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Extreme Eolian Delivery of Reactive Iron to Late Paleozoic Icehouse Seas

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Extreme Eolian Delivery of Reactive Iron to Late Paleozoic Icehouse Seas Downloaded from geology.gsapubs.org on November 19, 2015 Extreme eolian delivery of reactive iron to late Paleozoic icehouse seas Sohini Sur1, Jeremy D. Owens2,3, Gerilyn S. Soreghan1*, Timothy W. Lyons2, Robert Raiswell4, Nicholas G. Heavens5, and Natalie M. Mahowald6 1School of Geology and Geophysics, University of Oklahoma, Norman, Oklahoma 73019, USA 2Department of Earth Sciences, University of California–Riverside, Riverside, California 92521, USA 3Earth, Ocean, and Atmospheric Science, Florida State University, Tallahassee, Florida 32306, USA 4School of Earth and Environment, University of Leeds, Leeds LS2 9JT, UK 5Department of Atmospheric and Planetary Sciences, Hampton University, Hampton, Virginia 23669, USA 6Department of Earth and Atmospheric Sciences, Cornell University, Ithaca, New York 14853, USA ABSTRACT directly in ancient sediment. Furthermore, prior The biogeochemical impacts of iron-rich dust to the oceans are known for Earth’s recent to deposition, these phases would have been record but unexplored for deep time, despite recognition of large ancient dust fluxes, par- amenable to enhanced secondary bioavailability ticularly during the late Paleozoic. We report a unique Fe relationship for Upper Pennsylva- though photochemical or cloud/aerosol process- nian mudrock of eolian origin that records lowstand (glacial) conditions within a carbonate ing during eolian transport (Shi et al., 2012). An buildup of western equatorial Pangaea (western United States) well removed from other detri- accurate measure of initial bioavailability for Fe tal inputs. Here, reactive Fe unambiguously linked to dust is enriched without a correspond- phases buried, recrystallized, and now preserved ing increase in total Fe. More broadly, data from thick coeval loess deposits of western equa- remains a challenge even for the modern, but our torial Pangaea show the same marked enrichment in reactive Fe. This enrichment—atypical approach advances this goal. Here, we assess Fe compared to modern marine, fluvial, glacial, loess, and soil sediments—suggests an enhance- reactivity from Pennsylvanian glacial-stage dust ment of the reactivity of the internal Fe pool that increased the bioavailability of the Fe for preserved in an isolated reef and in paleo-loesses marine primary production. Regardless of the mechanism behind this enhancement, our data of greater western equatorial Pangaea (western in combination with other evidence for high dust fluxes imply delivery of extraordinarily large United States). Collectively, these findings sug- amounts of biogeochemically reactive Fe to glacial-stage late Paleozoic seas, and modeling of gest remarkable fluxes of highly reactive Fe that this indicates major impacts on carbon cycling and attendant climatic feedbacks. should have profoundly influenced biogeochem- ical cycling of the late Paleozoic. INTRODUCTION ide bioavailable precursors such as ferrihydrite, In much of the modern ocean, iron is a lim- then ancient FeHR correspondingly scales to initial GEOLOGICAL BACKGROUND AND iting nutrient for marine primary productivity, bioavailability and thus can be used as a proxy for METHODS which in turn influences atmospheric CO2 (e.g., primary productivity, assuming ancient oceans During Pennsylvanian–Permian time, high- Martin et al., 1994; Boyd et al., 2007). Atmo- had Fe-limited regions like today’s oceans. lands and basins of the Ancestral Rocky Moun- spheric dust is a key source of bioavailable Fe to This scaling assumes that initial bioavail- tains formed in western tropical Pangaea (Figs. the ocean (e.g., Jickells et al., 2005), despite un- able Fe would have converted diagenetically to 1A and 1B). Strata within this greater region in- certainty regarding the processes that enhance crystalline oxides and can never be measured clude the thickest (>700 m) dust/loess deposits Fe bioavailability from dust (e.g., Mahowald et al., 2009; Raiswell and Canfield, 2012). Clari- Figure 1. A: Late Paleozoic fication of the role of Fe in ocean biogeochem- Pangaea, showing (boxed) A C D 30° istry thus remains a goal for the modern and 2080 Unit region of interest in western Age Name Epoch Period SB recent, and is completely unexplored for Earth’s tropical Pangaea (western Laurentia USA; detailed in B). B: Part deep-time record. Panthalassa 0° The role of Fe in ancient ecosystems is elu- of paleogeographic map of North America for 300 Ma Palaeo- Asselian Tethys Permian Cisuralian cidated by techniques enabling identification (from Blakey, 2013). Map de- Wolfcamp 299 Gondwana 30° of three Fe pools within the total Fe (FeT) pool: picts highstand conditions, with many epeiric seas (light highly reactive (FeHR), poorly reactive, and un- Late Penn. mbs blue colors); epeiric regions, Gondwanan Ice Cisco reactive (Canfield, 1989; Raiswell et al., 1994; Gzhelian including Horseshoe atoll, Raiswell and Canfield, 1998; Poulton and Can- were exposed during low- 2090 field, 2005). FeHR in mineral dust consists pre- stand (glacial) conditions. dominantly of amorphous and crystalline iron Core location is depicted B Mudrock oxides and (oxyhydr)oxides. These phases are with black circle. TX—Texas. most likely to have been soluble and thus bio- C: Chronostratigraphy of Horseshoe atoll study inter- Grst available at the time of deposition. This original val (Cisco unit; designated Maroon Loess (shallow) FeHR is present in ancient dust dominantly as by black box). Penn.—Penn- sylvanian. D: Facies log crystalline oxides, soluble in a citrate-bicarbon- Pkst and dust content (in wt%) 2100 ate–buffered sodium dithionite (CBD) solution Midland of Horseshoe atoll study Cutler Basin Loess (FeD). In some cases, a portion of those oxides sequence (see Sur et al., Wkst may have been diagenetically transformed to 2010a). Blue colors are car- (deep) 105o 100oW SB pyrite (Fe ). If the crystalline oxide phases ex- bonate facies (deeper hues paleoequator py 35oN tracted from the geologic record at least partially depict deeper-water facies). Horseshoe TX atoll “SB” (sequence boundary) 00.4 0.8 1.2 reflect less-crystalline, more-soluble oxyhydrox- 200 km denotes lowstand (glacial) 25o wt% dust exposure surfaces. mbs— *E-mail: [email protected] meters below surface; Wkst—wackestone; Pkst—packstone; Grst—grainstone. GEOLOGY, December 2015; v. 43; no. 12; p. 1099–1102 | Data Repository item 2015366 | doi:10.1130/G37226.1 | Published online 6 November 2015 GEOLOGY© 2015 Geological | Volume Society 43 | ofNumber America. 12 For | www.gsapubs.orgpermission to copy, contact [email protected]. 1099 Downloaded from geology.gsapubs.org on November 19, 2015 yet documented on Earth (Soreghan et al., 2008), Fig. 2A) in sharp contact with subtidal carbon- and marine carbonate in epeiric systems. One ate above and below. Within the mudrock, sub- such epeiric system, the Midland Basin, contains angular blocky microstructures, pedotubules, Horseshoe atoll, an isolated Upper Pennsylva- clay coatings, and localized centimeter-scale nian–Lower Permian algal reef (Fig. 1B) devoid slickensides mark pedogenesis (Fig. 2B); addi- of siliciclastic material excepting that delivered tionally, euhedral pyrite crystals and aggregates via eolian input (Sur et al., 2010a). The prov- (spore pseudomorphs) are common (Fig. 2C). enance of this dust indicates continental sources Quartz and illite are the dominant components. (e.g., Ancestral Rocky Mountains uplifts) with Modal grain size is 5 µm (mean = 6 µm; median minor contributions from the Ouachita orogen = 5.5 µm). (Sur et al., 2010a). An important implication Five samples through the ~0.4 m mudrock of this setting is that chemical fingerprints of were analyzed for bulk-rock geochemistry this dust and its inferred bioavailability can be (ICP-MS), total organic carbon (TOC), total extrapolated to the vast loess and dust deposits sulfur (ST), dithionite-soluble Fe concentration preserved in the coeval continental record. Fur- (FeD), pyrite S concentration (Spy), and pyrite 34 thermore, these large volumes of continental dust S isotope composition (d Spy). FeHR is deter- suggest that parts of the ocean received similarly mined by summing FeD and Fepy (Poulton and large Fe inputs (Large et al., 2015; Soreghan et Canfield, 2005), yielding ratios of FeHR to FeT al., 2015) with analogous bioreactivity. The sec- ranging from 0.66 to 0.78 (Table 1; Fig. 3). tion (Cisco unit) at Horseshoe atoll contains Very low inorganic carbon contents of <0.1 several glacioeustatic sequences (~18–24 m wt% confirm that Fe associated with carbonate thick) separated by paleosols recording glacial is negligible. Magnetite Fe was not analyzed; (lowstand) conditions that exposed the buildups however, the addition of magnetite would only to dust fall, much like the Bahamian reef incor- increase FeHR/FeT but not affect total Fe values. porates Saharan dust today. The middle Gzhelian The FeHR/FeT values are appreciably higher than (Upper Pennsylvanian) interval consists predom- those reported from modern riverine particulates inantly (99%) of carbonate, with <1% siliciclas- (average 0.43 ± 0.03; Poulton and Raiswell, tic mudrock concentrated at sequence boundaries 2002), oxic and dysoxic continental margin and (Sur et al., 2010a). We highlight analyses on the deep-sea sediments (0.26 ± 0.09; Anderson and sequence-bounding, glacial-stage mudrock from Raiswell, 2004), and Saharan soil dust (0.33 ± two sequences. The section is subsurface, hence 0.01; Poulton and Raiswell, 2002; cf. Shi et al., we used a continuous, air-drilled core. For dust 2012).
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