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A growing body of observations reveals rapid changes in both the total inventory and distribution of marine oxygen over the later half of the 21st century, leading to increased interest in extending oxygenation records into the past. Use of paleo-oxygen proxies have the potential to extend the spatial and temporal range of current records, bound pre-anthropogenic baselines, provide datasets necessary to test climate models under different boundary conditions, and ultimately understand how ocean oxygenation responds beyond decadal scale changes. This review seeks to summarize the current state-ofknowledge about proxies for reconstructing Cenozoic marine oxygen: sedimentary features, sedimentary redox-sensitive trace elements and isotopes, biomarkers, nitrogen isotopes, foraminiferal trace elements, foraminifera assemblages, foraminifera morphometrics, and benthic foraminifera carbon isotope gradients. Taking stock of each proxy reveals some common limitations in that the majority of proxies function best at low-oxygen concentrations and many reflect multiple environmental drivers. We also highlight recent breakthroughs in geochemistry and proxy approaches for constraining pelagic (in addition to benthic) oxygenation that are rapidly advancing the field. In light of both the emergence of new proxies and the persistent multiple driver problem, the need for multi-proxy approaches and FAIR data storage and sharing is emphasized. Continued refinement of proxy approaches and both proxy-proxy and proxy-model comparisons are likely to support the growing needs of both oceanographer and paleoceanographers interested in paleo-oxygenation records. [ABSTRACT FROM AUTHOR]

The article focuses on the use of hydrogen and carbon isotopes in aquatic plant waxes from Greenland lakes to understand shifts in methane cycling during past Holocene warming, revealing significant changes in methane dynamics in response to elevated temperatures and productivity during the Middle Holocene. This research suggests that ongoing warming may lead to increased methane-derived carbon in Arctic lakes, even in lakes where methane is not a major component of the carbon cycle today.

Abstract: Transfer of organic carbon (OC) from the terrestrial to the oceanic carbon pool is largely driven by riverine and aeolian transport. Before transport, however, terrigenous organic matter can be retained in intermediate terrestrial reservoirs such as soils. Using compound-specific radiocarbon analysis of terrigenous biomarkers their average terrestrial residence time can be evaluated. Here we show compound-specific radiocarbon (14C) ages of terrigenous biomarkers and bulk 14C ages accompanied by geochemical proxy data from core top samples collected along transects in front of several river mouths in the Black Sea. 14C ages of long chain n-alkanes, long chain n-fatty acids and total organic carbon (TOC) are highest in front of the river mouths, correlating well with BIT (branched and isoprenoid tetraether) indices, which indicates contribution of pre-aged, soil-derived terrigenous organic matter. The radiocarbon ages decrease further offshore towards locations where organic matter is dominated by marine production and aeolian input potentially contributes terrigenous organic matter. Average terrestrial residence times of vascular plant biomarkers deduced from n-C29+31 alkanes and n-C28+30 fatty acids ages from stations directly in front of the river mouths range from 900±70years to 4400±170years. These average residence times correlate with size and topography in climatically similar catchments, whereas the climatic regime appears to control continental carbon turnover times in morphologically similar drainage areas of the Black Sea catchment. Along-transect data imply petrogenic contribution of n-C29+31 alkanes and input via different terrigenous biomarker transport modes, i.e., riverine and aeolian, resulting in aged biomarkers at offshore core locations. Because n-C29+31 alkanes show contributions from petrogenic sources, n-C28+30 fatty acids likely provide better estimates of average terrestrial residence times of vascular plant biomarkers. Moreover, sedimentary n-C28 and n-C30 fatty acids appear clearly much less influenced by autochthonous sources than n-C24 and n-C26 fatty acids as indicated by increasing radiocarbon ages with increasing chain-length and are, thus, more representative as vascular plant biomarkers. [Copyright &y& Elsevier]

A negative carbon isotope excursion recorded in terrestrial and marine archives reflects massive carbon emissions into the exogenic carbon reservoir during the Paleocene-Eocene Thermal Maximum. Yet, discrepancies in carbon isotope excursion estimates from different sample types lead to substantial uncertainties in the source, scale, and timing of carbon emissions. Here we show that membrane lipids of marine planktonic archaea reliably record both the carbon isotope excursion and surface ocean warming during the Paleocene-Eocene Thermal Maximum. Novel records of the isotopic composition of crenarchaeol constrain the global carbon isotope excursion magnitude to −4.0 ± 0.4‰, consistent with emission of >3000 Pg C from methane hydrate dissociation or >4400 Pg C for scenarios involving emissions from geothermal heating or oxidation of sedimentary organic matter. A pre-onset excursion in the isotopic composition of crenarchaeol and ocean temperature highlights the susceptibility of the late Paleocene carbon cycle to perturbations and suggests that climate instability preceded the Paleocene-Eocene Thermal Maximum. The Paleocene-Eocene Thermal Maximum (c. 55 million years ago) was a period associated with massive carbon injection into the atmosphere, yet discrepancies in carbon isotope proxy records have led to substantial uncertainties in the source, scale, and timing of carbon emissions. Here, the authors propose that membrane lipids of marine planktonic archaea can reliably record the carbon isotope excursion and surface ocean warming, giving a new constraint for the source and size of the PETM carbon emissions. [ABSTRACT FROM AUTHOR]

Thaumarchaeota, the major sources of marine glycerol dibiphytanyl glycerol tetraether lipids (GDGTs), are believed to fix the majority of their carbon directly from dissolved inorganic carbon (DIC). The δ 13 C values of GDGTs ( δ 13 C GDGT ) may be powerful tools for reconstructing variations in the ocean carbon cycle, including paleoproductivity and water mass circulation, if they can be related to values of δ 13 C DIC . To date, isotope measurements primarily are made on the C 40 biphytane skeletons of GDGTs, rather than on complete tetraether structures. This approach erases information revealed by the isotopic heterogeneity of GDGTs within a sample and may impart an isotopic fractionation associated with the ether cleavage. To circumvent these issues, we present δ 13 C values for GDGTs from twelve recent sediments representing ten continental margin locations. Samples are purified by orthogonal dimensions of HPLC, followed by measurement of δ 13 C values by Spooling Wire Microcombustion (SWiM)-isotope ratio mass spectrometry (IRMS) with 1 σ precision and accuracy of ±0.25‰. Using this approach, we confirm that GDGTs, generally around −19‰, are isotopically “heavy” compared to other marine lipids. However, measured δ 13 C GDGT values are inconsistent with predicted values based on the 13 C content of DIC in the overlying water column and the previously-published biosynthetic isotope fractionation for a pure culture of an autotrophic marine thaumarchaeon. In some sediments, the isotopic composition of individual GDGTs differs, indicating multiple source inputs. The data appear to confirm that crenarchaeol primarily is a biomarker for Thaumarchaeota, but its δ 13 C values still cannot be explained solely by autotrophic carbon fixation. Overall the complexity of the results suggests that both organic carbon assimilation ( ca. 25% of total carbon) and multiple source(s) of exogenous GDGTs (contributing generally <30% of input to sediments) are necessary to explain the observed δ 13 C GDGT values. The results suggest caution when interpreting the total inputs of GDGTs to sedimentary records. Biogenic or open-slope sediments, rather than clastic basinal or shallow shelf sediments, are preferred locations for generating minimally-biased GDGT proxy records. [ABSTRACT FROM AUTHOR]