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The speciation of iron(III) in oxic seawater is dominated by its hydrolysis and sedimentation of insoluble iron(III)-oxyhydroxide. As a consequence, many oceanic areas have very low iron levels in surface seawater which leads to iron deficiency since phytoplankton require iron as a micronutrient in order to grow. Fortunately, iron solubility is not truly as low as Fe(III) solubility measurements in inorganic seawater would suggest, since oceanic waters contain organic molecules which tend to bind the iron and keep it in solution. Various iron-binding organic ligands which combine to stabilize dissolved iron have been detected and thoroughly investigated in recent years. However, the role of iron-binding ligands from terrestrial sources remains poorly constrained. Blackwater rivers supply large amounts of natural organic material (NOM) to the ocean. This NOM (which consists mainly of vascular plant-derived humic substances) is able to greatly enhance iron bioavailability in estuaries and coastal regions, however, breakdown processes lead to a rapid decrease of river-derived NOM concentrations with increasing distance from land. It has therefore been argued that the influence of river-derived NOM on iron biogeochemistry in offshore seawater does not seem to be significant. Here we used a standard method based on 59Fe as a radiotracer to study the solubility of Fe(III)-oxyhydroxide in seawater in the presence of riverine NOM. We aimed to address the question how effective is freshwater NOM as an iron chelator under open ocean conditions where the concentration of land-derived organic material is about 3 orders of magnitude smaller than in coastal regions, and does this iron chelating ability vary between NOM from different sources and between different size fractions of the river-borne NOM. Our results show that the investigated NOM fractions were able to substantially enhance Fe(III)-oxyhydroxide solubility in seawater at concentrations of the NOM ≥ 5 μg L− 1. Terrigenous NOM concentrations ≥ 5 μg L− 1 are in no way unusual in open ocean surface waters especially of the Arctic and the North Atlantic Oceans. River-derived humic substances could therefore play a greater role as iron carriers in the ocean than previously thought.

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[1] Primary production in large areas of the open ocean is limited by low iron concentrations. Rivers are potential sources of iron to the ocean, however, riverine iron is prone to intense flocculation and sedimentation in the estuarine mixing zone. Here we report the detection of iron-rich nanoparticles in a typical peatland-draining creek which are resistant against salt-induced flocculation i.e., their behavior is in sharp contrast to the well-known behavior of Fe colloids in river waters. Sample fractionation by AsFlFFF (Asymmetric Flow Field Flow Fractionation) revealed that these powerful iron carriers are in the size range of only 0.5-3.0 nm hydrodynamic diameter. They were isolated from the water phase using solid phase extraction/gel permeation chromatography, and analyzed by a CuO oxidation/GC-MS method. Our results suggest that the particles consist mainly of lignin catabolites and that gymnosperm as well as angiosperm tissues are contributors to the seawater-resistant iron-bearing DOM. Lignin phenols, which have no autochthonous source in the ocean, have been nevertheless found in low concentrations throughout the entire Arctic, Atlantic, and Pacific oceans. It is therefore tempting to speculate that peatland-derived iron-bearing lignin particles may have a sufficiently long half-life in ocean waters to sustain iron concentration in extended regions of the ocean.

Abstract. The influence of natural metal chelators on the bio-available iron input to the ocean by river water was studied. Ferrous and ferric ions present as suspended colloidal particles maintaining the semblance of a dissolved load are coagulated and settled as their freshwater carrier is mixed with seawater at the continental boundary. However, we might argue that different iron-binding colloids become sequentially destabilized in meeting progressively increasing salinities. By use of a 59 Fe tracer method, the partitioning of the iron load from the suspended and dissolved mobile fraction to storage in the sediments was measured with high accuracy in mixtures of natural river water with artificial sea water. The results show a characteristic sequence of sedimentation. Various colloids of different stability are removed from a water of increasing salinity, such as it is the case in the transition from a river water to the open sea. However, the iron transport capacities of the investigated river waters differed greatly. A mountainous river in the Austrian Alps would add only about 5% of its dissolved Fe load, that is about 2.0 µg L −1 Fe, to coastal waters. A small tributary draining a sphagnum peat-bog, which acts as a source of refractory low-molecular-weight fulvic acids to the river water, would add approximately 20% of its original Fe load, that is up to 480 µg L −1 Fe to the ocean's bio-available iron pool. This points to a natural mechanism of ocean iron fertilization by terrigenous fulvic-iron complexes originating from weathering processes occurring in the soils upstream.

This study presents the distribution of 15 major and trace elements in sediments and fish and their pericardial parasites from Lake Naivasha, Kenya. The lake is one of the few freshwater lakes in the Great Rift Valley and is under strong anthropogenic pressure mainly due to agricultural activities. Its fish provide a valuable protein source for approximately 100,000 people in the area. Fish and their parasites have been acknowledged as indicators of environmental quality due to their accumulation potential for both essential and nonessential trace elements. A total of 34 specimens of the blue spotted tilapia Oreochromis leucostictus and pooled samples of their pericardial parasite, the anisakid nematode Contracaecum multipapillatum (larvae 3), were examined. Element concentrations were determined by inductively coupled plasma-optical emission spectroscopy (ICP-OES) and graphite furnace atomic absorption spectrometry (GF-AAS). The concentrations of elements in the sediments reflected the geology of the area and did not point to pollution: none of the investigated trace elements, including Pb, Cd, Cu, and Zn, showed elevated values. In contrast, concentrations in the fish muscle were elevated for Li, Sr, Cd, and Zn, with high target hazard quotients (THQ > 0.1) indicating a potential health risk to the consumers of this fish. Fish liver showed significantly higher concentrations of the trace elements Fe, Mn, Cd, and Cu compared to the muscle and C. multipapillatum. In the parasite, Zn had the highest concentration, but the worms only minimally accumulated trace elements in relation to their fish host.

Oil fortification with retinyl palmitate is intended to lower the prevalence of vitamin A deficiency in populations at risk. Although the stability of vitamin A in vegetable oil has been shown to depend on environmental factors, very little information is known about the stability of vitamin A in preoxidized vegetable oils. The present study investigated the stability of retinyl palmitate in mildly oxidized (peroxide value < 2 mequiv O2/kg) and highly oxidized (peroxide value > 10 mequiv O2/kg) soybean oil stored under domestic and retail conditions. Soybean oil was filled in transparent bottles, which were exposed to cold fluorescent light at 22 or 32 °C for 56 days. Periodic oil sampling increased the headspace, thereby mimicking consumer handling. Loss of retinyl palmitate in soybean oil by a maximum of 84.8 ± 5.76% was accompanied by a decrease of vitamin E by 53.3 ± 0.87% and by an increase of the peroxide value from 1.20 ± 0.004 to 24.3 ± 0.02 mequiv O2/kg. Fortification of highly oxidized oil with 31.6 IU/g retinyl palmitate led to a doubling of the average decrease of retinol per day compared to fortification of mildly oxidized oil. In conclusion, oil fortification programs need to consider the oxidative status of the oil used for retinyl palmitate fortification.

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