Comprehensive two-dimensional gas chromatography thermodynamic modeling and selectivity evaluation for the separation of polychlorinated dibenzo-p-dioxins and dibenzofurans in fish tissue matrix.

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.

The Rtx-Dioxin2 and Rxi-17SilMS as Alternative Gas Chromatographic Confirmation Columns for Dioxin Analysis.

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.

Characterization of 9 gas chromatography columns by Kovats and Lee retention indices for dioxin analysis.

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 13C 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.

Evaluation of multiple alternative instrument platforms for targeted and non-targeted dioxin and furan analysis.

The use of gas chromatography coupled to high-resolution magnetic sector mass spectrometers (GC-HRMS) is well established for dioxin and furan analysis. However, the use of gas chromatography coupled to triple quadrupole (MS/MS) and time of flight (TOF) mass spectrometers with atmospheric pressure ionization (API) and traditional electron ionization (EI) for dioxin and furan analysis is emerging as a viable alternative to GC-HRMS screening. These instruments offer greater versatility in the lab for a wider range of compound identification and quantification as well as improved ease of operation. The instruments utilized in this study included 2 API-MS/MS, 1 traditional EI-MS/MS, an API-quadrupole time of flight mass spectrometer (API-QTOF), and a EI-high-resolution TOF (EI-HRTOF). This study compared these 5 instruments to a GC-HRMS using method detection limit (MDLs) samples for dioxin and furan analysis. Each instrument demonstrated acceptable MDL values for the 17 chlorinated dioxin and furans studied. The API-MS/MS instruments provide the greatest overall improvement in MDL value over the GC-HRMS with a 1.5 to 2-fold improvement. The API-QTOF and EI-TOF demonstrate slight increases in MDL value as compared with the GC-HRMS with a 1.5-fold increase. The 5 instruments studied all demonstrate acceptable MDL values with no MDL for a single congener greater than 5 times that for the GC-HRMS. All 5 instruments offer a viable alternative to GC-HRMS for the analysis of dioxins and furans and should be considered when developing new validated methodologies.