Since innovation is a key element in the sampling and analytical method development process, detailed experiments for the initial development of the sampling approach and optimization of the analytical procedure are better left to the discretion of the researcher. During development, it should be recognized that appropriate, statistically designed experiments will optimize the amount of information obtained. Therefore, consultation with a statistician about appropriately designed experiments will be of value during this phase of the research.
a. Preliminary Experimentation
Several key points, including calibration and selection of measurement technique and sampling media, should be studied during the initial method development experiments. The selection of sampling medium and procedure is a decision that usually is made early in the method development process. The physical state of the analyte (i.e., gas, aerosol, vapor, or combination thereof) plays an important factor in the selection of an appropriate sampler. Analytes which can exist in more than one physical state may require a combination of sampling media in one sampler for efficient collection [1]. Where possible, commonly available and easily used samplers should be investigated initially. As the preliminary testing of a sampling method progresses, further modification in the sampling medium or sampler design may be required and may affect the measurement procedure. Sampler design and media selection considerations should include U.S. Department of Transportation regulations and restrictions for shipment back to a laboratory for analysis.
Since industrial hygiene analytical methods are geared toward measuring personal exposure, the size, weight, and convenience of the sampler are important elements in sampler design. The personal sampler should allow freedom of movement and should be unobtrusive, unbreakable, and not prone to leakage. The pressure drop across the sampler should not be so great as to limit sample collection times to 10 h with personal sampling pumps. For situations where only a short term sample will be required (i.e., 15 min for ceiling determinations), this 10 h recommendations can be reduced to 1 h. The use of potentially toxic reagents should be avoided unless they can be used safely. Reagents used should not pose any exposure hazard to the worker wearing the sampler or to the industrial hygienist taking the samples.
b. Recovery of the Analyte from the Medium During the course of method development experiments, the ability to recover the analyte from the sampling medium should be determined. A suggested experiment to accomplish this entails the fortification of sets of 6 samplers with amounts of analyte equivalent to sampling concentrations of 0.1, 0.5, 1.0, and 2.0 (or higher) times the exposure limit for a minimum of 4 h at the typical sampling rate used for that type of sampler. If the analyte has a ceiling or short-term exposure limit, the amount of analyte fortified should be adjusted for the shorter sampling time required for this type of exposure limit. If the sampler has a backup section, then a like number of separate backup sections should be fortified with amounts of analyte equivalent to 25% of the amount fortified on the front sections of the samplers, since this amount has been used to characterize the breakthrough limit of useful samples [2]. Samples (and backup sections) should be prepared for analysis and analyzed according to previously determined procedures. Results of these analyses should be expressed in terms of estimated percent recovery according to the following formula:
