Sampling rates , SPMD

PESs by the end of the exposure. Differences in exposure concentrations did not affect the sampling rates of PESs, which indicate that these devices obey first-order uptake kinetics. The sampling rate of " C-2,2 ,5,5 -TCB by PESs (4.8 L d ) was similar to that observed for 1 mL triolein SPMDs, with the same surface area. 

Some introductory comments on the conceptual basis of SPMD uptake (ku) and release (ke) rate constants and the associated sampling rates (i.e., Rs) are in order. The can be conceptualized as the volume of air or water cleared of chemical per unit sampler mass or volume per unit time (e.g., mL g d or mL mL d ) and Rs is the volume of air or water cleared per unit time (e.g., L d ). Thus, the only difference between ku and Rs is that Rs is not normalized to a unit mass or unit volume of sampler. In the context of organism exposure (see Section l.L), the SPMD is equivalent to the encounter volume times the fractional bioavailability of the chemical (which excludes dietary uptake). The release rate constant (d ) is equal to kuK J. 

Huckins, J.N. Petty, J.D. Orazio, C.E. Lebo, J.A. Clark, R.C. Gibson, V.L. Gala, W.R. Echols, K.R. 1999, Determination of uptake kinetics (sampling rates) by lipid-containing semipermeable membrane devices (SPMDs) for polycyclic aromatic hydrocarbons (PAHs) in water. Environ. Sci. Technol. 33 3918-3923. 

When the k and SPMD-water partition coefficient of the PRC are known, its Rs can be calculated from Eq. 3.20. More precisely, we assume that the PRC is representative of the in situ sampling rates of target compounds with similar physicochemical properties as the PRC. Various approaches have been used to estimate sampling rates for all analytes from the PRC-derived sampling rates (see Section 3.6.). 

A general conclusion that can be drawn from Figure 3.6 is that sampling rates of compounds with log values between 6 and 7 are in the range 2 to 12 L d at flow velocities below 10 cm s, with a geometric mean of 4.2 L d These data underscore the importance of using PRCs for a site- and SPMD-speciflc assessment of the effects of exposure conditions. 

Figure 3.9 Ratio of sampling rates with biofouled and non-biofouled SPMDs as a function of...

No large variation in sampling rates is observed among the different studies, despite differences in exposure conditions, such as wind speeds, temperature, and SPMD mounting layout. It should be noted, however, that the effect of temperature is partially accounted for by our use of temperature-corrected log A oa values. An example of the application of Eq. 3.68 for calculating atmospheric concentrations is given in Box 3.3. 

Sampling rates for the case of total boundary layer-control can be expected to be nearly independent of temperature, since both the diffusion coefficients in air, and the kinematic viscosity of air are only weak functions of temperature (Shoeib and Harner, 2002). This leaves the air-flow velocity as the major factor that can be responsible for the seasonal differences among sampling rates observed by Ockenden et al. (1998). The absence of large R differences between indoor and outdoor exposures may be indicative of membrane-control, but it may also reflect the efficient damping of high flow velocities by the deployment devices used for SPMD air exposures (Ockenden et al., 2001). 

Although Rs values of high Ks compounds derived from Eq. 3.68 may have been partly influenced by particle sampling, it is unlikely that the equation can accurately predict the summed vapor plus particulate phase concentrations, because transport rates through the boundary layer and through the membrane are different for the vapor-phase fraction and the particle-bound fraction, due to differences in effective diffusion coefficients between molecules and small particles. In addition, it will be difficult to define universally applicable calibration curves for the sampling rate of total (particle -I- vapor) atmospheric contaminants. At this stage of development, results obtained with SPMDs for particle-associated compounds provides valuable information on source identification and temporal... 

Huckins, J.N. Petty, J.D. Gale, R.W. Booij, K. Prest, H.F. Clark, R.C. 1998, Observations on Declining SPMD Sampling Rates for High Kow Compounds. Presented at the 19 Annual Meeting of Society of Envirorrmental Toxicology and Chemistry November 15, 2004 Charlotte, NC Abstract PWA173. 

Because SPMDs have high sampling rates (Rs s) for vapor phase contaminants, all SPMDs are assembled in an environmentally controlled room equipped with an activated carbon air filtration system for the removal of airborne contaminants. SPMDs of almost any length can be prepared after allowance of space for the molecular welds or heat seals (i.e., 2.5 cm for each end). However, different... 

When environmental conditions at an exposure site differ from those used for laboratory calibrations or when calibration data for an analyte are not available, at least one SPMD per site is spiked with PRCs. The type of compounds used for PRCs and their spiking levels were discussed earlier. PRC samples and standard SPMD samples (i.e., field-deployed SPMDs) differ only by the presence of the PRCs. Handling, processing and analysis are also identical. As implied above, the purpose of the PRC sample is to provide data for estimation of in situ sampling rates of target compounds. 

Based on the examination of analytical data from polychlorinated biphenyls (PCBs), OCPs and PAHs spiked into SPMDs, which have subsequently been subjected to the entire SPMD analytical procedure described herein, recoveries are generally >75% with good precision (i.e., C.Fs < 20%). Surprisingly, the C. Vis for the analysis of contaminants present in replicate SPMDs deployed contiguously at the same sites and treated identically during analysis are often equivalent to C.Fs of SPMD spikes. This observation suggests that the variability of analyte sampling rates of replicate SPMDs in the field is small and that the analytical methods used for field-deployed SPMDs are robust. 

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