Refining the interpretation of lacustrine carbonate isotope records: Implications of a mineralogy-specific Lake Van case study

Oxygen and carbon isotope (δ18O and δ13C) data from bulk carbonates are widely applied proxies for temperature, the precipitation/evaporation ratio and productivity in lacustrine palaeohydrology and palaeoclimatology. In case of the terminal and alkaline Lake Van, however, previous studies have shown that bulk oxygen isotope compositions are in disagreement with other proxies when interpreted in a conventional manner. Similarly, the reports on the nature and the timing and site of carbonate precipitation in Lake Van are inconsistent. This study provides evidence on the mineralogy (X-ray powder diffraction analysis, scanning electron microscope imaging, confocal Raman microscopy, electron microprobe analysis) and isotope composition (δ18O and δ13C) of non-skeletal carbonate minerals in a Lake Van sedimentary profile spanning the last ca. 150 kyr. Carbonate phases present in the sediment include aragonite, low-Mg calcite, and calcian dolomite. Dolomite forms as an early diagenetic phase and occurs episodically in high concentrations driving the bulk isotope record towards the higher dolomite δ18O and varying δ13C values. Aragonite and low-Mg calcite precipitate in the surface water and are present in the sediments in varying amounts (relative aragonite to calcite content for dolomite-poor samples Ar/(Ar + Cc) of 93 to 41 wt%). In an attempt to explain this variation, we revised a precipitation model based on annually laminated sediments containing both aragonite and calcite spatially separated in light and dark coloured laminae, respectively. According to our model, spring calcite precipitation, under close-to-freshwater conditions, is followed by evapoconcentration-driven aragonite precipitation in late summer. The precipitation of these carbonate polymorphs from chemically differing surface waters (i.e. freshwater-influenced and evapoconcentrated) leads to distinctly different oxygen and carbon isotope signatures between sedimentary penecontemporaneous aragonite and calcite. The δ18O and δ13C values of aragonite relative to calcite are significantly higher by several per mille than inferred from aragonite-calcite fractionation factors alone, suggesting that the generalised assumption of sedimentary coeval calcite and aragonite precipitating from water with the same isotopic composition is flawed. The here proposed revised hydrologically-separated carbonate precipitation model is not only taking (i) differences in the isotopic fractionation between carbonate minerals into account, but also (ii) considering the hydrological conditions and the processes favouring the precipitation of a given mineral and ultimately controlling its isotopic composition. If mixed mineralogies are present, this mineralogy-specific approach has the potential of refining environmental reconstructions and reconciling apparently equivocal interpretations of different proxy records

Laboratory study on coprecipitation of phosphate with ikaite in sea ice

Ikaite (CaCO3�6H2O) has recently been discovered in sea ice, providing first direct evidence of CaCO3 precipitation in sea ice. However, the impact of ikaite precipitation on phosphate (PO4) concentration has not been considered so far. Experiments were set up at pH from 8.5 to 10.0, salinities from 0 to 105, temperatures from 24°C to 0°C, and PO4 concentrations from 5 to 50 mmol kg-1 in artificial sea ice brine so as to understand how ikaite precipitation affects the PO4 concentration in sea ice under different conditions. Our results show that PO4 is coprecipitated with ikaite under all experimental conditions. The amount of PO4 removed by ikaite precipitation increases with increasing pH. Changes in salinity (S >=35) as well as temperature have little impact on PO4 removal by ikaite precipitation. The initial PO4 concentration affects the PO4 coprecipitation. These findings may shed some light on the observed variability of PO4 concentration in sea ice

EMP and SIMS studies on Mn/Ca and Fe/Ca systematics in benthic foraminifera from the Peruvian OMZ: a contribution to the identification of potential redox proxies and the impact of cleaning protocols

In this study we present an initial dataset of Mn/Ca and Fe/Ca ratios in tests of benthic foraminifera from the Peruvian oxygen minimum zone (OMZ) determined with SIMS. These results are a contribution to a better understanding of the proxy potential of these elemental ratios for ambient redox conditions. Foraminiferal tests are often contaminated by diagenetic coatings, like Mn rich carbonate- or Fe and Mn rich (oxyhydr)oxide coatings. Thus, it is substantial to assure that the cleaning protocols are efficient or that spots chosen for microanalyses are free of contaminants. Prior to the determination of the element/Ca ratios, the distributions of several elements (Ca, Mn, Fe, Mg, Ba, Al, Si, P and S) in tests of the shallow infaunal species Uvigerina peregrina and Bolivina spissa were mapped with an electron microprobe (EMP). To visualize the effects of cleaning protocols uncleaned and cleaned specimens were compared. The cleaning protocol included an oxidative cleaning step. An Fe rich phase was found on the inner test surface of uncleaned U. peregrina specimens. This phase was also enriched in Al, Si, P and S. A similar Fe rich phase was found at the inner test surface of B. spissa. Specimens of both species treated with oxidative cleaning show the absence of this phase. Neither in B. spissa nor in U. peregrina were any hints found for diagenetic (oxyhydr)oxide or carbonate coatings. Mn/Ca and Fe/Ca ratios of single specimens of B. spissa from different locations have been determined by secondary ion mass spectrometry (SIMS). Bulk analyses using solution ICP-MS of several samples were compared to the SIMS data. The difference between SIMS analyses and ICP-MS bulk analyses from the same sampling sites was 14.0–134.8 μmol mol−1 for the Fe/Ca and 1.68(±0.41) μmol mol−1 for the Mn/Ca ratios. This is in the same order of magnitude as the variability inside single specimens determined with SIMS at these sampling sites (1σ[Mn/Ca] = 0.35–2.07 μmol mol−1; 1σ[Fe/Ca] = 93.9–188.4 μmol mol−1). The Mn/Ca ratios in the calcite were generally relatively low (2.21–9.93 μmol mol−1) but in the same magnitude and proportional to the surrounding pore waters (1.37–6.67 μmol mol−1). However, the Fe/Ca ratios in B. spissa show a negative correlation to the concentrations in the surrounding pore waters. Lowest foraminiferal Fe/Ca ratios (87.0–101.0 μmol mol−1) were found at 465 m water depth, a location with a strong sharp Fe peak in the pore water next to the sediment surface and respectively, high Fe concentrations in the surrounding pore waters. Previous studies found no living specimens of B. spissa at this location. All these facts hint that the analysed specimens already were dead before the Fe flux started and the sampling site just recently turned anoxic due to fluctuations of the lower boundary of the OMZ near the sampling site (465 m water depth). Summarized Mn/Ca and Fe/Ca ratios are potential proxies for redox conditions, if cleaning protocols are carefully applied. The data presented here may be rated as base for the still pending detailed calibration

Anomalous magnetic ordering in PrBa_2Cu_3O_{7-y} single crystals: Evidence for magnetic coupling between the Cu and Pr sublattices

In Al-free PrBa_2Cu_3O_{7-y} single crystals the kink in the temperature dependence of magnetic susceptibility chi_{ab}(T), connected with Pr antiferromagnetic ordering, disappears after field cooling (FC) in a field H || ab-plane. The kink in chi_c(T) remains unchanged after FC in H || c-axis. As a possible explanation, freezing of the Cu magnetic moments, lying in the ab-plane, caused by FC in H || ab, hinders their reorientation and, due to coupling between the Pr and Cu(2) sublattices, ordering of the Pr^{3+} moments. A field induced phase transition and a field dependence of the Pr^{3+} ordering temperature have been found for both H || c and H || ab.Comment: 11 pages (LaTex with elsart.sty), 5 EPS figs. Accepted to Physica

Endolithic Algae Affect Modern Coral Carbonate Morphology and Chemistry

While burial diagenetic processes of tropical corals are well investigated, current knowledge about factors initiating early diagenesis remains fragmentary. In the present study, we focus on recent Porites microatolls, growing in the intertidal zone. This growth form represents a model organism for elevated sea surface temperatures (SSTs) and provides important but rare archives for changes close to the seawater/atmosphere interface with exceptional precision on sea level reconstruction. As other coral growth forms, microatolls are prone to the colonization by endolithic green algae. In this case, the algae can facilitate earliest diagenetic alteration of the coral skeleton. Algae metabolic activity not only results in secondary coral porosity due to boring activities, but may also initiate reprecipitation of secondary aragonite within coral pore space, a process not exclusively restricted to microatoll settings. In the samples of this initial study, we quantified a mass transfer from primary to secondary aragonite of around 4% within endolithic green algae bands. Using δ 18 O, δ 13 C, Sr/Ca, U/Ca, Mg/Ca, and Li/Mg systematics suggests that the secondary aragonite precipitation followed abiotic precipitation principles. According to their individual distribution coefficients, the different isotope and element ratios showed variable sensitivity to the presence of secondary aragonite in bulk samples, with implications for microatoll-based SST reconstructions. The secondary precipitates formed on an organic template, presumably originating from endolithic green algae activity. Based on laboratory experiments with the green algae Ostreobium quekettii, we propose a conceptual model that secondary aragonite formation is potentially accelerated by an active intracellular calcium transport through the algal thallus from the location of dissolution into coral pore spaces. The combined high-resolution imaging and geochemical approach applied in this study shows that endolithic algae can possibly act as a main driver for earliest diagenesis of coral aragonite starting already during a coral’s life span

Distinct roles for two Caenorhabditis elegans acid-sensing ion channels in an ultradian clock

Biological clocks are fundamental to an organism’s health, controlling periodicity of behaviour and metabolism. Here, we identify two acid-sensing ion channels, with very different proton sensing properties, and describe their role in an ultradian clock, the defecation motor program (DMP) of the nematode Caenorhabditis elegans. An ACD-5-containing channel, on the apical membrane of the intestinal epithelium, is essential for maintenance of luminal acidity, and thus the rhythmic oscillations in lumen pH. In contrast, the second channel, composed of FLR-1, ACD-3 and/or DEL-5, located on the basolateral membrane, controls the intracellular Ca2+ wave and forms a core component of the master oscillator that controls the timing and rhythmicity of the DMP. flr-1 and acd-3/del-5 mutants show severe developmental and metabolic defects. We thus directly link the proton-sensing properties of these channels to their physiological roles in pH regulation and Ca2+ signalling, the generation of an ultradian oscillator, and its metabolic consequences