A Method for Concentrating and Determining Trace Organic Compounds in the Atmosphere


Book Description

Determination of subpart-per-billion (sub-ppb) levels of volatile organic compounds in the atmosphere by flame ionization gas chromatography requires sample sizes of at least several hundred milliters of air. Cryogenic methods of concentrating trace compounds before analysis have the disadvantage of also concentrating large amounts of water, a serious problem in gas-liquid chromatography. A simple method was developed for sample collection and concentration using porous polymer adsorbants with the unique properties of high capacity for retention of organic compounds and minimal capacity for retention of water. This technique was used to determine sub-ppb levels of volatile organic compounds in a typical rural atmosphere. Probable sources of these organic compounds were vehicle exhaust, biological processes, natural gas leaks, and industrial chemicals.










Analysis of Ambient Polar Volatile Organic Compounds Using Chemical Ionization-ion Trap Detector


Book Description

The current approach to measuring trace levels of volatile organic compounds (VOCs) in ambient air requires cryogenic trapping of the analytes, followed by thermal desorption and low-temperature refocusing onto a column for analysis by capillary gas chromatography/mass spectrometry (GC/MS). The approach has been successfully applied to nonpolar VOCs, but its use for more polar species has been complicated by the problems associated with the ambient water vapor collected with the VOCs. A promising technique for measuring polar VOCs is chemical ionization GC/MS (GC/CI-MS) in the quadrupole ion trap. The approach allows whole air samples to be taken since the water present in the air is used as the CI reagent gas. Water CI leads to appreciable intensities for the proton transfer agent H3O+, which produces intense pseudomolecular ions and class-specific fragmentation patterns for various low molecular weight polar compounds. Standard mixtures of polar species at low concentrations in humidified zero air were analyzed without a membrane dryer, using a cryogenic trap and CI-GC/MS with the ion trap detector in the full scan model.




Final Report on Proposal to Develop and Test a Membrane Sampling Module for the Extraction of Volatile Organic Compounds from Water


Book Description

A new technique is describe for the direct detection of volatile organic compounds in aqueous solutions at levels in the parts per trillion range. The sample is enriched in analyte in two consecutive stages, one utilizes a semi-permeable membrane interface and the other a jet separator. The analyte solution is sampled as it flows coaxially over a semi-permeable capillary membrane, the interior of which is continuously purged by helium. The permeate is pneumatically transported to the mass spectrometer via a jet separator, which is used to remove excess helium and water from the analyte vapor stream. Data are reported for an ion trap mass spectrometer used in conjunction with a conventional fixed-gap quartz jet separator. Typical analyte response times are 2-5 minutes and flow injection methods are used for sample delivery. Detection limits in the range 30 to parts per billion are observed for selected volatile organic compounds and the response is linear over 3 orders of magnitude. Details of the construction of the interface are provided.







Novel Applications of the Waterloo Membrane Sampler (WMS) in Volatile Organic Compound Sampling from Different Environmental Matrices


Book Description

The Waterloo Membrane Sampler (WMS) is a polydimethylsiloxane (PDMS)-based permeation passive sampler developed at the University of Waterloo. This sampler has found numerous applications in the sampling of volatile organic compounds (VOCs) from air and soil gas. In the presented thesis, studies were conducted to expand the WMS applicability to different environmental matrices. In the first part of this work, a modified version of the sampler, with a smaller area of the sampling surface, was calibrated towards seventeen VOCs listed as sources of concern in guidance documents for vapor intrusion. The calibration constant values obtained at different exposure periods demonstrated high reproducibility and independency of the exposure time. Furthermore, the application of the WMS for VOC sampling from groundwater was examined. This study involved seven VOCs considered as important groundwater pollutants. The performance of the sampler was examined at different concentration levels and for different exposure times. The effects of the sorbent type and bubble formation at the surface of the membrane on the sampling efficiency were evaluated in order to optimize the performance of the WMS. A hypothesis regarding the calibration constant values in water sampling compared to their values in air sampling was examined. The WMS demonstrated linear uptake of the targeted compounds over the studied periods of time and at different concentration levels. Very low detection limits were achieved for all studied compounds. The calibration constant values for the sampler towards the studied compounds were measured with a reasonable reproducibility. Nonetheless, the experimental values of the calibration constants in water sampling did not comply with the theory. Furthermore, a new method of bulk soil sampling was tested. In this approach, the soil sample is enclosed in a container along with the WMS placed in the headspace of the sample. The capability of the WMS to perform exhaustive extraction of volatile organic compounds trapped in the sample was tested in this case. Two compounds, TCE and PCE were used as model compounds to test the introduced method. The initial experiments involved sampling from spiked sand soil as the simplest scenario. The experimental setup was evaluated and modified accordingly to achieve the desired extraction. The effects of the exposure parameters on the extraction efficiency were examined through experimental design starting with extraction from sand followed by extraction from a soil with a high organic content. The three-factor factorial design used for this purpose included the three factors: temperature, water content, and exposure time. The results demonstrated high extraction efficiency achieved when sampling from sand and lower extraction efficiency when sampling from the soil with a high organic content. The recovery was enhanced to a large extent in the latter case at a higher temperature with very low detection limits. The results presented in this thesis indicate that the WMS can be a potential universal tool for sampling from all environmental matrices in vapor intrusion investigations.