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.

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.