Variations in the physico-chemical speciation of the rare earth elements (REE) have been investigated in a subarctic boreal river during an intense spring flood event using prefiltered (<100 μm) samples, cross-flow (ultra)filtration (CFF), flow field-flow fractionation (FlFFF), and diffusive gradients in thin films (DGT). This combination of techniques has provided new information regarding the release and transport of the REE in river water. The colloidal material can be described in terms of two fractions dominated by carbon and iron, respectively. These two fractions, termed colloidal carrier phases, showed significant temporal changes in concentration and size distribution. Before the spring flood, colloidal carbon concentrations were low, the colloids being dominated by relatively large iron colloids. Colloidal concentrations increased sharply during the spring flood, with smaller carbon colloids dominating. Following the spring flood, colloidal concentrations decreased again, smaller carbon colloids still dominating. The REE are transported mainly in the particulate and colloidal phases. Before the spring flood, the REE composition of all measured fractions was similar to local till. During the spring flood, the REE concentrations in the colloidal and particulate fractions increased. The increase was most marked for the lighter REE, which therefore showed a strong enrichment when normalized to local till. Following the spring flood, the REE concentrations decreased again and reverted to a distribution similar to local till. These changes in the concentration and distributions of carbon iron and REE are interpreted in terms of changing hydrological flow paths in soil and bedrock which occur during the spring flood.
The role of particles for U isotope transport was investigated in the Kalix River watershed, a particle-poor, Fe/Mn-rich river in northern Sweden, and in the Baltic Sea estuary. Particles >0.45 μm are strongly enriched in U and contain 20-50% of the total riverine uranium budget and <1% of the total U in brackish waters (3-7 PSU). The particles have high δ234U which is close to that of dissolved U in the associated water, indicating that U on particles is dominantly nondetrital and isotopically exchanges rapidly with the ambient dissolved U. Particles at the river mouth are dominated by nondetrital Fe-Mn oxyhydroxides. Uranium and Fe are strongly correlated, clearly demonstrating that secondary Fe-oxyhydroxide is the major carrier of U in river water. There is no evidence for significant association of U with Mn-oxyhydroxide. Apparent U distribution coefficients ... were calculated for U between the authigenic Fe on particles and the solution. These values appear to be relatively constant throughout the year. This suggests an equilibrium between Fe in solution and authigenic Fe-oxyhydroxides on detrital particles. High values of .... calculated for one summer as well as high U concentrations in brackish waters can be explained by U scavenging by biogenic phases with low authigenic Fe content.
In this study the Nd concentrations (CNd) from 18 months of weekly sampling of filtered water (<0.45 μm) in the Kalix River, northern Sweden, are reported with εNd(0) and 147Sm/144Nd ratios determined in samples representing major flow events as well as maxima and minima in CNd. The CNd varies by a factor of ten, between 200 pmol/L to 2100 pmol/L, and there is a strong relation between high discharge and high CNd. The Nd in the Kalix River is mainly transported on particles (>90%), dominated by a colloidal phase primarily composed of organic C and Fe. The εNd(0) and 147Sm/144Nd only vary within a narrow range, -27.1 to -24.8 and 0.103 to 0.110 respectively, with no obvious relationship to CNd and discharge. The εNd(0) and 147Sm/144Nd in the river water is significantly lower than in the unweathered till and average bedrock in the catchment and show a closer resemblance with the isotopic characteristics found in humic substances and plant material. These data show that the isotopic composition of Nd exported from a large boreal drainage basin does not directly reflect that of the bulk bedrock in the catchment. The isotopic composition is controlled by selective weathering and the Nd transport is dominated by organic colloidal particles.
Particle-mediated removal processes of U isotopes were investigated during spring flood discharge in the low-salinity zone (LSZ, up to 3 practical salinity units [psu]) of a stable estuary. A shipboard ultrafiltration cross-flow filtration (CFF) technique was used to separate particles (>0.2 μm) and colloids (between 3000 daltons (3 kD) and 0.2 μm) from ultrafiltered water (<3 kD) containing "dissolved" species. Sediment traps were used to collect sinking material. Concentration of Fe and organic C, which are indicators of the major U carrier phases, were used to interpret the behavior of 234U-238U during estuarine mixing. Colloids dominated the river water transport of U, carrying ≈90% of the U. On entering the estuary, colloids accounted for the dominant fraction of U to about a salinity of 1 psu, but only a minor fraction (<5%) at 3 psu. A substantial fraction of the total U is removed at <1 psu by Fe-organic rich colloids that aggregate and sink during initial estuarine mixing in the Kalix River estuary. In contrast, at salinities >1 psu, there is a general correlation between U and salinity in all filtered fractions. The 234U/238U ratios in different filtered fractions and sinking particles were generally indistinguishable at each station and showed enrichment in 234U, compared with secular equilibrium (δ234U = 266-567). This clearly shows that all size fractions are dominated by nondetrital U. Consideration of U isotope systematics across the estuary reveals that substantial U exchange must occur involving larger particles at least to 1 psu and involving colloids at least to ≈1.5 psu. Further exchange at higher salinities may also occur, as the proportion of U on colloids decreases with increasing salinity. This may be due to decreasing colloid concentration and increasing stabilization of uranyl carbonate complexes during mixing in the estuary. The results show that although U is a soluble element that shows generally conservative mixing in estuaries, removal occurs in the very low salinity zone, and this zone represents a significant sink of U. Variation in composition and concentration of colloidal particles between different estuaries might thus be an important factor for determining the varying behavior of U between estuaries.
With data generated from cruises to the Canada Basin in 2000, to the Eurasian and Central Arctic Ocean basins in 2001, to the Fram Strait in 2002 and to the Chuckchi Sea in 2005 we now have a good general view of the distribution and isotopic composition of Nd (εNd) in the Arctic Ocean [1, 2]. The restricted Arctic Ocean basin is surrounded by large continental shelves, covering more than 50% of its total area.Distinct from other oceans, with surface water Nd depletion, there is throughout the Arctic a pattern of high Nd concentrations, up to 58pM, at the surface that gradually diminish with depth to 15-18pM in the deep waters. A range of isotopic variations across the Arctic and within individual depth profiles reflects the different sources of waters. The dominant source of water and Nd is the Atlantic (εNd= -10.7). Radiogenic isotope Nd signatures can be traced in Pacific water flowing into the Canada Basin and further into the Eurasian Basin (up to εNd= -6.5). The variation of εNd and concentration in the Arctic Ocean suggest that Nd input from rivers and shelf sediments is also of great importance.Improving our understanding of the vast Siberian Shelves influence on Nd and trace element behaviour in the Arctic Ocean was one of the main objectives of the International Siberian Shelf Study 2008 (ISSS-08). The ISSS-08 cruise recovered filtered water (<0.2µm), particles and sediments from the Laptev and East Siberian Seas as well as estuarine and river water from Lena, Indigirka and Kolyma. Crucial processes, including loss of river water Nd in the estuarine region and shelf sediment-sea water exchange will be discussed in terms of controlling the Nd concentration and isotopic composition of sea water.[1] Andersson et al. (2008) GCA 72, 2854-2867. [2] Porcelli et al. (2009, in press) GCA. (2009, in press)
This study examines the dynamics of sulfur and trace elements (As, Co, Mo, Ni, Ti and Zn) when brackish-water sediments, unusually rich in metastable iron sulfide (probably a mixture of mackinawite and greigite), are brought into the oxidation zone by postglacial isostatic land uplift and farmland drainage. When subaqueous sediments approach the sea level, metastable iron sulfide is oxidized in the upmost layers and pyrite preserved and even accumulated concomitantly trapping Co, Ni and Zn but not As and Mo. When the land uplift has brought the sediments above sea level and natural drainage thus is initiated, the pyrite is oxidized and Co, Ni and Zn are released and transported down the profile. If this setting remained undisturbed, the slightly oxidized sediment (unripe soil) would become covered by peat and thus protected from further oxidation and metal translocation. Often these sediments are, however, artificially drained resulting in extensive oxidation and fast soil-profile development. The soil is an acid sulfate (AS) soil, characterized by low pH (<4), extensive leaching of metals and an abundance of disseminated brownish Fe(III) precipitates. We suggest that the fast soil development is due to initial oxidation of metastable iron sulfide, followed by pyrite oxidation. Drain bottom sediment, which in terms of chemistry and S-isotopes resembled that of the surfacing sea bottom strata, acted during the sampling period as a sink for metals. The abundant preservation of metastable iron sulfide below the groundwater table, even long periods after uplift above the sea level, is a puzzling feature. We suggest that it is the net result of sulfur starvation, an abundance of Fe(II) and strongly reducing conditions.
Elemental size distributions, from truly dissolved through colloidal to particulate, have been studied in a subarctic boreal river. The measurements, carried out during 2002, ranged from winter to summer conditions, including an intense spring flood event. Results are reported for a total of 42 elements. Size distributions were characterised using a combination of cross-flow (ultra)filtration (CFF), flow field-flow fractionation (FlFFF), and diffusive gradients in thin-films (DGT). The three techniques showed similar trends, but quantitative comparisons reveal some important differences that warrant further investigation.
A considerable amount of colloidally bound Ca has been detected in water samples from Amazonian rivers and the Kalix River, a sub-arctic boreal river. Fractionation experiments using several analytical techniques and processing tools were conducted in order to elucidate the matter. Results show that on average 84% of the total Ca concentration is present as free Ca. Particulate, colloidal and complexed Ca constitute the remaining 16%, of which the colloidal fraction is significant. Ultrafiltration experiments show that the colloidal fraction in the sampled Amazonian rivers and the Kalix River range between 1% and 25%. In both the Amazonian and the Kalix rivers the technique of cross-flow ultrafiltration was used to isolate particles and colloids. The difference in concentration measured with ICP-AES and a Ca ion-selective electrode in identical samples was used to define the free Ca concentration and thus indirectly the magnitude of the particulate, colloidal and complexed fractions. Results from the Kalix and Amazonian rivers are in excellent agreement. Furthermore, the results show that the colloidal concentrations of Ca can be greatly overestimated (up to 227%) when conventional analysis and calculation of ultrafiltration data is used due to retention of free Ca ions during the ultrafiltration process. Calculation methods for colloidal matter are presented in this work, using complementary data from ISE analysis. In the Kalix River temporal changes in the fractionation of Ca were studied before, during and after a spring-flood event. Changes in the size distribution of colloidally associated Ca was studied using FlFFF (Flow Field-Flow Fractionation) coupled on-line to a HR ICP-MS. The FlFFF–HR ICP-MS fractograms clearly show the colloidal component of Ca, supporting the ultrafiltration findings. During winter conditions the size distribution of colloidally associated Ca has a concentration maximum at 5 to 10 nm in diameter, shifting to smaller sizes (<5 nm) during and after the spring flood. This shift in size distribution follows a change in the river during this period from ironoxyhydroxy colloids being the most important colloidal carrier phase to humic substances during and after the spring flood. WHAM and NICA-Donnan models were used to calculate the amount of colloidally bound Ca. The results similar for both models, show that on average 16% of the Ca may be associated to a colloidal phase, which is in broad agreement with the measurements.
During the last decade, the potential plant impact on the biogeochemical cycle of Si via the large terrestrial biogenic Si reservoir formed by vegetation has attracted considerable interest. It has been concluded that the release of silicic acid from dissolution of soil phytoliths might exceed the Si mobilized by weathering of Si-containing primary minerals, which implies that the biogenic contribution to the total content of Si in the soil profile must be considered in weathering studies. Information about Si isotopes can potentially be used for differentiation between relative contributions from biogenic and mineral sources in natural waters, soil solutions and plants. This would, however, require thorough characterization of the terrestrial biogenic Si reservoir, a task that received somewhat limited attention to date. The aim of the present study was to characterize the Si isotopic composition of a boreal forest, with bedrock consisting of dolomitic limestone, in Northern Sweden. Representative biomass from the forest area exhibited a surprisingly homogenous Si isotopic composition, ranging from δ29Si (-0.14 ± 0.05)‰ (2σ) to (0.13 ± 0.04)‰. Further, a change in the Si isotopic composition of (+0.39 ± 0.04)‰ has been detected in Leymus arenarius, indicating predominant accumulation of heavier isotopes from spring to autumn. Recent studies of Si isotopic composition in plants have been focused on the root uptake of dissolved silicic acid as the only Si accumulation path. Results acquired during the present study provide compelling evidence to suggest that exogenous Si is also incorporated in the surface structure of the plant material. A surface contribution in excess of 5% of the total Si would introduce a significant shift in the bulk isotopic composition (>0.1‰) assuming that the exogenous material differed by 2‰ from the biogenic Si. This strongly suggests that the surface contribution must be carefully considered during in situ uptake studies.
Interest in quantifying the biogenic impact on the terrestrial biogeochemical Si cycle has increased significantly since biological control has been suggested. Previous observations of isotopic fractionation of Si during biogeochemical and geochemical processes imply that seasonal dissolved Si isotopic patterns in rivers have the potential for use in extracting information about the riverineand terrestrial biogeochemical Si cycles.Therefore, variations in the isotopic composition of dissolved riverine Si were investigated for the Kalix River, Northern Sweden, one of the largest pristine rivers in Europe, based on high-frequency sampling during a period of 25 weeks from early April to early October 2006. Temporal variations spanning 0.4. for δ29Si and 0.8. for δ30Si of dissolved Si in the Kalix River were observed during the period, suggesting that the riverine Si input to the oceans cannot be considered to have a constant Si isotopic composition even on a short time scale. The results implicate biogeochemical Si-cycling via formation and dissolution of biogenic silica as major processes controlling the Si transport in boreal systems. The Si budget in the river system appeared to be controlled by relative Si accretions during high discharge events and relative Si depletions in the subarctic mountainous and lake dominated areas. There were also temporal variations in Si isotopic composition with accretion (relative Si contribution), accompanied by depletion of the heavier Si isotopes, while the opposite trend was observed during periods of riverine Si depletion. These isotope variations can be explained by release of plant derived silica, depleted in heavier Si isotopes, during the spring snowmelt. Further, increased volumetric contribution from the headwater and losses of Si due to biogenic silica formation by diatoms in the subarctic lakes at a later period are expected to be responsible for the preferential losses of lighter isotopes. These conclusions are further verified by land cover analysis.
Size fractionated classes of Fe in surface water at two stations, one in central Baltic Sea (the Landsort Deep) and one in Bothnian Sea, were measured from spring until autumn to evaluate temporal variations in the physicochemical speciation. Membrane filtration, cross-flow ultrafiltration and DGT (diffusive gradients in thin films) were among the applied techniques. Average concentrations for total,
Stable Fe isotope compositions have been measured in water samples of the subarctic Kalix River, a first-order stream, and soil water samples from a riparian soil profile adjacent to the first-order stream (Northern Sweden). In the first-order stream, dominated by forest, both the particulate (>0.22 µm) and dissolved (<0.22 µm) phase showed negative δ56Fe values (relative to IRMM-014) during base flow and meltwater discharge in May (−0.97 to −0.09‰). The Fe isotope composition in the water from the riparian soil profile varied between −0.20 and +0.91‰ with sharp gradients near the groundwater table. A linear correlation between the δ56Fe values and the TOC/Febulk ratio was measured during snowmelt in the unfiltered river waters (δ56Fe from −0.02 to +0.54‰), suggesting mixing of two Fe components. Two groups of Fe aggregates, with different Fe isotope compositions, are formed in the boreal landscape. We propose that carbon-rich aggregates, Fe(II)(III)-OC, have negative δ56Fe values and Fe-oxyhydroxides have positive δ56Fe values. A mixture of these two components can explain temporal variations of the Fe isotope composition in the Kalix River. This study suggests that stable Fe isotopes can be used as a tool to track and characterize suspended Fe-organic carbon aggregates during transport from the soil, via first-order streams and rivers, to coastal sediment. Furthermore, the differences in Fe isotope values in the Kalix River and the first-order stream during base flow conditions suggest that the primary Fe sources for river water change throughout the year. This model is combining the Fe isotope composition of first-order streams and rivers to weathering and transport processes in the riparian soil.
Iron isotopes were measured in suspended matter (>0.2 µm) in the Ob, Yenisey and Lena River freshwater plumes during the International Siberian Shelf Study 2008 (ISSS-08). The δ56Fe value was around zero within the Lena River and close to the river mouth, but changed to more negative values in the outer parts of the plume. In both the Ob and Yenisey plumes suspended matter in the surface water had clearly negative values whereas samples close to the bottom showed values close to zero.
It has previously been suggested that total Fe in river suspended matter (>0.2µm) in boreal regions is roughly a mixture of three phases, detrital particles (δ56Fe around zero), oxyhydroxide particles (δ56Fe positive) and C-Fe particles (δ56Fe negative). We suggest that the δ56Fe pattern observed in this study is the result of relatively rapid removal of detrital particles and Fe-oxyhydroxides, leaving a suspended fraction with negative values in the surface water in the outer parts of the freshwater plumes. Hence, during estuarine mixing of suspended particles heavy iron isotopes are deposited close to the river mouth, whereas light isotopes are exported to open ocean water.
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.
Scavenging of alkali and alkaline-earth elements by suspended Fe and Mn in the Kalix River, northern Sweden, has been studied for a period of seventeen months. More than 95% (by weight) of suspended nondetrital concentrations of Ca, Mg, and Sr are scavenged on suspended nondetrital Fe throughout all seasons. Barium is correlated to suspended Fe during winter, but during the summer a significant fraction of nondetrital Ba is associated with Mn-rich particles. Porewater profiles for Ca, Mg, and Sr are similar to the dissolved Fe profile, suggesting desorption from a Fe-rich carrier phase. Compared with the river water concentration, Ba is enriched twenty-five times in porewater and shows, together with Mn, a post-depositional subsurface maximum in the solid sediment. The alkali elements Na and K show a linear correlation to suspended nondetrital Fe during the winter. However, the summer concentrations cannot be explained by scavenging onto Fe alone, and sediment and porewater data show no clear association with Fe or Mn. The distribution coefficients for the alkaline-earth elements are two orders of magnitude larger than coefficients obtained for model Fe-oxyhydroxides. This suggests that surface complexation occurs via other functional groups and/or the alkaline-earths are more firmly bound to the natural Fe-rich phase.
Phase equilibria and thermodynamic properties of the quaternary H2S-CO2-H2O-NaCl system were studied using a statistical associating fluid theory (SAFT)-based equation of state (EOS) at temperatures from 0 to 200 °C (373.15 to 473.15 K), pressures up to 600 bar (60 MPa) and concentration of NaCl up to 6 mol/kgH2O. The understanding of the physical-chemical properties of this system is critical for predicting the consequences of co-injection of CO2 and H2S into geological formations (geological carbon sequestration) as an option for mitigating the global warming trend. Equation of state parameters were generated from regression of available and reliable experimental data and incorporation of existing parameters for some subsystems. Densities were predicted and compared with available experimental results. Using the EOS developed in this study, we predicted equilibrium composition in both liquid and vapor phases, fugacity coefficients of components, the equilibrium pressures at a given composition of the H2O-rich phase in electrolyte solutions with NaCl varying from 0 to 4 mol/kgH2O, and the aqueous solution densities. These predicted values are tabulated and available as supplementary data in the electronic version online. These predictions provide information and guidance for future experiments regarding the thermodynamic properties and phase behaviors in the H2S-CO2-H2O-NaCl system
The speciation of aqueous dissolved sulfur was determined in hydrothermal waters in Iceland. The waters sampled included hot springs, acid-sulfate pools and mud pots, sub-boiling well discharges and two-phase wells. The water temperatures ranged from 4 to 210°C, the pHT was between 2.20 and 9.30 at the discharge temperature and the SO4 and Cl concentrations were 0.020-52.7 and <0.01-10.0mmolkg-1, respectively. The analyses were carried out on-site within ~10min of sampling using ion chromatography (IC) for sulfate (SO42-), thiosulfate (S2O32-) and polythionates (SxO62-) and titration and/or colorimetry for total dissolved sulfide (S2-). Sulfite (SO32-) could also be determined in a few cases using IC. Alternatively, for few samples in remote locations the sulfur oxyanions were stabilized on a resin on site following elution and analysis by IC in the laboratory. Dissolved sulfate and with few exceptions also S2- were detected in all samples with concentrations of 0.02-52.7mmolkg-1 and <1-4100μmolkg-1, respectively. Thiosulfate was detected in 49 samples of the 73 analyzed with concentrations in the range of <1-394μmolkg-1 (S-equivalents). Sulfite was detected in few samples with concentrations in the range of <1-3μmolkg-1. Thiosulfate and SO32- were not detected in <100°C well waters and S2O32- was observed only at low concentrations (<1-8μmolkg-1) in ~200°C well waters. In alkaline and neutral pH hot springs, S2O32- was present in significant concentrations sometimes corresponding to up to 23% of total dissolved sulfur (STOT). In steam-heated acid-sulfate waters, S2O32- was not a significant sulfur species. The results demonstrate that S2O32- and SO32- do not occur in the deeper parts of <150°C hydrothermal systems and only in trace concentrations in ~200-300°C systems. Upon ascent to the surface and mixing with oxygenated ground and surface waters and/or dissolution of atmospheric O2, S2- is degassed and oxidized to SO32- and S2O32- and eventually to SO42- at pH >8. In near-neutral hydrothermal waters the oxidation of S2- and the interaction of S2- and S0 resulting in the formation of Sx2- are considered important. At lower pH values the reactions seemed to proceed relatively rapidly to SO42- and the sulfur chemistry of acid-sulfate pools was dominated by SO42-, which corresponded to >99% of STOT. The results suggest that the aqueous speciation of sulfur in natural hydrothermal waters is dynamic and both kinetically and source-controlled and cannot be estimated from thermodynamic speciation calculations. © 2011 Elsevier Ltd.
Previous research [1] has suggested that the boron (B) isotope system has a potential to be used as a tracer for detecting historic wood fire events. It was hypothesized that highly elevated B concentrations in sediments of a lake, accompanied by an enrichment of 10B, were a result of an urban wood fire event in the 19th century. The δ11B decrease in these sediments exceeded 9 ., coinciding with a peak in the B concentration.To evaluate this hypothesis, seasonal isotopic pattern of boron (B) was investigated during spring and summer 2007 in a small stream draining a boreal forest area which was severely burnt in a major forest fire in the summer of 2006. Dissolved (< 0.22 µm) boron concentrations of the burnt area were significantly higher compared to a non-burnt reference stream, while 11B/10B ratios were significantly lower. Dissolved δ11B differences between the reference and the burnt area stream were found to be -9 to -22 .. We interpret the elevated B concentrations, accompanied by enrichment of 10B, in the burnt stream as wood and plant ash leaching of biogenic B from the burnt forest by surface run-off. Our results suggest that a boreal forest fire event significantly increases the leached amount of isotopically lighter B in the dissolved phase of stream run-off.[1] Peltola & Åström (2006), Appl. Geochem. 21 (2006) 941-948.
New developments in micron-scale measurements of trace metals and sulphur contents within sediments by DGT (diffusive gradients in thin-films) have revealed micro-niche structures. The origin of micro-niches is unclear and it is important to understand the relative roles played by inorganic and biological processes in the localised remobilisation of metals. We have undertaken a S and Fe isotope study of micro-niches, to better understand their mechanisms of formation. With their inbuilt pre-concentration, element selection and simple matrix, DGTs are an ideal medium for laser ablation ICPMS. In contrast to analysis of mineral phases, fully matrix-matched standards can be easily made. We have initially concentrated on the measurement of S isotopes and will also present experiments where Fe isotopes have been measured in DGT gels. S and Fe isotopes were measured on a Neptune at mass resolutions of >9000. A New-Wave UP-213 nm laser was used with Ar as the carrier gas. Instrumental mass bias (IMB) for S was corrected for using sample-standard bracketing. Ablation experiments on two S DGT gel standards, 10 Hz, 40% power, 170 μm wide line, scan speed 70 μms-1, show in-run δ34S precisions for DGT gels with 2.1 μmol/cm2 S (3 V of 32S) of <0.2‰ (2SE). There is no observed correlation between δ34S and 32S intensity. Reproducibility on δ34S for individual analytical sessions (4-8 standards) is better than 0.3‰ while the reproducibility over 4 sessions is 0.19‰. Further tests to mimic ablation over micro-niches (continuous ablation across a gel with two isotopic compositions) show similar internal precisions and only slightly worse reproducibility-0.48‰ (2SD; n = 6). The accuracy of the LA δ34S measurements on a BaSO4 gel relative to the reference value of the starting BaSO4, bracketed by a AgI gel of known isotopic composition, is better than 1‰, showing negligible S isotopic fractionation during gel deployment. δ34S variations in micro-niches can be easily resolved at the 1‰ level and 100 μm scale whereas variations in natural micro-niches are expected to be 10‰ or more. Fe measurements, using external normalisation to a 60Ni/61Ni ratio and an exponential law to correct for IMB, suggest internal precisions and external reproducibility of <0.15‰ (2SE) and 0.07‰ (2SD) should be possible.
Dissolved and suspended Mn in the Kalix River, northern Sweden, were measured weekly over a period of eighteen months. During the same period four lakes in the Kalix catchment were sampled at their outlets and in vertical profiles within the lakes, together with a stream draining a series of mires with shallow lakes. Snow melting in mid-May increased the dissolved Mn concentration in the river tenfold, compared with a concentration of 5 μg L-1 during the winter discharge (January to April). We suggest that the increase was caused by Mn-rich mire water mixing with melting snow and being transported to the river. Large concentrations of dissolved Mn built up in the hypolimnion of the lakes studied during the icecovered period. Break-up of the ice and spring-overturn in June increased the dissolved Mn concentration tenfold in lake discharge and a concomitant peak in the dissolved Mn concentration was observed in the river. Lake-derived Mn was the dominant source for Mn in the river during this time. Suspended Mn in the river was hosted mainly in detrital particles during flood in May. In mid-June, non-detrital suspended Mn started to accumulate and reached a maximum in late July and early August. The Mn/Al ratio was 25 times higher during this period than during flood in May, suggesting the precipitation of an Mn-oxyhydroxide phase. The precipitation of the non-detrital Mn-rich phase was correlated in time with increased temperature, increased pH and increased concentration of suspended biogenic particles. The precipitation of dissolved Mn was biologically mediated. Sedimentation and mineralisation of the non-detrital Mn phase in river and lake sediments resulted in a steady increase of the dissolved Mn concentration in the river water during autumn.
The importance of colloids and organic deposits for the transport of uranium isotopes from continental source regions and through the estuarine environment was investigated in the mire-rich Kalix River drainage basin in northern Sweden and the Baltic Sea. Ultrafiltration techniques were used to separate uranium and other elements associated with colloids > 10 kD and >3 kD from "solute" uranium and provided consistent results and high recovery rates for uranium as well as for other elements from large volume samples. Uranium concentrations in 0.45 μm-filtered Kalix River water samples increased by a factor of 3 from near the headwaters in the Caledonides to the river mouth while major cation concentrations were relatively constant. 234U/238U ratios were high (δ234U = 770-1500) throughout the basin, without showing any simple pattern, and required a supply of 234U-rich water. Throughout the Kalix River, a large fraction (30-90%) of the uranium is carried by >10 kD colloids, which is compatible with uranium complexation with humic acids. No isotopic differences were found between colloid-associated and solute uranium. Within the Baltic Sea, about half of the uranium is removed at low salinities. The proportion that is lost is equivalent to that of river-derived colloid-bound uranium, suggesting that while solute uranium behaves conservatively during estuarine mixing, colloid-bound uranium is lost due to rapid flocculation of colloidal material. The association of uranium with colloids therefore may be an important parameter in determining uranium estuarine behavior. Mire peats in the Kalix River highly concentrate uranium and are potentially a significant source of recoil 234U to the mirewaters and river waters. However, mirewater data clearly demonstrate that only small 234U/238U shifts are generated relative to inflowing groundwater. A simple box model of uranium accumulation in peat and transport through the mire that is compatible with the mire data demonstrates that with efficient removal of uranium from solution, only small shifts in 234U/238U ratios can be generated in mirewater uranium. The measurements and model calculations show that mirewaters are not the primary source of the uranium in the river. Bedrock groundwaters with high 234U/238U ratios and uranium concentrations must be the dominant source of riverine uranium.
Sediment samples and porewater of an enclosed bay (Skutviken) affected by stormwater discharge near the centre of Luleå, northern Sweden, were analyzed for major and trace elements and 16 polycyclic aromatic hydrocarbons (PAHs), and compared to a reference site and local till. Among the studied metals, Cd, Cu, Pb and Zn were enriched at Skutviken. The use of trace metal ratios provided indications of pollutant sources for the sediment. Also, the PAH content was enriched, in particular for phenantrene, anthracene, fluoranthene and pyrene, which are regarded as common constituents in stormwater. Pb-210 dating was used to determine historical changes in metal and PAH fixation in the sediment. The bay Skutviken was enclosed by the construction of a road bank in 1962. The enclosure led to reduced water circulation in the bay, which promoted the occurrence of anoxic conditions with sulphate reduction within the bay. As a consequence of these conditions, metals are trapped in the sediments as sulphides. This study suggests that enclosed bays with restricted water circulation may be efficient traps for urban pollutants. In areas with postglacial rebound, where such bays are common, enclosure may have an important impact on water and sediment qualities. Due to the postglacial uplift, presently water covered sediments may rise above the groundwater level in the future. These sediments may then become a secondary pollution source if metal sulphides are oxidized.
Minerals with a low thermal stability strongly constrain the history of cooling and later tectonic reworking of an area, provided these minerals can be dated. The possible use of stilbite, a Ca---Al-silicate of the zeolite group, for geochronologic studies was investigated. Open fractures in the Palaeoproterozoic Malmberget iron ore, northern Sweden, contain low-temperature mineral assemblages with various combinations of apatite, stilbite, calcite, biotite, and less commonly titanite and monazite. Two generations of fractures, that are characterized by calcite and stilbite with distinctly radiogenic initial 87Sr/86Sr at ca. 0.720 and ca. 0.708, are dated at ca. 1740 Ma (monazite) and 1620-1613 Ma (titanite), respectively. Apatite samples, even those intimately intergrown with ca. 1740 Ma old monazite, yield U-Pb ages at 1620-1600 Ma, which indicates that apatite apparently recrystallized and reset its U---Pb system. Older stilbite yields a secondary lead isochron at 1730 ± 6.4 Ma (2σ), which unequivocally demonstrates that the ambient temperature in the Malmberget area from then on remained below the thermal stability of stilbite (ca. 150°C). Stilbite is a natural ion-exchanger and its U-Pb systematics indicates recent mobility of uranium and lead. However, the 1730 ± 6.4 Ma (2σ) age demonstrates that some of the older stilbite was not disturbed during younger fracturing. Hydrothermally altered and secondary stilbite samples yield scattered lead arrays that correspond to secondary isochrons at ca. 1650-1600 D4a, which agrees with the U-Pb titanite and apatite ages. Thus, in combination with other geochronometers, the generally imprecise stilbite ages provide information on the cooling history of an area.
Lead isotope data from sulfide deposits of the western part of the Baltic Shield define mixing lines in the 206Pb 204Pb- 207Pb 204Pb diagram. Lead from two types of sulfide deposits have been investigated: 1. (1) Exhalative and volcanogenic deposits that are syngenetic with their host rocks 2. (2) vein deposits. The syngenetic deposits locally show a very wide range of lead isotopic compositions that reflect a variable addition of highly radiogenic lead, while the vein deposits, although they have radiogenic lead isotopic compositions, exhibit only limited isotopic variations. In different provinces of the shield, both types of deposits fall on the same lead mixing array. The slope of the lead mixing lines varies as a function of the age of basement rocks and the age of the tectonic event which produced the lead mobilization and therefore relates the source rock age with the age of lead mobilization. Calculated mixing ages fall into several short time periods that correspond either to orogenic events or to major phases of continental rifting. The orogenic events are the ca 360-430 Ma Caledonian, ca 900-1100 Ma Sveconorwegian, and the ca 1800-1900 Ma Svecofennian orogenic cycles. The rifting events correspond to the formation of the ca 280 Ma Oslo rift and the Ordovician (ca 450 Ma) graben system in the area of the present Gulf of Bothnia. Each mixing age indicates that lead was mobilized, probably as a consequence of mild thermal disturbances, and that the crust was permeable to lead migration. The data show that the geographic distribution of sulfide deposits with highly radiogenic lead isotopic compositions coincides with old graben systems, orogenic belts, and orogenic forelands on the Baltic Shield. The ages of vein deposits and their geographic distribution demonstrate multiple tectonic reactivation of the interior of the Baltic Shield in response to orogenic events at its margin.
We have developed techniques for the U-Pb analysis of the mineral columbite [(Fe,Mn)(Ta,Nb)2O6], and report U-Pb ages obtained for three early Proterozoic columbites from the Baltic Shield of northern Sweden. The U-Pb ages of these columbites agree with other available geochronological data. U-Pb dating of columbite is therefore a potentially powerful tool in establishing reliable ages of pegmatites, alkaline and carbonatitic intrusions, and ore deposits of Sn, W, and REEs, all of which often contain columbite. Furthermore, columbite can be used to date peraluminous granites as it often occurs within Li-P-REE pegmatites associated with such granites.
This study focuses on attenuation of rare earth elements (REE) when a boreal creek, acidified and loaded with REE and other metals as a result of wetland drainage, empties into a brackish-water estuary (salinity < 6 ‰). Surface water was collected in a transect from the creek mouth to the outer estuary, and settling (particulate) material in sediment traps moored at selected locations in the estuary. Ultrafiltration, high-resolution ICP-MS and modeling were applied on the waters, and a variety of chemical reagents were used to extract metals from the settling material. Aluminium, Fe and REE transported by the acidic creek were extensively removed in the inner/central estuary where the acidic water was neutralised, whereas Mn was relatively persistent in solution and thus redistributed to particles and deposited further down the estuary. The REE removal was caused by several contemporary mechanisms: co-precipitation with oxyhydroxides (mainly Al but also Fe), complexation with flocculating humic substances and sorption to suspended particles. Down estuary the dissolved REE pool, remaining after removal, was fractionated: the <1kDa pool became depleted in the middle REE and the colloidal (0.45 μm (1kDa) pool depleted in the middle and heavy REE. This fractionation was controlled by the removal process, such that those REE with highest affinity for the settling particles became most depleted in the remaining dissolved pool. Modeling, based on Visual MINTEQ version 3.0 and the Stockholm Humic Model after revision and updating, predicted that the dissolved (<0.45 μm) REE pool in the estuary is bound almost entirely to humic substances. Acid sulphate soils, the source of the REE and other metals in the creek water, are widespread on coastal plains worldwide and therefore the REE attenuation patterns and mechanisms identified in the studied estuary are relevant for recognition of similar geochemical processes and conditions in a variety of coastal locations.
Weathering of till in northern Sweden results in the formation of well-developed spodosols. The till is dominated by 1.9–1.8 Ga granitic material. The REE are among the elements most strongly depleted during weathering, and the loss of REE from the E-horizon decreases as the atomic number increases. To study if weathering leads to a change of the Nd isotope composition, we have analysed the Nd isotopic composition of the various horizons including living plants and humus of two profiles of weathered till (typic haplocryods) in northern Sweden. As much as between 65.6 and 75.3% of the Sm and Nd in the <0.2 mm fraction has been lost from the E-horizon, and between 32.5 and 54.7% from the B-horizon. Nd has been lost to a slightly greater extent than Sm. The two C-horizon samples have εNd(0) values of −22.1 and −23.2. Corresponding E-horizon values are −18.1 and −20.2. The B-horizon values are intermediate between the values of the E and C horizons. It is concluded that the weathering leads to a change in the Sm/Nd ratio resulting in a change of the Sm-Nd isotope composition. The plant and humus samples deviate even more from the unweathered till. For one station the results could be interpreted as if the Sm and Nd taken up by the plants had similar isotope characteristics as the amounts of these elements released by weathering in the E-horizon. For the other station it is probable that the Nd isotope composition of the organic samples is dominated by Nd released by till weathering which, however, is mixed with another Nd-source, possibly an airborne component. The explanation to the change of isotope compostion in the till is that a larger proportion of the Nd released by weathering is released from minerals with a lower Sm/Nd ratio than the bulk soil, compared with the amount released from minerals with a higher Sm/Nd ratio. Although the various REE-carrying minerals had the same initial Nd isotopic composition, 1.8–1.9 Ga of decay of 147Sm to 143Nd has resulted in a higher present 143Nd/144Nd ratio in the minerals with a higher Sm/Nd ratio.