The role of root exuded low molecular weight organic anions in facilitating petroleum hydrocarbon degradation: current knowledge and future directions

Rhizoremediation is a bioremediation technique whereby enhanced microbial degradation of organic contaminants occurs within the plant root zone (rhizosphere). It is considered an effective and affordable ‘green technology’ for remediating soils contaminated with petroleum hydrocarbons (PHCs). This paper critically reviews the potential role of root exuded compounds in rhizoremediation, with emphasis on commonly exuded low molecular weight aliphatic organic acid anions (carboxylates). The extent to which remediation is achieved shows wide disparity among plant species. Therefore, plant selection is crucial for the advancement and widespread adoption of this technology. Root exudation is speculated to be one of the predominant factors leading to microbial changes in the rhizosphere and thus the potential driver behind enhanced petroleum biodegradation. Carboxylates can form a significant component of the root exudate mixture and are hypothesised to enhance petroleum biodegradation by: i) providing an easily degradable energy source; ii) increasing phosphorus supply; and/or iii) enhancing the contaminant bioavailability. These differing hypotheses, which are not mutually exclusive, require further investigation to progress our understanding of plant–microbe interactions with the aim to improve plant species selection and the efficacy of rhizoremediation.

Remediation of soils contaminated with petrol and diesel with lime

Lime treatment of hydrocarbon-contaminated soils offers the potential to stabilize and solidify these materials, with a consequent reduction in the risks associated with the leachate emanating from them. This can aid the disposal of contaminated soils or enable their on-site treatment. In this study, the addition of hydrated lime and quicklime significantly reduced the leaching of total petroleum hydrocarbons (TPH) from soils polluted with a 50:50 petrol/diesel mixture. Treatment with quicklime was slightly more effective, but hydrated lime may be better in the field because of its ease of handling. It is proposed that this occurs as a consequence of pozzolanic reactions retaining the hydrocarbons within the soil matrix. There was some evidence that this may be a temporary effect, as leaching increased between seven and 21 days after treatment, but the TPH concentrations in the leachate of treated soils were still one order of magnitude below those of the control soil, offering significant protection to groundwater. The reduction in leaching following treatment was observed in both aliphatic and aromatic fractions, but the latter were more affected because of their higher solubilty. The results are discussed in the context of risk assessment, and recommendations for future research are made.

Mesozoic climates: General circulation models and the rock record

General circulation models (GCMs) use the laws of physics and an understanding of past geography to simulate climatic responses. They are objective in character. However, they tend to require powerful computers to handle vast numbers of calculations. Nevertheless, it is now possible to compare results from different GCMs for a range of times and over a wide range of parameterisations for the past, present and future (e.g. in terms of predictions of surface air temperature, surface moisture, precipitation, etc.). GCMs are currently producing simulated climate predictions for the Mesozoic, which compare favourably with the distributions of climatically sensitive facies (e.g. coals, evaporites and palaeosols). They can be used effectively in the prediction of oceanic upwelling sites and the distribution of petroleum source rocks and phosphorites. Models also produce evaluations of other parameters that do not leave a geological record (e.g. cloud cover, snow cover) and equivocal phenomena such as storminess. Parameterisation of sub-grid scale processes is the main weakness in GCMs (e.g. land surfaces, convection, cloud behaviour) and model output for continental interiors is still too cold in winter by comparison with palaeontological data. The sedimentary and palaeontological record provides an important way that GCMs may themselves be evaluated and this is important because the same GCMs are being used currently to predict possible changes in future climate. The Mesozoic Earth was, by comparison with the present, an alien world, as we illustrate here by reference to late Triassic, late Jurassic and late Cretaceous simulations. Dense forests grew close to both poles but experienced months-long daylight in warm summers and months-long darkness in cold snowy winters. Ocean depths were warm (8 degrees C or more to the ocean floor) and reefs, with corals, grew 10 degrees of latitude further north and south than at the present time. The whole Earth was warmer than now by 6 degrees C or more, giving more atmospheric humidity and a greatly enhanced hydrological cycle. Much of the rainfall was predominantly convective in character, often focused over the oceans and leaving major desert expanses on the continental areas. Polar ice sheets are unlikely to have been present because of the high summer temperatures achieved. The model indicates extensive sea ice in the nearly enclosed Arctic seaway through a large portion of the year during the late Cretaceous, and the possibility of sea ice in adjacent parts of the Midwest Seaway over North America. The Triassic world was a predominantly warm world, the model output for evaporation and precipitation conforming well with the known distributions of evaporites, calcretes and other climatically sensitive facies for that time. The message from the geological record is clear. Through the Phanerozoic, Earth's climate has changed significantly, both on a variety of time scales and over a range of climatic states, usually baldly referred to as "greenhouse" and "icehouse", although these terms disguise more subtle states between these extremes. Any notion that the climate can remain constant for the convenience of one species of anthropoid is a delusion (although the recent rate of climatic change is exceptional). (c) 2006 Elsevier B.V. All rights reserved.

Good governance and the extractive industries in sub-saharan Africa

This article critically examines the challenges that come with implementing the Extractive Industries Transparency Initiative (EITI)a policy mechanism marketed by donors and Western governments as a key to facilitating economic improvement in resource-rich developing countriesin sub-Saharan Africa. The forces behind the EITI contest that impoverished institutions, the embezzlement of petroleum and/or mineral revenues, and a lack of transparency are the chief reasons why resource-rich sub-Saharan Africa is underperforming economically, and that implementation of the EITI, with its foundation of good governance, will help address these problems. The position here, however, is that the task is by no means straightforward: that the EITI is not necessarily a blueprint for facilitating good governance in the region's resource-rich countries. It is concluded that the EITI is a policy mechanism that could prove to be effective with significant institutional change in host African countries but, on its own, it is incapable of reducing corruption and mobilizing citizens to hold government officials accountable for hoarding profits from extractive industry operations.

Biofuel policies in the EU, US and Brazil

The development of biofuels has been one of the most visible and controversial manifestations of the use of biomass for energy. Biofuels policies in the EU, US and Brazil have been particularly important for the development of the industry in these three important markets. All three have used a variety of measures, including consumption or use mandates, tax incentives and import protection to promote the production and use of biofuels. Despite this, it is uncertain whether the EU will achieve its objective of a 10 per cent share for renewables in transport fuels by 2020. The US is also running into difficulties in meeting consumption mandates for biofuels. Questions are being raised about the continuation of tax credits and import protection. Brazil has liberalised its domestic ethanol market and adopted a more market-oriented approach to biofuels policy, but the management of domestic petroleum prices and the inter-relationship between the sugar market and ethanol production are important factors affecting domestic consumption and exports. In both the EU and the US an ongoing debate about the benefits of reliance on biofuels derived from food crops and concern about the efficacy of current biofuels policies may put their future in doubt.

Formation of vesicles through solvent assisted self-assembly of hydrophobic pentapeptides: encapsulation and pH responsive release of dyes by the vesicles

In the biomimetic design two hydrophobic pentapetides Boc-Ile-Aib-Leu-Phe-Ala-OMe ( I) and Boc-Gly-Ile-Aib-Leu-Phe-OMe (II) (Aib: alpha-aminoisobutyric acid) containing one Aib each are found to undergo solvent assisted self-assembly in methanol/water to form vesicular structures, which can be disrupted by simple addition of acid. The nanovesicles are found to encapsulate dye molecules that can be released by the addition of acid as confirmed by fluorescence microscopy and UV studies. The influence of solvent polarity on the morphology of the materials generated from the peptides has been examined systematically, and shows that fibrillar structures are formed in less polar chloroform/petroleum ether mixture and vesicular structures are formed in more polar methanol/water. Single crystal X-ray diffraction studies reveal that while beta-sheet mediated self-assembly leads to the formation of fibrillar structures, the solvated beta-sheet structure leads to the formation of vesicular structures. The results demonstrate that even hydrophobic peptides can generate vesicular structures from polar solvent which may be employed in model studies of complex biological phenomena.

Advanced multivariate analysis to assess remediation of hydrocarbons in soils

Accurate monitoring of degradation levels in soils is essential in order to understand and achieve complete degradation of petroleum hydrocarbons in contaminated soils. We aimed to develop the use of multivariate methods for the monitoring of biodegradation of diesel in soils and to determine if diesel contaminated soils could be remediated to a chemical composition similar to that of an uncontaminated soil. An incubation experiment was set up with three contrasting soil types. Each soil was exposed to diesel at varying stages of degradation and then analysed for key hydrocarbons throughout 161 days of incubation. Hydrocarbon distributions were analysed by Principal Coordinate Analysis and similar samples grouped by cluster analysis. Variation and differences between samples were determined using permutational multivariate analysis of variance. It was found that all soils followed trajectories approaching the chemical composition of the unpolluted soil. Some contaminated soils were no longer significantly different to that of uncontaminated soil after 161 days of incubation. The use of cluster analysis allows the assignment of a percentage chemical similarity of a diesel contaminated soil to an uncontaminated soil sample. This will aid in the monitoring of hydrocarbon contaminated sites and the establishment of potential endpoints for successful remediation.

Terrestrial exposure of oilfield flowline additives diminish soil structural stability and remediative microbial function

Onshore oil production pipelines are major installations in the petroleum industry, stretching many thousands of kilometres worldwide which also contain flowline additives. The current study focuses on the effect of the flowline additives on soil physico-chemical and biological properties and quantified the impact using resilience and resistance indices. Our findings are the first to highlight deleterious effect of flowline additives by altering some fundamental soil properties, including a complete loss of structural integrity of the impacted soil and a reduced capacity to degrade hydrocarbons mainly due to: (i) phosphonate salts (in scale inhibitor) prevented accumulation of scale in pipelines but also disrupted soil physical structure; (ii) glutaraldehyde (in biocides) which repressed microbial activity in the pipeline and reduced hydrocarbon degradation in soil upon environmental exposure; (iii) the combinatory effects of these two chemicals synergistically caused severe soil structural collapse and disruption of microbial degradation of petroleum hydrocarbons.

Hydrocarbon biodegradation and soil microbial community response to repeated oil exposure

Bioremediation strategies continue to be developed to mitigate the environmental impact of petroleum hydrocarbon contamination. This study investigated the ability of soil microbiota, adapted by prior exposure, to biodegrade petroleum. Soils from Barrow Is. (W. Australia), a class A nature reserve and home to Australia’s largest onshore oil field, were exposed to Barrow production oil (50 ml/kg soil) and incubated (25 °C) for successive phases of 61 and 100 days. Controls in which oil was not added at Phase I or II were concurrently studied and all treatments were amended with the same levels of additional nutrient and water to promote microbial activity. Prior exposure resulted in accelerated biodegradation of most, but not all, hydrocarbon constituents in the production oil. Molecular biodegradation parameters measured using gas chromatography–mass spectrometry (GC–MS) showed that several aromatic constituents were degraded more slowly with increased oil history. The unique structural response of the soil microbial community was reflected by the response of different phospholipid fatty acid (PLFA) sub-classes (e.g. branched saturated fatty acids of odd or even carbon number) measured using a ratio termed Barrow PLFA ratio (B-PLFAr). The corresponding values of a previously proposed hydrocarbon degrading alteration index showed a negative correlation with hydrocarbon exposure, highlighting the site specificity of PLFA-based ratios and microbial community dynamics. B-PLFAr values increased with each Phase I and II addition of production oil. The different hydrocarbon biodegradation rates and responses of PLFA subclasses to the Barrow production oil probably relate to the relative bioavailability of production oil hydrocarbons. These different effects suggest preferred structural and functional microbial responses to anticipated contaminants may potentially be engineered by controlled pre-exposure to the same or closely related substrates. The bioremediation of soils freshly contaminated with petroleum could benefit from the addition of exhaustively bioremediated soils rich in biota primed for the impacting hydrocarbons.

Sequential hydrocarbon biodegradation of a soil from arid coastal Australia oil-treated under laboratory controlled conditions

A general consistency in the sequential order of petroleum hydrocarbon reduction in previous biodegradation studies has led to the proposal of several molecularly based biodegradation scales. Few studies have investigated the biodegradation susceptibility of petroleum hydrocarbon products in soil media, however, and metabolic preferences can change with habitat type. A laboratory based study comprising gas chromatography–mass spectrometry (GC–MS) analysis of extracts of oil-treated soil samples incubated for up to 161 days was conducted to investigate the biodegradation of crude oil exposed to sandy soils of Barrow Island, home to both a Class ‘‘A” nature reserve and Australia’s largest on-shore oil field. Biodegradation trends of the hydrocarbon-treated soils were largely consistent with previous reports but some unusual behaviour was recognised both between and within hydrocarbon classes. For example, the n-alkanes persisted at trace levels from day 86 to 161 following the removal of typically more stable dimethyl naphthalenes and methyl phenanthrenes. The relative susceptibility to biodegradation of different di- tri- and tetramethylnaphthalene isomers also showed several features distinct from previous reports. The unique biodegradation behaviour of Barrow Is. soil likely reflects difference in microbial functioning with physiochemical variation in the environment. Correlation of molecular parameters, reduction rates of selected alkyl naphthalene isomers and CO2 respiration values with a delayed (61 d) oil-treated soil identified a slowing of biodegradation with microcosm incubation; a reduced function or population of incubated soil flora might also influence the biodegradation patterns observed.