Composition of volcanic rocks from the Alchan Basin, Northwestern Primorie

Geological, petrochemical, and geochemical data are reported for volcanic rocks of a Cretaceous pull-apart basin in the Tan Lu strike-slip system, Asian continental margin. A comparison of these volcanic rocks with magmatic rocks from typical Cenozoic transform margins in the western North America and rift zones of Korea made it possible to distinguish some indicator features of transform-margin volcanic rocks. Magmatic rocks from strike-slip extension zones bear island-arc, intraplate, and occasionally depleted MORB geochemical signatures. In addition to calc-alkaline rocks there are bimodal volcanic series. The rocks are characterized by high K2O, MgO, and TiO2 contents. They show variable enrichment in LILE relative to HFSE, which is typical of island-arc magmas. At the same time they are rich in compatible transition elements, which is a characteristic of intraplate magmas. Trace element distribution patterns normalized to MORB or primitive mantle usually show a negative Ta-Nb anomaly typical of suprasubduction settings. Their Ta/Nb ratio is lower, whereas Ba/Nb, Ba/La, and La/Yb ratios are higher than those of some MORB and OIB. In terms of trace element systematics, for example, Ta-Th-Hf, Ba/La-(Ba/La)_n, (La/Sm)_n-La/Hf, and others, they fall within the area of mixing of magmas from several sources (island arc, intraplate, and depleted reservoirs). Magmatic rocks of transform settings show a sigmoidal chondrite-normalized REE distribution pattern with a negative slope of LREE, depletion in MREE, and an enriched or flat HREE pattern. Magmas with mixed geochemical characteristics presumably originated in a transform margin setting in local extension zones under influence of mantle diapirs, which caused metasomatism and melting of the lithosphere at different levels, and mixing of melts from different sources in variable proportions.

Rare earth elements of modern seeps from the Gulf of Mexico, the Black Sea, and the Congo Fan

At marine seeps, methane is microbially oxidized resulting in the precipitation of carbonates close to the seafloor. Methane oxidation leads to sulfate depletion in sediment pore water, which induces a change in redox conditions. Rare earth element (REE) patterns of authigenic carbonate phases collected from modern seeps of the Gulf of Mexico, the Black Sea, and the Congo Fan were analyzed. Different carbonate minerals including aragonite and calcite with different crystal habits have been selected for analysis. Total REE content (SumREE) of seep carbonates varies widely, from 0.1 ppm to 42.5 ppm, but a common trend is that the SumREE in microcrystalline phases is higher than that of the associated later phases including micospar, sparite and blocky cement, suggesting that SumREE may be a function of diagenesis. The shale-normalized REE patterns of the seep carbonates often show different Ce anomalies even in samples from a specific site, suggesting that the formation conditions of seep carbonates are variable and complex. Overall, our results show that apart from anoxic, oxic conditions are at least temporarily common in seep environments.

Chemical and isotopic compositions of basalts and glasses from lavas of the Sierra Leone fault site

According to detailed petrological, geochemical, and isotope-geochemical study, fragments of fresh pillow lavas with chilled glass margins dredged at the Sierra-Leone test site in the axial rift zone of the MAR between 5° and 7°N correspond to MORB tholeiites, which are not primitive mantle melts, but were differentiated in intermediate magmatic (intrusive) chambers. Small-scale geochemical and Sr-Nd isotope heterogeneities were established for the first time in basalts and their glasses. It was shown that some samples have significant nonsystematic differences in the 87Sr/86Sr ratio between basalts and their chilled glasses and less significant difference in e-Nd; higher Sr ratios can be observed both in glasses and basalts of the same lava fragments. No significant correlation is observed between isotope characteristics of samples and their geochemistry; it was also shown that seawater did not affect Sr and Nd isotope compositions of the chilled glasses from the studied pillow lavas. It is suggested that such differences in isotope ratios are related to small-scale heterogeneity of melts owing to incomplete homogenization during their rapid ascent to the surface. Heterogeneity of basaltic melts is explained by their partial contamination by older plutonic rocks (especially gabbroids) of the lower oceanic crust, through which they ascended to the surface of the ocean floor. The wider scatter of the Sr isotopic ratios relative to Nd ones is related to presence of xenocrysts of calcic plagioclase; correspondingly, absence of a Nd mineral carrier in the rocks results in less distinct Nd isotope variations. It was shown that all studied basalts define a single trend along the mantle correlation array in the Sr-Nd isotope diagram. Causes of this phenomenon remain unclear.

Composition and age of volcanic rocks from the Sinii Utes Depression, Southern Primoye

New data are reported on structure of sections, chemical composition, and age of volcano-sedimentary and volcanic rocks from the Sinii Utes Depression in the Southern Primorye region. The Sinii Utes Depression is filled with two sequences: the lower sequence composed of sedimentary-volcanogenic coaliferous rocks (the stratotype of the Sinii Utes Formation) and the upper sequence consisting of tephroid with overlying basalts. This work considers chemical composition and problems of K-Ar dating of basalts. The uppermost basaltic flow has K-Ar age 22.0±1.0 Ma. The dates obtained for the middle and upper parts of lava flows are underestimated. It is explained by their heating due to combustion of brown coals of the Sinii Utes Formation underlying the lava flow. Calculations show that argon could only partly have been removed from the basalts owing to conductive heat transfer and was lost largely due to infiltration of hot gases in heterogeneous fissured medium. Basaltic volcanism on continental margins of the southern Primorye region and the adjacent Korean and Chinese areas at the Oligocene-Miocene boundary preceded Early-Middle Miocene spreading and formation of the Sea of Japan basin. Undifferentiated moderately alkaline basalts of intraplate affinity developed in the Amba Depression and some other structures of the southern Primorye region and intraplate alkali basalts of the Phohang Graben in the Korean Peninsula serve as indicators of incipient spreading regime in the Sea of Japan. Potassic basalt-trachybasalt eruptions occurred locally in riftogenic depressions and shield volcanoes. In some structures this volcanism was terminated by eruptions of intermediate and acid lavas. Such evolution of volcanism is explained by selective contamination of basaltic melts during their interaction with crustal acid material and generation of acid anatectic melts.

Geochemical processes and rare earth element analysis in cold-seep pore waters of Hydrate Ridge, northeast Pacific Ocean

The concentrations of rare earth elements (REEs), sulphate, hydrogen sulphide, total alkalinity, calcium, magnesium and phosphate were measured in shallow (<12 cm below seafloor) pore waters from cold-seep sediments on the northern and southern summits of Hydrate Ridge, offshore Oregon. Downward-decreasing sulphate and coevally increasing sulphide concentrations reveal sulphate reductionas dominant early diagenetic process from ~2 cm depth downwards. A strong increase of total dissolved REE concentrations is evident immediately below the sediment-water interface, which can be related to early diagenetic release of REEs into pore water resulting from the remineralization of particulate organic matter. The highest pore water REE concentrations were measured close to the sediment-water interface at ~2 cm depth. Distinct shale normalized REE patterns point to particulate organic matter and iron oxides as main REE sources in the upper ~2-cm depth interval. In general, the pore waters have shalenormalized patterns reflecting heavy REE (HREE) enrichment, which suggests preferential complexation of HREEs with carbonate ions. Below ~2 cm depth, a downward decrease in REE correlates with a decrease in pore water calcium concentrations. At this depth, the anaerobic oxidation of methane (AOM) coupled to sulphate reduction increases carbonate alkalinity through the production of bicarbonate, which results in the precipitation of carbonate minerals. It seems therefore likely that the REEs and calcium are consumed during vast AOM-induced precipitation of carbonate in shallow Hydrate Ridge sediments. The analysis of pore waters from Hydrate Ridge shed new light on early diagenetic processes at cold seeps, corroborating the great potential of REEs to identify geochemical processes and to constrain environmental conditions.

Ordinary and duplicate analysis from major and trace elements of ODP Holes 146-888B and 168-1027B

Oceanic sediments deposited at high rate close to continents are dominated by terrigenous material. Aside from dilution by biogenic components, their chemical compositions reflect those of nearby continental masses. This study focuses on oceanic sediments coming from the juvenile Canadian Cordillera and highlights systematic differences between detritus deriving from juvenile crust and detritus from old and mature crust. We report major and trace element concentrations for 68 sediments from the northernmost part of the Cascade forearc, drilled at ODP Sites 888 and 1027. The calculated weighted averages for each site can then be used in the future to quantify the contribution of subducted sediments to Cascades volcanism. The two sites have similar compositions but Site 888, located closer to the continent, has higher sandy turbidite contents and displays higher bulk SiO2/Al2O3 with lower bulk Nb/Zr, attributed to the presence of zircons in the coarse sands. Comparison with published data for other oceanic sedimentary piles demonstrates the existence of systematic differences between modern sediments deriving from juvenile terranes (juvenile sediments) and modern sediments derived from mature continental areas (cratonic sediments). The most striking systematic difference is for Th/Nb, Th/U, Nb/U and Th/Rb ratios: juvenile sediments have much lower ratios than cratonic sediments. The small enrichment of Th over Nb in cratonic sediments may be explained by intracrustal magmatic and metamorphic differentiation processes. In contrast, their elevated Th/U and Nb/U ratios (average values of 6.87 and 7.95, respectively) in comparison to juvenile sediments (Th/U ~ 3.09, Nb/U ~ 5.15) suggest extensive U and Rb losses on old cratons. Uranium and Rb losses are attributed to long-term leaching by rain and river water during exposure of the continental crust at the surface. Over geological times, the weathering effects create a slow but systematic increase of Th/U with exposure time.

Geochemistry and isotopic ratios of samples from the Tiger gabbroic complex, Northern Victoria Land, Antarctica

Subduction related mafic/ultramafic complexes marking the suture between the Wilson Terrane and the Bowers Terrane in northern Victoria Land (Antarctica) are well-suited for evaluating the magmatic and structural evolu- tion at the Palaeo-Pacific continental margin of Gondwana. One of these intru- sions is the "Tiger Gabbro Complex" (TGC), which is located at the southern end of the island-arc type Bowers Terrane. The TGC is an early Palaeozoic island-arc related layered igneous complex characterized by extraordinarly fresh sequences of ultramafic, mafic and evolved lithologies and extensive development of high-temperature high-strain zones. The goal of the present study is to establish the kinematic, petrogenetic and temporal development of the TGC in order to evaluate the magmatic and structural evolution of the deep crustal roots of this Cambrian-aged island-arc. Fieldwork during GANOVEX X was carried out to provide insight into: (i) the spatial relations between the different igneous lithologies of the TGC, (ii) the nature of the contact between the TGC and Bowers Terrane, and (iii) the high-temperature shear zones exposed in parts of the TGC. Here, we report the results of detailed field and petrological observations combined with new geochronological data. Based on these new data, we tentatively propose a petrogenetic-kinematic model for the TGC, which involves a two-phase evolution during the Ross orogeny. These phases can be summarized as: (i) an early phase (maximum age c. 530 Ma) involving tectono-magmatic processes that were active at the deep crustal level represented by the TGC within the Bowers island arc and within a general NE-SW directed contractional regime and (ii) a late phase (maximum age c. 490 Ma) attributed to the late Ross orogenic intrusion of the TGC into the higher-crustal metasedimentary country rocks of the Bowers Terrane under NE-SW directed horizontal maximum stress and subsequent cooling.

Rare earth element data for sediments from ODP Leg 127

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the recorded rare earth element (REE) chemistry of Japan Sea sediments are evaluated by investigating REE total abundances and relative fractionations in 59 samples from Ocean Drilling Program Leg 127. REE total abundances (Sum REE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 (Yamato Basin) overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO2 within the late Miocene-Pliocene diatomaceous sequence. Eu/Eu* values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu* with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. Sum REE at Site 795 (Japan Basin) also is affiliated strongly with aluminosilicate phases, yet is diluted only slightly by siliceous input. At Site 797 (Yamato Basin), REE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. The biogenic influence is largest at Site 794, moderately developed at Site 797, and of only minor importance at Site 795, reflecting basinal contrasts in productivity such that the Yamato Basin records greater biogenic input than the Japan Basin, while the most productive waters overlie the easternmost sequence of Site 794. Ce/Ce* profiles at all three sites increase monotonically with depth, and record progressive diagenetic LREE fractionation. The observed Ce/Ce* record does not respond to changes in oxygenation state of the overlying water, and Ce/Ce* correlates slightly better with depth than with age. The downhole increase in Ce/Ce* at Site 794 and Site 797 is a passive response to diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and La_n/Yb_n suggests that other processes are occurring which mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column, and that an additional ~38% is recycled at or near the seafloor (data from Masuzawa and Koyama, 1989). Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce* is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply-buried interstitial waters.

(Table 1) Chemical composition of volcanic rocks from the Mariisky sequence and extrusive vent rocks of the Mary Cape, Schmidt Peninsula (North Sakhalin)

Early Cretaceous volcanic rocks of the Mariisky sequence and Early Cenozoic extrusive-vent rocks of the Mary Cape are exposed at the most northwest of the Schmidt Peninsula, North Sakhalin. In chemical composition, all the rocks are subdivided into four groups. Three groups include volcanic rocks of the Mariisky sequence, which consists, from bottom to top, of calc-alkaline rocks, transitional calc-alkaline-tholeiite rocks, and incompatible element-depleted tholeiites. These rocks show subduction geochemical signatures and are considered as a fragment of the Moneron-Samarga island arc system. Trace-element modeling indicates their derivation through successive melting of a garnet-bearing mantle and garnet-free shallower mantle sources containing amphibole; pyroxene; and, possibly, spinel. The mixed subduction and intra-plate characteristics of the extrusive vent rocks of the Mary Cape attest to their formation in a transform continental margin setting.

Description, geochemistry and mineral composition of ODP Site 193-1189 jasperoids, PACMANUS field

Bright red "jasperoids" were recovered at three positions during Leg 193 drilling below Roman Ruins (Site 1189) in the PACMANUS hydrothermal field. These do not represent fossil exhalative oxide deposits equivalent to those associated with sulfide chimneys at the Roman Ruins seafloor. Rather, they constitute an integral, relatively early stage involving oxidized fluids in the development of veins and breccias that characterize the mostly sulfidic stockwork zone intersected below Roman Ruins in Hole 1189B. They formed by growth of quartz in open spaces created by hydrofracturing, the characteristic feature being mostly euhedral cores dusted by tiny hematite flakes. In one occurrence there are also frondlike aggregates and possible earlier cavity linings of hematite, overgrown by quartz, that potentially formed by maturation of ferruginous gels first deposited in the openings. The trace element geochemistry of the jasperoids, apart from minor enrichment in uranium, provides no indication that they represent subsurface conduits for fluids that deposit Fe-Mn-Si at the seafloor, though this remains a possibility for some such deposits.

Chemical composition of bottom sediments at DSDP Sites 91-595 and 91-596 and ODP Sites 114-701 and 129-801

Subducted sediments play an important role in arc magmatism and crust-mantle recycling. Models of continental growth, continental composition, convergent margin magmatism and mantle heterogeneity all require a better understanding of the mass and chemical fluxes associated with subducting sediments. We have evaluated subducting sediments on a global basis in order to better define their chemical systematics and to determine both regional and global average compositions. We then use these compositions to assess the importance of sediments to arc volcanism and crust-mantle recycling, and to re-evaluate the chemical composition of the continental crust. The large variations in the chemical composition of marine sediments are for the most part linked to the main lithological constituents. The alkali elements (K, Rb and Cs) and high field strength elements (Ti, Nb, Hf, Zr) are closely linked to the detrital phase in marine sediments; Th is largely detrital but may be enriched in the hydrogenous Fe-Mn component of sediments; REE patterns are largely continental, but abundances are closely linked to fish debris phosphate; U is mostly detrital, but also dependent on the supply and burial rate of organic matter; Ba is linked to both biogenic barite and hydrothermal components; Sr is linked to carbonate phases. Thus, the important geochemical tracers follow the lithology of the sediments. Sediment lithologies are controlled in turn by a small number of factors: proximity of detrital sources (volcanic and continental); biological productivity and preservation of carbonate and opal; and sedimentation rate. Because of the link with lithology and the wealth of lithological data routinely collected for ODP and DSDP drill cores, bulk geochemical averages can be calculated to better than 30% for most elements from fewer than ten chemical analyses for a typical drill core (100-1000 m). Combining the geochemical systematics with convergence rate and other parameters permits calculation of regional compositional fluxes for subducting sediment. These regional fluxes can be compared to the compositions of arc volcanics to asses the importance of sediment subduction to arc volcanism. For the 70% of the trenches worldwide where estimates can be made, the regional fluxes also provide the basis for a global subducting sediment (GLOSS) composition and flux. GLOSS is dominated by terrigenous material (76 wt% terrigenous, 7 wt% calcium carbonate, 10 wt% opal, 7 wt% mineral-bound H2O+), and therefore similar to upper continental crust (UCC) in composition. Exceptions include enrichment in Ba, Mn and the middle and heavy REE, and depletions in detrital elements diluted by biogenic material (alkalis, Th, Zr, Hf). Sr and Pb are identical in GLOSS and UCC as a result of a balance between dilution and enrichment by marine phases. GLOSS and the systematics of marine sediments provide an independent approach to the composition of the upper continental crust for detrital elements. Significant discrepancies of up to a factor of two exist between the marine sediment data and current upper crustal estimates for Cs, Nb, Ta and Ti. Suggested revisions to UCC include Cs (7.3 ppm), Nb (13.7 ppm), Ta (0.96 ppm) and TiO2 (0.76 wt%). These revisions affect recent bulk continental crust estimates for La/Nb and U/Nb, and lead to an even greater contrast between the continents and mantle for these important trace element ratios. GLOSS and the regional sediment data also provide new insights into the mantle sources of oceanic basalts. The classical geochemical distinction between 'pelagic' and 'terrigenous' sediment sources is not valid and needs to be replaced by a more comprehensive understanding of the compositional variations in complete sedimentary columns. In addition, isotopic arguments based on surface sediments alone can lead to erroneous conclusions. Specifically, the Nd/Hf ratio of GLOSS relaxes considerably the severe constraints on the amount of sediment recycling into the mantle based on earlier estimates from surface sediment compositions.