Vibrational spectroscopy of synthetic stercorite H(NH4)Na(PO4)•4H2O – a comparison with the natural cave mineral

In order to mimic the chemical reactions in cave systems, the analogue of the mineral stercorite H(NH4)Na(PO4)•4H2O has been synthesised. X-ray diffraction of the stercorite analogue matches the stercorite reference pattern. A comparison is made with the vibrational spectra of synthetic stercorite analogue and the natural Cave mineral. The mineral in nature is formed by the reaction of bat guano chemicals on calcite substrates. A single Raman band at 920 cm-1 (Cave) and 922 cm-1 (synthesised) defines the presence of hydrogen phosphate in the mineral. In the synthetic stercorite analogue, additional bands are observed and are attributed to the dihydrogen and phosphate anions. The vibrational spectra of synthetic stercorite only partly match that of the natural stercorite. It is suggested that natural stercorite is more pure than that of synthesised stercorite. Antisymmetric stretching bands are observed in the infrared spectrum at 1052, 1097, 1135 and 1173 cm-1. Raman spectroscopy shows the stercorite mineral is based upon the hydrogen phosphate anion and not the phosphate anion. Raman and infrared bands are found and assigned to PO43-, H2O, OH and NH stretching vibrations. Raman spectroscopy shows the synthetic analogue is similar to the natural mineral. A mechanism for the formation of stercorite is provided.

The two faces of normative commitment : a qualitative study of the dual nature of normative commitment

Organisational commitment is extensively represented in the human resource management and organisational behaviour literature as a key factor in the relationship between employees and their organisations. Although Allen and Meyer (1990) noted that an employee can experience the three components of organisational commitment simultaneously, in terms of commitment profiles, the majority of studies have looked at the antecedents and outcomes of affective, continuance, and normative commitment independently. There is still only limited research that has investigated the nature of commitment profiles and their implications for employee work-related behaviours (Gellatly Meyer and Luchak 2006; Herscovitch & Meyer 2002; Somers 2010; Wasti 2005). An area where the commitment profiles approach potentially provides new insights is on the nature of normative commitment.

Stability of hydrotalcites formed from Bayer refinery environmental control processes

Bauxite refinery residues (red mud) are derived from the Bayer process by the digestion of crushed bauxite in concentrated sodium hydroxide at elevated temperatures and pressures. This slurry residue, if untreated, is unsuitable for discharge directly into the environment and is usually stored in tailing dams. The liquid portion has the potential for discharge, but requires pre-treatment before this can occur. The seawater neutralisation treatment facilitates a significant reduction in pH and dissolved metal concentrations, through the precipitation of hydrotalcite-like compounds and some other Mg, Ca, and Al hydroxide and carbonate minerals. The hydrotalcite-like compounds, precipitated during seawater neutralisation, also remove a range of transition metals, oxy-anions and other anionic species through a combination of intercalation and adsorption reactions: smaller anions are intercalated into the hydrotalcite matrix, while larger molecules are adsorbed on the particle surfaces. A phenomenon known as ‘reversion’ can occur if the seawater neutralisation process is not properly controlled. Reversion causes an increase in the pH and dissolved impurity levels of the neutralised effluent, rendering it unsuitable for discharge. It is believed that slow dissolution of components of the red mud residue and compounds formed during the neutralisation process are responsible for reversion. This investigation looked at characterising natural hydrotalcite (Mg6Al2(OH)16(CO3)∙4H2O) and ‘Bayer’ hydrotalcite (synthesised using the seawater neutralisation process) using a variety of techniques including X-ray diffraction, infrared and Raman spectroscopy, and thermogravimetric analysis. This investigation showed that Bayer hydrotalcite is comprised of a mixture of 3:1 and 4:1 hydrotalcite structures and exhibited similar chemical characteristic to the 4:1 synthetic hydrotalcite. Hydrotalcite formed from the seawater neutralisation of Bauxite refinery residues has been found not to cause reversion. Other components in red mud were investigated to determine the cause of reversion and this investigation found three components that contributed to reversion: 1) tricalcium aluminate, 2) hydrocalumite and 3) calcium hydroxide. Increasing the amount of magnesium in the neutralisation process has been found to be successful in reducing reversion.

Sulfate intercalated layered double hydroxides prepared by the reformation effect

The removal of the sulfate anion from water using synthetic hydrotalcite (Mg/Al LDH) was investigated using powder x-ray diffraction (XRD) and thermogravimetric analysis (TG). Synthetic hydrotalcite Mg6Al2(OH)16(CO3)∙4H2O was prepared by the co-precipitation method from aluminum and magnesium chloride salts. The synthetic hydrotalcite was thermally activated to a maximum temperature of 380°C. Samples of thermally activated hydrotalcite where then treated with aliquots of 1000ppm sulfate solution. The resulting products where dried and characterized by XRD and TG. Powder XRD revealed that hydrotalcite had been successfully prepared and that the product obtained after treatment with sulfate solution also conformed well to the reference pattern of hydrotalcite. The d(003) spacing of all samples was found to be within the acceptable region for a LDH structure. TG revealed all products underwent a similar decomposition to that of hydrotalcite. It was possible to propose a reasonable mechanism for the thermal decomposition of a sulfate containing Mg/Al LDH. The similarities in the results may indicate that the reformed hydrotalcite may contain carbonate anion as well as sulfate. Further investigation is required to confirm this.

Vibrational spectroscopy of synthetic archerite (K,NH4)H2PO4 : and in comparison with the natural cave mineral

In order to mimic the formation of archerite in cave minerals, the mineral analogue has been synthesised. The cave mineral is formed by the reaction of the chemicals in bat guano with calcite substrates. X-ray diffraction proves that the synthesised archerite analogue was pure. The vibrational spectra of the synthesised mineral are compared with that of the natural cave mineral. Raman and infrared bands are assigned to H2PO4-, OH and NH stretching and bending vibrations. The Raman band at 917 cm-1 is assigned to the HOP stretching vibration of the H2PO4- units. Bands in the 1200 to 1800 cm-1 region are associated with NH4+ bending modes. Vibrational spectroscopy enables the molecular structure of archerite to be analysed.

Sustaining a healthy workforce

The changing demographics of the mining workforce and the increasing demand for skilled workers increases the importance of sustaining a healthy workforce now and for the future. Although health is strongly related to safety, the two areas are not well integrated and the relationship is poorly understood. As such there is an important need to raise the profile of health within the Occupational Health and Safety (OH&S) domain. The mining industry carries health and safety risks, often greater than other occupations. Whilst the mining industry is regulated by stringent OH&S controls, the very nature of the work and environmental influences expose employees to a greater number of injury risk factors than many other industries. In contrast to its excellent safety record, compared to most other industries, the mining workforce has a high proportion of chronic health problems. These problems can be exacerbated by the ageing of the workforce, regional location of sites and organisational issues influencing work demands. A major focus has been on the treatment of these conditions with relatively limited attention to prevention strategies. An important prevention strategy is the raising of awareness among the workforce of health issues and the significant increase in the volume of health related information has provided an excellent opportunity to access relevant information. Unfortunately, this information is of varying quality, may not be evidence based, and may provide the wrong guidance to the development of interventions designed to improve health. Limited time of most employees and potential lack of knowledge of ability to differentiate quality information presents additional problems or barriers to increasing awareness of health issues...

Separation of acoustic emission signals from small size multi-cylinder diesel engine

This paper presents techniques which can lead to diagnosis of faults in a small size multi-cylinder diesel engine. Preliminary analysis of the acoustic emission (AE) signals is outline, including time-frequency analysis and selection of optimum frequency band.The results of applying mean field independent component analysis (MFICA) to separate the AE root mean square (RMS) signals and the effects of changing parameter values are also outlined. The results on separation of RMS signals show thsi technique has the potential of increasing the probability to successfully identify the AE events associated with the various mechanical events within the combustion process of multi-cylinder diesel engines.

Photocatalytic disinfection of bacterial pollutants using suspended and immobilized TiO(2) powders

The photocatalytic disinfection of Enterobacter cloacae and Enterobacter coli using microwave (MW), convection hydrothermal (HT) and Degussa P25 titania was investigated in suspension and immobilized reactors. In suspension reactors, MW-treated TiO(2) was the most efficient catalyst (per unit weight of catalyst) for the disinfection of E. cloacae. However, HT-treated TiO(2) was approximately 10 times more efficient than MW or P25 titania for the disinfection of E. coli suspensions in surface water using the immobilized reactor. In immobilized experiments, using surface water a significant amount of photolysis was observed using the MW- and HT-treated films; however, disinfection on P25 films was primarily attributed to photocatalysis. Competitive action of inorganic ions and humic substances for hydroxyl radicals during photocatalytic experiments, as well as humic substances physically screening the cells from UV and hydroxyl radical attack resulted in low rates of disinfection. A decrease in colony size (from 1.5 to 0.3 mm) was noted during photocatalytic experiments. The smaller than average colonies were thought to occur during sublethal (•) OH and O(2) (•-) attack. Catalyst fouling was observed following experiments in surface water and the ability to regenerate the surface was demonstrated using photocatalytic degradation of oxalic acid as a model test system

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.

Zinc aluminium layered double hydroxides for the removal of iodine and iodide from aqueous solutions

129I is a radioactive isotope of iodine that is readily absorbed by the body. In this paper we investigated the potential of a 3:1 Zn/Al layered double hydroxide (LDH) as a sorbent for the removal of iodine and iodide from water. Synthetic Zn6Al2(OH)16(CO3)∙4H2O was prepared by the co-precipitation before thermal activation. The LDH was treated with solutions containing iodide and iodine. It was found that iodine could be more easily removed from solution than iodide. Powder X-ray diffraction revealed the destruction of the LDH structure during thermal activation and the successful reformation of a similar LDH material after treatment with the iodide or iodine solution. Thermal decomposition of all samples studied by thermogravimetry appeared to be similar. A new decomposition mechanism similar to one previously described in the literature was proposed for the Zn/Al LDH. The total mass loss of samples treated with iodide and iodine was significantly lower than that of the original LDH indicating that iodine species may form non-removable anions when intercalated into the LDH structure. Evolved gas mass spectrometry failed to detect any iodine species lost as gases during the decomposition of iodide treated LDH however, small quantities of iodine species were observed during decomposition of samples treated with iodine solution.

Damage quantification techniques in acoustic emission monitoring

Acoustic emission (AE) analysis is one of the several diagnostic techniques available nowadays for structural health monitoring (SHM) of engineering structures. Some of its advantages over other techniques include high sensitivity to crack growth and capability of monitoring a structure in real time. The phenomenon of rapid release of energy within a material by crack initiation or growth in form of stress waves is known as acoustic emission (AE). In AE technique, these stress waves are recorded by means of suitable sensors placed on the surface of a structure. Recorded signals are subsequently analysed to gather information about the nature of the source. By enabling early detection of crack growth, AE technique helps in planning timely retrofitting or other maintenance jobs or even replacement of the structure if required. In spite of being a promising tool, some challenges do still exist behind the successful application of AE technique. Large amount of data is generated during AE testing, hence effective data analysis is necessary, especially for long term monitoring uses. Appropriate analysis of AE data for quantification of damage level is an area that has received considerable attention. Various approaches available for damage quantification for severity assessment are discussed in this paper, with special focus on civil infrastructure such as bridges. One method called improved b-value analysis is used to analyse data collected from laboratory testing.

Vibrational spectroscopic study of the minerals cavansite and pentagonite Ca(V4+O)Si4O10.4H2O

The bright blue minerals cavansite and pentagonite, a calcium vanadium silicate Ca(V4+O)Si4O10.4H2O, have been studied by UV–Visible, Raman and infrared spectroscopy. Cavansite shows an open porous structure with very small micron sized holes. Strong UV–Visible absorption bands are observed at around 403, 614 and 789 nm for cavansite and pentagonite. The Raman spectrum of cavansite is dominated by an intense band at 981 cm -1 and pentagonite by a band at 971 cm-1 attributed to the stretching vibrations of (SiO3)n units. Cavansite is characterised by two intense bands at 574 and 672 cm-1 whereas pentagonite by a single band at 651 cm-1. The Raman spectrum of cavansite in the hydroxyl stretching region shows bands at 3504, 3546, 3577, 3604 and 3654 cm-1 whereas pentagonite is a single band at 3532 cm_1. These bands are attributed to water coordinated to calcium and vanadium. XPS studies show that bond energy of oxygen in oxides is 530 eV, and in hydroxides -531.5 eV and for water -533.5 eV. XPS studies show a strong peak at 531.5 eV for cavansite, indicating some OH units in the structure of cavansite.

The effect of Tenofovir on vitamin D metabolism in HIV-infected adults is dependent on sex and ethnicity

Background: Tenofovir has been associated with renal phosphate wasting, reduced bone mineral density, and higher parathyroid hormone levels. The aim of this study was to carry out a detailed comparison of the effects of tenofovir versus non-tenofovir use on calcium, phosphate and, vitamin D, parathyroid hormone (PTH), and bone mineral density. Methods: A cohort study of 56 HIV-1 infected adults at a single centre in the UK on stable antiretroviral regimes comparing biochemical and bone mineral density parameters between patients receiving either tenofovir or another nucleoside reverse transcriptase inhibitor. Principal Findings: In the unadjusted analysis, there was no significant difference between the two groups in PTH levels (tenofovir mean 5.9 pmol/L, 95% confidence intervals 5.0 to 6.8, versus non-tenofovir; 5.9, 4.9 to 6.9; p = 0.98). Patients on tenofovir had significantly reduced urinary calcium excretion (median 3.01 mmol/24 hours) compared to non-tenofovir users (4.56; p,0.0001). Stratification of the analysis by age and ethnicity revealed that non-white men but not women, on tenofovir had higher PTH levels than non-white men not on tenofovir (mean difference 3.1 pmol/L, 95% CI 5.3 to 0.9; p = 0.007). Those patients with optimal 25-hydroxyvitamin D (.75 nmol/L) on tenofovir had higher 1,25-dihydroxyvitamin D [1,25(OH)2D] (median 48 pg/mL versus 31; p = 0.012), fractional excretion of phosphate (median 26.1%, versus 14.6;p = 0.025) and lower serum phosphate (median 0.79 mmol/L versus 1.02; p = 0.040) than those not taking tenofovir. Conclusions: The effects of tenofovir on PTH levels were modified by sex and ethnicity in this cohort. Vitamin D status also modified the effects of tenofovir on serum concentrations of 1,25(OH)2D and phosphate.

Vitamin D intake, sun exposure and 25-hydroxy vitamin D status in Peritoneal dialysis (PD) and Haemodialysis (HD) patients

Inadequate vitamin D levels have been linked to bone disease but more recently have been associated with wider health implications. Limited studies suggest a high prevalence of Vitamin D deficiency in dialysis patients, although evidence is lacking on whether this is due to dietary restrictions, limited mobility and time outdoors or a combination of these. The aim of this study was to assess the contributions of diet, supplements and sunlight exposure to serum Vitamin D (25(OH)D) levels in dialysis patients. Cross-sectional data were obtained from 30 PD (Mean±SD age 56.9±16.2 y; n=13 male) and 22 HD (Mean±SD age 65.4±14.0 y; n=18 male) patients between 2009 and 2010. Serum 25(OH)D was measured and oral vitamin D intake estimated through a food-frequency-questionnaire and quantifying inactive supplementation. Sunlight exposure was assessed using a validated questionnaire. Prevalence of inadequate/insufficient vitamin D differed between dialysis modality (31% and 43% insufficient (<50nmol/L); 4% and 34% deficient (<25nmol/L) in HD and PD patients respectively (p=0.002)). In HD patients, there was a significant correlation between diet plus supplemental vitamin D intake and 25(OH)D (ρ=0.84, p<0.001). Results suggest a higher frequency of 25(OH)D inadequacy/deficiency in PD compared to HD patients. No other relationships between intake, sun exposure and 25(OH)D were seen. This could reflect limitations of the study design or the importance of other factors such as age, ethnicity and sun protection as interactions in the analysis. Understanding these factors is important given Vitamin D’s emerging status as a biomarker of systemic ill health.

Proposed structures for poorly characterized phases in C2M carbonaceous chondrite meteorites

Structure and chemistry of poorly characterized phases (PCP). We suggest here that approximately 10 angstrom PCP, a dominant matrix variety, has a structure equivalent to iron-rich tochilinite [6Fe (sub 0.9) S 5(Fe, Mg) (OH) (sub 2) ] which consists of coherently interstratified mackinawite and brucite sheets. approximately 17 angstrom PCP, previously described as an SBB-type mixed-layer structure, is a commensurate intergrowth of serpentine and tochilinite layers. A wide range of cation substitutions is possible within both tochilinite and serpentine-tochilinite structural types. Various forms of PCP observed in carbonaceous chondrites are intergrowths of tochilinite, serpentine, serpentine-tochilinite and/or valleriite-type minerals.--Modified journal abstract.