The passivation of calcite by acid mine water. Column experiments with ferric sulfate and ferric chloride solutions at pH 2

Column experiments, simulating the behavior of passive treatment systems for acid mine drainage, have been performed. Acid solutions (HCl or H₂SO₄, pH 2), with initial concentrations of Fe(III) ranging from 250 to 1500 mg L⁻¹, were injected into column reactors packed with calcite grains at a constant flow rate. The composition of the solutions was monitored during the experiments. At the end of the experiments (passivation of the columns), the composition and structure of the solids were measured. The dissolution of calcite in the columns caused an increase in pH and the release of Ca into the solution, leading to the precipitation of gypsum and Fe–oxyhydroxysulfates (Fe(III)–SO₄–H⁺ solutions) or Fe–oxyhydroxychlorides (Fe(III)–Cl–H⁺ solutions). The columns worked as an efficient barrier for some time, increasing the pH of the circulating solutions from 2 to 6–7 and removing its metal content. However, after some time (several weeks, depending on the conditions), the columns became chemically inert. The results showed that passivation time increased with decreasing anion and metal content of the solutions. Gypsum was the phase responsible for the passivation of calcite in the experiments with Fe(III)–SO₄–H⁺ solutions. Schwertmannite and goethite appeared as the Fe(III) secondary phases in those experiments. Akaganeite was the phase responsible for the passivation of the system in the experiments with Fe(III)–Cl–H⁺ solutions.     

Fluxes and sources of suspended organic matter in an estuarine turbidity maximum region during low discharge conditions

Water column concentrations of total suspended solids (TSS), particulate organic carbon (POC) and particulate nitrogen (PN) were measured at three different depths in four different locations bracketing the estuarine turbidity maximum (ETM) along the main channel of a temperate riverine estuary (Winyah Bay, South Carolina, USA). Measurements were carried out over full tidal cycle (over 24 h). Salinity, temperature, current magnitude and direction were also monitored at the same time throughout the water column. Tidally averaged net fluxes of salt, TSS, POC and PN were calculated by combining the current measurements with the concentration data. Under the extreme low river discharge conditions that characterized the study period, net landward fluxes of salt were measured in the lower part of the study area, suggesting that the landward transport through the main channel of the estuary was probably balanced by export out through the sides. In contrast, the net fluxes of salt in the upper reaches of the study area were near zero, indicating a closed salt balance in this part of the estuary. In contrast to salt, the net fluxes of TSS, POC and PN in the deeper parts of the water column were consistently landward at all four sites in Winyah Bay indicating the non-conservative behavior of particulate components and their active transport up the estuary in the region around the ETM.The carbon contents (%POC), carbon:nitrogen ratios (org[C:N]a) and stable carbon isotopic compositions (δ¹³C_POC) of the suspended particles varied significantly with depth, location and tidal stage. Tidally averaged compositions showed a significant increase up the estuary in the %POC and org[C:N]a values of suspended particles consistent with the preferential landward transport of carbon-rich particles with higher vascular plant debris content. The combination of tidal resuspension and flood-dominated flow appeared to be responsible for the hydrodynamic sorting of particles along the estuary that resulted in denser, organic-poor particles being transported landward less efficiently. The elemental and isotopic compositions indicated that vascular C₃ plants and estuarine algae were the major sources of the particulate organic matter of all the samples, without any significant contributions from salt marsh C₄ vegetation (Spartina alterniflora) and/or marine phytoplankton.     

The European vision for oceans and seas—Social and political dimensions of the Green Paper on Maritime Policy for the EU

The EU Green Paper on Maritime Policy is the European response to the new generation of ocean strategies based on science, technology and innovation aimed at new objectives, such as the strengthening of security and access to new resources. The European character of the proposal is found in the presence of social, cultural and historical elements, what is called the “European vision”. The viability of a European vision of the oceans and the idea of maritime empire as an extension of the current concept of empire within the general context of emerging ocean strategies are the elements offered up for debate on this European Union initiative.     

Sources and distribution of organic matter in a river-dominated estuary (Winyah Bay, SC, USA)

The sources and distribution of organic matter (OM) in surface waters and sediments from Winyah Bay (South Carolina, USA) were investigated using a variety of analytical techniques, including elemental, stable isotope and organic biomarker analyses. Several locations along the estuary salinity gradient were sampled during four different periods of contrasting river discharge and tidal range. The dissolved organic carbon (DOC) concentrations of surface waters ranged from 7 mg l⁻¹ in the lower bay stations closest to the ocean to 20 mg l⁻¹ in the river and upper bay samples. There was a general linear relationship between DOC concentrations and salinity in three of the four sampling periods. In contrast, particulate organic carbon (POC) concentrations were significantly lower (0.1–3 mg l⁻¹) and showed no relationship with salinity. The high molecular weight dissolved OM (HMW DOM) isolated from selected water samples collected along the bay displayed atomic carbon:nitrogen ratios ([C/N]a) and stable carbon isotopic compositions of organic carbon (δ¹³C_OC) that ranged from 10 to 30 and from −28 to −25‰, respectively. Combined, such compositions indicate that in most HMW DOM samples, the majority of the OM originates from terrigenous sources, with smaller contributions from riverine and estuarine phytoplankton. In contrast, the [C/N]a ratios of particulate OM (POM) samples varied significantly among the collection periods, ranging from low values of 5 to high values of >20. Overall, the trends in [C/N]a ratios indicated that algal sources of POM were most important during the early and late summer, whereas terrigenous sources dominated in the winter and early spring.In Winyah Bay bottom sediments, the concentrations of the mineral-associated OM were positively correlated with sediment surface area. The [C/N]a ratios and δ¹³C_OC compositions of the bulk sedimentary OM ranged from 5 to 45 and from −28 to −23‰, respectively. These compositions were consistent with predominant contributions of terrigenous sources and lesser (but significant) inputs of freshwater, estuarine and marine phytoplankton. The highest terrigenous contents were found in sediments from the river and upper bay sites, with smaller contributions to the lower parts of the estuary. The yields of lignin-derived CuO oxidation products from Winyah Bay sediments indicated that the terrigenous OM in these samples was composed of variable mixtures of relatively fresh vascular plant detritus and moderately altered soil OM. Based on the lignin phenol compositions, most of this material appeared to be derived from angiosperm and gymnosperm vascular plant sources similar to those found in the upland coastal forests in this region. A few samples displayed lignin compositions that suggested a more significant contribution from marsh C₃ grasses. However, there was no evidence of inputs of Spartina alterniflora (a C₄ grass) remains from the salt marshes that surround the lower sections of Winyah Bay.     

Freezing as a method of sample preservation for the analysis of dissolved inorganic nutrients in seawater

It is often desirable or necessary to store collected seawater samples prior to analysis for dissolved inorganic nutrients. It is therefore important to establish preservation and storage techniques that will ensure sample integrity and will not alter the precision or accuracy of analysis. We have performed a series of experiments on the storage of nutrient samples collected at the oligotrophic North Pacific benchmark Station ALOHA, using both standard autoanalyses and low-level techniques. Our results reveal that for oligotrophic oceanic waters, the immediate freezing of an unfiltered water sample in a clean polyethylene bottle is a suitable preservation method. This procedure is simple, it avoids potentially contaminating sample manipulations and chemical additions, and it adequately preserves the concentrations of nitrate + nitrite, soluble reactive phosphate, and soluble reactive silicate within a single water sample.     

Seasonal use of coastal resources by otters: Comparing sandy and rocky stretches

Seasonal patterns of use of coastal resources by otters have been studied, simultaneously performing diet analyses and spraint counts (expressed as marking intensity, MI). In spite of the small size of the study area, two different sectors could be clearly identified, a sandy and a rocky one. The origin (freshwater or coastal) of most prey types could also be determined. Surveys were performed bimonthly and classified as autumn–winter (A–W) or spring–summer (S–S).In the sandy sector, eels, flatfish and grey mullets were more frequently consumed in A–W, while crayfish was more frequently consumed in S–S. None of the identified prey types in the rocky sectors showed different frequency of occurrence values between the two periods. In this sector otter fed mainly on coastal prey throughout the year, while in the sandy one there was a clear shift from coastal prey to freshwater ones in S–S. The decrease of coastal prey consumption in S–S in the sandy sector coincided with the lowest MI values, showing that in this period otters use coastal areas less intensely. Though shifts in otter diet and use of space in the sandy sector are probably influenced by the population dynamics of estuarine fish species and crayfish, the increased tourist disturbance during spring and summer in the sandy sector could be an important determinant of the observed patterns. Finally, the results show that MI can be used as a reliable measure of habitat use by otters, at least in small areas.     

Retention of arsenic and phosphorus in iron-rich concretions of Tagus salt marshes

Iron-rich concretions are frequently found around plant roots in Tagus estuary (Portugal) where radial delivery of O₂ takes place. Salt marsh sediments exhibit cracks that are an additional feature to introduce O₂ and other solutes in the upper sediments. Metal concentrations in salt marsh sediments are clearly above the background levels reflecting the anthropogenic sources from a large city with 2.5 million inhabitants, and several industrial centres. In order to evaluate how both oxidised structures influences the redistribution of redox sensitive elements in salt marsh sediments, concretions were collected from roots of Halimione portucaloides below the oxygenated zone. These tubular cylindrical structures were analysed for Fe, Al, Mn, As, and P along 1-cm radial transect in a millimetre scale from the inner part to the adjacent anoxic sediment. In addition, oxidised cracks were analysed for the same spatial resolution, from the sediment–water interface to anoxic layers (2-cm transept). The parallelism between Fe, As, and P concentrations at this microscale is the most noticeable aspect. Iron and As presented very high concentrations in the 4-mm concretions (3.4 mmol g⁻¹ and 3.1 μmol g⁻¹, respectively) and decreased sharply to the host sediment. Oxygen released from roots oxidise the solid sulphides, and the reduced Fe and As are transported towards the root by both diffusion and pore water flow associated with the root water uptake. Subsequently, Fe(III) precipitates and As is retained by sorption and/or coprecipitation. These elements are also enriched in the first 2-mm of oxidised cracks, but in lower concentrations (50% and 30%, respectively). Manganese concentrations in concretions were low (11.8 μmol g⁻¹), indicating that Fe dominates the sediment chemistry. Phosphorus and iron concentrations in the ascorbate fraction were higher in the oxidising surfaces of concretions (10.7 μmol g⁻¹ and 1.6 mmol g⁻¹, respectively) and of cracks (5.1 μmol g⁻¹ and 0.47 mmol g⁻¹). The parallelism of Fe and As distributions includes not only their similar redox chemistries, but also that to phosphate, including control by coprecipitation of the host iron phases. The mechanisms involved in the mobilisation of As and P are however different, whereas As comes from the oxidation of iron sulphides; dissolved P derives from reduction of ferri-hydroxide phases.