Chemical composition and age of metamorphic rocks from the Khavyven Highland, Eastern Kamchatka

Metamorphic rocks of the Khavyven Highland in eastern Kamchatka were determined to comprise two complexes of metavolcanic rocks that have different ages and are associated with subordinate amounts of metasediments. The complex composing the lower part of the visible vertical section of the highland is dominated by leucocratic amphibole-mica (+/-garnet) and epidote-mica (+/-garnet) crystalline schists, whose protoliths were andesites and dacites and their high-K varieties of island-arc calc-alkaline series. The other complex composing the upper part of the vertical section consists of spilitized basaltoids transformed into epidote-amphibole and phengite-epidote-amphibole green schists, which form (together with quartzites, serpentinized peridotites, serpentinites, and gabbroids) a sea-margin ophiolitic association. High LILE concentrations, high K/La, Ba/Th, Th/Ta, and La/Nb ratios, deep Ta-Nb minima, and low (La/Yb)_N and high 87Sr/86Sr ratios of the crystalline schists of the lower unit are demonstrated to testify to their subduction nature and suggest that their protolithic volcanics were produced in the suprasubduction environment of the Ozernoi-Valaginskii (Achaivayam-Valaginskii) island volcanic arc of Campanian-Paleogene age. The green schists of the upper unit show features of depleted MOR tholeiitic melts and subduction melts, which cause the deep Ta-Nb minima, and low K/La and 87Sr/86Sr ratios suggesting that the green schists formed in a marginal basin in front of the Ozernoi-Valaginskaya island arc. Recently obtained K-Ar ages in the Khavyven Highland vary from 32.4 to 39.3 Ma and indicate that metamorphism of the protolithic rocks occurred in Eocene under effect of collision and accretion processes of the arc complexes of the Ozernoi-Valaginskii and Kronotskii island arcs with the Asian continent and the closure of forearc oceanic basins in front of them. The modern position of the collision suture that marks the fossil subduction zone of the Ozernoi-Valaginskii arc and is spatially restricted to the buried Khavyven uplift in the Central Kamchatka Depression characterized by well-pronounced linear gravity anomalies.

Major and trace element composition of sepentine muds and metabasic rocks of ODP Leg 195 and Leg 125 sites

New geochemical data on serpentinite muds and metamorphic clasts recovered during Ocean Drilling Program Legs 195 (Holes 1200A-1200E) and 125 (Holes 778A and 779A) provide insights into the proportions of rock types of various sources that compose the serpentinite mudflows and the fluid-rock interactions that predominate in these muds. We interpret the metamorphic rock fragments as derivatives of mostly metamorphosed mafic rocks from the descending Pacific oceanic crust. Based on their mid-ocean-ridge basalt (MORB)-like Al2O3, TiO2, CaO, Si/Mg, and rare earth element (REE) systematics, these metamorphic rocks are classified as metabasalts/metagabbros and, therefore, ~30-km depths represent an active subduction zone setting. The serpentinite muds from Holes 1200A and 1200E have slightly lower REE when compared to Hole 1200D, but overall the REE abundance levels range between 0.1-1 x chondrite (CI) levels. The chondrite-normalized patterns have [La/Sm]N ~ 2.3 and [Sm/Yb]N ~ 2. With the exception of one sample, the analyzed metamorphic clasts show flat to slightly depleted light REE patterns with 1.0-15 x CI levels, resembling MORBs. Visually, ~6 vol% of the serpentinized muds are composed of 'exotic' materials (metamorphic clasts [schists]). Our mixing calculations confirm this result and show that the serpentinite muds are produced by additions of ~5% metamafic materials (with flat and up to 10 x CI REE levels) to serpentinized peridotite clast material (with very low REE abundances and U-shaped chondrite-normalized patterns). The preferential incorporation of B, Cs, Rb, Li, As, Sb, and Ba into the structure of H2O-bearing sheet silicates (different than serpentine) in the Leg 125 and Leg 195 metamorphic clasts (chlorite, amphibole, and micas) have little effect on the overall fluid-mobile element (FME) enrichments in the serpentinite muds (average B = ~13 ppm; average Cs = ~0.05 ppm; average As = ~1.25 ppm). The extent of FME enrichment in the serpentinized muds is similar to that described for the serpentinized peridotites, both recording interaction with fluids very rich in B, Cs, and As originating from the subducting Pacific slab.

Petrology and geochemistry of basalts from the Vavilov Basin

During ODP Leg 107, two holes were drilled in the basement of Vavilov Basin, a central oceanic area of the Tyrrhenian sea. Hole 655B is located near the Gortani ridge in off-axis position at the western rim of the basin; Hole 651A is located on a basement swell at the axis of the basin. This paper deals with mineral chemistry, major and trace element geochemistry, and petrogenesis of the basalts recovered in the two holes. The mineralogy of the basalts is broadly homogeneous, but all of them have suffered important seawater alteration. Their major-element compositions are similar to both normal-mid-ocean-ridge-basalts (N-MORB) and back-arc-basalts (BAB) except for Na2O contents (BAB-like), and K2O which is somewhat enriched in upper unit of Hole 651 A. Their affinity with N-MORB and BAB is confirmed by using immobile trace elements such as Zr, Y, and Nb. However, basalts from the two sites present contrasting geochemical characteristics on spidergrams using incompatible elements. Hole 655B basalts are homogeneous enriched tholeiites, similar to those from DSDP Hole 373 (located on the opposite side of the basin near the eastern rim), and show affinities with enriched MORB (E-MORB). At Hole 651 A, the two basalt units are chemically distinct. One sample recovered in lower unit is rather similar to those from Hole 655B, but basalts from upper unit display calc-alkaline characteristic evidenced by the increase of light-ion-lithophile-element (LILE)/high-field-strength-element (HFSE) ratio, and appearance of a negative Nb-anomaly, making them comparable with orogenic lavas from the adjacent Eolian arc. The observed chemical compositions of the basalts are consistent with a derivation of the magmas from a N-MORB type source progressively contaminated by LILE-enriched fluids released from dehydration of the bordering subducted plate. Implications for evolution of the Tyrrhenian basin are tentatively proposed taking into consideration geochemical and chronological relationships between basalts from Leg 107 Holes 655B and 651 A, together with data from Leg 42 Site 373 and Vavilov Seamount. These data illustrate back-arc spreading in ensialic basin closely associated with the maturation of the adjacent subduction, followed by the growth of late off-axis central volcano, whereas the active subduction retreats southeastward.

Sr, Nd and Pb isotopic composition of volcanic and volcaniclastic samples of ODP Leg 134

A suite of volcanic and volcaniclastic rocks selected from Ocean Drilling Program Leg 134 Sites 832 and 833 in the North Aoba Basin (Central New Hebrides Island Arc) has been analyzed for Sr, Nd, and Pb isotopes to investigate the temporal evolution of the arc magmatism. This arc shows two unusual features with respect to other western Pacific arcs: 1) subduction is eastdirected; and 2) a major submarine ridge, the d'Entrecasteaux Zone, has been colliding almost perpendicularly with the central part of the arc since about 3 Ma. Volcanic rocks from the upper parts of both holes, generated during the last 2 m.y., show higher 87Sr/86Sr and significantly lower 206Pb/204Pb and 143Nd/144 Nd values compared to those volcanics erupted before the collision of this ridge, as represented by samples from the lower section of both holes, or remote from the collisional region, in the southern part of the arc. These isotopic differences in the respective mantle sources cannot be interpreted in terms of geochemical input into the mantle wedge induced by the collision itself. Rather, they require long term (>500 m.y.) enrichment processes. The enriched mantle source could be, on a regional scale, a DUPAL-type reservoir with strong similarities to the source of Indian Ocean basalts. Isotopic analyses of drilled rocks from the DEZ show that the anomalous, enriched mantle component is not derived from this feature. We currently cannot identify a source for this enriched component, but note that it also exists in Lau Basin backarc volcanics, lavas from the West Philippine Sea, and also some lavas from the Mariana-Izu-Bonin arc.

Geochemistry of volcanivlastic sediments of ODP Sites 134-832 and 134-833

Volcaniclastic sediments of North Aoba Basin (Vanuatu) recovered during Ocean Drilling Program (ODP) Leg 134 show a mineralogical and chemical overprint of low grade hydrothermal alteration superimposed on the primary magmatic source compositions. The purpose of this study was to identify authigenic mineral phases incorporated in the volcaniclastic sediments, to distinguish authigenic chemical and mineralogical signals from the original volcaniclastic mineralogical and chemical compositions, and to determine the mechanism of authigenic minerals formation. Mineralogical, micro-chemical and bulk chemical analyses were utilized to identify and characterize authigenic phases and determine the original unaltered ash compositions. 117 volcaniclastic sediment samples from North Aoba Basin Sites 832 and 833 were analyzed. Primary volcaniclastic materials accumulated in North Aoba Basin can be divided into three types. The older basin-filling sequences show three different magmatic trends: high K, calc-alkaline, and low K series. The most recent accumulations are rhyodacitic composition and can be attributed to Santa Maria or Aoba volcanic emissions. Original depositional porosity of volcaniclastic sediments is an important factor in influencing distribution of authigenic phases. Finer-grained units are less altered and retain a bulk mineralogical and chemical composition close to the original pyroclastic rock composition. Coarser grained units (microbreccia and sandstones) are the major hosts of authigenic minerals. At both sites, authigenic minerals (including zeolites, clay minerals, Mg-carbonates, and quartz) exhibit complex zonation with depth that crosses original ash depositional boundaries and stratigraphic limits. The zeolite minerals phillipsite and analcime are ubiquitous throughout the altered intervals. At Site 832, the first zeolite minerals (phillipsite) occur in Pleistocene deposits as shallow as 146 meters below seafloor (mbsf). At Site 833 the first zeolite minerals (analcime) occur in Pleistocene deposits as shallow as 224 mbsf. The assemblage phillipsite + analcime + chabazite appears at 635 mbsf (Site 832) and at 376 mbsf (Site 833). Phillipsite + analcime + chabazite + thomsonite + heulandite are observed between 443 and 732 mbsf at Site 833. Thomsonite is no longer observed below 732 mbsf at Site 833. Heulandite is present to the base of the sections cored. The zeolite assemblages are associated with authigenic clay minerals (nontronite and saponite), calcite, and quartz. Chlorite is noticeable at Site 832 as deep as 851 mbsf. Zeolite zones are present but are less well defined at Site 832. Dolomite and rare magnesite are present below 940 m at Site 832. The coarse-grained authigenic mineral host intervals exhibit geochemical signatures that can be attributed to low grade hydrothermal alteration. The altered intervals show evidence of K2O, CaO, and rare earth elements mobilization. When compared to fine-grained, unaltered units, and to Santa Maria Island volcanics rocks, the altered zones are relatively depleted in rare earth elements, with light rare earth elements-heavy rare earth elements fractionation. Drilling at Site 833 penetrated a sill complex below 840 m. No sill was encountered at Site 832. Complex zonation of zeolite facies, authigenic smectites, carbonates and quartz, and associated geochemical signatures are present at both sites. The mineralogical and chemical alteration overprint is most pronounced in the deeper sections at Site 832. Based on mineralogical and chemical evidence at two locations less than 50 km apart, there is vertical and lateral variation in alteration of the volcaniclastic sediments of North Aoba Basin. The alteration observed may be activated by sill intrusion and associated expulsion of heated fluids into intervals of greater porosity. Such spatial variation in alteration could be attributed to the evolution of the basin axis associated with subduction processes along the New Hebrides Trench.

Geochemistry and trace elements at DSDP Hole 78-543A

The upper part of the basaltic substratum of the Atlantic abyssal plain, approaching subduction beneath the Barbados Ridge and thus presumably beneath the Lesser Antilles island arc, is made of typical LREE-depleted oceanic tholeiites. Mineralogical (microprobe) and geochemical (X-ray fluorescence, neutron activation analyses) data are given for 12 samples from the bottom of Hole 543A, which is 3.5 km seaward of the deformation front of the Barbados Ridge complex. These basalts are overlain by a Quaternary to Maestrichtian-Campanian sedimentary sequence. Most of the basalts are relatively fresh (in spite of the alteration of olivine and development of some celadonite, clays, and chlorite in their groundmass), and their mineralogical and geochemical compositions are similar to those of LREE-depleted recent basalts from the Mid-Atlantic Ridge. The most altered samples occur at the top of the basaltic sequence, and show trends of enrichment in alkali metals typical of altered oceanic tholeiites.

Geochemical history at DSDP Leg 56 Holes

A geological model of subduction postulated by Karig, Ingle, et al. (1975) and Karig and Sharman (1975) proposes that the sedimentary prism at the foot of the landward wall is being actively built as sediment is scraped off the subducting oceanic and plastered onto the base of the wedge, forming an accretionary wedge containing overthrust sedimentary layers or intense sedimentary folding. Because overlying layers must continually be uplifted and compressed to accommodate new matter at the base, the accreting wedge will provide a geochemical record of this process at or near the Japan Trench. Several recent papers have discussed the metalliferous sediments on the active oceanic ridges. The geochemistry of such sediments is now reasonably well known: generally these deposits are considered products of volcanic processes (Boström and Peterson, 1969; Böstrom et al., 1969; Horowitz, 1970, 1974; Cronan et al., 1972; Cronan and Garrett, 1973). The geochemistry of subduction zone sediments, however, is less well known, and the need for studies of these sediments is particularly urgent if such sediments provide a record of the effects of subduction of oceanic plates under continental crust. Because the Japan Trench contains welldeveloped subduction zone deposits, Leg 56 sampling was of utmost importance to the discovery of how they originate.

Geochemistry at DSDP Hole 57-439

Dating of a hornblende concentrate by the 40Ar/39Ar method gives an age of 23.4±5.5 m.y. for a dacite boulder from conglomerate in Deep Sea Drilling Project Hole 439. The conglomerate clasts range up to 1 meter in diameter and are nearly monolithologic, suggesting that a nearby former volcano erupted the dacite. The dacite is only 90 km landward from the Japan Trench, whereas modern trench-related volcanoes lie at least 120 km from their trenches. The dacite locality is on strike with and is probably an extension of a magmatic arc on the island of Hokkaido that crosses the Kuril arc at an angle of 65° and which was active 16 to 36 m.y. ago. The part of the former arc landward from the Kuril arc argues against an origin from a leaking subduction zone or from subduction of an active spreading ridge. The part seaward both from the Kuril and Japan arcs weakens an explanation based on migration of a trench-trenchtrench triple junction. The magmatic rocks probably formed along a middle-Tertiary plate boundary that had stepped seaward from a more-landward Cretaceous position. Later, the boundary stepped farther seaward at the Kuril arc and landward again at the Japan arc. If so, the present Japan subduction zone must have consumed most of the strata that had accumulated between it and the earlier trench.

Petrographic data for samples from DSDP Holes 63-471 and 65-485

Detrital modes of middle Miocene sandstone recovered at Deep Sea Drilling Project Site 471 on the Magdalena Fan support the hypothesis that the fan has been displaced northward from a source hundreds of kilometers to the south near the present mouth of the Gulf of California. The modes are dissimilar to those of modern sand derived from onshore outcrops of Miocene volcanic and volcaniclastic rocks, Neogene sedimentary rocks, and Mesozoic subduction complex. They most closely match sand associated with the mouth of Gulf of California. The overall stratigraphy, sand composition, and diagenesis at Site 471 are consistent with deposition of the Magdalena Fan on young oceanic crust near a spreading ridge at a triple junction.

Petrology and chemistry of ODP Site 134-828 magmatic rocks

Petrography, major and trace elements, mineral chemistry, and Sr, Nd, and Pb isotopic ratios are reported for igneous rocks drilled on the northern flank of the North d'Entrecasteaux Ridge (NDR) during Ocean Drilling Program (ODP) Leg 134 Site 828. These rocks comprise a breccia unit beneath a middle Eocene foraminiferal ooze. Both geophysical characteristics and the variety of volcanic rocks found at the bottom of Holes 828A and 828B indicate that a very immature breccia or scree deposit was sampled. Basalts are moderately to highly altered, but primary textures are well preserved. Two groups with different magmatic affinities, unrelated to the stratigraphic height, have been distinguished. One group consists of aphyric to sparsely plagioclase + clinopyroxene-phyric basalts, characterized by high TiO2 (~2 wt%) and low Al2O3 (less than 15 wt%) contents, with flat MORB-normalized incompatible element patterns and LREE-depleted chondrite-normalized REE patterns. This group resembles N-MORB. The other group comprises moderately to highly olivine + plagioclase-phyric basalts with low TiO2 (<1 wt%) and high Al2O3 (usually >15 wt%) contents, and marked HFSE depletion and LFSE enrichment. Some lavas in this group are picritic, with relatively high modal olivine abundances, and MgO contents up to 15 wt%. Both the basalts and picritic basalts of this group reflect an influence by subduction-related processes, and have compositions transitional between MORB and IAT. Lavas with similar geochemical features have been reported from small back-arc basins such as the Mariana Trough, Lau Basin, Sulu Sea, and the North Fiji Basin and are referred to as back-arc basin basalts. However, regional tectonic considerations suggest that the spreading that produced these backarc basin basalts may have occurred in the forearc region of the southwest-facing island arc that existed in this region in the Eocene.

Geochemistry of serpentinized peridotites from ODP Holes 207-1272A and 207-1274A

Despite the key importance of altered oceanic mantle as a repository and carrier of light elements (B, Li, and Be) to depth, its inventory of these elements has hardly been explored and quantified. In order to constrain the systematics and budget of these elements we have studied samples of highly serpentinized (>50%) spinel harzburgite drilled at the Mid-Atlantic Ridge (Fifteen-Twenty Fracture zone, ODP Leg 209, Sites 1272A and 1274A). In-situ analysis by secondary ion mass spectrometry reveals that the B, Li and Be contents of mantle minerals (olivine, orthopyroxene, and clinopyroxene) remain unchanged during serpentinization. B and Li abundances largely correspond to those of unaltered mantle minerals whereas Be is close to the detection limit. The Li contents of clinopyroxene are slightly higher (0.44-2.8 µg/g) compared to unaltered mantle clinopyroxene, and olivine and clinopyroxene show an inverse Li partitioning compared to literature data. These findings along with textural observations and major element composition obtained from microprobe analysis suggest reaction of the peridotites with a mafic silicate melt before serpentinization. Serpentine minerals are enriched in B (most values between 10 and 100 µg/g), depleted in Li (most values below 1 µg/g) compared to the primary phases, with considerable variation within and between samples. Be is at the detection limit. Analysis of whole rock samples by prompt gamma activation shows that serpentinization tends to increase B (10.4-65.0 µg/g), H2O and Cl contents and to lower Li contents (0.07-3.37 µg/g) of peridotites, implying that-contrary to alteration of oceanic crust-B is fractionated from Li and that the B and Li inventory should depend essentially on rock-water ratios. Based on our results and on literature data, we calculate the inventory of B and Li contained in the oceanic lithosphere, and its partitioning between crust and mantle as a function of plate characteristics. We model four cases, an ODP Leg 209-type lithosphere with almost no igneous crust, and a Semail-type lithosphere with a thick igneous crust, both at 1 and 75 Ma, respectively. The results show that the Li contents of the oceanic lithosphere are highly variable (17-307 kg in a column of 1 m * 1 m * thickness of the lithosphere (kg/col)). They are controlled by the primary mantle phases and by altered crust, whereas the B contents (25-904 kg/col) depend entirely on serpentinization. In all cases, large quantities of B reside in the uppermost part of the plate and could hence be easily liberated during slab dehydration. The most prominent input of Li into subduction zones is to be expected from Semail-type lithosphere because most of the Li is stored at shallow levels in the plate. Subducting an ODP Leg 209-type lithosphere would mean only very little Li contribution from the slab. Serpentinized mantle thus plays an important role in B recycling in subduction zones, but it is of lesser importance for Li.