Preliminary results of high resolution paleoceanography and paleoclimatology during sapropel S1 deposition (South Limnos Basin, North Aegean Sea).

Οι παλαιοπεριβαλλοντικές συνθήκες κατά τη διάρκεια απόθεσης του σαπροπηλού S1 στο Βόρειο Αιγαίο (πυρήνας βαρύτητας Μ-4, μήκους 2,53 m, λεκάνης νότιας Λήμνου) προσδιορίζονται με βάση την ποσοτική ανάλυση μικροπαλαιοντολογικών (βενθονικά και πλαγκτονικά τρηματοφόρα) και γεωχημικών (OC, δ13Corg) δεικτών. Χαρακτηριστικό του πυρήνα Μ-4 είναι η μεγάλη εμφάνιση του S1 που φτάνει το πάχος των 96 cm. Η μελέτη κατέδειξε ότι, το κατώτερο σαπροπηλικό στρώμα S1a αποτέθηκε σε θερμότερες συνθήκες, εντονότερης δυσοξίας, σε σχέση με το ανώτερο σαπροπηλικό στρώμα S1b.. Αύξηση της παραγωγικότητας και καλύτερη διατήρηση του οργανικού υλικού πιστοποιήθηκαν στο κατώτερο τμήμα του S1. Η διακοπή των σαπροπηλικών συνθηκών στα 8,0 Ka BP που χαρακτηρίζεται κυρίως από την αύξηση της σχετικής συχνότητας των συμφυρματοπαγών μορφών των βενθονικών τρηματοφόρων υποστηρίζει συνθήκες υψηλής οξυγόνωσης του πυθμένα και εισροή γλυκών υδάτων.The paleoenviromental conditions during the depositional interval of sapropel S1 in the northeastern Aegean (gravity core M-4, length 2.53 m; south Limnos basin) are studied based on quantitative micropaleontological (benthic and planktonic foraminifera) and geochemical (OC, δ13Corg) analyses. Special feature of core M-4 is the thickness of S1 layer (96 cm). Our study points that sapropelic layer S1a has been deposited in more dysoxic and warmer conditions in respect to S1b. Both primary productivity and preservation of organic material are more intense during the lower part of S1. An interruption of the sapropelic conditions at 8.0 Ka BP which is mainly characterized by the increase of agglutinated foraminiferal forms confirms both higher oxygen bottom conditions and freshwater input

Origins of archaeal tetraether lipids in sediments : insights from radiocarbon analysis

Author Posting. © Elsevier B.V., 2008. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 72 (2008): 4577-4594, doi:10.1016/j.gca.2008.06.021.Understanding the supply and preservation of glycerol dibiphytanyl glycerol tetraethers (GDGTs) in marine sediments helps inform their use in paleoceanography. Compound-specific radiocarbon measurements of sedimentary alkenones from multiple environments have been used to gain insight into processes that affect paleo-temperature reconstructions. Similar analyses are warranted to investigate how analogous processes affecting GDGTs impact TEX86 paleotemperatures. Here we present radiocarbon measurements on individual GDGTs from Bermuda Rise and Santa Monica Basin sediments and discuss the results in the context of previous studies of co-depositional alkenones and foraminifera. The 149 C contents of GDGTs and planktonic foraminifera in Bermuda Rise are very similar, suggesting a local source; and TEX86- derived temperatures agree more closely with foraminiferal temperatures than do temperatures. In contrast, GDGTs in Santa Monica Basin are depleted in 1412 C relative to both alkenones and foraminifera, and TEX86 temperatures agree poorly with known surface water values. We propose three possible factors that could explain these results: (i) GDGTs may be labile relative to alkenones during advective transport through oxic waters; (ii) archaeal production deep in the water column may contribute 1416 C-depleted GDGTs to sediments; and (iii) some GDGTs also may derive from sedimentary archaeal communities. Each of these three processes is likely to occur with varying relative importance depending on geographic location. The latter two may help to explain why TEX86 temperature reconstructions from Santa Monica Basin do not appear to reflect actual sea surface temperatures. Terrigenous GDGTs are unlikely to be major contributors to Bermuda Rise or Santa Monica Basin sediments, based on values of the BIT index. The results also indicate that the crenarchaeol regioisomer is governed by processes different from other GDGTs. Individual measurements of the crenarchaeol regioisomer are significantly depleted in 1424 C relative to co-occurring GDGTs, indicating an alternative origin for this compound that presently remains unknown. Re-examination of the contribution of crenarchaeol regioisomer to the TEX86 index shows that it is a significant influence on the sensitivity of temperature reconstructions.This work was supported by the David & Lucille Packard Foundation and by NSF-OCE-0241363 and EAR-0311937 (to A.P.)

Precision of the current methods to measure the alkenone proxy UK'37 and absolute alkenone abundance in sediments : results of an interlaboratory comparison study

Measurements of the UK'37 index and the absolute abundance of alkenones in marine sediments are increasingly used in paleoceanographic research as proxies of past sea surface temperature and haptophyte (mainly coccolith-bearing species) primary productivity, respectively. An important aspect of these studies is to be able to compare reliably data obtained by different laboratories from a wide variety of locations. Hence the intercomparability of data produced by the research community is essential. Here we report results from an anonymous interlaboratory comparison study involving 24 of the leading laboratories that carry out alkenone measurements worldwide. The majority of laboratories produce data that are intercomparable within the considered confidence limits. For the measurement of alkenone concentrations, however, there are systematic biases between laboratories, which might be related to the techniques employed to quantify the components. The maximum difference between any two laboratories for any two single measurements of UK'37 in sediments is estimated, with a probability of 95%, to be <2.18C. In addition, the overall within-laboratory precision for the UK'37 temperature estimates is estimated to be <1.68C (95% probability). Similarly, from the analyses of alkenone concentrations the interlaboratory reproducibility is estimated at 32%, and the repeatability is estimated at 24%. The former is compared to a theoretical estimate of reproducibility and found to be excessively high. Hence there is certainly scope and a demonstrable need to improve reproducibility and repeatability of UK'37 and especially alkenone quantification data across the community of scientists involved in alkenone research

Direct application of compound-specific radiocarbon analysis of leaf waxes to establish lacustrine sediment chronology

Author Posting. © Springer, 2007. This is the author's version of the work. It is posted here by permission of Springer for personal use, not for redistribution. The definitive version was published in Journal of Paleolimnology 39 (2008): 43-60, doi:10.1007/s10933-007-9094-1.This study demonstrates use of compound-specific radiocarbon analysis (CSRA) for dating Holocene lacustrine sediments from carbonate-hosted Ordy Pond, Oahu, Hawaii. Long-chain odd-numbered normal alkanes (n-alkanes), biomarkers characteristic of terrestrial higher plants, were ubiquitous in Ordy Pond sediments. The δ13C of individual n-alkanes ranged from −29.9 to −25.5‰, within the expected range for n-alkanes synthesized by land plants using the C3 or C4 carbon fixation pathway. The 14C ages of n-alkanes determined by CSRA showed remarkably good agreement with 14C dates of rare plant macrofossils obtained from nearby sedimentary horizons. In general, CSRA of n-alkanes successfully refined the age-control of the sediments. The sum of n-alkanes in each sample produced 70–170 μg of carbon (C), however, greater age errors were confirmed for samples containing less than 80 μg of C. The 14C age of n-alkanes from one particular sedimentary horizon was 4,155 years older than the value expected from the refined age-control, resulting in an apparent and arguable age discrepancy. Several lines of evidence suggest that this particular sample was contaminated by introduction of 14C-free C during preparative capillary gas chromatography. This study simultaneously highlighted the promising potential of CSRA for paleo-applications and the risks of contamination associated with micro-scale 14C measurement of individual organic compounds.This project was funded by Petroleum Research Fund (PRF #40088-ACS) and in part by Sigma Xi, The Scientific Research Society (Grants in aid of research, 2003)

Discerning natural and anthropogenic organic matter inputs to salt marsh sediments of Ria Formosa lagoon (South Portugal)

Sedimentary organic matter (OM) origin and molecular composition provide useful information to understand carbon cycling in coastal wetlands. Core sediments from threors' Contributionse transects along Ria Formosa lagoon intertidal zone were analysed using analytical pyrolysis (Py-GC/MS) to determine composition, distribution and origin of sedimentary OM. The distribution of alkyl compounds (alkanes, alkanoic acids and alkan-2-ones), polycyclic aromatic hydrocarbons (PAHs), lignin-derived methoxyphenols, linear alkylbenzenes (LABs), steranes and hopanes indicated OM inputs to the intertidal environment from natural-autochthonous and allochthonous-as well as anthropogenic. Several n-alkane geochemical indices used to assess the distribution of main OM sources (terrestrial and marine) in the sediments indicate that algal and aquatic macrophyte derived OM inputs dominated over terrigenous plant sources. The lignin-derived methoxyphenol assemblage, dominated by vinylguaiacol and vinylsyringol derivatives in all sediments, points to large OM contribution from higher plants. The spatial distributions of PAHs (polyaromatic hydrocarbons) showed that most pollution sources were mixed sources including both pyrogenic and petrogenic. Low carbon preference indexes (CPI > 1) for n-alkanes, the presence of UCM (unresolved complex mixture) and the distribution of hopanes (C-29-C-36) and steranes (C-27-C-29) suggested localized petroleum-derived hydrocarbon inputs to the core sediments. Series of LABs were found in most sediment samples also pointing to domestic sewage anthropogenic contributions to the sediment OM.EU Erasmus Mundus Joint Doctorate fellowship (FUECA, University of Cadiz, Spain)EUEuropean Commission [FP7-ENV-2011, 282845, FP7-534 ENV-2012, 308392]MINECO project INTERCARBON [CGL2016-78937-R]info:eu-repo/semantics/publishedVersio

Precision of the current methods to measure the alkenone proxy U₃₇ K’ and absolute alkenone abundance in sediments: results of an interlaboratory comparison study

Measurements of the U₃₇ K’ index and the absolute abundance of alkenones in marine sediments are increasingly used in paleoceanographic research as proxies of past sea surface temperature and haptophyte (mainly coccolith-bearing species) primary productivity, respectively. An important aspect of these studies is to be able to compare reliably data obtained by different laboratories from a wide variety of locations. Hence the intercomparability of data produced by the research community is essential. Here we report results from an anonymous interlaboratory comparison study involving 24 of the leading laboratories that carry out alkenone measurements worldwide. The majority of laboratories produce data that are intercomparable within the considered confidence limits. For the measurement of alkenone concentrations, however, there are systematic biases between laboratories, which might be related to the techniques employed to quantify the components. The maximum difference between any two laboratories for any two single measurements of U₃₇ K’ in sediments is estimated, with a probability of 95%, to be <2.1°C. In addition, the overall within-laboratory precision for the U₃₇ K’ temperature estimates is estimated to be <1.6°C (95% probability). Similarly, from the analyses of alkenone concentrations the interlaboratory reproducibility is estimated at 32%, and the repeatability is estimated at 24%. The former is compared to a theoretical estimate of reproducibility and found to be excessively high. Hence there is certainly scope and a demonstrable need to improve reproducibility and repeatability of U₃₇ K’ and especially alkenone quantification data across the community of scientists involved in alkenone research

Stratégies d'échantillonnage et d'analyse appliquées à l'étude des polluants organiques dans les eaux côtières

Les hydrocarbures sont un danger majeur pour l'océan. Dans les eaux côtières ce type de contamination est exacerbé par les effets de synergie entre de multiples sources de pollution. Le développement de programmes permettant de dresser des bilans des différents apports et la nécessité de concevoir des modèles prédictifs permettant d'évaluer l'impact des hydrocarbures et des autres contaminants sur la qualité des eaux marines et sur les écosystèmes côtiers reposent sur la qualité des stratégies d'échantillonnage et d'analyse mises en place. Cette revue décrit certains points importants de ces stratégies, appliquées au delta du Rhône et au bassin Méditerranéen Nord-occidental. L'échantillonnage doit comprendre des prélèvements effectués aux étapes clés du fonctionnement du fleuve et des activités biologiques se développant dans les zones frontales, au large du fleuve. La stratégie d'échantillonnage comprend l'étude de la diffusion des eaux fluviales et de leurs polluants associés en milieu marin et I'étude des zones de création et d'accumulation de particules. L'échantillonnage s'intéresse à divers compartiments: eau, particules en suspension (y compris les organismes vivants), couches turbides se développant près du fond, sédiments superficiels. Après une couverture complète de paramètres clés, tels salinité, MES, Carbone organique, O2, pH, une étude détaillée et quantitative sera effectuée sur les hydrocarbures par combinaison de diverses techniques chromatographiques. Les empreintes obtenues peuvent être discutées en termes d'identification de diverses sources naturelles et anthropiques, de leur disponibilité pour les organismes vivants en fonction de leur répartition entre phases dissoute et particulaire, de transport, de dégradation et d'ultime dépôt dans les sédiments. Des exemples illustrent l'intérêt des analyses d'hydrocarbures aromatiques polycycliques dans les sédiments; ils signent des empreintes fidèles des divers types de contamination que l'on peut rencontrer en milieu marin côtier