Second-Dimension Temperature Programming System for Comprehensive Two-Dimensional Gas Chromatography. Part 1: Precise Temperature Control Based on Column Electrical Resistance.

A second-dimension temperature programming system (2DTPS) for comprehensive two-dimensional gas chromatography (GC × GC) is introduced, and its performance is characterized. In the system, a commercial stainless-steel capillary column was used for the separation, as a heating element, and as a temperature sensor. The second dimension (2D) column was resistively heated and controlled using an Arduino Uno R3 microcontroller. Temperature measurement was accomplished by measuring the overall 2D column's electrical resistance. A diesel sample was used to compare the 2D peak capacity (2nc) and resolution (2Rs), while a perfume sample was used to compare the reproducibility of the system for within-day (n = 5) and day-to-day (n = 5) results. The 2nc improved by 52% with the 2DTPS compared to the secondary oven. The GC × GC system utilizing the 2DTPS had an average within-day and day-to-day relative standard deviation (RSD) of 0.02 and 0.12% for the 1D retention time (1tR), 0.56 and 0.58% for the 2D retention time (2tR), and 1.18 and 1.53% for the peak area, respectively.

Second-Dimension Temperature Programming System for Comprehensive Two-Dimensional Gas Chromatography. Part 2: Technical Improvements and Compatibility with Flow Modulation and Time-of-Flight Mass Spectrometry.

The second-dimension (2D) temperature programming system (2DTPS) for comprehensive two-dimensional gas chromatography (GC × GC) described in Part 1 was updated and tested with the time-of-flight mass spectrometer (TOFMS) and flow modulator. Addition of a real-time clock and remote port allowed the 2DTPS to be a truly standalone system to be used with any GC × GC instrument. GC × GC reproducibility with the 2DTPS was tested with thermal and flow modulation, coupled with the TOFMS and/or FID to demonstrate compatibility with all typical GC × GC setups. An improvement in the match factor, reverse match factor, and signal-to-noise ratio was found when performing 2D temperature programming. Within-day and day-to-day reproducibility of the 2DTPS for the 1D retention time (≤0.04 and ≤0.05%), 2D retention time (≤0.36 and ≤0.52%), and peak area (≤2.47 and ≤3.37%) were acceptable, while providing flexibility in 2D optimization and improved peak capacity.

Green comprehensive two-dimensional liquid chromatography (LC × LC) for the analysis of phenolic compounds in grape juices and wine.

Grape juices and wines are rich in numerous groups of polyphenolic compounds which require a dedicated separation technique for such complex samples. LC × LC is considered the best technique for the analysis of such samples as it can achieve better resolution and higher peak capacity compared to 1D LC. The ever-growing demand for protecting the environment necessitates reducing or eliminating hazardous solvents to improve the environmental friendliness of analytical procedures. In this study, propylene carbonate was used as an eco-friendly mobile phase component in comprehensive two-dimensional liquid chromatography to analyze phenolic compounds in grape juices and a dealcoholized wine sample. Novel green RPLC × RPLC-DAD and RPLC × RPLC-MS methods were developed for the first time to identify phenolic compounds in five samples (two red grape juice samples, two white grape juice samples, and one dealcoholized wine sample). Four different RPLC × RPLC systems were developed; three systems were connected to a diode array detector (RPLC × RPLC-DAD), while the fourth system was connected to DAD and MS detectors (RPLC × RPLC-DAD-ESI-MS). Solvent X (propylene carbonate:ethanol, 60:40) was adopted as a green organic modifier in the first dimension (1D) and methanol in the second dimension (2D). The practical peak capacity and the surface coverage were calculated as metrics to measure the separation performance of all proposed systems. The orthogonality values for the setups ranged from 0.64 to 0.92 when calculated by the convex hull method, and from 0.54 to 0.80 when calculated by the asterisk equations method. The practical peak capacity production rate ranged from 14.58 to 22.52 peaks/min. The results revealed that the phenolic compounds were separated efficiently with good coverage of the 2D separation space and high peak capacity. A total of 70 phenolic compounds were detected based on MS data and information from the literature.

Green Approaches to Sample Preparation Based on Extraction Techniques.

Preparing a sample for analysis is a crucial step of many analytical procedures. The goal of sample preparation is to provide a representative, homogenous sample that is free of interferences and compatible with the intended analytical method. Green approaches to sample preparation require that the consumption of hazardous organic solvents and energy be minimized or even eliminated in the analytical process. While no sample preparation is clearly the most environmentally friendly approach, complete elimination of this step is not always practical. In such cases, the extraction techniques which use low amounts of solvents or no solvents are considered ideal alternatives. This paper presents an overview of green extraction procedures and sample preparation methodologies, briefly introduces their theoretical principles, and describes the recent developments in food, pharmaceutical, environmental and bioanalytical chemistry applications.

Temperature Programming of the Second Dimension in Comprehensive Two-Dimensional Gas Chromatography.

Comprehensive two-dimensional gas chromatography (GC × GC) provides a significant increase in selectivity and peak capacity for the separation of complex mixtures. Optimization of the system is often complicated, with many interconnected parameters between the two dimensions and additional problems like peak wraparound that need to be eliminated or minimized. Wraparound peaks are compounds with retention times in the second dimension that are longer than the modulation period. This results in broad peaks that elute in subsequent modulation cycles, potentially coeluting with separated compounds. The use of a secondary oven is often the solution to the problem. By applying a constant positive temperature offset from the main oven temperature, the retention of all analytes can be reduced so that they elute within their respective modulation periods. However, this reduces the separation of less retained compounds, a classical consequence of the general elution problem due to the isothermal conditions during the limited separation time in the second dimension. To overcome this problem, the second dimension was temperature-programmed by resistively heating an electrically conductive secondary column using constant current. The column was cooled through forced convection inside the GC oven within the time frame of a single modulation period. Temperature programming in the second dimension of GC × GC was able to improve separation while eliminating wraparound peaks and reducing peak widths, leading to significantly increased second dimension peak capacity.

The quantification of short-chain chlorinated paraffins in sediment samples using comprehensive two-dimensional gas chromatography with µECD detection.

The analysis of persistent organic pollutants in environmental samples is a challenge due to the very large number of compounds with varying chemical and physical properties. Chlorinated paraffins (CPs) are complex mixtures of chlorinated n-alkanes with varying chain lengths (C10 to C30) and degree of chlorination (30 to 70% by weight). Their physical-chemical properties make these compounds persistent in the environment and able to bioaccumulate in living organisms. Comprehensive two-dimensional gas chromatography (GC × GC) coupled with micro-electron capture detection (µECD) was used to separate and quantify short-chain chlorinated paraffins (SCCP) in sediment samples. Distinct ordered bands were observed in the GC × GC chromatograms pointing to group separation. Using the Classification function of the ChromaTOF software, summary tables were generated to determine total area counts to set up multilevel-calibration curves for different technical mixes. Fortified sediment samples were analyzed by GC × GC-µECD with minimal extraction and cleanup. Recoveries ranged from 120 to 130%. To further validate the proposed method for the analysis of SCCPs, the laboratory participated in interlaboratory studies for the analysis of standards and sediment samples. The results showed recoveries between 75 and 95% and z-score values <2, demonstrating that the method is suitable for the analysis of SCCPs in soil/sediment samples. Graphical abstract Quantification of SCCPs by 2D-GC-µECD.

Analysis of honeybush tea (Cyclopia spp.) volatiles by comprehensive two-dimensional gas chromatography using a single-stage thermal modulator.

The applicability of comprehensive two-dimensional gas chromatography (GC×GC) using a single-stage thermal modulator was explored for the analysis of honeybush tea (Cyclopia spp.) volatile compounds. Headspace solid phase micro-extraction (HS-SPME) was used in combination with GC×GC separation on a non-polar × polar column set with flame ionisation (FID) detection for the analysis of fermented Cyclopia maculata, Cyclopia subternata and Cyclopia genistoides tea infusions of a single harvest season. Method optimisation entailed evaluation of the effects of several experimental parameters on the performance of the modulator, the choice of columns in both dimensions, as well as the HS-SPME extraction fibre. Eighty-four volatile compounds were identified by co-injection of reference standards. Principal component analysis (PCA) showed clear differentiation between the species based on their volatile profiles. Due to the highly reproducible separations obtained using the single-stage thermal modulator, multivariate data analysis was simplified. The results demonstrate both the complexity of honeybush volatile profiles and the potential of GC×GC separation in combination with suitable data analysis techniques for the investigation of the relationship between sensory properties and volatile composition of these products. The developed method therefore offers a fast and inexpensive methodology for the profiling of honeybush tea volatiles. Graphical abstract Surface plot obtained for the GC×GC-FID analysis of honeybush tea volatiles.

Development and Design of a Single-Stage Cryogenic Modulator for Comprehensive Two-Dimensional Gas Chromatography.

A new liquid nitrogen-based single-stage cryogenic modulator was developed and characterized. In addition, a dedicated liquid nitrogen delivery system was developed. A well-defined restriction placed inside a deactivated fused silica capillary was used to increase the cooling surface area and provide very efficient trapping. At the same time, it enabled modulation of the carrier gas flow owing to changes in gas viscosity with temperature. Gas flow is almost unimpeded at the trapping temperature but reduced to nearly zero at the desorption temperature, which prevents analyte breakthrough. Peak widths for n-alkanes of 30-40 ms at half height were obtained. Most importantly, even the solvent peak could be modulated, which is not feasible with any commercially available thermal modulator. Evaluation of the newly developed system in two-dimensional gas chromatography (GC × GC) separations of some real samples such as regular gasoline and diesel fuel showed that the analytical performance of this single-stage modulator is fully competitive to those of the more complicated dual-stage modulators.

Two-dimensional liquid chromatography with reversed phase in both dimensions: A review.

Two-dimensional liquid chromatography (2D-LC), and in particular comprehensive two-dimensional liquid chromatography (LC×LC), offers increased peak capacity, resolution and selectivity compared to one-dimensional liquid chromatography. It is commonly accepted that the technique produces the best results when the separation mechanisms in the two dimensions are completely orthogonal; however, the use of similar separation mechanisms in both dimensions has been gaining popularity as it helps avoid difficulties related to mobile phase incompatibility and poor column efficiency. The remarkable advantages of using reversed phase in both dimensions (RPLC×RPLC) over other separation mechanisms made it a promising technique in the separation of complex samples. This review discusses some physical and practical considerations in method development for 2D-LC involving the use of RP in both dimensions. In addition, an extensive overview is presented of different applications that relied on RPLC×RPLC and 2D-LC with reversed phase column combinations to separate components of complex samples in different fields including food analysis, natural product analysis, environmental analysis, proteomics, lipidomics and metabolomics.

Green ultra-fast high-performance liquid chromatographic method using a short narrow-bore column packed with fully porous sub-2 µm particles for the simultaneous determination of selected pharmaceuticals as surface water and wastewater pollutants.

Fast separations are very desirable in laboratories that analyze large numbers of samples per day or those needing short turn-around times. Traditional HPLC methods using conventional stationary phases and standard column dimensions require significant amounts of organic solvents and generate large volumes of waste. With growing awareness about the environment, the development of green technologies has been receiving increasing attention. In this work, a very fast green analytical method based on LC-UV using a short narrow bore column packed with fully porous sub-2 µm particles has been developed for simultaneous determination of nine pharmaceuticals in wastewater and surface water. The chromatographic separation was optimized in order to achieve short analysis time and good resolution for all analytes in a single run. All analytes could be separated in 1 min with good resolution. Sample preparation was executed by solid phase extraction using Oasis HLB cartridges. The method developed was validated based on parameters such as linearity, precision, accuracy, detection, and quantification limits. The recovery ranged from 70.9 to 92.5% with SDs not higher than 5.4%, except for acetaminophen and sulphanilamide. LODs ranged from 0.6-2.5 µg/L, while the LOQs were in the range 2-8 µg/L.

Optimization and validation of a fast ultrahigh-pressure liquid chromatographic method for simultaneous determination of selected sulphonamides in water samples using a fully porous sub-2 µm column at elevated temperature.

High temperature in HPLC is considered a valuable tool helping to overcome the increase in the column backpressure when using small packing particles such as sub-2 µm, as it allows reduction in the mobile-phase viscosity. In this study, a fast analytical method based on HPLC-UV was developed using a sub-2 µm column at elevated temperature for the simultaneous determination of nine sulphonamides. Owing to the lower viscosity of the mobile phase, the separation could be achieved in 3 min at 60°C for all analytes. The effect of temperature, the organic modifier percentage and the flow rate on the retention time was studied. The method developed was used for the determination of selected sulphonamides in surface and wastewater samples. Sample preparation was carried out by solid-phase extraction on Oasis HLB cartridges. The method developed was validated based on the linearity, precision, accuracy, detection and quantification limits. The recovery ranged from 70.6 to 96 % with standard deviations not higher than 4.7%, except for sulphanilamide. Limits of detection ranged from 1 to 10 µg/L after optimization of all analytical steps. This method has the highest performance in terms of analytical speed compared with other published HPLC-UV methods for the determination of sulphonamides in water.

Modulation in comprehensive two-dimensional gas chromatography: 20 years of innovation.

With almost 20 years having passed since John B. Phillips described the first comprehensive two-dimensional gas chromatography (GC × GC) separation, much has occurred in this ever-expanding field of separation science. GC × GC is currently one of the most effective techniques for the separation and analysis of complex mixtures, offering significantly greater peak capacities than conventional chromatographic methods. The technique is generally based upon separations performed on two chromatographic columns characterized by considerably different selectivities, joined together through a modulating interface. The modulator periodically traps or samples the primary column effluent, usually refocuses it into a narrow chromatographic band and injects the focused fraction into the secondary column. The modulator is often referred to as the 'heart' of the instrument, since a GC × GC separation is impossible without its use. This article reviews major innovations in GC × GC modulator development since its first use by Phillips in 1991. Emphasis has been placed on modulator design and function.

Spatial and seasonal patterns of benzene, toluene, ethylbenzene, and xylenes in the Gdansk, Poland and surrounding areas determined using radiello passive samplers.

Atmospheric concentrations of benzene, toluene, ethylbenzene, and xylenes (BTEX) were assessed in the Gdansk-Sopot-Gdynia Tricity area and in the city of Tczew using diffusive-type Radiello passive samplers. Samples were collected at the monitoring stations belonging to the Agency of Regional Air Quality Monitoring Foundation. The results indicated that the BTEX concentrations measured in the urban air in the Tricity area and in Tczew were dependent on the season, being somewhat higher in winter and spring than in summer. Maps of BTEX pollution in the Tricity and in Tczew were prepared by interpolating the results for the areas between the sampling points covering the mapped areas. This allowed the assessment of time-weighted average concentrations of the compounds studied at locations where measurements were not made.

Parallel gradients in comprehensive multidimensional liquid chromatography enhance utilization of the separation space and the degree of orthogonality when the separation mechanisms are correlated.

Comprehensive two-dimensional liquid chromatography (LC×LC) offers increased peak capacity, resolution and selectivity compared to one-dimensional liquid chromatography. It is commonly accepted that the technique produces the best results when the separation mechanisms in the two dimensions are completely orthogonal, which necessitates the use of gradient elution for each second-dimension fraction. Recently, the use of similar separation mechanisms in both dimensions has been gaining popularity, but full or shifted gradients are still used for each second dimension fraction. Herein, we argue that when the separation mechanisms are correlated in the two dimensions, the best results can be obtained with the use of parallel gradients in the second dimension, which makes the technique nearly as user-friendly as comprehensive two-dimensional gas chromatography. This has been illustrated through the separation of a mixture of 39 pharmaceutical compounds using reversed phase in both dimensions. Different selectivity in the second dimension was obtained through the use of different stationary phase chemistries and/or mobile phase organic modifiers. The best coverage of the separation space was obtained when parallel gradients were applied in both dimensions, and the same was true for practical peak capacity.

Theory and modelling approaches to passive sampling.

Designs and applications of passive samplers for various environmental compartments have been broadened significantly since their introduction. Understanding the theory behind passive sampling is essential for proper development of sampling methods and for accurate interpretation of the results. Theoretical underpinnings of passive sampling have been explored using different approaches. The aim of this review is to describe passive sampling theory and modelling approaches presented in the literature in a manner that allows researchers to obtain comprehensive understanding of them and to recognize the assumptions behind each approach together with their applicability to a given passive sampling technique. A common approach originates from Whitman's two-film theory and produces an exponential model that describes the entire passive sampling process. This approach, however, is based on several assumptions including linear exchange kinetics between the sampled medium and the passive sampler. Two-phase air passive samplers with a well-defined barrier are commonly modeled based on the zero-sink assumption, which assumes efficient trapping of analytes in the receiving phase. This assumption may become invalid under various scenarios; consequently, other approaches to modelling have been introduced including simulation of the sampling process by approximate temporal-steady states in hypothetical segments in the adsorption phase. Another approach uses dynamic models to determine accumulation of analytes in passive samplers. Dynamic models are capable of describing mass accumulation in the passive sampler, its transient response, and its response to fluctuations in environmental concentrations. Finally, empirically calibrated models, attempting to simplify the process of passive sampling rate determination, are also presented. In general, dynamic models are used to establish a profound understanding of the sampling process and analyse the applicability of the simpler models and their assumptions, while the simplified models are desirable and practical for most users. Nonetheless, due to the advancement in the computational tools, application of the dynamic models could be made simple and user-friendly.

New applications of the mathematical model of a permeation passive sampler: prediction of the effective uptake rate and storage stability.

As the applications of passive sampling in environmental analysis are increasing, it is crucial to ensure that the methods applied in the measurement of pollutant concentrations provide sufficient accuracy in compliance with existing regulations. Additionally, as with any sampling method in an analytical process, sample integrity is essential for accurate determination of contaminants and their concentrations. In a recent study, a mathematical model was developed to describe the sampling process in permeation passive samplers. The model was able to predict the significance of potential uptake rate changes during sampling. The model also predicted the distribution of the sampled analyte within the different compartments of the sampler. In the present work, the model was extended to include two practical applications. In the first part, a novel method allowing prediction of the effective uptake rate of the sampler is presented. The method accounts for changes in the uptake rate during the exposure time caused by resistance to mass transfer in the sorbent bed, allowing accurate calculation of the time weighted average concentrations. The method was proven to be successful through experimental verification that involved sampling toluene and trichloroethylene using the Waterloo Membrane Sampler (WMS). In the second part, the post-sampling storage period of analytes in the WMS was evaluated. It was found both theoretically and experimentally that analyzing the sorbent only is sufficient to quantify the analytes collected, as the amount retained in the remaining compartments of the sampler (PDMS membrane, air inside the sampler and the storage vial) is negligible after sampling. The amounts of analytes collected by the sorbent were stable over up to three-weeks of storage at room temperature. These findings establish confidence in the use of the WMS for sampling Volatile Organic Compounds (VOCs).

Modelling permeation passive sampling: intra-particle resistance to mass transfer and comprehensive sensitivity analysis.

A mathematical model developed previously to describe the sampling process in permeation passive samplers with non-porous adsorbents and evaluated using the Waterloo Membrane Sampler (WMS) is here extended to include adsorbents with porous particles. This work was motivated by the need to expand the model applicability to include the various types of adsorbents used in the WMS, and to develop a deep understanding of the model sensitivity towards required parameters. The effects of intraparticle porosity on the effective diffusivity of the analyte in a bed of porous particles and on the mass transfer coefficient for analyte transport from the interparticle void phase to the porous solid phase are both evaluated. Experimental validation of the applicability of the model on adsorbents with microporous particles was carried out using the WMS containing Anasorb 747, a carbon-based adsorbent with highly porous particles. Good agreement between the experimental and model results was found. A comprehensive sensitivity analysis was also conducted to identify the parameters with the greatest influence on the results of the calculated uptake rate. This analysis included two types of adsorbents with different sorption strengths. The results showed that the uptake rate sensitivity is limited to parameters related to mass transfer in the membrane for strong adsorbents. On the other hand, sensitivity to parameters related to mass transfer in the sorbent bed becomes more significant as the strength of the adsorbent decreases; however, this effect can be reduced by increasing the membrane thickness. Influential parameters in the sorbent bed are also affected by the temperature. Nevertheless, the contribution of this change to the total effect of temperature change on the uptake rate is expected to be negligible within the small range of temperature variations usually encountered during a single environmental sampling event, especially in soil-gas sampling which is the most widely used application of the WMS.

Passive sampling in environmental analysis.

Since its invention more than three decades ago, passive sampling technology has been widely used for environmental monitoring throughout the world. In many cases, it is the only practical means of determining pollution levels caused by numerous anthropogenic chemicals. Passive sampling technology today is used in various areas ranging from workplace exposure monitoring to global issues of climate change arising due to the presence of various chemicals in the atmosphere. In this review, the present status of the technology and its applications will be discussed along with aspects related to its regulatory acceptance and recent trends.

Thermal desorption comprehensive two-dimensional gas chromatography for in-situ measurements of organic aerosols.

The complexity of organic composition and temporal variability of atmospheric aerosols presents an extreme analytical challenge. Comprehensive two-dimensional gas chromatography (GC x GC) has been used on time integrated filter samples to reveal the presence of thousands of individual organic compounds in aerosols, but without defining the temporal variability in composition ideal for providing information on source resolution and human exposure to specific pollutants. We hereby introduce a new instrument, 2D-TAG, which combines our in-situ thermal desorption aerosol GC (TAG) instrument with GC x GC allowing for dramatically improved separation of organics with automated measurements at hourly timescales.

Stop-flow comprehensive two-dimensional gas chromatography with pneumatic switching.

A new method for performing comprehensive GC x GC in the stop-flow mode is presented. A device was used to pneumatically stop the flow in the first dimension ((1)D) (by applying pressure pulses at the junction between the two columns), while flow was maintained in the second dimension ((2)D). This allowed for better preservation of resolution in the (1)D of the GC x GC chromatograms, and the extension of the (2)D's separation space, reducing or eliminating the extent of wraparound. When increased flow rates in the (2)D were used, sensitivity enhancements were also observed.