Fractionation of oxygen and hydrogen isotopes in evaporating water

Variations in oxygen and hydrogen isotope ratios of water and ice are powerful tools in hydrology and ice core studies. These variations are controlled by both equilibrium and kinetic isotope effects during evaporation and precipitation, and for quantitative interpretation it is necessary to understand how these processes affect the isotopic composition of water and ice. Whereas the equilibrium isotope effects are reasonably well understood, there is controversy on the magnitude of the kinetic isotope effects of both oxygen and hydrogen and the ratio between them. In order to resolve this disagreement, we performed evaporation experiments into air, argon and helium over the temperature range from 10 to 70 °C. From these measurements we derived the isotope effects for vapor diffusion in gas phase (ε_{diff(HD¹⁶O)} for D/H and ε_{diff(H2¹⁸O)} for ¹⁸O/¹⁶O). For air, the ratio ε_{diff(HD¹⁶O)}/ε_{diff(H2¹⁸O)} at 20 °C is 0.84, in very good agreement with Merlivat (1978) (0.88), but in considerable inconsistency with Cappa et al. (2003) (0.52). Our results support Merlivat’s conclusion that measured ε_{diff(HD¹⁶O)}/ε_{diff(H2¹⁸O)} ratios are significantly different than ratios calculated from simplified kinetic theory of gas diffusion. On the other hand, our experiments with helium and argon suggest that this discrepancy is not due to isotope effects of molecular collision diameters. We also found, for the first time, that the ε_{diff(HD¹⁶O)}/ε_{diff(H2¹⁸O)} ratio tends to increase with cooling. This new finding may have important implications to interpretations of deuterium excess (d-excess = δD − 8δ¹⁸O) in ice core records, because as we show, the effect of temperature on d-excess is of similar magnitude to glacial interglacial variations in the cores.     

Asbestiform and non-asbestiform morphologies in a talc and vermiculite mine from the province of Córdoba (Argentina): a case study

In this work, a talc and vermiculite mine from the province of Córdoba (Argentina) was investigated with special emphasis on the occurrence of asbestiform and non-asbestiform phases. The meta-ultramafic rock was studied by a multimethodological approach, complementing field studies with petrographic-mineralogical, compositional and morphological analyses. Samples were examined by stereomicroscopy, polarizing light microscopy, SEM–EDS, XRD, DSC-TGA and FTIR. Complementary, compositional and textural analyses were performed with FE-SEM–EDS and EPMA. Talc-rich veins with a laminar and fibrous appearance were at first recognized. However, the fibrous morphology observed both in the field and by microscopy is due to an apparent habit because of the sample orientation. To avoid erroneous interpretations, studies by secondary electron images (SEM) are fundamental to carrying out this type of analysis. Tremolite was identified in different zones of the outcrop; however, only ~40% of the crystals located in the vermiculite zone have dimensions to be considered as asbestiform fibres in the range of respirable particles. In these types of complex deposits affected by superimposed metamorphic, igneous and deformational events, multimethodological approaches are necessary to develop models of occurrence of asbestiform morphologies that may be applicable to other with similar characteristics.     

Thermal state of the Campi Flegrei caldera inferred from seismic attenuation tomography

A three-dimensional Qp image of the Campi Flegrei caldera between 0 and 3 km of depth has been inferred by the inversion of P rise time and pulse width data of 87 local earthquakes recorded during the last bradiseismic crisis by a local array deployed in the area by the University of Wisconsin. The availability of both thermal measurements in 5 deep boreholes and of a heat flow surface map of the area allowed us to calibrate the local temperature F vs. Qp relationship. The comparison of Qp, Vp and Vp/Vs images, combined with hydrogeological and geochemical data from deep boreholes, allowed us to distinguish some low-Qp anomalies related to the presence of fluids in the rocks from a deep low-Qp anomaly related to the conductive cooling of a magma reservoir. The deep anomaly is located in the same zone where several authors believe that the volcanic and magmatic activity migrated after the Neapolitan Yellow Tuff eruption. Moreover this anomaly includes the area where the existence of a magma chamber at depth between 4 and 5 km was inferred by an active seismic experiment.     

New Insights into Crustal Contributions to Large-volume Rhyolite Generation in the Mid-Tertiary Sierra Madre Occidental Province, Mexico, Revealed by U Pb Geochronology

Voluminous (3·9 x 10⁵ km³), prolonged (18 Myr) explosivesilicic volcanism makes the mid-Tertiary Sierra Madre Occidentalprovince of Mexico one of the largest intact silicic volcanicprovinces known. Previous models have proposed an assimilation–fractionalcrystallization origin for the rhyolites involving closed-systemfractional crystallization from crustally contaminated andesiticparental magmas, with <20% crustal contributions. The lackof isotopic variation among the lower crustal xenoliths inferredto represent the crustal contaminants and coeval Sierra MadreOccidental rhyolite and basaltic andesite to andesite volcanicrocks has constrained interpretations for larger crustal contributions.Here, we use zircon age populations as probes to assess crustalinvolvement in Sierra Madre Occidental silicic magmatism. Laserablation-inductively coupled plasma-mass spectrometry analysesof zircons from rhyolitic ignimbrites from the northeasternand southwestern sectors of the province yield U–Pb agesthat show significant age discrepancies of 1–4 Myr comparedwith previously determined K/Ar and ⁴⁰Ar/³⁹Ar ages from thesame ignimbrites; the age differences are greater than the errorsattributable to analytical uncertainty. Zircon xenocrysts withnew overgrowths in the Late Eocene to earliest Oligocene rhyoliteignimbrites from the northeastern sector provide direct evidencefor some involvement of Proterozoic crustal materials, and,potentially more importantly, the derivation of zircon fromMesozoic and Eocene age, isotopically primitive, subduction-relatedigneous basement. The youngest rhyolitic ignimbrites from thesouthwestern sector show even stronger evidence for inheritancein the age spectra, but lack old inherited zircon (i.e. Eoceneor older). Instead, these Early Miocene ignimbrites are dominatedby antecrystic zircons, representing >33 to 100% of the datedpopulation; most antecrysts range in age between 20 and 32 Ma.A sub-population of the antecrystic zircons is chemically distinctin terms of their high U (>1000 ppm to 1·3 wt %) andheavy REE contents; these are not present in the Oligocene ignimbritesin the northeastern sector of the Sierra Madre Occidental. Thecombination of antecryst zircon U–Pb ages and chemistrysuggests that much of the zircon in the youngest rhyolites wasderived by remelting of partially molten to solidified igneousrocks formed during preceding phases of Sierra Madre Occidentalvolcanism. Strong Zr undersaturation, and estimations for veryrapid dissolution rates of entrained zircons, preclude coevalmafic magmas being parental to the rhyolite magmas by a processof lower crustal assimilation followed by closed-system crystalfractionation as interpreted in previous studies of the SierraMadre Occidental rhyolites. Mafic magmas were more probablyimportant in providing a long-lived heat and material flux intothe crust, resulting in the remelting and recycling of oldercrust and newly formed igneous materials related to Sierra MadreOccidental magmatism. KEY WORDS: ignimbrite; rhyolite; Sierra Madre Occidental; Tertiary; U–Pb geochronology; zircon; antecryst; crustal melting     

The environmental history of a mountain lake (Lago Paione Superiore, Central Alps, Italy) for the last c. 100 years: a multidisciplinary, palaeolimnological study

A palaeoecological study of an oligotrophic alpine lake, Paione Superiore (Italy), provided a record of historical changes in water quality. Historical trends in lake acidification were reconstructed by means of calibration and regression equations from diatoms, chrysophycean scales and pigment ratios. The historical pH was inferred by using two different diatom calibration data sets, one specific to the alpine region. These pH trends, together with the record of sedimentary carbonaceous particles and chironomid remains, indicate a recent acidification of this low alkalinity lake.Concentration of total organic matter, organic carbon, nitrogen, biogenic silica (BSiO₂), chlorophyll derivatives (CD), fucoxanthin, diatom cell concentration and number of chironomid head capsules increased during the last 2–3 decades. When expressed as accumulation rates, most of these parameters tended to decrease from the past century to c. 1950, then all except P increased to the present day. A marked increase in sedimentary nitrogen may be related to atmospheric pollution and to the general increases in output of N in Europe. High C/N ratios indicate a prevailing allochthonous source of organic matter.Finally, the increase in measured air temperature from the mid-1800's appeared to be related to lake water pH before industrialization: cold periods generally led to lower pH and vice-versa. The more recent phenomenon of anthropogenic acidification has apparently decoupled this climatic-water chemistry relationship.     

A Geoarchaeological Survey of the Marine Extension of the Roman Archaeological Site Villa del Pezzolo,Vico Equense,on the Sorrento Peninsula,Italy

The Roman Villa on the Marina di Equa (Vico Equense, Sorrento Peninsula, Italy), built in the first century A.D., is an important coastal site where the geological effects of the A.D. 79 eruption of Vesuvius are combined with archaeological remains, thus representing an interaction of both human and natural events. At this site, a patrician Roman villa, located at the outlet of a steep V‐shaped valley on the northern flank of a ridge in the Lattari Mountains, was completely destroyed by the A.D. 79 eruption and by subsequent mud/debris flows and floods. During these catastrophic events, the villa was rebuilt twice, in the second and third centuries A.D., as shown by archaeological evidence on the beach. A marine geophysical survey was conducted to study the unexplored portion of this archaeological site. A geographical information system (GIS) analysis of integrated geophysical survey data has identified and mapped (in two and three dimensions) the major underwater archaeological structures on and below the seabed in the villa harbor. A map of the ancient port of the Roman villa has been created by correlating the submerged remains with the construction phases of the villa.     

Sources of ground movement at Vesuvius before the AD 79 eruption: Evidence from contemporary accounts and archaeological studies

Historical sources have recorded earthquake shocks, their effects and difficulties that local inhabitants experienced before the AD 79 Pompeii eruption. Archaeological studies pointed out the effects of such seismicity, and have also evidenced that several water crises were occurring at Pompeii in that period. Indeed numerous sources show that, at the time of eruption, and probably some time before, the civic aqueduct, having ceased to be supplied by the regional one, was out of order and that a new one was being built. Since Roman aqueducts were usually built with a recommended minimum mean slope of 20 cm/km and Pompeii's aqueduct sloped from the nearby Apennines toward the town, this slope could have been easily cancelled by uplift that occurred in the area even if this was only moderate.     

Evidence for short-lived oscillations in the biological records from the sediments of Lago Albano (Central Italy) spanning the period ca. 28 to 17 k yr BP

We report the results of analyses of pigments (derived from algae and photosynthetic bacteria), diatoms and invertebrate fossil remains (ostracods, cladocerans, chironomids) in two late Pleistocene sediment cores from Lago Albano, a crater lake in Central Italy. The record contains evidence for oscillations in lake biota throughout the period ca. 28 to 17 k yr BP. The earliest of these are contained in the basal 3.5 m of light olive-gray and yellowish-gray spotted muds sampled in core PALB 94-1E from 70 m water depth. The later oscillations are best represented in the more extended sediment sequence recovered from a second core site, PALB 94-6B, in 30 m water depth. The sediments at site 1E, containing the earlier oscillations (ca. 28-24 k yr BP), predate any sedimentation at the shallower site, from which we infer an initially low lake level rising to permit sediment accumulation at site 6B from ca. 24 k yr onwards. At site 6B, massive silts rich in moss remains are interbedded with laminated silts and carbonates. These sediments span the period ca. 24 to 17 k yr and are interpreted as representing, respectively, times of shallow water alternating with higher lake stands, when the lake was stratified and bottom water was stagnant. A range of mutually independent chronological constraints on the frequency and duration of the oscillations recorded in the lake biota indicate that they were aperiodic and occurred on millennial to century timescales. We interpret them as responses to climate forcing through its impact on lake levels and changing aquatic productivity. The time span they occupy, their frequency and their duration suggest that at least some of these changes may parallel both the Dansgaard-Oeschger events recorded in Greenland Ice Cores and the contemporary oscillations in North Atlantic circulation documented in marine sediment cores.