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- Dahlqvist, Ralf, 1973, et al.
(författare)
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Association of calcium with colloidal particles and speciation of calcium in the Kalix and Amazon rivers
- 2004
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Ingår i: Geochimica Et Cosmochimica Acta. - : Elsevier BV. - 0016-7037 .- 1872-9533. ; 68:20, s. 4059-4075
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Tidskriftsartikel (refereegranskat)abstract
- 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 similar to5 to 10 nm in diameter, shifting to smaller sizes (<5 mm) 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. Copyright (C) 2004 Elsevier Ltd.
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| 2. |
- Dahlqvist, Ralf, 1973-
(författare)
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Speciation and fractionation of Ca and the REE in fresh and marine waters
- 2004
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This study is concerned with speciation and fractionation of the rare earth elements (REE) and calcium (Ca) in aqueous solutions. The aim is to investigate the chemical states and physical sizes in which these elements can be present. The REE (including neodymium) and Ca have contrasting geochemical behavior in aqueous solutions. Ca is a major dissolved element, while the REE are trace components and highly reactive with aquatic particles.The major interests of the five papers included in this thesis are the following:· Papers I and V deal with the behavior of neodymium (Nd) and its isotopes in the Kalix River and some marine waters.· The diffusive gradients in thin-films (DGT) method is developed for measuring Ca and Mg in Paper II.· Paper III presents a speciation and fractionation study of Ca in the Kalix and Amazonian rivers.· The rare earth elements and their carrier phases are investigated in the Kalix river in Paper IV.For most elements a detailed study of speciation and fractionation can not be performed using only one method. This is due to the overall heterogeneity of the material, considering both size and chemical composition, which is present in aquatic solutions. During this project the aquatic geochemistry of the REE and Ca has been studied using mainly three methods; cross-flow filtration (CFF), field-flow fractionation (FFF) and diffusive gradients in thin-films (DGT). Field work has to a large part been conducted in the Kalix River, in northern Sweden, which is one of the last pristine river systems in Europe. Some field work has also been conducted in the Baltic Sea and the Arctic Ocean. Results from Amazonian rivers are also presented.These are the main conclusions from this work:The DGT technique works equally well for measuring Ca and Mg in natural waters as previously reported for trace metal.A significant colloidal phase for Ca could be detected in the Kalix River and in different Amazonian rivers. This was concluded independently using both CFF and FFF.Variations in REE signatures in the Kalix River suggests two different pathways for the REE during weathering and release form soil profiles and transport in the river.No significant variation in Nd-isotopic composition could be detected in the Kalix River although concentrations varied by a factor of ~10. This suggests that there is one major source for Nd in the river although different pathways for the REE may exist.A study of Nd in the Kalix River, the Baltic Sea and the Arctic Ocean showed that the isotopic compositions in the diffusible fractions were similar to water samples. However, the relative amount of diffusible Nd increased with salinity, probably reflecting the lower concentration of colloidal and particulate material in marine waters.
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