Controls on alkenone unsaturation ratios along the salinity gradient between the open ocean and the Baltic Sea

Alkenone unsaturation ratios of sedimentary lipids are used as a geochemical proxy for sea surface temperatures, and interest is growing in their potential as indicators of different water masses and possibly of salinity. We analyzed the abundance of unsaturated C₃₇ to C₃₈ ketones in lipid extracts of 57 surface sediment (0-1 cm) samples along a salinity gradient from 8 to 33 psu in the transition from the Skagerrak to the Baltic Sea (NW Europe). In addition to surface sediments, we analyzed alkenones in suspended particulate matter at 13 stations—over a gradient in salinity from 25 to 33 psu—during a bloom of the coccolithophore Emiliania huxleyi. Alkenones were detected in all samples (suspended matter and sediment) with variable contributions of the tetra-unsaturated C₃₇ alkenone compound (%C_37:4; range from 2 to 10% of total C₃₇ alkenone content). Comparing the alkenone unsaturation index (U₃₇^K′) and %C_37:4 data to climatological sea surface temperature and sea surface salinity data sets revealed that SST estimated from U₃₇^K′ of saline end members (samples from the Skagerrak) is in the general range of modern SST during bloom periods of haptophytes. At salinities below ∼30 psu %C_37:4 increases to above 5% and the unsaturation ratios cease to be related to climatological annual or seasonal sea surface temperatures. On the other hand, the %C_37:4 appears to be inversely and significantly correlated to salinity: Highest C_37:4 proportions in the inner Baltic Sea are caused by an unidentified organism, but in the transition area at salinities down to 10 psu, the producer apparently is E. huxleyi. The suspended matter data together with those from the water column support the hypothesis of changing biosynthesis of alkenones under salt stress by the coccolithophore E. huxleyi, but constrain the maximum of %C_37:4 attributable to salt stress to 10% of all C₃₇ alkenones.     

Salinity control on long-chain alkenone distributions in lake surface waters and sediments of the northern Qinghai-Tibetan Plateau, China

Long-chain alkenones in lacustrine settings are potentially excellent biomarkers for the reconstruction of past terrestrial environmental conditions, and have been found in many different types of lakes around the globe. A wider range of factors influence the occurrence and distribution of alkenones in lake sediments and waters when compared to marine systems. Lake environmental conditions, such as temperature (in particular) and salinity, are among the key factors controlling alkenone distributions in lacustrine settings. Here we investigated alkenone distribution patterns in lakes of the northern Qinghai-Tibetan Plateau, China, and their possible relationship with environmental conditions, by analyzing paired samples of suspended particulate matter in surface waters and surface sediments. Salinity of investigated lake waters ranges from almost 0 to ∼100 g/L, while temperature variation among the lakes is minimal, effectively eliminating temperature effects on the alkenone distribution patterns observed here. We show that (1) alkenone concentrations vary substantially between the lakes, yet controlling mechanisms remain elusive; (2) C₃₇/C₃₈ ratios are substantially lower in the lakes of the Qaidam Basin than in the Lake Qinghai region, probably indicating different alkenone producers in the two regions; and (3) large variations in %C_37:4 (the percentage of the C_37:4 alkenone), determined from both surface waters and sediments, are negatively correlated with salinity. We suggest that the %C_37:4 index could be used as a salinity indicator at least on a regional scale, with careful considerations of other potentially complicating factors. However, potential reasons for why salinity could significantly affect %C_37:4 values need further investigation.     

Characteristics of alkenones synthesized by a bloom of emiliania huxleyi in the Bering Sea

We investigated the characteristics of the alkenones produced by a bloom of Emiliania huxleyi in the eastern Bering Sea in 2000. Alkenones were detected in surface waters between 57°N and 63°N, where phosphate concentrations were low and the ammonium/nitrate ratio was high. The total alkenone content (C_37:2, C_37:3, and C_37:4) ranged from 22.0 to 349 μg g⁻¹ in suspended particles and from 0.109 to 1.42 μg g⁻¹ in surface sediments. This suggests that a large proportion of the particulate alkenones synthesized in the surface water rapidly degraded within the water column and/or at the water-sediment interface of the Bering Shelf. The change in the stable carbon isotopic composition (δ¹³C) of C_37:3 alkenone could not be explained only by variation in [CO₂(aq)] in the surface water but also depended on the growth rate of E. huxleyi. The alkenone unsaturation index (U^K′₃₇) was converted into an alkenone “temperature” with three equations [Prahl et al 1988], [Sikes et al 1997] and [Müller et al 1998]; Sikes et al.’s (1997) equation gave the best correlation with the observed sea surface temperature (SST) in the eastern Bering Sea. However, some temperatures estimated by Sikes et al.’s (1997) equation from the U^K′₃₇ varied from the observed SST, possibly because of the rapidly changing rate of alkenone synthesis in the logarithmic growth stage or the low rate of alkenone synthesis when nutrients were limiting. Temperatures estimated from U^K′₃₇ in the surface sediments (6.8-8.2°C) matched the observed SST in September (7-8°C) but differed from the annual average SST of 4 to 5°C, suggesting that most of the alkenone in the eastern Bering Sea was synthesized during limited periods, for instance, in September. The relative amounts of C_37:4 alkenone as proportions of the total alkenones (referred to as C_37:4%) were high, ranging from 18.3 to 41.4%. Low-salinity water (<32 psu) within the study area would have contributed to the high C_37:4% because a negative linear relationship between C_37:4% and salinity was found in this study.     

Distribution and significance of long-chain alkenones as salinity and temperature indicators in Spanish saline lake sediments

We investigated relationships between sedimentary solvent-extractable long-chain alkenone (LCA) concentration and composition and environmental factors in a suite of endorheic lakes from inland Spain. LCAs were found in 14 of the 54 lakes examined, with concentrations comparable with those from previously published lacustrine settings. The composition of LCAs in our sites, however, contrast from the majority of those previously reported from lake environments; in our study the tri-unsaturated component is the most abundant component at most sites where LCAs are detected, and C_38:3 is the most abundant LCA in the majority of sites. LCA occurrence appears to be restricted to brackish-hypersaline sites and C₃₇ LCAs are absent above a salinity of ∼40 g L⁻¹ suggesting a salinity control on LCA-producing organisms in these sites. Low concentrations of C₃₇ LCA components means and temperature indices are generally not applicable. Instead we find good relationships between C₃₈ components and (in particular mean autumn) temperature and the strongest LCA-temperature relationships are found when using a combination of all C₃₇ and C₃₈ compounds. We propose a new alkenone temperature index for lakes with elevated salinity and where the C₃₈ components dominate the LCA distributions. This is expressed as (r² = 0.80, n = 13). In this paper, we provide the first account of sedimentary LCA distributions from lakes in inland Spain, extending the range of environments within which these compounds have been found and highlighting their significance as indicators of both salinity and temperature in saline, endorheic lake environments. This has important implications for extending the potential role of LCAs as palaeoclimatic indicators in lacustrine environments.     

Climatic and environmental controls on the occurrence and distributions of long chain alkenones in lakes of the interior United States

Long chain alkenones (LCA) are temperature-sensitive lipids with great potential for quantitative reconstruction of past continental climate. We conducted the first survey for alkenone biomarkers from 55 different lakes in the Northern Great Plains and Nebraska Sand Hills of the United States. Among those surveyed, we found 13 lakes that contain LCAs in the surface sediments. The highest concentrations of alkenones in sediments are found in cold (mean annual air temperature ∼11 °C versus 17 °C in our warmest sites), brackish to mesosaline (salinity = 8.5-9.7 g/L), and alkaline (pH = 8.4-9.0) lakes with high concentrations of sodium and sulfate. The dynamics of stratification and nutrient availability also appear to play a role in LCA abundance, as early spring mixing promotes a bloom of alkenone-producing haptophytes. Four of the alkenone-containing sites contain the C_37:4 alkenone; however, we discovered an unprecedented lacustrine alkenone distribution in a cluster of lakes, with a total absence of C_37:4 alkenone. We attribute this unusual composition to a different haptophyte species and show that the sulfate:carbonate ratio may control the occurrence of these two distinct populations. We created a new in-situ temperature calibration for lacustrine sites that contain C_37:4 using a water-column calibration from Lake George, ND and show that is linearly correlated to lake water temperature (R² = 0.74), but is not. A number of lakes contain an unidentified compound series that elutes close to the LCAs, highlighting the importance of routine GC-MS examination prior to using lacustrine LCAs for paleotemperature reconstructions.     

Temperature and Salinity Effects on Alkenone Ratios Measured in Surface Sediments from the Indian Ocean

We compare alkenone unsaturation ratios measured on recent sediments from the Indian Ocean (20°N–45°S) with modern sea oceanographic parameters. For each of the core sites we estimated average seasonal cycles of sea surface temperature (SST) and salinity, which we then weighted with the seasonal productivity cycle derived from chlorophyll satellite imagery. The unsaturation index (U₃₇^K′) ranges from 0.2 to 1 and correlates with water temperature but not with salinity. TheU₃₇^K′versus SST relationship for Indian Ocean sediments (U₃₇^K′= 0.033 SST + 0.05) is similar to what has been observed for core tops from the Pacific and Atlantic oceans and the Black Sea. A global compilation for core tops givesU₃₇^K′= 0.031 T + 0.084 (R= 0.98), which is close to a previously reported calibration based on particulate organic matter from the water column. For temperatures between 24° and 29°C, however, the slope seems to decrease to about 0.02U₃₇^K′unit/°C. For Indian Ocean core tops, the ratios of total C₃₇alkenones/total C₃₈alkenones and the slope of theU₃₇^K′-SST relationship are similar to those previously observed for cultures ofEmiliania huxleyibut different from those previously published forGephyrocapsa oceanica.EitherE. huxleyiis a major producer of alkenones in the Indian Ocean or strains ofG. oceanicaliving in the northern Indian Ocean behave differently from the one cultured. In contrast with coccolithophorid assemblages, the ratios of C₃₇alkenones to total C₃₈alkenones lack clear geographic pattern in the Indian Ocean.     

Long-chain alkenone distributions and temperature dependence in lacustrine surface sediments from China

Long-chain alkenones (LCK) of lacustrine surface sediments were analyzed in 37 lakes from China. The results obtained were complemented by published data from 13 other Chinese lakes. These lakes are located across large temperature and precipitation gradients, therefore allowing for an assessment of the distribution pattern of LCK and their temperature dependency. Different distribution patterns of LCK (C₃₇ predominant pattern and C₃₈ predominant pattern) were detected in the surface sediment samples. The ratio of C_37:4 methyl ketone to the sum of C₃₇ alkenones observed in the different lakes is highly variable (5%-96%, with mean value of 55%), and more than that seen in marine systems. The finding that some of the ocean LCK precursor algae (Gephyrocapsa oceanica, Coccolithus pelagicus) were also present in the limnic systems suggested that both systems might have similar biosynthetic sources. Empirical relationships between the alkenone unsaturation index U₃₇^k′ and different temperature sets (mean annual air temperature, mean annual air temperature in different seasons, and lake surface water temperature of July) were tested. The best correlation between U₃₇^k′ and temperature was obtained using mean annual air temperature. A general linear regression of U₃₇^k′ and MAAT can be expressed as U₃₇^k′ = 0.0328 × T + 0.126 (n = 38, r² = 0.83). Although questions such as species-uncertainty and other unknown factors for U₃₇^k′ temperature dependence still remain, the equation might be representative of the average contribution of LCK to sediments for these data over a wide range of surface temperatures, water chemistry and different alkenones-producer algal populations. The general relationship of U₃₇^k′ and mean annual air temperature is consistent with that in marine systems. It supports the suggestion that the biosynthetic pathway of alkenones and the mechanism of their temperature signal may be similar in both marine and limnic systems. LCK might be used as an important paleotemperature proxy in limnic environment.     

Evidence for differential degradation of alkenones under contrasting bottom water oxygen conditions: implication for paleotemperature reconstruction

The successful reconstruction of sea surface temperatures using alkenone paleothermometry (U₃₇^k′) has relied on the premise that there is no significant differential degradation of alkenones with different states of unsaturation during diagenetic processes. To test this assumption, we conducted a comparative study of contemporary sediments in oxic and anoxic bottom waters from the Santa Monica Basin, offshore California. Long-chain alkenones were quantified and sea surface temperature were calculated using the calibrated U₃₇^k′–T relationship of Prahl et al. (1988). Our results show that temperature record from the oxic sediments is higher by as much as 4°C compared to those from time-equivalent anoxic sediments as a result of differential degradation of long-chain unsaturated alkenones and bioturbation mixing in the oxic sediments. The differential degradation of C_37:3 vs. C_37:2 alone could account for up to 2.5°C difference between these two records. This finding has significant implication in the interpretation of paleo–sea surface temperature data using alkenone paleothermometry.     

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.     

Hydrogen isotopes in individual alkenones from the Chesapeake Bay estuary

Hydrogen isotope ratios of individual alkenones from haptophyte algae were measured in suspended particles and surface sediment from the Chesapeake Bay (CB) estuary, eastern USA, in order to determine their relationship to water δD values and salinity. δD values of four alkenones (MeC_37:2, MeC_37:3, EtC_38:2, EtC_38:3) from particles and sediments were between −165‰ and −221‰ and increased linearly (R² = 0.7-0.9) with water δD values from the head to the mouth of the Bay. Individual alkenones were depleted in deuterium by 156-188‰ relative to water. The MeC₃₇ alkenones were consistently enriched by ∼12‰ relative to the EtC₃₈ alkenones, and the di-unsaturated alkenones of both varieties were consistently enriched by ∼20‰ relative to the tri-unsaturated alkenones. All of the increase in alkenone δD values could be accounted for by the water δD increase. Consequently, no net change in alkenone-water D/H fractionation occurred as a result of the salinity increase from 10 to 29. This observation is at odds with results from culture studies with alkenone-producing marine coccolithophorids, and from two field studies, one with a dinoflagellate sterol in the CB, and one with a wide variety of lipids in saline ponds on Christmas Island, that indicate a decline in D/H fractionation with increasing salinity. Why D/H fractionation in alkenones in the CB showed no dependence on salinity, while D/H fractionation in CB dinsoterol decreased by 1‰ per unit increase in salinity remains to be determined. Two hypotheses we consider to be valid are that (i) the assemblage of alkenone-producing haptophytes changes along the Bay and each species has a different sensitivity to salinity, such that no apparent trend in α_{alkenone-water} occurs along the salinity gradient, and (ii) greater osmoregulation capacity in coastal haptophytes may result in a diminished sensitivity of alkenone-water D/H fractionation to salinity changes.     

Note on the isotopic geochemistry of fossil-lacustrine tufas in carbonate plateau—A study from Dungul region (SW Egypt)

Lithological, chemical, and stable isotope data are used to characterize lacustrine tufas dating back to pre-late Miocene and later unknown times, capping different surfaces of a Tertiary carbonate (Sinn el-Kedab) plateau in Dungul region in the currently hyperarid south-western Egypt. These deposits are composed mostly of calcium carbonate, some magnesium carbonate and clastic particles plus minor amounts of organic matter. They have a wide range of (Mg/Ca)_molar ratios, from 0.03 to 0.3. The bulk-tufa carbonate has characteristic isotope compositions: (δ¹³C_mean = −2.49 ± 0.99‰; δ¹⁸O_mean = −9.43 ± 1.40‰). The δ¹³C values are consistent with a small input from C4 vegetation or thinner soils in the recharge area of the tufa-depositing systems. The δ¹⁸O values are typical of fresh water carbonates. Covariation between δ¹³C and δ¹⁸O values probably is a reflection of climatic conditions such as aridity. The tufas studied are isotopically similar to the underlying diagenetic marine chalks, marls and limestones (δ¹³C_mean = −2.06 ± 0.84‰; δ¹⁸O_mean = −10.06 ± 1.39‰). The similarity has been attributed to common meteoric water signatures. This raises large uncertainties in using tufas (Mg/Ca)_molar, δ¹³C and δ¹⁸O records as proxies of paleoclimatic change and suggests that intrinsic compositional differences in material sources within the plateau may mask climatic changes in the records.     

Solubility of cyclooctasulfur in pure water and sea water at different temperatures

The solubility of cyclooctasulfur in water and sea water at various temperatures in the range between 4 and 80 °C was determined. Cyclooctasulfur in equilibrium with rhombic sulfur reacted with hot acidic aqueous potassium cyanide to form thiocyanate anion which was measured by anion chromatography. Sulfur solubility in pure water was found to increase with temperature by more than 78 times: from 6.1 nM S₈ at 4 °C to 478 nM S₈ at 80 °C. The following thermodynamic values for solubilisation of S₈ in water were calculated from the experimental data: K° = 3.01 ± 1.04 × 10⁻⁸, ΔG_r° = 42.93 ± 0.73 kJ mol⁻¹, ΔH_r° = 47.4 ± 3.6 kJmol⁻¹, ΔS_r° = 15.0 ± 11.7 J mol⁻¹ K⁻¹). Solubility of cyclooctasulfur in sea water was found to be 61 ± 13% of the solubility in pure water regardless of the temperature.     

Quantifying seasonal precipitation using high-resolution carbon isotope analyses in evergreen wood

High-resolution natural abundance stable carbon isotope analyses across annual growth rings in evergreen trees reveal a cyclic increase and decrease in the measured carbon isotopic composition (δ¹³C), but the causes of this pattern are poorly understood. We compiled new and published high-resolution δ¹³C data from across annual growth rings of 33 modern evergreen trees from 10 genera and 15 globally distributed sites to quantify the parameters that affect the observed δ¹³C pattern. Across a broad range of latitude, temperature, and precipitation regimes, we found that the average, measured seasonal change in δ¹³C (Δδ¹³C_meas, ‰) within tree rings of evergreen species reflects changes in the carbon isotopic composition of atmospheric carbon dioxide (Δδ¹³C_CO2) and changes in seasonal precipitation (ΔP) according to the following equation: Δδ¹³C_meas = Δδ¹³C_CO2 - 0.82(ΔP) + 0.73; R² = 0.96. Seasonal changes in temperature, pCO₂, and light levels were not found to significantly affect Δδ¹³C_meas. We propose that this relationship can be used to quantify seasonal patterns in paleoprecipitation from intra-ring profiles of δ¹³C measured from non-permineralized, fossil wood.     

Recent increase in atmospheric deposition of mercury to California aquatic systems inferred from a 300-year geochronological assessment of lake sediments

Age-dated sediment cores from 4 remote lakes across California were analyzed for total Hg (Hg_T) concentration as a function of pre- and post-industrialization. Particle size, magnetic susceptibility and organic C and N, were measured to determine if the Hg concentration in sediment cores could be related to atmospheric deposition and/or watershed processes. Results indicate that (a) for each lake modern (1970–2004) Hg_T lake sediment concentrations have increased by an average factor of 5 times more than historic (pre-1850) Hg_T concentrations; (b) the ratio of modern to pre-industrial lake sediment Hg_T for these lakes are higher than estimated for other locations where atmospheric deposition is presumed to be the main source of Hg; (c) 2 of the 4 studied lakes demonstrated significant relationships between Hg_T concentrations and percentage organic material (r² = 0.68 and p < 0.01; r² = 0.67 and p < 0.01) whereas the other two indicated no significant relationship (r² = 0.05 and p = 0.51; r² = 0.12 and p = 0.36).     

Speciation and thermodynamic properties for cobalt chloride complexes in hydrothermal fluids at 35-440 °C and 600 bar: An in-situ XAS study

Aqueous Co(II) chloride complexes play a crucial role in cobalt transport and deposition in ore-forming hydrothermal systems, ore processing plants, and in the corrosion of special Co-bearing alloys. Reactive transport modelling of cobalt in hydrothermal fluids relies on the availability of thermodynamic properties for Co complexes over a wide range of temperature, pressure and salinity. Synchrotron X-ray absorption spectroscopy was used to determine the speciation of cobalt(II) in 0-6 m chloride solutions at temperatures between 35 and 440 °C at a constant pressure of 600 bar. Qualitative analysis of XANES spectra shows that octahedral species predominate in solution at 35 °C, while tetrahedral species become increasingly important with increasing temperature. Ab initio XANES calculations and EXAFS analyses suggest that in high temperature solutions the main species at high salinity (Cl:Co >> 2) is CoCl₄²⁻, while a lower order tetrahedral complex, most likely CoCl₂(H₂O)_2(aq), predominates at low salinity (Cl:Co ratios ∼2). EXAFS analyses further revealed the bonding distances for the octahedral Co(H₂O)₆²⁺ (^octCo-O = 2.075(19) Å), tetrahedral CoCl₄²⁻ (^tetCo-Cl = 2.252(19) Å) and tetrahedral CoCl₂(H₂O)_2(aq) (^tetCo-O = 2.038(54) Å and ^tetCo-Cl = 2.210(56) Å). An analysis of the Co(II) speciation in sodium bromide solutions shows a similar trend, with tetrahedral bromide complexes becoming predominant at higher temperature/salinity than in the chloride system. EXAFS analysis confirms that the limiting complex at high bromide concentration at high temperature is CoBr₄²⁻. Finally, XANES spectra were used to derive the thermodynamic properties for the CoCl₄²⁻ and CoCl₂(H₂O)_2(aq) complexes, enabling thermodynamic modelling of cobalt transport in hydrothermal fluids. Solubility calculations show that tetrahedral CoCl₄²⁻ is responsible for transport of cobalt in hydrothermal solutions with moderate chloride concentration (∼2 m NaCl) at temperatures of 250 °C and higher, and both cooling and dilution processes can cause deposition of cobalt from hydrothermal fluids.     

Limitations on the climatic and ecological signals provided by the δC values of phytoliths from a C4 North American prairie grass

Silica phytoliths, which are deposits of opal-A that precipitate in the intra- and intercellular spaces of plant tissues during transpiration, commonly contain small amounts of occluded organic matter. In this paper, we investigate whether the δ¹³C values of phytoliths from a C₄ grass, Calamovilfa longifolia, vary in response to climatic variables that can affect the carbon-isotope composition of plant tissues. There is no significant correlation (r² < 0.3) between climate variables and the δ¹³C values of C. longifolia tissues (average δ¹³C_tissue = −13.1 ± 0.6 ‰; n = 70) across the North American prairies. However, plant tissue δ¹³C values are lower for grasses collected in populated areas where the δ¹³C value of atmospheric CO₂ is expected to be lower because of fossil fuel burning. Phytolith δ¹³C values are more variable (δ¹³C = −27.3 to −23.0‰; average = −25.1 ± 1.3‰; n = 34) and more sensitive to changes in aridity than whole tissue δ¹³C values. The strongest correlations are obtained between the δ¹³C values of stem or sheath phytoliths and humidity (r² = 0.3), latitude (r² = 0.4) and amount of precipitation (r² = 0.5). However, use of these relationships is limited by the wide spread in δ¹³C values of phytoliths from different plant tissues at the same location. We have been unable to infer any relationship between δ¹³C values of phytoliths and expected variations in the δ¹³C values of atmospheric CO₂. The C. longifolia phytoliths are depleted of ¹³C relative to tissue carbon by 10-14‰. This means that the phytoliths examined in this study have carbon isotopic compositions within the range reported previously for phytoliths from C₃ plants. This observation may further limit the usefulness of soil-phytolith assemblage δ¹³C values for identifying shifts in grassland C₃:C₄ ratios.     

XPS spectra of uranyl minerals and synthetic uranyl compounds. I: The U 4f spectrum

The occurrence and binding energies of the U⁶⁺, U⁵⁺ and U⁴⁺ bands in the U 4f_7/2 peak of 19 uranyl minerals of different composition and structure were measured by XPS. The results suggest that these minerals can be divided into the following four groups: (1) Uranyl-hydroxy-hydrate compounds with no or monovalent interstitial cations; (2) Uranyl-hydroxy-hydrate minerals with divalent interstitial cations; (3) Uranyl-oxysalt minerals with (TO_n) groups (T = Si, P, and C) in which all equatorial O-atoms of the uranyl-polyhedra are shared with (TO_n) groups; (4) Uranyl-oxysalt minerals with (TO_n) groups (T = S and Se), in which some equatorial O-atoms are shared only between uranyl polyhedra. The average binding energies of the U⁶⁺and U⁴⁺ bands shift to lower values with (1) incorporation of divalent cations and (2) increase in the Lewis basicity of the anion group bonded to U. The first observation is a consequence of an increase in the bond-valence transfer from the interstitial species (cations, H₂O) groups to the O-atoms of the uranyl-groups, which results in an electron transfer from O to U⁶⁺. The second trend correlates with an increase in the covalency of the UO bonds with increase in Lewis basicity of the anion group, which results in a shift of the electron density from O to U. The presence of U⁴⁺ on the surface of uranyl minerals can be detected by the shape of the U 4f_7/2 peak, and the occurrence of the U 5f peak and satellite peaks belonging to the U 4f_5/2 peak. The presence of U⁴⁺ in some of the uranyl minerals and synthetics examined may be related to the conditions during their formation. A charge-balance mechanism is proposed for the incorporation of lower-valence U in the structure of uranyl minerals. Exposure of a Na-substituted metaschoepite crystal in air and to Ultra-High Vacuum results in dehydration of its surface structure associated with a shift of the U⁶⁺ bands to higher binding energies. The latter observation indicates a shift in electron density from U to O, which must be related to structural changes inside the upper surface layers of Na-substituted metaschoepite.     

Sea-Surface Temperatures and the History of Monsoon Upwelling in the Northwest Arabian Sea during the Last 500,000 Years

Arabian Sea sediments record changes in the upwelling system off Arabia, which is driven by the monsoon circulation system over the NW Indian Ocean. In accordance with climate models, and differing from other large upwelling areas of the tropical ocean, a 500,000-yr record of productivity at ODP Site 723 shows consistently stronger upwelling during interglaciations than during glaciations. Sea-surface temperatures (SSTs) reconstructed from the alkenone unsaturation index (U^K′₃₇) are high (up to 27°C) during interglaciations and low (22-24°C) during glaciations, indicating a glacial-interglacial temperature change of >3°C in spite of the dampening effect of enhanced or weakened upwelling. The increased productivity is attributed to stronger monsoon winds during interglacial times relative to glacial times, whereas the difference in SSTs must be unrelated to upwelling and to the summer monsoon intensity. The winter (NE) monsoon was more effective in cooling the Arabian Sea during glaciations then it is now.     

Stable carbon and oxygen isotope fractionation in bivalve (Placopecten magellanicus) larval aragonite

The relationship between stable isotope composition (δ¹³C and δ¹⁸O) in seawater and in larval shell aragonite of the sea scallop, Placopecten magellanicus, was investigated in a controlled experiment to determine whether isotopes in larval shell aragonite can be used as a reliable proxy for environmental conditions. The linear relationship between δ¹³C_DIC and δ¹³C_aragonite (r² = 0.97, p < 0.0001, RMSE = 0.18) was:

δ¹³C_DIC=1.15(±0.05)∗δ¹³C_aragonite-0.85(±0.04)