Content Science

Marine Polyphosphate: A Key Player in Geologic

Phosphorus Sequestration

Julia Diaz, et al.

Science 320, 652 (2008);

DOI: 10.1126/science.1151751

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Marine Polyphosphate: A Key Player on organic forms (1, 13). The lack of commonly

used analytical techniques that cleanly evaluate

polyphosphate within samples has further re-

in Geologic Phosphorus Sequestration sulted in a paucity of research on the importance

of this phase. With the recent development of

high-resolution x-ray spectromicroscopy methods,

Julia Diaz,1 Ellery Ingall,1* Claudia Benitez-Nelson,2 David Paterson,3 Martin D. de Jonge,3

various particulate organic, mineral, and poly-

Ian McNulty,3 Jay A. Brandes4

meric phosphorus-containing phases like poly-

The in situ or authigenic formation of calcium phosphate minerals in marine sediments is a phosphate can now be identified and mapped at

major sink for the vital nutrient phosphorus. However, because typical sediment chemistry is not submicrometer scales. In addition, a new com-

kinetically conducive to the precipitation of these minerals, the mechanism behind their formation bined electrodialysis/reverse osmosis technique

has remained a fundamental mystery. Here, we present evidence from high-sensitivity x-ray allows for a more comprehensive examination

and electrodialysis techniques to describe a mechanism by which abundant diatom-derived of phosphorus composition in the dissolved

polyphosphates play a critical role in the formation of calcium phosphate minerals in marine phase. We have developed insights into the origin

sediments. This mechanism can explain the puzzlingly dispersed distribution of calcium and transformation of marine polyphosphate

phosphate minerals observed in marine sediments worldwide. through the application of these high-resolution

x-ray (14) and high-recovery electrodialysis (15, 16)

techniques.

hosphorus is a vital macronutrient that pro- trient availability and biological production, an

P We collected organisms, sediments, and dis-

foundly influences global oceanic primary understanding of the underlying mechanisms that

solved and particulate matter during April and

production on both modern and geologic lead to the formation and burial of apatite in mod-

July 2007 from Effingham Inlet, a Pacific fjord

time scales (1, 2). Over the past several decades, ern and ancient sediments is critically important.

located on Vancouver Island, British Columbia

the residence time of phosphorus in the ocean has Here, we show that polyphosphate is a key com-

(fig. S2) (16). During the spring bloom of April

been repeatedly revised downwards as previous- ponent in the formation of apatite in marine

2007, intracellular polyphosphate inclusions were

ly unidentified sedimentary sinks have been dis- sediments.

observed in individual diatoms, including the glob-

covered (1, 3). Among these sinks are ubiquitous Polyphosphate is a relatively understudied

ally ubiquitous and abundant Skeletonema spp.

fine-grained authigenic apatite minerals (4), whose component of the marine phosphorus cycle. A

(fig. S3). On the basis of bulk 31P nuclear

origin is enigmatic (5). Given the strong influence linear polymer of orthophosphate units linked by

of this mineral sink on the global cycling of phos- phosphoanhydride bonds (fig. S1), polyphosphate magnetic resonance (NMR) characterization of

phorus and its potential impact on long-term nu- is present in cells as dense, calcium-associated the spring bloom plankton community (16), inor-

cytoplasmic inclusions (6). Under phosphate- ganic polyphosphate represented a substantial 7%

enriched conditions, cultured marine algae syn- of total phosphorus in surface water biomass.

1

School of Earth and Atmospheric Sciences, Georgia Institute

thesize polyphosphate as a luxury nutrient reserve Surface water dissolved phosphate concentrations

of Technology, Atlanta, GA 30332-0340, USA. 2Marine Science

(7 12). The biological synthesis of substantial were 0.5 mM, which reflects a level of phospho-

Program and Department of Geological Sciences, University of

South Carolina, Columbia, SC 29208, USA. 3Advanced Photon amounts of polyphosphate in natural marine sys- rus availability typical of coastal marine systems.

Source, Argonne National Laboratory, 9700 South Cass Avenue, tems, in contrast, has been hypothesized to be Nutrient ratios were also consistent with phospho-

Argonne, IL 60439, USA. 4Skidaway Institute of Oceanography, inconsequential (12), as phosphorus is present at rus limitation in our field site (nitrogen:phosphorus =

10 Ocean Science Circle, Savannah, GA 31411, USA.

biologically limiting concentrations in much of ~ 40). By comparison, in laboratory cultures

*To whom correspondence should be addressed. E-mail:

with enriched, ~mM phosphate concentrations,

the global ocean (1, 3). Correspondingly, inves-

******@***.******.***

tigations into the composition of marine biogenic Skeletonema spp. and Thalassiosira spp. can

Present address: Australian Synchrotron, 800 Blackburn Road,

phosphorus compounds have typically focused accumulate polyphosphate to correspondingly

Clayton, Victoria 3168, Australia.

652 2 MAY 2008 VOL 320 SCIENCE www.sciencemag.org

REPORTS

high levels of 30% and 19 to 43% of total of these cells, including variably sized polyphos- Individual diatoms containing intracellular poly-

cellular phosphorus, respectively (10, 12). The phate inclusions. Consistent with these processes, phosphates were observed throughout the water

population of diatom-dominated plankton in we observed a substantial amount of polyphos- column, which suggests that sinking polyphos-

phate in the

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