Cu isotope ratios are meaningful in ovarian cancer diagnosis.

BACKGROUND: Ovarian cancer diagnosis is currently based on imaging and circulating CA-125 concentrations with well-known limits to sensitivity and specificity. New biomarkers are required to complement CA-125 testing to increase effectiveness. Increases in sensitivity of isotopic separation via multi collector inductively coupled plasma-mass spectrometry have recently allowed highly accurate measurement of copper (Cu) isotopic variations. Studies in breast cancer patients have revealed changes of serum copper isotopic composition demonstrating the potential for development as a cancer biomarker. Evaluating 65Cu/63Cu ratios (δ65Cu) in serum samples from cancer patients has revealed a strong correlation with cancer development. In this study blood samples from forty-four ovarian cancer patients, and 13 ovarian biopsies were investigated. RESULTS: Here we demonstrate that changes in Cu isotopes also occurs in ovarian cancer patients. Copper composition determined by multiple collector inductively coupled plasma mass spectrometry revealed that the copper isotopic ratio δ65Cu in the plasma of 44 ovarian cancer patient cohort was significantly lower than in a group of 48 healthy donors, and indicated that serum was enriched for 63Cu. Further analysis revealed that the isotopic composition of tumour biopsies was enriched for 65Cu compared with adjacent healthy ovarian tissues. CONCLUSIONS: We propose that these changes are due to increase lactate and Cu transporter activities in the tumour. These observations demonstrate that, combined with existing strategies, δ65Cu could be developed for use in ovarian cancer early detection.

Sub-ppm level high energy resolution fluorescence detected X-ray absorption spectroscopy of selenium in articular cartilage.

The speciation of highly-diluted elements by X-ray absorption spectroscopy in a diverse range of materials is extremely challenging, especially in biological matrices such as articular cartilage. Here we show that using a high energy resolution fluorescence detected X-ray absorption spectroscopy (HERFD-XAS) technique coupled to an array of crystal analyzers, selenium speciation down to 400 ppb (µg kg-1) within articular cartilage can be demonstrated. This is a major advance in the speciation of highly-diluted elements through X-ray absorption spectroscopy and opens new possibilities to study the metabolic role of selenium and other elements in biological samples.

Physical stability of highly concentrated injectable drugs solutions used in intensive care units.

BACKGROUND: The intensive care department of the institution use drug solutions within higher concentration to avoid fluid overload. The purpose of the study is to prove the physical stability of different injectable drugs within high concentration (amiodarone 25mg/mL, isosorbide 0.60mg/mL, lorazepam 0.16mg/mL, noradrenalin 0.120 and 0.240mg/mL, salbutamol 0.06mg/mL and sodium valproate 12mg/mL) to ensure the patients safety. METHODS: Five of 30 or 50mL polypropylene syringes were prepared for each solution under aseptic conditions and stored at room temperature. Immediately after the preparation (hour 0) and after 1, 4, 8, 24 and 48hours, 2mL of each solution were withdrawn from each syringe and placed in glass tubes to proceed to the stability test. All specimens were visually inspected in front of a black and of a white background and aliquots of each solution were centrifuged to proceed to microscopic inspection with a ten-fold magnification. The pH of each solution was measured with glass electrode pH-meter (Inolab level 1, WTW Weilhem, Germany with biotrode electrode, Hamilton, Bonaduz, Switzerland) and spectrophotometric measurements (Genesys 10 series, New-York, USA) were performed at three wavelengths (350, 410 and 550nm) to avoid the apparition of turbidity. RESULTS: For all the drugs included in the study, there was no significant change in pH, no color change, no turbidity or opacity and no precipitation observed in the solutions during the storage at room temperature for 48hours. No microaggregates were detected by microscope neither revealed by a change of absorbance. CONCLUSION: Within these limits, the preparations of amiodarone in 5% glucose polypropylene syringes and isosorbide, lorazepam, noradrenalin, salbutamol, valproate in 0.9% sodium chloride polypropylene syringes are physically stable at room temperature for 48hours. These results allow us to consider a study of chemical stability by high-performance liquid chromatography (HPLC).

Selenium distribution and speciation in plant parts of wheat (Triticum aestivum) and Indian mustard (Brassica juncea) from a seleniferous area of Punjab, India.

The concentration, distribution, and speciation of selenium in different parts of wheat and Indian mustard, grown in a seleniferous area in Punjab, were investigated using synchrotron based (XAS) and classical acid digestion and extraction methods. The analyses revealed a high Se enrichment in all investigated plant parts, with Se levels in the range of 133-931 mg/kg (dry weight, dw). Such high Se enrichment is mainly due to the considerable amounts of easily available Se detected in the soil, which are renewed on a yearly basis to some extent via irrigation. Speciation analysis in soil and plants indicated selenate and organic Se as major Se species taken up by plants, with a minor presence of selenite. The analyses also revealed that the highest Se enrichment occurs in the upper plant parts, in agreement with the high uptake rate and mobility of selenate within plants. In both wheat and mustard, highest Se enrichments were found in leaves (387 mg/kg·dw in wheat and 931 mg/kg·dw in mustard). Organic species (dimethylselenide and methylselenocysteine) were found in different parts of both plants, indicating that an active detoxification response to the high Se uptake is taking place through methylation and/or volatilization. The high proportion of selenate in wheat and mustard leaves (47% and 70%, respectively) is the result of the inability of the plant metabolism to completely transform selenate to non-toxic organic forms, if oversupplied. Methylselenocysteine, a common Se species in accumulating plants, was detected in wheat, suggesting that, in the presence of high Se concentration, this plant develops similar response mechanisms to accumulator plants.

Effect of pH on aqueous Se(IV) reduction by pyrite.

Interaction of aqueous Se(IV) with pyrite was investigated using persistently stirred batch reactors under O2-free (<1 ppm) conditions at pH ranging from 4.5 to 6.6. Thermodynamic calculations, an increase in pH during the experiments, and spectroscopic observation indicate that the reduction of aqueous Se(IV) by pyrite is dominated by the following reaction: FeS2+3.5HSeO3−+1.5H+=2SO4(2−)+Fe2++3.5Se(0)+2.5H2O. The released Fe(II) was partitioned between the bulk solution and pyrite surface at pH≈4.5 and 4.8, with the Fe2+ density at pyrite-solution interface about 4 orders of magnitude higher than that in the bulk solution, while iron oxyhydroxide precipitated at pH≈6.6, resulting in the decrease of dissolved iron. In the Se(IV) concentration range of the experiments, aqueous Se(IV) reduction rate follows the pseudofirst order which is in the form of ln mSe(IV)=−k't+ln mSe(IV)0, where k' is apparent rate constant combining the rate constant k and pyrite surface area to mass of solution ratio (A/M). And the aqueous Se(IV) reduction rate constant for a standard system (k) with 1 m2 pyrite surface area per 1 kg solution was obtained to be 1.65×10(−4) h(−1), 3.28×10(−4) h(−1), and 4.76×10(−4) h(−1) at pH around 4.5, 4.8, and 5.1, respectively. The positive correlation between reaction rate and pH disagrees with the theories that protons are consumed when HSeO3− is reduced to Se0, and negative charge density on pyrite surface increases as pH increases. Thus, a ferrous iron mediated electron transfer mechanism is proposed to operate during the reduction of aqueous Se(IV) by pyrite. pH and iron concentration affect significantly on Se(IV) reaction rate and reaction product.

Uranium facilitated transport by water-dispersible colloids in field and soil columns.

The transport of uranium through a sandy podzolic soil has been investigated in the field and in column experiments. Field monitoring, numerous years after surface contamination by depleted uranium deposits, revealed a 20 cm deep uranium migration in soil. Uranium retention in soil is controlled by the <50 microm mixed humic and clayey coatings in the first 40 cm i.e. in the E horizon. Column experiments of uranium transport under various conditions were run using isotopic spiking. After 100 pore volumes elution, 60% of the total input uranium is retained in the first 2 cm of the column. Retardation factor of uranium on E horizon material ranges from 1300 (column) to 3000 (batch). In parallel to this slow uranium migration, we experimentally observed a fast elution related to humic colloids of about 1-5% of the total-uranium input, transferred at the mean porewater velocity through the soil column. In order to understand the effect of rain events, ionic strength of the input solution was sharply changed. Humic colloids are retarded when ionic strength increases, while a major mobilization of humic colloids and colloid-borne uranium occurs as ionic strength decreases. Isotopic spiking shows that both (238)U initially present in the soil column and (233)U brought by input solution are desorbed. The mobilization process observed experimentally after a drop of ionic strength may account for a rapid uranium migration in the field after a rainfall event, and for the significant uranium concentrations found in deep soil horizons and in groundwater, 1 km downstream from the pollution source.

Mineral sequestration of CO(2) by aqueous carbonation of coal combustion fly-ash.

The increasing CO(2) concentration in the Earth's atmosphere, mainly caused by fossil fuel combustion, has led to concerns about global warming. A technology that could possibly contribute to reducing carbon dioxide emissions is the in-situ mineral sequestration (long term geological storage) or the ex-situ mineral sequestration (controlled industrial reactors) of CO(2). In the present study, we propose to use coal combustion fly-ash, an industrial waste that contains about 4.1 wt.% of lime (CaO), to sequester carbon dioxide by aqueous carbonation. The carbonation reaction was carried out in two successive chemical reactions, first, the irreversible hydration of lime. second, the spontaneous carbonation of calcium hydroxide suspension. A significant CaO-CaCO(3) chemical transformation (approximately 82% of carbonation efficiency) was estimated by pressure-mass balance after 2h of reaction at 30 degrees C. In addition, the qualitative comparison of X-ray diffraction spectra for reactants and products revealed a complete CaO-CaCO(3) conversion. The carbonation efficiency of CaO was independent on the initial pressure of CO(2) (10, 20, 30 and 40 bar) and it was not significantly affected by reaction temperature (room temperature "20-25", 30 and 60 degrees C) and by fly-ash dose (50, 100, 150 g). The kinetic data demonstrated that the initial rate of CO(2) transfer was enhanced by carbonation process for our experiments. The precipitate calcium carbonate was characterized by isolated micrometric particles and micrometric agglomerates of calcite (SEM observations). Finally, the geochemical modelling using PHREEQC software indicated that the final solutions (i.e. after reaction) are supersaturated with respect to calcium carbonate (0.7 < or = saturation index < or = 1.1). This experimental study demonstrates that 1 ton of fly-ash could sequester up to 26 kg of CO(2), i.e. 38.18 ton of fly-ash per ton of CO(2) sequestered. This confirms the possibility to use this alkaline residue for CO(2) mitigation.

Comparison of arsenic concentrations in simultaneously-collected groundwater and aquifer particles from Bangladesh, India, Vietnam, and Nepal.

One of the reasons the processes resulting in As release to groundwater in southern Asia remain poorly understood is the high degree of spatial variability of physical and chemical properties in shallow aquifers. In an attempt to overcome this difficulty, a simple device that collects groundwater and sediment as a slurry from precisely the same interval was developed in Bangladesh. Recently published results from Bangladesh and India relying on the needle-sampler are augmented here with new data from 37 intervals of grey aquifer material of likely Holocene age in Vietnam and Nepal. A total of 145 samples of filtered groundwater ranging in depth from 3 to 36 m that were analyzed for As (1-1000 mug/L), Fe (0.01-40 mg/L), Mn (0.2-4 mg/L) and S (0.04-14 mg/L) are compared. The P-extractable (0.01-36 mg/kg) and HCl-extractable As (0.04-36 mg/kg) content of the particulate phase was determined in the same suite of samples, in addition to Fe(II)/Fe ratios (0.2-1.0) in the acid-leachable fraction of the particulate phase. Needle-sampler data from Bangladesh indicated a relationship between dissolved As in groundwater and P-extractable As in the particulate phase that was interpreted as an indication of adsorptive equilibrium, under sufficiently reducing conditions, across 3 orders of magnitude in concentrations according to a distribution coefficient of 4 mL/g. The more recent observations from India, Vietnam and Nepal show groundwater As concentrations that are often an order of magnitude lower at a given level of P-extractable As compared to Bangladesh, even if only the subset of particularly reducing intervals characterized by leachable Fe(II)/Fe >0.5 and dissolved Fe >0.2 mg/L are considered. Without attempting to explain why As appears to be particularly mobile in reducing aquifers of Bangladesh compared to the other regions, the consequences of increasing the distribution coefficient for As between the particulate and dissolved phase to 40 mL/g for the flushing of shallow aquifers of their initial As content are explored.

Formation of dissolved gaseous mercury in a tropical lake (Petit-Saut reservoir, French Guiana).

Formation of dissolved gaseous mercury (DGM) and its volatilization from aquatic systems can be considered as a natural attenuation process, which limits the methylation of mercury (Hg) and Hg accumulation in fish. Although gold-mining activity and erosion of tropical soils lead to increased Hg concentration in aquatic systems, little is known about DGM production and distribution in tropical aqueous systems. Our work explores the vertical distribution and principal sources of DGM in a meromictic Amazonian reservoir. Dissolved gaseous mercury measurements carried out in Petit-Saut reservoir (French Guiana, South America) revealed DGM increase in the surface waters and at the bottom layers of the reservoir during the dry season. As in arctic and temperate lakes, high DGM concentrations in surface waters were attributed to sunlight-mediated photochemical processes. Dissolved gaseous mercury concentrations in the anaerobic hypolimnion were larger than in temperate or arctic lakes. In order to elucidate Hg(II) reduction pathways in the bottom layer of tropical reservoir, laboratory Hg(II) reduction experiments were performed with anoxic aqueous suspensions of surface sediments either untreated or treated by gamma-ray and NaN3. Our results indicated that DGM production at the bottom layer of Petit-Saut reservoir was biologically mediated. Dissolved gaseous mercury formation rates in the surface sediment suspensions were of the same order of magnitude as formation rates in freshwater lakes reported in literature.

[The verrucous laryngeal carcinoma. A rare tumor with a difficult diagnosis]. / Le carcinome verruqueux du larynx. Une tumeur rare, de diagnostic difficile.

OBJECTIVES: The authors report a single case of laryngeal verrucous carcinoma and review the literature. MATERIALS AND METHOD: The delay of the diagnosis, the difficulties in its establishment and the therapeutic methods are discussed in a review of the literature. RESULTS: Histopathological diagnosis remains difficult. This may explain a great number of mistakes and the subsequent delay of in treatment. The role of radiotherapy is discussed. CONCLUSION: The diagnosis and management of the laryngeal verrucous carcinoma is difficult.

[Anatomy of the external laryngeal nerve: surgical implications. Report of 30 dissections]. / Anatomie du nerf laryngé externe: implications chirurgicales. A propos de 30 dissections.

OBJECTIVES: This anatomic study aimed to detail the anatomy of the external laryngeal nerve and to determine the possible variations of nerves at risk. MATERIAL AND METHOD: Fifteen cadavers (30 nerves) were dissected. The peri pharyngo laryngeal route, the anatomic rapports, the branches of division and the distal penetration point of the external laryngeal nerve were noted. RESULTS: The external laryngeal nerve gave branches to the inferior pharyngeal constrictor muscle in 90% of cases and to the thyroid gland in 70% of cases. There was an adherence between the nerve and the trunk of the superior thyroid artery in 13.33% of cases. The nerve had a distal superficial route even on the cricothyroid muscle in 6.67% of cases. In one case the nerve was situated close to the medial face of the superior thyroid lobe. DISCUSSION/CONCLUSION: The external laryngeal nerve has numerous anatomic variations. The anatomic variations at risk during thyroid surgery are: an adherence between the nerve and the thyroid artery (or a course of the nerve between the branches of the superior thyroid artery); a superficial distal route; a distal situation close to the medial face of the thyroid lobe. In this study, 7 nerves were considered at risk (23.33% of cases).

Surface complexation of ferrous iron and carbonate on ferrihydrite and the mobilization of arsenic.

Surface complexation models are commonly used to predict the mobility of trace metals in aquifers. For arsenic in groundwater, surface complexation models cannot be used because the database is incomplete. Both carbonate and ferrous iron are often present at a high concentration in groundwater and will influence the sorption of arsenic, but the surface complexation constants are absent in the database of Dzombak and Morel. This paper presents the surface complexation constants for carbonate and ferrous iron on ferrihydrite as derived for the double-layer model. For ferrous iron the constants were obtained from published data supplemented by new experiments to determine the sorption on the strong sites of ferrihydrite. For carbonate the constants were derived from experiments by Zachara et al., who employed relatively low concentrations of carbonate. The double-layer model, optimized for low concentrations, was tested against sorption experiments of carbonate on goethite at higher concentration by Villalobos and Leckie, and reasonable agreement was found. Sorption was also estimated using linear free energy relations (LFER), and results compared well with our derived constants. Model calculations confirm that sorption of particularly carbonate at common soil and groundwater concentrations reduces the sorption capacity of arsenic on ferrihydrite significantly. The displacing effect of carbonate on sorbed arsenate and arsenite has been overlooked in many studies. It may be an important cause for the high concentrations of arsenic in groundwater in Bangladesh. Sediments containing high amounts of sorbed arsenic are deposited in surface water with low carbonate concentrations. Subsequently the sediments become exposed to groundwater with a high dissolved carbonate content, and arsenic is mobilized by displacement from the sediment surface.

A dynamic study of the sorption and the transport processes of cadmium in calcareous sandy soils.

The interactions of Cd2+ with silica and calcite were observed through laboratory dynamic experiments. Cd2+ sorption processes were characterised as a function of reaction kinetics in aqueous solutions saturated or not with respect to calcite. Chromatographic column experiments show that Cd2+ sorption on silica can be considered as a reversible equilibrate reaction which depends on water composition and pH. For a porous medium composed by a mixture of silica and calcite, the Cd2+ migration behaviours are predominantly controlled by calcite. The amount and the reversibility of sorbed Cd on calcite are strongly affected by kinetic limitations. Stirred flow through reactor experiments provide an original method to separate and characterise the 'fast' and 'slow' Cd sorption on calcite processes. The 'fast' Cd reversible adsorption isotherms and the rate of Cd subsequent uptake by 'slow' reactions are determined. In addition, the inhibition of calcite dissolution is observed as a function of sorbed Cd in order to provide a complete mechanistic database for coupled transport-geochemistry models.

First Report of Charcoal Rot (Macrophomina phaseolina) on Sunflower in North and South Dakota.

In September 1998, symptoms suggestive of charcoal rot were observed on oilseed sunflower (Helianthus annuus L.) plants in western North and South Dakota. Symptoms first observed on plants approaching physiological maturity consisted of silver-gray lesions girdling the stem at the soil line, premature plant death, and reduced head diameter. The pith in the lower stem was completely absent or compressed into horizontal layers. Black, spherical microsclerotia were observed in the pith of the lower stem, underneath the epidermis, and on the exterior of the taproot. Confirmation of Macrophomina phaseolina (Tossi) Goid. as the causal agent was based on the size of the microsclerotia, which ranged from 80 to 90 µm in diameter, from both infected sunflowers and pure cultures (1). The only other sunflower pathogen known to form microsclerotia is Verticillium dahliae Kleb., whose microsclerotia are irregular in shape and are 15 to 50 µm in diameter. Some prematurely dead sunflower plants lacked typical charcoal rot stem lesions, but contained Macrophomina microsclerotia. Plants with atypical symptoms were colonized by the sunflower stem weevil (Cylindrocopturus adspersus (LeConte)) and the black sunflower stem weevil (Apion occidentale Fall). This agrees with observations in Texas, where Macrophomina-infected sunflower plants parasitized by stem-feeding insects often displayed atypical charcoal rot symptoms (3). Charcoal rot incidence in 1998 in western North Dakota was 25%, compared with 0% in eastern North Dakota. Charcoal rot was not observed in 1999, the fourth wettest growing season on record, but was observed again in 2000 and 2001. The recent increase in sunflower production in western North and South Dakota, areas typically hotter and drier than the eastern portions of both states, and the potential involvement of stem weevils as vectors of Macrophomina (2) may lead to an increased incidence of charcoal rot in sunflower. References: (1) P. Holliday and E. Punithalingam. Macrophomina phaseolina. No. 275 in: Description of Pathogenic Fungi and Bacteria, CMI, Kew, Surrey, UK, 1970. (2) S. M. Yang et al. Phytopathology 73:1467, 1983. (3) S. M. Yang and D. F. Owen. Phytopathology 72:819, 1982.

First Report of Puccinia xanthii on Sunflower in North America.

Puccinia xanthii Schwein., commonly known as cocklebur rust, is circumglobal on species of Xanthium and Ambrosia. This microcyclic rust has only been observed on oilseed sunflower (Helianthus annuus L.) in Australia (1) and on ornamental sunflowers in South Africa (4). In September 1999, large (4 to 10 mm), raised, chlorotic pustules were observed on the adaxial leaf surface of oilseed sunflower plants (Dekalb 3790) near Hettinger, ND. Telia were associated with the pustules on the abaxial leaf surface. No cocklebur (X. strumarium L.) plants were found in the field, but rust-infected cocklebur plants were collected several kilometers away. Approximately 10% of sunflower plants in the field were affected, and generally only one or two pustules were observed on one or two leaves per plant. In contrast, numerous leaves of cockleur plants were infected with 12 or more pustules. Teliospores from sunflower were brown, two-celled, and averaged 49 × 17 µm, with a distinctly thicker wall at the spore apex and a persistent pedicel averaging 40 µm long. Teliospores from cocklebur were morphologically similar to those from sunflower and averaged 46 × 16 µm. Size and morphology of teliospores from both hosts fit the description of P. xanthii (2). P. xanthii can be distinguished easily from the ubiquitous P. helianthi Schwein. because the latter has smaller telia (1 to 2 mm diameter) and produces wider teliospores (21 to 30 µm diameter). P. xanthii was not found in surveys of 20 other sunflower fields in southwestern North Dakota nor in 45 fields in eastern ND in 1999, nor was P. xanthii found in this or any other sunflower field in 2000 or 2001. To our knowledge, this is the first report of P. xanthii on cultivated or wild sunflower in North America. The relatively few pustules observed on oilseed sunflower agree with the observation that oilseed sunflowers are much less susceptible to P. xanthii (3) than Xanthium spp. References: (1) J. L. Alcorn and J. K. Kochman. Austral. Plant Pathol. Soc. Newsl. 5:33, 1976. (2) G. B. Cummins. Rust Fungi on Legumes and Composites in North America. University of Arizona Press, Tucson, 1978. (3) J. B. Morin et al. Can. J. Bot. 71:959, 1993. (4) Z. A. Pretorius et al. Plant Dis. 84:924, 2000.

Risk of arsenic transfer to a semi-confined aquifer and the effect of water level fluctuation in North Mortagne, France at a former industrial site.

Groundwater contamination by arsenic was studied in the area of a former larger zinc refinery in France. Maximum contamination was observed under the former sulfuric acid factory, while the overall waste storage area was less contaminated. Arsenic concentrations there were controlled by the solubility of 3:2 calcium arsenate mineral Ca3(AsO4)2 (s) and probably a gypsum/calcium arsenate CaSO4 (s)/Ca3(AsO4)2 (s) solid solution. The speciation of As below the former sulfuric acid factory indicates an overall predominance of As(III) species. The sorption by the clay aquitard was complete for As(V), but limited to approximately 30% for As(III) under our experimental conditions. A potential risk exists, although very limited in area, of contamination of the underlying sandy aquifer and drinking water wells.

Uranyl Surface Speciation on Silica Particles Studied by Time-Resolved Laser-Induced Fluorescence Spectroscopy.

The sorption of uranyl ions onto amorphous silica has been studied in the presence of atmospheric CO(2) by laser-induced time-resolved fluorescence spectroscopy at trace concentrations (1.0 and 0.1 &mgr;M). Two fluorescent uranyl surface complexes have been identified in the pH range 4 to 9. Both complexes could be differentiated by lifetimes (170+/-25 &mgr;s at low pH and 360+/-50 &mgr;s at high pH) and fluorescence emission spectra. Within the constant capacitance model framework they are described by mononuclear (1 : 1) complexes with release of two and three protons, respectively. When fluorescence data were compared to wet chemistry sorption data, a third "silent" ternary uranyl-silica-carbonate surface complex had to be postulated to account partly for adsorption between pH 8.0 and 9.0. Three independent data sets led therefore to the identification of three surface complexes, postulated as &tbond;SiO(2)UO(2) degrees,&tbond;SiO(2)UO(2)OH(-), and &tbond;SiO(2)UO(2)OHCO(3)(3-). Copyright 2001 Academic Press.

Evidence for the Formation of Trioctahedral Clay upon Sorption of Co(2+) on Quartz.

The sorption mechanism of Co on quartz at room temperature has been investigated by an in-depth analysis of published extended X-ray absorption fine structure (EXAFS) spectroscopy and solution chemistry data. In particular, the 3.5-5 Å mid-range atomic environment of Co has been determined with unprecedented precision by combining ad initio FEFF7.02 calculations and results obtained by polarized EXAFS on the mid-distance structure of sheet silicate minerals. The local atomic environment around sorbed Co atoms is identical to that of Co in trioctahedral clays and substantially different from that in the cobalt hydroxide Co(OH)(2(s)). Neoformation of a trioctahedral clay is consistent with calculated thermodynamic solubilities, which indicate that 2:1 and 1:1 Co-rich hydrous silicates, similar to kerolite and chrysotile, are less soluble than Co(OH)(2(s)). Consequently, precipitation of Co-rich clay is favored over that of Co(OH)(2(s)) at pH values below 9 and for a dissolved Si concentration equal to quartz solubility. New experimental data show that dissolved Si concentrations can approach, and even exceed, that of quartz solubility during the short times of sorption experiments. Based on the available data, it is not possible to conclude unequivocally if the Co layer silicate grew epitaxially on the quartz surface, topotactically in a surface amorphous layer, or independently of the quartz framework structure. The structural and chemical interpretation is supported by recent published studies in which sorption of a hydrolyzable cation leads to the neoformation of a mixed layer phase formed from the sorbate species and the sorbent metal. This surface-induced precipitation mechanism is a general phenomenon that may account for the formation of secondary clays as coatings on silicates. Copyright 1999 Academic Press.

Sorption of Metal Ions on Clay Minerals.

The mechanism of Co uptake from aqueous solution onto hectorite (a magnesian smectite) and its impact on the stability of this clay mineral were investigated as a function of Co concentration (TotCo = 20 to 200 µM, 0.3 M NaNO(3)) and ionic strength (0.3 and 0.01 M NaNO(3), TotCo = 100 µM) by combining kinetics measurements and Co K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. The morphology of the sorbent phase was characterized by atomic force microscopy (AFM) and consists of lath-type particles bounded by large basal planes and layer edges. At low ionic strength (0.01 M NaNO(3)), important Co uptake occurred within the first 5 min of reaction, consistent with Co adsorption on exchange sites of hectorite basal planes. Thereafter, the sorption rate dramatically decreased. In contrast, at high ionic strength (0.3 M NaNO(3)), Co uptake rate was much slower within the first 5 min and afterward higher than at 0.01 M NaNO(3), consistent with Co adsorption on specific surface sites located on the edges of hectorite. Time-dependent isotherms for Co uptake at high ionic strength indicated the existence of several sorption mechanisms having distinct equilibration times. The dissolution of hectorite was monitored before and after Co addition. A congruent dissolution regime was observed prior to Co addition. Just after Co addition, an excess release of Mg relatively to congruent dissolution rates occurred at both high and low ionic strengths. At high ionic strength, this excess release nearly equaled the amount of sorbed Co. The dissolution rate of hectorite then decreased at longer Co sorption times. EXAFS spectra of hectorite reacted with Co at high and low ionic strengths and for reaction times longer than 6 h, exhibited similar features, suggesting that the local structural environments of Co atoms are similar. Spectral simulations revealed the occurrence of approximately 2 Mg and approximately 2 Si neighboring cations at interatomic distances characteristic of edge-sharing linkages between Co and Mg octahedra and corner-sharing linkages between Co octahedra and Si tetrahedra, respectively. This local structure is characteristic of inner sphere mononuclear surface complexes at layer edges of hectorite platelets. The occurrence of these complexes even at low ionic strength apparently conflicts with kinetics results, as exchangeable divalent cations are known to form outer sphere surface complexes. To clarify this issue, the amount of Co adsorbed on exchange sites was calculated from the solute Co concentration, assuming that cation exchange was always at equilibrium. These calculations showed that sorbed Co was transferred within 48 h from exchange sites to edge sorption sites. Copyright 1999 Academic Press.

Sorption of Metal Ions on Clay Minerals.

The local structural environment of Co sorbed on hectorite (a magnesian smectite) has been investigated by polarized EXAFS (P-EXAFS) spectroscopy on a self-supporting film of Co-sorbed hectorite. This sorption sample was prepared by contacting Co and hectorite at pH 6.5 and at high ionic strength (0.3 M NaNO3) to favor pH-dependent sorption reaction over cation exchange. A self-supporting film was elaborated after 120 h of reacting time, when apparent quasi-equilibrium conditions were attained. The half-width at half maximum of the orientation distribution of c* axis of individual clay platelets off the film normal was determined by quantitative texture analysis, and found to be equal to 18.9 degrees. Co K-edge P-EXAFS spectra were recorded at angles between the incident beam and the film normal equal to 0 degrees, 35 degrees, 50 degrees, and 60 degrees; the 90 degrees spectrum was obtained by extrapolation. Spectral analysis led to the identification of the two nearest cationic subshells containing 1.6 +/- 0.4 Mg at 3.03 Å and 2.2 +/- 0.5 Si at 3.27 Å. These distances are respectively characteristic of edge-sharing linkages between Mg and Co octahedra and of corner-sharing linkages between Co octahedra and Si tetrahedra, as in clay structures. The angular dependence of the Co-Mg and Co-Si contributions indicates that Co-Mg pairs are oriented parallel to the film plane, whereas Co-Si pairs are not. These results are interpreted by the formation of Co inner-sphere mononuclear surface complexes located at the edges of hectorite platelets, in the continuity of the (Mg, Li) octahedral sheet. Copyright 1999 Academic Press.