Monitoring for occupational exposure to 4,4'-methylenebis(2-chloroaniline) by gas chromatographic-mass spectrometric analysis of haemoglobin adducts, blood, plasma and urine.

The feasibility of using plasma, blood and haemoglobin adducts for monitoring occupational exposure to the suspected human carcinogen 4,4'-methylenebis(2-chloroaniline) (MOCA) was investigated. A method utilising capillary gas chromatography-negative-ion chemical-ionisation mass spectrometry (GC-MS) for the determination of pentafluoropropionyl (PFP) derivatives of MOCA, released by alkaline hydrolysis from protein adducts and conjugates, was both sensitive and selective. When selected ion monitoring was used, sub-femtomole amounts of PFP-MOCA could be measured. The detection limit for haemoglobin adducts of MOCA was below 10 fmol/g Hb, well below the levels found for occupationally exposed individuals. Capillary GC with electron-capture detection also had the required sensitivity for the determination of MOCA in blood samples, however, the presence of interfering compounds in some samples limited its use. The levels of MOCA in the blood and urine of five individuals who were exposed to MOCA during the manufacture of polyurethane elastomers were determined by the GC-MS method. The MOCA concentrations for the various blood fractions and urine were within the following ranges: haemoglobin adducts, 0.73-43.3 pmol MOCA/g Hb; plasma alkaline hydrolysate, 0.05-22.0 nmol/l; whole blood, 0.13-17.4 nmol/l; urine, 4.5-2390 nmol/l. Because the products of MOCA in the blood reflect metabolic activation of MOCA and integrate exposure over a period of weeks, the use of blood samples for monitoring exposure to MOCA offers advantages over the currently used urinary MOCA measurements.

Transcranial Doppler ultrasound findings in cerebral venous sinus thrombosis. Case report.

Transcranial Doppler ultrasound (TCD) findings are described in a patient with acute thrombosis of the sagittal venous sinus. The TCD finding of prominent venous signals adjacent to the middle cerebral artery gave the first indication of the diagnosis, which was subsequently confirmed by computerized tomography. Awareness of the possible TCD findings in patients with a similar history may lead to a more rapid diagnosis of cerebral venous sinus thrombosis.

Platinum in the human diet, blood, hair and excreta.

Baseline levels of platinum in the blood, hair and urine of 21 adults from Sydney, Australia, and three adults from the relatively unpolluted area of Lord Howe Island, Australia, were determined by adsorptive voltammetry. The median concentrations of platinum in samples from residents in Sydney were: whole blood, 0.56 microgram Pt l-1; hair, 3.84 micrograms Pt kg-1; urine, 0.18 microgram Pt l-1 (0.23 microgram Pt g creatinine). Samples from residents of Lord Howe Island had platinum levels that were within the range of values of the corresponding samples from Sydney residents. For faeces samples, the median platinum concentration was 10.5 micrograms kg-1 FW. The excretion of platinum over a 4-day period was measured in one adult male. Urinary excretion of platinum was between 0.76 and 1.07 micrograms Pt day-1 and in faeces it was between 0.61 and 0.73 microgram Pt day-1. The concentrations of platinum in a range of foodstuffs from Sydney were between 8.11 micrograms kg-1 FW for liver and 0.13 microgram kg-1 FW for full-cream milk. This information as well as the amounts of these foods in hypothetical diets for Australians was used to calculate the total dietary intake of platinum. The average diet of a Sydney adult contains 1.44 micrograms of platinum per day (adult male, 1.73 micrograms Pt day-1; adult female, 1.15 micrograms Pt day-1). The uptake of dietary platinum from the gut was estimated to be at least 42% and, therefore, diet appears to make a substantial contribution to total platinum intake.

Determination of platinum in blood by adsorptive voltammetry.

This work describes a sensitive method for the determination of platinum in blood, which can be used for determining the natural levels of platinum in human blood, for monitoring patients treated with platinum cytotoxic drugs, and for monitoring occupational exposure to these drugs and other platinum compounds. The method involves dry ashing of blood samples in a muffle furnace and determination of platinum by adsorptive voltammetric (AV) measurement of the catalytic reduction of protons by the platinum-formazone complex. The detection limit for a 100-microL sample of blood is 0.017 micrograms/L, with a recovery of 94% and a relative standard deviation of 7% at a platinum level of 1 microgram/L. By using this method, the natural levels of platinum in human blood were found to be in the range 0.1-2.8 micrograms/L (median = 0.6 micrograms/L). These results were verified by inductively coupled plasma mass spectrometry (ICP-MS) with blood prepared by wet ashing and using gold as an internal standard.

Resolution of RS-abscisic acid and the separation of abscisic acid metabolites from plant tissue by high-performance liquid chromatography.

Attempts to resolve the enantiomers of racemic abscisic acid (ABA) by high-performance liquid chromatography on a chiral stationary-phase column were unsuccessful. However, reduction of RS-methyl ABA (RS-Me-ABA) with sodium borohydride generates a new chiral centre and one of the two isomeric products, the RS-Me-1',4'-cis-diol of ABA, was separated into its enantiomers by high-performance liquid chromatography on an optically active Pirkle column. High-performance liquid chromatography on a mu Bondapak C18 column separated the metabolites and conjugates of [2-14C]ABA fed to tomato shoots. The resolution method was used to measure the relative proportions of R and S enantiomers in the free acid liberated from conjugates of ABA.