The boreal environment is high in dissolved organic carbon (DOC) and iron concentrations. This DOC is enriched in functional groups allowing it to bind strongly with iron and act as a significant source of iron to the coastal and marine environment. As climate change intensifies more extreme weather events will affect the northern hemisphere and boreal environment. These weather events can lead to massive fluxes of material but the impact it will have is currently unknown. Hurricane Larry made landfall on Newfoundland (NL) in 2021 providing an opportunity to investigate how the boreal environment will react to extreme weather events. We sampled three rivers before and after the hurricane to see how DOC and iron concentrations, and colour (a350) were affected by the hurricane. Temperature and pH were found to decrease in a statistically significant manner following the storm with iron and a350 having a significant increase, DOC despite increasing following the storm failed to meet the statistical significance threshold. The rivers chosen had a high abundance of natural landcover which buffered the catchment's response from the hurricane. Pearson's correlations were calculated between the landcover and the ∆ of the variables to access the resilience of the catchments to extreme weather events. Due to the small sample size Pearson's corelations could not achieve statistical significance but the results still provide a novel look into the resilience of the northern boreal regions to extreme weather events. These preliminary results show that a high percentage of forest and peatlands buffered against increases in DOC and colour, with wetlands buffering an increase in iron concentrations. This study represents one of the first to observe boreal catchment responses to extreme weather events such as hurricanes and can serve as basis for more robust studies based in the boreal region.

This study traces dissolved organic matter (DOM) in different water masses of the Arctic Ocean and its effect on the distributions of trace elements (TEs; Fe, Cu, Mn, Ni, Zn, Cd) using fluorescent properties of DOM and the terrigenous biomarker lignin. The Nansen, Amundsen, and Makarov Basins were characterized by the influence of Atlantic water and the fluvial discharge of the Siberian Rivers with high concentrations of terrigenous DOM (tDOM). The Canada Basin and the Chukchi Sea were characterized by Pacific water, modified through contact with productive shelf sediments with elevated levels of marine DOM. Within the surface layer of the Beaufort Gyre, meteoric water (river water and precipitation) was characterized by low concentrations of lignin and tDOM fluorescence proxies as DOM is removed during freezing. High-resolution in situ fluorescence profiles revealed that DOM distribution closely followed isopycnals, indicating the strong influence of sea-ice formation and melt, which was also reflected in strong correlations between DOM fluorescence and brine contributions. The relationship of DOM and hydrography to TEs showed that terrigenous and marine DOM were likely carriers of dissolved Fe, Ni, Cu from the Eurasian shelves into the central Arctic Ocean. Chukchi shelf sediments were important sources of dCd, dZn, and dNi, as well as marine ligands that bind and carry these TEs offshore within the upper halocline in the Canada Basin. Our data suggest that tDOM components represent stronger ligands relative to marine DOM components, potentially facilitating the long-range transport of TE to the North Atlantic.

Humic ligands from boreal rivers have been identified as important sources of iron-binding ligands to the coastal marine environment but remain poorly characterized. A novel method using Fourier transformed infrared spectroscopy (FTIR) was used to identify and quantify iron-binding ligands present in a boreal river in Newfoundland, Canada. 20 to 35% of the total iron load was carried through an artificial salinity gradient, and remained in solution at 35 salinity. Using FTIR combined with linear regression and 2D correlation analysis, we identified two pools of organic ligands, with different behaviour with regards to iron across the salinity gradient. The weaker ligand pool consisted of alkenes, ethers, and esters, and was found to release iron to flocculation at low salinities, and not contribute to iron transport into the marine environment. The stronger ligand group contained carboxylic acids and aliphatic functional groups. This group appears to contain two subgroups, one which was able to retain iron in the dissolved phase at 35 salinity, and another that flocculated out with iron across the salinity gradient. The strong ligands that retain iron in solution through the salinity gradient provide a much-needed source of the micronutrient to the coastal and marine environment, while the other subgroup sequesters iron and carbon in estuarine sediments. The balance between these two subgroups appears to be controlled by the hydrographic and weather conditions at the time of sampling, suggesting a dynamic ligand-iron relationship throughout the year, impacting the biogeochemical cycles of both iron and carbon in contrasting ways.

Phytoplankton growth in the open ocean is critical to carbon fixation and often limited by low iron concentrations. Owing to its low solubility, phytoplankton employ ligands for iron uptake; therefore, ligand binding characterization is important. Herein, a micro immiscible liquid/liquid interface was employed with four ligands through an electrochemically induced facilitated ion-transfer process. Ligands 1,10-phenathroline (phen), 1-nitroso-2-naphthol (N2N), 2-(2-thiazolylazo)-p-cresol (TAC), and salicylaldoxime (SAL), where tested using established facilitated ion-transfer thermodynamics combined with differential pulse voltammetry. Three metal ion/ligand binding stoichiometries were observed for Fe2+:phen, whereas only one was observed with Fe2+ with SAL, N2N, and TAC. Overall binding constants were calculated such that binding strengths can be ranked highest to lowest as phen>N2N>TAC>SAL. Additionally, the formal ion transfer for Fe2+ (0.66 V) for an aqueous/1,2-dichloroethane interface was also determined.

The Arctic Ocean receives a large supply of dissolved organic matter (DOM) from its catchment and shelf sediments, which can be traced across much of the basin's upper waters. This signature can potentially be used as a tracer. On the shelf, the combination of river discharge and sea-ice formation, modifies water densities and mixing considerably. These waters are a source of the halocline layer that covers much of the Arctic Ocean, but also contain elevated levels of DOM. Here we demonstrate how this can be used as a supplementary tracer and contribute to evaluating ocean circulation in the Arctic. A fraction of the organic compounds that DOM consists of fluoresce and can be measured using in-situ fluorometers. When deployed on autonomous platforms these provide high temporal and spatial resolution measurements over long periods. The results of an analysis of data derived from several Ice Tethered Profilers (ITPs) offer a unique spatial coverage of the distribution of DOM in the surface 800 m below Arctic sea-ice. Water mass analysis using temperature, salinity and DOM fluorescence, can clearly distinguish between the contribution of Siberian terrestrial DOM and marine DOM from the Chukchi shelf to the waters of the halocline. The findings offer a new approach to trace the distribution of Pacific waters and its export from the Arctic Ocean. Our results indicate the potential to extend the approach to separate freshwater contributions from, sea-ice melt, riverine discharge and the Pacific Ocean.

The Cover Feature depicts the schematic of the micropipette apparatus along with the electrolytically induced facilitated ion transfer process as well as an example differential pulse voltammetry (DPV). This is overlaid onto a photo of the Newfoundland coast at sunset. More information can be found in the Aricle by Q. Jiang et al.

A major surface circulation feature of the Arctic Ocean is the Transpolar Drift (TPD), a current that transports river-influenced shelf water from the Laptev and East Siberian Seas toward the center of the basin and Fram Strait. In 2015, the international GEOTRACES program included a high-resolution pan-Arctic survey of carbon, nutrients, and a suite of trace elements and isotopes (TEIs). The cruises bisected the TPD at two locations in the central basin, which were defined by maxima in meteoric water and dissolved organic carbon concentrations that spanned 600 km horizontally and similar to 25-50 m vertically. Dissolved TEIs such as Fe, Co, Ni, Cu, Hg, Nd, and Th, which are generally particle-reactive but can be complexed by organic matter, were observed at concentrations much higher than expected for the open ocean setting. Other trace element concentrations such as Al, V, Ga, and Pb were lower than expected due to scavenging over the productive East Siberian and Laptev shelf seas. Using a combination of radionuclide tracers and ice drift modeling, the transport rate for the core of the TPD was estimated at 0.9 +/- 0.4 Sv (10(6) m(3)s(-1)). This rate was used to derive the mass flux for TEIs that were enriched in the TPD, revealing the importance of lateral transport in supplying materials beneath the ice to the central Arctic Ocean and potentially to the North Atlantic Ocean via Fram Strait. Continued intensification of the Arctic hydrologic cycle and permafrost degradation will likely lead to an increase in the flux of TEIs into the Arctic Ocean. Plain Language Summary A major feature of the Arctic Ocean circulation is the Transpolar Drift (TPD), a surface current that carries ice and continental shelf-derived materials from Siberia across the North Pole to the North Atlantic Ocean. In 2015, an international team of oceanographers conducted a survey of trace elements in the Arctic Ocean, traversing the TPD. Near the North Pole, they observed much higher concentrations of trace elements in surface waters than in regions on either side of the current. These trace elements originated from land, and their journey across the Arctic Ocean is made possible by chemical reactions with dissolved organic matter that originates mainly in Arctic rivers. This study reveals the importance of rivers and shelf processes combined with strong ocean currents in supplying trace elements to the central Arctic Ocean and onward to the Atlantic. These trace element inputs are expected to increase as a result of permafrost thawing and increased river runoff in the Arctic, which is warming at a rate much faster than anywhere else on Earth. Since many of the trace elements are essential building blocks for ocean life, these processes could lead to significant changes in the marine ecosystems and fisheries of the Arctic Ocean.

Coastal waters have strong gradients in dissolved organic matter (DOM) quantity and characteristics, originating from terrestrial inputs and autochthonous production. Enclosed seas with high freshwater input therefore experience high DOM concentrations and gradients from freshwater sources to more saline waters. The brackish Baltic Sea experiences such salinity gradients from east to west and from river mouths to the open sea. Furthermore, the catchment areas of the Baltic Sea are very diverse and vary from sparsely populated northern areas to densely populated southern zones. Coastal systems vary from enclosed or open bays, estuaries, fjords, archipelagos and lagoons where the residence time of DOM at these sites varies and may control the extent to which organic matter is biologically, chemically or physically modified or simply diluted with transport off-shore. Data of DOM with simultaneous measurements of dissolved organic (DO) nitrogen (N), carbon (C) and phosphorus (P) across a range of contrasting coastal systems are scarce. Here we present data from the Roskilde Fjord, Vistula and Öre estuaries and Curonian Lagoon; four coastal systems with large differences in salinity, nutrient concentrations, freshwater inflow and catchment characteristics. The C:N:P ratios of DOM of our data, despite high variability, show site specific significant differences resulting largely from differences residence time. Microbial processes seemed to have minor effects, and only in spring did uptake of DON in the Vistula and Öre estuaries take place and not at the other sites or seasons. Resuspension from sediments impacts bottom waters and the entire shallow water column in the Curonian Lagoon. Finally, our data combined with published data show that land use in the catchments seems to impact the DOC:DON and DOC:DOP ratios of the tributaries most.

Dissolved organic matter (DOM) concentrations in sediment porewaters are often orders of magnitude higher than in the overlying water column resulting in a diffusive flux of DOM from sediments. The intensity and fate of this DOM flux is poorly understood. The Gulf of Gdansk in the Southern Baltic Sea is dominated by the Vistula River, one of the largest and most anthropogenically impacted rivers in the Baltic Sea catchment. The sediment characteristics of the region are varied, from mixed sandy conditions near shore to mud sediments in the Gdansk Deep. We investigated the significance of sediment‐derived DOM in the Gulf of Gdansk in comparison to that supplied by the river. Sediment‐derived DOM in the region was found to have an organic matter fluorescence signature distinct from the DOM in the water column. The visible wavelength fluorescence could be used to distinguish organic matter from near shore sediments influenced by riverine sources and organic matter from deeper offshore sediments, influenced by more pelagic sources. Ultraviolet‐A wavelength fluorescence dominated the sediment flux but was rapidly removed in bottom waters suggesting that it may contribute to bottom water oxygen consumption. While there is potential for DOM fluxes from sediments in the Gulf of Gdansk, the high background pelagic concentration of DOM in these waters and the much stronger influence of the Vistula River can mask the contributions from sediments.

Coastal ecosystems act as filters of nutrients from land to the open sea. We investigated the role of eelgrass ( Zostera marina ) metabolism in the coastal filter transforming nitrogen, phosphorus, and organic carbon. Field campaigns following identical methodologies were carried out at two contrasting coastal locations: the mesohaline and nutrient-rich Roskilde Fjord, Denmark, and the mesotrophic brackish Tvärminne archipelago, Finland. Over the 24-h in situ benthic incubations, we measured oxygen concentrations continuously and assessed changes in DOM characteristics and net fluxes of carbon, nitrogen, and phosphorus. Ecosystem metabolism modeled on the basis of the O 2 data showed that the systems were either net heterotrophic (Roskilde Fjord; − 1.6 and − 2.4 g O 2 m −2 day −1 in eelgrass meadow and bare sand, respectively) or had balanced primary production and respiration (Tvärminne; 0.0 and 0.2 g O 2 m −2 day −1 ). Overall, initial nutrient stoichiometry was a key factor determining benthic–pelagic fluxes of nutrients, which exacerbated the deviations from Redfield ratios of N and P, indicating an efficient use of the limiting nutrient. A net diel uptake of dissolved inorganic N was observed at both locations (− 2.3 μmol l −1 day −1 in Roskilde Fjord and − 0.1 μmol l −1 day −1 in Tvärminne). Despite minor changes in dissolved organic carbon concentrations during the incubations, a marked increase of fluorescent DOM was observed at both locations, suggesting rapid heterotrophic processing of the DOM pool. Our results underline that the biogeochemical role of eelgrass in the coastal filter is not inherent, but strongly dependent on the environmental conditions.

Long-term deterioration of water quality is known to reduce the importance of benthic ecosystem metabolism in shallow coastal ecosystems, but drivers of spatial and short-term variability in ecosystem metabolism are poorly understood. We addressed this knowledge gap through detailed seasonal measurements of ecosystem metabolism across depth gradients from shallow (2 to 3 m) eelgrass-dominated to deeper (4 to 5 m) muddy regions of a shallow, productive estuary. Combined measurements of gross primary production (GPP), respiration (R) and, by difference, net ecosystem production (NEP) by the open-water diel oxygen technique and in situ chamber incubations showed high importance of shallow eelgrass habitats for metabolism at the system scale. Seasonal variations in GPP, R and NEP increased with light availability and temp erature with highest NEP in all habitats during the warm and sunny mid-summer. The shallow eelgrass-dominated and neighboring habitats were seasonally net autotrophic (NEP = 0.54 and 0.31 mg O-2 m(-2) d(-1), respectively), compared to net heterotrophy (NEP = -0.26 mg O-2 m(-2) d(-1)) at the deeper muddy site. Detailed studies along depth gradients further confirmed the role of eelgrass as a key driver of spatial differences in ecosystem metabolism across the estuary. Strong northerly winds (> 8 m s(-1)) caused short-term (< 24 h) periods of similar oxygen dynamics and similar apparent productivity in shallow and deeper waters, indicative of efficient lateral mixing, while calm periods (< 4 m s(-1)) enabled formation of 'pockets', i.e. water masses with limited connectivity, which exacerbated the metabolic differences between shallow and deep sites.

The bio-essential trace metal iron (Fe) has poor inorganic solubility in seawater, and therefore dissolution is dependent on organic complexation. The Arctic Ocean is subject to strong terrestrial influences which contribute to organic solubility of Fe, particularly in the surface. These influences are subject to rapid changes in the catchments of the main contributing rivers. Here we report concentrations and binding strengths of Fe-binding organic ligands in relation to spectral properties of Dissolved Organic Matter (DOM) and concentrations of humic substances. Full-depth profiles of Fe and Fe-binding organic ligands were measured for 11 stations, good agreement to previous studies was found with ligand concentrations between 0.9 and 2.2equivalentnM of Fe (Eq.nMFe) at depths>200m. We found nutrient-like profiles of Fe in the Atlantic-influenced Nansen basin, surface enrichment in the surface over the Amundsen and Makarov basins and scavenging effects in the deep Makarov basin. A highly detailed surface transect consisting of two sections crossing the surface flow from the Siberian continental shelf to the Fram Strait, the TransPolar Drift (TPD), clearly indicates the flow path of the riverine contribution to Fe and Fe-binding organic ligands with concentrations of 0.7 to 4.4nM and 1.6 to 4.1Eq.nMFe, respectively. This is on average 4.5 times higher in DFe and 1.7 times higher in Fe-binding organic ligands than outside the TPD flow path. Conditional binding strengths of ligands in the entire dataset were remarkably similar at 11.45≤LogK′≤12.63. Increased organic Fe-binding organic ligand concentrations were evident in the Arctic Ocean surface. To better identify the organic substances responsible for Fe complexation in the Arctic Ocean, diverse analytical approaches and a standard other than Suwannee River Fulvic Acid are recommended.

Table S1.Nutrients (in µM) and metabolic rates (mmol O 2 m -3 d -1 ) for all days and treatments for the four experiments.Experiment Day Samp le Mean TDN (µM) SE Mean NOx SE Mean NO2 SE Mean

In the summer of 2015 a coordinated pan-arctic GEOTRACES study was executed by the Canadian CCGS Amundsen, the US CGC Healy and the German RV Polarstern. For intercalibration purposes, three cross-over stations were visited, one of them at the North Pole. The Polarstern expedition visited the Nansen, Amundsen and Mendeleev basins. On sections across these basins and the Gakkel and Lomonosov Ridge we collected samples for the full set of GEOTRACES key parameters and many additional analyses. The team of natural radionuclides took samples for U-series nuclides. During earlier work in the central Arctic with Polarstern we have quantified export production with 234Th, studied the interaction between scavenging and deep water ventilation using 230Th and 231Pa, and investigated the shelf-basin exchange with radium isotopes. I will give an overview of these results obtained on earlier expeditions, mention first results of the 2015 expedition, and discuss how these tracers can help us to observe changes in deep water circulation and particle flux that may be related to Arctic Oscillation or caused by sea ice retreat.

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 a 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.

Recent studies report trends of strongly increasing iron (Fe) concentrations in freshwaters. Since Fe is a key element with a decisive role in the biogeochemical cycling of major elements, it is important to understand the mechanisms behind these trends. We hypothesized that variations in Fe concentration are driven mainly by redox dynamics in hydraulically connected soils. Notably, Fe(III), which is the favored oxidation state except in environments where microbial activity provide strong reducing intensity, has several orders of magnitude lower water solubility than Fe(II). To test our hypothesis, seasonal variation in water chemistry, discharge, and air temperature was studied in three Swedish rivers. Methylmercury and sulfate were used as indicators of seasonal redox changes. Seasonal variability in water chemistry, discharge, and air temperature in the Emån and Lyckeby Rivers implied that the variation in Fe was primarily driven by the prevalence of reducing conditions in the catchment. In general, high Fe concentrations were observed when methylmercury was high and sulfate was low, indicative of reducing conditions. The Fe concentrations showed no or weak relationships with variations in dissolved organic matter concentration and aromaticity. The seasonal variation in Fe concentration of the Ume river was primarily dependent on timing of the snowmelt in high‐ versus low‐altitude areas of the catchment. There were long‐term trends of increasing temperature in all catchments and also trends of increasing discharge in the southern rivers, which should increase the probability for anaerobic conditions in space and time and thereby increase Fe transport to the aquatic systems.