Fate of ah receptor agonists during biological treatment of an industrial sludge containing explosives and pharmaceutical residues

GOAL, SCOPE AND BACKGROUND: Sweden is meeting prohibition for deposition of organic waste from 2005. Since 1 million tons of sludge is produced every year in Sweden and the capacity for incineration does not fill the demands, other methods of sludge management have to be introduced to a higher degree. Two biological treatment alternatives are anaerobic digestion and composting. Different oxygen concentrations result in different microbial degradation pathways and, consequently, in a different quality of the digestion or composting residue, It is therefore necessary to study sludge treatment during different oxygen regimes in order to follow both degradation of compounds and change in toxicity. In this study, an industrial sludge containing explosives and pharmaceutical residues was treated with anaerobic digestion or composting, and the change in toxicity was studied. Nitroaromatic compounds, which are the main ingredients of both pharmaceutical and explosives, are well known to cause cytotoxicity and genotoxicity. However, little data are available concerning sludge with nitroaromatics and any associated dioxin-like activity. Therefore, we studied the sludge before and after the treatments in order to detect any changes in levels of Ah receptor (AhR) agonists using two bioassays for dioxin-like compounds. METHODS: An industrial sludge was treated with anaerobic digestion or composting in small reactors in a semi-continuous manner. The same volume as the feeding volume was taken out daily and stored at -20 degrees C. Sample preparation for the bioassays was done by extraction using organic solvents, followed by clean up with silica gel or sulphuric acid, yielding two fractions. The fractions were dissolved in DMSO and tested in the bioassays. The dioxin-like activity was measured using the DR-CALUX assay with transfected H4IIE rat hepatoma pGudluc cells and an EROD induction assay with RTL-W1 rainbow trout liver cells. RESULTS AND DISCUSSION: The bioassays showed that the sludge contained AhR agonists at levels of TCDD equivalents (TEQs) higher than other sludge types in Sweden. In addition, the TEQ values for the acid resistant fractions increased considerably after anaerobic digestion, resulting in an apparent formation of acid resistant TEQs in the anaerobic reactors. Similar results have been reported from studies of fermented household waste. There was a large difference in effects between the two bioassays, with higher TEQ levels in the RTL-W1 EROD assay than in the DR-CALUX assay. This is possibly due to a more rapid metabolism in rat hepatocytes than in trout hepatocytes or to differences in sensitivities for the AhR agonists in the sludge. It was also demonstrated by GC/FID analysis that the sludge contained high concentrations of nitroaromatics. It is suggested that nitroaromatic metabolites, such as aromatic amines and nitroanilines, are possible candidates for the observed bioassay effects. It was also found that the AhR agonists in the sludge samples were volatile. CONCLUSIONS: The sludge contained fairly high concentrations of volatile AhR agonists. The increase of acid resistant AhR agonist after anaerobic digestion warrants further investigations of the chemical and toxic properties of these compounds and of the mechanisms behind this observation. RECOMMENDATION AND OUTLOOK: This study has pointed out the benefits of using different types of mechanism-specific bioassays when evaluating the change in toxicity by sludge treatment, in which measurement of dioxin-like activity can be a valuable tool. In order to study the recalcitrant properties of the compounds in the sludge using the DR-CALUX assay, the exposure time can be varied between 6 and 24 hours. The properties of the acid-resistant AhR agonists formed in the anaerobic treatment have to be investigated in order to choose the most appropriate method for sludge management.     

über Bilche oder ?Schl?fer’: Gartenschl?fer, Baumschl?fer, Siebenschl?fer und Haselm?use

Ohne Zusammenfassung     

Significance of platinum group metals emitted from automobile exhaust gas converters for the biosphere

Intention, Goal, Scope, Background  Following the introduction of automobile catalytic converters the platinum group metals (PGM) platinum (Pt), palladium (Pd) and rhodium (Rh) gain on increasing interest in environmental research as these metals are emitted with exhaust fumes into the environment. Consequently, elevated PGM levels were found in different environmental matrices uch as road dusts, soils along heavily frequented roads, sediments of urban rivers etc. Accordingly, the effects of increasing PGM emissions on the biosphere are controversially discussed. Objective  This paper summarizes the present knowledge on the biological availability of PGM to plants and animals. As biological availability is one of the most decisive factors determining the toxicologi-cal potential of xenobiotics, this information is very important to evaluate the possible threat of the noble metals to ecosystems. Results and Discussion  The availability of soluble as well as particle bound PGM to terrestrial plants was demonstrated in several studies. Experimental investigations revealed uptake of Pt, Pd and Rh also by aquatic plants. Additionally, the biological availability of the noble metals for animals has been verified in experimental studies using soluble metal salts, catalytic converter model substances, sediments of urban rivers, road dust or tunnel dust as metal sources. These studies refer mainly to aquatic animals. Beside of free living organisms, in particular worms parasitizing fish demonstrated a high potential to accumulate PGM. This could be of great interest in respect of biomonitoring purposes. Generally, for plants as well as for animals Pd turns out to be the best available metal among the PGM. Compared to other heavy metals, the biological availability of PGM from road dust to zebra mussels(Dreissena polymorpha) ranged between that of Cd and Pb. Conclusion  Especially chronic effects of PGM on the biosphere can not be excluded due to (1) their cumulative increase in the environment, (2) their unexpected high biological availability and bioaccumulation and (3) their unknown toxicological and ecotoxicological potential. However, it appears that acute effects on ecosystems due to anthropogenic PGM emission are not likely. Recommendation and Outlook  Research on environmental PGM contamination of the biosphere, especially the fauna, and on long-term toxiciry of low PGM concentrations is highly appreciated. These studies require very sensitive analytical techniques to determine PGM even in low sample amounts. Research has to be done in particular on reliable determination of (ultra) trace levels of Pd and Rh as the lack of data on these two metals is mainly due to analytical problems.     

含油固体废弃物综合利用技术的研究

就油田含油固体废弃物的存放及其对周边环境存在的潜在隐患 ,全面分析了该废弃物的组成与成分 ,并介绍了几种可用于石油污染土壤治理技术的方法特点 ,尤其是针对这种固体含量和油分含量皆较高的含油固体废弃物 ,开展了综合利用治理技术方面的试验 ,以固体废弃物细粉作为制砖助燃配料成分 ,考查了砖块质量与细粉掺入量及其他因素之间的关系 ,取得了较好的效果     

富营养化湖泊底泥污染控制技术评估

回顾了我国在富营养化湖泊底泥污染控制技术方面的研究进展,并从富营养化湖泊底泥污染控制技术的运用效果、环境影响、社会影响、经济性、适用性以及与其他技术的相关性等六个方面,全面评估了破坏分层、人工曝气、化学增氧、底泥疏浚和底泥封闭等五类技术.     

Ligand exchange rate of metal-nom complexes by EDTA

Metal complexation by natural ligands is important for metal transport and distribution in surface and ground water. The goal of the work was to study the ligand exchange rate for two important metal ions in natural aquatic systems (Al, Fe) was determined using EDTA and natural organic matter (NOM) of humic type as ligands. After adding EDTA to a solution containing metal-NOM complexes, these complexes dissociated and metal-EDTA complexes were formed. Metal-NOM complexes were separated from metal-EDTA complexes with the help of size-exclusion chromatography and detected by on-line inductively coupled plasma-mass spectrometry (ICP-MS). Injecting the samples into the system over time after addition of EDTA allowed us to measure the rate of the exchange of NOM by EDTA. The experiments could be well described with a first-order rate law assuming that the dissociation of the metal-NOM complexes is the rate-determining step. The exchange rate of Fe was found to be faster than that of Al. This corresponds well with the exchange rate of water molecules from the coordination sphere of the metal ions, which is also faster for Fe than for Al. Furthermore, the UV and the fluorescence signal of the chromatograms were measured. The results indicate that no disaggregation of NOM molecules took place, although about 75-85% of the aggregate-forming metal ions exchanged NOM by EDTA in their coordination sphere. This suggests clearly the fundamental role of NOM in colloidal transport of metals and in their bioavailability.     

What is the lesson from the unprecedented event over antarctica in 2002

Varotsos (2002a,b), suggested that both the smaller-sized ozone hole over Antarctica and its splitting in two holes in September 2002 occurred due to an unprecedented major sudden stratospheric warming caused by very strong planetary waves propagated in the southern hemisphere. Subsequently, a NASA press release of December 6, 2002, also reported the prevalence of very strong planetary waves in Antarctica. The aim of this Letter is to further discuss the morphology of the Antarctic ozone hole, to detect the causes that allowed the Antarctic stratosphere to exhibit this exceptional warming and to examine what it denotes about its mechanisms. Concerning the morphology, among the principal findings is that the ozone hole split occurred not only in the stratosphere but extended in the lower altitudes (upper troposphere). As to the causes of the major sudden stratospheric warming of 2002, a comparison with the previous warmings in Antarctica since 1964 is made. The smaller-sized Antarctic ozone hole of 2002 is approximately equal to that of 1988 when a strong sudden stratospheric warming occurred. If only the destruction of ozone by chlorofluorocarbons resulted in the delayed sudden stratospheric warmings in Antarctica, then the early sudden stratospheric warmings of 1988 and 2002 would not have occurred, since chlorofluorocarbon loading of the stratosphere has remained relatively stable in recent years. Furthermore, it appears that the El Nino characteristics in 1988 and 2002 are not similar.     

Effects of uncontrolled particulate matter release on precipitation under warfare conditions

This study has shown theoretical, observed and experimental evidence of pollutants released, transported and deposited during the Kosovo conflict in 1999 and their effects on precipitation in Serbia. The greatest bombardment of the chemical industry, oil refineries and fuel storage in Serbia which occurred during April, resulted in releases of many hazardous, toxic and cancerogenic substances. The number of April's days with precipitation greater or equal to 0.1 mm in 1999 are compared to those in the period from 1961 to 1990 registered at thirty meteorological stations in Serbia and especially at the Belgrade-Observatory station in the period from 1888 to 1995. The maximums of days with precipitation greater or equal to 0.1 mm were at the wider Belgrade area and at the central and southwestern parts of Serbia during April 1999. This is confirmed by using the Eta trajectory analysis.     

Dehalogenation Potential of Municipal Waste Incineration Fly Ash

BACKGROUND, AIMS AND SCOPE: In the first part of this paper the main principles which control the dehalogenation of polychlorinated aromatic compounds on municipal waste incineration fly ash (MWI-FA) have been discussed and the model fly ash of similar dehalogenation activity has been proposed. Even if both systems show comparable dehalogenation properties, the main question concerning the postulated identical reaction mechanism in both cases is left unanswered. The other very important point is to what extent is this dechlorination mechanism thermodynamically controlled. The same problem is often discussed in the literature also for the de novo synthetic reactions. From the data it is clear that metallic copper plays a decisive role in the mechanism of the dehalogenation reaction. Although the results reported in the first part strongly support the idea that copper acts in this dechlorination as the reaction component, in contrast to its generally accepted catalytic behaviour, we believed that additional support for this conclusion can be obtained with the help of a thermodynamic interpretation of the mechanism of the reaction. RESULTS AND DISCUSSION: The pathways of hexachlorobenzene dechlorination on MWI-FA and model fly ash were studied in a closed system at 260-300 degrees C under nitrogen atmosphere. These pathways were the same for both systems, with the following prevailing sequences: hexachlorobenzene --> pentachlorobenzene --> 1,2,3,5-tetrachlorobenzene --> 1,3,5-trichlorobenzene --> 1,3-dichlorobenzene. Thermodynamic calculations were carried out by using the method of minimization total Gibbs energy of the whole system. In the calculations, the following reaction components were taken into account: all gaseous chlorinated benzenes, benzene, hydrogen chloride, a gaseous trimer Cu3Cl3, and also Cu2O and CuCl2 as solid components. The effect of the reaction temperature and the amount of copper and water vapour were considered as well. The effect of reaction temperature was determined from the data calculated for the 500 to 750 K temperature region. The effect of the initial composition was determined for the molar amounts of copper = 0.01-3 moles and water vapour = 0.2 to 3 moles per mole of chlorobenzene isomer CONCLUSIONS: The results of hexachlorobenzene dechlorination by MWI-FA and model fly ash under comparable reaction conditions allow us to conclude that both dechlorinations proceed via the same dechlorination pathways, which can be taken as an evidence of the identical dehalogenation mechanism for both systems. The relative percentual distribution of the dehalogenated products depends on the temperature, but not on the initial amount of water vapour or copper metal. On the other hand, the initial amount of copper substantially affects the conversion of the dehalogenation as well as the molar ratio of Cu3Cl3 to HCl in the equilibrium mixture. Comparison of the experimental with thermodynamic results supports the idea that dehalogenation reactions are thermodynamically controlled. RECOMMENDATIONS AND OUTLOOK: Thermodynamic analysis of the dehalogenation reactions may prove useful for a wide range of pollutants. The calculations concerning polychlorinated biphenyls and phenols are under study.