Stable carbon isotope ratios of carbon dioxide from EDC and Berkner Island ice cores for 40-50 ka BP

The stable carbon isotopic signature of carbon dioxide (d13CO2) measured in the air occlusions of polar ice provides important constraints on the carbon cycle in past climates. In order to exploit this information for previous glacial periods, one must use deep, clathrated ice, where the occluded air is preserved not in bubbles but in the form of air hydrates. Therefore, it must be established whether the original atmospheric d13CO2 signature can be reconstructed from clathrated ice. We present a comparative study using coeval bubbly ice from Berkner Island and ice from the bubble-clathrate transformation zone (BCTZ) of EPICA Dome C (EDC). In the EDC samples the gas is partitioned into clathrates and remaining bubbles as shown by erroneously low and scattered CO2 concentration values, presenting a worst-case test for d13CO2 reconstructions. Even so, the reconstructed atmospheric d13CO2 values show only slightly larger scatter. The difference to data from coeval bubbly ice is statistically significant. However, the 0.16 per mil magnitude of the offset is small for practical purposes, especially in light of uncertainty from non-uniform corrections for diffusion related fractionation that could contribute to the discrepancy. Our results are promising for palaeo-atmospheric studies of d13CO2 using a ball mill dry extraction technique below the BCTZ of ice cores, where gas is not subject to fractionation into microfractures and between clathrate and bubble reservoirs.

Experiment: The effect of temperature, salinity and growth rate on the stable hydrogen isotopic composition of long chain alkenones produced by Emiliania huxleyi and Gephyrocapsa oceanica

Two haptophyte algae, Emiliania huxleyi and Gephyrocapsa oceanica, were cultured at different temperatures and salinities to investigate the impact of these factors on the hydrogen isotopic composition of long chain alkenones synthesized by these algae. Results showed that alkenones synthesized by G. oceanica were on average depleted in D by 30 compared to those of E. huxleyi when grown under similar temperature and salinity conditions. The fractionation factor, alpha alkenones-H2O, ranged from 0.760 to 0.815 for E. huxleyi and from 0.741 to 0.788 for G. oceanica. There was no significant correlation of alpha alkenones-H2O with temperature but a positive linear correlation was observed between alpha alkenones-H2O and salinity with ~3 change in fractionation per salinity unit and a negative correlation between alpha alkenones-H2O and growth rate. This suggests that both salinity and growth rate can have a substantial impact on the stable hydrogen isotopic composition of long chain alkenones in natural environments.

The South Atlantic carbon isotope record of planktic foraminifera

We reviewed the paleoceanographic application of the carbon isotope composition of planktic foraminifera. Major controls on the distribution of d13C of dissolved CO2 (d13CSCO2) in the modern ocean are photosynthesis-respiration cycle, isotopic fractionation during air-sea exchange, and circulation. The carbon isotope composition of surface waters is not recorded without perturbations by planktic foraminifera. Besides d13CSCO2 of the surrounding seawater, the d13C composition of planktic foraminifera is affected by vital effects, the water depth of calcification and postdepositional dissolution. We compared several high-resolution (>10cm/ka) carbon isotope records from the Southern Ocean, the Benguela upwelling system, and the tropical Atlantic. In the Southern Ocean, carbon isotope values are about 1.2 per mil lower during the LGM and up to 1.7 per mil lower during the last deglaciation, when compared to the Holocene. These depletions might be explained with a combination of a subsurface nutrient enrichment and reduced air-sea exchange due to an increased stratification of surface waters. In the Benguela Upwelling system, waters originating in the south are upwelled. While the deglacial minimum is transferred and recorded in its full extent in the d13C record of Globigerina bulloides, glacial values show only little changes. This might suggest, that the lower glacial d13C values of high-latitude surface waters are not upwelled off Namibia, or that G. bulloides records post-upwelling conditions, when increased seasonal production has already increased surface-water d13C. Synchronous to the d13C depletions in high latitudes, low d13C values were recorded in Globigerinoides sacculifer during the LGM and during the last deglaciation in the nutrient-depleted western equatorial Atlantic. Hence, part of the glacial-interglacial variability presumably transferred from high to low latitudes seems to be related to changes in thermodynamic fractionation. The variability in d13C is lowest in the northernmost core M35003-4 from the eastern Caribbean, implying that the Antarctic Intermediate Water might have acted as a conduit to transfer the deglacial minimum to tropical surface waters.

(Appendix) Carbon and nitrogen isotope ratios of ODP Site 160-964

Nitrogen isotopes of chlorins, degradation products of chlorophyll, reflect the isotopic composition of nutrient N utilized by marine phytoplankton communities. Here we show that in sediments of the eastern Mediterranean Pleistocene and Holocene, values of d15N for chlorins and total nitrogen vary in concert, with a consistent offset of ~5 per mil reflecting the fractionation imparted during chlorophyll biosynthesis. Samples from the Integrated Ocean Drilling Program Sites 964 and 969 were analyzed at a sampling resolution of ~4-10 cm, clustered around sapropel events 2, 3, 4 and 5 (~100-170 ka). In low organic content sediments, chlorin values of ~0 per mil coincident with total nitrogen values of ~+ 5 per mil indicate that the latter reflects the original biomass and is not a consequence of diagenetic isotope enrichment. In sapropel horizons, the chlorin and total nitrogen values are 5 per mil more negative (~-5 per mil and ~ 0 per mil, respectively), resembling previously-reported, modern-day water-column particulates (~0 per mil). We suggest that nutrient conditions in the Eastern Mediterranean correspond to three scenarios and that the similarity between sapropel and modern-day bulk d15N is coincidental. Organic-poor marl sediments formed under oligotrophic conditions where surface productivity resulted from upwelling of Atlantic-sourced nitrate. Sapropels were characterized by enhanced diazotrophy that was likely fueled by increased riverine P fluxes to surface waters. Present-day conditions are dominated by anthropogenic N sources. These scenarios agree with a model of sapropel formation in which stratification caused by increased fresh-water inputs led to N fixation due to P:N nutrient imbalance. Enhanced production combined with stratification promoted and maintained anoxic deep waters, consequently increasing organic matter preservation. Such a model may be relevant to interpreting other episodes of intense organic matter deposition in past oceans.

(Table 1) Stable oxygen isotope ratios of benthic foraminifera from Pacific Ocean deep-sea sediments

The thermal structure of the Pacific Ocean between water depths of about 1 and 4.5 kilometers is estimated from the oxygen isotopic ratio of benthonic foraminifera from deep-drilled and piston cores of early Pliocene age (about 3 to 5 million years ago). The ratio of oxygen-18 to oxygen-16 in the early Pliocene at each site varies by an average of only ± 0.12 per mil (1 standard deviation). A plot of the oxygen isotopic ratio against modern bottom-water temperature is adequately fit by a line having a slope of - 0.26 per mil per degree Celsius (the equilibrium temperature dependence of calcite-water fractionation), suggesting that the temperature gradient of the Pacific Ocean during the early Pliocene was similar to that of today.

Younger Dryas-Holocene sedimentary plant-wax hydrogen isotopes from the southern European Alps

We present a Younger Dryas-Holocene record of the hydrogen isotopic composition of sedimentary plant waxes (dDwax) from the southern European Alps (Lake Ghirla, N-Italy) to investigate its sensitivity to climatic forcing variations in this mid-latitude region (45°N). A modern altitudinal transect of dD values of river water and leaf waxes in the Lake Ghirla catchment is used to test present-day climate sensitivity of dDwax. While we find that altitudinal effects on dDwax are minor at our study site, temperature, precipitation amount, and evapotranspiration all appear to influence dDwax to varying extents. In the lake-sediment record, dDwax values vary between -134 and -180 per mil over the past 13 kyr. The long-term Holocene pattern of dDwax parallels the trend of decreasing temperature and is thus likely forced by the decline of northern hemisphere summer insolation. Shorter-term fluctuations, in contrast, may reflect both temperature and moisture-source changes. During the cool Younger Dryas and Little Ice Age (LIA) periods we observe unexpectedly high dDwax values relative to those before and after. We suggest that a change towards a more D-enriched moisture source is required during these intervals. In fact, a shift from northern N-Atlantic to southern N-Atlantic/western Mediterranean Sea sources would be consistent with a southward migration of the Westerlies with climate cooling. Prominent dDwax fluctuations in the early and middle Holocene are negative and potentially associated with temperature declines. In the late Holocene (<4 kyr BP), excursions are partly positive (as for the LIA) suggesting a stronger influence of moisture-source changes on dDwax variation. In addition to isotopic fractionations of the hydrological cycle, changes in vegetation composition, in the length of the growing season, and in snowfall amount provide additional potential sources of variability, although we cannot yet quantitatively assess these in the paleo-record. We conclude that while our dDwax record from the Alps does contain climatic information, it is a complicated record that would require additional constraints to be robustly interpreted. This also has important implications for other water-isotope-based proxy records of precipitation and hydro-climate from this region, such as cave speleothems.

Molecular hydrogen (H2) mixing ratio and stable isotopic composition (dD) at the Cabauw tall tower in the Netherlands (2008-2012)

Measurements of the stable isotopic composition (dD(H2) or dD) of atmospheric molecular hydrogen (H2) are a useful addition to mixing ratio (X(H2)) measurements for understanding the atmospheric H2 cycle. dD datasets published so far consist mostly of observations at background locations. We complement these with observations from the Cabauw tall tower at the CESAR site, situated in a densely populated region of the Netherlands. Our measurements show a large anthropogenic influence on the local H2 cycle, with frequently occurring pollution events that are characterized by X(H2) values that reach up to 1 ppm and low dD values. An isotopic source signature analysis yields an apparent source signature below -400 per mil, which is much more D-depleted than the fossil fuel combustion source signature commonly used in H2 budget studies. Two diurnal cycles that were sampled at a suburban site near London also show a more D-depleted source signature (-340 per mil), though not as extremely depleted as at Cabauw. The source signature of the Northwest European vehicle fleet may have shifted to somewhat lower values due to changes in vehicle technology and driving conditions. Even so, the surprisingly depleted apparent source signature at Cabauw requires additional explanation; microbial H2 production seems the most likely cause. The Cabauw tower site also allowed us to sample vertical profiles. We found no decrease in (H2) at lower sampling levels (20 and 60m) with respect to higher sampling levels (120 and 200m). There was a significant shift to lower median dD values at the lower levels. This confirms the limited role of soil uptake around Cabauw, and again points to microbial H2 production during an extended growing season, as well as to possible differences in average fossil fuel combustion source signature between the different footprint areas of the sampling levels. So, although knowledge of the background cycle of H2 has improved over the last decade, surprising features come to light when a non-background location is studied, revealing remaining gaps in our understanding.

Oxygen isotope ratios amd Li concentrations in spilitized basaltic rocks of DSDP Hole 83-504B (Table 5)

Li-delta18O-SiO2 relationships have been examined for suites of spilitized basaltic rocks (DSDP 504B; Xigaze Ophiolite; Blanco Fracture Zone; Greater Caucasus; Rhenohercynian Fold Belt) and intra-plate evolved tholeiites (Northern Hessian Depression and Vogelsberg, W Germany; Mount Falla, Transantarctic Mountains). Relative to unaltered MORB and intra-plate primary olivine tholeiites, both the spilitic rocks and the evolved tholeiites are characterized by Li and 18O enrichment. For the spilitic rocks, Li and 18O enrichment is accompanied by a loss of SiO2 as a result of seawater hydrothermal alteration, whereas the evolved tholeiites have gained SiO2, Li and 18O from fractionation of mafic phases and assimilation of crustal rocks. On Li vs. SiO2 and delta18O vs. SiO2 diagrams, the two rock groups plot largely in distinct fields, suggesting the possibility of so distinguishing between such lithologies in the ancient rock record. Mafic granulite xenoliths from the Northern Hessian Depression have elevated Li and 18O abundances at low SiO2 contents. Even after correction for extraction of felsic components, their Li-delta18O-SiO2 signatures plot within the field of spilitic protoliths, suggesting that the lower crust in this region contains relics of spilitic rocks from a former oceanic crust.

Diatom isotope data from ODP Hole 178-1098A for the last deglaciation (12.2-12.8 ka BP)

Understanding the response of the Antarctic ice sheets during the rapid climatic change that accompanied the last deglaciation has implications for establishing the susceptibility of these regions to future 21st Century warming. A unique diatom d18O record derived from a high-resolution deglacial seasonally laminated core section off the west Antarctic Peninsula (WAP) is presented here. By extracting and analysing single species samples from individual laminae, season-specific isotope records were separately generated to show changes in glacial discharge to the coastal margin during spring and summer months. As well as documenting significant intra-annual seasonal variability during the deglaciation, with increased discharge occurring in summer relative to spring, further intra-seasonal variations are apparent between individual taxa linked to the environment that individual diatom species live in. Whilst deglacial d18O are typically lower than those for the Holocene, indicating glacial discharge to the core site peaked at this time, inter-annual and inter-seasonal alternations in excess of 3 per mil suggest significant variability in the magnitude of these inputs. These deglacial variations in glacial discharge are considerably greater than those seen in the modern day water column and would have altered both the supply of oceanic warmth to the WAP as well as regional marine/atmospheric interactions. In constraining changes in glacial discharge over the last deglaciation, the records provide a future framework for investigating links between annually resolved records of glacial dynamics and ocean/climate variability along the WAP.