"Cold" solid-phase microextraction method for the determination of volatile halocarbons present in the atmosphere at ultra-trace levels

Anthropogenic volatile halocarbons are compounds of great enviromnental concern because of their involvement in global change phenomena. They are present in the atmosphere at concentration levels in the order of parts per trillion by volume. The chosen analytical method for their determination is capillary gas chromatography coupled to mass spectrometry, preceded by an enrichment step on suitable adsorbent resins. The method here presented makes use of the solid-phase microextraction as a pre-analytical technique, using sub-ambient temperature in order to enhance the retention capability of the fiber coating. The proposed method was evaluated in terms of extraction efficiency, linearity, reproducibility, andlimits of detection. Results obtained showed that trace atmospheric halocarbons are detectable even when enriching very small air sample volumes. A good chromatographic resolution is obtained as a consequence of the extremely low injection volume. Finally a standard GC-MS instrumentation equipped with a simple split-splitless injector was employed, thus avoiding the use of expensive dedicated apparatus. The method was also applied to the analysis of actual samples collected both in remote, and in semi-remote sites.     

A Ten Years Monitoring of Chlorofluorocarbons at the Antarctica: Results and Perspectives

Abstract

Chlorofluorocarbons are man-made long lasting atmospheric pollutants of great environmental concern, responsible for important global change phenomena. Recently, they were replaced by hydrogenated halocarbons that, even if less persistent, do not lack in environmental impact. Atmospheric concentrations of these compounds were measured in Antarctica by gas chromatography. The extremely low atmospheric mixing ratios of these compounds require a pre-concentration step of the air sample on suitable adsorbent in order to meet the sensitivity of the analytical method Results obtained analyzing air samples collected in Antarctica since 1988 for the determination of CFC-12 and CFC-11 are reported, together with data concerning the less abundant species.     

Separation of mixed halocarbons of environmental interest on a new type of silica-based porous-layer open tubular capillary gas chromatographic column

A new type of capillary porous-layer open tubular (PLOT) column consisting of a hydrophobic silica layer on a fused-silica capillary has been tested for the separation of a mixture of environmentally sensitive halocarbons present in tropospheric air. The column shows high retention for a wide range of halocarbons, with elution orders following both boiling point order and hydrogen bonding capability. The resolution of the halocarbons is good and only one pair of halocarbons [CHFClCF₃ (HCFC 124) and CH₃CF₂Cl (HCFC 142b)] cannot be resolved on this column type at all column temperature profiles. Unlike alumina PLOT columns, the silica PLOT column does not dehydrohalogenate labile halocarbons. Excellent reproducibility of retention times and peak areas for halocarbons on the column are reported.     

Simultaneous analysis of atmospheric halocarbons and non-methane hydrocarbons using two-dimensional gas chromatography

A gas chromatographic system was constructed to simultaneously measure ambient non-methane hydrocarbons (NMHCs) and halocarbons, which play significant roles in tropospheric ozone formation and stratospheric ozone loss, respectively. A heart-cut device based on a Deans switch was connected to two capillary columns to cover the full range of NMHCs and halocarbons. Analytes more volatile than C₆ NMHCs and the halocarbon CFC-113 were separated with a PLOT column, while the remaining less volatile compounds were separated with a DB-1 column. Merge-and-split of the flows at the end of the two columns allowed the NMHCs and halocarbons to be observed simultaneously by electron capture detection (ECD) and flame ionization detection (FID). To avoid peak-overlap from the two columns while merging, programmed pressures were incorporated to control the Deans switch. In addition to the advantage of measuring two important classes of compounds in the atmosphere at the same time, this method has the additional benefit of using the homogeneity of atmospheric CFC-113 as an “intrinsic” internal reference. Thus, better data continuity, less consumption of gas standards, and real-time quality control can all be achieved.     

Gas chromatography of low molecular weight halocarbons on macroporous silica modified by a thin liquid phase film

Summary The use of the silica adsorbent Silochrom C-80 modified by a thin liquid stationary phase film is proposed for the gas chromatographic analysis of low molecular weight halocarbons. Such modified adsorbents are characterized by good retention of the volatile halocarbons and high selectivity with respect to halocarbons. The thermodynamic sorption characteristics of alkanes, chloroalkanes and chloromethanes on Silochrom modified by three liquid phases (Apiezon L, methylsilicone and polyethylene glycol 20M) and on Chromaton N with thick films of the same phases were studied. The heats of sorption (−ΔH) and free sorption energy changes (−ΔF) of these substances and the increments −Δ(ΔH) and −Δ(ΔF) per chlorine atom in the chloralkane molecule compared with n-alkanes with the same number of carbon atoms were determined. The “chlorine” retention indices of low molecular weight volatile halocarbons on three sorbents were determined to identify them in aqueous solutions using the electron-capture detector. The analysis of drinking water by this technique is demonstrated.     

On-line flow injection analysis of volatile organic compounds in seawater by membrane introduction mass spectrometry

The combination of flow injection analysis with membrane introduction mass spectrometry for analysis of volatile organic compounds (VOCs) in seawater is examined and is compared to measurements made in water. Membrane introduction mass spectrometry is performed using a benchtop ion trap mass spectrometer, and characterization of various aspects of the flow injection and ion trap combination for the analysis of volatile organic compounds (including anthropogenic halocarbons) in seawater is carried out. The analyte responses are shown to be linear over several orders of magnitude (e.g. for methylene chloride), independent of seawater pH (e.g. for chlorobenzene) and independent of matrix effects for the VOCs studied. A comparison of the performance of a microporous (Teflon) membrane with that of an amorphous silicone membrane is made, and the former is shown to provide lower detection limits which are in the parts-per-trillion range (300 ppt for chlorobenzene, 190 ppt for trans-1,2-dichloroethene). The microporous membrane provides faster response times by a factor of four to five for relatively more polar compounds, such as chlorobenzene. An analysis of a seven-component mixture demonstrates the ability of this on-line combination to allow multicomponent analysis of mixtures of some complexity.     

Generation of standard gas mixtures of halogenated, aliphatic, and aromatic compounds and prediction of the individual output rates based on molecular formula and boiling point

In this work, we describe a simple diffusion capillary device for the generation of various organic test gases. Using a set of basic equations the output rate of the test gas devices can easily be predicted only based on the molecular formula and the boiling point of the compounds of interest. Since these parameters are easily accessible for a large number of potential analytes, even for those compounds which are typically not listed in physico-chemical handbooks or internet databases, the adjustment of the test gas source to the concentration range required for the individual analytical application is straightforward. The agreement of the predicted and measured values is shown to be valid for different groups of chemicals, such as halocarbons, alkanes, alkenes, and aromatic compounds and for different dimensions of the diffusion capillaries. The limits of the predictability of the output rates are explored and observed to result in an underprediction of the output rates when very thin capillaries are used. It is demonstrated that pressure variations are responsible for the observed deviation of the output rates. To overcome the influence of pressure variations and at the same time to establish a suitable test gas source for highly volatile compounds, also the usability of permeation sources is explored, for example for the generation of molecular bromine test gases.     

Problems caused by the activity of Al2O3-PLOT columns in the capillary gas chromatographic analysis of volatile organic compounds

Summary Al₂O₃-PLOT columns are used with great advantage for the analysis of volatiles, because of the increased capacity ratio and selectivity compared to WCOT-columns. Their applicability is limited to relatively non-polar components with relatively low boiling points i. e. eluting before n-decane.In the analysis of the halocarbons in stratospheric air, the decomposition of certain compounds was observed. In this study the stability of a number of volatile organic compounds was determined in function dependence of the column temperature using a two-dimensional GC-system.A possible reaction mechanism for the decomposition is proposed and confirmed for several chlorinated ethanes.     

Construction and validation of a cryogen free gas chromatography-electron-capture detection system for the measurement of ambient halocarbons

A fully automated GC-ECD system was constructed to perform unattended on site measurement of airborne halocarbons. To adequately manage water vapor during analysis a retractable thermoelectric cooling device was built and incorporated into the automated GC-ECD system for retaining water vapor during sample preconcentration. This device allows the trap tubing to engage with the cooling block when trapping, or disengage for flash thermal desorption. Thus, no cryogen was needed either in preconcentration or column separation. Unattended continuous hourly measurement of halocarbons was then performed in the field to evaluate effect of water vapor on halocarbon measurement by targeting compounds that are more subject to surface adsorption, such as CCl₄. Excellent reproducibility of CCl₄ was observed during the measurement period by cooling the trap at 5 °C. By contrast, when trapping at 30 °C without sufficient water retention the reproducibility of CCl₄ suffered greatly, exhibiting an obvious systematic error with the measurement.     

New detectors in environmental monitoring using tritium sources

A new generation of ion mobility spectrometers has been designed especially for the environmental monitoring due to toxic compounds in ambient air: phosgene, halocarbons, isofluorane, halothane, formaldehyde, ethylenoxide, acrolein, chemical warfares and many others. The IMS is equipped by means of tritium ionization sources, which have lower radiation hazards than nickel-63 sources. Aromatics are monitored by means of a special version using photoionization. Minimal detectable concentrations are in the ppb-range, mostly even below.     

STUDIES ON SULFINATODEHALOGENATION:THE REACTION OF POLYFLUOROALKYL IODIDES WITH 4-PENTENOIC ACID COMPOUNDS

The radical addition of polyfluoroalkyl iodides to carbon-carbon multiple bonds is one of the most important and general methods for synthesis of a variety of fluorine-containing organic compounds.^[1] Studies in our laboratory on stulfinatodehalogenation reaction showed that sodium dithionite was a excellent initiation reagent for the addition of polyfluoroalkyl iodides, bromides and halocarbons to alkenes, alkynes and conjugated dienes effectively under mild conditions.^[2]     

Problems connected with the analysis of halocarbons and hydrocarbons in the non-urban atmosphere

The problems connected with the measurement of hydrocarbons outside urban areas are considerable: The atmospheric mixing ratios of most of the hydrocarbons are very low--from a few ppb down to some ppt; the mixture of hydrocarbons is extremely complex, ranging from light n-alkanes to alkyl benzenes and terpenes; for measurements in remote areas the logistic conditions often restrict the instrumentation which can be used for sample collection or in situ measurements (such as lack of electric power supply, weight restrictions etc.). Nevertheless, sensitive and sufficiently reliable measurements of hydrocarbons in the non-urban atmosphere are important. Hydrocarbons are important factors in the tropospheric photochemistry (e.g. ozone formation) and can be used as valuable tracers for man-made atmospheric pollutants etc. Other useful tracers for anthropogenic emission are halocarbons such as dichlormethane, tri- and tetrachloroethen etc. The impact of man-made hydrocarbons on the chemistry of the troposphere can only be understood if the extent of natural (biogenic) contributions is known. From measurements of a large variety of hydrocarbons and halocarbons it is often possible to obtain information about the sources of the most important atmospheric hydrocarbon species, even for trace gases with both significant anthropogenic and biogenic sources. In this presentation some of the problems and their solutions connected with such measurements of atmospheric hydrocarbons and halocarbons are presented and discussed. Some of the results obtained by several series of measurements are described, indicating that man-made as well as biogenic hydrocarbons can be important factors for the chemistry of the atmosphere.     

Sampling of organic volatiles in the atmosphere at moderate and low pollution levels

Several techniques are available for measuring organic volatiles in the atmosphere. For measurements at low and moderate pollution levels (between several μg m^?3 and a fraction of a μg m^?3), the existing methods can be adopted to a broad range of different compounds. Whole-air sampling in stainless-steel containers with metal bellows valves combined with subsequent gas chromatographic separation after preconcentration in the laboratory is probably the best procedure for low and medium molecular weight trace gases of moderate or low polarity and reasonable chemical stability (e.g., hydrocarbons and halocarbons). For organic compounds of lower volatility, adsorptive sampling on non-polar porous organic polymers (e.g., Tenax) and thermal desorption combined with cryotrapping and gas chromatographic separation of the sampled compounds is widely used. However, there are often substantial problems due to artefact formation or loss reactions. Owing to the generally larger sample volumes, these problems are even more pronounced for sorptive sampling techniques combined with sample recovery by solvent extraction. Unfortunately, the general understanding of the various processes of sample degradation due to chemical reactions of reactive components of the atmosphere with each other or with the sorbent is not yet sufficient to allow reasonable estimates of the extent of such interferences without elaborate test procedures.     

A novel porous carbon and its perspectives for the solid phase extraction of volatile organic compounds

A porous carbon sorbent prepared by controlled pyrolysis of saccharose in a matrix of silica gel was tested for the preconcentration of a variety of compounds differing in polarity and volatility (hydrocarbons, halocarbons, oxygenated compounds) in simulated and real air samples. The trapped components were desorbed off-line by liquid-(carbon disulphide and carbon disulphide with 1% methanol) and on-line by thermo-desorption in combination with HRCGC. Adsorption-desorption properties of the sorbent were evaluated according to the determined recovery values, whereby physicochemical interactions of both the sorbent and solute were taken into consideration. With oxygenated compounds recovery data indicate the presence of active sites on the surface of the sorbent.Dedicated to Professor Dr. Dr. h.c. mult. J. F. K. Huber on the occasion of his 70th birthday     

Application of Headspace Liquid-Phase Microextraction to the Analysis of Volatile Halocarbons in Water

The determination of four volatile halocarbons (CHCl₃, CCl₄, C₂HCl₃ and C₂Cl₄) in water by headspace liquid-phase microextraction (HS-LPME) with gas chromatography using a micro electron capture detector (GC-μECD) is described. The effects of the type and volume of the extraction solvent, headspace volume, stirring rate, extraction temperature and time and ionic strength on the extraction performance are investigated and optimized. The developed protocol yields a linear calibration curve in the concentration range from 0.05 to 50 µg L^?1 for the target analytes; the detection limits ranged from 0.003 to 0.146 µg L^?1 and the relative standard deviation (R.S.D.) values below 8.45%. The results demonstrate that HS-LPME followed with GC-μECD is a simple and reliable technique for the determination of volatile halocarbons in water samples.     

Microwave induced plasma atomic emission spectrometry: a suitable detection system for the determination of volatile halocarbons

Microwave induced plasma atomic emission spectrometry (MIP-AES), a highly sensitive detection system for organometal compounds, was coupled to an automated purge and trap gas chromatographic system for the determination of volatile halogenated hydrocarbons in environmental water samples. Optimisation of the parameters affecting the injection and detection system led to relative detection limits from 1 to 14 ng · L^–1 for chlorine- and bromine-compounds and from 10 to 75 ng · L^–1 for iodine-compounds, on basis of a 10 mL sample volume. A comparison of the analytical characteristics between atomic emission detection (AED) and electron capture detection (ECD) showed a lower sensitivity of the atomic emission detector for halocarbons, but the detection thresholds are low enough to use the method for the determination of volatile halocarbons in trace level concentrations. The ability of the atomic emission detector provides increased selectivity for monitoring individual halogenated compounds under simplified and rapid chromatographic conditions, within a total analysis time of only 30 min. The method was applied with gas chromatographic separation for the analysis of sea water samples. Concentrations for the different elements between 0.05 and 15.28 μg · L^–1 were determined.     

Trace analysis of halocarbons in water; Direct aqueous injection with electron capture detection

Interest in monitoring halogenated organics in drinking water and natural surface and ground water in the low ppb range continues to grow. There is a tendency to include still more volatile halocarbons, the trace determination of which is known to be rather demanding. This prompted us to re-examine the feasibility of large-volume direct aqueous injection onto capillary columns, coupled with ECD. A primary problem was to avoid simultaneous elution of water with halocarbons, since water suppresses the ground current of the ECD. The following measures contributed to the solution of this problem. Apolar, extremely inert, columns are required to elute water completely, and even before very light halocarbons. Their coatings have to be far thicker (≈? 5 mUm) than commonly employed thick films since they must permit isothermal analysis at a column temperature around 100°C in order to ensure rapid and complete elution of water. Finally, it is essential that sampling be carried out on-column for two reasons: diffusion of water vapor in the injector, resulting in delayed elution, is then eliminated, and peak distortion during splitless injection is avoided. Although we now know that persilylated columns with immobilized coatings withstand routine water injections, more longterm experience is needed to provide detailed recommendations for the handling of these columns.     

Enantiomer separation by gas chromatography on cyclodextrin chiral stationary phases

Fused silica capillary columns coated with several alkyl or acyl cyclodextrin derivatives, especially those of α- and β-cyclodextrins, are suitable for the enantiomer separation of a wide variety of volatile compounds of different molecular size and functionality. Positional isomers and more than 250 pairs of optical isomers have been resolved, including chiral hydrocarbons, acetals, ethers, epoxides, carbonates, lactones, esters, acids, ketones, aldehydes, alcohols, halocarbons, and also nitrogen-and sulfur-containing compounds. The physical properties of the cyclodextrin derivatives, even those obtained as viscous fluids, could be improved by dissolving them in polysiloxane liquid phases commonly used for GLC.