A preliminary investigation of the release of oil from contaminated clays and other fine-grained sediments during consolidation

Fine-grained sediments on land, or in a freshwater or marine environment, may become contaminated with a wide range of pollutants including hydrocarbons. This paper is concerned with preliminary studies of the mobilization and transportation of hydrocarbons, during the process of consolidation, to adjacent sediments or water bodies. A modified Rowe Cell was used to measure the consolidation properties of prepared kaolinite and bentonite clay-water slurries, with and without the addition of oil, along with hydrocarbon-bearing drill-cuttings samples taken from the sea-bed adjacent to two North Sea oil-well platforms. The consolidation properties of the kaolinite and bentonite clay slurries were little altered by the addition of oil, which was present at concentrations of between 8073 and 59 572 mg kg(-1). During each consolidation stage, samples of the expelled pore-fluids were collected and analysed for oil content. These values were very low in comparison with the original oil concentration in the samples and changed little between each consolidation stage. Analysis of the slurry samples both before and after consolidation confirms that, proportionally, little oil is removed as a result of consolidation. The implication of these results is that, for the range of samples tested, the very high hydraulic gradients and particle rearrangements that occur during the process of consolidation are capable of releasing only proportionally small amounts of oil bound to the fine-grained clay and silt particles.

Reduction of arsenic uptake by lettuce with ferrous sulfate applied to contaminated soil

Soil contamination by arsenic (As) presents a hazard in many countries and there is a need for techniques to minimize As uptake by plants. A proposed in situ remediation method was tested by growing lettuce (Lactuca sativa L. cv. Kermit) in a greenhouse pot experiment on soil that contained 577 mg As kg(-1), taken from a former As smelter site. All combinations of iron (Fe) oxides, at concentrations of 0.00, 0.22, 0.54, and 1.09% (w/w), and lime, at concentrations of 0.00, 0.27, 0.68, and 1.36% (w/w), were tested in a factorial design. To create the treatments, field-moist soil, commercial-grade FeSO4, and ground agricultural lime were mixed and stored for one week, allowing Fe oxides to precipitate. Iron oxides gave highly significant (P < 0.001) reductions in lettuce As concentrations, down to 11% of the lettuce As concentration for untreated soil. For the Fe oxides and lime treatment combinations where soil pH was maintained nearly constant, the lettuce As concentration declined in an exponential relationship with increasing FeSO4 application rate and lettuce yield was almost unchanged. Iron oxides applied at a concentration of 1.09% did not give significantly lower lettuce As concentrations than the 0.54% treatment. Simultaneous addition of lime with FeSO4 was essential. Ferrous sulfate with insufficient lime lowered soil pH and caused mobilization of Al, Ba, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, and Zn. At the highest Fe oxide to lime ratios, Mn toxicity caused severe yield loss.

Complexation of copper by sewage sludge-derived dissolved organic matter: Effects on soil sorption behaviour and plant uptake

The complexation of Cu by sewage sludge-derived dissolved organic matter (SSDOM) is a process by which the environmental significance of the element may become enhanced due to reduced soil sorption and, hence, increased mobility. The work described in this paper used an ion selective electrode procedure to show that SSDOM complexation of Cu was greatest at intermediate pH values because competition between hydrogen ions and Cu for SSDOM binding sites, and between hydroxyl ions and SSDOM as Cu ligands, was lowest at such values. Batch sorption experiments further showed that the process of Cu complexation by SSDOM provided an explanation for enhanced desorption of Cu from the solid phase of a contaminated, organic matter-rich, clay loam soil, and reduced adsorption of Cu onto the solid phase of a sandy loam soil. Complexation of Cu by SSDOM did not affect uptake of Cu by spring barley plants, when compared to free ionic Cu, in a sand-culture pot experiment. However, it did appear to lead to greater biomass yields of the plant; perhaps indicating that the Cu-SSDOM complex had a lower toxicity towards the plant than the free Cu ion.

Biosensor-based diagnostics of contaminated groundwater: assessment and remediation strategy

Shallow groundwater beneath a former airfield site in southern England has been heavily contaminated with a wide range of chlorinated solvents. The feasibility of using bacterial biosensors to complement chemical analysis and enable cost-effective, and focussed sampling has been assessed as part of a site evaluation programme. Five different biosensors, three metabolic (Vibrio fischeri, Pseudomonas fluorescens 10568 and Escherichia coli HB101) and two catabolic (Pseudomonas putida TVA8 and E. coli DH5alpha), were employed to identify areas where the availability and toxicity of pollutants is of most immediate environmental concern. The biosensors used showed different sensitivities to each other and to the groundwater samples tested. There was generally a good agreement with chemical analyses. The potential efficacy of remediation strategies was explored by coupling sample manipulation to biosensor tests. Manipulation involved sparging and charcoal treatment procedures to simulate remediative engineering solutions. Sparging was sufficient at most locations. (C) 2004 Elsevier Ltd. All rights reserved.

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.

Fate of prions in soil: Longevity and migration of recPrP in soil columns

Research into transmissible spongiform encephalopathy (TSE) diseases has become a high priority worldwide in recent years yet remarkably little is known about the behaviour of TSE infectivity in the environment. The resilience and stability of prion proteins could lead to soils becoming a potential reservoir of TSE infectivity as a result of contamination from activities such as infected carcass burial or the dispersion of effluents from slaughter houses, or by contamination of pastures by infected animals, (e.g. scrapie in sheep). Knowledge of the fate of prion proteins in soils, and associated physico-chemical conditions which favour migration, can be used to help prevent re-infection of animals through grazing, to protect watercourses and develop good management practices. In two consecutive experiments of 9 and 6 months, the migration of recombinant ovine PrP (recPrP) in soil columns was followed under contrasting levels of microbial activity (normal versus reduced), under varying regimes of soil water content and redox potential, and in two different soil types (loamy sand and clay loam). At each analysis time (1, 3, 6 or 9 months), in both soil types, full-length recPrP was detected in the original contaminated layer, indicating the resilience and stability of recPrP under varied soil conditions, even in the presence of active soil microbial populations. Evidence of protein migration was found in every soil column at the earliest analysis time (1 or 3 months), but was restricted to a maximum distance of 1 cm, indicative of limited initial mobility in soils followed by strong adsorption over the following days to weeks. The survival of recPrP in the soil over a period of at least 9 months was demonstrated. In this study, recPrP was used as an indicator for potential TSE infectivity, although infectivity tests should be carried out before conclusions can be drawn regarding the infection risk posed by prions in soil. However, it has been demonstrated that soil is likely to act as a significant barrier to the dispersion of contaminated material at storage or burial sites. (c) 2007 Elsevier Ltd. All rights reserved.

A preliminary investigation into the use of ochre as a remedial amendment in arsenic-contaminated soils

Ochre is an unwanted waste product that accumulates in wetlands and streams draining abandoned coal and metal mines. A potential commercial use for ochre is to remediate As contaminated soil. Arsenic contaminated soil (605 mg kg(-1)) was mixed with different ochres (A, B and C) in a mass ratio of 1:1 and shaken in 20 mL of deionised water. After 72 h As concentration in solution was ca. 500 mu g kg(-1) in the control and 1-2.5 mu g kg(-1) in the ochre treated experiments. In a second experiment soil:ochre mixtures of 0.05-1:1 were shaken in 20 mL of deionised water for 24 h. For Ochres A and C, as Solution concentration was reduced to ca. 1 mu gkg(-1) by 0.2-1:1 ochre:soil mixtures. For Ochre B, as concentration only reached ca. 1 mu g kg(-1) in the 1:1 ochre:soil inix. Sorption of As was best modelled by a Freundlich isotherm using As sorption per mass of goethite in the ochre (log K= 1.64, n = 0.79, R-2 = 0.76, p <= 0.001). Efficiency of ochre in removing As from solution increased with increasing total Fe, goethite, citrate dithionite extractable Fe and surface area. (c) 2005 Elsevier Ltd. All rights reserved.

Characterization and identification of mixed-metal phosphates in soils: the application, of Raman spectroscopy

The development of protocols for the identification of metal phosphates in phosphate-treated, metal-contaminated soils is a necessary yet problematical step in the validation of remediation schemes involving immobilization of metals as phosphate phases. The potential for Raman spectroscopy to be applied to the identification of these phosphates in soils has yet to be fully explored. With this in mind, a range of synthetic mixed-metal hydroxylapatites has been characterized and added to soils at known concentrations for analysis using both bulk X-ray powder diffraction (XRD) and Raman spectroscopy. Mixed-metal hydroxylapatites in the binary series Ca-Cd, Ca-Pb, Ca-Sr and Cd-Pb synthesized in the presence of acetate and carbonate ions, were characterized using a range of analytical techniques including XRD, analytical scanning electron microscopy (SEM), infrared spectroscopy (IR), inductively coupled plasma-atomic emission spectrometry (ICP-AES) and Raman spectroscopy. Only the Ca-Cd series displays complete solid solution, although under the synthesis conditions of this study the Cd-5(PO4)(3)OH end member could not be synthesized as a pure phase. Within the Ca-Cd series the cell parameters, IR active modes and Raman active bands vary linearly as a function of Cd content. X-ray diffraction and extended X-ray absorption fine structure spectroscopy (EXAFS) suggest that the Cd is distributed across both the Ca(1) and Ca(2) sites, even at low Cd concentrations. In order to explore the likely detection limits for mixed-metal phosphates in soils for XRD and Raman spectroscopy, soils doped with mixed-metal hydroxylapatites at concentrations of 5, 1 and 0.5 wt.% were then studied. X-ray diffraction could not confirm unambiguously the presence or identity of mixed-metal phosphates in soils at concentrations below 5 wt.%. Raman spectroscopy proved a far more sensitive method for the identification of mixed-metal hydroxylapatites in soils, which could positively identify the presence of such phases in soils at all the dopant concentrations used in this study. Moreover, Raman spectroscopy could also provide an accurate assessment of the degree of chemical substitution in the hydroxylapatites even when present in soils at concentrations as low as 0.1%.

Brief and precarious lives: Infant mortality in contrasting sites from medieval and post-medieval England (AD 850-1859)

This study compares the infant mortality profiles of 128 infants from two urban and two rural cemetery sites in medieval England. The aim of this paper is to assess the impact of urbanization and industrialization in terms of endogenous or exogenous causes of death. In order to undertake this analysis, two different methods of estimating gestational age from long bone lengths were used: a traditional regression method and a Bayesian method. The regression method tended to produce more marked peaks at 38 weeks, while the Bayesian method produced a broader range of ages and were more comparable with the expected "natural" mortality profiles. At all the sites, neonatal mortality (28-40 weeks) outweighed post-neonatal mortality (41-48 weeks) with rural Raunds Furnells in Northamptonshire, showing the highest number of neonatal deaths and post-medieval Spitalfields, London, showing a greater proportion of deaths due to exogenous or environmental factors. Of the four sites under study, Wharram Percy in Yorkshire showed the most convincing "natural" infant mortality profile, suggesting the inclusion of all births (i.e., stillbirths and unbaptised infants).

The social life of ruins: sites of memory and the politics of a Zimbabwean periphery

This article explores conflicts over a series of ruins located within Zimbabwe's flagship National Park. The relics have long been regarded as sacred places by local African communities evicted from their vicinity, and have come to be seen as their ethnic heritage. Local intellectuals' promotion of this heritage was an important aspect of a defensive mobilization of cultural difference on the part of a marginalized minority group. I explore both indigenous and colonial ideas about the ruins, the different social movements with which they have been associated and the changing social life they have given the stone relics. Although African and European ideas sometimes came into violent confrontation - as in the context of colonial era evictions - there were also mutual influences in emergent ideas about tribe, heritage and history. The article engages with Pierre Nora's notion of 'sites of memory', which has usefully drawn attention to the way in which ideas of the past are rooted and reproduced in representations of particular places. But it criticizes Nora's tendency to romanticize pre-modern 'memory', suppress narrative and depoliticize traditional connections with the past. Thus, the article highlights the historicity of traditional means of relating to the past, highlighting the often bitter and divisive politics of traditional ritual, myth, kinship, descent and 'being first'. It also emphasizes the entanglement of modern and traditional ideas, inadequately captured by Nora's implied opposition between history and memory. (c) 2005 Elsevier Ltd. All rights reserved.

Availability of heavy metals for uptake by Salix viminalis on a moderately contaminated dredged sediment disposal site

Extractability of Cd. Cr, Cu, Ni, Pb, and Zn in a dredged sediment disposal site was assessed using single extraction Procedures (H2O; 0.01 M CaCl2; 1 M NH4OAc NH4OAc-EDTA. CaCl2-TEA-DTPA). Only Cd and Zn were Found to exceed statutory threshold values for total content. The field was planted with Salix viminalis "Orm" and accumulation of heavy metals in bark, leaves, roots, and wood was evaluated at seven sampling locations along an observed gradient in texture and pollution. Biomass production was high, ranging from 13.2 to 17.8 t ha(1) y(1) dry weight. Metal accumulation in aboveground Plant parts Was low. amounting to the following annually extracted mass or metals per ha: 5034 g Zn, 83 g Cd. W g Cu. 83 g Pb, 12 g Ni and 6 g Cr. The use of accumulating clones and the use of soil amendments might enhance extraction efficiency in future research. (C) 2005 Elsevier Ltd. All rights reserved.

Effect of pH on the development of acidic sites in clayey and sandy loam Oxisol from the Cerrado Region, Brazil

Titration curves were determined for soil from horizon samples of a clayey and a sandy loam Oxisol by (a) adding NaOH to soil suspensions and (b) incubating moist soils with Ca(OH)(2). The organic fraction was primarily responsible for buffering in both soils. Humic acids were more important than fulvic acids in buffering against NaOH additions. With Ca(OH)(2), greater buffer capacities were found due to carboxyl sites, primarily on fulvic acids, becoming complexed with Ca2+ so that in the clay soil humic and fulvic acids were equally important as buffering components while fulvic acids were more important in the sandy loam soil. The buffer capacity of organic matter against Ca(OH)(2) additions was 1.1 mol(c) kg(-1) pH(-1). In the incubated soils, exchangeable cations were also determined and changes in the amounts of exchangeable and non-exchangeable Ca2+ acidity and effective cation exchange capacity were calculated. Up to half the added Ca2+ became complexed and was nonexchangeable. Aluminum complexed by organic matter appears to be an important buffering component, together with non exchangeable H+. With the increase of pH the dissociated sites from the carboxyl groups could complex Ca2+. (c) 2005 Elsevier B.V. All rights reserved.