Determination of chlorinated and brominated micropollutants by capillary gas chromatography coupled with on-column radio frequency plasma atomic emission detection

Capillary gas chromatography (GC) combined with on-column radio frequency plasma atomic emission detection was evaluated for the determination of polychlorinated and polybrominated biphenyls (PCBs and PBBs). Quantitation was possible utilizing a single chlorine or bromine calibration curve based on a randomly selected reference compound, because the signal per ng of halogen ranged within 17 % for 29 congeners. Combined with an internal standard to correct for potential plasma quenching from matrix components, this type of universal quantitation represented a sub-stantial simplification of current calibration procedures. In combi-nation with relatively low detection limits (1–5 pg/s of halogen), the present work suggested that GC, coupled with on-column atomic emission detection is a promising technique for the determination of halogenated micropollutants.     

Environmental applications of capillary gas chromatography coupled with atomic emission detection — a review

Environmental applications of capillary gas chromatography coupled with atomic emission derection (GC-AED) have been reviewed with emphasis on both the commercial and laboratory-built systems. Attention was focused on (1) element-selective detection of non-metallic as well as metallic pollutants, (2) identification of contaminants, and (3) sample preparation considerations.     

Assay of the nerve agent Soman in serum by capillary gas chromatography with nitrogen-phosphorus detection and splitless injection

Summary A procedure is described for the determination of the nerve agent Soman in serum. The nerve agent is separated from the serum on C₁₈ modified silica and then eluted with benzene. The concentrated sample, to which butylacetate is added, is injected splitless into a polyethylene glycol (CP Wax 57) coated fused silica column. Solvent trapping of the analytes occurs due to the added butyl-acetate. The detection is performed with a nitrogen-phosphorus detector (NPD). The determination limit of the method is 40 pg/ml.     

An automated large volume on-column injection technique for capillary gas chromatography

Automated large volume (25-200 μl) on-column injections into a gas chromatograph with a capillary column were successfully performed by coupling a retention gap technique with an air actuated rotary valve. The linearity, injection precision, and carryover were evaluated. Slight boiling point discrimination was observed. This technique is compatible with commonly used chromatographic detectors (FID, ECD, MS) and conditions, while requiring very little instrument modification. The work is directed at the eventual reduction of manpower and turnaround time for sample collection and extraction, and Kuderna-Danish concentration when dealing with methods similar to EPA 625.     

Applications of gas chromatography with an atomic emission detector

An atomic emission detector for gas chromatography has been developed which is, in principle, capable of detecting selectively any element (except helium) which can elute from a gas chromatographic column. Software methods have been developed so far for 23 elements and on isotope, including all of the organic elements along with mercury, lead, tin, silicon, and deuterium. Element-specific analyses are shown for several petroleum, environmental, and aroma samples. A table for the detector's element-specific detection limits, selectivities, and linear dynamic ranges is given for 12 elements and deuterium.     

Element-selective detection using capillary gas chromatography with atomic emission detection

Capillary GC coupled to an atomic emission detector (AED) provides a powerful new hyphenated technique for the separation and characterization of complex mixtures and compounds. The AED provides simultaneous and truly specific multi-element detection. The specificity of detection reduces the need for the complex sample pretreatment procedures which are necessary to reduce the interference from co-eluted substances which is experienced with detectors such as the FID and the ECD. A range of environmentally significant problems has been studied, including PCB analysis, the characterization of the reaction products of a novel waste treatment process, and the profiling of sulfur-containing species formed by the pyrolysis of various types of coal.     

Evaluation of a low-resolution near-IR monochromator for atomic emission detection in capillary gas chromatography

A single 0.2 m focal length near-IR monochromator providing a 0.8–3.2 nm effective bandpass was evaluated as spectrometer for F-, Cl-, Br-, I-, S-, and P-selective atomic emission detection in capillary gas chromatography. With optimized plasma conditions and careful wavelength selection, interferences from eluting hydrocarbons were almost eliminated for all the elements studied (element-to-carbon selectivities between 1000:1 and 10000:1). For Cl and S, other heteroatoms were found not to cause cross-interferences. F-, Br-, I-, and P-selective detection, however, was complicated by this second type of non-specificity. For these atoms, elemental confirmation was carried out by analyzing the samples also for heteroatoms potentially causing interferences.     

A new configuration for coupling purge-and-trap/cryogenic focusing/capillary column gas chromatography with splitless injection mode

A new configuration for coupling a purge-and-trap unit to a capillary column gas chromatograph via a cryogenic focusing interface has been developed. In this configuration, the precolumn of the cryogenic focusing interface was inserted through the septum of a split/splitless injection port where it served as both sample transfer and carrier gas supply lines. The injection port of the gas chromatograph was modified by plugging the carrier gas and the septum purge lines. This configuration allowed for the desorption of analytes at high flow rates while maintaining low, analytical-column flow rates which are necessary for optimum capillary column operation. The capillary column flow rate is still controlled by the column backpressure regulator. Chromatograms of purgeable aromatics exhibited improved resolution, especially for early eluting components compared to those obtained by direct liquid injection using the normal splitless injection mode. Quantitative sample transfer to the analytical column afforded excellent linearity and reproducibility of compounds studied.     

Factors affecting C:H and C:N ratios determined by gas chromatography coupled with atomic emission detection

An atomic emission detector has been evaluated for the estimation of C:H and C:N ratios of compounds eluted in gas chromatography. When C:H and C:N ratios were estimated using external reference compounds, the greatest accuracy was obtained when the quantity of the reference compound was similar to that of the analyte of interest. The accuracy of the C:H and C:N ratios determined was also affected by the molecular structure of the reference compound. C:H ratios of the greatest accuracy were obtained by using reference compounds having structures similar or close to those of the compound of interest; this was not always so for C:N ratios.     

Concurrent solvent recondensation large sample volume splitless injection

Concurrent Solvent Recondensation Large Sample Volume (CRS‐LV) splitless injection overcomes the limitation of the maximum sample volume to 1–2 μL valid for classical splitless injection. It is based on control of the evaporation rate in the vaporizing chamber, utilization of a strong pressure increase in the injector resulting from solvent evaporation, and greatly accelerated transfer of the sample vapors from the injector into the inlet of an uncoated precolumn by recondensation of the solvent. The sample vapors are transferred into the column as rapidly as they are formed in the injector (concurrent transfer). 20–50 μL of liquid sample is injected with liquid band formation. The sample liquid is received by a small packing of deactivated glass wool positioned slightly above the column entrance at the bottom of the vaporizing chamber. Solvent evaporation strongly increases the pressure in the injector (auto pressure surge), provided the septum purge outlet is closed and the accessible volumes around the vaporizing chamber are small, driving the first vapors into the precolumn. Transfer continues to be fast because of recondensation of the solvent, obtained by keeping the oven temperature below the pressure‐corrected solvent boiling point. The uncoated precolumn must have sufficient capacity to retain most of the sample as a liquid. The experimental data show virtually complete absence of discrimination of volatile or high boiling components as well as high reproducibility.     

An investigation of gas chromatography with atomic emission detection for the determination of empirical formulas

The atomic emission detector (AED) is a valuable tool for the identification of unknowns in complex mixtures. To the extent that elemental response factors are independent of compound structure, gas chromatographic results allow calculation of atomic ratios for unknown compounds. In favorable cases, empirical formulas can be found. An algorithm for automated calculation of empirical formulas for all the peaks in a chromatogram has been developed. When finite accuracy prevents an exact determination of empirical formulas, the algorithm gives a list of all formulas for each compound which are compatible with the user-defined limits. Examples are given of calculations for fatty acid methyl esters, substituted phenols, and pesticides. Analyses of volatile pollutants and polychlorinated biphenyls reveal a nonlinearity for hydrogen response, and an interference of chlorine on hydrogen. A lubricating oil analysis is used to illustrate the identification of unknowns.     

Detection of C,H, N,and O in capillary gas chromatography by atomic emission

Using a new atomic emission detector for gas chromatography, the quantitative and qualitative aspects of selective elemental detection of carbon, hydrogen, nitrogen, and oxygen were investigated. Sensitivity, precision, degree of tailing, and response variation between compounds are reported for capillary applications. Earlier atomic emission detectors reported poor sensitivity and selectivity for the analysis of oxygen. These problems have been greatly reduced due to lower interactions between elements in the sample and the silica wall of the water-cooled discharge tube. Using near-optimal sample amounts and chromatographic conditions, area precision was found to be very good with little variation in response factors among different compounds. For the compounds tested, response factors varied over a span of 2% to 3% for carbon, hydrogen, and nitrogen, and over 7% for oxygen. For quantitative analysis, area ratios were calibrated directly from the area ratios of two elements of an internal standard, and yielded better precision and compound independence than the individual calibrated response of each element. Empirical formulas were calcualted using one peak as a qualitative internal standard. Unambiguous formulas were determined for some, but not all, of the compounds tested. Further increases in precision and/or compound independence is needed before empirical formula determination can be used as a routine tool.     

Solute focusing technique for on-column injection in capillary gas chromatography

A novel solute focusing technique for on-column injection of liquid samples onto capillary GC columns is described. The focusing technique allows injection of 8.0 microliters or more of sample without producing the peak distortion or splitting observed under conventional on-column injection conditions. The experimentally determined performance of the technique is given for a wide volatility range sample. Solute focusing is useful in situations where on-column injection of 1.0 microliter or greater is required.     

Improving splitless injection with electronic pressure programming

An experimental injection port has been designed for split or splitless sample introduction in capillary gas chromatography; the inlet uses electronic pressure control, in order that the column head pressure may be set from the GC keyboard, and the inlet may be used in the constant flow or constant pressure modes. Alternatively, the column head pressure may be programmed up or down during a GC run in a manner analogous to even temperature programming. Using electronic pressure control, a method was developed which used high column head pressures (high column flow rates) at the time of injection, followed by rapid reduction of the pressure to that required for optimum GC separation. In this way, high flow rates could be used at the time of splitless injection to reduce sample discrimination, while lower flow rates could be used for the separation. Using this method, up to 5 μl of a test sample could be injected in the splitless mode with no discrimination; in another experiment, 2.3 times as much sample was introduced into the column by using electronic pressure programming. Some GC peak broadening was observed in the first experiment.