Process studies of the biological pump of carbon dioxide in the North Sea and Southern Ocean

Sinds 1960 is de wereldbevolking gegroeid van 3 miljard tot nu meer dan 6 miljard mensen. Het verbruik van fossiele brandstoffen (aardolie, aardgas, steenkool) is nog sneller gestegen van 2 Petagram koolstof per jaar in 1960 tot nu bijna 7 Petagram koolstof per jaar (1 Petagram C = PgC = 1015 gram C). .... Zie: Samenvattin

Heteroleptic diimine copper(i) complexes with large extinction coefficients: synthesis, quantum chemistry calculations and physico-chemical properties.

International audience: Using the HETPHEN approach, five new heteroleptic copper(i) complexes composed of a push-pull 4,4'-styryl-6,6'-dimethyl-2,2'-bipyridine ligand and a bulky bis[(2-diphenylphosphino)phenyl]-ether (DPEphos) or a bis2,9-mesityl phenanthroline (Mes2Phen) were prepared and characterized by electronic absorption spectroscopy, electrochemistry, and TD-DFT calculations. These complexes exhibit very intense absorption bands in the visible region with extinction coefficient in the range of 5-7 × 10(4) M(-1) cm(-1). The analysis of the position, intensity and band shape indicates a strong contribution from an intra-ligand charge-transfer transition centered on the styrylbipyridine ligand along with MLCT transitions. These new complexes experimentally demonstrate that good light harvesting properties with bis-diimine copper(i) complexes are a reality if one chooses suitable ligands in the coordination sphere. This constitutes a milestone towards using bis-diimine copper(i) complexes for solar energy conversion (artificial photosynthesis and solar cells)

Mechanisms controlling the air-sea CO2 flux in the North Sea

The mechanisms driving the air–sea exchange of carbon dioxide (CO2CO2) in the North Sea are investigated using the three-dimensional coupled physical–biogeochemical model ECOHAM (ECOlogical-model, HAMburg). We validate our simulations using field data for the years 2001–2002 and identify the controls of the air–sea CO2CO2 flux for two locations representative for the North Sea's biogeochemical provinces. In the seasonally stratified northern region, net CO2CO2 uptake is high (View the MathML source2.06molm-2a-1) due to high net community production (NCP) in the surface water. Overflow production releasing semi-labile dissolved organic carbon needs to be considered for a realistic simulation of the low dissolved inorganic carbon (DIC) concentrations observed during summer. This biologically driven carbon drawdown outcompetes the temperature-driven rise in CO2CO2 partial pressure (pCO2pCO2) during the productive season. In contrast, the permanently mixed southern region is a weak net CO2CO2 source (View the MathML source0.78molm-2a-1). NCP is generally low except for the spring bloom because remineralization parallels primary production. Here, the pCO2pCO2 appears to be controlled by temperature

Carbon exchange between a shelf sea and the ocean: The Hebrides Shelf, west of Scotland

Global mass balance calculations indicate the majority of particulate organic carbon (POC) exported from shelf seas is transferred via downslope exchange processes. Here we demonstrate the downslope flux of POC from the Hebrides Shelf is approximately 3-to-5-fold larger per unit length/area than the global mean. To reach this conclusion we quantified the offshore transport of particulate and dissolved carbon fractions via the “Ekman Drain”, a strong downwelling feature of the NW European Shelf circulation, and subsequently compared these fluxes to simultaneous regional air-sea CO2 fluxes and on-shore wind-driven Ekman fluxes to constrain the carbon dynamics of this shelf. Along the shelf break we estimate a mean offshelf total carbon (dissolved + particulate) flux of 4.2 tonnes C m−1 d−1 compared to an onshelf flux of 4.5 tonnes C m−1 d−1. Organic carbon represented 3.3% of the onshelf carbon flux but 6.4% of the offshelf flux indicating net organic carbon export. Dissolved organic carbon represented 95% and POC 5% of the exported organic carbon pool. When scaled along the shelf break the total offshelf POC flux (0.007 Tg C d−1) was found to be three times larger than the regional air-sea CO2 ingassing flux (0.0021 Tg C d−1), an order of magnitude larger than the particulate inorganic carbon flux (0.0003 Tg C d−1) but far smaller than the DIC (2.03 Tg C d−1) or DOC (0.13 Tg C d−1) fluxes. Significant spatial heterogeneity in the Ekman drain transport confirms that offshelf carbon fluxes via this mechanism are also spatially heterogeneous. This article is protected by copyright. All rights reserved

Carbon exchange between a shelf sea and the ocean: The Hebrides Shelf, west of Scotland

Global mass balance calculations indicate the majority of particulate organic carbon (POC) exported from shelf seas is transferred via downslope exchange processes. Here we demonstrate the downslope flux of POC from the Hebrides Shelf is approximately 3-to-5-fold larger per unit length/area than the global mean. To reach this conclusion we quantified the offshore transport of particulate and dissolved carbon fractions via the “Ekman Drain”, a strong downwelling feature of the NW European Shelf circulation, and subsequently compared these fluxes to simultaneous regional air-sea CO2 fluxes and on-shore wind-driven Ekman fluxes to constrain the carbon dynamics of this shelf. Along the shelf break we estimate a mean offshelf total carbon (dissolved?+?particulate) flux of 4.2 tonnes C m?1 d?1 compared to an onshelf flux of 4.5 tonnes C m?1 d?1. Organic carbon represented 3.3% of the onshelf carbon flux but 6.4% of the offshelf flux indicating net organic carbon export. Dissolved organic carbon represented 95% and POC 5% of the exported organic carbon pool. When scaled along the shelf break the total offshelf POC flux (0.007 Tg C d?1) was found to be three times larger than the regional air-sea CO2 ingassing flux (0.0021 Tg C d?1), an order of magnitude larger than the particulate inorganic carbon flux (0.0003 Tg C d?1) but far smaller than the DIC (2.03 Tg C d?1) or DOC (0.13 Tg C d?1) fluxes. Significant spatial heterogeneity in the Ekman drain transport confirms that offshelf carbon fluxes via this mechanism are also spatially heterogeneous. This article is protected by copyright. All rights reserved

Rapid decline of the CO2 buffering capacity in the North Sea and implications for the North Atlantic Ocean

Author Posting. © American Geophysical Union, 2007. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 21 (2007): GB4001, doi:10.1029/2006GB002825.New observations from the North Sea, a NW European shelf sea, show that between 2001 and 2005 the CO2 partial pressure (pCO2) in surface waters rose by 22 μatm, thus faster than atmospheric pCO2, which in the same period rose approximately 11 μatm. The surprisingly rapid decline in air-sea partial pressure difference (ΔpCO2) is primarily a response to an elevated water column inventory of dissolved inorganic carbon (DIC), which, in turn, reflects mostly anthropogenic CO2 input rather than natural interannual variability. The resulting decline in the buffering capacity of the inorganic carbonate system (increasing Revelle factor) sets up a theoretically predicted feedback loop whereby the invasion of anthropogenic CO2 reduces the ocean's ability to uptake additional CO2. Model simulations for the North Atlantic Ocean and thermodynamic principles reveal that this feedback should be stronger, at present, in colder midlatitude and subpolar waters because of the lower present-day buffer capacity and elevated DIC levels driven either by northward advected surface water and/or excess local air-sea CO2 uptake. This buffer capacity feedback mechanism helps to explain at least part of the observed trend of decreasing air-sea ΔpCO2 over time as reported in several other recent North Atlantic studies.S. Doney and I. Lima were supported by NSF/ONR NOPP (N000140210370) and NASA (NNG05GG30G)

The elemental stoichiometry (C, Si, N, P) of the Hebrides Shelf and its role in carbon export

A detailed analysis of the internal stoichiometry of a temperate latitude shelf sea system is presented which reveals strong vertical and horizontal gradients in dissolved nutrient and particulate concentrations and in the elemental stoichiometry of those pools. Such gradients have implications for carbon and nutrient export from coastal waters to the open ocean. The mixed layer inorganic nutrient stoichiometry shifted from balanced N:P in winter, to elevated N:P in spring and to depleted N:P in summer, relative to the Redfield ratio. This pattern suggests increased likelihood of P limitation of fast growing phytoplankton species in spring and of N limitation of slower growing species in summer. However, as only silicate concentrations were below potentially limiting concentrations during summer and autumn the stoichiometric shifts in inorganic nutrient N:P are considered due to phytoplankton nutrient preference patterns rather than nutrient exhaustion. Elevated particulate stoichiometries corroborate non-Redfield optima underlying organic matter synthesis and nutrient uptake. Seasonal variation in the stoichiometry of the inorganic and organic nutrient pools has the potential to influence the efficiency of nutrient export. In summer, when organic nutrient concentrations were at their highest and inorganic nutrient concentrations were at their lowest, the organic nutrient pool was comparatively C poor whilst the inorganic nutrient pool was comparatively C rich. The cross-shelf export of these pools at this time would be associated with different efficiencies regardless of the total magnitude of exchange. In autumn the elemental stoichiometries increased with depth in all pools revealing widespread carbon enrichment of shelf bottom waters with P more intensely recycled than N, N more intensely recycled than C, and Si weakly remineralized relative to C. Offshelf carbon fluxes were most efficient via the inorganic nutrient pool, intermediate for the organic nutrient pool and least efficient for the particulate pool. N loss from the shelf however was most efficient via the dissolved organic nutrient pool. Mass balance calculations suggest that 28% of PO43−, 34% of NO3− and 73% of Si drawdown from the mixed layer fails to reappear in the benthic water column thereby indicating the proportion of the nutrient pools that must be resupplied from the ocean each year to maintain shelf wide productivity. Loss to the neighbouring ocean, the sediments, transference to the dissolved organic nutrient pool and higher trophic levels are considered the most likely fate for these missing nutrients