Reagent Free Ion Chromatography
Lisa Lenehan, Mike Kinderman, Kannan Srinivasan, and Chris Pohl - Dionex Corporation

Dionex introduces Reagent-Free IC (RFIC) which redefines the way ion chromatography is performed. RFIC combines automated eluent generation, self-regenerating suppression, and continuously-regenerated traps for a true “Just Add Water” system that eliminates reagent preparation and guarantees day-to-day consistency and reliability. This presentation explores the theory and instrumentation of RFIC, and displays the obtainable benefits in chromatograms of both trace level anion and cation analyses.

Monitoring Cooling Waters For Corrosion And Scale Using Ion Chromatography
Lisa Lenehan, Maria Rey, and Beverly Newton - Dionex Corporation

A variety of techniques exist to monitor those components that can cause corrosion and scale build-up in cooling water systems. Dionex Ion Chromatography is one technique capable of measuring the presence of corrosion and scale-causing analytes at trace levels. This presentation focuses on the analytical methods used to determine anions, cations, organic acids and amine additives in process streams and cooling waters.

Chromeleon: an Adaptable Chromatography Management System
Matthew Neely, Andreas Becker, Lisa Lenehan, and Graham Webster - Dionex Corporation

We will demonstrate the advances in Chromeleon 6 Chromatography Data System to meet the changing analytical environment. New features such as trend plots, IC application templates, new third party drivers, and report columns in sequence make it a powerful tool for your GC, IC, and LC needs. The client/server architecture allows it to be expanded from a single instrument to your entire enterprise. Validation of your instruments becomes almost effortless with the new AutoQ automated qualification features

New Electrochemical Solid State Detector and Customized Detection Systems for Measurement of Low Sulfur Concentrations in Mineral Oil Products
Andreas Sterner, Rex Keel, Richard Cleveland - Analytik Jena USA, Inc.

Stricter limitations for petrochemical products require flexible and precise determination methods for accurate measurement results in lower detection limits. Comparison data of UV-Fluorescence detector with electrochemical solid state detector will be shown by using the multi EA 3100 analyzer from Analytik Jena AG. Both detectors were successively attached to the multi EA 3100 and different samples were run. Results will be presented that show the clients can now customize their own units. The multi EA 3100 can be customized with all different kinds of detectors for the detection of sulfur, nitrogen and chloride in liquid, solid and gaseous samples.

The Do's and Don'ts in the Analysis of Sulfur for Polyolefin Producers
Benjamin Biela, Roger Moore, Robert Benesch, Bruce Talbert and Tracey Jacksier - Air Liquide

A major issue facing polyolefin producers is the need to continuously improve the efficiency of their process. One solution is to monitor the level of sulfur species present in the feedstock streams before it reaches the catalyst. High levels of sulfur can decrease the catalyst life, product yields and consistency. Considerable progress by instrument manufacturers to lower detection limits of sulfur detectors to keep pace with decreasing specifications has been ongoing. However, detection limits are not the sole criteria. Problems associated with reliable delivery of the sulfur containing compounds must also be addressed. This study will examine the effects of sulfur on polyolefin process’ and issues relating to consistent delivery of sulfur containing species to the detector.

Improved Performance of ASTM Method D5769 for the Analysis of Aromatics in Gasoline by GC/MS
James D. McCurry - Agilent Technologies

ASTM method D5769 is designed for the complete analysis of aromatic hydrocarbons in gasoline using gas chromatography/mass spectrometry (GC/MS). One challenge with using this method is to analyze high concentrations components, such as toluene, along with lower levels of the other aromatic species. The new Agilent 5973Inert GC/MS provides linear dynamic response for all aromatic compounds in gasoline without the need for second-order calibration curves. The 5973Inert system also combines retention time locking (RTL) technology and Chemstation macros to make compound identification and system calibration easy and automated.

Novel Instrumental Techniques in Ambient Air Analysis
Andrew Tipler, Frank DeLorenzo, Zoe Grosser and Heidi Griffith - PerkinElmer LAS

A thermal desorption GC-MS system is described that employs novel technologies to enhance the performance of ambient air analysis: • A double dry-purge capability removes moisture from the adsorbed sample. • A fixed volume of internal standard is added to each tube prior to desorption to validate MS tuning and improve quantitative performance. • The MS quadrupole detector collects simultaneously both full scan and single ion monitoring data to provide optimum identification and detection limits respectively. The system was evaluated with standard US-EPA Air Toxics mixtures and real-life air samples. Examples of the chromatography and performance will be presented.

Determination of Estrogen Levels in a Simulated Spacecraft Wastewater Solution Using LC/MS
Leticia Vega - GB Tech, Carl Zhang - University of Houston-Clear Lake, Joe Hedrick - Agilent Technologies

There is an increasing level of concern in the scientific community regarding the presence and levels of natural and synthetic estrogens in the environment. In terrestrial systems, high concentrations of estrogenic compounds may lead to adverse health conditions in humans and wildlife. For water recovery systems used onboard spacecraft, the concern is multiplied due to the fact that the water will be in a constant state of reuse and therefore possible exposure is more pronounced. The goal of this study is to determine estrogen levels in several concentrated wastewater effluents using an LC/MS method. The identification of estrogen compounds in wastewater effluent will enable development of technology that removes estrogenic compounds in spacecraft water recovery systems.

Emission Rate Certification of Permeation Tubes Containing Hygroscopic Compounds
Danet M. Vrazel, Robin M. Chelette - Kin-Tek Laboratories, Inc.

The permeation tube industry relies on gravimetric weight loss for the accurate certification of calibration gas standards. By procedure, Teflon™ permeation tubes containing pure compound are weighed routinely to establish a stable emission rate based on weight loss over time. Tubes are held at a constant temperature with a slight flow of carrier gas to vent the permeating compound, and are certified traceable to N.I.S.T. Hygroscopic compounds challenge the current certification procedure because they absorb moisture from external sources and gain weight, ultimately resulting in questionable accuracy, longer certification time, and less emission rate stability. Nitric acid, sulfuric acid and n-methylpyrrolidinone (NMP) were studied using continuous weight loss measurement to determine weight change characteristics in extreme dry conditions and various levels of humidity. A comparison was made to the current certification procedure to characterize the linear trends of each compound and to establish a more accurate and efficient means of emission rate certification for hygroscopic compounds.

The Analysis Petroleum Product with Final Boiling Point of 700°C in 240 seconds By Using Fast Simulated Distillation Chromatography.
Joaquin Lubkowitz, Jimmy Coleman, Steve Elliott, Roberto Meneghini - Separation Systems, Inc., Robert Mustacich - RVM Scientific

Advances were made in column selection, temperatures selections in order to elute carbon 86 in 240 seconds. This opened the possibility to analyze lubricating oil bases with this methodology (ASTM D6352). This has been achieved by utilizing direct column heating with temperature program rates of 250°C/min to 350°C/min. The repeatability of 0.2-2.0°F is easily achieved in the range of Boiling point of 800°F-1200°F. Differences of the boiling point temperatures obtained with this technique and conventional oven programming was never larger than 0.7-1.5°F.

The Development of a Model for the Determination of Boiling Distribution of Blends Based on the Boiling Point Distribution of Blending Components as Determined by Simulated Distillation Chromatography.
Roberto Meneghini, Joaquin Lubkowitz - Separation Systems, Inc.

A model has been developed that utilizes the linear response properties of the Flame Ionization Detector so as to determine the boiling point distribution of blends of diesels, gas oil and crude oils based on the Simulated Distillation of the components of the blend. Gravimetric binary and ternary mixtures of heavy gas oil and crude oils were prepared and their boiling distribution analyzed by Simulated Distillation. Subsequently, the linear model was tested by analyzing the individual constituents of the blend by Simulated Distillation and blending the boiling points by utilizing the model so as to predict the boiling point distribution of the blends. Good agreement within 2-4°F were obtained by comparing the Simulated Distillation of the blends and the Simulated Distillation obtained by the model.

Stretching ASTM Method 4815 to the Lower Limit or How Low Can we really Go?
Steve Elliott, Roberto Meneghini, Joaquin Lubkowitz - Separation Systems, Inc. Separation Systems

Recent assessment of the environmental implications in the use of the C1-C5 oxygenates used in gasoline, has sent chromatographers to search for methodologies to analyze all of the oxygenates covered by the scope of ASTM D4815 in the range of 600-50ppm (V/V) in which lower limits are accepted gradually within the next 5 years. This study attempted to calibrate in the range of 50-1000ppm (V/V) by utilizing the ASTM 4815 hardware optimized for this range, which exceeds the limit defined in the scope of this method of 0.1 mass % for both ethers and alcohols. The implications of the changes and their effect on the repeatability and reproducibility of this method are discussed as well as alternative strategies to solve the problem.

High Speed Petroleum Microdistillation Analysis Using Silicon Microtube Technology
D.Sparks, T.Hubbard, A.Chimbayo - Company: Integrated Sensing Systems Inc

Microsystem technology has been utilized to develop a new fluidic density meter capable of testing microliter samples. This test sample volume requirement is 1000X to 3000X lower than that of conventional glass or metal tube density meters. Results taken with this meter from petroleum distillations, and refined petroleum products like gasoline, diesel fuel, motor oil and kerosene will be presented. Density data of various oils and lubricants versus temperature will be covered, as will comparisons to larger conventional meters. By coupling this new measurement technology with commercially available or custom minidistillation systems, a large increase in analysis speed and efficiency can be obtained.

Quantification and Characterization of Sulfur in Low-Sulfur Reformulated Gasolines by GC/ICP-MS
Joe Hedrick, Steve Wilbur, Emmett Soffey - Agilent Technologies

Reducing total sulfur in motor fuels has become a critical air pollution control goal worldwide. As countries mandate increasingly lower permissible levels of total sulfur in fuels, the environmental monitoring and fuel manufacturing industries have been forced to find more sensitive techniques for analysis. GC/ICP-MS has the capability to meet current and projected detection limits for both total sulfur in reformulated gasolines as well as individual sulfur species. Additionally, GC/ICP-MS can identify and quantify other volatile organometallic species in fuels. In this work, total sulfur quantification in reformulated gasoline using compound independent calibration and sulfur speciation are examined.

Online Monitoring Of VOCs In Cooling Towers Water
Amos Linenberg – INFICON, Inc.

Measurement of specific VOCs in cooling tower water is essential for compliance as well as protection of the cooling system operation from unexpected excess contaminations. Online methods can provide semi-specific analysis, with high susceptibility to water matrices, such as oils and turbidity. The alternative method is the use of laboratory analysis, which is not only a costly and cumbersome exercise, but also does not prove the results in time to take a preventive measure to avoid costly incidents. INFICON Inc., is manufacturing an online monitoring system, which analyses specific hydrocarbons in water online and provides the results at the site. The unattended system operates automatically and detects traces of these chemicals in water. The system is unaffected by any water matrix and there in no need for pretreatment, filtration or purification prior to the analysis. A number of these systems are already in use for online applications.

Low Bleed True 100% Methyl Silicone Capillary Columns for GC and GC/MS
Reginald Bartram,Robert T. Wiedemer, Scott E. Adams – Alltech Associates

Column bleed in gas chromatography is typified by an increase in detector signal that corresponds with increasing GC oven temperature. It is usually caused by the elution of 3-, 4-, 5-, and 6-ring cyclic siloxanes, which result from the fragmentation of the stationary phase and low molecular weight, unbonded polymer strands. New proprietary stationary phase synthesis techniques have been developed that produce a pure dimethylpolysiloxane phase that exhibits excellent inertness and extremely low bleed without the use of arylene/silphenylene chemistries. This results in a low bleed non-polar capillary column that provides true methyl silicone elution patterns. This poster will present information, applications, and performance data on Alltech's new AT-1ms capillary column.

A New GC Capillary Column Designed for High Temperature Analysis
Robert T. Wiedemer, Scott E. Adams, Reginald Bartram - Alltech Associates

Analysis of samples with a high molecular weight, or a wide range of molecular weights in a sample mixture, requires a high isothermal GC oven temperature or a temperature program of the GC oven. This may result in excess column bleed, which can cause problems with both quantitative and qualitative analysis. The AT-1ht GC capillary column is a high performance, low bleed column specifically designed for the analysis of samples containing high boiling compounds. The column is specially processed from a low bleed non-polar stationary phase and high temperature fused silica tubing that provides a maximum isothermal operating temperature limit of 380°C. The stationary phase is manufactured using proprietary synthesis techniques that ensure low column bleed and elution patterns identical to standard methyl silicone capillary columns. This column is especially suited for petroleum industry applications. This poster will present information, performance data and applications on Alltech's AT-1ht Capillary Column.

Isolation and Concentration of Phenols Compounds from Water by Solid Phase Extraction
Martin Fetner, Al Kaziunas - Applied Separations

Non-polar organic analytes are easily extracted from aqueous samples, but polar organic compounds like phenols are quite difficult to extract from water. In order to broaden the application of solid phase extraction to include the removal of polar organic molecules from aqueous samples, a new chemically modified polymeric resin was developed which overcomes the problems associated with using the extremely non-polar surfaces of C18 and polystyrene divinyl benzene resin (PS-DVB) beads. C18 bonded silica and PS-DVB resin beads were compared with ADVANTA, a new polymeric resin bead chemically modified with a polar functional group, in the removal of phenols and other polar organic analytes from water. The ADVANTA polymer is functionalized so that the beads were easily wetted with water and also able to easily retain polar organic compounds. Analysis showed 90% plus recoveries from most phenolic compounds.

The Rapid, Simultaneous Solvent Extraction of Six Soil Samples for Total Petroleum Hydrocarbons (TPH)
Martin Fetner, Al Kaziunas - Applied Separations

Environment laboratories are under increased pressure to reduce solvent consumption and improve laboratory productivity. The parallel processing of samples greatly increases throughput and laboratory productivity. A new, fully automated pressurized solvent extraction instrument, the fast PSE, was used to demonstrate increased laboratory productivity and reduced solvent consumption in the extraction of total petroleum hydrocarbons (TPH) from soil samples. Solvent is pumped into extraction cells containing the samples, then heated and pressurized. After a short extraction time, the extract is discharged to standard collection vials for clean-up or analysis. The parallel extraction of six (6) samples simultaneously was conducted on various environmental reference and "weathered" samples. TPH extraction reproducibility was evaluated by running the same samples simultaneously in six (6) extraction vessels, and the result were compared to other standard methods.

The Extraction of Additives and Monomers from Polymer Samples using Supercritical CO2
Martin Fetner, Al Kaziunas - Applied Separations

Supercritical fluids can easily swell polymer samples and rapidly dissolve and extract common additives and unreacted monomers and oligomers from the polymer matrix. This alternate technique to standard solvent extraction procedures reduces the use and disposal of hazardous solvents. The parallel supercritical CO2 extraction of various polymer samples for additives and oligomers was compared to standard techniques. Additives, including Irganox 1010, Irganox 1076 and Irafos 168 and various oligomers, were extracted from several polymers including polyethylene, polystyrene and polyethylene terephthate.

PANalytical's Annual XRF Users Group Meeting
PANalytical

Measuring Trace Metals by ICP-MS: - Controlling Interferences from Industrial and Environmental Samples
Gordon F. Wallace, Ph.D. - PerkinElmer Corporation

Industrial and environmental samples can contain high levels of major components which may seriously interfere with the accurate determination of trace elements. Matrix components such as carbon, chloride, and elevated levels of calcium and other metals can lead to serious positive interferences. Recent advances in ICP-MS technology, specifically reaction cell chemistry, allow the reduction or elimination of these types of interferences. Applications for seawater, samples of high metal content, and samples having high carbon content will be discussed.

Precision of Gas Chromatographic Replacements of D86
Gerben de Jonge, Gertjan Schaatsbergen - AC Analytical Controls

The AC 8612 and 8634 applications calculate D86 data for samples class 0 through 4 from gas chromatographic analysis. The AC 8634 application is based on a method that will be included in ASTM D 2887. The AC 8612 application is based on the fugacity film model. This presentation demonstrates results from an already substantial installed base, as well as from a field study where the gas chromatographic analyses have been run in parallel to the D86 analysis. Results are shown in terms of superior repeatability and long-term stability. Also the comparison between D86 and gas chromatographic data is demonstrated.

The Analysis of traces Oxygenates - OxyTracer
Gerben de Jonge, Gertjan Schaatsbergen - AC Analytical Controls

The analysis of traces of oxygenated compounds in various matrices is becoming increasingly important. Standard methodology for oxygenates analyses is not sufficient to reach the lower detection limits required nowadays. AC has developed the OxyTracer, an analyser based on Deans technology. This technology allows the user to cut the oxygenates from the matrix on a pre column and analyse this cut on an analysis column, separating the oxygenates from the remaining matrix. Greatest advantage of this set up is that the analysis becomes independent of the matrix. Examples of analyses in naphtha, gasoline, crude and condensate are shown.

Method 18: A Laboratory Perspective
Wade Bontempo - Air Toxics Limited

Method 18, which is found in 40 CFR Part 60 Appendix A, is a method used to determine VOCs in source streams by gas chromatography. Method 18 is the required method for flare testing found in 40 CFR 60.18 as well as being a cited method in TCEQ Chapter 115, Subchapter H. This presentation will cover several aspects of Method 18 from a laboratory perspective including the preanalytical survey, bag recovery study, audit samples, tedlar bags vs. canisters, and other quality control requirements.

Speciated Characterization of HRVOCs, VOCs, as well as Total Strippable VOCs in Cooling Tower Monitoring
Wade Bontempo - Air Toxics Limited

A method for stripping volatile organics from cooling tower water was developed in the early 1970s by the El Paso Products Company. The effluent from the dynamic flow-through sampling system can either by continuously monitored for total VOCs using a flame ionization detector, or collected in a Summa canister for a speciated VOC analysis. This presentation will cover the speciated analysis of HRVOCs, VOCs, as well as total strippable VOCs conducted by Method TO-14A.

Comprehensive Two-Dimensional GC Symposium Chemometric Analysis of GC x GC Data
Robert E. Synovec, Center for Process Analytical Chemistry (CPAC), Department of Chemistry, Box 351700, University of Washington, Seattle, WA, 98195-1700, U.S.A. synovec@chem.washington.edu

Two-dimensional comprehensive gas chromatography (GC x GC) is a powerful chemical separation technique. Extraction of useful information from GC x GC/FID data using chemometric methods will be reported, such as the generalized rank annihilation method (GRAM), tri-linear partial least squares (tri-PLS) and principal component analysis (PCA). More recently, the development and implementation of time-of-flight mass spectrometry (TOFMS) with GC x GC has raised more challenges for data analysis. Advances in chemometric analysis of GC x GC/TOFMS data will be reported. The chemometric methodology utilizes tri-linear decomposition (TLD) followed by PARAFAC to obtain excellent deconvolution results under conditions of severe chromatographic overlap (resolution less than 0.1) and very similar mass spectra. Basic principles and several examples will be presented.

Comprehensive Two-Dimensional GC Symposium Visualization, Analysis, And Processing Of GCxGC – TOF MS DATA
Visweswara Rao Kottapallia, Stephen E. Reichenbacha, Mingtian Nia, Arvind Visvanathana - aComputer Science and Engineering Department, University of Nebraska-Lincoln, Lincoln, NE 68588-0115, USA reich@sioux.unl.edu

Comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GCxGC – TOF MS) produces large data sets that pose processing challenges. The column bleed, GC septum, and unresolved neighboring components often contaminate the GCxGC – TOF MS data. These extraneous contributions, called background, distort the relative intensities in the mass spectra. Using the distorted mass spectra to identify the compounds in a mass spectral library leads to missing and incorrect identifications. So, removing background from the contaminated mass spectra is important. To reduce the size of data sets, GCxGC – TOF MS data may be stored in a sparse format with only a few of the highest intensity values in each mass spectrum. Discarding some of the less significant intensity values in each mass spectrum complicates the process of background estimation. This work develops and evaluates an algorithm to remove background from sparse GCxGC – TOF MS data. The algorithm estimates and subtracts background from all the ion images of GCxGC – TOF MS data, producing ion images and total ion count (TIC) in which the peaks rise above a near-zero mean background. The experiments evaluate three alternative background estimation methods: most-recent background value, oldest background value replacement, and largest background value replacement. The performance of the three background estimation methods is evaluated using library search results for mass spectra of aromatic compounds in a gasoline sample. Removing background from the mass spectra improved the library search factors: rank, match factor, reverse match factor, and probability. Though all three methods improved the library search results, the oldest background value replacement algorithm produced better results in more cases.

Comprehensive Two-Dimensional GC Symposium Large Sample Volume Splitless Injection - Comprehensive Two Dimensional Gas Cromatography
Daniela Cavagnino, Paolo Magni, Giacinto Zilioli and Sorin Trestianu Thermo Electron, Str Rivoltana, 20090 Rodano(Milan) Italy

The new Large Sample Volume Splitless Injection technique has been recently proposed [1, 2] as a simple, reliable and robust technique for injecting larger sample volumes up to 50uL. This technique is based on the Concurrent Solvent Recondensation effect which makes the whole process to be fully self-regulated. The facility of the operations makes this LVI technique suitable to be used with the comprehensive two-dimensional GC as a powerful tool for the analysis of traces in complex matrices. The very high separation power of the comprehensive two-dimensional GC allows to separate target compounds from the matrix interferences even when large sample volumes are injected. The experiments were performed using a special version of Finnigan TRACE GC Ultra (TRACE 2DGC) provided with a dual CO2 jet modulator (as proposed by J. Beens et al.[3]), operating in a broad range of temperatures up to 350°C. The liquid CO2 is supplied alternatively by two jets as a laminar flow capable of cooling down a length of about 4mm of the second dimension column and ensuring second dimension peak widths of about 100ms. The heating step is obtained thanks to the hot circulating air of the GC oven when the coolant flow is interrupted. Besides, a dedicated electronic is implemented into the TRACE 2DGC for the timing control of the modulator. A dedicated ChromCard based software (HyperChromä) was used to acquire and manage the generated data set, visualize them as colour plots or 3D view and perform peaks integration for qualitative and quantitative analysis. The detection of semi-volatile pollutants at low ppb levels in complex matrices have been reported to illustrate how it is possible to attain such low detection limits even with a non-selective detector as the FID. Moreover, thanks to the peak compression achieved during the modulation step, an improved detectability is reached. Very good repeatability data have been obtained to confirm the reliability of the system. Quantitative data are provided illustrating the capabilities of the software used for the data handling. In particular, high frequency data acquisition, generation of colour plot, peaks identification, calibration and quantitation are performed automatically by the data system, making the data handling an easier task. Reference [1] P.Magni, T.Porzano, Proc. 25th Int. Symp. On Capillary Chromatography, Riva del Garda, 2002 [2] P.Magni, T.Porzano, in publication [3] J. Beens, M. Adahchour, R. Vreuls, K. van Altena, U. Brinkman, J. Chromatogr. A, 919 (2001) 127-132

Comprehensive Two-Dimensional GC Symposium Characterization of Maleic Anhydride Grafted Polyethylene by GCxGC/TOF MS
Bruce Gerhart, Kefu Sun, Bill Winniford, The Dow Chemical Company, USA Tincuta Veriotti and Jay Hardee, LECO Corporation, MI, USA. Bgerhart@dow.com

Pyrolysis comprehensive two-dimensional GC coupled with time of flight MS (PyGCxGC/TOFMS) is a new analytical tool to characterize polymers by separating polar fragments from non-polar matrix, grouping fragments on a contour map and identifying fragments by TOF MS to give structural information on polymers. Maleic anhydride grafted polyethylenes were pyrolyzed at high temperature into fragments. Polar maleic anhydride is well separated from the non-polar matrix by GCXGC and identified by TOF MS. Compared to traditional PyGC/MS, PyGCxGC/TOFMS improves separations of fragments and is more sensitive. A series of maleic anhydride related fragments are found by TOFMS and will be discussed.

Comprehensive Two-Dimensional GC Symposium A New Data Analysis Tool For Two-Dimensional Comprehensive Gas Chromatography-Time-Of-Flight Mass Spectrometry (GCXGC-TOFMS)
Ralf ZIMMERMANN1,2,3, Werner WELTHAGEN1,2, Jürgen SCHNELLE-KREIS13, 1GSF – Forschungszentrum für Umwelt und Gesundheit, Institut für Ökologische Chemie, 85764 Neuherberg, Germany, 2Universität Augsburg, Institut für Physik, 86159 Augsburg, Germany, 3BIfA - Bayerisches Institut für Umweltforschung und –technik GmbH, Augsburg, Germany ralf.zimmermann@gsf.de

Two-dimensional comprehensive gas chromatography (GCxGC) with thermal modulation represents a novel and powerful technique for gas chromatographic separation of a large amount of volatile (VC) and semi-volatile compounds (SVOC) from highly complex mixtures. From particulate matter samples, several thousands of individual peaks can be chromatographically resolved. The coupling of GCxGC with a fast mass spectrometric detection (TOFMS with EI ionisation) now enables identification or at least classification of a considerable fraction of the chromatographically resolved compounds. First applications of GCxGC-TOFMS on ambient particulate matter are presented. A PC-based data analyis tool has been devloped [1]. This tool uses characteristic MS-fragmentation pattern information as well as the information on two-dimensional retention times for classification of peaks into “substance classes”. The principle of the classification routine will be demonstated using a real-life aerosol sample. [1] W. Welthagen, J. Schnelle-Kreis, R. Zimmermann, J. Chromatography A (2003) in press

Comprehensive Two-Dimensional GC Symposium Experimental Considerations of GCxGC
Bill Winniford, Kefu Sun, James Griffith, Shayne Green and Matthias Pursch, The Dow Chemical Company, Texas, USA Bwinniford@dow.com

Compared to regular one-dimensional GC, comprehensive two-dimensional GC (GCxGC) has more experimental conditions to consider, such as GCxGC column configuration and modulation period. Generally, a 0.25 mm or 0.32 mm ID column is used as the first dimensional column and a 0.10 mm ID column is used as the second dimensional column. The GC system often equipped with an electronic pressure control (EPC) valve. A new column configuration method will be presented to set up the EPC valve for a combination of two different dimension columns to achieve a required flow rate. A theoretical analysis of selection of column dimensions and carrier gas types will be discussed.

Comprehensive Two-Dimensional GC Symposium Quantification of GCxGC Analysis
Kefu Sun, Bill Winniford, James Griffith, Shayne Green, Bruce Gerhart and Matthias Pursch, The Dow Chemical Company, Texas, USA Ksun@dow.com

The GCxGC data is displayed in a different way than one-dimensional GC. Generally, one displays three-dimensional GCxGC data in a contour plot. For quantification in GCxGC, correct integration of peak volumes is still a challenge since GCxGC data are more complicated. Integration of GCxGC peaks is evaluated by two methods: using a standard GC integration program summing contributions from second dimension chromatograms and a new GCxGC integration program that calculates peak volume. Consistent results are obtained using both programs for well-separated GCxGC peaks with relative differences for individual peak ranging from 0.04% to 1.6%. Results are also shown for more difficult cases where peaks are not completely resolved by GCxGC.

Comprehensive Two-Dimensional GC Symposium Prediction of GCxGC Separations Through The Use Of Retention Index Data
J.-M. D. Dimandja, Department of Chemistry, Spelman College 350 Spelman Lane, SW, Box 279, Atlanta, GA 30314 jdimandja@spelman.edu

The selection of primary and secondary columns in GCxGC is based more on empirical knowledge than on a formalized process. A method is reported that makes use of conventional one-dimensional GC retention index data for the compounds of interest in order to generate simulated GCxGC chromatograms. The primary column retention is simply predicted by the retention index of the compound on that stationary phase. The secondary column retention is obtained by the retention index difference between the secondary column and primary column as an estimation of the specific contribution of the secondary stationary phase to the separation. The utility of the predictive model will be demonstrated for a model mixture on several different column-set combinations, and results will be compared to actual GCxGC runs.

Comprehensive Two-Dimensional GC Symposium Use of Agilent Mass Selective Detector with Comprehensive Two-Dimensional GC to Characterize Polymers
James Griffith, Kefu Sun and Bill Winniford, The Dow Chemical Company, Texas, USA jfgriffith2@dow.com

Comprehensive two-dimensional GC (GCxGC) as an emerging technology generates a significant interest in chromatographic community. However, sharp GCxGC peaks, typically 100 ms peak width, require a fast scan mass spectrometer to acquire high quality mass spectra, such as time of flight mass spectrometer (TOFMS). Most R&D labs do not own TOFMS, which limits GCxGC applications for unknown samples. This presentation will discuss experimental considerations in use of an Agilent MSD and Zoex thermal modulator for MS identification. Applications of characterization of polymers and determination of additives by GCxGC/MSD will be presented.

Comprehensive Two-Dimensional GC Symposium Determination of Additives in Competitive Products Using Comprehensive Two-Dimensional Gas Chromatography
Shayne Green, Kefu Sun, Bruce Gerhart, and Bill Winniford, The Dow Chemical Company, Texas, USA Lsgreen@dow.com

Determination of polymer additives in competitive products is tedious and time consuming. In competitive analysis, samples must be prepared and analyzed using many different analytical methods. In some situations, the additives may not be identified because of loss of the additive during sample preparations or analyses. A procedure has been developed using pyrolysis comprehensive two-dimensional gas chromatography (Py-GCxGC) for identification of additives. In GCxGC there is a significant improvement in selectivity and detectability, which allows for identification of additives in complex pyrograms. The technology and problem solving capabilities of pyrolysis GCxGC in competitive additives analysis will be presented.

Comprehensive Two-Dimensional GC Symposium Choosing an Appropriate Second-Dimension Column for Comprehensive Two-Dimensional Gas Chromatography (GCxGC)
James Harynuk, Tadeusz Gorecki (University of Waterloo), Jaap de Zeeuw, (Varian Inc.) jharynuk@uwaterloo.ca

GCxGC is a separation technique that is receiving much attention. The technique couples two different GC columns with an interface that samples the effluent from the primary column and launches the fractions onto the secondary column for another separation. As the second dimension column must perform its separation in only a few seconds, 100 µm columns are often used in this dimension. These narrow columns can be easily overloaded, degrading the separation. A series of second dimension columns of varying internal diameters were tested to determine the actual effects of overloading on the second-dimension separation space.

Comprehensive Two-Dimensional GC Symposium A Pulsed Flow Modulator for Comprehensive Two-Dimensional Gas Chromatography (GCxGC)
Huamin Cai* and Stanley D. Stearns, VICI Valco Instruments Co. Inc. USA Cai@vici.com

Different modulators have been used for comprehensive two-dimensional GCxGC separation. They can be roughly divided into three types - (1) the mechanical valve switch modulator, (2) the thermal heater modulator that includes a resistance heater and heated sweeper, and (3) the thermal cryogenic modulator that includes a jacked tubing trap, a linearly movable trap, and a jet trap. All these modulators use the full modulation method and have advantages and disadvantages. We have developed a new pulsed flow modulator, which differs from all the above modulators in that it uses a pulsed carrier gas flow introduced between the primary and secondary column to create the modulation signal, and it uses a partial modulation method. The modulator has the following advantages: (1) it can get the primary signal and the 2D signal simultaneously, so it can utilize the higher power of the primary separation; (2) the device is simple, inexpensive, and durable, and has the potential to be used in a portable GC; (3) the sample does not pass through any valves or other devices between the column connections, eliminating the problems of carry over, condensation, and peak broadening; and (4) there is no oven temperature limit for the modulator, since it doesn't involve any mechanical devices inside the oven.

Comprehensive Two-Dimensional GC Symposium Archiving and Reporting Formats for Two-Dimensional Gas Chromatography
Arvind Visvanathan, Stephen E. Reichenbach, Mingtian Ni, Visweswara Rao Kottapalli Department of Computer Science & Engineering, University of Nebraska, Lincoln NE 68588, USA. EMail: {avisvan | reich | mni | viskott}@cse.unl.edu reich@sioux.unl.edu

Comprehensive two-dimensional gas chromatography (GCxGC) is a new technology for chemical separation that provides an order-of-magnitude increase in separation capacity over traditional gas chromatography. In GCxGC two independent separations are applied to the entire sample. Co-elution is reduced by a great extent in GCxGC as compared to traditional one dimensional gas chromatography. In a GCxGC chromatogram, unlike conventional onedimensional gas chromatography, the compound classes can be clearly observed. GCxGC allows better correction for hardware artifacts such as column bleed. With its order-of-magnitude increase in separation capacity, GCxGC generates data in significantly larger quantity and with significantly greater complexity than traditional one dimensional gas chromatography. GCxGC creates a greater demand for digital storage and archiving GCxGC images. There are many archiving methods, each of which has its own limitations. The shortcomings of the existing file formats motivate a need for a new file format that is more generic and extensible. This paper proposes the following solutions: · An eXtensible Markup Language (XML) format for archiving GCxGC data. · A hierarchical XML-based project management scheme to store groups of related GCxGC images. · Enhancements of existing standard reporting methods that take advantage of the greater separation power in GCxGC, including an XML file format for archiving GCxGC reports. XML has important characteristics for GCxGC archiving and reporting. XML is an emerging, open, cross-disciplinary standard. XML is a hierarchical tagged format, extensible to future changes. XML documents can be validated using methods such as Document Type Definitions and XML Schemas. XML documents can be presented as Hyper Text Markup Language (HTML) when accompanied with eXtensible Stylesheet Language Transformations (XSLT).

Comprehensive Two-Dimensional GC Symposium ASTM Method D5880, Aromatics in Gasoline, by GC x GC
Edward B. Ledford, Jr, Joel R. Termaat, and Chris A. Billesbach, Zoex Corporation, Lincoln, NE - Stephen E. Reichenbach, Arvind Visvanathan, Visveswara Rao Kottapalli, and Mingtian Ni ,University of Nebraska, Lincoln, NE ed@zoex.com

GC x GC is a well established research technique, but has not yet proven its value as a routine production analytical technique suitable for analytical service laboratories, or for routine industrial chemical analysis. As a result of new software developments, it is clear that GC x GC is indeed suitable for routine analytical applications. Examples are analysis for aromatics in gasoline based upon ASTM method D5880, and boiling point analysis for petroleum products based upon ASTM method D2887. It is found that a single GC x GC instrument can perform both ASTM methods with no physical changes to the instrument, and that modern software permits almost effortless generation of ASTM compliant reports. Moreover, the GC x GC approach to these classical analyses permits them to be extended. ASTM D5880, for example, can be extended to the diesel range. ASTM D2887 can be extended to facile separation of aromatic and non-aromatic compound classes, and boiling curves for both classes can be generated in addition to total boiling curve. The ease of analytical workup together with the simplicity of the GC x GC apparatus bode well for industrial scale, routine chemical analysis by GC x GC.

Comprehensive Two-Dimensional GC Symposium Differential Flow GCxGC Without Diaphragm Valves: A Simple and Robust Way to Produce Two-Dimensional Separations
John V. Seeley, Russell LaClair, and Pedro A. Bueno, Jr. Department of Chemistry, Oakland University, Rochester, MI 48309, USA seeley@oakland.edu

A simple flow-switching device has been developed that allows differential flow modulation GC x GC separations to be produced without a diaphragm valve. The device is assembled from tubing, four tee unions, and a solenoid valve. The solenoid valve is located outside the oven of the gas chromatograph and does not come in contact with the sample components. Secondary peaks with widths less than 100 ms are produced when operating in GC x 2GC mode with a 2.0 s modulation period. This modulation technique has no inherent temperature restrictions and is capable of passing 100% of the primary column effluent to the secondary column(s). The efficacy of this approach is demonstrated through the analysis of a variety of complex mixtures including gasoline, diesel fuel, and the volatile organic compounds found in the atmosphere.

Determination of Trace Water in Pure Helium by using On Column Metal Tubing as a Concentrator and a Pulsed Discharge Detector (PDD)
Stanley D. Stearns, Sunsanee Sutippantupat* and Huamin Cai - VICI Valco Instruments Co. Inc. USA

Undesirable trace water present in pure helium gas can cause inaccurate analytical results, especially in gas chromatograhy (GC), which often uses helium as a carrier. This problem has come to the attention of several researchers, but none of the standard methods proposed can detect extremely low level water concentrations in pure gases. To solve this problem, we have developed a new technique to monitor ppb-level water in helium gas by using a short metal tube connected between the GC column and the helium source. The technique is based on the idea that water can be absorbed onto the active internal surface of the metal tube and be desorbed by heat. After the metal surface is activated by electrical resistance heat, it absorbs the water at a specific time interval, finally releasing the absorbed water when the metal tube is heated again. The amount of water present can be determined with the pulsed discharge detector (PDD). This technique is quite simple and offers a potential solution for detecting extremely low level water concentrations in purified grade helium. Moreover, this technique could be applied to detect ppb-level water in other gases, such as N2 or Ar.

Improved Performance from Packed GC Columns Used for the Analysis of Natural Gas and Natural Gas Liquids in Reference to GPA and ASTM Methods
R.B. George, L.M. Sidisky, M.V. Robillard, M.R. McCoy - Supelco/Sigma Aldrich Supelco Inc.

Packed GC columns continue to be used in valved-GC configurations for the analysis of natural gas and natural gas liquids as described in Gas Processors Association (GPA) Methods 2261, 2177 and American Society for Testing and Materials (ASTM) Test Method 2597. Column manufacturing procedures have been optimized resulting in column sets that provide highly reproducible analyses. Tests using commercial reference gas standards show retention time and individual component peak area variation from multiple column sets not exceeding 2% rsd. Chromatograms demonstrating column performance, analysis times and critical separations according to the GPA methods are shown with statistical analysis of results.

Guidelines for the Selection of PLOT Columns for Petrochemical/ Chemical Applications
W.R. Betz, M.J. Keeler, and L.M. Sidisky - Supelco/ Sigma Aldrich

Carbons, porous polymers, and other adsorbents have been used for decades for Gas-Solid Chromatographic separations. The choice of adsorbent perties (physical characteristics and surface chemistry) depends on the properties of the analytes to be separated. The evolution of GSC to incorporate these adsorbents into Porous Layer Open Tubular columns (PLOT columns) with relatively small diameters has considerably improved resolution for key analytes requiring GSC for effective chromatographic separations. Fused silica PLOT columns have been coated with carbon molecular sieves, zeolite molecular sieves, porous polymers, and activated alumina adsorbents. Each of these adsorbents offers a unique selectivity for the separation of petrochemical and chemical samples. We will demonstrate the selectivity of the various PLOT columns with a variety of petrochemical samples and provide guidelines for the appropriate PLOT column selection based on the sample type.

Fast GC Using 100m ID Capillary Columns
L.M. Sidisky, K.E. Stenerson, J.L. Desorcie, G.A. Baney - Supelco/ Sigma Aldrich

Speed of analysis has become an important parameter in many modern laboratories, as analysts look for faster methods to improve sample throughput. Approaches to improve the speed of analysis include shorter capillary columns, decreased column internal diameter, thinner stationary phase films, higher carrier gas linear velocities, and faster oven temperature programming rates. Many times, analysts change only one of these parameters and the change produces a loss of sample resolution. Our focus is on using 100m ID capillary columns, in combination with higher carrier gas linear velocities and fast temperature programming rates. This reduces analysis time, while maintaining sample resolution. Theoretical aspects of the performance of 100m ID columns is presented, with a series of complex petrochemical, food & beverage and environmental applications. Applications show use of 100m ID columns with changes in operating parameters, reducing analysis times, and maintaining sample resolution, compared to standard dimension capillary columns.

Getting Started with Solid Phase Microextraction (SPME)
L.M. Sidisky, M.V. Robillard, R.E.Shirey - Supelco Inc

Solid Phase Microextraction (SPME) has rapidly become a fast, cost-effective solvent-less approach to sample preparation. It is particularly useful for methods that have relied on headspace analysis and liquid-liquid extraction for sample preparation. The technique is often used for the extraction of volatile and semi-volatile analytes from aqueous and solid materials. This seminar will provide a brief background on the principles of SPME and will then lead into guidance on selecting the proper SPME fiber chemistry selection for your application. Tips on "getting started" using SPME will be provided to assist new users in being successful with the technique on the first attempt. Emphasis will be placed on petrochemical and environmental applications.

Static Headspace Analysis for Characterization of Petroleum and Petroleum Products
Michael Markelov,Olga Bershevits - ACS Labs

The major advantage of static headspace analysis is its ability to introduce in Gas Chromatograph only those constituents of the matrix that can be chromatographed , while leaving behind heavy non-volatile species. The determination of chlorinated solvents in crude, direct analysis of soils for the presence of hydrocarbons, determination of volatile constituents in heavy oils are just a few examples that will be covered in this presentation. The paper will also address the challenges of quantification with static headspace analysis. It will also show several ways of determination of partition coefficients for many chemicals in real industrial streams.

Analyses of Additives and Wear Metals in Lube Oil and S in Gasoline by New Low Cost Dual Detector Bench-Top EDXRF
Sanjay Kamtekar, Matt Kreiner - Oxford Instruments America Inc., and, Robert Lovicz -Predict USA, Inc.

The used lube oils becomes the working history of the machinery as wear from the effects of friction between contacting surfaces and destructive changes caused by oxygen, combustion gases and high temperature alter the condition of oil. In this study, we are presenting the data for the analysis of additives in unused lubricating oil by new bench-top EDXRF. In addition, we are providing the data for comparing analysis of wear metals in used lube oils, analyzed by three different techniques; new dual detector EDXRF, Rotating anode emission spectrometer and ICP. Extensive data will be presented for the analysis of S in gasoline to achieve the limit of detection of 2.5 ppm (3 sigma).

Current Practices in the Dioxin Sample Collection, Preparation, and Analyses Referencing Japanese Industrial Standard (JIS) Methods K 0311 and K 0312
Mark Robillard and Len Sidisky - Supelco Inc.

Polychlorinated dibenzodioxins (PCDDs), often termed dioxins, and polychlorinated dibenzofurans (PCDFs) are considered environmental contaminants. The primary sources of these contaminants are industrial processes and waste incineration. This seminar examines current methodologies, including JIS K 0311 and K 0312, used for sample collection, sample preparation, and GC/MS analysis of PCDDs/PCDFs found in stack gases, industrial water, wastewater, and soil. Discussions will include the various resins, adsorbents, and filters used for sample collection and extraction. Information will be presented on a new prep system that offers analysts an efficient means of extracting and classifying dioxins, furans, and coplanar PCBs. The seminar will conclude with a discussion of non-polar and highly selective capillary GC columns for separation of PCDDs/PCDFs.

A Comparison of Comprehensive Two-Dimensional Gas Chromatography and IP 391.
Paul Adams, Wayne Rathbun - UOP LLC

High performance liquid chromatography method IP 391 determines mono-aromatic, di-aromatic, and polyaromatic hydrocarbon contents in diesel fuels and petroleum distillates boiling in the range from 150 oC to 400oC. Comprehensive two-dimensional gas chromatography (GCxGC) provides unique capabilities in high resolution gas chromatography enabling separation of the polar aromatics from the non-polar aliphatics. Recent advances in GCxGC data handling now allow for reporting of aromatic groups to enable direct comparison of with IP391.

Advances in Water Content Determination of Crude Oil and Petroleum Products by Coulometric Karl Fischer Titration
George Robertson - PAC

The standard test methods for water content determination of crude oil samples by coulometric Karl Fischer titration (ASTM D 4928, API MPMS Chapter 10.9 and IP 386) stipulate that the Karl Fischer reagent be mixed 60:40 with xylene. This modification to the reagent affects the resistance/capacitance of the titration vessel. When the resistance is increased beyond certain limits the coulometer is unable to operate efficiently and provides incorrect results.Incorporating the recently patented A.C.E. control system, the new KF Series from ISL overcomes this problem and guarantees that the electrolysis current produced and count rate displayed are always correctly synchronised, thereby providing the correct result.

Laser Analyzer for Measuring Incompatibility/Fouling in Hydrocarbon Fluids
G. Dickakian Ph.D., J. Szyinyei B.S.E.E. - Fouling and Coking Technology, Inc., PAC

A portable, battery operated laser analyzer has been developed for characterization of incompatibility and fouling tendencies of hydrocarbon fluids. The technology is based on light-scattering, whereby a laser beam passes through fluid containing suspended particles like asphaltene, coke, inorganic or colloidal. The scattered light caused by flocculated particles is collected, detected, and translated into incompatibility and fouling. This analyzer is a useful tool for research and oil processing e.g. monitoring crude oil fouling, asphaltene incompatibility, blending crude oils and lighter hydrocarbons (naphtha and condensates), and is ideal for use in both laboratory and plant environments.

Measurement of Thermal Fouling of Hydrocarbon Fuels
G. Dickakian Ph.D. - Fouling and Coking Technology, Inc.

To measure fouling characteristics of hydrocarbons on heated metal surfaces, ALCOR's Liquid Process Simulator utilize a tube-in-shell heat exchanger that can be heated up to 1050 F. Fouling is measured by monitoring changes in exchanger liquid outlet temperature or pressure. These test units provide test methods to mitigate fouling in refinery operations by processing, chemical additive or selection of equipment metallurgy. Test results simulating fouling in various refinery equipment, crude oil blending, exchangers, furnaces and fouling caused by asphaltene, salt, clay, acid, polymers and dissolved oxygen will be presented.

Water, TAN and Catalyst Activity
Jim Sasser, Traude Sadtler - Sanda Corporation

Rapid and accurate analyses for the Petrochemical Industry are performed with an advanced, computerized Multi-Titration system, including: Water, without Karl Fischer reagents, is analyzed by thermometric titration using DMP with a choice of solvents. DMP is a stable titrant and not affected by the humidity. There are no interferences with amines, sulfur, oxides, oxidizers, etc. like as in Karl Fischer titration. Acid-Sites in inert solvents are analyzed in a three minute thermometric titration, and compare favorably with the time-consuming TGA and TPD desorption techniques. TAN (Total Acid Number) by chemiluminescence titration and remote signal detection, which has proven to be more accurate than pH titrations.

TD-NMR for Polymer QC
Harry Xie, Alison Barrett and Peter Krygsman - Bruker Optics Inc.,

TD (Time Domain) NMR is a powerful technique that provides rapid and quantitative information about molecular mobility and diffusion. It has been successfully applied in many industrial environments to precisely determine contents of ingredients such as oil, water, surfactant and additives in polymers. TD-NMR exploits the different relaxation properties of solids (ordered, crystalline molecules) and liquids (disordered, amorphous molecules). The more tightly bound fractions have a more rapid decay signal than the mobile fractions. In this paper examples of TD-NMR applications in polymer industries including xylene soluble content and cross link density measurements are discussed.

Calibration Standards for HRVOCs in Water
J. J. McKinley - Kin-Tek Laboratories, Inc.

The Texas Commission on Environmental Quality has pinpointed industrial emission of certain highly reactive volatile organic compounds as a substantial factor in ground level ozone formation in the Gulf Coast region. As part of the effort to reduce these emissions TCEQ is requiring industry to monitor cooling water for these HRVOCs. Gases such as ethylene, propylene, 1,3butadiene, and butenes as well as a number of liquid compounds must be monitored. The preparation and use of calibration standards for these measurements is a particularly pesky problem. This paper describes the adaptation of the permeation tube method to the creation of standards for ppb concentrations of HRVOCs dissolved in water.

Validation Studies and Applications Development Progress Using Microwave Heated Gas Chromatography Columns.
John S. Crnko - Antek Instruments, LP

Despite its status as a "mature" technology, gas chromatography (GC) improvements that even alter elements of the technology core continue to emerge. The microwave GC oven is one of these newest innovations, providing a heating technology that provides very fast heating and cooling times for the capillary column. This advantage is realized because microwave energy is absorbed and converted to heat by a compound imbedded only on the columns outer surface. A summary of improvements in apparatus function, new applications and several ruggedness studies is presented.

New Developments in ICP and FTIR Instrumentation for the Oil Condition Monitoring Laboratory
David R. Hilligoss, Mark R. Parman - Perkin Elmer Life and Analytical Instruments

As demands have increased on oil condition monitoring laboratories for higher throughput, less maintenance and better quality data, Perkin Elmer Instruments and its industry partners have developed new products and services to meet these more rigorous requirements. This paper will discuss new and enhanced ICP, FTIR, sample preparation and data handling products.

Chemiluminescence
Rick Trevino - University of Houston, Houston, Texas

In the last thirty years, many strides have been made to effectively utilize chemiluminescence as an analytical technique for determining concentrations of different elements. This poster will describe the various factors for measuring and comprehending this technique that has come to the forefront of analytical chemistry.

Improved Developments of Chemiluminescence Detectors: New Furnace Design
Michael King, Antek Instruments, Jeffrey Werner, DCG Partnership, Todd Ion, Antek Instruments, Jean-Francois Borny, DCG Partnership

Chemiluminescence technology has been and is being used in the detection of sulfur and nitrogen species. Most of the technology utilizes tubular ceramics to contain the extremely high temperature reaction zone. Tubular ceramics, though high temperature tolerant, are somewhat friable. Antek has been working to develop a new design to bring a higher level of stability, easier to handle and improved sensitivity. In cooperation with others, Antek has achieved these goals by providing a design that completely eliminates the use of friable ceramic tubes. This presentation will provide insight into the design and performance characteristics of the new furnace versus the current design as well as data review of various samples and standards. The use of this new design will allow for easier handling and increased stability through the elimination of tubes.

A Sulfur Simulated Distillation Standard
Alejandro Gonzalez, Jean-Francois Borny, Jeff Werner - DCG Partnership 1, Ltd.

Simulated distillation by gas chromatography has been used as an alternative to actual distillation to save time and reduce sample size. With the recent emphasis on reducing sulfur concentration in fuels, ASTM International (The American Society of Testing & Material) has been pursuing the development of a sulfur simulated distillation method. Estimating the boiling point distribution of the hydrocarbon content in fuels has been accomplished for many years now, with the advent of specific detector, it is now possible to also estimate a sulfur boiling point distribution. To aid in this process DCG has created a gravimetrically traceable retention time index standard of sulfur compounds. A simulated distillation curve was made using the available information about the different sulfur compounds, and the results of the analysis are discussed. The GC system included the following: Column: RTX1, 30 m, 1fÝm film thickness. GC: HP 5890 series II. Detector: Sulfur Chemiluminescense The standards analyzed were: - aromatic thiophenics: from thiophene to dibenzothiophene. - mercaptans: from methylmercaptan to nonadecylmercaptan. - symmetric sulfides: from dimethylsulfide, diethylsulfide to diphenylsulfide. - asymmetric sulfides: from methylethylsulfide. With this data, a curve of boiling point vs retention time was made for the appropriates conditions.

Natural Gas Analysis by Micro GC
Crissa Martin, Jean-François Borny - DCG Partnership 1, Ltd.

The Micro GC Analyzer consists of four GC columns in one instrument; an alumina column, a boiling point column, a mole sieve column, and a porepak column. A sample is taken from the target cylinder and is run through each column. A single analysis takes about five minutes to complete and a multiple replicate analysis. By using multiple calibration levels and external standards, a method has been successfully developed to analyze most basic natural gas standards. Using other methods, a full analysis of heavy components from C7 to aromatic C12s is possible as well as peak identification up to the C10 level. To allow for more efficient analysis, a 16-port multi-valve system, an internal automation program, and a helium purge have been installed. Future endeavors include developing improved methods and calibration levels to analyze for carbon monoxide, oxygen, refinery gases, including isomers, and "non-generic" natural gases, including those natural gases that have higher levels of ethane and propane.

Comparison of Different Sulfur Detectors and Capillary Columns for the Analysis of Sulfur Compounds in Hydrocarbon Matrices
Nelson Carvajal, Carmen Sanchez - DCG Partnership 1, Ltd.

Within the next few years, European and U.S. governmental regulations will require refiners to drastically lower the sulfur content of gasoline and diesel as part of the continuing effort to reduce air pollution from gasoline and diesel engines. Sulfur is targeted because it significantly reduces the efficiency of vehicle catalytic converters. Emissions of SO2 and other contaminants from the fluid catalytic cracking (FCC) regenerator and from refinery heater stacks continue to be an issue with refiners throughout the United States and the rest of the world. >From the analytical chemistry point of view the most interesting compounds and the major source of sulfur in gasoline and diesel fuels come from components produced by the FCC unit which are sulfur compounds of the aromatic type such as thiophenes, alkylthiophenes, benzothiophenes, alkylbenzothiophenes, dibenzothiophenes and alky dibenzothiophenes. This presentation presents a comparison of different detectors and capillary columns for detection and separation of the many sulfur species present in gasoline and diesel fuel. Some of the detectors evaluated will include the sulfur chemiluminescence detector, the pulse flame photometric detector and the atomic emission detector; GC-MS technique will be use for identification purposes and uv fluorescence analysis will be used to determine total sulfur in the samples

The Making of a Certified Standard
Jeffrey Werner, Louis D'Agostaro - DCG Partnership 1, Ltd.

Calibration standards are among the most scrutinized products a laboratory uses. Making certified or traceable standards is also taken for granted by most chemists. Regardless of the type of standards, liquid ampoules, gas, or LPG, all of DCG's Primary Standards are prepared gravimetrically and are certified N.I.S.T. traceable. Before a standard is blended, the raw materials must be analyzed for impurities, and the weights and balances must be evaluated to ensure traceability. After the standard is prepared, it is analyzed to verify the gravimetric concentrations. In most cases this involves gas chromatography but some elemental methods are also employed. The chromatographic detection techniques used for this verification include flame ionization (FID), thermal conductivity (TCD), pulsed flame photometric (PFPD), sulfur chemiluminescence (SCD), nitrogen chemiluminescence (NCD), and mass selective (MSD). This presentation will give an inside look at the processes involved in making, certifying, and verifying a calibration standard.

The Use of Extended Temperature Range Liquid Chromatography and Temperature Programming for Petroleum Product Analysis
Jody Clark, Stephanie J Marin, W. Dale Felix, Brian A. Jones, Chris Biddulph - Selerity Technologies Inc.

Normal phase HPLC is routinely used as a separation technique in the analysis of fractions in petroleum products. However, the process can be quite extensive with poor resolution and efficiency. To obtain the polycyclic aromatic hydrocarbon ring member separations sub-ambient column temperatures must be used to maximize the interaction with the column phases. This in conjunction with slow flow rates leads to long analysis times. In this paper, we will present the use of temperature programmed HPLC, taking advantage of increased efficiency and decreased analysis times for separating aromatic hydrocarbons. We have looked at the effect that temperature has on the entire range of polycyclic aromatic hydrocarbons found in petroleum fractions and we will discuss the selectivity towards ring numbers as a function of temperature flow programming for speed improvement.

Acceptance of Supercritical Fluid Chromatography (SFC) Methods for Class Separations in the Petroleum Industry: Gasoline, Diesel and Additives
Jody Clark, Chris Bidduph, Stephanie J. Marin, W. Dale Felix - Selerity Technologies Inc.

Supercritical fluid class fractionation techniques have become increasingly accepted in the petroleum industry to conveniently provide total aromatic and olefinic content in fuels. SFC offers some distinct advantages over other more widely accepted separation techniques, such as the use of the flame ionization detector (FID), increased solubility, and the capability of group-type separations. In this paper, we will discuss the current ASTM methods using SFC and review how to optimize these methods. We will also show some new, unique class fractionation methods that can easily be incorporated into your analytical laboratory and will be beneficial in monitoring and/or regulating petroleum products.

Automatic Quantitative Analysis of BTEX and Total Aromatics in Gasoline Using GCxGC Time-of-Flight (TOF) MS
Peter Combe, Tincuta Veriotti - Leco Corporation

The increase in resolving power obtained from comprehensive two-dimensional GC (GCxGC) made petroleum products one of the main applications for this technique. In addition to the high complexity of the samples, all the analytes present are of interest and cannot be treated as interfering components. This sample characteristic makes mass spectrometry an attractive technique for detection. The very narrow chromatographic peaks obtained from the second dimension of a GCxGC system require fast acquisition rates for adequate peak characterization, precluding most other mass spectrometric techniques from being used for detection. With the high acquisition rate capabilities of up to 500 spectra/s, time-of-flight (TOF) MS becomes the most viable mass detector that can be coupled with the GCxGC technique. In addition to data collection speed, spectral continuity across the chromatographic peak profile enables peak deconvolution for the cases where the achieved peak separa! tion proves not to be sufficient. Increased environmental concerns in the past decade lead to more stringent control of some of the toxic and ozone forming compounds present in gasoline. Benzene, toluene, ethylbenzene, xylenes (BTEX), and other EPA regulated aromatics are components that are either naturally present or/and added to gasoline in order to increase the octane number. The highly organized chemical class pattern obtained from GCXGC analysis enables easier qualitative and quantitative analysis of these components, but the large amount of information obtained makes manual processing a very difficult task. This study presents the results obtained for the quantitative analysis of BTEX and total aromatics in gasoline using a completely automated GCxGC TOF MS system. Over 20 components are calibrated using 4 internal standards in about 10 minutes. The calibration curves obtained are then used for the quantitative analysis of a reference gasoline material.

Ultra Fast GC with Directly Heated Capillary Columns Implemented on a New GC Platform: Advantages and Applications
Flavio Bedini, Paolo Magni, Daniela Cavagnino, Riccardo Facchetti and Sorin Trestianu, Thermo Electron, Str Rivoltana, 20090 Rodano (Milan), Italy, and Michael Harter, Thermo Electron, USA

Ultra Fast gas chromatography is obtained by applying very high temperature programming rates to short narrow bore columns. It allows to generate fast peaks, in the range of 50-200ms, and obtain separation in 1minute or less. Very fast temperature ramps are only possible by directly heating the capillary column, since a conventional air circulating oven can hardly reach rates higher than 120°C/min. A direct resistively heated capillary column system capable of programming rates as high as 20°C/s up to maximum temperatures of 350°C or higher, was used to demonstrate the applicability of this technology to various analytical fields, with the advantage of reducing the analysis time maintaining a sufficient resolution for several applications [1]. The capillary column is assembled with its heating and temperature sensing elements in a module that is housed, as a removable accessory, in a new GC platform (Finnigan TRACE GC Ultra) and connected to the GC inlet and detector. The precision of column module temperature control ensures high repeatability of retention times allowing fully automated operations and unambiguous identification of components by fast acquisition rate (>100Hz) data system. Appropriate detection and injection systems are provided to accomplish the requirements of the ultra fast separations. In particular a fast FID, with a time constant in the ms range, and a TOF-MS for a proper detection of very narrow peaks. Injection using splitless mode were also performed to illustrate the possibilities for trace analysis. Increased sensitivity was achieved thanks to enhancement of the signal to noise ratio produced by the narrow peaks. Different types of modules featuring different stationary phases, film thickness, internal diameters and column lengths (usually ranging from 2.5 to 10 m) were used for a broad range of applications and for illustrating applicability of Ultra Fast GC also for complex mixtures. Reference [1] P.Magni, D.Cavagnino, R.Facchetti, S.Trestianu, Proc. 25th Int. Symp. On Capillary Chromatography, Riva del Garda, 2002

Comprehensive Two-Dimensional GC Symposium The Applications of Comprehensive Two-Dimensional Gas Chromatography in the Petroleum Industry
Frank Cheng-Yu Wang*, Frank P. DiSanzo and Frank C. McElroy

Comprehensive two-dimensional gas chromatography (GCxGC or 2D-GC), provides unique capabilities in high resolution gas chromatography (GC). GCxGC employs a single GC containing two separation columns of different selectivity connected in series with a modulation unit in between to perform solute focusing and re-injection into a short, high-speed second column. GCxGC may be considered a 'Continuous' heart-cutting form of a conventional single heart-cutting multidimensional GC that has been established for many years. When analyzing a complex mixture, conventional one-dimensional GC most often results in (1) unresolved peaks in a limited time region and (2) limited detection sensitivities. However, with GCxGC compound resolution has been significantly enhanced. In addition, the resulting two-dimensional chromatogram can provide unique component information on a boiling point basis in one dimension as well as on a polarity basis in the second dimension. This means that in the GCxGC chromatogram, unlike conventional GC, the information of compound classes can be clearly observed. This presentation will describe applications of GCxGC to the characterization of petroleum streams such as hydrocarbons using flame ionization detector (FID) and nitrogen compound using nitrogen chemiluminescence detector (NCD). For example, in the hydrocarbon analysis by FID, paraffins, naphthenes, and aromatics will form distinct two-dimensional separated groups. In the analysis with NCD, nitrogen-containing compound classes can be distinguished by boiling point and polarity as distinct different classes. The GCxGC/NCD approach offers significant resolution and identification advantage over conventional GC/FID and GC/NCD analysis.

Development Of A Lube Oil Anti-Rust Additive From A Plant Source
Dr Kwame Ankoma Kwakye - Quality Control Laboratory, Tema Lube Oil Company Limited

Local metal artisans especially blacksmiths here in our part of the world have been coating their wares with a concoction which is prepared from palm kernel oil and the bark, root or leaves of a particular local plant. This is a very old traditional practice which is proven to being able to arrest the rusting of their wares effectively. My investigations using infra red spectroscopy have revealed that the plant extracts contain a mixture of esters of alkyl-substituted succinic acids which disperses in the palm kernel oil acting as a liquid carrier to facilitate application by brushing. Admixtures of the plant extracts in the vegetable oil and in a mineral base oil were evaluated for their anti-rust and anti-corrosion effectiveness according to standard methods such as ASTM D 130 and D 665 and appropriate comparisons made. This Paper will show the results of the investigations so far.

The Use Of Local Clays As Adsorbents For The Chromatographic Determination Of The Saturates Content Of Base Oils
Kwame Ankoma Kwakye, PhD,MRSC, CHEM - TEMA LUBE OIL COMPANY LIMITED

Lubricating oils are normally blended from base oils and chemical additives. The hydrocarbon components of the base oils can be categorized into Saturates, Aromatics and Polar fractions and knowledge of the amount of these fractions provide very useful information for the development of formulation of specific lubricants. Usually the fractionation of base oils is done through adsorption chromatography (1) or high pressure liquid chromatography ( 2 ) all of which employ various clay adsorbents. The quality of clay used for such application is specified by its Azobenzene Activity Value (AAV) which should lie between 30-35 ( 1 ). In order to curtail the costly importation of clay adsorbent, it became necessary to search for a locally available clay type which could meet this AAV specification level. This Paper reports on the experiments done to evaluate several clay deposits obtained locally by the determination of the AAV of each. One hundred different types of clays from different locations were tested this way. Ten(10) varieties passed the test and were found to be suitable for this application and have been employed routinely for the fractionation of base oils to permit the quantification of the Saturate content of base oils which is a standard quality parameter that governs the purchase of the product. The critical factor in the clay’s ability to meet the AAV specification was found to be the mesh size and the mineralogical composition of the clay. The study has helped us to locate deposits of clay which are suitable for this analytical application and has substantially saved us foreign exchange which would otherwise have gone into the importation of this adsorbent.

REFERENCES:

( 1 ) Annual Book of ASTM Standards, Year 2000 edition, Volume 05.01, D-1319 & D-2007 published by the American Society of Testing and Materials, 100 Barr Harbor Drive, West Conshohocken, PA, USA

( 2 ) Standard Methods For Analysis & Testing Of Petroleum Products, Volume 2, IP 368, 1992 published by the Institute of Petroleum, London.