Optimized Demineralization Technique for the Measurement of Stable Isotope Ratios of Nonexchangeable H in Soil Organic Matter

To make use of the isotope ratio of nonexchangeable hydrogen (δ2Hn (nonexchangeable)) of bulk soil organic matter (SOM), the mineral matrix (containing structural water of clay minerals) must be separated from SOM and samples need to be analyzed after H isotope equilibration. We present a novel technique for demineralization of soil samples with HF and dilute HCl and recovery of the SOM fraction solubilized in the HF demineralization solution via solid-phase extraction. Compared with existing techniques, organic C (Corg) and organic N (Norg) recovery of demineralized SOM concentrates was significantly increased (Corg recovery using existing techniques vs new demineralization method: 58% vs 78%; Norg recovery: 60% vs 78%). Chemicals used for the demineralization treatment did not affect δ2Hn values as revealed by spiking with deuterated water. The new demineralization method minimized organic matter losses and thus artificial H isotope fractionation, opening up the opportunity to use δ2Hn analyses of SOM as a new tool in paleoclimatology or geospatial forensics.

Helium transfer from water into quartz crystals: A new approach for porewater dating

Several important fundamental and applied problems require a quantification of slow rates of groundwater flow. To resolve these problems helium appears to be a promising tracer. In this contribution we discuss a new approach, which gives the helium inventory in a rock – pore water system by using the relevant mineral record, i.e., without extraction and investigation of the porewater samples. Some U- and Th-poor minerals such as quartz (quartz separates from Permo-Carboniferous Formation, sandstone–shale interlayering, Molasses Basin, Northern Switzerland, hereafter PCF, are used in this study) contain excessive helium having migrated into their internal helium-accessible volume (HAV) from the surrounding porewater [I.N. Tolstikhin, B.E. Lehmann, H.H. Loosli, A. Gautschi, Helium and argon isotopes in rocks, minerals and related groundwaters: a case study in Northern Switzerland, Geochim. Cosmochim. Acta 60 (1996) 1497–1514]. These volumes are estimated by using helium as a nano-size penetrating tool, i.e., by saturation of the minerals with helium under controlled pressure–temperature conditions and subsequent measurements of the helium-saturated concentrations. In the quartz separates HAV/total volume ratios vary from 0.017% to 0.16%; along with the measured initial (unsaturated) He concentration the HAV gives the internal helium pressure, the mean value obtained for 7 samples (25 sample aliquots) is P=0.45F0.15 atm (1 r). The product of helium pressure and solubility (7.35_10_3 cc STP He/cc H2O for the temperature and salinity of PCF aquifers reported in [F.J. Pearson, W. Balderer, H.H. Loosli, B.E. Lehmann, A. Matter, T. Peters, H. Schmassmann, A. Gautschi, Applied Isotope Hydrogeology–A Case Study in Northern Switzerland, Elsevier Amsterdam, 1991, 439 pp.]) is the mineral-derived He concentration in the respective porewater, CPW=0.0035F0.0017 cc He/cc H2O. This value is in full accord with measured He concentrations in PCF aquifers, CPCF, varying from 0.0045 to 0.0016 cc He/cc H2O. This agreement validates the proposed approach and also shows that the mineral–porewater helium–concentration equilibrium has been established. Indeed, estimates of the He-migration rates through our quartz samples show that in ~6000 years the internal pressure should equilibrate with He-concentration in related porewater of PCF, and this time interval is short compared to independent estimates [I.N. Tolstikhin, B.E. Lehmann, H.H. Loosli, A. Gautschi, Helium and argon isotopes in rocks, minerals and related groundwaters: a case study in Northern Switzerland, Geochim. Cosmochim. Acta 60 (1996) 1497–1514]. The helium inventory in the rock–porewater assemblage shows that helium abundance in pore waters is indeed important. In shale samples (with ~15% porosity) porewaters contain more helium than the host minerals altogether. Porewater heliumconcentration profiles, available from the mineral record, along with helium production rates are input parameters allowing model(s) of helium migration through a hydrological structure to be developed. Quite high helium concentrations in PCF porewaters imply slow removal mechanisms, which will be discussed elsewhere.

Lithium isotope constraints on crust–mantle interactions and surface processes on Mars

Lithium abundances and isotope compositions are reported for a suite of martian meteorites that span the range of petrological and geochemical types recognized to date for Mars. Samples include twenty-one bulk-rock enriched, intermediate and depleted shergottites, six nakhlites, two chassignites, the orthopyroxenite Allan Hills (ALH) 84001 and the polymict breccia Northwest Africa (NWA) 7034. Shergottites unaffected by terrestrial weathering exhibit a range in δ7Li from 2.1 to 6.2‰, similar to that reported for pristine terrestrial peridotites and unaltered mid-ocean ridge and ocean island basalts. Two chassignites have δ7Li values (4.0‰) intermediate to the shergottite range, and combined, these meteorites provide the most robust current constraints on δ7Li of the martian mantle. The polymict breccia NWA 7034 has the lowest δ7Li (−0.2‰) of all terrestrially unaltered martian meteorites measured to date and may represent an isotopically light surface end-member. The new data for NWA 7034 imply that martian crustal surface materials had both a lighter Li isotope composition and elevated Li abundance compared with their associated mantle. These findings are supported by Li data for olivine-phyric shergotitte NWA 1068, a black glass phase isolated from the Tissint meteorite fall, and some nakhlites, which all show evidence for assimilation of a low-δ7Li crustal component. The range in δ7Li for nakhlites (1.8 to 5.2‰), and co-variations with chlorine abundance, suggests crustal contamination by Cl-rich brines. The differences in Li isotope composition and abundance between the martian mantle and estimated crust are not as large as the fractionations observed for terrestrial continental crust and mantle, suggesting a difference in the styles of alteration and weathering between water-dominated processes on Earth versus possibly Cl–S-rich brines on Mars. Using high-MgO shergottites (>15 wt.% MgO) it is possible to estimate the δ7Li of Bulk Silicate Mars (BSM) to be 4.2 ± 0.9‰ (2σ). This value is at the higher end of estimates for the Bulk Silicate Earth (BSE; 3.5 ± 1.0‰, 2σ), but overlaps within uncertainty.

Estimation and calibration of the water isotope differential diffusion length in ice core records

Palaeoclimatic information can be retrieved from the diffusion of the stable water isotope signal during firnification of snow. The diffusion length, a measure for the amount of diffusion a layer has experienced, depends on the firn temperature and the accumulation rate. We show that the estimation of the diffusion length using power spectral densities (PSDs) of the record of a single isotope species can be biased by uncertainties in spectral properties of the isotope signal prior to diffusion. By using a second water isotope and calculating the difference in diffusion lengths between the two isotopes, this problem is circumvented. We study the PSD method applied to two isotopes in detail and additionally present a new forward diffusion method for retrieving the differential diffusion length based on the Pearson correlation between the two isotope signals. The two methods are discussed and extensively tested on synthetic data which are generated in a Monte Carlo manner. We show that calibration of the PSD method with this synthetic data is necessary to be able to objectively determine the differential diffusion length. The correlation-based method proves to be a good alternative for the PSD method as it yields precision equal to or somewhat higher than the PSD method. The use of synthetic data also allows us to estimate the accuracy and precision of the two methods and to choose the best sampling strategy to obtain past temperatures with the required precision. In addition to application to synthetic data the two methods are tested on stable-isotope records from the EPICA (European Project for Ice Coring in Antarctica) ice core drilled in Dronning Maud Land, Antarctica, showing that reliable firn temperatures can be reconstructed with a typical uncertainty of 1.5 and 2 °C for the Holocene period and 2 and 2.5 °C for the last glacial period for the correlation and PSD method, respectively.

Triple isotope (δD, δ17O, δ18O) study on precipitation, drip water and speleothem fluid inclusions for a Western Central European cave (NW Switzerland)

Deuterium (δD) and oxygen (δ18O) isotopes are powerful tracers of the hydrological cycle and have been extensively used for paleoclimate reconstructions as they can provide information on past precipitation, temperature and atmospheric circulation. More recently, the use of δ17O excess derived from precise measurement of δ17O and δ18O gives new and additional insights in tracing the hydrological cycle whereas uncertainties surround this proxy. However, 17O excess could provide additional information on the atmospheric conditions at the moisture source as well as about fractionations associated with transport and site processes. In this paper we trace water stable isotopes (δD,δ17O and δ18O) along their path from precipitation to cave drip water and finally to speleothem fluid inclusions for Milandre cave in northwestern Switzerland. A two year-long daily resolved precipitation isotope record close to the cave site is compared to collected cave drip water (3 months average resolution) and fluid inclusions of modern and Holocene stalagmites. Amount weighted mean δD,δ18O and δ17O are -71.0‰, -9.9‰, -5.2‰ for precipitation, -60.3‰, -8.7‰, -4.6‰ for cave drip water and -61.3‰, -8.3‰, -4.7‰ for recent fluid inclusions respectively. Second order parameters have also been derived in precipitation and drip water and present similar values with 18 per meg for 17O excess whereas d-excess is 1.5‰ more negative in drip water. Furthermore, the atmospheric signal is shifted towards enriched values in the drip water and fluid inclusions (Δ of ~ + 10‰ for δD). The isotopic composition of cave drip water exhibits a weak seasonal signal which is shifted by around 8 - 10 months (groundwater residence time) when compared to the precipitation. Moreover, we carried out the first δ17O measurement in speleothem fluid inclusions, as well as the first comparison of the δ17 O behaviour from the meteoric water to the fluid inclusions entrapment in speleothems. This study on precipitation, drip water and fluid inclusions will be used as a speleothem proxy calibration for Milandre cave in order to reconstruct paleotemperatures and moisture source variations for Western Central Europe.

Diet and mobility of an Iron Age population in Switzerland; Stable carbon, nitrogen and sulphur isotope analysis of the human remains from Münsingen

The 220 abundantly equipped burials from the Late Iron Age cemetery of Münsingen (420 – 240 BC) marked a milestone for Iron Age research. The evident horizontal spread throughout the time of occupancy laid the foundation for the chronology system of the Late Iron Age. Today the skulls of 77 individuals and some postcranial bones are still preserved. The aim was to obtain information about nutrition, social stratification and migration of the individuals from Münsingen. Stable isotope ratios of carbon, nitrogen and sulphur were analysed. The results of 63 individuals show that all consumed C3 plants as staple food with significant differences between males and females in δ13C and δ15N values. The results indicate a gender restriction in access to animal protein. Stable isotope values of one male buried with weapons and meat as grave goods suggest a diet with more animal proteins than the other individuals. It is possible that he was privileged due to high status. Furthermore, the δ34S values indicate minor mobility. Assuming that the subadults represent the local signal of δ34S it is very likely that adults with enriched δ34S could have migrated to Münsingen at some point during their lives. This study presents stable isotope values of one of the most important Late Iron Age burial sites in Central Europe. The presented data provide new insight into diet, migration and social stratification of the population from Münsingen.

Northern Mediterranean climate since the Middle Pleistocene: a 637 ka stable isotope record from Lake Ohrid (Albania/Macedonia)

Lake Ohrid (Macedonia/Albania) is an ancient lake with unique biodiversity and a site of global significance for investigating the influence of climate, geological, and tectonic events on the generation of endemic populations. Here, we present oxygen (δ18O) and carbon (δ13C) isotope data from carbonate over the upper 243 m of a composite core profile recovered as part of the Scientific Collaboration on Past Speciation Conditions in Lake Ohrid (SCOPSCO) project. The investigated sediment succession covers the past ca. 637 ka. Previous studies on short cores from the lake (up to 15 m, < 140 ka) have indicated the total inorganic carbon (TIC) content of sediments to be highly sensitive to climate change over the last glacial–interglacial cycle. Sediments corresponding to warmer periods contain abundant endogenic calcite; however, an overall low TIC content in glacial sediments is punctuated by discrete bands of early diagenetic authigenic siderite. Isotope measurements on endogenic calcite (δ18Oc and δ13Cc) reveal variations both between and within interglacials that suggest the lake has been subject to palaeoenvironmental change on orbital and millennial timescales. We also measured isotope ratios from authigenic siderite (δ18Os and δ13Cs) and, with the oxygen isotope composition of calcite and siderite, reconstruct δ18O of lake water (δ18Olw) over the last 637 ka. Interglacials have higher δ18Olw values when compared to glacial periods most likely due to changes in evaporation, summer temperature, the proportion of winter precipitation (snowfall), and inflow from adjacent Lake Prespa. The isotope stratigraphy suggests Lake Ohrid experienced a period of general stability from marine isotope stage (MIS) 15 to MIS 13, highlighting MIS 14 as a particularly warm glacial. Climate conditions became progressively wetter during MIS 11 and MIS 9. Interglacial periods after MIS 9 are characterised by increasingly evaporated and drier conditions through MIS 7, MIS 5, and the Holocene. Our results provide new evidence for long-term climate change in the northern Mediterranean region, which will form the basis to better understand the influence of major environmental events on biological evolution within Lake Ohrid.

Dating prograde fluid pulses during subduction by in situ U–Pb and oxygen isotope analysis

Keywords High-pressure fluids · Whiteschists · U–Pb dating · Oxygen isotopes · Ion microprobe · Metasomatism Introduction The subduction of crustal material to mantle depths and its chemical modification during burial and exhumation contribute to element recycling in the mantle and the formation of new crust through arc magmatism. Crustal rocks that Abstract The Dora-Maira whiteschists derive from metasomatically altered granites that experienced ultrahighpressure metamorphism at ~750 °C and 40 kbar during the Alpine orogeny. In order to investigate the P–T–time– fluid evolution of the whiteschists, we obtained U–Pb ages from zircon and monazite and combined those with trace element composition and oxygen isotopes of the accessory minerals and coexisting garnet. Zircon cores are the only remnants of the granitic protolith and still preserve a Permian age, magmatic trace element compositions and δ18O of ~10 ‰. Thermodynamic modelling of Si-rich and Si-poor whiteschist compositions shows that there are two main fluid pulses during prograde subduction between 20 and 40 kbar. In Si-poor samples, the breakdown of chlorite to garnet + fluid occurs at ~22 kbar. A first zircon rim directly overgrowing the cores has inclusions of prograde phlogopite and HREE-enriched patterns indicating zircon growth at the onset of garnet formation. A second main fluid pulse is documented close to peak metamorphic conditions in both Si-rich and Si-poor whiteschist when talc + kyanite react to garnet + coesite + fluid. A second metamorphic overgrowth on zircon with HREE depletion was observed in the Si-poor whiteschists, whereas a single metamorphic overgrowth capturing phengite and talc inclusions was observed in the Si-rich whiteschists. Garnet rims, zircon rims and monazite are in chemical and isotopic equilibrium for oxygen, demonstrating that they all formed at peak metamorphism at 35 Ma as constrained by the age of monazite (34.7 ± 0.4 Ma) and zircon rims (35.1 ± 0.8 Ma). The prograde zircon rim in Si-poor whiteschists has an age that is within error indistinguishable from the age of peak metamorphic conditions, consistent with a minimum rate of subduction of 2 cm/year for the Dora-Maira unit. Oxygen isotope values for zircon rims, monazite and garnet are equal within error at 6.4 ± 0.4 ‰, which is in line with closed-system equilibrium fractionation during prograde to peak temperatures. The resulting equilibrium Δ18Ozircon-monazite at 700 ± 20 °C is 0.1 ± 0.7 ‰. The in situ oxygen isotope data argue against an externally derived input of fluids into the whiteschists. Instead, fluidassisted zircon and monazite recrystallisation can be linked to internal dehydration reactions during prograde subduction. We propose that the major metasomatic event affecting the granite protolith was related to hydrothermal seafloor alteration post-dating Jurassic rifting, well before the onset of Alpine subduction.

Stable oxygen isotope record and Sr/Ca ratios of corals from IODP Holes M0009D and M0023A

We present monthly resolved records of strontium/calcium (Sr/Ca) and oxygen isotope (d18O) ratios from well-preserved fossil corals drilled during the Integrated Ocean Drilling Program (IODP) Expedition 310 'Tahiti Sea Level' and reconstruct sea surface conditions in the central tropical South Pacific Ocean during two time windows of the last deglaciation. The two Tahiti corals examined here are uranium/thorium (U/Th)-dated at 12.4 and 14.2 ka, which correspond to the Younger Dryas (YD) cold reversal and the Bølling-Allerød (B-A) warming of the Northern Hemisphere, respectively. The coral Sr/Ca records indicate that annual average sea surface temperature (SST) was 2.6-3.1 °C lower at 12.4 ka and 1.0-1.6 °C lower at 14.2 ka relative to the present, with no significant changes in the amplitude of the seasonal SST cycle. These cooler conditions were accompanied by seawater d18O (d18Osw) values higher by ~0.8 per mill and ~0.6 per mill relative to the present at 12.4 and 14.2 ka, respectively, implying more saline conditions in the surface waters. Along with previously published coral Sr/Ca records from the island [Cohen and Hart (2004), Deglacial sea surface temperatures of the western tropical Pacific: A new look at old coral. Paleoceanography 19, PA4031, doi:10.1029/2004PA001084], our new Tahiti coral records suggest that a shift toward lower SST by ~1.5 °C occurred from 13.1 to 12.4 ka, which was probably associated with a shift toward higher d18Osw by ~0.2 per mill. Along with a previously published coral Sr/Ca record from Vanuatu [Corrège et al. (2004), Interdecadal variation in the extent of South Pacific tropical waters during the Younger Dyras event. Nature 428, 927-929], the Tahiti coral records provide new evidence for a pronounced cooling of the western to central tropical South Pacific during the Northern Hemisphere YD event.

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.

Zircons, isotope ratios and element analyses from tonalite and oxide gabbro of the mid-ocean ridge from ODP Hole 176-735B

A limiting factor in the accuracy and precision of U/Pb zircon dates is accurate correction for initial disequilibrium in the 238U and 235U decay chains. The longest-lived-and therefore most abundant-intermediate daughter product in the 235U isotopic decay chain is 231Pa (T1/2 = 32.71 ka), and the partitioning behavior of Pa in zircon is not well constrained. Here we report high-precision thermal ionization mass spectrometry (TIMS) U-Pb zircon data from two samples from Ocean Drilling Program (ODP) Hole 735B, which show evidence for incorporation of excess 231Pa during zircon crystallization. The most precise analyses from the two samples have consistent Th-corrected 206Pb/238U dates with weighted means of 11.9325 ± 0.0039 Ma (n = 9) and 11.920 ± 0.011 Ma (n = 4), but distinctly older 207Pb/235U dates that vary from 12.330 ± 0.048 Ma to 12.140 ± 0.044 Ma and 12.03 ± 0.24 to 12.40 ± 0.27 Ma, respectively. If the excess 207Pb is due to variable initial excess 231Pa, calculated initial (231Pa)/(235U) activity ratios for the two samples range from 5.6 ± 1.0 to 9.6 ± 1.1 and 3.5 ± 5.2 to 11.4 ± 5.8. The data from the more precisely dated sample yields estimated DPazircon/DUzircon from 2.2-3.8 and 5.6-9.6, assuming (231Pa)/(235U) of the melt equal to the global average of recently erupted mid-ocean ridge basaltic glasses or secular equilibrium, respectively. High precision ID-TIMS analyses from nine additional samples from Hole 735B and nearby Hole 1105A suggest similar partitioning. The lower range of DPazircon/DUzircon is consistent with ion microprobe measurements of 231Pa in zircons from Holocene and Pleistocene rhyolitic eruptions (Schmitt (2007; doi:10.2138/am.2007.2449) and Schmitt (2011; doi:10.1146/annurev-earth-040610-133330)). The data suggest that 231Pa is preferentially incorporated during zircon crystallization over a range of magmatic compositions, and excess initial 231Pa may be more common in zircons than acknowledged. The degree of initial disequilibrium in the 235U decay chain suggested by the data from this study, and other recent high precision datasets, leads to resolvable discordance in high precision dates of Cenozoic to Mesozoic zircons. Minor discordance in zircons of this age may therefore reflect initial excess 231Pa and does not require either inheritance or Pb loss.

(Table 1) U and Th isotope analyses of pyrite and anhydrite of ODP Site 158-957

Hydrothermal circulation at oceanic spreading ridges causes sea water to penetrate to depths of 2 to 3 km in the oceanic crust where it is heated to ~400 °C before venting at spectacular 'black smokers'. These hydrothermal systems exert a strong influence on ocean chemistry (Edmond et al., 1979, doi:10.1016/0012-821X(79)90061-X), yet their structure, longevity and magnitude remain largely unresolved (Elderfield and Schultz., 1996, doi:10.1146/annurev.earth.24.1.191). The active Transatlantic Geotraverse (TAG) deposit, at 26° N on the Mid-Atlantic Ridge, is one of the largest, oldest and most intensively studied of the massive sulphide mounds that accumulate beneath black-smoker fields. Here we report ages of sulphides and anhydrites from the recently drilled (Humphris et al., 1995, doi:10.1038/377713a0) TAG substrate structures -determined from 234U-230Th systematics analysed by thermal ionization mass spectrometry. The new precise ages combined with existing data (Lalou et al., 1993, doi:10.1029/92JB01898; 1998, doi:10.2973/odp.proc.sr.158.214.1998) show that the oldest material (11,000 to 37,000 years old) forms a layer across the centre of the deposit with younger material (2,300-7,800 years old) both above and below. This stratigraphy confirms that much of the sulphide and anhydrite are precipitated within the mound by mixing of entrained sea water with hydrothermal fluid (James and Elderfield, 1996, doi:10.1130/0091-7613(1996)024<1147:COOFFA>2.3.CO;2). The age distribution is consistent with episodic activity of the hydrothermal system recurring at intervals of up to 2,000 years.

Nd isotope data for planktonic foraminifera from within and around sapropels S1 and S5 from ODP Site 160-967

The development of widespread anoxic conditions in the deep oceans is evidenced by the accumulation and preservation of organic-carbon-rich sediments, but its precise cause remains controversial. The two most popular hypotheses involve (1) circulation-induced increased stratification resulting in reduced oxygenation of deep waters or (2) enhanced productivity in the surface ocean, increasing the raining down of organic matter and overwhelming the oxic remineralization potential of the deep ocean. In the periodic development of deep-water anoxia in the Pliocene-Pleistocene Mediterranean Sea, increased riverine runoff has been implicated both as a source for nutrients that fuel enhanced photic-zone productivity and a source of a less dense freshwater cap leading to reduced circulation, basin-wide stagnation, and deep-water oxygen starvation. Monsoon-driven increases in Nile River discharge and increased regional precipitation due to enhanced westerly activity-two mechanisms that represent fundamentally different climatic driving forces-have both been suggested as causes of the altered freshwater balance. Here we present data that confirm a distinctive neodymium (Nd) isotope signature for the Nile River relative to the Eastern Mediterranean-providing a new tracer of enhanced Nile outflow into the Mediterranean in the past. We further present Nd isotope data for planktonic foraminifera that suggest a clear increase in Nile discharge during the central intense period of two recent anoxic events. Our data also suggest, however, that other regional freshwater sources were more important at the beginning and end of the anoxic events. Taken at face value, the data appear to imply a temporal link between peaks in Nile discharge and enhanced westerly activity.

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.