Geochemical processes controlling the spatial distribution of selenium in soil and water,west central South Dakota,USA

Selenium (Se) is essential in the human diet, but has a low threshold for toxic concentration. It is recommended that nutrients such as Se should be consumed through foods as part of a normal diet. Se concentrations in crops and meat depend on the amount of labile Se in the soil where crops and forage are grown. Therefore, managing agriculture for optimal Se in grain crops and forage requires an understanding of the distribution and mobility of Se. Elevated concentrations of Se occur in waters, soils, and forage 120 km west of Pierre in west central South Dakota, USA. The research site lies in an elevated, dissected plain where soils developed on gently dipping Pierre Shale. Soils were sampled along catena transects and waters collected from soil, ponds, and shallow borings in areas of known elevated forage and crop Se. Soil extracts from saturated-paste extraction and acid (aqua regia and hydrofluoric acid) extraction were analyzed. Selenate was the dominant Se species in both acid and saturated-paste extracts; selenite and organic Se were below detection (<0.2 ppb) in the same soil extracts. On average, 98% of soil Se was not water-soluble. The distribution of total Se shows much less spatial variation than water-soluble Se in the areas sampled. Se shows correlation with organic carbon in soils and waters, suggesting its association with organic carbon. Ca shows some correlation to Se in acid extracts, but not in saturated-paste extracts or in waters. Total Se shows no significant correlation to Na, Mg, and total S in the soils. Se in saturated-paste extracts and water samples shows good correlations with Na, Mg, and SO₄, suggesting that evaporitic Na–Mg–sulfate minerals may temporarily concentrate water-soluble Se in shallow soils. The dissolution and precipitation of these Na–Mg–sulfate salts together with pH and oxidation–reduction conditions apparently control water-soluble Se distribution and mobilization in shallow subsurface environments.     

Retrograde alteration of chromian kyanite in metachert and amphibolite whiteschist from the Southern Alps,New Zealand,with implications for uplift on the Alpine Fault

Chromian kyanites with a maximum content of 2.88 wt.% Cr₂O₃ occur in metachert and amphibolite from the Southern Alps, New Zealand. The presence of the whiteschist assemblage kyanite-talc, together with kyanite-zoisite assemblages in calc silicate bands imply high pressure metamorphism, with climactic conditions of approximately 10 kb at 650°–700° C. Mylonitization caused by a change to oblique-slip movements on the Alpine Fault is succeeded by retrograde alteration of kyanite-bearing assemblages. Kyanite is pseudomorphed by Cr-margarite-fuchsite-Cr-zoisite assemblages in metachert and by less chromian margarite and zoisite in amphibolite. Contemporaneously hornblende and phlogopite break down to chlorite. Subsequently the metachert pseudomorphs are mantled by muscovite and those in amphibolite by anorthite and chromite. The breakdown of margarite and zoisite to anorthite implies decompression under a low thermal gradient, compatible with almost isothermal uplift on the Alpine Fault. Late stage retrograde products include fibrous kyanite (probably forming by recrystallization of primary alluminosilicate) and scapolite (possibly orginating through interaction of Cl-bearing fluids in a geothermal system).In the Southern Alps there is a significant uplift following the Cretaceous Rangitata Orogeny, probably in the order of 11–15 km. However, the bulk of the uplift, approximately 25 km, took place in the past 10 m.y. during Kaikoura Orogenic uplift on the Alpine Fault. It is during this latest and continuing phase of uplift that the sequence of kyanite alteration reactions occurred.     

Kinetic study of the dehydroxylation of chrysotile asbestos with temperature by in situ XRPD

 The kinetics of the dehydroxylation of chrysotile was followed in situ at high temperature using real-time conventional and synchrotron powder diffraction (XRPD). This is the first time kinetics parameters have been calculated for the dehydroxylation of chrysotile. The value of the order of the reaction mechanism calculated using the Avrami model indicates that the rate-limiting step of the reaction is a one-dimensional diffusion with an instantaneous nucleation or a deceleratory rate of nucleation of the reaction product. Hence, the rate-limiting step is the one-dimensional diffusion of the water molecules formed in the interlayer region by direct condensation of two hydrogen atoms and an oxygen atom. The calculated apparent activation energy of the reaction in the temperature range 620–750 °C is 184 kJ mol⁻¹. The diffusion path is along the axis of the fibrils forming the fibers. The amorphous or short-range ordered dehydroxylate of chrysotile is extremely unstable because forsterite readily nucleates in the Mg-rich regions. Moreover, it is less stable than the dehydroxylate of kaolinite, the so-called metakaolinite, which forms mullite at about 950 °C. This difference is interpreted in terms of the different nature of the two ions Mg²⁺ and Al³⁺ and their function as glass modifier and glass-forming ion, respectively. Received: 10 April 2002 / Accepted: 7 January 2003 Acknowledgements This work is part of a COFIN project (04 Scienze della Terra, NR 17, 2000) supported by MURST. Dr Dapiaggi is kindly acknowledged for help during the data collection at the Dipartimento di Scienze della Terra, University of Milan.     

The Catoca kimberlite pipe, Republic of Angola: A paleovolcanological model

The Catoca kimberlite pipe is among the world’s largest primary diamond deposits. The Catoca volcanic edifice is only slightly eroded. Kimberlitic rocks of various facies compose a crater of about 1 km in diameter and a diatreme. The structure of the pipe and mining conditions of the deposit are complicated by intense intrapipe tectonic processes related to large-amplitude subsidence. Based on geological data, we propose a structural model of the deposit and a paleovolcanological model of the Catoca pipe formed during a full cycle beginning with a stage of active volcanism and completed by stages of gradually waning volcanic activity and sedimentation. It is suggested that the banded tuffisitic kimberlite of the crater zone was deposited at the stage of active volcanic eruption from specific pyroclastic suspension as a low-viscosity mixture of crystals and aqueous sol rich in serpentine.     

Heavy metals in sediments of the Tecate River, Mexico

Ten sites along the Tecate River, Mexico were sampled to evaluate the cadmium, lead, nickel and chromium concentrations in sediments. The result shows contamination for cadmium in most of the sites, where two sites were class 4 (polluted to strongly polluted) according to geoaccumulation index proposed by Muller. Two sites were found polluted for all the heavy metals analyzed (Cr, Cd, Pb and Ni), indicating the effect of anthropogenic activities. A correlation between Ni and Cd concentration had been found indicating a common source. These metals are usually used in electroplating industry. The results of this study can be used for decision makers to prioritize measures to control the pollution for these metals.     

Factors controlling the development of prism faces in granite zircons: a microprobe study

Based on microprobe work, we present arguments that the size relations of the two common prisms {100} and {110} of accessory granite zircons are strongly influenced by chemical factors. Magmatic growth zoning patterns, which we have studied by means of backscattered electron imaging in special zircon sections orientated perpendicular to the c-axis, do not support previous models which assumed temperature or the degree of ZrSiO₄ supersaturation to be the primary prism-form-directing factors. The element U, which usually occupies the Zr-sites of granite zircoms to some degree, is strongly suspected of producing an (adsorptive) growth-blocking effect for {110}-type faces thus creating crystals with {110}-dominated prism morphology. A second independent mechanism that is likely to form zircons with large {110} prisms is the common substitution Zr⁴⁺+Si⁴⁺ versus Y(REE) and P contents (relative to Zr) are, according to our model, predestinated to produce zircons with large {100} prisms and vice versa.Dedicated to Prof. Günther Frasl on the occasion of his seventieth birthday     

Estimating the settling velocity of bioclastic sediment using common grain‐size analysis techniques

Most techniques for estimating settling velocities of natural particles have been developed for siliciclastic sediments. Therefore, to understand how these techniques apply to bioclastic environments, measured settling velocities of bioclastic sedimentary deposits sampled from a nearshore fringing reef in Western Australia were compared with settling velocities calculated using results from several common grain‐size analysis techniques (sieve, laser diffraction and image analysis) and established models. The effects of sediment density and shape were also examined using a range of density values and three different models of settling velocity. Sediment density was found to have a significant effect on calculated settling velocity, causing a range in normalized root‐mean‐square error of up to 28%, depending upon settling velocity model and grain‐size method. Accounting for particle shape reduced errors in predicted settling velocity by 3% to 6% and removed any velocity‐dependent bias, which is particularly important for the fastest settling fractions. When shape was accounted for and measured density was used, normalized root‐mean‐square errors were 4%, 10% and 18% for laser diffraction, sieve and image analysis, respectively. The results of this study show that established models of settling velocity that account for particle shape can be used to estimate settling velocity of irregularly shaped, sand‐sized bioclastic sediments from sieve, laser diffraction, or image analysis‐derived measures of grain size with a limited amount of error. Collectively, these findings will allow for grain‐size data measured with different methods to be accurately converted to settling velocity for comparison. This will facilitate greater understanding of the hydraulic properties of bioclastic sediment which can help to increase our general knowledge of sediment dynamics in these environments.     

Andradite and andradite-grossular solid solutions in very low-grade regionally metamorphosed rocks in Southern New Zealand

Almost pure andradite and intermediate members of the andradite-grossular series (gros_40–49, and _47–54, py_0–3, alm_0–3, spess_0–2, hydrogarnet_0–3), often framboidal in habit, are widespread in metabasites including lavas, minor intrusions, and volcanic sandstones and breccias metamorphosed under prehnite-pumpellyite and pumpellyite-actinolite facies conditions, possibly extending into the zeolite facies. Coexisting phases include iron-rich epidotes (100 Fe*/Fe*+Al=22–34), pumpellyite, prehnite, actinolite, and chlorite, electron microprobe analyses of which are given, as well as quartz, albite, and calcite. Zoisite (100 Fe*/Fe*+Al=1–5) and iron-poor epidote (100 Fe*/Fe*+Al=11–18) occur in 2 rocks in pseudomorphs after plagioclase together with more iron-rich epidote, but not in close association with the garnets. Coexisting pumpellyite is iron-rich (FeO* 9–14%) in the prehnite-pumpellyite facies and iron-poor (FeO* 5%) in the pumpellyiteactinolite facies. Chlorites and actinolites vary widely and sympathetically in FeO/MgO+FeO ratio. Andradite is also described from a stilpnomelane-actinolite-hematite-bearing andradite quartzite of the pumpellyite-actinolite facies. Conditions of formation involved temperatures of 300 to 400 ° or less, at pressures up to a few kilobars. A wide range of oxygen fugacities is possible, but in the fluid phase was low. Grandite and chlorite are incompatible in the pumpellyite-actinolite and greenschist facies in the presence of quartz but the 2 minerals occur together in some pumpellyite-actinolite facies assemblages as a result of incomplete reaction and/or local deficiency in silica. In the greenschist facies the association is replaced by epidote-actinolite±hematite and sodic amphibole. Whereas at medium to high grades of metamorphism andradite and grandite are characteristic of skarns irrespective of , at very low grades they are found in mafic volcanic rocks and volcanogenic sediments as well as in certain cherty rocks of unusual composition, rodingites, and serpentinites, where was very low.     

Method of Data Reduction and Uncertainty Estimation for Platinum-Group Element Data Using Inductively Coupled Plasma-Mass Spectrometry

A data reduction method is described for determining platinum-group element (PGE) abundances by inductively coupled plasma-mass spectrometry (ICP-MS) using external calibration or the method of standard addition. Gravimetric measurement of volumes, the analysis of reference materials and the use of procedural blanks were all used to minimise systematic errors. Internal standards were used to correct for instrument drift. A linear least squares regression model was used to calculate concentrations from drift-corrected counts per second (cps). Furthermore, mathematical manipulations also contribute to the uncertainty estimates of a procedure. Typical uncertainty estimate calculations for ICP-MS data manipulations involve: (1) Carrying standard deviations from the raw cps through the data reduction or (2) calculating a standard deviation from multiple final concentration calculations. It is demonstrated that method 2 may underestimate the uncertainty estimate of the calculated data. Methods 1 and 2 do not typically include an uncertainty estimate component from a regression model. As such models contribute to the uncertainty estimates affecting the calculated data, an uncertainty estimate component from the regression must be included in any final error calculations. Confidence intervals are used to account for uncertainty estimates from the regression model. These confidence intervals are simpler to calculate than uncertainty estimates from method 1, for example. The data reduction and uncertainty estimation method described here addresses problems of reporting PGE data from an article in the literature and addresses both precision and accuracy. The method can be applied to any analytical technique where drift corrections or regression models are used.