δC of low-molecular-weight organic acids generated by the hydrous pyrolysis of oil-prone source rocks

Low-molecular-weight (LMW) aqueous organic acids were generated from six oil-prone source rocks under hydrous-pyrolysis conditions. Differences in total organic carbon-normalized acid generation are a function of the initial thermal maturity of the source rock and the oxygen content of the kerogen (OI). Carbon-isotope analyses were used to identify potential generation mechanisms and other chemical reactions that might influence the occurrence of LMW organic acids. The generated LMW acids display increasing ¹³C content as a function of decreasing molecular weight and increasing thermal maturity. The magnitudes of observed isotope fractionations are source-rock dependent. These data are consistent with δ¹³C values of organic acids presented in a field study of the San Joaquin Basin and likely reflect the contributions from alkyl-carbons and carboxyl-carbons with distinct δ¹³C values. The data do not support any particular organic acid generation mechanism. The isotopic trends observed as a function of molecular weight, thermal maturity, and rock type are not supported by either generation mechanisms or destructive decarboxylation. It is therefore proposed that organic acids experience isotopic fractionation during generation consistent with a primary kinetic isotope effect and subsequently undergo an exchange reaction between the carboxyl carbon and dissolved inorganic carbon that significantly influences the carbon isotope composition observed for the entire molecule. Although generation and decarboxylation may influence the δ¹³C values of organic acids, in the hydrous pyrolysis system described, the nondestructive, pH-dependent exchange of carboxyl carbon with inorganic carbon appears to be the most important reaction mechanism controlling the δ¹³C values of the organic acids.     

New W-isotope evidence for rapid terrestrial accretion and very early core formation

The short-lived ¹⁸²Hf-¹⁸²W-isotope system is an ideal clock to trace core formation and accretion processes of planets. Planetary accretion and metal/silicate fractionation chronologies are calculated relative to the chondritic ¹⁸²Hf-¹⁸²W-isotope evolution. Here, we report new high-precision W-isotope data for the carbonaceous chondrite Allende that are much less radiogenic than previously reported and are in good agreement with published internal Hf-W chronometry of enstatite chondrites. If the W-isotope composition of terrestrial rocks, representing the bulk silicate Earth, is homogeneous and 2.24 ε_182W units more radiogenic than that of the bulk Earth, metal/silicate differentiation of the Earth occurred very early. The new W-isotope data constrain the mean time of terrestrial core formation to 34 million years after the start of solar system accretion. Early terrestrial core formation implies rapid terrestrial accretion, thus permitting formation of the Moon by giant impact while ¹⁸²Hf was still alive. This could explain why lunar W-isotopes are more radiogenic than the terrestrial value.     

Determining Q of near-surface materials from Rayleigh waves

High-frequency (≥2 Hz) Rayleigh wave phase velocities can be inverted to shear (S)-wave velocities for a layered earth model up to 30 m below the ground surface in many settings. Given S-wave velocity (V_S), compressional (P)-wave velocity (V_P), and Rayleigh wave phase velocities, it is feasible to solve for P-wave quality factor Q_P and S-wave quality factor Q_S in a layered earth model by inverting Rayleigh wave attenuation coefficients. Model results demonstrate the plausibility of inverting Q_S from Rayleigh wave attenuation coefficients. Contributions to the Rayleigh wave attenuation coefficients from Q_P cannot be ignored when Vs/V_P reaches 0.45, which is not uncommon in near-surface settings. It is possible to invert Q_P from Rayleigh wave attenuation coefficients in some geological setting, a concept that differs from the common perception that Rayleigh wave attenuation coefficients are always far less sensitive to Q_P than to Q_S. Sixty-channel surface wave data were acquired in an Arizona desert. For a 10-layer model with a thickness of over 20 m, the data were first inverted to obtain S-wave velocities by the multichannel analysis of surface waves (MASW) method and then quality factors were determined by inverting attenuation coefficients.     

Solar–terrestrial effects possibly stronger in biblical times

Paleomagnetic studies have shown that, moving backwards in time, the geomagnetic dipole moment increased to a peak nearly 50% greater than at present ca. 2500 years ago. Attempts to model how changes in dipole moment affect solar–terrestrial relations have hitherto invoked a scaling relation for the size of the magnetosphere based on finding where the magnetic pressure of the dipole field balances the ram pressure of the solar wind. This approach predicts that, following a solar storm, the strength of the terrestrial response represented by the electrical potential across the auroral zones in the ionosphere should vary as the 1/3 power of dipole moment. Such a weak dependence suggests that a 50% increase in dipole moment would minimally effect (14%) terrestrial manifestations of solar storms. Recent work, however, based on a feedback mechanism involving electrical currents coupling the magnetosphere and ionosphere has identified a stronger 4/3, power scaling relation applicable to storm conditions. Here we use a global MHD simulation to calculate for a 50% increased dipole moment the correspondingly increased auroral-zone potential and its extension to low latitudes.     

African monsoon variability during the previous interglacial maximum

Little is known about centennial- to millennial-scale climate variability during interglacial times, other than the Holocene. We here present high-resolution evidence from anoxic (unbioturbated) sediments in the eastern Mediterranean Sea that demonstrates a sustained ∼800-yr climate disturbance in the monsoonal latitudes during the Eemian interglacial maximum (∼125 ka BP). Results imply that before and after this event, the Intertropical Convergence Zone (ITCZ) penetrated sufficiently beyond the central Saharan watershed (∼21°N) during the summer monsoon to fuel flooding into the Mediterranean along the wider North African margin, through fossil river/wadi systems that to date have been considered only within a Holocene context. Relaxation in the ITCZ penetration during the intra-Eemian event curtailed this flux, but flow from the Nile - with its vast catchment area - was not affected. Previous work suggests a concomitant Eurasian cooling event, with intensified impact of the higher-latitude climate on the Mediterranean basin. The combined signals are very similar to those described for the Holocene cooling event around 8 ka BP. The apparent type of concurrent changes in the monsoon and higher-latitude climate may reflect a fundamental mechanism for variability in the transfer of energy (latent heat) between the tropics and higher latitudes.     

Spatial variation of seismic motion induced by propagation of body waves

Spatial variation of earthquake ground motion is an important phenomenon that cannot be ignored in the design and safety of strategic structures. Several models have been developed to describe this variation using statistical, mathematical or physical approaches. The latter approach is not specific to an event. A recent contribution, which uses such an approach and called complete stochastic deamplification approach (CSDA), was developed [1]. The aim of this paper is to analyze the spatial variation of earthquake motion induced by the propagation of body waves using the CSDA. Coherency functions are evaluated for the cases of SH–SV–P waves propagating through stratified soil. Results obtained show that the variation of the coherency function is not the same for vertical and horizontal components and that the motion is more coherent at depth than at the free surface. In fact, we found that the rate of decrease with frequency and distance is not the same if P–SV waves propagate through stratified soil.     

Production of selected cosmogenic radionuclides by muons: 2. Capture of negative muons

We have determined the production yields for radionuclides in Al₂O₃, SiO₂, S, Ar, K₂SO₄, CaCO₃, Fe, Ni and Cu targets, which were irradiated with slow negative muons at the Paul Scherrer Institute in Villigen (Switzerland). The fluences of the stopped negative muons were determined by measuring the muonic X-rays. The concentrations of the long-lived and short-lived radionuclides were measured with accelerator mass spectrometry (AMS) and γ-spectroscopy, respectively. Special emphasis was put on the radionuclides ¹⁰Be, ¹⁴C and ²⁶Al produced in quartz targets, ²⁶Al in Al₂O₃ and S targets, ³⁶Cl in K₂SO₄ and CaCO₃ targets, and ⁵³Mn in Fe₂O₃ targets. These targets were selected because they are also the naturally occurring target minerals for cosmic ray interactions in typical rocks. We also present results of calculations for depth-dependent production rates of radionuclides produced after cosmic ray μ⁻ capture, as well as cosmic ray-induced production rates of geologically relevant radionuclides produced by the nucleonic component, by μ⁻ capture, by fast muons and by neutron capture.     

A theoretical analysis of the observed variability of the geomagnetic dipole field

We present a detailed analysis of the Sint-800 virtual axial dipole moment (VADM) data in terms of an Ω mean field model of the geodynamo that features a non-steady generation of poloidal from toroidal magnetic field. The result is a variable excitation of the dipole mode and the overtones, and there are occasional dipole reversals. The model permits a theoretical evaluation of the statistical properties of the dipole mode. We show that the model correctly predicts the distribution of the VADM and the autocorrelation function inferred from the Sint-800 data. The autocorrelation technique allows us to determine the turbulent diffusion time τ_d=R²/β of the geodynamo. We find that τ_d is about 10–15 kyr. The model is able to reproduce the observed secular variation of the dipole mode, and the mean time between successive dipole reversals. On the other hand, the duration of a reversal is a factor 2 too long. This could be due to imperfections in the model or to unknown systematics in the Sint-800 data. The use of mean field theory is shown to be selfconsistent.