Analysis and compound of carbon sequestration and serpentinization from the Iberian Margin and the Northern Apennine

Fluid circulation in peridotite-hosted hydrothermal systems influences the incorporation of carbon into the oceanic crust and its long-term storage. At low to moderate temperatures, serpentinization of peridotite produces alkaline fluids that are rich in CH4 and H2. Upon mixing with seawater, these fluids precipitate carbonate, forming an extensive network of calcite veins in the basement rocks, while H2 and CH4 serve as an energy source for microorganisms. Here, we analyzed the carbon geochemistry of two ancient peridotite-hosted hydrothermal systems: 1) ophiolites cropping out in the Northern Apennines, and 2) calcite-veined serpentinites from the Iberian Margin (Ocean Drilling Program (ODP) Legs 149 and 173), and compare them to active peridotite-hosted hydrothermal systems such as the Lost City hydrothermal field (LCHF) on the Atlantis Massif near the Mid-Atlantic Ridge (MAR). Our results show that large amounts of carbonate are formed during serpentinization of mantle rocks exposed on the seafloor (up to 9.6 wt.% C in ophicalcites) and that carbon incorporation decreases with depth. In the Northern Apennine serpentinites, serpentinization temperatures decrease from 240 °C to < 150 °C, while carbonates are formed at temperatures decreasing from ~ 150 °C to < 50 °C. At the Iberian Margin both carbonate formation and serpentinization temperatures are lower than in the Northern Apennines with serpentinization starting at ~ 150 °C, followed by clay alteration at < 100 °C and carbonate formation at < 19-44 °C. Comparison with various active peridotite-hosted hydrothermal systems on the MAR shows that the serpentinites from the Northern Apennines record a thermal evolution similar to that of the basement of the LCHF and that tectonic activity on the Jurassic seafloor, comparable to the present-day processes leading to oceanic core complexes, probably led to formation of fractures and faults, which promoted fluid circulation to greater depth and cooling of the mantle rocks. Thus, our study provides further evidence that the Northern Apennine serpentinites host a paleo-stockwork of a hydrothermal system similar to the basement of the LCHF. Furthermore, we argue that the extent of carbonate uptake is mainly controlled by the presence of fluid pathways. Low serpentinization temperatures promote microbial activity, which leads to enhanced biomass formation and the storage of organic carbon. Organic carbon becomes dominant with increasing depth and is the principal carbon phase at more than 50-100 m depth of the serpentinite basement at the Iberian Margin. We estimate that annually 1.1 to 2.7 × 1012 g C is stored within peridotites exposed to seawater, of which 30-40% is fixed within the uppermost 20-50 m mainly as carbonate. Additionally, we conclude that alteration of oceanic lithosphere is an important factor in the long-term global carbon cycle, having the potential to store carbon for millions of years.

Past circulation along the western Iberian margin

Fifteen Iberian margin sediment cores, distributed between 43°12'N and 35°53'N, have been used to reconstruct spatial and temporal (sub)surface circulation along the Iberian margin since the Last Glacial period. Time-slice maps of planktonic foraminiferal derived summer sea surface temperature (SST) and export productivity (Pexp) were established for specific time intervals within the last 35 ky: the Holocene (Recent and last 8 ky), Younger Dryas (YD), Heinrich Stadials (HS) 1, 2a, 2b, 3, and the Last Glacial Maximum (LGM). The SST during the Holocene shows the same latitudinal gradient along the western Iberian margin as present-day with cold but productive areas that reflect the influence of coastal upwelling centers. The LGM appears as a slightly less warm, but more productive period relative to the Holocene and present-day conditions, suggesting that sea-level minima forced a westward displacement of the coastal upwelling centers possibly accompanied by a strengthening of northward winds. During the YD, a longitudinal thermal front is depicted at 10°W, with cold polar waters offshore and warmer subtropical waters inshore, suggesting that the subtropical Paleo-Iberian Poleward Current more likely flowed at a more inshore location masking the local SST signal and amplitude of variation. A substantial cooling and drop in productivity is observed during all HS, in particular HS1 and HS3, reflecting the penetration of icebergs-derived meltwater. These most extreme southward extensions of very cold waters define a strong SST gradient that marks a possible Paleo-Azores Front. Higher production south of this front was likely fed by frontal nutrient advection.

Heat flow ratios of stations from the Iberian abyssal plain (Table 1)

New heat flow observations have been made in the Iberia abyssal plain off the Galicia margin along the transeat of Ocean Drilling Program Leg 149 drill sites. in order to investigate the nature of this unusually wide and deep continet-ocean transition region. Our results indicate the presence of three separate zones. Average values of 47.5 +/- 3 mW/m in the westernmost zone III agree with predictions of standard oceanic lithospheric models for its estimated age of 126 Ma. In contrast, the heat flow within zone II is 5-15 mW/m higher than predicted. assuming that the mantle heat flow remains constant across the basin. This region of high values is coincident with the location of a major intra-crustal "S"-type reflector east of ODP Site 900. and the anomaly is consistent with the presence of 2-3 km of primarily upper continental crust above the reflector, with concentrations of radiogenic components similar to those from granodiorite samplles dredged off Galicia Bank. It is not, however, consistent with the low values of heat production measured on gabbroic sanhples from its western end at ODP Site 900. In zone I, detailed measurements across the tilted fault block south of ODP Site 901 show consistent variations which closely match predictions due to the effects of basement structure and sediment deposition. There is no evidence for variations due to vertical convective transport along the dipping basement fault block. Once corrected for these variations. measurements in zone I yield average values that agree quite well with previous measurements across Calicia Bank. indicating no systematic landward increase in heat flow with decreasing amounts of continental, extension.

Age determination and sea surface temperature reconstruction from marine and lake records, Iberian Peninsula

Selected multi-proxy and accurately dated marine and terrestrial records covering the past 2000 years in the Iberian Peninsula (IP) facilitated a comprehensive regional paleoclimate reconstruction for the Medieval Climate Anomaly (MCA: 900-1300 AD). The sequences enabled an integrated approach to land-sea comparisons and, despite local differences and some minor chronological inconsistencies, presented clear evidence that the MCA was a dry period in the Mediterranean IP. It was a period characterized by decreased lake levels, more xerophytic and heliophytic vegetation, a low frequency of floods, major Saharan eolian fluxes, and less fluvial input to marine basins. In contrast, reconstruction based on sequences from the Atlantic Ocean side of the peninsula indicated increased humidity. The data highlight the unique characteristics of the MCA relative to earlier (the Dark Ages, DA: ca. 500-900 years AD) and subsequent (the Little Ice Age, LIA: 1300-1850 years AD) colder periods. The reconstruction supports the hypothesis of Trouet et al. (2009, doi:10.1126/science.1166349), that a persistent positive mode of the North Atlantic Oscillation (NAO) dominated the MCA.

Distribution of benthic abyssal gastropods in the Iberian Deep-Sea Basin (Table 2)

During the cruises 3 and 15 of R.V. "Meteor", representatives of 7 families of benthic abyssal gastropods were collected. The prevalent group was the Turridae; the Naticidae are represented by 2 species, the remaining families by a single species each. A survey of the frequency and distribution of the species within the study area is given. A systematic part deals with the individual species in detail, including notes on taxonomy, material and distribution. Concerning the composition of the abyssal gastropod fauna of the present material, Neogastropoda are 4 times as many as Archaeogastropoda and 6 times as many as Mesogastropoda and Opisthobranchia. 89 % of all specimens are Neogastropoda. Usually deep-sea organisms have a non-pelagic development, but many of the Iberian deep-sea Turrids have a planktotrophic protoconch, that means a long pelagic larval period. Among the 19 species, 2 are cosmopolitan, 9 show a transatlantic distribution and 8 are confined to East-Atlantic basins.

Iberian Margin 420 kyr geochemical and color variations record

Here we report 420 kyr long records of sediment geochemical and color variations from the southwestern Iberian Margin. We synchronized the Iberian Margin sediment record to Antarctic ice cores and speleothem records on millennial time scales and investigated the phase responses relative to orbital forcing of multiple proxy records available from these cores. Iberian Margin sediments contain strong precession power. Sediment "redness" (a* and 570-560 nm) and the ratio of long-chain alcohols to n-alkanes (C26OH/(C26OH + C29)) are highly coherent and in-phase with precession. Redder layers and more oxidizing conditions (low alcohol ratio) occur near precession minima (summer insolation maxima). We suggest these proxies respond rapidly to low-latitude insolation forcing by wind-driven processes (e.g., dust transport, upwelling, precipitation). Most Iberian Margin sediment parameters lag obliquity maxima by 7-8 ka, indicating a consistent linear response to insolation forcing at obliquity frequencies driven mainly by high-latitude processes. Although the lengths of the time series are short (420 ka) for detecting 100 kyr eccentricity cycles, the phase relationships support those obtained by Shackleton []. Antarctic temperature and the Iberian Margin alcohol ratios (C26OH/(C26OH + C29)) lead eccentricity maxima by 6 kyr, with lower ratios (increased oxygenation) occurring at eccentricity maxima. CO2, CH4, and Iberian SST are nearly in phase with eccentricity, and minimum ice volume (as inferred from Pacific d18Oseawater) lags eccentricity maxima by 10 kyr. The phase relationships derived in this study continue to support a potential role of the Earth's carbon cycle in contributing to the 100 kyr cycle.

Magnetic properties of two cores from the Iberian Margin

Magnetic properties of late Quaternary sediments on the SW Iberian Margin are dominated by bacterial magnetite, observed by transmission electron microscopy (TEM), with contributions from detrital titanomagnetite and hematite. Reactive hematite from eolian dust, together with low organic matter concentrations and the lack of sulfate reduction, lead to dissimilatory iron reduction and availability of Fe(II) for abundant magnetotactic bacteria. Magnetite grain-size proxies (kARM/k and ARM/IRM) and S-ratios (sensitive to hematite) vary on stadial/interstadial timescales, contain orbital power, and mimic planktic d18O. The detrital/biogenic magnetite ratio and hematite concentration are greater during stadials and glacial isotopic stages, reflecting increased detrital (magnetite) input during times of lowered sea level, coinciding with atmospheric conditions favoring hematitic dust supply. Magnetic susceptibility, on the other hand, has a very different response being sensitive to coarse detrital multidomain (MD) magnetite associated with ice-rafted debris (IRD). High susceptibility and/or magnetic grain size coarsening, mark Heinrich stadials (HS), particularly HS2, HS3, HS4, HS5, HS6 and HS7, as well as older Heinrich-like detrital layers, indicating the sensitivity of this region to fluctuations in the position of the polar front. Relative paleointensity (RPI) records have well-constrained age models based on planktic d18O correlation to ice-core chronologies, however, they differ from reference records (e.g. PISO) particularly in the vicinity of glacial maxima, mainly due to inefficient normalization of RPI records in intervals of enhanced detrital/eolian hematite input.

Stable isotope record of planktonic foraminifera from the western Iberian margin during marine isotope stage 2

The surface water hydrography along the western Iberian margin, as part of the North Atlantic's eastern boundary upwelling system, consists of a complex, seasonally variable system of equatorward and poleward surface and subsurface currents and seasonal upwelling. Not much information exists to ascertain if the modern current and productivity patterns subsisted under glacial climate conditions, such as during marine isotope stage (MIS) 2, and how North Atlantic meltwater events, especially Heinrich events, affected them. To help answer these questions we are combining stable isotope records of surface to subsurface dwelling planktonic foraminifer species with sea surface temperature and export productivity data for four cores distributed along the western and southwestern Iberian margin (MD95-2040, MD95-2041, MD99-2336, and MD99-2339). The records reveals that with the exception of the Heinrich events and Greenland Stadial (GS) 4 hydrographic conditions along the western Iberian margin were not much different from the present. During the Last Glacial Maximum (LGM), subtropical surface and subsurface waters penetrated poleward to at least 40.6°N (site MD95-2040). Export productivity was, in general, high on the western margin during the LGM and low in the central Gulf of Cadiz, in agreement with the modern situation. During the Heinrich events and GS 4, on the other hand, productivity was high in the Gulf of Cadiz and suppressed in the upwelling regions along the western margin where a strong halocline inhibited upwelling. Heinrich event 1 had the strongest impact on the hydrography and productivity off Iberia and was the only period when subarctic surface waters were recorded in the central Gulf of Cadiz. South of Lisbon (39°N), the impact of the other Heinrich events was diminished, and not all of them led to a significant cooling in the surface waters. Thus, climatic impacts of Heinrich events highly varied with latitude and the prevailing hydrographic conditions in this region.

Pliocene-Pleistocene calcareous nannofossils from the Iberian Abyssal Plain

During Ocean Drilling Program Leg 149, five sites were drilled on the Iberia Abyssal Plain, west of the Iberian Peninsula. Five holes (Holes 897A, 897C, 898A, 899A, and 900A) yielded Pliocene-Pleistocene sediments, which consist mainly of turbidites. Among these, Holes 897C and 898A yielded significant Pliocene-Pleistocene sediments that provided a high-resolution nannofossil biostratigraphy essential for locating paleomagnetic polarity events and for interpreting the age and frequency of turbidite sedimentation in the Iberia Abyssal Plain. Pliocene-Pleistocene nannofossils recovered during Leg 149 are generally abundant and well to moderately preserved. Although reworking is evident in most samples, the Pliocene-Pleistocene nannofossils proved quite reliable for dating the sediments. Most Pleistocene zonal boundaries proposed by S. Gartner in 1977 and the Pliocene standard zonal boundaries proposed by E. Martini in 1971 were easily recognized. In addition, several other nannofossil events proposed by D. Rio et al. in 1990 and by T. Sato and T. Takayama in 1992 were recognized and proved valuable for improving the resolution of Pliocene-Pleistocene nannofossil biostratigraphy. The Pliocene-Pleistocene nannofossil biostratigraphic results of Holes 897C and 900A coincide rather well with the discerned paleomagnetic polarity events. As a result, the combination of nannofossil biostratigraphic and paleomagnetic studies provides important information for fulfilling the second objective of this leg: to determine the history of turbidite sedimentation in the Iberia Abyssal Plain. The general trend of sedimentation rates inferred by nannofossil biostratigraphy indicates that sedimentation rates increase from the continental margin to the deep sea along with increasing water depth.

Stable isotope record, and abundances of ice rafted debris and Neogloboquadrina pachyderma in sediments of the Iberian margin

This paper documents the migration of the Polar Front (PF) over the Iberian margin during some of the cold climatic extremes of the last 45 ka. It is based on a compilation of robust and coherent paleohydrological proxies obtained from eleven cores distributed between 36 and 42°N. Planktonic delta18O (Globigerina bulloides), ice-rafted detritus concentrations, and the relative abundance of the polar foraminifera Neogloboquadrina pachyderma sinistral were used to track the PF position. These three data sets, compared from core to core, show a consistent evolution of the sea surface paleohydrology along the Iberian margin over the last 45 ka. We focused on five time slices representative of cold periods under distinct paleoenvironmental forcings: the 8.2 ka event and the Younger Dryas (two recent cold events occurring within high values of summer insolation), Heinrich events 1 and 4 (reflecting major episodes of massive iceberg discharges into the North Atlantic), and the Last Glacial Maximum (typifying the highest ice volume accumulated in the Northern Hemisphere). For each event, we generated schematic maps mirroring past sea surface hydrological conditions. The maps revealed that the Polar Front presence along the Iberian margin was restricted to Heinrich events. The sea surface conditions during the Last Glacial Maximum were close to those at present day, except for the northern sites which briefly experienced subarctic conditions.