Geochimica Et Cosmochimica Acta Research Articles

Sulfur oxidation state and solubility in silicate melts

We have determined the solubility of sulfur (S) as sulfide (S2–) for 13 different natural melt compositions at temperatures of 1473–1773 K under controlled conditions of oxygen and sulfur fugacities (fO2 and fS2, respectively). The S and major element contents of the quenched glasses were determined by electron microprobe. The sulfide capacity parameter (CS2–) was used to express S2– solubility as a function of the oxygen and sulfur fugacities according to the equation: log C_{{S^{2 - } }} = log S_{melt} left( {wt% } right) + 0.5log left( {frac{{fO_{2} }}{{fS_{2} }}} right). Sulfide capacities of silicate melts were found to increase with temperature and the FeO content of the melt. We combined our sulfide data at 1473–1773 K with (O’Neill and Mavrogenes, J Petrol 43:1049–1087, 2002) results at 1673 K, and obtained by stepwise linear regression the following equation for sulfide capacity log C_{{S^{2 - } }} = 0.225 + left( {25237X_{FeO} + 5214X_{CaO} + 12705X_{MnO} + 19829X_{{K_{2} O}} - 1109X_{{Si_{0.5} O}} - 8879} right)/T{ }. XMO is the mole fraction of the oxide of M on a single-oxygen basis, and T is in Kelvin. The sulfide capacity equation was combined with sulfate capacity (CS6+) data for similar compositions and at the same temperatures (Boulliung and Wood, Geochim Cosmochim Acta 336:150–164, 2022), to estimate the S redox state (S6+/S2– ratio) as a function of melt composition, temperature and oxygen fugacity. Results obtained are in good agreement with earlier measurements of S6+/S2– for basaltic and andesitic compositions. We observe a significant increase, however, relative to FMQ of the oxygen fugacity of the S2– to S6+ transition as temperature is lowered from 1773 to 1473 K. We used our results to simulate sulfur-degassing paths for basaltic compositions under various redox conditions (FMQ –2 log fO2 units to FMQ + 2). The calculations indicate that, given an initial concentration of 0.12 wt% S in an ascending melt at 250 MPa, most of the S (> 80%) will be degassed before the magma reaches 100 MPa pressure.

Environmental hazard assessment of metals in marine sediments of Sabah and Sarawak, Malaysia

The fractionation of 10 metals (As, Co, Cr, Cu, Mn, Ni, Pb, Se, V, and Zn) within labile fractions in shallow marine sediments collected from the coasts of Sabah and Sarawak, Malaysia, was evaluated. Spatial distribution revealed that coastal sediments from Sabah were approximately 10% higher in metal content than sediments from Sarawak. Risk assessment code, enrichment factor, and pollution accumulation index calculations were used to investigate the environmental hazards of elements. For the risk assessment code, the modified Tessier sequential extraction procedure was applied. The risk assessment code values showed that metal V recorded the lowest environment risk (~ 10%) while As, Co, Cr, Cu, Mn, and Zn exhibited medium risk (Risk assessment code range of 11%–30%). The element Ni displayed no risk (0.67%) to the environment, whereas Se and Pb recorded the highest risk with values of 47% and 52%, respectively. For the enrichment factor calculation, the continental crust data presented by Taylor (Taylor, Geochim Cosmochim Acta 28:1273–1285, 1964) were used as background, with metal Al used as a reference element. Results illustrated that most of the metals show enrichment (enrichment factor > 1). However, Se was considered extremely severe to the environment (enrichment factor > 50). While the pollution accumulation index calculation demonstrated that all metals under study can be considered as non-contaminant elements except for Ni, V, and Co. These findings indicated that marine sediments in Sabah are more polluted with metal contaminants than the sediments in Sarawak, despite both states having numerous active oil- and gas-related production facilities.

Hydrogen defects in feldspars: kinetics of D/H isotope exchange and diffusion of hydrogen species in alkali feldspars

Diffusion of hydrogen in natural alkali feldspars (Eifel sanidine and adularia from unknown locality) containing strongly bonded OH defects was investigated by D/H isotope exchange in the T range 600–1050 °C at ambient pressure and at elevated pressures up to 8 kbar. Runs at 1 atm were performed in a fused silica tube connected to a liquid D2O reservoir at room temperature. In the high- pressure experiments samples were sealed with D2O in gold capsules and processed up to 4 kbar in externally heated pressure vessels using Ar/D2O as the pressure medium. Experiments at 6–8 kbar were performed in an internally heated gas pressure vessel using the double capsule technique to minimize isotopic contamination by the pressure medium. Diffusion coefficients were determined either by measuring concentration-distance profiles of OH and OD with an IR microscope or by measuring the total exchange of oriented plates after various run durations using a macroscopic IR technique. Both methods gave consistent data. D/H interdiffusion, DD/H, is almost identical in the adularia and in the sanidine implying that the chemical composition and the degree of Al/Si disorder have minor influence on the hydrogen isotope exchange in alkali feldspars. Furthermore, no effect of crystallographic orientation was found for DD/H in both feldspars. DD/H in sanidine, however, depends on the thermal pre-treatment. Heating for several days at 900 °C leads to a lowering of D by a factor of 2.3, indicating a corresponding decrease in mobile hydrogen species. Data for sanidine pre-annealed at 900 °C are well described in the T range 600–1050 °C by DD/Hm2/s=6.9·10-6exp-162kJ/molR·T\\documentclass[12pt]{minimal}\t\t\t\t\\usepackage{amsmath}\t\t\t\t\\usepackage{wasysym}\t\t\t\t\\usepackage{amsfonts}\t\t\t\t\\usepackage{amssymb}\t\t\t\t\\usepackage{amsbsy}\t\t\t\t\\usepackage{mathrsfs}\t\t\t\t\\usepackage{upgreek}\t\t\t\t\\setlength{\\oddsidemargin}{-69pt}\t\t\t\t\\begin{document}$$~D_{{{\\text{D/H}}}} \\left( {{\\text{m}}^{2} {\\text{/s}}} \\right) = 6.9 \\cdot 10^{{ - 6}} \\exp \\left( {\\frac{{ - 162{\\text{~kJ}}/{\\text{mol}}}}{{R \\cdot T}}} \\right)$$\\end{document}The diffusivity is strongly enhanced by water pressures (PH2O), i.e., in the range of 0–2 kbar. At PH2O = 2 kbar the following equation applies in the T-range of 645–800 °C: DD/Hm2/s=1.2·10-6exp-131kJ/molR·T\\documentclass[12pt]{minimal}\t\t\t\t\\usepackage{amsmath}\t\t\t\t\\usepackage{wasysym}\t\t\t\t\\usepackage{amsfonts}\t\t\t\t\\usepackage{amssymb}\t\t\t\t\\usepackage{amsbsy}\t\t\t\t\\usepackage{mathrsfs}\t\t\t\t\\usepackage{upgreek}\t\t\t\t\\setlength{\\oddsidemargin}{-69pt}\t\t\t\t\\begin{document}$$~D_{{D/H}} \\left( {{\\text{m}}^{2} /{\\text{s}}} \\right) = 1.2 \\cdot 10^{{ - 6}} \\exp \\left( {\\frac{{ - 131~{\\text{kJ}}/{\\text{mol}}}}{{R \\cdot T}}} \\right)$$\\end{document}Experiments with D2O/CO2 mixture of ratio 1:1 gave smaller exchange rates compared to pure D2O fluids, confirming that that not the pressure but the water fugacity leads to the increase in the mobility of hydrogen species. At 720 °C and pressures of 4–8 kbar, chemical diffusivities of H2O, tilde{D}_{{{text{H}}_{2} {text{O}}}}, were determined by fitting the weighted sum of the absorbances of the OH and the OD band vs. distance. The tilde{D}_{{{text{H}}_{2} {text{O}}}} values are similar to those reported by Kronenberg et al. (Geochim Cosmochim Acta 60:4075–4094, 1996) for dehydration of Kristallina adularia at ambient pressure. It is concluded that in both cases high concentrations of H2O molecules on interstitial sites govern the transport of hydrogen. Comparison of D/H interdiffusion to O diffusion in sanidine (Freer et al. in Phil Mag A75:485–503, 1997) implies that not only interstitial H2O but also protons contribute to the transport of hydrogen under hydrothermal conditions. On the other hand, the high DD/H at ambient pressure is attributed to an interdiffusion of protons and Na+, which is supported by Na tracerdiffusion data for sanidine (Wilangowski et al. in Defect Diffus Forum 363:79–84, 2015). A basic conclusion of this research is that hydrogen storage capacity and hydrogen diffusion in feldspars are largely determined by extrinsic defects, such as substitutional defects (i.e., Al3+ + H+ for Si4+) and associates of water molecules with vacancies. The bonding of hydrogen species to the defects can vary greatly, depending on the genesis of the feldspars, so that quantitative predictions are difficult.

The Abiotic Nitrite Oxidation by Ligand-Bound Manganese (III): The Chemical Mechanism

Given their environmental abundances, it has been long hypothesized that geochemical interactions between reactive forms of manganese and nitrogen may play important roles in the cycling of these elements. Indeed, recent studies have begun shedding light on the possible role of soluble, ligand-bound Mn(III) in promoting abiotic transformations under environmentally relevant conditions. Here, using the kinetic data of Karolewski et al. (Geochim Cosmochim Acta 293:365–378, 2021), we provide the chemical mechanism for the abiotic oxidation of nitrite (NO2−) by Mn(III)-pyrophosphate, MnIIIPP, to form nitrate (NO3−). Nitrous acid (HNO2), not NO2−, is the reductant in the reaction, based on thermodynamic and kinetic considerations. As soluble Mn(III) complexes react in a one-electron transfer reaction, two one-electron transfer steps must occur. In step one, HNO2 is first oxidized to nitrogen dioxide, ·NO2, a free radical via a hydrogen atom transfer (HAT) reaction. We show that this inner sphere reaction process is the rate-limiting step in the reaction sequence. In step two, ·NO2 reacts with a second MnIIIPP complex to form the nitronium ion (NO2+), which is isoelectronic with CO2. Unlike the poor electron-accepting capability of CO2, NO2+ is an excellent electron acceptor for both OH− and H2O, so NO2+ reacts quickly with water to form the end-product NO3− (step 3 in the reaction sequence). Thus, water provides the O atom in this nitrification reaction in accordance with the O-isotope data. This work provides mechanistic perspective on a potentially important interaction between Mn and nitrogen species, thereby offering a framework in which to interpret kinetic and isotopic data and to further investigate the relevance of this reaction under environmental conditions.

Investigations of mechanism of Ca2+ adsorption on silica and alumina based on Ca-ISE monitoring, potentiometric titration, electrokinetic measurements and surface complexation modeling

Research on Ca2+ adsorption onto the mineral surface is of significant importance with regard to geochemical processes. Sverjensky (Geochim Cosmochim Acta 70(10), 2427–2453, 2006) assumed that alkaline earths form two types of surface species on oxides: tetranuclear (> SOH)2(> SO−)2_M(OH)+ and mononuclear > SO−_M(OH)+. To look into the above assumption we investigated calcium adsorption on SiO2 and Al2O3 because they are the most widespread minerals in the environment. We have determined the proton surface charge, electrokinetic potential and metal adsorption as a function of pH. The Ca2+ uptake and concentration in the system were monitored by the calcium ion-selective electrode (Ca-ISE). The Ca-ISE measurements indicated a similar affinity of Ca2+ for both materials despite their differently charged surface, negative for silica and mainly positive for alumina. This may suggest that simple electrostatic interactions are not the primary driving force for calcium adsorption, and that solvation of calcium ions at the surface may be crucial. We have analyzed our experimental data using the 2-pK triple-layer model (2-pK TLM). Three calcium complexes on the mineral surface were reported. Two of them were the same for both oxides, i.e. the tetranuclear (> SOH)2(> SO−)2_Ca2+ and mononuclear complexes > SO−_CaOH+. Additionally, minor contribution from >SOH…Ca2+ for silica was assumed. In the case of Al2O3 the hydrolyzed tetranuclear complexes (> SOH)2(> SO−)2_CaOH+ at pH > 7.5 occurred based on the modeling results. Two types of surface complexes suggested by Sverjensky allowed for the correct description of proton and calcium uptake for alumina. However, the electrokinetic data excluded hydrolyzed tetranuclear surface species for this oxide.

Geobarometry for spinel peridotites using Ca and Al in olivine

Experiments were performed from 950 to 1250 °C and 1.5–2.4 GPa to determine the effect of pressure (P) on the temperature (T)-dependent partitioning of Al between olivine and spinel, using mixtures of natural spinel, olivine, clino- and ortho-pyroxene. When compared to 100 kPa experiments, the results show that there is no discernible effect of pressure on the Al-in-olivine thermometer at PT conditions relevant to the spinel peridotite facies. In our experiments with high-Cr spinel, we see no change in Al in olivine from starting values, likely due to the refractory nature of high-Cr spinel. Phase boundary flourescence prevented accurate quantification of Ca in olivine in the run products by electron microprobe analysis but measurements by laser ablation are consistent with the Kohler and Brey (Geochim Cosmochim Acta 54:2375–2388, 1990) Ca-in-olivine thermobarometer. The combination of Al (for T) and Ca (for P) in olivine thus has great potential for thermobarometry in spinel facies peridotites. As a test we apply this approach to published high precision Ca and Al data for olivine from the Ray Pic spinel peridotite xenoliths from the Massif Central (De Hoog et al. Chem Geol 270:196–215, 2010). Reassuringly, the calculated PT conditions (1.0–1.8 GPa; 900–1080 °C) for all samples lie beneath the Moho, within the spinel peridotite facies and fall along a geophysically constrained geotherm.

Fluorine-controlled composition of biotite in granulites of Madagascar: the effect of fluorine on thermometry of biotite–garnet gneisses

Because of the strong preference of fluorine (F) for “hydrous” magnesian silicate minerals, the temperature T(0F) given by the reaction (Bi–Gt) of Fe–Mg exchange between biotite and garnet [phlogopite (Phl) + almandine (Alm) = annite (Ann) + pyrope (Py)] can be dramatically underestimated when the reciprocal effects between octahedral and hydroxyl site occupancies in biotite are ignored. In the granulites of southeastern Madagascar, widespread Mg metasomatism was associated with F-rich fluids. It is mainly manifested by the regional occurrence of diopside skarns hosting F-phlogopite and thorianite mineralisation. At first, biotite- and garnet-bearing granites and leucogneisses appear unaffected by this event. However, their biotites are rich in F [up to 6 wt%; XF = XF/(F + OH) = 0.69) and in Mg (XMg = Mg/(Mg + Fe) up to 0.8], which shows the tendency of equilibrium with the regional fluids. This equilibration leads to low values of Fe/Mg, which in turn cause strong underestimation of the temperature: T(0F) as low as 500 °C, whereas the temperature T(Ti) given by the TiO2 content of biotite is approximately 750 °C. The slightly modified thermodynamic model of Zhu and Sverjensky (Geochim Cosmochim Acta 56:3435–3467, 1992) for reciprocal solid solution is applied to a set of 19 samples to correct this underestimation and to quantify the effect of F on thermometry. The reciprocal activity coefficients for phlogopite (λ(Phl)) and annite (λ(Ann)) calculated by the model are added to the winTWQ software to obtain corrected values T(F) of the temperature. Similar values of ΔT = T(F) − T(0F) are obtained by (1) the linear fit of the whole set of the samples and (2) RTlnKλ = RTlnλ(Ann) − RTlnλ(Phl) = 33.417XF − 0.1092 (r2 = 0.9994) equation applied to a median sample: ΔT = 30–40, 60–70, 95–100, 160, and 200 °C for XF = 0.1, 0.2, 0.3, 0.5, and 0.7, respectively. The same calculations based on the Thermocalc thermodynamic data set lead to values of ΔT 1.5 times higher than those given by winTWQ. Thus, the results of these calculations confirm (for the first time from a set of natural samples) the validity of the thermodynamic model of reciprocal solid solution and the necessity of accounting for F in thermometry based on Fe–Mg exchanges involving biotite.

Book Review: Geochemical Rate Models: An Introduction to Geochemical Kineticsby J. Donald Rimstidt

Book Review: Geochemical Rate Models: An Introduction to Geochemical Kinetics. By J. Donald Rimstidt (2013) Cambridge University Press, 232 p. $84.99 Hardback, ISBN: 9781107029972. The book Geochemical Rate Models: An Introduction to Geochemical Kinetics by Don Rimstidt is a delight to read and fills an urgent need for students of geochemistry. Over the last two decades, there has been a tremendous increase in the literature on the topic of reaction kinetics. For example, a search on the Web of Science database using the keyword “kinetics” shows that over the last 25 years, there has been an increased number of articles in the leading journal Geochimica et Cosmochimica Acta (GCA), totaling 1193 publications (Fig. 1). In contrast, only a total of 176 articles published in GCA used keyword “thermodynamics” between 1990 and 2015. As evidenced, a book on the topic of geochemical kinetics is timely and relevant. Figure 1 Search statistic of articles published in Geochimica et Cosmochimica Acta that used the key word “kinetics.” Data are arranged in five year intervals. Search was made in August 2015. (Color online.) The surge in kinetics studies reflects the fact that many reactions in …

The Speciation of Metals in Natural Waters

The equilibria and rates of reactions of trace metals in natural waters are affected by their speciation or the form of the metal in the solution phase. Many workers have shown, for example, that biological uptake (Anderson and Morel in Limnol Oceanogr 27:789–813, 1982), the toxicity (Sunda and Ferguson in Trace metals in seawater, Plenum Press, New York, 1983) as well as the solubility (Millero et al. in Mar Chem 50:21–39, 1995; Liu and Millero in Geochim Cosmochim Acta 63:3487–3497, 1999) are affected by the speciation. For example, Fe(II) and Mn(II) are biologically available for marine organisms, while Fe(III) and Mn(IV) are normally not available. The speciation of metals also affects the rates of oxidation (Millero in Geochim Cosmochim Acta 49:547–553, 1985, Res Trends Curr Top Sol Chem 1:141–169, 1994; Sharma and Millero in Geochim Cosmochim Acta 53:2269–2276, 1989; Vazquez et al. in Geophys Res Lett 16:1363–1366, 1989) and reduction (Res Trends Curr Top Sol Chem 1:141–169, 1994; Millero et al. in Mar Chem 36:71–83, 1991) of metals in natural waters. The ionic interactions of metals are controlled by interactions with inorganic (Cl−, OH−, CO3 2−, etc.) and organic ligands (e.g., Fulvic and Humic acids). The speciation of metals is also affected by the oxidation potential (Eh) and the pH in the solution. In this paper we have developed a Pitzer Model (Pitzer in J Phys Chem 77:268–277, 1973, Activity coefficients in electrolyte solutions, 2nd edn, CRC Press, Boca Raton, 1991) that can be used to determine the speciation of trace metals in seawater and other natural waters. It is based upon the Miami Pitzer Model (Millero and Pierrot in Aquatic Geochem 4:153–199, 1998) that has been shown to predict reliable activity coefficients for the major components of seawater. The computer code (Pierrot in Ph.D. Thesis, University of Miami, Miami, Florida, 2002) for these calculations is described in detail, in this paper. It has been used in an earlier paper (Millero and Pierrot in Chemistry of marine water and sediments, Springer, Berlin, 2002) and more recently used to examine the effect of pH on the speciation of metals in seawater (Millero et al. in Oceanography 22(4):72–85, 2009).

Mineralization and trace element distribution in pyrite using EMPA in exploration drill holes from Cheshmeh Zard gold district, Khorasan Razavi Province, Iran

ناحیه مطالعاتی در شمال استان خراسان رضوی و 45 کیلومتری جنوب نیشابور قرار دارد. رگه های طلادار درون سنگهای گرانیت، گرانودیوریت، گرانودیوریت پورفیری، آندزیت، برش و توف نفوذ کرده اند. رگه ها از جنس کوارتز و کلسیت هستند. مناطق اصلی دگرسانی شامل منطقه سرسیتیک، سیلیسی، پروپلیتیک و منطقه کربنات است. کانی زایی به‌طور نزدیکی با دگرسانیهای سیلیسی و سرسیتیک به شکل رگه‌چه و با منطقه پروپلیتیک به شکل افشان همراه است. کانی شناسی کانیهای باطله کوارتز، کلسدونی، سرسیت، آدولاریا، کلسیت، دولومیت، ایلیت، دیکیت، آلبیت، کائولینیت و کلریت است. کانی زایی رگه ای عمدتا با رگه‌چه ها، برش، افشان و استوک ورک همراه هستند. رگه‌چه ها از پیریت، مارکازیت، آرسنوپیریت و کمتر کالکوپیریت، اسفالریت، گالن، مگنتیت و هماتیت تشکیل شده اند. بیشترین عیار طلا در رگه های سیلیسی دیده می شود. پیریت کانی سولفیدی اصلی در کانی سازی اولیه است. سه نوع پیریت بر اساس ترکیب شیمیایی شناسایی شده است: پیریت خالص، پیریت غنی از آرسنیک و پیریت تیتانیوم- وانادیوم دار. تجزیه های ریزکاوشگر الکترونی بیشترین غلظت آرسنیک، تیتانیوم و وانادیوم را به ترتیب 62/3، 91/3 و 53/0 درصد وزنی در پیریتهای رگه های طلادار نشان می دهند. طلا معمولا همراه با پیریت آرسنیک دار و پیریت تیتانیوم- وانادیوم دار است. براساس مطالعه بافت و ترکیب پیریتها، رگه‌چه‌های پیریت آرسنیک دار همراه با کانیهای سولفیدی آرسنوپیریت، کالکوپیریت، گالن، اسفالریت در دمای بالا و با کاهش دما و فشار، پیریتهای فرامبوئیدال با حاشیه حاوی آرسنیک و طلا شکل گرفته اند و در ادامه پیریتهای درشت تیتان دار به‌وجود آمده اند. پیریتهای خالص و تأخیری درشت بلور آخرین فاز کانی ساز در منطقه هستند.

Slab and sediment melting during subduction initiation: granitoid dykes from the mantle section of the Oman ophiolite

New geochemical data are presented for a suite of tonalites, granodiorites, trondhjemites and granites intrusive into depleted mantle harzburgites of the Oman–UAE ophiolite. A detailed field, petrological and geochemical examination suggests that these ‘mantle granitoids’ are the product of three processes: (a) the mixing of melts derived from both mafic and metasedimentary sources, (b) interaction with the mantle harzburgite host and (c) the fractional crystallisation of plagioclase, hornblende ± accessory phases. Geochemical data are used to characterise the identity of the protolith(s) by first screening the data for those samples which have experienced fractional crystallisation during emplacement. The resultant ‘reduced’ data set has moderately fractionated REE, with small negative Eu anomalies and fractionated primitive mantle-normalised trace element patterns with high concentrations of fluid mobile elements and lower concentrations of HFS elements and with positive peaks for Rb and Pb and negative troughs for Ba, Nb, Sr and Ti. The character of the protolith was quantified using a melting model based upon a MORB-type basalt similar in composition to the Oman Geotimes lavas and a model using the MUQ (MUd from Queensland) global sediment composition (Kamber et al. Geochim Cosmochim Acta 69:1041–1058, 2005) both with an amphibolite/granulite facies mineralogy. The two compositions bracket the mantle granitoid data set with partial melts of the MORB source yielding trace element compositions lower than the granitoids, whereas melts of the MUQ source yield melts with compositions higher than the granitoids. Mixing of the calculated melt compositions indicates that the measured granitoid compositions represent between 10 and 30 % mixing of a metasedimentary melt into the melt of a mafic source. Current petrological, structural and geochronological data suggest a model for the origin of the Oman ophiolite in which it is formed by spreading above a subduction zone. The results of this study support this model in three ways: (a) trace element data show that the granitoids have interacted with the mantle, implying that they originated below the mantle section of the ophiolite and were emplaced into the mantle wedge from below; (b) a most probable setting for the melting of a sediment–basalt mix is in the upper part of a subducting slab; (c) the high temperature/shallow melting of the sediment and basaltic slab mix can only have been driven by the high temperatures of the overlying mantle wedge; this is most likely during subduction initiation. Thus, sediment melting during subduction initiation represents an important means of refertilising what is otherwise highly depleted mantle.

An H2O–CO2 mixed fluid saturation model compatible with rhyolite-MELTS

A thermodynamic model for estimating the saturation conditions of H2O–CO2 mixed fluids in multicomponent silicate liquids is described. The model extends the capabilities of rhyolite-MELTS (Gualda et al. in J Petrol 53:875–890, 2012a) and augments the water saturation model in MELTS (Ghiorso and Sack in Contrib Mineral Petrol 119:197–212, 1995). The model is internally consistent with the fluid-phase thermodynamic model of Duan and Zhang (Geochim Cosmochim Acta 70:2311–2324, 2006). It may be used independently of rhyolite-MELTS to estimate intensive variables and fluid saturation conditions from glass inclusions trapped in phenocrysts. The model is calibrated from published experimental data on water and carbon dioxide solubility, and mixed fluid saturation in silicate liquids. The model is constructed on the assumption that water dissolves to form a hydroxyl melt species, and that carbon dioxide both a molecular species and a carbonate ion, the latter complexed with calcium. Excess enthalpy interaction terms in part compensate for these simplistic assumptions regarding speciation. The model is restricted to natural composition liquids over the pressure range 0–3 GPa. One characteristic of the model is that fluid saturation isobars at pressures greater than ~100 MPa always display a maximum in melt CO2 at nonzero H2O melt concentrations, regardless of bulk composition. This feature is universal and can be attributed to the dominance of hydroxyl speciation at low water concentrations. The model is applied to four examples. The first involves estimation of pressures from H2O–CO2-bearing glass inclusions found in quartz phenocrysts of the Bishop Tuff. The second illustrates H2O and CO2 partitioning between melt and fluid during fluid-saturated equilibrium and fractional crystallization of MORB. The third example demonstrates that the position of the quartz–feldspar cotectic surface is insensitive to melt CO2 contents, which facilitates geobarometry using phase equilibria. The final example shows the effect of H2O and CO2 on the crystallization paths of a high-silica rhyolite composition representative of the late-erupted Bishop Tuff. Software that implements the model is available at ofm-research.org, and the model is incorporated into the latest version (1.1+) of rhyolite-MELTS.

A reactive transport benchmark on modeling biogenic uraninite re-oxidation by Fe(III)-(hydr)oxides

A reactive transport benchmark on uranium (U) bioreduction and concomitant reoxidation has been developed based on the multicomponent biogeochemical reaction network presented by Spycher et al. (Geochim Cosmochim Acta 75:4426–4440, 2011). The benchmark problem consists of a model inter-comparison starting with the numerical simulations of the original batch experiments of Sani et al. (Geochim Cosmochim Acta 68:2639–2648, 2004). The batch model is then extended to 1D and 2D reactive transport models, designed to evaluate the model results for the key biogeochemical reaction processes and their coupling with physical transport. Simulations are performed with four different reactive transport simulators: PHREEQC, PHT3D, MIN3P, and TOUGHREACT. All of the simulators are able to capture the complex biogeochemical reaction kinetics and the coupling between transport and kinetic reaction network successfully in the same manner. For the dispersion-free variant of the problem, a 1D-reference solution was obtained by PHREEQC, which is not affected by numerical dispersion. PHT3D using the sequential non-iterative approach (SNIA) with an explicit TVD scheme and MIN3P using the global implicit method (GIM) with an implicit van Leer flux limiter provided the closest approximation to the PHREEQC results. Since the spatial weighting schemes for the advection term and numerical dispersion played an important role for the accuracy of the results, the simulators were further compared using different solution schemes. When all codes used the same spatial weighting scheme with finite-difference approximation, the simulation results agreed very well among all four codes. The model intercomparison for the 2D-case demonstrated a high level of sensitivity to the mixing of different waters at the dispersive front. Therefore this benchmark problem is well-suited to assess code performance for mixing-controlled reactive transport models in conjunction with complex reaction kinetics.

176Lu–176Hf geochronology of garnet I: experimental determination of the diffusion kinetics of Lu3+ and Hf4+ in garnet, closure temperatures and geochronological implications

The 176Lu–176Hf and 147Sm–143Nd decay systems are routinely used to determine garnet (Grt)–whole-rock (WR) ages; however, the 176Lu–176Hf age of garnet is typically older than the 147Sm–143Nd age determined from the same aliquots. Here we present experimental data for Lu3+ and Hf4+ diffusion in garnet as functions of temperature, pressure and oxygen fugacity and show that the diffusivity of Hf4+ in almandine/spessartine garnet is significantly slower than that of Lu3+. The diffusive closure temperature (T C) of Hf4+ is significantly higher than that of Nd3+, and although this property is partly responsible for the observed 176Lu–176Hf and 147Sm–143Nd Grt–WR age discrepancies, the difference between the T C-s of Lu3+ and Hf4+ could lead to apparent Grt–WR 176Lu–176Hf ages that are skewed from the age of Hf4+ closure in garnet. In addition, the slow diffusivity of Hf4+ indicates that the bulk of metamorphic garnets retain a substantial fraction of prograde radiogenic 176Hf throughout peak metamorphic conditions, a phenomenon that further complicates the interpretation of 176Lu–176Hf garnet ages and invalidates the use of analytical T C expressions. We argue that the diffusion of trivalent rare earth elements in garnet becomes much faster when their concentration level falls below a few hundred ppm, as in the experiments of Tirone et al. (Geochim Cosmochim Acta 69: 2385–2398, 2005), and further argue that this low-concentration mechanism is appropriate for modeling the susceptibility of 147Sm–143Nd garnet ages to diffusive resetting.

Coupled alkali feldspar dissolution and secondary mineral precipitation in batch systems: 5. Results of K-feldspar hydrolysis experiments

This paper explores how dissolution and precipitation reactions are coupled in batch reactor experimental systems at elevated temperatures. This is the fifth paper in our series of “Coupled Alkali Feldspar Dissolution and Secondary Mineral Precipitation in Batch Systems.” In the previous four papers we presented batch experiments of alkali-feldspar hydrolysis and explored the coupling of dissolution and precipitation reactions (Fu et al. in Chem Geol 91:955–964, 2009; Zhu and Lu in Geochim Cosmochim Acta 73:3171–3200, 2009; Zhu et al.in Geochim Cosmochim Acta 74:3963–3983, 2010; Lu et al. in Appl Geochem 30:75–90, 2013). Here, we present the results of additional K-rich feldspar hydrolysis experiments at 150 °C. Our solution chemistry measurements have constrained feldspar dissolution rates, and our high resolution transmission electron microscopy work has identified boehmite precipitation. Reaction path modeling of K-feldspar dissolution and boehmite precipitation simulated the coupled reactions, but only with forced changes of boehmite rate law in the middle of experimental duration. The results which are reported in this article lend further support to our hypothesis that slow secondary mineral precipitation explains part of the well-known apparent discrepancy between lab measured and field estimated feldspar dissolution rates (Zhu et al. in Water–rock interaction, 2004).

Water contents of Roberts Victor xenolithic eclogites: primary and metasomatic controls

A suite of eclogites from the Roberts Victor kimberlite has been extensively characterized in terms of petrology and geochemical compositions (Greau et al. in Geochim Cosmochim Acta 75(22):6927–6954, 2011; Huang et al. in Lithos 142–143:161–181, 2012a). In the present study, the water contents of eclogitic garnet and omphacite were analyzed by Fourier transform infrared spectrometry. Garnet does not contain measureable OH in any sample. The water content of omphacite in the studied eclogites ranges from 211 to 1,496 ppm. Mantle metasomatism has modified the water content of some of the eclogites, while others retain water contents characteristic of their original environment. The OH contents of the metasomatized eclogites may be mainly controlled by the H2O fugacity and mineral compositions. The OH contents of the non-metasomatized samples are interpreted to be more sensitive to their mantle equilibration temperature, pressure, and the local fugacities of H2O and O2. The calculated water content of the metasomatic medium is similar to that of carbonatitic–kimberlitic melts/fluids. Eclogites contain more water than peridotites recorded in the literature (341 ± 161 vs 122 ± 54 ppm) and represent an important water reservoir in the lithospheric mantle wherever they occur. This is an important parameter to be considered in the interpretation of mantle processes and geophysical data such as seismic wave speeds and electrical conductivity, and in geodynamic modeling.

Thermodynamic properties of chlorite and berthierine derived from calorimetric measurements

In the context of the deep waste disposal, we have investigated the respective stabilities of two iron-bearing clay minerals: berthierine ISGS from Illinois [USA; (Al0.975FeIII0.182FeII1.422Mg0.157Li0.035Mn0.002)(Si1.332Al0.668)O5(OH)4] and chlorite CCa-2 from Flagstaff Hill, California [USA; (Si2.633Al1.367)(Al1.116FeIII0.215Mg2.952FeII1.712Mn0.012Ca0.011)O10(OH)8]. For berthierine, the complete thermodynamic dataset was determined at 1 bar and from 2 to 310 K, using calorimetric methods. The standard enthalpies of formation were obtained by solution-reaction calorimetry at 298.15 K, and the heat capacities were measured by heat-pulse calorimetry. For chlorite, the standard enthalpy of formation is measured by solution-reaction calorimetry at 298.15 K. This is completing the entropy and heat capacity obtained previously by Gailhanou et al. (Geochim Cosmochim Acta 73:4738–4749, 2009) between 2 and 520 K, by using low-temperature adiabatic calorimetry and differential scanning calorimetry. For both minerals, the standard entropies and the Gibbs free energies of formation at 298.15 K were then calculated. An assessment of the measured properties could be carried out with respect to literature data. Eventually, the thermodynamic dataset allowed realizing theoretical calculations concerning the berthierine to chlorite transition. The latter showed that, from a thermodynamic viewpoint, the main factor controlling this transition is probably the composition of the berthierine and chlorite minerals and the nature of the secondary minerals rather than temperature.

Organic Delivery Device

Planetary Science![Figure][1] CREDIT: K. L. THOMAS-KEPRTA ET AL., GEOCHIMICA ET COSMOCHIMICA ACTA (15 MARCH 2014) © 2014 ELSEVIER B.V. Several plausible mechanisms could produce complex organic molecules on the Moon, including synthesis by energetic UV radiation or impact shocks, delivery from meteorites, and even decay of biotic matter. However, Apollo samples have shown surprisingly low levels of carbon. Thomas-Keprta et al. have now detected complex organics larger than methane within lunar samples from Shorty Crater. They probed glassy beads tens of micrometers in diameter for fluorescence, revealing some with thin layers of carbonaceous material that were apparently embedded while the silicate surface was still molten. Chemical characterization with micro-Raman spectroscopy indicated the presence of macromolecular matter similar to kerogen, a compound that composes the bulk of stony meteorites. The authors favor a production scenario in which these abiotic organics were delivered via micrometeorites around the time that the volcanic glass beads formed. More substantial meteoritic accretion from cometary and asteroidal fragments also is thought to have occurred on the early Earth. The specific quantity and nature of these organics remain under investigation in the context of possible precursors for life in the solar system. Geochim. Cosmochim. Acta 10.1016/j.gca.2014.02.047 (2014). [1]: pending:yes

The structure and transformation of the nanomineral schwertmannite: a synthetic analog representative of field samples

The phase transformation of schwertmannite, an iron oxyhydroxide sulfate nanomineral synthesized at room temperature and at 75 °C using H2O2 to drive the precipitation of schwertmannite from ferrous sulfate (Regenspurg et al. in Geochim Cosmochim Acta 68:1185–1197, 2004), was studied using high-resolution transmission electron microscopy. The results of this study suggest that schwertmannite synthesized using this method should not be described as a single phase with a repeating unit cell, but as a polyphasic nanomineral with crystalline areas spanning less than a few nanometers in diameter, within a characteristic ‘pin-cushion’-like amorphous matrix. The difference in synthesis temperature affected the density of the needles on the schwertmannite surface. The needles on the higher-temperature schwertmannite displayed a dendritic morphology, whereas the needles on the room-temperature schwertmannite were more closely packed. Visible lattice fringes in the schwertmannite samples are consistent with the powder X-ray diffraction (XRD) pattern taken on the bulk schwertmannite and also matched d-spacings for goethite, indicating a close structural relationship between schwertmannite and goethite. The incomplete transformation from schwertmannite to goethite over 24 h at 75 °C was tracked using XRD and TEM. TEM images suggest that the sample collected after 24 h consists of aggregates of goethite nanocrystals. Comparing the synthetic schwertmannite in this study to a study on schwertmannite produced at 85 °C, which used ferric sulfate, reveals that synthesis conditions can result in significant differences in needle crystal structure. The bulk powder XRD patterns for the schwertmannite produced using these two samples were indistinguishable from one another. Future studies using synthetic schwertmannite should account for these differences when determining schwertmannite’s structure, reactivity, and capacity to take up elements like arsenic. The schwertmannite synthesized by the Regenspurg et al. method produces a mineral that is consistent with the structure and morphology of natural schwertmannite observed in our previous study using XRD and TEM, making this an ideal synthetic method for laboratory-based mineralogical and geochemical studies that intend to be environmentally relevant.

Activities and volatilities of trace components in silicate melts: a novel use of metal–silicate partitioning data

Ian Carmichael spent 45 years thinking about and working on the activities of components in silicate melts and their use to estimate physicochemical conditions at eruption and in the source regions of igneous rocks. These interests, principally in major components such as SiO2, led us to think about possible ways of determining the complementary activity coefficients of trace components in silicate melts. While investigating the conditions of accretion and differentiation of the Earth, a number of authors have determined the partitioning of trace elements such as Co, Ni, Mo and W between liquid Fe metal and liquid silicate. These data have the potential to provide activity information for a large number of trace components in silicate melts. In order to turn the partitioning measurements into activities, however, we need to know the activity coefficient of FeO, γFeO in the silicate. We obtained γFeO as a function of melt composition by fitting a simple model to 83 experimental data for which the authors had measured the FeO content of the silicate melt in equilibrium with metal (Fe-bearing alloy) at known fO2. The compositional dependence of γFeO is weak, but, when calculated in the system Diopside–Anorthite–Forsterite, it decreases towards the Forsterite apex. A similar approach for Ni, for which twice as many data are available, leads to similar composition dependence of activity coefficient and confirms the suggestion that γNiO/γFeO is almost constant over a wide range of silicate melt composition. The activity coefficients for FeO were used in conjunction with measured Mo and W partitioning between Fe-rich metal and silicate melt to estimate activity coefficients for trace MoO2 and WO3 dissolved in silicate melt. When combined with data on Mo- and W-saturated silicate melts a strong dependence of activity coefficient is observed. Calculated in the system Diopside–Anorthite–Forsterite, both MoO2 and WO3 exhibit similar behaviour to FeO and NiO in that activity coefficients decrease as Forsterite content increases. The effect is much larger for Mo and W, however, γMoO2 and γWO3 varying by factors of 20 and nearly 100, respectively, in this system. In order to illustrate the potential applications of the metal–silicate partitioning approach to determine the activity coefficients of volatile elements, we used it to determine activity coefficients of PbO, CuO0.5 and InO1.5 in a silica-saturated melt at 1,650 °C. We find values of 0.22, 3.5 and 0.02, respectively, indicating a strong dependence on cation charge. The value for CuO0.5 is in excellent agreement with experimental data of Holzheid and Lodders (Geochim Cosmochim Acta 65:1933–1951, 2001), which shows that the method is viable. When combined with thermodynamic data on the gas species, we find that Pb is the most volatile of the 3 elements under ‘normal’ terrestrial conditions of oxygen fugacity but that In should become the most volatile under strongly reducing conditions such as those of the solar nebula. The oxygen fugacity dependence of volatility has implications for the high relative abundance of In in silicate Earth. We conclude that metal–silicate partitioning experiments are a viable means for determining activities of trace components in silicate melts and are particularly useful if the metal of the element is unstable or volatile at igneous temperatures.