Biological remediation of explosives and related nitroaromatic compounds

Nitroaromatics form an important group of recalcitrant xenobiotics. Only few aromatic compounds, bearing one nitro group as a substituent of the aromatic ring, are produced as secondary metabolites by microorganisms. The majority of nitroaromatic compounds in the biosphere are industrial chemicals such as explosives, dyes, polyurethane foams, herbicides, insecticides and solvents. These compounds are generally recalcitrant to biological treatment and remain in the biosphere, where they constitute a source of pollution due to both toxic and mutagenic effects on humans, fish, algae and microorganisms. However, relatively few microorganisms have been described as being able to use nitroaromatic compounds as nitrogen and/or carbon and energy source. The best-known nitroaromatic compound is the explosive TNT (2,4,6-trinitrotoluene). This article reviews the bioremediation strategies for TNT-contaminated soil and water. It comes to the following conclusion: The optimal remediation strategy for nitroaromatic compounds depends on many site-specific factors. Composting and the use of reactor systems lend themselves to treating soils contaminated with high levels of explosives (e.g. at former ammunition production facilities, where areas with a high contamination level are common). Compared to composting systems, bioreactors have the major advantage of a short treatment time, but the disadvantage of being more labour intensive and more expensive. Studies indicate that biological treatment systems, which are based on the activity of the fungus Phanerochaete chrysosporium or on Pseudomonas sp. ST53, might be used as effective methods for the remediation of highly contaminated soil and water. Phytoremediation, although not widely used now, has the potential to become an important strategy for the remediation of soil and water contaminated with explosives. It is best suited where contaminant levels are low (e.g. at military sites where pollution is rather diffuse) and where larger contaminated surfaces or volumes have to be treated. In addition, phytoremediation can be used as a polishing method after other remediation treatments, such as composting or bioslurry, have taken place. This in-situ treatment method has the advantage of lower treatment costs, but has the disadvantage of a considerable longer treatment time. In order to improve the cost-efficiency, phytoremediation of nitroaromatics (and other organic xenobiotics) could be combined with bio-energy production. This requires, however, detailed knowledge on the fate of the contaminants in the plants as well as the development of efficient treatment methods for the contaminated biomass that minimise the spreading of the contaminants into the environment during post harvest treatment.     

Boating and navigation activities influence the recruitment of fish in a Baltic Sea archipelago area

We studied the effects of boating and navigation activities on the recruitment of coastal fish in the Stockholm archipelago in the NW Baltic proper. The impacts were quantified by sampling metamorphosed young-of-the-year (Y-O-Y) fish in inlets adjacent to i) routes for medium-sized passenger ferries; ii) berths (small marinas) with small boats; and iii) references. Species with high preference for vegetation were negatively influenced by boating and navigation activities and species with low preference positively influenced. Pike (Esox lucius) Y-O-Y were significantly more abundant in reference areas, while bleak (Alburnus alburnus) were more abundant in dredged marinas. No statistically significant patterns were identified for perch (Perca fluviatilis) although there was a trend of low abundance along ferry routes. Many species of nearshore fishes are dependent on submerged vegetation as spawning and larval substrate, structural refuge and feeding habitat. Our results suggest that the negative effects from boating and navigation activities on the coverage and height of vegetation, especially on species of Chara and Potamogeton spp., may contribute to changes in the Y-O-Y fish community.     

Kinetics of carbosulfan hydrolysis to carbofuran and the subsequent degradation of this last compound in irrigated rice fields

The objectives of this work were estimate the reaction rates of hydrolysis of carbosulfan to carbofuran and subsequent degradation of this last compound in irrigated rice fields, and the respective half life, in aquatic environment and soil solution, by mean of numerical solution of differential ordinary linear equations system that describes the kinetics of insecticide concentrations. The results indicated that the carbosulfan and carbofuran have low persistence in water and medium persistence in soil solution of tropical irrigated rice fields. However, both compounds can be found in laminar water and soil solution in concentration above environmental and human safety limits.     

Online hourly determination of 62 VOCs in ambient air: system evaluation and comparison with another two analytical techniques

This paper presents results of the processing and validation of data collected by an automatic gas chromatograph (AGC). This system was used to monitor 62 volatile organic compounds (VOCs) in urban air in the Basque Country, Spain. The nonpolar compounds (C2-C10) identified-paraffins, olefins, aromatics, and chlorinated compounds-accounted for 88% of the mass of total non-methane hydrocarbons (TNMHCs) in ambient air. The evaluation of linearity, precision, detection limits (DLs), and stability of retention times (RTs) indicates that the equipment is suitable for measuring ambient air automatically for prolonged periods (6 months). The calibration of the equipment using response factors calculated on the basis of the effective carbon number (ECN) showed variations of over 10% for acetylene, isoprene, and n-hexane. The results provided by the automatic chromatograph correlated significantly with simultaneous results from other widely used techniques for determining VOCs in ambient air: (1) portable GC, equipped with photoionization detector (PID), and (2) active adsorption on Tenax-TA followed by thermal desorption and chromatographic analysis.     

Use of treated bark for the removal of lipids from water

Raw, biologically treated bark and bark impregnated with transition metal ions were used to retain the lipids from synthetic emulsions. Several experimental parameters affecting the lipid removal efficiency (RE) were studied (initial concentration of lipids, temperature, time, pH, carboxylic acid chain length, etc.). Saturated bark was characterized using Fourier transform infrared (FTIR) spectroscopy and light microscopy, and the treated bark wetting index was determined. Results show that lipid removal can exceed 95% of the initial concentration at a pH lower than 7. The uptake of lipids by these sorbents varied from 0.2 to 2.5 g/g of dry bark. Trials for regenerating the sorbent saturated by lipids allowed the recovery of approximately 95% of lipids. The calorific value of the saturated bark was approximately 79% that of domestic fuel and can be considered as an energy source, thus avoiding its waste disposal. These results may upgrade the treatment of wastewater generated by several industrial sectors, such as the food industry, surface treatment, and so on.     

Interaction of limestone grains and acidic solutions from the oxidation of pyrite tailings

To characterise the coatings formed and to analyse element partitioning between the aqueous and solid phase, suspensions were prepared with four grain sizes of limestone and three different amounts of acidic solution from oxidized pyrite tailings. In all cases, red coatings with three different layers covered the grain surface, sealing off the acidic solution. The inner layer was composed mainly of basaluminite, the middle layer of schwertmannite, and the outer layer of gypsum and jarosite. Zn, Cd and Tl were co-precipitated by Fe and Al; As and Pb were co-precipitated almost completely by Fe; and Cu formed mainly Cu sulphates. All trace elements reached almost total precipitation at pH 6.3, but the precipitation of As and Pb tended to decrease as the pH rose. Consequently, liming should be calculated so that the soil pH does not exceed 6.3. This calculation should take into account that the armouring of the limestone grains can cause underestimations in the amount of liming material needed.     

Spatial variation of mercury levels in nesting Bonelli's eagles from Southwest Portugal: effects of diet composition and prey contamination

Mercury (Hg) was determined in adult Bonelli's eagles (Hieraaetus fasciatus) and their avian prey, from samples of feathers collected between 1992 and 2001 at the nesting sites of 21 pairs in Southwest Portugal. Eagle Hg levels showed great variation, reflecting primarily differences in diet composition and food chain biomagnification. Concentrations were positively correlated with the dietary proportion of insectivorous and omnivorous birds (e.g. egrets, corvids and thrushes), with very low levels for pairs feeding mainly on herbivores (e.g. rabbits, pigeons and partridges). Differences in prey contamination among breeding territories added to dietary effects in determining variation of Hg levels in eagles, shaping a spatial pattern that was largely consistent with a source of contamination in a coal-burning power-plant lying upwind of the study area. Despite this presumed contamination, Hg levels seemed to be of little concern to this eagle population, though there might be subtle deleterious effects on the reproductive output of a few pairs. This study emphasizes the need to account for dietary effects when biomonitoring Hg contamination using birds of prey.     

Oxygen levels versus chemical pollutants: do they have similar influence on macrofaunal assemblages? A case study in a harbour with two opposing entrances

Generally, harbours are polluted zones characterised by low values of hydrodynamism and oxygen in the water column and high concentrations of pollutants in sediments. The harbour of Ceuta, North Africa, has an unusual structure; it is located between two bays connected by a channel, which increases the water movement and exchange in the harbour, maintaining moderate oxygen levels in the water-sediment interface. Nevertheless, high concentration of organic matter, nutrients and heavy metals were measured in sediments from this harbour. Under these unusual conditions (high levels of pollution but total saturation of oxygen in the water column) we studied the responses of soft-bottom macrobenthic communities using uni and multivariate analyses. The number of species was similar inside and outside the harbour but the species composition differed between internal and external stations; oxygen levels seem to control the "quantity" of species whereas pollutants control the "quality" of them.     

Catalytic NO(chi) reduction with simultaneous dioxin and furan oxidation

The engineering, construction, performance and running costs of a catalytic flue gas cleaning component in the low dust area of a municipal waste incinerator is discussed. For this purpose, the case study of a Flemish incineration plant is presented, covering the history, the design procedure of the catalyst, relevant process data and the financial aspects. A reliable PCDD/F-destruction by means of oxidation by the catalyst to typical values of 0.001 ng TEQ/Nm3 has been demonstrated. At the same time, NO(chi)- and CO-emissions are reduced by 90% and 20% to about 50 mg/N m3 andbelow 10 mg/N m3, respectively.     

Study of fractionation and potential mobility of metal in sludge from pyrite mining and affected river sediments: changes in mobility over time and use of artificial ageing as a tool in environmental impact assessment

Sludge from mining exploitation can be a source of land and water contamination in the adjacent zone. Accidents such as the break of waste mining pools in the Aznalcollar Mine (Seville, Spain) in 1998 produce important ecological disasters. In this work is presented a study of the evolution of aqua regia leachable concentration and mobility of metals in sediment samples of Guadiamar River basin from the accident date up to 2001. The application of BCR standard extraction procedures provides valuable information about the mobility and toxicity of the spill and the metal mobility in Guadiamar River polluted sediments. As a rule, themobility of several metals in the initial sludge (sulphides) is low, except for copper. Otherwise, the results of aqua regia leachable concentration and mobility of metal obtained for sediments samples indicate that the cleaning and inertisation works carried out in the zone have been adequate but insufficient, being the metal levels observed in the zone are higher than natural levels. To establish the initial impact of the spill and the mobility changes with time, mineralogical composition of the pyritic sludge and its evolution after the natural weathering and after the induction, of accelerated ageing processes by light and temperature was studied in the laboratory. Oxidation of initial sulphides to sulphates was observed. Both environmental and laboratory oxidation of the metallic sulphides increase the mobility of all metals, especially of copper, zinc and lead. The proposed laboratory procedure allows to predict the changes in mobility and therefore in toxicity that can occur at short or long term after exposure of sludge at environ-mental conditions. The mobility results in sludge and sediment samples are interpreted in terms of the mineral composition of the samples.