Stability of the Cadmium Complex with the Bacterial Trihydroxamate Siderophore Desferrioxamine B at Seawater Ionic Strength

The divalent transition metal cadmium occurs in seawater at ultra-trace levels. In the open ocean, dissolved Cd(II) displays a nutrient-like profile characterized by a strong gradient from low picomolar concentrations in surface waters to a mid-depth maximum of around 1 nM. Its vertical distribution is highly correlated with that of dissolved phosphate, seemingly at odds with the general perception that Cd is a very toxic element. On the other hand, in Zn-depleted waters Cd(II) has been found to replace Zn(II) or Co(II) in a functional, albeit less efficient form of carbonic anhydrase, a key enzyme enabling the assimilation of bicarbonate into organic matter. Considering these opposing roles, it is likely that phytoplankton regulates the toxicity and/or bioavailability of Cd(II) through the production of certain strong organic ligands, as it has been shown to do for example in the case of Cu(II). Siderophores are a fascinating class of organic ligands excreted by microorganisms to facilitate the acquisition of micronutrient Fe(III), preciously scarce due to its extremely low solubility in seawater. The linear trihydroxamic acid desferrioxamine B (DFOB) is naturally present in open ocean surface waters at picomolar concentrations and, because of its use as a pharmaceutical agent in the treatment of human iron overload disorders, the only purified siderophore commercially available in practicable quantities. The optimal spacing of three bidentate O-bearing functional groups along a flexible carbon frame allows the molecule to wrap around the Fe3+ ion in a polydentate heterocyclic structure that perfectly matches its ionic radius and preferred coordination. Despite its resultant exceptional affinity and selectivity for Fe3+ (β ~ 1031), DFOB also forms very stable complexes with an array of differently sized and charged cations. The only previous report on the stability constant of the Cd(II)-DFOB complex, dating from 1963, proposes a values of 108 at 0.1 M ionic strength. Whereas this is orders of magnitude smaller than values for DFOB complexes of other divalent transition metals (e.g., β(Cu2+) ~ 1014), it nevertheless makes DFOB one of the strongest known biogenic Cd ligands, rivaling synthetic ligands such as NTA. We present measurements of the stability constant of the Cd(II)-DFOB complex that were obtained by potentiometric titration of DFOB in the presence of Cd in a non-complexing background electrolyte (NaClO4) at seawater ionic strength (0.7 M). The titrations were corrected for hydrolysis and also performed at different Cd:DFOB ratios to detect any polynuclear species. Stability constants were derived from non-linear regressions of the data using FITEQL4.0. The results may provide new insights into the marine biogeochemistry of cadmium and its potential effects on primary productivity.