Manganese metalliferous sediments of the Deryugin Basin (Sea of Okhotsk): Chemical composition and geological setting

This paper reports the results of an investigation of the chemical composition and distribution of manganese-rich metalliferous sediments in the Deryugin Basin. They compose an upper sedimentary layer up to 30 cm thick within a strip up to 40 km wide and 180 km long in the central part of the basin along the East Deryugin suture zone bounding the Deryugin sedimentary basin to the east. The sediments are enriched relative to the regional background composition in Mn (by a factor of 35); Au; Ni; Zn; Co (by a factor of 3–5); and, locally, in Mo, V, Ba, Cu, Pb, and Hg. It was supposed that their formation was controlled by several processes: precipitation of Mn and some other trace elements from hydrothermal plumes of seawater that occasionally form above submarine hot vents in the northern part of the basin, precipitation from anoxic bottom waters at the eastern boundary of the Deryugin sedimentary basin, and early diagenetic migration of Mn into the surface sediments.     

Mercury in the Sedimentary Cover and Basalts of the Basement in the Recent Hydrothermal Activity Area,Middle Valley,Juan de Fuca Ridge

The content and distribution of mercury in Holocene–Upper Pleistocene turbidites, hemipelagic sediments intercalating therein, as well as basement basalts are studied. Samples of sediments were taken from the core of Holes 858A, 858B, 858C, 858D, and 858F. Basalt samples were taken from Holes 858F and 858G drilled during Leg 139 ODP in the Middle Valley (Juan de Fuca Ridge) in the Dead Dog hydrothermal field with a high heat flow (4–20 W/m²) and numerous vents with temperature ranging from 234 to 276°C. Samples of sediments and basalts with the background Hg content were taken from the core of Holes 855A, 855C, and 855D are located beyond the hydrothermal system in the base of the fault scarp on the eastern Middle Valley. In rocks, the content of Hg and its occurrence form were determined by the atomic absorption spectrometry with thermal atomization method; the chemical composition, by the XFA and ICP-MS methods. Sections of the sedimentary cover and basalt basement are marked by an alternation of “layer cake” type units with low and high contents of Hg. Mercury occurs in rocks in the physically adsorbed and mineral forms. The Hg concentration in some parts of the sedimentary section is anomalously high: up to 9696 ppb in Hole 858B and 7260 ppb in Hole 858C. In metalliferous sediments, the Hg content is 3130 ppb. Its maximum content (up to 23200 ppb) is recorded in basalts.     

Phenols in hydrothermal petroleums and sediment bitumen from Guaymas Basin, Gulf of California

The aliphatic, aromatic and polar (NSO) fractions of seabed petroleums and sediment bitumen extracts from the Guaymas Basin hydrothermal system have been analyzed by gas chromatography and gas chromatography-mass spectrometry (free and silylated). The oils were collected from the interiors and exteriors of high temperature hydrothermal vents and represent hydrothermal pyrolyzates that have migrated to the seafloor by hydrothermal fluid circulation. The downcore sediments are representative of both thermally unaltered and thermally altered sediments. The survey has revealed the presence of oxygenated compounds in samples with a high degree of thermal maturity. Phenols are one class of oxygenated compounds found in these samples. A group of methyl-, dimethyl- and trimethyl-isoprenoidyl phenols (C27-C29) is present in all of the seabed NSO fractions, with the methyl- and dimethyl-isoprenoidyl phenols occurring as major components, and a trimethyl-isoprenoidyl phenol as a minor component. A homologous series of n-alkylphenols (C13-C33) has also been found in the seabed petroleums. These phenols are most likely derived from the hydrothermal alteration of sedimentary organic matter. The n-alkylphenols are probably synthesized under hydrothermal conditions, but the isoprenoidyl phenols are probably hydrothermal alteration products of natural product precursors. The suites of phenols do not appear to be useful tracers of high temperature hydrothermal processes.     

Distribution and accumulation rate of ore elements in Holocene and Late Glacial Sediments of the Deryugin Basin,Sea of Okhotsk

Results of the study of contents and accumulation rates of Fe, Mn, and a number of trace elements in Upper Quaternary sediments of the Deryugin Basin are presented. Maps of the average contents and accumulation rates of excess Fe, Mn, Zn, Ba, Ni, Pb, Cu, and Mo in sediments of the first oxygen isotope stage (OIS) have been plotted. Anomalous contents and accumulation rates are confined to peripheral zones of the Deryugin sedimentary basin and large fracture zones. Different mechanisms of the influence of fluid-dynamic processes on the rate of hydrogenic and biogenic accumulation of ore elements are assumed.Translated from Litologiya i Poleznye Iskopaemye, No. 2, 2005, pp. 115–132.Original Russian Text Copyright © 2005 by Astakhov, Gorbarenko, Bakhareva, Gretskaya, Sattarova.     

Iron isotope constraints on the metal source and depositional environment of the Neoproterozoic banded iron- and manganese deposits in Urucum,Brazil

The Urucum area of Brazil hosts a series of Cryogenian ironstones intercalated by oxide-dominated manganese layers. The Urucum iron and manganese formations (IF-MnF) are among the largest sedimentary iron and associated manganese deposits of the Neoproterozoic, however, the depositional model and the source of metals for the IF-MnF in this area are highly controversial. In this study, we performed systematic Fe isotope analysis on fresh and geochemically characterized drill core samples of the Urucum iron and manganese formation deposited in the center of the ancient Urucum graben system. The samples have a large variation in Fe isotope composition, with a δ⁵⁶Fe range of −2.04‰ to +0.75‰, and exhibit a general trend of decreasing δ⁵⁶Fe values with increasing manganese contents. The low δ⁵⁶Fe values of the IF and MnF samples reflect Rayleigh fractionation processes of contineous partial oxidation of aqueous Fe(II) prior to deposition at the sampling site. Using a mixing model and previously published Nd isotope data on the same samples, we estimated that benthic (i.e., porewaters released from submarine sediments in the Urucum basin) Fe fluxes provided 7–50% of total Fe in the Urucum IF-MnF, and the rest of Fe source was from low-temperature hydrothermal vents. Based on combined Fe and Nd isotope data of the Urucum IF-MnF, we propose that low-temperature hydrothermal fluids and benthic fluxes of pore waters were mixed and transported by an upwelling current. The fluid subsequently experienced partial oxidation during the transportation process and became enriched in light Fe isotopes. In the Urucum graben basin, the iron- and manganese-rich oxides deposition occurred progressively under increasingly oxidizing conditions, and such process could have operated repeatedly to produce the alternation of iron and manganese formations. The chemical sediments of the Urucum IF-MnF deposits thus reflect the existence of a sharp redox gradient in the marine environment during the late Cryogenian period.     

Dissolved organic carbon in ridge-axis and ridge-flank hydrothermal systems

The circulation of hydrothermal fluid through the upper oceanic crustal reservoir has a large impact on the chemistry of seawater, yet the impact on dissolved organic carbon (DOC) in the ocean has received almost no attention. To determine whether hydrothermal circulation is a source or a sink for DOC in the oceans, we measured DOC concentrations in hydrothermal fluids from several environments. Hydrothermal fluids were collected from high-temperature vents and diffuse, low-temperature vents on the basalt-hosted Juan de Fuca Ridge axis and also from low-temperature vents on the sedimented eastern flanks. High-temperature fluids from Main Endeavour Field (MEF) and Axial Volcano (AV) contain very low DOC concentrations (average = 15 and 17 μM, respectively) compared to background seawater (36 μM). At MEF and AV, average DOC concentrations in diffuse fluids (47 and 48 μM, respectively) were elevated over background seawater, and high DOC is correlated with high microbial cell counts in diffuse fluids. Fluids from off-axis hydrothermal systems located on 3.5-Ma-old crust at Baby Bare Seamount and Ocean Drilling Program (ODP) Hole 1026B had average DOC concentrations of 11 and 13 μM, respectively, and lowered DOC was correlated with low cell counts. The relative importance of heterotrophic uptake, abiotic sorption to mineral surfaces, thermal decomposition, and microbial production in fixing the DOC concentration in vent fluids remains uncertain. We calculated the potential effect of hydrothermal circulation on the deep-sea DOC cycle using our concentration data and published water flux estimates. Maximum calculated fluxes of DOC are minor compared to most oceanic DOC source and sink terms.     

Geochemistry of rare earth elements in bottom sediments of the Brazil Basin, Atlantic Ocean

The sedimentation and ore formation were studied in sediments from nine stations located in the 24°W profile in the Brazil Basin of the Atlantic Ocean. The sediments are represented by mio- and hemipelagic muds, which are variably enriched in hydrothermal iron and manganese oxyhydroxides. As compared to the sediments from other basins of the Atlantic Ocean, these rocks are marked by extremely high manganese contents (up to 1.33%) and maximal enrichment in Ce. It was shown that the positive Ce anomaly is related to the REE accumulation on iron oxyhydroxides. Influence of hydrothermal source leads to the decrease of Ce anomaly and LREE/HREE ratio. In the reduced sediments, preservation of positive Ce anomaly and/or its disappearance was observed after iron and manganese reduction. The REE contents were determined for the first time in the Ethmodiscus oozes of the Brazil Basin. Ore deposits of the Brazil Basin are represented by ferromanganese crust and ferromanganese nodules. Judging from the contents of iron, manganese, rare, and trace elements, these formations are ascribed to the sedimentation (hydrogenic) deposits. They are characterized by a notable positive Ce anomaly in the REE pattern. The extremely high Ce content (up to 96% of total REE) was discovered for the first time in the buried nodules (Mn/Fe = 0.88).     

Changes of planktonic and benthic foraminiferal assemblages in upper quaternary sediments of the Deryugin Basin, Sea of Okhotsk

The analysis of foraminiferal assemblages in sediments that were deposited during the last 30 kyr revealed similar patterns in their distribution in the central and marginal parts of the Deryugin Basin. The similar composition of foraminifers through the entire basin implies similarity in natural environments within its limits. The absence of benthic foraminifers or extreme impoverishment of the assemblages during the maximum of the last glaciation could result from a combination of several factors: drastic decrease in bioproductivity due to general cooling, development of bottom anoxia, and presumably unfavorable influence of seeps on geochemical parameters of bottom waters. The weak activity of barite-methane seeps in the central part of the basin during the Holocene is evident from some variations in the structure of benthic foraminiferal assemblages against the background of their similar taxonomic compositions.     

Geochemistry of diffuse low-temperature hydrothermal fluids in the North Fiji basin

Low-temperature (<13°C) diffuse hydrothermal fluids were sampled directly at the seafloor with a specially designed Hydro Bottom Station in the North Fiji Basin and analyzed for gases, major and minor elements, and a large number of trace metals. The fluids were significantly enriched in CO₂, Si, Li, Rb, Cs, Ba, Mn, and several trace metals compared to ambient seawater, had high CH₄ and H₂S concentrations, and had a slightly decreased salinity. Calculated end-member concentrations of the low-temperature fluids show a strong similarity to the neighboring hot vents, implying that the diffuse fluids are hot vent waters diluted by seawater. According to the chemical composition, the sampled fluids derive from vapor-phase fluids produced by subseafloor boiling and phase separation. Compared to hot vents from other regions, Mn, Fe, and other trace metal concentrations are low. Subsurface metal sulfide precipitation during cooling and dilution with seawater has further decreased the dissolved metal contents of the diffuse fluids, thus creating a very favorable environment for the hydrothermal fauna, as indicated by a very low Fe/H₂S ratio. Therefore, the fluids support high bioproductivity but no hydrothermal mineral precipitation. The emanation of the condensed vapor phase appears to have been stable during the past 10 years; however, the occurrence of metal sulfide particles in some fluid and sediment samples and small areas of dead fauna indicate that the hydrothermal system may be evolving toward the emanation of the stored brine phase.     

Geochemical characteristics of the surface layer of bottom sediments from the Deryugin Basin, Sea of Okhotsk

This paper reports data, including new analyses, on the contents of Ni, Co, V, Mo, Fe, Mn, Zn, Ba, Sc, Y, Cd, Rb, Cs, and W in the sediments of the Deryugin Basin. The features of the distribution of chemical elements in the bottom area were identified, and the zones of maximum accumulation of the major and trace elements were allocated. A correlation between the elements was shown.     

冲绳海槽海底沉积物汞异常──现代海底热水效应的“指示剂”

基于６０余种化学元素丰度的比较，发现冲绳海槽海底存在汞异常，论证了“过剩汞”系源自海底热水，指出汞异常可作为现代海底热水效应的一个地球化学指示剂。     

Unstable Climate Oscillations during the Late Holocene in the Eastern Bransfield Basin, Antarctic Peninsula

Core A9-EB2 from the eastern Bransfield Basin, Antarctic Peninsula, consists of pelagic (diatom ooze-clay couplets and bioturbated diatom ooze) and hemipelagic (bioturbated mud) sediments interbedded with turbidites (homogeneous mud and silt–clay couplets). The cyclic and laminated nature of these pelagic sediments represents alternation between the deposition of diatom-rich biogenic sediments and of terrigenous sediments. Sediment properties and geochemical data explain the contrasting lamination, with light layers being finer-grained and relatively rich in total organic carbon and biogenic silica content. Also, the high-resolution magnetic susceptibility (MS) variations highlight distinct features: high MS values coincide with clastic-rich sections and low MS values correspond to biogenic sections. The chronology developed for core A9-EB2 accounts for anomalous ages associated with turbidites and shows a linear sedimentation rate of approximately 87 cm/10³ yr, which is supported by an accumulation rate of 80 cm/10³ yr calculated from ²¹⁰Pb activity. The late Holocene records clearly identify Neoglacial events of the Little Ice Age (LIA) and Medieval Warm Period (MWP). Other unexplained climatic events comparable in duration and amplitude to the LIA and MWP events also appear in the MS record, suggesting intrinsically unstable climatic conditions during the late Holocene in the Bransfield Basin of Antarctic Peninsula.     

中国汞的地球化学空间分布特征

20世纪80年代以来中国积累了岩石、土壤和水系沉积物中的大量可靠的汞分析数据和图件,为分析汞的地球化学空间分布特征提供了依据.从空间分布上看,从中国北部到南部,从西部到东部,土壤和水系沉积物中汞的含量背景值逐渐增高,汞在以干旱荒漠区、半干旱荒漠区、黄土地区和高寒山区为主的西部和北部呈低背景,在东部的森林沼泽区和半湿润低山丘陵区为中等背景,在南部的湿润低山丘陵区、热带雨林区和高山峡谷区为高背景,尤其在以云南东南部、贵州、广西西部、湖南西部岩溶区为中心的低温成矿域内,无论岩石、土壤还是水系沉积物,汞含量背景值达到最高.一般情况下,岩石、土壤和水系沉积物之间的汞含量具有继承性,在地理空间分布上呈明显的对栽应关系,并且土壤和水系沉积物之间的汞含量具有相近性,土壤和水系沉积物较岩石更为富集汞.     

First Data about Mercury in Modern Hydrothermal Process in the Ocean,Juan de Fuca Ridge

The results of studying Hg in an underwater hydrothermal system in the ocean using the Middle Valley of the Juan de Fuca ridge as an example are presented. A significant part of Hg is accumulated in the basalt fundament (Holes 858F, G), forming anomalously high concentrations (up to 29.30 ppm) in certain parts. The high Hg contents were established in metalliferous sediments (323 ppm) of the sedimentary cover (Hole 858D) and in sulfide deposits (up to 10.30 ppm). In other parts of the section, Hg content is 0.02–0.76 ppm (Holes 858B, D, F), background Hg contents in sediments—0.08–0.28 ppm and in basalts—0.17–0.31 ppm (Holes 855A, C, D).     

Geodynamics of ophiolites and formation of hydrocarbon fields on the shelf of eastern Sakhalin

A model is proposed showing the formation of hydrocarbon fields on the shelf of eastern Sakhalin as being caused by sustained (from the Late Cretaceous to the present) extension in the adjacent deepwater Deryugin Basin with exposure of the upper mantle rocks at the bottom of the sedimentary basin. The thrust faults and detachments formed through this process facilitated the penetration of seawater into ultramafic rocks, thus providing large-scale serpentinization accompanied by generation of hydrocarbons. Extension in the Deryugin Basin was compensated by horizontal shortening at its margins, and as a result, by the formation of ophiolitic allochthons as constituents of the accretionary prism of eastern Sakhalin. Hydrocarbons were injected and pumped in the root zones of the allochthons, giving rise to their westward migration and the formation of petroleum pools in fault-line and underthrust traps on the shelf of Sakhalin Island. The Deryugin Basin is a petroleum-collecting area for oil and gas fields localized in the upper part of its western margin. More broadly, the work considers interrelations between hydrocarbon generation and the geodynamics of tectonic couples of ophiolitic allochthons and adjacent deepwater basins of marginal seas, in particular, in the western Pacific.     

南海沉积物中烃类气体(酸解烃)特征及其成因与来源

烃类气体是形成天然气和天然气水合物的物质基础,可通过顶空气、吸附烃和酸解烃等方法来探测。南海473个站位767件沉积物样品的酸解烃分析结果表明,甲烷含量为0.8~22153.6μl/kg,平均为335.8μl/kg,并可分成台西南—东沙、笔架南、琼东南—西沙海槽、中建南—中业北、万安—南薇西和南沙海槽等6大异常区,其中南沙海槽是异常最强烈的地区,台西南盆地次之。154件甲烷样品的碳同位素分析结果表明,其δ13C1值为-101.7‰~-24.4‰(PDB标准,下同),平均为-44.5‰,其中南沙海槽的δ13C1值明显偏低,为-101.7‰~-71.4‰,应是微生物气或是以微生物气为主的混合气,而南海其他地区的δ13C1值相对较高,为-51.0‰~-24.4‰,明显属于热解气。     

Cenozoic lithogenesis in the Baikal rift zone

New data on the geological history and Cenozoic lithogenesis in depressions of the Baikal rift zone are considered with areas adjacent to Lake Baikal as example. In this region, rifting developed during the plain (Late Oligocene?Early Pliocene) and orogenic (Late Pliocene?Holocene) stages and was accompanied by the accumulation of plain coaliferous fan and orogenic molasses formations, respectively. The examination of Quaternary sequences in the Baikal region reveals that deposition and postsedimentary transformations of riftogenic sediments were intensely influenced by deep-seated water sources of the so far undivided stratal?infiltration, elision, and exfiltration types, according to the classification in (Kislyakov and Shchetochkin, 2000). Deep processes in this region determined the elevated heat flow, volcanism, and extensive discharge of hydrothermal solutions and gas fluids. In our opinion, gaseous?hydrothermal activity stimulated the formation of hydrothermal?sedimentary rocks (dolomitic and calcitic travertines, geyserites, aluminosulfates), the accumulation of diatomaceous and carbonaceous oozes in Baikal, and the formation of a large methane gas hydrate deposit.     

Abundances and sources of rare-earth elements in the modern volcanogenic hydrothermal systems of Kamchatka

Sources of modern hydrothermal systems are considered on the basis of high-precision REE data on representative samples of characteristic hydrochemical types of hydrothermal systems of the Eastern Volcanic Belt of Kamchatka and data available on modern magmatogenic fluid systems of the Kamchatka, Kuriles, and oceanic rift zones. It was found that modern high-temperature chloride-sodium hydrothermal vents have elevated REE contents and that all considered hydrochemical types of the Kamchatka hydrothermal systems are characterized by similar REE patterns. High REE contents in the hydrothermal vents with pH up to 5.0 show bimodal distribution. Correlations established between La/Yb ratios in the hydrothermal vents of various types and in the igneous rocks of the Eastern Volcanic Belt of Kamchatka are interpreted in genetic terms. A positive correlation was found between rare-earth elements, chlorine and boron contents. It was noted that all considered hydrochemical types show distinct negative europium anomaly, whereas submarine hydrothermal vents of oceanic rift zones are characterized by positive europium anomaly. It was proposed that REE was transported in the hydrothermal vents from apical zones of deep-seated magma chambers containing acid derivatives.     

南海陆坡中新世以来沉积物特性与气体水合物分布初探

通过对南海陆坡地区中新世以来沉积物的一些属性和特征的研究,获得了下面的初步认识：（1）南海陆坡有几个沉积速率较高的地区, 如东沙一带、西沙海槽、中建南地区,以及南沙西南部和西北部（曾母、万安盆地）;（2）大洋钻探钻井资料的研究表明,中新世与早上新世为高碳酸盐比值的低速堆积期,而近200万a以来为低碳酸盐比值的高速堆积期,上新世晚期至全新世沉积物以粘土质粉砂和粉砂质粘土为最主要成分;（3）南海不同时期的沉积速率不同,全新世为沉积速率最高的时期,其次为更新世;上新世和中新世为沉积速率较低的时期。南海利于气体水合物存藏的沉积可能为全新世和更新世的沉积;（4）对南海晚第四纪以来沉积物的综合研究表明南海陆坡的A区（东沙附近）、B区（西沙海槽）、D区（南海西部、越南以东）等地区可能利于气体水合物的形成和分布;而E区（南沙西南部）、F区（南沙中上部）和G区(南沙海槽)则是气体水合物调查值得关注的地区。     

Geochemistry and morphology of metalliferous sediments and oxyhydroxides from the Endeavour segment, Juan de Fuca Ridge

We present first data on the geochemistry, mineralogy and morphology of near-vent sediments (35 and 200 m from active vent) and ridge flank sediments (approximately 3 km from the vent field) as well as oxyhydroxide deposits from the Endeavour segment, Juan de Fuca Ridge. The purpose of the study was to understand better the origin and characteristic features of metalliferous sediments associated with base and precious metal massive sulfides in volcanic terrains. Hydrothermal components in sediments are Fe-Si ± S-rich and Mn-Fe-Si-rich phases, sulfides and barite, which were exclusively derived from plume fallout. Sulfides are only a minor constituent of near-vent sediments (2-4 wt%) and were not detected in ridge flank sediments. The study suggests that the distribution of hydrothermal phases and associated elements in near-vent and ridge flank sediments is affected mainly by processes of agglomeration, dissolution, absorption and settling that take place within a plume and to a lesser extent post-depositional processes. Rapid deposition of sulfides in the vicinity of the vents is reflected in a sharp drop of the Cu concentrations in sediments with increasing distance from the vents. Besides sulfides, important carriers of Pb, Cu, Zn and Co in near-vent sediments are Fe-Mn oxyhydroxides that occur together with silica as aggregates of gel-like material and flaky particles and as coatings on filaments. Away from the vents, trace metals are mostly in Fe-Mn oxyhydroxides and authigenic Fe-rich montmorillonite. Oxyhydroxides at the Main Endeavour field are interpreted to have originated from oxidation of mound sulfides accompanied by precipitation of primary Fe-oxyhydroxide + silica from low-temperature fluids. At the Mothra field, seafloor deposits and chimney crusts composed of Fe-oxyhydroxide ± Mn + silica are considered to be direct precipitates from hydrothermal fluids that have been less diluted with seawater. Oxyhydroxide deposits exhibit unique microtextures that resemble mineralized microorganisms and may indicate existence of diverse microbial communities.