Polarized electronic absorption spectra of 3d3-configurated tetravalent manganese in octahedral fields of Mn(SeO3)2

Polarized optical absorption spectra of Mn(IV) in octahedral crystal fields of Mn(SeO₃)₂ have been studied by means of microscope-spectrometry in the range 40000-4000 cm^?1 and at temperatures between 113 K and 293 K. Intense charge-transfer absorptions (linear absorption coefficient α ? 30000 cm^?1) completely mask the d-d transitions in the UV and VIS region above ≈23000 cm^?1. The optical electronegativity χ _opt of Mn(IV) in Mn(SeO₃)₂ is estimated to be 2.7. In accordance with the d ₃ configuration of tetravalent manganese three d-d bands observed at ambient temperatures at 13250, 14137 (α≈50 cm^?1) and ≈18500 cm^?1 (α≈500–800 cm^?1) are assigned to the spin forbidden ⁴ A _2g →² E _g and ⁴ A _2g →² T _1g transitions as well as to the first spin allowed ⁴ A _2g →⁴ T ^2g transition, respectively. These assignments allow the calculation of the following ligand field parameters: Dq ≈ 1850 cm^?1, B ₅₅ = 869 cm^?1 (β ₅₅ = 0.82), and C = 2346 cm^?1 (293 K).     

Polarized single-crystal FTIR-spectra of natural staurolite

Polarized infrared absorption spectra of thin single-crystal slabs parallel to (010) and (001) of a staurolite from Pizzo Forno, Ticino, with analyzed composition (Fe_2.9Mg_0.9Zn_0.1Mn_0.1)Al_17.5Ti_0.1(Si_7.7Al_0.3)O₄₈H₃ have been measured in the range of 3000–4000 cm^?1. From the pleochroitic behaviour of the OH-vibrations three groups of bands can be distinguished: the bands of group I, a strong band at 3445 cm^?1 plus a weak shoulder at 3358 cm^?1, and the bands of group II, a weak band centered at 3677 cm^?1 plus a shoulder at 3635 cm^?1, are assigned to the H1 and H2 protons, respectively. The bands of group III, a weak band at 3577 cm^?1 plus a shoulder, cannot be interpreted on the basis of the proton positions known so far. We assign them to an additional proton H3, which is bonded to O1 and shows a bifurcated hydrogen bridge to two O5 in a vacant T2 site.     

River stabilisation due to changing climate and vegetation during the late Quaternary in western Tasmania, Australia

The Stanley River in western Tasmania, Australia, contains sub-fossil rainforest logs within the channel and floodplain. Of the more than 85 radiocarbon dates obtained, all but 3 date from 17 ka to the present and permit an interpretation of fluvial and related environmental changes over this period. Particular attention is focused on the interactive relationship between the river and its riparian rainforest. Following the Last Glacial Maximum, the Stanley River was a laterally active gravel-load system reworking most of its valley floor in the upstream reaches. With ameliorating conditions at the end of the Pleistocene, climate became less seasonal and flow regimes less energetic. Huon pines already present in the catchment, re-asserted themselves in the form of dense tree cover along the river banks and floodplains with basal floodplain deposition shifting from gravels to coarse sands and granules. By about 3.5 ka, a further change in climate reduced stream discharges substantially. As a result the channel reduced in size, transported finer sediment, became laterally stable, and the floodplain accreted with overbank deposits of sand and silt. Huon pines falling into the channel formed obstructions of woody debris, some surviving for 2 ka. These have reduced stream power and boundary shear stress, further contributing to channel stability. Generational sequences of Huon pines on the river banks, some extending back 1–2 ka, are additional evidence of this stability. Since the Pleistocene, changing climate and the re-establishment of dense riparian rainforest appear to have stabilised the river channels and floodplains of western Tasmania.     

Fluctuation dissipation in a general circulation model

This paper considers the climate response to step function changes in the solar constant in two versions of a general circulation model with simplified geography. The NCAR CCM0 model is applied to an all-land planet with no topography (Terra Blanda). In one version there is moisture in the air (as well as self-generated clouds) as evaporated from an ideal surface at a fixed 80% of saturation. In the other version there is no moisture in the atmosphere. We examine the decay of natural anomalies in the large-scale temperature field in each model and compare the time dependence of the ensemble average with the average temporal behavior of the response to step function changes in the solar constant. The fluctuation-dissipation theorem of statistical mechanics makes specific predictions about the relationship between the two curves. We conduct the experiments for both versions of the model since the sensitivity is quite different for each. The theorem is found to hold reasonably well in each case.     

Greenhouse sensitivity experiments with penetrative cumulus convection and tropical cirrus albedo effects

Results are presented from two versions of a global R15 atmospheric general circulation model (GCM) coupled to a nondynamic, 50-m deep, slab ocean. Both versions include a penetrative convection scheme that has the effect of pumping more moisture higher into the troposphere. One also includes a simple prescribed functional dependence of cloud albedo in areas of high sea-surface temperature (SST) and deep convection. Previous analysis of observations has shown that in regions of high SST and deep convection, the upper-level cloud albedos increase as a result of the greater optical depth associated with increased moisture content. Based on these observations, we prescribe increased middle- and upper-level cloud albedos in regions of SST greater than 303 K where deep convection occurs. This crudely accounts for a type of cloud optical property feedback, but is well short of a computed cloud-optical property scheme. Since great uncertainty accompanies the formulation and tuning of such schemes, the prescribed albedo feedback is an intermediate step to examine basic feedbacks and sensitivities. We compare the two model versions (with earlier results from the same model with convective adjustment) to a model from the Canadian Climate Centre (CCC) having convective adjustment and a computed cloud optical properties feedback scheme and to several other GCMs. The addition of penetrative convection increases tropospheric moisture, cloud amount, and planetary albedo and decreases net solar input at the surface. However, the competing effect of increased downward infrared flux (from increased tropospheric moisture) causes a warmer surface and increased latent heat flux. Adding the prescribed cirrus albedo feedback decreases net solar input at the surface in the tropics, since the cloud albedos increase in regions of high SST and deep convection. Downward infrared radiation (from increased moisture) also increases, but this effect is overpowered by the reduced solar input in the tropics. Therefore, the surface is somewhat cooler in the tropics, latent heat flux decreases, and global average sensitivity to a doubling of CO₂ with regard to temperature and precipitation/evaporation feedback is reduced. Similar processes, evident in the CCC model with convective adjustment and a computed cloud optical properties feedback scheme, occur over a somewhat expanded latitudinal range. The addition of penetrative convection produces global effects, as does the prescribed cirrus albedo feedback, although the strongest local effects of the latter occur in the tropics.Portions of this study are supported by the Office of Health and Environmental Research of the U.S. Department of Energy as part of its Carbon Dioxide Research Program, and by the Electric Power Research Institute as part of its Model Evaluation Consortium for Climate Assessment ProjectThe National Center for Atmospheric Research is sponsored by the National Science Foundation     

Contemporary and palaeo channel patterns and the late quaternary stratigraphy of Cooper Creek,Southwest Queensland,Australia

Braided and anastomosing channels make up two major coexistent networks in the mud-dominated fluvial system of Cooper Creek, Southwest Queensland. The floodplain is characterized by a system of mud braids operative when floods inundate the whole alluvial surface. Anastomosing channels are inset deeper into the floodplain, operate at modern flows, and transport a traction load of sand. Shallow stratigraphic data show that an underlying sand sheet is unrelated to surface channel patterns and was formed by a system of meandering streams. According to preliminary dates based on thermoluminescence, the change from a sand- to mud-dominated fluvial regime took place between 50 000 and 200 000 years B.P., and probably reflects increasing aridity.     

Crystal field spectra and jahn teller effect of Mn3+ in clinopyroxene and clinoamphiboles from India

Blanfordite (I), winchite (II), and juddite (III), all showing vivid colors and pleochroism, from highly oxidized parageneses of Indian gondites were studied by microprobe, Mössbauer, and microscope-spectrophotometric techniques and by X-ray structure refinements. The compositions of the Mn-bearing minerals were close to diopsideacmite (I) and magnesio-arfvedsonite to magnesio-riebeckite (II and III). Transition metal ions are located inM(1)-octahedra (I) or predominantlyM(2)-octahedra (II, III). Mössbauer spectra of⁵⁷Fe(IS, ΔE _Q) are typical of octahedral Fe³⁺ only. Polarized absorption spectra in the UV/VIS/NIR ranges explain color and pleochroism of the minerals. The position of the UV-“edge” is correlated with Fe³⁺-contents of the minerals, except for judditeE ∥Z, where the edge shows an unusual low energy position. This is most likely due to Mie-scattering of submicroscopic inclusions of braunite with nearly uniform dimensions. In the VIS range, the spectra are dominated by a complex band system between 15,000 and 20,000 cm^?1. Energies and ?-values of component bands are compatible with those of Mn³⁺ d-d transitions in other Mn³⁺-bearing silicates. The polarization behavior of component bands can best be explained by aC ₂(C2″) symmetry of the crystal field. The Jahn-Teller splitting (<9,000 cm^?1) of the⁵ E _g ground state of Mn³⁺ inO _h crystal fields is appreciably smaller than in other Mn³⁺-silicates. Crystal field parameters 10Dq, (I) 13,650, (II) ca. 11,640, and (III) 11,925 cm^?1, are near to that in piemontite. The crystal field stabilization energy of Mn³⁺, (I) 146, (II) ca. 140, (III) 142 \({{{\text{kJ}}} \mathord{\left/ {\vphantom {{{\text{kJ}}} {\text{g}}}} \right. \kern-0em} {\text{g}}}{\text{ - atom}}_{{\text{Mn}}^{{\text{3 + }}} } \) , is appreciably smaller than that found in other Mn³⁺-silicates (piemontites and manganian andalusites, viridines and kanonaite).