Distribution of polycyclic aromatic hydrocarbons in eolian and eolian-deluvial sediments from the North Iceland

This work considers results of a study of Holocene cover sediments in Iceland. They are largely composed of wind-transported palagonitized hyaloclastite particles and coeval horizons of acid and basic tephras. It is established that polyciclic aromatic hydrocarbons (PAH) are released from basaltic glass in natural environments only in case of intense physicochemical alteration and destruction of its structure. This process does not influence PAH composition and their quantitative proportions. No new PAH formed during several thousands of years in Holocene section. Hydrocarbons are transferred from fixed state in basaltic glass into free state in palagonites practically without any changes. PAH were mainly redeposited by winds, derived together with palagonite from weathered hyaloclastites, and precipitated from atmosphere with tephra during eruptions.

X-ray fluorescence scanning of discrete samples on the Schwalbenberg II loess-paleosol sequence, raw data, magnetic susceptibility, organic carbon and U-ratio as grainsize index

The Schwalbenberg II loess-paleosol sequence (LPS) denotes a key site for Marine Isotope Stage (MIS 3) in Western Europe owing to eight succeeding cambisols, which primarily constitute the Ahrgau Subformation. Therefore, this LPS qualifies as a test candidate for the potential of temporal high-resolution geochemical data obtained X-ray fluorescence (XRF) scanning of discrete samplesproviding a fast and non-destructive tool for determining the element composition. The geochemical data is first contextualized to existing proxy data such as magnetic susceptibility (MS) and organic carbon (Corg) and then aggregated to element log ratios characteristic for weathering intensity [LOG (Ca/Sr), LOG (Rb/Sr), LOG (Ba/Sr), LOG (Rb/K)] and dust provenance [LOG (Ti/Zr), LOG (Ti/Al), LOG (Si/Al)]. Generally, an interpretation of rock magnetic particles is challenged in western Europe, where not only magnetic enhancement but also depletion plays a role. Our data indicates leaching and top-soil erosion induced MS depletion at the Schwalbenberg II LPS. Besides weathering, LOG (Ca/Sr) is susceptible for secondary calcification. Thus, also LOG (Rb/Sr) and LOG (Ba/Sr) are shown to be influenced by calcification dynamics. Consequently, LOG (Rb/K) seems to be the most suitable weathering index identifying the Sinzig Soils S1 and S2 as the most pronounced paleosols for this site. Sinzig Soil S3 is enclosed by gelic gleysols and in contrast to S1 and S2 only initially weathered pointing to colder climate conditions. Also the Remagen Soils are characterized by subtle to moderate positive excursions in the weathering indices. Comparing the Schwalbenberg II LPS with the nearby Eifel Lake Sediment Archive (ELSA) and other more distant German, Austrian and Czech LPS while discussing time and climate as limiting factors for pedogenesis, we suggest that the lithologically determined paleosols are in-situ soil formations. The provenance indices document a Zr-enrichment at the transition from the Ahrgau to the Hesbaye Subformation. This is explained by a conceptual model incorporating multiple sediment recycling and sorting effects in eolian and fluvial domains.

Major, trace and rare earth element concentrations of sediments from ODP Leg 207 sites

The Cretaceous and Paleogene sediments recovered during Ocean Drilling Program Leg 207 can be divided into three broad modes of deposition: synrift clastics (lithologic Unit V), organic matter-rich, laminated black shales (Unit IV), and open-marine chalk and calcareous claystones (Units III-I). The aim of this study is to provide a quantitative geochemical characterization of sediments representing these five lithologic units. For this work we used the residues (squeeze cakes) obtained from pore water sampling. Samples were analyzed for bulk parameters (total inorganic carbon, total organic carbon, and S) and by X-ray fluorescence for major (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, and P) and selected minor (As, Ba, Co, Cr, Cu, Mo, Ni, Pb, Rb, Sr, U, V, Y, Zn, and Zr) elements. Inductively coupled plasma-mass spectrometry analyses for rare earth elements (REEs) were performed on acid digestions of the squeeze cake samples from Site 1258. The major element composition is governed by the mixture of a terrigenous detrital component of roughly average shale (AS) composition with biogenous carbonate and silica. The composition of the terrigenous detritus is close to AS in Units II-IV. For Unit I, a more weathered terrigenous source is suggested. Carbonate contents reach >60 wt% on average in chalks and calcareous claystones of Units II-IV. The SiO2 contribution in excess of the normal terrigenous-detrital background indicates the presence of biogenous silica, with highest amounts in Units II and III. The contents of coarse-grained material (quartz) are enhanced in Unit V, where Ti and Zr contents are also high. This indicates a high-energy depositional environment. REE patterns are generally similar to AS. A more pronounced negative Ce anomaly in Unit IV may indicate low-oxygen conditions in the water column. The Cretaceous black shales of Unit IV are clearly enriched in redox-sensitive and stable sulfide-forming elements (Mo, V, Zn, and As). High phosphate contents point toward enhanced nutrient supply and high bioproductivity. Ba/Al ratios are rather high throughout Unit IV despite the absence of sulfate in the pore water, indicating elevated primary production. Manganese contents are extremely low for most of the interval studied. Such an Mn depletion is only possible in an environment where Mn was mobilized and transported into an expanded oxygen minimum zone ("open system"). The sulfur contents show a complete sulfidation of the reactive iron of Unit IV and a significant excess of sulfur relative to that of iron, which indicates that part of the sulfur was incorporated into organic matter. We suppose extreme paleoenvironmental conditions during black shale deposition: high bioproductivity like in recent coastal upwelling settings together with severe oxygen depletion if not presence of hydrogen sulfide in the water column.

Geochemistry of ODP Hole 121-752A

The present study involves the analysis and interpretation of geochemical data from a suite of sediment samples recovered at ODP Hole 752A. The samples encompass the time period that includes the lithospheric extension and uplift of Broken Ridge, and they record deposition below and above the mid-Eocene angular unconformity that denotes this uplift. A Q-mode factor analysis of the geochemical data indicates that the sediments in this section are composed of a mixture of three geochemical end members that collectively account for 94.2% of the total variance in the data. An examination of interelement ratios for each of these end members suggests that they represent the following sedimentary components: (1) a biogenic component, (2) a volcanogenic component, and (3) a hydrothermal component. The flux of the biogenic component decreases almost thirtyfold across the Eocene unconformity. This drastic reduction in the deposition of biogenic materials corresponds to the almost complete disappearance of chert layers, diatoms, and siliceous microfossils and is coincident with the uplift of Broken Ridge. The volcanogenic component is similar in composition to Santonian ash recovered at Hole 755A on Broken Ridge and is the apparent source of the Fe-stained sediment that immediately overlies the angular unconformity. This finding suggests that significant amounts of Santonian ash were subaerially exposed, weathered, and redeposited and is consistent with data that suggest that the vertical uplift of Broken Ridge was both rapid and extensive. The greatest flux of hydrothermal materials is recorded in the sediments immediately below the angular unconformity. This implies that the uplift of Broken Ridge was preceded by a significant amount of rifting, during which faulting and fracturing of the lithosphere led to enhanced hydrothermal circulation. This time sequence of events is consistent with (but not necessarily diagnostic of) the passive model of lithospheric extension and uplift.

(Table 1) K-Ar age determinations on biotite from coarse sand within DSDP Sample 72-516F-76-4,107-115

Qualitative petrographic study of selected clastic horizons within the Eocene section of Hole 516F has revealed the presence of abundant fine-grained lithic fragments, probably volcanic, along with coarser fragments of quartz and feldspar apparently derived from a nearby plutonic terrain. In detail, poor sorting, presence of graded bedding, and an abundance of clay suggest these are turbidite horizons locally derived from a mixed volcanic/plutonic terrain, possibly with some direct contribution from contemporary volcanic ash falls. A progressive increase in plutonic versus volcanic components with time is, however, more consistent with an erosional origin for most of this material. Unusual euhedral dark biotite is abundant in several of the lower clastic horizons; it is most easily interpreted as microphenocrysts weathered in situ out of alkalic volcanic ash. Biotite separated from Sample 516F-76-4,107-115 cm, has been dated by the K-Ar method at about 46 Ma. Alkaline volcanoes active on the Rio Grande Rise in the middle Eocene would be the most probable source of this ash and would be consistent with other evidence for potassic, alkaline volcanism along the Rio Grande Rise and at the Tristan da Cunha hot spot.

(Table 1) Estimated e-Nd(0) input calculated using the relative fraction of ODP Hole 105-647A amphibole grains originated from different provinces of the North America

Many marine radiogenic isotope records show both spatial and temporal variations, reflecting both the degree of mixing of distinct sources in the oceans and changes in the distribution of chemical weathering on the continents. However, changes in weathering and transport processes may themselves affect the composition of radiogenic isotopes released into seawater. The provenance of physically weathered material in the Labrador Sea, constrained through the use of Ar-Ar ages of individual detrital minerals, has been used to estimate the relative contributions of chemically weathered terranes releasing radiogenic isotopes into the Labrador Sea. A simple box-model approach for balancing observed Nd-isotope variations has been used to constrain the relative importance of localised input in the Labrador Sea, and the subsequent mixing of Labrador Sea Water into North Atlantic Deep-Water. The long-term pattern of erosion and deep-water formation around the North Atlantic seems to have been a relatively stable feature since 1.5 Ma, although there has been a dramatic shift in the nature of physical and chemical weathering affecting the release of Hf and Pb isotopes. The modelled Nd isotopes imply a relative decrease in water mass advection into the Labrador Sea between 2.4 and 1.5 Ma, accompanied by a decrease in the rate of overturning, possibly caused by an increased freshwater input into the Labrador Sea.

Hydrocarbons in bottom sediments during a seasonal flood 2005 in the Dvina River estuary

The results of studying hydrocarbons during the flood in May 2005 are discussed. The concentration of aliphatic and polycyclic aromatic hydrocarbons are shown to match their concentrations in water areas with steady input of pollutants. Weathered oil and pyrogenic compounds dominated in their composition. The geochemical barrier the Northern Dvina River-Dvina Gulf is shown to become a filter during floods and prevents pollutants from penetrating into the White Sea.

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.

Clay mineral assemblages for the last 10 Ma off northeastern Australia

Clay mineral assemblages for the last 10 m.y. are described for Site 823, at 16°S in the Queensland Trough, to the northeast of Australia. Largely unaffected by diagenetic influences, these mostly express the evolution of northeastern Australian continental environments during the late Neogene: (1) beginning during the late Miocene at about 7.0 Ma is an increase of illite derived from rocky substrates at the expense of smectite from deeply weathered soils; this increase was the result of increasing aridity in the Australian interior and globally cooler temperatures, associated with increases in Antarctic glaciation; (2) concomitant and further increases of kaolinite fluxes to the Queensland Trough during the late Miocene-early Pliocene largely reflect an increase in rainfall in northeastern Australia; (3) increases in both soil- and rock-derived minerals probably intensified as a result of late Neogene uplift of the eastern highlands; (4) clay-mineral associations during the Pliocene and Pleistocene display minor variations only and probably resulted in part from differential settling and sea-level changes; (5) similar trends of clay-mineral variations occur at both ODP Site 823 and DSDP Site 588 (Lord Howe Rise). Less abundant kaolinite relative to illite at Site 588 nevertheless suggests a southward decrease of continental humidity and/or of the eastern highlands uplift; (6) influences of global climate and oceanic and atmospheric circulations on clay-mineral associations dominated during the late Miocene and were progressively replaced by influences of more regional environmental variations during the Pliocene and especially the Pleistocene.

Composition of Cretaceous basalts from DSDP Hole 16-163

Basalt underlying early Campanian chalk at Deep Sea Drilling Project (DSDP) Site 163 is divided into seven extrusive cooling units bounded by glassy margins. The margins have dips of 15° to 70°, suggestive of pillow flows rather than tabular flows. The margins are fresh sideromelane (glass) grading inward to opaque and reddish-brown globules containing microcrystalline material with radial, undulose extinction. Relative to adjacent sideromelane, the reddish-brown globules are enriched in sodium and calcium, whereas the opaque globules are depleted in these elements and enriched in iron and magnesium. It appears that basalt just inside the pillow margins has differentiated in place into globules of two distinct compositions. This globule zone grades inward to less rapidly cooled pyroxene varioles and intergrowths of plagioclase and opaque minerals. In the center of the thicker cooling units, the texture is diabasic. Alteration and calcite vein abundance are greatest at pillow margins and decrease inward; the interior of the thickest cooling unit is only slightly altered, and calcite veins are absent. Chemical analysis of whole rock by atomic absorption spectrophotometry, and of sideromelane by electron microprobe, indicates that the rock is a slightly weathered tholeiite. The atomic absorption analyses, except the one nearest the top of the basalt, are relatively uniform and similar to the sideromelane microprobe analyses, including those near the top of the basalt. This suggests that deep penetration is not necessary to get through the severely altered layer at the basalt surface, and that within this altered layer, analyses of sideromelane may be more representative of crustal composition than analyses of whole rock.

Strontium, oxygen and hydrogen isotope ratios of basalts from DSDP Hole 504B

DSDP Hole 504B was drilled into 6 Ma crust, about 200 km south of the Costa Rica Rift, Galapagos Spreading Center, penetrating 1.35 km into a section that can be divided into four zones-Zone I: oxic submarine weathering; Zone II: anoxic alteration; Zones III and IV: hydrothermal alteration to greenschist facies. In Zone III there is intense veining of pillow basalts. Zone IV consists of altered sheeted dikes. Isotopic geochemical signatures in relation to the alteration zones are recorded in Hole 504B, as follows: Zone Depth(m) Average87Sr/86Sr Average delta18O (?) Average deltaD (?) I 275-550 0.7032 7.3 -63 II 550-890 0.7029 6.5 -45 III 890-1050 0.7035 5.6 -31 IV 1050-1350 0.7032 5.5 -36 Alteration temperatures are as low as 10°C in Zones I and II based on oxygen isotope fractionation. Strontium isotopic data indicate that a circulation of seawater is much more restricted in Zone II than in Zone I. Fluid inclusion measurements of vein quartz indicate the alteration temperature was mainly 300 +/- 20°C in Zones III and IV, which is consistent with secondary mineral assemblages. The strontium, oxygen, and hydrogen isotopic compositions of hydrothermal fluids which were responsible for the greenschist facies alteration in Zones III and IV are estimated to be 0.7037, 2?, and 3?, respectively. Strontium and oxygen isotope data indicate that completely altered portions of greenstones and vein minerals were in equilibrium with modified seawater under low water/rock ratios (in weight) of about 1.6. This value is close to that of the end-member hydrothermal fluids issuing at 21°N EPR. Basement rocks are not completely hydrothermally altered. About 32% of the greenstones in Zones III and IV have escaped alteration. Thus 1 g of fresh basalt including the 32% unaltered portion are required in order to make 1 g of end-member solution from fresh seawater in water-rock reactions.

Accumulation and composition of terrigenous material on Ceara rise over the past 55 Ma

Ceara Rise, located east the Amazon River mouth, is covered with a thick blanket of pelagic carbonate and hemipelagic terrigenous sediment. The terrigenous component has been extracted from 57 bulk sediment samples at Ocean Drilling Program (ODP) Sites 925 and 929 on Ceara Rise to obtain a Cenozoic record of riverine discharge from northern South America. From the early Eocene to early Miocene (55-20 Ma), terrigenous accumulation was dominated by moderate amounts of generally large-grained, gray to green sediment especially depleted in elements that are enriched in post-Archaean shale (e.g. Cs, Th, Yb). However, pulsed inputs of relatively small-grained, gray to green terrigenous sediment less depleted in the above elements occurred in the late Eocene and Oligocene. The accumulation of terrigenous sediment decreased significantly until 16.5 Ma. In the middle Miocene (16.5-13 Ma), terrigenous accumulation was dominated by small amounts of small-grained, tan sediment notably depleted in Na and heavy rare earth elements. The accumulation rate of terrigenous sediment increased markedly from the latest Miocene (10 Ma) to the present day, a change characterized by deposition of gray-green sediment enriched in elements that are enriched in post-Archaean shale. Observed changes in terrigenous sediment at Ceara Rise record tectonism and erosion in northern South America. The Brazil and Guyana shields supplied sediment to the eastern South American margin until the middle Miocene (20-16.5 Ma) when a period of thrusting, shortening and uplift changed the source region, probably first to highly weathered and proximal Phanerozoic sediments. By the late Miocene (9 Ma), there was a transcontinental connection between the Andes and eastern South America. Weathering products derived from the Andes have increasingly dominated terrigenous deposition at Ceara Rise since the Late Miocene and especially since the late Pliocene.