Magnetite scavenging and the buoyancy of bubbles in magmas. Part 1: Discovery of a pre-eruptive bubble in Bishop rhyolite

Little is known about the presence, distribution and size of bubbles in rhyolitic magmas prior to eruption. Using X-ray tomography to study pumice from early-erupted Bishop rhyolite, we discovered a large vesicle with abundant magnetite crystals attached to its walls. Attachment of magnetite crystals to bubble walls under pre-eruptive conditions can explain the cluster of magnetite crystals as a result of bubbles rising and collecting magnetite crystals. Alternatively, bubbles may have nucleated on magnetite crystals and then coalesced to form one large bubble with multiple magnetite crystals attached to it. We argue that the clusters of magnetite crystals could not have formed during or after eruptive decompression, and conclude that this vesicle corresponds to a bubble present prior to eruptive decompression. The inferred presence of pre-eruptive bubbles in the Bishop magma confirms the interpretation that the magma was volatile-saturated prior to eruption. The pre-eruptive size of this bubble is estimated based on three independent approaches: (1) the current size of the vesicle, (2) the total cross-sectional area of the magnetite crystals, and (3) the bubble size required for the aggregate to be neutrally buoyant. These approaches suggest a pre-eruptive bubble 300–850 μm in diameter, with a preferred value of 600–750 μm. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Segregating gas from melt: an experimental study of the Ostwald ripening of vapor bubbles in magmas

Diffusive coarsening (Ostwald ripening) of H₂O and H₂O-CO₂ bubbles in rhyolite and basaltic andesite melts was studied with elevated temperature–pressure experiments to investigate the rates and time spans over which vapor bubbles may enlarge and attain sufficient buoyancy to segregate in magmatic systems. Bubble growth and segregation are also considered in terms of classical steady-state and transient (non-steady-state) ripening theory. Experimental results are consistent with diffusive coarsening as the dominant mechanism of bubble growth. Ripening is faster in experiments saturated with pure H₂O than in those with a CO₂-rich mixed vapor probably due to faster diffusion of H₂O than CO₂ through the melt. None of the experimental series followed the time^1/3 increase in mean bubble radius and time⁻¹ decrease in bubble number density predicted by classical steady-state ripening theory. Instead, products are interpreted as resulting from transient regime ripening. Application of transient regime theory suggests that bubbly magmas may require from days to 100 years to reach steady-state ripening conditions. Experimental results, as well as theory for steady-state ripening of bubbles that are immobile or undergoing buoyant ascent, indicate that diffusive coarsening efficiently eliminates micron-sized bubbles and would produce mm-sized bubbles in 10²–10⁴ years in crustal magma bodies. Once bubbles attain mm-sizes, their calculated ascent rates are sufficient that they could transit multiple kilometers over hundreds to thousands of years through mafic and silicic melt, respectively. These results show that diffusive coarsening can facilitate transfer of volatiles through, and from, magmatic systems by creating bubbles sufficiently large for rapid ascent.     

Water and magmas: application of the Gibbs-Duhem equation

Burnham (1975a, b) has shown that in several alumino-silicate systems Henry's law constant is independent of silicate melt composition up to X^melt_H2O = 0.5. He has used this fact to conclude that such silicate melts behave ideally over a wide range of compositions based on the application of the Gibbs-Duhem relation. Unless Henry's law is valid up to X^melt_H2O = 1.0, the application of the Gibbs—Duhem relation to three component systems only shows that if one component obeys Henry's law, the other two components follow the two component Gibbs-Duhem equation. There is no thermodynamic requirement of ideality.     

Silicate liquid immiscibility in magmas and in the system K2O-FeO-AI2O3-SiO2: an example of serendipity

The concept of silicate liquid immiscibility was invoked early in the history of petrology to explain certain pairs of compositionally divergent rocks, but. as a result of papers by Greig (Am. J. Sci.13, 1–44, 133–154) and Bowen (The Evolution of the Igneous Rocks), it fell into disfavor for many years. The discovery of immiscibility in geologically reasonable temperature ranges and compositions in experimental work on the system K₂O-FeO-Al₂O₃-SiO₂, and of evidence for immiscibility in a variety of lunar and terrestrial rocks, has reinstated the process.Phase equilibria in the high-silica corner of the tetrahedron representing the system K₂O- FeO-Al₂O₃-SiO₂ are presented, in the form of constant FeO sections through the tetrahedron, at 10% increments. Those sections, showing the tentative relationships of the primary phase volumes, are based on 5631 quenching runs on 519 compositions, made in metallic iron containers in pure nitrogen. Thirteen crystalline compounds are involved, of which at least six show two or more crystal modifica-tions. Two separate phase volumes, in each of which two immiscible liquids, one iron-rich and the other iron-poor, are present at the liquidus. One of these volumes is entirely within the quaternary system, astride the 1:1 K₂O:Al₂O₃ plane. No quaternary compounds as such have been found, but evidence does point toward at least partial quaternary solid solution, with rapidly lowering liquidus temperatures, from K₂O·Al₂O₃· 2SiO₂ (‘potash nepheline’, kalsilite. kaliophilite) to the isostructural compound K₂O·FeO·3SiO₂, and from K₂O·Al₂O₃·4SiO₂ (leucite) to the isostructural compound K₂O·FeO·5SiO₂, Both of these series apparently involve substitution, in tetrahedral coordination. of a ferrous iron and a silicon ion for two aluminum ions. Some of the ‘impurities’ found in analyses of the natural phases may reflect these substitutions.As a result of the geometry of the immiscibility volume located entirely within the quaternary system, compositions near it show a number of phase changes and large amounts of crystallization with small temperature changes, generally in the range 1100–1150 C. Similar low-temperature, high-alkali immiscibility was discovered in a few exploratory runs in the equivalent systems with Rb or Cs substituting for K. But not in those with Li or Na.A review of the compositions and general behavior of systems involving immiscibility, both stable and metastable, and of the evidence for natural immiscibility. indicates that it may be a much more common feature than generally thought. Several examples of natural immiscibility are detailed; most yield a felsic. alkali-aluminosilicate melt and a mafic melt. from a wide variety of generally basaltic parental magmas, both under- and over saturated. Unfortunately, the best line of evidence for immiscibility in terrestrial rocks, a sharply defined meniscus between two compositionally disparate glasses, is by its very nature self-destructing, since it is effectively eliminated by either crystallization or gravitative separation and coalescence into separate magmas. Verification of operation of the exosolutionor ‘splitting’ process on a large scale will probably require careful study of isotopic and trace element partitioning in both laboratory and field.     

Nickel content of basaltic magmas: identification of primary magmas and a measure of the degree of olivine fractionation

Available NiO analyses of olivine in peridotites of probable mantle origin are consistent in giving values around 0.40 weight per cent. Assuming that basaltic magma forming from the mantle was in equilibrium with such peridotitic olivine, the NiO content of primary basaltic magmas is estimated to be about 0.030–0.050 weight per cent. The fractionation behaviour of nickel in basaltic magma due to the crystallization of olivine has been calculated using constant NiMg and FeMg exchange partition coefficients between olivine and magma. It is shown that the NiO content of both magma and olivine decreases by 50 per cent after fractional crystallization of 6–12 per cent of olivine. The nickel distribution in some basaltic rocks and olivines is examined in the light of these results, and it is suggested that basaltic magmas, such as some of the ocean-floor basalt and the Hawaiian tholeiite and alkali basalts, represent primary magmas from mantle peridotites.     

磁铁矿单矿物研究现状、存在问题和研究方向

磁铁矿在自然界分布广泛,是重要的成岩矿物和矿石矿物。磁铁矿的物理化学特征一直是研究的热点,尤其是近年来随着单矿物激光ICP-MS测试技术的成熟,利用磁铁矿的微量元素特征进行矿床成因机制研究已成为矿床学研究的前沿,已取得一系列成果。本文对这些成果进行了综述和介绍,同时也指出在开展这一研究中面临的主要问题,如分析方法不一致,缺乏重要的铁矿床类型实例,物理结构研究薄弱和勘查应用研究亟待加强等,并认为这些问题的解决应是今后开展磁铁矿研究的重要方向。     

Crystallization conditions of leucite-bearing magmas and their implications on the magmatological evolution of ultrapotassic magmas: the Vico Volcano, Central Italy

Summary Mineral compositions in leucite-bearing and leucite-free rocks from Vico volcano are reported. FeO/MgO partitioning (Kd_ol/liq) between olivine and latite (0.14–0.22), and between olivine and trachyte (0.06–0.10) indicates a lack of equilibrium between mineral and host rock. This suggests that mingling and/or mixing between magmas was a leading process during magmatic differentiation. In addition, a phono-tephrite olivine population with high (0.84) and equilibrium (0.23–0.29) Kd_ol/liq values has been produced by the interaction of differently evolved magmas. Zoning in clinopyroxene and plagioclase from these rocks recorded the same processes. In addition, resorbed quartz xenocrysts with coronas of clinopyroxene microlites indicate that digestion of crustal rocks occurred during the residence of magma in a shallow level reservoir. Increasing Fe coupled with decreasing Ca in diopside crystals from some phonolites, together with the petrographic and trace element data, indicate that polybaric fractional crystallisation also may be involved in the genesis of magmas of the second period of Vico activity. Leucite-free trachybasalts erupted in a late stage contain highly forsteritic olivine phenocrysts (forsterite 84–88 mol.%) in-equilibrium (Kd_ol/liq = 0.24–0.35) with the host rock, which indicate that they did not suffer chemical modification at low pressure. Received November 28, 2000; revised version accepted September 27, 2001     

Nd and Sr isotopes in the Aleutians: multicomponent parenthood of island-arc magmas

Young volcanic rocks from different sections of the Aleutian Islands-Alaska Peninsula Arc have been measured for ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd and some trace elements. We found the ¹⁴³Nd/¹⁴⁴Nd to be highly restricted in range ( _Nd=6 to 7) and low as compared to midocean ridge ba-salts (MORB). This indicates that the source of the Aleutian Arc magmas is different from MORB and remarkably isotopically homogeneous with respect to Nd. The range reported here for arc rocks is substantially smaller than found by other workers. However, the Sr isotope ratios vary considerably ( _Sr=–24 to –14). Those samples from small volcanic centers north of the main arc (second arc) are characterized by low _Sr. Our data in combination with previous studies suggest that there are slight geochemical differences between discrete sections of the arc. The general uniformity of Nd isotope ratios are thought to be the surface expression of an efficient mixing or homogenization process beneath the arc plate, but which still causes a wide dispersion in Sr isotopic composition.To relate the arc rocks to the broader tectonic setting and to identify possible sources of arc magmas, measurements were done on volcanic and sedimentary rocks from the North Pacific/Bering Sea area. Alkali basalts from the back-arc islands St. George, Nunivak and St. Lawrence and alkali-rich tholeiites from the fore-arc have _Nd=+4 to +9 and are correlated on the _Sr- _Nddiagram parallel to the mantle array but shifted to lower _Sr. These samples are thought to be isotopically representative of the mantle transported to that region. A tholeiitic basalt from the Kamchatka Basin ocean floor (back-arc), however, yielded typical MORB values ( _Nd=10, _Sr=–24). Composite sediment samples were made from DSDP cores in the Aleutian Abyssal Plain, Gulf of Alaska and the Alka Basin which represent mixtures of continentally and arc-derived materials. These composites have intermediate Nd isotopic ( _Nd= –2 and +2) and high Sr isotopic values ( _Sr=+9 and +37). These data show that possible source materials of the Aleutian Arc volcanics are isotopically different from and much more heterogeneous than the arc rocks themselves.On the basis of this study and of literature data, we developed a set of alternative models for volcanic arc magma generation, based on the restricted range in _Nd and the wider range in _Sr for arc rocks. Different isotopic and trace element characteristics found in different arcs or arc sections are explained by varying mixing proportions or concentrations in source materials. The basic observations require rather strict mixing ratios to obtain constant _Nd. The preferred model is one where the melting of subducted oceanic crust is controlled by the amount of trapped sediment with the melting restricted to the upper part of the altered basaltic layer. Homogenization within the upper part of the oceanic crust is brought about by hydrothermal circulation attending dewatering of the slab during subduction and possibly some oxygen exchange of the magmas on ascent.Division Contribution Number 3849 (411)     

Iron oxide incrustations in wells. Part 2: chemical dissolution and modeling

The formation of Fe oxide and Mn incrustations seriously affects the performance of wells, piezometers and drains. Chemical dissolution can be a valuable tool for their removal. Standardized dissolution experiments were performed to study the efficiency of different chemicals on synthetic Fe oxides. They showed that buffered Na-dithionite and oxalic acid are the most effective agents, followed by ascorbic, malonic and sulfamic acid. Citric acid and especially NaOH proved to be ineffective. As expected, a strong dependency of the dissolution rates on the surface area of the individual Fe oxides was observed, goethite being far less soluble than ferrihydrite. In many cases linear, zeroeth order rate laws were sufficient to model the measured dissolution curves. In other cases more advanced model approaches had to be applied. Sometimes different models were equally well suited to describe a dissolution process.     

Oceanic potassic magmas: An example of the Atlantic Ocean

Statistical study of volcanic rocks from oceanic islands and seamounts in the Atlantic Ocean based on approximately 6000 analyses (data from the authors’ databank) makes it possible to recognize rocks close to the parental melts (approximately 2000 analyses). This set is demonstrated to include a unique group of high-potassium (K₂O/Na₂O > 1) rocks, whose K₂O/Na₂O ratio is several times higher than in the mantle and calls for the explanation of the mechanism that increased the K₂O concentration during the melting of the mantle and for the identification of an additional K₂O source in the mantle and a process responsible for K and Na differentiation. A new model is proposed to account for the genesis of high-potassium melts-fluids, whose ascent brings about extensive mantle metasomatism. The genesis of high-potassium fluid is related to solid-state reactions at deep mantle levels.     

A simple thermodynamic model for estimating the solubility of H2O in magmas

A symmetrical, strictly regular solution model is used to estimate H₂O solubilities in silicate melts. The standard state chemical potential of dissolved H₂O and the adjustable parameter in the activity coefficient are determined by least squares analyses of data on H₂O solubility in silicate melts. The adjustable parameter in the expression for the activity coefficient (In) is a function only of the anhydrous melt composition and eleven values are provided for melts ranging in composition from picrite to rhyolite. At the 95% confidence level, the model should estimate H₂O contents to within 4.8% of the amount present if the amount present is less than 10 wt.%. This compares to the reproducibility of 2.25% of the amount present for experimental determinations. To apply the model to rocks and magmas estimates ofT, P, and the fugacity of H₂O are required.Variation of the H₂O content of the melt changes the activity of other components. Knowledge of this variation removes the requirement that the fugacity of H₂O be estimated. Application of the properties of exact differentials to the Gibbs function for the hydrous melt provides an expression relating the chemical potential of a feldspar component to the H₂O content of the melt. This expression contains a second adjustable parameter which depends on the anhydrous melt composition. Using this second expression, the H₂O content can be estimated ifT, P, and feldspar composition are known. Data are too meagre to evaluate the quantitative success of the second method.     

Carbon dioxide and argon diffusion in silicate melts: Insights into the CO2 speciation in magmas

To investigate the influence of temperature and composition on the diffusivities of dissolved carbon dioxide and argon in silicate melts, diffusion experiments were performed at magmatic pressure and temperature conditions in (a) albite melts with excess Na₂O (0-8.6 wt%) and a constant Si/Al ratio of 3, and (b) albite₇₀quartz₃₀ to jadeite melts with decreasing SiO₂ content and a constant Na/Al ratio of 1. We obtained diffusion coefficients at 500 MPa and 1323-1673 K. In the fully polymerized system Ab₇₀Qz₃₀ - Jd, the change in composition only has a weak effect on bulk CO₂ diffusivity, but Ar diffusivity increases clearly with decreasing SiO₂ content. In the system Ab + Na₂O, bulk CO₂ and Ar diffusivity increase significantly with gradual depolymerisation. The relatively small change in composition on molar basis in the depolymerized system leads to a significantly larger change in diffusivities compared to the fully polymerized Ab₇₀Qz₃₀-Jd join. Within error, activation energies for bulk CO₂ and Ar diffusion in both systems are identical with decreasing silica content (Ab + Na₂O: 159 ± 25 kJ mol⁻¹ for bulk CO₂ and 130 ± 8 kJ mol⁻¹ for Ar; Ab₇₀Qz₃₀-Jd: 163 ± 16 kJ mol⁻¹ for bulk CO₂ and 148 ± 15 kJ mol⁻¹ for Ar) even though this results in depolymerisation in one system and not the other.Although there is a variation in CO₂ speciation with changing composition as observed in quenched glasses, it has previously established that this is not a true representation of the species present in the melt, with the ratio of molecular CO₂ to carbonate decreasing during quenching. Thus, diffusion coefficients for the individual CO₂ species cannot be directly derived by measuring molecular CO₂ and CO₃^2- concentration-distance profiles in the glasses. To obtain diffusivities of individual CO₂ species, we have made two assumptions that (1) inert Ar can be used as a proxy for molecular CO₂ diffusion characteristics as shown by our previous work and (2) the diffusivity of CO₃²⁻ can be calculated assuming it is identical to network forming components (Si⁴⁺ and Al³⁺). This is derived from viscosity data (Eyring eqn.) and suggests that CO₃²⁻ diffusion would be several orders of magnitude slower than molecular CO₂ diffusion.The systematics of measured bulk CO₂ diffusivity rates and comparison with the Ar proxy all suggest that the faster molecular CO₂ species is much more dominant in melts than measurements on resulting quenched glasses would suggest. This study has confirmed an observation of surprisingly consistent bulk CO₂ diffusivity across a range of natural compositions were Ar diffusivity significantly increases. This is consistent with an actual increase in molecular CO₂ mobility (similar to Ar) that is combined with an increase in the proportion of the slower carbonate in the melt.These results demonstrate that the CO₂ diffusion and speciation model provides an insight into the transport processes in the melt and is promising and an alternative tool to in situ speciation measurements at magmatic conditions, which at the moment are technically extremely difficult. We present the first high pressure high temperature in situ MIR spectra of a CO₂ bearing albitic glass/melt suggesting that molecular CO₂ is a stable species at high temperature, which is qualitatively consistent with the modelled CO₂ speciation data.     

Energetics of glasses in the system diopside-anorthite-forsterite

Enthalpies of mixing in glasses in the experimentally accessible region of the system Di-An-Fo are generally less than 4 kJ/mol in magnitude. Enthalpies of mixing of liquids in this and in several other petrologically relevant melts are also small; thus, if magmas of different compositions mix isothermally, the heat released or absorbed can be neglected in any consideration of the thermal evolution of the magmas, unless melting or crystallization takes place. The enthalpy of vitrification of Mg₂SiO₄ (to form a hypothetical glass at 700°C) is estimated to be 61±4 kJ/mol, in contrast to the enthalpy of fusion at 1500°C, 89±12 kJ/mol (Navrotsky et al. 1989). This suggests an average difference in heat capacity ( C _p) between liquid and crystal of 35 J/K. mol, half that estimated by Ghiorso and Carmichael (1980, 1987).     

Ultrabasic magmas and high-degree melting of the mantle

As the degree of melting of mantle peridotite increases, the liquids that are formed become more basic and less viscous, and the spacing between residual crystals increases. The settling velocities of residual crystals in partial melts consequently will increase by several orders of magnitude, from 9.4 × 10^–4 cm/s to 4.3 × 10^–1 cm/s for a 1 cm olivine grain, as the proportion of liquid increases from 15 to 60%.To produce an ultrabasic komatiitic magma from a source with commonly assumed mantle composition requires 50 to 80% melting. Before this degree of melting can be reached, a highly fluid picritic magma produced by 30 to 50% melting will segregate from the source. Ultrabasic magmas probably form by a sequential melting process and are derived from a residuum composed of refractory minerals and trapped liquid left by previous episodes of partial melting and magma extraction. Trace element concentrations in ultrabasic komatiite lavas are consistent with this theory.     

Trace element partitioning between mica- and amphibole-bearing garnet lherzolite and hydrous basanitic melt: 2. Tasmanian Cainozoic basalts and the origins of intraplate basaltic magmas

Oligocene volcanics from Oatlands in Tasmania, Australia, include olivine tholeiites, alkali olivine basalts, nepheline basanites and olivine nephelinites. They have compositional characteristics that are typical of intraplate basalts worldwide. They are generally enriched in incompatible elements relative to the primitive mantle and are strongly enriched in Nb, Ta and light rare earths, but not heavy rare earths. At the same time, they have Sr and Nd isotope compositions that are similar to those in some incompatible-element-depleted mid-ocean ridge basalts (E-type MORB). Experimentally obtained mineral/melt partition coefficients for an Oatlands basanite allow the relative concentrations of incompatible elements in the volcanics to be produced by small degrees of melting (≤1%) of a source similar to the E-type MORB source of Workman and Hart (2005). However, the absolute concentrations that can be achieved in this way are much less than present in the most incompatible-element-enriched basanites and nephelinites at Oatlands. This contradiction can be explained by open-system melting under the influence of a conductive geotherm. This would have involved upwardly migrating near-solidus melts from the asthenosphere cooling along a sub-adiabatic geotherm. Cooling of the melts would have caused them to re-crystallize and accumulate in the overlying mantle, thereby enriching both the new host rocks and any residual melts in incompatible elements. This would also have increased the buoyancy of the host rocks leading to upwelling and further (decompression) melting of incompatible-element-enriched peridotite. We were able to use our partition coefficients to quantitatively model the development of incompatible-element enrichments in the Oatlands magmas by these processes. Our explanation is consistent with the characteristically scattered but widespread distributions and long time scales of intraplate volcanism in a broad variety of tectonic settings. This is because the conditions required to initiate volcanism (i.e. those of near-solidus melting of the asthenosphere) are relatively easy to produce and can therefore be caused by both near-surface tectonics and deeper mantle processes. Furthermore, the super-enrichments of incompatible elements in some intraplate volcanics can be attributed to the influence of normal geothermal gradients on melting processes. Without the very strong fractionation imposed by this combination of factors, the Oatlands volcanics would more closely resemble mid-ocean-ridge basalts.     

Systemic geopolitical modeling. Part 2: subjectivity in prediction of geopolitical events

This paper studies subjective priorities for the data amounts in the processing of geopolitical data accoding to Mazis I. Th., theoretical paradigm of Systemic Geopolitical Analysis. After defining geopolitical plans and geopolitical focus sets, they are introduced geopolitical preferences and geopolitical management capacities. The geopolitical rational choice is studied, as well as the geopolitical preference-capacity distributions. Then, they are investigated geopolitical contrasts of subjective priorities by several geopolitical operators, and it is shown that there are cores and equilibriums of geopolitical contrasts, the study of which may provide useful information.     

Fe-Ti oxide geothermometry: thermodynamic formulation and the estimation of intensive variables in silicic magmas

A new thermodynamic formulation of the Fe–Ti oxide geothermometer/oxygen barometer is developed. The method is based upon recently calibrated models for spinel solid solutions in the quinary system (Fe²⁺, Mg)(Al,Fe³⁺,Cr)₂O₄–(Fe²⁺, Mg)₂TiO₄ by Sack and Ghiorso, and rhombohedral oxides in the quaternary system (Fe²⁺,Mg,Mn)TiO₃–Fe₂O₃ (this paper). The formulation is internally consistent with thermodynamic models for (Fe²⁺,Mg)-olivine and -orthopyroxene solid solutions and end-member thermodynamic properties tabulated by Berman. The constituent expressions account for compositional and temperature dependent cation ordering and reproduce miscibility gap features in all of the component binaries. The calibration does not account for the excess Gibbs energy resulting from compositional and temperature dependent magnetic ordering in either phase. This limits application of the method to assemblages that equilibrated at temperatures above 600° C. Practical implementation of the proposed geothermometer/oxygen barometer requires minimal use of projection algorthms in accommodating compositions of naturally occurring phases. The new formulation is applied to the estimation of temperature and oxygen fugacity in a wide variety of intermediate to silicic volcanic rocks. In combination with previous work on olivine and orthopyroxene thermodynamics, equilibration pressures are computed for a subset of these volcanics that contain the assemblage quartz, oxides and either ferromagnesian silicate. The calculated log₁₀ f _{O 2}-T relations are reflected in coexisting ferromagnesian mineral assemblages. Volcanics with the lowest relative oxygen fugacity (log₁₀ f _{O 2}) are characterized by the assemblage olivine-quartz, those with slightly higher log₁₀ f _{O 2} s, by the assemblage orthopyroxene-quartz. The sequence proceeds with the necessary phases biotite-feldspar, then hornblende-quartz-clinopyroxene, and finally at the highest log₁₀ f _{O 2} s, sphene-quartz-clinopyroxene. Quantitative analysis of these trends, utilizing thermodynamic data for the constituent phases, establishes that, in most cases, the T-log₁₀ f _{O 2}value computed from the oxides is consistent with the compositions of coexisting silicate phases, indicating that phenocryst equilibrium was achieved prior to eruption. There is, however, considerable evidence of oxide-silicate disequilibrium in samples collected from more slowly cooled domes and obsidians. In addition, T-log₁₀ f _{O 2}trends from volcanic rocks that contain biotite and orthopyroxene are interpreted to imply a condition of Fe²⁺–Mg exchange disequilibrium between orthopyroxene and coexisting ferromagnesian silicates and melt. It is suspected that many biotite-feldspar-quartz-orthopyroxene bearing low temperature volcanic rocks inherit orthopyroxene xenocrysts which crystallized earlier in the cooling history of the magma body.The problem is probably at least as complex as that of the feldspars... A.F. Buddington (1956)     

Trace element cycling in a subterranean estuary: Part 2. Geochemistry of the pore water

Submarine groundwater discharge (SGD) is an important source of dissolved elements to the ocean, yet little is known regarding the chemical reactions that control their flux from sandy coastal aquifers. The net flux of elements from SGD to the coastal ocean is dependent on biogeochemical reactions in the groundwater-seawater mixing zone, recently termed the “subterranean estuary.” This paper is the second in a two part series on the biogeochemistry of the Waquoit Bay coastal aquifer/subterranean estuary. The first paper addressed the biogeochemistry of Fe, Mn, P, Ba, U, and Th from the perspective of the sediment composition of cores Charette et al. [Charette, M.A., Sholkovitz, E.R., Hansell, C.M., 2005. Trace element cycling in a subterranean estuary: Part 1. Geochemistry of the permeable sediments. Geochim. Cosmochim. Acta, 69, 2095-2109]. This paper uses pore water data from the subterranean estuary, along with Bay surface water data, to establish a more detailed view into the estuarine chemistry and the chemical diagenesis of Fe, Mn, U, Ba and Sr in coastal aquifers. Nine high-resolution pore water (groundwater) profiles were collected from the head of the Bay during July 2002. There were non-conservative additions of both Ba and Sr in the salinity transition zone of the subterranean estuary. However, the extent of Sr release was significantly less than that of its alkaline earth neighbor Ba. Pore water Ba concentrations approached 3000 nM compared with 25-50 nM in the surface waters of the Bay; the pore water Sr-salinity distribution suggests a 26% elevation in the amount of Sr added to the subterranean estuary. The release of dissolved Ba to the mixing zone of surface estuaries is frequently attributed to an ion-exchange process whereby seawater cations react with Ba from river suspended clay mineral particles at low to intermediate salinity. Results presented here suggest that reductive dissolution of Mn oxides, in conjunction with changes in salinity, may also be an important process in maintaining high concentrations of Ba in the pore water of subterranean estuaries. In contrast, pore water U was significantly depleted in the subterranean estuary, a result of SGD-driven circulation of seawater through reducing permeable sediments. This finding is supported by surface water concentrations of U in the Bay, which were significantly depleted in U compared with adjacent coastal waters. Using a global estimate of SGD, we calculate U removal in subterranean estuaries at 20 × 10⁶ mol U y⁻¹, which is the same order of magnitude as the other major U sinks for the ocean. Our results suggest a need to revisit and reevaluate the oceanic budgets for elements that are likely influenced by SGD-associated processes.