Ecosystems for future generations

Environmental Science and Pollution Research -     

Source diagnostic and weathering indicators of tar balls utilizing acyclic, polycyclic and S-heterocyclic components

This study represents a forensic chemical analysis to define the liability for the coastal bitumens polluting the beaches of the Mediterranean city of Alexandria. Six tar balls collected from several locations along the coast of the city were analyzed for their acyclic and polycyclic hydrocarbons as well as sulfur heterocycles using GC/FID, GC/AED and gas chromatography/mass spectrometry techniques. The analysis of one Egyptian crude oil is also included as a possible source oil. The tar ball samples were at early stages of weathering. Based on the GC traces and biomarker signatures, the tar balls could be genetically different. One sample collected from the Eastern Harbor region appears to be a Bunker C type fuel produced from Egyptian crudes. The refining process has removed the low molecular weight components. On the other hand, the wide n-alkane distribution together with the absence of an unresolved complex mixture suggests that crude oils probably from tank washings, ballast discharges or accident spills from tankers could have contributed significantly to the other tar ball samples. The distribution of source specific hopane and sterane markers revealed that the tar samples probably originate from different oil fields.     

Solvent and surfactant enhanced solubilization, stabilization, and degradation of amitraz

In an effort to help with the development of effective dip vat management and waste disposal strategies this study determined how solution properties such as pH, buffer composition, ionic strength, temperature, solubility in organic solvents and the addition of commonly used solubilizing agents influenced the hydrolysis of amitraz. Amitraz degrade by means of hydrolysis described by a pseudo-first order rate process and a type ABCD pH rate profile. Hydrolysis increased with temperature and was fastest at low pH, slowest at neutral to slightly alkaline pH, and slightly increased above pH 10. However, buffer concentration and ionic strength influenced the hydrolysis rate and had to be accounted for before constructing a pH rate profile. Hydrolysis seems to depend on the dielectric constant of solvent mixtures and was fastest in water, slower in propylene glycol and ethanol solutions, and slowest in DMSO mixtures. In surfactant solutions, anionic micelles enhanced and cationic micelles retarded the hydrolysis rate. The magnitude of micellar effects decreased with increasing concentrations of the surfactants. The increased solubility and faster hydrolysis of amitraz in the sodium lauryl sulfate solutions showed that anionic surfactants potentially could be used for cleaning up amitraz spills, because it both solubilized the drug and catalyzed hydrolysis.     

Effects of storage method and duration on the toxicity of marine sediments to embryos of Crassostrea gigas oysters

The objective of laboratory sediment bioassays is to estimate in situ toxicity. This goal is difficult to achieve, as one of the main limitations of sediment toxicity tests is disruption of sediment geochemistry during sampling, handling and preservation. The effects of storage on the estimation of marine sediment toxicity to Crassostrea gigas embryos and larvae were investigated. Three storage methods and four storage periods were compared with three different sediment types contaminated by heavy metals, polycyclic aromatic hydrocarbons (PAHs) and both contaminants. Freezing and freeze-drying considerably increased the toxicity of decanted sediments and their elutriates as compared to the toxicity obtained with fresh sediments. Concerning the elutriates, the toxicity found with frozen and freeze-dried sediments was correlated with DOC, ammonia and PAH contents. However, the toxicity of fresh sediments kept at 4 degrees C increased with increasing duration of storage and was also correlated with the amount of ammonia in the elutriates.     

Spatio-temporal behaviour and mass balance of fluorine in forest soils near an aluminium smelting plant: short- and long-term aspects

With the help of a large number of monitoring sites, the behaviour of F in forested ecosystems of a formerly polluted area (M?hlin and Rheinfelden, Switzerland) could be studied over 30 years. An aluminium smelting plant originated the pollution of this area in the past: however, after the installation of a filtration plant in 1958 the F emissions were reduced and since 1991 almost absent the primary production of aluminium was stopped. The present-day area with elevated F contents (water-soluble F with >20 mg/kg) is restricted to a radius of about 1000 m from the plant. In 1969 this area had a radius of about 3 and 5 km. Between 1969 and 2000 a significant decrease in the soluble F content in the soil was observed together with a substantial decrease of F in the vegetation. The net losses of water-soluble F in the soil were in the range of 35 up to more than 70% of the original concentration and the F losses in the vegetation between 60 up to more than 80%. After the reduction of high F deposition rates the accumulated SOM was decomposed within the observation period 1969-1993. The combined decrease in F and humus led to chain reactions with losses of major elements and a dealumination of clay minerals, i.e. removal of interlayered Al of 2:1 minerals and consequent formation of smectites.     

Distribution and fractionation of phosphorus, cadmium, nickel, and lead in calcareous soils amended with composts

Composts improve organic carbon content and nutrients of calcareous soils but the accumulation and distribution of phosphorus and heavy metals among various fractions in soil may vary under the south Florida conditions. The accumulation of P, Cd, Ni, and Pb with depth and the distribution of water soluble, exchangeable, carbonate, Fe-Mn oxides, organic and residual forms of each element were investigated in soils amended with municipal solid waste (MSW) compost, co-compost and biosolids compost and inorganic fertilizer (as control). Total concentrations of P, Cd, Ni, and Pb were higher in the 0-22 cm soil layers and decreased considerably in the rock layers. These elements were in the decreasing order of P > Pb > Ni > Cd. Amounts of water soluble and exchangeable forms of P, Cd, Ni and Pb were negligible at 0-22 cm soil depths except for Cd in the 10-22 cm depth. Amending calcareous soil with either organic or inorganic amendments rendered phosphorus, nickle and lead in the residual form followed by Fe-Mn oxides form in the 0-10 and 10-22 cm soil layers. Cadmium was predominantly in the Fe-Mn oxides fraction followed by the residual and carbonate forms in both soil layers. A significant positive correlation was found between various organic carbon fractions and organic forms of P, Cd and Pb in the surface soil layer. Soil amended with MSW compost had higher concentration of Cd in the organic fraction whereas, co-compost and MSW compost amended soil had higher concentrations of organic Ni fraction in the 0-10 cm soil layer.     

Degradation of toxaphene in water during anaerobic and aerobic conditions

The degradation of technical toxaphene in water with two kinds of bioreactors operating in sequence was studied. One packed bed reactor was filled with Poraver (foam glass particles) running at anaerobic conditions and one suspended carrier biofilm reactor working aerobically. Chemical oxygen demand (COD), chloride, sulphate, pH, dissolved oxygen, total toxaphene and specific toxaphene isomers were measured. After 6 weeks approx. 87% of the total toxaphene was degraded reaching 98% by week 39. The majority of the conversion took place in the anaerobic reactor. The concentrations of toxaphene isomers with more chlorine substituents decreased more rapidly than for isomers with less chlorine substituents.     

Oxidation of MCPA and 2,4-D by UV radiation, ozone, and the combinations UV/H2O2 and O3/H2O2

The phenoxyalkyl acid derivative herbicides MCPA (4-chloro 2-methylphenoxyacetic acid) and 2,4-D (2,4-dichlorophenoxyacetic acid) were oxidized in ultrapure water by means of a monochromatic UV irradiation and by ozone, as well as by the combinations UV/H2O2 and O3/H2O2. In the direct photolysis of MCPA, the quantum yield at 20 degrees C was directly evaluated and a value of 0.150 mol Eins(-1) was obtained in the pH range 5-9, while a lower value of 0.41 x 10(-2) mol Eins(-1) was determined at pH=3. Similarly, for 2,4-D a value of 0.81 x 10(-2) mol Eins(-1) was deduced, independent of the pH of work. The influence of the additional presence of hydrogen peroxide was established in the combined process UV/H2O2, and the specific contribution of the radical pathway to the global photo-degradation was evaluated. The oxidation by ozone and by the combination O3/H2O2 was also studied, with the determination of the rate constants for the reactions of both herbicides with ozone and hydroxyl radicals at 20 degrees C. These rate constants for the direct reactions with ozone were 47.7 and 21.9 M(-1) s(-1) for MCPA and 2,4-D respectively, while the found values for the rate constants corresponding to the radical reactions were 6.6 x 10(9) and 5.1 x 10(9) M(-1) s(-1).     

Flood-risk management strategies for an uncertain future: living with Rhine River floods in The Netherlands?

Social pressure on alluvial plains and deltas is large, both from an economic point of view and from a nature conservation point of view. Gradually, flood risks increase with economic development, because the expected damage increases, and with higher dikes, because the flooding depth increases. Global change, changing social desires, but also changing views, require a revision of flood-risk management strategies for the long term. These should be based on resilience as opposed to the resistence strategy of heightening dikes. Resilience strategies for flood-risk management imply that the river is allowed to temporarily flood large areas, whereas the flood damage is minimized by adapting land use. Such strategies are thus based on risk management and 'living with floods' instead of on hazard control. For The Netherlands, one of the most densely populated deltas in the world, alternative resilience strategies have been elaborated and assessed for their hydraulic functioning and 'sustainability criteria'.     

Degradation of 1,1,2,2-tetrachloroethane and accumulation of vinyl chloride in wetland sediment microcosms and in situ porewater: biogeochemical controls and associations with microbial communities

The biodegradation pathways of 1,1,2,2-tetrachloroethane (TeCA) and 1,1,2-trichloroethane (112TCA) and the associated microbial communities in anaerobic wetland sediments were evaluated using concurrent geochemical and genetic analyses over time in laboratory microcosm experiments. Experimental results were compared to in situ porewater data in the wetland to better understand the factors controlling daughter product distributions in a chlorinated solvent plume discharging to a freshwater tidal wetland at Aberdeen Proving Ground, Maryland. Microcosms constructed with wetland sediment from two sites showed little difference in the initial degradation steps of TeCA, which included simultaneous hydrogenolysis to 112TCA and dichloroelimination to 1,2-dichloroethene (12DCE). The microcosms from the two sites showed a substantial difference, however, in the relative dominance of subsequent dichloroelimination of 112TCA. A greater dominance of 112TCA dichloroelimination in microcosms constructed with sediment that was initially iron-reducing and subsequently simultaneously iron-reducing and methanogenic caused approximately twice as much vinyl chloride (VC) production as microcosms constructed with sediment that was methanogenic only throughout the incubation. The microcosms with higher VC production also showed substantially more rapid VC degradation. Field measurements of redox-sensitive constituents, TeCA, and its anaerobic degradation products along flowpaths in the wetland porewater also showed greater production and degradation of VC with concurrent methanogenesis and iron reduction. Molecular fingerprinting indicated that bacterial species [represented by a peak at a fragment size of 198 base pairs (bp) by MnlI digest] are associated with VC production from 112TCA dichloroelimination, whereas methanogens (190 and 307 bp) from the Methanococcales or Methanobacteriales family are associated with VC production from 12DCE hydrogenolysis. Acetate-utilizing methanogens (acetotrophs) appear to be involved in the biodegradation of VC. The relative abundance of Methanosarcinaceae, the only methanogen group with acetotrophic members, doubled in microcosms in which degradation of VC was observed. In addition, molecular analyses using primers specific for known dehalorespiring bacteria in the Dehalococcoides and Desulfuromonas groups showed the presence of these bacteria in microcosm slurry from the site that showed the highest VC production and degradation. Determination of biogeochemical controls and microbial consortia involved in TeCA degradation is leading to a better understanding of the heterogeneity in biodegradation rates and daughter product distribution in the wetland, improving capabilities for developing remediation and monitoring plans.