A Raman spectroscopic study on the structural disorder of monazite–(Ce)

This study addresses whether Raman spectra can be used to estimate the degree of accumulated radiation damage in monazite-(Ce) samples whose chemical composition was previously determined. Our results indicate that the degree of disorder in monazite–(Ce), as observed from increasing Raman band broadening, generally depends on both the structural state (i.e., radiation damage) and the chemical composition (i.e., incorporation of non-formula elements). The chemical effects were studied on synthetic orthophosphates grown using the Li-Mo flux method, and non radiation-damaged analogues of the naturally radiation-damaged monazite–(Ce) samples, produced by dry annealing. We found that the “chemical” Raman-band broadening of natural monazite–(Ce) can be predicted by the empirical formula, $$ {\hbox{FWHM}} {\hbox{[c}}{{\hbox{m}}^{ - {1}}}{]} = {3}{.95} + {26}{.66} \times {\hbox{(Th}} + {\hbox{U}} + {\hbox{Ca}} + {\hbox{Pb)}} {\hbox{[apfu]}} $$ where, FWHM = full width at half maximum of the main Raman band of monazite–(Ce) (i.e., the symmetric PO₄ stretching near 970?cm^?1), and (Th+U+Ca+Pb) = sum of the four elements in apfu (atoms per formula unit). Provided the chemical composition of a natural monazite–(Ce) is known, this “chemical band broadening” can be used to estimate the degree of structural radiation damage from the observed FWHM of the ν₁(PO₄) band of that particular sample using Raman spectroscopy. Our annealing studies on a wide range of monazite–(Ce) reference materials and other monazite–(Ce) samples confirmed that this mineral virtually never becomes highly radiation damaged. Potential advantages and the practical use of the proposed method in the Earth sciences are discussed.     

Silica-merrihueite/roedderite-bearing chondrules and clasts in ordinary chondrites: New occurrences and possible origin

Abstract Merrihueite (K,Na)₂(Fe, Mg)₅Si₁₂O₃₀ (na < 0.5, fe > 0.5, where na = Na/(Na + K), fe = Fe/(Fe + Mg) in atomic ratio) is a rare mineral described only in several chondrules and irregularly-shaped fragments in the Mezö-Madaras L3 chondrite (Dodd et al., 1965; Wood and Holmberg, 1994). Roedderite (Na,K)₂(Mg, Fe)₅Si₁₂O₃₀ (na > 0.5, fe < 0.5) has been found only in enstatite chondrites and in the reduced, subchondritic silicate inclusions in IAB irons (Fuchs, 1966; Rambaldi et al., 1984; Olsen, 1967). We describe silica-roedderite-bearing clasts in L/LL3.5 ALHA77011 and LL3.7 ALHA77278, a silica-roedderite-bearing chondrule in L3 Mezö-Madaras, and a silica-merrihueite-bearing chondrule in L/LL3.5 ALHA77115. The findings of merrihueite and roedderite in ALHA77011, ALHA77115, ALHA77278 and Mezö-Madaras fill the compositional gap between previously described roedderite in enstatite chondrites and silicate inclusions in IAB irons and merrihueite in Mezö-Madaras, suggesting that there is a complete solid solution of roedderite and merrihueite in meteorites. We infer that the silica- and merrihueite/roedderite-bearing chondrules and clasts experienced a complex formational history including: (a) fractional condensation in the solar nebula that produced Si-rich and Al-poor precursors, (b) melting of fractionated nebular solids resulting in the formation of silica-pyroxene chondrules, (c) in some cases, fragmentation in the nebula or on a parent body, (d) reaction of silica with alkali-rich gas that formed merrihueite/roedderite on a parent body, (e) formation of fayalitic olivine and ferrosilite-rich pyroxene due to reaction of silica with oxidized Fe on a parent body, and (f) minor thermal metamorphism, possibly generated by impacts.     

Contrasting rifted margin styles south of Greenland: implications for mantle plume dynamics

We present new and reprocessed seismic reflection data from the area where the southeast and southwest Greenland margins intersected to form a triple junction south of Greenland in the early Tertiary. During breakup at 56 Ma, thick igneous crust was accreted along the entire 1300-km-long southeast Greenland margin from the Greenland Iceland Ridge to, and possibly 100 km beyond, the triple junction into the Labrador Sea. However, highly extended and thin crust 250 km to the west of the triple junction suggests that magmatically starved crustal formation occurred on the southwest Greenland margin at the same time. Thus, a transition from a volcanic to a non-volcanic margin over only 100–200 km is observed. Magmatism related to the impact of the Iceland plume below the North Atlantic around 61 Ma is known from central-west and southeast Greenland. The new seismic data also suggest the presence of a small volcanic plateau of similar age close to the triple junction. The extent of initial plume-related volcanism inferred from these observations is explained by a model of lateral flow of plume material that is guided by relief at the base of the lithosphere. Plume mantle is channelled to great distances provided that significant melting does not take place. Melting causes cooling and dehydration of the plume mantle. The associated viscosity increase acts against lateral flow and restricts plume material to its point of entry into an actively spreading rift. We further suggest that thick Archaean lithosphere blocked direct flow of plume material into the magma-starved southwest Greenland margin while the plume was free to flow into the central west and east Greenland margins. The model is consistent with a plume layer that is only moderately hotter, 100–200°C, than ambient mantle temperature, and has a thickness comparable to lithospheric thickness variations, 50–100 km. Lithospheric architecture, the timing of continental rifting and viscosity changes due to melting of the plume material are therefore critical parameters for understanding the distribution of magmatism.     

Effect of snow cover on pan-Arctic permafrost thermal regimes

This study quantitatively evaluated how insulation by snow depth (SND) affected the soil thermal regime and permafrost degradation in the pan-Arctic area, and more generally defined the characteristics of soil temperature (T_SOIL) and SND from 1901 to 2009. This was achieved through experiments performed with the land surface model CHANGE to assess sensitivity to winter precipitation as well as air temperature. Simulated T_SOIL, active layer thickness (ALT), SND, and snow density were generally comparable with in situ or satellite observations at large scales and over long periods. Northernmost regions had snow that remained relatively stable and in a thicker state during the past four decades, generating greater increases in T_SOIL. Changes in snow cover have led to changes in the thermal state of the underlying soil, which is strongly dependent on both the magnitude and the timing of changes in snowfall. Simulations of the period 2001–2009 revealed significant differences in the extent of near-surface permafrost, reflecting differences in the model’s treatment of meteorology and the soil bottom boundary. Permafrost loss was greater when SND increased in autumn rather than in winter, due to insulation of the soil resulting from early cooling. Simulations revealed that T_SOIL tended to increase over most of the pan-Arctic from 1901 to 2009, and that this increase was significant in northern regions, especially in northeastern Siberia where SND is responsible for 50 % or more of the changes in T_SOIL at a depth of 3.6 m. In the same region, ALT also increased at a rate of approximately 2.3 cm per decade. The most sensitive response of ALT to changes in SND appeared in the southern boundary regions of permafrost, in contrast to permafrost temperatures within the 60°N–80°N region, which were more sensitive to changes in snow cover. Finally, our model suggests that snow cover contributes to the warming of permafrost in northern regions and could play a more important role under conditions of future Arctic warming.     

Seasonal prediction of global sea level anomalies using an ocean–atmosphere dynamical model

Advanced warning of extreme sea level events is an invaluable tool for coastal communities, allowing the implementation of management policies and strategies to minimise loss of life and infrastructure damage. This study is an initial attempt to apply a dynamical coupled ocean–atmosphere model to the prediction of seasonal sea level anomalies (SLA) globally for up to 7 months in advance. We assess the ability of the Australian Bureau of Meteorology’s operational seasonal dynamical forecast system, the Predictive Ocean Atmosphere Model for Australia (POAMA), to predict seasonal SLA, using gridded satellite altimeter observation-based analyses over the period 1993–2010 and model reanalysis over 1981–2010. Hindcasts from POAMA are based on a 33-member ensemble of seasonal forecasts that are initialised once per month for the period 1981–2010. Our results show POAMA demonstrates high skill in the equatorial Pacific basin and consistently exhibits more skill globally than a forecast based on persistence. Model predictability estimates indicate there is scope for improvement in the higher latitudes and in the Atlantic and Southern Oceans. Most characteristics of the asymmetric SLA fields generated by El-Nino/La Nina events are well represented by POAMA, although the forecast amplitude weakens with increasing lead-time.     

Transient soil response in a porous seabed with variable permeability

The soil permeability of many natural marine sediments decreases with depth because of consolidation under overburden pressure. This is accompanied by a decrease in porosity and void ratio that also affect the permeability. Conventional theories for wave-induced soil response have assumed a homogeneous porous seabed. This paper presents a new approach for the wave-induced response in a soil matrix, with variable permeability as a function of burial depth. The soil matrix considered is unsaturated and anisotropic, and is subject to a three-dimensional wave system. The pore pressure and effective stresses induced by such a system are obtained from a set of equations incorporating a variable permeability. Verification is available through reduction to the simple case of uniform permeability. The results indicate that the effect of variable soil permeability on pore pressure and vertical effective stress may be significant, especially in a gravelled seabed and for unsaturated sandy soils.     

A mixed spectral finite-difference model for pollutant concentrations over a hill

Given incident logarithmic profiles of wind and pollutant concentration above a rough, absorbing surface, the three-dimensional distribution of pollutant concentration over a hill of gentle slope is determined from a linearized model. The model is applied in neutrally stratified flow, without chemistry, and is integrated using spectral methods in the horizontal and a finite-difference scheme in the vertical. This approach allows for flexibility in choosing a closure scheme and a variety of surface boundary conditions. This was not possible in the analytic approach of Padro (1987) who added pollutant concentration and flux to the MS3DJH/1 model of Walmsley et al. (1980). The present model requires as input the turbulent kinetic energy, E, dissipation, , and the perturbation vertical velocity, w, from the three-dimensional boundary-layer flow model of Beljaars et al. (1987), hereinafter referred to as MSFD, The latter model also supplies wind velocity perturbations at the upper boundary, as input to upper boundary conditions on the pollutant flux perturbations.The present study describes applications of the model to idealized terrain features: isolated two- and three-dimensional hills and ridges and an infinite series of ridges. (Application to real terrain, however, presents no difficulties.) Comparisons were made with different (though uniform) surface roughnesses. Tests were performed to examine the effect of upstream terrain features in the periodic domain and to illustrate the importance of the vertical resolution of the output for interpreting results from the sinusoidal terrain case.     

Rb-Sr dating of Paleozoic glauconite from the Llano region,central Texas

Glauconite from eight stratigraphic horizons (Cambrian to Pennsylvanian) in the Llano Uplift, central Texas and two Cretaceous glauconites were analyzed by the Rb-Sr method. Only two untreated samples provide ages in agreement with those anticipated from current best estimates of the geologic time scale. With one exception all the other apparent ages fall short of the estimated age of deposition by as much as 22%. Low ages, the pattern customarily observed, are attributed to postdepositional loss of radiogenic ⁸⁷Sr from expandable layers by weathering or during diagenesis.Detailed leaching experiments using a variety of reagents were performed to characterize the behavior of glauconite. The most promising treatment, which we recommend as standard procedure in all future studies, is with ammonium acetate which is able to purge the mineral of loosely-bound Rb and Sr while leaving tightly-bound components intact. After appropriate leach, three other Rb-Sr ages were brought into coincidence with their estimated ages of deposition.In contrast an Upper Cambrian glauconite was found to be extremely resistant to further alteration by chemical attack′, providing an age of 429 ± 17 M yr. Although 17% short of the age of deposition, this age is interpreted as the time of a real event: diagenetic recrystallization induced by burial. Comparison of data from four samples indicates that for Paleozoic glauconite, conditions exist in which the Rb-Sr system is less susceptible to mild disturbance than is the K-Ar system.     

Geoarchaeological and Bioarchaeological Studies at Mira,an Early Upper Paleolithic Site in the Lower Dnepr Valley,Ukraine

New geoarchaeological and bioarcheological research was undertaken at the open‐air site of Mira, which is buried in deposits of the Second Terrace of the Dnepr River, roughly 15 km downstream from the city of Zaporozhye in Ukraine. Previous excavation of the site revealed two occupation layers dating to ∼32,000 cal BP. The lower layer (II/2) yielded bladelets similar to those of the early Gravettian, while the upper layer (I) contained traces of an artificial shelter and hundreds of bones and teeth of horse (Equus latipes). Mira represents the only firmly dated early Upper Paleolithic (EUP) site in the Dnepr Basin, and occupies a unique topographic setting for the EUP near the center of the broad floodplain of the Dnepr River. The site was visited during a period of floodplain stability, characterized by overbank deposition and weak soil formation under cool climate conditions. Mira was used as a long‐term camp, but also was the locus of large‐mammal carcass processing associated with a nearby kill of a group of horses (Layer I).