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SUPPLEMENTAL INFORMATION Evlution of Modified Boehm Titrtion Methods for Use with Lignoellulosi Biohrs Rivk B. Fidel, Dvid A. Lird*, Mihel L. Thompson Deprtment of Agronomy, Iow Stte University, Ames, IA, 50011, USA *Corresponding uthor Tel.: +1 515-294-1581; Emil: dlird@istte.edu Contents (6 pges totl) Figure S1 Funtionl group onentrtions of CE500 iohr s mesured with ll three methods nd ll retnts, nd sornes of the prepred extrts t 250 nm (A 250 ). Figure S2 Comprison etween titrtion urves mde y Goertzen et l (2010) nd this study. Figure S3 Comprison of funtionl group onentrtions etween orse (> 0.5 mm) nd fine (< 0.5 mm) frtions of RO500 FP iohr. Figure S4 Comprison etween the numer of times 7 ml liquots of 0.05 M NHCO 3 solution were run through n ENVI-Chrom P solid phse extrtion rtridge nd the mount of NOH needed to k-titrte n idified nd sprged 5 ml liquot. Figure S5 Funtionl group onentrtions of slow pyrolysis nd gsifition iohrs mesured using the sprge-rium-rtridge method. Figure S6 A 250 vlues of extrts from slow pyrolysis nd gsifition iohrs. S1

B B B A A A A A AB A B A B A A B AB A Figure S1 () Funtionl group onentrtions of CE500 iohr s mesured with ll three methods nd ll retnts, nd () sornes of the prepred extrts t 250 nm (A 250 ). In (), lowerse letters indite signifint differenes etween retnts within eh method, nd upperse letters indite signifine etween methods within eh retnt. In () upperse letters indite signifint differenes etween retnts within eh method, nd lowerse letters indite signifine etween methods within eh retnt. Error rs indite stndrd devitions in oth () nd (). S2

Figure S2 () Goertzen et l. (2010) showed tht, following 2h of sprging with N 2 gs, further degssing during the titrtion n remove dditionl CO 2 from solution nd therey prevent positive is (CSF is defined s Cron Surfe Funtionlities). Positive is ws indited y the presene of n dditionl infletion point. () In this study, no evidene of dissolved CO 2 ws found fter 2h of sprging without further degssing during the titrtion. Dshed lines indite ph 7. S3

C C B B A A Figure S3 Comprison of funtionl group onentrtions etween orse (> 0.5 mm) nd fine (< 0.5 mm) frtions of RO500 FP iohr mesured using the integrted sprge-rium-rium method. Lowerse letters indite signifint differenes etween size frtions within eh retnt, nd upperse letters indite signifint differenes etween retnts within eh size frtion. Error rs indite stndrd devitions. S4

Figure S4 Comprison etween the numer of times 7 ml liquots of 0.05 M NHCO 3 solution were pulled through stk of two ENVI-Chrom P solid phse extrtion rtridges nd the mount of NOH needed to k-titrte n idified nd sprged 5 ml liquot. Aliquots were idified using 2:1 volume rtio of 0.05M HCl to rtridge-treted smple, then sprged for 2h. Eh dt point represents single mesurement (R 2 = 0.999, p = 0.001). S5

Figure S5 Funtionl group onentrtions of slow pyrolysis nd gsifition iohrs s mesured with the sprge-rium-rtridge integrted method. Lowerse letters indite signifint differenes etween retnts within eh iohr (p < 0.05). Error rs indite stndrd devitions. S6

Figure S6 A 250 vlues of slow pyrolysis nd gsifition iohrs otined from extrts of iohrs prepred with different methods. Method-retnt omintions re listed t right. Lowerse letters indite signifint differenes etween retnts within eh iohr (p < 0.05). Error rs indite stndrd devitions. S7