Ion microprobe analysis of oxygen isotope ratios in granulite facies magnetites: diffusive exchange as a guide to cooling history

Ion microprobe analysis of magnetites from the Adirondack Mountains, NY, yields oxygen isotope ratios with spatial resolution of 2–8 m and precision in the range of 1 (1 sigma). These analyses represent 11 orders of magnitude reduction in sample size compared to conventional analyses on this material and they are the first report of routinely reproducible precision in the 1 per mil range for analysis of ¹⁸O at this scale. High precision micro-analyses of this sort will permit wide-ranging new applications in stable isotope geochemistry. The analyzed magnetites form nearly spherical grains in a calcite matrix with diopside and monticellite. Textures are characteristic of granulite facies marbles and show no evidence for retrograde recrystallization of magnetite. Magnetites are near to Fe₃O₄ in composition, and optically and chemically homogeneous. A combination of ion probe plus conventional BrF₅ analysis shows that individual grains are homogeneous with ¹⁸O=8.9±1 SMOW from the core to near the rim of 0.1–1.2 mm diameter grains. Depth profiling into crystal growth faces of magnetites shows that rims are 9 depleted in ¹⁸O. These low ¹⁸O values increase in smooth gradients across the outer 10 m of magnetite rims in contact with calcite. These are the sharpest intracrystalline gradients measured to date in geological materials. This discovery is confirmed by bulk analysis of 150–350 m diameter magnetites which average 1.2 lower in ¹⁸O than coarse magnetites due to low ¹⁸O rims. Conventional analysis of coexisting calcite yields °¹⁸O=18.19, suggesting that bulk ¹⁸O (Cc-Mt)=9.3 and yielding an apparent equilibration temperature of 525° C, over 200° C below the temperature of regional metamorphism. Consideration of experimental diffusion data and grain size distribution for magnetite and calcite suggests two contrasting cooling histories. The data for oxygen in calcite under hydrothermal conditions at high P(H₂O) indicates that diffusion is faster in magnetite and modelling of the low ¹⁸O rims on magnetite would suggest that the Adirondacks experienced slow cooling after Grenville metamorphism, followed by a brief period of rapid cooling, possibly related to uplift. Conversely, the data for calcite at low P(H₂O) show slower oxygen diffusion than in magnetite. Modelling based on these data is consistent with geochronology that shows slow cooling through the blocking temperature of both minerals, suggesting that the low ¹⁸O rims form by exchange with late, low temperature fluids similar to those that infiltrated the rock to serpentinize monticellite and which infiltrated adjacent anorthosite to form late calcite veinlets. In either case, the ion microprobe results indicate that two distinct events are recorded in the post-metamorphic exchange history of these magnetites. Recognition of these events is only possible through microanalysis and has important implications for geothermometry.     

The demographic responses to famine: The case of China 1958–61

Pre-1949 China was The Sick Man of Asia, The Land of Famine. In 1949 Mao brought the communists to power and in the re-ordered world, all such problems were supposedly overcome — but not so. Thirty years ago China suffered one of the world's worst famines. Over the four years 1958–61, China suffered some 25–30 million more deaths and experienced some 30–35 million fewer births than might have been expected under normal conditions. Yet for almost a quarter of a century there would be few, outside of China, who were aware of the existence let alone the dimensions of the disaster. Access to Chinese census data since the mid-1980s has permitted a preliminary analysis of the demographic impact of the famine.Abbreviations JPRS-CEA-81-128 Joint Publications Research Service, China Economic Affairs Report 128, 1981 - JPRS-CPS-85-028 Joint Publications Research Service. China Report, Political, Sociological & Military Affairs 28, 1985     

Archean high-Mg monzodiorite–syenite,epidote skarn,and biotite–sericite gold lodes in the Granny Smith–Wallaby district,Australia: U–Pb and Re–Os chronometry of two intrusion-related hydrothermal systems

The Granny Smith (37 t Au production) and Wallaby deposits (38 t out of a 180 t Au resource) are located northeast of Kalgoorlie, in 2.7 Ga greenstones of the Eastern Goldfields Province, the youngest orogenic belt of the Yilgarn craton, Western Australia. At Granny Smith, a zoned monzodiorite–granodiorite stock, dated by a concordant titanite–zircon U–Pb age of 2,665 ± 3 Ma, cuts across east-dipping thrust faults. The stock is fractured but not displaced and sets a minimum age for large-scale (1 km) thrust faulting (D2), regional folding (D1), and dynamothermal metamorphism in the mining district. The local gold–pyrite mineralization, controlled by fractured fault zones, is younger than 2,665 ± 3 Ma. In augite–hornblende monzodiorite, alteration progressed from a hematite-stained alkali feldspar–quartz–calcite assemblage and quartz–molybdenite–pyrite veins to a late reduced sericite–dolomite–albite assemblage. Gold-related monazite and xenotime define a U–Pb age of 2,660 ± 5 Ma, and molybdenite from veins a Re–Os isochron age of 2,661 ± 6 Ma, indicating that mineralization took place shortly after the emplacement of the main stock, perhaps coincident with the intrusion of late alkali granite dikes. At Wallaby, a NE-trending swarm of porphyry dikes comprising augite monzonite, monzodiorite, and minor kersantite intrudes folded and thrust-faulted molasse. The conglomerate and the dikes are overprinted by barren (<0.01 g/t Au) anhydrite-bearing epidote–actinolite–calcite skarn, forming a 600-m-wide and >1,600-m-long replacement pipe, which is intruded by a younger ring dike of syenite porphyry pervasively altered to muscovite + calcite + pyrite. Skarn and syenite are cut by pink biotite–calcite veins, containing magnetite + pyrite and subeconomic gold–silver mineralization (Au/Ag = 0.2). The veins are associated with red biotite–sericite–calcite–albite alteration in adjacent monzonite dikes. Structural relations and the concordant titanite U–Pb age of the skarn constrain intrusion-related mineralization to 2,662 ± 3 Ma. The main-stage gold–pyrite ore (Au/Ag >10) forms hematite-stained sericite–dolomite–albite lodes in stacked D2 reverse faults, which offset skarn, syenite, and the biotite–calcite veins by up to 25 m. The molybdenite Re–Os age (2,661 ± 10 Ma) of the ore suggests a genetic link to intrusive activity but is in apparent conflict with a monazite–xenotime U–Pb age (2,651 ± 6 Ma), which differs from that of the skarn at the 95% confidence level. The time relationships at both gold deposits are inconsistent with orogenic models invoking a principal role for metamorphic fluids released during the main phase of compression in the fold belt. Instead, mineralization is related in space and time to late-orogenic, magnetite-series, high-Mg monzodiorite–syenite intrusions of mantle origin, characterized by Mg/(Mg + Fe_TOTAL) = 0.31–0.57, high Cr (34–96 ppm), Ni (22–63 ppm), Ba (1,056–2,321 ppm), Sr (1,268–2,457 ppm), Th (15–36 ppm), and rare earth elements (total REE: 343–523 ppm). At Wallaby, shared Ca–K–CO₂ metasomatism and Th-REE enrichment (in allanite) link Au–Ag mineralization in biotite–calcite veins to the formation of the giant epidote skarn, implicating a Th + REE-rich syenite pluton at depth as the source of the oxidized hydrothermal fluid. At Granny Smith, lead isotope data and the Rb–Th–U signature of early hematite-bearing wall-rock alteration point to fluid released by the source pluton of the differentiated alkali granite dikes.     

Detailed <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar dating of geologic events associated with the Mantos Blancos copper deposit,northern Chile

The ⁴⁰Ar/³⁹Ar geochronological method was applied to date magmatic and hydrothermal alteration events in the Mantos Blancos mining district in the Coastal Cordillera of northern Chile, allowing the distinction of two separate mineralization events. The Late Jurassic Mantos Blancos orebody, hosted in Jurassic volcanic rocks, is a magmatic-hydrothermal breccia-style Cu deposit. Two superimposed mineralization events have been recently proposed. The first event is accompanied by a phyllic hydrothermal alteration affecting a rhyolitic dome. The second mineralization event is related to the intrusion of bimodal stocks and sills inside the deposit. Because of the superposition of several magmatic and hydrothermal events, the obtained ⁴⁰Ar/³⁹Ar age data are complex; however, with a careful interpretation of the age spectra, it is possible to detect complex histories of successive emplacement, alteration, mineralization, and thermal resetting. The extrusion of Jurassic basic to intermediate volcanic rocks of the La Negra Formation is dated at 156.3 ± 1.4 Ma (2σ) using plagioclase from an andesitic lava flow. The first mineralization event and associated phyllic alteration affecting the rhyolitic dome occurred around 155–156 Ma. A younger bimodal intrusive event, supposed to be equivalent to the bimodal stock and sill system inside the deposit, is probably responsible for the second mineralization event dated at ca. 142 Ma. Other low-temperature alteration events have been dated on sericitized plagioclase at ca. 145–146, 125, and 101 Ma. This is the first time that two distinct mineralization events have been documented from radiometric data for a copper deposit in the metallogenic belt of the Coastal Cordillera of northern Chile. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Relationship between footwall composition,crustal contamination,and fluid–rock interaction in the Platreef,Bushveld Complex,South Africa

In the northern limb of the 2.06-Ga Bushveld Complex, the Platreef is a platinum group elements (PGE)-, Cu-, and Ni-mineralized zone of pyroxenite that developed at the intrusion margin. From north to south, the footwall rocks of the Platreef change from Archaean granite to dolomite, hornfels, and quartzite. Where the footwall is granite, the Sr-isotope system is more strongly perturbed than where the footwall is Sr-poor dolomite, in which samples show an approximate isochron relationship. The Nd-isotope system for samples of pyroxenite and hanging wall norite shows an approximate isochron relationship with an implied age of 2.17 ± 0.2 Ga and initial Nd-isotope ratio of 0.5095. Assuming an age of 2.06 Ga, the ɛNd values range from −6.2 to −9.6 (ave. −7.8, n = 17) and on average are slightly more negative than the Main Zone of the Bushveld. These data are consistent with local contamination of an already contaminated magma of Main Zone composition. The similarity in isotope composition between the Platreef pyroxenites and the hanging wall norites suggests a common origin. Where the country rock is dolomite, the Platreef has generally higher plagioclase and pyroxene δ ¹⁸O values, and this indicates assimilation of the immediate footwall. Throughout the Platreef, there is considerable petrographic evidence for sub-solidus interaction with fluids, and the Δ _{plagioclase–pyroxene} values range from −2 to +6, which indicates interaction at both high and low temperatures. Whole-rock and mineral δD values suggest that the Platreef interacted with both magmatic and meteoric water, and the lack of disturbance to the Sr-isotope system suggests that fluid–rock interaction took place soon after emplacement. Where the footwall is granite, less negative δD values suggest a greater involvement of meteoric water. Consistently higher values of Δ _{plagioclase–pyroxene} in the Platreef pyroxenites and hanging wall norites in contact with dolomite suggest prolonged interaction with CO₂-rich fluid derived from decarbonation of the footwall rocks. The overprint of post crystallization fluid–rock interaction is the probable cause of the previously documented lack of correlation between PGE and sulfide content on the small scale. The Platreef in contact with dolomite is the focus of the highest PGE grades, and this suggests that dolomite contamination played a role in PGE concentration and deposition, but the exact link remains obscure. It is a possibility that the CO₂ produced by decarbonation of assimilated dolomite enhanced the process of PGE scavenging by sulfide precipitation.     

The Mordor Alkaline Igneous Complex,Central Australia: PGE-enriched disseminated sulfide layers in cumulates from a lamprophyric magma

The Mordor Alkaline Igneous Complex (MAIC) is a composite intrusion comprising a body of syenite and a funnel-shaped layered mafic–ultramafic intrusion of lamprophyric parentage, the Mordor Mafic–Ultramafic Intrusion or MMUI. The MMUI is highly unusual among intrusions of lamprophyric or potassic parentage in containing primary magmatic platinum-group element (PGE)-enriched sulfides. The MMUI sequence consists largely of phlogopite-rich pyroxenitic cumulates, with an inward dipping conformable layer of olivine-bearing cumulates divisible into a number of cyclic units. Stratiform-disseminated sulfide accumulations are of two types: disseminated layers at the base of cyclic units, with relatively high PGE tenors; and patchy PGE-poor disseminations within magnetite-bearing upper parts of cyclic units. Sulfide-enriched layers at cycle bases contain anomalous platinum group element contents with grades up to 1.5 g/t Pt+Pd+Au over 1-m intervals, returning to background values of low parts per billion (ppb) on a meter scale. They correspond to reversals in normal fractionation trends and are interpreted as the result of new magma influxes into a continuously replenished magma chamber. Basal layers have decoupled Cu and PGE peaks reflecting increasing PGE tenors up-section, due to increasing R factors during the replenishment episode, or progressive mixing of between resident PGE-poor magma and more PGE-enriched replenishing magma. The presence of PGE enriched sulfides in cumulates from a lamprophyric magma implies that low-degree partial melts do not necessarily leave sulfides and PGEs in the mantle restite during partial melting. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Fluid and source magma evolution of the Questa porphyry Mo deposit,New Mexico,USA

Combined fluid inclusion microthermometry and microanalysis by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) are used to constrain the hydrothermal processes forming a typical Climax-type porphyry Mo deposit. Molybdenum mineralisation at Questa occurred in two superimposed hydrothermal stages, a magmatic-hydrothermal breccia and later stockwork veining. In both stages, texturally earliest fluids were single-phase, of low salinity (~7 wt.% NaCl_equiv.) and intermediate-density. Upon decompression to ~300 bar, they boiled off a vapour phase, leaving behind a residual brine (up to 45 wt.% NaCl_equiv) at temperatures of ~420°C. The highest average Mo concentrations in this hot brine were ~500 μg/g, exceeding the Mo content of the intermediate-density input fluid by about an order of magnitude and reflecting pre-concentration of Mo by fluid phase separation prior to MoS₂ deposition from the brine. Molybdenum concentrations in brine inclusions, then, decrease down to 5 μg/g, recording Mo precipitation in response to cooling of the saline liquid to ~360°C. Molybdenite precipitation from a dense, residual and probably sulphide-depleted brine is proposed to explain the tabular shape of the ore body and the absence of Cu-Fe sulphides in contrast to the more common Cu-Mo deposits related to porphyry stocks. Cesium and Rb concentrations in the single-phase fluids of the breccia range from 2 to 8 and from 40 to 65 μg/g, respectively. In the stockwork veins, Cs and Rb concentrations are significantly higher (45–90 and 110–230 μg/g, respectively). Because Cs and Rb are incompatible and hydrothermally non-reactive elements, the systematic increase in their concentration requires two distinct pulses of fluid exsolution from a progressively more fractionated magma. By contrast, major element and ore metal concentrations of these two fluid pulses remain essentially constant. Mass balance calculations using fluid chemical data from LA-ICPMS suggest that at least 25 km³ of melt and 7 Gt of deep input fluid were necessary to provide the amount of Mo contained in the stockwork vein stage alone. While the absolute amounts of fluid and melt are uncertain, the well-constrained element ratios in the fluids together with empirical fluid/melt partition coefficients derived from the inclusion analyses suggest a high water content of the source melt of ~10%. In line with other circumstantial evidence, these results suggest that initial fluid exsolution may have occurred at a confining pressure exceeding 5 kbar. The source of the molybdenum-mineralising fluids probably was a particularly large magma chamber that crystallised and fractionated in the lower crust or at mid-crustal level, well below the shallow intrusions immediately underlying Questa and other porphyry molybdenum deposits. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Late Carboniferous porphyry copper mineralization at La Voluntad,Neuquén,Argentina: Constraints from Re–Os molybdenite dating

The La Voluntad porphyry Cu–Mo deposit in Neuquén, Argentina, is one of several poorly known porphyry-type deposits of Paleozoic to Early Jurassic age in the central and southern Andes. Mineralization at La Voluntad is related to a tonalite porphyry from the Chachil Plutonic Complex that intruded metasedimentary units of the Piedra Santa Complex. Five new Re–Os molybdenite ages from four samples representing three different vein types (i.e., quartz–molybdenite, quartz–sericite–molybdenite and quartz–sericite–molybdenite ± chalcopyrite–pyrite) are identical within error and were formed between ~312 to ~316 Ma. Rhenium and Os concentrations range between 34 to 183 ppm and 112 to 599 ppb, respectively. The new Re–Os ages indicate that the main mineralization event at La Voluntad, associated to sericitic alteration, was emplaced during a time span of 1.7 ± 3.2 Ma and that the deposit is Carboniferous in age, not Permian as previously thought. La Voluntad is the oldest porphyry copper deposit so far recognized in the Andes and indicates the presence of an active magmatic arc, with associated porphyry style mineralization, at the proto-Pacific margin of Gondwana during the Early Pennsylvanian.     

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.     

The bituminous mixtures of Tall-e Abu Chizan: A Vth millennium BC settlement in southwestern Iran

Various bituminous artifacts were excavated from the Tall-e Abu Chizan, a late prehistoric (Middle Susiana to Middle Uruk) settlement on the middle of the Curvy plain, between the Karun River and the Ram Hormoz Plain. All samples dated from the Vth millennium BC and cover three periods: 5000–4700 BC (Late Middle Susiana), 4700–4200 BC (Late Susiana 1) and 4200–3900 BC (Late Susiana 2). The bitumens were studied using the techniques of petroleum geochemistry and were compared both to the unaltered crude oils produced from the main oil fields in the area and to the famous Mamatain oil seeps. All samples are very rich in bitumen (average 46 wt%) which has been biodegraded and oxidized. Despite these alteration phenomena, δ¹³C of asphaltenes occur within a narrow range of less than 1‰ PDB. Biodegradation affected the steranes, terpanes, dibenzothiophenes and mono- and triaromatic steroids. Molecular characteristics of terpanes, especially the occurrence of 18α (H)-oleanane, suggest that the bitumen from Tall-e Abu Chizan is a mixture generated from Cretaceous Kazdhumi and Eocene Pabdeh petroleum source rocks. In that respect, bitumens from Tall-e Abu Chizan belong to the same oil family as oil from the Naft Safid field, which is in the vicinity of the archaeological site. In fact, the bitumen at Tall-e Abu Chizan likely originated from oil seepages at Naft Safid. These oil seeps have not yet been sampled or analysed.