Geochemistry of selected Ferrar samples from Northern Victoria Land and George V Land during GANOVEX VIII

Newly sampled basaltic andesites and andesites from the tholeiitic Ferrar Supergroup of northern Victoria Land and George V Land, Antarctica, are attributed to the known low-Ti and high-Ti series. Aside from known sparsely distributed high-Ti extrusives, a high-Ti sill was found in the Alamein Range outside the Rennick Graben. Low-Ti lavas, sills and dikes display wide petrographical, mineral and geochemical variations, reflecting extensive in-situ differentiation. High-Ti rocks from Litell Rocks are homogeneous with respect to mineralogy and geochemistry, minor deviations are shown by the sampled sill. Chilled margins of low-Ti sills, dikes and lava flows exhibit nearly constant bulk-rock chemistry (mg# ~60) within the studied area. Compared to chilled margins from Tasmanian sills, the striking uniformity of the pre-emplacement chemistry of Ferrar magmas over large distances supports the magma transport model of Elliot et al. (1999, doi:10.1016/S0012-821X(99)00023-0). In the area investigated, compositional variations within the low-Ti series, caused by in-situ differentiation, increase towards the Wilson-Bowers Terrane boundary, possibly displaying the asymmetrical distribution of outcrops over this area. Absence of Ferrar occurrences east of the Bowers Terrane remains a matter of palaeo-geodynamic discussion. Besides, the secondary mineralogy of extrusives from Litell Rocks and Monument Nunataks exhibits noticeable differences, which indicates an elevated thermal gradient in the vicinity of Litell Rocks compared to Monument Nunataks during the Cretaceous.

Chemistry of low-temperature hydrothermal altered basement of ODP Site 129-801

Low-temperature hydrothermal alteration of basement from Site 801 was studied through analyses of the mineralogy, chemistry, and oxygen isotopic compositions of the rocks. The more than 100-m section of 170-Ma basement consists of 60 m of tholeiitic basalt separated from the overlying 60 m of alkalic basalts by a >3-m-thick Fe-Si hydrothermal deposit. Four alteration types were distinguished in the basalts: (1) saponite-type (Mg-smectite) rocks are generally slightly altered, exhibiting small increases in H2O, d18O, and oxidation; (2) celadonite-type rocks are also slightly altered, but exhibit uptake of alkalis in addition to hydration and oxidation, reflecting somewhat greater seawater/rock ratios than the saponite type; (3) Al-saponite-type alteration resulted in oxidation, hydration, and alkali and 18O uptake and losses of Ca and Na due to the breakdown of plagioclase and clinopyroxene; and (4) blue-green rocks exhibit the greatest chemical changes, including oxidation, hydration, alkali uptake, and loss of Ca, Na, and Mg due to the complete breakdown of plagioclase and olivine to K-feldspar and phyllosilicates. Saponite- and celadonite-type alteration of the tholeiite section occurred at a normal mid-ocean ridge basalt spreading center at temperatures <20°C. Near- or off-axis intrusion of an alkali basalt magma at depth reinitiated hydrothermal circulation, and the Fe-Si hydrothermal deposit formed from cool (<60°C) distal hydrothermal fluids. Focusing of fluid flow in the rocks immediately underlying the deposit resulted in the extensive alteration of the blue-green rocks at similar temperatures. Al-saponite alteration of the subsequent alkali basalts overlying the deposit occurred at relatively high water/rock ratios as part of the same low-temperature circulation system that formed the hydrothermal deposit. Abundant calcite formed in the rocks during progressive "aging" of the crust during its long history away from the spreading center.

Geochemistry of Lesser Antilles forearc sediments

Oceanic sediments contain the products of erosion of continental crust, biologic activity and chemical precipitation. These processes create a large diversity of their chemical and isotopic compositions. Here we focus on the influence of the distance from a continental platform on the trace element and isotopic compositions of sediments deposited on the ocean floor and highlight the role of zircons in decoupling high-field strength elements and Hf isotopic compositions from other trace elements and Nd isotopic compositions. We report major and trace element concentrations as well as Sr and Hf isotopic data for 80 sediments from the Lesser Antilles forearc region. The trace-element characteristics and the Sr and Hf isotopic compositions are generally dominated by detrital material from the continental crust but are also variably influenced by chemical or biogenic carbonate and pure biogenic silica. Next to the South American continent, at DSDP Site 144 and on Barbados Island, sediments, coarse quartz arenites, exhibit marked Zr and Hf excesses that we attribute to the presence of zircon. In contrast, the sediments from DSDP Site 543, which were deposited farther away from the continental platform, consist of fine clay and they show strong deficiencies in Zr and Hf. The enrichment or depletion of Zr-Hf is coupled to large changes in Hf isotopic compositions (-30 < epsilon-Hf < +4) that vary independently from the Nd isotopes. We interpret this feature as a clear expression of the "zircon effect" suggested by Patchett and coauthors in 1984. Zircon-rich sediments deposited next to the South American continent have very low epsilon-Hf values inherited from old zircons. In contrast, in detrital clay-rich sediments deposited a few hundred kilometers farther north, the mineral fraction is devoid of zircon and they have drastically higher epsilon-Hf values inherited from finer, clay-rich continental material. In the two DSDP sites, average Hf isotopes are very unradiogenic relative to other oceanic sediments worldwide (epsilon-Hf = -14.4 and -7.4) and they define the low Hf end member of the sedimentary field in Hf-Nd space. Their compositions correspond to end members that, when mixed with mantle, are able to reproduce the pattern of volcanic rocks from the Lesser Antilles. More generally, we find a relationship between Nb/Zr ratios and the vertical deviation of Hf isotope ratios from the Nd-Hf terrestrial array and we suggest that this relationship can be used as a tool to distinguish sediment input from fractionation during melting during the formation of arc lavas.

Geochemistry of ODP Hole 135-841B

Two igneous rock units were recovered at Site 841. More than 200 m of island-arc rhyolites, rhyolitic tuffs, lapilli tuffs, and pumice breccias, divided into five units, compose the basement at the site. These rhyolitic volcanics are late middle Eocene or older and formed part of a subaerial rhyolitic volcano. These low-K rhyolites were produced by fractional crystallization of a more mafic arc-tholeiitic lava or by dehydration melting of lower crustal arc tholeiites. The Site 841 basement rocks are similar in composition to high-SiO2 lavas in the Eocene basement on 'Eua and crystallized from depleted island-arc-tholeiitic basalts like those exposed on 'Eua. No evidence is present in the rhyolites, or in the clasts enclosed within them, for boninite series magmas at Site 841. The Site 841 rhyolitic complex bears no resemblance to Cretaceous rhyolites from the Lord Howe Rise, which are enriched in K and incompatible elements. The volcanic rocks at Site 841 are part of a widely distributed Eocene volcanic episode that marked the earliest phases of subduction in the Tonga region; they are not part of an older crustal fragment. The second igneous sequence is a series of basaltic dikes and sills that intruded Miocene sediments. These basalts have trace element abundances and ratios identical to upper Miocene lavas from the Lau Ridge. The Site 841 basalts do not have any geochemical characteristics that suggest they were generated by unusual thermal conditions in the shallow sub-forearc mantle. They are most reasonably interpreted as intrusions fed by basement dikes propagated from the associated active arc. No evidence for local serpentinite exposures, like those that are common in the Mariana forearc, was found at Site 841. The results from Site 841 provide strong support for hypotheses of forearc evolution that have been advanced for the Izu-Bonin-Mariana system.

Whole-rock and mineral geochemistry of ODP Hole 176-735B gabbros

We report mineral chemistry, whole-rock major element compositions, and trace element analyses on Hole 735B samples drilled and selected during Leg 176. We discuss these data, together with Leg 176 shipboard data and Leg 118 sample data from the literature, in terms of primary igneous petrogenesis. Despite mineral compositional variation in a given sample, major constituent minerals in Hole 735B gabbroic rocks display good chemical equilibrium as shown by significant correlations among Mg# (= Mg/[Mg + Fe2+]) of olivine, clinopyroxene, and orthopyroxene and An (=Ca/[Ca + Na]) of plagioclase. This indicates that the mineral assemblages olivine + plagioclase in troctolite, plagioclase + clinopyroxene in gabbro, plagioclases + clinopyroxene + olivine in olivine gabbro, and plagioclase + clinopyroxene + olivine + orthopyroxene in gabbronorite, and so on, have all coprecipitated from their respective parental melts. Fe-Ti oxides (ilmenite and titanomagnetite), which are ubiquitous in most of these rocks, are not in chemical equilibrium with olivine, clinopyroxene, and plagioclase, but precipitated later at lower temperatures. Disseminated oxides in some samples may have precipitated from trapped Fe-Ti-rich melts. Oxides that concentrate along shear bands/zones may mark zones of melt coalescence/transport expelled from the cumulate sequence as a result of compaction or filter pressing. Bulk Hole 735B is of cumulate composition. The most primitive olivine, with Fo = 0.842, in Hole 735B suggests that the most primitive melt parental to Hole 735B lithologies must have Mg# 0.637, which is significantly less than Mg# = 0.714 of bulk Hole 735B. This suggests that a significant mass fraction of more evolved products is needed to balance the high Mg# of the bulk hole. Calculations show that 25%-45% of average Eastern Atlantis II Fracture Zone basalt is needed to combine with 55%-75% of bulk Hole 735B rocks to give a melt of Mg# 0.637, parental to the most primitive Hole 735B cumulate. On the other hand, the parental melt with Mg# 0.637 is far too evolved to be in equilibrium with residual mantle olivine of Fo > 0.89. Therefore, a significant mass fraction of more primitive cumulate (e.g., high Mg# dunite and troctolite) is yet to be sampled. This hidden cumulate could well be deep in the lower crust or simply in the mantle section. We favor the latter because of the thickened cold thermal boundary layer atop the mantle beneath slow-spreading ridges, where cooling and crystallization of ascending mantle melts is inevitable. These observations and data interpretation require reconsideration of the popular concept of primary mantle melts and relationships among the extent of mantle melting, melt production, and the composition and thickness of igneous crust.

Iodine and boron concentrations in pore fluids, ultramafic clasts and interstitial serpentinite mud of ODP Hole 125-779A and Site 195-1200

Iodine and boron were analyzed in pore fluids, serpentinized ultramafic clasts, and the serpentinized mud matrix of the South Chamorro Seamount mud volcano (Ocean Drilling Program Leg 195 Site 1200) to determine the distribution of these elements in deep forearc settings. Similar analyses of clasts and muds from the Conical Seamount mud volcano (Leg 125 Site 779) were also carried out. Interstitial pore fluids are enriched in boron and iodine without appreciable change in chloride concentration relative to seawater. Both the ultramafic clasts and the associated serpentinized mud present the highest documented iodine concentrations for all types of nonsedimentary rocks (6.3-101.7 µmol/kg). Such high iodine concentrations, if commonplace in marine forearc settings, may constitute a significant, previously unknown reservoir of iodine. This serpentinized forearc mantle reservoir may potentially contribute to the total crustal iodine budget and provide a mechanism for its recycling at convergent plate margins. Both clasts and mud show concurrent enrichments in boron and iodine, and the similarity in pore fluid profiles also suggests that these two incompatible, fluid-mobile elements behave similarly at convergent plate margins.

Chemical analysis of ODP Hole 104-642E

During Ocean Drilling Program Leg 104 a 900-m-thick sequence of volcanic rocks was drilled at Hole 642E on the Vøring Plateau, Norwegian Sea. This sequence erupted in two series (upper and lower series) upon continental basement. The upper series corresponds to the seaward-dipping seismic reflectors and comprises a succession of about 122 flows of transitional oceanic tholeiite composition. They have been subdivided into several formations consisting of flows related to each other by crystal fractionation processes, magma mixing, or both. Major- and trace-element chemistry indicates affinities to Tertiary plateau lavas of northeast Greenland and to Holocene lavas from shallow transitional segments of the Mid-Atlantic Ridge, such as Reykjanes Ridge. The tholeiitic magmas have been derived from a slightly LREE-depleted mantle source. Two tholeiitic dikes that intruded the lower series derive from an extremely depleted mantle source. Interlayered volcaniclastic sediments are dominantly ferrobasaltic and more differentiated. They appear to come from a LREE-enriched mantle source, and may have been erupted in close vicinity of the Vøring Plateau during hydroclastic eruptions. The two tholeiitic dikes that intruded the lower series as well as some flows at the base of the upper series show evidence of assimilation of continental upper crustal material.

Chemical composition of phosphorites, Fe-Mn nodules and crusts, and basalts from the West Pacific

The monograph gives the first systematic description of ore-bearing guyots from the West Pacific. It is mostly based on data obtained in numerous expeditions of Russian vessels during 1984-1992. Ore deposits located on upper parts of all slopes and tops of the guyots include phosphorites associated with cobalt- and platinum-rich ferromanganese crusts. Location, origin and prospecting of mineral deposits are discussed on the base of new data on metallogenic factors (geodynamics, tectonics, magmatism, sedimentation and morphostructures).

Sm-Nd, Rb-Sr, and He isotopic composition and hydrocarbon gases in rocks and minerals from the Markov Deep, Mid-Atlantic Ridge rift valley

The paper presents characteristics of the Nd and Sr isotopic systems of ultrabasic rocks, gabbroids, plagiogranites, and their minerals as well as data on helium and hydrocarbons in fluid inclusions of the same samples. Materials presented in this publication were obtained by studying samples dredged from the MAR crest zone at 5°-6°N (U/Pb zircon dating, geochemical and petrological-mineralogical studies). It was demonstrated that variations in the isotopic composition of He entrapped in rocks and minerals were controlled by variable degrees of mixing of juvenile He, which is typical of basaltic glass for MAR (DM source), and atmospheric He. Increase in the atmospheric He fraction in plutonic rocks and, to a lesser degree, in their minerals reflects involvement of seawater or hydrated material of the oceanic crust in magmatic and postmagmatic processes. This conclusion finds further support in positive correlation between the fraction of mantle He (R ratio) and 87Sr/86Sr ratio. High-temperature hydration of ultrabasic rocks (amphibolization) was associated with increase in the fraction of mantle He, while their low-temperature hydration (serpentinization) was accompanied by drastic decrease in this fraction and significant increase in 87Sr/86Sr ratio. Insignificant variations in 143Nd/144Nd (close to 0.5130) and 87Sr/86Sr (0.7035) in most of gabbroids and plagiogranites as well as the fraction of mantle He in these rocks, amphibolites, and their ore minerals indicate that the melts were derived from the depleted mantle. Similar e-Nd values of gabbroids, plagiogranites, and fresh harzburgites (6.77-8.39) suggest that these rocks were genetically related to a single mantle source. e-Nd value of serpentinized lherzolites (2.62) likely reflects relations of these relatively weakly depleted mantle residues to another source. Aforementioned characteristics of the rocks generally reflect various degrees of mixing of depleted mantle components with crustal components (seawater) during metamorphic and hydrothermal processes that accompanied formation of the oceanic crust.

Clay mineralogy of late Eocene to early Miocene sediments of McMurdo Sound, Antarctica

The clay mineral assemblages of upper Eocene to lower Miocene sediments recovered at the CIROS-1 and MSSTS-1 drill sites on the McMurdo Sound shelf, Antarctica, were analyzed in order to reconstruct the Cenozoic Antarctic paleoclimate and ice dynamics. The assemblages are dominated by smectite and illite, with minor amounts of chlorite and kaolinite. The highest smectite amounts and best smectite crystallinities occur in the upper Eocene part of CIROS-1, below 425-445 mbsf. They indicate that during their deposition, chemical weathering conditions prevailed on the nearby continent. Large parts of East Antarctica were probably ice-free at that time, but some glaciers reached the sea and contributed to the glaciomarine sedimentation. In contrast, only minor total amounts of smectite are present in Oligocene and younger sediments due to the shift to mainly physical weathering on an ice-covered Antarctic continent. However, relative smectite percentages rise to more than 60% during two late Oligocene intervals (ca. 27.5-26.2 and 25.0-24.5 Ma) and during one early Miocene interval starting at ca. 23.3 Ma. These intervals are characterized by ice masses coming probably from the south, where volcanic rocks acted as a source, as also indicated by the composition of the sand and gravel fractions. During the other intervals, the ice came from the west, where the physical erosion of basement rocks and sedimentary rocks of the Beacon Supergroup in the Transantarctic Mountains provided high illite concentrations. Because the two drill sites are only 4 km apart, their clay mineral records can be correlated. This led to a new interpretation of the Oligocene paleomagnetic data of the MSSTS-1 site and to a more detailed lithostratigraphic correlation of the Miocene parts of the cores.

Contents of P2O5 and REE in phosphorites from shelves and Pacific seamounts

Recent phosphorites from the Namibian shelf are characterized by low REE contents, depletion in REE compared to host sediments and sharp deficiency of lanthanum and europium. In Late Quaternary and Pre-Quaternary phosphorites from ocean shelves REE contents and patterns in general are the same as in host sediments. Phosphorites from seamounts are enriched in REE compared to shelf phosphorites and their patterns are close to one of seawater. Behavior of REE in shelf phosphorites is determined by the fact that in early stages of phosphorite formation REE are associated not primarily with phosphate, but with organic matter and terrigenous impurities. Only in the later stages of diagenesis phosphate begins to play a leading role in concentration of REE. In metasomatic phosphorites on seamounts concentration of REE depends on age and depth of these rocks, i.e. it is determined by duration and conditions of contact with sea water.

A numerical discrete element study on the influence of an embedded viscoelastic-plastic layer at different viscosity values

The major aim of this study was to examine the influence of an embedded viscoelastic-plastic layer at different viscosity values on accretionary wedges at subduction zones. To quantify the effects of the layer viscosity, we analysed the wedge geometry, accretion mode, thrust systems and mass transport pattern. Therefore, we developed a numerical 2D 'sandbox' model utilising the Discrete Element Method. Starting with a simple pure Mohr Coulomb sequence, we added an embedded viscoelastic-plastic layer within the brittle, undeformed 'sediment' package. This layer followed Burger's rheology, which simulates the creep behaviour of natural rocks, such as evaporites. This layer got thrusted and folded during the subduction process. The testing of different bulk viscosity values, from 1 × 10**13 to 1 × 10**14 (Pa s), revealed a certain range where an active detachment evolved within the viscoelastic-plastic layer that decoupled the over- and the underlying brittle strata. This mid-level detachment caused the evolution of a frontally accreted wedge above it and a long underthrusted and subsequently basally accreted sequence beneath it. Both sequences were characterised by specific mass transport patterns depending on the used viscosity value. With decreasing bulk viscosities, thrust systems above this weak mid-level detachment became increasingly symmetrical and the particle uplift was reduced, as would be expected for a salt controlled forearc in nature. Simultaneously, antiformal stacking was favoured over hinterland dipping in the lower brittle layer and overturning of the uplifted material increased. Hence, we validated that the viscosity of an embedded detachment strongly influences the whole wedge mechanics, both the respective lower slope and the upper slope duplex, shown by e.g. the mass transport pattern.