The Late Cretaceous Impact of the Trindade Mantle Plume: Evidence from Large-volume, Mafic, Potassic Magmatism in SE Brazil

When the subcontinental lithospheric mantle undergoes heatingand/or extension, some of the earliest mafic melts to be generatedare those rich in volatUes and potassium. In some cases, e.g.when a plume impinges on thick cratonic lithosphere or whenthe amount of extension is very small, K-rich mafic igneousrocks may be the only surface expression of mantle melting.The Alto Paranaiba Igneous Province, in SE Brazil, is one ofthe world's most voluminous mafic potassic provinces (>15000km³),which until recently was relatively unknown. The magmas wereemplaced into a narrow Proterozoic mobile belt close to thesurface margin of the Sao Francisco craton, and it is one ofseveral Cretaceous alkaline igneous provinces that are locatedaround the margin of the Parana sedimentary basin in Braziland Paraguay.Detailed geochemical analyses of samples from throughoutthe Alto Paranaiba Igneous Province show that it is composedof a relatively diverse suite of ultrapotassic-potassic, ultramaficmqfic,silica-undersaturated lavas and hypabyssal intrusions, i.e.kimberlites, madupitic olivine lamproites and kamafugitic rocks.These all have very high concentrations of incompatible traceelements and are all strongly enriched in light rare earth relativeto heavy rare earth elements (e.g. La/Yb=50-230). Wide variationsin major element ratios, which are unrelated to the effectsof crystal fractionation in these magmas (e.g. CaO/Al₂O₃), suggestthat the mafic potassic rocks were derived from a heterogeneousmantle source. They show relatively restricted ranges of initial⁸⁷Sr/⁸⁶Sr (070436-070588) and Nd₂₅ values of -4 to -8, intermediatebetween Group I and II South African kimberlites. T_DM Nd isotopemodel ages of 900 Ma suggest that the magmas were derived bythe remobilization of subcontinental lithospheric mantle thathad been enriched by small-volume K-rich melt fractions sincethe Late Proterozoic.New K/Ar ages for mica separates show thatthe kimberlites, madupitic olivine lamproites and kamafugiticrocks were emplaced together with large carbonatite-bearingplutonic complexes at 85 Ma. Reconstructions of plate motionsshow that, at this time, the location of the Alto ParanaibaIgneous Province coincided with the postulated position of thepresent-day Trindade(or Martin Vaz) plume. We propose that thewidespread Late Cretaceous alkaline magmatism in SE Brazil mayhave been caused by impingement of this plume on the base ofthe subcontinental lithosphere. Heat penetrating the lithosphere,both by conduction and advection by asthenospheric-source decompressionmelts, may have caused melting of the readily fusible partsof the lithospheric mantle and the genesis of mafic potassicand (after fractionation) carbonatite magmas. The Proterozoicmobile belt (the Brasilia Belt) appears to have acted as a Hhinspofrelative to the adjacent Sao Francisco craton, allowing greaterupwelling and melting of the asthenosphere. Subsequently, asthe craton passed over the plume, volcanism was switched off'until the Early Tertiary when the plume reemerged from beneaththe westward drifting South America continent and was the magmasource for oceanic-islands and seamounts of the Trindade-Vitriachain. Corresponding author     

Importance of heavy metal-organic matter interactions in natural waters

The role of organic ligands in metal complexing in natural waters has received little attention because of uncertainties regarding both the abundance and nature of dissolved organic carbon compounds. Recent data show that the bulk of dissolved organic matter in natural waters consists of highly oxidized and chemically and biologically stable polymeric compounds closely resembling soil humic substances. Average molar concentrations of these aquatic humics in major U.S. rivers range from 5 × 10^?6to 3 × 10^?5 moles 1^?1. Fractional elution of soil organic matter by meteoric waters may be considered to be the main process contributing to the presence of humic matter in rivers. The aquatic humic polymers participate in complex formation through ionizable functional groups with a range of differential acidities. The stabilities of metal-humic complexes in natural waters are higher than those of the corresponding inorganic metal complexes. Quantitative evaluation of the metal-organic interactions can be approached by applying variable equilibrium functions which take into account the differential physico-chemical characteristics of the active complexing sites on the polymer molecule. Assuming an average humic concentration of 10 mg 1^?1, complexation of trace metals can be significant even in the presence of excess concentrations of major cations.     

Effect of nano-hematite morphology on photocatalytic activity

Nano-hematites, i.e., hematites with nanoparticle-, nanorod-, and nanotube-like morphologies, were synthesized via the hydrothermal method by controlling the reaction time, temperature, and reactant concentration. The nano-hematites of different crystal shapes all exhibited band gaps within the visible-light region (1.56–2.1 eV). Further, they showed weak ferromagnetic behavior, and their coercive magnetic field was larger than that of the bulk hematite. Moreover, all the nano-hematites also exhibited high photocatalytic activities during the degradation of methylene blue under visible-light irradiation. The experimental data fitted the Langmuir–Hinshelwood kinetics model very well. The nanorods had the highest photocatalytic rate constant per unit surface area, possibly owing to a higher aspect ratios; this lowers the electron–hole recombination rate. These results suggest that the crystal morphology of hematites has a significant effect on their physical and photocatalytic properties. Therefore, controlling the morphology of the materials is essential for obtaining well-tailored photocatalysts.     

An infrared spectroscopic study of lawsonite to 20 GPa

The infrared spectrum of CaAl₂Si₂O₇ · H₂O-lawsonite, has been characterized to pressures of 20 GPa at 300 K. Our results constrain the response to compression of the silicate tetrahedra, hydroxyl units, and water molecules in this material. The asymmetric and symmetric stretching and bending vibrations of the Si₂O₇ groups (at zero pressure frequencies between 600 and 1000 cm⁻¹) increase in frequency with pressure at rates between 3.6 and 5.9 cm⁻¹/GPa. All silicate modes appear to shift continuously with pressure to 20 GPa, although the lowest frequency stretching vibration becomes unresolvable above 18 GPa, and a splitting of the main bending vibration is observed near this pressure. The O-H stretches of the hydroxyl units exhibit a discontinuity in their mode shifts at ∼8–9 GPa, which we interpret to be produced by a pressure-induced change in hydrogen bonding. The stretching and bending vibrations of the water molecule are relatively unaffected by compression to 20 GPa, thus demonstrating that the structural cavities in which water molecules reside are relatively rigid. Significant changes in the amplitude of the O-H stretches of the hydroxyl and water units are observed at this pressure as well; nevertheless, our results demonstrate that the dominant structural units in lawsonite persist metastably at 300 K with only modest structural modifications well beyond the known stability field of this phase. Received: 10 July 1998 / Revised, accepted: 23 October 1998     

Groundwater contamination with arsenic and other trace elements in an area of the pampa,province of Córdoba,Argentina

A geochemical study of groundwater of the pampa in the province of Córdoba, Argentina, was performed; the area covered approximately 10,000 km².Physical-chemical parameters, dissolved solids, and seven trace elements were determined in 60 selected water samples. Systematic and accurate measurements of arsenic, flourine, and vanadium were performed for the first time. Three trace element contaminants not reported earlier were found: an important one, selenium, and two others of less known effects, uranium and molybdenum.Eighty-four percent of the water analyzed showed arsenic contents over 0.05 mg/L, maximum contaminant level established by the U.S. Environmental Protection Agency (1982). The frequency distribution of trace elements was analyzed, and its fit to the lognormal distribution was proved by means of the Pearson and Kolmogorov-Smirnov test; the geographic distribution of the seven trace elements was mapped and its correlation with the anion-cation composition of the water was studied.The maximum arsenic, fluorine, vanadium, and uranium contents were found in the western part of the area under study, in waters containing dominant alkali metals in the cation composition. Maximum selenium and antimony contents were found in the eastern part of the area, while molybdenum distribution does not show any relationship with the other two groups. In addition, the geographic distribution of the trace elements seems to be related to the subsurface structure, which has been inferred using interactive digital analysis of Landsat imagery. The movements of the subsoil have disturbed surface and subsurface drainage influencing the water salinity and trace element contents.In order to investigate the origin of the contamination, 54 loess samples were collected in wells at depths ranging from the surface down to the water table. This loess, which has a high proportion of volcanic components, mainly rhyolitic glass, exhibits a chemical composition corresponding to that of a dacite.The loess and the volcanic glass show anomalous contents of all contaminant trace elements, mainly arsenic and selenium. For this reason loess is considered the most important contamination source in the groundwater under study.     

XPS identification of bulk hole defects and itinerant Fe 3d electrons in natural troilite (FeS)

XPS measurements have been made of vacuum-fractured monoclinic pyrrhotite and troilite that highlight sulfur coordination (S 2p) and iron electronic state (Fe 2p) differences between these two minerals as a result of iron lattice site occupancy. Metal-like Fe states are observed in the Fe 2p spectrum of troilite due to increased occupancy of Fe lattice sites and increased Fe-Fe 3d orbital interaction within the constraints of the mineral structure. Additional electron population near the top of the troilite valence band is confirmed by XPS measurement. These results provide comprehensive experimental evidence for itinerent 3d electrons in the natural iron sulfides.     

Petrogenesis of Peraluminous Granites, Monashee Mountains, Southeastern Canadian Cordillera

Two-mica granites that locally contain garnet and sillimaniteoccur as dikes, sills, and sheets up to 50 m thick within thesillimanite zonc of the Monashee Mountains in the southeasternCanadian Cordillera of British Columbia. Syn-kinematic and post-kinematicgranites are recognized. U-Pb dating of zircon demonstrates that the syn-kinematic granitesare 100.4?0.3 Ma old, based on duplicate concordant single abradedzircon analyses. Other zircons have slightly older Pb/Pb dates,indicating small amounts of inherited zircons. Monazites are99?10 Ma old. Post-kinematic granites have 62.5?0.2 Ma zirconages and 634+0.1 Ma monazite ages. High initial 87 ratios (0.71492–0.74181)and evidence of Precambrian Pb inheritance indicates that bothsyn- and post-kinematic granites were derived from a crustalsource. Geobarometric estimates suggest that both generationsof granites equilibrated at 6–8 kb (22–30 km). Zirconand monazite saturation temperatures range from 660–824?Cand indicate that these minerals were liquidus phases earlyin the crystallization history of the granites. Because monazitesaturation temperatures generally exceed those of zircon, itis possible that some monazites may be inherited. Apatite saturationtemperatures in excess of 900?C suggest that both generationsof granites contain source inherited apatite. Syn- and post-kinematic granites have essentially identicalmajor and trace element chemistries. Syn-kinematic graniteshave steep light rare earth element (LREE) enriched patternswith pronounced negative Eu anomalies. The REE patterns of post-kinematicgranites range from steep LREE enriched patterns with negativeNd and Eu anomalies to flat patterns with low LREE contents,negative Nd anomalies, and both positive and negative Eu anomalies.Modelling of REE, Rb, Sr, and Ba contents demonstrates thatsyn-kinematic gramtes could have been generated by a low degreeof partial melting (with 10–25% feldspar fractionationof the melt) of Late Proterozoic Horsethief Creek Group metapelitesleaving a monazite-bearing upper amphibolite facies residue.Post-kinematic granites were produced by partial melting ofa geochemically and isotopically similar metapelitic source.The suite of post-kinematic granites can be related by a smallamount (up to 0.1%) of monazite crystal fractionation.     

Application of multivariate statistical methods to indicate the origin and geochemical behavior of potentially hazardous elements in sediment around the Sarcheshmeh copper mine,SE Iran

Multivariate statistical techniques, i.e., correlation coefficient analysis, principal components analysis (PCA), and hierarchical cluster analysis (CA), were applied to the total and water-soluble concentrations of potentially hazardous metals in sediments associated with the Sarcheshmeh mine, one of the largest Oligo-Miocene porphyry copper deposits in the world. The samples were analyzed for hazardous metal concentration levels by inductively coupled plasma mass spectrometry method. Results indicate that the contaminant metals As, Cd, Cu, Mo, S, Sb, Sn, Se, Pb, and Zn were positively correlated with the total concentrations. These hazardous metals also have strong association in the PCA and CA results. Different anthropic versus natural sources of contaminant metals were distinguished by using CA method. Water-soluble fraction of hazardous metals showed that the hydro-geochemical behavior of these metals in sediments is different considerably. Elements such as Cd, Co, Cr, Cu, Fe, Mn, Ni, S, and Zn are readily water soluble from contaminated samples, especially from evaporative mineral phases, while the release of As, Mo, Sb, and Pb into the water is limited by adsorption processes. Results obtained from the application of multivariate techniques on the water-soluble fraction data set show that the hazardous metals are categorized into three groups including (1) Ni, S, Co, Cu, Cr, and Fe; (2) Se, Mn, Cd, and Zn; and (3) Sb, As, Mo, and Sn. This classification describes the hydro-geochemical behavior of hazardous metals in water–sediment environments of the Sarcheshmeh porphyry copper mine and can be used as a basis in remedial and treatment strategies.     

Constraints on the timing of granite emplacement, deformation and metamorphism in the Shamva area, Zimbabwe

In order to constrain the temporal relationship between granite (sensu lato) emplacement and metamorphism, isotope work was carried out on the minerals zircon and apatite (U-Pb), garnet (Pb-Pb) and hornblende (Ar-Ar) from wall rock samples in the Shamva area in Zimbabwe. The area, encompassing parts of the Chinamora and Murehwa batholiths and a wedge-shaped greenstone belt segment in between, is commonly quoted in the literature as an example illustrating pluton emplacement processes and deformational models for the Archean. New U-Pb dating of apatite from a boudinaged pegmatite within mafic schists in the batholith-greenstone contact zone has yielded an age of 2619 +28/-24 Ma. This age is interpreted as the best estimation of the intrusion age of this unit, depending on the assumed closure temperature, and provides an upper age limit for the syntectonic emplacement of the now gneissic granites. Pb-Pb dating of late kinematic garnets in cordierite-bearing rocks within the greenstone belt wall rocks gives an age of 2623NJ Ma. Together, this timing of relatively late, syntectonic plutonism and metamorphic mineral growth at ca. 2.62 Ga compares well with existing zircon crystallization ages for felsic volcanics (2645dž Ma, 2643NJ Ma) and post-tectonic porphyritic monzogranites (2601ᆢ Ma). Ar-Ar hornblende ages for mafic schists from different areas within the greenstone belt wall rocks range between 2621 and 2498 Ma and have been interpreted to indicate mixing between metamorphic ages and cooling ages. The data support a geological model whereby volcanism and sedimentation are associated with an early phase of regional deformation at ca. 2.64 Ga, which may have started earlier and lasted longer, and evolves into the voluminous emplacement of granites (now gneissic granites) in the batholiths at approximately 2.62 Ga. Emplacement of post-tectonic tabular monzogranites takes place at ca. 2.60 Ga.     

Raman spectrum of natural and synthetic stishovite

Raman spectra of natural and synthetic samples of stishovite have been measured with a micro-optical spectrometer system. These spectra have a pattern that is characteristic of rutile-structured oxides. The spectrum of synthetic stishovite is characterized by well-resolved bands at 231, 589, 753, and 967 cm^?1, which are assigned as theB _1g,E _g,A _1g, andB _2g fundamentals, respectively, of the first-order Raman spectrum of the ideal, ordered structure. Natural stishovite obtained from Meteor Crater, Arizona has a first-order Raman spectrum that is fully consistent with that of the synthetic material. The observed spectrum of the natural sample, however, is weaker and has bands in addition to those identified as fundamentals in the spectrum of the synthetic material. A broad band at ～475 cm^?1 may be indicative of glass or contaminants derived from the extraction procedure. Alternatively, this band may arise from multiphonon scattering that is enhanced by poor crystallinity or structural disorder in the natural shocked sample.