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# Identification of instrumental artifacts in terpene detection: field studies and follow-up chamber campaign ACROSS-HECTIC

Fanny Bachelier, Max R Mcgillen, R. Veyrat, Benoit Grosselin, Marina

Jamar, Sébastien Dusanter, Thérèse Salameh, Pierre-Marie Flaud, Emilie

Perraudin, Eric Villenave, et al.

► To cite this version:

Fanny Bachelier, Max R Mcgillen, R. Veyrat, Benoit Grosselin, Marina Jamar, et al. Identification of instrumental artifacts in terpene detection: field studies and follow-up chamber campaign ACROSS-HECTIC. Colloque francophone combustion et pollution atmosphérique (COMPOLA 2024), May 2024, Ben Guérir, Morocco. 10.5194/egusphere-egu23-12435. [hal-05190342](https://hal.science/hal-05190342v1)

HAL Id: hal-05190342

https://hal.science/hal-05190342v1

Submitted on 28 Jul 2025

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# Identification of instrumental artifacts in terpene detection: field studies and follow-up chamber campaign ACROSS-HECTIC

F. Bachelier¹,², M. R. McGillen¹, R. Veyrat¹, B. Grosselin¹, M. Jamar³, S. Dusanter³, T. Salameh³, P.M. Flaud⁴, E. Perraudin⁴, E. Villenave⁴, M. Cazaunau⁵, A. Bauville⁵, T. Bertin⁵, C. Gaimoz⁵, V. Michoud⁵, V. Gros⁶, D. Baisnée⁶, F. Lafouge⁷, R. Ciuraru⁷, G. Krysztofiak⁸, G. Berthet⁸, C. Dufresne⁹, A. Chartier⁹, R. Nasreddine⁹, J.P. Amiet², D. Bazin², V. Daële¹

¹ICARE - UPR 3021 - CNRS, 1C Av. de la Recherche Scientifique, CS 50060, F-45071, Orléans cedex 2, ²Chromatotec, 1, Av. Jean-Honoré Olibet, 33240 Saint-André de Cubzac, ³IMT Nord Europe, Univ. Lille, SAGE, Lille,

⁴Université de Bordeaux, EPOC, UMR 5805, 33405 Talence CEDEX, ⁵LISA, Université de Paris, Université Paris-Est-Créteil, UMR CNRS 7583, Institut Pierre Simon Laplace (IPSL), Créteil, ⁶LSCE, UMR CNRS-CEA-UVSQ, IPSL, 91191 Gif-sur-Yvette, France, ⁷Université Paris-Saclay, UMR ECOSYS, INRAE, AgroParisTech, 78850, Thivernal-Grignon, ⁸LPC2E - UMR 7328 - CNRS, 3 Av. de la Recherche Scientifique, CS 50060, F-45071, Orléans cedex 2, ⁹Institut de Chimie Orgánique et Analytique, ICOA - UMR 7311, Université d'Orléans, Pôle de chimie, Rue de Chartres, 45100 Orléans - FRANCE

## Introduction

### Context:

Terpenes are a subset of Biogenic Volatile Organic Compounds (BVOCs)

They represent major emissions affecting the air chemistry of forested environments

Two technologies commonly used:

- Proton Transfer Reaction Time of Flight Mass Spectrometry (PTR-ToF-MS)

- Thermal Desorption Gas Chromatography with Flame Ionization / Mass Spectrometry detections (TD-GC-FID/MS)

**Problem:** Their quantification and speciation remain challenging

For example: monoterpene and isoprene measurements with 2 techniques during the ACROSS (Atmospheric ChemistRy Of the Suburban ForeSt) campaign in the Rambouillet Forest (Cantrell et al. (2023) 10.5194/egusphere-egu23-12435)

→ Strong disagreement observed from tens of ppt to low ppbs

**Goal:** Identify some possible causes of these discrepancies during a laboratory intercomparison campaign with ACROSS participants

→ **HECTIC: HElios Chamber Terpenes Instrumental Comparison**

<figure><img src="image_2.png" /></figure>

<figure><img src="image_3.png" /></figure>

Time series of monoterpenes and isoprene obtained by PTR-ToF-MS and TD-GCs above the canopy during the ACROSS 2022 campaign

<figure><img src="image_4.png" /></figure>

## Material & Method

*National
Facility

<figure><img src="image_5.png" /></figure>

<figure><img src="image_6.png" /><figcaption>Experimental set-up of the HECTIC campaign</figcaption></figure>

<table><thead><tr><th>Tests</th><th>Experiments</th></tr></thead><tbody><tr><td>Responses and calibrations</td><td>Injection of isoprene, α-pinene, β-pinene, 3-carene and limonene<br>Calibration with NPL cylinder containing isoprene and 3-carene</td></tr><tr><td>Effect of humidity</td><td>From 0% to 40% of relative humidity added in the manifolds</td></tr><tr><td>Effect of ozone in the GC traps</td><td>40 ppb of ozone added in the manifolds</td></tr><tr><td>Effects of terpenes<br>interferents</td><td>2-methyl-3-buten-2-ol (MBO), linalool and α-terpineol spiked in the manifolds</td></tr></tbody></table>

## Responses and calibrations

<figure><img src="image_7.png" /></figure>

Time series of monoterpenes concentration obtained by each technique

Monoterpene injection 20.3 ± 2.43 ppb

NPL cylinder injection: [3-carene] = 0.9 ± 0.101 ppb

→ Overall good agreement between GC systems and the expected concentration

→ Increased variability for PTR-MS techniques, especially for PTR 1, 2 and 4.

→ Similar observations for the NPL calibration with 3-carene

## Results
### Effect of Ozone in the GC traps

<figure><img src="image_8.png" /></figure>

<figure><img src="image_9.png" /></figure>

Time series of monoterpenes experimental and theoretical concentrations and resulting deviation with 40 ppb of O₃

<table><thead><tr><th>Instruments</th><th>Sampling line</th><th>Sampling time</th></tr></thead><tbody><tr><td>GC 1</td><td>1 m 1/8" heated stainless steel (140°C) + 1 m 1/8" PFA</td><td>30 min</td></tr><tr><td>GC 2</td><td>1 m 1/8" T<sub>amb</sub> stainless steel + 1 m 1/8" PFA</td><td>30 min</td></tr><tr><td>GC 3</td><td>O<sub>3</sub> scrubber (KI) + 1 m 1/8" T<sub>amb</sub> stainless steel + 1 m 1/8" PFA</td><td>30 min</td></tr><tr><td>GC 4</td><td>2 m, 1/8" PFA</td><td>10 min</td></tr><tr><td>Adsorbent tube 1 (Tenax)</td><td>2 m, 1/8" PFA</td><td>60 min</td></tr></tbody></table>

→ No significant effect of O₃ for α- and β-pinene

→ Reactions with O₃ observed for 3-carene and limonene generated deviation between 10 % and 30 % depending the instrumental conditions

→ Some terpenes seems more reactive in the traps

→ No effects observed on the PTR-MS results

## Effect of terpenes
### Interferents

<figure><img src="image_10.png" /></figure>

Time series of monoterpenes and isoprene concentrations with spikes of linalool, α-terpineol and MBO

<figure><img src="image_11.png" /></figure>

MBO ≈ 6 ppb

→ Strong effect of linalool and MBO for PTR-MS signals at m/z 137 and 69 respectively where almost 100% of signals are interfering

→ α-terpineol interference seems significant as well despite the longer passivation time than linalool

→ No significant impacts of linalool and α-terpineol on the GCs, but MBO interference observed for GC 1 and GC 5 (similar column and temperatures)

## Conclusion

* Sample line effects and calibration differences encountered

* For the GCs, a sensitivity to ozone and humidity, sample line temperature/material were observed in some cases, with more sensitive terpenes (β-pinene)

* For the PTR, injection of MBO, linalool and α-terpineol showed positive interferences on m/z 69 and 137

* Tendency of GC to underestimate and PTR to overestimate, same direction than observed in the field

→ These results highlight potential chemical analytical problems and help to establish best practice for making terpenes measurements in ambient conditions

## Acknowledgements

This work was carried out as part of a thesis with a CIFRE #2020/1563 agreement from the National Association for Technical Research (ANRT),

supported by the French National program LEFE (Les Enveloppes Fluides et l'Environnement) of the CNRS (Centre National de la Recherche Scientifique - Terre et Univers) in the framework of project ACROSS-GO,

and has been partly supported by the French MITI Internal White Program (PIB 2023) from CNRS