Historical global map of NH4+ and NO3- application in synthetic nitrogen fertilizer, link to NetCDF files

This paper provides a method for constructing a new historical global nitrogen fertilizer application map (0.5° × 0.5° resolution) for the period 1961-2010 based on country-specific information from Food and Agriculture Organization statistics (FAOSTAT) and various global datasets. This new map incorporates the fraction of NH+4 (and NONO-3) in N fertilizer inputs by utilizing fertilizer species information in FAOSTAT, in which species can be categorized as NH+4 and/or NO-3-forming N fertilizers. During data processing, we applied a statistical data imputation method for the missing data (19 % of national N fertilizer consumption) in FAOSTAT. The multiple imputation method enabled us to fill gaps in the time-series data using plausible values using covariates information (year, population, GDP, and crop area). After the imputation, we downscaled the national consumption data to a gridded cropland map. Also, we applied the multiple imputation method to the available chemical fertilizer species consumption, allowing for the estimation of the NH+4/NO-3 ratio in national fertilizer consumption. In this study, the synthetic N fertilizer inputs in 2000 showed a general consistency with the existing N fertilizer map (Potter et al., 2010, doi:10.1175/2009EI288.1) in relation to the ranges of N fertilizer inputs. Globally, the estimated N fertilizer inputs based on the sum of filled data increased from 15 Tg-N to 110 Tg-N during 1961-2010. On the other hand, the global NO-3 input started to decline after the late 1980s and the fraction of NO-3 in global N fertilizer decreased consistently from 35 % to 13 % over a 50-year period. NH+4 based fertilizers are dominant in most countries; however, the NH+4/NO-3 ratio in N fertilizer inputs shows clear differences temporally and geographically. This new map can be utilized as an input data to global model studies and bring new insights for the assessment of historical terrestrial N cycling changes.

Geochemistry of sediment core HE337/001-1, North Sea

Reactive iron (oxyhydr)oxide minerals preferentially undergo early diagenetic redox cycling which can result in the production of dissolved Fe(II), adsorption of Fe(II) onto particle surfaces, and the formation of authigenic Fe minerals. The partitioning of iron in sediments has traditionally been studied by applying sequential extractions that target operationally-defined iron phases. Here, we complement an existing sequential leaching method by developing a sample processing protocol for d56Fe analysis, which we subsequently use to study Fe phase-specific fractionation related to dissimilatory iron reduction in a modern marine sediment. Carbonate-Fe was extracted by acetate, easily reducible oxides (e.g. ferrihydrite and lepidocrocite) by hydroxylamine-HCl, reducible oxides (e.g. goethite and hematite) by dithionite-citrate, and magnetite by ammonium oxalate. Subsequently, the samples were repeatedly oxidized, heated and purified via Fe precipitation and column chromatography. The method was applied to surface sediments collected from the North Sea, south of the Island of Helgoland. The acetate-soluble fraction (targeting siderite and ankerite) showed a pronounced downcore d56Fe trend. This iron pool was most depleted in 56Fe close to the sediment-water interface, similar to trends observed for pore-water Fe(II). We interpret this pool as surface-reduced Fe(II), rather than siderite or ankerite, that was open to electron and atom exchange with the oxide surface. Common extractions using 0.5 M HCl or Na-dithionite alone may not resolve such trends, as they dissolve iron from isotopically distinct pools leading to a mixed signal. Na-dithionite leaching alone, for example, targets the sum of reducible Fe oxides that potentially differ in their isotopic fingerprint. Hence, the development of a sequential extraction Fe isotope protocol provides a new opportunity for detailed study of the behavior of iron in a wide-range of environmental settings.

Chemical composition of manganese micronodules from expedition VA-05/1 in the Pacific Ocean

A radioisotope energy-dispersive X-ray (EDX) system has been used on board the German research vessel "Valdivia" during an exploration expedition in the northern equatorial Pacific in 1973. The instrumentation used consisted of an X-ray detection system incorporating a 30 mm2 effective-area Si (Li) detector with a measured energy resolution of 195 eV for Mn K alpha X-rays, standard nuclear electronics, a 1024-channel analyser and a data read-out unit. The X-ray spectra in the manganese-nodule samples were excited by a 30-mCi 238Pu source. The six elements Mn, Fe, Co, Ni, Cu and Zn were analysed on board. Precision values for the analyses were less than 3% for Mn, Fe, Ni, Cu and Zn and about 5% for Co. A total amount of 350 analyses was carried out during a one-month cruise. Average contents of 190 analysed whole manganese-nodule samples from all the sampling sites of the covered area were 23.3% Mn, 6.7% Fe, 0.23% Co, 1.16% Ni, 0.94% Cu and 0.10% Zn. The average content of the base metals expressed as the sum of the Co, Ni, Cu and Zn contents was 2.48%. A linear relationship between Mn and Ni in all analysed samples, including whole manganese-nodule samples, zones of manganese nodules and manganese crusts, was observed. The Mn/Ni ratio calculated by regression analysis was 23.0. Zonal variations of the chemical contents of the six elements in the manganese nodules were found. A size classification of the manganese nodules has been suggested. Geochemical correlations of Cu and Ni versus Mn/Fe in the investigated samples are given.

Microbial community composition in sediments of the Hydrate Ridge (Cascadian Margin) collected during RV SONNE cruises SO143 (1999) and SO148-1 (2000)

Cold seep environments such as sediments above outcropping hydrate at Hydrate Ridge (Cascadia margin off Oregon) are characterized by methane venting, high sulfide fluxes caused by the anaerobic oxidation of methane, and the presence of chemosynthetic communities. This investigation deals with the diversity and distribution of sulfate-reducing bacteria, some of which are directly involved in the anaerobic oxidation of methane as syntrophic partners of the methanotrophic archaea. The composition and activity of the microbial communities at methane vented and nonvented sediments are compared by quantitative methods including total cell counts, fluorescence in situ hybridization (FISH). Bacteria involved in the degradation of particulate organic carbon (POC) are as active and diverse as at other productive margin sites of similar water depths. The availability of methane supports a two orders of magnitude higher microbial biomass (up to 9.6×10**10cells/cm**3). Sediment samples were obtained during RV SONNE cruises SO143-2 and SO148-1 at the crest of southern Hydrate Ridge at the Cascadia convergent margin off the coast of Oregon. Sediment cores of 20 - 40 cm length were obtained using a video-guided multiple corer from gas hydrate bearing sediments and from reference sites not enriched in methane in the surface sediments. Samples for total cell counts were obtained from 1 cm core slices, fixed with 2% formaldehyde and stored cold (4°C) and the quantification of aggregates was done via epifluorescence microscopy after staining the sediments with Acridine Orange Direct Counts (AODC) according to the method of Meyer- Reil (1983, doi:10.1007/BF00395813). Total cell counts were defined as the sum of single cells plus the aggregated cells in the syntrophic consortia. DAPI staining was used to measure ANME2/DSS aggregate sizes via epifluorescence microscopy of FISH-treated samples. For FISH, subsamples of sediment cores were sliced into 1 cm intervals and fixed for 2-3 h with 3% formaldehyde (final concentration), washed twice with 1×PBS (10 mM sodium phosphate; 130 mM NaCl), and finally stored in 1×PBS/EtOH (1:1) at -20°C.

Phosphorus geochemistry of eastern equatorial Pacific Ocean sediments

We determined phosphorus (P) concentrations in Leg 138 sediment samples from Sites 844, 846, and 851, using a sequential extraction technique to identify the P associated with five sedimentary components. Total concentrations of P (sum of the five components) ranged from 4 to 35 µmol P/g sediment, with mean values relatively similar between the three sites (11, 14, and 12 for Sites 844,846, and 851, respectively). Authigenic/biogenic P was the most important component in terms of percentage of total P (about 75%), with iron-bound P (13%), adsorbed P (2%-9%), and organic P (4%) of secondary importance; detrital P was a minor P sink (1%) in these sediments. Profiles of adsorbed P and iron-bound P show decreasing concentrations with age, indicating that these components have been affected by diagenesis and reorganization of P. A peak in iron-bound P may reflect higher fluxes of hydrothermally derived Fe to eastern equatorial Pacific Ocean sediments from 11 to 8 Ma. Lower detrital P values for western Site 851 reflect a greater distance of this site from a terrigenous source area, compared to that of Sites 844 and 846. Phosphorus mass accumulation rates (P-MARs; units of µmol P/cm**2/k.y.) were calculated using total P concentrations (not including the minor and oceanically unreactive detrital P component) and sedimentation rates and dry-bulk densities averaged over time intervals of 0.5 m.y. P-MARs generally decrease from 17 Ma to the present. Eastern transect Sites 844 and 846 display a decrease in P-MARs from about 30 to 10 in the interval from 17 to 8 Ma, while western transect Site 851 is highly variable during this interval. P-MARs increase to about 45 and stay relatively high from 8 to 6 Ma, then decrease toward the present to some of the lowest values of the record (about 10). The general trend of high P-MARs at about 6 Ma and decreasing values toward the present is correlated with other geochemical and sedimentary trends through this interval and may reflect (1) a change in net sediment and P burial, (2) a reorganization of fluxes with no change of net burial, or (3) a combination of the two.

(Table) Content of organic compounds in the bottom sediments of the Volga River estuary

Materials from different spheres of the Earth are ultimately delivered to bottom sediments, which serve as a natural recorder of the functioning of other spheres and originate as a result of the accumulation of their substances. Sedimentary material and species of river-transported elements are subjected to dramatic reworking in marginal filters, where river and sea waters are mixed. These processes are most important for the Caspian Sea, where runoffs of rivers (especially the Volga River) and the intense development and transportation of hydrocarbon fuel by tankers and pipelines (related to the coastal petroleum industry in the Sumgait and Baku ports, Apsheron Peninsula) are potential sources of hydrocarbon pollution. Previously obtained data showed that the total content of hydrocarbon fraction (i.e., the sum of aliphatic hydrocarbons (AHC) and polycyclic aromatic hydrocarbons (PAH)) in bottom sediments varied within 29-1820 µg/g. The content of petroleum hydrocarbons in the northeastern Caspian region varied from 0.052 to 34.09 µg/g with the maximum content in the Tengiz field. The content of six polyarenes in the Volga delta sediments was no more than 40 ng/g. To determine the recent HC pollution of bottom sediments and trends in the functioning of the Volga marginal filter, in summer of 2003 and 2004 we analyzed bottom sediments (58 samples) in the river waterway; Kirovsk channel; Bakhtemir and Ikryanoe branches; tributaries of the Kizan, Chagan, and other rivers; and the Caspian seashore.

Collection of aboveground community and species-specific plant biomass from the Jena Experiment (time series since 2002).

This data set comprises time series of aboveground community plant biomass (Sown plant community, Weed plant community, Dead plant material, and Unidentified plant material; all measured in biomass as dry weight) and species-specific biomass from the sown species of several experiments at the field site of a large grassland biodiversity experiment (the Jena Experiment; see further details below). Aboveground community biomass was normally harvested twice a year just prior to mowing (during peak standing biomass twice a year, generally in May and August; in 2002 only once in September) on all experimental plots in the Jena Experiment. This was done by clipping the vegetation at 3 cm above ground in up to four rectangles of 0.2 x 0.5 m per large plot. The location of these rectangles was assigned by random selection of new coordinates every year within the core area of the plots. The positions of the rectangles within plots were identical for all plots. The harvested biomass was sorted into categories: individual species for the sown plant species, weed plant species (species not sown at the particular plot), detached dead plant material (i.e., dead plant material in the data file), and remaining plant material that could not be assigned to any category (i.e., unidentified plant material in the data file). All biomass was dried to constant weight (70°C, >= 48 h) and weighed. Sown plant community biomass was calculated as the sum of the biomass of the individual sown species. The data for individual samples and the mean over samples for the biomass measures on the community level are given. Overall, analyses of the community biomass data have identified species richness as well as functional group composition as important drivers of a positive biodiversity-productivity relationship. The following series of datasets are contained in this collection: 1. Plant biomass form the Main Experiment: In the Main Experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). 2. Plant biomass from the Dominance Experiment: In the Dominance Experiment, 206 grassland plots of 3.5 x 3.5 m were established from a pool of 9 species that can be dominant in semi-natural grassland communities of the study region. In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 3, 4, 6, and 9 species). 3. Plant biomass from the monoculture plots: In the monoculture plots the sown plant community contains only a single species per plot and this species is a different one for each plot. Which species has been sown in which plot is stated in the plot information table for monocultures (see further details below). The monoculture plots of 3.5 x 3.5 m were established for all of the 60 plant species of the Jena Experiment species pool with two replicates per species like the other experiments in May 2002. All plots were maintained by bi-annual weeding and mowing.

Pigments of sediment cores of the Northwest European Continental Margin

In the context of the European OMEX Programme this investigation focused on gradients in the biomass and activity of the small benthic size spectrum along a transect across the Goban Spur from the outer Celtic Sea into Porcupine Abyssal Plain. The effects of food pulses (seasonal, episodic) on this part of the benthic size spectrum were investigated. Sediments sampled during eight expeditions at different seasons covering a range from 200 m to 4800 m water depth were assayed with biochemical bulk measurements: determinations of chloroplastic pigment equivalents (CPE), the sum of chlorophyll a and its breakdown products, provide information concerning the input of phytodetrital matter to the seafloor; phospholipids were analyzed to estimate the total biomass of small benthic organisms (including bacteria, fungi, flagellata, protozoa and small metazoan meiofauna). A new term 'small size class biomass' (SSCB) is introduced for the biomass of the smallest size classes of sediment-inhabiting organisms; the reduction of fluorescein-di-acetate (FDA) was determined to evaluate the potential activity of ester-cleaving bacterial exoenzymes in the sediment samples. At all stations benthic biomass was predominantly composed of the small size spectrum (90% on the shelf; 97-98% in the bathyal and abyssal parts of the transect). Small size class biomass (integrated over a 10 cm sediment column) ranged from 8 g C/m**2 on the shelf to 2.1 g C/m**2 on the adjacent Porcupine Abyssal Plain, exponentially decreasing with increasing water depth. However, a correlation between water depth and SSCB, macrofauna biomass as well as metazoan meiofauna biomass exhibited a significantly flatter slope for the small size classes in comparison to the larger organisms. CPE values indicated a pronounced seasonal cycle on the shelf and upper slope with twin peaks of phytodetrital deposition in mid spring and late summer. The deeper stations seem to receive a single annual flux maximum in late summer. SSCB and heterotrophic activity are significantly correlated to the amount of sediment-bound pigments. Seasonality in pigment concentrations is clearly followed by SSCB and activity. In contrast to macro- and megafauna which integrate over larger periods (months/years), the small benthic size classes, namely bacteria and foraminifera, proved to be the most reactive potential of the benthic communities to any perturbations on short time scales (days/weeks). The small size classes, therefore, occupy a key role in early diagenetic processes.