Racemization of amino acids in marine sediments determined by gas chromatography

Ratios of d- to l-amino acids in acid hydrolysates from foraminifera of two deep-sea cores from the Caribbean Sea and Atlantic Ocean increase with depth and consequently with age over a span from 40,000 to 2,000,000 yr. The changing ratios do not seem to follow first-order reversible rate laws. Valine, leucine and glutamic acid apparently racemize (isoleucine epimerizes) at slower rates than do phenylalanine, alanine, aspartic acid and proline. The general relative order for rates of racemization of total (free and bound) amino acids may depend on the electron-withdrawing capacity of the R substituents of the amino acids and on the rates with which the amino acids are naturally hydrolyzed. In contrast to the total amino acids, the free amino acids in these samples are more extensively racemized, probably as a result of various catalytic and hydrolytic reactions.Previous related work based on ion-exchange chromatography has considered only ratios of alloisoleucine to isoleucine. With the gas chromatographic method used here, d/l ratios of all common asymmetric amino acids can be estimated. Measurement of the extent of racemization of amino acids in marine sediments seems to provide the basis for a geochronological tool covering the last few million years.     

The suburbanisation of poverty in British cities, 2004-16: extent,processes and nature

This paper tracks changes in relative centralisation and relative concentration of poverty for the 25 largest British cities, analysing change for poor and non-poor groups separately, and examining parallel changes in spatial segregation. The paper confirms that poverty is suburbanising, at least in the larger cities, although poverty remains over-represented in inner locations. Suburbanisation is occurring through both the reduction in low income populations in inner locations and the growth non-poor groups in these places, consistent with a process of displacement. Relative centralisation of poverty has fallen more stronglythan relative concentration of poverty, as the outward shift of poorer groups leaves them still living in denser neighbourhoods on average. The paper also shows that spatial segregation (unevenness) declined at the same time although it remains to be seen whether this indicates a long-term shift to less segregated urban forms or a transitional outcome before new forms of segregation emerge around suburban poverty concentrations.     

Chemical compositions and classifica tion of five thermally altered carbonaceous chondrites

To establish the chemical group provenance of the five thermally altered carbonaceous chondrites Asuka (A‐) 881551, Asuka‐882113, Elephant Moraine (EET) 96026, Mulga (west), and Northwest Africa (NWA) 3133, we quantified 44 trace elements in each of them. We also analyzed Larkman Nunatak (LAR) 04318 (CK4), Miller Range (MIL) 090001 (CR2), Roberts Massif (RBT) 03522 (CK5) as reference samples as their chemical group affinity is already recognized. We conclude that Asuka‐881551, Asuka‐882113, and Mulga (west) are thermally metamorphosed CK chondrites. Compositionally, Elephant Moraine 96026 most resembles the CV chondrites. NWA 3133 is the most significantly thermally altered carbonaceous chondrite in our suite of samples. It is completely recrystallized (no chondrules or matrix remain), but its bulk composition is consistent with a CV–CK clan provenance. The thermally labile element (e.g., Se, Te, Zn, and Bi) depletion in NWA 3133 indicates a chemically open system during the heating episode. It remains unclear if the heat necessary for its thermal alteration of NWA 3133 was due to the decay of ²⁶Al or was impact related. Finally, we infer that MIL 090001, Mulga (west), and NWA 3133 show occasional compositional signatures indicative of terrestrial alteration. The alteration is especially evident within the elements Sr, Ba, La, Ce, Th, U, and possibly Sb. Despite the alteration, we can still confidently place each of the altered chondrites within an established chemical group or clan.     

Ancient porosity preserved in ordinary chondrites: Examining shock and compaction on young asteroids

We use a combination of 2D and 3D petrographic examination and ⁴⁰Ar‐³⁹Ar analyses to examine the impact histories of a suite of seven ordinary chondrites (Baszkówka, Miller, NWA 2380, Mount Tazerzait, Sahara 98034, Tjerebon, and MIL 99301) that partially preserve their ancient, but postaccretionary, porosity ranging from 10 to 20%. We examine whether materials that seem to be only mildly processed (as their large intergranular pore spaces suggest) may have more complex shock histories. The ages determined for most of the seven OCs studied here indicate closure of the ⁴⁰Ar‐³⁹Ar system after primary accretion, but during (Baszkówka) or shortly after (others) thermal metamorphism, with little subsequent heating. Exceptions include Sahara 98034 and MIL 99301, which were heated to some degree at later stages, but retain some evidence for the timing of thermal metamorphism in the ⁴⁰Ar‐³⁹Ar system. Although each of these chondrites has olivine grains with sharp optical extinction (signaling an apparent shock stage of S1), normally indicative of an extremely mild impact history, all of the samples contain relict shock indicators. Given the high porosity and relatively low degree of compaction coupled with signs of shock and thermal annealing, it seems plausible that impacts into materials that were already hot may have produced the relict shock indicators. Initial heating could have resulted from prior collisions, the decay of ²⁶Al, or both processes.     

Morphology of craters generated by hypervelocity impacts of micron‐sized polypyrrole‐coated olivine particles

To understand the process of cosmic dust particle impacts and translate crater morphology on smoothed metallic surfaces to dust properties, correct calibration of the experimental impact data is needed. This article presents the results of studies of crater morphology generated by impacts using micron‐sized polypyrrole (PPy)‐coated olivine particles. The particles were accelerated by an electrostatic dust accelerator to high speeds before they impacted onto polished aluminum targets. The projectile diameter and velocity ranges were 0.3–1.2 μm and 3–7 km s^?1. After impact, stereopair images of the craters were taken using scanning electron microscope and 3‐D reconstructions made to provide diameter and depth measurements. In this study, not just the dimensions of crater diameters and depths, but also the shape and dimensions of crater lips were analyzed. The craters created by the coated olivine projectiles are shown to have complicated shapes believed to be due to the nonspherical shape of the projectiles.     

Metal phases in ordinary chondrites: Magnetic hysteresis properties and implications for thermal history

Magnetic properties are sensitive proxies to characterize FeNi metal phases in meteorites. We present a data set of magnetic hysteresis properties of 91 ordinary chondrite falls. We show that hysteresis properties are distinctive of individual meteorites while homogeneous among meteorite subsamples. Except for the most primitive chondrites, these properties can be explained by a mixture of multidomain kamacite that dominates the induced magnetism and tetrataenite (both in the cloudy zone as single‐domain grains, and as larger multidomain grains in plessite and in the rim of zoned taenite) dominates the remanent magnetism, in agreement with previous microscopic magnetic observations. The bulk metal contents derived from magnetic measurements are in agreement with those estimated previously from chemical analyses. We evidence a decreasing metal content with increasing petrologic type in ordinary chondrites, compatible with oxidation of metal during thermal metamorphism. Types 5 and 6 ordinary chondrites have higher tetrataenite content than type 4 chondrites. This is compatible with lower cooling rates in the 650–450 °C interval for higher petrographic types (consistent with an onion‐shell model), but is more likely the result of the oxidation of ordinary chondrites with increasing metamorphism. In equilibrated chondrites, shock‐related transient heating events above approximately 500 °C result in the disordering of tetrataenite and associated drastic change in magnetic properties. As a good indicator of the amount of tetrataenite, hysteresis properties are a very sensitive proxy of the thermal history of ordinary chondrites, revealing low cooling rates during thermal metamorphism and high cooling rates (e.g., following shock reheating or excavation after thermal metamorphism). Our data strengthen the view that the poor magnetic recording properties of multidomain kamacite and the secondary origin of tetrataenite make equilibrated ordinary chondrites challenging targets for paleomagnetic study.     

US presidents and the failure to ratify multilateral environmental agreements

Whereas the US President signed the Kyoto Protocol, the failure of the US Congress to ratify it seriously hampered subsequent international climate cooperation. This recent US trend, of signing environmental treaties but failing to ratify them, could thwart attempts to come to a future climate agreement. Two complementary explanations of this trend are proposed. First, the political system of the US has distinct institutional features that make it difficult for presidents to predict whether the Senate will give its advice and consent to multilateral environmental agreements (MEAs) and whether Congress will pass the required enabling legislation. Second, elected for a fixed term, US presidents might benefit politically from supporting MEAs even when knowing that legislative support is not forthcoming. Four policy implications are explored, concerning the scope for unilateral presidential action, the potential for bipartisan congressional support, the effectiveness of a treaty without the US, and the prospects for a deep, new climate treaty.

Policy relevance

Why does the failure of US ratification of multilateral environmental treaties occur? This article analyses the domestic political mechanisms involved in cases of failed US ratification. US non-participation in global environmental institutions often has serious ramifications. For example, it sharply limited Kyoto's effectiveness and seriously hampered international climate negotiations for years. Although at COP 17 in Durban the parties agreed to negotiate a new agreement by 2015, a new global climate treaty may well trigger a situation resembling the one President Clinton faced in 1997 when he signed Kyoto but never obtained support for it in the Senate. US failure to ratify could thwart future climate agreements.     

Oxygen fugacity control in piston-cylinder experiments: a re-evaluation

Jakobsson (Contrib Miner Petrol 164(3):397–407, 2012) investigated a double capsule assembly for use in piston-cylinder experiments that would allow hydrous, high-temperature, and high-pressure experiments to be conducted under controlled oxygen fugacity conditions. Using a platinum outer capsule containing a metal oxide oxygen buffer (Ni–NiO or Co–CoO) and H₂O, with an inner gold–palladium capsule containing hydrous melt, this study was able to compare the oxygen fugacity imposed by the outer capsule oxygen buffer with an oxygen fugacity estimated by the AuPdFe ternary system calibrated by Barr and Grove (Contrib Miner Petrol 160(5):631–643, 2010). H₂O loss or gain, as well as iron loss to the capsule walls and carbon contamination, is often observed in piston-cylinder experiments and often go unexplained. Only a few have attempted to actually quantify various aspects of these changes (Brooker et al. in Am Miner 83(9–10):985–994, 1998; Truckenbrodt and Johannes in Am Miner 84:1333–1335, 1999). It was one of the goals of Jakobsson (Contrib Miner Petrol 164(3):397–407, 2012) to address these issues by using and testing the AuPdFe solution model of Barr and Grove (Contrib Miner Petrol 160(5):631–643, 2010), as well as to constrain the oxygen fugacity of the inner capsule. The oxygen fugacities of the analyzed melts were assumed to be equal to those of the solid Ni–NiO and Co–CoO buffers, which is incorrect since the melts are all undersaturated in H₂O and the oxygen fugacities should therefore be lower than that of the buffer by 2 log $a_{{{\text{H}}_{ 2} {\text{O}}}}$ .     

The Late Pleistocene Afton Lodge Clay Formation,Ayrshire, Scotland: evidence for Early to Middle Devensian climatic changes and Late Devensian onshore ice flow and rafting from the Firth of Clyde

An investigation into the late Pleistocene sediments exposed at Afton Lodge has helped to clarify the glacial history of western central Scotland. The sequence includes several allochthonous bodies of ‘shelly clay’ (Afton Lodge Clay Formation) associated with Late Devensian (Weichselian) age diamict. The shelly clay contains abundant marine macro- and microfauna, as well as palynomorphs consistent with its deposition within a shallow marine to estuarine environment. Faunal changes within the main body of marine clay record at least one, millennial-scale cycle of Arctic-Boreal, to Boreal, and back to Arctic-Boreal climatic conditions. A radiocarbon date of over 41 ka ¹⁴C BP obtained from the foraminifera indicates that the marine clays are older than the surrounding till. Afton Lodge is thus one of a suite of ‘high-level’ shelly clay occurrences around the Scottish coasts that are now considered to be glacially transported. Together with closely associated ‘shelly tills’, the rafts were emplaced during an early phase of the last glaciation by ice flowing from the western Grampian Highlands of Scotland through the topographically-confined Firth of Clyde basin. The blocks of marine sediment were detached subglacially, unfrozen, and carried at least 10 km by ice that splayed out onshore against reversed slopes favouring raft emplacement and the creation of closely associated ribbed moraine. Transport of the rafts was facilitated by water-lubricated décollement surfaces and their accretion was accompanied by dewatering. The shelly tills were formed mainly by the attenuation and crushing of rafts of shelly clay during their transport within the subglacial deforming bed.