On the relevance of iron adsorption to container materials in small-volume experiments on iron marine chemistry:: 55Fe-aided assessment of capacity, affinity and kinetics

Iron chemistry in seawater has been extensively studied in the laboratory, mostly in small-volume sample bottles. However, little has been reported about iron wall sorption in these bottles. In this paper, radio-iron Fe-55 was used to assess iron wall adsorption, both in terms of capacity, affinity and kinetics. Various bottle materials were tested. Iron sorption increased from polyethylene/polycarbonate to polymethylmetacrylate (PMMA)/high-density polyethylene/polytetrafluoroethylene to glass/quartz, reaching equilibrium in a 25-70 h period. PMMA was studied in more detail: ferric iron (Fe(III)) adsorbed on the walls of the bottles, whereas ferrous iron (Fe(II)) did not. Considering that in seawater the inorganic iron pool mostly consists of ferric iron, the wall will be a factor that needs to be considered in bottle experiments. The present data indicate that for PMMA with specific surface (S)-to-volume (P)ratioS/V, both iron capacity (42 +/- 16 x 10(-9) mol/m(2) or 1.7 x 10(-9) mol/L recalculated for the S/V-specific PMMA bottles used) and affmity (log K-Fe'w=11.0 +/- 0.3 m(2)/mol or 12.4 +/- 0.3 L/mol, recalculated for the S/V-specific PMMA, bottles used) are of similar magnitude as the iron capacity and -affinity of the natural ligands in the presently used seawater and thus cannot be ignored. Calculation of rate constants for association and dissociation of both Fe'L (iron bound to natural occurring organic ligands) and Fe'W (iron adsorbed on the wall of vessels) suggests that the two iron complexes are also of rather similar kinetics, with rate constants for dissociation in the order of 10(-4)-10(-5) L/s and rate constants for association in the order of 10(8) L/(mol s). This makes that iron wall sorption should be seriously considered in small-volume experiments, both in assessments of shorter-tenn dynamics and in end-point observations in equilibrium conditions. Therefore, the present data strongly advocate making use of iron mass balances throughout in experiments in smaller volume set-ups on marine iron (bio) chemistry. (c) 2007 Elsevier B.V. All rights reserved.