Arsenic incorporation into FeS2 pyrite and its influence on dissolution: A DFT study

FeS₂ pyrite can incorporate large amounts of arsenic (up to ca. 10 wt%) and hence has a strong impact on the mobility of this toxic metalloid. Focussing on the lowest arsenic concentrations for which the incorporation occurs in solid solution, the substitution mechanisms involved have been investigated by assuming simple incorporation reactions in both oxidising and reducing conditions. The solution energies were calculated by Density Functional Theory (DFT) calculations and we predict that the formation of AsS dianion groups is the most energetically favourable mechanism. The results also suggest that the presence of arsenic will accelerate the dissolution and thus the generation of acid drainage, when the crystal dissolves in oxidising conditions.     

Investigation of the Ablation Behaviour of Andradite-Grossular Garnets and Rutile with Implications for U-Pb Geochronology

U-Pb dating of andradite-grossular garnet (grandite) and rutile by LA-ICP-MS can be used to constrain various metamorphic, metasomatic and igneous geological processes. In this study, we examine and compare the impact of different analytical conditions (fluence, pulse width, laser beam size and ablation frequency) on the ablation crater morphology, ablation rates, down-hole fractionation and U-Pb ages of grandite and rutile samples of different compositions. The shapes of grandite ablation craters suggest the mineral ablates by classical evaporation with significant melting that cannot be eliminated even at fluences just above the ablation threshold. Grandite garnets with higher andradite proportions have faster ablation rates. The overall low U contents of grandite require using large laser beam sizes to obtain acceptable precision of U-Pb ages. At such conditions and crater depths < 10 μm, fluences of 2.1 and 3.5 J cm^-2, laser pulse width of 5 ns and 20 ns, and ablation frequencies between 3.5 and 6.5 Hz, obtain similar and reproducible ages when the proportion of grossular is < 35%. Rutile ablation crater morphology shows evidence of melt splashing and thermal stress cracking. They have significant crater bottom features, which increase in relief with lower fluences and a higher number of laser shots, indicating the features are probably energy-related and making higher fluences, such as 5 J cm^-2, necessary for uniform ablation when using 193 nm excimer lasers. The slow ablation rate at low fluences and then steep increase at around 2.0 J cm^-2 suggests a transition in the ablation mechanism from exfoliation to classical vaporisation. Crater bottom features and other ablation behaviour vary between samples, which could be related to their difference in colour. Although the down-hole fractionation patterns of the samples are similar at 5 J cm^-2, the U-Pb ages of some samples vary significantly with different analytical conditions and/or measurement sessions, particularly when using laser beam sizes of 30 μm, suggesting differences in mass bias and more variable ablation behaviour. A laser beam size of at least 60 μm is recommended for reproducible U-Pb dating of rutile.     

Prairie or planted? Using time-series NDVI to determine grassland characteristics in Montana

Temperate grasslands are a highly threatened global biome. Complicating management and conservation strategy development, modern grasslands can be difficult to characterize across landscapes since they range from native and semi-native to completely non-native species compositions such as those found in heavily managed pastures. Similar to methods used to differentiate C3 and C4 grasses, we investigate the ability of using temporal variations in growth characteristics as an alternative pathway to predicting native versus introduced species composition across grassland landscapes. To do this, we conducted an exploratory analysis using a time-series of Normalized Difference Vegetation Index values as a measure of vegetation greenness with Landsat 5 TM imagery across a growing season and performed an unsupervised classification. Results from the classification were compared with field observation to determine if we can differentiate between native and introduced grassland types in the Northwest Glaciated Plains subecoregion of northeastern Montana. Our results indicated that we predicted grassland cover with 81% accuracy within our 200 km² study area and 71% accuracy in our 5000 km² secondary study area. Further extrapolation of our methodology, combined with the refinement of vegetation indices of time-series imagery, classification algorithms and the availability of data from planned Landsat and Sentinel missions, may provide the spatial detail necessary to improve grassland monitoring and rangeland management over large areas.     

Vegetation controls on channel stability in the Bell River,Eastern Cape,South Africa

Channel instability has occurred in the Bell River in the form of meander cutoffs, a number of which have occurred since 1952. Increased sediment loading from widespread gully erosion in the catchment has been proposed as the trigger for this instability. Willow species of the Salix family, in particular S. caprea, have been planted along the banks in an effort to prevent further channel shifting. This study reports the results of an investigation into the effect of vegetation on channel form and stability over a 17 km stretch of channel. Results indicate that riparian vegetation has significant effects on channel form which have implications for channel stability. Riparian vegetation increases bank stability and reduces channel cross-sectional area, thereby inducing stability at flows less than bankfull. Evidence indicates that narrow stable stretches are associated with relatively high levels of riparian vegetation. Wider, unstable channels are associated with relatively less riparian vegetation. The effectiveness of riparian vegetation relative to bank sediments was investigated. A dense growth of willows was found to have an equivalent effect to banks with a silt-clay ratio of about 70 per cent. The channel narrowing induced by vegetation may contribute to channel shifting at high flows. The reduced channel capacity is thought to result in more frequent overbank flooding which may ultimately lead to channel avulsion. Thus where increased sediment loading is pushing the channel towards instability, vegetation may be effective in imparting local stability, but it is unable to prevent long-term channel shifts, and may rather help to push the system towards more frequent avulsions. Copyright © 1999 John Wiley & Sons, Ltd.     

Growing new generations of critical zone scientists

Critical zone (CZ) science is entering its second decade. A new generation of scientists is emerging trained specifically in CZ science and are contributing to advances in environmental science across disciplines. Concurrently, the global scope of CZ science is being elevated as new countries invest in CZ observatories. Global CZ science has great potential to address a diverse array of questions beyond any single discipline. In this commentary we discuss a series of CZ science grand challenges that should be targeted by early‐career researchers: understanding water availability in the CZ; expanding CZ science into new environments; communicating the societal relevance of CZ science including earthcasting to the public; seamlessly integrating biological sciences within the CZ framework; and scaling CZ processes over large spatial and temporal gradients. Targeting these grand challenges will push CZ science well into the future. We also highlight mechanisms for increased leadership within the CZ community. Copyright © 2017 John Wiley & Sons, Ltd.     

Shades of green in local authority policy-making: a regional case study

Summary Local authorities have been seen as an important agent in the development of more sustainable economies. This paper explores the level and form of 'greening' taking place amongst local authorities in the Midland region of the UK. Particular attention is paid to intra-regional variations in environmental policy-making.     

Analysis of phospholipid fatty acids (PLFA) to characterize microbial communities in aquifers

This paper reviews published applications of lipid-based biochemical techniques for characterizing microbial communities in aquifers and other deep subsurface habitats. These techniques, such as phospholipid fatty acid (PLFA) analysis, can provide information on a variety of microbial characteristics, such as biomass, physiology, taxonomic and functional identity, and overall community composition. In addition, multivariate statistical analysis of lipid data can relate spatial or temporal changes in microbial communities to environmental factors. The use of lipid-based techniques in the study of groundwater microbiology is advantageous because they do not require culturing and can provide quantitative data on entire communities. However, combined effects of physiological and phylogenetic changes on the lipid composition of a community can confound interpretation of the data, and many questions remain about the validity of various lipid techniques. Despite these caveats, lipid-based research has begun to show trends in community composition in contaminated and pristine aquifers that contribute to our understanding of groundwater microbial ecology and have potential for use in optimization of bioremediation of groundwater pollutants. Résumé Ce papier passe en revue les applications des techniques biochimiques basées sur les lipides pour caractériser les communautés microbiennes présentes dans les aquifères et dans les autres habitats souterrains profonds. Ces techniques, telles que l'analyse des acides gras phospholipidiques (PLFA), peuvent fournir des informations sur un ensemble de caractères microbiens, tels que la biomasse, la physiologie, l'identité taxonomique et fonctionnelle, et surtout la composition de la communauté. En outre, l'analyse statistique multivariée des données sur les lipides peut établir les liens entre des changements spatiaux ou temporels dans la communauté microbienne et des facteurs environnementaux. L'utilisation des techniques basées sur les lipides dans l'étude de la microbiologie des eaux souterraines est intéressante parce qu'elle ne nécessite pas de mise en culture et qu'elle peut fournir des données quantitatives sur les communautés dans leur ensemble. Toutefois, les effets combinés de changements physiologiques et phylogénétiques sur la composition d'une communauté peuvent brouiller l'interprétation des données; de nombreuses questions se posent sur la validité des différentes techniques lipidiques. Malgré ces oppositions, la recherche basée sur les lipides a commencé à montrer des tendances dans la composition des communautés dans les aquifères pollués et dans ceux non perturbés; ces résultats contribuent ainsi à notre compréhension de l'écologie microbienne des eaux souterraines et montrent qu'il existe un potentiel pour leur utilisation en vue d'une optimisation de la dépollution biologique des eaux souterraines. Resumen Se revisan distintas técnicas bioquímicas que se basan en el análisis de lípidos para caracterizar las comunidades microbianas en hábitats subsuperficiales, incluyendo acuíferos. Estas técnicas, entre las que se incluye el análisis de ácidos grasos fosfolípidos (PLFA), pueden proporcionar información sobre toda una serie de características de las comunidades microbianas, como su biomasa, fisiología, identidad taxonómica y funcional y composición. Además, el análisis estadístico multivariado de los datos de lípidos permite relacionar los cambios espaciales o temporales en las comunidades microbianas con factores ambientales. Las técnicas basadas en lípidos son muy útiles para el estudio microbiológico de las aguas subterráneas, puesto que no requieren cultivos y además proporcionan datos cuantitativos de comunidades completas. Sin embargo, la acción combinada de los cambios fisiológicos y filogenéticos en la composición de lípidos en una comunidad pueden confundir la interpretación de los datos, por lo existen muchas cuestiones abiertas respecto a la validez de algunas de estas técnicas. A pesar de estas dificultades, estas técnicas han permitido detectar diferentes tendencias en la composición de las comunidades en acuíferos con y sin contaminación, lo que contribuye a nuestro entendimiento de la ecología microbiana de los acuíferos. Este último aspecto tiene un uso potencial en la optimización de los métodos de biorremediación de acuíferos.     

Modified sediments and subsurface hydrology in natural and recreated salt marshes and implications for delivery of ecosystem services

Recreation or restoration of salt marsh through the deliberate removal of flood defences (managed realignment or de‐embankment) is a common practice across Europe and the USA, with potential to enhance delivery of ecosystem services. However, recent research suggests that physical, chemical and ecological processes may be impaired in recreated sites as a result of the modified morphology, sediment structure and hydrology associated with both the restoration process and historic land use. This paper compares physical sediment properties and subsurface water levels recorded in paired natural and de‐embanked (recreated) salt marshes in SE England. Using a combination of statistical and time‐series modelling, significant differences between the natural and recreated marshes are identified. Sediment properties (bulk density, moisture content and organic content) within each marsh were statistically different and imply that de‐embanked sediments are compacted, which may affect subsurface water movement. Analysis of hydrological time series reveals that the de‐embanked salt marsh is characterized by a damped response to tidal flooding with elevated and less variable water levels. This, combined with analysis of hydrographs and hysteresis patterns over individual tidal cycles, suggests that fast, horizontal near‐surface flows enhanced by the relict land surface may play a greater role in drainage of the de‐embanked salt marsh. The importance of hydrological functioning in governing many important physical and biogeochemical processes in salt marshes suggests any modifications would have significant implications for the delivery of ecosystem services. Copyright © 2014 John Wiley & Sons, Ltd.     

Creating Residential and Tenure Histories from Multi‐Year White Pages

In epidemiology research, a list of residences a person has occupied as well as a history of tenants for a residence are useful pieces of information for investigating geographically localized risk factors, environmental exposures, and for analyzing disease clusters. This article reports on a methodology for constructing residential and tenure histories using multi‐year white page phone listings. Residential histories associate a person with a list of addresses of residence and the length of occupancy at each address. Tenure histories document the list of persons occupying a residence along with length of occupancy. These histories were created using fuzzy matching on name address pairs between sequential years. Simulated annual phone listing data were used to develop and test the methodology which was then applied to an actual white page phone listing for a study town in Maine. The approach is applied locally and generates partial local residential and tenure histories that capture local migrations. We see these local history sets as building blocks for constructing more geographically extensive histories over time. Geocoded results were compared against numbers of housing units reported in the 2000 and 2010 US Census to assess the proportion of local residences captured by phone listings.