Equilibrium samplers

More recently, Harner et al. (2003) coated ethylene vinyl acetate (EVA) onto glass (polymer coated glass [POG]) for use as fugacity sensors or equilibrium samplers of SVOCs in indoor and outdoor air. The EVA film fhickness was 1.1 and 2.4 qm depending on the application and as expected, SVOC sorption capacity and times to equilibrium were shown to be directly proportional to film thickness. The clearance capacity Ey volume of sample medium cleared of chemical) of a sorbent for an analyte is given by... 

Systematic attempts have been made to develop passive sampling systems that accumulate chemicals, and from which reliable exposure concentrations can be calculated. The passive samplers used in such systems are usually designed either as "kinetic samplers" or as "equilibrium samplers."... 

The concept of the equilibrium sampler is analogous to that of the octanol-water equilibrium partition coefficient (fQ,w) used since the 1970s to predict the potential for persistent nonpolar contaminants to concentrate in aquatic organisms [71]. The use of equilibrium-t) e passive samplers in the aquatic environment depends on the development of a sampler-water partition coefficient (fCs ) defined as the ratio of sampler to water concentration of the compound of interest at thermod)mamic equilibrium. The other key parameter determining the utility of an equilibrium-type passive sampler is the time taken to reach an approximate equilibrium condition. A range of approaches applied in developing equilibrium-t)q)e passive samplers include polyethylene or silicon sheets of various volume to surface area ratio [72] and solid-phase microextraction techniques [73]. 

Even when using LDPE and PP, the diffusive losses of most nonpolar solvents may be unacceptably large for A designs that exceeded 1 cm . This is especially true at higher exposure temperatures because both solute diffusion and polymer free volume increase with temperature (Comyn, 1985). Even when solvent losses were not excessive, uptake of HOCs by membrane-enclosed solvents appeared to become curvilinear well before thermodynamic equilibrium was approached. This phenomenon is likely due to the outward flux of sampler solvent with elevated HOC levels (relative to water), which appears to facilitate residue... 

Volume of water or air cleared ( v) by a specific sampler configuration at equilibrium. We use PCB congener 52 in diis example. 

If the aim of an investigator is to determine equilibrium concentrations in samplers, then the residence time (tm) is a logical parameter to compare among samplers. The tm is the mean length of time that a molecule spends in a passive sampling device, where solute exchange follows first-order kinetics. Residence time is given by... 

The principal implication of these studies for the accurate measurement of strong acids in gaseous and aerosol phases is that sampling must be performed in a way that does not disturb the equilibrium significantly in the process. This necessity has led to the development of the diffusion denuder sampler (61), which measures nitric acid after its removal to the walls of a... 

Automatic headspace samplers are available from manufacturers of gas chromatographs. These devices are based on the technique of sampling an amount of vapor above the sample itself. Samples are sealed, neat or in a suitable solvent, in containers, and hold at a preset temperature in a thermostatted liquid bath. The headspace vapor results as a partition equilibrium is established between the liquid or solid and the gaseous phase of the volatiles. As each sample is presented to the analyzer, the vessel is punctured and a portion of the headspace gas is withdrawn by a pneumatic injection technique and forced into the column. The main application for those samplers is in the routine analysis of low-boiling fractions in samples containing nonvolatile solids or high-boiling components. Some of the more popular applications today are ... 

The substance-specific kinetic constants, kx and k2, and partition coefficient Ksw (see Equations 3.1 and 3.2) can be determined in two ways. In theory, kinetic parameters characterizing the uptake of analytes can be estimated using semiempirical correlations employing mass transfer coefficients, physicochemical properties (mainly diffusivities and permeabilities in various media), and hydro-dynamic parameters.38 39 However, because of the complexity of the flow of water around passive sampling devices (usually nonstreamlined objects) during field exposures, it is difficult to estimate uptake parameters from first principles. In most cases, laboratory experiments are needed for the calibration of both equilibrium and kinetic samplers. 

Mazzella, N., J.-F. Dubemet, and F. Delmas. 2007. Determination of kinetic and equilibrium regimes in the operation of polar organic chemical integrative samplers application to the passive sampling of the polar herbicides in aquatic environments. J. Chromatogr. A 1154 42-51. 

Boyer and Probecker [191] determined organic solvents in several pharmaceutical forms using a Perkin-Elmer HS-6 headspace sampler. Typically, the samples were heated at 90°C for 10 min to establish equilibrium. Head-space samples were injected onto a Chromosorb 102 column. Ten injections of a mixed ethanol-acetone standard using methanol as the internal standard gave better precision than manual injections as measured by the relative standard deviation 1.63% and 2.48% for ethanol and acetone, respectively, using the sampler as compared to 4.77% and 3.93% by manual injection, respectively. Methods were reported for acetone and ethanol in dry forms such as tablets and microgranules, ethanol of crystallization in raw materials, and ethanol in syrups. Denaturants such as n-butanol and isopropanol in ethyl alcohol were determined using ethyl acetate as the internal standard. 

Figure 3-48. Bending motion and a sampler of potential energy functions. Top bending vibration of a linear triatomic molecule, where r is the instantaneous distance between the end atoms and re is the equilibrium distance of the linear configuration (r

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