41 resultados para reductive paraphrase


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Four species of planktic foraminifera from core-tops spanning a depth transect on the Ontong Java Plateau were prepared for Mg/Ca analysis both with (Cd-cleaning) and without (Mg-cleaning) a reductive cleaning step. Reductive cleaning caused etching of foraminiferal calcite, focused on Mg-rich inner calcite, even on tests which had already been partially dissolved at the seafloor. Despite corrosion, there was no difference in Mg/Ca of Pulleniatina obliquiloculata between cleaning methods. Reductive cleaning decreased Mg/Ca by an average (all depths) of ~ 4% for Globigerinoides ruber white and ~ 10% for Neogloboquadrina dutertrei. Mg/Ca of Globigerinoides sacculifer (above the calcite saturation horizon only) was 5% lower after reductive cleaning. The decrease in Mg/Ca due to reductive cleaning appeared insensitive to preservation state for G. ruber, N. dutertrei and P. obliquiloculata. Mg/Ca of Cd-cleaned G. sacculifer appeared less sensitive to dissolution than that of Mg-cleaned. Mg-cleaning is adequate, but SEM and contaminants (Al/Ca, Fe/Ca and Mn/Ca) show that Cd-cleaning is more effective for porous species. A second aspect of the study addressed sample loss during cleaning. Lower yield after Cd-cleaning for G. ruber, G. sacculifer and N. dutertrei confirmed this to be the more aggressive method. Strongest correlations between yield and Delta[CO3^2-] in core-top samples were for Cd-cleaned G. ruber (r = 0.88, p = 0.020) and Cd-cleaned P. obliquiloculata (r = 0.68, p = 0.030). In a down-core record (WIND28K) correlation, r, between yield values > 30% and dissolution index, XDX, was -0.61 (p = 0.002). Where cleaning yield < 30% most Mg-cleaned Mg/Ca values were biased by dissolution.

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We present new isotopic data for sedimentary planktonic foraminifera, as well as for potential water column and sedimentary sources of neodymium (Nd), which confirm that the isotopic composition of the foraminifera is the same as surface seawater and very different from deep water and sedimentary Nd. The faithfulness with which sedimentary foraminifera record the isotopic signature of surface seawater Nd is difficult to explain given their variable and high Nd/Ca ratios, ratios that are often sedimentary foraminifera, ratios that are often much higher than is plausible for direct incorporation within the calcite structure. We present further data that demonstrate a similarly large range in Nd/Ca ratios in plankton tow foraminifera, a range that may be controlled by redox conditions in the water column. Cleaning experiments reveal, in common with earlier work, that large amounts of Nd are released by cleaning with both hydrazine and diethylene triamine penta-acetic acid, but that the Nd released at each step is of surface origin. While further detailed studies are required to verify the exact location of the surface isotopic signature and the key controls on foraminiferal Nd isotope systematics, these new data place the use of planktonic foraminifera as recorders of surface water Nd isotope ratios, and thus of variations in the past supply of Nd to the oceans from the continents via weathering and erosion, on a reasonably sure footing.

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In this study we present a late Miocene - early Pliocene record of sixty-four zones with prominent losses in the magnetic susceptibility signal, taken on a sediment drift (ODP Site 1095) on the Pacific continental rise of the West Antarctic Peninsula. The zones are comparable in shape and magnitude and occur commonly at glacial-to-interglacial transitions. High resolution records of organic matter, magnetic susceptibility and clay mineral composition from early Pliocene intervals demonstrate that neither dilution effects nor provenance changes of the sediments have caused the magnetic susceptibility losses. Instead, reductive dissolution of magnetite under suboxic conditions seems to be the most likely explanation. We propose that during the deglaciation exceptionally high organic fluxes in combination with weak bottom water currents and prominent sediment draping diatom ooze layers produced temporary suboxic conditions in the uppermost sediments. It is remarkable that synsedimentary suboxic conditions can be observed in one of the best ventilated open ocean regions of the World.

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Fossil fish teeth from pelagic open ocean settings are considered a robust archive for preserving the neodymium (Nd) isotopic composition of ancient seawater. However, using fossil fish teeth as an archive to reconstruct seawater Nd isotopic compositions in different sedimentary redox environments and in terrigenous-dominated, shallow marine settings is less proven. To address these uncertainties, fish tooth and sediment samples from a middle Eocene section deposited proximal to the East Antarctic margin at Integrated Ocean Drilling Program Site U1356 were analyzed for major and trace element geochemistry, and Nd isotopes. Major and trace element analyses of the sediments reveal changing redox conditions throughout deposition in a shallow marine environment. However, variations in the Nd isotopic composition and rare earth element (REE) patterns of the associated fish teeth do not correspond to redox changes in the sediments. REE patterns in fish teeth at Site U1356 carry a typical mid-REE-enriched signature. However, a consistently positive Ce anomaly marks a deviation from a pure authigenic origin of REEs to the fish tooth. Neodymium isotopic compositions of cleaned and uncleaned fish teeth fall between modern seawater and local sediments and hence could be authigenic in nature, but could also be influenced by sedimentary fluxes. We conclude that the fossil fish tooth Nd isotope proxy is not sensitive to moderate changes in pore water oxygenation. However, combined studies on sediments, pore waters, fish teeth and seawater are needed to fully understand processes driving the reconstructed signature from shallow marine sections in proximity to continental sources. This article is protected by copyright. All rights reserved.

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Results and discussion cover pigment analyses of 36 sediment samples recovered by Deep Sea Drilling Project Leg 64, and six samples from the Leg 64 site-survey cruise in the Guaymas Basin (Scripps Institution of Oceanography, Leg 3). Pigments investigated were tetrapyrroles, tetraterpenoids, and the PAH compound perylene. Traces of mixed nickel and copper ETIO-porphyrins were ubiquitous in all sediment samples, except for the very surface (i.e., <2 m sub-bottom), and their presence is taken as an indication of minor influxes of previously oxidized allochthonous (terrestrial) organic matter. Phorbides and chlorins isolated from Site 479 sediment samples (i.e., the oxygen-minimum locale, northeast of the Guaymas Basin) well represent the reductive diagenesis ("Treibs Scheme"; see Baker and Palmer, 1978; Treibs, 1936) of chlorophyll derivatives. Three forms of pheophytin-a, plus a variety of phorbides, were found to give rise to freebase porphyrins, nickel phylloerythrin, and nickel porphyrins, with increasing depth of burial (increasing temperature). Sediments from Sites 481, 10G, and 18G yielded chlorophyll derivatives characteristic of early oxidative alterations. Included among these pigments are allomerized pheophytin-a, purpurin-18, and chlorin-p6. The high thermal gradient imposed upon the late Quaternary sediments of Site 477 greatly accelerated chlorophyll diagenesis in the adjacent overlying sediments, that is, the production of large quantities of free-base desoxophylloerythroetioporphyrin (DPEP) occurred in a section (477-7-5) presently only 49.8 meters sub-bottom. Present depth and age of these sediments are such that only chlorins and phorbides would be expected. Carotenoid (i.e., tetraterpenoids) concentrations were found to decrease rapidly with increasing sub-bottom depth. Less deeply buried sediments (e.g., 0-30 m) yielded mixtures of carotenes and oxygen-substituted carotenoids. Oxygencontaining (oxy-, oxo-, epoxy-) carotenoids were found to be lost preferentially with increased depth of burial. Early carotenoid diagenesis is suggested as involving interacting reductions and dehydrations whereby dehydro-, didehydro-, and retro-carotenes are generated. Destruction of carotenoids as pigments may involve oxidative cleavage of the isoprenoid chain through epoxy intermediates, akin to changes in the senescent cells of plants. Perylene was found to be a common component of the extractable organic matter from all sediments investigated. The generation of alkyl perylenes was found to parallel increases in the existing thermal regime at all sites. Igneous sills and sill complexes within the sediment profile of Site 481 altered (i.e., scrambled) the otherwise straightforward thermally induced alkylation of perylene. The degree of perylene alkylation is proposed as an indicator of geothermal stress for non-contemporaneous marine sediments.

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Constraining the magnitude of high-latitude temperature change across the Eocene-Oligocene transition (EOT) is essential for quantifying the magnitude of Antarctic ice-sheet expansion and understanding regional climate response to this event. To this end, we constructed high-resolution stable oxygen isotope (d18O) and magnesium/calcium (Mg/Ca) records from planktic and benthic foraminifera at four Ocean Drilling Program (ODP) sites in the Southern Ocean. Planktic foraminiferal Mg/Ca records from the Kerguelen Plateau (ODP Sites 738, 744, and 748) show a consistent pattern of temperature change, indicating 2-3 °C cooling in direct conjunction with the first step of a two-step increase in benthic and planktic foraminiferal d18O values across the EOT. In contrast, benthic Mg/Ca records from Maud Rise (ODP Site 689) and the Kerguelen Plateau (ODP Site 748) do not exhibit significant temperature change. The contrasting temperature histories derived from the planktic and benthic Mg/Ca records are not reconcilable, since vertical d18O gradients remained nearly constant at all sites between 35.0 and 32.5 Ma. Based on the coherency of the planktic Mg/Ca records from the Kerguelen Plateau sites and complications with benthic Mg/Ca paleothermometry at low temperatures, the planktic Mg/Ca records are deemed the most reliable measure of Southern Ocean temperature change. We therefore interpret a uniform cooling of 2-3 °C in both deep surface (thermocline) waters and intermediate deep waters of the Southern Ocean across the EOT. Cooling of Southern Ocean surface waters across the EOT was likely propagated to the deep ocean, since deep waters were primarily sourced on the Antarctic margin throughout this time interval. Removal of the temperature component from the observed foraminiferal d18O shift indicates that seawater d18O values increased by 0.6 ± 0.15 per mil across the EOT interval, corresponding to an increase in global ice volume to a level equivalent with 60-130% modern East Antarctic ice sheet volume.

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With various low-temperature experiments performed on magnetic mineral extracts of marine sedimentary deposits from the Argentine continental slope near the Rio de la Plata estuary, a so far unreported style of partial magnetic self-reversal has been detected. In these sediments the sulphate-methane transition (SMT) zone is situated at depths between 4 and 8 m, where reductive diagenesis severely alters the magnetic mineral assemblage. Throughout the sediment column magnetite and ilmenite are present together with titanomagnetite and titanohematite of varying compositions. In the SMT zone (titano-)magnetite only occurs as inclusions in a siliceous matrix and as intergrowths with lamellar ilmenite and titanium-rich titanohematite, originating from high temperature deuteric oxidation within the volcanic host rocks. These abundant structures were visualized by scanning electron microscopy and analysed by energy dispersive spectroscopy. Warming of field-cooled and zero-field-cooled low-temperature saturation remanence displays magnetic phase transitions of titanium-rich titanohematite below 50 K and the Verwey transition of magnetite. A prominent irreversible decline characterizes zero-field cooling of room temperature saturation remanence. It typically sets out at ~210 K and is most clearly developed in the lower part of the SMT zone, where low-temperature hysteresis measurements identified ~210 K as the blocking temperature range of a titanohematite phase with a Curie temperature of around 240 K. The mechanism responsible for the marked loss of remanence is, therefore, sought in partial magnetic self-reversal by magnetostatic interaction of (titano-)magnetite and titanohematite. When titanohematite becomes ferrimagnetic upon cooling, its spontaneous magnetic moments order antiparallel to the (titano-)magnetite remanence causing an drastic initial decrease of global magnetization. The loss of remanence during subsequent further cooling appears to result from two combined effects (1) magnetic interaction between the two phases by which the (titano-)magnetite domain structure is substantially modified and (2) low-temperature demagnetization of (titano-)magnetite due to decreasing magnetocrystalline anisotropy. The depletion of titanomagnetite and superior preservation of titanohematite is characteristic for strongly reducing sedimentary environments. Typical residuals of magnetic mineral assemblages derived from basaltic volcanics will be intergrowths of titanohematite lamellae with titanomagnetite relics. Low-temperature remanence cycling is, therefore, proposed as a diagnostic method to magnetically characterize such alteration (palaeo-)environments.

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Low-temperature (LT) magnetic remanence and hysteresis measurements, in the range 300-5 K, were combined with energy dispersive spectroscopy (EDS) in order to characterize the magnetic inventory of strongly diagenetically altered sediments originating from the Niger deep-sea fan. We demonstrate the possibility of distinguishing between different compositions of members of the magnetite-ulvöspinel and ilmenite-hematite solid solution series on a set of five representative samples, two from the upper suboxic and three from the lower sulfidic anoxic zone of gravity core GeoB 4901. Highly sensitive LT magnetic measurements were performed on magnetic extracts resulting in large differences in the magnetic behavior between samples from the different layers. This emphasizes that both Fe-Ti oxide phases occur in different proportions in the two geochemical environments. Most prominent are variations in the coercivity sensitive parameter coercive field (BC). At room-temperature (RT) hysteresis loops for all extracts are narrow and yield low coercivities (6-13 mT). With decreasing temperature the loops become more pronounced and wider. At 5 K an approximately 5-fold increase in BC for the suboxic samples contrasts a 20-25-fold increase for the samples from the anoxic zone. We demonstrate that this distinct increase in BC at LT corresponds to the increasing proportion of the Ti-rich hemoilmenite phase, while Fe-rich (titano-)magnetite dominates the magnetic signal at RT. This trend is also seen in the room-temperature saturation isothermal remanent magnetization (RT-SIRM) cycles: suboxic samples show remanence curves dominated by Fe-rich mineral phases while anoxic samples display curves clearly dominated by Ti-rich particles. We show that the EDS intensity ratios of the characteristic Fe Kalpha and Ti Kalpha lines of the Fe-Ti oxides may be used to differentiate between members of the magnetite-ulvöspinel and ilmenite-hematite solid solution series. Furthermore it is possible to calculate an approximate composition for each grain if the intensity ratios of natural particles are linked to well-known standards. Thus, element spectra with high Fe/Ti intensity ratios were found to be rather typical of titanomagnetite while low Fe/Ti ratios are indicative of hemoilmenite. The EDS analyses confirm the LT magnetic results, Fe-rich magnetic phases dominate in the upper suboxic environment whereas Ti-rich magnetic phases comprise the majority of particles in the lower anoxic domain: The mineral assemblage of the upper suboxic environments is composed of magnetite (~19%), titanomagnetite (~62%), hemoilmenite (~17%) and ~2% other particles. In the lower anoxic sediments, reductive diagenetic alteration has resulted in more extensive depletion of the (titano-)magnetite phase, resulting in a relative enrichment of the hemoilmenite phase (~66%). In these strongly anoxic sediments stoichiometric magnetite is barely preserved and only ~5% titanomagnetite was detected. The remaining ~28% comprises Ti-rich particles such as pseudobrookite or rutile.

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On the eastern flank of the Juan de Fuca Ridge, reaction between upwelling basement fluid and sediment alters hydrothermal fluxes of Ca, SiO2(aq), SO4, PO4, NH4, and alkalinity. We used the Global Implicit Multicomponent Reactive Transport (GIMRT) code to model the processes occurring in the sediment column (diagenesis, sediment burial, fluid advection, and multicomponent diffusion) and to estimate net seafloor fluxes of solutes. Within the sediment section, the reactions controlling the concentrations of the solutes listed above are organic matter degradation via SO4 reduction, dissolution of amorphous silica, reductive dissolution of amorphous Fe(III)-(hydr)oxide, and precipitation of calcite, carbonate fluorapatite, and amorphous Fe(II)-sulfide. Rates of specific discharge estimated from pore-water Mg profiles are 2 to 3 mm/yr. At this site the basement hydrothermal system is a source of NH4, SiO2(aq), and Ca, and a sink of SO4, PO4, and alkalinity. Reaction within the sediment column increases the hydrothermal sources of NH4 and SiO2(aq), increases the hydrothermal sinks of SO4 and PO4, and decreases the hydrothermal source of Ca. Reaction within the sediment column has a spatially variable effect on the hydrothermal flux of alkalinity. Because the model we used was capable of simulating the observed pore-water chemistry by using mechanistic descriptions of the biogeochemical processes occurring in the sediment column, it could be used to examine the physical controls on hydrothermal fluxes of solutes in this setting. Two series of simulations in which we varied fluid flow rate (1 to 100 mm/yr) and sediment thickness (10 to 100 m) predict that given the reactions modeled in this study, the sediment section will contribute most significantly to fluxes of SO4 and NH4 at slow flow rates and intermediate sediment thickness and to fluxes of SiO2(aq) at slow flow rates and large sediment thickness. Reaction within the sediment section could approximately double the hydrothermal sink of PO4 over a range of flow rates and sediment thickness, and could slightly decrease (by

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In anoxic environments, volatile methylated sulfides like methanethiol (MT) and dimethyl sulfide (DMS) link the pools of inorganic and organic carbon with the sulfur cycle. However, direct formation of methylated sulfides from reduction of dissolved inorganic carbon has previously not been demonstrated. When studying the effect of temperature on hydrogenotrophic microbial activity, we observed formation of DMS in anoxic sediment of Lake Plußsee at 55 °C. Subsequent experiments strongly suggested that the formation of DMS involves fixation of bicarbonate via a reductive pathway in analogy to methanogenesis and engages methylation of MT. DMS formation was enhanced by addition of bicarbonate and further increased when both bicarbonate and H2 were supplemented. Inhibition of DMS formation by 2-bromoethanesulfonate points to the involvement of methanogens. Compared to the accumulation of DMS, MT showed the opposite trend but there was no apparent 1:1 stoichiometric ratio between both compounds. Both DMS and MT had negative d13C values of -62 per mil and -55 per mil, respectively. Labeling with NaH**13CO3 showed more rapid incorporation of bicarbonate into DMS than into MT. The stable carbon isotopic evidence implies that bicarbonate was fixed via a reductive pathway of methanogenesis, and the generated methyl coenzyme M became the methyl donor for MT methylation. Neither DMS nor MT accumulation were stimulated by addition of the methyl-group donors methanol and syringic acid or by the methyl-group acceptor hydrogen sulphide. The source of MT was further investigated in a H2**35S labeling experiment, which demonstrated a microbially-mediated process of hydrogen sulfide methylation to MT that accounted for only <10% of the accumulation rates of DMS. Therefore, the major source of the 13C-depleted MT was neither bicarbonate nor methoxylated aromatic compounds. Other possibilities for isotopically depleted MT, such as other organic precursors like methionine, are discussed. This DMS-forming pathway may be relevant for anoxic environments such as hydrothermally influenced sediments and fluids and sulfate-methane transition zones in marine sediments.

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The Ross Sea polynya is among the most productive regions in the Southern Ocean and may constitute a significant oceanic CO2 sink. Based on results from several field studies, this region has been considered seasonally iron limited, whereby a "winter reserve" of dissolved iron (dFe) is progressively depleted during the growing season to low concentrations (~0.1 nM) that limit phytoplankton growth in the austral summer (December-February). Here we report new iron data for the Ross Sea polynya during austral summer 2005-2006 (27 December-22 January) and the following austral spring 2006 (16 November-3 December). The summer 2005-2006 data show generally low dFe concentrations in polynya surface waters (0.10 ± 0.05 nM in upper 40 m, n = 175), consistent with previous observations. Surprisingly, our spring 2006 data reveal similar low surface dFe concentrations in the polynya (0.06 ± 0.04 nM in upper 40 m, n = 69), in association with relatively high rates of primary production (~170-260 mmol C/m**2/d). These results indicate that the winter reserve dFe may be consumed relatively early in the growing season, such that polynya surface waters can become "iron limited" as early as November; i.e., the seasonal depletion of dFe is not necessarily gradual. Satellite observations reveal significant biomass accumulation in the polynya during summer 2006-2007, implying significant sources of "new" dFe to surface waters during this period. Possible sources of this new dFe include episodic vertical exchange, lateral advection, aerosol input, and reductive dissolution of particulate iron.

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Chemical analyses have been carried out on 40 samples from the sediment surface and 210 samples from cores that were taken from the edge of the African continental block at the Arabian Sea (coasts of Somalia and Kenya, from Cape Guardafui to Mombasa) on the occasion of the Indian Ocean Expedition of the German research vessel "Meteor" during the years 1964/65. The carbonate content shows its maximum on the northern part of the continental shelf of Africa, where fossil reef debris furnish the detritic portion of carbonate. In the southern part of the continental shelf of Africa the portion of carbonate is low, as it is heavily diluted by the non-carbonatic detritus. It is also in the deep-sea that a lower carbonate content is encountered below the calcite compensation depth. Trace elements in the carbonates: On the shelf and in its vicinity Sr and Mg are enriched. The enrichment has been brought about by the portion of reef debris, as this latter contains aragonite (enrichment of Sr) as well as high-magnesium calcite. The greatest part of the slope contains carbonates that are poor in trace elements and mainly made up of foraminifera (and of coccoliths). Below the carbonate compensation depth another enrichment of Mg takes place in the carbonates, which is probably due to a selective dissolution of calcite in comparison to dolomite. The iron and manganese contents of the carbonates are high (iron higher in coast proximity, manganese higher in the depth), but not genuine, as they come about in the course of the extraction of the carbonates as a result of the dissolution of authigenic Mn-Fe-minerals. Non-carbonatic portion of the sediments: In coast proximity an enrichment of quartz comes about. Within the quartz-rich zone it is the elements V, Cr, Fe, Ti, and B that have been enriched in the non-carbonatic components. This enrichment must be attributed to an elevated content of heavy minerals. In the case of Ti and Fe the preliminary enrichment brought about by processes of lateritisation on the continent plays a certain role. Toward the deep-sea an enrichment of the elements Mn Ni, Cu, and Zn takes place; these enrichments must be explained by authigenic Mn-Fe-minerals. Within the Mn-rich zone a belt running parallel to the coast stands out that shows an increased Mn-enrichment. However, this increase in enrichment does not apply to the elements Ni, Cu, and Zn. It is probable that this latter increased enrichment comes about as a result of the migration of manganese to the sediment surface. (Within the sediments there prevail reductive conditions, in the presence of which Mn is capable of migration, whereas at the sediment surface its precipitation comes about under oxidizing conditions). The quantity of organic matter mainly is dependent on grain size and on the rate of sedimentation. On the shelf an impoverishment of organic matter is to be encountered, as the sediments are coarse-grained. In the depth the impoverishment must be explained on the strength of a small rate of sedimentation. Between those two ranges organic substance is enriched. P and N show an enrichment in comparison to Corg with this applying all the more the smaller the absolute quantity of Corg is. In this particular case one has to do with an enrichment coming about during the diagenetic processes of organic matter. A comparison with the sediments from the Indian and Pakistani continental border in Arabian Sea shows as follows: on the African continental border the coarse detrital material has been transported farther out to deep-sea, which has something to do with the greater inclination of the surface of sedimentation. Carbonate is found in greater abundance on the African side. Its chemical composition is influenced by reef-debris which is missing by Indian-Pakistani side. The content of organic matter is lower on the African side. Contrary to that, the enrichments of N and P compared to organic matter are of an equal order of magnitude on both sides of the Arabian Sea.

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Despite intensive research on the different domains of the marine phosphorus (P) cycle during the last decades, frequently discussed open questions still exist especially on controlling factors for the benthic behaviour of P and its general distribution in sediment-pore water systems. Steady state or the internal balance of all relevant physical and (bio)geochemical processes are amongst the key issues. In this study we present and discuss an extended data set from surface sediments recovered from three locations on the NW African continental slope. Pore water data and results from sequential sediment extractions give clear evidence to the well-known close relationship between the benthic cycles of P and iron. Accordingly, most of the dissolved phosphate must have been released by microbially catalyzed reductive dissolution of iron (oxhydr)oxides. However, rates of release and association of P and iron, respectively, are not directly represented in profiles of element specific sediment compositions. Results from steady-state based transport-reaction modelling suggest that particle mixing due to active bioturbation, or rather a physical net downward transport of P associated to iron (oxyhydr)oxides, is an essential process for the balance of the inspected benthic cycles. This study emphasizes the importance of balancing analytical data for a comprehensive understanding of all processes involved in biogeochemical cycles.