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Spring flood induced shifts in Fe speciation and fate at increased salinity
Department of Science and Environment, Roskilde University, Roskilde, Denmark.
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering. (Applied Geochemistry)ORCID iD: 0000-0002-7313-5833
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering. (Applied Geochemistry)ORCID iD: 0000-0003-2276-0564
Centre for Environmental and Climate Research & Department of Biology, Lund University, Lund, Sweden.
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2019 (English)In: Applied Geochemistry, ISSN 0883-2927, E-ISSN 1872-9134, Vol. 109, article id 104385Article in journal (Refereed) Published
Abstract [en]

Rivers have traditionally been viewed as negligible sources of iron (Fe) to marine waters, as most Fe gets lost during estuarine mixing. However, recent findings demonstrate that Fe from boreal rivers display a higher resistance towards salinity-induced aggregation, presumably due to stabilizing interactions with organic matter. Previous studies have shown that Fe (oxy)hydroxides are selectively removed by aggregation processes, and that organic Fe complexes are less affected by increasing salinity. It has been further proposed that Fe speciation varies in response to seasonal differences in hydrology. In this study X-ray absorption spectroscopy (XAS) was used to determine the temporal variation in Fe speciation and the connection to Fe stability in response to increasing salinity in two boreal rivers (Kalix and Råne River), with the purpose to better understand the fate of riverine Fe export. Sampling was done from winter pre-flood, over the spring flood, to post-flood conditions (early April until mid June). In addition, parallel analyses for Fe speciation and isotope composition (δ56Fe relative to IRMM-14) were made on river samples, as well as salinity-induced aggregates and the fraction remaining in suspension, with the main objective to test if δ56Fe reflect the speciation of Fe.

The contribution of organically complexed Fe increased during spring flood compared to the pre- and post-flood, as did Fe transport capacity. However, since Fe (oxy)hydroxides were dominating throughout the sampling period, the seasonal variability was small. Interestingly, salinity-induced aggregation experiments revealed that Fe (oxy)hydroxides, which dominated aggregates, displayed lower δ56Fe than in the river samples Fe, while organic Fe complexes in suspension had higher δ56Fe values. The seasonal variability in Fe isotope signature could not be simply linked to Fe speciation, but was probably also influenced by variation in source areas of Fe and processes along the flow-path that alter both Fe speciation and isotopic composition.

Place, publisher, year, edition, pages
Elsevier, 2019. Vol. 109, article id 104385
Keywords [en]
Fe geochemistry, Fe speciation, Fe isotopes, Organically complexed Fe, Fe (oxy)hydroxides, Boreal, Sub-arctic, Transport capacity, Salinity gradient, XAS
National Category
Geochemistry
Research subject
Applied Geochemistry
Identifiers
URN: urn:nbn:se:ltu:diva-73761DOI: 10.1016/j.apgeochem.2019.104385ISI: 000490982400019Scopus ID: 2-s2.0-85070319579OAI: oai:DiVA.org:ltu-73761DiVA, id: diva2:1306843
Note

Validerad;2019;Nivå 2;2019-08-20 (johcin);

Artikeln har tidigare förekommit som manuskript i avhandling.

Available from: 2019-04-25 Created: 2019-04-25 Last updated: 2021-10-24Bibliographically approved
In thesis
1. Iron isotopes in aquatic systems
Open this publication in new window or tab >>Iron isotopes in aquatic systems
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Alternative title[sv]
Järnisotoper i akvatiska system
Abstract [en]

The cycling of iron (Fe) is a key component for understanding water quality and biogeochemical processes. It serves as mediator during biotic and abiotic processes, as electron acceptor during the degradation of organic matter, as surface for trace element and organic matter adsorption, and is necessary for primary production processes. Since the beginning of Fe isotope studies, researchers focussed on the ratios in soils, rivers and oceans in various environments. The aim of this study was to characterize the Fe isotope ratios from the source (e.g. soils), along the river course, through the estuaries and into the adjacent sea within the boreal landscape. Therefore, seasonal sampling of water from Swedish headwater streams (2016/2017), rivers (2016), estuaries (2013/2014) and the Baltic Sea (2013/2014) were conducted, with the purpose to better understand the role and fate of riverine Fe export. Fe is transported in two main phases from the headwater streams into the oceans: organic Fe complexes and Fe(oxy)hydroxide. It has been proposed that these Fe phases varies in response to seasonal differences in hydrology.

                      This thesis includes the first Fe isotope dataset describing seasonal variations of headwater streams on a regional scale. In the headwater streams positive and negative Fe isotopes ratios can be used to distinguish between different Fe phases. Furthermore, Fe isotope ratios in headwater streams could verify regional drought periods and the subsequent rewetting of the subsurface soils.

Within the rivers and estuaries, we found positive Fe isotopes in the dissolved phase (< 0.22µm) and negative Fe isotopes (> 0.22µm) in the particulate phase during high discharge. The correlation between different chemical parameters, Fe and DOC showed that the Fe isotope composition during spring flood is evolving in the upper soil layers of headwater streams. Therefore, the lighter Fe isotope signal is correlated to the organic-rich soil layers of the riparian zones in forested catchments. During baseflow, particulate Fe has a positive Fe isotope signal. This shows that the Fe has different origin throughout the season within one catchment.

Salt-induced flocculation in the estuaries and under experimental conditions, is removing about 80 % of the dissolved and particulate Fe. Newly formed colloids and particles aggregate and sediment due to small changes in salinity. This major flocculation at low salinities might cause an underestimation of riverine Fe flux. Interestingly, salinity-induced aggregation experiments revealed that Fe(oxy)hydroxide, which dominated aggregates, displayed lower Fe isotope ratios than in the river samples Fe, while organic Fe complexes in the suspension had higher Fe isotope values. The seasonal variability in Fe isotope values could not be simply linked to Fe phases but was probably also influenced by variation in source areas of Fe and processes along the flow-path that alter both Fe phases and isotopic composition.

Within the estuarine mixing zone, no Fe isotope fractionation was observed. The Fe isotope signal is constant over time and space, which excludes fractionation processes for example by oxidation. The Fe isotope signal within the Bothnian Bay was positive showing that different surface properties of Fe-OC and Fe(oxy)hydroxide aggregates lead to the flocculation of negative Fe aggregates.

Place, publisher, year, edition, pages
Luleå: Luleå University of Technology, 2019
Series
Doctoral thesis / Luleå University of Technology 1 jan 1997 → …, ISSN 1402-1544
National Category
Geochemistry
Research subject
Applied Geochemistry
Identifiers
urn:nbn:se:ltu:diva-73763 (URN)978-91-7790-376-5 (ISBN)978-91-7790-377-2 (ISBN)
Public defence
2019-06-20, F531, Luleå, 10:00 (English)
Opponent
Supervisors
Available from: 2019-04-25 Created: 2019-04-25 Last updated: 2019-06-05Bibliographically approved

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Conrad, SarahIngri, Johan

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