Astrophysical molecules of AlH and CaH: RKR potential and dissociation energies

The true potential energy curves for the electronic ground states of astrophysically important AlH and CaH molecules are constructed by the Rydberg-Klein-Rees method. Empirical potential functions, of three-parameters by Lippincott, of five-parameters by Hulburt and Hirsch-felder and, of electronegativity by Szöke and Baitz, are examined for the adequacy to represent the true curve. From the best-fitting function, the dissociation energiesD ₀ ⁰ of AlH and CaH molecules are estimated to be 2.99 ± 0.08 and 2.72 ± 0.06 eV respectively. The force constants indicate that these values are of correct magnitude.     

Deciphering polymetamorphic episodes in high-grade metamorphic orogens: Constraints from PbSL, Sm/Nd and Lu/Hf garnet dating of low- to high-grade metasedimentary rocks from the Kaoko belt (Namibia)

Three dating techniques for metamorphic minerals using the Sm–Nd, Lu–Hf and Pb isotope systems are combined and interpreted in context with detailed petrologic data from crustal segments in NW Namibia. The combination of isochron ages using these different approaches is a valuable tool to testify for the validity of metamorphic mineral dating. Here, PbSL, Lu–Hf and Sm–Nd garnet ages obtained on low- to medium-grade metasedimentary rocks from the Central Kaoko Zone of the Neoproterozoic Kaoko belt (NW Namibia) indicate that these samples were metamorphosed at around 550–560 Ma. On the other hand, granulite facies metasedimentary rocks from the Western Kaoko Zone underwent two phases of high-grade metamorphism, one at ca. 660–625 Ma and another at ca. 550 Ma providing substantial evidence that the 660–625 Ma-event was indeed a major tectonothermal episode in the Kaoko belt. Our age data suggest that interpreting metamorphic ages by applying a single dating method only is not reliable enough when studying complex metamorphic systems. However, a combination of all three dating techniques used here provides a reliable basis for geochronological age interpretation.     

Petrochemistry of the Paleoproterozoic Udokan copper-bearing sedimentary complex

The maturity of terrigenous material of the Paleoproterozoic Udokan copper-bearing sedimentary complex is considered. The average values of hydrolyzate module (HM), alumina-silica module (AM), and Pettijohn’s coefficient of maturity appreciably vary throughout the Udokan Complex. Among cupriferous sandstones, rocks of the Aleksandrovka Formation are characterized by the highest maturity, whereas rocks of the Chitkanda Formation are distinguished by the lowest maturity. The maturity of cupriferous sandstones of the Sakukan Formation corresponds to that of host rocks. The maturity of cupriferous sandstones from the Aleksandrovka Formation is much higher than that of host rocks. In the Chitkanda Formation, the cupriferous sandstones are much less mature than host rocks. Climatic conditions in provenances estimated from the Nesbitt index of chemical weathering or chemical index of alteration (CIA) may be characterized as temperate ones without prominent climatic features. Most CIA values range from 46 to 66. The formation of copper-bearing sediments was closely related to the periods of volcanic activity.     

Cenozoic Eucla Basin and associated palaeovalleys,southern Australia — Climatic and tectonic influences on landscape evolution,sedimentation and heavy mineral accumulation

The Eucla Basin including the vast Nullarbor Plain lies on the margins of the Yilgarn, Musgrave and Gawler cratons in southern Australia and owes its distinctive landscape to a unique set of interactions between eustatic, climatic and tectonic processes over the last ~ 50 Ma. Understanding of the history of the basin and the palaeovalleys that drained from the surrounding cratons are important because they contain major mineral deposits, and the sediments derived from them contain remobilised gold, uranium, and heavy minerals. In particular, a remarkably preserved palaeoshoreline sequence along the north-eastern margin of the Eucla Basin is highly prospective for heavy mineral placer deposits. The record of marine, marginal marine, estuarine, fluvial and lacustrine environments, as constrained mainly by an extensive borehole dataset, reflects major depositional events during the Palaeocene–Early Eocene, Middle–Late Eocene, Oligocene–Early Miocene, Middle Miocene–Early Pliocene and Pliocene–Quaternary. These events reflect the key role of eustatic sea-level variation which, during highstands, inundated the craton margins, flooding palaeovalleys to up to 400 km inboard of the present coastline. However, a systematic eastward migration of the depocentre across the Eucla Basin during the Neogene, together with apparent flow reversals in a number of palaeovalley systems draining the Gawler Craton, suggest that the Eucla Basin has also been subject to differential vertical movements, expressed as a west-side up, east-side down tilting of ~ 100–200 m. This differential movement forms part of a broader north-down–southwest-up dynamic topographic tilting of the Australian continent associated with relatively fast (6–7 cm/yr) northward plate motion since fast spreading commenced in the Southern Ocean at ~ 43 Ma. We suggest that the evolving dynamic topography field has played a key role in facilitating development of placer deposits, largely through multistage, eastward reworking of near-shore sequences during highstand transgressive cycles on a progressively tilting platform under the influence of persistent westerly weather systems.     

Giant submarine landslide grooves in the Neoproterozoic/Lower Cambrian Phe Formation, northwest Himalaya: Mechanisms of formation and palaeogeographic implications

Giant groove casts have been found in the upper Proterozoic to Lower Cambrian Phe Formation (Haimanta Group), a siliciclastic sandstone/shale succession in the Tethyan Zone of the Higher Himalaya tectonic unit. The grooves are among the largest linear erosion structures related to submarine mass-movements observed in the geologic record. They are up to 4 m wide, about 0.2 m deep and can be traced for more than 35 m without changing their character. The grooves are straight, subparallel to cross-cutting striations with shallow semi-circular cross-sections and well-defined superimposed minor ridges and grooves. Groove casts exist on the soles of several sandstone beds within a 73 m thick logged section, commonly associated with flute casts. Their characteristics were compared with several other types of ancient and modern submarine linear erosion structures. A sand-rich, non-channelized basin floor depositional environment is inferred from the lithofacies, the combination of sedimentary structures, the lack of coarse-grained pebbly facies, the lateral continuity of beds, and the lack of channel structures. The grooves probably formed by laminar debris flows/concentrated density flows dragging blocks of already lithified sediment across the basin floor. When the bedding is structurally rotated back to horizontal, the groove casts show consistent North–South oriented palaeocurrent trends, with South-directed palaeocurrent directions indicated by flute casts. These palaeocurrent orientations contrast with previous palaeogeographic reconstructions of this area, which propose sediment delivery from the South. We therefore suggest a new “double provenance” model for the spatial relationship of late Proterozoic to Early Cambrian strata of the Himalaya, in which Lesser and Tethyan Himalayan age-equivalent sediment was deposited in a connected basin, where the former received detritus from the South, and the latter from a hitherto unknown source in the North. One possible candidate for this northern source is the South China Block and an associated Neoproterozoic volcanic arc.     

Development of the mixed conifer forest in northern New Mexico and its relationship to Holocene environmental change

Chihuahueños Bog (2925 m) in the Jemez Mountains of northern New Mexico contains one of the few records of late-glacial and postglacial development of the mixed conifer forest in southwestern North America. The Chihuahueños Bog record extends to over 15,000 cal yr BP. An Artemisia steppe, then an open Picea woodland grew around a small pond until ca. 11,700 cal yr BP when Pinus ponderosa became established. C/N ratios, δ¹³C and δ¹⁵N values indicate both terrestrial and aquatic organic matter was incorporated into the sediment. Higher percentages of aquatic algae and elevated C/N ratios indicate higher lake levels at the opening of the Holocene, but a wetland developed subsequently as climate warmed. From ca. 8500 to 6400 cal yr BP the pond desiccated in what must have been the driest period of the Holocene there. C/N ratios declined to their lowest Holocene levels, indicating intense decomposition in the sediment. Wetter conditions returned after 6400 cal yr BP, with conversion of the site to a sedge bog as groundwater levels rose. Higher charcoal influx rates after 6400 cal yr BP probably result from greater biomass production rates. Only minor shifts in the overstory species occurred during the Holocene, suggesting that mixed conifer forest dominated throughout the record.     

Detrital zircon provenance of Neoproterozoic to Cenozoic deposits in Iran: Implications for chronostratigraphy and collisional tectonics

Ion-microprobe U–Pb analyses of 589 detrital zircon grains from 14 sandstones of the Alborz mountains, Zagros mountains, and central Iranian plateau provide an initial framework for understanding the Neoproterozoic to Cenozoic provenance history of Iran. The results place improved chronological constraints on the age of earliest sediment accumulation during Neoproterozoic–Cambrian time, the timing of the Mesozoic Iran–Eurasia collision and Cenozoic Arabia–Eurasia collision, and the contribution of various sediment sources of Gondwanan and Eurasian affinity during opening and closure of the Paleotethys and Neotethys oceans. The zircon age populations suggest that deposition of the extensive ~ 1 km-thick clastic sequence at the base of the cover succession commenced in latest Neoproterozoic and terminated by Middle Cambrian time. Comparison of the geochronological data with detrital zircon ages for northern Gondwana reveals that sediment principally derived from the East African orogen covered a vast region encompassing northern Africa and the Middle East. Although most previous studies propose a simple passive-margin setting for Paleozoic Iran, detrital zircon age spectra indicate Late Devonian–Early Permian and Cambrian–Ordovician magmatism. These data suggest that Iran was affiliated with Eurasian magmatic arcs or that rift-related magmatic activity during opening of Paleotethys and Neotethys was more pronounced than thought along the northern Gondwanan passive-margin. For a Triassic–Jurassic clastic overlap assemblage (Shemshak Formation) in the Alborz mountains, U–Pb zircon ages provide chronostratigraphic age control requiring collision of Iran with Eurasia by late Carnian–early Norian time (220–210 Ma). Finally, Cenozoic strata yield abundant zircons of Eocene age, consistent with derivation from arc magmatic rocks related to late-stage subduction and/or breakoff of the Neotethys slab. Together with the timing of foreland basin sedimentation in the Zagros, these detrital zircon ages help bracket the onset of the Arabia–Eurasia collision in Iran between middle Eocene and late Oligocene time.     

Stable carbon-isotopic compositions of lipids isolated from the ammonia-oxidizing chemoautotroph Nitrosomonas europaea

For the ammonia-oxidizing bacterium Nitrosomonas europaea, grown autotrophically using semicontinuous culturing, average biomass was depleted in ¹³C relative to CO₂ dissolved in the medium by ca. 20‰ and the total-lipid extract was depleted in ¹³C relative to biomass by 3.7‰. The n-alkyl lipids (weighted average of fatty acids) and isoprenoid lipids (weighted average of hopanoids) were both depleted in ¹³C relative to biomass by about 9‰. The large depletion in the isoprenoid lipids seems to indicate that isotopic fractionations associated with the biosynthesis of methylerythritol phosphate (MEP) affected at least two carbon positions in each isoprene unit. Among the fatty acids, trans-9-hexadecenoic acid was most depleted (13.0‰ relative to biomass), followed by cis-9- hexadecenoic acid (9.6‰) and hexadecanoic acid (6.9‰). Isotopic relationships between the three acids suggest that significant isotope effects were associated with the desaturation and cis to trans isomerization of fatty acids. Given these observations, hopanoids produced by ammonia-oxidizing bacteria growing in natural waters are likely to be depleted in ¹³C by 26–30‰ relative to dissolved CO₂. Since CO₂ at aquatic oxyclines is often depleted in ¹³C, the range of δ values expected for hopanoids is ca. −34‰ to −55‰. The δ values of geohopanoids observed in numerous studies and attributed to unspecified chemoautotrophs fall within this range.     

Ultrahigh pressure macro diamonds from Copeton (New South Wales, Australia), based on Raman spectroscopy of inclusions

Mining of Cenozoic alluvial deposits at Copeton and Bingara (Eastern Australia) has produced two million macrodiamonds (0.25 ct median size). Raman spectroscopy is used to identify included minerals within uncut Copeton diamonds, with sealed chamber remnant pressures of 31.7 to 35.6 kbar for coesite, 13.6 and 22.7 kbar for clinopyroxene, and 7.6 kbar for grossular garnet. Assuming elastic behaviour, these values generate inclusion entrapment PT loci which intersect, restricting diamond formation conditions: from 250 °C, 43 kbar to 800 °C, 52 kbar. Larger than error (± 100 °C and ± 4 kbar), this range shows a systematic variation in inclusion composition with diamond zoning and N properties. Published research shows 1) Copeton and Bingara diamonds are unique, and 2) modern alluvium in the Bingara district carries mantle-formed garnet, captured by post-tectonic alkali basalt from an extensive diamondiferous ultrahigh pressure (UHP) terrane that stalled at depth because it is dominated by mafic eclogite. The combined Raman and geological results indicate two sets of subduction UHP diamond formation conditions/protolith are required, firstly cooler oceanic slab and secondly including higher temperature continental crust. The Copeton and Bingara stones are UHP macrodiamonds, and Carboniferous ⁴⁰Ar/³⁹Ar age dates on clinopyroxene inclusions should be interpreted as ages of crystallisation, representing the termination of subduction. The characteristic features of ruptured inclusions and etched percussion marks on Copeton and Bingara diamond indicate volcanic delivery to the earth's surface. Alluvial deposits elsewhere in Eastern Australia may carry similar diamond along with diamond of different origin.     

Organic carbon deposition and phosphorus accumulation during Oceanic Anoxic Event 2 in Tarfaya, Morocco

With a multi-proxy approach, an attempt was made to constrain productivity and bottom-water redox conditions and their effects on the phosphorus accumulation rate at the Mohammed Plage section on the Tarfaya coast, Morocco, during the Cenomanian-Turonian Anoxic Event (OAE 2). A distinct δ¹³C_org isotope excursion of +2.5‰ occurs close to the top of the section. The unusually abrupt shift of the isotope excursion and disappearance of several planktonic foraminiferal species (e.g. Rotalipora cushmani and Rotalipora greenhornensis) in this level suggests a hiatus of between 40–60 kyrs at the excursion onset. Nevertheless, it was possible to determine both the long-term environmental history as well as the processes that took place immediately prior to and during OAE 2. TOC% values increase gradually from the base of the section to the top (from 2.5% to 10%). This is interpreted as the consequence of a long-term eustatic sea-level rise and subsidence causing the encroachment of less oxic waters into the Tarfaya Basin. Similarly a reduction in the mineralogically constructed ‘detrital index’ can be explained by the decrease in the continental flux of terrigenous material due to a relative sea-level rise. A speciation of phosphorus in the upper part of the section, which spans the start and mid-stages of OAE 2, shows overall higher abundances of P_reactive mass accumulation rates before the isotope excursion onset and lower values during the plateau. Due to the probable short hiatus, the onset of the decrease in phosphorus content relative to the isotope excursion is uncertain, although the excursion plateau already contains lower concentrations. The C_org/P_total and V/Al ratios suggest that this reduction was mostly likely caused by a decrease in the available bottom oxygen content (probably as a result of higher productivity) and a corresponding fall in the phosphorus retention ability of the sediment. Productivity appears to have remained high during the isotope plateau possibly due to a combination of ocean-surface fertilisation via increased aridity (increased K/Al and Ti/Al ratios) and/or higher dissolved inorganic phosphorus content in the water column as a result of the decrease in sediment P retention. The evidence for decreased P-burial has been observed in many other palaeoenvironments during OAE 2. Tarfaya's unique upwelling paleosituation provides strong evidence that the nutrient recycling was a global phenomenon and therefore a critical factor in starting and sustaining OAE 2.