Iron-mediated anaerobic ammonium oxidation recorded in the early Archean ferruginous ocean

The nitrogen isotopic composition of organic matter is controlled by metabolic activity and redox speciation and has therefore largely been used to uncover the early evolution of life and ocean oxygenation. Specifically, positive δ¹⁵N values found in well-preserved sedimentary rocks are often interpreted as reflecting the stability of a nitrate pool sustained by water column partial oxygenation. This study adds much-needed data to the sparse Paleoarchean record, providing carbon and nitrogen concentrations and isotopic compositions for more than fifty samples from the 3.4 Ga Buck Reef Chert sedimentary deposit (BRC, Barberton Greenstone Belt). In the overall anoxic and ferruginous conditions of the BRC depositional environment, these samples yield positive δ¹⁵N values up to +6.1‰. We argue that without a stable pool of nitrates, these values are best explained by non-quantitative oxidation of ammonium via the Feammox pathway, a metabolic co-cycling between iron and nitrogen through the oxidation of ammonium in the presence of iron oxides. Our data contribute to the understanding of how the nitrogen cycle operated under reducing, anoxic, and ferruginous conditions, which are relevant to most of the Archean. Most importantly, they invite to carefully consider the meaning of positive δ¹⁵N signatures in Archean sediments.     

Evidence for the development of local anoxia during the Cambrian SPICE event in eastern North America

The later Cambrian Steptoean Positive Carbon Isotope Excursion (SPICE) event was an episode marked by pronounced changes to the global biogeochemical cycles of carbon and sulfur and significant extinctions on several paleocontinents including Laurentia (North America). While the exact cause(s) of these events remains debated, various lines of evidence suggest an increase in the areal extent of anoxia at the seafloor was a likely feature. Here, we explore whether changes in local oxygenation accompanied the onset of the SPICE in southern Laurentia using cores of the Nolichucky and Eau Claire Formations from Ohio and Kentucky, USA, that represent a transect into the Rome Trough/Conasauga intrashelf basin. At our study locations, the initial positive δ¹³C shift of the SPICE occurs in conjunction with increases in the abundance and δ³⁴S of sedimentary pyrite. Further local redox conditions, tracked using iron speciation analysis, indicate anoxic conditions developed at the two proximal locations after the start of the paired isotopic excursions. However, the location near the basin center shows no indication for anoxia before or during the onset of the SPICE. While this signal may reflect the structure of local redox conditions within the basin, with the development of anoxia limited to the basin margins, we argue that authigenic iron enrichments were muted by sedimentary dilution and/or the enhanced authigenesis of iron‐bearing sheet silicates near the basin center, masking the signal for anoxia there. Regardless of the areal extent of anoxia within the basin, in either scenario the timing of the development of anoxic bottom waters was concurrent with local faunal turnover, features broadly consistent with a global expansion of anoxia playing a role in driving the isotopic trends and extinctions observed during the event.     

High-precision iron isotope analysis of whole blood,erythrocytes, and serum in adults

BackgroundIron isotopic composition serves as a biological indicator of Fe metabolism in humans. In the process of Fe metabolism, essential carriers of Fe circulate in the blood and pass through storage organs and intestinal absorptive tissues. This study aimed to establish an analytical method for high-precision Fe isotopic measurement, investigate Fe concentration and isotopic composition in different parts of whole blood, and explore the potential of Fe isotopic composition as an indicator for Fe status within individuals.Analytical methodsA total of 23 clinically healthy Taiwanese adults of Han descent were enrolled randomly and Fe isotopic compositions of their whole blood, erythrocytes, and serum were measured. The Fe isotopic analysis was performed by Neptune Plus multiple-collector inductively coupled plasma mass spectrometry with double-spike technique. The precision and reproducibility of the Fe isotopic analysis were monitored by international biological and geological reference materials.Main findingsHigh-precision Fe isotopic measurements were achieved alongside with high consistency in the isotopic data for well-characterized reference materials. The Fe isotopic signatures of whole blood and erythrocytes were resolvable from that of serum, where both whole blood and erythrocytes contained significantly lighter Fe isotopic compositions compared to the case of serum (P = 0.0296 and P = 0.0004, respectively). The δ^56/54Fe value of the serum sample was 0.2‰ heavier on an average than those of whole blood or erythrocytes. This isotopic fractionation observed in different parts of whole blood may indicate redox processes involved in Fe cycling, e.g. erythrocyte production and Fe transportation. Moreover, the δ^56/54Fe values of whole blood and serum significantly correlated with the hemoglobin level (P = 0.0126 and P = 0.0020, respectively), erythrocyte count (P = 0.0014 and P = 0.0005, respectively), and Mentzer index (P = 0.0055 and P = 0.0011, respectively), suggesting the Fe isotopic composition as an indicator of functional Fe status in healthy adults. The relationships between blood Fe isotopic compositions and relevant biodemographic variables were also examined. While the average Fe concentration of whole blood was significantly higher in males than in females (P = 0.0028), females exhibited a heavier Fe isotopic composition compared to that of males in whole blood (P = 0.0010) and serum (P < 0.0001). A significantly inverse correlation of the whole blood δ^56/54Fe value with body mass index of individuals (P = 0.0095) was also observed.ConclusionThe results presented herein reveal that blood Fe isotopic signature is consequentially linked to baseline erythrocyte parameters in individuals and is significantly affected by the gender and body mass index in the adult population. These findings support the role of Fe isotopic composition as an indicator for the variance of Fe metabolism among adult individuals and populations and warrant further study to elucidate the underlying mechanisms.     

Sedimentary pyrite sulfur isotope compositions preserve signatures of the surface microbial mat environment in sediments underlying low-oxygen cyanobacterial mats

The sedimentary pyrite sulfur isotope (δ³⁴S) record is an archive of ancient microbial sulfur cycling and environmental conditions. Interpretations of pyrite δ³⁴S signatures in sediments deposited in microbial mat ecosystems are based on studies of modern microbial mat porewater sulfide δ³⁴S geochemistry. Pyrite δ³⁴S values often capture δ³⁴S signatures of porewater sulfide at the location of pyrite formation. However, microbial mats are dynamic environments in which biogeochemical cycling shifts vertically on diurnal cycles. Therefore, there is a need to study how the location of pyrite formation impacts pyrite δ³⁴S patterns in these dynamic systems. Here, we present diurnal porewater sulfide δ³⁴S trends and δ³⁴S values of pyrite and iron monosulfides from Middle Island Sinkhole, Lake Huron. The sediment–water interface of this sinkhole hosts a low-oxygen cyanobacterial mat ecosystem, which serves as a useful location to explore preservation of sedimentary pyrite δ³⁴S signatures in early Earth environments. Porewater sulfide δ³⁴S values vary by up to ~25‰ throughout the day due to light-driven changes in surface microbial community activity that propagate downwards, affecting porewater geochemistry as deep as 7.5 cm in the sediment. Progressive consumption of the sulfate reservoir drives δ³⁴S variability, instead of variations in average cell-specific sulfate reduction rates and/or sulfide oxidation at different depths in the sediment. The δ³⁴S values of pyrite are similar to porewater sulfide δ³⁴S values near the mat surface. We suggest that oxidative sulfur cycling and other microbial activity promote pyrite formation in and immediately adjacent to the microbial mat and that iron geochemistry limits further pyrite formation with depth in the sediment. These results imply that primary δ³⁴S signatures of pyrite deposited in organic-rich, iron-poor microbial mat environments capture information about microbial sulfur cycling and environmental conditions at the mat surface and are only minimally affected by deeper sedimentary processes during early diagenesis.     

Chromium geochemistry of the ca. 1.85 Ga Flin Flon paleosol

Fractionation of stable Cr isotopes has been measured in Archaean paleosols and marine sedimentary rocks and interpreted to record the terrestrial oxidation of Cr(III) to Cr(VI), providing possible indirect evidence for the emergence of oxygenic photosynthesis. However, these fractionations occur amidst evidence from other geochemical proxies for a pervasively anoxic atmosphere. This study examined the Cr geochemistry of the ca. 1.85 Ga Flin Flon paleosol, which developed under an atmosphere unambiguously oxidising enough to quantitatively convert Fe(II) to Fe(III) during pedogenesis. The paleosol shows an extreme range in Cr isotope composition of 2.76 ‰ δ^53/52Cr. The protolith greenstone (δ^53/52Cr: ?0.23 ‰), the deepest weathering horizon (δ^53/52Cr: ?0.15 to ?0.23 ‰) and a residual corestone in the upper paleosol (δ^53/52Cr: ?0.01 ‰) all exhibit Cr isotopic compositions comparable to unaltered igneous rocks. The most significant isotopic fractionation is preserved in the areas influenced by oxidative subaerial weathering (i.e. increase in Fe(III)/Fe(II)) and the greatest loss of mobile elements. The uppermost paleosol horizon is both Cr and Mn depleted and offset to significantly ⁵³Cr‐enriched compositions (δ^53/52Cr values between +1.50 and +2.38 ‰), which is not easily modelled with the oxidation of Cr(III) and loss of isotopically heavy Cr(VI). Instead, the currently preferred model for these data invokes the open‐system removal of isotopically light aqueous Cr(III) during either pedogenesis or subsequent hydrothermal/metamorphic alteration. The ⁵³Cr enrichment would then represent the preferential dissolution or complexation of isotopically light aqueous Cr(III) species (enhanced by lower pH conditions and possibly the presence of complexing ligands) and/or the residual signature from preferential adsorption of isotopically heavy Cr(III). Both scenarios would contradict the widely held assumption that only redox reactions of Cr can generate large magnitude isotopic fractionations and, if substantiated, non‐redox isotope effects would complicate the conclusive fingerprinting of ancient atmospheric O₂ from Cr isotope data alone.     

The deposition and significance of an Ediacaran non-glacial iron formation

Most Neoproterozoic iron formations (NIF) are closely associated with global or near-global “Snowball Earth” glaciations. Increasingly, however, studies indicate that some NIFs show no robust evidence of glacial association. Many aspects of non-glacial NIF genesis, including the paleo-environmental setting, Fe(II) source, and oxidation mechanisms, are poorly understood. Here, we present a detailed case study of the Jiapigou NIF, a major non-glacial NIF within a Neoproterozoic volcano-sedimentary sequence in North Qilian, northwestern China. New U–Pb geochronological data place the depositional age of the Jiapigou NIF at ~600 Ma. Petrographic and geochemical evidence supports its identification as a primary chemical sediment with significant detrital input. Major and trace element concentrations, REE + Y systematics, and ε_Nd(t) values indicate that iron was sourced from mixed seawater and hydrothermal fluids. Iron isotopic values (δ⁵⁶Fe = −0.04‰–1.43‰) are indicative of partial oxidation of an Fe(II) reservoir. We infer that the Jiapigou NIF was deposited in a redox stratified water column, where hydrothermally sourced Fe(II)-rich fluids underwent oxidation under suboxic conditions. Lastly, the Jiapigou NIF has strong phosphorous enrichments, which in other iron formations are typically interpreted as signals for high marine phosphate concentrations. This suggests that oceanic phosphorus concentrations could have been enriched throughout the Neoproterozoic, as opposed to simply during glacial intervals.     

Microbiological and isotopic geochemical investigation of Lake Kislo-Sladkoe,a meromictic water body at the Kandalaksha Bay shore (White Sea)

Microbiological, biogeochemical, and isotopic geochemical investigation of Lake Kislo-Sladkoe (Polusolenoe in early publications) at the Kandalaksha Bay shore (White Sea) was carried out in September 2010. Lake Kislo-Sladkoe was formed in the mid-1900s out of a sea gulf due to a coastal heave. At the time of investigation, the surface layer was saturated with oxygen, while near-bottom water contained sulfide (up to 32 mg/L). Total number of microorganisms was high (12.3 × 10⁶ cells/mL on average). Light CO₂ fixation exhibited two pronounced peaks. In the oxic zone, the highest rates of photosynthesis were detected at 1.0 and 2.0 m. The second, more pronounced peak of light CO₂ fixation was associated with activity of anoxygenic phototrophic bacteria in the anoxic layer at the depth of 2.9 m (413 μg C L^?1 day^?1). Green-colored green sulfur bacteria (GSB) predominated in the upper anoxic layer (2.7–2.9 m), their numbers being as high as 1.12 × 10⁴ cells/mL, while brown-colored GSB predominated in the lower horizons. The rates of both sulfate reduction and methanogenesis peaked in the 2.9 m horizon (1690 μg S L^?1 day^?1 and 2.9 μL CH₄ L^?1 day^-1). The isotopic composition of dissolved methane from the near-bottom water layer (δ¹³C (CH₄) = ?87.76‰) was significantly lighter than in the upper horizons (δ¹³C (CH₄) = ?77.95‰). The most isotopically heavy methane (δ¹³C (CH₄) = ?72.61‰) was retrieved from the depth of 2.9 m. The rate of methane oxidation peaked in the same horizon. As a result of these reactions, organic matter (OM) carbon of the 2.9 m horizon became lighter (?36.36‰), while carbonate carbon became heavier (?7.56‰). Thus, our results demonstrated that Lake Kislo-Sladkoe is a stratified meromictic lake with active microbial cycles of carbon and sulfur. Suspended matter in the water column was mostly of autochthonous origin. Anoxygenic photo-synthesis coupled to utilization of reduced sulfur compounds contributed significantly to OM production.     

Isotopic indicators of environmental change in a subtropical wetland

The δ¹⁵N and δ¹³C signatures of major organic matter (OM) pools were measured across chemical and hydrologic gradients in a large (58,800 ha) subtropical wetland to evaluate whether stable isotopes were useful indicators of environmental change. Once a rainfall-driven wetland, the Loxahatchee National Wildlife Refuge in the Florida Everglades now receives agricultural and urban drainage that has increased phosphorus (P) and mineral loads around the wetland perimeter. Additionally, water impoundment at the southern end has produced a latitudinal hydrologic gradient, with extended hydroperiods in the south and overdrained conditions in the north.Detritus (?4.8‰ to 8.6‰), floc (?1.4‰ to 3.6‰), and metaphyton (?6.6‰ to +7.4‰) δ¹⁵N declined southward with changes in hydrology as indicated by water depth. This pattern was attributed to higher mineralization rates under shorter hydroperiods. These signatures were also strongly correlated with increased nutrient and mineral loading. Rooted macrophyte δ¹⁵N, by contrast, appeared more responsive to soil nutrient pools. Cattail (?8.9‰ to +7.7‰) was restricted to the wetland perimeter and had the widest δ¹⁵N range, which was positively correlated with soil P. Sawgrass (?5.3‰ to +7.7‰) occurred across most of the wetland, but its δ¹⁵N was not strongly correlated to any gradient. Patterns for δ¹³C were more strongly related to chemical gradients caused by canal intrusion than to latitude or hydrology. Again, metaphyton and detrital signatures were more sensitive to water chemistry changes than macrophytes. This pattern is consistent with their locations at the soil–water (detritus-floc), and air–water (metaphyton) interface. Metaphyton δ¹³C (?36.1‰ to ?21.5‰) which had the broadest range, was affected by DIC source and pool size. In contrast, cattail δ¹³C (?28.7‰ to ?26.4‰) was more closely related to soil P and sawgrass δ¹³C (?30.1‰ to ?24.5‰) was not related to any environmental gradient except latitude. There was no correlation between the two isotopes for any OM pool except cattail.These results indicate that isotopic signatures of microbial (metaphyton and detrital) pools are more responsive to changes in wetland hydrology and water chemistry while those of rooted macrophytes respond only to the extent that soil chemistry is altered. Rooted macrophytes also differ in the sensitivity of their isotopic signatures to environmental change. The selection of OM pools for isotopic analysis will, therefore, affect the sensitivity of the analysis and the resulting patterns. Furthermore, δ¹⁵N may be more robust and interpretable than δ¹³C as an indicator of ecosystem change in wetlands exposed to multiple or complex anthropogenic gradients.     

Pigment carbon and nitrogen isotopic signatures in euxinic basins

The carbon and nitrogen isotopic signatures of chloropigments and porphyrins from the sediments of redox‐stratified lakes and marine basins reveal details of past biogeochemical nutrient cycling. Such interpretations are strengthened by modern calibration studies, and here, we report on the C and N isotopic composition of pigments and nutrients in the water column and surface sediment of redox‐stratified Fayetteville Green Lake (FGL; New York). We also report δ¹³C and δ¹⁵N values for pyropheophytin a (Pphe a) and bacteriochlorophyll e (Bchl e) deposited in the Black Sea during its transition to a redox‐stratified basin ca. 7.8 ka. We propose a model for evolving nutrient cycling in the Black Sea from 7.8 to 6.4 ka, informed by the new pigment data from FGL. The seasonal study of water column nutrients and pigments at FGL revealed population dynamics in surface and deep waters that were also captured in the sediments. Biomass was greatest near the chemocline, where cyanobacteria, purple sulfur bacteria (PSB), and green sulfur bacteria (GSB) had seasonally variable populations. Bulk organic matter in the surface sediment, however, was derived mainly from the oxygenated surface waters. Surface sediment pigment δ¹³C and δ¹⁵N values indicate intact chlorophyll a (Chl a) was derived from near the chemocline, but its degradation product pheophytin a (Phe a) was derived primarily from surface waters. Bacteriopheophytin a (Bphe a) and Bchl e in the sediments came from chemocline populations of PSB and GSB, respectively. The distinctive δ¹³C and δ¹⁵N values for Chl a, Phe a, and Bphe a in the surface sediment are inputs to an isotopic mixing model that shows their decomposition to a common porphyrin derivative can produce non‐specific sedimentary isotope signatures. This model serves as a caveat for paleobiogeochemical interpretations in basins that had diverse populations near a shallow chemocline.     

Neutrophilic Iron-Oxidizing Bacteria in the Ocean: Their Habitats,Diversity, and Roles in Mineral Deposition,Rock Alteration,and Biomass Production in the Deep-Sea

The importance of metals to life has long been appreciated. Iron (Fe) is the fourth most abundant element overall, and the second most abundant element that is redox-active in near-surface aqueous habitats, rendering it the most important environmental metal. While it has long been recognized that microorganisms participate in the global iron cycle, appreciation for the pivotal role that redox cycling of iron plays in energy conservation among diverse prokaryotes has grown substantially in the past decade. In addition, redox reactions involving Fe are linked to several other biogeochemical cycles (e.g., carbon), with significant ecological ramifications. The increasing appreciation for the role of microbes in redox transformations of Fe is reflected in a recent surge in biological and environmental studies of microorganisms that conserve energy for growth from redox cycling of Fe compounds, particularly in the deep ocean. Here we highlight some of the key habitats where microbial Fe-oxidation plays significant ecological and biogeochemical roles in the oceanic regime, and provide a synthesis of recent studies concerning this important physiological group. We also provide the first evidence that microbial Fe-oxidizing bacteria are a critical factor in the kinetics of mineral dissolution at the seafloor, by accelerating dissolution by 6–8 times over abiotic rates. We assert that these recent studies, which indicate that microbial Fe-oxidation is widespread in the deep-sea, combined with the apparent role that this group play in promoting rock and mineral weathering, indicate that a great deal more attention to these microorganisms is warranted in order to elucidate the full physiological and phylogenetic diversity and activity of the neutrophilic Fe-oxidizing bacteria in the oceans.     

Hydroxyl Radical Production from Irradiated Arctic Dissolved Organic Matter

The hydroxyl radical (OH·) plays an important role in the environmental chemistry and biogeochemistry of surface waters. OH· acts as a strong oxidant within the irradiated water column, and affects the bioavailability, cycling, and mineralization of dissolved organic matter (DOM), the speciation and redox state of important trace metals e.g., iron and copper, and the fate of persistent organic pollutants (POPs). The generation of this species from irradiated DOM may be especially important in Arctic surface waters during the boreal summer, which contains high levels of DOM and experiences continual solar irradiance. Here, we investigate the OH· produced from laser irradiated Arctic DOM isolated from Toolik Lake, AK (68°38′ N, 149°43′ W). We measured the wavelength dependence of OH· production for aqueous solutions of DOM and report that the greatest OH· production occurs at wavelengths less than 360 nm. OH· production rates ranged from 1.7 (±0.1)×10⁻⁷ M h⁻¹ to 6.4 (±0.2)×10⁻⁷ M h⁻¹, with the rate depending on both irradiation wavelength and to a lesser degree the method used to isolate the DOM matrix. These findings lead to a better understanding of the potentially important photo-oxidation processes that may impact DOM cycling in the Arctic.     

Biogeochemical cycling of sulphur in karst and transfer into speleothem archives at Grotta di Ernesto, Italy

Trace amounts of sulphur in speleothems suggest that stalagmites may act as archives of sulphur deposition, thereby recording aspects of atmospheric variability in sulphur content. Accurate interpretation of this novel sulphur archive depends upon understanding how biogeochemical cycling in the soil and epikarst above the cave may modify the precursor atmospheric values of sulphur concentration and isotopic composition prior to incorporation into the speleothem record. Dual isotope analysis of δ³⁴S-SO₄ and δ¹⁸O-SO₄ is used to trace biogeochemical transformations of atmospheric sulphur through the cave system at Grotta di Ernesto in the Italian Alps and builds towards a framework for interpretation of speleothem sulphur archives which depends on overlying ecosystem dynamics and karst hydrological properties. A three component model of atmospheric sulphate signal modification is proposed to be driven by (1). vegetation and soil cycling, (2). the degree of groundwater mixing in the karst aquifer; and (3). redox status. The relative influence of each process is specific to individual drip flow sites and associated stalagmites, rendering each sulphur archive a unique signal of environmental conditions. Under conditions found in the soil and epikarst above Grotta di Ernesto, the dual isotope signatures of sulphate sulphur and oxygen incorporated into speleothem carbonate, closely reflect past conditions of industrial sulphur loading to the atmosphere and the extent of signal modification through biogeochemical cycling and aquifer mixing.     

Evolution of iron and oxygen biogeochemical cycles during the Precambrian

Iron (Fe) is an essential element for life, and its geochemical cycle is intimately linked to the coupled history of life and Earth's environment. The accumulated geologic records indicate that ferruginous waters existed in the Precambrian oceans not only before the first major rise of atmospheric O₂ levels (Great Oxidation Event; GOE) during the Paleoproterozoic, but also during the rest of the Proterozoic. However, the interactive evolution of the biogeochemical cycles of O₂ and Fe during the Archean–Proterozoic remains ambiguous. Here, we develop a biogeochemical model to investigate the coupled biogeochemical evolution of Fe–O₂–P–C cycles across the GOE. Our model demonstrates that the marine Fe cycle was less sensitive to changes in the production rate of O₂ before the GOE (atmospheric pO₂ < 10⁻⁶ PAL; present atmospheric level). When the P supply rate to the ocean exceeds a certain threshold, the GOE occurs and atmospheric pO₂ rises to ~10⁻³–10⁻¹ PAL. After the GOE, the marine Fe(II) concentration is highly sensitive to atmospheric pO₂, suggesting that the marine redox landscape during the Proterozoic may have fluctuated between ferruginous conditions and anoxic non-ferruginous conditions with sulfidic water masses around continental margins. At a certain threshold value of atmospheric pO₂ of ~0.3% PAL, the primary oxidation pathway of Fe(II) shifts from the activity of Fe(II)-utilizing anoxygenic photoautotrophs in sunlit surface waters to abiotic process in the deep ocean. This is accompanied by a shift in the primary deposition site of Fe(III) hydroxides from the surface ocean to the deep sea, providing a plausible mechanistic explanation for the observed cessation of iron formations during the Proterozoic.     

Some aspects of iron cycling in maritime antarctic lakes

Iron occurs in extremely high concentrations in certain maritime Antarctic freshwater lakes which seasonally develop an anoxic zone. In oligotrophic Sombre Lake the data show that Fe(II) precipitates as Fe(III) oxyhydroxides which bind phosphorus and return it to the sediments. In nutrient-enriched Amos lake, significant quantities of sulphide are also produced and this binds a proportion of the released Fe(II) so reducing the ratio of total iron to phosphorus at the redox boundary where the oxyhydroxides are formed. A proportion of the sediment-released phosphorus therefore reaches the upper waters of this lake (unlike in Sombre Lake) and provides the initial nutrient source for under-ice phytoplankton development in spring. Iron-reducing bacteria have been isolated, from Sombre Lake sediments, which apparently utilise the abundant Fe(III) oxyhydroxides. From thermodynamic considerations (assuming Fe(III) is not limiting) these should outcompete sulphate reducers and methanogens (both previously reported from Sombre and Amos Lakes) and could therefore constitute an important component of the anaerobic mineralisation of organic carbon in such lakes.     

Modeling the carbon cycle in Lake Matano

Lake Matano, Indonesia, is a stratified anoxic lake with iron‐rich waters that has been used as an analogue for the Archean and early Proterozoic oceans. Past studies of Lake Matano report large amounts of methane production, with as much as 80% of primary production degraded via methanogenesis. Low δ¹³C values of DIC in the lake are difficult to reconcile with this notion, as fractionation during methanogenesis produces isotopically heavy CO₂. To help reconcile these observations, we develop a box model of the carbon cycle in ferruginous Lake Matano, Indonesia, that satisfies the constraints of CH₄ and DIC isotopic profiles, sediment composition, and alkalinity. We estimate methane fluxes smaller than originally proposed, with about 9% of organic carbon export to the deep waters degraded via methanogenesis. In addition, despite the abundance of Fe within the waters, anoxic ferric iron respiration of organic matter degrades <3% of organic carbon export, leaving methanogenesis as the largest contributor to anaerobic organic matter remineralization, while indicating a relatively minor role for iron as an electron acceptor. As the majority of carbon exported is buried in the sediments, we suggest that the role of methane in the Archean and early Proterozoic oceans is less significant than presumed in other studies.     

Trace metal complexation by the triscatecholate siderophore protochelin: structure and stability

Although siderophores are generally viewed as biological iron uptake agents, recent evidence has shown that they may play significant roles in the biogeochemical cycling and biological uptake of other metals. One such siderophore that is produced by A. vinelandii is the triscatecholate protochelin. In this study, we probe the solution chemistry of protochelin and its complexes with environmentally relevant trace metals to better understand its effect on metal uptake and cycling. Protochelin exhibits low solubility below pH 7.5 and degrades gradually in solution. Electrochemical measurements of protochelin and metal–protochelin complexes reveal a ligand half-wave potential of 200 mV. The Fe(III)Proto³⁻ complex exhibits a salicylate shift in coordination mode at circumneutral to acidic pH. Coordination of Mn(II) by protochelin above pH 8.0 promotes gradual air oxidation of the metal center to Mn(III), which accelerates at higher pH values. The Mn(III)Proto³⁻ complex was found to have a stability constant of log β₁₁₀ = 41.6. Structural parameters derived from spectroscopic measurements and quantum mechanical calculations provide insights into the stability of the Fe(III)Proto³⁻, Fe(III)H₃Proto, and Mn(III)Proto³⁻ complexes. Complexation of Co(II) by protochelin results in redox cycling of Co, accompanied by accelerated degradation of the ligand at all solution pH values. These results are discussed in terms of the role of catecholate siderophores in environmental trace metal cycling and intracellular metal release.     

Brine Assemblages of Ultrasmall Microbial Cells within the Ice Cover of Lake Vida,Antarctica

The anoxic and freezing brine that permeates Lake Vida''s perennial ice below 16 m contains an abundance of very small (≤0.2-μm) particles mixed with a less abundant population of microbial cells ranging from >0.2 to 1.5 μm in length. Fluorescent DNA staining, electron microscopy (EM) observations, elemental analysis, and extraction of high-molecular-weight genomic DNA indicated that a significant portion of these ultrasmall particles are cells. A continuous electron-dense layer surrounding a less electron-dense region was observed by EM, indicating the presence of a biological membrane surrounding a cytoplasm. The ultrasmall cells are 0.192 ± 0.065 μm, with morphology characteristic of coccoid and diplococcic bacterial cells, often surrounded by iron-rich capsular structures. EM observations also detected the presence of smaller unidentified nanoparticles of 0.020 to 0.140 μm among the brine cells. A 16S rRNA gene clone library from the brine 0.1- to 0.2-μm-size fraction revealed a relatively low-diversity assemblage of Bacteria sequences distinct from the previously reported >0.2-μm-cell-size Lake Vida brine assemblage. The brine 0.1- to 0.2-μm-size fraction was dominated by the Proteobacteria-affiliated genera Herbaspirillum, Pseudoalteromonas, and Marinobacter. Cultivation efforts of the 0.1- to 0.2-μm-size fraction led to the isolation of Actinobacteria-affiliated genera Microbacterium and Kocuria. Based on phylogenetic relatedness and microscopic observations, we hypothesize that the ultrasmall cells in Lake Vida brine are ultramicrocells that are likely in a reduced size state as a result of environmental stress or life cycle-related conditions.     

Neutrophilic, nitrate-dependent, Fe(II) oxidation by a Dechloromonas species

A species of Dechloromonas, strain UWNR4, was isolated from a nitrate-reducing, enrichment culture obtained from Wisconsin River (USA) sediments. This strain was characterized for anaerobic oxidation of both aqueous and chelated Fe(II) coupled to nitrate reduction at circumneutral pH. Dechloromonas sp. UWNR4 was incubated in anoxic batch reactors in a defined medium containing 4.5–5 mM NO₃ ^?, 6 mM Fe²⁺ and 1–1.8 mM acetate. Strain UWNR4 efficiently oxidized Fe²⁺ with 90 % oxidation of Fe²⁺ after 3 days of incubation. However, oxidation of Fe²⁺ resulted in Fe(III)-hydroxide-encrusted cells and loss of metabolic activity, suggested by inability of the cells to utilize further additions of acetate. In similar experiments with chelated iron (Fe(II)-EDTA), encrusted cells were not produced and further additions of acetate and Fe(II)-EDTA could be oxidized. Although members of the genus Dechloromonas are primarily known as perchlorate and nitrate reducers, our findings suggest that some species could be members of microbial communities influencing iron redox cycling in anoxic, freshwater sediments. Our work using Fe(II)-EDTA also demonstrates that Fe(II) oxidation was microbially catalyzed rather than a result of abiotic oxidation by biogenic NO₂ ^?.     

Petrobactin,a siderophore produced by Alteromonas,mediates community iron acquisition in the global ocean

It is now widely accepted that siderophores play a role in marine iron biogeochemical cycling. However, the mechanisms by which siderophores affect the availability of iron from specific sources and the resulting significance of these processes on iron biogeochemical cycling as a whole have remained largely untested. In this study, we develop a model system for testing the effects of siderophore production on iron bioavailability using the marine copiotroph Alteromonas macleodii ATCC 27126. Through the generation of the knockout cell line ΔasbB::km^r, which lacks siderophore biosynthetic capabilities, we demonstrate that the production of the siderophore petrobactin enables the acquisition of iron from mineral sources and weaker iron-ligand complexes. Notably, the utilization of lithogenic iron, such as that from atmospheric dust, indicates a significant role for siderophores in the incorporation of new iron into marine systems. We have also detected petrobactin, a photoreactive siderophore, directly from seawater in the mid-latitudes of the North Pacific and have identified the biosynthetic pathway for petrobactin in bacterial metagenome-assembled genomes widely distributed across the global ocean. Together, these results improve our mechanistic understanding of the role of siderophore production in iron biogeochemical cycling in the marine environment wherein iron speciation, bioavailability, and residence time can be directly influenced by microbial activities.Subject terms: Biogeochemistry, Marine microbiology     

Planktonic marine iron oxidizers drive iron mineralization under low‐oxygen conditions

Observations of modern microbes have led to several hypotheses on how microbes precipitated the extensive iron formations in the geologic record, but we have yet to resolve the exact microbial contributions. An initial hypothesis was that cyanobacteria produced oxygen which oxidized iron abiotically; however, in modern environments such as microbial mats, where Fe(II) and O₂ coexist, we commonly find microaerophilic chemolithotrophic iron‐oxidizing bacteria producing Fe(III) oxyhydroxides. This suggests that such iron oxidizers could have inhabited niches in ancient coastal oceans where Fe(II) and O₂ coexisted, and therefore contributed to banded iron formations (BIFs) and other ferruginous deposits. However, there is currently little evidence for planktonic marine iron oxidizers in modern analogs. Here, we demonstrate successful cultivation of planktonic microaerophilic iron‐oxidizing Zetaproteobacteria from the Chesapeake Bay during seasonal stratification. Iron oxidizers were associated with low oxygen concentrations and active iron redox cycling in the oxic–anoxic transition zone (<3 μm O₂, <0.2 μm H₂S). While cyanobacteria were also detected in this transition zone, oxygen concentrations were too low to support significant rates of abiotic iron oxidation. Cyanobacteria may be providing oxygen for microaerophilic iron oxidation through a symbiotic relationship; at high Fe(II) levels, cyanobacteria would gain protection against Fe(II) toxicity. A Zetaproteobacteria isolate from this site oxidized iron at rates sufficient to account for deposition of geologic iron formations. In sum, our results suggest that once oxygenic photosynthesis evolved, microaerophilic chemolithotrophic iron oxidizers were likely important drivers of iron mineralization in ancient oceans.