Abstract
Trace concentrations of labile dissolved organic phosphorus (LDOP) in oligotrophic seawater were measured by use of an enzymatic procedure and a nanomolar phosphate analytical system consisting of a gas-segmented continuous flow analyzer with a liquid waveguide capillary cell. LDOP, defined as DOP hydrolyzed by alkaline phosphatase (AP) from Escherichia coli, was quantified as the difference between the phosphate concentrations of the seawater sample with and without AP treatment. For sensitive measurement of LDOP, we found that phosphate contamination derived from commercially available AP must be corrected, and azide treatment before AP treatment proved effective in removing biological effect that occurs during DOP hydrolysis. Field observations at six stations of the western North Pacific and the East China Sea during the boreal summer revealed that, in the upper 200 m of the water column, LDOP concentrations ranged from the detection limit (3 nM) to 243 nM, and phosphate concentrations ranged from 5 to 374 nM. The spatial distribution patterns of LDOP were similar to those of phosphate. Most of the depth profiles for LDOP and phosphate showed concentrations were extremely low, <25 nM, between the surface and the deep chlorophyll maximum layer (DCML) and increased below the DCML. Strongly depleted LDOP and phosphate above the DCML suggest that LDOP is actively hydrolyzed under phosphate-depleted conditions and utilized by microbes.
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Brzezinski MA, Nelson DM (1995) The annual silica cycle in the Sargasso Sea near Bermuda. Deep Sea Res I 42:1215–1237
Brzezinski MA, Nelson DM (1996) Chronic substrate limitation of silicic acid uptake rates in the western Sargasso Sea. Deep Sea Res II 43:437–453
Brzezinski MA, Villareal TA, Lipschultz F (1998) Silica production and the contribution of diatoms to new and primary production in the central North Pacific. Mar Ecol Prog Ser 167:89–104
Cavender-Bares KK, Karl DM, Chisholm SW (2001) Nutrient gradients in the western North Atlantic Ocean: relationship to microbial community structure and comparison to patterns in the Pacific Ocean. Deep Sea Res I 48:2373–2395
Cembella AD, Antia NJ, Harrison PJ (1982) The utilization of inorganic and organic phosphorus compounds as nutrients by eukaryotic microalgae: a multidisciplinary perspective: part 1. Crit Rev Microbiol 10:317–391
Cutter GA, Cutter LS (2006) Biogeochemistry of arsenic and antimony in the North Pacific Ocean. Geochem Geophys Geosyst 7:Q05M08. doi:10.1029/2005GC001159
Cutter GA, Cutter LS, Featherstone AM, Lohrenz SE (2001) Antimony and arsenic biogeochemistry in the western Atlantic Ocean. Deep Sea Res II 48:2895–2915
Dore JE, Houlihan T, Hebel DV, Tien G, Tupas L, Karl DM (1996) Freezing as a method of sample preservation for the analysis of dissolved inorganic nutrients in seawater. Mar Chem 53:173–185
Eppley RW, Peterson BJ (1979) Particulate organic matter flux and planktonic new production in the deep ocean. Nature 282:677–680
Feuillade M, Dorioz JM (1992) Enzymatic release of phosphate in sediments of various origins. Water Res 26:1195–1201
Gimbert LJ, Haygarth PM, Worsfold PJ (2007) Determination of nanomolar concentrations of phosphate in natural waters using flow injection with a long path length liquid waveguide capillary cell and solid-state spectrophotometric detection. Talanta 71:1624–1628
Hansen HP, Koroleff F (1999) Determination of nutrients. In: Grasshodd K, Kremling K, Ehrhardt M (eds) Methods of Seawater Analysis, 3rd edn. Wiley, Weinheim, pp 159–228
Hashihama F, Furuya K, Kitajima S, Takeda S, Takemura T, Kanda J (2009) Macro-scale exhaustion of surface phosphate by dinitrogen fixation in the western North Pacific. Geophys Res Lett 36:L03610. doi:10.1029/2008GL036866
Hashihama F, Sato M, Takeda S, Kanda J, Furuya K (2010) Mesoscale decrease of surface phosphate and associated phytoplankton dynamics in the vicinity of the subtropical South Pacific islands. Deep Sea Res I 57:338–350
Hoppe H-G (2003) Phosphatase activity in the sea. Hydrobiologia 493:187–200
Huang X-L, Zhang J-Z (2009) Neutral persulfate digestion at sub-boiling temperature in an oven for total dissolved phosphorus determination in natural waters. Talanta 78:1129–1135
Karl DM, Tien G (1992) MAGIC: a sensitive and precise method for measuring dissolved phosphorus in aquatic environments. Limnol Oceanogr 37:105–116
Kodama T, Furuya K, Hashihama F, Takeda S, Kanda J (2011) Occurrence of rain-origin nitrate patches at the nutrient-depleted surface in the East China Sea and the Philippine Sea during summer. J Geophys Res 116:C08003. doi:10.1029/2010JC006814
Li QP, Hansell DA (2008) Intercomparison and coupling of magnesium-induced co-precipitation and long-path liquid-waveguide capillary cell techniques for trace analysis of phosphate in seawater. Anal Chim Acta 611:68–72
Li QP, Hansell DA, Zhang J-Z (2008) Underway monitoring of nanomolar nitrate plus nitrite and phosphate in oligotrophic seawater. Limnol Oceanogr: Methods 6:319–326
Ma J, Yuan D, Liang Y (2008a) Sequential injection analysis of nanomolar soluble reactive phosphorus in seawater with HLB solid phase extraction. Mar Chem 111:151–159
Ma J, Yuan D, Liang Y, Dai M (2008b) A modified analytical method for the shipboard determination of nanomolar concentrations of orthophosphate in seawater. J Oceanogr 64:443–449
Mather RL, Reynolds SE, Wolff GA, Williams RG, Torres-Valdes S, Woodward EMS, Landolfi A, Pan X, Sanders R, Achterberg EP (2008) Phosphorus cycling in the North and South Atlantic Ocean subtropical gyres. Nat Geosci 1:439–443
Miller JC, Miller JN (1993) Statistics for analytical chemistry, 2nd edn. Ellis Horwood, New York, p 233
Mills MM, Ridame C, Davey M, LaRoche L, Geider RJ (2004) Iron and phosphorus co-limit nitrogen fixation in the eastern tropical North Atlantic. Nature 429:292–294
Moore CM, Mills MM, Achterberg EP, Geider RJ, LaRoche J, Lucas MI, McDonagh EL, Pan X, Poulton AJ, Rijkenberg MJA, Suggett DJ, Ussher SJ, Woodward EMS (2009) Large-scale distribution of Atlantic nitrogen fixation controlled by iron availability. Nat Geosci 2:867–871
Moutin T, Thingstad TF, Wambeke FV, Marie D, Slawyk G, Raimbault P, Claustre H (2002) Does competition for nanomolar phosphate supply explain the predominance of the cyanobacterium Synechococcus? Limnol Oceanogr 47:1562–1567
Moutin T, Karl DM, Duhamel S, Rimmelin P, Raimbault P, Mooy BASV, Claustre H (2008) Phosphate availability and the ultimate control of new nitrogen input by nitrogen fixation in the tropical Pacific Ocean. Biogeosciences 5:95–109
Murphy J, Riley JP (1962) A modified single solution method for determination of phosphate in natural waters. Anal Chim Acta 27:31–36
Patey MD, Achterberg EP, Rijkenberg MJA, Statham PJ, Mowlem M (2010) Interferences in the analysis of nanomolar concentrations of nitrate and phosphate in oceanic waters. Anal Chim Acta 673:109–116
Sañudo-Wilhelmy SA, Kustka AB, Gobler CJ, Hutchins DA, Yang M, Lwiza K, Burns J, Capone DG, Raven JA, Carpenter EJ (2001) Phosphorus limitation of nitrogen fixation by Trichodesmium in the central Atlantic Ocean. Nature 411:66–69
Strickland JDH, Parsons TR (1972) A Practical handbook of seawater analysis, 2nd edn. Bull Fish Res Bd Can, Ottawa, p 310
Suzumura M, Ishikawa K, Ogawa H (1998) Characterization of dissolved organic phosphorus in coastal seawater using ultrafiltration and phosphohydrolytic enzymes. Limnol Oceanogr 43:1553–1564
Suzumura M, Hashihama F, Yamada N, Kinouchi S (2012) Dissolved phosphorus pools and alkaline phosphatase activity in the euphotic zone of the western North Pacific Ocean. Front Microbiol 3:99. doi: 10.3389/fmicb.2012.00099
Wu J, Sunda W, Boyle EA, Karl DM (2000) Phosphate depletion in the western North Atlantic Ocean. Science 289:759–761
Zhang JZ, Chi J (2002) Automated analysis of nanomolar concentrations of phosphate in natural waters with liquid waveguide. Environ Sci Technol 36:1048–1053
Acknowledgments
We are grateful to the officers, crew members, and members of the scientific party of the R/V Tansei-maru cruises for their cooperation at sea. We particularly acknowledge H Ogawa and K Furuya for organizing the cruises KT-10-13 and KT-10-19, respectively. This work was financially supported by Grant-in-Aid No. 22710006 for Young Scientists (B) from the Japan Society for Promotion of Science, and Grant-in-Aid No. 18067007 for Scientific Research in Priority Areas (Western Pacific Air-Sea Interaction Study “W-PASS”) and Grant-in-Aid No. 24121003 for Scientific Research in Innovative Areas (New Ocean Paradigm on Its Biogeochemistry, Ecosystem and Sustainable Use “NEOPS”) from the Ministry of Education, Culture, Sports, Science and Technology, Japan.
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Hashihama, F., Kinouchi, S., Suwa, S. et al. Sensitive determination of enzymatically labile dissolved organic phosphorus and its vertical profiles in the oligotrophic western North Pacific and East China Sea. J Oceanogr 69, 357–367 (2013). https://doi.org/10.1007/s10872-013-0178-4
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DOI: https://doi.org/10.1007/s10872-013-0178-4