Combined Standard Uncertainty of the measurement#

The combination of all the standard uncertainties associated with the input quantities in the measurement model (VIM (BIPM)). Also called overall uncertainty.

The combined uncertainty, or overall uncertainty, is calculated using the law of propagation of the uncertainties (considering that the standard uncertainties are not correlated) according to the Guide to the Expression of Uncertainty in Measurement .

Formula:

\[u\left(\chi _{\mathrm{sample}}\right)^{2} = u\left(\chi _{\mathrm{precision}}\right)^{2}+u\left(\chi _{\mathrm{calibration}}\right)^{2}+u\left(\chi _{\mathrm{instrument}}\right)^{2}+u\left(\chi _{\mathrm{sampling}}\right)^{2}\]

Uncertainty linked to the reproducibility of the measurement method (Precision)#

The precision is a measure for the closeness of the agreement between measured values obtained by replicate measurements on the same or similar objects under specified conditions (VIM (BIPM)). This is expressed as standard uncertainty reflecting the variability of the measurement system due to random errors.

Formula:

\[u\left(\chi _{\mathrm{precision}}\right)^{2} = (\chi _{\mathrm{sample}} * \sigma^{\mathrm{rel}}_{\mathrm{series}})^2+\left(\frac{\mathrm{LOD}}{3}\right)^{2}\]

Uncertainty of the Calibration#

Standard uncertainty due to the calibration. Behaviour not defined for calculation using the FID formula.

Formula:

\[u\left(\chi _{\mathrm{calibration}}\right)^{2} = \left(\frac{\left(A_{\mathrm{sample}}-A_{\mathrm{blank}}\right)*V_{\mathrm{calib}}}{V_{\mathrm{sample}}*\left(A_{\mathrm{calib}}-A_{\mathrm{blank}}\right)}*u_{\mathrm{calib}}\right)^{2}=\left(\frac{\chi _{\mathrm{sample}}}{\chi _{\mathrm{calib}}}*u_{\mathrm{calib}}\right)^{2}\]

Uncertainty of the Instrument#

The overall uncertainty of the instrument is the result of combining the standard uncertainties of the peak integration, sample volume, further instrumental problems (e.g. sampling line artefacts) and the uncertainty due to the lack of linearity.

Formula:

\[u\left(\chi _{\mathrm{instrument}}\right)^{2} = u\left(\chi _{\mathrm{peak\ integration}}\right)^{2}+u\left(\chi _{\mathrm{volume}}\right)^{2}+u\left(\chi _{\mathrm{further\ instrumental\ problems}}\right)^{2}+u\left(\chi _{\mathrm{linearity}}\right)^{2}\]

Uncertainty of the Peak Integration#

The standard uncertainty due to peak integration.

Formula:

\[u\left(\chi _{\mathrm{peak\ integration}}\right)^{2} = \left(\frac{f_{\mathrm{calib}}}{V_{\mathrm{sample}}}*\frac{u\left(A_{\mathrm{int,}sample}\right)}{A_{\mathrm{sample}}}\right)^{2}+\left(\frac{A_{\mathrm{sample}}*V_{\mathrm{calib}}*\chi _{\mathrm{calib}}}{V_{\mathrm{sample}}*A_{\mathrm{calib}}^{2}}*\frac{u\left(A_{\mathrm{int,}calib}\right)}{A_{\mathrm{calib}}}\right)^{2}\]

Uncertainty of the Volume#

The standard uncertainty due to the difference between sampling and calibration volumes.

Formula:

\[u\left(\chi _{\mathrm{volume}}\right)^{2} = \left(\frac{\chi _{\mathrm{sample}}}{V_{\mathrm{sample}}}*u\left(V_{\mathrm{sample}}\right)\right)^{2}+\left(\frac{\chi _{\mathrm{sample}}}{V_{\mathrm{calib}}}*u\left(V_{\mathrm{calib}}\right)\right)^{2}\]

Uncertainty of the Further Instrumental Problems#

Standard uncertainty due to specific instrumental problems.

Formula:

\[u\left(\chi _{\mathrm{further\ instrumental\ problems}}\right)^{2} = \left(\chi _{\mathrm{sample}}*u_{\mathrm{instrument}}\right)^{2}\]

Uncertainty of the Linearity#

Standard uncertainty due to lack of linearity of the measurement system.

Formula:

\[u\left(\chi _{\mathrm{linearity}}\right)^{2} = u_{\mathrm{linearity}}^{2}\]

Uncertainty of the sampling method#

The standard uncertainty due to application of off-line sampling techniques depends on the technique used. Contributions to the uncertainty common to all off-line techniques (cleaning of the samplers, storage, adsorption effects, etc.) should be evaluated case-by-case and per individual component. If not available in literature, a proper validation of the sorbent tubes is recommended prior to their use in the field to establish the efficiency of adsorption/desorption and the safe sampling volume at different composition levels and atmospheric conditions.

Formula:

\[u\left(\chi _{\mathrm{sampling}}\right)^{2} = u_{\mathrm{sampling}}^{2}\]

Uncertainty of the Blank#

The uncertainty due to the deviation of blank samples from the mean blank values.

Formula:

\[u\left(\chi _{\mathrm{blank}}\right)^{2} = \sigma _{\mathrm{blank}}^{2}\]

Expanded Uncertainty#

The combined uncertainty is the product of the combined standard uncertainty of the measurement by a number greater than 1 (the coverage factor k).

Formula:

\[U\chi _{\mathrm{sample}} = 2*u\left(\chi _{\mathrm{sample}}\right)\]
  • \(u\left(\chi _{\mathrm{sample}}\right)\) : Combined Standard Uncertainty