Design and optimization of electrochemical microreactors for continuous electrosynthesis

The study focuses on the design and construction, as well as the theoretical and experimental optimization of electrochemical filter press microreactors for the electrosynthesis of molecules with a high added value. The main characteristics of these devices are firstly a high-specific electrochemical area to increase conversion and selectivity, and secondly the shape and size of themicrochannels designed for a uniform residence time distribution of the fluid. A heat exchanger is integrated into the microstructured electrode to rapidly remove (or supply) the heat required in exo- or endothermic reactions. The microreactors designed are used to perform-specific electrosynthesis reactions such as thermodynamically unfavorable reactions (continuous NADH regeneration), or reactions with high enthalpy changes

A reference time scale for Site U1385 (Shackleton Site) on the SW Iberian Margin

Weproduced a composite depth scale and chronology for Site U1385 on the SWIberianMargin. Using log(Ca/Ti)measured by core scanning XRF at 1-cm resolution in all holes, a composite section was constructed to166.5 meter composite depth (mcd) that corrects for stretching and squeezing in each core. Oxygen isotopesof benthic foraminifera were correlated to a stacked d18O reference signal (LR04) to produce an oxygen isotopestratigraphy and age model.Variations in sediment color contain very strong precession signals at Site U1385, and the amplitude modulationof these cycles provides a powerful tool for developing an orbitally-tuned agemodel.We tuned the U1385 recordby correlating peaks in L* to the local summer insolation maxima at 37°N. The benthic d18O record of Site U1385,when placed on the tuned agemodel, generally agrees with other time scaleswithin their respective chronologicuncertainties.The age model is transferred to down-core data to produce a continuous time series of log(Ca/Ti) that reflectrelative changes of biogenic carbonate and detrital sediment. Biogenic carbonate increases during interglacialand interstadial climate states and decreases during glacial and stadial periods. Much of the variance in thelog(Ca/Ti) is explained by a linear combination of orbital frequencies (precession, tilt and eccentricity), whereasthe residual signal reflects suborbital climate variability. The strong correlation between suborbital log(Ca/Ti)variability and Greenland temperature over the last glacial cycle at Site U1385 suggests that this signal can beused as a proxy for millennial-scale climate variability over the past 1.5 Ma.Millennial climate variability, as expressed by log(Ca/Ti) at Site U1385, was a persistent feature of glacial climatesover the past 1.5Ma, including glacial periods of the early Pleistocene (‘41-kyrworld’)when boundary conditionsdiffered significantly from those of the late Pleistocene (‘100-kyr world’). Suborbital variability was suppressedduring interglacial stages and enhanced during glacial periods, especially when benthic d18O surpassed ~3.3–3.5‰. Each glacial inception was marked by appearance of strong millennial variability and each deglaciatio

Steppes, savannahs, forests and phytodiversity reservoirs during the Pleistocene in the Iberian Peninsula

A palaeobotanical analysis of the Pleistocene floras and vegetation in the Iberian Peninsula shows the existence of patched landscapes with Pinus woodlands, deciduous and mixed forests, parklands (savannah-like), shrublands, steppes and grasslands. Extinctions of Arctotertiary woody taxa are recorded during the Early and Middle Pleistocene, but glacial refugia facilitated the survival of a number of temperate, Mediterranean and Ibero-North African woody angiosperms. The responses of Iberian vegetation to climatic changes during the Pleistocene have been spatially and temporarily complex, including rapid changes of vegetation in parallel to orbital and suborbital variability, and situations of multi-centennial resilience or accommodation to climatic changes. Regional characteristics emerged as soon as for the Middle Pleistocene, if not earlier: Ericaceae in the Atlantic coast indicating wetter climate, thermo-mediterranean elements in the south as currently, and broad-leaf trees in the northeastern. Overall, steppe landscapes and open Pinus woodlands prevailed over many continental regions during the cold spells of the Late Pleistocene. The maintenance of a high phytodiversity during the glacials was linked to several refuge zones in the coastal shelves of the Mediterranean and intramountainous valleys. Northern Iberia, especially on coastal areas, was also patched with populations of tree species, and this is not only documented by palaeobotanical data (pollen, charcoal) but also postulated by phylogeographical models

Modern relationships between microscopic charcoal in marine sediments and fire regimes on adjacent landmasses to refine the interpretation of marine paleofire records: An Iberian case study

Marine microcharcoal records provide invaluable information to understand changes in biomass burning and its drivers over multiple glacial and interglacial cycles and to evaluate fire models under warmer climates than today. However, quantitative reconstructions of burnt area, fire intensity and frequency from these records need calibration studies of the current fire-microcharcoal relationship. Here, we present the analysis of microcharcoal concentration and morphology in 102 core-top sediment samples collected in the Iberian margin and the Gulf of Cádiz. We show that microcharcoal concentrations are influenced by the water depth or the distance from the river mouth. At regional scale, the mean microcharcoal concentrations and microcharcoal elongation (length to width ratio) show a marked latitudinal variation in their distribution, primarily controlled by the type of burnt vegetation in the adjacent continent. High microcharcoal concentrations in marine sediments represent rare, large and intense fires in open Mediterranean woodlands. Based on these results, the increasing trend of microcharcoal concentrations recorded since 8 ka in the well-known marine sedimentary core MD95-2042 off the Iberian margin indicates the occurrence of large and infrequent fires of high intensity due to the progressive degradation of the Mediterranean forest and the expansion of shrublands

Unraveling the forcings controlling the vegetation and climate of the best orbital analogues for the present interglacial in SW Europe

The suitability of MIS 11c and MIS 19c as analogues of our present interglacial and its natural evolution is still debated. Here we examine the regional expression of the Holocene and its orbital analogues over SW Iberia using a model-data comparison approach. Regional tree fraction and climate based on snapshot and transient experiments using the LOVECLIM model are evaluated against the terrestrial-marine profiles from Site U1385 documenting the regional vegetation and climatic changes. The pollen-based reconstructions show a larger forest optimum during the Holocene compared to MIS 11c and MIS 19c, putting into question their analogy in SW Europe. Pollen-based and model results indicate reduced MIS 11c forest cover compared to the Holocene primarily driven by lower winter precipitation, which is critical for Mediterranean forest development. Decreased precipitation was possibly induced by the amplified MIS 11c latitudinal insolation and temperature gradient that shifted the westerlies northwards. In contrast, the reconstructed lower forest optimum at MIS 19c is not reproduced by the simulations probably due to the lack of Eurasian ice sheets and its related feedbacks in the model. Transient experiments with time-varying insolation and CO2 reveal that the SW Iberian forest dynamics over the interglacials are mostly coupled to changes in winter precipitation mainly controlled by precession, CO2 playing a negligible role. Model simulations reproduce the observed persistent vegetation changes at millennial time scales in SW Iberia and the strong forest reductions marking the end of the interglacial "optimum".SFRH/BD/9079/2012, SFRH/BPD/108712/2015, SFRH/BPD/108600/2015info:eu-repo/semantics/publishedVersio

Late Holocene climate: Natural or anthropogenic?

For more than a decade, scientists have argued about the warmth of the current interglaciation. Was the warmth of the preindustrial late Holocene natural in origin, the result of orbital changes that had not yet driven the system into a new glacial state? Or was it in considerable degree the result of humans intervening in the climate system through greenhouse gas emissions from early agriculture? Here we summarize new evidence that moves this debate forward by testing both hypotheses. By comparing late Holocene responses to those that occurred during previous interglaciations (in section 2), we assess whether the late Holocene responses look different (and thus anthropogenic) or similar (and thus natural). This comparison reveals anomalous (anthropogenic) signals. In section 3, we review paleoecological and archaeological syntheses that provide ground truth evidence on early anthropogenic releases of greenhouse gases. The available data document large early anthropogenic emissions consistent with the anthropogenic ice core anomalies, but more information is needed to constrain their size. A final section compares natural and anthropogenic interpretations of the δ13C trend in ice core CO2

Extending the tephra and palaeoenvironmental record of the Central Mediterranean back to 430 ka: A new core from Fucino Basin, central Italy

Here we present the first tephrostratigraphic, palaeomagnetic, and multiproxy data from a new ∼98 m-deep sediment core retrieved from the Fucino Basin, central Italy, spanning the last ∼430 kyr. Palaeoenvironmental proxy data (Ca-XRF, gamma ray and magnetic susceptibility) show a cyclical variability related to interglacial-glacial cycles since the Marine Isotope Stage (MIS) 12-MIS 11 transition. More than 130 tephra layers are visible to the naked eye, 11 of which were analysed (glass-WDS) and successfully correlated to known eruptions and/or other equivalent tephra. In addition to tephra already recognised in the previously investigated cores spanning the last 190 kyr, we identified for the first time tephra from the eruptions of: Tufo Giallo di Sacrofano, Sabatini (288.0 ± 2.0 ka); Villa Senni, Colli Albani (367.5 ± 1.6 ka); Pozzolane Nere and its precursor, Colli Albani (405.0 ± 2.0 ka, and 407.1 ± 4.2 ka, respectively) and Castel Broco, Vulsini (419–490 ka). The latter occurs at the bottom of the core and has been 40Ar/39Ar dated at 424.3 ± 3.2 ka, thus providing a robust chronological constrain for both the eruption itself and the base of the investigated succession. Direct 40Ar/39Ar dating and tephra geochemical fingerprinting provide a preliminary radioisotopic-based chronological framework for the MIS 11-MIS 7 interval, which represent a foundation for the forthcoming multiproxy studies and for investigating the remaining ∼110 tephra layers that are recorded within this interval. Such future developments will contribute towards an improved MIS 11-MIS 7 Mediterranean tephrostratigraphy, which is still poorly explored and exploited

Enhanced climate instability in the North Atlantic and southern Europe during the Last Interglacial

Considerable ambiguity remains over the extent and nature of millennial/centennial-scale climate instability during the Last Interglacial (LIG). Here we analyse marine and terrestrial proxies from a deep-sea sediment sequence on the Portuguese Margin and combine results with an intensively dated Italian speleothem record and climate-model experiments. The strongest expression of climate variability occurred during the transitions into and out of the LIG. Our records also document a series of multi-centennial intra-interglacial arid events in southern Europe, coherent with cold water-mass expansions in the North Atlantic. The spatial and temporal fingerprints of these changes indicate a reorganization of ocean surface circulation, consistent with low-intensity disruptions of the Atlantic meridional overturning circulation (AMOC). The amplitude of this LIG variability is greater than that observed in Holocene records. Episodic Greenland ice melt and runoff as a result of excess warmth may have contributed to AMOC weakening and increased climate instability throughout the LIG

Pleistocene tephrostratigraphy and palaeoclimatology in the central Mediterranean region: ongoing research in Fucino Basin (central Apennines, Italy)

Palaeoclimatic records spanning beyond the radiocarbon range generally derive their chronologies from orbital tuning strategies. These chronologies can introduce a priori assumptions that are difficult to test and, possibly, circular arguments in palaeoclimatic reconstructions. We elaborate two high-resolution, multi-proxy and tephrochronologically-constrained records (F1-F3 and F4-F5) of past environmental and climatic changes in the central Mediterranean region. We perform geochemical (X-ray fluorescence scanning, carbon, nitrogen and sulphur elemental analysis through combustion), isotopic (C and O stable isotope mass spectrometry on bulk carbonates and organic matter), mineralogical (X-ray powder diffraction) and grain-size analyses on lacustrine marls recovered from palaeolake Fucino (Abruzzo, central Italy). Lacustrine sediments were acquired during two scientific drilling campaigns (F1-F3 and F4-F5) interesting the first ca. 85 m of the 1 km-thick and 2 Ma-old Fucino sedimentary succession. We make use of detailed tephrostratigraphic and tephrochronological frameworks to produce robust and independent chronologies based on new and published 40Ar/39Ar and 14C dating of tephra layers. On the basis of our chronologies, the F1-F3 and F4-F5 records continuously span over the last two glacial-interglacial cycles and over the last five glacial-interglacial cycles, respectively. We combine our geological data into proxies for catchment- and regional-scale environmental processes. Our proxy time-series depict prominent orbital and sub-orbital environmental changes that can be tracked in other lacustrine, marine and speleothem records across the Mediterranean and North Atlantic regions. Thanks to tephrostratigraphic correlations and chronological matching, we produce spatially coherent palaeoclimatic reconstructions recognising a complex interplay between regional environmental processes and broad-scale climatic events. We highlight strong orbital forcing for past climate changes