Lacustrine, riverine, and spring carbonates are archives of terrestrial climate change and are extensively used to study paleoenvironments. Clumped isotope thermometry has been applied to freshwater carbonates to reconstruct temperatures, however, limited work has been done to evaluate comparative relationships between clumped isotopes and temperature in different types of modern freshwater carbonates. Therefore, in this study, we assemble an extensive calibration dataset with 135 samples of modern lacustrine, fluvial, and spring carbonates from 96 sites and constrain the relationship between independent observations of water temperature and the clumped isotopic composition of carbonates (denoted by Δ47). We restandardize and synthesize published data and report 159 new measurements of 25 samples. We derive a composite freshwater calibration and also evaluate differences in the Δ47-temperature dependence for different types of materials to examine whether material-specific calibrations may be justified. When material type is considered, there is a convergence of slopes between biological carbonates (freshwater gastropods and bivalves), micrite, biologically-mediated carbonates (microbialites and tufas), travertines, and other recently published syntheses, but statistically significant differences in intercepts between some materials, possibly due to seasonal biases, kinetic isotope effects, and/or varying degrees of biological influence. Δ47-based reconstructions of water δ18O generally yield values within 2‰ of measured water δ18O when using a material-specific calibration. We explore the implications of applying these new calibrations in reconstructing temperature in three case studies.

Polar marine ecosystems are particularly vulnerable to the effects of climate change. Warming temperatures, freshening seawater and disruption to sea ice formation potentially all have detrimental cascading effects on food webs. New approaches are needed to better understand spatio-temporal interactions among biogeochemical processes at the base of Southern Ocean food webs, and how these interactions vary seasonally. In marine systems, isoscapes (models of the spatial variation in the stable isotopic composition) of carbon and nitrogen identify the spatial expression of varying biogeochemical processes on nutrient utilization by phytoplankton. Isoscapes also provide a baseline for interpreting stable isotope compositions of higher trophic level animals in movement, migration and diet research. Here we produce carbon and nitrogen isoscapes across the entire Southern Ocean (>40°S) using surface particulate organic matter (POM) isotope data, collected from multiple sources over the past 50 years and throughout the annual cycle. We use Integrated Nested Laplace Approximation (INLA)-based approaches to predict mean annual isoscapes and four seasonal isoscapes using a suite of environmental data as predictor variables. Clear spatial gradients in δ13C and δ15N values were predicted across the Southern Ocean, consistent with previous statistical and mechanistic isoscape views of isotopic variability in this region. We identify strong seasonal variability in both carbon and nitrogen isoscapes, with key implications for the use of static or annual average isoscape baselines in animal studies attempting to document seasonal migratory or foraging behaviours.