Laboratory investigation of the mass stability of sampling cassettes from inhalable aerosol samplers.

A study was conducted to evaluate the mass stability of the materials used in the construction of samplers with internal cassettes for the gravimetric measurement of inhalable aerosol exposures. The internal cassettes from IOM samplers were studied. Results indicate that the mass stability of filters is uniform, but the mass stability of the cassette material may dramatically affect the results of the measurement. Cassettes constructed from plastic exhibited drastic shifts in mass depending on the environmental conditions of their storage. Under room humidity, the plastic cassettes absorbed 1 to 2 mg of water over several days. When these cassettes were placed in a desiccator, they lost mass consistently but did not approach a stable mass. Studies repeated with cassettes made of stainless steel showed negligible mass variability. Based on this study, the use of stainless steel cassettes is recommended for gravimetric determinations of aerosol exposure, although field blanks may in some cases be used for correction of data from plastic cassettes. This study shows the need to evaluate the mass stability of the cassette material of any sampling device where an internal cassette is weighed together with the filter.

A sampling and analytical method for the simultaneous determination of multiple organonitrogen pesticides in air.

An air sampling and analytical method was developed for organonitrogen pesticides using a combined filter and XAD-2 sorbent sampler and high performance liquid chromatography-ultraviolet detection. The method was evaluated for 14 organonitrogen pesticides by National Institute for Occupational Safety and Health evaluation guidelines and procedures. Evaluation experiments addressed limits of detection and quantitation, analytical recovery, sampler capacity, sample stability, and precision and bias over a range of 12 to 240 micrograms per sample. Samples were stable when stored for up to 30 days under either ambient or refrigerated conditions. Based on the finding of this work, 10 of the 14 compounds studied (aldicarb, captan, carbaryl, carbofuran, chlorpropham, diuron, formetanate, methiocarb, oxamyl, propham) can be successfully determined simultaneously using one method with an accuracy of better than +/- 25% of the true value with 95% confidence. Two other compounds (carbendazim/benomyl, methomyl) can be measured with the same accuracy over a more limited concentration range. The remaining two compounds (propoxur, thiobencarb) may meet this criterion, but additional samples would need to be included in the data analysis. With the current data, these two compounds can be determined with an accuracy of better than +/- 27% of the true value with 95% confidence.

A computer program to promote understanding of the monitoring method evaluation guidelines used at NIOSH.

A computer-based training program has been devised to promote better understanding of the recently revised National Institute for Occupational Safety and Health (NIOSH) test guidelines applicable to methods requiring on-site sample collection and laboratory sample analysis of airborne toxic substances. A statistics section explains the basis of the NIOSH accuracy criterion (NAC); an experiments section provides details on the evaluation experiments; and a calculations section calculates method statistics based on data entered by the user. The statistics section graphically explains concepts such as the NAC and limit of detection, allowing the user to experiment with some parameters to see how the results are affected. This section also provides background material to show how some of the performance criteria evolved. The experiments section provides a summary of the experiments used to generate the data for method evaluation. The calculations section has several screens that work like customized spreadsheets for the entry of data collected during the laboratory evaluation of a method. A separate screen then calculates the precision (relative standard deviation) of analytical results at each of four concentrations, tests to see if the precision values are statistically homogeneous, and combines the homogeneous data for calculation of the relative standard deviation. It does the same for bias, and combines the precision with method bias to arrive at an estimate of method accuracy. Other screens in the calculations section facilitate the determination of method limit of detection and sample storage stability.

Determination of hexavalent chromium in industrial hygiene samples using ultrasonic extraction and flow injection analysis.

A simple, fast, and sensitive method was developed for the determination of hexavalent chromium (CrVI) in workplace samples. Ultrasonic extraction in alkaline solutions with 0.05 M (NH4)2SO4-0.05 M NH3 provided good extraction efficiency of CrVI from the sample and allowed the retention of CrVI on an ion-exchange resin (95%). The CrVI in the sample solution was then separated as an anion from trivalent chromium [CrIII] and other cations by elution from the anion-exchange resin with 0.5 M (NH4)2SO4 in 0.1 M NH3 (pH 8) buffer solution. The eluate was then acidified with hydrochloric acid and complexed with 1,5-diphenylcarbazide reagent prior to flow injection analysis. By analyzing samples with and without oxidation of CrIII to CrVI using CeIV, the method can measure CrVI and total Cr. For optimizing the separation and determination procedure, preliminary trials conducted with two certified reference materials (CRMs 013-050 and NIST 1633a) and three spiked samples (ammonia buffer solution, cellulose ester filters and acid washed sand) indicated that the recovery of CrVI was quantitative (> 90%) with this method. The limit of detection for FIA-UV/VIS determination of the Cr-diphenylcarbazone complex was in the sub-nanogram range (0.11 ng). The technique was also applied successfully to a workplace coal fly ash sample that was collected from a power plant and paint chips that were collected from a heating gas pipe and a university building. The principal advantages of this method are its simplicity, sensitivity, speed and potential portability for field analysis.

Summary of the NIOSH guidelines for air sampling and analytical method development and evaluation.

Suggested guidelines for the development and evaluation of sampling and analytical methods for industrial hygiene monitoring have recently been published in a NIOSH technical report. These guidelines are based in part on various published approaches for method development and evaluation and serve as an attempt at a more unified experimental approach. This paper presents some salient features of this unified approach for method development and evaluation. The basic goal of the approach is to determine if the method under study meets the criterion to produce a result that fell within 25% of the true value 95 times out of 100 on average, although other factors of method performance are evaluated. The experiments proposed for the evaluation of method performance include determination of analytical recovery from the sampler, sampler capacity, storage stability of samples and effect of environmental factors. Evaluation criteria for the experimental data and procedures for the calculation of method bias, precision and accuracy are also included.

A sampling and analytical method for the simultaneous determination of multiple organophosphorus pesticides in air.

A sampling and analytical method for organophosphorus pesticides using a combined filter/XAD-2 sorbent sampler and gas chromatography (GC)-flame photometric detection (FPD) was developed. The method was evaluated for 19 organophosphorus pesticides based on the joint Occupational Safety and Health Administration/National Institute for Occupational Safety and Health Standards Completion Program methods evaluation protocol. The evaluation addressed analyte recovery, sampler capacity, sample stability, and precision and accuracy. Additional experiments addressed long-term sample stability (30-day storage), short-term exposure limits, limits of detection, and concentration levels down to 0.1 times an exposure limit value. Samples were stable for 30 days of storage under either ambient or refrigerated conditions. Based on this research, all 19 compounds studied can be successfully determined simultaneously using one method with an accuracy of +/- 25% of the true value 95 times out of 100.

Strategies for the simultaneous collection of vapours and aerosols with emphasis on isocyanate sampling.

Workplace air frequently contains hazardous substances that may be present as vapours or as aerosols with a wide range of particle sizes. Depending upon a chemical species' volatility and use, it may be present in significant amounts in both the vapour and particulate phases. Unfortunately, the mechanisms by which vapours and particles are removed from an air stream during pumped sampling are substantially different. Collection of vapour molecules relies on their diffusion to a surface during their residence time in a sampler. Once in contact with a surface, vapour molecules are trapped either by adsorption onto a solid surface, absorption by a liquid, or by reaction with the medium or chemicals in the medium. Aerosol particles are most frequently collected by filtration or inertial impaction. However, if it is necessary to collect both phases simultaneously, a sampler with two stages is generally required. The exact nature of the sampler depends upon the size of the aerosol particles and the physical and chemical characteristics of the species of interest. A number of recent projects undertaken by researchers at the National Institute for Occupational Safety and Health have dealt with development of sampling and analytical methods for compounds present in workplace air as both vapour and aerosol particles. One strategy invoked in several instances consisted of a filter for particle collection followed by an appropriate second stage for vapour collection. For organophosphorus pesticides, the second stage was a sorbent tube. For gaseous hydrogen fluoride, it was an alkaline-impregnated back-up pad. For formaldehyde, the second stage was an impinger containing an aqueous solution of sodium hydrogensulfite.(ABSTRACT TRUNCATED AT 250 WORDS)

Application of multidimensional gas chromatography-mass spectrometry to the determination of glycol ethers in air.

The applicability of multidimensional gas chromatography-mass spectrometry to the analysis of five glycol ethers in air was demonstrated. Air samples were collected on charcoal tubes and desorbed with 5% methanol in methylene chloride as is described in method 1403 of the National Institute for Occupational Safety and Health Manual of Analytical Methods. The glycol ethers were determined by multidimensional gas chromatography-mass spectrometry. The limit of detection was 5 to 7 micrograms/sample for each compound.

Evaluation of the Du Pont Pro-Tek Formaldehyde Badge and the 3M Formaldehyde Monitor.

The 3M Formaldehyde Monitor and the DuPont Pro-Tek Formaldehyde Badge were evaluated for performance and reliability. This evaluation revealed that the 3M monitor results were variable and lower than reference concentrations determined independently. When the monitors were humidified before use and then exposed in humid (ca. 80% RH) formaldehyde-containing atmosphere, the monitors did give accurate results. Results of additional experiments led to the conclusion that quantitative reaction between formaldehyde generated in our chamber and the absorbent pad in the 3M monitor required the presence of a minimum level of absorbed water. The DuPont badges gave good agreement with the reference concentrations determined independently under the following conditions: sampling period of 1 to 12 hr with a minimum integrated sample loading of 4 ppm-hr; at least 3 m/min (10 ft/min) face velocity; correction for blank badges; and correction for loss of reagent from the samples. The evaluation indicated that the DuPont badge was not well suited to short term sampling and was subject to evaporation of liquid from the absorbing liquid blister. Blank values also were found to be variable, necessitating the analysis of several blanks to be used for blank correction with each set of samples. This blank variability also contributed to high variability found when short term measurements were made. The badge also had a negative interference from phenol at high phenol-to-formaldehyde ratios. Some of the major problems observed with both passive monitors were found only after devices which had been aged under storage conditions were analyzed and these results interpreted. If all testing had been done with fresh sampling devices, many of the problems would not have been noticed. Based on the results of this study, this factor of diffusive monitor aging needs to be addressed in any further work on passive monitor evaluation.

Deoxyribonucleic acid base composition in the taxonomy of Staphylococcus.

Twenty-four strains of Staphylococcus aureus, including eight known mutants of S. aureus and strains growing under a variety of environmental conditions or exposed to a number of physical and chemical agents, maintained a remarkably narrow range of guanine plus cytosine (GC) content (32.4 to 35.1%). The wide range of GC content (30.7 to 40%) reported in the literature was due to the variety of methods and calculations used rather than to any substantial variation in base composition. The UV-2 "mutant" (ATCC 13680) with a GC content of 67.6% reported to be derived from S. aureus (ATCC 13679) was a species of Corynebacterium. The data presented were consistent with the concept that base composition changes only to a very slight degree by mutation.