A Raman and infrared spectroscopic study of the mineral delvauxite CaFe3+4(PO4,SO4)2(OH)8•4-6H2O- a ‘colloidal’ mineral

The mineral delvauxite CaFe3+4(PO4,SO4)2(OH)8•4-6H2O has been characterised by Raman spectroscopy and infrared spectroscopy. The mineral is associated with the minerals diadochite and destinezite. Delvauxite appears to vary in crystallinity from amorphous to semi-crystalline. The mineral is often X-ray non-diffracting. The minerals are found in soils and may be described as ‘colloidal’ minerals. Vibrational spectroscopy enables determination of the molecular structure of delvauxite. Bands are assigned to phosphate and sulphate stretching and bending modes. Two symmetric stretching modes for both the phosphate and sulphate symmetric stretching modes support the concept of non-equivalent phosphate and sulphate units in the mineral structure. Multiple water bending and stretching modes imply that non-equivalent water molecules in the structure exist with different hydrogen bond strengths.

Online alcohol interventions : a systematic review

Background: There has been a significant increase in the availability of online programs for alcohol problems. A systematic review of the research evidence underpinning these programs is timely. Objectives: Our objective was to review the efficacy of online interventions for alcohol misuse. Systematic searches of Medline, PsycINFO, Web of Science, and Scopus were conducted for English abstracts (excluding dissertations) published from 1998 onward. Search terms were: (1) Internet, Web*; (2) online, computer*; (3) alcohol*; and (4) E\effect*, trial*, random* (where * denotes a wildcard). Forward and backward searches from identified papers were also conducted. Articles were included if (1) the primary intervention was delivered and accessed via the Internet, (2) the intervention focused on moderating or stopping alcohol consumption, and (3) the study was a randomized controlled trial of an alcohol-related screen, assessment, or intervention. Results: The literature search initially yielded 31 randomized controlled trials (RCTs), 17 of which met inclusion criteria. Of these 17 studies, 12 (70.6%) were conducted with university students, and 11 (64.7%) specifically focused on at-risk, heavy, or binge drinkers. Sample sizes ranged from 40 to 3216 (median 261), with 12 (70.6%) studies predominantly involving brief personalized feedback interventions. Using published data, effect sizes could be extracted from 8 of the 17 studies. In relation to alcohol units per week or month and based on 5 RCTs where a measure of alcohol units per week or month could be extracted, differential effect sizes to post treatment ranged from 0.02 to 0.81 (mean 0.42, median 0.54). Pre-post effect sizes for brief personalized feedback interventions ranged from 0.02 to 0.81, and in 2 multi-session modularized interventions, a pre-post effect size of 0.56 was obtained in both. Pre-post differential effect sizes for peak blood alcohol concentrations (BAC) ranged from 0.22 to 0.88, with a mean effect size of 0.66. Conclusions: The available evidence suggests that users can benefit from online alcohol interventions and that this approach could be particularly useful for groups less likely to access traditional alcohol-related services, such as women, young people, and at-risk users. However, caution should be exercised given the limited number of studies allowing extraction of effect sizes, the heterogeneity of outcome measures and follow-up periods, and the large proportion of student-based studies. More extensive RCTs in community samples are required to better understand the efficacy of specific online alcohol approaches, program dosage, the additive effect of telephone or face-to-face interventions, and effective strategies for their dissemination and marketing.

Efficient simulation of unsaturated flow using exponential time integration

We assess the performance of an exponential integrator for advancing stiff, semidiscrete formulations of the unsaturated Richards equation in time. The scheme is of second order and explicit in nature but requires the action of the matrix function φ(A) where φ(z) = [exp(z) - 1]/z on a suitability defined vector v at each time step. When the matrix A is large and sparse, φ(A)v can be approximated by Krylov subspace methods that require only matrix-vector products with A. We prove that despite the use of this approximation the scheme remains second order. Furthermore, we provide a practical variable-stepsize implementation of the integrator by deriving an estimate of the local error that requires only a single additional function evaluation. Numerical experiments performed on two-dimensional test problems demonstrate that this implementation outperforms second-order, variable-stepsize implementations of the backward differentiation formulae.

Raman spectroscopy of selected borate minerals of the pinakiolite group

The Raman spectra of a series of related minerals of the pinakiolite group of minerals have been collected and the spectra related to the mineral structure. These minerals are based upon an isolated BO33- ion. The site symmetry is reduced from D3h to C1. Intense Raman bands are observed for the minerals takeuchiite, pinakiolite, fredrikssonite and azoproite at 1084, 1086, 1086 and 1086 cm-1. These bands are assigned to the ν1 BO33- symmetric stretching mode. Low intensity Raman bands are observed for the minerals at 1345, 1748; 1435, 1748; 1435, 1750; 1436, 1749 cm-1. One probable assignment is to ν3 BO33- antisymmetric stretching mode. Intense Raman bands of takeuchiite, pinakiolite, fredrikssonite and azoproite at 712 cm-1 attributed to the ν2 out-of-plane bending mode. Importantly, through the comparison of the Raman spectra, the molecular structure of borate minerals with ill-defined structures can be obtained.

Raman spectroscopy of hydrogen arsenate group (AsO3OH)2− in solid-state compounds: cobalt-containing zinc arsenate mineral, koritnigite (Zn,Co)(AsO3OH)·H2O

Raman spectra of two well-defined types of koritnigite crystals from the Jáchymov ore district, Czech Republic, were recorded and interpreted. No substantial differences were observed between both crystal types. Observed Raman bands were attributed to the (AsO3OH)2- stretching and bending vibrations, stretching and bending vibrations of water molecules and hydroxyl ions. Non-interpreted Raman spectra of koritnigite from the RRUFF database, and published infrared spectra of cobaltkoritnigite were used for comparison. The O-H...O hydrogen bond lengths in the crystal structure of koritnigite were inferred from the Raman spectra and compared with those derived from the X-ray single crystal refinement. The presence of (AsO3OH)2- units in the crystal structure of koritnigite was proved from the Raman spectra which supports the conclusions of the X-ray structure analysis.

Mechanical evaluation of a new minimally invasive device for stabilization of proximal humeral fractures in elderly patients : a cadaver study

BACKGROUND: Treatment of proximal humerus fractures in elderly patients is challenging because of reduced bone quality. We determined the in vitro characteristics of a new implant developed to target the remaining bone stock, and compared it with an implant in clinical use. METHODS: Following osteotomy, left and right humeral pairs from cadavers were treated with either the Button-Fix or the Humerusblock fixation system. Implant stiffness was determined for three clinically relevant cases of load: axial compression, torsion, and varus bending. In addition, a cyclic varus-bending test was performed. RESULTS: We found higher stiffness values for the humeri treated with the ButtonFix system--with almost a doubling of the compression, torsion, and bending stiffness values. Under dynamic loading, the ButtonFix system had superior stiffness and less K-wire migration compared to the Humerusblock system. INTERPRETATION: When compared to the Humerusblock design, the ButtonFix system showed superior biomechanical properties, both static and dynamic. It offers a minimally invasive alternative for the treatment of proximal humerus fractures.

A Raman spectroscopic study of M2+M3+ sulfate minerals, römerite Fe2+Fe23+ (SO4)4· 14H2O and botryogen Mg2+Fe3+ (SO4)2(OH)·7H2O

The mixed valency (M2+M3+) sulphate minerals, römerite Fe2+Fe23+(SO4)4•14H2O and botryogen Mg2+Fe3+(SO4)2(OH).7H2O have been studied by Raman spectroscopy. The Raman spectra of the two types of crystals proved very similar but not identical. The observation of two symmetric stretching modes confirmed the presence of the two non-equivalent sulphate units in the römerite structure. The observation of multiple bands in the antisymmetric stretching region and in the bending regions proves the symmetry of the sulphate anion is significantly reduced in the römerite structure. The number of Raman bands related to the (SO4)2- symmetric and antisymmetric vibrations support the X-ray single crystal structure conclusion that two symmetrically distinct S6+ are present in the structure of botryogen. Römerite is a mineral of environmental significance as it is commonly found in tailings and dumps.

Raman spectroscopic study of the uranyl titanate mineral brannerite (U,Ca,Y,Ce)2(Ti,Fe)2O6 –Effect of Metamictization

Raman spectra of the uranyl titanate mineral brannerite were analysed and related to the mineral structure. A comparison is made with the Raman spectra of uranyl oxyhydroxide hydrates. Observed bands are attributed to the TiO and (UO2)2+ stretching and bending vibrations, U-OH bending vibrations, H2O and (OH)- stretching, bending and libration modes. U-O bond lengths in uranyls and O-H…O bond lengths are calculated from the wavenumbers assigned to the stretching vibrations. Raman bands of brannerite are in harmony with those of the uranyl oxyhydroxides. The mineral brannerite is metamict as is evidenced by the intensity of the UO stretching and bending modes being of lower intensity than expected and with bands that are significantly broader.

Vibration of L-shaped plates under a deterministic force or moment excitation : a case of statistical energy analysis application

Analytical and closed form solutions are presented in this paper for the vibration response of an L-shaped plate under a point force or a moment excitation. Inter-relationships between wave components of the source and the receiving plates are clearly defined. Explicit expressions are given for the quadratic quantities such as input power, energy flow and kinetic energy distributions of the L-shaped plate. Applications of statistical energy analysis (SEA) formulation in the prediction of the vibration response of finite coupled plate structures under a single deterministic forcing are examined and quantified. It is found that the SEA method can be employed to predict the frequency averaged vibration response and energy flow of coupled plate structures under a deterministic force or moment excitation when the structural system satisfies the following conditions: (1) the coupling loss factors of the coupled subsystems are known; (2) the source location is more than a quarter of the plate bending wavelength away from the source plate edges in the point force excitation case, or is more than a quarter wavelength away from the pair of source plate edges perpendicular to the moment axis in the moment excitation case due to the directional characteristic of moment excitations. SEA overestimates the response of the L-shaped plate when the source location is less than a quarter bending wavelength away from the respective plate edges owing to wave coherence effect at the plate boundary

Secure data aggregation in wireless sensor networks

A Wireless Sensor Network (WSN) is a set of sensors that are integrated with a physical environment. These sensors are small in size, and capable of sensing physical phenomena and processing them. They communicate in a multihop manner, due to a short radio range, to form an Ad Hoc network capable of reporting network activities to a data collection sink. Recent advances in WSNs have led to several new promising applications, including habitat monitoring, military target tracking, natural disaster relief, and health monitoring. The current version of sensor node, such as MICA2, uses a 16 bit, 8 MHz Texas Instruments MSP430 micro-controller with only 10 KB RAM, 128 KB program space, 512 KB external ash memory to store measurement data, and is powered by two AA batteries. Due to these unique specifications and a lack of tamper-resistant hardware, devising security protocols for WSNs is complex. Previous studies show that data transmission consumes much more energy than computation. Data aggregation can greatly help to reduce this consumption by eliminating redundant data. However, aggregators are under the threat of various types of attacks. Among them, node compromise is usually considered as one of the most challenging for the security of WSNs. In a node compromise attack, an adversary physically tampers with a node in order to extract the cryptographic secrets. This attack can be very harmful depending on the security architecture of the network. For example, when an aggregator node is compromised, it is easy for the adversary to change the aggregation result and inject false data into the WSN. The contributions of this thesis to the area of secure data aggregation are manifold. We firstly define the security for data aggregation in WSNs. In contrast with existing secure data aggregation definitions, the proposed definition covers the unique characteristics that WSNs have. Secondly, we analyze the relationship between security services and adversarial models considered in existing secure data aggregation in order to provide a general framework of required security services. Thirdly, we analyze existing cryptographic-based and reputationbased secure data aggregation schemes. This analysis covers security services provided by these schemes and their robustness against attacks. Fourthly, we propose a robust reputationbased secure data aggregation scheme for WSNs. This scheme minimizes the use of heavy cryptographic mechanisms. The security advantages provided by this scheme are realized by integrating aggregation functionalities with: (i) a reputation system, (ii) an estimation theory, and (iii) a change detection mechanism. We have shown that this addition helps defend against most of the security attacks discussed in this thesis, including the On-Off attack. Finally, we propose a secure key management scheme in order to distribute essential pairwise and group keys among the sensor nodes. The design idea of the proposed scheme is the combination between Lamport's reverse hash chain as well as the usual hash chain to provide both past and future key secrecy. The proposal avoids the delivery of the whole value of a new group key for group key update; instead only the half of the value is transmitted from the network manager to the sensor nodes. This way, the compromise of a pairwise key alone does not lead to the compromise of the group key. The new pairwise key in our scheme is determined by Diffie-Hellman based key agreement.

Raman spectroscopic study of the uranyl titanate mineral euxenite (Y,Ca,U,Ce,Th) (Nb,Ta,Ti)2O6

Raman spectra of the uranyl titanate mineral euxenite were analyzed and related to the mineral structure. A comparison is made with the Raman spectra of uranyl oxyhydroxide hydrates. The obsd. bands are attributed to the Ti[n.63743]O and (UO2)2+ stretching and bending vibrations, as well as lattice vibrations of rare-earth ions. The Raman bands of euxenite are in harmony with those of the uranyl oxyhydroxides. The mineral euxenite is metamict as is evidenced by the intensity of the U[n.63743]O stretching and bending modes, which are of lower intensity than expected, and with bands that are significantly broader.

Vibrational spectroscopic study of the antimonate mineral bindheimite Pb2Sb2O6(O,OH)

Raman spectroscopy complimented with infrared spectroscopy has been used to characterise the antimonate mineral bindheimite Pb2Sb2O6(O,OH). The mineral is characterised by an intense Raman band at 656 cm-1 assigned to SbO stretching vibrations. Other lower intensity bands at 664, 749 and 814 cm-1 are also assigned to stretching vibrations. This observation suggests the non-equivalence of SbO units in the structure. Low intensity Raman bands at 293, 312 and 328 cm-1 are assigned to the OSbO bending vibrations. Infrared bands at 979, 1008, 1037 and 1058 cm-1 may be assigned to δ OH deformation modes of SbOH units. Infrared bands at 1603 and 1640 cm-1 are assigned to water bending vibrations, suggesting that water is involved in the bindheimite structure. Broad infrared bands centred upon 3250 cm-1 supports this concept. Thus the true formula of bindheimite is questioned and probably should be written as Pb2Sb2O6(O,OH,H2O)

An infrared study of adsorption of paranitrophenol on mono, di and trialkyl surfactant intercalated organoclays

Infrared spectroscopy has been used to study the adsorption of paranitrophenol on mono, di and tri alkyl surfactant intercalated montmorillonite. Organoclays were obtained by the cationic exchange of mono, di and tri alkyl chain surfactants for sodium ions [hexadecyltrimethylammonium bromide (HDTMAB), dimethyldioctadecylammonium bromide (DDOAB), methyltrioctadecylammonium bromide (MTOAB)] in an aqueous solution with Na-montmorillonite. Upon formation of the organoclay, the properties change from strongly hydrophilic to strongly hydrophobic. This change in surface properties is observed by a decrease in intensity of the OH stretching vibrations assigned to water in the cation hydration sphere of the montmorillonite. As the cation is replaced by the surfactant molecules the paranitrophenol replaces the surfactant molecules in the clay interlayer. Bands attributed to CH stretching and bending vibrations change for the surfactant intercalated montmorillonite. Strong changes occur in the HCH deformation modes of the methyl groups of the surfactant. These changes are attributed to the methyl groups locking into the siloxane surface of the montmorillonite. Such a concept is supported by changes in the SiO stretching bands of the montmorillonite siloxane surface. This study demonstrates that paranitrophenol will penetrate into the untreated clay interlayer and replace the intercalated surfactant in surfactant modified clay, resulting in the change of the arrangement of the intercalated surfactant.

A Raman spectroscopic study of the ‘cave’ mineral ardealite Ca2(HPO4)(SO4)•4H2O

The mineral ardealite Ca2(HPO4)(SO4)•4H2O is a ‘cave’ mineral and is formed through the reaction of calcite with bat guano. The mineral shows disorder and the composition varies depending on the origin of the mineral. Raman spectroscopy complimented with infrared spectroscopy has been used to characterise the mineral ardealite. The Raman spectrum is very different from that of gypsum. Bands are assigned to SO42- and HPO42- stretching and bending modes.

A biomechanical investigation of vertebral staples for fusionless scoliosis correction

Background: Fusionless scoliosis surgery is an early-stage treatment for idiopathic scoliosis which claims potential advantages over current fusion-based surgical procedures. Anterior vertebral stapling using a shape memory alloy staple is one such approach. Despite increasing interest in this technique, little is known about the effects on the spine following insertion, or the mechanism of action of the staple. The purpose of this study was to investigate the biomechanical consequences of staple insertion in the anterior thoracic spine, using in vitro experiments on an immature bovine model. Methods: Individual calf spine thoracic motion segments were tested in flexion, extension, lateral bending and axial rotation. Changes in motion segment rotational stiffness following staple insertion were measured on a series of 14 specimens. Strain gauges were attached to three of the staples in the series to measure forces transmitted through the staple during loading. A micro-CT scan of a single specimen was performed after loading to qualitatively examine damage to the vertebral bone caused by the staple. Findings: Small but statistically significant decreases in bending stiffness occurred in flexion,extension, lateral bending away from the staple, and axial rotation away from the staple. Each strain-gauged staple showed a baseline compressive loading following insertion which was seen to gradually decrease during testing. Post-test micro-CT showed substantial bone and growth plate damage near the staple. Interpretation: Based on our findings it is possible that growth modulation following staple insertion is due to tissue damage rather than sustained mechanical compression of the motion segment.