Geochemical characterization of volcanic ashes from recent events in Northern Patagonia Andean Range by INAA

Summary Volcanic ashes erupted by recent magmatic events were collected from one sedimentary sequence of lake Nahuel Huapi (Patagonia, Argentina) and then analyzed by Instrumental Neutron Activation Analysis. Primary volcanic components, including white and brownish pumice fragments, scoriae and glass shards, as well as bulk sediments from four tephra layers identified in the sedimentary sequence, were characterized by their major and trace element contents. The two tephra layers being in the upper section of the sequence can be linked to the eruptions of Cordon Caulle fissure (Puyehue-Cordon Caulle region) occurred in 1921-1922 and 1960, according to core dating. The third tephra layer, which is clearly associated to an event occurred in the 1890-1900 decade, has different compositional patterns showing a different source from those upper tephras. Whereas, the fourth, which could be associated to an event occurred at the end of the 18 th century, shows the same composition patterns as those registered for the Cordon Caulle fissure.     

Elution behaviour and environmental impact of heavy metals and rare-earth elements from volcanic ashes of Mt. Oyama,Miyake Island

To obtain information on the environmental impact of materials eluted from volcanic ashes of Mt. Oyama, Miyake Island, which erupted in July 2000, the dissolution behaviours of heavy metals and rare-earth elements from the volcanic ashes were examined. The most important characteristic of the Mt. Oyama eruption is that sulphur dioxide (SO₂) gas has been continuously released, and all persons living on Miyake Island have been required to evacuate. To estimate in terms of the volcanic eruption using SO₂ gas, the ash nature in Mt. Usu, Hokkaido, was also examined and compared with that in Mt. Oyama. When rain water mixed the ashes, the water from the ashes of Mt. Oyama became acidic because of the sulphuric acid. Therefore, SO₂ gas in Mt. Oyama can accelerate the dissolution of protons and heavy metals in the ashes, whereas the rain water in Mt. Usu was not acidic and the dissolution of the heavy metals was not so evident compared with that in the case of Mt. Oyama. With this sulphuric acid, heavy metals such as As, Cd, Pb and Hg in the ashes in Mt. Oyama easily dissolved owing to the low pH. The ashes in Mt. Oyama had been released for eight years and the amount of fallen ashes was estimated to be 33 billion tons. The weights of the harmful heavy metals in the volcanic ashes, such as As, Cd, Pb and Hg, were estimated to be 3.8?×?10², 1.3?×?10³, 1.1?×?10³ and 29?kg, respectively, and these heavy metals were dissolved and diluted in seawater. Therefore, the concentration and species (chemical form) of these metals should be carefully monitored in the future. Moreover, SO₂ gas, which has a direct effect on human health and has been monitored continuously, causes other effects, such as facilitation of metal ion elution and rock aeration.     

Application of surface complexation modeling on the leaching of radionuclides from fly ashes

Surface complexation modeling based on diffuse double layer model (DDLM) has been employed to simulate the leaching behaviors of radionuclides (i.e., ⁶⁰Co²⁺, ⁶³Ni²⁺, ⁶⁴Cu²⁺ and UO₂ ²⁺) on fly ashes from hospital wastes. The fly ashes were characterized by X-ray diffraction (XRD), potentiometric acid–base titration, and scanning electron microscopy (SEM). The effect of pH, the ratio of solid-to-liquid (RSL), and particle size on the leaching of radionuclides was also conducted under the batch techniques. According to XRD patterns analysis, the main components of fly ashes was determined to be quartz and clay minerals such as kaolinite, illite and smectite. The site density and pH_PNZC (pH at point of net zero charge) of fly ashes calculated from potentiometric titration data was found to be 4.53 × 10^?4 mol/g and 7.4, respectively. One can see that the small amount of metal oxides attached on the surface of fly ashes by SEM images, corrosion surface of fly ashes was observed after leaching experiments. Results of the batch leaching experiments indicated that the leaching amount of radionuclides in fly ashes significantly depended on pH, the ratio of solid-to-liquid, and particle size. It is found that the leaching amount of radionuclides decreased in the order of ⁶⁴Cu²⁺ ? ⁶³Ni²⁺ > ⁶⁰Co²⁺ > UO₂ ²⁺ under the different pH, the RSL or particle size conditions. In this paper, DDLM has successfully been applied to describe the leaching behaviors of radionuclides from fly ashes. This research provides critical information for application of surface complexation modeling on the simulation of radionuclides leaching from fly ashes, which would clarify the leaching mechanism of radionuclides from fly ashes.     

Chemical fractionation of a fly ash sample by a sequential leaching method

A five-stage sequential leaching procedure was optimized for the analysis of the fly ash sample, CW6, as a candidate reference material. The distribution of particulate elements was achieved for Cd, Cr, Cu, Pb, Zn, and V into different fractions: (1) exchangeable, (2) bound to carbonate, (3) bound to Fe/Mn oxides, (4) bound to sulfide compounds, and (5) acid soluble, residual fraction. The leachability of the metals proved to be different, so various distribution patterns have been achieved. The results of the total elemental analysis and the sequential leaching method were compared and a good agreement was found. The uncertainty of the leaching method is reasonable, even when experimental parameters are strictly fixed and the analysis is quite tedious. The ratio of environmentally mobile fractions was compared to that from the conventional test method and a reasonable conformity has been found. This characterization method can be used to interpret the leaching behavior of element species and mode of binding to the matrix. Using the optimized sequential procedure, a new aspect can be interpreted to understand the behavior of toxic elements released from fly ashes into nature.     

Release of coprecipitated uranium from iron oxides

Summary The removal of uranium (VI) from zerovalent iron permeable reactive barriers and wetlands can be explained by its association with iron oxides. The long term stability of immobilized U is yet to be addressed. The present study investigates the remobilization of U(VI) from iron oxides via diverse reaction pathways (acidification, reduction, complex formation). Prior, uranium coprecipitation experiments were conducted under various conditions. The addition of various amounts of a pH-shifting agents (pyrite), an iron complexing agent (EDTA) or iron (III) reduction agent (TiCl₃) yielded in uranium remobilization, concentrations above the US EPA allowedmaximum contaminant level(MCL=30 μg/l). This study demonstrates that U(VI) release in nature strongly depends on the conditions and the mechanism of its fixation by geological materials.     

Multielemental analyses of tree rings by inductively coupled plasma mass spectrometry

Inductively coupled plasma mass spectrometry (ICP-MS) was evaluated for major, minor, trace, and ultra-trace elemental analyses of individual tree rings. The samples were obtained from an old-growth Douglas fir (Pseudotsuga menziesii) growing 15 km northeast of Mount St. Helens volcano, Washington, USA and from trees at various other North American sites. Samples were brought into solution by microwave digestion in sealed Teflon vessels. Eightly percent of elements from Li to U had detection limits in the solid (wood) below 8.0 ng g^–1 (parts per billion, ppb). When selected element concentrations in the Mount St. Helens samples are plotted against time, two anomalous peaks occur at A. D. 1478 and 1490 that closely correlate with past eruptions of the volcano. These preliminary results show that ICP-MS is a rapid and sensitive analytical method for multielemental analyses of individual tree rings.     

Speciation of the inorganic components in brown coal

Brown coal samples from different deposits have been analyzed for the bonding forms of their inorganic components. Besides the analysis of the dried coals, ashing techniques (high and low temperature ashing) and extraction procedures with different solvents (acids, bases, complexation agents, organic solvents with different polarity) have also been investigated. ESCA, PIXE, INAA, ICP-Atomic Emission Spectroscopy, NMR and Ionchromatography have been applied to the analysis of coals, ashes, wet ashing and extraction products. The bonding behavior of more than 40 elements could be characterized. Conclusions about geological and geochemical processes during and after coalification could be drawn.     

Determination of trace elements in fly ash samples by FAAS after applying different digestion procedure

The fly ash samples obtained from Kangal Power Plant were prepared for FAAS analysis by a new approach. The trace elements of the fly ash samples were leached with appropriate solvents under suitable conditions. The leaching method is known as an effective technique for substances dissolving very hard and refractory materials. The leaching effects of solvents and their mixtures were investigated on fly ash samples that are used largely in analysis of soil and sediment samples.The fly ashes mainly consist of glassy aluminosilicates. The major components of the samples are SiO₂, Al₂O₃, CaO and Fe₂O₃. Therefore, decomposition of the silicate lattice of the fly ash is required for liberation of trace elements. The dissolution process can be completed by using a mineral acid such as concentrated HCl. This technique has an advantage that the fly ash can be dissolved without any oxidation at room temperature.Maximum element recoveries were obtained by the procedure of 37% HCl leaching after the samples were treated with 2.0 ml of concentrated HF. It was also observed that maximum mass loss occurred in this procedure. The effect of the four leaching reagents, which are HCl, HNO₃, HClO₄ and HNO₃ + HClO_4, were investigated on fly ash samples that were treated with concentrated HF. An optimum leaching method was determined based on the confidence of analytical results and element recovery rates.     

Platinum solubility of a substance designed as a model for emissions of automobile catalytic converters

Automobile catalytic converters emit nanocrystalline platinum attached to alumina particles. For investigations about the bioavailability of Pt from these particles a model substance with approx. 5% Pt on alumina has been prepared and characterized by physical methods (ESCA, XRD, TEM, DTA, TG). Measuring the platinum solubility of these samples in different solvents revealed high amounts that can be explained assuming a corrosion process. The portion of soluble platinum is dependent on the particle size distribution. For a comparative study platinum black has been used. In general the platinum determination has been carried out by electrothermal atomic absorption spectrometry (ET-AAS). The comparison of ET-AAS results with determinations by adsorptive voltammetry (formazone method) allowed to distinguish between elemental and ionic platinum; in solution samples only ionic platinum has been present. UV spectra of extracts have been used for the semi-quantitative platinum speciation in solutions.     

Platinum solubility of a substance designed as a model for emissions of automobile catalytic converters

Automobile catalytic converters emit nanocrystalline platinum attached to alumina particles. For investigations about the bioavailability of Pt from these particles a model substance with approx. 5% Pt on alumina has been prepared and characterized by physical methods (ESCA, XRD, TEM, DTA, TG). Measuring the platinum solubility of these samples in different solvents revealed high amounts that can be explained assuming a corrosion process. The portion of soluble platinum is dependent on the particle size distribution. For a comparative study platinum black has been used. In general the platinum determination has been carried out by electrothermal atomic absorption spectrometry (ET-AAS). The comparison of ET-AAS results with determinations by adsorptive voltammetry (formazone method) allowed to distinguish between elemental and ionic platinum; in solution samples only ionic platinum has been present. UV spectra of extracts have been used for the semi-quantitative platinum speciation in solutions.     

Neutron activation studies of trace elements in tree rings

The levels of twelve elements most of which are either considered essential to plant growth or have been detected in air filter samples in an air pollution survey, have been monitored in three transverse sections of trees, two elms (ring porous trees) and one cedar (a conifer). Two dimensional distributions of these elements around the tree rings of the section and radially from ring to ring, have been obtained to see if tree rings can be analysed for use as a record of historical pollution.     

Use of Adsorbents for Recovery of Acetic Acid from Aqueous Solutions Part III—Solvent Regeneration

Solvent leaching was investigated as a method of regeneration for activated carbons and polymer sorbents loaded with acetic acid by contact with aqueous solutions. Both batch-equilibration and fixed-bed experiments were employed. Methanol, methyl acetate, and acetone are suitable regeneration solvents for most activated carbons. Amoco GX-031 is an exception, giving incomplete regeneration. Methanol provides still more efficient regeneration for macroreticular styrene-divinylbenzenes adsorbents. Among basic sorbents, amine resins give incomplete regeneration by solvent leaching, as does a poly N oxide. Polybenzimidazole, a weaker base, gives higher recoveries of acetic acid when leached by solvents. Poly(4-vinylpyridine) is regenerated completely and efficiently by methanol, methyl acetate, and acetone in a fixed-bed geometry. It thus appears that an intermediate degree of basicity is desirable in a synthetic sorbent for acetic acid – strong enough to give the uptake benefits of acid-base interactions, but weak enough to be regenerable.     

Denaturation and Leaching Study of Horseradish Peroxidase Encapsulated in Sol-Gel Matrices

Sol-gel matrices have been shown to be relatively inert while preserving the spectroscopic properties and biological activity of the encapsulated proteins. Horseradish peroxidase (HRP) is a hemeprotein widely used in the field of biosensors because of its high specificity for hydrogen peroxide. However, partial inactivation of the protein has been reported when incorporated in aged gels. Whether that inactivation comes from the unfolding of some of the encapsulated proteins or from the leaching of the heme non-covalent active site of HRP is evaluated by absorption and fluorescence spectroscopy. This study shows that the single Trytophan (Trp) fluorescence of HRP may be used to distinguish denaturation processes from leaching of the heme group, as well as to estimate the extent of the denaturation.     

A homogeneous, recyclable polymer support for Rh(I)-catalyzed C-C bond formation

A robust and practical polymer-supported, homogeneous, recyclable biphephos rhodium(I) catalyst has been developed for C-C bond formation reactions. Control of polymer molecular weight allowed tuning of the polymer solubility such that the polymer-supported catalyst is soluble in nonpolar solvents and insoluble in polar solvents. Using the supported rhodium catalysts, addition of aryl and vinylboronic acids to the electrophiles such as enones, aldehydes, N-sulfonyl aldimines, and alkynes occurs smoothly to provide products in high yields. Additions of terminal alkynes to enones and industrially relevant hydroformylation reactions have also been successfully carried out. Studies show that the leaching of Rh from the polymer support is low and catalyst recycle can be achieved by simple precipitation and filtration.     

Radiocarbon ages of lacustrine deposits in volcanic sequences of the Lomas Coloradas area, Socorro Island, Mexico

Extensive eruptions of alkalic basalt from low-elevation fissures and vents on the southern flank of the dormant volcano, Cerro Evermann, accompanied the most recent phase of volcanic activity on Socorro Island, and created the Lomas Coloradas, a broad, gently sloping terrain comprising the southern part of the island. We obtained 14C ages of 4690 +/- 270 BP (5000-5700 cal BP) and 5040 +/- 460 BP (5300-6300 cal BP) from lacustrine deposits that occur within volcanic sequences of the lower Lomas Coloradas. Apparently, the sediments accumulated within a topographic depression between two scoria cones shortly after they formed. The lacrustine environment was destroyed when the cones were breached by headward erosion of adjacent stream drainages. This was followed by the eruption of a thin basaltic flow from fissures near the base of the northernmost cone. The flow moved downslope for a short distance and into the drainages that presently bound the study area on the east and west. The flow postdates development of the present drainage system and may be very recent. Our 14C data, along with historical accounts of volcanic activity over the last century, including submarine eruptions that occurred a few km west of Socorro in early 1993, underscore the high risk for explosive volcanism in this region and the need for a detailed volcanic hazards plan and seismic monitoring.     

Azolium-linked cyclophanes: effects of structure, solvent, and counteranions on solution conformation behavior

This paper describes the synthesis, structural characterization, and solution behavior of some xylyl-linked imidazolium and benzimidazolium cyclophanes decorated with alkyl or alkoxy groups. The addition of alkyl/alkoxy chains to the cyclophanes allows for studies in chlorinated solvents, whereas previous solution studies of azolium cyclophanes have generally required highly polar solvents. The azolium cyclophanes may exist in a syn/syn conformation (azolium rings mutually syn, arene rings mutually syn) or a syn/anti conformation (azolium rings mutually syn, arene rings mutually anti). The preferred conformation is significantly affected by (i) binding of bromide (ion pairing) to the protons on the imidazolium or benzimidazolium rings, which occurs in solutions of bromide salts of the cyclophanes in chlorinated solvents, and (ii) the addition of alkoxy groups to the benzimidazolium cyclophanes. These structural modifications have also led to cyclophanes that adopt conformations not previously identified for similar azolium cyclophane analogues. Detailed (1)H NMR studies for one cyclophane identified binding of bromide at two independent sites within the cyclophane.     

South Aegean Volcanic Glass: Separation and Analysis by INAA and EPMA

Pumice from the major volcanic sources (Milos, Nisyros, Yali, Kos and Santorini) in the South Aegean region was investigated to reveal the differences between the composition of the bulk material, which contains a certain percentage of crystallites, and the pure glass phase, which is the main constituent. The knowledge of these differences is important for the identification of vitric tephra layers found in the Eastern Mediterranean region in archacological context, in deep sea drilling cores and lake sediments. Eruption products, deposited at some distance, show not only a decrease in their grain size, but also have usually lost their crystalline fraction due to gravity separation and consist only of glass shards. Major element distributions in such layers and in pumiceous glass are not sufficient for a reliable identification of the volcanic source, as several eruptions are known to have produced chemically very similar tephra layers in this region. Trace element data, especially of the rather immobile rare earth elements (REEs), can provide greater information on tephra originating from different volcanic eruptions. Therefore, a technique has been developed to separate the glass phase from different primary pumices to reveal differences in their trace element distributions. The concentrations of the major constituents, in particular Al, Ca, Fe, Mg, Mn, Na, Si, and Ti were determined by electron probe microanalysis (EPMA), those of Al, As, Ba, Ca, Ce, Co, Cr, Cs, Dy, Eu, Fe, Hf, K, La, Lu, Mn, Na, Nd, Rb, Sb, Sc, Sm, Ta, Th, Ti, U, V, Yb and Zr by instrumental neutron activation analysis. Subtle differences between the compositions of the glass phase and the bulk material are explained by differentiation during partial crystallization. Their applicability to the classification of tephra layers is demonstrated.     

Competitive formation of 10- and 7-membered hydrogen-bonded rings of proline-containing model peptides

Intramolecularly hydrogen-bonded structures of proline-containing model peptides with a sequence of N-tert-butoxycarbonyl-prolyl-Xaa-NHCH3 [Xaa = Gly (glycyl), Ala (alanyl), Phe (phenylalanyl), Leu (leucyl), Ile (isoleucyl), and Val (valyl)] were studied by proton nuclear magnetic resonance and infrared spectroscopy. Variation of chemical shifts of amide protons with composition change of DMSO-d6/CDCl3 mixed solvents were found to be a good measure of intramolecular hydrogen bonding of peptides in CDCl3 solution. It has been shown that 10- and 7-membered hydrogen-bonded rings, which should have the beta- and gamma-turn like structures in proteins, respectively, form competitively with each other. It is suggested that the equilibrium between the two hydrogen-bonded rings is determined by steric hindrance due to a side chain of the Xaa residue. Free energies for formation of the 10- and 7-membered hydrogen-bonded rings, deltaG10 and deltaG7, were estimated from the solvent composition-dependent change of the chemical shifts. A good correlation between deltaG10 and the occurrence frequencies of residues Xaa at the (i + 2)th position for the beta-turns in proteins has been found.     

The Boron and Lithium Content of South African Coals and Coal Ashes

Abstract

Boron and lithium were determined in over a hundred coals and power station ashes by inductively coupled plasma atomic emission spectroscopy. The levels of boron in coals and fly ashes range from 15 to 83 μg.g^?1 and from 23 to 600 μg.g^?1, respectively, while lithium occurred at levels of between 45 and 81μg.g^?1 in coals and 77 and 359μg.g^?1 in fly ashes. Both elements were found to vary considerably between different coals and ashes produced. In most cases the boron concentration was found to increase systematically between the first and last precipitators where smaller particle size fractions are collected. The availability of boron from the leaching of fly ashes by water was investigated. Leachabilities were found to vary for ashes produced at different power stations.     

Variations of trace element contents within single tree rings

X-ray fluorescence was used to measure variations in relative and absolute trace-element concentrations within single tree rings taken from a 32-year-old pine tree near a coalburning power plant. The Zn/Cu ratio was found to have a constant value, both along individual rings and between different rings. The Fe, Ca and 8 concentrations varied in a single tree ring and depended on the age of the tree. The results indicate that the variations in concentrations of elements along a single ring are caused by heterogeneous tree tissue structure.