The fluoride in the groundwater of Guarani Aquifer System: the origin associated with black shales of Paraná Basin

This work presents petrological and geochemical results of the black shales interval from Permian and Devonian strata of the Paraná Basin, Brazil and its relationships with fluoride of groundwater from Guarani Aquifer System. The Guarani Aquifer, located in South Brazil, Uruguay, Paraguay and Argentine, presents contents of fluoride higher than the Brazilian accepted potability limits. Several hypotheses have been presented for the origin of the fluoride in the groundwater of the Guarani Aquifer. Microcrystalline fluorite was registered in black shales of Ponta Grossa and Irati formations from Paraná Basin. The results shown in this work suggest that fluoride present in groundwater of Guarani Aquifer can be originated in deeper groundwater that circulates in Ponta Grossa and Irati formations. The interaction of the groundwater coming from deeper black shales with the groundwater-bearing Aquifer Guarani System occurs through regional fragile structures (faults and fractures) that constitute excellent hydraulic connectors between the two sedimentary packages. The microcrystalline fluorite registered in Ponta Grossa and Irati Formations can be dissolved promoting fluoride enrichment in groundwater of these black shales and Guarani Aquifer System.     

Hydrogeochemistry and Water Quality Evaluation along the Flow Path in the Unconfined Aquifer of the Düzce Plain,North-western Turkey

The Düzce Plain has a multi-aquifer system, which consists of a near surface unconfined aquifer, along with first and second deeper confined aquifers. Hydrochemical evolution and water quality are related to infiltration of the precipitation, recharge from the formations surrounding the plain, flow path of groundwater and the relationship between surface and groundwater. The groundwater in the unconfined aquifer flows towards the Efteni Lake and the Büyük Melen River. Surface waters are divided into two main hydrochemical facies in the study area: (a) Ca2+–HCO3?; and (b) Ca2+, Mg2+–HCO3-, SO42-. The groundwater has generally three main hydrochemical facies: (a) Ca2+–HCO3-; (b) Ca2+, Mg2+–HCO3-; and (c) Ca2+, Mg2+–HCO3-, Cl-. The hydrochemical facies "a" and "b" dominate within shallow depths in recharge areas under rapid flow conditions, while hydrochemical facies "c" characterizes shallow and mixed groundwater, which dominate intermediate or discharge areas (near Efteni Lake and Büyük Melen River) during low flow conditions and agricultural contamination. Calcium and bicarbonate ions, total hardness and electrical conductivity of total dissolved solids (EC–TDS) values increase along the groundwater flow path; but these parameters remain within the limits specified by the standards set for industrial and agricultural usages.     

Hydrochemical dynamics of TOC and NO3 − contents as natural tracers of infiltration in karst aquifers

Analysis of Total Organic Carbon (TOC) and NO₃ ^? contents in the water at six springs in the province of Malaga (Southern Spain), sampled under different hydrologic conditions, revealed two different hydrochemical behaviour patterns for these natural tracers of infiltration. TOC content increased during every recharge period, following the rapid arrival of water infiltrating through the soil. On the other hand, NO₃ ^? content only rose during the first flood episodes (normally in autumn), and fell during the winter and spring ones. This difference is consequence of the distinctive biogeochemical kinetics of nitrogen with respect to organic carbon, both in the soil and within the aquifer. Unlike the mineralisation undergone by TOC from the surface to the spring, the NO₃ ^? ion remains in the aquifer almost unaffected, due to the oxidizing conditions prevailing within the karst medium, which do not allow its denitrification and favour its preservation within the saturated zone. In non-polluted aquifers, TOC and NO₃ ^? have a common origin in the soil and can be used to determine infiltration processes and the hydrogeological functioning of karst aquifers. Their different hydrochemical evolution provides information about mineralization and degradation processes of organic matter within karst aquifers, which can be used to validate the vulnerability to contamination in this type of medium.     

Hydrogeochemical and Geophysical Evaluation of the Recharge Zone of Guarani Aquifer in Municipally of Candelária,Rio Grande do Sul,Brazil

Geotechnical and Geological Engineering - A large part of the Guarani Aquifer is located in the state of Rio Grande do Sul (Brazil) and additionally possesses a recharge area located in its central...     

A chromate-contaminated site in southern Switzerland – Part 1: Site characterization and the use of Cr isotopes to delineate fate and transport

The risk of groundwater contamination by chromate at a former chromite ore processing industrial site in Rivera (Switzerland) was assessed by determining subsoil Cr(VI) concentrations and tracking naturally occurring Cr(VI) reduction with Cr isotopes. Using a hot alkaline extraction procedure, a total Cr(VI) contamination of several 1000 kg was estimated. Jarosite, KFe₃((SO₄)_x(CrO₄)_1−x)₂(OH)₆, and chromatite (CaCrO₄) were identified as Cr(VI) bearing mineral phases using XRD, both limiting groundwater Cr(VI) concentrations. To track assumed Cr(VI) reduction at field scale δ⁵³Cr values of contaminated subsoil samples in addition to groundwater δ⁵³Cr data are used for the first time. The measurements showed a fractionation of groundwater δ⁵³Cr values towards positive values and subsoil δ⁵³Cr towards negative values confirming reduction of soluble Cr(VI) to insoluble Cr(III). Using a Rayleigh fractionation model, a current Cr(VI) reduction efficiency of approximately 31% along a 120 m long flow path was estimated at an average linear groundwater velocity of 3.3 m/d. Groundwater and subsoil δ⁵³Cr values were compared with a site specific Rayleigh fractionation model proposing that subsoil δ⁵³Cr values can possibly be used to track previous higher Cr(VI) reduction efficiency during the period of industrial activity. The findings strongly favor monitored natural attenuation to be part of the required site remediation measures.     

Variolitic lavas in the axial rift of the Mid-Atlantic Ridge and their origin (Sierra Leone area, 6°18′N)

Altered variolites described for the first time in the axial zone of the Mid-Atlantic Ridge are represented by rounded globules of andesite (icelandite) composition with light trachyandesite rim embedded in a picrobasaltic matrix. The globules were transferred with picrobasaltic melt and then floated to the surface of lava flow, while formation of leucocratic rims was presumably related to thermodiffusion (Soret effect) in a cooling heterogeneous melt. This heterogeneous melt was formed by penetration of ascending column of picrobasaltic magma in already existing small intracructsal magmatic chamber filled with residual icelanditetype andesite melt and involvement of the latter into a general upward movement. The rapid ascent of the melts in the oceanic spreading zones by means of turbulent flowing caused dispersion of the extragenous melt into small drops in a jet of picrobasaltic magma, without their interaction. Variolites were formed during cooling of such heterogeneous lava flow. No signs of liquid immiscibility were found in the studied variolites.     

Tracing sources of pollution in soils from the Jinding Pb–Zn mining district in China using cadmium and lead isotopes

Systematic variations in the Cd and Pb isotope ratios in polluted topsoils surrounding the Jinding Pb–Zn mine in China were measured so that the sources of the metals could be traced. The average δ^114/110Cd value and ²⁰⁶Pb/²⁰⁷Pb isotope ratio in background soils from the region were +0.41‰ and 1.1902, respectively, whereas the contaminated soil samples had different values, with the δ^114/110Cd values varying between −0.59‰ and +0.33‰ and the ²⁰⁶Pb/²⁰⁷Pb isotope ratios varying between 1.1764 and 1.1896. We also measured the Cd and Pb isotopic compositions in oxide ores, sulfide ores, and slags, and found that binary mixing between ores and background soils could explain almost all of the variations in the Cd and Pb isotope ratios in the contaminated soils. This suggests that Cd and Pb pollution in the soils was mainly caused by the deposition of dust emitted during anthropogenic activities (mining and refining). The Pb and Cd isotope ratios clearly showed that contamination in soils in the northeastern part of the area was caused by surface mines and zinc smelters and their slagheaps, while contamination in soils in the southwestern part of the area also came from tailing ponds and underground mines. The main area of soil polluted by dust from Pb–Zn mining processes roughly extended for up to 5 km from the mine itself.     

EPR investigation of NO2 and CO2 − and other radicals in beryl

A number of different impurities are located in the open channels of natural beryl crystals. The rare Maxixe beryl contains an unusual amount of NO₂. The isoelectronic CO₂ ⁻ radical is found in the irradiated Maxixe-type beryl. The NO₂ radicals are distributed in the Be–Al plane of the crystal, with the nitrogen atom close to the oxygens of the beryl cavity wall. These oxygens repel the negative CO₂ ⁻ radical, which is located at the center of the beryl cavity and rotates around its O–O axis, which is parallel to the crystal c-axis. When there is a nearby alkali ion at the center of the beryl channel, it reorients the CO₂ ⁻ radical so that its bisector is parallel to the c-axis and points toward the positive ion. Different signals are analyzed for Li⁺, Na⁺, and another counter-ion, which probably is Cs⁺. The related NO₃ and CO₃ ⁻ radicals are the color centers in the investigated deep blue beryls. The slow decay of the color, which makes these beryls useless as gem stones, is related to the decay of the hydrogen atoms which are present in these crystals. Evidence is given that NO₃ is created in Maxixe beryl by a natural process, while CO₃ ⁻ in Maxixe-type beryl has been created by irradiation. The temperature dependence of the EPR signals of these two radicals was investigated, but a definitive proof that they rotate at the center of the beryl cavity could not be given. EPR signals from some other radicals in beryl have been observed and described.     

The origin of variable-δ18O zircons in Jurassic and Cretaceous Mo-bearing granitoids in the eastern Xing–Meng Orogenic Belt,Northeast China

This study reports new zircon U–Pb ages, Lu–Hf isotope data, and oxygen isotope data for Mesozoic Mo-bearing granitoids in the eastern Xing–Meng Orogenic Belt (XMOB) of Northeast China, within the eastern Central Asian Orogenic Belt. Combining these new laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) zircon U–Pb ages with the results of previous research indicates that two stages of Mo-bearing granitoid magmatism occurred in the eastern XMOB, during the Early–Middle Jurassic (200–165 Ma) and the Early Cretaceous (ca. 111 Ma). The eastern XMOB also contains Mo-bearing granitoids with variable δ¹⁸O compositions that record variations in source oxygen isotopic compositions. Combining δ¹⁸O data with zircon U–Pb and Hf isotopic data provides evidence of the origin of these granitoids. Three types of zircon have been identified within these granitoids. Type 1 zircons formed during the Mesozoic and having high δ¹⁸O values (5.71–7.05‰) that are consistent with the compositions of magmatic zircons from the Luming, Jiapigou, and Kanchuangou areas. These zircons suggest that the Mo-bearing granitoids were derived from a source containing supracrustal materials. The type 2 zircons have extremely low and heterogeneous δ¹⁸O values (4.64–4.89‰) that are consistent with the compositions of magmatic zircons from the Jidetun and Fuanpu areas. These magmas were generated by the remelting of juvenile crustal material that was previously significantly modified by interaction with fluids. Type 3 zircons generally have mantle-like δ¹⁸O values (5.42–5.57‰), with several zircons yielding higher δ¹⁸O values, suggesting that these intrusions formed from mantle-derived magmas that assimilated and were metasomatized by crustal material. Combining these geochemical data with the geology of this region indicates that the Mo-bearing granitoids were generated as a result of subduction of the Palaeo-Pacific Plate beneath the Eurasian continent.     

Application of lead stable isotopes to the Guadiamar Aquifer study after the mine tailings spill in Aznalcóllar (SW Spain)

On 25 April 1998 the tailings dam of the Aznalcóllar mine burst, a great quantity of pyrite waste sludge and acid water was spilled reaching the vicinity of the Doñana National Park. In surface and ground water samples taken a week after dam breaking, metals, trace elements and Pb isotopic ratios (²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb) were analysed. In September 1998 a second sampling survey was carried out. The surface waters have a similar isotopic composition as the lead contained in the pyrite from the Aznalcóllar mine. The polluted groundwater of the Guadiamar aquifer also shows the influence of the mining origin of the lead. Lead isotope ratios (²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb) in the groundwater of the Almonte-Marismas are very low and they differ clearly from the rest of groundwater samples. A further group of wells has a lead isotope composition intermediate between the Aznalcóllar mine and the atmospheric aerosols of the Iberian Peninsula.     

The nature,origin and modification of insoluble organic matter in chondrites,the major source of Earth’s C and N

All chondrites accreted ∼3.5 wt.% C in their matrices, the bulk of which was in a macromolecular solvent and acid insoluble organic material (IOM). Similar material to IOM is found in interplanetary dust particles (IDPs) and comets. The IOM accounts for almost all of the C and N in chondrites, and a significant fraction of the H. Chondrites and, to a lesser extent, comets were probably the major sources of volatiles for the Earth and the other terrestrial planets. Hence, IOM was both the major source of Earth’s volatiles and a potential source of complex prebiotic molecules.Large enrichments in D and ¹⁵N, relative to the bulk solar isotopic compositions, suggest that IOM or its precursors formed in very cold, radiation-rich environments. Whether these environments were in the interstellar medium (ISM) or the outer Solar System is unresolved. Nevertheless, the elemental and isotopic compositions and functional group chemistry of IOM provide important clues to the origin(s) of organic matter in protoplanetary disks. IOM is modified relatively easily by thermal and aqueous processes, so that it can also be used to constrain the conditions in the solar nebula prior to chondrite accretion and the conditions in the chondrite parent bodies after accretion.Here we review what is known about the abundances, compositions and physical nature of IOM in the most primitive chondrites. We also discuss how the IOM has been modified by thermal metamorphism and aqueous alteration in the chondrite parent bodies, and how these changes may be used both as petrologic indicators of the intensity of parent body processing and as tools for classification. Finally, we critically assess the various proposed mechanisms for the formation of IOM in the ISM or Solar System.     

Cordierite-garnet-sillimanite-quartz equilibrium: I. New experimental calibration in the system FeO−Al2O3−SiO2−H2O and certain P-T-X H2O relations

The equilibrium in which hydrous Fe-cordierite breaks down to almandine, sillimanite, quartz, and water was previously experimentally determined by Richardson (1968) and Holdaway and Lee (1977) using QMF buffer and by Weisbrod (1973) using QIF buffer. All these studies yielded similar results — a negative dP/dT slope for the equilibrium curve. However, based on theoretical arguments, Martignole and Sisi (1981), and based on Fe-Mg partitioning experiments on coexisting cordierite and garnet in equilibrium with sillimanite and quartz, Aranovich and Podlesskii (1983) suggested that this equilibrium curve has a positive dP/dT slope and its position depends on the water content of the equilibrium cordierite. We have redetermined this equilibrium using a much improved tecnique of detecting reaction direction, and cordierite starting material that contained virtually no hercynite. Hercynite was present as a contaminant in the cordierites of previous experimental studies and possibly reacted with quartz during the experimental runs to expand the apparent stability field of Fe-cordierite. We synthesized Fe-cordierite from reagent grade oxides at 710°C and 2 kbar (using QMF buffer) with two intermediate stages of grinding and mixing. The cordierite has a unit cell volume of 1574.60 ų (molar volume=23.706 J/bar) and no Fe³⁺ as indicated by X-ray diffraction and room temperature Mössbauer studies respectively. Reaction direction was concluded by noting20% change of the ratios of intensities of two key X-ray diffraction peaks of cordierite and almandine. Our results show that the four-phase equilibrium curve passes through the points 2.1 kbar, 650°C and 2.5 kbar, 750°C. This disagrees with all previous experimental studies. H₂O in the Fe-cordierite, equilibrated at 2.2 kbar and 700°C and determined by H-extraction line in the stable isotope laboratory, is 1.13 wt% (n=0.41 moles). H₂O content of pure Mg-cordierite equilibrated under identical conditions and determined by thermogravimentric conditions and determined by thermogravimetric analysis is 1.22 wt% (n=0.40). Similar determinations on Fe-cordierite and Mg-cordierite equilibrated at 2.0 kbar and 650°C show 1.27 wt% (n=0.46) and 1.47 wt% (n=0.48) of H₂O respectively. Thus, H₂O content appears to be independent of Fe/Mg ratio in cordierite, a conclusion which supports previous experimental determinations. The experimentally determined equilibrium curve represents conditions of P_H2O=P_total. From this we calculated the anhydrous curve representing equilibrium under conditions of X _H2O ^V =0.0. A family of calculated equilibrium curves of constant n _H2O ^Cord cut the experimentally determined curve at a very small angle indicating a slight variation in n _H2O ^Cord in cordierite in equilibrium with almandine, sillimanite, and quartz under the conditions of constant X _H2O ^V . Ancther set of calculated equilibrium curves, each representing constant a _H2O ^V demonstrate that the slopes of the curves vary with X _H2O ^V , and are all positive in the full range of 0.0X _H2O ^V 1.0.     

Evaluation of the effects of uncertainty on the predictions of landslide occurrences using the Shannon entropy theory and Dempster–Shafer theory

Natural Hazards - One of the requirements for planning and decision-making to develop the infrastructures is to prepare the landslide occurrence hazard map. For this purpose, in this article, the...     

Pb−Sr−Nd−O isotopic constraints on the origin of rhyolites from the Taupo Volcanic Zone of New Zealand: evidence for assimilation followed by fractionation from basalt

A comprehensive Sr–Nd–Pb–O isotopic study is reported for rhyolites from the Maroa Volcanic Centre in the Taupo Volcanic Zone (TVZ) of New Zealand. The Sr–Nd isotopic compositions of the rhyolites (⁸⁷Sr/⁸⁶Sr=0.705236 to 0.705660 and _Nd = 2.0 to 0.2) are intermediate between those of primitive basalts (⁸⁷Sr/⁸⁶Sr=0.70387 and _Nd = 5.3) and the Torlesse basement (⁸⁷Sr/⁸⁶Sr=0.709 and _Nd = -4.5). The relatively low mantle-like oxygen isotopic compositions of ¹⁸ O = 7 ± 0.5 are consistent with the Nd-Sr isotopic constraints in that they can be accounted for by 15% to 25% crustal contamination of a basaltic parent by relatively ¹⁸ O-rich Torlesse metasediment. High precision Pb isotopic analyses of plagioclase separates from the Maroa rhyolites show that they have essentially the same compositions as the Torlesse metasedimentary terrane which is itself distinctive from the Western or Waipapa metasediments. Due to the high concentration of Pb in the Torlesse metasediments (>20 ppm) compared to the basalts (<2 ppm), the Pb isotopic composition of the volcanics may be controlled by relatively small amounts (>10%) of crustal contamination. All these results are shown to be consistent with derivation of the rhyolites by 15% to 25% contamination of relatively primitive basaltic magmas with Torlesse metasedimentary crust, followed by extensive, essentially closed system fractionation of the basalt to a magma of rhyolite composition. It is argued that the processes of assimilation and fractionation are separated in both space and time. The voluminous high silica rhyolites, which make up >97% of the exposed volcanism in the continental margin back-are basin environment of the TVZ, therefore appear to be a product of predominantly new additions to the crust with assimilation-recycling of pre-existing crust being of secondary importance.     

The age and source of late Hercynian magmatism in the central Alps: evidence from precise U−Pb ages and initial Hf isotopes

This study presents U–Pb ages for zircon, titanite, allanite and epidote, and initial Hf isotopic compositions for zircon of Upper Carboniferous granites, diorites and syenites from the Aar massif, central Alps. The rocks were emplaced during three magmatic pulses after Hercynian collisional tectonics: (A) a shoshonitic-ultrapotassic series at 334±2.5 Ma; (B) scattered diorites and granites at 308–310 Ma; and (C) a high-K cale-alkaline granite batholith at 298±2 Ma. Inheritance of old zircons is negligible among all three groups. The Southern Aar granite, in contrast, is a syn-tectonic, probably ca. 350 Ma old granite that contains large amounts of inherited Precambrian zircons. Alpine metamorphism caused weak lead loss in many analyzed zircon fractions, but left the titanite U–Pb system undisturbed: thorites were almost completely reset by Alpine and recent lead loss. Mineral isochrons defined by titanite, allanite, epidote and apatite yield initial Pb isotopic compositions that are in agreement with the model values of Stacey and Kramers. Initial Hf isotopic compositions range from _Hf=–8 to +3.5. The data follow a trend of increasing _Hf with decreasing age. The _Hf versus element concentration relationships suggest mixing between a mantle and a crustal component. These relationships can be explained in terms of generation of the melts from a subcontinental mantle that had been enriched during subduction events at about 1 Ga and by 300 Ma had developed an isotopic signature distinct from that of MORB-type mantle. Further contamination of the melts occurred during ascent and differentiation in the crust. This late Hercynian magmatism can be related to post-collisional strike-slip tectonics.     

Estimation of the Incorporation of Impurity K and Na Ions in the CaSiO3 and MgSiO3 Crystal Structures at Pressures of 18–25 GPa

Doklady Earth Sciences - Based on atomistic modeling data, various schemes of the isomorphic incorporation of K+ and Na+ ions into the crystal structures of CaSiO3 and MgSiO3 in the pressure range...     

The effects of K2O on the compositions of near-solidus melts of garnet peridotite at 3 GPa and the origin of basalts from enriched mantle

Enrichment in K₂O in oceanic island basalts (OIB) is correlated with high SiO₂, low CaO/Al₂O₃, and radiogenic isotopic signatures indicative of enriched mantle sources (EM1 and EM2). These are also chemical characteristics of the petit-spot lavas, which are highly enriched in K₂O (3–4 wt%) compared to other primitive oceanic basalts. We present experimentally derived liquids with varying concentrations of K₂O in equilibrium with a garnet lherzolite residue at 3 GPa to test the hypothesis that the major element characteristics of EM-type basalts are related to their enrichment in K₂O. SiO₂ is known to increase with K₂O at pressures less than 3 GPa, but it was previously unknown if this effect was significant at the high pressures associated with partial melting at the base of the lithosphere. We find that at 3 GPa for each 1 wt% increase in the K₂O content of a garnet lherzolite saturated melt, SiO₂ increases by ~0.5 wt% and CaO decreases by ~0.5 wt%. MgO and $K_{D}^{{{\text{Fe}} - {\text{Mg}}}}$ K D Fe - Mg each decrease slightly with K₂O concentration, as do Na₂O and Cr₂O₃. The effect of K₂O alone is not strong enough to account for the SiO₂ and CaO signatures associated with high-K₂O OIB. The SiO₂, CaO, and K₂O concentrations of experimentally derived partial melts presented here resemble those of petit-spot lavas, but the Al₂O₃ concentrations from the experimental melts are greater. Partitioning of K₂O between peridotite and melt suggests that petit spots, previously considered to sample ambient asthenosphere, require a source more enriched in K₂O than the MORB source.     

Magma mixing and the generation of isotopically juvenile silicic magma at Yellowstone caldera inferred from coupling 238U–230Th ages with trace elements and Hf and O isotopes in zircon and Pb isotopes in sanidine

The nature of compositional heterogeneity within large silicic magma bodies has important implications for how silicic reservoirs are assembled and evolve through time. We examine compositional heterogeneity in the youngest (~170 to 70 ka) post-caldera volcanism at Yellowstone caldera, the Central Plateau Member (CPM) rhyolites, as a case study. We compare ²³⁸U–²³⁰Th age, trace-element, and Hf isotopic data from zircons, and major-element, Ba, and Pb isotopic data from sanidines hosted in two CPM rhyolites (Hayden Valley and Solfatara Plateau flows) and one extracaldera rhyolite (Gibbon River flow), all of which erupted near the caldera margin ca. 100 ka. The Hayden Valley flow hosts two zircon populations and one sanidine population that are consistent with residence in the CPM reservoir. The Gibbon River flow hosts one zircon population that is compositionally distinct from Hayden Valley flow zircons. The Solfatara Plateau flow contains multiple sanidine populations and all three zircon populations found in the Hayden Valley and Gibbon River flows, demonstrating that the Solfatara Plateau flow formed by mixing extracaldera magma with the margin of the CPM reservoir. This process highlights the dynamic nature of magmatic interactions at the margins of large silicic reservoirs. More generally, Hf isotopic data from the CPM zircons provide the first direct evidence for isotopically juvenile magmas contributing mass to the youngest post-caldera magmatic system and demonstrate that the sources contributing magma to the CPM reservoir were heterogeneous in ¹⁷⁶Hf/¹⁷⁷Hf at ca. 100 ka. Thus, the limited compositional variability of CPM glasses reflects homogenization occurring within the CPM reservoir, not a homogeneous source.