A high-resolution analyser for the measurement of ammonium in oligotrophic seawater
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In this work, we describe a high-resolution fluorometric shipboard analyser and an improved method to determine NH 4 + in oligotrophic seawater. The limit of detection is <5 nM, calculated with 95% confidence level using the weighted regression line applied to the standard addition method using real samples prepared with low nutrient seawater from the Atlantic. The results are summarised and cross-compared with spiked artificial seawater (ASW) and spiked Milli-Q water samples. The analyser has a precision of ±1–4% with a high performance over a wide range from 5 nM to 25 μM. The methodology of NH 4 + analysis is based on the fluorescent product formed between o-pthaldialdehyde and NH 4 + in the presence of sulfite. Due to the high resolution of the developed system, we were able to study in depth the sensitivity of the method to salinity, amines, amino acids and potential interferences from particles/algae. The method was found to be sensitive to salinity variations, reducing the signal by up to 85% at 5 nM; this effect decreased at higher concentrations of ammonium. It was noted that the interference from amines at low concentrations was negligible; however, at either high amino acid or high amine concentrations, the signal was depressed. To test for the effect of particles on the system, the system was tested with samples containing phytoplankton (Dunaliella primolecta) cells at different concentrations prepared with ASW to simulate the effect of a phytoplankton bloom. This experiment assessed the potential impact of both particles and other potential fluorescence interferences from cells and/or ammonium leaching from cells. This experiment showed that a phytoplankton bloom could potentially have an impact of up to 12% on the signal of interest. Thus, we propose that this method is suitable for oligotrophic environments rather than coastal and eutrophic environments. The reagent was found to be stable for 17 days and standards of 1 μM were stable for 6 days under laboratory conditions. The developed analyser was successfully demonstrated in the North Atlantic Ocean, in an area of oligotrophic, low NH 4 + oceanic waters.
KeywordsAmmonium Shipboard Analyser Fluorometric Resolution
This research is funded by the UK Natural Environment Research Council Oceans 2025 theme 5 & 8.1 research programme. This work is also supported by SENSEnet, a Marie Curie Initial Training Network (ITN) funded by the European Commission Seventh Framework Programme, Contract Number PITN-GA-2009-237868. The authors wish to thank Prof. Ralf Prien, Dr. Cedric Flouquet, Dr. Maria-Nefeli Tsaloglou and Dr. Sarah Bennett for their useful guidance during the experimental phases of this work and comments on this manuscript. Thanks also to Lee Fowler, Jennifer Riley, Catherine Burd, Bahi Mahadji, Dr. David Barat and Ed Smith for their help during the laboratory and field studies.
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