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Sorption and distribution of aged atrazine residues in the drainag

outdoor lysimeter experiment

N. D. Jablonowski

+, S. Köppchen, A. Schäffer*, P. Burauel

Agrosphere - ICG-4, Forschungszentrum Jülich GmbH, D - 52425 Jülich, Germany

*RWTH Aachen University - Institute for Environmental Research (Biology V), 52074 Aachen, Germany

+Author for correspondence: Nicolai D. Jablonowski – n.d.jablonowski@fz-juelich.de; +49-2461-61-2696

REFERENCES(1) Kegley, S.E., Hill, B.R., Orme S., Cho

http:www.pesticideinfo.org. 2009.

(2) U.S. Department of Agriculture; National Agric

2004. USDA/NASS: Washington, D.C., 2004.

(3) Jablonowski, N. D., Koeppchen, S., Hofmann, D

lysimeter soil after 22 years. In Press: Env. Poll.

(4) Jablonowski, N. D., Koeppchen, S., Hofmann, 

14C-labeled atrazine residues in soil. J. Agric. F

(5) Jablonowski, N. D., Modler, J., Schäffer, A.

agriculturally used soil and its particle-size aggr

(6) Brun, G. L., MacDonald, R. M., Verge, J., and A

Canada; 1980-2000. Chemosphere, 2008, 71, 3

(7) Glotfelty, D. E., Seiber, J. N., and Liljedahl, L. A

(8) USEPA: National Pesticide Survey: Summary R

ACKNOWLEDGEMENTSThe SEM analysis by Henrik Daniels, the chemico

are gratefully acknowledged. Thanks to AHenkelmann, LfL Munich, for the lysimete

RESULTS

CONCLUSIONS

•The presented results proof the long-term (>22 years) persistence of atrazine and its metabolites in the environment

and their sorption on gravel, clay-particles and carbonaceous slag-like particles.•Two percent of the gravel-drainage system consisted of carbonaceous slag-like particles of unknown origin – retaining 31% of 

total residual 14C-activity in the drainage system

•Aside atrazine and its metabolite 2-hydroxy-atrazine (as described previously (3)), all possible atrazine metabolites were 

detected at least in the first extract of the carbonaceous slag-like particles (Figure 1, Figure 2, and Table 1)

•The porous structure and the high organic carbon content in the slag-like particles promoted the long-term sorption of atrazine and its metabolites (Figure 3, Table 2)•Porous structure of natural materials likely enhances sorption of organic chemicals in general, due to a high surface area 

(Figure 3 – Figure 5)•The fact that atrazine and its metabolites were found in the drainage system of a long-term outdoor lysimeter experiment proves 

the leaching character of these compounds into deeper soil and/or ground water layers•Carbonaceous materials such as “biochar”, black carbon, etc. can foster the retention of (agro-) chemicals in soils and waters

OUTLOOK•Quantification of all detected atrazine metabolites in the ASE-extracts from carbonaceous slag-like particles, gravel and clay is in progress.

clay 81.55 ± 3.80 1.37 ± 0.04 0.69 ± 0.02 

gravel 24.44 ± 0.54 0.36 ± 0.004 10.3 ± 0.0 

slag 1602.85 ± 9.17 20.0 ± 0.14 0.182 ± 0.025 

C 

Bq g Corg. inorg. -1

Figure 3: Surface structure of the carbonaceous slag-like particles. High porosity likely promotes binding and sorption of atrazine and its residues on a long-time scale over decades.

Table 2: Chemico-physical analysis of the solid s

which were separated by aqueous shaking extractio

Figure 1: Extraction efficiency of aged 

14C-atrazine 

residues from carbonaceous slaglike particles, gravel and clay, using ASE and methanol-water solution.

Figure 2: Detection of atrazine and all of its metabolites was possible in the first extract of the slag-like material. 

INTRODUCTION•Atrazine: s-triazine herbicide, one of the largest selling pesticides worldwide•Severely restricted in the EU, but still widely used in North America, in Africa, in Asia and the Pacific region (1)

•Applied on 70% of all corn acreage in the US, corresponding to approx. 26,000 metric tons for the US program states only (2) 

Unexpectedly high persistence of this chemical in the environment (3-5) gives reason to alert, since atrazine has been detected 

in ground-, surface and rainwater frequently, and also in fog, ambient air, arctic ice and seawater (e.g. 6-8)

•Strong sorption and persistence of atrazine and its metabolites on carbonaceous particles is highlighted, providing novel findings 

on the overall long-term persistence of this chemical and its residues/metabolites on natural soil components.

MATERIAL AND METHODS•Used material: gravel-mixture of drainage system 

successive annual 14C-labeled atrazine applications 

•Sample partitioning: 1) gravel; 2) slag-like particles•Microscopic surface analysis of the different partic

•Sample preparation: samples were freeze dried, cr

•The chemico-physical analysis: ICP-OES (TJA-IRI

•14C-determination: solid samples were oxidized via 

•Solid sample extraction: ASE device (ASE 200, Dio

•14C-activity detection: liquid scintillation counter (LS

•Detection and quantification of atrazine and its met

Table 1: Atrazine and its metabolites detected in sample extracts:

5) desisopropyl: slag 1/5-3/5 and gravel 1/5; 6) desethyl: slag 1/5 and gravel 1/5; 

7) 2-hydroxy: slag 1/5-5/5, gravel 1/5 and 2/5, clay 1/5-5/5; 8) atrazine: slag 1/5, gravel 1/5, clay 1/5.

1) desethyl-desisopropyl-2-hydroxy: 

slag 1/5-5/5, clay 1/5-3/5;2) desethyl-desisopropyl: slag 1/5 and 5/5; 

3) desisopropyl-2-hydroxy: slag 1/5-5/5; 

4) desethyl-2-hydroxy: slag 1/5-5/5;