Environmental contextSphagnum moss is a widespread species in peatlands globally and responsible for a large fraction of carbon storage in these systems. We used synchrotron infrared microspectroscopy to characterise the acid-base properties of Sphagnum moss and the conditions under which calcium uptake can occur (essential for plant tissue integrity). The work allows a chemical model for Sphagnum distribution in the landscape to be proposed. AbstractSphagnum is one the major moss types responsible for the deposition of organic soils in peatland systems. The cell walls of this moss have a high proportion of carboxylated polysaccharides (polygalacturonic acids), which act as ion exchangers and are likely to be important for the structural integrity of the cell walls. We used synchrotron light source infrared microspectroscopy to characterise the acid-base and calcium complexation properties of the cell walls of Sphagnum cristatum stems, using freshly sectioned tissue confined in a flowing liquid cell with both normal water and D2O media. The Fourier transform infrared spectra of acid and base forms are consistent with those expected for protonated and deprotonated aliphatic carboxylic acids (such as uronic acids). Spectral deconvolution shows that the dominant aliphatic carboxylic groups in this material behave as a monoprotic acid (pKa=4.97–6.04). The cell wall material shows a high affinity for calcium, with a binding constant (K) in the range 103.9–104.7 (1:1 complex). The chemical complexation model developed here allows for the prediction of the chemical environment (e.g. pH, ionic content) under which Ca2+ uptake can occur, and provides an improved understanding for the observed distribution of Sphagnum in the landscape.