Abstract: River sediments from all of the major drainage basins (except the Indus) in the Indian sub-continent were collected and analysed by thin-film X-ray fluorescence technique (XRF) to determine their chemical composition. On the basis of analysis of more than 120 samples, average chemical compositions of river-borne sediments from the Indian sub-continent have been calculated. Also, average concentration values for sediments from each of the river basins, and the sub-continent average and the inter-basin differences are discussed in relation to weathering processes in the drainage basins. Comparisons have been made with the chemistry of sediments from the Bay of Bengal (which receives the bulk of sediments delivered by Indian rivers). Our observations are discussed in the light of average chemical composition of world-river sediments and the world surface rock exposed for continental weathering.

Abstract: A laser microprobe mass analyser and a highly automated electron probe X-ray microanalysis unit have been used to study the elemental composition, inorganic speciation and morphology of atmospheric aerosols collected at various remote to polluted and marine to continental locations.

Abstract: The methodology of direct hair analysis by energy-dispersive x-ray fluorescence was studied. The effect on the XRF result of having a non-homogeneous radial distribution of the analyte in a single hair strand and the macroscopic effects in a bundle of hairs were calculated to evaluate possible systematic errors. The detection limits were mapped as a function of the target thickness and surface fraction. It appeared that a 10 mg cm−2 sample thickness, i. e. a target with about four layers of hair strands, is recommended. The standard deviation of this simple direct analytical method is 619% for some important elements. Discrepancies with neutron activation analysis had a mean value of around 15%. About twelve elements can be determined simultaneously on a routine basis.

Abstract: Four decomposition procedures frequently used for biological material (dry ashing, open wet digestion, wet digestion in a teflon bomb and low-temperature ashing) are optimized for the conversion of biological samples to conducting electrodes suitable for multi-element trace determinations by spark-source mass spectrometry or emission spectrometry. The optimized procedures are evaluated with respect to contamination, retention and preconcentration of the trace elements, homogeneity of the electrodes and precision of the final results. Both dry-ashing methods are prone to losses by volatilization; simple dry ashing suffers from contamination problems during electrode preparation. Wet digestion gives better precision; digestion with nitric/sulfuric acids in an open flask is the method of choice for most elements being simpler and giving lower blanks than the bomb method.

Abstract: An investigation was made to determine the influence of the dumping of a 1000 ton day−1, on the average, of acid-iron waste from the titanium dioxide industry into the shallow but turbulent Southern Bight of the North Sea. This waste contains some 20% sulfuric acid and 2% iron. After the passage of the barge that discharges 10 ton of waste min−1 into its wake, the vertical and horizontal distributions of the pH, iron-concentration and turbidity were measured as a function of time. It appeared that a few seconds after the discharge and for a very brief period, the pH was down to approx. 4 and the Fe-concentration was 13 mg l−1. More than 1 min after the discharge a pH below 6 and an iron-level above 3 mg l−1 could not be detected anywhere. The measured factor for waste dilution by sea water, based on the observed acid and iron concentration in the waste and in the discharge track, were around 5000 after 5 min, 9000 after 10 min and 80,000 after 20 min. Before and long after the dumping, the total iron-concentration in this Southern Bight area was around 100 μg l−1, but this high level might be due to natural causes.

Abstract: The rate of iron(II) oxidation in North Sea water of pH 5.510 in the range 1025°C has been studied. The oxygenation rate depends linearly on the iron(II) and dissolved oxygen concentrations. The second-order dependence on [OH−], found by several investigators for synthetic solutions, was confirmed in seawater, but only for pOH > 6.9. For pOH < 5.9 the rate appeared to be independent of the pOH. In the intermediate range, pOH 5.96.9, corresponding to the natural pH of seawater, a first-order dependence on the pOH is obeyed. The important discrepancy in the literature between the second-order rate constant for NaCHO3 solutions and for seawater can be attributed predominantly to the incorrect assumption of a second-order pOH dependence in natural seawater. The results can be useful, for example, in predicting the effect of dumping acidic iron waste from the titanium-dioxide industry into the ocean.

Abstract: Laser Microprobe Mass Spectrometry (LAMMA) is used to examine micrometric particles of calcium oxyanion salts (CaCO3, CaSO4, CaSO4·2H2O) and calcium oxide, in both the positive and negative ion mode. The major molecular ions, appearing in the positive mass spectrum, can be divided into three series, namely CamOm-1+, (CaO)m+ and (CaO)mH+ (m = 1-4). In the case of the former two series the relative intensities of the mass peaks as a function of the fragment valence K = (1 + 2n)/m, for CamOn+, can be fitted to a Gaussian distribution curve, as was earlier demonstrated for secondary ion mass spectrometry. The high stability of the (CaO)mH+ series can be explained by the favourable fragment valence of +2 corresponding to the usual oxidation state of calcium.

Abstract: By using a polyester sailboat as sampling platform, a series of duplicate aerosol samples was collected by cascade impactors on a trip from Panama to Tahiti in 1979. Elemental analysis mainly by particle-induced X ray emission (PIXE) indicated, in the samples collected between Panama and the Galapagos Islands, the presence of a substantial crustal component (∼0.4 μg/m3), fine Cu (∼0.4 ng/m3) and Zn (∼0.6 ng/m3), and excess fine S and K (∼100 and ∼2.4 ng/m3, respectively) in addition to the major sea salt elements. The crustal component and fine Cu and Zn are suggested to result from natural continental sources (i.e., eolian dust transport from the American continents and perhaps geothermal emissions). Samples collected west of the Galapagos Islands in the southern trades showed significantly lower concentrations for the nonseawater components. The average Si and Fe levels were as low as 4.8 and 3.3 ng/m3, corresponding to a maximum of 0.066 μg/m3 for an assumed mineral dust component, whereas heavy metal concentrations were all below the detection limits (typically ranging from 0.05 to 0.15 ng/m3 for V, Cr, Mn, Ni, Cu, Zn, and Se). Excess fine S decreased to a mean of 46 ng/m3, a level similar to those reported for other remote marine and continental locations. This all indicates that the marine atmosphere west of the Galapagos was little influenced by natural continental source processes or by anthropogenic emissions. Under these truly marine conditions, several concentration ratios of the major seawater elements were significantly different from those in bulk seawater. Ca, Sr, and S in >1 μm diameter particles were enriched relative to K and Na, with the enrichment being substantially more pronounced (up to 50% or higher) for l4-μm diameter particles than for particles >4 μm. Comparison of these data with a similar data set from samples collected over the Atlantic indicates that the departures from seawater composition are significantly larger for the Pacific. Differences in sea-to-air fractionation processes, probably involving binding of divalent cations to organic matter in the oceanic surface microlayer, are suggested as being responsible for these observations.

Abstract: Selenium is determined in the ng g−1 to μg g−1 range in biological and environmental samples. A wet digestion procedure was optimized with respect to volatility losses and recovery yields, by using 75Se metabolically incorporated into rat organs. Selenium is preconcentrated from the digestion liquid by a two-step reduction with 4 M HCl and ascorbic acid. The colloidal selenium formed is adsorbed on activated carbon and filtered on a Nucleopore membrane for measurement by energy-dispersive x-ray fluorescence. Almost complete recovery was obtained, and the detection limit was 20 ng, corresponding to 10 ng g−1 for a 2-g sample. Biological reference materials were analyzed with satisfactory results, and the accuracy of the method was good.

Abstract: All published procedures for multi-element preconcentration of trace elements, prior to x-ray fluorescence analysis of water, are reviewed and critically evaluated. Most preconcentration methods applied to the determination of single elements in water are also listed.