Source Apportionment of Volatile Organic Compounds (VOCs) by Positive Matrix Factorization (PMF) supported by Model Simulation and Source Markers - Using Petrochemical Emissions as a Showcase.

This study demonstrates the use of positive matrix factorization (PMF) in a region with a major Petrochemical Complex, a prominent source of volatile organic compounds (VOCs), as a showcase of PMF applications. The PMF analysis fully exploited the quality and quantity of the observation data, sufficed by a cluster of 9 monitoring sites within a 20 km radius of the petro-complex. Each site provided continuous data of 54 speciated VOCs and meteorological variables. Wind characteristics were highly seasonal and played a decisive role in the source-receptor relationship, hence the dataset was divided into three sub-sets in accordance with the prevailing wind flows. A full year of real-time data were analyzed by PMF to resolve into various distinct source types including petrochemical, urban, evaporative, long-range air parcels, etc., with some sites receiving more petro-influence than others. To minimize subjectivity in the assignment of the PMF source factors, as commonly seen in some PMF works, this study attempted to solidify PMF results by supporting with two tools of spatially/temporally resolved air-quality model simulations and observation data. By exploiting the two supporting tools, the dynamic process of individual sources to a receptor were rationalized. Percent contributions from these sources to the receptor sites were calculated by summing over the occurrence of different source types. Interestingly, although the Petro-complex is the single largest local VOC source in the 20 km radius study domain, all monitoring sites in the region received far less influence from the Petro-complex than from other emission types within or outside the region, which together add up to more than 70% of the total VOC abundance.

Full-range analysis of ambient volatile organic compounds by a new trapping method and gas chromatography/mass spectrometry.

This study investigated the feasibility of analyzing a full range of ambient volatile organic compounds (VOCs) from C(3) to C(12) using gas chromatograph mass spectrometry (GC/MS) coupled with thermal desorption. Two columns were used: a PLOT column separated compounds lighter than C(6) and a DB-1 column separated C(6)-C(12) compounds. An innovative heart-cut technique based on the Deans switch was configured to combine the two column outflows at the ends of the columns before entering the MS. To prevent the resolved peaks from re-converging after combining, two techniques were attempted (hold-up vs. back-flush) to achieve the intended "delayed" elution of heavier components. Thus, the resulting chromatogram covering the full range of VOCs is a combination of two separate elutions, with the heavier section following the lighter section. With the hold-up method, band-broadening inevitably occurred for the delayed C(6)-C(7) DB-1 compounds while the light compounds eluted from the PLOT column. This broadening problem resulted in peak tailing that was largely alleviated by adding a re-focusing stage while the DB-1 compounds were back-flushed, and this modified technique is referred to as the back-flush method. With this modification, the separation of the C(6)-C(7) compounds improved dramatically, as revealed by the decrease in peak asymmetry (As) and increase in resolution. Linearity and precision for these peaks also improved, yielding R(2) and RSD values better than 0.9990 and 2.8%, respectively.

Mesoporous silicate MCM-48 as an enrichment medium for ambient volatile organic compound analysis.

This study investigated the sorption/desorption properties of MCM-48 and its applicability as a sorbent for on-line gas chromatographic analysis of ambient volatile organic compounds (VOCs). To establish a valid comparison, commercially available carbon sorbents were evaluated under similar analytical conditions. Two trapping temperatures of 30 degrees C and -20 degrees C, representing ambient and sub-ambient temperatures, were tested by trapping a full range of VOCs from C(2)-C(12). At ambient temperatures, due to the mesoporosity, the MCM-48 showed considerably limited trapping efficiency compared to microporous carbon sorbents on the highly volatile section of VOCs and only began to show effective trapping for compounds larger than C(7). Cooling to sub-ambient temperatures (e.g., -20 degrees C) extended the effective trapping down to C(4) VOCs, drastically increasing the applicability of MCM-48 as an in-line enrichment medium for gas chromatographic analysis of VOCs. The mesoporosity of MCM-48 also aided desorption. Much lower desorption temperatures (100-180 degrees C) were required for full desorption as compared to the temperatures (greater than 200 degrees C) required for carbon sorbents. Moreover, the easy desorption was accompanied by a low memory effect, as the large pores of MCM-48 can clean up more efficiently after desorption, with little residue left behind.

Construction of an automated gas chromatography/mass spectrometry system for the analysis of ambient volatile organic compounds with on-line internal standard calibration.

An automated sampling and enrichment apparatus coupled with a gas chromatography/mass spectrometry (GC/MS) technique was constructed for the analysis of ambient volatile organic compounds (VOCs). A sorbent trap was built within the system to perform on-line enrichment and thermal desorption of VOCs onto GC/MS. In order to improve analytical precision, calibration accuracy, and to safe-guard the long-term stability of this system, a mechanism to allow on-line internal standard (I.S.) addition to the air sample stream was configured within the sampling and enrichment apparatus. A sub-ppm (v/v) level standard gas mixture containing 1,4-fluorobenzene, chloropentafluorobenzene, 1-bromo-4-fluorobenzene was prepared from their pure forms. A minute amount of this I.S. gas was volumetrically mixed into the sample stream at the time of on-line enrichment of the air sample to compensate for measurement uncertainties. To assess the performance of this VOC GC/MS system, a gas mixture containing numerous VOCs at sub-ppb (v/v) level served as the ambient air sample. Various internal standard methods based on total ion count (TIC) and selective ion monitoring (SIM) modes were attempted to assess the improvement in analytical precision and accuracy. Precision was improved from 7-8% RSD without I.S. to 2-3% with I.S. for the 14 target VOCs. Uncertainties in the calibration curves were also improved with the adoption of I.S. by reducing the relative standard deviation of the slope (Sm%) by an average a factor of 4, and intercept (Sb%) by a factor of 2 for the 14 target VOCs.