Changes in nutrient structure of river-dominated coastal waters: stoichiometric nutrient balance and its consequences

We present an analysis of extensive nutrient data sets from two river-dominated coastal ecosystems, the northern Adriatic Sea and the northern Gulf of Mexico, demonstrating significant changes in surface nutrient ratios over a period of 30 years. The silicon:nitrogen ratios have decreased, indicating increased potential for silicon limitation. The nitrogen:phosphorus and the silicon:phosphorus ratios have also changed substantially, and the coastal nutrient structures have become more balanced and potentially less limiting for phytoplankton growth. It is likely that net phytoplankton productivity increased under these conditions and was accompanied by increasing bottom water hypoxia and major changes in community species composition. These findings support the hypothesis that increasing coastal eutrophication to date may be associated with stoichiometric nutrient balance, due to increasing potential for silicon limitation and decreasing potential for nitrogen and phosphorus limitation. On a worldwide basis, coastal ecosystems adjacent to rivers influenced by anthropogenic nutrient loads may experience similar alterations.

Degradation products formed during UV-irradiation of humic waters

Natural humic lake water and aqueous solutions of humic substances were treated with ultraviolet (UV) radiation (λ = 254 nm). The effects on the dissolved organic carbon content (DOC) and the absorbance at 254 nm (Abs254) and 460 nm (Abs460) were monitored and the identity and concentrations of gas chromatographable organic degradation products were determined. The DOC content and the (Abs254) of the humic solutions decreased continuously with increasing UV-dose. Several aromatic and aliphatic degradation products were identified and roughly quantified The concentrations of aromatic hydroxy carboxylic acids and hydroxy aldehydes increased when relatively low UV-doses were used, but declined following further irradiation. The concentrations of aliphatic dibasic acids increased over the full range of UV-doses

Interference effects in the extraction of trace metals from estuarine waters

We have found that a commonly used complexation and solvent extraction technique (using mixed dithiocarbamates/Freon/HNO3) does not always extract Cd, Co, Cu and Ni from estuarine samples with the same efficiency as from Milli-Q water. For samples collected from the Derwent Estuary (Australia), the reduced extraction efficiency only occurred for unfiltered samples, but low extraction efficiencies were also observed for a (filtered) riverine certified reference material (SLRS-3) suggesting that the effect may be widespread. We have not been able to identify the reason for the low extraction efficiency and, although it is strongly correlated with the presence of high concentrations of suspended solids, dissolved organic matter and particulate iron, we have no experimental evidence to directly link any of these parameters to the effect. It is possible that similar effects may occur in other techniques which rely on a preconcentration step prior to analysis and that some literature values of heavy metals in estuarine waters may be low. We propose a modification of the standard complexation/solvent extraction method which overcomes these difficulties without adding significantly to the time taken for analyses.