Net community production, Thorium-234 activity and particle flux during the Southern Ocean iron fertilization experiment LOHAFEX

A closed eddy core in the Subantarctic Atlantic Ocean was fertilized twice with two tons of iron (as FeSO4), and the 300 km**2 fertilized patch was studied for 39 days to test whether fertilization enhances downward particle flux into the deep ocean. Chlorophyll a and primary productivity doubled after fertilization, and photosynthetic quantum yield (FV/FM) increased from 0.33 to >0.40. Silicic acid (<2 µmol/L) limited diatoms, which contributed <10% of phytoplankton biomass. Copepods exerted high grazing pressure. This is the first study of particle flux out of an artificially fertilized bloom with very low diatom biomass. Net community production (NCP) inside the patch, estimated from O2:Ar ratios, averaged 21 mmol POC/m**2/d, probably ±20%. 234Th profiles implied constant export of ~6.3 mmol POC/m**2/d in the patch, similar to unfertilized waters. The difference between NCP and 234Th-derived export partly accumulated in the mixed layer and was partly remineralized between the mixed layer and 100 m. Neutrally buoyant sediment traps at 200 and 450 m inside and outside the patch caught mostly <1.1 mmol POC/m**2/d, predominantly of fecal origin; flux did not increase upon fertilization. Our data thus indicate intense flux attenuation between 100 and 200 m, and probably between the mixed layer and 100 m. We attribute the lack of fertilization-induced export to silicon limitation of diatoms and reprocessing of sinking particles by detritus feeders. Our data are consistent with the view that nitrate-rich but silicate-deficient waters are not poised for enhanced particle export upon iron addition.

Chemistry of Late Quaternary sediments and their interstitial waters of sediment cores from the Nort-West African continental margin

In the sediments of the NW African continental margin the mainly biogenic carbonate constituents become increasingly diluted with terrigenous material as one approaches the coast, as indicated by the carbonate-CO2 content, the Al2O3/SiO2-ratios, and the presence of ammonia fixed to alumino-silicates, predominantly to illites. In the norther area of the investigation - off Cape Blanc and Cape Bojador . the terrigenous constituents are mainly quartz from the Sahara Desert, whereas in the south - off Senegal - more alumino-silicates as clay minerals are admixed with the carbonate constituents. The organic carbon content of the continental slope sediments off Senegal is higher than in samples of the continental rise or of the preservation of organic matter as a result of high production and relatively rapid sedimentation. The zone of manganese-oxide enrichment follows the redox potential of + 330 mV from the surface (0-5 cm) into the sediments (20-30 cm deep) at 2000--3000 m and 3700 m of water depths, respectively. At shallower water depths, low redox potentials preclude deposition of manganese oxides and cause their mobilization from the sediments. About 1/3 of the total sedimentary Zn and 1/4 of the Cu is associated with the carbonate mineral fraction, probably in calcium phosphate overgrowths as a result of the mineralization of phosphorus-containing organic matter. Besides the precipitation of calcium phosphate, the mineralization of organic matter mediated by bacterial sulfate reduction also results in calcium carbonate precipitation and the exchange of ammonia for potassium on illites. Because of these simultaneous reactions, the depth distribution of all mineralization constituents in the interstitial water can be determined using the actual molar carbon-to-nitrogen-to phosphorus ratios of the sedimentary organic matter. The amount of sulfide sulfur in this process indicates the predominance of bacterial sulfate reduction in the sediments off NW Africa. This process also preferentially decomposes nitrogen- and phosphorus-containing organic compounds so organic matter deficient in these elements is characteristic for the rapidly accumulating sediments than today, indicating there was increased production of organic carbon compounds and more favorable conditions of their preservations. During the last interglacial times conditions were similar to those to today. This differentiation with time has also been observed in sediments from the Argentine Basin and from slope off South India indicating perhaps world-wide environmental changes throughout Late Quaternary times.

Middle to Late Quaternary sedimentation and rock-magnetic of ODP Site 105-646

We examine rock-magnetic, carbonate, and planktonic foraminiferal fluxes to identify climatically controlled changes of terrigenous and pelagic sedimentation at Ocean Drilling Program (ODP) Site 646 (the Labrador Sea). Terrigenous sediments are brought to the site principally by bottom currents. We use a rock-magnetic parameter sensitive to changes in magnetic mineral grain size, the ratio of anhysteretic susceptibility to low-field magnetic susceptibility (XARM/X), to monitor changes in bottom-current intensity over time, with large values of XARM/X (finer-grained magnetic minerals) indicating weaker bottom currents. A second rock-magnetic parameter, magnetic mineral accumulation rate (KaT) was used to indicate variations in terrigenous flux. Planktonic foraminiferal and carbonate accumulation rates (Pfar and CaC03ar) are used as indicators of pelagic flux. Absolute age assignments are based on correlation between the planktonic foraminiferal oxygen-isotope variations for Site 646 and the SPECMAP master oxygen-isotope curve. Cross-correlation analyses of the parameters that we studied with respect to the SPECMAP curve suggest that from oxygen-isotope stages 21 to 11, sedimentation rate, KaT, X, CaCO3ar, and Pfar were at their maximums, whereas XARM/X was at its minimum during peak interglacials (i.e., 0 k.y. lag time with respect to minimum ice volume). However, all parameters we examined lag behind minimum ice volume from stages 11 to 1, indicating a change in timing of both pelagic and terrigenous fluxes at approximately 400 k.y. BP. The negative correlation coefficient between XARM/X and the SPECMAP curve further suggest that finer-grained magnetic minerals are deposited during glacial periods, which probably reflects weaker bottom currents. The shift observed in the lag times of parameters examined with respect to the SPECMAP record is attributed to a change in significance of orbital parameters. Spectral results exhibit strong power in eccentricity (about 100 k.y.) throughout the record. Kap X, CaCO3flr, and Pfar show significant power in obliquity (about 41 k.y.), whereas XARM/X shows significant power at 73 k.y. from stages 21 to 11. The 73-k.y. period in XARM/X is near the difference tone of obliquity and eccentricity: 1/43-1/102 = 1/69. Kar and XARM/X show power only in eccentricity from stages 11 to 1. X and Pfar show significant power in precession (about 18 and 22 k.y.) whereas CaC03ar has power at 34 k.y, which could be a combination of precession and obliquity. The shift in power of orbital parameters may by attributed to the effect of the about 413-k.y. signal of eccentricity.

Accumulation of particulate organic carbon at the Eurasian continental margin during late Quaternary times

Data on the amount and composition of organic carbon were determined in sediment cores from the Kara and Laptev Sea continental margin, representing oxygen isotope stages 1-6. The characterization of organic matter is based on hydrogen index (HI) values, n-alkanes and maceral composition, indicating the predominance of terrigenous organic matter through space and time. The variations in the amount and composition of organic carbon are mainly influenced by changes in fluvial sediment supply, Atlantic water inflow, and continental ice sheets. During oxygen isotope stage (OIS) 6, high organic carbon contents in sediments from the Laptev Sea and western East Siberian Sea continental margin were probably caused by the increased glacial erosion and further transport in the eastward-flowing boundary current along the continental margin. During OIS 5 and early OIS 3, some increased amounts of marine organic matter were preserved in sediments east of the Lomonosov Ridge, suggesting an influence of nutrient-rich Pacific waters. During OIS 2, terrigenous organic carbon supply was increased along the Barents and western Kara Sea continental margin caused by extended continental ice sheets in the Barents Sea (Svalbard to Franz Josef Land) area and increased glacial erosion. Along the Laptev Sea continental margin, on the other hand, the supply of terrigenous (organic) matter was significantly reduced due to the lack of major ice sheets and reduced river discharge. Towards the Holocene, the amount of total organic carbon (TOC) increased along the Kara and Laptev Sea continental margin, reaching average values of up to 0.5 g C/cm**2/ky. Between about 8 and 10 ka (9 and 11 Cal ka), i.e., during times when the inner shallow Kara and Laptev seas became largely flooded for the first time after the Last Glacial Maximum, maximum supply of terrigenous organic carbon occurred, which is related to an increase in coastal erosion and Siberian river discharge. During the last 8000 years, the increased amount of marine organic carbon preserved in the sediments from the Kara and Laptev Sea continental margin is interpreted as a result of the intensification of Atlantic water inflow along the Eurasian continental margin.

Sedimentology and benthic foraminiferal assemblages of the late Younger Dryas and early Holocene in the Skagerrak

A high-resolution study of palaeoenvironmental changes through the late Younger Dryas and early Holocene in the Skagerrak, the eastern North Atlantic, is based on multi-proxy analyses of core MD99-2286 combined with palaeo-water depth modelling for the area. The late Younger Dryas was characterized by a cold ice-distal benthic foraminiferal fauna. After the transition to the Preboreal (c. 11 650 cal. a BP) this fauna was replaced by a Cassidulina neoteretis dominated fauna, indicating the influence of chilled Atlantic Water at the sea floor. Persisting relatively cold bottom-water conditions until c. 10 300 cal. a BP are presumably a result of an outflow of glacial meltwater from the Baltic area across south-central Sweden, which develops a strong stratification of the water column at MD99-2286. A short-term peak in the C/N ratio at c. 10 200 cal. a BP is suggested to indicate input of terrestrial material, which may represent the drainage of an ice-dammed lake in southern Norway, the Glomma event. After the last drainage route across south-central Sweden closed, c. 10 300 cal. a BP, the meltwater influence diminished, and the Skagerrak resembled a fjord with stable inflow of waters from the North Atlantic through the Norwegian Channel and a gradual increase in boreal species. Full interglacial conditions were established at the sea floor from c. 9250 cal. a BP. Subsequent warm stable conditions were interrupted by a short-term cooling around 8300-8200 cal. a BP, representing the 8.2 ka event.

Late pleistocene and holocene sedimentation in the central and eastern Persian Gulf

The sandfraction of the sediment was analysed in five cores, taken from 65 m water depth in the central and eastern part of the Persian Gulf. The holocene marls are underlayn by aragonite muds, which are probably 10-11,000 years old. 1. The cores could be subdivided into coarse grained and fine grained layers. Sorting is demonstrated by the following criteria: With increasing median values of the sandfraction - the fine grained fraction decreases within each core; - the median of each biogenic component, benthonic as well as planktonic, increases; - the median of the relict sediment, which in core 1179 was carried upward into the marl by bioturbation, increases; - the percentages of pelecypods, gastropods, decapods and serpulid worms in the sandfraction increase, the percentages of foraminifera and ostracods decrease; - the ratios of pelecypods to foraminifera and of decapods to ostracods increase; - the ratios of benthonic molluscs to planktonic molluscs (pteropods) and of benthonic foraminifera to planktonic foraminifera increase (except in core 1056 and 1179); - the ratio of planktonic molluscs (pteropods) to planktonic foraminifera increases; - the globigerinas without orbulinas increase, the orbulinas decrease in core 1056. Different settling velocities of these biogenic particles help in better understanding the results : the settling velocities, hence the equivalent hydrodynamic diameters, of orbulinas are smaller than those of other globigerinas, those of planktonic foraminifera are smaller than those of planktonic molluscs, those of planktonic molluscs are smaller than those of benthonic molluscs, those of pelecypods are smaller than those of gastropods. Bioturbation could not entirely distroy this "grain-size-stratification". Sorting has been stronger in the coarse layers than in the finer ones. As a cause variations in the supply of terrigenous material at constant strength of tidal currents is suggested. When much terrigenous material is supplied (large contents of fine grained fraction) the sedimentation rates are high: the respective sediment surface is soon covered and removed from the influence of tidal currents. When, however, the supply of terrigenous material is small, more sandy material is taken away in all locations within the influence of terrigenous supply. Thus the biogenic particles in the sediment do not only reflect the organic production, but also the influence of currents. 2. There is no parameter present in all cores that is independently variable from grain size and can be used for stratigraphic correlation. The two cores from the Strait of Hormus were correlated by their sequences of coarse and fine grained layers. 3. The sedimentation rates of terrigenous material, of total planktonic and benthonic organisms and of molluscs, foraminifera, echinoids and ophiuroids are shown in table 1 (total sediment 6.3-75.5 cm/1000 yr, biogenic carbonate 1.9-3.6 cm/1000 yr). The sedimentation rates of benthonic organisms are nearly the same in the cores of the Strait of Hormus, whereas near the Central Swell they are smaller. In the upper parts of the two cores of the Strait of Hormus sedimentation rates are higher than in the deeper parts, where higher median values point to stronger reworking. 4. The sequence of coarse and fine grained intervals in the two cores of the Hormus Strait, attributed to variations in climate, as well as the increase of terrigenous supply from the deeper to the upper parts of the cores, agrees with the descriptions in the literature of the post Pleistocene climate as becoming more humid. The rise of sea level is sedimentologically not measurable in the marly sediments - except perhaps for the higher content of echinoids in the lower part of core 1056. These may be attributed to the influence of a migrating wave-base. 5. The late Pleistocene aragonite mud is very fine grained (> 50%< 2 p) and poor in fossils (0.5-1.8%) biogenic particles of total sediment. The sand fraction consists almost entirely of white clumps, c. 0.1 mm in diameter (1177), composed of aragonite needles and of detrital minerals with the same size (1201). The argonite mud was probably not formed in situ, because the water depth at time of formation was at most 35 m at least 12 m. The sorting of the sediment (predominance of the fine grained sand), the absence of larger biogenic components and of pellets, c. 0.2-0.5 mm in diameter, which are typical for Recent and Pleistocene locations of aragonite formation, as well as the sedimentological conditions near the sampling points, indicate rather a transport of aragonite mud from an area of formation in very shallow waters. Sorting as well as lenticular fabric in core 1201 point to sedimentation within the influence of currents. During alternating sedimentation - and reworking processes the aragonitic matrix was separated from the silt - and sand-sized minerals. The lenses grade into touches because of bioturbation. 6. In core 1056 D2 from Hormus Bay the percentages of organic carbon, total nitrogen and total carbonate were determined. With increasing amounts of smaller grain sizes the content of organic matter increases, whereas the amount of carbonate decreases. The amounts of organic carbon and of nitrogen decrease with increasing depth, probably due to early-diagenetic decomposition processes. Most of the total nitrogen is of organic origin, only about 10% may well be inorganically fixed as ammonium-nitrogen. In the upper part of the core the C/N-ratio increases with increasing depth. This may be connected with a stronger decomposition of nitrogen-containing organic compounds. The general decrease of the C/N-ratios in the lower part of the core may be explained by the relative increase of inorganically fixed ammonium-nitrogen with decreasing content of organic matter.

Stable carbon isotope record and geochemistry of late Miocene-early Pliocene sediments from DSDP Site 90-590 in the Tasman Sea

Biogenic components of sediment accumulated at high rates beneath frontal zones of the Indian and Pacific oceans during the late Miocene and early Pliocene. The delta13C of bulk and foraminiferal carbonate also decreased during this time interval. Although the two observations may be causally linked, and signify a major perturbation in global biogeochemical cycling, no site beneath a frontal zone has independent records of export production and delta13C on multiple carbonate phases across the critical interval of interest. Deep Sea Drilling Project (DSDP) site 590 lies beneath the Tasman Front (TF), an eddy-generating jetstream in the southwest Pacific Ocean. To complement previous delta13C records of planktic and benthic foraminifera at this location, late Neogene records of CaCO3 mass accumulation rate (MAR), Ca/Ti, Ba/Ti, Al/Ti, and of bulk carbonate and foraminiferal delta13C were constructed at site 590. The delta13C records include bulk sediment, bulk sediment fractions (<63 µm and 5-25 µm), and the planktic foraminifera Globigerina bulloides, Globigerinoides sacculifer (with and without sac), and Orbulina universa. Using current time scales, CaCO3 MARs, Ca/Ti, Al/Ti and Ba/Ti ratios are two to three times higher in upper Miocene and lower Pliocene sediment relative to overlying and underlying units. A significant decrease also occurs in all delta13C records. All evidence indicates that enhanced export production - the 'biogenic bloom' - extended to the southwest Pacific Ocean between ca. 9 and 3.8 Ma, and this phenomenon is coupled with changes in delta13C - the 'Chron C3AR carbon shift'. However, CaCO3 MARs peak ca. 5 Ma whereas elemental ratios are highest ca. 6.5 Ma; foraminiferal delta13C starts to decrease ca. 8 Ma whereas bulk carbonate delta13C begins to drop ca. 5.6 Ma. Temporal discrepancies between the records can be explained by changes in the upwelling regime at the TF, perhaps signifying a link between changes in ocean-atmosphere circulation change and widespread primary productivity.

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.

Comparison of nitrogen isotopic values from different preparation methods

We are writing to comment on the work of Tamburini et al. (2003, doi:10.1029/2000PA000616). During the course of subsequent discussions between the authors and ourselves, it has become clear that the published sedimentary nitrogen isotopic values for Ocean Drilling Program (ODP) Site 724 are in error. Our reanalysis of sediment samples from the same intervals has revealed a significant offset from the original d15N data, requiring a revised assessment of their initial interpretation. The purposes of this comment are to (1) address the origin of these errors; (2) outline a protocol for future validation of nitrogen isotopic analyses; and (3) provide revised interpretations of the sedimentary d15N data in terms of the regional relative contributions of denitrification and nitrogen fixation and mean state of the southwest monsoon. (2) Nitrogen isotopic values measured on late Quaternary sediments at Arabian Sea ODP Site 724 by Tamburini et al. (2003, doi:10.1029/2000PA000616) are inexplicably different from a number of published records of d15N from very nearby on the Oman margin (Altabet et al., 1995, doi:10.1038/373506a0; 1999, doi:10.1029/1999PA900035; 2002, doi:10.1038/415159a; Higginson et al., 2004, doi:10.1016/j.gca.2004.03.015) and elsewhere in the Arabian Sea (Reichart et al., 1998, doi:10.1029/98PA02203). These data were generated using similar instrumentation (elemental analyzer coupled with an isotope ratio mass spectrometer) and analytical methodology to those already published. Concerned by this clear discrepancy, we analyzed aliquots of sediment from the same depth intervals for nitrogen abundance and bulk sedimentary nitrogen isotopes. We have been unable to duplicate the values published by Tamburini et al. (2003, doi:10.1029/2000PA000616 ), even after analysis of multiple replicates and due consideration of natural sediment heterogeneities and postrecovery sample storage.

(Table 1) Organic and inorganic geochemical analysis of Late Jurassic to Early Cretaceous black shale sediments from the Norwegian-Greenland Seaway

The Late Jurassic to Early Cretaceous (Volgian-Ryazanian) was a period of a second-order sea-level low stand, and it provided excellent conditions for the formation of shallow marine black shales in the Norwegian-Greenland Seaway (NGS). IKU Petroleum Research drilling cores taken offshore along the Norwegian shelf were investigated with geochemical and microscopic approaches to (1) determine the composition of the organic matter, (2) characterize the depositional environments, and (3) discuss the mechanisms which may have controlled production, accumulation, and preservation of the organic matter. The black shale sequences show a wide range of organic carbon contents (0.5-7.0 wt %) and consist of thermally immature organic matter of type II to II/III kerogen. Rock-Eval pyrolysis revealed fair to very good petroleum source rock potential, suggesting a deposition in restricted shallow marine basins. Well-developed lamination and the formation of autochthonous pyrite framboids further indicate suboxic to anoxic bottom water conditions. In combination with very low sedimentation rates it seems likely that preservation was the principal control on organic matter accumulation. However, a decrease of organic carbon preservation and an increase of refractory organic matter from the Volgian to the Hauterivian are superimposed on short-term variations (probably reflecting Milankovitch cycles). Various parameters indicate that black shale formation in the NGS was gradually terminated by increased oxidative conditions in the course of a sea-level rise.