Abstract: The investigation of hunter-gatherers archaeological sites in the Limay river basin, Patagonia, Argentina, raised questions concerning the lithic technology. The chemical characterization of artifacts, rocks and possible sources of provenances could help to elucidate the hunter-gatherer mobility. In three archaeological sitesRincón Chico 2 (RCh2/87; 14C 710 ± 60 BP), Cueva Traful I (CTI; 14C 9430 ± 230 BP) and Casa de Piedra de Ortega (CPO; 14C 2840 ± 80 BP), tools and debitage or discarded flakes made in black volcanic rock have been found. Nearby an extensive rock outcrop of black volcanite, Paso Limay quarry (CPL), with similar characteristics was located. Samples coming from these four sites were analyzed by energy dispersive X-ray fluorescence spectrometry. This characterization allowed the geochemical classification of the lithic material and to correlate the samples with the suspected source after a previous statistical analysis. The majority of the samples were classified as dacites and rhyolites. Only samples coming from CPO site, the closest place to CPL were made exclusively with the quarry rocks. A set of five samples from RCh2/87 and two samples from CTI appear to have same chemical composition as CPL in spite of this site is placed in the opposite bank of the Limay river suggesting that hunter-gatherers could accede to the quarry, eventually. Finally, only a set of five samples coming from RCh2/87 and CTI do not group with the quarry. This fact evidences the existence of secondary sources of supply. The information of this research allowed inferring ancient human mobility patterns in the region.

Abstract: We aimed to achieve improved instrumental sensitivity and detection limits for the analysis of several elements (Cu, Ni, Zn, Pb and Cd) in aqueous samples with energy dispersive X-ray fluorescence spectrometry (EDXRF). The metals were pre-concentrated from aqueous solutions using commercially available organic-based solid-phase extraction (SPE) disks functionalized with iminodiacetate groups. These thin-layer organic materials provide an ideal support for XRF analysis. The elements were collected on the SPE extraction disks using a simple filtration procedure (starting with 1 L of aqueous sample) that allows direct XRF measurements to be performed in the field (in situ). We evaluated the analytical possibilities and drawbacks of using this pre-concentration procedure in combination with the following XRF configurations: a handheld unit, a benchtop EDXRF system and a high-energy polarized-beam EDXRF instrument (HE-P-EDXRF). Using the HE-P-EDXRF system, the detection limits for all metals were more than one order of magnitude lower than those attained using handheld and benchtop EDXRF instrumentation. For the detection of metal concentrations higher than similar to 20 mu g/L, however, handheld or benchtop systems remain a very good option due to their extreme simplicity of operation and low-cost, compact design. We demonstrate the application of these methodologies, using the three equipment systems, to the analysis of trace concentrations of metals in different types of aqueous samples, including tap water and waste water. (C) 2011 Elsevier B.V. All rights reserved.

Abstract: In the past years, and also within the framework of this CRP, we have used a combination of several nuclear and non-nuclear techniques in fundamental research and especially in various applications. Most work has been done with energy-dispersive X ray fluorescence in combination with electron probe X ray microanalysis, but several other more common analysis techniques have been used as well. The applications have included mostly preventive conservation (e.g. characterisation of damaging atmospheric particles in many museums) and environmental monitoring (e.g. for atmospheric particles in relation to their health effects in outdoor and especially indoor environments). Fundamental aspects have been in the optimising of interfaced electron microprobe and Raman microprobe analysis and the evaluation of the potential of such an instrument for atmospheric aerosols; quite a few unexpected and unpredicted problems have appeared in the latter study.

Abstract: Iron (Fe) and other trace elements such as Zn, Mn, Ni and Cu are known as key-factors in marine biogeochemical cycles. It is believed that ocean primary productivity blooms in iron deficient regions can be triggered by iron in aeolian dust. Up to now, scarce aerosol elemental composition, based on measurements over sea at the Western South Atlantic (WSA), exist. An association between the Patagonian semi-desert dust/Fe and chlorophyll-a variability at the Argentinean continental shelf is essentially inferred from models. We present here experimental data of Fe enriched aerosols over the WSA between latitudes 22°S62°S, during 4 oceanographic campaigns between 2002 and 2005. These data allowed inferring the atmospheric Fe flux onto different latitudinal bands which varied from 30.4 to 1688 nmolFe m−2 day−1 (October 29thNovember 15th, 2003); 5.831586 nmolFe m−2 day−1 (February 15thMarch 6th, 2004) and 4.73586 nmolFe m−2 day−1(October 21stNovember 5th, 2005).

Abstract: In medicinal chemistry, Pd is perhaps the most-widely utilized precious metal, as catalyst in reactions which represent key transformations toward the synthesis of new active pharmaceutical ingredients (APIs). The disadvantage of this metal-catalyzed chemistry is that expensive and toxic metal residues are invariably left bound to the desired product. Thus, stringent regulatory guidelines exist for the amount of residual Pd that a drug candidate is allowed to contain. In this work, a rapid and simple method for the determination of Pd in API samples by high-energy polarized-beam energy dispersive X-ray fluorescence spectrometry has been developed and validated according to the specification limits of current legislation (10 mg kg−1 Pd) and the International Conference on Harmonisation of Technical Requirements for Registration of Pharmaceuticals for Human Use (ICH guidelines). Sample and calibration standards preparation includes a first step of homogenization and then, in a second step, the pressing of the powdered material into pellets without any chemical treatment. The use of several synthetic calibration standards made of cellulose to simulate the API matrix appears to be an effective means to obtain reliable calibration curves with a good spread of data points over the working range. With the use of the best measuring conditions, the limit of detection (0.11 mg kg−1 Pd) as well as the limit of quantitation (0.37 mg kg−1 Pd) achieved meet rigorous requirements. The repeatability of the XRF measurement appeared to be less than 2%, while the precision of the whole method was around 7%. Trueness was evaluated by analyzing spiked API samples at the level of the specification limit and calculating the recovery factor, which was better than 95%. To study the applicability of the developed methodology for the intended purpose, three batches of the studied API were analyzed for their Pd content, and the attained results were comparable to those obtained by the daily routine method (acid digestion plus atomic spectroscopy) used in most pharmaceutical laboratories.

Abstract: Increasingmass tourismcan generate importantmicroclimatic perturbations and also elevate indoor pollution by the transport of fine particulatematter. The purpose of this researchwas to study the indoor air conditions in the RoyalMuseum ofWawel Castle in Cracow, Poland, displaying amongst other valuable works of art also a unique collection of Flemish tapestries. The investigation involved in the determination of transport and deposition of particulate matter brought in by visitors. The microclimate inside the exhibition rooms was also monitored. Samples of suspended particulateswere collected inside and outside themuseuminwinterand summer2006.On days with intensive tourist visits the concentration of total suspended particulates was significantly higher (i.e., 130 µg/m3 inwinter and 49 µg/m3 in summer) than on those days without tourists (i.e., 73 µg/m3 and 22 µg/m3 in winter and summer, respectively). The concentrations of all investigated elementswere also considerably higher during the tourist flow. This was especially valid for soil dust associated elements (Si, K, Ca, Al, and Ti), with considerably higher levels in summer than winter. This could be linked with much more frequent tourist activity in the summer period. Also, the concentration of Clwasmuch higher inwinter than summer, due to the use of deicing salts on the roads and pavements.