(Table 1) Age determination and isotopic signature of last glacial Patagonian caly/silt

Ice cores provide a record of changes in dust flux to Antarctica, which is thought to reflect changes in atmospheric circulation and environmental conditions in dust source areas (Forster et al., 2007; Diekmann et al. 2000, doi:10.1016/S0031-0182(00)00138-3; Winckler et al., 2008, doi:10.1126/science.1150595; Reader et al., 1999, doi:10.1029/1999JD900033; Mahowald et al., 1999, doi:10.1029/1999JD900084; Petit et al., 1999, doi:10.1038/20859; 1990, doi:10.1038/343056a0 Delmonte et al., 2009, doi:10.1029/2008GL033382; Lambert et al., 2008, doi:10.1038/nature06763). Isotopic tracers suggest that South America is the dominant source of the dust (Grousset et al., 1992, doi:10.1016/0012-821X(92)90177-W; Basile et al., 1997, doi:10.1016/S0012-821X(96)00255-5; Gaiero et al., 2007, doi:10.1016/j.chemgeo.2006.11.003), but it is unclear what led to the variable deposition of dust at concentrations 20-50 times higher than present in glacial-aged ice (Petit et al., 1990, doi:10.1038/343056a0; Lambert et al., 2008, doi:10.1038/nature06763). Here we characterize the age and composition of Patagonian glacial outwash sediments, to assess the relationship between the Antarctic dust record from Dome C (refs Lambert et al., 2008, doi:10.1038/nature06763; Wolff et al., 2006, doi:10.1038/nature04614) and Patagonian glacial fluctuations (Sugden et al., 2005; McCulloch et al., 2005, doi:10.1111/j.0435-3676.2005.00260.x; Kaplan et al., 2008, doi:10.1016/j.quascirev.2007.09.013) for the past 80,000 years. We show that dust peaks in Antarctica coincide with periods in Patagonia when rivers of glacial meltwater deposited sediment directly onto easily mobilized outwash plains. No dust peaks were noted when the glaciers instead terminated directly into pro-glacial lakes. We thus propose that the variable sediment supply resulting from Patagonian glacial fluctuations may have acted as an on/off switch for Antarctic dust deposition. At the last glacial termination, Patagonian glaciers quickly retreated into lakes, which may help explain why the deglacial decline in Antarctic dust concentrations preceded the main phase of warming, sea-level rise and reduction in Southern Hemisphere sea-ice extent (Wolff et al., 2006, doi:10.1038/nature04614).

Sedimentology of cores from the continental rise west of the Antarctic Peninsula

The continental rise west of the Antarctic Peninsula includes a number of large sediment mounds interpreted as contourite drifts. Cores from six sediment drifts spanning some 650 km of the margin and 48 of latitude have been dated using chemical and isotopic tracers of palaeoproductivity and diatom biostratigraphy. Interglacial sedimentation rates range from 1.1 to 4.3 cm/ka. Glacial sedimentation rates range from 1.8 to 13.5 cm/ka, and decrease from proximal to distal sites on each drift. Late Quaternary sedimentation was cyclic, with brown, biogenic, burrowed mud containing ice-rafted debris (IRD) in interglacials and grey, barren, laminated mud in glacials. Foraminiferal intervals occur in interglacial stages 5 and 7 but not in the Holocene. Processes of terrigenous sediment supply during glacial stages differed; meltwater plumes were more important in stages 2-4, turbidity currents and ice-rafting in stage 6. The terrigenous component shows compositional changes along the margin, more marked in glacials. The major oxides Al2O3 and K2O are higher in the southwest, and CaO and TiO2 higher in the northeast. There is more smectite among the clay minerals in the northeast. Magnetic susceptibility varies along and between drifts. These changes reflect source variations along the margin. Interglacial sediments show less clear trends, and their IRD was derived from a wider area. Downslope processes were dominant in glacials, but alongslope processes may have attained equal importance in interglacials. The area contrasts with the East Antarctic continental slope in the SE Weddell Sea, where ice-rafting is the dominant process and where interglacial sedimentation rates are much higher than glacial. The differences in glacial setting and margin physiography can account for these contrasts.

Images of a groundwater flow system in Nicaragua

Conceptualization of groundwater flow systems is necessary for water resources planning. Geophysical, hydrochemical and isotopic characterization methods were used to investigate the groundwater flow system of a multi-layer fractured sedimentary aquifer along the coastline in Southwestern Nicaragua. A geologic survey was performed along the 46 km2 catchment. Electrical resistivity tomography (ERT) was applied along a 4.4 km transect parallel to the main river channel to identify fractures and determine aquifer geometry. Additionally, three cross sections in the lower catchment and two in hillslopes of the upper part of the catchment were surveyed using ERT. Stable water isotopes, chloride and silica were analyzed for springs, river, wells and piezometers samples during the dry and wet season of 2012. Indication of moisture recycling was found although the identification of the source areas needs further investigation. The upper-middle catchment area is formed by fractured shale/limestone on top of compact sandstone. The lower catchment area is comprised of an alluvial unit of about 15 m thickness overlaying a fractured shale unit. Two major groundwater flow systems were identified: one deep in the shale unit, recharged in the upper-middle catchment area; and one shallow, flowing in the alluvium unit and recharged locally in the lower catchment area. Recharged precipitation displaces older groundwater along the catchment, in a piston flow mechanism. Geophysical methods in combination with hydrochemical and isotopic tracers provide information over different scales and resolutions, which allow an integrated analysis of groundwater flow systems. This approach provides integrated surface and subsurface information where remoteness, accessibility, and costs prohibit installation of groundwater monitoring networks.

Benthic foraminifera in Tertiary sediments of DSDP Leg 90 holes

Eocene through Pliocene benthic foraminifers were examined from seven sites located at middle and lower bathyal depths on the Lord Howe Rise in the Tasman Sea, from another site at lower bathyal depths in the Coral Sea, and from a site in the intermediate-depth, hemipelagic province of the Chatham Rise, east of southern New Zealand. Age-related, depth-related, and bioprovincial faunal variations are documented in this chapter. One new species, Rectuvigerina tasmana, is named. The paleoecologic indications of several key groups, including the miliolids, uvigerinids, nuttallitids, and cibicidids, are combined with sedimentologic and stable isotopic tracers to interpret paleoceanographic changes in the Tasman Sea. Because the total stratigraphic ranges of many bathyal benthic foraminifers are not yet known, most endpoints in the Tasman Sea are considered ecologically controlled events. The disappearances of Uvigerina rippensis and Cibicidoidesparki and the first appearances of U. pigmaea, Sphaeroidina bulloides, and Rotaliatina sulcigera at the Eocene/Oligocene boundary can be considered evolutionary events, as also can the first appearance of Cibicides wuellerstorfi in Zone NN5. Species which are restricted to the lower bathyal zone except during discrete pulses, most of which are related to the development of glacial conditions, include Melonis pompilioides, M. sphaeroides, Pullenia quinqueloba, Nuttallides umbonifera, and U. hispido-costata. Middle bathyal indigenes include U. spinulosa, U. gemmaeformis, Ehrenbergina marwicki, R. sulcigera, and all rectuvigerinids except Rectuvigerina spinea. Although the miliolids first occurred at lower bathyal depths, they were more common in the middle bathyal zone. Although the Neogene hispido-costate uvigerinids first developed at lower bathyal depths and at higher middle latitude sites, in the later Neogene this group migrated to shallower depths and became predominant also in the middle bathyal zone. Despite the relatively similar sedimentologic settings at the six middle bathyal Tasman sites, there was extensive intrageneric and intraspecific geographic variation. Mililiolids, strongly ornamented brizalinids, bolivinitids, Bulimina aculeata, Osangularia culter, and strongly porous morphotypes were more common at higher latitudes. Osangularia bengalensis, striate brizalinids such as Brizalina subaenariensis, Gaudryina solida, osangularids in general, and finely porous morphotypes were more common in the subtropics. There was strong covariance between faunas at lower middle latitude, lower bathyal Site 591, and higher middle latitude, middle bathyal Site 593. The following oceanographic history of the Tasman Sea is proposed; using the stable isotopic record as evidence for glacials and examining the ecologic correlations between (1) miliolids and carbonate saturation, (2) nuttallitids and undersaturated, cooled, or "new" water masses, (3) uvigerinids with high organic carbon in the sediment and high rates of sediment accumulation, and (4) cibicidids and terrestrial organic carbon. The glacial located near the Eocene/Oligocene boundary is characterized by the penetration of cooler, more corrosive waters at intermediate depths in high southern latitudes. This may have caused overturn, upwelling pulses, in other Tasman areas. The development of Neogenelike conditions began in the late Oligocene (Zone NP24/NP25) with the evolution of several common Neogene species. A large number of Paleogene benthics disappeared gradually through the course of the early Miocene, which was not well preserved at any Tasman site. Corrosive conditions shallowed into the middle bathyal zone in several pulses during the early Miocene. The development of glacial conditions in the middle Miocene was accompanied by major changes throughout the Tasman Sea. Sediment accumulation rates increased and high-productivity faunas and corrosive conditions developed at all but the lowest-latitude Site 588. This increase in productivity and accumulation rate is attributed to the eutrophication of Antarctic water masses feeding Tasman current systems, as well as to invigorated circulation in general. It overlaps with the beginning of the Pacific High-productivity Episode (10-5 Ma). During the latest Miocene glacial episode, corrosive conditions developed at lower bathyal depths, while cooler water and lower nutrient levels shallowed to middle bathyal depths. Lower input of terrestrial organic carbon may be related to the lower nutrient levels of this time and to the termination of the Pacific High-productivity Episode. The moderate glacial episode during the mid-Pliocene (Zone NN15/NN16, ~3.2 Ma) corresponds to a decline in sediment accumulation rates and a reorganization of faunas unlike that of all other times. New genera proliferate and indices for cool, noncorrosive conditions and high organic carbon expand throughout the middle bathyal zone coeval with the sedimentation rate decreases. By the latest Pliocene (about 2.5 Ma), however, during another glacial episode, faunal patterns typical of this and later glacials develop throughout the Tasman Sea. Benthic foraminiferal patterns suggest increased input of terrestrial organic matter to Tasman Sea sediments during this episode and during later glacials.

Strontium isotopic ratios of evaporites of the Tyrrhenian Sea

Strontium isotopic ratios of gypsums recovered from upper Miocene (Messinian) evaporites at ODP Leg 107 Holes 652A, 653B, and 654A (Tyrrhenian Sea) are lower than expected. The values for the Messinian balatino-like gypsum, single gypsum crystals, and anhydrites range from 0.70861 to 0.70886 and are approximately 25 * 10**-5 less than would be expected for evaporites precipitated from Messinian seawater (0.70891-0.70902). Pre-evaporitic planktonic foraminifers from Hole 654A show variable degrees of dolomitization and 87Sr/86Sr values that irregularly decrease upward from normal marine values approximately 81m below the lowest evaporite occurrence. This suggests diagenetic alteration by advecting interstitial water with a low 87Sr/86Sr ratio or that the lower Sr isotopic ratios for the Messinian evaporites could have resulted from a greater influence of fresh water on the Sr isotopic composition of the desiccating Tyrrhenian Sea. Fluctuations of the 87Sr/86Sr-ratio for evaporites in the sedimentary cycles recognized for Holes 653B and 654A, the generally low Sr isotopic ratio of river water entering the Mediterranean Sea, and the presence of dwarf marine microfossils suggest that the 87Sr/86Sr ratio of the evaporites responded to hydrologic variations in a very restricted basin with variable rates of marine and fresh water input. The strontium isotopic ratios of the Messinian anhydrites from the proposed lacustrine sequence at Hole 652A fall in the same range as the marine evaporites from Holes 654A and 653B. This suggests a common or similar origin of the brines at the three locations. The complex depositional and hydrologic conditions in the Mediterranean during the Messinian salinity crisis preclude the use of Sr isotopic values from the evaporites for stratigraphic correlation and dating. They are, however, very useful in the interpretation of the depositional history of the basin. General calculations assuming a closed system suggest that the 87Sr/86Sr ratio of Messinian seawater (-0.7090) could be reduced to that of the evaporites (-0.7087) by mixing with fresh water (e.g., Nile River) in times of 10**4 to 10**5 yr.

Sr-Nd isotopic analyses of sand-sized sediment from the San Francisco Bay coastal system

A diverse suite of geochemical tracers, including 87Sr/86Sr and 143Nd/144Nd isotope ratios, the rare earth elements (REEs), and select trace elements were used to determine sand-sized sediment provenance and transport pathways within the San Francisco Bay coastal system. This study complements a large interdisciplinary effort (Barnard et al., 2012) that seeks to better understand recent geomorphic change in a highly urbanized and dynamic estuarine-coastal setting. Sand-sized sediment provenance in this geologically complex system is important to estuarine resource managers and was assessed by examining the geographic distribution of this suite of geochemical tracers from the primary sources (fluvial and rock) throughout the bay, adjacent coast, and beaches. Due to their intrinsic geochemical nature, 143Nd/144Nd isotopic ratios provide the most resolved picture of where sediment in this system is likely sourced and how it moves through this estuarine system into the Pacific Ocean. For example, Nd isotopes confirm that the predominant source of sand-sized sediment to Suisun Bay, San Pablo Bay, and Central Bay is the Sierra Nevada Batholith via the Sacramento River, with lesser contributions from the Napa and San Joaquin Rivers. Isotopic ratios also reveal hot-spots of local sediment accumulation, such as the basalt and chert deposits around the Golden Gate Bridge and the high magnetite deposits of Ocean Beach. Sand-sized sediment that exits San Francisco Bay accumulates on the ebb-tidal delta and is in part conveyed southward by long-shore currents. Broadly, the geochemical tracers reveal a complex story of multiple sediment sources, dynamic intra-bay sediment mixing and reworking, and eventual dilution and transport by energetic marine processes. Combined geochemical results provide information on sediment movement into and through San Francisco Bay and further our understanding of how sustained anthropogenic activities which limit sediment inputs to the system (e.g., dike and dam construction) as well as those which directly remove sediments from within the Bay, such as aggregate mining and dredging, can have long-lasting effects.

(Table 1) Osmium concentrations and isotopic ratios for ODP Leg 125 peridotites

Mantle peridotites drilled from the Izu-Bonin-Mariana forearc have unradiogenic 187Os/188Os ratios (0.1193 to 0.1273), which give Proterozoic model ages of 820 to 1230 million years ago. If these peridotites are residues from magmatism during the initiation of subduction 40 to 48 million years ago, then the mantle that melted was much more depleted in incompatible elements than the source of mid-ocean ridge basalts (MORB). This result indicates that osmium isotopes record information about ancient melting events in the convecting upper mantle not recorded by incompatible lithophile isotope tracers. Subduction zones may be a graveyard for ancient depleted mantle material, and portions of the convecting upper mantle may be less radiogenic in osmium isotopes than previously recognized.

(Table 6) Selenium isotopic composition of sediment samples from ODP Site 185-1149

Multiple-collector inductively coupled plasma mass spectrometry has been used for the precise measurement of the isotopic composition of Se in geological samples. Se is chemically purified before analysis by using cotton impregnated with thioglycollic acid. This preconcentration step is required for the removal of matrix-interfering elements for hydride generation, such as transitional metals, and also for the quantitative separation of other hydride-forming elements, such as Ge, Sb, and As. The analyte is introduced in the plasma torch with a continuous-flow hydride generation system. Instrumental mass fractionation is corrected with a "standard-sample bracketing" approach. By use of this new technique, the minimum Se required per analysis is lowered to 10 ng, which is one order of magnitude less than the amount needed for the N-TIMS technique. The estimated external precision calculated for the 82Se/76Se isotope ratio is 0.25? (2 sigma), and the data are reported as delta notation (?) relative to our internal standard (MERCK elemental standard solution). Measurements of Se isotopes are presented for samples of standard solutions and geological reference materials, such as silicate rocks, soils, and sediments. The Se isotopic composition of selected terrestrial and extraterrestrial materials are also presented. An overall Se isotope variation of 8? has been observed, suggesting that Se isotopes fractionate readily and are extremely useful tracers of natural processes.

(Table S1) Neodymium isotopic results from ODP Site 172-1063

The Atlantic Meridional Overturning Circulation (AMOC) plays an important role in the Northern Hemisphere climate system. Significant interest went into the question of how excessive freshwater input through melting of continental ice can affect its overturning vigor and, hence, heat supply, to higher northern latitudes. Such forcing can be tested by investigating its behavior during extreme iceberg discharge events into the open North Atlantic during the last glacial period, the so-called Heinrich events (HE). Here we present neodymium (Nd) isotope compositions of past seawater, a sensitive chemical water mass tag, extracted from sediments of Ocean Drilling Program Site 1063 in the western North Atlantic (Bermuda Rise), covering the period surrounding HE 2, the Last Glacial Maximum, and the early deglaciation. These data are compared with a record of the kinematic circulation tracer (231Pa/230Th)xs extracted from the same sediment core. Both tracers indicate significant circulation changes preceding intense ice rafting during HE 2 by almost 2 kyr. Moreover, the Nd isotope record suggests the presence of deeply ventilating North Atlantic Deep Water early during Marine Isotope Stage 2 until it was replaced by Southern Source Water at ~27 ka. The early switch to high (Pa/Th)xs and radiogenic epsilon-Nd in relation to intensified ice rafting during HE 2 suggests that ice rafting into the open North Atlantic during major HE 2 was preceded by an early change of the AMOC. This opens the possibility that variations in AMOC contributed to or even triggered the ice sheet instability rather than merely responding to it.

(Table 1) Li, B and Sr isotopic composition and concentration in ODP Leg 209 samples

Spinel harzburgites from ODP Leg 209 (Sites 1272A, 1274A) drilled at the Mid-Atlantic ridge between 14°N and 16°N are highly serpentinized (50-100%), but still preserve relics of primary phases (olivine >= orthopyroxene >> clinopyroxene). We determined whole-rock B and Li isotope compositions in order to constrain the effect of serpentinization on d11B and d7Li. Our data indicate that during serpentinization Li is leached from the rock, while B is added. The samples from ODP Leg 209 show the heaviest d11B (+29.6 to +40.52 per mil) and lightest d7Li (-28.46 to +7.17 per mil) found so far in oceanic mantle. High 87Sr/86Sr ratios (0.708536 to 0.709130) indicate moderate water/rock ratios (3 to 273, on the average 39), in line with the high degree of serpentinization observed. Applying the known fractionation factors for 11B/10B and 7Li/6Li between seawater and silicates, serpentinized peridotite in equilibrium with seawater at conditions corresponding to those of the studied drill holes (pH: 8.2; temperature: 200 °C) should have d11B of +21.52 per mil and d7Li of +9.7 per mil. As the data from ODP Leg 209 are clearly not in line with this, we modelled a process of seawater-rock interaction where d11B and d7Li of seawater evolve during penetration into the oceanic plate. Assuming chemical equilibrium between fluid and a rock with d11B and d7Li of ODP Leg 209 samples, we obtain d11B and d7Li values of +50 to +60 per mil, -2 to +12 per mil, respectively, for the coexisting fluid. In the oceanic domain, no hydrothermal fluids with such high d11B have yet been found, but are predicted by theoretical calculations. Combining the calculated water/rock ratios with the d7Li and d11B evolution in the fluid, shows that modification of d7Li during serpentinization requires higher water/rock ratios than modification of d11B. Extremely heavy d11B in serpentinized oceanic mantle can potentially be transported into subduction zones, as the B budget of the oceanic plate is dominated by serpentinites. Extremely light d7Li is unlikely to survive as the Li budget is dominated by the oceanic crust, even at small fractions.

(Table 1) Sulphur concentration and isotopic composition of ODP Leg 126 igneous rocks

Sulfur isotope ratios have been determined in 19 selected igneous rocks from Leg 126. The d34S of the analyzed rocks ranges from -0.1 â to +19.60 â. The overall variation in sulfur isotope composition of the rocks is caused by varying degrees of seawater alteration. Most of the samples are altered by seawater and only five of them are considered to have maintained their magmatic sulfur isotope composition. These samples are all from the backarc sites and have d34S values varying from +0.2 â to +1.6 â, of which the high d34S values suggest that the earliest magmas in the rift are more arc-like in their sulfur isotope composition than the later magmas. The d34S values from the forearc sites are similar to or heavier than the sulfur isotope composition of the present arc.

(Table 1) Nd and Sr isotopic analyses of ODP Leg 127 basalts

Sr and Nd isotopic compositions are reported for basaltic rocks collected during ODP Leg 127 from the Yamato Basin, a rifted backarc basin in the Japan Sea. The basalts are classified into two groups in terms of Nd isotopic composition: the upper sills at Site 797 are characterized by higher 143Nd/144Nd ratios (0.513083-0.513158, epsilon-Nd = 8.68-10.14) and the basalts from Site 794 and the lower sills at Site 797 have lower 143Nd/144Nd ratios (0.512684-0.512862, epsilon-Nd = 0.90-4.37). All of the basalts show higher Sr isotopic compositions than those of the mantle array, which is attributed to seawater alteration. The basalts with lower Nd isotopic values ranging in age from 20.6 to 17.3 Ma have tapped an enriched subcontinental upper mantle (SCUM) with the minor involvement of a depleted asthenospheric mantle (AM). Subsequent change in composition through the physical replacement of SCUM by AM yielded the basalts of the upper sills of higher Nd isotopic compositions. This event within the upper mantle was associated with the breakup of the overlying lithosphere during the rifting of the Japan Sea backarc basin.

Isotopic signature of specific biomarkers derived from anaerobic methanotrophic archaea (ANME groups) and sulphate-reducing bacteria (SRB) at different cold seep provinces

Anaerobic methane-oxidizing microbial communities in sediments at cold methane seeps are important factors in controlling methane emission to the ocean and atmosphere. Here, we investigated the distribution and carbon isotopic signature of specific biomarkers derived from anaerobic methanotrophic archaea (ANME groups) and sulphate-reducing bacteria (SRB) responsible for the anaerobic oxidation of methane (AOM) at different cold seep provinces of Hydrate Ridge, Cascadia margin. The special focus was on their relation to in situ cell abundances and methane turnover. In general, maxima in biomarker abundances and minima in carbon isotope signatures correlated with maxima in AOM and sulphate reduction as well as with consortium biomass. We found ANME-2a/DSS aggregates associated with high abundances of sn-2,3-di-O-isoprenoidal glycerol ethers (archaeol, sn-2-hydroxyarchaeol) and specific bacterial fatty acids (C16:1omega5c, cyC17:0omega5,6) as well as with high methane fluxes (Beggiatoa site). The low to medium flux site (Calyptogena field) was dominated by ANME-2c/DSS aggregates and contained less of both compound classes but more of AOM-related glycerol dialkyl glycerol tetraethers (GDGTs). ANME-1 archaea dominated deeper sediment horizons at the Calyptogena field where sn-1,2-di-O-alkyl glycerol ethers (DAGEs), archaeol, methyl-branched fatty acids (ai-C15:0, i-C16:0, ai-C17:0), and diagnostic GDGTs were prevailing. AOM-specific bacterial and archaeal biomarkers in these sediment strata generally revealed very similar d13C-values of around -100 per mill. In ANME-2-dominated sediment sections, archaeal biomarkers were even more 13C-depleted (down to -120 per mill), whereas bacterial biomarkers were found to be likewise 13C-depleted as in ANME-1-dominated sediment layers (d13C: -100 per mill). The zero flux site (Acharax field), containing only a few numbers of ANME-2/DSS aggregates, however, provided no specific biomarker pattern. Deeper sediment sections (below 20 cm sediment depth) from Beggiatoa covered areas which included solid layers of methane gas hydrates contained ANME-2/DSS typical biomarkers showing subsurface peaks combined with negative shifts in carbon isotopic compositions. The maxima were detected just above the hydrate layers, indicating that methane stored in the hydrates may be available for the microbial community. The observed variations in biomarker abundances and 13C-depletions are indicative of multiple environmental and physiological factors selecting for different AOM consortia (ANME-2a/DSS, ANME-2c/DSS, ANME-1) along horizontal and vertical gradients of cold seep settings.