Peat archives offer a diverse range of physical and chemical proxies from which it is possible to study past environmental and ecological changes. Direct numerical calibration and verification is difficult so process-based and mechanistic studies are therefore required to establish and quantify links between environmental changes and their associated proxy-responses. Traditional space-for-time' calibrations provide a solution to this calibration problem, but are often unable to isolate a single environmental variable from other potentially confounding variables. In this study, we explored the potential of a site-specific space-for-time' approach applied to a hummock-hollow transect on an ombrotrophic raised bog in Patagonia, southern Chile. Coupled stable carbon, oxygen and hydrogen isotopic measurements were made on individual samples of Sphagnum moss cellulose and compared with plant-associated waters, local hydrology, temperature and relative humidity, sampled at the same points along the study transect. Results reveal a range of environmental responses, which were supported by plant-physiological models in the case of carbon and oxygen isotopes. For hydrogen isotopes, the results obtained from cellulose indicated a need for further research into hydrogen isotope fractionation in Sphagnum. We recommend conducting site-specific characterization of plant response to support the development of peat-based isotope records for palaeoenvironmental research, and where logistically possible, that monitoring is conducted over timescales appropriate to the time-integrative nature of the Sphagnum record. Copyright (C) 2016 The Authors. Journal of Quaternary Science Published by John Wiley & Sons Ltd.