Raman spectroscopy of newberyite Mg(PO3OH)���3H2O ��� a cave mineral

Newberyite Mg(PO3OH)���3H2O is a mineral found in caves such as from Moorba cave, Jurien Bay, Western Australia, the Skipton Lava tubes (SW of Ballarat, Victoria, Australia) and in the Petrogale Cave (Madura , Eucla, Western Australia). Because these minerals contain oxyanions, hydroxyl units and water, the minerals lend themselves to spectroscopic analysis. Raman spectroscopy can investigate the complex paragenetic relationships existing between a number of ���cave��� minerals. The intense sharp band at 982 cm-1 is assigned to the PO43- ��1 symmetric stretching mode. Low intensity Raman bands at 1152, 1263 and 1277 cm-1 are assigned to the PO43- ��3 antisymmetric stretching vibrations. Raman bands at 497 and 552 cm-1 are attributed to the PO43- ��4 bending modes. An intense Raman band for newberyite at 398 cm-1 with a shoulder band at 413 cm-1 is assigned to the PO43- ��2 bending modes. The values for the OH stretching vibrations provide hydrogen bond distances of 2.728�� (3267 cm-1), 2.781�� (3374cm-1), 2.868�� (3479 cm-1), and 2.918�� (3515 cm-1). Such hydrogen bond distances are typical of secondary minerals. Estimates of the hydrogen-bond distances have been made from the position of the OH stretching vibrations and show a wide range in both strong and weak bonds.

A Raman spectroscopic study of bukovsk��ite Fe2(AsO4)(SO4)(OH)���7H2O-a mineral phase with a significant role in arsenic migration

The Raman spectrum of bukovsk��ite, Fe3+2(OH)(SO4)(AsO4)���7H2O has been studied and compared with the Raman spectrum of an amorphous gel containing specifically Fe, As and S elements and is understood as an intermediate product in the formation of bukovsk��ite. Observed bands are assigned to the stretching and bending vibrations of (SO4)2- and (AsO4)3- units, stretching and bending vibrations and librational modes of hydrogen bonded water molecules, stretching and bending vibrations of hydrogen bonded (OH)- ions and Fe3+-(O,OH) units. Approximate range of O-H...O hydrogen bond lengths is inferred from the Raman spectra. Raman spectra of crystalline bukovsk��ite and of the amorphous gel differ in that the bukovsk��ite spectrum is more complex, observed bands are sharp, the degenerate bands of (SO4)2- and (AsO4)3- are split and more intense. Lower wavenumbers of ��� H2O bending vibration in the spectrum of the amorphous gel may indicate the presence of weaker hydrogen bonds compared with those in bukovsk��ite.

A vibrational spectroscopic study of the mineral hinsdalite (Pb,Sr)Al3(PO4)(SO4)(OH)6

The objective of this research is to determine the molecular structure of the mineral hinsdalite using vibrational spectroscopy. The mineral hinsdalite (Pb,Sr)Al3(PO4,SO4)2(OH)6 is a hydroxy phosphate-sulphate mineral belonging to the beudantite subgroup of alunites. The mineral is interesting because it contains two oxyanions, phosphate and sulphate, which is unusual. The formation of hinsdalite offers a mechanism for the removal of phosphate from the environment. The mineral has been characterised by Raman spectroscopy and infrared spectroscopy. The spectra are then related to the molecular structure of the mineral. Bands at various wavenumbers are assigned to the different vibrational modes of hinsdalite, which were then associated to the molecular structure of the mineral. Bands were primarily assigned to phosphate and sulphate stretching and bending modes. The Raman spectrum is characterised by an intense sharp band at 982 cm-1 with a component band at 997 cm-1 assigned to the ��1 (PO4)3- symmetric stretching modes. Two symmetric stretching modes for both phosphate and sulphate supported the concept of non-equivalent phosphate and sulphate units in the mineral structure. Bands in the OH stretching region enabled hydrogen bond distances to be calculated. Hinsdalite is characterised by disordered phosphate/sulphate tetrahedra and non-equivalent phosphate units are observed in the vibrational spectrum of hinsdalite.

Deceit and Bruno Taut's Glashaus

The historical context surrounding Bruno Taut's Glashaus has been established through work of authors like Reyner Banham, Dennis Sharp and Ian Boyd-Whyte. However, these English language translations, are mostly derived from secondary sources such as Adolf Behne and Paul Scheerbart. Surprisingly, Taut's own writings largely do not feature in this prevailing account of his work. Since 1990, strong doubts have arisen about this conventional picture of Taut's Glashaus. Manfred spiedel, for instance, minimizes Paul Scheerbart's contribution to the design by arguing that Scheerbart met Taut only a few months before the construction of the Glashaus, that is, after Taut had finished his preliminary sketches. Kurt Junghanns goes further and asserts that the Glashaus design was complete beefore Taut and Scheerbart ever met. In 2005, Kai Gutschow published The Culture of Criticism: Adolf Behne and the Development of Modern Architecture in Germany, 1910 - 1914. Most startling, Gutschow asserts that Behne acts as the propagandist for the Glashaus by fabricating its link with Expressionism. This is particularly troubling because nobody contributed more to establishing the link between the Glashaus, Bruno Taut and Expressionism than Behne. As a result of this new evidence, this paper concurs that the established historical understanding of the Glashaus is flawed. By returning to Taut's own writings, a reinterpretation can be offered that strongly links the Glashaus to the Victoria regia lily and Strasbourg Cathedral. The significance of this approach is that it re-establishes Taut's own rational behind the design of the Glashaus, and thus contributes to the re-evaluation of the generally accepted histories of the Modern movement.

Empirical minimization

We investigate the behavior of the empirical minimization algorithm using various methods. We first analyze it by comparing the empirical, random, structure and the original one on the class, either in an additive sense, via the uniform law of large numbers, or in a multiplicative sense, using isomorphic coordinate projections. We then show that a direct analysis of the empirical minimization algorithm yields a significantly better bound, and that the estimates we obtain are essentially sharp. The method of proof we use is based on Talagrand���s concentration inequality for empirical processes.

On the optimality of sample-based estimates of the expectation of the empirical minimizer

We study sample-based estimates of the expectation of the function produced by the empirical minimization algorithm. We investigate the extent to which one can estimate the rate of convergence of the empirical minimizer in a data dependent manner. We establish three main results. First, we provide an algorithm that upper bounds the expectation of the empirical minimizer in a completely data-dependent manner. This bound is based on a structural result due to Bartlett and Mendelson, which relates expectations to sample averages. Second, we show that these structural upper bounds can be loose, compared to previous bounds. In particular, we demonstrate a class for which the expectation of the empirical minimizer decreases as O(1/n) for sample size n, although the upper bound based on structural properties is ��(1). Third, we show that this looseness of the bound is inevitable: we present an example that shows that a sharp bound cannot be universally recovered from empirical data.

Sparseness vs estimating conditional probabilities : some asymptotic results

One of the nice properties of kernel classifiers such as SVMs is that they often produce sparse solutions. However, the decision functions of these classifiers cannot always be used to estimate the conditional probability of the class label. We investigate the relationship between these two properties and show that these are intimately related: sparseness does not occur when the conditional probabilities can be unambiguously estimated. We consider a family of convex loss functions and derive sharp asymptotic results for the fraction of data that becomes support vectors. This enables us to characterize the exact trade-off between sparseness and the ability to estimate conditional probabilities for these loss functions.

Reversed bias Pt/nanostructured ZnO Schottky diode with enhanced electric field for hydrogen sensing

In this paper, the effect of electric field enhancement on Pt/nanostructured ZnO Schottky diode based hydrogen sensors under reverse bias condition has been investigated. Current-voltage characteristics of these diodes have been studied at temperatures from 25 to 620 ��C and their free carrier density concentration was estimated by exposing the sensors to hydrogen gas. The experimental results show a significantly lower breakdown voltage in reversed bias current-voltage characteristics than the conventional Schottky diodes and also greater lateral voltage shift in reverse bias operation than the forward bias. This can be ascribed to the increased localized electric fields emanating from the sharp edges and corners of the nanostructured morphologies. At 620 ��C, voltage shifts of 114 and 325 mV for 0.06% and 1% hydrogen have been recorded from dynamic response under the reverse bias condition. �� 2010 Elsevier B.V. All rights reserved.

A compact interferometric sensor design using three waveguide coupling

The use of metal stripes for the guiding of plasmons is a well established technique for the infrared regime and has resulted in the development of a myriad of passive optical components and sensing devices. However, the plasmons suffer from large losses around sharp bends, making the compact design of nanoscale sensors and circuits problematic. A compact alternative would be to use evanescent coupling between two sufficiently close stripes, and thus we propose a compact interferometer design using evanescent coupling. The sensitivity of the design is compared with that achieved using a hand-held sensor based on the Kretschmann style surface plasmon resonance technique. Modeling of the new interferometric sensor is performed for various structural parameters using finite-difference time-domain and COMSOL Multiphysics. The physical mechanisms behind the coupling and propagation of plasmons in this structure are explained in terms of the allowed modes in each section of the device.

A large change in temperature between neighbouring days increases the risk of mortality

Background: Previous studies have found high temperatures increase the risk of mortality in summer. However, little is known about whether a sharp decrease or increase in temperature between neighbouring days has any effect on mortality. Method: Poisson regression models were used to estimate the association between temperature change and mortality in summer in Brisbane, Australia during 1996���2004 and Los Angeles, United States during 1987���2000. The temperature change was calculated as the current day���s mean temperature minus the previous day���s mean. Results: In Brisbane, a drop of more than 3 ��C in temperature between days was associated with relative risks (RRs) of 1.157 (95% confidence interval (CI): 1.024, 1.307) for total non external mortality (NEM), 1.186 (95%CI: 1.002, 1.405) for NEM in females, and 1.442 (95%CI: 1.099, 1.892) for people aged 65���74 years. An increase of more than 3 ��C was associated with RRs of 1.353 (95%CI: 1.033, 1.772) for cardiovascular mortality and 1.667 (95%CI: 1.146, 2.425) for people aged < 65 years. In Los Angeles, only a drop of more than 3 ��C was significantly associated with RRs of 1.133 (95%CI: 1.053, 1.219) for total NEM, 1.252 (95%CI: 1.131, 1.386) for cardiovascular mortality, and 1.254 (95%CI: 1.135, 1.385) for people aged ���75 years. In both cities, there were joint effects of temperature change and mean temperature on NEM. Conclusion : A significant change in temperature of more than 3 ��C, whether positive or negative, has an adverse impact on mortality even after controlling for the current temperature.

The structure of the mineral leogangite Cu10(OH)6(SO4)(AsO4)4���8H2O���implications for arsenic accumulation and removal

The objective of this research is to determine the molecular structure of the mineral leogangite. The formation of the types of arsenosulphate minerals offers a mechanism for arsenate removal from soils and mine dumps. Raman and infrared spectroscopy have been used to characterise the mineral. Observed bands are assigned to the stretching and bending vibrations of (SO4)2- and (AsO4)3- units, stretching and bending vibrations of hydrogen bonded (OH)- ions and Cu2+-(O,OH) units. The approximate range of O-H...O hydrogen bond lengths is inferred from the Raman spectra. Raman spectra of leogangite from different origins differ in that some spectra are more complex, where bands are sharp and the degenerate bands of (SO4)2- and (AsO4)3- are split and more intense. Lower wavenumbers of ��� H2O bending vibration in the spectrum may indicate the presence of weaker hydrogen bonds compared with those in a different leogangite samples. The formation of leogangite offers a mechanism for the removal of arsenic from the environment.

The mixed anion mineral parnauite Cu9[(OH)10|SO4|(AsO4)2]���7H2O ��� a Raman spectroscopic study

The mixed anion mineral parnauite Cu9[(OH)10|SO4|(AsO4)2].7H2O from two localities namely Cap Garonne Mine, Le Pradet, France and Majuba Hill mine, Pershing County, Nevada, USA has been studied by Raman spectroscopy. The Raman spectrum of the French sample is dominated by an intense band at 975 cm-1 assigned to the ��1 (SO4)2- symmetric stretching mode and Raman bands at 1077 and 1097 cm-1 may be attributed to the ��3 (SO4)2- antisymmetric stretching mode. Two Raman bands 1107 and 1126 cm-1 are assigned to carbonate CO32- symmetric stretching bands and confirms the presence of carbonate in the structure of parnauite. The comparatively sharp band for the Pershing County mineral at 976 cm-1 is assigned to the ��1 (SO4)2- symmetric stretching mode and a broad spectral profile centered upon 1097 cm-1 is attributed to the ��3 (SO4)2- antisymmetric stretching mode. Two intense bands for the Pershing County mineral at 851 and 810 cm-1 are assigned to the ��1 (AsO4)3- symmetric stretching and ��3 (AsO4)3- antisymmetric stretching modes. Two Raman bands for the French mineral observed at 725 and 777 cm-1 are attributed to the ��3 (AsO4)3- antisymmetric stretching mode. For the French mineral, a low intensity Raman band is observed at 869 cm-1 and is assigned to the ��1 (AsO4)3- symmetric stretching vibration. Chemical composition of parnauite remains open and the question may be raised is parnauite a solid solution of two or more minerals such as a copper hydroxy-arsenate and a copper hydroxy sulphate.

Vertical growth and resonator properties of hexagonally shaped zinc oxide nanonails

We synthesized vertically aligned nail-shaped ZnO nanocrystal arrays on silicon substrates via a combination of a carbothermal reduction method and textured ZnO seeding layers that were precoated on silicon substrates by thermally decomposing zinc acetate, and studied their optical properties using cathodoluminescence (CL) and photoluminescence techniques. The ZnO nanonails show a sharp band-gap edge UV emission and a defect-related broad green emission. Monochromatic CL images of an individual ZnO nanonail show variations in spatial distributions of respective CL bands that had different origins. We attribute the spatial variation of CL images to an uneven distribution of luminescent defects and/or a structure-related light out-coupling from hexagonal ZnO nanostructures. The most distinct CL feature from the hexagonal head of an individual ZnO nanonail was the occurrence of a series of distinct resonant peaks within the visible wavelength range. It appeared that the head of a nanonail played the role of a hexagonal cavity so that polarizationdependent whispering gallery modes were stimulated by electron beam excitation.

Characteristics of airborne ultrafine and coarse particles during the Australian dust storm of 23 September 2009

Particle number concentrations and size distributions, visibility and particulate mass concentrations and weather parameters were monitored in Brisbane, Australia, on 23 September 2009, during the passage of a dust storm that originated 1400 km away in the dry continental interior. The dust concentration peaked at about mid-day when the hourly average PM2.5 and PM10 values reached 814 and 6460 ��g m-3, respectively, with a sharp drop in atmospheric visibility. A linear regression analysis showed a good correlation between the coefficient of light scattering by particles (Bsp) and both PM10 and PM2.5. The particle number in the size range 0.5-20 ��m exhibited a lognormal size distribution with modal and geometrical mean diameters of 1.6 and 1.9 ��m, respectively. The modal mass was around 10 ��m with less than 10% of the mass carried by particles smaller than 2.5 ��m. The PM10 fraction accounted for about 68% of the total mass. By mid-day, as the dust began to increase sharply, the ultrafine particle number concentration fell from about 6x103 cm-3 to 3x103 cm-3 and then continued to decrease to less than 1x103 cm-3 by 14h, showing a power-law decrease with Bsp with an R2 value of 0.77 (p<0.01). Ultrafine particle size distributions also showed a significant decrease in number during the dust storm. This is the first scientific study of particle size distributions in an Australian dust storm.

Vibrational spectroscopy of the multi anion mineral zykaite Fe4(AsO4)(SO4)(OH)���15H2O ��� implications for arsenate removal

Some minerals are colloidal and are poorly diffracting . Vibrational spectroscopy offers one of the few methods for the assessment of the structure of these types of minerals. Among this group of minerals is zykaite with formula Fe4(AsO4)(SO4)(OH)���15H2O. The objective of this research is to determine the molecular structure of the mineral zykaite using vibrational spectroscopy. Raman and infrared bands are attributed to the AsO43-, SO42- and water stretching vibrations. The sharp band at 3515 cm-1 is assigned to the stretching vibration of the OH units. This mineral offers a mechanism for the formation of more crystalline minerals such as scorodite and bukovskyite. Arsenate ions can be removed from aqueous systems through the addition of ferric compounds such as ferric chloride. This results in the formation of minerals such as zykaite and pitticite (Fe3+,AsO4,SO4,H2O).