Dispersion of natural arsenic in the Malcantone watershed, Southern Switzerland: field evidence for repeated sorption-desorption and oxidation-reduction processes

In recent years, elevated arsenic concentrations have been found in waters and soils of many, countries, often resulting in a health threat for the local population. Switzerland is not an exception and this paper deals with the release and subsequent fate of arsenic in a 200-km(2) mountainous watershed, characterized by crystalline silicate rocks (gneisses, schists, amphibolites) that contain abundant As-bearing sulfide ore deposits, some of which have been mined for iron and gold in the past. Using analytical methods common for mineralogical, ground water and soil studies (XRD, XRF, XAS-XANES and -EXAFS, electron microprobe, extraction, ICP, AAS with hydride generator, ion chromatography), seven different field situations and related dispersion processes of natural arsenic have been studied: (1) release by rock weathering, (2) transport and deposition by water and ice; (3) release of As to the ground and surface water due to increasing pH; (4) accumulation in humic soil horizons; (5) remobilization by reduction in water-saturated soils and stagnant ground waters; (6) remobilization by using P-rich fertilizers or dung and (7) oxidation, precipitation and dilution in surface waters. Comparison of the results with experimental adsorption studies and speciation diagrams from the literature allows us to reconstruct and identify the typical behavior of arsenic in a natural environment under temperate climatic conditions. The main parameters identified are: (a) once liberated from the primary minerals, sorption processes on Fe-oxy-hydroxides dominate over Al-phases, such as Al-hydroxides or clay minerals and limit the As concentrations in the spring and well waters between 20 and 300 mug/l. (b) Precipitation as secondary minerals is limited to the weathering domain, where the As concentrations are still high and not yet too diluted by rain and soils waters. (c) Although neutral and alkaline pH conditions clearly increase the mobility of As, the main factor to mobilize As is a low redox potential (Eh close or below 0 mV), which favors the dissolution of the Fe-oxy-hydroxides on which the As is sorbed. (d) X-ray absorption spectroscopy (XAS) of As in water-logged humic forest soils indicates that the reduction to As III only occurs at the solid-water interface and that the solid contains As as As V (e) A and Bh horizons of humic cambisols can effectively capture As when As-rich waters flow through them. Complex spatial and temporal variation of the various parameters in a watershed results in repeated mobilization and immobilization of As, which continuously transports As from the upper to the lower part of a watershed and ultimately to the ocean. (C) 2004 Elsevier B.V. All rights reserved.

Clinical evaluation of iron treatment efficiency among non-anemic but iron-deficient female blood donors: a randomized controlled trial.

ABSTRACT: Iron deficiency without anemia (IDWA) is related to adverse symptoms that can be relieved by supplementation. Since a blood donation can induce such an iron deficiency, we investigated the clinical impact of an iron treatment after blood donation. METHODS: One week after donation, we randomly assigned 154 female donors with IDWA aged <50 years to a 4-week oral treatment of ferrous sulfate vs. placebo. The main outcome was the change in the level of fatigue before and after the intervention. Also evaluated were aerobic capacity, mood disorder, quality of life, compliance and adverse events. Biological markers were hemoglobin and ferritin. RESULTS: Treatment effect from baseline to 4 weeks for hemoglobin and ferritin were 5.2 g/L (p < 0.01) and 14.8 ng/mL (p < 0.01) respectively. No significant clinical effect was observed for fatigue (-0.15 points, 95% confidence interval -0.9 to 0.6, p = 0.697) or for other outcomes. Compliance and interruption for side effects was similar in both groups. Additionally, blood donation did not induce overt symptoms of fatigue in spite of the significant biological changes it produces. CONCLUSIONS: These data are valuable as they enable us to conclude that donors with IDWA after a blood donation would not clinically benefit from iron supplementation. Trial registration: NCT00689793.

Uranium-enrichment in soils and plants in the vicinity of a pitchblende vein at La Creusaz-Les Marecottes (W of Martigny, Valais, Switzerland)

In the NE part of the Aiguilles Rouges Massif near Martigny, at the eastern contact of the Variscan Vallorcine granite to adjacent gneisses, a series of pitchblende (UO2)-veins occur. This paper determines the level of enrichment and mobility of uranium in soils situated in the vicinity of such a UO2-vein 7 km west of Martigny. Within an area of 50 x 100 m, situated on a relatively steep slope and characterized by a strong gramma-ray anomaly, six soil profiles including their plant cover and a reference soil profile outside the influence of the UO2-vein have been examined. The soil shows pH-values between 4 and 5 and is colluvial. The applied analytical methods for the metal contents include extraction methods, common for soil studies, and bulk analysis performed with X-ray fluorescence and ICP-MS. Uranium contents found in the uppermost 20 cm of the soil profiles vary from 2,500 ppm close to the vein to 15 ppm at the lowermost point of the study area. The reference soil has around 3 ppm uranium. At greater depth (20 to 40 cm) the U-content decreases to about half of the surface values, indicating a vertical transport of uranium within the soil profile. No systematic dependance of uranium-contents to grain size (amount of clay) nor to the amount of organic matter has been found. However, the good correlation between uranium and free iron oxide concentration suggests adsorption of uranium on iron oxy-hydroxides. The ashes of grass and mosses contain up to 90 ppm U, the blueberry and redwood only up to 3 ppm. Our observations suggest that at the surface the uranium is transported by downhill creep (solifluxion) of uranium-rich rock fragments. Liberated by oxidation of the uppermost fragments in a given soil column, the uranium migrates vertically until the conditions are favourable to adsorption onto Fe-oxy-hydroxides. However, as high U-contents of local surface water show, this adsorption does not lead to a significant retention of the uranium.

Evaluation of uptake and transport of cationic and anionic ultrasmall iron oxide nanoparticles by human colon cells

Nanoparticles (NPs) are in clinical use or under development for therapeutic imaging and drug delivery. However, relatively little information exists concerning the uptake and transport of NPs across human colon cell layers, or their potential to invade three-dimensional models of human colon cells that better mimic the tissue structures of normal and tumoral colon. In order to gain such information, the interactions of biocompatible ultrasmall superparamagnetic iron oxide nanoparticles (USPIO NPs) (iron oxide core 9-10 nm) coated with either cationic polyvinylamine (aminoPVA) or anionic oleic acid with human HT-29 and Caco-2 colon cells was determined. The uptake of the cationic USPIO NPs was much higher than the uptake of the anionic USPIO NPs. The intracellular localization of aminoPVA USPIO NPs was confirmed in HT-29 cells by transmission electron microscopy that detected the iron oxide core. AminoPVA USPIO NPs invaded three-dimensional spheroids of both HT-29 and Caco-2 cells, whereas oleic acid-coated USPIO NPs could only invade Caco-2 spheroids. Neither cationic aminoPVA USPIO NPs nor anionic oleic acid-coated USPIO NPs were transported at detectable levels across the tight CacoReady? intestinal barrier model or the more permeable mucus-secreting CacoGoblet? model.

Extraction of soil water by plants: development and validation of a model

A quantitative model of water movement within the immediate vicinity of an individual root is developed and results of an experiment to validate the model are presented. The model is based on the assumption that the amount of water transpired by a plant in a certain period is replaced by an equal volume entering its root system during the same time. The model is based on the Darcy-Buckingham equation to calculate the soil water matric potential at any distance from a plant root as a function of parameters related to crop, soil and atmospheric conditions. The model output is compared against measurements of soil water depletion by rice roots monitored using γ-beam attenuation in a greenhouse of the Escola Superior de Agricultura "Luiz de Queiroz"/Universidade de São Paulo(ESALQ/USP) in Piracicaba, State of São Paulo, Brazil, in 1993. The experimental results are in agreement with the output from the model. Model simulations show that a single plant root is able to withdraw water from more than 0.1 m away within a few days. We therefore can assume that root distribution is a less important factor for soil water extraction efficiency.

Simple and fast methods based on solid-phase extraction coupled to liquid chromatography with UV detection for the monitoring of caffeine in natural and waste waters as marker of anthropogenic impact

Two concentration methods for fast and routine determination of caffeine (using HPLC-UV detection) in surface, and wastewater are evaluated. Both methods are based on solid-phase extraction (SPE) concentration with octadecyl silica sorbents. A common “offline” SPE procedure shows that quantitative recovery of caffeine is obtained with 2 mL of an elution mixture solvent methanol-water containing at least 60% methanol. The method detection limit is 0.1 μg L−1 when percolating 1 L samples through the cartridge. The development of an “online” SPE method based on a mini-SPE column, containing 100 mg of the same sorbent, directly connected to the HPLC system allows the method detection limit to be decreased to 10 ng L−1 with a sample volume of 100 mL. The “offline” SPE method is applied to the analysis of caffeine in wastewater samples, whereas the “on-line” method is used for analysis in natural waters from streams receiving significant water intakes from local wastewater treatment plants

Iron oxides in plinthic soils on sedimentary deposits in northeastern Brazil

This study was conducted to examine the distribution and nature of Fe oxides in plinthic soils on the sediments of Barreiras Group (in the state of Piauí) and Itapecuru Formation (in the state of Maranhão) in Northeastern Brazil. Four pedons were selected: a "plinthic, dystrophic, epieutrophic Gray Podzolic with low activity clay" and a "dystrophic Plinthosol with low activity clay" (both Plinthic Kandiustalfs) on the Barreiras sediments, as well as an "eutrophic Plinthosol with low activity clay" and an "allic Plinthosol with low activity clay" (both Plinthustalfs) on the Itapecuru sediments. Soil samples were fractionated into > 2 mm (pisoliths), water-stable aggregates (plinthite) and matrices; the aggregates and matrices were further fractionated into sand, silt and clay sizes. Dithionite extractable iron (Fe d) and aluminum (Al d), as well as oxalate extractable iron (Fe o), were determined for all fractions, and X-ray diffraction analyses were performed on the pisoliths. It was observed that the Plinthustalfs contain more iron oxides, exhibit more extensive plinthite development and have a greater potential for further plinthite development than the Kandiustalfs. The distribution of values for the Fe d indicates that plinthite formation and induration in all soils were accompanied by an enrichment of Fe oxides in all particle size fractions. This Fe segregation was accompanied by aggregation of particles leading to a greater degree of crystallinity, as indicated by analysis of the ratios of Al d:Fe d. Larger ratios of goethite to hematite, and relatively smaller amounts of silicates in the more mature pisoliths were revealed by X-ray diffraction analysis. Ratios of Al d:Fe d were larger in the Kandiustalfs than in the Plinthustalfs, and also larger than expected for Al-substituted Fe oxides. According to ratios of Al d:Fe d, Fe mobilization in all soils has likely occurred under reducing conditions, facilitated by organic matter on the soil surface.

Compositional and structural variabilities of Mg-rich iron oxide spinels from tuffite

Maghemite (γFe2O3) from tuffite is exceptionally rich in Mg, relatively to most of those reportedly found in other mafic lithosystems. To investigate in detail the compositional and structural variabilities of this natural magnetic iron oxide, sets of crystals were isolated from samples collected at different positions in a tuffite weathering mantle. These sets of crystal were individually powdered and studied by X-ray diffractometry, Mössbauer spectroscopy, magnetization measurements and chemical analysis. Lattice parameter of the cubic cell (a0) was found to vary from 0.834(1) to 0.8412(1) nm. Lower a0-values are characteristic of maghemite whereas higher ones are related to a magnetite precursor. FeO content ranges up to 17 mass % and spontaneous magnetization ranges from 8 to 32 J T-1 kg-1. Zero-field room temperature Mössbauer spectra are rather complex, indicating that the hyperfine field distributions due to Fe3+ and mixed valence Fe3+/2+ overlap. The structural variabilities of the (Mg, Ti)-rich iron oxide spinels is essentially related to the range of chemical composition of its precursor (Mg, Ti)-rich magnetite, and probably to the extent to which it has been oxidized during transformation in soil.

Iron supplementation in a large Swiss cohort of IBD patients demonstrates a shift from oral to intravenous iron over time

Background: The 2007 European Crohn's and Colitis Organization guidelines on anemia in inflammatory bowel disease (IBD) favour intravenous (iv) over oral (po) iron supplementation due to better effectiveness and tolerance. We aimed to determine the percentage of IBD patients under iron supplementation therapy and the dynamics of prescription habits (iv versus po) over time. Methods: Helsana, a leading Swiss health insurance company provides coverage for approximately 18% of the Swiss population, corresponding to about 1.2 million enrollees. Patients with Crohn's disease (CD) and ulcerative colitis (UC) were analyzed from the anonymised Helsana database. Results: In total, 629 CD (61% female) and 398 UC (57% female) patients were identified, mean observation time was 31.8 months for CD and 31.0 months for UC patients. Of the entire study population, 27.1% were prescribed iron (21.1% in males and 31.1% in females). Patients treated with IBDspecific drugs (steroids, immunomodulators, anti-TNF agents) were more frequently treated with iron compared to patients without any medication (35.0% vs. 20.9%, OR 1.91, 95%- CI 1.41 2.61). The prescription of iv iron increased from 2006/2007 (48.8% of all patients receiving any iron priscription) to 65.2% in 2008/2009 by a factor of 1.89. Conclusions: One third of the IBD population was treated with iron supplementation. A gradual shift from oral to iv iron was observed over time. This switch in prescription habits goes along with the implementation of the ECCO consensus guidelines on anemia in IBD.

Multicentre validation study of nucleic acids extraction from FFPE tissues.

In most pathology laboratories worldwide, formalin-fixed paraffin embedded (FFPE) samples are the only tissue specimens available for routine diagnostics. Although commercial kits for diagnostic molecular pathology testing are becoming available, most of the current diagnostic tests are laboratory-based assays. Thus, there is a need for standardized procedures in molecular pathology, starting from the extraction of nucleic acids. To evaluate the current methods for extracting nucleic acids from FFPE tissues, 13 European laboratories, participating to the European FP6 program IMPACTS (www.impactsnetwork.eu), isolated nucleic acids from four diagnostic FFPE tissues using their routine methods, followed by quality assessment. The DNA-extraction protocols ranged from homemade protocols to commercial kits. Except for one homemade protocol, the majority gave comparable results in terms of the quality of the extracted DNA measured by the ability to amplify differently sized control gene fragments by PCR. For array-applications or tests that require an accurately determined DNA-input, we recommend using silica based adsorption columns for DNA recovery. For RNA extractions, the best results were obtained using chromatography column based commercial kits, which resulted in the highest quantity and best assayable RNA. Quality testing using RT-PCR gave successful amplification of 200 bp-250 bp PCR products from most tested tissues. Modifications of the proteinase-K digestion time led to better results, even when commercial kits were applied. The results of the study emphasize the need for quality control of the nucleic acid extracts with standardised methods to prevent false negative results and to allow data comparison among different diagnostic laboratories.

Old ferricrete landscape dismantling in Central Africa rain forest zone: formation of the present downslope iron accumulations.

Present downslope iron accumulations were investigated in the rainforest zone in southern Cameroon. Six clay and Fe-hydroxide dominated patterns have been identified and occur on the lower part of hill slopes. They can be subdivided in three different sequences, related to gentle, moderate or steep slopes. They are discontinuous with respect to the dismantling zone of the old ferricrete cap formed at Cretaceous period. They show a gradual development from a soft Fe-crust (carapace) to a vesicular facies that will, with time, cover the whole landscape again.

Positive contrast MR-lymphography using inversion recovery with ON-resonant water suppression (IRON).

PURPOSE: To investigate the utility of inversion recovery with ON-resonant water suppression (IRON) to create positive signal in normal lymph nodes after injection of superparamagnetic nanoparticles. MATERIALS AND METHODS: Experiments were conducted on six rabbits, which received a single bolus injection of 80 mumol Fe/kg monocrystalline iron oxide nanoparticle (MION-47). Magnetic resonance imaging (MRI) was performed at baseline, 1 day, and 3 days after MION-47 injection using conventional T(1)- and T(2)*-weighted sequences and IRON. Contrast-to-noise ratios (CNR) were measured in blood and in paraaortic lymph nodes. RESULTS: On T(2)*-weighted images, as expected, signal attenuation was observed in areas of paraaortic lymph nodes after MION-47 injection. However, using IRON the paraaortic lymph nodes exhibited very high contrast enhancement, which remained 3 days after injection. CNR with IRON was 2.2 +/- 0.8 at baseline, increased markedly 1 day after injection (23.5 +/- 5.4, P < 0.01 vs. baseline), and remained high after 3 days (21.8 +/- 5.7, *P < 0.01 vs. baseline). CNR was also high in blood 1 day after injection (42.7 +/- 7.2 vs. 1.8 +/- 0.7 at baseline, P < 0.01) but approached baseline after 3 days (1.9 +/- 1.4, P = NS vs. baseline). CONCLUSION: IRON in conjunction with superparamagnetic nanoparticles can be used to perform 'positive contrast' MR-lymphography, particularly 3 days after injection of the contrast agent, when signal is no longer visible within blood vessels. The proposed method may have potential as an adjunct for nodal staging in cancer screening.

Feature Extraction from Whole-Sky Ground-Based Images for Cloud-Type Recognition

Several features that can be extracted from digital images of the sky and that can be useful for cloud-type classification of such images are presented. Some features are statistical measurements of image texture, some are based on the Fourier transform of the image and, finally, others are computed from the image where cloudy pixels are distinguished from clear-sky pixels. The use of the most suitable features in an automatic classification algorithm is also shown and discussed. Both the features and the classifier are developed over images taken by two different camera devices, namely, a total sky imager (TSI) and a whole sky imager (WSC), which are placed in two different areas of the world (Toowoomba, Australia; and Girona, Spain, respectively). The performance of the classifier is assessed by comparing its image classification with an a priori classification carried out by visual inspection of more than 200 images from each camera. The index of agreement is 76% when five different sky conditions are considered: clear, low cumuliform clouds, stratiform clouds (overcast), cirriform clouds, and mottled clouds (altocumulus, cirrocumulus). Discussion on the future directions of this research is also presented, regarding both the use of other features and the use of other classification techniques

Steady-state equilibrium phase inversion recovery ON-resonant water suppression (IRON) MR angiography in conjunction with superparamagnetic nanoparticles. A robust technique for imaging within a wide range of contrast agent dosages.

PURPOSE: To investigate the ability of inversion recovery ON-resonant water suppression (IRON) in conjunction with P904 (superparamagnetic nanoparticles which consisting of a maghemite core coated with a low-molecular-weight amino-alcohol derivative of glucose) to perform steady-state equilibrium phase MR angiography (MRA) over a wide dose range. MATERIALS AND METHODS: Experiments were approved by the institutional animal care committee. Rabbits (n = 12) were imaged at baseline and serially after the administration of 10 incremental dosages of 0.57-5.7 mgFe/Kg P904. Conventional T1-weighted and IRON MRA were obtained on a clinical 1.5 Tesla (T) scanner to image the thoracic and abdominal aorta, and peripheral vessels. Contrast-to-noise ratios (CNR) and vessel sharpness were quantified. RESULTS: Using IRON MRA, CNR and vessel sharpness progressively increased with incremental dosages of the contrast agent P904, exhibiting constantly higher contrast values than T1 -weighted MRA over a very wide range of contrast agent doses (CNR of 18.8 ± 5.6 for IRON versus 11.1 ± 2.8 for T1 -weighted MRA at 1.71 mgFe/kg, P = 0.02 and 19.8 ± 5.9 for IRON versus -0.8 ± 1.4 for T1-weighted MRA at 3.99 mgFe/kg, P = 0.0002). Similar results were obtained for vessel sharpness in peripheral vessels, (Vessel sharpness of 46.76 ± 6.48% for IRON versus 33.20 ± 3.53% for T1-weighted MRA at 1.71 mgFe/Kg, P = 0.002, and of 48.66 ± 5.50% for IRON versus 19.00 ± 7.41% for T1-weighted MRA at 3.99 mgFe/Kg, P = 0.003). CONCLUSION: Our study suggests that quantitative CNR and vessel sharpness after the injection of P904 are consistently higher for IRON MRA when compared with conventional T1-weighted MRA. These findings apply for a wide range of contrast agent dosages.