Dissolution rate spectra data of calcite single crystal and micrite material

The large discrepancy between field and laboratory measurements of mineral reaction rates is a long-standing problem in earth sciences, often attributed to factors extrinsic to the mineral itself. Nevertheless, differences in reaction rate are also observed within laboratory measurements, raising the possibility of intrinsic variations as well. Critical insight is available from analysis of the relationship between the reaction rate and its distribution over the mineral surface. This analysis recognizes the fundamental variance of the rate. The resulting anisotropic rate distributions are completely obscured by the common practice of surface area normalization. In a simple experiment using a single crystal and its polycrystalline counterpart, we demonstrate the sensitivity of dissolution rate to grain size, results that undermine the use of "classical" rate constants. Comparison of selected published crystal surface step retreat velocities (Jordan and Rammensee, 1998) as well as large single crystal dissolution data (Busenberg and Plummer, 1986) provide further evidence of this fundamental variability. Our key finding highlights the unsubstantiated use of a single-valued "mean" rate or rate constant as a function of environmental conditions. Reactivity predictions and long-term reservoir stability calculations based on laboratory measurements are thus not directly applicable to natural settings without a probabilistic approach. Such a probabilistic approach must incorporate both the variation of surface energy as a general range (intrinsic variation) as well as constraints to this variation owing to the heterogeneity of complex material (e.g., density of domain borders). We suggest the introduction of surface energy spectra (or the resulting rate spectra) containing information about the probability of existing rate ranges and the critical modes of surface energy.

40Ar/39Ar single-crystal dating of detrital muscovite and K-feldspar of ODP Holes 116-717A and 116-718C

Detrital K-feldspars and muscovites from Ocean Drilling Program Leg 116 cores that have depositional ages from 0 to 18 Ma have been dated by the 40Ar/39Ar technique. Four to thirteen individual K-feldspars have been dated from seven stratigraphic levels, each of which have a very large range, up to 1660 Ma. At each level investigated, at least one K-feldspar yielded an age minimum which is, within uncertainty, identical to the age of deposition. One to twelve single muscovite crystals from each of six levels have also been studied. The range of muscovite ages is less than that of the K-feldspars and, with one exception, reveal only a 20-Ma spread in ages. As with the K-feldspars, each level investigated contains muscovites with mineral ages essentially identical to depositional ages. These results indicate that a significant portion of the material in the Bengal Fan is first-cycle detritus derived from the Himalayas. Therefore, the significant proportion of sediment deposited in the distal fan in the early to mid Miocene can be ascribed to a significant pulse of uplift and erosion in the collision zone. Moreover, these data indicate that during the entire Neogene, some portion of the Himalayan orogen was experiencing rapid erosion (<= uplift). The lack of granulite facies rocks in the eastern Himalayas and Tibetan Plateau suggests that very rapid uplift must have been distributed in brief pulses in different places in the mountain belt. We suggest that the great majority of the crystals with young apparent ages have been derived from the southern slope of the Himalayas, predominantly from near the main central thrust zone. These data provide further evidence against tectonic models in which the Himalayas and Tibetan plateaus are uplifted either uniformly during the past 40 m.y. or mostly within the last 2 to 5 m.y.

Messinian and pre-Messinian sediments of ODP Holes 107-652A and 107-654A

Sedimentology, mineralogy, and petrology of the pre-Pliocene sediments drilled at ODP Sites 652 and 654 in the Tyrrhenian Sea (Leg 107) have been studied with emphasis on the lower Messinian to pre-Messinian intervals. Messinian at Site 652 is essentially turbiditic and basinal in character; it was deposited during the syn-rift phase in a strongly subsiding half-graben and is correlatable with emerged coeval sequences; in part with the Laga Formation of the foredeep of Apennines, and in part with the filling of grabens dissecting that chain in the Tyrrhenian portion of Tuscany. The sequence found in Site 654 indicates an upper Tortonian to Messinian transgression accompanying crustal stretching in the western Tyrrhenian Sea and is perfectly correlatable with the so-called "Sahelian cycle" and with "postorogenic" cycles recognized in peninsular Italy and in Sicily.

(Table 1) Compressional- and share-wave velocieties at elevated confining pressure of ODP Holes 136-842C and 136-843A

Identification of a sediment/basement contact using seismic reflection recordings has proven to be extremely difficult in wide areas of the North Pacific Ocean owing to the presence of massive, highly reflective chert layers within the sediment column. Leg 136 of the Ocean Drilling Program recovered coherent pieces of chert of sufficient size for the first comprehensive laboratory measurements of the seismic properties of this material. Compressional-wave velocities of six samples at 40-MPa confining pressure averaged 5.33 km/s, whereas shear-wave velocities at the same pressure averaged 3.48 km/s. Velocities were independent of porosity, which ranged from 5% to 13%, suggesting that pores within the samples were mostly high aspect ratio vugs as opposed to low aspect ratio cracks. Back-scattered electron images made with a scanning electron microscope confirmed this observation. Acoustic impedances were calculated for the chert samples and from shipboard measurements of the red clay sediment overlying the chert layers. An extremely large compressional-wave reflection coefficient (0.73) characterized the interface between the two lithologies. A synthetic seismogram was calculated using chert and typical pelagic carbonate properties to illustrate the influence of chert layers on a marine seismic-reflection section. Compressional-wave to shear-wave velocity ratios of the chert samples (Vp/Vs =1.53) are close to that of single-crystal quartz in spite of variable porosity. Shear-wave reflection coefficients are estimated to be approximately 0.94. A compressional-wave reflection coefficient for a basement/sediment (carbonate) interface is estimated to be approximately 0.50, significantly less than that of sediment/chert.

Trioctahedral micas in xenolithic ejecta from recent volcanism of the Somma-Vesuvius

This study reports the first crystal chemical database resulting from a detailed structural investigation of trioctahedral micas found in xenolithic ejecta produced during the AD 1631, 1872 and 1944 eruptions, three explosive episodes of recent volcanic period of Vesuvius volcano (Southern Italy). Three xenolith types were selected: metamorphic/metasomatic skarns, pyrometamorphic/hydrothermally altered nodules and mafic cumulates. They are related to different magma chemistry and effusive styles: from sub-plinian and most evolved (AD 1631 eruption) to violent strombolian with medium evolution degree (AD 1872 eruption) to vulcanian-effusive, least evolved (AD 1944 eruption) event, respectively. Both xenoliths and micas were investigated employing multiple techniques: the xenoliths were characterized by X-ray fluorescence, inductively-coupled plasma-mass spectrometry, optical microscopy, X-ray powder diffraction, and quantitative energy-dispersive microanalysis; the micas were studied by electron probe microanalysis and single crystal X-ray diffraction. The mica-bearing xenoliths show variable texture and mineralogical assemblage, clearly related to their different origin. Based on the major oxide chemistry, only one xenolithic sample falls in the skarn compositional field from the Somma-Vesuvius literature, some fall close to the skarns and cumulate fields, others plot close to the syenite/foidolite/essexite field. A subgroup of the selected ejecta does not fall or approach any of the compositional fields. Trace and rare earth element patterns show some petrological affinity between studied xenoliths and erupted magmas with typical Eu, Ta and Nb negative anomalies. Strongly depleted patterns were detected for the 1631 metamorphic/metasomatic skarns xenoliths. Three distinct mica groups were distinguished: 1) Mg-, Al-rich, low Ti-bearing, low to moderate F-bearing varieties (1631 xenolith), 2) Al-moderate, F- and Mg-rich, Ti-, Fe-poor varieties (1872 xenolith), and 3) Al-, Ti- and Fe-rich, F-poor phases (1944 xenolith). All the analysed mica crystals are 1M polytypes with the expected space group C2/m. Micas from xenoliths of the 1631 Vesuvius eruption are phlogopites characterized by a combination of low extent of oxy-type and variable extent OH-F-substitutions, as testified by the range of F concentration (from ~ 0.20 to 0.80 apfu). Micas from xenoliths of the 1872 Vesuvius eruption exhibit structural peculiarities typical of fluorophlogopites, i.e. OH-F-substitution is predominant. Micas from the xenolith of the 1944 Vesuvius eruption display features typical of oxy-substituted micas. The variability of the crystal chemical features of the studied micas are consistent with the remarkable variation of their host rocks. Micas from 1631 nodules are related to metasomatic, skarn-type environment, deriving from the metamorphosed wall-rocks hosting the magma reservoir. The fluorophlogopites from the 1872 xenoliths testify for strongly dehydrated environmental conditions compared to those of the 1631 and 1944 hosts. Finally, magma storage condition at depth, associated to a decreasing aH2O may have promoted major oxy-type substitutions in 1944 biotites.

(Table 1) Fluorine concentrations in Pacific waters

An express potentiometric method for determination of total and ionic concentrations of fluorine in sea water was developed, using a fluorine selective electrode as a sensor, with a lanthanum fluoride single crystal membrane. The minimum fluorine concentration measurable by the method is 0.2 mg/liter. Relative accuracy of determinations is +/-4% in 1 to 2 mg/liter fluorine concentration range. One determination requires no more than 20 minutes.

Geochemistry of Apatite from rapid cooled samples

Apatite (U-Th-Sm)/He (AHe) thermochronology is increasingly used for reconstructing geodynamic processes of the upper crust and the surface. Results of AHe thermochronology, however, are often in conflict with apatite fission track (AFT) thermochronology, yielding an inverted age-relationship with AHe dates older than AFT dates of the same samples. This effect is mainly explained by radiation damage of apatite, either impeding He diffusion or causing non-thermal annealing of fission tracks. So far, systematic age inversions have only been described for old and slowly cooled terranes, whereas for young and rapidly cooled samples 'too old' AHe dates are usually explained by the presence of undetected U and/or Th-rich micro-inclusions. We report apatite (U-Th-Sm)/He results for rapidly cooled volcanogenic samples deposited in a deep ocean environment with a relatively simple post-depositional thermal history. Robust age constraints are provided independently through sample biostratigraphy. All studied apatites have low U contents (< 5 ppm on average). While AFT dates are largely in agreement with deposition ages, most AHe dates are too old. For leg 43, where deposition age of sampled sediment is 26.5-29.5 Ma, alpha-corrected average AHe dates are up to 45 Ma, indicating overestimations of AHe dates up to 50%. This is explained by He implantation from surrounding host U-Th rich sedimentary components and it is shown that AHe dates can be "corrected" by mechanically abrading the outer part of grains. We recommend that particularly for low U-Th-apatites the possibility of He implantation should be carefully checked before considering the degree to which the alpha-ejection correction should be applied.

Paleoclimate records from maar Monticchio

Oxygen-isotope records from Greenland ice cores indicate numerous rapid climate fluctuations during the last glacial period. North Atlantic marine sediment cores show comparable variability in sea surface temperature and the deposition of icerafted debris. In contrast, very few continental records of this time period provide the temporal resolution and environmental sensitivity necessary to reveal the extent and effects of these environmental fluctuations on the continents. Here we present high-resolution geochemical, physical and pollen data from lake sediments in Italy and from a Mediterranean sediment core, linked by a common tephrochronology. Our lacustrine sequence extends to the past 102,000 years. Many of its features correlate well with the Greenland ice-core records, demonstrating that the closely coupled ocean-atmosphere system of the Northern Hemisphere during the last glacial extended its influence at least as far as the central Mediterranean region. Numerous vegetation changes were rapid, frequently occurring in less than 200 years, showing that the terrestrial biosphere participated fully in lastglacial climate variability. Earlier than 65,000 years ago, our record shows more climate fluctuations than are apparent in the Greenland ice cores. Together, the multi-proxy data from the continental and marine records reveal differences in the seasonal character of climate during successive interstadials, and provide a step towards determining the underlying mechanisms of the centennial-millennial-scale variability.

Summary of 40Ar/39Ar results from sediment core CRP-2A (Table 1)

40Ar/39Ar analyses of tephra and clasts of volcanic rock provide age constraints for upper parts of the CRP-2A core. Single-crystal laser-fusion analyses of anorthoclase phenocrysts from three tephra-bearing layers yielded the most precise age constraints for CRP-2A. The dated tephra layers are: 1) a 2.7-m-thick interval of pumice and ash layers between 111.5 and 114.2 meters below sea floor (mbsf) (weighted mean age = 21.44 ± 0.05 Ma, +2.2); 2) a concentration of pumice near 193.4 mbsf (23.98 ± 0.13 Ma): and 3) a concentration of pumice near 280 mbsf (24,22 ± 0.03 Ma) (all ages are calibrated relative to Fish Canyon Tuff sanidine at 27.84 Ma). The 111 to 114 mbsf tephra is almost entirely non-reworked, and the 193 mbsf and 280 mbsf tephra concentrations are interpreted as being reworked and redeposited soon after eruption. All three of the tephra ages are therefore considered to be equivalent to depositional ages. The variation in precision of these three age determinations is largely a function of phenocryst size and abundance. The accuracy of these ages is equal to the accuracy of the current calibration of the 40Ar/39Ar methode (about ± 1 %). 40Ar/39Ar results from volcanic clasts provide three additional maximum age constraints for the CRP-2A core. Single-crystal laser-fusion of sanidine phenocrysts from a rhyolitic clast from 294 mbsf yielded a precise maximum depositional age of 24.98 ± 0.08 Ma, and plateau ages of groundmass concentrates from basaltic clasts near 36.02 mbsf and 125.92 mbsf yielded maximum depositional ages of 19.18 ± 0.12 Ma, and 22.56 ± 0.14 Ma, respectively. The 40Ar/39Ar data, in association with biostratigraphic, paleomagnetic, and isotopic age constraints for CRP-2A, confirm interpretation for rapid sedimentation rates in the 36 to 280 mbsf interval, particularly in the 193 to 280 mbsf interval where they support interpretations for sedimentation cycles spanning 100 k.y. intervals. In addition to the 19 to 25 Ma ages measured from thephra layers and clasts, provenance-related ages ranging from 150 to 450 Ma were determined from clasts and individual detrital or xenocrystic crystals from CRP-2A.