Determinants of isotopic coupling of CO₂ and water vapour within a Quercus petraea forest canopy

Concentration and isotopic composition (δ¹³C and δ¹⁸O) of ambient CO₂ and water vapour were determined within a Quercus petraea canopy, Northumberland, UK. From continuous measurements made across a 36-h period from three heights within the forest canopy, we generated mixing lines (Keeling plots) for δ_a¹³CO₂, δ_a C¹⁸O¹⁶O and δ_a H₂¹⁸O, to derive the isotopic composition of the signal being released from forest to atmosphere. These were compared directly with measurements of different respective pools within the forest system, i.e. δ¹³C of organic matter input for δ_a¹³CO₂, δ¹⁸O of exchangeable water for δ_a C¹⁸O¹⁶O and transpired water vapour for δ_a H₂¹⁸O. [CO₂] and δ_a¹³CO₂ showed strong coupling, where the released CO₂ was, on average, 4 per mil enriched compared to the organic matter of plant material in the system, suggesting either fractionation of organic material before eventual release as soil-respired CO₂, or temporal differences in ecosystem discrimination. δ_a C¹⁸O¹⁶O was less well coupled to [CO₂], probably due to the heterogeneity and transient nature of water pools (soil, leaf and moss) within the forest. Similarly, δ_a H₂¹⁸O was less coupled to [H₂O], again reflecting the transient nature of water transpired to the forest, seen as uncoupling during times of large changes in vapour pressure deficit. The δ¹⁸O of transpired water vapour, inferred from both mixing lines at the canopy scale and direct measurement at the leaf level, approximated that of source water, confirming that an isotopic steady state held for the forest integrated over the daily cycle. This demonstrates that isotopic coupling of CO₂ and water vapour within a forest canopy will depend on absolute differences in the isotopic composition of the respective pools involved in exchange and on the stability of each of these pools with time.