Size exclusion chromatogram of the Tannermoor 2009 sample after saltout experiments

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 to 64 mg/L, iron 4.4 to 5.5 mg/L. 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 per mil) 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, 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.

Phosphorus components, trace metals and Ba excess of ODP Site 202-1237 sediments

We determined the sedimentary concentrations of phosphorus (P), barium (Ba), manganese (Mn), titanium (Ti), aluminum (Al), and uranium (U) for sediment samples from the southeast Pacific Nazca Ridge, Ocean Drilling Program Site 1237. This unique record extends to 31 Ma over 360 meters composite depth (mcd), recording depositional history as the site progressed eastward over its paleohistory. We sampled with a temporal resolution of ~0.2 m.y. throughout the sequence, equivalent to an average spacing of 1.63 m/sample. Concentrations of sequentially extracted components of P (oxide-associated, authigenic, organic, and detrital) increase toward the modern. Al/Ti ratios indicate that the background detrital source material is consistent with upper continental crust. U enrichment factors (U EFs) generally exceed crustal values and indicate slightly reducing environments. However, authigenic U precipitation can also be influenced by the organic carbon rain rate and may not be solely an indicator of redox conditions. Dramatic changes in Mn EFs at ~162 mcd, from values between 12 and 93 to values <12 after this depth, and a sharp color contact boundary lead us to believe that a paleoredox boundary from an oxygenated to a more reducing depositional environment occurred near this depth. Estimates of biogenic barite concentrations from a total sediment digestion technique (Ba excess) are greater than those from a barite extraction (Ba barite) for selected samples across the entire depth range. Applying a range of Ba/Ti ratios from different source materials to correct for detrital inputs does not change the lack of agreement with Ba barite concentrations. Reactive P (P reactive) concentrations (the sum of oxide-associated, authigenic, and organic P concentrations) increase toward the modern with values typically <12 µmol P/g from the base of our record through ~100 mcd, with a gradual increase to concentrations >15 µmol P/g. Ba excess follows the same general trends as Preactive, with concentrations <14 µmol Ba/g in the lower portion of the record to values >15 µmol Ba/g. Accumulation rate records of these proxies will be needed to infer paleoproductivity. P reactive/Ba excess ratios, an indicator of the relative burial of the nutrient P to organic carbon export, exhibit higher values, similar to modern, from the base of our record through ~180 mcd. The remainder of the record exhibits values lower than modern, indicating that organic carbon export to the sediments was higher relative to nutrient burial.