Rare earth elements and stable isotope geochemistry (δ13C and δ18O) of phosphorite deposits in the Gafsa Basin, Tunisia

Rare earth elements (REE) and stable isotope compositions (delta C-13 and delta O-18) of shark teeth and phosphatic coprolites were analyzed from the Lower Maastrichtian layers of the El Haria Formation and two sequences of the Paleocene-Eocene (P/E) Chouabine Formation in the Gafsa Basin (south western of Tunisia) in order to trace the sedimentological, climatic and oceanographic conditions. The REE chemistry and their distribution in the two archives are the same for each of the studied layers indicating that the coprolites and shark teeth experienced the same early diagenetic environments. However major differences occur between the Maastrichtian and the P/E reflecting changes in the depositional conditions. The Early Maastrichtian burial environment tended to be more anoxic with REE derived from reduced FeO. While in the P/E the REE patterns mimic the modern oxic-suboxic seawater, the REE source from remineralisation of organic coating could have more significance. The oxygen isotope compositions of the structural phosphates (delta O-18(PO4)) indicate a stable and warm climate during both studied time intervals. A small offset (-0.4 parts per thousand) in the delta O-18 value between the coprolites and shark teeth show minor thermal gradient between bottom and surface water. The pronounced negative shift of 34%. in delta C-13 values recorded in the upper part of the Chouabine Formation was ascribed to the Paleocene-Eocene boundary. At the same time the lack of negative change in the delta O-18 is explained by the semi-closed situation of the Gafsa Basin, which situation also played an important role in the evolution of the organic matters in the sediment resulting in the exceptional low delta C-13 values. (C) 2008 Elsevier B.V. All rights reserved.

Stable isotope and trace element stratigraphy across the Permian-Triassic transition: A redefinition of the boundary in the Velebit Mountain, Croatia

Stable isotopes of carbonates (delta(13)C(carb), delta(18)O(carb)), organic matter (delta(13)C(org), delta(15)N(org)) and major, trace and rare earth element (REE) compositions of marine carbonate rocks of Late Permian to Early Triassic age were used to establish the position of the Permian-Triassic boundary (PTB) at two continuous sections in the Velebit Mountain, Croatia. The chosen sections - Rizvanusa and Brezimenjaca - are composed of two lithostratigraphic units, the Upper Permian Transitional Dolomite and the overlying Sandy Dolomite. The contact between these units, characterized by the erosional features and sudden occurrence of ooids and siliciclastic grains, was previously considered as the chronostratigraphic PTB. The Sandy Dolomite is characterized by high content of non-carbonate material (up to similar to 30 wt.% insoluble residue), originated from erosion of the uplifted hinterland. A relatively rich assemblage of Permian fossils (including Geinitzina, Globivalvulina, Hemigordius, bioclasts of gastropods, ostracods and brachiopods) was found for the first time in Sandy Dolomite, 5 m above the lithologic boundary in the Rizvanusa section. A rather abrupt negative delta(13)C(carb) excursion in both sections appears in rocks showing no recognizable facies change within the Sandy Dolomite, -2 parts per thousand at Rizvanusa and -1.2 parts per thousand at Brezimenjaca, 11 m and 0.2 m above the lithologic contact, respectively. This level within the lower part of the Sandy Dolomite is proposed as the chemostratigraphic PTB. In the Rizvanusa section, the delta(13)C(org) values decline gradually from similar to-25 parts per thousand in the Upper Permian to similar to-29 parts per thousand in the Lower Triassic. The first negative delta(13)C(org) excursion occurs above the lithologic contact, within the uppermost Permian deposits, and appears to be related to the input of terrigenous material. The release of isotopically light microbial soil-biomass into the shallow-marine water may explain this sudden decrease of delta(13)C(org) values below the PTB. This would support the hypothesis that in the western Tethyan realm the land extinction, triggering a sudden drop of woody vegetation and related land erosion, preceded the marine extinction. The relatively low delta(15)N(org) values at the Permian-Triassic (P-Tr) transition level, close to approximate to 0 parts per thousand, and a secondary negative delta(13)C(org) excursion of -0.5 parts per thousand point to significant terrestrial input and primary contribution of cyanobacteria. The profiles of the concentrations of redox-sensitive elements (Ce, Mn, Fe, V), biogenic or biogenic-scavenged elements (P, Ba, Zn, V), Ce/Ce* values, and normalized trace elements, including Ba/Al, Ba/Fe, Ti/Al, Al/(Al + Fe + Mn) and Mn/Ti show clear excursions at the Transitional Dolomite-Sandy Dolomite lithologic boundary and the chemostratigraphic P-Tr boundary. The stratigraphic variations indicate a major regression phase marking the lithologic boundary, transgressive phases in the latest Permian and a gradual change into shallow/stagnant anoxic marine environment towards the P-Tr boundary level and during the earliest Triassic. (C) 2010 Elsevier B.V. All rights reserved.

Metallogenic model of the Trepca Pb-Zn-Ag skarn deposit, Kosovo: Evidence from fluid inclusions, Rare Earth Elements, and stable isotope data

The Trepca Pb-Zn-Ag skarn deposit (29 Mt of ore at 3.45% Pb, 2.30% Zn, and 80 g/t Ag) is located in the Kopaonik block of the western Vardar zone, Kosovo. The mineralization, hosted by recrystallized limestone of Upper Triassic age, was structurally and lithologically controlled. Ore deposition is spatially and temporally related with the postcollisional magmatism of Oligocene age (23-26 Ma). The deposit was formed during two distinct mineralization stages: an early prograde closed-system and a later retrograde open-system stage. The prograde mineralization consisting mainly of pyroxenes (Hd(54-100)Jo(0-45)Di(0-45)) resulted from the interaction of magmatic fluids associated with Oligocene (23-26 Ma) postcollisional magmatism. Whereas there is no direct contact between magmatic rocks and the mineralization, the deposit is classified as a distal Pb-Zn-Ag skarn. Abundant pyroxene reflects low oxygen fugacity (<10(-31) bar) and anhydrous environment. Fluid inclusion data and mineral assemblage limit the prograde stage within a temperature range between 390 degrees and 475 degrees C. Formation pressure is estimated below 900 bars. Isotopic composition of aqueous fluid, inclusions hosted by hedenbergite (delta D = -108 to -130 parts per thousand; delta O-18 = 7.5-8.0 parts per thousand), Mn-enriched mineralogy and high REE content of the host carbonates at the contact with the skarn mineralization suggest that a magmatic fluid was modified during its infiltration through the country rocks. The retrograde mineral assemblage comprises ilvaite, magnetite, arsenopyrite, pyrrhotite, marcasite, pyrite, quartz, and various carbonates. Increases in oxygen and sulfur fugacities, as well as a hydrous character of mineralization, require an open-system model. The opening of the system is related to phreatomagmatic explosion and formation of the breccia. Arsenopyrite geothermometer limits the retrograde stage within the temperature range between 350 degrees and 380 degrees C and sulfur fugacity between 10(-8.8) and 10(-7.2) bars. The principal ore minerals, galena, sphalerite, pyrite, and minor chalcopyrite, were deposited from a moderately saline Ca-Na chloride fluid at around 350 degrees C. According to the isotopic composition of fluid inclusions hosted by sphalerite (delta D = -55 to -74 parts per thousand; delta O-18 = -9.6 to -13.6 parts per thousand), the fluid responsible for ore deposition was dominantly meteoric in origin. The delta S-31 values of the sulfides spanning between -5.5 and +10 parts per thousand point to a magmatic origin of sulfur. Ore deposition appears to have been largely contemporaneous with the retrograde stage of the skarn development. Postore stage accompanied the precipitation of significant amount of carbonates including the travertine deposits at the deposit surface. Mineralogical composition of travertine varies from calcite to siderite and all carbonates contain significant amounts of Mn. Decreased formation temperature and depletion in the REE content point to an influence of pH-neutralized cold ground water and dying magmatic system.

Trace element partitioning in HP-LT metamorphic assemblages during subduction-related metamorphism, Ile de Groix, France: a detailed LA-ICPMS study

Devolatilization reactions and subsequent transfer of fluid from subducted oceanic crust into the overlying mantle wedge are important processes, which are responsible for the specific geochemical characteristics of subduction-related metamorphic rocks, as well as those of arc magmatism. To better understand the geochemical fingerprint induced by fluid mobilization during dehydration and rehydration processes related to subduction zone metamorphism, the trace element and rare earth element (REE) distribution patterns in HP-LT metamorphic assemblages in eclogite-, blueschist- and greenschist-facies rocks of the Ile de Groix were obtained by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) analysis. This study focuses on 10 massive basic rocks representing former hydrothermally altered mid-ocean ridge basalts (MORB), four banded basic rocks of volcano-sedimentary origin and one micaschist. The main hosts for incompatible trace elements are epidote (REE, Th, U, Pb, Sr), garnet [Y, heavy REE (HREE)], phengite (Cs, Rb, Ba, B), titanite [Ti, Nb, Ta, REE; HREE > LREE (light REE)], rutile (Ti, Nb, Ta) and apatite (REE, Sr). The trace element contents of omphacite, amphibole, albite and chlorite are low. The incompatible trace element contents of minerals are controlled by the stable metamorphic mineral assemblage and directly related to the appearance, disappearance and reappearance of minerals, especially epidote, garnet, titanite, rutile and phengite, during subduction zone metamorphism. Epidote is a key mineral in the trace element exchange process because of its large stability field, ranging from lower greenschist- to blueschist- and eclogite-facies conditions. Different generations of epidote are generally observed and related to the coexisting phases at different stages of the metamorphic cycle (e.g. lawsonite, garnet, titanite). Epidote thus controls most of the REE budget during the changing P-T conditions along the prograde and retrograde path. Phengite also plays an important role in determining the large ion lithophile element (LILE) budget, as it is stable to high P-T conditions. The breakdown of phengite causes the release of LILE during retrogression. A comparison of trace element abundances in whole-rocks and minerals shows that the HP-LT metamorphic rocks largely retain the geochemical characteristics of their basic, volcano-sedimentary and pelitic protoliths, including a hydrothermal alteration overprint before the subduction process. A large part of the incompatible trace elements remained trapped in the rocks and was recycled within the various metamorphic assemblages stable under changing metamorphic conditions during the subduction process, indicating that devolatilization reactions in massive basic rocks do not necessarily imply significant simultaneous trace element and REE release.

Trace element chemistry and U-Pb dating of zircons from oceanic gabbros and their relationship with whole rock composition (Lanzo, Italian Alps)

The U-Pb ages and the trace element content of zircon U-Pb along with major and trace element whole rock data on gabbroic dikes from the Lanzo lherzolitic massif, N-Italy, have been determined to constrain crustal accretion in ocean-continent transition zones. Three Fe-Ti gabbros were dated from the central and the southern part of the massif providing middle Jurassic ages of 161 +/- 2, 158 +/- 2 and 163 +/- 1 Ma, which argue for magmatic activity over few millions of years. Zircon crystals are characterized by high but variable Th/U ratios, rare earth element patterns enriched in heavy rare earths, pronounced positive Ce and negative Eu-anomalies consistent with crystallization after substantial plagioclase fractionation. The zircon trace element composition coupled with whole rock chemistry was used to reconstruct the crystallization history of the gabbros. A number of gabbros crystallized in situ, and zircon precipitated from trapped, intercumulus liquid, while other gabbros represent residual liquids that were extracted from a cumulus pile and crystallized along syn-magmatic shear zones. We propose a model in which the emplacement mechanism of gabbroic rocks in ocean-continent transition zones evolves from in situ crystallization to stratified crystallization with efficient extraction of residual liquid along syn-magmatic shear zones. Such an evolution of the crystallization history is probably related to the thermal evolution of the underlying mantle lithosphere.

Migration of sharks into freshwater systems during the Miocene and implications for Alpine paleoelevation

Trace-element and isotopic compositions of fossilized shark teeth sampled from Miocene marine sediments of the north Alpine Molasse Basin, the Vienna Basin, and the Pannonian Basin generally show evidence of formation in a marine environment under conditions geochemically equivalent to the open ocean. In contrast, two of eight shark teeth from the Swiss Upper Marine Molasse locality of La Moliere have extremely low delta O-18 values (10.3% and 11.3%) and low Sr-87/Sr-86 ratios (0.707840 and 0.707812) compared to other teeth from this locality (21.1%,22.4%o and 0.708421-0.708630). The rare earth element (REE) abundances and patterns from La Moliere not only differ between dentine and enameloid of the same tooth, but also between different teeth, supporting variable conditions of diagenesis at this site. However, the REE patterns of enameloid from the ``exotic'' teeth analyzed for O and Sr isotopic compositions are similar to those of teeth that have O and Sr isotopic compositions typical of a marine setting at this site. Collectively, this suggests that the two ``exotic'' teeth were formed while the sharks frequented a freshwater environment with very low O-18-content and Sr isotopic composition controlled by Mesozoic calcareous rocks. This is consistent with a paleogeography of high-elevation (similar to 2300 m) Miocene Alps adjacent to a marginal sea.

Hydrocarbon biomarkers in the Topla-Mezica zinc-lead deposits, northern Karavanke/Drau Range, Slovenia: Paleoenvironment at the site of ore formation

The Mississippi Valley-type zinc and lead deposits at Topla (250,150 metric tons (t) of ore grading 1.0 wt % Zn and 3.3 wt % Pb) and Mezica (19 million metric tons (Mt) of ore grading 5.3 wt % Pb and 2.7 wt % Zn) occur within the Middle to Upper Triassic platform carbonate rocks of the northern Karavanke/Drau Range geotectonic units of the Eastern Alps, Slovenia. The ore and host rocks of these deposits have been investigated by a combination of inorganic and organic geochemical methods to determine major, trace, and rare earth element (REE) concentrations, hydrocarbon distribution, and stable isotope ratios of carbonates, kerogen, extractable organic matter, and individual hydrocarbons. These data combined with sedimentological evidence provide insight into the paleoenvironmental conditions at the site of ore formation. The carbonate isotope composition, the REE patterns, and the distribution of hydrocarbon biomarkers (normal alkanes and steranes) suggest a marine depositional environment. At Topla, a relatively high concentration of redox sensitive trace elements (V, Mo, U) in the host dolostones and REE patterns parallel to that of the North American shale composite suggest that sediments were deposited in a reducing environment. Anoxic conditions enhanced the preservation of organic matter and resulted in relatively higher total organic carbon contents (up to 0.4 wt %). The isotopic composition of the kerogen (delta C-13(kerogon) = -29.4 to -25.0 parts per thousand, delta N-15(kerogen) = -.13.6 to 6.8 parts per thousand) suggests that marine algae and/or bacteria were the main source of organic carbon with a very minor contribution from detrital continental plants and a varying degree of alteration. Extractable organic matter from Topla ore is generally depleted in C-13 compared to the associated kerogen, which is consistent with an indigenous source of the bitumens. The mineralization correlates with delta N-15(kerogen) values around 0 per mil, C-13 depleted kerogen, C-13 enriched n-heptadecane, and relatively high concentrations of bacteria] hydrocarbon biomarkers, indicating a high cyanobacterial biomass at the site of ore formation. Abundant dissimilatory sulfate-reducing bacteria, feeding on the cyanobacterial remains, led to accumulation of biogenic H2S in the pore water of the sediments. This biogenic H2S was mainly incorporated into sedimentary organic matter and diagenetic pyrite. Higher bacterial activity at the ore site also is indicated by specific concentration ratios of hydrocarbons, which are roughly correlated with total Pb plus Zn contents. This correlation is consistent with mixing of hydrothermal metal-rich, fluids and local bacteriogenic sulfide sulfur. The new geochemical data provide supporting evidence that Topla is a low-temperature Mississippi Valley-type deposit formed in an anoxic supratidal saline to hypersaline environment. A laminated cyanobacterial mat, with abundant sulfate-reducing bacteria was the main site of sulfate reduction.

Accreted fragments of the Late Cretaceous Caribbean-Colombian Plateau in Ecuador

The eastern part of the Western Cordillera of Ecuador includes fragments of an Early Cretaceous ( approximate to 123 Ma) oceanic plateau accreted around 85-80 Ma (San Juan unit). West of this unit and in fault contact with it, another oceanic plateau sequence (Guaranda unit) is marked by the occurrence of picrites, ankaramites, basalts, dolerites and shallow level gabbros. A comparable unit is also exposed in northwestern coastal Ecuador (Pedernales unit). Picrites have LREE-depleted patterns, high epsilonNd(i) and very low Pb isotopic ratios, suggesting that they were derived from an extremely depleted source. In contrast, the ankaramites and Mg-rich basalts are LREE-enriched and have radiogenic Pb isotopic compositions similar to the Galapagos HIMU component; their epsilonNd(i) are slightly lower than those of the picrites. Basalts, dolerites and gabbros differ from the picrites and ankaramites by flat rare earth element (REE) patterns and lower epsilonNd; their Pb isotopic compositions are intermediate between those of the picrites and ankaramites. The ankaramites, Mg-rich basalts, and picrites differ from the lavas from the San Juan-Multitud Unit by higher Pb ratios and lower epsilonNd(i). The Ecuadorian and Gorgona 88-86 Ma picrites are geochemically similar. The Ecuadorian ankaramites and Mg-rich basalts share with the 92-86 Ma Mg-rich basalts of the Caribbean-Colombian Oceanic Plateau (CCOP) similar trace element and Nd and Pb isotopic chemistry. This suggests that the Pedernales and Guaranda units belong to the Late Cretaceous CCOR The geochemical diversity of the Guaranda and Pedernales rocks illustrates the heterogeneity of the CCOP plume source and suggests a multi-stage model for the emplacement of these rocks. Stratigraphic and geological relations strongly suggest that the Guaranda unit was accreted in the late Maastrichtian (approximate to 68-65 Ma). (C) 2002 Elsevier Science B.V. All rights reserved.

Entrained macrocryst minerals as a key to the source region of olivine nephelinites: Humberg, Kaiserstuhl, Germany

Olivine nephelinites commonly contain macrocrysts of olivine and clinopyroxene. Some of these macrocrysts might represent fragments of the source region of the host magma transported to the Earth surface. If this hypothesis is correct these fragments can be used to characterize the composition of the source region and to put constraints on the magma generation process. In this study, we investigate the origin of macrocrysts and mineral aggregates from an olivine nephelinite from the Kaiserstuhl, Germany. We focus on clinopyroxenes (Cpx), which can be divided into three groups. Cpx I is relict Cpx from aggregates with deformed olivine that is depleted in Ca and characterized by strong light rare earth element (LREE) fractionation, low Ti/Eu and negative high field strength element (HFSE) anomalies. Its geochemical signature is consistent with formation by carbonatite metasomatism and with equilibration in the Presence of orthopyroxene. Cpx II is Ca-rich Cpx, forming both aggregates with deformed olivine and individual macrocrysts. The LREE, as for Cpx I, are strongly fractionated. Convex REE patterns may be present. The depletion in HFSE is less pronounced. Cpx III is oscillatory zoned Cpx phenociysis showing enrichment in Ca, convex REE patterns and no HFSE anomalies. The transition in the trace element abundances between the Cpx of the three groups is gradual. However, Cpx I and H did not crystallize from the host magma, as demonstrated by the presence of kink-bands and undulose extinction in the associated olivine and by the composition of alkali aluminosilicate glass inclusions in Cpx H. Based on the Cpx relationships, we interpret the studied suite of macrocrysts and mineral aggregates as a mixture of disintegrated fragments of the source region of the host olivine nephelinite. The process of melt generation was multi-stage. A primary carbonatite melt ascending from deeper levels in the mantle, probably from the dolomite-garnet peridotite stability field, reacted with mantle peridotite along the solidus ledge in the system lherzolite-CO2 (< 20-22 kbar) and started to crystallize carbonate minerals. Because of its low solidus temperature, the resulting carbonate-wehrlite assemblage melted incongruently with the formation of additional clinopyroxene. The carbonatite melt evolved during crystallization of carbonate minerals and concomitant incongruent melting of the carbonate-wehrlite, accompanied by the segregation of incipient alkali aluminosilicate melts. As a consequence of fast reaction rates in the presence of a carbonatite melt, this process probably took place under disequilibrium conditions. Further melting of the assemblage wehrlite + alkali aluminosilicate melt led to the generation of the olivine nephelinite magma. It entrained fragments of the wehrlite and brought them to the surface.

Organic and inorganic geochemistry of Ljubija siderite deposits, NW Bosnia and Herzegovina

The Ljubija siderite deposits, hosted by a Carboniferous sedimentary complex within the Inner Dinarides, occur as stratabound replacement-type ore bodies in limestone blocks and as siderite-sulfides veins in shale. Three principal types of ore textures have been recognized including massive dark siderite and ankerite, siderite with zebra texture, and siderite veins. The ore and host rocks have been investigated by a combination of inorganic (major, trace, and rare earth element concentrations), organic (characterization of hydrocarbons including biomarkers), and stable isotope geochemical methods (isotope ratios of carbonates, sulfides, sulfates, kerogen, and individual hydrocarbons). New results indicate a marine origin of the host carbonates and a hydrothermal-metasomatic origin of the Fe mineralization. The differences in ore textures (e.g., massive siderite, zebra siderite) are attributed to physicochemical variations (e.g., changes in acidity, temperature, and/or salinity) of the mineralizing fluids and to the succession and intensity of replacement of host limestone. Vein siderite was formed by precipitation from hydrothermal fluids in the late stage of mineralization. The equilibrium fractionation of stable isotopes reveals higher formation temperatures for zebra siderites (around 245A degrees C) then for siderite vein (around 185A degrees C). Sulfur isotope ratios suggest Permian seawater or Permian evaporites as the main sulfur source. Fluid inclusion composition confirms a contribution of the Permian seawater to the mineralizing fluids and accord with a Permian mineralization age. Organic geochemistry data reflect mixing of hydrocarbons at the ore site and support the hydrothermal-metasomatic origin of the Ljubija iron deposits.

Multiple plume events in the genesis of the peri-Caribbean Cretaceous oceanic plateau province

The oceanic crust fragments exposed in central America, in north-western South America, and in the Caribbean islands have been considered to represent accreted remnants of the Caribbean-Colombian Oceanic Plateau (CCOP). On the basis of trace element and Nd, Sr, and Pb isotopic compositions we infer that cumulate rocks, basalts, and diabases from coastal Ecuador have a different source than the basalts from the Dominican Republic. The latter suite includes the 86 Ma basalts of the Duarte Complex which are light rare earth element (REE) -enriched and display (relative to normal mid-ocean ridge basalts, NMORB) moderate enrichments in large ion lithophile elements, together with high Nb, Ta, Pb, and low Th contents. Moreover, they exhibit a rather restricted range of Nd and Pb isotopic ratios consistent with their derivation from an ocean island-type mantle source, the composition of which includes the HIMU (high U-238/Pb-204) component characteristic of the Galapagos hotspot. In contrast, the 123 Ma Ecuadorian oceanic rocks have flat REE patterns and (relative to NMORB) are depleted in Zr, Hf, Th, and U. Moreover, they show a wide range of Nd and Pb isotopic ratios intermediate between those of ocean island basalts and NMORB. It is unlikely, on geochemical grounds, that the plume source of the Ecuadorian fragments was similar to that of the Galapagos. In addition, because of the NNE motion of the Farallon plate during the Early Cretaceous, the Ecuadorian oceanic plateau fragments could not have been derived from the Galapagos hotspot but were likely formed at a ridge-centered or near-ridge hotspot somewhere in the SE Pacific.

The alkaline intraplate volcanism of the Antalya nappes (Turkey): a Late Triassic remnant of the Neotethys

Late Triassic submarine alkali basalts and hawaiites were collected from two superimposed tectonic slices belonging to the Kara Dere - Sayrun unit of the Middle Antalya nappes, southwestern Turkey. New determinations on conodont faunas allow to date this sequence to the Lower Carnian (Julian). The volcanic rocks show rather homogeneous compositions, with high TiO2 and relatively low MgO and Ni contents which suggest olivine fractionation. Their primitive mantle-normalised multi-elements plots show Nb and Ta enrichments relative to La, Pb negative anomalies and heavy rare earth element and Y depletions typical of intraplate ocean island basalts. These characteristics are consistent with the major and trace element compositions of their primary clinopyroxene phenocrysts, which do not show any feature ascribable to crustal contamination. The studied lavas display a restricted range of epsilon Nd (+4.6 to +5.2) which falls within the range of ocean island basalts. Their initial (Nd-143/Nd-144)i ratios are too low to be explained by a simple mixing line between depleted MORB mantle (DMM) and HIMU components. Their Pb and Nd isotopic compositions plot along a mixing line between HIMU component and an enriched mantle, the composition of which could be the result of the addition of about 5 to 8% of an EM2 component (recycled marine sediments) to DMM. The lack of evidence for any continental crustal component. in their genesis could be consistent with their emplacement in an intra-oceanic setting.

Early diagenesis of bone and tooth apatite in fluvial and marine settings: Constraints from combined oxygen isotope, nitrogen and REE analysis

Fossil bones and teeth of Late Pleistocene terrestrial mammals from Rhine River gravels (RS) and the North Sea (NS), that have been exposed to chemically and isotopically distinct diagenetic fluids (fresh water versus seawater), were investigated to study the effects of early diagenesis on biogenic apatite. Changes in phosphate oxygen isotopic composition (delta O-18(PO4)), nitrogen content (wt.% N) and rare earth element (REE) concentrations were measured along profiles within bones that have not been completely fossilized, and in skeletal tissues (bone, dentine, enamel) with different susceptibilities to diagenetic alteration. Early diagenetic changes of elemental and isotopic compositions of apatite in fossil bone are related to the loss of the stabilizing collagen matrix. The REE concentration is negatively correlated with the nitrogen content, and therefore the amount of collagen provides a sensitive proxy for early diagenetic alteration. REE patterns of RS and NS bones indicate initial fossilization in a fresh water fluid with similar REE compositions. Bones from both settings have nearly collagen-free, REE-, U-, F- and Sr-enriched altered outer rims, while the collagen-bearing bone compacta in the central part often display early diagenetic pyrite void-fillings. However, NS bones exposed to Holocene seawater have outer rim delta O-18(PO4) values that are 1.1 to 2.6 parts per thousand higher compared to the central part of the same bones (delta O-18(PO4) = 18.2 +/- 0.9 parts per thousand, n = 19). Surprisingly, even the collagen-rich bone compacta with low REE contents and apatite crystallinity seems altered, as NS tooth enamel (delta O-18(PO4) =15.0 +/- 0.3 parts per thousand, n=4) has about 3%. lower delta O-18(PO4) values, values that are also similar to those of enamel from RS teeth. Therefore, REE concentration, N content and apatite crystallinity are in this case only poor proxies for the alteration of delta O-18(PO4) values. Seawater exposure of a few years up to 8 kyr can change the delta O-18(PO4) values of the bone apatite by > 3 parts per thousand. Therefore, bones fossilized in marine settings must be treated with caution for palaeoclimatic reconstructions. However, enamel seems to preserve pristine delta O-18(PO4) values on this time scale. Using species-specific calibrations for modern mammals, a mean delta O-18(H2O) value can be reconstructed for Late Pleistocene mammalian drinking water of around -9.2 +/- 0.5 parts per thousand, which is similar to that of Late Pleistocene groundwater from central Europe. (c) 2008 Elsevier B.V. All rights reserved.

An evaluation of the inorganic and organic geochemistry of the San Vicente Mississippi Valley-type zinc-lead district, central Peru: Implications for ore fluid composition, mixing processes, and sulfate reduction

Mississippi Tialley-type zinc-lead deposits and ore occurrences in the San Vicente belt are hosted in dolostones of the eastern Upper Triassic to Lower Jurassic Pucara basin, central Peru. Combined inorganic and organic geochemical data from 22 sites, including the main San Vicente deposit, minor ore occurrences, and barren localities, provide better understanding of fluid pathways and composition, ore precipitation mechanisms, Eh-pH changes during mineralization, and relationships between organic matter and ore formation. Ore-stage dark replacement dolomite and white sparry dolomite are Fe and rare earth element (REE) depleted, and Mn enriched, compared to the host dolomite. In the main deposit, they display significant negative Ce and probably Eu anomalies. Mixing of an incoming hot, slightly oxidizing, acidic brine (H2CO3 being the dominant dissolved carbon species), probably poor in REE and Fe, with local intraformational, alkaline, reducing waters explains the overall carbon and oxygen isotope variation and the distributions of REE and other trace elements in the different hydrothermal carbonate generations. The incoming ore fluid flowed through major aquifers, probably basal basin detrital units, with limited interaction with the carbonate host rocks. The hydrothermal carbonates show a strong regional chemical homogeneity, indicating access of the ore fluids by interconnected channelways near the ore occurrences. Negative Ce anomalies in the main deposit, that are absent at the district scale, indicate local ore-fluid chemical differences. Oxidation of both migrated and indigenous hydrocarbons by the incoming fluid provided the local reducing conditions necessary for sulfate reduction to H2S, pyrobitumen precipitation, and reduction of Eu3+ to Eu2+. Fe-Mn covariations, combined with the REE contents of the hydrothermal carbonates, are consistent with the mineralizing system shifting from reducing/rock-dominated to oxidizing/fluid-dominated conditions following ore deposition. Sulfate and sulfide sulfur isotopes support sulfide origin from evaporite-derived sulfate by thermochemical organic reduction; further evidence includes the presence of C-13-depleted calcite cements (similar to-12 parts per thousand delta(13)C) as sulfate pseudomorphs, elemental sulfur, altered organic matter in the host dolomite, and isotopically heavier, late, solid bitumen. Significant alteration of the indigenous and extrinsic hydrocarbons, with absent bacterial membrane biomarkers (hopanes) is observed. The light delta(34)S of sulfides from small mines and occurrences compared to the main deposit reflect a local contribution of isotopically light sulfur, evidence of local differences in the ore-fluid chemistry.

The Mont Collon mafic complex (Austroalpine Dent Blanche nappe) : permian evolution of the Western European mantle

Résumé: Le complexe du Mont Collon (nappe de la Dent Blanche, Austroalpin) est l'un des exemples les mieux préservés du magmatisme mafique permien des Alpes occidentales. Il est composé d'affleurements discontinus et d'une stratification magmatique en son centre (Dents de Bertol) et est composé à 95% de roches mafiques cumulatives (gabbros à olivine et/ou cpx, anorthositiques, troctolites, wehrlites et wehrlites à plagioclase) et localement de quelques gabbros pegmatitiques. Ces faciès sont recoupés par de nombreux filons acides (aphtes, pegmatites quartziques, microgranodiorites et filons anorthositiques) et mafiques tardifs (dikes mélanocrates riches en Fe et Ti). Les calculs thermométriques (équilibre olivine-augite) montrent des températures de 1070-1120 ± 6°C, tandis que le thermomètre amphibole-plagioclase indique une température de 740 ± 40°C à 0.5 GPa pour les amphiboles magmatiques tardives. La geobarométrie sur pyroxène donne des pressions moyennes de 0.3-0.6 GPa, indiquant un emplacement dans la croûte moyenne. De plus, les températures obtenues sur des amphiboles coronitiques indiquent des températures de l'ordre de 700 ± 40°C confirmant que les réactions coronitiques apparaissent dans des conditions subsolidus. Les âges concordants U/Pb sur zircons de 284.2 ± 0.6 et 282.9 ± 0.6 Ma obtenus sur un gabbro pegmatitique et une pegmatitique quartzique, sont interprétés comme des âges de cristallisation. Les datations 40Ar/39Ar sur amphiboles des filons mélanocrates donnent un âge plateau de 260.2 ± 0.7 Ma, qui est probablement très proche de l'âge de cristallisation. Ainsi, cet age 40Ar/39Ar indique un second évènement magmatique au sein du complexe. Les compositions des roches totales en éléments majeurs et traces montrent peu de variations, ainsi que le Mg# (75-80). Les éléments traces enregistrent le caractère cumulatif des roches (anomalie positive en Eu) et révèlent des anomalies négatives systématiques en Nb, Ta, Zr, Hf et Ti dans les faciès basiques. Le manque de corrélation entre éléments majeurs et traces est caractéristique d'un processus de cristallisation in situ impliquant une quantité variable de liquide interstitiel (L) entre les phases cumulus. Les distributions des éléments traces dans les minéraux sont homogènes, indiquant une rééquilibration .subsolidus entre cristaux et liquide interstitiel. Un modèle quantitatif basé sur les équations de cristallisation in situ de Langmuir reproduisent correctement les concentrations en terres rares légères des minéraux cumulatifs montrant la présence de 0 à 35% de liquide interstitiel L pour des degrés de différenciation F de 0 à 45%, par rapport au faciès les moins évolués du complexe. En outre, les valeurs de L sont bien corrélées avec les proportions modales d'amphibole interstitielle et les concentrations en éléments incompatibles des roches (Zr, Nb). Le liquide parental calculé des cumulats du Mont Collon est caractérisé par un enrichissement relatif en terres rares légères et Th, un appauvrissement en terres rares lourdes typique d'une affinité transitionnelle (T-MORB) et une forte anomalie négative en Nb-Ta. Les roches cumulatives montrent des compositions isotopiques en Nd-Sr proches de la terre globale silicatée (BSE), soit 0.6<εNdi<+3.2, 0.7045<87Sr/86Sri<0.7056. Les rapports initiaux en Pb indiquent une source dans le manteau enrichi subcontinental lithosphérique, préalablement contaminé par des sédiments océaniques. Les dikes mélanocrates Fe-Ti sont représentatifs de liquides et ont des spectres de terres rares enrichis, une anomalie positive en Nb-Ta et des εNdi de +7, des 87Sr/86Sri de 0.703 et des rapports initiaux en Pb, similaires à ceux des basaltes d'île océanique, indiquant une source asthénosphérique modérément appauvrie. Ainsi, la fusion partielle du manteau lithosphérique subcontinental est induite par l'amincissement post-orogénique et la remontée de l'asthénosphère. Les filons mélanocrates proviennent, après délamination du manteau lithosphérique, de la fusion de l'asthénosphère. Abstract The early Permian Mont Collon mafic complex (Dent Blanche nappe, Austroalpine nappe system) is one of the best preserved examples of the Permian mafic magmatism in the Western Alps. It is composed of discontinuous exposures and a well-preserved magmatic layering (the Dents de Bertol cliff) crops out in the center part of the complex. It mainly consists of cumulative mafic rocks, which represent 95 vol-% of the mafic complex (ol- and cpx-bearing gabbros and rare anorthositic layers, troctolites, wehrlites and plagioclase-wehrlites) and locally pegmatitic gabbros. All these facies are crosscut by widespread acidic (aplites, quartz-rich pegmatites, microgranodiorites) and late mafic Fe-Ti melanocratic dikes. Olivine-augite thermometric calculations yield a range of 1070-1120 ± 6°C, while amphibole-plagioclase thermometer yields a temperature of 740 ± 40°C at 0.5 GPa. Pyroxene geobarometry points to a pressure of 0.3-0.6 GPa, indicating a middle crustal level of emplacement. Moreover, temperature calculations on the Mont Conon coronitic amphiboles indicate temperatures of 700 ± 40°C, close to those calculated for magmatic amphiboles. These temperatures confirm that coronitic reactions occurred at subsolidus conditions. ID-TIMS U/Pb zircon ages of 284.2 ± 0.6 and 282.9 ± 0.6 Ma obtained on a pegmatitic gabbro and a quartz-pegmatitic dike, respectively, were interpreted as the crystallization ages of these rocks. 40Ar/39Ar dating on amphiboles from Fe-Ti melanocratic dikes yields a plateau age of 260.2 ± 0.7 Ma, which is probably very close to the crystallization age. Consequently, this 40Ar/P39Ar age indicates a second magmatic event. Whole-rock major- and trace-element compositions show little variation across the whole intrusion and Mg-number stays within a narrow range (75-80). Trace-element concentrations record the cumulative nature of the rocks (e.g. positive Eu anomaly) and reveal systematic Nb, Ta, Zr, Hf and Ti negative anomalies for all basic facies. The lack of correlation between major and trace elements is characteristic of an in situ crystallization process involving variable amounts of interstitial liquid (L) trapped between the cumulus mineral phases. LA-ICPMS measurements show that trace-element distributions in minerals are homogeneous, pointing to subsolidus re-equilibration between crystals and interstitial melts. A quantitative modeling based on Langmuir's in situ crystallization equation successfully reproduced the Rare Earth Element (REE) concentrations in cumulitic minerals. The calculated amounts of interstitial liquid L vary between 0 and 35% for degrees of differentiation F of 0 to 45%, relative to the least evolved facies of the intrusion. Furthermore, L values are well correlated with the modal proportions of interstitial amphibole and whole-rock incompatible trace-element concentrations (e.g. Zr, Nb) of the tested samples. The calculated parental melt of the Mont Collon cumulates is characterized by a relative enrichment in Light REE and Th, a depletion in Heavy REE, typical of a transitional affinity (T-MORB), and strong negative Nb-Ta anomaly. Cumulative rocks display Nd-Sr isotopic compositions close to the BSE (-0.6 < εNdi < +3.2, 0.7045 < 87Sr/86Sri < 0.7056). Initial Pb ratios point to an origin from the melting of an enriched subcontinental lithospheric mantle source, previously contaminated at the source by oceanic sediments. The contrasted alkaline Fe-Ti melanocratic dikes are representative of liquids. They display enriched fractionated REE patterns, a positive Nb-Ta anomaly and εNdi of +7, 87Sr/86Sri of 0.703 and initial Pb ratios, all reminiscent of Ocean Island Basalt-type rocks, pointing to a moderately