Geochemistry and stable carbon isotope composition of kerogen of DSDP Site 124-767

Celebes Basin sediments from Ocean Drilling Program Site 767 (Leg 124) containing both marine and terrestrial organic matter have been investigated through palynofacies and geochemical analyses. The main degradation processes affecting or having affected organic matter are recorded in the sedimentary column as shown by ammonium, phosphate and sulfate pore-water profiles, and by petrographic and geochemical analyses of sediments. In the upper part of the sedimentary section (down to 200 mbsf), the decrease of the ratio of total organic carbon to sulfur (TOC/S) with depth, generally related to the sulfate reduction process, is accompanied by an increase of framboidal pyrite content in the marine organic matter, and by an increasing amount of amorphous marine organic matter relative to the total organic matter. However, as the terrestrial organic input also varies with depth, dilution effects are superimposed on diagenesis. This continental supply affects the TOC/S ratio by increasing total organic carbon and decreasing the ability of the bulk organic matter to be metabolized through sulfate reduction. A positive relationship between the TOC/P ratio and the amount of degraded organic matter of marine origin clearly displays the effect of an organic source on the composition of the sediment. Each lithostratigraphic unit possesses its own characteristics in terms of composition and preservation of organic matter. The effects of diagenesis can only be appreciated within a single lithostratigraphic unit and mainly affect the less-resistant marine organic matter.

Sea surface temperature reconstruction based on dinoflagellates from the North Atlantic

The application of quantitative and semiquantitative methods to assemblage data from dinoflagellate cysts shows potential for interpreting past environments, both in terms of paleotemperature estimates and in recognizing water masses and circulation patterns. Estimates of winter sea-surface temperature (WSST) were produced by using the Impagidinium Index (II) method, and by applying a winter-temperature transfer function (TFw). Estimates of summer sea-surface temperature (SSST) were produced by using a summer-temperature transfer function (TFs), two methods based on a temperature-distribution chart (ACT and ACTpo), and a method based on the ratio of gonyaulacoid:protoperidinioid specimens (G:P). WSST estimates from the II and TFw methods are in close agreement except where Impagidinium species are sparse. SSST estimates from TFs are more variable. The value of the G:P ratio for the Pliocene data in this paper is limited by the apparent sparsity of protoperidinioids, which results in monotonous SSST estimates of 14-26°C. The ACT methods show two biases for the Pliocene data set: taxonomic substitution may force 'matches' yielding incorrect temperature estimates, and the method is highly sensitive to the end-points of species distributions. Dinocyst assemblage data were applied to reconstruct Pliocene sea-surface temperatures between 3.5-2.5 Ma from DSDP Hole 552A, and ODP Holes 646B and 642B, which are presently located beneath cold and cool-temperate waters north of 56°N. Our initial results suggest that at 3.0 Ma, WSSTs were a few degrees C warmer than the present and that there was a somewhat reduced north-south temperature gradient. For all three sites, it is likely that SSSTs were also warmer, but by an unknown, perhaps large, amount. Past oceanic circulation in the North Atlantic was probably different from the present.

Zooplankton data of M83/1

Oxygen-deficient waters in the ocean, generally referred to as oxygen minimum zones (OMZ), are expected to expand as a consequence of global climate change. Poor oxygenation is promoting microbial loss of inorganic nitrogen (N) and increasing release of sediment-bound phosphate (P) into the water column. These intermediate water masses, nutrient-loaded but with an N deficit relative to the canonical N:P Redfield ratio of 16:1, are transported via coastal upwelling into the euphotic zone. To test the impact of nutrient supply and nutrient stoichiometry on production, partitioning and elemental composition of dissolved (DOC, DON, DOP) and particulate (POC, PON, POP) organic matter, three nutrient enrichment experiments were conducted with natural microbial communities in shipboard mesocosms, during research cruises in the tropical waters of the southeast Pacific and the northeast Atlantic. Maximum accumulation of POC and PON was observed under high N supply conditions, indicating that primary production was controlled by N availability. The stoichiometry of microbial biomass was unaffected by nutrient N:P supply during exponential growth under nutrient saturation, while it was highly variable under conditions of nutrient limitation and closely correlated to the N:P supply ratio, although PON:POP of accumulated biomass generally exceeded the supply ratio. Microbial N:P composition was constrained by a general lower limit of 5:1. Channelling of assimilated P into DOP appears to be the mechanism responsible for the consistent offset of cellular stoichiometry relative to inorganic nutrient supply and nutrient drawdown, as DOP build-up was observed to intensify under decreasing N:P supply. Low nutrient N:P conditions in coastal upwelling areas overlying O2-deficient waters seem to represent a net source for DOP, which may stimulate growth of diazotrophic phytoplankton. These results demonstrate that microbial nutrient assimilation and partitioning of organic matter between the particulate and the dissolved phase are controlled by the N:P ratio of upwelled nutrients, implying substantial consequences for nutrient cycling and organic matter pools in the course of decreasing nutrient N:P stoichiometry.

Biogeochemistry of mesocosm experiments in the tropical Pacific and Atlantic Ocean

Oxygen-deficient waters in the ocean, generally referred to as oxygen minimum zones (OMZ), are expected to expand as a consequence of global climate change. Poor oxygenation is promoting microbial loss of inorganic nitrogen (N) and increasing release of sediment-bound phosphate (P) into the water column. These intermediate water masses, nutrient-loaded but with an N deficit relative to the canonical N:P Redfield ratio of 16:1, are transported via coastal upwelling into the euphotic zone. To test the impact of nutrient supply and nutrient stoichiometry on production, partitioning and elemental composition of dissolved (DOC, DON, DOP) and particulate (POC, PON, POP) organic matter, three nutrient enrichment experiments were conducted with natural microbial communities in shipboard mesocosms, during research cruises in the tropical waters of the southeast Pacific and the northeast Atlantic. Maximum accumulation of POC and PON was observed under high N supply conditions, indicating that primary production was controlled by N availability. The stoichiometry of microbial biomass was unaffected by nutrient N:P supply during exponential growth under nutrient saturation, while it was highly variable under conditions of nutrient limitation and closely correlated to the N:P supply ratio, although PON:POP of accumulated biomass generally exceeded the supply ratio. Microbial N:P composition was constrained by a general lower limit of 5:1. Channelling of assimilated P into DOP appears to be the mechanism responsible for the consistent offset of cellular stoichiometry relative to inorganic nutrient supply and nutrient drawdown, as DOP build-up was observed to intensify under decreasing N:P supply. Low nutrient N:P conditions in coastal upwelling areas overlying O2-deficient waters seem to represent a net source for DOP, which may stimulate growth of diazotrophic phytoplankton. These results demonstrate that microbial nutrient assimilation and partitioning of organic matter between the particulate and the dissolved phase are controlled by the N:P ratio of upwelled nutrients, implying substantial consequences for nutrient cycling and organic matter pools in the course of decreasing nutrient N:P stoichiometry.

Rock magnetic properties of ODP Hole 109-670A

The magnetic properties of 11 samples from Site 670 of Leg 109, 3 harzburgites and 8 highly serpentinized peridotites, have been studied. Reflected light microscopy and Curie temperatures confirm that magnetite is the dominant magnetic mineral in all samples. However, both rock types show different magnetic behavior. Susceptibility, saturation magnetization, and NRM are higher for the serpentinites, because of the higher magnetite content. The hysteresis parameters indicate magnetite particles with pseudosingle domain structure for both rock types. For the remarkable anisotropy of the magnetic susceptibility no definite explanation could be found, because of the complex texture of the samples. In both rock types the presence of maghemite, a product of low temperature oxidation of magnetite, has been indicated by reflected light microscopy and by thermomagnetic analysis. As the maghemite converts to hematite at temperatures above 350°C, the temperature during the serpentinization was below this value assuming that the maghemitization took place at the same time.

Effects of pCO2 and iron on the elemental composition and cell geometry of the marine diatom Pseudo-nitzschia pseudodelicatissima//(Bacillariophyceae)

Partial pressure of CO2 (pCO2) and iron availability in seawater show corresponding changes due to biological and anthropogenic activities. The simultaneous change in these factors precludes an understanding of their independent effects on the ecophysiology of phytoplankton. In addition, there is a lack of data regarding the interactive effects of these factors on phytoplankton cellular stoichiometry, which is a key driving factor for the biogeochemical cycling of oceanic nutrients. Here, we investigated the effects of pCO2 and iron availability on the elemental composition (C, N, P, and Si) of the diatom Pseudo-nitzschia pseudodelicatissima (Hasle) Hasle by dilute batch cultures under 4 pCO2 (~200, ~380, ~600, and ~800 µatm) and five dissolved inorganic iron (Fe'; ~5, ~10, ~20, ~50, and ~100 pmol /L) conditions. Our experimental procedure successfully overcame the problems associated with simultaneous changes in pCO2 and Fe' by independently manipulating carbonate chemistry and iron speciation, which allowed us to evaluate the individual effects of pCO2 and iron availability. We found that the C:N ratio decreased significantly only with an increase in Fe', whereas the C:P ratio increased significantly only with an increase in pCO2. Both Si:C and Si:N ratios decreased with increasing pCO2 and Fe'. Our results indicate that changes in pCO2 and iron availability could influence the biogeochemical cycling of nutrients in future oceans with high- CO2 levels, and, similarly, during the time course of phytoplankton blooms. Moreover, pCO2 and iron availability may also have affected oceanic nutrient biogeochemistry in the past, as these conditions have changed markedly over the Earth's history.

Methane measurements during POLARSTERN cruise ARK-XXII/2

A methane surplus relative to the atmospheric equilibrium is a frequently observed feature of ocean surface water. Despite the common fact that biological processes are responsible for its origin, the formation of methane in aerobic surface water is still poorly understood. We report on methane production in the central Arctic Ocean, which was exclusively detected in Pacific derived water but not nearby in Atlantic derived water. The two water masses are distinguished by their different nitrate to phosphate ratios. We show that methane production occurs if nitrate is depleted but phosphate is available as a P source. Apparently the low N:P ratio enhances the ability of bacteria to compete for phosphate while the phytoplankton metabolite dimethylsulfoniopropionate (DMSP) is utilized as a C source. This was verified by experimentally induced methane production in DMSP spiked Arctic sea water. Accordingly we propose that methylated compounds may serve as precursors for methane and thermodynamic calculations show that methylotrophic methanogenesis can provide energy in aerobic environments.

Half-degree gridded nitrogen and phosphorus fertilizer use for global agriculture production during 1900-2013

In addition to enhance agricultural productivity, synthetic nitrogen (N) and phosphorous (P) fertilizer application in croplands dramatically altered global nutrient budget, water quality, greenhouse gas balance, and their feedbacks to the climate system. However, due to the lack of geospatial fertilizer input data, current Earth system/land surface modeling studies have to ignore or use over-simplified data (e.g., static, spatially uniform fertilizer use) to characterize agricultural N and P input over decadal or century-long period. We therefore develop a global time-series gridded data of annual synthetic N and P fertilizer use rate in croplands, matched with HYDE 3,2 historical land use maps, at a resolution of 0.5º latitude by longitude during 1900-2013. Our data indicate N and P fertilizer use rates increased by approximately 8 times and 3 times, respectively, since the year 1961, when IFA (International Fertilizer Industry Association) and FAO (Food and Agricultural Organization) survey of country-level fertilizer input were available. Considering cropland expansion, increase of total fertilizer consumption amount is even larger. Hotspots of agricultural N fertilizer use shifted from the U.S. and Western Europe in the 1960s to East Asia in the early 21st century. P fertilizer input show the similar pattern with additional hotspot in Brazil. We find a global increase of fertilizer N/P ratio by 0.8 g N/g P per decade (p< 0.05) during 1961-2013, which may have important global implication of human impacts on agroecosystem functions in the long run. Our data can serve as one of critical input drivers for regional and global assessment on agricultural productivity, crop yield, agriculture-derived greenhouse gas balance, global nutrient budget, land-to-aquatic nutrient loss, and ecosystem feedback to the climate system.

Sediment geochemistry PASOM research cruise (2009) - Murray Ridge region, northern Arabian Sea

In this study, we investigate phosphorus (P) and iron (Fe) cycling in sediments along a depth transect from within to well below the oxygen minimum zone (OMZ) in the northern Arabian Sea (Murray Ridge). Pore-water and solid-phase analyses show that authigenic formation of calcium phosphate minerals (Ca-P) is largely restricted to where the OMZ intersects the seafloor topography, likely due to higher depositional fluxes of reactive P. Nonetheless, increased ratios of organic carbon to organic P (Corg/Porg) and to total reactive P (Corg/Preactive) in surface sediments indicate that the overall burial efficiency of P relative to Corg decreases under the low bottom water oxygen concentrations (BWO) in the OMZ. The relatively constant Fe/Al ratio in surface sediments along the depth transect suggest that corresponding changes in Fe burial are limited. Sedimentary pyrite contents are low throughout the ~25 cm sediment cores at most stations, as commonly observed in the Arabian Sea OMZ. However, pyrite is an important sink for reactive Fe at one station in the OMZ. A reactive transport model (RTM) was applied to quantitatively investigate P and Fe diagenesis at an intermediate station at the lower boundary of the OMZ (bottom water O2: ~14 µmol/L). The RTM results contrast with earlier findings in showing that Fe redox cycling can control authigenic apatite formation and P burial in Arabian Sea sediment. In addition, results suggest that a large fraction of the sedimentary Ca-P is not authigenic, but is instead deposited from the water column and buried. Dust is likely a major source of this Ca-P. Inclusion of the unreactive Ca-P pool in the Corg/P ratio leads to an overestimation of the burial efficiency of reactive P relative to Corg along the depth transect. Moreover, the unreactive Ca-P accounts for ~85% of total Ca-P burial. In general, our results reveal large differences in P and Fe chemistry between stations in the OMZ, indicating dynamic sedimentary conditions under these oxygen-depleted waters.

Biogeochemical parameters and processes in waters and bottom sediments of the Chukchi Sea

Study of biogeochemical processes in waters and sediments of the Chukchi Sea in August 2004 revealed atypical maxima of biogenic element (N, P, and Si) concentrations and rate of microbial sulfate reduction in the surface layer (0-3 cm) of marine sediments. The C/N/P ratio in organic matter (OM) of this layer does not fit the Redfield-Richards stoichiometric model. Specific features of biogeochemical processes in the sea are likely related to the complex dynamics of water, high primary produc¬tivity (110-1400 mg C/m**2/day), low depth of the basin (<50 m for 60% of the water area), reduced food chain due to low population of zooplankton, high density of zoobenthos (up to 4230 g/m**2), and high activity of microbial processes. Drastic decrease in concentrations of biogenic elements, iodine, total alkalinity, and population of microorganisms beneath the 0-3 cm layer testify to large-scale OM decay at the water-seafloor barrier. Our original experimental data support high annual rate of OM mineralization at the bottom of the Chukchi Sea.

Reduced calcification decreases photoprotective capability in the Coccolithophorid Emiliania huxleyi

Intracellular calcification of coccolithophores generates CO2 and consumes additional energy for acquisition of calcium and bicarbonate ions; therefore, it may correlate with photoprotective processes by influencing the energetics. To address this hypothesis, a calcifying Emiliania huxleyi strain (CS-369) was grown semi-continuously at reduced (0.1 mM, LCa) and ambient Ca2+ concentrations (10 mM, HCa) for 150 d (>200 generations). The HCa-grown cells had higher photosynthetic and calcification rates and higher contents of Chl a and carotenoids compared with the naked (bearing no coccoliths) LCa-grown cells. When exposed to stressfull levels of photosynthetically active radiation (PAR), LCa-grown cells displayed lower photochemical yield and less efficient non-photochemical quenching (NPQ). When the LCa- or HCa-grown cells were inversely shifted to their counterpart medium, LCa to HCa transfer increased photosynthetic carbon fixation (P), calcification rate (C), the C/P ratio, NPQ and pigment contents, whereas those shifted from HCa to LCa exhibited the opposite effects. Increased NPQ, carotenoids and quantum yield were clearly linked with increased or sustained calcification in E. huxleyi. The calcification must have played a role in dissipating excessive energy or as an additional drainage of electrons absorbed by the photosynthetic antennae. This phenomenon was further supported by testing two non-calcifying strains, which showed insignificant changes in photosynthetic carbon fixation and NPQ when transferred to LCa conditions