Biomarker and XRD results for the last 3.4 Ma from IODP Site 306-U1313

Various types of abrupt/millennial-scale climate variability such as Dansgaard/Oeschger and Heinrich Events characterized the last glacial period. Over the last decade, a number of studies demonstrated that such millennial-scale climate variability was not limited to the last glacial but inherent to Quaternary climate. Here we review the occurrence and origin of millennial ice-rafting events in the North Atlantic during the late Pliocene and Pleistocene (last 3.4 Ma) with a special focus on North Atlantic Hudson Strait (HS) Heinrich(-like) Events. Besides a clear biomarker signature, we show that Heinrich Layers 5, 4, 2, and 1 in marine sediment cores from across the North Atlantic all bear the organic geochemical fingerprint of the Hudson area. Using this framework and combining previously published results, detailed investigations into the organic and inorganic chemistry of ice-rafted debris (IRD) found across the North Atlantic demonstrate that prior to MIS 16 (~ 650 ka) IRD in the North Atlantic did not originate from the Hudson area of northern Canada. The signature of this early IRD is distinctly different compared to that of HS Heinrich Layers. Rather ice-rafting events during the late Pliocene and early Pleistocene predominantly emanated from the calving of the Greenland and Fennoscandian ice sheets and possibly minor contributions from local ice streams from the North American and British ice sheets. Compared to North Atlantic HS Heinrich Events, these early Pleistocene IRD-events had a limited impact on surface water characteristics in the North Atlantic. North Atlantic HS Heinrich(-like) Events first occurred during MIS 16. At the same time, the dominant frequency in silicate-rich IRD accumulation shifted from the obliquity (41-ka) to a 100-ka frequency across the North Atlantic. Iceberg survivability or a change in iceberg trajectory likely did not control this change in IRD-regime. These results lend further support for the existing hypothesis that an increase in size (thickness) of the Laurentide ice sheet controls the occurrence of North Atlantic HS Heinrich Events, favoring an internal dynamic mechanism for their occurrence.

Mineral composition, major element oxides and trace element concentration of sediments from ODP Leg 180 sites

Middle Miocene to Holocene fine-grained argillaceous sediments (clays, claystones/muds, and mudstones), which volumetrically dominated the sediment recovery in the Woodlark Basin during Leg 180, were chemically analyzed for major elements, trace elements, and some rare earth elements by X-ray fluorescence. Selected samples also underwent X-ray diffraction (XRD) analysis for mineral determination. The results shed light on sediment provenance when combined with shipboard sediment descriptions, smear slide study, and XRD. The oldest sediments recovered (Site 1108) of middle-late Miocene age include volcanogenic muds with distinctive high MgO and K2O, indicative of a relatively basic calc-alkaline source related to an inferred Miocene forearc succession. The forearc basement, composed of diabase and basalt, was locally exposed (Site 1109) and eroded in the late Miocene (<5.4-9.93 Ma), giving rise to fluvial conglomerates (Sites 1109, 1115, and 1118). Chemically distinctive fine-grained claystones and siltstones (with relatively high Ti, low K) are compatible with derivation from tropically weathered basic igneous rocks, correlated with the Paleogene Papuan ophiolite. Overlying latest Miocene-Pleistocene fine-grained sediments throughout the Woodlark Basin were partly derived from calc-alkaline volcanic sources. However, relatively high abundances of Al2O3 and related element oxides (K2O and Na2O) and trace elements (e.g., Rb and Y) reflect an additional terrigenous input throughout the basin, correlated with pelitic metamorphic rocks exposed on Papua New Guinea and adjacent areas. In addition, sporadic high abundances of Cr and Ni, some other trace metals, and related minerals (talc, crysotile, and chlorite) reflect input from an ophiolitic terrain dominated by ultramafic rocks, correlated with the Paleogene Papuan ophiolite. The source areas possibly included serpentinized ultramafic ophiolitic rocks exposed in the Papua New Guinea interior highlands. Chemical evidence further indicates that fine-grained terrigenous sediment reached the Woodlark Basin throughout its entire late Miocene-Holocene history. Distinctive high-K volcanogenic muds rich in tephra and volcanic ash layers that appear at <2.3 Ma (Sites 1109 and 1115) are indicative of high-K calc-alkaline volcanic centers, possibly located in the Dawson Strait, Moresby Strait, or Dobu Seamount area. Chemical diagenesis of fine-grained sediments within the Woodlark Basin is reflected in clay neomorphism and localized formation of minerals including dolomite, ankerite, and zeolite but has had little effect on the bulk chemical composition of most samples.

Temperature and d18O measurements from different ODP Sites at the shelf and upper slope of the Peru Margin

The first experimentally determined temperature dependent oxygen-18 fractionation factor between dolomite and water at low temperatures [Vasconcelos et al. 1995 doi:10.1130/G20992.1] allows now the precise calculation of temperatures during early diagenetic dolomite precipitation. We use d18O values of early diagenetic dolomite beds sampled during ODP Legs 112 and 201 on the Peru continental margin (Sites 1227, 1228 and 1229) [Meister et al. 2007, doi:10.1111/j.1365-3091.2007.00870.x] to calculate paleo-porewater temperatures at the time of dolomite precipitation. We assumed unaltered seawater d18O values in the porewater, which is supported by d18O values of the modern porewater presented in this study. The dolomite layers in the Pleistocene part of the sedimentary columns showed oxygen isotope temperatures up to 5 °C lower than today. Since Sites 1228 and 1229 are located at 150 and 250 m below sealevel, respectively, their paleo-porewater temperatures would be influenced by considerably colder surface water during glacial sealevel lowstands. Thus, Pleistocene dolomite layers in the Peru Continental margin probably formed during glacial times. This finding is consistent with a model for dolomite precipitation in the Peru Margin recently discussed by Meister et al. [Meister et al. 2007, doi:10.1111/j.1365-3091.2007.00870.x], where dolomite forms episodically at the sulphate methane interface. It was shown that the sulphate methane interface migrates upwards and downwards within the sedimentary column, but dolomite layers may only form when the sulphate-methane interface stays at a fixed depth for a sufficient amount of time. We hypothesize that the sulphate-methane interface persists within TOC-rich interglacial sediments, while this zone is buried by TOC-poor sedimentation during glacial times. Thus, the presented oxygen isotope data provide additional information on the timing of early diagenetic dolomite formation and a possible link between episodicity in dolomite formation and sealevel variations. A similar link between early diagenesis and oceanography may also explain spacing of dolomite layers in a Milankovitch type pattern observed in the geological record, such as in the Miocene Monterey Formation.

Geochemical analysis of sediments from three coring sites in the Mediterranean

In a gravity core from the eastern Mediterranean Sea, a chemically and mineralogically distinct, 5.5-cm-thick layer is present above sapropel S-1 and overlain by hemipelagic marls. Calcite is completely absent in this exotic layer, dolomite is present only in small amounts, and the Cr concentrations are significantly enhanced. The layer was deposited primarily under reducing conditions, but the distributions of redox-sensitive elements show that a large part of the exotic layer is now oxidised by a downward-progressing oxidation front. Sediments from within the nearby anoxic, hypersaline Urania Basin are similar to those from the exotic layer, in particular in S-, C-, and O-isotope distributions of pyrite and dolomite, as well as increased Cr concentrations. Mud expulsion due to expansion of gas-rich mud is proposed to explain the presence of the exotic layer outside the Urania Basin. The deposition of an anoxic layer above S-1 shielded the sapropel from oxidation which resulted in the rare occurrence of a complete preservation of S-1 and provides the first minimum age for the start of anoxic mud accumulation in the Urania Basin.

Composition of suspended matter and bottom sediments from the North Dvina mouth area

Grain-size, mineral and chemical compositions of suspended particulate matter (SPM) from waters of the Severnaya (North) Dvina River mouth area during the spring flood in May 2004 is studied. Data published on composition of riverine SPM in the White Sea basin are very poor. The spring flood period when more than half of annual runoff is supplied from the river to the sea in during short time is understood more poorly. The paper considers comparison results of the grain size compositions of SPM and bottom sediments. Data of laser and hydraulic techniques of grain size analysis are compared. Short-period variations of SPM concentration and composition representing two diurnal peaks of the tide level are studied. It is found that SPM is mainly transferred during the spring flood as mineral aggregates up to 40 µm diameter. Sandy-silty fraction of riverine SPM settles in delta branches and channels, and bulk of clay-size material is supplied to the sea. Mineral and chemical compositions of SPM from the North Dvina River are determined by supply of material from the drainage basin. This material is subjected to intense mechanic separation during transfer to the sea. Key regularities of formation of mineral composition of SPM during the flood time are revealed. Effect of SPM grain size composition on distribution of minerals and chemical elements in study in the dynamic system of the river mouth area are characterized.

(Supplement) Groundwater quality in Lahore Pakistan: emphasis on Arsenic and Fluoride levels

The dataset provides detailed information on the study that was conducted in Lahore's 7 major towns. The sample was taken from 472 tubewells and analyzed for major cations and anions using APHA 2012 techniques as explained herein. Besides, E.coli determination was done to check for microbial contamination. The data includes results from PHREEQC modeling of As(III)/ As(V) species and saturation indices as well as Aquachem's computed hydrochemical water facies. The WHO (2011) and EPA standards included in Aquachem identified the parameters that where in violation. Bicarbonates dominated the groundwater types with 50.21% of the samples exceeding the EPA maximum permissible limit of 250 mg/L in drinking water. Similarly, 30.51% of the samples had TDS values greater than 500 mg/L while 85.38 % of the samples exceed 10 µg/L threshold limit value of arsenic. Also, instances of high magnesium hazard values were observed which requires constant assessment if the groundwater is used for irrigation. Higher than 50% MH values are detrimental to crops which may reduce the expected yields. The membrane filtration technique using m-Endo Agar indicated that 3.59% samples had TNC (too numerous to count) values for E.coli while 5.06% showed values higher than 0 cfu/ 100 ml acceptable value in drinking water. Any traces of E-coli in a groundwater sample indicate recent fecal contamination. Such outcomes signify presence of enteric pathogens. If the groundwater is not properly dosed with disinfectants it may cause harm to human health. It is concluded that more studies are needed and proper groundwater management implement to safeguard the lives of communities that depend solely on groundwater in the city.

(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

Minerals of bulk samples and clay fraction at DSDP Leg 80 Holes

At the request of the Leg 80 scientific party, selected samples of Cretaceous age were processed by X-ray diffraction at the mineralogy laboratories at the Ecole des Mines (Albian to Late Cretaceous samples) and at the Institut de Géologie at Dijon (Barremian samples). The results were used in developing the lithostratigraphy and sedimentology discussed in this volume by Rat et al. 1985 (doi:10.2973/dsdp.proc.80.140.1985) in their study of Barremian-Albian paleoenvironment, by Graciansky and Gillot in their study of Albian and Cenomanian limestones, and by Graciansky and Bourbon in their paleoenvironmental reconstructions for the Late Cretaceous chalks.

Mineralogy, lithology and stable isotope composition of diagenetic siliceous rocks from ODP Leg 129 sites

Ocean Drilling Program Leg 129 recovered chert, porcellanite, and radiolarite from Middle Jurassic to lower Miocene strata from the western Pacific that formed by different processes and within distinct host rocks. These cherts and porcellanites formed by (1) replacement of chalk or limestone, (2) silicification and in-situ silica phase-transformation of bedded clay-bearing biosiliceous deposits, (3) high-temperature silicification adjacent to volcanic flows or sills, and (4) silica phase-transformation of mixed biosiliceous-volcaniclastic sediments. Petrologic and O-isotopic studies highlight the key importance of permeability and time in controlling the formation of dense cherts and porcellanites. The formation of dense, vitreous cherts apparently requires the local addition and concentration of silica. The influence of permeability is shown by two examples, in which: (1) fragments of originally identical radiolarite that were differentially isolated from pore-water circulation by cement-filled fractures were silicified to different degrees, and (2) by the development of secondary porosity during the opal-CT to quartz inversion within conditions of negligible permeability. The importance of time is shown by the presence of quartz chert below, but not above, a Paleogene hiatus at Site 802, indicating that between 30 and 52 m.y. was required for the formation of quartz chert within calcareous-siliceous sediments. The oxygen-isotopic composition for all Leg 129 carbonate- and Fe/Mn-oxide-free whole-rock samples of chert and porcellanite range widely from d18O = 27.8 per mil to 39.8 per mil vs. V-SMOW. Opal-CT samples are consistently richer in 18O (34.1 per mil to 39.3 per mil) than quartz subsamples (27.8 per mil to 35.7 per mil). Using the O-isotopic fractionation expression for quartz-water of Knauth and Epstein (1976) and assuming d18Opore water = -1.0 per mil, model temperatures of formation are 7°-26°C for carbonate-replacement quartz cherts, 22°-25°C for bedded quartz cherts, and 32°-34°C for thermal quartz cherts. Large variations in O-isotopic composition exist at the same burial depth between co-existing silica phases in the same sample and within the same phase in adjacent lithologies. For example, quartz has a wide range of isotopic compositions within a single breccia sample; d18O = 33.4 per mil and 28.0 per mil for early and late stages of fracture-filling cementation, and 31.6 per mil and 30.2 per mil for microcrystalline quartz precipitation within enclosed chert and radiolarite fragments. Similarly, opal-CT d101 spacing varies across lithologic or diagenetic boundaries within single samples. Co-occurring opal-CT and chalcedonic quartz in shallowly buried chert and porcellanite from Sites 800 and 801 have an 8.7 per mil difference in d18O, suggesting that pore waters in the Pigafetta Basin underwent a Tertiary shift to strongly 18O-depleted values due to alteration of underlying Aptian to Albian-Cenomanian volcaniclastic deposits after opal-CT precipitation, but prior to precipitation of microfossil-filling chalcedony.

Compositions of paleosols from the Salarevo Formation, Sukhona River valley (Severnaya Dvina basin)

Paleosols crop out in the Sukhona River valley as several members up to 10 m thick embedded into the Salarevo Formation sediments. Principal characteristics of the paleosols include a dense network of root channels, indications of eluvial gley alteration, redistribution and formation of secondary carbonates represented by several generations, and formation of block-prismatic soil structure with specific clayey films at structural jointing faces. The paleosols are divided into a number of genetically interrelated horizons (from top to bottom): presumably organogenic accumulation (AElg), eluvial gley horizon (Elg), illuvial horizons (B1 and B2), illuvial gley horizon (Bg), and transitional horizons (ElBg and BElg). The paleosols formed under conditions of a semiarid climate with sharp seasonal or secular and multisecular oscillations of atmospheric precipitation. Such soils point to specific ecological environments existed in the northern semiarid belt of the Earth before the greatest (in Phanerozoic) biospheric crisis at the Permian-Triassic boundary.