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Iron (Fe) is a limiting nutrient for phytoplankton productivity in many different oceanic regions. A critical aspect underlying iron limitation is its low solubility in seawater as this controls the distribution and transport of iron through the ocean. Processes which enhance the solubility of iron in seawater, either through redox reactions or organic complexation, are central to understanding the biogeochemical cycling of iron. In this work we combined iron solubility measurements with parallel factor (PARAFAC) data analysis of Coloured Dissolved Organic Matter (CDOM) fluorescence along a meridional transect through the Atlantic (PS ANT XXVI-4) to examine the hypothesis that marine humic fluorescence is a potential proxy for iron solubility in the surface ocean. PARAFAC analysis revealed 4 components (C1-4), two humic like substances (C2&4) and two protein-like (Cl&3). Overall none of the 4 components were significantly correlated with iron solubility, though humic-like components were weakly correlated with iron solubility in iron replete waters. Our analysis suggests that the ligands responsible for maintaining iron in solution in the euphotic zone are sourced from both remineralisation processes and specific ligands produced in response to iron stress and are not easily related to bulk CDOM properties. The humic fluorescence signal was sharply attenuated in surface waters presumably most likely due to photo bleaching, though there was only a weak correlation with the transient photo product H2O2, suggesting longer lifetimes in the photic zone for the fluorescent components identified here. [ABSTRACT FROM AUTHOR]

The bulk of particulate transition metals transported by Patagonian rivers shows an upper crustal composition. Riverine particulate 0.5 N HCl leachable trace metal concentrations are mainly controlled by Fe-oxides. Complexation of Fe by dissolved organic carbon (DOC) appears to be an important determinant of the phases transporting trace metals in Patagonian rivers. In contrast, aeolian trace elements have a combined crustal and anthropogenic origin. Aeolian materials have Fe, Mn, and Al contents similar to that found in regional topsoils. However, seasonal concentrations of some metals (e.g., Co, Pb, Cu, and Zn) are much higher than expected from normal crustal weathering and are likely pollutant derived.We estimate that Patagonian sediments are supplied to the South Atlantic shelf in approximately equivalent amounts from the atmosphere (∼30 × 106 T yr−1) and coastal erosion (∼40 × 106 T yr−1) with much less coming from the rivers (∼2.0 × 106 T yr−1). Low trace metal riverine fluxes are linked to the low suspended particulate load of Patagonian rivers, inasmuch most of it is retained in pro-glacial lakes as well as in downstream reservoirs. Based on our estimation of aeolian dust fluxes at the Patagonian coastline, the high nutrient-low chlorophyll sub Antarctic South Atlantic could receive 1.0 to 4.0 mg m−2 yr−1 of leachable (0.5 N HCl) Fe. Past and present volcanic activity in the southern Andes—through the ejection of tephra—must be highlighted as another important source of Fe to the South Atlantic Ocean. Based on the 1991 Hudson volcano eruption, it appears that volcanic events can contribute several thousand-fold the mass of “leachable” Fe to the ocean as is introduced by annual Patagonian dust fallout. [Copyright &y& Elsevier]

The occurrence and geochemical behaviour of Fe, Mn, Pb, Cu, Ni, Cr, Zn and Co are studied in riverine detrital materials transported by Patagonian rivers. Their riverine inputs have been estimated and the nature of these inputs to the Atlantic Ocean is discussed. Most of the metals are transported to the ocean via the suspended load; there is evidence that Fe oxides and organic matter are important phases controlling their distribution in the detrital non-residual fraction. Most heavy metal concentrations found in bed sediments, in suspended matter, and in the dissolved load of Patagonian rivers were comparable to those reported for non-polluted rivers. There is indication that human activity is altering riverine metal inputs to the ocean. In the northern basins – and indicating anthropogenic effects – heavy metals distribution in the suspended load is very different from that found in bed sediments. The use of pesticides in the Negro River valley seems correlated with increased riverine input of Cu, mostly bound to the suspended load. The Deseado and Chico Rivers exhibit increased specific yield of metals as a consequence of extended erosion within their respective basins. The Santa Cruz is the drainage basin least affected by human activity and its metal-exporting capacity should be taken as an example of a relatively unaffected large hydrological system. In contrast, coal mining modifies the transport pattern of heavy metals in the Gallegos River, inasmuch as they are exported to the coastal zone mainly as dissolved load. [ABSTRACT FROM AUTHOR]

The Suquia is a semiarid (rainfall, 700--900 mm y{sup}-1{end}), medium-size (7700 km{sup}2{end}) river system located in central Argentina. Its mountainous upper catchment includes pristine areas as well asa variety of human settlements and a reservoir lake. A large city (Cordoba, ca. 1.3 million inhabitants) and a terminal hypersaline lake are included in the middle and lower basin. Total non-residual (TNR) heavy metals (Pb, Cu, Ni, Zn, Mn, and Fe) have been determined in river bed sediments in two seasons (spring and autumn), seeking to establish the factors which control the temporal and spatial variability. The major findings were: a) concentrations of TNR metals were, in general, higher during springtime than during autumn, particularly downstream from the city of Cordoba; b) organic matter played a significant role as a controlling factor wherever it defined reducing conditions, lowering the concentrations of Mn and Fe hydrous oxides; c) a higher organic load (e.g., downstream the city) and more pronounced reducing conditions could be the causes for the increased Fe concentration, probably precipitated as sulfides; d) organic matter exhibited a closer correlation with some TNR metals in autumn, probably caused by alarger capacity for complexation in the biologically-processed organic debris; and, e) the existence of pristine areas in the drainage basin allowed for the calculation of enrichment factors (EF) which showthe significance of several environmental impacts in the Suquia system. [ABSTRACT FROM AUTHOR]