Clinical Laboratory Standards (NCCLS) protocol (Document EP10-A2), and validated using controls, standards, and authentic urine samples. Ten anions, ClO-, CrO4(-2), NO3-, HCO3-, I-, CH3COO-, F-, SO4-, S2O8(-2), and Cl-, were tested for potential interference with the assay. Interferences with quantitation were noted for only CrO4(-2) and S2O8(-2). High concentrations of Cl- interfered with the chromatography. The method had acceptable accuracy, precision, and specificity.     

The application of NIST's Fire Dynamics Simulator to the investigation of carbon monoxide exposure in the deaths of three Pittsburgh fire fighters

A case is reported in which computer fire modeling was used to reevaluate a fire that killed three fire fighters. NIST's Fire Dynamics Simulator (FDS) was employed to model the fire in order to estimate the concentration of carbon monoxide present in the dwelling, which was the immediate cause of death of two of the fire fighters, who appear to have removed their face pieces in order to share available air. This estimate, along with an assumed respiration volume and known blood carboxyhemoglobin, was plugged into a standard equation to estimate the time of exposure. The model indicated that 27 min into the fire, the carbon monoxide concentration had already reached approximately 3600 ppm. At this concentration, and a respiration of 70 L/min, an estimated 3 to 8 min of exposure would have been required to accumulate the concentrations of carboxyhemoglobin (49, 44, and 10%) measured on the fire fighters at autopsy.     

A selection of some of Dr. McCrone's high and low profile cases in the forensic analysis of art

Throughout Dr. McCrone's active professional career of over 60 years, he worked on many cases involving the forensic analysis of art. This is an overview of a small portion of these cases. Included (exposed as fakes) are the Shroud of Turin, the Vinland Map, Mayan pottery illustrations and Larionov pastels. Also included, with strong support for authentication, are three paintings attributed to Manet, Giorgione, and Leonardo da Vinci.