An experimental study on felsic rock–artificial seawater interaction: implications for hydrothermal alteration and sulfate formation in the Kuroko mining area of Japan

Experimental studies on the interactions between artificial seawater (ASW) and fresh rhyolite, perlite and weakly altered dacitic tuff containing a small amount of smectite suggest changing cation transfer during smectite-forming processes. Initially, dissolution of K from the rocks accompanies incorporation of Mg and Ca from ASW during both earlier (devitrification stage) and later smectite formation, whereas Ca incorporated with early smectite formation redissolves with progressive reaction. Barium mobility increases toward the later smectite-forming reactions. Therefore, the large amounts of barite, anhydrite and gypsum in Kuroko ore deposits are considered to have precipitated from hydrothermal solutions derived from the interaction with previously altered felsic rocks during late smectite formation, rather than by the reaction with fresh felsic rocks.Editorial handling: D. Lentz     

Mineralogical and geochemical characteristics of hydrothermal alteration of basalt in the Kuroko mine area, Japan: implications for the evolution of a Back Arc Basin hydrothermal system

Basalt in the Furutobe District of the Kuroko mine area in Japan is characterized by abundant chlorite and epidote. Fluid inclusion studies indicate that chlorite is formed at lower temperatures (230–250°C) than epidote (250–280°C). The seawater/basalt mass ratio for the early chlorite-rich alteration was high (max. 40), but that for the later alteration was low (0.1–1.8). The CaO, Na₂O and SiO₂ of the bulk rock correlate negatively with MgO, while FeO and Σ Fe correlate positively with MgO. These changes in the characteristic features of hydrothermal alteration from early to late are generally similar to those for a mid-ocean ridge geothermal system accompanying basalt alteration.The MgO/FeO ratios of chlorite and actinolite and the Fe₂O₃ concentration of epidote from the basalt are greater than those of mid-ocean ridge basalt probably owing to the differences in the Fe₂O₃/FeO and MgO/FeO ratios of the parent rocks. The lower CaO concentration and the higher Na₂O concentration of the bulk rock compared with altered mid-ocean ridge basalt can be interpreted in terms of the difference in original bulk rock compositions.The Furutobe basalt, as well as other submarine back arc basalts, contains more vesicles filled with hydrothermal minerals (epidote, calcite, quartz, chlorite, pyrite) than do the mid-ocean ridge basalts. The abundance of vesicles plays an important role in controlling the secondary mineralogy and geochemistry of hydrothermally altered submarine back arc basin basalts.     

Ore‐forming Ages and Sulfur Isotope Study of Hydrothermal Deposits in Kamchatka,Russia

In Kamchatka, Central Koryak, Central Kamchatka and East Kamchatka metallogenic belts are distributed from northwest to southeast. K–Ar age, sulfur isotopic composition of sulfide minerals, and bulk chemical compositions of ores were analyzed for 13 ore deposits including hydrothermal gold‐silver and base metal, in order to elucidate the geological time periods of ore formation, relationship to regional volcanic belts, type of mineralization, and origin of sulfur in sulfides. The dating yielded ore‐forming ages of 41 Ma for the Ametistovoe deposit in the Central Koryak, 17.1 Ma for the Zolotoe deposit and 6.9 Ma for the Aginskoe deposit in the Central Kamchatka, and 7.4 Ma for the Porozhistoe deposit and 5.1 Ma for the Vilyuchinskoe deposit in the East Kamchatka metallogenic belt. The data combined with previous data of ore‐forming ages indicate that the time periods of ore formation in these metallogenic belts become young towards the southeast. The averaged δ³⁴S_CDT of sulfides are ?2.8‰ for the Ametistovoe deposit in Central Koryak, ?1.8‰ to +2.0‰ (av. ?0.1‰) for the Zolotoe, Aginskoe, Baranievskoe and Ozernovskoe deposits in Central Kamchatka, and ?0.7 to +3.8‰ (av. +1.7‰) for Bolshe‐Bannoe, Kumroch, Vilyuchinskoe, Bystrinskoe, Asachinskoe, Rodnikovoe, and Mutnovskoe deposits in East Kamchatka. The negative δ³⁴S_CDT value from the Ametistovoe deposit in Central Koryak is ascribed to the contamination of ³²S‐enriched sedimentary sulfur in the Ukelayat‐Lesnaya River trough of basement rock. Comparison of the sulfur isotope compositions of the mineral deposits shows similarity between the Central Koryak and Magadan metallogenic belts, and East Kamchatka and Kuril Islands belts. The Central Kamchatka belt is intermediate between these two groups in term of sulfur isotopic composition.     

Interpretation of Mineral Zoning in Submarine Hydrothermal Ore Deposits in Terms of Coupled Fluid Flow‐Precipitation Kinetics Model

Major minerals (sulfates, sulfides, quartz) are distributed in different parts of submarine hydrothermal ore deposits. For instance, the abundance of barite increases stratigraphically upwards in the massive orebodies of the Kuroko deposits (black and yellow ores), while quartz is abundant in the lower parts (siliceous ore). The different distribution of barite and quartz in the Kuroko deposits can not be accounted for by thermochemical equilibrium calculations based on the precipitation due to mixing of ascending hydrothermal solutions with ambient cold seawater. In the present study, a coupled fluid flow‐precipitation kinetics model was used to calculate the amounts of quartz, barite, and anhydrite precipitated from a hydrothermal solution mixed with seawater, assuming reasonable values for temperature, precipitation rate, fluid flow velocity, mineral surface area/fluid mass ratio (A/M), and initial concentrations of hydrothermal solution and seawater before mixing occurred. The results indicate that barite precipitates more efficiently than quartz from discharging fluids with relatively higher flow velocity, lower temperatures and under the condition of lower A/M ratios on the seafloor (black ore), whereas quartz precipitates more effectively from solutions with lower flow velocity, higher temperatures and higher A/M ratios beneath the seafloor (siliceous ore) and in the orebody (barite ore, ferruginous chert ore). Anhydrite precipitates in shallow sub‐seafloor environments with lower precipitation rates and higher A/M ratios than barite and higher precipitation rates and lower A/M ratios than quartz. These results explain the observed occurrences of barite, anhydrite, and quartz in the Kuroko deposits. Namely, barite is abundant in black ore and barite ore which formed above the seafloor, anhydrite formed in high‐permeability tuff breccias, and quartz formed in low permeability dacite intrusive bodies in the sub‐seafloor environment.     

Uranium Behavior in the Process of Primary Pitchblende Ores Alteration by the Post‐ore Hydrothermal Solutions: An Application to Assessment of Uranium Migration from Underground Spent Nuclear Fuel Repositories

It has been shown that the main uranium ore mineral, pitchblende (uranium dioxide), is a natural analog of synthetic uraninite (also uranium dioxide), which constitutes 96% of spent nuclear fuel (SNF). Geochronological studies of the U‐Pb isotope systems in unaltered pitchblende from the orebodies reveal that these systems remained completely closed over the entire period (approximately 135 Ma) since the formation of the deposits. The bulk of the primary uranium ores within the Streltsovskoye ore field was influenced to various degrees by post‐ore hydrothermal solutions that led to pitchblende spherulites being replaced by pseudomorphs of an amorphous phase with a U‐Si composition; this phase also re‐precipitated in veinlets proximal to the pitchblende pseudomorphs. A technique specially developed by the authors was used to carry out quantitative counts of the abundance of uranium minerals by calculating the uranium mass balance in one of the orebodies subjected to hydrothermal alteration. The calculations reveal minimal uranium loss from the orebody. Uranium liberated in the process of the pseudomorphic replacement of pitchblende was immediately fixed, in situ, in the newly formed coffinite‐like amorphous U‐Si phase as a result of the development of an efficient geochemical barrier that prevented the long‐distance migration of uranium. In assessing the long‐term safety of underground SNF repositories, the results of the present study give us confidence that SNF uraninite, in terms of the preservation of its integrity as a mineral phase, provides for the reliable long‐term isolation of uranium, transuranium elements, and fission products that are “sealed” in the uraninite matrix. In the case of the mineral transformation of the uraninite matrix by hydrothermal solutions, the liberated uranium would be efficiently immobilized by the newly formed amorphous U‐Si phase.     

Factors Controlling the Fractionation and Seasonal Mobility Variations of Ga and In in Systems Impacted by Acidic Thermal Waters: Effects of Thermodynamics and Bacterial Activity

This work assessed both the fractionation and the seasonal mobility variations of Ga and In in systems impacted by acidic thermal waters. This was accomplished by performing thermodynamic calculations using the PHREEQC algorithm and by assessing the activity of acidophilic iron-oxidizing bacteria. The pH of the Kusatsu thermal waters in Gunma Prefecture, central Japan, is rapidly increased following the addition of a lime suspension. After an abrupt pH increase, under which conditions free ions of Ga and In and their complexes with Cl^? and SO₄^2? exist only in negligible quantities, the majority of dissolved Ga and In is removed by sorption onto suspended hydrous ferric oxides (HFOs). These HFOs are then transported to an artificial lake without significant sedimentation along the river. Subsequently, the suspended HFOs settle out and are added to sediments without significant fractionation between Ga and In. The Tamagawa thermal waters in Akita Prefecture, northeast Japan, are also treated with lime. However, complete neutralization requires mixing with some tributary streams, leading to a gradual downstream increase in pH. Dissolved Ga is, in general, sorbed by HFOs in upstream areas, leading to wide dispersal of Ga across the entire watershed. In comparison, In is transported to the lake inlet predominantly as a Cl^? complex species without significant removal along the river, with the majority being precipitated in an artificial lake, where Cl^? concentrations are too low to form stable complex species with In, and thus, dissolved In is sorbed by HFOs. As a result, In is effectively concentrated within downstream lakebed sediments, whereas Ga is dispersed along the river. Seasonal variations in Ga mobility within the Tamagawa field between snowmelt and low-flow seasons are primarily controlled by pH, because hydrolysis reactions of these metals, which are related to sorption reactions, tend to occur in the upstream regions in the snowmelt season. However, under warmer conditions, HFO formation preferably occurs due to the activity of acidophilic iron-oxidizing bacteria. Thus, under similar pH variations, dissolved Ga is more effectively removed by HFOs during warmer seasons. On the contrary, because HFOs are abundantly formed in low-flow season, even under colder conditions, before In hydrolysis reaction starts to occur, In mobility is less affected by water temperature and then bacterial activity.     

Zinc contamination in river water and sediments at Taisyu Zn–Pb mine area,Tsushima Island,Japan

Tsushima Island is one of the oldest zinc-lead mining areas in Japan. River water and sediment samples were collected mainly from Taishu area to determine the contamination level of Zn and to clarify its behaviour in the natural system. Among the water samples analysed, 64% exceeded the standard environmental limit of 0.03 µg ml^− 1 for Zn. In most cases, Zn concentration in sediment samples also exceeded the standard value, and the concentration varied from 86.75–7490.07 µg g^− 1. The mineralogical constituents in sediments were almost similar and quartz had the strongest peak, but the interior part of the ores had many minerals, with galena having the highest proportion. Considering the enrichment factor values (EFc), 12 samples have values of more than 50, indicating a high pollution load for Zn. This study revealed that the sulphide ores, and contaminated sediments, are the possible contamination sources of Shiine River, and Zn dissolution occurred by reactions, such as desorption and ion exchange.