A robust heterogeneous chiral phosphoric acid enables multi decagram scale production of optically active N,S-ketals.

Asymmetric organocatalysis has been recognized as one of the "top 10 emerging technologies" in chemistry by IUPAC in 2019. Its potential to make chemical processes more sustainable is promising, but there are still challenges that need to be addressed. Developing new and reliable enantioselective processes for reproducing batch reactions on a large scale requires a combination of chemical and technical solutions. In this manuscript, we combine a robust immobilized chiral phosphoric acid with a new packed-bed reactor design. This combination allows scaling up of the enantioselective addition of thiols to imines from a few milligrams to a multi-decagram scale in a continuous flow process without physical or chemical degradation of the catalyst.

Warm, not cold temperatures contributed to a Late Miocene reef decline in the Coral Sea.

Evidence shows that in the modern ocean, coral reefs are disappearing, and these losses are tied to climate change. However, research also shows that coral reefs can adapt rapidly to changing conditions leading some researchers to suggest that some reef systems will survive future climate change through adaptation. It is known that there were changes in the area covered by coral reefs in the past. Therefore, it is important to investigate the long-term response of coral reefs to environmental changes and high sea-surface temperatures (SSTs). However, because of diagenetic issues with SST proxies in neritic, metastable carbonate-rich environments, there is an incomplete and sometimes even incorrect understanding of how changes in SSTs affect carbonate reef systems. A good example is the Queensland Plateau offshore northeast Australia next to the threatened Great Barrier Reef. In the Late Miocene, between 11 and 7 Ma, a partial drowning caused the reef area on the Queensland Plateau to decline by ~ 50% leading to a Late Miocene change in platform geometry from a reef rimmed platform to a carbonate ramp. This reef decline was interpreted to be the result of SSTs at the lower limit of the modern reef growth window (20-18 °C). This article presents a new Late Miocene-ased SST record from the Coral Sea based on the TEX86H molecular paleothermometer, challenging this long held view. Our new record indicates warm tropical SSTs (27-32 °C) at the upper end of the modern reef growth window. We suggest that the observed temperatures potentially exceeded the optimal calcification temperatures of corals. In combination with a low aragonite supersaturation in the ocean, this could have reduced coral growth rates and ultimately lowered the aggradation potential of the reef system. These sub-optimal growth rates could have made the coral reefs more susceptible to other stressors, such as relative sea-level rise and/or changes in currents leading to reef drowning. Given that these changes affected coral reefs that were likely adapted to high temperature/low aragonite saturation conditions suggests that reefs that have adapted to non-ideal conditions may still be susceptible to future climate changes due to the interaction of multiple stressors associated with climate change.

Foraminifera assemblages from Fantangisña serpentinite mud seamount in the NW Pacific Ocean during the Pleistocene (IODP Expedition 366).

The Mariana forearc system, in the northwestern Pacific, is known as the only convergent margin setting with currently active serpentine mud volcanism. The Fantangisña serpentinite mud volcano lies 62 km west of the Mariana trench, within the influence of the North Equatorial Current (NEC). Cores recovered by International Ocean Discovery Program (IODP) Expedition 366 contain pelagic sediments overlying layered serpentinite mud deposits. At the bottom of the sequence, nannofossil-rich forearc deposits were recovered from under the seamount edifice. In this study, we investigated 47 samples from Site U1498A on the southern flank of the seamount for benthic and planktonic foraminifera assemblages. Statistical analyses on planktonic assemblages differentiated two sample groups related to the ratio between thermocline/mixed layer taxa, which indicate fluctuations in the depth of the thermocline (DOT) during the Pleistocene. Variations in the DOT reflect changes in the intensity of the NEC associated with El Niño/La Niña conditions. Mudflows do not influence the ecology of planktonic foraminifera but possibly enhance their preservation against dissolution, which was instead detected in the pelagic deposit as suggested by common Globigerinoides conglobatus. Benthic foraminifers were rare in serpentinite mud deposits as they are severely affected by mudflows. Conversely, they showed high diversity pre-/post-mud-volcanism, and indicate oligotrophic bottom-water conditions.

Marine facies differentiation along complex paleotopography: an example from the Middle Miocene (Serravallian) of Lower Austria.

In the area of Bad Deutsch-Altenburg (Hainburg Mountains, Lower Austria) a Middle Miocene transgression over Mesozoic basement was explored in the course of the Danube power plant project "Hainburg". The Mesozoic basement forms a narrow ridge dipping to the northeast towards the Vienna Basin, covered by various Miocene sediments. The ridge represents a specific paleotopography that required a detailed study with 78 shallow, fully cored drill holes in an area of c. 0.5 km2. Ten drillings were selected for this study based on sedimentary composition and position relative to the Mesozoic ridge. These 10 cores, ranging in drilling depth from 26.5 to 96.4 m, were studied in respect to sedimentology, corallinacean algae, calcareous nannoplankton, foraminifers and ostracodes to reconstruct sediment distribution and paleoenvironment. Sediment distribution clearly shows that the Mesozoic ridge formed a physical barrier with siliciclastics dominating in the SW of the ridge and carbonate sediments prevailing in the NE. Based on biostratigraphy (calcareous nannoplankton, foraminifera, ostracodes, dinoflagellates) the majority of the sediments can be dated to the late Badenian (early Serravallian) only in some drillholes lower Sarmatian (upper Serravallian) sediments were detected. In terms of sequence stratigraphy, the Badenian sediments represent the transgressive and highstand systems tract of 3rd order sequence TB 2.5 (bound by the lowstands Ser 2 and Ser 3), the lower Sarmatian sediments can be correlated to sequence TB 2.6. Carbonate sediments show a wide spectrum of 13 facies which are mostly dominated by coralline algae. According to the relative positions of the drill holes a water depth between 0 and about 50 m can be reconstructed what is supported by the occurrence of the benthic biota. This biota indicates that the sedimentary succession started from the very beginning under full marine conditions. Except of basal conglomerates/breccias water energy conditions were low and turbidity high. Close to the Sarmatian boundary a reduction in salinity and depth may have occurred which is also observed in the Sarmatian sediments. Carbonate sediments and, in particular, larger benthic foraminifers indicate tropical to warm-temperate conditions for the late Badenian of the studied sections. The siliciclastic sediments NW of the Mesozoic ridge reflect riverine input indicated by the occurrence of freshwater ostracodes and characean oogonias. Calcareous nannoplankton and dinoflagellates show a high share of reworking from Upper Cretaceaous and Paleogene sediments. Supplementary Information: The online version contains supplementary material available at 10.1186/s00015-022-00425-w.

Nanocrystals as phenotypic expression of genotypes-An example in coralline red algae.

Coralline red algae (CRA) are important ecosystem engineers in the world's oceans. They play key roles as primary food source and carbonate producers in marine habitats. CRA are also vital for modern reef systems where they act as substrate for coral growth and stabilizers of reef frameworks. However, morphotaxonomic identification of these important marine organisms is hampered by the fact that morphological concepts used for their classification do not correspond to molecular data. We present the first analysis of nanoscale features in calcified cell walls of CRA in a globally distributed sample set. We use new morphological traits based on these cell wall ultrastructures to construct an independent morphological phyletic tree that shows a promising congruency with existing CRA molecular phylogenies. Our results highlight cellular ultrastructures as a tool to define the phenotypic expression of genotypic information showing their potential to unify morphology with molecular phylogeny.

Glacial Indonesian Throughflow weakening across the Mid-Pleistocene Climatic Transition.

The Indonesian Throughflow (ITF) controls the oceanic flux of heat and salt between the Pacific and Indian Oceans and therewith plays an important role in modulating the meridional overturning circulation and low latitude hydrological cycle. Here, we report new sea surface temperature and aridity records from the west coast of Australia (IODP Site U1460), which allow us to assess the sensitivity of the eastern Indian Ocean to the major reorganization of Earth's climate that occurred during the Mid-Pleistocene Transition. Our records indicate glacial coolings at 1.55 and 0.65 million years ago that are best explained by a weakening of the ITF as a consequence of global sea level and tectonic changes. These coincide with the development of pronounced gradients in the carbon isotope composition of the different ocean basins and with substantial changes in regional aridity, suggesting that the restrictions of the ITF influenced both the evolution of global ocean circulation and the development of the modern hydrological cycle in Western Australia.

Australian shelf sediments reveal shifts in Miocene Southern Hemisphere westerlies.

Global climate underwent a major reorganization when the Antarctic ice sheet expanded ~14 million years ago (Ma) (1). This event affected global atmospheric circulation, including the strength and position of the westerlies and the Intertropical Convergence Zone (ITCZ), and, therefore, precipitation patterns (2-5). We present new shallow-marine sediment records from the continental shelf of Australia (International Ocean Discovery Program Sites U1459 and U1464) providing the first empirical evidence linking high-latitude cooling around Antarctica to climate change in the (sub)tropics during the Miocene. We show that Western Australia was arid during most of the Middle Miocene. Southwest Australia became wetter during the Late Miocene, creating a climate gradient with the arid interior, whereas northwest Australia remained arid throughout. Precipitation and river runoff in southwest Australia gradually increased from 12 to 8 Ma, which we relate to a northward migration or intensification of the westerlies possibly due to increased sea ice in the Southern Ocean (5). Abrupt aridification indicates that the westerlies shifted back to a position south of Australia after 8 Ma. Our midlatitude Southern Hemisphere data are consistent with the inference that expansion of sea ice around Antarctica resulted in a northward movement of the westerlies. In turn, this may have pushed tropical atmospheric circulation and the ITCZ northward, shifting the main precipitation belt over large parts of Southeast Asia (4).

Orbitally paced phosphogenesis in Mediterranean shallow marine carbonates during the middle Miocene Monterey event.

During the Oligo-Miocene, major phases of phosphogenesis occurred in the Earth's oceans. However, most phosphate deposits represent condensed or allochthonous hemipelagic deposits, formed by complex physical and chemical enrichment processes, limiting their applicability for the study regarding the temporal pacing of Miocene phosphogenesis. The Oligo-Miocene Decontra section located on the Maiella Platform (central Apennines, Italy) is a widely continuous carbonate succession deposited in a mostly middle to outer neritic setting. Of particular interest are the well-winnowed grain to packstones of the middle Miocene Bryozoan Limestone, where occurrences of authigenic phosphate grains coincide with the prominent carbon isotope excursion of the Monterey event. This unique setting allows the analysis of orbital forcing on phosphogenesis, within a bio, chemo, and cyclostratigraphically constrained age-model. LA-ICP-MS analyses revealed a significant enrichment of uranium in the studied authigenic phosphates compared to the surrounding carbonates, allowing natural gamma-radiation (GR) to be used as a qualitative proxy for autochthonous phosphate content. Time series analyses indicate a strong 405 kyr eccentricity forcing of GR in the Bryozoan Limestone. These results link maxima in the GR record and thus phosphate content to orbitally paced increases in the burial of organic carbon, particularly during the carbon isotope maxima of the Monterey event. Thus, phosphogenesis during the middle Miocene in the Mediterranean was controlled by the 405 kyr eccentricity and its influence on large-scale paleoproductivity patterns. Rare earth element data were used as a tool to reconstruct the formation conditions of the investigated phosphates, indicating generally oxic formation conditions, which are consistent with microbially mediated phosphogenesis.

Correlating carbon and oxygen isotope events in early to middle Miocene shallow marine carbonates in the Mediterranean region using orbitally tuned chemostratigraphy and lithostratigraphy.

During the Miocene prominent oxygen isotope events (Mi-events) reflect major changes in glaciation, while carbonate isotope maxima (CM-events) reflect changes in organic carbon burial, particularly during the Monterey carbon isotope excursion. However, despite their importance to the global climate history they have never been recorded in shallow marine carbonate successions. The Decontra section on the Maiella Platform (central Apennines, Italy), however, allows to resolve them for the first time in such a setting during the early to middle Miocene. The present study improves the stratigraphic resolution of parts of the Decontra section via orbital tuning of high-resolution gamma ray (GR) and magnetic susceptibility data to the 405 kyr eccentricity metronome. The tuning allows, within the established biostratigraphic, sequence stratigraphic, and isotope stratigraphic frameworks, a precise correlation of the Decontra section with pelagic records of the Mediterranean region, as well as the global paleoclimatic record and the global sea level curve. Spectral series analyses of GR data further indicate that the 405 kyr orbital cycle is particularly well preserved during the Monterey Event. Since GR is a direct proxy for authigenic uranium precipitation during increased burial of organic carbon in the Decontra section, it follows the same long-term orbital pacing as observed in the carbon isotope records. The 405 kyr GR beat is thus correlated with the carbon isotope maxima observed during the Monterey Event. Finally, the Mi-events can now be recognized in the δ18O record and coincide with plankton-rich, siliceous, or phosphatic horizons in the lithology of the section.

High-resolution calcareous nannoplankton palaeoecology as a proxy for small-scale environmental changes in the Early Miocene.

Within a 5.5-m-thick succession of upper Burdigalian (CNP-zone NN4) shallow neritic sediments from the North Alpine Foreland Basin in Lower Austria a high-resolution section of finely laminated sediment with a thickness of 940.5 mm was logged. The section was continuously sampled, resulting in 100 samples, covering a thickness of ~ 10 mm each. An integrated approach was applied to these samples in order to study proxy records including calcareous nannoplankton, geochemical and geophysical data. Multivariate statistics on the autochthonous assemblage were used to evaluate the ecological preferences of each taxon and to rule out possible contamination of the signal by taphonomic processes. In order to assess changes in the assemblage composition throughout the section, three taphogroups were defined using both the autochthonous and allochthonous nannofossils. Based on the distribution of these taphogroups five distinct intervals were defined that are indicative of centennial to decadal changes in palaeoenvironmental conditions. Combining these results with other proxies (geochemistry, geophysics) we were able to reconstruct short-term, small-scale variations in terms of temperature, primary productivity, bottom water oxygenation, organic matter flux, freshwater influx and changes in relative sea level in a highly dynamic shallow marine setting. This study represents the first such high-resolution analysis performed on a marine succession of late Burdigalian age. It is also a first attempt to analyse outcrop data on such a high-resolution, sub-Milankovitch scale, with respect to calcareous nannoplankton in conjunction with geochemical and sedimentological data.