Page:NIOSH Manual of Analytical Methods - 3800.pdf/44
ORGANIC AND INORGANIC GASES by FTIR Spectrometry: METHOD 3800, Issue 1, dated 15 March 2003 - Page 44 of 47
| Synthetic Sample Spectrum File Name | TFE Synth. Conc. (ppm) | TFE LSF Result (ppm) | TFE LSF 3σ Uncert. (%) | DFE Synth. Conc. (ppm) | DFE LSF Result (ppm) | DFE LSF 3σ Uncert. (%) | H2O LSF Result (arb) | H2O LSF 3σ Uncert. (%) |
|---|---|---|---|---|---|---|---|---|
| S0011.spc | 0 | 1.00 | 39.6 | 0 | -1.58 | 26.5 | 1.65 | 0.89 |
| S0022.spc | 0 | 2.01 | 39.5 | 0 | -3.16 | 26.4 | 3.29 | 1.78 |
| S5511.spc | 25.0 | 25.06 | 1.51 | 25.0 | 22.65 | 1.89 | 1.43 | 43.3 |
| S5112.spc | 25.0 | 25.73 | 2.90 | 5.00 | 1.57 | 53.8 | 1.99 | 61.4 |
| S1511.spc | 5.00 | 5.53 | 6.64 | 25.0 | 22.67 | 1.84 | 1.63 | 37.0 |
| S5522.spc | 25.0 | 25.73 | 2.90 | 25.0 | 21.05 | 4.01 | 3.10 | 39.2 |
| S5121.spc | 25.0 | 25.09 | 1.52 | 5.00 | 3.29 | 13.1 | 2.55 | 24.4 |
| S1522.spc | 5.00 | 6.20 | 11.87 | 25.0 | 21.09 | 3.96 | 3.30 | 36.4 |
| Average Abs. % Concentration Uncertainty[1] | 4.56 | 13.1 | 40.3 |
- ↑ *The average excludes the spectra (S0011 and S0022) with zero synthetic TFE and DFE concentrations.
The results shown in the last rows of Table E4 (those of the original LSF analysis without HFP interference) and Table E6 (those of the original LSF analysis with HFP interference) are clearly quite different. Averaged over the six synthetic spectra containing TFE and DFE in each case, the (absolute) percent concentration uncertainties for TFE, DFE, and H2O are greater for the spectra with HFP interference. For TFE and DFE, the average percent uncertainties of Table E6 are over ten times greater than those of Table E4.
This exercise shows that:
- For sample spectra containing substantial TFE and DFE concentrations, the HFP interference causes large increases in the TFE and DFE relative absolute concentration uncertainties.
- For sample spectra containing low or zero concentrations TFE and DFE, the relative absolute uncertainties are NOT a reliable indicator of the HFP interference. However, for such spectra, the concentration results themselves are often clearly unreliable; note that the DFE concentration results are negative and large compared to the LOD estimate for this compound. (Note also that negative concentration results which are small compared to the LOD are statistically valid, and do not necessarily indicate a failure of the analysis.)
If the concentration results show anomalies such as those noted above, the residual spectra from the analyses will also exhibit anomalous behavior. This is illustrated in Figure E7, which shows the residual spectra for four analyses. Compared to the residual spectra resulting from analyses of spectra without the HFP interference, those with HFP interference show large absorbance features which cannot be modeled by the three reference spectra employed. The analyst needs to identify the interfering compound before proceeding. This can often be done by visually comparing the suspect residual spectra to reference spectra of a number of likely interferants, as illustrated in Figure E8.
NIOSH Manual of Analytical Methods, Fourth Edition