Changes of dissolved organic matter compositions in artifical and natural seawater during Pseudovibrio growth experiment

To study the consumption of dissolved organic matter (DOM) by bacteria living in untra-oligotrophic artificial or natural seawater, we analyzed the composition of DOM before (timepoint t0, directly after inoculation) and after (timepoint t2, 3 weeks of incubation) growth of the bacteria using Fourier transform ion cyclotron mass spectrometry (ESI FT-ICR-MS). The oligotrophic natural seawater used originates from the South Pacific Gyre. Our data show that the bacteria were able to utilize a variety of different organic compounds. These compounds belong to different chemical compound groups and likely fuel the bacterial energy, carbon and nitrogen requirements under the ultra-oligotrophic conditions.

Diatom biostratigraphy and datum levels of sediments from ODP Leg 167 sites

Ocean Drilling Program Leg 167 represents the first time since 1978 that the North American Pacific margin was drilled to study ocean history. More than 7500 m of Quaternary to middle Miocene (14 Ma) sediments were recovered from 13 sites, representing the most complete stratigraphic sequence on the California margin. Diatoms are found in most samples in variable abundance and in a moderately well-preserved state throughout the sequence, and they are often dominated by robust, dissolution-resistant species. The Neogene North Pacific diatom zonation of Yanagisawa and Akiba (1998, doi:10.5575/geosoc.104.395) best divides the Miocene to Quaternary sequences, and updated ages of diatom biohorizons estimated based on the geomagnetic polarity time scale of Cande and Kent (1995, doi:10.1029/94JB03098) are slightly revised to adjust the differences between the other zonations. Most of the early middle Miocene through Pleistocene diatom datum levels that have been proven to be of stratigraphic utility in the North Pacific appear to be nearly isochronous within the level of resolution constrained by sample spacing. The assemblages are characterized by species typical of middle-to-high latitudes and regions of high surface-water productivity, predominantly by Coscinodiscus marginatus, Stephanopyxis species, Proboscia barboi, and Thalassiothrix longissima. Latest Miocene through Pliocene assemblages in the region of the California Current, however, are intermediate between those of subarctic and subtropical areas. As a result, neither the existing tropical nor the subarctic (high latitude) zonal schemes were applicable for this region. An interval of pronounced diatom dissolution detected throughout the Pliocene sequence apparently correspond to a relatively warmer paleoceanographic condition resulting in a slackening of the southward flow of the California Current.

Molecular dissolved organic matter composition and environmental parameters from a laboratory incubation study

Dissolved organic matter (DOM) in the oceans constitutes a major carbon pool involved in global biogeochemical cycles. More than 96% of the marine DOM resists microbial degradation for thousands of years. The composition of this refractory DOM (RDOM) exhibits a molecular signature which is ubiquitously detected in the deep oceans. Surprisingly efficient microbial transformation of labile into RDOM was shown experimentally, implying that microorganisms produce far more RDOM than needed to sustain the global pool. By assessing the microbial formation and transformation of DOM in unprecedented molecular detail for 3 years, we show that most of the newly formed RDOM is molecularly different from deep sea RDOM. Only <0.4% of the net community production was channeled into RDOM molecularly undistinguishable from deep sea DOM. Our study provides novel experimentally derived molecular evidence and data for global models on the production, turnover and accumulation of marine DOM.

Calcareous nannofossil bioevents of early-middle Pleistocene sediments from the Mediterranean Sea and the Noth Atlantic

Quantitative distributions of calcareous nannofossils are analysed in the early-middle Pleistocene at the small Gephyrocapsa and Pseudoemiliania lacunosa zone transition in deep-sea cores from the Mediterranean Sea and North Atlantic Ocean (Ocean Drilling Program [ODP] Sites 977, 964 and 967, Deep Sea Drilling Project [DSDP] Site 607). The temporal and spatial mode of occurrence of medium-sized gephyrocapsids and reticulofenestrids has been examined to refine biostratigraphic constraints and evaluate possible relationships of stratigraphic patterns to environmental changes during a period of global climatic deterioration. The timing of bioevents has been calibrated using high-resolution sampling and correlation to the delta18O record in chronologically well-constrained sections. Newly identified events and ecostratigraphical signals enhance the stratigraphic resolution at the early-middle Pleistocene. The first occurrence (FO) of intermediate morphotypes between Pseudoemiliania and Reticulofenestra (Reticulofenestra sp.) is proposed as a reliable event within marine isotope stage (MIS) 35 or at the MIS 35/34 transition. The distribution of Reticulofenestra asanoi is characterized by rare and scattered occurrences in its lowest range, but the first common occurrence (FCO) is consistently identified at MIS 32 or 32/31; the last common occurrence (LCO) of the species is a distinctive event at MIS 23. In the studied interval, Gephyrocapsa omega dominates among medium-sized Gephyrocapsa. The FO of G. omega and contemporaneous re-entry of medium-sized gephyrocapsids at the lower-middle Pleistocene transition are diachronous between the Atlantic Ocean and Mediterranean Sea and from the western to eastern Mediterranean. In the Mediterranean, the LO of G. omega falls at MIS 15, insolation cycle 54 and is isochronous among the sites. Abundance fluctuations of G. omega show notable relations to early-middle Pleistocene climate changes; they considerably increase in abundance at the interglacial stages, suggesting warm water preferences. Gephyrocapsa omega temporarily disappears during the glacial MIS 22 and MIS 20. Above MIS 20, an impoverishment in G. omega and in the total abundance of medium-sized gephyrocapsids occurs. A decrease in abundance of G. omega is observed between the western Site 977 and the easternmost Site 967 in the Mediterranean Sea, as a possible response to high salinity and/or low nutrient content. Possible environmental influences on the distribution of R. asanoi and of Reticulofenestra sp. are discussed.

Barremian-Aptian dinoflagellate cyst assemblages

Quantified organic-walled dinoflagellate cyst (dinocyst) assemblages are presented for two sedimentary successions deposited in neritic environments of the Tethys Ocean during the Barremian and Aptian in an attempt to reconcile established dinocyst biostratigraphic schemes for Tethyan and Austral regions. One section is at Angles, southeast France (the Barremian stratotype section); the other is at Deep Sea Drilling Project Site 263, off northwest Australia. We also construct a carbon isotope record for Site 263 using bulk organic carbon. Both sections contain abundant, well-preserved dinocyst assemblages. These are diverse, with 89 taxa identified at Angles and 103 taxa identified at Site 263. Of these, more than 93% are cosmopolitan. When combined with other work at Angles and Site 263, we found that nine dinocysts have their first occurrence (FO) or last occurrence (LO) at both locations. These dinocyst events are, in alphabetical order: LO of Cassiculosphaeridia magna, FO of Criboperidinium? tenuiceras, LO of Kleithriasphaeridium fasciatum, LO of Muderongia staurota, FO of Odontochitina operculata, LO of Phoberocysta neocomica, FO of Prolixosphaeridium parvispinum, FO of Pseudoceratium retusum var. securigerum, and FO of Tehamadinium sousense. Although these events support a Barremian-Aptian age for both sections, their stratigraphic order is not the same in the sections. The d13Corg record at Site 263 displays a characteristic series of changes that have also been recorded in other carbon isotope curves spanning the Late Barremian-Early Aptian. Such independent dating (along with ammonite zones at Angles) suggests that three of the nine dinocyst events are approximately isochronous at Angles and Site 263: the LO of K. fasciatum in the mid Barremian, the FO of P. retusum var. securigerum and the FO of C.? tenuiceras in the earliest Aptian; the other six dinocyst events are diachronous. Dinocyst assemblages at Site 263 can be loosely placed within existing Australian zonation schemes, providing much-needed calibration. Our data suggest that the Muderongia testudinaria Zone ends in sediments of mid Barremian age, the succeeding Muderongia australis Zone extends into the Early Aptian, and the younger Odontochitina operculata Zone begins in Early Aptian deposits. The boundary between the M. australis and O. operculata zones, and the Ovoidinium cinctum (as Ascodinium) Subzone, positioned at the top of the M. australis Zone when present, could not be recognized incontrovertibly. Interestingly, however, this horizon broadly correlates with the onset and extent of the Selli Event, a time of major biogeochemical change.

Neogene diatoms of the Japan Sea

A series of excellent upper Miocene through Quaternary diatomaceous sequences recovered at four sites during Leg 127 was examined for diatoms. The diagenetic transition from opal-A to opal-CT is a diachronic horizon from the uppermost part of the Denticulopsis katayamae Zone (8.5 Ma) at Hole 797B to the uppermost part of the Neodenticula kamtschatica Zone (5.73 Ma) at Hole 795A. The diatom zonation of Koizumi (1985) best divides the upper Miocene to Quaternary sequences above the opal-A/opal-CT boundary and also is useful to date carbonate concretions including diatoms below the boundary. Forty diatom datum levels were evaluated biostratigraphically based on the sediment accumulation rate curve, and several isochronous datum levels are newly proposed for the Japan Sea area. A warm-water current did not penetrated into the Japan Sea through the Tsushima strait during the late Miocene and Pliocene time, because subtropical warm-water diatoms are essentially not present in such sediment samples. The occurrences of diatom are cyclic throughout the Quaternary sediments and are affected by eustatic sea level changes.

Age model and grain size distribution of the fine fraction of ODP Site 114-704

The physical properties of sediments beneath an upwelling area in the southern part of the Atlantic Ocean (ODP Hole 704A) were investigated. Highly significant correlations characterize the relationship of carbonate content to bulk density (R = 0.85), carbonate content to porosity (R = 0.84), and carbonate content to impedance (R = 0.84). No relationship exists between carbonate content and compressional-wave velocity (R = 0.24), indicating that amplitude variations in impedance are primarily controlled by variations in bulk density, which, in turn, are controlled by climatically driven biogenic opal and carbonate deposition. In general, maxima in impedance correspond to maxima in carbonate content (minima in opal content). The impedance record exhibits its most drastic change at about 2.4 Ma, marking dramatic increases in the average content of biogenic opal and the beginning of large-amplitude fluctuations. Between 0.7 and 0.4 Ma carbonate content, bulk density, and grain density decrease while opal content drastically increases. Similar changes have been observed in sediments beneath an upwelling cell off northwest Africa, indicating an oceanwide enhancement in upwelling or in the calcite corrosiveness of bottom water that appears to be isochronous.

Revision of the early-middle Pleistocene calcareous nannofossil biochronology

The extant nannofossil biostratigraphic and biochronologic framework for the early-middle Pleistocene time interval has been tested through the micropaleontological analysis of globally distributed high-quality low- to mid-latitude deep-sea successions. The quantitative temporal distribution patterns of relative abundances of selected taxa were reconstructed in critical intervals, and the following biohorizons were defined: first occurrence of medium-sized Gephyrocapsa spp. (bmG); last occurrence of Calcidiscus macintyrei (tCm); first occurrence of large Gephyrocapsa spp. (blG); last occurrence of large Gephyrocapsa spp. (tlG); first occurrence of Reticulofenestra asanoi (bRa); re-entrance of medium-sized Gephyrocapsa spp. (reemG) and last occurrence of Reticulofenestra asanoi (tRa). The detailed patterns of abundance change at these biohorizons were used to generate a detailed biostratigraphy, and the biostratigraphic data were transformed into a precise biochronology by means of correlation to isotope stratigraphies and astronomical timescales. The degree of isochrony or diachrony of the biohorizons was evaluated. Biohorizons tlG and tRa are isochronous occurring close to marine isotope stages (MIS)55 and MIS 22, respectively, and bmG and blG are slightly diachronous on the order of 30-40 kyr, whereas biohorizons tCm, reemG and bRa are confirmed as diachronous on the order of 100, 80 and 60 kyr, respectively. Some of the events are clearly controlled by environmental conditions, e.g. the last occurrence of R. asanoi, related to significant environmental changes associated with the first large-amplitude glaciation of the late Quaternary, MIS 22.

Chemical composition of volcanic glass of some tephra layers in Northeastern Pacific Ocean

Five widespread upper Cenozoic tephra layers that are found within continental sediments of the western United States have been correlated with tephra layers in marine sediments in the Humboldt and Ventura basins of coastal California by similarities in major-and trace-element abundances; four of these layers have also been identified in deep-ocean sediments at DSDP sites 34, 36, 173, and 470 in the northeastern Pacific Ocean. These layers, erupted from vents in the Yellowstone National Park area of Wyoming and Idaho (Y), the Cascade Range of the Pacific Northwest (C), and the Long Valley area, California (L), are the Huckleberry Ridge ash bed (2.0 Ma, Y), Rio Dell ash bed (ca. 1.5 Ma, C), Bishop ash bed (0.74 Ma, L), Lava Creek B ash bed (0.62 Ma, Y), and Loleta ash bed (ca. 0.4 Ma, C). The isochronous nature of these beds allows direct comparison of chronologic and climatic data in a variety of depositional environments. For example, the widespread Bishop ash bed is correlated from proximal localities near Bishop in east-central California, where it is interbedded with volcanic and glacial deposits, to lacustrine beds near Tecopa, southeastern California, to deformed on-shore marine strata near Ventura, southwestern California, to deep-ocean sediments at site 470 in the eastern Pacific Ocean west of northern Mexico. The correlations allow us to compare isotopic ages determined for the tephra layers with ages of continental and marine biostratigraphic zones determined by magnetostratigraphy and other numerical age control and also provide iterative checks for available age control. Relative age variations of as much as 0.5 m.y. exist between marine biostratigraphic datums [for example, highest occurrence level of Discoaster brouweri and Calcidiscus tropicus (= C. macintyrei)], as determined from sedimentation rate curves derived from other age control available at each of several sites. These discrepancies may be due to several factors, among which are (1) diachronism of the lowest and highest occurrence levels of marine faunal and floral species with latitude because of ecologic thresholds, (2) upward reworking of older forms in hemipelagic sections adjacent to the tectonically active coast of the western United States and other similar analytical problems in identification of biostratigraphic and magnetostratigraphic datums, (3) dissolution of microfossils or selective diagenesis of some taxa, (4) lack of precision in isotopic age calibration of these datums, (5) errors in isotopic ages of tephra beds, and (6) large variations in sedimentation rates or hiatuses in stratigraphic sections that result in age errors of interpolated datums. Correlation of tephra layers between on-land marine and deep-ocean deposits indicates that some biostratigraphic datums (diatom and calcareous nannofossil) may be truly time transgressive because at some sites, they are found above and, at other sites, below the same tephra layers.

Miocene to Pliocene calcareous nannofossil biostratigraphy at ODP Leg 117 Sites 1088 and 1090, Southern Ocean

The calcareous nannofossil biostratigraphy of ODP Leg 177 Sites 1088 and 1090 (Subantarctic sector from the Atlantic Ocean) is discussed. Most nannofossil zonal boundaries of Martini (1971) and Okada and Bukry (1980) were recognized for the studied mid-high-latitude sediments. Conventional low-latitude marker species such as Amaurolithus spp., Discoaster spp., Triquetrorhabdulus spp., Ceratolithus spp. were recorded as rare and scattered, which impeded the development of a detailed nannofossil biostratigraphic zonation of some Miocene and Pliocene intervals. Because of the absence of some primary biostratigraphic marker species, additional second-order bioevents, such as the first occurrence of Calcidiscus macintyrei and the last occurrence of Coccolithus miopelagicus, have been used to approximate the base of zones NN7 and NN8, respectively. Several disconformities disturbing the Pliocene and Miocene intervals of Site 1090 could be determined based on nannofossil distribution although the occurrence of intervals with dissolved nannofloras and low species diversity prevented a reliable age assignment. An acme of small Gephyrocapsa was recognized near the lower/middle Pliocene boundary, close to the NN15-NN16 zonal boundary, presenting an event for further improvement of the calcareous nannofossil biostratigraphy of this interval time. The first occurrence of Pseudoemiliania lacunosa (>4 µm) occurs close to this interval, representing a fairly reliable event to approximate the base of NN15 zone when other biozonal events are absent. A paracme of R. pseudoumbilicus (>7 µm) was detected in the lower Pliocene NN12 and in the upper Miocene NN11. These temporary absences of the species seem to be isochronous between high-latitude and low-middle-latitude areas.

NADW Photodegradation FTICR-MS

Duplicate, filtered samples of North Atlantic Deep Water (NADW) were irradiated for 28 days in a solar simulator. Duplicate dark controls were placed alongside the irradiated samples. After 28 days, samples were extensively photo-degraded based upon colored dissolved organic matter (CDOM) photo-bleaching (> 95%). Samples were solid phase extracted using PPL resin to isolate, concentrate and desalt the dissolved organic matter (DOM) in the samples. Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) enabled 3024 molecular formulas to be identified in the dark control. Photo-degradation decreased molecular diversity, with 2402 formulas assigned post-irradiation. Molecular formulas were classified based upon their photo-lability as 1) photo-resistant; 2) photo-labile; and, 3) photo-produced. Photo-resistant DOM made up 73% of all formulas and was dominated by highly unsaturated molecular signatures consistent with carboxylic-rich alicyclic molecules, suggesting that these apparently bio-refractory compounds may also survive multiple passages through sunlit surface waters and thus accumulate for timeframes exceeding ocean ventilation. Photo-labile DOM was enriched in low molecular weight formulas, aromatic molecular formulas, and sulfur and phosphorous containing formulas. Compounds containing both sulfur and nitrogen were particularly photo-labile and may represent an underappreciated component of the photo-reactive CDOM pool. Photo-produced DOM was enriched in higher molecular weight formulas, as well as aliphatic and peptide formulas. Molecular formulas are indexed by their photo-lability classification in the supplementary information.