Geochemistry of a sediment push-core from the Lucky Strike hydrothermal field,Mid-Atlantic Ridge

Hydrothermal sediment mineralogy and geochemistry can provide insights into seafloor mineralization processes and changes through time. We report a geochemical investigation of a short (22 cm) near-vent hydrothermal metalliferous sediment core from the Lucky Strike site (LS), on the Mid-Atlantic Ridge (MAR). The sediment was collected from the base of an active white smoker vent and comprises pure hydrothermal precipitates, mainly chalcopyrite, sphalerite, pyrite and barite, with negligible detrital and biogenic inputs. Geochemically, the core is enriched in elements derived from high-temperature hydrothermalism (Fe, Cu, Zn and Ba) and depleted in elements derived from low-temperature hydrothermalism (Mn), and metasomatism (Mg). The U/Fe content ratio is elevated, particularly in the deeper parts of the core, consistent with uptake from seawater associated with sulphide alteration. Rare earth elements (REE) concentrations are low and chondrite-normalized patterns are characteristic of high-temperature vent fluids with an enrichment in light REE and a pronounced positive Eu anomaly. A stronger positive Eu anomaly associated with higher La_n/Sm_n at the core top is controlled by barite precipitation. The hydrothermal influence on the REE decreases downcore with some evidence for a stronger seawater influence at depth. Nd isotopes also exhibit an increased detrital/seawater influence downcore. Pb isotope ratios are uniform and plot on the Northern Hemisphere Reference Line in a small domain defined by LS basalts and exhibit no detrital or seawater influence. Lucky Strike sediments are derived from high-temperature mineralization and are overprinted by a weak seawater–sediment interaction when compared with other Atlantic hydrothermal sites such as TAG. The larger seawater input and/or a larger detrital contribution in deeper layers can be explained by variable hydrothermal activity during sediment formation, suggesting different pulses in activity of the LS hydrothermal system.     

Third dimension of a presently forming VMS deposit: TAG hydrothermal mound, Mid-Atlantic Ridge, 26°N

ODP drilling of the active TAG hydrothermal mound at 26°N on the Mid-Atlantic Ridge provided the first insights into the third dimension of a volcanic-hosted massive sulfide (VMS) deposit on a sediment-free mid-ocean ridge. Sulfide precipitation at this site started at least 20,000 years ago and resulted in the formation of a distinctly circular, 200-m diameter, 50-m-high pyritic mound and a silicified stockwork complex containing approximately 3.9 million tonnes of sulfide-bearing material with an average of 2.1 wt% Cu and 0.6 wt% Zn in 95 samples collected from 1–125 m below the seafloor. The periodic release of high-temperature hydrothermal fluids at the same location for several thousand years with intermittent periods of hydrothermal quiesence is the dominating process in the formation of the TAG hydrothermal mound. Distinct geochemical, mineralogical and isotopic zonation as well as a complex assemblage of sulfide-anhydrite-quartz bearing breccias can be related to this process. Geochemical depth profiles indicate extremely low base and trace element concentrations for the interior of the mound, which clearly contrasts with published analyses of samples collected from the surface of the TAG mound. This is explained by continued zone refining during which metals were mobilized from the interior of the mound by upwelling, hot (>350 °C) hydrothermal fluids. Mixing of these fluids with infiltrating ambient seawater subsequently caused redeposition of metals close to the mound-seawater interface. The sulfur isotopic composition of bulk sulfides (+4.4 to +8.2‰δ³⁴S; average +6.5‰) is unusually heavy when compared to other sediment-free mid-ocean ridge deposits and implies the introduction of heavy seawater sulfur to the hydrothermal fluid. The slight increase in sulfur isotope ratios with depth and distinct variations between early, disseminated sulfides related to wallrock alteration, and massive as well as late vein sulfides indicates widespread entrainment of seawater deep into the system. Fluid inclusion measurements in quartz and anhydrite reveal high formation temperatures throughout the TAG mound (up to 390 °C) at one time with an overall increase in trapping temperatures with depth. Lower formation temperatures close to the paleo-seafloor indicate local entrainment of seawater into the mound. Formation temperatures for a central anhydrite-bearing zone range from 340–360 °C and are slightly lower than the exit temperature of hydrothermal fluids presently venting at the Black Smoker Complex (360–369 °C). Fluid inclusions in quartz and anhydrite from the stockwork zone are characterized by formation temperatures higher than 375 °C, indicating conductive cooling of the hydrothermal fluids or mixing with ambient seawater prior to venting. Formation temperatures for quartz from an area of extremely low heat flow at the western side of the mound reach up to 390 °C, implying that this area was once part of a high-temperature hydrothermal upflow zone. The low heat flow and the absence of anhydrite within this part of the mound are strong indications that the recent pulse of high-temperature hydrothermal activity is not affecting this area and provides evidence for significant changes in the fluid flow regime underneath the deposit between hydrothermal cycles. Received: 16 November 1998 / Accepted: 19 August 1999     

Insights to magmatic-hydrothermal processes in the Manus back-arc basin as recorded by anhydrite

Microchemical analyses of rare earth element (REE) concentrations and Sr and S isotope ratios of anhydrite are used to identify sub-seafloor processes governing the formation of hydrothermal fluids in the convergent margin Manus Basin, Papua New Guinea. Samples comprise drill-core vein anhydrite and seafloor massive anhydrite from the PACMANUS (Roman Ruins, Snowcap and Fenway) and SuSu Knolls (North Su) active hydrothermal fields. Chondrite-normalized REE patterns in anhydrite show remarkable heterogeneity on the scale of individual grains, different from the near uniform REE_N patterns measured in anhydrite from mid-ocean ridge deposits. The REE_N patterns in anhydrite are correlated with REE distributions measured in hydrothermal fluids venting at the seafloor at these vent fields and are interpreted to record episodes of hydrothermal fluid formation affected by magmatic volatile degassing. ⁸⁷Sr/⁸⁶Sr ratios vary dramatically within individual grains between that of contemporary seawater and that of endmember hydrothermal fluid. Anhydrite was precipitated from a highly variable mixture of the two. The intra-grain heterogeneity implies that anhydrite preserves periods of contrasting hydrothermal versus seawater dominant near-seafloor fluid circulation. Most sulfate δ³⁴S values of anhydrite cluster around that of contemporary seawater, consistent with anhydrite precipitating from hydrothermal fluid mixed with locally entrained seawater. Sulfate δ³⁴S isotope ratios in some anhydrites are, however, lighter than that of seawater, which are interpreted as recording a source of sulfate derived from magmatic SO₂ degassed from underlying felsic magmas in the Manus Basin. The range of elemental and isotopic signatures observed in anhydrite records a range of sub-seafloor processes including high-temperature hydrothermal fluid circulation, varying extents of magmatic volatile degassing, seawater entrainment and fluid mixing. The chemical and isotopic heterogeneity recorded in anhydrite at the inter- and intra-grain scale captures the dynamics of hydrothermal fluid formation and sub-seafloor circulation that is highly variable both spatially and temporally on timescales over which hydrothermal deposits are formed. Microchemical analysis of hydrothermal minerals can provide information about the temporal history of submarine hydrothermal systems that are variable over time and cannot necessarily be inferred only from the study of vent fluids.     

Silicon isotope and trace element constraints on the origin of ∼3.5 Ga cherts: Implications for Early Archaean marine environments

Silicon (Si) isotope variability in Precambrian chert deposits is significant, but proposed explanations for the observed heterogeneity are incomplete in terms of silica provenance and fractionation mechanisms involved. To address these issues we investigated Si isotope systematics, in conjunction with geochemical and mineralogical data, in three well-characterised and approximately contemporaneous, ∼3.5 Ga chert units from the Pilbara greenstone terrane (Western Australia).We show that Si isotope variation in these cherts is large (−2.4‰ to +1.3‰) and was induced by near-surface processes that were controlled by ambient conditions. Cherts that formed by chemical precipitation of silica show the largest spread in δ³⁰Si (−2.4‰ to +0.6‰) and are characterised by positive Eu, La and Y anomalies and overall depletions in lithophile trace elements. Silicon isotope systematics in these orthochemical deposits are explained by (1) mixing between hydrothermal fluids and seawater, and/or (2) fractionation of hydrothermal fluids by subsurface losses of silica due to conductive cooling. Rayleigh-type fractionation of hydrothermal fluids was largely controlled by temperature differences between these fluids and seawater. Lamina-scale Si isotope heterogeneity within individual chemical chert samples up to 2.2‰ is considered to reflect the dynamic nature of hydrothermal activity. Silicified volcanogenic sediments lack diagnostic REE+Y anomalies, are enriched in lithophile elements, and exhibit a much more restricted range of positive δ³⁰Si (+0.1‰ to +1.1‰), which points to seawater as the dominant source of silica.The proposed model for Si isotope variability in the Early Archaean implies that chemical cherts with the most negative δ³⁰Si formed from pristine hydrothermal fluids, whereas silicified or chemical sediments with positive δ³⁰Si are closest to pure seawater deposits. Taking the most positive value found in this study (+1.3‰), and assuming that the Si isotope composition of seawater is governed by input of fractionated hydrothermal fluids, we infer that the temperature of ∼3.5 Ga seawater was below ∼55 °C.     

Hydrothermal Fe-Si-Mn oxide deposits from the Central and South Valu Fa Ridge, Lau Basin

A series of samples from the Hine Hina hydrothermal field (HHF) and the Mariner hydrothermal field (MHF) in the Central and Southern Valu Fa Ridge (VFR), Lau Basin were examined to explain the source origin and formation of the hydrothermal Fe-Si-Mn oxide deposits. The mineralogy was studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), Mössbauer spectroscopy, and energy-dispersive spectroscopy (EDS). For the Fe-Mn oxide crusts in the HHF, varying amounts of volcanic fragments and some seawater contributions were recognized, along with higher concentrations of Mn, Al, Co, Ni, Zn, Sr, Mo, elevated ∑REE and negative Ce anomalies. In contrast, the Si-rich oxide samples of the MHF were enriched in Cu, Pb and Ba, indicative of proximity to a hydrothermal jet. Moreover, conductive cooling of hydrothermal fluid evoked the Si-rich deposit formation in the MHF. The Sr, Nd and Pb isotope data provided further constraints regarding the source and formation of the Fe-Si-Mn deposits in the VFR by showing that the samples of the HHF are a mixture of three components, namely, hydrothermal fluid, seawater and volcanic materials, whereas the samples of the MHF were dominated by hydrothermal fluids. The seawater had a minor influence on the Nd isotope data, and the Pb isotope data exhibited a close association with the substrate rock and preformed volcaniclastic layers in this area. The occurrence of relatively high Mn/Fe ratios in the hydrothermal deposits of this area may be a good indicator of the propagating activities of the VFR over geological time.     

云南大平掌铜多金属矿床稀土元素地球化学特征

滇西大平掌铜多金属矿床具典型的“双层结构”。对上部盆地相的块状硫化物和下部通道相的细脉浸染状硫化物的稀土元素分析表明,前者具正Eu异常的球粒陨石标准化配分模式,后者具负Eu异常的配分模式。这种变化与成矿流体演化有关。通过与大西洋中脊TAG热液活动区表层沉积硫化物和黑烟囱流体等的稀土元素配分模式对比,可以认为成矿是火山喷流沉积作用的结果。     

Formation of Thetis Deep metal-rich sediments in the absence of brines,Red Sea

Almost all Red Sea deeps contain metal-rich sediments covered by brine pools. It is generally agreed that these metal-rich deposits precipitated from overlying metal-rich brines that originated from migrating hydrothermal fluids. No brine pool has ever been reported in Thetis Deep, inciting us to evaluate if such a brine layer ever occurred in the deep during the past. In order to address that questioning, a study combining mineralogical, geochemical (major-, minor-, rare-earth elements) and isotopic (Sr, Nd, Pb) approaches was completed on cored sediments and extracted interstitial waters from inside and outside the deep.The sediments have an overall hydrothermal origin, as shown by the REE concentrations and patterns, metal contents, and Pb–Nd isotopic data, all pointing to a mantle signature. The intensity of the hydrothermal activity varied with time in the deep; the most intense episode resulting in an almost pure Fe-oxi-hydroxide layer. Varied chemical arguments, especially the Zr and REE data of the sediments, favor the fact that the whole sedimentation in Thetis Deep occurred in the absence of a stable, salt-rich and mineralized brine pool, and that no brine layer ever existed. This conclusion is supported by the constant Sr isotope composition of the sediment and its interstitial waters that are almost identical to that of the Red Sea seawater. The study also suggests that hydrothermal activity monitored fluid supplies that interacted differently with seawater in the different Red Sea deeps, resulting in an overall formation of metal-rich sediments, but along varied local conditions.     

Geochemical patterns of a sheared fluorite vein, Parzan, Spanish Central Pyrenees

The formation of Parzán fluorite-lead «extension-type» vein (Spanish Central Pyrenees) is related to the post-Hercynian hydrothermal activity widespread not only in the Pyrenees but in Western Europe as well. The lode was later strongly deformed during the Alpine orogeny with textural modifications and destruction of primary fluid inclusions. In order to determine if geochemical signatures of the vein were disturbed during Alpine deformation, post-ore fluid inclusions and quartz oxygen-isotopes have been addressed. Microthermometry and X-ray microanalysis of frozen inclusions confirm the Na-Ca-Cl character of post-ore fluid circulations and indicate that they were originally derived from a single source: Triassic connate waters. Oxygen isotope data on quartz formed during deformation along with trace element geochemistry suggest that the geochemical signatures of the vein (mainly REE and ⁸⁷Sr/⁸⁶Sr) were apparently not reset during deformation. The REE content of fluorites is very high (up to 0.12%); the chondrite normalized REE patterns display a continuous decrease from La to Lu. Sulphur isotope data for the Parzán vein is outside the typical “deep seated” range, suggesting dominantly crustal sources of sulphur for sulphides, while formation waters may be proposed for barite. Parzán fluorites have the most radiogenic Sr values of all the investigated fluorite deposits in Central Pyrenees. They scatter in the range of both the igneous rocks and the Cambrian-Ordovician and Triassic detrital sequences of the Parzán area. If REE contents and ⁸⁷Sr/⁸⁶Sr ratios reflect the primary stage of vein filling as suggested by the good correlation between both geochemical signatures, the linear array between ⁸⁷Sr/⁸⁶Sr and 1/ΣREE is suggestive of a mixing process. The δ³⁴S, δ¹⁸O and ⁸⁷Sr/⁸⁶Sr parameters in barite, which postdates the fluorite, also provide strong evidence that barite deposition is a result of fluid mixing. Such an interpretation is in line with present-day ideas for the genesis of many of the F-Ba-Pb-Zn vein deposits in the Hercynian belt of Iberia.     

Fe Isotope Compositions of Cyprus Umbers

Submarine metalliferous sedimentary rocks are chemical precipitates resulted from hydrothermal exhalation near mid‐ocean ridge or faults. They record the submarine hydrothermal activity between lithosphere and hydrosphere and are critical for understanding Fe cycling in marine environment. Fe was expelled from the hydrothermal vent systems and was oxidized and precipitated in the ambient seawater, where the precipitation of hydrothermal Fe is largely controlled by oxidation state of seawater and is potentially revealed by its Fe isotope compositions. This hydrothermal process in modern hydrothermal vent systems have been well observed, but that for the ancient ones are still not well known. Umbers, or ferromanganoan sediments, overlying Troodos ophiolite in Cyprus of Mid‐Cretaceous age thus provides an excellent example for understanding the Fe cycles in ancient submarine hydrothermal process. Samples were collected from Margi village in Troodos and are mostly amorphous Fe‐Mn oxy‐hydroxides with very minor quartz, goethite, smectite and silicates such as clinopyroxene derived from the volcanic rocks. There is no terrestrial, detrital component. Samples were analyzed for their whole‐rock element and Fe isotope compositions. The results show that samples are composed mainly of SiO₂ (13～80 wt%), Fe₂O₃ (9～54 wt%) and MnO (1.5～10.4 wt%), with minor Al₂O₃ (0.7～4.3 wt%). PAAS‐normalized REE patterns are near flat with significantly negative Ce anomalies (Ce/Ce* is from 0.2 to 0.5) and slightly positive Eu anomalies (Eu/Eu* is around 1.1), indicating a source from the oxidized seawater and the high‐temperature hydrothermal fluids. δ⁵⁶FeIRMM‐014 values of samples are ‐0.32‰ to ‐0.15‰, with an average of ‐0.20‰, which are consistent with those of the hydrothermal fluids previously reported. The narrow Fe isotope compositions of Cyprus umbers that are close to those of submarine hydrothermal fluids indicates near complete oxidation of hydrothermal Fe²⁺ during its expulsion from the hydrothermal vent.     

Chemical and isotopic investigations into the origin of clay minerals from the Galapagos hydrothermal mounds field

A dark green authigenic nontronite is the major component of the Galapagos hydrothermal mounds field sediments. Oxygen isotopic compositions of the chemically purified, <0.2-μm fraction of the nontronitic clays indicate formation temperatures of 25° to 47°C, in contrast with measured in situ mounds temperatures of up to 15°C. Assuming an authigenic origin, the Fe-rich montmorillonite that dominates in the noncarbonate clay fraction of the surrounding pelagic ooze has isotopic formation temperatures of 27° to 39°C, compared with measured in situ temperatures of ca. 3.5° to 6.5°C. The higher isotopic formation temperatures calculated for the hydrothermal nontronite suggest either complex patterns of fluid circulation and nontronite precipitation presently within the mounds or a higher thermal history associated with rapid and episodic periods of deposition during the Holocene-Pleistocene. The apparent high isotopic temperature of the Fe-rich montmorillonite may reflect: (1) formation under hydrothermal conditions at spreading centers with subsequent dispersal by bottom currents, (2) a detrital origin of the mineral, or (3) a mixture of authigenic Fe-montmorillonite and detrital Al-montmorillonite in this region.     

Rare earth element and strontium isotope geochemistry in Dujiali Lake,central Qinghai-Tibet Plateau,China: Implications for the origin of hydromagnesite deposits

Rare earth element (REE) and strontium isotope data (⁸⁷Sr/⁸⁶Sr) are presented for hydromagnesite and surface waters that were collected from Dujiali Lake in central Qinghai-Tibet Plateau (QTP), China. The goal of this study is to constrain the solute sources of hydromagnesite deposits in Dujiali Lake. All lake waters from the area exhibit a slight LREE enrichment (average [La/Sm]_PAAS = 1.36), clear Eu anomalies (average [Eu/Eu*]_PAAS = 1.31), and nearly no Ce anomalies. The recharge waters show a flat pattern (average [La/Sm]_PAAS = 1.007), clear Eu anomalies (average [Eu/Eu*] _PAAS = 1.83), and nearly no Ce anomalies (average [Ce/Ce*]_PAAS = 1.016). The REE+Y data of the surface waters indicate the dissolution of ultramafic rock at depth and change in the hydrogeochemical characteristics through fluid-rock interaction. These data also indicate a significant contribution of paleo-groundwater to the formation of hydromagnesite, which most likely acquired REE and Sr signatures from the interaction with ultramafic rocks. The ⁸⁷Sr/⁸⁶Sr data provide additional insight into the geochemical evolution of waters of the Dujiali Lake indicating that the source of Sr in the hydromagnesite does not directly derive from surface water and may have been influenced by both Mg-rich hydrothermal fluids and meteoric water. Additionally, speciation modeling predicts that carbonate complexes are the most abundant dissolved REE species in surface water. This study provides new insights into the origins of hydromagnesite deposits in Dujiali Lake, and contributes to the understanding of hydromagnesite formation in similar modern and ancient environments on Earth.     

Origins of Nd–Sr–Pb isotopic variations in single scheelite grains from Archaean gold deposits,Western Australia

Accessory gangue scheelite (CaWO₄) from the Archaean Mt. Charlotte lode Au deposit can be divided into two types with different rare earth element (REE) signatures. In some scheelite grains, specific REE signatures are reflected by different cathodoluminescence colours, which can be used to map their often complex oscillatory intergrowths. Domains with specific REE contents from two grains were sampled for Sm/Nd, Rb/Sr and Pb isotopic analyses using a micro-drilling technique.Type I scheelite is strongly enriched in middle REE (MREE) and Eu anomalies are either absent or slightly positive. Four fragments collected from Type I regions of two crystals have initial ⁸⁷Sr/⁸⁶Sr and ε_Nd values ranging from 0.70141 to 0.70163 and +2.5 to +3.5, respectively, and Pb isotope ratios reflecting the composition of greenstone sequence. This may indicate that Nd and Pb have their source, either locally or regionally, in the greenstones. Basic greenstone lithologies have ⁸⁷Sr/⁸⁶Sr<0.7015, and the radiogenic Sr signatures indicate that part of the Sr originated from felsic lithologies located either within or beneath the host greenstone pile. Alternatively, the Sr signature may have evolved from preferential leaching of a Rb-rich mineral during hydrothermal alteration of the greenstone.The REE patterns of Type II scheelite are either flat or MREE-depleted and have strong positive Eu anomalies. Three fragments collected from Type II regions of the same two crystals have initial ⁸⁷Sr/⁸⁶Sr ratios and ε_Nd values between 0.70130 and 0.70146, and +1.1 to +2.6, respectively, and Pb isotope signatures that are once again similar to that of the greenstone. This implies that ⁸⁷Sr/⁸⁶Sr ratios in Type II fluids were closer to those of the host dolerite (0.7008–0.7013), due to more extensive fluid interaction with the dolerite.A positive correlation between Na and REE suggests that REE³⁺ are accommodated by the coupled substitution REE³⁺+Na⁺=2 Ca²⁺ into both Type I and Type II scheelite. This is consistent with a fractional crystallisation model to explain the change in REE patterns from Type I to Type II, but not with a model involving different coupled substitutions and fluids from different origins. We propose that the complex REE and isotopic signatures of scheelite at Mt. Charlotte are related to small (<m) to medium (<km) scale processes involving mixing between “fresh” batches of hydrothermal fluid with fluids that had already been involved in extensive wall-rock alteration.The very high-ε_Nd values measured in some scheelites have been previously used to link gold mineralisation with komatiites containing unusually high Sm/Nd ratios. However, tiny (<20 μm) grains of secondary hydroxyl-bastnäsite were found within micro-fractures of one scheelite grain containing an extremely high-ε_Nd signature. The hydroxyl-bastnäsite probably formed during recent REE redistribution within the scheelite as a result of meteoric fluid circulation. The scale of this cryptic low-temperature alteration is sufficient to explain the anomalously high-ε_Ndi values observed in scheelite from Western Australia.     

Submarine hydrothermal contribution for the extreme element accumulation during the early Cambrian,South China

Throughout the geological history of the Earth, submarine hydrothermal activity has played an important role in seawater chemistry, biological evolution and enrichment of metals in the Earth crust. However, the prospect of hydrothermal activity for extreme element accumulation during the early Cambrian, a key geological period, in South China has not been well-constrained. This study reports geochemical (e.g. REE and Sr isotope) investigations of a coarse-grained limestone layer and associated calcite veins in Zunyi and Nayong areas, Guizhou Province, to constrain the hydrothermal activity and evaluate the significance of hydrothermal contribution to extreme element accumulation during the early Cambrian, South China. Our results reveal positive Eu anomalies and higher initial ⁸⁷Sr/⁸⁶Sr ratios (0.7083–0.7150) for carbonate samples than those of early Cambrian seawater, indicating the presence of hydrothermal processes. Combined with constraints from the spatial relationships and coincidence with adjacent mineralization, these hydrothermal processes provide the most probable contribution for polymetallic Ni–Mo–PGE mineralization. Furthermore, there are abundant hydrothermal dolomite and barite-calcite veins in the dolostone of the Dengying Formation, indicating the occurrence of a variety of hydrothermal fluids. Overall, multi-stage hydrothermal pulses with different fluid compositions spanned the Ediacaran–Cambrian transition in South China. In particular, these hydrothermal fluids with positive Eu anomalies and enriched radiogenic Sr, originating from Proterozoic mafic/ultramafic rocks, may have flowed through the underlying Precambrian silicate clastic rocks (e.g., Xiajiang, Banxi and Lengjiaxi Groups) and may have been crucial for the marine environment, biological diversity and extreme element accumulation during the early Cambrian, South China.     

The nature of crystalline silica from the TAG submarine hydrothermal mound, 26°N Mid Atlantic Ridge

Silica occurs in abundance in a variety of hydrothermal samples from the Trans-Atlantic Geotraverse (TAG) hydrothermal mound, 26°N Mid-Atlantic Ridge. The water content, trace element chemistry, and mineralogy of crystalline silica from 15 different samples have been examined by vibrational spectroscopy and probe microanalysis. The samples are from: shallow subsurface ferric iron oxyhydroxide silica deposits (n=4), a fragment of an active white smoker chimney (n=1), anhydrite bearing hydrothermal breccias (n=2), pyrite silica breccias (n=3), and silicified wall rock breccias (n=5). Length-fast chalcedony occurs in association with variable quantities of ferric iron oxyhydroxides in hydrothermal breccias from the mound flanks, within shallower subsurface chert samples, and within white smoker chimney walls. Samples from the anhydrite zone contain textures which are suggestive of an origin involving replacement of anhydrite. Samples taken from TAG 1 and 5 from below the anhydrite zone contain no chalcedony. Instead they contain subhedral quartz crystals which show oscillatory zoning in aluminium. Two types of crystalline silica namely, type A and type B quartz, are defined on the basis of the infrared spectra in the OH region from 3200 cm⁻¹ to 3600 cm⁻¹. The type A quartz occurs beneath the anhydrite zone at TAG 1 and 5. We propose a model that relates specific varieties of crystalline silica to different thermal and chemical environments within the mound interior. Length-fast chalcedony occurs in an outer low temperature envelope across the top and sides of the mound. The common association between length-fast chalcedony and ferric iron oxyhydroxides suggests that chalcedony crystallization is favoured where catalysis by ferric iron can occur. The apparent suppression of fibrous silica at the expense of single quartz crystals with increasing depth is attributed to differing growth rates and degrees of supersaturation of silica-bearing solutions with increasing temperature within the mound. The transition from type A to type B single crystal growth is interpreted to occur at temperatures approaching ˜360 °C due to decreasing solubility of aluminium in quartz, so that aluminium is rendered unavailable for type A valence compensation. Received: 10 September 1998 / Accepted: 6 July 1999     

Deducing the source and composition of rare earth mineralising fluids in carbonatites: insights from isotopic (C,O, <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr) data from Kangankunde,Malawi

Carbonatites host some of the largest and highest grade rare earth element (REE) deposits but the composition and source of their REE-mineralising fluids remains enigmatic. Using C, O and ⁸⁷Sr/⁸⁶Sr isotope data together with major and trace element compositions for the REE-rich Kangankunde carbonatite (Malawi), we show that the commonly observed, dark brown, Fe-rich carbonatite that hosts REE minerals in many carbonatites is decoupled from the REE mineral assemblage. REE-rich ferroan dolomite carbonatites, containing 8–15 wt% REE₂O₃, comprise assemblages of monazite-(Ce), strontianite and baryte forming hexagonal pseudomorphs after probable burbankite. The ⁸⁷Sr/⁸⁶Sr values (0.70302–0.70307) affirm a carbonatitic origin for these pseudomorph-forming fluids. Carbon and oxygen isotope ratios of strontianite, representing the REE mineral assemblage, indicate equilibrium between these assemblages and a carbonatite-derived, deuteric fluid between 250 and 400 °C (δ¹⁸O + 3 to + 5‰_VSMOW and δ¹³C ? 3.5 to ? 3.2‰_VPDB). In contrast, dolomite in the same samples has similar δ¹³C values but much higher δ¹⁸O, corresponding to increasing degrees of exchange with low-temperature fluids (< 125 °C), causing exsolution of Fe oxides resulting in the dark colour of these rocks. REE-rich quartz rocks, which occur outside of the intrusion, have similar δ¹⁸O and ⁸⁷Sr/⁸⁶Sr to those of the main complex, indicating both are carbonatite-derived and, locally, REE mineralisation can extend up to 1.5 km away from the intrusion. Early, REE-poor apatite-bearing dolomite carbonatite (beforsite: δ¹⁸O + 7.7 to + 10.3‰ and δ¹³C ?5.2 to ?6.0‰; ⁸⁷Sr/⁸⁶Sr 0.70296–0.70298) is not directly linked with the REE mineralisation.     

Formation of Fe-Mn-Si oxide and nontronite deposits in hydrothermal fields on the Valu Fa Ridge, Lau Basin

Hydrothermal Fe-Mn-Si oxides and nontronite are pervasive in the Hine Hina, Vai Lili and Mariner hydrothermal fields along the central Valu Fa Ridge, Lau Basin. Morphometric and mineralogical analyses reveal that the iron-rich filaments are the most important constituents of these Fe-Mn-Si oxide deposits. Both the morphologies and chemical composition of the filaments indicate that neutrophilic Fe-oxidizing bacteria have played a key role in the formation of these deposits. A key process of the formation of these deposits is the creation of a complicated filamentous network in which a series of metabolic activities and passive sorption and nucleation processes occur. The precipitation of dissolved Si in unsaturated and saturated states leads to a “two-generation” growth model in the hydrothermal vents. The precipitation of amorphous opal occurs in a relatively narrow temperature range (41.1-42.9 °C) based on oxygen isotope analyses, indicating a fast precipitation rate of opal-A when conductive cooling of the hydrothermal fluid occurrs. Patchy nontronite in the Mariner fields is a product of the direct precipitation from hydrothermal fluids at a temperature of ∼87.9 °C, whereas the scattered nontronite at the Hine Hina field is the product of the replacement of hydrothermal Fe-Si oxides at a temperature of ∼46.2 °C.     

Controls of fluid chemistry and complexation on rare-earth element contents of anhydrite from the Pacmanus subseafloor hydrothermal system,Manus Basin,Papua New Guinea

Ocean Drilling Program (ODP) leg 193 successfully drilled four deep holes (126 to 386 m) into basement underlying the active dacite-hosted Pacmanus hydrothermal field in the eastern Manus Basin. Anhydrite is abundant in the drill core material, filling veins and vesicles, cementing breccias, and occasionally replacing igneous material. We report rare-earth element (REE) contents of anhydrite from a site of diffuse venting (Site 1188) which show extreme variability, in terms of both absolute concentrations (e.g., 0.08–28.3 ppm Nd) and pattern shape (La_N/Sm_N=0.08–3.78, Sm_N/Yb_N=0.48–23.1, Eu/Eu*=0.59–6.1). The range of REE patterns in anhydrite includes enrichments in the middle and heavy REEs and variable Eu anomalies. The patterns differ markedly from those of anhydrite recovered during ODP Leg 158 from the TAG hydrothermal system at the Mid-Atlantic Ridge which display uniform LREE-enriched patterns with positive Eu anomalies, very similar to TAG vent fluid patterns. As the system is active, the host-rock composition is uniform, and the anhydrite veins appear to relate to the same hydrothermal stage, we can rule out predominant host-rock and transport control. Instead, we propose that the variation in REE content reflects waxing and waning input of magmatic volatiles (HF, SO₂) and variable complexation of REEs in the fluids. REE speciation calculations suggest that increased fluoride and possibly sulfate concentrations at Pacmanus may affect REE complexation in fluids, whereas at TAG only chloride and hydroxide complexes play a significant role. The majority of the anhydrites do not show positive Eu anomalies, suggesting that the fluids were more oxidizing than in typical mid-ocean ridge hydrothermal systems. We use other hydrothermal fluids from the Manus Basin (Vienna Woods and Desmos), which bracket the Pacmanus fluids in terms of acidity and ligand concentrations, to examine the dependence of REE complexation on fluid composition. Geochemical modeling reveals that under the prevailing conditions at Pacmanus (pH~3.5, T=250–300 °C), Eu oxidation state and the relative importance of fluoride versus chloride complexing are very sensitive to small variations in oxygen fugacity, temperature, and pH. Patterns with extreme mid-REE enrichment may reflect speciation effects (free-ion abundance) coupled with crystal chemical control. We conclude that the great variability in REE concentrations and pattern shape is likely due to variable fluid composition and REE complexation in the fluids. Editorial handling: L. Meinert     

An experimental study of alteration of oceanic crust and terrigenous sediments at moderate temperatures (51 to 350°C): insights as to chemical processes in near-shore ridge-flank hydrothermal systems

Studies of hydrothermal circulation within partly buried basement on the eastern flank of the Juan de Fuca Ridge (JFR) have shown that ridge-flank geochemical fluxes are potentially important for the global budgets of some elements. There are major uncertainties in these flux calculations, however, because the composition of these basement fluids is strongly dependent on temperature and because they may be modified by interaction with the overlying terrigenous sediments, either by diffusive exchange with basement or during upwelling to the seafloor. To better understand the nature and temperature control of basalt-fluid and sediment-fluid reactions at the JFR flank, we have conducted laboratory experiments between 51 and 350°C and at 400 bars pressure. K, Rb, and Si are leached from basalt between 150 and 351°C, and Sr and U are taken up. The direction of exchange of Li and Ca with basalt varies with temperature. Li and Sr are removed from fluid at 150°C, but isotope studies show that there is simultaneous release of both elements from basalt, indicating that uptake is controlled by the formation of secondary minerals. Moreover, our experiments confirm that Sr isotope exchange with oceanic crust occurs at moderate temperature and is not confined to high-temperature axial hydrothermal systems. Our data and field data from the JDR flank indicate that uptake of U into basalt at moderate temperature could remove between 9.9 and 15 × 10⁶ mol U yr⁻¹ from the oceans. This is higher than a recent estimate based on measurements of U in altered ocean crust (5.7 ± 3.3 × 10⁶ mol yr⁻¹), which concords with arguments that the Δ_element/heat ratios of JDR flank fluids are too large to be representative of average global flank fluids. K, Ca, Sr, Ba, Li, Si, and B are leached from terrigenous sediments between 51 and 350°C, and U is taken up. Cs and Rb are removed from the fluid below 100°C and leached from the sediment at higher temperature. Sr isotope data show that Sr is preferentially mobilised from volcanic components within terrigenous sediments, which may lead to an overestimation of the ridge-flank Sr isotope flux at the JDR if there is exchange of sediment pore fluids with basement.     

Origin of fluids in iron oxide–copper–gold deposits: constraints from δ 37Cl, 87Sr/86Sri and Cl/Br

The origin of the hypersaline fluids (magmatic or basinal brine?), associated with iron oxide (Cu–U–Au–REE) deposits, is controversial. We report the first chlorine and strontium isotope data combined with Cl/Br ratios of fluid inclusions from selected iron oxide–copper–gold (IOCG) deposits (Candelaria, Raúl–Condestable, Sossego), a deposit considered to represent a magmatic end member of the IOCG class of deposit (Gameleira), and a magnetite–apatite deposit (El Romeral) from South America. Our data indicate mixing of a high δ ³⁷Cl magmatic fluid with near 0‰ δ ³⁷Cl basinal brines in the Candelaria, Raúl–Condestable, and Sossego IOCG deposits and leaching of a few weight percent of evaporites by magmatic-hydrothermal (?) fluids at Gameleira and El Romeral. The Sr isotopic composition of the inclusion fluids of Candelaria, Raúl–Condestable, and El Romeral confirms the presence of a non-magmatic fluid component in these deposits. The heavy chlorine isotope signatures of fluids from the IOCG deposits (Candelaria, Raúl–Condestable, Sossego), reflecting the magmatic-hydrothermal component of these fluids, contrast with the near 0‰ δ ³⁷Cl values of porphyry copper fluids known from the literature. The heavy chlorine isotope compositions of fluids of the investigated IOCG deposits may indicate a prevailing mantle Cl component in contrast to porphyry copper fluids, an argument also supported by Os isotopes, or could result from differential Cl isotope fractionation processes (e.g. phase separation) in fluids of IOCG and porphyry Cu deposits.