A photochemical model of the martian atmosphere

The factors governing the amounts of CO, O2, and O3 in the martian atmosphere are investigated using a minimally constrained, one-dimensional photochemical model. We find that the incorporation of temperature-dependent CO2 absorption cross sections leads to an enhancement in the water photolysis rate, increasing the abundance of OH radicals to the point where the model CO abundance is smaller than observed. Good agreement between models and observations of CO, O2, O3, and the escape flux of atomic hydrogen can be achieved, using only gas-phase chemistry, by varying the recommended rate constants for the reactions CO + OH and OH + HO2 within their specified uncertainties. Similar revisions have been suggested to resolve discrepancies between models and observations of the terrestrial mesosphere. The oxygen escape flux plays a key role in the oxygen budget on Mars; as inferred from the observed atomic hydrogen escape, it is much larger than recent calculations of the exospheric escape rate for oxygen. Weathering of the surface may account for the imbalance. Quantification of the escape rates of oxygen and hydrogen from Mars is a worthwhile objective for an upcoming martian upper atmospheric mission. We also consider the possibility that HOx radicals may be catalytically destroyed on dust grains suspended in the atmosphere. Good agreement with the observed CO mixing ratio can be achieved via this mechanism, but the resulting ozone column is much higher than the observed quantity. We feel that there is no need at this time to invoke heterogeneous processes to reconcile models and observations.     

Production of a molybdophore during metal-targeted dissolution of silicates by soil bacteria

Although many bioessential metals are scarce in natural water and rock systems, microbial secretion of high-affinity ligands for metal extraction from solid phases has only been documented for Fe. However, we have discovered that Mo is extracted from a silicate by a high-affinity ligand (a possible “molybdophore”) secreted by an N₂-fixing soil bacterium. The putative molybdophore, aminochelin, is secreted as a siderophore under Fe-depleted conditions, but is also secreted under Fe-sufficient, Mo-depleted conditions. Presumably, molybdophore production facilitates uptake of Mo for use in Mo enzymes. In contrast, an Fe-requiring soil bacterium without a special Mo requirement only enhances the release of Fe from the silicate. Fractionation of Mo stable isotopes during uptake to cells may provide a “fingerprint” for the importance of chelating ligands in such systems. Many such metal-specific ligands secreted by prokaryotes for extraction of bioessential metals, their effects on Earth materials, and their possible utility in the recovery of economic metals remain to be discovered.     

The behavior of molybdenum and its isotopes across the chemocline and in the sediments of sulfidic Lake Cadagno, Switzerland

Molybdenum (Mo) isotope studies in black shales can provide information about the redox evolution of the Earth’s oceans, provided the isotopic consequences of Mo burial into its major sinks are well understood. Previous applications of the Mo isotope paleo-ocean redox proxy assumed quantitative scavenging of Mo when buried into sulfidic sediments. This paper contains the first complete suite of Mo isotope fractionation observations in a sulfidic water column and sediment system, the meromictic Lake Cadagno, Switzerland, a small alpine lake with a pronounced oxygen-sulfide transition reaching up to H₂S ∼ 200 μM in the bottom waters (or about 300 μM total sulfide: ΣS²⁻ = H₂S + HS⁻ + S²⁻). We find that Mo behaves conservatively in the oxic zone and non-conservatively in the sulfidic zone, where dissolved Mo concentrations decrease from 14 nM to 2-8 nM across this transition. Dissolved Mo in the upper oxic waters has a δ⁹⁸Mo_oxic = 0.9 ± 0.1‰, which matches that of the riverine input, δ⁹⁸Mo_river = 0.9 ± 0.1‰. In the deeper sulfidic waters, a subaquatic source delivers Mo at 1.55 ± 0.1‰, but the dissolved Mo is even heavier at δ⁹⁸Mo_sulfidic = 1.8‰. Sediment traps in the sulfidic zone of the lake collect particles increasingly enriched in Mo with depth, with δ⁹⁸Mo values significantly fractionated at −0.8‰ to −1.2‰ both near the chemocline and in the deepest trap. Suspended particulates in the sulfidic waters carry lighter Mo than the ambient dissolved Mo pool by ∼0.3-1.5‰. Sedimentary Mo concentrations correlate with total organic carbon and yield Mo levels which are two orders of magnitude higher than typical crustal values found in rocks from the catchment area. Solid-phase Mo in the sediment shows a slightly positive δ⁹⁸Mo trend with depth, from δ⁹⁸Mo = 1.2‰ to 1.4‰ while the pore waters show dramatic enrichments of Mo (>2000 nM) with a relatively light isotope signature of δ⁹⁸Mo = 0.9-1.0‰.These data are explained if Mo is converted to particle-reactive oxythiomolybdates in the sulfidic waters and is fractionated during removal from solution onto particles. Isotope fractionation is expressed in the water column, despite the high sulfide concentrations, because the rate of Mo removal is fast compared to the slow reaction kinetics of thiomolybdate formation. However, elemental and isotopic mass balances show that Mo is indeed quantitatively removed to the lake sediments and thus the isotopic composition of the sediments reflects sources to the sulfidic water. This efficient Mo drawdown is expected to occur in settings where H₂S is very much in excess over Mo or in a restricted setting where the water renewal rate is slow compared to the Mo burial rate. We present a model for the Mo isotope fractionation in sulfidic systems associated with the slow reaction kinetics and conclude that quantitative removal will occur in highly sulfidic and restricted marine systems.     

Synoblique convergent and extensional deformation and metamorphism in the Neoproterozoic rocks along Wadi Fatira shear zone, Northern Eastern Desert, Egypt

The Wadi Fatira area occurs at the southern margin of the Northern Eastern Desert (NED) of Egypt and is occupied by highly sheared metavolcanics tectonically alternated with banded iron formations and intruded by Barud tonalite–granodiorite, post-tectonic gabbroic and granitic intrusions. Detailed structural investigation showed that the schists and migmatitic amphibolites are formed by shearing in metavolcanics and syntectonic Barud tonalite–granodiorite due to movement along the Wadi Fatira shear zone (WFSZ). This shear zone starts as a NW–SE striking fault along Wadi Barud Al Azraq and the Eastern part of Wadi Fatira and turns to a E–W trending fault to the north of Wadi Fatira. Microstructural shear sense indicators such as asymmetric geometry of porphyroclasts such as σ-type and asymmetric folds deforming fine-grained bands which are frequently found around porphyroclasts indicate sinistral sense of shearing along the WFSZ. This shear zone is characterized by transitions from local convergence to local extension along their E–W and NW–SE trending parts, respectively. The NW–SE part of the WFSZ is of about 200 m in width and characterized by synmagmatic extensional features such as intrusion of synkinematic tonalite, creation of NE–SE trending normal faults, and formation of migmatitic amphibolites and schlieric tonalites. This part of the shear zone is metamorphosed under synthermal peak metamorphic conditions (725°C at 2–4 kbar). The E–W compressional part of the WFSZ is up to 3 km in width and composed of hornblende, chlorite, actinolite, and biotite schists together with sheared intermediate and acidic metatuffs. Contractional and transpressional structures in this part of the WFSZ include E–W trending major asymmetrical anticline and syncline, nearly vertical foliation and steeply pitching stretching lineations, NNE dipping minor thrusts, and minor intrafolial folds with their hinges parallel to the stretching lineation. P–T estimates using mineral analyses of plagioclase and hornblende from schists and foliated metavolcanics indicate prograde metamorphism under medium-grade amphibolite facies (500–600°C at 3–7 kbar) retrogressed to low-grade greenschist facies (227–317°C). The foliation in Barud tonalite–granodiorite close to the E–W part of the WFSZ runs parallel to the plane of shearing and the tonalite show numerous magmatic flow structures overprinted by folding and ductile shearing. The WFSZ is similar to structures resulted from combined simple shear and orthogonal shortening of oblique transpressive shear zones and their sense of movement is comparable with the characteristics of the Najd Fault System.     

Methyl bromide: ocean sources, ocean sinks, and climate sensitivity

The oceans play an important role in the geochemical cycle of methyl bromide (CH3Br), the major carrier of O3-destroying bromine to the stratosphere. The quantity of CH3Br produced annually in seawater is comparable to the amount entering the atmosphere each year from natural and anthropogenic sources. The production mechanism is unknown but may be biological. Most of this CH3Br is consumed in situ by hydrolysis or reaction with chloride. The size of the fraction which escapes to the atmosphere is poorly constrained; measurements in seawater and the atmosphere have been used to justify both a large oceanic CH3Br flux to the atmosphere and a small net ocean sink. Since the consumption reactions are extremely temperature-sensitive, small temperature variations have large effects on the CH3Br concentration in seawater, and therefore on the exchange between the atmosphere and the ocean. The net CH3Br flux is also sensitive to variations in the rate of CH3Br production. We have quantified these effects using a simple steady state mass balance model. When CH3Br production rates are linearly scaled with seawater chlorophyll content, this model reproduces the latitudinal variations in marine CH3Br concentrations observed in the east Pacific Ocean by Singh et al. [1983] and by Lobert et al. [1995]. The apparent correlation of CH3Br production with primary production explains the discrepancies between the two observational studies, strengthening recent suggestions that the open ocean is a small net sink for atmospheric CH3Br, rather than a large net source. The Southern Ocean is implicated as a possible large net source of CH3Br to the atmosphere. Since our model indicates that both the direction and magnitude of CH3Br exchange between the atmosphere and ocean are extremely sensitive to temperature and marine productivity, and since the rate of CH3Br production in the oceans is comparable to the rate at which this compound is introduced to the atmosphere, even small perturbations to temperature or productivity can modify atmospheric CH3Br. Therefore atmospheric CH3Br should be sensitive to climate conditions. Our modeling indicates that climate-induced CH3Br variations can be larger than those resulting from small (+/- 25%) changes in the anthropogenic source, assuming that this source comprises less than half of all inputs. Future measurements of marine CH3Br, temperature, and primary production should be combined with such models to determine the relationship between marine biological activity and CH3Br production. Better understanding of the biological term is especially important to assess the importance of non-anthropogenic sources to stratospheric ozone loss and the sensitivity of these sources to global climate change.     

Variation of Mo isotopes from molybdenite in high-temperature hydrothermal ore deposits

Measurable molybdenum isotope fractionation in molybdenites from different ore deposits through time provides insights into ore genesis and a new technique to identify open-system behavior of Re–Os in molybdenites. Molybdenite samples from six porphyry copper deposits, one epithermal polymetallic vein deposit, four skarns, and three Fe-oxide Cu–Au deposits were analyzed. The δ⁹⁷Mo‰ (where ) for all samples varied from 1.34 ± 0.09‰ to −0.26 ± 0.04‰. This is the largest molybdenum isotopic variation in molybdenite from high-temperature ore deposits recorded to date. δ⁹⁷Mo‰ of molybdenite varies as a function of the deposit type and the rhenium and osmium concentrations of the samples. Isotope values for Mo also vary within the individual deposits. In general, molybdenites from porphyry copper deposits have the lightest values averaging 0.07 ± 0.23‰ (1σ). Molybdenites from the other deposit types average 0.49 ± 0.26‰ (1σ). The variations could be related to the fractionation of Mo into different mineral phases during the ore-forming processes. A comparison of the Mo isotope ratios and the Re–Os ages obtained from the same aliquot may possess a geochronological evaluation tool. Samples that yielded robust ages have different Mo isotopic compositions in comparison to samples that yielded geologically unreasonable ages. Another observed relationship between the Re–Os and Mo isotope data reveals a weak correspondence between Re concentration and Mo isotope composition. Molybdenites with higher concentrations of Re correspond to lighter Mo isotope values.     

Formation of syngenetic and early diagenetic iron minerals in the late Archean Mt. McRae Shale, Hamersley Basin, Australia: New insights on the patterns, controls and paleoenvironmental implications of authigenic mineral formation

A section through the late Archean Mt. McRae Shale comprising, in ascending order, a lower shale interval (LSI), a banded iron formation (BIF), an upper shale (USI) and a carbonate (C1) has been analyzed for total Fe and Al contents and authigenic Fe present as carbonate, oxide, sulfide and silicate phases. The authigenic mineralogy is controlled by the episodic addition of Fe from hydrothermal activity and removal of Fe by sulfide, relative to rates of clastic sedimentation. The LSI and BIF have mean Fe_T/Al values of 2 and 5, respectively, that record iron enrichment from hydrothermal sources. Iron was precipitated primarily as siderite accompanied by Fe-rich chlorite from anoxic bottom waters rich in dissolved Fe. Pyrite formation was probably limited by the availability of sulfate, which was present at low concentrations and became rapidly depleted. The USI has generally lower Fe_T/Al values (0.6-1.3), similar to those found in Paleozoic shales, with the exception of one interval where enrichment may reflect either a weak hydrothermal source or the operation of an iron shuttle. This interval contains authigenic Fe predominantly as pyrite, where high values for DOP (>0.8) indicate the existence of a water column that became rich in dissolved sulfide (euxinic) when sulfate concentrations increased due to a transient or secular increase in ocean/atmosphere oxygenation. High concentrations of dissolved sulfide maintained low concentrations of dissolved Fe, which allowed only minor amounts of Fe to be precipitated as carbonates and silicates. The USI also has elevated concentrations of organic matter that most probably reflect increased productivity and likely limited euxinia to midportions of the water column on the basin margin. The carbonate C1 represents a basinal chemistry where sulfide has been removed and Fe_T/Al values are ∼1 indicating that hydrothermal activity again produced dissolved Fe-rich bottom waters. Detailed iron speciation of the Mt. McRae Shale can be used to recognize spatial and temporal variations in iron and sulfur inputs to the late Archean Hamersley Basin, just prior to the Paleoproterozoic rise in atmospheric oxygenation, and our refined methods have relevance to all Fe-rich deposits.     

The photochemistry of manganese and the origin of Banded Iron Formations

The photochemical oxidation of Fe(2+) -hydroxide complexes dissolved in anoxic Precambrian oceans has been suggested as a mechanism to explain the deposition of Banded Iron Formations (BIFs). Photochemical studies have not yet addressed the low levels of manganese in many of these deposits, which probably precipitated from solutions bearing similar concentrations of Fe2+ and Mn2+. Depositional models must also explain the stratigraphic separation of iron and manganese ores in manganiferous BIFs. In this study, solutions containing 0.56 M NaCl and approximately 180 micromoles MnCl2 with or without 3 to 200 micromoles FeCl2 were irradiated with filtered and unfiltered UV light from a medium-pressure mercury-vapor lamp for up to 8 hours. The solutions were deaerated and buffered to pH approximately 7, and all experiments were conducted under O2-free (< 1 ppm) atmospheres. In experiments with NaCl + MnCl2, approximately 20% of the Mn2+ was oxidized and precipitated as birnessite in 8 hours. Manganese precipitation was only observed when light with lambda < 240 nm was used. In experiments with NaCl + MnCl2 + FeCl2, little manganese was lost from solution, while Fe2+ was rapidly oxidized to Fe3+ and precipitated as gamma-FeOOH or as amorphous ferric hydroxide. The Mn:Fe ratio of these precipitates was approximately 1:50, similar to the ratios observed in BIFs. A strong upper limit on the rate of manganese photo-oxidation during the Precambrian is estimated to be 0.1 mg cm-2 yr-1, a factor of 10(3) slower than the rate of iron photo-oxidation considered reasonable in BIF depositional basins. Thus, a photochemical model for the origin of oxide facies BIFs is consistent with field observations, although models that invoke molecular O2 as the oxidant of Fe2+ and Mn2+ are not precluded. Apparently, oxide facies BIFs could have formed under anoxic, as well as under mildly oxygenated atmospheres.     

ESR and Th/U dating of speleothems from Aladağlar Mountain Range (AMR) in Turkey

Electron spin resonance (ESR) and ²³⁰Th/²³⁴U ages of speleothem samples collected from karstic caves located around 3000 m elevation in the Alada?lar Mountain Range (AMR), south-central Turkey, were determined in order to provide new insight and information regarding late Pleistocene climate. ESR ages were validated with the ²³⁰Th/²³⁴U ages of test samples. The ESR ages of 21 different layers of six speleothem samples were found to range mostly between about 59 and 4 ka, which cover the Marine Oxygen Isotope Stages (MIS) MIS 3 to MIS 1. Among all, only six layers appear to have deposited during MIS 8 and 5. Most of the samples dated were deposited during the late glacial stage (MIS 2). It appears that a cooler climate with a perennial and steady recharge was more conducive to speleothem development rather than a warmer climate with seasonal recharge in the AMR during the late Quaternary. This argument supports previous findings that suggest a two -fold increase in last glacial maximum mean precipitation in Turkey with respect to the present value.     

Molybdenum isotope evidence for mild environmental oxygenation before the Great Oxidation Event

We use the molybdenum isotope paleoredox proxy to look for evidence of small amounts of O₂ in the environment ∼50 Ma before the Great Oxidation Event (GOE) in a high resolution profile from the ∼2.5 Ga Mt. McRae Shale. The molybdenum isotope compositions (δ^98/95Mo) from samples throughout the sequence span a range from 0.99‰ to 1.86‰. All samples have heavier δ^98/95Mo compared to average upper continental crust. In addition, the upper (S1) and lower (S2) black shale units within the Mt. McRae Shale exhibit systematic differences in average isotopic compositions and distinct patterns of δ^98/95Mo variation. Heavier δ^98/95Mo values occur in the S1 unit, where δ^98/95Mo correlates with Mo enrichments. In the S2 unit, δ^98/95Mo is not as heavy and is relatively invariant.Based on sedimentary Fe proxies we infer that S1 sediments were deposited under euxinic conditions, so that Mo removal from bottom waters was likely quantitative. Thus, δ^98/95Mo in this interval likely records coeval seawater. The lighter δ^98/95Mo values in the S2 unit may indicate a less fractionated ocean Mo inventory relative to the S1 unit. However, sedimentary Fe proxies suggest that S2 sediments accumulated under a water column that was ferruginous rather than euxinic, raising the possibility of non-quantitative Mo scavenging and hence an expressed δ^98/95Mo fractionation relative to coeval seawater. Because any associated fractionations during this process would have favored the light isotope in sediments, the lighter δ^98/95Mo values in the S2 unit represent a lower limit on the value in contemporaneous seawater.After evaluating a range of hypotheses, we conclude that the isotopically heavy δ^98/95Mo values seen throughout the Mt. McRae Shale likely reflect the effects of oxidative weathering and adsorption of Mo to oxide mineral surfaces on land or in surface oceans. The extent of environmental oxygenation in either unit is difficult to assess due to uncertainties in the global Mo isotope budget. Because of the small ocean Mo inventory in the Late Archean, documented by low concentrations of Mo and low Mo/TOC, the extent of oxygenation required to account for the observed fractionations is much smaller than in modern oceans. However, when juxtaposed against the record of δ^98/95Mo through time, our findings provide further evidence of the onset of environmental oxygenation before the GOE.