Experimental determination of rare earth element partitioning between hydrous silicate melt,amphibole and garnet peridotite minerals at upper mantle pressures and temperatures

Partition coefficients of Ce, Sm and Tm involving garnet peridotite minerals, amphibole and hydrous silicate melt have been determined experimentally in the temperature and pressure ranges 950–1075°C and 10–25 kbar.Only several parts per million to several tens of parts per million of rare earth element (REE) can dissolve in the minerals before the crystal-liquid partition coefficients begin to vary as a function of REE content. The concentration ranges of constant partition coefficient increase with increasing temperature and are also positively correlated with the magnitude of the crystal-liquid partition coefficients. The upper concentration limits of constant partition coefficient and the value of the crystal-liquid partition coefficient for REE decrease in the order garnet > clinopyroxene > amphibole > orthopyroxene > olivine.Partition coefficients may vary by at least an order of magnitude as a function of bulk composition of the liquid phase (e.g. changing from basaltic to andesitic). The approximate ranges of the values of the partition coefficients as a function of bulk liquid composition are as follows:

$\text{Ce}\text{Sm}\text{Tm}\text{K}{}^{\mathrm{<mtext>ga-liq</mtext>}}\text{0.01–0.1}\text{0.3–3.4}\text{1–10}\text{K}{}^{\mathrm{<mtext>cpx-liq</mtext>}}\text{0.05–0.4}\text{0.09–0.7}\text{0.04–0.4}\text{K}{}^{\mathrm{<mtext>amph-liq</mtext>}}\text{0.04–0.4}\text{0.08–0.8}\text{0.07–0.7}\text{K}{}^{\mathrm{<mtext>opx-liq</mtext>}}\text{0.04–0.1}\text{0.05–0.1}\text{0.08–0.1}\text{K}{}^{\mathrm{<mtext>ol-liq</mtext>}}\text{0.01–0.02}\text{0.01–0.02}\text{0.01–0.02}$

where the values increase with increasing acidity of the melt.     

Flow behavior and microstructures of hydrous olivine aggregates at upper mantle pressures and temperatures

Deformation experiments on olivine aggregates were performed under hydrous conditions using a deformation-DIA apparatus combined with synchrotron in situ X-ray observations at pressures of 1.5–9.8 GPa, temperatures of 1223–1800 K, and strain rates ranging from 0.8 × 10^?5 to 7.5 × 10^?5 s^?1. The pressure and strain rate dependencies of the plasticity of hydrous olivine may be described by an activation volume of 17 ± 6 cm³ mol^?1 and a stress exponent of 3.2 ± 0.6 at temperatures of 1323–1423 K. A comparison between previous data sets and our results at a normalized temperature and a strain rate showed that the creep strength of hydrous olivine deformed at 1323–1423 K is much weaker than that for the dislocation creep of water-saturated olivine and is similar to that for diffusional creep and dislocation-accommodated grain boundary sliding, while dislocation microstructures showing the [001] slip or the [001](100) slip system were developed. At temperatures of 1633–1800 K, a much stronger pressure effect on creep strength was observed for olivine with an activation volume of 27 ± 7 cm³ mol^?1 assuming a stress exponent of 3.5, water fugacity exponent of 1.2, and activation energy of 520 kJ mol^?1 (i.e., power-law dislocation creep of hydrous olivine). Because of the weak pressure dependence of the rheology of hydrous olivine at lower temperatures, water weakening of olivine could be effective in the deeper and colder part of Earth’s upper mantle.     

Solubility of CO2 in olivine melilitite at high pressures and role of CO2 in the earth's upper mantle

The positions of the liquidi and the near-liquidus phases of olivine-melilitite+CO₂ have been determined under MH-buffered and furnace-buffered conditions up to 40 kb. It is found that CO₂ alone lowers the liquidus compared to dry conditions, yet its influence is minor compared to H₂O. The major role of CO₂ is to favour the growth of orthopyroxene and garnet over that of olivine at least at high pressures. CO₂-contents of glasses from experiments just above the liquidus (MH-buffered) were determined as 5.1 % at 10kb; 7.5 % at 20kb, 9.3 % at 30kb and 10–11 % (estimated) at 40 kb. Experiments on (pyrolite –40 % olivine)+H₂O+CO₂ show that CO₂ occurs under mantle conditions as carbonate under subsolidus conditions and dissolved in a melt above the solidus. At 30kb, the solidus lies between 1,000 ° C and 1,050 ° C for vapour-saturated conditions, at and at .     

Compositions of aqueous fluids in equilibrium with pyroxenes and olivines at mantle pressures and temperatures

Solubility experiments were performed at 30 kbars in the system Mg₂SiO₄-SiO₂-H₂O, and at 20 and 30 kbars on omphacitic pyroxene-water mixtures. They confirm that the solubility of the forsterite component in aqueous fluids remains rather low (up to 5 wt.%), whereas the solubility of the SiO₂ component from solids of appropriate SiO₂-rich compositions in the system Mg₂SiO₄-SiO₂-H₂O increases with temperature up to some 75% at 1,100° C. At this temperature a simplified harzburgite consisting of forsterite and enstatite coexists with a fluid containing about 35% (MgO+SiO₂). Hydrous fluids coexisting with omphacitic clinopyroxenes leach sodium silicate component from the solid leaving less jadeitic pyroxenes behind. Most interestingly, the amount of sodium leached at constant temperature increases with decreasing pressure.Comparison of the results with previous solubility studies in the system K₂O-MgO-Al₂O₃-SiO₂-H₂O indicates that hydrous fluids in the mantle must be alkaline rather than silicanormative. Alkali metasomatism caused by such fluids would lead to potassium enrichment in deeper portions of the upper mantle and to sodium enrichment at shallower levels, where amphiboles become stable. This K/Na fractionation in the upper mantle may explain the generation of K-rich or of Na-rich magmas through partial melting at different depths.     

CO2 solubility and solubility mechanisms in silicate melts at high pressures

CO₂ solubility has a slight negative temperature dependence in olivine melilitite at 30 kb with 9% CO₂ dissolved at 1,450 °C, 8.5% at 1,550 °C and 8.3% at 1,650° C. CO₂ is dissolved as the carbonate molecule (CO ₃ ^2– ) only. Feldspar melts (albite-anorthite) dissolve much less CO₂ at 30 kb (around 2%) with a slight increase with increasing anorthite content. A CO₂ absorption peak in infrared spectra of albite-rich glasses diappears in favour of the CO ₃ ^2– peak with increasing anorthite content. It is inferred that CO₂ was present as CO ₃ ^2– in albite-rich melts also, but reverts to CO₂ during quenching because of bonding differences related to Ca²⁺ and Na⁺ in the melts.     

Water in the structure of minerals from mantle peridotites as controlled bythermal and redox conditions in the upper mantle

Hydrous species and the amount of water (OH^? ions and crystal hydrate H₂O) in structures of nominally anhydrous rock-forming minerals (olivine, ortho- and clinopyroxenes) were studied with Fourier spectroscopy in peridotite nodules (19 samples) from Cenozoic alkali basalts of the Baikal-Mongolia region (Dariganga Plateau, Taryat Depression, and Vitim Plateau). Single-crystal samples oriented relative to the crystallographic axes of minerals were examined with an FTIR spectrometer equipped with an IR microscope at the points of platelets free from fluid inclusions. FTIR spectra were measured in regions of stretching vibrations of OH^? and H₂O (3800–3000 cm^?1) and deformation vibrations of H₂O (1850–1450 cm^?1). The water content in mineral structures was determined from integral intensities. To estimate the conditions of entrapment and loss of structural water in minerals, their chemical composition, including Fe²⁺ and Fe³⁺ contents, was determined with an electron microprobe analysis and Mössbauer spectroscopy. The bulk chemical composition of some nodules was determined with XRF and ICP MS. The total water content (OH^? + H₂O) varies from 150 to 1140 ppm in olivines, from 45 to 870 ppm in clinopyroxenes, and from 40 to 1100 ppm in orthopyroxenes. Both water species in the mineral structures are retained down to a depth of 150–160 km in wide temperature and pressure ranges (1100–1500 °C, 32–47 kbar) at the oxygen fugacity of ?1.4 to ?0.1 log units relative to that of the quartz-fayalite-magnetite buffer.     

Solubility of platinum and palladium in silicate melts under high water pressure as a function of redox conditions

The solubility of platinum and palladium in a silicate melt of the composition Di ₅₅ An ₃₅ Ab ₁₀ was determined at 1200°C and 2 kbar pressure in the presence of H₂O-H₂ fluid at an oxygen fugacity ranging from the HM to WI buffer equilibria. The influence of sulfur on the solubility of platinum in fluid-bearing silicate melt was investigated at a sulfur fugacity controlled by the Pt-PtS equilibrium at 1200°C and a pressure defined in such a way that the \(f_{H_2 O} \) and \(f_{O_2 } \) values were identical to those of the experiments without sulfur. The experiments were conducted in a high pressure gas vessel with controlled hydrogen content in the fluid. Oxygen fugacity values above the NNO buffer were controlled by solid-phase buffer mixtures using the two-capsule technique. Under more reducing conditions, the contents of H₂O and H₂ were directly controlled by the argon to hydrogen ratio in a special chamber. The hydrogen fugacity varied from 5.2 × 10^?2 bar (HM buffer) to 1230 bar (\(X_{H_2 } \) = 0.5). Pt and Pd contents were measured in quenched glass samples by neutron activation analysis. The results of these investigations showed that the solubility of Pt and Pd increases significantly in the presence of water compared with experiments in dry systems. The content of Pd within the whole range of redox conditions and that of Pt at an oxygen fugacity between the HM to MW buffer reactions are weakly dependent on \(f_{O_2 } \) and controlled mainly by water fugacity. This suggests that, in addition to oxide Pt and Pd species soluble at the ppb level in haplobasaltic melts, much more soluble (ppm level) hydroxide complexes of these metals are formed under fluid-excess conditions. Despite a decrease in water fugacity under reducing conditions, Pt solubility increases sharply near the MW buffer. It was shown by electron paramagnetic resonance spectrometry that, in contrast to dry melts, fluid-saturated silicate melts do not contain a pure metal phase (micronuggets). Therefore, the increase in Pt solubility under reducing conditions can be explained by the formation of Pt hydride complexes or Pt-fluid-silicate clusters. At a sulfur fugacity controlled by the Pt-PtS equilibrium, the solubility of Pt in iron-free silicate melts as a function of redox conditions is almost identical to that obtained in the experiments without sulfur at the same water and oxygen fugacity values. These observations also support Pt dissolution in iron-free silicate melts as hydroxide species.     

Stability conditions of polycyclic aromatic hydrocarbons at high pressures and temperatures

The first results of study of stability of diverse polycyclic aromatic hydrocarbons at around 7 GPa and 773–1073 K are reported. Experiments were carried out in hydraulic multi-anvil presses. The run products after quenching were analyzed using a method of matrix-assisted laser desorption-ionization (MALDI). The formation of polymers of starting matters was determined at 7 GPa and 773–883 K. The polymers are characterized by atomic masses up to 5000 Da, that are multiple by masses of starting matters. At higher temperatures (873–1073 K), the selected PAHs and their polymers become unstable. The decomposition temperature of PAHs and their polymers exclude their stability under Earth’s mantle conditions. The studies could be of great significance for the low-temperature near-surface geodynamics of small and large planetary bodies, which supposedly contain hydrocarbon compounds.     

Vanadium partitioning between orthopyroxene,spinel and silicate melt and the redox states of mantle source regions for primary magmas

The partitioning of V between orthopyroxene-liquid and spinel-liquid has been investigated in synthetic and natural mafic and ultramafic compositions as a function of temperature and oxygen fugacity (fO₂) at 100 kPa and in one experiment at higher pressure. The purpose of the experiments was to understand redox relationships for V in silicate melts with a view to deriving an empirical oxygen barometer for geochemically altered mafic and ultramafic magmas in the geologic record. Partitioning data for both orthopyroxene-liquid and spinel-liquid show profound changes at an fO₂ approximately 3 orders of magnitude below the nickel-nickel oxide (NNO) buffer, suggesting changes in the dominant valence state of V in silicate liquids from V³⁺ to V⁴⁺, near this fO₂.The results of the experiments on orthopyroxene-liquid are combined with published data for olivine-liquid and are applied to suites of mafic and ultramafic magmas that have equilibrated with a harzburgite residue in the mantle. The results show that Archean alumina-undepleted komatiites could have formed at fairly high oxygen fugacities, near ΔNNO ∼ 0, somewhat higher than Cretaceous komatiites and related picrites in the Caribbean region (between ΔNNO ∼ −1 to −3), and plume-related picrites from West Greenland (ΔNNO ∼ − 3). Picrites and boninites from convergent margins record the highest fO₂’s by this method, (ΔNNO = +1 to +2), consistent with other petrological estimates of their redox states. The approach developed in this study can thus provide estimates for the redox states of altered, mantle-derived magmas in the geological record, to which more conventional methods of oxygen barometry cannot be applied.     

Stability and chemical composition of pargasitic amphibole in MORB pyrolite under upper mantle conditions

The stability field of pargasitic amphibole in a model mantle composition (MORB pyrolite) has been experimentally determined for a fixed water content. A solidus for a pargasite-bearing lherzolite has been defined at pressures below the limit of amphibole stability of 30 kbar at T = 925 °C. The maximum temperature for pargasitic amphibole in MORB pyrolite occurs at 1075 °C between P = 18 and 25 kbar. This maximum lies between that determined for a fertile peridotite composition (Hawaiian pyrolite) and a depleted peridotite composition (Tinaquillo lherzolite). A comparison of the new results with those from earlier studies suggests that the stability for a particular bulk H₂O content is mostly controlled by alkali content of the lherzolite composition. The systematic compositional variation of pargasitic amphibole as a function of pressure and temperature can be represented as an increase of the richterite component with increase in both pressure and temperature. For a given pressure the tschermakite component increases with increasing temperature. The compositions of coexisting clinopyroxenes also show a systematic variation with pressure and temperature. The phase relationships in MORB pyrolite combined with the modal abundance of coexisting phases show that the breakdown reactions of pargasitic amphibole occur continuously throughout the subsolidus region studied. The temperature stability limit of pargasitic amphibole coincides with the water-undersaturated solidus (amphibole-dehydration solidus) at pressures below 30 kbar. The experimental results are applicable to pargasitic amphibole-bearing natural peridotites. Cooling and decompression paths and heating events observed in natural peridotites can be interpreted from changes in the composition of pargasitic amphibole. The data are also applicable to a model for peridotite melting and hydration process in the subduction environment. Received: 27 October 1997 / Accepted: 6 November 1998     

The distribution of strontium between coexisting silicate and carbonate liquids at elevated pressures and temperatures

Strontium is characteristically enriched in carbonatites and associated igneous rocks. Experiments between 600 and 800°C at 5 and 10 kb show that Sr fractionates strongly toward both liquid phases of a carbonate liquid-silicate liquid-solid assemblage, with the crystalline phases depleted in Sr. Considering that the alkalic igneous rocks associated with carbonatites are not significantly depleted in Sr compared with the carbonatites, it is concluded that these complexes are formed by a pair of immiscible magmas, rather than the carbonatites being late-stage fractionation products of the alkalic silicate magmas.     

The thermodynamics of substances at very high pressures and temperatures and some mineral reactions in the earth's mantle

The thermodynamic properties of 25 substances (elements, compounds, modifications) are calculated on the basis of an extrapolation of their caloric values and compressibilities into the region of pressures up to 2mbar and temperatures up to 4,000K. The extrapolation methods are described. The ratio of molar volumes is used to predict the thermodynamic properties of the high pressure modifications. It is inferred that water vapour and oxides of Mg, Fe, and Si ought to be stable in the entire mantle. In the lower mantle garnet should be more stable than the perovskite-type phase of MgSiO₃ (in presence of Al₂O₃ or Fe₂O₃). ‘Perovskite’ phase plus MgO are more stable here than forsterite, Mg₂SiO₄. Pyrrhotite, FeS, reveals astonishing stability in the entire mantle and in the outer core as well. Carbon dioxide, CO₂, may exist only in the upper mantle, whereas methane, CH₄, remains stable in the entire mantle.     

On the Chemical Evolution of Upper Mantle of the Early Earth—An Experimental Study on Melting of the Silicate Phase in Jilin Chondrite at High Pressures

Relatively old ages of chondrites(normally around 4.5Ga)suggest that their parent bodies did not experience any mely-fractionation under high temperature and high pressure conditions pertaining to the interior of terrestrial plaets.Therefore,it is reasonable to take chondrites as starting materials in the study of the chemical evolution of the early earth.The sillicate phase in the Jilin chondrite (H5)was chosen for this purpose because it possesses a chemical composition similar to that of the primitive mantle.The melting experiment was carried out at 20-30 k bar and has rsulted in a product which contains1-5% melts in addition to solid cryustal phase.The chemical composition of the melt phases and the partitioning of various elements between the coexisting silicate melts are geochemically similar to those of anatectic rocks on the earth.This can thus serve as the basis for discussing the chemical evolution of the early upper mantle.     

Effects of experimental reheating of natural basaltic ash at different temperatures and redox conditions

A set of experiments have been performed on volcanic materials from Etna, Stromboli and Vesuvius in order to evaluate how the exposure to thermal and redox conditions close to that of active craters affects the texture and composition of juvenile pyroclasts. Selected samples were placed within a quartz tube, in presence of air or under vacuum, and kept at T between 700 and 1,130 °C, for variable time (40 min to 12 h). Results show that reheating reactivates the melt, which, through processes of chemical and thermal diffusion, reaches new equilibrium conditions. In all the experiments performed at T = 700–750 °C, a large number of crystal nuclei and spherulites grows in the groundmass, suggesting conditions of high undercooling. This process creates textural heterogeneities at the scale of few microns but only limited changes of groundmass composition, which remains clustered around that of the natural glasses. Reheating at T = 1,000–1,050 °C promotes massive groundmass crystallization, with a different mineral assemblage as a function of the redox conditions. Morphological modifications of clasts, from softening to sintering as temperature increases, occur under these conditions, accompanied by progressive smoothing of external surfaces, and a reduction in size and abundance of vesicles, until the complete obliteration of the pre-existing vesicularity. The transition from sintering to welding, characteristic of high temperature, is influenced by redox conditions. Experiments at T = 1,100–1,130 °C and under vacuum produce groundmass textures and glass compositions similar to that of the respective starting material. Collapse and welding of the clasts cause significant densification of the whole charge. At the same temperature, but in presence of air, experimental products at least result sintered and show holocrystalline groundmass. In all experiments, sublimates grow on the external surfaces of the clasts or form a lining on the bubble walls. Their shape and composition is a function of temperature and fO₂ and the abundance of sublimates shows a peak at 1,000 °C. The identification of the features recorded by pyroclasts during complex heating–cooling cycles allows reconstructing the complete clasts history before their final emplacement, during weakly explosive volcanic activity. This has a strong implication on the characterization of primary juvenile material and on the interpretation of eruption dynamics.     

Semi-brittle behavior of wet olivine aggregates: the role of aqueous fluid in faulting at upper mantle pressures

The role of aqueous fluid in fracturing in subducting slabs was investigated through a series of deformation experiments on dunite that was undersaturated (i.e., fluid-free) or saturated with water (i.e., aqueous-fluid bearing) at pressures of 1.0–1.8 GPa and temperatures of 670–1250 K, corresponding to the conditions of the shallower regions of the double seismic zone in slabs. In situ X-ray diffraction, radiography, and acoustic emissions (AEs) monitoring demonstrated that semi-brittle flow associated with AEs was dominant and the creep/failure strength of dunite was insensitive to the dissolved water content in olivine. In contrast, aqueous fluid drastically decreased the creep/failure strength of dunite (up to ~?1 GPa of weakening) over a wide range of temperatures in the semi-brittle regime. Weakening of the dunite by the aqueous fluid resulted in the reduction of the number of AE events (i.e., suppression of microcracking) and shortening of time to failure. The AE hypocenters were located at the margin of the deforming sample while the interior of the faulted sample was aseismic (i.e., aseismic semi-brittle flow) under water-saturated conditions. A faulting (slip rate of ~?10^?3 to 10^?4 s^?1) associated with a large drop of stress (Δσ?~?0.5 to 1 GPa) and/or pressure (ΔP?~?0.5 GPa) was dominant in fluid-free dunite, while a slow faulting (slip rate?<?8?×?10^?5 s^?1) without any stress/pressure drop was common in water-saturated dunite. Aseismic semi-brittle flow may mimic silent ductile flow under water-saturated conditions in subducting slabs.     

Self-diffusion of Si and O in diopside-anorthite melt at high pressures

Self-diffusion coefficients for Si and O in Di₅₈An₄₂ liquid were measured from 1 to 4 GPa and temperatures from 1510 to 1764°C. Glass starting powders enriched in ¹⁸O and ²⁸Si were mated to isotopically normal glass powders to form simple diffusion couples, and self-diffusion experiments were conducted in the piston cylinder device (1 and 2 GPa) and in the multianvil apparatus (3.5 and 4 GPa). Profiles of ¹⁸O/¹⁶O and ^29,30Si/²⁸Si were measured using secondary ion mass spectrometry. Self-diffusion coefficients for O (D(O)) are slightly greater than self-diffusion coefficients for Si (D(Si)) and are often the same within error. For example, D(O) = 4.20 ± 0.42 × 10⁻¹¹ m²/s and D(Si) = 3.65 ± 0.37 × 10⁻¹¹ m²/s at 1 GPa and 1662°C. Activation energies for self-diffusion are 215 ± 13 kJ/mol for O and 227 ± 13 kJ/mol for Si. Activation volumes for self-diffusion are −2.1 ± 0.4 cm³/mol and −2.3 ± 0.4 cm³/mol for O and Si, respectively. The similar self-diffusion coefficients for Si and O, similar activation energies, and small, negative activation volumes are consistent with Si and O transport by a cooperative diffusion mechanism, most likely involving the formation and disassociation of a high-coordinated intermediate species. The small absolute magnitudes of the activation volumes imply that Di₅₈An₄₂ liquid is close to a transition from negative to positive activation volume, and Adam-Gibbs theory suggests that this transition is linked to the existence of a critical fraction (∼0.6) of bridging oxygen.     

Solubility and solution mechanism of H2O in alkali silicate melts and glasses at high pressure and temperature

The solubility behavior of H₂O in melts in the system Na₂O-SiO₂-H₂O was determined by locating the univariant phase boundary, melt = melt + vapor in the 0.8-2 GPa and 1000°-1300°C pressure and temperature range, respectively. The NBO/Si-range of the melts (0.25-1) was chosen to cover that of most natural magmatic liquids. The H₂O solubility in melts in the system Na₂O-SiO₂-H₂O (X_H2O) ranges between 18 and 45 mol% (O = 1) with (∂X_H2O/∂P)_T∼14-18 mol% H₂O/GPa. The (∂X_H2O/∂P)_T is negatively correlated with NBO/Si (= Na/Si) of the melt. The (∂X_H2O/∂T)_P is in the −0.03 to +0.05 mol% H₂O/°C range, and is negatively correlated with NBO/Si. The [∂X_H2O/∂(NBO/Si)]_P,T is in the −3 to −8 mol% H₂O/(NBO/Si) range. Melts with NBO/Si similar to basaltic liquids (∼0.6-∼1.0) show (∂X_H2O/∂T)_P<0, whereas more polymerized melts exhibit (∂X_H2O/∂T)_P>0. Complete miscibility between hydrous melt and aqueous fluid occurs in the 0.8-2 GPa pressure range for melts with NBO/Si ≤0.5 at T >1100°C. Miscibility occurs at lower pressure the more polymerized the melt.     

On saturation of magnesian cordierite with alkanes at high temperatures and pressures

 Incorporation of hydrocarbons (CH₄, C₂H₆, C₃H₈, C₄H₁₀) in cordierite channels was experimentally studied at 700 °C and at pressures from 200 to 1000 MPa, (avoiding recrystallization). The maximum concentrations of hydrocarbons determined by gas chromatographic analysis are CH₄=78.3, C₂H₆=134, C₂H₄ + C₂H₆=26, C₃H₈=28, C₄H₁₀=32, C₅H₁₂=23, and C₆H₁₄=7 × 10⁻³ wt%). According to IR spectroscopy data, the channel forms of hydrocarbons differ from the forms on the surface. As a result of interactions with the framework oxygen, normal hydrocarbons are converted to saturated oligomers and their fragments. Small amounts of water molecules of the first and second types (up to 0.3 wt%) are formed in the same way. As pressure grows from 200 to 1000 MPa, the total content of structural hydrocarbons is nearly doubled. Special runs on cordierite saturation in mixtures of hydrocarbons with water showed that low contents of hydrocarbons in natural cordierites correspond to their large concentrations in fluid. Received: 7 May 2001 / Accepted: 17 July 2001     

Rare earth elements in seep carbonates as tracers of variable redox conditions at ancient hydrocarbon seeps

Marine hydrocarbon seeps are dynamic systems, which are typically reflected in complex lithologies of limestones forming at these sites. In order to test if seep limestones with their multiple generations of carbonate phases reflect variable redox conditions, the rare earth element (REE) patterns of limestones from five ancient hydrocarbon-seep localities, Hollard Mound (Middle Devonian), Iberg (Mississippian), Beauvoisin (Oxfordian), Canyon and Satsop River (Oligocene), and Marmorito (Miocene) have been investigated. The total REE contents vary widely (0.3–43.7 p.p.m.). Early microcrystalline phases tend to show higher contents than spatially associated later phases (microspar, sparite, and blocky cement). The shale-normalized REE patterns of the carbonates show both negative and positive Ce anomalies even for individual deposits, suggesting that the redox conditions varied significantly. It is apparent that in addition to anoxic conditions, oxic conditions were common in some ancient seep environments. Intermittent oxygenation is presumed to have resulted from abrupt changes in fluid flow.