A new method based on low background instrumental neutron activation analysis for major,trace and ultra-trace element determination in atmospheric mineral dust from polar ice cores

Dust found in polar ice core samples present extremely low concentrations, in addition the availability of such samples is usually strictly limited. For these reasons the chemical and physical analysis of polar ice cores is an analytical challenge. In this work a new method based on low background instrumental neutron activation analysis (LB-INAA) for the multi-elemental characterization of the insoluble fraction of dust from polar ice cores is presented. Thanks to an accurate selection of the most proper materials and procedures it was possible to reach unprecedented analytical performances, suitable for ice core analyses. The method was applied to Antarctic ice core samples. Five samples of atmospheric dust (μg size) from ice sections of the Antarctic Talos Dome ice core were prepared and analyzed. A set of 37 elements was quantified, spanning from all the major elements (Na, Mg, Al, Si, K, Ca, Ti, Mn and Fe) to trace ones, including 10 (La, Ce, Nd, Sm, Eu, Tb, Ho, Tm, Yb and Lu) of the 14 natural occurring lanthanides. The detection limits are in the range of 10⁻¹³–10⁻⁶ g, improving previous results of 1–3 orders of magnitude depending on the element; uncertainties lies between 4% and 60%.     

Study on the difference in adsorption thermodynamics for water on swelling and non-swelling clays with implications for prevention and treatment of pneumoconiosis

Excessive inhalation of mineral dust can cause irreversible damage such as diffuse fibrosis of lung tissue. Water-based dust reduction technology can effectively control the dust concentration. The study of the interaction of water-clay mineral dust is helpful to the prevention and treatment of pneumoconiosis by water-based dust removal technology. To better understand the underlying adsorption mechanisms of water molecules on clay mineral dust, the detailed adsorption thermodynamics analysis is necessary. In this paper, we research the thermodynamics of adsorption of water molecules on swelling clay of montmorillonite and non-swelling clay of illite. First, the adsorption isotherms of water molecules on montmorillonite and illite at 293–313 K were measured by gravimetric method. Then, the key thermodynamic variables, including entropy change (ΔS), surface potential (Ω), isosteric heat of adsorption (Q_st) and variation of Gibbs free energy (ΔG), were analyzed. Results illustrate that the adsorption amount for water molecules on illite is one order of magnitude smaller than that on montmorillonite, suggesting that swelling clay plays a dominant role in water molecules adsorption process. For water molecules adsorption on montmorillonite, the contribution of secondary adsorption to total adsorption (a₂/a) is always less than 30%. For water molecules adsorption on illite, the contribution of primary adsorption to total adsorption (a₁/a) is greater than a₂/a at the low pressure region, while a₂/a can exceed 60% at the high pressure region. The difference in the uptakes of water molecules adsorption on non-swelling and swelling clays is mainly resulted from the difference in primary adsorption on two clays. The Henry’s constant (K_AA) for montmorillonite is in the range of 21.37–75.08 mmol/g/kPa, which is evidently larger than the K_AA values of 0.34–0.98 mmol/g/kPa for illite. Compared with non-swelling clay, the adsorption spontaneity degree for water molecules on swelling clay is higher, and the interaction of swelling clay-water molecules is stronger. Meanwhile, the movement of adsorbed water molecules in swelling clay is more confined than that in non-swelling clay. These findings can offer meaningful guidelines for the prevention and treatment of pneumoconiosis.     

Radiotracer estimation of laterite grain erosion in a fluidized bed calciner

By means of radiotracers the erosion of a laterite in an industrial fluidized bed calciner was estimated experimentally. Based on experimental data a simplified formula is found which permits calculation of the mass of the dust deriving from erosion when the granulometric composition of the mineral on entry to the calciner is known. Application of this formula in a current industrial case shows that erosion is the main cause of the production of dust. A method for reducing the quantity of dust is proposed.     

Surface-catalyzed chlorine and nitrogen activation: mechanisms for the heterogeneous formation of ClNO, NO, NO2, HONO, and N2O from HNO3 and HCl on aluminum oxide particle surfaces

It is well-known that chlorine active species (e.g., Cl(2), ClONO(2), ClONO) can form from heterogeneous reactions between nitrogen oxides and hydrogen chloride on aerosol particle surfaces in the stratosphere. However, less is known about these reactions in the troposphere. In this study, a potential new heterogeneous pathway involving reaction of gaseous HCl and HNO(3) on aluminum oxide particle surfaces, a proxy for mineral dust in the troposphere, is proposed. We combine transmission Fourier transform infrared spectroscopy with X-ray photoelectron spectroscopy to investigate changes in the composition of both gas-phase and surface-bound species during the reaction under different environmental conditions of relative humidity and simulated solar radiation. Exposure of surface nitrate-coated aluminum oxide particles, from prereaction with nitric acid, to gaseous HCl yields several gas-phase products, including ClNO, NO(2), and HNO(3), under dry (RH < 1%) conditions. Under humid more conditions (RH > 20%), NO and N(2)O are the only gas products observed. The experimental data suggest that, in the presence of adsorbed water, ClNO is hydrolyzed on the particle surface to yield NO and NO(2), potentially via a HONO intermediate. NO(2) undergoes further hydrolysis via a surface-mediated process, resulting in N(2)O as an additional nitrogen-containing product. In the presence of broad-band irradiation (λ > 300 nm) gas-phase products can undergo photochemistry, e.g., ClNO photodissociates to NO and chlorine atoms. The gas-phase product distribution also depends on particle mineralogy (Al(2)O(3) vs CaCO(3)) and the presence of other coadsorbed gases (e.g., NH(3)). These newly identified reaction pathways discussed here involve continuous production of active ozone-depleting chlorine and nitrogen species from stable sinks such as gas-phase HCl and HNO(3) as a result of heterogeneous surface reactions. Given that aluminosilicates represent a major fraction of mineral dust aerosol, aluminum oxide can be used as a model system to begin to understand various aspects of possible reactions on mineral dust aerosol surfaces.     

Soft X-ray spectromicroscopy on solid-stabilized emulsions

Oil–water emulsions stabilized by solids have been imaged with sub-100 nm spatial resolution and analyzed spectroscopically using a scanning transmission X-ray microscope. The emulsions are stabilized by particle heterocoagulate cages surrounding the oil droplets. These cages form due to the interaction of negatively charged clay mineral particles (sodium montmorillonite, Wyoming) and positively charged particles of calcium/aluminum layered double hydroxide (LDH). The emulsions were studied at atmospheric pressure, without any pretreatment using carbon K and calcium L X-ray absorption edges. Oil- and calcium-rich LDH were separately mapped, and the clay mineral dispersions were also imaged. Applying X-ray absorption-edge contrast, oil could be distinguished from water in the emulsion near the carbon K absorption edge (284 eV, 4.4 nm). Spectromicroscopy near the calcium L absorption edge (346 eV, 3.6 nm) allowed the structural details of heterocoagulate formation to be revealed. Received: 11 December 1998 Accepted in revised form: 10 January 1999     

Retrospective Analysis of Anthropogenic Inputs of Lead and Other Heavy Metals to the Hawaiian Sedimentary Environment

In this paper we present and discuss heavy-metal concentrations in sediment cores from the Ala Wai Canal, a small urban drainage estuary in Honolulu, Hawaii (Oahu Island), and from selected soils and sediments collected in less impacted areas of Hawaii. We focus on lead and its isotope ratios to document the introduction, proliferation and subsequent phasing-out of alkyl-lead fuel additives in Honolulu over the past 60 years. Sedimentary lead increases from <10 ppm in the oldest (deepest) unimpacted portions of the cores to ˜750 ppm in sediments from the mid-1970s; lead contents then decrease to a range of 100–300 ppm in the most recent deposits. Lead concentrations in the canal sediments closely track the consumption of alkyl-lead fuel additives used on Oahu in the middle of this century. More than 90% of the lead in certain core intervals is of anthropogenic origin. Stable lead isotope ratios reflect changes in the estuary's sources of lead and show that this lead has an isotopic signature distinct from natural samples. Undisturbed layers of sediments in the Ala Wai canal track the average composition of anthropogenic lead used in its Honolulu watershed through time. The distinctive pattern of lead isotopes measured in Ala Wai Canal sediments can be used to distinguish anthropogenic from natural lead in Hawaiian rural locations. Soils located away from point-sources of contamination have isotopic compositions defined by mixtures of locally erupted volcanic rock, atmospheric dust and components similar to Ala Wai Canal anthropogenic lead. Natural lead concentrations in Hawaii are in the range of a few to a few tens of parts per million, with the high-concentration end-member occurring in a few selected intramountain basins where soils contain a significant component of continental dust fines scavenged by rainfall and concentrated by local geological conditions. Rural watershed material exhibits small but discernible elevations in lead concentrations due to anthropogenic effects. Other metals (cadmium, copper and zinc) in the Ala Wai Canal sediments also display patterns consistent with increased fluxes of metals attributable to anthropogenic activity. Unlike lead, no clear maxima are observed in sediments deposited during the mid 1970s. Rather, a continued input of these metals is attributed to expanding anthropogenic activity in the Ala Wai Canal watershed. © 1997 by John Wiley & Sons, Ltd.     

μ-Synchrotron radiation excited X-ray fluorescence microprobe trace element studies on spherules of the Cretaceous/Tertiary boundary transitions of NE-Mexico and Haiti samples

Synchrotron radiation, collimated to a μm scale was used for the determination of trace elements in micro-tektites and spherule material for the first time. The experimental set-up of the SXRF microprobe at beamline L at HASYLAB at DESY offers a suitable method for performing non-destructive in situ multi-element analysis focusing on spatial trace element distributions and mineral phases of the melted ejecta material from the Cretaceous/Tertiary boundary. The spatial distribution of trace elements was determined in melt inclusions as well as in phase transitions in selected parts of chlorite–smectite spherules and tektite glass material by using a beam with a diameter of 15 μm collimated with a glass capillary for line- and area scans as well as for single point measurements for elements with Z between 19 and 92. The analyzed spherules show alteration features but also zonation and carbonate inclusions, originating from the Chicxulub impact event. These initial results demonstrate the potential of μ-SXRF analysis for the discrimination of alteration and primary signals of the spherules and re-construction of their genetic evolution. It could be shown that the spherules represent a complex mixture of different materials from the subsurface at the Chicxulub impact site.     

Mineral–water interfacial structures revealed by synchrotron X-ray scattering

Chemical reactions occurring at the mineral–water interface are controlled by an interfacial layer, nanometers thick, whose properties may deviate from those of the respective bulk mineral and water phases. The molecular-scale structure of this interfacial layer, however, is poorly constrained, and correlations between macroscopic phenomena and molecular-scale processes remain speculative. The application of high-resolution X-ray scattering techniques has begun to provide substantial new insights into the molecular-scale structure of the mineral–water interface. In this review, we describe the characteristics of synchrotron-based X-ray scattering techniques that make them uniquely powerful probes of mineral–water interfacial structures and discuss the new insights that have been derived from their application. In particular, we focus on efforts to understand the structure and distribution of interfacial water as well as their dependence on substrate properties for major mineral classes including oxides, carbonates, sulfates, phosphates, silicates, halides and chromates. We compare these X-ray scattering results with those from other structural and spectroscopic techniques and integrate these to provide a conceptual framework upon which to base an understanding of the systematic variation of mineral–water interfacial structures.     

Evaluation of sorption of uranium onto metakaolin using X-ray photoelectron and Raman spectroscopies

Metakaolin prepared from a natural clay mineral ore of aluminium kaolinite is a promising low cost and high activity aluminosilicate material that has been investigated for studying the sorption behavior of uranium. Here, metakaolin was characterized using X-ray photoelectron spectroscopy (XPS) and the effects of pH, contact time and initial metal ion concentration on its sorption behavior were studied. The sorption process was found to initially be rapid (∼60% at time 0 min) but became slower with time; equilibrium was established within 24 h (∼80% sorption). The data were applied to study the kinetics of the sorption process. The Langmuir and Dubinin-Radushkevich (D-R) sorption isotherms were used to describe partitioning behavior for the system at room temperature. The binding of metal ions was found to be pH dependent, with optimal sorption occurring at pH 5. The retained metal ions were eluted with 5 mL of 0.1 M HNO₃. Raman spectroscopy and XPS were used to evaluate the sorption mechanism of U(VI).     

Cosmic dust in the earth's atmosphere

This review discusses the magnitude of the cosmic dust input into the earth's atmosphere, and the resulting impacts from around 100 km to the earth's surface. Zodiacal cloud observations and measurements made with a spaceborne dust detector indicate a daily mass input of interplanetary dust particles ranging from 100 to 300 tonnes, which is in agreement with the accumulation rates of cosmic-enriched elements (Ir, Pt, Os and super-paramagnetic Fe) in polar ice cores and deep-sea sediments. In contrast, measurements in the middle atmosphere - by radar, lidar, high-flying aircraft and satellite remote sensing - indicate that the input is between 5 and 50 tonnes per day. There are two reasons why this huge discrepancy matters. First, if the upper range of estimates is correct, then vertical transport in the middle atmosphere must be considerably faster than generally believed; whereas if the lower range is correct, then our understanding of dust evolution in the solar system, and transport from the middle atmosphere to the surface, will need substantial revision. Second, cosmic dust particles enter the atmosphere at high speeds and undergo significant ablation. The resulting metals injected into the atmosphere are involved in a diverse range of phenomena, including: the formation of layers of metal atoms and ions; the nucleation of noctilucent clouds, which are a sensitive marker of climate change; impacts on stratospheric aerosols and O(3) chemistry, which need to be considered against the background of a cooling stratosphere and geo-engineering plans to increase sulphate aerosol; and fertilization of the ocean with bio-available Fe, which has potential climate feedbacks.     

Deliquescence behavior of internally mixed clay and salt aerosols by optical extinction measurements

Internal mixtures of montmorillonite, a clay component of mineral dust, with sodium chloride or ammonium sulfate were studied optically using cavity ring down spectroscopy. The effects of the addition of the clay to the optically observed deliquescence relative humidity (DRH) and water uptake of these salts were considered by investigating a series of different salt mass fractions. In most cases, montmorillonite alters the hygroscopic properties, lowering the DRH in comparison to the pure salt, and causes the particles to transition from solid to liquid at a lower relative humidity than is expected based on the salt alone. Predictions based on volume-weighted mixing rules were not accurate for most measurements around the DRH. We attribute deviations from theory to changes in the Gibbs free energy of the system caused by disturbances in the ion-ion interactions and lattice structure allowing water uptake prior to the DRH of the salt. Our optical results contradict some current measurements in the literature that suggest little change in the hygroscopic behavior of salts when insoluble mineral dust components are added.     

Localized damage response of carbon fiber reinforced polymer composite sandwich panel after thermal exposure

An experimental study was conducted to investigate the effect of thermal exposure on indentation behavior of carbon fiber reinforced polymer composite sandwich panel (CFRPCSP) with pyramidal truss cores. Composite sandwich panels were fabricated by the hot press molding method. Subsequently, composite sandwich panels were exposed to different temperatures for 6 h. After thermal exposure, quasi-static indentation tests were carried out at room temperature. Then, the effect of thermal exposure on the failure mechanism, indentation load and energy absorption were analyzed and discussed. The results showed that the indentation load and energy absorption decreased as exposure temperature increased, which was caused by the degradation of the matrix properties and fiber-matrix interface properties at high temperature. In addition to the decrease of the indentation load and energy absorption, the failure modes also changed with exposure temperature. It is expected that this study can provide useful information for the design and application of composite sandwich panel with pyramidal truss cores at high temperature.     

The investigations on K and L X-ray fluorescence parameters of gold compounds

The study aimed to determine the chemical effects on the K and L X-ray intensity ratios and the K and L X-ray production cross sections for gold compounds. The K shell fluorescence yields and L shell average yields were also investigated. The samples were excited by 59.5 keV γ-rays from an ²⁴¹Am annular radioactive source and 123.6 keV γ-rays from a ⁵⁷Co annular radioactive source. K and L X-rays emitted from samples were counted by an Ultra-LEGe detector with a resolution of 0.150 keV at 5.9 keV. The experimental values were compared with theoretical, the semi-empirical and other experimental values.     

The heterogeneous decomposition of ozone on atmospheric mineral dust surrogates at ambient temperature

The rate of uptake of ozone on various mineral dust surrogates, expressed as uptake coefficient γ, has been studied employing a Knudsen flow reactor. Experiments were performed at T = 298 ± 2 K on substrates of kaolinite, CaCO₃, natural limestone, Saharan dust, and Arizona test dust. Initially, the uptake coefficients have been calculated on the basis of the geometric surface area of the powder samples. Both initial and steady‐state uptake coefficients γ₀ and γ_ss were found very similar for all the examined substrates. In addition, additional uptake experiments on marble sample have shown that γ₀ and γ_ss may be overestimated between a factor of 50 and 100, respectively. Based on these considerations, we proposed initial and steady‐state uptake values of the order of 10^?4 and 10^?5, respectively. On kaolinite, the uptake coefficient decreased with increasing O₃ residence time τ_g thus indicating a complex mechanism. In contrast, γ decreased and became independent of τ_g at long residence time after long exposure to O₃. For all uptake experiments the disappearance of O₃ was accompanied by the formation of O₂. The different mineral dust surrogates may be more accurately distinguished by their time‐dependent O₂ yield r(t) rather than the magnitude of γ. The heterogeneous reaction of O₃ on mineral dust has been found to be noncatalytic and of limited importance in the atmosphere. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 407–419, 2006     

Oil refinery dusts: morphological and size analysis by TEM

The objectives of this work were to develop a means of sampling atmospheric dusts on the premises of an oil refinery for electron microscopic study to carry out preliminary morphological analyses and to compare these dusts with those collected at sites beyond the refinery limits. Carbon and collodion membranes were used as a support for collection of dust particles straight on transmission electron microscopy (TEM) grids. Micrographs of the dust particles were taken at magnifications from ×4,000 to ×80,000 with a Tesla BS500 transmission electron microscope. Four parameters were defined on the basis of the micrographs: surface area, Feret diameter, circumference, and shape coefficient. The micrographs and literature data were used to classify the atmospheric dusts into six groups: particles with an irregular shape and rounded edges; particles with an irregular shape and sharp edges; soot and its aggregates; spherical particles; singly occurring, ultrafine dust particles; and particles not allocated to any of the previous five groups. The types of dusts found in all the samples were similar, although differences did exist between the various morphological parameters. Dust particles with the largest Feret diameter were present in sample 3 (mean, 0.739 μm)—these were collected near the refinery's effluent treatment plant. The particles with the smallest diameter were found in the sample that had been intended to be a reference sample for the remaining results (mean, 0.326 μm). The dust particles collected in the refinery had larger mean Feret diameters, even 100% larger, than those collected beyond it. Particles with diameters from 0.1 to 0.2 μm made up the most numerous group in all the samples collected in the refinery.     

Pressurized-Liquid Extraction as an Efficient Method for Valorization of Thymus serpyllum Herbal Dust towards Sustainable Production of Antioxidants

The aim of this study was to valorize Thymus serpyllum herbal dust, a particular fraction distinguished as an industrial waste from filter-tea production. Pressurized liquid extraction (PLE) was used with the aim of overcoming certain obstacles of conventional extraction techniques in terms of shortening extraction time, reducing solvent consumption and energy costs, using “green” solvents and obtaining high yield and quality products. In order to optimize PLE of T. serpyllum herbal dust, the preliminary screening of the independent variables in order to define the most influential parameters and their domain was done first. After the screening, the optimization study using the face-centered central composite experimental design (CCD) with response surface methodology (RSM) was implemented. Additionally, taking into account the high awareness of the positive influence of antioxidants on the human health and associating it with high content of polyphenolic compounds in various members of Lamiaceae family, PLE has proven to be a great approach for antioxidants recovery from T. serpyllum herbal dust.     

Static and dynamic molecular mechanics modelling and X-ray scattering calculations for a cyclic siloxane macromolecule

A liquid crystalline system consisting of cyclic penta(methylsiloxane) cores with biphenylyl 4-propoxybenzoate mesogens is studied with respect to its molecular conformation and the intermolecular ordering of pendant groups by employing molecular mechaincs calculations, while a molecular dynamics simulation indicates the degree of conformational flexibility. The calculated X-ray scattering patterns for these structures provide insight into the origin of the experimentally observed results. A good agreement is found between the calculated and experimental reflections data, supporting the ‘cylinder’ global topology as the basis for forming a ‘columnar’ structure. Further, a comparison of the calculated and experimental meriodional sections shows a strong similarity of both the meridional intensities and d-spacings.     

Local and non-local sources of airborne particulate pollution at Beijing

A new element tracer technique has firstly been established to estimate the contributions of mineral aerosols from both inside and outside Beijing. The ratio of Mg/Al in aerosol is a feasible element tracer to distinguish between the sources of inside and outside Beijing. Mineral aerosol, inorganic pollution aerosol mainly as sulfate and nitrate, and organic aerosol are the major components of airborne particulates in Beijing, of which mineral aerosol accounted for 32%–-67% of total suspended particles (TSP), 10% –70% of fine particles (PM2.5), and as high as 74% and 90% of TSP and PM_2.5, respectively, in dust storm. The sources from outside Beijing contributed 62% (38%–-86%) of the total mineral aerosols in TSP, 69% (52%–-90%) in PM₁₀, and 76% (59%–-93%) in PM_2.5 in spring, and 69% (52%–-83%), 79% (52%–-93%), and 45% (7% – 79%) in TSP, PM₁₀, and PM_2.5, respectively, in winter, while only ≈20% in summer and autumn. The sources from outside Beijing contributed as high as 97% during dust storm and were the dominant source of airborne particulates in Beijing. The contributions from outside Beijing in spring and winter are higher than those in summer, indicating clearly that it was related to the various meteorological factors.     

Al-Zn-Sn Phase Diagram X-ray diffraction study at various temperatures

Further studies of the ternary phase diagram Al-Zn-Sn have been carried out by X-ray diffraction at various temperatures and by thermodilatometry in order to confirm our earlier experimental results which have been refuted by some recent work based on thermodynamic optimization. These new results, in particular the change with temperature of the crystallized fraction for Al-Zn-Sn mixtures containing up to 31.5 mass% of tin, confirm our previous results on the existence of a significant retrograde miscibility of tin in a solid solution α′ss (in the temperature range 286 to 335°C) which protrudes into the ternary system starting from the Al-Zn binary up to a tin concentration of about 50 mass%. This disagreement between theory and experiment highlights the difficulties of a thermodynamic optimization approach based on solid state solubilities in the binary systems and on ternary liquidus data which disregards the ternary interaction parameters in the solid state. Besides, this experimental study highlights the difficulties in understanding the phenomena which depend on phase stabilities. This revised version was published online in July 2006 with corrections to the Cover Date.     

Ultra-trace determination of Persistent Organic Pollutants in Arctic ice using stir bar sorptive extraction and gas chromatography coupled to mass spectrometry

This study presents the optimization and application of an analytical method based on the use of stir bar sorptive extraction (SBSE) gas chromatography coupled to mass spectrometry (GC–MS) for the ultra-trace analysis of POPs (Persistent Organic Pollutants) in Arctic ice. In a first step, the mass-spectrometry conditions were optimized to quantify 48 compounds (polycyclic aromatic hydrocarbons, brominated diphenyl ethers, chlorinated biphenyls, and organochlorinated pesticides) at the low pg/L level. In a second step, the performance of this analytical method was evaluated to determine POPs in Arctic cores collected during an oceanographic campaign. Using a calibration range from 1 to 1800 pg/L and by adjusting acquisition parameters, limits of detection at the 0.1–99 and 102–891 pg/L for organohalogenated compounds and polycyclic aromatic hydrocarbons, respectively, were obtained by extracting 200 mL of unfiltered ice water. α-hexachlorocyclohexane, DDTs, chlorinated biphenyl congeners 28, 101 and 118 and brominated diphenyl ethers congeners 47 and 99 were detected in ice cores at levels between 0.5 to 258 pg/L. We emphasise the advantages and disadvantages of in situ SBSE in comparison with traditional extraction techniques used to analyze POPs in ice.