IBAMar DATABASE: 4 decades of oceanographic sampling on the Western Mediterranean Sea

IBAMar (http://www.ba.ieo.es/ibamar) is a regional database that puts together all physical and biochemical data obtained by multiparametric probes (CTDs equipped with different sensors), during the cruises managed by the Balearic Center of the Spanish Institute of Oceanography (COB-IEO). It has been recently extended to include data obtained with classical hydro casts using oceanographic Niskin or Nansen bottles. The result is a database that includes a main core of hydrographic data: temperature (T), salinity (S), dissolved oxygen (DO), fluorescence and turbidity; complemented by bio-chemical data: dissolved inorganic nutrients (phosphate, nitrate, nitrite and silicate) and chlorophyll-a. In IBAMar Database, different technologies and methodologies were used by different teams along the four decades of data sampling in the COB-IEO. Despite of this fact, data have been reprocessed using the same protocols, and a standard QC has been applied to each variable. Therefore it provides a regional database of homogeneous, good quality data. Data acquisition and quality control (QC): 94% of the data are CTDs Sbe911 and Sbe25. S and DO were calibrated on board using water samples, whenever a Rossetta was available (70% of the cases). All CTD data from Seabird CTDs were reviewed and post processed with the software provided by Sea-Bird Electronics. Data were averaged to get 1 dbar vertical resolution. General sampling methodology and pre processing are described in https://ibamardatabase.wordpress.com/home/). Manual QC include visual checks of metadata, duplicate data and outliers. Automatic QC include range check of variables by area (north of Balearic Islands, south of BI and Alboran Sea) and depth (27 standard levels), check for spikes and check for density inversions. Nutrients QC includes a preliminary control and a range check on the observed level of the data to detect outliers around objectively analyzed data fields. A quality flag is assigned as an integer number, depending on the result of the QC check.

Nannofossil biostratigraphy of ODP Site 210-1276 sediments

Ocean Drilling Program (ODP) Leg 210 is one of very few deep-sea legs drilled along the eastern Canadian continental margin. Most other drilling on this margin has been carried out by the petroleum industry on the shallow-water regions of the Scotian shelf and the Grand Banks (see Doeven, 1983, for nannofossil studies). Deep Sea Drilling Project (DSDP) Leg 12 Site 111 and ODP Leg 105 Site 647 were drilled in the general vicinity of Leg 210 but recovered no appreciable Lower Cretaceous (Albian-Cenomanian) sediments. Site 111 yielded indurated limestones dated tentatively as late Albian-early Cenomanian, whereas Site 647 encountered no Albian-Cenomanian sediments. Two sites (Sites 1276 and 1277) were drilled during Leg 210 in the Newfoundland Basin with the primary objective of recovering basement rocks to elucidate the rifting history of the North Atlantic Basin. The location for Leg 210 was selected because it is conjugate to the Iberia margin, which was drilled extensively during DSDP/ODP Legs 47B, 103, 149, and 173. A secondary but equally important objective was to recover the overlying sediments with the purpose of studying the postrift sedimentation history of this margin.

Current meter data from mooring stations in the English Channel (Table 1)

A new technique for the harmonic analysis of current observations is described. It consists in applying a linear band pass filter which separates the various species and removes the contribution of non-tidal effects at intertidal frequencies. The tidal constituents are then evaluated through the method of least squares. In spite of the narrowness of the filter, only three days of data are lost through the filtering procedure and the only requirement on the data is that the time interval between samples be an integer fraction of one day. This technique is illustrated through the analysis of a few French current observations from the English Channel within the framework of INOUT. The characteristics of the main tidal constituents are given.

Spatially explicit methane inventory for Switzerland with 500 m x 500 m resolution for 2011 (NetCDF 25 MB)

We present the first high-resolution (500 m × 500 m) gridded methane (CH4) emission inventory for Switzerland, which integrates the national emission totals reported to the United Nations Framework Convention on Climate Change (UNFCCC) and recent CH4 flux studies conducted by research groups across Switzerland. In addition to anthropogenic emissions, we also include natural and semi-natural CH4 fluxes, i.e., emissions from lakes and reservoirs, wetlands, wild animals as well as uptake by forest soils. National CH4 emissions were disaggregated using detailed geostatistical information on source locations and their spatial extent and process- or area-specific emission factors. In Switzerland, the highest CH4 emissions in 2011 originated from the agricultural sector (150 Gg CH4/yr), mainly produced by ruminants and manure management, followed by emissions from waste management (15 Gg CH4/yr) mainly from landfills and the energy sector (12 Gg CH4/yr), which was dominated by emissions from natural gas distribution. Compared to the anthropogenic sources, emissions from natural and semi-natural sources were relatively small (6 Gg CH4/yr), making up only 3 % of the total emissions in Switzerland. CH4 fluxes from agricultural soils were estimated to be not significantly different from zero (between -1.5 and 0 Gg CH4/yr), while forest soils are a CH4 sink (approx. -2.8 Gg CH4/yr), partially offsetting other natural emissions. Estimates of uncertainties are provided for the different sources, including an estimate of spatial disaggregation errors deduced from a comparison with a global (EDGAR v4.2) and a European CH4 inventory (TNO/MACC). This new spatially-explicit emission inventory for Switzerland will provide valuable input for regional scale atmospheric modeling and inverse source estimation.

Highly dealkylated copper and nickel etioporpyfrins in marine sediments

Copper porphyrins have been recognized as natural constituents of marine sediments only within the past 5 years (Palmer and Baker, 1978, Science201, 49-51). In that report it was suggested that these pigments may derive from and be markers for oxidized terrestrial organic matter redeposited in the marine environment. In the present study we describe the distribution of copper porphyrins in sediments from several north Pacific and Gulf of California DSDP/IPQD sites (Legs 56,63,64). These allochthonous pigments have now been found to be accompanied by identical arrays of highly dealkylated nickel etioporphyrins. Evaluation of data from this and past studies clearly reveals that there is a strong carbon-number distribution similarity betweeen coincident Cu and Ni etioporphyrins. This homology match is taken as reflecting a common source for the tetrapyrrole ligands of this population of Cu and Ni chelates. Predepositional generation of these highly dealkylated etioporphyrins is concluded from the occurrence of these pigments in sediments continuing essentially all stages of in situ chlorophyll diagenesis (cf. Baker and Louda, 1983). That is, their presence is not regulated by the in situ diagenetic continuum. Thus, the highly dealkylated Cu and Ni etioporphyrins represent an 'allochthonous' background over which 'autochthonous' (viz. marine produced) chlorophyll derivatives are deposited and are undergoing in situ diagenesis.

Geochemistry of plagioclase from the Mid-Atlantic Ridge

We have studied the chemical zoning of plagioclase phenocrysts from the slow-spreading Mid-Atlantic Ridge and the intermediate-spreading rate Costa Rica Rift to obtain the time scales of magmatic processes beneath these ridges. The anorthite content, Mg, and Sr in plagioclase phenocrysts from the Mid-Atlantic Ridge can be interpreted as recording initial crystallisation from a primitive magma (~11 wt% MgO) in an open system. This was followed by crystal accumulation in a mush zone and later entrainment of crystals into the erupted magma. The initial magma crystallised plagioclase more anorthitic than those in equilibrium with any erupted basalt. Evidence that the crystals accumulated in a mush zone comes from both: (1) plagioclase rims that were in equilibrium with a Sr-poor melt requiring extreme differentiation; and (2) different crystals found in the same thin section having different histories. Diffusion modelling shows that crystal residence times in the mush were <140 years, whereas the interval between mush disaggregation and eruption was ?1.5 years. Zoning of anorthite content and Mg in plagioclase phenocrysts from the Costa Rica Rift show that they partially or completely equilibrated with a MgO-rich melt (>11 wt%). Partial equilibration in some crystals can be modelled as starting <1 year prior to eruption but for others longer times are required for complete equilibration. This variety of times is most readily explained if the mixing occurred in a mush zone. None of the plagioclase phenocrysts from the Costa Rica Rift that we studied have Mg contents in equilibrium with their host basalt even at their rims, requiring mixing into a much more evolved magma within days of eruption. In combination these observations suggest that at both intermediate- and slow-spreading ridges: (1) the chemical environment to which crystals are exposed changes on annual to decadal time scales; (2) plagioclase crystals record the existence of melts unlike those erupted; and (3) disaggregation of crystal mush zones appears to precede eruption, providing an efficient mechanism by which evolved interstitial melt can be mixed into erupted basalts.

Porphyrin geochemistry of DSDP Hole 71-511

Late Jurassic-early Cretaceous black shales and an overlying sequence of Albian-Campanian zeolitic claystones from the Falkland Plateau (DSDP/IPOD Leg 71, Site 511) were analyzed for tetrapyrrole pigment type and abundance. The "black shale" sequence was found to be rich in DPEP-series dominated free-base, nickel (Ni) and, to a lesser extent, vanadyl (V = 0) porphyrins. A low level of organic maturity (i.e. precatagenesis) is indicated for these strata as nickel chelation by free-base porphyrins is only 50-75% complete, proceeding down-hole to 627 meters sub-bottom. Electronic and mass spectral data reveal that the proposed benzo-DPEP (BD) and tetrahydrobenzo-DPEP (THBD) series are present in the free-base and Ni species, as well as the more usual occurrence in V = 0 porphyrin arrays. Highly reducing conditions are suggested by an abundance of the PAH perylene, substantial amounts of the THBD/BD series and a redox equilibrium between free-base DPEP and 7,8-dihydro-DPEP series, which exist in a 7:1 molar ratio. The Albian-Campanian claystone strata were found to be tetrapyrrolepoor, and those pigments present were typed as Cu/Ni highly dealkylated (C26 max.) etioporphyrins, thought to be derived via redeposition and oxidation of terrestrial organic matter (OM). Results from the present study are correlated to our past analyses of Jurassic-Cretaceous sediments from Atlantic margins in an effort to relate tetrapyrrole quality and quantity to basin evolution and OM sources in the proto-Atlantic.

Particle camera and settling chamber measurements at site PC (GeoB11834-3) and SC (GeoB12914-4) off Cape Blanc/Mauritania

Particles sinking out of the euphotic zone are important vehicles of carbon export from the surface ocean. Most of the particles produce heavier aggregates by coagulating with each other before they sink. We implemented an aggregation model into the biogeochemical model of Regional Oceanic Modelling System (ROMS) to simulate the distribution of particles in the water column and their downward transport in the Northwest African upwelling region. Accompanying settling chamber, sediment trap and particle camera measurements provide data for model validation. In situ aggregate settling velocities measured by the settling chamber were around 55 m d**-1. Aggregate sizes recorded by the particle camera hardly exceeded 1 mm. The model is based on a continuous size spectrum of aggregates, characterised by the prognostic aggregate mass and aggregate number concentration. Phytoplankton and detritus make up the aggregation pool, which has an averaged, prognostic and size dependent sinking. Model experiments were performed with dense and porous approximations of aggregates with varying maximum aggregate size and stickiness as well as with the inclusion of a disaggregation term. Similar surface productivity in all experiments has been generated in order to find the best combination of parameters that produce measured deep water fluxes. Although the experiments failed to represent surface particle number spectra, in the deep water some of them gave very similar slope and spectrum range as the particle camera observations. Particle fluxes at the mesotrophic sediment trap site off Cape Blanc (CB) have been successfully reproduced by the porous experiment with disaggregation term when particle remineralisation rate was 0.2 d**-1. The aggregation-disaggregation model improves the prediction capability of the original biogeochemical model significantly by giving much better estimates of fluxes for both upper and lower trap. The results also point to the need for more studies to enhance our knowledge on particle decay and its variation and to the role that stickiness play in the distribution of vertical fluxes.