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- ν1 symmetric stretching mode. Low intensity Raman bands at 1152, 1263 and 1277 cm-1 are assigned to the PO43- ν3 antisymmetric stretching vibrations. Raman bands at 497 and 552 cm-1 are attributed to the PO43- ν4 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- ν2 bending modes. The values for the OH stretching vibrations provide hydrogen bond distances of 2.728Å (3267 cm-1), 2.781Å (3374cm-1), 2.868Å (3479 cm-1), and 2.918Å (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 vibrational spectroscopic study of the mixed anion mineral sanjuanite Al2(PO4)(SO4)(OH)•9H2O

The mineral sanjuanite Al2(PO4)(SO4)(OH)•9H2O has been characterised by Raman spectroscopy complimented by infrared spectroscopy. The mineral is characterised by an intense Raman band at 984 cm-1, assigned to the (PO4)3- ν1 symmetric stretching mode. A shoulder band at 1037 cm-1 is attributed to the (SO4)2- ν1 symmetric stretching mode. Two Raman bands observed at 1102 and 1148 cm-1 are assigned to (PO4)3- and (SO4)2- ν3 antisymmetric stretching modes. Multiple bands provide evidence for the reduction in symmetry of both anions. This concept is supported by the multiple sulphate and phosphate bending modes. Raman spectroscopy shows that there are more than one non-equivalent water molecules in the sanjuanite structure. There is evidence that structural disorder exists, shown by the complex set of overlapping bands in the Raman and infrared spectra. At least two types of water are identified with different hydrogen bond strengths. The involvement of water in the sanjuanite structure is essential for the mineral stability.

Crowdsourcing information systems : a systems theory perspective

Crowdsourcing harnesses the potential of large and open networks of people. It is a relatively new phenomenon and attracted substantial interest in practice. Related research, however, lacks a theoretical foundation. We propose a system-theoretical perspective on crowdsourcing systems to address this gap and illustrate its applicability by using it to classify crowdsourcing systems. By deriving two principal dimensions from theory, we identify four fundamental types of crowdsourcing systems that help to distinguish important features of such systems. We analyse their respective characteristics and discuss implications and requirements for various aspects related to the design of such systems. Our results demonstrate that systems theory can inform the study of crowdsourcing systems. The identified system types and the implications on their design may prove useful for researchers to frame future studies and for practitioners to identify the right crowdsourcing systems for a particular purpose.

Single crystal raman spectroscopy of natural finnemanite and comparison with the synthesised analogue

The single crystal Raman spectra of natural mineral finnemanite Pb5(AsO3)3Cl from the Långban locality, Filipstad district, Värmland province, Sweden are presented for the first time. It is a hexagonal mineral belonging to the ortho arsenite group, where the [AsO3]3- ion is isolated. The spectra of finnemanite are characterized by a strong band at 734 cm-1 overlying a shoulder at 726 cm-1, and broad overlapping bands in the lower wavenumber with the strongest band positioned at 174 cm-1. Band assignments were made based on band symmetry, experimental band positions from literature and DFT calculated Raman spectrum, and spectral comparison with other ortho arsenite minerals reinerite, cafarsite, and nealite and synthetic lead arsenite compounds Pb2(AsO2)3Cl, Pb2As2O5, and PbAs2O4 . The band at 734 cm-1 was assigned to υ1(AsO3), bands at 726 and 640 cm-1 assigned to υ3, 372 and 357 cm-1 to υ2, and 244, 239 and 207 cm-1 to υ4. The single crystal spectra of finnemanite showed good mode separation, allowing bands to be assigned a symmetry species of Ag, E1g, or E2g.

Screening to identify large truck potential blackspots : methodological issues and concerns

1. Overview of hotspot identification (HSID)methods 2. Challenges with HSID 3. Bringing crash severity into the ‘mix’ 4. Case Study: Truck Involved Crashes in Arizona 5. Conclusions • Heavy duty trucks have different performance envelopes than passenger cars and have more difficulty weaving, accelerating, and braking • Passenger vehicles have extremely limited sight distance around trucks • Lane and shoulder widths affect truck crash risk more than passenger cars • Using PDOEs to model truck crashes results in a different set of locations to examine for possible engineering and behavioral problems • PDOE models point to higher societal cost locations, whereas frequency models point to higher crash frequency locations • PDOE models are less sensitive to unreported crashes • PDOE models are a great complement to existing practice

Whelanite Ca5Cu2(OH)2CO3,Si6O17•4H2O – A vibrational spectroscopic study

Whelanite Ca5Cu2(OH)2CO3,Si6O17•4H2O is a hydrated hydroxy mixed anion compound with both silicate and carbonate anions in the formula. The structural characterisation of the mineral whelanite remains incomplete. Whelanite is probably a neosilicate with Cu2+ in square planar coordination. Two Raman bands at 1070 and 1094 cm-1 are assigned to the ν1 symmetric stretching modes of the CO32- units. The observation of two symmetric stretching modes supports the concept of two non-equivalent CO32- units in the whelanite structure. The intense sharp Raman band at 1006 cm-1 is assigned to the ν1 (A1g) symmetric stretching vibration of the Si6O17 units. The splitting of the ν3 vibrational mode offers support to the concept that the SiO4 tetrahedron in whelanite is strongly distorted. A very intense Raman band observed at 666 cm-1 with a shoulder at 697 cm-1 is assigned to the ν4 vibrational modes. Intense Raman bands at 3534, 3556, 3550 and 3595 cm-1 are assigned to the stretching vibrations of the OH units. Low intensity Raman bands at 2910, 3187 and 3453 cm-1 are assigned to water stretching modes. Thus, vibrational spectroscopy has been used to characterise the molecular structure of whelanite. Whelanite is a mineral that could be conceived as a healing mineral

Raman spectroscopic study of the mineral arsenogorceixite BaAl3AsO3(OH)(AsO4,PO4)(OH,F)6

Arsenogorceixite BaAl3AsO3(OH)(AsO4,PO4)(OH,F)6 belongs to the crandallite mineral subgroup of the alunite supergroup. Arsenogorceixite forms a continuous series of solid solutions with related minerals including gorceixite, goyazite, arsenogoyazite, plumbogummite and philipsbornite. Two minerals from (a) Germany and (b) from Ashburton Downs, Australia were analysed by Raman spectroscopy. The spectra show some commonality but the intensities of the peaks vary. Sharp intense Raman bands for the German sample, are observed at 972 and 814 cm−1 attributed to the ν1 PO43− and AsO43− symmetric stretching modes. Raman bands at 1014, 1057, 1148 and 1160 cm−1 are attributed to the ν1 PO2 symmetric stretching mode and ν3 PO43− antisymmetric stretching vibrations. Raman bands at 764 and 776 cm−1 and 758 and 756 cm−1 are assigned to the ν3 AsO43− antisymmetric stretching vibrations. For the Australian mineral, the ν1 PO43− band is found at 973 cm−1. The intensity of the arsenate bands observed at 814, 838 and 870 cm−1 is greatly enhanced. Two low intensity Raman bands at 1307 and 1332 cm−1 are assigned to hydroxyl deformation modes. The intense Raman band at 441 cm−1 with a shoulder at 462 cm−1 is assigned to the ν2 PO43− bending mode. Raman bands at 318 and 340 cm−1 are attributed to the (AsO4)3−ν2 bending. The broad band centred at 3301 cm−1 is assigned to water stretching vibrations and the sharper peak at 3473 cm−1 is assigned to the OH stretching vibrations. The observation of strong water stretching vibrations brings into question the actual formula of arsenogorceixite. It is proposed the formula is better written as BaAl3AsO3(OH)(AsO4,PO4)(OH,F)6·xH2O. The observation of both phosphate and arsenate bands provides a clear example of solid solution formation.

Raman spectroscopy of synthetic CaHPO4•2H2O– and in comparison with the cave mineral brushite

The mineral brushite has been synthesised by mixing calcium ions and hydrogen phosphate anions to mimic the reactions in a Cave. The vibrational spectra of the synthesised brushite were compared with that of the natural Cave mineral. Bands attributable to the PO43- and HPO42- anions are observed. Brushite, both synthetic and natural, is characterised by an intense sharp band at 985 cm-1 with a shoulder at 1000 cm-1. Characteristic bending modes are observed in the 300 to 600 cm-1 region. The spectra of the synthesised brushite matches very well the spectrum of brushite from the Moorba Cave, Western Australia.

Cryotherapy and joint position sense in healthy participants: a systematic review

Objective: To (1) search the English-language literature for original research addressing the effect of cryotherapy on joint position sense (JPS) and (2) make recommendations regarding how soon healthy athletes can safely return to participation after cryotherapy. Data Sources: We performed an exhaustive search for original research using the AMED, CINAHL, MEDLINE, and SportDiscus databases from 1973 to 2009 to gather information on cryotherapy and JPS. Key words used were cryotherapy and proprioception, cryotherapy and joint position sense, cryotherapy, and proprioception. Study Selection: The inclusion criteria were (1) the literature was written in English, (2) participants were human, (3) an outcome measure included JPS, (4) participants were healthy, and (5) participants were tested immediately after a cryotherapy application to a joint. Data Extraction: The means and SDs of the JPS outcome measures were extracted and used to estimate the effect size (Cohen d) and associated 95% confidence intervals for comparisons of JPS before and after a cryotherapy treatment. The numbers, ages, and sexes of participants in all 7 selected studies were also extracted. Data Synthesis: The JPS was assessed in 3 joints: ankle (n 5 2), knee (n 5 3), and shoulder (n 5 2). The average effect size for the 7 included studies was modest, with effect sizes ranging from 20.08 to 1.17, with a positive number representing an increase in JPS error. The average methodologic score of the included studies was 5.4/10 (range, 5–6) on the Physiotherapy Evidence Database scale. Conclusions: Limited and equivocal evidence is available to address the effect of cryotherapy on proprioception in the form of JPS. Until further evidence is provided, clinicians should be cautious when returning individuals to tasks requiring components of proprioceptive input immediately after a cryotherapy treatment.

Vibrational spectroscopic study of the minerals nekoite Ca3Si6O15•7H2O and okenite Ca10Si18O46•18H2O : implications for the molecular structure

Nekoite Ca3Si6O15•7H2O and okenite Ca10Si18O46•18H2O are both hydrated calcium silicates found respectively in contact metamorphosed limestone and in association with zeolites from the alteration of basalts. The minerals form two-Dimensional infinite sheets with other than six-membered rings with 3-, 4-, or 5-membered rings and 8-membered rings. The two minerals have been characterised by Raman, near-infrared and infrared spectroscopy. The Raman spectrum of nekoite is characterised by two sharp peaks at 1061 and 1092 cm-1 with bands of lesser intensity at 974, 994, 1023 and 1132 cm-1. The Raman spectrum of okenite shows an intense single Raman band at 1090 cm-1 with a shoulder band at 1075 cm-1.These bands are assigned to the SiO stretching vibrations of Si2O5 units. Raman water stretching bands of nekoite are observed at 3071, 3380, 3502 and 3567 cm-1. Raman spectrum of okenite shows water stretching bands at 3029, 3284, 3417, 3531 and 3607 cm-1. NIR spectra of the two minerals are subtly different inferring water with different hydrogen bond strengths. By using a Libowitzky empirical formula, hydrogen bond distances based upon these OH stretching vibrations. Two types of hydrogen bonds are distinguished: strong hydrogen bonds associated with structural water and weaker hydrogen bonds assigned to space filling water molecules.

Entertainment architecture : constructing a framework for the creation of an emerging transmedia form

This thesis investigates the radically uncertain formal, business, and industrial environment of current entertainment creators. It researches how a novel communication technology, the Internet, leads to novel entertainment forms, how these lead to novel kinds of businesses that lead to novel industries; and in what way established entertainment forms, businesses, and industries are part of that process. This last aspect is addressed by focusing on one exemplary es-tablished form: movies. Using a transdisciplinary approach and a combination of historical analysis, industry interviews, and an innovative mode of ‘immersive’ textual analysis, a coherent and comprehensive conceptual framework for the creation of and re-search into a specific emerging entertainment form is proposed. That form, products based on it, and the conceptual framework describing it are all re-ferred to as Entertainment Architecture (‘entarch,’ for short). The thesis charac-terises this novel form as Internet-native transmedia entertainment, meaning it fully utilises the unique communicative characteristics of the Internet, and is spread across media. The thesis isolates four constitutive elements within Entertainment Architec-ture: story, play, ‘dance,’ and ‘glue.’ That is, entarch tells a story; offers playful interaction; invites social interaction between producer and consumer, and amongst consumers (‘dance’); and all components of it can be spread across many media, but are so well interconnected and mutually dependent that they are perceived as one product instead of many (‘glue’). This sets entarch apart from current media franchises like Star Wars or Halo, which are perceived as many products spread across many media. Entarch thus embraces the commu-nicative behaviour of Internet-native consumers instead of forcing them to de-sist from it, it harnesses the strengths of various media while avoiding some of their weaknesses, and it can sustain viable businesses. The entarch framework is an innovative contribution to scholarship that al-lows researchers to investigate this emerging entertainment form in a structured way. The thesis demonstrates this by using it to survey business models appro-priate to the entarch environment. The framework can also be used by enter-tainment creators — exemplified in the thesis by moviemakers — to delimit the room for manoeuvre available to them in a changing environment.

Outcomes following operative and non-operative management of humeral midshaft fractures: a prospective, observational cohort study of 47 patients

Background Although the non-operative management of closed humeral midshaft fractures has been advocated for years, the increasing popularity of operative intervention has left the optimal treatment choice unclear. Objective To compare the outcomes of operative and non-operative treatment of traumatic closed humeral midshaft fractures in adult patients. Methods A multicentre prospective comparative cohort study across 20 centres was conducted. Patients with AO type 12 A2, A3 and B2 fractures were treated with a functional brace or a retrograde-inserted unreamed humeral nail. Follow-up measurements were taken at 6, 12 and 52 weeks after the injury. The primary outcome was fracture healing after 1 year. Secondary outcomes included sub-items of the Constant score, general patient satisfaction, complications and cost-effectiveness parameters. Functions of the uninjured extremity were used as reference parameters. Intention-to-treat analysis was applied with the use of t-tests, Fisher’s exact tests, Mann–Whitney U-tests and adjusted analysis of variance (ANOVA). Results Forty-seven patients were included. The patient sample consisted of 23 women and 24 men, with a mean age of 52.7 years (range 17–86 years). Of the 47 cases, 14 were treated non-operatively and 33 operatively. The follow-up rate at 1 year was 81%. After 1 year, 11 fractures (100%) healed in the non-operative group and at least 24 fractures (≥89%) healed in the operative group [1 non-union patient (4%) and no data for 2 patients (7%)]. There were no significant differences in pain, range of motion (ROM) of the shoulder and elbow, and return to work after 6 weeks, 12 weeks and 1 year. Although operatively treated patients showed significantly greater shoulder abduction strength (p = 0.036), elbow flexion strength (p = 0.021), functional hand positioning (p = 0.008) and return to recreational activities (p = 0.043) after 6 weeks, no statistically significant differences existed in any outcome measure at the 1-year follow-up. Conclusions Our findings indicate that the non-operative management of humeral midshaft fractures can be expected to have similar functional outcomes and patient satisfaction at 1 year, despite an early benefit to operative treatment. If no radiological evidence of fracture healing exists in non-operatively treated patients during early follow-up, a switch to surgical treatment results in good functional outcomes and patient satisfaction. Keywords: Humeral shaft fracture, Non-operative treatment, Functional brace, Operative treatment, Unreamed humeral nail (UHN), Prospective, Cohort study

Secondary curve behavior in Lenke Type 1C adolescent idiopathic scoliosis after thoracoscopic selective anterior thoracic fusion

Study Design. Analysis of a case series of 24 Lenke 1C adolescent idiopathic scoliosis (AIS) patients receiving selective thoracoscopic anterior scoliosis correction. Objective. To report the behaviour of the compensatory lumbar curve in a group of Lenke IC AIS patients following thoracoscopic anterior scoliosis correction, and to compare the results of this study with previously published data. Summary of Background Data. Several prior studies have reported spontaneous lumbar curve correction for both anterior and posterior selective fusion in Lenke 1C/King-Moe II patients; however to our knowledge no previous studies have reported outcomes of thoracoscopic anterior correction for this curve type. Methods. All AIS patients with a curve classification of Lenke 1C and a minimum of 24 months follow-up were retrieved from a consecutive series of 190 AIS patients who underwent thoracoscopic anterior instrumented fusion. Cobb angles of the major curve, instrumented levels, compensatory lumbar curve, and T5-T12 kyphosis were recorded, as well as coronal spinal balance, T1 tilt angle and shoulder balance. All radiographic parameters were measured before surgery and at 2, 6, 12 and 24 months after surgery. Results. Twenty-four female patients with right thoracic curves had a mean thoracic Cobb angle of 53.0° before surgery, decreasing to 24.9° two years after surgery. The mean lumbar compensatory Cobb angle was 43.5° before surgery, spontaneously correcting to 25.4° two years after surgery, indicating balance between the thoracic and lumbar scoliotic curves. The lumbar correction achieved (41.8%) compares favourably to previous studies. Conclusions. Selective thoracoscopic anterior fusion allows spontaneous lumbar curve correction and achieves coronal balance of main thoracic and compensatory lumbar curves, good cosmesis and patient satisfaction. Correction and balance are maintained 24 months after surgery.

Water-based exercise for patients with chronic arm lymphedema : a randomized controlled pilot trial

Objective: To evaluate the feasibility and effect of a water-based exercise (WBE) program on lymphedema status and shoulder range of motion (ROM) among women with breast cancer related lymphedema. Design: Single-blinded, randomized controlled pilot trial. Twenty-nine eligible breast cancer survivors (median 10 years after surgery) with arm lymphedema (median 21% inter limb difference) were included and randomized into intervention (n= 15) or control (n=14). Twenty-five participants completed the study. The intervention was at least twice weekly WBE for 8 weeks; supervised initially but performed independently during the study period. Outcomes of interest were feasibility as measured by retention and adherence, lymphedema status as measured by optoelectronic perometry, bioimpedance spectroscopy and tissue dielectric constant, and shoulder range of motion (ROM) as measured by goniometer. Results: Four participants were not measured at post-intervention and were not included in the analysis (retention). Four participants in the intervention group did not perform the minimum WBE criteria set (adherence). No effect was found on lymphedema status. Compared to the control group, median ROM change for flexion was 6 (1-10) degrees (p<0.001) and 6 (0-15.5) degrees (p=0,07) for external rotation. Clinically relevant increase in the intervention group was found for 36% in flexion (p≤0.05) and (57%) in external rotation (p≤0.05) compared to controls. Conclusions: This study shows WBE is feasible for breast cancer survivors with arm lymphedema and that shoulder ROM can be improved years after cancer treatment has been completed.

Intratherapist reliability in the rating of scapula posture in multiple planes of reference

Background: Evaluation of scapular posture is a fundamental component in the clinical evaluation of the upper quadrant. This study examined the intrarater reliability of scapular posture ratings. Methods: A test-retest reliability investigation was undertaken with one week between assessment sessions. At each session physical therapists conducted visual assessments of scapula posture (relative to the thorax) in five different scapula postural planes (plane of scapula, sagittal plane, transverse plane, horizontal plane, and vertical plane). These five plane ratings were performed for four different scapular posture perturbating conditions (rest, isometric shoulder; flexion, abduction, and external rotation). Results. A total of 100 complete scapular posture ratings (50 left, 50 right) were undertaken at each assessment. The observed agreement between the test and retest postural plane ratings ranged from 59% to 87%; 16 of the 20 plane-condition combinations exceeded 75% observed agreement. Kappa (and prevalence adjusted bias adjusted kappa) values were inconsistent across the postural planes and perturbating conditions. Conclusions: This investigation generally revealed fair to moderate intrarater reliability in the rating of scapular posture by visual inspection. However, enough disagreement between assessments was present to warrant caution when interpreting perceived changes in scapula position between longitudinal assessments using visual inspection alone.