. Practical applications of stable isotopes technologies for timber tracking 1 16.08.2012 GmbH
. Our analytic tools. Stable isotopes in bioelements Not radioactive Found in all nature Different distribution and pattern hydrogen D/H 18 O/ 16 O 34 S/ 32 S stable 13 C/ 12 C The physical fingerprint of the nature 87 Sr/ 86 Sr 15 N/ 14 N radioactive Physical tracking tool In relation to one million atoms from Variation in the nature hydrogen the biomass consists of oxygen nitrogen carbon sulfur 150 heavy hydrogen 2000 heavy oxygen 3600 heavy nitrogen 11000 heavy carbon 42000 heavy sulfur 2 16.08.2012 GmbH
ppm [18O]. The stable isotopic scale. 2025 2020 2015 2010 2005 2000 1995 1990 The stable isotopic scale is relative to an international standard (deviation in ). -8,9 0 +4 1985 1980 Kinetic fractionation incomplete processes, e.g. 1. distillation 2. diffusion Rhine water ocean water Nile water 3. chemical reactions Increased amount of heay oxygen: 18 O Complete processes, no fractionation!!
. Isotopic patterns in the global water cycle. Bowen J., Geology, 4, 315-318 4 16.08.2012 GmbH
. Stable isotopes Information to track back agricultural products Country level: The D/H (hydrogen) and 18O/16O (oxygen) ratios depending on the water / rainfall cycle could differentiate a wide region. Regional level: The 13C/12C (carbon), as a climate and 87Sr/86Sr (strontium) as a geological parameter could differentiate a closer region.. Local / soil level: The 34S/32S (sulfur) and 15N/14N (nitrogen) as geological parameter reflect the local soil. 5 16.08.2012 GmbH
. IRMS laboratories in Germany. Official food laboratories of the authority using stable isotope to check the origin of food. Is the stable isotope application applicable for timber? Projects (2006-2011): Muenster Oldenburg Berlin 2006-2007: database of spruce boreal timber project. 2008-2010: database of teak, mahogany 2009-2010: concession project Freiburg Wuerzburg Muenchen 6 16.08.2012 GmbH
D/H. WWF-Project I D/H database of spruce out of Russia and Europe water 7
. WWF-project II: Differentiation of teak (tectonia grandis) (2008-2010) Laos Birma Indonesia Honduras Costa Rica India Panama Brasil Java / Ind. Papua-New sampling locations: Teak (Tectonia grandis) 8
F2 (13,93 %). WWF-project II: Differentiation of tropical timber (2008-2010) Teak (tectonia grandis) in the Asian region (DA analysis:d, 13 C, 15 N, 18 O, 34 S) 6 observation (Achsen F1 und F2: 100,00 %) 4 2 Laos Java 0-8 -6-4 -2 0 2 4 6 8-2 Birma von \ nach Birma Java Laos Gesamtwert % korrekt Birma 12 2 1 15-4 80.00% Java 0 72 0 72 100.00% Laos 1 0 34 35 97.14% Gesamtwert 13 74 35 122 96.72% -6 F1 (86,07 %) Burma Java Laos Zentroide 9
15N/14N [ ] v.s. AIR. WWF-project II: Differentiation of tropical timber (2008-2010) Teak (tectonia grandis) in the Asian region: Stable isotope of nitrogen ( 15 N/ 14 N) 5 4 3 2 1 0 15 N/ 14 N -1-2 -3 Burma Java Laos Geological, Anthropogenic 10
F2 (43,34 %). WWF-project II: Differentiation of tropical timber (2008-2010) Teak (tectonia grandis) in the Asian region (DA analysis:d,13c,15n,18o,34s) Beobachtungen (Achsen F1 und F2: 94,80 %) 6 5 4 from \ to India Indonesia Java Laos PNG total % correct India 22 0 0 0 0 22 100% Indonesia 0 7 0 0 0 7 100% Java 0 0 127 1 0 128 99% Laos 0 0 0 29 1 30 97% PNG 0 1 1 1 15 18 83% total 22 8 128 31 16 205 98% PNG Laos 3 2 Indonesien 1 0-5 -4-3 -2-1 0 1 2 3 4 5 Indien 6 7 Java -1-2 -3-4 -5 F1 (51,46 %) India Indonesia Java Laos Papua New Guinia Zentroide 11
. WWF-project II: Differentiation of teak (tectonia grandis) (2008-2010) Laos Birma Indonesia Honduras Costa Rica India Panama Brasil Java / Ind. Papua-New sampling locations: Teak (Tectonia grandis) 12
F2 (17,45 %). WWF-project II: Differentiation of tropical timber (2008-2010) Teak (tectonia grandis) in Central America (DA analysis: D, 18 O, 13 C, 15 N, 34 S, 87 Sr) 10 Beobachtungen (Achsen F1 und F2: 97,08 %) Honduras Panama WEST 5 0 Panama EAST Costa Panama Rica Sampling point Brasilien -10-5 0 5 10 from \ to Brasil Costa Rica Honduras Panama total % -5 correkt Brasil 22 0 0 0 22 100,00% Costa Rica 0 10 0 5 15 66,67% Honduras 0 0 16 0 16 100,00% Panama 0 3 0 35 38 92,11% total 22 13 16 40 91 91,21% -10 F1 (79,63 %) Brasilien Costa Rica Honduras Panama Zentroide 13
F2 (4,16 %). WWF-project II: Differentiation of tropical timber (2008-2010) Teak (tectonia grandis): Closer comparison with Panama and Costa Rica: D, 18 O, 13 C, 15 N, 34 S) Beobachtungen (Achsen F1 und F2: 100,00 %) 4 3 2 1 0-1 -2-3 -4-4 -3-2 -1 0 1 2 3 4 F1 (95,84 %) Costa Rica Panama EAST Panama WEST 14
F2 (13,43 %). WWF-project II: Mahogany (2008-2010) Mahogany species (DA analysis:d,13c,15n,18o,34s 5 Beobachtungen (Achsen F1 und F2: 96,63 %) Honduras Costa Rica Honduras Costa Rica 0-5 0 5 10 Kongo Java Panama Java Panama Kongo Costa Rica Honduras Java Kongo Panama Zentroide -5 F1 (83,20 %) 15
. WWF-project: Teak, Mahogany: blind test Nr. Declaration Species Evaluation TR WWF Verification Origin Remark 1 Java Teak fraud O.K. 2 Honduras Mahogony fraud O.K. 3 Panama Teak fraud wrong Costa Rica NIR not used 4 Panama Teak O.K. O.K. 5 Java Teak fraud O.K. 6 Burma Teak fraud O.K. 7 Laos Teak O.K. O.K. 8 Costa Rica Teak O.K. wrong Ghana Ghana is not in database 9 Honduras Mahogany fraud O.K. 10 Java Teak O.K. O.K. 11 Laos Teak fraud O.K. 12 Costa Rica Teak fraud O.K. 13 Java Teak O.K. O.K. 14 Java Teak fraud O.K. 15 Bavaria Spuce fraud O.K. 16 16.08.2012 GmbH
. GTZ-project: Differentiation of timber from concession (2009-10) sampling locations: Cameron, Africa Kamerun 17
. GTZ-project: Differentiation of timber from concession (2009-10) sampling locations: Cameron in detail: Task: It is possible to differentiate FMU 10-003/04? FMU 00-004 FMU 10-051 FMU 10-026 ~100km FMU 10-004 FMU 10-003 FMU 10-007 18
. F2 (22,55 %) GTZ-project: Differentiation of timber from concession (2009-10) Iroko and Sapelli from concession in Cameron (DA Rotating: D, 18 O, 13 C, 15 N, 34 S) Beobachtungen (Achsen F1 und F2: 98,76 %) 5 10-026-FMU 10-007-FMU 10-003/004-FMU 00-004-FMU -8-3 2 0 10-026/051FMU 10-004-FMU from \ to 00-004-FMU 10-003/004-FMU 10-004-FMU 10-007-FMU 10-026-FMU 10-026/051FMU total % correct 00-004-FMU 167 0 0 0 0 3 170 98,24% 10-003/004-FMU 1 192 12 2 1 6 214 89,72% 10-004-FMU 0 3 186 0 0 14 203 91,63% 10-007-FMU 0 2 0 12 4 3 21 57,14% 10-026-FMU 0 2 0 2 16 0 20 80,00% 10-026/051FMU 0 4 41 0 1 16 62 25,81% total 168 203 239 16 22 42 690 85,36% F1 (76,21 %) 00-004-FMU 10-003/004-FMU 10-004-FMU 10-007-FMU 10-026-FMU 10-026/051FMU Zentroide -5 19
. Concession project Kamerun: blind test Nr. species yes NO origin of the concession delivered by 1 Iroko - Ivory Coast East Brothers I, J Likely from CFC 2 Sapelli + Cameroon (CFC concession) East Brothers E, F Likely from CFC 3 Sapelli + Cameroon (CFC concession) East Brothers A, B Likely from CFC 4 Utile - Sipo Timber - Congo East Brothers G, H Outside CFC 5 Sapelli - Congo (CIB concession - SGS) Latham E, F Outside CFC 6 Sapelli - Congo (CIB concession - FSC) Latham A, B Likely from CFC 7a Sapelli + Cameroon (CFC concession) East Brothers C, D Likely from CFC 7 Iroko - Cameroon, Alpi FMU 10-026 (<100km Distanz) Treemex H Likely from CFC 8 Iroko - Cameroon, Alpi FMU 10-026 (<100km Distanz) Treemex F Outside CFC 9 Iroko - Cameroon, Alpi FMU 10-026 (<100km Distanz) Treemex E Outside CFC 10 Sapelli - Congo (CIB concession - FSC) Latham C, D Outside CFC 11 Iroko - Cameroon, Alpi FMU 10-026 (<100km Distanz) Treemex A 12 Iroko - Cameroon, Alpi FMU 10-026 (<100km Distanz) Treemex D 13 Iroko - Cameroon, Alpi FMU 10-026 (<100km Distanz) Treemex B 14 Iroko - Cameroon, Alpi FMU 10-026 (<100km Distanz) Treemex G 15 Iroko - Cameroon, Alpi FMU 10-026 (<100km Distanz) Treemex E Nr Evaluation Outside concession Outside concession Outside concession Outside concession Outside concession 20
. GTZ-project: Differentiation of timber from concession (2009-10) Comparison of Iroko (African teak) and Sapelli (Mahogany species) - D, 18 O, 13 C 0.0-5.0-10.0-15.0-20.0 18O/16O(org.) v.s. VSMOW (+offset: -50 ) D/H(org.) v.s VSMOW 13C/12C v.s. PDB Similar water balance of different tree species and similar physiological structures should lead to similar isotopic ratios of hydrogen, carbon and oxygen. -25.0-30.0-35.0-40.0 Iroko: n=47 samples Sapelli: n=326-45.0 Iroko (FMU 10-001-4) Sapelli (FMU-10-001-4) 21
18O/16O v.s. SMOW D/H v.s. SMOW Teak-Honduras Mah-Honduras Teak-Java Mah-Java Teak-Costa Rica Mah-Costa Rica Teak-Panama Mah-Panama Teak-Honduras Mah-Honduras Teak-Java Mah-Java Teak-Costa Rica Mah-Costa Rica Teak-Panama Mah-Panama. Comparison of Teak and Mahogany from various regions. Comparison of different timber species. Test of data transfer = Mahogany = Teak 0-20 -40-60 -80-100 -120-56,550-72,390-74,810-69,150-79,900-78,607-70,217-57,606-60,293-61,235-90,400-93,019-78,900-84,579-90,750-94,100 Panama Costa Rica Java Honduras 30 There is the opportunity to find transfer parameters for different kind of wood 25 20 20,950 20,744 19,200 19,075 20,940 20,511 19,600 21,283 19,551 21,350 20,393 20,300 23,272 23,250 22,505 22,490 15 Panama Costa Rica Java Honduras 22
. Tracking system Samples information e.g. GPS coordinates Web server Isotopic Database server Stable isotopic data Experts (Full access for test report) 23
. Summary The stable isotopes use a physical property of the material (timber) Even manufactured wood (e.g. chair) could be analyzed The stable isotopes could deliver confirmation or exclusion of declared origin Stable isotope data should be transferable to other species of the botanical family Further stable isotopes could enhance the differentiation possibilities Reference samples are necessary For regional differentiation natural gradients are necessary. Problem: human borders are not natural isotopic borders Significance of the stable isotope method depends on the numbers of data in the database Closer differentiation <200km have to be verified or combined with other methods (Genetic) Experience in interpretation is necessary 24 16.08.2012 GmbH
. Thanks to Thank you very much Your attention 25
34 S/ 32 S Sulfur ratio from 3 samples per sampling location. WWF-project II: Differentiation of tropical timber (2008-2010) Sampling locations in Java: 26
D/H [ ] v.s. SMOW. Comparison of extracted and nitrated cellulose 20 Java Costa Rica Kongo Java Costa Rica Kongo Java Costa Rica Kongo Java-NitriertCosta Rica nitriert Kongo nitriert 4,680 0 3,741-20 -35,600-37,090-40 -44,411-36,878-38,942-44,810-60 -80-78,607-78,900-79,900-80,850-100 -120 extracted nitrated 27
. Overview preparation of samples Timber samples combustion / micro wave digestion / crown ether extraction Dried, crushed and ball milled 87Sr Total extraction with methylene chloride and methanol. nitration IRMS measurement D 18O 13C 15N 34S Offline preparation 28 16.08.2012 GmbH
. Stable isotopes Information to track back agricultural products water D/H 18 O/ 16 O Geology (soil) 34 S / 32 S 87 Sr / 86 15 Sr N / 14 N Îsotopic fingerprint Fertilisation 15 N/ 14 N Plant species / climate History 13 C/ 12 C 34 S/ 32 S 15 N/ 14 N