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Phosphatized globular microfossils from the Ediacaran and Lower Cambrian of South China represent an impressive record of early animal evolution and development, however their affinity based on putative embryonic metazoan, bacterial and inorganic features is strongly debated. Understanding key processes and conditions that cause exceptional egg and embryo preservation and fossilization are therefore crucial for a reliable interpretation of their phylogenetic position. Taphonomic experiments on eggs of the marbled crayfish indicate a close link between early mineralization and rapid anaerobic decay of the endochorional envelope, producing different preservational stages of degradation resembling the various decay stages observed in the fossil record. Stabilization of the spherical morphology was achieved by pre-heating of the eggs. Complete surface mineralization occurred under reduced conditions within one to two weeks, with fine-grained brushite (CaHPO4 ⋅ 2H2O) over calcite as the dominating mineral phase. Although the endochorional envelope was not preserved, experiments resulted in exceptional preservation of the embryonic tissue at the cellular level. Thus our findings suggest that the mechanisms of decay, preservation of surface structures, and mineral replacement in the experiment and during fossilization of Cambrian embryos were likely operating at a similar rationale. [ABSTRACT FROM AUTHOR]

The accurate reconstruction of sea surface temperature (SST) history in climatesensitive regions (e.g. tropical and polar oceans) became a challenging task in palaeoceanographic research. However, biogenic shell carbonate SST proxies successfully developed for tropical regions often fail in cool water environments. Their major regional shortcomings and the cryptic diversity now found within the major high latitude proxy carrier Neogloboquadrina pachyderma (sin.) highlight an urgent need to develop complementary SST proxies for these cool water regions. Here we incorporate the genetic component into a calibration study of a new SST proxy for the high latitudes. We found that the calcium isotopic composition (δ44/40Ca) of calcite from genotyped net catches and core-top samples of the planktonic foraminifera Neogloboquadrina pachyderma (sin) is strongly related to temperature and unaffected by genetic variations. The temperature sensitivity has been found to be 0.17 (±0.04)‰ per 1°C highlighting its potential for downcore applications in open marine cool-water environments. Our results further indicate that however in extreme polar environments, below a critical threshold temperature of 2.0 (±0.5)°C and salinity of 33.0 (±0.5)‰ a prominent shift in biomineralization affect the Ca isotope composition of N. pachyderma (sin.) becoming insensitive to temperature. These findings highlight the need of systematic calibration studies to unravel the influencing factors on Ca isotope fractionation and to validate the proxies' applicability. [ABSTRACT FROM AUTHOR]

Rationale: Complete decomposition of silicate rock matrices is crucial in determining their isotopic compositions, but acid dissolution in a high-pressure steel-jacketed bomb, which has been the only powerful, effective technique thus far, is time-consuming and expensive. Rock dissolution using ammonium bifluoride (ABF), as described here, is a viable alternative., Methods: Geological reference materials (GRMs) were digested using ABF in closed Teflon beakers at temperatures of 220/230°C in a convection oven and subsequently treated with HNO 3 . Hf-Sr-Nd were separated and purified using ion-exchange chemistry columns calibrated for 50-2 mg samples. The isotopic compositions of Sr-Nd were measured by Thermal Ionization Mass Spectrometry, while that of Hf by Multi-Collector Inductively Coupled Plasma Mass Spectrometry, both with normal 10 11  Ω and gain calibrated 10 13  Ω amplifiers., Results: Total procedural blanks of our protocol are 0.5 ng for Sr, 0.2 ng for Nd and <25 pg for Hf. Test runs with GRMs, ranging in composition from basic to felsic and dissolved in ABF, yield accurate 87 Sr/ 86 Sr, 143 Nd/ 144 Nd and 176 Hf/ 177 Hf isotope ratios as compared with those obtained with the bomb dissolution technique. Reproducibilities were comparable, on the order of 10-20 ppm. Our technique allows combined Hf-Sr-Nd isotope analyses of low-mass (50-2 mg) samples., Conclusions: The ABF digestion is an alternative technique to high-pressure bomb dissolution in matrix decomposition for accurate and reproducible Hf-Nd-Sr isotope analyses of geological samples within a reasonable time (3-4 days), with high sample throughput and low costs in geochemistry and environmental sciences., (© 2021 John Wiley & Sons Ltd.)

We undertook 87 Sr/ 86 Sr analyses for a range of carbonate bearing geological reference materials, and combined these with δ 26 Mg for a subset of samples. Following chemical purification in a series of chromatographic extractions, isotope ratios were measured by Multi-Collector-ICP-MS using a Plasma II (Nu instruments, Wrexham, UK). To validate efficient sample digestion procedures of carbonate fractions, total samples were treated with either 3 mol l -1 HNO 3 and 0.5 mol l -1 HCl, respectively. Results of both leaching procedures are identical within reproducibility. Reference values for SRM 88A (formerly NBS 88A), SRM 1B (formerly NBS 1B), SARM 40, SARM 43, JDo-1, JLs-1, and San Carlos olivine range from 0.70292 to 0.73724 in 87 Sr/ 86 Sr and from -2.80 to -0.41 ‰ for δ 26 Mg, respectively. This set of geological reference materials can be used for sedimentary rock material with different carbonate mineral and matrix composition as quality control measurements of combined stable Mg and radiogenic Sr isotope analyses.•We present a protocol that facilitates the chemical separation of Mg and Sr in carbonate bearing geological reference materials including 87 Sr/ 86 Sr and δ 26 Mg of certified reference materials., (© 2020 The Author(s).)

Amorphous calcium phosphate (Ca 3 (PO 4 ) 2 xnH 2 O; n = 3-4.5; ACP) is a precursor phase of the mineral hydroxyapatite (Ca 5 (PO 4 ) 3 (OH); HAP) that in natural settings occurs during both authigenic and biogenic mineral formation. In aqueous solutions ACP transforms rapidly to the crystalline phase. The transformation rate is highly dependent on the prevailing physico-chemical conditions, most likely on: Ca & PO 4 concentration, pH and temperature. In this study, we conducted a calcium phosphate precipitation experiment at 20 °C and pH 9.2, in order to study the temporal evolution of the phosphate mineralogy. We monitored and assessed the transformation process of ACP to crystalline HAP using highly time-resolved in-situ Raman spectroscopy at 100 spectra per hour, in combination with solution chemistry and XRD data. Transformation of ACP to crystalline HAP occurred within 18 h, as it is illustrated in a clear peak shift in Raman spectra from 950 cm -1 to 960 cm -1 as well as in a sharpening of the 960 cm -1 peak. The advantages of this method are: •In-situ Raman spectroscopy facilitates quasi - continuous monitoring of phase transitions.•It is an easy to handle and non-invasive method.

In this contribution, we present the synthesis and characterization of the mixed-anion halogenobismuthate(III) (CH 3 NH 3 ) 6 BiI 5.22 Cl 3.78 (MBIC) as an alternative lead-free perovskite-type semiconductor, and discuss its optical, electronic, and photovoltaic properties in comparison to the methylammonium bismuth iodide (CH 3 NH 3 ) 3 Bi 2 I 9 (MBI) compound. The exchange of iodide with chloride during synthesis leads to the formation of an orthorhombic A 6 BX 9 -type crystal structure ( Cmma, No. 67) with isolated BiX 6 octahedra and methylammonium chloride interlayers. The experimentally found optical indirect band gap of 2.25 eV is in good agreement with the calculated value of 2.50 eV derived from DFT simulations. The valence band maximum and the conduction band minimum were determined to be at -6.2 eV and -4.0 eV vs vacuum. Similar to MBI, thin films of MBIC are composed of microcrystalline platelets. Time-resolved photoluminescence measurements show electron transfer of MBIC to mesoporous TiO 2 . The photovoltaic behavior of both compounds is compared in solar cells with the following device architecture: glass/ITO/compact TiO 2 /mesoporous TiO 2 /MBIC or MBI/spiro-OMeTAD/Au. Despite the zero-dimensional structure of MBIC, a maximum power conversion efficiency of 0.18% and a high fill factor of almost 60% were obtained with this material as absorber layer. When stored under inert conditions, these solar cells show an excellent long-term stability over the investigated period of more than 700 days.

The Cambrian explosion, the rapid appearance of most animal phyla in the geological record, occurred concurrently with bottom seawater oxygenation. Whether this oxygenation event was triggered through enhanced nutrient supply and organic carbon burial forced by increased continental weathering, or by species engaging in ecosystem engineering, remains a fundamental yet unresolved question. Here we provide evidence for several simultaneous developments that took place over the Ediacaran-Cambrian transition: expansion of siliceous sponges, decrease of the dissolved organic carbon pool, enhanced organic carbon burial, increased phosphorus removal and seawater oxygenation. This evidence is based on silicon and carbon stable isotopes, Ge/Si ratios, REE-geochemistry and redox-sensitive elements in a chert-shale succession from the Yangtze Platform, China. According to this reconstruction, sponges have initiated seawater oxygenation by redistributing organic carbon oxidation through filtering suspended organic matter from seawater. The resulting increase in dissolved oxygen levels potentially triggered the diversification of eumetazoans.The Ediacaran-Cambrian oxygenation of seawater is thought to have been caused by lifeforms engaging in ecosystem engineering. Here, the authors show that siliceous sponges increased seawater dissolved oxygen concentrations by redistributing organic carbon oxidation through filtering suspended organic matter.