ALBERT

Description: Ferromanganese concretions from ten stations in the Barents Sea have been analysed for 24 elements. The deposits occur as discoidal and flat concretions and as coatings, in the latter case on lithified or detrital material or as extensive pavements on the Svalbard shelf. The concretions are compositionally similar to Baltic concretions but differ considerably from deep-ocean nodules, particularly in Cu, Ni and Co contents. Statistical analyses reveal distinct correlations between Mn, Na, Ba, Ni and Cu; the Mn-rich coatings showed enrichment of Mo, Zn and possibly Co in a Mn-phase. The iron phase holds high concretions of P and As. Two iron-rich concretions with high contents of P, Ca, Sr, Y, Yb and La were found east and northeast of Spitsbergen Banken, probably indicating upwelling of nutrient-rich, cold polar water along the Svalbard shelf.

Description: Ferromanganese concretions from the Svalbard shelf in the Barents Sea show slightly convex shale-normalized REE patterns with no Eu anomalies. Concretions from the Gulf of Bothnia, northern part of the Baltic Sea, exhibit an enrichment of light REE and negative Eu anomalies. This difference is interpreted as a consequence of different conveyor mechanisms of the REE to the sediment. It is suggested that dissolving biogenic debris contributes to the convex pattern obtained in the Barents Sea, whereas an inorganic suspended fraction with scavenged REE is the main carrier in the Gulf of Bothnia. During oxic diagenesis in the sediment, the scavenged REE are set free into the porewater and contribute to the distribution pattern in concretions found in the Gulf of Bothnia. Small Mn-rich spheroidal concretions are enriched two to five times in REE compared to average shale, whereas Mn-poor flat concretions are low in REE. Specific surface area of the concretion and the depth of burial in the oxidized surface sediment are two factors that strongly affect the enrichment of the REE. Weak Ce anomalies are present in the analysed concretions and a redox level dependence is seen.

Description: Ferromanganese concretions cover large areas of the Gulf of Bothnia. They are flat to well-rounded, the rounded ones being richer in oxyhydroxides of iron and manganese. Rounded and ellipsoidal nodules, particularly those in the northern Gulf of Bothnia, are richest in Mn, Ni, Ba and Cu, which probably coexist in a Mn oxyhydroxide phase. Flat nodules are enriched in Fe, P, rare earths and As, probably associated with an Fe oxy-hydroxide component. Aluminum, V, Cr and Ti occur in still another phase. The sediments of the gulf generally consist of a 10-50 mm-thick layer of oxidized surface sediment, enriched in Mn, Ba, P and Ni lying on top of reduced sediments which are diagenetically depleted in these elements. The remobilized elements have redeposited in the nodules, but this process cannot explain the origin of all the nodular material. Some released Mn, Ba and Ni furthermore enter into suspended phases, which eventually leave the Baltic Sea. The economic value of the nodules in the Gulf of Bothnia is probably limited at present.

Description: Ferromanganese concretions from ten stations in the Barents Sea have been analysed for 24 elements. The deposits occur as discoidal and flat concretions and as coatings, in the latter case on lithified or detrital material or as extensive pavements on the Svalbard shelf. The concretions are compositionally similar to Baltic concretions but differ considerably from deep-ocean nodules, particularly in Cu, Ni and Co contents. Statistical analyses reveal distinct correlations between Mn, Na, Ba, Ni and Cu; the Mn-rich coatings showed enrichment of Mo, Zn and possibly Co in a Mn-phase. The iron phase holds high concretions of P and As. Two iron-rich concretions with high contents of P, Ca, Sr, Y, Yb and La were found east and northeast of Spitsbergen Banken, probably indicating upwelling of nutrient-rich, cold polar water along the Svalbard shelf.

Description: Four metal speciation and fractionation techniques – DGT (diffusive gradients in thin films), 1-kDa ultrafiltration, 0.22-µm membrane filtration and aquatic moss – were simultaneously applied to a small, contaminated freshwater stream in northern Sweden to investigate differences and similarities between the methods regarding trace metal speciation and their dependence on geochemical water properties. The investigated metals comprise Al, Cd, Co, Cu, Fe, Mn, Ni, and Zn. The normal DGT devices with Chelex cation exchanger were used. Shoots from the aquatic moss Fontinalis antipyretica L ex Hedw. were collected in a non-polluted brook and transplanted to the sampling site for exposure. It was evident that 0.22-µm membrane filtration, 1-kDa ultrafiltration and DGT generally measured different metal fractions where 〈1-kDa ultrafiltered concentrations were lower than DGT labile concentrations which in turn were lower than 〈0.22-µm concentrations. The differences between DGT and 〈1-kDa concentrations indicate the occurrence of labile colloids discriminated by ultrafiltration. Strong correlations between DGT and 〈1 kDa concentrations were found for Al, Cu, Cd, Co and Zn. Despite a rigorous sample cleaning, retention of particulate matter on the moss samples was revealed by a significant correlation between metal concentrations in moss and particulate Fe. Generally, elevated trace metal concentrations were found in moss exposed at the sampling site compared to reference moss from the non-polluted brook. No significant correlations were found between DGT-labile concentrations and moss concentrations. Supplementary material: DGT – labile concentrations of Al, Cd, Co, Cu, Fe, Mn, Ni and Zn from deployments in Gråbergsbäcken Stream is available online at http://www.geolsoc.org.uk/SUP18566 . A hard copy can be obtained from the Society Library.

Description: The efficiency of biogeochemical mapping for identifying acid sulphate soils (AS soils) was studied by sampling and analysing water, transplanted aquatic moss ( Fontinalis antipyretica ) and leaves of the vascular plant Calamagrostis purpurea at two sites in a stream in northern Sweden with AS soils in its drainage area. One upstream sampling station (Mårtsmarken) was situated in an area dominated by till, and a downstream station (Persraningen) was situated in an area where AS soils are common. Metal contents in F. antipyretica and C. purpurea at these sites were compared to those in water (both unfiltered samples, and samples subjected to 0.22 µm membrane filtration and 1 kDa ultrafiltration to obtain data on metal speciation and its effects on uptake). Oxidation of sulphides with associated increases in acidity and release of metals were clearly reflected by differences in the water samples. At Persraningen the pH was lower than at Mårtsmarken, and the unfiltered concentrations of Al, Ca, Cd, Co, Cu, K, Mg, Mn, Ni, P, S, Sr, Y and Zn were higher. At the upstream station, Mårtsmarken, the suspended fraction was an important carrier of Fe and P, and the colloidal concentrations were higher than or similar to the dissolved concentrations for all determined elements except Na and K. At Persraningen the low pH resulted in changes of speciation, so that the dissolved concentrations were higher than the colloidal concentrations for most elements. For Al, As, Cr, Cu, Pb and Y, the dissolved and colloidal concentrations were similar. For Fe, the colloidal concentration was usually higher than the dissolved concentration, and suspended Fe was detected. Aluminium, Cr, Cu, Fe and Y concentrations were significantly higher in Fontinalis antipyretica at Persraningen than at Mårtsmarken. In addition, concentrations of Al and Fe in C. purpurea were significantly higher at Persraningen. Our results highlight the potential of biogeochemical mapping for predicting the occurrence of AS soils. A limitation is the strong pH dependence of the uptake of metals in the aquatic mosses resulting in that only a few of the elements typically occurring at high concentrations in waters draining AS soils are enriched in the macrophytes. A combination of maps showing both absolute concentrations and elemental ratios would be useful for this, including not only ratios of previously suggested utility (e.g. Y:Pb and Ni:Pb), but also others, such as Y:Ca, Al:Ca, Cu:Ca, Y:Mg, Al:Mg and Cu:Mg.