Evolution of the oceanic calcium cycle during the late Mesozoic: Evidence from δ44/40Ca of marine skeletal carbonates

The Ca isotope compositions of 37 late Mesozoic skeletal carbonates, belemnites and brachiopods, from the Tethyan realm were analyzed by thermal (TIMS) and plasma (MC-ICP-MS) ionization mass spectrometry. A poor correlation between δ^44/40Ca and δ¹⁸O values of belemnites suggests only a weak temperature dependency for the Ca isotope composition of belemnites, likely less than 0.02‰/°C. The δ^44/40Ca record of belemnites was therefore used to reconstruct the Ca isotope composition of paleo-seawater (δ^44/40Ca_SW), based on an experimentally determined fractionation factor between seawater Ca and belemnite calcite (α_CC–SW) of ∼ 0.9986. The inferred δ^44/40Ca_SW record, with an average stratigraphic resolution of 1 Ma, shows systematic temporal variation of ∼ 0.5‰ with the Middle/Late Jurassic (∼ 154 Ma) minimum of ∼ 1.4‰ and a subsequent general increase to the Early Cretaceous (∼ 124 Ma) maximum of ∼ 1.9‰. The global nature of the δ^44/40Ca_SW record is supported by identical Ca isotope compositions of coeval (Kimmeridgian) belemnites collected from two distinct paleogeographic regions, the southern (New Zealand) and northern (Germany) margin of the Tethys Ocean. The observed late Mesozoic δ^44/40Ca_SW record was simulated using a simple Ca isotope mass balance model, and the results indicate that the variation in δ^44/40Ca_SW record can be explained by changes in oceanic input fluxes of Ca that were independent of the carbonate ion fluxes, such as the hydrothermal Ca flux or the release of Ca to the oceans via dolomitization of marine carbonates.     

The Himalayan foreland basin crust and upper mantle

Modeling of multimode surface wave group velocity dispersion data sampling the eastern and the western Ganga basins, reveals a three layer crust with an average V_s of 3.7 km s^?1, draped by ～2.5 km foreland sediments. The Moho is at a depth of 43 ± 2 km and 41 ± 2 km beneath the eastern and the western Ganga basins respectively. Crustal V_p/V_s shows a felsic upper and middle crust beneath the eastern Ganga basin (1.70) compared to a more mafic western Ganga basin crust (1.77). Due to higher radiogenic heat production in felsic than mafic rocks, a lateral thermal heterogeneity will be present in the foreland basin crust. This heterogeneity had been previously observed in the north Indian Shield immediately south of the foreland basin and must also continue northward below the Himalaya. The high heat producing felsic crust, underthrust below the Himalayas could be an important cause for melting of midcrustal rocks and emplacement of leucogranites. This is a plausible explanation for abundance of leucogranites in the east-central Himalaya compared to the west. The uppermost mantle V_s is also significantly lower beneath the eastern Ganga basin (4.30 km s^?1) compared to the west (4.44 km s^?1).     

Minor element and Ca isotope composition of calcareous dinoflagellate cysts of cultured Thoracosphaera heimii

We investigated the influences of temperature, salinity and pH on the calcium isotope as well as trace and minor element (uranium, strontium, magnesium) to Ca ratios on calcium carbonate cysts of the calcareous dinoflagellate species Thoracosphaera heimii grown in laboratory cultures. The natural habitat of this species is the photic zone (preferentially at the chlorophyll maximum depth) of temperate to tropical oceans, and it is abundant in deep-sea sediments over the entire Cenozoic. In our experiments, temperatures ranged from 12 to 30 °C, salinity from 36.5 to 38.8 and pH from 7.9 to 8.4. The δ^44/40Ca of T. heimii cysts resembles that of other marine calcifiers, including coccolithophores, foraminifers and corals. However, its temperature sensitivity is considerably smaller and statistically insignificant, and T. heimii might serve as a recorder of changes in seawater δ^44/40Ca over geologic time. The Sr/Ca ratios of T. heimii cysts show a pronounced temperature sensitivity (0.016 mmol/mol °C^? 1) and have the potential to serve as a palaeo-sea surface temperature proxy. No clear temperature- and pH-dependences were observed for Mg/Ca. U/Ca seems to be influenced by temperature and pH, but the correlations change sign at 23 °C and pH 8.2, respectively.     

Time-Domain Moment Tensors for shallow (h ≤ 40 km) earthquakes in the broader Aegean Sea for the years 2006 and 2007: The database of the Aristotle University of Thessaloniki

We present a catalog of moment tensor (MT) solutions and moment magnitudes, M_w, for 119 shallow (h ≤ 40 km) earthquakes in Greece and its surrounding lands (34°N–42°N, 19°E–30°E) for the years 2006 and 2007, computed with the 1D Time-Domain Moment Tensor inversion method (TDMT_INV code of Dreger, 2003). Magnitudes range from 3.2 ≤ M_w ≤ 5.7. Green's functions (GF) have been pre-computed to build a library, for a number of velocity profiles applicable to the broader Aegean Sea region, to be used in the inversion of observed broad band waveforms (10–50 s). All MT solutions are the outcome of a long series of tests of different reported source locations and hypocenter depths. Quality factors have been assigned to each MT solution based on the number of stations used in the inversion and the goodness of fit between observed and synthetic waveforms. In general, the focal mechanisms are compatible with previous knowledge on the seismotectonics of the Aegean area. The new data provide evidence for strike-slip faulting along NW–SE trending structures at the lower part of Axios basin, close to the heavily industrialized, and presently subsiding, region of the city of Thessaloniki. Normal faulting along E–W trending planes is observed at the Strimon basin, and in Orfanou Gulf in northern Greece. A sequence of events in the east Aegean Sea close to the coastline with western Anatolia sheds light on an active structure bounding the north coastline of Psara–Chios Islands about 20–25 km in length exhibiting right lateral strike-slip faulting.     

Co-sequestration of SO2 with supercritical CO2 in carbonates: An experimental study of capillary trapping,relative permeability,and capillary pressure

In this study we performed three categories of steady- and unsteady-state core-flooding experiments to investigate capillary trapping, relative permeability, and capillary pressure, in a scCO₂ + SO₂/brine/limestone system at elevated temperature and pressure conditions, i.e., 60 °C and 19.16 MPa. We used a Madison limestone core sample acquired from the Rock Springs Uplift in southwest Wyoming. We carried out two sets of steady-state drainage-imbibition relative permeability experiments with different initial brine saturations to study hysteresis. We found that the final scCO₂ + SO₂ drainage relative permeability was very low, i.e., 0.04. We also observed a rapid reduction in the scCO₂-rich phase imbibition relative permeability curve, which resulted in a high residual trapping. The results showed that between 62.8% and more than 76% of the initial scCO₂ + SO₂ at the end of drainage was trapped by capillary trapping mechanism (trapping efficiency). We found that at higher initial brine saturations, the trapping efficiency was higher. The maximum initial and residual scCO₂-rich phase saturations at the end of primary drainage and imbibition were 0.525 and 0.329, respectively. Each drainage-imbibition cycle was followed by a dissolution process to re-establish S_w = 1. The dissolution brine relative permeabilities for both cycles were also obtained. We characterized the scCO₂ + SO₂/brine capillary pressure hysteresis behavior through unsteady-state primary drainage, imbibition, and secondary drainage experiments. We observed negative imbibition capillary pressure curve indicative of possible wettability alteration throughout the experiments due to contact with scCO₂ + SO₂/brine fluid system. The trapping results were compared to those reported in literature for other carbonate core samples. We noticed slightly more residual trapping in our sample, which might be attributed to heterogeneity, different viscosity ratio, and pore-space topologies. The impact of dynamic effects, i.e., high brine flow rate imbibition tests, on trapping of the scCO₂-rich phase was also explored. We performed two imbibition experiments with relatively high brine flow rates. The residual scCO₂ saturation dropped to 0.291 and 0.262 at the end of the first and second imbibition tests, i.e., 11.5% and 20.4%, respectively, compared to 0.329 under capillary-dominated regime.     

Immune responses to combined effect of hypoxia and high temperature in the green-lipped mussel Perna viridis

Flow cytometry was used to examine immune responses in haemocytes of the green-lipped mussel Perna viridis under six combinations of oxygen level (1.5 mg O₂ l⁻¹, 6.0 mg O₂ l⁻¹) and temperature (20 °C, 25 °C and 30 °C) at 24 h, 48 h, 96 h and 168 h. The mussels were then transferred to normoxic condition (6.0 mg O₂ l⁻¹) at 20 °C for further 24 h to study their recovery from the combined hypoxic and temperature stress. Esterase (Est), reactive oxygen species (ROS), lysosome content (Lyso) and phagocytosis (Pha) were reduced at high temperatures, whereas hypoxia resulted in higher haemocyte mortality (HM) and reduced phagocytosis. For HM and Pha, changes were observed after being exposed to the stresses for 96 h, whereas only a 24 h period was required for ROS and Lyso, and a 48 h one for Est. Recovery from the stresses was observed for HM and Pha but not other immune responses.     

Stratification and mixing of a post-glacial Neoproterozoic ocean: Evidence from carbon and sulfur isotopes in a cap dolostone from northwest China

To improve our knowledge about the geochemical and environmental aftermath of Neoproterozoic global glaciations, we analyzed stable isotopes (δ¹³C, δ¹⁸O, δ³⁴S) and elemental concentrations (Ca, Mg, S, Sr, Fe, and Mn) of the ～ 10-m-thick Zhamoketi cap dolostone atop the Tereeken diamictite in the Quruqtagh area, eastern Chinese Tianshan. Available chemostratigraphic data suggest that the Tereeken diamictite is probably equivalent to the Marinoan glaciation. Our new data indicate that organic and carbonate carbon isotopes of the Zhamoketi cap dolostone show little stratigraphic variations, averaging ? 28.2‰ and ? 4.6‰, respectively. In contrast, sulfur isotopes show significant stratigraphic variations. Carbonate associated sulfate (CAS) abundance decreases rapidly in the basal cap dolostone and δ³⁴S_CAS composition varies between + 9‰ and + 15‰ in the lower 2.5 m. In the overlying interval, CAS abundance remains low while δ³⁴S_CAS rises ～ 5‰ and varies more widely between + 10‰ and + 21‰. The range of δ³⁴S_py of the cap dolostone overlaps with that of δ³⁴S_CAS, but direct comparison shows that δ³⁴S_py is typically greater than δ³⁴S_CAS measured from the same samples. Hypotheses to explain the observations must account for both the remarkable sulfur isotope enrichment of pyrites and the inverse fractionation. We propose that CAS and pyrite were derived from two isotopically distinct reservoirs in a chemically stratified basin or a basin with a sulfate minimum zone. In this model, CAS was derived from shallow, oxic surface waters with moderate sulfate concentration and depleted in ³⁴S due to the post-glacial influx of sulfur from continental weathering. In contrast, pyrite was derived from anoxic bottom waters (or a sulfate minimum zone) with low sulfate concentration and ³⁴S enrichment due to long-term syn-glacial sulfate reduction. The rapid shift in CAS abundance and sulfur isotope composition within the cap dolostone is interpreted to reflect the mixing of the two reservoirs after initial deglaciation. Comparison with other post-Marinoan cap carbonates shows significant spatial heterogeneity in δ³⁴S_CAS, which together with strong temporal variation in δ³⁴S_CAS, points to generally low sulfate concentrations in post-Marinoan oceans.     

Latitudinal patterns of export production recorded in surface sediments of the Chilean Patagonian fjords (41–55°S) as a response to water column productivity

The Chilean Patagonian fjords region (41–56°S) is characterized by highly complex geomorphology and hydrographic conditions, and strong seasonal and latitudinal patterns in precipitation, freshwater discharge, glacier coverage, and light regime; all of these directly affect biological production in the water column. In this study, we compiled published and new information on water column properties (primary production, nutrients) and surface sediment characteristics (biogenic opal, organic carbon, molar C/N, bulk sedimentary δ¹³C_org) from the Chilean Patagonian fjords between 41°S and 55°S, describing herein the latitudinal pattern of water column productivity and its imprint in the underlying sediments. Based on information collected at 188 water column and 118 sediment sampling sites, we grouped the Chilean fjords into four main zones: Inner Sea of Chiloé (41° to ～44°S), Northern Patagonia (44° to ～47°S), Central Patagonia (48–51°S), and Southern Patagonia (Magellan Strait region between 52° and 55°S). Primary production in the Chilean Patagonian fjords was the highest in spring–summer, reflecting the seasonal pattern of water column productivity. A clear north–south latitudinal pattern in primary production was observed, with the highest average spring and summer estimates in the Inner Sea of Chiloé (2427 and 5860 mg C m^?2 d^?1) and Northern Patagonia (1667 and 2616 mg C m^?2 d^?1). This pattern was closely related to the higher availability of nutrients, greater solar radiation, and extended photoperiod during the productive season in these two zones. The lowest spring value was found in Caleta Tortel, Central Patagonia (91 mg C m^?2 d^?1), a site heavily influenced by glacier meltwater and river discharge loaded with glacial sediments. Biogenic opal, an important constituent of the Chilean fjord surface sediments (Si_OPAL ～1–13%), reproduced the general north–south pattern of primary production and was directly related to water column silicic acid concentrations. Surface sediments were also rich in organic carbon content and the highest values corresponded to locations far away from glacier influence, sites within fjords, and/or semi-enclosed and protected basins, reflecting both autochthonous (water column productivity) and allochthonous sources (contribution of terrestrial organic matter from fluvial input to the fjords). A gradient was observed from the more oceanic sites to the fjord heads (west–east) in terms of bulk sedimentary δ¹³C_org and C/N ratios; the more depleted (δ¹³C_org ?26‰) and higher C/N (23) values corresponded to areas close to rivers and glaciers. A comparison of the Chilean Patagonian fjords with other fjord systems in the world revealed high variability in primary production for all fjord systems as well as similar surface sediment geochemistry due to the mixing of marine and terrestrial organic carbon.     

Magnetic susceptibility and Cs-137 inventory variability as influenced by land use change and slope positions in a hilly,semiarid region of west-central Iran

The objective of this study was to explore the slope position and land use change effects on the variability in magnetic susceptibility and ¹³⁷Cs inventory as the soil redistribution indicators in a hilly semiarid calcareous area in Iran. The selected study area is located in a hilly region with pasture and cultivation land use of Fereydunshahr, Isfahan Province in west-central Iran. In the two mentioned dominant ecosystems, four slope positions including summit, shoulder, backslope and footslope were identified and in each land use and slope position, three cores were selected to collect 72 soil samples from three depths (0–10, 10–20, 20–30 cm) in an area of 15 × 15 cm. Additional 28 soil samples were collected from the reference site for soil loss and deposition calculations by using the Cs-137 measurement. The results of the study with the use of the Cs-137 technique showed that the average soil loss in the pasture land (46.4 t ha^− 1 yr^− 1) was significantly (p < 0.05) lower than the average soil loss in the cultivated land (80.4 t ha^− 1 yr^− 1). The highest soil loss in both land uses was obtained in the shoulder position, 60.1 and 84.4 t ha^− 1 yr^− 1, respectively, for the pasture and cultivated lands. Moreover, the highest rates of soil deposition was observed in a footslope position in both land uses and they were 34 and 32.4 t ha^− 1 yr^− 1 for the pasture and cultivated lands, respectively. Magnetic susceptibility was significantly (p < 0.05) greater in pasture (χ_lf = 41.51 × 10^− 8 m³/kg) than in the cultivated land (χ_lf = 34.90 × 10^− 8 m³/kg). The pasture land with a lower soil loss rate, indicated significantly higher magnetic susceptibility in all landform positions as compared to that in the cultivated land. The results of the correlation analysis showed that among the studied soil physico-chemical properties, χ_lf (r = 0.83, p < 0.01) in the pasture land had the highest correlation with the Cs-137 inventory. Throughout the non-linear regression analysis, χ_lf was introduced for relating soil parameters and the cesium inventory explained 68% and 79% of the total variability of ¹³⁷Cs in the pasture and cultivated lands, respectively. The results implied that the variability in the magnetic susceptibility within the hillslope is consistent with the variation of the Cs-inventory; and the results thus demonstrate the slope and land use effects on soil redistribution.     

The current performance of the in situ 14C extraction line at ETH

We present the new ¹⁴C extraction line at ETH Zürich. This system is designed to extract in situ-produced cosmogenic ¹⁴C from terrestrial quartz samples, and to obtain pure CO₂ gas for analysis with a gas ion source Accelerator Mass Spectrometry (AMS) system. Samples are degassed at 1550–1600 °C without the use of a fluxing agent. Gas purification is achieved by a series of cryogenic traps and passage through hot Ag and Cu wool/mesh. Graphitization and, thus, sample dilution is not required. Tests to determine the CO₂ recovery after gas extraction and cleaning yielded consistently good recovery rates of >99.8% (n = 7). The ¹⁴C blank contribution from the all-metal tubing system is negligible. Our preliminary procedural blank estimate – deriving mostly from the hot extraction furnace – is <5 × 10^{5 14}C atoms. Extraction tests on two quartz samples by stepped-heating show a quantitative separation of atmospheric ¹⁴C at ≤500 °C from the in situ component above 1200 °C. Based on these data, we estimate to achieve a complete ¹⁴C extraction from a quartz sample.     

Optical signatures of dissolved organic matter in the watershed of a globally large river (Yangtze River,China)

Parallel factor analysis of fluorescence excitation emission matrices of surface water samples of a globally large river (Yangtze River, China) watershed identified three classes of fluorescent dissolved organic matter (FDOM) that had ex/em = 280/330 nm, 305/385 nm and 350/450 nm respectively, resembling “peak T”, “peak M” and “peak C” commonly identified in natural water, respectively. Peak T (a tyrosine/tryptophan-like FDOM) did not show correlations to peak M or C which were humic-like substances, while a positive correlation (r = 0.935, p < 0.001) was present between the natural log-transformed maximum fluorescence intensity (F_max) of peaks T and M indicating a tight link during their production and processing. F_max values (in Raman unit nm^?1) normalized to dissolved organic carbon (DOC) concentration were low, varying in ranges 15.93–85.95, 29.83–83.54 and 19.73–51.05 × 10^?5 nm^?1 (μmol/L)^?1 for peaks T, M and C, respectively, in line with the history of strong photobleaching of the water samples as indicated by fairly high absorption spectral slope ratios (0.75–1.53 with a mean 1.03). Intermediate fluorescence index (FI) (1.46–1.83 with a mean 1.61) and small specific absorption at 254 nm (0.64–1.93 with a mean 1.15 m^?1 mg^?1 L) of the water samples, indicated the presence of both aquatic microbial DOM (e.g. peak T) and soil DOM (e.g. peak C). Peak C could be substantially removed by UV-A (320–400 nm) irradiation, while peak M was slightly increased when a microbe-containing water was exposed to the same UV-A irradiation. Taken together, peak C was attributed to diffuse soil source while peak M was likely attributed to joint effects of microbial activities and solar irradiation on the chromophores in the sample.     

Importance of reversible attachment in predicting E. coli transport in saturated aquifers from column experiments

Drinking water wells indiscriminatingly placed adjacent to fecal contaminated surface water represents a significant but difficult to quantify health risk. Here we seek to understand mechanisms that limit the contamination extent by scaling up bacterial transport results from the laboratory to the field in a well constrained setting. Three pulses of Escherichia coli originating during the early monsoon from a freshly excavated pond receiving latrine effluent in Bangladesh were monitored in 6 wells and modeled with a two-dimensional (2-D) flow and transport model conditioned with measured hydraulic heads. The modeling was performed assuming three different modes of interaction of E. coli with aquifer sands: (1) irreversible attachment only (best-fit k_i = 7.6 day⁻¹); (2) reversible attachment only (k_a = 10.5 and k_d = 0.2 day⁻¹); and (3) a combination of reversible and irreversible modes of attachment (k_a = 60, k_d = 7.6, k_i = 5.2 day⁻¹). Only the third approach adequately reproduced the observed temporal and spatial distribution of E. coli, including a 4-log₁₀ lateral removal distance of ∼9 m. In saturated column experiments, carried out using aquifer sand from the field site, a combination of reversible and irreversible attachment was also required to reproduce the observed breakthrough curves and E. coli retention profiles within the laboratory columns. Applying the laboratory-measured kinetic parameters to the 2-D calibrated flow model of the field site underestimates the observed 4-log₁₀ lateral removal distance by less than a factor of two. This is promising for predicting field scale transport from laboratory experiments.     

Age estimation of the deposition of the cretaceous Upper Sandstones and a later remagnetization event,from Hirna area,SE Ethiopia

Outcrops of the Cretaceous Upper sandstone formation some 375 km to the East of Addis Ababa on the motor Highway to Harar was paleomagnetically investigated. About seventy core samples were collected at various stratigraphic levels from 250–300 meters thick sedimentary formation. After standard sample preparations in the laboratory the resulting specimens were subjected to routine paleomagnetic demagnetization protocol. In the first steps of demagnetizations process the recent and viscous magnetizations were removed by heating until a temperature of level of 300 °C. Further demagnetization of the samples resulted in the isolation of the final magnetization with stable line segments that is directed towards the origin, which is interpreted as Characteristic Remanent Magnetization (ChRM). Rock – magnetic experiments have identified goethite (αFeOOH), hematite (αFe₂O₃), detritial hematite, and magnetite as the magnetic mineral phases carrying the remanence. The ChRM identified resulted in an average value of (D_s = 0.5°, I_s = ?0.7°, α₉₅ = 4.3°, N = 34) for the red sandstones while an average value of (D_s = 335.8°, I_s = ?31.8°, α₉₅ = 4.7°, N = 14) for the limestone intercalations. The former ChRM in the red sandstone is determined to be secondary while the latter ChRM is known to be primary. Comparison of these directional results and their pole equivalents with the African plate Apparent Polar Wander Path curve established by Besse and Courtillot (2003) give ages of between 115–130 Million years for the limestone intercalation and ages of 30 million years for red sandstone unit. These are interpreted respectively as estimates of the age of deposition and a later remagnetization respectively.     

Recycling of harbor sediment as lightweight aggregate

Sediment sampled from Taichung Harbor was mixed with local reservoir sediment at different weight ratios to prepare lightweight aggregate at 1050, 1100, and 1150 °C. A pressure of 3000 or 5000 psi was used to shape the powder mixtures into pellets before the heating processes. The results indicate that the leaching levels of trace metals from the lightweight aggregate samples are considerably reduced to levels less than Taiwan Environmental Protection Administration regulatory limits. Increasing final process temperature tends to reduce the bulk density and crushing intensity of lightweight aggregate with a concomitant increase in water sorption capability. Lightweight aggregate with the lowest bulk density, 0.49 g cm⁻³ for the 5000 psi sample, was obtained with the heating process to 1150 °C. Based on the X-ray absorption near edge structure results, FeSO₄ decomposition with a concomitant release of SO_x (x = 2, 3) is suggested to play an important role for the bloating process in present study.     

Whistlers observed at low-latitude ground-based VLF facility in Fiji

The propagation features of nighttime whistlers to low-latitude station, Suva (−18.2°, 178.3°, geomag. lat. −22.1°, geomag. long. 253.5°, L=1.15), Fiji, from preliminary observations made during the period from September 2003–2005, are reported. The observations of ELF–VLF signals commenced in September 2003 using the VLF set-up of World Wide Lightning Location Network at our station. The whistlers were observed during the severe magnetic storm of 20–22 November 2003 and moderate magnetic storm of 17–19 July 2005. A whistler with dispersion D=12.7 s^1/2 occurred on 22 November at 00:11 h LT. On 20 July at 01:00 h LT, a short whistler with dispersion D=20.9 s^1/2 and two whistler events having two-component whistlers with D=15.8, 16.7 s^1/2 and 16.7, 17.3 s^1/2 were observed. Non-ducted pro-longitudinal mode of the whistler propagation supported by negative latitudinal electron density gradients in the ionosphere that are enhanced by magnetic storms, seems most likely mode of propagation for the whistlers with dispersion of 12.7–17.3 s^1/2 to this low-latitude station.     

Seasonal and diurnal variation of electron and iron concentrations at the meteor heights above Arecibo

We report observations of seasonal and local time variation of the averaged electron and iron concentrations, as well as simultaneous measurements of the two species, above the Arecibo Observatory (18.35°N, 66.75°N), Puerto Rico. The average Fe profile between 21:00 and 24:00 LT has a single peak at about 85 km with the exception of the summer when an additional peak exists at about 95 km. The higher Fe peak in the summer is correlated with higher electron concentrations in this season. The three nights of simultaneous measurements of electron and iron concentrations show that narrow layers of Fe and electrons are well correlated. Comparison of the climatological and simultaneous Fe and electron data suggests that recombination of Fe⁺ plays an important role in determining the Fe profile in the upper part of the Fe layer. Above 93 km, the Fe concentration appears to increase after sunset if the electron concentration exceeds about 4000 electrons cm⁻³. The average rate of Fe production is about 0.1 atom cm⁻³ s⁻¹ for all seasons at 100 km in the early evening hours. A chemical model reveals that the concentration of Fe⁺ must be 50–80% of the total ionization over Arecibo for typical equinox conditions to explain the observed rate of Fe production. These high relative Fe⁺ concentrations are consistent with in situ observations that Fe⁺ is usually the dominant ion in sporadic E layers in the nighttime lower E region. This suggests that the source of Fe⁺ is provided by sporadic E layers descending over Arecibo after sunset. The Fe density between 80 and 85 km decreases during the night, for all seasons. This is attributed to the formation of stable molecular Fe species, such as FeOH, due to the increase in O₃ and decrease in atomic O and H during the night at these altitudes.     

Century-long record of Mo isotopic composition in sediments of a seasonally anoxic estuary (Chesapeake Bay)

A double-spike method was used to obtain Mo isotope data for sediments and waters of the seasonally anoxic Chesapeake Bay, and its primary tributary, the Susquehanna River. The dissolved Mo distribution in the estuary is non-conservative, reflecting minor Mo loss to the sediments, although removal of Mo to the sediments does not have a large influence on the isotopic composition of the water column. The δ⁹⁸Mo of dissolved Mo in most of the estuary is dominated by seawater. Six samples with salinity > 15 have an average δ⁹⁸Mo = + 2.17‰ (± 0.12), which agrees well with a δ⁹⁸Mo value for the CASS-4 seawater standard of + 2.23‰. A single sample of Susquehanna River water has a δ⁹⁸Mo of + 1.02‰, consistent with recent findings of positive δ⁹⁸Mo in rivers worldwide. Susquehanna river sediments, in contrast, have δ⁹⁸Mo ～ ? 0.1‰. The difference between the river water and sediment values implies that isotopic fractionation occurs within the river basin. The δ⁹⁸Mo values for estuarine sediments are offset from values in the overlying water. Most samples deposited before 1925 have δ⁹⁸Mo less than 0‰, similar to the Susquehanna sediments. Subsequently, there is an increase in the variability of δ⁹⁸Mo, with values ranging up to + 0.8‰. The transition to increased variability coincides with the onset of authigenic Mo deposition, which was previously attributed to escalating summertime anoxia. Authigenic Mo concentrations correlate poorly with δ⁹⁸Mo in core samples, suggesting that independent mechanisms influence the two parameters. Authigenic Mo concentrations may be controlled by shifting pore water H₂S levels, while δ⁹⁸Mo may be primarily affected by annual variations in Mn refluxing.     

Paleomagnetism of the Late Cretaceous ignimbrite from the Okhotsk-Chukotka Volcanic Belt,Kolyma-Omolon Composite Terrane: Tectonic implications

New Late Cretaceous paleomagnetic results from the Okhotsk-Chukotka Volcanic Belt in the Kolyma-Omolon Composite Terrane yield stable and consistent remanent directions. The Late Cretaceous (86–81 Ma) ignimbrites from the Kholchan and Ola suites were sampled at 19 sites in the Magadan area (60.4° N, 151.0° E). We isolated the characteristic paleomagnetic directions from 16 sampled sites using an alternating field demagnetization procedure. The primary nature of these directions is ascertained by dual polarities and positive fold tests. A tilt-corrected mean direction (D = 42.8°, I = 84.7°, k = 46.0, α₉₅ = 10.0°) yields a paleomagnetic pole of 66.7° N, 168.5° E (A₉₅ = 18.8°) which appears almost identical to the 90–67 Ma pole reported from the Lake El’gygytgyn area of the Okhotsk-Chukotka Volcanic Belt (Chukotka Terrane). This consistency suggests that the Kolyma-Omolon Composite Terrane and Chukotka Terrane has acted as a single tectonic unit since 80 Ma without any significant internal deformation. Accordingly, we calculate a combined 80 Ma characteristic paleomagnetic pole (Long. = 164.7° E, Lat. = 68.0°, A₉₅ = 10.9°, N = 12) for the Kolyma-Omolon-Chukotka Block which falls 16.5–17.5° south of the same age poles from Europe and East Asia. We ascribe this discrepancy in pole positions to tectonic activity in the area and infer a southward displacement of 1640 ± 1380 km for the Kolyma-Omolon-Chukotka Block with respect to the North American and Eurasian blocks since 80 Ma; more than 260 km of it is attributed to tectonic displacement in the Arctic Ocean due to the opening of the Canadian Basin.     

Magnesium isotopes constraints on the origin of Mg-rich olivines from the Allende chondrite: Nebular versus planetary?

High precision Mg isotope measurements by multi-collector ion microprobe show that refractory olivines from the Allende chondrite, either olivines isolated in the matrix (2 samples studied) or olivines in type I chondrules (6 samples studied), have variable δ²⁶Mg* enrichments and deficits (calculated in permil as the ²⁶Mg deviation from the instrumental mass fractionation line) relative to the Earth. Most average δ²⁶Mg* (noted δ²⁶Mg*_av) values (between 10 and 20 analyses per chondrule) are negative but the total range is from ?0.029 (± 0.010) ‰ (2 sigma errors) to + 0.011 (± 0.011) ‰ with an exception of one olivine at + 0.043 (± 0.023) ‰. These variations in δ²⁶Mg*_av reflect the formation of the olivines from reservoirs enriched in various amounts of ²⁶Mg by the decay of short-lived ²⁶Al (T_1/2 = 0.73 Ma). Similarly, 30 analyses of olivines from the Eagle Station pallasite show a δ²⁶Mg*_av value of ?0.033 ± 0.008‰, as negative as some olivines from Allende chondrules and the Solar system initial δ²⁶Mg* value of ?0.038 ± 0.004‰ (defined at the time of formation of type B Ca–Al-rich inclusions – CAIs – when ²⁶Al/²⁷Al = 5.23 × 10^?5, Jacobsen et al., 2008).Because olivines are Al-poor and because their Mg isotopic compositions are not reset during the chondrule forming events, their δ²⁶Mg*_av can be used to calculate model crystallization ages relative to various theoretical Mg isotope growth curves. The two end-member scenarios considered are (i) a “nebular” growth in which the Al/Mg ratio remains chondritic and (ii) a “planetary” growth in which a significant increase of the Al/Mg ratio can be due to, for instance, olivine magmatic fractionation. The low δ²⁶Mg*_av value of olivines from the Eagle Station pallasite demonstrate that metal-silicate differentiation occurred as early as ~ 0. 15_- 0. 23^+ 0. 29 Ma after CAIs in either of the growth scenarios. Similarly the variable δ²⁶Mg*_av values of refractory olivines can be understood if they were formed in planetesimals which started to differentiate as early as the Eagle Station parent body. Accretion of these planetesimals must have been coeval to the formation of CAIs and their disruption could explain why their fragments (Mg-rich olivines) were distributed in the chondrule forming regions of the disk.     

Elasticity of antigorite,seismic detection of serpentinites,and anisotropy in subduction zones

Serpentinization of the mantle wedge is an important process that influences the seismic and mechanical properties in subduction zones. Seismic detection of serpentines relies on the knowledge of elastic properties of serpentinites, which thus far has not been possible in the absence of single-crystal elastic properties of antigorite. The elastic constants of antigorite, the dominant serpentine at high-pressure in subduction zones, were measured using Brillouin spectroscopy under ambient conditions. In addition, antigorite lattice preferred orientations (LPO) were determined using an electron back-scattering diffraction (EBSD) technique. Isotropic aggregate velocities are significantly lower than those of peridotites to allow seismic detection of serpentinites from tomography. The isotropic V_P/V_S ratio is 1.76 in the Voigt–Reuss–Hill average, not very different from that of 1.73 in peridotite, but may vary between 1.70 and 1.86 between the Voigt and Reuss bonds. Antigorite and deformed serpentinites have a very high seismic anisotropy and remarkably low velocities along particular directions. V_P varies between 8.9 km s^? 1 and 5.6 km s^? 1 (46% anisotropy), and 8.3 km s^? 1 and 5.8 km s^? 1 (37%), and V_S between 5.1 km s^? 1 and 2.5 km s^? 1 (66%), and 4.7 km s^? 1 and 2.9 km s^? 1 (50%) for the single-crystal and aggregate, respectively. The V_P/V_S ratio and shear wave splitting also vary with orientation between 1.2 and 3.4, and 1.3 and 2.8 for the single-crystal and aggregate, respectively. Thus deformed serpentinites can present seismic velocities similar to peridotites for wave propagation parallel to the foliation or lower than crustal rocks for wave propagation perpendicular to the foliation. These properties can be used to detect serpentinite, quantify the amount of serpentinization, and to discuss relationships between seismic anisotropy and deformation in the mantle wedge. Regions of high V_P/V_S ratios and extremely low velocities in the mantle wedge of subduction zones (down to about 6 and 3 km.s^?1 for V_P and V_S, respectively) are difficult to explain without strong preferred orientation of serpentine. Local variations of anisotropy may result from kilometer-scale folding of serpentinites. Shear wave splittings up to 1–1.5 s can be explained with moderately thick (10–20 km) serpentinite bodies.