Carbonyl compounds air sampling method.
Que Hee-SS; Wong-WK
Atlanta, GA: U.S. Department of Health and Human Services, Public Health Service, Centers for Disease Control and Prevention, National Institute for Occupational Safety and Health, R01-OH-003120, 1999 Nov; :1-20
The objective was to develop workplace passive (diffusive) sampling and dynamic sampling methods for the regulated aldehydes and ketones for use in the workplace, both indoors and at hazardous waste sites. The specific aims were: (1) To synthesize pure 0(2,3,4,5,6-pentafluorobenzylamine hydrochloride) [PFBHA] derivatives of representative carbonyl compounds and quantify them using both gas chromatography and liquid chromatography; (2) To identify a generation of static (gas bag) and air dilution system (syringe pump air dilution system) with concentrations of hygienic interest for vapors of representative carbonyl compounds to demonstrate that the dynamic sampling method is quantitative at 0% and 90% relative humidity; and (3) To develop accurate diffusive sampling badges at 0% and 90% relative humidity that are sensitive for carbonyl carcinogens. Field studies were conducted on pathology laboratory personnel and workers exposed to formalin, glutaraldehyde, aldehydes and ketones. This study found: (1) the PFBHA coated solid sorbent technique allow pg sensitivity with selectivity using GC/ECD or GC/MS-SIM for the aldehyde and ketone homologs. Less sensitivity was found with HPLC/UVD but both sets of O-oxime standards can be used for GC and HPLC if acetonitrile is the solvent. (2) Both the dynamic and passive sampling techniques for vapors of aldehydes and ketones show recoveries of at least 75% except for ketones that are sterically hindered by substitution at both _ carbons to the carbonyl carbon, and those structures may effect these sites in the gas phase. (3) The field results of the passive and dynamic samplers appear to differ. When passive sampler was validated using a different technique the results are closer to the "correct" answer. More research is needed to further investigate aim 3. Passive sampling rates for ketones not completed in this study as well as defining the sampling rates using the new ACGIH ceiling limits. Analysis could also be initiated to determine sampling techniques using defined mixtures. The extreme sensitivity of ECD for detection of PFBHA O-oximes of carbonyl compounds allows a high screening sensitivity that exceeds that for the standard EP A 2,4-dinitrophenyl hydrazine (DNPH) solid sorbent/HPLC-UVD method. Capillary GC allows far greater resolution than a C 18 reversed-phase HPLC column. While a nitrogen detector can be used for the sensitive screening detection of oxazolidine derivatives used for the current NIOSH and OSHA methods, PFBHA is more reactive than 2(hydroxymethyl)piperidine and shows better recoveries for conjugated aldehydes like acrolein and crotonaldehyde, and much better recoveries for ketones. The nitrogen detector for oxazolidines is more costly, and more expensive to run than a ECD detector. GC/MS-SIM is far more selective (m/z 181) and sensitive for PFBHA O-oximes, than HPLC/MS as a confirmatory technique for 2,4-dinitrophenylhydrazones. GC/MS can be used to confirm oxazolidines for the NIOSH and OSHA methods, but the selectivity and sensitivity is worse. The passive sampling configuration requires no pump calibration, and no investment in pumps as do dynamic sampling methods. Both passive and dynamic PFBHA samplers have a sampling rate for the aldehydes that is independent of temperature, RH, and intermittent sampling. There is a temperature dependence for the GMD passive sampler based on DNPH, and there is no 2-(hydroxymethyl)piperidine based passive sampler. In addition DNPH, being colored, is photochemically active in the ultraviolet/visible region of the spectrum. The PFBHA passive sampler is potentially patentable. Passive samplers are much more convenient to wear for the worker than the dynamic sampler-tubing-pump ensemble. Passive sampling does not potentially upset the protectiveness of quantitatively fitted respirators under field conditions, unlike a dynamic sampler technique which might pull contaminated air through the cartridge or at the face to respirator seal. Since the breath is near 100% RH, and there is a temperature variation from workplace temperature to body temperature, it is advantageous to conduct studies of workplace protection factors (WPFS) for a badge that is not dependent on temperature and RH, unlike the GMD badge or charcoal-based diffusive samplers. Thus, at least for most carbonyl compounds, feasible measurements of WPFs are now possible.
Carbinols; Air-sampling; Air-sampling-techniques; Sampling-methods; Workplace-monitoring; Hazardous-waste-cleanup; Gas-chromatography; Carcinogens; Ketones; Aldehydes
Department of Environmental Health Sciences, University of California at Los Angeles, School of Public Health, 10833 Le Conte Avenue, Los Angeles, CA 90095-1772
111-30-8; 107-02-8; 4170-30-3
Final Grant Report
Research Tools and Approaches: Exposure Assessment Methods
National Institute for Occupational Safety and Health
University of California Los Angeles, Los Angeles, CA