Water sorption/desorption in polyacid-modified composite resins for dentistry

The water sorption and desorption behaviour of three commercial polyacid-modified composite resins used in clinical dentistry have been studied in detail. Cured specimens of each material were subjected to two successive water uptake cycles in an atmosphere of 93% relative humidity, with one intervening desorption cycle in a desiccating atmosphere over concentrated sulfuric acid. Specimens were found to absorb and desorb water according Fick's law until Mt/M(infinity) values of approximately 0.5. Diffusion rates for uptake varied between cycles, ranging from 2.37-4.53 x 10(-9 )cm(2) s(-1) for 1st cycle to 0.85-2.72 x 10(-8 )cm(2 )s(-1) for 2nd cycle. Desorption rates were similar to those for 2nd cycle sorption, and ranged from 0.86 to 5.47 x 10(-8 )cm(2 )s(-1). Equilibration times for 1st cycle water uptake were greater than for 2nd cycle sorption and for desorption and overall the behaviour of polyacid-modified composites in a high humidity atmosphere was similar to that of conventional composites in water. It is concluded that the hydrophilic components of the former do not bring about an enhanced rate of water transport.

Kinetic studies of water uptake and loss in glass-ionomer cements

The water sorption and desorption behaviour of three commercial glass-ionomer cements used in clinical dentistry have been studied in detail. Cured specimens of each material were found to show slight but variable water uptake in high humidity conditions, but steady loss in desiccating ones. This water loss was found to follow Fick's law for the first 4-5 h. Diffusion coefficients at 22 degrees C were: Chemflex 1.34 x 10(-6) cm(2) s(-1), Fuji IX 5.87 x 10(-7) cm(2) s(-1), Aquacem 3.08 x 10(-6) cm(2) s(-1). At 7 degrees C they were: Chemflex 8.90 x 10(-7) cm(2) s(-1), Fuji IX 5.04 x 10(-7) cm(2) s(-1), Aquacem 2.88 x 10(-6) cm(2) s(-1). Activation energies for water loss were determined from the Arrhenius equation and were found to be Chemflex 161.8 J mol(-1), Fuji IX 101.3 J mol(-1), Aquacem 47.1 J mol(-1). Such low values show that water transport requires less energy in these cements than in resin-modified glass-ionomers. Fick's law plots were found not to pass through the origin. This implies that, in each case, there is a small water loss that does not involve diffusion. This was concluded to be water at the surface of the specimens, and was termed "superficial water". As such, it represents a fraction of the previously identified unbound (loose) water. Superficial water levels were: Chemflex 0.56%, Fuji IX 0.23%, Aquacem 0.87%. Equilibrium mass loss values were shown to be unaffected by temperature, and allowed ratios of bound:unbound water to be determined for all three cements. These showed wide variation, ranging from 1:5.26 for Chemflex to 1:1.25 for Fuji IX.

The kinetics of water loss from zinc phosphate and zinc polycarboxylate dental cements

The water desorption behaviour of three different zinc oxide dental cements (two polycarboxylates, one phosphate) has been studied in detail. Disc-shaped specimens of each material were prepared and allowed to lose water by being subjected to a low humidity desiccating atmosphere over concentrated sulfuric acid. In all three cements, water loss was found to follow Fick's second law for at least 6 h (until M(t)/M(infinity) values were around 0.5), with diffusion coefficients ranging from 6.03 x 10(-8 )cm(2 )s(-1) (for the zinc phosphate) to 2.056 x 10(-7 )cm(2 )s(-1) (for one of the zinc polycarboxylates, Poly F Plus). Equilibration times for desorption were of the order of 8 weeks, and equilibrium water losses ranged from 7.1% for zinc phosphate to 16.9% and 17.4% for the two zinc polycarboxylates.

The interaction of zinc oxide-based dental cements with aqueous solutions of potassium fluoride

The ability of zinc oxide-based dental cements (zinc phosphate and zinc polycarboxylate) to take up fluoride from aqueous solution has been studied. Only zinc phosphate cement was found to take up any measurable fluoride after 5 h exposure to the solutions. The zinc oxide filler of the zinc phosphate also failed to take up fluoride from solution. The key interaction for this uptake was thus shown to involve the phosphate groups of the set cement. However, whether this took the form of phosphate/fluoride exchange, or the formation of oxyfluoro-phosphate groups was not clear. Fluoride uptake followed radicaltime kinetics for about 2 h in some cases, but was generally better modelled by the Elovich equation, dq(t)/dt = alpha exp(-beta q(t)). Values for alpha varied from 3.80 to 2.48 x 10(4), and for beta from 7.19 x 10(-3) to 0.1946, though only beta showed any sort of trend, becoming smaller with increasing fluoride concentration. Fluoride was released from the zinc phosphate cements in processes that were diffusion based up to M(t)/M(infinity) of about 0.4. No further release occurred when specimens were placed in fresh volumes of deionised water. Only a fraction of the fluoride taken up was re-released, demonstrating that most of the fluoride taken up becomes irreversibly bound within the cement.

Current status and perspectives of accelerated carbonation processes on municipal waste combustion residues

The increasing volumes of municipal solid waste produced worldwide are encouraging the development of processes to reduce the environmental impact of this waste stream. Combustion technology can facilitate volume reduction of up to 90%, with the inorganic contaminants being captured in furnace bottom ash, and fly ash/APC residues. The disposal or reuse of these residues is however governed by the potential release of constituent contaminants into the environment. Accelerated carbonation has been shown to have a potential for improving the chemical stability and leaching behaviour of both bottom ash and fly ash/APC residues. However, the efficacy of carbonation depends on whether the method of gas application is direct or indirect. Also important are the mineralogy, chemistry and physical properties of the fresh ash, the carbonation reaction conditions such as temperature, contact time, CO2 partial pressure and relative humidity. This paper reviews the main issues pertaining to the application of accelerated carbonation to municipal waste combustion residues to elucidate the potential benefits on the stabilization of such residues and for reducing CO2 emissions. In particular, the modification of ash properties that occur upon carbonation and the CO2 sequestration potential possible under different conditions are discussed. Although accelerated carbonation is a developing technology, it could be introduced in new incinerator facilities as a "finishing step" for both ash treatment and reduction of CO2 emissions.

Shear bond strengths of glass-ionomer cements to sound and to prepared carious dentine

The aim of this study was determine whether bonding of glass-ionomer cements to non-carious dentine differed from that to carious dentine. Five commercial cements were used, namely Fuji IX GP, Fuji IX capsulated, Fuji IX Fast capsulated (all GC, Japan), Ketac-Molar and Ketac-Molar Aplicap (both 3M-ESPE, Germany). Following conditioning of the substrate with 10% poly (acrylic acid) for 10 s, sets of 10 samples of the cements were bonded to prepared teeth that had been removed for orthodontic reasons. The teeth used had either sound dentine or sclerotic dentine. Shear bond strengths were determined following 24 h storage. For the auto-mixed cements, shear bond strength to sound dentine was found not to differ statistically from shear bond strength to sclerotic dentine whereas for hand-mixed cements, shear bond to sound dentine was found to be higher than to carious dentine (to at least p < 0.05). This shows that the chemical effects arising from interactions of glass-ionomer cements with the mineral phase of the tooth are the most important in developing strong bonds, at least in the shorter term.

Ion release by endodontic grade glass-ionomer cement

Cylindrical specimens (6 mm high x 4 mm diameter) of the endodontic grade glass-ionomer (Ketac Endo) were exposed to various media for 1 week, after which changes in their mass, pH of storage medium, and ion release were determined. In water, this cement was shown to release reasonable amounts of sodium, aluminium and silicon, together with smaller amounts of calcium and phosphorus, as well as taking up 2.41% by mass of water. A comparison with the restorative grade materials (Ketac Molar, ex 3M ESPE and Fuji IX, ex GC) showed both ion release and water uptake to be greater. All three cements shifted pH from 7 to around 6 with no significant differences between them. Other storage media were found to alter the pattern of ion release. Lactic acid caused an increase, whereas both saturated calcium hydroxide and 0.6% sodium hypochlorite, caused decreases. This suppression of ion-release may be significant clinically. Aluminium is the most potentially hazardous of the ions involved but amounts released were low compared with levels previously reported to show biological damage.

Organisational whistleblowing policies: making employees responsible or liable?

This paper explores the possible impact of the recent legal developments on organizational whistleblowing on the autonomy and responsibility of whistleblowers. In the past thirty years numerous pieces of legislation have been passed to offer protection to whistleblowers from retaliation for disclosing organisational wrongdoing. An area that remains uncertain in relation to whistleblowing and its related policies in organisations, is whether these policies actually increase the individualisation of work, allowing employees to behave in accordance with their conscience and in line with societal expectations or whether they are another management tool to control employees and protect organisations from them. The assumptions of whistleblower protection with regard to moral autonomy are examined in order to clarify the purpose of whistleblower protection at work. The two extreme positions in the discourse of whistleblowing are that whistleblowing legislation and policies either aim to enable individual responsibility and moral autonomy at work, or they aim to protect organisations by allowing them to control employees and make them liable for ethics at work.

‘The trouble with Year 10’: 13 – 16 year old school students’ attitudes to higher education

This study looked at the impact of Widening Participation interventions on the attitudes of young people towards higher education. A total of 2731 adolescents aged 13–16 years completed a self-report measure of their attitudes to higher education, general and academic self concept and identification with school, family and peers. This was matched with data on the students’ academic attainment and social backgrounds. As expected, attainment scores were significantly positively correlated with take up of Widening Participation activities aimed at increasing participation in higher education, attitudes towards going to university and academic motivation. However, attainment was negatively correlated with perceptions of family attending university and identification with family. Regression analyses found that perceptions of family views about attending university were not a predictor of taking part in Widening Participation activities but were a predictor of attitudes towards higher education. Students in Year 10 aged 14–15 were significantly more negative on most factors than either older or younger students.

Phytoplankton carbon fixation chlorophyll-biomass and diagnostic pigments in the Atlantic Ocean

We have made daily measurements of phytoplankton pigments, size-fractionated (<2 and >2-μm) carbon fixation and chlorophyll-a concentration during four Atlantic Meridional Transect (AMT) cruises in 2003–04. Surface rates of carbon fixation ranged from <0.2-mmol C m−3 d−1 in the subtropical gyres to 0.2–0.5-mmol C m−3 d−1 in the tropical equatorial Atlantic. Significant intercruise variability was restricted to the subtropical gyres, with higher chlorophyll-a concentrations and carbon fixation in the subsurface chlorophyll maximum during spring in either hemisphere. In surface waters, although picoplankton (<2-μm) represented the dominant fraction in terms of both carbon fixation (50–70%) and chlorophyll-a (80–90%), nanoplankton (>2-μm) contributions to total carbon fixation (30–50%) were higher than to total chlorophyll-a (10–20%). However, in the subsurface chlorophyll maximum picoplankton dominated both carbon fixation (70–90%) and chlorophyll-a (70–90%). Thus, in surface waters chlorophyll-normalised carbon fixation was 2–3 times higher for nanoplankton and differences in picoplankton and nanoplankton carbon to chlorophyll-a ratios may lead to either higher or similar growth rates. These low chlorophyll-normalised carbon fixation rates for picoplankton may also reflect losses of fixed carbon (cell leakage or respiration), decreases in photosynthetic efficiency, grazing losses during the incubations, or some combination of all these. Comparison of nitrate concentrations in the subsurface chlorophyll maximum with estimates of those required to support the observed rates of carbon fixation (assuming Redfield stoichiometry) indicate that primary production in the chlorophyll maximum may be light rather than nutrient limited.

Speed tuning of direction repulsion describes an inverted U-function

Direction repulsion describes the phenomenon in which observers typically overestimate the direction difference between two superimposed motions moving in different directions (Marshak & Sekuler, Science 205(1979) 1399). Previous research has found that, when a relatively narrow range of distractor speeds is considered, direction repulsion of a target motion increases monotonically with increasing speed of the distractor motion. We sought to obtain a more complete measurement of this speed-tuning function by considering a wider range of distractor speeds than has previously been used. Our results show that, contrary to previous reports, direction repulsion as a function of distractor speed describes an inverted U-function. For a target of 2.5deg/s, we demonstrate that the attenuation of repulsion magnitude with high-speed disractors can be largely explained in terms of the reduced apparent contrast of the distractor. However, when we reduce target motion speed, this no longer holds. When considered from the perspective of Edwards et al.s (Edwards, Badcock, & Smith, Vision Research 38 (1998) 1573) two global-motion channels, our results suggest that direction repulsion is speed dependent when the distractor and target motions are processed by different globalmotion channels, but is not speed dependent when both motions are processed by the same, high-speed channel. The implications of these results for models of direction repulsion are discussed.

Mire ontogeny, environmental and climate change inferred from fossil beetle successions from Hatfield Moors, eastern England

Results of a fossil Coleoptera (beetle) fauna from a fen edge sequence from Hatfield Moors, Humberhead Levels, are presented. Mire ontogeny inferred from this location and others are discussed, particularly in the light of previous palynological and plant macrofossil investigations. Peat initiation across most of the site centres around 3000 cal BC, characterised by a Calluna-Eriophorum heath with areas of Pinus-Betula woodland. The onset of peat accumulation on the southern margins of the site was delayed until 1520-1390 cal BC and appears to overlap closely with a recurrence surface at a pollen site (HAT 2) studied by Brian Smith (1985, 2002) dated to 1610-1440 cal BC, suggesting that increased surface wetness may have caused mire expansion at this time. The faunas illustrate the transition from eutrophic and mesotrophic fen to ombrotrophic raised mire, although the significance of both Pinus- and Calluna-indicating species through the sequence suggests that heath habitats may have continued to be important. Elsewhere, this earlier phase of rich fen is lacking and mesotrophic mire developed immediately above nutrient poor sands, with ombrotrophic conditions indicated soon after. Correspondence analysis of the faunas provides valuable insights into the importance of sandy heath habitats on Hatfield Moors. The continuing influence of the underlying coversands suggests these may have been instrumental in mire ontogeny. The research highlights the usefulness of using Coleoptera to assess mire ontogeny, fluctuations in site hydrology and vegetation cover, particularly when used in conjunction with other peatland proxies. The significance of a suite of extinct beetle species is discussed with reference to forest history and climate change.