Mixing of Rhône River water in Lake Geneva (Switzerland-France) inferred from stable hydrogen and oxygen isotope profiles

Depth profiles were sampled at different locations throughout Lake Geneva on a monthly and seasonal basis over the course of 2 years and analysed for their stable hydrogen and oxygen isotope compositions. The isotopic compositions indicate an isotopic stratification in the metalimnion during summer and fall. This is related to mixing of Rhône River water, which in summer is dominated by snow and glacier melt waters, and lake water, with the latter having a homogenous isotopic composition. The observed interflow layer is 7-15 m thick and can be traced by the distinct stable isotope composition of the water for about 55 km throughout the lake as well as into shallow bay regions. Depth of the interflow layer close to the Rhône River mouth is similar to those previously described based on echo-soundings and turbidity profiles of sediment dispersion. In contrast to previous descriptions of the interflow within Lake Geneva, the stable isotope compositions allow for direct, natural tracing of the Rhône River water even in cases where the turbidity and conductivity measurements do not indicate such an interflow. In addition, the method allows for a quantification of the Rhône River and lake water in the interflow with the fraction of Rhône River water within the interflow estimated to be up to 37% in summer. The isotopic composition further indicates different vertical mixing processes within the two lake basins of Lake Geneva, related to the density gradients and local stability within the water column. The method may be applicable to other lakes in catchments with large differences in the topography as water that originates from high altitudes or glaciers has a distinct oxygen and hydrogen isotope composition compared to other sources of water originating at lower altitudes and/or from direct precipitation over the lake. Stable isotope measurements thus improve the understanding of the circulation of water within the lake, which is fundamental for an evaluation of the water residence times, dissolved pollutant and nutrient transport as well as oxygenation.

Stable carbon and oxygen isotopes in tree rings show physiological responses of Pericopsis elata to precipitation in the Congo Basin

In equatorial regions, where tree rings are less distinct or even absent, the response of forests to high-frequency climate variability is poorly understood. We measured stable carbon and oxygen isotopes in anatomically distinct, annual growth rings of four Pericopsis elata trees from a plantation in the Congo Basin, to assess their sensitivity to recorded changes in precipitation over the last 50 y. Our results suggest that oxygen isotopes have high common signal strength (EPS = 0.74), and respond to multi-annual precipitation variability at the regional scale, with low δ18O values (28–29‰) during wetter conditions (1960–1970). Conversely, δ13C are mostly related to growth variation, which in a light-demanding species are driven by competition for light. Differences in δ13C values between fast- and slow-growing trees (c. 2‰), result in low common signal strength (EPS = 0.37) and are driven by micro-site conditions rather than by climate. This study highlights the potential for understanding the causes of growth variation in P. elata as well as past hydroclimatic changes, in a climatically complex region characterized by a bimodal distribution in precipitation.

Molar gas ratios and stable oxygen and nitrogen isotopes of air entrapped in ice, North America

The molar ratios of atmospheric gases change during dissolution in water due to differences in their relative solubilities. We exploited this characteristic to develop a tool to clarify the origin of ice formations in permafrost regions. Extracted from ice, molar gas ratios can distinguish buried glacier ice from intrasedimental ground ice formed by freezing groundwaters. An extraction line was built to isolate gases from ice by melting and trapping with liquid He, followed by analysis of N2, O2, Ar, 18O-O2 and 15N-N2, by continuous flow mass spectrometry. The method was tested using glacier ice, aufeis ice (river icing) and intrasedimental ground ice from sites in the Canadian Arctic. O2/Ar and N2/Ar ratios clearly distinguish between atmospheric gas in glacial ice and gases from intrasedimental ground ice, which are exsolved from freezing water. 615NN2 and 618OO2 in glacier ice, aufeis ice and intrasedimental ground ice do not show clear distinguishing trends as they are affected by various physical processes during formation such as gravitational settling, excess air addition, mixing with snow pack, and respiration.

Water stable oxygen isotope records from six Antarctic ice core sites for the present and last interglacial periods

We compare the present and last interglacial periods as recorded in Antarctic water stable isotope records now available at various temporal resolutions from six East Antarctic ice cores: Vostok, Taylor Dome, EPICA Dome C (EDC), EPICA Dronning Maud Land (EDML), Dome Fuji and the recent TALDICE ice core from Talos Dome. We first review the different modern site characteristics in terms of ice flow, meteorological conditions, precipitation intermittency and moisture origin, as depicted by meteorological data, atmospheric reanalyses and Lagrangian moisture source diagnostics. These different factors can indeed alter the relationships between temperature and water stable isotopes. Using five records with sufficient resolution on the EDC3 age scale, common features are quantified through principal component analyses. Consistent with instrumental records and atmospheric model results, the ice core data depict rather coherent and homogenous patterns in East Antarctica during the last two interglacials. Across the East Antarctic plateau, regional differences, with respect to the common East Antarctic signal, appear to have similar patterns during the current and last interglacials. We identify two abrupt shifts in isotopic records during the glacial inception at TALDICE and EDML, likely caused by regional sea ice expansion. These regional differences are discussed in terms of moisture origin and in terms of past changes in local elevation histories, which are compared to ice sheet model results. Our results suggest that elevation changes may contribute significantly to inter-site differences. These elevation changes may be underestimated by current ice sheet models

Stable oxygen isotope record from Greenland ice cores

Twenty ice cores drilled in medium to high accumulation areas of the Greenland ice sheet have been used to extract seasonally resolved stable isotope records. Relationships between the seasonal stable isotope data and Greenland and Icelandic temperatures as well as atmospheric flow are investigated for the past 150-200 years. The winter season stable isotope data are found to be influenced by the North Atlantic Oscillation (NAO) and very closely related to SW Greenland temperatures. The linear correlation between the first principal component of the winter season stable isotope data and Greenland winter temperatures is 0.71 for seasonally resolved data and 0.83 for decadally filtered data. The summer season stable isotope data display higher correlations with Stykkisholmur summer temperatures and North Atlantic SST conditions than with SW Greenland temperatures. The linear correlation between Stykkisholmur summer temperatures and the first principal component of the summer season stable isotope data is 0.56, increasing to 0.66 for decadally filtered data. Winter season stable isotope data from ice core records that reach more than 1400 years back in time suggest that the warm period that began in the 1920s raised southern Greenland temperatures to the same level as those that prevailed during the warmest intervals of the Medieval Warm Period some 900-1300 years ago. This observation is supported by a southern Greenland ice core borehole temperature inversion. As Greenland borehole temperature inversions are found to correspond better with winter stable isotope data than with summer or annual average stable isotope data it is suggested that a strong local Greenland temperature signal can be extracted from the winter stable isotope data even on centennial to millennial time scales.

Stable isotope ratios and chemistry on corals from the Caribbean Sea

Instrumental climate data are limited in length and only available with low spatial coverage before the middle of the 20th century. This is too short to reliably determine and interpret decadal and longer scale climate variability and to understand the underlying mechanisms with sufficient accuracy. A proper knowledge of past variability of the climate system is needed to assess the anthropogenic impact on climate and ecosystems, and also important with regard to long-range climate forecasting. Highly-resolved records of past climate variations that extend beyond pre-industrial times can significantly help to understand long-term climate changes and trends. Indirect information on past environmental and climatic conditions can be deduced from climate-sensitive proxies. Large colonies of massive growing tropical reef corals have been proven to sensitively monitor changes in ambient seawater. Rapid skeletal growth, typically ranging between several millimeters to centimeters per year, allows the development of proxy records at sub-seasonal resolution. Stable oxygen isotopic composition and trace elemental ratios incorporated in the aragonitic coral skeleton can reveal a detailed history of past environmental conditions, e.g., sea surface temperature (SST). In general, coral-based reconstructions from the tropical Atlantic region have lagged behind the extensive work published using coral records from the Indian and Pacific Oceans. Difficulties in the analysis of previously utilized coral archives from the Atlantic, typically corals of the genera Montastrea and Siderastrea, have so far exacerbated the production of long-term high-resolution proxy records. The objective of this study is the evaluation of massive fast-growing corals of the species Diploria strigosa as a new marine archive for climate reconstructions from the tropical Atlantic region. For this purpose, coral records from two study sites in the eastern Caribbean Sea (Guadeloupe, Lesser Antilles; and Archipelago Los Roques, Venezuela) were examined. At Guadeloupe, a century-long monthly resolved multi-proxy coral record was generated. Results present the first d18O (Sr/Ca)-SST calibration equations for the Atlantic braincoral Diploria strigosa, that are robust and consistent with previously published values using other coral species from different regions. Both proxies reflect local variability of SST on a sub-seasonal scale, which is a precondition for studying seasonally phase-locked climate variations, as well as track variability on a larger spatial scale (i.e., in the Caribbean and tropical North Atlantic). Coral Sr/Ca reliably records local annual to interannual temperature variations and is higher correlated to in-situ air temperature than to grid-SST. The warming calculated from coral Sr/Ca is concurrent with the strong surface temperature increase at the study site during the past decades. Proxy data show a close relationship to major climate signals from the tropical Pacific and North Atlantic (the El Niño Southern Oscillation (ENSO) and the North Atlantic Oscillation (NAO)) affecting the seasonal cycle of SST in the North Tropical Atlantic (NTA). Coral oxygen isotopes are also influenced by seawater d18O (d18Osw) which is linked to the hydrological cycle, and capture large-scale climate variability in the NTA region better than Sr/Ca. Results from a quantitative comparison between extreme events in the two most prominent modes of external forcing, namely the ENSO and NAO, and respective events recorded in seasonal coral d18O imply that SST variability at the study site is highly linked to Pacific and North Atlantic variability, by this means supporting the assumptions of observational- and model-based studies which suggest a strong impact of ENSO and NAO forcings onto the NTA region through a modulation of trade wind strength in winter. Results from different spectral analysis tools suggest that interannual climate variability recorded by the coral proxies is II largely dictated by Pacific ENSO forcing, whereas at decadal and longer timescales the influence of the NAO is dominan. tThe Archipelago Los Roques is situated in the southeastern Caribbean Sea, north of the Venezuelan coast. Year-to-year variations in monthly resolved coral d18O of a nearcentury- long Diploria strigosa record are significantly correlated with SST and show pronounced multidecadal variations. About half of the variance in coral d18O can be explained by variations in seawater d18O, which can be estimated by calculating the d18Oresidual via subtracting the SST component from measured coral d18O. The d18Oresidual and a regional precipitation index are highly correlated at low frequencies, suggesting that d18Osw variations are primarily atmospheric-driven. Warmer SSTs at Los Roques broadly coincide with higher precipitation in the southeastern Caribbean at multidecadal time scales, effectively strengthening the climate signal in the coral d18O record. The Los Roques coral d18O record displays a strong and statistically significant relationship to different indices of hurricane activity during the peak of the Atlantic hurricane season in boreal summer and is a particularly good indicator of decadal-multidecadal swings in the latter indices. In general, the detection of long-term changes and trends in Atlantic hurricane activity is hampered due to the limited length of the reliable instrumental record and the known inhomogeneity in the observational databases which result from changes in observing practice and technology over the years. The results suggest that coral-derived proxy data from Los Roques can be used to infer changes in past hurricane activity on timescales that extend well beyond the reliable record. In addition, the coral record exhibits a clear negative trend superimposed on the decadal to multidecadal cycles, indicating a significant warming and freshening of surface waters in the genesis region of tropical cyclones during the past decades. The presented coral d18O time series provides the first and, so far, longest continuous coral-based record of hurricane activity. It appears that the combination of both signals (SST and d18Osw) in coral d18O leads to an amplification of large-scale climate signals in the record, and makes coral d18O even a better proxy for hurricane activity than SST alone. Atlantic hurricane activity naturally exhibits strong multidecadal variations that are associated with the Atlantic Multidecadal Oscillation (AMO), the major mode of lowfrequency variability in the North Atlantic Ocean. However, the mechanisms underlying this multidecadal variability remain controversial, primarily because of the limited instrumental record. The Los Roques coral d18O displays strong multidecadal variability with a period of approximately 60 years that is closely related to the AMO, making the Archipelago Los Roques a very sensitive location for studying low-frequency climate variability in the Atlantic Ocean. In summary, the coral records presented in this thesis capture different key climate variables in the north tropical Atlantic region very well, indicating that fast-growing Diploria strigosa corals represent a promising marine archive for further proxy-based reconstructions of past climate variability on a range of time scales.

Element contents, sulfur and oxygen isotopes, and molecular biomarkers of phosphatic crust samples from the Chimbote Platform of the shelf off Peru

Authigenic phosphatic laminites enclosed in phosphorite crusts from the shelf off Peru (10°01' S and 10°24' S) consist of carbonate fluorapatite layers, which contain abundant sulfide minerals including pyrite (FeS2) and sphalerite (ZnS). Low d34Spyrite values (average -28.8 per mill) agree with bacterial sulfate reduction and subsequent pyrite formation. Stable sulfur isotopic compositions of sulfate bound in carbonate fluorapatite are lower than that of sulfate from ambient sea water, suggesting bacterial reoxidation of sulfide by sulfide-oxidizing bacteria. The release of phosphorus and subsequent formation of the autochthonous phosphatic laminites are apparently caused by the activity of sulfate-reducing bacteria and associated sulfide-oxidizing bacteria. Following an extraction-phosphorite dissolution-extraction procedure, molecular fossils of sulfate-reducing bacteria (mono-O-alkyl glycerol ethers, di-O-alkyl glycerol ethers, as well as the short-chain branched fatty acids i/ai-C15:0, i/ai-C17:0 and 10MeC16:0) are found to be among the most abundant compounds. The fact that these molecular fossils of sulfate-reducing bacteria are distinctly more abundant after dissolution of the phosphatic laminite reveals that the lipids are tightly bound to the mineral lattice of carbonate fluorapatite. Moreover, compared with the autochthonous laminite, molecular fossils of sulfate-reducing bacteria are: (1) significantly less abundant and (2) not as tightly bound to the mineral lattice in the other, allochthonous facies of the Peruvian crusts consisting of phosphatic coated grains. These observations confirm the importance of sulfate-reducing bacteria in the formation of the phosphatic laminite. Model calculations highlight that organic matter degradation by sulfate-reducing bacteria has the potential to liberate sufficient phosphorus for phosphogenesis.

Surface sediment samples from several fore-arc basins west and southwest of the Indonesian Archipelago, analyzed by planktonic foraminifera, stable oxygen and carbon isotopic signals and opal and CaCO3 contents in bulk sediment

A total of 69 surface sediment samples from several fore-arc basins located west and southwest of the Indonesian Archipelago was analyzed with respect to the faunal composition of planktonic foraminifera, the stable oxygen and carbon isotopic signal of a surface-dwelling (Globigerinoides ruber) and a thermocline-dwelling (Neogloboquadrina dutertrei) species, and the opal and CaCO3 contents in bulk sediment. Our results show that the distribution pattern of opal in surface sediments corresponds well to the upwelling-induced chlorophyll concentration in the upper water column and thus, represents a reliable proxy for marine productivity in the coastal upwelling area off S and SW Indonesia. Present-day oceanography and marine productivity are also reflected in the tropical to subtropical and upwelling assemblages of planktonic foraminifera in the surface sediments, which in part differ from previous studies in this region probably due to different coring methods and dissolution effects. The average stable oxygen isotopic values (d18O) of G. ruber in surface sediments vary between 2.9 per mill and 3.2 per mill from basin to basin and correspond to the oceanographic settings during the SE monsoon (July-October) off west Sumatra, whereas off southern Indonesia, they reflect the NW monsoon (December-March) or annual average conditions. The d18O values of N. dutertrei show a stronger interbasinal variation between 1.6 per mill and 2.2 per mill and correspond to the upper thermocline hydrology in July-October. In addition, the difference between the shell carbon isotopic values (d13C) of G. ruber and N. dutertrei (Delta d13C) appears to be an appropriate productivity recorder only in the non-upwelling areas off west Sumatra. Consequently, joint interpretation of the isotopic values of these species is distinctive for different fore-arc basins W and SW of Indonesia and should be considered in paleoceanographic studies.

Stable oxygen isotope and Mg/Ca ratios of planktonic foraminifera from the Holocene and the Last Glacial Maximum

We measured oxygen isotopes and Mg/Ca ratios in the surface-dwelling planktonic foraminifer Globigerinoides ruber (white s.s.) and the thermocline dweller Pulleniatina obliquiloculata to investigate upper ocean spatial variability in the Indo-Pacific Warm Pool (IPWP). We focused on three critical time intervals: the Last Glacial Maximum (LGM; 18-21.5 ka), the early Holocene (8-9 ka), and the late Holocene (0-2 ka). Our records from 24 stations in the South China Sea, Timor Sea, Indonesian seas, and western Pacific indicate overall dry and cool conditions in the IPWP during the LGM with a low thermal gradient between surface and thermocline waters. During the early Holocene, sea surface temperatures increased by ~3°C over the entire region, indicating intensification of the IPWP. However, in the eastern Indian Ocean (Timor Sea), the thermocline gradually shoaled from the LGM to early Holocene, reflecting intensification of the subsurface Indonesian Throughflow (ITF). Increased surface salinity in the South China Sea during the Holocene appears related to northward displacement of the monsoonal rain belt over the Asian continent together with enhanced influx of saltier Pacific surface water through the Luzon Strait and freshwater export through the Java Sea. Opening of the freshwater portal through the Java Sea in the early Holocene led to a change in the vertical structure of the ITF from surface- to thermocline-dominated flow and to substantial freshening of Timor Sea thermocline waters.