Reconstruction of the biogeochemistry and ecology of photoautotrophs based on the nitrogen and carbon isotopic compositions of vanadyl porphyrins from Miocene siliceous sediments

We determined both the nitrogen and carbon isotopic compositions of various vanadyl alkylporphyrins isolated from siliceous marine sediments of the Onnagawa Formation (middle Miocene, northeastern Japan) to investigate the biogeochemistry and ecology of photoautotrophs living in the paleo-ocean. The distinctive isotopic signals support the interpretations of previous works that the origin of 17-nor-deoxophylloerythroetioporphyrin (DPEP) is chlorophylls-<i>c</i><sub>1-3</sub>, whereas 8-nor-DPEP may have originated from chlorophylls-<i>a</i><sub>2</sub> or <i>b</i><sub>2</sub> or bacteriochlorophyll-<i>a</i>. Although DPEP and cycloheptanoDPEP are presumably derived from common precursory pigments, their isotopic compositions differed in the present study, suggesting that the latter represents a specific population within the photoautotrophic community. The average δ<sup>15</sup>N value for the entire photoautotrophic community is estimated to be –2 to +1‰ from the δ<sup>15</sup>N values of DPEP (–6.9 to –3.6‰; <i>n</i>=7), considering that the empirical isotopic relationships that the tetrapyrrole nuclei of chloropigments are depleted in <sup>15</sup>N by ~4.8‰ and enriched in <sup>13</sup>C by ~1.8‰ relative to the whole cells. This finding suggests that nitrogen utilized in the primary production was supplied mainly through N<sub>2</sub>-fixation by diazotrophic cyanobacteria. Based on the δ<sup>13</sup>C values of DPEP (–17.9 to –15.6‰; <i>n</i>=7), we estimated isotopic fractionation associated with photosynthetic carbon fixation to be 8–14‰. This range suggests the importance of β-carboxylation and/or active transport of the carbon substrate, indicating in turn the substantial contribution of diazotrophic cyanobacteria to primary production. Based on the δ<sup>15</sup>N values of 17-nor-DPEP (–7.4 to –2.4‰ <i>n</i>=7), the δ<sup>15</sup>N range of chlorophylls-<i>c</i>-producing algae was estimated to be –3 to +3‰. This relative depletion in sup>15</sup>N suggests that these algae mainly utilized nitrogen regenerated from diazotrophic cyanobacteria. Given that diatoms are likely to have constituted the chlorophylls-<i>c</i>-producing algae within the biogenic-silica-rich Onnagawa Formation, cyanobacteria-hosting diatoms may have been important contributors to primary production

Radiocarbon dating of alkenones from marine sediments : I. Isolation protocol

Author Posting. © Arizona Board of Regents on behalf of the University of Arizona, 2005. This article is posted here by permission of Dept. of Geosciences, University of Arizona for personal use, not for redistribution. The definitive version was published in Radiocarbon 47 (2005): 401-412.The chemical and isotopic compositions of long-chain (C36–C39) unsaturated ketones (alkenones), a unique class of algal lipids, encode surface ocean properties useful for paleoceanographic reconstruction. Recently, we have sought to extend the utility of alkenones as oceanic tracers through measurement of their radiocarbon contents. Here, we describe a method for isolation of alkenones from sediments as a compound class based on a sequence of wet chemical techniques. The steps involved, which include silica gel column chromatography, urea adduction, and silver nitrate-silica gel column chromatography, exploit various structural attributes of the alkenones. Amounts of purified alkenones estimated by GC/FID measurements were highly correlated with CO2 yields after sample combustion, indicating purities of greater than 90% for samples containing ≥100 μg C. The degree of alkenone unsaturation ( ) also varied minimally through the procedure. We also describe a high-performance liquid chromatography (HPLC) method to isolate individual alkenones for molecular-level structural and isotopic determination.This work was funded through grants from the National Science Foundation (OCE-9809624; OCE- 9907129) and the Japan Society for the Promotion of Science

Antarctic sediment chronology by programmed-temperature pyrolysis : methodology and data treatment

Author Posting. © American Geophysical Union, 2008. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 9 (2008): Q04005, doi:10.1029/2007GC001816.We report a detailed programmed-temperature pyrolysis/combustion methodology for radiocarbon (14C) dating of Antarctic sub-ice shelf sediments. The method targets the autochthonous organic component in sediments that contain a distribution of acid-insoluble organic components from several sources of different ages. The approach has improved sediment chronology in organic-rich sediments proximal to Antarctic ice shelves by yielding maximum age constraints significantly younger than bulk radiocarbon dates from the same sediment horizons. The method proves adequate in determining isotope ratios of the pre-aged carbon end-member; however, the isotopic compositions of the low-temperature measurements indicate that no samples completely avoided mixing with some proportion of pre-aged organic material. Dating the unresolved but desired young end-member must rely on indirect methods, but a simple mixing model cannot be developed without knowledge of the sedimentation rate or comparable constraints. A mathematical approach allowing for multiple mixing components yields a maximum likelihood age, a first-order approximation of the relative proportion of the autochthonous component, and the temperature at which allochthonous carbon begins to volatilize and mix with the autochthonous component. It is likely that our estimation of the cutoff temperature will be improved with knowledge of the pyrolysis kinetics of the major components. Chronology is improved relative to bulk acid-insoluble organic material ages from nine temperature interval dates down to two, but incorporation of inherently more pre-aged carbon in the first division becomes more apparent with fewer and larger temperature intervals.The project was paid for in part by NSF research grants OPP 02-30089 and OPP 03-38142 to Hamilton College (E. Domack) and NSF Cooperative Agreement OCE- 0228996 to Woods Hole Oceanographic Institution

Isotopic insights into the early Medieval (600-1100 CE) diet in the Luistari cemetery at Eura, Finland

In this article, we present the results of an isotopic study of diet for the early medieval (Merovingian, Viking, Early Christian) humans buried in the unique Luistari cemetery at Eura (ca. 600-1400 CE), southwestern Finland, the largest cemetery of the region. Isotope analysis was conducted on 37 humans for dentine and bone collagen (delta C-13, delta N-15, and delta S-34), and five of them were also studied using compound-specific nitrogen isotope analysis. Dental enamel and/or bone carbonate delta C-13 values were studied from altogether 65 humans, five cattle, and five sheep/goats. The bone and dentine collagen and carbonate data show that throughout the centuries, freshwater fish was a stable part of the diet for the population. Our results do not show systematic dietary differences between estimated males and females, but differences can be large on the individual level. We also discovered a possible temporal change in the enamel carbonate delta C-13 values that could be related to the increasing role of carbohydrates (e.g., crops) in the diet. Luistari burials are well comparable to contemporary Swedish Viking trading communities like Birka in their higher protein intake. But contrary to the wider Viking network, they do not show the same marine signal.Peer reviewe

Developing Ultra Small-Scale Radiocarbon Sample Measurement at the University of Tokyo

From the 20th International Radiocarbon Conference held in Kona, Hawaii, USA, May 31-June 3, 2009.We have developed accelerator mass spectrometry (AMS) measurement techniques for ultra small-size samples ranging from 0.01 to 0.10 mg C with a new type of MC-SNICS ion source system. We can generate 4 times higher ion beam current intensity for ultra-small samples by optimization of graphite position in the target holder with the new ionizer geometry. CO2 gas graphitized in the newly developed vacuum line is pressed to a depth of 1.5 mm from the front of the target holder. This is much deeper than the previous position at 0.35 mm depth. We measured 12C4+ beam currents generated by small standards and ion beam currents (15-30 mu-A) from the targets in optimized position, lasting 20 min for 0.01 mg C and 65 min for 0.10 mg C. We observed that the measured 14C/12C ratios are unaffected by the difference of ion beam currents ranging from 5 to 30 mu-A, enabling measurement of ultra-small samples with high precision. Examination of the background samples revealed 1.1 mu-g of modern and 1 mu-g of dead carbon contaminations during target graphite preparation. We make corrections for the contamination from both the modern and background components. Reduction of the contamination is necessary for conducting more accurate measurement.The Radiocarbon archives are made available by Radiocarbon and the University of Arizona Libraries. Contact [email protected] for further information.Migrated from OJS platform February 202

Diazotrophy drives primary production in the organic-rich shales deposited under a stratified environment during the messinian salinity crisis (Vena Del Gesso, Italy)

Density stratification between freshwater and brine is periodically formed during massive evaporation events, which often associates deposition of organic-rich sediments. Here, we investigated phototrophic communities and nitrogen cycle during the deposition of two organic-rich shale beds of gypsum\u2013shale alternation, representing the initial stage of the Messinian salinity crisis (Vena del Gesso, Northern Apennines, Italy). The structural distributions and the carbon and nitrogen isotopic compositions of geoporphyrins show a common pattern in the two shales, indicating the predominance of a particular phototrophic community under freshwater\u2013brine stratified conditions. The 3c6\u2030 difference in \u3b413C of total organic carbon between PLG 4 and 5 shales was associated with similar shift in \u3b413C of the porphyrins derived from chlorophyll c, suggesting that the eukaryotic algae producing chlorophyll c were the major constituent of the phototrophic community. Importantly, these porphyrins show \u3b415N values (-7.6\u2013-4.7\u2030) indicative of N2-fixation. We suggest that nitrate-depletion in the photic zone induced the predominance of diazotrophic cyanobacteria, which supplied new nitrogen for the chlorophyll c-producing eukaryotic algae. The large difference in the \u3b413C values of porphyrins and total organic carbon between PLG 4 and 5 shales are interpreted to reflect the depth of the chemocline, which fluctuates in response to changes in the regional evaporation\u2013precipitation balance. Such variation in the chemocline depth may have dynamically changed the mode of the nitrogen cycle (i.e., nitrification\u2013denitrification\u2013N2-fixation coupling vs. phototrophic assimilation of ammonium) in the density-stratified marginal basins during the Messinian salinity crisis

Biomarker records and mineral compositions of the Messinian halite and K–Mg salts from Sicily

The evaporites of the Realmonte salt mine (Sicily, Italy) are important archives recording the most extreme conditions of the Messinian Salinity Crisis (MSC). However, geochemical approach on these evaporitic sequences is scarce and little is known on the response of the biological community to drastically elevating salinity. In the present work, we investigated the depositional environments and the biological community of the shale–anhydrite–halite triplets and the K–Mg salt layer deposited during the peak of the MSC. Both hopanes and steranes are detected in the shale–anhydrite–halite triplets, suggesting the presence of eukaryotes and bacteria throughout their deposition. The K–Mg salt layer is composed of primary halites, diagenetic leonite, and primary and/or secondary kainite, which are interpreted to have precipitated from density-stratified water column with the halite-precipitating brine at the surface and the brineprecipitating K–Mg salts at the bottom. The presence of hopanes and a trace amount of steranes implicates that eukaryotes and bacteria were able to survive in the surface halite-precipitating brine even during the most extreme condition of the MSC.This work was performed with the support of Japan Society for the Promotion of Science (JSPS) Research Fellowship (16 J07844) to YI and JAMSTEC President Fund to NO

Stratigraphy around the Cretaceous-Paleogene boundary in sediment cores from the Lord Howe Rise, Southwest Pacific

During Deep Sea Drilling Project (DSDP) Leg 21, Cenozoic and latest Cretaceous sediments were recovered at Site 208 on the Lord Howe Rise, Southwest Pacific. We provide new biostratigraphic, magnetostratigraphic and chemostratigraphic data from Site 208 to constrain the stratigraphy around the Cretaceous-Paleogene (K-Pg) boundary and to determine the depth of the K-Pg boundary more precisely. Biostratigraphic data from calcareous nannofossils indicate a near-continuous succession of sediments from the mid-Maastrichtian (Late Cretaceous) to lowermost Thanetian (Paleocene) at depths of 540−590 m below seafloor (mbsf). The biostratigraphic data suggest that the K-Pg boundary corresponds to a siliceous claystone at the base of an interval of silicified sediments (576.0−576.8 mbsf). Carbonate carbon isotopic composition (δ^{13}_{Ccarb}) reveals a negative shift across this interval, which is consistent with global patterns of δ^{13}C across the K-Pg boundary. Osmium concentration and Os isotopic composition ({187}^Os/{188}^Os) can also be used to identify the K-Pg boundary interval, as it is marked by a peak in Os concentration and a drop in 187^{Os}/{188}^Os values to 0.12−0.15, both of which are the result of the Chicxulub impact event. Our {187}^Os/{188}^Os data show trends similar to those of coeval global seawater with the lowest value of 0.12−0.16 in the siliceous claystone (576.8 mbsf). However, the concentration of Os is low (<80 pg g^{−1}) in this sample, which suggests that this siliceous claystone was deposited around the K-Pg boundary but may not include the boundary itself. Although the sedimentary record across the K-Pg interval at Site 208 may not be completely continuous, it nevertheless captures a time interval that is close to the Chicxulub impact event

Nutritional sources of meio- and macrofauna at hydrothermal vents and adjacent areas: Natural-abundance radiocarbon and stable isotope analyses

© The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Nomaki, H., Uejima, Y., Ogawa, N. O., Yamane, M., Watanabe, H. K., Senokuchi, R., Bernhard, J. M., Kitahashi, T., Miyairi, Y., Yokoyama, Y., Ohkouchi, N., & Shimanaga, M. Nutritional sources of meio- and macrofauna at hydrothermal vents and adjacent areas: Natural-abundance radiocarbon and stable isotope analyses. Marine Ecology Progress Series, 622, (2019): 49-65, doi:10.3354/meps13053.Deep-sea hydrothermal vents host unique marine ecosystems that rely on organic matter produced by chemoautotrophic microbes together with phytodetritus. Although meiofauna can be abundant at such vents, the small size of meiofauna limits studies on nutritional sources. Here we investigated dietary sources of meio- and macrofauna at hydrothermal vent fields in the western North Pacific using stable carbon and nitrogen isotope ratios (δ13C, δ15N) and natural-abundance radiocarbon (Δ14C). Bacterial mats and Paralvinella spp. (polychaetes) collected from hydrothermal vent chimneys were enriched in 13C (up to -10‰) and depleted in 14C (-700 to -580‰). The δ13C and Δ14C values of dirivultid copepods, endemic to hydrothermal vent chimneys, were -11‰ and -661‰, respectively, and were similar to the values in the bacterial mats and Paralvinella spp. but distinct from those of nearby non-vent sediments (δ13C: ~-24‰) and water-column plankton (Δ14C: ~40‰). In contrast, δ13C values of nematodes from vent chimneys were similar to those of non-vent sites (ca. -25‰). Results suggest that dirivultids relied on vent chimney bacterial mats as their nutritional source, whereas vent nematodes did not obtain significant nutrient amounts from the chemolithoautotrophic microbes. The Δ14C values of Neoverruca intermedia (vent barnacle) suggest they gain nutrition from chemoautotrophic microbes, but the source of inorganic carbon was diluted with bottom water much more than those of the Paralvinella habitat, reflecting Neoverruca’s more distant distribution from active venting. The combination of stable and radioisotope analyses on hydrothermal vent organisms provides valuable information on their nutritional sources and, hence, their adaptive ecology to chemosynthesis-based ecosystems.We are grateful to the crews and scientists of the R/V ‘Natsushima’ and the ROV ‘Hyper-Dolphin’ of the Japan Agency for Marine-Earth Science and Technology (JAMSTEC) during the NT12-10, NT13-09 and NT14-06 cruises, and the R/V ‘Kaimei’ and the KM-ROV of JAMSTEC during the KM-ROV training cruise. We thank Yuki Iwadate for her help on sample preparations and 2 anonymous reviewers and the editor, who provided helpful comments on an earlier version of this manuscript. This work was supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology, Japan (Scientific Research C 26440246 to M.S.), the Japan Society for the Promotion of Science (Invitational fellowships for research in Japan, S14032 to J.M.B.), the WHOI Robert W. Morse Chair for Excellence in Oceanography, and The Investment in Science Fund at WHOI