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.     

Loss of metals from pelites during regional metamorphism

In aluminous metapelites the ratio H₂O⁺/K₂O decreases with increasing metamorphic grade and degree of reaction. This ratio is a very practical indicator for the progress of the mineral reconstitution during progressive metamorphism. With decreasing values of the ratio H₂O⁺/ K₂O the Cu concentration and the following element ratios also decrease either continuously or in stepwise fashion: Tl/K₂O, Ba/K₂O, Pb/K₂O, Bi/K₂O, Hg/K₂O, Sr/Na₂O, Zn/(Fe²⁺+Mg), Cd/(Fe²⁺+Mg); Rb/K₂O remains approximately constant. In the aluminous metapelites of the Damara Orogen in Namibia the following losses occur between the biotite isograd and anatexis: 61% Cu, 20% Tl, 34% Ba, 59% Pb, 86% Bi, 46% Hg, 30% Sr, 25% Zn, 31% Cd. Thus the potential of regional metamorphism to form hydrothermal deposits in the low grade environment should not be neglected.     

Two magmatic series with island arc affinities within the vourinos ophiolite

Within the Vourinos ophiolite evidence of two magmatic series has been preserved in cognate cumulates and in effusive and hypabyssal rocks, which constitute the earlier Krapa sequence and the younger Asprokambo sequence. The Asprokambo dyke basic magmas which are poor in incompatible elements and relatively Ni and Cr rich, bear some resemblance to very low Ti basalts (transitional to boninites) found in subduction related arcs or interarc basins. Krapa series magmas from sills, massive and pillow lavas are best equated with low-K tholeiites of island arc suites. Compositions of Al- and Ti- poor Cpx in lavas from both series are comparable to those in island arc basalts, the Asprokambo Cpx being richer in Ca and Cr than those from Krapa.The large volume of cumulates from the Krapa sequence displays the following crystallization order: Ol±Sp, Cpx, Pl±Opx, Mt. Periodic influx of fresh magma batches into the magma chamber occurred mainly during the formation of the lower cumulates (wehrlite, Ol-clinopyroxenite and melagabbro). The upper cumulates, gabbronorite and leucogabbronorite with minor Mt-bearing gabbronorite, crystallized in the upper levels of a magma chamber which became progressively smaller with time. In the Asprokambo sequence, Ol+Sp, Opx, Cpx, PI and Amph are the successively crystallizing phases. The ortho to heteradcumulates consist of websterite, Pl-websterite, gabbronorite, amphibole bearing leuconorite, diorite and granophyre. In cumulates, especially in the lower Krapa sequence, significant subsolidus reaction was probably induced by the persistence of high geothermal gradients linked to continuous magmatism. Petrological features indicate that the evolution of the Krapa series is more compatible with an intermediate fractional/equilibrium crystallization history in an initially open system, whereas nearly perfect fractional crystallization in closed system may have occurred in the small Asprokambo magma chambers. Chemical variations in the lavas of both series can be explained in terms of crystallization of the observed cumulates. Significantly, the Asprokambo intrusives have igneous Mg-hornblende and vanadium bearing, chromian, aluminous titaniferous magnetite, crystallization of which is responsible for the calcalkaline evolutionary trend of these rocks. Major and trace element modelling necessitates a two stage model for the petrogenesis of the Vourinos parental melts, involving high-degree remelting of previously depleted mantle sources favoured by the influx of subduction derived hydrous fluids. The primary magmas parental to the Krapa and Asprokambo series could have been derived respectively by 20 and 30% equilibrium partial fusion of variably depleted lherzolitic sources, leaving residua having a harzburgitic to dunitic composition.     

Significance of Europium anomalies in silicate melts and crystal-melt equilibria: a re-evaluation

Although europium speciation in silicate melts partly reflects prevailing oxygen fugacities, melt composition and structure play the major role in determining Eu²⁺/ Eu³⁺ ratios and europium partitioning into mineral phases. Experimental evidence by different investigators on the magnitude of the compositional effect on Eu²⁺/Eu³⁺ provides consistent results only if account is taken of the oxygen buffer system employed in the experiments. The medium-dependent reduction of europium can be understood in terms of the preferential stabilization of Eu²⁺ by a strong aluminosilicate complex in the melt phase, and to a much lesser degree by metasilicate complexes. The stability of these complexes increases as the field strength of the associated cation species decreases. Hence Eu²⁺-aluminosilicate complexes are preferentially stabilized relative to trivalent lanthanides in melts of appropriate composition and their presence minimizes the enthalpy of the melt. The influence of these complexes is particularly pronounced in melts with a high feldspathic component and a strongly polymerized structure. Their petrogenetic influence is best documented through the behaviour of europium relative to the other lanthanides during anhydrous anatexis in high-grade metamorphic terrains and in the anomalous europium partition coefficients of phenocryst phases which formed during the crystallization of highly silicic magmas.     

Sr-gorceixite,a weathering product in rich iron ores from the Córrego do Feijão Mine,Minas Gerais,Brazil

A sulfate-bearing Sr-Ba phosphate (Sr-gorceixite) formed by supergene alteration in rich iron ores from Minas Gerais, Brazil, has been studied by means of microprobe techniques. Analytical data and the structural formula are presented.     

The role of metamorphic fluid transport in the Rb-Sr isotopic resetting of shear zones: evidence from Nordre Strømfjord,West Greenland

The Nordre Strømfjord shear zone is about 20 km wide and is exposed for 170 km along strike. It formed under granulite to amphibolite facies conditions as part of the 1,850 Ma-old Nagssugtoqidian orogeny affecting the largely Archean terrain of central West Greenland. We have made Rb-Sr isotope measurements on ca. 130 whole rock samples from the shear zone and have made microprobe analyses of biotite and plagioclase on 40 of them in order to evaluate the effects of shear zone formation on the Rb-Sr isotope system. Seven separate localities were sampled, four of them extensively; large whole rock samples and small, cm-scale thin slices were used in this study.The Rb-Sr isotope systems and the biotite compositions of the large whole rocks show variable degrees of re-equilibration during shear zone formation. Rb-Sr data for the least affected suites still scatter about Archean isochrons and the biotite compositions show wide variations both within and between samples. In other more affected suites, the Rb-Sr system was reset to approximate the age of shear zone formation on the scale of 10's of meters, and the biotite compositions are consistent within individual samples. The most strongly affected suites underwent profound chemical and isotopic changes. Whole rock suites preserve virtually no Rb-Sr isotopic record of their preshear zone history and the biotite compositions of entire suites are very homogeneous. The cm-scale suites of thin slices all show some degree of Proterozoic re-equilibration, although sharp Sr isotopic discontinuities between groups of lithologic layers are preserved.Among the suites of large whole rocks, the observed variations do not correlate with variations in shear strain, size of sampling domain, average Rb/Sr, range of Rb/Sr or ppm Sr. The combined Rb-Sr and microprobe data suggest that the responses are most likely to represent differences in total fluid/rock ratio in a system undergoing significant fluid transport. Our data suggest an uneven distribution of fluid pathways within the shear zone and a strongly preferred direction of fluid flow parallel to lithologic boundaries.Data from previous studies are also consistent with the conclusion that fluid transport is the major agent of Rb-Sr isotopic resetting in shear zones. This conclusion has implications for optimum sampling strategies in Rb-Sr dating of high strain events and for the processes by which Rb-Sr isotopic resetting occurs during regional metamorphism.     

A Biotite Isograd in South-Central Maine, U.S.A.: Mineral Reactions, Fluid Transfer, and Heat Transfer

The biotite isograd in pelitic schists of the Waterville Formationinvolved reaction of muscovite + ankerite + rutile + pyrite+graphite + siderite or calcite to form biotite + plagioclase+ ilmenite. There was no single reaction in all pelites; eachrock experienced a unique reaction depending on the mineralogyand proportions of minerals in the chlorite-zone equivalentfrom which it evolved. Quartz, chlorite, and pyrrhotite werereactants in some rocks and products in others. All inferredbiotite-forming reactions involved decarbonation and desulfidation;some were dehydration reactions and others were hydration reactions.P-T conditions at the biotite isograd were near 3500 bars and400 °C. C-O-H-S fluids in equilibrium with the pelitic rockswere close to binary CO₂-H₂O mixtures with X_CO2 = 0.02–0.04.During the biotite-forming reaction, pelitic rocks (a) decreasedby 2–5 percent in volume, (b) performed – (4–11)kcal/liter P-V work on their surroundings, (c) absorbed 38–85kcal/liter heat from their surroundings, and (d) were infiltratedby at least 0.9–2.2 rock volumes H₂O fluid. The biotite isograd sharply marks the limit of a decarbonationfront that passed through the terrane during regional metamorphism.Decarbonation converted meta-shales with 6–10 per centcarbonate to carbonate-free pelitic schists. One essential causeof the decarbonation event was pervasive infiltration of theterrane by at least 1–2 rock volumes H₂O fluid early inthe metamorphic event under P-T conditions of the biotite isograd.Average shale contains 4–13 per cent siderite, ankerite,and/or calcite, but average pelitic schist is devoid of carbonateminerals. If the Waterville Formation serves as a general modelfor the metamorphism of pelitic rocks, it is likely that worldwidemany pelitic schists developed by decarbonation of shale caused,in part, by pervasive infiltration of metamorphic terranes byseveral rock volumes of aqueous fluid during an early stageof the metamorphic event.     

Seasonal and spatial variability of particulate matter of a muddy intertidal flood front

The concentration and composition of suspended particulate matter (SPM) were measured weekly for a period of one year in the flood front waters traversing a muddy tidal flat. SPM concentrations were lowest in the winter when portions of the tidal flat were covered with ice, and biological activity was minimal. In contrast, the summer months had the highest SPM concentrations which reflected increased bottom resuspension. The two main sources of SPM were suspended matter carried in from offshore on the flooding tide and resuspended in situ bottom sediments. The offshore source was characterized by low SPM concentrations, coarse textures, and a high content of protein and chlorophyll ‘a’. Samples taken during resuspension events (storms/showers) had high SPM concentrations, finer textures, and were enriched in dead detrital organic material (phaeophytin). At any one time the SPM was primarily an admixture of these two sources. The highest SPM measurements were taken during storm events, with rainfall seeming to play a dominant physical role in aiding resuspension. SPM concentrations, textures, and compositions collected during the storms closely approximated SPM measurements made over newly dug ‘clam flats’.     

Application of the technique to ellipitical markers deformed by pressure-solution

Compression and extension axes are deduced from quartz deformation lamellae in a quartzite and a graywacke folded into an asymetrical syncline. Deformation lamellae fabrics in the two sandstones are distinctly different. In the graywacke, regardless of bedding orientation or position on the fold, compression axes are normal or nearly normal to the axial planar rough cleavage. Extension axes generally lie in the cleavage plane, parallel to dip. In most quartzite samples, compression axes are parallel or subparallel to bedding, at high angles to the fold axis and extension axes are normal to bedding. Two samples from the very base of the formation indicate compression parallel to the fold axis with extension parallel to bedding, at high angles to the fold axis. One of these two shows both patterns. The lamellae fabric geometry in these two samples suggests the presence of a neutral surface in the quartzite. The lamellae-derived compression and extension axes are in good agreement with the buckling behavior of a viscous layer (quartzite) embedded in a less viscous medium (graywacke and shale below and shale and carbonate above).     

The origin of tectonic stress in the lithosphere

The sources of lithospheric stress and their distinctive features are briefly reviewed. It is suggested that there are two main categories of lithospheric stress: renewable stress which persists despite continuing stress relaxation and non-renewable stress which can be dissipated by relief of the initial strain. The two most important types of renewable stress arise from plate boundary forces and from isostatically compensated loads. Non-renewable stress systems include bending stresses, membrane stresses and thermal stresses. An important phenomenon generating large stresses at shallow depth is stress amplification caused by lower lithospheric creep. This applies to renewable stresses but not to the non-renewable type. It is suggested that only renewable stresses contribute significantly to tectonic activity. However, bending and thermal stresses are locally important in subducting lithosphere.