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: We used SEM/EDX and micro-Raman spectroscopy to investigate the chemical changes (both on the level of elementary and molecular composition) of mice bones when strontium is incorporated in their microstructure after being administered in the form of two salts: chloride and ranelate. Strontium accumulated mainly in vicinity of bone edges, both cortical and close to bone marrow. The distribution of other elements comprising bone samples (Ca, P, Mg, K etc.) was also determined by energy-dispersive X-ray analysis (EDX). The area adjacent to a cortical bone edge with accumulated strontium has presented modified Raman spectral profiles. Besides most of the Raman bands typical for both mineral (hydroxyapatite with carbonate substitution type B) and organic phases of a bone, we observed a Raman band at 811 cm− 1. It was detected regularly in the sample with high strontium concentration.

Abstract: Here we show that mineral dust retrieved from an ice core in the central West Antarctic sector, spanning the last five decades, provides evidence that northerly air mass incursions into Antarctica, tracked by dust microparticles, have slightly declined. This result contrasts with dust in ice core records reported in West/coastal Antarctica, which show significant increases to the present day. We attribute that difference, in part, to changes in the regional climate regime triggered by the ozone depletion and its consequences for the polar vortex intensity. The vortex maintains the Antarctic central region relatively isolated from mid-latitude air mass incursions with implications to the intensification of the Westerlies and to a persistent positive phase of the Southern Annular Mode. We also show that variability of the diameter of insoluble microparticles in central West Antarctica can be modeled by linear/quadratic functions of both cyclone depth (energy) and wind intensity around Antarctica.

Abstract: Two sampling campaigns in suburban places in the north zone of Santa Clara city, Cuba, have been carried out on a weekly base with the use of Radiello passive diffusion tubes in order to monitor the tropospheric ozone (O3) levels in 2010. The first campaign was scheduled from February to April (cold season) and the second one in August and October (warm season), both of them at two sampling sites, i.e., Farm and School of Art Instructors. After aqueous extraction, the samples were analyzed by UVVIS spectrophotometry. A seasonal trend was observed with the maximum O3 concentrations in the cold season and the minimum levels in the warm season. Samples collected during the cold season showed the highest O3 levels. Higher levels were reached at the Farm site with average values of about 58 ± 12 μg/m3, which exceeded the limit of the Cuban Standard 99:1999. In the warm season, the O3 concentrations were similar for both sites, but lower than those observed in the cold season. The overall, seasonal average value was found to be 24 μg/m3. Despite the higher weekly average temperatures in August, the O3 concentrations during this month showed the lowest values of the whole sampling period, which finding is in agreement with that reported by the Meteorological Institute of Cuba. Mathematical models, based on the Cochrane-Orcutt algorithm, were fitted to the acquired data set to explain the change in the tropospheric ozone concentrations under various meteorological conditions during the two campaigns. The correlation coefficients for both the cold and the warm seasons demonstrated a strong correlation, i.e., 0.779 and 0.951, respectively. The high correlation of wind speed in the model from the first sampling campaign explains the sharp decrease in O3 concentrations at the SAI sampling site from the sixth week of sampling.

Abstract: Most of the marine precipitation of CaCO3 is due to the biological activities of planktonic and benthic organisms in waters largely oversaturated with respect to calcium carbonates. This saturation state is expected to decrease as CO2 increases in seawater. A conventional view in oceanography suggests that calcium carbonates organisms are preserved in oversaturated waters and dissolve only below the lysocline. However, it has be postulated that a fraction of the CaCO3 precipitated biogenically could dissolve in oversaturated waters due to the formation of microenvironments in which respired CO2 decreases the saturation state of seawater (Ù) in the vicinity of CaCO3 crystals. In the present study, cells of the coccolithophore Emiliania huxleyi obtained from laboratory cultures and field samples collected in the Gulf of Biscay, were examined using variable-energy electron-probe microanalysis, to determine the presence and thickness of their organic coating. In addition, a new approach for transferring micrometer-sized particles from a filter onto transmission electron microscope grids using manipulators was used to investigate individual coccolithophores. The dry thickness of an organic coating over the coccolithophore surface was found to range between 280 and 350 nm. The resemblance of this coating to the carbohydrates produced and released by the cell is discussed as well as their potential for constituting a microenvironment that hosts bacteria. The properties of this organic coating and its role in the preservation/dissolution and export of biogenic carbonates in the water column are one of the major issues of carbonate geochemistry.

Abstract: Photoactive layers based on aryl- and aryloxy-substituted naphthalocyanines and conductive polymer poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylene vinylene] (MEH-PPV) were prepared using the spin-coating technique and their conductivity was tested in dark and under illumination. For this purpose novel octa-2-naphthoxy-substituted naphthalocyanines were synthesized starting from 6,7-di(2-naphthoxy)naphthalene-2,3-dicarbonitrile. For those novel naphthalocyanine complexes, spectral and electrochemical data were measured and compared with corresponding ones for other aryl-substituted analogues. In comparison to the previously studied naphthalocyanines with alkyl- and phenyl- groups, the formal oxidation and reduction potentials were rather similar. All target complexes demonstrate intense near-infrared absorption at 760-790 nm, which is about 30 nm bathochromically shifted in thin films. The photo-resistive effect was found increasing from composites comprised of naphthoxy- to phenyl-substituted naphthalocyanines. This peculiarity was explained by using optical and atomic force microscopy in terms of different sizes of aggregates formed. The photo-response time for novel composited was approximately 3 s, which is about 20 times faster than measured previously for the films deposited via the drop-casting technique.

Abstract: Energy-dispersive X-ray fluorescence analysis was applied for the analysis of hair. The hair samples were digested in a mixture of nitric and perchloric acid and the heavy metals were precipitated with ammonium pyrrolidine dithiocarbamate. The accuracy, precision and recovery of the method for the elements Fe, Ni, Cu, Zn and Pb were evaluated through the analysis of a standard hair sample. The procedure was applied to the analysis of hair from an occupationally exposed group of Sudanese workers and a control group. The hair of the exposed group showed a range of 80550 ppm Fe, 612 ppm Cu, 57190 ppm Zn and 703700 ppm Pb, while that of the control group had a range of 60310 ppm Fe, 722 ppm Cu, 89170 ppm Zn and 317 ppm Pb.

Abstract: During the recultivation of the uranium mining area of Kõvágószõlõs (Hungary), the tailings were covered with clay and loess soil layers having a thickness of 30 cm and 100 cm, respectively. In the loess covering layer, acacia (Robinia pseudoacacia), poplars (Populus × albus, Populus × canescens), oak (Quercus pubescens), silver tree (Eleagnus angustifolia) were planted between 1996 and 2004. In order to establish the extent of the uranium and thorium transport from the sludge to the leaves by uptake and translocation processes through roots with a length higher than 1.3 m results in a remarkable redistribution of these pollutants, a gray poplar tree, growing spontaneously in the last uncovered tailing, being selected as reference tree. The U and Th concentrations in the leaves of the above-mentioned trees, in the covering layers as well as in the original sludge were determined by inductively coupled plasma sector field mass spectrometry (ICP-SF-MS). Generally, the Th concentration of the soils was about 4 times higher than that of uranium, while uranium concentration was about 10130 times higher than that of thorium in the leaf samples and its concentration ranged from 28 to 1045 ng g− 1, the last value belonging to the poplar tree growing on the last uncovered tailing. In order to assume the mobility and bioavailability of uranium if the dry leaves fall down, the uranium species in the leaves of the poplar tree growing in the uncovered reservoir were determined applying ultrasound-assisted extraction with distilled water and ammonium acetate as well as high performance liquid chromatographic (HPLC)-ICP-SF-MS technique. About 20% of total uranium could be extracted in form of uranyl cations and a presumably negatively charged uranium compound. Estimations revealed that the annual increment of U in the soil surface layer due to the dead fallen leaves in case of the investigated gray poplar (Populus × canescens) is about 1.2%.

Abstract: Oil paints comprise pigments, drying oils, and additives that together confer desirable properties, but can react to form metal carboxylates (soaps) that may damage artworks over time. To obtain information on soap formation and aggregation, we introduce a new tapping-mode measurement paradigm for the photothermal induced resonance (PTIR) technique that enables nanoscale IR spectroscopy and imaging on highly heterogenous and rough paint thin sections. PTIR is used in combination with mu-computed tomography and IR microscopy to determine the distribution of metal carboxylates in a 23-year old oil paint of known formulation. Results show that heterogeneous agglomerates of Al-stearate and a Zn-carboxylate complex with Zn-stearate nano-aggregates in proximity are distributed randomly in the paint. The gradients of zinc carboxylates are unrelated to the Al-stearate distribution. These measurements open a new chemically sensitive nanoscale observation window on the distribution of metal soaps that can bring insights for understanding soap formation in oil paint.

Abstract: This article reviews the different methods used for the determination of selenium species in all types of environmental waters. Basic difficulties are discussed and the efficiency of the methods is explained in view of the sub-μg/1. concentration levels. Special attention is paid to preconcentration steps. Published data on speciation and concentration levels in various water samples are critically reviewed.