drop should be less than 40 inches (1016 mm) of water for total loading less than 2 mg. Larger filters may tolerate higher loadings.
If the collection process is based primarily on adsorption, breakthrough time should be proportional to the inverse of the flow rate [14]. This relationship can be checked by plotting the 5% breakthrough time versus the inverse of the flow rate. If the resulting plot is a straight line, then this relationship should hold for all flow rates in the flow rate range studied. Some nonlinearity in the plot may be noted due to experimental variability and assumptions made to simplify the relationship of breakthrough time and flow rate. Results from these experimental trials should provide a prediction of the capacity of the sampler at various flow rates and sampling times. If the flow rates and sampling times used in the experiment do not provide for sufficient capacity, a lower flow rate range may have to be studied and the experiment repeated.
With samplers which use reagents for collection of the analyte, the amount of the reagent in the sampler will also be a limiting factor in the capacity of the sampler, based on the stoichiometry of the reaction. Other factors, such as residence time in the sampler and kinetics of reaction between analyte and reagent, may affect the capacity of this type of sampler.
The combined temperature and humidity conditions that reduce sampler capacity to the greatest extent should be used in all further experiments. The Maximum Recommended Sampling Time (MRST) for a specific flow rate is defined as the time at which sampler capacity was reached, multiplied by 0.667. This adds a measure of safety to this determination. The relationship of breakthrough time with flow rate can be used to adjust flow rates to optimize specific sampling times.
c. Sampling and Analysis Evaluation
To assess the performance of a method, certain additional experimental parameters should be evaluated through a series of defined experiments. The effect of environmental conditions (e.g., pressure, interferences) on sampling efficiency of the sampling medium can be evaluated by a factorial design [15]. The temperature, relative humidity, flow rate, and sampling times, determined in the experiment described above to have most severely limited sampler capacity, should be used in these experimental runs. At a minimum, the effect of concentration on method performance should be investigated. Three sets of 12 samples should be collected from an atmosphere containing concentrations of 0.1, 1.0, and 2.0 times the exposure limit at the humidity determined above to have reduced sampler capacity for the MRST determined in the preceding experiment. If the analyte has a short-term or ceiling exposure limit in addition to a 8-hour time-weighted average, an additional 12 samplers should be collected at the STEL or C limit for the recommended sampling period at the appropriate flow rate. Potential interferences in the work environment should be included in the generation experiments to assess their impact on method performance. Concentrations up to 2 times the exposure limit value for the interference should be included. Other environmental factors may be studied, but will require a more comprehensive experimental design.
The effects of environmental conditions on analyte recovery should be assessed. A factorial design can be used to evaluate these factors to determine which exert a significant effect on analyte recovery. Those factors which are found to influence analyte recovery should be investigated further to determine if their impact is predictable. If these effects are not predictable, the utility of the method will be limited, based on the conditions defined by this experiment. If only concentration is evaluated, the analyte recovery should be the same at all
concentrations after correctable biases have been included, such as desorption efficiency.
