CHERNOZEMS in the Baltic Sea region indications of an anthropo-pedogenesis

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Heini Bretz
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1 CHERNOZEMS in the Baltic Sea region indications of an anthropo-pedogenesis Workshop on Anthrosols in Brazil 2016 Andre Acksel and Peter Leinweber Soil science - University of Rostock, Germany

2 Occurrence of STUDY Chernozems AREA in central Europe North Sea Hamburg Rostock Baltic Sea Berlin Frankfurt 2

3 SOIL CHARACTERISTICS P-1 P-2 P-3 P-4 P-5 F-6 F-7 F-8 S-9 3

SOIL CHARACTERISTICS Mollic horizons (Axh) Thickness: 20 60 cm C

4 SOIL CHARACTERISTICS Mollic horizons (Axh) Thickness: cm C org : 0.5 to 2.2 % Soil color: 10 YR 4/1 Intensive bioturbation 4

5 OBJECTIVES to characterize the SOM composition of the mollic horizons (Axh) by: Pyrolysis-Field Ionization Mass Spectrometry (Py-FIMS) X-ray Absorption Near-Edge Spectroscopy (XANES) Benzene polycarboxylic acids (BPCA) to understanding the formation of the mollic horizons (Axh) 5

6 Pyrolysis-Field Ionization Mass Spectrometry (Py-FIMS) Soft ionization in high electrity field prevented fragmentation Allows the recording molecule peaks (fingerprints) Indicator marker for biogenic compound classes in the SOM 6

7 Py-FIMS Mass spectra 7

8 % in TII Py-FIMS Compound classes *** ** *** ** * *** *** Ap Axh * P<0.05 ** P<0.01 *** P<0.001 (n = 3) 2 * 0 CHYDR PHLM LDIM LIPID ALKYL NCOMP STEROL PEPTI SUBER FATTY Compound classes 8

9 X-RAY ABSORPTION NEAR-EDGE SPECTROSCOPY (XANES) Electron binding energy Element specific 9

10 X-RAY ABSORPTION NEAR-EDGE SPECTROSCOPY (XANES) carboxylic C aliphatic C aromatic C 10

11 XANES CARBON a) Quinone b) C=C in protonated/alkylated aromatic c) N-substituted aromatic P-5 d) aliphatic C e) carbonyl-c (C=O) in amides f) carboxylic(o=c-o) f) carbohydrates F-6 11

Benzene polycarboxylic acids (BPCA) 20 18 Ap/Ah Axh BPCA in % of C org 16

8 6 4 2 0 P - 1 P - 2 P - 3 P - 4 P - 5 F - 6 F - 7 F - 8 S - 9 Mean Site

12 Benzene polycarboxylic acids (BPCA) Ap/Ah Axh BPCA in % of C org The BPCA indicated an input 12 of 10 pyrogenic organic matter P - 1 P - 2 P - 3 P - 4 P - 5 F - 6 F - 7 F - 8 S - 9 Mean Site 14% 10% Py-FIMS and C-XANES supported the BPCA P-1 P-2 P-3 P-4 P-5 F-6 F-7 F-8 S-9 12

13 Phthalsäure Isophthalsäure Terephthalsäure BPCAs RATIOS Prehnitsäure Mellophansäure Benzoesäure Hemimellitsäure Trimellitsäure Trimesinsäure B5CA The pattern of BPCA Prehnitsäure Pyromelli Benzolpentacarbonsäure Mellitsäure Phthalsäure Isophthalsäure Terephtha HNO 3 Mellophansäure 170 C Pyromellitsäure Hemimellitsäure Trimellitsäure Trime B3CA B6CA Benzolpentacarbonsäure Mellitsäure B4CA Prehnitsäure 13 Mellophansäure Pyromel

14 BPCAs RATIOS The portions of B6CA compared to B5CA are dependent on the fire temperature. B5CA/B6CA ratios indicated different fire regimes: = forest/grass fires = shrub fires = domestic fires (Schneider et al., 2010; Wolf et al., 2013) 14

B5CA/B6CA BPCAs RATIOS 2.5 2.0 1.5 Ah Axh B5CA/B6CA ratio: 1.3-1.9 = forest/grass fires 0.8-1.7 = shrub fires 0.3-0.8 = domestic fires (Wolf et al., 2013) 1.

15 B5CA/B6CA BPCAs RATIOS Ah Axh B5CA/B6CA ratio: = forest/grass fires = shrub fires = domestic fires (Wolf et al., 2013) BPCAs ratios indicated vegetation fires 0.0 P - 1 P - 2 P - 3 P - 4 P - 5 F - 6 F - 7 F - 8 S - 9 Mean P-1 P-2 P-3 P-4 P-5 F-6 F-7 F-8 S-9 Site 15

16 CONCLUSIONS The portions of BPCA indicated that the Baltic Chernozems are anthropogenic developed by fire regimes! 16

17 OUTLOOK Deep topsoils in Orkney (Simpson et al., 1993) Plaggen soils (Giani et al., 2014) Baltic Chernozems Black soils in Germany (Wiedner et al., 2014) 17

18 THANK YOU for your attention. 18

19 ACKNOWLEDGEMENT We thank Canadian Light Source (CLS) and the University of Saskatchewan, the German Academic Exchange Service (D/05/50492), W. Amelung, M. Wolf and A. Kappenberg (INRES, University of Bonn) for BPCA analyses E. Heilmann for lab assistance and K.-U. Eckhardt for Py-FIMS measurements and A. W. Gillespie and J. Dynes at the SGM beamline of the CLS. 19

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