Geochemistry of the oceanic crust from ocean drilling samples

This book presents new data on chemical and mineral compositions and on density of altered and fresh igneous rocks from key DSDP and ODP holes drilled on the following main tectonomagmatic structures of the ocean floor: 1. Mid-ocean ridges and abyssal plains and basins (DSDP Legs 37, 61, 63, 64, 65, 69, 70, 83, and 91 and ODP Legs 106, 111, 123, 129, 137, 139, 140, 148, and 169); 2. Seamounts and guyots (DSDP Legs 19, 55, and 62 and ODP Legs 143 and 144); 3. Intraplate rises (DSDP Legs 26, 33, 51, 52, 53, 72, and 74 and ODP Legs 104, 115, 120, 121, and 183); and 4. Marginal seas (DSDP Legs 19, 59, and 60 and ODP Legs 124, 125, 126, 127, 128, and 135). Study results of altered gabbro from the Southwest Indian Ridge (ODP Leg 118) and serpentinized ultramafic rocks from the Galicia margin (ODP Leg 103) are also presented. Samples were collected by the authors from the DSDP/ODP repositories, as well as during some Glomar Challenger and JOIDES Resolution legs. The book also includes descriptions of thin sections, geochemical diagrams, data on secondary mineral assemblages, and recalculated results of chemical analyses with corrections for rock density. Atomic content of each element can be quantified in grams per standard volume (g/1000 cm**3). The suite of results can be used to estimate mass balance, but parts of the data need additional work, which depends on locating fresh analogs of altered rocks studied here. Results of quantitative estimation of element mobility in recovered sections of the upper oceanic crust as a whole are shown for certain cases: Hole 504B (Costa Rica Rift) and Holes 856H, 857C, and 857D (Middle Valley, Juan de Fuca Ridge).

Geochemistry of Fe-Mn crusts in sediments of the Central Indian Ridge

Layered Fe-Mn crusts from the off-axis region of the first segment of the Central Indian Ridge north of the Rodrigues Triple Junction were studied geochemically and mineralogically. Vernadite (delta-MnO2) is the main mineral oxide phase. 230Thxs and Co concentrations suggest high growth rates of up to 29 mm/Myr and a maximum age of the basal crust layer of 1 Ma. Whereas most of the major and minor elements show concentrations which are typical of hydrogenetic formation, Co, Pb, Ni and Ti concentrations are strikingly lower. Concentrations and distribution of the strictly trivalent rare-earths and yttrium (REY) are typical of hydrogenetic ferromanganese oxide precipitates, but in marked contrast, the crusts are characterized by negative CeSN (shale normalized) anomalies and (Ce/Pr)SN ratios less than unity. Profiles through the crusts reveal only minor variations of the REY distribution and (Ce/Pr)SN ratios range from 0.45 to 0.68 (compared to ratios of up to 2 for typical hydrogenetic crusts from the Central Indian Basin). The apparent bulk partition coefficients between the crusts and seawater suggest that for the strictly trivalent REY the adsorption-desorption equilibrium has been reached. Positive Ce anomalies in the partition coefficient patterns reveal preferential uptake of Ce, but to a lesser extent than in normal hydrogenetic crusts. A new parameter (excess Ce, Cexs) to quantify the degree of decoupling of Ce from REY(III) is established on the basis of partition coefficients. Cexs/Cebulk ratios suggest that the CIR crusts formed by precipitation of Fe-Mn oxides from a hydrothermal plume and that in hydrothermal plumes and normal seawater the enrichment of Ce results from the same oxidative sorption process. The growth rates, calculated with 230Thxs data as well as with the Co formula, are inversely related to Cexs.

Accumulation rates for western Dronning Maud Land from firn cores and snow pits

As a result of intensive field activities carried out by several nations over the past 15 years, a set of accumulation measurements for western Dronning Maud Land, Antarctica, was collected, based on firn-core drilling and snow-pit sampling. This new information was supplemented by earlier data taken from the literature, resulting in 111 accumulation values. Using Geographical Information Systems software, a first region-wide mean annual snow-accumulation field was derived. In order to define suitable interpolation criteria, the accumulation records were analyzed with respect to their spatial autocorrelation and statistical properties. The resulting accumulation pattern resembles well known characteristics such as a relatively wet coastal area with a sharp transition to the dry interior, but also reveals complex topographic effects. Furthermore, this work identifies new high-return shallow drilling sites by uncovering areas of insufficient sampling density.

Geochemistry at DSDP Hole 76-534A

At Site 534 in the Blake-Bahama Basin, western North Atlantic, an interval of 68 m of Maestrichtian (Upper Cretaceous) and upper middle to upper Eocene sediments consists of terrigenous siltstones, mudstones, and varicolored zeolitic claystones; minor recovery of micritic limestones, porcellanites, and quartzitic chert was made at this site as well. Comparisons with other Deep Sea Drilling Project (DSDP) sites in the western North Atlantic suggest that the following formations are present in this interval: Hatteras (Maestrichtian), Plantagenet (Maestrichtian and upper Eocene), Bermuda Rise (upper middle to upper Eocene), and the basal Blake Ridge Formation (upper middle to upper Eocene). Recognition of a Tertiary interval of the Plantagenet allows that formation to be divided into lower and upper informal units. Condensation makes this formal lithostratigraphic subdivision difficult. Together the formations record marked net condensed sedimentation (average rate ca. 2.5 m/m.y.) in strongly oxidizing bottom waters. From sedimentary structures and petrography, it is inferred that the terrigenous siltstones and micritic limestones were redeposited from the continental margin by turbidity currents. Chemical data plus petrography confirm relatively high plankton productivity during the upper Eocene. Much of the nonrecovered Eocene interval may represent chert and porcellanite. Fragments recovered were formed by replacement of relatively porous calciturbidites by opal-CT and quartz. Radiolarians in interbedded claystones rich in clinoptilolite show extensive dissolution. Relative to typical hemipelagic sediments, the claystones are enriched in many metals (Cu, Ni, Zn, Pb), particularly within manganese micronodules. The metal accumulation is related to a 30-m.y. period of slow net sediment accumulation, rather than to hydrothermal enrichment or to upward mobilization of metals from the underlying reduced Hatteras black shale facies. Elsewhere in the Blake-Bahama Basin, at Site 391, 22 km to the northwest, upper Eocene facies are missing, reportedly due to deep seafloor erosion of up to 800 m of the sedimentary succession. By contrast, the discovery that this interval is preserved at nearby Site 534 points to much less extensive seafloor erosion, possibly mostly in the Oligocene, which is missing at both DSDP Sites.

Meteorological measurements from the Fourcade and Polar Club Glacier, Warszawa Icefield, King George Island, West Antarctica

The South Shetland Islands are located at the northern tip of the AP which is among the fastest warming regions on Earth. The islands are especially vulnerable to climate change due to their exposure to transient low-pressure systems and their maritime climate. Surface air temperature increases (2.5K in 50 years) are concurrent with retreating glacier fronts, an increase in melt areas, ice surface lowering and rapid break-up and disintegration of ice shelves. We have compiled a unique meteorological data set for the King George Island (KGI)/Isla 25 de Mayo, the largest of the South Shetland Islands. It comprises high-temporal resolution and spatially distributed observations of surface air temperature, wind directions and wind velocities, as well as glacier ice temperatures in profile with a fully equipped automatic weather station on the Warszawa Icefield, from November 2010 and ongoing. In combination with two long-term synoptic datasets (40 and 10 years, respectively) and NCEP/NCAR reanalysis data, we have looked at changes in the climatological drivers of the glacial melt processes, and the sensitivity of the inland ice cap with regard to winter melting periods and pressure anomalies. The analysis has revealed, a positive trend of 5K over four decades in minimum surface air temperatures for winter months, clearly exceeding the published annual mean statistics, associated to a decrease in mean monthly winter sea level pressure. This concurs with a positive trend in the Southern Annular Mode (SAM) index, which gives a measure for the strength and extension of the Antarctic vortex. We connect this trend with a higher frequency of low-pressure systems hitting the South Shetland Islands during austral winter, bringing warm and moist air masses from lower latitudes. Due to its exposure to the impact of transient synoptic weather systems, the ice cap of KGI is especially vulnerable to changes during winter glacial mass accumulation period. A revision of seasonal changes in adiabatic air temperature lapse rates and their dependency on exposure and elevation has shown a clear decoupling of atmospheric surface layers between coastal areas and the higher-elevation ice cap, showing the higher sensitivity to free atmospheric flow and synoptic changes. Observed surface air temperature lapse rates show a high variability during winter months (standard deviations up to ±1.0K/100 m), and a distinct spatial variability reflecting the impact of synoptic weather patterns. The observed advective conditions bringing warm, moist air with high temperatures and rain, lead to melt conditions on the ice cap, fixating surface air temperatures to the melting point. This paper assesses the impact of large-scale atmospheric circulation variability and climatic changes on the atmospheric surface layer and glacier mass accumulation of the upper ice cap during winter season for the Warszawa Icefield on KGI.

Geochemistry and petrology of ODP Site 136-843 basalts

About 13 m of Cretaceous, tholeiitic basalt, ranging from normal (N-MORB) to transitional (T-MORB) mid-ocean-ridge basalts, was recovered at Ocean Drilling Program Site 843 west of the island of Hawaii. These moderately fractionated, aphyric lavas are probably representative of the oceanic basement on which the Hawaiian Islands were built. Whole-rock samples from parts of the cores exhibiting only slight, low-temperature, seawater alteration were analyzed for major element, trace element, and isotopic composition. The basalts are characterized by enrichment in the high field strength elements relative to N-MORB, by a distinct positive Eu anomaly, and by Ba/Nb and La/Nb ratios that are much lower than those of other crustal or mantle-derived rocks, but their isotope ratios are similar to those of present-day N-MORB from the East Pacific Rise. Hole 843A lavas are isotopically indistinguishable from Hole 843B lavas and are probably derived from the same source at a lower degree of partial melting, as indicated by lower Y/Nb and Zr/Nb ratios and by higher concentrations of light and middle rare earth elements and other incompatible elements relative to Hole 843B lavas. Petrographic and trace-element evidence indicates that the Eu anomaly was the result of neither plagioclase assimilation nor seawater alteration. The Eu anomaly and the enrichments in Ta, Nb, and possibly U and K relative to N-MORB apparently are characteristic of the mantle source. Age-corrected Nd and Sr isotopic ratios indicate that the source for the lavas recovered at ODP Site 843 was similar to the source for Southeast Pacific MORB. An enriched component within the Cretaceous mantle source of these basalts is suggested by their initial 208Pb/204Pb-206Pb/204Pb and epsilon-Nd-206Pb/204Pb ratios. The Sr-Pb isotopic trend of Hawaiian post-shield and post-erosional lavas cannot be explained by assimilation of oceanic crust with the isotopic composition of the Site 843 basalts.

Radioisotope stratigraphy, sedimentology and geochemistry of Late Quaternary sediments from the Eastern Arctic Ocean

To reconstruct Recent and past sedimentary environments, marine sediments of Upper Pleistocene and Holocene ages from the eastern Arctic Ocean and especially from the Nansen-Gakkel Ridge (NGR) were investigated by means of radioisotopic, geochemical and sedimentological methods. In combination with mass physical property data and lithological analysis these investigations allow clearly to characterize the depositional environments. Age dating by using the radioisotope 230Th gives evidence that the investigated sediments from the NGR are younger than 250,000 years. Identical lithological sediment sequences within and between sediment cores from the NGR can be related to sedimentary processes which are clearly controlled by palaeoclimate. The sediments consist predominantly of siliciclastic, terrigenous ice-rafted detritus (IRD) deriving from assorted and redeposited sediments from the Siberian shelfs. By their geochemical composition the sediments are similar to mudstone, graywacke and arcose. Sea-ice as well as icebergs play a major roll in marine arctic sedimentation. In the NGR area rapid change in sedimentary conditions can be detected 128,000 years ago. This was due to drastic change in the kind of ice cover, resulting from rapid climatic change within only hundreds of years. So icebergs, deriving mostly from Siberian shelfs, vanished and sea-ice became dominant in the eastern Arctic Ocean. At least three short-period retreats of the shelf ice between 186,000 and 128,000 years are responsible for the change of coarse to fine-grained sediments in the NGR area. These warmer stages lasted between 1,000 and 3,000 years. By monitoring and comparing the distribution patterns of sedimentologic, mass physical and geochemical properties with 230Th ex activity distribution patterns in the sediment cores from the NGR, there is clear evidence that sediment dilution is responsible for high 230Th ex activity variations. Thus sedimentation rate is the controlling factor of 230Th ex activity variations. The 230Th flux density in sediments from the NGR seems to be highly dependent On topographic Position. The distribution patterns of chemical elements in sediment cores are in general governed by lithology. The derivation of a method for dry bulk density determination gave the opportunity to establish a high resolution stratigraphy on sediment cores from the eastern Arctic Ocean, based on 230Thex activity analyses. For the first time sedimentation and accumulation rates were determined for recent sediments in the eastern Arctic Ocean by 230Th ex analyses. Bulk accumulation rates are highly variable in space and time, ranging between 0.2 and 30 g/cm**2/ka. In the sediments from the NGR highly variable accumulation rates are related to the kind of ice cover. There is evidence for hydrothermal input into the sediments of the NGR. Hydrothermal activity probably also influences surficial sediments in the Sofia Basin. High contents of As are typical for surficial sediments from the NGR. In particular SL 370-20 from the bottom of the rift valley has As contents exceeding in parts 300 ppm. Hydrothermal activity can be traced back to at least 130,000 years. Recent to subrecent tectonic activity is documented by the rock debris in KAL 370 from the NGR. In four other sediment cores from the NGR rift valley area tectonically induced movements can be dated to about 130,000 years ago, related most probably to the rapid climate change. Processes of early diagenesis in sediments from the NGR caused the aobilization and redeposition of Fe, Mn and Mo. These diagenetic processes probably took place during the last 130,000 years. In sediment cores from the NGR high amounts of kaolinite are related to coarse grained siliciclastic material, probably indicating reworking and redeposition of siberian sandstones with kaolinitic binding material. In contrast to kaolinite, illite is correlated to total clay and 232Th contents. Aragonite, associated with serpentinites in the rift valley area of the NGR, was precipitated under cold bottom-water conditions. Preliminary data result in a time of formation about 60 - 80 ka ago. Manganese precipitates with high Ni contents, which can be related to the ultrabasic rocks, are of similar age.

Geochemistry and physics on sediment cores from the Peru Basin

We studied preservation/dissolution cycles and paleoproductivity in eight sediment cores from the Peru Basin south of the highly productive surface waters of the eastern equatorial Pacific. Stratigraphy is based on stable oxygen isotopes and on combined magnetostratigraphy and biostratigraphy. Sediment cores which span the last 8 m.y., were retrieved during cruise 79 with RV SONNE close to the carbonate compensation depth (CCD). In general, sediments show Pacific-type carbonate cycles. We interpret a pronounced carbonate peak between 6 and 7 Ma as the result of a western and northern extension of the highly productive Peru Current. Decreased carbonate contents from the late Miocene to the late Pliocene might be associated with a slow contraction of the latitudinal extent of the high-productivity belt north of the study areas. During the Pliocene, carbonate variations showed 400 kyr cycles indicating the growth and decay of ice sheets, which should have been associated with pulsations of the Antarctic ice cap. An abrupt collapse of the carbonate system occurred at 2.4 Ma. Higher frequency variations of the carbonate record indicate the major increase of the northern hemisphere glaciation. During the Quaternary, carbonate fluxes are high during glacials and low during interglacials. Large amplitude variations with long broad minima and maxima, associated with small migrations of the lysocline and the CCD (< 200 m), are indicative of the preservation/dissolution history in the Peru Basin. During the early Pleistocene, climatic forcing by the 41 kyr obliquity cycle is not observed in the carbonate record. During the last 800 kyr, variability in the carbonate record was dominated by the 100 kyr eccentricity cycle. Fluxes of biogenic material (calcium carbonate, organic carbon, opal, and barium) were greatest during glacials, which imply higher productivity and export production of the Peru Current during cold climatic periods. Dissolution was greatest during interglacials as inferred from the relatively poor preservation of planktonic foraminifera and from the low accumulation rate of carbonate. After the Mid-Brunhes Event (400 ka), we observe a plateaulike shift to enhanced dissolution and to intensified productivity.

Igneous geochemistry of OP Leg 126 samples

Major element, trace element, and radiogenic isotope compositions of samples collected from Ocean Drilling Program Leg 126 in the Izu-Bonin forearc basin are presented. Lavas from the center of the basin (Site 793) are high-MgO, low-Ti, two-pyroxene basaltic andesites, and represent the products of synrift volcanism in the forearc region. These synrift lavas share many of the geochemical and petrographic characteristics of boninites. In terms of their element abundances, ratios, and isotope systematics they are intermediate between low-Ti arc tholeiites from the active arc and boninites of the outer-arc high. These features suggest a systematic geochemical gradation between volcanics related to trench distance and a variably depleted source. A basement high drilled on the western flank of the basin (Site 792) comprises a series of plagioclase-rich two-pyroxene andesites with calc-alkaline affinities. These lavas are similar to calc-alkaline volcanics from Japan, but have lower contents of Ti, Zr, and low-field-strength elements (LFSE). Lavas from Site 793 show inter-element variations between Zr, Ti, Sr, Ni, and Cr that are consistent with those predicted during crystallization and melting processes. In comparison, concentrations of P, Y, LFSE, and the rare-earth elements (REE) are anomalous. These elements have been redistributed within the lava pile, concentrating particularly in sections of massive and pillowed flows. Relative movement of these two-element groupings can be related to the alteration of interstitial basaltic andesite glass to a clay mineral assemblage by a post-eruptive process. Fluid-rock interaction has produced similar effects in the basement lavas of Site 792. In this sequence, andesites and dacites have undergone a volume change related to silica mobility. As a result of this process, some lithologies have the major element characteristics of basaltic andesite and rhyolite, but can be related to andesitic or dacitic precursors by silica removal or addition.

Geochemical composition of sediments from ODP Site 164-997, Blake Ridge

Twenty-two trace elements in 355 sediment samples from Site 997 on the Blake Ridge were examined by inductively coupled plasma-optical emission spectrometry and inductively coupled plasma-mass spectrometry, for respective fractions of acid-soluble and insoluble compositions. Downhole profiles of these elements exhibit complicated fluctuations throughout late Miocene to Pleistocene, principally due to the variations in the acid-soluble fraction. Noncarbonate composition is given from the acid-insoluble residues, which permits us to recognize secular feature of selected element variance for four intervals. These intervals (I: 0-183 mbsf; II: 183- 440 mbsf; III: 440-618 mbsf; and IV: 618-750 mbsf) are interpreted to have originated from changes in the suite of sediments of particular sources and chemical composition, sedimentation rate, dilution of biogenic carbonate abundance, and possibly the current system that controlled deposition and reworking of the terrigenous materials.

Elements and isotopic measurements of magmatic rock samples from ODP Hole 104-642E

Trace element and isotopic signatures of magmatic rock samples from ODP Hole 642E at the Vøring Plateau provide insight into the interaction processes of mantle melt with crust during the initial magma extrusion phases at the onset of the continental breakup. The intermediate (basaltic-andesitic) to felsic (dacitic and rhyolitic) Lower Series magmas at ODP Hole 642E appear to be produced by large amounts of melting of upper crustal material. This study not only makes use of the traditional geochemical tools to investigate crust-mantle interaction, but also explores the value of Cs geochemistry as an additional tool. The element Cs forms the largest lithophile cation, and shows the largest contrast in concentration between (depleted) mantle and continental crust. As such it is a very sensitive indicator of involvement of crustal material. The Cs data reinforce the conclusion drawn from isotopic signatures that the felsic magmas are largely anatectic crustal melts. The down-hole geochemical variation within ODP Hole 642E defines a decreasing continental crustal influence from the Lower Series into the Upper Series. This is essential information to distinguish intrinsic geochemical properties of the mantle melts from signatures imposed by crustal contamination. A comparison with data from the SE Greenland margin highlights the compositional asymmetry of the crust-mantle interactions at both sides of the paleo-Iapetus suture. While Lower Series and Middle Series rocks from the SE Greenland margin have isotopic signatures reflecting interactions with lower and middle crust, such signatures have not been observed at the mid-Norwegian margin. The geochemical data either point to a dissimilar Caledonian crustal composition and/or to different geodynamic pre-breakup rifting history at the two NE Atlantic margin segments.

Carbon and Lead chemistry of sediments from the Middle Atlantic Bight

A mass budget was constructed for organic carbon on the upper slope of the Middle Atlantic Bight, a region thought to serve as a depocenter for fine-grained material exported from the adjacent shelf. Various components of the budget are internally consistent, and observed differences can be attributed to natural spatial variability or to the different time scales over which measurements were made. The flux of organic carbon to the sediments in the core of the depocenter zone, at a water depth of 1000 m, was measured with sediment traps to be 65 mg C m**-2 day**-1, of which 6-24 mg C m**-2 day**-1 is buried. Oxygen fluxes into the sediments, measured with incubation chambers attached to a free vehicle lander, correspond to total carbon remineralization rates of 49-70 mg C m**-2 day**-1. Carbon remineralization rates estimated from gradients of Corg within the mixed layer, and from gradients of dissolved ammonia and phosphate in pore waters, sum to only 4-6 mg C m**-2 day**-1. Most of the Corg remineralization in slope sediments is mediated by bacteria and takes place within a few mm of the sediment-water interface. Most of the Corg deposited on the upper slope sediments is supplied by lateral transport from other regions, but even if all of this material were derived from the adjacent shelf, it represents <2% of the mean annual shelf productivity. This value is further lowered by recognizing that as much as half of the Corg deposited on the slope is refractory, having originated by reworking from older deposits. Refractory Corg arrives at the sea bed with an average 14C age 600-900 years older than the pre-bomb 14C age of DIC in seawater, and has a mean life in the sediments with respect to biological remineralization of at least 1000 years. Labile carbon supplied to the slope, on the other hand, is rapidly and (virtually) completely remineralized, with a mean life of < 1 year. Carbon-14 ages of fine-grained carbonate and organic carbon present within the interstices of shelf sands are consistent with this material acting as a source for the old carbon supplied to the slope. Winnowing and export of reworked carbon may contribute to the often-described relationship between organic carbon preservation and accumulation rate of marine sediments.

Trace metals in sediments of the Var Canyon turbidite system at the DYFAMED station in the Ligurian Sea

The magnitude and the chronology of anthropogenic impregnation by Hg and other trace metals of environmental concern (V, Cr, Ni, Cu, Zn, Ag, Cd and Pb, including its stable isotopes) in the sediments are determined at the DYFAMED station, a site in the Ligurian Sea (Northwestern Mediterranean) chosen for its supposed open-sea characteristics. The DYFAMED site (VD) is located on the right levee of the Var Canyon turbidite system, at the end of the Middle Valley. In order to trace the influence of the gravity current coming from the canyon on trace metal distribution in the sediment, we studied an additional sediment core (VA) from a terrace of the Var Canyon, and material collected in sediment traps at the both sites at 20 m above sea bottom. The patterns of Hg and other trace element distribution profiles are interpreted using stable Pb isotope ratios as proxies for its sources, taking into account the sedimentary context (turbidites, redox conditions, and sedimentation rates). Major element distributions, coupled with the stratigraphic examination of the sediment cores point out the high heterogeneity of the deposits at VA, and major turbiditic events at both sites. At the DYFAMED site, we observed direct anthropogenic influence in the upper sediment layer (<2 cm), while on the Var Canyon site (VA), the anthropization concerns the whole sedimentary column sampled (19 cm). Turbiditic events superimpose their specific signature on trace metal distributions. According to the 210Pbxs-derived sedimentation rate at the DYFAMED site (0.4 mm yr-1), the Hg-enriched layer of the top core corresponds to the sediment accumulation of the last 50 years, which is the period of the highest increase in Hg deposition on a global scale. With the hypothesis of the absence of significant post-depositional redistribution of Hg, the Hg/C-org ratio changes between the surface and below are used to estimate the anthropogenic contribution to the Hg flux accumulated in the sediment. The Hg enrichment, from pre-industrial to the present time is calculated to be around 60%, consistent with estimations of global Hg models. However, based on the chemical composition of the trapped material collected in sediment traps, we calculated that epibenthic mobilization of Hg would reach 73%. Conversely, the Cd/C-org ratio decreases in the upper 5 cm, which may reflect the recent decrease of atmospheric Cd inputs or losses due to diagenetic processes.

Chemical composition of ferromanganese manifestations from the Sea of Okhotsk

New data on microstructures and mineral and chemical compositions of ferromanganese crusts sampled from the western slope of the Kuril Island Arc in the Sea of Okhotsk during cruises of R/V Vulkanolog are discussed. The study of the crusts using analytical electron microscopy methods revealed that their manganese phase is represented by vernadite, Fe-vernadite, todorokite, asbolane, and asbolane-buserite, while iron phase consists of hematite, hydrohematite, ferroxyhite, and magnetite. Lithic mineral assemblage includes apatite, quartz, epidote, and montmorillonite. According to chemical analysis most of the crusts contain significant part of volcanogenic and hydrothermal material. It is evident from elevated values of Mn/Fe and (Mn+Fe)/Ti ratios, low concentrations of some trace elements, and positive Eu anomaly.