The complex provenance of Cu-binding ligands in the South-East Atlantic

R Zitoun,E.P Achterberg,T.J Browning,L.J Hoffmann,S Krisch,S.G Sander,A Koschinsky

doi:10.1016/j.marchem.2021.104047

Abstract

Organic ligands play a key role in the marine biogeochemical cycle of copper (Cu), a bio-essential element, regulating its solubility and bioavailability. However, the sources, abundance, and distribution of these ligands are still poorly understood. In this study, we examined vertical Cu speciation profiles from the South-East Atlantic (GEOTRACES section GA08). Profiles were collected from a range of ocean conditions, including the Benguela upwelling region, the oligotrophic South Atlantic Gyre, and the Congo River outflow. In general, the lack of a significant correlation between most of the parameters assessed here with Cu speciation data obscures the provenance of Cu-binding ligands, suggesting that Cu speciation in the South-East Atlantic is influenced by a complex interplay between biotic and abiotic processes. Nevertheless, the total dissolved Cu (CuT) illustrated an allochthonous origin in the working area, while Cu-binding ligands showed both an allochthonous and a biogenic, autochthonous origin. Pigment concentrations showed that the phylogeography of different microorganisms influenced the spatial features of the Cu-binding ligand pool in the South-East Atlantic. Allochthonous Cu-binding ligand sources in the upper water column are likely associated with dissolved organic matter which originated from the Congo River and the Benguela upwelling system. Deep water ligand sources could include refractory dissolved organic carbon (DOC), resuspended benthic inputs, and lateral advected inputs from the shelf margin. The degradation of L1-type ligands and/or siderophores in low oxygen conditions may also be a source of L2-type ligands in the deep. Free Cu ion levels (1.7 to 156 fM), the biologically available form of CuT, were below the putative biolimiting threshold of many marine organisms. Two classes of ligands were found in this study with total ligand concentrations ([LT]) ranging from 2.5 to 283.0 nM and conditional stability constants (logKCuL, Cu2+cond) ranging from 10.7 to 14.6. The Cu speciation values were spatially variable across the three subregions, suggesting that biogeochemical processes and sources strongly influence Cu speciation.

Highlights

Greater understanding of the distribution and speciation of trace elements in the ocean is critical for understanding their geochemical cycling and impact on biological processes (Flemming and Trevors, 1989; Heller and Croot, 2015; Sunda, 2012; Sunda, 1994)
Elevated [CuT] in the nearshore Cape Basin were likely associated with Benguela upwelling of trace metal rich deep-water rather than atmospheric inputs, which are expected to be low in this region (BC station: median of 0.93 nM and up to 2.12 nM CuT; Maho wald et al, 2005; Barraqueta et al, 2019; Noble et al, 2012)
This study investigated Cu speciation in the South-East Atlantic to identify the provenance of Cu-binding ligands in the Angola Basin and the northernmost Cape Basin (GEOTRACES section GA08)

Summary

Introduction

Greater understanding of the distribution and speciation of trace elements in the ocean is critical for understanding their geochemical cycling and impact on biological processes (Flemming and Trevors, 1989; Heller and Croot, 2015; Sunda, 2012; Sunda, 1994). 1.0 pM have been shown to adversely affect some microorganisms (Amin et al, 2013; Annett et al, 2008; Brand et al, 1986; Glass and Orphan, 2012; Guo et al, 2010; Jacquot et al, 2014; Mann et al, 2002), while [Cu2+] ≤ 0.01 pM (≤ 0.2 pM for ammonia-oxidizing Archaea; Amin et al, 2013; Jacquot et al, 2014) have been found to be biolimiting (Maldonado et al, 2006; Peers et al, 2005; Sunda and Hunts man, 1995) Whilst these values are commonly cited as ‘critical Cu2+

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