Calcium isotope record of Phanerozoic oceans: Implications for chemical evolution of seawater and its causative mechanisms

A total of 280 brachiopods of Ordovician to Cretaceous age, complemented by published data from belemnites and planktonic foraminifera, are used to reconstruct the evolution of calcium isotope composition of seawater (δ^44/40Ca_SW) over the Phanerozoic. The compiled δ^44/40Ca_SW record shows a general increase from ∼1.3‰ (NIST SRM 915a) at the beginning of the Ordovician to ∼2‰ at present. Superimposed on this trend is a major long-term positive excursion from the Early Carboniferous to Early Permian as well as several short-term, mostly negative, oscillations.A numerical model of the global cycles of calcium, carbon, magnesium and strontium was used to estimate whether the recorded δ^44/40Ca_SW variations can be explained by varying magnitudes of input and output fluxes of calcium to the oceans. The model uses the record of marine ⁸⁷Sr/⁸⁶Sr ratios as proxy for seafloor spreading rates, a record of oceanic Mg/Ca ratios to estimate rates of dolomite formation, and reconstructed atmospheric CO₂, discharge and erosion rates to estimate continental weathering fluxes.The model results indicate that varying magnitudes of the calcium input and output fluxes cannot explain the observed δ^44/40Ca_SW trends, suggesting that the isotope signatures of these fluxes must also have changed. As a possible mechanism we suggest variable isotope fractionation in the sedimentary output flux controlled by the dominant mineralogy in marine carbonate deposits, i.e. the oscillating ‘calcite-aragonite seas’. The ultimate control of the calcium isotope budget of the Phanerozoic oceans appears to have been tectonic processes, specifically variable rates of oceanic crust production that modulated the hydrothermal calcium flux and the oceanic Mg/Ca ratio, which in turn controlled the dominant mineralogy of marine carbonates, hence the δ^44/40Ca_SW. As to the causes of the short-term oscillations recorded in the secular δ^44/40Ca_SW trend, we tentatively propose that these are related to variable rates of dolomite formation and/or to changing chemical composition of the riverine flux, in particular and ratios, induced by variable proportions of silicate vs. carbonate weathering rates on the continents.     

<Superscript>10</Superscript>Be surface exposure dating of the last deglaciation in the Aare Valley,Switzerland

The combined Rhone and Aare Glaciers presumably reached their last glacial maximum (LGM) extent on the Swiss Plateau prior to 24 ka. Two well-preserved, less extensive moraine stades, the Gurten and Bern Stade, document the last deglaciation of the Aare Valley, yet age constraints are very scarce. In order to establish a more robust chronology for the glacial/deglacial history of the Aare Valley, we applied ¹⁰Be surface exposure dating on eleven boulders from the Gurten and Bern Stade. Several exposure ages are of Holocene age and likely document post-depositional processes, including boulder toppling and quarrying. The remaining exposure ages, however yield oldest ages of 20.7 ± 2.2 ka for the Gurten Stade and 19.0 ± 2.0 ka for the Bern Stade. Our results are in good agreement with published chronologies from other sites in the Alps.     

High spatio-temporal resolution measurements of cohesive sediment erosion

In this study, we present a novel approach to measure fundamental processes of cohesive sediment erosion. The experimental setup consists of a laboratory erosion flume (SETEG) and a photogrammetric method to detect sediment erosion (PHOTOSED). Detailed data are presented for three erosion experiments, which were conducted with a natural non-cohesive/cohesive sediment mixture at increasing sediment depths (4, 8, 16 cm). In each experiment, the sediment was exposed to a set of incrementally increasing shear stresses and the erosion was measured dynamically, pixel-based, and approximate to the process scale given the resolution of PHOTOSED. This enables us to distinguish between (i) individual emerging erosion spots caused by surface erosion and (ii) large holes torn open by detached aggregate chunks. Moreover, interrelated processes were observed, such as (iii) propagation of the erosion in the longitudinal and lateral direction leading to merging of disconnected erosion areas and (iv) progressive vertical erosion of already affected areas. By complementing the (bulk) erosion volume profiles with additional quantitative variables, which contain spatial information (erosion area, specific deepening, number of disconnected erosion areas), conclusions on the erosion behaviour (and the dominant processes) can be drawn without requiring qualitative information (such as visual observations). In addition, we provide figures indicating the spatio-temporal erosion variability and the (bulk) erosion rates for selected time periods. We evaluate the variability by statistical quantities and show that significant erosion is mainly confined to only a few events during temporal progression, but then considerably exceeds the time-averaged median of the erosion (factors between 7.0 and 16.0). Further, we point to uncertainties in using (bulk) erosion rates to assess cohesive sediment erosion and particularly the underlying processes. As a whole, the results emphasise the need to measure cohesive sediment erosion with high spatio-temporal resolution to obtain reliable and robust information. © 2020 The Authors. Earth Surface Processes and Landforms published by John Wiley & Sons Ltd     

Investigation of the ingrowth of radioactive daughters of in Mediterranean sapropels as a potential dating tool

Five different sapropels (S1, S3–S6) from two sites (2750 m and 3308 m water depth) in the eastern Mediterranean were analysed for C_org content and specific activities of , , and . Anoxia in the sapropel sediments during or shortly after deposition leads to U enrichment, and the observed excess of over activity is consistent with a seawater source for authigenic U. In certain cases, the U profile shape in and around the sappropels is interpreted to indicate that oxidation shortly after sapropel formation has caused a post-depositional downwards migration of both U isotopes. Systematic variability of the activity ratio across the sapropel units indicates that a different diagenetic process has also led to preferential relocation of produced in situ from the parent. The construction of quasi-isochrons in successively older sapropel units demonstrate that radioactive secular equilibrium is approached by a systematic ingrowth of over time from the marked initial disequilibrium between and the U isotopes. The effects of post-depositional diagenesis violate the isochron model boundary conditions, however, and lead to a deviation of the isochron ages from the expected stratigraphic ages. Following assessment of each data point, some improvements in the calculated ages were achieved in one case by exclusion from the calculations of those points most severely affected by open system behaviour.     

Biosorption of Cadmium(II) Ions by Citrus Peels in a Packed Bed Column: Effect of Process Parameters and Comparison of Different Breakthrough Curve Models

The efficiency of low cost citrus peels as biosorbents for removal of cadmium ions from aqueous solution was investigated in a fixed bed column, a process that could be applied to treat industrial wastewaters similar to commonly used ion exchange columns. Effluent concentration versus time profiles (i.e., breakthrough curves) were experimentally determined in a laboratory‐scale packed bed column for varying operational parameters such as flow rate (2, 9, and 15.5 mL/min), influent cadmium concentration (5, 10, and 15 mg/L), and bed height (24, 48, and 72 cm) at pH 5.5. Column operation was most efficient for empty bed contact times of at least 10 min, which were apparently necessary for mass transfer. While the sorption capacity was largely unaffected by operational variables, the Thomas (Th) rate constant increased with the flow rate, and slightly decreased with increasing column length. Three widely used semi‐mechanistic models (Th, Bohart–Adams, and Yoon–Nelson) were shown to be equivalent and the generalized model was compared with a two‐parameter empirical model (dose‐response). The latter was found to be able to better simulate the breakthrough curve in the region of breakthrough and saturation.     

Extreme aridity prior to lake expansion deciphered from facies evolution in the Miocene Ili Basin,south‐east Kazakhstan

Central Asia witnessed progressive aridification during the Miocene, commonly related to mountain uplift, the Paratethys retreat and global climate cooling. However, the formation of Miocene lakes in Central Asia seems to oppose drier conditions, suggesting that the precise timing, extent and forcing of the aridification is still not well constrained. This study presents a facies model for the alluvial–lacustrine part of the Middle to Late Miocene of the Ili Basin, obtained from two successions. The model enables the semi‐quantitative assessment of regional water level and salinity, and characterizes the control of water level on evaporite formation and diagenesis. Both the proximal Kendyrlisai and the distal Aktau successions show an overall increase in water availability from dry mudflat deposits to lacustrine sedimentation with a transitional playa phase. Increasing evaporation rates outpaced the water supply and caused groundwater salinization. Subsequent lake expansion coincided with a basin‐wide desalinization and required a shift to a positive water budget. A climatic control of the hydrological evolution is inferred due to abrupt salinization and a minor tectonic influence. The long‐term water accumulation is probably related to the hydrological closure of the basin in the early Middle Miocene (15·3 Ma). Starting at 14·3 Ma, the step‐wise salinization occurred simultaneously with the global cooling of the Miocene Climate Transition. The Miocene Climate Transition led to extreme aridity in the Ili Basin, highlighted by the early diagenetic formation of displacive anhydrite in the basin centre. The expansion of the freshwater lake (12·7 to 11·5 Ma) was possibly promoted by lower evaporation rates due to decreasing air temperatures in the Ili Basin after the Miocene Climate Transition. The extreme aridity in the Ili Basin is interpreted as a continental counterpart to the Badenian Salinity Crisis in the Central Paratethys. This emphasizes the role of atmospheric forcing on evaporite sedimentation across Eurasia during the Middle Miocene.     

The origin of clay minerals in active and relict hydrothermal deposits

Samples of Fe-oxide-rich hydrothermal sediments were collected from active and inactive portions of the TransAtlantic Geotraverse (TAG) hydrothermal field on the Mid-Atlantic Ridge. Clays separated from TAG metalliferous sediments in this study all consist of Al-poor nontronite. Oxygen isotope thermometry of the clays yields formation temperatures of 54-67°C for samples from the inactive Alvin mound compared with 81-96°C for samples from the active TAG site. The latter are the highest recorded temperatures for authigenic hydrothermal clays. Sr isotope analysis of the clays from the active mound suggests that they precipitated from seawater-dominated fluids, containing less than 15% hydrothermal end-member fluid. In contrast, nontronite from the inactive Alvin mound has ⁸⁷Sr/⁸⁶Sr values that closely resemble that of detrital North Atlantic clays, suggesting a dominantly continental source for the Sr. Rare earth element data are consistent with a significant detrital input to the inactive site but also demonstrate the extent of hydrothermal input to the low temperature fluid. Crystallographic fractionation of the trivalent REE is apparent in the heavy REE enrichments for all nontronite samples. The inferred formation-mechanism for nontronite-rich Fe-oxyhydroxide deposits at the surface of the active mound is by direct precipitation from low temperature fluids. At the inactive Alvin site, in contrast, the deposits form during alteration of pelagic sediments by diffuse fluids and replacement of biogenic carbonate with nontronite and Fe-oxyhydroxide. These two modes of formation are both important in seafloor hydrothermal settings where clay minerals are a significant component of the hydrothermal deposit.     

Measurement of Ambient,Interstitial, and Residual Aerosol Particles on a Mountaintop Site in Central Sweden using an Aerosol Mass Spectrometer and a CVI

The Aerodyne aerosol mass spectrometer (Q-AMS) was coupled with a counterflow virtual impactor (CVI) for the first time to measure cloud droplet residuals of warm tropospheric clouds on Mt. Åreskutan in central Sweden in July 2003. Operating the CVI in different operational modes generated mass concentration and species-resolved mass distribution data for non-refractory species of the ambient, interstitial, and residual aerosol. The ambient aerosol measurements revealed that the aerosol at the site was mainly influenced by long-range transport and regional photochemical generation of nitrate and organic aerosol components. Four different major air masses were identified for the time interval of the experiment. While two air masses that approached the site from northeastern Europe via Finland showed very similar aerosol composition, the other two air masses from polar regions and the British Islands had a significantly different composition. During cloud events the larger aerosol particles were found to be activated into cloud droplets. On a mass basis the activation cut-off diameter was approximately 150 nm for nitrate and organics dominated particles and 200 nm for sulfate dominated particles. Generally nitrate and organics were found to be activated into cloud droplets with higher efficiency than sulfate. While a significant fraction of the nitrate in ambient particles was organic nitrates or nitrogen-containing organic species, the nitrate found in the cloud droplet residuals was mainly ammonium nitrate. After passage of clouds the ambient aerosol size distribution had shifted to smaller particle sizes due to the predominantly activation of larger aerosol particles without a significant change in the relative composition of the ambient aerosol.     

Contrasting genetic diversity with phenotypic diversity in coloration and size in Xantho poressa (Brachyura: Xanthidae), with new results on its ecology

The ecology of Xantho poressa (Olivi, 1792) (Brachyura) was studied during field trips to the Mediterranean Sea, the Black Sea and the Spanish Atlantic Ocean. Our results reveal that X. poressa lives from the intertidal to the shallow subtidal zone, and inhabits relatively protected rocky shores, often with pebble underground, from juvenile to adult stages. A mark–recapture experiment revealed a high population density in this habitat. All stages, but predominantly juveniles, show a variability of colour patterns, which allow the crabs to blend in with the rocky substratum, thereby hiding from predators as passive defence. Adulthood can be reached with a carapace length smaller than 6 mm. The morphometric analysis of the species revealed allometric growth in carapace shape. Variability in overall size could be observed at different collecting sites. Neither the colour morphs nor the size differences could be attributed to differences of Cytochrome Oxidase subunit I mitochondrial DNA sequences, suggesting that ecological rather than genetic patterns are responsible for the different phenotypes.