Iron Speciation Data Research Articles

A global transition to ferruginous conditions in the early Neoproterozoic oceans

Eukaryotic life expanded during the Proterozoic eon1, 2.5 to 0.542 billion years ago, against a background of fluctuating ocean chemistry2, 3, 4. After about 1.8 billion years ago, the global ocean is thought to have been characterized by oxygenated surface waters, with anoxic and sulphidic waters in middle depths along productive continental margins and anoxic and iron-containing (ferruginous) deeper waters5, 6, 7. The spatial extent of sulphidic waters probably varied through time5, 6, but this surface-to-deep redox structure is suggested to have persisted until the first Neoproterozoic glaciation about 717 million years ago8, 9, 10, 11. Here we report an analysis of ocean redox conditions throughout the Proterozoic using new and existing iron speciation and sulphur isotope data from multiple cores and outcrops. We find a global transition from sulphidic to ferruginous mid-depth waters in the earliest Neoproterozoic, coincident with the amalgamation of the supercontinent Rodinia at low latitudes. We suggest that ferruginous conditions were initiated by an increase in the oceanic influx of highly reactive iron relative to sulphate, driven by a change in weathering regime and the uptake of sulphate by extensive continental evaporites on Rodinia. We propose that this transition essentially detoxified ocean margin settings, allowing for expanded opportunities for eukaryote diversification following a prolonged evolutionary stasis before one billion years ago.

Assessing the utility of Fe/Al and Fe-speciation to record water column redox conditions in carbonate-rich sediments

Geochemical proxies based on Fe abundance (Fe/Al) and Fe-speciation have been widely applied to marine sediments in order to unravel paleo-depositional redox conditions though geological time. To date, however, these Fe proxies have only been calibrated in relation to modern and ancient fine-grained siliciclastic marine sediments. This clearly limits their use, particularly in relation to carbonate-rich sediments and rocks. To address this, we here explore the applicability of Fe-based redox proxies in carbonates through three approaches. First, we have compiled Fe/Al data for modern marine sediments to investigate variability in Fe-enrichments as a function of carbonate content and depositional setting. Second, we have expanded this approach with a compilation of new and existing Fe-speciation data for modern and ancient marine sediments deposited under oxic and euxinic (anoxic sulfidic) water column conditions. Finally, we show new data from paired limestone and dolomite sample sets to demonstrate the potential significance of deep burial dolomitization on the Fe-speciation redox proxy.Modern marine sediments deposited under oxic conditions show no relationship between Fe/Al and carbonate content. These sediments have an average Fe/Al ratio of 0.55±0.11, with some higher values potentially being attributable to steady-state early diagenetic remobilization of Fe towards the sediment–water interface. In contrast, significant Fe/Al enrichments occur as a consequence of water column Fe mineral formation and deposition, either under anoxic conditions, or due to input of anoxic hydrothermal fluids into oxic seawater. Iron speciation data also show no direct correlation with carbonate content, and instead three groups can be distinguished based on total Fe (FeT) and organic C contents. Sediments deposited under oxic water column conditions, with FeT >0.5wt.%, generally plot below the lower FeHR/FeT siliciclastic reference threshold (0.38) for distinguishing anoxic environments, regardless of carbonate content. Also consistent with siliciclastic calibrations, carbonate-rich sediments deposited under anoxic water column conditions tend to have FeHR/FeT ratios >0.38. In contrast, oxic carbonate-rich sediments with low FeT (<0.5wt.%) and low organic C (<0.5wt.%) routinely give spuriously high FeHR/FeT ratios, suggesting that the use of Fe-speciation for such samples is not appropriate for evaluating water column redox conditions. Taken together, our data suggest that an FeT content of >0.5wt.%, rather than carbonate content, represents the most suitable basis for identifying whether carbonate-rich sediments are appropriate for Fe-based redox proxy analyses. Analysis of burial dolostones suggests that the Fe-speciation proxy may also be compromised by deep burial dolomitization, where there has been a source of mobile Fe to enrich rocks during recrystallization. However, pre-screening can identify such samples. This new assessment expands the utility of Fe-based redox proxies to also incorporate appropriate carbonate-rich rocks, provided that care is taken to assess the possible impact of deep burial dolomitization.

The spread of marine anoxia on the northern Tethys margin during the Paleocene-Eocene Thermal Maximum

Records of the paleoenvironmental changes that occurred during the Paleocene-Eocene Thermal Maximum (PETM) are preserved in sedimentary rocks along the margins of the former Tethys Ocean and Peri-Tethys. This paper presents new geochemical data that constrain paleoproductivity, sediment delivery, and seawater redox conditions, from three sites that were located in the Peri-Tethys region. Trace and major element, iron speciation, and biomarker data indicate that water column anoxia was established during episodes when inputs of land-derived higher plant organic carbon and highly weathered detrital clays and silts became relatively higher. Anoxic conditions are likely to have been initially caused by two primary processes: (i) oxygen consumption by high rates of marine productivity, initially stimulated by the rapid delivery of terrestrially derived organic matter and nutrients, and (ii) phosphorus regeneration from seafloor sediments. The role of the latter process requires further investigation before its influence on the spread of deoxygenated seawater during the PETM can be properly discerned. Other oxygen-forcing processes, such as temperature/salinity-driven water column stratification and/or methane oxidation, are considered to have been relatively less important in the study region. Organic carbon enrichments occur only during the initial stages of the PETM as defined by the negative carbon isotope excursions at each site. The lack of observed terminal stage organic carbon enrichment does not support a link between PETM climate recovery and the sequestration of excess atmospheric CO2 as organic carbon in this region; such a feedback may, however, have been important in the early stages of the PETM.

Phosphorus sources for phosphatic Cambrian carbonates

The fossilization of organic remains and shell material by calcium phosphate minerals provides an illuminating, but time-bounded, window into Ediacaran–Cambrian animal evolution. For reasons that remain unknown, phosphatic fossil preservation declined significantly through Cambrian Series 2. Here, we investigate the phosphorus (P) sources for phosphatic Cambrian carbonates, presenting sedimentological, petrographic, and geochemical data from the Cambrian Series 2–3 Thorntonia Limestone, Australia, some of the youngest Cambrian strata to display exceptional phosphatic preservation of small shelly fossils. We find that within Thorntonia sediments, phosphate was remobilized by organic decay and bacterial iron reduction, with subsequent reprecipitation largely as apatite within the interiors of small shelly fossils. We discuss the merits of bioclastic-derived, organic matter–bound, or iron-bound P as potential sources to these strata. Petrographic observations suggest that the dissolution of phosphatic skeletal material did not provide the P for fossil preservation. In contrast, high organic carbon contents imply significant organic fluxes of P to Thorntonia sediments. Sedimentology and iron-speciation data indicate that phosphorus enrichment occurred during times of expanded anoxic, ferruginous conditions in subsurface water masses, suggesting that phosphorus adsorption to iron minerals precipitating from the water column provided a second significant P source to Thorntonia sediments. Simple stoichiometric models suggest that, by themselves, neither organic carbon burial nor an iron shuttle can account for the observed phosphorus enrichment. Thus, we infer that both processes were necessary for the observed phosphorus enrichment and subsequent fossil preservation in the Thorntonia Limestone.

Late Ediacaran redox stability and metazoan evolution

The Neoproterozoic arrival of animals fundamentally changed Earth's biological and geochemical trajectory. Since the early description of Ediacaran and Cambrian animal fossils, a vigorous debate has emerged about the drivers underpinning their seemingly rapid radiation. Some argue for predation and ecology as central to diversification, whereas others point to a changing chemical environment as the trigger. In both cases, questions of timing and feedbacks remain unresolved. Through these debates, the last fifty years of work has largely converged on the concept that a change in atmospheric oxygen levels, perhaps manifested indirectly as an oxygenation of the deep ocean, was causally linked to the initial diversification of large animals. What has largely been absent, but is provided in this study, is a multi-proxy stratigraphic test of this hypothesis. Here, we describe a coupled geochemical and paleontological investigation of Neoproterozoic sedimentary rocks from northern Russia. In detail, we provide iron speciation data, carbon and sulfur isotope compositions, and major element abundances from a predominantly siliciclastic succession (spanning>1000m) sampled by the Kel'tminskaya-1 drillcore. Our interpretation of these data is consistent with the hypothesis that the pO2 threshold required for diversification of animals with high metabolic oxygen demands was crossed prior to or during the Ediacaran Period. Redox stabilization of shallow marine environments was, however, also critical and only occurred about 560 million years ago (Ma), when large motile bilaterians first enter the regional stratigraphic record. In contrast, neither fossils nor geochemistry lend support to the hypothesis that ecological interactions altered the course of evolution in the absence of environmental change. Together, the geochemical and paleontological records suggest a coordinated transition from low oxygen oceans sometime before the Marinoan (∼635Ma) ice age, through better oxygenated but still redox-unstable shelves of the early Ediacaran Period, to the fully and persistently oxygenated marine environments characteristic of later Ediacaran successions that preserve the first bilaterian macrofossils and trace fossils.

Evolution from an anoxic to oxic deep ocean during the Ediacaran–Cambrian transition and implications for bioradiation

The Ediacaran–Cambrian transition, one of the most critical intervals in Earth's history, is marked by dramatic biological, oceanic and geochemical turnovers. Here high-resolution carbon and sulfur isotopic data respectively for organic carbon and pyrite, and iron speciation data are presented from the deep-water Liuchapo and Niutitang Formations on the Yangtze block, South China. The carbon isotopic data, together with biostratigraphic and radiometric dating, offer the compelling evidence for the placement of Ediacaran–Cambrian boundary within the Liuchapo Formation (chert succession), and for its correlation with shallow-water equivalents elsewhere. In this context, iron speciation and sulfur isotopic data further suggest a predominant anoxic and ferruginous deep ocean over the transitional time until the middle Early Cambrian (Atdabanian or Stage 3) when the deep ocean was rapidly oxygenated. Coincidently, during this interval, large-body metazoans (i.e., sponges) abruptly appeared in the deep ocean, which was temporally associated with the highly diversified large-body skeletonized animals (i.e., Chengjiang Biota) which colonized in shallow-water niches particularly in southwestern China. This scenario suggests a causal link between deep oceanic oxygenation and the explosive diversification of large-body skeletonized organisms in the Early Cambrian.

Sulfur isotopic trends and iron speciation from the c. 2.0 Ga Pilgujärvi Sedimentary Formation, NW Russia

Sulfide sulfur isotope values and iron speciation data are reported here for sediments from the 2.0 Ga old Pilgujärvi Sedimentary Formation, Pechenga Greenstone Belt, NW Russia. Sulfides are abundant throughout the c. 1400m thick turbiditic sandstone-siltstone-shale succession and present as pyrite and pyrrhotite. A stratigraphic trend is discernible with respect to sulfide mineralogy and sulfur isotopic compositions, changing up-section from highly to less variable and positive δ34S values. The occurrence of pyrrhotite, particularly high in the upper part of the section, is thought to be the result of decomposition of pyrite during low-grade metamorphism. This is evidenced by the crystallographic habit and sulfur isotopic composition of the different sulfide minerals. The δ34S of both sulfur species is quite variable in the lower part of the formation (−9.5% to 18.7%) while the upper part displays a smaller fluctuation in δ34S (4.4%–13.3%). The pyrrhotite is generally depleted in 34S by approximately 3.6% (average isotopic difference between pyrrhotite and pyrite) compared to the pyrite; this shift in the sulfur isotopic composition results from thermal decomposition of pyrite.The overall spread in δ34S is indicative for the microbial reduction of sulfate, but δ34S values suggest a sulfate limited environment in the upper part of the formation. We note, however, that the sulfate limitation is restricted to the pore water realm, caused by high sedimentation rates that inhibited a sufficiently high sulfate flux from the overlying water column into the sediment.Based on iron speciation data, a previous characterization of the depositional environment as non-euxinic can be specified more precisely. We note that the siliciclastic succession of the Pilgujärvi Sedimentary Formation was deposited under anoxic and ferruginous water column conditions derived from high ratios of FeHR/FeT and low ratios of Fepy/FeHR.

Molybdenum evidence for expansive sulfidic water masses in ~ 750 Ma 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 (pO 2). 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. δ 98 Mo 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 O 2 level, consistent with the hypothesis that pO 2 acted as an evolutionary barrier to the emergence of large motile bilaterian animals prior to the Ediacaran Period.

Vertical distributions of iron-(III) complexing ligands in the Southern Ocean

Electrochemically derived iron speciation data from four vertical profiles to 1000 m depth were obtained during the SAZ-Sense voyage to offshore waters south of Australia in summer (January/February, 2007). The dual aims of this study were firstly to devise a new operational definition to represent the ‘complexing capacity’, or total concentration of iron-complexing ligands, and subsequently derive vertical profiles of these ligand classes. Secondly, to compare the vertical trends for each ligand class with vertical distributions in oceanic properties thought to control ligand production (i.e. siderophores produced by bacteria and particle remineralisation). Based on simulated ligand titrations, we operationally defined Σ L as the overall class of ligands, which represents all iron-complexing ligands detectable under the analytical conditions chosen. The stability constant of ΣL is a weighted average for these ligands. The ligand titration data suggests the presence of an excess of iron-complexing ligands throughout the water column with an average concentration of [Σ L]=0.75±0.20 nM ( n=47), and an average stability constant of log K FeS L , Fe 3 + =21.50±0.24 ( n=47). Here, based on the range of observed stability constants we define a distinctly different class of extremely strong ligands ( L 1) to be the ligand class with a stability constant of log K Fe L 1 , Fe 3 + ≥22 , whereas Σ L ranged from 21.00 to 21.95 for log K Fe L 1 , Fe 3 + . L 1 had an average concentration and stability constant of 0.42±0.10 nM ( n=14) and 22.97±0.48 ( n=14), respectively. L 1 was only found in three of the four depth profiles, and was restricted to the upper ocean (i.e. <200 m depth), whereas Σ L was observed at all sampling depths down to 1000 m. Heterotrophic bacterial abundances (a proxy for siderophore production) were always the highest in the surface mixed layer (50–72 m depth for the 4 stations) then decreased sharply, whereas POC downward flux (a proxy for remineralisation) was greatest below the surface mixed layer then decreased exponentially. It has been suggested that siderophores control L 1 production whereas the remainder of Σ L may be set by particle breakdown (Hunter and Boyd, 2007). Hence we should expect some vertical partitioning of L 1 (present<70 m depth) and Σ L (present over the water column). However, profiles at all stations in subtropical, subantarctic, and polar waters exhibited distinguishable concentrations of L 1 to 200 m depth (i.e. straddling both regions of putative L 1 and Σ L production). There remain issues with the separation of different ligand classes, such that since [ L 1]≤ [Fe] , deeper in the water column, the concentration of L 1 cannot be resolved, and hence the provenance of both L 1 and Σ L cannot be clearly assigned.

A Late Archean Sulfidic Sea Stimulated by Early Oxidative Weathering of the Continents

Iron speciation data for the late Archean Mount McRae Shale provide evidence for a euxinic (anoxic and sulfidic) water column 2.5 billion years ago. Sulfur isotope data compiled from the same stratigraphic section suggest that euxinic conditions were stimulated by an increase in oceanic sulfate concentrations resulting from weathering of continental sulfide minerals exposed to an atmosphere with trace amounts of photosynthetically produced oxygen. Variability in local organic matter flux likely confined euxinic conditions to midportions of the water column on the basin margin. These findings indicate that euxinic conditions may have been common on a variety of spatial and temporal scales both before and immediately after the Paleoproterozoic rise in atmospheric oxygen, hinting at previously unexplored texture and variability in deep ocean chemistry during Earth's early history.

The chemical speciation of iron in the north-east Atlantic Ocean

The distribution of dissolved iron and its chemical speciation (organic complexation and redox speciation) were studied in the northeastern Atlantic Ocean along 23°W between 37 and 42°N at depths between 0 and 2000 m, and in the upper-water column (upper 200 m) at two stations further east at 45°N10°W and 40°N17°W in the early spring of 1998. The iron speciation data are here combined with phytoplankton data to suggest cyanobacteria as a possible source for the iron binding ligands. The organic Fe-binding ligand concentrations were greater than that of dissolved iron by a factor of 1.5–5, thus maintaining iron in solution at levels well above it solubility. The water column distribution of the organic ligand indicates in-situ production of organic ligands by the plankton (consisting mainly of the cyanobacteria Synechococcus sp.) in the euphotic layer and a remineralisation from sinking biogenic particles in deeper waters. Fe(II) concentrations varied from below the detection limit (<0.1 nM) up to 0.55 nM but represented only a minor fraction of 0% to occasionally 35% of the dissolved iron throughout the water column. The water column distribution of the Fe(II) suggests biologically mediated production in the deep waters and photochemical production in the euphotic layer. Although there was no evidence of iron limitation in these waters, the aeolian iron input probably contributed to a shift in the phytoplankton assemblage towards increased Synechococcus growth.

Stability of Silicate Coatings on Pyrite Surfaces in a Low pH Environment

The suppression of pyrite oxidation due to the formation of stable coatings of Fe3+ –silica and/or Fe3+ –hydroxy–silica complexes over pyrite surfaces in near-neutral and neutral solution pHs is well documented. On the contrary, there is currently no convincing experimental evidence that proves the existence of such a coating under low pH environments. Aqueous continuous flow kinetic experiments were conducted using coating solutions containing Na2 Si O3 ∙5 H2 O and H2 O2 at pH 6, 4, 3, and 2. Results showed that at pH 2, pyrite oxidation in the presence of silica is pseudofirst order and oxidation is not inhibited by silica. At pH 6, silica significantly reduced pyrite oxidation via a pseudofirst-order reaction that takes on several stages related to changes in the relative contributions of H2 O2 and Fe3+ . Iron speciation data suggests a surface adsorption mechanism at pH 6 and an electrochemical mechanism at pH 2 for pyrite oxidation. Scanning electron microscopy and energy dispersive x-ray spectroscop...

Reply to Comments on 'Measuring Marine Iron(III) Complexes by CLE-AdSV'

Environmental Context. The interpretation of CLE-AdSV based iron(iii) speciation data for marine waters has been called into question in light of the kinetic features of the measurement. The implications of the re-think may have consequences for understanding iron biogeochemistry and its impact on ecosystem functioning. The challenging of previously accepted results stimulated this debate on what is actually being measured by the CLE-AdSV technique.

Measuring Marine Iron(III) Complexes by CLE-AdSV

Environmental Context. Iron is an essential element for life in the world's oceans, and in some regions its concentration limits the growth of phytoplankton. The amount of iron(iii) which is available to an organism depends on the exact chemical form in which it exists, for example as dissolved ions or associated with organic compounds. There are widespread reports that marine iron(iii) is predominantly bound in extremely strong complexes. We show that such claims might be the result of an artefact of the measurement technique, CLE-AdSV. Ensuing ideas about the iron biogeochemistry in marine systems might require reconsideration as well. Abstract. Iron(iii) speciation data, as determined by competitive ligand exchange?adsorptive stripping voltammetry (CLE-AdSV), is reconsidered in the light of the kinetic features of the measurement. The very large stability constants reported for iron(iii) in marine ecosystems are shown to be possibly due to an artefact of the technique, arising from the assumption that equilibrium is achieved between all iron(iii) species of relevance. Particular kinetic properties, related to the special nature of hydroxide as a metal complexant, have the consequence that CLE-AdSV measurements of iron(iii) in seawater generally correspond to the hydroxide complexes only. By the same token, dissolved hydroxide complexes are the key components of the bioavailable iron(iii) pool. The analysis presented herein opens opportunities to exploit CLE-AdSV for more rigorous investigation of the links between the speciation and the bioavailability of iron(iii).

Sources and mechanisms for the enrichment of highly reactive iron in euxinic Black Sea sediments

The deep basinal euxinic sediments of the Black Sea are enriched in iron that is highly susceptible to sulfidization compared to oxic/suboxic continental margin sediments in the Black Sea and oxic/dysoxic continental margin and deep-sea sediments worldwide. A mass balance treatment of iron speciation data from three deep basin sediment cores shows that this enrichment is due to a combination of (1) highly reactive iron-bearing phases (sulfides and oxides) whose ultimate source was by diagenetic mobilization from the shelf (Wijsman and others, 2001) and (2) enhanced iron reactivity in the lithogenous component of deep basinal sediments. The cause of the enhanced reactivity of lithogenous iron is problematical. Possible mechanisms include microbial oxidation of non-reactive iron silicates and the preferential deposition of a fine-grained, reactive iron-enriched lithogenous component in the deep basin by the fractionation of the lithogenous flux during transport across the shelf. The application of paleoredox indicators based on iron reactivity (Degree of Pyritization, Indicator of Anoxicity) should take into account that the availability of highly reactive iron, and hence the concentration of reactive iron phases in the sediment, is controlled by a variety of chemical, physical and biological factors, some of which are not related directly to redox conditions in the water column.

Continuous flow analysis of iron in zinc electrowinning electrolyte using an iron chalcogenide glass ion-selective electrode: Part I. Synthetic media

It is shown that the iron(III) chalcogenide glass membrane ion-selective electrode (ISE) can be calibrated in continuous flow analysis (CFA) using acidified iron(III) nitrate standards, yielding a 60±3 mV per decade change in activity of Fe 3+ response in the range 10 −7–10 −2 M total iron(III). Extended ageing of the iron(III) ISE in 2 M zinc(II) sulphate did not alter the potentiometric response characteristics of the electrode. Furthermore, electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy in the presence and absence of zinc(II) sulphate failed to detect a zinc(II) interference on the iron(III) ISE. CFA/ISE determined activities of Fe 3+ in synthetic zinc electrolyte containing 2×10 −3–2×10 −1 M total iron(III) yielded results falling within ±0.2 log aFe 3+ unit of the corresponding iron speciation data calculated using the minteqa2 program.