Pronounced occurrence of long-chain alkenones and dinosterol in a 25,000-year lipid molecular fossil record from Lake Titicaca, South America

Our analysis of lipid molecular fossils from a Lake Titicaca (16° S, 69° W) sediment core reveals distinct changes in the ecology of the lake over an ∼25,000-yr period spanning latest Pleistocene to late Holocene time. Previous investigations have shown that over this time period Lake Titicaca was subject to large changes in lake level in response to regional climatic variability. Our results indicate that lake algal populations were greatly affected by the changing physical and chemical conditions in Lake Titicaca. Hydrocarbons are characterized by a combination of odd-numbered, mid- to long-chain (C₂₁-C₃₁) normal alkanes and alkenes. During periods when lake level was higher (latest Pleistocene, early Holocene, and late Holocene), the C₂₁n-alkane, and the C₂₅ and C₂₇ alkenes dominate hydrocarbon distributions and indicate contribution from an algal source, potentially the freshwater alga Botryococcus braunii. The C₃₀ 4 α-methyl sterol (dinosterol) increases sharply during the mid-Holocene, suggesting a greatly increased dinoflagellate presence at that time. Long-chain alkenones (LCAs) become significant during the early Holocene and are highly abundant in mid-Holocene samples. There are relatively few published records of LCA detection in lake sediments but their occurrence is geographically widespread (Antarctica, Asia, Europe, North America). Lake Titicaca represents the first South American lake and the first low-latitude lake in which LCAs have been reported. LCA abundance and distribution may be related to the temperature-dependent response of an unidentified algal precursor. Although the LCA unsaturation indices cannot be used to determine absolute Lake Titicaca temperatures, we suspect that the published LCA U₃₇^K unsaturation calibrations can be applied to infer relative temperatures for early to mid-Holocene time when LCA concentrations are high. Using these criteria, the U₃₇^K unsaturation indices suggest relatively warmer temperatures in the mid-Holocene. In contrast to previous speculation, lipid analysis provides little evidence of a greatly increased presence of aquatic plants during the mid-Holocene. Instead, it appears that a few algal species were dominant in the lake. Based on the dramatic rise in abundances of LCAs and dinosterol during the early to mid-Holocene, we suspect that the algal producers of these compounds rose in response to a combination of physical and chemical changes in the lake. These include temperature, salinity, and alkalinity changes that occurred as lake level dropped sharply during a multi-millennial drought affecting the Central Andean Altiplano.     

Anaerobic diagenesis of silica and carbon in continental margin sediments: Discrete zones of TCO2 production

Pore water profiles of dissolved Si, Ca²⁺, SO₄^2-, CH₄, and TCO₂ (Dissolved Inorganic Carbon; DIC) were determined from multicores and gravity cores collected at nine sites off Southern California, the west coast of Mexico, and within the Gulf of California. These sites were located within the eastern North Pacific oxygen minimum zone at depths of 400 to 900 m and in settings where bottom water oxygen concentrations were <3 μM and sediments were laminated. Pore water profiles were defined at a resolution of millimeters (whole core squeezing), centimeters (sectioning and squeezing) and meters (gravity core sectioning and squeezing), and diffusive fluxes were calculated for different zones within the sediment column. The flux of dissolved silica across the sediment-water interface (SWI) ranged from 0.3 to 3.4 mmol Si m^-2d^-1, and TCO₂ fluxes ranged from 0.8 to 4.6 mmol C m^-2d^-1. A positive correlation (r = 0.74) existed between these fluxes, yet these two constituents exhibited significantly different diagenetic behavior downcore; dissolved Si generally reached a constant concentration (between 450 and 900 μM) in the upper few cm, whereas TCO₂ concentrations increased monotonically with depth.Methane was detected at micromolar levels in sediment intervals between 0 and 60 cm and at five sites, increased to millimolar levels at depths of 80 to 170 cm. At the horizon marking the appearance of millimolar levels of methane, there was a distinct change in slope of the sulfate and TCO₂ gradients. A flux budget for this horizon was determined by using linear fits to pore water profiles; these budgets indicate that the upward TCO₂ flux away from this horizon is 40 to 50% greater than the downward sulfate flux to this horizon. Given that the TCO₂ flux to this horizon from below was quite small, this imbalance suggests that anaerobic oxidation of methane by sulfate is not the only process producing TCO₂ within this horizon. A budget for TCO₂ at this horizon is balanced when 40 to 80% of the sulfate flux is attributed to organic carbon remineralization. Of the DIC that diffuses across the SWI, 20 to 40% is generated by reactions occurring within or below this deep reaction horizon.     

Concentration, isotopic composition, and sources of lead in Southern Ocean air during 1999/2000, measured at the Cape Grim Baseline Air Pollution Station, Tasmania

Southern Ocean aerosols were collected at the Cape Grim Baseline Air Pollution Station from onshore air under baseline conditions between February 1999 and April 2000. Thermal ionization techniques (TIMS) and isotope dilution mass spectrometry (IDMS) were used to measure the isotopic composition and concentration of lead in the air giving concentrations as low as 0.6 ± 0.1 pg · m⁻³. Air collected under baseline conditions for 12 months (May 1999-April 2000) yielded an overall lead concentration of 11.0 ± 0.2 pg · m⁻³ and isotopic composition of ²⁰⁶Pb/²⁰⁷Pb = 1.154, ²⁰⁸Pb/²⁰⁷Pb = 2.387 and ²⁰⁶Pb/²⁰⁴Pb = 17.93. The range in isotopic ratios was consistent with the mixing of lead from major population centers in the Southern Hemisphere in the mid to high latitudes, except for the presence of highly radiogenic lead in some samples. Contributions from radiogenic lead of up to ∼0.8% were observed. Three periods with the highest percentage contribution of radiogenic lead (>0.5%) were investigated in more detail, and 4-d back-trajectories and radon concentrations were used to help identify the sources. The sources are probably associated with the mining and processing of uranium rich ores in southern Africa and possibly South Australia.     

Zircon M127 – A Homogeneous Reference Material for SIMS U–Pb Geochronology Combined with Hafnium,Oxygen and,Potentially, Lithium Isotope Analysis

In this article, we document a detailed analytical characterisation of zircon M127, a homogeneous 12.7 carat gemstone from Ratnapura, Sri Lanka. Zircon M127 has TIMS‐determined mean U–Pb radiogenic isotopic ratios of 0.084743 ± 0.000027 for ²⁰⁶Pb/²³⁸U and 0.67676 ± 0.00023 for ²⁰⁷Pb/²³⁵U (weighted means, 2s uncertainties). Its ²⁰⁶Pb/²³⁸U age of 524.36 ± 0.16 Ma (95% confidence uncertainty) is concordant within the uncertainties of decay constants. The δ¹⁸O value (determined by laser fluorination) is 8.26 ± 0.06‰ VSMOW (2s), and the mean ¹⁷⁶Hf/¹⁷⁷Hf ratio (determined by solution ICP‐MS) is 0.282396 ± 0.000004 (2s). The SIMS‐determined δ⁷Li value is ?0.6 ± 0.9‰ (2s), with a mean mass fraction of 1.0 ± 0.1 μg g^?1 Li (2s). Zircon M127 contains ~ 923 μg g^?1 U. The moderate degree of radiation damage corresponds well with the time‐integrated self‐irradiation dose of 1.82 × 10¹⁸ alpha events per gram. This observation, and the (U–Th)/He age of 426 ± 7 Ma (2s), which is typical of unheated Sri Lankan zircon, enable us to exclude any thermal treatment. Zircon M127 is proposed as a reference material for the determination of zircon U–Pb ages by means of SIMS in combination with hafnium and stable isotope (oxygen and potentially also lithium) determination.     

Exploring the impact of diagenesis on (isotope) geochemical and microstructural alteration features in biogenic aragonite

For the Quaternary and Neogene, aragonitic biogenic and abiogenic carbonates are frequently exploited as archives of their environment. Conversely, pre‐Neogene aragonite is often diagenetically altered and calcite archives are studied instead. Nevertheless, the exact sequence of diagenetic processes and products is difficult to disclose from naturally altered material. Here, experiments were performed to understand biogenic aragonite alteration processes and products. Shell subsamples of the bivalve Arctica islandica were exposed to hydrothermal alteration. Thermal boundary conditions were set at 100°C, 175°C and 200°C. These comparably high temperatures were chosen to shorten experimental durations. Subsamples were exposed to different ¹⁸O‐depleted fluids for durations between two and twenty weeks. Alteration was documented using X‐ray diffraction, cathodoluminescence, fluorescence and scanning electron microscopy, as well as conventional and clumped isotope analyses. Experiments performed at 100°C show redistribution and darkening of organic matter, but lack evidence for diagenetic alteration, except in Δ₄₇ which show the effects of annealing processes. At 175°C, valves undergo significant aragonite to calcite transformation and neomorphism. The δ¹⁸O signature supports transformation via dissolution and reprecipitation, but isotopic exchange is limited by fluid migration through the subsamples. Individual growth increments in these subsamples exhibit bright orange luminescence. At 200°C, valves are fully transformed to calcite and exhibit purple‐blue luminescence with orange bands. The δ¹⁸O and Δ₄₇ signatures reveal exchange with the aqueous fluid, whereas δ¹³C remains unaltered in all experiments, indicating a carbonate‐buffered system. Clumped isotope temperatures in high‐temperature experiments show compositions in broad agreement with the measured temperature. Experimentally induced alteration patterns are comparable with individual features present in Pleistocene shells. This study represents a significant step towards sequential analysis of diagenetic features in biogenic aragonites and sheds light on reaction times and threshold limits. The limitations of a study restricted to a single test organism are acknowledged and call for refined follow‐up experiments.     

Late-Stage Mafic Injection and Thermal Rejuvenation of the Vinalhaven Granite, Coastal Maine

The Vinalhaven intrusive complex consists mainly of coarse-grainedgranite, inward-dipping gabbro–diorite sheets, and a fine-grainedgranite core. Small bodies of porphyry occur throughout thecoarse-grained granite. The largest porphyry body (roughly 0·5km by 2·5 km) occurs with coeval gabbro, hybrid rocks,and minor fine-grained granite in the Vinal Cove complex, whichformed during the waning stages of solidification of the coarse-grainedVinalhaven granite. Porphyry contacts with surrounding coarse-grainedgranite are irregular and gradational. Compositions of wholerocks and minerals in the porphyry and the coarse-grained graniteare nearly identical. Neighboring phenocrysts in the porphyryvary greatly in degree of corrosion and reaction, indicatingthat the porphyry was well stirred. Thermal rejuvenation ofa silicic crystal mush by a basaltic influx can explain thecomposition and texture of the porphyry. Comparable rejuvenationevents have been recognized in recent studies of erupted rocks.Weakly corroded biotite phenocrysts in the porphyry requirethat hydrous interstitial melt existed in the granite duringremelting. Field relations, along with thermal calculations,suggest that cooling and crystallization of coeval mafic magmacould have generated the porphyry by thermal rejuvenation ofgranite crystal-mush containing about 20% melt. Field relationsalso suggest that some of the porphyry matrix may representnew felsic magma that was emplaced during remelting. KEY WORDS: granite; magma chamber; mafic replenishment; rejuvenation     

The peterson limestone — early cretaceous lacustrine carbonate deposition in western wyoming and southeastern idaho

The lacustrine Peterson Limestone of western Wyoming and southeastern Idaho comprises six lithofacies throughout its 20,000 km² aerial extent. These are: (1) calcareous sandstone and shale, (2) red nodular limestone, (3) pink sandy micrite, (4) biomicrite, (5) graded silty micrite, and (6) limestone conglomerate. The first two represent floodplain deposition and paleosols, whereas the remaining are shallow nearshore and deeper lacustrine sediments.This sequence was developed in a large fresh, hardwater lake surrounded by fluvial systems and associated flood plains in a warm temperate climate. Well-oxidized sandy terrigenous rocks, together with calcareous paleosol nodules, indicate that flood-plain deposition both preceded and was concurrent with lacustrine carbonate deposition. Micrite and biomicrite formed in deeper parts of the basin while sandy and silty carbonate accumulated in shallower lake-margin areas. Less-calcareous shale units which are interbedded with deeper-water carbonate were deposited either during rapid basin subsidence and deepening of the lake center or during periods of slower carbonate precipitation. Turbidity currents and subaqueous debris flows generated along steeper lake margins, resulted in the deposition of rhythmic layers of graded silty micrite and diamictic limestone conglomerate in the deepest part of the basin. The carbonate-rich sediments comprising these two lithofacies were originally deposited on shallow lake-margin benches and subsequently were transported downslope toward the lake center.Comparison with other carbonate-precipitating lacustrine systems indicates that this lake was not like modern playas. Although no known modern lacustrine system is precisely like Lake Peterson, the flora, fauna, composition, and distribution of facies within modern temperate-region lakes most closely resemble those of the Peterson Limestone.     

Mo isotope fractionation during adsorption to Fe (oxyhydr)oxides

Molybdenum (Mo) isotopes have great potential as a paleoredox indicator, but this potential is currently restricted by an incomplete understanding of isotope fractionations occurring during key (bio)geochemical processes. To address one such uncertainty we have investigated the isotopic fractionation of Mo during adsorption to a range of Fe (oxyhydr)oxides, under variable Mo/Fe-mineral ratios and pH. Our data confirm that Fe (oxyhydr)oxides can readily adsorb Mo, highlighting the potential importance of this removal pathway for the global Mo cycle. Furthermore, adsorption of Mo to Fe (oxyhydr)oxides is associated with preferential uptake of the lighter Mo isotopes. Fractionations between the solid and dissolved phase (Δ⁹⁸Mo) increase at higher pH, and also vary with mineralogy, increasing in the order magnetite (Δ⁹⁸Mo = 0.83 ± 0.60‰) < ferrihydrite (Δ⁹⁸Mo = 1.11 ± 0.15‰) < goethite (Δ⁹⁸Mo = 1.40 ± 0.48‰) < hematite (Δ⁹⁸Mo = 2.19 ± 0.54‰). Small differences in isotopic fractionation are also seen at varying Mo/Fe-mineral ratios for individual minerals. The observed isotopic behaviour is consistent with both fractionation during adsorption to the mineral surface (a function of vibrational energy) and adsorption of different Mo species/structures from solution. The different fractionation factors determined for different Fe (oxyhydr)oxides suggests that these minerals likely exert a major control on observed natural Mo isotope compositions during sediment deposition beneath suboxic through to anoxic (but non-sulfidic) bottom waters. Our results confirm that Mo isotopes can provide important information on the spatial extent of different paleoredox conditions, providing they are used in combination with other techniques for evaluating the local redox environment and the mineralogy of the depositing sediments.