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Vol 57, No 3 (2019)

Article

Effect of Hydrous Pyrolysis on the Distribution of Carbon and Hydrogen Isotopes between Fractions of Organic Matter. The Nature of Oil Seeps in the Uzon Caldera, Kamchatka, Russia

Sevast’yanov V.S., Karpov G.A., Bychkov A.Y., Kuznetsova O.V., Fedulov V.S.

Abstract

The paper presents data on the transformations of oil from seeps in the caldera of Uzon volcano under the effect of hydrous pyrolysis at a temperature of 350°C in an argon and oxygen atmosphere. The carbon and hydrogen isotopic-fractionation characteristics (IFC) are proved to reflect processes occurring in the organic matter at its hydrous pyrolysis in oxidizing and neutral environments. Similarities in configuration are detected between the carbon IFC of Uzon oil seeps, Bogachevskoe field, and the biota of hydrothermal springs. The hydrogen IFC are of more complicated form, perhaps, because of exchange processes in the hydrothermal water. It is hypothesized that oil seeps in the interiors of the Uzon caldera can provide material for the origin of oil at the Bogachevskoe field. At the same time, it cannot be ruled out that hydrothermal water circulating in the caldera of Uzon volcano brings the material of the Bogachevskoe oil to the surface.

Geochemistry International. 2019;57(3):233-242
pages 233-242 views

Characteristics of Acid Melts That Produced the Tephra of Pleistocene–Holocene Eruptions of Ichinsky Volcano, Kamchatka: Evidence from Melt Inclusions

Tolstykh M.L., Pevzner M.M., Naumov V.B., Babansky A.D.

Abstract

The paper reports data on glassy melt inclusions in minerals of tephra that was produced by the most significant eruptions of Ichinsky volcano, Kamchatka, and marked the major evolutionary stages of the volcanic center in the Pleistocene–Holocene. The melts are of dacite–rhyodacite composition (68–77 wt % SiO2, 0.1–0.6 wt % MgO) and contain 2–4 wt % H2O (3.3 wt % on average). Most of the melts are potassic (3.8–4.8 wt % K2O), but some of them are less alkaline (2.5 wt % K2O) and richer in iron and calcium. The trace-element composition of the glasses also suggests the presence of melts of two types. The high-K melts are relatively deficient in Nb and HREE (Nb = 10–14 ppm, La/Yb = 10–20), whereas the low-K melts typically show more clearly pronounced Nb minima, are relatively depleted in LREE, and are enriched in HREE (Nb = 3–4 ppm, La/Yb = 3–5). The two melt types likely sampled a long-lived magmatic chamber and, perhaps, also one of the components of magmatic mixing, whose addition to the system may have provoked the beginning of a reactivation stage of the volcanic center.

Geochemistry International. 2019;57(3):243-265
pages 243-265 views

Geochemical Evidence for the Depositional Environment of the Esfandaghe Manganese Deposit, Kerman Province, Iran

Ahmadi J., Mirnejad H., Modabberi S., Niroomand S.

Abstract

The Esfandaghe manganese deposit is located in the east of Esfandaghe village, Kerman province in Iran. Late Jurassic basalt, lithic tuff, radiolarian chert, shale, flysch turbidite, sandstone, mudstone and dark shale as well as mid-early Jurassic volcanic rocks of rhyolitic crystal tuff and tuffaceous sandstone are the typical stratigraphic units in the study area. Mn ore occurs as interlayers with radiolarian chert and shale overlaying the late Jurassic volcanic rocks. Mn/Fe ratio in manganese ore bodies varies from 0.10 to 43.82 and the position of samples on Fe–Si × 2-Mn, Mn–Fe–(Co + Ni + Cu) × 10, Ni–Zn–Co and (Co + Ni)–(Zn + Cu + Pb + V) diagrams reveals that hydrothermal activity was the main process responsible for mineralization in the Esfandaghe manganese deposit. Cu, Zn, Ni, Co and HREEs are enriched in Esfandaghe manganese relative to Post-Archean Australian Shale. REE contents in the Esfandaghe Mn deposit vary from 22 to 313 ppm, conformable with REE concentration ranges of hydrothermal ferromanganese deposits.

Geochemistry International. 2019;57(3):266-281
pages 266-281 views

Mobility of Dissolved Palladium and Platinum Species during the Water–Rock Interaction in a Chloride Environment: Modeling of PGE Behavior during Interaction between Oceanic Serpentinites and Seawater Derivatives

Kubrakova I.V., Tyutyunnik O.A., Silantyev S.A.

Abstract

Abstract—The palladium and platinum behavior was simulated under conditions of low-temperature hydrothermal alteration of oceanic crust serpentinites in order to reveal the possibility of PGE transfer by highly saline chloride solutions. Flow-through water–rock experiments performed using columns filled with crushed ultrabasic rocks of ocean floor (variably carbonated harzburgitic serpentinites of MOR) showed that the efficiency of the palladium transfer depends of the degree of alteration (carbonation) of peridotites and is 80–100% under experimental conditions. It is suggested that palladium is transferred as a strong complex compound with thiosulfate ion, which represents the intermediate oxidation product in the “sulfide–sulfate” system. Platinum hydrolyzing under near-neutral pH conditions and forming no compounds with thiosulfate-ion is completely retained by serpentinites likely owing to the sorption interaction with silicates. Thus, it was confirmed that palladium is highly mobile during the low-temperature alteration of abyssal peridotites, and its distribution in the studied rocks depends on the serpentinization and carbonation.

Geochemistry International. 2019;57(3):282-289
pages 282-289 views

Adsorption of Trace Elements by Bentonite in the Presence of Bacteria

Perelomov L.V., Sizova O.I., Atroshchenko Y.M.

Abstract

Abstract—The paper addresses the lead and copper adsorption by calcium bentonite, living and destroyed cells of the gram-positive bacteria Bacillus subtilis, as well as in systems including mineral and one of biotic component within the element concentration range of 25–250 μM. The effect of acidity on the biosorption of the studied trace elements is demonstrated. The maximum biosorption of lead and copper of 0.72 and 0.52 mM/g dry matter, respectively, is observed at рН 6. Biosorption by destroyed cells also reached maximum values at рН 6: 0.81 mM/g (Pb) and 0.71 mM/g (Cu). Accumulation of trace elements by living and destroyed cells is an order of magnitude more than their adsorption by calcium bentonite. Three-component bio-mineral systems, including bentonite and bacterial cells or bentonite and cell fragments, showed an increase of lead and copper adsorption as compared to bentonite. The adsorption of trace elements by a mixture of bentonite and cell fragments was lower than the additively calculated sorption by individual components both for lead and for copper at all studied concentrations. Similar tendency was observed in the bentonite–living cell system for copper and in the same system for lead at its low concentration in the sorption solution. The calculated sorption of lead by bentonite and cells was slightly lower than the experimental one, which can be explained by the formation of new specific sorption sites under the influence of living cells.

Geochemistry International. 2019;57(3):290-297
pages 290-297 views

Regularities in the Evolution of Groundwater Quality at Abandoned Copper Sulfide Mines at the Levikha Ore Field, Central Urals, Russia

Rybnikova L.S., Rybnikov P.A.

Abstract

Over the past decades, dozens of copper sulfide mines in the Urals were decommissioned, abandoned, and flooded. At many of them, acidic mine waters are still generated and poured out on the surface. Concentrations of most components in these waters are several orders of magnitude higher than the maximum permissible concentrations. The chemical composition of the acidic groundwaters is generated in a highly dynamic regime: the concentrations of all components in the water first drastically increase after flooding and then decrease during many years. At the Levikha copper sulfide deposit, Sverdlovsk oblast, the filling of the depression cone in 2007 was followed by the origin of focused groundwater discharge: an anthropogenically produced water body (pond) in a caving within the collapse and subsidence zone. The concentrations of many indicator components were higher ten years after the flooding was terminated than when the mining operations were in progress. The dominant source of the acidic waters with elevated mineralization (total dissolved solids, TDS) is the collapse zone, in which an anthropogenically generated sulfuric-acid weathering crust enriched in secondary minerals developed for tens of years in the process of mine drainage. According to results of numerical geofiltration simulations, the lateral flow makes up 60% of the hydrodynamic balance and dilutes the solution generated in the collapse zone. The movement time of this flow through the collapse zone is six–eight years, and this period of time is marked by extremely high values of practically all indicators in the anthropogenic pond. The composition of rocks whose dissolution–precipitation controls the composition of groundwater in the area of the flooded mine was determined by numerical simulations with the Visual MINTEQ ver.3.0/3.1 software. The duration of the process that forms the composition of the acidic groundwaters is estimated at tens of years.

Geochemistry International. 2019;57(3):298-313
pages 298-313 views

Transformation of Structure and Adsorption Properties of Montmorillonite under Thermochemical Treatment

Krupskaya V.V., Zakusin S.V., Tyupina E.A., Dorzhieva O.V., Chernov M.S., Bychkova Y.V.

Abstract

Abstract—Complex studies revealed transformations of composition, structure, and properties of bentonite clays of the Taganskoe (Kazakhstan) and Dahskovskoe (Moscow oblast) deposits under thermochemical treatment. Leaching of cations from interlayer and octahedral sites, protonation of interlayer and OH-groups lead to the modification of interlayer and 2 : 1 layer composition. This, in turn, causes significant changes of properties: a decrease of cation exchange capacity owing to the decrease of layer charge and increase of specific surface through the decomposition and partial amorphization of structure. Bentonites of the Dashkovskoe deposit showed the higher resistance to the thermochemical impact than bentonites of the Taganskoe deposit owing to the isolating action of organic matter. Obtained results demonstrated that bentonite clays preserve most of adsorption properties even under such strong thermochemical influence (13 М HNO3, 90°С, 5 h).

Geochemistry International. 2019;57(3):314-330
pages 314-330 views

Short Communications

Structure of Glasses of the Li2O–K2O–GeO2 System: Raman Spectroscopic Data

Koroleva O.N., Korobatova N.M., Shtenberg M.V., Ivanova T.N.

Abstract

Abstract—Glasses of the three-component Li2O–K2O–GeO2 system are studied by Raman spectroscopy. Spectra are curve-fitted and the main structural units formed in the system are established. Conditions of formation of highly coordinated germanium atoms are determined and non-statistic distribution of network-modifying cations is found. It is shown that lithium for potassium substitution is accompanied by a change of coordination number of germanium, which could cause the destruction of Ge–O–Ge bonds with formation of non-bridging oxygens.

Geochemistry International. 2019;57(3):331-340
pages 331-340 views

Dependence of the Timing of Hydrogeochemical Earthquake Precursor in the Southern Baikal Area on the Energy Classes of the Earthquakes and Their Epicentral Distances

Semenov R.M., Lopatin M.N., Chechel’nitskii V.V.

Abstract

Data obtained on dissolved He concentrations in the waters of blowing wells in the southern Baikal area indicate that these concentrations show certain variations on the eve of earthquakes. Based on these data, a correlation dependence was calculated for the function log τR (logarithm of the product of the precursor time of a seismic event by its epicentral distance) on the energy class of the earthquake. Variations in the He concentrations are suggested to be viewed as a short-term precursor of earthquakes.

Geochemistry International. 2019;57(3):341-348
pages 341-348 views

The Occurrences of Gold and Its Dissolution Method of Geochemical Mapping Sample of Swamp-Forest Area, China

Hanjiang Pan ., Cheng Z., Yang R., Xie X.

Abstract

The Au value of stream sediments in swamp-forest areas in Northeast China is lower than in other areas, according to results from the Regional Geochemistry–National Reconnaissance Program. Two dissolution methods for measurement of Au levels were compared in this study. The Au values in samples dissolved by using four acids (HClO4 + HF + HNO3 + HCl) are larger than those dissolved by using aqua regia, especially when the Au content is greater than 1.25 ng/g. We found that a large amount of Au may be absorbed to or/and included in SiO2 colloids, apart from that occurring in organically bound forms in organic-rich sediments of swamp-forest areas. The Au absorbed to or/and included in SiO2 colloids is related to plant metabolism. This Au can migrate for long distances protected by high-concentration organic acids in water solution, but cannot be dissolved by aqua regia. The results of a pilot survey with an ultra-low sampling density in the Jiayin area, Heilongjiang Province, show that the Au anomalies obtained by using four-acid dissolution are not only larger in scale but also more coincident with corresponding metallogenic belts than those using aqua regia dissolution.

Geochemistry International. 2019;57(3):349-356
pages 349-356 views