Groundwater in fractured crystalline rocks, the Clara mine, Black Forest (Germany)

The chemical composition of water sampled in a 700 m deep underground barite-fluorite mine in the crystalline basement of the Black Forest area (SW Germany) varies systematically with depth and the length of flow paths trough, the fracture porosity of the gneiss matrix. Calcium and sulfate increase as a result of a combined sulfide oxidation and plagioclase alteration reaction. The gneiss contains andesine–plagioclase (An₂₀–An₄₀) and is rich in primary sulfide. As an effect of Ca and SO₄ release by the prime water–rock reaction, dissolved oxygen decreases and the waters become more reduced. The waters have Cl/Br mass ratios of about 50, which is very close to that of experimentally leached gneiss powders indicating that the rock matrix is the source of the halogens. The waters are undersaturated with respect to calcite in the upper parts of the mine. With increasing reaction progress, calcite saturation is reached and carbonate forms as a reaction product of the prime reaction that also controls the partial pressure of CO₂ to progressively lower values. The chemical evolution of groundwater in fractured basement of the Clara mine suggests that the partial pressure of CO₂ is an internally buffered parameter rather than a controlling external variable.     

Genetic Type and Metallogenic Mechanism of Bankuan Gold Deposit in Special Reference to the Studies of Fluid Inclusions and Isotopes in Minerals

Auriferous quartz veins in the Bankuan gold deposit occur in the interlayer broken zone of the basal conglomerate of the Tietonggou Formation or at the unconformity between the Tietonggou Formation and the crystalline basement.The composition of fluid inclusions in the minerals indicates that the nature and composition of ore-forming hydrothermal solutions show a drastical change soon after the solutions reached the Tietonggou Formation from the crystalline basement,resulting in gold precipitation.So the Bankuan gold deposit can be assigned to the conglomerate stata-bound-type deposits.137 thermometric data are concentrated in the three ranges 400-340℃,330-220℃ and 180-160℃,representing three episodes of metalogenesis,Oxygen isotope studies demonstrate the evolution of ore-forming hydrothermal solutions from early metamorphic to late meteoric,Diversity of ore-forming materials dominated by deep-source material is supported by sulphur and lead isotope data.From the above discussions it may be concluded that the deposit formed by metamorphism induced as a result of Mesozoic northward intracontinental subduction along the Machaoying fault.     

中国镁质碳酸盐岩型温石棉矿床的成矿规律

镁质碳酸盐岩型温石棉矿床是成矿热液交代镁质碳酸盐岩生成的,一般均产于地台环境。按地台稳定性不同,成矿环境分为地台隆起区的基底建造类型和地台拗陷区的盖层建造类型。产于地台隆起区的矿床,以前震旦纪镁质碳酸盐岩为控矿层位。产于太古代及早、中元古代深变质结晶基底中的矿床,由区域变质及混合岩化过程中的变质热液交代碳酸盐岩成矿。产于晚元古代浅变质褶皱基底(扬子准地台)中的矿床,以岩浆期后热液或接触交代(湿矽卡岩)热液为成矿热液来源。产于地台拗陷区的矿床,均以震旦纪镁质碳酸盐岩为控矿层位。其成矿时期较晚,一般与拗陷区内岩浆活动同期,由岩浆期后热液或接触交代(湿矽卡岩)热液对镁质碳酸盐岩进行交代成矿。     

Fluid inclusions in late minerals from the paleovalley-type uranium deposits of the West Siberian ore region: Thermochemical characteristics and genetic applications

Comprehensive microthermometric investigations revealed similar temperature ranges (280–120°C) for the formation of late carbonates in the Khokhlovskoe, Semizbai, and Malinovskoe deposits of the West Siberian uranium ore region. A close chemical similarity was definitely established between the solutions of fluid inclusions and thermal nitrogen-methane waters with elevated CO₂ concentrations typical of this region in general. It was noted that such CO₂-rich mineral waters (Yessentuki no. 4 type) are common in the Mesozoic sequences of the Shadrinsk region, where Transuralian uranium deposits occur, and are similar in composition and temperature to the modern CO₂-rich formation waters of the host sequences of the Khokhlovskoe deposit. The mineralogical and geochemical features of newly formed late minerals and uranium ores were considered as the most probable reflection of the exfiltration of such thermal solutions into the host levels. Two late mineral assemblages were distinguished: (1) hematite-calcite and (2) goethite-berthierine and goethite-smectite-chlorite with siderite or goethite-kaolinite-illite with siderite; they occur both in the host sequences and in the underlying basement rocks. The development of the latter assemblage causes a significant change in rock color (bleaching); it is widespread and was observed in all the deposits. It was shown that these altered rocks and uranium ores (especially high-grade) are very similar in mineral and chemical composition to the products of acid leaching and accompanying mineralization, which could be related to low-temperature argillization. It was suggested that exogenic epigenetic processes of ancient soil-bedrock oxidation contributed certainly to the development of uranium mineralization, and the modern character of the uranium ores and their host rocks is related to a large extent to the influence of hydrothermal CO₂-rich solutions related to the neotectonic activation of the region. This resulted in the development of their specific mineral and chemical compositions and corresponding technological characteristics. It seems expedient to estimate the possible contributions of exogenic and endogenic factors to the formation of the uranium mineralization rather than oppose the roles of these processes of different stages.     

New data on the present-day active fluid regime of fractured zones of crystalline basement and sedimentary cover in the eastern part of Volga-Ural region

The study area is the South Tatarstan Arch located in the Volgo-Ural Region, which is an enigmatic crustal segment occupying one third of the East European Platform. Monitoring studies have shown that fluid discharge processes are still active and time-dependent. This paper presents an integrated review of the geological, geophysical, hydrochemical and geochemical studies of the crystalline basement of Tatarstan. These studies are based on the stratigraphic and compositional schemes within the crystalline basement, the drilling of deep wells, the geodynamic activity of the fractured zones of the crystalline basement and the presence of fluids therein. Furthermore, the changes in the chemical composition of the basement waters are taken into account.     

Origin of salinity of deep groundwater in crystalline rocks

Deep groundwater in fractured crystalline basement has been reported from deep mines and from scientific deep wells. Highly saline brines have been described from several km depth in the continental basement of the Canadian, Fennoscandian and Ukrainian shields and elsewhere in the world. The origin of salinity is unknown and many different possibilities have been presented. We compare the compositional evolution of deep waters in the Black Forest basement, SW Germany, with those of other deep crystalline waters, and use halogen systematics (e.g. Cl/Br ratios) and other parameters of the waters to deduce the origin of their salinity. In the Black Forest the composition of deep thermal waters results from chemical interaction of surface water with the rock matrix (mainly weathering of plagioclase and mica) and from mixing of the reacted water with stagnant saline deep water. Here we show by Na/TDS-and Cl/TDS-investigations, by molality-ratios of the Na and Cl concentrations, and by Cl/Br systematics that these deep saline waters have a marine origin. The Cl/Br ratios in deep crystalline waters are very close to normal marine ratios (Cl/Br = 288 ppm basis). In contrast, Cl/Br ratios of other possible sources of salinity show distinctly different Cl/Br ratios: water derived from dissolved Tertiary halite deposits of the rift valley is in the order of Cl/Br = 2400 and water from dissolved Muschelkalk halite deposits has values of about Cl/Br = 9900. Leaching experiments on crystalline rocks, on the other hand, show that the average Cl/Br ratio of crystalline rocks is far below Cl/Br = 100.     

Remobilisation of deep Na-Cl waters by a regional flow system in the Alps: Case study of Saint-Gervais-les-Bains (France)

The hydrothermal system of Saint-Gervais-les-Bains, France is located in a south western low-elevation point of the Aiguilles Rouges crystalline Massif. The crystalline rocks are not directly outcropping in the studied area but certainly exist beyond 300 m depth. Uprising waters are pumped from two different aquifers below the Quaternary deposits of the Bon Nant Valley. In the Lower Trias-Permian aquifer crossed by De Mey boreholes (27–36 °C), the ascending Na-SO₄ and high-Cl thermal water from the basement (4.8 g/L) is mostly mixed by a Ca-SO₄ and low-Cl cold water circulating in the autochthonous cover of the Aiguilles Rouges Basement. The origin of the saline thermal water probably results from infiltration and circulation in the basement until it reaches deep thrust faults with leaching of residual brines or fluid inclusions at depth (Cl/Br molar ratio lower than 655). The dissolution of Triassic halite (Cl/Br > 1000) is not possible at Saint-Gervais-les-Bains because the Triassic cold waters have a low-Cl concentration (< 20 mg/L). Water–rock interactions occur during the upflow via north–south strike-slip faults in the basement and later on in the autochthonous cover. For the De Mey Est borehole, gypsum dissolution is occurring with cationic exchanges involving Na, as well as low-temperature Mg dissolution from dolomite in the Triassic formations. The aquifer of imbricated structures (Upper-Middle Trias) crossed by the Lépinay well (39 °C) contains thermal waters, which are strongly mixed with a low-Cl water, where gypsum dissolution also occurs. The infiltration area for the thermal end-member is in the range 1700–2100 m, close to the Lavey-les-Bains hydrothermal system corresponding to the Aiguilles Rouges Massif. For the Ca-SO₄ and low-Cl end-member, the infiltration area is lower (1100–1300 m) showing circulation from the Mont Joly Massif. The geothermometry method indicates a reservoir temperature of probably up to 65 °C but not exceeding 100 °C.     

Chemical evolution of waters during long term interaction with granitic rocks in northern Switzerland

As part of an assessment of crystalline rock as a potential host for a nuclear waste repository, water samples were collected from more than 50 locations from the crystalline basement where it is under sedimentary cover in Northern Switzerland and where it is at the surface in the Black Forest. These samples describe the changing chemistry of water in an extended flow system from dilute recharge waters far from chemical equilibrium with its host rock to saline waters at temperatures of 50 to 100°C with residence times far in excess of 105 a that have reached chemical equilibrium with their host rock.This unique set of samples allows an analysis of the chemical evolution of granitic waters from surficial waters far from equilibrium to almost equilibrated waters. Mobile ions, rare gases and isotopic data are used to estimate the extent of reaction between waters and their host rock. The evolution of controlled elements is interpreted as a function of this extent of reaction. Silica contents correspond to approximate equilibrium even in the recharge waters. The relative concentrations of Ca and especially Mg are significantly lower in the borehole waters than in recharge waters indicating a trend towards equilibrium. The Na/K ratios correspond to equilibrium only in the most evolved, older, waters which are shown to be at full equilibrium.     

pH-dilution curves of saline waters

The pH of various saline solutions — waters from the Dead Sea, Red Sea, the Mediterranean and salt springs from the Tiberias area — and of their artificial equivalents was found to increase on dilution with distilled water. The effect is confined to waters containing more than 1.2–1.5% dissolved solids, and is roughly proportional to the original salinity of the solution. The effect is not found in solutions devoid of HCO₃⁻ salts. It is concluded that in strong brines, dissociation of bicarbonate salts is depressed; on dilution dissociation increases, hydroxide ions are formed and the pH increases. It follows that in evaporate sediments carbonate minerals might be stable at pH-values as low as 5.5.     

Major and trace element compositions (including REE) of mineral,thermal, mine and surface waters in SW Germany and implications for water–rock interaction

The near-surface water cycle in a geologically complex area comprises very different sources including meteoric, metamorphic and magmatic ones. Fluids from these sources can react with sedimentary, magmatic and/or metamorphic rocks at various depths. The current study reports a large number of major, minor and trace element analyses of meteoric, mineral, thermal and mine waters from a geologically well-known and variable area of about 200 × 150 km in SW Germany. The geology of this area comprises a Variscan granitic and gneissic basement overlain in parts by Triassic and Jurassic shales, sandstones and limestones. In both the basement and the sedimentary rocks, hydrothermal mineralization occurs (including Pb, Cu, As, Zn, U, Co and many others) which were mined in former times. Mineral waters, thermal waters and meteoric waters flowing through abandoned mines (mine waters) are distributed throughout the area, although the mine waters concentrate in and around the Schwarzwald.The present analyses show, that the major element composition of a particular water is determined by the type of surrounding rock (e.g., crystalline or sedimentary rocks) and the depth from which the water originates. For waters from crystalline rocks it is the origin of the water that determines whether the sample is Na–Cl dominant (deeper origin) or Ca–HCO₃ dominant (shallow origin). In contrast, compositions of waters from sedimentary rocks are determined by the availability of easily soluble minerals like calcite (Ca–HCO₃ dominant), halite (Na–Cl dominant) or gypsum (Ca–SO₄ dominant). Major element data alone cannot, therefore, be used to trace the origin of a water. However, the combination of major element composition with trace element data can provide further information with respect to flow paths and fluid–rock interaction processes. Accordingly, trace element analyses showed, that:

• −Ce anomalies can be used as an indicator for the origin of a water. Whereas surface waters have negative or strongly negative Ce anomalies, waters originating from greater depths show no or only weak negative Ce anomalies.
• −Eu anomalies can be used to differentiate between host rocks. Waters from gneisses display positive Eu anomalies, whereas waters from granites have negative ones. Waters from sedimentary rocks do not display any Eu anomalies.
• −Rb and Cs can also be indicators for the rock with which the fluid interacted: Rb and Cs correlate positively in most waters with Rb/Cs ratios of ∼2, which suggests that these waters are in equilibrium with the clay minerals in the rocks. Rb/Cs ratios >5 indicate reaction of a water with existing clay minerals, whereas Rb/Cs ratios <2 are probably related to host rock alteration and clay mineral formation.

The chemical compositions of carbonate precipitates from thermal waters indicate that rare earth elements (REEs), Rb and Cs concentrations in the minerals are controlled by the incorporation of clay particles that adsorb these elements.     

秦岭陆内造山带岩石圈结构

重新处理和解释叶县—南漳反射地震剖面,并综合利用油气勘探地震剖面,地震层析、大地电磁测深、地热流、气体测量等地球物理和地球化学数据,得到秦岭造山带岩石圈构造模型。识别出秦岭地壳不同时代的重要构造:(1)加里东期华北克拉通向秦岭微板块的俯冲,并造成中上地壳内华北地壳和北秦岭地壳形成锯齿状楔入构造。(2)印支—燕山期扬子克拉通与秦岭微陆块的对冲走滑软碰撞,形成了以南阳地区为中心由一系列规模宏大的逆冲断层组成的负花状构造。(3)白垩纪后,由正副片麻岩交互成层的结晶基底形成的穹隆。(4)盖在结晶基底上的近透明浅变质元古宙地层形成的褶皱基底。白垩纪后,秦岭地区和中国东部其他地区一样,岩石圈地幔遭受到软流圈上升形成蘑菇云构造,岩石圈活化,严重影响构造演化过程。     

新疆觉罗塔格构造带新元古代变质核杂岩锆石U-Pb年龄与地质意义

沙尔德兰变质核杂岩位于准噶尔板块东南部的觉罗塔格构造带西段。糜棱岩化花岗岩、斜长角闪岩、黑云母变粒岩等构成了变质核杂岩的内核系统,石炭系阿奇山组、雅满苏组、土古土布拉克组和下二叠统恰特喀尔组等构成了滑脱系统,下侏罗统八道湾组构成了盖层系统。变质核杂岩平面上呈椭圆形,滑脱构造系统围绕核部向外倾,构成叠瓦状、铲状正断层系统。滑脱系统的地层单元有不同程度的减薄和缺失。糜棱岩化花岗岩具有A₂型花岗岩地球化学特征,形成于板内环境。其锆石U-Pb SHRIMP 谐和年龄为921.7±8.1Ma,代表岩浆结晶年龄。746~721Ma和630~600Ma年龄可能分别代表糜棱岩化的时间和静态重结晶年龄。斜长角闪岩和黑云母变粒岩地层可能形成于中元古代。沙尔德兰变质核杂岩的存在证明觉罗塔格构造带存在前震旦纪结晶基底。这种结晶基底与准噶尔板块东北部的褶皱基底一起共同构成了该板块的双层基底。     

Zircon geochronology of basement rocks from the Pelagonian Zone,Greece: constraints on the pre-Alpine evolution of the westernmost Internal Hellenides

The Pelagonian Zone of Greece is the westernmost segment of the Internal Hellenides comprising widespread crystalline basement exposures of granites and orthogneisses. We dated these basement rocks in order to identify the major crust-forming episodes and to understand the evolutionary history of the area. In our study we investigated granites, gneisses, meta-rhyolites and mylonites from the major occurrences of the Pelagonian Zone. We applied single-zircon dating techniques such as Pb–Pb evaporation, conventional U–Pb and SHRIMP. The majority of the basement rocks gave Permo-Carboniferous intrusion ages, thus emphasizing the importance of this crust-forming event for the Internal Hellenides of Greece. Triassic intrusion ages were obtained, however, for a meta-rhyolite from the western Pelagonian Zone and two mylonites from the eastern Pelagonian Zone. These ages are interpreted to reflect magmatism accompanying early rifting that led to the subsequent opening of the Pindos Ocean to the west and the Meliata Ocean to the east of the Pelagonian Zone. The geochronological results demonstrate that the magmatic episodes during which most of the Pelagonian Zone crystalline basement formed are predominantly pre-Alpine in age.     

Petrological features of a Numidian section in the Lucanian Apennine (southern Italy)

A continuous section of Numidian sandstones cropping out along the eastern margin of the Lucanian Apennine (southern Italy) has been studied in relation to its petrographic and geochemical aspects. Owing to their simple mineralogy, both chemical and petrographic classifications indicate that the sandstones are subarkoses. They are characterized by high mineralogical maturity, poor sorting, abundant siliciclastic matrix and subangular quartz grains. The principal composition is Q_80–94 F_6–20 L_0–1 corresponding to SiO₂/Al₂O₃ and Fe₂O₃/K₂O ratios ranging from 37·216 to 17·124 and from 1·182 to 0·514 respectively. Two quartz grain types were distinguished: deformed and undeformed quartz grains, the former generally subangular in shape and the latter rounded. Two distinct origins of detritus can be suggested; (i) the undeformed and rounded quartz grains derive from arenaceous continental sequences; (ii) the siliciclastic matrix, the deformed subangular quartz grains, the heavy minerals and the large crystals of K-feldspar probably derive from a crystalline basement formed by low–medium–high grade metamorphic rocks and granitoids. The Numidian subarkoses represent the mixing of these two components. Both kinds of detritus can be referred to the African Craton where crystalline basement is extensively overlain by Palaeozoic and Mesozoic sandstones. The different proportions of the two components in the mixture account for the variability of the sandstone composition and might explain the mixed Numidian successions cropping out in various sectors of the Mediterranean area. Copyright © 1998 John Wiley & Sons, Ltd.     

Temperature distribution and anomalies in the crystalline basement of the tataria arch

We made temperature measurements in the crystalline basement of the superdeep and deep boreholes located in the central-eastern part of the East European platform. The basement in the studied region is characterized by an average heat flow of 60 mW m⁻². Our experiments have revealed temperature anomalies in the crystalline basement that we interpreted as unconsolidated zones. The studies indicate that fluid injection anomalies, sheet flow and overflow zones and gas anomalies can be detected by temperature measurements.     

The Early Baikalian crystalline complex in the basement of the Dzabkhan microcontinent of the Early Caledonian orogenic area, Central Asia

Fragments of continental blocks or microcontinents are represented in the Early Caledonian orogenic area of Central Asia (or Early Caledonian superterrane); the largest of these are the Dzabkhan and Tuva-Mongolian microcontinents, with Early and Late Precambrian crystalline basements, respectively. In the linkage zone of these microcontinents, crystalline rocks of the Tarbagatai and Songino blocks that are considered as units of the Early Precambrian ensialic basement of the superterrane are also known. They are composed of strongly metamorphosed rocks formed during the Early Baikalian orogeny about 790 to 820 Ma. U-Pb zircon dating and Nd isotope studies revealed, within the northwestern Dzabkhan microcontinent, the Dzabkhan-Mandal zone of crystalline rocks associated with the Riphean crust-forming process. The age of the gneiss substrate of this zone is estimated as 1.3 to 0.86 Ga. An early episode of metamorphism is dated at about 856 ± 2 Ma. The data available so far indicate a heterogeneous structure of the Dzabkhan microcontinent basement represented by Early Precambrian and Early and Late Baikalian crystalline formations.     

A possible Caledonide arm through the Barents Sea imaged by OBS data

The assembly of the crystalline basement of the western Barents Sea is related to the Caledonian orogeny during the Silurian. However, the development southeast of Svalbard is not well understood, as conventional seismic reflection data does not provide reliable mapping below the Permian sequence. A wide-angle seismic survey from 1998, conducted with ocean bottom seismometers in the northwestern Barents Sea, provides data that enables the identification and mapping of the depths to crystalline basement and Moho by ray tracing and inversion. The four profiles modeled show pre-Permian basins and highs with a configuration distinct from later Mesozoic structural elements. Several strong reflections from within the crystalline crust indicate an inhomogeneous basement terrain. Refractions from the top of the basement together with reflections from the Moho constrain the basement velocity to increase from 6.3 km s⁻¹ at the top to 6.6 km s⁻¹ at the base of the crust. On two profiles, the Moho deepens locally into root structures, which are associated with high top mantle velocities of 8.5 km s⁻¹. Combined P- and S-wave data indicate a mixed sand/clay/carbonate lithology for the sedimentary section, and a predominantly felsic to intermediate crystalline crust. In general, the top basement and Moho surfaces exhibit poor correlation with the observed gravity field, and the gravity models required high-density bodies in the basement and upper mantle to account for the positive gravity anomalies in the area. Comparisons with the Ural suture zone suggest that the Barents Sea data may be interpreted in terms of a proto-Caledonian subduction zone dipping to the southeast, with a crustal root representing remnant of the continental collision, and high mantle velocities and densities representing eclogitized oceanic crust. High-density bodies within the crystalline crust may be accreted island arc or oceanic terrain. The mapped trend of the suture resembles a previously published model of the Caledonian orogeny. This model postulates a separate branch extending into central parts of the Barents Sea coupled with the northerly trending Svalbard Caledonides, and a microcontinent consisting of Svalbard and northern parts of the Barents Sea independent of Laurentia and Baltica at the time. Later, compressional faulting within the suture zone apparently formed the Sentralbanken High.     

Catagenetic Mineralization in the Platform Cover of the Mikhailov Deposit, Kursk Magnetic Anomaly

Superimposed catagenetic transformations are sharply expressed at the Mikhailov deposit, Kursk Magnetic Anomaly. They are confined to the base of Devonian and Juarassic rocks, which transgressively overlap martite eluvium formed after jaspilites on the surface of a buried uplift. These processes resulted in the appearance of massive lenticular and domal bodies (sandstones and siltstones cemented by calcite or iron sulfides) among friable terrigenous rocks, ferruginization of limestones and their transformation into sideroplesite ores, and formation of carbonate and pyrite concretions. Secondary processes are likely to be related to both descending waters and confined solutions (often thermal) ascending from the aquiferous horizons in the lower part of the sedimentary cover and basement.     

ON THE PROBLEM OF THE GENESIS OF CINNABAR AND METACINNABARITE

Experiments have been made on the synthesis of cinnabar and metacinnabarite in conditions close to those of hydrothermal processes of the formation of mercury deposits in nature. If may be concluded that during the formation processes of mercury the first to fall out .is metacinnabarite, The fate of metacinnabarite depends on the medium that surrounds it. If hydrothermal waters carrying alkaline solutions Me₂HgS₂ will continue to effect the formed metacinnabrite, the latter will gradually become a more stable red modification HgS, i. e., ,cinnabar. If the inflow of the mercury sulfide solutions stops or becomes so weak that under the counteraction of acid or even neutral vadose waters there will not be enough solvent in the form of ions S^2-, necessary for the changing of metacinnabarite into cinnabar, then the former will be preserved in the same state for a long time. — auth. English Summ.     

Synvolcanic mixing of ore lead and the development of lead isotopic provinces in the Skellefte district,Sweden

Ore lead isotope ratios have been analysed in galenas and sulphosalts from nineteen massive sulphide deposits hosted by Svecofennian (1.9 Ga) supracrustals in the Skellefte ore district, northern Sweden. The ore lead data can be grouped on the basis of their geographical distribution. Most probably, this feature is reflecting a number of lead isotopic provinces which correspond to crustal blocks. The obtained ore lead data define linear trends in conventional Pb-Pb plots. The ore lead signatures are due to synvolcanic mixing processes as lead was leached from mafic and acid volcanic sources. The relationships inferred for initial ratios in source rocks at 1.89 Ga require a pre-Svecofennian crustal history. It is suggested that magmatic processes at c. 2.0 Ga involved recycling of Archean sedimentary material into the mantle and the formation of a crystalline, felsic basement. The metasomatized mantle and the basement melted at the time of Svecofennian magmatism (1.89 Ga) which created mafic and acid magma sources. Subsequently, basalts and rhyolites were extruded onto the sea floor. Ore was formed as hot solutions penetrated isotopically different levels of the volcanic pile.