skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


  • NSF Public Access
  • Search Results
  • Isotopic Compositions of Sulfides in Exhumed High‐Pressure Terranes: Implications for Sulfur Cycling in Subduction Zones
Title: Isotopic Compositions of Sulfides in Exhumed High‐Pressure Terranes: Implications for Sulfur Cycling in Subduction Zones
Abstract Subduction is a key component of Earth's long‐term sulfur cycle; however, the mechanisms that drive sulfur from subducting slabs remain elusive. Isotopes are a sensitive indicator of the speciation of sulfur in fluids, sulfide dissolution‐precipitation reactions, and inferring fluid sources. To investigate these processes, we report δ34S values determined by secondary ion mass spectroscopy in sulfides from a global suite of exhumed high‐pressure rocks. Sulfides are classified into two petrogenetic groups: (1) metamorphic, which represent closed‐system (re)crystallization from protolith‐inherited sulfur, and (2) metasomatic, which formed during open system processes, such as an influx of oxidized sulfur. The δ34S values for metamorphic sulfides tend to reflect their precursor compositions: −4.3 ‰ to +13.5 ‰ for metabasic rocks, and −32.4 ‰ to −11.0 ‰ for metasediments. Metasomatic sulfides exhibit a range of δ34S from −21.7 ‰ to +13.9 ‰. We suggest that sluggish sulfur self‐diffusion prevents isotopic fractionation during sulfide breakdown and that slab fluids inherit the isotopic composition of their source. We estimate a composition of −11 ‰ to +8 ‰ for slab fluids, a significantly smaller range than observed for metasomatic sulfides. Large fractionations during metasomatic sulfide precipitation from sulfate‐bearing fluids, and an evolving fluid composition during reactive transport may account for the entire ~36 ‰ range of metasomatic sulfide compositions. Thus, we suggest that sulfates are likely the dominant sulfur species in slab‐derived fluids.  more » « less
Award ID(s):
1664308
PAR ID:
10367900
Author(s) / Creator(s):
 ;  ;  
Publisher / Repository:
DOI PREFIX: 10.1029
Date Published:
Journal Name:
Geochemistry, Geophysics, Geosystems
Volume:
20
Issue:
7
ISSN:
1525-2027
Page Range / eLocation ID:
p. 3347-3374
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; ; ; ; (, Nature Communications)
    Abstract Sulfur belongs among H2O, CO2, and Cl as one of the key volatiles in Earth’s chemical cycles. High oxygen fugacity, sulfur concentration, and δ34S values in volcanic arc rocks have been attributed to significant sulfate addition by slab fluids. However, sulfur speciation, flux, and isotope composition in slab-dehydrated fluids remain unclear. Here, we use high-pressure rocks and enclosed veins to provide direct constraints on subduction zone sulfur recycling for a typical oceanic lithosphere. Textural and thermodynamic evidence indicates the predominance of reduced sulfur species in slab fluids; those derived from metasediments, altered oceanic crust, and serpentinite have δ34S values of approximately −8‰, −1‰, and +8‰, respectively. Mass-balance calculations demonstrate that 6.4% (up to 20% maximum) of total subducted sulfur is released between 30–230 km depth, and the predominant sulfur loss takes place at 70–100 km with a net δ34S composition of −2.5 ± 3‰. We conclude that modest slab-to-wedge sulfur transport occurs, but that slab-derived fluids provide negligible sulfate to oxidize the sub-arc mantle and cannot deliver34S-enriched sulfur to produce the positive δ34S signature in arc settings. Most sulfur has negative δ34S and is subducted into the deep mantle, which could cause a long-term increase in the δ34S of Earth surface reservoirs. 
    more » « less
  2. ; ; ; ; ; (, Mineralium Deposita)
    Abstract Stibnite is a relatively common mineral in epithermal deposits, with little known about Sb transport and efficient stibnite precipitation. The famous Kremnica Au-Ag low-sulfidation deposit and Zlatá Baňa intermediate-sulfidation Pb-Zn-Cu-Au-Ag-Sb deposit are hosted in two different Neogene volcanic fields in Western Carpathians, Slovakia. In both deposits, stibnite-rich veins occur outside of major vein structures, accompanied by illite, illite/smectite, and kaolinite alteration, and affiliated to late-stage fluids (< 2 wt% NaCl eq., < 150 °C). Sulfur isotopic composition of stibnite and sulfides is different at both deposits, likely due to a different magmatic-hydrothermal evolution of the parental magmatic chambers in the Central and Eastern Slovak Volcanic Fields. The Sb isotopes (δ123Sb), however, show similar values and trends of gradual simultaneous increase with δ34S values, explained by a progressive precipitation of stibnite and its fractionation with the fluid. The data were modeled by two coupled Rayleigh fractionation models, (for Sb and for S), assuming a predominant Sb transport in HSb2S4–with a variable amount of S species. Higher molality ratio mS/mSbof fluids was found in Kremnica (~ 3–4) than in Zlatá Baňa (~ 2). At both deposits, the heaviest δ123Sb values are accompanied by a decrease in the δ34S values probably due to the commencement of pyrite/marcasite precipitation. According to thermodynamic models of solubility of Sb(III) complexes and observations from active geothermal fields, stibnite precipitation was triggered by temperature decrease accompanied by mixing with a mildly acidic fluid (pH 4–5) of a steam-heated CO2-rich condensate on margins and in the final stages of epithermal systems. The proposed model for the origin of stibnite-bearing veins in epithermal systems can be used for their better targeting and efficient mineral exploration. 
    more » « less
  3. ; ; ; (, Geochemistry, Geophysics, Geosystems)
    Abstract During the subduction of an oceanic plate, fluids are released from metabasaltic crust, metasediment, and serpentinite under high‐pressure/low‐temperature conditions. Although some fluids may eventually leave the slab, some participate in metamorphic reactions within the slab during subduction and exhumation. To identify fluid sources and other controls influencing mineral composition, we report the in situ‐measured δ18O of lawsonite and garnet in blueschist‐ to eclogite‐facies rocks from 10 subduction zones that represent various field settings, including mélanges, structurally coherent terranes, and an eclogite xenolith derived from a subducted plate. Lawsonite records distinct δ18O depending on the host rock type and other rock types that were fluid sources during lawsonite growth. In general, lawsonite in metabasalt (7.6 ± 0.2–14.8 ± 1.1‰) is isotopically lighter than in metasediment (20.6 ± 1.4–24.1 ± 1.3‰) but heavier than in metagabbro (4.0 ± 0.4–7.9 ± 0.3‰). The extent of δ18O fractionation was evaluated for lawsonite–fluid and lawsonite–garnet pairs as a function of temperature (T). Results demonstrate that variations of >1.7‰ in lawsonite and >0.9‰ in garnet are not related to changingT. More likely, the relative contributions of fluids derived from isotopically heavier lithologies (e.g., sediments) versus lighter lithologies (e.g., ultramafic rocks) are the major control. Monte Carlo simulations were performed to investigate the sources of metasomatic fluids and the water/rock ratio that formed lawsonite‐bearing metasomatite. Results indicate that δ18OLwsand δ18OGrtrecord interactions with fluids sourced from diverse lithologies (sediment, serpentinite), further supporting that δ18OLwsis a useful indicator of subduction fluid‐rock interactions. 
    more » « less
  4. ; ; ; (, Geochemistry, Geophysics, Geosystems)
    Abstract Basalts from the Samoan volcanoes sample contributions from all of the classical mantle endmembers, including extreme EM II and high3He/4He components, as well as dilute contributions from the HIMU, EM I, and DM components. Here, we present multiple sulfur isotope data on sulfide extracted from subaerial and submarine whole rocks (N = 16) associated with several Samoan volcanoes—Vailulu‘u, Malumalu, Malutut, Upolu, Savai‘i, and Tutuila—that sample the full range of geochemical heterogeneity at Samoa and upon exhaustive compilation of S‐isotope data for Samoan lavas, allow for an assessment of the S‐isotope compositions associated with the different mantle components sampled by the Samoan hotspot. We observe variable S concentrations (10–1,000 ppm) and δ34S values (−0.29‰ ± 0.30 to +4.84‰ ± 0.30, 2σ). The observed variable S concentrations are likely due to sulfide segregation and degassing processes. The range in δ34S reflects mixing between the mantle origin and recycled components, and isotope fractionations associated with degassing. The majority of samples reveal Δ33S within uncertainty of Δ33S = 0‰ ± 0.008. Important exceptions to this observation include: (a) a negative Δ33S (−0.018‰ ± 0.008, 2σ) from a rejuvenated basalt on Upolu island (associated with a diluted EM I component) and (b) previously documented small (but resolvable) Δ33S values (up to +0.027 ± 0.016) associated with the Vai Trend (associated with a diluted HIMU component). The variability we observed in Δ33S is interpreted to reflect contributions of sulfur of different origins and likely multiple crustal protoliths. Δ36S versus Δ33S relationships suggest all recycled S is of post‐Archean origin. 
    more » « less
  5. ; ; ; ; ; ; ; ; ; (, Geobiology)
    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
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email