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.

Carbonate system of surface sediments from the South Pacific

B/Ca ratios in Cibicides mundulus and Cibicides wuellerstorfi have been shown to correlate with the degree of calcite saturation in seawater (D[CO32-]). In the South Pacific, a region of high importance in the global carbon cycle, these species are not continuously present in down-core records. Small numbers of epibenthic foraminifera in samples present an additional challenge, which can be overcome by using laser ablation-inductively coupled-mass spectrometry (LA-ICP-MS). We present a laser ablation based core-top calibration for Cibicides cf. wuellerstorfi, a C. wuellerstorfi morphotype that is abundant in the South Pacific and extend the existing global core top calibration for C. mundulus and C. wuellerstorfi to this region. B/Ca in C. cf. wuellerstorfi are linearly correlated with D[CO32-] and possibly display a higher sensitivity to calcite saturation changes than C. wuellerstorfi. Trace element profiles through C. wuellerstorfi and C. mundulus reveal an intra-shell B/Ca variation of ±36% around the mean shell value. Mg/Ca and B/Ca display opposite trends along the shell. Both phenomena likely result from ontogenetic effects. Intra-shell variability equals intra-sample variability, mean sample B/Ca values can thus be reliably calculated from averaged spot results of single specimen. In the global B/Ca-D[CO32-] range, we observe an inverse relationship between water mass age and D[CO32-].

Sr/Ca ratios of Cenozoic benthic foraminifera

A Cenozoic multi-species record of benthic foraminiferal calcite Sr/Ca has been produced and is corrected for interspecific offsets (typically less than 0.3 mmol/mol) and for the linear relationship between decreasing benthic foraminiferal Sr/Ca and increasing water depth. The water depth correction, determined from Holocene, Late Glacial Maximum and Eocene paleowater-depth transects, is ~0.1 mmol/mol/km. The corrected Cenozoic benthic foraminiferal Sr/Ca record ranges from 1.2 to 2.0 mmol/mol, and has been interpreted in terms of long-term changes in seawater Sr/Ca, enabling issues related to higher-resolution variability in Sr/Ca to be ignored. We estimate that seawater Sr/Ca was ~1.5 times modern values in the late Cretaceous, but declined rapidly into the Paleogene. Following a minimum in the Eocene, seawater Sr/Ca increased gradually through to the present day with a minimum superimposed on this trend centered in the late Miocene. By assuming scenarios for changing seawater calcium concentration, and using published carbonate accumulation rate data combined with suitable values for Sr partition coefficients into carbonates, the seawater Sr/Ca record is used to estimate global average river Sr fluxes. These fluxes are used in conjunction with the seawater strontium isotope curve and estimates of hydrothermal activity/tectonic outgassing to calculate changes in global average river 87Sr/86Sr through the Cenozoic. The absolute magnitude of Sr fluxes and isotopic compositions calculated in this way are subject to relatively large uncertainties. Nevertheless, our results suggest that river Sr flux increased from 35 Ma to the present day (roughly two-fold) accompanied by an overall increase in 87Sr/86Sr (by ~0 to 0.001). Between 75 and 35 Ma, river 87Sr/86Sr also increased (by ~0.001 to 0.002) but was accompanied by a decrease (two- to three-fold) in river Sr flux.

Sedimentology and geochemistry on core Co1204

Lakes Prespa and Ohrid, in the Balkan region, are considered to be amongst the oldest lakes in Europe. Both lakes are hydraulically connected via karst aquifers. From Lake Ohrid, several sediment cores up to 15 m long have been studied over the last few years. Here, we document the first long sediment record from nearby Lake Prespa to clarify the influence of Lake Prespa on Lake Ohrid and the environmental history of the region. Radiocarbon dating and dated tephra layers provide robust age control and indicate that the 10.5 m long sediment record from Lake Prespa reaches back to 48 ka. Glacial sedimentation is characterized by low organic matter content and absence of carbonates in the sediments, which indicate oligotrophic conditions in both lakes. Holocene sedimentation is characterized by particularly high carbonate content in Lake Ohrid and by particularly high organic matter content in Lake Prespa, which indicates a shift towards more mesotrophic conditions in the latter. Long-term environmental change and short-term events, such as related to the Heinrich events during the Pleistocene or the 8.2 ka cooling event during the Holocene, are well recorded in both lakes, but are only evident in certain proxies. The comparison of the sediment cores from both lakes indicates that environmental change affects particularly the trophic state of Lake Prespa due to its lower volume and water depth.

Mg/Ca, Sr/Ca and Ca isotope ratios in benthonic foraminifers of surface sediment samples

We analysed Mg/Ca, Sr/Ca and Ca isotope ratios of benthonic foraminifers from sediment core tops retrieved during several research cruises in the Atlantic Ocean, in order to improve the understanding of isotope fractionation and element partitioning resulting from biomineralisation processes and changes in ambient conditions. Species include foraminifers secreting tests composed of hyaline low magnesium calcite, porcelaneous high magnesium calcite as well as aragonite. Our results demonstrate systematic isotope fractionation and element partitioning patterns specific for these foraminiferal groups. Calcium isotope fractionation is similar in porcelaneous and hyaline calcite tests and both groups demonstrate the previously described anomaly with enrichment of heavy isotopes around 3 - 4 °C (Gussone and Filipsson, 2010). Calcium isotope ratios of the aragonitic species Hoeglundina elegans, on the other hand, are about 0.4 per mil lighter compared to the calcitic species, which is in general agreement with stronger fractionation in inorganic aragonite compared to calcite. However, the low and strongly variable Sr content suggests additional processes during test formation, and we propose that transmembrane ion transport or a precursor phase to aragonite may be involved. Porcelaneous tests, composed of high Mg calcite, incorporate higher amounts of Sr compared to hyaline low Mg calcite, in agreement with inorganic calcite systematics, but also porcelaneous tests with reduced Mg/Ca show high Sr/Ca. While calcium isotopes, Sr/Ca and Mg/Ca in benthonic foraminifers primarily appear to fractionate and partition with a dominant inorganic control, d44/40Ca temperature and growth rate dependencies of benthonic foraminifer tests favour a dominant contribution of light Ca by transmembrane transport relative to unfractionated seawater Ca to the calcifying fluid, thus controlling the formation of foraminiferal d44/40Ca and Sr/Ca proxy signals.

Chemistry of low-temperature hydrothermal altered basement of ODP Site 129-801

Low-temperature hydrothermal alteration of basement from Site 801 was studied through analyses of the mineralogy, chemistry, and oxygen isotopic compositions of the rocks. The more than 100-m section of 170-Ma basement consists of 60 m of tholeiitic basalt separated from the overlying 60 m of alkalic basalts by a >3-m-thick Fe-Si hydrothermal deposit. Four alteration types were distinguished in the basalts: (1) saponite-type (Mg-smectite) rocks are generally slightly altered, exhibiting small increases in H2O, d18O, and oxidation; (2) celadonite-type rocks are also slightly altered, but exhibit uptake of alkalis in addition to hydration and oxidation, reflecting somewhat greater seawater/rock ratios than the saponite type; (3) Al-saponite-type alteration resulted in oxidation, hydration, and alkali and 18O uptake and losses of Ca and Na due to the breakdown of plagioclase and clinopyroxene; and (4) blue-green rocks exhibit the greatest chemical changes, including oxidation, hydration, alkali uptake, and loss of Ca, Na, and Mg due to the complete breakdown of plagioclase and olivine to K-feldspar and phyllosilicates. Saponite- and celadonite-type alteration of the tholeiite section occurred at a normal mid-ocean ridge basalt spreading center at temperatures <20°C. Near- or off-axis intrusion of an alkali basalt magma at depth reinitiated hydrothermal circulation, and the Fe-Si hydrothermal deposit formed from cool (<60°C) distal hydrothermal fluids. Focusing of fluid flow in the rocks immediately underlying the deposit resulted in the extensive alteration of the blue-green rocks at similar temperatures. Al-saponite alteration of the subsequent alkali basalts overlying the deposit occurred at relatively high water/rock ratios as part of the same low-temperature circulation system that formed the hydrothermal deposit. Abundant calcite formed in the rocks during progressive "aging" of the crust during its long history away from the spreading center.

Geochemistry of Lesser Antilles forearc sediments

Oceanic sediments contain the products of erosion of continental crust, biologic activity and chemical precipitation. These processes create a large diversity of their chemical and isotopic compositions. Here we focus on the influence of the distance from a continental platform on the trace element and isotopic compositions of sediments deposited on the ocean floor and highlight the role of zircons in decoupling high-field strength elements and Hf isotopic compositions from other trace elements and Nd isotopic compositions. We report major and trace element concentrations as well as Sr and Hf isotopic data for 80 sediments from the Lesser Antilles forearc region. The trace-element characteristics and the Sr and Hf isotopic compositions are generally dominated by detrital material from the continental crust but are also variably influenced by chemical or biogenic carbonate and pure biogenic silica. Next to the South American continent, at DSDP Site 144 and on Barbados Island, sediments, coarse quartz arenites, exhibit marked Zr and Hf excesses that we attribute to the presence of zircon. In contrast, the sediments from DSDP Site 543, which were deposited farther away from the continental platform, consist of fine clay and they show strong deficiencies in Zr and Hf. The enrichment or depletion of Zr-Hf is coupled to large changes in Hf isotopic compositions (-30 < epsilon-Hf < +4) that vary independently from the Nd isotopes. We interpret this feature as a clear expression of the "zircon effect" suggested by Patchett and coauthors in 1984. Zircon-rich sediments deposited next to the South American continent have very low epsilon-Hf values inherited from old zircons. In contrast, in detrital clay-rich sediments deposited a few hundred kilometers farther north, the mineral fraction is devoid of zircon and they have drastically higher epsilon-Hf values inherited from finer, clay-rich continental material. In the two DSDP sites, average Hf isotopes are very unradiogenic relative to other oceanic sediments worldwide (epsilon-Hf = -14.4 and -7.4) and they define the low Hf end member of the sedimentary field in Hf-Nd space. Their compositions correspond to end members that, when mixed with mantle, are able to reproduce the pattern of volcanic rocks from the Lesser Antilles. More generally, we find a relationship between Nb/Zr ratios and the vertical deviation of Hf isotope ratios from the Nd-Hf terrestrial array and we suggest that this relationship can be used as a tool to distinguish sediment input from fractionation during melting during the formation of arc lavas.

Mg/Ca and Sr/Ca ratios of Hoeglundina elegans from surface sediments

Core top samples from Atlantic (Little Bahama Banks (LBB)) and Pacific (Hawaii and Indonesia) depth transects have been analyzed in order to assess the influence of bottom water temperature (BWT) and aragonite saturation levels on Mg/Ca and Sr/Ca ratios in the aragonitic benthic foraminifer Hoeglundina elegans. Both the Mg/Ca and Sr/Ca ratios in H. elegans tests show a general decrease with increasing water depth. Although at each site the decreasing trends are consistent with the in situ temperature profile, Mg/Ca and Sr/Ca ratios in LBB are substantially higher than in Indonesia and Hawaii at comparable water depths with a greater difference observed with increasing water depth. Because we find no significant difference between results obtained on "live" and "dead" specimens, we propose that these differences are due to primary effects on the metal uptake during test formation. Evaluation of the water column properties at each site suggests that in situ CO3 ion concentrations play an important role in determining the H. elegans Mg/Ca and Sr/Ca ratios. The CO3 ion effect is limited, however, only to aragonite saturation levels ([DeltaCO3]aragonite) below 15 µmol/kg. Above this level, temperature exerts a dominant effect. Accordingly, we propose that Mg/Ca and Sr/Ca in H. elegans tests can be used to reconstruct thermocline temperatures only in waters oversaturated with respect to the mineral aragonite using the following relationships: Mg/Ca = (0.034 ± 0.002)BWT + (0.96 ± 0.03) and Sr/Ca = (0.060 ± 0.002)BWT + (1.53 ± 0.03) (for [DeltaCO3]aragonite > 15 µmol/kg). The standard error associated with these equations is about ±1.1°C. Reconstruction of deeper water temperatures is complicated because in undersaturated waters, changes in Mg/Ca and Sr/Ca ratios reflect a combination of changes in [CO3] and BWT. Overall, we find that Sr/Ca, rather than Mg/Ca, in H. elegans may be a more accurate proxy for reconstructing paleotemperatures.

Physical properties nd chemistry of igneous rocks from the Pigafetta and East Mariana Basins

Physical properties of basalts from Ocean Drilling Program Sites 800 and 801 in the Pigafetta Basin and Site 802 in the East Mariana Basin, including porosity, wet-bulk density, grain density, compressional wave velocity, and thermal conductivity, were measured aboard JOIDES Resolution during Leg 129. The ranges for the properties are large, as typified by the velocity, which varies from 3.46 to 6.59 km/s. Extensively altered basalts immediately above and below a silicified hydrothermal deposit (60-69 m sub-basement depth) at Site 801 display the highest porosity, and lowest bulk density, velocity, and thermal conductivity, whereas the slightly altered rocks from Site 802 and the lowermost part of Site 801 represent the other extreme in physical properties variations. In order to better establish the relationship between physical properties and alteration of the rocks, the compressional wave velocities were compared with results from major and trace elemental analyses and petrographic examination of select samples. For the Leg 129 basalts, velocity displays a generally consistent decrease with increasing K2O, H2O+, loss on ignition, and Rb contents and the value of Fe3+/FeT and decreasing concentrations of SiO2, FeOT, CaO, MgO, and MnO. These trends are consistent with trends documented for the progressive alteration of oceanic crust and indicate that on a laboratory sample scale, basalt alteration is largely responsible for the variation of the physical properties of basalts sampled at Sites 800, 801, and 802.

Jurassic sedimentation history at DSDP Hole 76-534A

Site 534 reflects a complex interplay of global, basinal, and local influences on sedimentation during the Callovian and Late Jurassic. Rifting and rapid subsidence of the continental margins of the North Atlantic-Tethys seaway occurred during the late Early Jurassic (Sinemurian-Pliensbachian), but rapid spreading between the North American margin (Blake Spur Ridge and magnetic lineation) and the northwest African margin did not commence until the Bathonian or earliest Callovian. Site 534, drilled on marine magnetic anomaly "M-28" of Bryan et al. (1980), was initially about 150 km from either continental margin. The ?middle Callovian basal sediments are dusky red silty marl. Callovian transgression led to active carbonate platforms on the margin, recorded at Site 534 as a rise in the CCD (carbonate compensation depth), then arrival of lime-rich turbidites from the Blake Plateau platform across the Blake Spur Ridge. The host pelagic sediment is greenish black, organic-rich, radiolarian-rich, silty claystone. Hydrothermal activity on the nearby spreading ridge enriched this lower unit in metals. In the Oxfordian, the input of terrestrial silt rapidly diminished; radiolarians or other bioclasts were not preserved. The dark variegated claystone has fine-grained marl and reddish claystone turbidite beds. The late Callovian-Oxfordian Western Tethys has radiolarian chert deposition, marine hiatuses, or organic-rich sediments. The Kimmeridgian and Tithonian had a stable or receding sea level. Near the end of the Jurassic many of the carbonate platforms of the margins were buried beneath prograding fan or alluvial deposits. Carbonate deposition shifted to the deep sea. Site 534 records the deepening of the CCD and ACD (aragonite compensation depth) during the Kimmeridgian and early Tithonian, then a rise of the ACD in the middle Tithonian. Similar trends occurred throughout the Western Tethys-Atlantic. High nannofossil productivity of the seaway led to deposition of very widespread white micritic limestone in the late Tithonian-Berriasian. The underlying sediment had a slower deposition rate of carbonate, therefore its higher clay and associated Fe content produced a red marl. A short sea-level incursion occurred on the Atlantic margins during the Kimmeridgian and is reflected in the Site 534 greenish gray marl unit by numerous turbidite beds of shallow-water carbonates.

Supplementary material: XRF core scanning data, CaCO3 values, foraminiferal carbon and oxygen isotope data, Mg/Ca data, clay mineralogy and helium isotope results

The Paleocene-Eocene Thermal Maximum (PETM; ~56 Ma) is associated with abrupt climate change, carbon cycle perturbation, ocean acidification, as well as biogeographic shifts in marine and terrestrial biota that were largely reversed as the climatic transient waned. We report a clear exception to the behavior of the PETM as a reversing climatic transient in the eastern North Atlantic (Deep-Sea Drilling Project Site 401, Bay of Biscay) where the PETM initiates a greatly prolonged environmental change compared to other places on Earth where records exist. The observed environmental perturbation extended well past the d13C recovery phase and up to 650 kyr after the PETM onset according to our extraterrestrial 3He-based age-model. We observe a strong decoupling of planktic foraminiferal d18O and Mg/Ca values during the PETM d13C recovery phase, which in combination with results from helium isotopes and clay mineralogy, suggests that the PETM triggered a hydrologic change in western Europe that increased freshwater flux and the delivery of weathering products to the eastern North Atlantic. This state change persisted long after the carbon-cycle perturbation had stopped. We hypothesize that either long-lived continental drainage patterns were altered by enhanced hydrological cycling induced by the PETM, or alternatively that the climate system in the hinterland area of Site 401 was forced into a new climate state that was not easily reversed in the aftermath of the PETM.

Calcite saturation and yield and Mg/Ca, Mn/Ca, Al/Ca, Fe/Ca for four species of planktic foraminifera cleaned using Mg-cleaning and Cd-cleaning methods

Four species of planktic foraminifera from core-tops spanning a depth transect on the Ontong Java Plateau were prepared for Mg/Ca analysis both with (Cd-cleaning) and without (Mg-cleaning) a reductive cleaning step. Reductive cleaning caused etching of foraminiferal calcite, focused on Mg-rich inner calcite, even on tests which had already been partially dissolved at the seafloor. Despite corrosion, there was no difference in Mg/Ca of Pulleniatina obliquiloculata between cleaning methods. Reductive cleaning decreased Mg/Ca by an average (all depths) of ~ 4% for Globigerinoides ruber white and ~ 10% for Neogloboquadrina dutertrei. Mg/Ca of Globigerinoides sacculifer (above the calcite saturation horizon only) was 5% lower after reductive cleaning. The decrease in Mg/Ca due to reductive cleaning appeared insensitive to preservation state for G. ruber, N. dutertrei and P. obliquiloculata. Mg/Ca of Cd-cleaned G. sacculifer appeared less sensitive to dissolution than that of Mg-cleaned. Mg-cleaning is adequate, but SEM and contaminants (Al/Ca, Fe/Ca and Mn/Ca) show that Cd-cleaning is more effective for porous species. A second aspect of the study addressed sample loss during cleaning. Lower yield after Cd-cleaning for G. ruber, G. sacculifer and N. dutertrei confirmed this to be the more aggressive method. Strongest correlations between yield and Delta[CO3^2-] in core-top samples were for Cd-cleaned G. ruber (r = 0.88, p = 0.020) and Cd-cleaned P. obliquiloculata (r = 0.68, p = 0.030). In a down-core record (WIND28K) correlation, r, between yield values > 30% and dissolution index, XDX, was -0.61 (p = 0.002). Where cleaning yield < 30% most Mg-cleaned Mg/Ca values were biased by dissolution.