TNT in Komposten und Flüssigkultur

The formation of aromatic amines was investigated using a summarized test (NEDA-test) during the composting of 2,4,6-trinitrotoluene (TNT) contaminated soil. In this test, the aromatic amines were diazolated and then coupled to N-1-Naphthyl-ethylenediamine-dihydrochloride (NEDA) to yield an azo dye which can be monitored photometrically. The test was calibrated for known TNT-metabolites with an active amine-group. Liquid samples from composting- and liquid-culture-experiments were analyzed by HPLC for these known metabolites. Moreover, the samples were monitored by the NEDA-test and the expected extinction of the TNT-metabolites found with amine function were extrapolated with the help of calibration curves. It was shown that substantial differences are obvious between the monitored and extrapolated values. After separation into polar and non-polar aromatic amines, it became clear that these differences are made by the polar aromatic amines. Polar aromatic amines, which are not detectable by presently available analytical tests, were generated during the composting of TNT-contaminated soils. Contaminated stagnant water, which was generated during anaerobization of a compost prephase, was treated aerobically for 70 days in a biofermenter. During this treatment TNT and its known metabolites were eliminated almost entirely. Simultaneously, the toxicity in the Lumis Tox-test decreased drastically. In striking contrast, the sum of aromatic amines decreased only to a minor extent. Moreover, the percentage of polar compounds from total amount of aromatic amines increased drastically from 48% to more than 95%. At present, the chemical identification of these polar compounds is still missing and is the object for further research.     

A solid-phase microextraction method for the in vivo sampling of MTBE in common reed (Phragmites australis)

Phytoscreening of phytoremediation-based plantings is discussed as a promising monitoring tool in literature. We developed and applied an analytical procedure for the in vivo sampling of methyl tert-butyl ether (MTBE) in the common reed (Phragmites australis) from a phytoremediation site highly polluted with MTBE. The approach uses solid-phase microextraction (SPME) with the SPME fibre directly introduced into the aerenchyma of the plant stem. For optimising the analytical procedure and estimating the capability of the proposed method, laboratory tests on the microcosm scale and field studies over one vegetation period were carried out. Furthermore, the results of in vivo SPME sampling were compared with those obtained with the traditional approach for analysing plants using dynamic headspace analysis. The MTBE signals detected within the plants were also correlated with the concentration in the water phase. The discussion of results showed the feasibility of the proposed method for a qualitative phytoscreening of volatile organic compounds present in wetland plants.     

National PCDD/PCDF release inventories under the Stockholm Convention on Persistent Organic Pollutants

National inventories to estimate releases of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans have been undertaken since the mid 1980s. These inventories were scattered and hard to compare since there was no harmonized method available. With the conclusion of the Stockholm Convention on Persistent Organic Pollutants and its entry into force, Parties to the Convention at the global level, have to establish PCDD/PCDF release inventories and report these results. UNEP Chemicals has developed a methodology that allows developing and developed countries to make estimates of PCDD/PCDF releases into the environment along all vectors. Presently, there are 23 national release inventories available that have been made with this methodology, the Toolkit. Among the most important sources, open fires in agriculture/forests as well as open burning of wastes have been identified as the major sources of PCDD/PCDF. The results from these inventories may serve as the starting point for interventions to reduce or eliminate sources of PCDD/PCDF by application of best available techniques and best environmental practices. The Toolkit will be updated as needs arise.     

Simultaneous monitoring of PCDD/Fs and PCBs in contaminated air with semipermeable membrane devices and fresh spruce needles

The contaminated air with burning plastic floor and electronic scrap was monitored with semipermeable membrane devices (SPMDs) and fresh unpolluted spruce needles at the same time for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). It was found that there were more polychlorinated dibenzofurans (PCDFs) than polychlorinated dibenzo-p-dioxins (PCDDs) collected from contaminated air. The total amounts of PCBs were much higher than that of PCDD/Fs, but the contribution of them to the WHO-TEQ was less than that of PCDD/Fs. Triolein-containing SPMDs can absorb much more PCDD/Fs and PCBs than spruce needles when they were exposed in contaminated air simultaneously. The logarithm of the concentrations of PCDD/Fs and PCBs in SPMDs and in spruce needles at the same sampling time exhibited a significant linear correlation, the correlation coefficients were larger than 0.86 for PCDD/Fs and 0.92 for PCBs. SPMDs and spruce needles are effective passive air sampler for PCDD/Fs and PCBs. SPMDs and spruce needles can complement each other in passive air sampling.     

Application of QSARS to predict potential aquatic toxicities of organochlorine pesticides∗

On the basis of physico‐chemical data, such as water solubility and vapour pressure as well as acute toxicity tests we developed an ecotoxicological model for preliminary hazard assessment. By use of the reciprocal product from log H and LC₅₀ we developed a suitable ranking system that allows us to predict potential damage to aquatic organisms through pesticides.     

Emission factors for PCDD/PCDF and dl-PCB from open burning of biomass

The Stockholm Convention on Persistent Organic Pollutants includes in its aims the minimisation of unintentional releases of polychlorinated dibenzo-dioxins and dibenzofurans (PCDD/PCDF) and dioxin like PCB (dl-PCB) to the environment. Development and implementation of policies to achieve this aim require accurate national inventories of releases of PCDD/PCDF/dl-PCB. To support this objective, the Conference of Parties established a process to review and update the UNEP Standardized Toolkit for Identification and Quantification of Dioxin and Furan Releases. An assessment of all emission inventories was that for many countries open burning of biomass and waste was identified as the major source of PCDD/PCDF releases. However, the experimental data underpinning the release estimates used were limited in number and, consequently, confidence in the accuracy of the emissions predictions was low. There has been significant progress in measurement technology since the last edition of the Toolkit in 2005. In this paper we reassess published emission factors for release of PCDD/PCDF and dl-PCB to land and air.In total, four types of biomass and 111 emission factors were assessed. It was found that there are no systematic differences in emission factors apparent between biomass types or fire classes. The data set is best described by a lognormal distribution. The geometric mean emission factors (EFs) for releases of PCDD/PCDF to air for the four biomass classes used in the Toolkit (sugarcane, cereal crops, forest and savannah/grass) are 1.6 μg TEQ (t fuel)⁻¹, 0.49 μg TEQ (t fuel)⁻¹, 1.0 μg TEQ (t fuel)⁻¹ and 0.4 μg TEQ (t fuel)⁻¹, respectively. Corresponding EFs for release of PCDD/PCDF to land are 3.0 ng TEQ (kg ash)⁻¹, 1.1 ng TEQ (kg ash)⁻¹, 1.1 ng TEQ (kg ash)⁻¹ and 0.67 ng TEQ (kg ash)⁻¹. There are now also sufficient published data available to evaluate EFs for dl-PCB release to air for sugarcane, forest and grass/savannah; these are 0.03 μg TEQ (t fuel)⁻¹, 0.09 μg TEQ (t fuel)⁻¹ and 0.01 μg TEQ (t fuel)⁻¹, respectively. The average EF for dl-PCB release to land is 0.19 ng TEQ (kg ash)⁻¹. Application of these EFs to national emissions of PCDD/PCDF for global estimates from open burning will lower previous estimates of PCDD/PCDF releases to air and to land by 85% and 90%, respectively. For some countries, the ranking of their major sources will be changed and open burning of biomass will become less significant than previously concluded.     

Ecological half-lives of 90Sr and 137Cs in terrestrial and aquatic ecosystems

This paper describes the long-term behaviour of (90)Sr and (137)Cs in foods, feeds and a variety of environmental media. The long-term behaviour is quantified by means of the ecological half-life which integrates all processes that cause a decrease of activity in a given medium such as leaching, fixation and erosion. A large number of long-term time series of concentrations of radiocaesium and radiostrontium in these media have been identified and re-evaluated using a standardised statistical procedure to establish reference data sets of ecological half-lives. By example of undisturbed soils and marine water bodies it is shown that the ecological half-life concept is questionable if the distribution of the radionuclide of interest within the medium studied is non-uniform and if mixing and transport processes within this medium, therefore, are of considerable importance during the time period of observation.