Constraining the sources and cycling of dissolved organic carbon in a large oligotrophic lake using radiocarbon analyses

© The Author(s), 2017. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 208 (2017): 102-118, doi:10.1016/j.gca.2017.03.021.We measured the concentrations and isotopic compositions of solid phase extracted (SPE) dissolved organic carbon (DOC) and high molecular weight (HMW) DOC and their constituent organic components in order to better constrain the sources and cycling of DOC in a large oligotrophic lacustrine system (Lake Superior, North America). SPE DOC constituted a significant proportion (41-71 %) of the lake DOC relative to HMW DOC (10-13%). Substantial contribution of 14C-depleted components to both SPE DOC (Δ14C = 25 to 43‰) and HMW DOC (Δ14C = 22 to 32‰) was evident during spring mixing, and depressed their radiocarbon values relative to the lake dissolved inorganic carbon (DIC; Δ14C ~ 59‰). There was preferential removal of 14C-depleted (older) and thermally recalcitrant components from HMW DOC and SPE DOC in the summer. Contemporary photoautotrophic addition to HMW DOC was observed during summer stratification in contrast to SPE DOC, which decreased in concentration during stratification. Serial thermal oxidation radiocarbon analysis revealed a diversity of sources (both contemporary and older) within the SPE DOC, and also showed distinct components within the HMW DOC. The thermally labile components of HMW DOC were 14C-enriched and are attributed to heteropolysaccharides (HPS), peptides/amide and amino sugars (AMS) relative to the thermally recalcitrant components reflecting the presence of older material, perhaps carboxylic-rich alicyclic molecules (CRAM). The solvent extractable lipid-like fraction of HMW DOC was very 14C-depleted (as old as 1270-2320 14C years) relative to the carbohydrate-like and protein-like substances isolated by acid hydrolysis of HMW DOC. Our data constrain relative influences of contemporary DOC and old DOC, and DOC cycling in a modern freshwater ecosystem.This work was funded by the National Science Foundation OCE 0825600 to E.C.M. and J.P.W., a graduate student internship fellowship to P.K.Z by National Ocean Sciences Accelerator Mass Spectrometry Facility (OCE 0753487), and the Postdoctoral Scholar Program at the Woods Hole Oceanographic Institution to P.K.Z, with funding provided by the National Ocean Sciences Accelerator Mass Spectrometry Facility (OCE 0753487)

Allochthonous sources and dynamic cycling of ocean dissolved organic carbon revealed by carbon isotopes

Author Posting. © American Geophysical Union, 2017. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 44 (2017): 2407–2415, doi:10.1002/2016GL071348.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.NSF Cooperative Agreement for the Operation of a National Ocean Sciences Accelerator Mass Spectrometry Facility Grant Number: OCE-0753487; Gordon and Betty Moore Foundation Grant Numbers: GBMF3298, GBMF3794; Simons Foundation Grant Number: 3291082017-09-0

Assessing the blank carbon contribution, isotope mass balance, and kinetic isotope fractionation of the Ramped Pyrolysis/Oxidation instrument at NOSAMS

Author Posting. © The Author(s), 2017. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Radiocarbon 59 (2017): 179-193, doi:10.1017/RDC.2017.3.We estimate the blank carbon mass over the course of a typical Ramped PyrOx (RPO) analysis (150 to 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 (13–12ΔE) of 0.3 to 1.8 J×mol-1, indicating that blank and mass-balance corrected RPO δ13C values accurately retain carbon source isotope signals to within 1 to 2‰.J.D.H. was partly supported by the NSF Graduate Research Fellowship Program under grant number 2012126152; V.V.G. was partly supported by the US National Science Foundation (grants OCE- 0851015 and OCE-0928582), the WHOI Coastal Ocean Institute (grant 27040213) and an Independent Study Award (grant 27005306) from WHOI; G.S. and P.K.Z. were supported by the WHOI Postdoctoral Scholar Program with funding provided by NOSAMS (OCE-1239667)

Tracing the methane cycle with lipid biomarkers in Lake Rotsee (Switzerland)

We analysed the distributions of glycerol dialkyl glycerol tetraethers (GDGTs) and other lipid biomarkers [glycerol dialkyl diethers (DGDs), fatty acids (FAs), sterols, hopanoids and phytol] in the water column and sediments of Lake Rotsee (Switzerland) to understand the processes and organisms involved in CH4 cycling. In the sediment we found substantial amounts of GDGT-0. This originates mainly from acetoclastic methanogens, as indicated by microbial data, high GDGT-0/crenarchaeol ratio and δ13C signature of the isoprenoid alkyl chains (ca. −35‰ to −30‰). The more depleted δ13C values of archaeol (as low as −62‰) can be attributed to hydrogenotrophic methanogens, with a potential contribution from methanotrophic archaea (anaerobic CH4 oxidising archaea). An increase in GDGT-0 in sediment layers deposited in the early 1920s [driven by an increase in organic matter supply to the sediment] indicates a maximum in methanogenic biomass and thus a potential peak in CH4 production, which fits with the eutrophication history of the lake. Excess methanogenesis most probably led to CH4 liberation to the water column and subsequent aerobic CH4 oxidation (MOx) as indicated by a higher concentration of diploptene and 17β,21β-homohopanoic acid, with δ13C values as low as −60‰ and −64‰, respectively.Variation in these markers in the sediment indicated changes in the abundance of aerobic CH4 oxidising bacteria (MOB), which thrive at the oxic/anoxic interface in the water column. In the water column, the presence of the C16:1ω8 FA indicated that the MOx community was dominated by Type I MOB. Incorporation of CH4-derived carbon into microbial biomass was also indicated by 13C-depleted diagnostic FAs with δ13C values as low as −53‰ (10-methyl-C16:0, C16:1ω7, C16:1ω5, C18:1ω7, C18:1ω5). In addition, CH4-derived carbon could also be traced into the biomass of photosynthetic organisms. In the water column, the sterols and phytol, originating from photosynthetic organisms, were 13C-depleted. This indicates significant CH4 turnover in the water column, leading to a 12C enrichment in the dissolved organic carbon (DIC)/CO2 pool, which was subsequently fixed by primary producers