An official website of the United States government
Abstract 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.
more »
« less
Cracking the superheavy pyrite enigma: possible roles of volatile organosulfur compound emission
Abstract The global deposition of superheavy pyrite (pyrite isotopically heavier than coeval seawater sulfate in the Neoproterozoic Era and particularly in the Cryogenian Period) defies explanation using the canonical marine sulfur cycle system. Here we report petrographic and sulfur isotopic data (δ34Spy) of superheavy pyrite from the Cryogenian Datangpo Formation (660–650 Ma) in South China. Our data indicate a syndepositional/early diagenetic origin of the Datangpo superheavy pyrite, with 34S-enriched H2S supplied from sulfidic (H2S rich) seawater. Instructed by a novel sulfur-cycling model, we propose that the emission of 34S-depleted volatile organosulfur compounds (VOSC) that were generated via sulfide methylation may have contributed to the formation of 34S-enriched sulfidic seawater and superheavy pyrite. The global emission of VOSC may be attributed to enhanced organic matter production after the Sturtian glaciation in the context of widespread sulfidic conditions. These findings demonstrate that VOSC cycling is an important component of the sulfur cycle in Proterozoic oceans.
more »
« less
- Award ID(s):
- 2021207
- PAR ID:
- 10271583
- Date Published:
- Journal Name:
- National Science Review
- ISSN:
- 2095-5138
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract The Ordovician (Hirnantian; 445 Ma) hosts the second most severe mass extinction in Earth history, coinciding with Gondwanan glaciation and increased geochemical evidence for marine anoxia. It remains unclear whether cooling, expanded oxygen deficiency, or a combination drove the Late Ordovician Mass Extinction (LOME). Here, we present combined iodine and sulfur isotope geochemical data from three globally distributed carbonate successions to constrain changes in local and global marine redox conditions. Iodine records suggest locally anoxic conditions were potentially pervasive on shallow carbonate shelves, while sulfur isotopes suggest a reduction in global euxinic (anoxic and sulfidic) conditions. Late Katian sulfate‐sulfur isotope data show a large negative excursion that initiated during elevated sea level and continued through peak Hirnantian glaciation. Geochemical box modeling suggests a combination of decreasing pyrite burial and increasing weathering are required to drive the observed negative excursion suggesting a ∼3% decrease of global seafloor euxinia during the Late Ordovician. The sulfur datasets provide further evidence that this trend was followed by increases in euxinia which coincided with eustatic sea‐level rise during subsequent deglaciation in the late Hirnantian. A persistence of shelf anoxia against a backdrop of waning then waxing global euxinia was linked to the two LOME pulses. These results place important constraints on local and global marine redox conditions throughout the Late Ordovician and suggest that non‐sulfidic shelfal anoxia—along with glacioeustatic sea level and climatic cooling—were important environmental stressors that worsened conditions for marine fauna, resulting in the second‐largest mass extinction in Earth history and the only example during an icehouse climate.more » « less
-
Abstract An imbalance in pyrite weathering and burial is a primary mechanism responsible for oxygenation of the atmosphere and oceans, but key processes governing the terrestrial sulfur cycle remain nebulous. Here, we investigate components of the terrestrial sulfur cycle in a highly productive, glacier‐fed catchment, and use a global mass balance model to constrain riverine sulfur fluxes. Chemistry of stream water and plant debris in the Jostedal watershed, Norway suggests sulfur isotope discrimination is occurring in the porewater. Global models also corroborate additional, previously overlooked pyrite burial with a modest isotope fractionation (<20‰), similar to values reported from freshwater ecosystems. Collectively, our results indicate that a significant amount of sulfate produced by weathering remains trapped in terrestrial environments. This terrestrial sulfur sink might have waxed and waned over geologic time in response to major biogeochemical events such as terrestrial afforestation.more » « less
-
Naphthoquinone (1,4-NQ) and its derivatives (NQs, juglone, plumbagin, 2-methoxy-1,4-NQ, and menadione) have a variety of therapeutic applications, many of which are attributed to redox cycling and the production of reactive oxygen species (ROS). We previously demonstrated that NQs also oxidize hydrogen sulfide (H2S) to reactive sulfur species (RSS), potentially conveying identical benefits. Here we use RSS-specific fluorophores, mass spectroscopy, EPR and UV-Vis spectrometry, and oxygen-sensitive optodes to examine the effects of thiols and thiol-NQ adducts on H2S-NQ reactions. In the presence of glutathione (GSH) and cysteine (Cys), 1,4-NQ oxidizes H2S to both inorganic and organic hydroper-/hydropolysulfides (R2Sn, R=H, Cys, GSH; n = 2–4) and organic sulfoxides (GSnOH, n = 1, 2). These reactions reduce NQs and consume oxygen via a semiquinone intermediate. NQs are also reduced as they form adducts with GSH, Cys, protein thiols, and amines. Thiol, but not amine, adducts may increase or decrease H2S oxidation in reactions that are both NQ- and thiol-specific. Amine adducts also inhibit the formation of thiol adducts. These results suggest that NQs may react with endogenous thiols, including GSH, Cys, and protein Cys, and that these adducts may affect both thiol reactions as well as RSS production from H2S.more » « less
-
Abstract Organic sulfur plays a crucial role in the biogeochemistry of aquatic sediments, especially in low sulfate (< 500 μM) environments like freshwater lakes and the Earth's early oceans. To better understand organic sulfur cycling in these systems, we followed organic sulfur in the sulfate‐poor (< 40 μM) iron‐rich (30–80 μM) sediments of Lake Superior from source to sink. We identified microbial populations with shotgun metagenomic sequencing and characterized geochemical species in porewater and solid phases. In anoxic sediments, we found an active sulfur cycle fueled primarily by oxidized organic sulfur. Sediment incubations indicated a microbial capacity to hydrolyze sulfonates, sulfate esters, and sulfonic acids to sulfate. Gene abundances for dissimilatory sulfate reduction (dsrAB) increased with depth and coincided with sulfide maxima. Despite these indicators of sulfide formation, sulfide concentrations remain low (< 40 nM) due to both pyritization and organic matter sulfurization. Immediately below the oxycline, pyrite accounted for 13% of total sedimentary sulfur. Both free and intact lipids in this same interval accumulated disulfides, indicating rapid sulfurization even at low concentrations of sulfide. Our investigation revealed a new model of sulfur cycling in a low‐sulfate environment that likely extends to other modern lakes and possibly the ancient ocean, with organic sulfur both fueling sulfate reduction and consuming the resultant sulfide.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1093/nsr/nwab034
