Phillip Walsh

Vacuum ultraviolet detector for gas chromatography

Analytical performance characteristics of a new vacuum ultraviolet (VUV) detector for gas chromatography (GC) are reported. GC-VUV was applied to hydrocarbons, fixed gases, polyaromatic hydrocarbons, fatty acids, pesticides, drugs, and estrogens. Applications were chosen to feature the sensitivity and universal detection capabilities of the VUV detector, especially for cases where mass spectrometry performance has been limited. Virtually all chemical species absorb and have unique gas phase absorption cross sections in the approximately 120-240 nm wavelength range monitored. Spectra are presented, along with the ability to use software for deconvolution of overlapping signals. Some comparisons with experimental synchrotron data and computed theoretical spectra show good agreement, although more work is needed on appropriate computational methods to match the simultaneous broadband electronic and vibronic excitation initiated by the deuterium lamp. Quantitative analysis is governed by Beer-Lambert Law relationships. Mass on-column detection limits reported for representatives of different classes of analytes ranged from 15 (benzene) to 246 pg (water). Linear range measured at peak absorption for benzene was 3-4 orders of magnitude. Importantly, where absorption cross sections are known for analytes, the VUV detector is capable of absolute determination (without calibration) of the number of molecules present in the flow cell in the absence of chemical interferences. This study sets the stage for application of GC-VUV technology across a wide breadth of research areas.

Gas chromatography-vacuum ultraviolet spectroscopy for analysis of fatty acid methyl esters.

A new vacuum ultraviolet (VUV) detector for gas chromatography was recently developed and applied to fatty acid methyl ester (FAME) analysis. VUV detection features full spectral acquisition in a wavelength range of 115-240nm, where virtually all chemical species absorb. VUV absorption spectra of 37 FAMEs, including saturated, monounsaturated, and polyunsaturated types were recorded. Unsaturated FAMEs show significantly different gas phase absorption profiles than saturated ones, and these classes can be easily distinguished with the VUV detector. Another advantage includes differentiating cis/trans-isomeric FAMEs (e.g. oleic acid methyl ester and linoleic acid methyl ester isomers) and the ability to use VUV data analysis software for deconvolution of co-eluting signals. As a universal detector, VUV also provides high specificity, sensitivity, and a fast data acquisition rate, making it a powerful tool for fatty acid screening when combined with gas chromatography. The fatty acid profile of several food oil samples (olive, canola, vegetable, corn, sunflower and peanut oils) were analyzed in this study to demonstrate applicability to real world samples.

Gas chromatography-vacuum ultraviolet spectroscopy for multiclass pesticide identification.

A new vacuum ultraviolet detector for gas chromatography was recently developed and applied to multiclass pesticide identification. VUV detection features full spectral acquisition in a wavelength range of 115-240nm, where virtually all chemical species absorb. VUV absorption spectra of 37 pesticides across different classes were recorded. These pesticides display rich gas phase absorption features across various classes. Even for isomeric compounds, such as hexachlorocyclohexane (HCH) isomers, the VUV absorption spectra are unique and can be easily differentiated. Also demonstrated is the ability to use VUV data analysis software for deconvolution of co-eluting signals. As a universal detector, VUV provides both qualitative and quantitative information. It offers high specificity, sensitivity (pg on-column detection limits), and a fast data acquisition rate, making it a powerful tool for multiclass pesticide screening when combined with gas chromatography.

Permanent gas analysis using gas chromatography with vacuum ultraviolet detection.

The analysis of complex mixtures of permanent gases consisting of low molecular weight hydrocarbons, inert gases, and toxic species plays an increasingly important role in todays economy. A new gas chromatography detector based on vacuum ultraviolet (VUV) spectroscopy (GC-VUV), which simultaneously collects full scan (115-240 nm) VUV and UV absorption of eluting analytes, was applied to analyze mixtures of permanent gases. Sample mixtures ranged from off-gassing of decomposing Li-ion and Li-metal batteries to natural gas samples and water samples taken from private wells in close proximity to unconventional natural gas extraction. Gas chromatography separations were performed with a porous layer open tubular column. Components such as C1-C5 linear and branched hydrocarbons, water, oxygen, and nitrogen were separated and detected in natural gas and the headspace of natural gas-contaminated water samples. Of interest for the transport of lithium batteries were the detection of flammable and toxic gases, such as methane, ethylene, chloromethane, dimethyl ether, 1,3-butadiene, CS2, and methylproprionate, among others. Featured is the capability for deconvolution of co-eluting signals from different analytes.

Analysis and deconvolution of dimethylnaphthalene isomers using gas chromatography vacuum ultraviolet spectroscopy and theoretical computations

An issue with most gas chromatographic detectors is their inability to deconvolve coeluting isomers. Dimethylnaphthalenes are a class of compounds that can be particularly difficult to speciate by gas chromatography - mass spectrometry analysis, because of their significant coelution and similar mass spectra. As an alternative, a vacuum ultraviolet spectroscopic detector paired with gas chromatography was used to study the systematic deconvolution of mixtures of coeluting isomers of dimethylnaphthalenes. Various ratio combinations of 75:25; 50:50; 25:75; 20:80; 10:90; 5:95; and 1:99 were prepared to test the accuracy, precision, and sensitivity of the detector for distinguishing overlapping isomers that had distinct, but very similar absorption spectra. It was found that, under reasonable injection conditions, all of the pairwise overlapping isomers tested could be deconvoluted up to nearly two orders of magnitude (up to 99:1) in relative abundance. These experimental deconvolution values were in agreement with theoretical covariance calculations performed for two of the dimethylnaphthalene isomers. Covariance calculations estimated high picogram detection limits for a minor isomer coeluting with low to mid-nanogram quantity of a more abundant isomer. Further characterization of the analytes was performed using density functional theory computations to compare theory with experimental measurements. Additionally, gas chromatography - vacuum ultraviolet spectroscopy was shown to be able to speciate dimethylnaphthalenes in jet and diesel fuel samples.

Determination of Hydrocarbon Group-Type of Diesel Fuels by Gas Chromatography with Vacuum Ultraviolet Detection

A GC-vacuum ultraviolet (UV) method to perform group-type separations of diesel range fuels was developed. The method relies on an ionic liquid column to separate diesel samples into saturates, mono-, di-, and polyaromatics by gas chromatography, with selective detection via vacuum UV absorption spectroscopy. Vacuum UV detection was necessary to solve a coelution between saturates and monoaromatics. The method was used to measure group-type composition of 10 oilsands-derived Synfuel light diesel samples, 3 Syncrude light gas oils, and 1 quality control sample. The gas chromatography (GC)-vacuum UV results for the Synfuel samples were similar (absolute % error of 0.8) to historical results from the supercritical fluid chromatography (SFC) analysis. For the light gas oils, discrepancies were noted between SFC results and GC-vacuum UV results; however, these samples are known to be challenging to quantify by SFC-flame ionization detector (FID) due to incomplete resolution between the saturate/monoaromatic and/or monoaromatic/diaromatic group types when applied to samples heavier than diesel (i.e., having a larger fraction of higher molecular weight species). The quality control sample also performed well when comparing both methods (absolute % error of 0.2) and the results agreed within error for saturates, mono- and polyaromatics.

Flow-modulated comprehensive two-dimensional gas chromatography combined with a vacuum ultraviolet detector for the analysis of complex mixtures

The present paper is focused on the use of a vacuum ultraviolet absorption spectrometer (VUV) for gas chromatography (GC), within the context of flow modulated comprehensive two-dimensional gas chromatography (FM GC×GC). The features of the VUV detector were evaluated through the analysis of petrochemical and fatty acids samples. Besides responding in a predictable fashion via Beers law principles, the detector provides additional spectroscopic information for qualitative analysis. Virtually all chemical species absorb and have unique gas phase absorption features in the 120-240nm wavelength range monitored. The VUV detector can acquire up to 90 full range absorption spectra per second, allowing its coupling with comprehensive two-dimensional gas chromatography. This recent form of detection can address specific limitations related to mass spectrometry (e.g., identification of isobaric and isomeric species with very similar mass spectra or labile chemical compounds), and it is also able to deconvolute co-eluting peaks. Moreover, it is possible to exploit a pseudo-absolute quantitation of analytes based on pre-recorded absorption cross-sections for target analytes, without the need for traditional calibration. Using this and the other features of the detector, particular attention was devoted to the suitability of the FM GC×GC-VUV system toward qualitative and quantitative analysis of bio-diesel fuel and different kinds of fatty acids. Satisfactory results were obtained in terms of tailing factor (1.1), asymmetry factor (1.1), and similarity (average value 97%), for the FAMEs mixtures analysis.

Pseudo-absolute quantitative analysis using gas chromatography - Vacuum ultraviolet spectroscopy - A tutorial

The vacuum ultraviolet detector (VUV) is a new non-destructive mass sensitive detector for gas chromatography that continuously and rapidly collects full wavelength range absorption between 120 and 240xa0nm. In addition to conventional methods of quantification (internal and external standard), gas chromatography - vacuum ultraviolet spectroscopy has the potential for pseudo-absolute quantification of analytes based on pre-recorded cross sections (well-defined absorptivity across the 120-240xa0nm wavelength range recorded by the detector) without the need for traditional calibration. The pseudo-absolute method was used in this research to experimentally evaluate the sources of sample loss and gain associated with sample introduction into a typical gas chromatograph. Standard samples of benzene and natural gas were used to assess precision and accuracy for the analysis of liquid and gaseous samples, respectively, based on the amount of analyte loaded on-column. Results indicate that injection volume, split ratio, and sampling times for splitless analysis can all contribute to inaccurate, yet precise sample introduction. For instance, an autosampler can very reproducibly inject a designated volume, but there are significant systematic errors (here, a consistently larger volume than that designated) in the actual volume introduced. The pseudo-absolute quantification capability of the vacuum ultraviolet detector provides a new means for carrying out system performance checks and potentially for solving challenging quantitative analytical problems. For practical purposes, an internal standardized approach to normalize systematic errors can be used to perform quantitative analysis with the pseudo-absolute method.

Gas chromatography-vacuum ultraviolet detection for classification and speciation of polychlorinated biphenyls in industrial mixtures☆

Polychlorinated biphenyls (PCBs) are a group of synthetic chlorinated compounds that have been widely used as dielectric fluids in capacitors and transformers. Due to their toxicity, persistence, and bioaccumulation in the food chain, PCBs are an environmental concern and among the most analyzed compounds in environmental analysis. The most common analytical methods for analysis of PCBs are based on gas chromatography-electron capture detection (GC-ECD) and gas chromatography-mass spectrometry (GC-MS). However, the number of possible congeners (209), similarities of physical and chemical properties, and complexity of sample matrices make it difficult to distinguish and accurately speciate PCB congeners using existing methods. This study presents a new method using gas chromatography with vacuum ultraviolet detection (GC-VUV), which offers absorption detection in the range of 120-240nm, where all chemical species have absorption. The VUV absorption spectra for all 209 PCB congeners were collected and shown to be differentiable. The capability of VUV data analysis software for deconvolution of co-eluting signals was also demonstrated. An automated time interval deconvolution (TID) procedure was applied to rapidly speciate individual PCBs, as well as classify commercial Aroclor mixtures based on their degree of chlorination. The data showed excellent agreement between the stated nominal and determined degrees of chlorination (less than 1% deviation for highly chlorinated mixtures). GC-VUV was verified to provide excellent specificity, high sensitivity (100-150pg limit of detection), and fast data acquisition for this application.

Impact of thin film metrology on the lithographic performance of 193-nm bottom antireflective coatings

The performance needs of a bottom antireflection coating (BARC) used in advanced optical lithography are extremely demanding, with reflectivities as low as 0.1% and even lower often required. BARC thickness and complex refractive index values (n = n + iκ) must be highly optimized, requiring accurate knowledge of the BARC, resist and substrate optical properties. In this paper, we have performed a theoretical analysis of the BARC optimization process with respect to the propagation of BARC n and κ measurement errors. For several realistic cases, specifications on the measurement accuracy of these optical parameters will be derived and the lithographic consequences of BARC metrology errors will be explored. Approaches to improving the measurement of BARC thickness and refractive index will be suggested.