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NASA NTRS1989

High-resolution infrared spectroscopy of Io and possible surface materials

A comparison of new spectra of Io with laboratory-simulated frosts confirms that the dominant materials on Io are SO2 frost in conjunction with a spectrally neutral material presumed to be sulfur. While the 4-micron region spectra are largely explainable in these terms, attention is drawn to a shoulder in the spectrum at 4.04 microns that is suggestive of adsorbed SO2 gas; two shallow, unidentified bands are also noted at 3.85 and 3.91 microns. The isotopic ratios of oxygen and sulfur appear to be normal. The absence of distinct bands in the new spectra in the 5-micron region limits the abundance of sulfate and sulfite compounds.

Howell, Robert R.↗
NASA NTRS1992

Geochemistry of Precambrian carbonates. V - Late Paleoproterozoic seawater

A study of mineralogy, chemistry, and isotopic composition of the Coronation Supergroup (about 1.9 Ga, NWT), Canada, and the McArthur Group (about 1.65 NT), Australia, is reported in order to obtain better constrained data for the first- and second-order variations in the isotopic composition of late Paleoproterozoic (1.9 +/- 0.2 Ga) seawater. Petrologically, both carbonate sequences are mostly dolostones. The McArthur population contains more abundant textural features that attest to the former presence of sulfates and halite, and the facies investigated represent ancient equivalents of modern evaporitic sabkhas and lacustrine playa lakes. It is suggested that dolomitization was an early diagenetic event and that the O-18 depletion of the Archean to late Paleoproterozoic carbonates is not an artifact of postdepositional alteration.

Veizer, Jan↗
NASA NTRS2002

Hypersaline Microbial Mat Lipid Biomarkers

Lipid biomarkers and compound specific isotopic abundances are powerful tools for studies of contemporary microbial ecosystems. Knowledge of the relationship of biomarkers to microbial physiology and community structure creates important links for understanding the nature of early organisms and paleoenvironments. Our recent work has focused on the hypersaline microbial mats in evaporation ponds at Guerrero Negro, Baja California Sur, Mexico. Specific biomarkers for diatoms, cyanobacteria, archaea, green nonsulfur (GNS), sulfate reducing, sulfur oxidizing and methanotrophic bacteria have been identified. Analyses of the ester-bound fatty acids indicate a highly diverse microbial community, dominated by photosynthetic organisms at the surface. The delta C-13 of cyanobacterial biomarkers such as the monomethylalkanes and hopanoids are consistent with the delta C-13 measured for bulk mat (-10%o), while a GNS biomarker, wax esters (WXE), suggests a more depleted delta C-13 for GNS biomass (-16%o). This isotopic relationship is different than that observed in mats at Octopus Spring, Yellowstone National Park (YSNP) where GNS appear to grow photoheterotrophic ally. WXE abundance, while relatively low, is most pronounced in an anaerobic zone just below the cyanobacterial layer. The WXE isotope composition at GN suggests that these bacteria utilize photoautotrophy incorporating dissolved inorganic carbon (DIC) via the 3-hydroxypropionate pathway using H2S or H2.

Jahnke, Linda L.↗
NASA NTRS2019

A Diversity of Calcium-Rich Carbonates in EETA 79001

Carbonate minerals of martian origin are present in several martian meteorites in trace concentrations (less than 1 percent) and possess unique isotopic signatures that suggest that the martian environment and/or isotopic reservoirs are very different from the Earth’s. Carbonates are most common in the older martian meteorites (ALH 84001 and the nakhlites), however, there have been reports of carbonate in the younger shergottites including EETA 79001 (Mars meteorite Elephant Moraine 79001). Acidification studies of Zagami and Shergotty have shown that CO2 is released suggesting that carbonate phases are present in these meteorites, but the origin of these phases is controversial. The young ages of the shergottites makes them important samples for understanding the modern martian environment. The carbonates in EETA 79001 are the best-characterized secondary minerals in a shergottite, but their origin remains controversial. Gooding et al. argued that two types of carbonate occur with-in the glassy parts of the meteorite. One type, nearly pure CaCO3 associated with Ca-sulfate shows textural evidence for being present in the rock prior to it being shocked, suggesting formation on Mars. The second was more abundant and consists of Ca-rich carbonate, possibly with finely intergrown Mg-phosphate, but does not possess any textural relationships indicative of a martian origin. Carbon and oxygen isotopic studies of this carbonate yielded oxygen isotopes that potentially suggest a martian origin as well

Niles, P. B.↗
NASA NTRS2018

Chain Formation as a Mechanism for Mass-Independent Fractionation of Sulfur Isotopes in the Archean Atmosphere

The anomalous abundances of sulfur isotopes in ancient sediments provide the strongest evidence for an anoxic atmosphere prior to ∼2.45 Ga, but the mechanism for producing this 'mass-independent' fractionation pattern remains in question. The prevailing hypothesis has been that it is created by differences in the UV photolysis rates of different SO2 isotopologues. We investigate here a recently proposed additional source of fractionation during gas-phase formation of elemental sulfur (S4 and S8). Because two minor S isotopes rarely occur in the same chain, the longer S4 and S8 chains should be strongly, and roughly equally, depleted in all minor isotopes. This gives rise to negative ∆(sup 33) S values and positive ∆(sub 36) S values in elemental sulfur-just the opposite of (and much larger than) what is predicted from SO2 photolysis itself. Back-reactions during chain formation, specifically photolysis of S2 and S3, pass sulfur having the opposite fractionation back to atomic S, and thence to other sulfur species, causing H2S, SO2, sulfate, and short-chain elemental sulfur to have positive ∆(sup 33) S and negative ∆(sup 36) S. Positive ∆(sup 33) S values in elemental sulfur produced in laboratory SO2 photolysis experiments could be caused by the initial fractionation during photolysis, combined with rapid condensation of short-chain sulfur species on the walls of the reaction chamber, along with a scarcity of back-reactions. The simulated fractionations produced by the chain formation mechanism do not directly match fractionations from the rock record. The mismatch might be explained if the isotopic signals leaving the atmosphere were significantly modulated by life, by uncertainties in the rates of reactions of both major and minor isotopic sulfur species, or by the relatively large potential range of atmospheric parameters. Further work is needed to better constrain these uncertainties, but this novel mechanism suggests new avenues to explore in our search for a explanation for the S-MIF record.

Great Oxidation Event↗
NASA NTRS2018

Chain Formation as a Mechanism for Mass-Independent Fractionation of Sulfur Isotopes in the Archean Atmosphere

The anomalous abundances of sulfur isotopes in ancient sediments provide the strongest evidence for an anoxic atmosphere prior to ∼2.45 Ga, but the mechanism for producing this ‘mass-independent’ fractionation pattern remains in question. The prevailing hypothesis has been that it is created by differences in the UV photolysis rates of different SO2 isotopologues. We investigate here a recently proposed additional source of fractionation during gas-phase formation of elemental sulfur (S4 and S8). Because two minor S isotopes rarely occur in the same chain, the longer S4 and S8 chains should be strongly, and roughly equally, depleted in all minor isotopes. This gives rise to negative Δ(exp 33)S values and positive Δ(exp 33)S values in elemental sulfur—just the opposite of (and much larger than) what is predicted from SO2 photolysis itself. Back-reactions during chain formation, specifically photolysis of S2 and S3, pass sulfur having the opposite fractionation back to atomic S, and thence to other sulfur species, causing H2S, SO2, sulfate, and short-chain elemental sulfur to have positive Δ(exp 33)S and negative Δ(exp 33)S. Positive Δ(exp 33)S values in elemental sulfur produced in laboratory SO2 photolysis experiments could be caused by the initial fractionation during photolysis, combined with rapid condensation of short-chain sulfur species on the walls of the reaction chamber, along with a scarcity of back-reactions. The simulated fractionations produced by the chain formation mechanism do not directly match fractionations from the rock record. The mismatch might be explained if the isotopic signals leaving the atmosphere were significantly modulated by life, by uncertainties in the rates of reactions of both major and minor isotopic sulfur species, or by the relatively large potential range of atmospheric parameters. Further work is needed to better constrain these uncertainties, but this novel mechanism suggests new avenues to explore in our search for a explanation for the S-MIF record.

C. E. Harman↗
NASA NTRS1996

Stable light isotope biogeochemistry of hydrothermal systems

The stable isotopic composition of the elements O, H, S and C in minerals and other chemical species can indicate the existence, extent, conditions and the processes (including biological activity) of hydrothermal systems. Hydrothermal alteration of the 18O/16O and D/H values of minerals can be used to detect fossil systems and delineate their areal extent. Water-rock interactions create isotopic signatures which indicate fluid composition, temperature, water-rock ratios, etc. The 18O/16O values of silica and carbonate deposits tend to increase with declining temperature and thus help to map thermal gradients. Measurements of D/H values can help to decipher the origin(s) of hydrothermal fluids. The 34S/32S and 13C/12C values of fluids and minerals reflect the origin of the S and C as well as oxygen fugacities and key redox processes. For example, a wide range of 34S/32S values which are consistent with equilibration below 100 degrees C between sulfide and sulfate can be attributed to sulfur metabolizing bacteria. Depending on its magnitude, the difference in the 13C/12C value of CO2 and carbonates versus organic carbon might be attributed either to equilibrium at hydrothermal temperatures or, if the difference exceeds 1% (10/1000), to organic biosynthesis. Along the thermal gradients of thermal spring outflows, the 13C/12C value of carbonates and 13C-depleted microbial organic carbon increases, principally due to the outgassing of relatively 13C-depleted CO2.

Review, Tutorial↗
NASA NTRS2002

Shergottite Impact Melt Glasses Contain Soil from Martian Uplands

Martian meteorite (shergottite) impact melt glasses that contain high concentrations of martian atmospheric noble gases and show significant variations in Sr-87/Sr-86 isotopic ratios are likely to contain Martian surface fines mixed with coarser regolith materials. The mixed soil constituents were molten due to shock at the time of meteoroid impact near the Martian surface and the molten glass got incorporated into the voids and cracks in some shergottite meteorites. Earlier, Rao et al. found large enrichments of sulfur (sulfate) during an electron-microprobe study of several impact melt glass veins and pods in EET79001,LithC thin sections. As sulfur is very abundant in Martian soil, these S excesses were attributed to the mixing of a soil component containing aqueously altered secondary minerals with the LithC precursor materials prior to impact melt generation. Recently, we studied additional impact melt glasses in two basaltic shergottites, Zagami and Shergotty using procedures similar to those described by Rao et al. Significant S enrichments in Zagami and Shergotty impact melt glass veins similar to the EET79001, LithC glasses were found. In addition, we noticed the depletion of the mafic component accompanied by the enrichment of felsic component in these impact melt glass veins relative to the bulk host rock in the shergottites. To explain these observations, we present a model based on comminution of basaltic rocks due to meteroid bombardment on martian regolith and mechanical fractionation leading to enrichment of felsics and depletion of mafics in the fine grained dust which is locally mobilized as a result of saltation and deflation due to the pervasive aeolian activity on Mars.

Rao, M. N.↗
NASA NTRS2002

Shergottite Impact Melt Glasses Contain Soil from Martian Uplands

Martian meteorite (shergottite) impact melt glasses that contain high concentrations of martian atmospheric noble gases and show significant variations in Sr-87/Sr-86 isotopic ratios are likely to contain Martian surface fines mixed with coarser regolith materials. The mixed soil constituents were molten due to shock at the time of meteoroid impact near the Martian surface and the molten glass got incorporated into the voids and cracks in some shergottite meteorites. Earlier, Rao et al. found large enrichments of sulfur (sulfate) during an electron-microprobe study of several impact melt glass veins and pods in EET79001,LithC thin sections. As sulfur is very abundant in Martian soil, these S excesses were attributed to the mixing of a soil component containing aqueously altered secondary minerals with the LithC precursor materials prior to impact melt generation. Recently, we studied additional impact melt glasses in two basaltic shergottites, Zagami and Shergotty using procedures similar to those described. Significant S enrichments in Zagami and Shergotty impact melt glass veins similar to the EET79001, LithC glasses were found. In addition, we noticed the depletion of the mafic component accompanied by the enrichment of felsic component in these impact melt glass veins relative to the bulk host rock in the shergottites. To explain these observations, we present a model based on comminution of basaltic rocks due to meteoroid bombardment on martian regolith and mechanical fractionation leading to enrichment of felsics and depletion of mafics in the fine grained dust which is locally mobilized as a result of saltation and deflation due to the pervasive aeolian activity on Mars.

Rao, M. N.↗
NASA NTRS1984

Concentrations and isotope ratios of carbon, nitrogen and sulfur in ocean-floor basalts

Ocean floor basalts studied from the Galapagos Ridge, FAMOUS area, Cayman Trough and Kilauea east rift contain 20-200 ppm carbon and 0.3-2.8 ppn nitrogen as sums of the vesicle-filling gases CO2 and N2 and dissolved species. The wide range of carbon contents found is due partly to the different extent of outgassing of vesicle-filling gases and partly to depth dependency of dissolved CO2 in the basalts. Sulfate commonly exists with sulfide in these basalts, and the sulfate/sulfide ratio increases with increasing water content, perhaps reflecting the higher oxidation potential in basalt melt of the higher water content.

Sakai, H.↗
NASA NTRS1985

Microanalysis of dissolved iron and phosphate in pore waters of hypersaline sediment

Diurnal fluctuations of reduced iron concentrations, expected to occur in reduced sediments in the photic zone, were studied. Iron concentration was compared to O2-H2S, a microcanalysis of sulfate reduction was performed, as well as an examination of diurnal concentration of dissolved phosphate and changes in interstitial CO2. The iron profiles suggest a strong correlation between iron remobilization and processes occurring in the light. Phosphate profiles suggest the removal of phosphate is strongly correlated with precipitation of oxidized iron in the upper 2 mm to 5 mm of the sediments. Pore water CO2 concentrations and carbon isotope ratios are presented. These data are from the analyses of minisediment cores collected from the 42 per mil salt pond and incubated in the laboratory under light and dark conditions.

Haddad, R.↗
NASA NTRS2005

Lunar and Planetary Science XXXVI, Part 20

The topics include: 1) Virtual Reality Technology as a Tool to Enhance Collaboration Between Space Exploration and Public Outreach: The Case Using the Mars Exploration Rover Images; 2) Atmospheric Electron-induced X-Ray Spectrometer (AEXS) Instrument Development; 3) Impact of Low Thermal Conductivity Layers on the Bulk Conductivity of a Martian Crustal Column; 4) Impacting Classroom Teachers Through Long-Term Professional Development; 5) Oxygen, Ca, and Ti Isotopic Compositions of Hibonite-bearing Inclusions; 6) Phenomenological Excitation Functions of Xe Isotopes with Protons on Nuclei of Cs, La and Ce; 7) Double-Diffusive Convection and Other Modes of Salinity-modulated Heat and Material Transport in Europa s Ocean; 8) Slope Morphologies of the Hellas Mensae Constructs, Eastern Hellas Planitia, Mars; 9) Development of Polygonal Thermal Contraction Patterns in a South Polar Trough, Mars 3 Years of Observations; 10) Martian Relevance of Dehydration and Rehydration in the Mg-Sulfate System; 11) Formation of Martian Volcanic Provinces by Lower Mantle Flushing? 12) Can Glasses Help Us to Unravel the Origin of Barred Olivine Chondrules? 13) Loki Patera: A Magma Sea Story; 14) Compositions of Partly Altered Olivine and Replacement Serpentine in the CM2 Chondrite QUE93005; 15) Model of Light Scattering by Lunar Regolith at Moderate Phase Angles: New Results; 16) Radiation Resistance of a Silicone Polymer Grease Based Regolith Collector for the HERA Near-Earth Asteroid Sample Return Mission; 17) Analysis of the Tectonic Lineaments in the Ganiki Planitia (V14) Quadrangle, Venus; 18) Nanometer-sized Diamonds from AGB Stars; 19) Quantifying Exact Motions Along Lineaments on Europa; 20) Geometry of Thrust Faults Beneath Amenthes Rupes, Mars; 21) Mapping of the Physical Characteristics and Mineral Composition of a Superficial Layer of the Moon or Mars and Ultra-Violet Polarimetry from the Orbital Station; 22) Negative Searches for Evidence of Aqueous Alteration on Asteroid Surfaces; 23) What Processes Have Shaped Basalt Boulders on Earth and Mars? Studies of Feature Persistence Using Facet Mapping and Fractal Analysis; 24) The Popigai Fluidizites: Dense Water Inclusions in Lechatelierite; Evidence for Shock-generated Carbonate and Hydrous Silicate Melts; 25) Missing Xenon Problem and Climate of the Early Earth; and 26) More on Magnetic Spectra from Correlated Crustal Sources on Mars

Source record↗
NASA NTRS2010

Sulfur Isotopes in Gas-rich Impact-Melt Glasses in Shergottites

Large impact melt glasses in some shergottites contain huge amounts of Martian atmospheric gases and they are known as gas-rich impact-melt (GRIM) glasses. By studying the neutron-induced isotopic deficits and excesses in Sm-149 and Sm-150 isotopes resulting from Sm-149 (n,gamma) 150Sm reaction and 80Kr excesses produced by Br-79 (n,gamma) Kr-80 reaction in the GRIM glasses using mass-spectrometric techniques, it was shown that these glasses in shergottites EET79001 and Shergotty contain regolith materials irradiated by a thermal neutron fluence of approx.10(exp 15) n/sq cm near Martian surface. Also, it was shown that these glasses contain varying amounts of sulfates and sulfides based on the release patterns of SO2 (sulfate) and H2S (sulfide) using stepwise-heating mass-spectrometric techniques. Furthermore, EMPA and FE-SEM studies in basaltic-shergottite GRIM glasses EET79001, LithB (,507& ,69), Shergotty (DBS I &II), Zagami (,992 & ,994) showed positive correlation between FeO and "SO3" (sulfide + sulfate), whereas those belonging to olivine-phyric shergottites EET79001, LithA (,506, & ,77) showed positive correlation between CaO/Al2O3 and "SO3".

Rao, M. N.↗
NASA NTRS2010

Jarosite in the Shergottite Que 94201

Veins of the hydroxylated, potassium ferric sulfate mineral jarosite - KFe3(SO4)2(OH)6 - have been identified in the martian meteorite Queen Alexandra Range (QUE) 94201. Iron potassium sulfate had been reported in QUE 94201 by Wentworth and Gooding. Jarosite has been reported in other Martian meteorites - Roberts Massif (RBT) 04262, Miller Range (MIL) 03346, and Yamato 000593 - and it has been identified on the Martian surface by Moessbauer spectroscopy. Given the presence of jarosite on Mars, and the burgeoning interest in water-rock interactions on Mars, the question arises whether jarosite in Martian meteorites is formed by aqueous alteration on Mars, or in Antarctica. Hydrogen isotopes are potentially sensitive indicators of the site of formation or last equilibration of hydrous alteration minerals, because of the large difference between D/H ratio of the Martian atmosphere (and also presumably the cryosphere) and terrestrial hydrogen. The Martian atmospheric delta D(sub SMOW) ratio is approximately +4200%o, igneous minerals with substantial hydrogen (phosphates) have high D, ~ +2000%o to +4700%o versus terrestrial waters with approximately 480%o to +130%o. The crystal chemistry and structure of jarosite are reviewed in Papi ke et al. Here we report hydrogen isotopes measured in jarosite in QUE 94201 by ion microprobe, and also report on the major element composition of jarosite measured by electron microprobe.

Ross, D. K.↗
NASA NTRS2013

The Mineralogical and Chemical Case for Habitability at Yellowknife Bay, Gale Crater, Mars

Sediments of the Yellowknife Bay formation (Gale crater) include the Sheepbed member, a mudstone cut by light-toned veins. Two drill samples, John Klein and Cumberland, were collected and analyzed by the CheMin XRD/XRF instrument and the Sample Analysis at Mars (SAM) evolved gas and isotopic analysis suite of instruments. Drill cuttings were also analyzed by the Alpha Particle X-ray Spectrometer (APXS) for bulk composition. The CheMin XRD analysis shows that the mudstone contains basaltic minerals (Fe-forsterite, augite, pigeonite, plagioclase), as well as Fe-oxide/hydroxides, Fe-sulfides, amorphous materials, and trioctahedral phyllosilicates. SAM evolved gas analysis of higher-temperature OH matches the CheMin XRD estimate of ~20% clay minerals in the mudstone. The light-toned veins contain Ca-sulfates; anhydrite and bassanite are detected by XRD but gypsum is also indicated from Mastcam spectral mapping. These sulfates appear to be almost entirely restricted to late-diagenetic veins. The sulfate content of the mudstone matrix itself is lower than other sediments analyzed on Mars. The presence of phyllosilicates indicates that the activity of water was high during their formation and/or transport and deposition (should they have been detrital). Lack of chlorite places limits on the maximum temperature of alteration (likely <100 C). The presence of Ca-sulfates rather than Mg- or Fe-sulfates suggests that the pore water pH was near-neutral and of relatively low ionic strength (although x-ray amorphous Mg-and Fe- sulfates could be present and undetectable by CheMin). The presence of Fe and S in both reduced and oxidized states represents chemical disequilibria that could have been utilized by chemolithoautotrophic biota, if present. When compared to the nearby Rocknest sand shadow mineralogy or the normative mineralogy of Martian soil, both John Klein and Cumberland exhibit a near-absence of olivine and a surplus of magnetite (7-9% of the crystalline component). The magnetite is interpreted as an authigenic product formed when olivine was altered to phyllosilicate. Saponitization of olivine (a process analogous to serpentinization) could have produced H2 in situ. Indeed, early diagenetic hollow nodules ("minibowls") present in the Cumberland mudstone are interpreted by some as forming when gas bubbles accumulated in the unconsolidated mudstone. Lastly, all of these early diagenetic features appear to have been preserved with minimal alteration since their formation, as indicated by the ease of drilling (weak lithification, lack of cementing phases), the presence of 20-30% amorphous material, and the late-stage fracturing with emplacement of calcium sulfate veins and minibowl infills, where they were intersected by veins. A rough estimate of the minimum duration of the lacustrine environment is provided by the minimum thickness of the Sheepbed member. Given 1.5 meters, and applying a mean sediment accumulation rate for lacustrine strata of 1 m/1000 yrs yields a duration of 1,500 years. If the aqueous environments represented by overlying strata are considered, such as Gillespie Lake and Shaler, then this duration increases. The Sheepbed mudstone meets all the requirements of a habitable environment: Aqueous deposition at clement conditions of P, T, pH, Eh and ionic strength, plus the availability of sources of chemical energy.

Blake, David Frederick↗
NASA NTRS2003

Lipid Biomarkers for a Hypersaline Microbial Mat Community

The use of lipid biomarkers and their carbon isotopic compositions are valuable tools for establishing links to ancient microbial ecosystems. As witnessed by the stromatolite record, benthic microbial mats grew in shallow water lagoonal environments where microorganisms had virtually no competition apart from the harsh conditions of hypersalinity, desiccation and intense light. Today, the modern counterparts of these microbial ecosystems find appropriate niches in only a few places where extremes eliminate eukaryotic grazers. Answers to many outstanding questions about the evolution of microorganisms and their environments on early Earth are best answered through study of these extant analogs. Lipids associated with various groups of bacteria can be valuable biomarkers for identification of specific groups of microorganisms both in ancient organic-rich sedimentary rocks (geolipids) and contemporary microbial communities (membrane lipids). Use of compound specific isotope analysis adds additional refinement to the identification of biomarker source, so that it is possible to take advantage of the 3C-depletions associated with various functional groups of organisms (i.e. autotrophs, heterotrophs, methanotrophs, methanogens) responsible for the cycling of carbon within a microbial community. Our recent work has focused on a set of hypersaline evaporation ponds at Guerrero Negro, Baja California Sur, Mexico which support the abundant growth of Microcoleus-dominated microbial mats. Specific biomarkers for diatoms, cyanobacteria, archaea, green nonsulfur (GNS), sulfate reducing, and methanotrophic bacteria have been identified. Analyses of the ester-bound fatty acids indicate a highly diverse microbial community, dominated by photosynthetic organisms at the surface.

Jahnke, Linda L.↗
NASA NTRS2016

Hemispherically Asymmetric Volcanic Forcing of Tropical Hydroclimate During the Last Millennium

Volcanic aerosols exert the most important natural radiative forcing of the last millennium. State-of-the-art paleoclimate simulations of this interval are typically forced with diverse spatial patterns of volcanic forcing, leading to different responses in tropical hydroclimate. Recently, theoretical considerations relating the intertropical convergence zone (ITCZ) position to the demands of global energy balance have emerged in the literature, allowing for a connection to be made between the paleoclimate simulations and recent developments in the understanding of ITCZ dynamics. These energetic considerations aid in explaining the well-known historical, paleoclimatic, and modeling evidence that the ITCZ migrates away from the hemisphere that is energetically deficient in response to asymmetric forcing. Here we use two separate general circulation model (GCM) suites of experiments for the last millennium to relate the ITCZ position to asymmetries in prescribed volcanic sulfate aerosols in the stratosphere and related asymmetric radiative forcing. We discuss the ITCZ shift in the context of atmospheric energetics and discuss the ramifications of transient ITCZ migrations for other sensitive indicators of changes in the tropical hydrologic cycle, including global streamflow. For the first time, we also offer insight into the large-scale fingerprint of water isotopologues in precipitation (delta sup 18 Op) in response to asymmetries in radiative forcing. The ITCZ shifts away from the hemisphere with greater volcanic forcing. Since the isotopic composition of precipitation in the ITCZ is relatively depleted compared to areas outside this zone, this meridional precipitation migration results in a large-scale enrichment (depletion) in the isotopic composition of tropical precipitation in regions the ITCZ moves away from (toward). Our results highlight the need for careful consideration of the spatial structure of volcanic forcing for interpreting volcanic signals in proxy records and therefore in evaluating the skill of Common Era climate model output.

Radiative forcing↗