Geochemistry of tetrapyrrole, carotenoid, and perylene pigments in sediments at DSDP Holes 63-467 and 63-471

Twenty-one core samples from DSDP/IPOD Leg 63 were analyzed for products of chlorophyll diagenesis. In addition to the tetrapyrrole pigments, perylene and carotenoid pigments were isolated and identified. The 16 core samples from the San Miguel Gap site (467) and the five from the Baja California borderland location (471) afforded the unique opportunity of examining tetrapyrrole diagenesis in clay-rich marine sediments that are very high in total organic matter. The chelation reaction, whereby free-base porphyrins give rise to metalloporphyrins (viz., nickel), is well documented within the downhole sequence of sediments from the San Miguel Gap (Site 467). Recognition of unique arrays of highly dealkylated copper and nickel ETIO-porphyrins, exhibiting nearly identical carbonnumber homologies (viz., C-23 to C-30; mode = C-26), enabled subtraction of this component (thought to be derived from an allochthonous source) and thus permitted description of the actual in situ diagenesis of autochthonous chlorophyll derivatives.

Clay mineralogy of carbonate-rich sediments of ODP Leg 101 sites

The insoluble residues of samples from ODP Sites 626 and 627 can be subdivided into four groups: (1) illite, 7 A minerals, quartz and feldspar; (2) smectite and zeolite (clinoptilolite); (3) palygorskite and in places sepiolite; and (4) glauconite and pyrite. Whereas group 1 is clearly terrigenous and group 4 authigenic, group 2 is most probably authigenic, as indicated by its abundance in samples with small insoluble residues and its appearance in SEM photographs. Group 3 is authigenic in Albian peritidal dolomite and possibly terrigenous in middle Miocene slumps and debris flows. Smectite crystallinity increases with age. This increase, however, is less pronounced in the Bahamian carbonate-rich samples than in the carbonate-poor silts south of Guatemala (DSDP Leg 84, Sites 569 and 570, the only comparable investigation) as far as can be judged from such a small number of samples.

Clay mineral assemblages in the western Baltic Sea

Surface samples and nine cores from the western Baltic Sea and marginal water bodies were investigated for clay mineral composition. The clay mineral assemblages of recent sediments are rather homogeneous. Variations result mainly from the erosion of different glacial source deposits. High percentages of illite and low kaolinite/chlorite and quartz/feldspar ratios are characteristic for this glacial source. Advection of kaolinite-rich suspensions from the North Sea is believed to account for higher kaolinite/chlorite ratios in the Mecklenburg Bight. A contribution of the rivers Trave and Oder to the western Baltic Sea is indicated by increased smectite values in marginal water bodies. They correspond to increased kaolinite/chlorite and quartz/feldspar ratios. In the main basins the river signal is diluted beyond recognition. Cores from the Arkona, Bornholm and Gotland Basins penetrate through post-Littorina muds and sediments of the Ancylus Lake/Yoldia Sea into Late Glacial sediments of the Baltic Ice Lake. Clay mineral assemblages are characterized by an increase in kaolinite/chlorite ratios from Late Glacial to Holocene sediments, with a distinct shift at each facies change. This allows the distinction and core to core correlation of main lithological units with kaolinite/chlorite ratios. Kaolinite enrichment of Holocene muds corresponds to a brackish-marine facies and may reflect influx of kaolinite-rich suspensions from the North Sea. Cores from the lagoon of the Oderhaff show fluctuations in the contributions of the two main sediment sources: river suspension and glacial deposits during the Late Glacial and Postglacial sequence. Lacustrine sediments, which were deposited prior to 5500 years B.P. are characterized by smectite, kaolinite and quartz from the drainage area of the Oder river. Erosion of coastal and offshore glacial boulder clays with the Littorina transgression supplied a marine component rich in illite, chlorite and feldspars to the brackish muds of the Oderhaff.

Clay mineralogy and multi-element chemistry of surface sediments on the Aiberian-Arctic Shelf

Clay mineral and bulk chemical (Si, Al, K, Mg, Sr, La, Ce, Nd) analyses of terrigenous surface sediments on the Siberian-Arctic shelf indicate that there are five regions with distinct, or endmember, sedimentary compositions. The formation of these geochemical endmembers is controlled by sediment provenance and grain size sorting. (1) The shale endmember (Al, K and REE rich sediment) is eroded from fine-grained marine sedimentary rocks of the Verkhoyansk Mountains and Kolyma-Omolon superterrain, and discharged to the shelf by the Lena, Yana, Indigirka and Kolyma Rivers. (2) The basalt endmember (Mg rich) originates from NE Siberia's Okhotsk-Chukotsk volcanic belt and Bering Strait inflow, and is prevalent in Chukchi Sea Sediments. Concentrations of the volcanically derived clay mineral smectite are elevated in Chukchi fine-fraction sediments, corroborating the conclusion that Chukchi sediments are volcanic in origin. (3) The mature sandstone endmember (Si rich) is found proximal to Wrangel Island and sections of the Chukchi Sea's Siberian coast and is derived from the sedimentary Chukotka terrain that comprises these landmasses. (4) The immature sandstone endmember (Sr rich) is abundant in the New Siberian Island region and reflects inputs from sedimentary rocks that comprise the islands. (5) The immature sandstone endmember is also prevalent in the western Laptev Sea, where it is eroded from sedimentary deposits blanketing the Siberian platform that are compositionally similar to those on the New Siberian Islands. Western Laptev can be distinguished from New Siberian Island region sediments by their comparatively elevated smectite concentrations and the presence of the basalt endmember, which indicate Siberian platform flood basalts are also a source of western Laptev sediments. In certain locations grain size sorting noticeably affects shelf sediment chemistry. (1) Erosion of fines by currents and sediment ice rafting contributes to the formation of the coarse-grained sandstone endmembers. (2) Bathymetrically controlled grain size sorting, in which fines preferentially accumulate offshore in deeper, less energetic water, helps distribute the fine-grained shale and basalt endmembers. An important implication of these results is that the observed sedimentary geochemical endmembers provide new markers of sediment provenance, which can be used to track sediment transport, ice-rafted debris dispersal or the movement of particle-reactive contaminants.

Geochemistry, clay mineralogy and grain size distribution in various sediment cores drilled during ODP Leg 119 on the Antarctic continental shelf off Prydz Bay

Drilling was undertaken at five sites (739-743) on ODP Leg 119 on a transect across the continental shelf of Prydz Bay, East Antarctica, to elucidate the long-term glacial history of the area and to examine the importance of the area with respect to the development of the East Antarctic ice sheet as a whole. In addition to providing a record of glaciation spanning 36 m.y. or more, Leg 119 has provided information concerning the development of a continental margin under the prolonged influence of a major ice sheet. This has allowed the development of a sedimentary model that may be applicable not only to other parts of the Antarctic continental margin, but also to northern high-latitude continental shelves. The cored glacial sedimentary record in Prydz Bay consists of three major sequences, dominated by diamictite: 1. An upper flat-lying sequence that ranges in thickness from a few meters in inner and western Prydz Bay to nearly 250 m in the outer or eastern parts of the bay. The uppermost few meters consist of Holocene diatom ooze and diatomaceous mud with a minor ice-rafted component overlying diamicton and diamictite of late Miocene to Quaternary age. The diamictite is mainly massive, but stratified varieties and minor mudstone and diatomite also occur. 2. An upper prograding sequence cored at Sites 739 and 743, unconformly below the flat-lying sequence. This consists of a relatively steep (4° inclination) prograding wedge with a number of discrete sedimentary packages. At Sites 739 and 743 the sequence is dominated by massive and stratified diamictite, some of which shows evidence of slumping and minor debris flowage. 3. A lower, more gently inclined, prograding sequence lies unconformably below the flat-lying sequence at Site 742 and the upper prograding sequence at Site 739. This extends to the base of both sites, to 316 and 487 mbsf, respectively. It is dominated by massive, relatively clast-poor diamictite which is kaolinite-rich, light in color, and contains sporadic carbonate-cemented layers. The lower part of Site 742 includes well-stratified diamictites and very poorly sorted mudstones. The base of this site has indications of large-scale soft-sediment deformation and probably represents proximity to the base of the glacial sequence. Facies analysis of the Prydz Bay glacial sequence indicates a range of depositional environments. Massive diamictite is interpreted largely as waterlain till, deposited close to the grounding line of a floating glacier margin, although basal till and debris flow facies are also present. Weakly stratified diamictite is interpreted as having formed close to or under the floating ice margin and influenced by the input of marine diatomaceous sediment (proximal glaciomarine setting). Well-stratified diamictite has a stronger marine input, being more diatom-rich, and probably represents a proximal-distal glaciomarine sediment with the glaciogenic component being supplied by icebergs. Other facies include a variety of mudstones and diatom-rich sediments of marine origin, in which an ice-rafted component is still significant. None of the recovered sediments are devoid of a glacial influence. The overall depositional setting of the prograding sequence is one in which the grounded ice margin is situated close to the shelf edge. Progradation was achieved primarily by deposition of waterlain till. The flat-lying sequence illustrates a complex sequence of advances and retreats across the outer part of the shelf, with intermittent phases of ice loading and erosion. The glacial chronology is based largely on diatom stratigraphy, which has limited resolution. It appears that ice reached the paleoshelf break by earliest Oligocene, suggesting full-scale development of the East Antarctic ice sheet by that time. The ice sheet probably dominated the continental margin for much of Oligocene to middle Miocene time. Retreat, but not total withdrawal of the ice sheet, took place in late Miocene to mid-Pliocene time. The late Pliocene to Pleistocene was characterized by further advances across, and progradation of, the continental shelf. Holocene time has been characterized by reduced glacial conditions and a limited influence of glacial processes on sedimentation.

(Supplement T1) Clay mineral compositions at the Aleutian Basin of the Bering Sea from IODP sites 323-U1343

The clay mineral composition at IODP Exp. 323 Site U1343 in the Bering Sea was analyzed so as to unravel their provenance over glacial-interglacial cycles for the last 2.4 Ma. Smectite was negatively correlated with the sum of illite and chlorite; therefore, their ratio [S/(I + C)] was used as an indicator of clay mineral composition changes. In general, the S/(I + C) ratio was rather similar for glacial and interglacial periods during most of the last 2.4 Ma. In addition, these results overlap with those of surface sediments in the modern East Aleutian Basin, which suggests that smectite-rich clay particles are delivered from the Aleutians by the northward Bering Slope Current (BSC) rather than from rivers in western Alaska. However, some clay mineral compositions of the glacial periods after the Mid-Pleistocene Transition (MPT: 1.25-0.7 Ma) were characterized by low illite and relatively high smectite. During this period, extensive ice-rafting might have transported the smectite-rich clay particles to Site U1343 from the glacial shelf off Alaska and/or from glacial rivers from that area.

Chemical composition of clay minerals from ODP Leg 168 sites

The exchangeable cation compositions of organic-poor terrigenous sediments containing smectite as primary ion exchanger from a series of holes along ODP Leg 168 transect on the eastern flank of the Juan de Fuca Ridge have been examined as a function of distance from the ridge axis and burial depth. The total cation exchange capacity (CEC) values of the sediments ranged from 2 to 59 meq/100 g, increasing with increases in the wt.% smectite. At the seafloor, the exchangeable cation compositions involving Na, K, Mg, and Ca, expressed in terms of equivalent fraction, are nearly constant regardless of the different transect sites: XNa = 0.21 ± 0.04, XK = 0.08 ± 0.01, XMg = 0.33 ± 0.09, and XCa = 0.38 ± 0.09. The calculated selectivity coefficients of the corresponding quaternary exchange reactions, calculated using porewater data, are in log units -5.45 ± 0.39 for Na, 1.97 ± 0.49 for K, 0.42 ± 0.41 for Mg, and 3.06 ± 0.69 for Ca. The exchangeable cation compositions below the seafloor change systematically with distance from the ridge crest and burial depth, conforming to the trends of the same cations in the porewaters. The selectivities for Na and Mg are roughly constant at temperatures from 2 to 66°C, indicating that the equivalent fractions of these two cations are independent of sediment alteration taking place on the ridge flank. Unlike Na and Mg, the temperature influence is significant for K and Ca, with Ca-selectivity decreases being coupled with increases in K-selectivity. Although potentially related to diagenetic and/or hydrothermal mineral precipitation or recrystallization, no evidence of such alteration was detected by XRD and TEM. In sites where upwelling of hydrothermal fluids from basement is occurring, the K-selectivity of the sediment is appreciably higher than at the other sites and corresponds to the formation of (Fe, Mg) rich smectite and zeolites. Our study indicates that local increases in K-selectivity at hydrothermal sites are caused by the formation of these authigenic minerals.

Radiocarbon ages and clay minerals in sediment cores obtained during a 2009 Jan Mayen cruise to the Norwegian Sea

The origin of two acoustic sediment units has been studied based on lithological facies, chronology and benthic stable isotope values as well as on foraminifera and clay mineral assemblages in six marine sediment cores from Kveithola, a small trough west of Spitsbergenbanken on the western Barents Sea margin. We have identified four time slices with characteristic sedimentary environments. Before c. 14.2 cal. ka, rhythmically laminated muds indicate extensive sea ice cover in the area. From c. 13.9 to 14.2 cal. ka, muds rich in ice-rafted debris were deposited during the disintegration of grounded ice on Spitsbergenbanken. From c. 10.3 to 13.1 cal. ka, sediments with heterogeneous lithologies suggest a shifting influence of suspension settling and iceberg rafting, probably derived from a decaying Barents Sea Ice Sheet in the inner-fjord and land areas to the north of Kveithola. Holocene deposition was episodic and characterized by the deposition of calcareous sands and shell debris, indicative of strong bottom currents. We speculate that a marked erosional boundary at c. 8.2 cal. ka may have been caused by the Storegga tsunami. Whilst deposition was sparse during the Holocene, Kveithola acted as a sediment trap during the preceding deglaciation. Investigation of the deglacial sediments provides unprecedented details on the dynamics and timing of glacial retreat from Spitsbergenbanken.

Bulk and clay mineralogy of ODP Leg 110 holes

The mineralogy of both bulk- and clay-sized fractions of samples from Sites 671, 672, and 674 of ODP Leg 110 was determined by X-ray diffraction. The major minerals include quartz, calcite, plagioclase feldspar, and the clay minerals smectite, illite, and kaolinite. The smectite is a dioctahedral montmorillonite and is derived primarily from degradation of volcanic ash. Percentage of smectite varies with sediment age; Miocene and Eocene sediments are the most smectite-rich. High smectite content tends to correlate with elevated porosity, presumably because of the ability of smectite clays to absorb significant amounts of interlayer water. Because of a change in physical properties, the decollement zone at Site 671 formed in sediments immediately subjacent to a section of smectite-rich, high-porosity, Miocene-age sediments. Sediments above the decollement at Site 671, as well as all sediments analyzed from Sites 672 and 674, contain nearly pure smectite characteristic of the alteration of volcanic ash. Within the decollement zone and underthrust sequence, however, the smectite contains up to 65% illite interlayers. Although the illite/smectite could be interpreted as detrital clay derived from South America, its absence in the sediments stratigraphically equivalent to the decollement and underthrust sequences at Sites 672 and 674 favors the interpretation that it originated by diagenetic alteration of pre-existing smectite similar to that in the overlying sediments. A significant percentage of the freshening of the pore waters observed in these zones could be due to the water released during smectite dehydration.

Chemical composition of siderites and clay minerals from DSDP Holes 70-506G and 70-507B

As soon as they are emplaced on the sea floor, oceanic basalts go through a low-temperature alteration process which produces black halos concentrical with exposed surfaces and cracks, whereas the grey internal parts of the basaltic pieces apparently remain unaltered. This paper reports for the first time the occurrence of authigenic siderite and ankerite in oceanic basalts and more particularly in the grey internal parts of the latter. Small (8-50 µm) crystals of zoned siderite and ankerite have been observed in ten vesicles of two samples recovered from DSDP Holes 506G and 507B drilled south of the Galápagos Spreading Center (GSC). These Fe-carbonates show a large range of chemical composition (FeCO3 = 47-88%; CaCO3 = 5-40%; MgCO3 = 1-20%; MnCO3 = 0-11%). Most of them are Ca-richer than siderite reported in the literature. The chemical composition of the carbonate clearly reflects the fluctuation of the fluid chemical composition during crystallization. Mn and at least part of the Fe are thought to be hydrothermal in origin, whereas Mg and probably Ca were provided by seawater. It is proposed that siderite and ankerite formed at relatively low temperature (<85°C) and is metastable. The alteration of the GSC basalts seems to have proceeded in two stages: during the first, reducing stage, pyrite precipitated from hydrothermal fluids. A little further in the rock, siderite precipitated from the fluid which had already been modified by the formation of pyrite, and thus in a microenvironment where particular conditions prevailed (high P_CO2, increasing p_S**2- or increasing pH or increasing or decreasing pe). During the second, oxidizing, stage of alteration, a seawater-dominated fluid allowed crystallization of mixtures of Fe-rich smectites and micas, and Fe-hydroxides forming the black halos in the external portion of the basalt pieces and locally oxidizing pyrite and siderite in their innermost part. It is shown in this paper that, even at its earliest stage, and at low temperature, alteration of the upper oceanic crust (lavas) involves fluids enriched in Fe and Mn, interpreted to be of hydrothermal origin.

Clay mineralogy of sediments from the Bengal Fan

We have measured the relative abundances of smectite, illite, chlorite, and kaolinite in a composite section of the distal Bengal Fan. Two sources of sediment appear to dominate, a smectite-poor, illite-rich source associated with rapid denudation of the Himalayas and a smectite-rich, illite-poor source probably on the continental margin of the Indian sub-continent. Changes in source appear to be related to uplift in the Himalayas and Tibetan Plateau both directly and through the climatic and oceanographic consequences of uplift.

Thermal diagenesis of clay minerals within volcanogenic material from ODP Site 135-841

Clay minerals are examined in detail in the sediment from the Tonga Trench margin at Site 841 (Leg 135 ODP). The changes in amount and nature of secondary clays with depth provide an alternative explanation for the intensive alteration of volcanogenic material at convergent margins. A characteristic distribution of clay minerals with depth shows four distinct zones unexplainable by simple burial diagenesis processes. These are named the upper, reactive, lower and rhyolitic zones. The reactive zone is intercalated with numerous sills and is characterized by the dominant iron-rich clays such as saponite, corrensite and chlorite associated with analcime. The occurrence of such iron-rich clays, mostly associated with a large amount of analcime, yields chemical and mineralogical evidence for thermal diagenesis. The required heat for the diagenetic process was transferred from recently intruded basaltic andesite sills. In the vicinity of these intrusions, the iron-rich clay minerals may have formed at temperatures up to 200°C. A zoning with respect to clay and zeolite minerals indicates that the influence of the palaeoheat flow decreased with the distance from the intrusion. The formation of interlayered I/S, illite, kaolinite and aluminous chlorite, which are recognized as major secondary minerals within the rhyolitic complex, was mainly controlled by both early diagenesis at moderately elevated temperatures, and since the Eocene by burial diagenesis at low temperatures. The occurrence of a steam zone in an early stage of the intrusion is restricted to Miocene tuffs and has overprinted the early alteration of the volcanogenic material within the tuffs and has changed the originally pristine composition of the pore fluids.

Mineral content, major oxides and trace elements concentrations in clay from different IODP Holes of 331-C0013, 331-C0017, East China sea shelf and different Taiwan rivers

The Okinawa Trough (OT) in the East Asian continental margin is characterized by thick terrigenous sediment and ubiquitous volcanic-hydrothermal activities. In this study, the clays collected during IODP Expedition 331 to the middle OT (Iheya North Knoll) were analyzed for mineralogical and geochemical compositions. By comparing with the clays from the East China Sea shelf and surrounding rivers, we examine different clay origins. The hydrothermal field in the mid-OT is dominated by Mg-rich chlorite, while the recharge zone has clay mineral assemblages similar to the shelf and rivers, showing high content of illite, subordinate chlorite and kaolinite and scarce smectite. Compared to the terrigenous clays, the hydrothermal clays in the OT have high concentrations of Mg, Mn and Zr but low Fe, Na, K, Ca, Ba, Sr, P, Sc and Ti, while the hydrothermal clays in the mid-ocean ridge are relatively enriched in Fe and V and depleted in Al, Mg, Zr, Sc and Ti. Different fractionation patterns of rare earth elements also register in the terrigenous and hydrothermal clays, diagnostic of variable clay origins. We infer that the OT hydrothermal clay was primarily formed by the chemical alteration of detrital sediments subject to the hydrothermal fluids. The remarkably different compositions of hydrothermal clays between the sediment-rich back arc basin like OT and the sediment-starved ocean ridge suggest different physical and chemical processes of hydrothermal fluids and fluid-rock/sediment reactions under various geologic settings.

Sedimentary history and chemical characteristics of clay minerals from the Bengal Fan

The purpose of this study is to clarify the sedimentary history and chemical characteristics of clay minerals found in sediments deposited in the distal part of the Bengal Fan since the Himalayas were uplifted 17 m.y. ago. A total of seventy-eight samples were collected from three drilled cores which were to be used for the clay mineral analyses by means of XRD and ATEM. The results obtained from the analyses show that individual clay mineral species in the sediment samples at each site have similar features when the samples are of the same age, whereas these species have different features in samples of differing geological ages. Detrital clay minerals such as illite and chlorite were deposited in greater amounts than kaolinite and smectite during the Early to Middle Miocene. This means that the Himalayan uplift was vigorous at least until the Middle Miocene. In the Pliocene chemical weathering was more prevalent so that instead, in the distal part of the Bengal Fan, kaolinite shows the highest concentrations. This would accord with weaker uplift in the Himalayas. In the Pleistocene period, vigorous Himalayan uplift is characterized by illite-rich sediment in place of kaolinite. In the Holocene, smectite shows the highest concentration in place of the illite and kaolinite which were the predominant clay minerals of the earlier periods. Increasing smectite concentration suggests the Himalayan uplift to have been stable after the Pleistocene period. The smectite analyzed here is found to be dioctahedral Fe-beidellite, and it originated largely from the augite-basalt on the Indian Deccan Traps. The tri-octahedral chlorite is subdivided into three sub-species, an Fe-type, a Mg-type and an intermediate type. The mica clay mineral can be identified as di-octahedral illite which is rich in potassium. The chemical composition and morphology of each clay mineral appears to exhibit no change with burial depth in the sedimentary columns. This implies that there was no systematic transformation of clay minerals with time.