Hostname: page-component-78c5997874-4rdpn Total loading time: 0 Render date: 2024-11-13T02:51:08.688Z Has data issue: false hasContentIssue false

Elemental stoichiometry of marine particulate matter measured by wavelength dispersive X-ray fluorescence (WDXRF) spectroscopy

Published online by Cambridge University Press:  22 July 2013

A.I. Paulino
Affiliation:
Department of Biology, University of Bergen, Post Box 7803, N-5020 Bergen, Norway
M. Heldal
Affiliation:
Department of Biology, University of Bergen, Post Box 7803, N-5020 Bergen, Norway
S. Norland
Affiliation:
Department of Biology, University of Bergen, Post Box 7803, N-5020 Bergen, Norway
J.K. Egge*
Affiliation:
Department of Biology, University of Bergen, Post Box 7803, N-5020 Bergen, Norway
*
Correspondence should be addressed to: J.K. Egge, Department of Biology, University of Bergen, Thormøhlensgate 53 A/B, N-5020 Bergen, Norway email: Jorun.Egge@bio.uib.no

Abstract

This paper describes the development of a method for quantitative measurement of the elemental composition of particulate matter (PM) in seawater. This method is based on use of wavelength dispersive X-ray fluorescence (WDXRF) analysing PM harvested on various filter types. As the amount of material is less than a monolayer of cells on the filters we reduced the need for absorption correction. Given the appropriate combination of filters and elements the detection limits are low: <1 µg/filter for carbon (C), nitrogen (N), and <0.1 µg/filter for silicon (Si), phosphorus (P), calcium (Ca) and iron (Fe). The analytical range used was 90–750 µg C, 23–116 µg N and 7–30 µg P, depending on the filters applied. Calibration constants for the elements included in this study were obtained from analysis of known quantities of chemical compounds on filters or silver plates. For carbon and nitrogen we also used comparative measurements of Synechococcus sp. cultures by CHN analyser and WDXRF. We harvested PM from 150 ml to 2000 ml on each filter in three replicates, obtaining less than 5% analytical variability between the replicates. One of the challenges using WDXRF as proposed here is the absorption of X-ray signals by the filter and variability of cell/particle sizes, and, consequentlyly, the variability of harvested PM on various filters. We find that an anodisc filter is best suited for C and N, while polycarbonate filters are best for heavier elements. Here we present analytical details and some data from field experiments related to C, N, P, Si, Ca and Fe in particles from seawater.

Type
Research Article
Copyright
Copyright © Marine Biological Association of the United Kingdom 2013 

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

Altabet, M.A., Bishop, J.K.B. and McCarthy, J.J. (1992) Differences in particulate nitrogen concentration and isotopic composition for samples collected by bottles and large-volume pumps in Gulf-Stream warm-core rings and the Sargasso Sea. Deep-Sea Research Part A—Oceanographic Research Papers 39(1A), S405S417.CrossRefGoogle Scholar
Arrigo, K.R. (2005) Marine microorganisms and global nutrient cycles. Nature 437, 349355.Google Scholar
Barrett, P.M., Resing, J.A., Buck, N.J., Buck, C.S., Landing, W.M. and Measures, C.I. (2012) The trace element composition of suspended particulate matter in the upper 1000 m of the eastern North Atlantic Ocean: A16N. Marine Chemistry 142–144 4153.Google Scholar
Bobrov, V.A., Phedorin, M.A., Leonova, G.A. and Kolmogorov, Y.P. (2005) SR XRF element analysis of sea plankton. Nuclear Instruments & Methods in Physics Research Section A—Accelerators Spectrometers Detectors and Associated Equipment 543, 259265.Google Scholar
Bonvin, D., Yellepeddi, R. and Buman, A. (2000) Applications and perspectives of a new innovative XRF-XRD Spectrometer in industrial process control. JCPDS—International Centre for Diffraction Data 2000, Advances in X-ray Analysis 42, 126136.Google Scholar
Fagerbakke, K.M., Heldal, M. and Norland, S. (1996) Content of carbon, nitrogen, oxygen, sulfur and phosphorus in native aquatic and cultured bacteria. Aquatic Microbial Ecology 10, 1527.Google Scholar
Field, C.B., Behrenfeld, M.J., Randerson, J.T. and Falkowski, P. (1998) Primary production of the biosphere: integrating terrestrial and oceanic components. Science 281(5374), 237240.Google Scholar
Garivait, S., Quisefit, J.P., de Chateaubourg, P. and Malingre, G. (1997) Multi-element analysis of plants by WDXRF using the scattered radiation correction method. X-Ray Spectrometry 26, 257264.Google Scholar
Goldstein, J.I., Newbury, D.E., Echlin, P., Jo, D.C., Romig, A.D. Jr, Lyman, C.E., Fiori, C. and Lifshin, E. (1992) Scanning electron microscopy and X–ray microanalysis. A text for biologists. 2nd edition. New York: Plenum Press.CrossRefGoogle Scholar
Grasshoff, K., Ehrhardt, M. and Kremling, K. (1983) Methods of seawater analysis. 2nd edition. Weinheim: Verlag Chemie.Google Scholar
Heimdal, B.R., Egge, J.K., Veldhuis, M.J.W. and Westbroek, P. (1994) The 1992 Norwegian Emiliania–Huxleyi experiment—an overview. Sarsia 79, 285290.Google Scholar
Heldal, M., Fagerbakke, K.M., Tuomi, P. and Bratbak, G. (1996) Abundant populations of iron and manganese sequestering bacteria in coastal water. Aquatic Microbial Ecology 11, 127133.Google Scholar
Heldal, M., Norland, S., Erichsen, E.S., Thingstad, T.F. and Bratbak, G. (2012) An unaccounted fraction of marine biogenic CaCO3 particles. PLoS ONE 7, e47887. doi:10.1371/journal.pone.0047887.Google Scholar
Ho, T.Y., Quigg, A., Finkel, Z.V., Milligan, A.J., Wyman, K., Falkowski, P.G. and Morel, F.M.M. (2004) The elemental composition of some marine phytoplankton (vol 39, pg 1145, 2003). Journal of Phycology 40, 227–227.Google Scholar
Klausmeier, C.A., Litchman, E. and Levin, S.A. (2004) Phytoplankton growth and stoichiometry under multiple nutrient limitation. Limnology and Oceanography 49, 14631470.Google Scholar
Libes, S.M. (1992). An introduction to marine biogeochemistry. Chichester: John Wiley & Sons.Google Scholar
Mahrok, M. and Shamoon, S. (2008) Effect of geometrical factors on the validity of XRF Spectrometer data. Journal of Applied Spectroscopy 75, 295299.Google Scholar
Marie, D., Brussaard, C.P.D., Partensky, F. and Vaulot, D. (1999) Enumeration of phytoplankton, bacteria, viruses in marine samples. Current Protocols in Cytometry, 11.11.111.11.15.Google Scholar
Menden-Deuer, S. and Lessard, E.J. (2000) Carbon to volume relationships for dinoflagellates, diatoms, and other protist plankton. Limnology and Oceanography 45, 569579.Google Scholar
Nayar, S. and Chou, L.M. (2003) Relative efficiencies of different filters in retaining phytoplankton for pigment and productivity studies. Estuarine, Coastal and Shelf Science 58, 241248.Google Scholar
Norrman, B. (1993) Filtration of water samples for DOC studies. Marine Chemistry 41, 239242.CrossRefGoogle Scholar
Olenina, I., Hajdu, S., Edler, L., Andersson, A., Wasmund, N., Bruch, S., Göbel, J., Gromisz, S., Huseby, S., Huttunrn, M., Jaanis, A., Kokkonen, P., Ledaine, I. and Niemkiewicz, E. (2006) Biovolumes and size-classes of phytoplankton in the Baltic Sea. In Baltic Sea Environment Proceedings No. 106. Helsinki: Baltic Marine Environment Protection Commission.Google Scholar
Paasche, E. (1980) Silicon content of five marine planktonic diatom species measured with a rapid filter method. Limnology and Oceanography 25, 474480.Google Scholar
Paasche, E. (2002) A review of the coccolithophorid Emiliania huxleyi (Prymnesiophyceae), with particular reference to growth, coccolith formation, and calcification–photosynthesis interactions. Phycologia 40, 503529.CrossRefGoogle Scholar
Paasche, E. and Ostergren, I. (1980) The annual cycle of plankton diatom growth and silica production in the inner Oslo fjord. Limnology and Oceanography 25, 481494.Google Scholar
Paulino, A.I., Egge, J.K. and Larsen, A. (2008) Effects of increased atmospheric CO2 on small and intermediate sized osmotrophs during a nutrient induced phytoplankton bloom. Biogeosciences 5, 739748.Google Scholar
Redfield, A.C. (1934) On the proportions of organic derivatives in sea water and their relation to the composition of plankton. In James Johnstone memorial volume. Liverpool: University Press, pp. 176192.Google Scholar
Sansoni, B. (1987) Multielement analysis for environmental characterization. Pure and Applied Chemistry 59, 579610.Google Scholar
Seydel, U., Haas, M., Rietschel, E.T. and Lindner, B. (1992) Laser microprobe mass-spectrometry of individual bacterial organisms and of isolated bacterial compounds—a tool in microbiology. Journal of Microbiological Methods 15, 167183.Google Scholar
Sondergaard, M. and Middelboe, M. (1993) Measurements of particulate organic-carbon—a note on the use of glass-fiber (GF/F) and anodisc (R) filters. Archiv für Hydrobiologie 127, 7385.Google Scholar
Sterner, R.W. and Elser, J.J. (2002) Ecological stoichiometry: the biology of elements from molecules to the biosphere. Princeton, NJ: Princeton University Press.Google Scholar
Thingstad, T.F., Bellerby, R.G.J., Bratbak, G., Borsheim, K.Y., Egge, J.K., Heldal, M., Larsen, A., Neill, C., Nejstgaard, J., Norland, S., Sandaa, R.A., Skjoldal, E.F., Tanaka, T., Thyrhaug, R. and Topper, B. (2008) Counterintuitive carbon-to-nutrient coupling in an Arctic pelagic ecosystem. Nature 455(7211), 337387.Google Scholar
Twining, B.S., Baines, S.B., Fisher, N.S., Maser, J., Vogt, S., Jacobsen, C., Tovar-Sanchez, A. and Sanudo-Wilhelmy, S.A. (2003) Quantifying trace elements in individual aquatic protist cells with a synchrotron X-ray fluorescence microprobe. Analytical Chemistry 75(15), 38063816.Google Scholar
Twining, B.S., Baines, S.B., Vogt, S. and de Jonge, M.D. (2008) Exploring ocean biogeochemistry by single-cell microprobe analysis of protist elemental composition. Journal of Eukaryotic Microbiology 55, 151162.CrossRefGoogle ScholarPubMed
Wu, P., He, S.P., Luo, B. and Hou, X.D. (2009) Flame furnace atomic absorption spectrometry: a review. Applied Spectroscopy Reviews 44(5), 411437.Google Scholar
Utermöhl, H. (1931) Neue wege in der quantitativen Erfassung des planktons. (Mit besonderer Berücksichtigung des ultraplanktons). Verhandlungen der Internationalen Verienigung für Theoretische und Angewandte Limnologie 5, 567596.Google Scholar
Verity, P.G., Whipple, S.J., Nejstgaard, J.C. and Alderkamp, A.C. (2007) Colony size, cell number, carbon and nitrogen contents of Phaeocystis pouchetii from western Norway. Journal of Plankton Research 29, 359367.CrossRefGoogle Scholar