Effect of contaminant concentration on in situ bacterial sulfate reduction and methanogenesis in phenol-contaminated groundwater

The availability of dissolved O₂ can limit biodegradation of organic compounds in aquifers. Where O₂ is depleted, biodegradation proceeds via anaerobic processes, including NO₃-, Mn(IV)-, Fe(III)- and SO₄-reduction and fermentation/methanogenesis. The environmental controls on these anaerobic processes must be understood to support implementation of management strategies such as monitored natural attenuation (MNA). In this study stable isotope analysis is used to show that the relative significance of two key anaerobic biodegradation processes (bacterial SO₄ reduction (BSR) and methanogenesis) in a phenol-contaminated sandstone aquifer is sensitive to spatial and temporal changes in total dissolved phenols concentration (TPC) (= phenol + cresols + dimethylphenols) over a 5-a period. In general, ³⁴SO₄-enrichment (characteristic of bacterial SO₄ reduction) is restricted spatially to locations where TPC < 2000 mg L⁻¹. In contrast, ¹³C-depleted CH₄ and ¹³C-enriched CO₂ isotope compositions (characteristic of methanogenesis) were measured at TPC up to 8000 mg L⁻¹. This is consistent with previous studies that demonstrate suppression of BSR at TPC of >500 mg L⁻¹, and suggests that methanogenic microorganisms may have a higher tolerance for TPC in this contaminant plume. It is concluded that isotopic enrichment trends can be used to identify conditions under which in situ biodegradation may be limited by the properties of the biodegradation substrate (in this case TPC). Such data may be used to deduce the performance of MNA for contaminated groundwater in similar settings.     

East African food security as influenced by future climate change and land use change at local to regional scales

Climate change impacts food production systems, particularly in locations with large, vulnerable populations. Elevated greenhouse gases (GHG), as well as land cover/land use change (LCLUC), can influence regional climate dynamics. Biophysical factors such as topography, soil type, and seasonal rainfall can strongly affect crop yields. We used a regional climate model derived from the Regional Atmospheric Modeling System (RAMS) to compare the effects of projected future GHG and future LCLUC on spatial variability of crop yields in East Africa. Crop yields were estimated with a process-based simulation model. The results suggest that: (1) GHG-influenced and LCLUC-influenced yield changes are highly heterogeneous across this region; (2) LCLUC effects are significant drivers of yield change; and (3) high spatial variability in yield is indicated for several key agricultural sub-regions of East Africa. Food production risk when considered at the household scale is largely dependent on the occurrence of extremes, so mean yield in some cases may be an incomplete predictor of risk. The broad range of projected crop yields reflects enormous variability in key parameters that underlie regional food security; hence, donor institutions’ strategies and investments might benefit from considering the spatial distribution around mean impacts for a given region. Ultimately, global assessments of food security risk would benefit from including regional and local assessments of climate impacts on food production. This may be less of a consideration in other regions. This study supports the concept that LCLUC is a first-order factor in assessing food production risk.     

Molecular scale investigations of the reactivity of magnetite with formic acid, pyridine, and carbon tetrachloride

The (111) surface of magnetite, a dominant growth and fracture surface of this mineral, has been studied using Scanning Tunneling Microscopy (STM) at atomic resolution. In line with previous work, this surface shows three possible terminations which can be related to different level slices through the bulk structure. The reactivities of these different surface terminations have been explored by exposing them, under highly controlled conditions, to formic acid, pyridine, and carbon tetrachloride and undertaking further imaging at atomic resolution. These investigations have, themselves, helped to discriminate between competing models of surface structure. The so-called A′ surface termination we now regard as exposing 1/4 monolayer of tetrahedrally coordinated Fe ions over a close packed oxygen layer, and the A surface termination as being these same Fe ions but each capped by a single oxygen. The so-called B surface termination, previously thought to expose 1/2 monolayer of equal numbers of octahedral and tetrahedral Fe ions over a close packed oxygen layer, we now regard as this same arrangement but again with each Fe capped with an oxygen. For all three molecules, the A′ surface is most reactive but the reactions observed are markedly different. Formic acid undergoes dissociation at the magnetite surface, apparently chemisorbing at the A′ surface via a bidentate non-bridging complex. On the same A′ surface, pyridine is chemisorbed through a monodentate linkage via the ‘basal’ nitrogen of the molecule. For both formate and pyridine, a weaker interaction (a ‘physisorption’) was observed with the A and B surfaces, interpreted as involving attachment of the intact molecule. The exceptions to this were where the interaction involved chemisorption at defects on A and B type surfaces. The behavior of carbon tetrachloride on the magnetite surface is very different to the other molecules studied. Only the A′ surface is significantly reactive, and the molecule undergoes a series of temperature-dependant dissociation and surface chemical reactions. These involve sorption of intact CCl₄ molecules at the lowest temperatures, dissociation into CCl₂ and Cl species at around room temperature, and removal from the magnetite of surface oxygens to form OCCl₂ and then Fe to form FeCl₂ at successively higher temperatures. At around room temperature, both strongly bonded Cl atoms and weakly bonded CCl₂ molecules appear to co-exist on the same (A′ type) surface, a situation not previously observed in iron oxide systems.     

Palaeogene igneous rocks reveal new insights into the geodynamic evolution and petroleum potential of the Rockall Trough, NE Atlantic Margin

Data acquired from petroleum exploration well 164/7‐1 drilled in the UK sector of the Rockall Trough have yielded fresh insights into the igneous and thermal history of this frontier region. The well targeted a large four‐way dip closed structure of presumed Mesozoic age named ‘The Dome Prospect’. The structure is now known to have a magmatic, rather than a purely structural origin, which was the preferred pre‐well interpretation. The well encountered 1.2 km of Palaeocene age basaltic lavas, overlying Late Cretaceous mudstones which were intruded by over 70 dolerite sills ranging from <1.5‐ to 152‐m thick. ⁴⁰Ar/³⁹Ar dating of the dolerite intrusions indicates an Early Palaeocene age (63–64±0.5 Ma), which are among the oldest ⁴⁰Ar/³⁹Ar dates recognised in the North Atlantic Igneous Province. Radiometric dating of the overlying basaltic lavas proved unsuccessful, because of excessive alteration. Biostratigraphic dating of underlying and overlying sedimentary strata was utilised to constrain the age of the lavas to Late Paleocene to Early Eocene age (～55 Ma). Despite being related to two distinct events separated by ～8 Ma, the intrusives and extrusives are compositionally similar. The basaltic rocks from well 164/7‐1 possess Sr–Nd isotopic, major and trace‐element geochemical compositions similar to other volcanic and intrusive rocks of the British Tertiary Igneous Province and represent partial melts of both lithospheric and asthenospheric mantle associated with the proto‐Icelandic mantle plume head. Joint consideration of thermal maturity, potential fields and 3D seismic data indicate a deeper igneous body in addition to the sills encountered in well 164/7‐1. Jack‐up and arching mechanisms associated with both scales of intrusive body are believed to have developed the dome structure. The preferred interpretation is of a mafic laccolith, 17 km in diameter, ～7 km thick, intruded at 64.5 Ma, situated ～2.5 km below the bottom of the well. 3D thermal modelling suggests that all of Tranche 52 was thermally affected by the intrusion of the magmatic body. The thermal aureole, between 27 and 51 km in diameter, is not thought to play an important role in the hydrocarbon prospectivity of the surrounding Tranches in the NE Rockall Basin. Results show that hydrocarbon exploration prospects that are circular in map view should be interpreted with caution on volcanic continental margins. In sedimentary basins, where salt domes and shale diapirs are absent and igneous rocks prevalent, periclinal structures such as ‘The Dome Prospect’ should undergo a thorough multi‐disciplinary risk assessment.     

Modelling the Impact of Rockmass and Blast Design Variation on Blast Fragmentation

Most blast fragmentation models assume the rock mass properties. explosive properties and blast design variables to be constants and uniformly distributed within a blast. However, in reality all these input variables vary within a blast resulting in variation in the resulting fragmentation size distribution. A stochastic modelling approach is introduced in this paper to quantify this variation. This technique takes the input variables as statistical distributions rather than constants and through several thousand iterations, generates a statistical representation of the expected fragmentation resulting from a poduction blast. A case study of three production blasts from a large open pit mine are presented and the modelled fragmentation 'envelope' shows good agreement with the fragmentation 'envelope' estimated from Split image analysis. The various blast-related parameters influence different parts of the fragmentation distribution, e.g., rock strength and explosive velocity of detonation have most impact on the fines. The technique is used to identify the parameters that have the greatest influence on various size fractions. Such an analysis will be useful to direct resources to efficiently minimise the variation.     

Determination of trace aqueous dimethylsulfoxide concentrations by isotope dilution gas chromatography/mass spectrometry: Application to rain and sea water

A method has been developed for determining trace quantities of dimethyl sulfoxide (DMSO) in aqueous solutions using isotope dilution gas chromatography/mass spectrometry. The method consisted of first reducing DMSO to dimethyl sulfide (DMS), followed by purge and trap preconcentration of DMS. The concentration of DMSO was determined from the signal ratio obtained for the parent ions of DMS and d₆-DMS, and the known aqueous concentration of d₆-DMSO. The precision of this method was determined to be ± 2.9 %, based on replicate DMSO determinations of a test solution prepared by adding isotopically unenriched (h₆-DMSO) to distilled water. The detection limit was 0.010 nmoles/L for the sampling conditions used in this study. This method was applied to the determination of DMSO concentrations in both rain and sea water. The concentration of DMSO in rain was found to be in the range of 2–4 nmoles/L for samples collected at an inland location (Phila, PA) and 8–11 nmoles/L for samples collected at a coastal location (Lewes, DE). Determination of DMSO in sea water required special sample preparation steps to eliminate positive interferences. A depth profile of DMS, DMSO, and dimethyl sulfoniopropionate (DMSP) concentrations is reported for sea water collected off the coast of Ocean City, Md, in August, 1990     

Colonization of the Krakatau islands by vertebrates

80 species of non-marine, non-migrant vertebrates, excluding also shore birds, have been recorded from the Krakatau archipelago since the explosive eruption of 1883.73 of these are believed to have established breeding populations and successfully colonized the islands (47 resident land birds species, 13 bats, 11 reptiles and 2 rats). A large proportion of these colonizers consists of species with wide distributions, broad ecological tolerances and/or association with urban or rural situations. 11 of the 73 colonizing species (8 resident land birds, 2 reptiles and a bat) have become extinct on the islands. No amphibian species has yet been recorded and successful non-volant mammal colonists consist only of rats.Species turnover is considered to be largely associated with successional change of habitat. Progressive loss of coastal habitat through marine erosion and of open inland habitats through forest formation and canopy closure has been important and volcanic activity is indicated in the case of one or two extinctions.Active flight has been the predominant dispersal method (63 of the recored species, 79%, are birds or bats). Of the 17 recorded non-volant vertebrates, 6 species are assessed as having dispersed by swimming, 4 by means of natural rafts and 7 most likely through human agency (on boats). Human-assisted dispersal is seen to be of increasing importance with the increasing number of tourist visits and this may prove to be significant in determining the nature and rate of future colonization by vertebrates.     

Photographic evidence of rate of development of plant cover on the emergent island Anak Krakatau from 1971 to 1991 and implications for the effect of volcanism

Photographs of the vegetated North and East Forelands of Anak Krakatau, which emerged from the sea in 1930 and was totally devastated by volcanic activity in 1952/53 provide some evidence of rate of change of plant cover from grassland to woodland between 1971 and 1991. The series of photographs demostrate that vegetational stages of the two forelands have not been synchronous and suggest that the North Foreland is lagging the East Foreland by about 12 years.A recent hypothesis that Anak Krakatau's vegetation was destroyed, totally or almost so, by eruptions in 1972/73 and the island's vegetation has regenerated since that time is not easily accommodated by the photographic evidence, nor by the relative rates of change on Rakata (Krakatau's post-1883 remnant) and Anak Krakatau. The photographic evidence accords more closely with a hypothesis that the 1972/73 eruptions affected the North Foreland's vegetation only, or affected it to a much greater degree than that of the East Foreland, allowing the latter's post-1952/53 succession to proceed relatively unhampered.