Alkylation of polycyclic aromatic hydrocarbons in carbonaceous chondrites

Using microprobe laser-desorption, laser-ionization mass spectrometry (μL²MS), we measured the distributions of alkylated and unalkylated polycyclic aromatic hydrocarbons (PAHs) in the free organic material of 20 carbonaceous chondrites. These meteorites represent a variety of meteorite classes and alteration histories, including CI, CK, CM, CO, CR, CV, and Tagish Lake. This work provides information on free organic compounds that is complementary to studies of the structure and composition of meteoritic macromolecular content.For the nine CM2 meteorites analyzed, we observe that higher relative abundances of alkylated PAHs correlate with more intense aqueous activity. We attribute this correlation to the differences in solubility and volatility between unalkylated and alkylated PAHs. Naphthalene and its alkylation series are more susceptible to the effects of aqueous exposure than the less-soluble PAH phenanthrene and its alkylated derivatives. These observations are consistent with the possibility of chromatographic separations on the meteorite parent bodies. We identify six CM2 meteorites with similar PAH distributions that may represent the original, unaltered organic composition of the parent body.Increased metamorphic intensity reduces the abundance of all PAHs. The thermally metamorphosed CK chondrites had no detectable levels of typical meteoritic PAHs. This observation might be explained either by a loss of PAHs caused by volatilization or by a significantly different organic content of the CK parent body.     

Redistribution of HFSE elements during rutile replacement by titanite

Titanite growth at the expense of rutile during retrograde hydration of eclogite into amphibolite is a common phenomenon. We investigated an amphibolite sample from the Tromsø eclogite facies terrain in Northern Norway to gain insight into the trace element distribution between rutile and titanite during incomplete resorption of the rutile by titanite. Patchy compositional zoning of Al, Ti, and F in titanite relates to the presence of a fluid with variable Ti/Al and/or F during its growth. Laser ablation ICP–MS and electron microprobe data for high field strength elements (HFSE: Nb, Zr, Ta, and Hf) of rutile resorbed by titanite indicate a pronounced enrichment of these elements in the rim of a large single rutile crystal (~8 mm) and a systematic decrease towards uniform HFSE contents in the large core. HFSE contents of smaller rutile grains (~0.5 mm) and rutile inclusions (<100 μm) in the titanite overgrowth are similar or higher than in the rims of large rutile crystals. Element profiles from the rim inward demonstrate that HFSE enrichment in rutile is controlled by diffusion. HFSE ratios in diffusion-altered rutile show systematic variations compared with the uniform core composition of the large rutile. Modelling of Zr and Nb diffusion in rutile indicates that diffusion coefficients in rutile in fluid-dominated natural systems must be considerably higher than those determined experimentally at 1 bar in dry systems. Variations of HFSE contents in the newly formed titanite show no systematic spatial distribution. HFSE ratios in titanite and the rims of rutile are different, indicating different solid/fluid distribution coefficients in these minerals. Element fractionation by diffusion into the relict rutile and during fluid-mediated growth of new titanite could substantially change the HFSE budget of these minerals and could affect their use for geochemical tracing and other applications, such as Zr-based geothermobarometry.     

Comparison of isotope pairing and N2:Ar methods for measuring sediment denitrification—Assumption, modifications, and implications

Denitrification has been measured during the last few years using two different methods in particular: isotope pairing measured on a triple-collector isotopic ratio mass spectrometer and N₂:Ar ratios measured on a membrane inlet mass spectrometer (MIMS). This study compares these two techniques in short-term batch experiments. Rates obtained using the original N₂∶Ar method were up to 3 to 4 times higher than rates obtained using the isotope pairing technique due to O₂ reacting with the N₂ during MIMS analysis. Oxygen combines with N₂ within the mass spectrometer ion source forming NO⁺ which reduces the N₂ concentration. The decrease in N₂ is least at lower O₂ concentrations and since oxygen is typically consumed during incubations of sediment cores, the result is often a pseudo-increase in N₂ concentration being interpreted as denitrification activity. The magnitude of this ocygen effect may be instrument specific. The reaction of O₂ with N₂ and the subsequent decrease in N₂ was only partly correctly using an O₂ correction curve for the relationship between N₂ and O₂ concentrations. The O₂ corrected N₂∶Ar denitrification rates were lower, but still did not match the isotope pairing rates and the variability between replicates was much higher. Using a copper reduction column heated to 600°C to remove all of the O₂ from the sample before MIMS analysis resulted in comparable rates (slightly lower), and comparable variability between replicates, to the isotope pairing technique. The N₂:Ar technique determines the net N₂ production as the difference between N₂ production by denitrification and N₂ consumption by N-fixation, while N-fixation has little effect on the isotope pairing technique which determines a rate very close to the gross N₂ production. When the two different techniques were applied on the same sediment, the small difference in rates obtained by the two methods seemed to reflect N-fixation as also supported from measurements of ethylene production in acetylene enriched sediment cores. The N₂:Ar and isotope pairing techniques may be combined to provide simultaneous measurements of denitrification and N-fixation. Both techniques have several assumptions that must be met to achieve accurate rates; a number of tests are outlined that can be applied to demonstrate that these assumptions are being meet.     

Pre-Cenozoic intra-plate magmatism along the Central Andes (17–34°S): Composition of the mantle at an active margin

Sr–Nd–Pb isotope ratios of alkaline mafic intra-plate magmatism constrain the isotopic compositions of the lithospheric mantle along what is now the eastern foreland or back arc of the Cenozoic Central Andes (17–34°S). Most small-volume basanite volcanic rocks and alkaline intrusive rocks of Cretaceous (and rare Miocene) age were derived from a depleted lithospheric mantle source with rather uniform initial ¹⁴³Nd/¹⁴⁴Nd ( 0.5127–0.5128) and ⁸⁷Sr/⁸⁶Sr ( 0.7032–0.7040). The initial ²⁰⁶Pb/²⁰⁴Pb ratios are variable (18.5–19.7) at uniform ²⁰⁷Pb/²⁰⁴Pb ratios (15.60 ± 0.05). A variety of the Cretaceous depleted mantle source of the magmatic rocks shows elevated Sr isotope ratios up to 0.707 at constant high Nd isotope ratios. The variable Sr and Pb isotope ratios are probably due to radiogenic growth in a metasomatized lithospheric mantle, which represents the former sub-arc mantle beneath the early Palaeozoic active continental margin. Sr–Nd–Pb isotope signatures of a second mantle type reflected in the composition of Cretaceous (one late Palaeozoic age) intra-plate magmatic rocks (¹⁴³Nd/¹⁴⁴Nd  0.5123, ⁸⁷Sr/⁸⁶Sr  0.704, ²⁰⁶Pb/²⁰⁴Pb  17.5–18.5, and ²⁰⁷Pb/²⁰⁴Pb  15.45–15.50) are similar to the isotopic composition of old sub-continental lithospheric mantle of the Brazilian Shield.

Published Nd and Sr isotopic compositions of Mesozoic to Cenozoic arc-related magmatic rocks (18–40°S) represent the composition of the convective sub-arc mantle in the Central Andes and are similar to those of the Cretaceous (and rare Miocene) intra-plate magmatic rocks. The dominant convective and lithospheric mantle type beneath this old continental margin is depleted mantle, which is compositionally different from average MORB-type depleted mantle. The old sub-continental lithospheric mantle did not contribute to Mesozoic to Cenozoic arc magmatism.     

Adjustments by the Charwell River, New Zealand, to uplift and climatic changes

Major climatic changes and rapid local and regional tectonic movements were common in New Zealand during the late Quaternary and caused a diversity of adjustments in the drainage-basin and piedmont reaches of the Charwell River, which are separated by the Hope Fault. The onset of semi-arid, frigid climates during the latest Pleistocene probably greatly increased hillslope sediment yields in a periglacial environment, and the piedmont reach aggraded as much as 42 m on top of a broad strath. With the return of humid, mesic climates in the Holocene sediment yields decreased as dense forests again mantled the slopes, and the piedmont reach degraded as mush as 81 m. Dating of eleven cut-and-strath terraces by radiocarbon-calibrated weathering rind measurements on greyawake cobbles shows the degradation rates varied greatly during the last 14 ka (1 ka = 1000 yr). Initial degradation rates of < 4 m ka⁻¹ increased to 30 m ka ⁻¹ by 6 ka ago during a mid-Holocene climatic optimum. Since 4 ka ago degradation rates have been only 1.2 m ka⁻¹, comparable to uplift rates in the piedmont reach inferred from marine-terrace studies, and the river is again cutting a broad strath. Each broad strath represents equilibrium conditions attained by this powerful stream during interglacial times despite episodes of being overwhelmed by climatically induced sediment-yield increases during full-glacial climates and having to maintain a long-term degradation rate equal to the uplift rate.The 75–81 m of degradation since formation of the latest Pleistocene fill-terrace tread is the sum of the amount of late Pleistocene valley-floor aggradation and the amount of regional uplift that occurred between the estimated times of major strath formation at about 30 and 0 ka. The 39 m of tectonically induced degradation below the pre-aggradation strath is sufficiently large that post-30 ka uplift may have doubled Holocene degradation rates.Each of the eleven degradation terraces represents pauses of a few centuries in Holocene downcutting. Brief equilibrium conditions were attained by streambed armoring and concurrent growth of riparian plants; both processes progressively increased hydraulic roughness and the shear stresses needed to entrain streambed materials. Occasional floods, possibly from rare cyclones derived from tropical moisture sources, destroyed streambed armor and channel downcutting was renewed. Thus the formation of eleven equilibrium terraces can be accounted for without postulating additional tectonic perturbations or secular climatic changes.     

Oxygen and nutrient dynamics within mats of the filamentous macroalga Chaetomorpha linum

Concentration profiles of O₂, NH₄ ⁺, NO₃ ⁻, and PO₄ ³⁻ were measured at high spatial resolution in a 12-cm thick benthic mat of the filamentous macroalga Chaetomorpha linum. Oxygen and nutrient concentration profiles varied depending on algal activity and water turbulence. High surface irradiance stimulated O₂ production in the surface layers and introduced O₂ to deeper parts of the mat while the bottom layers of the mat and the underlying sediment were anoxic. Nutrient concentrations were highest in the bottom layers of the mat directly above the sediment nutrient source and decreased towards the surface layers due to algal assimilation and enhanced mixing with the overlying water column. Increased turbulence during windy periods resulted in more homogeneous oxygen and nutrient concentration profiles and shifted the oxic-anoxic interface downward. Denitrification within the mat, as measured by the isotope pairing technique on addition of ¹⁵NO₃ ⁻, was found to take place directly below the oxic-anoxic interface. Denitrification activity was always due to coupled nitrification-denitrification, whereby nitrifiers in the mat utilize NH₄ ⁺ diffusing from below and O₂ diffusing from above. The denitrification rate in the mat ranged from 22 μmol m⁻² h⁻¹ to 28 μmol m⁻² h⁻¹, approximately equivalent to that measured in the surrounding nonvegetated sediment. Although sediment denitrification is suppressed when the sediment surface is covered by a dense macroalgal mat, the denitrification zone may migrate up into the mat. In eutrophic estuaries with a large area of macroalgal cover, the physical structure and growth stage of algal mats may thus play an important role in the regulation of nitrogen removal by denitrification.     

Amino acid nitrogen in atmospheric aerosols: Occurrence,sources and photochemical modification

The presence of amino acids in atmospheric precipitation and aerosols has been noted for many years, yet relatively little is known about these or other nitrogen containing organic compounds in the atmosphere. Marine and continental rainwater analyses indicate that atmospheric aerosols, and subsequently atmospheric precipitation, may contain substantial levels of free and combined amino acids. The most likely source of amino N in the remote marine atmosphere appears to be the injection of proteinaceous material through the action of bursting bubbles at the sea-air interface or the long range transport from terrestrial sources. The capacity of these substrates to undergo photooxidation and photodegradation in the atmosphere to simpler species, such as ammonium ions, carboxylic acids, and for the S containing amino acids, oxidized forms of sulfur, has received little attention from atmospheric chemists. The photochemistry of covalently bound amino groups, particularly as found in peptides and amino acids, is discussed here with the purpose of summarizing what is known of their occurrence and their possible importance to atmospheric chemistry.     

Lake District hillslopes

The Lake District is a region of great scenic beauty in north‐west England that has inspired artists and poets alike, and which comes high on the list of classic geological localities in Great Britain in terms of both bedrock and geomorphological features. With its inspiring views, the Lake District is often portrayed as the product of repeated glaciation, mainly because of the clarity of the erosional and depositional features that can be seen there. But since the last glaciers disappeared other processes have been modifying the landscape, processes that have superimposed their own signatures on to the glacial features. Hillslopes in particular have undergone significant changes, as a result of slope failures in both bedrock and superficial sediments. Although these landforms are not unknown, they have not received the same level of investigation as the glacial features, resulting in a limited appreciation of their spatial distribution and significance in reshaping the landscape. This article outlines the characteristics and origins of some slope failure types, and demonstrates that there is still much to learn about the Lake District landscape.