The water quality in headwater streams depends on the groundwater origin and its transport pathways before it eventually discharges as surface water. In this case study, we present the Ce anomaly of over 100 hemiboreal headwater streams in Sweden and discuss the potential of the Ce anomaly to define two stream end members as proxies for the stream origin. The data show a relation between topography and the Ce anomaly, with more negative values (−0.8 to −0.4) in hilly catchments with distinct slopes, defined as an oxidized groundwater end member. The second end member is dominated by groundwater discharge from reduced, organic-rich riparian and wetland soils (reduced groundwater) having small Ce anomalies (−0.3 to zero). Element concentrations show a wide range, depending on the end member of the stream. For example, redox elements (Fe, Mn, S and N) show concentrations up to five times in streams with small negative Ce anomalies (reduced groundwater) compared to the concentrations in streams with large negative Ce anomalies. While element concentrations (of the classic redox elements Fe, Mn, S, N) show seasonal variations due to a summer drought period and the resulting reduced conditions, the Ce anomaly is constant, offering an excellent indicator of the dominant groundwater flow paths regardless of seasonal variations.

Riverine Fe input is the primary Fe source for the ocean. This study is focused on the distribution of Fe along the Lena River freshwater plume in the Laptev Sea using samples from a 600 km long transect in front of the Lena River mouth. Separation of the particulate ( >  0.22 μm), colloidal (0.22 μm–1 kDa), and truly dissolved (<  1 kDa) fractions of Fe was carried out. The total Fe concentrations ranged from 0.2 to 57μM with Fe dominantly as particulate Fe. The loss of >  99% of particulate Fe and about 90% of the colloidal Fe was observed across the shelf, while the truly dissolved phase was almost constant across the Laptev Sea. Thus, the truly dissolved Fe could be an important source of bioavailable Fe for plankton in the central Arctic Ocean, together with the colloidal Fe. Fe-isotope analysis showed that the particulate phase and the sediment below the Lena River freshwater plume had negative δ⁵⁶Fe values (relative to IRMM-14). The colloidal Fe phase showed negative δ⁵⁶Fe values close to the river mouth (about -0.20 ‰) and positive δ⁵⁶Fe values in the outermost stations (about +0.10 ‰). We suggest that the shelf zone acts as a sink for Fe particles and colloids with negative δ⁵⁶Fe values, representing chemically reactive ferrihydrites. The positive δ⁵⁶Fe values of the colloidal phase within the outer Lena River freshwater plume might represent Fe oxyhydroxides, which remain in the water column, and will be the predominant δ⁵⁶Fe composition in the Arctic Ocean.

During recent decades, much focus has been put on the iron (Fe) isotope ratios in soils, rivers, and oceans, while studies on the variation in headwater streams are scarce. Here we assess seasonal water chemical data from 104 hemiboreal headwater streams. Between summer and late autumn, decreasing Fe concentrations and simultaneously increasing sulfate and nitrate concentrations suggest a shift from reduced to oxidized conditions in the soils along the main groundwater flow paths. Fe isotope data, obtained from a subpopulation of 16 streams, show low δ56Fe ratios during summer drought, indicating an important influx of reduced groundwater to the streams with primarily Fe(II) as an important Fe source. In total, the δ56Fe data ranged between −0.8 ± 0.1 and 1.8 ± 0.1‰ with the lowest values in summer and maximum δ56Fe ratios in late autumn or spring, indicating an influx of more oxidized, less Fe(II) rich groundwater during those seasons. Local differences in δ56Fe ratios between the headwater streams, seemed to be driven by the different soil redox status of the catchments. The streams with the lowest δ56Fe ratios during summer are characterized by a small share (4.4 ± 6.6%) of wetlands, indicating discharge of reduced groundwater from mainly anoxic, moist, organic-rich mineral soils during drought. Relatively high total organic carbon (TOC) concentrations (2.4 ± 1.1 mM) and low pH (5.2 ± 0.8) may have restricted efficient Fe(II) oxidation in streamwater especially during the late autumn survey. Our results from hemiboreal headwater streams reveal the importance of climatic, pedogenic, and land cover-derived controls on the provenance of stream Fe loads that is likely broadly applicable to similar streams elsewhere.

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.

We have studied iron (Fe)-isotope signals in particles (> 0.22 µm) and the dissolved phase (< 0.22 µm) in two subarctic, boreal rivers, their estuaries and the adjacent sea in northern Sweden. Both rivers, the Råne and the Kalix, are enriched in Fe and organic carbon (up to 29 µmol/L and up to 730 µmol/L, respectively). Observed changes in the particulate and dissolved phase during spring flood in May suggest different sources of Fe to the rivers during different seasons. While particles show a positive Fe-isotope signal during winter, during spring flood, the values are negative. Increased discharge due to snowmelt in the boreal region is most times accompanied by flushing of the organic-rich sub-surface layers. These upper podzol soil layers have been shown to be a source for Fe-organic carbon aggregates with a negative Fe-isotope signal. During winter, the rivers are mostly fed by deep groundwater, where Fe occurs as Fe(oxy)hydroxides, with a positive Fe-isotope signal. Flocculation during initial estuarine mixing does not change the Fe-isotope compositions of the two phases. Data indicate that the two groups of Fe aggregates flocculate diversely in the estuaries due to differences in their surface structure. Within the open sea, the particulate phase showed heavier δ56Fe values than in the estuaries. Our data indicate the flocculation of the negative Fe-isotope signal in a low salinity environment, due to changes in the ionic strength and further the increase of pH.

The geochemistry of tungsten (W) in the environment is poorly studied. Tungsten usually occurs in low concentrations in natural waters and is not very mobile. For this study, we analyzed W together with molybdenum (Mo) in the dissolved and particulate fractions of two boreal estuaries during different seasons. Additionally, we sampled first-order streams that drain different landscape types and the receiving northern Baltic Sea. Furthermore, surface sediment from the estuaries was analyzed to obtain a comprehensive overview of the distribution of W and Mo in a boreal environment.

Both elements showed different distribution patterns during different seasons. While they decreased in the dissolved fraction during spring discharge, in winter, their concentrations were elevated. Molybdenum exhibited non-conservative behavior along the salinity gradient in winter, which was probably caused by its release from underlying sediments. In the particulate fraction, we found opposite behaviors for Mo and W, with higher particulate W and lower particulate Mo during spring discharge.

Molybdenum and W underwent fractionation from land to sea, indicating the different mobilities of these oxyanions. The Mo/W ratio in the dissolved fraction was mainly determined by the Mo concentration, as the W concentration varied only in a narrow range from first-order streams to the Bothnian Bay. In the particulate fraction, the Mo/W ratio appeared to be affected by scavenging processes and showed only small variations.

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/Fe_bulk 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.

Isotopic information may provide powerful insight into the elemental cycling processes which occur in natural compartments. Further implementation of isotopic techniques in natural sciences requires a better understanding of the range of elemental and isotopic compositional variability in environmental matrices. This study assesses the local-scale concentration and isotopic composition variability of nine elements: boron (B), cadmium (Cd), chromium (Cr), copper (Cu), iron (Fe), lead (Pb), strontium (Sr), thallium (Tl), and zinc (Zn) in lysimetric waters, mushrooms, litter, needles, leaves, and lichens. Sequential extractions were also performed on soil samples from 6 depth profiles providing more detailed information on the variability of elemental concentrations and isotope ratios between the elemental pools present in soil. For most of the sample types studied the range of isotopic variability between samples spans almost the entire ranges reported in the literature for natural samples. These results represent a starting point for discussing the role of natural variability in isotopic studies (for example, as a limiting factor in the use of isotopic mixing models) and a baseline for future in-depth studies examining the controls on isotope fraction in natural systems

Understanding geochemical processes in mining environments are essential to waste management decisions including remediation. In an attempt to understand geochemical processes, chemical data have mostly been used but these have oft en led to inaccurate conclusions. Th erefore, in this work 87Sr/86Sr, Sr/Ca and other elemental ratios (Ca/K and Rb/Sr) in leachates were employed to constrain the geochemical processes in an abandoned tungsten (W) tailings in Yxsjöberg, South-Central Sweden. Th e results of this study indicate that coupling chemical ratios with 87Sr/86Sr ratios off er better insights in discriminating between diff erent geochemical processes in mine wastes

Interpretation of geochemical data based primarily on elemental concentrations often lead to ambiguous results due to multiple potential sources including mineral weathering, atmospheric input, biological cycling, mineral precipitation and exchange processes. The ⁸⁷Sr/⁸⁶Sr ratio is however not fractionated by these processes. In this study, Sr isotope (⁸⁷Sr/⁸⁶Sr) ratios have been coupled with chemical data of Sr and Rb-bearing minerals, tailings and leachates (water-soluble) to gain insight into the geochemical processes occurring within the Yxsjöberg Cu-W mine tailings, Sweden. The tailings have been exposed to oxidizing conditions resulting in three geochemical zones namely (i) oxidized, (ii) transition and (iii) unoxidized zones. Leachates from the oxidized zone are acidic (pH = 3.6–4.5) and contain elevated concentrations of metals (e.g. Fe, Cu and Zn) and SO4. The low pH has also led to subsequent weathering of most silicates, releasing Al, Ca, Mg and Na into solution. The ⁸⁷Sr/⁸⁶Sr ratio in the tailings ranges from 0.84787 to 1.26640 in the oxidized zone, 0.92660–1.06788 in the transition zone, whilst the unoxidized zone has values between 0.76452 and 1.05169. For the leachates, the ⁸⁷Sr/⁸⁶Sr ratio ranges from 2.44479 to 5.87552 in the oxidized zone, 1.37404–1.68844 in the transition zone and 1.03697–2.16340 in the unoxidized zone. Mixing (between mineral weathering and atmospheric sources) was identified as the major process regulating the Sr composition of the tailings and leachates. The highly radiogenic signatures of the leachates in the oxidized zone suggests weathering of biotite, K-feldspar and muscovite. Despite the very radiogenic signatures in the oxidized zone, increments in Ca/K ratios, Be, Ce, Tl, Al, Fe and SO4 concentrations in the water-soluble phase were recorded in its lower parts which suggests the dissolution of amphibole, pyroxene, plagioclase, fluorite, gypsum, Al and Fe –(oxy) hydroxides as well as cation exchange by clay minerals. Presence of clay minerals has led to the partial retainment of radiogenic ⁸⁷Sr/⁸⁶Sr resulting in increased ⁸⁷Sr/⁸⁶Sr in the solid tailings material at these depths. The ⁸⁷Sr/⁸⁶Sr ratios of the water-soluble phase in the transition zone is similar to that of helvine and could indicate its dissolution. In the upper part of the oxidized zone, the ⁸⁷Sr/⁸⁶Sr ratios and trends of Be, Ca, SO4, Tl and Zn in the water-soluble phase suggest the dissolution of gypsum which precipitated from a leachate with the isotopic signature of helvine. In the lower part of the unoxidized zone, elevated concentrations of W were recorded suggesting scheelite weathering. But the ⁸⁷Sr/⁸⁶Sr ratios are higher than that expected from dissolution of scheelite and indicates additional processes. Possible sources include biotite weathering and groundwater. This study reveals that when interpreting geochemical processes in mine waste environments, ⁸⁷Sr/⁸⁶Sr should be considered in addition to chemical constituents, as this isotopic tracer offers better insights into discriminating between different solute sources.