The d
13C of the soil surface efflux of carbon dioxide (d 13 CR S ) has emerged as a powerful tool enabling investigation of a wide range of soil processes from characterising entire ecosystem respiration to detailed compound-specific isotope studies. d 13 CR S can be used to trace assimilated carbon transfer below ground and to partition the overall surface efflux into heterotrophic and autotrophic components. Despite this wide range of applications no consensus currently exists on the most appropriate method of sampling this surface efflux of CO 2 in order to measure d 13 CR S . Here we consider and compare the methods which have been used, and examine the pitfalls. We also consider a number of analysis options, isotope ratio mass spectrometry (IRMS), tuneable diode laser spectroscopy (TDLS) and cavity ring-down laser spectroscopy (CRDS Increasing levels of atmospheric carbon dioxide (CO 2 ) and predicted climate change have intensified research efforts to better understand the global carbon (C) cycle. Within terrestrial ecosystems, soils hold substantial amounts of C and through the exchange of CO 2 with the atmosphere have the ability to act as either a C source or a sink.[1] It is this balance and how it may be influenced by future climate change and/or land use change which has been the focus of considerable debate for some time.[2-5] The net exchange of CO 2 across a landscape can be measured using a specialist technique called eddy covariance.[6] However, eddy covariance measurements do not provide any detailed information on the underlying mechanisms which drive the terrestrial C cycle, namely photosynthesis and respiration. [7] For several decades now the stable carbon isotope 13 C has been used extensively to provide a better understanding of these two processes at a range of scales. At the ecosystem scale so-called isofluxes [8] can be measured by combining micrometeorological measurements with the 13 C analysis of CO 2 within and above the plant canopy. This type of measurement allows total ecosystem respiration to be measured -a combination of both plant (stem/leaf) respiration and the respiration from soil, or efflux rate. With the contribution of soil-derived CO 2 being important as this can provide information on the longterm overall net C balance of the system. Two basic processes contribute to the soil surface CO 2 efflux rate (R S ): autotrophic respiration from roots and the rhizosphere, and heterotrophic respiration from the turnover of soil organic matter (SOM).Against this background, measuring the rate at which CO 2 leaves the soil surface coupled with the measurement of its 13 C/ 12 C ratio (d 13 CR S ) has emerged as a key tool in ecophysiological research and global terrestrial C cycle studies. Isotopic analyses provide a means of distinguishing the C sources which contribute to this overall flux, allowing either the autotrophic or the heterotrophic components to be quantified. For example, d13 CR S measurements have been used to assess the speed at which assimilated C is transfe...