(Table 2) Carbonate chemistry and isotopes from northern Cascadia margin samples

Most authigenic carbonates previously recovered from the Cascadia slope have 87Sr/86Sr signatures that reflect shallow precipitation in equilibrium with coeval seawater. There is also evidence for carbonate formation supported by fluids that have been modified by reactions with the incoming Juan de Fuca plate (87Sr/86Sr = 0.7071; Teichert et al., 2005, doi:10.1016/j.epsl.2005.08.002) or with terrigenous turbidites (87Sr/86Sr = 0.70975 to 0.71279; Sample et al., 1993, doi:10.1130/0091-7613(1993)021<0507:CCICFF>2.3.CO;2). We report on the strontium isotopic composition of carbonates and fluids from IODP Site U1329 and nearby Barkley Canyon (offshore Vancouver Island), which have strontium isotope ratios as low as 0.70539. Whereas the strontium and oxygen isotopic compositions of carbonates from paleoseeps in the uplifted Coast Range forearc indicate formation in ambient bottom seawater, several samples from the Pysht/Sooke Fm. show a 87Sr-depleted signal (87Sr/86Sr = 0.70494 and 0.70511) similar to that of the anomalous Site U1329 and Barkley Canyon carbonates. Our data, when analyzed in the context of published elemental and isotopic composition of these carbonates (Joseph et al., 2012, doi:10.1016/j.palaeo.2013.01.012 ), point to two formation mechanisms: 1) shallow precipitation driven by the anaerobic oxidation of methane (AOM) with d13C values as low as -50 per mil and contemporaneous 87Sr/86Sr seawater ratios, and 2) carbonate precipitation driven by fluids that have circulated through the oceanic crust, which are depleted in 87Sr. Carbonates formed from the second mechanism precipitate both at depth and at sites of deep-sourced fluid seepage on the seafloor. The 87Sr-depleted carbonates and pore fluids found at Barkley Canyon represent migration of a deep, exotic fluid similar to that found in high permeability conglomerate layers at 188 mbsf of Site U1329, and which may have fed paleoseeps in the Pysht/Sooke Fm. These exotic fluids likely reflect interaction with the 52-57 Ma igneous Crescent Terrane, which supplies fluids with high calcium, manganese and strontium enriched in the non-radiogenic nucleide. Tectonic compression and dehydration reactions then force these fluids updip, where they pick up the thermogenic hydrocarbons and 13C-enriched dissolved inorganic carbon that are manifested in fluids and carbonates sampled at Barkley Canyon and at Site U1329. The Crescent Terrane may have sourced cold seeps in this margin since at least the late Oligocene.

Stable carbon isotope ratios and accumulation rates of organic carbon and nutrients of DSDP Hole 79-545 (Appendix A)

Future warming is predicted to shift the Earth system into a mode with progressive increase and vigour of extreme climate events possibly stimulating other mechanisms that invigorate global warming. This study provides new data and modelling investigating climatic consequences and biogeochemical feedbacks that happened in a warmer world ~112 Myr ago. Our study focuses on the Cretaceous Oceanic Anoxic Event (OAE) 1b and explores how the Earth system responded to a moderate ~25,000 yr lasting climate perturbation that is modelled to be less than 1 °C in global average temperature. Using a new chronological model for OAE 1b we present high-resolution elemental and bulk carbon isotope records from DSDP Site 545 from Mazagan Plateau off NW Africa and combine this information with a coupled atmosphere-land-ocean model. The simulations suggest that a perturbation at the onset of OAE 1b caused almost instantaneous warming of the atmosphere on the order of 0.3 °C followed by a longer (~45,000 yr) period of ~0.8 °C cooling. The marine records from DSDP Site 545 support that these moderate swings in global climate had immediate consequences for African continental supply of mineral matter and nutrients (phosphorous), subsequent oxygen availability, and organic carbon burial in the eastern subtropical Atlantic, however, without turning the ocean anoxic. The match between modelling results and stratigraphic isotopic data support previous studies [summarized in Jenkyns 2003, doi:10.1098/rsta.2003.1240] in that methane emission from marine hydrates, albeit moderate in dimension, may have been the trigger for OAE 1b, though we can not finally rule out alternative mechanisms. Following the hydrate mechanism a total of 1.15 * 10**18 g methane carbon (delta13C=-60 ?), equivalent to about 10% to the total modern gas hydrate inventory, generated the delta13Ccarb profile recorded in the section. Modelling suggests a combination of moderate-scale methane pulses supplemented by continuous methane emission at elevated levels over ~25,000 yr. The proposed mechanism, though difficult to finally confirm in the geological past, is arguably more likely to occur in a warmer world and apparently perturbs global climate and ocean chemistry almost instantaneously. This study shows that, once set-off, this mechanism can maintain Earth's climate in a perturbed mode over geological time leading to pronounced changes in regional climate.

Middle and late Cenomanian oceanic anoxic events in shallow and deeper shelf environments of western Morocco

The response of shallow-water sequences to oceanic anoxic event 2 and mid-Cenomanian events 1a and 1b was investigated along the west African margin of Morocco north of Agadir (Azazoul) and correlated with the deep-water sequence of the Tarfaya Basin (Mohammed Beach) based on biostratigraphy, mineralogy, phosphorus and stable isotopes. In the deeper Mohammed Beach section results show double peaks in delta 13C(org) for mid-Cenomanian events 1a and 1b (Rotalipora reicheli biozone, lower CC10a biozone), the characteristic oceanic anoxic event 2 delta 13C excursion (Rotalipora cushmani extinction, top of CC10a biozone) and laminated (anoxic) black shale. In the shallow environment north of Agadir, a fluctuating sea-level associated with dysoxic, brackish and mesotrophic conditions prevailed during the middle to late Cenomanian, as indicated by oyster biostromes, nannofossils, planktonic and benthonic foraminiferal assemblages. Anoxic conditions characteristic of oceanic anoxic event 2 (for example, laminated black shales) did not reach into shallow-water environments until the maximum transgression of the early Turonian. Climate conditions decoupled along the western margin of Morocco between mid-Cenomanian event 1b and the Cenomanian-Turonian boundary, as also observed in eastern Tethys. North of Agadir alternating humid and dry seasonal conditions prevailed, whereas in the Tarfaya Basin the climate was dry and seasonal. This climatic decoupling can be attributed to variations in the Intertropical Convergence Zone and in the intensity of the north-east trade winds in tropical areas.

Genetic variation for carbon isotope composition in Juglans regia L.: relationships with growth, phenology and climate of origin

Among the traits of breeding interest for the common walnut tree Juglans regia L., characteristics such as timing of budbreak and leaf fall, water-use efficiency and growth performance are regarded as being of utmost relevance in Mediterranean conditions. The authors evaluated intraspecific variation in $\delta$13C (carbon isotope composition, surrogate of intrinsic water-use efficiency, WUE$_{\rm i}$) for 22 J. regia families grown in a progeny test under supplementary irrigation, and investigated whether such variation correlated with climatic indicators of native habitats. The genetic relationships between $\delta$13C, growth and phenology were also assessed during two consecutive years. Overall, the most water-use-efficient families (i.e. with higher $\delta$13C), which originated mainly from drought-prone provenance regions which have a high vapour pressure deficit and low rainfall, exhibited less height growth and smaller DBH. Using a stepwise regression procedure, $\delta$13C was included as the main explanatory variable of genotypic variation in growth traits, together with growing season duration (for DBH in both years) and flushing (for height in 2007). It was concluded that WUE$_{\rm i}$ is largely unconnected to phenology effects in the explanation of growth performance for J. regia, therefore suggesting the opportunity of simultaneously selecting for low WUE$_{\rm i}$ and extended growing period to maximise productivity in non-water-limited environments.

Produktion und Nutzung von mikrobiellen Residuen als labile Zwischenspeicher für Nährstoffe

Mit dem Ziel, die Bildung und den Verbrauch von mikrobiellen Residuen zu ermitteln, wurden zwei Inkubationsversuche durchgeführt. Die Versuchsdauer betrug jeweils 67 Tage, wobei an den Tagen 5, 12, 33, 38, 45 und 67 Proben entnommen und auf Ct, Cmik, CO2 sowie die δ13C-Werte, Nt, Nmin und Ergosterol untersucht wurden. In Versuch 1 wurden als leicht umsetzbare Kohlenstoffquelle 3 mg C4-Kohlenstoff g-1Boden in Form von Rohrzucker bzw. Maiscellulose und als N-Ausgleich 200 µg NH4NO3-N g-1Boden hinzugegeben. Der verwendete Boden war ein Lößboden. In Versuch 2 wurden 3 mg C4-Kohlenstoff g-1Boden in Form von Rohrzucker und 100 µg NH4NO3-N g-1Boden in den Boden eingearbeitet. Als Substrat wurde hier ein gebrannter Lößboden verwendet. Bei beiden Versuchen erfolgte an Tag 33 nochmals eine Zugabe von 3 mg C3-Kohlenstoff g-1Boden in Form von Cellulose. Die Zugabe des C4-Kohlenstoffs führte in beiden Versuchen zu einer Zunahme des C4-Anteils in der mikrobiellen Biomasse. Insgesamt wurden im ersten Versuch ca. 78 % des C4-Kohlenstoffs und im zweiten Versuch ca. 64 % mineralisiert. In Versuch 1 wurde bei der Rohrzuckervariante der größte Teil an C4-C innerhalb der ersten 5 Tage mineralisiert, in der Cellulosevariante konnte dagegen eine geringere, aber länger anhaltende Mineralisation bis Tag 33 beobachtet werden. Dies sowie die Entwicklung des C4-C der mikrobiellen Biomasse deuten darauf hin, dass die Cellulose erst zu diesem Zeitpunkt vollständig umgesetzt war, der Rohrzucker dagegen aber schon nach 5 Inkubationstagen. Der Anteil an C4-C in den mikrobiellen Residuen lag an Tag 33 bei 28 % (Cellulosevariante) bzw. 22 % (Rohrzuckervariante) des zugegebenen C4-Kohlenstoffs. Dagegen lag im zweiten Versuch der Anteil an C4-Kohlenstoff in den mikrobiellen Residuen bei 40 %. In Versuch 1 führte die Zugabe der C3-Cellulose an Tag 33 nicht zu einem Verbrauch von mikrobiellen Residuen, im Versuch 2 hingegen zu einer signifikanten Abnahme. Der zugegebene Stickstoff wurde in beiden Versuchen durch die Zugabe des Rohrzuckers in hohen Anteilen immobilisiert, aber nur in geringem Umfang in die mikrobielle Biomasse inkorporiert. An Tag 33 lag der Anteil Stickstoff in den mikrobiellen Residuen bei 52 % (Versuch 1) bzw. 84 % (Versuch 2) des zugegebenen Stickstoffs. In Versuch 1 setzte nach 33 Tagen eine Remineralisation des immobilisierten Stickstoffs ein, unabhängig von der Zugabe der C3-Cellulose. In Versuch 2 wurde der immobilisierte Stickstoff zu keinem Zeitpunkt remineralisiert. Die Zugabe der C3-Cellulose führte hier nicht zu einer Remineralisation des immobilisierten Stickstoffs. Es bestätigte sich die Annahme, dass durch die Zugabe von leicht umsetzbaren Kohlstoffsubstraten die Bildung von mikrobiellen Residuen gesteigert werden kann. Die zweite Annahme, dass durch die Zugabe von N-freiem Substrat, hier C3-Cellulose, die mikrobiellen Residuen bevorzugt abgebaut werden, konnte nicht bestätigt werden.

Teores de carbono e nitrogênio dos solos de duas microbacias hidrográficas com diferentes usos da terra no município de Ibiúna-SP

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Stable isotope composition of atmospheric carbon monoxide : a modelling study

Stable isotope composition of atmospheric carbon monoxide: A modelling study.rnrnThis study aims at an improved understanding of the stable carbon and oxygen isotope composition of the carbon monoxide (CO) in the global atmosphere by means of numerical simulations. At first, a new kinetic chemistry tagging technique for the most complete parameterisation of isotope effects has been introduced into the Modular Earth Submodel System (MESSy) framework. Incorporated into the ECHAM/MESSy Atmospheric Chemistry (EMAC) general circulation model, an explicit treatment of the isotope effects on the global scale is now possible. The expanded model system has been applied to simulate the chemical system containing up to five isotopologues of all carbon- and oxygen-bearing species, which ultimately determine the δ13C, δ18O and Δ17O isotopic signatures of atmospheric CO. As model input, a new stable isotope-inclusive emission inventory for the relevant trace gases has been compiled. The uncertainties of the emission estimates and of the resulting simulated mixing and isotope ratios have been analysed. The simulated CO mixing and stable isotope ratios have been compared to in-situ measurements from ground-based observatories and from the civil-aircraft-mounted CARIBIC−1 measurement platform.rnrnThe systematically underestimated 13CO/12CO ratios of earlier, simplified modelling studies can now be partly explained. The EMAC simulations do not support the inferences of those studies, which suggest for CO a reduced input of the highly depleted in 13C methane oxidation source. In particular, a high average yield of 0.94 CO per reacted methane (CH4) molecule is simulated in the troposphere, to a large extent due to the competition between the deposition and convective transport processes affecting the CH4 to CO reaction chain intermediates. None of the other factors, assumed or disregarded in previous studies, however hypothesised to have the potential in enriching tropospheric CO in 13C, were found significant when explicitly simulated. The inaccurate surface emissions, likely underestimated over East Asia, are responsible for roughly half of the discrepancies between the simulated and observed 13CO in the northern hemisphere (NH), whereas the remote southern hemisphere (SH) compositions suggest an underestimated fractionation during the oxidation of CO by the hydroxyl radical (OH). A reanalysis of the kinetic isotope effect (KIE) in this reaction contrasts the conventional assumption of a mere pressure dependence, and instead suggests an additional temperature dependence of the 13C KIE, which is driven by changes in the partitioning of the reaction exit channels. This result is yet to be confirmed in the laboratory.rnrnApart from 13CO, for the first time the atmospheric distribution of the oxygen mass-independent fractionation (MIF) in CO, Δ17O, has been consistently simulated on the global scale with EMAC. The applicability of Δ17O(CO) observations to unravelling changes in the tropospheric CH4-CO-OH system has been scrutinised, as well as the implications of the ozone (O3) input to the CO isotope oxygen budget. The Δ17O(CO) is confirmed to be the principal signal for the CO photochemical age, thus providing a measure for the OH chiefly involved in the sink of CO. The highly mass-independently fractionated O3 oxygen is estimated to comprise around 2% of the overall tropospheric CO source, which has implications for the δ18O, but less likely for the Δ17O CO budgets. Finally, additional sensitivity simulations with EMAC corroborate the nearly equal net effects of the present-day CH4 and CO burdens in removing tropospheric OH, as well as the large turnover and stability of the abundance of the latter. The simulated CO isotopologues nonetheless hint at a likely insufficient OH regeneration in the NH high latitudes and the upper troposphere / lower stratosphere (UTLS).rn

Geochemical and palynological results of IODP Hole 302-M0004A from Lomonosov Ridge, Arctic Ocean

Several episodes of abrupt and transient warming, each lasting between 50,000 and 200,000 years, punctuated the long-term warming during the Late Palaeocene and Early Eocene (58 to 51 Myr ago) epochs**1,2. These hyperthermal events, such as the Eocene Thermal Maximum 2 (ETM2) that took place about 53.5 Myr ago**2, are associated with rapid increases in atmospheric CO2 content. However, the impacts of most events are documented only locally**3,4. Here we show, on the basis of estimates from the TEX86' proxy, that sea surface temperatures rose by 3-5 °C in the Arctic Ocean during the ETM2. Dinoflagellate fossils demonstrate a concomitant freshening and eutrophication of surface waters, which resulted in euxinia in the photic zone. The presence of palm pollen implies**5 that coldest month mean temperatures over the Arctic land masses were no less than 8 °C, in contradiction of model simulations that suggest hyperthermal winter temperatures were below freezing**6. In light of our reconstructed temperature and hydrologic trends, we conclude that the temperature and hydrographic responses to abruptly increased atmospheric CO2 concentrations were similar for the ETM2 and the better-described Palaeocene-Eocene Thermal Maximum**7,8, 55.5 Myr ago.

Geochemical and physical sediment properties of sediment cores from the Portuguese shelf

Marine sediments from the Portuguese shelf are influenced by environmental changes in the surrounding continental and marine environment. These are largely controlled by the North Atlantic Oscillation, but additional impacts may arise from episodic tsunamis. In order to investigate these influences, a high resolution multi-proxy study has been carried out on a 5.4 m long gravity core and five box cores from the Tagus prodelta on the western Portuguese margin, incorporating geochemical (Corg/Ntotal ratios, d13Corg, d15N, d18O, Corg and CaCO3 content) and physical sediment properties (magnetic susceptibility, grain-size). Subsurface data of the five box cores indicate no major effect of early postdepositional alteration. Surface data show a higher fraction of terrigenous organic material close to the river mouth and in the southern prodelta. Gravity core GeoB 8903 covers the last 3.2 kyrs with a temporal resolution of at least 0.1 cm/yr. Very high sedimentation rates between 69 and 140 cm core depth indicate a possible disturbance of the record by the AD1755 tsunami, although no evidence for a disturbance is observed in the data. Sea surface temperature and salinity on the prodelta, the local budget of marine NO3- as well as the provenance of organic matter remained virtually constant during the past 3.2 kyrs. A positive correlation between magnetic susceptibility (MS) and North Atlantic Oscillation (NAO) is evident for the past 250 years, coinciding with a negative correlation between mean grain-size and NAO. This is assigned to a constant riverine supply of fine material with high MS, which is diluted by the riverine input of a coarser, low-MS component during NAO negative, high-precipitation phases. End-member modelling of the lithic grain-size spectrum supports this, revealing a third, coarse lithic component. The high abundance of this coarse end-member prior to 2 kyr BP is interpreted as the result of stronger bottom currents, concentrating the coarse sediment fraction by winnowing. As continental climate was more arid prior to 2 kyr BP (Subboreal), the coarse end-member may also consist of dust from local sources. A decrease in grain-size and CaCO3 content after 2 kyr BP is interpreted as a result of decreasing wind strength. The onset of a fining trend and a further decrease in CaCO3 around AD900 occurs simultaneous to climatic variations, reconstructed from eastern North Atlantic records. A strong increase in MS between AD1400 and AD1500 indicates higher lithic terrigenous input, caused by deforestation in the hinterland.

A relationship between aerosol transport and compound-specific d13C land plant biomarker and pollen records

We examined near-surface, late Holocene deep-sea sediments at nine sites on a north-south transect from the Congo Fan (4°S) to the Cape Basin (30°S) along the Southwest African continental margin. Contents, distribution patterns and molecular stable carbon isotope signatures of long-chain n-alkanes (C27-C33) and n-alkanols (C22-C32) are indicators of land plant vegetation of different biosynthetic types, which can be correlated with concentrations and distributions of pollen taxa in the same sediments. Calculated clusters of wind trajectories and satellite Aerosol Index imagery afford information on the source areas for the lipids and pollen on land and their transport pathways to the ocean sites. This multidisciplinary approach on an almost continental scale provides clear evidence of latitudinal differences in lipid and pollen composition paralleling the major phytogeographic zonations on the adjacent continent. Dust and smoke aerosols are mainly derived from the western and central South African hinterland dominated by deserts, semi-deserts and savannah regions rich in C4 and CAM plants. The northern sites (Congo Fan area and northern Angola Basin), which get most of their terrestrial material from the Congo Basin and the Angolan highlands, may also receive some material from the Chad region. Very little aerosol from the African continent is transported to the most southerly sites in the Cape Basin. As can be expected from the present position of the phytogeographic zones, the carbon isotopic signatures of the n-alkanes and n-alkanols both become isotopically more enriched in 13C from north to south. The results of the study suggest that this combination of pollen data and compound-specific isotope geochemical proxies can be effectively applied in the reconstruction of past continental phytogeographic developments.

Benthic foraminiferal stable isotope record from ODP Site 138-849 on the East Pacific Rise

Benthic foraminifer and delta13C data from Site 849, on the west flank of the East Pacific Rise (0°11 'N, 110°31'W; 3851 m), give relatively continuous records of deep Pacific Ocean stable isotope variations between 0 and 5 Ma. The mean sample spacing is 4 k.y. Most analyses are from Cibicides wuellerstorfi, but isotopic offsets relative to Uvigerina peregrina appear roughly constant. Because of its location west of the East Pacific Rise, Site 849 yields a suitable record of mean Pacific Ocean delta13C, which approximates a global oceanic signal. The ~100-k.y.-period climate cycle, which is prevalent in delta18O does not dominate the long-term delta13C record. For delta13C, variations in the ~400- and 41-k.y. periods are more important. Phase lags of delta13C relative to ice volume in the 41- and 23-k.y. bands are consistent with delta13C as a measure of organic biomass. A model-calculated exponential response time of 1-2 k.y. is appropriate for carbon stored in soils and shallow sediments responding to glacial-interglacial climate change. Oceanic delta13C leads ice volume slightly in the 100-k.y. band, and this suggests another process such as changes in continental weathering to modulate mean river delta13C at long periods. The delta13C record from Site 849 diverges from that of Site 677 in the Panama Basin mostly because of decay of 13C-depleted organic carbon in the relatively isolated Panama Basin. North Atlantic to Pacific delta13C differences calculated using published data from Sites 607 and 849 reveal variations in Pliocene deep water within the range of those of the late Quaternary. Maximum delta13C contrast between these sites, which presumably reflects maximum influx of high-delta13C northern source water into the deep North Atlantic Ocean, occurred between 1.3 and 2.1 Ma, well after the initiation of Northern Hemisphere glaciation. Export of high-delta13C North Atlantic Deep Water from the Atlantic to the circumpolar Antarctic, as recorded by published delta13C data from Subantarctic Site 704, appears unrelated to the North Atlantic-Pacific delta13C contrast. To account for this observation, we suggest that deep-water formation in the North Atlantic reflects northern source characteristics, whereas export of this water into the circumpolar Antarctic reflects Southern Hemisphere wind forcing. Neither process appears directly linked to ice-volume variations.

n-Alkane analyses from an transect of marine surface sediments off southwest Africa

An isobathic transect of marine surface sediments from 1°N to 28°S off southwest Africa was used to further evaluate the potential of the chain length distribution and carbon stable isotope composition of higher plant n-alkanes as proxies for continental vegetation and climate conditions. We found a strong increase in the n-C29-33 weighted mean average d13C values from -33 per mil near the equator to around -26 per mil further south. Additionally, C25-35n-alkanes reveal a southward trend of increasing average chain length from 30.0 to 30.5. The data reflect the changing contribution of plants employing different photosynthetic pathways (C3 and C4) and/or being differently influenced by the environmental conditions of their habitat. The C4 plant proportions calculated from the data (ca. 20% for rivers draining the rainforest, to ca. 70% at higher latitude) correspond to the C4 plant abundance in continental catchment areas postulated by considering prevailing wind systems and river outflows. Furthermore, the C4 plant contribution to the sediments correlates with the mean annual precipitation and aridity at selected continental locations in the postulated catchment areas, suggesting that the C4 plant fraction in marine sediments can be used to assess these environmental parameters.