Iron isotopes in aquatic systems

• 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.

Ämnesord

NATURVETENSKAP  -- Geovetenskap och miljövetenskap -- Geokemi (hsv//swe)

NATURAL SCIENCES  -- Earth and Related Environmental Sciences -- Geochemistry (hsv//eng)

Nyckelord

Applied Geochemistry

Tillämpad geokemi

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