Hydrogen and oxygen stable isotope analyses of precipitation sampled at Erlangen (southern Germany) between 2010 and 2013

Shallow groundwater aquifers are often influenced by anthropogenic contaminants or increased nutrient levels. In contrast, deeper aquifers hold potentially pristine paleo-waters that are not influenced by modern recharge. They thus represent important water resources, but their recharge history is often unknown. In this study groundwater from two aquifers in southern Germany were analyzed for their hydrogen and oxygen stable isotope compositions. One sampling campaign targeted the upper aquifer that is actively recharged by modern precipitation, whereas the second campaign sampled the confined, deep Benkersandstein aquifer. The groundwater samples from both aquifers were compared to the local meteoric water line to investigate sources and conditions of groundwater recharge. In addition, the deep groundwater was dated by tritium and radiocarbon analyses. Stable and radiogenic isotope data indicate that the deep-aquifer groundwater was not part of the hydrological water cycle in the recent human history. The results show that the groundwater is older than ~20,000 years and most likely originates from isotopically depleted melt waters of the Pleistocene ice age. Today, the use of this aquifer is strictly regulated to preserve the pristine water. Clear identification of such non-renewable paleo-waters by means of isotope geochemistry will help local water authorities to enact and justify measures for conservation of these valuable resources for future generations in the context of a sustainable water management.

Stable isotope geochemistry of pore waters and marine sediments from the New Jersey shelf: Methane formation and fluid origin

Interstitial water and sediment samples of the Integrated Ocean Drilling Program (IODP) expedition 313 "New Jersey Shallow Shelf" were analyzed for chemical composition and stable isotope ratios. A total of 222 water samples were collected from the cores by Rhizon samplers and squeezing of fresh core material. Water was analyzed for its stable oxygen and hydrogen isotope geochemistry (d2H and d18O) at sites M0027A and M0029A, and the carbon isotope composition of the dissolved inorganic carbon (d13CDIC) (all sites). In addition, organic material (Corg) and inorganic carbonates from sediments were analyzed for their carbon ratios (d13Corg and d13Ccarb), and in case of the carbonates also for oxygen (d18Ocarb). Carbon isotopes were also analyzed in samples containing enough methane gas (d13Cmeth). Pore fluids from site M0027A were analyzed for the sulfur isotope composition of dissolved sulfate (d34S). The combination of isotope analyses of all phases (interstitial water, sediment, and gas) with pore water chemistry is expected to enable a better understanding of processes in the sediment and will help to identify the origin of fluids under the New Jersey shelf.

Stable isotope ratios of interstitial fluids from ODP Leg 110 sites

Delta18O values of pore waters from the northern Barbados accretionary prism range from -0.3 to -3.6? and reflect pervasive reaction of volcanic ash to form smectite within the sedimentary sequence and continued low temperature alteration of basalt in the underlying ocean crust with the overprint of diffusive exchange between water in the sediment pores and the open ocean. Delta D values of pore waters in sediments sampled seaward of the deformation front drop from +5? at the sediment surface to -6? at the deepest levels sampled. These changes may also be related to alteration processes but remain largely enigmatic. Sediment deformation caused by impingement of the Caribbean plate on the Atlantic plate has instigated migration of chemically and isotopically distinct fluid along faults and coarse-grained sedimentary beds; delta18O values of pore waters are also locally affected by thrust stacking which increases diffusive pathlengths and possibly modifies diagenetic reaction rates in Pleistocene sediments. Migrating fluids are distinguished by anomalous delta18O values that are as much as 1? higher than those of surrounding fluids. Uncertainties in hydrogen isotope fractionation resulting from processes occurring under these conditions hinder identification of the hydrogen isotope composition of expelled fluid. Stable isotope analyses of pore waters help constrain the fluid migration history of the accretionary prism by limiting the source of fluids, the paths along which fluid flows, and the timing of faulting and subsequent fluid flow.

Table 2: Water stable isotope results and sampling site information of samples taken between 2003 and 2009 on the island of Corsica (western Mediterranean)

The Mediterranean is regarded as a region of intense climate change. To better understand future climate change, this area has been the target of several palaeoclimate studies which also studied stable isotope proxies that are directly linked to the stable isotope composition of water, such as tree rings, tooth enamel or speleothems. For such work, it is also essential to establish an isotope hydrology framework of the region of interest. Surface waters from streams and lakes as well as groundwater from springs on the island of Corsica were sampled between 2003 and 2009 for their oxygen and hydrogen isotope compositions. Isotope values from lake waters were enriched in heavier isotopes and define a local evaporation line (LEL). On the other hand, stream and spring waters reflect the isotope composition of local precipitation in the catchment. The intersection of the LEL and the linear fit of the spring and stream waters reflect the mean isotope composition of the annual precipitation (dP) with values of -8.6(±0.2) per mil for d18O and -58(±2) per mil for d2H. This value is also a good indicator of the average isotope composition of the local groundwater in the island. Surface water samples reflect the altitude isotope effect with a value of -0.17(±0.02) per mil per 100 m elevation for oxygen isotopes. At Vizzavona Pass in central Corsica, water samples from two catchments within a lateral distance of only a few hundred metres showed unexpected but systematic differences in their stable isotope composition. At this specific location, the direction of exposure seems to be an important factor. The differences were likely caused by isotopic enrichment during recharge in warm weather conditions in south-exposed valley flanks compared to the opposite, north-exposed valley flanks.

Benthic foraminiferal stable isotope record from ODP Site 138-849 on the East Pacific Rise

Benthic foraminifer and delta13C data from Site 849, on the west flank of the East Pacific Rise (0°11 'N, 110°31'W; 3851 m), give relatively continuous records of deep Pacific Ocean stable isotope variations between 0 and 5 Ma. The mean sample spacing is 4 k.y. Most analyses are from Cibicides wuellerstorfi, but isotopic offsets relative to Uvigerina peregrina appear roughly constant. Because of its location west of the East Pacific Rise, Site 849 yields a suitable record of mean Pacific Ocean delta13C, which approximates a global oceanic signal. The ~100-k.y.-period climate cycle, which is prevalent in delta18O does not dominate the long-term delta13C record. For delta13C, variations in the ~400- and 41-k.y. periods are more important. Phase lags of delta13C relative to ice volume in the 41- and 23-k.y. bands are consistent with delta13C as a measure of organic biomass. A model-calculated exponential response time of 1-2 k.y. is appropriate for carbon stored in soils and shallow sediments responding to glacial-interglacial climate change. Oceanic delta13C leads ice volume slightly in the 100-k.y. band, and this suggests another process such as changes in continental weathering to modulate mean river delta13C at long periods. The delta13C record from Site 849 diverges from that of Site 677 in the Panama Basin mostly because of decay of 13C-depleted organic carbon in the relatively isolated Panama Basin. North Atlantic to Pacific delta13C differences calculated using published data from Sites 607 and 849 reveal variations in Pliocene deep water within the range of those of the late Quaternary. Maximum delta13C contrast between these sites, which presumably reflects maximum influx of high-delta13C northern source water into the deep North Atlantic Ocean, occurred between 1.3 and 2.1 Ma, well after the initiation of Northern Hemisphere glaciation. Export of high-delta13C North Atlantic Deep Water from the Atlantic to the circumpolar Antarctic, as recorded by published delta13C data from Subantarctic Site 704, appears unrelated to the North Atlantic-Pacific delta13C contrast. To account for this observation, we suggest that deep-water formation in the North Atlantic reflects northern source characteristics, whereas export of this water into the circumpolar Antarctic reflects Southern Hemisphere wind forcing. Neither process appears directly linked to ice-volume variations.

Great Barrier Reef coral element/Ca and stable isotope data and U-Th ages from IODP Expedition 325

Tropical south-western Pacific temperatures are of vital importance to the Great Barrier Reef (GBR), but the role of sea surface temperatures (SSTs) in the growth of the GBR since the Last Glacial Maximum remains largely unknown. Here we present records of Sr/Ca and d18O for Last Glacial Maximum and deglacial corals that show a considerably steeper meridional SST gradient than the present day in the central GBR. We find a 1-2 °C larger temperature decrease between 17° and 20°S about 20,000 to 13,000 years ago. The result is best explained by the northward expansion of cooler subtropical waters due to a weakening of the South Pacific gyre and East Australian Current. Our findings indicate that the GBR experienced substantial meridional temperature change during the last deglaciation, and serve to explain anomalous deglacial drying of northeastern Australia. Overall, the GBR developed through significant SST change and may be more resilient than previously thought.

Stable isotope records of corals from the northern Red Sea

We present a study based on X-ray chronologies and the stable isotopic composition of fossil Porites spp. corals from the northern Gulf of Aqaba (Red Sea) covering the mid-Holocene period from 5750 to 4450 14C years BP (before present). The stable oxygen and carbon isotopic compositions of five specimens reveal regular annual periodicities. Compared with modern Porites spp. from the same environment, the average seasonal delta18O amplitude of the fossil corals is higher (by ca. 0.35-0.60?), whereas annual growth rates are lower (by ca. 3.5 to 2 mm/year). This suggests stronger seasonality of sea surface temperatures and increased variability of the oxygen isotopic composition of the sea water due to changes in the precipitation and evaporation regime during the mid-Holocene. Most likely, summer monsoon rains reached the northern end of the Red Sea at that time. Average annual coral growth rates are diminished probably due to an increased input and resuspension of terrestrial debris to the shallow marine environment during more humid conditions. Our results corroborate published reports of paleodata and model simulations suggesting a northward migration of the African monsoon giving rise to increased seasonalities during the mid-Holocene over northeastern Africa and Arabia.

Stable isotope analysis and temperature reconstruction data from DSDP Hole 94-609B and ODP Hole 162-984B

The Greenland ice sheet is accepted as a key factor controlling the Quaternary glacial scenario. However, the origin and mechanisms of major Arctic glaciation starting at 3.15 Ma and culminating at 2.74 Ma are still controversial. For this phase of intense cooling Ravelo et al. proposed a complex gradual forcing mechanism. In contrast, our new submillennial-scale paleoceanographic records from the Pliocene North Atlantic suggest a far more precise timing and forcing for the initiation of northern hemisphere glaciation (NHG), since it was linked to a 2-3 °C surface water warming during warm stages from 2.95 to 2.82 Ma. These records support previous models, claiming that the final closure of the Panama Isthmus (3.0- ~2.5 Ma induced an increased poleward salt and heat transport. Associated strengthening of North Atlantic Thermohaline Circulation and in turn, an intensified moisture supply to northern high latitudes resulted in the build-up of NHG, finally culminating in the great, irreversible climate crash at marine isotope stage G6 (2.74 Ma). In summary, there was a two-step threshold mechanism that marked the onset of NHG with glacial-to-interglacial cycles quasi-persistent until today.

Stable isotope record of planktonic foraminifera from sediment core MD96-2085

A high-resolution (~4-5cm/kyr) giant piston core record (MD962085) retrieved during an IMAGES II-NAUSICAA cruise from the continental slope of the southeast Atlantic Ocean reveals striking variations in planktonic foraminifer faunal abundances and sea-surface temperatures (SST) during the past 600 000 yr. The location and high-quality sedimentary record of the core provide a good opportunity to assess the variability of the Benguela Current system and associated important features of the ocean-climate system in the southeast Atlantic. The planktonic foraminifer faunal abundances of the core are dominated by three assemblages: (1) Neogloboquadrina pachyderma (right coiling) + Neogloboquadrina dutertrei, (2) Globigerina bulloides, and (3) Globorotalia inflata. The assemblage of N. pachyderma (right coiling) + N. dutertrei shows distinctive abundance changes which are nearly in-phase with glacial-interglacial variations. The high abundances of this assemblage are associated with major glacial conditions, possibly representing low SST/high nutrient level conditions in the southwestern Africa margin. In contrast, the G. bulloides and G. inflata assemblages show greater high-frequency abundance change patterns, which are not parallel to the glacial-interglacial changes. These patterns may indicate rapid oceanic frontal movements from the south, and a rapid change in the intensity of the Benguela upwelling system from the east. A single episode of maximum abundances of a polar water species N. pachyderma (left coiling) occurred in the beginning of stage 9 (~340-330 kyr). The event of the maximum occurrence of this species shown in this record may indicate instability in the Benguela coastal upwelling, or the Antarctic polar front zone position. A winter season SST estimate using transfer function techniques for this record shows primarily glacial-interglacial variations. The SST is maximal during the transitions from the major glacial to interglacial stages (Terminations I, II, IV, V), and is associated with the abundance maxima of a warm water species indicator Globigerinoides ruber. Cross-spectral analyses of the SST record and the SPECMAP stack reveal statistically significant concentrations of variance and coherencies in three major orbital frequency bands. The SST precedes changes in the global ice volume in all orbital frequency bands, indicating a dominant southern Hemispheric climate effect over the Benguela Current region in the southeast Atlantic.

(Table 3) Stable isotope composition of sof t tissues of specimens from the Sea of Okhotsk

We discovered and investigated several cold-seep sites in four depth zones of the Sea of Okhotsk off Northeast Sakhalin: outer shelf (160-250 m), upper slope (250-450 m), intermediate slope (450-800 m), and Derugin Basin (1450-1600 m). Active seepage of free methane or methane-rich fluids was detected in each zone. However, seabed photography and sampling revealed that the number of chemoautotrophic species decreases dramatically with decreasing water depth. At greatest depths in the Derugin Basin, the seeps were inhabited by bacterial mats and bivalves of the families Vesicomyidae (Calyptogena aff. pacifica, C. rectimargo, Archivesica sp.), Solemyidae (Acharax sp.) and Thyasiridae (Conchocele bisecta). In addition, pogonophoran tubeworms of the family Sclerolinidae were found in barite edifices. At the shallowest sites, on the shelf at 160 m, the seeps lack chemoautotrophic macrofauna; their locations were indicated only by the patchy occurrence of bacterial mats. Typical seep-endemic metazoans with chemosynthetic symbionts were confined to seep sites at depths below 370 m. A comparative analysis of the structure of seep and background communities suggests that differences in predation pressure may be an important determinant of this pattern. The abundance of predators such as carnivorous brachyurans and asteroids, which can invade seeps from adjacent habitats and efficiently prey on sessile seep bivalves, decreased very pronouncedly with depth. We conclude from the obvious correlation with the conspicuous pattern in the distribution of seep assemblages that, on the shelf and at the upper slope, predator pressure may be high enough to effectively impede any successful settlement of viable populations of seep-endemic metazoans. However, there was also evidence that other depth-related factors, such as bottom-water current, sedimentary regimes, oxygen concentrations and the supply of suitable settling substrates, may additionally regulate the distribution of seep fauna in the area. As a consequence of the pronounced pattern in the distribution of seep communities, their ecological significance as food sources of surrounding background fauna increased with water depth. Isotopic analyses suggest that in the Derugin Basin seep colonists feed on chemoautotrophic seep organisms, either directly or by preying on metazoans with chemosynthetic symbionts. In contrast, seep organisms apparently do not contribute to the nutrition of the adjacent background fauna on the shelf and at the slope. In this area, elevated epifaunal abundances at seep sites were caused primarily by the availability of suitable settling substrates rather than by an enrichment of food supply.

Stable isotope and geochemical record of sediments from the Bering Sea

here is controversy over the role of marine methane hydrates in atmospheric methane concentrations and climate change during the last glacial period. In this study of two sediment cores from the southeast Bering Sea (700 m and 1467 m water depth), we identify multiple episodes during the last glacial period of intense methane flux reaching the seafloor. Within the uncertainty of the radiocarbon age model, the episodes are contemporaneous in the two cores and have similar timing and duration as Dansgaard-Oeschger events. The episodes are marked by horizons of sediment containing 13C-depleted authigenic carbonate minerals; 13C-depleted archaeal and bacterial lipids, which resemble those found in ANME-1 type anaerobic methane oxidizing microbial consortia; and changes in the abundance and species distribution of benthic foraminifera. The similar timing and isotopic composition of the authigenic carbonates in the two cores is consistent with a region-wide increase in the upward flux of methane bearing fluids. This study is the first observation outside Santa Barbara Basin of pervasive, repeated methane flux in glacial sediments. However, contrary to the "Clathrate Gun Hypothesis" (Kennett et al., 2003), these coring sites are too deep for methane hydrate destabilization to be the cause, implying that a much larger part of the ocean's sedimentary methane may participate in climate or carbon cycle feedback at millennial timescales. We speculate that pulses of methane in these opal-rich sediments could be caused by the sudden release of overpressure in pore fluids that builds up gradually with silica diagenesis. The release could be triggered by seismic shaking on the Aleutian subduction zone caused by hydrostatic pressure increase associated with sea level rise at the start of interstadials.

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.

Planktonic foraminifera fluxes and stable isotope ratios in the Irminger Sea

Past water column stratification can be assessed through comparison of the d18O of different planktonic foraminiferal species. The underlying assumption is that different species form their shells simultaneously, but at different depths in the water column. We evaluate this assumption using a sediment trap time-series of Neogloboquadrina pachyderma (s) and Globigerina bulloides from the NW North Atlantic. We determined fluxes, d18O and d13C of shells from two size fractions to assess size-related effects on shell chemistry and to better constrain the underlying causes of isotopic differences between foraminifera in deep-sea sediments. Our data indicate that in the subpolar North Atlantic differences in the seasonality of the shell flux, and not in depth habitat or test size, determine the interspecies Delta d18O. N. pachyderma (s) preferentially forms from early spring to late summer, whereas the flux ofG. bulloides peaks later in the season and is sustained until autumn. Likewise, seasonality influences large and small specimens differently, with large shells settling earlier in the season. The similarity of the seasonal d18O patterns between the two species indicates that they calcify in an overlapping depth zone close to the surface. However, their d13C patterns are markedly different (>1 per mil). Both species have a seasonally variable offset from d13CDIC that appears to be governed primarily by temperature, with larger offsets associated with higher temperatures. The variable offset from d13CDIC implies that seasonality of the flux affects the fossil d13C signal, which has implications for reconstruction of the past oceanic carbon cycle.