Minimum detectable amount, chromatographic

The gaseous atmosphere was then vented through a trap at -78° (to remove most of the benzene vapor) into an evacuated vessel. Samples were removed by gas-tight syringe and injected into a Hewlett-Packard 5790 gas chromatograph, equipped with a U ft, 1/8 in Porapak P column and a flame ionization detector. Use of known samples of hydrocarbons (methane and ethane) established that the minimum detectable amounts of product by this procedure were about 0.5-1 0 % (based on starting Nb complex). Several of the reactions (Mo(CO)g, W(C0)g and Ru (CO) p) gave small amounts (around 1-2 %) of these alkanes only with Cr(C0)g was a substantial yield of hydrocarbon product consistently observed (see below). 

Interfacing the TEA to both a gas and a HPLC has been shown to be selective to nitro-based explosives (NG, PETN, EGDN, 2,4-DNT, TNT, RDX and HMX) determined in real world samples, such as pieces of explosives, post-blast debris, post-blast air samples, hand swabs and human blood, at picogram level sensitivity [14], The minimum detectable amount for most explosives reported was 4-5 pg injected into column. A pyrolyser temperature of 550°C for HPLC-TEA and 900°C for GC/TEA was selected. As the authors pointed out, GC uses differences in vapour pressure and solubility in the liquid phase of the column to separate compounds, whereas in HPLC polarity, physical size and shape characteristics determine the chromatographic selectivity. So, the authors reported that the use of parallel HPLC-TEA and GC-TEA techniques provides a novel self-confirmatory capability, and because of the selectivity of the technique, there was no need for sample clean-up before analysis. The detector proved to be linear over six orders of magnitude. In the determination of explosives dissolved in acetone and diluted in methanol to obtain a 10-ppm (weight/volume) solution, the authors reported that no extraneous peaks were observed even when the samples were not previously cleaned up. Neither were they observed in the analysis of post-blast debris. Controlled experiments with handswabs spiked with known amounts of explosives indicated a lower detection limit of about 10 pg injected into column. 

However, a detectivity of 10 9 g/mL for a concentration detector means that this concentration is the smallest one that can be detected at that concentration in the detector cell. Consequently if a sample of this concentration is introduced into a chromatograph and run, its concentration will be somewhat less when it reaches the detector, because we have seen that an analyte is diluted and its zone becomes wider as it passes through the column. Thus, the amount of analyte that can actually be run and detected can differ from the MDQ. This situation has produced other terms like minimum detectable concentration, MDC, which will depend on the peak width (in milliliters). Analogously, for the mass flow rate detectors, the minimum detectable mass, MDM, will depend on the peak width in time units. In both cases, the quantity to be injected depends on... 

Methane gas served as both the gas chromatographic carrier gas and the reagent gas in the chemical ionization source (at 1000 y pressure). The mass spectrometer was operated in the selected ion recording mode, and the quasimolecular ions of PF and Ara-Virazole were monitored at m/e 692 and m/e 517, respectively two fragment ions (loss of methyl group) were also monitored. A calibration curve was established using known amounts of PF added to pooled human serum. The observed areas of PF and the internal standard were used to calculate area ratios which, in turn, were used to determine the amount of PF in serum. Using this method minimum detectable quantity is 10 ng/ml serum lowest level at which quantification is still reliable is 100 ng/ml serum. 

Riggin and Howard (1979, 1982), Matsui et al. (1983), Fabre et al. (1984), and Ahuja et al. (1988) reported that High Performance Liquid Chromatography (HPLC) with UV or electrochemical detection is capable of analyzing 1,2-diphenylhydrazine. Reversed phase chromatographic columns have been used most often (Ahuja et al. 1988 Fabre et al. 1984 Riggin and Howard 1979, 1982). Cyano-amino polar bonded phase columns also have been used (Matsui et al. 1983). Using a reversed phase and UV detection, the minimum amount detected (on column amounts) is approximately 6-7 ng and the minimum amount quantifiable is less than 1 pg (Ahuja et al. 1988 ... 

At this point, single-wavelength data acquisition remained a bottleneck, restricting the analyst to one basic characteristic tool to identify the analyte the amount of time the analyte is retained on the chromatographic column (i.e., the retention time). If there are four compounds in the sample to be analyzed, this would require a minimum of four injections to identify them. Additional work would be needed for crossidentification and so on. The concept of multiple-wavelength detection was introduced. 

High Performance Liquid Chromatography. Tissue extracts were analyzed with a Varian model 5020 liquid chromatograph equipped with a Rheo-dyne model 7120 loop injector valve, a Tracer 970 variable wavelength detector set at 257 nm, an automated Hewlett-Packard 3385A printer-plotter system for determining retention times and peak areas, and a Waters /x Bondapak column (3.9 mm i.d. X 300 mm) for carbohydrate analysis. The buffer was eluted isocratically at 1 mL/min with a 1 4 (v/v) mixture of 0.01 M monobasic sodium phosphate (pH 4.46) and methanol. The minimum amount detectable was 10 ng. 

The lower detection limit of a detector is defined as the minimum amount of compound detectable at a given signal-to-noise ratio. Ideally the detection limit should be determined independently of the chromatographic separation system using standard dilution devices. Detection limits are often expressed in g/s (mass flow-sensitive detectors) or g/mL (concentration-sensitive detectors) to obtain a value which is independent of the measuring conditions (flow rate, etc.). 

---