Error in digital network and basin area delineation using d8 method: A case study in a sub-basin of the Ganga

Digital elevation model (DEM) is one of the input data derived from different satellite sensors for hydrologic and hydraulic modelings. Two prime questions could be answered before using these DEMs. First, the acceptability of datasets for our use and second appropriate resolution of the dataset. Three widely used DEMs SRTM 30m, ASTER 30m and SRTM 90m are analyzed to evaluate their suitability to delineate river network and basin boundary area. The hydrology tool of spatial analyst extension inbuilt in ArcGIS 10.2 (which uses the D8 method for calculation of flow direction) has been used for the delineation of both river networks and basin boundary. The assessment of river network alignment and boundary delineation is carried out in the seven sub-catchments of Gandak river basin having different morphological characteristics. The automatically delineated boundary area for all the three DEMs reflects a significant difference when compared with the digitized basin area from the Ganga flood control commission (GFCC) map. The maximum boundary area delineation error is 39137.20 km₂ forASTER 30m, and minimum delineation error of 13239.28 km₂ for SRTM 90m. In the stream network, delineation accuracy is good for SRTM 90m while, except Gandak trunk, ASTER 30m DEM shows better delineation accuracy indicated by mean absolute error (MAE) and standard deviation (SD).     

Uncertainty of soil erosion modelling using open source high resolution and aggregated DEMs

Digital Elevation Model (DEM) is one of the important parameters for soil erosion assessment. Notable uncertainties are observed in this study while using three high resolution open source DEMs. The Revised Universal Soil Loss Equation (RUSLE) model has been applied to analysis the assessment of soil erosion uncertainty using open source DEMs (SRTM, ASTER and CARTOSAT) and their increasing grid space (pixel size) from the actual. The study area is a part of the Narmada river basin in Madhya Pradesh state, which is located in the central part of India and the area covered 20,558 km². The actual resolution of DEMs is 30 m and their increasing grid spaces are taken as 90, 150, 210, 270 and 330 m for this study. Vertical accuracy of DEMs has been assessed using actual heights of the sample points that have been taken considering planimetric survey based map (toposheet). Elevations of DEMs are converted to the same vertical datum from WGS 84 to MSL (Mean Sea Level), before the accuracy assessment and modelling. Results indicate that the accuracy of the SRTM DEM with the RMSE of 13.31, 14.51, and 18.19 m in 30, 150 and 330 m resolution respectively, is better than the ASTER and the CARTOSAT DEMs. When the grid space of the DEMs increases, the accuracy of the elevation and calculated soil erosion decreases. This study presents a potential uncertainty introduced by open source high resolution DEMs in the accuracy of the soil erosion assessment models. The research provides an analysis of errors in selecting DEMs using the original and increased grid space for soil erosion modelling.     

Structure and phase transition of CaGe<Subscript>2</Subscript>O<Subscript>5</Subscript> revisited

The structure of CaGe₂O₅ between room temperature and 923 K has been determined by X-ray powder diffraction. A continuous phase transition from triclinic C1¯ to monoclinic C2/c symmetry at T_c=714±3 K is observed. The transition is accompanied by a weak heat capacity anomaly. This anomaly and the strain analysis based on the measured lattice parameters indicate a classical second-order phase transition. The order parameter, as measured by the strain component e₂₃, is associated with the displacement of the Ca cation. Electronic structure optimization by density functional methods is used to verify the centric space group of the low-temperature structure of CaGe₂O₅.     

Thermal expansion of new arsenate minerals,bradaczekite, NaCu<Subscript>4</Subscript>(AsO<Subscript>4</Subscript>)<Subscript>3</Subscript>, and urusovite,Cu(AsAlO<Subscript>5</Subscript>)

Thermal behavior of two new exhalation copper-bearing minerals, bradaczekite and urusovite, from the Great Tolbachik Fissure Eruption (1975–1976, Kamchatka Peninsula, Russia) has been studied by X-ray thermal analysis within the range 20–700°C in air. The following major values of the thermal expansion tensor have been calculated for urusovite: α₁₁ = 10, α₂₂ = α_b = 7, α₃₃ = 4, α_V = 21 × 10⁻⁶°C⁻¹, μ = c∧α₃₃ = 49° and bradaczekite: α_11aver = 23, α₂₂ = 8, α_33aver = 6 × 10⁻⁶°C⁻¹, μ(c∧α₃₃) = 73°. The sharp anisotropy of thermal deformations of these minerals, absences of phase transitions, and stability of the minerals in the selected temperature range corresponding to conditions of their formation and alteration during the posteruption period of the volcanic activity are established.     

First-principles-based calculations of the CaCO<Subscript>3</Subscript>–MgCO<Subscript>3</Subscript> and CdCO<Subscript>3</Subscript>–MgCO<Subscript>3</Subscript> subsolidus phase diagrams

 Planewave pseudopotential calculations of supercell total energies were used as bases for first-principles calculations of the CaCO₃–MgCO₃ and CdCO₃–MgCO₃ phase diagrams. Calculated phase diagrams are in qualitative to semiquantitative agreement with experiment. Two unobserved phases, Cd₃Mg (CO₃)₄ and CdMg₃(CO₃)₄, are predicted. No new phases are predicted in the CaCO₃–MgCO₃ system, but a low-lying metastable Ca₃Mg(CO₃)₄ state, analogous to the Cd₃Mg(CO₃)₄ phase is predicted. All of the predicted lowest-lying metastable states, except for huntite CaMg₃(CO₃)₄, have dolomite-related structures, i.e. they are layer structures in which A _m B _n cation layers lie perpendicular to the rhombohedral [111] vector. Received: 6 May 2002 / Accepted: 23 October 2002 Acknowledgements This work was partially supported by NSF contract DMR-0080766 and NIST.     

Calorimetric study on high-pressure transitions in KAlSi<Subscript>3</Subscript>O<Subscript>8</Subscript>

KAlSi₃O₈ sanidine dissociates into a mixture of K₂Si₄O₉ wadeite, Al₂SiO₅ kyanite and SiO₂ coesite, which further recombine into KAlSi₃O₈ hollandite with increasing pressure. Enthalpies of KAlSi₃O₈ sanidine and hollandite, K₂Si₄O₉ wadeite and Al₂SiO₅ kyanite were measured by high-temperature solution calorimetry. Using the data, enthalpies of transitions at 298 K were obtained as 65.1 ± 7.4 kJ mol^–1 for sanidine wadeite + kyanite + coesite and 99.3 ± 3.6 kJ mol^–1 for wadeite + kyanite + coesite hollandite. The isobaric heat capacity of KAlSi₃O₈ hollandite was measured at 160–700 K by differential scanning calorimetry, and was also calculated using the Kieffer model. Combination of both the results yielded a heat-capacity equation of KAlSi₃O₈ hollandite above 298 K as C_p=3.896 × 10²–1.823 × 10³T^–0.5–1.293 × 10⁷T^–2+1.631 × 10⁹T^–3 (C_p in J mol^–1 K^–1, T in K). The equilibrium transition boundaries were calculated using these new data on the transition enthalpies and heat capacity. The calculated transition boundaries are in general agreement with the phase relations experimentally determined previously. The calculated boundary for wadeite + kyanite + coesite hollandite intersects with the coesite–stishovite transition boundary, resulting in a stability field of the assemblage of wadeite + kyanite + stishovite below about 1273 K at about 8 GPa. Some phase–equilibrium experiments in the present study confirmed that sanidine transforms directly to wadeite + kyanite + coesite at 1373 K at about 6.3 GPa, without an intervening stability field of KAlSiO₄ kalsilite + coesite which was previously suggested. The transition boundaries in KAlSi₃O₈ determined in this study put some constraints on the stability range of KAlSi₃O₈ hollandite in the mantle and that of sanidine inclusions in kimberlitic diamonds.     

New insights on pressure,temperature, and chemical stability of CsAlSi<Subscript>5</Subscript>O<Subscript>12</Subscript>, a potential host for nuclear waste

A Cs-bearing polyphase aggregate with composition (in wt%): 76(1)_CsAlSi5O12 + 7(1)_CsAlSi2O6 + 17(1)_amorphous, was obtained from a clinoptilolite-rich epiclastic rock after a beneficiation process of the starting material (aimed to increase the fraction of zeolite to 90 wt%), cation exchange and then thermal treatment. CsAlSi₅O₁₂ is an open-framework compound with CAS topology; CsAlSi₂O₆ is a pollucite-like material with ANA topology. The thermal stability of this polyphase material was investigated by in situ high-T X-ray powder diffraction, the combined P–T effects by a series of runs with a single-stage piston cylinder apparatus, and its chemical stability following the “availability test” (“AVA test”) protocol. A series of additional investigations were performed by WDS–electron microprobe analysis in order to describe the P–T-induced modification of the material texture, and to chemically characterize the starting material and the run products. The “AVA tests” of the polyphase aggregate show an extremely modest release of Cs⁺: 0.05 mg/g. In response to applied temperature and at room P, CsAlSi₅O₁₂ experiences an unquenchable and displacive Ama2-to-Amam phase transition at about 770 K, and the Amam polymorph is stable in its crystalline form up to 1600 K; a crystalline-to-amorphous phase transition occurs between 1600 and 1650 K. In response to the applied P = 0.5 GPa, the crystalline-to-amorphous transition of CsAlSi₅O₁₂ occurs between 1670 and 1770 K. This leads to a positive Clapeyron slope (i.e., dP/dT > 0) of the crystalline-to-amorphous transition. When the polyphase aggregate is subjected at P = 0.5 GPa and T > 1770 K, CsAlSi₅O₁₂ melts and only CsAlSi₂O₆ (pollucite-like; dominant) and Cs-rich glass (subordinate) are observed in the quenched sample. Based on its thermo-elastic behavior, P–T phase stability fields, and Cs⁺ retention capacity, CsAlSi₅O₁₂ is a possible candidate for use in the immobilization of radioactive isotopes of Cs, or as potential solid hosts for ¹³⁷Cs γ-radiation source in sterilization applications. More in general, even the CsAlSi₅O₁₂-rich aggregate obtained by a clinoptilolite-rich epiclastic rock appears to be suitable for this type of utilizations.     

Thermodynamic properties,low-temperature heat-capacity anomalies,and single-crystal X-ray refinement of hydronium jarosite, (H<Subscript>3</Subscript>O)Fe<Subscript>3</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH)<Subscript>6</Subscript>

Crystals of hydronium jarosite were synthesized by hydrothermal treatment of Fe(III)–SO₄ solutions. Single-crystal XRD refinement with R₁=0.0232 for the unique observed reflections (|F_o| > 4_F) and wR₂=0.0451 for all data gave a=7.3559(8) Å, c=17.019(3) Å, V^o=160.11(4) cm³, and fractional positions for all atoms except the H in the H₃O groups. The chemical composition of this sample is described by the formula (H₃O)_0.91Fe_2.91(SO₄)₂[(OH)_5.64(H₂O)_0.18]. The enthalpy of formation (H^o_f) is –3694.5 ± 4.6 kJ mol^–1, calculated from acid (5.0 N HCl) solution calorimetry data for hydronium jarosite, -FeOOH, MgO, H₂O, and -MgSO₄. The entropy at standard temperature and pressure (S^o) is 438.9±0.7 J mol^–1 K^–1, calculated from adiabatic and semi-adiabatic calorimetry data. The heat capacity (C_p) data between 273 and 400 K were fitted to a Maier-Kelley polynomial C_p(T in K)=280.6 + 0.6149T–3199700T^–2. The Gibbs free energy of formation is –3162.2 ± 4.6 kJ mol^–1. Speciation and activity calculations for Fe(III)–SO₄ solutions show that these new thermodynamic data reproduce the results of solubility experiments with hydronium jarosite. A spin-glass freezing transition was manifested as a broad anomaly in the C_p data, and as a broad maximum in the zero-field-cooled magnetic susceptibility data at 16.5 K. Another anomaly in C_p, below 0.7 K, has been tentatively attributed to spin cluster tunneling. A set of thermodynamic values for an ideal composition end member (H₃O)Fe₃(SO₄)₂(OH)₆ was estimated: G^o_f= –3226.4 ± 4.6 kJ mol^–1, H^o_f=–3770.2 ± 4.6 kJ mol^–1, S^o=448.2 ± 0.7 J mol^–1 K^–1, C_p (T in K)=287.2 + 0.6281T–3286000T^–2 (between 273 and 400 K).     

High-pressure phase transitions of CaRhO<Subscript>3</Subscript> perovskite

High-pressure phase transitions of CaRhO₃ perovskite were examined at pressures of 6–27 GPa and temperatures of 1,000–1,930°C, using a multi-anvil apparatus. The results indicate that CaRhO₃ perovskite successively transforms to two new high-pressure phases with increasing pressure. Rietveld analysis of powder X-ray diffraction data indicated that, in the two new phases, the phase stable at higher pressure possesses the CaIrO₃-type post-perovskite structure (space group Cmcm) with lattice parameters: a = 3.1013(1) Å, b = 9.8555(2) Å, c = 7.2643(1) Å, V _m  = 33.43(1) cm³/mol. The Rietveld analysis also indicated that CaRhO₃ perovskite has the GdFeO₃-type structure (space group Pnma) with lattice parameters: a = 5.5631(1) Å, b = 7.6308(1) Å, c = 5.3267(1) Å, V _m  = 34.04(1) cm³/mol. The third phase stable in the intermediate P, T conditions between perovskite and post-perovskite has monoclinic symmetry with the cell parameters: a = 12.490(3) Å, b = 3.1233(3) Å, c = 8.8630(7) Å, β = 103.96(1)°, V _m  = 33.66(1) cm³/mol (Z = 6). Molar volume changes from perovskite to the intermediate phase and from the intermediate phase to post-perovskite are –1.1 and –0.7%, respectively. The equilibrium phase relations determined indicate that the boundary slopes are large positive values: 29 ± 2 MPa/K for the perovskite—intermediate phase transition and 62 ± 6 MPa/K for the intermediate phase—post-perovskite transition. The structural features of the CaRhO₃ intermediate phase suggest that the phase has edge-sharing RhO₆ octahedra and may have an intermediate structure between perovskite and post-perovskite.     

Synthesis,TEM characterization and thermal behaviour of LiNiSi<Subscript>2</Subscript>O<Subscript>6</Subscript> pyroxene

A pyroxene with composition LiNiSi₂O₆ was synthesized at T = 1,473 K and P = 2.0 GPa; the cell parameters at T = 298 K are a = 9.4169(6) Å, b = 8.4465(7) Å, c = 5.2464(3) Å, β = 110.534(6)°, V = 390.78(3) Å³. TEM examination of the LiNiSi₂O₆ pyroxene showed the presence of h + k odd reflections indicative of a primitive lattice, and of antiphase domains obtained by dark field imaging of the h + k odd reflections. A HT in situ investigation was performed by examining TEM selected area diffraction patterns collected at high temperature and synchrotron radiation powder diffraction. In HTTEM the LiNiSi₂O₆ was examined together with LiCrSi₂O₆ pyroxene. In LiCrSi₂O₆ the h + k odd critical reflections disappear at about 340 K; they are sharp up to the transition temperature and do not change their shape until they disappear. In LiNiSi₂O₆ the h + k odd reflections are present up to sample deterioration at 650 K. A high temperature synchrotron radiation powder diffraction investigation was performed on LiNiSi₂O₆ between 298 and 773 K. The analysis of critical reflections and of changes in cell parameters shows that the space group is P-centred up to the highest temperature. The comparative analysis of the thermal and spontaneous strain contributions in P2₁/c and C2/c pyroxenes indicates that the high temperature strain in P-LiNiSi₂O₆ is very similar to that due to thermal strain only in C2/c spodumene and that a spontaneous strain contribution related to pre-transition features is not apparent in LiNiSi₂O₆. A different high-temperature behaviour in LiNiSi₂O₆ with respect to other pyroxenes is suggested, possibly in relation with the presence of Jahn–Teller distortion of the M1 polyhedron centred by low-spin Ni³⁺.     

LiFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript> and NaFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript> at low temperatures: an infrared spectroscopic study

 Synthetic aegirine LiFeSi₂O₆ and NaFeSi₂O₆ were characterized using infrared spectroscopy in the frequency range 50–2000 cm⁻¹, and at temperatures between 20 and 300 K. For the C2/c phase of LiFeSi₂O₆, 25 of the 27 predicted infrared bands and 26 of 30 predicted Raman bands are recorded at room temperature. NaFeSi₂O₆ (with symmetry C2/c) shows 25 infrared and 26 Raman bands. On cooling, the C2/c–P2₁/c structural phase transition of LiFeSi₂O₆ is characterized by the appearance of 13 additional recorded peaks. This observation indicates the enlargement of the unit cell at the transition point. The appearance of an extra band near 688 cm⁻¹ in the monoclinic P2₁/c phase, which is due to the Si–O–Si vibration in the Si₂O₆ chains, indicates that there are two non-equivalent Si sites with different Si–O bond lengths. Most significant spectral changes appear in the far-infrared region, where Li–O and Fe–O vibrations are mainly located. Infrared bands between 300 and 330 cm⁻¹ show unusually dramatic changes at temperatures far below the transition. Compared with the infrared data of NaFeSi₂O₆ measured at low temperatures, the change in LiFeSi₂O₆ is interpreted as the consequence of mode crossing in the frequency region. A generalized Landau theory was used to analyze the order parameter of the C2/c–P2₁/c phase transition, and the results suggest that the transition is close to tricritical. Received: 21 January 2002 / Accepted: 22 July 2002     

Low-temperature heat capacities,entropies and high-pressure phase relations of MgSiO<Subscript>3</Subscript> ilmenite and perovskite

Low-temperature isobaric heat capacities (C _p ) of MgSiO₃ ilmenite and perovskite were measured in the temperature range of 1.9–302.4 K with a thermal relaxation method using the Physical Properties Measurement System. The measured C _p of perovskite was higher than that of ilmenite in the whole temperature range studied. From the measured C _p , standard entropies at 298.15 K of MgSiO₃ ilmenite and perovskite were determined to be 53.7 ± 0.4 and 57.9 ± 0.3 J/mol K, respectively. The positive entropy change (4.2 ± 0.5 J/mol K) of the ilmenite–perovskite transition in MgSiO₃ is compatible with structural change across the transition in which coordination of Mg atoms is changed from sixfold to eightfold. Calculation of the ilmenite–perovskite transition boundary using the measured entropies and published enthalpy data gives an equilibrium transition boundary at about 20–23 GPa at 1,000–2,000 K with a Clapeyron slope of −2.4 ± 0.4 MPa/K at 1,600 K. The calculated boundary is almost consistent within the errors with those determined by high-pressure high-temperature in situ X-ray diffraction experiments.     

A study of turbulent characteristics of atmospheric boundary layer over monsoon trough region using Kytoon and Doppler sodar

As a part of the MONTBLEX-90 observational programme, Kytoon and Doppler sodar observations were taken at Kharagpur. These data are analysed to study the turbulent characteristics of the atmospheric boundary layer in terms of stability, temperature structure function (C _T ² ) and velocity structure function (C _v ² ).C _T ² follows aZ ^−4/3 law on most of the days, whereas the variation ofC _V ² is not systematic.C _V ² andC _T ² values are found to vary between 10⁻⁵−10⁻¹ m^4/3s⁻² and 10⁻⁵−10⁻²°C² m^−2/3 respectively.     

Adsorption of H<Subscript>2</Subscript>O,NH<Subscript>3</Subscript> and C<Subscript>6</Subscript>H<Subscript>6</Subscript> on alkali metal cations in internal surface of mordenite and in external surface of smectite: a DFT study

Adsorption of H₂O, NH₃ and C₆H₆ on H- and alkali metal-exchanged structures of mordenite and on corresponding cations on the smectite layer is investigated by ab initio density-functional calculations. Proton or an alkali metal cation compensates one Al/Si framework substitution and resides in the extra-framework position of zeolite or above flat smectite layer close to the Al/Si substitution. Pronounced similarities between zeolite and smectite are observed in changes of the adsorption energies and location of the external cation with changing character of the external cation. Calculated adsorption energies exhibit the following trend: E(NH₃) > E(H₂O) > E(C₆H₆). Because of looser contact with the framework, zeolitic cations are stronger adsorption centers and calculated adsorption energies of zeolites are by ~20–30% larger than cations of smectites. The highest adsorption energy is calculated for H-exchanged structures and down the group of alkali metal cations a decrease of the adsorption energy is observed. Deviations from the smooth variation of the adsorption energy are caused by: (1) formation of strong hydrogen bonds in H-exchanged structures, (2) adsorption induced migration of the external Li⁺ cation, and (3) steric hindrances of the flat C₆H₆ molecule adsorbed on the cation in the cage of zeolite.     

Total column density variations of ozone (O<Subscript>3</Subscript>) in presence of different types of clouds

The zenith sky scattered light spectra were carried out using zenith sky UV-visible spectrometer in clear and cloudy sky conditions during May-November 2000 over the tropical station Pune (18°32′N, 73°51′E). These scattered spectra are obtained in the spectral range 462–498 nm between 75° and 92° solar zenith angles (SZAs). The slant column densities (SCDs) as well as total column densities (TCDs) of NO₂, O₃, H₂O and O₄ are derived with different SZAs in clear and cloudy sky conditions. The large enhancements and reductions in TCDs of the above gases are observed in thick cumulonimbus (Cb) clouds and thin high cirrus (Ci) clouds, respectively, compared to clear sky conditions. The enhancements in TCDs of O₃ appear to be due to photon diffusion, multiple Mie-scattering and multiple reflections between layered clouds or isolated patches of optically thick clouds. The reductions in TCDs due to optically thin clouds are noticed during the above period. The variations in TCDs of O₃ measured under cloudy sky are discussed with total cloud cover (octas) of different types of clouds such as low clouds (C _L ), medium clouds (C _M ) and high clouds (C _H ) during May-November 2000. The variations in TCDs of O₃ measured in cloudy sky conditions are found to be well matched with cloud sensitive parameter colour index (CI) and found to be in good correlation. The TCD_cloudy are derived using airmass factors (AMFs) computed without considering cloud cover and CI in radiative transfer (RT) model, whereas TCD_model are derived using AMFs computed with considering cloud cover, cloud height and CI in RT model. The TCD_model is the column density of illuminated cloudy effect. A good agreement is observed between TCD_model, TCD_Dob and TCD_GOME.     

The intermetallic compound Ni<Subscript>3</Subscript>Au and gold-nickel solid solutions in metalliferous sediments of the triassic chert formation in Sikhote-Alin in the Far East

The intermetallic compound Ni₃Au and Au-Ni solid solutions (native nickel Au and Au-bearing native Ni) were found in the contact metamorphosed metalliferous sediments of the Triassic chert formation in Sikhote-Alin. The metalliferous rocks are characterized by high contents of Au, Ag, and PGE, as well as the presence of diverse minerals of precious metals. Nickel gold (Au0._91-0.88 Ni_0.09-0.12) is found as grains and crystals (3 to 4 im in size) in Au-bearing cherts with hematite, which are conventionally defined as “itabir-ites” and in the altered siliceous rocks of the Dal’nerechensky district (the upper reaches of the Gornya River). The nickel gold is associated with copper Au, pure native Au (Au_1.00), and Au-Ag and Au-Ag-Pb solid solutions (Au_0.86/_0.84Ag_0.14__0.16 and Au_0.78Ag_0.19Pb_0.03, respectively). The Au-bearing Ni is found in the metamorphosed carbonaceous mudstones and Au-bearing “itabirites” of the Shirokopadninsky area (Olgin-sky district). The Au content varies from 6.09 wt % (Ni_0.98Au_0.02) to 11.30 wt % (Ni_0.96Au_0.04) in some Au-bearing Ni grains (about 10—15 im in diameter) taken from the metamorphosed mudstones. The grains of Au-bearing Ni (Co_0.001__0.00Au_00.2 - _0.17 Ni _0.98__0.83) in the “itabirites” are also characterized by their heterogeneous composition and the fine impregnation of the Ni₃ Au intermetallic compound (Ni_2.99Au_1.01 based on the microprobe analysis).     

Low-temperature heat capacities of MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> and spinels of the MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript>–MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> solid solution

We present results from low-temperature heat capacity measurements of spinels along the solid solution between MgAl₂O₄ and MgCr₂O₄. The data also include new low-temperature heat capacity measurements for MgAl₂O₄ spinel. Heat capacities were measured between 1.5 and 300 K, and thermochemical functions were derived from the results. No heat capacity anomaly was observed for MgAl₂O₄ spinel; however, we observe a low-temperature heat capacity anomaly for Cr-bearing spinels at temperatures below 15 K. From our data we calculate standard entropies (298.15 K) for Mg(Cr,Al)₂O₄ spinels. We suggest a standard entropy for MgAl₂O₄ of 80.9 ± 0.6 J mol⁻¹ K⁻¹. For the solid solution between MgAl₂O₄ and MgCr₂O₄, we observe a linear increase of the standard entropies from 80.9 J mol⁻¹ K⁻¹ for MgAl₂O₄ to 118.3 J mol⁻¹ K⁻¹ for MgCr₂O₄.     

Statistical evaluation of PM<Subscript>10</Subscript> and distribution of PM<Subscript>1</Subscript>, PM<Subscript>2.5</Subscript>, and PM<Subscript>10</Subscript> in ambient air due to extreme fireworks episodes (Deepawali festivals) in megacity Delhi

Temporal variation of PM₁₀ using 2-year data (January, 2007–December, 2008) of Delhi is presented. PM₁₀ varied from 42 to 200 μg m⁻³ over January to December, with an average 114.1 ± 81.1 μg m⁻³. They are comparable with the data collected by Central Pollution Control Board (National Agency which monitors data over the entire country in India) and are lower than National Ambient Air Quality (NAAQ) standard during monsoon, close to NAAQ during summer but higher in winter. Among CO, NO₂, SO₂, rainfall, temperature, and wind speed, PM₁₀ shows good correlation with CO. Also, PM₁₀, PM_2.5, and PM₁ levels on Deepawali days when fireworks were displayed are presented. In these festive days, PM₁₀, PM_2.5, and PM₁ levels were 723, 588, and 536 μg m⁻³ in 2007 and 501, 389, and 346 μg m⁻³ in 2008. PM₁₀, PM_2.5, and PM₁ levels in 2008 were 1.5 times lower than those in 2007 probably due to higher mixing height (446 m), temperature (23.8°C), and winds (0.36 ms⁻¹).     

The P21/m↔ C2/m phase transition in synthetic amphibole Na NaMg Mg5 Si8 O22 (OH)2: thermodynamic and crystal-chemical evaluation

The P2₁/mC2/m displacive phase transition in the synthetic end-member amphibole Na NaMg Mg₅ Si₈ O₂₂ (OH)₂ has been studied by monitoring changes in unit-cell parameters and the intensities of superlattice reflections at 25–400 °C. This amphibole allows investigation of the effects of compositional variations at the A- and B-group sites upon the transition. Polynomial fitting of a 24 Landau potential to the evolution of the order parameter with T yielded a T _c of 257 ± 3 °C, and Landau coefficients compatible with a second-order transition. Structure refinement of single-crystal data collected at 25, 140, 270 and 370 °C allowed modelling of the structural changes as a function of T and symmetry. Crystal-chemical analysis suggests that differences in T _c in cummingtonites and in the crystal of this work depend mainly upon the relations between the aggregate ionic radii of the B- and C-group cations. Electronic Supplementary Material: of Table 5 is available in the online version of this article at http://dx.doi.org/10.1007/s00269-003-0348-9     

Ternary system H<Subscript>2</Subscript>O-CO<Subscript>2</Subscript>-NaCl at high <Emphasis Type="Italic">T</Emphasis>-<Emphasis Type="Italic">P</Emphasis> parameters: An empirical mixing model

New experimental data on the solubility of NaCl in gaseous CO₂ were obtained at pressures (P) of 30–70 MPa and temperatures of 623 and 673 K on experimental equipment making possible to sample a portion of the gas in the course of the experiment. The new measures have demonstrated that the NaCl solubility increases with increasing temperature (T) and pressure and is approximately four to five orders of magnitude higher than the saturated vapor pressure of NaCl at the corresponding temperature. The paper also reports newly obtained experimental data on the equilibrium conditions of the reaction of talc decomposition into enstatite and quartz at a variable H₂O/NaCl ratio in the fluid. The results of the experiments validate the empirical equations previously suggested for H₂O and NaCl activities in concentrated aqueous salt solutions that can be used in describing silica-saturated fluids at high T-P parameters. A new empirical equation is suggested for the Gibbs free mixing energy in the H₂O-CO₂-NaCl ternary system, with the parameters of the equation calibrated against experimental data on phase equilibria in marginal binary systems and on the location of the boundary of the region of homogeneous three-component fluid according to data on synthetic fluid inclusions in quartz.