Methodological perspectives on the application of compound-specific stable isotope fingerprinting for sediment source apportionment

Compound-specific stable isotope (CSSI) fingerprinting of sediment sources is a recently introduced tool to overcome some limitations of conventional approaches for sediment source apportionment. The technique uses the C-13 CSSI signature of plant-derived fatty acids (delta C-13-fatty acids) associated with soil minerals as a tracer. This paper provides methodological perspectives to advance the use of CSSI fingerprinting in combination with stable isotope mixing models (SIMMs) to apportion the relative contributions of different sediment sources (i.e. land uses) to sediments. CSSI fingerprinting allows quantitative estimation of the relative contribution of sediment sources within a catchment at a spatio-temporal resolution, taking into account the following approaches. First, application of CSSI fingerprinting techniques to complex catchments presents particular challenges and calls for well-designed sampling strategies and data handling. Hereby, it is essential to balance the effort required for representative sample collection and analyses against the need to accurately quantify the variability within the system. Second, robustness of the CSSI approach depends on the specificity and conservativeness of the delta C-13-FA fingerprint. Therefore, saturated long-chain (> 20 carbon atoms) FAs, which are biosynthesised exclusively by higher plants and are more stable than the more commonly used short-chain FAs, should be used. Third, given that FA concentrations can vary largely between sources, concentration-dependent SIMMs that are also able to incorporate delta C-13-FA variability should be standard operation procedures to correctly assess the contribution of sediment sources via SIMMs. This paper reflects on the use of delta C-13-FAs in erosion studies and provides recommendations for its application. We strongly advise the use of saturated long-chain (> 20 carbon atoms) FAs as tracers and concentration-dependent Bayesian SIMMs. We anticipate progress in CSSI sediment fingerprinting from two current developments: (i) development of hierarchical Bayesian SIMMs to better address catchment complexity and (ii) incorporation of dual isotope approaches (delta C-13- and delta H-2-FA) to improve estimates of sediment sources.