Geochemistry at DSDP Leg 92 Holes

The major-element and most of the trace-element data from the different laboratories that contributed to the study of samples recovered during Leg 82 are presented in the following tables. The different basalt groups, identified on the basis of their chemical properties (major and trace elements), were defined from the data available on board the Glomar Challenger as the cruise progressed (see site chapters, all sites, this volume). Most of the data obtained since the end of the cruise and presented in these tables confirm the classification that was proposed by the shipboard party (see site chapters, all sites, this volume). Nevertheless, special mention should be made about Site 564. The shipboard party proposed a single chemical group at this site but noticed significant variations down the hole, mainly in trace-element data. However, the range of variation was small compared to the precision of the measurements. These variations were confirmed by the onshore studies (see papers in Part IV of this volume, especially Brannon's paper, partly devoted to this topic).

Mineralogy and geochemistry of altered ash, pelagic clay, and a clay vein in basalt from DSDP Leg 62 Holes

Volcanic ash was recovered from lower Aptian to Albian deposits from DSDP Sites 463, 465, and 466; pelagic clay of the upper Pleistocene to Upper Cretaceous was recovered mainly from Site 464, with minor amounts at Sites 465 and 466. We present X-ray-mineralogy data on pelagic clay and altered volcanic ash recovered from the four Leg 62 sites. In addition, two ash samples from Sites 463 and 465, a pelagic clay from Site 464, and a clay vein from the basaltic basement at Site 464 each were analyzed for major, minor, and trace elements. Our purpose is to describe the mineralogy and chemistry of altered ash and pelagic clays, to determine the sources of their parent material, and to delineate the diagenetic history of these clay-rich deposits. Correlation of chemistry and mineralogy of ash and pelagic clay with volcanic rocks suspected to be their parent material is not always straightforward, because weathering and diagenetic alteration caused depletion or enrichment of many elements.

Geochemistry and petrology of basalts from Celebes Sea

Major-, trace-, and rare-earth element analyses are presented from a suite of basaltic rocks from the basement of the Celebes Sea. The major elements and trace-elements were determined by X-ray fluorescence techniques, and the rare-earth elements were analyzed by instrumental neutron activation analysis. Compositionally the Celebes Sea basalts are very similar to typical normal mid-ocean ridge basalts, such as those described from the Indian Ocean triple junction. Petrogenetic modeling shows that all of the basalts analyzed can be formed by 10% to 20% partial melting of a light rare-earth element-depleted spinel lherzolite followed by fractional crystallization of mixtures of olivine, Plagioclase, and iron oxide. The Celebes Sea is interpreted as a fragment of the basement of the Jurassic Argo abyssal plain trapped during the Eocene to the north of Australia.

Mineralogical and geochemical analyses of serpentines from ODP Hole 125-778A

Thirty-five samples from Hole 778A were prepared for X-ray diffraction (XRD) mineralogical analyses and for chemical analyses of major and trace elements. Most of the selected samples were silt- and sand-sized sedimentary serpentinites or microbreccias except for a soft clast of mafic rock, a hard clast of massive serpentinized peridotite, and a pebble of consolidated, undeformed serpentine microbreccia that contained planktonic foraminifers. Both mineralogical and geochemical analyses allow discrimination of three groups among the analyzed samples. These groups correspond to three stratigraphic intervals present along the drilled section. Group A contains the upper samples (lithologic Unit I). These consist of poorly consolidated serpentine muds carrying hard-rock clasts (serpentinized peridotites, metabasalts). They are characterized by the following mineralogical assemblage: serpentine, Fe-oxides and hydroxides, aragonite, and halite. They exhibit variable SiO2, MgO contents, but are characterized by a SiO2/MgO ratio near 1. CaO content is high in relation to development of aragonite. Al2O3 content is low. Relatively high K2O, Na2O, and Sr contents are present, presumably in relation to interactions with seawater. Group B (30-77 mbsf) contains samples exhibiting very homogeneous chemical and mineralogical compositions. They consist of serpentinite microbreccias exhibiting frequent shear structures. Hard-rock clasts are also present (serpentinized peridotites, metabasalts, one possible chert fragment). The mineralogy of the Group B samples is characterized by the presence of serpentine and authigenic minerals: hydroxycarbonates and hydrogrossular. Calcite and chlorite are also present, but all the samples lack aragonite. Their chemical compositions are remarkably similar to compositions of their parent rocks. Group C contains silt- and sand-sized serpentine and serpentine microbreccias, which are locally rich in red clasts, probably strongly altered (oxidized?) mafic fragments. Intervals having clasts of more diverse origin than those higher in the section were recovered. Clast lithology includes serpentinized peridotites, metabasalts, metavolcaniclastite, meta-olivine gabbro, and amphibolite sandstone. Mineralogy and geochemistry reflect these compositions. Serpentine content of the samples is less than in previous groups. Correlatively, sepiolite, palygorskite, and chlorite-smectite are mineral phases present in the analyzed samples. Accessory igneous minerals (amphiboles, pyroxenes, hematite) also were found. The chemical compositions of most of Group C samples differ from that of massive serpentinized peridotites. The main differences are (1) higher SiO2, CaO, TiO2 and Al2O3 contents, (2) a SiO2/MgO ratio greater than 1, and (3) a negative correlation between Al2O3, and MgO, Cr, and Ni. These characteristics suggest new constraints relative to the flow structure of the flank of Conical Seamount.

Geochemistry of ODP Site 123-765 sediments

Drilling at Site 765 in the Argo Abyssal Plain sampled sediments and oceanic crust adjacent to the Australian margin. Some day, this site will be consumed in the Java Trench. An intensive analytical program was conducted to establish this site as a geochemical reference section forcrustal recycling calculations. About 150 sediment samples from Site 765 were analyzed for major and trace elements. Downhole trends in the sediment analyses agree well with trends in sediment mineralogy, as well as in Al and K logs. The primary signal in the geochemical variability is dilution of a detrital component by both biogenic silica and calcium carbonate. Although significant variations in the nonbiogenic component occur through time, its overall character is similar to nearby Canning Basin shales, which are typical of average post-Archean Australian shales (PAAS). The bulk composition of the hole is calculated using core descriptions to weight the analyses appropriately. However, a remarkably accurate estimate of the bulk composition of the hole can be made simply from PAAS and the average calcium carbonate and aluminum contents of the hole. Most elements can be estimated within 30% in this way. This means that estimating the bulk composition of other sections dominated by detrital and biogenic components may require little analytical effort: calcium carbonate contents, average Al contents, and average shale values can be taken from core descriptions, geochemical logs, and the literature, respectively. Some of the geochemical systematics developed at Site 765 can be extrapolated along the entire Sunda Trench. However, results are general, and Site 765 should serve as a useful reference for estimating the compositions of other continental margin sections approaching trenches around the world (e.g., outboard of the Lesser Antilles, Aegean, and Eolian arcs).

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.

Composition of standard reference samples of Fe-Mn nodules and bottom sediments

The first series of Soviet standard reference samples of composition of ore materials and ocean pelagic sediments has been created. It includes iron-manganese nodules (SDO-4, SDO-5 and SDO-6), ore crusts (SDO-7) diatomaceous ooze (SDO-8), and deep-sea red clays (SDO-9). The standards are intended to serve as a metrologic basis for physical, physicochemical and chemical analyses of iron-manganese minerals and ocean sediments. The standards are provided with certified analyses of rock-forming components and certain trace elements. Certified characteristics are based on statistical analysis of data obtained from an inter-laboratory experiment involving analysis of the standard reference samples by a variety of methods.

Geochemistry and oxidation state of Lau Basin basalts

The backarc glasses recovered during Ocean Drilling Program Leg 135 are unique among submarine tholeiitic glasses with respect to their oxygen fugacity and sulfur concentrations. Unlike mid-ocean-ridge basalt glasses, fO2 in these samples (inferred from ratios Fe3+/Fe2+) is high and variable, and S variations (90-1140 ppm) are not coupled with FeO concentration. Strong correlations occur between the alkali and alkaline-earth elements and both fO2 (positive correlations) and S concentrations (negative correlations). Correlations between fO2 and various trace elements are strongest for those elements with a known affinity for hydrous fluids (perhaps produced during slab dehydration), suggesting the presence of a hydrous fluid with high fO2 and high alkali and alkaline earth element concentrations in the Lau Basin mantle. Concentrations of S and fO2 are strongly correlated; high fO2 samples are characterized by low S in addition to high alkali and alkaline earth element concentrations. The negative correlations between S and these trace elements are not consistent with incompatible behavior of S during crystallization. Mass balance considerations indicate that the S concentrations cannot result simply from mixing between low-S and high-S sources. Furthermore, there is no relationship between S and other trace elements or isotope ratios that might indicate that the S variations reflect mixing processes. The S variations more likely reflect the fact that when silicate coexists with an S-rich vapor phase the solubility of S in the silicate melt is a function of fO2 and is at a minimum at the fO2 conditions recorded by these glasses. The absence of Fe-sulfides and the high and variable vesicle contents are consistent with the idea that S concentrations reflect silicate-vapor equilibria rather than silicate-sulfide equilibria (as in MORB). The low S contents of some samples, therefore, reflect the high fO2 of the supra-subduction zone environment rather than a low-S source component.

Concentrations of Fe, Mn, Cu, Zn, Co, Ni, Pb, Cd, B, and SiO2 in interstitial waters from bottom sediments of the Atlantis II and Discovery Deeps, Red Sea rift zone

Chemical analyzes show that interstitial waters from ore-bearing bottom sediments of the Atlantis II and Discovery Deeps are enriched in Fe, Mn, Cu, Ni, Co, Zn, Pb, and Cd compared to sea water. Enrichment factors of these trace elements in the interstitial waters of the Atlantis II Deep relative to the sea water vary within the following ranges: for Fe from 100 to 7000, for Mn from 19047 to 32738, for Zn from 500 to 1600, for Pb from 78333 to 190000, for Cu from 107 to 654. Comparison of average weighted concentrations of Fe, Mn, Zn, Pb, Cu, Ni in the bottom sediments and the interstitial waters of the Atlantis II Deep indicates common regularities and good relationship in distribution of these elements along sediment cores. Differences in concentrations and distribution of the studied trace elements in the interstitial waters of the Atlantis II and Discovery Deeps result from different chemical compositions of hydrothermal fluids entering these deeps.

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.

Geochemistry of recent sediments of the East African continental margin, Arabian Sea

Chemical analyses have been carried out on 40 samples from the sediment surface and 210 samples from cores that were taken from the edge of the African continental block at the Arabian Sea (coasts of Somalia and Kenya, from Cape Guardafui to Mombasa) on the occasion of the Indian Ocean Expedition of the German research vessel "Meteor" during the years 1964/65. The carbonate content shows its maximum on the northern part of the continental shelf of Africa, where fossil reef debris furnish the detritic portion of carbonate. In the southern part of the continental shelf of Africa the portion of carbonate is low, as it is heavily diluted by the non-carbonatic detritus. It is also in the deep-sea that a lower carbonate content is encountered below the calcite compensation depth. Trace elements in the carbonates: On the shelf and in its vicinity Sr and Mg are enriched. The enrichment has been brought about by the portion of reef debris, as this latter contains aragonite (enrichment of Sr) as well as high-magnesium calcite. The greatest part of the slope contains carbonates that are poor in trace elements and mainly made up of foraminifera (and of coccoliths). Below the carbonate compensation depth another enrichment of Mg takes place in the carbonates, which is probably due to a selective dissolution of calcite in comparison to dolomite. The iron and manganese contents of the carbonates are high (iron higher in coast proximity, manganese higher in the depth), but not genuine, as they come about in the course of the extraction of the carbonates as a result of the dissolution of authigenic Mn-Fe-minerals. Non-carbonatic portion of the sediments: In coast proximity an enrichment of quartz comes about. Within the quartz-rich zone it is the elements V, Cr, Fe, Ti, and B that have been enriched in the non-carbonatic components. This enrichment must be attributed to an elevated content of heavy minerals. In the case of Ti and Fe the preliminary enrichment brought about by processes of lateritisation on the continent plays a certain role. Toward the deep-sea an enrichment of the elements Mn Ni, Cu, and Zn takes place; these enrichments must be explained by authigenic Mn-Fe-minerals. Within the Mn-rich zone a belt running parallel to the coast stands out that shows an increased Mn-enrichment. However, this increase in enrichment does not apply to the elements Ni, Cu, and Zn. It is probable that this latter increased enrichment comes about as a result of the migration of manganese to the sediment surface. (Within the sediments there prevail reductive conditions, in the presence of which Mn is capable of migration, whereas at the sediment surface its precipitation comes about under oxidizing conditions). The quantity of organic matter mainly is dependent on grain size and on the rate of sedimentation. On the shelf an impoverishment of organic matter is to be encountered, as the sediments are coarse-grained. In the depth the impoverishment must be explained on the strength of a small rate of sedimentation. Between those two ranges organic substance is enriched. P and N show an enrichment in comparison to Corg with this applying all the more the smaller the absolute quantity of Corg is. In this particular case one has to do with an enrichment coming about during the diagenetic processes of organic matter. A comparison with the sediments from the Indian and Pakistani continental border in Arabian Sea shows as follows: on the African continental border the coarse detrital material has been transported farther out to deep-sea, which has something to do with the greater inclination of the surface of sedimentation. Carbonate is found in greater abundance on the African side. Its chemical composition is influenced by reef-debris which is missing by Indian-Pakistani side. The content of organic matter is lower on the African side. Contrary to that, the enrichments of N and P compared to organic matter are of an equal order of magnitude on both sides of the Arabian Sea.

Geochemistry and mineralogy of coal samples from Dingji Mine, Huainan Coalfield, China

To investigate the geochemistry of trace elements in coals from the Dingji Mine of the Huainan Coalfield, Anhui province, China, 416 borehole samples of coal, one parting, two floor and two roof mudstones were collected from 9 minable coal seams in 24 boreholes drilled during exploration. The abundances of 47 elements in each sample were determined by various instruments. The boron concentration in the coals suggests that marine influence decreased from coal seam 1 to 13-1. The geometric means of the elements Sn, Bi, Sb, and B are higher than the average for the corresponding elements in the coals from China, the U.S., and world. The enrichment of certain elements in the Shanxi or Upper Shihezi Formations is related to their depositional environment. The roof, floor and parting samples have higher contents of some elements than coal seams. The mineral matters in the coals from the Dingji Mine were found to consist mainly of granular quartz, clay minerals, and carbonate minerals. The elements are classified into two groups based on their stratigraphic distribution from coal seam 1 to 13-1, and the characteristics of each group are discussed. Based on the correlation coefficients of elemental concentrations with ash yield, four groups of elements with different affinities were identified.

Geochemistry and petrology of the volcanic rocks from the Sulu Sea

Major-, trace-, and rare-earth element analyses of the basaltic rocks recovered from the basement of the Sulu Sea and of lithic clasts from the pyroclastic unit representing the acoustic basement of the Cagayan Ridge, are presented. The major and trace elements were measured by X-ray fluorescence techniques, and rare-earth elements by instrumental neutron activation analysis. These data show that the Sulu Sea basalts are back-arc tholeiites and the lithic clasts are basalts, basaltic andesites, and andesites typical of volcanic arc suites erupted on continental crust. Petrogenetic modeling is used to show that the Sulu Sea basalts were derived from a heterogeneous mantle, probably representing subcontinental lithosphere, with contributions from a subduction component. The Sulu Sea is interpreted as a back-arc basin formed by rifting of an Oligocene to early Miocene volcanic arc leaving the Cagayan Ridge as a remnant arc. This event occurred during northward subduction of the Celebes Sea basement beneath the Oligocene to early Miocene arc.