Real time analysis of atmospheric single particles in urban environments using aerosol time of flight mass spectrometry

In order to determine the size-resolved chemical composition of single particles in real-time an ATOFMS was deployed at urban background sites in Paris and Barcelona during the MEGAPOLI and SAPUSS monitoring campaigns respectively. The particle types detected during MEGAPOLI included several carbonaceous species, metal-containing types and sea-salt. Elemental carbon particle types were highly abundant, with 86% due to fossil fuel combustion and 14% attributed to biomass burning. Furthermore, 79% of the EC was apportioned to local emissions and 21% to continental transport. The carbonaceous particle types were compared with quantitative measurements from other instruments, and while direct correlations using particle counts were poor, scaling of the ATOFMS counts greatly improved the relationship. During SAPUSS carbonaceous species, sea-salt, dust, vegetative debris and various metal-containing particle types were identified. Throughout the campaign the site was influenced by air masses altering the composition of particles detected. During North African air masses the city was heavily influenced by Saharan dust. A regional stagnation was also observed leading to a large increase in carbonaceous particle counts. While the ATOFMS provides a list of particle types present during the measurement campaigns, the data presented is not directly quantitative. The quantitative response of the ATOFMS to metals was examined by comparing the ion signals within particle mass spectra and to hourly mass concentrations of; Na, K, Ca, Ti, V, Cr, Mn, Fe, Zn and Pb. The ATOFMS was found to have varying correlations with these metals depending on sampling issues such as matrix effects. The strongest correlations were observed for Al, Fe, Zn, Mn and Pb. Overall the results of this work highlight the excellent ability of the ATOFMS in providing composition and mixing state information on atmospheric particles at high time resolution. However they also show its limitations in delivering quantitative information directly.

Quantum chemical study of the effect of precursor stereochemistry on dissociative chemisorption and surface redox reactions during the atomic layer deposition of the transition metal copper

Using quantum chemical calculations, we investigate surface reactions of copper precursors and diethylzinc as the reducing agent for effective Atomic Layer Deposition (ALD) of Cu. The adsorption of various commonly used Cu(II) precursors is explored. The precursors vary in the electronegativity and conjugation of the ligands and flexibility of the whole molecule. Our study shows that the overall stereochemistry of the precursor governs the adsorption onto its surface. Formation of different Cu(II)/Cu(I)/Cu(0) intermediate complexes from the respective Cu(II) compounds on the surface is also explored. The surface model is a (111) facet of a Cu55 cluster. Cu(I) compounds are found to cover the surface after the precursor pulse, irrespective of the precursor chosen. We provide new information about the surface chemistry of Cu(II) versus Cu(I) compounds. A pair of CuEt intermediates or the dimer Cu2Et2 reacts in order to deposit a new Cu atom and release gaseous butane. In this reaction, two electrons from the Et anions are donated to copper for reduction to metallic form. This indicates that a ligand exchange between the Cu and Zn is important for the success of this transmetalation reaction. The effect of the ligands in the precursor on the electron density before and after adsorption onto the surface has also been computed through population analysis. In the Cu(I) intermediate, charge is delocalized between the Cu precursor and the bare copper surface, indicating metallic bonding as the precursor densifies to the surface.

Deposition of silver nanoparticles in geochemically heterogeneous porous media: predicting affinity from surface composition analysis.

The transport of uncoated silver nanoparticles (AgNPs) in a porous medium composed of silica glass beads modified with a partial coverage of iron oxide (hematite) was studied and compared to that in a porous medium composed of unmodified glass beads (GB). At a pH lower than the point of zero charge (PZC) of hematite, the affinity of AgNPs for a hematite-coated glass bead (FeO-GB) surface was significantly higher than that for an uncoated surface. There was a linear correlation between the average nanoparticle affinity for media composed of mixtures of FeO-GB and GB collectors and the relative composition of those media as quantified by the attachment efficiency over a range of mixing mass ratios of the two types of collectors, so that the average AgNPs affinity for these media is readily predicted from the mass (or surface) weighted average of affinities for each of the surface types. X-ray photoelectron spectroscopy (XPS) was used to quantify the composition of the collector surface as a basis for predicting the affinity between the nanoparticles for a heterogeneous collector surface. A correlation was also observed between the local abundances of AgNPs and FeO on the collector surface.

Magneto-hydro-dynamic analysis of an electrolysis cell for aluminum production

An electrolytic cell for Aluminum production contains molten metal subject to high currents and magnetic flux density. The interaction between these two fields creates electromagnetic forces within the liquid metal and can generate oscillations of the fluid similar to the waves at the free surface of oceans and rivers. The study of this phenomenon requires the simulation of the current density field, of the magnetic flux density field and the solution of the equations of motion of the liquid mass. An attempt to analyze the dynamical behavior of this problem is made by coupling different codes, based on different numerical techniques, in a single tool. The simulations are presented and discussed.

Maintenance of a case-base for the retrieval of rotationally symmetric shapes for the design of metal castings

In this paper, we discuss the problem of maintenance of a CBR system for retrieval of rotationally symmetric shapes. The special feature of this system is that similarity is derived primarily from graph matching algorithms. The special problem of such a system is that it does not operate on search indices that may be derived from single cases and then used for visualisation and principle component analyses. Rather, the system is built on a similarity metric defined directly over pairs of cases. The problems of efficiency, consistency, redundancy, completeness and correctness are discussed for such a system. Performance measures for the CBR system are given, and the results for trials of the system are presented. The competence of the current case-base is discussed, with reference to a representation of cases as points in an n-dimensional feature space, and a Gramian visualisation. A refinement of the case base is performed as a result of the competence analysis and the performance of the case-base before and after refinement is compared.

Experimental and modeling analysis of the reliability of the anisotropic conductive films

Experiments as well as computer modeling methods have been used to investigate the effect of the solder reflow process on the electrical characteristics and reliability of anisotropic conductive film (ACF) interconnections. In the experiments, the contact resistance of the ACF interconnections was found to increase after a subsequent reflow and the magnitude of this increase was strongly correlated to the peak temperature of the reflow profile. In fact, nearly 40 percent of the joints were opened (i.e. lifted away from the pad) after the reflow with a peak temperature of 260 OC while no openings was observed when the peak temperature was 210 "C. It is believed that the CTE mismatch between the polymer particle and the adhesive matrix is the main cause of this contact degradation. To understand this phenomenon better, a 3-D model of an ACF joint structure was built and Finite Element Analysis was used to predict the stress distrihution in the conductive particles, adhesive matrix and metal pads during the reflow process. The effects of the peak temperature, the CTE of the adhesive matrix and the bump height on the reliability of the ACF interconnections were discussed.

Case-based retrieval of 3-dimensional shapes for the design of metal castings

This paper describes research into retrieval based on 3-dimensional shapes for use in the metal casting industry. The purpose of the system is to advise a casting engineer on the design aspects of a new casting by reference to similar castings which have been prototyped and tested in the past. The key aspects of the system are the orientation of the shape within the mould, the positions of feeders and chills, and particular advice concerning special problems and solutions, and possible redesign. The main focus of this research is the effectiveness of similarity measures based on 3-dimensional shapes. The approach adopted here is to construct similarity measures based on a graphical representation deriving from a shape decomposition used extensively by experienced casting design engineers. The paper explains the graphical representation and discusses similarity measures based on it. Performance measures for the CBR system are given, and the results for trials of the system are presented. The competence of the current case-base is discussed, with reference to a representation of cases as points in an n-dimensional feature space, and its principal components visualization. A refinement of the case base is performed as a result of the competence analysis and the performance of the case-base before and after refinement is compared.

Manufacturing of uniformly-sized silicon particles for solar cell from molten metal jet by electromagnetic pinch force

Spherical silicon solar cells are expected to serve as a technology to reduce silicon usage of photovoltaic (PV) power systems[1, 2, 3]. In order to establish the spherical silicon solar cell, a manufacturing method of uniformly sized silicon particles of 1mm in diameter is required. However, it is difficult to mass-produce the mono-sized silicon particles at low cost by existent processes now. We proposed a new method to generate liquid metal droplets uniformly by applying electromagnetic pinch force to a liquid metal jet[4]. The electromagnetic force was intermittently applied to the liquid metal jet issued from a nozzle in order to fluctuate the surface of the jet. As the fluctuation grew, the liquid jet was broken up into small droplets according to a frequency of the intermittent electromagnetic force. Firstly, a preliminary experiment was carried out. A single pulse current was applied instantaneously to a single turn coil around a molten gallium jet. It was confirmed that the jet could be split up by pinch force generated by the current. And then, electromagnetic pinch force was applied intermittently to the jet. It was found that the jet was broken up into mono-sized droplets in the case of a force frequency was equal to a critical frequency[5], which corresponds to a natural disturbance wave length of the jet. Numerical simulations of the droplet generation from the liquid jet were then carried out, which consisted of an electromagnetic analysis and a fluid flow calculation with a free surface of the jet. The simulation results were compared with the experiments and the agreement between the two was quite good.

A guide to the assessment of heavy metal contamination in estuaries using biological indicators. Occasional Publication of the Marine Biological Association 4

The rationale behind the use of analyses of estuarine organisms to assess levels of heavy-metal contamination is described and compared with alternative methods such as the analysis of waters or sediments. Based on field observations in United Kingdom estuaries and on evidence from the literature, an assessment is made of the suitability of 17 species as the indicators of metals and metalloids including Ag, As, Cd, Co, Cr, Cu, Hg, Ni, Se, Sn, Pb and Zn.

Heavy metal accumulation reflecting natural sedimentary processes and anthropogenic activities in two contrasting coastal wetland ecosystems, eastern China

Due to the impacts of natural processes and anthropogenic activities, different coastal wetlands are faced with variable patterns of heavy metal contamination. It is important to quantify the contributions of pollutant sources, in order to adopt appropriate protection measures for local ecosystems. The aim of this research was to compare the heavy metal contamination patterns of two contrasting coastal wetlands in eastern China. In addition, the contributions from various metal sources were identified and quantified, and influencing factors, such as the role of the plant Spartina alterniflora, were evaluated. Materials and methods Sediment samples were taken from two coastal wetlands (plain-type tidal flat at the Rudong (RD) wetland vs embayment-type tidal flat at Luoyuan Bay (LY)) to measure the content of Al, Fe, Co, Cr, Cu, Mn, Mo, Ni, Sr, Zn, Pb, Cd, and As. Inductively coupled plasma atomic emission spectrometry, flame atomic absorption spectrometry, and atomic fluorescence spectrometry methods were used for metal detection. Meanwhile, the enrichment factor and geoaccumulation index were applied to assess the pollution level. Principle component analysis and receptor modeling were used to quantify the sources of heavy metals. Results and discussion Marked differences in metal distribution patterns between the two systems were present. Metal contents in LY were higher than those in RD, except for Sr and Mo. The growth status of S. alterniflora influenced metal accumulations in RD, i.e., heavy metals were more easily adsorbed in the sediment in the following sequence: Cu > Cd > Zn > Cr > Al > Pb ≥ Ni ≥ Co > Fe > Sr ≥ Mn > As > Mo as a result of the presence and size of the vegetation. However, this phenomenon was not observed in LY. A higher potential ecological risk was associated with LY, compared with RD, except for Mo. Based on a receptor model output, sedimentary heavy metal contents at RD were jointly influenced by natural sedimentary processes and anthropogenic activities, whereas they were dominated by anthropogenic activities at LY. Conclusions A combination of geochemical analysis and modeling approaches was used to quantify the different types of natural and anthropogenic contributions to heavy metal contamination, which is useful for pollution assessments. The application of this approach reveals that natural and anthropogenic processes have different influences on the delivery and retention of metals at the two contrasting coastal wetlands. In addition, the presence and size of S. alterniflora can influence the level of metal contamination in sedimentary environments.

Xanthoria parietina as a biomonitor of airborne heavy metal pollution in forest sites in the North East of Morocco

Xanthoria parietina, common foliose lichen, growing in its natural habitat, was analysed for the concentration of five heavy metals (Fe, Cr, Zn, Pb and Cu) from different forest sites of North East of Morocco (Kenitra, Sidi Boughaba, Mkhinza, Ceinture Verte near Temara city, Skhirate, Bouznika and Mohammedia). The quantification was carried out by inductively coupled plasma - atomic emission spectrometry (ICP-AES). Results were highly significant p<0,001. The concentration of metals is correlated with the vehicular activity and urbanization. The total metal concentration is highest at the Kenitra area, followed by Ceinture Verte site near Temara city, which experience heavy traffic throughout the year. Scanning electron microscopy (SEM) of particulate matter on lichen of Xanthoria parietina was assessed as a complementary technique to wet chemical analysis for source apportionment of airborne contaminant. Analysis revealed high level of Cu, Cr, Zn and Pb in samples near roads.  

General rules for predicting where a catalytic reaction should occur on metal surfaces: A density functional theory study of C-H and C-O bond breaking/making on flat, stepped, and kinked metal surfaces

To predict where a catalytic reaction should occur is a fundamental issue scientifically. Technologically, it is also important because it can facilitate the catalyst's design. However, to date, the understanding of this issue is rather limited. In this work, two types of reactions, CH4 CH3 + H and CO C + 0 on two transition metal surfaces, were chosen as model systems aiming to address in general where a catalytic reaction should occur. The dissociations of CH4 - CH3 + H and CO --> C + O and their reverse reactions on flat, stepped, and kinked Rh and Pd surfaces were studied in detail. We find the following: First, for the CH4 Ch(3) + H reaction, the dissociation barrier is reduced by similar to0.3 eV on steps and kinks as compared to that on flat surfaces. On the other hand, there is essentially no difference in barrier for the association reaction of CH3 + H on the flat surfaces and the defects. Second, for the CO C + 0 reaction, the dissociation barrier decreases dramatically (more than 0.8 eV on Rh and Pd) on steps and kinks as compared to that on flat surfaces. In contrast to the CH3 + H reaction, the C + 0 association reaction also preferentially occurs on steps and kinks. We also present a detailed analysis of the reaction barriers in which each barrier is decomposed quantitatively into a local electronic effect and a geometrical effect. Our DFT calculations show that surface defects such as steps and kinks can largely facilitate bond breaking, while whether the surface defects could promote bond formation depends on the individual reaction as well as the particular metal. The physical origin of these trends is identified and discussed. On the basis of our results, we arrive at some simple rules with respect to where a reaction should occur: (i) defects such as steps are always favored for dissociation reactions as compared to flat surfaces; and (ii) the reaction site of the association reactions is largely related to the magnitude of the bonding competition effect, which is determined by the reactant and metal valency. Reactions with high valency reactants are more likely to occur on defects (more structure-sensitive), as compared to reactions with low valency reactants. Moreover, the reactions on late transition metals are more likely to proceed on defects than those on the early transition metals.

A detailed abundance analysis of the hot post-AGB star ZNG-1 in M10

We present a model-atmosphere analysis for the bright (V similar to 13) star ZNG-1, in the globular cluster M10. From high-resolution (R similar to 40 000) optical spectra we confirm ZNG-1 to be a post-asymptotic giant branch (post-AGB) star. The derived atmospheric parameters are T-eff = 26 500 +/- 1000 K and log g = 3.6 +/- 0.2 dex. A differential abundance analysis reveals a chemical composition typical of hot post-AGB objects, with ZNG-1 being generally metal poor, although helium is approximately solar. The most interesting feature is the large carbon underabundance of more than 1.3 dex. This carbon deficiency, along with an observed nitrogen enhancement relative to other elements, may suggest that ZNG-1 evolved off the AGB before the third dredge-up occurred. Also, iron depletions observed in other similar stars suggest that gas- dust fractionation in the AGB progenitor could be responsible for the observed composition of these objects. However, we need not invoke either scenario since the chemical composition of ZNG-1 is in good agreement with abundances found for a Population II star of the same metallicity.

A non-LTE abundance analysis of the post-AGB star ROA 5701

An analysis of high-resolution Anglo-Australian Telescope (AAT)/University College London Echelle Spectrograph (UCLES) optical spectra for the ultraviolet (UV)-bright star ROA 5701 in the globular cluster omega Cen (NGC 5139) is performed, using non-local thermodynamic equilibrium (non-LTE) model atmospheres to estimate stellar atmospheric parameters and chemical composition. Abundances are derived for C, N, O, Mg, Si and S, and compared with those found previously by Moehler et al. We find a general metal underabundance relative to young B-type stars, consistent with the average metallicity of the cluster. Our results indicate that ROA 5701 has not undergone a gas-dust separation scenario as previously suggested. However, its abundance pattern does imply that ROA 5701 has evolved off the asymptotic giant branch (AGB) prior to the onset of the third dredge-up.

On the generation of metal clusters with the electrochemical scanning tunneling microscope

In the present work we consider two aspects of the deposition of metal clusters on an electrode surface. The formation of such clusters with the tip of a scanning tunneling microscope is simulated by atom dynamics. Subsequently the stability of these clusters is investigated by Monte Carlo simulations in a grand-canonical ensemble. In particular, the following systems were considered explicitly: Pd clusters on Au(111), Cu on Au(111), Ag on Au(111), Pb on Au(111) and Cu on Ag(111). The analysis of the results obtained for the different systems leads to the conclusion that optimal systems for nanostructuring are those where the metals participating have similar cohesive energies and negative heats of alloy formation. In this respect, the system Cu-Pd(111) is predicted as a good candidate for the formation of stable clusters. (c) 2005 Elsevier B.V. All rights reserved.