definitions of these attributes.) In instances where the concentration of the generator can be based only on calculations using flow rates in the generator and the amount of analyte injected, the generation system should be well characterized [1] so that analyte losses are minimized.
In some instances, generation of an analyte may be difficult and even hazardous. As an alternative to direct generation in these cases, samplers may be fortified with an amount of analyte expected to be sampled over a specified period of time at a specific flow rate. When this is necessary, fortification of the sampler by vaporization of a known amount of analyte onto the sampling medium is a more appropriate method, since this approach more closely approximates a generated atmosphere. The alternative of direct application of a solution of analyte onto the collection medium is less desirable but may be necessary in some instances. After fortification, air, conditioned at both high and low humidity, should be drawn through samplers at the flow rate and time period used in the calculations for the amount of analyte expected to be collected. In the method report, the fact that samples were not collected from a generated atmosphere should be discussed.
b. Capacity of the Sampler and Sampling Rate
To determine the applicability of the sampling method, the capacity of the sampler should be determined as a function of flow rate and sampling time. This is particularly important if the analyte has both a short-term exposure limit (STEL) and a time-weighted average.
Flow rates typical for the media selected should be used. These may range from 0.01 - 4 L/min, depending on sampler type. At extremely low flow rates (ca. 5 mL/min), the effect of diffusion of the analyte into the sampler must be considered. Flow rates should be kept at a high enough rate to prevent diffusion from having a positive bias in the sampler. Sampling should be performed at three different flow rates covering the range appropriate for the particular sampler type, unless the sampler is designed to operate at only one flow rate. Sampling times should range from 22.5 min for STELs to 900 min (15 h) for time-weighted averages. Shorter sampling times (e.g., 7.5 to 22.5 min) may be used for ceiling © measurements. Flow rates should be based on accurately calibrated sampling pumps or critical orifices. The amount of analyte collected at the lowest flow rate and shortest sampling time should be greater than the limit of quantitation of the method. The generated concentration used for capacity determination should be at least 2 times the highest published exposure limit and verified by an independent method.
Sampling should be conducted at ambient, elevated (>35 C), and low (<20 C) temperatures to assess the effect of temperature on sampling. To assess the effect of humidity on capacity, sampling should be performed at both low and high humidities ( 20% and 80%, since both have been observed to affect capacity [11,3]. Triplicate samplers at three different flow rates should be included to verify capacity at each of the six different humidity and temperature levels. For samplers which contain backup sampling media, only the front section of the sampler should be used. A means is required to quantitate analyte in the effluent from the sampler. This may involve the use of a backup sampler, continuous monitor or other appropriate means which can provide a measure of analyte concentration in the sampler effluent (ca. 1 - 5% of the influent concentration). If the mass of analyte found on a backup sampler totals 5% of the mass found on the front sampler or if the effluent concentration of the sampler contains 5% of the influent concentration, breakthrough has occurred and the capacity of the sampler has been exceeded.
If the analyte is a particulate material and collected with a filter, the capacity of the filter is defined by the
pressure drop across the sampler or by the loading of the filter. For 37-mm filter-based samplers, pressure
