The molecular composition of ambers

Bulk (elemental composition, IR, CP/MAS ¹³C NMR) and molecular (GC-MS) analyses have been performed on a series of ambers and resins derived from different locations (Dominican Republic, Philippines, Canada, Israel, New Zealand, Chile) having diverse botanical affinities (Araucariaceae, Hymenaea) and variable age (from Holocene to Early Cretaceous). No major differences have been observed from the elemental composition and the spectroscopic data; however, the molecular analyses of the solvent extractable fraction show that a specific mixture of components is present in each sample. These are mainly diterpenoid products that in general are also found abundantly in the higher plants from which the ambers and resins originate. Nevertheless, a direct relationship between major terpenoid constituents in fossil resins and precursor plant materials can only be established for the younger samples.Irrespective of the geographical or botanical origin of the ambers and resins, several common age-dependent molecular transformation trends can be recognized: (1) progressive loss of olefinic bonds (especially those located in exocyclic positions), (2) decrease of functionalized products, and (3) increasing proportion of aromatized components. However, even in the samples of older age (Cretaceous) the degree of aromatization is very low when compared with that of other higher-plant related materials such as fossilized woods or low rank coals. This indicates that maturation must involve essentially olefin polymerization processes instead of extensive aromatization.     

Determination of the Jenkinson and Collison’s weather types for the western Mediterranean basin over the 1948-2009 period. Temporal analysis

We determined the weather type, according to the Jenkinson and Collison procedure, of the 22 646 days in the 1948-2009 period for the western Mediterranean basin. The analysis is based upon the surface pressure values of the NCEP/NCAR reanalysis, for a grid of nine points with extreme vertices at 45º N, 5º W and 35º N, 15º E, which provides a broad synoptic catalogue for this region. We analyzed the trends of the types and their different groupings during the same period. The most frequent type is U (undetermined), with an annual average of approximately 100 days (99.4, 27.2%), followed by type A (anticyclone), with 75.5 days/ year (20.7%), and C (depression), with 67.8 days/year (18.6%). The high frequency of type U is due to the habitual pressure of baric fields with a low gradient over Mediterranean waters in the warm half of the year. According to their directions, the types from the west are the most frequent and those from the south, the least. The monthly regime of the most frequent types and groupings is quite regular; type C groups, as well as advective and cyclonic curvature groups, present summertime minima and maxima in the cold half of the year, whereas the opposite occurs with types U and A. The main statistically significant annual trends in the 1948-2009 period involve a decrease in type A (–4.19 days/decade, that is, –29.0%) and an increase in type U, the cyclonic types and those presenting an easterly component. On comparing the 31-yr sub-periods 1948-1978 and 1979-2009, the tendencies of A and U were confirmed, and increases can generally be seen in the types presenting an easterly component and a decrease in those with a westerly component. The variation in type A ranged from 2490 days in the first sub-period to 2192 in the second one (p = 0.000), mainly concentrated in summer and autumn. This evident reduction of type A coincides, paradoxically, with an increase in the sea surface pressure variable (+0.31 hPa/decade) throughout the 62 years of analysis. The negative trend found in type A differs from the results of some studies. The different analysis periods, the different scales or areas of study and the variety of methods used to determine the weather types can account for the fact that these results are discordant. Moreover, warming over the last few decades in the waters of the western Mediterranean basin, as well as the clearly cyclogenetic character of the gulfs of Lion and Genoa, might account for the decrease in type A and the increase in the cyclonic curvature types.     

Lipid biogeochemistry of Phormidium and Microcoleus mats

A study on the predominant sources of organic matter and the main diagenetic processes in two different cyanobacterial mats from evaporite-controlled environments was performed. Fatty acids, hydrocarbons, alcohols, ketones and aldehydes were anlyzed in selected millimetre and submillimetre core sections. The changes in lipid composition were evaluated by comparison with the vertical distributions of the populations observed by optic microscopy and with the lipid patterns of enrichment cultures of species such as cyanobacteria, diatoms, purple bacteria, sulphate-reducers and methanogens obtained from the mats.The cyanobacteria Phormidium valderianum and Microcoleus chthonoplastes are the predominant primary producers, and occur almost as monocultures in the respective top layers. However, these mat-forming organisms only leave minor features in the solvent-extractable lipid sedimentary record. The predominant fatty acid distributions parallel the composition observed in the enrichment cultures of purple bacteria and appear mixed with acids characteristic of heterotrophic eubacteria such as sulphate-reducers. The concentrations of these lipids are, however, 5–10 times lower than the cyanobacterial acids from the top layer. De novo heterotrophic eubacterial synthesis is also observed in cases such as the highly branched isoprenoid eicosenes, the major hydrocarbon in the deep layers (>2 mm) of the Phormidium mat. Other major diagenetic changes involve dehydration and hydrogenation. These two processes take place concurrently under anoxic conditions and have been observed among the sterols and the isoprenoid alcohols. Significant amounts of 5ß(H)-stanols were observed in the more reducing sections where molecular indicators of methanogenic bacteria were also found.     

Organic geochemistry of Cuban oils—I. The northern geological province

The isoprenoid, hopanoid and steroid compositions of 15 oils from the most productive oil fields in Cuba were studied to determine source-rock depositional environments and organic matter sources. The oils, which are from the northern geological province of Cuba and can be defined by the position with respect to the overthrust belt, can be grouped into two families: those from the Remedios (1) and those from the Placetas (2) tectonostratigraphic units.Remedios oils contain 17α(H)-diahopane, high relative amounts of 18α(H)-22,29,30-trisnorneohopane and diasteranes, which is indicative of generation from clay-rich source rocks. The crude oils of the Placetas Unit exhibit a sterane/hopane composition consistent with a carbonate origin. Nevertheless, these polycyclic hydrocarbons exhibit significant changes in composition, indicating that several organic matter sources, e.g. a carbonate/evaporitic origin of Varadero and Varadero Sur oils, have contributed to the oils from this Unit. The Remedios oils are more mature [evaluated from the and sterane indices] than the Placetas oils.A wide range of biodegradation levels are encountered in these oils (from 0 to 7–8 using the scale derived by Volkman et al. (1983). The high relative abundance of 25-norhopanes is a distinctive feature of Remedios oils. The presence of these compounds in lightly biodegraded or nondegraded oils corresponds to a mixing of paleobiodegraded oil with more recently sourced nondegraded oil in the reservoir. The most biodegraded oil, Cantel, exhibits and sterane ratios, and hopane ratios that have been altered by microbial attack.     

Use of regionalized stormflow coefficients with a view to hydroclimatological hazard mapping

Abstract

An attempt was made to compensate for the lack of long hydrological time series and the lack of information on maximum streamflow in the Alzette River basin (Luxembourg) via the regionalization of stormflow coefficients. Streamflow data recorded since 1995 with a very dense streamgauge network allowed the determination of maximum stormflow coefficients in 18 sub-basins of the Alzette. The stormflow coefficients were then regionalized via stepwise multiple regression analysis for 83 different sub-basins of the Alzette. Combined with 10-year daily rainfall heights (statistical estimation), this regionalization allowed the spatial variability of storm runoff in the Alzette basin to be mapped, thus providing a view of hazard and risk-producing areas, as well as of risk-exposed areas. In a basin with little historical hydrological information this technique can help identify areas where storm runoff reducing measures should be applied from the outset.     

Reactions in Amphibolite, Greenschist and Blueschist

Mineral assemblages in which chlorite [CHL], epidote [EPI],clinoamphibole [AMP], plagioclase [PLG] and quartz [QTZ] aremajor phases are characteristic of many low-grade mafic schists.The possible heterogeneous reactions in such an assemblage maybe separated into two types, exchange reactions and net-transferreactions. Only the latter alter significantly the modal proportionsof the minerals. A set of linearly independent reactions defines a reaction spaceof as many dimensions as there are independent reactions. Thespace defined by the net-transfer reactions alone is a sub-spacethat can be portrayed in three dimensions for the above assemblage.A procedure is presented herein that gives a set of independentreactions that may be taken as basis reactions for definingsuch a reaction space. All other reactions that can be writtenfor this assemblage, as well as observed whole-rock reactions,can be portrayed as vectors in these reaction spaces. Thesevectors connect the region (mineral facies) accessible to theabove assemblage. The whole-rock reactions of Laird (1980) relatinggreenschist, blueschist and various low-grade amphibolites fromVermont, provide informative examples, as do the whole-rockexperiments of Liou et al. (1974). Although reaction spaces apply to both equilibrium and disequilibriumassemblages the reactions selected as basis vectors correspondone-for-one to the chemical conditions for equilibrium thatmust obtain in any fully equilibrated assemblage. The set selectedis one that provides maximum sensitivity for geothermometric,geobarometric and geohygrometric purposes.     

Shallow-marine sediment cores record climate variability and earthquake activity off Lisbon (Portugal) for the last 2000 years

Sea Surface Temperature (SST), river discharge and biological productivity have been reconstructed from a multi-proxy study of a high-temporal-resolution sedimentary sequence recovered from the Tagus deposition center off Lisbon (Portugal) for the last 2000 years. SST shows 2 °C variability on a century scale that allows the identification of the Medieval Warm Period (MWP) and the Little Ice Age (LIA).High Iron (Fe) and fine-sediment deposition accompanied by high n-alkane concentrations and presence of freshwater diatoms during the LIA (1300–1900 AD) (Science 292 (2001) 662) suggest augmented river discharge, whereas higher total-alkenone concentrations point to increased river-induced productivity. During the MWP (550–1300 AD) (Science 292 (2001) 662) larger mean-grain size and low values of magnetic susceptibility, and concentrations of Fe, n-alkanes, and n-alcohols are interpreted to reflect decreased runoff. At the same time, increased benthic and planktonic foraminifera abundances and presence of upwelling related diatoms point to increased oceanic productivity. On the basis of the excellent match found between the negative phases of the North Atlantic Oscillation (NAO) index and the intensified Tagus River discharge observed for the last century, it is hypothesized that the increased influx of terrigenous material during the LIA reflects a negative NAO-like state or the occurrence of frequent extreme NAO minima. During the milder few centuries of the MWP, stronger coastal upwelling conditions are attributed to a persistent, positive NAO-like state or the frequent occurrence of extreme NAO maxima.The peak in magnetic susceptibility, centered at 90 cm composite core depth (ccd), is interpreted as the result of the well-known 1755 AD Lisbon earthquake. The Lisbon earthquake and accompanying tsunami are estimated to have caused the loss of 39 cm of sediment (355 years of record—most of the LIA) and the instantaneous deposition of a 19-cm sediment bed.     

Saharan Dust Transport and High-Latitude Glacial Climatic Variability: The Alboran Sea Record

Millennial to submillennial marine oscillations that are linked with the North Atlantic's Heinrich events and Dansgaard–Oeschger cycles have been reported recently from the Alboran Sea, revealing a close ocean-atmosphere coupling in the Mediterranean region. We present a high-resolution record of lithogenic fraction variability along IMAGES Core MD 95-2043 from the Alboran Sea that we use to infer fluctuations of fluvial and eolian inputs to the core site during periods of rapid climate change, between 28,000 and 48,000 cal yr B.P. Comparison with geochemical and pollen records from the same core enables end-member compositions to be determined and to document fluctuations of fluvial and eolian inputs on millennial and faster timescales. Our data document increases in northward Saharan dust transports during periods of strengthened atmospheric circulation in high northern latitudes. From this we derive two atmospheric scenarios which are linked with the intensity of meridional atmospheric pressure gradients in the North Atlantic region.     

The sedimentary expression of oceanic anoxic event 1b in the North Atlantic

The Aptian/Albian oceanic anoxic event 1b contains the record of several perturbations in the global carbon cycle and multiple black shale levels, particularly in the Western Tethys. The local lithological expression of an oceanic anoxic event depends on palaeogeographical and depositional setting as well as on regional palaeoclimate. Marine sediments at a particular location may therefore be more or less organic‐rich (or not at all) and they may consist of different lithologies. In most studies, however, much of the lithological variability associated with oceanic anoxic events is left unaccounted for and, thus, the exact processes leading to the enrichment of organic matter in these marine sediments and their subsequent preservation in the geological record are unknown. This study focuses on the local sedimentary processes behind the deposition of organic‐rich sediments at Deep Sea Drilling Project Site 545 and Ocean Drilling Program Sites 1049 and 1276 in the North Atlantic during oceanic anoxic event 1b. Although specifically dealing with the sediments deposited during this particular event at these localities, it is expected that the same processes were responsible for determining the exact sedimentary products at localities in similar settings, as well as during other similar events in the Mesozoic. Here, it is shown that the deposition of organic‐rich sediments during oceanic anoxic event 1b was a consequence of the enhanced productivity favoured by upwelling and by riverine nutrient input, or aeolian fertilization of the euphotic zone depending on geographical location. Slope instability processes resulted in the transfer of part of these organic‐rich sediments from the shelf to deep sea depocentres as mud‐laden organic‐rich turbidites, especially in the northern North Atlantic. The so‐called ‘black shales’ are much more varied than their name implies. The end product of sedimentation during an oceanic anoxic event at a particular location is commonly the result of several equifinal processes acting on a local scale rather than the direct result of basinal or even global mechanisms.