Molecular weight and chemical reactivity of dissolved trace metals (Cd, Cu, Ni) in surface waters from the Mississippi River to Gulf of Mexico

It is generally assumed that estuarine mixing is continuous for metals from terrestrial sources, gradually decreasing towards the open ocean endmember. Here we show that, chemical reactivity, determined by ion exchange method, and molecular weight distributions, obtained using cross-flow ultrafiltration, of dissolved Cd, Cu, and Ni in the surface waters of the Gulf of Mexico varied systematically across the estuarine mixing zone of the Mississippi River. Most size or chemical affinity fractions of dissolved metals (<0.4 mu m) were linearly related to salinity (10.8-36.6), suggesting that the distribution of these elements was mainly controlled by continuous mixing processes. Dissolved concentrations across the salinity gradient ranged for Cd: 87-187 pM; Cu: 1.4-18.3 nM; and Ni: 2.6-18.8 nM, with highest values near the Mississippi river mouth, and lowest concentrations in a warm core ring in the Gulf of Mexico. Dissolved Cd was mostly present as a truly dissolved (<10 kDa, 97 +/- 1%) and cationic fraction (Chelex-100 extractable, 94 +/- 4%). A novel observation across the estuarine mixing zone was that colloidal metal concentrations were identical to either inert (for Cu. Ni) or AMPG-labile anionic (Cu, Cd) fractions. The difference in behavior between Cu and the other two metals might indicate differences in the bio-polymeric nature of the metal organic chelates. In particular, the anionic-organic Cd fractions accounted for just 3 +/- 1%, on average. However, for Cu, it was 24 +/- 4%, and for Ni, it was 9 +/- 6%. The fractions of the total dissolved metal fractions that were "inert" averaged 31 +/- 10% for Cu and 29 +/- 12% for Ni. Small but noticeable amounts (6 +/- 3%) of dissolved inert Cd fractions were also present. Apparent non-local transport processes, likely associated with cross-shelf sediment resuspension processes, could have been responsible for the relatively high concentrations of 'inert' and 'anionic' metal fractions in high salinity coastal waters, and accounting for the persistence of metals bound to humic substances in the Gulf of Mexico. (C) 2011 Elsevier Ltd. All rights reserved.