An indirect-calibration method for non-target quantification of trace gases applied to a time series of fourth-generation synthetic halocarbons at the Taunus Observatory (Germany)

Production and use of many synthetic halogenated trace gases are regulated internationally due to their contribution to stratospheric ozone depletion or climate change. In many applications they have been replaced by shorter-lived compounds, which have become measurable in the atmosphere as emissions increased. Non-target monitoring of trace gases rather than targeted measurements of well-known substances is needed to keep up with such changes in the atmospheric composition. We regularly deploy gas chromatography (GC) coupled to time-of-flight mass spectrometry (TOF-MS) for analysis of flask air samples and in situ measurements at the Taunus Observatory, a site in central Germany. TOF-MS acquires data over a continuous mass range that enables a retrospective analysis of the dataset, which can be considered a type of digital air archive. This archive can be used if new substances come into use and their mass spectrometric fingerprint is identified. However, quantifying new replacement halocarbons can be challenging, as mole fractions are generally low, requiring high measurement precision and low detection limits. In addition, calibration can be demanding, as calibration gases may not contain sufficiently high amounts of newly measured substances or the amounts in the calibration gas may have not been quantified. This paper presents an indirect data evaluation approach for TOF-MS data, where the calibration is linked to another compound which could be quantified in the calibration gas. We also present an approach to evaluate the quality of the indirect calibration method, select periods of stable instrument performance and determine well suited reference compounds. The method is applied to three short-lived synthetic halocarbons: HFO-1234yf, HFO-1234ze(E), and HCFO-1233zd(E). They represent replacements for longer-lived hydrofluorocarbons (HFCs) and exhibit increasing mole fractions in the atmosphere. The indirectly calibrated results are compared to directly calibrated measurements using data from TOF-MS canister sample analysis and TOF-MS in situ measurements, which are available for some periods of our dataset. The application of the indirect calibration method on several test cases can result in uncertainties of around 6 % to 11 %. For hydro(chloro-)fluoroolefines (denoted H(C)FOs), uncertainties up to 23 % are achieved. The indirectly calculated mole fractions of the investigated H(C)FOs at Taunus Observatory range between measured mole fractions at urban Dübendorf and Jungfraujoch stations in Switzerland.

Non-target analysis using gas chromatography with time-of-flight mass spectrometry: application to time series of fourth generation synthetic halocarbons at Taunus Observatory (Germany)

Production and use of many synthetic halogenated trace gases are regulated internationally because of their contribution to stratospheric ozone depletion or to climate change. In many applications they have been replaced by shorter-lived compounds which have become measurable in the atmosphere as emissions increased. Non-target monitoring of trace gases rather than targeted measurements of well-known substances is needed to keep up with such changes in the atmospheric composition. We regularly deploy gas chromatography (GC) coupled to time-of-flight mass spectrometry (TOF-MS) for analysis of flask air samples and in situ measurements at the Taunus Observatory, a site in central Germany. TOF-MS record data over a continuous mass range enable a retrospective analysis of the data set, which can thus be considered a type of digital air archive. This archive can be made use of if new substances come into use and their mass spectrometric fingerprint is identified. However, quantifying new replacement halocarbons can be challenging, as mole fractions are generally low, requiring high measurement precision and low detection limits. In addition, calibration can be demanding, as calibration gases may not contain sufficiently high amounts of newly used substances or the amounts in the calibration gas have not been quantified. This paper presents an indirect data evaluation approach for TOF-MS data, where the calibration is linked to another compound which could be quantified in the calibration gas. We also present an approach to evaluate the quality of the indirect calibration method and to select periods of stable instrument performance and well suited reference compounds. The method is applied to three short-lived synthetic halocarbons: HFO-1234-yf, HFO-1234ze(E), and HCFO-1233zd(E). They represent replacements for longer-lived HFCs and exhibit increasing mole fractions in the atmosphere. The indirectly calibrated results are compared to directly calibrated measurements using data from TOF-MS canister sample analysis and TOF-MS in situ measurements, which are available for some periods of our data set. The application of the indirect calibration method on several test cases can result into accuracies around 13 % to 20 %. For H(C)FOs accuracies up to 25 % are achieved. The indirectly calculated mole fractions of the investigated H(C)FOs at Taunus Observatory range between measured mole fractions at urban Dübendorf and Jungfraujoch stations in Switzerland.

DEVELOPMENT OF CALIBRATION GAS MIXTURES (CARBON DIOXIDE AND OXYGEN IN NITROGEN MATRIX) AT A TYPICAL CONCENTRATION RANGE OF MODIFIED ATMOSPHERE PACKAGING

Measurement of carbon dioxide (CO2), oxygen (O2), and nitrogen (N2) concentration in modified atmosphere packaging (MAP) food is critical to be carried out by the food industry. A slight variation in concentrations of CO2, O2, and N2 in food packaging may have a significant impact on product quality and safety for human health. Accurate and reliable measurement of CO2, O2, and N2 concentrations in food packaging is crucial, and it can only be achieved by calibrating the gas analyzer. This study aimed to develop gas mixtures for the calibration of CO2, O2, and N2 gas analyzers at a typical concentration range of modified atmosphere packaging. The calibration gas mixtures were prepared gravimetrically by following ISO 6142. The concentration ranges of CO2, O2, and N2 for calibration gas mixtures were set at 9-19% mol/mol, 1-5% mol/mol, and 74-88% mol/mol, respectively. Each parent gas was identified for its impurities using gas chromatography with a pulsed discharge helium ionization detector (GC-PDHID). The compositions of CO2, O2, and N2 in the mixtures were verified by evaluating the internal consistency within the prepared gas mixtures using gas chromatography with a thermal conductivity detector (GC-TCD). The short term stability of the prepared gas mixtures was evaluated using an equal division method. The result showed that good internal consistency was achieved between the gravimetrical and GC’s verification values, having linear regression coefficient (R2) ≥ 0.999. The t-test result has shown that CO2 has better short term stability than O2 and N2. In conclusion, the developed calibration gas mixtures at a typical concentration range of modified atmosphere packaging have shown satisfying results for CO2 component. However, further evaluation is still required to minimize the instability of O2 and N2 components.

Use of FTIR spectroscopy for the measurement of CO2 carbon stable isotope ratios

Carbon dioxide (CO2) is one of the most important long-lived anthropogenic greenhouse gases. Ocean, land and biosphere contribute to take up CO2 emissions, but approximately half of fossil fuel CO2 accumulates in the atmosphere. The study of isotopic composition of CO2 can give useful information for assessing and quantifying the uptake of CO2 in the environmental compartments, as well as for distinguishing natural from anthropogenic carbon in the atmosphere. In this work, an activity for the development of a Fourier Transform Infrared spectroscopy (FTIR) based method for δ13C-CO2 determination in CO2 in air mixtures is presented. The FTIR can be calibrated by a classical approach based on primary calibration gas standards, but an alternative calibration can be based on the generation of synthetic spectra, by means of radiative transfer calculation codes such as the Multiple Atmospheric Layer Transmission (MALT University of Wollongong, Australia). Another software (B-FOS) developed at the Bureau International des Poids et Mesures (BIPM) allows to interface MALT and the FTIR management software. This calibration approach is fast and reliable and can be used when the classical calibration based on reference gas mixtures might be demanding. The uncertainty obtained for δ13C-CO2 measurements is around 0.1 ‰, at a nominal CO2 mole fraction of 400 μmol mol-1 in air.