Attention:The NSF Public Access Repository (PAR) system and access will be unavailable from 5:00 PM ET until 8:00 PM ET on Friday, September 11 due to maintenance. We apologize for the inconvenience.


Title: Sulfur isotopes reveal agricultural changes to the modern sulfur cycle
Abstract The environmental fates and consequences of intensive sulfur (S) applications to croplands are largely unknown. In this study, we used S stable isotopes to identify and trace agricultural S from field-to-watershed scales, an initial and timely step toward constraining the modern S cycle. We conducted our research within the Napa River Watershed, California, US, where vineyards receive frequent fungicidal S sprays. We measured soil and surface water sulfate concentrations ([SO42−]) and stable isotopes (δ34S–SO42−), which we refer to in combination as the ‘S fingerprint’. We compared samples collected from vineyards and surrounding forests/grasslands, which receive background atmospheric and geologic S sources. Vineyardδ34S–SO42−values were 9.9 ± 5.9‰ (median ± interquartile range), enriched by ∼10‰ relative to forests/grasslands (−0.28 ± 5.7‰). Vineyards also had roughly three-fold higher [SO42−] than forests/grasslands (13.6 and 5.0 mg SO42−–S l−1, respectively). Napa Riverδ34S–SO42−values, reflecting the watershed scale, were similar to those from vineyards (10.5 ± 7.0‰), despite vineyard agriculture constituting only ∼11% of the watershed area. Combined, our results provide important evidence that agricultural S is traceable at field-to-watershed scales, a critical step toward determining the consequences of agricultural alterations to the modern S cycle.  more » « less
Award ID(s):
1945388
PAR ID:
10570001
Author(s) / Creator(s):
; ;
Publisher / Repository:
Environmental Research Letters
Date Published:
Journal Name:
Environmental Research Letters
Volume:
17
Issue:
5
ISSN:
1748-9326
Page Range / eLocation ID:
054032
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract The Southern Ocean has emerged as a key region for constraining aerosol‐climate interactions due to its relatively low anthropogenic influence. Sulfate is an important aerosol over the Southern Ocean, and models suggest dimethyl sulfide (DMS) is the largest source of sulfate during summer. However, sulfur isotopes of sulfate (δ34S(SO42−)) in Antarctic ice cores suggest a significant contribution from a previously unexplained non‐DMS source. Here we show that the fractional contribution from passive volcanic degassing (fvolc) explains observed δ34S(SO42−), and that a global chemical transport model underestimatesfvolcacross Antarctica. Underestimatedfvolcimplies that the model mischaracterizes sulfate sources in this important region. The discrepancy between observed and modeled sulfate sources can be reconciled by increasing passive volcanic sulfur degassing emissions and decreasing DMS emissions. Our results imply that current biases in emissions inventories could bias assessments of aerosol‐cloud interactions in the Southern Ocean region and globally. 
    more » « less
  2. Abstract Stable isotope fractionation of sulfur offers a window into Io's tidal heating history, which is difficult to constrain because Io's dynamic atmosphere and high resurfacing rates leave it with a young surface. We constructed a numerical model to describe the fluxes in Io's sulfur cycle using literature constraints on rates and isotopic fractionations of relevant processes. Combining our numerical model with measurements of the34S/32S ratio in Io's atmosphere, we constrain the rates for the processes that move sulfur between reservoirs and model the evolution of sulfur isotopes over time. Gravitational stratification of SO2in the upper atmosphere, leading to a decrease in34S/32S with increasing altitude, is the main cause of sulfur isotopic fractionation associated with loss to space. Efficient recycling of the atmospheric escape residue into the interior is required to explain the34S/32S enrichment magnitude measured in the modern atmosphere. We hypothesize this recycling occurs by SO2surface frost burial and SO2reaction with crustal rocks, which founder into the mantle and/or mix with mantle‐derived magmas as they ascend. Therefore, we predict that magmatic SO2plumes vented from the mantle to the atmosphere will have lower34S/32S than the ambient atmosphere, yet are still significantly enriched compared to solar‐system average sulfur. Observations of atmospheric variations in34S/32S with time and/or location could reveal the average mantle melting rate and hence whether the current tidal heating rate is anomalous compared to Io's long‐term average. Our modeling suggests that tides have heated Io for >1.6 Gyr if Io today is representative of past Io. 
    more » « less
  3. Abstract Sulfur isotopes in mantle plume‐derived magmas show heterogeneities attributed to recycling of material from the Earth's surface. The sedimentary sulfur isotope record exhibits dramatic temporal variations over Earth history, raising the question of whether its secular evolution is echoed in mantle plume‐derived magmas. We present new secondary ion mass spectrometry and X‐ray absorption near‐edge structure measurements of δ34S and Fe3+/ΣFe in naturally glassy melt inclusions from the 2.7 Ga Belingwe komatiites. We find that δ34S of Belingwe melt inclusions is relatively homogeneous (+3.2 ± 0.9) and elevated relative to the depleted upper mantle. We evaluate explanations for elevated magmatic δ34S including degassing, sulfide fractionation, assimilation, subduction‐like processes, and mantle recycling. We find no evidence for significant sulfur isotope fractionation via degassing or sulfide saturation. The elevated δ34S in the Belingwe komatiites could reflect late‐stage assimilation of sediments or seawater. Alternatively, Belingwe komatiites may have formed in a subduction‐like setting, as modern arcs display a bias toward positive δ34S. However, we find these scenarios less favorable. Instead, our preferred interpretation is that elevated δ34S was supplied to the komatiite mantle source via recycled lithologies such as sediments, altered oceanic crust, and/or pyroxenite. Combined with δ34S data from mantle plume‐derived magmas spanning a wide age range, our results resemble the secular evolution of δ34S in surface reservoirs. We suggest that the δ34S record in mantle plume‐derived magmas may echo secular evolution in the surficial sulfur reservoir with a delay of several hundred million years, linking Earth's surface and interior sulfur cycles. 
    more » « less
  4. 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 HSb2S4with 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
  5. Abstract Recycling of oxidized sulfur from subducting slabs to the mantle wedge provides simultaneous explanations for the elevated oxygen fugacity (fO2) in subduction zones, their high hydrothermal and magmatic sulfur outputs, and the enriched sulfur isotopic signatures (i.e., δ34S > 0‰) of these outputs. However, a quantitative understanding of the abundance and speciation of sulfur in slab fluids consistent with high pressure experiments is lacking. Here we analyze published experimental data for anhydrite solubility in H2O‐NaCl solutions to calibrate a high‐pressure aqueous speciation model of sulfur within the framework of the deep earth water model. We characterize aqueous complexes, required to account for the high experimental anhydrite solubilities. We then use this framework to predict the speciation and solubility of sulfur in chemically complex fluids in equilibrium with model subducting mafic and ultramafic lithologies, from 2 to 3 GPa and 400 to 800°C at logfO2from FMQ‐2 to FMQ+4. We show that sulfate complexes of calcium and sodium markedly enhance the stability of sulfate in moderately oxidized fluids in equilibrium with pyrite atfO2conditions of FMQ+1 to +2, causing large sulfur isotope fractionations up to 10‰ in the fluid relative to the slab. Such fluids could impart oxidized, sulfur‐rich and high δ34S signatures to the mantle wedge that are ultimately transferred to arc magmas, without the need to invoke34S‐rich subducted lithologies. 
    more » « less