ALBERT

Description: Reconstructed sea surface temperatures (SSTs) derived from Mg/Ca measurements in nine encrusting coralline algal skeletons from the Aleutian archipelago in the northernmost Pacific Ocean reveal an overall increase in SST from 1665 to 2007. In the Aleutian SST reconstruction, decadal-scale variability is a transient feature present during the 1700s and early 1800s and then fully emerging post-1950. SSTs vary coherently with available instrument records of cyclone variance and vacillate in and out of coherence with multicentennial Pacific Northwest drought reconstructions as a response to SST-driven alterations of storm tracks reaching North America. These results indicate that an influence of decadal-scale variability on the North Pacific storm tracks only became apparent during the midtwentieth century. Furthermore, what has been assumed as natural variability in the North Pacific, based on twentieth century instrumental data, is not consistent with the long-term natural variability evident in reconstructed SSTs predating the anthropogenic influence.

Description: This study reports Mo isotopic compositions for fifty-two Palaeozoic granitic rocks with contrasting source affinities (A-, I- and S-type) from the Lachlan Fold Belt (LFB) and the New England Batholith (NEB), both in SE Australia, and three compositionally zoned plutons (Loch Doon, Criffell, and Fleet) located in the Southern Uplands of Scotland. The results show relatively large variations in δ98Mo for igneous rocks ranging from −1.73‰ to 0.59‰ with significant overlaps between different types. No relationships between δ98Mo and δ18O or ASI (Alumina Saturation Index) are observed, indicating that Mo isotopes do not clearly distinguish igneous vs. sedimentary source types. Instead, effects of igneous processes, source mixing, regional geology, as well as hydrothermal activity control the Mo isotope compositions in these granites. It is found that Mo is mainly accommodated in biotite and to a lesser extent in hornblende. Hornblende and Fe3+-rich minerals may preferentially incorporate light isotopes, as reflected by negative correlations between δ98Mo and K/Rb and [Fe2O3]. There is a positive correlation between initial 87Sr/86Sr and δ98Mo in I-type granitic rocks, reflecting the admixing of material from isotopically distinct sources. Granitic rocks from Scotland and Australia display strikingly similar curvilinear trends in δ98Mo vs. initial 87Sr/86Sr despite the differing regional geology. Localized hydrothermal effects can result in low δ98Mo in granite, as seen in three samples from Loch Doon and Criffell which have anomalously light δ98Mo of 〈−1‰. Based on this study, an estimate of δ98Mo = 0.14 ± 0.07‰ (95% s.e.) for the Phanerozoic upper crust is proposed. This is slightly heavier than basalts indicating an isotopically light lower crust and/or a systematic change to the crust resulting from subduction of isotopically light dehydrated slab and/or pelagic sediment over time.

Description: We investigated the controls of hydrography and of scavenging on the distribution of the particle reactive radionuclides 231Pa and 230Th in the water column and in surface sediments off Southwest Africa (Angola and Cape basins). Based on a vertical section of total 230Thex concentrations in the water column we show that small differences in the salinity between the North Atlantic Deep Water (NADW) in the Angola Basin and the NADW in the Cape Basin as well as the advection of NADW associated with the Namib Col Current are reflected in total 230Thex concentrations. These variable total concentrations are believed to reflect the flow path and mixing history of NADW with the NADW in the Angola Basin being relatively older and 230Th enriched compared to the NADW in the Cape Basin. In the area investigated we found high 231Paex/230Thex ratios (231Paex/230Thex 〉 0.093) in surface sediments at the continental margin and lower ones (231Paex/230Thex 〈 0.093) in the open ocean. Such a distribution is normally interpreted to result from high particle flux at ocean margins (boundary scavenging). However, the lack of any significant depletion of dissolved 230Th and 231Pa in the water column does not indicate extensive scavenging at the continental margin. High 231Paex/230Thex ratios are constrained to shallow waters depths (〈 2000 m) only and coincide with low fractionation between 231Pa and 230Th indicating that preferential scavenging of 231Pa on opal may have caused high 231Paex/230Thex ratios in the sediments. The observed close negative correlation (r2 = 0.82) between 231Paex/230Thex ratios in sediments and water depths is believed to reflect changes in the particle composition, i.e. a decrease in opal content with water depth. In the Angola and Cape basins the total 231Paex concentrations in NADW were the highest observed so far in the Atlantic Ocean, and they are attributed to the meridional export of 231Pa from the North Atlantic. This caused the average dissolved 231Pa/230Th in the Southeast Atlantic to be about a factor 2 higher when compared to the North Atlantic (Labrador Sea). These differences in the dissolved 231Pa/230Th were not reflected in 231Pa/230Th ratios of surface sediments because the fractionation is lower in the Labrador Sea compared to the Southeast Atlantic, i.e. fractionation counteracts changes in the dissolved 231Pa/230Th. This suggests that fractionation is more important for the determination of 231Paex/230Thex ratios in sediments than the meridional export of 231Pa from the North Atlantic.

Description: While recent changes in subarctic North Pacific climate had dramatic effects on ecosystems and fishery yields, past climate dynamics and teleconnection patterns are poorly understood due to the absence of century-long high-resolution marine records. We present the first 117-year long annually resolved marine climate history from the western Bering Sea/Aleutian Island region using information contained in the calcitic skeleton of the long-lived crustose coralline red alga Clathromorphum nereostratum, a previously unused climate archive. The skeletal δ18O-time series indicates significant warming and/or freshening of surface waters after the middle of the 20th century. Furthermore, the time series is spatiotemporally correlated with Pacific Decadal Oscillation (PDO) and tropical El Niño-Southern Oscillation (ENSO) indices. Even though the western Bering Sea/Aleutian Island region is believed to be outside the area of significant marine response to ENSO, we propose that an ENSO signal is transmitted via the Alaskan Stream from the Eastern North Pacific, a region of known ENSO teleconnections.

Description: Here, we present a new technique for the direct measurement of 44Ca/40Ca isotope ratios on a Multicollector Inductively Coupled Plasma Mass Spectrometer (MC–ICP–MS, AXIOM) using the “cool plasma” technique. By reducing the plasma energy to about 400 W, the isobaric effect resulting from 40Ar+ can be significantly reduced, enabling the simultaneous and precise measurement of 44Ca and 40Ca beam intensities in different Faraday cups. In contrast to the TIMS technique requiring a 43Ca/48Ca double spike, the isotope measurements on MC–ICP–MS can be performed by bracketing standards. We express the calcium isotope variation relative to NIST SRM 915a (δ44/40Ca [‰]=[((44Ca/40Ca)sample/(44Ca/40Ca)NIST SRM 915a)−1]*1000). Isobaric effects of 24Mg16O+ and 23Na16OH+ interfering with 40Ca and 26Mg16OH2+ with 44Ca can be neglected by measuring calcium isotopes near the low-mass edge of the peaks. No influence of 87Sr2+ monitored on 43.5 atomic mass units (amu) was found. Repeated measurements of two Johnson Matthey CaCO3 standards (lot No. 4064 and lot No. 9912) revealed values of about −11.29 (‰ SRM 915a) and 0.57 (‰ SRM 915a). These values are in accordance with previous values published by Russell et al. [Geochim. Cosmochim. Acta 42 (1978) 1075], Heuser et al. [Int. J. Mass Spectrom. 220 (2002) 385], Hippler et al. [Geostand. Newsl. 27 (2003) 267] and Schmitt et al. [Geochim. Cosmochim. Acta 67 (2003) 2607]. Repeated measurement of the NIST SRM 915a CaCO3 standard showed that the variance of a single δ44/40Ca measurement is about 0.14‰ RSD being comparable with TIMS. MC–ICP–MS-based δ44/40Ca values measured on inorganically precipitated aragonite samples are indistinguishable from earlier measurements based on TIMS, confirming the positive correlation of δ44/40Ca and temperature. MC–ICP–MS-based δ44/40Ca measurements on cultured Orbulina universa showed a slope of about 0.026‰/°C being similar to the TIMS-based δ44/40Ca measurements showing a slope of about 0.019‰/°C. The large offset of about 5‰ between the two techniques is shown to be caused by a “matrix” effect, indicating that any δ44/40Ca measurements on MC–ICP–MS are sensitively controlled by the Ca concentration and the acidity of the solution. Our study demonstrates the possibility to measure the whole dispersion of calcium isotopes with MC–ICP–MS, showing that 40Ca can be used for normalization of 44Ca.

Description: Hydrothermal vent deposits form on the seafloor as a result of cooling and mixing of hot hydrothermal fluids with cold seawater. Amongst the major sulfide and sulfate minerals that are preserved at vent sites, barite (BaSO4) is unique because it requires the direct mixing of Ba-rich hydrothermal fluid with sulfate-rich seawater in order for precipitation to occur. Because of its extremely low solubility, barite crystals preserve geochemical fingerprints associated with conditions of formation. Here, we present data from petrographic and geochemical analyses of hydrothermal barite from the Endeavour Segment of the Juan de Fuca Ridge, northeast Pacific Ocean, in order to determine the physical and chemical conditions under which barite precipitates within seafloor hydrothermal vent systems. Petrographic analyses of 22 barite-rich samples show a range of barite crystal morphologies: dendritic and acicular barite forms near the exterior vent walls, whereas larger bladed and tabular crystals occur within the interior of chimneys. A two component mixing model based on Sr concentrations and 87Sr/86Sr of both seawater and hydrothermal fluid, combined with 87Sr/86Sr data from whole rock and laser-ablation ICP-MS analyses of barite crystals indicate that barite precipitates from mixtures containing as low as 17% and as high as 88% hydrothermal fluid component, relative to seawater. Geochemical modelling of the relationship between aqueous species concentrations and degree of fluid mixing indicates that Ba2+ availability is the dominant control on mineral saturation. Observations combined with model results support that dendritic barite forms from fluids of less than 40% hydrothermal component and with a saturation index greater than ∼0.6, whereas more euhedral crystals form at lower levels of supersaturation associated with greater contributions of hydrothermal fluid. Fluid inclusions within barite indicate formation temperatures of between ∼120 °C and 240 °C during barite crystallization. The comparison of fluid inclusion formation temperatures to modelled mixing temperatures indicates that conductive cooling of the vent fluid accounts for 60–120 °C reduction in fluid temperature. Strontium zonation within individual barite crystals records fluctuations in the amount of conductive cooling within chimney walls that may result from cyclical oscillations in hydrothermal fluid flux. Barite chemistry and morphology can be used as a reliable indicator for past conditions of mineralization within both extinct seafloor hydrothermal deposits and ancient land-based volcanogenic massive sulfide deposits.

Description: Conflicting results have been reported for the stable Sr isotope fractionation, specifically with respect to the influence of temperature. In an experimental study we have investigated the stable Sr isotope systematics for inorganically precipitated and biogenic (coral) aragonite (natural and laboratory-cultured). Inorganic aragonite precipitation experiments were performed from natural seawater using the CO2 diffusion technique. The experiments were performed at different temperatures and different carbonate ion concentrations. 88Sr/86Sr of the inorganic aragonite precipitated in the experiments are 0.2‰ lighter than seawater, but showed no correlation to the water temperature or to CO32− concentration. Similar observations are made in different coral species (Cladocora caespitosa, Porites sp. and Acropora sp.), with identical fractionation from the bulk solution and no correlation to temperature or CO32− concentration. The lack of 88Sr/86Sr variability in corals at different environmental parameters and the similarity to the 88Sr/86Sr fractionation in inorganic aragonite may indicate a similar Sr incorporation mechanism in corals skeleton and inorganic aragonite, and therefore the previously proposed Rayleigh-based multi element model (Gaetani et al., 2011) cannot explain the process of Sr incorporation in the coral skeletal material. It is proposed that the relatively constant 88Sr/86Sr fractionation in aragonite can be used for paleo reconstruction of seawater 88Sr/86Sr composition. The seawater 88Sr/86Sr ratio reconstruction can be further used in calcite samples to reconstruct paleo precipitation rates.

Description: Blue mussel individuals (Mytilus edulis) were cultured at four different salinities (17, 20, 29, and 34). During the course of the experiment, temperature was gradually increased from 6°C to 14°C. Mg/Ca and Sr/Ca ratios of the shell calcite portions produced during the 9 weeks of experimental treatment as well parts that were precipitated before the treatment phase were measured by laser ablation–multicollector–inductively coupled plasma–mass spectrometry. Mg/Ca ratios show a positive correlation with temperature for individuals cultured at salinity 29 and 34 (Mg/Ca (mmol/mol) ∼ (0.2–0.3)*T (°C)), while for individuals cultured at low salinities (17, 20) no trend was observed. Sr/Ca ratios were not affected by temperature but strongly by salinity. The data show very strong biological influence (“individual differences” and “physiological variability”) on elemental ratios (79% on Mg/Ca and 41% on Sr/Ca) in M. edulis calcite. The results challenge the use of blue mussel shell data as environmental proxies.

Description: The internal microstructure of a ferromanganese nodule (#2392, from 154°37.52′W, 9°37.56′N, at water depth 5194 m) was examined in detail on polished sections, and radiometrically dated (230Thex/232Th) along a high-resolution (0.1 mm) depth profile (0–1.3 mm), spanning approximately 271 ka. The fabric shows typical stromatolithic structure and exhibits four orders of basic cyclic growth pattern, namely laminae bands, laminae zones, laminae groups and laminae pairs having average thicknesses of 402–454, 185–206, 58–67 and 15–18 μm, respectively. A profile from the depth of 200–2661 μm was selected to obtain the geochemical series using line-scanning electron microprobe analyses, which provide a record of paleoceanographic oscillations during the growth period. Power spectral analysis of the geochemical series for Al, Mn, Fe and Fe/Mn from the depth of 200–1220 μm, where no obvious discontinuity could be observed, display conspicuous cyclicities. The cycles of laminae zones, laminae groups and laminae pairs are reflected in the spectral patterns as well. The significant spectral peaks are located at 186, 108, 66 μm. Together with the cycle of laminae bands, the ratios of these cyclicities are close to those of Milankovitch orbital cycles. Through tuning to orbital cycles, a net growth rate of 4.5 mm/Ma is derived for the profile, which is in perfect agreement with the growth rate of 4.6 mm/Ma determined by 230Thex/232Th dating. Therefore, the rhythmic growth of ferromanganese nodules appears definitely associated with Milankovitch cycles, and the growth cyclicities may offer a new tool for estimating growth rates of ferromanganese nodules and paleoenvironmental reconstruction at substage resolution when supported by radiometric dating.