Coprecipitation of Ti,Mo, Sn and Sb with fluorides and application to determination of B,Ti, Zr,Nb, Mo,Sn, Sb,Hf and Ta by ICP-MS

We examined the coprecipitation behavior of Ti, Mo, Sn and Sb in Ca–Al–Mg fluorides under two different fluoride forming conditions: at < 70 °C in an ultrasonic bath (denoted as the ultrasonic method) and at 245 °C using a Teflon bomb (denoted as the bomb method). In the ultrasonic method, small amounts of Ti, Mo and Sn coprecipitation were observed with 100% Ca and 100% Mg fluorides. No coprecipitation of Ti, Mo, Sn and Sb in Ca–Al–Mg fluorides occurred when the sample was decomposed by the bomb method except for 100% Ca fluoride. Based on our coprecipitation observations, we have developed a simultaneous determination method for B, Ti, Zr, Nb, Mo, Sn, Sb, Hf and Ta by Q-pole type ICP-MS (ICP-QMS) and sector field type ICP-MS (ICP-SFMS). 9–50 mg of samples with Zr–Mo–Sn–Sb–Hf spikes were decomposed by HF using the bomb method and the ultrasonic method with B spike. The sample was then evaporated and re-dissolved into 0.5 mol l^− 1 HF, followed by the removal of fluorides by centrifuging. B, Zr, Mo, Sn, Sb and Hf were measured by ID method. Nb and Ta were measured by the ID-internal standardization method, based on Nb/Mo and Ta/Mo ratios using ICP-QMS, for which pseudo-FI was developed and applied. When 100% recovery yields of Zr and Hf are expected, Nb/Zr and Ta/Hf ratios may also be used. Ti was determined by the ID-internal standardization method, based on the Ti/Nb ratio from ICP-SFMS. Only 0.053 ml sample solution was required for measurement of all 9 elements. Dilution factors of ≤ 340 were aspirated without matrix effects. To demonstrate the applicability of our method, 4 carbonaceous chondrites (Ivuna, Orgueil, Cold Bokkeveld and Allende) as well as GSJ and USGS silicate reference materials of basalts, andesites and peridotites were analyzed. Our analytical results are consistent with previous studies, and the mean reproducibility of each element is 1.0–4.6% for basalts and andesites, and 6.7–11% for peridotites except for TiO₂.     

The coagulation,solubility and adsorption properties of Fe,Mn, Cu,Ni, Cd,Co and humic acids in a river water

River water (Water of Luce, Scotland) is used in laboratory experiments designed to investigate physical and chemical properties of Fe. Mn, Cu, Ni, Co, Cd and humic acids in riverine and estuarine systems. Using NaCl, MgCl₂ and CaCl₂ as coagulating agents, coagulation of dissolved (0.4 μm filtered) Fe, Cu, Ni, Cd and humic acids increases in a similar matter with increasing salt molarily: Ca²⁺ is the most dominant coagulating agent. Removal by coagulation with Ca²⁺ at seawater concentrations ranges from large (Fe-80%. HA-60%, Cu-40%) to small (Ni, Cd-15%) to essentially nothing (Cd, Mn-3%). Destabilization of colloids is the indicated mechanism. Solubility-pH measurements show that between a pH of 3 and 9, Fe, Cu, Ni, Mn, Co and Cd are being held in the dissolved phase by naturally occurring organic substances. Between pH of 2.2 and 1.2 a large proportion of dissolved Fe, Cu. Ni and Cd (72, 35,44 and 36% respectively) is precipitated along with the humic acids; in contrast, Mn and Co show little precipitation (3%). Adsorption-pH experiments, using unfiltered river water spiked with Cu, indicate that adsorption of Cu onto suspended particles is inhibited to a large extent by the formation of dissolved Cu-organic complexes.The experimental results demonstrate that solubilities and adsorption properties of certain trace metals in freshwaters can be opposite to those observed with artificial solutions or predicted with chemical models. Interaction with organic substances is a critical factor.     

Roles of xenomelts,xenoliths, xenocrysts,xenovolatiles, residues,and skarns in the genesis,transport, and localization of magmatic Fe-Ni-Cu-PGE sulfides and chromite

Most sulfide-rich magmatic Ni-Cu-(PGE) deposits form in dynamic magmatic systems by partial melting S-bearing wall rocks with variable degrees of assimilation of miscible silicate and volatile components, and generation of barren to weakly-mineralized immiscible Fe sulfide xenomelts into which Ni-Cu-Co-PGE partition from the magma. Some exceptionally-thick magmatic Cr deposits may form by partial melting oxide-bearing wall rocks with variable degrees of assimilation of the miscible silicate and volatile components, and generation of barren Fe ± Ti oxide xenocrysts into which Cr-Mg-V ± Ti partition from the magma. The products of these processes are variably preserved as skarns, residues, xenoliths, xenocrysts, xenomelts, and xenovolatiles, which play important to critical roles in ore genesis, transport, localization, and/or modification. Incorporation of barren xenoliths/autoliths may induce small amounts of sulfide/chromite to segregate, but incorporation of sulfide xenomelts or oxide xenocrysts with dynamic upgrading of metal tenors (PGE > Cu > Ni > Co and Cr > V > Ti, respectively) is required to make significant ore deposits. Silicate xenomelts are only rarely preserved, but will be variably depleted in chalcophile and ferrous metals. Less dense felsic xenoliths may aid upward sulfide transport by increasing the effective viscosity and decreasing the bulk density of the magma. Denser mafic or metamorphosed xenoliths may also increase the effective viscosity of the magma, but may aid downward sulfide transport by increasing the bulk density of the magma. Sulfide wets olivine, so olivine xenocrysts may act as filter beds to collect advected finely dispersed sulfide droplets, but other silicates and xenoliths may not be wetted by sulfides. Xenovolatiles may retard settling of – or in some cases float – dense sulfide droplets. Reactions of sulfide melts with felsic country rocks may generate Fe-rich skarns that may allow sulfide melts to fractionate to more extreme Cu-Ni-rich compositions. Xenoliths, xenocrysts, xenomelts, and xenovolatiles are more likely to be preserved in cooler basaltic magmas than in hotter komatiitic magmas, and are more likely to be preserved in less dynamic (less turbulent) systems/domain/phases than in more dynamic (more turbulent) systems/domains/phases. Massive to semi-massive Ni-Cu-PGE and Cr mineralization and xenoliths are often localized within footwall embayments, dilations/jogs in dikes, throats of magma conduits, and the horizontal segments of dike-chonolith and dike-sill complexes, which represent fluid dynamic traps for both ascending and descending sulfides/oxides. If skarns, residues, xenoliths, xenocrysts, xenomelts, and/or xenovolatiles are present, they provide important constraints on ore genesis and they are valuable exploration indicators, but they must be included in elemental and isotopic mass balance calculations.     

The Determination of Total Hydrogen, Carbon, Nitrogen and Sulfur in Silicates, Silicate Rocks, Soils and Sediments

Determinations of the volatile elements carbon, hydrogen, sulfur and nitrogen in many geological RM, performed with the LECO CHN and SC analysers, are presented. The method allowed the determination of S in concentrations from a few % m/m to 0.001% m/m or less, of C from % m/m to 0.01% m/m and of H from % m/m to 0.004% m/m. Accuracy was usually better than the XRF method (for S). All obtained values passed the Sutarno-Steger test, which establishes that |(mean_analysed - mean_certified)|/ S_certified < 2, for the cases with an appropriate number of determinations (n > 10 for each element). It was possible to perform routine determination of C, H and S with the instrumentation, coupled with the determination of major and minor elements in geological materials. Determination of nitrogen could also be performed on an exploratory basis, with improvements in the method dependent on the future availability of more reference materials with reliable composition of this element.     

Terrestrial geochemistry of Cd,Bi, Tl,Pb, Zn and Rb

About 2000 common magmatic, metamorphic and sedimentary rocks and rockforming minerals contained in 465 individual samples have been analyzed for 6 trace metals and potassium with high precision, mainly by combined distillation and AAS methods. Estimates of average abundances in the continental crust are: 98 ppb Cd. 82 ppb Bi. 490 ppb Tl, 14.8 ppm Pb, 77 ppm Zn and 98 ppm Rb (K/Rb: 223). These averages are close to the mean concentrations of the 6 elements in sedimentary and in low to medium grade metamorphic rocks. In relation to the upper mantle the earth's crust has very effectively accumulated Rb, Pb, Tl (and Bi). Cd and Zn are equally distributed between the upper and lower crust. Bi, Tl, Rb, Pb and K are accumulated in the upper relative to the lower continental crust by factors between 3.5 and 1.4. This is mainly due to higher concentrations in granites and lower abundances in granulites relative to gneisses and schists. The five metals form large ions with bulk coefficients less than one for the partition between metamorphic rocks and anatectic granitic melts. The major hosts of Rb, Tl, Pb and Bi in rocks are minerals with 8- to 12-coordinated sites such as mica, K-feldspar, plagioclase etc. (except for some preference of Bi for sphene and apatite). As examples of significant correlations those of Pb with Tl, K, Bi and Rb in mafic rocks and of Bi with K, Rb, Tl and Pb in sedimentary rocks can be reported. In granites and gneisses hydroxyl containing Fe²⁺-Mg-silicates are major host minerals for Zn and Cd. Except in some carbonate rocks Cd has no preference for Ca minerals.     

Neutron-capture elements in halo, thick-disk, and thin-disk stars. Strontium, yttrium, zirconium, cerium

We derived Sr, Y, Zr, and Ce abundances for a sample of 74 cool dwarfs and subgiants with iron abundances, [Fe/H], between 0.25 and ?2.43. These estimates were obtained using synthetic spectra, assuming local thermodynamic equilibrium (LTE) for Y, Zr, and Ce, allowing for non-LTE conditions for Sr. We used high-resolution (λ/Δλ?40 000 and 60 000) spectra with signal-to-noise ratios between 50 and 200. We find that the Zr/Y, Sr/Y, and Sr/Zr ratios for the halo stars are the same in a wide metallicity range (?2.43 ≤ [Fe/H] ≤ ?0.90), within the errors, indicating a common origin for these elements at the epoch of halo formation. The Zr/Y ratios for thick-disk stars quickly decrease with increasing Ba abundance, indicating a lower rate of production of Zr compared to Y during active thick-disk formation. The thick-disk and halo stars display an increase in the [Zr/Ba] ratio with decreasing Ba abundance and a correlation of the Zr and Eu overabundances relative to Ba. The evolutionary behavior of the abundance ratios found for the thick-disk and halo stars does not agree with current models for the Galaxy’s chemical evolution. The abundance ratios of Y and Zr to Fe and Ba for thin-disk stars, as well as the abundance ratios within each group, are, on average, solar, though we note a slight decrease of Zr/Ba and Zr/Y with increasing Ba abundance. These results provide evidence for a dominance of asymptotic-giant-branch stars in the enrichment of the interstellar medium in heavy elements during the thin-disk epoch, in agreement with the predictions of the nucleosynthesis theory for the main s-process component.     

Chemical speciation of Cd,Cu, Pb,and Zn in mixed freshwater,seawater, and brine solutions

A theoretical model was developed to study the chemical speciation of the trace elements Zn, Cd, Cu and Pb aqueous solutions and their responses to variations in ionic strength and complexation. Two mixing solutions were investigated, a freshwater-seawater system and a freshwater-brine system. The brine was a calcium, sodium-chloride solution with a molal ionic strength of two. Trace element associations with the ligands OH^?, Cl^?, CO^2?₃, SO^2?₄, and HCO^?₃ were considered at pHs from 3.5 to 11.0 at 25°C. In general, the relative importance of the various ligand-trace element complexes can be predicted from a comparison of their stability constants. However, the effect of pH on the importance of a given complex is not readily apparent from the stability constants. Freshwater-seawater mixtures, as might be found in a totally mixed estuary, show that seawater composition is the dominant control on chemical complexing. Chloride complexing is similar for lead and zinc in the freshwater-brine mixtures. This similarity may account in part for the association of lead and zinc in strata-bound ore deposits.     

Interactions between Cd,Cu, Pb,and Zn and four different mine soils

The chemical associations of Cd, Cu, Pb, and Zn in four mine soil samples from the Amizour-Bejaia Pb/Zn mine (Algeria) have been investigated by a five-step sequential extraction procedure. Although Cd preferentially binds to carbonates, Cu, Pb, and Zn are mainly associated with the organic and reducible fractions. Batch adsorption experiments with either mono- or multi-metallic solutions are described with the Freundlich isotherm model. Whatever the nature of the soil sample, the sorption behavior for each given metal except Pb is very similar, indicating that the binding sites at the soil surface are progressively occupied by the metal from the solution. On each soil sample, the decreasing order of sorption can be established as Pb >> Cu > Cd > Zn. When the four metals are simultaneously applied to each soil sample, their specific behavior is strongly affected by their interactions and/or competition for the available surface sites: we generally observed isotherm curves with a slight maximum before the plateau at higher solution concentration. Although Cu is only slightly affected by the other metals, in the case of Pb, Cd, and Zn, the sorbed amounts strongly decreased.     

Metals,arsenic, and sulfur in the Aue and Eibenstock granites,Erzgebirge

Average concentrations of Pb, Zn, Cu, and other metals, as well as S and As, were calculated for the Aue granitic cupola, the contact aureole of which hosts the large vein-type uranium deposit of Schlema-Alberoda and the Schneeberg uranium-base metal deposit (Erzgebirge, Germany). The cupola was exposed by mine workings and boreholes, which provided an opportunity to evaluate variations in the abundances of metals in the granites over a vertical interval of more than 2.5 km and estimate their losses in the upper oxidized part of the investigated volume of the cupola (coefficient of iron oxidation, KO _Fe, increases in the granites from bottom to top from 7 to 70%) compared with the lower unaltered and unoxidized part (with a KO _Fe plateau at about 5%). The average concentrations of metals in the upper part of the cupola are lower than those in the lower part by a factor of 2.5 for Pb, 1.56 for Zn, 1.45 for Cu, 1.3 for Co, etc. A similar decrease in the abundances of ore elements along the vertical section associating with the relative epigenetic alteration and oxidation of the granite was previously described by us for U and Th and for the components of high-temperature ores, W, Sn, and Mo. The removal of ore elements from the granite was accompanied by a decrease in the bulk contents of sulfur and arsenic by a factor of 1.35 and 1.65, respectively. The leaching of trace metals from the granites of the upper part of the Aue cupola was followed by their partial redeposition above the cupola in the ore veins of the Schlema and Schneeberg deposits. Original Russian Text ? Vikt. L. Barsukov, N.T. Sokolova, O.M. Ivanitskii, 2006, published in Geokhimiya, 2006, No. 9, pp. 967–982.     

Cretaceous climate, volcanism, impacts, and biotic effects

Cretaceous volcanic activities (LIPs and CFBPs) appear to have had relatively minor biotic effects, at least at the generic level. Major biotic stress during the Cretaceous was associated with OAEs and related to nutrient availability largely from weathering, greenhouse warming, drowning of platform areas, and volcanism. The biotic effects of OAEs were often dramatic at the species level, causing the extinction of larger specialized and heavily calcified planktonic foraminifera (rotaliporid extinction) and nannoconids (nannoconid crises), the temporary disappearances of other larger species, and the rapid increase in r-selected small and thin-walled species, such as the low oxygen tolerant heterohelicids and radially elongated taxa among planktic foraminifera and thin walled nannofossils. Biotic diversity increased during cool climates, particularly during the late Campanian and Maastrichtian, reaching maximum diversity during the middle Maastrichtian. High biotic stress conditions began during greenhouse warming and Deccan volcanism about 400 ky before the K-T boundary; it reduced abundances of large specialized tropical planktic foraminiferal species and endangered their survival. By K-T time, renewed Deccan volcanism combined with a large impact probably triggered the demise of this already extinction prone species group.Evidence from NE Mexico, Texas, and the Chicxulub crater itself indicates that this 170 km-diameter crater predates the K-T boundary by 300,000 years and caused no species extinctions. The Chicxulub impact, therefore, can no longer be considered a direct cause for the K-T mass extinction. However, the K-T mass extinction is closely associated with a global Ir anomaly, which is considered too large, too widespread, and too concentrated in a thin layer to have originated from volcanic activity, leaving another large impact as the most likely source. This suggests that a second still unknown larger impact may have triggered the K-T mass extinction.     

Sedimentology, stratigraphy, and glacier dynamics, western Scottish Highlands

Glacial sediments of the western Scottish Highlands are comprehensively described and characterized here for the first time, enabling the first glacial stratigraphy for the area to be proposed. This classification is based on the results of extensive geological mapping and field investigation of sedimentary sequences and their structures, X-ray diffraction and particle size distribution analyses, and comparison with deposits formed in contemporary glaciated environments. These new data are subsequently appraised in terms of their implications for late Pleistocene glacier evolution and dynamics. Together, the data suggest that much of the landscape is palimpsest, and can be attributed to the Weichselian (Late Devensian) glaciation. Subsequent glacier advance during the Younger Dryas did little to modify the area, suggesting that ice flow was dominated by sliding on a meltwater-lubricated rigid bed, with deformation of basal sediments playing a more limited role. Final deglaciation was marked by a significant increase in basal meltwater flux, reflecting the warming climate and increasing precipitation. These new palaeoglaciological and palaeoenvironmental insights advance our understanding of former glacier dynamics in the western Scottish Highlands, improve our knowledge of Pleistocene landscape evolution of this area, and enable comparisons to be made with sedimentary sequences elsewhere.     

Distribution of REE,LILE, and HFSE between biotite,feldspar, and the melt in the granulite facies migmatite,nimnyr block,Aldan shield

The behavior of trace elements under conditions of partial melting of granitoid rocks has been studied. The element’s partition coefficients between minerals and the melt D_i^min/melt depends, in the first place, on the composition of the primary melt. In biotite the HREE D_i are a little below 1, while those of LREE, especially D_i for Ce, are 1–3 orders of magnitude less. This leads to an efficient differentiation of REEs in anatexic melts especially when biotite is the main mineral phase of restite. On the contrary, there are feldspars, the D_i of which cannot provide such a magnitude of differentiation. Unlike garnets and pyroxenes, whose stability in restite permits enrichment of anatexic melts produced in migmatization zones with Nb, Ti, and Cr, the presence of biotite in restite causes depletion of melts with those elements as well as with Rb. Feldspars, under conditions of their fractional crystallization or during differentiation of an anatexic melt, deplete the latter with Sr, Ba, and Rb, but enrich it with Nb, Ti, Cr, Y, Zr, and V.     

Chemistry of Kornerupine and Associated Minerals, a Wet Chemical, Ion Microprobe, and X-Ray Study Emphasizing Li, Be, B and F Contents

Kornerupine and associated minerals in 31 samples of high-graderocks relatively rich in Al and Mg were analysed by wet chemistry,ion microprobe mass analyser, electron microprobe and X-raypowder diffraction. For 11 samples of kornerupine and threesamples of biotite (F only) analysed by both wet chemical andion microprobe methods, the best agreement was obtained forB₂O₃, whereas the ion microprobe Li₂O values were systematicallysomewhat higher than the wet chemical values. The wet chemicalmethods give Li₂O=0–0?19 wt.%; BeO=0–0?032 wt.%;B₂O₃=0–4?01 wt.%; and F=0?07–0?77 wt.% in kornerupine,whereas ion microprobe analyses on other kornerupines give valuesup to 0?35 wt.% Li₂O, O066 wt.% BeO, and 4?72 wt.% B₂O₃. Thesum B+Al+Fe³⁺+Cr is close to 6?9 atoms per 22 (O, OH, F) or21?5 (O) in kornerupine. In general, Li/Fe ratios decrease as follows: kornerupine ?sapphirinebiotite> Crd (Na<0?03 per 18 oxygens)>tourmaline, garnet,orthopyroxene. However, for cordierite with Na>004, Li/Fedecreases as follows: cordierite>kornerupine. Sapphirineand sillimanite are the only associated minerals to incorporatesignificant boron (0?1–0?85 wt.% B₂O₃) and then only whenthe single site for B in kornerupine is approaching capacity.Sillimanite B₂O₃ contents increase regularly with kornerupineF. Fractionation of fluorine increases as follows: kornerupine<biotite<tourmaline,and K^krn-BtD=(F/OH)^Krn/(F/(OH)^Bt (assuming ideal anion composition)increases with biotite Ti. Kornerupine B₂O₃ content is a measureof B₂O₃ activity in associated metamorphic fluid, whereas sillimaniteB₂O₃ content increases with temperature, exceeding 0?4 wt.%whenT=900?C at very low water activities. New data on 11 kornerupines and literature data indicate thatthe unit cell parameters a, c, and V decrease with increasingB content and b, c, and V increase with increasing Fe³⁺ content.In Fe³⁺-poor kornerupines, b increases with Mg and with (Mg+ Fe²⁺) but the effect of Mg on b via the substitution ^VIMg+^IVSi=^VIAl+^IVAloverwhelms the effect of Fe²⁺=Mg substitution.     

Parents,permission, and possibility: Young women,college, and imagined futures in Gujarat,India

This article advances critical geographies of youth through examining the spatiality implicit in the imagined futures of young women in rural India. Geographers and other scholars of youth have begun to pay more attention to the interplay between young people’s past, present, and imagined futures. Within this emerging body of scholarship the role of the family and peer group in influencing young people’s orientations toward the future remain underexamined. Drawing on eleven months of ethnographic fieldwork, my research focuses on a first generation of college-going young women from socioeconomically marginalized backgrounds in India’s westernmost state of Gujarat. I draw on the “possible selves” theoretical construct in order to deploy a flexible conceptual framework that links imagined post-educational trajectories with motivation to act in the present. In tracing the physical movement of these young women as they navigate and complete college, my analysis highlights the ways in which particular kinds of spaces and spatial arrangements facilitate and limit intra- and inter-generational contact, and the extent to which this affects young women’s conceptions of the future. I conclude by considering the wider implications of my research for ongoing debates surrounding youth transitions, relational geographies of age, and education in the Global South.     

Determination of REE, Y, Nb, Zr, Hf, Ta, Th and U in Geological Reference Materials LSHC-1 and Amf-1 by Solution and Laser Ablation ICP-MS

This paper presents data on REE and Y, Nb, Zr, Hf, Ta, Th and U abundances for two candidate reference materials (RMs), spinel lherzolite LSHC-1 and amphibole Amf-1, being currently developed at the Institute of Geochemistry SB RAS, Irkutsk. To determine the contents of these elements inductively coupled plasma-mass spectrometry was applied with: (i) solution nebulisation (solution ICP-MS) and (ii) laser ablation (LA-ICP-MS) of fused glass disks. The precision of results obtained by both techniques was better than 6% RSD for most elements. Accuracy was assessed by using the geochemical RMs JB-2, JGb-1 (GSJ) and MAG-1 (USGS). The trace element results by solution ICP-MS for JGb-1 and JB-2 agree with reference values presented by Imai et al. (1995, this Journal) within 1–10%. Significant differences were found for Nb and Ta determinations. The accuracy of LA-ICP-MS results evaluated by RM MAG-1 was within 4%, except for Eu (about 10%). The analytical results obtained for LSHC-1 and Amf-1 by solution ICP-MS and LA-ICP-MS were in good agreement with each other and with INAA and XRF data presented for the certification of these RMs. They can be considered as the indicative values for assigning certified values to the above-mentioned RMs.     

Rare earth elements, yttrium and H, O, C, Sr, Nd and Pb isotope studies in mineral waters and corresponding rocks from NW-Bohemia, Czech Republic

The sparkling waters from the area of Kyselka near Karlovy Vary at the western slope of the Doupovske hory, Bohemia (Czech Republic), and CO₂-poor waters from two underground boreholes at Jachymov, Krusne hory, Bohemia, have been studied with the aim of characterizing the distribution of rare earth elements, yttrium, and H, O, C, Sr, Nd, Pb isotopes during the low-temperature alteration processes of the host rocks. Additionally, leaching experiments were performed at pH 3 on the granitic and basaltic host rocks from Kyselka and the granite of Jachymov. All REE patterns of the granite- and the basalt-derived waters from the Kyselka area are different from those of their source rocks and the leachates of the latter. This elucidates the inhomogeneous distribution of REE and Y among the solid phases in the altered magmatic rocks. The Eu and Ce anomalies in granite-derived waters are inherited, the Y anomaly is achieved by fluid migration. Yttrium is always preferentially leached by mineral waters, whereas Y/Ho ratios of rocks and their leachates are very similar. The REE abundances in waters from the wells in Jachymov are derived from rocks intensely leached and depleted in easily soluble REE-bearing minerals, whereas the granites and basalts from Kyselka still contain soluble, REE-bearing minerals. A comparison of REE/Ca patterns of the experimental leachates with those of the mineral waters elucidate the high retention of REE in rocks during water–rock interaction. In strongly altered rocks Sr isotope ratios of mineral waters and rocks differ widely, whereas the corresponding Nd isotope ratios are very similar. ²⁰⁷Pb/²⁰⁸Pb, ²⁰⁶Pb/²⁰⁸Pb and ²⁰⁶Pb/²⁰⁷Pb ratios in mineral waters are independent from U/Th ratios in the rocks. ²⁰⁶Pb/²⁰⁸Pb and ²⁰⁶Pb/²⁰⁷Pb are lower in mineral waters than in their source rocks and their leachates, which indicates that Pb is primarily derived from solid phases that do not contain significant contents of leachable U and Th. Thus, mineral waters, although CO₂ rich, only interact with surface films on minerals and not with the bulk of the minerals as in the leaching experiments.Calculation of mixing ratios of waters from the granitic and basaltic sources of the waters from the Kyselka area yield about 40% of water from the underlying granite in water recovered from the basalt, whereas the granite-derived water is mixed with only about 5% of the water from the basalt.     

Natural speciation of Ni, Zn, Ba, and As in ferromanganese coatings on quartz using X-ray fluorescence, absorption, and diffraction

The mineralogy of natural ferromanganese coatings on quartz grains and the crystal chemistry of associated trace elements Ni, Zn, Ba, and As were characterized by X-ray microfluorescence, X-ray diffraction, and EXAFS spectroscopy. Fe is speciated as ferrihydrite and Mn as vernadite. The two oxides form alternating Fe- and Mn-rich layers that are irregularly distributed and not always continuous. Unlike naturally abundant Fe-vernadite, in which Fe and Mn are mixed at the nanoscale, the ferrihydrite and vernadite are physically segregated and the trace elements clearly partitioned at the microscopic scale. Vernadite consists of two populations of interstratified one-water layer (7 Å phyllomanganate) and two-water layer (10 Å phyllomanganate) crystallites. In one population, 7 Å layers dominate, and in the other 10 Å layers dominate. The three trace metals Ni, Zn, and Ba are associated with vernadite and the metalloid As with ferrihydrite. In vernadite, nickel is both substituted isomorphically for Mn in the manganese layer and sorbed at vacant Mn layer sites in the interlayer. The partitioning of Ni is pH-dependent, with a strong preference for the first site at circumneutral pH and for the second at acidic pH. Thus, the site occupancy of Ni in vernadite may be an indicator of marine vs. continental origin, and in the latter, of the acidity of streams, lakes, or soil pore waters in which the vernadite formed. Zinc is sorbed only in the interlayer at vacant Mn layer sites. It is fully tetrahedral at a Zn/Mn molar ratio of 0.0138, and partly octahedral at a Zn/Mn ratio of 0.1036 consistent with experimental studies showing that the ^VIZn/^IVZn ratio increases with Zn loading. Barium is sorbed in a slightly offset position above empty tetrahedral cavities in the interlayer. Arsenic tetrahedra are retained at the ferrihydrite surface by a bidentate-binuclear attachment to two adjacent iron octahedra, as commonly observed. Trace elements in ferromanganese precipitates are partitioned at a few, well-defined, crystallographic sites that have some elemental specificity, and thus selectivity. The relative diversity of sorption sites contrasts with the simplicity of the layer structure of vernadite, in which charge deficit arises only from Mn⁴⁺ vacancies (i.e., no Mn³⁺ for Mn⁴⁺ substitution). Therefore, sorption mechanisms primarily depend on physical and chemical properties of the sorbate and competition with other ions in solution, such as protons at low pH for Ni sorption.     

Morphometric,statistical, and hazard analyses using ASTER data and GIS technique of WADI El-Mathula watershed,Qena, Egypt

An attempt to carry out morphometric, statistical, and hazard analyses using ASTER data and GIS technique of Wadi El-Mathula watershed, Central Eastern Desert, Egypt. Morphometric analysis with application of GIS technique is essential to delineate drainage networks; basin geometry, drainage texture, and relief characteristics, through detect forty morphometric parameters of the study watershed and its sub-basins. Extract new drainage network map with DEM, sub-basin boundaries, stream orders, drainage networks, slope, drainage density, flow direction maps with more details is very necessary to analyze different morphometric and hydrologic applications for the study basin. Statistical analysis of morphometric parameters was done through cluster analysis, regression equations, and correlation coefficient matrix. Clusters analyses detect three independents variables which are stream number, basin area, and stream length have a very low linkage distance of 0.001 (at very high similarity of 99.95%) in a cluster with the basin width. Main channel length and basin perimeter (at very high similarity of 99.83%) are in a cluster with basin length. Using the regression equations and graphical correlation matrix indicates the mathematical relationships and helps to predict the behavior between any two variables. Hazard analysis and hazard degree assessment for each sub-basin were performed. The hazardous factors were detected and concluded that most of sub-basins are classified as moderately to highly hazardous. Finally, we recommended that the flood possibilities should be taken in consideration during future development of these areas.     

Occurrence, distribution and probable source of the trace elements in ghugus coals, wardha valley, districts chandrapur and yeotmal, maharashtra, India

Trace-element determinations of 15 coal samples have been made in order to know their distribution, behaviour and associations with the organic and inorganic fractions in the coal. The coal samples have been systematically collected in stratigraphic sequences so that the vertical variation of the trace-elements can be studied. The elements determined by spectographic analysis are W, V, Cr, Sc, Y, Cu, Co, Pb, Be, Ni and Ba. The results indicate that the concentration of trace elements in these coals varies greatly from bottom to top sections. The elements V and Co are extremely poor in the top and middle sections, whereas in the bottom section they are fairly distributed. Be is extremely poor in the bottom section, and fairly distributed in the middle and top sections. W, Sc, Y have poor concentration in the bottom section as compared to the middle and top sections. Ni is fairly distributed in the bottom section whereas its concentration is poor in the middle and top sections. Cr and Cu are fairly distributed in the bottom, middle and top sections. Ba has unusually high concentration in all the sections.It appears from the present study that W, Cr, Sc, Y and Be are concentrated more in silicate minerals (clay, quartz, etc.) associated with coal, and the elements like , Co, and Ni have intimate relation with organic matters in coal and are present as organometallic compounds as well as absorbed cations. Cu and Pb which are present in the coals are derived from the inorganic matter, mainly from the pyrites, whereas W has affinity with carbonate minerals in the coals. The Ba is mainly associated with the inoraanic matter of coal; its unusually high concentration indicates association with carbonates, clays and other silicate minerals.     

Recent and historical tsunami deposits from Lake Tokotan,eastern Hokkaido,Japan, inferred from nondestructive,grain size,and radioactive cesium analyses

Geological evidence of recent tsunamis from sediment samples collected from Lake Tokotan, a coastal lagoon in eastern Hokkaido, northern Japan, was detected using computed tomography (CT) and soft X-ray images, grain size, and radionuclide profiles. Initial field observations revealed that sediments had no discernable sedimentary structures at the top of the core. However, results of CT imaging, soft X-ray, and grain size analyses show evidence for three invisible sand layers that are intercalated with mud layers. These sand layers exhibit trends of landward fining and thinning. Furthermore, the distribution of sand layers was limited to the center and seaward parts of the lake. Vertical profiles of cesium and lead concentrations in combination with recent eyewitness accounts indicated that these sand layers are correlated with the 1973 Nemuro-oki, 1960 Chilean, and 1952 Tokachi-oki tsunami events. The deeper part of the sediment cores includes three volcanic ash layers and three prehistoric coarse sand layers. The prehistoric layers are correlated with unusually large tsunamis that were geologically identified in previous studies from eastern Hokkaido. These findings suggest that nondestructive techniques, in combination with radionuclide analysis, allow for detection of frequent but faint tsunami deposits. This technique allows for an improved understanding of the history of tsunami inundation in Lake Tokotan and of other locations for which stratigraphic evidence for faint tsunamis layers is not readily apparent from field assessments.