Isotope and chemical composition of gases from mud volcanoes in the Taman Peninsula and problem of their genesis

Variations in the carbon isotope composition in gases and waters of mud volcanoes in the Taman Peninsula are studied. The δ¹³C values in CH₄ and CO₂ vary from ?59.5 to ?44.0‰ (δ¹³C_av = ?52.4 ± 5.4‰) and from ?17.8 to +22.8‰ (δ¹³C_av = +6.9 ± 9.3‰), respectively. In waters from most mud volcanoes of the peninsula, this parameter ranges from +3.3 to +33.1‰, although locally lower values are also recorded (up to ?12‰. Fractionation of carbon isotopes in the CO₂-HCO₃ system corresponds to the isotope equilibrium under Earth’s surface temperatures. The growth of carbon dioxide concentration in the gaseous phase and increase in the HCO₃ ion concentration in their water phase is accompanied by the enrichment of the latter with the heavy ¹³C isotope. The δ¹³C_TDIC value in the water-soluble carbon depends on the occurrence time of water on the Earth’s surface (exchange with atmospheric CO₂, methane oxidation, precipitation of carbonates, and other processes), in addition to its primary composition. In this connection, fluctuations in δ¹³C_TDIC values in mud volcanoes with stagnant waters may amount to 10–20‰. In the clayey pulp, concentrations of carbonate matter recalculated to CaCO₃ varies from 1–4 to 36–50 wt %. The δ¹³C value in the latter ranges from ?3.6 to +8.4‰. Carbonate matter of the clayey pulp represents a mixture of sedimentogenic and authigenic carbonates. Therefore, it is usually unbalanced in terms of the carbon isotope composition with the water-soluble CO₂ forms.     

Strontium and oxygen isotopic systems in waters of mud volcanoes of the Taman Peninsula

Ten of eleven analyzed water samples from mud volcanoes of the Taman Peninsula are characterized by ⁸⁷Sr/⁸⁶Sr ratio within 0.70734–0.70957, which overlaps the values typical of the Mesozoic and Cenozoic sedimentary carbonates, but sharply differs from the value in the clayey sediments of the Maikop Group (0.7157 ± 0.0022). These data indicate that the strontium isotopic composition is mainly defined by carbonate reservoirs, with relatively little effect of elision solutions, input of which is noticeable only in the water of Gladkovsky Volcano (⁸⁷Sr/⁸⁶Sr = 0.71076). The high δ¹⁸O in mud volcanic waters (up to 14.2‰) can also be attributed to ionic exchange with sedimentary carbonates at temperatures around 150°C.     

Hydrogeochemical Features of Thermal Waters of South Trungbo (Central Vietnam)

The results of studying the features of the hydrogeological structure and chemical and isotope composition of thermal waters from the central part of Vietnam that are characterized by intense manifestations of intrusive magmatism are presented. It is established that low–and high–thermal waters with temperature varying within 30–85°C are developed in the area under study. The value of total mineralization of the hydrotherms ranges from 0.05 to 10.05 g/dm³. It is assumed that the circulation of thermal waters that are different in temperature and chemical composition occurs at two levels. The regular change of the hydrotherm composition in the direction from mineralized chloride sodium, including with increased Ca content, to fresh sodium bicarbonate is revealed. The ratio of δ¹⁸O–δ²H isotopes indicates that the water component is based on meteoric water. In the coastal areas, there is an isotope shift towards the ocean waters, which is also confirmed by the hydrogeochemical data. The key factors for forming the chemical composition of the thermal waters in South Trungbo are their genetic type, the interaction processes in the “water–rock–gas–organic substance” system, and their equilibrium–nonequilibrium state.     

Geochemistry of mud volcano fluids in the Taiwan accretionary prism

Taiwan is located at the collision boundary between the Philippine Sea Plate and the Asian Continental Plate and is one of the most active orogenic belts in the world. Fluids sampled from 9 sub-aerial mud volcanoes distributed along two major geological structures in southwestern Taiwan, the Chishan fault and the Gutingkeng anticline, were analyzed to evaluate possible sources of water and the degree of fluid-sediment interaction at depth in an accretionary prism. Overall, the Taiwanese mud volcano fluids are characterized by high Cl contents, up to 347 mM, suggesting a marine origin from actively de-watering sedimentary pore waters along major structures on land. The fluids obtained from the Gutingkeng anticline, as well as from the Coastal Plain area, show high Cl, Na, K, Ca, Mg and NH₄, but low SO₄ and B concentrations. In contrast, the Chishan fault fluids are much less saline (1/4 seawater value), but show much heavier O isotope compositions (δ¹⁸O=5.1–6.5 ‰). A simplified scenario of mixing between sedimentary pore fluids and waters affected by clay dehydration released at depth can explain several crucial observations including heavy O isotopes, radiogenic Sr contents (⁸⁷Sr/⁸⁶Sr=0.71136–0.71283), and relatively low salinities in the Chishan fluids. Gases isolated from the mud volcanoes are predominantly CH₄ and CO₂, where the CH₄–C isotopic compositions show a thermogenic component of δ¹³C=−38 ‰. These results demonstrate that active mud volcano de-watering in Taiwan is a direct product of intense sediment accretion and plate collision in the region.     

Geochemical patterns and origin of alkaline thermal waters in Central Greece (Platystomo and Smokovo areas)

This study investigates the origin and chemical composition of the thermal waters of Platystomo and Smokovo areas in Central Greece as well as any possible relationships of them to the neighboring geothermal fields located in the south-eastern part of Sperchios basin. The correlations between different dissolved salts and the temperature indicate that the chemical composition of thermal waters are controlled by, the mineral dissolution and the temperature, the reactions due to CO₂ that originates possibly by diffusion from the geothermal fields of Sperchios basin and the mixing of thermal waters with fresh groundwater from karst or shallow aquifers. Two major groups of waters are recognized on the basis of their chemistry: thermal waters of Na–HCO₃–Cl type and thermal waters mixed with fresh groundwater of Ca–Mg–Na–HCO₃ type. All thermal waters of the study area are considered as modified by water–rock interaction rainwater, heated in depth and mixed in some cases with fresh groundwater when arriving to the surface. Trace elements present low concentrations. Lithium content suggests discrimination between the above two groups of waters. Boron geochemistry confirms all the above remarks. Boron concentration ranges from 60 μg L^?1 to 10 mg L^?1, while all samples’ constant isotopic composition (δ¹¹B ≈ 10 ‰) indicates leaching from rocks. The positive correlation between the chemical elements and the temperature clearly indicates that much of the dissolved salts are derived from water–rock interactions. The application of geothermometers suggests that the reservoir temperature is around 100–110 °C. Chalcedony temperatures are similar to the emergent temperatures and this is typical of convective waters in fault systems in normal thermal gradient areas.     

Abnormal composition of carbon isotopes in underground alkaline waters of Kuzbass

The first data on abnormally high δ¹³С values in hydrocarbonates (НСО ₃^-) dissolved in underground waters of coal deposits of Kuzbass (up to +30.9‰) are reported. It is shown that such an unusual isotope composition of waters results from the long, strictly directed interaction in the water–rock–gas–organic material system occurring under the conditions of hindered water exchange. Extensive fractionation of C isotopes is the result of the evolution of the water–rock–gas–coal system after penetration of infiltration waters into the coal deposits and their long interaction with all these components, rather than metamorphism of organic material upon its transformation into coal. With respect to such an approach, the isotope composition of dissolved C may indicate the duration of the evolution in the water–rock–gas–organic material system.     

Hydrogeochemistry,groundwater ages and sources of salts in a granitic batholith on the Canadian Shield,southeastern Manitoba

The hydrogeochemistry of the Lac du Bonnet granitic batholith has been determined for the region of the Whiteshell Research Area (WRA) in southeastern Manitoba, Canada. This work forms part of the geosciences studies performed for the Canadian Nuclear Fuel Waste Management Program over the period 1980–1995 by Atomic Energy of Canada Limited (AECL). Knowledge of the variation of groundwater chemistry and its causes is useful in assessing the performance and safety of a nuclear fuel waste vault located at depths of up to 1000 m in a crystalline rock formation of the Canadian Shield. Groundwaters and matrix pore fluids have been obtained by standard sampling methods from shallow piezometers in clay-rich overburden, from packer-isolated borehole zones intersecting fractures or fault zones in the bedrock, and from boreholes in unfractured rock in AECL's Underground Research Laboratory (URL). Eighty-six individual fracture groundwaters have been sampled and analysed from permeable zones in 53 boreholes drilled to depths of up to 1000 m in the Lac du Bonnet batholith. In addition, 28 groundwaters from piezometers in a large wetland area near the URL have been sampled and analysed to determine the influence of clay-rich overburden on the bedrock hydrogeochemistry. Analyses have been made for major and minor ions, pH, Eh, trace metals, and stable and radioactive isotopes, to characterise these groundwaters and relate them to their hydrogeologic regimes. Shallow groundwaters in the fractured bedrock are generally dilute (TDS <0.3 g/l), Ca–Na–HCO₃ waters and show little indication of mixing with Ca–Mg–HCO₃–SO₄ groundwater from overburden sediments. The near-modern levels of ³H and ¹⁴C, and a warm-climate ²H/¹⁸O signature in these groundwaters, indicates that the upper ∼200 m of fractured bedrock contains an active groundwater circulation system with a residence time of tens to hundreds of years. Deeper fracture groundwaters (200–400 m depth) in recharge areas, are more alkaline, Na–Ca–HCO₃ waters and evolve to Na–Ca–HCO₃–Cl–SO₄ waters with increasing distance along the flow path. Isotopic data indicate the presence of a glacial melt-water component suggesting that the residence times of these waters are 10³–10⁵ a. These waters form a transition zone between the upper, advective flow regime and a deeper regime in sparsely fractured rock where groundwater in fractures and fracture zones is largely stagnant. At these depths (> 500 m), Na–Ca–Cl–SO₄ waters of increasing salinity (up to 50 g/l) with depth are found and in some fractures the waters have evolved to a Ca–Na–Cl composition. Isotopic data indicate that these waters are warm-climate and pre-glacial in origin, with residence times of over 1 Ma. Pore fluids observed to drain from the unfractured rock matrix in the URL facility are almost pure Ca–Cl in composition, ∼90 g/l salinity, and have a ²H/¹⁸O composition displaced well to the left of the global meteoric water line, about which all other WRA groundwaters lie. This information indicates that these pore fluids have undergone prolonged water-rock interaction and have residence times of 10¹–10³ Ma. Most of the deeper fracture groundwaters and pore fluids have low Br/Cl ratios and moderate to high δ³⁴S values of dissolved SO₄ which indicates that their salinity could be derived from a marine source such as the basinal sedimentary brines and evaporites to the west of the batholith. These fluids may have entered the batholith during early Paleozoic times when sedimentary rocks were deposited over the granite and were driven by a hydraulic gradient resulting from higher ground in western Canada. The hydrogeochemical data and interpretations show that below ∼500 m in the WRA, fracture-hosted groundwaters are very saline, reducing and old, and are, therefore, indicative of stagnant conditions over the period of concern for nuclear waste disposal (1 Ma). The intact rock matrix at these depths is extremely impermeable as indicated by the presence of pore fluids with unusual geochemical and isotopic characteristics. The pore fluids may represent basinal brines that have evolved geochemically and isotopically to their current composition over periods as long as 10³ Ma.     

Conditions of the formation of thermomineral waters in the Talysh fold zone of the Lesser Caucasus (Azerbaijan) based on isotope-geochemical data (3Не/4Не, $${\delta ^{13}}{C_{c{o_2}}},{\delta ^{13}}{C_{c{h_4}}},{\delta ^{15}}{N_{{N_2}}}{,^{87}}Sr{/^{86}}Sr,\delta {D_{{H_2}O}},and{\delta ^{18}}{O_{{H_2}O}}$$)

It is shown that the gas and water phases of the thermal nitrogen–methane waters in the Talysh fold zone of the Lesser Caucasus mountain system contain helium and strontium with mantle isotope signatures (³Не/⁴Не from 200 × 10^–8 to 401 × 10^–8 and ⁸⁷Sr/⁸⁶Sr from 0.70490 to 0.70562). At the same time, clear signs of the mantle component in other gases (nitrogen, methane, and carbon dioxide) are absent. The δ¹⁵N value in nitrogen varies from +0.3 to +1.7‰, methane is mainly characterized by δ¹³C from–57.4 to–38.0‰, while δ¹³C(CО₂) varies from–24.4 to–11.3‰. An increase of the CО₂ content is accompanied by the decrease of δ¹³C in CО₂, against the background of increasing SO₄ content in the salt composition of waters. This indicates a microbial nature of CO₂ in the studied gases. Thus, the presence of mantle helium and strontium in the thermal waters is likely related to their leaching from the Pleogene–Neogene host volcanic rocks. The studies of the oxygen and hydrogen isotope composition in water revealed quite different mechanisms for the formation of cold and thermal waters of the region. The cold waters are mainly fed by local infiltration, whereas the feeding of thermal nitrogen–methane waters is strongly provided by transit atmogenic waters (>50%), which are formed in the mountain ranges at altitudes no less than 1600 m and spaced at 20–40 km or more from the thermal discharge sites.     

Lead Isotope composition and origin of the quaternary lavas of Elbrus Volcano, the Greater Caucasus: High-precision MC-ICP-MS data

A systematic study of Pb isotope composition was carried out for Elbrus Volcano, one of the Europe’s largest volcanoes, using high-precision method of multi-collector inductively coupled plasma mass spectrometry. The measurement error of Pb isotope ratios was estimated from the results of replicate analyses of international BCR-1 and AGV-1 standards as ±0.03% (±2SD). The study of a representative collection showed that dacites of all three phases of the Elbrus eruptive activity are characterized by relatively small-scale variations of Pb isotope composition: ²⁰⁶Pb/²⁰⁴Pb 18.621–18.670, ²⁰⁷Pb/²⁰⁴Pb 15.636–15.659, and ²⁰⁸Pb/²⁰⁴Pb 38.762–38.845. New Pb isotope geochemical characteristics in combination with existing Sr-Nd data indicate that the parental magmas of Elbrus are of mixed mantle-crust origin. They were formed by interaction of mantle-derived melts with continental crust of the Greater Caucasus during continental collision between the Eurasian, Arabian, Turkish, and Iranian plates.     

Geochemistry and isotope geochemistry of the Monfalcone thermal waters (northern Italy): inference on the deep geothermal reservoir

Geochemical investigations were carried out to define the origin of the low- to moderate-temperature thermal waters feeding the Monfalcone springs in northern Italy. Chemical data indicate that waters approach the composition of seawater. Mixing processes with cold low-salinity waters are highlighted. The δ¹⁸O and δD values are in the range ?5.0 to ?6.4 ‰, and ?33 to ?40 ‰, respectively, suggesting the dilution of the saline reservoir by karst-type freshwaters. A surplus of Ca²⁺ and Sr²⁺ ions with respect to a conservative mixing is ascribed to diagenetic reactions of the thermal waters with Cretaceous carbonates at depth. The measured Sr isotopic composition (⁸⁷Sr/⁸⁶Sr ratio) ranges between 0.70803 and 0.70814; after correction for the surplus Sr, a ⁸⁷Sr/⁸⁶Sr ratio indicating Miocene paleo-seawater is obtained. The dissolved gases indicate long-lasting gas–water interactions with a deep-originated gas phase of crustal origin, dominated by CO₂ and marked by a water TDIC isotopic composition in the range ?5.9 to?8.8 and helium signature with 0.08?<?R/Ra?<?0.27, which is a typical range for the crust. A possible scenario for the Monfalcone thermal reservoir consists of Miocene marine paleowaters which infiltrated through the karstic voids formed within the prevalently Cretaceous carbonates during the upper Eocene emersion of the platform, and which were entrapped by the progressive burial by terrigenous sediments.     

Influence of hydrostratigraphy and structural setting on the arsenic occurrence in groundwater of the Cimino-Vico volcanic area (central Italy)

Arsenic occurrence in groundwater near the Cimino-Vico volcanoes (central Italy) was analysed considering the hydrostratigraphy and structural setting and the shallow and deep flows interacting within the Quaternary volcanics. Groundwater is the local source of drinking water. As documented in the past, arsenic in the groundwater has become a problem, and the European maximum allowable contaminant level was recently lowered to 10 μg/L. Chemical analyses of groundwater were conducted, sampled over an area of about 900 km², from 65 wells and springs representative of the volcanic aquifer and thermal waters. Considering the type of aquifer, the nature of the aquifer formation and its substratum, the hydrochemical data highlight that the arsenic content of the groundwater is mainly connected with the hydrothermal processes in the volcanic area. Thermal waters (54–60°C) fed from deep-rising fluids show higher arsenic concentrations (176–371 μg/L). Cold waters sampled from the volcanic aquifer are characterized by a wide variability in their arsenic concentration (1.6–195 μg/L), and about 62% exceed the limit of 10 μg/L. Where the shallow volcanic aquifer is open to deep-rising thermal fluids, relatively high arsenic concentrations (20–100 μg/L) are found. This occurs close to areas of the more recent volcano-tectonic structures.     

Geochemical assessment,mixing behavior and environmental impact of thermal waters in the Guelma geothermal system,Algeria

A study of thirteen geothermal springs located in the geothermal field of Guelma, northeastern Algeria, was conducted. Samples were collected during the period between January 2014 and February 2016. Geochemical processes responsible for the chemical composition of thermal and mineralized water were evaluated. The hydrochemical analysis shows that the thermal waters are characterized by the presence of two different chemical facies, the first type SO₄–Ca in the east, west and south of Guelma, the second type HCO₃–Ca in the south. This analysis also attributed to sodium, chlorides, and sulfates to an evaporitic terrigenous origin by the molar ratio Sr²⁺/Ca²⁺. The thermal spring waters from Guelma geothermal system have a meteoric origin, and all samples are immature with strong mixing between hot and shallow waters with 19–38.5% rate of mixing. The silica geothermometer shows that these thermal waters have a temperature varying from 84 to 122 °C and that the water came from a depth of 2100–3000 m through a fault system that limits the pull-apart basin of Guelma. Potential environmental effluent from thermal spas could pollute in both the irrigation and drinking waters, and which imposes danger on the health of the inhabitants of the region.

     

Sedimentary matter and organic compounds in the aerosols and surface waters along the Transatlantic section

Concentrations and composition of suspended particulate matter and organic compounds (OC), including Сorg, lipids, hydrocarbons (HC), and pigments, were determined in the near-water aerosol layer and in surface waters on the meridional section across the Atlantic Ocean from the port of Ushuaia to the port of Gdansk (Cruise 47^th of the R/V Akademic Ioffe, March 26–May, 7, 2015). It was established that the distribution of OC (except for pigments) in aerosols, in general, repeats the distribution of particle number and weight concentrations of aerosols, with maximums in the influence zone of fluxes from Patagonia and African deserts. The concentrations of aerosols changed within wide ranges: from 1237 to 111739 particles/L for 0.3–1 μm fraction; and from 0.02 to 19.890 μg/m³ for aerosols collected by network method (flux of 0.02–34.4 mg/m² day). The contrasting mineral composition of aeolian material reflects the diversity of its provenances. In surface waters, the studied compounds were accumulated in the frontal river–sea area (runoff of the Rio-Colorado River) and with approaching the coast, especially in the English Channel. A simultaneous change of concentrations of suspended particulate matter and OC is observed only in open oceanic waters.     

Hydrogeochemical characteristics and genetic implications of Edipsos thermal springs, north Euboea, Greece

Edipsos area, situated in northern Euboea, has been well known since ancient times for the existence of thermal springs. In order to assess the hydrogeochemical conditions, thermal and cold water samples were collected and analyzed by ICP method for major and trace elements. The results revealed the direct impact of seawater, a process which is strongly related to the major tectonic structures of the area. Seawater impact was confirmed by the Cl/Br and Na/Cl ionic ratios, as well as from statistical processing and graphical interpretation of the analytical results, which classified the sampled waters into three groups (two for cold waters and one for the thermal ones). Trace element ranges for thermal waters are: As (44–84 ppb), Pb (23–154 ppb), Ag (1–2 ppb), Mn (31–680 ppb), Cu (61–97 ppb), Cs (66–244 ppb), Se (0–76 ppb), Li (732–3269 ppb), Fe (0–1126 ppb), Sr (14000–34100 ppb), B (4300–9600 ppb). Compared with the chemical composition of other thermal springs from the Hellenic Volcanic Arc, Edipsos thermal waters are enriched in Ca²⁺, Na⁺, Cl^?, SO₄ ^2?, Li, B and K⁺, reflecting the influence from seawater. Cold waters are free of heavy metals compared with other natural waters and are characterized by good quality based on the major element chemistry. Finally, several geothermometers were applied in order to assess the reservoir temperatures, but none of them appear to be applicable, mainly due to the impact of seawater on the initial hydrogeochemistry of the geothermal fluids.     

Origin of rapidly solidified metal-troilite grains in chondrites and iron meteorites

Inclusions of troilite and metallic Fe,Ni 0.2–4 mm in size with a dendritic or cellular texture were observed in 12 ordinary chondrites. Cooling rates in the interval 1400?950°C calculated from the spacing of secondary dendrite arms or cell widths and published experimental data range from 10^?7 to 10⁴°C/sec. In 8 of these chondrites, which are breccias containing some normal slow-cooled metal grains, the inclusions solidified before they were incorporated into the breccias. Their cooling rates of 1–300 °C/sec indicate cooling by radiation, or by conduction in contact with cold silicate or hot silicate volumes only 6–40 mm in size. This is quantitative evidence that these inclusions and their associated clasts were melted on the surface of a parent body (by impact), and were not formed at depth from an internally derived melt. In Ramsdorf, Rose City and Shaw, which show extensive reheating to ? 1000°C, Fe-FeS textures in melted areas are coarser and indicate cooling rates of 10^?1 to 10^?4°C/sec during solidification. This metal may have solidified inside hot silicate volumes that were 10–300 cm in size. As Shaw and Rose City are breccias of unmelted and melted material, their melted metal did not necessarily cool through 1000°C within a few m of the surface. Shock-melted, fine-grained, irregular intergrowths of metal and troilite formed in situ in many irons and some chondrites by rapid solidification at cooling rates of ? 10⁵°C/sec. Their kamacite and taenite compositions may result from annealing at ~250°C of metallic glass or exceedingly fine-grained quench products.     

Groundwater and volcanoes: examples from the Azores archipelago

Groundwater at the Azores archipelago is a strategic resource for the freshwater supply. Freshwater, mineral and thermal water discharges occur in the archipelago, and especially at the Fogo and Furnas volcanoes (São Miguel). These discharges provide data for case studies of groundwater chemistry from volcanic monitoring due to the stable composition of the sampled waters. The mineral and thermal discharges are mainly of sodium bicarbonate types and present a large range of temperatures, from cold springs to waters at about 90 °C. Some boiling discharges have a sulfate-dominated composition, suggesting a steam-heating mechanism. Geochemical studies on these mineral and thermal waters began in the 19th century. Data gathered since these earlier studies provide a baseline for pH, temperature, CO₂ and major-element composition. Weekly measurements of pH and temperature also denote a rather stable behavior.     

Hydrogeochemistry and strontium isotopes of spring and mineral waters from Monte Vulture volcano,Italy

This paper describes the results of a study that was conducted to determine the relationship between hydrogeochemical composition and ⁸⁷Sr/⁸⁶Sr isotope ratios of the Mt. Vulture spring waters. Forty samples of spring waters were collected from local outcrops of Quaternary volcanites. Physico-chemical parameters were measured in the field and analyses completed for major and minor elements and ⁸⁷Sr/⁸⁶Sr isotopic ratios. A range of water types was distinguished varying from alkaline-earth bicarbonate waters, reflecting less intense water–rock interaction processes to alkali bicarbonate waters, probably representing interaction with volcanic rocks of Mt. Vulture and marine evaporites. The average ⁸⁷Sr/⁸⁶Sr isotope ratios suggest at least 3 different sources. However, some samples have average Sr isotope ratios (0.70704–0.70778) well above those of the volcanites. These ratios imply interaction with other rocks having higher ⁸⁷Sr/⁸⁶Sr ratios, probably Triassic evaporites, which is substantiated by their higher content of Na, SO₄ and Cl. The Sr isotope ratios for some samples (e.g. Toka and Traficante) are intermediate between the value for the Vulture volcanites and that for the local Mesozoic rocks. The salt content of these samples also lies between the value for waters interacting solely with the volcanites and the value measured in the more saline samples. These waters are thus assumed to result from the mixing of waters circulating in volcanic rocks with waters presumably interacting with the sedimentary bedrock (marine evaporites).     

Pre-Imbrian craters and basins: ages,compositions and excavation depths of Apollo 16 breccias

Breccia fragments have been analyzed from the 2–4 mm sieve fraction of three Apollo 16 soils collected in the vicinity of North Ray Crater (63503,17 at Station 13; 67603,1 and 67703,14 at Station 11). Ar³⁹-Ar⁴⁰ ages, Ar³⁷-Ar³⁸ exposure ages, abundances of major and certain trace elements, and petrographie data relevant to thermal history have been obtained for up to 48 individual fragments.Among the samples. 30 gave Ar³⁹-Ar⁴⁰ release patterns that allowed the assignment of a high- or intermediate-temperature plateau age and the recognition of three age groups. Group I (10 fragments) are 4.12-4.21 AE, Group 2 (13 fragments) are 3.89-4.02 AE, and Group 3 (6 fragments) are <2.5 AE in age. Only one fragment (3.60 AE) falls outside this grouping and possibly represents Theophilus ejecta. The probability that the gap between 4.12 and 4.02 AE is a statistical fluctuation is only ～2%. The exposure ages cluster strongly around 50 × 10⁶y. the age of North Ray Crater.The oldest, Group 1 fragments are all anorthositic metamorphosed breccias of light-matrix type. The younger. Group 2 fragments are noritic anorthosite and anorthositic norite breccias with textures indicative of greater annealing (melted matrix), one totally melted sample being of KREEP-basalt texture. The very young. Group 3 fragments are chiefly of glass or devitrified glass. There is a marked distinction between Groups 1 and 2 in compositional as well as textural properties. The Group 2 breccias are generally enriched in Mg, K and REE relative to the aluminous Group I breccias (eg. K ≤ 400 ppm in Group 1 and mostly ≥ 600 ppm in Group 2). This difference is attributed to the introduction of KREEP and mafic ANT components during the formation of the Group 2 breccias.The results are interpreted as reflecting two magnitudes of cratering. The older craters (>4.1 AE) were of medium size (diameters up to a few hundred kilometers), large enough to reset the ages but not capable of excavating deeper than predominantly feldspathic (anorthositic) layers of the crust. The younger craters (～3.9-4.0 AE) were, in contrast, those ascribed to major basin-forming events and were therefore capable of excavating a deeper and wider spectrum of crustal lithologies. The latter resulted in admixture of KREEP and mafic ANT components with the feldspathic ANT, cover layer. KREEP was thus only excavated in abundance during the basin-forming events, from a sub-crustal layer formed initially at ～4.4 AE but incorporated in the breccias at ～4 AE.The KREEP-contaminated. Group 2 breccias have—except two fragments—ages between 3.95 and 4.02 AE. This group includes a crystallized melt (3.97 ± 0.04 AE), close in composition and texture to 14310 (3.87 ± 0.04 AE) which is generally attributed to the Imbrian basin-forming event (～3.88 AE). The pre-Imbrian. Group 2 breccias of Apollo 16 can best be attributed to the Nectaris basin-forming event, which according to the clustered ages probably occurred at ～3.98 AE. Our results support a multi-impact lunar cataclysm with the formation of Nectaris (3.98 AE). Humorum. South Serenitatis, Crisium and Imbrium (3.88 AE) within a 0.1 AE time interval.     

Discussion: Stratigraphy and structural summary of the Cooma metamorphic complex

Field and petrographic studies on granitic, hematitic and chloritic breccias in the central portion of the Mount Painter Inlier, South Australia, indicate that: (i) breccias and brecciated basement extend to depths exceeding 400 m and have gradational contacts; (ii) clasts are mainly autochthonous and contain fine‐scale hematite, chlorite or quartz veinlets and fractures; (iii) K‐metasomatism preceded hematitisation and chloritisation; (iv) hematitic breccia intrudes a pegmatite dyke correlated with the Ordovician Arkaroola Pegmatite; and (v) U, F and REE‐containing minerals are present in the Proterozoic basement rocks, and concentrated in the breccias.

With a single exception, δ³⁴S values for pyrite from the breccias and brecciated granites fall in the narrow range —2.9% to +3.5%, implying formation from magmatic emanations or reducing fluids that leached sulphide minerals of magmatic derivation. δ³⁴S values for three barite samples are all close to +16%o, and firm conclusions cannot be drawn from these data. Calcites from the same rock‐types as the pyrite have δ¹³C values of — 22.3%o to —4.2%o and δ¹⁸O values of —4.0%o to +23.1%., with an inverse δ¹³C/δ¹⁸O relationship. The more ¹³C‐depleted calcites probably incorporated CO₂ from organic C, and their δ¹⁸O values are compatible with precipitation from magmatic or metamorphic fluids; mixing of such fluids with meteoric waters is implied by the calcites with variably lower δ¹⁸O values.

The above features indicate that the major processes leading to brecciation and associated metasomatism were hydraulic fracturing and hydrothermal activity resulting from ascent of granitic magmas to shallow crustal levels during late stages (late Ordovician‐?Silurian) of the Delamerian Orogeny. Tectonic and sedimentary processes appear to have played relatively minor roles in breccia formation.     

A geochemical and stable isotope investigation of groundwater/surface-water interactions in the Velenje Basin,Slovenia

The geochemical and isotopic composition of surface waters and groundwater in the Velenje Basin, Slovenia, was investigated seasonally to determine the relationship between major aquifers and surface waters, water–rock reactions, relative ages of groundwater, and biogeochemical processes. Groundwater in the Triassic aquifer is dominated by HCO₃ ^–, Ca²⁺, Mg²⁺ and δ¹³C_DIC indicating degradation of soil organic matter and dissolution of carbonate minerals, similar to surface waters. In addition, groundwater in the Triassic aquifer has δ¹⁸O and δD values that plot near surface waters on the local and global meteoric water lines, and detectable tritium, likely reflecting recent (<50 years) recharge. In contrast, groundwater in the Pliocene aquifers is enriched in Mg²⁺, Na⁺, Ca²⁺, K⁺, and Si, and has high alkalinity and δ¹³C_DIC values, with low SO₄ ^2– and NO₃ ^– concentrations. These waters have likely been influenced by sulfate reduction and microbial methanogenesis associated with coal seams and dissolution of feldspars and Mg-rich clay minerals. Pliocene aquifer waters are also depleted in ¹⁸O and ²H, and have ³H concentrations near the detection limit, suggesting these waters are older, had a different recharge source, and have not mixed extensively with groundwater in the Triassic aquifer.