WP1. Agriculturl iomss qulity Poul Erik Lærke, N Liu & Uffe Jørgensen, Dept. of Agroecology
Influencing fctors Genotype Hrvest time Storge Soil type nd climte Anlyses Work content Yield nd qulity of dedicted energy crops: willow, poplr (from HNEE) nd miscnthus Elementl nlysis y ICP-OES for reserch NIR/NIT for industry
Ojectives for the PhD study (N Liu) 1. to investigte the sptil distriution of minerls within the plnt 2. to investigte whether stem section smpling cn determine, rther thn whole tree smpling, cn e used to predict the iomss qulity of lrger scle 3. to explore the concentrtion of elements mong genotypes to select the most pproprite genotype for iodust comustion
Content of elements in reltion qulity Mjor Minor Al, C, Fe, Cd, Cu, K, Mg, N, + Mn, Zn + Cl, S P, Si Ash melting Deposit formtion Fly sh Aerosol emissions Corrosion Utiliztion/disposl of the shes
High-Throughput Microwve Digestion nd ICP-OES nlysis 1). Store in pper gs, dry t 60 o C 2). 3ml H2O2 + 6ml HNO3 + 50µl HF 4). Anlyse y ICP-OES 3). Digest in Microwve system
Sumitted Mnuscript Qulity Determintion of Biomss for Comustion: A New High-Throughput Microwve Digestion Method Prior to Elementl Anlysis y ICP-OES N Liu *, Uffe Jørgensen, Poul Erik Lærke Tle 4. Documented vlues for SRM NIST 1515 pple leves nd SRM NIST 1575 pine needles, nd certified vlues for the ioenergy crop Miscnthus x Gignteus on the concentrtions of twelve elements nd their uncertinties compred with vlues mesured y the new high-throughput method descried in this study. NIST 1515 Apple leves NIST 1575 Pine needles Miscnthus x Gignteus Element Documented Mesured (n= 8) % Recoveries Documented Mesured (n= 8) % Recoveries Certified Mesured (n= 55) % Recoveries (mg kg -1 ) (mg kg -1 ) (mg kg -1 ) (mg kg -1 ) (mg kg -1 ) (mg kg -1 ) Al 286 ± 9 285 ± 6 100 580 ± 30 541 ± 10 93 < 14 22 ± 3 154 C 15260 ± 150 15056 ± 291 99 2500 ± 100 2519 ± 42 101 870 ± 50 930 ± 9 107 Cd 0.013 ± 0.002 - - 0.233 ± 0.004 0.248 ± 0.011 107 0.11 ± 0.05 0.11 ± 0.01 98 Cu 5.64 ± 0.24 5.69 ± 0.11 101 2.8 ± 0.2 3.2 ± 0.2 115 2.1 ± 0.5 2.3 ± 0.1 108 Fe 83 ± 5 82 ± 7 98 46 ± 2 47 ± 1 102 18 ± 5 21 ± 2 115 K 16100 ± 200 15832 ± 285 98 4170 ± 70 4030 ± 51 97 8900 ± 500 8788 ± 67 99 Mg 2710 ± 80 2628 ± 35 97 1060 ± 170 954 ± 9 90 470 ± 30 489 ± 5 104 Mn 54 ± 3 51 ± 1 95 488 ± 12 474 ± 3.2 97 40 ± 2 41 ± 0.4 103 N 24.4 ± 1.2 23.3 ± 1.9 95 63 ± 1 58 ± 4 93 180 ± 20 185 ± 2 103 P 1590 ± 110 1494 ± 16 94 1070 ± 80 1039 ± 9 97 590 ± 50 634 ± 5 107 Si - 697 ± 101 - - 3069 ± 153-2900 ± 300 2974 ± 71 103 Zn 12.5 ± 0.3 11.8 ± 0.4 94 38 ± 2 37 ± 1 97 8.9 ± 1 10 ± 0.3 114 Determined y the EU stndrd method (DS/EN 15290, 2011) t DONG energy, Enstedværket, Aenr, DK. Men ± 95% confidence intervls.
Willow single shoots from Norwy 16 Brnch<10mm 15 14 13 12 11 All rest prt Elements distriution within shoots: 5 shoots 18 sections 83 smples in totl Blnce Center 17 Brnch>10mm 10 9 8 finger 7 18 Ded rnch 6 5 10 cm 4 25 cm 3 40 cm 2 40 cm 1 10 cm Ground Stump 10 cm
K Cd K nd Cd concentrtion, K nd Cd content nd DM distriution of single-shoot willow (shoot N) ccording to the sections (without ded shoots).
Poplr Hochschule für nchhltige Entwicklung (HNE), Eerswlde, Germny Hrvested in Fe 2012 Site Lindhorst, Germny 3-yer shoots from the 2nd rottion/6 yers old root stocks 9 clones + 1 reference willow 3 smpling types: Whole tree Blnce center Brk/wood 5 replictes 102 + 96 + 32 = 230 smples in totl
7000 6000 Poplr (9 clones) willow (1clone) mg/kg, sed on DM 5000 4000 3000 2000 1000 0 Al C Cu Fe K Mg Mn N P Si Zn Fig 1. Box plot of eleven elements in poplr (9 clones, 91 smples in totl) nd willow (1 clone, 11 smples in totl).
K concentrtion in 9 poplr genotypes nd 1 willow genotype 4500 Poplr Willow 4000 mg/kg, sed on DM 3500 3000 2500 2000 1500 Mx1 Mx3 Mx4 Weser6 Androscoggin AF2 MuhleLrsen NE42 Monviso Fig 2. Box plot of K concentrtion in poplr (MAX1, NE42, Androscoggin, AF2, Muhle Lrsen, Monviso, Weser6, MAX3, MAX4), nd willow (Inger). Inger
8000 7000 K concentrtion (mg/kg, sed on DM) 6000 5000 4000 3000 2000 MAX1 NE42 MAX1 Bse MAX1 Blnce Center NE42 Bse NE42 Blnce Center 1000 c c c c 0 Wood Brk Whole tree Fig 3. K concentrtion in poplr MAX1 nd NE42 (2 smpling positions: se nd lnce center; 2 frctions: wood nd rk, compred to smples from whole tree).
Concentrtion (mg/kg, sed on DM) 4000 3500 3000 2500 2000 1500 120 100 80 60 40 Elements in poplr (MAX1, NE42, Androscoggin, AF2, Muhle Lrsen, Monviso, Weser6, MAX3, MAX4), nd willow (Inger), compring two smpling types: whole tree smpling vs. lnce center smpling. PT2/PT!1 (%) 1000 500 0 20 0 PT1 whole shoot PT2 Grvity Center PT2/PT1 (%) Al C Cu Fe K Mg Mn N P Si Zn
Conclusion Poplr nd willow mterils significntly differ in elements concentrtion. Poplr rk frctions contined up to 5 time more minerls thn the wood frctions Lrge sptil vrition of elements ws reveled within willow shoots Concentrtion of elements round the lnce center were pproximtely 80% of the men for the complete shoot. Suitle hrvest nd post-hrvest prctices on reducing rk portion of iomss my improve the iomss qulity for comustion.
Numer of smples 96 miscnthus smples from Foulum 230 poplr smples from HNEE 83 willow smples from Agder University, Norwy 80 Dnish willow smples from 8 clones nd two soil types 400+ Germn (HNEE) poplr smples were collected from 10 clones nd 4 soil types Fe/Mrch 2013 144 willow smples from storge experiments (wood chip nd whole stem) 48 Dnish poplr smples from 6 clones nd two soil types Jn 2014
Pulictions nd dissemintion 1. Qulity Determintion of Biomss for Comustion: A New High-Throughput Microwve Digestion Method Prior to Elementl Anlysis y ICP-OES (Sumitted Aug 2013 to Energy & Fuels). 2. Predicting moisture content nd eleven elements concentrtion of whole Tordis willow shoots using smller stem sections (To e sumitted to Biomss nd Bioenergy y Oct. 2013). 3. Willow yield is highly dependent on clone nd site (To e sumitted Nov 2013 to Bioenergy Reserch) 4. Minerl composition of willow ffected y soil types, ges nd cultivrs: study on iomss qulity (To e sumitted 2014) Conferences Biomss Qulity Vrition of Poplr nd Willow in Reltion to Bio-Dust Comustion: Comprisons mong Genotypes nd within Shoots for the 21st EUROPEAN BIOMASS CONFERENCE AND EXHIBITION, Copenhgen, Denmrk, 03-07 June 2013. Compring Biomss Qulity (for Bio-Dust Comustion Purpose) of Poplr nd Willow mong Genotypes nd within Shoots BIT's 3rd Annul World Congress of Bioenergy, April 2013
Future work Willow storge smples re tken i-monthly throughout 2013. This ctivity hs een postponed one yer ccording to the Gntt chrt. Hrvest of poplr clone experiment Decemer 2013 Anlysis of new iomss smples y ICP-OES will continue throughout 2013. Totl sh content will e determined on ll smples. Determintion of Cl nd S y IC is ongoing Anlyses of AU smples t DTU? (sh deformtion nd melting temperture, STA comined with GCMS or FTIR)