Observation of ions and particles near busy roads using a Neutral Cluster and Air Ion Spectrometer (NAIS)

Motor vehicles emit large quantities of ions in the form of both charged particles and molecular cluster ions. While, the health effects of inhalation of charged particles is largely unexplored, the concentrations near busy roads and the distance to which these particles and ions are carried have important implications for the exposure of the large percentage of the population that lives close to such roadways. We measured ion concentrations using a neutral cluster and air ion spectrometer (NAIS) near seven busy roads carrying on the average approximately 7000 vehicles hr-1 including about 15% heavy duty diesel vehicles. In this study, charged particle concentrations were measured as a function of downwind distance from the road for the first time. We show that, at a moderate wind speed of 2.0 m s-1, mean charged particle concentrations at the kerb were of the order of 2x104 cm-3 and, more importantly, decreased as d 0.6 where d is the distance from the road. While cluster ions were rapidly depleted by attachment to particles and were not carried to more than about 20 m from the road, elevated concentrations of charged particle were detected up to at least 400 m from the road. Most of the charge on the downwind side was carried on the larger particles, with no excess charge on particles smaller than about 10 nm. At 30 nm, particles carried more than double the charge they would normally carry in equilibrium. There are very few measurements of ions near road traffic and this is the first study of the spatial dispersion of charged particles from a road.

Observation of solution-induced corneal staining with fluorescein, rose bengal and lissamine green

Ever since sodium fluorescein (‘fluorescein’ [FL]) was first used to investigate the ocular surface over a century ago, the term ‘staining’ has been taken to mean the presence of ocular surface fluorescence [1]. This term has not been necessarily taken to infer any particular mechanism of causation, and indeed, can be attributed to a variety of possible aetiologies [2]. In recent times, there has been considerable interest in a form of ocular surface fluorescence seen in association with the use of certain combinations of soft contact lenses and multipurpose solutions. The first clinical account of this phenomenon was reported by Jones et al. [3], which was followed by a more formal investigation by the same author in 2002 [4]. Jones et al described this appearance as a ‘classic solution-based toxicity reaction’. Subsequently, this appearance has come to be known as ‘solution-induced corneal staining’ or more recently by the acronym ‘SICS’ [5]. The term SICS is potentially problematic in that from a cell biology point of view, there is an inference that ‘staining’ means the entry of a dye into corneal epithelial cells. Morgan and Maldonado-Codina [2] noted there was no foundation of solid scientific literature underpinning our understanding of the true basic causative mechanisms of this phenomenon; since that time, further work has been published in this field [6] and [7] but questions still remain about the precise aetiology of this phenomenon...

Direct Observation of Photodissociation Products from Phenylperoxyl Radicals Isolated in the Gas Phase

Gas phase peroxyl radicals are central to our chemical understanding of combustion and atmospheric processes and are typically characterized by strong absorption in the UV (lambda(max) approximate to 240 nm). The analogous maximum absorption feature for arylperoxyl radicals is predicted to shift to the visible but has not previously been characterized nor have any photoproducts arising from this transition been identified. Here we describe the controlled synthesis and isolation in vacuo of an array of charge-substituted phenylperoxyl radicals at room temperature, including the 4-(N,N,N-trimethylammonium)methyl phenylperoxyl radical cation (4-Me3N[+]CH2-C6H4OO center dot), using linear ion-trap mass spectrometry. Photodissociation mass spectra obtained at wavelengths ranging from 310 to 500 nm reveal two major photoproduct channels corresponding to homolysis of aryl-OO and arylO-O bonds resulting in loss of O-2 and O, respectively. Combining the photodissociation yields across this spectral window produces a broad (FWHM approximate to 60 nm) but clearly resolved feature centered at lambda(max) = 403 nm (3.08 eV). The influence of the charge-tag identity and its proximity to the radical site are investigated and demonstrate no effect on the identity of the two dominant photoproduct channels. Electronic structure calculations have located the vertical (B) over tilde <- (X) over tilde transition of these substituted phenylperoxyl radicals within the experimental uncertainty and further predict the analogous transition for unsubstituted phenylperoxyl radical (C6H5OO center dot) to be 457 nm (2.71 eV), nearly 45 nm shorter than previous estimates and in good agreement with recent computational values.

Superoxide does react with peroxides : direct observation of the haber-weiss reaction in the gas phase

The fact that nature provides specific enzymes to selectively remove superoxide (O2.−) from aerobic organisms, namely, the superoxide dismutase enzymes,1 has led to the suggestion that this radical ion may cause the oxidative damage associated with degradative disease and aging.2 Intriguingly, however, superoxide itself is relatively unreactive toward most cellular components, which suggests that dismutase enzymes may ultimately protect the cell against more pernicious oxidants formed from superoxide. As such, there is increasing interest in the endogenous chemistry of superoxide and the pathways by which it might beget more reactive oxygen species. Protonation of superoxide to form the hydroperoxyl radical (HOO.) and dismutation of the same species to hydrogen peroxide (HOOH), with subsequent metal-catalyzed reduction to the hydroxyl radical (HO.), are well-characterized processes in which both the HOO. and HO. radicals are significantly more reactive than their common progenitor.2 Recent examples, however, have also linked superoxide to the putative production of singlet oxygen3 and ozone,4, 5 although the definitive characterization of these chemistries in the cellular milieu has proved challenging

Direct observation of the gas phase reaction of the cyclohexyl radical with dioxygen using a distonic radical ion approach

Alkylperoxyl radicals are intermediates in the oxidation Of hydrocarbons. The reactive nature of these intermediates, however, has made therin elusive to direct observation and isolation. We have employed ion trap mass spectrometry to synthesize and characterize 4-carboxylatocyclohexyl radical anions ((center dot)C(6)H(10)-CO(2)(-)) and observe their reactivity in the presence of dioxygen. The resulting reaction is facile (k = 1.8 x 10(-10) cm(3) molecule(-1) s(-1) or 30% of calculated collision rate) and results in (i) the addition Of O(2) to form stabilized 4-carboxylatocyclohexylperoxyl radical anions ((center dot)OO-C(6)H(10)-CO(2)(-)), providing the first direct observation of a cyclohexylperoxyl radical, and (ii) elimination of HO(2)(center dot) and HO(center dot) radicals consistent with recent laser-induced fluorescence studies of the reaction of neutral cyclohexyl radicals with O(2). Electronic structure calculations at the B3LYP/6-31+G(d) level of theory reveal viable pathways for the observed reactions showing that formation of the peroxyl radical is exothermic by 37 kcal mol(-1) with subsequent transition states its low as -6.6 kcal mol(-1) (formation of HO(2)(center dot)) and -9.1 kcal mol(-1) (formation of HO(center dot)) with respect to the entrance channel. The combined computational and experimental data Suggest that the structures of the reaction products correspond to cyclohexenes and epoxides from HO(2)(center dot) and HO(center dot) loss, respectively, while alternative pathways leading to cyclohexanone or ring-opened isomers ate not observed, Activation of the charged peroxyl radical (center dot)OO-C(6)H(10)-CO(2)(-) by collision induced disassociation also results in the loss Of HO(2)(center dot) and HO(center dot) radicals confirming that these products are directly connected to the peroxyl radical intermediate.

Child observation as teachers' work in contemporary Australian early childhood programs

This article reports data from a study of how teachers use child observations in one State in Australia. It argues that the current economic and political climate has meant changes for most early childhood settings catering for children prior to school entry. How teachers in these various settings deal with changes in relation to child observation depends on the contexts in which they work. The paper suggests that the purpose of observing children is changing and that traditionally accepted ways of writing child observations may be under threat.

Architecture in the South Pacific : the Ocean of Islands

Architecture in the South Pacific: The Ocean of Islands recounts the recent developments of the South Pacific and its fascinating architecture. This volume traces the European architectural overlay onto this scattered group of islands as well as the transition of these same islands towards a regional identity that has been fashioned by the remoteness of each location, the incomparable setting, and the distinctive ethnic mix of its inhabitants. A series of themed essays present the story of architectural development in the Solomon Islands, Vanuatu, New Caledonia, Fiji, Wallis and Futuna, Tonga, the Cook Islands, Samoa and American Samoa, and French Polynesia. Recent architecture typifies the evolution of the islands as they have been subjected to the transformative waves of alien trade, religion, colonization, war and tourism, followed by post-colonialism and revived nationalism. As with the Pacific region itself, the most prominent characteristic of the architecture is its diversity. The blending of the universal and the local sets the stage for a fresh vision of the South Pacific across a wide range of building types, from spectacular mission churches to sensational resorts in paradise. This book, in full colour, will appeal to architects, armchair-tourists, students and all those for whom the South Pacific is the idyll of their dreams.

Reduced motor facilitation during action observation in schizophrenia : a mirror neuron deficit?

Impairments in social cognitive functioning are well documented in schizophrenia, however the neural basis of these deficits is unclear. A recent explanatory model of social cognition centers upon the activity of mirror neurons, which are cortical brain cells that become active during both the performance and observation of behavior. Here, we test for the first time whether mirror neuron functioning is reduced in schizophrenia. Fifteen individuals with schizophrenia or schizoaffective disorder and fifteen healthy controls completed a transcranial magnetic stimulation (TMS) experiment designed to assess mirror neuron activation. While patients demonstrated no abnormalities in cortical excitability, motor facilitation during action observation, putatively reflecting mirror neuron activity, was reduced in schizophrenia. Dysfunction within the mirror neuron system may contribute to the pathophysiology of schizophrenia.

An observation about circular shortest paths: Dealing with additional constraints using branch and bound

Circular shortest paths represent a powerful methodology for image segmentation. The circularity condition ensures that the contour found by the algorithm is closed, a natural requirement for regular objects. Several implementations have been proposed in the past that either promise closure with high probability or ensure closure strictly, but with a mild computational efficiency handicap. Circularity can be viewed as a priori information that helps recover the correct object contour. Our "observation" is that circularity is only one among many possible constraints that can be imposed on shortest paths to guide them to a desirable solution. In this contribution, we illustrate this opportunity under a volume constraint but the concept is generally applicable. We also describe several adornments to the circular shortest path algorithm that proved useful in applications. © 2011 IEEE.

Real-time assessment of GNSS observation noise with single receivers

Stochastic modelling is critical in GNSS data processing. Currently, GNSS data processing commonly relies on the empirical stochastic model which may not reflect the actual data quality or noise characteristics. This paper examines the real-time GNSS observation noise estimation methods enabling to determine the observation variance from single receiver data stream. The methods involve three steps: forming linear combination, handling the ionosphere and ambiguity bias and variance estimation. Two distinguished ways are applied to overcome the ionosphere and ambiguity biases, known as the time differenced method and polynomial prediction method respectively. The real time variance estimation methods are compared with the zero-baseline and short-baseline methods. The proposed method only requires single receiver observation, thus applicable to both differenced and un-differenced data processing modes. However, the methods may be subject to the normal ionosphere conditions and low autocorrelation GNSS receivers. Experimental results also indicate the proposed method can result on more realistic parameter precision.

Large variations in the Holocene marine radiocarbon reservoir effect reflect ocean circulation and climatic changes

Accurate radiocarbon dating of marine samples requires knowledge of the marine radiocarbon reservoir effect. This effect for a particular site/region is generally assumed constant through time when calibrating marine 14C ages. However, recent studies have shown large temporal variations of several hundred to a couple of thousand years in this effect for a number of regions during the late Quaternary and Holocene. Here we report marine radiocarbon reservoir correction (ΔRΔR) for Heron Reef and Moreton Bay in southwestern (SW) Pacific for the last 8 ka derived from 14C analysis of 230Th-dated corals. Most of our ΔRΔR for the last ∼5.4 ka agree well with their modern value, but large ΔRΔR variability of ∼410 yr (from trough to peak) with possible decadal/centennial fluctuations is evident for the period ∼5.4–8 ka. The latter time interval also has significant variations with similar features in previously published ΔRΔR values for other sites in the Pacific, including southern Peru–northern Chile in southeastern (SE) Pacific, the South China Sea, Vanuatu and Papua New Guinea, with the largest magnitude of ∼920 yr from SE Pacific. The mechanisms for these large ΔRΔR variations across the Pacific during the mid-Holocene are complex processes involving (1) changes in the quantity and 14C content of upwelled waters in tropical east Pacific (TEP) (frequency and intensity of ocean upwelling in the TEP, and contribution of Subantarctic Mode Water to the upwelled waters, which is influenced by the intensity and position of southern westerly winds), and (2) variations in ocean circulation associated with climate change (La Niña/El Niño conditions, intensity of easterly trade winds, positions of the Intertropical Convergence Zone and the South Pacific Convergence Zone), which control the spreading of the older upwelled surface waters in the TEP to the western sites. Our results imply the need for employing temporal changes in ΔRΔR values, instead of constant (modern) values, for age calibration of Holocene marine samples not only for the SW Pacific sites but also for other tropical and subtropical sites in the Pacific.

Pt metal-CeO2 interaction: Direct observation of redox coupling between Pt-0/Pt2+/Pt4+ and Ce4+/Ce3+ states in Ce0.98Pt0.02O2-delta catalyst by a combined electrochemical and x-ray photoelectron spectroscopy study

Pt ions-CeO2 interaction in Ce1-xPtxO2-delta (x=0.02) has been studied for the first time by electrochemical method combined with x-ray diffraction and x-ray photoelectron spectroscopy. Working electrodes made of CeO2 and Ce0.98Pt0.02O2-delta mixed with 30% carbon are treated electrochemically between 0.0-1.2 V in potentiostatic (chronoamperometry) and potentiodynamic (cyclic voltametry) mode with reference to saturated calomel electrode. Reversible oxidation of Pt-0 to Pt2+ and Pt4+ state due to the applied positive potential is coupled to simultaneous reversible reduction of Ce4+ to Ce3+ state. CeO2 reduces to CeO2-y (y=0.35) after applying 1.2 V, which is not reversible; Ce0.98Pt0.02O2-delta reaches a steady state with Pt2+:Pt4+ in the ratio of 0.60:0.40 and Ce4+:Ce3+ in the ratio of 0.55:0.45 giving a composition Ce0.98Pt0.02O1.74 at 1.2 V, which is reversible. Composition of Pt ion substituted compound is reversible between Ce0.98Pt0.02O1.95 to Ce0.98Pt0.02O1.74 within the potential range of 0.0-1.2 V. Thus, Ce0.98Pt0.02O2-delta forms a stable electrode for oxidation of H2O to O-2 unlike CeO2. A linear relation between oxidation of Pt2+ to Pt4+ with simultaneous reduction in Ce4+ to Ce3+ is observed demonstrating Pt-CeO2 metal support interaction is due to reversible Pt-0/Pt2+/Pt4+ interaction with Ce4+/Ce3+ redox couple.

The first observation of a Na2TiS2 related structure in a 2-D anionic manganese trimesate intercalated by cationic imidazole

A hydrothermal reaction of Mn(OAc)2·4H2O, trimesic acid, imidazole, KOH and water at 75 °C for 24 h gave rise to a 2-D compound, [HImd][Mn(BTC)(H2O)] (Imd = imidazole; BTC = trimesate), with protonated imidazole molecules occupying the inter-lamellar space, and the structure resembles the classic inorganic compound, the sodium intercalated TiS2 (Na2TiS2).

Ocean atmosphere coupling over monsoon regions

In monsoon regions, the seasonal migration of the intertropical convergence zone (ITCZ) is manifested as a seasonal reversal of winds. Most of the summer monsoon rainfall over India occurs owing to synoptic and large-scale convection associated with the continental ITCZ (Fig. 1). We have investigated the interaction between these large-scale convective systems and the ocean over which they are generated1â3, concentrating on the relationship between organized convection over the Indian Ocean and sea surface temperature (SST). We report here that on a monthly basis the degree of cloudiness correlates well with SST for the relatively colder oceans, but when SST is maintained above 28 °C it ceases to be an important factor in determining the variability of cloudiness. Over the major regions of convection east of 70°E, which are warm year after year, the observed cloudiness cannot be correlated with variations in SST.