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Biochar is a carbonaceo s material prod ced from ario s feedstocks thro gh p rol sis, and it has recei ed great attention as an eco-friendl biosorbent beca se of its considerable sorption capacit for poll tants. P rol sis and en ironmental conditions determine the ph sicochemical characteristics of biochar and the sorption beha ior of poll tants; ho e er, the comple interaction bet een biochar and poll tants has not et been comprehensi el e amined. Therefore, in this st d , a literat re re ie regarding the ph sicochemical characteristics of biochar based on p rol sis conditions and the sorption of poll tants to biochar ere cond cted, and laborator e periments sing sorption isotherm ith spectroscop anal sis ere performed to el cidate and interpret the sorption mechanisms of organic sima ine, cationic cadmi m and anionic arsenate to Miscanth s biochar b changing p rol sis temperat re, pH and backgro nd electrol tes. The res lts indicated that electron donor-acceptor and h drophobic interactions ere the main sorption mechanisms for sima ine, and calci m as the backgro nd electrol te sho ed pore-filling effects b decreasing the sorption capacit compared ith sodi m. The sorption mechanisms of cadmi m and arsenate ere identified as partitioning and an o ter-sphere comple ation. Additionall , an inner-sphere comple ation and precipitation ere confirmed for cadmi m, and an electrostatic cation bridging comple ation and h drophobic interaction ere confirmed for arsenate. D ring sorption ith biochar, red ced arsenate species as fo nd. The pH and p rol sis temperat re did not sho a general pattern ith regard to the sorption of poll tants. The sorption of sima ine decreased ith increasing pH, hile the opposite pattern as obser ed for cadmi m and arsenate. An increased p rol sis temperat re red ced the
ii
sorption of sima ine, b t the obser ed trend as inconsistent for cadmi m and arsenate. Based on the obser ations, different p rol sis temperat re and en ironmental conditions led to distinct sorption patterns bet een biochar and poll tants beca se ario s sorption mechanisms are in ol ed in the sorption process, and the dominant sorption mechanism aries ith en ironmental conditions. Changes in p rol sis temperat re and en ironmental conditions dominantl affected leachabilit , bioa ailabilit and to icit of poll tants; th s, it is essential to comprehensi el nderstand the f ndamental interactions among the ph sicochemical characteristics of biochar, beha ior of poll tants and en ironmental conditions before the tili ation of biochar as a biosorbent.
Ke o d: Biochar, P rol sis temperat re, Sorption mechanism,
pH-dependent, Electrol te sol tion, Sima ine, Cadmi m, Arsenate
iii
LI
OF CON EN
ABSTRACT ... LIST OF CONTENTS ... LIST OF TABLES AND FIGURES ... LIST OF ABBREVIATIONS ... i
CHA E 1. GENE AL IN OD C ION ... 1-1
1.1. Defini i n f bi cha ... 1-1 1.2. Bi cha f en i nmen al ec ... 1-2 1.3. I ni able ll an in he en i nmen ... 1-5 1.4. Iden ifica i n f i n mechani m ... 1-10 1.5. Aim f di e a i n ... 1-11 Refe ence ... 1-15 CHA E 2. LI E A E E IE ... 2-1 Li f c n en ... 2-1 Ab ac ... 2-2 2.1. In c i n ... 2-3 2.2. Ph ic chemical cha ac e i ic f bi cha ... 2-6 2.3. Bi cha a ni e al ben ... 2-20 2.4. Une ec ed e l in emedia i n f ll a n ... 2-27 2.5. C ncl i n ... 2-31 Refe ence ... 2-32
CH A E 3. IN E E ING HE H-DE ENDEN MECHANI M OF IMA INE O ION O MISCANTH S BIOCHA OD CED A DIFFE EN OL I EM E A E FO I A LICA ION O OIL ... 3-1
Li f c n en ... 3-1 Ab ac ... 3-2 3.1. In d c i n ... 3-3 3.2. Ma e ial and me h d ... 3-6 3.3. Re l and di c i n ... 3-13 3.4. C ncl i n ... 3-37 Refe ence ... 3-39
iv
CH E 4. IN E AC I E EFFEC OF H AND CA ION ALENCE IN BACKG O ND ELEC OL E OL ION ON IMA INE O ION O MISCANTH S BIOCHA OD CED A O DIFFE EN OL I EM E A E ... 4-1 Li f c n en ... 4-1 Ab ac ... 4-2 4.1. In d c i n ... 4-3 4.2. Ma e ial and me h d ... 4-6 4.3. Re l and di c i n ... 4-12 4.4. C ncl i n ... 4-32 Refe ence ... 4-35
CHA E 5. COM EHEN I E IN E E A ION FO HE O ION MECHANI M OF C 2+ AND A ( ) ON MISCANTH S
BIOCHA ING CANNING ELEC ON MIC O CO , - A DIFF AC ION AND HO OEMI ION EC O CO ... 5-1 Li f c n en ... 5-1 Ab ac ... 5-2 5.1. In d c i n ... 5-3 5.2. Ma e ial and me h d ... 5-6 5.3. Re l and di c i n ... 5-10 5.4. C ncl i n ... 5-56 Refe ence ... 5-58
CHA E 6. MMA AND CONCL ION ... 6-1
6.1. S mma ... 6-1 6.2. C ncl i n ... 6-5
ABSTRACT IN KOREAN ... i LIST OF PUBLICATION ... i ACKNOWLEDGEMENT ...
v
LI
OF ABLE AND FIG
E
CHA E 1. GENE AL IN OD C ION ... 1-1 F . 1-1 P e en d ic f bi cha . ... 1-6
F . 1-2 Schema ic ill a i n f en i nmen ll an beha i in he il en i nmen . ... 1-12
CHA E 2. LI E A E E IE ... 2-1 2-1 A h and elemen al c n en f he bi cha d ced a i
feed ck and l i em e a e . ... 2-15
2-2 S mma f he i n i he m a ame e and ma i in l ed
in he i n f ganic ll an d ced f m a i feed ck a
diffe en l i em e a e . ... 2-21
2-3 S mma f he i n i he m a ame e and ma i in l ed
in he i n f in ganic ll an d ced f m a i feed ck
a diffe en l i em e a e . . ... 2-22
F . 2-1 Schema ic ill a i n f e l i n f c e i h
inc ea ing l i em e a e. Thi fig e i f m he e i
D nie e al. (2012) d , i i incl ded f be e nde anding he m lec la cale an f ma i n f bi cha c e. ... 2-9
F . 2-2 Van K e elen diag am f a i bi cha de i ed f m a i
feed ck nde diffe en l i em e a e. The g a mb l
indica ed he e i d acc ding Ahmad e al. (2014) and
c l ed mb l e e en ed he da ed e l in he he e i
die . ... 2-13
F . 2-3 Va ia i n f cha ged face f bi cha i h inc ea ing H b de na ed acidic f nc i nalg g (e.g., ca b lic, lac nic and hen lic) n bi cha face. ... 2-17
F . 2-4 Schema ic ill a a i n f in e ac i n be een bi cha and i ni able en i nmen al ll a n nde changing en i nmen al fac (e.g., H, i nic alence f ca i n and ani n, and ganic ma e ). ... 2-25
CH A E 3. IN E E ING HE H-DE ENDEN MECHANI M OF IMA INE O ION O MISCANTH S BIOCHA OD CED A DIFFE EN OL I EM E A E FO I A LICA ION O OIL ... 3-1
3-1 Ph ic chemical cha ac e i i f M ca bi cha d ced a l i em e a e a 400 C (B400) and 700 C (B700). . 3-15
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3-2 X- a fl e cence (XRF) ec c e l f d ied M ca and bi cha d ced a 400 C (B400) and 700 C (B700). ... 3-16
3-3 I he m a ame e f i n f ima ine n he M ca
bi cha d ced l i em e a e a 400 C (B400) and 700 C
(B700). ... 3-33
F . 3-1 S acked ATR FT-IR ec a f d ied M ca and bi cha d ced a 400 C (B400) and 700 C (B700). A and n mbe indica e he f e enc f he ib a i n m de in he m lec la c e. ... 3-19
F . 3-2 Scanning elec n mic g a h f M ca bi cha d ced a 400 C (B400) and 700 C (B700). All image e e ec ded i h a be c en f 15.5 kV. ... 3-21
F . 3-3 S i n kine ic f ima ine M ca bi cha d ced a 400 C (B400; lid ci cle) and 700 C (B700; en ci cle). The ini ial H f ima ine l i n a 4.5, and he final H f he mi e a 7.9 f B400 and 9.6 f B700. The ini ial c ncen a i n f ima ine a 5 mg L-1. ... 3-23
F . 3-4 M la f ac i n f na ed (g a da hed line) and ne al (g a lid line) ima ine calc la ed ing he Hende n-Ha elbach e a i n and f ne al ima ine b ained f m ba ch e e imen ( lid iangle) a a f nc i n f l i n H and he fi - de deg ada i n kine ic ( d) f
ima ine e ima ed b a ing he H ( lid ci cle i h a line). .... 3-25
F . 3-5 Fi ing f he F e ndlich i he m each da a e f ima ine i n b ained a h ee e H al e [3.0 (ci cle), 5.5 ( ec angle) and 9 ( iangle)] f (a) B400 and (b) B700. ... 3-31
F . 3-6 Sca cha d l ( -a i : he a i f bi cha -b nd ima ine f ee
ima ine, /C ; - a i : ) h ing e f i n mechani m
be een ima ine and bi cha b ained a : (a) H = 3.8 ( lid ci cle) and (b) H = 7.7 ( lid iangle) f B400, and (c) H = 3.6 ( en ci cle) and (d) H = 7.9 ( en iangle) f B700. Da a in e e en e e imen al e l . S lid line e e en elec a ic in e ac i n; da hed line den e h d h bic in e ac i n. ... 3-35
CH E 4. IN E AC I E EFFEC OF H AND CA ION ALENCE IN BACKG O ND ELEC OL E OL ION ON IMA INE O ION O MISCANTH S BIOCHA OD CED A O DIFFE EN OL I EM E A E ... 4-1 4-1 Ph ic chemical cha ac e i ic f M ca bi cha l ed a em e a e f 400 C (B400) and 700 C (B700). ... 4-13
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em e a e f 400 C (B400) and 700 C (B700). ... 4-16
4-3 Linea F e ndlich and Langm i i n i he m a ame e f
ima ine i n n M ca bi cha d ced a l i
em e a e f 400 C (B400) and 700 C (B700) b ained a h ee H al e in 0.1 M NaCl and 0.05 M CaCl2 l i n , i h he e l f
- a anal i f a iance (ANOVA) h ing he ignificance f he effec f fac and hei in e ac i n n each i he m a ame e . The mi e a haken a 160 m f 81h a 25 0.5 C. ... 4-25
4-4 FE-SEM/EDS elemen al anal i e l f e f bi cha d ced a 400 and 700 C (B400 and B700) b ained af e ima ine i n a H 3.5 and 10 in 0.1 M NaCl 0.05 M CaCl2. ... 4-26
F . 4-1 S face cha ge den i (SCD) f M ca bi cha d ced a l i em e a e f 400 C (B400) and 700 C (B700) a a f nc i n f H de e mined b en i me ic i a i n in 0.05 M CaCl2. ... 4-17
F . 4-2 Sima ine i n i he m fi ed he linea F e ndlich m del in 0.1 M NaCl ( ec angle ) and 0.05 M CaCl2 ( iangle ) f B400 (a-c,
indica ed n he lef ide i h lid mb l ) and B700 (d-f, indica ed n he igh ide i h en mb l ) a h ee H al e f 3.5, 7.5 and 10.
The mi e a agi a ed a 160 m f 81 h a m em e a e f 25
0.5 C. ... 4-23
F . 4-3 FE-SEM/EDS image f (a) m h l g (black), (b) C ( ell ), (c) O
( ange), (d) Si (bl e), and (e) Na ( le) Ca ( ed) f e f
bi cha d ced a 400 and 700 C (B400 and B700, e ec i el ), b ained af e ima ine i n a H 3.5 and 10 in 0.1 M NaCl 0.05 M CaCl2. ... 4-27
CHA E 5. COM EHEN I E IN E E A ION FO HE O ION MECHANI M OF C 2+ AND A ( ) ON MISCANTH S
BIOCHA ING CANNING ELEC ON MIC O CO , - A DIFF AC ION AND HO OEMI ION EC O CO ... 5-1
5-1 Ph ic chemical cha ac e i i f M ca bi cha l ed a em e a e f 400 C (B400) and 700 C (B700). ... 5-11
5-2 Fi ing e l ing he F e ndlich i he m f Cd2+ A (V)
i n n M ca bi cha l ed a em e a e f 400 C
(B400) and 700 C (B700) nde h ee H c ndi i n (3.5, 7.0 and 10). The mi e a agi a ed a 160 m f 120 h a m em e a e (25 C). The al e f KF i a c n an ela ed i n ca aci (mm l
g-1(mm l L-1)-n), and 1/n is the sorption intensity. The R2 value means the
viii
5-3 Di l ed i n c m i i n f B400 and B700 b ind c i el c led
la ma ical emi i n ec c (ICP-OES) mea emen . The
b ld elemen e e em l ed f i al MINTEQ calc la i n, in hich he c ncen a i n a ab e 0.01 mM (c ncen a i n le han 0.01 mM e e n incl ded f he calc la i n). ... 5-23
5-4 P ible eci i a e calc la ed ing Vi al MINTEQ f a e i h di l ed c ncen a i n f i maj i n (Ca, K, Mg, Mn, Si and Na) i h Cd2+ A (V) i n a H 3.5, 7.0 and 10. The li ed eci i a e e e
ca eg i ed beca e he e ceeded a a i n ( a a i n inde :
(SI= 10(IAP/K ) 0). The calc la i n a c nd c ed a H in e al f
0.5, b 3 H in a e li ed. ... 5-24
F . 5-1 S face cha ge den i (SCD) f M ca bi cha d ced a l i em e a e f 400 C (B400) and 700 C (B700) a a f nc i n f H de e mined b en i me ic i a i n in 0.05 M CaCl2. ... 5-13
F . 5-2 Kine ic d f he Cd2+ and A (V) i n i h c n lling he
H c ndi i n f 120 h. T h nd ed millig am f bi cha a mi ed i h 20 mL f 1 mM CdCl2 1 mM Na2HA O4 i h 100 mM NaCl a
he backg nd elec l e. The final H f Cd2+ a 6.4 and 6.8 f
B400 and B700 and f A (V), and i a 7.1 and 9.9 f B400 and B700, e ec i el . ... 5-18
F . 5-3 S i n i he m f Cd2+ and A (V) a i c ncen a i n (1, 2, 3, 4,
5, 10 mM) and h ee H al e (3.5, 7.0 and 10) n B400 (a and c) and B700 (b and d). E ba indica e he anda d de ia i n f i lica e mea emen . The d ed line indica ed he fi ing e l f F e ndlich m del, hile he ci cle, ec ang la and iangle indica e H al e f 3.5, 7.0 and 10, e ec i el . ... 5-19
F . 5-4 X- a diff ac i n a e n f B400 (a) and B700 (b) bef e he i n e e imen (ligh g a ) and af e i n f Cd2+ (da k g a ) and A (V)
(black) a diffe en c ncen a i n (1 and 5 mM) a h ee diffe en H al e (3.5, 7.0 and 10). Se en c al c e e e iden ified and li ed i h c de f m he Ame ican Mine al gi C al S c e Da aba e (AMCSD). Ca i al le e indica e he i i n f he maj eak f each c al c e li ed ab e. ... 5-27
F . 5-5 High- e l i n C1 (a and d), O1 (b and e) and Si2 (c and f) XPS
ec a f he bi cha (B400 and B700) bef e he i n
ix
dec n l i n ing Ig P 8 f a e and X- a Ph elec n
S ec c T l i h he Na i nal In i e f S anda d and
Techn l g XPS da aba e. Whi e ci cle and black line indica e e e imen al da a and he fi ing e l , e ec i el . The mall ec a in he fi ing e l indica e he c m nen iden ified b dec n l i n.
All ec a e e fi ed a mme ic Ga ian-L en ian f nc i n (70%
Ga ian and 30% L en ian). ... 5-31
F . 5-6 High- e l i n Na1 XPS ec a f bi cha (B400 and B700) af e i n e e imen f Cd2+ and A (V) a H 7.0 and 10. The
ec a a H 3.5 e e n ill a ed beca e n ignifican ignal e e b e ed. S ec al c m nen e e b ained and add e ed b eak
dec n l i n ing Ig P 8 f a e and X- a Ph elec n
S ec c T l i h Na i nal In i e f S anda d and Techn l g
XPS da aba e. Whi e ci cle and black line efe e e imen al da a and he fi ing e l , e ec i el . The mall ec a in he fi ing e l indica e he c m nen b dec n l i n. All ec a e e fi ed
a mme ic Ga ian-L en ian f nc i n (70% Ga ian and 30%
L en ian). ... 5-33
F . 5-7 High- e l i n Ca2 XPS ec a f bi cha (B400 and B700) bef e he A (V) i n e e imen (a and d) and af e he i n e e imen a H 7.0 and 10. The ec a in he Cd2+ i n e e imen
e e n ill a ed beca e n ignifican ignal e e b e ed.
S ec al c m nen e e b ained and add e ed b eak
dec n l i n ing Ig P 8 f a e and X- a Ph elec n
S ec c T l i h Na i nal In i e f S anda d and Techn l g
XPS da aba e. Whi e ci cle and black line efe e e imen al da a and he fi ing e l , e ec i el . The mall ec a in he fi ing e l indica e he c m nen b dec n l i n. All ec a e e fi ed
a mme ic Ga ian L en ian f nc i n (70% Ga ian and 30%
L en ian). ... 5-35
F . 5-8 Field emi i n canning elec n mic c e e i ed i h an ene g
di e i e X- a ec c (FE-SEM/EDS) image f bi cha am le
nde diffe en l i em e a e (B400 and B700) a H
al e (3.5 and 10). The c l ed image e e en he elemen al di ib i n f C ( ell ), O ( ange), Si (bl e), Na (ligh i le ), Cl ( i le ), Ca ( ed), Al (g een) and K (ligh bl e) a he ame cale ing
x
SEM-EDS mea emen . The FE-SEM/EDS a e a ed a an
accele a ing l age f 10 kV ing SE2 m de. Thi FE-SEM/EDS g a h
a e i l e ed, b i a incl ded he e a ing
inf ma i n f he c n enience f eade . ... 5-41
F . 5-9 High- e l i n Cd3d XPS ec a f bi cha (B400 and B700) a h ee diffe en H al e (3.5, 7.0 and 10). S ec al c m nen e e b ained and iden ified b eak dec n l i n ing Ig P 8 f a e
and X- a Ph elec n S ec c T l i h Na i nal In i e f
S anda d and Techn l g XPS da aba e. Whi e ci cle and black line indica e e e imen al da a and he fi ing e l , e ec i el . The mall ec a in he fi ing e l indica e he c m nen iden ified b
dec n l i n. All ec a e e fi ed a mme ic Ga ian
L en ian f nc i n (70% Ga ian and 30% L en ian). ... 5-43
F . 5-10 High- e l i n A 3d XPS ec a f bi cha (B400 and B700) a h ee diffe en H al e (3.5, 7.0 and 10). S ec al c m nen e e b ained and iden ified b eak dec n l i n ing Ig P 8 f a e
and X- a Ph elec n S ec c T l i h Na i nal In i e f
S anda d and Techn l g XPS da aba e. Whi e ci cle and black line indica e e e imen al da a and he fi ing e l , e ec i el . The mall ec a in he fi ing e l indica e he c m nen iden ified b
dec n l i n. All ec a e e fi ed a mme ic Ga ian
L en ian f nc i n (70% Ga ian and 30% L en ian). ... 5-45
F . 5-11 The e l f H adj men f he i n i he m d a H 3.5. The da a indica e he H bef e H adj men , and he H a adj ed H 3.5. A di inc a e n be een Cd2+ and A (V) a
b e ed, hich a ca ed b he ed c i n f A (V) A (III) and A (0). ... 5-49
xi
LI
OF ABB E IA ION
AFG: Acidic f nc i nal g ANO A: Anal i f a iance A : A en a ed al eflec ance BE : B na e -Emme -Telle BFG: Ba ic f nc i nal g
CEC: Ca i n e change ca aci
C : E ilib i m c ncen a i n f ba e (mg L-1)
C : Ca i n alence
C0: Ini ial c ncen a i n f ba e (mg L-1)
EC: Elec ical c nd c i i EDA: Elec n d n acce
ED : Ene g di e i e ec c
FE- EM: Field-emi i n canning elec n mic c
F I : F ie an f m inf a ed ec c
GC: Ga ch ma g a h
IC -OE : Ind c i el c led la ma ical emi i n ec c
IO : I ni able ganic ll an : Ra e f deg ada i n
KF: E ilib i m c n an indica ing i n ca aci (mg kg-1(mg L-1)-n)
KL: C n an ela ed ene g (L mg-1)
L D: Lea ignificance diffe ence AH: P l c clic a ma ic h d ca b n
: P l i em e a e
NC: P in f e ne cha ge
: E ima ed i n ca aci f ba e (mg kg-1)
: C ncen a i n f ba e bed n bi cha (mg kg-1)
: Mea ed i n ca aci f ba e (mg kg-1)
: Ma im m i n ca aci (mg kg-1)
: Pe cen n mali ed anda d de ia i n CD: S face cha ge den i
: Elec a ic a ac i n
: H d h bic a ac i n
A: S ecific face a ea
ECD: Mic elec n ca e de ec
: an de Waal F: X- a fl e cence
D: X- a diff ac i n
1-1
CHA
E 1. GENE AL IN
OD C ION
1.1. D
Bi cha i d ced f m he l i f a i feed ck ch a
d, lea e , man e nde gen-limi ed c ndi i n (Lehmann 2007a; Chen e al. 2008; Zha e al. 2013). D ing l i , feed ck i an f med an ec -f iendl f m f ene g a bi -e han l and a ca b n- ich b d c ; hi i called bi cha , and i e e a highe ecalci an ca b n c n en c m a ed i h he a feed ck (Lehmann e al. 2006). The d c i n f
bi -e han l h gh he he mal dec m i i n f feed ck ed ce he
emi i n f me hane he a m he e c m a ed i na al dec m i i n
in il (W lf e al. 2010; Ma ic 2011). Bi cha ha a c e
beca e he ecific ganic m lec la c e in feed ck dec m e
d ing he l i ce ; hi c e can f nc i n a i able i n
i e f he emedia i n f ll an (Q e al. 2011; Al-Wabel e al. 2013; Han e al. 2016). C n e en l , bi cha ha ecei ed a g ea a en i n a a nece a b d c f d cing ene able ene g , mi iga i n f clima e change h gh g eenh e ga emi i n ed c i n, ec cle f e fl feed ck , amendmen f im ing he il and a e en i nmen , and
emedia i n f en i nmen al ll i n (W lf e al. 2010; K kana e al. 2011; M han e al. 2014b).
The h ic chemical cha ac e i ic f bi cha a e mainl de e mined b he l i em e a e, e idence ime, hea an fe a e, and e f feed ck (Kl e al. 2012; Angin 2013; Qin e al. 2017). Bi cha d ced f m lan ch a d and lea e ha di inc h ic chemical cha ac e i ic d ced f m animal man e e id e (Zha e al. 2013; L e al. 2016). In gene al, lan bi cha ha a highe a ma ic ca b n c n en han animal
1-2
bi ma bi cha a he ame l i em e a e f 350, 450, and 750 C, hile alkaline chemical ecie and ca i n e change ca aci (CEC) a e highe in he animal e id e bi cha (D ming e e al. 2017). Thi i beca e lan bi ma ha highe c n en f cell l e and lignin, he ea animal bi ma c n ain m e mine al . E en if an iden ical feed ck e e em l ed f he
bi cha d c i n, he l i em e a e c n l he h ic chemical
cha ac e i ic , ch a ecific face a ea and a ma ic ca b n c n en , and b h inc ea e a highe l i em e a e. Thi i a e l f he ea angemen f a ma ic c m nd , fea ed b a ing f i ca b n a m
linked ge he i h gen h d gen, f acked and aligned hee
(Chen e al. 2007; Fang e al. 2014). The e a ie ie f bi cha ha e ca ed ad e e effec ne ec ed e l beca e f he lack f a f ndamen al nde anding f he h ic chemical cha ac e i ic f bi cha , and he
in e ac i n be een he a i face f bi cha and he fa e f
en i nmen all fl c a ing ll an e e changed (Ole c k e al. 2013; B e al. 2015).
1.2. B
The he e genei f bi cha ca ed b a i e f feed ck
and di e e l i c ndi i n ha ca ed ad e e effec ne ec ed
e l ; h e e , i ha al e l ed in en m i i e effec a
en i nmen al ec (M han e al. 2014b; In ang and Dicken n 2015; Xia e al. 2018). Thi gge ha an e en i e nde anding f he d c i n, f ndamen al cha ac e i ic , and en i nmen al c ndi i n ld enable he de ign f he b d c and f ndamen al cha ac e i ic f bi cha . A b iefl men i ned ab e, bi cha ha been e ed a a maj c n ib in fi e a ea : 1) ec -f iendl ene g d c i n, ch a bi e han l and bi -die el (Nanda e al. 2013; Y an and Mac a ie 2015); 2) clima e change
1-3
mi iga i n h gh he e e a i n f ca b n in he il and ed c i n in he ca b n di ide (Feng e al. 2012; Wang e al. 2012; M a e al. 2018) and me hane ga (C imc ik and Ma iell 2007; Windea e al. 2014); 3) ec cling f ag ic l al and en i nmen al a e ch a d, lea e , man e, ea , and edimen (M k me e al. 2013; R n e e al. 2013); 4) abili a i n f ll an and e en i n f n ien f m leaching (Zhang e al. 2013c; Ahmad e al. 2014; Tan e al. 2015; Xie e al. 2015).
The e ea ch field f bi cha can be ca eg i ed a d c i n and ili a i n (Fig. 1-1). The d f d c i n can be cha ac e i ed a e amining he a ia i n f feed ck , l i ce c ndi i n , c m i ing l i em e a e, e idence ime, and hea an fe a e. F he bi cha d c i n ce , Kl e al. (2012) e ed ha bi cha d ced f m a , ce, and la a l i em e a e f 400, 460, and 525 C had diffe en h ic chemical cha ac e i ic , a diffe en elemen al c m i i n
f feed ck dec m ed a diffe en l i em e a e . Mimm e al.
(2014) f nd ha M ca bi cha acc m la ed ca b n i h inc ea ing l i em e a e, inc ea ing he ecific face a ea and a ma ici . Chen e al. (2014) al h ed ha bi cha de i ed f m m nici al e age l ed a 500 900 C had inc ea ed c n en f a h, H, and CEC, e l ing in diffe en em al ca aci ie f cadmi m f m he e ec i e bi cha . F m he e die f bi cha d c i n, he a ia i n f feed ck
and l i em e a e a e ignifican ke fac ha de e mine he
h i chemical cha ac e i ic f bi cha , and e en i e die ha e al ead been c nd c ed a e he ela i n hi be een he e ke fac and he h i chemical cha ac e i ic f bi cha (Can ell e al. 2012; Zha e al. 2013).
Bi cha i ili ed f ca b n e e a i n in he mi iga i n f clima e change, ec cling f b - d c f m ag ic l al ac i i , im ing il
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fe ili , and emedia ing ll an (Cha e al. 2016). Man e ea che ha e e en i el f c ed n bi cha in he field f clima e change mi iga i n beca e f i gen challenge (Ba 2012; Ahmad e al. 2014; Shaaban e al. 2014). In ed cing g eenh e ga emi i n , bi cha ha been ec gni ed a ne f he effec i e a alle ia e gl bal a ming. W lf e al. (2010) calc la ed ha he d c i n f bi cha c ld ed ce he ann al ne emi i n f ca b n di ide, me hane, and ni ide b gene a ing ec -f iendl ene g hile ed cing he g eenh e ga emi i n. Vacca i e al. (2011) dem n a ed ha bi cha had emained a l ng ime in he il i h l a e f dec m i i n; h , i h an inc ea e in i a ef l manage ca b n e e a i n i h inc ea ing he il ganic ca b n c n en . The a lica i n f bi cha in he il en i nmen n nl ca e ca b n e e a i n b al ield addi i nal effec , ch a ene g c n e a i n f m ec cling f feed ck and im emen in il fe ili . S n and L (2014) c nfi med ha
cla e il ea ed i h bi cha d ced f m a , dchi , and
a e a e l dge de el ed mac agg ega e (5-2 and 0.25 0.5 mm) h gh e i ance laking and he inc a i n f a a ic la c he i n. Th , he a ailable a e e en i n ca aci f il a al inc ea ed d e he
enhancemen f agg ega e abili and e gani a i n f e ace
di ib i n. Rajk ich e al. (2012) h ed ha he c l i a i n f c n a
m e d c i e in il amended i h bi cha l ed a diffe en
em e a e , beca e f he bi cha e en i n f he n ien c n en . Zha e al. (2016) al died he effec f l i f feed ck i h h ha e fe ili e im e he bi cha ca abili f n ien e en i n, dem n a ing a i i e effec f c l i a i n.
Be ide ca b n e e a i n and n ien e en i n, he emedia i n f ll an ing bi cha ha al ecei ed a c n ide able am n f in e e , ing he ec -f iendline and c -effec i ene f bi cha a a bi ben
1-5
(Tang e al. 2013; In ang e al. 2016). Zheng e al. (2010) died he i n f ia ine bi cha d ced g een a e; in addi i n, Zhang e al. (2011)
died he i n f ima ine, bel nging he ia ine g ; h e e , hei e l e e diffe en f m h e f Zheng e al. (2010), ing he e f
diffe en bi cha . Chen and Chen (2009) h ed ha he i n f
na h halene and 1-na h h l bi cha d ced ange eel ielded diffe en
e l de ending n l i em e a e, e l ing in a a ie f
h ic chemical cha ac e i ic f bi cha . The i n f bi cha a h n be m e effec i e, beca e he em l ed diffe en bi cha . Bi cha a effec i e f n nl ganic ll an b al in ganic ll an . M han e
al. (2014) h ed ha bi cha d ced ak d and ak ba k e e ef l
f he emedia i n f cadmi m and lead. L e al. (2012) gge ed ha lead i n bi cha a affec ed b H, a he lead a eci i a ed a lead h ha e ilica e.
A men i ned ab e, he he e genei f bi cha led ad e e effec ne ec ed e l ; h e e , he e a e en m ad an age f ing bi cha in he en i nmen . H e e , effec i el e bi cha a a i i e bi ben and f ca b n e e a i n, he c m le ela i n hi be een d c i n and ili a i n h ld be f ll nde d. Wi h f ndamen al kn ledge f he mechani m and beha i f bi cha , ne ec ed ide effec in he en i nmen ma e l . C n e en l , f ll nde anding he f ndamen al cha ac e i ic f bi cha i e en ial f i ili a i n in he eal en i nmen .
1.3. I
O ganic ll an in he il en i nmen a e defined a ha mf l m lec le li ing gani m i h e i ance chemical, bi l gical, and h l ic deg ada i n (Reid e al. 2000). O ing hei e i enc , ganic
1-6
1-8
ll an e e acc m la ed i h a i ad e e effec n h man heal h and he ec em (Kel e and Ale ande 1997; Ke e e al. 2005). Iden ified b fl c a i n in he n c ncen a i n, he e a e ecific m lec le ha change hei m lec la cha ge, called i ni able ganic ll an (IOP ), hich e l in na i n de na i n (T l e al. 2009; Xia and Pigna ell 2014). O ganic acid a e ima il nega i el cha ged a a ce ain H al e ab e hei nega i e l ga i hmic acid di cia i n c n an ( Ka)
ing de na i n, he ea he a e ne all cha ged bel hei Ka (An
and D l 2007). On he c n a , ganic ba e a H al e ab e hei Ka
ing na i n, hile he a e i i el cha ged bel hei Ka
(S a le n e al. 1994). The beha i and fa e f IOP e e g e ned n nl b H c ndi i n b al b i nic eng h, ca i n alence and e, ani n alence and e, and c n en f ganic ma e in he nding en i nmen ; h , he emedia i n a egie f IOP h ld f ll a e he a i en i nmen al fac de c ibed ab e.
In ganic ll an c n i f idi ed elemen and chemical
c m nd , in hich m e chemical elemen a e made f m lack f
ganic ca b n c e (Wilc and S l i n 2005). The e in ganic ll an a e bi i beca e he a e e en n nl in lid and li id ha e b al in he ga ha e a ambien em e a e (S mme and S i 1985). O ing ha e an i i n and chemical an f ma i n, he effec i e emedia i n f in ganic ll an i n ea il add e ed (Ple ch e al. 1999; Alc n a a e al. 2012; Re ania e al. 2015), and e ce i e am n ha e been e ed in he en i nmen d e he n e f a id ind iali a i n i h e en i e an h genic ac i i (S ng e al. 2017). Hea me al a e e e en a i e in ganic ll an , he eb m f he hea me al n Ea h a e l ca ed in he li h he e; h e e , an h genic ac i i ie ch a mining
1-9
ed he e. In gene al, hea me al a e e en a i i el cha ged m lec le nde idi ing c ndi i n in he ed he e and h d he e, hich ca e e e e idi ing e li ing gani m (G a e al. 1996; Lim e al. 2008). H e e , me hea me al and me all id eac i h gen in he en i nmen , a ming a nega i el cha ged a e i h m e han gen (He e be g 1998; M ndal e al. 2006). The maj i f ani n a e e en ial ch a h ha e, lfa e, ca b na e, and ni a e; h e e , ic ani n al e i , ca ing a e e e en i nmen al h ea he ec em, ch a a ena e, eleni e, and an im na e. Ba ed n he ed en ial, he
ani n a e an f med ed ced ecie , and he elec chemical
e ie and ici a e changed. In he il and a e en i nmen , ca i nic hea me al and ani nic ani n c -e i a a i c ncen a i n and c m i i n ; h , i i im an abili e hei affini il c m nen and ed ce hei ac i i and bi a ailabili . Ba ed n elemen al m lec la cha ge , he an f ma i n f in ganic ll an ecie a ie i h e ec
H, ing na i n de na i n; hea me al in a il
en i nmen a e le abili ed nde l H c ndi i n , he ea he a e ea il imm bili ed a high H b i n n he nega i el cha ged face and eci i a i n i h h d l i n (Fa ah and Picke ing 1979). The cha ge
f ani n nde high H c ndi i n icall inc ea e h gh
de na i n (Kaila am and R enbe g 2012); mean hile, i e i n
end e e b e ed c m a ed i h h e f ca i nic hea me al . The ef e,
nde anding he beha i f i ni able ll an nde fl c a ing
en i nmen al c ndi i n i im an ade a el in e e hei fa e in he na al en i nmen ; h e e , diffic l ie emain beca e f he n me en i nmen al fac g e ning he beha i and fa e f he e i ni able
ll an . In addi i n, ch c m le in e ac i n emain blema ic beca e f limi a i n f anal ical mea emen in he e gene en i nmen .
1-10
1.4. I
Man e i die ha e a em ed iden if he i n
mechani m f en i nmen al ll an n bi cha ing a adi i nal i n
i he m (Ca e al. 2009; Zhang e al. 2013c; Venega e al. 2015), hich can be e e ed a a f nc i n f ba e c ncen a i n, ch a ganic in ganic ll an , n he bi cha a c n an em e a e . Se e al he e ical i he m ha e been ed e lain he i n mechani m indi ec l ; f
e am le, a Langm i i he m a me m n la e i n f a ingle ba e
n a ingle i n i e (Zhang e al. 2013a), he ea F e ndlich i he m i
m i able f em i ical da a, a ming f ene ge ic face he e genei
(Ya e al. 2013). The D binin Rad hke ich i he m i an he em i ical
m del de c ibed f n n-ideal i n a he e gene face (Pin e al.
2010). Th , a c m a i n f he fi ing e l b ained f m i n
i he m can enable he edic i n f he i n mechani m; h e e , ch
i n i he m l nl indi ec ; h , i i diffic l iden if he binding affini d ing i n.
Recen l , ec c ha been idel ed e eal he in e ac i n f en i nmen al ll an in he bi cha (X e al. 2011; Chia e al. 2012; Fan e al. 2018). Ba ed n he a eleng h f ligh , he e a e e e al ec c ie ha ha e enabled iden if i n mechani m , namel , X- a - and
inf a ed-ba ed ec c ie . F ie - an f m inf a ed ec c (FTIR)
i e i ed i h de e mine e e al fac , ch a a en a ed al eflec i n
and diff e eflec ance, he ea h ac ic ec c i ed
e e en he c al c nfig a i n f b h he bi cha and he in e ac i n f en i nmen al ll an a he in e face be een he bi cha and li id ha e
(Minne e al. 2017). X- a ab i n nea edge c e and e ended X- a
ab i n fine c e a e effec i e echni e in iden if ing he
1-11
ec a (XPS) a e ed c nfi m he an i a i e mea e f elemen al c m i i n f bi cha in e ac ing i h en i nmen al ll an , in hich i e l de e mine he binding a e be een bi cha and en i nmen al
ll an (A m and K nn 2016). X- a fl e cence (XRF) ec me i
ed anal e he c ncen a i n f he in ganic elemen f bi cha , hile
X- a diff ac i n (XRD) ide e l ega ding he c all g a hic
c e, chemical c m i i n, and h ical cha ac e i ic f bi cha af e ll an i n (Cha e jee e al. 2016). N j ligh -ba ed echni e b
al elec n-ba ed mea emen a e ef l in iden if ing he c e
f bi cha . Field emi i n canning elec n mic c (SEM) ili ing an
ene g di e i e X- a ec c de ec all he m h l g and
elemen al c m i i n f bi cha in e ac ing i h chemical c m nd be anal ed (Rade e al. 2014). All he anal ical echni e ha e ad an age and di ad an age ; h , nl limi ed inf ma i n i ided i h a ingle mea emen echni e. C n e en l , i i e en ial c mbine he da a f m
a i anal ical echni e e if he e l , dimini hing he
di ad an age f indi id al mea emen . T d , hi d ha a em ed iden if he i n mechani m and beha i f ganic and in ganic
ll an n bi cha i h b e a i n f m e e al a ec .
1.5. A
The emedia i n f en i nmen al ll an ing bi cha ha ecei ed c n ide able a en i n beca e bi cha i an ec -f iendl and c -effec i e bi - ben . H e e , ne ec ed e l ha e f e en l been
e ed in e i bi cha die , ince he h ic chemical cha ac e i ic f bi cha ha e n been f ll add e ed. Va ia i n in he d c i n f bi cha ca e a ignifican diffe ence in he h ic chemical cha ac e i ic f bi cha ;
1-12
F . 1-2. Schema ic ill a i n f en i nmen ll an beha i in he il en i nmen .
1-14
De i e he g ea en ial f bi cha f he emedia i n f ganic and
in ganic ll an , i a ia e e a a bi - ben nde a i
nding en i nmen al c ndi i n ha n e been c m ehen i el cha ac e i ed. The ef e, i i nece a nde and he in e ac i n f ganic and in ganic ll an i h bi cha nde a i en i nmen al c ndi i n f he f he ili a i n f bi cha a a bi - ben .
Th , hi e ie aim ide c m ehen i e in igh in he f ndamen al in e ac i n f ganic and in ganic ll an i h bi cha
d ced a diffe en l i em e a e nde a i en i nmen al
c ndi i n . The ided li e a e e ie mma i e he e i die
ega ding he a ia i n f he h ic chemical cha ac e i ic f bi cha nde nding en i nmen al c ndi i n , i n f ganic and in ganic ll an bi cha , and he ea n h en i nmen al change i c cial f
he i n die . The h ic chemical cha ac e i ic f bi cha d ced
a l i em e a e f 400 and 700 C (B400 and B700) e e f ll e amined i h m de n anal ic be e nde and hei im ac n he i n mechani m. Sima ine a an ganic ll an , cadmi m a a ca i nic hea me al, and a ena e a an ani nic ani n e e elec ed, and hei
i n mechani m e e c m ehen i el in e e ed nde and he
f ndamen al i n mechani m and e ima e hei beha i and fa e f f he im lica i n in il and a e en i nmen . Ba ed n he e e l and in e e a i n, bi cha h ld ecei e a g ea am n f a en i n in he eff ma imi e he i n ca aci and affini f ll an abili a i n in he
il and minimi e ne ec ed c me e l ing f m he mi nde anding
1-15
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2-1
CHAPTER 2. LITERATURE REVIEW
L f c e ... 2-1
Ab ac ... 2-2 2.1. In d c i n ... 2-3 2.2. Ph ic chemical cha ac i ic f bi cha ... 2-6
2.2.1. M lec la c e ... 2-7 2.2.2. S face a ea ... 2-8 2.2.3. P i ... 2-8 2.2.4. H, in f e ne cha ge, EC and a h c n en ... 2-11 2.2.5. Elemen al c m i i n and a mic a i ... 2-12 2.2.6. O gen c n aining acidic f nc i nal g ... 2-16 2.2.7. In ganic c n en ... 2-19 2.3. Bi cha a ni e al ben ... 2-20
2.3.1. Remedia i n f ganic ll an ... 2-20 2.3.2. Remedia i n f in ganic ll an ... 2-24 2.4. Une ec ed e l in emedia i n f ll an ... 2-27
2.4.1. Pe ec i e in h ic chemical cha ac e i ic f bi cha ... 2-27 2.4.2. Pe ec i e in en i nmen al fac ... 2-28 2.4.3. Pe ec i e in anal ic f bi cha cha ac e i a i n ... 2-30 2.5. C ncl i n ... 2-31 Refe ence ... 2-32
2-2
Ab ac
Bi cha i a ca b nace ma e ial d ced f m feed ck h gh
l i . I ha ecei ed a c n ide able a en i n a a ni e al ben f ganic and in ganic ll an ; h e e , i effec ha dem n a ed a a ie f e l , ing he a ia i n in he h ic chemical cha ac e i ic f bi cha and ll an nde fl c a ing en i nmen al c ndi i n . Wi h
inc ea ing l i em e a e, bi cha e hibi a def med c e,
in hich a ma ic ca b n hee a e c nden ed in an aligned b a ic c e i h a la ge face a ea and i . The H, in f e ne cha ge, elec ical c nd c i i (EC), and a h c n en f bi cha inc ea e d e he
de i i n f alkali al b he g e i e he mal dec m i i n f
feed ck . F he m e, he beha i f ll an diffe ba ed n nding
en i nmen al c ndi i n , a he i ni able ganic ll an changed i h he
pKa, and he inc ea e in he i nic alence f hea me al and ani n i
infl enced b he in e ac i n i h h d gen h d l i n in a e l i n . C n e en l , ne ec ed e l cc in he emedia i n f
ll an bi cha nde a ing en i nmen al c ndi i n . Thi e ie aim ide an e ie f he changing h ic chemical cha ac e i ic f bi cha e al a e a a bi ben , and di c he ea n f he ne ec ed e l f m he e ec i e f bi cha cha ac e i ic , en i nmen al fac , and mea emen echn l g . We belie e ha lab- cale die f iden if ing he i n mechani m be een bi cha and ll an a e e en ial f
de igning emedia i n a egie m e effec i el b c n lling he
bi a ailabili and leachabili in eal en i nmen .
Ke d
2-3
2.1. I d c
Bi cha i ca b n- ich ma e ial d ced f m feed ck , ch a
d, lea e , man e h gh l i nde gen deficien c ndi i n
(Lehmann 2007a; Y an e al. 2011). Va ia i n in feed ck e and l i em e a e ca e diffe en h ic chemical cha ac e i ic f bi cha (Kl e al. 2012; R n e e al. 2013; Mimm e al. 2014), ince he he mal
dec m i i n f m lec la c e in feed ck cc a ecific l i
em e a e (Chen e al. 2008; Ph ng e al. 2015). De i e he e f he ame feed ck f he d c i n f bi cha , he h ic chemical cha ac e i ic f
bi cha a i h he l i em e a e ed in he d c i n. F
e am le, ine needle bi cha d ced a l e l i em e a e ha an
am h ali ha ic f ac i n; h e e , i h inc ea ing l i em e a e,
hi bi cha e hibi an inc ea ing a ma ic f ac i n i h a c nden ed a ma ic c e (Chen e al. 2008). Thi i beca e he cell l e and lignin in lan bi ma a e deg aded a 220 315 C and a > 400 C, e ec i el (Q e al. 2011; Mimm e al. 2014). Miscan h s bi cha inc ea e in ca b n c n en and
ecific face a ea i h inc ea ing l i em e a e , ing
g e i e he mal dec m i i n (Mimm e al. 2014; Elma e al. 2015); mean hile, gen c n aining acidic f nc i nal g and i i el cha ged face a ea e e dec ea ed (Lee e al. 2018). N nl d e lan de i ed bi cha ha e diffe en h ic chemical cha ac e i ic c m a ed i h bi cha d ced f m animal man e, b i al c n ain a la ge in ganic f ac i n (Zhang e al. 2013b). S ch a i h ic chemical cha ac e i ic d ing he d c i n f bi cha ld ca e a blem a a bi ben beca e he i n ca aci and affini f bi cha ld n be nif m f he emedia i n f ll an .
The emedia i n f ll ed il and a e en i nmen i h ganic and in ganic m lec le i an gen blem, a ll i n i a di ec h ea
2-4
h man heal h (Wa i e al. 2013; Abdel-Shaf and Man 2016). H e e ,
l ing he blem f ll i n i challenging beca e b h bi cha and ll an nde g an i i n and an f ma i n i h change in en i nmen al c ndi i n , ch a H, i n c m i i n, em e a e, and ed c ndi i n . F he m e, ll an can in e ac i h a i elemen in il and a e en i nmen , e l ing in a a ie f i n beha i . O ganic acid ch a 2,4-D, ben ic acid, and chl ina ed hen l ha e a ne al cha ge bel pKa
(Uchimi a e al. 2012), he ea he a e nega i el cha ged a H ab e pKa,
ing de na i n. Mean hile, he ganic ba e, c m ed f ima ine
and ia ine, i i i el cha ged bel pKa beca e f na i n, hile i
ha a ne al cha ge ab e pKa (Lee e al. 2018). Hea me al a e icall
kn n a i i el cha ged i n nde ne al H c ndi i n ; h , he ld
be an ed f m il a e i h ake b gani m , e l ing in
ida i e e . Unde alkali c ndi i n , hea me al c ld be eci i a ed
i h h d l i n , he ea m lec la c e ld be an f med in he
e ence f he nega i el cha ged elemen in he il and a e (Ba al e al. 2006; B a ai e al. 2013). O ani n a e nega i el cha ged m lec le f med i h gen, and h ha e and a ena e (A (V)) a e e e en a i e ani n ecie . Ph ha e i ell kn n a an e en ial elemen f lan
g h, he ea A (V) i c n ide ed a n i ani n beca e f i
c m le fa e in il and a e en i nmen . Unde ic c ndi i n , A (V) c e i i h H3A O4, H2A O4-, HA O42-, and A O43- d e ha e h ee pKa
(K ng e al. 2017); i al an f m a eni e (A ( )), hich i a ed ced f m f A (V) and i f e en l e ed a e iding in he b ic and an ic c ndi i n f il . C n e en l , ani n c ld be eci i a ed i h i i el cha ged elemen bed i h he i i el cha ged face f il and a e c m nen . A ch, hei beha i de end n he nding en i nmen al c ndi i n , ch a H, ed en ial, and i n c m i i n.
2-5
Of he a i emedia i n echn l gie f ll an , i n,
hich cc a he ba e ( ganic and in ganic ll an ) i a ached he ben , i he m adi i nal and effec i e echni e (El-Ge ndi 1991;
Dab ki 2001). The e a e n me die n he i n f ll an , and
ben i icall ed ed ce he m bili and bi a ailabili f ll an in il and a e . F e am le, calci e, a il mine al d ced f m na al b ance , ha been h n efficien l b a ena e (S e al. 2008); in
addi i n, h ll ilica e , me al ide , and n he ic gan mine al
c m le e a e effec i e ben f a ena e and h ha e (Vi lan e and Pigna 2002). S il ganic ma e i ell kn n a ben f ganic ll an . H min, hich i he in l ble f ac i n f il ganic c m nen , i al able f ed cing he ca aci f lfame ha ine (G e al. 2017); mean hile, h mic f l ic acid, hich i he l ble f ac i n f il ganic c m nen , i effec i e in managing e i m (Tan e al. 2008). Recen l , n he i ed l me , ch a ca b n nan be and ac i a ed ca b n, ha e been f e en l ed f emedia i n f ll an (Abdel-Halim and Al-De ab
2011). M l i all ca b n nan be ha e been h n dimini h he am n
f ca aci f ene, henan h ene, and na h halene (Yang e al. 2006), hile ac i a ed ca b n ha dem n a ed a c m a a i e effec in ed cing hea
me al c ncen a i n (P ka and B eje ki 2010).
Bi cha i he m effec i e ec -f iendl and c -effec i e ben
f en i nmen al ll an in il and a e en i nmen (Ahmad e al.
2014), e l ing in he e gene h ic chemical cha ac e i ic (S n e al. 2011a; Ya e al. 2011; Deng e al. 2017). The e a e n me die ega ding
he i n f bi cha i h ll an . F e am le, he i n am n f
ganic ll an bi cha d ced f m dchi e e dec ea ed in
Minne a il (S ka e al. 2009); in addi i n, ine needle bi cha amended
2-6
h d ca b n (Chen and Y an 2011). H e e , bi cha l ed a
em e a e f 200 700 C (100 C in e al) dem n a ed diffe en le el f effec i ene f he i n f h halic acid e e beca e f diffe ence in he la and ali ha ic d main f bi cha (S n e al. 2012). The i n f hea me al e e al imm bili ed b he bi cha d ced f m lan bi ma (Pa k e al. 2013), and he i n f amm ni m, ni a e, and
h ha e bi cha l ed f m c n e and ak d inc ea ed
ing he de i i n f mine al n he face f bi cha (H lli e e al. 2013). The emedia i n efficienc f ll an a ied in bi cha , a he h ic chemical cha ac e i ic f bi cha g e n he i n mechani m ; h e e , hi ha n e been c m ehen i el de ailed. The ef e, i i im an nde and n nl he h ic chemical cha ac e i ic f bi cha b al he i ni able ecie f ll an nde fl c a ing en i nmen al c ndi i n e ima e he i n ca aci and affini in il and a e en i nmen .
Thi e ie mma i e he di e i in he h ic chemical
cha ac e i ic f bi cha b feed ck e and l i em e a e, he effec i ene f bi cha a bi ben f ganic and in ganic ll an in il a e en i nmen , and he ne ec ed e l f he emedia i n f
ll an .
2.2. Ph c che ca cha ac e c f b cha
Each bi cha ha di inc i e h ic chemical cha ac e i ic ing he a ie f c n i en and m lec la c e in feed ck (M k me e al. 2013; X e al. 2014; Xie e al. 2015). Bi cha de i ed f m animal bi ma ha m e en ichmen mine al c n en , al ng i h highe elec ic c nd c i i and a h c n en , a c m a ed i h bi cha d ced f m lan bi ma (Uchimi a and Hi ada e 2014). Plan bi cha ha an ab ndance in ganic
2-7
ca b n c n en d e he c n en f cell l e, hemicell l e, and lignin (X e al. 2014). H e e , he a ia i n in he h ic chemical cha ac e i ic f bi cha i h inc ea ing l i em e a e dem n a e a imila endenc ,
ega dle f he e f feed ck (Singh and C ie 2010; R n e e al. 2013). 2.2.1. M lec la c e
Wi h inc ea ing l i em e a e, lne able ganic
c m nen in feed ck a e elea ed b he mal dec m i i n (Q e al. 2011; Mimm e al. 2014). The m lec la c e f feed ck , hich e hibi a highe f ac i n f a ma ic ca b n and a highl di de ed
am h c e, i de el ed h gh c nj ga ed a ma ic ca b n hee
and an aligned b a ic c e (Fig. 2-1). The f he g e i e he mal
dec m i i n f bi ma led a g a hi e c e (Chen e al. 2007; Mimm e al. 2014). Ph ng e al. (2015) dem n a ed ha he c e f ma i n f
ice h k and ice a e e am h , he ea he bi cha a
cha ac e i ed a ha ing a g a hi e-like c e c nfi med b SEM anal i .
G me -Z illa Ma n e al. (2013) e ed ha he highe l i
em e a e e l ed in he di a ea ance f c alline cell l e in he d
bi ma , indica ing he ab ence f an am h c e. The e l f hi
a he f ma i n f a g a hi e c e i h im ed la e a ignmen , a
dem n a ed b SEM and XRD anal i . Bekia i e al. (2016) b e ed he
c al an f ma i n f bi cha i h inc ea ing l i em e a e
ing FTIR ec a; he n ed ha he eak c e nded he O-H
e ching ib a i n, i h he a mme ic and mme ic C-H e ching
ib a i n dimini hed; mean hile, he C=C e ching ib a i n in a ma ic c e a inc ea ed, ega dle f feed ck e.
