CSIRO PUBLISHING
Rapid Communication
www.publish.csiro.au/journals/env A. R. Bowie et al., Environ. Chem. 2007, 4, 1–4. doi:10.1071/EN06073
Intercomparison between FI-CL and ICP-MS for the
determination of dissolved iron in Atlantic seawater
Andrew R. Bowie,
A,B
Simon J. Ussher,
C
William M. Landing
D
and Paul J. Worsfold
C,E
A
Antarctic Climate and Ecosystems Cooperative Research Centre (ACE CRC), Hobart,
Tas. 7001, Australia.
B
Australian Centre for Research on Separation Science (ACROSS), School of Chemistry,
University of Tasmania, Hobart, Tas. 7001, Australia.
C
School of Earth, Ocean and Environmental Sciences (SEOES), University of Plymouth,
Drake Circus, Plymouth, PL4 8AA, UK.
D
Department of Oceanography, Florida State University,Tallahassee, FL 32306-4320, USA.
E
Corresponding author. Email: pworsfold@plymouth.ac.uk
Environmental context. Iron is arguably the most important trace element for the growth of marine organisms and
is the limiting micronutrient for primary production in many parts of the world’s oceans.The concentration of dissolved
iron in seawater therefore influences the global carbon cycle and consequently Earth’s climate. Hence, it is important to
understand the marine biogeochemistry of iron and quantify its spatial and temporal distribution. In order to achieve this
objective, it is essential that reported open-ocean concentrations of dissolved iron are accurate.
Abstract. Results from a 3-laboratory blind intercomparison exercise with two widely used analytical methods for the
determination of iron in seawater are presented. The two methods used are coprecipitation followed by isotope dilution
inductively coupled plasma mass spectrometry (ICP-MS) and chemical reduction to iron(ii) followed by flow injection
with chemiluminescence detection (FI-CL). The five samples used were collected from the South Atlantic Ocean as part
of the IRONAGES intercomparison exercise. To avoid any inter-bottle variability, the same sample bottles were sent
sequentially to three laboratories in England, Australia and the United States over a 12-month period. The results show
that there is no statistical difference (P = 0.05) between the shipboard FI-CL method and the directly traceable, low blank,
isotope dilution ICP-MS method for the determination of iron in surface South Atlantic seawater. There was also excellent
agreement between the overall mean of the three laboratories (0.54 ± 0.03 nM) and the consensus value from an earlier
community-wide separate bottle intercomparison using the same IRONAGES sample water (0.59 ± 0.21 nM).
Additional keywords: biogeochemistry, environmental cycles, iron, seawater analysis.
The discovery of basin-scale iron limitation in high-nutrient,
low-chlorophyll (HNLC) regions,
[1–3]
and limitation of nitro-
gen fixation in subtropical regions,
[4]
have demonstrated the
importance of iron in the biogeochemical control and feedback
mechanisms that affect ocean primary productivity.
[5]
In order
to determine the distributions of iron in the ocean and under-
stand iron biogeochemistry
[6]
and its impact on the functioning
of marine ecosystems and carbon cycling, it is imperative that
iron is measured routinely and accurately during oceanographic
research cruises. Moreover, unless the oceanographic commu-
nity can constrain uncertainties in the global distribution of iron,
the development of accurate biogeochemical models will be
restricted.
Following the development of improved trace metal sam-
pling and processing techniques
[7]
and the introduction of new
highly sensitive and selective shipboard and laboratory ana-
lytical methods,
[8]
reported dissolved iron concentrations in
seawater have decreased by up to two orders of magnitude,
[9]
thus
enabling oceanographers to obtain the first reliable open-ocean
profiles.
[10]
Indeed, it is now possible to observe oceanographic
consistency in vertical dissolved iron distributions over decadal
time scales (see Fig. 1).
0
100
200
300
400
500
600
700
800
900
1000
0.0 0.2 0.4 0.6 0.8
Dissolved Fe [nM]
Depth [m]
A16N-Sta 31
NABE 47N
NABE 59N
Fig. 1. Comparison of the distribution of dissolved iron in the north-east
Atlantic. A16N-Sta 31 (50
◦
N, 20
◦
W) data was collected in 2005 by Florida
State University using
57
Fe isotope dilution ICP-MS. North Atlantic Bloom
Experiment (NABE) data was collected in 1989 by Moss Landing Marine
Laboratories (Martin et al.
[21]
) using chelation solvent extraction–graphite
furnace atomic absorption spectrometry.
© CSIRO 2007 1 1448-2517/07/010001