On determination of low oxygen concentrations with Winkler technique

The accuracy and detection limit of the oxygen technique is an actual problem in studying the processes that occur in the redox zone. The formal accuracy of the Winkler technique is 1 μM (0.02 mL L⁻¹) and its detection limit is about 3.0 μM (0.06 mL L⁻¹). These values are significantly higher than the similar characteristics (in molar concentrations) for such parameters as the hydrogen sulphide, nitrates, manganese, and others. In this work, we describe some recommendations for increasing the accuracy of the Winkler technique. The results of the application of these recommendations for the suboxic zone of the Black Sea are presented. During the 100th cruise of the R/V Professor Shtokman, argon-filled balloons were attached to the upper valves of Niskin bottles during the sampling, which allowed protecting the samples from contamination with atmospheric oxygen. The titration was performed with an automatic Metrohm Titrino burette with potentiometric end point detection. That allowed us to significantly increase the accuracy and decrease the detection limit compared with the visual techniques. The oxidized forms of metals present in the sea water (Mn(IV), Mn(III); Fe(III)) were measured, which allowed us to correct the Winkler technique calculations for the oxidizers. The studies performed during the 100th cruise of the R/V Professor Shtokman confirmed the absence of a layer of the coexistence of oxygen and hydrogen sulphide.     

Late Cenozoic volcanic activity in western Georgia: Evidence from new isotope geochronological data

The products of volcanic activity from the Kutaisi area and Guria (western Georgia) were studied in terms of isotope geochronology to determine the age of rocks and to confirm their attribution to Cenozoic formations. The results obtained show that the erupted rocks in the Kutaisi area were formed during the three pulses of Mesozoic volcanic activity: the Bajocian, Kimmeridgian-Tithonian, and Turonian-Santonian. It was shown that no displays of Late Cenozoic volcanism occurred in this region of the western Georgia. Because of this, its inclusion into the Central Georgian neovolcanic province, earlier supposed, seems to be improper. By the data of isotope geochronology, Guria is the only region of western Georgia where volcanic activity occurred in post-Paleogene period. Two pulses of young volcanism were revealed: of about 15.5 and 9–7.5 My. The former was related to the introduction of syenite intrusion, and the latter, to subaqueous exudation of subalkaline Neogene lavas. All the outcrops of Neogene rocks we found and dated in Guria fit within the well-pronounced sublatitudinal linear band which probably represents the occurrence in the Middle Miocene of a local zone of extension appearing under conditions of total compression during the collision of the Eurasian and Arabian lithospheric plates.

     

Fine hydrochemical structure of the redox zone in the black sea according to the results of measurements with an open oxygen sensor and with bottle samplers

This study is based on the data obtained on July 14–17, 2004 over a section across the coastal anticyclonic eddy near the town of Tuapse. The data on the oxygen distribution obtained by the Winkler procedure and with an open (membrane-free) sensor with a 15-cm spatial resolution were compared. The divergence of the results in the lower part of the oxycline was 3 μmol or lower; the sensor error was estimated as 1 μmol. The previous data on the absence of the layer of oxygen and hydrogen sulfide coexistence were confirmed. It was shown that the lower boundary of oxygen permeation (where its concentration appeared to be below 1.0 μmol) closely coincided with the upper boundary of the bivalent manganese occurrence, because their coexistence layer was 1 ± 1 m in thickness. Within the same layer or 1–2 m above it, the upper boundary of the deep-sea ammonium and the phosphate minimum were situated. These data may be treated in the following way: oxygen is completely utilized for the oxidation of ammonia and bivalent manganese, and the oxidized suspended manganese formed sinks and is utilized in the reactions of hydrogen sulfide oxidation. The role of the near-slope downwelling (the supply of oxygen-enriched waters to the layers close to the redox zone), which was also observed in the cross section, is discussed.     

Analysis of the water column oxic/anoxic interface in the Black and Baltic seas with a numerical model

A 1D hydrophysical-biogeochemical model was developed to study the cycling of the main elements in the pelagic redox layer in seas with anoxic conditions. The formation and decay of organic matter; the reduction and oxidation of nitrogen, sulfur, manganese, and iron species; and the transformation of phosphorus species were parameterized. Temporal and spatial developments of the model's variables were described by a system of horizontally integrated vertical diffusion equations for non-conservative substances. The calculated spatial and temporal distributions of the above-mentioned parameters were in good agreement with observed vertical distribution patterns of these processes.     

Age and origin of Miocene gabbroid intrusions in the northern part of the Lesser Caucasus

The results of isotope-geochronological and petrological-geochemical study are reported for Neogene mafic intrusive rocks distributed in the northern part of the Lesser Caucasus (Georgia). It is shown that the young plutonic bodies were formed here in two magmatic stages: in the Middle Miocene (around 15.5 Ma) and in the terminal Miocene (9-7.5 Ma). The first age group includes a microsyenitic massif in Guria (Western Georgia), which was formed in a setting of active continental margin related to the subduction of oceanic part of the Arabian plate beneath the Transcaucasus. The Late Miocene intrusive magmatism already records the incipient within-plate activity: small polyphase bodies of alkaline gabbroids and lamprophyres of Samtskhe (South Georgia) dated around 9-8.5 Ma and teschenite intrusions of Guria dated at 7.5Ma. Petrological-geochemical and isotope-geochemical data indicate that the parental melts of the rocks of all studied Neogene plutonic bodies of the Lesser Caucasus were derived from a single mantle source. Its characteristics are close to those of a Common hypothetical reservoir, which is usually regarded as a source of oceanic and continental hot spot basalts (OIB) but shows some regional peculiarity. The role of crustal assimilation and crystallization differentiation in the genesis of the Miocene rocks of Guria was limited, which is related to the rapid ascent of deep melts to the surface (in a setting of local extension) without intense interaction with host sequences under the absence of consolidated continental lithosphere beneath this part of the Transcaucasus. The parental mantle-derived magmas of the Neogene gabbroids of Samtskhe were strongly contributed by upper crustal material, which caused a change in their isotope (⁸⁷Sr/⁸⁶Sr up to 0.70465, ?_Nd up to + 2.8) and geochemical characteristics relative to the regional mantle source. In addition, the crustal contamination of mantle basic melts during the late phases of the Samtskhe plutonic bodies formation led to their intense fractionation with precipitation of mainly olivine and pyroxene. The larger scale mantle-crustal interaction during formation of the Samtskhe intrusions was probably related to the fact that the upper lithosphere in this sector of the Transcaucasus contained large Paleozoic blocks, which were made up of granite-metamorphic complexes and prevented a rapid ascent of mantle melts to the surface. The rocks of these blocks were presumably assimilated by mantle magmas in the intermediate chambers at the upper crustal levels.     

First data on composition of the volcanic rocks of the IVS 50th anniversary Fissure Tolbachik eruption (Kamchatka)

First data on major, minor and trace element (XRF. 1CP-MS) concentrations in the volcanic rocks of the IVS 50th anniversary Fissure Tolbachik eruption are reported for the period from 27.11.2012 to 25.01.2013; scheme of lava flows distribution by March 2013 is made. The volcanic rocks of the new eruption are substantially different from the other studied volcanic rocks of Tolbachinsky Dol by their higher alkalis and incompatible elements content. The rocks of the first three days of eruption (Menyailov Vent) have higher silica and alkalis content than all previously reported volcanic rocks of Tolbachinsky Dol. Volcanic rocks of the Naboko Vent, at silica content similar to high-Al basalts of Tolbachinsky Dol, have different concentrations of trace elements and some major elements (K₂O, CaO, TiO₂, P₂O₅). REE and other incompatible element concentrations in the rocks of the Menyailov Vent are higher than in the rocks of the Naboko Vent at the same element ratios. The differences of the volcanic rocks of the two vents of the new eruption may be caused by the fact that the erupted lavas came from the different levels of the same magma chamber.     

The Dal’negorsk borosilicate skarn deposit,primorye, Russia: Composition of ore-bearing solutions and boron sources

The Dal’negorsk borosilicate skarn deposit (44° 34′ N and 135° 37′ E), located in the center of the ore field bearing the same name, is referred to the category of giant deposits. The currently predominant genetic concept assumes that ore mineralization at this deposit is related to a mantle source and that boron and ore-bearing alkaline fluids are derivatives of a juvenile source as well. The alternative model considered in this paper suggests that sedimentary sequences, probably, evaporites of a local basin, were immediate boron sources and hot subsurface water served as an agent of ore deposition. The authors’ conclusions are based on (1) mineralogical and geochemical features of alteration of premineral dikes as evidence for the composition of percolating ore-bearing fluids, (2) results of fluid inclusion study, and (3) boron and oxygen isotopic compositions of datolite.The latite bodies immediately predating deposition of economic datolite ore do not show mineralogical or geochemical attributes of their belonging to alkaline rock series. According to our data, these bodies are composed of Paleogene premineral basalts that intruded into the future borosilicate deposit close to the central channel of ore-bearing fluid, served as fluid conduits, and were altered to ultrapotassic rocks under the effect of such fluid. It is suggested that hot aqueous ore-bearing fluid was enriched in highly soluble compounds of Ba, K, and B and extremely depleted in poorly soluble compounds of Zr, Nb, Ta, La, and Ce. This suggestion does not contradict the properties and composition of primary and pseudosecondary two-phase fluid inclusions in danburite, datolite, quartz, and fluorite from orebodies. Judging from the boron isotopic composition of datolite (δ¹¹B = ?9 to ?31 ‰), the main amount of boron was extracted from metasedimentary rocks of the Mesozoic basement. The oxygen isotopic composition of datolite from the Dal’negorsk deposit (δ¹⁸O_SMOW = ?1.64 to ?2.97 and less frequently up to ?5‰) indicates a significant contribution of subsurface water to the transport of boron. A model of multistage accumulation of boron in ore of the Dal’negorsk borosilicate skarn deposit is proposed.     

The Role of Suspended Manganese in Hydrogen Sulfide Oxidation in the Black Sea Redox-Zone

The role of suspended manganese in oxidizing deep H₂S is assessed for explaining the persistence of a distance separating the horizon of H₂S wedging out and the appearance of O₂.