Pb isotopes in Cenozoic sediments of ODP Site 177-1090

Nd and Pb isotopic compositions extracted from bulk deep sea sediments have been shown to be robust proxies for deep water circulation as well as weathering provenance and intensity over geologically young time scales. In this study we evaluated ten deep sea samples from Ocean Drilling Program (ODP) site 1090 ranging in age from mid Eocene to early-Miocene to test whether Pb isotopic compositions extracted from geologically older sediments record reliable seawater isotopic ratios and to evaluate the source of the extracted Pb. The sequential extraction protocol used in this study is similar to protocols reported for previous studies and produces acetic acid, hydroxylamine hydrochloride (HH) and residue fractions. Each extracted fraction was analyzed for Pb isotopes, rare earth elements (REEs), and a suite of major elements. Similar 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios are recorded from the acetic acid and HH fractions for ~70-80% of the samples, suggesting that either the acetic acid dissolves Fe-Mn oxides or multiple phases are recording the same seawater isotopic value. Several indirect tests, such as Al mass balance, comparison of Sr isotopes in HH extracts to contemporaneous seawater Sr isotopes, and comparison of Nd isotopic compositions in HH extracts to published fossil fish teeth values, provide evidence that Pb isotopic compositions measured in our bulk HH extracts record bottom water values. The relationship between Pb, Mn and Ca concentrations in HH fractions indicates that Fe-Mn oxides and a Mn-bearing carbonate are the dominant phases contributing seawater Pb. Comparison of REE patterns derived from the HH fraction and total digestions of Fe-Mn nodule standards reveals that the trivalent REEs exhibit patterns consistent with the parent archive, but Ce can be fractionated during extraction. Ratios of REEs also produce unique fields for each fraction and can be used to test the purity of the seawater signal of the extraction protocol. Finally, an initial evaluation of Pb isotopic compositions in fossil fish indicates that this archive is not suitable for bottom water Pb isotope studies.

Grain entrainment and transport rates of magnetic minerals of coastal sediment samples from the Bay of Plenty, New Zealand

Heavy (magnetic & non-magnetic) minerals are found concentrated by natural processes in many fluvial, estuarine, coastal and shelf environments with a potential to form economic placer deposits. Understanding the processes of heavy mineral transport and enrichment is prerequisite to interpret sediment magnetic properties in terms of hydro- and sediment dynamics. In this study, we combine rock magnetic and sedimentological laboratory measurements with numerical 3D discrete element models to investigate differential grain entrainment and transport rates of magnetic minerals in a range of coastal environments (riverbed, mouth, estuary, beach and near-shore). We analyzed grain-size distributions of representative bulk samples and their magnetic mineral fractions to relate grain-size modes to respective transport modes (traction, saltation, suspension). Rock magnetic measurements showed that distribution shapes, population sizes and grain-size offsets of bulk and magnetic mineral fractions hold information on the transport conditions and enrichment process in each depositional environment. A downstream decrease in magnetite grain size and an increase in magnetite concentration was observed from riverine source to marine sink environments. Lower flow velocities permit differential settling of light and heavy mineral grains creating heavy mineral enriched zones in estuary settings, while lighter minerals are washed out further into the sea. Numerical model results showed that higher heavy mineral concentrations in the bed increased the erosion rate and enhancing heavy mineral enrichment. In beach environments where sediments contained light and heavy mineral grains of equivalent grain sizes, the bed was found to be more stable with negligible amount of erosion compared to other bed compositions. Heavy mineral transport rates calculated for four different bed compositions showed that increasing heavy mineral content in the bed decreased the transport rate. There is always a lag in transport between light and heavy minerals which increases with higher heavy mineral concentration in all tested bed compositions. The results of laboratory experiments were validated by numerical models and showed good agreement. We demonstrate that the presented approach bears the potential to investigate heavy mineral enrichment processes in a wide range of sedimentary settings.

Isotopic composition of the fine fraction of ODP Site 114-704

Ocean Drilling Program Site 704 in the subantarctic South Atlantic was drilled to investigate the response of the Southern Ocean to climatic and Oceanographic developments during the late Neogene. Stable oxygen and carbon isotopes of fine-fraction (<63 µm) carbonate were analyzed to supplement similar analyses of benthic and planktonic foraminifers. The fine fraction is generally composed primarily of coccoliths, and isotopic analyses of the fine fraction were made to complement the foraminiferal analyses. The isotopic curves thus generated suggest paleoceanographic changes not recognizable by the use of benthic and planktonic foraminifers alone. The global Chron 6 carbon isotope shift, found at 253-244 mbsf (6.39-6.0 Ma) at Site 704 in the planktonic and benthic record, is seen in the fine-fraction d13C record as a gradual decrease from 255 mbsf (6.44 Ma) to 210 mbsf (4.24 Ma). At 170 mbsf, mean d18O values of Neogloboquadrina pachyderma increase by 0.6 per mil-0.7 per mil (Hodell and Ciesielski, 1991, doi:10.2973/odp.proc.sr.114.150.1991), reflecting decreased temperature and increased continental ice volume. Accumulation rates increase by 3.3 times above this depth (which corresponds to an age of 2.5 Ma), suggesting increased upwelling and biologic productivity. Carbon isotopic values of fine-fraction carbonate decrease by about 1.5 per mil at 2.6 Ma; however, no change is recorded in the d13C of N. pachyderma. The fine-fraction d13C shift slightly precedes an average l per mil decrease in d13C in benthic foraminifers. The cause of the benthic d13C shift (most likely due to a change in deep water circulation; Hodell and Ciesielski, 1991) is probably not directly related to the fine-fraction shift. The fine-fraction shift is most likely caused by (1) a change in the upwelling to productivity ratio at this site, with increased upwelling bringing lighter carbon to surface waters, more productivity, and higher sedimentation rates and (2) a change in the particle composition of the fine fraction. The increased upwelling is probably due to a northward migration of the Antarctic Polar Front to a position nearer Site 704.

(Table 2) Stratigraphic position of midpoints of reddish and beige layers of lithologic cycles in the Loulja-A Section and their astronomical ages after tuning to the ETP and Summer Insolation Curves of the La2004 solution

An integrated high-resolution stratigraphy and orbital tuning is presented for the Loulja sections located in the Bou Regreg area on the Atlantic side of Morocco. The sections constitute the upward continuation of the upper Messinian Ain el Beida section and contain a well-exposed, continuous record of the interval straddling the Miocene-Pliocene (M-P) boundary. The older Loulja-A section, which covers the interval from ~5.59 to 5.12 Ma, reveals a dominantly precession-controlled color cyclicity that allows for a straightforward orbital tuning of the boundary interval and for detailed cyclostratigraphic correlations to the Mediterranean; the high-resolution and high-quality benthic isotope record allows us to trace the dominantly obliquity-controlled glacial history. Our results reveal that the M-P boundary coincides with a minor, partly precession-related shift to lighter "interglacial" values in d18O. This shift and hence the M-P boundary may not correlate with isotope stage TG5, as previously thought, but with an extra (weak) obliquity-controlled cycle between TG7 and TG5. Consequently, the M-P boundary and basal Pliocene flooding of the Mediterranean following the Messinian salinity crisis are not associated with a major deglaciation and glacio-eustatic sea level rise, indicating that other factors, such as tectonics, must have played a fundamental role. On the other hand, the onset of the Upper Evaporites in the Mediterranean marked by hyposaline conditions coincides with the major deglaciation step between marine isotope stage TG12 and TG11, suggesting that the associated sea level rise is at least partly responsible for the apparent onset of intermittently restricted marine conditions following the main desiccation phase. Finally, the Loulja-A section would represent an excellent auxiliary boundary stratotype for the M-P boundary as formally defined at the base of the Trubi marls in the Eraclea Minoa section on Sicily.

Major nannofossils, carbon and oxygen isotopes and carbon composition of ODP leg 194 site survey gravity cores

Biostratigraphic, sedimentologic, and geochemical analyses of hemipelagic periplatform sediments from shallow gravity cores taken during the Ocean Drilling Program Leg 194 site survey reveal that, despite the strong currents and almost infilled intraplatform bathymetric depressions, recent sedimentation at the location of the Leg 194 drill sites recorded glacial-interglacial cycles. Sediment analyses included determination of sediment type, carbonate content, bulk stable oxygen isotope composition, and calcareous nannofossil zones. Glacial periods, identified by elevated bulk d18O, are characterized by darker sediment color, coarser grain size, and lower carbonate content, whereas interglacial periods yield lighter-colored, finer, and carbonate-rich sediments. These data from the shallowmost few meters of Marion Plateau sediments complement the subsurface information of Leg 194 holes, in which the top few meters have not been analyzed in such a high-resolution fashion. In addition, these gravity cores are more likely to have recovered the sediments closest to the sediment/water interface as compared to the hydraulic piston cores collected during Leg 194.

Gas content, composition of gas hydrate and volumetric gas/water ratios of ODP and DSDP sites

Gas hydrate samples were recovered from four sites (Sites 994, 995, 996, and 997) along the crest of the Blake Ridge during Ocean Drilling Program (ODP) Leg 164. At Site 996, an area of active gas venting, pockmarks, and chemosynthetic communities, vein-like gas hydrate was recovered from less than 1 meter below seafloor (mbsf) and intermittently through the maximum cored depth of 63 mbsf. In contrast, massive gas hydrate, probably fault filling and/or stratigraphically controlled, was recovered from depths of 260 mbsf at Site 994, and from 331 mbsf at Site 997. Downhole-logging data, along with geochemical and core temperature profiles, indicate that gas hydrate at Sites 994, 995, and 997 occurs from about 180 to 450 mbsf and is dispersed in sediment as 5- to 30-m-thick zones of up to about 15% bulk volume gas hydrate. Selected gas hydrate samples were placed in a sealed chamber and allowed to dissociate. Evolved gas to water volumetric ratios measured on seven samples from Site 996 ranged from 20 to 143 mL gas/mL water to 154 mL gas/mL water in one sample from Site 994, and to 139 mL gas/mL water in one sample from Site 997, which can be compared to the theoretical maximum gas to water ratio of 216. These ratios are minimum gas/water ratios for gas hydrate because of partial dissociation during core recovery and potential contamination with pore waters. Nonetheless, the maximum measured volumetric ratio indicates that at least 71% of the cages in this gas hydrate were filled with gas molecules. When corrections for pore-water contamination are made, these volumetric ratios range from 29 to 204, suggesting that cages in some natural gas hydrate are nearly filled. Methane comprises the bulk of the evolved gas from all sites (98.4%-99.9% methane and 0%-1.5% CO2). Site 996 hydrate contained little CO2 (0%-0.56%). Ethane concentrations differed significantly from Site 996, where they ranged from 720 to 1010 parts per million by volume (ppmv), to Sites 994 and 997, which contained much less ethane (up to 86 ppmv). Up to 19 ppmv propane and other higher homologues were noted; however, these gases are likely contaminants derived from sediment in some hydrate samples. CO2 concentrations are less in gas hydrate than in the surrounding sediment, likely an artifact of core depressurization, which released CO2 derived from dissolved organic carbon (DIC) into sediment. The isotopic composition of methane from gas hydrate ranges from d13C of -62.5 per mil to -70.7 per mil and dD of -175 per mil to -200 per mil and is identical to the isotopic composition of methane from surrounding sediment. Methane of this isotopic composition is mainly microbial in origin and likely produced by bacterial reduction of bicarbonate. The hydrocarbon gases here are likely the products of early microbial diagenesis. The isotopic composition of CO2 from gas hydrate ranges from d13C of -5.7 per mil to -6.9 per mil, about 15 per mil lighter than CO2 derived from nearby sediment.

Shape-invariant multibeam backscatter data of the eastern slope of the Porcupine Seabight (50 m grid size)

In this study multibeam angular backscatter data acquired in the eastern slope of the Porcupine Seabight are analysed. Processing of the angular backscatter data using the 'NRGCOR' software was made for 29 locations comprising different geological provinces like: carbonate mounds, buried mounds, seafloor channels, and inter-channel areas. A detailed methodology is developed to produce a map of angle-invariant (normalized) backscatter data by correcting the local angular backscatter values. The present paper involves detailed processing steps and related technical aspects of the normalization approach. The presented angle-invariant backscatter map possesses 12 dB dynamic range in terms of grey scale. A clear distinction is seen between the mound dominated northern area (Belgica province) and the Gollum channel seafloor at the southern end of the site. Qualitative analyses of the calculated mean backscatter values i.e., grey scale levels, utilizing angle-invariant backscatter data generally indicate backscatter values are highest (lighter grey scale) in the mound areas followed by buried mounds. The backscatter values are lowest in the inter-channel areas (lowest grey scale level). Moderate backscatter values (medium grey level) are observed from the Gollum and Kings channel data, and significant variability within the channel seafloor provinces. The segmentation of the channel seafloor provinces are made based on the computed grey scale levels for further analyses based on the angular backscatter strength. Three major parameters are utilized to classify four different seafloor provinces of the Porcupine Seabight by employing a semi-empirical method to analyse multibeam angular backscatter data. The predicted backscatter response which has been computed at 20° is the highest for the mound areas. The coefficient of variation (CV) of the mean backscatter response is also the highest for the mound areas. Interestingly, the slope value of the buried mound areas are found to be the highest. However, the channel seafloor of moderate backscatter response presents the lowest slope and CV values. A critical examination of the inter-channel areas indicates less variability within the estimated three parameters.

Strontium concentrations and isotopic compositions of anhydrites from the TAG active mound

Sr isotope analyses have been conducted on anhydrite samples from the TAG (Trans-Atlantic Geotraverse) active hydrothermal mound (26°08?N, Mid-Atlantic Ridge) that have previously been shown to exhibit two distinct patterns of REE behavior when normalized to TAG end-member hydrothermal fluid. Despite differences in REE patterns, the Sr isotope data indicate that all the anhydrites precipitated from fluids with a similar range of hydrothermal fluid and seawater components, and all but one were seawater-dominated (52%-75%). Speciation calculations using the EQ3/6 software package for geochemical modeling of aqueous systems suggest that the REE complexation behavior in different fluid mixing scenarios can explain the variations in the REE patterns. Anhydrites that exhibit relatively flat REE patterns [(La_bs)/(Yb_bs) = 0.8-2.0; subscript bs indicates normalization to end-member black smoker hydrothermal fluid] and a small or no Eu anomaly [(Eu_bs)/(Eu*_bs) = 0.8-2.0] are inferred to have precipitated from mixes of end-member hydrothermal fluid and cold seawater. REE complexes with hard ligands (e.g., fluoride and chloride) are less stable at low temperatures and trivalent Eu has an ionic radius similar to that of Ca2+ and the other REE, and so they behave coherently. In contrast, anhydrites that exhibit slight LREE-depletion [(La_bs)/(Yb_bs) = 0.4-1.4] and a distinct negative anomaly [(Eu_bs)/(Eu*_bs) = 0.2-0.8] are inferred to have precipitated from mixes of end-member hydrothermal fluid and conductively heated seawater. The LREE depletion results from the presence of very stable LREE chloro-complexes that effectively limit the availability of the LREE for partitioning into anhydrite. Above 250°C, Eu is present only in divalent form as chloride complexes, and discrimination against Eu2+ is likely due to both the mismatch in ionic radii between Eu2+ and Ca2+, and the strong chloro-complexation of divalent Eu which promotes stability in the fluid and inhibits partitioning of Eu2+ into precipitating anhydrite. These variations in REE behavior attest to rapid fluctuations in thermal regime, fluid flow and mixing in the subsurface of the TAG mound that give rise to heterogeneity in the formation conditions of individual anhydrite crystals.

Geochemistry of ODP Sites 128-798 and 128-799 sediments

Nineteen trace elements, including seven rare earth elements (REE's), and 10 major and minor elements in 76 sediment samples from Sites 798 (Oki Ridge) and 799 (Yamato Trough) were determined by means of instrumental neutron activation analysis and X-ray fluorescence spectrometry. Most REE patterns (chondrite-normalized) of the sediments from both sites were nearly identical to the patterns of terrigenous materials. The cerium anomaly (slightly positive) frequently appeared in REE patterns of the sediments (200-750 mbsf) from Site 799. Cerium may be selectively incorporated into the sediments with hydrogenous manganese precipitation. However, the degree of the anomaly was not well correlated with manganese content, suggesting that cerium may behave as a trivalent REE (like the other REE's) during diagenesis while manganese is transported in the sediment column accompanied by reduction to a lower oxidation state. The Th/Sc ratio of the sediments from Sites 798 and 799 tended to decrease with penetration depth. Such a depth profile may indicate a decrease in basic volcanism activities from the Pliocene (Site 798) and Miocene (Site 799). The La/Yb ratio and degree of europium anomaly also varied with depth, which may imply that two or more components with different REE patterns were supplied throughout sedimentation at sites in the Japan Sea.

Physical oceanography during two METEOR cruises in the subpolar North Atlantic

The detection of multi-decadal trends in the oceanic oxygen content and its possible attribution to global warming is protracted by the presence of a substantial amount of interannual to decadal variability, which hitherto is poorly known and characterized. Here we address this gap by studying interannual to decadal changes of the oxygen concentration in the Subpolar Mode Water (SPMW), the Intermediate Water (IW) and the Mediterranean Outflow Water (MOW) in the eastern North Atlantic. We use data from a hydrographic section located in the eastern North Atlantic at about 48°N repeated 12 times over a period of 19 years from 1993 through 2011, with a nearly annual resolution up to 2005. Despite a substantial amount of year-to-year variability, we observe a long-term decrease in the oxygen concentration of all three water masses, with the largest changes occurring from 1993 to 2002. During that time period, the trends were mainly caused by a contraction of the subpolar gyre associated with a northwestward shift of the Subpolar Front (SPF) in the eastern North Atlantic. This caused SPMW to be ventilated at lighter densities and its original density range being invaded by subtropical waters with substantially lower oxygen concentrations. The contraction of the subpolar gyre reduced also the penetration of IW of subpolar origin into the region in favor of an increased northward transport of IW of subtropical origin, which is also lower in oxygen. The long-term oxygen changes in the MOW were mainly affected by the interplay between circulation and solubility changes. Besides the long-term signals, mesoscale variability leaves a substantial imprint as well, affecting the water column over at least the upper 1000 m and laterally by more than 400 km. Mesoscale eddies induced changes in the oxygen concentration of a magnitude that can substantially alias analyses of long-term changes based on repeat hydrographic data that are being collected at intervals of typically 10 years.

Geochemistry of reduction haloes in ODP Holes 135-834A and 135-837A

The sediment column overlying basement in the Lau Basin consists of a sequence of volcaniclastic turbidites interbedded with hemipelagic clayey nannofossil mixed sediments, overlain in turn by a sequence of hemipelagic clayey nannofossil oozes containing sporadic calcareous turbidites. The clayey nannofossil oozes and mixed sediments are pervasively stained by hydrothermally derived iron and manganese oxyhydroxides. Sharply defined, lighter colored bands occur in the hemipelagic sediments, immediately beneath some (but by no means all) volcaniclastic and calcareous turbidites. These are identified as reduction haloes, of a type previously identified in quite different turbidite/pelagic sequences. The haloes are attributed to the burial of labile surficial Corg by turbidites, followed by the remineralization of this Corg with Mn and Fe oxyhydroxides as electron acceptors. The resultant characteristic Mn and Fe concentration/depth profiles are described, and a model is proposed for their development. The color alteration of the halo is ascribed to the removal of Mn oxyhydroxides, because, although the Fe content fluctuates through the haloes, this does not appear to affect their color. Other elements (Co, Cu, and Ni) are also at low concentration levels in the haloes like Mn, consistent with remobilization and migration out of the halo section, although the profile shapes are not identical with those of Mn. The behavior of V is distinctive in that it appears to have migrated into the haloes to be enriched there. Haloes are unlikely to form if turbidite emplacement is erosive and removes the near-surface layer, which generally is the most fluid part of the sediment and contains the highest levels of reactive Corg to drive the reduction process. Conversely, the presence of a halo implies that emplacement of the overlying turbidite did not significantly erode the pre-existing sediment/water interface.

Benthic foraminifers, isotopes and varimax factors at DSDP Holes 72-517 and 72-518

Pliocene changes in the vertical water mass structure of the western South Atlantic are inferred from changes in benthic foraminiferal assemblages and stable isotopes from DSDP Holes 516A, 517, and 518. Factor analysis of 34 samples from Site 518 reveals three distinct benthic foraminiferal assemblages that have been associated with specific subsurface water masses in the modern ocean. These include a Nuttalides umbonifera assemblage (Factor 1) associated with Antarctic Bottom Water (AABW), a Globocassidulina subglobosa-Uvigerina peregrina assemblage (Factor 2) associated with Circumpolar Deep Water (CPDW), and an Oridorsalis umbonatus-Epistominella exigua assemblage associated with North Atlantic Deep Water (NADW). Bathymetric gradients in d13C between Holes 516A (1313 m), 517 (2963 m), and 518 (3944 m) are calculated whenever possible to monitor the degree of similarity and/or difference in the apparent oxygen utilization (AOU) of water masses located at these depths during the Pliocene. Changes in bathymetric d13C gradients coupled with benthic foraminiferal assemblages record fundamental changes in the vertical water mass structure of the Vema Channel during the Pliocene from 4.1 to 2.7 Ma. At Site 518, the interval from 4.1 to 3.6 Ma is dominated by the N. umbonifera (Factor 1) and O. umbonatus-E. exigua (Factor 3) assemblages. The d13C gradient between Holes 518 (3944 m) and 516A (1313 m) undergoes rapid oscillations during this interval though no permanent increase in the gradient is observed. However, d13C values at Site 518 are clearly lighter during this interval. These conditions may be related to increased bottom water activity associated with the re-establishment of the West Antarctic Ice Sheet in the late Gilbert Chron (-4.2 to 3.6 Ma) (Osborn et al., 1982). The interval from 3.6 to 3.2 Ma is marked by a dominance of the G. subglobosa-U. peregrina (Factor 2) assemblage and lack of a strong d13C gradient between Holes 518 (3944 m) and 516A (1313 m). We suggest that shallow circumpolar waters expanded to depths of a least 3944 m (Site 518) during this time. The most profound faunal and isotopic change occurs at 3.2 Ma, and is marked by dominance of the N. umbonifera (Factor 1) and O. umbonatus-E. exigua (Factor 3) assemblages, a 1.1 per mil enrichment in d18O, and a large negative increase in the d13C gradient between Holes 518 and 516A. These changes at Site 518 record the vertical displacement of circumpolar waters by AABW and NADW. This change in vertical water mass structure at 3.2 Ma was probably related to a global cooling event and/or final closure of the Central American seaway. A comparison of the present-day d13C structure of the Vema Channel with a reconstruction between 3.2 and 2.7 Ma indicates that circulation patterns during this late Pliocene interval were similar to those of the modern western South Atlantic.

Geochemistry and morphometry on planktonic foraminifera

About one third of the anthropogenic carbon dioxide (CO2) released into the atmosphere in the past two centuries has been taken up by the ocean. As CO2 invades the surface ocean, carbonate ion concentrations and pH are lowered. Laboratory studies indicate that this reduces the calcification rates of marine calcifying organisms, including planktic foraminifera. Such a reduction in calcification resulting from anthropogenic CO2 emissions has not been observed, or quantified in the field yet. Here we present the findings of a study in the Western Arabian Sea that uses shells of the surface water dwelling planktic foraminifer Globigerinoides ruber in order to test the hypothesis that anthropogenically induced acidification has reduced shell calcification of this species. We found that light, thin-walled shells from the surface sediment are younger (based on 14C and d13C measurements) than the heavier, thicker-walled shells. Shells in the upper, bioturbated, sediment layer were significantly lighter compared to shells found below this layer. These observations are consistent with a scenario where anthropogenically induced ocean acidification reduced the rate at which foraminifera calcify, resulting in lighter shells. On the other hand, we show that seasonal upwelling in the area also influences their calcification and the stable isotope (d13C and d18O) signatures recorded by the foraminifera shells. Plankton tow and sediment trap data show that lighter shells were produced during upwelling and heavier ones during non-upwelling periods. Seasonality alone, however, cannot explain the 14C results, or the increase in shell weight below the bioturbated sediment layer. We therefore must conclude that probably both the processes of acidification and seasonal upwelling are responsible for the presence of light shells in the top of the sediment and the age difference between thick and thin specimens.

CPI, d13C, Corg and diploptene from ODP Hole 169-1034B varved sediments

Saanich Inlet has been a highly productive fjord since the last glaciation. During ODP Leg 169S, nearly 70 m of Holocene sediments were recovered from Hole 1034 at the center of the inlet. The younger sediments are laminated, anaerobic, and rich in organic material (1-2.5 wt.% Corg), whereas the older sediments below 70 mbsf are non-laminated, aerobic, with glacio-marine characteristics and have a significantly lower organic matter content. This difference is also reflected in the changes of interstitial fluids, and in biomarker compositions and their carbon isotope signals. The bacterially-derived hopanoid 17alpha(H),21beta(H)-hop-22(29)-ene (diploptene) occurs in Saanich Inlet sediments throughout the Holocene but is not present in Pleistocene glacio-marine sediments. Its concentration increases after ~6000 years BP up to present time to about 70 µg/g Corg, whereas terrigenous biomarkers such as the n-alkane C31 are low throughout the Holocene (<51 µg/g Corg) and even slightly decrease to 36 µg/g Corg at the most recent time. The increasing concentrations of diploptene in sediments younger than ~6000 years BP separate a recent period of higher primary productivity, stronger anoxic bottom waters, and higher bacterial activity from an older period with lesser activity, heretofore undifferentiated. Carbon isotopic compositions of diploptene in the Holocene are between ~31.5 and ~39.6 per mil PDB after ~6000 years BP. These differences in the carbon isotopic record of diploptene probably reflect changes in microbial community structure of bacteria living at the oxic-anoxic interface of the overlying water column. The heavier isotope values are consistent with the activity of nitrifying bacteria and the lighter isotope values with that of aerobic methanotrophic bacteria. Therefore, intermediate delta13C values probably represent mixtures between the populations. In contrast, carbon isotopic compositions of n-C31 are roughly constant at ~31.4 ± 1.1 per mil PDB throughout the Holocene, indicating a uniform input from cuticular waxes of higher plants. Prior to ~6000 years BP, diploptene enriched in 13C of up to -26.3 per mil PDB is indicative of cyanobacteria living in the photic zone and suggests a period of lower primary productivity, more oxygenated bottom waters, and hence lower bacterial activity during the earliest Holocene.

Late Miocene development of the western Pacific warm pool: Planktonic foraminifer and oxygen isotopic evidence

The disappearance at ~10 Ma of the deep dwelling planktonic foraminifer Globoquadrina dehiscens from the western Pacific including the South China Sea was about 3 Myr earlier than its final extinction elsewhere. Accompanying this event at ~10 Ma was a series of faunal turnover characterized by increase in mixed layer, warm-water species and decrease to a minimum in deepwater species. Paleobiological and isotopic evidence indicates sea surface warming and a deepened local thermocline that we interpret as related to the development of an early western Pacific warm pool. The stepwise decline of G. dehiscens and other deep dwelling species from the NW and SW Pacific suggests more intensive warm water pileup than equatorial localities where surface bypass flow through the narrowing Indonesia seaway appears to remain efficient during the late Miocene. Planktonic delta18O values from the South China Sea consistently lighter than the tropical western Pacific during the Miocene also suggest, similar to today, more variable hydrologic conditions along the periphery than in the core of the warm pool. Stronger hydrologic variability affected mainly by monsoons and increased thermal gradient along the western margin of the late Miocene warm pool may have contributed to the decline of deep dwelling planktonic species including the early extinction of G. dehiscens from the South China Sea region. The late Miocene warm pool became influential and paleobiologically detectable from ~10 Ma, but the modern warm pool did not appear until about 4 Ma, in the middle Pliocene.