University of Groningen
Carbonyl sulfide, a way to quantify photosynthesis
Kooijmans, Linda Maria Johanna
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Kooijmans, L. M. J. (2018). Carbonyl sulfide, a way to quantify photosynthesis. University of Groningen.
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Carbonyl Sulfide,
a Way to Quantify
Photosynthesis
Carbonyl Sulfide, a Way to Quantify Photosynthesis Linda M.J. Kooijmans PhD thesis, 2018 University of Groningen The Netherlands ISBN: 978-94-034-1079-1
ISBN: 978-94-034-1078-4 (electronic version) Printed by: Ridderprint BV, the Netherlands
The work described in this thesis was performed at the Centre for Isotope Research (CIO), which is part of the Energy and Sustainability Research Institute Groningen (ESRIG) of the University of Groningen, the Netherlands.
Carbonyl Sulfide,
a Way to Quantify
Photosynthesis
PhD thesis
to obtain the degree of PhD at the University of Groningen
on the authority of the Rector Magnificus Prof. E. Sterken
and in accordance with
the decision by the College of Deans. This thesis will be defended in public on Friday 30 November 2018 at 16.15 hours
by
Linda Maria Johanna Kooijmans
born on 16 March 1990Promotores
Prof. H. Chen Prof. H.A.J. Meijer
Assessment Committee
Prof. W. Peters Prof. D. Yakir Prof. T. Roeckmann
C
ONTENTS
1 Introduction 11
1.1 Climate change . . . 12
1.2 Vegetative CO2uptake through photosynthesis. . . 13
1.3 A tracer for photosynthesis: carbonyl sulfide . . . 16
1.4 The COS budget. . . 17
1.4.1 Global scale . . . 17
1.4.2 Ecosystem scale . . . 18
1.4.3 Leaf scale . . . 18
1.5 COS measurement techniques . . . 19
1.6 Objective and approach of this thesis. . . 20
2 Continuous and high-precision atmospheric concentration measurements of COS, CO2, CO and H2O using a quantum cascade laser spectrometer 23 2.1 Introduction . . . 24 2.2 Experimental setup. . . 26 2.2.1 Instrumentation . . . 26 2.2.2 Calibration strategy . . . 27 2.2.2.1 Instrument response . . . 28 2.2.2.2 Working standards . . . 29
2.2.2.3 Background and reference strategy . . . 30
2.2.3 Water vapor interference correction . . . 31
2.2.4 Flow schematics for measurements at the Lutjewad station . . . 34
2.2.5 Temperature stability . . . 36
2.2.6 Measurements of COS from flasks . . . 36
2.3 Results and discussion . . . 38
2.3.1 Precision and accuracy. . . 38
2.3.2 Measurement comparison. . . 44
2.3.3 Continuous COS, CO2, CO and H2O observations from Lutjewad . . 48
2.4 Conclusions. . . 50
3 Canopy uptake dominates nighttime carbonyl sulfide fluxes in a boreal forest 53 3.1 Introduction . . . 54
3.2 Field measurements and data. . . 55
3.2.1 Measurement site . . . 55
3.2.2 Instrumentation for measurements of COS, CO2, and H2O . . . 55
3.2.2.1 QCLS for vertical profile and soil flux measurements . . . . 55
3.2.2.2 QCLS for eddy covariance measurements. . . 56
6 CONTENTS 3.2.3 Soil chambers . . . 56 3.2.4 Auxiliary data . . . 56 3.2.4.1 222Rn . . . 56 3.2.4.2 Stomatal conductance . . . 57 3.2.4.3 Meteorological data. . . 57 3.3 Flux derivations. . . 57
3.3.1 The EC-based method. . . 57
3.3.1.1 Eddy-covariance fluxes . . . 57
3.3.1.2 Storage fluxes. . . 59
3.3.2 The radon-tracer method . . . 59
3.3.3 Soil fluxes . . . 61
3.4 Results . . . 62
3.4.1 COS and CO2storage fluxes . . . 62
3.4.2 COS and CO2 nighttime fluxes through the radon-tracer and EC-based method . . . 63
3.4.3 FCOScorrelation with gsCOS, VPD, Tairand u§ . . . 64
3.5 Discussion . . . 65
3.5.1 Vertical distribution of sinks and sources of COS and CO2compared to that of222Rn. . . 65
3.5.2 The effect of canopy layer mixing on flux derivations . . . 66
3.5.3 Sensitivity of FCOS-ECto u§. . . 67
3.5.4 Stomatal control of nighttime FCOS . . . 67
3.5.5 Effect of nighttime COS fluxes on GPP derivation . . . 68
3.6 Conclusions. . . 68
A3 Appendices . . . 70
4 Influences of light and humidity on carbonyl sulfide-based estimates of pho-tosynthesis 75 4.1 Introduction . . . 76
4.2 Methods . . . 77
4.2.1 Site description . . . 77
4.2.2 Branch chamber measurements. . . 77
4.2.3 Stomatal conductance. . . 79
4.2.4 GPP estimates . . . 79
4.2.5 Meteorological data . . . 80
4.2.6 Statistical tests. . . 80
4.3 Results and Discussion . . . 81
4.3.1 Responses of FCOSand FCO2 to light and stomatal conductance . . . 81
4.3.2 Internal conductance of COS limits FCOSduring daytime . . . 83
4.3.3 Seasonal variation of LRU influenced by environmental variables . . 83
4.3.4 Light and humidity-dependent LRU required for accurate COS-based GPP estimates . . . 84
4.3.5 The implications in large-scale GPP estimates. . . 86
4.4 Conclusion . . . 87
A4 Appendices . . . 88
A4.1 Seasonal change of FCOSand FCO2 . . . 89
A4.2 Effect of PAR on daytime LRU . . . 89
CONTENTS 7
A4.4 Correlations of LRU with VPD, gs,COS, RH and T . . . 90
A4.5 Internal conductance . . . 91
A4.6 Temperature response of FCOSvaries over the season . . . 92
A4.7 Fit of LRU against PAR . . . 93
A4.8 Time-integrated LRU. . . 93
A4.9 Chamber types. . . 94
A4.10 Blank measurements. . . 94
A4.11 Respiration. . . 96
5 Sources and sinks of carbonyl sulfide inferred from atmospheric observations at the Lutjewad tower 99 5.1 Introduction . . . 100
5.2 Methodology . . . 101
5.2.1 Measurement sites. . . 101
5.2.2 Measurements of COS CO2and CO . . . 101
5.2.3 Measurements of SF6 . . . 102
5.2.4 Seasonal fit. . . 103
5.2.5 Nighttime ecosystem flux in Lutjewad . . . 103
5.3 Results . . . 105
5.3.1 Diurnal cycle of COS and CO2mole fractions . . . 105
5.3.2 Sources and sinks by wind directions . . . 106
5.3.3 Estimate of nighttime COS and CO2fluxes. . . 106
5.3.4 Sources of COS from agricultural field during ploughing. . . 107
5.3.4.1 Spikes in October 2014 . . . 108
5.3.4.2 Spikes in January 2015 . . . 108
5.3.4.3 Spikes in February 2018. . . 110
5.4 Discussion . . . 110
5.4.1 Understanding the diurnal change of atmospheric COS mole frac-tions . . . 110
5.4.2 COS spikes in the atmosphere . . . 111
5.4.2.1 COS production in agricultural soil. . . 111
5.4.2.2 Anthropogenic source of COS. . . 112
5.4.3 Spatial distribution of COS and CO2sources and sinks. . . 113
5.5 Conclusion . . . 114
A5 Appendix . . . 115
6 Discussion and Outlook 117 6.1 Discussion . . . 117
6.1.1 Measurements of COS . . . 117
6.1.2 Nighttime fluxes of COS . . . 118
6.1.3 Controls on leaf COS fluxes . . . 119
6.1.4 The relation between COS and CO2fluxes . . . 120
6.1.5 Non-vegetative ecosystem sources and sinks of COS. . . 120
6.1.6 COS-based GPP estimates . . . 122
6.2 Perspectives and recommendations . . . 122
6.2.1 The role of COS in obtaining GPP estimates . . . 122
8 CONTENTS
Summary 127
Samenvatting 133
References 139
Acknowledgements 153
About the Author 157
