Iodine chemistry in deep anoxic basins and overlying waters of the Mediterranean Sea

Iodate (IO₃⁻) is the predominant dissolved species of iodine in the oxygenated waters of the Mediterranean Sea. Iodide (I⁻) is present in significant quantities (up to 65 nM) in oxygenated waters in the photic zone and near the interface above the anoxic and saline Bannock Basin. Lesser quantities of I⁻ (< 10 nM) are found throughout the rest of the oxic water column. An additional unidentified dissolved iodine species is present immediately above the anoxic interface.Total dissolved iodine (ΣI) increases dramatically across the seawater/brine interface. Part of this increase is undoubtedly the result of the dissolution of iodine-rich evaporites during formation of the brine bodies at the Tyro and Bannock Basins. The vertical distribution of ΣI and other dissolved chemical species (particularly PO₄³⁻) in the Bannock Basin brine, however, suggests an additional, present-day, diagenetic source of dissolved iodine to the brine. Based on the increase in the concentration of the most soluble major ions across the seawater/brine interface, 5–7 μM of the 11.5-μM increase in ΣI concentration must be attributed to diagenesis.     

The GeoForschungsZentrum Potsdam/Groupe de Recherche de Gèodésie Spatiale satellite-only and combined gravity field models: EIGEN-GL04S1 and EIGEN-GL04C

The recent improvements in the Gravity Recovery And Climate Experiment (GRACE) tracking data processing at GeoForschungsZentrum Potsdam (GFZ) and Groupe de Recherche de Géodésie Spatiale (GRGS) Toulouse, the availability of newer surface gravity data sets in the Arctic, Antarctica and North-America, and the availability of a new mean sea surface height model from altimetry processing at GFZ gave rise to the generation of two new global gravity field models. The first, EIGEN-GL04S1, a satellite-only model complete to degree and order 150 in terms of spherical harmonics, was derived by combination of the latest GFZ Potsdam GRACE-only (EIGEN-GRACE04S) and GRGS Toulouse GRACE/LAGEOS (EIGEN-GL04S) mean field solutions. The second, EIGEN-GL04S1 was combined with surface gravity data from altimetry over the oceans and gravimetry over the continents to derive a new high-resolution global gravity field model called EIGEN-GL04C. This model is complete to degree and order 360 and thus resolves geoid and gravity anomalies at half- wavelengths of 55 km at the equator. A degree-dependent combination method has been applied in order to preserve the high accuracy from the GRACE satellite data in the lower frequency band of the geopotential and to form a smooth transition to the high-frequency information coming from the surface data. Compared to pre-CHAMP global high-resolution models, the accuracy was improved at a spatial resolution of 200 km (half-wavelength) by one order of magnitude to 3 cm in terms of geoid heights. The accuracy of this model (i.e. the commission error) at its full spatial resolution is estimated to be 15 cm. The model shows a reduced artificial meridional striping and an increased correlation of EIGEN-GL04C-derived geostrophic meridional currents with World Ocean Atlas 2001 (WOA01) data. These improvements have led to select EIGEN-GL04C for JASON-1 satellite altimeter data reprocessing. Electronic Supplementary Material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Regional development in the United States during the 1980s: population redistribution and economic restructuring

The reduction of the rate of growth of the Brazilian population from 3% in the 1960s to 2% by 1993 resulted from a significant reduction of fertility. According to the 1986 national maternal-child health and family planning survey (PNSMIPF) results, 43.3% of women were using some type of contraception: 65.6% of married or cohabiting women. Women relied most on sterilization (17.2%), followed by oral contraceptives (OCs) (17%), the rhythm method (2.8%), the condom (1.1%), and others (5.2%). Only in the south was OC use more prevalent (28.5%) than sterilization (12.2%). The proportion of sterilization reached 27.8% in the north/center-east urban regions. In urban areas sterilization averaged 18.7% vs. 12.7% in rural areas. 26.9% of currently married women in the age range of 15-44 years had been sterilized. A 1990 international estimation indicated that the proportion of sterilization amounted to 36.9% in China, 30.95 in India, 29.7% in Brazil, 47.6% in South Korea, 30.4% in Thailand, and 36.5% in the Dominican Republic. The 1986 PNSMIPF survey also indicated that sterilized women were better informed than other women about contraception. 75% of the former had used OCs, 5% had used the diaphragm, 3% the IUD, 30% the condom, and 35% coitus interruptus at one time or other. The sterilized women had an average of 1.7 more children than those who were using other methods of contraception. 48.6% of women were sterilized before the age of 30, when they had had an average of 3.6 children. 66.6% of the sterilized women who had given birth before the age of 20 had 4 or more live births as compared to 5.9% of sterilized women aged 30 with the same number of children. 47% of women without any schooling were using some kind of contraception vs. 77% of those who had completed secondary school. A multivariate analysis also showed that the age of the mother, the number of live births, the educational status of the mother, and family income were positively correlated with sterilization.     

The partial molar volume, thermal expansivity, and compressibility of H2O in NaAlSi3O8 liquid: new measurements and an internally consistent model

The molar volumes of 19 hydrous albitic liquids (1.9 to 6.1 wt% H₂O^total) were determined at one bar and 505–765 K. These volume data were derived from density measurements on hydrous glasses at 298 K, followed by measurements of the thermal expansion of each glass from 298 K to its respective glass transition temperature. The technique exploits the fact that the volume of a glass is equal to that of the corresponding liquid at the limiting fictive temperature (T _f′), and that T _f′ can be approximated as the temperature near the onset of the rapid increase in thermal expansion that occurs in the glass transition interval. The volume data of this study were combined with available volume data for anhydrous, Na₂O-Al₂O₃-SiO₂ liquids to derive the partial molar volume (±1) of the H₂O component in an albitic melt at ∼565 K and one bar. To extend the determination of to higher temperatures and pressures, the molar volumes of the hydrous albitic liquids determined in this study were combined with those measured by previous authors at 1023–1223 K and 480–840 MPa, leading to the following fitted values (±1) at 1673 K and one bar: (±0.46)×10⁻³ cm⁻³/mol-K, and dVˉ ^H ₂ ^{O total} /dP=−3.82 (±0.36)×10⁻⁴ cm³/mol-bar. The measured molar volumes of this study and those of previous authors can be recovered with a standard deviation of 0.5%, which is within the respective experimental errors. There is a significant difference between the values for derived in this study as a function of temperature and pressure and those obtained from an existing polynomial, primarily caused by the previous absence of accurate density measurements on anhydrous silicate liquids. The coefficients of thermal expansion (=4.72×10⁻⁴/K) and isothermal compressibility ( _T =1.66×10⁻⁵/bar) for the H₂O component at 1273 K and 100 MPa, indicate that H₂O^total is the single most expansive and compressible component in silicate liquids. For example, at 1473 K and 70 MPa (conditions of a mid-ocean ridge crustal magma chamber), the presence of just 0.4 wt% H₂O will decrease the density of a basaltic liquid by more than one percent. An equivalent decrease in melt density could be achieved by increasing the temperature by 175 degrees or the decreasing pressure by 230 MPa. Therefore, even minor quantities of dissolved water will have a marked effect on the dynamic properties of silicate liquids in the crustal environment. Received: 20 August 1996 / Accepted: 15 March 1997     

Transfer and early diagenesis of biogenic silica oxygen isotope signals during settling and sedimentation of diatoms in a temperate freshwater lake (Lake Holzmaar, Germany)

We have investigated the transfer of oxygen isotope signals of diatomaceous silica (δ¹⁸O_diatom) from the epilimnion (0-7 m) through the hypolimnion to the lake bottom (∼20 m) in freshwater Lake Holzmaar, Germany. Sediment-traps were deployed in 2001 at depths of 7 and 16 m to harvest fresh diatoms every 28 days. The 7 m trap collected diatoms from the epilimnion being the main zone of primary production, while the 16 m trap collected material already settled through the hypolimnion. Also a bottom sediment sample was taken containing diatom frustules from approximately the last 25 years. The δ¹⁸O_diatom values of the 7 m trap varied from 29.4‰ in spring/autumn to 26.2‰ in summer according to the temperature dependence of oxygen isotope fractionation and represent the initial isotope signal in this study. Remarkably, despite the short settling distance δ¹⁸O_diatom values of the 7 and the 16 m trap were identical only during spring and autumn seasons while from April to September δ¹⁸O_diatom values of the 16 m trap were roughly ∼1.5‰ enriched in ¹⁸O compared to those of the 7 m trap. Isotopic exchange with the isotopically lighter water of the hypolimnion would shift the δ¹⁸O_diatom value to lower values during settling from 7 to 16 m excluding this process as a cause for the deviation. Dissolution of opal during settling with intact organic coatings of the diatom cells and near neutral pH of the water should only cause a minor enrichment of the 16 m values. Nevertheless, opal from the bottom sediment was found to be 2.5‰ enriched in ¹⁸O compared to the weighted average of the opal from the 7 m trap. Thus, resuspension of bottom material must have contributed to the intermediate δ¹⁸O_diatom signal of the 16 m trap during summer. Dissolution experiments allowed further investigation of the cause for the remarkably enriched δ¹⁸O_diatom value of the bottom sediment. Experiments with different fresh diatomaceous materials show an increase of opaline ¹⁸O at high pH values which is remarkably reduced when organic coatings of the cells still exist or at near neutral pH. In contrast, high pH conditions do not affect the δ¹⁸O_diatom values of sub-fossil and even fossil opal. IR analyses show that the ¹⁸O enrichment of the sedimentary silica is associated with a decrease in Si-OH groups and the formation of Si-O-Si linkages. This indicates a silica dehydroxylation process as cause for the isotopic enrichment of the bottom sediment. Silica dissolution and dehydroxylation clearly induce a maturation process of the diatom oxygen isotope signal presumably following an exponential behaviour with a rapid initial phase of signal alteration. The dynamics of this process is of particular importance for the quantitative interpretation of sedimentary δ¹⁸O_diatom values in terms of palaeothermometry.     

Geochemistry and Rb–Sr geochronology of a ductile shear zone in the Orlica-Śnieżnik dome (West Sudetes, Poland)

Amphibolite-facies orthogneisses of the Orlica-vnie™nik dome in the West Sudetes (Poland) show a local continuous transition from weakly deformed augen gneisses to finely laminated mylonites. Field evidence indicates that ductile shearing developed pre- or syntectonically to a migmatization event. Bulk-rock compositions of variably deformed samples yield no indications for deformation- and/or fluid-enhanced element mobility and redistribution. ⁸⁷Rb-⁸⁶Sr geochronology (biotite, phengite, whole rock) places time constraints on the deformation process and the post-orogenic cooling history. Phengite- and biotite-whole-rock pairs yield Rb-Sr ages of 340 to 334 Ma and 335 to 294 Ma, respectively, independent of the degree of deformation. The weighted mean of phengite-whole-rock pairs indicates an age of 337.4DŽ.3 Ma. Combining most of the biotite-whole-rock data yields a weighted mean age of 328.6dž.4 Ma. Because of their different closure temperatures for the Rb-Sr system, these differences are interpreted to date cooling after a thermal event. Direct dating of the deformation is not possible, but the cooling history record defines a minimum age for the development of ductile shearing and the last migmatization event. These time constraints provide evidence for the initiation of crustal collapse during or immediately following peak metamorphic conditions. The results of this study further document the importance of Variscan metamorphism in the Orlica-vnie™nik dome.     

Occurrence of naphthalenesulfonates and their condensates with formaldehyde in a landfill leachate and their transport behavior in groundwater of the Upper Rhine Valley, Germany

. Naphthalenesulfonates and their condensation products with formaldehyde are manufactured in the chemical industry for broad application as tanning agents, dispersing agents, and as superplasticizers for concrete. With the disposal of waste they have found their way into the aquatic environment. Five monomeric naphthalenesulfonates and a group of dimeric sulfonated naphthalene-formaldehyde condensates (SNFC) were identified in the leachate and in groundwater observation wells downstream in the plume of the Karlsruhe-West landfill, situated in the Upper Rhine Valley in southwest Germany. For the main monomer of technical SNFC products, 2-naphthalenesulfonate (2-NS), the concentration in the leachate was 170 µg l^–1, which decreased to 9.5 µg l^–1 at a distance of about 300 m from the boundary of the landfill. In the Merdingen tracer test field, the transport of these compounds was studied under more controlled conditions in two tracer experiments with (1) two model compounds, and (2) a technical SNFC product and uranine as a reference tracer. In these experiments, the monomeric naphthalenesulfonates and the SNFC with n=2 behave as conservative tracers. Thus, the findings of the landfill study were supported by these results. Higher molecular SNFC were strongly retarded, which is attributed to adsorption to soil particles. The results of the second tracer experiment suggest a degradation of 2-NS and 2,6-naphthalenedisulfonate (2,6-NDS) after adaptation of the microorganisms in the groundwater aquifer as a consequence of the first tracer experiment.     

Quaternary minettes and associated volcanic rocks of Mascota,western Mexico: a consequence of plate extension above a subduction modified mantle wedge

 Pleistocene-Holocene volcanism in the Jalisco block of western Mexico is confined to two conspicuous grabens, where potassic eruptives range from absarokites (48–52% SiO₂) and minettes (49–54% SiO₂) through basaltic andesites (53–57% SiO₂), the most voluminous type, to andesites and their lamprophyric equivalent spessartite (58–62% SiO₂); there are no contemporary rhyolitic rocks. This suite has high concentrations of Mg, Cr (<550 ppm) and Ni (<450 ppm) accompanied by large concentrations of K, P, Ba (<4000 ppm) and Sr (<5000 ppm) and elements such as LREE and Zr (<600 ppm). No combination of crystal fractionation and/or crustal contamination can reproduce the compositional range of these magmas, which nevertheless are believed to be genetically related because of their proximity in time and space. Hydrous minerals in the lamprophyres and the typical absence of plagioclase phenocrysts in both basaltic andesites and andesites reflect the relatively high concentrations of water in the magmas, which suppressed the crystallisation of feldspar. Experimental verification of the minimal amounts of water required to reproduce the phenocryst assemblages in selected rocks range from 3.5 to 6%. During ascent in a volcanic conduit, andesitic magma may lose water and consequently precipitate plagioclase, or it may ascend more rapidly, retaining more of its initial water, which stabilises phenocrysts of hornblende at the expense of plagioclase. Our estimates of water concentrations, which are consistent with the various low pressure phenocryst assemblages, will be minimal for the magmas in their source regions, and the process of magmatic dewatering on ascent may be typical in well established volcanic conduits. In accord with the compositions of phenocrystic olivine in the basaltic andesites and the minettes, the values of FeO and Fe₂O₃ of the bulk lavas and scoriae are demonstrably pristine. As a consequence, there are two characteristic features of the Mascota suite: the high range of relative oxygen fugacities (ΔNNO=1–5) and the high Mg# (MgO/MgO+FeO) that ranges from 0.70 to 0.91 (with only one andesite as low as 0.66). From the evidence of phlogopite phenocrysts, a partial melt involving phlogopite would have a higher Mg# than one from olivine (Fo₉₀) and pyroxene alone. As the Mascota series shows a correlation between K₂O and Mg#, we conclude that it was generated by partial fusion of the mantle wedge, with a variable contribution of phlogopite and apatite from veins throughout the lherzolitic assemblage. In conformity with an origin by varying increments of partial fusion of a phlogopite-bearing mantle, all incompatible elements vary linearly with Ti (or K) as if phlogopite (+apatite) in the source dominated their contribution to the partial melts. Fluids from dehydration of the subducting slab presumably deposit hydrous and other minerals in veins in the mantle wedge and also increase its redox state. As the Mascota volcanism occurs in grabens closer to the trench than the main andesite arc, it is concluded that the eruption of these small volumes of hydrous magmas require the tectonically favored ascent paths offered by the extensional grabens to reach the surface from their mantle sources. Received: 24 January 1995 / Accepted: 21 February 1996     

Self-sedimentation of phytoplankton blooms in the geologic record

Understanding the formation of laminated, organic-rich sediments is an essential topic for researchers interested in fossil fuels, biogeochemical cycles, Earth's environmental history and global change. Biologists have very recently demonstrated that some marine phytoplankton blooms actively govern their own sedimentation by the formation of sticky transparent gels that facilitate rapid aggregation, accelerated sinking and efficient export flux. Here we present fossil evidence of unfragmented, low-diversity phytoplankton assemblages preserved as sedimentary laminae and irregular flocs that are attributable to a similar phytoplankton-driven sedimentary mechanism we term ‘self-sedimentation’. The geological evidence suggests that self-sedimentation precludes significant heterotrophic grazing, propels the formation of some conspicuous hemipelagic sedimentary laminae and results in efficient carbon and opal flux to the sediments. We suggest that the self-sedimentation phenomenon may have broad implications for the geological history of biogeochemical cycling, oceanic ecological dynamics, and abrupt atmospheric/environmental change. Broader recognition of the self-sedimentation phenomenon as explicitly defined here is a prerequisite to testing these unconventional hypotheses.