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Science 7 March 2008:
Vol. 319. no. 5868, p. 1336
DOI: 10.1126/science.1151414
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Technical Comments

Response to Comment on "Early Archaean Microorganisms Preferred Elemental Sulfur, Not Sulfate"

Pascal Philippot,1* Mark Van Zuilen,1 Kevin Lepot,1 Christophe Thomazo,1 James Farquhar,2 Martin J. Van Kranendonk3

Our knowledge of the sulfur cycle on early Earth is still in its infancy. Nevertheless, there exist enough geochemical constraints from the rock record to show that the theoretical mixing models proposed by Bao et al. are highly unlikely to account for the range of {delta}34S and {Delta}33S values recorded for the microscopic sulfides at the North Pole.

1 Equipe Géobiosphère Actuelle et Primitive, Institut de Physique du Globe de Paris, Centre National de la Recherche Scientifique and Université Denis Diderot, 4 place Jussieu, 75005 Paris cedex, France.
2 Earth System Science Interdisciplinary Center, Department of Geology, University of Maryland, College Park, Maryland 20742, USA.
3 Geological Survey of Western Australia, 100 Plain Street, East Perth, WA 6004, Australia.

* To whom correspondence should be addressed. E-mail: philippot{at}ipgp.jussieu.fr

Bao et al. (1) propose that the relatively large range of {delta}34S and {delta}33S values reported for microscopic sulfides preserved in bedded barite from the Dresser Formation at the North Pole could be accounted for by mixing between photolytic elemental sulfur (+{delta}33S) and surface sulfides derived from inorganic or microbial sulfate reduction (–{delta}33S).

Two main types of models have been considered to explain the observed range in {Delta}33S and {delta}34S values of microscopic sulfides. The first supposes that there was a pool of atmospheric S0 that was temporally or spatially heterogeneous in {Delta}33S. This hypothesis is poorly constrained and not supported by the sulfur isotope data reported so far in ~3800- to 2700-million-year-old Archaean rocks. As shown in Fig. 1, more than 90% of Early to Mid-Archaean sulfides show a narrow range of {delta}34S values of ±5 per mil ({per thousand}) and {Delta}33S values between +6 and –1{per thousand}. The only exception concerns the microscopic sulfides at the North Pole. Although a heterogeneous source of positive {Delta}33S sulfides cannot be excluded, it would imply that it developed only once in a time span of more than 1000 million years and was restricted to the microscopic pyrites but not the adjacent macroscopic pyrites surrounding the barite crystals hosting the microscopic sulfides, which seems highly unlikely.


Figure 1 Fig. 1. (A) Experimental results of photolyzed sulfur dioxide to elemental sulfur (+{Delta}33S, large black diamonds) and sulfate (–{Delta}33S, large black squares) (large empty circles correspond to the residual SO2) when it is exposed to ultraviolet radiation at a wavelength of 193 nm (5, 7). Superposed onto this diagram is the range of sulfide pools and array used in (1) ("Bao array"). These include: (i) photolyzed S0 (dark blue) formed from interaction with ultraviolet at 193 nm and associated sulfide (light blue) formed from atmospheric S0 reduction or disproportionation and (ii) "surface" oceanic sulfate pool (red) and associated sulfides formed from sulfate reduction of microbial or inorganic origin (yellow). The light gray array labeled "Philippot array" represents the range of the photolyzed sulfur pool considered in (4). This array passes through the mean of the photolyzed S0 and sulfate-residual SO2 pools defined by (5, 7). Also shown are S isotope data from the literature covering the period 3800 to 2700 million years ago [data from (2, 4, 5, 7–17)]. (B) S istope systematics of Archaean sulfides for the period 3800 to 2700 million years ago. Blue diamonds and red squares correspond to North Pole sulfides and barites, respectively. Strongly 34S-depleted microscopic sulfides are shown in light blue. Black and red crosses correspond to sulfides and barites from other localities. More than 90% of the S isotope data are comprised within the 193-nm array used in (4). [View Larger Version of this Image (21K GIF file)]
 

The second model envisions mixing a small pool of homogeneous atmospheric S0 with extreme {Delta}33S values of about +70{per thousand} with a large pool of oceanic "sulfides" displaying negative {Delta}33S values of about 0 to –4{per thousand} and a large range of {Delta}34S values between +5 and –25{per thousand}. This model is based in part on geologically relevant observations and therefore must be considered with caution. The sulfate endmember used is typical of North Pole barite [negative {Delta}33S anomaly of about –1{per thousand} (2)]. The range of {delta}34S values considered for the "surface" sulfides are similar to the data reported by Shen et al. (3) and our original study (see Fig. 1 in (4)]. Following our data interpretation, Bao et al. (1) considered that such strongly 34S-depleted microscopic sulfides with negative {Delta}33S values could have formed from inorganic or microbial sulfate reduction. In contrast, the extreme positive {Delta}33S values of atmospheric S0 used by Bao et al. are derived from the experimental results of (5). Such extreme values were not found in the rock record. The highest positive {Delta}33S anomaly reported so far does not exceed 10{per thousand} (6). Product sulfate in equilibrium with this experimentally determined atmospheric endmember shows lower negative {Delta}33S values of about –25{per thousand} (see Fig. 1) than the one used by Bao et al. in their mixing model (0 to–4{per thousand}). To satisfy their model, they introduced the notion of "poor" mixing of small amounts of extremely fractionated atmospheric S0 raining down in a vast sulfide reservoir derived from the reduction of oceanic sulfate. Although conceptually feasible, this scenario does not fit with the geological observations.

Figure 2 shows a general framework of sulfur cycling during the Early Archaean. The diagrams in inset compare the sulfur isotope results recorded in North Pole drill cores with the prediction of the Bao et al. poor-mixing model. The small pool of particulate atmospheric S0 with extreme {Delta}33S anomalies should affect the entire rock sequence and should not be restricted to the microscopic sulfides lining barite overgrowth zones. Adjacent macroscopic pyrite laminae should show the same type of {Delta}33S/{delta}34S variation. In addition, sulfides located higher up in the sequence—namely the macroscopic sulfides in the bedded barite and the sedimentary sulfides in the volcano-sedimentary layer (orange layer) and cherty carbonate (pink layer) —should be increasingly exposed to the atmospheric S0 derived from the overlying water column. This should have resulted in a progressive increase in {Delta}33S values and a progressive decrease in {delta}34S values (indicated as a large dashed orange circle along the "Bao Array"). Although the sedimentary sulfides at the North Pole show a systematic positive {Delta}33S value, which indicates that the main sulfur component involved in their formation is indeed derived from atmospheric S0 aerosols, they display a narrow range of {Delta}33S and {delta}34S values close to the origin.


Figure 2 Fig. 2. {Delta}33S versus {delta}34S versus plots of sulfides (black diamonds) and barite (red squares) analyzed in (4). All analyses were performed on drill core samples shown as "rock sequence" on right [see (4) for details]. Diagrams on the left-hand side show the effect of mixing small amounts of extremely fractionated ({Delta}33S ~ +70{per thousand}) atmospheric sulfur with a large volume of sulfides derived from the reduction of oceanic sulfates. The highest amount of particulate atmospheric S0 aerosols will be stored in the sedimentary layers located on the sea floor. This in turn should result in increasing mechanically the {Delta}33S scatter of the sedimentary sulfides (large dashed orange circle evolving toward the "S0 atmospheric pool") compared with the macroscopic and microscopic sulfides present in the underlying bedded barite. The range of measured {Delta}33S versus {delta}34S values of North Pole sulfides are shown for comparison (black areas). Recognition that the sedimentary sulfides show systematic positive {Delta}33S anomalies indicates that the source of sedimentary sulfur was indeed almost exclusively derived from atmospheric S0, which agrees with the sulfide source defined in (1). However, the limited range of {Delta}33S and {delta}34S values of sedimentary sulfides argue against their mixing scenario. [View Larger Version of this Image (23K GIF file)]
 

Although we agree with Bao et al. (1) that our understanding of the Early Archaean sulfur cycle is limited, a number of basic observations should be kept in mind before developing complex mixing models. The basic premise of their model is that the original pool of oceanic sulfate with negative {Delta}33S anomaly is to be reduced microbially or inorganically into strongly 34S-depleted sulfides. This interpretation forms the crux of the reasoning of Shen et al. (3) and Philippot et al. (4). We see no need of invoking a complex mixing scenario at this stage.


References and Notes

Received for publication 24 October 2007. Accepted for publication 11 February 2008.

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Science. ISSN 0036-8075 (print), 1095-9203 (online)