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Produced water from conventional oil and gas wells (O&G PW) is beneficially reused as an inexpensive alternative to commercial dust suppressants which minimize inhalable particulate matter (PM 10 ) from unpaved roads. The efficacy and environmental impacts of using O&G PW instead of commercial products have not been extensively investigated, although O&G PW has been used for dust suppression for decades and often has elevated concentrations of environmental pollutants. In this study, the effectiveness of O&G PW is compared to commercial products under variable humidity conditions by measuring total generated PM 10 emissions from treated road aggregate discs. To measure environmental impacts, model roadbeds were treated with six O&G PW and commercial products then subjected to a simulated two-year, 24-h storm event. Generated runoff water was collected and characterized. In efficacy studies, O&G PW offered variable dust reduction (10-85 %) compared to rainwater controls under high humidity (50 %) conditions but performed similarly or worse than controls when humidity was low (20 %). Conversely, all but two commercial products reduced dust emissions by over 90 % regardless of humidity. In rainfall-runoff experiments, roads treated with O&G PWs and CaCl 2 Brine generated runoff that was hypersaline, indicating that mobilization of soluble salts could contribute to freshwater salinization. Though most runoff concentrations were highest from roadbeds treated with CaCl 2 Brine, runoff from roadbeds treated with O&G PW had the highest concentrations of combined radium (83.6 pCi/L), sodium (3560 mg/L), and suspended solids (5330 mg/L). High sodium concentrations likely dispersed clay particles, which increased road mass loss by 47.2 kg solids/km/storm event compared to rainwater controls. Roadbeds treated with CaCl 2 Brine, which had low sodium concentrations, reduced solid road mass loss by 98.1 kg solids/km/storm event. Based on this study, O&G PW do not perform as well as commercial products and pose unique risks to environmental health., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Smallmouth bass in the Susquehanna River Basin, Chesapeake Bay Watershed, USA, have been exhibiting clinical signs of disease and reproductive endocrine disruption (e.g., intersex, male plasma vitellogenin) for over fifteen years. Previous histological and targeted chemical analyses have identified infectious agents and pollutants in fish tissues including organic contaminants, mercury, and perfluorinated compounds, but a common causative link for the observed signs of disease across this widespread area has not been determined. This study examines 146 young-of-year smallmouth bass collected from 14 sampling sites in the Susquehanna River Basin, Pennsylvania, USA with varying levels of disease prevalence. Whole fish were extracted by a recently developed modification to the quick, easy, cheap, effective, rugged, and safe extraction method and analyzed by comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry. A targeted analysis was conducted to identify the presence and quantity of 127 known contaminants, including polychlorinated biphenyls, brominated diphenyl ethers, organochlorinated pesticides, and pharmaceutical and personal care products. A non-targeted analysis was conducted on the same data set to identify analytes of interest not included on routine target compound lists. Chromatographic alignment through Statistical Compare (ChromaTOF GC) was followed by Fisher ratio and principal component analysis to reduce the data set from thousands of peaks per sample to a final data set of 65 analytes of interest. Comparisons of these 65 compounds between Normal (no observed health anomalies) and Lesioned (observed health anomaly at time of collection) fish revealed increased levels of three chemical families in Lesioned fish including esters, ketones, and nitrogen containing compounds., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Liquid-liquid extraction (LLE) and stir bar sorptive extraction (SBSE) are extraction methods used for the analysis of contaminants in aqueous samples. In this study, both LLE and SBSE were compared for the extraction of priority pollutants and contaminants of emerging concern (CECs) in wastewater influent and effluent samples, for analysis with comprehensive two-dimensional gas chromatography with time of flight mass spectrometry (GC × GC-TOFMS). The methods were compared for their extraction efficiency of a broad range of compounds, matrix effects, accurate and reliable quantification of targets, and sensitivity. The target analytes studied were semi-volatile organic compounds (SVOC) including polycyclic aromatic hydrocarbons, phenols, phthalate esters, anilines, ethers, aromatic nitro compounds, and nitrosamines. LLE allowed for a higher number of target analytes to be extracted with over 70% recovery and quantified more targets in the influent samples. Matrix interference effects had a negative impact on the recovery of non-polar contaminants, such as polycyclic aromatic hydrocarbons (PAHs), in the influent water samples especially with SBSE. In SBSE, 24 target analytes demonstrated significant matrix interference leading to poor analyte recovery and 13 analytes were negatively affected in the same way in LLE. Generally, polar compounds also demonstrated poor extraction with SBSE in both effluent and influent water samples. However, SBSE effluent chromatograms contained about three times as many total analytes as compared with LLE, suggesting that SBSE is more sensitive for trace contaminants in effluent samples. Based on this research, LLE is recommended for studies seeking to quantify a broad range of target analytes in complex matrices, like wastewater influent. SBSE is an appropriate method for the non-target and survey analysis of trace contaminants in less complex water samples., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Comprehensive two-dimensional gas chromatography (GC×GC) is a powerful tool for complex separations. The selectivity and sensitivity benefits from thermally modulated GC×GC were applied to the analysis of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Thermodynamic indices of 50 PCDD/Fs, including the 17 toxic 2378-substituted congeners, were collected and used to model one-dimensional and two-dimensional separations with the Rtx-Dioxin2 and Rxi-17SilMS capillary GC columns. Thermodynamic modeling was used to determine the optimal conditions to take advantage of the selectivity differences between the Rxi-17SilMS and Rtx-Dioxin2 to separate all PCDD/Fs congeners from the 2378-substituted compounds by GC×GC. The modeled elution order patterns closely matched the experimental elution order in 40 of the 45 tetrachlorinated through hexchlorinated compounds analyzed. The heptachlorinated and octachlorinated congeners were not included in the elution order modeling as they are readily resolved from other dioxin congeners. The Rxi-17SilMS crossed with the Rtx-Dioxin2 was able to separate all 2378-substituted compounds in a single separation in a fish matrix. Thirty-three additional PCDD/F congeners were added to the fish matrix that coelute with the 2378-substituted congeners. The Rxi-17SilMS crossed with the Rtx-Dioxin2 was able to fully resolve 11 of the 2378-substituted congeners with the other six congeners exhibiting coelutions with only one other congener., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier B.V.)

Polychlorinated dibenzo-p-dioxins and furans are environmentally persistent and highly toxic compounds. 136 chlorinated dioxins and furan congeners contain at least four chlorine atoms and pose a complex separation challenge in environmental and biological matrixes. The complexity arises from the dioxin and furan molecules with substitutions at positions 2, 3, 7, and 8, which are toxicologically relevant but are not easily separated from the other non-/less toxic congeners. Many regulatory methods require the use of two columns with different polarities or selectivity for dioxin analysis. The most common confirmation column pair is a (5% phenyl)-methylpolysiloxane and a (biscyanopropyl-/ cyanopropylphenyl)-methylpolysiloxane. These phases are required in USEPA-1613 for 2,3,7,8-tetrachlorodibenzo-p-dioxin and 2,3,7,8-tetrachlorodibenzofuran specificity. However, other column phases, such as the Rxi-17SilMS and the Rtx-Dioxin2, offer alternatives to the traditional column pairing and provide a similar or better separation of 2,3,7,8-substituted congeners. This study compares four columns for dioxin analysis: the Rtx-Dioxin2, Rxi-17SilMS, Rxi-5SilMS, and Rtx-2330. All columns used in this study are capable of meeting the requirements for dioxin analysis required by USEPA-1613. However, the Rtx-Dioxin2 demonstrated improved selectivity for a wider range of dioxin compounds than the Rxi-5SilMS. The Rtx-Dioxin2 is capable of resolving 2,3,7,8-tetrachlorodibenzo-p-dioxin and 2,3,7,8-tetrachlorodibenzofuran from common interferants better than the Rxi-5SilMS and can be used as a confirmation column with either the Rtx-2330 or Rxi-17SilMS., Competing Interests: Declaration of Competing Interest None., (Copyright © 2020. Published by Elsevier B.V.)

A method to thermodynamically model the alkane isovolatility curves of a comprehensive two dimensional gas chromatography (GC × GC) separation is presented. This method omits all instrument modifications, additional chromatogram collection, or method alterations which typical isovolatility curve generation requires. Provided that the thermodynamic indices of reference alkanes are available, chromatographers only need to specify the GC × GC method parameters of their separation to output the isovolatility curves. The curves can then be used alongside reference retention indices to generate two dimensional retention times for each analyte. Agreement between the modeled and experimental retention times provides a secondary mechanism for compound identification, supporting the results of a mass spectral search. The technique was used to model the retention times of a GC × GC separation of aromatic hydrocarbons, achieving an average first dimension retention time modeling error of 11 s and an average second dimension retention time modeling error of 0.09 s. Retention indices modeled retention times provide a simpler analyte identification procedure compared to conventional two dimensional retention indices matching., Competing Interests: Declaration of Competing Interests The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier B.V.)

Polychlorinated dibenzo-p-dioxins and furans offer a complex separation challenge due to their chemical similarity and 5020 possible congeners, including the Br/Cl congeners. Not only are these compounds difficult to separate, but they are also difficult to identify. Expensive reference materials are needed for conventional "dioxin analysis", usually requiring 13 C labeled and native compounds. A retention index database offers a potential solution to lower the difficulty and cost to identify dioxins. This study describes the use of Kovats and Lee retention indices for the identification of chlorinated dioxins and furans as well as their brominated and mixed chloro/bromo counterparts. Eight columns were characterized with all 136 tetra through octa substituted chlorinated dioxins and furans as well as 32 brominated and mixed chloro/bromo congeners. Columns were then compared to identify which stationary phases provided the best resolution for critical congeners, like the 2,3,7,8 substituted compounds. Column phase selectivity was also investigated to identify best commercially-available column pairings for confirmatory analyses and GC × GC separations. The Rtx-Dioxin2 and Rxi-17SilMS showed unique selectivity for dioxins and furans and could be used as confirmatory columns or as a powerful GC × GC column set., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019. Published by Elsevier B.V.)

Thermodynamic modeling of GC × GC separations provides a tool for rapid method evaluation and optimization. Separations of 95 hydrocarbons on two cryogenically modulated GC × GC systems (atmospheric outlet and vacuum outlet) are modeled, displaying average second dimension retention time modeling absolute errors of 0.17 s and 0.12 s respectively, and generating modeled chromatograms which sufficiently represent experimental data. A web-based GC × GC modeling routine is presented which allows users to model separations, currently focused on hydrocarbons, with full control over all system parameters. The method translation capabilities of the application are further demonstrated by replicating Piotrowski et al.'s GC × GC-HRT temporal distribution plots of hydraulic fracturing flowback fluid hydrocarbons [28]., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019. Published by Elsevier B.V.)

The presence of contaminants of emerging concern (CECs), such as antibiotics, antimicrobial disinfectants, nonprescription drugs, personal care products, pharmaceuticals, and steroids, in water resources can impact aquatic and human health. A large portion of the CECs entering regional wastewater treatment plants originate from hospitals. The purposes of this study were to conduct exploratory analytical work to characterize two hospital wastewaters and to evaluate treatment of CECs at hospitals before dilution with domestic wastewater. A 24-h batch reaction with biogenic manganese oxides coated onto coir fiber was used to treat the wastewaters. Organic contaminants in the wastewaters were concentrated by both liquid-liquid extraction (LLE) and solid-phase extraction (SPE). LLE extracts were analyzed by Comprehensive Two-Dimensional Gas Chromatography/Time-of-Flight Mass Spectrometry (GC × GC-TOFMS) while SPE extracts were analyzedby UltraHigh Performance Liquid Chromatography/Time-of-Flight Mass Spectrometry (UHPLC-TOFMS). Fifty-two organic micropollutants were detected (26 by GC × GC-TOFMS, 25 by UHPLC-TOFMS, 1 by both) in the wastewaters, while 29 were removed by >90% and six were degraded by <50% after treatment. Control experiments revealed that sorption to coir fiber and oxidation by manganese oxides were the primary contaminant removal mechanisms. Both the LLE and SPE extracts were used to evaluate potential human toxicity of the hospital wastewaters before and after treatment. Twenty-eight human cell-based bioreceptor assays were used to screen the wastewaters, and secondary tests were run to quantify toxicity equivalents to activated receptors. The wastewaters initially contained organic micropollutants that strongly activated the Androgen Receptor, Estrogen Receptor β, and the Mineralocorticoid Receptor but no bioactive compounds were detected after treatment. Point-of-entry treatment of hospital wastewater should reduce bioactive compounds from entering the environment., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Wastewater treatment plants (WWTPs) are one of the major sources of contaminants of emerging concern (CECs) in the environment. Benzotriazole corrosion inhibitors are a class of CECs that are resistant to biodegradation and have been reported in waters varying from WWTP effluent to groundwater and drinking water. This study examined wastewater influent and effluent grab samples over three years using Comprehensive Two-Dimensional Gas Chromatography (GC × GC) to discover six target benzotriazoles, four of which have never been properly characterized in water prior to this work. The six benzotriazoles were two methyl isomers (4-methyl-1H-benzotriazole and 5-methyl-1H-benzotriazole) as well as four chloromethyl isomers (previously unidentified). Using targeted analysis, the benzotriazoles were quantified and semi-quantified in the wastewater. In all seasons sampled but one, the concentration of three of the four chloromethyl-benzotriazoles increased from the influent to effluent waters. For the first time, it was observed that the 4 and 5-methyl-benzotriazoles interact with the sodium hypochlorite in the tertiary treatment step of the WWTP leading to the formation of the four chloromethyl-benzotriazoles. This was confirmed with lab scale synthesis of the reaction where the products were chromatographically analyzed and matched mass spectral and retention time data of the water samples. Assisted by the mass spectral fragmentation information, the four chloromethyl-benzotriazole isomers were tentatively identified as 4-chloromethyl-2H-benzotriazole, 5-chloromethyl-1H-benzotriazole, 4-chloromethyl-1H-benzotriazole, and 5-chloromethyl-2H-benzotriazole, in order of elution. No analytical standards are available for the chloromethyl-benzotriazole compounds and this is the first attempted identification of them in waters. The yearly mass loadings of total benzotriazoles were estimated to average between 148.86 and 394.64 kg/year at this particular facility. The WWTP studied reuses all effluent water for irrigation of crop and forested land so this high value of benzotriazoles entering the environment is concerning and the impacts need to be further studied., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Thermodynamic retention modeling to a thermally modulated comprehensive two-dimensional gas chromatography (GC × GC) system run under constant flow is performed. Significant errors in modeled second dimension retention time (t r,2 ) were observed, in line with past work on thermally modulated GC × GC modeling. A comprehensive study of t r,2 modeling error for alkane separations across a wide range of heating ramp rates and carrier gas flow rates was performed. Modeling errors were found to be systematic and a function of analyte elution temperature and mobile phase velocity. A model to account for these systematic errors was generated, and associated coefficients were determined which reduced average t r,2 retention time error in 144 hydrocarbon separations by an order of magnitude resulting in significant improvement in prediction accuracy. The model was used to correct the separation of 139 Grob mix analyte separations, providing an average t r,2 modeling error of 0.030 ± 0.022 s. The model successfully predicted the separation of n-alkanes on a longer second dimension column configuration., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Development of shale gas resources through the use of hydraulic fracturing has raised a multitude of environmental concerns and motivated research towards the understanding of shale gas systems. Previous research has demonstrated the potential of utilizing hydrocarbon distributions towards the fingerprinting of a potential environmental contamination event arising from shale gas operations. However, to apply hydrocarbon distributions from shale gas wells towards point-source identification and apportionment, a better understanding of hydrocarbon origins must be achieved. Here we present an efficient and repeatable thermal desorption method, as a sample introduction methodology for GC × GC analysis of shale rock samples that results in comparable chromatograms to those produced by solvent extraction. This novel and robust characterization technique of shale cores from Marcellus and Utica formations by thermal desorption followed by GC × GC enables the understanding of hydrocarbon speciation within the native rock with minimal sample preparation time and solvent use. The detailed shale chemistry gives insight into utilizing hydrocarbon differences towards point-source identification methodologies of environmental contamination events associated with unconventional gas development. Additionally, this analytical technique may provide a more detailed analysis of hydrocarbons than what is currently implemented in the industry to pinpoint the most advantageous areas to exploit by hydraulic fracturing, yet avoiding undesirable areas such as those with a high abundance of sulfur containing compounds., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The field of environmental forensics emerged in the 1980s as a consequence of legislative frameworks enacted to enable parties, either states or individuals, to seek compensation with regard to contamination or injury due to damage to the environment. This legal environment requires stringent record keeping and defendable data therefore analysis can sometimes be confined to data to be obtained from certified laboratories using a standard accredited analytical method. Many of these methods were developed to target specific compounds for risk assessment purposes and not for environmental forensics applications such as source identification or age dating which often require larger data sets. The determination of persistent organic pollutants (POPs) for environmental forensic applications requires methods that are selective but also cover a wide range of target analytes which can be identified and quantified without bias. POPs are used in a wide variety of applications such as flame retardants, fire suppressants, heat transfer agents, surfactants and pesticides mainly because of their chemical inertness and stability. They also include compounds such as dioxins that can be unintentionally produced from industrial activities. POPs are persistent in the environment, bioaccumulative and/or toxic and therefore require analytical methods that are sensitive enough to meet the low detection limits needed for the protection of the environment and human health. A variety of techniques, procedures and instruments can be used which are well suited for different scenarios. Optimised methods are important to ensure that analytes are quantitatively extracted, matrix coextractables and interferences are removed and instruments are used most effectively and efficiently. This can require deviation from standard methods which can open the data up to further scrutiny in the courtroom. However, when argued effectively and strict QA/QC procedures are followed the development and optimization of methods based on investigation specific scenarios has the potential to generate better quality and more useful data., (Copyright © 2016 Elsevier B.V. All rights reserved.)

An analytical method for identification of emerging contaminants of concern, such as pesticides and organohalogens has been developed and utilized for true discovery-based analysis. In order to achieve the level of sensitivity and selectivity necessary for detecting compounds in complex samples, comprehensive gas chromatography coupled with time-of-flight mass spectrometry (GC×GC-TOFMS) was utilized to analyze wastewater samples obtained from the Pennsylvania State University wastewater treatment facility (WWTF). Determination of emerging contaminants through a process of combining samples which represent "normal background" and comparing this to new samples was developed. Results show the presence of halogenated benzotriazoles in wastewater samples as well as soil samples from Pennsylvania State University agricultural fields. The trace levels of chlorinated benzotriazoles observed in the monitoring wells present on the property indicate likely environmental degradation of the chlorinated benzotriazoles. Preliminary investigation of environmental fate of the substituted benzotriazoles indicates their likely degradation into phenol; an Environmental Protection Agency (USEPA) priority pollutant., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A comprehensive approach was taken to characterize the polyhalogenated dibenzo-p-dioxin and dibenzofuran contents of fire debris. Household and electronics fire simulations were performed to create samples representative of those firefighters most typically come in contact with. Sample analysis was performed using GC×GC-TOFMS to provide a comprehensive profile of the halogenated dioxins and furans present among the two types of fire debris. Both the household fire and electronics fire simulations produced a significant amount of polybrominated dibenzofurans. Only the electronics rich fire simulation produced mixed halogenated (Br/Cl) dibenzofurans in amounts above the limit of detection of the analytical method. Of the mixed halogenated dibenzofurans identified, a majority were those having no commercially available standard to allow for specific congener identification. GC×GC-TOFMS was extremely beneficial for the identification of compound classes due to the manner in which compounds classify in the two-dimensional chromatographic plane, thus aiding data reduction for these materials., (Copyright © 2014 Elsevier B.V. All rights reserved.)

This work focuses on the development and experimental evaluation of micromachined chromatographic columns for use in a commercial gas chromatography (GC) system. A vespel/graphite ferrule based compression sealing technique is presented using which leak-proof fluidic interconnection between the inlet tubing and the microchannel was achieved. This sealing technique enabled separation at temperatures up to 350°C on a μGC column. This paper reports the first high-temperature separations in microfabricated chromatographic columns at these temperatures. A 2m microfabricated column using a double Archimedean spiral design with a square cross-section of 100μm×100μm has been developed using silicon microfabrication techniques. The microfabricated column was benchmarked against a 2m 100μm diameter commercial column and the performance between the two columns was evaluated in tests performed under identical conditions. High temperature separations of simulated distillation (ASTM2887) and polycyclic aromatic hydrocarbons (EPA8310) were performed using the μGC column in temperature programmed mode. The demonstrated μGC column along with the high temperature fixture offers one more solution toward potentially realizing a portable μGC device for the detection of semi-volatile environmental pollutants and explosives without the thermal limitations reported to date with μGC columns using epoxy based interconnect technology., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A comparison of septum degradation data obtained from a variety of standard GC septa, including the Thermogreen LB-2, AG3 (Green), Thermolite, BTO and the Merlin Microseal were evaluated. This study was conducted to determine analytical system lifetime between inlet maintenance based on chromatographic performance of reactive compounds as a function of septum aging through repeated injections. It is widely accepted that gas chromatographic septa degrade relative to the operating temperature of the injector and also based on the physical interaction with the syringe needle. This interaction may cause shedding of particles which then accumulate in the injection port liner, or possibly on the GC column in rare cases. This will likely lead to reactive compound breakdown in the injection port of flash-vaporizing inlets and thus reduce the amount of time that an instrument may be operated between inlet maintenance. Evaluations of the septa were based on the performance of the organochlorine compounds, endrin and 4,4'-DDT. These two compounds act as general indicators for the overall inertness of the GC injector, and their performance may be used to extrapolate to the performance of many other compounds. The average lifetime in terms of the number of injections for the studied septa was determined to range from 151 injections to nearly 2000 injections, depending on the septum. These values were found to be repeatable within the same septa material, or within class. The injection lifetime was found to be statistically different between different septa, however, indicating that not all septa are equivalent in terms of their durability to repeated injections. Additionally, some septa were found to predominately cause degradation of endrin, while others were found to cause reactivity of 4,4'-DDT, indicating that a difference in septa material may cause differences in what types of compounds become reactive in the GC inlet., (Copyright © 2012 Elsevier B.V. All rights reserved.)

A comprehensive, sensitive and high-throughput liquid chromatography-atmospheric pressure photoionization tandem mass spectrometry (LC-APPI-MS/MS) method has been developed for analysis of 36 halogenated flame retardants (HFRs). Under the optimized LC conditions, all of the HFRs eluted from the LC column within 14min, while maintaining good chromatographic separation for the isomers. Introduction of the pre-heated dopant to the APPI source decreased the background noise fivefold, which enhanced sensitivity. An empirical equation was proposed to describe the relation between the ion intensity and dopant flow. The excellent on-column instrument detection limits averaged 4.7pg, which was similar to the sensitivity offered by gas chromatography-high-resolution mass spectrometry (GC-HRMS). This method was used to analyze a series of fish samples. Good agreement was found between the results for PBDEs from LC-APPI-MS/MS and GC-HRMS., (Copyright (c) 2009 Elsevier B.V. All rights reserved.)

In order to fully realize the separation power of comprehensive two-dimensional gas chromatography (GC x GC), a means of predicting and optimizing separations based on operating variables was developed. This approach initially calculates the enthalpy (DeltaH) and entropy (DeltaS) for the target compounds from experimental input data, and then uses this information to simultaneously optimize all column and runtime variables, including stationary phase composition, by comparing the performance of large numbers of simulated separations. This use of computer simulation has been shown to be a useful aid in conventional separations. It becomes almost essential for GC x GC optimization because of the large number of variables involved and their very complex interaction. Agreement between experimental and predicted values of standard test samples (Grob mix) using GC x GC separation shows that this approach is accurate. We believe that this success can be extended to more challenging mixtures resulting in optimizations that are simpler and transferable between GC x GC instruments.

Comprehensive two-dimensional gas chromatography with isotope-dilution time-of-flight mass spectrometry (GC x GC-IDTOFMS) was used to measure polychlorinated dibenzo-p-dioxin (PCDD), polychlorinated dibenzofuran (PCDF), and coplanar polychlorinated biphenyl (cPCB) concentrations in ash, sediment, vegetation, and fish samples. The GC x GC capability was achieved by using a quad jet, dual stage, thermal modulator. Zone compression of the GC peaks from modulation resulted in a significant increase of the signal intensity over classical GC-IDTOFMS. The GC x GC column set used an Rtx-Dioxin 2 phase as the first dimension ((1)D ) and an Rtx-500 as the second dimension ((2)D ). The chromatographic separation of the 17 PCDD/Fs and the 4 cPCBs was attained in (1)D except for 2,3,7,8-TCDD and CB126 for which deconvoluted ion currents (DIC) were required to be reported separately. The Rtx-500 phase separated the bulk matrix interfering compounds from the target analytes in (2)D . The instrumental limit of detection (iLODs) was 0.5pg for 2,3,7,8-TCDD. The calibration curves showed good correlation coefficients for all the compounds investigated in the concentration range of 0.5-200pg. GC x GC-IDTOFMS results compared favorably to those from conventional isotope-dilution one-dimensional gas chromatography-high resolution mass spectrometry (GC-IDHRMS). The comprehensive mass analysis of the TOFMS further permitted the identification of other contaminants of concern in the samples.

High-speed gas chromatographic (GC) separation of residual solvents in pharmaceutical preparations, using a flow-modulation technique, is described. These volatile compounds are separated on a series-coupled (tandem) column ensemble consisting of a polyethylene glycol column and a trifluoropropylmethyl/dimethylpolysiloxane column. This column ensemble is operated in stop-flow mode to enhance, or "tune", the separation. A valve between the junction point of the tandem column ensemble and a source of carrier gas at a pressure above the GC inlet pressure is opened for intervals of 2-8 s. This stops or slightly reverses the flow of carrier gas in the first column. Stop-flow pulses are used to increase the separation of target analytes that overlap in the total ensemble chromatogram, compared to non-stop-flow, or conventional, operation. All 36 target compounds, based on ICH Classes I and II residual solvent lists, are resolved in 12 min using the stop-flow technique and a single chromatographic analysis.