Petrogenesis of rift-related tephrites, phonolites and trachytes (Central European Volcanic Province, Rhon, FRG): Constraints from Sr, Nd, Pb and O isotopes

The volcanic rocks of the Rhön area (Central European Volcanic Province, Germany) belong to a moderately alkali basaltic suite that is associated with minor tephriphonolites, phonotephrites, tephrites, phonolites and trachytes. Based on isotope sytematics (87Sr/86Sr: 0.7033–0.7042; 143Nd/144Nd: 0.51279–0.51287; 206Pb/204Pb: 19.1–19.5), the inferred parental magmas formed by variable degrees of partial melting of a common asthenospheric mantle source (EAR: European Asthenospheric Reservoir of Cebriá and Wilson, 1995). Tephrites, tephriphonolites, phonotephrites, phonolites and trachytes show depletions and enrichments in some trace elements (Sr, Ba, Nb, Zr, Y) indicating that they were generated by broadly similar differentiation processes that were dominated by fractionation of olivine, clinopyroxene, amphibole, apatite and titaniferous magnetite ± plagioclase ± alkalifeldspar. The fractionated samples seem to have evolved by two distinct processes. One is characterized by pure fractional crystallization indicated by increasing Nb (and other incompatible trace element) concentrations at virtually constant 143Nd/144Nd ~ 0.51280 and 87Sr/86Sr ~ 0.7035. The other process involved an assimilation–fractional crystallization (AFC) process where moderate assimilation to crystallization rates produced evolved magmas characterized by higher Nb concentrations at slightly lower 143Nd/144Nd down to 0.51275. Literature data for some of the evolved rocks show more variable 87Sr/86Sr ranging from 0.7037 to 0.7089 at constant 143Nd/144Nd ~ 0.51280. These features may result from assimilation of upper crustal rocks by highly differentiated low-Sr (< 100 ppm Sr) lavas. However, based on the displacement of the differentiated rocks from this study towards lower 143Nd/144Nd ratios and modeled AFC processes in 143Nd/144Nd vs. 87Sr/86Sr and 207Pb/204Pb vs. 143Nd/144Nd space assimilation of lower crustal rocks seems more likely. The view that assimilation of lower crustal rocks played a role is confirmed by high-precision double-spike Pb isotope data that reveal higher 207Pb/204Pb ratios (15.62–15.63) in the differentiated rocks than in the primitive basanites (15.58–15.61). This is compatible with incorporation of radiogenic Pb from lower crustal xenoliths (207Pb/204Pb: 15.63–15.69) into the melt. However, 206Pb/204Pb ratios are similar for the differentiated rocks (19.13–19.35) and the primitive basanites (19.12–19.55) implying that assimilation involved an ancient crustal end member with a higher U/Pb ratio than the mantle source of the basanites. In addition, alteration-corrected δ18O values of the differentiated rocks range from c. 5 to 7‰ which is the same range as observed in the primitive alkaline rocks. This study confirms previous interpretations that highlighted the role of AFC processes in the evolution of alkaline volcanic rocks in the Rhön area of the Central European Volcanic Province.

Prediction of water–rock interaction and porosity evolution in a granitoid-hosted enhanced geothermal system, using constraints from the 5 km Basel-1 well

Numerical simulations based on plans for a deep geothermal system in Basel, Switzerland are used here to understand chemical processes that occur in an initially dry granitoid reservoir during hydraulic stimulation and long-term water circulation to extract heat. An important question regarding the sustainability of such enhanced geothermal systems (EGS), is whether water–rock reactions will eventually lead to clogging of flow paths in the reservoir and thereby reduce or even completely block fluid throughput. A reactive transport model allows the main chemical reactions to be predicted and the resulting evolution of porosity to be tracked over the expected 30-year operational lifetime of the system. The simulations show that injection of surface water to stimulate fracture permeability in the monzogranite reservoir at 190 °C and 5000 m depth induces redox reactions between the oxidised surface water and the reduced wall rock. Although new calcite, chlorite, hematite and other minerals precipitate near the injection well, their volumes are low and more than compensated by those of the dissolving wall-rock minerals. Thus, during stimulation, reduction of injectivity by mineral precipitation is unlikely. During the simulated long-term operation of the system, the main mineral reactions are the hydration and albitization of plagioclase, the alteration of hornblende to an assemblage of smectites and chlorites and of primary K-feldspar to muscovite and microcline. Within a closed-system doublet, the composition of the circulated fluid changes only slightly during its repeated passage through the reservoir, as the wall rock essentially undergoes isochemical recrystallization. Even after 30 years of circulation, the calculations show that porosity is reduced by only ∼0.2%, well below the expected fracture porosity induced by stimulation. This result suggests that permeability reduction owing to water–rock interaction is unlikely to jeopardize the long-term operation of deep, granitoid-hosted EGS systems. A peculiarity at Basel is the presence of anhydrite as fracture coatings at ∼5000 m depth. Simulated exposure of the circulating fluid to anhydrite induces a stronger redox disequilibrium in the reservoir, driving dissolution of ferrous minerals and precipitation of ferric smectites, hematite and pyrite. However, even in this scenario the porosity reduction is at most 0.5%, a value which is unproblematic for sustainable fluid circulation through the reservoir.

“Sweating meteorites”-Water-soluble salts and temperature variation in ordinary chondrites and soil from the hot desert of Oman

The common appearance of hygroscopic brine (“sweating”) on ordinary chondrites (OCs) from Oman during storage under room conditions initiated a study on the role of water-soluble salts on the weathering of OCs. Analyses of leachates from OCs and soils, combined with petrography of alteration features and a 11-month record of in situ meteorite and soil temperatures, are used to evaluate the role of salts in OC weathering. Main soluble ions in soils are Ca2+, SO42−, HCO3−, Na+, and Cl−, while OC leachates are dominated by Mg2+ (from meteoritic olivine), Ca2+ (from soil), Cl− (from soil), SO42− (from meteoritic troilite and soil), and iron (meteoritic). “Sweating meteorites” mainly contain Mg2+ and Cl−. The median Na/Cl mass ratio of leachates changes from 0.65 in soils to 0.07 in meteorites, indicating the precipitation of a Na-rich phase or loss of an efflorescent Na-salt. The total concentrations of water-soluble ions in bulk OCs ranges from 600 to 9000 μg g−1 (median 2500 μg g−1) as compared to 187–14140 μg g−1 in soils (median 1148 μg g−1). Soil salts dissolved by rain water are soaked up by meteorites by capillary forces. Daily heating (up to 66.3 °C) and cooling of the meteorites cause a pumping effect, resulting in a strong concentration of soluble ions in meteorites over time. The concentrations of water-soluble ions in meteorites, which are complex mixtures of ions from the soil and from oxidation and hydrolysis of meteoritic material, depend on the degree of weathering and are highest at W3. Input of soil contaminants generally dominates over the ions mobilized from meteorites. Silicate hydrolysis preferentially affects olivine and is enhanced by sulfide oxidation, producing local acidic conditions as evidenced by jarosite. Plagioclase weathering is negligible. After completion of troilite oxidation, the rate of chemical weathering slows down with continuing Ca-sulfate contamination.

High exchangeable calcium concentrations in soils on Barro Colorado Island, Panama

The soils on four lithologies (basaltic conglomerates, Bohio; Andesite; volcanoclastic sediments with basaltic agglomerates, Caimito volcanic; foraminiferal limestone, Caimito marine) on Barro Colorado Island (BCI) have high exchangeable Ca concentrations and cation-exchange capacities (CEC) compared to other tropical soils on similar parent material. In the 0–10 cm layer of 24 mineral soils, pH values ranged from 5.7 (Caimito volcanic and Andesite) to 6.5 (Caimito marine), concentrations of exchangeable Ca from 134 mmolc kg− 1 (Caimito volcanic) to 585 mmolc kg− 1 (Caimito marine), and cation exchange capacities from 317 mmolc kg− 1 (Caimito volcanic) to 933 mmolc kg− 1 (Caimito marine). X-ray diffractometry of the fraction < 2 μm revealed that smectites dominated the clay mineral assemblage in soil except on Caimito volcanic, where kaolinite was the dominant clay mineral. Exchangeable Ca concentrations decreased with increasing soil depth except on Caimito marine. The weathering indices Chemical Index of Alteration (CIA), Plagioclase Index of Alteration (PIA) and Weathering Index of Parker (WIP) determined for five soils on all geological formations, suggested that in contrast to expectation the topsoil (0–10 cm) appeared to be the least and the subsoil (50–70 cm) and saprolite (isomorphically weathered rock in the soil matrix) the most weathered. Additionally, the weathering indices indicated depletion of base cations and enrichment of Al-(hydr)oxides throughout the soil profile. Tree species did not have an effect on soil properties. Impeded leaching and the related occurrence of overland flow seem to be important in determining clay mineralogy. Our results suggest that (i) edaphic conditions favor the formation of smectites on most lithologies resulting in high CEC and thus high retention capacity for Ca and (ii) that there is an external source such as dust or sea spray deposition supplying Ca to the soils.

Age of cleft monazites in the eastern Tauern Window: constraints on crystallization conditions of hydrothermal monazite

Monazite-bearing Alpine clefts located in the Sonnblick region of the eastern Tauern Window, Austria, are oriented perpendicular to the foliation and lineation. Ion probe (SIMS) Th–Pb and U–Pb dating of four cleft monazites yields crystallization ages of different growth domains and aggregate regions ranging from 18.99 ± 0.51 to 15.00 ± 0.51 Ma. The crystallization ages obtained are overlapping or slightly younger than zircon fission track ages but older than zircon (U–Th)/He cooling ages from the same area. This constrains cleft monazite crystallization in this area to *300–200 �C. LA-ICP-MS data of dated hydrothermal monazites indicate that in graphite-bearing, reduced host lithologies, cleft monazite is poor in As and has higher La/Yb values and U concentrations, whereas in oxidised host rocks opposite trends are observed. Monazites show negative Eu anomalies and variable La/Yb values ranging from 520 to 6050. The positive correlation between Ca and Sr concentration indicates dissolution of plagioclase or carbonates as the source of these elements. The data show that early exhumation and cleft formation in the Tauern is related to metamorphic dome formation caused by the collision of the Adriatic with the European plate and that monazite crystallization in the clefts occurred later. Our data also demonstrate that hydrothermal monazite ages offer great potential in helping to constrain the chronology of exhumation in collisional orogens.

XMapTools: a MATLAB©-based program for electron microprobe X-ray image processing and geothermobarometry

XMapTools is a MATLAB©-based graphical user interface program for electron microprobe X-ray image processing, which can be used to estimate the pressure–temperature conditions of crystallization of minerals in metamorphic rocks. This program (available online at http://www.xmaptools.com) provides a method to standardize raw electron microprobe data and includes functions to calculate the oxide weight percent compositions for various minerals. A set of external functions is provided to calculate structural formulae from the standardized analyses as well as to estimate pressure–temperature conditions of crystallization, using empirical and semi-empirical thermobarometers from the literature. Two graphical user interface modules, Chem2D and Triplot3D, are used to plot mineral compositions into binary and ternary diagrams. As an example, the software is used to study a high-pressure Himalayan eclogite sample from the Stak massif in Pakistan. The high-pressure paragenesis consisting of omphacite and garnet has been retrogressed to a symplectitic assemblage of amphibole, plagioclase and clinopyroxene. Mineral compositions corresponding to ~165,000 analyses yield estimates for the eclogitic pressure–temperature retrograde path from 25 kbar to 9 kbar. Corresponding pressure–temperature maps were plotted and used to interpret the link between the equilibrium conditions of crystallization and the symplectitic microstructures. This example illustrates the usefulness of XMapTools for studying variations of the chemical composition of minerals and for retrieving information on metamorphic conditions on a microscale, towards computation of continuous pressure–temperature-and relative time path in zoned metamorphic minerals not affected by post-crystallization diffusion.

Variations of clinopyroxene/melt element partitioning during assimilation of olivine/peridotite by low-Mg diorite magma

The effects of crystal chemistry and melt composition on the control of clinopyroxene/melt element partitioning (D) during the assimilation of olivine/peridotite by felsic magma have been investigated in Mesozoic high-Mg diorites from North China. The assimilation resulted in significant increase of Mg, Cr and Ni and only slight (< 30%) decrease of incompatible elements of the magma, and the compositional variations have been mirrored by the normally and reversely zoned clinopyroxene microphenocrysts formed at the early stage of the magma evolution. The Mg# [100 × Mg / (Mg + Fe)] values of the reversely zoned clinopyroxenes increase from 65 to 75 in the core to 85–90 in the high-Mg midsection, and reduce back to 73–79 at the rim. Trace element profiles across all these clinopyroxene domains have been measured by LA-ICP-MS. The melt trace element composition has been constrained from bulk rock analyses of the fine-grained low- and high-Mg diorites. Clinopyroxene/melt partition coefficients for rare earth elements (REE) and Y in the high-Mg group zonings (Mg# > 73–79, DDy < 1.2) are positively correlated with tetrahedral IVAl and increase by a factor of 3–4 as tetrahedral IVAl increases from 0.01 to 0.1 per formula unit (pfu). These systematic variations are interpreted to be controlled by the clinopyroxene composition. In contrast, partition coefficients for low-Mg group zonings (Mg# < 75–79, DDy > 1.2) are elevated by up to an order of magnitude (for REE and Y) or more (for Zr and Hf) at similar IVAl, indicating dominant control of melt composition/structure. DZr and DHf show a larger sensitivity to the compositional change of crystal and melt than DREE. DTi values for the low- and high-Mg zonings show a uniform dependence on IVAl. DSr and DLi are insensitive to the compositional change of clinopyroxene and melt, resulting in Sr depletions in the clinopyroxene zonings with elevated REE without crystallization of plagioclase. Our observations show that crystal chemistry and melt composition/structure may alternatively control clinopyroxene/melt partitioning during the assimilation of peridotite by felsic magma, and may be useful for deciphering clinopyroxene compositions and related crust–mantle processes.

Petrology and geochemistry at DSDP Site 89-462

The 16 samples of Deep Sea Drilling Project (DSDP) Leg 89 basalts that we analyzed for whole rock major and trace elements and for mineralogic compositions are identical to some of the basalts recovered during Leg 61. Leg 89 samples are mostly olivine-plagioclase-clinopyroxene sparsely phyric basalts and exhibit a wide variety of textures. These basalts have lower TiO2 at a given Mg/(Mg+Fe2+)*100 than MORB (midocean ridge basalt). We recognize three major chemical types of basalts in the Nauru Basin. We believe that different degrees of partial melting, modified by fractional crystallization and possibly by magma mixing at shallow depths, can explain the chemical differences among the three groups. This petrogenetic model is consistent with the observed downhole chemical-chronostratigraphic relations of the samples. New 87Sr/86Sr and U3Nd/144Nd analyses of basalt samples from DSDP Site 462 indicate that the Nauru Basin igneous complex is within the Sr-Nd isotopic range of ocean island basalt. Thus the Nauru Basin igneous complex resembles MORB in many aspects of its chemistry, morphology, and secondary alteration patterns (Larson, Schlanger, et al., 1981), but not in its isotopic characteristics. If it were not for the unambiguous evidence that the Nauru Basin complex was erupted off-ridge, the complex could easily be interpreted as normal oceanic layer 2. For this reason, we speculate that the Nauru Basin igneous complex was produced in an oceanic riftlike environment when multiple, fast-propagating rifts were formed during the fast seafloor spreading episode in the Cretaceous.

(Table 1) Geochemistry of realatively fresh rocks of ODP Sites 127-794 and 127-797

The flows and sills drilled at Sites 794 and 797 in the Yamato Basin of the Japan Sea are subalkalic, olivine, and/or plagioclase phyric basalts. Compositionally, the rocks can be divided into a depleted, low-K type and an enriched, relatively high-K type. In addition, two contrasting evolution trends are reflected in the rock compositions, which allow four different magmatic suites to be identified. It is suggested that the depleted or enriched nature of these suites represent primary characteristics, while the different evolution trends are related to fractionation processes in crustal magma chambers. A tholeiitic evolution trend, with increasing FeO and TiO2 and decreasing Al2O3, can be modelled by fractional crystallization of 40%-50% plagioclase, olivine, and augite. A mildly calc-alkalic evolution trend, with decreasing FeO, increasing Al2O3, and nearly constant TiO2, can be modelled by 8%-12% olivine fractionation. Mineralogical evidence suggests that these differences may be related to the effect of small amounts of water during crystallization of the calc-alkalic suites. The tholeiitic suites occur in the lower parts of the drill cores, while the calc-alkalic suites occur in the upper parts. This suggests a complex tectonic and magmatic evolution, perhaps reflecting a transition between calc-alkalic magmatism related to subduction zone activity and tholeiitic magmatism related to back-arc spreading. Furthermore, any magmatic model must be able to account for the range in parental magmas from depleted to enriched throughout the tectonic history of the Yamato Basin.

Clay mineral and heavy metal composition of sea-bed surface sediments and pre-Holocene sediment samples taken during POLARSTERN cruise ANT-XXIII/9

Surface mineralogical compositions and their association to modern processes are well known from the east Atlantic and south-west Indian sectors of the Southern Ocean, but data from the interface of these areas - the Prydz Bay-Kerguelen region - is still missing. The objective of our study was to provide mineralogical data of reference samples from this region and to relate these mineralogical assemblages to hinterland geology, weathering, transport and depositional processes. Clay mineral assemblages were analysed by means of X-ray diffraction technique. Heavy mineral assemblages were determined by counting of gravity-separated grains under a polarizing microscope. Results show that by use of clay mineral assemblages four mineralogical provinces can be subdivided: i) continental shelf, ii) continental slope, iii) deep sea, iv) Kerguelen Plateau. Heavy mineral assemblages in the fine sand fraction are relatively uniform except for samples taken from the East Antarctic shelf. Our findings show that mineralogical studies on sediment cores from the study area have the potential to provide insights into past shifts in ice-supported transport and activity and provenance of different water masses (e.g. Antarctic slope current and deep western boundary current) in the Prydz Bay-Kerguelen region.

Investigation of diagenesis in sediment core CRP-1 from the Ross Sea, Antarctica

A diagenetic study was carried out on the cored Miocene section in CRP-1 by thin-section, X-ray diffraction, scanning electron microscope, electron microprobe and stable isotopic analysis. Carbonate (calcite, siderite) microconcretions occur locally within intergranular pores and open fractures, and some sands are cemented by microcrystalline calcite. Calcite cement at 115.12 mbsf (metres below sea floor) and possibly microconcretionary calcite at 44.62 mbsf record infiltration of meteoric waters into the section, consistent with sequence stratigraphic evidence for multiple glacial advances over the CRP-1 drillsite. Diagenetic carbonates incorporated carbon derived from both organic matter and marine carbonate. Carbon isotope data are consistent with microconcretion formation at shallow depths. Sandstones are poorly compacted and, despite containing a large component of chemically unstable grains, are virtually unaltered. Preservation of the chemically unstable grain component reflects the cold climate depositional setting and shallow maximum burial depths.

Geochemical analyses of secondary minerals from ODP Leg 115 basalts (Tables 1+2)

Basalts recovered along the Reunion hotspot track on Ocean Drilling Program (ODP) Leg 115 range in age from 34 Ma at Site 706 to 64 Ma at Site 707. They have undergone various degrees of secondary alteration. Within single holes the amount of alteration can vary from a few percent to near complete replacement of phenocrysts and groundmass by secondary minerals. Olivine appears to be the most susceptible to alteration and in some sections it is the only mineral altered. In other sections, olivine, pyroxene and plagioclase phenocrysts, and groundmass have been completely replaced by secondary minerals. Clays are the predominant form of secondary mineralization. In addition to replacing olivine, pyroxene, glass, and groundmass, clays have filled veins, vesicles, and voids. Minor amounts of calcite, zeolites, and K-feldspar were also detected. The clays that filled vesicles and veins often show color zonations of dark, opaque bands near the edges that grade into tan or green transparent regions in the centers of the veins. The electron microprobe was used to obtain chemical analyses of these veins as well as to characterize isolated clays that replaced specific minerals and filled voids and vesicles.

Rb, Sr, Sm and Nd concentrations and isotopic composition of basalts from DSDP Leg 74 (Table 1)

Basement intersected in DSDP holes 525A, 528 and 527 on the Walvis Ridge consists of submarine basalt flows and pillows with minor intercalated sediments. These holes are situated on the crest and mid and lower northwest flank of a NNW-SSE-trending ridge block which would have closely paralleled the paleo mid-ocean ridge (Rabinowitz and LaBrecque, 1979 doi:10.1029/JB084iB11p05973, Moore et al. (1983 doi:10.1130/0016-7606(1983)94<907:TWRTDS>2.0.CO;2). The basalts were erupted approximately 70 m.y. ago, an age equivalent to that of immediately adjacent oceanic crust in the Angola Basin and coraistent with formation at the paleo mid-ocean ridge (Moore et al., 1983). The basalt types vary from aphyric quartz tholeiites on the ridge crest to highly plagioclase phyric olivine tholeiites on the ridge flank. These show systematic differences in incompatible trace element and isotopic composition. Many element and isotope ratio pairs form systematic trends with the ridge crest basalts at one end and the highly phyric ridge flank basalts at the other. The low 143Nd/144Nd (0.51238), 206Pb/204Pb (17.54), 207Pb/204Pb (15.47), 208Pb/204Pb (38.14) and high 87Sr/86Sr (0.70512) ratios of the ridge crest basalts suggest derivation from an old Nd/Sm-, Rb/Sr- and Pb/U-enriched mantle source. This isotopic signature is similar to that of alkaline basalts on Tristan da Cunha but offset to significantly lower Nd and Pb isotopic ratios. The isotopic ratio trends may be extrapolated beyond the ridge flank basalts with higher 143Nd/144Nd (0.51270), 206Pb/204Pb (18.32), 207Pb/204Pb (15.52), 208Pb/204Pb (38.77) and lower 87Sr/86Sr (0.70417) ratios in the direction of increasingly Nd/Sm-, Rb/Sr- and Pb/U-depleted source compositions. These isotopic correlations are equally consistent with mixing of depleted and enriched end member melts or partial melting of an inhomogeneous, variably enriched mantle source. However, observed Zr-Ba-Nb-Y interelement relationships are inconsistent with any simple two-component model of magma mixing, as might result from the rise of a lower mantle plume through the upper mantle. Incompatible element and Pb isotopic systematics also preclude extensive involvement of depleted (N-type) MORB material or its mantle sources. In our preferred petrogenetic model the Walvis Ridge basalts were derived by partial melting of mantle similar to an enriched (E-type) MORB source which had become heterogeneous on a small scale due to the introduction of small-volume melts and metasomatic fluids.

Geochemistry of Cretaceous sills and lava flows of ODP Holes 129-800A and 129-802A

On the basis of their respective eruptive environments and chemical characteristics, alkalic dolerite sills from the northern Pigafetta Basin (Site 800) and tholeiitic pillow lavas from the Mariana Basin (Site 802) sampled during Ocean Drilling Program Leg 129 are considered to represent examples of the widespread mid-Cretaceous volcanic event in the western Pacific. Both groups of basic rocks feature mild, low-grade, anoxic smectite-celadonite-carbonate-pyrite alteration; late-stage oxidation is very limited in extent, with the exception of the uppermost sill unit at Site 800. The aphyric and nonvesicular Site 800 alkalic dolerite sills are all well-evolved mineralogically and chemically, being mainly of hawaiite composition, and are similar to ocean island basalts. They are characterized by high contents of incompatible elements (for example, 300-400 ppm Zr), well-fractionated rare earth element patterns ([La/Yb]N 18-21) and HIMU isotopic characters. They probably represent deep-sea, lateral, intrusive off-shoots from nearby seamounts of similar age. The olivine-plagioclase +/- clinopyroxene phyric tholeiitic pillow lavas and thin flows of Site 802 are nonvesicular and quench-textured throughout. Relative to normal-type mid-ocean ridge basalt, they are enriched in large-ion-lithophile elements, exhibit flat (unfractionated) rare earth element patterns and have distinctive (lower) Zr/Nb, Zr/Ta, La/Ta, and Hf/Th ratios. Overall they are compositionally and isotopically similar to the mid-Cretaceous tholeiites of the Nauru basin and the Ontong-Java and Manihiki plateaus. The Site 802 tholeiites differ from the thickened crustal segments of the oceanic plateaus, however, in apparently representing only a thin veneer over the local basement in an off-axis environment.