Composition of hydrothermal manifestations in the World Ocean

The monograph summarizes results of studies of hydrothermal fields on the ocean floor, hydrothermal plumes and metalliferous sediments. Hydrothermal ore manifestations formed in different geodynamic settings, with different character of volcanism in different facial conditions of deposition are described. Causes of non-uniformity of hydrothermal system functioning in different parts of the ocean and therefore variability of hydrothermal deposits are under consideration. On the base of found relationships of these irregularities with geodynamics, volcanism and sedimentation a new classification of hydrothermal processes and genetic models of hydrothermal ore formation in the ocean have been created. Regularities of hydrothermal sedimentary material dispersion in bottom waters are discussed.

Major- and trace-element chemistry of DSDP Leg 70 Holes basalts and their alteration products

Major and trace element compositions of basalts from the lower part of Hole 504B indicate their cogenetic nature. The cored sequence of interlayered pillow lavas and massive lava flows was produced by eruption of lavas, slightly variable in composition. Plagioclase and olivine crystallization in a shallow magma chamber, followed by small-scale fractionation at higher levels, is responsible for these variations. Except in highly fractured zones within the basement, there are systematic variations in the style and degree of rock alteration with depth. Trace element characteristics of altered rocks and secondary minerals indicate that progressive changes in sea water composition occurred as it reacted with basaltic crust.

Chemical composition of rocks and minerals from the Mid-Atlantic Ridge near 15°20'N

The monograph summarizes results of petrological and geochemical studies of rocks from the ocean floor collected by the authors during expeditions to the Central Atlantic. Detailed work in the Capa Verde transform fault zone gave a large amount of new information about magmatic and hydrothermal systems of the Mid-Atlantic Ridge.

Platinum-group, major, and trace element abundances in ODP Leg 183 basalts

Seventeen basalts from Ocean Drilling Program (ODP) Leg 183 to the Kerguelen Plateau (KP) were analyzed for the platinum-group elements (PGEs: Ir, Ru, Rh, Pt, and Pd), and 15 were analyzed for trace elements. Relative concentrations of the PGEs ranged from ~0.1 (Ir, Ru) to ~5 (Pt) times primitive mantle. These relatively high PGE abundances and fractionated patterns are not accounted for by the presence of sulfide minerals; there are only trace sulfides present in thin-section. Sulfur saturation models applied to the KP basalts suggest that the parental magmas may have never reached sulfide saturation, despite large degrees of partial melting (~30%) and fractional crystallization (~45%). First order approximations of the fractionation required to produce the KP basalts from an ~30% partial melt of a spinel peridotite were determined using the PELE program. The model was adapted to better fit the physical and chemical observations from the KP basalts, and requires an initial crystal fractionation stage of at least 30% olivine plus Cr-spinel (49:1), followed by magma replenishment and fractional crystallization (RFC) that included clinopyroxene, plagioclase, and titanomagnetite (15:9:1). The low Pd values ([Pd/Pt]_pm < 1.7) for these samples are not predicted by currently available Kd values. These Pd values are lowest in samples with relatively higher degrees of alteration as indicated by petrographic observations. Positive anomalies are a function of the behavior of the PGEs; they can be reproduced by Cr-spinel, and titanomagnetite crystallization, followed by titanomagnetite resorption during the final stages of crystallization. Our modeling shows that it is difficult to reproduce the PGE abundances by either depleted upper or even primitive mantle sources. Crustal contamination, while indicated at certain sites by the isotopic compositions of the basalts, appears to have had a minimal affect on the PGEs. The PGE abundances measured in the Kerguelen Plateau basalts are best modeled by melting a primitive mantle source to which was added up to 1% of outer core material, followed by fractional crystallization of the melt produced. This reproduces both the abundances and patterns of the PGEs in the Kerguelen Plateau basalts. An alternative model for outer core PGE abundances requires only 0.3% of outer core material to be mixed into the primitive mantle source. While our results are clearly model dependent, they indicate that an outer core component may be present in the Kerguelen plume source.

Chemical composition of DSDP and ODP cherts

Rare earth element (REE), major, and trace element abundances and relative fractionations in forty nodular cherts sampled by the Deep Sea Drilling Project (DSDP) and Ocean Drilling Program (ODP) indicate that the REE composition of chert records the interplay between terrigenous sources and scavenging from the local seawater. Major and (non-REE) trace element ratios indicate that the aluminosilicate fraction within the chert is similar to NASC (North American Shale Composite), with average Pacific chert including ~7% NASC-like particles, Indian chert ~11% NASC, Atlantic chert ~17% NASC, and southern high latitude (SHL) chert 53% NASC. Using La as a proxy for sum REE, approximations of excessive La (the amount of La in excess of that supplied by the detrital aluminosilicate fraction) indicate that Pacific chert contains the greatest excessive La (85% of total La) and SHL chert the least (38% of total La). As shown by interelement associations, this excessive La is most likely an adsorbed component onto aluminosilicate and phosphatic phases. Accordingly, chert from the large Pacific Ocean, where deposition occurs relatively removed from significant terrigenous input, records a depositional REE signal dominated by adsorption of dissolved REEs from seawater. Pacific chert Ce/Ce* <<1 and normative La/Yb ~ 0.8-1, resulting from adsorption of local Ce-depleted seawater and preferential adsorption of LREEs from seawater (e.g., normative La/Yb ~0.4), which increases the normative La/Yb ratio recorded in chert. Chert from the Atlantic basin, a moderately sized ocean basin lined by passive margins and with more terrigenous input than the Pacific, records a mix of adsorptive and terrigenous REE signals, with moderately negative Ce anomalies and normative La/Yb ratios intermediate to those of the Pacific and those of terrigenous input. Chert from the SHL region is dominated by the large terrigenous input on the Antarctic passive margin, with inherited Ce/Ce* ~1 and inherited normative La/Yb values of ~1.2-1.4. Ce/Ce* does not vary with age, either throughout the entire data base or within a particular basin. Overall, Ce/Ce* does not correlate with P2O5 concentrations, even though phosphatic phases may be an important REE carrier.

Element stratigraphy across the Cretaceous-Tertiary boundary in ODP Hole 119-738C

Neutron activation analyses of iridium and other chemical elements were performed across a 1-m-thick, partly nonbioturbated, clay-rich interval at the Cretaceous/Tertiary boundary in ODP Hole 738C. The results show that the boundary interval holds one of the highest Ir enrichments (320 ng Ir/cm2) of all known Cretaceous/Tertiary boundary layers. Iridium concentrations are highest (18 ppb Ir, whole-rock samples) a few centimeters above the base of the clayrich interval and gradually tail off upsection. Compared with background levels the most Ir-rich interval also shows strongly enhanced concentrations of Cr (215 ppm) and slightly elevated Co concentrations (13 ppm). The Ir-rich interval shows low As (< 15 ppm) and Sb (<0.8 ppm) concentrations, a fact that is congruent with absence of abundant authigenic sulfides in the sediment. Irregularly distributed Fe enrichments and a greenish gray color of the Fe-rich intervals may indicate the presence of glauconitic clay minerals and suboxic, slightly reducing conditions during deposition. Rare earth element (REE) abundance patterns change considerably across the Cretaceous/Tertiary boundary interval, reflecting either a change in Cretaceous/Tertiary boundary seawater REE composition or the occurrence of different REE fractionation processes due to changing depositional environment. Element-vs.-element ratios of Hf, Ta, Th, U, Cs, and Sc are similar between the most Ir-rich layers of the boundary section and other levels with lower Ir concentrations. This may imply that the clay fraction of the Ir-rich layers of the Cretaceous/Tertiary boundary interval is made up predominantly of locally derived material. Calculated calcite-free abundances of Hf, Ta, Th, U, Cs, and Sc, on the other hand, are reconcilable with an extraneous origin of the bulk of the clay in the most Ir-rich layers. The Ir in the Cretaceous/Tertiary boundary clay-rich zone in Hole 738C is most likely derived from an earth-impacting asteroid; however, the origin of the clay-rich zone remains enigmatic.

Trace-element contents in ash samples from DSDP Leg 19 sediments

The Sr, Rb, Ti, and Zr concentrations of 16 volcanic ash samples from Leg 19 of the Deep Sea Drilling Project were determined by X-ray fluorescence. The age of each ash sample had been established previously by faunal criteria and had been confirmed by fission-track dating. Variations in the trace-element concentrations through the past 8 m.y. are clearly seen. Seven of the ashes are older than 4 m.y., have low TiO2 contents, and have Sr concentrations of less than 200 ppm; they are thus similar to tholeiitic basalts of island arcs. Nine ashes are younger than 4 m.y. and are similar in trace-element content to andesite. Magmatic evolution of the Aleutian arc over the past 8 m.y. is clearly shown.

Annual variations in composition of the North Dvina River water

New data on elemental composition of particulate matter from the North Dvina River are presented. In May (period of snowmelt flood) it is similar to the upper layer of the continental crust due to active erosion of crust material in the catchment area. In August (summer low water period) impact of biogenic components increases and elevated concentrations of Cd, Sb, Mn, Zn, Pb, and Cu are observed. At other seasons no significant increase in heavy and rare earth element concentrations is observed.

Composition of drilled sediments and pore waters from the continental slope of the Northern Gulf of Mexico

Pore waters were analyzed from 6 holes drilled from M.V. "Eureka" as a part of the Shell Oil Co. deeper offshore study. The holes were drilled in water depths of 600-3000 ft. (approximately 180-550 m) and penetrated up to 1000 ft. (300 m) of Pliocene-Recent clayey sediments. Salt and anhydrite caprock was encountered in one diapiric structure on the continental slope. Samples from holes drilled near diapiric structures showed systematic increases of pore-water salinity with depth, suggestive of salt diffusion from underlying salt plugs. Anomalous concentrations of K and Br indicate that at least one plug contains late-stage evaporite minerals. Salinities approaching halite saturation were observed. Samples from holes away from diapiric structures showed little change in pore-water chemistry, except for loss of SO4 and other variations attributable to early-stage diagenetic reactions with enclosing sediments. Thus, increased salt concentrations in even shallow sediments from this part of the Gulf appear to provide an indicator of salt masses at depth.

Chemical composition of sediments from DSDP Legs 45 and 71

Results of mineralogical and geochemical investigations of post-Middle Jurassic deposits of the Atlantic Ocean are based on materials of the Deep Sea Drilling Project. Comparative characteristics of primary matter for ''black shales'' are given. Exhalative origin of heavy metal accumulation in near-axial sedimentary deeps of the Mid-Atlantic Ridge (23°N) are shown. History of post-Middle Jurassic sedimentation is considered on the base of clay mineral-, clastic component-, trace and rare- chemical element studies.

Sediment and pore water C and N composition of ODP Holes 201-1227A and 201-1230A

This study addresses the problem of diagenetic fractionation of d15N in sedimentary organic matter by constructing isotopic mass balances for the sedimentary nitrogen and pore water ammonium at two Ocean Drilling Program (ODP) sites, 1227 and 1230. At Site 1230, ammonium production flux integrated through the sedimentary column indicates that >60% of organic matter is lost to decomposition. The d15N of pore water ammonium is <0.7 per mil different from that of the sedimentary organic matter, which implies that very little isotopic fractionation is associated with degradation of organic matter at this site. The constant d15N of the solid-phase sedimentary nitrogen through the whole profile supports this conclusion. Atomic C/N ratios (9-12) indicate that organic matter at this site is primarily of marine origin. At Site 1227, the sedimentary organic matter appears to be a mixture of terrestrial and marine components. Ammonium is ~4 heavier than the organic matter. The observed isotopic enrichment of pore water ammonium relative to the sedimentary nitrogen might indicate either the preferential decomposition of isotopically heavier marine fraction of the organic matter, or possibly, a nonsteady-state condition of the ammonium concentration and d15N profiles. Interpretation of the results at Site 1227 is further complicated by the contribution of ammonium with d15N of ~4 per mil that is diffusing upward from Miocene brines.

Major element chemistr yof fallout tephra from ODP Hole 125-782A

New and published analyses of major element oxides (SiO2, TiO2, Al2O3, FeO*, MnO, MgO, CaO, K2O, Na2O and P2O5) from the central Izu Bonin and Mariana arcs (IBM) were compiled in order to investigate the evolution of the IBM in terms of major elements since arc inception at ~49 million years ago. The database comprises ?3500 volcanic glasses of distal tephra fallout and ?500 lava samples, ranging from the Quaternary to mid-Eocene in age. The data were corrected to 4 wt% MgO in order to display the highly resolved temporal trends. These trends show that the IBM major elements have always been "arc-like" and clearly distinct from N-MORB. Significant temporal variations of some major element oxides are apparent. The largest variations are displayed by K4.0. The data support a model wherein the K2O variability is caused by the addition of slab component with strongly differing K2O contents to a fairly depleted subarc mantle; variable extents of melting, or mantle heterogeneity, appear to play a negligible role. The other major element oxides are controlled by the composition and processes of the subarc mantle wedge. The transition from the boninitic and tholeiitic magmatism of the Eocene and Oligocene to the exclusively tholeiitic magmatism of the Neogene IBM is proposed to reflect a change in the composition of the subarc mantle wedge. The early boninitic magmas originate from an ultra-depleted subarc mantle, that is residual to either the melting of E-MORB mantle, or of subcontinental lithospheric mantle. During the Eocene and Oligocene, this residual mantle is gradually replaced by Indian MORB mantle advected from the backarc regions. The Indian MORB mantle is more radiogenic in Nd isotope ratios but also more fertile with respect to major and trace elements. Therefore the Neogene tholeiites have higher Al2O3 and TiO2 contents and lower mg# numbers at given SiO2 content. After the subarc mantle replacement was complete in the late Oligocene or early Miocene, the Neogene IBM entered a "steady state" that is characterized by the continuous advection of Indian MORB mantle from the reararc, which is fluxed by fluids and melt components from slab. The thickness of the IBM crust must have grown with time, but any effects of crustal thickening on the major element chemistry of the IBM magmas appear to be minor relative to the compositional changes that are related to source composition. Therefore next to the processes of melting, the composition of the mantle sources must play a major role in creating substantiative heterogeneities in the major element chemistry of the arc crust.

Organic matter and trace element concentrations in sapropels from ODP Leg 160 sites

A distinct Pliocene eastern Mediterranean sapropel (i-282), recovered from three Ocean Drilling Program (ODP) Leg 160 Sites, has been investigated for its organic and inorganic composition. This sapropel is characterized by high organic carbon (Corg) and trace element contents, and the presence of isorenieratene derivatives. The latter suggests that the base of the photic zone was sulphidic during formation of the sapropel. Combined with evidence of bottom water anoxia (preservation of laminae, high redox-sensitive trace element contents, and the abundance and isotopic composition of pyrite) this leads to the tentative conclusion that almost the entire water column may have been anoxic. This anoxia resulted from high productivity and not from stagnation, because an approximation of the trace element budget during sapropel formation shows that water exchange with the western Mediterranean is needed. Entire water column anoxia has been suggested earlier for several black shales. With regard to the depositional environment and the Corg content, however, only the Cenomanian=Turonian Boundary Event (CTBE) black shales appear to be comparable to this sapropel. The proposed trace element removal mechanism of scavenging and (co-)precipitation in an anoxic water column, is thought to be similar for both types of deposits. The ultimate trace element source for the sapropel, however, is seawater, whereas it is hydrothermal and fluvial input for CTBE black shales (because they have a larger temporal and spatial distribution). Nonetheless, the Corg-rich eastern Mediterranean Pliocene sapropel discussed here may be considered to be a younger analogue of CTBE black shales.