The Cenomanian/Turronian Boundary Event at ODP Hole 103-641A

Drilling at ODP Site 641 (on the western margin of Galicia Bank, off northwestern Spain) revealed a thin, but pronounced, interval of black shale and gray-green claystone. Our high-resolution study combines the sedimentology, micropaleontology (palynomorphs and others), organic and inorganic geochemistry, and isotopic values of this layer to demonstrate the distinct nature of the sediment and prove that the sequence represents the local sedimentary expression of the global Cenomanian/Turonian Oceanic Anoxic Event (OAE) of Schlanger and Jenkyns (1976), Arthur and Schlanger (1979), and Jenkyns (1980), also called the Cenomanian/Turonian Boundary Event (CTBE). The most striking evidence is that the strong positive d13C excursion characterizing the CTBE sequences in shallow areas can be traced into a pronounced deep-sea expression, thus providing a good stratigraphic marker for the CTBE in various paleosettings. The isotopic excursion at Site 641 coincides with an extremely enriched trace metal content, with values that were previously unknown for the Cretaceous Atlantic. Similar to other CTBE occurrences, the organic carbon content is high (up to 11%) and the organic matter is of dominantly marine origin (kerogen type II). The bulk mineralogy of the CTBE sediments does not differ significantly from the general trend of Cretaceous North Atlantic sediments (dominance of smectite and zeolite with minor amounts of illite and scattered palygorskite, kaolinite, and chlorite); thus, no evidence for either increased volcanic activity nor a drastic climatic change in the borderlands was found. Results from Site 641 are compared with the CTBE section found at Site 398, DSDP Leg 47B (Vigo Seamount at the southern end of the Galicia Bank).

Geochemistry of Cenozoic sediments from the central Artic Ocean

Integrated Ocean Drilling Program (IODP) Expedition 302 (Arctic Coring Expedition, ACEX) recovered a unique sediment record from the central Arctic Ocean, revealing that this region underwent major environmental fluctuations since the Late Cretaceous. Major and trace element composition of 1,300 samples were determined using X-ray fluorescence (XRF). The results show significant compositional variability of the sediments with depth that can be attributed to changes in (a) provenance and pathways of detrital material, (b) paleoenvironmental conditions and depositional processes, and (c) diagenetic overprint of the primary record. In addition to existing lithological units, we introduce new geochemical units for a more process-related approach interpreting the ACEX record. In detail, via the geochemical signature of Siberian flood basalts we are able to reconstruct the discontinuous rifting and deepening of the central Lomonosov Ridge during the Paleogene, accompanied by changing current regimes and the onset of sea ice. Eocene biosiliceous sedimentation took place in a relatively shallow setting under predominantly anoxic bottom water conditions, causing a positive anoxia-productivity feedback, although water column stratification was repeatedly interrupted by ventilation events. Anoxic to sulfidic conditions were even more extreme after biosilica production ceased, and significant amounts of pyrite were deposited on the Lomonosov Ridge. Especially in organic matter-rich Paleogene deposits, diagenetic processes obscured the paleoenvironmental signals. Fundamental environmental changes occurred in the Middle Eocene, but geochemical and micropaleontological proxies point not to the identical sediment depth. After approximately 26 Ma of non-deposition or erosion, the Middle Miocene record shows the transition to dominantly oxic bottom water conditions, although suboxic diagenesis seemingly affected these deposits.

Metal content of nodules at Sea Scope stations based upon different analysis methods

Information on possible resource value of sea floor manganese nodule deposits in the eastern north Pacific has been obtained by a study of records and collections of the 1972 Sea Scope Expedition.

Geochemistry of mafic clasts of ODP Holes 125-778A and 125-779A

Clasts of metamorphosed mafic igneous rock of diverse composition were recovered in two drill sites on a serpentine mud volcano in the outer Mariana forearc during Ocean Drilling Program Leg 125. These clasts are xenolithic fragments that have been entrained in the rising serpentine mud, and make up less that 9% of the total rock recovered at Sites 778 and 779. Most samples are metabasalt or metadiabase, although one clast of possible boninite and one cumulate gabbro were recovered. On the basis of trace element signatures, samples are interpreted to represent both arc-derived and mid-ocean ridge-derived compositions. Rocks with extremely low TiO2 (<0.3 wt%) and Zr (<30 ppm) are similar to boninite series rocks. Samples with low TiO2 (<0.9 wt%) and Zr (<50 ppm) and extreme potassium enrichment (K2O/Na2O >3.9) may represent island arc rocks similar to shoshonites. However, the K2O/Na2O ratios are much higher than those reported for shoshonites from modem or ancient arcs and may be the result of metamorphism. Samples with moderate TiO2 (1.4 to 1.5 wt%) and Zr (72 to 85 ppm) are similar to rocks from mid-ocean ridges. A few samples have TiO2 and Zr intermediate between island arc and mid-ocean ridge basalt-like rocks. Two samples have high iron (Fe2O3* = >12.8 to 18.5 wt%) (Fe2O3* = total iron calculated as Fe2O3) and TiO2 (>2.3 wt%) and resemble FeTi basalt recovered from mid-ocean ridges. Metamorphism in most samples ranges from low-temperature zeolite, typical of ocean floor weathering, to prehnite-pumpellyite facies and perhaps lower greenschist. Blue amphibole and lawsonite minerals are present in several samples. One diabase clast (Sample 9) exhibits Ca enrichment, similar to rodingite metamorphism, typical of mafic blocks in serpentinized masses. The presence of both low-grade (clays and zeolites) and higher grade (lawsonite) metamorphism indicates retrograde processes in these clasts. These clasts are fragments of the forearc crust and possibly of the subducting plate that have been entrained in the rising serpentine and may represent the deepest mafic rocks ever recovered from the Mariana forearc. The variable compositions and degree of metamorphism of these clasts requires at least two tectonic origins. The recovery of clasts with mid-ocean ridge and arc chemical affinities in a single drill hole requires these clasts to have been "mixed" on a small scale either (1) in the forearc crustal sequence, or (2) after inclusion in the rising serpentine mud. The source of the MORB-like samples and an explanation for the presence of both MORB-like and arc-like rocks in close proximity is critical to any model of the evolution of the Mariana forearc. The source of the MORB-like samples likely will be one (or more) of the following: (1) accretion of Pacific plate lithosphere, (2) remnants of original forearc crust (trapped plate), (3) volcanism in the supra-subduction zone (arc or forearc) environment, or (4) derivation from the subducting slab by faulting along the dÈcollement.

Geochemistry and petrology of ODP Leg 121 basalts

Basement lavas from Sites 756, 757, and 758 on Ninetyeast Ridge are tholeiitic basalts. Lavas from Sites 756 and 757 appear to be subaerial eruptives, but the lowermost flows from Hole 758A are pillow lavas. In contrast to the compositional variation during the waning stages of Hawaiian volcanism, no alkalic lavas have been recovered from Ninetyeast Ridge and highly evolved lavas were recovered from only one of seven drill sites (DSDP Site 214). All lavas from Site 758 have relatively high MgO contents (8-10 wt%), and they are less evolved than lavas from Sites 756 and 757. Although abundances of alkali metals in these Ninetyeast Ridge basalts were significantly modified by postmagmatic alteration, abundances of other elements reflect magmatic processes. At Site 757 most of the lavas are Plagioclase cumulates, but lava compositions require two compositionally distinct, AhCb-rich parental magmas, perhaps segregated at relatively low mantle pressures. In addition, at both Sites 756 and 758 more than one compositionally distinct parental magma is required. The compositions of these Ninetyeast Ridge lavas, especially those from Site 758, require a source component with a depleted composition; specifically, the abundance ratios Th/Ta, Th/La, Ba/Nb, Ba/La, and La/Ce in these lavas are generally less than the ratios inferred for primitive mantle. Lavas from Ninetyeast Ridge and the Kerguelen Archipelago have very different chondrite-normalized REE patterns, with lower light REE/heavy REE (LREE/HREE) ratios in lavas from Ninetyeast Ridge. However, lavas from Sites 757 and 758 have Pb isotope ratios that overlap with the field defined by lavas from the Kerguelen Archipelago (Weis and Frey, this volume). Therefore, these Ninetyeast Ridge lavas contain more of a component that is relatively depleted in LREE and other highly incompatible elements, but have similar amounts of the component that controls radiogenic Pb isotopes. A model involving mixing between components related to a depleted source and an enriched plume source has been proposed for the oldest Kerguelen Archipelago basalts and Ninetyeast Ridge lavas. Although the incompatible element characteristics of the Ninetyeast Ridge lavas are intermediate between depleted MORB and Kerguelen Archipelago basalts, these data are not consistent with a simple two-component mixing process. A more complex model is required.

Chemical composition and isotopic ratios of basic lavas from Iceland and the surrounding ocean floor

Major and trace dement data are used to establish the nature and extent of spatial and temporal chemical variations in basalts erupted in the Iceland region of the North Atlantic Ocean. The ocean floor samples are those recovered by legs 38 and 49 of the Deep Sea Drilling Project. Within each of the active zones on Iceland there are small scale variations in the light rare earth elements and ratios such as K/Y: several central complexes and their associated fissure swarms erupt basalts with values of K/Y distinct from those erupted at adjacent centres; also basalts showing a wide range of immobile trace element ratios occur together within single vertical sections and ocean floor drill holes. Although such variations can be explained in terms of the magmatic processes operating on Iceland they make extrapolations from single basalt samples to mantle sources underlying the outcrop of the sample highly tenuous. 87Sr/86Sr ratios measured for 25 of the samples indicate a total range from 0.7028 in a tholeiite from the Reykjanes Ridge to 0.7034 in an alkali basalt from Iceland and are consistent with other published ratios from the region. A positive correlation between 87Sr/86Sr and Ce/Yb ratios indicates the existence of systematic isotopic and elemental variations in the mantle source region. An approximately fivefold variation in Ce/Yb ratio observed in basalts with the same 87Sr/86Sr ratio implies that different degrees and types of partial melting have been involved in magma genesis from a single mantle composition. 87Sr/86Sr ratios above 0.7028, Th/U ratios close to 4 and La/Ta ratios close to 10 distinguish most basalts erupted in this part of the North Atlantic Ocean from normal mid-ocean ridge basalt (N-type MORB) - although N-type MORB has been erupted at extinct spreading axes just to the north and northeast of Iceland as well as the presently active Iceland-Jan Mayen Ridge. Comparisons with the hygromagmatophile element and radiogenic isotope ratios of MORB and the estimated primordial mantle indicate that the mantle sources producing Iceland basalts have undergone previous depletion followed by more recent enrichment events. A veined mantle source region is proposed in preference to the mantle plume model to explain the chemical variations.

Sediment and pore water geochemistry of sediment cores, Potter Cove, King George Island

Redox-sensitive trace metals (Mn, Fe, U, Mo, Re), nutrients and terminal metabolic products (NO3-, NH4+, PO43-, total alkalinity) were for the first time investigated in pore waters of Antarctic coastal sediments. The results of this study reveal a high spatial variability in redox conditions in surface sediments from Potter Cove, King George Island, western Antarctic Peninsula. Particularly in the shallower areas of the bay the significant correlation between sulphate depletion and total alkalinity, the inorganic product of terminal metabolism, indicates sulphate reduction to be the major pathway of organic matter mineralisation. In contrast, dissimilatory metal oxide reduction seems to be prevailing in the newly ice-free areas and the deeper troughs, where concentrations of dissolved iron of up to 700 µM were found. We suggest that the increased accumulation of fine-grained material with high amounts of reducible metal oxides in combination with the reduced availability of metabolisable organic matter and enhanced physical and biological disturbance by bottom water currents, ice scouring and burrowing organisms favours metal oxide reduction over sulphate reduction in these areas. Based on modelled iron fluxes we calculate the contribution of the Antarctic shelf to the pool of potentially bioavailable iron (Feb) to be 6.9x10**3 to 790x10**3 t/yr. Consequently, these shelf sediments would provide an Feb flux of 0.35-39.5/mg/m**2/yr (median: 3.8 mg/m**2/yr) to the Southern Ocean. This contribution is in the same order of magnitude as the flux provided by icebergs and significantly higher than the input by aeolian dust. For this reason suboxic shelf sediments form a key source of iron for the high nutrient-low chlorophyll (HNLC) areas of the Southern Ocean. This source may become even more important in the future due to rising temperatures at the WAP accompanied by enhanced glacier retreat and the accumulation of melt water derived iron-rich material on the shelf.

X-ray fluorescence (XRF) scannings and grain size analysis at sites in the Gulf of Cádiz

Contourites in the Gulf of Cádiz preserve a unique archive of Mediterranean Outflow Water (MOW) variability over the past 5.3 Ma. In our study we investigate the potential of geochemical data obtained by XRF scanning to decipher bottom current processes and paleoclimatic evolution at two different sites drilled through contourite deposits in the northern Gulf of Cadiz: Site U1387, which is bathed by the upper MOW core, and Site U1389, located more proximal to the Straits of Gibraltar. The lack of major downslope transport at both locations during the Pleistocene makes them ideal locations for the purpose of our study. The results indicate that the Zr/Al ratio, representing the relative enrichment of heavy minerals (zircon) over less dense alumosilicates under strong bottom current flow, is the most useful indicator for a semi-quantitative assessment of current strength. While most elements are biased by current-related processes, the bromine record, representing organic content, preserves the most pristine climate signal rather independent of grain size changes. Hence, Br can be used for chronostratigraphy and site-to-site correlation in addition to stable isotope stratigraphy. Based on these findings we reconstructed MOW variability for Marine Isotope Stages 1-5 using the Zr/Al ratio from Site U1387. The results reveal abrupt, millennial-scale variations of MOW strength during Greenland Stadials (GS) and Interstadials (GI) with strong MOW during GS and glacial Terminations and a complex behavior during Heinrich Stadials. Millennial-scale variability persisting during periods of poorly expressed GS/GI cyclicities implies a strong internal oscillation of the Mediterranean/North Atlantic climate system.

Geochemical parameters of sediments and water of the Black Sea, data of Cruise 8 of R/V Vityaz-2

The book presents results of comprehensive geological investigations carried out during Cruise 8 of R/V "Vityaz-2" to the western part of the Black Sea in 1984. Systematic studies in the Black Sea during about hundred years have not weakened interest in the sea. Lithological and geochemical studies of sediments in estuarine areas of the Danube and the Kyzyl-Irmak rivers, as well as in adjacent parts of the deep sea and some other areas were the main aims of the cruise. Data on morphological structures of river fans, lithologic and chemical compositions of sediments in the fans and their areal distribution, forms of occurrence of chemical elements, role of organic matter and gases in sedimentation and diagenesis are given and discussed in the book.

Analyses of lake La Thuile sediment core

Lake La Thuile, in the Northern French Prealps (874 m a.s.l.), provides an 18 m long sedimentary sequence spanning the entire Lateglacial/Holocene period. The high resolution multi-proxy (sedimentological, palynological, geochemical) analysis of the uppermost 6.2 meters reveals the Holocene dynamics of erosion in the catchment in response to landscape modifications. The mountain belt is at relevant altitude to study past human activities and the watershed is sufficiently disconnected from large valleys to capture a local sedimentary signal. From 12,000 to 10,000 cal. BP (10 to 8 ka cal. BC), the onset of hardwood species triggered a drop in erosion following the Lateglacial/Holocene transition. From 10,000 to 4500 cal. BP (8 to 2.5 ka cal. BC), the forest became denser and favored slope stabilization while erosion processes were very weak. A first erosive phase was initiated at ca . 4500 cal. BP without evidence of human presence in the catchment. Then, the forest declined at approximately 3000 cal. BP, suggesting the first human influence on the landscape. Two other erosive phases are related to anthropic activities: approximately 2500 cal. BP (550 cal. BC) during the Roman period and after 1600 cal. BP (350 cal. AD) with a substantial accentuation in the Middle Ages. In contrast, the lower erosion produced during the Little Ice Age, when climate deteriorations are generally considered to result in an increased erosion signal in this region, suggests that anthropic activities dominated the erosive processes and completely masked the natural effects of climate on erosion in the late Holocene.

Physics, geochemistry and bulk sedimentology on cores from the Peru Basin

Empirical relationships between physical properties determined non-destructively by core logging devices and calibrated by carbonate and opal measurements determined on discrete samples allow extraction of carbonate and opal records from the non-destructive measurements in biogenic settings. Contents of detrital material can be calculated as a residual. For carbonate and opal the correlation coefficients (r) are 0.954 and ?0.916 for sediment density, ?0.816 and 0.845 for compressional-wave velocity, 0.908 and ?0.942 for acoustic impedance, and 0.886 and ?0.865 for sediment color (lightness). Carbonate contents increase in concert with increasing density and acoustic impedance, decreasing velocity and lighter sediment color. The opposite is true for opal. The advantages of deriving the sediment composition quantitatively from core logging are: (i) sampling resolution is increased significantly, (ii) non-destructive data can be gathered rapidly, and (iii) laboratory work on discrete samples can be reduced. Applied to paleoceanographic problems, this method offers the opportunity of precise stratigraphic correlations and of studying processes related to biogenic sedimentation in more detail. Density is most promising because it is most strongly affected by changes in composition.

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.

Geochemistry of pore water and sediments from ODP Leg 136 sites

During Leg 136 drilling was conducted at two sites in pelagic sediments of the north central Pacific Ocean. In this report, pore-water analyses for major seawater constituents, alkalinity, ammonia, nitrate, phosphate, silica, Ba, Fe, Li, Mn, and Sr are presented. Although concentration gradients are generally weak, resulting from slow sedimentation and concomitant diffusive communication with overlying water, there is evidence of sediment/pore-water interactions, associated sediment diagenesis, and formation of authigenic minerals. Bulk major and trace element compositions of the sediments are consistent with reactions inferred to occur within the sediments and with the lithology and mineralogy. Elemental compositions of the sediments are not strongly affected by diagenesis and are primarily related to the dominant mineralogy. Sediments are typical of deep ocean pelagic settings with a significant contribution from the alteration of volcanic ash and the formation of zeolites. Sedimentary rare earth element patterns also provide evidence of active scavenging processes by Mn and Fe oxide phases in the deeper sediments at Site 842.

Geochemistry of phosphatic crusts from the shelf off Peru

Authigenic phosphorite crusts from the shelf off Peru (9°40°S to 13°30°S) consist of a facies with phosphatic coated grains covered by younger phosphatic laminite. The crusts are composed of carbonate fluorapatite, which probably formed via an amorphous precursor close to the sediment water interface as indicated by low F/P2O5 ratios, Sr and Ca isotopes, as well as rare earth element patterns agreeing with seawater-dominated fluids. Small negative Ce anomalies and U enrichment in the laminite suggest suboxic conditions close to the sediment-water interface during its formation. Increased contents of chalcophilic elements and abundant sulfide minerals in the facies with phosphatic coated grains as well as in the laminite denote sulfate reduction and, consequently, point to episodical development of anoxic conditions during phosphogenesis. The Peruvian phosphorites formed episodically over an extended period of time lasting from Middle Miocene to Pleistocene. Individual phosphatic coated grains show a succession of phosphatic layers with varying contents of organic matter and sulfide-rich phosphatic layers. Coated grains supposedly formed as a result of episodic suspension caused by high turbulence and shifting redox conditions. Episodic anoxia in the pore water induced pyritization in the outermost carbonate fluorapatite layer. Phosphatic coated grains were later transported to the place of crust formation, where subsequent laminite formation was favored under lower energy conditions. A similar succession of phosphatic layers with varying contents of organic matter and sulfide-rich layers in the laminite suggests a formation mechanism analogous to that of individual coated grains.

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.