Flame photometric detector, sulfur

Sulfur compounds play a major role in determining the flavor and odor characteristics of many food substances. Often sulfur compounds are present in trace levels in foods making their isolation and quantification very difficult for chromatographers. This study compares three gas chromatographic detectors the flame photometric detector, sulfur chemiluminescence detector and the atomic emission detector, for the analysis of volatile sulfur compounds in foods. The atomic emission detector showed the most linearity in its response to sulfur the upper limit of the linear dynamic range for the atomic emission detector was 6 to 8 times greater than the other two detectors. The atomic emission detector had the greatest sensitivity to the sulfur compounds with minimum detectable levels as low as 1 pg. 

FIGURE 6.6 Chromatograms of a mixture of 10 pesticide standards, extracted from miUc, and run on various detectors (a) flame ionization detector (b) flame photometric detector, sulfur mode (c) flame photometric detector (d) electron-capture detector. (Adapted from Reference 6 with permission. Copyright 1975 American Chemical Society.)... 

Other Detectors Two additional detectors are similar in design to a flame ionization detector. In the flame photometric detector optical emission from phosphorus and sulfur provides a detector selective for compounds containing these elements. The thermionic detector responds to compounds containing nitrogen or phosphorus. 

The flame-photometric detector (FPD) is selective for organic compounds containing phosphoms and sulfur, detecting chemiluminescent species formed ia a flame from these materials. The chemiluminescence is detected through a filter by a photomultipher. The photometric response is linear ia concentration for phosphoms, but it is second order ia concentration for sulfur. The minimum detectable level for phosphoms is about 10 g/s for sulfur it is about 5 x 10 g/s. 

Flame Photometric Detector3 With the flame photometric detector (FPD), as with the FID, the sample effluent is burned in a hydrogen/air flame. By using optical filters to select wavelengths specific to sulfur and phosphorus and a photomultiplier tube, sulfur or phosphorus compounds can be selectively detected. 

Flame photometric detector fitted with a 394-nm sulfur-specific filter 240 °C... 

Ethylenethiourea (ETU) is a toxic decomposition product/metabolite of alky-lenebis(dithiocarbamates). This compound could be generated during processing of treated crops at elevated temperature. Different chromatographic methods to determine the residue levels of ETU have been published. After extraction with methanol, clean-up on a Gas-Chrom S/alumina column and derivatization (alkylation) with bro-mobutane, ETU residues can be determined by GC with a flame photometric detector in the sulfur mode. Alternatively, ETU residues can also be determined by an HPLC method with UV detection at 240 nm or by liquid chromatography/mass spectrometry (LC/MS) or liquid chromatography/tandem mass spectrometry (LC/MS/MS) (molecular ion m/z 103). ... 

Gas chromatograph for fused-silica capillary or packed columns, equipped with a flame photometric detector (with sulfur filter), Hewlett-Packard, Carlo Erba, or equivalent... 

The chemiluminescent reaction with chlorine dioxide provides a highly sensitive and highly selective method for only two sulfur compounds, hydrogen sulfide and methane thiol [81]. As in the flame photometric detector (FPD), discussed below, atomic sulfur emission, S2(B3S -> ) is monitored in the wave-... 

Elemental composition H 5.92%, S 94.08. Hydrogen sulfide may be distinguished by its characteristic odor. The gas turns a paper soaked in lead acetate solution black. Many infrared sensors are commercially available for in-situ measurements of H2S. It may be monitored semiquantitatively by Draeger tubes. It also may be analyzed by GC following trapping over molecular sieves and thermal desorption. Either a flame photometric detector or a sulfur chemiluminescence detector may be used for GC analysis. It may be separated on a capillary column such as Carboxen 1006 PLOT or SPB-1 SULFUR (Supelco Catalog 1999 Supelco Inc., BeUefonte, PA). 

Sulfur can be analyzed by x-ray, GC and GC/MS techniques. Alpha-octacy-closulfur is dissolved in benzene, toluene, or chloroform and analyzed for sulfur by GC using a flame photometric detector or by GC/MS. The characteristic mass ions for its identification are multiples of 32 (i.e. 32, 64, 128, and 256). Sulfur may be identified by mixing a little powder with copper, silver, or mercury at room temperature and identifying the metal sulfide from color change and various instrumental methods. 

A flame photometric detector measures optical emission from phosphorus, sulfur, lead, tin, or other selected elements. When eluate passes through a Hrair flame, as in the flame ionization detector, excited atoms emit characteristic light. Phosphorus emission at 536 nm or sulfur emission at 394 nm can be isolated by a narrow-band interference filter and detected with a photomultiplier tube. 

Eluate from a chromatography column can be passed through a plasma to atomize and ionize its components and measure selected elements by atomic emission spectroscopy or mass spectrometry. An atomic emission detector directs eluate through a helium plasma in a microwave cavity. Every element of the periodic table produces characteristic emission that can be detected by a photodiode array polychromator (Figure 20-14). Sensitivity for sulfur can be 10 times better than the sensitivity of a flame photometric detector. 

Sulfur Dioxide. Both flame photometric and pulsed fluorescence methods have been applied to the continuous measurement of S02 from aircraft. In the flame photometric detector (FPD), sulfur compounds are reduced in a hydrogen-rich flame to the S2 dimer. The emission resulting from the transition of the thermally excited dimer to its ground state at 394 nm is measured by using a narrow band-pass filter and a photomultiplier tube. 

Because the FPD responds to both aerosol and gaseous sulfur species, it has also been possible to modify these instruments to continuously measure aerosol sulfur by selectively removing gaseous sulfur compounds with a lead(II) oxide-glycerol coated denuder (55). Use of such an instrument for airborne measurements of aerosol sulfur in and around broken clouds has been reported (57). In principle, speciation between aerosol sulfate, disulfate, and sulfuric acid by selective thermal decomposition (58, 59) can also be achieved. Flame photometric detectors have also been used as selective detectors for gas chromatography. Thornton and Bandy (60) reported the use of a chromatographic system with a flame photometric detector for airborne measurement of S02 and OCS with a detection limit of 25 pptrv. 

On-line measurements of the sulfur content of atmospheric aerosols have been made by removing gaseous sulfur species from the aerosol and then analyzing the particles for sulfur with a flame photometric detector (24) or by using an electrostatic precipitator to chop the aerosol particles from the gas so that the sulfur content could be measured by the difference in flame photometric detector response with and without particles present. These and similar methods could be extended to the analysis of size-classified samples to provide on-line size-resolved aerosol composition data, although the analytical methods would have to be extremely sensitive to achieve the size resolution possible in size distribution analysis. 

Continuous Sampling and Determination. There are no truly continuous techniques for the direct determination of sulfuric acid or other strong acid species in atmospheric aerosols. The closest candidate method is a further modification of the sensitivity-enhanced, flame photometric detector, in which two detectors are used, one with a room-temperature de-nuder and one with a denuder tube heated to about 120 °C. Sulfuric acid is potentially determined as the difference between the two channels. In fact, a device based on this approach did not perform well in ambient air sampling (Tanner and Springston, unpublished data, 1990). Even with the SF6-doped H.2 fuel gas for enhanced sensitivity, the limit of detection is unsuitably high (5 xg/m3 or greater) because of the difficulty in calibrating the two separate FPD channels with aerosol sulfates. 

The flame photometric detector, which is sensitive to sulfur or phosphorus, shows diminished response to sulfur compounds, if large amounts of hydrocarbons are eluted simultaneously. This happens even though there is no significant response on the chromatogram from the interfering hydrocarbons. The opposite effect can also occur. In some of the newer types of electron... 

The impact of the flame photometric detector (FPD) resides in its simultaneous sensitivity and specificity for the determination of sulfur and phosphorus. It is inherently compatible with the FID and as such affords the analytical chemist a discriminating ability beneficial to many analyses. In 1966, Brody and Chaney published data on their design of an FPD (26)(Figure 5.18). 

The saturated hydrocarbon fractions contain traces of sulfur. The gas-solid chromatography of the Lloydminster saturates boiling in the range of the C2s normal alkane, using a Melpar flame photometric detector, shows that the sulfur compounds are retained much longer than the hydrocarbons. This is typical for alkyl sulfides. 

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