A significant portion of the work of developing and validating methods for volatile organic compound (VOC) sampling in workplace atmospheres involves the use of laboratory-generated atmospheres. The sample variability was evaluated from the dynamic atmosphere generation system used for VOC atmosphere generation and sampling. Characterization of the bias and variability of samples was done for a variety of atmospheres containing neat n-heptane and mixtures of VOCs sampled on activated coconut shell charcoal. Estimates of sampling variability ranged from 2% for neat n-heptane to 12% for a component in the 10 VOC mix. Sample variability increased for lower concentration samples and for mixtures of VOCs compared to single component atmospheres. This study can serve as a baseline for future atmosphere sampling experiments evaluating performance at lower concentrations and mixed VOC environments.

Determining worker exposure to hazardous volatile organic compounds (VOCs) in air at levels exceeding the Permissible Exposure Limits and Recommended Exposure Limits established by the U.S. federal agencies of Occupational Safety and Health Administration (OSHA) and the National Institute for Occupational Safety and Health (NIOSH), respectively, will continue to be an important part of environmental and occupational health risk assessments. The purpose of this work was to develop a reliable analytical method for rapid and on-site assessments of occupational VOC exposures using field-capable thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) instrumentation (i.e. the HAPSITE ER). The experiments involved in this study included determining TD-GC-MS parameters suitable for efficient analyte separation and quantitation on the HAPSITE ER, determinations of analyte mass loadings that cause mass spectrometer detector saturations, generation of calibration curves, estimations of the limits of detection (LODs) and quantification (LOQs), as well as desorption efficiency and relative response factor repeatability. The LODs using Carbopack B and Tenax TA sampling media were estimated and ranged from 0.21.9 ng and 0.0450.3 ng, respectively. The LOQs using Carbopack B and Tenax TA sampling media were estimated and ranged from 1.06.3 ng and 0.21.1 ng, respectively. We have developed a reliable analytical method for chloroform, benzene, trichloroethylene, and heptane using field-portable HAPSITE ER instrumentation and Tenax TA sorbent media. Reliable and accurate methods were developed for chloroform and trichloroethylene using Carbopack B sorbent media, however, this particular sorbent hadlow desorption efficiency and insufficient repeatability in relative response factors for many analytes. Our current and ongoing work in determining the uptake rates for analytes on Tenax TA sorbent media will make the methods described herein applicable for on-site occupational VOC exposure assessments of chloroform, benzene, trichloroethylene, and heptane using either passive or active air sampling techniques. This work was authored as part of the Contributors official duties as an Employee of the United States Government and is therefore a work of the United States Government. In accordance with 17 USC 105, no copyright protection is available for such works under US Law.

A method for measuring peracetic acid vapors in air using impinger sampling and field-portable colorimetric analysis is presented. The capture efficiency of aqueous media in glass and plastic impingers was evaluated when used for peracetic acid vapor sampling. Measurement of peracetic acid was done using an N,N-diethyl-p-phenylenediamine colorimetric method with a field portable spectrometer. The linearity of the N,N-diethyl-p-phenylenediamine method was determined for peracetic acid both in-solution and captured from vapor phase using glass or plastic impingers. The Limits of Detection for the glass and plastic impingers were 0.24 mg/m(3) and 0.28 mg/m(3), respectively, for a 15 L air sample. The Limits of Quantitation were 0.79 mg/m(3) and 0.92 mg/m(3) for the glass and plastic impingers, respectively. Both metrics were below the American Conference of Governmental Industrial Hygienists Threshold Limit Value Short-Term Exposure Limit of 1.24 mg/m(3) (0.4 ppmv) during a 15-minute period. This impinger sampling method presented herein allows for an easy to use and rapid in-field measurement that can be used for evaluating occupational exposure to peracetic acid.

A system for controlled generation of peracetic acid (PAA) atmospheres used to test and evaluate sampling and measurement devices was developed and characterized. Stable atmospheric conditions were maintained in a dynamic flow system for hours while multiple sensors were simultaneously exposed to equivalent atmospheres of PAA vapors. Atmospheres characterized by a range of PAA concentrations at a controlled flow rate, temperature, and humidity were generated. Presented herein is a system for vaporization of PAA solutions to generate controlled atmospheres with less than 3% relative standard deviation (RSD) of the PAA concentrations over time.