不同围压下孔隙度不同的干燥及水饱和岩样中的纵横波速度及衰减

选择具有不同孔隙度的三种岩石样品,在最高达600MPa （干燥样品）或300MPa （水饱和样品）的不同围压条件下,同时测量了在其中传播的纵、横波的速度及衰减。对于低孔隙度的花岗岩,干燥和水饱和样品的 Q 值几乎没有差别,但与干燥样品相比,水饱和样品中的纵波速度较高而横波速度稍低。对于中等孔隙度的杂砂岩,干燥样品和水饱和样品的波速和 Q 值及其随围压的变化有明显的不同。在高孔隙度的砂岩中这种不同更加显著。综合分析同时测得的纵、横波速度和 Q 值可以发现,当围压增加时,低孔隙度的花岗岩中同体应变相关的能量损失与同剪切应变相关的能量损失之比减小,但在中等孔隙度的杂砂岩和高孔隙度的砂岩中这一比值增大;同时,水饱和样品中的这一比值要比干燥样品中的大,而且它们之间的差别同样品的孔隙度正相关。     

Kinetics of the Abiotic Reduction of Polymeric Manganese Dioxide by Nitrite: An Anaerobic Nitrification Reaction

Manganese oxides are strong environmental oxidants recently found to be involvedin the nitrogen cycle. Of the several possible reactions with reduced nitrogen species,the reduction of MnO₂ by nitrite has only received marginal attention. Yet, this reaction might explain why nitrification can occur in the absence of O₂, observed in both sediments and water columns. We have determined the stoichiometry of this reaction, as well as the chemical kinetics and the activation parameters, using a soluble polymeric form of MnO₂. The reaction rate decreases with increasing pH and decreasing temperature. The reaction is first order in each reactant with a second order rate constant (k) = 493 M^-1 min^-1 at 21.5 °C and pH = 5.00. The energy of activation (Ea = 9.370 kJ/mole) and the entropy of activation ( S = -169.5 J/mole) show the reaction to be associative and diffusion controlled, occurring via an inner-sphere mechanism, likely with O atom transfer from MnO₂ to HNO₂. The reaction is proton assisted and slowsdown at pH 5.5 where NO₂ ^- and MnO₂ (unprotonated and negatively charged) become the dominant species. In natural waters and sediments where anaerobic nitrification has been observed the pH is higher than this. Thus, the thermodynamically favorable reaction will likely proceed by microbial mediation.     

Determination of Chloroethers in Aqueous Samples Using Solid-phase Microextraction

A method for the determination of di- and tetrachlorinated ethers (haloethers) in aqueous samples using solid-phase microextraction (SPME) combined with capillary GC has been developed. Using 100-μm polydimethylsiloxane fibers, the influence of several parameters on the SPME procedure like the exposure time of the fiber in the aqueous sample, the desorption temperature, and the salt content of the sample have been studied. Salt addition has a strong effect on the extraction efficiency of the haloethers investigated. Working with saturated salt solutions, the factor increase of the peak areas was in the range from 5 to 12. These improvements are accompanied by decreased precision and increased equilibration times. The SPME method combined with several detectors (FID, ECD, MS in SIM mode) was evaluated with respect to detection limits, linearities, and precisions. Working with salt addition and FID, detection limits of all compounds investigated were in the range of 0.3 to 1.2 μg/L. Using ECD, the LOD values (limits of detection) were only improved for the tetrachlorinated bis(propyl) ethers (<10 ng/L). Employing mass-spectrometric detection in SIM mode for all chlorinated ethers, detection limits lower than 100 ng/L could be reached. Working with saturated salt solutions, the coefficients of variation were <9% RSD. However, without salt addition, the precision is better than 2.5% RSD for all analytes. Investigations showed that the analysis of the haloethers with SPME is not influenced significantly by the matrix Elbe water. The results of two series of samples demonstrate that SPME-GC-MS allows the sensitive determination of the di- and tetrahalogenated ethers in Elbe river water.     

Porphyrin and chlorin distributions in a Late Pliocene lacustrine sediment

The tetrapyrroles in a highly immature Late Pliocene lacustrine sediment (Willershausen, Germany) show a simple distribution of both chlorin and porphyrin components as the free bases. The major components are C32 desoxophylloerythroaetioporphyrin (DPEP), a C33 bicycloalkano porphyrin, the chlorin analogue of the latter, and desoxophylloerythrin and its chlorin counterpart. The structure of the novel bicycloalkano chlorin was determined using a combination of two-dimensional phase-sensitive COSY NMR and nOe studies. Measurements of delta 13C and other data indicate that DPEP and the bicycloalkano porphyrin were derived from the chlorophyll(s) of photosynthetic organisms utilising a common source of CO2, probably diatoms. The occurrence of DPEP and other minor alkyl porphyrins indicates that the chlorophyll defunctionalisation pathway leading to these components can occur at low temperature and was probably biologically mediated, as was the condensation leading to the fused ring components.     

The influence of dry and water saturated cracks on seismic velocities of crustal rocks - A comparison of experimental data with theoretical model

The pressure dependence of P- and S-wave velocities, velocity anisotropy, shear wave splitting and crack-porosity has been investigated in a number of samples from different crustal rock types for dry and wet (water saturated) conditions. At atmospheric pressure, P-wave velocities of the saturated, low-porosity rocks (< 1%) are significantly higher than in dry rocks, whereas the differences for S-wave velocities are less pronounced. The effect of intercrystalline fluids on seismic properties at increased pressure conditions is particularly reflected by the variation of the Poisson's ratio because P-wave velocities are more sensitive to fluids than S-wave velocities in the low-porosity rocks. Based on the experimental data, the respective crack-density parameter (), which is a measure of the number of flat cracks per volume unit contained within the background medium (crack-free matrix), has been calculated for dry and saturated conditions. There is a good correlation between the calculated crack-densities and crack-porosities derived from the experimentally determined volumetric strain curves. The shear wave velocity data, along with the shear wave polarisation referred to a orthogonal reference system, have been used to derive the spatial orientation of effective oriented cracks within a foliated biotite gneiss. The experimental data are in reasonable agreement with the self consistent model of O'Connell and Budiansky (1974). Taking the various lithologies into account, it is clear from the present study, that combined seismic measurements ofV _p andV _s , using theV _p V _s -ratio, may give evidence for fluids on grain boundaries and, in addition, may provide an estimate on the in-situ crack-densities.     

Implications for groundwater recharge from stable isotopic composition of precipitation in Hawai'i during the 2017–2018 La Niña

The project captured a subset of the hydrological cycle for the tropical island of O'ahu, linking precipitation to groundwater recharge and aquifer storage. We determined seasonal storm events contributed more to aquifer recharge than year-round baseline orographic trade wind rainfall. Hydrogen and oxygen isotope values from an island-wide rain collector network with 20 locations deployed for 16 months and sampled at 3-month intervals were used to create the first local meteoric water line for O'ahu. Isotopic measurements were influenced by the amount effect, seasonality, storm type, and La Niña, though little elevation control was noted. Certain groundwater compositions from legacy data showed a strong similarity with collected precipitation from our stations. The majority of these significant relationships were between wet season precipitation and groundwater. A high number of moderate and heavy rainfall days during the dry season, large percentage of event-based rainfall, and wind directions outside of the typical NE trade wind direction were characteristics of the 2017–2018 wet season. This indicates that the majority of wet season precipitation is from event-based storms rather than typical trade wind weather. The deuterium-excess values provided the strongest evidence of a relationship between groundwater and different precipitation sources, indicating that this may be a useful metric for determining the extent of recharge from different rain events and systems.     

Mineral-solution equilibria—IV. Solubilities and the thermodynamic properties of FeCl20 in the system Fe2O3-H2-H2O-HCl

The solubility of hematite in chloride-bearing hydrothermal fluids was determined in the temperature range 400–600°C and at 1000 and 2000 bars using double-capsule, rapid-quench hydrothermal techniques and a modification of the Ag + AgCl buffer method (Frantz and Popp, 1979). The changes in the molalities of associated hydrogen chloride () as a function of the molality of total iron in the fluid at constant temperature and pressure were used to identify the predominant species of iron in the hydrothermal fluid. The molality of associated HCl varied from 0.01 to 0.15. Associated FeCl₂⁰ was found to be the most abundant species in equilibrium with hematite. Determination of Cl/Fe in the fluid in equilibrium with hematite yields values approximately equal to 2.0 suggesting that ferrous iron is the dominant oxidation state.The equilibrium constant for the reaction Fe₂O₃ + 4HCl⁰ + H₂ = 2FeCl₂⁰ + 3H₂O was calculated and used to estimate the difference in Gibbs free energy between FeCl₂⁰ and HCl⁰ in the temperature range 400–600°C at 1000 and 2000 bars pressure.     

Compound-specific isotopic analyses: a novel tool for reconstruction of ancient biogeochemical processes

Patterns of isotopic fractionation in biogeochemical processes are reviewed and it is suggested that isotopic fractionations will be small when substrates are large. If so, isotopic compositions of biomarkers will reflect those of their biosynthetic precursors. This prediction is tested by consideration of results of analyses of geoporphyrins and geolipids from the Greenhorn Formation (Cretaceous, Western Interior Seaway of North America) and the Messel Shale (Eocene, lacustrine, southern Germany). It is shown (i) that isotopic compositions of porphyrins that are related to a common source, but which have been altered structurally, cluster tightly and (ii) that isotopic differences between geolipids and porphyrins related to a common source are equal to those observed in modern biosynthetic products. Both of these observations are consistent with preservation of biologically controlled isotopic compositions during diagenesis. Isotopic compositions of individual compounds can thus be interpreted in terms of biogeochemical processes in ancient depositional environments. In the Cretaceous samples, isotopic compositions of n-alkanes are covariant with those of total organic carbon, while delta values for pristane and phytane are covariant with those of porphyrins. In this unit representing an open marine environment, the preserved acyclic polyisoprenoids apparently derive mainly from primary material, while the extractable, n-alkanes derive mainly from lower levels of the food chain. In the Messel Shale, isotopic compositions of individual biomarkers range from -20.9 to -73.4% vs PDB. Isotopic compositions of specific compounds can be interpreted in terms of origin from methylotrophic, chemautotrophic, and chemolithotrophic microorganisms as well as from primary producers that lived in the water column and sediments of this ancient lake.     

Sediment provenance of late Quaternary morainic,fluvial and loess‐like deposits in the southwestern Verkhoyansk Mountains (eastern Siberia) and implications for regional palaeoenvironmental reconstructions

A provenance analysis of late Quaternary deposits from tributaries of the Aldan and Lena rivers in Central Yakutia (eastern Siberia) was carried out using analysis of heavy minerals and clay mineralogy. Cluster analysis revealed one assemblage that is characterized by relatively high proportions of amphibole, orthopyroxene and garnet as well as pedogenic clay minerals, reflecting a sediment provenance from the wide catchment area of the Lena and Aldan rivers. In contrast, the three other clusters are dominated by stable heavy minerals with varying amounts of clinopyroxene, apatite and garnet, as well as high percentages of illite and chlorite that are indicative of source rocks of the Verkhoyansk Mountains. Glacial moraines reveal the local mountain source signal that is overprinted by the Lena‐Aldan signal in the oldest moraines by reworking processes. Alluvial sediments in the Verkhoyansk Foreland show a clear Lena source signal through intervals of the middle and late Pleistocene, related to a stream course closer to the mountains at that time. Loess‐like cover sediments are characterized by the dominant Lena provenance with increasing proportions of local mountain sources towards the mountain valleys. Aeolian sands in an alluvial terrace section at the mountain margin covering the time between 30 ka and 10 ka BP reflect temporarily dominant inputs of aeolian materials from the Lena Plains. Copyright © 2007 John Wiley & Sons, Ltd.