Transfer of CO2, N2O and CH4 to butyl rubber (polyisobutylene) septa during storage

Greenhouse gases are more sampled than ever because of environmental interests. Gas samples are often inserted into vials with gas tight butyl rubber septa before concentration analysis. Little is known on the global transfer property of butyl rubber septa for CO2, N2O and CH4. Sorption kinetics were measured by injecting CO2, N2O or CH4 into glass vials with either one of four butyl rubber septa types and stored during 90 days. CO2 and N2O concentrations decreased during storage depending upon septa type and initial concentration, with the highest linear rate being 0.023 for CO2 and 0.0015 mg L(-3) day(-1) for N2O. When a low concentration was injected, CH4 concentration changes over time were small and did not differ between septa types. Sorption isotherms were measured using nine concentrations and stored during 45 days. CO2 sorption isotherms ranged from 0 to 3.7 x 10(-3) m(3) m(-2) and N2O from 0.3 to 1.4 x 10(-3) m(3) m(-2). Examples of errors associated with the use of these butyl rubber septa are given.     

Gas-phase sorption-desorption of propargyl bromide and 1,3-dichloropropene on plastic materials

The goal of this research was to provide information for choosing appropriate materials for studying gas-phase concentrations of propargyl bromide (3BP) and 1,3-dichloropropene (1,3-D) in laboratory experiments. Several materials were tested and found to sorb both gas-phase chemicals in the following order: stainless steel (SS) < Teflon polytetrafluoroethylene (PTFE-FEP) approximately flexible polyvinyl chloride (PVC) approximately acrylic < low-density polyethylene (PE) < vinyl approximately silicone < polyurethane foam (PUF). Sorption of SS was insignificant and PUF sorbed all the fumigant that was applied. For the other materials, linear sorption coefficients (Kd) for 3BP ranged from 3.0 cm3 g(-1) for PVC to 215 cm3 g(-1) for silicone. Freundlich sorption coefficients for 1,3-D ranged from 11.5 to 371 cm3 g(-1). First-order desorption rate constants in an open system ranged from 0.05 to 1.38 h(-1) for 3BP and from 0.07 to 1.73 h(-1) for 1,3-D. In a closed system, less than 2% of sorbed fumigant desorbed from vinyl while up to 99% desorbed from PVC within 24 h when equilibrated at the highest headspace concentration. Sorption of both fumigants was linearly related to the square root of time except for vinyl and silicone. This may indicate non-fickian diffusion of fumigant into the polymer matrix. Vinyl, silicone, PE, and PUF should be avoided for quantitative study of organic gases, except possibly as a trapping medium. Use of PTFE, PVC, and acrylic may require correction for sorption-desorption and diffusion.