• Oxygen and hydrogen isotopes of cellulose in plant biology are commonly used to infer environmental conditions, often from time series measurements of tree rings. However, the covariation (or the lack thereof) between δ¹⁸O and δ²H in plant cellulose is still poorly understood.
• We compared plant water, and leaf and branch cellulose from dominant tree species across an aridity gradient in Northern Australia, to examine how δ¹⁸O and δ²H relate to each other and to mean annual precipitation (MAP).
• We identified a decline in covariation from xylem to leaf water, and onwards from leaf to branch wood cellulose. Covariation in leaf water isotopic enrichment (Δ) was partially preserved in leaf cellulose but not branch wood cellulose. Furthermore, whilst δ²H was well-correlated between leaf and branch, there was an offset in δ¹⁸O between organs that increased with decreasing MAP.
• Our findings strongly suggest that postphotosynthetic isotope exchange with water is more apparent for oxygen isotopes, whereas variable kinetic and nonequilibrium isotope effects add complexity to interpreting metabolic-induced δ²H patterns. Varying oxygen isotope exchange in wood and leaf cellulose must be accounted for when δ¹⁸O is used to reconstruct climatic scenarios. Conversely, comparing δ²H and δ¹⁸O patterns may reveal environmentally induced shifts in metabolism.