Brandkatastrophe in Schweizerhalle 1986 — Rückblick und Bilanz

Background

On November 1st 1986, a fire at a Sandoz Ltd. storehouse at Schweizerhalle, an industrial area near Basel, Switzerland, resulted in a chemical contamination of the environment. The storehouse, which was completely destroyed by the fire, contained pesticides, solvents, dyes, and various raw and intermediate materials. The majority of the approximately 1,250 tons of stored chemicals was destroyed in the fire, but large quantities were introduced into the atmosphere, into the Rhine river through runoff of the fire-fighting water and into the soil and groundwater at the site. The chemicals discharged into the Rhine caused massive kills of benthic organisms and fish, particularly eels and salmonides. The public and private reaction to the fire and the subsequent chemical spill was very strong. This catastrophe happened only a few months after the Chernobyl accident and destroyed the myth of the immunity of Switzerland.

Aim

This article reviews the damaging events of November 1986 and aims at striking the balance two decades later.

Results and Discussion

In the aftermath of this once-per-century accident, it was the aim was to gain increased knowledge and understanding in the environmental sciences and to achieve progress for water pollution control issues.The following themes are discussed: Mitigation measures by the chemical industry and by the governmental authorities, activities of environmental protection organisations, chemical and biological monitoring, alert organisation, ecological damages, ecotoxicological effect assessment, recovery and alteration of river biology, return of the salmon, drinking water supplies, research programs, education of environmental scientists and visions for the future.

Conclusions

The catastrophic pollution of the Rhine in November 1986, and the obvious damages of the river biology, triggered significant progress towards the prevention of such environmental catastrophes. The crucial risk reduction measures in the chemical industry, legal regulations and controls as well as chemical and biological monitoring of the river water quality were substantially improved. Politics and chemical industry learned their lectures and proceeded accordingly.

Recommendations

Such a drastic acute contamination, as happened at Schweizerhalle in 1986, is clearly recognizable by the toxic effects. This led to long-term mitigation activities. However, also the less obvious effects of chronic water pollution should receive more attention as well as the on-going alteration of the biocenosis. A high water quality must be demanded in terms of using the Rhine water for drinking water supply. In that context, micropollutants should also be considered, and particular attention should be paid to emerging contaminants.

Perspectives

The big chemical storehouse fire of 1986 induced the transboundary cooperation and improved the willingness for international cooperation. Overall, the effects of the fire catastrophe are positive in terms of a long-term perspective. The whole-basin approach is, on a global basis, an example for other, even more heavily polluted river systems.

     

Analytik sprenstofftypischer Substanzen—Ein Methodenvergleich

Six different extraction methods for the determination of nitroaromatics in soil samples were investigated regarding the comparability of the analytical results as well as the trueness and precision of the results. The analysed soil samples came from the intermediate store of the former Hessian ammunition production site Stadtallendorf near Marburg, Germany. The analysis was carried out using gas chromatography with electron capture detector (ECD), and HPLC with a UV-detector. The statistical evaluation of the analytical results was performed according to DIN 38402 part 42, as an interlaboratory trial. Ten explosive-relevant compounds were the subject of investigation. For most compounds a good or at least sufficient comparability of the six methods was evident. Only the two amino-dinitrotoluenes and RDX demonstrated a great extraction-dependent variation.     

Arsenaufnahme von Wildpflanzen auf einem kampfstoffkontaminierten Rüstungsaltlastenstandort

The risk assessment of former ammunition factories, where chemical weapons consisting of diphenylarsenic compounds have been produced or stored is difficult because of the lack of data concerning bioavailability and metabolism of the residues of these sternutators. In order to estimate the contamination of fodder plants by typical pollutants of the former Heeresmunitionsanstalt Löcknitz, the total concentration of arsenic was determined in 186 samples of wild plants. The total arsenic concentration in plants of high feed value did not exceed 1 ppm, whereas 15% of the samples of plants of middle and little value in regard to animal fodder showed arsenic concentrations above 1ppm. The uptake of arsenic by wild plants, however, appears to be comparably low taken the high-grade contamination of the soil into account. A final toxicological evaluation of the risk potential is not yet possible because it requires the characterization of the anorganic and organic arsenic compounds in these plants.     

HPLC-MS/MS in der Rückstandsanalytik von Pflanzenschutzmitteln

Goal and Scope

Increasing demands from the regulatory authorities of plant protection products for residue analytical methods on the one hand and the need for cost reduction by shorter development times on the other hand have led to a significant displacement of conventional methods (e.g. HPLC-UV or GC-MS) by HPLC-MS/MS with atmospheric pressure ionization (API) in residue analysis since the mid of the 1990s. This development started in the pharmaceutical industries where HPLC-MS/MS had already been used for the quantitation of drugs and their metabolites in plasma since the late 1980s.

Methods

The reason for the high acceptability of HPLC-MS/MS with electrospray ionisation (ESI) or chemical ionization at atmosheric pressure (APCI) compared with alternative methods are shown with respect to analytical quality parameters, compliance with international registration guidelines and economic reasons.

Results and Conclusion

HPLC-MS/MS is being applied for solving ca. 75% of all analytical problems occuring in modern residue analytical laboratories. This technique offers convincing advantages for the determination of plant protection products and their metabolites in various matrices. These are a reduced number of or no clean-up steps after extraction of the samples, high throughput besides high ruggedness, low limits of detection and a large linear measuring range. In addition, several analytes of various chemical classes can be determined within one chromatographic run. Due to the high selectivity there is only little need for additional confirmatory methods. For enforcement purposes HPLC-MS/MS is accepted by the European authorities since 2002. However, due to high costs for instrumentation and specially skilled personnel only few enforcement laboratories have invested into this technology, so far.

Recommendation and Perspective

The importance of HPLC-MS/MS in residue analysis will further increase, as new ionization techniques will enable the analysis of more analytes and as the investment costs will decrease in the future. However, proven conventional methods will still survive in some cases. New concepts, such as parallel HPLC-MS/MS or on-line purification of extracts by column switching which are already widely used in the pharmaceutical industry could help to further increase the throughput. However, for a sound evaluation with respect to their applicability in residue analysis there is so far too little experience.     

Umweltrelevanz von Diphenylamin — Ein Stoff der 3. EU-Altstoffprioritätenliste

Diphenylamine (DPA), the simplest secondary aromatic amine, is a compound from the third European Union (EU) list of priority pollutants. It was assigned to Germany to assess and control its environmental risks. DPA is most commonly used as a stabilizer agent in nitrocellulose-containing explosives and propellants, in the perfumery, and as an antioxidant in the rubber and elastomer industry. DPA is also widely used to prevent the post-harvest deterioration of apple and pear crops. It is a parent compound of many derivatives which are used for the production of dyes, pharmaceuticals, photography chemicals and further small-scale applications. At the beginning of the eighties, the estimated world production of DPA was ?40,000 tons per year (in Germany ?4,000 tons per year). The compound is still produced world-wide by the chemical industries. Recently published reports showed that DPA was found in soil and groundwater (within the ppb to ppm range). Some ecotoxicological reports demonstrated the potential hazard of various diphenylamines to the aquatic environment and to bacteria and animals as well. Studies on the biodegradability of DPA and its derivatives are very sparse. Therefore, further investigations are required to determine the complete dimensions of the potential environmental hazard and to introduce possible (bio)remediation techniques for sites that are contaminated with this compound or its derivatives. This review summarizes the environmental relevance of DPA as has been published in the literature thus far. It may possibly support the German authorities in their assessment of the risks of this priority pollutant.     

Bestimmung von Nitrodiphenylaminen und verwandten Verbindungen im Sickerwasser einer Rüstungsaltlast

Goal, Scope and Background

Nitrodiphenylamines can be found at abandoned military sites where the explosive 2,2′,4,4′,6,6′-hexanitrodiphenylamine (hexyl) or diphenylamine as a stabilizer of smokeless powder was handled. Aim of the present study is the development of HPLC methods for the analysis of contaminants which can be expected in particular under aerobic conditions at premises which are contaminated by nitrodiphenyl-amines and related compounds.

Methods

A list of 13 compounds which can be expected at these explosives factories was deduced from literature studies. HPLC methods were developed for the analytes. Water samples from the unsaturated zone of a former hexyl-producing factory were collected by suction cups and the material was analysed according to these procedures to demonstrate the practicability of the new methods and to verify the existence of the postulated compounds in the environment of the former nitration plant.

Results and Conclusion

The new HPLC methods are suitable for the exploration of sites contaminated by nitrodiphenylamines. Beside some hexyl its intermediates 1-chloro-2,4-dinitrobenzene, 2,4-dinitrodiphenylamine und 2,2′,4,4′-tetranitrodiphenylamine were identified in the leachate water.

Recommendation and Perspective

It is advisable to include at least these 4 compounds in the examination of former hexyl-producing plants. Several unknown peaks were observed in the HPLC-chromatogram. It is recommendable to perform further investigations of the unidentified compounds to compile a final list of analytes for military sites polluted by nitrodiphenylamines.     

SETAC GLB — Gründung und Entwicklung

Goal, Scope, and Background

In the context of the ISO-standardisation of the in vitro micronucleus test for (waste) water testing (ISO/DIS 21427-2), a national collaborative study was organized by the German Federal Institute of Hydrology (BfG) involving ten laboratories of private companies, universities and public authorities. The formation of micronuclei (MN) is a special kind of chromosomal aberration. To meet the standardisation requirements for this method, encoded waste water samples, some of them spiked with known genotoxins, had to be tested in a collaborative study. The study should demonstrate practicability of the in vitro micronucleus test for waste water testing and should provide validity data.

Material and Methods

The micronucleus assay was performed with the permanently growing Chinese hamster lung fibroblast cell line V79. Four encoded samples from one municipal and one industrial wastewater treatment plant were tested with and without metabolic activation by S9-mix. Two of these samples were spiked in advance with defined concentrations of the clastogenic substances cyclophosphamide and mytomycin C. The defined assessment criterion for genotoxicity was the lowest dilution of a sample that does not show any significant induction of micronuclei (LID; lowest ineffective dilution). Cytotoxicity was judged by determining the survival-index, i.e. the percentage growth rate of the cells compared with the respective negative controls. As supplementary qualitative criteria, the mitotic index and the proliferation index were assessed.

Results

Although some of the laboratories had little or even no experience with the protocol of the in vitro micronucleus test described in the ISO-draft, all participants suceeded in establishing the assay within few weeks and in generating viable test results. The two nongenotoxic samples were detected as negative by 90% or 100% of the participants. The mitomycin C-spiked sample (expected to be positive without S9 supplementation) was correctly evaluated as positive by all laboratories. The cyclophosphamide-spiked sample (expected to be positive with S9 supplementation) was evaluated correctly as genotoxic by 80% of the laboratories. A post-test analysis found evidence that the false-negative results were due to technical failure, but not of a methodological nature. The sample LID values varied by no more than one dilution step around the median LID-value for all samples investigated. The survival index was proven to be a robust measure for estimation of cytotoxicity.

Discussion

The measurement of micronuclei is an important parameter for the detection of cytogenetic damage. In contrast to the single-cell gel electrophoresis assay (Comet assay), which is used as an indicator test, the in vitro micronucleus test detects non-repairable and thus manifested genetic damage. Consequently, the in vitro micronucleus test can be regarded as the more significant test system. A more frequent occurrence of micronuclei in treated cells suggests a risk of severe genetic damage for subsequent cell generations. In the interest of a precautionary environmental protection and health protection no municipal or industrial waste-water samples should show any significant induction of micronuclei in the treated cell populations.

Perspectives

The presented collaborative study was the first interlaboratory comparison of the in vitro micronucleus test using wastewater samples. The test system is intended to complement the already DIN- and ISO-standardised bacterial tests, i.e. the umu-test and the Ames plate incorporation assay. The data generated in the course of this project justify the transformation of the draft standard into the final draft international standard (FDIS), the preliminary stage of an international norm, so that a valid, standardised test system for the detection of cukaryotic genotoxicity in water samples might become available.     

Batterienrecycling: Möglichkeiten zur Erhöhung der Rücklaufquote

Separate collection and exploitation of used batteries facilates the recycling and eventual waste management of such heavy metals as mercury and cadmium. It is thereby possible to regain raw materials like zinc, manganese and iron for the raw material cycle. Although the collection and recycling of used batteries in Switzerland is financed by a prepaid disposal fee, their returning rate of almost 60% is too low for several reasons. A questionnaire survey carried out on 2000 households revealed the following frequenthy: People collecting paper, glass, aluminium, compost and tinplate, are more separate used batteries from ordinary garbage. The number of collecting points is supposed to be sufficient, but not all of them are sufficiently marked. The prepaid disposal fee (VEG) should become obligatory so that it would be possible to compensate the collecting points. It is not obvious from the results of the survey if the introduction of a deposit of batteries would raise the retourning rate. As far as advertising is concerned, only the “battery bag” sent to every household by the BESO seemed to influence the collecting behaviour in a positive way, poster advertising had only little effect. Appeals in newspapers, radio and television did not show any changement of the collecting behaviour. However, information and knowledge about batteries and their recycling do have a positive influence in the collecting behaviour of the consumers in this specific case.     

Schwermetalle in Regenwürmern Baden-Württembergs

Goal and Scope

The heavy metal burden of the soil and of earthworms from representative long-term forest observation plots has been measured since 1984 as one component of the media-embracing environmental monitoring network of the State of Baden-Wuerttemberg. These investigations are aimed at elucidating and assessing adverse effects of pollutants on the soil biocenosis

Methods

So-called characteristic curves for the metals Cd, Cu, Ni, Pb, and Zn were developed for the assessment. Earthworm toxicity data and background values in soil served as criteria. This procedure facilitates a comparative assessment of different pollutants. The mobility of the metals, which greatly influences their bioavailability and toxicity, was taken into account for the effects assessment.

Results and Conclusion

Besides inventorying the heavy metals (Part 1), the question of threshold values for toxic reactions as well as for accumulation was raised. The metal concentrations were assessed in the soil with regard to its habitat function. The ecotoxicological assessment revealed that the heavy metal burden of the investigated plots lies within the background- or precautionary range, well below the screening value established here to indicate the effect threshold in earthworms. This result means that a pollution of the forest observation plots with the metals cadmium, copper, lead, nickel, and zinc is low or absent. Only the distribution of the lead content is centered slightly above background (but clearly below the toxicity threshold). This slight lead burden of the soil of the observation plots can be explained by emissions from motor vehicles. Investigations at sites that are contaminated with either chromium or copper or cadmium showed that an accumulation of these metals in the body of the worms can be observed only above a threshold concentration of several hundred micrograms of mobile metal per kilogram in the upper layer of the soil.

Recommendations and Perspectives

The hitherto unknown threshold values for the accumulation in the body of the earthworm should be statistically validated and extended to other elements. Further research is needed in order to build a well founded basis for the ecotoxicological assessment of soil pollution. Acute and chronic earthworm effect thresholds are neither available yet for arsenic, cobalt, and mercury nor for some other elements occurring less frequently as soil pollutants. Background values depending on the kind of rock have been measured so far for total chromium only. They are lacking for the more toxic chromium (VI) which is a frequent soil pollutant but naturally occurs in traces only.     

Treibhausgas-Emissionen zukünftiger Erdgas-Bereitstellung für Deutschland

Background

Natural gas makes a significant contribution to the current energy supply and its importance, in relation to both the German and worldwide energy supplies, will increase further in decades to come. In addition to its high degree of efficiency, the low level of direct GHG combustion emissions is also an advantageous factor. However, around 90% of natural gas is methane (CH₄), which is the second most significant GHG due to its high greenhouse potential (21 times higher than CO₂). Therefore, high levels of direct gas losses of natural gas in its production, processing, transport and distribution could neutralise its low emission advantages. This is particularly apparent when considering the growing distances between production and use, the demanding production processes and the upcoming worldwide market for LNG (liquefied natural gas).

Aim

This paper aims to analyse and illustrate the future GHG emissions of the whole process chain of natural gas (indirect emissions) to be supplied to the German border over the next 2 decades. This should allow the comparison of total GHG emissions (indirect and direct) of natural gas with the GHG emissions of other fossil fuels. By considering likely changes in gas origin as well as dynamic changes in the infrastructure and technology of gas production, processing and transport until 2030, all relevant factors are included. The study focuses on the emissions of Russian natural gas as Russia is already, and will be in the future, the most important gas supplier to the German and European gas markets.

Results and Discussion

The analysis illustrates a significant change in the gas supply over the next two decades. The EU Gas Fields are in decline and it is predicted that these will run dry. In parallel the share of Russian and Norwegian natural gas, and also the levels of LNG production (e.g. from Algeria or Egypt), will increase. Although the potential for GHG emissions tends to grow as a result of greater transport distances and demanding production and processing activities, high investment in necessary mitigation options (e.g. through replacing older and inefficient technology; updating to state-of-the-art technology) may neutralise the increase. The overall result of these counteracting trends will be to decrease GHG emissions, in a range of around 12% per TJ of direct emissions of natural gas, depending on the level of investment in the modernisation of the Russian gas infrastructure and the improvements of the LNG process. In the two given scenarios the indirect emissions of the natural gas used in Germany will decrease from about 23 million t CO₂-eq (2005) to 19.5 or 17.6 million t CO₂-eq in the year 2030. In spite of a significant higher gas consumption the emissions are reduced in the first scenario due to technical modifications. In the second scenario the emission reduction is based on the lower gas consumption.

Conclusions

At present, the indirect GHG emissions of the natural gas process chain are comparable to the indirect emissions produced by oil and coal. The emission trend of the natural gas process chain will markedly decrease if the mitigation options are followed consistently. However, in order to ensure the long-term security of natural gas supply for future decades, a high level of investment is essential. With regard to future emissions, the best available technology and, therefore, that which is most economically feasible in the long term, should be used. Under these conditions natural gas — as the fossil fuel with the lowest levels of GHG emissions — can play a major role in the transition to a renewable energy supply for the future.