Phosphorus components, trace metals and Ba excess of ODP Site 202-1237 sediments

We determined the sedimentary concentrations of phosphorus (P), barium (Ba), manganese (Mn), titanium (Ti), aluminum (Al), and uranium (U) for sediment samples from the southeast Pacific Nazca Ridge, Ocean Drilling Program Site 1237. This unique record extends to 31 Ma over 360 meters composite depth (mcd), recording depositional history as the site progressed eastward over its paleohistory. We sampled with a temporal resolution of ~0.2 m.y. throughout the sequence, equivalent to an average spacing of 1.63 m/sample. Concentrations of sequentially extracted components of P (oxide-associated, authigenic, organic, and detrital) increase toward the modern. Al/Ti ratios indicate that the background detrital source material is consistent with upper continental crust. U enrichment factors (U EFs) generally exceed crustal values and indicate slightly reducing environments. However, authigenic U precipitation can also be influenced by the organic carbon rain rate and may not be solely an indicator of redox conditions. Dramatic changes in Mn EFs at ~162 mcd, from values between 12 and 93 to values <12 after this depth, and a sharp color contact boundary lead us to believe that a paleoredox boundary from an oxygenated to a more reducing depositional environment occurred near this depth. Estimates of biogenic barite concentrations from a total sediment digestion technique (Ba excess) are greater than those from a barite extraction (Ba barite) for selected samples across the entire depth range. Applying a range of Ba/Ti ratios from different source materials to correct for detrital inputs does not change the lack of agreement with Ba barite concentrations. Reactive P (P reactive) concentrations (the sum of oxide-associated, authigenic, and organic P concentrations) increase toward the modern with values typically <12 µmol P/g from the base of our record through ~100 mcd, with a gradual increase to concentrations >15 µmol P/g. Ba excess follows the same general trends as Preactive, with concentrations <14 µmol Ba/g in the lower portion of the record to values >15 µmol Ba/g. Accumulation rate records of these proxies will be needed to infer paleoproductivity. P reactive/Ba excess ratios, an indicator of the relative burial of the nutrient P to organic carbon export, exhibit higher values, similar to modern, from the base of our record through ~180 mcd. The remainder of the record exhibits values lower than modern, indicating that organic carbon export to the sediments was higher relative to nutrient burial.

Global assessment of soil phosphorus retention potential

Limited availability of P in soils to crops may be due to deficiency and/or severe P retention. Earlier studies that drew on large soil profile databases have indicated that it is not (yet) feasible to present meaningful values for "plant-available" soil P, obtained according to comparable analytical methods, that may be linked to soil geographical databases derived from 1:5 million scale FAO Digital Soil Map of the World, such as the 5 x 5 arc-minute version of the ISRIC-WISE database. Therefore, an alternative solution for studying possible crop responses to fertilizer-P applied to soils, at a broad scale, was sought. The approach described in this report considers the inherent capacity of soils to retain phosphorus (P retention), in various forms. Main controlling factors of P retention processes, at the broad scale under consideration, are considered to be pH, soil mineralogy, and clay content. First, derived values for these properties were used to rate the inferred capacity for P retention of the component soil units of each map unit (or grid cell) using four classes (i.e., Low, Moderate, High, and Very High). Subsequently, the overall soil phosphorus retention potential was assessed for each mapping unit, taking into account the P-ratings and relative proportion of each component soil unit. Each P retention class has been assigned to a likely fertilizer P recovery fraction, derived from the literature, thereby permitting spatially more detailed, integrated model-based studies of environmental sustainability and agricultural production at the global and continental level (< 1:5 million). Nonetheless, uncertainties remain high; the present analysis provides an approximation of world soil phosphorus retention potential.

Geochemistry of sediments of stage 5 of the Nordic seas

Stable isotope, foraminifera and ice rafted detritus (IRD) records covering the last interglacial (the Eemian) from 7 sediment cores in a transect from the Norwegian to the Greenland Sea are presented. The percentages of Neogloboquadrina pachyderma (s.) and Globigerina quinqueloba, foraminiferal content, and to some extent planktonic stable isotope records, demonstrate marked, regional changes in surface water conditions. Importantly, the variability in the abundances of subpolar foraminifera and foraminiferal content are not coherent, implying that these two types of proxies fluctuated independently of each other and most likely reflect changes in sea surface temperature and surface water carbonate productivity, respectively. Paleoceanographic reconstructions demonstrate significant movements of the oceanographic fronts. At the warmest periods, the Arctic front was located far west of the present-day location, at least within the Iceland Sea region. At 126-125 ka, this was most probably due to a stronger or more westerly located Norwegian current. Within the later warm intervals, higher heat flux to the western part of the basin reflects a combination of a stronger Irminger current and/or a weaker east Greenland current. During the main cold spell at ~124 ka, a diffuse Arctic front had a more southeasterly location than today, and intrusion of Atlantic surface waters was probably limited to a narrow corridor in the Eastern Norwegian Sea. A general correspondence between minima in sea surface temperatures and light benthic delta18O may indicate enhanced influx of freshwater to the basin within the cold events. At least in the Norwegian Sea, we find some evidence that the changes in surface water conditions are associated with changes in deep water ventilation. The majority of the fluctuations may be related to occasional breakdown or reduction of the thermohaline circulation within the Nordic seas. In the earliest Eemian, this could result from meltwater forcing. During the remaining part of the last interglacial the fine balance between temperature and salinity, which the deep water formation is depending on, may have been disturbed by periodic increases in fresh water supply or variable influx of warm Atlantic surface waters.

Nitrogen isotopic composition and chemical composition of altered oceanic crust from ODP Legs 129 and 185

Knowledge of the subduction input flux of nitrogen (N) in altered oceanic crust (AOC) is critical in any attempt to mass-balance N across arc-trench systems on a global or individual-margin basis. We have employed sealed-tube, carrier-gas-based methods to examine the N concentrations and isotopic compositions of AOC. Analyses of 53 AOC samples recovered on DSDP/ODP legs from the North and South Pacific, the North Atlantic, and the Antarctic oceans (with larger numbers of samples from Site 801 outboard of the Mariana trench and Site 1149 outboard of the Izu trench), and 14 composites for the AOC sections at Site 801, give N concentrations of 1.3 to 18.2 ppm and d15N_air of -11.6? to +8.3?, indicating significant N enrichment probably during the early stages of hydrothermal alteration of the oceanic basalts. The N-d15N modeling for samples from Sites 801 and 1149 (n=39) shows that the secondary N may come from (1) the sedimentary N in the intercalated sediments and possibly overlying sediments via fluid-sediment/rock interaction, and (2) degassed mantle N2 in seawater via alteration-related abiotic reduction processes. For all Site 801 samples, weak correlation of N and K2O contents indicates that the siting of N in potassic alteration phases strongly depends on N availability and is possibly influenced by highly heterogeneous temperature and redox conditions during hydrothermal alteration. The upper 470-m AOC recovered by ODP Legs 129 and 185 delivers approximately 800 kg/km N annually into the Mariana margin. If the remaining less-altered oceanic crust (assuming 6.5 km, mostly dikes and gabbros) has MORB-like N of 1.5 ppm, the entire oceanic crust transfers 5100 kg/km N annually into that trench. This N input flux is twice as large as the annual N input of 2500 kg/km in seafloor sediments subducting into the same margin, demonstrating that the N input in oceanic crust, and its isotopic consequences, must be considered in any assessment of convergent margin N flux.

Chemical observations in the Red Sea and the inner Gulf of Aden during the International Indian Ocean Expedition 1964/65

The Red Sea has a special place among the adjacent seas of the world. High evaporation, exclusion of its deep water from contact with the Indian Ocean proper and complete absence of continental drainage may result special conditions of the chemistry of the Red Sea. This paper aims to describe and explain the peculiarity of the hydrochemical situation. The influence of the topography, of the inflow and outflow through the straights of Bab el Mandeb, of the evaporation, of the stability of the water layers, and of the circulation will be studied. An attempt is made to estimate the apparent oxygen ultilisation in order to obtain an indication of the biological activity. A further attempt is made toward the quantitative estimation of the circulation of the nutrients and also to obtain some information about transport, dissolution, and precipitation of calcium carbonate. The basis of these investigations are mainly observations of R. V. "Meteor" during the International Indian Ocean Expedition 1964/65. The determination of dissolved oxygen, dissolved inorganic phosphate, nitrate, nitrite, ammonia, pH, alkalinity, silicate as well as salinity and temperature forms the necessary basis for such an investigation of the chemical conditions. In the first chapter the methods and some modifications for the determination of the chemical properties as applied during the I.I.O.E. cruise of R. V. "Meteor" are described. The new methods, as worked out and tested under sea going conditions during several years by the author, are described in more detail. These are the methods for nitrate, silicate, the automatic determination of dissolved inorganic phosphate and silicate, the automated determination of total phosphorus, the in situ recording of the oxygen tension, and the modification for the determination of ammonia, calcium, and dissolved oxygen. With these revised methods more than 18,000 determinations have been carried out during the Indian Ocean cruise. The complete working up of the chemical data of the Indian Ocean Expedition of R. V. "Meteor" is devided into four sections: Contributions 1) to the Chemistry of the Red Sea and the Inner Gulf of Aden, 2) to the Gulf of Aden and the Somali Coast Region, 3) to the Western Indian Coast Region, and 4) to the Persian Gulf and the Straits of Oman. This paper presents the first contribution. The special hydrographical conditions are discussed. It can be shown, that the increase of salinity in the surface waters from the south to the north of the Red Sea is only to about 30 % due to evaporation. The remaining increase is presumed to be due to the admixture of deep water to the surface layers. A special rate for the consumption of oxygen (0.114 ml/ l/a) is derived for the deep water of the Red Sea at 1500 m. Based upon the distribution of the dissolved oxygen along the axii of the Red Sea, a chematic model for the longitudinal circulation of the Red Sea is constructed. This model should be considered as a first approximation and may explain the special distribution of phosphate, nitrate, and silicate. Based upon the evaluation of the residence time of the deep water a dissolution rate for silicate is estimated as 1 mygat/a. It seems possible to calculate residence times of water masses outside the Red Sea from the silicate content. The increase of silicate and the consumption of oxygen lead to residence times of the water below the thermocine of 30 to 48 years. The distribution of oxygen in the Straits of Bab el Mandeb is described and discussed. The rate of consumption of the oxygen in the outflowing Red Sea water is estimated to 8.5 ml/ l/a. This rather high rate is explained with reference to the special conditions in the outflowing water. The Red Sea water is characterized initially by a relative high content of oxygen and a low content of nutrients. The increase in nutrients and the decrease in the oxygen content is a secondary process of the Red Sea water on its way to the Arabian Sea. Based upon the vertical distribution of the dissolved inorganic phosphate vertical exchange coefficients of 1 - 4 g/cm/sec and vertical current speeds of 10**-5 to 10**-4 cm/sec are calculated for some stations in the Red Sea. The distribution of phosphate, silicate, nitrate, nitrite and ammonia for the Red Sea and the Straits of Bab el Mandeb are discussed. The special circulation is evaluated and the balance of the nutrients is estimated by means of the brutto transport. The nutrient deficit is assumed to be balanced by sporadic inflow of intermediate water from the Gulf of Aden. An example for such an inflow has been observed and is demonstrated. The silicate-salinity relationships are a suitable way for characterizing water masses in the Red Sea. Equations for the calculation of the different components from the carbonate system, the ion activities, and the calcium carbonate saturation are evaluated. The influence of temperature and pressure is taken into account. The carbonate saturation is calculated from the determined concentrations of calcium, alkalinity, and the hydrogen ion activity. Saturation values of 320 % are found for the surface layer and of 100% ± 1 for the deep water. The extraordinary equilibrium conditions may explain the constant Ca/Cl ratio and also the sedimentation of undissolved carbonate skelecons even in greater depths. A main sedimentation rate of 2 * 10**-3cm/year is evaluated from a total sedimentation of 10 * 106 to/a of calcium carbonate in the Red Sea. The appendix contains those data, which are not published in the data volume of the I.I.O.E. expedition of R. V. "Meteor".