Fluxes of iron and manganese across the sediment–water interface under various redox conditions

Fluxes of dissolved forms of iron and manganese across the sediment–water interface were studied in situ in the Gulf of Finland and the Vistula Lagoon (Baltic Sea), and in the Golubaya Bay (Black Sea) from 2001 to 2005. Fluxes were measured using chamber incubations, and sediment cores were collected and sliced to assess the porewater and solid phase metal distribution at different depths. Measured and calculated benthic fluxes of manganese and iron were directed out of sediment for all sites and were found to vary between 70–4450 and 5–1000 µmole m^− 2 day^− 1 for manganese and iron, respectively. The behavior of the studied metals at various redox conditions in the near-bottom water and in the sediment was the main focus in this study. Our results show the importance of bottom water redox conditions for iron fluxes. We measured no fluxes at oxic conditions, intermediate fluxes at anoxic conditions (up to 200 μmole m^− 2 day^− 1) and high fluxes at suboxic conditions (up to 1000 μmole m^− 2 day^− 1). Total dissolved iron fluxes were generally dominated by iron(II). Contribution of iron(III) to the total iron flux did not exceed 20%. Obtained fluxes of manganese at all studied regions showed a linear correlation (r² = 0.97) to its concentration in the porewater of the top sediment layer (0–5 mm) and did not depend on dissolved oxygen concentrations of bottom water. Organically complexed iron and manganese were in most cases not involved in the benthic exchange processes.     

Time dependence of organic matter decay and mixing processes in Framvaren, a permanently anoxic fjord in South Norway

Three different layers have been identified in Framvaren, which has a maximum water depth of 184 m. One oxic layer above the redoxcline at 18–20 m. One anoxic layer from 20 to 100 m which is occasionally ventilated by a flow over the sill (which has a depth of 2.5 m), and finally a stagnant layer below 100 m. Using the release rate of silica from the bottom and measurements of the concentration of HTO it is possible to make some calculations on the annual volume of interleaving in the layers 25–50 m, 50–75 m, and 75–100 m together with the advective flows. Reliable values of the sulfide concentration were obtained by precipitating and weighing HgS together with careful protection of all anoxic water samples with argon. The light yellow color of the precipitate in the depth range 25 to 80 m indicates that the occasional ventilation will cause such reactions as 0.50₂ + H₂S S(colloidal) + H₂O. The elemental sulfur, being stabilized with HS^–, is set free upon the precipitation of HgS. The new data for the concentration of sulfide give an acceptable stoichiometry for the decay reaction of organic matter. This is not the case with the data of Yao and Millero. The mean values for the concentrations of ammonium and phosphate agree with the new data of Yao and Millero. The mol/mol C/N ratio of 10.1 found in trapped material by Naess and coworkers (1988) agrees with the stoichiometry of the dissolved constituents, i.e. C/N = 9.92 ± 0.45. A denitrification reaction is suggested to explain the high values of C/N. The vertical diffusion coefficient at 100 m calculated from the depth profile of silica was 0.92 × 10^–6 m² s^–1 which lies in the range of values given by Fröyland. Finally, the ¹⁴C age of the total dissolved inorganic carbon (Ct) in the water below 90 m was about 1600 years indicating a bioproduction in the period 8000 years B.P. to A.D. 1853 when a channel was opened between the fjord outside (Helvikfjord) and Framvaren.     

Holocene glacial history and sea-level changes on James Ross Island,Antarctic Peninsula

A reconstruction of deglaciation and associated sea-level changes on northern James Ross Island, Antarctic Peninsula, based on lithostratigraphical and geomorphological studies, shows that the initial deglaciation of presently ice-free areas occurred slightly before 7400 ¹⁴C yr BP. Sea-level in connection with the deglaciation was around 30 m a.s.l. A glacier readvance in Brandy Bay, of at least 7 km, with the initial 3 km over land, reached a position off the present coast at ca. 4600 yr BP. The culmination of the advance was of short duration, and by 4300 yr BP the coastal lowlands again were ice-free. A distinct marine level at 16–18 m a.s.l. was contemporaneous with or slightly post-dates the Brandy Bay advance, thus indicating the relative sea-level around 4600–4500 yr BP. Our results from James Ross Island confirm that over large areas in this part of Antarctica the last deglaciation occurred late. © 1997 John Wiley & Sons, Ltd.     

Fourier-transform Infrared Spectroscopy (FTIRS), a New Method to Infer Past Changes in Tree-line Position and TOC using Lake Sediment

This study tests the hypothesis that Fourier-transform infrared spectroscopy (FTIRS) of lake sediments can be used to infer past changes in tree-line position and total organic carbon (TOC) content of lake water. A training set of 100 lakes from northern Sweden spanning a broad altitudinal and TOC gradient from 0.7 to 14.9 mg/l was used to assess whether vegetation zones and TOC can be modelled from FTIR spectra of surface sediments (0–1 cm) using principal component analysis (PCA) and partial least squares (PLS) regression. Preliminary results show that FTIRS of lake sediments can be used to reconstruct past changes in tree line and the TOC content of lake water, which is hardly surprising since FTIRS registers the properties of organic and minerogenic material derived from the water mass and the drainage area. The FTIRS model for TOC gives a root mean squared error (RMSECV) of calibration of 1.4 mg/l (10% of the gradient) assessed by internal cross-validation (CV) yielding an R_cv² of 0.64. This should be compared with a near-infrared spectroscopy (NIRS) and diatom transfer function for TOC from the same set of lakes, which have a R_cv² of 0.61 and 0.31, and RMSECV of 1.6 and 2.3 mg/l, respectively. The FTIRS-TOC model was applied to a Holocene sediment core from a tree-line lake and the results show similar trends as inferences from NIRS and pollen from the same core. Overall, the results indicate that changes in FTIR spectra from lake sediments reflect differences in catchment vegetation and TOC, and that FTIRS-models based on surface-sediment samples can be applied to sediment cores for retrospective analysis.     

Intrinsic biodegradation of toluene coupled to the microbial reduction of ferric iron: laboratory column experiments

Intrinsic biodegradation of toluene coupled with the microbial reduction of ferric iron (Fe(III)) as the terminal electron acceptor was studied by using laboratory column experiments under continuous flow conditions. Columns were packed with contaminated aquifer sediment and N₂-purged groundwater taken from the western part of the Gardermoen aquifer. The columns were operated anaerobically at 8 °C (in-situ temperature). Chloride was initially used to characterize flow properties of the columns. Intrinsic biodegradation of toluene, including abiotic loss and biological loss, was estimated by comparing breakthrough curves of toluene for live columns and sterilized control columns based on mass balance in steady-state conditions. The column experiments were run at two different flow velocities. The estimated average intrinsic rate was -0.73 and -0.53 mM day^-1 for pore-water velocities of 1.75 and 2.68 cm h^-1, respectively, corresponding to -0.27 and -0.22 mM day^-1 in biological loss rate. The results indicate that intrinsic biodegradation of toluene could be used as an efficient remediation approach for contaminated groundwater at the Gardermoen fire-fighting training site.     

Late Quaternary glaciation history of Isla de los Estados,southeasternmost South America

Isla de los Estados is a mountainous island southeast of Tierra del Fuego, in southernmost South America. Its central and eastern parts have an alpine topography, transected by U-shaped valleys, small, partly over-deepened fjords, and a multitude of abandoned cirques, all associated with extensive former local glaciations. Traces of glacial erosion generally reach 400–450 m a.s.l., and above that trimline a distinct sharp-edged nunatak derived landscape is present. The westernmost part of the island has a lower, more subdued topography, reflecting its “softer” geology but possibly also over-running and erosion by mainland-derived ice streams. The present study concentrated on glacigenic sediment sequences exposed along coastal erosional cliffs. A combination of OSL and ¹⁴C datings show that these sediments mostly date from the latest (Wisconsinan/Weichselian) glacial cycle, i.e. from the last ca. 100 ka with the oldest (glaciolacustrine) deposits possibly as old as 90–80 ka. The upper parts of overlying tills, with associated lateral and terminal moraines from glaciers that expanded onto an eustatically exposed dry shelf north of the island, date from the last global glacial maximum (LGM). Radiocarbon ages of peat and lake sediments indicate that deglaciation began 17–16 cal ka BP.     

Micas of the muscovite-lepidolite series from the fregeneda pegmatites (Salamanca,Spain)

Summary In the Fregeneda area different types of pegmatites can be recognized by their mineralogy, morphology, internal structure and field relationships. The most common type corresponds to a simple pegmatite with homogeneous internal structure, but zoned Li-bearing pegmatites also are relatively widespread. Cassiterite-bearing pegmatites are subordinate. The pegmatites are spatially associated to the Lumbrales granite. This is a parautochthonous, fine- to medium-grained, two-mica granite, one of the syntectonic massifs which were deformed during the third phase of Hercynian deformation. Representative micas selected from the different groups of pegmatites were studied to determine wether the pegmatites can be related by a common fractionation path, and how different pegmatite types are related to the spatially associated Lumbrales granite. Compositional variations in the micas depend on the pegmatite type. Muscovite coexisting with Li-micas in the Li-bearing pegmatites is one of the richest in Al₂O₃ (35.4–37.7 wt%) and the poorest in FeO (0.2–1.5 wt%) and MgO (0–0.3 wt%), whereas muscovite of the simple discordant pegmatites shows the highest FeO (2.2–3.3 wt%) and that from the Lumbrales granite is the richest in MgO (0.5–0.7 wt%) and TiO₂ (0.6–1.1 wt%). On the other hand, Sn (70–1168 ppm), Li (< 5–22253 ppm), F (880–21470 ppm), Cs (< 5–1696 ppm), Rb (800–9181 ppm) and other trace elements seem to increase with distance from the Lumbrales granite, and K/Rb decreases. According to this ratio, the exterior Li-bearing pegmatites are the more evolved, whereas the interior pegmatites are less evolved, and are richer in Cs, Li and Zn than other pegmatite types.

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Glimmerminerale der Muscovit-Lepidolith-Serie aus den Pegmatiten von Fregeneda, Salamanca, Spanien

Zusammenfassung Im Gebiet von Fregeneda sind auf Grund ihrer Mineralogie, Morphologie, Internstruktur und Geländebeziehungen verschiedene Pegmatittypen zu unterscheiden. Am häufigsten sind einfache homogen aufgebaute Pegmatite. Zonar gebaute Li-Pegmatite sind ebenfalls weit verbreitet, Zinnstein-führende Pegmatite treten hingegen zurück, Die Pegmatite sind räumlich mit dem Lumbrales Granit, einem paraautochtonen, fein- bis mittelkörnigen Zwei-Glimmergranit, assoziiert, Dieser gehört einem der syntektonischen Massive, die während der dritten Phase der hercynischen Deformation deformiert wurden, an. Repräsentative, aus den verschiedenen Pegmatittypen separierte Glimmerminerale wurden untersucht, um zu klären, inwieweit die Pegmatite über einen direkten Fraktionierungspfad zu verbinden sind und in welcher Beziehung sie zu dem Lumbrales Granit stehen. Die Variation der Zusammensetzung der Glimmer hängt vom Pegmatittyp ab. Muscovite, die mit Li-Glimmern koexistieren, sind die relativ Al₂O₃-reichsten (32–37.7 Gew.%) und Fe- (0.2–1.5 Gew.%.) und Mg-ärmsten (0–0.3 Gew.%). Jene aus dem Lumbrales Granit sind die reich an MgO (0.5–0.7) und TiO₂ (0.6–1.1 Gew.%). Die Gehalte von Sn (70–1168 ppm), Li (< 5–22253 ppm). F (880-21470 ppm), Cs (< 5–1696 ppm), Rb (800–9181 ppm) und anderer Spurenelemente nehmen mit der Entfernung vom Lumbrales Granit zu, während K/Rb abnimmt. Auf Grund dieses Verhältnisses sind die externen Li-führenden Pegmatite höher, die internen Pegmatite hingegen geringfügiger entwickelt. Erstere sind daher auch reicher an Cs, Li und Zn.

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With 4 Figures     

Elimination of Interferences in the Determination of Palladium,Platinum and Rhodium Mass Fractions in Moss Samples using ICP‐MS/MS

Moss samples (Pleurozium schreberi) exposed to traffic‐related emission of Pd, Pt and Rh were analysed in this study. Successful elimination of interferences was achieved in the determination of Pd, Pt and Rh mass fractions in these samples using inductively coupled plasma‐tandem mass spectrometry (ICP‐MS/MS). Based on the results, a reliable determination of Pd, Pt and Rh mass fractions in microwave‐digested moss samples was obtained using ammonia (10% NH₃ in He) in the collision/reaction cell when ¹⁰³Rh was measured either on‐mass (103→103) or with mass‐shift (103→171) and mass‐shifts for ¹⁰⁸Pd (108→159) and ¹⁹⁵Pt (195→229) were used. The ICP‐MS/MS procedure was validated using BCR‐723 (road dust) as a reference material. In addition, a good agreement between the ICP‐MS/MS results and the results obtained with cloud point extraction and quadrupole ICP‐MS was observed for the moss samples.     

Estimation of winter leaf area index and sky view fraction for snow modelling in boreal coniferous forests: consequences on snow mass and energy balance

Leaf area index (LAI) and canopy coverage are important parameters when modelling snow process in coniferous forests, controlling interception and transmitting radiation. Estimates of LAI and sky view factor show large variability depending on the estimation method used, and it is not clear how this is reflected in the calculated snow processes beneath the canopy. In this study, the winter LAI and sky view fraction were estimated using different optical and biomass‐based approximations in several boreal coniferous forest stands in Fennoscandia with different stand density, age and site latitude. The biomass‐based estimate of LAI derived from forest inventory data was close to the values derived from the optical measurements at most sites, suggesting that forest inventory data can be used as input to snow hydrological modelling. Heterogeneity of tree species and site fertility, as well as edge effects between different forest compartments, caused differences in the LAI estimates at some sites. A snow energy and mass balance model (SNOWPACK) was applied to detect how the differences in the estimated values of the winter LAI and sky view fraction were reflected in simulated snow processes. In the simulations, an increase in LAI and a decrease in sky view fraction changed the snow surface energy balance by decreasing shortwave radiation input and increasing longwave radiation input. Changes in LAI and sky view fraction affected directly snow accumulation through altered throughfall fraction and indirectly snowmelt through the changed surface energy balance. Changes in LAI and sky view fraction had a greater impact on mean incoming radiation beneath the canopy than on other energy fluxes. Snowmelt was affected more than snow accumulation. The effect of canopy parameters on evaporation loss from intercepted snow was comparable with the effect of variation in governing meteorological variables such as precipitation intensity and air temperature. Copyright © 2012 John Wiley & Sons, Ltd.