Geochemical composition of the Trincheira Complex in the southwestern Amazon craton, Brazil

We document the first-known Mesoproterozoic ophiolite from the southwestern part of the Amazon craton, corresponding to the Trincheira Complex of Calymmian age, and propose a tectonic model that explains many previously enigmatic features of the Precambrian history of this key craton, and discuss its role in the reconstruction of the Columbia supercontinent. The complex comprises extrusive rocks (fine-grained amphibolites derived from massive and pillowed basalts), mafic-ultramafic intrusive rocks, chert, banded iron formation (BIFs), pelites, psammitic and a smaller proportion of calc-silicate rocks. This sequence was deformed, metasomatized and metamorphosed during the development of the Alto Guaporé Belt, a Mesoproterozoic accretionary orogen. The rocks were deformed by a single tectonic event, which included isoclinal folding and metamorphism of the granulite-amphibolite facies. Layered magmatic structures were preserved in areas of low strain, including amygdaloidal and cumulate structures. Metamorphism was pervasive and reached temperatures of 780-853°C in mafic granulites and 680-720°C in amphibolites under an overall pressure of 6.8 kbar. The geochemical composition of the extrusive and intrusive rocks indicates that all noncumulus mafic-ultramafic rocks are tholeiitic basalts. The mafic-ultramafic rocks display moderately to strongly fractionation of light rare earth elements (LREE), near-flat heavy rare earth elements (HREE) patterns and moderate to strong negative high field strength elements (HFSE) anomalies (especially Nb), a geochemical signature typical of subduction zones. The lowest units of mafic granulites and porphyroblastic amphibolites in the Trincheira ophiolite are similar to the modern mid-ocean ridge basalt (MORB), although they locally display small Ta, Ti and Nb negative anomalies, indicating a small subduction influence. This behavior changes to an island arc tholeiites (IAT) signature in the upper units of fine-grained amphibolites and amphibole rich-amphibolites, characterized by progressive depletion in the incompatible elements and more pronounced negative Ta and Nb anomalies, as well as common Ti and Zr negative anomalies. Tectono-magmatic variation diagrams and chondrite-normalized REE and primitive mantle normalized patterns suggest a back-arc to intra-oceanic island arc tectonic regime for the eruption of these rocks. Therefore, the Trincheira ophiolite appears to have originated in an intraoceanic supra-subduction setting composed of an arc-back-arc system. Accordingly, the Trincheira Complex is a record of oceanic crust relics obducted during the collision of the Amazon craton and the Paraguá block during the Middle Mesoproterozoic. Thus, the recognition of the Trincheira ophiolite and suture significantly changes views on the evolution of the southern margin of the Amazon craton, and how it can influence the global tectonics and the reconstruction of the continents.

Strike-slip faults mediate the rise of crustal-derived fluids and mud volcanism in the deep sea

We report on newly discovered mud volcanoes located at about 4500 m water depth 90 km west of the deformation front of the accretionary wedge of the Gulf of Cadiz, and thus outside of their typical geotectonic environment. Seismic data suggest that fluid flow is mediated by a >400-km-long strike-slip fault marking the transcurrent plate boundary between Africa and Eurasia. Geochemical data (Cl, B, Sr, 87Sr/86Sr, Delta18O, DeltaD) reveal that fluids originate in oceanic crust older than 140 Ma. On their rise to the surface, these fluids receive strong geochemical signals from recrystallization of Upper Jurassic carbonates and clay-mineral dehydration in younger terrigeneous units. At present, reports of mud volcanoes in similar deep-sea settings are rare, but given that the large area of transform-type plate boundaries has been barely investigated, such pathways of fluid discharge may provide an important, yet unappreciated link between the deeply buried oceanic crust and the deep ocean.

(Table 1) Surface water chemistry of northern Victoria Land lakes

Concentrations of major ions, silicate and nutrients (total N and P) were measured in samples of surface water from 28 lakes in ice-free areas of northern Victoria Land (East Antarctica). Sixteen lakes were sampled during austral summers 2001/02, 2003/04, 2004/05 and 2005/06 to assess temporal variation in water chemistry. Although samples showed a wide range in ion concentrations, their composition mainly reflected that of seawater. In general, as the distance from the sea increased, the input of elements from the marine environment (through aerosols and seabirds) decreased and there was an increase in nitrate and sulfate concentrations. Antarctic lakes lack outflows and during the austral summer the melting and/or ablation of ice cover, water evaporation and leaching processes in dry soils determine a progressive increase in water ion concentrations. During the five-year monitoring survey, no statistically significant variation in the water chemistry were detected, except for a slight (hardly significant) increase in TN concentrations. However, Canonical Correspondence Analysis (CCA) indicated that other factors besides distance from the sea, the presence of nesting seabirds, the sampling time and percentage of ice cover affect the composition of water in Antarctic cold desert environments.

Geochemistry on manganese nodules from Loch Fyne, Scotland

Manganese nodules and manganese carbonate concretions occur in the upper 10-15 cm of the Recent sediments of Loch Fyne, Argyllshire in water depths of 180-200 m. The nodules are spherical, a few mm to 3 cm in diameter, and consist of a black, Mn-rich core and a thin, red, Fe-rich rim. The carbonate occurs as irregular concretions, 0.5-8 cm in size, and as a cement in irregular nodule and shell fragment aggregates. It partially replaces some nodule material and clastic silicate inclusions, but does not affect aragonitic and calcitic shell fragments. The nodules are approximately 75% pure oxides and contain 30% Mn and 4% Fe. In the cores, the principal mineral phase is todorokite, with a Mn/Fe ratio of 17. The rim consists of X-ray amorphous Fe and Mn oxides with a Mn/Fe ratio of 0.66. The cores are enriched, relative to Al, in K, Ba, Co, Mo, Ni and Sr while the rims contain more P, Ti, As, Pb, Y and Zn. The manganese carbonate has the composition (Mn47.7 Ca45.1 Mg7.2) CO3. Apart from Cu, all minor elements are excluded from significant substitution in the carbonate lattice. Manganese nodules and carbonates form diagenetically within the Recent sediments of Loch Fyne. This accounts for the high Mn/Fe ratios in the oxide phases and the abundance of manganese carbonate concretions. Mn concentrations in the interstitial waters of sediment cores are high (ca. 10 ppm) as also, by inference, are the dissolved carbonate concentrations.

Geochemical composition and crystallization temperatures of ODP Hole 176-735B gabbroic rocks

The transition from magmatic crystallization to high-temperature metamorphism in deep magma chambers (or lenses) beneath spreading ridges has not been fully described. High-temperature microscopic veins found in olivine gabbros, recovered from Ocean Drilling Program Hole 735B on the Southwest Indian Ridge during Leg 176, yield information on the magmatic-hydrothermal transition beneath spreading ridges. The microscopic veins are composed of high-temperature minerals, (i.e., clinopyroxene, orthopyroxene, brown amphibole, and plagioclase). An important feature of these veins is the 'along-vein variation' in mineralogy, which is correlated with the magmatic minerals that they penetrate. Within grains of magmatic plagioclase, the veins are composed of less calcic plagioclase. In grains of olivine, the veins are composed of orthopyroxene + brown amphibole + plagioclase. In clinopyroxene grains, the veins consist of plagioclase + brown amphibole and are accompanied by an intergrowth of brown amphibole + orthopyroxene. The mode of occurrence of the veins cannot be explained if these veins were crystallized from silicate melts. Consequently, these veins and nearby intergrowths were most likely formed by the reaction of magmatic minerals with fluid phases under the conditions of low fluid/rock ratios. Very similar intergrowths of brown amphibole + orthopyroxene are observed in clinopyroxene grains with 'interfingering' textures. It is believed, in general, that the penetration of seawater does not predate the ductile deformation within Layer 3 gabbros of the slow-spreading ridges. If this is the case, the fluid responsible for the veins did not originate from seawater because the formation of the veins and the interfingering textures preceded ductile deformation and, perhaps, complete solidification of the gabbroic crystal mush. It has been proposed, based on fluid inclusion data, that the exsolution of fluid from the latest-stage magma took place at temperatures >700°C in the slow-spreading Mid-Atlantic Ridge at the Kane Fracture Zone (MARK) area. No obvious mineralogical evidence, however, has been found for these magmatic fluids. The calculated temperatures for the veins and nearby intergrowths found in Hole 735B gabbros are up to 1000°C, and these veins are the most plausible candidate for the mineralogical expression of the migrating magmatic fluids.

Magnesium/Calcium ratios and sea surface temperature estimation for sediments of the Timor Sea

We use a multiproxy approach to monitor changes in the vertical profile of the Indonesian Throughflow as well as monsoonal wind and precipitation patterns in the Timor Sea on glacial-interglacial, precessional, and suborbital timescales. We focus on an interval of extreme climate change and sea level variation: marine isotope (MIS) 6 to MIS 5e. Paleoproductivity fluctuations in the Timor Sea follow a precessional beat related to the intensity of the Australian (NW) monsoon. Paired Mg/Ca and d18O measurements of surface- and thermocline-dwelling planktonic foraminifers (G. ruber and P. obliquiloculata) indicate an increase of >4°C in both surface and thermocline water temperatures during Termination II. Tropical sea surface temperature changed synchronously with ice volume (benthic d18O) during deglaciation, implying a direct coupling of high- and low-latitude climate via atmospheric and/or upper ocean circulation. Substantial cooling and freshening of thermocline waters occurred toward the end of Termination II and during MIS 5e, indicating a change in the vertical profile of the Indonesian Throughflow from surface- to thermocline-dominated flow.

Geochemistry and stable isotopes of peridotites of ODP Hole 103-637A

A ridge of strongly serpentinized, plagioclase-bearing peridotite crops out at the boundary between the Atlantic oceanic crust and the Galicia continental margin (western Spain). These peridotites, cored at Hole 637A (ODP Leg 103) have been mylonitized at high-temperature, low-pressure conditions and under large deviatoric stress during their uplift (Girardeau et al., 1988, doi:10.2973/odp.proc.sr.103.135.1988). After this main ductile deformation event, the peridotite underwent a polyphase metamorphic static episode in the presence of water, with the crystallization of Ti- and Cr-rich pargasites at high-temperature (800°-900°C) interaction with a metasomatic fluid or alkaline magma. Introduction of water produced destabilization of the pyroxenes and the subsequent development of hornblendes and tremolite at temperatures decreasing from 750° to 350°C. The main serpentinization of the peridotite occurred at a temperature below 300°C, and possibly around 50°C, as a consequence of the introduction of a large amount of seawater, which is suggested by stable isotope (d18O and SD) data. Finally, calcite derived from seawater precipitated in late-formed fractures or locally pervasively impregnated the peridotite at low temperature (~10°C).

Chemical and strontium isotopic compositions of interstitial waters from sediments of ODP Site 135-841

The depth variations in the major chemical components dissolved in interstitial waters from the Tonga margin (ODP Site 841) are much more pronounced than those usually observed in deep-sea sediments. The extensive alteration of volcanic Miocene sediments to secondary minerals such as analcime, clays, and thaumasite forms a CaCl2-rich brine. The brine results from a high exchange of Ca to Na, K, and Mg and an increase in Cl concentrations due to removal of H2O from the fluid during the authigenesis of hydrous minerals. The formation of thaumasite could have partly controlled the concentration of dissolved SO4, HCO3, and Ca in the Miocene sediments. The strontium isotopic signature of the interstitial water suggests that alteration of the volcanic Miocene sediments occurred a long time after sedimentation. A transient diffusion model indicates that molecular diffusion was not prevented by lithologic barriers and that the formation of secondary minerals in the Miocene sediment occurred over a short period of time (e.g.,

Chemical and Sr isotopic compositions of 3 step leachates and residues of bulk samples, zeolites, and smectites from Lower Miocene sediments at ODP Site 166-1007

Massive clinoptilolite authigenesis was observed at about 1105 meters below sea floor (mbsf) in lower Miocene wellcompacted carbonate periplatform sediments from the Great Bahama Bank [Ocean Drilling Program, ODP Leg 166, Site 1007]. The diagenetic assemblage comprises abundant zeolite crystallized within foraminifer tests and sedimentary matrix, as well as Mg smectites. In carbonate-rich deposits, the formation of the zeolite requires a supply of silica. Thus, the objective of the study is to determine the origin of the silica supply, its diagenetic evolution, and consequently the related implications on interpretation of the sedimentary record, in terms of local or global paleoceanographic change. For lack of evidence for any volcaniclastic input or traces of Si-enriched deep fluids circulation, an in situ biogenic source of silica is validated by isotopic data and chemical modeling for the formation of such secondary minerals in shallow-water carbonate sequences. Geochemical and strontium isotopic data clearly establish the marine signature of the diagenetic zeolite, as well as its contemporaneous formation with the carbonate deposition (Sr model ages of 19.6-23.2 Ma). The test of saturation for the pore fluids specifies the equilibrium state of the present mineralogical assemblage. Seawater-rock modeling specifies that clinoptilolite precipitates from the dissolution of biogenic silica, which reacts with clay minerals. The amount of silica (opal-A) involved in the reaction has to be significant enough, at least 10 wt.%, to account for the observed content of clinoptilolite occurring at the most zeolite-rich level. Modeling also shows that the observed amount of clinoptilolite (~19%) reflects an in situ and short-term reaction due to the high reactivity of primary biogenic silica (opal-A) until its complete depletion. The episodic occurrence of these well-lithified zeolite-rich levels is consistent with the occurrence of seismic reflectors, particularly the P2 seismic sequence boundary located at 1115 mbsf depth and dated as 23.2 Ma. The age range of most zeolitic sedimentary levels (biostratigraphic ages of 21.5-22 Ma) correlates well with that of the early Miocene glaciation Mi-1 and Mi-1a global events. Thus, the clinoptilolite occurrence in the shallow carbonate platform environment far from volcanogenic supply, or in other sensitive marine areas, is potentially a significant new proxy for paleoproductivity and oceanic global events, such as the Miocene events, which are usually recognized in deep-sea pelagic sediments and high latitude deposits.

Chemical and isotope compositions of bottom sediments from ODP Leg 168, Eastern Flank of the Juan de Fuca Ridge

Ten sites were drilled in the eastern flank of the Juan de Fuca Ridge (North East Pacific) along a 100 km-long east-west transect during Leg ODP 168. This study focuses on the mineralogical and chemical study of sediments that overly basaltic basement through which seawater circulates. Silicate authigenesis was observed in the sediment layer just above basement at sites located more than 30 km from the ridge axis. This sediment alteration is particularly abundant at ODP Sites 1031 and 1029 where authigenic formation of Fe-Mg rich smectite and zeolite and the dissolution of biogenic calcite are observed. Comparison of the distribution of the alteration in the basal sediment collected along this transect suggests that diffusional transport of aqueous solutes from the basement into the overlying sediment cannot produce the mineralogical and chemical changes in the basal sediments at Sites 1031 located on a basement topographic high, and at Site 1029 located at about 50 km from the ridge axis on a buried basement area. Vertical advection of basement fluid though the sediment section is required to produce this alteration. These processes are still active at Site 1031, based on systematic variations in pore-water profiles and temperatures obtained from stable isotopic data on calcium carbonates and the nature of authigenic minerals. At Site 1029, there is no present-day advection of basement fluids though the sediment section, suggesting that this is a relic site for fluid flow.

Mineralogy and geochemistry of ODP Hole 176-735B minerals

We present a synthesis of some 20,504 mineral analyses of ~500 Hole 735B gabbros, including 10,236 new analyses conducted for this paper. These are used to construct a mineral stratigraphy for 1.5-km-deep Hole 735B, the only long section of the lower crust drilled in situ in the oceans. At long wavelengths, generally >200 m, there is a good chemical correlation among the principal silicate phases, consistent with the in situ crystallization of three or four distinct olivine gabbro bodies, representing at least two major cycles of intrusion. Initial cooling and crystallization of these bodies must have been fairly rapid to form a crystal mush, followed by subsequent compaction and migration of late iron-titanium-rich liquids into shear zones and fractures through which they were emplaced to higher levels in the lower crust where they crystallized and reacted with the olivine gabbro host rock to form a wide variety of ferrogabbros. At the wave lengths of the individual intrusions, as represented by the several olivine gabbro sequences, there is a general upward trend of iron and sodium enrichment but a poor correlation between the compositions of the major silicate phases. This, together with a wide range in minor incompatible and compatible element concentrations in olivine and pyroxene at a given Mg#, is consistent with widespread permeable flow of late melt through these intrusions, in contrast to what has been documented for a 600-m section of reputedly fast-spreading ocean crust in the Oman Ophiolite. This unexpected finding could be related to enhanced compaction and deformation-controlled late-stage melt migration at the scale of intrusion at a slow-spreading ocean ridge, compared to the relatively static environment in the lower crust at fast-spreading ridges.