The seasonal cycling and physico-chemical speciation of iron on the Celtic and Hebridean shelf seas

Birchill, A. J., A. Milne, E. M. S. Woodward, A. L. Annett, W. Giebert, S. Ussher, P. J. Worsfold, D. Rusiecka, E. P. Achterberg, C. Harris, M. Gledhill, M. C. Lohan (2017). Seasonal iron depletion in temperate shelf seas. Geophysical Research Letters. doi: 10.1002/2017GL073881 Klar, J., W. B. Homoky, P. J. Statham, A. J. Birchill, E. Harris, E. M. S. Woodward, B. Silburn, M. Cooper, R. H. James, D. P. Connelly (2017). Stability of dissolved and soluble Fe (II) in shelf sediment pore waters and release to an oxic water column. Biogeochemistry. doi:10.1007/s10533-017-0309-x Hopwood, M. J., A. J. Birchill, M. Gledhill, A. Milne, E. P. Achterberg (2017). A 4 method comparison for the measurement of Fe(II) at nanomolar concentrations in coastal seawater. Frontiers in Chemistry. doi.org/10.3389/fmars.2017.00192Shelf seas represent an important source of iron (Fe) to the open ocean. Additionally, shelf seas are highly productive environments which contribute to atmospheric carbon dioxide drawdown and support large fisheries. The work presented in this thesis describes the seasonal cycle of Fe in the Celtic and Hebridean Shelf Seas, and determines the physico-chemical speciation of Fe supplied from oxic margins. The results from repeated field surveys of the central Celtic Sea showed a nutrient type seasonal cycling of dissolved Fe (< 0.2 µm; dFe), which is surprising in a particle rich shelf system, suggesting a balance of scavenging and remineralisation processes. Coincident drawdown of dFe and nitrate (NO3-) was observed during the phytoplankton spring bloom. During the bloom, preferential drawdown of soluble Fe (< 0.02 µm; sFe) over colloidal Fe (0.02-0.2 µm; cFe) indicated greater bioavailability of the soluble fraction. Throughout summer stratification, it is known that NO3- is drawn down to < 0.02 µM in surface waters. This study revealed that both dFe and labile particulate Fe (LpFe) were also seasonally drawn down to < 0.2 nM. Consequently, it is hypothesised that the availability of Fe seasonally co-limits primary production in this region. At depth both dFe and NO3- concentrations increased from spring to autumn, indicating that remineralisation is an important process governing the seasonal cycling of dFe in the central Celtic Sea. In spring, summer and autumn, distinctive intermediate nepheloid layers (INL) were observed emanating from the Celtic Sea shelf slope. The INLs were associated with elevated concentrations of dFe (up to 3.25 ± 0.16 nM) and particulate Fe (up to 315 ± 1.8 nM) indicating that they are a persistent conduit for the supply of Fe to the open ocean. Typically > 15% of particulate Fe was labile and 60-90% of dFe was in the colloidal fraction. Despite being < 50 km from the 200 m isobath, the concentration of dFe was < 0.1 nM in surface waters at several stations. Broadly, the concentration of nutrients in surface waters described an oligotrophic environment where co-limitation between multiple nutrients, including Fe, appears likely. Over the Hebridean shelf break, residual surface NO3- concentrations (5.27 ± 0.79 µM) and very low concentrations of dFe (0.09 ± 0.04 nM) were observed during autumn, implying seasonal Fe limitation. The dFe:NO3- ratio observed is attributed to sub-optimal vertical supply of Fe relative to NO3- from sub-surface waters. In contrast to the shelf break, surface water in coastal regions contained elevated dFe concentrations (1.73 ± 1.16 nM) alongside low NO3-. Seasonal Fe limitation is known to occur in the Irminger and Iceland Basins; therefore, the Hebridean shelf break likely represents the eastern extent of sub-Arctic Atlantic seasonal Fe limitation, thus indicating that the associated weakening of the biological carbon pump exists over a wider region of the sub-Arctic Atlantic than previously recognised. These key findings demonstrate that the availability of Fe to phytoplankton may seasonally reach limiting levels in temperate shelf waters and that oxic margins persistently supply Fe dominated by colloidal and particulate fractions to the ocean