Chieh-Heng Wang

Two-dimensional gas chromatographic analysis of ambient light hydrocarbons

Ambient level hydrocarbons lighter than C6 were analyzed by the Deans switch-modulated comprehensive two-dimensional gas chromatography (GC×GC) method with flame ionization detection (FID). A thermal desorption (TD) device built in-house connects the GC×GC system to pre-concentrate the target compounds at ambient levels prior to GC analysis. Because the conventional orthogonality based on polarity difference for normal GC×GC separation does not provide sufficient retention for the target compounds of extremely high volatility, the orthogonality of non-polar vs. adsorptive force was adopted instead. The system employed a 100% polydimethyl siloxane column serving as the first-dimension column to provide separation based on dispersive interaction, with a short PLOT column serving as the second-dimension column to provide the needed retention based on gas-solid adsorption interactions. The shortest possible length of the PLOT column was tested to minimize the modulation period (PM) and wraparound and, at the same time, to maintain the desired resolution. The tests led to the final optimal parameters of 1.1m for the PLOT column length, 9s for the PM, 0.013 for the modulation duty cycle (DC) and a modulation ratio (MR) of 3.7 with minimal wraparound. Important criteria for quality assurance of precision and linearity are reported. The low cost and ease of construction and operation make the in-house Deans switch TD-GC×GC-FID system practical and useful for the analysis of light hydrocarbons in urban or industrial environments.

Air quality impacted by local pollution sources and beyond – Using a prominent petro-industrial complex as a study case

The present study combines high-resolution measurements at various distances from a world-class gigantic petrochemical complex with model simulations to test a method to assess industrial emissions and their effect on local air quality. Due to the complexity in wind conditions which were highly seasonal, the dominant wind flow patterns in the coastal region of interest were classified into three types, namely northeast monsoonal (NEM) flows, southwest monsoonal (SEM) flows and local circulation (LC) based on six years of monitoring data. Sulfur dioxide (SO2) was chosen as an indicative pollutant for prominent industrial emissions. A high-density monitoring network of 12 air-quality stations distributed within a 20-km radius surrounding the petrochemical complex provided hourly measurements of SO2 and wind parameters. The SO2 emissions from major industrial sources registered by the monitoring network were then used to validate model simulations and to illustrate the transport of the SO2 plumes under the three typical wind patterns. It was found that the coupling of observations and modeling was able to successfully explain the transport of the industrial plumes. Although the petrochemical complex was seemingly the only major source to affect local air quality, multiple prominent sources from afar also played a significant role in local air quality. As a result, we found that a more complete and balanced assessment of the local air quality can be achieved only after taking into account the wind characteristics and emission factors of a much larger spatial scale than the initial (20 km by 20 km) study domain.

Characterization of thermal desorption with the Deans-switch technique in gas chromatographic analysis of volatile organic compounds.

This study presents a novel application based on the Deans-switch cutting technique to characterize the thermal-desorption (TD) properties for gas chromatographic (GC) analysis of ambient volatile organic compounds (VOCs). Flash-heating of the sorbent bed at high temperatures to desorb trapped VOCs to GC may easily produce severe asymmetric or tailing GC peaks affecting resolution and sensitivity if care is not taken to optimize the TD conditions. The TD peak without GC separation was first examined for the quality of the TD peak by analyzing a standard gas mixture from C2 to C12 at ppb level. The Deans switch was later applied in two different stages. First, it was used to cut the trailing tail of the TD peak, which, although significantly improved the GC peak symmetry, led to more loss of the higher boiling compounds than the low boiling ones, thus suggesting compound discrimination. Subsequently, the Deans switch was used to dissect the TD peak into six 30s slices in series, and an uneven distribution in composition between the slices were found. A progressive decrease in low boiling compounds and increase in higher boiling ones across the slices indicated severe inhomogeneity in the TD profile. This finding provided a clear evidence to answer the discrimination problem found with the tail cutting approach to improve peak symmetry. Through the use of the innovated slicing method based on the Deans-switch cutting technique, optimization of TD injection for highly resolved, symmetric and non-discriminated GC peaks can now be more quantitatively assessed and guided.