Radiation-induced defects in quartz. III. Single-crystal EPR,ENDOR and ESEEM study of a peroxy radical

The X- and W-band single-crystal electron paramagnetic resonance spectra of an electron-irradiated natural quartz permit quantitative analysis of a ²⁹Si hyperfine structure (A ~12.6 MHz) and an ²⁷Al hyperfine structure (A ≤ 0.8 MHz) for a previously reported hole-like center. The ²⁹Si hyperfine structure arises from interaction with two equivalent Si atoms and is characterized by the direction of the unique A axis close to a Si–O bond direction. The ²⁷Al hyperfine structure, confirmed by pulsed electron nuclear double resonance and electron spin echo envelope modulation spectra, is characterized by the unique A axis approximately along a twofold symmetry axis. These ²⁹Si and ²⁷Al hyperfine data, together with published theoretical results on peroxy radicals in SiO₂ as well as our own density functional theory (DFT) calculations on model peroxy centers, suggest this hole-like center to have the unpaired spin on a pair of oxygen atoms linked to two symmetrically equivalent Si atoms and a substitutional Al³⁺ ion across the c-axis channel, a first peroxy radical in quartz. The nuclear quadrupole matrix P also suggests that the Al³⁺ ion corresponds closely to the diamagnetic precursor to the [AlO₄]⁰ center. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Overpressure within upper continental slope sediments from CPTU data,Gulf of Lion,NW Mediterranean Sea

Data from in situ piezocone tests (CPTU) and laboratory analyses are utilized for the interpretation of the stress history of Quaternary sedimentary sequences in the upper continental slope of the Gulf of Lion, northwestern Mediterranean Sea. A CPTU based preconsolidation pressure profile referenced to the current effective stress indicates that the deposit is underconsolidated from 12 meters below the seafloor (mbsf) down to at least 150 mbsf. Excess pore pressure below 12 mbsf is further supported by results from oedometer and dissipation tests. Subseafloor pockmarks and indications of free gas in seismic reflection profiles reveal four main overpressure sources (SI–SIV) with overpressure ratios >0.3 at subseafloor depths coinciding with levels where the dominantly silty-clayey sediment contains increased proportions of sand. We relate the excess pore pressure related to free gas due to gas exsolution processes and sea level variations driven by Pleistocene sea level changes.     

Rheological gravity model of the crust and upper mantle of Transbaikalia

Based on rheological interpretation of formalized gravity models, earlier known deep-seated structures in the Earth’s crust and mantle of Transbaikalia have been detailed and new ones discovered. The structures are asymmetric and transverse relative to the Baikal rift zone. Their presence explains the peculiar features of the Baikal rift, including the one-way southeasterly direction of horizontal displacement of tectonic masses and northwestern migration of the Earth’s crust extension processes. The prolonged history (more than 250 Ma) of the Baikal rift zone and Transbaikalia mountainous country involved gravity or rotational detachments of rigid tectonic slabs from the craton and their sliding along intracrustal and subcrustal decollement zones into the above-dome area of the Transbaikalia asthenolith.     

Metamorphic reactions in dry and aluminous granulites: a Perple_X <Emphasis Type="Italic">P–T</Emphasis> pseudosection analysis of the influence of effective reaction volume

In high-Mg, Al metapelites, monophase sapphirine corona occur around spinel–corundum aggregates in monomineralic cordierite layers, and bi-phase orthopyroxene–sillimanite aggregates replace locally warped sapphirine in polygonized cordierite aggregates. P–T phase topologies computed (Perple_X software) using compositions of cordierite-rich layers that host the reaction textures did not match the assemblages for the discontinuous reactions spinel + corundum + cordierite → sapphirine and sapphirine + cordierite → orthopyroxene + sillimanite. Instead, the reaction assemblages were reproduced using P–T pseudosection analysis for micro-domain reaction volumes estimated from compositions of product phases in the volume proportion they occur. The results are consistent with known phase relations deduced using Schreinmakers P–T grids. Apparently, the compositions of cordierite-rich layers that hosted the reaction textures were inadequate chemical proxies for determining P–T–X relations of phase-boundary controlled reactions influenced by compositions of the nearest-neighbor minerals in the proportion they react (effective composition), and not in the proportion they existed in the layer/bulk rock. In other words, P–T–X phase topologies and reconstructed P–T paths in dry and aluminous rocks may be best understood by thermodynamic modeling of reactions using effective reaction volume compositions rather than the bulk composition of the rock or the mineralogical layer that host the reaction textures.     

Crack damage stress as a composite function of porosity and elastic matrix stiffness in dolomites and limestones

Twenty-five uniaxial compression tests were performed to determine stress at onset of dilation, referred to herein as “the crack damage stress,” in heterogeneous dolomites and limestones. A simplified model for crack damage stress (σ_cd) is developed here using porosity, elastic modulus, Poisson's ratio and three empirical coefficients. The model shows that when porosity decreases and elastic modulus increases, σ_cd rapidly increases and approaches its maximum value. On the other hand, when porosity increases and elastic modulus decreases, σ_cd rapidly decreases and approaches its minimum value. The proposed model is validated for six heterogeneous limestone and dolomite formations which are widely distributed in Israel.     

Chemical evolution and petrogenetic implications of loparite in the layered,agpaitic Lovozero complex,Kola Peninsula,Russia

Summary Lovozero, the largest of the world’s layered peralkaline intrusions, includes gigantic deposits of Nb + REE-loparite ore. Loparite, (Na,Ce,Ca)₂(Ti,Nb)₂O₆, became a cumulus phase after crystallisation of about 35% of the ‘Differentiated Complex’, and its compositional evolution has been investigated through a 2.35 km section of the intrusion. The composition of the cumulus loparite changes systematically upwards through the intrusion with an increase in Na, Sr, Nb and Th and decrease in REE and Ti. This main trend of loparite evolution records differentiation of the peralkaline magma through crystallisation of 1600 m of the intrusion. The formation of the loparite ores was the result of several factors including the chemical evolution of the highly alkaline magma and mechanical accumulation of loparite at the base of a convecting unit. At later stages of evolution, when concentrations of alkalis and volatiles reached very high levels, loparite reacted with the residual melt to form a variety of minerals including barytolamprophyllite, lomonosovite, steenstrupine-(Ce), vuonnemite, nordite, nenadkevichite, REE, Sr-rich apatite, vitusite-(Ce), mosandrite, monazite-(Ce), cerite and Ba, Si-rich belovite. The absence of loparite ore in the “Eudialyte complex” is likely to be a result of the wide crystallisation field of lamprophyllite, which here became a cumulus phase. Received November 6, 2000; revised version accepted January 18, 2001     

KARSTIC: a sensitivity method for carbonate aquifers in karst terrain

. Groundwater in karstic aquifers can be dangerously sensitive to contamination. Many cities in the western USA rely on karstic carbonate aquifers for municipal water supplies. For example, Rapid City, South Dakota, pumps more than half of its drinking water from wells in the Madison Limestone. This work examined the sensitivity of karstic aquifers to surface contamination in mountainous terrain. Where karstic carbonate aquifers are exposed at their outcrop areas, they are particularly susceptible to the introduction of contamination through diffuse recharge or through point recharge at swallow holes along streams. Residential developments in mountainous regions of the western USA are encroaching on the recharge areas of karstic aquifers. Many of these residential developments are served by onsite wastewater disposal systems such as septic tanks and drain fields, with the attendant danger of introduction of pathogens from malfunctioning treatment systems above fractured limestone which offers little filtering. Where streams disappear into karstic aquifers at swallow holes, microbial contaminants such as Giardia or Cryptosporidium are a concern, as well as potential spills, leaks, or accidents along roads near these streams. The KARSTIC method developed and modified in this work puts greater emphasis on karst features than previous sensitivity procedures such as the US Environmental Protection Agency's DRASTIC method. The modified method gives increased attention to highly sensitive areas of karstic carbonate aquifers by weighting the synergistic effects of fracturing, karst development, and swallow holes of recharging streams. In a field application, hydrogeologic maps of a watershed in the Black Hills, USA, were digitized into a geographic information system. The resulting sensitivity map and report can be used by planners, managers, and the public as a screening tool for assessing groundwater sensitivity in regions which include karstic aquifers.     

A Model for the polar motion of the deformable Earth adequate for astrometric data

Refined analytical expressions for the frequencies corresponding to the Chandler motion of the pole and the diurnal rotation of the deformable Earth are derived. Numerical estimates of the period and amplitude of the polar oscillations are presented. The trajectory of the Chandler polar motion derived via numerical modeling is in qualitative and quantitative agreement with experimental data from the International Earth Rotation Service (IERS). An evolutionary model describing slow variations in the Earth’s rotation parameters under the action of the dissipative moments of the tidal gravitational forces on time scales considerably longer than the precession period of the Earth’s axis is constructed. The axis of the Earth’s figure tends to approach the angular momentum vector of the proper rotation.