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.     

Effect of the Red Sea brine-filled deeps (Shaban and Kebrit) on the composition and abundance of benthic and planktonic foraminifera

Composition and abundance of benthic and planktonic foraminifera in surface sediments of the brine-filled Shaban and Kebrit Deeps and some bathyal-slope environments in the northern Red Sea were examined for correlation with environmental conditions (e.g., bathymetry, sediment grain-size, organic matter, and carbonates) of the brine-filled deeps and normal Red Sea water. About 67 benthic foraminiferal species were recorded in these sediments. The lowest faunal density and diversity were recorded in the Shaban and Kebrit Deeps, whereas the highest density and diversity were recorded in the bathyal-slope sediments. Cluster analysis divided the benthic foraminiferal species into three major faunal assemblages. Buccella granulata–Gyroidinoides soldanii–Bolivina persiensis assemblage dominated the 650–1,300 m depth due to predominance of oligotrophic, highly oxygenated bottom waters. The Melonis novozealandicum–Spirophthalmidium acutimargo assemblage was recorded in the deep and bathyal-slope sediments indicating its tolerance for wider ranges of environmental conditions. The deeps were only dominated by the Brizalina spathulata assemblage indicating existence of un-totally anoxic conditions. The deeps yielded also very low planktonic foraminiferal density that may be attributed to occurrence of the seawater–brine interface which not only minimized the deposition of high buoyancy, large-test species (Globigerinoides sacculifer, Globigerinella siphonifera, and Orbulina universa), but also overestimated the small-test species (Globigerinoides ruber, Globoturborotalita rubescens, and Globigerinita glutinata) in the sediments. These findings should be taken into consideration when reconstructing paleoceanographic conditions of the Red Sea using core sediments from the brine-filled deeps.     

Ore transport and deposition in the Red Sea geothermal system: a geochemical model

Thermodynamic calculation of distribution of dissolved aqueous species in the Red Sea geothermal brine provides a model of ore transport and deposition in good agreement with observed accumulations of base metal sulfides, anhydrite, and barite.The Red Sea brine is recirculated seawater that acquires high salinity by low-temperature interaction with Miocene evaporites and is subsequently heated to temperatures in excess of 200°C by interaction with recent rift zone intrusive rocks. At temperatures up to 250°C, NaSO^?₄ and MgSO⁰₄ are the dominant sulfur-bearing species. H₂S forms by inorganic sulfate reduction at the higher temperatures but is maintained at a uniform concentration of about 2 ppm by the strength of the sulfate complexes.Chloride complexes solubilize metals at the higher temperatures, and thus sulfide and metals are carried together into the Atlantis II Deep. Below 150°C, the brine becomes supersaturated with respect to chalcopyrite, sphalerite, galena, and iron monosulfide due to chloride-complex dissociation. Sulfide precipitation rates, based on the rate of brine influx, are in good agreement with measured sedimentation rates. Anhydrite precipitates as crystalline fissure infillings from high-temperature inflowing brine. Barite forms from partial oxidation of sulfides at the interface between the lower hot brine and the transitional brine layer.     

Mineralogy,parageneses, and phase relations of copper-iron sulfides in the Atlantis II deep,red sea

New investigations are carried out on the mineralogy and mineral chemistry of sulfide assemblages obtained in samples from one core in the hydrothermally active, southwest basin of the Atlantis II deep, Red Sea. The most abundant sulfide phases are the exsolved intermediate solid solution (ISS) and chalcopyrite. Sphalerite, pyrrhotite, marcasite, mackinawite, and presumably wurtzite are also observed. Two distinct groups of paragenesis were encountered: (a) Intermediate solid solution with sphalerite incrustations and intergrowths, and (b) intermediate solid solution barren of sphalerite intergrowths. The first group is confined to the upper part of the Co zone and the SOAN zone (Bäcker and Richter 1973), and the second is present in the entire core 100-3-7. An optically isotropic chalcopyrite is found for the first time as a natural mineral in Atlantis II, Red Sea. Yet its existence as a novel phase needs x-ray confirmation. It exhibits a lower reflectivity than normal chalcopyrite and is isotropic. Chalcopyrite occurs either as a single phase or in association with tetragonal chalcopyrite. Our investigations indicate that the formation of Atlantis II deposits is a result of complex processes. These processes are characterized by compositional changes in the ore-bearing fluids and the change in sulfur fugacity (especially with depth). The presence of exsolved chalcopyrite lamellae in ISS indicates slow cooling below 450°C. However, it is difficult to understand why the cubic chalcopyrite is not converted to the tetragonal form even though the temperature of transformation lies above 450°C (470° – 500°C, Cabri 1973). The Cu/Fe ratio changes in the exsolved chalcopyrite lamellae from core to rim of the composite grains. The ratio is higher in the rims. This suggests that primary inhomogenous ISS grains formed from solutions with a continuous increase in the Cu/Fe ratio. Slow cooling is also required to account for the exsolution of chalcopyrite lamellae in ISS. The low sulfur content in isotropic chalcopyrite is also suggestive of low fs₂. The low S content in the chalcopyrite may be the controlling factor for the sluggish conversion from cubic to tetragonal chalcopyrite. Mackinawite lamellae show the same orientation in ISS and exsolved isotropic chalcopyrite indicating that mackinawite exsolved before the breakdown of ISS. This strongly suggests that mackinawite is stable above 300°C (contrary to experimental results by Zoka et al. 1973). Pyrrhotite was probably formed by the sulfurization of ilvaite. The pyrrhotite grains with several complex successive zones show the sequence of the sulfurization episodes.Metalliferous sediments related to hot brines were discovered in the Red Sea in 1964 (Miller et al. 1966). Since then, several papers have been published on this subject (Degens and Ross 1969, Bäcker and Schoell 1972, Bäcker and Richter 1973, Bignell et al. 1976, Shanks and Bishoff 1977, Weber-Diefenbach 1977, Nöltner 1979, Pottorf 1980, Pottorf and Barnes 1983, Oudin et al. 1984).Complex sulfide phases including intermediate solid solution (ISS), chalcopyrite, and a chalcopyritelike mineral (which exhibits a lower reflectivity than normal chalcopyrite and appears to be isotropic occur in the metalliferous sediments. These phases were found in association with several minerals in different parageneses. In an attempt to understand the origin of the formation of the sulfide-bearing sediments in the Atlantis II deep of the Red Sea, a detailed study of the phase relations of the Cu-Fe sulfide ores of this locality was carried out.     

Untersuchung von suspendiertem Material in den Hydrothermallaugen des Atlantis-II-Tiefs

Suspended matter was separated from the hydrothermal brines of the Atlantis-II Deep in the Red Sea. Contents of iron, manganese, copper, and zink collected on membrane filters were measured by X-ray-flourescence, and the main results were:

1. Metal concentrations in suspended form were lower by 10^?1 to 10^?5 compared to the dissolved concentrations of the brines.
2. Suspended copper and zink were enriched most pronounced in the deeper brine zone — markedly so in the SW-basin, values there ranged between 10 and 30μg/l, one Zn-value was as high as 60μ/l, the other basins contained mostly less than 1 to 10μg/l.
3. Iron, copper, and zink in the deeper brine zone and in few cases also in the 50°-brine were suspended in the form of sulfide compounds. This conclusion is based only on the slightly purple-, green-, and blue-colored gray hues of the material on the filters and its rapid oxidation upon contact with the air.
4. In the transition zone of the 50°/60°-brine iron hydroxides were highly concentrated with values ranging up to 1000μg Fe/l.
5. Suspended manganese is found only within the transition zone of brine to the normal sea water, where up to 200μg Mn/l in form of darkbrown manganese hydroxides were found.
6. Concurrently with the increased thermal activity since 1966 more strongly reducing conditions within the brines seemed apparent which were caused by discharge of higher amounts of Sulfides into the basins. Increased precipitation of heavy metal sulfides was found to be most pronounced in the SW-basin.

     

High-resolution methane profiles across anoxic brine–seawater boundaries in the Atlantis-II, Discovery, and Kebrit Deeps (Red Sea)

A decrease in temperature (ΔT up to 45.5 °C) and chloride concentration (ΔCl up to 4.65 mol/l) characterises the brine–seawater boundary in the Atlantis-II, Discovery, and Kebrit Deeps of the Red Sea, where redox conditions change from anoxic to oxic over a boundary layer several meters thick. High-resolution (100 cm) profiles of the methane concentration, stable carbon isotope ratio of methane, and redox-sensitive tracers (O₂, Mn⁴⁺/Mn²⁺, Fe³⁺/Fe²⁺, and SO₄²⁻) were measured across the brine–seawater boundary layer to investigate methane fluxes and secondary methane oxidation processes.

Substantial amounts of thermogenic hydrocarbons are found in the deep brines (mostly methane, with a maximum concentration up to 4.8×10⁵ nmol/l), and steep methane concentration gradients mainly controlled by diffusive flow characterize the brine–seawater boundary (maximum of 2×10⁵ nmol/l/m in Kebrit Deep). However, locally the actual methane concentration profiles deviate from theoretical diffusion-controlled concentration profiles and extremely positive δ¹³C–CH₄ values can be found (up to +49‰ PDB in the Discovery Deep). Both, the actual CH₄ concentration profiles and the carbon-13 enrichment in the residual CH₄ of the Atlantis-II and Discovery Deeps indicate consumption (oxidation) of ¹²C-rich CH₄ under suboxic conditions (probably utilizing readily available—up to 2000 μmol/l—Mn(IV)-oxihydroxides as electron acceptor). Thus, a combined diffusion–oxidation model was used to calculate methane fluxes of 0.3–393 kg/year across the brine–seawater boundary layer. Assuming steady-state conditions, this slow loss of methane from the brines into the Red Sea bottom water reflects a low thermogenic hydrocarbon input into the deep brines.     

Saline brines and metallogenesis in a modern sediment-filled rift: the Salton Sea geothermal system, California, U.S.A.

The Salton Sea geothermal system (SSGS) is the site of active hydrothermal metamorphism and metallogenesis in the delta of the Colorado River, which partially fills the Salton Trough rift zone at the head of the Gulf of California. Growth of the delta across the rift has isolated the northern part of the Salton Trough since the Pleistocene, forming the evaporative Salton Sea basin whose sediments host the SSGS. More than 70 commercial geothermal wells, including a 3.2 km deep research borehole drilled as part of the Salton Sea Scientific Drilling Project (SSSDP), are yielding a wealth of new data from this system.Within the SSGS, active greenschist facies metamorphism is occuring at temperatures 365°C at only 2–3 km depth, by reaction of NaCaKFeMnCl brines with the deltaic and lacustrine Pilo-Pleistocene sediments. Two kinds of base metal ore mineralization occur at depth: stratabound diagenetic Fe sulfides, and epigenetic vertical veins containing FeZnCuPb sulfides and Fex oxides. The vein mineralization occurs as two types: an older, reduced carbonate-sulfide assemblage, and a modern, oxidized, silicate-hematite-sulfide assemblage. The earlier assemblage formed at temperatures up to 100°C higher than the ambient temperatures measured in the wells today, implying that cooler, oxidized fluids have displaced hot, reduced fluids.A sharp interface between shallow fluids containing <12 wt % TDS and deep hypersaline brines containing 15–27 wt % TDS exists in the SSGS. The deeper hypersaline brines are rich in base metals (Fe 1500 ppm, Mn 1000 ppm, Zn 500 ppm) whereas the overlying lower-salinity fluids contain less than 100 ppm each of Fe, Mn and Zn. The modern silicate-hematite-sulfide vein assemblage is precipitating where the two fluids appear to be mixing. The two fluid types also have distincty different δ¹⁸O and δD relations. The shallow lower-salinity fluids have only partially-exchanged oxygen with deltaic and lacustrine host rocls. The deep hypersaline brines have exchanged oxygen extensively at 250°C with the deltaic sediments. δD values of the hypersaline brines are typically lighter than either the lower-salinity fluids or the modern evaporating groundwaters occupying the Salton Trough, implying a different source for the original fluids.The high salinities of the geothermal brines are derived from a combination of evaporation of fossil lakewaters, groundwater dissolution of shallow lacustrine evaporites, and subsurface hydrothermal metamorphism of buried lacustrine evaporites. Episodic filling and desiccation of the closed Salton Sea basin has allowed cold saline brines to form and percolate down into the sedimentary section. In some wells anyhydrite meta-evaporites and interbedded solution collapse breccias occur at 1 km depth. The anyhydrite contains fluid inclusions that are saturated in halite at their homogenization temperatures of 300°C, recording the hydrothermal dissolution of bedded salt. Based on Sr and Pb isotopic data and whole-rock chemical data, the source of the metals in the hypersaline brines is from leaching of the host sediments. However, the origin of reduced S for ore mineralization remains an enigma. δ³⁴S values for vein sulfides cluster uniformly around zero per mil, implying that an isotopically-homogeneous source of reduced sulfide exists in the brines. It is possible that the vein sulfides receive a constribution from a magmatic S source.Movement and mixing of brines of different chemistry and oxidation states play a major role in ore genesis. Our model envisages an early stage in which a deep brine pool accumulated at depth in the sedimentary section by partial section by partial evaporation of basin and dissolution of bedded salts. Intrusion of rift-related basaltic magma into the base of the sedimentary caused heatingand fracturing of the sediments, resulting in precipitation of the carbonate-sulfide veins during pore fluid expulsion. Heating also caused a diapir of the hypersaline brine to rise and displace colder, less saline, shallower pore fluids. This brine intrusion was accompanied by pervasive and extensive mineralization. As this diapir cooled it began to move downward, drawing in shallow, more oxidized fluids and causing the formation of the modern silicate-hematite-sulfide vein ore zone.     

Light hydrocarbons in Red Sea brines and sediments

Light hydrocarbon (C₁-C₃) concentrations in the water from four Red Sea brine basins (Atlantis II, Suakin, Nereus and Valdivia Deeps) and in sediment pore waters from two of these areas (Atlantis II and Suakin Deeps) are reported. The hydrocarbon gases in the Suakin Deep brine (T = ~ 25°C, $\text{Cl}{}^{\mathrm{?}}\text{= ~ 85‰}$, $\text{CH}{}_4\text{=}\text{~ 71}\text{1}$) are apparently of biogenic origin as evidenced by $\text{C}{}_1\text{(C}{}_2\text{+ C}{}_3$) ratios of ~ 1000. Methane concentrations (6–8 μl/l) in Suakin Deep sediments are nearly equal to those in the brine, suggesting sedimentary interstitial waters may be the source of the brine and associated methane.The Atlantis II Deep has two brine layers with significantly different light hydrocarbon concentrations indicating separate sources. The upper brine (T = ~ 50°C, $\text{Cl}{}^{\mathrm{?}}\text{= ~ 73‰}$, CH₄ = ~ 155 μl/l) gas seems to be of biogenic origin [$\text{C}{}_1\text{(C}{}_2\text{+ C}{}_3\text{) = ~1100}$], whereas the lower brine (T = ~ 61°C, $\text{Cl}{}^{\mathrm{?}}\text{= ~ 155‰}$, CH₄ = ~ 120μl/l) gas is apparently of thermogenic origin [$\text{C}{}_1\text{(C}{}_2\text{+ C}{}_3\text{) = ~ 50}$]. The thermogenic gas resulting from thermal cracking of organic matter in the sedimentary column apparently migrates into the basin with the brine, whereas the biogenic gas is produced in situ or at the seawater-brine interface. Methane concentrations in Atlantis II interstitial waters underlying the lower brine are about one half brine concentrations; this difference possibly reflects the known temporal variations of hydrothermal activity in the basin.     

Origin of CaCl2 brines by basalt-seawater interaction: Insights provided by some simple mass balance calculations

Modern rift zone hydrothermal brines are typically CaCl₂-bearing brines, an unusual chemical signature they share with certain oil field brines, fluid inclusions in ore minerals and a few uncommon saline lakes. Many origins have been suggested for such CaCl₂ brines but in the Reykjanes, Iceland, geothermal system a strong empirical case can be made for a basalt-seawater interaction origin. To examine this mechanism of CaCl₂ brine evolution some simple mass balance calculations were carried out. Average Reykjanes olivine tholeiite was “reacted” with average North Atlantic seawater to make an albite-chlorite-epidotesphene rock using Al₂O₃ as the conservative rock component and Cl as the conservative fluid component. The excess components released by the basalt to the fluid were “precipitated” at 275° C as quartz, calcite, anhydrite, magnetite and pyrite to complete the conversion to greenstone. The resulting fluid was a CaCl₂ brine of seawater chlorinity with a composition remarkably similar to the actual Reykjanes brine at 1750 m depth. Thus, the calculations strongly support the idea that the Reykjanes CaCl₂ brines result from “closed system” oceanic basalt-seawater interaction (albitization — chloritization mechanism) at greenschist facies temperatures. The calculation gives a seawater: basalt mass ratio of 3∶1 to 4∶1 (vol. ratio of 9∶1 to 12∶1), in keeping with experimental results, submarine vent data and with ocean crust cooling calculations. The brine becomes anoxic because there is insufficient dissolved or combined oxygen to balance all the Fe released from the basalt during alteration. Large excesses of Ca are released to the fluid and precipitate out in the form of anhydrite which essentially sweeps the brine free of sulfate leaving an elevated Ca concentration. The calculated rock-water interaction basically involves Na + Mg + SO₄ ? Ca + K, simulating chemical differences observed between oceanic basalts and greenstones from many mid-ocean ridges.     

β-FeOOH · Cln (akaganéite) and Fe1-xO (wüstite) in hot brine from the Atlantis II Deep (Red Sea) and the uptake of amino acids by synthetic β-FeOOH · Cln

A yellowish brown precipitate in samples of Red Sea hot brine has been identified as β-FeOOH · Cl_n (akaganéite) by Guinier-Hägg X-ray diffraction techniques, transmission electron microscopy (TEM), electron diffraction and electron excited X-ray fluorescence. Microcrystals of Fe_1-xO (wüstite) were also identified by electron diffraction. Synthetic β-FeOOH · Cl_n characterized by the same techniques was identical with the brine precipitate.Bonding between β-FeOOH · Cl_n and ¹⁴C labeled amino acids is pH dependent: between pH 3 and pH 7.6 amino acids were bound to the extent of 40 to 60% or 0.6 to 0.9 mmol per kg of iron oxide hydroxide. Some selectivity in affinity for different amino acids was observed, however, the effect is insufficient to explain the unusual distribution in the Atlantis II Deep brine reported in the literature.     

Low temperature hydrothermal maturation of organic matter in sediments from the Atlantis II Deep,Red Sea

Hydrocarbons and bulk organic matter of two sediment cores (No. 84 and 126, CHAIN 61 cruise) located within the Atlantis II Deep have been analyzed. Although the brines overlying the coring areas were reported to be sterile, microbial inputs and minor terrestrial sources represent the major sedimentary organic material. This input is derived from the upper water column above the brines.Both steroid and triterpenoid hydrocarbons show that extensive acid-catalyzed reactions are occurring in the sediments. In comparison with other hydrothermal (Guaymas Basin) or intrusive systems (Cape Verde Rise), the Atlantis II Deep exhibits a lower degree of thermal maturation. This is easily deduced from the elemental composition of the kerogens and the absence of polynuclear aromatic hydrocarbons of a pyrolytic origin in the bitumen.The lack of carbon number preference among the n-alkanes suggests, especially in the case of the long chain homologs, that the organic matter of Atlantis II Deep sediments has undergone some degree of catagenesis. However, the yields of hydrocarbons are much lower than those observed in other hydrothermal areas. The effect of lower temperature and poor source-rock characteristics appear to be responsible for the differences.     

Conrad Deep, Northern Red Sea: Development of an early stage ocean deep within the axial depression

The northern Red Sea represents a continental rift in its final stage and close to the following stage of seafloor spreading. Ocean deeps within the evaporites of the northern Red Sea seem to accompany this process and are thought to be surface expressions of first seafloor spreading cells. In 1999 during R/V Meteor cruise M44/3 a dense multichannel seismic and hydroacoustic survey was conducted in order to investigate the initial formation process of the Conrad Deep, a young northern Red Sea deep. Three seismic units were differentiated in the uppermost part of the Miocene evaporites and the Plio-Quaternary sediments. A weakness zone within the evaporites, oblique to the main extension direction of the Red Sea, led to a transtension process within the evaporites that opened the deep. Its formation is directly related to the emplacement of magmatic bodies in its vicinity and the focusing of the Red Sea extension to the axial depression. The Conrad Deep is an intra-evaporite basin that cannot be regarded as surficial expression of a basement structure as the low shear strength of the evaporites decouple the sediments from the basement. However, its position and shape in combination with the accompanying geophysical anomalies point to a strong correlation with the Red Sea rifting process.     

Amorphous copper and zinc sulfides in the metalliferous sediments of the Red Sea

Detailed studies on the copper and zinc distribution in metalliferous sediments from the Atlantis II Deep (Red Sea) demonstrate that beside chalcopyrite and sphalerite appreciable amounts of copper and zinc are found in X-ray amorphous copper and zinc sulfides not previously described. Only low contents of copper and zinc are present in nontronites, hydroxides and carbonates.     

Age, thermal evolution and history of the Black Sea Basin based on heat flow and multichannel reflection data

Multichannel reflection data (Tugolessov et al., 1985) have revealed two deeps in the basement topography of the Black Sea which are filled with sediments from 12 to 15 km thick. The deeps lack the “granitic layer” and are underlain by oceanic-type crust which we assume to be generated by seafloor spreading processes. The age of the deeps was interpreted previously, in a highly controversial manner, as being from the Paleozoic — Early Mesozoic to the Recent. In the paper, age estimations were undertaken using surficial heat flow data, assuming that they are related to deep-seated age-dependent heat flow generated by the cooling oceanic lithosphere, but that they are strongly distorted by the heating of continuously accumulating sediments as well as by additional heat input from radiogenic production within sediments. Using reliable thermophysical parameters of compacting sediments, the distorted heat flow in the sediments was evaluated numerically. This allowed us to estimate the age of the Black Sea deeps floor. The results show that the West Black Sea deep is 130 to 95 m.y. old, and the East Black Sea deep is nearly 110 m.y. old. These figures support an interpretation of the Black Sea deeps as remnants of a Late Mesozoic back-arc basin that evolved behind the Lesser Caucasian — Pontide island arc. The inferred Middle Cretaceous age of the deeps is the first estimate obtained quantitatively, and corresponds well with available heat flow and multichannel reflection data.     

Geology and ore genesis of the late Paleozoic Heijianshan Fe oxide–Cu (–Au) deposit in the Eastern Tianshan,NW China

The Heijianshan Fe–Cu (–Au) deposit, located in the Aqishan-Yamansu belt of the Eastern Tianshan (NW China), is hosted in the mafic–intermediate volcanic and mafic–felsic volcaniclastic rocks of the Upper Carboniferous Matoutan Formation. Based on the pervasive alteration, mineral assemblages and crosscutting relationships of veins, six magmatic–hydrothermal stages have been established, including epidote alteration (Stage I), magnetite mineralization (Stage II), pyrite alteration (Stage III), Cu (–Au) mineralization (Stage IV), late veins (Stage V) and supergene alteration (Stage VI). The Stage I epidote–calcite–tourmaline–sericite alteration assemblage indicates a pre-mineralization Ca–Mg alteration event. Stage II Fe and Stage IV Cu (–Au) mineralization stages at Heijianshan can be clearly distinguished from alteration, mineral assemblages, and nature and sources of ore-forming fluids.Homogenization temperatures of primary fluid inclusions in quartz and calcite from Stage I (189–370 °C), II (301–536 °C), III (119–262 °C) and V (46–198 °C) suggest that fluid incursion and mixing probably occurred during Stage I to II and Stage V, respectively. The Stage II magmatic–hydrothermal-derived Fe mineralization fluids were characterized by high temperature (>300 °C), medium–high salinity (21.2–56.0 wt% NaCl equiv.) and being Na–Ca–Mg–Fe-dominated. These fluids were overprinted by the external low temperature (<300 °C), medium–high salinity (19.0–34.7 wt% NaCl equiv.) and Ca–Mg-dominated basinal brines that were responsible for the subsequent pyrite alteration and Cu (–Au) mineralization, as supported by quartz CL images and H–O isotopes. Furthermore, in-situ sulfur isotopes also indicate that the sulfur sources vary in different stages, viz., Stage II (magmatic–hydrothermal), III (basinal brine-related) and IV (magmatic–hydrothermal). Stage II disseminated pyrite has δ³⁴S_fluid values of 1.7–4.3‰, comparable with sulfur from magmatic reservoirs. δ³⁴S_fluid values (24.3–29.3‰) of Stage III Type A pyrite (coexists with hematite) probably indicate external basinal brine involvement, consistent with the analytical results of fluid inclusions. With the basinal brines further interacting with volcanic/volcaniclastic rocks of the Carboniferous Matoutan Formation, Stage III Type B pyrite–chalcopyrite–pyrrhotite assemblage (with low δ³⁴S_fluid values of 4.6–10.0‰) may have formed at low fO₂ and temperature (119–262 °C). The continuous basinal brine–volcanic/volcaniclastic rock interactions during the basin inversion (∼325–300 Ma) may have leached sulfur and copper from the rocks, yielding magmatic-like δ³⁴S_fluid values (1.5–4.1‰). Such fluids may have altered pyrite and precipitated chalcopyrite with minor Au in Stage IV. Eventually, the Stage V low temperature (∼160 °C) and low salinity meteoric water may have percolated into the ore-forming fluid system and formed late-hydrothermal veins.The similar alteration and mineralization paragenetic sequences, ore-forming fluid sources and evolution, and tectonic settings of the Heijianshan deposit to the Mesozoic Central Andean IOCG deposits indicate that the former is probably the first identified Paleozoic IOCG-like deposit in the Central Asian Orogenic Belt.     

Geochemical evaluation of flowback brine from Marcellus gas wells in Pennsylvania,USA

Large quantities of highly saline brine flow from gas wells in the Marcellus Formation after hydraulic stimulation (“fracking”). This study assesses the composition of these flowback waters from the Marcellus shale in Pennsylvania, USA. Concentrations of most inorganic components of flowback water (Cl, Br, Na, K, Ca, Mg, Sr, Ba, Ra, Fe, Mn, total dissolved solids, and others) increase with time from a well after hydraulic stimulation. Based on results in several datasets reported here, the greatest concentration of Cl⁻ in flowback water is 151,000 mg/L. For total Ra (combined ²²⁶Ra and ²²⁸Ra) in flowback, the highest level reported is 6540 pCi/L. Flowback waters from hydraulic fracturing of Marcellus wells resemble brines produced from conventional gas wells that tap into other Paleozoic formations in the region. The Br/Cl ratio and other parameters indicate that both types of brine formed by the evaporation of seawater followed by dolomitization, sulfate reduction and subsurface mixing with seawater and/or freshwater. Trends and relationships in brine composition indicate that (1) increased salt concentration in flowback is not mainly caused by dissolution of salt or other minerals in rock units, (2) the flowback waters represent a mixture of injection waters with highly concentrated in situ brines similar to those in the other formations, and (3) these waters contain concentrations of Ra and Ba that are commonly hundreds of times the US drinking water standards.     

The tempo-spatial characteristics and forming mechanism of Lithium-rich brines in China

With the technological development of exploitation and separation, the primary sources of lithium have gradually changed from ore to brine, which has become the main raw material, accounting for more than 80% of the total production. Resources of lithium-bearing brine are abundant in China. This paper has summarized the spatial and temporal distribution, characteristics, and formation mechanism of the lithium-rich brine in China, aiming to provide a comprehensive set of guidelines for future lithium exploitation from brines. Lithium-rich brines usually exist in modern saline lakes and deep underground sedimentary rocks as subsurface brines. The metallogenic epoch of China’s lithium-rich brine spans from the Triassic to the Quaternary, and these brines exhibit obvious regional distribution characteristics. Modern lithium-rich saline lakes are predominately located in the Qinghai-Tibet Plateau. In comparison, the subsurface lithium-rich brines are mainly distributed in the sedimentary basins of Sichuan, Hubei, Jiangxi provinces and so on in south Block of China, and some are in the western part of the Qaidam Basin in Qinghai province in northwestern China. Lithium-rich saline lakes are belonging to chloride-enriched, sulfate-enriched, and carbonate-enriched, while the deep lithium-rich brines are mainly chloride-enriched in classification. On the whole, the value of Mg/Li in deep brine is generally lower than that of brine in saline lakes. The genesis of lithium-rich brines in China is not uniform, generally there are two processes, which are respectively suitable for salt lakes and deep brine.     

Submarine exhalative gold mineralization at the London-Virginia Mine,Buckingham County,Virginia

Low grade submarine exhalative gold mineralization occurs at the London-Virginia deposit in central Virginia Piedmont. The deposit consists of a series of localized but conformable units — basal garnetiferous-chlorite schist, magnetite schist, quartz-muscovite schist, ferruginous quartzite, and chlorite-biotite schist — which represent a mixture of submarine epiclastic volcanic debris and exhalative chemical sediments. Finely disseminated gold occurs dispersed with minor amounts of pyrite, sphalerite, chalcopyrite, galena, and tennantite in the ferruginous quartzite and quartz-muscovite schist. The deposit is believed to have formed by processes analogous to those currently active in the Atlantis II Deep of the Red Sea. Silicarich, hypersaline brines discharged through fractures in the sea floor and ponded in a local basin. Epiosodic influx of clastic debris and extensive deposition of hydrothermal silica diluted the concentration of sulfides and gold to produce a low-grade, siliceous mineralized zone. Emanation from the exhalative vent was terminated when the basin was capped by a lava flow. Subsequent regional greenschist grade metamorphism has recrystallized the silica into a granular quartzite and produced minor remobilization of the gold and sulfides.     

The evolution of marine evaporitic brines in inland basins: The Jordan-Dead Sea Rift valley

Marine-evaporitic brines frequently display Na, Cl and Br concentrations that significantly deviate from seawater evaporation paths, yielding markedly conflicting degrees of evaporation calculated for a specific brine. Here we present 493 new and 33 previously reported analyses of Ca-chloridic waters of Neogene age from the Dead Sea Rift (DSR) valley to explain such offsets. The DSR brines plot along an almost perfect mixing line (R² = 0.990) on a Br/Cl-Na/Cl diagram, extending between two end members A and B. Points A and B are located at Na/Cl = 0.804 and Br/Cl = 0.00193, and at Na/Cl = 0.00773 and Br/Cl = 0.0155, respectively, within the halite and bischofite stability fields.Brines A and B originated in a dual-mode evaporation basin. Brine A formed under the classic lagoon scenario (mode A), with seawater inflow and brine outflow at steady state. Occasional drops in water level, imposed by climatic or tectonic causes, resulted in outflow cutoff and in rapid concentration buildup. The second mode (B) initiated upon equilibration of the activity of water in the brine with the overlying relative humidity, resulting in composition and salinity approaching that of brine B, sustaining it until the next reversal to mode A.Thick evaporite deposits inhibited infiltration of brines A and B into the subsurface terrain, a process that was enabled only when the brine reached the permeable carbonate rock rim and border faults of the basin. Hence, brines that formed during the relatively short shifts from mode A to mode B could not penetrate into the deep subsurface, and bittern minerals that were formed during the frequent mode shifts were dissolved and flushed out into the sea upon the next resumption of outflow.The proposed model accounts for the deviations of brines from the marine evaporitic evolution curve by brine mixing, rather than due to a change in ocean chemistry. It also explains the absence of bittern minerals in the thick halite and gypsum/anhydrite succession, and the compositional gap between the widely different end member hypersaline fluids. This model applies directly to the studied DSR brines and evaporites, but it may be relevant to other inland evaporitic basins.     

江汉盆地大型富锂卤水矿床成因与资源勘查进展:综述

古近纪时期,华南江汉盆地的潜江凹陷和江陵凹陷发育盐湖,沉积了巨厚的蒸发岩,并形成和储藏了富锂、钾、铷、铯、溴、碘等元素的卤水资源,这些元素含量达到工业品位或综合利用品位;富锂卤水属于深层地下卤水型锂矿资源,镁锂比值低,是非常优质的锂资源。本文总结了江汉盆地大地构造特征、火成岩及古气候背景,论述了古盐湖沉积岩相特征、富锂卤水水化学、分布及储层特征、卤水中锂的来源与富集机理、卤水型锂矿成矿模式以及富锂卤水勘查与开采技术进展,提出了卤水开发利用中存在的问题和解决途径。江汉盆地富锂卤水成因包括:古盐湖锂可能主要来自高温水岩反应产生的富锂热液流体的补给;在干旱的气候下,古湖水不断蒸发浓缩,导致卤水中锂浓缩富集;在盐湖演化末期,逐渐埋藏的盐类晶间富锂卤水被转移至裂隙、砂岩及玄武岩储层中储集;在较高的地热背景值下,埋藏卤水与储层岩石可能发生水岩反应,进一步促进了卤水中锂的富集。江汉盆地深层卤水初步勘查显示,氯化锂资源量已达到大型工业规模,展示了巨大的资源潜力。此外,卤水锂开采技术已基本形成,建议进一步加强富锂卤水的绿色开发技术研究,制定相关勘查开发规范。