Immobilization of Agaricus bisporus Polyphenol Oxidase 4 on mesoporous silica: Towards mimicking key enzymatic processes in peat soils.

HYPOTHESIS: The use of immobilized enzyme-type biocatalysts to mimic specific processes in soil can be considered one of the most promising alternatives to overcome the difficulties behind the structural elucidation of riverine humic-derived iron-complexes. Herein, we propose that the immobilization of the functional mushroom tyrosinase, Agaricus bisporus Polyphenol Oxidase 4 (AbPPO4) on mesoporous SBA-15-type silica could contribute to the study of small aquatic humic ligands such as phenols. EXPERIMENTS: The silica support was functionalized with amino-groups in order to investigate the impact of surface charge on the tyrosinase loading efficiency as well as on the catalytic performance of adsorbed AbPPO4. The oxidation of various phenols was catalyzed by the AbPPO4-loaded bioconjugates, yielding high levels of conversion and confirming the retention of enzyme activity after immobilization. The structures of the oxidized products were elucidated by integrating chromatographic and spectroscopic techniques. We also evaluated the stability of the immobilized enzyme over a wide range of pH values, temperatures, storage-times and sequential catalytic cycles. FINDINGS: This is the first report where the latent AbPPO4 is confined within silica mesopores. The improved catalytic performance of the adsorbed AbPPO4 shows the potential use of these silica-based mesoporous biocatalysts for the preparation of a column-type bioreactor for in situ identification of soil samples.

Combining iron affinity-based fractionation with non-targeted LC-ESI-TOFMS for the study of iron-binding molecules in dissolved organic matter.

The low solubility of inorganic iron(III) in seawater leads to very limited availability of this important micronutrient for marine organisms. Estuarine or oceanic iron is almost entirely bound to organic ligands of mainly unknown chemical structure. In this context, riverine input of iron rich, land-derived dissolved organic matter (DOM) can play an important role in coastal areas and investigation of potential Fe-ligands in DOM is of high interest. Previous studies have suggested that iron is predominantly bound to the high molecular weight fraction of DOM, but distributed over the entire size range. Logically, structural elucidation needs to start from the smallest building blocks. A model study targeting low molecular weight iron-binding constituents in Suwannee River natural organic matter (NOM) using Fe-loaded Chelex or silica for immobilized-metal affinity (IMAC)-based fractionation was undertaken. The binding strengths of different compounds could be qualitatively assessed using a differential analysis workflow. IMAC-fractionated samples were acidified and analyzed via liquid chromatography high resolution mass spectrometry (LC-HRMS) and molecular formulas were assigned using state of the art software. A total of 144 Fe-binding constituents in Suwannee River NOM were found to be of interest with the largest number observed to interact with Chelex at pH 4 (55%), and the smallest with silica at neutral pH (24%). Most binding constituents were found in the lignin- and tannin-type region of the van Krevelen plot. Results from this study support the hypothesis that very low molecular weight constituents (below 300 Da) can play a role in the iron binding mechanism of DOM and demonstrate that the employed analytical workflow is suitable for their detection.

Northern High-Latitude Organic Soils As a Vital Source of River-Borne Dissolved Iron to the Ocean.

Organic soils in the Arctic-boreal region produce small aquatic humic ligands (SAHLs), a category of naturally occurring complexing agents for iron. Every year, large amounts of SAHLs-loaded with iron mobilized in river basins-reach the oceans via river runoff. Recent studies have shown that a fraction of SAHLs belong to the group of strong iron-binding ligands in the ocean. That means, their Fe(III) complexes withstand dissociation even under the conditions of extremely high dilution in the open ocean. Fe(III)-loaded SAHLs are prone to UV-photoinduced ligand-to-metal charge-transfer which leads to disintegration of the complex and, as a consequence, to enhanced concentrations of bioavailable dissolved Fe(II) in sunlit upper water layers. On the other hand, in water depths below the penetration depth of UV, the Fe(III)-loaded SAHLs are fairly resistant to degradation which makes them ideally suited as long-lived molecular transport vehicles for river-derived iron in ocean currents. At locations where SAHLs are present in excess, they can bind to iron originating from various sources. For example, SAHLs were proposed to contribute substantially to the stabilization of hydrothermal iron in deep North Atlantic waters. Recent discoveries have shown that SAHLs, supplied by the Arctic Great Rivers, greatly improve dissolved iron concentrations in the Arctic Ocean and the North Atlantic Ocean. In these regions, SAHLs play a critical role in relieving iron limitation of phytoplankton, thereby supporting the oceanic sink for anthropogenic CO2. The present Critical Review describes the most recent findings and highlights future research directions.

Expression, Purification, and Characterization of a Well-Adapted Tyrosinase from Peatlands Identified by Partial Community Analysis.

In peatlands, bacterial tyrosinases (TYRs) are proposed to act as key regulators of carbon storage by removing phenolic compounds, which inhibit the degradation of organic carbon. Historically, TYR activity has been blocked by anoxia resulting from persistent waterlogging; however, recent events of prolonged summer drought have boosted TYR activity and, consequently, the release of carbon stored in the form of organic compounds from peatlands. Since 30% of the global soil carbon stock is stored in peatlands, a profound understanding of the production and activity of TYRs is essential to assess the impact of carbon dioxide emitted from peatlands on climate change. TYR partial sequences identified by degenerated primers suggest a versatile TYR enzyme community naturally present in peatlands, which is produced by a phylogenetically diverse spectrum of bacteria, including Proteobacteria and Actinobacteria. One full-length sequence of an extracellular TYR (SzTYR) identified from a soda-rich inland salt marsh has been heterologously expressed and purified. SzTYR exhibits a molecular mass of 30 891.8 Da and shows a pH optimum of 9.0. Spectroscopic studies and kinetic investigations characterized SzTYR as a tyrosinase and proved its activity toward monophenols (coumaric acid), diphenols (caffeic acid, protocatechuic acid), and triphenols (gallic acid) naturally present in peatlands.

Natural iron fertilization of the coastal ocean by "blackwater rivers".

The present study elucidates the role of natural iron fertilization of the coastal ocean by so-called "blackwater rivers". Areas of marsh, fen, peatland, boreal forest etc. are characterized by organic-rich soils. From those soils, humic substances (humic and fulvic acids) are leached to the aquatic system resulting in river water that is low in pH and dark-brown in color. The point is that "blackwater rivers" tend to be rich in dissolved iron due to the unique chelating properties of humic and fulvic acids which bind Fe(III) and keep it in solution. We performed algal physiological (growth rate) experiments under conditions of iron deficiency with the marine unicellular phytoplankton algae Chlorella salina and Diacronema lutheri in 0.2 µm cut-off filtered mixtures of natural "blackwater river" water and synthetic seawater. Our results demonstrate that the iron naturally present in "blackwater rivers" is readily bioavailable to both marine algal species. Furthermore, the humic and fulvic acids exert an additional stimulatory effect on the marine algae. Both algae thrive much better in the presence of natural humic and fulvic acids as compared to a medium where EDTA is used as an iron-chelating agent. Our results indicate that "blackwater rivers", in sharp contrast to other types of rivers, are excellent sources of bioavailable iron to marine phytoplankton. This natural iron fertilization may give rise to photosynthesis-driven sequestration of CO2 from the atmosphere to the sea, as can be seen from the visualization of CO2 surface concentrations by NASA (NASA GEOS-5 model) which shows the global sources and sinks of CO2 localized in time and space. The results by NASA suggest that strong marine CO2 sinks in coastal waters tend to occur close to "blackwater river" estuaries. It is thus evident that "blackwater rivers" act as important sources of a limiting nutrient (iron) to the ocean.

Uranium concentrations in sediment pore waters of Lake Neusiedl, Austria.

The goal of the present investigation was to measure 234U/238U activity ratios in pore waters of Lake Neusiedl, Austria, in order to learn more about uranium in groundwaters of the Lake Neusiedl/Seewinkel region. Pore waters of waterlogged sediments (at 1m depth) in the littoral zone of Lake Neusiedl were analyzed. The pore water samples were collected in the National Park Lake Neusiedl/Seewinkel from pristine sites that were not influenced by neighboring fertilized fields or vineyards. Uranium isotopes were extracted from 1.5L of sediment pore water and measured by α-particle spectrometry. Uranium concentrations were found to be unexpectedly high (up to 853µgL-1) especially in pore waters of salt-rich locations. 234U/238U activity ratios were between 0.91 and 1.09 for all pore water samples, irrespective of their origin from the east or west littoral zones of the lake. Uranium and mineral salts concentrations were strongly correlated. 222Rn concentrations were low (between 22 and 42BqL-1). The results provide insight into the high degree of mobility of U(VI) in sedimentary environments, in the presence of migrating Na2SO4-type saline waters.

Thioglycolate-based task-specific ionic liquids: Metal extraction abilities vs acute algal toxicity.

We studied the extraction behavior of two thioglycolate-based ionic liquids (ILs), for heavy metals from aqueous solutions; substances of interest were methyltrioctylammonium S-hexyl thioglycolate [N1888][C6SAc] and methyltrioctylphosphonium S-hexyl thioglycolate [P1888][C6SAc]. Theses ILs previously have shown very good extraction abilities towards cadmium and copper, therefore we investigated time-dependent metal removal experiments with aqueous solutions of cobalt(II), nickel(II) and zinc(II). The highest distribution ratio (RIL/Water) was determined for zinc (RIL/Water=2000). Recovery studies for zinc after extraction were performed with different stripping agents showing a successful recycling. Additionally, the two ILs were immobilized on active charcoal, displaying great potential for solid-liquid extraction. Regarding the extraction mechanism, quantum-mechanical calculations were included, which indicate that the metal extraction depends on the stability of the metal-water cluster. Ligands (water as well as ILs) are planar coordinated in nickel complexes but showed a tetrahedral configuration for zinc. As a first estimate of the ecotoxicity of the ILs, in vivo tests toward three freshwater green algae species Tetradesmus obliquus, Desmodesmus armatus and Raphidocelis subcapitata were carried out. The EC50 values (effective concentration after 72 h) confirm high toxicity of all tested ILs to all species, displaying only small differences between the species and EC50ies.

Heavy metals in the mallard Anas platyrhynchos from eastern Austria.

A total of 77 specimens of the mallard Anas platyrhynchos were sampled from the eastern part of Austria before the ban on lead gun shot for hunting water fowl. Samples of muscle and liver were analyzed for their content of Cr, Cu, Zn, Ag, Cd, Hg and Pb using atomic absorption spectrometry. In addition the Hg content of feather samples from this aquatic bird species was evaluated. Results generally show higher concentrations of the metals in the liver compared to muscle; for mercury the concentrations were feathers>liver>muscle. Elevated, in some cases critical concentrations of Cr, Cu, Cd, Hg and Pb were measured. Levels of Ag were recorded for the first time for this species from Europe, providing basic information for future evaluation of this upcoming pollutant in aquatic environments.

Task-specific thioglycolate ionic liquids for heavy metal extraction: Synthesis, extraction efficacies and recycling properties.

Eight novel task-specific ionic liquids (TSILs) based on the thioglycolate anion designed for heavy metal extraction have been prepared and characterized by 1H and 13C NMR, UV-Vis, infrared, ESI-MS, conductivity, viscosity, density and thermal properties. Evaluation of their time-resolved extraction abilities towards cadmium(II) and copper(II) in aqueous solutions have been investigated where distribution ratios up to 1200 were observed. For elucidation of the IL extraction mode, crystals were grown where Cd(II) was converted with an excess of S-butyl thioglycolate. It was found by X-ray diffraction analysis that cadmium is coordinated by five oxygen and one sulfur donor atoms provided by two thioglycolate molecules and one water molecule. Leaching behavior of the hydrophobic ionic liquids into aqueous systems was studied by TOC (total dissolved organic carbon) measurements. Additionally, the immobilization on polypropylene was elucidated and revealed slower metal extraction rates and similar leaching behavior. Finally, recovery processes for cadmium and copper after extraction were performed and recyclability was successfully proven for both metals.

Synthetic iron complexes as models for natural iron-humic compounds: Synthesis, characterization and algal growth experiments.

A series of monomeric and dimeric FeIII complexes with O,O-; O,N-; O,S-coordination motifs has been prepared and characterized by standard analytical methods in order to elucidate their potential to act as model compounds for aquatic humic acids. Due to the postulated reduction of iron in humic acids and following uptake by microorganisms, the redox behavior of the models was investigated with cyclic voltammetry. Most of the investigated compounds showed iron reduction potentials accessible to biological reducing agents. Additionally, observed reduction processes were predominantly irreversible, suggesting that subsequent reactions can take place after reduction of the iron center. Also the stability of the synthesized complexes in pure water and artificial seawater was monitored from 24h up to 21days by means of UV-Vis spectrometry. Several complexes remained stable even after 21days, showing only partially precipitation but some of them showed changes in UV-Vis spectra already after 24h which were connected to protonation/deprotonation processes as well as redox processes and degradation of the complexes. The ability to act as an iron source for primary producers was tested in algal growth experiments with two marine algae species Chlorella salina and Prymnesium parvum. Some of the compounds showed effects on the algal cultures, which are comparable with natural humic acids and better as for the samples kept under ideal conditions. Those findings help to understand which functional groups of humic acids could be responsible for the reversible iron binding and transport in aquatic humic substances.

Photoreduction of Terrigenous Fe-Humic Substances Leads to Bioavailable Iron in Oceans.

Humic substances (HS) are important iron chelators responsible for the transport of iron from freshwater systems to the open sea, where iron is essential for marine organisms. Evidence suggests that iron complexed to HS comprises the bulk of the iron ligand pool in near-coastal waters and shelf seas. River-derived HS have been investigated to study their transport to, and dwell in oceanic waters. A library of iron model compounds and river-derived Fe-HS samples were probed in a combined X-ray absorption spectroscopy (XAS) and valence-to-core X-ray emission spectroscopy (VtC-XES) study at the Fe K-edge. The analyses performed revealed that iron complexation in HS samples is only dependent on oxygen-containing HS functional groups, such as carboxyl and phenol. The photoreduction mechanism of FeIII-HS in oceanic conditions into bioavailable aquatic FeII forms, highlights the importance of river-derived HS as an iron source for marine organisms. Consequently, such mechanisms are a vital component of the upper-ocean iron biogeochemistry cycle.

Novel thiosalicylate-based ionic liquids for heavy metal extractions.

This study aims to develop novel ammonium and phosphonium ionic liquids (ILs) with thiosalicylate (TS) derivatives as anions and evaluate their extracting efficiencies towards heavy metals in aqueous solutions. Six ILs were synthesized, characterized, and investigated for their extracting efficacies for cadmium, copper, and zinc. Liquid-liquid extractions of Cu, Zn, or Cd with ILs after 1-24h using model solutions (pH 7; 0.1M CaCl2) were assessed using flame atomic absorption spectroscopy (F-AAS). Phosphonium-based ILs trihexyltetradecylphosphonium 2-(propylthio)benzoate [P66614][PTB] and 2-(benzylthio)benzoate [P66614][BTB] showed best extraction efficiency for copper and cadmium, respectively and zinc was extracted to a high degree by [P66614][BTB] exclusively.

Photoreduction of Terrigenous Fe-Humic Substances Leads to Bioavailable Iron in Oceans.

Humic substances (HS) are important iron chelators responsible for the transport of iron from freshwater systems to the open sea, where iron is essential for marine organisms. Evidence suggests that iron complexed to HS comprises the bulk of the iron ligand pool in near-coastal waters and shelf seas. River-derived HS have been investigated to study their transport to, and dwell in oceanic waters. A library of iron model compounds and river-derived Fe-HS samples were probed in a combined X-ray absorption spectroscopy (XAS) and valence-to-core X-ray emission spectroscopy (VtC-XES) study at the Fe K-edge. The analyses performed revealed that iron complexation in HS samples is only dependent on oxygen-containing HS functional groups, such as carboxyl and phenol. The photoreduction mechanism of Fe(III) -HS in oceanic conditions into bioavailable aquatic Fe(II) forms, highlights the importance of river-derived HS as an iron source for marine organisms. Consequently, such mechanisms are a vital component of the upper-ocean iron biogeochemistry cycle.

Sphagnum-dominated bog systems are highly effective yet variable sources of bio-available iron to marine waters.

Iron is a micronutrient of particular interest as low levels of iron limit primary production of phytoplankton and carbon fluxes in extended regions of the world's oceans. Sphagnum-peatland runoff is extraordinarily rich in dissolved humic-bound iron. Given that several of the world's largest wetlands are Sphagnum-dominated peatlands, this ecosystem type may serve as one of the major sources of iron to the ocean. Here, we studied five near-coastal creeks in North Scotland using freshwater/seawater mixing experiments of natural creek water and synthetic seawater based on a (59)Fe radiotracer technique combined with isotopic characterization of dissolved organic carbon by Accelerator Mass Spectrometry. Three of the creeks meander through healthy Sphagnum-dominated peat bogs and the two others through modified peatlands which have been subject to artificial drainage for centuries. The results revealed that, at the time of sampling (August 16-24, 2014), the creeks that run through modified peatlands delivered 11-15µg iron per liter creek water to seawater, whereas the creeks that run through intact peatlands delivered 350-470µg iron per liter creek water to seawater. To find out whether this humic-bound iron is bio-available to marine algae, we performed algal growth tests using the unicellular flagellated marine prymnesiophyte Diacronema lutheri and the unicellular marine green alga Chlorella salina, respectively. In both cases, the riverine humic material provided a highly bio-available source of iron to the marine algae. These results add a new item to the list of ecosystem services of Sphagnum-peatlands.

Determination of size-dependent metal distribution in dissolved organic matter by SEC-UV/VIS-ICP-MS with special focus on changes in seawater.

Iron is an essential micronutrient for all marine organisms, but it is also a growth limiting factor as the iron concentrations in the open ocean are below 1 nmol/L in sea water iron is almost entirely bound to organic ligands of the dissolved organic matter fraction, which are mostly of unknown structure. The input from rivers was traditionally considered as less important due to estuarine sedimentation processes of the mainly colloidal iron particles. However, recent studies have shown that this removal is not complete and riverine input may represent an important iron source in the open ocean. In this context, iron transport by land-derived natural organic matter (NOM), and dissolved organic matter (DOM) have been identified as carrier mechanisms for riverine iron. The aim of this work is to characterize complexes containing iron and other metals in waters simulating estuarine conditions in order to help understand which role iron-DOM compounds play in the open ocean. A method based on size-exclusion chromatography (SEC) with sequential UV/VIS and ICP-MS detection was developed for investigation of DOM size distribution and for assessment of the size-dependent metal distribution in NOM-rich surface water. Furthermore, sample matrix experiments were also performed revealing a dependence of DOM size distribution upon seawater concentration and different compounds present in seawater. Finally, efforts toward determination of DOM size with standardization with typical SEC standards indicate that only relative comparisons are possible with this approach, and that the sample matrix composition strongly influences obtained results.

River-derived humic substances as iron chelators in seawater.

The speciation of iron(III) in oxic seawater is dominated by its hydrolysis and sedimentation of insoluble iron(III)-oxyhydroxide. As a consequence, many oceanic areas have very low iron levels in surface seawater which leads to iron deficiency since phytoplankton require iron as a micronutrient in order to grow. Fortunately, iron solubility is not truly as low as Fe(III) solubility measurements in inorganic seawater would suggest, since oceanic waters contain organic molecules which tend to bind the iron and keep it in solution. Various iron-binding organic ligands which combine to stabilize dissolved iron have been detected and thoroughly investigated in recent years. However, the role of iron-binding ligands from terrestrial sources remains poorly constrained. Blackwater rivers supply large amounts of natural organic material (NOM) to the ocean. This NOM (which consists mainly of vascular plant-derived humic substances) is able to greatly enhance iron bioavailability in estuaries and coastal regions, however, breakdown processes lead to a rapid decrease of river-derived NOM concentrations with increasing distance from land. It has therefore been argued that the influence of river-derived NOM on iron biogeochemistry in offshore seawater does not seem to be significant. Here we used a standard method based on 59Fe as a radiotracer to study the solubility of Fe(III)-oxyhydroxide in seawater in the presence of riverine NOM. We aimed to address the question how effective is freshwater NOM as an iron chelator under open ocean conditions where the concentration of land-derived organic material is about 3 orders of magnitude smaller than in coastal regions, and does this iron chelating ability vary between NOM from different sources and between different size fractions of the river-borne NOM. Our results show that the investigated NOM fractions were able to substantially enhance Fe(III)-oxyhydroxide solubility in seawater at concentrations of the NOM ≥ 5 µg L- 1. Terrigenous NOM concentrations ≥ 5 µg L- 1 are in no way unusual in open ocean surface waters especially of the Arctic and the North Atlantic Oceans. River-derived humic substances could therefore play a greater role as iron carriers in the ocean than previously thought.

Extraction of natural radionuclides from aqueous solutions by novel maltolate-based task-specific ionic liquids.

Two novel maltol-based ionic liquids, namely [A336][Mal] and [C101][Mal], were synthesized as potential extracting agents for radionuclides from water. These two room temperature task-specific ionic liquids could be easily prepared by anion metathesis starting from commercially available materials. The isolated compounds were characterized by standard analytical methods. Their application as extraction agent for Unat., 234Th, 210Pb, 210Bi, 210Po and 226Ra was elucidated by liquid-liquid extraction and scintillation counting. Uranium was totally extracted by both ionic liquids over a broad pH range (2-8), while the other radionuclides were removed with differing efficacies depending on the respective pH value.

Total mercury in sediments, macrophytes, and fish from a shallow steppe lake in eastern Austria.

During summer 2011, samples of sediment, macrophytes, and fish tissues from the shallow, slightly alkaline Lake Neusiedl, Austria, were evaluated for their total Hg content. This is the first report of Hg levels from this lake. Sediments displayed Hg contents between 0.025 and 0.113 µg g(-1) dw (dry weight), significantly correlating with the proportion of organic components pointing to a small anthropogenic impact on the lake's Hg content. Hg Levels in plants and fish were unexpectedly high: both investigated submerged plant species, Potamogeton pectinatus and Myriophyllum spicatum, showed mean values of 0.245 ± 0.152 and 0.298 ± 0.115 µg g(-1) dw, respectively. Biomagnification was evident when comparing muscle samples of the planktivorous fish species rudd Scardinus erythrophthalmus (n = 10, mean = 0.084 µg g(-1) ww (wet weight)) with the piscivorous perch Perca fluviatilis (n = 21, mean = 0.184 µg g(-1) ww) or pike-perch Sander lucioperca (n = 9, mean = 0.205 µg g(-1) ww). Significantly lower values were found in the muscle of the piscivorous pike Esox lucius (n = 25, mean = 0.135 µg g(-1) ww), pointing to a specific Hg metabolism of this fish, presumably under the particular physicochemical properties of the lake. Hg Concentrations in fish could pose a risk to piscivorous birds in this protected wetland system.

Hexanuclear and undecanuclear iron(III) carboxylates as catalyst precursors for cyclohexane oxidation.

Two multinuclear complexes [Fe6(µ3-O)2(µ4-O2)L10(OAc)2(H2O)2]·2.625Et2O·2.375H2O (1) and [Fe(III)11Cl(µ4-O)3(µ3-O)5L16(dmf)(2.5)(H2O)(0.5)]·Et2O·1.25dmf·3.8H2O (2), where HL = 3,4,5-trimethoxybenzoic acid and dmf = dimethylformamide, have been prepared from trinuclear iron(III) carboxylates via their structural rearrangement in dimethylformamide or diethyl ether-dimethylformamide 9:1, respectively, and slow vapor diffusion of diethyl ether into the reaction mixture. Both compounds have been characterized by X-ray diffraction, optical, Mössbauer spectroscopy, and magnetic measurements. Complex 1 possesses a hexanuclear ferric peroxido-dioxido {Fe6(O2)(O)2}(12+) core unit, which adopts a recliner conformation, while complex 2 contains an unprecedented {Fe11O8Cl}(16+) core, in which 9 ferric ions are six-coordinate and the remaining two are five-coordinate. Another structural feature of note of the undecanuclear core is the presence of a deformed cubane entity {Fe4(µ3-O)(µ4-O)3}(4+). Both complexes act as catalyst precursors for the oxidation of cyclohexane to cyclohexanol and cyclohexanone with aqueous H2O2, in the presence of pyrazinecarboxylic acid. Remarkable TONs and TOFs (the latter mainly for 1) with concomitant quite good yields have been achieved under mild conditions. Moreover, 1 exhibits remarkably high activity in an exceptionally short reaction time (45 min), being unprecedented for any metal catalyzed alkane oxidation by H2O2. The catalytic reactions proceed via Fenton type chemistry.

Natural organic matter and iron export from the Tanner Moor, Austria.

Samples from a pristine raised peat bog runoff in Austria, the Tannermoor creek, were analysed for their iron linked to natural organic matter (NOM) content. Dissolved organic carbon < 0.45 µm (DOC) was 41-64 mg L-1, iron 4.4-5.5 mg L-1. Samples were analysed applying asymmetric field flow fractionation (AsFlFFF) coupled to UV-vis absorption, fluorescence and inductively coupled plasma mass spectrometry (ICP-MS). The samples showed an iron peak associated with the NOM peak, one sample exhibiting a second peak of iron independent from the NOM peak. As highland peat bogs with similar climatic conditions and vegetation to the Tanner Moor are found throughout the world, including areas adjacent to the sea, we examined the behaviour of NOM and iron in samples brought to euhaline (35‰) conditions with artificial sea salt. The enhanced ionic strength reduced NOM by 53% and iron by 82%. Size exclusion chromatography (SEC) of the samples at sea-like salinity revealed two major fractions of NOM associated with different iron concentrations. The larger one, eluting sharply after the upper exclusion limits of 4000-5000 g mol-1, seems to be most important for iron chelating. The results outline the global importance of sub-mountainous and mountainous raised peat bogs as a source of iron chelators to the marine environment at sites where such peat bogs release their run-offs into the sea.