Low-temperature Hydrothermal Activity Research Articles

Opening of a trans-Pangaean marine corridor during the Early Jurassic: Insights from osmium isotopes across the Sinemurian–Pliensbachian GSSP, Robin Hood's Bay, UK

The Hispanic Corridor represents a significant phase of continental reorganisation of the Early Jurassic that eventually provided connectivity between the western Tethyan and eastern Pacific oceans along the Central Atlantic rift zone. Although the initiation of this marine corridor profoundly impacted oceanic circulation and marine faunal exchange patterns, the timing of its formation hitherto remains poorly constrained with estimates spanning both the Hettangian and Sinemurian.The Sinemurian–Pliensbachian Global Stratotype Section and Point (GSSP) at Robin Hood's Bay, UK, comprises a succession of well-exposed, immature organic-rich sediments, only previously characterised by strontium, oxygen and carbon isotope geochemistry. New Re and Os isotope profiling indicates substantial variation in seawater chemistry at this time. Initial osmium isotope data become increasing unradiogenic (0.40 to 0.20) across the boundary, providing evidence for a continual flux of unradiogenic Os into the oceans during the latest Sinemurian. The initial unradiogenic 187Os/188Os values indicate the occurrence of low-temperature hydrothermal activity associated with the formation of the Hispanic Corridor during the breakup of Pangaea. Therefore, combined with biogeography and faunal exchange patterns, the Os isotope data demonstrates that connectivity between the Eastern Pacific and Tethyan oceans initiated during the latest Sinemurian. As a result this study better constrains the timing of establishment of the Hispanic Corridor, which was previously limited to poorly defined biogeography.

The connection between iron ore formations and “mud-shrimp” colonizations around sunken wood debris and hydrothermal sediments in a Lower Cretaceous continental rift basin, Mecsek Mts., Hungary

In the Early Cretaceous, the continental rift basin of the Mecsek Mts. (Hungary), was situated on the southern edge of the European plate. The opening of the North Atlantic Ocean created a dilatational regime that expanded to the southern edge of the European plate, where several extensional basins and submarine volcanoes were formed during the Early Cretaceous epoch. Permanent seaquake activity caused high swell events during which a large amount of terrestrial wood fragments entered into submarine canyons from rivers or suspended woods which had sunk into the deep seafloor. These fragments created extended wood-fall deposits which contributed large-scale flourishing of numerous burrowing thalassinid crustaceans. Twelve different thalassinid coprolite ichnospecies can be found in the Berriasian–Hauterivian volcano-sedimentary formations.According to the seladonitic crustacean burrows which associated with framboidal pyrite containing Zoophycos and Chondrites ichnofossils (i.e. a “fodinichnia” trace fossil association), the bottom water was aerobic and the pore water was anaerobic; in the latter sulfate reduction occurred. The preservation of wood fragments around thalassinid burrows can be explained by rapid sedimentation related to turbidity currents.Due to the low temperature hydrothermal circulations of seawater, large amounts of iron were released from intrusive, pillowed basaltic sills; these sills intruded into soft, water-saturated sediments containing large amounts of thalassinid excrement. In the coprolites can be found idiomorphic mineral particles originating from the basalts, and coprolites can often be found in peperitic interpillow sediments. This indicates that the life-activity of the decapoda crustaceans in many Lower Cretaceous occurrences initially preceded the first magmatic eruptions. The paroxysm of the rift volcanism took place during the Valanginian age, when some submarine volcanoes emerged above sea level, reaching a maximum height of 300m (above sea level); from these volcanoes further terrestrial plant debris got into the basin. Hydrothermal vents, which periodically occurred around basaltic bodies until the Hauterivian, could have contributed to the creation of favourable temperature or nutritional conditions for some decapoda crustaceans – e.g the recently described new callianassid (Nihonotrypaea thermophila), which is known only from hydrothermally infuenced habitats.Around the intrusive pillow basalts, hydrothermal circulation of oxygenated seawater occured and thick seladonitic and goethitic fills formed along the cracks and cavities of pillowed basalts. When oxidized, sulfate-rich fluids passed into the crustacean coprolite-rich, reductive and anaerobic interpillow sediments, these fluids underwent an intensive sulfate reduction. This was primarily due to termophil sulfate reducers which as proved by the negative sulfur isotope values (−35.9‰ and −28.0‰ δ 34S) of sulfidic hydrothermal chimneys which contain framboidal pyrite and which were formed between the pillow basalts. The largest chimney structure reached a height of 1m, with a mass of about 150kg. The sulfide phase is characterized by Mo enrichments up to 511ppm. The fluid inclusion measurements from the calcitic precipitations of the sulfide chimneys indicate low temperature (~129°C) hydrothermal activity, and the salinity of the primary fluid inclusions proves the seawater origin of the hydrothermal fluids. In some thalassinid crustacean coprolite rich interpillow sediments and in the cracks of some hydrothermal calcite, there is the presence of black, lustrous bitumine (gilsonite) which is the distillation product of hydrothermal petroleum formed mainly by the coprolites. Hydrothermal circulations of oxygenated seawater caused subsequent oxidation of the sulfidic, interpillow sediments and chimneys; these were altered to form goethite. Due to the short-period of the hydrothermal activity among the intrusive pillowed basalts, sulfidized interpillow sediments could not be oxidized completely.The texture of the goethitic iron ore (as an interpillow sediment) is network-like and dentritic, which is very similar to the iron-oxidic and microbial textured sediments of the Juan de Fuca Ridge. The dendritic iron-oxide-hydroxide particles which were involved in this study are not hollow and exceed the size-domain characteristic for bacterial products. However, in some cases hollow- and tube-like particles having a diameter of 1.2–1.5μm can refer to the activity of the Sphaerotilus–Leptothrix iron-oxidizer bacterial group.

Nd–Sr isotope and REY geochemistry of metalliferous sediments in a low-temperature off-axis hydrothermal environment (Costa Rica margin)

Metalliferous deposits are ubiquitous in marine sediments and play a major role in the elemental cycles of iron, manganese, and other trace elements. The metalliferous sediments studied here were sampled near a basaltic seamount named “Dorado”, on the eastern flank of the East Pacific Rise, west of Nicoya Peninsula (Costa Rica). Based on heat flow data and porewater profiles, this site is an area of active low-temperature hydrothermal discharge. Most samples are from gravity core GC50, which is characterized by the presence of abundant authigenic minerals (mainly Fe–Mn-oxyhydroxides and apatites).Our data suggest that these minerals have initially precipitated during the Miocene from a high-temperature hydrothermal plume when the Dorado site was located near the East Pacific Rise. With increasing distance from the ridge axis, the plume precipitates were buried under hemipelagic sediments. After the onset of the present-day low temperature hydrothermal activity these precipitates were dissolved and re-precipitated higher up in the sediment pile to form the observed assemblage of authigenic minerals.The study thus shows that the metalliferous deposits of the Dorado seamount have a very complex origin, which could be unraveled by a combined approach based on Nd–Sr isotopes, REY data (rare earth elements and yttrium), and mineralogical observations.

Multiple Sulfur and Iron Isotope Composition of Magmatic Ni-Cu-(PGE) Sulfide Mineralization from Eastern Botswana

We report here high-precision multiple sulfur and iron isotope compositions for a series of mineralized samples from Ni-Cu-(PGE) sulfide deposits in the Archean Tati greenstone belt and the Phikwe Complex of eastern Botswana. Mineralized samples from the Phoenix and Selkirk Ni-Cu-(PGE) deposits in the Tati greenstone belt display slightly positive δ 34S isotope values, ranging from 0.2 to 0.8‰ V-CDT. Δ33S values of sulfides at Phoenix and Selkirk are −0.01 to −0.08‰ V-CDT, suggesting either a dominantly mantle sulfur source or effective eradication of a crustal Δ33S anomaly through equilibration with large amounts of silicate melt. In the Selebi-Phikwe belt, a granite-gneiss terrane with abundant amphibolite lenses of either volcanic and/or intrusive nature, mineralized lower grade samples from the Phikwe, Phokoje, and Dikoloti Ni-Cu-(PGE) deposits have more variable δ 34S values ranging from −3.1 to +0.3‰ and display significant mass independent anomalies (Δ33S values ranging from −0.89 to −0.27‰), suggesting that barren sulfides associated with distal or low-temperature sea-floor hydrothermal activity contributed sulfur to these deposits. Iron isotopes of sulfides from these deposits show a relatively small range of negative Δ56Fe values (−0.29 to −0.04‰), consistent with high-temperature fractionations in magmatic systems, with the exception of one sample from the Dikoloti Ni-Cu-(PGE) deposit of the Selebi-Phikwe greenstone belt, which shows a more negative δ 56Fe value of −0.61‰, consistent with assimilation of sedimentary or hydrothermal sulfides rather than fractionations in high-temperature magmatic systems. Data from this study highlight the complexity and variability that characterize ore-forming processes in magmatic systems. We suggest that the presence of sulfur-bearing lithologic units in host rocks of mafic and ultramafic intrusions may not be essential toward the assessment of the prospectivity of a province to host orthomagmatic nickel sulfides. Geologic settings without any or little sulfur in the stratigraphy, which have been traditionally neglected in terms of their prospectivity, should thus be revisited and possibly reassessed considering the potential importance of external source of sulfur to generate ore deposits.

Occurrence, composition and paragenesis of the zeolites and associated minerals in the alkaline basalt of a maar-type volcano at Haláp Hill, Balaton Highland, Hungary

AbstractHaláp Hill is an eroded remnant of young (∼3 Ma) alkaline basalt in the western part of the Bakony–Balaton Highland Volcanic Field, Tapolca, Hungary. Cavities in the basalt contain miarolitic minerals (augite, apatite, magnetite, plagioclase and sanidine), zeolites (analcime, chabazite-Ca, chabazite-Na, garronite, gismondine, gmelinite-Ca, gmelinite-Na, gobbinsite, gonnardite-Na, natrolite, mesolite, phillipsite-Ca, phillipsite-K, phillipsite-Na and scolecite) and other secondary minerals (calcite, smectite-group minerals, goethite and Mn-oxides). Chabazite-Na, gmelinite-Ca, gonnardite-Na, phillipsite-Na and phillipsite-K are reported from Haláp Hill for the first time. The Ca-rich and Na-rich zeolites and abundant calcite were produced by hydrothermal alteration. Mineral assemblages were characterized by X-ray diffraction, differential thermal analysis, energy-dispersive spectrometry and wavelength-dispersive spectrometry. The secondary mineral assemblages were probably formed as a result of low-temperature hydrothermal activity at 50—100°C. Miarolitic minerals crystallized first in cavities in the basalt; they were followed by zeolite-group minerals and calcite. Analcime and phillipsite with or without chabazite/gmelinite/garronite or gobbinsite were the first zeolite-group minerals to crystallize; gonnardite-Na and natrolite crystallized later from Na-rich fluids. Calcite and smectite-group minerals crystallized continually. This paragenetic sequence is similar to others which have been reported in basalt from other localities in the Balaton Highland, Iceland and Northern Ireland.

Mineralogical and geochemical evidence for hydrothermal activity at the west wall of 12°50′N core complex (Mid-Atlantic ridge): A new ultramafic-hosted seafloor hydrothermal deposit?

Dredging along the west wall of the core complex at 12°50′N Mid-Atlantic Ridge sampled a number of black oxyhydroxide crusts and breccias cemented by black and dark brown oxyhydroxide matrix. Black crusts found on top of basalt clasts (rubble) are mainly composed of Mn-oxides (birnessite, 10-Å manganates) with thin films of nontronite and X-ray amorphous FeOOH on their surfaces. Their chemical composition (low trace- and rare earth-element contents, high Li and Ag concentrations, rare earth element distribution patterns with negative both Ce and Eu anomalies), Sr–Nd–Pb-isotope systematic and O-isotope data suggest low-temperature (~ 20 °C) hydrothermal deposition from a diffuse vent area on the seafloor. Mineralogical, petrographic and geochemical investigations of the breccias showed the rock clasts were hydrothermally altered fragments of MORBs. Despite the substantial mineralogical changes caused by the alteration the Sr–Nd–Pb-isotope ratios have not been significantly affected by this process. The basalt clasts are cemented by dark brown and black matrix. Dark brown cement exhibits geochemical features (very low trace- and rare earth- element contents, high U concentration, rare earth element distribution pattern with high positive Eu anomaly) and Nd–Pb-isotope systematics (similar to that of MORB) suggesting that the precursor was a primary, high-temperature Fe-sulfide, which was eventually altered to goethite at ambient seawater conditions. The data presented in this work points towards the possible existence of high- and low-temperature hydrothermal activity at the west wall of the core complex at 12°50′N Mid-Atlantic Ridge. Tectonic setting at the site implies that the proposed hydrothermal field is possibly ultramafic-hosted.

Afmite, Al3(OH)4 (H2O)3(PO4 )(PO3OH)· H2O, a new mineral from Fumade, Tarn, France: description and crystal structure

The new mineral afmite, Al_3(OH)_4(H_2O)_3(PO_4)(PO_3OH)·H_2O, is triclinic with space group Pl and cell parameters a = 7.386(3), b = 7.716(3), c = 11.345(4) A, a = 99.773(5), β = 91.141(6), y = 115.58(5)°, V = 571.6(3) A^3 and Z = 2. It occurs, sometimes in association with matulaite and variscite, in fractures and solution cavities in shale/siltstone at Fumade, Tarn, France. The formation is probably largely the result of remobilisation and crystallisation during low-temperature hydrothermal activity and/or weathering and ground water activity. Afmite forms in cockscomb aggregates of diamond-shaped tablets on {001}, ubiquitously contact-twinned on {001} and also commonly twinned by rotation on [010] with {010} and {110} composition planes, forming star-like sixlings. The streak of the mineral is white, the luster is pearly, and the Mohs hardness is about 11/2. The mineral is flexible, but not elastic, has an irregular fracture and three cleavage directions: {001} perfect, {010} and {1Formula 0} good. The measured density is 2.39(3) g/cm^3 and the calculated density is 2.391 g/cm^3 based upon the empirical formula. Optical properties (white light): biaxial (+), α = 1.554(1), β = 1.558(1), y = 1.566(1), 2V_(meas). = 70(5)° and 2V_(calc) = 71°. Electron microprobe analyses provided Al_2O_3 40.20 and P_2O_5 38.84 wt% and CHN analyses provided H_2O 25.64 wt%, total 103.68 wt%. Normalized EMP analyses and water based on the structure yield Al_2O_3 36.41, P_2O_5 35.17 and H_2O 28.42, total 100.00 wt%. Infrared and Raman spectra were consistent with the PO_3OH, OH and H_2O as indicated by the crystal-structure determination. The strongest powder X-ray diffraction lines are [d_(obs)(A),I_(obs),(hkl)]: 11.089,100,(001), 3.540,81,(013,112), 5.484,79,(002,101), 2.918,60(122), 3.089,33(113,201), 4.022,30,(102,112), 6.826,23,(010). The crystal structure, solved from twinned data, (R_1 = 10.4 % for 1262 F_o > 4σF reflections) consists of chains of AlO_6 octahedra parallel to [110] in which edge-sharing octahedral dimers share corners with individual octahedra. Both PO_4 and PO_3OH tetrahedra link the chains into sheets parallel to {001} and the PO_4 tetrahedra further serve to link two sheets together into a thick slab in which tetrahedral (T) and octahedral (O) layers alternate, forming a T-O-T-O-T sandwich. The linkage between these sandwiches in the c direction is via hydrogen bonding with isolated H_2O groups in the interlayer region. Afmite is closely related structurally to the turquoise-group minerals and specifically to planerite. The recently described mineral kobokoboite probably has a closely related sheet structure.

Volatile organic sulfur compounds as biomarkers complementary to methane: Infrared absorption spectroscopy of CH 3SH enables insitu measurements on Earth and Mars

As universal products of biological processes, volatile organic sulfur compounds such as methyl mercaptan (CH 3SH) may be essential in the search for signs of life on Mars and in exoplanet atmospheres. Methyl mercaptan is implicated in the origin of life at sites of low-temperature hydrothermal activity driven by serpentinization. Serpentinization may occur on Mars, in icy satellite oceans, and in other small wet bodies to a greater extent than on Earth, with important implications for life. We characterized absorption features in pure laboratory sample spectra of CH 3SH using the Carbon Isotope Laser Spectrometer (CILS), an infrared ( 3.27 μ m ) tunable diode laser spectrometer with capabilities nearly identical to those of the Tunable Laser Spectrometer (TLS) instrument on the Mars Science Laboratory. The molecular species proves detectable by CILS and TLS at the sensitivities approaching the level of parts per trillion with pre-concentration. These measurements demonstrate the possibility for detection of methyl mercaptan, with implications for its possible use as an in situ biosignature for Earth-based and extraterrestrial exploration.

Uranium minerals from the San Marcos District, Chihuahua, Mexico

The mineralogy of the two uranium deposits (Victorino and San Marcos I) of Sierra San Marcos, located 30 km northwest of Chihuahua City, Mexico, was studied by optical microscopy, powder X-ray diffraction with Rietveld analysis, scanning electron microscopy with energy dispersive X-ray analysis, inductively coupled plasma spectrometry, and gamma spectrometry. At the San Marcos I deposit, uranophane Ca(UO2)2Si2O7·6(H2O) (the dominant mineral at both deposits) and metatyuyamunite Ca(UO2)(V2O8)·3(H2O) were observed. Uranophane, uraninite (UO2+x), masuyite Pb(UO2)3O3(OH)·3(H2O), and becquerelite Ca(UO2)6O4(OH)6 ·(8H2O) are present at the Victorino deposit. Field observations, coupled with analytical data, suggest the following sequence of mineralization: (1) deposition of uraninite, (2) alteration of uraninite to masuyite, (3) deposition of uranophane, (4) micro-fracturing, (5) calcite deposition in the micro-fractures, and (6) formation of becquerelite. The investigated deposits were formed by high-to low-temperature hydrothermal activity during post-orogenic evolution of Sierra San Marcos. The secondary mineralization occurred through a combination of hydrothermal and supergene alteration events. Becquerelite was formed in situ by reaction of uraninite with geothermal carbonated solutions, which led to almost complete dissolution of the precursor uraninite. The Victorino deposit represents the second known occurrence of becquerelite in Mexico, the other being the uranium deposits at Pena Blanca in Chihuahua State.

Secondary magnetizations in shear and fault zones in southern Finland

Studies on remanent magnetization of shear and fault zones of crystalline rocks in southern Finland have been carried out to test juvenile fluid activity that can be dated paleomagnetically. Locating in the central part of Baltica, the area has been tectonically relatively quiet since the Precambrian. However, tectonism at the margins of the craton during the Caledonian, Hercynian and Uralian orogenies probably reactivated faults and resulted in low-temperature hydrothermal activity also within the craton. We identified two consistent remanent magnetization components in four (out of five) studied localities. One remanence component has an intermediate to high coercivity NNW directed magnetization ( D = 334.7°; I = 35.2°; k = 92.1; α 95 = 9.6°) and unblocking temperatures suggest that it resides in (titano)magnetite. The direction is similar to the remanence that is commonly observed in Svecofennian age (ca. ~ 1.9 Ga) rocks all over the Precambrian Fennoscandian Shield, and probably represents the primary Svecofennian magnetization preserved in the host rocks. Another common component is directed NE ( I = 30.8°; D = 35.3°; k = 264.5; α 95 = 5.7°) and is carried by hematite and maghemite. Its resulting paleomagnetic pole compares well with Phanerozoic paleopoles of Baltica, and is suggested to represent a Permian remagnetization. We interpret that this remanence reflects the reactivation of the Svecofennian crust in the late Paleozoic due to tectonic events related to the formation of the supercontinent Pangea. In addition, remagnetizations due to Mesoproterozoic rapakivi magmatism and younger (Mesozoic to present) events were identified.

New thermochronologic constraints on the evolution of the Zaldívar porphyry copper deposit, Northern Chile

Life spans and thermal evolution of hydrothermal systems are of fundamental metallogenic importance. We were able to establish the chronology and cooling history of the Zaldivar porphyry copper deposit (Northern Chile) by applying a combination of different isotopic dating methods in minerals with different closure temperatures, including 40Ar/39Ar geochronology and zircon fission track thermochronology, together with fluid inclusion thermometry and previous published U–Pb zircon geochronology. The hydrothermal mineralization in the Zaldivar deposit is genetically related to the Llamo Porphyry unit. Samples of igneous biotites from this intrusion yielded 40Ar/39Ar plateau ages between 35.5 ± 0.7 and 37.7 ± 0.4 Ma defining a weighted average of 36.6 ± 0.5 Ma (2σ). In contrast, one sample from the Zaldivar porphyry, one from the andesites, and two from the Llamo porphyry yielded considerably younger fission track ages of approximately 29 Ma with a weighted mean for all ages of 29.1 ± 1.7 Ma (2σ). Thermal and compositional constraints for the hydrothermal system in the Zaldivar deposit from fluid inclusions thermometry show that at least three fluid types broadly characterize two main hydrothermal episodes during the evolution of the deposit. The main mineralization and alteration event is characterized by high temperature (above 320°C) hypersaline fluids (salinity between 30 and 56 wt.% NaCl equivalents) coexisting with low-density gas-rich inclusions (salinity less than 17 wt.% NaCl equivalents) that homogenizing into the gas phase at temperatures above 350°C. The second episode corresponds to a low-temperature event which is characterized by liquid-rich fluid inclusions that homogenize into the liquid phase at temperatures ranging from 200°C to 300°C with salinities lower than 10 wt.% NaCl equivalents. The 40Ar/39Ar data (36.6 ± 0.5 Ma, weighted average) obtained from igneous biotites represent the minimum age for the last high-temperature (above 300°C) hydrothermal pulse. When compared with previously published U–Pb ages (38.7 ± 1.3 Ma) in zircons from the Llamo porphyry, a close temporal relationship between crystallization of the parental intrusion and the thermal collapse of the last high-temperature hydrothermal event is evident. Cooling took place from approximately 800°C (crystallization of the intrusive complex defined by zircon U–Pb ages) to below 300 ± 50°C (biotite 40Ar/39Ar closure temperature) within approximately 1.5 m.y. Because the thermal annealing of fission tracks in zircons occurs at temperatures of 240 ± 30°, the zircon fission track (ZFT) ages of 29.1 ± 1.7 Ma (2σ) mark the end of the thermal activity in the Zaldivar area, specifically the time when the whole area cooled below this temperature, well after the collapse of the main hydrothermal event in the Zaldivar porphyry copper deposit. This cooling age roughly coincides with the age defined for the emplacement of dacitic dikes at 31 ± 2.8 Ma (2σ) (published K–Ar whole rock), 5 km south of the Zaldivar deposit, in the Escondida area. This late magmatic pulse probably is responsible for high heat flow in the Zaldivar deposit as late as 29 Ma. There is no evidence that the low temperature hydrothermal pulse recognized by fluid inclusion studies is related to this thermal event. The zircon fission track cooling ages are interpreted to be related to the time lag required for complete relaxation of the perturbation of the isotherms in the geothermal field imposed by the intrusion of magmatic bodies, with or without any association with low temperature hydrothermal activity.

Single-crystal X-ray and Raman investigation on melanophlogite from Varano Marchesi (Parma, Italy)

The results of a new single-crystal structure refinement and of a Raman spectroscopy investigation on melanophlogite, a clathrate structure of SiO 2 , are reported. The studied sample comes from a new finding at Varano Marchesi (Parma, Italy), and occurs in small veins and pockets along fractures in a siliceous marl from a chaotic complex. Melanophlogite is invariably separated from the host rock by a thin crust of opal-CT. Raman spectroscopy was done to investigate the guest molecules that are hosted in the cages of the structure. In the Varano Marchesi melanophlogite, only CH 4 is present in the clathrate structure. During a comparative investigation of melanophlogite from different geological setting (Racalmuto, Sicily, Italy), H 2 S also was found, together with CH 4 , in the cavities of the structure. A single-crystal X-ray refinement of the Varano Marchesi sample was done using the Pm3̅n symmetry of β-melanophlogite [a = 13.399(2), R 4σ = 4.7%]. According to the site refinement from X-ray diffraction results, CH 4 occupies 71 and 91% of the 5 12 and 5 12 6 2 site cavities, respectively. The Varano Marchesi melanophlogite formed as a result of low-temperature hydrothermal activity. The mineral growth occurred at the expense of opal, in connection with CH 4 flux through the porous material.

Kamphaugite-(Y) from La Cabrera massif, Spain: a low-temperature hydrothermal Y-REE carbonate

AbstractKamphaugite-(Y) occurs as white to cream-coloured spherical to semi-spherical aggregates of radial crystals in the La Cabrera granitic pluton (Spanish Central System). It mainly occurs on the free surfaces of alkali feldspar, quartz, calcite, kainosite-(Y) and laumontite, and inside miarolitic cavities. La Cabrera kamphaugite-(Y) has an average composition of Ca0.94Y0.89REE0.21(CO3)2 [F0.05(OH)0.95]·1.19H2O. Negative δ13CV-PDB values (–14 to –15‰) indicate a meteoric carbon source. Textural relations between kamphaugite-(Y) and coexisting minerals, its relatively high δ18OV-SMOW values (+25 to +26‰), and the occurrence of laumontite inclusions in kamphaugite-(Y), point to a genesis at < 50°C during very low-temperature post-magmatic hydrothermal activity.

Middle Archean volcano-hydrothermal sequence: Bacterial microfossil-bearing 3.2 Ga Dixon Island Formation, coastal Pilbara terrane, Australia

The 3.2 Ga Dixon Island Formation in the Cleaverville Group of the coastal Pilbara terrane, Australia, is one of the most complete and best-preserved examples of middle Archean oceanic stratigraphy and contains possible microbial material. Field observations and geochemical evidence suggest that this formation contains a low-temperature hydrothermal vent system with a biogenic microbial colony from the Archean ocean. The Dixon Island Formation is ∼350 m thick and consists of the Rhyolite Tuff, Black Chert, and Varicolored Chert Members, in ascending order. The Rhyolite Tuff Member contains many vein swarms, such as quartz and black chert veins, and highly altered rhyolite tuff layers, which are identified as an underground bypass zone for circulating hydrothermal fluid. Many black chert vein swarms in the Rhyolite Tuff Member imply intensive low-temperature hydrothermal activity during deposition of the Black Chert Member, which is 10–15 m thick. The Black Chert Member is composed of massive black chert, laminated black chert, dark-greenish siliceous shale and tuffaceous laminated chert, which are mainly composed of very fine quartz. Abundant pseudomorphs of silica after aragonite, barite, and gypsum, and a distinctly continuous, stromatolite-like biomat layer (10–20 cm thick), are preserved within the laminated black chert bed. The stromatolite-like biomat bed is formed of fine iron or iron-coated quartz pisolite within fine-grained silica. The absence of detrital sediment of continental origin and the many vein injections imply that this sedimentary facies represents a pelagic hydrothermal environment at ∼500–2000 m paleodepth, and may have been on the slope of an immature island arc. Microbial material has been preserved well in the lower part of Black Chert Member. The massive black chert has carbonaceous peloids (0.3–2.0 mm in diameter), which are similar to those in the black chert veins. The massive black chert contains spiral-, rod, and dendrite-shaped bacterial material. The total organic carbon (TOC) value of massive black chert in the lower part of the Black Chert Member is higher (TOC = 0.15–0.45%) than that of the overlying laminated chert section (TOC = 0.02–0.15%) and the black chert vein (TOC = 0.1–0.13%), and the carbon isotope (δ 13 C) values of this lithology (−33‰ to ∼−27‰) are also lighter than for the black chert veins (−29‰ to ∼−26‰) and the laminated black chert in the upper part of the Black Chert Member and the Varicolored Chert Member (−27‰ to ∼−13‰). This evidence suggests that the carbonaceous grains and bacteria-shaped material in the lower part of the Black Chert Member are of bio-genic origin and were formed close to a low-temperature hydrothermal vent system. The microbial colony may have been rapidly fossilized by silicification related to hydrothermal activity. Laminated black chert in the upper part of the Black Chert and the Varicolored Chert Members may have formed by cyanobacterial sedimentation from the ocean surface.

Mineralogy and geochemistry of hydrothermal sediments from the serpentinite-hosted Saldanha hydrothermal field (36°34′N; 33°26′W) at MAR

The Saldanha hydrothermal field is located at the top of a serpentinized massif (Mount Saldanha, MS) at a non-transform offset (NTO5) along the Mid-Atlantic Ridge (MAR), south of the Azores. It is one of the rare known sites on a worldwide basis where direct evidence of low-temperature (7–9 °C) hydrothermal activity has been provided by direct observation of hydrothermal fluid venting through small orifices in the ocean floor sedimentary cover. This study focuses on the mineralogy and geochemistry of 14 sediment cores collected at MS. For comparison, four samples collected at the Rainbow site (NTO6) were also studied. Mount Saldanha hydrothermal sediments are highly “diluted” within a dominant foraminiferal nanofossiliferous ooze with small fragments of underlying rocks. The mineral assemblage of the hydrothermal component is characterized by sulphides, nontronite, smectites, poorly crystallized Mn oxyhydroxides and amorphous material. Cu, Zn and Fe sulphides, Mn–Mg oxy-hydroxides and putative manganobrucite were also identified in one sample collected at an orifice vent. In this sample, micro-chimneys (conduits) composed of isocubanite and sphalerite were also identified. Mount Saldanha sediments show a clear enrichment in elements such as Mn, Mg, Fe, Cu, P and V, derived from hydrothermal fluids, and Ni, Cr and Co, derived from ultramafic rocks. The geochemical data together with the observed mineral assemblage suggest that the hydrothermal fluids are at a higher temperature than those measured at the escape orifices (7–9 °C), and a strong enrichment in Mg, mainly at the top of the mount, agrees with extensive mixing of the hydrothermal fluid with unmodified seawater. Nevertheless, the mineral assemblage of MS sediments is consistent with the precipitation from hydrothermal fluids at much lower temperatures than at Rainbow. The presence of serpentinized and steatitized (talcshist) ultramafic rocks and the occurrence of a strong methane anomaly within the overlying water column collectively suggest that the hydrothermal circulation at MS is driven by exothermic reactions closely associated with the serpentinization process. Rainbow sediments have a higher concentration in transition metals and consequently an enrichment in sulphides. These differences are likely to be a consequence of the higher temperature of hydrothermal fluids, reflected in the composition of hydrothermal solutions, and of a stronger hydrothermal flux at the Rainbow site.

Cenozoic “radiobarite” occurrences in the Ohře (Eger) Rift, Bohemian Massif: Mineralogical and geochemical revision

Barite occurrences related to the Cenozoic (Late Alpine) low-temperature hydrothermal activity are present in the continental Ohře (Eger) Rift area. A specific, Ra-bearing type of barite has been known under the name “radiobarite” from this area since 1904. Revision of 12 localities revealed the presence of alleged radiobarite only in the Teplice (Lahošť–Jeníkov) and Karlovy Vary areas. Barite from other localities is radium-poor. Barite crystals showing concentric oscillation colour zoning totally prevail. Isomorphous substitution of Sr ( X×10 −1 to X×wt%), Ca ( X×10 −2 wt%) and Fe ( X×10 −1 wt%) for Ba was proved. Average SrO contents of 0.4 wt% are markedly exceeded in some samples from Lahošť–Jeníkov (max. 3.2 wt%) and Karlovy Vary (max. 4.9 wt%). Besides inclusions of stoichiometric iron disulphide, the same samples also contain iron disulphides with unusual high contents of Co (max. 12.2 wt%) and Ni (max. to 8.4 wt%). Specific activity of 238U in the studied barites is very low while that of 226Ra reaches 8 Bq/g in several samples. Therefore, 226Ra is not in equilibrium with its parent uranium. These “radiobarites” or their parts must be therefore relatively young, not older than 10–15 ka. Very low uranium contents (<0.4 ppm) were also confirmed by neutron activation analyses of barite samples. Unit-cell dimensions refined from X-ray powder diffraction data do not show any systematic variation with the measured chemical composition. Their values agree with the data given in the literature. Reflection half-widths, however, seem to correlate with chemistry. Peaks are wider in samples from Lahošť–Jeníkov and Karlovy Vary. Sulphur and oxygen stable isotope compositions of the Cenozoic barite mineralization of Teplice area are very uniform ( δ 34S values between 3.9‰ and 7.1‰ CDT, and δ 18O values between 6.1‰ and 7.7‰ SMOW), while the barites of Děc˘ín area show more variable sulphur sources. Sulphate derived from sediments of the Tertiary Most Basin seems to dominate for the Teplice area, while Cretaceous sediments are a more probable sulphur source in the Děc˘ín area. Calculation of oxygen isotope composition of hydrothermal fluids based on fluid inclusion homogenization temperatures and barite δ 18O data shows δ 18O fluid values in the range of meteoric waters or δ 18O – shifted deep circulating meteoric or basinal waters.

Mineral matter and potentially hazardous trace elements in coals from Qianxi Fault Depression Area in southwestern Guizhou, China

Mineralogy, coal chemistry and 21 potentially hazardous trace elements (PHTEs) of 44 coal samples from the Qianxi Fault Depression Area (QFDA) in southwestern Guizhou province, China have been systematically studied. The major minerals in coals studied are quartz, kaolinite, illite, pyrite, calcite, smectite, marcasite and accessory minerals, including rutile, dolomite, siderite, gypsum, chlorite, melanterite, apatite, collophane and florencite. The SiO 2 content shows a broad variation (0.8–30.7%). A high SiO 2 content in Late Permian coals reflects their enrichment in quartz. The Al 2O 3 content varies from 0.8% to 13.4%, Fe 2O 3 from 0.2% to 14.6%, CaO from <0.1% to 11.9% and the contents of other oxides are relatively low. The relationship between the major oxides and the ash content of coals from high to low is in the order of Si>Al>K>Ti>Na>Mg>Ca>Fe>S. A comparison with World coal averages shows that the Late Permian coals in QFDA are highly enriched in As, Hg, F and U, and are slightly enriched in Mo, Se, Th, V and Zn. The Late Triassic coals in QFDA are highly enriched in As and Hg, and are slightly enriched in Mo, Th and U. The concentrations of As, Hg, Mo, Se, Tl and Zn in the QFDA coal are higher than other Guizhou coal and Liupanshui coal nearby. The QFDA is an area strongly affected by the low-temperature hydrothermal activity during its geologic history (Yanshanian Age, about 189 Ma). The coals in QFDA are enriched in volatile PHTEs, including As, Hg, Se, Sb, Mo, among others. The regions where the coals are enriched in As, Hg and F have been mapped. The regions of coals enriched in volatile PHTEs overlap with the regions of noble metal ore deposits. These coals are located in the cores of anticline and anticlinorium, which are connected with the profound faults through the normal faults. Coals are enriched in volatile PHTEs as a result of the low-temperature hydrothermal activity associated with tectonic faulting.

Carbon and Oxygen Isotope Geochemistry of the Amba Dongar Carbonatite Complex, Gujarat, India

A carbon and oxygen isotope survey based on 42 samples from the Amba Dongar carbonatite complex of Gujarat, India, indicates that the magmatic differentiation series sövite → alvikite → ankeritic carbonatite is beset with a distinct isotope trend characterized by a moderate rise in 13C coupled with a sizeable increase in 18O. From an average of −4.6 ± 0.4 ‰ [PDB] for the least differentiated (coarse) sövite member, δ 13C values slowly increase in the alvikite (−3.7 ± 0.6 ‰) and ankeritic fractions (−3.0 ± 1.1 ‰), whereas δ 18O rises from 10.3 ± 1.7 ‰ [SMOW] to 17.5 ± 5.8 ‰ over the same sequence, reaching extremes between 20 and 28 ‰ in the latest generation of ankeritic carbonatite. While an apparent correlation between δ 13C and δ 18O over the δ 18O range of 7–13 ‰ conforms with similar findings from other carbonatite complexes and probably reflects a Rayleigh fractionation process, the observed upsurge of 18O notably in the ankeritic member is demonstrably related to a late phase of low-temperature hydrothermal activity involving large-scale participation of 18O-depleted groundwaters. As a whole, the Amba Dongar carbonatite province displays the characteristic 13C/ 12C label of deep-seated (primordial) carbon, reflecting the carbon isotope composition of the subcontinental upper mantle below the Narmada Rift Zone of the Indian subcontinent.

Hydrothermal activity associated with off-axis volcanism in the Peru Basin

Products of low temperature hydrothermal activity are widespread in the Peru Basin and are associated with late Tertiary oceanic island type intraplate volcanics. Hydrothermal activity is still taking place as indicated by a series of sharp, high and narrow temperature anomalies over one of the volcanic cones. Submarine hydrothermal activity associated with off-axis volcanism has been frequently observed elsewhere, but was usually found to be limited to seamounts. In the Peru Basin a hydrothermal halo was found in sediments surrounding hydrothermally active seamounts in addition to hydrothermal precipitates on the tops of the seamounts. Todorokite, birnessite, Fe-nontronite, goethite, and silica were found on top of young volcanic edifices and occur as coatings on volcanic rocks and in nuclei of manganese nodules. The hydrothermal precipitates in the sediments are Mg–Fe silicates, as is the case in the adjacent Bauer Basin. The proportion of hydrothermal precipitates in the sediments increases with depth in the cores, down to the appearance of the basalt that indicates the beginning of intraplate volcanism 5 million years ago. Sediments overlying Late Tertiary volcanic rocks are locally enriched in hydrothermal material by solutions percolating upwards directly into the sediment. In these sediments, apatite and phillipsite appear to have been precipitated directly from these ascending hydrothermal solutions.

Helium isotope evidence for off-axis degassing of the Icelandic hotspot

We report a helium and carbon survey of 16 hydrothermal localities from Vestfirdir—the northwest peninsula of Iceland. The region is situated ∼250 km away from the Icelandic rift-axis, and is characterized by low-temperature (<100°C) hydrothermal activity. A mantle-derived input dominates the helium systematics: nine localities have 3 He/ 4 He ratios ( R/ R A) values between those typical of MORB (8±1) and 30—the highest value matches the most extreme magmatic ratios reported worldwide to date. Four other localities have R/ R A ∼MORB ratios with the remaining three showing heavy dilution with crustal radiogenic helium ( R/ R A<MORB). Carbon isotope analysis of seven of the localities reveals a wide range in δ 13 C( CO 2) (−6 to −16‰ PDB), and CO 2/ 3 He ratios vary over 4 orders of magnitude (4×10 6 to 2.9×10 10). There appears no systematic relationship between the volatile systematics and geographic distribution or age of reservoir rocks. Stable isotope ( δ 18 O and δD) variations are consistent with a localized meteoric origin for the hydrothermal waters—the carrier phase of the volatiles. We conclude that release of magmatic volatiles in Vestfirdir occurs predominantly via incipient mantle melting with a negligible input of re-distributed volatiles from the rift zones. It is also highly unlikely that leaching of old reservoir rocks contribute to the mantle volatile flux: however, release of radiogenic helium from the uppermost crust does occur and this is accompanied by addition of isotopically light carbon most likely of organic origin. The light carbon input is most discernible when the mantle-derived carbon signal is reduced—most probably by reaction to form calcite. Although Vestfirdir makes a discernible (off-axis) input to the degassing history of the Icelandic hotspot, its contribution is extremely minor (∼0.04%) when compared to the degassing flux associated with rifting and volcanism along the Icelandic spreading zones.