Total- and semi-bare noble metal nanoparticles@silica core@shell catalysts for hydrogen generation by formic acid decomposition

Catalysts are involved in a number of established and emerging chemical processes as well as in environmental remediation and energy conversion. Nanoparticles (NPs) can offer several advantages over some conventional catalysts, such as higher efficiency and selectivity. Nowadays, versatile and scalable nanocatalysts that combine activity and stability are still lacking. Here, we report a comprehensive investigation on the production and characterization of hybrid nano-architectures bringing a partial or total bare surface together with their catalytic efficiency evaluation on, as a proof-of-concept, the formic acid decomposition reaction. In this regard, formic acid (FA) is a convenient and safe hydrogen carrier with appealing features for mobile applications, fuel cells technologies, petrochemical processes and energetic applications. Thus, the design of robust catalysts for FA dehydrogenation is strongly demanded. Due to this, we produced and evaluated nano-architectures with various equilibrium between the size-increase of the active part and the barer catalytic surface. Overall, this work paves the way for the development of new approaches for green energy storage and safe delivery

Phylogenetic position of a copper age sheep (Ovis aries) mitochondrial DNA.

Background: Sheep (Ovis aries) were domesticated in the Fertile Crescent region about 9,000-8,000 years ago. Currently, few mitochondrial (mt) DNA studies are available on archaeological sheep. In particular, no data on archaeological European sheep are available. Methodology/Principal Findings: Here we describe the first portion of mtDNA sequence of a Copper Age European sheep. DNA was extracted from hair shafts which were part of the clothes of the so-called Tyrolean Iceman or O¨ tzi (5,350 - 5,100 years before present). Mitochondrial DNA (a total of 2,429 base pairs, encompassing a portion of the control region, tRNAPhe, a portion of the 12S rRNA gene, and the whole cytochrome B gene) was sequenced using a mixed sequencing procedure based on PCR amplification and 454 sequencing of pooled amplification products. We have compared the sequence with the corresponding sequence of 334 extant lineages. Conclusions/Significance: A phylogenetic network based on a new cladistic notation for the mitochondrial diversity of domestic sheep shows that the O¨ tzi’s sheep falls within haplogroup B, thus demonstrating that sheep belonging to this haplogroup were already present in the Alps more than 5,000 years ago. On the other hand, the lineage of the O¨ tzi’s sheep is defined by two transitions (16147, and 16440) which, assembled together, define a motif that has not yet been identified in modern sheep populations

Analisi della suscettibilità da frana a scala di bacino (Bacino del Fiume Arno, Toscana-Umbria, Italia)

In questa nota vengono presentati i metodi applicati e i risultati ottenuti in una recente analisi della pericolosità da frana, condotta sul territorio del Bacino del Fiume Arno nell’ambito di una convenzione tra l’Autorità di Bacino e il Dipartimento di Scienze della Terra dell’Università di Firenze (2002-2005). Tutti i dati acquisiti, confluiti in una banca dati GIS, sono stati sintetizzati in carte tematiche e in una carta inventario delle frane. La sovrapposizione dei fattori predisponenti selezionati (pendenza, litologia, uso del suolo, curvatura di profilo e area drenata) ha permesso di definire le unità elementari per il trattamento statistico (Unità Territoriali Omogenee: UTO). La valutazione della pericolosità è stata estesa alle aree prive di movimenti franosi utilizzando metodi statistici multivariati implementati in Reti Neurali Artificiali. L’area di studio è stata suddivisa in cinque Macroaree morfologicamente e geologicamente omogenee: per ogni Macroarea, i predittori neurali sono stati addestrati su un opportuno sottoinsieme di dati, applicando poi i migliori all’intero data-set al fine di generare valori previsti dell’indice di suscettibilità per ogni UTO. Infine, i valori di uscita sono stati riclassificati in differenti livelli di pericolosità in base a criteri di soglia e validati per confronto con l’inventario. Una percentuale di area in frana compresa tra l’81 e il 96% risulta correttamente classificata dalla previsione nelle varie Macroare

Disturbances in groundwater chemical parameters related to seismic and volcanic activity in Kamchatka (Russia)

International audienceStarting from 1992 geochemical data are being collected with a mean sampling frequency of three days in the form of the pH value and of the most common ions and gases in the groundwater in one deep well located in Petropavlovsk, the capital city of Kamchatka (Russia). On 1 January 1996 a strong eruption started from the Karymsky volcano, that is located about 100km far from the well, in the north-northeastern direction. At the same time, a large earthquake (M=6.9) occurred in the Karymsky area. On 5 December 1997 a very large earthquake (M=7.7) occurred offshore, at a distance of 350km from the well and towards the same direction. The analysis of the geochemical data shows clear variations in the raw temporal trends on both cases. For the first event, a clear premonitory phase appeared; for the second one, some pre-seismic variations could be revealed but permanent modifications of the chemistry of the water subsequent to the earthquake are very clear. In both cases the feature of the geochemical variations is consistent with an afflux of new water in the aquifer connected with the well and with an escape of the Carbon dioxide gas from the ground in different directions. A schematic model able to justify such a phenomenology and the connections of the geochemical variations with the previous tectonic activities is proposed

A possible radio anomaly observed on the occasion of the MW=6.0 earthquake occurred in Dodecanese islands at the end of January 2020

Since 2009, several VLF/LF radio receivers have been installed throughout Europe in order to realize a European radio network for studying the radio precursors of earthquakes, called the INFREP network. The current network has nine VLF/LF receiving stations, two in Romania and Greece, one in Italy, Austria, Portugal, Cyprus, and Serbia. The receivers can measure with 1 min sampling rate the intensity of 10 radio signals in the band VLF (10-50 kHz) and LF (150-300 kHz). The scope of existing transmitters is manifold, e.g. they are used for radio broadcast (LF), for radio- navigation or time signals and mainly for military purposes in the VLF range. At the end of January 2020 an intense seismic crisis occurred in Dodecanese Islands; the main event (Mw= 6.0) occurred on January 30. This seismic activity occurred in the "sensitive" area of the INFREP network. The analysis of the data collected by INFREP receivers has revealed clear anomalies in three VLF signals appearing some days before the main earthquake. The anomalies appear in the trends collected by the Cyprus receiver and the epicenter is inside the 5th Fresnel ellipses defined by transmitters- receiver. Here we report the data analysis and we present in detail the anomalies. The possibility that they are precursors of the quoted earthquake seems significant. Biagi, P.F., Colella, R., Schiavulli, L., Ermini, A., Boudjada, M., Eichelberger, H., Schwingenschuh, K., Katzis, K., Contadakis, M.E., Skeberis, C., Moldovan, I.A. and Bezzeghoud, M. (2019) The INFREP Network: Present Situation and Recent Results. Open Journal of Earthquake Research,8, 101-115. https://doi.org/10.4236/ojer.2019.8200

Wavelet analysis applied on temporal data sets in order to reveal possible pre-seismic radio anomalies and comparison with the trend of the raw data

Since 2009, several radio receivers have been installed throughout Europe in order to realize the INFREP European radio network for studying the VLF (10-50 kHz) and LF (150-300 kHz) radio precursors of earthquakes. Precursors can be related to “anomalies” in the night-time behavior of VLF signals. A suitable method of analysis is the use of the Wavelet spectra. Using the “Morlet function”, the Wavelet transform of a time signal is a complex series that can be usefully represented by its square amplitude, i.e. considering the so-called Wavelet power spectrum. The power spectrum is a 2D diagram that, once properly normalized with respect to the power of the white noise, gives information on the strength and precise time of occurrence of the various Fourier components, which are present in the original time series. The main difference between the Wavelet power spectra and the Fourier power spectra for the time series is that the former identifies the frequency content along the operational time, which cannot be done with the latter. Anomalies are identified as regions of the Wavelet spectrogram characterized by a sudden increase in the power strength. On January 30, 2020 an earthquake with Mw= 6.0 occurred in Dodecanese Islands. The results of the Wavelet analysis carried out on data collected some INFREP receivers is compared with the trends of the raw data. The time series from January 24, 2020 till January 31, 2000 was analyzed. The Wavelet spectrogram shows a peak corresponding to a period of 1 day on the days before January 30. This anomaly was found for signals transmitted at the frequencies 19,58 kHz, 20, 27 kHz, 23,40 kHz with an energy in the peak increasing from 19,58 kHz to 23,40 kHz. In particular, the Powered by TCPDF (www.tcpdf.org) signal at the frequency 19,58 kHz, shows a peak on January 29, while the frequencies 20,27 kHz and 23,40 kHz are characterized by a peak starting on January 28 and continuing to January 29. The results presented in this work shows the perspective use of the Wavelet spectrum analysis as an operational tool for the detection of anomalies in VLF and LF signal potentially related to EQ precursors

Retrospective analysis for detecting seismic precursors in groundwater argon content

We examined the groundwater Argon content data sampled from 1988 to 2001 at two wells in Kamchatka (Russia) and anomalous increases appeared clearly during June-July&nbsp;1996. On 21&nbsp;June, a shallow (1km) earthquake with <i>M</i>=7.1 occurred at a distance less than 250km from the wells and so the previous increases could be related to this earthquake and, in particular, could be considered premonitory anomalies. In order to support this raw interpretation, we analysed the data collected in details. At first we smoothed out the high frequency fluctuations arising from the errors in a single measurement. Next we considered the known external effects on the water of a well that are the slow tectonic re-adjustment processes, the meteorology and the gravity tides and we separated these effects applying band-pass filters to the Argon content raw trends. Then we identified the largest fluctuations in these trends applying the 3 σ criterion and we found three anomalies in a case and two anomalies in other case. Comparing the time occurrence of the anomalies at the two wells we found out that a coincidence exists only in the case of the premonitory anomalies we are studying. The simultaneous appearance of well definite anomalies in the residual trends of the same parameter at two different sites supports their meaning and the possibility that they are related to some large scale effect, as the occurrence of a strong earthquake. But, other earthquakes similar to the June&nbsp;1996 event took place during the Argon content measurements time and no anomaly appeared in this content. In the past, some of the authors of this paper studied the Helium content data collected in three natural springs of the Caucasus during seven years. A very similar result, that is the simultaneous appearance of clear premonitory anomalies only on the occasion of a strong (<i>M</i>=7.0) but shallow (2–4km) earthquake, was obtained. The correspondence with the case of the Caucasus validates the interpretation of the Kamchatkian anomalies as precursors

A possible preseismic anomaly in the ground wave of a radio broadcasting (216 kHz) during July-August 1998 (Italy)

International audienceOn February 1996, a receiver able to measure the electric field strength of LF radio broadcastings, with a sampling frequency of ten minutes, was put into operation in a site (AS) located in central Italy. One of the broadcasting stations selected is MCO (f=216 kHz), located in southeast France, 518 km far from the receiver. The MCO data collected since February 1996 up to September 2004 were examined and, at first, the night time data and the day time data (in winter and summer) were separated. Then, the wavelet analysis on the night and day time data was applied. The main result of the analysis was the appearance of a very clear anomaly during summer (July?August) 1998, at day time and at night time. The anomaly is a strong exaltation of the signal components with period in the 25?40 days range. Theoretical calculations of electric field strength were made and the only way to justify this anomaly seems to be the occurrence of an increase of the ground wave propagation mode of the radio signal. Such an increase could have been produced by an increase of the ground conductivity and by modifications of some parameter of the troposphere, mainly the refractive index. On 15 August 1998 a seismic sequence started with 17 earthquakes (M=2.2?4.6) on the Reatini mountains, a seismogenic zone located 30 km far from the AS receiver along the path MCO-AS. In this paper, the possibility that the previous radio anomaly can be a precursor of this seismic sequence is proposed. </p

North Atlantic mid-latitude surface-circulation changes through the Plio-Pleistocene intensification of northern hemisphere glaciation

This is the final version. Available from American Geophysical Union (AGU) / Wiley via the DOI in this record.All new data presented are available at https://doi.pangaea.de/10.1594/PANGAEA.892805The North Atlantic Current (NAC) transports warm salty water to high northern latitudes, with important repercussions for ocean circulation and global climate. A southward displacement of the NAC and Subarctic Front, which separate subpolar and subtropical water masses, is widely suggested for the last glacial maximum (LGM) and may have acted as a positive feedback in glacial expansion at this time. However, the role of the NAC during the intensification of northern hemisphere glaciation (iNHG) ~3.5 to 2.5 Ma, is less clear. Here, we present new records from IODP Site U1313 (41°N) spanning ~2.8-2.4 Ma to trace the influence of Subarctic Front waters above this mid-latitude site. We reconstruct surface and permanent pycnocline temperatures and seawater δ18O using paired Mg/Ca-δ18O measurements on the planktic foraminifers Globigerinoides ruber and Globorotalia crassaformis, and determine abundances of the subpolar foraminifer Neogloboquadrina atlantica. We find that the first significant glacial incursions of Subarctic Front surface waters above Site U1313 did not occur until ~2.6 Ma. At no time during our study interval was (sub)surface reorganisation in the mid-latitude North Atlantic analogous to the LGM. Our findings suggest that LGM-like processes sensu stricto cannot be invoked to explain interglacial-glacial cycle amplification during iNHG. They also imply that increased glacial productivity at Site U1313 during iNHG was not only driven by southward deflections of the Subarctic Front. We suggest nutrient injection from cold-core eddies and enhanced glacial dust delivery may have played additional roles in increasing export productivity in the mid-latitude North Atlantic from 2.7 Ma.Funding for this research was provided by IODP France (CTB) and the German Research Foundation (DFG) (grant OF 2544/2 to OF). IB is grateful to the UK IODP for financial support for shipboard and post-cruise participation in IODP Exp. 306. CTB, KT, TDG, LV, CS, and ME acknowledge OSU Pythéas. MMR acknowledges support by the USGS Land Change Science Program. Any use of trade, firm, or product names is for descriptive purposes only and does not imply endorsement by the U.S. Government. PAW acknowledges NERC UK IODP NE/F00141X/1 and a Royal Society Wolfson Merit Award