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Degradative fate of 3-chlorocarbazole and 3,6-dichlorocarbazole in soil

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Abstract

Background, aim, and scope

3-Chlorocarbazole and 3,6-dichlorocarbazole were isolated from Bavarian soils. The stereospecific formation of the isomers of these chlorinated carbazols can be explained by quantum mechanical calculations using the DFT method. It was shown that chlorination of carbazole and 3-chlorocarbazole respectively is preferred via the sigma-complexes 3-chlorocarbazole and 3,6-dichlorocarbazole as the most stable products. The dioxin-like toxicological potential of 3,6-dichlorocarbazole, determined by the Micro-EROD Test, is in the range of some picogram TCDD equivalents per milligram carbazole. The degradative fate of 3-chlorocarbazole and 3,6-dichlorocarbazole was analysed within a long-term study (57 days) in soil.

Materials and methods

The soil was extracted by ASE (accelerated solvent extraction) and a further clean-up procedure with column chromatography and chromatography with C18-SPE stationary phases. Quantification of 3-chlorocarbazole and 3,6-dichlorocarbazole was performed employing the isotope-dilution method. The samples were measured with high-resolution GC/MS.

Results

The degradation (ln(c/c0) vs. time with best-fit line) showed in almost every storage condition a very small degradation (slopes (h−1) in −10−4 range). However, the decay for the controls were two to three times (−28°C) and six times (with sodium azide) higher, than the decrease of 3-chlorocarbazole and 3,6-dichlorocarbazole in the samples of environmental conditions.

Discussion

Especially because of the toxicological potential of 3-chlorocarbazole and 3,6-dichlorocarbazole the proven degradative fate is of large interest. The results show that the analysed carbazoles are not readily degradable in this time period.

Conclusions

The expected results of exponential decay behaviour could not be proven.

Recommendation and perspectives

Longer-lasting studies are expected to reveal more accurate half-lives, although it has been shown here, that the compounds are not readily degradable in their native soil environment.

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Abbreviations

A horizon:

Soil horizon; top soil

ASE:

Accelerated solvent extraction

Au:

Energy in atomic units; 1au = 627.51 kcal/mol

B horizon:

Soil horizon, first horizon after top soil

CHC:

Chlorinated hydrocarbons

CIS:

Cold injection system

DFT:

(Standard) density functional theory

E:

Enthalpy [au]

E rel :

Relative energy [kcal/mol]

EI:

Electron ionisation

EROD:

7-Ethoxyresorufin-O-deethylase

FW:

Fresh weight

GC/MS:

Gas chromatography and mass spectrometry

Go-Ah:

24–39 cm Transfer horizon: mineral top soil horizon with accumulation of organic substances and groundwater-swayed mineral soil horizon, oxidative circumstances

OCP:

Organochlorinated pesticides

PAH:

Polycyclic aromatic hydrocarbons

PCDD/F:

Polychlorinated dibenzo-p-dioxin and dibenzofuran

PCT:

Pentachlorotoluene

PSE:

Potential energy surface

PTFE:

Polytetrafluoroethylene

SIM:

Selective ion monitoring

SPE:

Solid phase extraction

STD:

Standard deviation

TCDD:

2,3,7,8-Tetrachlorodibenzodioxine

TE:

Toxicity equivalent

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Authors and Affiliations

  1. Helmholtz Zentrum München—German Research Center for Environmental Health, Institute of Ecological Chemistry, Ingolstädter Landstr. 1, 85764, Neuherberg, Germany

    Lisa Tröbs, Bernhard Henkelmann, Dieter Lenoir & Karl-Werner Schramm

  2. Bayerisches Landesamt für Umwelt, Hans-Högn-Straße 12, 95030, Hof, Germany

    Arthur Reischl

  3. Department für Biowissenschaftliche Grundlagen, TUM-Technische Universität München, Weihenstephaner Steig 23, 85350, Freising, Germany

    Karl-Werner Schramm

Authors
  1. Lisa Tröbs
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  2. Bernhard Henkelmann
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  3. Dieter Lenoir
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  4. Arthur Reischl
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  5. Karl-Werner Schramm
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Corresponding author

Correspondence to Karl-Werner Schramm.

Additional information

Responsible editor: Ake Bergman

This publication is dedicated to Prof. Sandermann on the occasion of his death on August 18th, 2009.

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Tröbs, L., Henkelmann, B., Lenoir, D. et al. Degradative fate of 3-chlorocarbazole and 3,6-dichlorocarbazole in soil. Environ Sci Pollut Res 18, 547–555 (2011). https://doi.org/10.1007/s11356-010-0393-0

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