Abstract: Gold-silver alloy nanoparticles display surface plasmon resonance (SPR) over a broad range of the UV-vis spectrum. We propose a model to predict the SPR wavelength of gold-silver alloy colloids based on the combined effect of alloy composition and particle size. The SPR wavelength is derived from extinction spectra simulated using available experimental dielectric constant data and accounts for particle size by applying Mie theory. Comparison of calculated values with experimental data evidences the accuracy of the model. The new SPR wavelength estimation tool will be of particular interest for developing dedicated bimetallic plasmonic nanostructures.

Abstract: An instrumental neutron activation method for V, Mn and W in alloy steels with a 241 Am/Be isotopic neutron source is described. The samples were irradiated to induce the nuclear reactions 51V(n, γ) 52V, 55Mn(n, γ)56Mn, and 186W(n, γ)187W. The activities were measured with a NaI(TI) detector. Interferences on the measured photopeaks were shown to be negligible by measuring the half-lives of 62V, 56Mn and 187W.These thre elementes were determined in the range 1.512.9% in special steels; manganese in the range 0.51.6% was measured in cast irons. Calibration was done by comparison with results from wet chemistry and x-ray fluorescence spectrometry. The processing times for the vanadium, manganese and tungsten determinations were 11 min, 3 h and 26.3 h, respectively, but these were reduced greatly by intoruding a scheme wherein six samples were simultaneously irradiated and the 56Mn and 187W nuclides were measured sequentially for a series of 66 samples. The average processing time was reduced to 45 min for tungsten with a precision of 4.0% and accuracy of 3.4% and 22.8 min for manganese with a precision of 3.8% and accuracy of 3.1%.

Abstract: Between 15 January and 26 February 1987, 51 fine and coarse mode aerosol samples were collected at the Universidad de Santiago de Chile Planetarium using a dichotomous sampler. The samples were analyzed by X-ray fluorescence for up to 17 elements (Mg, Al, Si, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br and Pb). Aerosol particles were individually studied by Electron Probe Microanalysis (EPMA) and Laser Microprobe Mass Analysis (LAMMA). The data set consisting of aerosol elemental concentrations and meteorological variables was subjected to Principal Factor Analysis (PFA), allowing the identification of six fine mode particle source classes (soil, industrial, sulfate particles, traffic, residual oil, wood-burnings), and five coarse mode particle source classes (soil, industrial, traffic, residual oil, sulfate particles). Both PFA solutions explained about 81 and 90% of the total variance in the data set, respectively. The regression of elemental mass concentrations on the Absolute Principal Factor Scores allowed the estimation of the contribution of the different source classes to the Santiago aerosol. Within the fine fraction, secondary SO42− particles were responsible for about 49% of the fine mode aerosol mass concentration, while 26, 13, 6.4 and 5.6% were attributed to wood-burning/car exhausts, residual oil combustion, soil dust/metallurgical, and soil dust/wood-burning releases, respectively. The coarse fraction source apportionment was mainly dominated by soil dust, accounting for 74% of the coarse mode aerosol mass concentration. A composite of soil dust and industrial release accounted for 13%; a composite of secondary sulfates contributed with 9%; a composite of soil dust and automotive emissions, and secondary sulfates were responsible for 4 and 0.03% of the coarse aerosol mass concentration, respectively. EPMA results are in satisfactory agreement with those from the bulk analysis and allowed the identification of eight particle types in both fine and coarse mode aerosols, pertaining to different source classes, namely soil, seaspray, secondary SO42−, metallurgical emissions and biomass burning release. EPMA also evidenced that one of the most abundant particle types corresponded to marine aerosol, having an average diameter of 0.7 μm for the fine mode and 2.2 μm for the coarse mode aerosol. LAMMA results indicate that, in fact, seaspray has been transported into the city of Santiago de Chile airshed, suffering several transformations and a sulfur enrichment. This analytical technique also provided evidence of the abundance of carbon-rich particles, which were not detected by either the bulk X-ray analysis or EPMA; they are probably due to fossil-fuel combustion releases.

Abstract: The ArmstrongBuseck correction for absorption effects in electron probe x-ray microanalysis of particles considers seven specific particle shapes, and for these geometries exact correction equations are used. This procedure implies that the analyst has to associate the particle to be analysed with a certain particle type; an arbitrary relative thickness is sometimes assumed. A theoretical study was made of this absorption correction as a function of the particle composition, type and thickness for micrometre-sized particles. It appears that a correct choice of the particle type is critical. However, when the analytical results are normalized to 100%, the differences between the models are much less pronounced, and it is justified to assume a spherical model in all cases.

Abstract: A semi-empirical approach is described for determining the mass per unit area of a sample being analysed. The method can be used to estimate the concentration of minor and trace elements in matrices containing a substantial amount of light elements. The procedure utilizes the coherently and incoherently scattered radiation induced in the sample by the filtered continuum radiation of a rhodium x-ray tube. The relationship between the intensity of the scattered radiation per unit mass and the average atomic number of the sample is established via calibration graphs, which can be applied for different x-ray tube voltages and for different primary beam filters. The overall procedure was validated by the analysis of several geological standards, deposited as thin slurries of unknown thickness either on Mylar foil or on Nuclepore filters.

Abstract: Adding 20mg of 1-(2-pyridylazo)-2-naphthol (PAN) to a water sample at 70°, and filtering off the precipitate after cooling, gives efficient preconcentration prior to X-ray fluorescence analysis of water. Up to the capacity of about 100 μeq of PAN used, the trace metal recoveries are around 90% or higher for Cr3+, Mn2+, Ni2+, Cu2+, Zn2+, Hg2+ and Eu3+, and above 70% for many other ions. The recovery yields usually do not vary critically with pH in the neutral pH-range, and are practically independent of the sample salinity, sample volume and trace-metal concentration. Enrichment factors as high as 2 × 105 can be achieved. Counting statistics would then allow detection limits of 0.03 ppM. The blank levels in commercial PAN, however, lead to typical detection limits of about 1 ppm. The coefficient of variation is typically in the 510% range at the 10-ppM level. The accuracy and applicability of the procedure are illustrated by comparative analyses on samples of synthetic solutions, river and drinking water.

Abstract: Chelation by oxine followed by adsorption on activated carbon results in the efficient collection of many trace metal ions, independent of the trace metal concentration and of high alkali and alkaline earth ion abundances. Preconcentration factors around 10000 are often achieved. When this preconcentration procedure is combined with energy-dispersive X-ray fluorescence, accurate and precise analysis can be carried out, as was proven in several experiments. The technique can also be applied for the determination of divalent ions in natural waters containing up to 10 ppm of humic substances. Trivalent ions can quantitatively be collected from natural water provided suKicient activated carbon is added. Omitting the oxine chelation prior to the activated carbon adsorption step still results in collection of a sometimes important fraction of the trace metal ions from natural waters. This is related to organically bound or colloidal forms of the trace metals.

Abstract: Plants mainly rely on a mixture of Fe complexes with different organic ligands, like carboxylates and soluble fractions of water-extractable humic substances (WEHSs), to sustain the supply of this micronutrient. It has been demonstrated that the Fe-WEHS complex is more efficiently acquired by plant roots as it enhances functionality of the mechanisms involved in Fe acquisition at the root and leaf levels, allowing a faster recovery of the Fe-deficiency symptoms. The aim of this work is to verify whether this recovery involves also the allocation and accumulation of nutrients other than Fe to and within the leaf tissues. Iron-deficient plants treated with Fe-WEHS recovered more quickly the functionality both to uptake nitrate at the root level and to fixate CO2 in the leaves than those supplied with Fe-citrate. Concomitantly, Fe-WEHS-treated plants also accumulated other cationic nutrients faster and at a higher extent. Synchrotron 2D-scanning μ-X-ray fluorescence analyses of the leaves revealed that the recovery promotes a change in the allocation of these nutrients from the vascular system (K, Cu, and Zn) or trichomes (Ca and Mn) to the entire leaf blade. Fe-WEHS treatment efficiently promotes the recovery from Fe-deficiency-induced chlorosis with an enhanced allocation of other nutrients into the leaves and promoting their distribution into the entire leaf blade.

Abstract: The capability of energy-dispersive X-ray fluorescence was investigated for fast and simple chemical analysis of trace elements in sediments and particulate matter in sea water. Nuclepore 0.4 μm pore-size membranes are recommended as optimal filters for a straightforward collection of suspended material. The collection of suspended trace metals by filtration seemed to give a sufficiently homogeneous filter load (s% <2.5). Data are presented on the concentrations of K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Br, Pb, Rb and Sr with a fair precision (s% < 5.6) and accuracy.

Abstract: Air particulate samples were collected at Chapiquiña near Arica (Chile) with a six-stage cascade impactor for about 17-day periods during a 31 month interval. Sixteen elements were determined by energy dispersive X-ray fluorescence analysis, and the elemental concentrations were subjected to principal factor analysis. The variability with time of the coarse particles was described by two factors both related to soil dispersion, whereas the fine particle variations could be explained by a third factor related to marine influence. Enrichment factors were compared with those obtained in other remote continental areas, in particular those of air particulate matter sampled at Chacaltaya, Bolivia. Results point to a negligible anthropogenic influence.

Abstract: The Maastricht limestone used for the construction of the 14th century O.L. Basilica in Tongeren, Belgium, is a light yellowish, porous, soft rock of the Late Cretaceous age. The limestone has a high carbonate content (> 95%); quartz and glauconite occur rarely. On the north side of the building, there is extensive growth of epilithic algae. On the south side, an assemblage of organisms was observed beneath the abiotic surface. This community, developed as a green layer 1 mm below the surface, is dominated by cyanobacteria. A moss was also present. The organisms were studied by transmitted light, phase contrast and scanning electron microscopy, and isolated in cultures. The cyanobacteria belong to the genera Synechococcus and Chroococcidiopsis, and the moss was identified as Tortula muralis Hedw. The organic matter present in the green layer was characterized in terms of molecular components using analytical pyrolysis. Pyrolysis products from polysaccharides and proteins, and evaporation/pyrolysis products from lipids, comprise the vast majority of identified compounds. The identification of specific biomarkers such as 7-methylheptadecane is further evidence of the presence of cyanobacteria. Phytenes and phytadienes are indicative of phototrophic organisms, as they are pyrolysis products from chlorophylls.