H.J. Annegarn

Proton microprobe and X-ray fluorescence investigations of nickel distribution in serpentine flora from South Africa

Abstract Certain plant species growing on serpentinite soils are hyperaccumulative of Ni. The ability to tolerate high Ni levels may have useful environmental and economic implications. However, the processes of Ni accumulation and tolerance are not well understood. The proton microprobe of the Schonland Research Centre was used in the PIXE mode to map the lateral and cross-sectional distribution of Ni and other elements in the tissue of species from the family Asteraceae, growing on serpentine outcrops in the Barberton district, south-eastern Transvaal. Elemental maps showed that the highest Ni enrichment was in the epidermis. Energy dispersive XRF fluorescence analysis was used for qualitative rapid scanning to select suitable metal-rich plants and for quantitative bulk analyses.

Lower tropospheric aerosol loadings over South Africa: The relative contribution of aeolian dust, industrial emissions, and biomass burning

The southern African haze layer is a ubiquitous subcontinental-scale feature of the lower atmosphere that extends to a depth of ∼5 km(∼500 hPa level) on non rain days, particularly in winter. Aerosols derived from biomass burning are commonly thought to contribute substantially to the total background aerosol loading within the layer. It is shown that in both summer and winter this supposition is without foundation over South Africa. Summer and winter aerosol loadings are derived from gravimetric analysis of stacked filter units and from proton-induced X ray emission (PIXE) analysis of one to four hourly resolved streaker samples. From concentrations of eleven inorganic elements, apportionment into four primary sources, biomass burning particulates, aeolian dust, industrial sulphur aerosols, and marine aerosols, has been effected. It is shown that the background biomass burning component of the total aerosol loading over South Africa in general, and within the plume of material being recirculated over South Africa and from there exported from the subcontinent south of 22°S to the Indian Ocean in particular, is minimal in both summer and winter. Except over coastal and adjacent inland areas, marine aerosols likewise make up a small fraction of the total loading. This is particularly so over the inland plateau areas. Crustally-derived aeolian dust and industrially-produced sulphur aerosols are demonstrated to be the major summer and winter constituents of the haze layer over South Africa and the particulate material being transported to the Indian Ocean region. Sulphur is transported within the aerosol plume exiting southern Africa to the Indian Ocean as agglomerates on aeolian dust nuclei.

Light volatiles in diamond: Physical interpretation and genetic significance

Abstract Natural diamond is characterised in terms of features in the infra-red and ultra-violet spectra. Additionally electron spin resonance, X-ray diffraction and topography, cathodoluminescence, mechanical and electrical measurements have been used to give more detail to such specification. It had been concluded that the major impurity in diamond was nitrogen and hence most physical phenomena have been interpreted as a manifestation of the mode(s) of occurrence of nitrogen. From neutron activation analysis studies some 58 elements have been identified in diamond, many of course at trace levels. It has been shown that these data reveal a distinctive trace and minor element chemistry for diamond. Recently ion beam analyses have quantified the role of nitrogen in diamond characterisation. Most recently ion beam analysis has revealed that hydrogen, nitrogen and oxygen are all major impurities in diamond. Quantitative studies have been made using (19F, α), (α, n) and (3He, p) reactions. High temperature annealing in ultra-high vacuum conditions results in a substantial increase in the hydrogen measured as well as in the shape of the depth profile. Hydrogen is released from defect centres and diffuses rapidly through the diamond. Some of these hydrogen atoms are trapped at defect sites which are concentrated near surface as a result of the ion beam bombardment. A lesser response to the annealing treatment is found for oxygen and the smallest change for nitrogen. These ion beam data lend independent support to our earlier interpretation of the neutron activation data that all diamonds contain defects distributed fairly uniformly and consisting of sub-microscopic inclusions, the elemental composition of which suggests that each is a magma droplet from the upper mantle in which the diamond crystallized. The water-richness of the magma is an essential feature of the diamond genesis conditions.

Source profiles by unique ratios (SPUR) analysis: Determination of source profiles from receptor-site streaker samples

A streaker total filter particulate sampler was operated for three weeks at an urban site in Milan, Italy. The filters were analysed by Particle Induced X-ray Emission (PIXE), yielding hourly concentrations of 15 elements. The data are used to extract source elemental profiles using a new method, SPUR (Source Profiles by Unique Ratios). The SPUR technique is a combination of event identification using unique elemental ratios in sources, and correction for background events by identifying events of differing time constants in the time domain. The elemental ratios are identified in plots of log([S]/[T])vs[T], referred to as SPUR plots, where T is a (non-unique) tracer and [S] is an element establishing the unique ratio. Using the SPUR technique, eight distinct sources are identified and profiles established. The sources are: two metallurgical smelters, two crustal sources, a potassium-rich source, automotive, regional crustal and regional sulphur. Results are compared with source profiles derived from Absolute Principal Component Scores analysis. SPUR analysis demonstrates powerful capability for deriving source profiles from receptor samples, including having the capability of distinguishing between sources of similar composition without using a unique tracer element.

Background aerosol composition in the namib desert, South West Africa (Namibia)

Abstract A remote site in the Namib Desert was selected for sampling background aerosols in southern Africa, as one of a wide network of stations spanning the Southern Hemisphere in a programme designed to measure the background concentrations of trace elements in the atmosphere. A series of samples was collected over a 6-month period using a single-orifice cascade impactor, which fractionated the particles into six size groups. Analysis was performed using particle-induced X-ray emission (PIXE), yielding results for S, Cl, K, Ca, Ti, Mn, Fe, Br and Sr, and occasionally also for V, Cr, Ni, Cu, Zn and Pb. No direct correlations with wind direction were observed excluding strong local or regional sources of particles. K, Ca, Ti, Mn and Fe can be identified with a dust dispersion source. Cl, large particle S and Br, and part of the K and Sr are derived from sea spray. Relative to the soil components small particle K is not enriched as it normally is in regions with less scarce vegetation. Cr, V, Ni, Cu, Zn and Pb concentrations and enrichments in the aerosol are lower than practically all values measured at any other location hitherto. The concentration of the small particle sulphur, 200 ng m−3, is believed to be related to anaerobic conditions and plankton blooms in the ocean upwelling zones off Namibia.

A seasonal air transport climatology for Kenya

A climatology of air transport to and from Kenya has been developed using kinematic trajectory modeling. Significant months for trajectory analysis have been determined from a classification of synoptic circulation fields. Five-point back and forward trajectory clusters to and from Kenya reveal that the transport corridors to Kenya are clearly bounded and well defined. Air reaching the country originates mainly from the Saharan region and northwestern Indian Ocean of the Arabian Sea in the Northern Hemisphere and from the Madagascan region of the Indian Ocean in the Southern Hemisphere. Transport from each of these source regions show distinctive annual cycles related to the northeasterly Asian monsoon and the southeasterly trade wind maximum over Kenya in May. The Saharan transport in the lower troposphere is at a maximum when the subtropical high over northern Africa is strongly developed in the boreal winter. Air reaching Kenya between 700 and 500 hPa is mainly from Sahara and northwest Indian Ocean in the months of January and March, which gives way to southwest Indian Ocean flow in May and November. In contrast, air reaching Kenya at 400 hPa is mainly from southwest Indian Ocean in January and March, which is replaced by Saharan transport in May and November. Transport of air from Kenya is invariant, both spatially and temporally, in the tropical easterlies to the Congo Basin and Atlantic Ocean in comparison to the transport to the country. Recirculation of air has also been observed but on a limited and often local scale and not to the extent reported in southern Africa.

Algorithm for fitting XRF, SEM and PIXE X-ray spectra backgrounds

Abstract Existing background fitting of energy dispersive X-ray spectra (X-ray, electron or proton excited) algorithms (e.g. parabolas or polynomials) are not universally applicable. Various limitations exist tying each algorithm to specific spectral shapes. This project aimed to find a generic algorithm which could reliably fit background independent of X-ray spectra source and form. A frequency differentiated non-linear digital filter “rolling ball” was chosen as a promising possibility. The algorithm is based on a square wave with an energy variable width as the structuring function, operated on by a gray scale morphological transformation. A wide range of spectra types have been successfully fitted. This algorithm behaves equivalently to traditional polynomial backgrounds in simple spectra e.g. PIXE aerosol spectra with funny filter, and is considerably more robust for multiple overlapping peaks, rapidly varying backgrounds, and is independent of X-ray energy filter or excitation mode.

PIXE analysis of caries related trace elements in tooth enamel

Abstract PIXE analysis has been applied to a set of twenty human teeth to determine trace element concentration in enamel from areas susceptible to dental caries (mesial and distal contact points) and in areas less susceptible to the disease (buccal surfaces), with the aim of determining the possible roles of trace elements in the curious process. The samples were caries-free anterior incisors extracted for periodontal reasons from subjects 10–30 years of age. Prior to extraction of the sample teeth, a detailed dental history and examination was carried out in each individual. PIXE analysis, using a 3 MeV proton beam of 1 mm diameter, allowed the determination of Ca, Mn, Fe, Cu, Zn, Sr and Pb above detection limits. As demonstrated in this work, the enhanced sensitivity of PIXE analysis over electron microprobe analysis, and the capability of localised surface analysis compared with the pooled samples required for neutron activation analysis, makes it a powerful and useful technique in dental analysis.

Combined application of INAA and PIXE for studying the regional aerosol composition in Southern Africa

As part of the SAFARI-92 biomass buming experiment, aerosol collections were carried out with several size-fractionating sampling devices at a number of sites in Southern Africa. One of the samplers used at all ground-based sites was a stacked filter unit (SFU). The SFU samples were analyzed by both INAA and PIXE analysis. The present paper gives an intercomparison of the analytical results obtained in order to assess the accuracy and to check the quality assurance of the analytical procedures. Twenty-one common elements were determined by both INAA and PIXE. Concentrations of 13 elements (i.e., Na, Mg, Al, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Zn and Br) were generally measured with sufficient precision in both techniques for performing the intercomparison. The INAA and PIXE data were compared in terms of PIXE/INAA concentration ratios on a sample by sample basis for the coarse and fine size fraction separately. the atmospheric concentrations for K, Mn and Fe agreed within 5–10%, the agreement between the data for the other common elements was typically better than 15%. Possible explanations for lower than 1.0 ratios for Cl, Br and Na are presented. The common elements were classified into groups according to their detectability and sensitivity in each technique.

Aerosol-soil fractionation for Namib Desert samples

Abstract Four soil samples, collected in the central Namib Desert, were fractionated by dry sieving and aerosol generation into 16 size fractions in the range 0.15–300 μm diameter. The mass-size function of each soil and the dust (mineral aerosol) generated from the soil were studied. Due to the preferential lifting of smaller soil particles by the air stream, the soil underwent strong physical fractionation resulting in the bulk of the dust being found in the range of 1.3–10.3 μm, whereas the bulk of the soil was found in the range 63–300 μm. The concentrations of 11 elements in eight soil size fractions (from 300 μm) obtained by dry sieving were measured by X-ray fluorescence analysis while the concentration for these elements in eight size ranges (from 10.3 μm) obtained by aerosol generation were determined by particle-induced X-ray emission. The concentrations of the elements Al, Si, K, Rb and Sr were found to vary by less than a factor of two throughout the particle size range studied. However, the concentration of the elements Ca, Ti, Mn, Fe, Y and Zr increased when the particle size decreased below 150 μm to reach a maximum around 63-45 μm and then to decrease. The concentrations of the elements in the generated aerosol particles were found to be more similar to those in the bulk soil than any particular size fraction. For the aerosol size fraction, elemental enrichment factors were calculated with respect to the composition of average crustal rock, average soil, the bulk Namib soil and the small size fraction of the Namib soil. For several elements, the enrichment factors varied quite significantly, depending on the choice of the reference material. The elemental ratios in the mineral aerosol were also compared to those in the atmospheric aerosol from the Namib Desert. It was confirmed that there is a marine contribution for S, Cl and Sr in the Namib natural aerosol. The composition of the mineral aerosol generated in this study should be useful in source apportionment studies for the Namib Desert and sorrounding regions.