Geochemistry of iron and manganese in soils and sediments of a mangrove system, Island of Pai Matos (Cananeia - SP, Brazil)

Five zones along a transect of 180 m were selected for study on the Island of Pai Matos (Sao Paulo, Brazil). Four of the zones are colonised by vascular plants (Spartina SP, Laguncularia LG, Avicennia AV and Rhizophora RH) and were denominated soils, and the other zone, which lacks vegetation, was denominated sediment (SD). The geochemical conditions differed significantly in soils and sediment and also at different depths. The soils were oxic (Eh > 350 mV) or suboxic (Eh: 350-100 mV) at the surface and anoxic (Eh < 100 mV) at depth, whereas in the sediment anoxic conditions prevailed at all depths, but with a lower concentration of sulphides in the pore water and pyrite in the solid fraction. Under these geochemical conditions Fe is retained in the soils, while the Mn tends to be mobilized and lost. The most abundant form of iron oxyhydroxide was lepidocrocite (mean concentration for all sites and depths, 45 +/- 19 mu mol g(-1)), followed by goethite (30 19 mu mol g(-1))and ferrihydrite (19 +/- 11 mu mol g(-1)),with significant differences among the mean concentrations. There was a significant decrease with depth in all the types of Fe oxyhydroxides measured, particularly the poorly crystalline forms. The pyrite fraction was an important component of the free Fe pool (non-silicate Fe) in all soils as well as in the sediment, especially below 20 cm depth (mean concentration for all sites and depths, 60 +/- 54 mu mol CI). Furthermore, the mean concentration of Fe-pyrite for all sites and depths was higher than that obtained for any of the three Fe oxyhydroxides measured. The Fe-AVS was a minor fraction, indicating that the high concentrations of dissolved Fe in the soils in the upper area of the transect result from the oxidation of Fe sulphides during low tide. Mossbauer spectroscopy also revealed that most of the Fe (III) was associated with silicates, in this case nontronite. The presence of crystals of pyrite associated with phyllosilicates in samples from the upper layer of the soils may indicate that pyritization of this form of Fe(III) is more rapid than usually reported for ocean bed sediments. The sequential extraction of Mn did not reveal any clearly dominant fraction, with the Mn-carbonate fraction being the most prevalent, followed by exchangeable Mn and oxides of Mn, whereas pyrite-Mn and Mn associated with crystalline Fe-oxides were present at significantly lower concentrations. The high concentration of dissolved Mn found in the soils in the lower part of the transect is consistent with the fact that the solubility is determined by the carbonate fraction. Unlike for Fe, in the soils in the higher zone, which are subject to intense drainage during low tide, there was loss of Mn, as reflected by the concentration of total Mn. (C) 2008 Elsevier B.V. All rights reserved.

Adsorsão e coeficientes de distribuição de selênio em solos do Estado de São Paulo

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Mineralogical and geochemical influences on sediment color of Amazon wetlands analyzed by visible spectrophotometry

Com base em dados sedimentológicos e geoquímicos, este trabalho relaciona medições espectrofotométricas com a composição do sedimento, e sua aplicação em estudos paleoecológicos das áreas alagáveis da Amazônia. Os dados CIELAB estão diretamente relacionados à composição mineralógica e química dos sedimentos, especialmente quartzo, oxihidróxidos e sulfetos de ferro, e carbono orgânico total. Conteúdos de carbono orgânico total entre 0,4-1%, 1-2%, 3-5% e 15-40% foram relacionados a dados de L* (luminosidade) de 27, 26-15, 7-10 e 7 ou menos, respectivamente. Os valores CIELAB de um depósito com turfa em Marabá, Pará, foram proporcionais a variações no conteúdo de quartzo e carbono orgânico total, mas mudanças nas zonas de cores similares, principalmente nos valores de +a* (vermelho) e +b* (amarelo), ao longo de outros depósitos em Calçoene, Amapá e Soure, Pará, indicam uma relação muito próxima entre os conteúdos de carbono orgânico total, oxihidróxidos e sulfetos de ferro. Além disso, o diagrama Q7/4 (razão entre valores percentuais de refletância em 700 nm e 400 nm, juntamente com dados de L*) indicou sedimentos ricos em ferro para a fácies lama bioturbada no depósito do Amapá, fácies lama bioturbada e areia bioturbada do depósito de Soure, e das fácies areia com laminação cruzada e areia maciça do depósito de Marabá. Ainda, sedimentos ricos em carbono orgânico foram encontrados na lama bioturbada no depósito do Amapá, fácies heterolítica lenticular e lama bioturbada do depósito de Soure, e das fácies lama laminado e turfa do depósito de Marabá. Na área de Marabá, os dados sugerem uma influência autóctone com formação de turfa. As áreas de zonas úmidas costeiras no Marajó e Amapá representam o desenvolvimento típico de planícies de maré com formação de sulfetos e oxihidróxidos de ferro durante alternâncias entre inundação e exposição.

Comparison of iron isotope variations in modern and Ordovician siliceous Fe oxyhydroxide deposits

Formation pathways of ancient siliceous iron formations and related Fe isotopic fractionation are still not completely understood. Investigating these processes, however, is difficult as good modern analogues to ancient iron formations are scarce. Modern siliceous Fe oxyhydroxide deposits are found at marine hydrothermal vent sites, where they precipitate from diffuse, low temperature fluids along faults and fissures on the seafloor. These deposits exhibit textural and chemical features that are similar to some Phanerozoic iron formations, raising the question as to whether the latter could have precipitated from diffuse hydrothermal fluids rather than from hydrothermal plumes. In this study, we present the first data on modern Fe oxyhydroxide deposits from the Jan Mayen hydrothermal vent fields, Norwegian-Greenland Sea. The samples we investigated exhibited very low δ56Fe values between -2.09‰ and -0.66‰. Due to various degrees of partial oxidation, the Fe oxyhydroxides are with one exception either indistinguishable from low-temperature hydrothermal fluids from which they precipitated (-1.84‰ and -1.53‰ in δ56Fe) or are enriched in the heavy Fe isotopes. In addition, we investigated Fe isotope variations in Ordovician jasper beds from the Løkken ophiolite complex, Norway, which have been interpreted to represent diagenetic products of siliceous ferrihydrite precursors that precipitated in a hydrothermal plume, in order to compare different formation pathways of Fe oxyhydroxide deposits. Iron isotopes in the jasper samples have higher δ56Fe values (-0.38‰ to +0.89‰) relative to modern, high-temperature hydrothermal vent fluids (ca. -0.40‰ on average), supporting the fallout model. However, formation of the Ordovician jaspers by diffuse venting cannot be excluded, due to lithological differences of the subsurface of the two investigated vent systems. Our study shows that reliable interpretation of Fe isotope variations in modern and ancient marine Fe oxyhydroxide deposits depends on comprehensive knowledge of the geological context. Furthermore, we demonstrate that very negative δ56Fe values in such samples might not be the result of microbial dissimilatory iron reduction, but could be caused instead by inorganic reactions.

Thermochromatography study of volatile polonium species in various gas atmospheres

Phenomena related to the volatilization of polonium and its compounds are critical issues for the safety assessment of the innovative lead–bismuth cooled type of nuclear reactor or accelerator driven systems. The formation and volatilization of different species of polonium and their interaction with fused silica was studied by thermochromatography using carrier gases with varied redox potential. The obtained results show that under inert and reducing conditions in the absence of moisture, elemental polonium is formed. Polonium compounds more volatile than elemental polonium can be formed if traces of moisture are present in both inert and reducing carrier gas. The use of dried oxygen as carrier gas leads to the formation of polonium oxides, which are less volatile than elemental polonium. It was also found that the volatility of polonium oxides increases with increasing oxidation state. In the presence of moisture in an oxidizing carrier gas, species are formed that are more volatile than the oxides and less volatile than the elemental polonium. Considering the redox potential of the carrier gas those species are likely oxyhydroxides.

Peak Last Glacial weathering intensity on the North American continent recorded by the authigenic Hf isotope composition of North Atlantic deep-sea sediments

We have retrieved radiogenic hafnium (Hf) isotope compositions (ɛHf) from authigenic Fe–Mn oxyhydroxides of deep northwest Atlantic sediments deposited over the past 26 ka to investigate the oceanic evidence of changes in dissolved weathering inputs from NE America during the last deglaciation. The extraction of seawater-derived Hf isotopic compositions from Fe–Mn oxyhydroxides is not a standard procedure. Comparisons between the Al/Hf ratios and Hf isotopic compositions of the chemically extracted authigenic phase on the one hand, and those of the corresponding detrital fractions on the other, provide evidence that the composition of past seawater has been reliably obtained for most sampled depths with our leaching procedures. This is endorsed most strongly by data for a sediment core from 4250 m water depth at the deeper Blake Ridge, for which consistent replicates were produced throughout. The Hf isotopic composition of the most recent sample in this core also closely matches that of nearby present day central North Atlantic seawater. Comparison with previously published seawater Nd and Pb isotope compositions obtained on the same cores shows that both Hf and Pb were released incongruently during incipient chemical weathering, but responded differently to the deglacial retreat of the Laurentide Ice Sheet. Hafnium was released more congruently during peak glacial conditions of the Last Glacial Maximum (LGM) and changed to typical incongruent interglacial ɛHf signatures either during or shortly after the LGM. This indicates that some zircon-derived Hf was released to seawater during the LGM. Conversely, there is no clear evidence for an increase in the influence of weathering of Lu-rich mineral phases during deglaciation, possibly since relatively unradiogenic Hf contributions from feldspar weathering were superimposed. While the authigenic Pb isotope signal in the same marine sediment samples traced peak chemical weathering rates on continental North America during the transition to the Holocene a similar incongruent excursion is notably absent in the Hf isotope record. The early change towards more radiogenic ɛHf in relation to the LGM may provide direct evidence for the transition from a cold-based to a warm-based Laurentide Ice Sheet on the Atlantic sector of North America.

Chemistry of hot waters sampled from basaltic basement at DSDP Hole 83-504B

Seawater that has been altered by reaction with basaltic basement has been sampled from Deep Sea Drilling Project Hole 504B, located on 5.9-m.y.-old crust on the southern flank of the Costa Rica Rift. Fourteen water samples have been collected on Legs 69, 70, and 83, both before and after renewed drilling on the latter two legs, at temperatures from 69 to 133°C and pressures from 390 to 425 bars. The water sampled prior to renewed drilling on Leg 83 had occupied the hole for nearly 2 yr. since it was last flushed with surface seawater at the end of Leg 70. Despite some contamination by seawater during sampling, the composition of two of these waters has been determined by using nitrate as a tag for the contaminant. Both the 80 and 115°C waters have seawater chlorinity, but have lost considerable Mg, Na, K, sulfate, and 02, and have gained Ca, alkalinity, Si, NH3 and H2S. The loss of sulfate is due to anhydrite precipitation, as indicated by the d34S value of the remaining dissolved sulfate. The 87Sr/86Sr ratio has been lowered to 0.7086 for the 80°C water and 0.7078 for the 115°C water, whereas the Sr concentration is nearly unchanged. The changes in major element composition relative to seawater are also larger for the 115°C water, indicating that the basement formation water at this site probably varies in composition with depth. Based on their direction relative to seawater, the compositional changes for the 80 and 115°C waters do not complement the changes inferred for the altered rocks from Hole 504B, suggesting that the bulk composition of the altered rocks, like their mineralogy, is largely unrelated to the present thermal and alteration regime in the hole. The exact nature of the reacted seawaters cannot be determined yet, however. During its 2 yr. residence in the hole, the surface seawater remaining at the end of Leg 70 would have reacted with the wall rocks and exchanged with their interstitial formation waters by diffusion and possibly convection. How far these processes have proceeded is not yet certain, although calculations suggest that diffusion alone could have largely exchanged the surface seawater for interstitial water. The d18O of the samples is indistinguishable from seawater, however, and the d14C of the 80°C sample is similar to that of ocean bottom water. Although the interpretation of these species is ambiguous, that of tritium should not be. Tritium analyses, which are in progress, should clarify the nature of the reacted seawaters obtained from the hole.

Documentation of sediment cores during SONNE Expedition SO228 from the western tropical Pacific

The core descriptions (chapter 7) summarize the most important results of the analysis of each sediment core following procedures applied during ODP/IODP expeditions. All cores were opened, described, and color-scanned. In the core descriptions the first column displays the lithological data that are based on visual analysis of the core and are supplemented by information from binocular and smear slide analyses. The sediment classification largely follows ODP/IODP convention. Lithological names consist of a principal name based on composition, degree of lithification, and/or texture as determined from visual description and microscopic observations. In the structure column the intensity of bioturbation together with individual or special features (turbidites, volcanic ash layers, plant debris, shell fragments, etc.) is shown. The hue and chroma attributes of color were determined by comparison with the Munsell soil color charts and are given in the color column in the Munsell notation. A GretagMacbethTM Spectrolino spectrophotometer was used to measure percent reflectance values of sediment color at 36 wavelength channels over the visible light range (380-730 nm) on all of the cores. The digital reflectance data of the spectrophotometer readings were routinely obtained from the surface (measured in 1 cm steps) of the split cores (archive half). The Spectrolino is equipped with a measuring aperture with folding mechanism allowing an exact positioning on the split core and is connected to a portable computer. The data are directly displayed within the software package Excel and can be controlled simultaneously. From all the color measurements, for each core the red/blue ratio (700 nm/450 nm) and the lightness are shown together with the visual core description. The reflectance of individual wavelengths is often significantly affected by the presence of minor amounts of oxyhydroxides or sulphides. To eliminate these effects, we used the red/blue ratio and lightness.

Chemistry of biogenic sediments from the equatorial Pacific

To increase our understanding of the mechanisms that control the distribution of Al and Ti within marine sediment, we performed sequential extractions targeting the chemical signatures of the loosely bound, exchangeable, carbonate, oxide, organic, opal, and residual fraction of sediment from a carbonate-dominated regime (equatorial Pacific) and from a mixed opal-terrigenous regime (West Antarctic Peninsula). We observe a systematic partitioning of Al and Ti between sediment phases that is related to bulk Al/Ti. We show that, where we can quantify an Al(excess) component, the dissolved Al is preferentially affiliated with the oxide fraction, resulting in Al/Ti molar ratios of 500-3000. This is interpreted as the result of surface complexation in the water column of dissolved Al onto oxyhydroxides. We also observe a previously undetected Ti(excess) with as much as 80% of the total Ti in the organic fraction, which is most likely a function of metal-organic colloidal removal from the water column. In samples where the excess metals are obscured by the detrital load, the Al and Ti are almost exclusively found in the residual phase. This argues for the paired removal of Al (preferentially by the oxide component) and Ti (preferentially by the organic component) from the water column by settling particulate matter. This research builds upon earlier work that shows changes in the bulk ratio of Al to Ti in carbonate sediment from the central-equatorial Pacific that coincide with changes in the sedimentary bulk accumulation rate (BAR). The ratios that are observed are as much as three times higher than typical shale values, and were interpreted as the result of scavenging of dissolved Al onto particles settling in the water column. Because this non-terrigenous Al(excess) accounts for up to 50% of the total sedimentary Al inventory and correlates best with BAR, the bulk Al/Ti may be a sensitive tracer of particle flux and, therefore, export production. Because we show that the excess metals are the result of scavenging processes, the bulk Al/Ti may be considered a sensitive proxy for this region.

Contents of rare earth and other chemical elements in Fe-Mn micronodules, nodules, and bottom sediments from the Clarion-Clipperton ore province in the Pacific Ocean

Processes governing the formation of rare earth element (REE) composition are under consideration for ferromanganese deposits (nodules, separate parts of nodules, and micronodules of different size fractions) within the Clarion-Clipperton ore province in the Pacific Ocean. It is shown that ferromanganese oxyhydroxide deposits with different chemical compositions can be produced in sediments under similar sedimentation conditions. In areas with high bioproductivity size of micronodules has positive correlation with Mn content and Mn/Fe and P/Fe ratios and negative correlation with Fe, P, REE, and Ce anomaly. Behavior of REE in micronodules from sediments within bioproductive zones is related to increase of influence of diagenetic processes in sediments as a response to the growth of size of micronodules. Distinctions in chemical composition of micronodules and nodules are related to their interaction with associated sediments. Micronodules grow in sediments using hydrogenous ferromanganese oxyhydroxides. As they grow, micronodules are enriched in labile fraction of sediments reworked during diagenesis. Sources of material of ferromanganese nodules are governed by their formation at the water bottom interface. Their upper part is formed by direct settling of iron oxyhydroxides from bottom water, whereas the lower part is accumulated due to diagenetic processes in sediments. Differences of REE compositions in ferromanganese deposits are caused by the reduction of manganese during diagenesis and its separation from iron. Iron oxyhydroxides form a sorption complex due to sorption of phosphate-ion from bottom and pore waters. Sorption of phosphate-ion results in additional sorption of REE.

Geochemistry of low-temperatuer altered basalts of ODP Hole 136-843B

The mineralogy and chemistry of altered basalts and the stable isotopic compositions of secondary vein carbonates were studied in cores from Ocean Drilling Program Hole 843B, located in 95-Ma crust of the Hawaiian Arch. Millimeter- to centimeter-sized dark alteration halos around veins are 5%-15% altered to celadonite and Fe-oxyhydroxides, plus minor saponite and calcite. Adjacent gray host rocks are about 15% altered to saponite and calcite. The dark halos are enriched in H2O+, CO2, FeT, K2O, MnO, and Fe3+/FeT and depleted in SiO2, Al2O3, MgO, and TiO2 relative to gray host rocks. Brown alteration halos occur around veins where veins are more abundant, and are similar to dark halos, but contain more Fe-oxyhydroxides and exhibit greater Fe2O3T contents and higher Fe3+/FeT. Stable isotopic compositions of vein carbonates are consistent with their precipitation from seawater at temperatures of 5°-40°C. Crosscutting relationships of veins and zoned vein and vesicle fillings reveal a sequence of secondary mineral formation and alteration conditions. Celadonite and Fe-oxyhydroxides formed and dark alteration halos developed relatively early, under oxidizing conditions at low temperatures (<50°C). Saponite formed later at lower seawater/rock ratios and under more reducing conditions. Calcite and pyrite formed last in veins and vesicles from more evolved, seawaterderived fluids at temperatures of 5°-40°C. A second stage of celadonite, with compositions distinct from the early celadonite, also occurred relatively late (within the "calcite stage"), and may be related to refracturing of the crust and introduction of less-evolved seawater solutions into the rocks. Trends to higher K2O contents are attributed to alteration, but high K/Ti, Ba, and Zr contents indicate the presence of enriched or transitional MORB. CO2 contents of Pacific ODP cores exhibit a general increase with age suggesting progressive fixation of CO2 as calcite in the crust, but this could be complicated by local heterogeneities in fracturing and calcite formation in the crust.

Bulk calcite minor element composition of ODP Leg 130 samples

We investigated minor element ratios (Sr/Ca and Mg/Ca) in bulk sediment samples from Sites 803-807 using a recently optimized sample treatment protocol for calcium-carbonate-rich sediments consisting of sequential reductive and ion exchange treatments. We evaluated this protocol relative to bulk sediment leaching using samples from Sites 804 and 806, the two end-member sites in the depth transect, reporting as well Mn/Ca and Fe/Ca ratios for sediments from these two sites processed by means of both methods. The Sr/Ca ratios were only slightly affected by the sample treatment, with an average reduction of 6%-7% caused primarily by the ion exchange step. The reductive sample treatment, designed to be effective at removing Mn-rich oxyhydroxides, has a major effect on Mg/Ca ratios, with up to 50% reduction, whereas little effect occurred in ion exchange alone on Mg/Ca ratios. The Mn/Ca and Fe/Ca ratios were not consistently offset by the sample treatment, and these ratios do not appear to be representative of calcite geochemistry reflecting either ocean history or diagenetic overprinting. Celestite solubility appears to be an important control on interstitial water Sr concentrations in these sites, and it must be considered when constructing Sr mass balance models of calcite recrystallization. Calcite Sr/Ca ratios (range 1-2 mmol/mol) are similar from site to site when plotted vs. age, with a pattern comparable to that for well-preserved foraminifer tests over the past 40 Ma. Interstitial water Mg and Ca gradients appear to reflect basement character and the intensity of alteration; they can vary substantially over a small area. Calcite Mg/Ca ratios (range 1.5-4.5 mmol/mol) differ from site to site, with generally higher ratios for sites at a shallower water depth. Increasing calcite Mg/Ca ratios correlate with decreasing Sr/Ca ratios in the treated samples. No consistent pattern exists for calcite Mg/Ca ratios vs. age or depth, nor is any direct correlation to interstitial water Mg/Ca ratios present.

Chemical composition of phillipsites from Core AKO26-35

Behavior of rare earth elements (REE) was examined in oceanic phillipsites collected from four horizons of eupelagic clay in the Southwest Basin of the Pacific Ocean. REE concentrations were determined in >50 ?m size fraction phillipsite samples by the ICP-MS method. Composition of separate phillipsite aggregates was studied by electron microprobe and secondary ion mass-spectrometry. Rare earth elements in phillipsite samples are related to admixture of ferrocalcium hydroxophosphates. Analysis of separate phillipsite aggregates reveals low (<0.1-18.1 ppm) REE(III) concentrations. Ce concentration varies between 2.7 and 140 ppm. The correlation analysis shows that REE(III) present in admixture of iron oxyhydroxides in separate phillipsite aggregates. Based on the REE(III) concentration in iron oxyhydroxides we can identify two generations of phillipsite aggregates. Massive rounded aggregates (phillipsite I) are depleted in REE, while pseudorhombic (phillipsite II) aggregates are enriched in REE and marked by a positive Ce anomaly. Oceanic phillipsites do not accumulate REE or inherit the REE signature of volcaniclastic material and oceanic deep water. Hence, REE distribution in phillipsites does not depend on sedimentation rate and composition of host sediments.

Chemistry of altered basalts from ODP Hole 123-765D

Volcanic basement recovered at Hole 765D is characterized by nonpervasive, oxidative alteration, typical of seafloor weathering. Chilled margins and the mesostasis of the lavas are variably altered to assemblages of celadonite, Fe-oxyhydroxides, zeolites, and calcite with trace saponite. Plagioclase is partially altered to Ca-Na zeolites and/or albite. Well-developed alteration halos parallel fracture surfaces and extend several centimeters into the surrounding rock. These clay-rich halos are enriched in K2O and Fe2O3 relative to the adjacent clay-poor rock. The halos and adjacent rock are characterized by d18O values 2 per mil-3 per mil higher than those of fresh MORB. The "freshness" of the samples and the scarcity of saponite suggest that the duration of seawater circulation was short-lived. Albitization of plagioclase indicates that the volcanic rocks were altered initially at low temperatures and were subsequently reheated off-axis in a closed environment. Reheating did not result in significant modification of the bulk composition of the crust.

Phosphorus partition and acumulation rates in sediments of ODP Legs 130 and 138

Understanding phosphorus (P) geochemistry and burial in oceanic sediments is important because of the role of P for modulating oceanic productivity on long timescales. We investigated P geochemistry in seven equatorial Pacific sites over the last 53 Ma, using a sequential extraction technique to elucidate sedimentary P composition and P diagenesis within the sediments. The dominant P-bearing component in these sediments is authigenic P (61-86% of total P), followed in order of relative dominance by iron-bound P (7-17%), organic P (3-12%), adsorbed P (2-9%), and detrital P (0-1%). Clear temporal trends in P component composition exist. Organic P decreases rapidly in younger sediments in the eastern Pacific (the only sites with high sample resolution in the younger intervals), from a mean concentration of 2.3 µmol P/g sediment in the 0-1 Ma interval to 0.4 µmol/g in the 5- 6 Ma interval. Over this same time interval, decreases are also observed for iron-bound P (from 2.1 to 1.1 µmol P/g) and adsorbed P (from 1.5 to 0.7 µmol P/g). These decreases are in contrast to increases in authigenic P (from 6.0-9.6 µmol P/g) and no significant changes in detrital P (0.1 µmol P/g) and total P (12 µmol P/g). These temporal trends in P geochemistry suggest that (1) organic matter, the principal shuttle of P to the seafloor, is regenerated in sediments and releases associated P to interstitial waters, (2) P associated with iron-rich oxyhydroxides is released to interstitial waters upon microbial iron reduction, (3) the decrease in adsorbed P with age and depth probably indicates a similar decrease in interstitial water P concentrations, and (4) carbonate fluorapatite (CFA), or another authigenic P-bearing phase, precipitates due to the release of P from organic matter and iron oxyhydroxides and becomes an increasingly significant P sink with age and depth. The reorganization of P between various sedimentary pools, and its eventual incorporation in CFA, has been recognized in a variety of continental margin environments, but this is the first time these processes have been revealed in deep-sea sediments. Phosphorus accumulation rate data from this study and others indicates that the global pre-anthropogenic input rate of P to the ocean (20x10**10 mol P/yr) is about a factor of four times higher than previously thought, supporting recent suggestions that the residence time of P in the oceans may be as short as 10000-20000 years.