Chlorcarbazole in Böden

Goal and Scope

In soil samples taken from several locations throughout Bavaria, the detection of p,p′-DDT by GC/MS was impeded by a superimposed peak. The authenticity of this compound, which has been identified as dichlorocarbazole by mass spectra databases, is confirmed and some characteristics of its occurrence in soils are described.

Methods

The authenticity of the unknown compound has been checked by comparing the low resolution mass spectra and chromatographic retention times with those of standard compounds. Some methodical studies concerning extraction and clean-up were also carried out.

Results and Conclusion

Mass spectra and retention of the unknown compound are identical with that of the 3,6-dichlorocarbazole standard compound; additionally, a second chlorocarbazole was found with mass spectrum and retention similar to 3-chlorocarbazole. In many topsoils (A-horizons) and subsoils (B-horizons) from 200 locations of different land-uses, the dichlorocarbazole could be detected. In contrast to PAH and other POPs, maximum concentrations occurred in the A- and upper B-horizons of forest soils rather than in the organic layers. Assuming the environmental distribution properties of the chlorocarbazoles to be similar to those of the PAH, this could indicate that the chlorocarbazoles are not deposited from the atmosphere as a result of anthropogenic activities but might be generated by natural processes in situ.

Recommendation and Perspective

To our knowledge, the occurrence of chlorocarbazoles in soils of unpolluted sites has not been previously described. Their widespread occurrence in relatively high concentrations and their detection using analytical standard procedures is surprising and requires further examination.     

Verunreinigte Böden

This article discusses the evaluative criteria which are applied for the assessment of contaminated soils. Guide values for materials in the soil (reference values, test values and action levels). Such guide values can be derived based upon either functional or constitutional criteria. The leachate from the soil must be analyzed for noxious materials in order to ensure the conservation of both ground- and surface-waters. Furthermore, existing concepts and drafts for evaluating soil contamination are discussed. The great diversity of the 37 regulatory publications for evaluating soil contamination is due to 1. different purposes these guidelines are aimend at, and 2. varying philosophies with regard to the degree of safety which is considered to be acceptable:

1. The approach of the LAGA (Länderarbeitsgemeinschaft Abfall-German federal cooperative for waste regulation) is to merely avert dangerous effects of polluted land rather than to take precautionary measures.
2. The approach of the state of Baden-Württemberg is to combine precautionary activities and defensive procedures in one scheme with the technical and financial feasibility as criteria for the final decision.

A summary of the valid legislation is discussed, based on the specific regulatory works of the individual German states:

- The federal soil protection act and the directives based on it

- Inherent problems with deriving test values from basic toxicological data as well as the question of a tolerable cancer risk level

The procedure of linking the test values with a concrete danger to health that was designed for the federal soil protection act is discussed and compared with an alternative procedure. A presentation is given of the LABO (Länderarbeitsgemeinschaft Bodenschutz — German federal and state cooperative on soil conservation) utilization concept for soils: The use of test values for assessing soil materials with regard to particular utilization goals. The article quotes the ?Guideline for monitoring the success in soil cleanup operations” as compiled by the GDCh working group on ?Environmental chemistry and ecotoxicology” (1996). This guideline provides a review of the evaluatory concepts applied in the German states of Hamburg, North Rhine-Westphalia, Brandenburg, Rhineland-Palatinate, Hessen, Baden-Württemberg, as well as those of the German federal cooperative for waste regulation (LAGA). The respective procedures and specifications of Holland, Canada, the USA are also noted in this guideline.     

Bestimmung von leicht freisetzbarem Cyanid in Böden und Wässern mit der Mikrodestillation

Easy-liberatable cyanide has to be analysed if soils and waters are contaminated by cyanide. The aim of this study was to determine easy-liberatable cyanide in these environmental samples using a micro-distillation apparatus by means of a modified digestion vessel. Pure aqueous solutions of different cyanide species, five contaminated and uncontaminated soil samples and two water samples were analysed by micro-distillation according to the German standards. Recovery was determined by analysis of spiked samples. When using the modified digestion vessels, the pH of 4 which is demanded by the standard method can be adjusted. The recovery of potassium cyanide and weakly-complexed zinc-cyanide ranged from 93–101% for standards, and from 87–98% for spiked samples. In contrast, the recovery of strong iron-cyanide complexes was below 4% both for pure solutions and spiked samples. The precision of the method expressed as a relative standard deviation was 25% in cases of very low easy-liberatable cyanide contents (< 1 mg CN kg^?1) and below 12% in case of high easy-liberatable cyanide contents (> 1 mg CN kg^?1) for contaminated soils. The determination of easily-liberatable cyanide in soils and waters using micro-distillation combined with the modified digestion sample is an alternative to other distillation methods.     

Einschätzung der Konzentrationsprofile polyzyklischer aromatischer Kohlenwasserstoffe (PAK) in Böden des Biosphärenreservates Spreewald

To work out background values, the information of concentration profiles of PAHs in soils of uncontaminated territories is indispensable. This investigation shows PAH concentrations of different soil samples like agricultural soils, grassland, forest and litter from the biosphere reserve in Spreewald, Germany. The mean values of the soil samples are about 460 μg Σ-PAK/kg d.m. A top value of 7.2 mg Σ-PAK/kg d.m. shows a sample of a flooded grassland area. The relation of the concentrations in the litter, forest, grassland and agricultural soil samples is about 5∶3∶2∶1. Compared to the other samples, the litter samples contain a higher amount of low molecular PAHs. Increasing distance to the former power plants Lübbenau and Vetschau (brown coal) lead to decreasing PAH contents in the soil samples of forests from 2190.9 after 4 km to 294.8 Σ-PAK/kg d.m. after 16 km. In comparison to results obtained in Nordrhein-Westfalen and Bayern, the PAH measurements indicate Spreewald to be an uncontaminated and rural area.     

Persistente organische Schadstoffe in Böden, Gewässern und in Firn der Region nördliches Piringebirge (Bulgarien)

Systematic environmental screenings are still the exception in South-Eastern Europe. Especially, there is a decisive lack of information concerning the occurrence and behaviour of xenobiotic and toxic compounds like volatile-and non volatile halogenated organics, suppressed by the surrogate AOX, synthetic chelating agents, pesticides, like DDT as well as chlorate in the biosphere. The analysis of soils, waters and firns of a representative area in Bulgaria, the Pirin mountains, indicate a relatively low back ground pollution. The accumulation of the xenobiotics in this high mountain region is recognised to be low. Nevertheless, traces of pesticides and chelating agents like EDTA and NTA in ice (firns) and soils were found. The surrogate AOX should be a parameter, suitable for routine environmental screenings of such areas.     

Screening zur Mobilisierbarkeit von Kupfer aus Böden und Schlämmen

In the presented paper, the pHstat-procedure is compared with four simple extraction procedures. These procedures make use of the following extraction solutions: distilled water (based on DIN 38414 part 4, DIN-S4), 1 mol/L ammonium nitrate, 1 mol/L ammonium acetate at pH 7.0 and 1 mol/L sodium acetate at pH 5.0, respectively. The extraction procedures were applied to 10 different soil samples and 2 sludges. The DIN-S4-procedure shows the lowest amounts of mobilized copper. The highest parts are extracted by sodium acetate solution. For the procedures investigated, the mobilized amounts extracted by ammonium acetate solution are most comparable with those of the pHstat-procedure. The simple sodium acetate procedure is useful for screening to select significant samples from a large number of soils. Thus, the high effort caused by the pHstat-procedure can be reduced to a minimum through the application of this screening procedure. The application of this screening, however, is difficult for samples containing large parts of organic compounds, e.g. sewage sludge. These samples show a different extracting behaviour.     

Bewertungsmaßstäbe zur Beurteilung von Schadstoffbelastungen in Böden anhand der Bioverfügbarkeit

Until now, assessment of contaminated sites is based on variable protection goals, whereby total contents and in part mobile contents are considered. Due to interactions of pollutants in soil and bound residues, total contents do not reflect the actual risk. In contrast an investigation based on availability/bioavailability of contaminants would enable a harmonization of the protection-goal-based evaluation and a closer-to-reality risk assessment for the individual location.     

Phthalatkonzentrationen in Böden naturnaher Standorte des Sollings (Niedersachsen)

The phthalat concentrations in soil samples from the Solling (Ecological Research Project Solling) were measured. The samples were collected from a beech and a spruce forest and aTrisetum flavescens meadow. The distance from the tree trunks and the different horizons were taken into consideration as well. Dimethylphthalat, diethylphthalat, dibutylphthalat, butylbenzylphthalat, di-(2-ethylhexyl) phthalat and dioctylphthalat were determinated using GC/MS. From the six phthalates investigated, four were detected in the samples. Dimethyl and diethylphthalat were found at very low concentrations in only one sample. Dibutyl- and di-(2-ethylhexyl)phthalat were detected in eight of 21 samples. No phthalates were found in the samples from theTrisetum flavescens meadow. Two of the nine samples from the beech forest showed phthalates. In six of the nine samples from the spruce forest phthalates were detected. Phthalate concentrations in the spruce forest were always higher than those found in the beech forest.     

Konzentration und Verteilung von Platingruppenelementen (PGE) in Böden

In Germany automobile exhaust control by platinum-group element (PGE) loaded catalysts is now well established. By mechanical or chemical attrition, these catalysts could act as a potential source for a significant increase of PGE abundances in the environment. During a recent research program concentrations and distributions of PGE in different soils were measured along the highway A66 Frankfurt-Wiesbaden. 71 nearsurface soil samples were analysed by graphite furnace atomic absorption spectrometry (GFAAS). The results revealed average abundances of 10 ppb platinum and 3 ppb ruthenium. Palladium as well as rhodium were below the analytical detection limit of 2 ppb. With increasing distance from the highway edge PGE values gradually decreased. Only the upmost soil layer, down to 20 cm depth, contains measurable PGE concentrations. Results: There are irregular PGE concentrations of anthropogenic origin in different soils along the highway A66 Frankfurt-Wiesbaden possibly arising from automobile exhaust catalysts. Further monitoring could help to avoid potential environmental hazards. *** DIRECT SUPPORT *** A00HP020 00002     

Umweltschäden durch Heizöl nach Hochwasserereignissen

Background Due to high safety measures in production, transport and storage of fuel oil it rarely occurs, that fuel oil will be released in the environment. One exception of this experience was the fuel oil releases of private fuel oil tanks during the “century flood” 2002 in Germany. By order of IWO (Institut für wirtschaftliche Oelheizung e.?V.), the authors investigated the environmental behaviour of fuel oil after flood incidents. Aim Due to the fast spreading of the fuel oil on water surfaces and the contamination of huge areas one expects large environmental harm. For appraisal the behaviour of fuel oil in water and soil must be studied in detail as well as the effect on high and low developed animals and plants, on water organisms and on the flora and fauna of soil. From the valuation of the environmental harm official measures and measures of precaution and safety by manufacturer and user of private fuel oil installations can be derived. Main features For considering the various aspects the authors studied the extensive analyses of the special measuring programme of Saxony-Anhalt, used interviews of concerned persons (private persons and officials), aerial photos, extensive study of literature including eco-toxicological investigations, experiences of more than 70-years applications of fuel oil in plant protection and practical experiences at large field redevelopment of oil damages following averages and accidents. The authors valuated on the base of results of analyses and on own calculations. Results The release of fuel oil in the air is no particular problem because about 40?% of the oil fast evaporate and will be decomposed to carbon dioxide and water. In addition to the evaporation a characteristic behaviour is fast spreading of the fuel oil on the water surface to very thin layers. For a typical coloured oil layer e.?g. one cubic meter of oil is spread on a water surface of about 3?km², this corresponds to 3?ml/m² surface and contaminates the soil after drying up with about 3?µg/kg soil some orders less than the natural content of hydrocarbons in soil. Because of the absorption capacity of soil and the microbial decomposition by everywhere existing hydrocarbons decomposing micro-organisms the oil infiltrates only a few centimetre and will be decomposed in a few months, so that ground water detriments not arise practically. By measurements a few months after fuel oil release in the flood 2002 oil components in the soil could not be detected. Discussion Acute injuries of micro-flora and -fauna in soil and water by fuel oil cannot be excluded from the first. Thus the limiting values of injuries for some water organisms are below 1?mg/l. According to the special measuring programme at the flood 2002 in Saxony-Anhalt however the measured values were mostly wide below of this limit. In detail the spreading and evaporation of fuel oil on water surfaces, the propagation and decomposition of fuel oil in soil will be described. A quantitative valuation of fuel oil distribution in a real flood incident will be given. Conclusions Particular measures of redevelopment of soil for fuel oil release after flood incidents are not necessary normally. Even at the redevelopment after transport damages or at devastated sites with essential higher oil contaminations of soil in comparison to fuel oil release after flood incidents high decomposition rates are obtained by normal soil improving measures supporting the natural micro-organisms in reducing the hydrocarbon concentration for 70–90?% after a few months. Perspectives With the described results a realistic valuation of the environmental harm of fuel oil release after flood incidents could be given. From this qualified measures can be derived for official decisions and precautionary and reliable activities at fuel oil installations of flood endangered areas.     

Bakterielle Mineralisierung von Dibenzofuran,Dibenzo-p-dioxin und 1,2,4,5-Tetrachlorbenzol in Böden

Quantitative degradation of dibenzofuran (DBF), dibenzo-p-dioxin (DBD), and 1,2,4,5-tetrachlorbenzene (TeCB) by the bacterial strains sphingomonas sp. HH 69, sphingomonas sp. RW1 and pseudomonas sp. PS 14 was investigated by radio-tracer techniques in liquid cultures and especially in samples of different soils. Pure strains converted DBF, DBD and TeCB up to 80% to CO₂ within few days. This degradation occurred not only in aerated liquid cultures but also in heterogeneous soils, with low levels of other pollutatns at favourable pH-values. Rate and degree of the mineralization of DBF, DBD and TeCB were independent of the DBF-, DBD-, or TeCB-concentration in the soils within a broad range. There was obviously a close correlation between the starting concentration of active cells (starting bacterial count) and the rate of degradation of the test substances in soil; by raising the starting bacterial count in the soil samples, mineralization of DBF, DBD, and TeCB, respectively, was clearly accelerated. However, under nearly the same coniditions in more acid soils (pH-values < 4) no significant degradation of DBF, DBD, and TeCB to CO₂ took place. As expected, this difficulty can be overcome by mixing CaCO₂ into the acid soils (liming). Easily utilizable substances like peptone, triolein, and glucose added as special carbon and energy sources to low contaminated soils, had only a small—if any—effect on the mineralization of DBF, DBD, and TeCB. In soils contaminated by a mixture of pollutants, the bacterial strains could develop their degradation capacity only to a limited extent and showed different degradation effects depending on the basic type of contamination. The efficiency of the degradation specialists was thus dependent on the “Chemical Environment” (type and concentration of contaminants present).     

Coplanare polychlorierte Biphenyle (PCB) in den Oberböden Hamburgs

Goal and Scope

In topsoil samples of areas with different land use within the agglomeration of Hamburg, the coplanar polychlorinated biphenyls PCB 77, 126 und 169 were determined to estimate the importance of coplanar PCBs in urban soils. Proportions relative to Balischmiter-PCBs (PCB 28, 52, 101, 138, 153 and 180) and PCDD/F concentrations were examined.

Methods

Soil samples were taken from different depths (litter horizon, 0–10 cm, 0–30 cm) at 24 different sites within the State territory of Hamburg. Coplanar PCBs, Ballschmiter-PCBs and PCDD/Fs were analysed by GC-MS-coupling in the soil fraction <2 mm. Congener distributions are discussed with respect to contamination sources.

Results and Conclusion

Land use and position of soil sample areas are only of subordinate importance for coplanar PCB concentration of the soil samples. The industrial centre of Hamburg (including harbour) shows higher contamination concentrations than the suburban areas. In levels, patterns and relative proportion to PCDD/F concentrations, the samples from dredging material disposal fields differ from all other samples. Calculation of coplanar TEQs related to total TEQs shows a contribution to total TEQs of 11–32% for the background (non dredging material influenced) samples.

Recommendation and Perspective

Estimation of coplanar PCB concentrations by determining Ballschmiter-PCB concentrations in top soil samples does merely work at samples which contamination is caused by the use of commercial PCB mixtures. Rating samples by TEQ concentrations, an increase of TEQs up to 30%, due to coplanar PCBs, should be reckonned. These considerations should be reason for extending the usual PCB determinations of Ballschmiter-PCBs to coplanar PCBs in more cases than is the general practice today.     

Erprobung und Erfolgskontrolle eines Phytoremediations-verfahrens zur Sanierung Sprengstoff-kontaminierter Böden

Results of a field experiment (please refer to Warrelmann et al. 2000a) document TNT-degradation and regeneration after the establishment of a phytoremediation. Various approaches are included in a complex monitoring system, which are conducted in the field (nitroaromatics in soil, seepage water, and plants; soil fauna; soil fungi; decomposition) as well as in the lab (a battery of 6 biotests). The data document a high heterogeneity of the TNT-contamination, a rapid initial decrease and a mediocre displacement of nitroaromatics in plants and seepage water. The initial rapid transformation of TNT to aminodinitrotoluenes ceases significantly after 3 months. Results of the biotest battery allow a sophisticated assessment of soil toxicity; the results from the soil ecological field investigations make the long-term effects of TNT-contamination likely. In a third part of the series of articles, a synopsis and judgement of the project will be delivered.     

Erprobung und Erfolgskontrolle eines Phytoremediationsverfahrens zur Sanierung Sprengstoff-kontaminierter Böden

The final article of a series of three evaluates the in situ-remediation of TNT(trinitrotoluene)-contaminated soil from ‘Werk Tanne’. The multidisciplinary approach allows a differentiated assessment. Grading with large-scale machinery leads to a depletion of TNT for almost 90% within the first 6 months, while ADNT(amino-dinitrotoluene)-content decreases more or less steadily over 1,5 years. Grading reduces the heterogenous distribution of the contamination only slightly. Results from field-monitoring and biotest-battery indicate residual toxicities of ecotoxicological relevance and a reduced capacity for biological regeneration, in comparison with the uncontamined site. Mycorrhized plants safe-guard the site and improve the soilecological conditions. Their role in reducing lower level residual toxicity requires further investigation. There is need for future research (1) on the dynamics and mechanisms of the initial decrease of TNT followed by stagnation, (2) on the fate of the primary metabolites, (3) on long-term effects of the phytoremediation, and (4) on the establishment of the complex monitoring for routine work.     

Erprobung und Erfolgskontrolle eines Phytoremediationsverfahrens zur Sanierung Sprengstoff-kontaminierter Böden

On the area of a former ordnance plant (‘Werk Tanne’, Clausthal-Zellerfeld, Germany), a field experiment for phytoremediation of TNT-contaminated soils has been carried out since May 1999. The concept is based on a stepwise degradation of TNT by white-rot fungi and mycorrhiza within the rhizosphere of site-specific seedlings. An appropiate site with contaminants in the surface-soil was prepared with a large-scale soil grader and subsequently divided into different experimental plots, including an uncontaminated control as well as a contaminated plot without treatment. Planting of the selected trees and shrubs (infected with mycorrhiza during nursery) and inoculation with wood chips (inoculated with white-rot fungi) is followed by a detailed monitoring of the experimental plots (chemical analyses, biotest-battery, ecological field indicators). For the evaluation of the results, multivariate methods are applied.     

Luzernemehl-induzierte Aktivitätserhöhung (LIA) in ökotoxikologisch-mikrobiologischen Tests

In previous trials, lucerne-meal induced increase in microbial activities (=LIA) was used as a new ecotoxicological indicator of pesticide effects on soil microorganisms. In the following, this technique has been applied to measure and compare the effects of the two dinitrophenol herbicides ‘Flüssig Herbogil’ (active ingredient dinoterb) and ‘Aretit flüssig’ (active ingredient dinoseb acetate) used as reference compounds. A loamy sand soil known for its sensitive microflora was treated with the herbicides and incubated up to 90 days under laboratory conditions. In order to ensure the comparison of the specific effects, equal amounts of the active ingredients of the two formulated herbicides, based on the field rate of ‘Flüssig Herbogil’, were applied. In a parallel trial, the soil was additionally amended with lucerne meal to enable the determination of its specific stimulatory effect on microbial activity. The two biomass-related microbial activities dehydrogenase (=DHA) and glucose-induced short-term respiration (=KZA) were measured, as well as the nitrogen mineralization (=N_min). Depending on the dosage, the activities of LIA-DHA, LIA-KZA and LIA-N_min as increased by lucerne meal, were affected by the herbicides. Normally, the biomass-related activities were inhibited with exception of LIA-DHA at the single dosage. However, the nitrogen mineralization was enhanced. In most cases, the effects caused by ‘Flüssig Herbogil’ (dinoterb) were more pronounced than those of ‘Aretit flüssig’ (dinoseb agetate) when the same amount of the active ingredients had been applied. The LIA of the tested microbial activities proved to be a sensitive indicator for pesticide effects on soil microorganisms. It enabled the differentiation of the ecotoxic effects of chemically similar pesticides. Using this indicator will support results from separate trials run with or without lucerne meal, because marked losses of microbial biomass will become more pronounced. In addition, this improves the interpretation of ecotoxicological effects of pesticides in soil.