XPS identification of bulk hole defects and itinerant Fe 3d electrons in natural troilite (FeS)

XPS measurements have been made of vacuum-fractured monoclinic pyrrhotite and troilite that highlight sulfur coordination (S 2p) and iron electronic state (Fe 2p) differences between these two minerals as a result of iron lattice site occupancy. Metal-like Fe states are observed in the Fe 2p spectrum of troilite due to increased occupancy of Fe lattice sites and increased Fe-Fe 3d orbital interaction within the constraints of the mineral structure. Additional electron population near the top of the troilite valence band is confirmed by XPS measurement. These results provide comprehensive experimental evidence for itinerent 3d electrons in the natural iron sulfides.     

Wildlife management and land reform in southeastern Zimbabwe: a compatible pairing or a contradiction in terms?

This paper examines the melding of two discourses in southeastern Zimbabwe: land reform and wildlife management. The former seeks to redistribute large, ‘under-utilized’ landholdings to smallholders whilst the latter needs extensive land holdings to be viable. These two discourses are rooted in very different models of development. The land reform exercise emphasizes direct redistribution, equity and land for crops; whilst the wildlife management discourse tends to stress maximizing foreign exchange earnings, encouraging public-private partnerships and trickle down. Yet there has been a recent flurry of interest in the development of ‘wildlife models’ for land reform which would combine the two. This paper investigates whether the competing discourses about land for smallholders and wildlife-based land reform are compatible or can be successfully reconciled. It traces the ways they have come together in Zimbabwe’s southeast lowveld and examines the ‘science’ and politics underlying their melding. Finally it explores the potential implications for rural people’s livelihoods of this development. It concludes that land reform and wildlife management can be reconciled, but probably not in a particularly equitable way: it is more likely to provide an opening for an equitable land reform agenda to be usurped by local and non-local elites with wildlife interests.     

Lu–Hf and U–Pb isotope systematics of zircons from the Storgangen intrusion, Rogaland Intrusive Complex, SW Norway: implications for the composition and evolution of Precambrian lower crust in the Baltic Shield

The Storgangen orebody is a concordantly layered, sill-like body of ilmenite-rich norite, intruding anorthosites of the Rogaland Intrusive Complex (RIC), SW Norway. 17 zircon grains were separated from ca. 5 kg of sand-size flotation waste collected from the on-site repository from ilmenite mining. These zircons were analysed for major and trace elements by electron microprobe, and for U–Pb and Lu–Hf isotopes by laser ablation microprobe plasma source mass spectrometry. Eight of the zircons define a well-constrained (MSWD=0.37) concordant population with an age of 949±7 Ma, which is significantly older than the 920–930 Ma ages previously reported for zircon inclusions in orthopyroxene megacrysts from the RIC. The remaining zircons, interpreted as inherited grains, show a range of ²⁰⁷Pb/²⁰⁶Pb ages up to 1407±14 Ma, with an upper intercept age at ca. 1520 Ma. The concordant zircons have similar trace element patterns, and a mean initial Hf isotope composition of ¹⁷⁶Hf/¹⁷⁷Hf_{949 Ma}=0.28223±5 (_Hf=+2±2). This is similar to the Hf-isotope composition of zircons in a range of post-tectonic Sveconorwegian granites from South Norway, and slightly more radiogenic than expected for mid-Proterozoic juvenile crust. The older, inherited zircons show Lu–Hf crustal residence ages in the range 1.85–2.04 Ga. One (undated) zircon plots well within the field of Hf isotope evolution of Paleoproterozoic rocks of the Baltic Shield. These findings indicate the presence of Paleoproterozoic components in the deep crust of the Rogaland area, but do not demonstrate that such rocks, or a Sveconorwegian mantle-derived component, contributed significantly to the petrogenesis of the RIC. If the parent magma was derived from a homogeneous, lower crustal mafic granulite source, the lower crustal protolith must be at least 1.5 Ga old, and it must have an elevated Rb/Sr ratio. This component would be indistinguishable in Sr, Nd and Hf isotopes from some intermediate mixtures between Sveconorwegian mantle and Paleoprotoerzoic felsic crust, but it cannot account for the initial ¹⁴³Nd/¹⁴⁴Nd of the most primitive, late Sveconorwegian granite in the region, without the addition of mantle-derived material.     

Inclusions in diamonds from the K14 and K10 kimberlites, Buffalo Hills, Alberta, Canada: diamond growth in a plume?

Analyses of mineral inclusions, carbon isotopes, nitrogen contents and nitrogen aggregation states in 29 diamonds from two Buffalo Hills kimberlites in northern Alberta, Canada were conducted. From 25 inclusion bearing diamonds, the following paragenetic abundances were found: peridotitic (48%), eclogitic (32%), eclogitic/websteritic (8%), websteritic (4%), ultradeep? (4%) and unknown (4%). Diamonds containing mineral inclusions of ferropericlase, and mixed eclogitic-asthenospheric-websteritic and eclogitic-websteritic mineral associations suggests the possibility of diamond growth over a range of depths and in a variety of mantle environments (lithosphere, asthenosphere and possibly lower mantle).

Eclogitic diamonds have a broad range of C-isotopic composition (δ¹³C=−21‰ to −5‰). Peridotitic, websteritic and ultradeep diamonds have typical mantle C-isotope values (δ¹³C=−4.9‰ av.), except for two ¹³C-depleted peridotitic (δ¹³C=−11.8‰, −14.6‰) and one ¹³C-depleted websteritic diamond (δ¹³C=−11.9‰). Infrared spectra from 29 diamonds identified two diamond groups: 75% are nitrogen-free (Type II) or have fully aggregated nitrogen defects (Type IaB) with platelet degradation and low to moderate nitrogen contents (av. 330 ppm-N); 25% have lower nitrogen aggregation states and higher nitrogen contents (30% IaB; <1600 ppm-N).

The combined evidence suggests two generations of diamond growth. Type II and Type IaB diamonds with ultradeep, peridotitic, eclogitic and websteritic inclusions crystallised from eclogitic and peridotitic rocks while moving in a dynamic environment from the asthenosphere and possibly the lower mantle to the base of the lithosphere. Mechanisms for diamond movement through the mantle could be by mantle convection, or an ascending plume. The interaction of partial melts with eclogitic and peridotitic lithologies may have produced the intermediate websteritic inclusion compositions, and can explain diamonds of mixed parageneses, and the overlap in C-isotope values between parageneses. Strong deformation and extremely high nitrogen aggregation states in some diamonds may indicate high mantle storage temperatures and strain in the diamond growth environment. A second diamond group, with Type IaA–IaB nitrogen aggregation and peridotitic inclusions, crystallised at the base of the cratonic lithosphere. All diamonds were subsequently sampled by kimberlites and transported to the Earth's surface.     

Mineral inclusions and geochemical characteristics of microdiamonds from the DO27, A154, A21, A418, DO18, DD17 and Ranch Lake kimberlites at Lac de Gras, Slave Craton, Canada

A mineral inclusion, carbon isotope, nitrogen content, nitrogen aggregation state and morphological study of 576 microdiamonds from the DO27, A154, A21, A418, DO18, DD17 and Ranch Lake kimberlites at Lac de Gras, Slave Craton, was conducted. Mineral inclusion data show the diamonds are largely eclogitic (64%), followed by peridotitic (25%) and ultradeep (11%). The paragenetic abundances are similar to macrodiamonds from the DO27 kimberlite (Davies, R.M., Griffin, W.L., O'Reilly, S.Y., 1999. Diamonds from the deep: pipe DO27, Slave craton, Canada. In: Gurney, J.J., Gurney, J.L., Pascoe, M.D., Richardson, S.H. (Eds.), The J. B. Dawson Vol., Proc. 7th Internat. Kimberlite Conf., Red Roof Designs, Cape Town, pp. 148–155) but differ to diamonds from nearby kimberlites at Ekati (e.g., Lithos (2004); Tappert, R., Stachel, T., Harris, J.W., Brey, G.P., 2004. Mineral Inclusions in Diamonds from the Panda Kimberlite, S. P., Canada. 8th International Kimberlite Conference, extended abstracts) and Snap Lake to the south (Dokl. Earth Sci. 380 (7) (2001) 806), that are dominated by peridotitic stones.

Eclogitic diamonds with variable inclusion compositions and temperatures of formation (1040–1300 °C) crystallised at variable lithospheric depths sometimes in changing chemical environments. A large range to very ¹³C-depleted C-isotope compositions (δ¹³C=−35.8‰ to −2.2‰) and an NMORB bulk composition, calculated from trace elements in garnet and clinopyroxene inclusions, are consistent with an origin from subducted oceanic crust and sediments. Carbon isotopes in the peridotitic diamonds have mantle compositions (δ¹³C mode −4.0‰). Mineral inclusion compositions are largely harzburgitic. Variable temperatures of formation (garnet T_Ni=800–1300 °C) suggest the peridotitic diamonds originate from the shallow ultra-depleted and deeper less depleted layers of the central Slave lithosphere. Carbon isotopes (δ¹³C av.=−5.1‰) and mineral inclusions in the ultradeep diamonds suggest they formed in peridotitic mantle (670 km). The diamonds may have been entrained in a plume and subcreted to the base of the central Slave lithosphere.

Poorly aggregated nitrogen (IaA without platelets) in a large number of eclogitic (67%) and peridotitic (32%) diamonds, with similar nitrogen contents, indicates the diamonds were stored in the mantle at low temperatures (1060–<1100 °C) following crystallisation in the Archean. Type IaA diamonds have largely cubo-octahedral growth forms, and Type II and Type IaAB diamonds, with higher nitrogen aggregation states, mostly have octahedral morphologies. However, no correlation between these groups and their mineral inclusion compositions, C-isotopes, and N-contents rules out the possibility of unique source origins and suggests eclogitic and peridotitic diamonds experienced variable mantle thermal states. Variation in mineral inclusion chemistries in single diamonds, possible overgrowths of ¹³C-depleted eclogitic diamond on diamonds with peridotitic and ultradeep inclusions, and Type I ultradeep diamond with low N-aggregation is consistent with diamond growth over time in changing chemical environments.     

The Taihua group on the southern margin of the North China craton: further insights from U–Pb ages and Hf isotope compositions of zircons

The "Taihua Group" is a collective term for a series of old terranes scattered along the southern margin of the North China Craton. The timing of formation and thermal overprinting of the Taihua Group have long been contentious, and its relationship with the Qinling orogenic belt has been unclear. In this study, new data from integrated in-situ U–Pb dating and Hf isotope analysis of zircons from an amphibolite (from the Xiong’ershan terrane) and a biotite gneiss (from the Lantian-Xiaoqinling terrane) indicate that the Upper Taihua Group formed during the Paleoproterozoic (2.3–2.5 Ga) and thus was originally part of the southern edge of North China Craton, detached during the Mesozoic Qinling orogeny and displaced about 100 km north from its original location. This suggests that the Taihua Group became part of the tectonic terrane associated with the Qinling orogeny and now forms part of the overthrust basement section of the Qinling belt. Before the Qinling orogeny, the Taihua Group was metamorphosed at 2.1 Ga. The initial Hf-isotope compositions of zircons, together with positive εNd(t) values for the whole-rocks, imply that the original magmas were derived from a juvenile source with some assimilation of an Archean crustal component.     

A chemical and thermodynamic model of oil generation in hydrocarbon source rocks

Thermodynamic calculations and Gibbs free energy minimization computer experiments strongly support the hypothesis that kerogen maturation and oil generation are inevitable consequences of oxidation/reduction disproportionation reactions caused by prograde metamorphism of hydrocarbon source rocks with increasing depth of burial.These experiments indicate that oxygen and hydrogen are conserved in the process.Accordingly, if water is stable and present in the source rock at temperatures ?25 but ?100 °C along a typical US Gulf Coast geotherm, immature (reduced) kerogen with a given atomic hydrogen to carbon ratio (H/C) melts incongruently with increasing temperature and depth of burial to produce a metastable equilibrium phase assemblage consisting of naphthenic/biomarker-rich crude oil, a type-II/III kerogen with an atomic hydrogen/carbon ratio (H/C) of ∼1, and water. Hence, this incongruent melting process promotes diagenetic reaction of detritus in the source rock to form authigenic mineral assemblages.However, in the water-absent region of the system CHO (which is extensive), any water initially present or subsequently entering the source rock is consumed by reaction with the most mature kerogen with the lowest H/C it encounters to form CO₂ gas and a new kerogen with higher H/C and O/C, both of which are in metastable equilibrium with one another.This hydrolytic disproportionation process progressively increases both the concentration of the solute in the aqueous phase, and the oil generation potential of the source rock; i.e., the new kerogen can then produce more crude oil.Petroleum is generated with increasing temperature and depth of burial of hydrocarbon source rocks in which water is not stable in the system CHO by a series of irreversible disproportionation reactions in which kerogens with higher (H/C)s melt incongruently to produce metastable equilibrium assemblages consisting of crude oil, CO₂ gas, and a more mature (oxidized) kerogen with a lower H/C which in turn melts incongruently with further burial to produce more crude oil, CO₂ gas, and a kerogen with a lower H/C and so forth.The petroleum generated in the process progresses from heavy naphthenic crude oils at low temperatures to mature petroleum at ∼150 °C. For example, the results of Computer Experiment 27 (see below) indicate that the overall incongruent melting reaction in the water-absent region of the system C-H-O at 150 °C and a depth of ∼4.3 km of an immature type-II/III kerogen with a bulk composition represented by C₂₉₂H₂₈₈O_12(c) to produce a mature (oxidized) kerogen represented by C₁₂₈H₆₈O_7(c), together with a typical crude oil with an average metastable equilibrium composition corresponding to C_8.8H_16.9 (C_8.8H_16.9(l)) and CO₂ gas (CO_2(g)) can be described by writing

(A)     

Characterization of permineralized kerogen from an Eocene fossil fern

The processes of organic maturation that occur during the permineralization of fossils and the detailed chemistry of the resulting products are incompletely understood. Primary among such processes is the geochemical alteration of biological matter to produce kerogen, such as that which comprises the cell walls of the fossils studied here: essentially unmetamorphosed, Eocene plant axes (specimens of the fossil fern Dennstaedtiopsis aerenchymata cellularly permineralized in cherts of the Clarno Formation of Oregon and the Allenby Formation of British Columbia). The composition and molecular structure of the kerogen that comprises the cell walls of such axes were analyzed using ultraviolet Raman spectroscopy (UV–Raman), solid state ¹³C nuclear magnetic resonance spectroscopy (¹³C NMR) and pyrolysis–gas chromatography–mass spectrometry (py–GC–MS).Cellularly well-preserved fern axes from both geologic units exhibit similar overall molecular structure, being composed primarily of networks of aromatic rings and polyene chains that, unlike more mature kerogens, lack large polycyclic aromatic hydrocarbon (PAH) constituents. The cell walls of the Allenby Formation specimens are, however, less altered than those of the Clarno chert, exhibiting more prevalent oxygen-containing and alkyl functional groups and comprising a greater fraction of rock mass.The study represents the first demonstration of the effectiveness (and limitations) of the combined use of UV–Raman, ¹³C NMR and py–GC–MS for the analysis of the kerogenous cell walls of chert-permineralized vascular plants.     

Salinity stratification in a river-dominated estuary

Analysis of salinity data from Mobile Bay indicates that stratification-destratification events within this broad, shallow estuary are not uncommon. These events are related to the strength of the winds, through their influence on wave generation and subsequent bottom drag coefficient increases, and to the strength of river discharge. They do not appear to be due to the strength of tidal currents, as has been observed elsewhere. Furthermore, river flow appears to be the dominant control, the winds being important only in the absence of large freshwater discharges. The annual spring freshet can flush most of the salt from the bay. During other times of the year the relative strengths of river discharge and wind stress change the bay from highly stratified to nearly homogeneous and back on a variety of time scales ranging from daily to seasonal.     

SIMS U-Pb dating of micro-zircons in the lunar meteorites Dhofar 1528 and Dhofar 1627

About half of the lunar meteorites in our collections are feldspathic breccias. Acquiring geochronologic information from these breccias is challenging due to their low radioactive-element contents and their often polymict nature. We used high-spatial-resolution (5 μm) NanoSIMS (nanoscale secondary ion mass spectrometry) U-Pb dating technique to date micro-zircons in the lunar feldspathic meteorites Dhofar 1528 and Dhofar 1627. Three NanoSIMS dating spots of two zircon grains from Dhofar 1528 show a discordia with an upper intercept at 4354 ± 76 Ma and a lower intercept at 332 ± 1407 Ma (2σ, MSWD = 0.01, p = 0.91). Three spots of two zircon grains in Dhofar 1627 define a discordia with an upper intercept at 3948 ± 30 Ma and a lower intercept at 691 ± 831 Ma (2σ, MSWD = 0.40, p = 0.53). Both samples likely experienced shock metamorphism caused by impacts. Based on the clastic nature, lack of recrystallization and the consistent U-Pb and Pb-Pb dates of the zircons in Dhofar 1528, the U-Pb date of 4354 Ma is interpreted as the crystallization age of its Mg-suite igneous precursor. Some of the Dhofar 1627 zircons show poikilitic texture, a crystallization from the matrix impact melt, so the U-Pb date of 3948 Ma corresponds to an impact event, likely the Imbrium basin-forming event. These data are the first radiometric ages for these two meteorites and demonstrate that in situ (high spatial resolution) U-Pb dating has potential for extracting geochronological information about igneous activities and impact events from lunar feldspathic and polymict breccias.