PIXE investigation of aerosol composition over the Zambian Copperbelt

Atmospheric sulphate aerosol concentrations are of interest in climate change studies because of their negative climate forcing potential. Quantification of their forcing strength requires the compilation of global sulphur emission inventories to determine the magnitude of regional sources. We report on measurements of the ambient aerosol concentrations in proximity to a copper refinery in the central African Copperbelt, along the border of Zambia and the Democratic Republic of the Congo. This region is historically regarded as one of the largest African sources of sulphate aerosols. Sulphate is produced by oxidation in the atmosphere of SO₂ emitted during the pyrometallurgical processing of Cu–Co sulphide ores. Since the last quantification of sulphur emissions (late 1960s), there has been large-scale reduction in copper production and more frequent use of the leaching technique with negligible sulphur emissions.

Samples were collected over four weeks, November–December 1996, at Kitwe, Zambia. A low volume two-stage time-resolving aerosol sampler (streaker) was used. Coarse and fine mode aerosols were separated at >2.5 and >10 μmad. Hourly elemental concentrations were determined by 3.2 MeV PIXE, and routinely yielded Si, S, K, Ca, Ti, Mn, Fe, Cu and Zn, above detection limits. Si, K, Ca and Fe (major crustal components) dominated the coarse elemental mass. In the fine stage, S and Si accounted for up to 80% of the measured mass, and S alone up to 60%. Time series analysis allowed the division of sulphur and crustal elements (Si, K, Ca, Fe) between (i) background concentrations representative of synoptic scale air masses; and (ii) contributions from local sources, i.e., copper smelter and re-suspended soil dust. Short duration episodes of S concentrations, up to 26 μg/m³, were found simultaneously with enhanced Cu, Fe and Zn. Contributions from individual pyrometallurgic processes and the cobalt slag dump could be distinguished from the elemental signatures. Periods of diminished sulphur concentrations were also identified, indicating a well-mixed regional air mass. These results will contribute towards validating global climate model predictions of aerosol forcing over central Africa.     

Study of particulate emissions near a steel plant in Genova by continuous sampling and PIXE hourly analysis

The particulate emissions near a large steel plant located in a densely inhabited suburb of the town of Genova (Italy) have been studied for a period of six months. We have used two-stage continuous streaker samplers and subsequent PIXE analysis with hourly resolution, to follow both seasonal and daily trends. The first streaker sampler remained installed very close to the plant cokery and furnaces, while another sampler was moved to different locations. Samples have been analysed by PIXE, deducing concentrations for elements from Na to Pb. During part of the campaign, the aerosol fractions with aerodynamic diameter (D_ae) < 2.5 μm (fine fraction) and with 2.5 < D_ae < 10 μm (coarse fraction) have been separately collected. We have measured and analysed about 8500 PIXE spectra: the steel plant emissions have been identified to some extent and resolved from other aerosol sources.     

Analysis of atmospheric aerosols by PIXE: the importance of real time and complementary measurements

Particle-Induced X-ray Emission (PIXE) has been used for more than 30 yr in many urban and background air pollution studies. The technique has certainly contributed to the understanding of source-receptor relationship for aerosol particles as well as to aerosol physics and chemistry. In the last few years, where aerosol issues were strongly linked to global climate change through the relationship between aerosol and atmospheric radiation points to new challenges in atmospheric sciences, where PIXE could play an important role. Also the recognition for the inter-relationship between aerosol and liquid and gas phases in the atmosphere makes important to integrate PIXE aerosol analysis with other complementary measurements. The use of Nephelometers and Aethalometers to measure scattering and absorption of radiation by aerosol particles can be done in parallel with particle filter collection for PIXE analysis. Parallel measurements of trace gases using traditional monitors as well as with new techniques such as Differential Optical Absorption Spectroscopy (DOAS) that can provide concentration of O₃, SO₂, NO₃, NO₂, HCHO, HNO₃, Benzene, Toluene, and Xylene, is also important for both urban and remote aerosol studies. They provide information that allows a much richer interpretation of PIXE data. Recently developed instruments that provide real time aerosol data such as the Tapered Element Oscillating Microbalance (TEOM) PM₁₀ monitor and automatic real time organic and elemental carbon analyzers provide extremely useful data to complement PIXE aerosol analysis. The concentrations of trace elements measured by PIXE comprise only 10–30% of the aerosol mass, leaving the organic aerosol characterization and measurement with an important role. The aerosol source apportionment provided by PIXE analysis can be extended with other aerosol measurements such as scattering and absorption, estimating for example, the radiative impact of each discriminated aerosol source. The aerosol bulk PIXE measurements can be complemented with soluble concentrations provided by Ion Chromatography (IC) and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). Recent developments in remote sensing techniques and products also enhance significantly regional aerosol studies. Three-dimensional air mass trajectories should be integrated in aerosol studies for urban and remote areas. The applications of these techniques to study urban aerosols from São Paulo and Santiago de Chile have broadened extensively the scientific scope of these studies.     

Identification and characterization of fine and coarse particulate matter sources in a middle-European urban environment

In this work a source apportionment study is presented which aimed to characterize the PM_2.5 and PM_2.5–10 sources in the urban area of Debrecen, East-Hungary by using streaker samples, IBA methods and positive matrix factorization (PMF) analysis.Samples of fine (PM_2.5) and coarse (PM_2.5–10) urban particulate matter were collected with 2 h time resolution in the frame of five sampling campaigns during 2007–2009 in different seasons in the downtown of Debrecen.Elemental concentrations from Al to Pb of over 1000 samples were obtained by particle induced X-ray emission (PIXE); concentrations of black carbon (BC) were determined with a smoke stain reflectometer. On this data base source apportionment was carried out by using the PMF method.Seven factors were identified for both size fractions, including soil dust, traffic, secondary aerosol – sulphates, domestic heating, oil combustion, agriculture and an unknown factor enriched with chlorine. Seasonal and daily variation of the different factors was studied as well as their dependence on meteorological parameters.Besides determining the time patterns characteristic to the city, several emission episodes were identified including a Saharan dust intrusion on 21st–24th May, 2008.     

Low energy nitrogen ion doping into GaAs using combined ion-beam and molecular-beam epitaxy method

Low energy nitrogen (N) ions were irradiated during the epitaxial growth of GaAs using combined ion beam and molecular beam epitaxy (CIBMBE) method as a function of N⁺ ion acceleration energy (E_a) and N⁺ ion beam current density (I_N). E_a was varied from 70 to 170 eV I_N from 900 pA/cm² to 75 nA/cm². GaAs growth rate was fixed to 1 μm/h. In 2 K photoluminescence (PL) spectra of the samples with I_N = 3 nA/cm² and E_a = 70–100 eV, two sharp emissions at 1.508 eV (X₁) and 1.495 eV (X₂), which have been attributed to the emissions of excitons bound to isolated N atoms, and another one at 1.443 eV (X₅) were observed. These results show that nitrogen (N) atom in GaAs becomes optically active as an isoelectronic impurity at least in as-grown condition. For N⁺ ion-irradiated samples with rather high I_N, e.g., with I_N = 75 nA/cm² and E_a = 100 eV, a broad emission together with multiple sharp ones were observed after furnace annealing at 750°C which were ascribed to emissions of excitons bound to nitrogen-nitrogen (N---N) pairs.     

Measurement of the H2-D mass difference with a nuclear microprobe

A 1.24 MeV deuteron (D) beam mixed with a H₂ molecular beam was separated with a microslit system of a nuclear microprobe consisting of a 100 μm diameter object and a 1 mm diameter aperture diaphragm. D was distinguished from H₂ by Rutherford backscattering (RBS) on a thin Au film. By slightly changing the magnetic field strength of the beam steerer installed in front of the object diaphragm, the maximum and the minimum RBS D/H₂ ratios were found to be 50.3 and 1.5, respectively. M/ΔM = 3.9 × 10³ was obtained as the mass resolution of the nuclear microprobe. The transmission of this system was 2 × 10⁻³.     

Research of Si and GaAs diode structures by Ion Beam Induced Charge (IBIC) collection

A Si pn junction diode and a GaAs Schottky diode were prepared for studying the basic mechanism of charge collection followed by high energy charged particle incidence in order to improve the resistance against single event upset. A 2 μm wide and 20 μm long rectangular Al electrode attached to a circular Al electrode with a 50 μm diameter was made on a 2.5 μm thick epilayer (minority carrier density 2 × 10¹⁵ /cm³). Both a Schottky electrode of Al (5 μm × 110 μm) and two ohmic electrodes of AuGe/Ni (110 μm × 110 μm) were made on a 2 μm thick epilayer (7.3 × 10¹⁵ /cm³) grown on a semi insulator GaAs substrate (1 × 10⁷ Ω cm). The internal device structure was examined by the IBIC (Ion Beam Induced Charge) method using a 2 MeV He⁺ ion microbeam. IBIC images clearly show an Al electrode, the SiO₂, and an epilayer. These results were then used to improve the qualities of the test diodes.     

用碳稳定同位素估算大气细颗粒物中多环芳烃的来源

建立了用碳稳定同位素比估算大气颗粒物中多环芳烃（PAHs）的方法,该方法包括二氯甲烷提取、薄层色谱纯化和气相色谱-燃烧系统-同位素质谱测定碳稳定同位素组成(δ¹³C);并用该方法对上海市大气颗粒物PM_2.5中PAHs的来源进行估算。结果表明:采样点PM_2.5中PAHs的δ¹³C值随着分子量的增加而减小;与潜在污染源中相应值相比,更接近于燃煤和生物质燃烧的相应值,表明采样点处PM_2.5中的PAHs受燃煤和生物质燃烧的影响大于机动车尾气。PAHs来自燃煤、机动车尾气和生物质的贡献分别为3%-21%、29%-33%和46%-67%。这一结果与采样点的特殊环境一致,表明碳稳定同位素比能够定量估算大气细颗粒物中PAHs的来源。     

Use of the nuclear microprobe at the University of Arizona for the study of heavy metal deposition in rabbit renal tissue

Industrial wastes consigned to disposal sites frequently contain substantial amounts of heavy metals. We have successfully applied proton induced X-ray emission analysis (PIXE) in the conduct of heavy metal (Hg, Cd, Cr, As) toxicity studies using precision cut rabbit renal cortical slices. The large beam diameter (4000 μm) of the proton macroprobe at The University of Arizona Ion Beam Analysis facility allowed an overall concentration of the metal(s) of interest in the samples to be determined, but lacked the ability to resolve point concentrations in the tissue. The ability to locate these areas has now been made available to us with the addition of a rastering microprobe (μ-PIXE) to the facility. Studies now being conducted in our laboratory using this micro-technique include analysis of renal tissue taken from rabbits injected intraperitoneally with HgCl₂, K₂Cr₂O₇, and NaAsO₂. The small beam size (3 μm) and the ability to raster this beam over areas of up to 125 μm × 125 μm has allowed regional mapping of endogenous and non-endogenous metal concentrations and revealed trends in heavy metal deposition in in vivo treated renal tissue, significantly increasing the amount of information obtained from these animal studies using PIXE alone. The combination of small beam size, high resolution, and multi-element detection makes μ-PIXE a powerful tool for investigating the impact of non-endogenous metals on the kidney.     

Investigation of metal matrix systems for cosmogenic Al analysis by accelerator mass spectrometry

We report experiments designed to help optimize accelerator mass spectrometry (AMS) of ²⁶Al (in the form of Al₂O₃) for geochronologic and geomorphologic applications. Analysis times are long and the precision of AMS are restricted by counting statistics for ²⁶Al, which are in turn limited by the intensity of Al⁻ beam currents. We show that ion beam currents are affected by the metal matrix in which Al₂O₃ is dispersed, by the matrix-to-Al₂O₃ mixing ratio, and for at least some matrices, such as Ag, by the depth to which the sample is packed in the AMS cathode. Typical instantaneous Al⁺⁷ currents (μA) produced by the LLNL CAMS Cs sputter ion source and measured in a Faraday cup after the accelerator are 2.26 for samples in Ag, 2.17 in Re, 2.00 in Nb, 1.92 in V and 1.73 in Mo. The AMS counting efficiency (Al⁻ ions detected per Al atom loaded in the target) for a constant analysis time (900 s) and for equimolar mixtures of Al₂O₃ and matrix is in the range of 6 × 10⁻⁵–9 × 10⁻⁵ in the order Ag > Re > Nb > V > Mo. Additionally, we observed a correlation between the ion detection efficiency (Al ions detected per Al atoms loaded) and the matrix work function and inverse vaporization enthalpy of the matrix and beam current. Typical currents (μA) obtained with elemental Al are 13.3 for samples in no matrix, 3.23 in V, 3.14 in Nb, 3.07 in Re, 2.85 in Mo, 1.46 in Ag. The ion detection efficiency for elemental Al correlates strongly with matrix electron affinity. Thus, our data indicate that the current practice of mixing Al₂O₃ with Ag is reasonable until a means is found to produce cathodes of elemental Al.     

Isomer separation of Cu and Cu with a resonance ionization laser ion source

Radioactive copper isotopes were ionized with the resonance ionization laser ion source (RILIS) at the on-line isotope separator ISOLDE (CERN). Using the different hyperfine structure in the 3d¹⁰ 4s  ²S_1/2 – 3d¹⁰ 4p  ²P⁰_1/2 transition the low- and high-spin isomers of ⁷⁰Cu were selectively enhanced by tuning the laser wavelength. The light was provided by a narrow-bandwidth dye laser pumped by copper vapor lasers (CVL) and frequency doubled in a BBO crystal. The ground state to isomeric state intensity ratio could be varied by a factor of 30, allowing to assign gamma transitions unambiguously to the decay of the individual isomers. It is shown that the method can also be used to determine magnetic moments. In a first experiment for the 1⁺ ground state of ⁷⁰Cu a magnetic moment of (+)1.8(3) μ_N and for the high-spin isomer of ⁷⁰Cu a magnetic moment of (±)1.2(3) μ_N could be deduced.     

Manganese survey in airborne particulate matter from a mining area at Hidalgo State, Mexico

A manganese (Mn) survey in airborne particulate matter from a mining area located in Hidalgo State (Mexico) was performed using PIXE. Deposits of Mn ore, first discovered in 1959 and under continuous exploitation since 1962, are nowadays considered as one of the most important of their kind in the American Continent. Afterwards, local inhabitants have been under continuous overexposure to dusts and water highly enriched with Mn. Since no information was available about Mn content in airborne particulate matter in that area, especially in the respirable fraction PM_2.5, airborne particles were collected simultaneously at two sites located on opposite sides of the rim of the mining valley, and along the line of prevailing local winds. The sample collection was performed on eight alternate days, taking two samples per day (day-time and night-time) at each sampling site, using Stacked Filter Units (SFUs) of the Davis design to separate particles into fine (PM_2.5) and coarse (PM₁₅) sizes. The samples were PIXE analyzed and the results of this study revealed that Mn content, in both fine and coarse fractions, were in excess of the general urban background level of 40 ng/m³ (US Environmental Protection Agency, 1990) in more than 50% of the samples, which indicate severe environmental deterioration in the place under study.     

Interactions of slow H, H2, and H3 with thin carbon foils

Interaction processes resulting from the transit of incident 2–30 keV H⁺, H⁺₂ and H⁺₃ through 1.2 to 2.5 μg cm⁻² carbon foils are investigated by examining the charge state and angular scatter distributions of atomic and molecular species that exit the foils. A comparison of the scatter distributions of exiting H⁺₂ and H⁰ from incident H⁺₂ and H⁺₃ show that the atomic components of transmitted molecules scatter independently from foil atoms. For a given foil thickness, the measured fractions of H⁺₂ from incident H⁺₂ and H⁺₃ are inversely proportional to the square of the angular scatter half-width.     

Reactive ion etching of PECVD silicon nitride in SF6 plasma

The reactive ion etching of PECVD silicon nitride thin films has been investigated using SF₆ plasma. Effects of variations of process parameters such as pressure (50–350 mTorr), RF power (50–250 W), gas flow rate (3–130 sccm) and additions of O₂ and He (0–50%) in SF₆, on the PECVD silicon nitride etch rate and selectivity to the AZ 1350J photoresist were examined. An etch rate of 1 μm/min has been obtained under the condition of 150 mTorr, 100 W and 60 sccm. Experimental results also indicated a maximum etch rate at approximately 30% O₂ while addition of He showed only dilution effect. A nitride/photoresist selectivity ranging from 1 to 3:1 has been obtained.     

Thermochemical study of vaporization of LiTiO by a mass spectrometric Knudsen effusion method

The vaporization of Li₄TiO₄ has been studied by a mass spectrometric Knudsen effusion method in the temperature range 1082–1582 K. Identified vapors are Li(g), LiO(g), Li₂O(g) and Li₃O(g). When the vaporization proceeds, the content of Li₂O in the Li₄TiO₄ sample decreases and the condensed phase of the sample changes to β-Li₄TiO₄ plus l-Li₂TiO₃ below 1323 K, to β-Li₄TiO₄ plus h-Li₂TiO₃ in the range 1323–1473 K and to h-Li₂TiO₃ plus liquid above 1473 K. On the basis of the partial pressure data, the enthalpies of formation for β-Li₄TiO₄ from elements and from constituent oxides have been determined to be ΔH_f,298^°(β-Li₄TiO₄,s) = −2247.8 ± 14.3 kJ mol⁻¹ and Δ_fox,298^°(β-Li₄TiO₄, s) = −107.3 ± 14.3 kJ mol⁻¹, respectively.     

Analysis of Cu and O in high-Tc superconductors by 7–9 MeV protons

The use of proton-induced γ-ray emission for the simultaneous analysis of Cu and O in high-T_c superconductors is demonstrated. Utilizing 7–9 MeV protons, the ratio of O relative to Cu can be determined reliably to a few percent accuracy in homogeneous bulk samples and films thicker than 130 μm using standard bulk samples of O and Cu. Results of the present method are compared with those of the analysis of YBa₂Cu₃O_7xdone by the Rutherford scattering of particles and the non-Rutherford scattering through the ¹⁶O(p,p₀)¹⁶O reaction.     

The interaction of iron with molten uranium

The rate of penetration of Armco iron by molten uranium, U-34 at % Fe eutectic and U-77 at % Fe eutectic was investigated in the range of 740 to 1300° C. This was done in an effort to understand the mode of penetration of uranium-base fuels through iron-base claddings. The phenomenon of particular interest was a penetration rate reversal, i.e. decreasing rate with increasing temperature, between 1150 and 1244° C.

Penetration rates at 1150° C were found to be 760 μm/sec in uranium, 690 μm/sec in U-34 at % Fe and 5.5 μm/sec in U-77 at % Fe. At 1244° C these rates changed to 150 μm/sec in uranium, 130 μm/sec in U-34 at % Fe and 5.7 μm/sec in U-77 at % Fe. The study showed that the penetration rate is related to the rate and mode of formation of UFe₂. The rate changes correlate well with the phases of the U-Fe equilibrium diagram.     

Detailed mass size distributions of atmospheric aerosol species in the Negev desert, Israel, during ARACHNE-96

As part of the 1996 summer intensive of the Aerosol, RAdiation and CHemistry Experiment (ARACHNE-96), the mass size distribution of various airborne particulate elements was studied at a remote site in the Negev Desert, Israel. Aerosol collections were made with 8-stage PIXE International cascade impactors (PCIs) and 12-stage small deposit area low pressure impactors (SDIs) and the samples were analyzed by PIXE for about 20 elements. The mineral elements (Al, Si, Ca, Ti, Fe) exhibited a unimodal size distribution which peaked at about 6 μm, but the contribution of particles larger than 10 μm was clearly more pronounced during the day than during night. Sulphur and Br had a tendency to exhibit two modes in the submicrometer size range, with diameters at about 0.3 and 0.6 μm, respectively. The elements V and Ni, which are indicators of residual fuel burning, showed essentially one fine mode (at 0.3 μm) in addition to a coarse mode which represented the mineral dust contribution. Overall, good agreement was observed between the mass size distributions from the PCI and SDI devices. The PCI was superior to the SDI for studying the size distribution in the coarse size range, but the SDI was clearly superior for unravelling the various modes in the submicrometer size range.     

Size-fractionated aerosol composition during an intensive 1997 summer field campaign in northern Finland

A 12-stage small deposit area low pressure impactor (SDI) was used to collect size-fractionated aerosol samples during an intensive 1997 summer field campaign in northern Finland. The samples were analyzed for over 20 elements by PIXE, and some “difficult” elements such as As and Se could be quantified. The sea-salt and crustal elements had essentially a unimodal coarse size distribution with geometric mean aerodynamic diameter (GMAD) of about 4–5 μm. In one third of the samples, S showed only one mode in the fine size range, with GMAD of 0.4–0.5 μm. In the other samples, this fine S mode broke up into two modes, with GMADs of 0.3 and 0.6 μm, respectively. V, Zn, As, Se and Pb were mainly present in a single submicrometer mode, with GMAD of 0.4–0.5 μm for V and Se, and slightly larger (i.e., 0.6 μm) for the other three elements. The highest concentrations of S, V, Ni, Cu, Zn, As, Se and Pb were encountered in the SDI sample which had been collected in the period 14–16 July. During this sampling, the air masses came in from the west, but had recirculated over northern Scandinavia and passed over the Kola peninsula.     

The formation of tritium permeation barriers by CVD

The effectiveness as permeation barriers of the following CVD coatings have been investigated: TiC (1 to 2 μm in thickness); a bi-layer of TiN on TiC (3 μm total thickness) and CVD A1₂O₃ on a TiN/TiC bi-layer. The substrate materials were TZM (a Mo alloy) and 316L stainless steel in the form of discs of diameter 48 mm and thickness 0.1 or 1 mm. Permeation measurements were performed in the temperature range 515–742 K using deuterium at pressures in the range 1–50 kPa. CVD layers were shown to form reasonably effective permeation barriers. At a temperature of 673 K TiC is around 6000 times less permeable to deuterium than 316L stainless steel.