Occurrence and origin of marialitic scapolite in the Humboldt lopolith,N.W. Nevada

The occurrence and origin of marialitic scapolite in the Humboldt lopolith was investigated in the field and in the laboratory using petrographic and experimental techniques. Scapolite occurs in three modes: as a pervasive replacement of plagioclase and other minerals in gabbro, diorite and extrusive rocks; as a poikiloblastic mineral in scapolitite dikes; and as a fracture-filling mineral with analcime, albite and sphene in scapolite veins. Additional secondary minerals associated with scapolite include epidote, prehnite, hornblende and diopside-salite clinopyroxene. Relations with these minerals suggest that most marialitic scapolite grew at temperatures around 400° C. Scapolite composition varies from EqAn₁₂ to EqAn₃₇, containing from 72 to 96 atomic% Cl in the R position. Experiments on systems of similar compositions indicate that NaCl-H₂O fluid having more than 40 mol% NaCl is needed to stabilize the scapolite.Variation in scapolite compositions is due to thermal and fluid compositional gradients normal to conduits of hydrothermal fluids, and occurs on a scale up to 100 m. The likely source of Na and Cl is pre-existing evaporites or evaporitic brine derived from the wallrocks. Salinity could have been increased to a level sufficient to stabilize scapolite by hydration of an originally dry magma, possibly aided by hydrothermal boiling. Results may be applied to hydrothermal alteration in areas of rifting or back-arc spreading, and in mid-ocean ridge hydrothermal systems.     

Cl/Br of scapolite as a fluid tracer in the earth's crust: insights into fluid sources in the Mary Kathleen Fold Belt,Mt. Isa Inlier,Australia

A combination of analytical methods, including trace element analysis of Br in scapolite by LA‐ICP‐MS, was employed to unravel the fluid–rock interaction history of the Mary Kathleen Fold Belt of northern Australia. Halogen ratios in the metamorphic and hydrothermally derived scapolite from a range of rock‐types record interaction between the host rocks and magmatic‐hydrothermal fluids derived from granite plutons and regional metamorphism. The results show that halite‐dissolution supplied at best only minor chlorine to fluids in the Fold Belt. Chlorine/bromine ratios in metamorphic scapolite indicate that fluids were dominantly derived from basinal brines formed from sub‐aerial evaporation of seawater beyond the point of halite saturation. This bittern fluid infiltrated the underlying sedimentary sequences prior to regional metamorphism. Zoned scapolite in a major late metamorphic mineralized shear‐zone records three discrete pulses of magmatic and metamorphic fluid, and it is suggested that fluid mixing may have assisted mineralization along and around this shear‐zone. As a crucial prerequisite for halogen fluid tracer studies using scapolite, we find in our samples that Cl and Br do not fractionate when incorporated in scapolite. Furthermore, unaltered rims of heavily retrogressed scapolite show indistinguishable Cl/Br signatures compared with fresh grains from the same sample indicating retrograde metamorphism did not significantly affect Cl and Br signatures in scapolite group minerals.     

The origin of scapolite in the regionally metamorphosed rocks of Mary Kathleen,Queensland, Australia

Scapolite at Mary Kathleen (North-Western Queensland) occurs in calcareous and non-calcareous metapelites, acid and basic metavolcanics and metadolerites. Graphical treatment of the relationship between scapolite composition (Me%) and the host rock oxide ratios CaO/Na₂O and Al₂O₃/(CaO + Na₂O) reveals the following points:

1. The calcareous metapelites are also very sodic.
2. Scapolite in calcareous metapelites is more marialitic than that in low-calcium equivalents.
3. In graphs of Me% against CaO/Na₂O and Al₂O₃/(CaO + Na₂O) the metasediments and the metaigneous rocks show markedly different trends.

It is concluded that scapolite in the metasediments originated by isochemical metamorphism of shales and marls containing evaporitic halite. The local abundance of halite was the main control on the composition and distribution of the scapolite, but the relative abundance of CaO and Na₂O was a modifying factor. In the metaigneous rocks scapolite formed metasomatically during regional metamorphism by the introduction of volatile-rich fluids derived from the adjacent evaporitic sediments. The relative availability of CO₂ and Cl₂ again appears to have been the primary control on scapolite composition and may in turn have been controlled by bulk rock composition.     

Metamorphic and post-metamorphic fluid flow in the low-grade rocks of the Harlech Dome, north Wales

A combination of fluid inclusion, stable isotope and geochemical techniques has been used to study the nature of fluids present and their behaviour during Caledonian low-grade metamorphism of the Harlech Dome, north Wales. Fluid inclusion studies show that in most of the metasedimentary sequence the peak metamorphic fluid was an aqueous Na–K–Cl brine but in the graphitic Clogau Formation and in parts of the overlying Maentwrog Formation immiscible H₂O-rich and CH₄-rich fluids coexisted. Late-stage inclusions are of calcium-rich brine and a dilute aqueous fluid. The chemical composition of chlorite in metamorphic veins and rocks varies between different formations and quartz-oxygen isotopic compositions show considerable variation between different units. Both of these features are taken to indicate that there was little or no pervasive movement of fluid between different units at the peak of metamorphism. After the metamorphic peak there was focused flow of fluid upward through the sequence along fractures, in response to end-Caledonian uplift and unloading. Where the migrating fluid crossed the graphitic shales, interaction between the fluid and the shales gave rise to the formation of the auriferous veins of the Dolgellau Gold Belt. Subsequent to this mineralizing event there was widespread development of ¹⁸O-enriched calcites and micas. In the case of vein minerals it is possible that these crystallized directly from late-stage fluids at lower temperature than the quartz in the same veins. Alternatively, the original vein minerals may have re-equilibrated with later ¹⁸O-enriched or cooler fluid. In the case of muscovites in the rock matrix it is proposed that the isotopically heavy compositions are the result of re-equilibration of initially light grains with an introduced fluid, requiring considerable influx of fluid. This event may relate to either of two late-stage fluids observed as inclusions.     

Calc-silicate reactions and bedding-controlled isotopic exchange in the Notch Peak aureole, Utah: implications for differential fluid fluxes with metamorphic grade

Fluid compositions and bedding‐scale patterns of fluid flow during contact metamorphism of the Weeks Formation in the Notch Peak aureole, Utah, were determined from mineralogy and stable isotope compositions. The Weeks Formation contains calc‐silicate and nearly pure carbonate layers that are interbedded on centimetre to decimetre scales. The prograde metamorphic sequence is characterized by the appearance of phlogopite, diopside, and wollastonite. By accounting for the solution properties of Fe, it is shown that the tremolite stability field was very narrow and perhaps absent in the prograde sequence. Unshifted oxygen and carbon isotopic ratios in calcite and silicate minerals at all grades, except above the wollastonite isograd, show that there was little to no infiltration of disequilibrium fluids. The fluid composition is poorly constrained, but X(CO₂)_fluid must have been >0.1, as indicated by the absence of talc, and has probably increased with progress of decarbonation reactions. The occurrence of scapolite and oxidation of graphite in calc‐silicate beds of the upper diopside zone provide the first evidence for limited infiltration of external aqueous fluids. Significantly larger amounts of aqueous fluid infiltrated the wollastonite zone. The aqueous fluids are recorded by the presence of vesuvianite, large decreases in δ¹⁸O values of silicate minerals from c. 16‰ in the diopside zone to c. 10‰ in the wollastonite zone, and extensive oxidation of graphite. The carbonate beds interacted with the fluids only along margins where graphite was destroyed, calcite coarsened, and isotopic ratios shifted. The wollastonite isograd represents a boundary between a high aqueous fluid‐flux region on its higher‐grade side and a low fluid‐flux region on its lower‐grade side. Preferential flow of aqueous fluids within the wollastonite zone was promoted by permeability created by the wollastonite‐forming reaction and the natural tendency of fluids to flow upward and down‐temperature near the intrusion‐wall rock contact.     

Evolution of metamorphic fluid recorded in granulite facies metacarbonate rocks from the middle segment of the Mogok metamorphic belt in central Myanmar

The Mogok metamorphic belt of Palaeogene age, which records subduction‐ and collision‐related events between the Indian and Eurasian plates, lies along the western margin of the Shan plateau in central Myanmar and continues northwards to the eastern Himalayan syntaxis. Reaction textures of clinohumite‐ and scapolite‐bearing assemblages in Mogok granulite facies metacarbonate rocks provide insights into the drastic change in fluid composition during exhumation of the collision zone. Characteristic high‐grade assemblages of marble and calcsilicate rock are clinohumite+forsterite+spinel+phlogopite+pargasite/edenite+calcite+dolomite, and scapolite+diopside+anorthite+quartz+calcite respectively. Calculated petrogenetic grids in CaO–MgO–Al₂O₃–SiO₂–H₂O–CO₂ and subsets of this system were employed to deduce the pressure–temperature–fluid evolution of the clinohumite‐ and scapolite‐bearing assemblages. These assemblages suggest higher temperature (>780–810°C) and [=CO₂/(CO₂+H₂O) >0.17–0.60] values in the metamorphic fluid for the peak granulite facies stage, assuming a pressure of 0.8 GPa. Calcite grains commonly show exsolution textures with dolomite particles, and their reintegrated compositions yield temperatures of 720–880°C. Retrograde reactions are mainly characterized by a reaction zone consisting of a dolomite layer and a symplectitic aggregate of tremolite and dolomite grown between clinohumite and calcite in marble, and a replacement texture of scapolite by clinozoisite in calcsilicate rock. These textures indicate that the retrograde reactions developed under lower temperature (<620°C) and (<0.08–0.16) conditions, assuming a pressure of 0.5 GPa. The metacarbonate rocks share metamorphic temperatures similar to the Mogok paragneiss at the peak granulite facies stage. The values of the metacarbonate rock at peak metamorphic stage are, however, distinctly higher than those previously deduced from carbonate mineral‐free paragneiss. Primary clinohumite, phlogopite and pargasite/edenite in marble have F‐rich compositions, and scapolite in calcsilicate rock contains Cl, suggesting a contrast in the halogen compositions of the metamorphic fluids between these two lithologies. The metamorphic fluid compositions were probably buffered within each lithology, and the effective migration of metamorphic fluid, which would have extensively changed the fluid compositions, did not occur during the prograde granulite facies stage throughout the Mogok metamorphic belt. The lower conditions of the Mogok metacarbonate rocks during the retrograde stage distinctly contrast with higher conditions recorded in metacarbonate rocks from other metamorphic belts of granulite facies. The characteristic low conditions were probably due to far‐ranging infiltration of H₂O‐dominant fluid throughout the middle segment of the Mogok metamorphic belt under low‐amphibolite facies conditions during the exhumation and hydration stage.     

Composition of barian mica in multiphase solid inclusions from orogenic garnet peridotites as evidence of mantle metasomatism in a subduction zone setting

Multiphase solid inclusions in minerals formed at ultra-high-pressure (UHP) provide evidence for the presence of fluids during deep subduction. This study focuses on barian mica, which is a common phase in multiphase solid inclusions enclosed in garnet from mantle-derived UHP garnet peridotites in the Saxothuringian basement of the northern Bohemian Massif. The documented compositional variability and substitution trends provide constraints on crystallization medium of the barian mica and allow making inferences on its source. Barian mica in the multiphase solid inclusions belongs to trioctahedral micas and represents a solid solution of phlogopite KMg₃(Si₃Al)O₁₀(OH)₂, kinoshitalite BaMg₃(Al₂Si₂)O₁₀(OH)₂ and ferrokinoshitalite BaFe₃(Al₂Si₂)O₁₀(OH)₂. In addition to Ba (0.24–0.67 apfu), mica is significantly enriched in Mg (X_Mg ~ 0.85 to 0.95), Cr (0.03–0.43 apfu) and Cl (0.04–0.34 apfu). The substitution vector involving Ba in the I-site which describes the observed chemical variability can be expressed as BaFe^IVAlClK_?1Mg_?1Si_?1(OH)_?1. A minor amount of Cr and ^VIAl enters octahedral sites following a substitution vector ^VI(Cr,Al)₂□^VI(Mg,Fe)_?3 towards chromphyllite and muscovite. As demonstrated by variable Ba and Cl contents positively correlating with Fe, barian mica composition is partly controlled by its crystal structure. Textural evidence shows that barian mica, together with other minerals in multiphase solid inclusions, crystallized from fluids trapped during garnet growth. The unusual chemical composition of mica reflects the mixing of two distinct sources: (1) an internal source, i.e. the host peridotite and its garnet, providing Mg, Fe, Al, Cr, and (2) an external source, represented by crustal-derived subduction-zone fluids supplying Ba, K and Cl. At UHP–UHT conditions recorded by the associated diamond-bearing metasediments (c. 1100 °C and 4.5 GPa) located above the second critical point in the pelitic system, the produced subduction-zone fluids transporting the elements into the overlying mantle wedge had a solute-rich composition with properties of a hydrous melt. The occurrence of barian mica with a specific chemistry in barium-poor mantle rocks demonstrates the importance of its thorough chemical characterization.     

Halogen contents of eclogite facies fluid inclusions and minerals: Caledonides,western Norway

Primary multiphase brine fluid inclusions in omphacite and garnet from low‐ to medium‐temperature eclogites have been analysed for Cl, Br, I, F, Li and SO₄. Halogen contents and ratios provide information about trapped lower crustal fluids, even though the major element (Na, K, Ca) contents of inclusion fluids have been modified by fluid–mineral interactions and (step‐) daughter‐crystal formation after trapping. Halogens in the inclusion fluids were analysed with crush–leach techniques. Cl/Br and Cl/I mass ratios of eclogite fluids are in the range 31–395 and 5000–33 000, respectively. Most fluids have a Cl/Br ratio lower than modern seawater and a Cl/I ratio one order of magnitude lower than modern seawater. Fluids with the lowest Cl/Br and highest Cl/I ratios come from an eclogite that formed by hydration of granulite facies rocks, and may indicate that Br and I are fractionated into hydrous minerals. Reconstructions indicate that the inclusion fluids originally contained 500–4000 ppm Br, 1–14 ppm I and 33–438 ppm Li. Electron microprobe analyses of eclogite facies amphibole, biotite, phengite and apatite indicate that F and Cl fractionate most strongly between phengite (F/Cl mass ratio of 1469 ± 1048) and fluid (F/Cl mass ratio of 0.008), and the least between amphibole and fluid. The chemical evolution of Cl and Br in pore fluids during hydration reactions is in many ways analogous to Cl and Br in seawater during evaporation: the Cl/Br ratio remains constant until the a_H2O value is sufficiently lowered for Cl to be removed from solution by incorporation into hydrous minerals.     

Remnants of premetamorphic fluid and oxygen isotopic signatures in eclogites and garnet clinopyroxenite from the Dabie-Sulu terranes, eastern China

A combined oxygen‐isotope and fluid‐inclusion study has been carried out on high‐ and ultrahigh‐pressure metamorphic (HP/UHPM) eclogites and garnet clinopyroxenite from the Dabie‐Sulu terranes in eastern China. Coesite‐bearing eclogites/garnet clinopyroxenite and quartz eclogites have a wide range in whole‐rock δ¹⁸O_VSMOW, from 0 to 11‰. The high‐T oxygen‐isotope fractionations preserved between quartz and garnet preclude significant retrograde isotope exchange during exhumation, and the wide range in whole‐rock oxygen‐isotope composition is thought to be a presubduction signature of the precursors. Aqueous fluids with variable salinities and gas species (N₂‐, CO₂‐, or CH₄‐rich), are trapped as primary inclusions in garnet, omphacite and epidote, and in quartz blebs enclosed within eclogitic minerals. In high‐δ¹⁸O HP/UHPM rocks from Hujialin and Shima, high‐salinity brine and/or N₂ inclusions occur in garnet porphyroblasts, which also contain inclusions of coesite, Cl‐rich blue amphibole and dolomite. In contrast, in low‐δ¹⁸O eclogites from Qinglongshan and Huangzhen, the Cl concentrations in amphibole are very low, < 0.2 wt.%, and low‐salinity aqueous inclusions occur in quartz inclusions in epidote porphyroblasts and in epidote cores. These low‐salinity fluid inclusions are believed to be remnants of meteoric water, although the fluid composition was modified during pre‐ and syn‐peak HP/UHPM. Eclogites at Houshuichegou and Hetang contain CH₄‐rich fluid inclusions, coexisting with high‐salinity brine inclusions. Methane was probably formed under the influence of CO₂‐rich aqueous fluids during serpentinisation of mantle‐derived peridotites prior to or during plate subduction. Remnants of premetamorphic low‐ to high‐salinity aqueous fluid with minor N₂ and/or other gas species preserved in the Dabie‐Sulu HP/UHPM eclogites and garnet clinopyroxenite indicate a great diversity of initial fluid composition in the precursors, implying very limited fluid–rock interaction during syn‐ and post‐peak HP/UHPM.     

New constraints on the release of noble gases during in vacuo crushing and application to scapolite Br–Cl–I and Ar/Ar age determinations

The release of irradiation-produced noble gas isotopes (³⁸Ar_Cl, ⁸⁰Kr_Br, ¹²⁸Xe_I and ³⁹Ar_K) during in vacuo crushing scapolite has been investigated and is compared to quartz. Three thousand crushing strokes released 98% of fluid inclusion-hosted noble gas from quartz. In comparison, 3000 crushing strokes released only 4% of the lattice-hosted ³⁸Ar_Cl from a scapolite gem. In vacuo crushing released lattice Ar preferentially relative to lattice Kr or Xe and prolonged crushing released 88% of the lattice-hosted noble gas in 96,000 crushing strokes. We suggest fast diffusion pathways generated by crushing are an important noble gas release mechanism and we demonstrate two applications of prolonged in vacuo crushing on irradiated scapolite.Firstly, scapolite molar Br/Cl and I/Cl values are shown to vary over a similar range as crustal fluids. The Cl-rich scapolite gem from Hunza, Pakistan has Br/Cl of 0.5–0.6 × 10⁻³ and I/Cl values of 0.3–2 × 10⁻⁶, that are similar to fluids that have dissolved evaporites. In contrast, three out of four skarn-related scapolites from the Canadian Grenville Province have molar Br/Cl values of 1.5–2.4 × 10⁻³, and I/Cl values of 11–24 × 10⁻⁶, that are broadly consistent with skarn formation by magmatic fluids. The fourth Grenvillian scapolite, with only 0.02 wt% Cl, has an exceptionally elevated molar Br/Cl value of up to 54 × 10⁻³ and I/Cl of 284 × 10⁻⁶. It is unclear if these values reflect the composition of fluids formed during metamorphism or preferential incorporation of Br and I in Cl-poor meionitic scapolite.Secondly, the Grenvillian scapolites give plateau ages of between 830 Ma and 400 Ma. The oldest ages post-date regional skarn formation by 200 Myr, but are similar to feldspar cooling ages in the Province. The age variation in these samples is attributed to a combination of factors including variable thermal history and the presence of mineral sub-grains in some of the samples. These sub-grains control the release of ³⁹Ar_K, ³⁸Ar_Cl and ⁴⁰Ar* during in vacuo crushing as well as the samples ⁴⁰Ar* retentivity in nature. Scapolite is suggested as a possible analogue for K-feldspar in thermochronologic studies.     

Fluid-rock history of granulite facies humite-marbles from Ambasamudram, southern India.

An extensive humite‐bearing marble horizon within a supracrustal sequence at Ambasamudram, southern India, was studied using petrological and stable isotopic techniques to define its metamorphic history and fluid characteristics. At peak metamorphic temperatures of 775±73°C, based on calcite‐graphite carbon isotope thermometry, the mineral assemblages suggest layer‐by‐layer control of fluid compositions. Clinohumite + calcite‐bearing assemblages suggest X_CO2 < 0.4 (at 700°C and 5 kbar), calcite + forsterite + K‐feldspar‐bearing assemblages suggest X_CO2>0.9 (at 790°C); and local wollastonite + scapolite + grossular‐bearing zones formed at X_CO2 of c. 0.3. Retrograde reaction textures such as scapolite + quartz symplectites after feldspar and calcite and replacement of dolomite + diopside or tremolite+dolomite after calcite+forsterite or calcite+clinohumite are indicative of retrogression under high X_CO2 conditions. Calcite preserves late Proterozoic carbon and oxygen isotopic signatures and the marble lacks evidence for extensive retrograde fluid infiltration, while during prograde metamorphism the possible infiltration of aqueous fluids did not produce significant isotopic resetting. Isotopic zonation of calcite and graphite grains was likely produced by localized CO₂ fluid infiltration during retrogression. Contrary to the widespread occurrence of humite‐marbles related to retrograde aqueous fluid infiltration, the Ambasamudram humite‐marbles record a prograde‐to‐peak metamorphic humite formation and retrogression under conditions of low X_H2O.     

Metasomatism of gabbro – mineral replacement and element mobilization during the Sveconorwegian metamorphic event

Widespread metasomatism affected the 100 km long and 25 km wide Proterozoic Bamble and Modum‐Kongsberg sectors, South Norway, resulting in the chemical and mineralogical transformation of wide segments of continental crust. Scapolitization was associated with veining, and was followed by albitization, transforming metagabbros pervasively over large areas. Fluids played an active role in these reactions, forming H₂O‐, CO₂‐ and Cl‐bearing phases at the expense of the primary volatile‐free minerals, causing depletion in Fe and infiltration of K, Mg, Na, B and P. The transformation of gabbro to scapolite metagabbro is observed as a fluid front replacing the primary magmatic mineral assemblage in three stages: during an incipient amphibolitization stage, the primary mafic minerals were replaced by anthophyllite or hastingsite, followed by pargasitic and edenitic Ca‐amphibole. Magnetite was dissolved, while rutile formed by the breakdown of ilmenite. Plagioclase was replaced by Cl‐rich scapolite (Me_19‐42) reflecting Cl‐saturation, while K‐ and Mg‐saturation produced phlogopite, enstatite, sapphirine and rare corundum. The high modal contents of chlorapatite and tourmaline in the scapolite metagabbro imply infiltration of B and P. The albitites consist dominantly of albite (Ab_95‐98) with varying, generally small, amounts of chlorite, calcite, rutile, epidote and pumpellyite. They formed from a H₂O–CO₂‐fluid rich in Na. The gabbro yields a zircon U–Pb age of 1149 ± 7 Ma and tonalite 1294 ± 38 Ma, whereas rutile from scapolite metagabbro and albitite has U–Pb ages of 1090–1084 Ma, and phlogopite produced during scapolitization Rb–Sr ages of 1070–1040 Ma. Temperature conditions for the scapolitization are inferred to have been 600–700 °C. The reported ages, combined with mineralogical and petrographic observations and inferred P–T conditions, indicate that the metasomatism was a part of the regional Sveconorwegian amphibolite facies metamorphic phase. Initial ⁸⁷Sr/⁸⁶Sr of the scapolite ranges from 0.704 to 0.709. The Sr‐signature, the Cl‐ and B‐rich environment and regional distribution of lithologies suggest that the fluid may have originated from evaporites that were mobilized during the regional metamorphism.     

Stable isotopic and petrological constraints on scapolitization of the Whitestone meta-anorthosite,Grenville Province,Ontario*

The Whitestone Anorthosite (WSA), located in the Central Gneiss Belt of the south-western Grenville Province, Ontario, exhibits a nearly concentric metamorphic envelope characterized by an increase in modal scapolite, hornblende, epidote and garnet, developed around a core of granulite facies clinopyroxene ± orthopyroxene ± garnet meta-anorthosite. Scapolite- and hornblende-bearing assemblages develop mainly at the expense of plagioclase and pyroxene within the envelope. Stable isotopic and petrological data for scapolite-bearing mineral assemblages within meta-anorthosite constrain the source of carbon responsible for CO₃-scapolite formation and the extent of fluid/rock interaction between the anorthosite and adjacent lithologies. Stable isotopic data indicate increasing δ¹⁸O and δ¹³C from core to margin of the meta-anorthosite and for samples from the southern extension of the WSA, where it is ductilely deformed within the Parry Sound Shear Zone (PSSZ). The average δ¹⁸O_SMOW value (whole rock) for the WSA core is 6.9‰, increasing to 11.5‰ where the WSA is in tectonic contact with marble breccia. The average δ¹³C_PBD value of scapolite in meta-anorthosite from the centre of the WSA is -3.4‰, increasing to -0.5‰ at the eastern (marble) contact. Average values of δ¹³C for scapolite and whole-rock δ¹⁸O for samples from the shear zone are -1.0 and 8.0‰, respectively. Marbles have average δ¹⁸O and δ¹³C values of 19.2 and -0.4‰, respectively. The sulphate content of texturally primary scapolite decreases from the core of the WSA (X_SO4= 0.48) to the eastern contact (≤0.05). Texturally late scapolite after plagioclase and garnet tends to be CO₃-rich relative to texturally primary scapolite, and some scapolite grains show zoning in the anion site with CO₃-enriched rims. Scapolite composition may vary at any scale from a single grain to outcrop. The pattern of isotopic enrichment in ¹³C and ¹⁸O preserved in the eastern margin of the WSA is consistent with marble as the major source of fluid contributing to the formation of the metamorphic envelope. The decrease in X_SO4 and increase in X_CO3 in scapolite toward the margin of the WSA indicate that the volatile content was reset by, or developed from, a CO₂-bearing fluid. Assuming derivation of fluid from marble, minimum fluid/rock values at the margin of the WSA range from 0.03 for the least enriched, to 0.30 for the most isotopically enriched samples. Although marble is not found in immediate contact with samples of sheared meta-anorthosite from the PSSZ, a marble source is also consistent with the C and O isotope composition and anion chemistry of scapolite within these samples.     

Fracturing,fluid flow and shear zone development: Relationships between chemical and mechanical processes in Proterozoic mafic dykes from southwestern Montana,USA

Fluids can play an important role in the localization of deformation in the deep crust, yet the specific mechanisms active during the complex interactions between metasomatism, metamorphism and deformation remain elusive. Precambrian metagabbronorite dykes in southwest Montana contain fractures filled with Hbl±Grt and discrete cm‐scale shear zones with well‐preserved strain gradients. This system offers an ideal opportunity to constrain the chemical and mechanical processes that facilitated strain localization. An early M₁ assemblage of Grt₁+Cpx₁+Pl₁+Qz developed at conditions of 0.51–0.85 GPa and 500–700°C and is preserved largely as a static replacement of relict igneous phases (Opx, Pgt, Pl) in coronitic textures. An M₂ assemblage characterized by Grt₂+Pl₂±Cpx₂+Hbl+Scp+Qz developed at 0.86–1.00 GPa and 660–730°C coincided with fluid flow and deformation associated with shear zone development. Microstructural observations in marginal protomylonite/mylonite and laminated ultramylonite suggest a shear zone evolution that involved (1) nucleation from pre‐existing fractures that were sites for major fluid infiltration, (2) initial widening coincident with grain‐size reduction by microfracturing, dislocation creep, and synkinematic metamorphic reaction by solution transfer, and (3) a switch in the dominant deformation mechanisms active in the ultramylonite from grain‐size insensitive mechanisms to grain‐size sensitive granular flow accommodated by fluid‐assisted diffusion. Throughout this evolution, the effective bulk compositions of the rock volumes responding to metamorphism changed through a combination of mechanical and metasomatic processes.     

Tennantite-tetrahedrite series from the Madan Pb-Zn deposits,Central Rhodopes,Bulgaria

Minerals from the tennantite-tetrahedrite series (fahlores) are found as single euhedral crystals and crustiform aggregates in hydrothermal veins of the Gradishte and Petrovitsa Pb-Zn deposits of the Madan ore field, southern Bulgaria. Unusually large compositional variations and fine oscillatory crystal zoning were investigated with electron microprobe analysis. The Gradishte samples correspond dominantly to tennantite, while Petrovitsa crystals have exclusively tetrahedrite composition. Fahlore compositions at Madan correspond to zincian varieties (1.6–1.95 apfu), with low Fe-content (<0.45 apfu). Minor silver is characteristic only for the Petrovitsa samples, reaching a maximum of 0.30 apfu. The (Cu+Ag) content of the Petrovitsa tennantites and the Cu content of the Gradishte tetrahedrites systematically exceed 10 apfu resulting in compensation of the excess Cu in the structure by Fe³⁺. Textural characteristics, mineral relationships and available fluid inclusion and stable isotope data suggest that fahlores precipitated in the late stages of mineralization at Madan, at temperature interval of 300–200 °C from oxidizing fluids with mixed (magmatic-meteoric) signatures.     

Electron Probe Microanalysis of Bromine in Minerals and Glasses with Correction for Spectral Interference from Aluminium,and Comparison with Microbeam Synchrotron X‐Ray Fluorescence Spectrometry

The strong spectral interference between Br‐ and Al‐induced X‐ray lines hampers the utilisation of electron probe microanalysis (EPMA) for measuring Br mass fractions in Al‐bearing minerals and glasses. Through measuring Br‐free Al‐bearing materials, we established an EPMA method to quantify the overlap from AlKα on BrLβ, which can be expressed as a linear function of the Al₂O₃ content. The count rate of the BrLβ peak signal was enhanced by high beam currents and long measurement times. Application of this EPMA method to Al‐ and Br‐bearing materials, such as sodalite and scapolite, and to five experimental glasses yielded Br mass fractions (in the range of 250–4000 μg g^?1) that are consistent with those measured by microbeam synchrotron X‐ray fluorescence (μ‐SXRF) spectrometry. The EPMA method has an estimated detection limit of ~ 100–300 μg g^?1. We propose that this method is useful for measuring Br mass fractions (hundreds to thousands of μg g^?1) in Al‐bearing minerals and glasses, including those produced in Br‐doped experiments. In addition, the natural marialitic scapolite (ON70) from Mpwapwa (Tanzania) containing homogeneously distributed high mass fractions of Br (2058 ± 56 μg g^?1) and Cl (1.98 ± 0.03% m/m) is an ideal reference material for future in situ analyses.     

流体的氯含量及其演化：来自岩石含氯矿物的记录

含氯流体是地质作用中重要的流体形式之一。通过含羟基矿物的氯含量来反演流体的组分及其演化是流体研究的一个重要方面。角闪石、黑云母、方柱石和磷灰石是主要的含氯矿物,可以揭示含氯流体与岩石的相互作用。这些矿物的氯含量受平衡流体的成分、温压条件以及自身的晶体化学结构等复杂因素制约。一方面,结合实验确定的热力学数据可以通过矿物氯含量在一定范围内定量计算流体的氯组分;另一方面,也可以根据矿物的氯含量变化特征来反演流体 岩石相互作用过程中流体成分的变化特征,这样的流体成分演化可能反映了特定的地质过程。     

Sulphide formation from granulite‐facies S‐rich scapolite breakdown

Scapolite in granulite facies terranes provides a reservoir for volatile components such as sulphur and carbon in rocks that are otherwise considered ‘dry’. Formed at lower crustal conditions, the high‐S end‐member of scapolite, silvialite, is a major host of sulphur in granulites. Compositional and textural changes involving scapolite reveal that S‐rich scapolite becomes unstable during hydration and deformation at amphibolite facies conditions. Either scapolite changes composition, whereby SO₄^2? is exchanged for CO₃^2? or Cl^? in its structure, or scapolite is replaced by amphibole and/or epidote. Sulphur that is released from silvialite is deposited as sulphides within the original silvialite grain boundaries and can remain relatively immobile in undeformed anorthosites. However, increased sulphide mobility is evident in areas of increased deformation and hydration. Reactions involving S‐bearing scapolite not only have important implications for sulphide deposition and the S‐cycle, but may also influence conductivity variation in the lower crust.     

Stability and phase equilibria of chloride and carbonate bearing scapolites at 750°C and 4000 bar

At 750°C and 4000 bar scapolite is stable relative to plagioclase + calcite over the range of plagioclase compositions An₅₃–An₈₃. The assemblage plagioclase + scapolite + calcite is stable relative to plagioclase + calcite over the ranges of plagioclase composition An₄₈-An₅₃ and An₈₃–An_91.5. When NaCl is present in the coexisting fluid the range of scapolite compositions stable relative to plagioclase increases. High mole fractions of NaCl in the fluid stabilize scapolite relative to plagioclases from An₂₅ to An₈₇ in the presence of excess calcite. Determination of the $\text{Cl}\text{(Cl + CO}{}_3\text{)}$ ratios of the synthetic scapolites shows that the range of stable scapolite compositions is significantly larger than heretofore proposed, and that even the chloride and carbonate bearing scapolites must be considered a four component solid solution. The K_D for the exchange of NaCl and CaCo₃ between coexisting scapolite, fluid and carbonate is given by the equation In $\text{K}{}_{\mathrm{D}}\text{= (?0.0028) [}\text{Al}\text{(Al + Si)}\text{]}{}^{\mathrm{?5.5580}}$. This equation implies that Cl-poor natural scapolites coexisted with fluids low in NaCl, and that regional occurrences of Cl-rich scapolites are likely to represent metamorphosed evaporite sequences.     

钙长辉长无球粒陨石NWA 11592的岩石矿物学特征及富铁橄榄石脉成因研究

灶神星是太阳系最大的硅酸盐质小行星,它的岩石样品(HED族陨石)是目前太阳系最古老的岩浆岩之一,很有可能记录了类地行星最早期地质流体活动的重要信息。本次工作首次在一块非角砾岩平衡型的Eucrite NWA 11592中发现了较粗长的富铁橄榄石脉。通过对NWA 11592陨石进行详细的岩相学和地球化学特征研究,将NWA 11592陨石划为玄武质非角砾岩型Eucrite,冲击变质程度至少为S4,热变质程度为6型。NWA 11592中富铁橄榄石脉最有可能为含H₂O流体沿裂隙的沉淀产物,反应系统应是开放且较为氧化的(f_O2达IW+0.9),且应发生在灶神星浅层地壳> 4 km的埋藏深度。含H₂O流体渗透作用除更多地发生在灶神星表面或近地表外,还有可能发生在灶神星内部的浅层地壳中。