Prediction of partition coefficients of organic compounds between SPME/PDMS and aqueous solution.

Polydimethylsiloxane (PDMS) is commonly used as the coated polymer in the solid phase microextraction (SPME) technique. In this study, the partition coefficients of organic compounds between SPME/PDMS and the aqueous solution were compiled from the literature sources. The correlation analysis for partition coefficients was conducted to interpret the effect of their physicochemical properties and descriptors on the partitioning process. The PDMS-water partition coefficients were significantly correlated to the polarizability of organic compounds (r = 0.977, p < 0.05). An empirical model, consisting of the polarizability, the molecular connectivity index, and an indicator variable, was developed to appropriately predict the partition coefficients of 61 organic compounds for the training set. The predictive ability of the empirical model was demonstrated by using it on a test set of 26 chemicals not included in the training set. The empirical model, applying the straightforward calculated molecular descriptors, for estimating the PDMS-water partition coefficient will contribute to the practical applications of the SPME technique.

Diffusion and solubility coefficients determined by permeation and immersion experiments for organic solvents in HDPE geomembrane.

The chemical resistance of eight organic solvents in high density polyethylene (HDPE) geomembrane has been investigated using the ASTM F739 permeation method and the immersion test at different temperatures. The diffusion of the experimental organic solvents in HDPE geomembrane was non-Fickian kinetic, and the solubility coefficients can be consistent with the solubility parameter theory. The diffusion coefficients and solubility coefficients determined by the ASTM F739 method were significantly correlated to the immersion tests (p<0.001). The steady state permeation rates also showed a good agreement between ASTM F739 and immersion experiments (r(2)=0.973, p<0.001). Using a one-dimensional diffusion equation based on Fick's second law, the diffusion and solubility coefficients obtained by immersion test resulted in over estimates of the ASTM F739 permeation results. The modeling results indicated that the diffusion and solubility coefficients should be obtained using ASTM F739 method which closely simulates the practical application of HDPE as barriers in the field.

Estimation of resistance of starch/polyvinyl alcohol blends to permeation by organic solvents.

The chemical resistance of chlorinated hydrocarbons in starch/polyvinyl alcohol (PVA) blends has been investigated using a permeation cell with an in-cell solid phase microextraction (SPME) sampling device. The chlorinated hydrocarbon with a large molecule size or lower polarity was found to be less permeable through the starch/PVA blends. The tensile strength and chemical resistance of chlorinated hydrocarbons decreased with an increase in the starch content of blends. For the starch/PVA blends, the solubility of chlorinated hydrocarbons was inversely proportional to their molecular weight, molar volume and log Kow. The diffusion coefficients and solubility of permeants were proportional to the content of starch in the starch/PVA blends. It is plausible that the blends will be inclined to the starch characteristics as the plasticizer (i.e. glycerin) disrupts the rigidity arrangements of the starch and PVA. The present work provides information on the extent of organic compound permeation through starch/PVA blends for the practical application.

Application of solid phase microextraction on dental composite resin analysis.

A direct immersion solid phase microextraction (DI-SPME) method was developed for the analysis of dentin monomers in saliva. Dentine monomers, such as triethylene glycol dimethacrylate (TEGDMA), urethane dimethacrylate (UDMA) and 2,2-bis-[4-(2-hydroxy-3-methacryloyloxypropoxy) phenyl]-propane (Bis-GMA), have a high molecular weight and a low vapor pressure. The polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber with a medium polarity was employed for DI-SPME, and 215 nm of detection wavelength was found to be optimum in the chromatogram of HPLC measurement. The calibration range for DI-SPME was 0.30-300 µg/mL with correlation coefficients (r) greater than 0.998 for each analyte. The DI-SPME method achieved good accuracy (recovery 96.1-101.2%) and precision (2.30-8.15% CV) for both intra- and inter-day assays of quality control samples for three target compounds. Method validation was performed on standards dissolved in blank saliva, and there was no significant difference (p>0.2) between the DI-SPME method and the liquid injection method. However, the detection limit of DI-SPME was as low as 0.03, 0.27 and 0.06 µg/mL for TEGDMA, UDMA and Bis-GMA, respectively. Real sample analyses were performed on commercial dentin products after curing for the leaching measurement. In summary, DI-SPME is a more sensitive method that requires less sample pretreatment procedures to measure the resin materials leached in saliva.

Assessment of skin exposure to N,N-dimethylformamide and methyl ethylketone through chemical protective gloves and decontamination of gloves for reuse purposes.

N,N-dimethylformamide (DMF) and methyl ethylketone (MEK) are the hazardous chemicals commonly used in the synthetic leather industries. Although chemical protective gloves provide adequate skin exposure protection to workers in these industries, there is currently no clear guideline or understanding with regard to the use duration of these gloves. In this study, the permeation of DMF/MEK mixture through neoprene gloves and the desorption of chemicals from contaminated gloves were conducted using the ASTM F739 cell. The acceptable use duration time of the gloves against DMF/MEK permeation was estimated by assuming a critical body burden of chemical exposure as a result of dermal absorption. In a re-exposure cycle of 5 days, decontamination of the gloves by aeration at 25°C was found to be inadequate in a reduction of breakthrough time as compared to a new unexposed glove. However, decontamination of the gloves by heating at 70 or 100°C showed that the protective coefficient of the exposed gloves had similar levels of resistance to DMF/MEK as that of new gloves. Implications of this study include an understanding of the use duration of neoprene gloves and proper decontamination of chemical protective gloves for reuse.

Modeling organic solvents permeation through protective gloves.

Several researchers have studied the diffusion of organic solvents through chemical protective gloves and have estimated the diffusion coefficients by using various models. In this study, permeation experiments of benzene, toluene, and styrene through nitrile and Neoprene gloves were conducted using the ASTM F-739 standard test method. The diffusion coefficients were estimated using several models from the literature. Using a one-dimensional diffusion equation based on Fick's second law and the estimated diffusion coefficients, the permeation concentrations were simulated and compared with the experimental results. The modeling results indicated that the solubility of the solvent in the glove materials obtained by immersion tests was not an appropriate boundary condition for organic solvent permeation through the polymer gloves. The modeling work of this study will assist industrial hygienists to assess exposure of chemicals to workers through the chemical protective gloves.