Seasonal contribution of terrestrial organic matter and biological oxygen demand to the Baltic Sea from three contrasting river catchments

To examine the potential influence of terrestrially derived DOM on the Baltic Sea, a year-long study of dissolved organic matter (DOM) was performed in three river catchments in Sweden. One catchment drains into the Bothnian Sea, while two southern catchments drain into the Baltic proper. Dissolved organic carbon (DOC) concentrations were positively correlated with discharge from forested catchments over the year. While the overall concentrations of DOC were several times higher in the southern two catchments, higher discharge in the northern catchment resulted in the annual loadings of DOC being on the same order of magnitude for all three catchments. Biological oxygen demand (BOD) was used as a proxy for the lability of carbon in the system. The range of BOD values was similar for all three catchments, however, the ratio of BOD to DOC (an indication of the labile fraction) in Ume river was four times higher than in the southern two catchments. Total annual BOD loading to the Baltic Sea was twice as high in the northern catchment than in the two southern catchments. Lower winter temperatures and preservation of organic matter in the northern catchment combined with an intense spring flood help to explain the higher concentrations of labile carbon in the northern catchment. Lower lability of DOM as well as higher colour in the southern catchments suggest that wetlands (i.e. peat bogs) may be the dominant source of DOM in these catchments, particularly in periods of low flow. With climate change expected to increase precipitation events and temperatures across the region, the supply and quality of DOM delivered to the Baltic Sea can also be expected to change. Our results indicate that DOM supply to the Baltic Sea from boreal rivers will be more stable throughout the year, and potentially have a lower bioavailability

Organic iron complexes enhance iron transport capacity along estuarine salinity gradients of Baltic estuaries

Rivers discharge a notable amount of dissolved Fe (1:5×109 mol yr-1) to coastal waters but are still not considered important sources of bioavailable Fe to open marine waters. The reason is that the vast majority of particular and dissolved riverine Fe is considered to be lost to the sediment due to aggregation during estuarine mixing. Recently, however, several studies demonstrated relatively high stability of riverine Fe to salinity-induced aggregation, and it has been proposed that organically complexed Fe (Fe-OM) can "survive" the salinity gradient, while Fe (oxy)hydroxides are more prone to aggregation and selectively removed. In this study, we directly identified, by X-ray absorption spectroscopy, the occurrence of these two Fe phases across eight boreal rivers draining into the Baltic Sea and confirmed a significant but variable contribution of Fe-OM in relation to Fe (oxy)hydroxides among river mouths. We further found that Fe-OM was more prevalent at high flow conditions in spring than at low flow conditions during autumn and that Fe-OM was more dominant upstream in a catchment than at the river mouth. The stability of Fe to increasing salinity, as assessed by artificial mixing experiments, correlated well to the relative contribution of Fe-OM, confirming that organic complexes promote Fe transport capacity. This study suggests that boreal rivers may provide significant amounts of potentially bioavailable Fe beyond the estuary, due to organic matter complexes

Spring flood induced shifts in Fe speciation and fate at increased salinity

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

Differential Trends in Iron Concentrations of Boreal Streams Linked to Catchment Characteristics

Increasing iron (Fe) concentrations have been reported for freshwaters across northern Europe over the last decades. This increase, together with elevated concentrations of dissolved organic carbon (DOC), leads to browning of freshwaters, which affects aquatic organisms, ecosystem functioning, biogeochemical cycles, and brings challenges to drinking water production. However, how such increasing trends in stream Fe concentrations reflect the contribution of different catchment sources remains poorly resolved. Here, we explored how catchment characteristics, that is, mires and coniferous soils, regulate spatial and temporal patterns of Fe in a boreal stream network. For this, we determined Fe speciation in riparian and mire soils, and studied temporal Fe dynamics in soil-water and stream-water over a span of 18 years. Positive Fe trends were found in the solution of the riparian soil, while no long-term trend was observed in the mire. These differences were reflected in stream-water, where three headwater streams dominated by coniferous cover also displayed positive Fe trends, whereas the mire dominated stream showed no trend. Surprisingly, the majority of higher order streams showed declining Fe trends, despite long-term increases in DOC. In addition, we found that an extreme drought event led to a prolonged release of Fe and DOC from the riparian soils, that could have long-term effects on stream Fe concentrations. Our results show that riparian forest soils can be major contributors to ongoing increases in freshwater Fe concentrations and that drought can further promote the release of Fe from organic soils

Spruce forest afforestation leading to increased Fe mobilization from soils

Increasing exports of Fe and DOC from soils, causing browning of freshwaters, have been reported in recent decades in many regions of the northern hemisphere. Afforestation, and in particular an increase of Norway spruce forest in certain regions, is suggested as a driver behind these trends in water chemistry. In this study, we tested the hypothesis that the gradual accumulation of organic soil layers in spruce forests, and subsequent increase in organic acid concentrations and acidity enhances mobilization of Fe. First generation Norway spruce stands of different ages (35, 61, 90 years) and adjacent arable control plots were selected to represent the effects of aging forest. Soil solutions were sampled from suction lysimeters at two depths (below organic soil layer and in mineral soil) during two years, and analyzed for Fe concentration, Fe speciation (XAS analysis), DOC, metals, major anions and cations. Solution Fe concentrations were significantly higher in shallow soils under older spruce stands (by 5- and 6-fold) than in control plots and the youngest forest. Variation in Fe concentration was best explained by variation in DOC concentration and pH. Moreover, Fe in all soil solutions was present as mononuclear Fe(III)-OM complexes, showing that this phase is dominating Fe translocation. Fe speciation in the soil was also analyzed, and found to be dominated by Fe oxides with minor differences between plots. These results confirmed that Fe mobilization, by Fe(III)-OM complexes, was higher from mature spruce stands, which supports that afforestation with spruce may contribute to rising concentrations of Fe in surface waters

Mass and UV-visible spectral fingerprints of dissolved organic matter: sources and reactivity

Advanced analytical techniques have revealed a high degree of complexity in the chemical makeup of dissolved organic matter (DOM). This has opened the door for a deeper understanding of the role of DOM in the aquatic environment. However, the expense, analytical cost, and challenges related to interpretation of the large datasets generated by these methods limit their widespread application. Optical methods, such as absorption and fluorescence spectroscopy are relatively inexpensive and easy to implement, but lack the detailed information available in more advanced methods. We were able to directly link the analysis of absorption spectra to the mass spectra of DOM using an in-line detector system coupled to multivariate data analysis. Monthly samples were taken from three river mouths in Sweden for one year. One subset of samples was exposed to photochemical degradation and another subset was exposed to long-term (4 months) biological degradation. A principle component analysis was performed on the coupled absorption-mass spectra data. Loading spectra for each principle component show distinct fingerprints for both reactivity (i.e. photochemical, biological degradation) and source (i.e. catchment land cover, temperature, hydrology). The fingerprints reveal mass-to-charge values that contribute to optical signals and characteristics seen in past studies, and emphasise the difficulties in interpreting changes in bulk CDOM characteristics resulting from multiple catchment processes. The approach provides a potential simple method for using optical indicators as tracers for more complex chemical processes both with regards to source material for DOM and the past reactive processing of DOM

Effects of wastewater treatment plant effluent inputs on planktonic metabolic rates and microbial community composition in the Baltic Sea

The Baltic Sea is the world's largest area suffering from eutrophication-driven hypoxia. Low oxygen levels are threatening its biodiversity and ecosystem functioning. The main causes for eutrophication-driven hypoxia are high nutrient loadings and global warming. Wastewater treatment plants (WWTP) contribute to eutrophication as they are important sources of nitrogen to coastal areas. Here, we evaluated the effects of wastewater treatment plant effluent inputs on Baltic Sea planktonic communities in four experiments. We tested for effects of effluent inputs on chlorophyll <i>a</i> content, bacterial community composition, and metabolic rates: gross primary production (GPP), net community production (NCP), community respiration (CR) and bacterial production (BP). Nitrogen-rich dissolved organic matter (DOM) inputs from effluents increased bacterial production and decreased primary production and community respiration. Nutrient amendments and seasonally variable environmental conditions lead to lower alpha-diversity and shifts in bacterial community composition (e.g. increased abundance of a few cyanobacterial populations in the summer experiment), concomitant with changes in metabolic rates. An increase in BP and decrease in CR could be caused by high lability of the DOM that can support secondary bacterial production, without an increase in respiration. Increases in bacterial production and simultaneous decreases of primary production lead to more carbon being consumed in the microbial loop, and may shift the ecosystem towards heterotrophy