Heavy metals as markers for assessing environmental pollution from chemical warehouse and plastics fires

Case histories of large, accidental fires are presented to illustrate that heavy metals may be used as markers to assess the extent of localized environmental contamination resulting from fires. Due to the complexity of fire chemistry with respect to organic pollutants, determination of organic pollutants in the environment following a fire would be time consuming and expensive. Using heavy metals as markers on the other hand is much cheaper and can be done very rapidly. © 1995.

Electrochemical promotion of catalysis controlled by chemical potential difference across a mixed ionic-electronic conducting ceramic membrane - An example of wireless NEMCA

A La_0.6Sr_0.4Co_0.2F_0.8O₃ mixed ionic electronic conducting (MIEC) membrane was used in a dual chamber reactor for the promotion of the catalytic activity of a platinum catalyst for ethylene oxidation. By controlling the oxygen chemical potential difference across the membrane, a driving force for oxygen ions to migrate across the membrane and backspillover onto the catalyst surface is established. The reaction is then promoted by the formation of a double layer of oxide anions on the catalyst surface. Thelectronic conductivity of the membrane material eliminates the need for an external circuit to pump the promoting oxide ion species through the membrane and onto the catalyst surface. This renders this "wireless" system simpler and more amenable for large-scale practical application. Preliminary experiments show that the reaction rate of ethylene oxidation can indeed be promoted by almost one order of magnitude upon exposure to an oxygen atmosphere on the sweep side of the membrane reactor, and thus inducing an oxygen chemical potential difference across the membrane, as compared to the rate under an inert sweep gas. Moreover, the rate does not return to its initial unpromoted value upon cessation of the oxygen flow on the sweep side, but remains permanently promoted. A number of comparisons are drawn between the classical electrochemical promotion that utilises an external circuit and the "wireless" system that utilises chemical potential differences. In addition a 'surface oxygen capture' model is proposed to explain the permanent promotion of the catalyst activity. © 2007 Springer Science+Business Media, LLC.

Separation Science and Technology - Theory

I have completed 80% of a teaching text book (text and graphics) on Separation Science and Technology - Theory. The book's content is what I've learned over many years of practice and teaching with an emphasis on clarifying and explaining the nuances within the theories associated with various practical approaches to chemical and biochemical separations.

The book is divided into self-contained Chapters with many worked examples and practice questions. It very much aligns with my teaching on CHM3005D, CHM2010, CHM2007 and is ideal for PMY8105 and the new proposed MSci in Analytical Chemistry Programme. The book brings together diverse material in single space and will be a valuable pedagogical resource for the teaching of this key discipline within QUB and elsewhere.

ALMA-resolved salt emission traces the chemical footprint and inner wind morphology of VY Canis Majoris

(abreviated) We aim to study the inner-wind structure (R<250 Rstar) of the well-known red supergiant VY CMa. We analyse high spatial resolution (~0".24x0".13) ALMA Science Verification (SV) data in band 7 in which four thermal emission lines of gaseous sodium chloride (NaCl) are present at high signal-to-noise ratio. For the first time, the NaCl emission in the inner wind region of VY CMa is spatially resolved. The ALMA observations reveal the contribution of up to four different spatial regions. The NaCl emission pattern is different compared to the dust continuum and TiO2 emission already analysed from the ALMA SV data. The emission can be reconciled with an axisymmetric geometry, where the lower density polar/rotation axis has a position angle of ~50 degrees measured from north to east. However, this picture can not capture the full morphological diversity, and discrete mass ejection events need to be invoked to explain localized higher-density regions. The velocity traced by the gaseous NaCl line profiles is significantly lower than the average wind terminal velocity, and much slower than some of the fastest mass ejections, signalling a wide range of characteristic speeds for the mass loss. Gaseous NaCl is detected far beyond the main dust condensation region. Realising the refractory nature of this metal halide, this hints at a chemical process preventing all NaCl from condensing onto dust grains. We show that in the case of the ratio of the surface binding temperature to the grain temperature being ~50, only some 10% of NaCl remains in gaseous form, while for lower values of this ratio thermal desorption efficiently evaporates NaCl. Photodesorption by stellar photons seems not to be a viable explanation for the detection of gaseous NaCl at 220 Rstar from the central star, and instead, we propose shock-induced sputtering driven by localized mass ejection events as alternative.

Chemical ecology of arthropods. 9. Structure and absolute configuration of hippodamine and convergine, two novel alkaloids from american ladybug hippodamia convergens (coleoptera- coccinellidae)

In a previous communication (2) the isolation of two defensive alkaloid, hippodamine and convergine, from the American ladybug Hippodamia convergens was reported. A preliminary chemical study (2) led to the hypothesis that hippodamine could be represented by (1), with unknown stereochemistry at carbon atom 2. Convergine was supposed to be a 3a or 6a hydroxyhippodamine.

Sustainable Chemical Regulation in a Global Environment

The globalisation and unintended impacts of chemicals sets substantial challenges for sustainable development and the protection of natural resources such as land and water. Currently, there are three key chemical Conventions, the Basel Convention on the Control of Transboundary Movements of Hazardous Wastes and their Disposal which came into force in 1992, the 1993 Rotterdam Convention on Trade in Dangerous Chemicals and the Stockholm Convention on Persistent Organic Pollutants (POPs) (2004). These Conventions have as common features a mechanism for assessment of chemical safety, a process for the addition of new chemicals to a list of controlled substances and capacity building in developed countries. However, they only cover a small fraction of the chemicals manufactured and traded across the world. Defining effective regulation of chemicals is an on-going debate that has the potential to have a significant impact on vested commercial and political interests. A sustainable chemical industry should take account of evidence-based standards and through legal mechanisms adopt long-term precautionary evaluations rather than short-term market driven decisions. It is argued in this paper that effective international chemical regulation in the future will come from the adoption of sound chemical management and corporate social responsibility, but it recognised that this will face the challenge of economic disparity between countries and the potential export of regulatory risk from big chemical conglomerates to poorly regulated jurisdictions.

Wine and grape polyphenols — a chemical perspective

Phenolic compounds constitute a diverse group of secondary metabolites which are present in both grapes and wine. The phenolic content and composition of grape processed products (wine) are greatly influenced by the technological practice to which grapes are exposed. During the handling and maturation of the grapes several chemical changes may occur with the appearance of new compounds and/or disappearance of others, and consequent modification of the characteristic ratios of the total phenolic content as well as of their qualitative and quantitative profile. The non-volatile phenolic qualitative composition of grapes and wines, the biosynthetic relationships between these compounds, and the most relevant chemical changes occurring during processing and storage will be highlighted in this review.

Microstructure, mechanical properties and chemical degradation of brazed AISI 316 stainless steel/alumina systems

The main aims of the present study are simultaneously to relate the brazing parameters with: (i) the correspondent interfacial microstructure, (ii) the resultant mechanical properties and (iii) the electrochemical degradation behaviour of AISI 316 stainless steel/alumina brazed joints. Filler metals on such as Ag–26.5Cu–3Ti and Ag–34.5Cu–1.5Ti were used to produce the joints. Three different brazing temperatures (850, 900 and 950 °C), keeping a constant holding time of 20 min, were tested. The objective was to understand the influence of the brazing temperature on the final microstructure and properties of the joints. The mechanical properties of the metal/ceramic (M/C) joints were assessed from bond strength tests carried out using a shear solicitation loading scheme. The fracture surfaces were studied both morphologically and structurally using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction analysis (XRD). The degradation behaviour of the M/C joints was assessed by means of electrochemical techniques. It was found that using a Ag–26.5Cu–3Ti brazing alloy and a brazing temperature of 850 °C, produces the best results in terms of bond strength, 234 ± 18 MPa. The mechanical properties obtained could be explained on the basis of the different compounds identified on the fracture surfaces by XRD. On the other hand, the use of the Ag–34.5Cu–1.5Ti brazing alloy and a brazing temperature of 850 °C produces the best results in terms of corrosion rates (lower corrosion current density), 0.76 ± 0.21 μA cm−2. Nevertheless, the joints produced at 850 °C using a Ag–26.5Cu–3Ti brazing alloy present the best compromise between mechanical properties and degradation behaviour, 234 ± 18 MPa and 1.26 ± 0.58 μA cm−2, respectively. The role of Ti diffusion is fundamental in terms of the final value achieved for the M/C bond strength. On the contrary, the Ag and Cu distribution along the brazed interface seem to play the most relevant role in the metal/ceramic joints electrochemical performance.

Physico-chemical characterization and oxidative reactivity evaluation of aged brake wear particles

Brake wear dust is a significant component of traffic emissions and has been linked to adverse health effects. Previous research found a strong oxidative stress response in cells exposed to freshly generated brake wear dust. We characterized aged dust collected from passenger vehicles, using microscopy and elemental analyses. Reactive oxygen species (ROS) generation was measured with acellular and cellular assays using 2′7-dichlorodihydrofluorescein dye. Microscopy analyses revealed samples to be heterogeneous particle mixtures with few nanoparticles detected. Several metals, primarily iron and copper, were identified. High oxygen concentrations suggested that the elements were oxidized. ROS were detected in the cell-free fluorescent test, while exposed cells were not dramatically activated by the concentrations used. The fact that aged brake wear samples have lower oxidative stress potential than fresh ones may relate to the highly oxidized or aged state of these particles, as well as their larger size and smaller reactive surface area.