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A Pan-Precambrian Link Between Deglaciation and Environmental Oxidation

Cooper, A. K., P. J. Barrett, H. Stagg, B. Storey, E. Stump, W. Wise, and the 10th ISAES editorial team, eds. (2008). Antarctica: A Keystone in a Changing World. Proceedings of the 10th International Symposium on Antarctic Earth Sciences. Washington, DC: The National Academies Press.

T. D. Raub and J. L. Kirschvink1

ABSTRACT

Despite a continuous increase in solar luminosity to the present, Earth’s glacial record appears to become more frequent, though less severe, over geological time. At least two of the three major Precambrian glacial intervals were exceptionally intense, with solid evidence for widespread sea ice on or near the equator, well within a “Snowball Earth” zone produced by ice-albedo runaway in energy-balance models. The end of the first unambiguously low-latitude glaciation, the early Paleoproterozoic Makganyene event, is associated intimately with the first solid evidence for global oxygenation, including the world’s largest sedimentary manganese deposit. Subsequent low-latitude deglaciations during the Cryogenian interval of the Neoproterozoic Era are also associated with progressive oxidation, and these young Precambrian ice ages coincide with the time when basal animal phyla were diversifying. However, specifically testing hypotheses of cause and effect between Earth’s Neoproterozoic biosphere and glaciation is complicated because large and rapid True Polar Wander events appear to punctuate Neoproterozoic time and may have episodically dominated earlier and later intervals as well, rendering geographic reconstruction and age correlation challenging except for an exceptionally well-defined global paleomagnetic database.

INTRODUCTION

Despite a 30 percent increase in solar luminosity during the past 4.6 billion years, we have solid geological evidence that liquid water was usually present on the surface. If the sun were to suddenly shift to even a 5-10 percent lower luminosity, our oceans would rapidly freeze over. We infer that this climatic regulation is due in large part to a combination of greenhouse gasses—principally H2O, CO2, and CH4—which have varied over time. For one of these, CO2, there is a clear inorganic feedback mechanism helping regulate climate (Walker et al., 1981), as CO2 removal by silicate weathering increases with temperature, a process that can act on a 106- to 107-year timescale.

Geologists observe that a major shift in redox state of Earth’s atmosphere happened sometime between 2.45 and 2.22 Ga ago, as signaled by the loss of a mass-independent fractionation signal in sulfur isotopes, the disappearance of common detrital pyrite and uraninite from stream deposits, and the appearance of true continental redbeds, documented by a reworked paleosol that cements together coherent hematitic chips magnetized in random directions (Evans et al., 2001). The sedimentary sulfate minerals barite and gypsum also become more prevalent in evaporative environments post ~2.3 Ga, as seen in the Barr River Formation of the Huronian Supergroup of Ontario (see Figure 1).

The reappearance of sedimentary sulfates after the Gowganda and Makganyene Glaciations at about 2.2 Ga follows a nearly 800 myr absence in the rock record (Huston and Logan, 2004), arguing that enough oxygen was then present in the atmosphere to oxidize pyrite to sulfate in quantities that sulfate-reducing organisms could not completely destroy.

Numerous hints in the rock record suggest a general relationship between changes in atmospheric redox state and severe glaciation. Most dramatically, the sedimentary package deposited immediately after the Paleoproterozoic low-latitude Makganyene glaciation in South Africa contains a banded iron formation-hosted manganese deposit that is the richest economic unit of this mineral known on Earth; Mn

1

Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125, USA.



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Cooper, A. K., P. J. Barrett, H. Stagg, B. Storey, E. Stump, W. Wise, and the 10th ISAES editorial team, eds. (2008). Antarctica: A Keystone in a Changing World. Proceedings of the 10th International Symposium on Antarctic Earth Sciences. Washington, DC: The National Academies Press. A Pan-Precambrian Link Between Deglaciation and Environmental Oxidation T. D. Raub and J. L. Kirschvink1 ABSTRACT were to suddenly shift to even a 5-10 percent lower luminos- ity, our oceans would rapidly freeze over. We infer that this Despite a continuous increase in solar luminosity to the pres- climatic regulation is due in large part to a combination of ent, Earth’s glacial record appears to become more frequent, greenhouse gasses—principally H2O, CO2, and CH4—which though less severe, over geological time. At least two of the have varied over time. For one of these, CO2, there is a clear three major Precambrian glacial intervals were exceptionally inorganic feedback mechanism helping regulate climate intense, with solid evidence for widespread sea ice on or near (Walker et al., 1981), as CO2 removal by silicate weathering the equator, well within a “Snowball Earth” zone produced increases with temperature, a process that can act on a 106- to by ice-albedo runaway in energy-balance models. The end 107-year timescale. of the first unambiguously low-latitude glaciation, the early Geologists observe that a major shift in redox state of Paleoproterozoic Makganyene event, is associated intimately Earth’s atmosphere happened sometime between 2.45 and with the first solid evidence for global oxygenation, includ- 2.22 Ga ago, as signaled by the loss of a mass-independent ing the world’s largest sedimentary manganese deposit. fractionation signal in sulfur isotopes, the disappearance of Subsequent low-latitude deglaciations during the Cryogenian common detrital pyrite and uraninite from stream deposits, interval of the Neoproterozoic Era are also associated with and the appearance of true continental redbeds, documented progressive oxidation, and these young Precambrian ice ages by a reworked paleosol that cements together coherent hema- coincide with the time when basal animal phyla were diver- titic chips magnetized in random directions (Evans et al., sifying. However, specifically testing hypotheses of cause 2001). The sedimentary sulfate minerals barite and gypsum and effect between Earth’s Neoproterozoic biosphere and also become more prevalent in evaporative environments glaciation is complicated because large and rapid True Polar post ~2.3 Ga, as seen in the Barr River Formation of the Wander events appear to punctuate Neoproterozoic time and Huronian Supergroup of Ontario (see Figure 1). may have episodically dominated earlier and later intervals The reappearance of sedimentary sulfates after the Gow- as well, rendering geographic reconstruction and age corre- ganda and Makganyene Glaciations at about 2.2 Ga follows lation challenging except for an exceptionally well-defined a nearly 800 myr absence in the rock record (Huston and global paleomagnetic database. Logan, 2004), arguing that enough oxygen was then present in the atmosphere to oxidize pyrite to sulfate in quantities that INTRODUCTION sulfate-reducing organisms could not completely destroy. Numerous hints in the rock record suggest a general Despite a 30 percent increase in solar luminosity during the relationship between changes in atmospheric redox state past 4.6 billion years, we have solid geological evidence that and severe glaciation. Most dramatically, the sedimentary liquid water was usually present on the surface. If the sun package deposited immediately after the Paleoproterozoic low-latitude Makganyene glaciation in South Africa contains a banded iron formation-hosted manganese deposit that is the 1 Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125, USA. richest economic unit of this mineral known on Earth; Mn 83

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84 ANTARCTICA: A KEYSTONE IN A CHANGING WORLD FIGURE 1 Gypsum casts, mud cracks, and ripples from the Barr River Formation north of Elliot Lake, Ontario, Canada. can only be precipitated from seawater by molecular oxy- peculiarities of low-latitude tillites, BIFs, abrupt and broadly gen (Kirschvink et al., 2000; Kopp et al., 2005). Similarly, synchronous glacial onset and termination, and many other Neoproterozoic glacial events are associated with apparent features of these events (Evans, 2000; Hoffman, 2007; Hoff- bursts of oxygenation and may have stimulated evolutionary man and Schrag, 2002; Hoffman et al., 1998). No alternative innovations like the Ediacara fauna and the rise of Metazoa. hypothesis even attempts to explain as many diverse features We argue here that Precambrian glaciations are generally of the Precambrian glacial record. followed by fluctuations in apparent redox parameters, con- Initially, the most fundamental result driving the Snow- sistent with a postulate by Liang et al. (2006) that significant ball Earth hypothesis was a soft-sediment fold test on a quantities of peroxide-generated oxidants are formed and varvite-like member of the ~635 Ma Marinoan-age Elatina released through glacial processes. formation in South Australia, which implied incursion of sea ice into subtropical latitudes (Figure 2) (Sumner et al., 1987). A few years later, Evans et al. (1997) demonstrated LOW-LATITUDE GLACIATION AS A SNOWBALL EARTH similarly robust results from the ~2.22 Ga Makganyene gla- Despite assertions to the contrary (Lovelock, 2006), climatic ciation in South Africa, indicating that at least two intervals regulatory mechanisms have not always maintained large of geological time, separated by more than a billion years, open areas of water on Earth’s surface. Substantial evidence experienced low-latitude glaciation. Comparison of less exists that large-scale continental ice sheets extended well robust paleomagnetic data for all Precambrian glaciations into the tropics, yielding sea ice at the equator (Embleton with well-documented paleolatitudes for Phanerozoic gla- and Williams, 1986; Evans et al., 1997; Sohl et al., 1999; cial deposits yields an interesting schism. With the possible Sumner et al., 1987). The deposition of banded iron oxide exception of the Archean Pongola event, there is a total formations (BIFs) associated with glacial sediments implies absence of evidence for polar or subpolar glaciation through- both sealing off of air-sea exchange and curtailing the input out the Precambrian, while marine glacial sedimentation of sulfate to the oceans, which otherwise would be reduced never breaches the tropics through the Phanerozoic (Evans, biologically to sulfide, raining out Fe as pyrite. The Snow- 2003). While the counterintuitive Precambrian polar glacial ball Earth hypothesis (Kirschvink, 1992) accounts for the gap must be largely an artifact of the paleogeographic and

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85 RAUB AND KIRSCHVINK B N A E W Before Fold Correction S N C W E After Fold Correction S FIGURE 2 Soft-sediment paleomagnetic fold test on the rhythmite member of the Elatina Formation, Pichi-Richi Pass, Australia. The initial paleomagnetic study on this member by Embleton and Williams (1986) displayed a nearly equatorial remanent magnetization held in hematite, but lacked a geological field test to verify that the characteristic magnetization was acquired at or near the time of deposition. As part of the Precambrian Paleobiology Research Group (PPRG) at the University of California, Los Angeles, in 1986, Bruce Runnegar provided J. L. K. with an oriented block sample of this unit (Figure 2A), which displayed an apparent soft-sediment deformation feature. Careful subsampling and demagnetization of this block by then undergraduate student Dawn Sumner (now at the University of California, Davis) revealed a horizontally aligned, elliptical distribution of directions consistent with the earlier result (Figure 2B). However, correction for the bedding deformation significantly tightened the distribution, making it Fisherian and passing the McElhinny (1964) fold test at P <0.05. This result, along with an equally interesting result from a layer deformed by a glacial drop stone in the Rapitan Banded Iron Forma- tion of Canada, was published as an American Geophysical Union abstract (Sumner et al., 1987); this led directly to the Snowball Earth Hypothesis (Kirschvink, 1992), and had the desired effect of stimulating further studies confirming the primary, low-latitude nature of the Elatina glacial event (Sohl et al., 1999; Williams et al., 1995). rock preservation records (Evans, 2006), the data consensus intervals dominated by dispersal of cratonic fragments points to an anomalously severe glacial mode in Proterozoic from previous supercontinents (Kenorland and Rodinia, time relative to the Phanerozoic Era. respectively), all Phanerozoic glacial events appear related Evans (2003) suggests that this shift in Earth’s glacial to episodes of continental amalgamation. (Possible Ordovi- mode reflects the evolution of macroscopic continental cian glaciation could mark the formation of Gondwanaland; life, especially of lichen and fungi through the Ediacaran- Carboniferous-Permian glaciation marks the assembly of Cambrian transition (see also Peterson et al., 2005). Such Pangea; and the Miocene-present glacial epoch arguably organisms might modulate the silicate-weathering feedback presages the formation of a future supercontinent termed to disfavor climate extremes, although the specifics of “SuperAsia” after the likely centroid of amalgamation.) whether endolithic organisms promote or hinder physical The characteristic length-scale of each supercontinent and chemical weathering is surprisingly still ambiguous (see was centered at the “equator” and spread, as a yellow Beerling and Berner, 2005). box, over the lifespan of that supercontinent. Blue wax- This fundamental Precambrian-Phanerozoic shift in ing triangles indicate intervals of dominant supercontinent Earth’s glacial mode also appears to manifest itself in the amalgamation, and red waning triangles indicate intervals relation of glacial events to a plate-tectonic supercontinent of dominant supercontinent fragmentation and dispersal. A cycle. Figure 3 relates a simplified compilation of Earth’s purple zone between the Paleoproterozoic supercontinent, glacial record to a schematic representation of Earth’s super- Nuna, and the Mesoproterozoic-Neoproterozoic supercon- continents through time. Whereas the Paleoproterozoic and tinent, Rodinia, indicates basic uncertainty as to whether Neoproterozoic low-paleolatitude glacial events occupied Nuna broke apart and reassembled into Rodinia, or whether

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86 ANTARCTICA: A KEYSTONE IN A CHANGING WORLD Supercontinents and Glaciations Gp El Po SP-H M Gb Ed Gk Go Pe Pl o 90 Length-Scale of Continents o 60 o 30 Super Asia P Gondwana FIGURE 3 Character of glaciations and Kenorland a Rodinia Nuna n o plate tectonics versus Earth history, mea- 0 g sured in geons (100-million-year blocks of e geological time). Surface areas for each of a o 30 the demonstrated or likely supercontinents in Earth history were estimated, and a characteristic length scale for each super- o 60 continent was defined as the square root of its surface area, converted from kilometers Past Future o 90 to degrees of arc. The vertical axis repre- sents a characteristic meridian on Earth, 30 25 20 15 10 5 0 -5 running from 90 degrees north latitude to 8 Time x 10 years (Geons) 90 degrees south. a single supercontinent simply grew monotonically over that cal box model called GEOCARBSULF (Berner, 2006) pre- interval. The future supercontinent SuperAsia is predicted to dicts monotonic increases in atmospheric oxygen concentra- begin its formal lifespan ~250 million years from now, when tion spanning the late Ordovician, Carboniferous-Permian, the oceanic lithosphere at the edge of the Atlantic ocean will and Miocene-present intervals of geologic time (for a recent have reached a foundering density and produced subduc- discussion of the Paleozoic data, see Huey and Ward, 2005), tion zones for enough time to reunite South America with with precipitous declines at the end-Permian. We suggest southern Africa and North America with northern Africa and that a recent model for ice-based peroxide formation (Liang Eurasia. Presumably Australia will have long since crumpled et al., 2006) contributes significantly to this Phanerozoic a neo-Himalayan orogenic belt still higher between its north- glaciation-oxygenation association, and extends even more ern margin and southeast Asia-eastern India. significantly through the more severe Precambrian glacial Maximum equatorward extents of ice ages were esti- episodes as well. mated from the paleomagnetic database (dark icicle fill) or using artistic license (light icicle fill) where paleomagnetic PONGOLA: EARTH’S OLDEST KNOWN GLACIATION data do not yet exist (e.g., for the Neoproterozoic Ghubrah event). An icicle was dropped from the North Pole to that The middle Archean Pongola Supergroup exposed in Swa- maximum equatorward latitude, with thickness approximat- ziland and parts of South Africa contains massive diamictite ing a plausible duration for each glacial event. Precambrian of the Klipwal and Mpatheni Members of the Delfkom For- glaciations are abbreviated as follows: Po = Pongola; H-SP = mation of the Mozaan Group (Young et al., 1998), which is Huronian and Snowy Pass Supergroups (at least two glacia- constrained to be younger than underlying volcanics of the tions not correlative to South African Makganyene glacia- Nsuze group dated at 2985 ± 1 (Hegner et al., 1994) and tion); M = Makganyene; Gp = Gariep; Gb = Ghubrah; Ed = older than a 2837 ± 5 Ma quartz porphyry sill (Gutzmer et al., Edwardsburg; El = Elatina-Ghaup; Gk = Gaskiers-Egan; Go 1999). The diamictites contain a diverse clast composition = Gondwana; Pe = Permian; Pl = Pleistocene. with striated and faceted pebbles, and occasional dropstones Whereas Precambrian glaciations appear restricted to that attest to a glacial origin. intervals of supercontinent fragmentation and dispersal, Although all sedimentary redox indicators throughout Phanerozoic glaciations appear more generally associated the Pongola Supergroup argue for widespread anoxia, stud- with supercontinent amalgamation and intervals of orogen- ies of sulfur isotopes that indicate that mass-independent esis. All glaciations are plausibly connected with minor or fractionation (MIF) decreases during and/or after the glacial major episodes of environmental oxidation or atmospheric intervals have been interpreted to support the presence of oxygenation. atmospheric oxygen (Bekker et al., 2005; Ohmoto et al., For most of Phanerozoic time, an integrated geochemi- 2006). Although this is the conventional interpretation, senso

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87 RAUB AND KIRSCHVINK mentation is not known, as all paleomagnetic components stricto this is not required. The presence of significant MIF identified so far have failed field stability tests (Hilburn et argues for O2 levels below that needed to form an ozone-UV al., 2005). shield, whereas the absence of MIF could indicate either a Glaciogenic units in southern Africa’s Transvaal Super- volcanic sulfur source or increased ocean and atmosphere group include the Duitschland, Timeball Hill, and Makg- mixing. In fact, before the studies were done, Kopp et al. anyene formations. Hannah et al. (2004) obtained a Re-Os (2005) predicted that a drop in sulfur MIF would be present pyrite isochron from the Timeball Hill Formation yielding in the Pongola sediments simply from increased ocean and an age of 2.32 Ga for the unit, while Cornell et al. (1996) atmosphere mixing expected for a time of glaciation com- obtained a Pb-Pb isochron indicating ~2.22 Ga for the age pared with an ice-free world. Nonetheless, relative oxidation of Ongeluk Formation volcanics that interfinger with the of the oceans that could also draw down atmospheric SO2 top of the Makganyene diamictite. The youngest detrital levels, even if unassociated with molecular oxygenation, zircons from thin sedimentary interbeds between flows of remains a viable explanation for the geochemical blips asso- the Ongeluk volcanics are ~2.23 Ga (Dorland, 2004), cor- ciated with Pongola glaciation. roborating the Pb-Pb isochron for the volcanics themselves. Nhelko (2004) studied the paleomagnetism of the Pon- Paleomagnetic data from the Ongeluk volcanics indicate gola diamictite and found an unusually strong and stable that the Makganyene is a low-latitude Snowball Earth event magnetization held in detrital magnetite, presumably derived (Evans et al., 1997; Kirschvink et al., 2000). Sedimentary from pulverizing basaltic-composition clasts present in the redox indicators in the Duitschland and most of the Timeball diamictite. He estimated the paleolatitude of deposition Hill imply reducing conditions, but the uppermost units of at ~48º, with positive fold and conglomerate tests on the the Timeball Hill formation contain a hematitic oolitic unit, characteristic, two-polarity magnetization. As other Snow- which if primary, hints again that the redox potential of the ball Earth lithostratigraphic markers such as cap carbonates atmosphere and ocean system reached the ferrous/ferric and carbonate clasts are generally absent, there is as yet no transition (which is energetically only halfway between the suggestion that Earth’s oldest glaciation might have been a hydrogen and oxygen redox potentials). low-latitude, global event. In Canada a paleosol at Ville St. Marie, Quebec (Rainbird et al., 1990) contains granule and pebble clasts with reddened PALEOPROTEROZIC GLACIAL INTERVALS rims at approximately the stratigraphic level of the Lorrain Formation. In South Africa the final pulse of the glaciogenic At least three (and potentially many more) discrete intervals succession records ice-rafted dropstones in the basal units of glacial activity punctuate the geological record between of the massive banded iron and sedimentary manganese in about 2.45 and 2.22 Ga (e.g., Hambrey and Harland, 1981). the Hotazel Formation. Together with the superjacent, ran- Of these, the best-known and best-preserved belong to the domly magnetized hematitic breccia paleosol (Evans et al., Huronian Supergroup of Canada and the Transvaal Super- 2001) (see “Background”), there is unequivocal evidence group of southern Africa. for significant oceanic oxidation as well as atmospheric In Canada the classic Huronian succession includes oxygenation in the immediate aftermath of low-paleolatitude the Ramsey Lake, Bruce, and Gowganda diamictites, sepa- Snowball Earth glaciation. rated from one another by thick successions of interbedded marine and fluvial sediments. A single carbonate unit (the Espanola formation) overlies the middle, Bruce Formation STURTIAN AND MARINOAN glacial horizon, with a gradual (not abrupt) transition from After at least a ~1-billion-year absence through late Paleo- the diamictite to carbonate in the Elliot Lake region (abrupt proterozoic time, all of the Mesoproterozoic Era, and the first transitions are seen elsewhere but could represent post- half of the Neoproterozoic Era, BIFs reappear at <720 Ma, glacial transgressions or unconformities). Basal volcanics intimately associated with early glacial deposits of the have been U-Pb dated at ~2.45 Ga, and the entire glacial “Cryogenian” interval (Klein and Beukes, 1993). At least succession is cut by dikes and sills of the Nipissing swarm, three discrete glaciations punctuate the latter half of Neopro- providing an upper age constraint of ~2.22 Ga. Sedimentary terozoic time (Evans, 2000), and current correlation schemes indicators of a generally reducing surface environment appear to permit five or more distinct events. The older are common in and around the Ramsey Lake and Bruce among these tend to be associated with hematite-enriched diamictites, but the first appearance of continental redbeds BIFs interrupting otherwise suboxic-to-anoxic, organic- appears just after the Gowganda event. This is either strong rich sediments, again suggesting penetration of oxidants to evidence for surface redox conditions reaching the ferrous- anomalous water depths accompanying deglaciation (Klein ferric transition, or else the evolution of terrestrial iron- and Beukes, 1993). oxidizing organisms. As with the Archean Pongola event, The younger two of the Neoproterozoic deglaciations MIF range of sulfur isotopes is diminished briefly after each occupy the newly defined Ediacaran Period (Knoll et al., glacial unit, hinting at but not proving transient oxidation 2006), at its base (~635 Ma, Condon et al., 2005; Hoffmann events. Unfortunately, the paleolatitude of Huronian sedi-

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88 ANTARCTICA: A KEYSTONE IN A CHANGING WORLD CORRELATION CAVEATS FOR EDIACARAN-CAMBRIAN et al., 2004) and approximately its middle (~580 Ma, EVENTS Bowring et al., 2003). At ~635 Ma the basal Ediacaran “Marinoan” low-latitude event is only rarely associated In a comprehensive study of inorganic and organic carbon, with banded iron and sedimentary manganese formation (in and sulfide as well as carbonate-associated-sulfate sulfur Brazil’s Urucum province), but it is frequently associated isotopes nearly spanning the Ediacaran Period, Fike et al. with reddened carbonate and shale dominating immediately (2006) infer at least 25 million years of increasing bacte- postglacial sea-level transgression (e.g., Halverson et al., rial sulfate reduction in the oceans following the Marinoan 2004). “Snowball” deglaciation. A sudden event known in Oman Patterns of sulfur isotopic fractionation in carbonate- as the Shuram anomaly then quickly oxidized a previously associated sulfate change across the Marinoan glaciation, isolated dissolved organic carbon reservoir, and the remain- such that seawater sulfate concentration was minimal during der of the Ediacaran Period experienced increasing levels of and after early Cryogenian glaciations, but significant fol- sulfur dissimilation reactions, permitted by enhanced oxygen lowing Marinoan glaciation (Hurtgen et al., 2005). Consis- concentrations (Fike et al., 2006). tent with this trend, the postglacial transgressive sequences Although the Shuram anomaly might correlate to the containing reddened carbonate and shale immediately after Gaskiers glacial event, in line with the general deglaciation- Marinoan deglaciation eventually culminate in black shale oxygenation association sketched in this paper, its age is horizons with microbialaminate textures and isotopic sig- strictly underconstrained, with widely varying estimates natures consistent with sulfate-reducing bacterial mat com- (e.g., see Condon et al., 2005, and Le Guerroue et al., 2006). munities (e.g., Calver and Walter, 2000; Calver et al., 2004; Because the Ediacaran Period is ubiquitously punctuated see also Hoffman et al., 2007). with paleomagnetic anomalies suggesting multiple, rapid true polar wander events (Evans, 1998; Evans, 2003; Raub et MID-EDIACARAN EGAN/GASKIERS GLACIATION al., 2007) which might also oxidize vast quantities of organic carbon (Kirschvink and Raub, 2003; Raub et al., 2007), While the basal Ediacaran deglaciation marks the end of an glaciations are not the only available and attractive correla- unambiguously low latitude, likely Snowball Earth event, tion targets for major isotopic excursions. In fact, decreased the middle interval of Ediacaran successions in northwest generation time and increased frequency of mutation fixa- Australia and in Newfoundland is punctuated by a glacial tion accompanying niche isolation and global warming in event of uncertain severity. Correlation between the Egan the aftermath of rapid true polar wander bursts has been glaciation in Australia’s Ediacaran carbonate belt (Corkeron, proposed as an explicit mechanism linking true polar wander 2007) and the Gaskiers glaciation in Newfoundland’s Avalon to the evolution of Ediacara and Metazoa (Kirschvink and terrane (Bowring et al., 2003) is not established, however Raub, 2003). In that respect, even the direct link between the both glacial events are younger than the Marinoan glaciation, final Precambrian, “Gaskiers” deglaciation and the evolution and both are associated with anomalous carbonate facies in of animal phyla must be regarded as still hypothesized more otherwise siliciclastic-dominated successions (Corkeron, than proven. 2007; Myrow and Kaufman, 1999). As with the basal-Ediacaran Marinoan deglaciation, THE PEROXIDE PUMP: the mid-Ediacaran Gaskiers deglaciation is associated with A MECHANISM FOR DEGLACIAL OXYGENATION postglacial reddening, culminating in pyrite-rich black shale at a presumed maximum flooding level. Silicate-hosted iron Many glaciologists have noted a semiregular oscillation in increases from pre-glacial to postglacial time, suggesting a the quantity of hydrogen peroxide contained in Antarctic step-function increase in atmospheric oxygen (Canfield et and Greenland ice cores, with concentrations increasing al., 2006). dramatically during the interval of enhanced ozone hole due Because the megascopic Ediacara fauna appear in the to anthropogenic emissions (Frey et al., 2005, 2006; Hutterli thick turbidite deposits following the Gaskiers deglaciation, et al., 2001, 2004). Similar peroxide peaks are inferred for back-of-the-envelope calculations suggest that the aftermath the polar regions of Mars and the ice sheet encasing Jupiter’s of the last Precambrian glaciation marked the first moment moon, Europa (Carlson et al., 1999). in Earth history when atmospheric oxygen levels exceeded Liang et al. (2006) generalize the phenomenon of per- ~15 percent of the present atmospheric level (Canfield et oxide snow produced by photolysis of water vapor above al., 2006). However, the Ediacara fauna have not yet been a cold ice sheet and applied 1-D mass-continuity models found in Newfoundland in the same, continuous stratigraphic of peroxide production to hypothetical glacial scenarios, section as the Gaskiers deglaciation, so the precise cause including Snowball Earths. and effect of postglacial oxygenation and the evolution of With modern volcanic outgassing and dry adiabatic complex life remains ambiguous. lapse rates, and at modern atmospheric pressure and UV inci-

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89 RAUB AND KIRSCHVINK Corkeron, M. 2007. “Cap carbonates” and Neoproterozoic glacigenic suc- dence, a ~10-million-year-long Snowball glacial event easily cessions from the Kimberley region, north-west Australia. Sedimentol- might rain out and capture in ice ~0.1 to 1.0 bar of molecular ogy 54:871-903. oxygen-equivalent hydrogen peroxide. The sensitivity of this Cornell, D. H., S. S. Schutte, and B. L. Eglington. 1996. The Ongeluk basal- astonishing result trends toward higher peroxide production tic andesite formation in Griqualand West, South-Africa—submarine for a depressed hydrologic cycle and lower global mean alteration in a 2222 Ma Proterozoic sea. Precambrian Research 79(1-2):101-123. temperature, both plausible in a Snowball Earth scenario. Dorland, H. 2004. Provenance, Ages, and Timing of Sedimentation of UV-depletion of stratospheric ozone and enhanced molecu- Selected Neoarchean and Paleoproterozoic Successions on the Kaapvaal lar hydrogen escape to space (both correlated, among other Craton. D.Phil. thesis. Rand Afrikaans University, Johannesburg. factors, to decreased geomagnetic field intensity) would also Embleton, B. J. J., and G. E. Williams. 1986. Low paleolatitude of depo- increase peroxide mixing rates at Earth’s surface. sition for late Precambrian periglacial varvites in South Australia— implications for Paleoclimatology. Earth and Planetary Science Letters We suggest that the model and mechanism of Liang 79(3-4):419-430. et al. (2006) can explain a pan-Precambrian association in Evans, D. A. 1998. True polar wander, a supercontinental legacy. Earth and the geologic record of deglaciation with trace or significant Planetary Science Letters 157(1-2):1-8. environmental oxidation and, during the aftermath of at least Evans, D. A. D. 2000. Stratigraphic, geochronological, and paleomagnetic the two most unambiguous Snowball Earth events, atmo- constraints upon the Neoproterozoic climatic paradox. American Jour- nal of Science 300:347-433. spheric oxygenation. We note that the Phanerozoic record Evans, D. A. D. 2003. A fundamental Precambrian-Phanerozoic shift in of relative atmospheric oxygen concentration inferred by Earth’s glacial style? Tectonophysics 375(1-4):353-385. the GEOCARBSULF model is also consistent with mono- Evans, D. A. D. 2006. Proterozoic low orbital obliquity and axial- tonic oxygen production during and immediately following dipolar geomagnetic field from evaporite palaeolatitudes. Nature glaciation. 444(7115):51-55. Evans, D. A., N. J. Beukes, and J. L. Kirschvink. 1997. Low-latitude glacia- . tion in the Paleoproterozoic. Nature 386(6622):262-266. ACKNOWLEDGMENTS Evans, D. A. D., J. Gutzmer, N. J. Beukes, and J. L. Kirschvink. 2001. . 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