This study applies radiocarbon and stable carbon isotopic distributions to investigate carbon sources and cycling within Lake Superior. We report the radiocarbon (D 14 C) and stable carbon isotope (d 13 C) values and the carbon concentrations within dissolved organic carbon (DOC), particulate organic carbon (POC), and dissolved inorganic carbon (DIC) in the lake's western basin water column. Samples were taken during spring mixing and late-summer thermal stratification over a 2-yr period (2007)(2008)(2009). Distinct processes operating in the surface (photosynthesis) and deep waters (sediment resuspension and pore-water intrusion) control the relative contribution of modern and ancient DOC and POC in the water column. The terrigenous carbon input to the open lake POC varied from 13% 6 4% during late summer stratification to 9% 6 3% during spring mixing, with most of the terrestrial carbon being 14 C-enriched (modern). The DIC reservoir cycles rapidly, with a bulk D 14 C DIC value that records atmospheric radiocarbon levels from 3 yr prior to sampling. The DOC pool recycles on a longer time scale than does the DIC, with a DOC residence time of # 60 yr. The suspended POC was in most cases older than co-occurring DOC, most likely as a result of resuspension of lake sediments.

We estimate the blank carbon mass over the course of a typical Ramped PyrOx (RPO) analysis (150–1000°C; 5°C×min–1) to be (3.7±0.6) μg C with an Fm value of 0.555±0.042 and a δ13C value of (–29.0±0.1) ‰ VPDB. Additionally, we provide equations for RPO Fm and δ13C blank corrections, including associated error propagation. By comparing RPO mass-weighted mean and independently measured bulk δ13C values for a compilation of environmental samples and standard reference materials (SRMs), we observe a small yet consistent 13C depletion within the RPO instrument (mean–bulk: μ=–0.8‰; ±1σ=0.9‰; n=66). In contrast, because they are fractionation-corrected by definition, mass-weighted mean Fm values accurately match bulk measurements (mean–bulk: μ=0.005; ±1σ=0.014; n=36). Lastly, we show there exists no significant intra-sample δ13C variability across carbonate SRM peaks, indicating minimal mass-dependent kinetic isotope fractionation during RPO analysis. These data are best explained by a difference in activation energy between 13C- and 12C-containing compounds (13–12∆E) of 0.3–1.8 J×mol–1, indicating that blank and mass-balance corrected RPO δ13C values accurately retain carbon source isotope signals to within 1–2‰.

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We present concentration and isotopic profiles of total, size, and polarity fractionated dissolved organic carbon (DOC) from Station ALOHA (A Long‐term Oligotrophic Habitat Assessment), an oligotrophic site in the North Pacific Ocean. The data show that, between the surface and 3500 m, low molecular weight (LMW) hydrophilic DOC, LMW hydrophobic DOC, and high molecular weight (HMW) DOC constitute 22–33%, 45–52%, and 23–35% of DOC, respectively. LMW hydrophilic DOC is more isotopically depleted (δ13C of −23.9‰ to −31.5‰ and Δ14C of −304‰ to −795‰; mean age of 2850 to 15000 years) than the LMW hydrophobic DOC (δ13C of −22‰ to −23‰ and Δ14C of −270‰ to −568‰; 2470 to 6680 years) and HMW DOC (δ13C of ~−21‰ and Δ14C of −24‰ to −294‰; 135–2700 years). Our analyses suggest that a large fraction of DOC may be derived from allochthonous sources such as terrestrial and hydrothermal DOC and cycle on much longer time scales of >10000 years or enter the ocean as preaged carbon.

We present a lake‐wide investigation of Lake Superior carbon and organic matter biogeochemistry using radiocarbon, stable isotope, and carbon concentrations. Dissolved inorganic carbon (DIC) abundance in the lake was 121–122 Tg C, with offshore concentration andδ13C values being laterally homogenous and tightly coupled to the physical and thermal regime and biochemical processes. Offshore Δ14C of DIC (50–65‰) exhibited lateral homogeneity and was more 14C enriched than co‐occurring atmospheric CO2 (∼38‰); nearshore Δ14C of DIC (36–38‰) was similar to atmospheric CO2. Dissolved organic carbon (DOC) abundance was 14.2–16.4 Tg C. DOC's concentration and δ13C were homogenous in June (mixed lake), but varied laterally during August (stratification) possibly due to spatial differences in lake productivity. Throughout sampling, DOC had modern radiocarbon values (14–58‰) indicating a semilabile nature with a turnover time of ≤60 years. Lake particulate organic carbon (POC, 0.9–1.3 Tg C) was consistently 13C depleted relative to DOC. The δ15N of epilimnetic particulate organic nitrogen shifted to more negative values during stratification possibly indicating greater use of nitrate (rather than ammonium) by phytoplankton in August. POC's radiocarbon was spatially heterogeneous (Δ14C range: 58‰ to −303‰), and generally 14C depleted relative to DOC and DIC. POC 14C depletion could not be accounted for by black carbon in the lake but, because of its spatial and temporal distribution, is attributed to sediment resuspension. The presence of old POC within the epilimnion of the open lake indicates possible benthic‐pelagic coupling in the lake's organic carbon cycle; the ultimate fate of this old POC bears further investigation.