Comparison of Fenton's Reagent and Ozone Oxidation of Polycyclic Aromatic Hydrocarbons in Aged Contaminated Soils (7 pp)

Background, Aim and Scope   Polycyclic aromatic hydrocarbons (PAHs) are formed as a result of incomplete combustion and are among the most frequently occurring contaminants in soils and sediments. PAHs are of great environmental concern due to their ubiquitous nature and toxicological properties. Consequently, extensive research has been conducted into the development of methods to remediate soils contaminated with PAHs. Fenton's reagent or ozone is the most commonly studied chemical oxidation methods. However, the majority of remediation studies use soils that have been artificially contaminated with either one or a limited number of PAH compounds in the laboratory. Hence, it is essential to extend such studies to soils contaminated with multiple PAHs under field conditions. Objectives   The objective of this study is to investigate the capacity of Fenton's reagent and ozone to degrade PAHs in soils. The soils have been collected from a number of different industrial sites and, therefore, will have been exposed to different PAH compounds in varying concentrations over a range of time periods. The capacity of Fenton's reagent and ozone to degrade PAHs in industrially contaminated soils is compared to results obtained in studies using soils artificially contaminated with PAHs in the laboratory. Materials and Methods: Nine soil samples, contaminated with PAHs, were collected from five different industrial sites in Sweden. For the Fenton's reagent procedure, the pH of the soil slurry samples was adjusted to pH 3 and they were kept at a constant temperature of 70oC whilst H2O2 was added. For the ozone procedure, soil samples were mixed with 50% water and 50% ethanol and kept at a constant temperature of 45 oC. Ozone was then continually introduced to each soil sample over a period of four hours. Following the Fenton's reagent and ozone oxidation procedures, the samples were filtered to isolate the solid phase, which was then extracted using pressurized liquid extraction (PLE). The sample extracts were cleaned up using open columns and then analysed by gas chromatography-mass spectrometry (GC-MS). Results: The relative abundance of the detected PAHs varied between soils, associated with different industries. For example, low molecular weight (LMW) PAHs were more abundant in soil samples collected from wood impregnation sites and high overall PAH degradation efficiencies were observed in soils originating from these sites. In the contaminated soils studied, PAHs were more effectively degraded using Fenton's reagent (PAH degradation efficiency of 40-86%) as opposed to ozone (PAH degradation efficiency of 10-70%). LMW PAHs were more efficiently degraded, using ozone as the oxidizing agent, whereas the use of Fenton's reagent resulted in a more even degradation pattern for PAHs with two through six fused aromatic rings. Discussion: The degradation efficiency for both methods was largely dependent on the initial PAH concentration in the soil sample, with higher degradation observed in highly polluted soils. LMW PAHs are more susceptible to degradation than high molecular weight (HMW) PAHs. As a result of this the relative abundance of large (often carcinogenic) PAHs increased after chemical oxidation treatment, particularly after ozone treatment. Repeated Fenton's reagent treatment did not result in any further degradation of soil PAHs, indicating that residual soil PAHs are strongly sorbed. The effectiveness of the two oxidation treatment approaches differed between industrial sites, thus highlighting the importance of further research into the influence of soil properties on the sorption capacity of PAHs. Conclusions: This study demonstrates that the degree to which chemical oxidation techniques can degrade soil bound PAHs chemical degradation is highly dependent on both the concentration of PAHs in the soils and the compounds present, i.e. the various PAH profiles. Therefore, similarities in the PAH degradation efficiencies in the nine soil samples studied were observed with the two chemical oxidation methods used. However, the degradation performance of Fenton's reagent and ozone differed between the two methods. Overall, Fenton's reagent achieved the highest total PAH degradation due to stronger oxidation conditions. LMW PAHs showed higher susceptibility to oxidation, whereas high molecular weight (HMW) PAHs appear to be strongly sorbed to the soils and therefore less chemically available for oxidation. This study highlights the importance of including soils collected from a range of contaminated sites in remediation studies. Such soil samples will contain PAH contaminants of varying concentrations, chemical and physical properties, and have been aged under field conditions. In addition to the chemical and physical properties of the soils, these factors will all influence the chemical availability of PAHs to oxidation. Recommendations and Perspectives: We recommend including aged contaminated soils in chemical degradation studies. In future chemical remediation work, we intend to investigate the potential influence of the chemical and physical properties of PAHs and soil parameters potential influence on the chemical oxidation efficiency in aged contaminated soils. Due to the vast number of contaminated sites there is a great need of efficient remediation methods throughout the world. This study shows the difficulties which may be experienced when applying remediation methods to a variation of contaminated sites.     

Structural characterization of potato protease inhibitor I (Cv. Bintje) after expression in Pichia pastoris

In the present study the structural properties of potato protease inhibitor 1 (PI-1) were studied as a function of temperature to elucidate its precipitation mechanism upon heating. A cDNA coding for PI-1 from cv. Bintje was cloned and expressed in Pichia pastoris. Using the recombinant PI-1 it was suggested that PI-1 behaves as a hexameric protein rather than as a pentamer, as previously proposed in the literature. The recombinant protein seems either to have a predominantly unordered structure or to belong to the beta-II proteins. Differential scanning calorimetry analysis of PI-1 revealed that its thermal unfolding occurs via one endothermic transition in which the hexameric PI-1 probably unfolds, having a dimer instead of a monomer as cooperative unit. The transition temperature for the recombinant PI-1 was 88 degrees C. Similar results were obtained for a partially purified pool of native PI-1 from cv. Bintje.     

Terrestrial sources of methylmercury in surface waters: The importance of the riparian zone on the Svartberget Catchment

The runoff of methylmercury (MeHg) from forested catchments to surface waters has been identified as a potentially significant input of MeHg to the aquatic ecosystem. Little, however, is known of the processes which control the transfer of MeHg from soils to surface waters. This study investigated the potential terrestrial sources of MeHg in runoff by sampling profiles of soil solution chemistry and determining the flux of water through those profiles into two tributaries on the Svartberget Catchment in northern Sweden. One study profile was from the podzol soil that covers most of the catchment area. The other profiles were taken in the riparian zone of each of the two tributaries. Soil solution was extracted from the soils by centrifugation. High catchment soil solution concentrations of MeHg (>1 ng l^?1) occur in the surface layers of the soil, but overland flow on the catchment is rare. MeHg concentrations in the podzol profile dropped to less than 0.2 ng l^?1 in the mineral soil just 5 cm below the mor layer. In the riparian soil profiles sampled in October, MeHg concentrations were higher (ca. 0.4 ng l^?1), but in a July sampling the concentrations in the riparian profiles were comparable to those in the podzol (i.e. < 0.2 ng l^?1). Very high concentrations of MeHg were found in the streambank sphagnum mosses (>2 ng l^?1) partially submerged within the stream. The concentrations of MeHg observed under the podzol soil were insufficient to sustain the concentration of MeHg in runoff from the forested subcatchments where podzol profiles cover more than 70% of the surface area. The only sources of additional MeHg that lie along major runoff flow pathways are the riparian soils and mosses on the streambanks. It is therefore hypothesized that output of MeHg from the forest areas of the catchment is controlled by the biogeochemical processes in the riparian zone.     

Monitoring ambient ozone with a passive measurement technique method,field results and strategy

A low-cost, accurate and sensitive passive measurement method for ozone has been developed and tested. The method is based on the reaction of ozone with indigo carmine which results in colourless reaction products which are detected spectrophotometrically after exposure. Coated glass filters are mounted in a short polystyrene badge-type vessel in which the diffusion path is restricted by a Teflon membrane filter. From wind tunnel experiments good concentration-independent linearity has been found. The detection limit of the method is about 23 ppbv for 1 hour exposure. Tests with interfering oxidants, such as peroxyacetyl nitrate and NO₂, indicated no significant effects for common ambient conditions. No humidity effect was found when the relative humidity varied from 20 to 80%. The uptake rate of the sampler is dependent on wind velocity. In general an average air velocity of approximately 0.5 m/s is necessary to ensure a stable collection rate of ozone. This implies the necessity to measure wind speed during exposure or to place the samplers in the wind stream of a small fan. The method is suitable for hourly to daily mean measurements of ambient ozone. Under field conditions an accuracy of 11 ± 9% (40 experiments) was established in comparison to a continuous UV photometric monitor.     

Relations between organic carbon and methylmercury in humic rich surface waters from Svartberget catchment in northern Sweden

Monthly sampling of a mire outlet and two tributaries, one of them originating in the mire, on the Svartberget catchment in northern Sweden was performed during one year. The concentration of total organic carbon (TOC) in the three waters was fairly high (10–40 mg/l). Methylmercury (MeHg) was analysed in the original water sample (MeHg-whl) and in the humic fraction (MeHg-hum). The MeHg-hum increased with increasing concentration of humic substances (HS; measured as absorbance at 254 nm) in the water. A seasonal variation of the MeHg-hum/TOC ratio was superimposed on a negative relationship to the water flow, which indicates that the methylation is a slow process which results in a rapid drainage of the storage during periods of high flow. A minimum of the MeHg-whl/TOC ratio observed during the spring flood was followed by a slow increase during the rest of the year.     

Tree species selection for land rehabilitation in Ethiopia: from fragmented knowledge to an integrated multi-criteria decision approach

Dryland regions worldwide are increasingly suffering from losses of soil and biodiversity as a consequence of land degradation. Integrated conservation, rehabilitation and community-based management of natural resources are therefore of vital importance. Local planting efforts should focus on species performing a wide range of functions. Too often however, unsuitable tree species are planted when both ecological suitability for the targeted area or preferences of local stakeholders are not properly taken into account during selection. To develop a decision support tool for multi-purpose species selection, first information needs to be pooled on species-specific ranges, characteristics and functions for a set of potentially valuable species. In this study such database has been developed for the highly degraded northern Ethiopian highlands, using a unique combination of information sources, and with particular attention for local ecological knowledge and preferences. A set of candidate tree species and potentially relevant criteria, a flexible input database with species performance scores upon these criteria, and a ready-to-use multi-criteria decision support tool are presented. Two examples of species selection under different scenarios have been worked out in detail, with highest scores obtained for Cordia africana and Dodonaea angustifolia, as well as Eucalyptus spp., Acacia abyssinica, Acacia saligna, Olea europaea and Faidherbia albida. Sensitivity to criteria weights, and reliability and lack of knowledge on particular species attributes remain constraints towards applicability, particularly when many species are jointly evaluated. Nonetheless, the amount and diversity of the knowledge pooled in the presented database is high, covering 91 species and 45 attributes.     

Effects of an anthelmintic treatment programme on sheep productivity in the Middle Atlas,Morocco

Summary This study evaluated the production advantages of the strategic anthelmintic treatment of both lambs and ewes in an area endemic for gastro-intestinal nematodes, lungworms and liver flukes. The liver fluke infections were generally chronic. The lambs were treated with albendazole (SmithKline Beecham), fenbendazole (Hoechst Roussel) or a vitamin supplement and their weight gains were followed over the next 7 months. The control group, which received a vitamin supplement only, gained 6·67 kg from July to January. The group that received fenbendazole, an anthelmintic with no activity against liver flukes, gained 10·42 kg over the study period. The third group which received albendazole, an anthelmintic with efficacy against liver flukes, gained 13·07 kg over the same period. Lamb deaths apparently due to liver flukes were 12, 4, and zero for the control, fenbendazole and albendazole groups, respectively. Similar advantages were observed in the ewes. Deaths were 16, 8, and zero in the control, fenbendazole and albendazole groups, respectively. The lambing rate in the control groupswas significantly lower than that in either of the 2 treated groups. The number of services per conception was significantly lower in the albendazole treated group than that in either of the other groups. These studies demonstrated the advantages of anthelmintic treatment in sheep in a helminth endemic area. While removing gastro-intestinal nematodes and lungworms improved production, the additional removal of liver flukes enhanced production gains as well as reducing deaths.

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Resumen Este estudio evaluó las ventajas de un tratamiento estratégico en corderos y ovejas en un área endémica de parásitos gastrointestinales, pulmonares y hepáticos. La infección con fasciola era crónica. Los corderos fueron tratados con albendazole (Smithkline Beecham), fenbendazole (Hoechst Roussel) o un suplemento vitamínico; el peso fue consignado durante 7 meses seguidos. El grupo control que recibió el suplemento vitamínico, ganó 6·67 kg desde julio hasta enero. El grupo que recibió fenbendazole, antihelmíntico sin acción contra la fasciola, ganó 10·42 kg durante el período de estudio. El tercer grupo que recibió albendazole, un antihelmíntico eficaz contra la fascioliasis, ganó 13·7 kg durante el mismo período. La mortalidad de los corderos aparentemente debida a fascioliasis fue de 12 animales, 4 animales y cero animales, en el grupo control, en el tratado con fenbendazole y en el tratado con albendazole, respectivamente. En ovéjas, las ventajas fueron similares. La mortalidad por fascioliasis fue de 16 animales, 8 animales y cero animales, en el grupo control, en el tratado con fenbendazole y en el tratado con albendazole, respectivamente. La tasa de pariciones en el grupo control, fue significativamente más baja, que aquella de los grupos tratados. El número de servicios por concepción fue menor en el grupo tratado con albendazole. Estos estudios demostraron, la ventaja de los tratamientos antihelmínticos en ovejas en áreas endémicas. Mientras que el tratamiento contra parásitos gastrointestinales y pulmonares mejoró la producción, el tratamiento contra fasciola mejoró las ganancias de peso y redujo las muertes.

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Résumé Cette étude évalue les avantages en matière de production d’une stratégie de traitements anthelminthiques des brebis et des agneaux dans une zone endémique pour les nématodes gastro-intestinaux, les Fasciola et les strongles pulmonaires. Les infections à Fasciola ont généralement un caractère chronique. Les agneaux ont été traités soit à l’albendazole (SmithKline, Beecham) ou au fenbendazole (Hoechst Roussel) ou avec un complément vitaminé. Leur gain de poids ont été suivis pendant les sept mois suivants. Le groupe des témoins qui n’a re?u qu’un complément vitaminé a gagné 6,67 kg de juillet à janvier. Celui traité au fenbendazole, anthelminthique dépourvu d’activité contre les douves a progressé de 10,42 kg pendant la période d’étude. Le troisième groupe a été traité à l’albendazole, produit actif contre les Fasciola. Il a gagné quant à lui 13,07 kg au cours du même laps de temps. La mortalité des agneaux, due apparemment aux douves a été pour les groupes témoins et fenbendazole et albendazole respectivement de 12,4 et zéro. Des avantages identiques ont été observés pour les brebis dont la mortalité a été de 16,8 et zéro respectivement pour les lots témoins et fenbendazole et albendazole. Le taux d’agnelage dans le groupe témoin a été significativement plus bas que celui de l’un et de l’autre des deux groupes traités. Le nombre d’accouplements par conception était significativement plus bas dans le lot traité à l’albendazole que dans n’importe lequel des autres lots. Ces facteurs confirment les avantages d’un traitement anthelminthique chez les ovins vivants dans une région de parasitisme endémique. Tandis que la production est améliorée par la suppression des nématodes gastro-intestinaux et des strongles pulmonaires, la disparition complémentaire des douves accro?t les gains de production au même titre qu’elle réduit la mortalité.

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This work was supported in part by the International Foundation for Science (Stockholm).     

Foaming properties of wheat gliadin

We studied gliadin solubility, surface tension and foam behavior, and the presence of different gliadin types in gliadin aqueous solutions and foams as a function of pH. Gliadin has excellent foaming properties only at neutral and alkaline pH. Its solubility is minimal near neutral pH, while almost complete at acidic and alkaline pH. Surface tensions of gliadin solutions are minimal around neutral pH, higher at alkaline pH, and highest at acidic pH, which corresponds well with their respective foaming properties. Foams at acidic and alkaline pH values are enriched in γ-gliadin, while foams at pH 8.0 have a similar distribution of α- and γ-gliadins. Thus, γ-gliadin predominantly contributes to the foaming properties of gliadin. The poor foaming properties of gliadin at pH 2.0 improve in the presence of 0.25 and 1.0% NaCl. It follows that the presence of positively charged amino acid residues hinders the formation of stable foam at acidic pH.     

Kinetics of heat-induced polymerization of gliadin

The kinetics of heat-induced polymerization of gliadin, that is, a mixture of monomeric wheat storage proteins, was studied using a model system. Samples were heated at pH 6.0 and 8.0 at 110, 120, and 130 °C for up to 240 min, and their extractabilities were compared under nonreducing and reducing (with 1% dithiothreitol) conditions. Extraction media were sodium dodecyl sulfate (SDS) containing buffer (pH 6.8, SDS buffer) and/or 70% ethanol. Gliadin cross-linking mainly resulted from intermolecular disulfide (SS) bond formation. At higher temperatures and, preferably, alkaline pH, intramolecular SS bonds in gliadin underwent β-elimination reactions, leading to the formation of dehydroalanine (DHA) and free sulfhydryl (SH) groups. The latter interchanged rapidly with SS bonds, leading to intermolecular SS bonds and gliadin extractability loss. When free SH groups had been formed, gliadin extractability in SDS buffer decreased following first-order reaction kinetics, the reaction rate constant of which increased with temperature and pH. Furthermore, the extractabilities of α- and γ-gliadin in 70% ethanol decreased according to first-order reaction kinetics. ω-Gliadin extractability was much less affected. Under the experimental conditions, gliadin polymerization through SH-SS interchange occurred much more rapidly than β-elimination of cystine.