富F熔体-溶液体系流体地球化学及其成矿效应--研究现状及存在问题

高度演化花岗岩类多为富F的熔体溶液体系 ,具有鲜明的、不同于其他体系的地球化学行为。富F岩浆固相线和液相线的降低和岩浆寿命的延长 ,使残余熔体与热水热液的性状差异减小 ,模糊了岩浆与热液之间的界线。最近对于富F、B和P伟晶岩中熔融包裹体的研究获得了新的进展。在约 70 0～ 5 0 0℃的温度和 1 0 0 0× 1 0 5Pa的压力下 ,在伟晶岩石英中发现两种不同类型的熔体包裹体 ,一种是富硅酸盐、贫水的熔体包裹体 ,另一种是贫硅酸盐、富水的熔体包裹体。两种熔体在硅酸盐 (+F +B +P) 水体系的溶离线边界上同时被圈闭。这表明 ,在地壳浅部侵位的侵入体 ,当温度≥ 70 0℃时 ,水在富F、B和P的熔体中可以无限混溶 ;而一旦温度降低 ,就会分离为两种共存的熔体并伴随强烈的元素分异作用。在溶离线的富水一侧形成与正常硅酸盐熔体有很大不同的高度富挥发份的熔体 ,这种致密、高粘度、高扩散性以及高活动性的超富水 (hyper aqueousmelt)熔体 ,可以与水溶液流体相类比。这为岩浆热液过渡性流体的假说提供了新的有利的证据。此外 ,在这种具有超富水和熔体特征的过渡性流体中 ,微迹元素可能具有特殊的地球化学行为 ,如在许多晚期花岗岩包括淡色花岗岩和伟晶岩中稀土元素配分模式所显示的四分组效应等。富F熔体溶液体?     

Apatite and scapolite as petrogenetic indicators in granolites of Milford Sound,New Zealand

A network of 5 cm wide subplanar zones of garnet-granolite with accessory apatite as the dominant hydrous mineral, is overprinted on basic hornblende-granolites in an area of present and past tectonic uplift. Fracturing and the garnet forming reactions appear to be caused by destabilisation of hornblende, as a hydrous phase, through a critical drop in the PT ratio. Whereas the apatites from the hornblende-granolite have normal compositions, apatites from the garnet-granolite zones are among the most chlorine enriched hydroxyfluorapatites known. A later amphibolite facies event has depleted hydrous minerals of fluorine and chlorine, affecting hornblende more strongly than apatite. Based on literature data on F and Cl in coexisting minerals, original hornblende compositions are tentatively restored. It is then possible to derive all the chlorine of the garnet zone apatites from the original rock, with differential loss of H₂O and HF over chlorine during the dehydration reaction. Diffusion coefficients would have been larger for H₂O and HF than for the large chloride ion, and if the gas phase was in contact with even minor anatectic melts, activity gradients would also have been relatively small for chlorine. Low-Cl scapolite is present in quartz-free pegmatoid veins. Field evidence for a genetic tie between the garnet zones and these veins is inconclusive, but liberation of H₂O and HF under granolite facies conditions is likely to have caused limited fusion of the plagioclase. Since many garnet zones do not contain even small pegmatoid veins, melts related to their formation could have collected in veins only after initial diffusion or infiltration over a distance, and without leaving segregated mafic residues.     

Composite carbonate and silicate multiphase solid inclusions in metamorphic garnet from ultrahigh‐P eclogite in the Dabie orogen

Composite multiphase solid (MS) inclusions composed of carbonate and silicate minerals have been found for the first time in metamorphic garnet from ultrahigh‐P eclogite from the Dabie orogen. These inclusions are morphologically euhedral to subhedral, and some show relatively regular shapes approaching the negative crystal shape of the host garnet. Radial fractures often occur in garnet hosting the inclusions. The inclusions are primarily composed of variable proportions of carbonate and silicate minerals such as calcite, quartz, K‐feldspar and plagioclase, with occasional occurrences of magnetite, zircon and barite. They are categorized into two groups based on the proportions of carbonate and silicate phases. Group I is carbonate‐dominated with variable proportions of silicate minerals, whereas Group II is silicate‐dominated with small proportions of carbonates. Trace element analysis by LA‐ICPMS for the two groups of MS inclusions yields remarkable differences. Group I inclusions exhibit remarkably lower REE contents than Group II inclusions, with significant LREE enrichment and large fractionation between LREE and HREE in the chondrite‐normalized REE diagram. In contrast, Group II inclusions show rather flat REE patterns with insignificant fractionation between LREE and HREE. In the primitive mantle‐normalized spidergram, Group I inclusions exhibit positive anomalies of Zr and Hf, whereas Group II inclusions show negative anomalies of Zr and Hf. Nevertheless, both groups exhibit positive anomalies of Ba, U, Pb and Sr, but negative anomalies of Nb and Ta, resembling the composition of common continental crust. Group I inclusions have higher Ba and U contents than Group II inclusions. Combined with petrological observations, the two groups of MS inclusions are interpreted as having crystallized from composite silicate and carbonate melts during continental subduction‐zone metamorphism. The differences in trace element composition between the two groups are primarily attributed to the proportions of carbonate and silicate phases in the MS inclusions. The silicate melts were derived from the breakdown of hydrous minerals such as paragonite and phengite, whereas the occurrence of carbonate melts indicates involvement of carbonate minerals in the partial melting and thus has great bearing on recycling of supracrustal carbon into the mantle. The coexistence of silicate and carbonate melts in the eclogitic garnet provides insights into the nature of hydrous melts in the subduction factory.     

Chemical variation in metabasites from a proterozoic amphibolite-granulite transition zone,South Norway

The metabasites were originally minor intrusions which are now characterised by wholly metamorphic textures and mineral assemblages diagnostic of an amphibolite-granulite facies transition. Two forms of chemical variation can be distinguished: (1) an igneous-type differentiation, involving tholeiitic iron enrichment accompanied by increases in some incompatible elements, and decreases in the transition trace elements; (2) metamorphic fractionation effects resulting in deficiencies in K, Rb, Sr, Ba, Zr, and enhancement in Na in the highest grade rocks. These distributions closely parallel those in the host acid-intermediate charnockitic gneisses. The data preclude the possibility that the deficiencies were caused by removal of melts from the granulites. The metamorphism closely followed intrusion, and it is unlikely that the fractionations were caused by secondary dehydration of once hydrous assemblages. The preferred model involves intrusion and crystallisation directly under high-grade conditions, possibly with CO₂-rich fluids playing an important role in suppressing the formation of hydrous minerals.     

General characteristics of the geochemical evolution of silicic melts during the development of massive sulfide magmatic ore systems: Evidence from the investigation of melt inclusions

The investigation of melt inclusions in the minerals of volcanic rocks from the massive sulfide deposits of Siberia and the Urals revealed some specific features in the development of their magmatic ore systems. It was shown that the petrochemical and rare earth element compositions of melt inclusions reflect the geodynamic conditions of their formation: island arc conditions for the massive sulfide deposits of Rudny Altai, eastern Tuva, and the Salair Range and a back arc basin environment for the Yaman-Kasy deposit. The silicic melts of inclusions from the volcanic rocks of massive sulfide deposits show some specific features with respect to the contents of volatile components. In all of the ore deposits studied, fluorine content was always low (0.03–0.08 wt %), whereas chlorine content (0.13–0.28 wt %) was higher than the average value for silicic melts (0.17 wt %). There is a strong differentiation of water content in melt inclusions, both between deposits and between various volcanics from a single deposit. Ore-bearing melts show the highest water contents of 3.34–4.07 wt %. High Cu contents in the silicic melts of the Yubileinoe and Kyzyl-Tashtyg deposits (up to 7118 and 3228 ppm, respectively) may indicate the affinity of some ore components to particular silicic magmas. This is supported by the elevated contents of Cu in the porphyry Cu deposits of Romania (Valea Morii), Mongolia (Bayan Ula), and Bolivia. On the other hand, the silicic melts of inclusions from the molybdenum-uranium deposit of the Strel’tsovka ore field show high contents of another group of ore components (U and F).     

锡在花岗质熔体和流体中的性质及分配行为研究进展

元素在流/熔体间的交换、分配过程是岩浆热液矿床形成的重要环节,作为与岩浆活动有密切成因联系的典型矿种之一,锡在花岗质熔体和流体中的存在形式、分配行为及其影响因素是认识其成矿机理的关键。锡在花岗质熔体和流体中的分配特征不仅受温度、压力、氧逸度等条件的制约,流体组成和熔体的NBO/T（非桥氧键/桥氧键）、碱含量、AlK/Al(总碱与铝含量比)也是制约锡分配行为的重要因素;挥发分F、Cl对锡在流体、熔体中的地球化学行为影响尤为明显。     

DETERMINATION OF FLUORINE, CHLORINE, BROMINE AND IODINE IN SEVEN GEOCHEMICAL REFERENCE SAMPLES

The concentrations of fluorine, chlorine, bromine and iodine of seven geochemical reference samples have been determined. Analytical techniques were neutron activation analysis for chlorine, bromine and iodine and ion-selective potentiometry for fluorine. After irradiation of the samples, these halogens were separated from the matrix elements by pyrohydrolysis in presence of vanadium (V) oxide. This extraction allows to measure the four halogens in the same sample.     

蛇绿岩中铬铁岩母岩浆的富Ca特征:矿物包裹体证据

铬铁矿作为蛇绿岩中的重要矿产,其成矿母岩浆性质及演化一直存在较大争议.铬铁矿的矿物包裹体同时或先于铬铁矿结晶,其成分和类别能很好地记录成矿母岩浆性质和演化过程.土耳其Pozant?-Karsant?蛇绿岩不同类型铬铁岩的铬铁矿中发现了多种类型包裹体:不含水硅酸盐矿物（如橄榄石和单斜辉石）、含水硅酸盐矿物（如角闪石和金云母）、复合型矿物包裹体（如蛇纹石、硅灰石和单斜辉石的复合型包裹体）和不常见矿物（如磷灰石、铂族元素硫化物）.含水矿物包裹体的出现以及矿物的高Mg#特征（如橄榄石Fo=95.4~97.1;单斜辉石Mg#=92.0~99.9;角闪石Mg#=88.9~99.8）表明结晶铬铁矿的母岩浆具有富水、富Mg的特征.同时,除钙铬榴石和磷灰石的包裹体外,在铬铁矿中首次发现富Ca矿物方解石和硅灰石,其中方解石和菱镁矿以复合型包裹体形式产出,硅灰石则分布于蛇纹石矿物包裹体中.这些富Ca矿物的出现以及硅酸盐矿物的高CaO含量均揭示了铬铁岩母岩浆的富Ca特征.母岩浆中的Ca组分可能来源于俯冲板块中富Ca岩石/矿物的部分熔融,Ca离子的大量出现使得Cr3+在熔体中更加稳定,同时富Ca矿物的结晶促进了岩浆中Cr的进一步富集而利于铬铁矿的大量结晶沉淀.      

金在花岗质熔体中溶解度的初步实验研究

以合成花岗岩、水、不同浓度的盐酸溶液、氢氟酸溶液作为反应初始物,在850℃,100 MPa,接近于NNO的条件下开展了金在不同花岗质熔体中溶解度的实验研究,实验固液相产物中的金含量使用石墨炉原子吸收法测定。实验结果显示,金在花岗质熔体中的溶解度变化范围为1.87～156.62μg/g,流体相中金的溶解度为0.31～6.92μg/g;金在熔体相中的溶解度较其在共存液相中的高。花岗质熔体相中金的溶解度明显受熔体化学组成的影响,过碱性富钠花岗质熔体中金的溶解度明显高些;金在花岗质熔体中的溶解度随着熔体中Na2O/K2O摩尔比增大而增大;在氟氯共存岩浆体系中,氟含量变化对金在熔体相中的溶解度影响不明显,而液相中氯含量增大有利于提高金在流体相中的含量。     

洋中脊富钛铁氧化物辉长岩成因的一个新思路:以西南印度洋脊ODP 735B岩心为例

西南印度洋脊的ODP 735B岩心中拥有大量富含钛铁氧化物的含氧化物辉长岩,此现象在岩性单元Ⅳ中表现尤为显著.同时,岩性单元1中主要硅酸盐矿物亦具有独特的成分变化趋势.以前研究将造成岩性单元I中氧化物辉长岩成因和主要造岩矿物成分变化趋势归因于具浮力的、高度分异的富钛铁熔体的作用,这些熔体应形成于735B钻孔之下或其附近...     

The speciation of water in silicate melts

Previous models of water solubility in silicate melts generally assume essentially complete reaction of water molecules to hydroxyl groups. In this paper a new model is proposed that is based on the hypothesis that the observed concentrations of molecular water and hydroxyl groups in hydrous silicate glasses reflect those of the melts from which they were quenched. The new model relates the proportions of molecular water and hydroxyl groups in melts via the following reaction describing the homogeneous equilibrium between melt species: H₂O_molecular (melt) + oxygen (melt) = 2OH (melt). An equilibrium constant has been formulated for this reaction and species are assumed to mix ideally. Given an equilibrium constant for this reaction of 0.1–0.3, the proposed model can account for variations in the concentrations of molecular water and hydroxyl groups in melts as functions of the total dissolved water content that are similar to those observed in glasses. The solubility of molecular water in melt is described by the following reaction: H₂O (vapor) = H₂O_molecular (melt).These reactions describing the homogeneous and heterogeneous equilibria of hydrous silicate melts can account for the following observations: the linearity between f_H2O and the square of the mole fraction of dissolved water at low total water contents and deviations from linearity at high total water contents; the difference between the partial molar volume of water in melts at low total water contents and at high total water contents; the similarity between water contents of vapor-saturated melts of significantly different compositions at high pressures versus the dependence on melt composition of water solubility in silicate melts at low pressures; and the variations of viscosity, electrical conductivity, the diffusivity of “water,” the diffusivity of cesium, and phase relationships with the total dissolved water contents of melts.This model is thus consistent with available observations on hydrous melt systems and available data on the species concentrations of hydrous glasses and is easily tested, since measurements of the concentrations of molecular water and hydroxyl groups in silicate glasses quenched from melts equilibrated over a range of conditions and total dissolved water contents are readily obtainable.     

The role of H2O in rapid emplacement and crystallization of granite pegmatites: resolving the paradox of large crystals in highly undercooled melts

Granite pegmatite sheets in the continental crust are characterized by very large crystals. There has been a shift in viewing pegmatites as products of very slow cooling of granite melts to viewing them as products of crystal growth in undercooled liquids. With this shift there has been a renewed debate about the role of H₂O in the petrogenesis of pegmatites. Based on data on nucleation of minerals and new viscosity models for hydrous granite melts, it is argued that H₂O is the essential component in the petrogenesis of granite pegmatites. H₂O is key to reducing the viscosity of granite melts, which enhances their transport within the crust. It also dramatically reduces the glass transition temperature, which permits crystallization of melts at hundreds of degrees below the thermodynamic solidus, which has been demonstrated by fluid inclusion studies and other geothermometers. Published experimental data show that because H₂O drastically reduces the nucleation rates of silicate minerals, the minerals may not be able to nucleate until melt is substantially undercooled. In a rapidly cooling intrusion, nucleation starts at its highly undercooled margins, followed by inward crystal growth towards its slower-cooling, hotter core. Delay in nucleation may be caused by competition for crystallization by several minerals in the near-eutectic melts and by the very different structures of minerals and the highly hydrated melts. Once a mineral nucleates, however, it may grow rapidly to a size that is determined by the distance between the site of nucleation and the point in the magma at which the temperature is approximately that of the mineral’s liquidus, assuming components necessary for mineral growth are available along the growth path. Granite pegmatites are apparently able to retain H₂O during most of their crystallization histories within the confinement of their wall rocks. Pegmatitic texture is a consequence of delayed nucleation and rapid growth at large undercooling, both of which are facilitated by high H₂O (±Li, B, F and P) contents in granite pegmatite melts. Without retention of H₂O the conditions for pegmatitic textural growth may be difficult to achieve. Loss of H₂O due to decompression and venting leads to microcrystalline texture and potentially glass during rapid cooling as seen in rhyolites. In contrast, slow cooling within a large magma chamber promotes continuous exsolution of H₂O from crystallizing magma, growth of equant crystals, and final solidification at the thermodynamic solidus. These are the characteristics of normal granites that distinguish them from pegmatites.     

Metasomatic events recorded in ultramafic xenoliths from the Hyblean area (Southeastern Sicily, Italy)

Three types of ultramafic xenoliths from the Hyblean area (Sicily) show prime evidence for mantle metasomatism, namely: 1) Spinel-facies depleted harzburgite veined by phlogopite-bearing clinopyroxenite; 2) Amphibole-bearing harzburgite; and 3) Al-spinel websterite. (2) and (3) exhibit glassy pockets having respectively mugearitic and basanitic compositions, but a little amount of glass with low Ca and very low alkalis in (2). Glasses generally show trace element distributions consistent with the partial melting of pargasite-dominated mineral assemblages. Abundant Ca-Mg-carbonate globules immersed in these glassy pockets testify to immiscibility between silicate and carbonatite melts. Silicate melts and hydrous-silicate supercritical fluids, which underwent phase separation during fluxing throughout the semi-brittle lithospheric mantle, may account for such metasomatizing processes. The nature and abundance of some fluid-mobile elements in glasses and hydrous minerals (especially the Ca-poor glass, with B?=?59 ppm, Li?=?27 ppm, Ba?=?700 ppm and phlogopite, with Ba?=?8,465 ppm, Sr?=?260 ppm, F?=?5,700 ppm) suggest that some hydrous fluids may derive from hydrothermally altered oceanic crust. Conversely, metasomatizing silicate melts probably have a deep-seated origin. These results confirm previous suggestions on the key role of mantle metasomatism in the origin of some alkaline Hyblean magmas.     

Melting of hydrous pyroxenites with alkali amphiboles in the continental mantle: 2. Trace element compositions of melts and minerals

The trace element compositions of melts and minerals from high-pressure experiments on hydrous pyroxenites containing K-richterite are presented. The experiments used mixtures of a third each of the natural minerals clinopyroxene, phlogopite and K-richterite, some with the addition of 5% of an accessory phase ilmenite, rutile or apatite. Although the major element compositions of melts resemble natural lamproites, the trace element contents of most trace elements from the three-mineral mixture are much lower than in lamproites. Apatite is required in the source to provide high abundances of the rare earth elements, and either rutile and/or ilmenite is required to provide the high field strength elements Ti, Nb, Ta, Zr and Hf. Phlogopite controls the high levels of Rb, Cs and Ba.Since abundances of trace elements in the various starting mixtures vary strongly because of the use of natural minerals, we calculated mineral/melt partition coefficients (D_Min/melt) using mineral modes and melting reactions and present trace element patterns for different degrees of partial melting of hydrous pyroxenites. Rb, Cs and Ba are compatible in phlogopite and the partition coefficient ratio phlogopite/K-richterite is high for Ba (1 3 6) and Rb (12). All melts have low contents of most of the first row transition elements, particularly Ni and Cu ((0.1–0.01) × primitive mantle). Nickel has high D_Min/melt for all the major minerals (12 for K-richterite, 9.2 for phlogopite and 5.6 for Cpx) and so behaves at least as compatibly as in melting of peridotites. Fluorine/chlorine ratios in melts are high and D_Min/melt for fluorine decreases in the order apatite (2.2) > phlogopite (1.5) > K-richterite (0.87). The requirement for apatite and at least one Ti-oxide in the source of natural lamproites holds for mica pyroxenites that lack K-richterite. The results are used to model isotopic ageing in hydrous pyroxenite source rocks: phlogopite controls Sr isotopes, so that lamproites with relatively low ⁸⁷Sr/⁸⁶Sr must come from phlogopite-poor source rocks, probably dominated by Cpx and K-richterite. At high pressures (>4 GPa), peritectic Cpx holds back Na, explaining the high K₂O/Na₂O of lamproites.     

Solubility of carbon dioxide in melts of andesite,tholeiite, and olivine nephelinite composition to 30 kbar pressure

Carbon dioxide solubilities in H₂O-free hydrous silicate melts of natural andesite (CA), tholeiite (K 1921), and olivine nephelinite (OM1) compositions have been determined employing carbon-14 beta-track mapping techniques. The CO₂ solubility increases with increasing pressure, temperature, and degree of silica-undersaturation of the silicate melt. At 1650° C, CO₂ solubility in CA increases from 1.48±0.05 wt % at 15 kbar to 1.95±0.03 wt % at 30 kbar. The respective solubilities in OM1 are 3.41±0.08 wt % and 7.11±0.10 wt %. The CO₂ solubility in K1921 is intermediate between those of CA and OM1 compositions. At lower temperatures, the CO₂ contents of these silicate melts are lower, and the pressure dependence of the solubility is less pronounced. The presence of H₂O also affects the CO₂ solubility (20–30% more CO₂ dissolves in hydrous than in H₂O-free silicate melts); the solubility curves pass through an isothermal, isobaric maximum at an intermediate CO₂/(CO₂+H₂O) composition of the volatile phase. Under conditions within the upper mantle where carbonate minerals are not stable and CO₂ and H₂O are present a vapor phase must exist. Because the solubility of CO₂ in silicate melts is lower than that of H₂O, volatiles must fractionate between the melt and vapor during partial melting of peridotite. Initial low-temperature melts will be more H₂O-rich than later high-temperature melts, provided vapor is present during the melting. Published phase equilibrium data indicate that the compositional sequence of melts from peridotite +H₂O+CO₂ parent will be andesite-tholeiite-nephelinite with increasing temperature at a pressure of about 20 kbar. Examples of this sequence may be found in the Lesser Antilles and in the Indonesian Island Arcs.     

Pressure dependence of viscosity of rhyolitic melts

Viscosity of silicate melts is a critical property for understanding volcanic and igneous processes in the Earth. We investigate the pressure effect on the viscosity of rhyolitic melts using two methods: indirect viscosity inference from hydrous species reaction in melts using a piston cylinder at pressures up to 2.8 GPa and direct viscosity measurement by parallel-plate creep viscometer in an internally-heated pressure vessel at pressures up to 0.4 GPa. Comparison of viscosities of a rhyolitic melt with 0.8 wt% water at 0.4 GPa shows that both methods give consistent results. In the indirect method, viscosities of hydrous rhyolitic melts were inferred based on the kinetics of hydrous species reaction in the melt upon cooling (i.e., the equivalence of rheologically defined glass transition temperature and chemically defined apparent equilibrium temperature). The cooling experiments were carried out in a piston-cylinder apparatus using hydrous rhyolitic samples with 0.8-4 wt% water. Cooling rates of the kinetic experiments varied from 0.1 K/s to 100 K/s; hence the range of viscosity inferred from this method covers 3 orders of magnitude. The data from this method show that viscosity increases with increasing pressure from 1 GPa to 3 GPa for hydrous rhyolitic melts with water content ?0.8 wt% in the high viscosity range. We also measured viscosity of rhyolitic melt with 0.13 wt% water using the parallel-plate viscometer at pressures 0.2 and 0.4 GPa in an internally-heated pressure vessel. The data show that viscosity of rhyolitic melt with 0.13 wt% water decreases with increasing pressure. Combining our new data with literature data, we develop a viscosity model of rhyolitic melts as a function of temperature, pressure and water content.     

Partitioning of halogens between mantle minerals and aqueous fluids: implications for the fluid flow regime in subduction zones

We have performed phase equilibrium experiments in the system forsterite–enstatite–pyrope-H₂O with MgCl₂ or MgF₂ at 1,100 °C and 2.6 GPa to constrain the solubility of halogens in the peridotite mineral assemblage and the fluid–mineral partition coefficients. The chlorine solubility in forsterite, enstatite and in pyrope is very low, 2.1–3.9 and 4.0–11.4 ppm, respectively, and it is independent of the fluid salinity (0.3–30 wt% Cl), suggesting that some intrinsic saturation limit in the crystal is reached already at very low chlorine concentrations. Chlorine is therefore exceedingly incompatible in upper-mantle minerals. The fluorine solubility is 170–336 ppm in enstatite and 510–1,110 ppm in pyrope, again independent of fluid salinity. Forsterite dissolves 1,750–1,900 ppm up to a fluid salinity of 1.6 wt% F. At higher fluorine contents in the system, forsterite is replaced by the minerals of the humite group. The lower solubility of chlorine by three orders of magnitude when compared to fluorine is consistent with increasing lattice strain. Fluid–mineral partition coefficients are 10⁰–10² for fluorine and 10³–10⁵ for chlorine. Since the latter values are orders of magnitude higher than those for hydroxyl partitioning, fluid flow from the subducting slab through the mantle wedge will lead to an efficient sequestration of H₂O into the nominally anhydrous minerals in the wedge, whereas chlorine becomes enriched in the residual fluid. Simple mass balance calculations reveal that rock–fluid ratios of up to >3,000 are required to produce the elevated Cl/H₂O ratios observed in some primitive arc magmas. Accordingly, fluid flow from the subducted slab into the zone of melting in the mantle wedge does not only occur rapidly in narrow channels, but at least in some subduction zones, fluid pervasively infiltrates the mantle peridotite and interacts with a large volume of the mantle wedge. Together with the Cl/H₂O ratios of primitive arc magmas, our data therefore constrain the fluid flow regime below volcanic arcs.     

Structure and properties of fluorine-bearing aluminosilicate melts: the system Na2O-Al2O3-SiO2-F at 1 atm

The chemical interaction between fluorine and highly polymerized sodium aluminosilicate melts [Al/(Al+Si)= 0.125–0.250 on the join NaAlO₂-SiO₂] has been studied with Raman spectroscopy. Fluorine is dissolved to form F^– ions that are electrically neutralized with Na⁺ or Al³⁺. There is no evidence for association of fluorine with either Si⁴⁺ or Al³⁺ in four-fold coordination and no evidence of fluorine in six-fold coordination with Si⁴⁺ in these melt compositions. Upon solution of fluorine nonbridging oxygens are formed and are a part of structural units with nonbridging oxygen per tetrahedral cations (NBO/T) about 2 and 1. The proportions of these two depolymerized units in the melts increase systematically with increasing F/(F+O) at constant Al/(Al+Si) and with decreasing Al/(Al+Si) at constant F/(F+O). Depolymerization (increasing NBO/T) of silicate melts results from a fraction of aluminum and alkalies (in the present study; Na⁺) reacting to form fluoride complexes. In this process an equivalent amount of Na⁺ (orginally required for Al-³⁺charge-balance) or Al³⁺ (originally required Na⁺ to exist in tetrahedral coordination) become network-modifiers.The structural data have been used to develop a method for calculating the viscosity of fluorine-bearing sodium aluminosilicate melts at 1 atm. Where experimental viscosity data are available, the calculated and measured values are within 5% of each other.A method is also suggested by which the liquidus phase equilibria of fluorine-bearing aluminosilicate melts may be predicted. In accord with published experimental data it is suggested, for example, that — on the basis of the determined solubility mechanism of fluorine in aluminosilicate melts — with increasing fluorine content of feldspar-quartz systems, the liquidus boundaries between aluminosilicate minerals (e.g., feldspars) and quartz shift away from silica.     

Iodine (and Other Halogens) in Twenty Six Geological Reference Materials by ICP-MS and Ion Chromatography

Analytical results for iodine in twenty six geological reference materials (RM) are presented. Bromine, fluorine and chlorine were also determined in some samples. Pyrohydrolysis in a heated quartz tube under a wet oxygen flow was used for the separation of the halogens from the matrix and the evolved gas was absorbed in a trap solution. The halogens were measured by ICP-MS and ion chromatography (IC). All four halogens can be collected in the trap solution from one combustion procedure. The analysed samples range in type from igneous rocks to terrestrial and marine sediments. Precision, detection limits, and accuracy are also presented.