Analysis of unresolved complex mixtures of hydrocarbons extracted from Late Archean sediments by comprehensive two-dimensional gas chromatography (GC×GC)

Hydrocarbon mixtures too complex to resolve by traditional capillary gas chromatography display gas chromatograms with dramatically rising baselines or “humps” of coeluting compounds that are termed unresolved complex mixtures (UCMs). Because the constituents of UCMs are not ordinarily identified, a large amount of geochemical information is never explored. Gas chromatograms of saturated/unsaturated hydrocarbons extracted from Late Archean argillites and greywackes of the southern Abitibi Province of Ontario, Canada contain UCMs with different appearances or “topologies” relating to the intensity and retention time of the compounds comprising the UCMs. These topologies appear to have some level of stratigraphic organization, such that samples collected at any stratigraphic formation collectively are dominated by UCMs that either elute early- (within a window of C₁₅–C₂₀ n-alkanes), early- to mid- (C₁₅–C₃₀ n-alkanes), or have a broad UCM that extends through the entire retention time of the sample (from C₁₅–C₄₂ n-alkanes). Comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC×GC–MS) was used to resolve the constituents forming these various UCMs. Early- to mid-eluting UCMs are dominated by configurational isomers of alkyl-substituted and non-substituted polycyclic compounds that contain up to six rings. Late eluting UCMs are composed of C₃₆–C₄₀ mono-, bi-, and tricyclic archaeal isoprenoid diastereomers. Broad UCMs spanning the retention time of compound elution contain nearly the same compounds observed in the early-, mid-, and late-retention time UCMs. Although the origin of the polycyclic compounds is unclear, the variations in the UCM topology appear to depend on the concentration of initial compound classes that have the potential to become isomerized. Isomerization of these constituents may have resulted from hydrothermal alteration of organic matter.     

Self-enrichment by asymptotic giant branch stars in globular clusters: comparison between intermediate and high metallicities

We present theoretical evolutionary sequences of intermediate-mass stars  ( M = 3 − 6.5 M_⊙)  with metallicity   Z = 0.004  . Our goal is to test whether the self-enrichment scenario by massive asymptotic giant branch stars may work for the high-metallicity globular clusters, after previous works by the same group showed that the theoretical yields by this class of objects can reproduce the observed trends among the abundances of some elements, namely the O–Al and O–Na anticorrelations, at intermediate metallicities, i.e.  [Fe/H]=−1.3  . We find that the increase in the metallicity favours only a modest decrease of the luminosity and the temperature at the bottom of the envelope for the same core mass, and also the efficiency of the third dredge-up is scarcely altered. On the contrary, differences are found in the yields, due to the different impact that processes with the same efficiency have on the overall abundance of envelopes with different metallicities. We expect the same qualitative patterns as in the intermediate-metallicity case, but the slopes of some of the relationships among the abundances of some elements are different. We compare the sodium–oxygen anticorrelation for clusters of intermediate metallicity ( Z ≈ 10⁻³) and clusters of metallicity large as in these new models. Although the observational data are still too scarce, the models are consistent with the observed trends, provided that only stars of   M ≳ 5 M_⊙  contribute to self-enrichment.     

Geochemistry of the Submarine Gaseous Emissions of Panarea (Aeolian Islands, Southern Italy): Magmatic vs. Hydrothermal Origin and Implications for Volcanic Surveillance

The marine sector surrounding Panarea Island (Aeolian Islands, South Italy) is affected by widespread submarine emissions of CO₂ -rich gases and thermal water discharges which have been known since the Roman Age. On November 3^rd, 2002 an anomalous degassing event affected the area, probably in response to a submarine explosion. The concentrations of minor reactive gases (CO, CH₄ and H₂) of samples collected in November and December, 2002 show drastic compositional changes when compared to previous samples collected from the same area in the 1980s. In particular the samples collected after the November 3^rd phenomenon display relative increases in H₂ and CO and a strong decrease in the CH₄ contents, while other gas species show no significant change. The interaction of the original gas with seawater explains the variable contents of CO₂, H₂S, N₂, Ar and He which characterize the different samples, but cannot explain the large variations of CO, CH₄ and H₂ which are instead compatible with changes in the redox, temperature and pressure conditions of the system. Two models, both implying an increasing input of magmatic fluids are compatible with the observed variations of minor reactive species. In the first one, the input of magmatic fluids drives the hydrothermal system towards atypical (more oxidizing) redox conditions, slowly pressurizing the system up to a critical state. In the second one, the hydrothermal system is flashed by the rising high-T volcanic fluid, suddenly released by a magmatic body at depth. The two models have different implications for volcanic surveillance and risk assessment: In the first case, the November 3^rd event may represent both the culmination of a relatively slow process which caused the overpressurization of the hydrothermal system and the beginning of a new phase of quiescence. The possible evolution of the second model is unforeseeable because it is mainly related to the thermal, baric and compositional state of the deep magmatic system that is poorly known.     

Columnar jointing in vapor-phase-altered,non-welded Cerro Galán Ignimbrite,Paycuqui, Argentina

Columnar jointing is thought to occur primarily in lavas and welded pyroclastic flow deposits. However, the non-welded Cerro Galán Ignimbrite at Paycuqui, Argentina, contains well-developed columnar joints that are instead due to high-temperature vapor-phase alteration of the deposit, where devitrification and vapor-phase crystallization have increased the density and cohesion of the upper half of the section. Thermal remanent magnetization analyses of entrained lithic clasts indicate high emplacement temperatures, above 630°C, but the lack of welding textures indicates temperatures below the glass transition temperature. In order to remain below the glass transition at 630°C, the minimum cooling rate prior to deposition was 3.0 × 10⁻³–8.5 × 10⁻²°C/min (depending on the experimental data used for comparison). Alternatively, if the deposit was emplaced above the glass transition temperature, conductive cooling alone was insufficient to prevent welding. Crack patterns (average, 4.5 sides to each polygon) and column diameters (average, 75 cm) are consistent with relatively rapid cooling, where advective heat loss due to vapor fluxing increases cooling over simple conductive heat transfer. The presence of regularly spaced, complex radiating joint patterns is consistent with fumarolic gas rise, where volatiles originated in the valley-confined drainage system below. Joint spacing is a proxy for cooling rates and is controlled by depositional thickness/valley width. We suggest that the formation of joints in high-temperature, non-welded deposits is aided by the presence of underlying external water, where vapor transfer causes crystallization in pore spaces, densifies the deposit, and helps prevent welding.     

Volcanic geomorphology and tectonics of the Aeolian archipelago (Southern Italy) based on integrated DEM data

The geomorphological and morphometric analysis of the sea floor topography surrounding the Aeolian Islands, South Tyrrhenian Sea, Italy, provides insights into the relationships between the volcanological evolution of the islands and their tectonic features. We constructed geomorphological maps of the submarine portions of the seven large edifices constituting the islands on the basis of a DEM with a 5 m resolution step. These maps include constructional and destructional landforms such as submarine volcanic vents located west of Lipari and north of Alicudi, and hummocky surfaces recognised north of Lipari and Salina. The latter landforms, together with the occurrence of large scars affecting the main edifices on land, suggest that sector collapses affected some islands. Geomorphological data indicate that the location of subaerial and submarine vents is strongly controlled by local tectonic structures striking WNW-ESE (Alicudi-Filicudi sector), NNW-SSE (Salina-Lipari-Vulcano sector) and NE-SW (Panarea-Stromboli sector). The islands can be divided into two groups on the basis of some morphometric parameters: a first group with a pancake-like shape, Dp/D (abrasion platform diameter/basal diameter) higher than 0.40 and H/D (total height/basal diameter) lower than 0.13, and a second group with a conical shape, characterised by Dp/D lower than 0.34 and H/D higher than 0.14. These ratios and other morphometric parameters reflect the different volcanological and structural evolution of the Aeolian Islands. The pancake-like shaped complexes have been created, in addition to their submarine stage, by extrusive and highly explosive activity, whereas the cone-shaped edifices have been characterised by effusive or moderate explosive activity.Editorial responsibility: C Kilburn