Investigation on the photoreactions of nitrate and nitrite ions with selected azaarenes in water

The photoreactions of selected azaarenes with nitrate and nitrite ions were investigated under irradiation at lambda = 313 nm. The excitation of both anions leads to several photochemical reactions forming mainly hydroxyl radicals and nitrogen oxides. The purification capability of natural waters i.e. the oxidation of inorganic and organic substances results from the formation of hydroxyl radicals. Nitrated isomers of azaarenes were found among the main products of the investigated photoreactions. The nitrogen oxides were responsible for the production of nitrated derivatives which possess a high toxic potential. Their formation was explained by the parallel occurance of two mechanism, a molecular and a radical one. The molecular mechanism became more important with increasing ionisation potentials of the azaarenes. The spectrum of oxidized products corresponded to the one got in the photoreactions of azaarenes with hydrogen peroxide. The formation of several oxidation and nitration products of the pyridine ring with its low electron density was explained by the reaction of excited states of azaarenes. The photoreactions with nitrite ions only led to the formation of oxidized and nitrated products. Nitroso products were not formed. The reactivity of nitrogen monoxide is too low for its reaction with the azaarenes.     

Algal-bacterial interactions in metal contaminated floodplain sediments

The aim of the present study was to investigate algal-bacterial interactions in a gradient of metal contaminated natural sediments. By means of multivariate techniques, we related the genetic structure (denaturing gradient gel electrophoresis, DGGE) and the physiological structure (community-level physiological profiling, CLPP) of the bacterial communities to the species composition of the algal communities and to the abiotic environmental variables, including metal contamination. The results revealed that genetic and physiological structure of the bacterial communities correlated with the species composition of the algal community, but hardly to the level of metal pollution. This must be interpreted as an indication for a strong and species-specific linkage of algal and bacterial species in floodplain sediments. Metals were, however, not proven to affect either the algal or the bacterial communities of the Dutch river floodplains.     

Certification of a long-term sampling system for PCDFs and PCDDs in the flue gas from industrial facilities

AMESA (adsorption method for sampling of dioxins) is a fully automatic system for long term monitoring of dioxin emissions from industrial processes based on the adsorption method. The system has been tested and undergoing a certification procedure according to the German guidelines for certification of systems for continuous monitoring of special substances. The certification covered parameters such as disposability of the system, reproducibility of the results and comparability of the sampling method with German and European standard methods. Furthermore break through, blanks and sample storability were investigated. The results prove that AMESA is a state of the art sampling system for continuous monitoring of dioxin/furan emissions.     

Microbial degradation of phthalic acid esters under anaerobic digestion of sludge

The microbial degradation by anaerobic sludge of three phthalates, priority pollutants, listed by both China National Environmental Monitoring Center and the U.S.EPA, namely, dimethyl (DMP), di-n-butyl (DBP) and di-n-octyl (DOP) phthalates was investigated. The experimental results indicated that the biodegradation rate and the biodegradability of three phthalates under anaerobic conditions appeared to be related to the length of the alkyl-side chains. More than 90% of DMP and DBP with the short alkyl-side chain phthalates can be degraded, whereas the DOP degradation appeared to be relatively slow under the same experimental conditions. The quantity of methane produced was measured and the results showed that both the ester groups and the phthalate ring were mineralized at a significant rate. The kinetics study demonstrated that the biodegradation of three phthalates conformed to the first-order model with respect to their concentrations.     

Determination of Q1, an unknown organochlorine contaminant, in human milk, Antarctic air, and further environmental samples

Q1, an organochlorine component with the molecular formula C(9)H(3)Cl(7)N(2) and of unknown origin was recently identified in seal blubber samples from the Namibian coast (southwest of Africa) and the Antarctic. In these samples, Q1 was more abundant than PCBs and on the level of DDT residues. Furthermore, Q1 was more abundant in seals from the Antarctic than the Arctic. To prove this assumption, gas chromatography-electron-capture negative ion mass spectrometry (GC/ECNI-MS), which is sensitive and selective for Q1, allowed for screening of traces of Q1 even in samples with particularly high levels of other organochlorine contaminants. Q1 was isolated by high-performance liquid chromatography (HPLC) from a skua liver sample. A 1:1 mixture with trans-nonachlor in electron-capture detectors (ECDs) was used to determine the relative response factor with ECNI-MS. The ECNI-MS response of Q1 turned out to be 4.5 times higher than that of trans-nonachlor in an ECD. With GC/ECNI-MS in the selected ion-monitoring mode, four Antarctic and four Arctic air samples were investigated for the presence of Q1. In the Antarctic air samples, Q1 levels ranged from 0.7 to 0.9 fg/m(3). In Arctic air samples, however, Q1 was below the detection limit (<0.06 fg/m(3) or 60 ag/m(3)). We also report on high Q1 levels in selected human milk samples (12-230 microg/kg lipid) and, therefore, suggested that the unknown Q1 is an environmental compound whose origin and distribution should be investigated in detail. Our data confirm that Q1 is a bioaccumulative natural organochlorine product. Detection of a highly chlorinated natural organochlorine compound in air and human milk is novel.     

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.     

Monitoring of toxicity during degradation of selected pesticides using ionizing radiation

The optimization of experimental conditions for radiolytic removal of organic pollutants from water and waste with the use of ionizing radiation via controlling the concentration of target compound(s) requires also monitoring the toxicity changes during the process. Commonly used herbicides 2,4-D and dicamba were shown to increase toxicity measured with the Microtox test at low irradiation doses resulting from formation of more toxic transient products, which can be decomposed at larger doses. The changes of toxicity were examined with respect to dose magnitude and the presence of commonly occurring scavengers of radiation.     

Synthesis of effects in four Arctic subregions

An assessment of impacts on Arctic terrestrial ecosystems has emphasized geographical variability in responses of species and ecosystems to environmental change. This variability is usually associated with north-south gradients in climate, biodiversity, vegetation zones, and ecosystem structure and function. It is clear, however, that significant east-west variability in environment, ecosystem structure and function, environmental history, and recent climate variability is also important. Some areas have cooled while others have become warmer. Also, east-west differences between geographical barriers of oceans, archipelagos and mountains have contributed significantly in the past to the ability of species and vegetation zones to relocate in response to climate changes, and they have created the isolation necessary for genetic differentiation of populations and biodiversity hot-spots to occur. These barriers will also affect the ability of species to relocate during projected future warming. To include this east-west variability and also to strike a balance between overgeneralization and overspecialization, the ACIA identified four major sub regions based on large-scale differences in weather and climate-shaping factors. Drawing on information, mostly model output that can be related to the four ACIA subregions, it is evident that geographical barriers to species re-location, particularly the distribution of landmasses and separation by seas, will affect the northwards shift in vegetation zones. The geographical constraints--or facilitation--of northward movement of vegetation zones will affect the future storage and release of carbon, and the exchange of energy and water between biosphere and atmosphere. In addition, differences in the ability of vegetation zones to re-locate will affect the biodiversity associated with each zone while the number of species threatened by climate change varies greatly between subregions with a significant hot-spot in Beringia. Overall, the subregional synthesis demonstrates the difficulty of generalizing projections of responses of ecosystem structure and function, species loss, and biospheric feedbacks to the climate system for the whole Arctic region and implies a need for a far greater understanding of the spatial variability in the responses of terrestrial arctic ecosystems to climate change.     

Uncertainties and recommendations

An assessment of the impacts of changes in climate and UV-B radiation on Arctic terrestrial ecosystems, made within the Arctic Climate Impacts Assessment (ACIA), highlighted the profound implications of projected warming in particular for future ecosystem services, biodiversity and feedbacks to climate. However, although our current understanding of ecological processes and changes driven by climate and UV-B is strong in some geographical areas and in some disciplines, it is weak in others. Even though recently the strength of our predictions has increased dramatically with increased research effort in the Arctic and the introduction of new technologies, our current understanding is still constrained by various uncertainties. The assessment is based on a range of approaches that each have uncertainties, and on data sets that are often far from complete. Uncertainties arise from methodologies and conceptual frameworks, from unpredictable surprises, from lack of validation of models, and from the use of particular scenarios, rather than predictions, of future greenhouse gas emissions and climates. Recommendations to reduce the uncertainties are wide-ranging and relate to all disciplines within the assessment. However, a repeated theme is the critical importance of achieving an adequate spatial and long-term coverage of experiments, observations and monitoring of environmental changes and their impacts throughout the sparsely populated and remote region that is the Arctic.     

The degradability of biodegradable plastics in aerobic and anaerobic waste landfill model reactors

Degradabilities of four kinds of commercial biodegradable plastics (BPs), polyhydroxybutyrate and hydroxyvalerate (PHBV) plastic, polycaprolactone plastic (PCL), blend of starch and polyvinyl alcohol (SPVA) plastic and cellulose acetate (CA) plastic were investigated in waste landfill model reactors that were operated as anaerobically and aerobically. The application of forced aeration to the landfill reactor for supplying aerobic condition could potentially stimulate polymer-degrading microorganisms. However, the individual degradation behavior of BPs under the aerobic condition was completely different. PCL, a chemically synthesized BP, showed film breakage under the both conditions, which may have contributed to a reduction in the waste volume regardless of aerobic or anaerobic conditions. Effective degradation of PHBV plastic was observed in the aerobic condition, though insufficient degradation was observed in the anaerobic condition. But the aeration did not contribute much to accelerate the volume reduction of SPVA plastic and CA plastic. It could be said that the recalcitrant portions of the plastics such as polyvinyl alcohol in SPVA plastic and the highly substituted CA in CA plastic prevented the BP from degradation. These results indicated existence of the great variations in the degradability of BPs in aerobic and anaerobic waste landfills, and suggest that suitable technologies for managing the waste landfill must be combined with utilization of BPs in order to enhance the reduction of waste volume in landfill sites.