Ions in motor vehicle exhaust and their dispersion near busy roads

Measurements in the exhaust plume of a petrol-driven motor car showed that molecular cluster ions of both signs were present in approximately equal amounts. The emission rate increased sharply with engine speed while the charge symmetry remained unchanged. Measurements at the kerbside of nine motorways and five city roads showed that the mean total cluster ion concentration near city roads (603 cm-3) was about one-half of that near motorways (1211 cm-3) and about twice as high as that in the urban background (269 cm-3). Both positive and negative ion concentrations near a motorway showed a significant linear increase with traffic density (R2=0.3 at p<0.05) and correlated well with each other in real time (R2=0.87 at p<0.01). Heavy duty diesel vehicles comprised the main source of ions near busy roads. Measurements were conducted as a function of downwind distance from two motorways carrying around 120-150 vehicles per minute. Total traffic-related cluster ion concentrations decreased rapidly with distance, falling by one-half from the closest approach of 2m to 5m of the kerb. Measured concentrations decreased to background at about 15m from the kerb when the wind speed was 1.3 m s-1, this distance being greater at higher wind speed. The number and net charge concentrations of aerosol particles were also measured. Unlike particles that were carried downwind to distances of a few hundred metres, cluster ions emitted by motor vehicles were not present at more than a few tens of metres from the road.

Alkaline hydrothermal treatment of titanate nanostructures

Since its initial proposal in 1998, alkaline hydrothermal processing has rapidly become an established technology for the production of titanate nanostructures. This simple, highly reproducible process has gained a strong research following since its conception. However, complete understanding and elucidation of nanostructure phase and formation have not yet been achieved. Without fully understanding phase, formation, and other important competing effects of the synthesis parameters on the final structure, the maximum potential of these nanostructures cannot be obtained. Therefore this study examined the influence of synthesis parameters on the formation of titanate nanostructures produced by alkaline hydrothermal treatment. The parameters included alkaline concentration, hydrothermal temperature, the precursor material‘s crystallite size and also the phase of the titanium dioxide precursor (TiO2, or titania). The nanostructure‘s phase and morphology was analysed using X-ray diffraction (XRD), Raman spectroscopy and transmission electron microscopy. X-ray photoelectron spectroscopy (XPS), dynamic light scattering (non-invasive backscattering), nitrogen sorption, and Rietveld analysis were used to determine phase, for particle sizing, surface area determinations, and establishing phase concentrations, respectively. This project rigorously examined the effect of alkaline concentration and hydrothermal temperature on three commercially sourced and two self-prepared TiO2 powders. These precursors consisted of both pure- or mixed-phase anatase and rutile polymorphs, and were selected to cover a range of phase concentrations and crystallite sizes. Typically, these precursors were treated with 5–10 M sodium hydroxide (NaOH) solutions at temperatures between 100–220 °C. Both nanotube and nanoribbon morphologies could be produced depending on the combination of these hydrothermal conditions. Both titania and titanate phases are comprised of TiO6 units which are assembled in different combinations. The arrangement of these atoms affects the binding energy between the Ti–O bonds. Raman spectroscopy and XPS were therefore employed in a preliminary study of phase determination for these materials. The change in binding energy from a titania to a titanate binding energy was investigated in this study, and the transformation of titania precursor into nanotubes and titanate nanoribbons was directly observed by these methods. Evaluation of the Raman and XPS results indicated a strengthening in the binding energies of both the Ti (2p3/2) and O (1s) bands which correlated to an increase in strength and decrease in resolution of the characteristic nanotube doublet observed between 320 and 220 cm.1 in the Raman spectra of these products. The effect of phase and crystallite size on nanotube formation was examined over a series of temperatures (100.200 �‹C in 20 �‹C increments) at a set alkaline concentration (7.5 M NaOH). These parameters were investigated by employing both pure- and mixed- phase precursors of anatase and rutile. This study indicated that both the crystallite size and phase affect nanotube formation, with rutile requiring a greater driving force (essentially �\harsher. hydrothermal conditions) than anatase to form nanotubes, where larger crystallites forms of the precursor also appeared to impede nanotube formation slightly. These parameters were further examined in later studies. The influence of alkaline concentration and hydrothermal temperature were systematically examined for the transformation of Degussa P25 into nanotubes and nanoribbons, and exact conditions for nanostructure synthesis were determined. Correlation of these data sets resulted in the construction of a morphological phase diagram, which is an effective reference for nanostructure formation. This morphological phase diagram effectively provides a .recipe book�e for the formation of titanate nanostructures. Morphological phase diagrams were also constructed for larger, near phase-pure anatase and rutile precursors, to further investigate the influence of hydrothermal reaction parameters on the formation of titanate nanotubes and nanoribbons. The effects of alkaline concentration, hydrothermal temperature, crystallite phase and size are observed when the three morphological phase diagrams are compared. Through the analysis of these results it was determined that alkaline concentration and hydrothermal temperature affect nanotube and nanoribbon formation independently through a complex relationship, where nanotubes are primarily affected by temperature, whilst nanoribbons are strongly influenced by alkaline concentration. Crystallite size and phase also affected the nanostructure formation. Smaller precursor crystallites formed nanostructures at reduced hydrothermal temperature, and rutile displayed a slower rate of precursor consumption compared to anatase, with incomplete conversion observed for most hydrothermal conditions. The incomplete conversion of rutile into nanotubes was examined in detail in the final study. This study selectively examined the kinetics of precursor dissolution in order to understand why rutile incompletely converted. This was achieved by selecting a single hydrothermal condition (9 M NaOH, 160 °C) where nanotubes are known to form from both anatase and rutile, where the synthesis was quenched after 2, 4, 8, 16 and 32 hours. The influence of precursor phase on nanostructure formation was explicitly determined to be due to different dissolution kinetics; where anatase exhibited zero-order dissolution and rutile second-order. This difference in kinetic order cannot be simply explained by the variation in crystallite size, as the inherent surface areas of the two precursors were determined to have first-order relationships with time. Therefore, the crystallite size (and inherent surface area) does not affect the overall kinetic order of dissolution; rather, it determines the rate of reaction. Finally, nanostructure formation was found to be controlled by the availability of dissolved titanium (Ti4+) species in solution, which is mediated by the dissolution kinetics of the precursor.

Sodium niobate adsorbents doped with tantalum (TaV) for the removal of bivalence radioactive ions in waste waters

Sodium niobates doped with different amount of tantalum (TaV) were prepared via thermal reaction process. It was found pure nanofibril and bar-like solids can be obtained when tantalum was introduced into the reaction system. For the well-crystallized fibril solids, the Na+ ions are difficult to be exchanged, and the radioactive ions such as Sr2+ and Ra2+ ions just deposit on the surface of the fibers during the sorption process, resulting in lower sorption capacity and distribution coefficients (Kd)`. However, the bar-like solids are poorly-crystallized and have lots of exchangeable Na+ ions. They are able to remove highly hazardous bivalent radioactive isotopes such as Sr2+ and Ra2+ ions. Even in the presence of lots of Na+ ions, they also have higher Kd. More importantly, such sorption finally intelligently triggers considerable collapse of the structure, resulting in the entrapment of the toxic bivalent cations permanently in the solids so that they can be safely disposed. This study highlights new opportunities for the preparation of Nb-based adsorbents to efficiently remove the toxic radioactive ions from contaminated water.

Effect of pH on the uptake of arsenate and vanadate and the stability of these anions in alkaline solutions – a Raman spectroscopic study

Hydrotalcites have been synthesised using three different pH solutions to assess the effect of pH on the uptake of arsenate and vanadate. The ability of these hydrotalcites to remove vanadate and arsenate from solution has been determined by ICP-OES. Raman spectroscopy is used to monitor changes in the anionic species for hydrotalcites synthesised at different pH values. The results show a reduction in the concentration of arsenate and vanadate anions that are removed in extremely alkaline solutions. Hydrotalcites containing arsenate and vanadate are stable in solutions up to pH 10. Exposure of these hydrotalcites to higher pH values results in the removal of large percentages of arsenate and vanadate from the hydrotalcite interlayer.

Bioactive SrO–SiO2 glass with well-ordered mesopores : characterization, physiochemistry and biological properties

For a biomaterial to be considered suitable for bone repair it should ideally be both bioactive and have a capacity for controllable drug delivery; as such, mesoporous SiO2 glass has been proposed as a new class of bone regeneration material by virtue of its high drug-loading ability and generally good biocompatibility. It does, however, have less than optimum bioactivity and controllable drug delivery properties. In this study, we incorporated strontium (Sr) into mesoporous SiO2 in an effort to develop a bioactive mesoporous SrO–SiO2 (Sr–Si) glass with the capacity to deliver Sr2+ ions, as well as a drug, at a controlled rate, thereby producing a material better suited for bone repair. The effects of Sr2+ on the structure, physiochemistry, drug delivery and biological properties of mesoporous Sr–Si glass were investigated. The prepared mesoporous Sr–Si glass was found to have an excellent release profile of bioactive Sr2+ ions and dexamethasone, and the incorporation of Sr2+ improved structural properties, such as mesopore size, pore volume and specific surface area, as well as rate of dissolution and protein adsorption. The mesoporous Sr–Si glass had no cytotoxic effects and its release of Sr2+ and SiO44− ions enhanced alkaline phosphatase activity – a marker of osteogenic cell differentiation – in human bone mesenchymal stem cells. Mesoporous Sr–Si glasses can be prepared to porous scaffolds which show a more sustained drug release. This study suggests that incorporating Sr2+ into mesoporous SiO2 glass produces a material with a more optimal drug delivery profile coupled with improved bioactivity, making it an excellent material for bone repair applications. Keywords: Mesoporous Sr–Si glass; Drug delivery; Bioactivity; Bone repair; Scaffolds

Effects of varied ionic calcium and phosphate on the proliferation, osteogenic differentiation and mineralization of human periodontal ligament cells in vitro

Background and Objective: A number of bone filling materials containing calcium (Ca++) and phosphate (P) ions have been used in the repair of periodontal bone defects; however, the effect that local release of Ca++ and P ions have on biological reactions is not fully understood. In this study, we investigated the effects of various levels of Ca++ and P ions on the proliferation, osteogenic differentiation, and mineralization of human periodontal ligament cells (hPDLCs). Materials and Methods: hPDLCs were obtained using an explant culture method. Defined concentrations and ratios of ionic Ca++ to inorganic P were added to standard culture and osteogenic induction media. The ability of hPDLCs to proliferate in these growth media was assayed using the Cell Counting Kit-8 (CCK-8). Cell apoptosis was evaluated by FITC-Annexin V/PI double staining method. Osteogenic differentiation and mineralization were investigated by morphological observations, alkaline phosphatase (ALP) activity, and Alizarin red S/von Kossa staining. The mRNA expression of osteogenic related markers was analyzed using a reverse transcriptase polymerase chain reaction (RT-PCR). Results: Within the ranges of Ca++ and P ions concentrations tested, we observed that increased concentrations of Ca++ and P ions enhanced cell proliferation and formation of mineralized matrix nodules; whereas ALP activity was reduced. The RT-PCR results showed that elevated concentrations of Ca++ and P ions led to a general increase of Runx2 mRNA expression and decreased ALP mRNA expression, but gave no clear trend on OCN mRNA levels. Conclusion: The concentrations and ratios of Ca++ and P ions could significantly influence proliferation, differentiation, and mineralization of hPDLCs. Within the range of concentrations tested, we found that the combination of 9.0 mM Ca++ ions and 4.5 mM P ions were the optimum concentrations for proliferation, differentiation, and mineralization in hPDLCs.

Physical characteristics of small ions and their interaction with ultrafine particles in the urban environment

In recent years, the effect of ions and ultrafine particles on ambient air quality and human health has been well documented, however, knowledge about their sources, concentrations and interactions within different types of urban environments remains limited. This thesis presents the results of numerous field studies aimed at quantifying variations in ion concentration with distance from the source, as well as identifying the dynamics of the particle ionisation processes which lead to the formation of charged particles in the air. In order to select the most appropriate measurement instruments and locations for the studies, a literature review was also conducted on studies that reported ion and ultrafine particle emissions from different sources in a typical urban environment. The initial study involved laboratory experiments on the attachment of ions to aerosols, so as to gain a better understanding of the interaction between ions and particles. This study determined the efficiency of corona ions at charging and removing particles from the air, as a function of different particle number and ion concentrations. The results showed that particle number loss was directly proportional to particle charge concentration, and that higher small ion concentrations led to higher particle deposition rates in all size ranges investigated. Nanoparticles were also observed to decrease with increasing particle charge concentration, due to their higher Brownian mobility and subsequent attachment to charged particles. Given that corona discharge from high voltage powerlines is considered one of the major ion sources in urban areas, a detailed study was then conducted under three parallel overhead powerlines, with a steady wind blowing in a perpendicular direction to the lines. The results showed that large sections of the lines did not produce any corona at all, while strong positive emissions were observed from discrete components such as a particular set of spacers on one of the lines. Measurements were also conducted at eight upwind and downwind points perpendicular to the powerlines, spanning a total distance of about 160m. The maximum positive small and large ion concentrations, and DC electric field were observed at a point 20 m downwind from the lines, with median values of 4.4×103 cm-3, 1.3×103 cm-3 and 530 V m-1, respectively. It was estimated that, at this point, less than 7% of the total number of particles was charged. The electrical parameters decreased steadily with increasing downwind distance from the lines but remained significantly higher than background levels at the limit of the measurements. Moreover, vehicles are one of the most prevalent ion and particle emitting sources in urban environments, and therefore, experiments were also conducted behind a motor vehicle exhaust pipe and near busy motorways, with the aim of quantifying small ion and particle charge concentration, as well as their distribution as a function of distance from the source. The study found that approximately equal numbers of positive and negative ions were observed in the vehicle exhaust plume, as well as near motorways, of which heavy duty vehicles were believed to be the main contributor. In addition, cluster ion concentration was observed to decrease rapidly within the first 10-15 m from the road and ion-ion recombination and ion-aerosol attachment were the most likely cause of ion depletion, rather than dilution and turbulence related processes. In addition to the above-mentioned dominant ion sources, other sources also exist within urban environments where intensive human activities take place. In this part of the study, airborne concentrations of small ions, particles and net particle charge were measured at 32 different outdoor sites in and around Brisbane, Australia, which were classified into seven different groups as follows: park, woodland, city centre, residential, freeway, powerlines and power substation. Whilst the study confirmed that powerlines, power substations and freeways were the main ion sources in an urban environment, it also suggested that not all powerlines emitted ions, only those with discrete corona discharge points. In addition to the main ion sources, higher ion concentrations were also observed environments affected by vehicle traffic and human activities, such as the city centre and residential areas. A considerable number of ions were also observed in a woodland area and it is still unclear if they were emitted directly from the trees, or if they originated from some other local source. Overall, it was found that different types of environments had different types of ion sources, which could be classified as unipolar or bipolar particle sources, as well as ion sources that co-exist with particle sources. In general, fewer small ions were observed at sites with co-existing sources, however particle charge was often higher due to the effect of ion-particle attachment. In summary, this study quantified ion concentrations in typical urban environments, identified major charge sources in urban areas, and determined the spatial dispersion of ions as a function of distance from the source, as well as their controlling factors. The study also presented ion-aerosol attachment efficiencies under high ion concentration conditions, both in the laboratory and in real outdoor environments. The outcomes of these studies addressed the aims of this work and advanced understanding of the charge status of aerosols in the urban environment.

Corona ions from high-voltage power lines : nature of emission and dispersion

Positive and negative small ions, aerosol ion and number concentration and dc electric fields were monitored at an overhead high-voltage power line site. We show that the emission of corona ions was not spatially uniform along the lines and occurred from discrete components such as a particular set of spacers. Maximum ion concentrations and atmospheric dc electric fields were observed at a point 20 m downwind of the lines. It was estimated that less than 7% of the total number of aerosol particles was charged. The electrical parameters decreased steadily with further downwind distance but remained significantly higher than background.

The cementogenic differentiation of periodontal ligament cells via the activation of Wnt/β-catenin signalling pathway by Li+ ions released from bioactive scaffolds

Lithium (Li) has been widely used as a long-term mood stabilizer in the treatment of bipolar and depressive disorders. Li+ ions are thought to enhance the remyelination of peripheral nerves and also stimulate the proliferation of neural progenitor cells and retinoblastoma cells via activation of the Wnt/β-catenin signalling pathway. Until now there have been no studies reporting the biological effects of released Li+ in bioactive scaffolds on cemetogenesis in periodontal tissue engineering applications. In this study, we incorporated parts of Li+ ions into the mesoporous bioactive glass (MBG) scaffolds and showed that this approach yielded scaffolds with a favourable composition, microstructure and mesopore properties for cell attachment, proliferation, and cementogenic differentiation of human periodontal ligament-derived cells (hPDLCs). We went on to investigate the biological effects of Li+ ions themselves on cell proliferation and cementogenic differentiation. The results showed that 5% Li+ ions incorporated into MBG scaffolds enhanced the proliferation and cementogenic differentiation of hPDLCs on scaffolds, most likely via activation of Wnt/β-catenin signalling pathway. Further study demonstrated that Li+ ions by themselves significantly enhanced the proliferation, differentiation and cementogenic gene expression of PDLCs. Our results indicate that incorporation of Li+ ions into bioactive scaffolds is a viable means of enhancing the Wnt canonical signalling pathway to stimulate cementogenic differentiation of PDLCs.