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.     

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.     

A 2000‐year lipid biomarker record preserved in a stalagmite from north‐west Scotland

Previous studies on lipid biomarkers preserved in Chinese stalagmites have indicated that ratios of low‐molecular‐weight (LMW) to high‐molecular‐weight (HMW) n‐alkanes, n‐alkan‐2‐ones, n‐alkanols and n‐alkanoic acids can be used as an index of vegetation versus microbial organic matter input to the system and, by extension, a marker of climatic changes, with increases in the proportion of LMW compounds coinciding with colder periods. Here we test whether this hypothesis is equally applicable to a different geographical region (north‐west Scotland), by examining a stalagmite record of the past 200 years, and a wider range of lipid markers. We also test the applicability of other lipid proxies in this context, including the use of n‐alkane ratios, to interpret vegetation changes, and unsaturated alkanoic acid ratios as climatic indicators. The results show that lipid proxies preserved in stalagmites, and especially those related to vegetation, are potentially extremely useful in palaeoenvironmental research. Of particular value is the use of C₂₇/C₃₁ n‐alkane ratios as a proxy for vegetation change, clearly indicating variations between herbaceous and arboreal cover. This proxy has now been successfully applied to samples from diverse environments, and can be considered sufficiently robust to be of use in analysing future stalagmite records. It will be of particular value in areas where reliable pollen records are not available, as is often the case with deeper cave deposits. However, the division between LMW and HMW aliphatic compounds is not a clear‐cut case of microbial versus plant activity, with the changes in LMW compounds relating more closely to those in their HMW analogues than in specific bacterial biomarkers. The use of unsaturated alkanoic acid ratios here gives conflicting results, with the observed variation through time depending on the isomer measured. The discrepancies between the findings of this study and previous work are likely to be due to the varying controls on the lipids (original organic matter input, and compound degradation), which in turn will be affected by whether the main climatic limiting factor on the soil is temperature or precipitation. This suggests that lipid proxies preserved in stalagmites must be interpreted with care, particularly in the case of bacterial compounds which may be derived from within the cave or from the soil. However, many of these issues can be resolved by the use of multi‐proxy studies. Copyright © 2011 John Wiley & Sons, Ltd.     

Analytical solutions for advective–dispersive solute transport in double‐layered finite porous media

Analytical solutions for advection and dispersion of a conservative solute in a one‐dimensional double‐layered finite porous media are presented. The solutions are applicable to five scenarios that have various combinations of fixed concentration, fixed flux and zero concentration gradient conditions at the inlet and outlet boundaries that provide a wide number of options. Arbitrary initial solute concentration distributions throughout the media can be considered via explicit formulations or numerical integration. The analytical solutions presented have been verified against numerical solutions from a finite‐element‐based approach and an existing closed‐form solution for double‐layered media with an excellent correlation being found in both cases. A practical application pertaining to advective transport induced by consolidation of underlying sediment layers on contaminant movement within a capped contaminated sediment system is presented. Comparison of the calculated concentrations and fluxes with alternative approaches clearly illustrates the need to consider advection processes. Consideration of the different features of contaminant transport due to varying pore‐water velocity fields in primary consolidation and secondary consolidation stages is achieved via the use of non‐uniform initial concentration distributions within the proposed analytical solutions. Copyright © 2010 John Wiley & Sons, Ltd.     

Oxygen‐18 dynamics in precipitation and streamflow in a semi‐arid agricultural watershed,Eastern Washington,USA

Understanding flow pathways and mechanisms that generate streamflow is important to understanding agrochemical contamination in surface waters in agricultural watersheds. Two environmental tracers, δ¹⁸O and electrical conductivity (EC), were monitored in tile drainage (draining 12 ha) and stream water (draining nested catchments of 6‐5700 ha) from 2000 to 2008 in the semi‐arid agricultural Missouri Flat Creek (MFC) watershed, near Pullman Washington, USA. Tile drainage and streamflow generated in the watershed were found to have baseline δ¹⁸O value of ?14·7‰ (VSMOW) year round. Winter precipitation accounted for 67% of total annual precipitation and was found to dominate streamflow, tile drainage, and groundwater recharge. ‘Old’ and ‘new’ water partitioning in streamflow were not identifiable using δ¹⁸O, but seasonal shifts of nitrate‐corrected EC suggest that deep soil pathways primarily generated summer streamflow (mean EC 250 µS/cm) while shallow soil pathways dominated streamflow generation during winter (EC declining as low as 100 µS/cm). Using summer isotopic and EC excursions from tile drainage in larger catchment (4700‐5700 ha) stream waters, summer in‐stream evaporation fractions were estimated to be from 20% to 40%, with the greatest evaporation occurring from August to October. Seasonal watershed and environmental tracer dynamics in the MFC watershed appeared to be similar to those at larger watershed scales in the Palouse River basin. A 0·9‰ enrichment, in shallow groundwater drained to streams (tile drainage and soil seepage), of δ¹⁸O values from 2000 to 2008 may be evidence of altered precipitation conditions due to the Pacific Decadal Oscillation (PDO) in the Inland Northwest. Copyright © 2009 John Wiley & Sons, Ltd.