A provisional diagenetic model for pH in anoxic porewaters: Application to the FOAM Site

This paper presents a diffusion-advection-reaction model for the pH of anoxic porewaters in nonirrigated sediments. Because of the couplings demanded by the organic-matter decay reaction, various acid-base interconversions, dissolved-iron generation, and CaCO3 and FeS precipitation, the model does not consider H+ alone, but deals simultaneously with 17 dissolved species. The complex and largely unknown kinetics of some of the processes affecting these species have been approximated by simple ad hoc formulations. For this reason, the model must be considered provisional. We have also made extensive use of the local (partial) equilibrium assumption to circumvent the computational problems generated by rapid association/dissociation reactions. The FOAM Site data are used as a vehicle to display the capabilities of this model. Assuming local equilibrium with FeS, the predicted pH profile is most sensitive to the reaction that liberates iron from the solid phase. The FOAM pH does not conform to a profile expected for anyone iron-source mineral, but appears to reflect a composite source. Based on currently available data, this source might include magnetite and silicate minerals, but is unlikely to involve ferric oxides and hydroxides. The pH of FOAM porewaters is much less sensitive to the precipitation of FeS and CaCO3 than would be suggested by past closed-system models. The overall pH stability of anoxic porewaters is attributable to the fact that the dissolved products of organic-matter decomposition are added in such a way as to form a self-buffering mixture

Nitrogen removal in marine environments: recent findings and future research challenges

Respiratory reduction of nitrate (denitrification) is recognized as the most important process converting biologically available (fixed) nitrogen to N2. In current N cycle models, a major proportion of global marine denitrification (50–70%) is assumed to take place on the sea floor, particularly in organic rich continental margin sediments. Recent observations indicate that present conceptual views of denitrification and pathways of nitrate reduction and N2 formation are incomplete. Alternative N cycle pathways, particularly in sediments, include anaerobic ammonium oxidation to nitrite, nitrate and N2 by Mn-oxides, and anaerobic ammonium oxidation coupled to nitrite reduction and subsequent N2 mobilization. The discovery of new links and feedback mechanisms between the redox cycles of, e.g., C, N, S, Mn and Fe casts doubt on the present general understanding of the global N cycle. Recent models of the oceanic N budget indicate that total inputs are significantly smaller than estimated fixed N removal. The occurrence of alternative N reaction pathways further exacerbates the apparent imbalance as they introduce additional routes of N removal. In this contribution, we give a brief historical background of the conceptual understanding of N cycling in marine ecosystems, emphasizing pathways of aerobic and anaerobic N mineralization in marine sediments, and the implications of recently recognized metabolic pathways for N removal in marine environments

No nitrogen fixation in the Bay of Bengal?

The Bay of Bengal (BoB) has long stood as a biogeochemical enigma, with subsurface waters containing extremely low, but persistent, concentrations of oxygen in the nanomolar range which – for some, yet unconstrained, reason – are prevented from becoming anoxic. One reason for this may be the low productivity of the BoB waters due to nutrient limitation and the resulting lack of respiration of organic material at intermediate waters. Thus, the parameters determining primary production are key in understanding what prevents the BoB from developing anoxia. Primary productivity in the sunlit surface layers of tropical oceans is mostly limited by the supply of reactive nitrogen through upwelling, riverine flux, atmospheric deposition, and biological dinitrogen (N2) fixation. In the BoB, a stable stratification limits nutrient supply via upwelling in the open waters, and riverine or atmospheric fluxes have been shown to support only less than one-quarter of the nitrogen for primary production. This leaves a large uncertainty for most of the BoB's nitrogen input, suggesting a potential role of N2 fixation in those waters. Here, we present a survey of N2 fixation and carbon fixation in the BoB during the winter monsoon season. We detected a community of N2 fixers comparable to other oxygen minimum zone (OMZ) regions, with only a few cyanobacterial clades and a broad diversity of non-phototrophic N2 fixers present throughout the water column (samples collected between 10 and 560 m water depth). While similar communities of N2 fixers were shown to actively fix N2 in other OMZs, N2 fixation rates were below the detection limit in our samples covering the water column between the deep chlorophyll maximum and the OMZ. Consistent with this, no N2 fixation signal was visible in δ15N signatures. We suggest that the absence of N2 fixation may be a consequence of a micronutrient limitation or of an O2 sensitivity of the OMZ diazotrophs in the BoB. Exploring how the onset of N2 fixation by cyanobacteria compared to non-phototrophic N2 fixers would impact on OMZ O2 concentrations, a simple model exercise was carried out. We observed that both photic-zone-based and OMZ-based N2 fixation are very sensitive to even minimal changes in water column stratification, with stronger mixing increasing organic matter production and export, which can exhaust remaining O2 traces in the BoB

Molybdenum evidence for expansive sulfidic water masses in ~750Ma oceans

The Ediacaran appearance of large animals, including motile bilaterians, is commonly hypothesized to reflect a physiologically enabling increase in atmospheric and oceanic oxygen abundances (pO2). To date, direct evidence for low oxygen in pre-Ediacaran oceans has focused on chemical signatures in the rock record that reflect conditions in local basins, but this approach is both biased to constrain only shallower basins and statistically limited when we seek to follow the evolution of mean ocean chemical state through time. Because the abundance and isotopic composition of molybdenum (Mo) in organic-rich euxinic sediments can vary in response to changes in global redox conditions, Mo geochemistry provides independent constraints on the global evolution of well-oxygenated environments. Here, we establish a theoretical framework to access global marine Mo cycle in the past from the abundance and isotope composition of ancient seawater. Further, we investigate the ~ 750 Ma Walcott Member of the Chuar Group, Grand Canyon, which accumulated in a rift basin with open connection to the ocean. Iron speciation data from upper Walcott shales indicate that local bottom waters were anoxic and sulfidic, consistent with their high organic content (up to 20 wt.%). Similar facies in Phanerozoic successions contain high concentrations of redox-sensitive metals, but in the Walcott Member, abundances of Mo and U, as well as Mo/TOC (~ 0.5 ppm/wt.%) are low. δ98Mo values also fall well below modern equivalents (0.99 ± 0.13‰ versus ~ 2.35‰ today). These signatures are consistent with model predictions where sulfidic waters cover ~ 1–4% of the global seafloor, corresponding to a ~ 20–80 fold increase compared to the modern ocean. Therefore, our results suggest globally expansive sulfidic water masses in mid-Neoproterozoic oceans, bridging a nearly 700 million-year gap in previous Mo data. We propose that anoxic and sulfidic (euxinic) conditions governed Mo cycling in the oceans even as ferruginous subsurface waters re-appeared 800–750 Ma, and we interpret this anoxic ocean state to reflect a markedly lower atmospheric and oceanic O2 level, consistent with the hypothesis that pO2 acted as an evolutionary barrier to the emergence of large motile bilaterian animals prior to the Ediacaran Period.Organismic and Evolutionary Biolog

An Emerging Picture of Neoproterozoic Ocean Chemistry: Insights from the Chuar Group, Grand Canyon, USA

Detailed iron, sulfur and carbon chemistry through the > 742 million year old ChuarGroup reveals a marine basin dominated by anoxic and ferrous iron-rich (ferruginous) bottom waters punctuated, late in the basin's development, by an intrusion of sulfide-rich (euxinic) conditions. The observation that anoxia occurred frequently in even the shallowest of Chuar environments (10s of meters or less) suggests that global atmospheric oxygen levels were significantly lower than today. In contrast, the transition from ferruginous to euxinic subsurface water is interpreted to reflect basinal control—specifically, increased export of organic carbon from surface waters. Low fluxes of organic carbon into subsurface water masses should have been insufficient to deplete oxygen via aerobic respiration, resulting in an oxic oxygen minimum zone (OMZ). Where iron was available, larger organic carbon fluxes should have depleted oxygen and facilitated anaerobic respiration using ferric iron as the oxidant, with iron carbonate as the expected mineralogical signature in basinal shale. Even higher organic fluxes would, in turn, have depleted ferric iron and up-regulated anaerobic respiration by sulfate reduction, reflected in high pyrite abundances. Observations from the ChuarGroup are consistent with these hypotheses, and gain further support from pyrite and sulfate sulfur isotope abundances. In general, Chuar data support the hypothesis that ferruginous subsurface waters returned to the oceans, replacing euxinia, well before the Ediacaran emergence of persistently oxygenated conditions, and even predating the Sturtian glaciation. Moreover, our data suggest that the reprise of ferruginous water masses may relate to widespread rifting during the break-up of Rodinia. This environmental transition, in turn, correlates with both microfossil and biomarker evidence for an expanding eukaryotic presence in the oceans, suggesting a physiologically mediated link among tectonics, environmental chemistry and life in the dynamic Neoproterozoic Earth system.Earth and Planetary Science

The Sirius Passet Lagerstätte of North Greenland—A geochemical window on early Cambrian low‐oxygen environments and ecosystems

The early Cambrian Sirius Passet fauna of northernmost Greenland (Cambrian Series 2, Stage 3) contains exceptionally preserved soft tissues that provide an important window to early animal evolution, while the surrounding sediment holds critical data on the palaeodepositional water‐column chemistry. The present study combines palaeontological data with a multiproxy geochemical approach based on samples collected in situ at high stratigraphic resolution from Sirius Passet. After careful consideration of chemical alterations during burial, our results demonstrate that fossil preservation and biodiversity show significant correlation with iron enrichments (FeHR/FeT), trace metal behaviour (V/Al), and changes in nitrogen cycling (δ15N). These data, together with Mo/Al and the preservation of organic carbon (TOC), are consistent with a water column that was transiently low in oxygen concentration, or even intermittently anoxic. When compared with the biogeochemical characteristics of modern oxygen minimum zones (OMZs), geochemical and palaeontological data collectively suggest that oxygen concentrations as low as 0.2–0.4 ml/L restricted bioturbation but not the development of a largely nektobenthic community of predators and scavengers. We envisage for the Sirius Passet biota a depositional setting where anoxic water column conditions developed and passed over the depositional site, possibly in association with sea‐level change, and where this early Cambrian biota was established in conditions with very low oxygen

Increased accumulation of sulfur in lake sediments of the high Arctic

Author Posting. © The Author(s), 2010. This is the author's version of the work. It is posted here by permission of American Chemical Society for personal use, not for redistribution. The definitive version was published in Environmental Science & Technology 44 (2010): 8415-8421, doi:10.1021/es101991p.We report a synchronous increase in accumulation of reduced inorganic sulfur since c. 1980 in sediment cores from eight of nine lakes studied in the Canadian Arctic and Svalbard (Norway). Sediment incubations and detailed analyses of sediment profiles from two of the lakes indicate that increases in sulfur accumulation may be due ultimately to a changing climate. Warming-induced lengthening of the ice-free season is resulting in well-documented increases in algal production and sedimentation of the resulting detrital matter. Algal detritus is a rich source of labile carbon, which in these sediments stimulates dissimilatory sulfate reduction. The sulfide produced is stored in sediment (as acid volatile sulfide), converted to other forms of sulfur, or reoxidized to sulfate and lost to the water column. An acceleration of the sulfur cycle in Arctic lakes could have profound effects on important biogeochemical processes, such as carbon burial and mercury methylation.Funding was provided by the WHOI Ocean and Climate Change Institute, the USGS WHOI Postdoctoral Scholar Program, Environment Canada, the Danmarks Grundforskningsfond, and the Norges forskningsråd (grant number 107745/730)