Isotopic order, biogeochemical processes, and earth history: Goldschmidt lecture, Davos, Switzerland, August 2002

The impetus to interpret carbon isotopic signals comes from an understanding of isotopic fractionations imposed by living organisms. That understanding rests in turn on studies of enzymatic isotope effects, on fruitful concepts of isotopic order, and on studies of the distribution of ¹³C both between and within biosynthetic products. In sum, these studies have shown that the isotopic compositions of biological products are governed by reaction kinetics and by pathways of carbon flow.Isotopic compositions of individual compounds can indicate specific processes or environments. Examples include biomarkers which record the isotopic compositions of primary products in aquatic communities, which indicate that certain bacteria have used methane as a carbon source, and which show that some portions of marine photic zones have been anaerobic. In such studies, the combination of structural and isotopic lines of evidence reveals relationships between compounds and leads to process-related thinking. These are large steps. Reconstruction of the sources and histories of molecular fossils redeems much of the early promise of organic geochemistry by resolving and clarifying paleoenviron-mental signals. In turn, contemplation of this new information is driving geochemists to study microbial ecology and evolution, oceanography, and sedimentology.     

Initial Al/Al in carbonaceous-chondrite chondrules: too little Al to melt asteroids

We report ²⁶Mg excesses correlated with Al/Mg ratios in five chondrules from the primitive CO3.0 chondrite Yamato 81020 that yield a mean initial ²⁶Al/²⁷Al ratio of only (3.8 ± 0.7) × 10⁻⁶, about half that of ordinary chondrite (OC) chondrules. Even if asteroids formed immediately after chondrule formation, this ratio and the mean Al content of CO chondrites is only capable of raising the temperature of a well-insulated CO asteroid to 940 K, which is more than 560 K too low to produce differentiation. The same ratio combined with the higher Al content of CV chondrites results in a CV asteroid temperature of 1100 K. We calculate that the mean initial ²⁶Al/²⁷Al ratio of about 7.4 × 10⁻⁶ found in LL chondrules is only able to produce small amounts of melting, too little to produce differentiation. These results cast serious doubt on the viability of ²⁶Al as the heat source responsible for asteroid differentiation. Inclusion of ⁶⁰Fe raises temperatures about 160 K, but this increment is not enough to cause differentiation, even of an LL-chondrite asteroid.     

Organic matter in small mesopores in sediments and soils

The three-way correlation among organic matter concentrations, specific surface area and small mesopores observed for many soils and sediments led to the hypothesis that enclosure within the pores might explain the apparent protection of organic matter by minerals. We test this hypothesis by examining whether the bulk of organic matter resides within small mesopores. Pore volumes as a function of pore width were measured before and after organic matter removal, and the volume differences ascribed to organic matter filling of pores. Minor changes in small mesopore size distributions upon treatments such as centrifugation and muffling indicate the robustness of the mineral matrices that form these pores. We developed an additional method to assess organic matter densities using high-resolution pycnometry, and used these densities to convert pore volumes to organic matter contents. Although smaller mesopores are shown to have sufficient volumes to contain significant fractions of the total organic matter, only small fractions of total organic matter were found to reside in them. These results are consistent with preferential association between organic matter and aluminous clay particle edges, rather than the largely siliceous clay faces that contribute most surface area and form pore walls. While simple enclosure within smaller mesopores cannot, therefore, explain protection, network effects working at larger size scales may account for exclusion of digestive agents and hence organic matter protection.     

Trapped Xe and I-Xe ages in aqueously altered CV3 meteorites

Twenty-two dark inclusions (DIs) from Allende (18), Leoville (2), Vigarano (1) and Efremovka (1) were studied by the I-Xe method. All except two of these DIs (Vigarano 2226 and Leoville LV2) produce well-defined isochrons, and precise I-Xe ages. The Allende DIs formed a tight group about 1.6 Ma older than Shallowater (4.566 ± 0.002 Ga), about 5 Ma older than four previously studied Allende CAIs. Most of the dark inclusions require trapped Xe with less ¹²⁹Xe (or more ¹²⁸Xe) than conventional planetary Xe (well restricted in composition by Q-Xe or OC-Xe). Studies of an irradiated/unirradiated DI pair from Allende demonstrate that the ¹²⁸Xe/¹³²Xe ratio in trapped is normal planetary, so that a ¹²⁹Xe/¹³²Xe ratio below planetary seems to be required. Yet, this is not possible given constraints on ¹²⁹Xe evolution in the early solar system. Trends among all of the Allende DIs suggest that an intimate mixture of partially decayed iodine and Xe formed a pseudo trapped Xe component enriched in both ¹²⁹Xe and ¹²⁷I, and subsequently in ¹²⁸Xe after n-capture during reactor irradiation. Enrichment in radiogenic ¹²⁹Xe, but with a ¹²⁹Xe/¹²⁷I ratio less than that observed in the iodine host phase, places closure of this trapped mixture ≥13 Ma after precipitation of the major iodine-bearing phase. Because the I-Xe isochron is a mixing line between iodine-derived and trapped Xe (pseudo or not), I-Xe ages, given by the slope of this mixing line, are not compromised by the presence of pseudo trapped Xe, and the precision of the I-Xe ages is given by the statistics of the line fit.     

The neoliberalization of ecosystem services: wetland mitigation banking and problems in environmental governance

Wetland mitigation banking is an American neoliberal environmental policy that has created a functioning market in `ecosystem services', commodities defined using the holistic measures of ecological science. The development of this market is discussed as a project of environmental governance, defined as the nation-state's regulation of ecological relations within its territory towards stabilizing capitalist relations of power and accumulation. I argue that the wetland banking industry serves as a bellwether that presages problems that other strategies of neoliberal environmental governance will experience. Ethnographic, economic and ecological data from the Chicago-area wetland banking industry inform a discussion of two major obstacles to neoliberal strategy: the problem of relying on ecological science to define the unit of trade, and the problem of aligning the somewhat independent relations of law, politics, markets and ecosystems across an array of spatial scales. Theoretical guidance is sought from recent work on `social natures' and from the Regulationist approach to institutional political economics.     

The effect of the ionization rate on the chemical composition of dense cores of dark molecular clouds

The effect of variations in the rate of ionization of neutral chemical species by cosmic rays, ζ, on the abundances of some observed molecules in the dense cores of dark molecular clouds is studied. Changes in molecular abundances accompanying an increased (decreased) ionization rate have a single origin: the acceleration (deceleration) of processes that are affected directly or indirectlybychemical reactions with charged species. In addition to affecting the gas-phase chemistry, an increased cosmic-ray flux leads to the more efficient destruction of dust-grain mantles and also accelerates the freezing of some components onto dust. In particular, in a model with an increased ζ, the destruction of the volatile N₂ molecule by ionized helium leads to the rapid accumulation of nitrogen atoms in dust-phase ammonia, which has a higher desorption energythan N₂. As a result, the gas-phase abundance of NH₃ and N₂H⁺ decreases significantly. This mechanism can explain the unusual chemical structures of some dense globules, such as B68, where surprisingly low abundances of nitrogen-bearing molecules are observed together with a central drop in the NH₃ and N₂H⁺ column densities. Observations of clouds in HCN and HNC lines can discriminate between the two possible origins of the reduced NH3 and N₂H⁺ abundances: an increased cosmic-ray flux or N₂ freezing due to the higher desorption energy of this molecule.     

Observed features of a two-phase stellar wind from WR 136 in the vicinity of NGC 6888

A number of features are detected outside the nebula NGC 6888, within 1.2° (30 pc) of the star WR 136, which can be explained in a two-phase stellar-wind model. These include regions with fine filamentary gas structure that do not contain sources of stellar wind, extended radial “streams,” ultra-compact HII regions with high-velocity gas motions, and high-velocity gas motions outside the envelope of NGC 6888. The two-phase wind consists of a rarefied component and dense compact condensations, or “bullets.” The bullets generate cylindrical shocks in the interstellar gas, resulting in the presence of high-velocity gas up 20–30 pc from the star, outside the cavity formed by the rarified component of the wind.     

Massive close binary stars and gamma-ray bursts

We analyze the observed parameters of massive extremely close binaries containing Wolf-Rayet stars and black holes, and identify those systems whose supernova outbursts lead to the formation of rapidly rotating Kerr black holes. It is proposed that the formation of such a black hole is accompanied by a strong gamma-ray burst. Several types of observed systems satisfy the conditions necessary for the formation of a Kerr black hole: BH+WR, BH+OB, WR+O, and BH+K,M.     

Analysis of a high-amplitude event in component A of the gravitational lens QSO 2237+0305

We present an analysis of a high-amplitude event in the flux curve of component A of the gravitational lens QSO 2237+0305 observed by the OGLE and GLITP groups in autumn 1999. Hypothesizing this event to be associated with microlensing of a fold caustic, we analyzed the observational data using a method for the successive reconstruction of branches of the one-dimensional strip brightness distribution across the source corresponding to positive and negative arguments. The search for the branches was carried out on compact sets of nonnegative, monotonically nonincreasing, convex downward functions. The resulting shape of the strip brightness distribution for the accretion disk of the quasar is in agreement with results obtained earlier via model fitting. Features in the lensing curve that could be associated with curvature of the caustic, nearness of a cusp, or the influence of nearby caustics are noted.     

Mantle Xenoliths from the Southeastern Slave Craton: Evidence for Chemical Zonation in a Thick, Cold Lithosphere

We present the first data on the petrology of the mantle lithosphereof the Southeastern (SE) Slave craton, Canada. These are basedon petrographic, mineralogical and geochemical studies of mantlexenoliths in Pipe 5034 of the Cambrian Gahcho Kué kimberlitecluster. Major types of mantle xenoliths include altered eclogite,coarse garnet or spinel peridotite, and deformed garnet peridotite.The peridotites belong to the low-temperature suite and formedat T=600–1300°C and P= 25–80 kbar in a thick(at least 220–250 km), cool lithosphere. The SE Slavemantle is cooler than the mantle of other Archaean cratons andthat below other terranes of the Slave craton. The thick lithosphereand the relatively cool thermal regime provide favourable conditionsfor formation and preservation of diamonds beneath the SE Slaveterrane. Similar to average Archaean mantle worldwide, the SESlave peridotite is depleted in magmaphile major elements andcontains olivine with forsterite content of 91–93·5.With respect to olivine composition and mode, all terranes ofthe Slave mantle show broadly similar compositions and are relativelyorthopyroxene-poor compared with those of the Kaapvaal and Siberiancratons. The SE Slave spinel peridotite is poorer in Al, Caand Fe, and richer in Mg than deeper garnet peridotite. Thegreater chemical depletion of the shallow upper mantle is typicalof all terranes of the Slave craton and may be common for thesubcontinental lithospheric peridotitic mantle in general. Peridotiticxenoliths of the SE Slave craton were impregnated by kimberliticfluids that caused late-stage recrystallization of primary clinopyroxene,spinel, olivine and spinel-facies orthopyroxene, and formationof interstitial clinopyroxene. This kimberlite-related recrystallizationdepleted primary pyroxenes and spinel in Al. The kimberliticfluid was oxidizing, Ti-, Fe- and K-rich, and Na-poor, and introducedserpentine, chlorite, phlogopite and spinel into peridotitesat P < 35 kbar. KEY WORDS: kimberlite xenolith; lithosphere; mantle terrane; chemical zoning; thermobarometry; Slave craton