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Q = 0.00042 kg/kgsol 

Aqueous HA Conc. (kg/m 3 0 

0 0.25 0.5 0.75 1 

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Sorbed HA (kg/kg sol.) 

Batch Sorption of Humic Acid to Aquifer Solids 

Aqueous HA (kg/m 3 ) 

10 1 

10 0 

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Ka= 39.1 α= 0.005 f= 0.47 Q= 0.00042 

observed 

simulated 

Aqueous Humic Acid 

0 25 50 75 100 125 150 

Time (days) 

Sorbed Humic Acid 

0 25 50 75 100 125 150 

Time (days) 

Iljxuh 618= Revhuyhg yv1 vlpxodwhg wudqvlhqw vruswlrq sur oh vkrzlqj hduo| htxl0 

oleulxp dqg odwh nlqhwlf ehkdylrxu1


dorqj wkh rz gluhfwlrq iurp 31349 p zlwklq wkh vrxufh wr 315 p wrzdugv wkh 

grzqjudglhqw erxqgdu|1 

Vsdwldo uhvroxwlrq zdv frqvwudlqhg e| wkh julg Shfohw fulwhuld +Gdxv hw do1/ 4


z(m) 

1 

0.5 

y(m) 

Y 

0 

1 

0.5 

Z 

0 

0 

X 

flow 

2 


4 

extraction 

well 

Iljxuh 619= Rxwolqh ri wkh 6G qlwh hohphqw phvk iru wkh slorw vfdoh prgho1 Wkh 

uhvlgxdo glhvho vrxufh lv orfdwhg dw wkh lqwhuvhfwlrq ri wkh qh0phvk duhdv/ 413 p 

iurp wkh lq rz erxqgdu|1 

6


(m) 

1 

0.5 

0 

0 1 2 3 4 5 


Iljxuh 61:= Sodq ylhz ri wkh slorw vfdoh prgho vkrzlqj vrxufh orfdwlrq dqg vwuhdp0 

olqhv frqyhujlqj wr wkh h{wudfwlrq zhoo1 

61 Dfwlylw| frh!flhqwv/ glvvroxwlrq udwhv dqg ghjudgdwlrq udwhv zhuh fdoleudwhg 

xvlqj euhdnwkurxjk ri wkh rujdqlf frpsrqhqwv1 

Sk|vlfdo gdwd iru wkh slorw vfdoh prgho duh surylghg lq Wdeoh 6161 Wkhvh sdudp0 

hwhuv duh frqvlghuhg dffxudwh dqg xqltxh ehfdxvh wkh| duh hlwkhu edvhg rq lqgh0 

shqghqw phdvxuhphqwv ru duh fdoleudwhg xvlqj d frqvhuydwlyh Eurplgh wudfhu1 Wkh 

rz yhorflw| ri 2 S6* o uhsuhvhqwv dq dyhudjh dfurvv wkh wdqn1 Wkh lqlwldo yhorflw| 

zlwklq wkh vrxufh gxulqj wkh glvvroxwlrq h{shulphqw lv dssur{lpdwho| 48 ( orzhu 

ehfdxvh wkh QDSO lv rffxs|lqj sruh vsdfh zklfk uhgxfhv wkh uhodwlyh shuphdelolw|1 

Wkh h hfw lv uhodwlyho| plqru/ krzhyhu/ dqg rz olqhv sdvv uhodwlyho| xqshuwxuehg 

wkurxjk wkh vrxufh/ frqyhujlqj grzqjudglhqw dw wkh zlwkgudzdo zhoo +Iljxuh 61:,1 

Dv wkh QDSO glvvroyhv/ wkh uhodwlyh shuphdelolw| lqfuhdvhv dqg yhorflwlhv zlwklq 

wkh vrxufh judgxdoo| uhfryhu wr edfnjurxqg ohyhov1 Wkh ghyldwlrq ri rz durxqg 

wkh vrxufh lv ohvv wkdq wkdw vlpxodwhg e| Iulqg hw do1 +4


frqfhqwudwlrq uhdfkhv derxw 318 }*u diwhu zklfk qrqolqhdu vruswlrq ri wkh fduulhu 

wr dtxlihu vrolgv lqgxfhv vljql fdqw wdlolqj1 Iru wklv vlpxodwlrq/ rqo| wkh nlqhwlf 

vruswlrq udwh frh!flhqw kdg wr eh fdoleudwhg +k 'ffD _@+ �� ,/ doo rwkhu sdudph0 

whuv zhuh rewdlqhg lqghshqghqwo| iurp edwfk h{shulphqwv +Wdeoh 615,1 Vlpxodwlrqv 

dvvxplqj wkh orzhu edwfk0fdoleudwhg udwh ri 31338 _@+ �� +qrw vkrzq, lqgxfhg d 

vwhhs duulydo fxuyh zlwk doprvw qr wdlolqj dqg fohduo| glg qrw pdwfk wkh revhuyhg 

ehkdylrxu1 

Wkh uhdvrq iru wkh glvfuhsdqf| ehwzhhq wkh vruswlrq udwh frh!flhqw iru wkh 

edwfk h{shulphqw +31338 _@+ �� dqgwkdw wwhgdwwkhslorwvfdoh+3138_@+ �� ,lv 

qrw fohdu1 Wkh g|qdplf qdwxuh ri wkh slorw vfdoh h{shulphqw dqg wkh h hfw ri pl{lqj 

ryhu wkh glvfuhwh hohphqwv pd| eh lpsruwdqw1


HA (g/L) 

HA (g/L) 

1 

0.8 

0.6 

0.4 

0.2 

HA btc at T3B4 

0 

0 25 50 75 100 125 150 175 200 

1 

0.8 

HA btc at T7C4 

0.6 

0.4 

0.2 

Pilot Scale Humic Acid Breakthrough 

0 

0 25 50 75 100 125 150 175 200 

Time (days) 

Iljxuh 61;= Vlpxodwhg yv1 revhuyhg euhdnwkurxjk ri wkh kxplf dflg fduulhu lq wkh 

slorw vfdoh h{shulphqw dw prqlwruv W6E7 +wrs, dqg W:F7 +erwwrp,1


Wdeoh 614= Iorz v|vwhp sdudphwhuv xvhg lq vlpxodwlqj wkh slorw vfdoh glvvroxwlrq 

whvw1 

Sdudphwhu Ydoxh Vrxufh 

glvshuvlylw|= 

orqjlwxglqdo +k� 31358 6 Eu wudfhu fdoleudwlrq 

wudqvyhuvh krul}rqwdo +k�� 31338 6 Iulqg hw do1 +4


Dgglwlrqdo sdudphwhuv shuwdlqlqj wr wkh glhvho ixho vrxufh duh surylghg lq Wd0 

eoh 6171 Pdvv hvwlpdwhv zhuh rewdlqhg iurp oderudwru| gdwd dqg iurp fxpxodwlyh 

x{ fdofxodwlrqv edvhg rq wkh revhuyhg euhdnwkurxjk gdwd +Ydq Vwhpsyrruw hw do1/ 

5333,1 Wkh pdvv ri wkh uhpdlqlqj/ xqnqrzq frpsrqhqwv lv wkhq frpsxwhg edvhg rq 

dvvxplqj dq dyhudjh prohfxodu zhljkw iru glhvho ixho ri 31563 nj2proh/ dq dyhudjh 

ghqvlw| ri 4333 &}*6� / dqg d vrxufh yroxph ri 833 pO1 

Wkh Vkhuzrrg qxpehu/ zklfk d hfwv wkh QDSO glvvroxwlrq udwh/ +htxdwlrq 6145, 

zdv xqnqrzq dqg kdg wr eh fdoleudwhg xvlqj wkh revhuyhg euhdnwkurxjk gdwd ri 

hdfk frpsrqhqw1 Iulqg hw do1 +4


433 gd|v +Iljxuh 61}*u zhuh


833/ 4533 dqg 4:33 gd|v iru wkh phwk|o0/ glphwk|o0 dqg wulphwk|oqdskwkdohqhv/ 

uhvshfwlyho|1 Wkh h{fhoohqw pdwfk wr wkh revhuyhg gdwd lv sduwlfxoduo| vljql fdqw 

ehfdxvh pdq| sdudphwhuv zhuh rewdlqhg iurp lqghshqghqw ode gdwd1 

Wkh prqlwru zhoov lpphgldwho| grzqjudglhqw iurp wkh vrxufh +urz W6, surylghg 

wkh ehvw gdwd iru fdoleudwlqj wkh hqkdqfhg vrxufh glvvroxwlrq vlqfh wkh| duh ohdvw 

d hfwhg e| rz wudqvlhqwv dqg glvshuvlrq/ dqg dovr vhhp ohvv d hfwhg e| elrghjud0 

gdwlrq1 Dv dq lqghshqghqw yhul fdwlrq/ wkh vlpxodwhg euhdnwkurxjk fxuyhv dw zhoov 

ixuwkhu grzqjudglhqw zhuh dovr frpsduhg wr wkh revhuyhg gdwd1 Iru h{dpsoh/ dw 

prqlwruv W9E7 +415 p grzqjudglhqw iurp wkh vrxufh, dqg W:P7 +418 p grzqjudgl0 

hqw,/ wkh prgho djdlq surylghv d jhqhudoo| jrrg pdwfk diwhu dgglwlrq ri wkh kxplf 

dflg/ dowkrxjk wkhuh lv vrphzkdw lqfuhdvhg vfdwwhu lq wkh revhuyhg gdwd +Iljxuh 

6146 dqg 6147,1 

Wkh revhuyhg hduo|0wlph wuhqgv + D gd|v, dw W9E7 dqg W:P7/ krzhyhu/ duh 

qrw dv zhoo uhsurgxfhg dv wkrvh dw W6E71 Zkhuhdv wkh revhuyhg wuhqg iurp 3083 

gd|v vkrzv d judgxdo frqfhqwudwlrq lqfuhdvh zlwkrxw d glvwlqfw vdwxudwlrq sodwhdx/ 

wkh vlpxodwhg frqfhqwudwlrqv vkrz d udslg ulvh iroorzhg e| d fohduo| ghfuhdvlqj 

wuhqg1 Wkh revhuyhg wuhqg pd| eh gxh wr qrqolqhdu vruswlrq ri wkh qdskwkdohqhv 

wr wkh dtxlihu vrolgv zkhuhdv lq wkh prgho wklv surfhvv lv dvvxphg wr eh olqhdu1 

Wkh glvfuhsdqf| pd| dovr ruljlqdwh iurp fkdqjhv lq wkh rz hog gxh wr plfureldo 

forjjlqj1 Eh|rqg 84 gd|v/ iroorzlqj dgglwlrq ri wkh kxplf dflg/ wkh revhuyhg wuhqgv 

duh zhoo uhsurgxfhg dw wkhvh wzr prqlwruv1 Wkh frqfhqwudwlrqv duh dw doo wlphv 

uhgxfhg uhodwlyh wr W6E7 ehfdxvh ri glvshuvlrq dqg elrghjudgdwlrq zlwklq wkhlu 

uhvshfwlyh vhsdudwlrq glvwdqfhv1 

Vhyhudo grzqjudglhqw prqlwru zhoov vkrzhg d uhodwlyho| frqvlvwhqw grxeoh0shdn 

wuhqg lq wkh euhdnwkurxjk sur ohv iru wkh qdskwkdohqhv +Ydq Vwhpsyrruw/ 5333,1 

DW W9E7 dqg W:P7/ iru h{dpsoh/ wkhuh lv d glvwlqfw gurs lq wkh euhdnwkurxjk frq0 

fhqwudwlrqv dw derxw 533 gd|v +Iljxuh 6146 dqg 6147,1 Wklv ehkdylrxu zdv wkrxjkw 

wr uhvxow iurp hlwkhu voljkw odwhudo vkliwlqj ri wkh soxph/ zklfk lq sodq ylhz frqwdlqv 

d glvwlqfw orz frqfhqwudwlrq }rqh grzq wkh fhqwuholqh/ ru iurp vsdwldo dqg whpsrudo 

yduldwlrqv lq wkh elrghjudgdwlrq udwh1 Gxh wr wkh xqfhuwdlqw| lq ruljlq/ qr dwwhpsw 

zdv pdgh wr uhsurgxfh wkhvh vhfrqgdu| wuhqgv zklfk dsshdu uhodwlyho| lqvljql fdqw 

uhodwlyh wr wkh vhyhudo rughuv0ri0pdjqlwxgh udqjh lq euhdnwkurxjk frqfhqwudwlrqv1 

Wkh vkdus ghfuhdvh lq wkh vlpxodwhg frpsrqhqw frqfhqwudwlrqv dw wkh lpphgldwh 

duulydo wlph ri wkh kxplf dflg +84 gd|v, lv gxh wr d orvv ri pdvv wr wkh vruehg kxplf 

dflg + hqkdqfhg vruswlrq ,1 Dv wkh fduulhu dgydqfhv wkurxjk wkh lqlwldoo| fduulhu0 

iuhh wdqn/ vruswlrq wr wkh vrolgv uhpryhv d vljql fdqw txdqwlw| iurp wkh dtxhrxv 

skdvh1 Dv wkh kxplf dflg iurqw uhdfkhv wkh glhvho vrxufh/ wkh rujdqlf frpsrqhqwv 

ehfrph vruehg wr wkh vruehg fduulhu zklfk fdxvhv d whpsrudu| exw glvwlqfw gurs


lq wkh dtxhrxv frqfhqwudwlrqv1 Dowkrxjk wkh h hfw lv vkruw0olyhg/ d fruuhvsrqglqj 

gurs lq vrph revhuyhg frqfhqwudwlrqv iurp 85088 gd|v vxjjhvwv wkdw wklv ehkdylrxu 

zdv lqghhg rffxuulqj lq wkh wdqn1 Wklv wuhqg lq wkh revhuyhg gdwd lv prvw dssduhqw 

dw prqlwruv W6E7 dqg W9E71


Wdeoh 616= Sk|vlfdo surshuwlhv ri wkh glhvho ixho frpsrqhqwv dvvxphg lq wkh slorw 

vfdoh prgho1 

Glhvho 4 �� ` �� 

� k �� 

� 

k� �� # 

Frpsrqhqw &}*6 � E&}*6J, E&}*6 � E6 � *&} E6 � *&} E6 � *r 

f �� f �� 

Ehq}hqh ;:919 313:; 41:; 13;39 313 :1: 

Wroxhqh ;:31 313


Wdeoh 618= Elrghjudgdwlrq sdudphwhuv iru wkh vlpxodwhg glhvho ixho frpsrqhqwv1 

Glhvho pd{1 udwh n N� NÈ \ 

Frpsrqhqw +nj��2nj��2gd|, nj2p � nj2p � nj��2nj�� 

Ehq}hqh 318 31335 31335 318 

Wroxhqh 318 31335 31335 318 

Hwk|oehq}hqh 318 31335 31335 318 

[|ohqhv 318 31335 31335 318 

Phwk|oqds1 3135 31335 31335 318 

Glphwk|oqds1 3135 31335 31335 318 

Wulphwk|oqds1 3135 31335 31335 318 

Rwkhu fsgv1 3153 31335 31335 318 

Wdeoh 619= Uhdfwlrq vwrlfklrphwulhv iru wkh vlpxodwhg glhvho ixho frpsrqhqwv1 

Glhvho Uhdfwlrq Vwrlfklrphwu| Pdvv udwlr [ 

Frpsrqhqw nj��2nj�� 

Ehq}hqh �M � n �� 

� � ', S � n M � 613; 

Wroxhqh �M � nb � ', . � neM � 6146 

Hwk|oehq}hqh �M �� n �� 

� � ', H � nDM � 614: 

[|ohqhv �M �� n �� 

� � ', H � nDM � 614: 

Phwk|oqds1 ��M �� n �� 

� � ', � nDM � 6137 

Glphwk|oqds1 ��M �� n D � ', 2 � nSM � 613; 

Wulphwk|oqds1 ��M �� n �� 

� � ', � n.M � 6144 

Rwkhu fsgv1 �M� nER n ^*e � ', R � nE^*2 M � 6153 

Wkh +wrwdo, qdskwkdohqh soxphv duh vkrzq lq sodq ylhz +wkurxjk wkh vrxufh 

fhqwuh, dw 74/ :3/ 6;8/ }*u1 Dovr/ wkh rxwhuprvw 83 >}*u frqwrxu kdv mxvw 

uhdfkhg wkh h{wudfwlrq zhoo zklfk lv lq jrrg djuhhphqw zlwk wkh revhuyhg soxph1 

Dowkrxjk wkh revhuyhg soxph dsshduv vrphzkdw zlghu wkdq wkh vlpxodwhg soxph/ 

wklv lv srvvleo| dq duwlidfw gxh wr wkh prqlwru zhoo vsdflqj dqg frqwrxu lqwhusrodwlrq 

ehwzhhq wkh prqlwruv1 Wkh uhodwlyho| qduurz vlpxodwhg soxph lv d uhvxow ri xvlqj 

d orz wudqvyhuvh krul}rqwdo glvshuvlylw| ri 31338 p/ zklfk lv frqvlvwhqw zlwk wkh


Conc. (g/L) 

0.0006 

0.0005 

0.0004 

0.0003 

0.0002 

0.0001 

model data 

Xylenes 

Ethylbenzene 

Toluene 

Benzene 

0 

0 50 100 

Time (days) 

Iljxuh 61


day 3 

day 10 

w Total BTEX 

day 46 

w 

day 95 

w 

Observed Total 

BTEX 

µg/L 

1 m 

:g/L 

1000 

1000 

800 

800 

600 600 

400 400 

200 200 

0 0 

Iljxuh 6143= Revhuyhg wrwdo EWH[ soxphv/ sodq ylhz wkurxjk vrxufh fhqwuh1 Diwhu 

Ydq Vwhpsyrruw hw do1 +5333,1


(m) 

(m) 

(m) 

(m) 

0.5 

1 3days Simulated 

0 

0.5 

0.5 

1 

0.5 

1 10 days 

0 

1 46 days 

0 

0 

95 days 

Total 

BTEX 

µg/L 

1600 

1400 

1200 

1000 

800 

600 

400 

200 

50 

10 

0 

Iljxuh 6144= Vlpxodwhg wrwdo EWH[ soxphv dw 6/ 43/ 79 dqg


Conc (g/L) 

Conc (g/L) 

10 -3 

10 -4 

10 -5 

10 -3 

10 -4 

10 -5 

total naphthalenes 

HA added (0.83 g/L) 

+ * 

simulated 

observed 

+ + + + + + 

++ 

+ 

++ 

+ + ++ + 10 

dimethylnaphthalene 

+ + ++ 

++ ++ 

+++ + 

+ + 

+ 

1 

10 2 

10 3 

* * * * * * * ***** * 

** * *** * * * * **** 

*** * * 

* * 

trimethylnaphthalene 

10 1 

10 2 

methylnaphthalene 

Time (days) 


Iljxuh 6145= Revhuyhg yv1 vlpxodwhg euhdnwkurxjk ri wkh qdskwkdohqh frpsrqhqwv 

dw prqlwru zhoo W6E7 +lpphgldwho| grzqjudglhqw iurp wkh vrxufh,1 

10 3 

* 

+


Conc (g/L) 

Conc (g/L) 

10 -3 

10 -4 

10 -5 

10 -3 

10 -4 

10 -5 

+ 


10 1 


10 2 

+ + + 

+ 

+ ++ 

++ 

+ 

+ 

++++ + dimethylnaphthalene 

+ 

+ 

+ 

* 


10 1 

* 

* 

* * * * *** 


+ +++ 

+ 

+ + 

* * ** ** **** * * * * **** ** * * 

10 2 

Time (days) 

simulated 

observed 

10 3 

+ * * + 

+ 

++ 

* * * 


dw prqlwru zhoo W9E7 +415 p grzqjudglhqw iurp wkh vrxufh,1 

10 3


Conc (g/L) 

Conc (g/L) 

10 -3 

10 -4 

10 -5 

10 -3 

10 -4 

10 -5 



10 1 

+ 


10 1 


+ 

+ 

+ 

* 

+ + 

+ + + 

+ 

+ ++ + 

+ + 

* * * * 

* 

* 

** ** 

* * 

* 

10 2 

* 

10 2 


Time (days) 

* + 

* 

+ 

* ++ 

** 

+ + 

* * 

+ 

+ * * 

+ 

simulated 

observed 


dw prqlwru zhoo W:P7 +418 p grzqjudglhqw iurp wkh vrxufh,1 

10 3 

* 

10 3


kxplf dflg iurqw lv orfdwhg dssur{lpdwho| 418 p iurp wkh khdg wdqn1 Wkh sur oh lv 

dv|pphwulf ehfdxvh ri wkh qrqolqhdu Odqjpxlu lvrwkhup dqg nlqhwlf olplwdwlrq ri 

wkh KD vruswlrq prgho1 

Wkh KD iurqw fruuhodwhv zlwk wkh orz0frqfhqwudwlrq euhdn lq wkh qdskwkdohqh 

soxph zkhuh hqkdqfhg vruswlrq kdv uhpryhg dtxhrxv skdvh rujdqlf pdvv1 Iurp 

88098 gd|v/ wkh KD iurqw dgydqfhv/ fdxvlqj wkh ghsuhvvlrq wr zlghq dqg e| 98 

gd|v/ wkh 83 >}*u frqwrxu ri wkh pdlq soxph kdv vhsdudwhg frpsohwho| iurp wkh 

dgydqfhg oreh1 Qr dwwhpsw zdv pdgh wr fruuhodwh wklv ehkdylrxu zlwk wkh revhuyhg 

glvwulexwlrq/ krzhyhu lw zdv revhuyhg lq vrph ri wkh euhdnwkurxjk gdwd dv d glvwlqfw 

frqfhqwudwlrq gurs diwhu duulydo ri wkh kxplf dflg +vhh Iljxuhv 614506147,1 

E| 6;8 gd|v/ wkh wrwdo qdskwkdohqh soxph kdv uh0dgydqfhg dowkrxjk frqfhqwud0 

wlrqv kdyh douhdg| ehjxq wr ghfuhdvh gxh wr vrxufh ghsohwlrq dqg elrghjudgdwlrq 

+Iljxuh 6149,1 E| }*u 

frqwrxu qr orqjhu uhdfkhv wkh h{wudfwlrq zhoo1 Diwhu 46;3 gd|v/ wkh vrxufh frqfhq0 

wudwlrq kdv ghfuhdvhg wr dssur{lpdwho| 533 >}*u dqg wkh soxph h{whqgv ohvv wkdq 

d phwuh iurp wkh vrxufh1 

Wkurxjkrxw wkh h{shulphqw/ elrghjudgdwlrq ri wkh vrxufh dqg glvvroyhg rujdqlfv 

zdv frqvlghuhg dfwlyh1 Vxssruwlqj hylghqfh fdph iurp phdvxuhg edfnjurxqg r{|0 

jhq frqfhqwudwlrqv rq wkh rughu ri 918 wr ;18 6}*u/ zkloh r{|jhq gdwd zlwklq wkh 

glvvroyhg soxph udqjhg iurp 3136 wr 51


jdqlf soxphv1 Vrphzkdw kljkhu frqfhqwudwlrqv duh dovr irxqg dw wkh h{wudfwlrq zhoo 

zkhuh hqkdqfhg pl{lqj idyrxuv plfureldo jurzwk1 Plfureh frqfhqwudwlrqv zlwklq 

wkh fhqwuh ri wkh rujdqlf soxphv uhpdlq dw plqlpxp ohyhov ehfdxvh ri doprvw frp0 

sohwh r{|jhq ghsohwlrq dqg qdwxudo plfureldo ghfd|1 Xqiruwxqdwho|/ plfureldo pdvv 

zdv qrw prqlwruhg gxulqj wkh h{shulphqw dqg frpsdulvrqv fdqqrw eh pdgh1 

Wkh vlpxodwhg plfureldo jurzwk sdwwhuq vxjjhvwv vrph lqwhuhvwlqj srvvlelolwlhv 

iru h{sodlqlqj revhuyhg wuhqgv lq wkh qdskwkdohqh frqfhqwudwlrqv wkdw zhuh qrw 

uhsurgxfhg lq wkh prgho1 Wkh revhuyhg orz qdskwkdohqh frqfhqwudwlrqv grzq wkh 

soxph fhqwuholqh/ iru h{dpsoh/ frxog eh d uhvxow ri wkh rz hog sduwldoo| e|sdvvlqj 

wkh vrxufh gxh wr plfureldo forjjlqj1 Wkh ghfuhdvh lq uhodwlyh shuphdelolw| gxh wr 

wkh suhvhqfh ri uhvlgxdo glhvho lv qrw vx!flhqw wr dffrxqw iru wklv wuhqg1 Dovr/ wkh 

revhuyhg gurs lq wkh qdskwkdohqh euhdnwkurxjk frqfhqwudwlrqv dw vhyhudo prqlwru 

zhoov frxog eh gxh wr vpdoo wudqvlhqwv lq wkh rz hog/ djdlq fdxvhg e| plfureldo 

jurzwk dqg ghfd|1 Ehfdxvh ri wkh kljk frqfhqwudwlrq judglhqwv/ d vpdoo odwhudo vkliw 

lq wkh soxph/ rq wkh rughu ri d ihz fhqwlphwuhv/ zrxog eh vx!flhqw wr fdxvh wkh 

revhuyhg wuhqg1 Wr vlpxodwh wkhvh h hfwv/ wkh prgho frxog eh prgl hg wr lqfoxgh 

frxsolqj ehwzhhq wkh plfureldo pdvv dqg wkh uhodwlyh shuphdelolw| whup1 

Wkh uhodwlrqvklsv ehwzhhq wkh glvvroylqj vrxufh/ wkh dtxhrxv skdvh rujdqlfv dqg 

wkh glvvroyhg r{|jhq duh vkrzq dorqj d fhqwudo orqjlwxglqdo sur oh lq Iljxuh 61531 

Vrxufh glvvroxwlrq/ dv vkrzq e| wkh wudqvlhqw vdwxudwlrq sur ohv/ surfhhgv iurp wkh 

xsjudglhqw idfh dqg e| 46;3 gd|v/ derxw rqh0kdoi ri wkh vrxufh kdv glvvroyhg1 Wkh 

dtxhrxv frqfhqwudwlrqv ulvh udslgo| dfurvv wkh vrxufh dqg judgxdoo| ghfolqh wrzdug 

wkh h{wudfwlrq zhoo gxh wr glvshuvlrq dqg elrghjudgdwlrq1 Wkh lqlwldo lqfuhdvh iurp 

73 wr :3 gd|v lv gxh wr wkh kxplf dflg hqkdqfhphqw/ dqg diwhu :3 gd|v/ wkh sur ohv 

judgxdoo| ghfolqh1 Wkh fruuhvsrqglqj r{|jhq ghsohwlrq sur ohv vkrz d judgxdo 

ghfuhdvh ehjlqqlqj dw wkh uhvlgxdo vrxufh dqg ulvlqj djdlq dw wkh h{wudfwlrq zhoo 

gxh wr pl{lqj zlwk edfnjurxqg xvklqj zdwhu1 D vwhdg| vwdwh ghsohwlrq sur oh lv 

hylghqw ehjlqqlqj dw 6;8 gd|v1


41 d 

w 

70 d 

w 

385 d 

w 

958 d 

1380 d 

Observed Total 

Naphthalenes 

w 0 

Total methynaphthalenes 

:g/L 

g/Lµ 

1600 

1400 

1400 

1200 

1200 

1000 

800 

800 

600 

400 

200 

1 m 

1600 

1000 

Iljxuh 6148= Revhuyhg wrwdo phwk|oqdskwkdohqh soxphv iurp wkh slorw vfdoh h{shu0 

lphqw +sodq ylhz wkurxjk vrxufh fhqwuh,1 Diwhu Ydq Vwhpsyrruw hw do1 +5333,1 

600 

400 

200 

0


(m) 

(m) 

(m) 

(m) 

(m) 

0.5 

0 

0.5 

1 70 days 

0 

0.5 

1 41 days 

1 385 days 

0 

1 

0.5 

0 

1 

0.5 

958 days 

1380 days 

0 

0 1 2 3 4 5 


Simulated 

Total 

Naphthalenes 

µg/L 

1600 

1400 

1200 

1000 

800 

600 

400 

200 

50 

Iljxuh 6149= Vlpxodwhg wrwdo phwk|oqdskwkdohqh soxphv fruuhvsrqglqj wr revhuyhg 

wlphv1 Sodq ylhz wkurxjk wkh vrxufh fhqwuh1


(m) 

g/L 

(m) 

g/L 

(m) 

g/L 

(m) 

0.5 

1 50 days 

0 

0.5 Humic Acid Profile 

0 

1 55 days Total Naphthalenes 

0.5 

0 

0.5 

0 

1 60 days 

0.5 

0 

0.5 

0 

1 

0.5 

65 days 

0 

0 1 2 3 4 5 


µg/L 

1600 

1400 

1200 

1000 

800 

600 

400 

200 

50 

Iljxuh 614:= Vlpxodwhg wrwdo phwk|oqdskwkdohqh soxphv dw 83098 gd|v vkrzlqj 

fruuhvsrqglqj kxplf dflg sur ohv1 Frqwrxu sorwv duh sodq ylhz/ orfdwhg wkurxjk 

wkh vrxufh fhqwuh1


(m) 

(m) 

(m) 

(m) 

(m) 

0.5 

1 41 days 

0 

0.5 

1 70 days 

0 

0.5 

1 385 days 

0 

1 958 days 

5 

4 

3 

0 

1380 days 

2 

1 

0.5 

1 

0.5 

0 

0 1 2 3 4 5 


Dissolved 

Oxygen 

mg/L 

Iljxuh 614;= Vlpxodwhg r{|jhq ghsohwlrq soxphv/ fdxvhg e| elrghjudgdwlrq ri wkh 

glhvho ixho frpsrqhqwv1 Wkh lpdjhv uhsuhvhqw d krul}rqwdo volfh wkurxjk wkh vrxufh 

fhqwuh1 Frqwrxuv duh rqo| rrghg iru ghsohwhg duhdv zlwk ohvv wkdq wkh edfnjurxqg 

frqfhqwudwlrq ri 9 pj2O1


(m) 

(m) 

(m) 

(m) 

(m) 

0.5 

0.5 

1 70 days 

6 

0 

1 

0.5 

1 41 days 

0 

0 

1 

0.5 

0 

1 

0.5 

385 days 

14 

958 days 

14 

1380 days 

14 

6 

0 

0 1 2 3 4 5 

6 


6 

6 

Microbes 

mg/L 

Iljxuh 614


Saturation 

µg/L 

µg/L 

µg/L 

mg/L 

0.1 

0.05 

0 

10 3 

10 2 

10 1 

10 3 

10 2 

10 3 

10 1 

10 2 

10 1 

10 1 

10 0 

10 -1 

10 -2 

40 days 

70 

385 

958 

1380 

40 days 

40 days 

70 

40 days 

Dissolved Oxygen 

40 days 

70 days 

70 

70 

385 days 

385 

958 

385 

958 

Diesel Saturation 

Methylnaphthalene 

Dimethylnaphthalene 

Trimethylnaphthalene 

1380 

385-1380 

0 1 2 3 4 5 


Iljxuh 6153= Vlpxodwhg orqjlwxglqdo sur ohv wkurxjk wkh vrxufh fhqwuh vkrzlqj 

glhvho vdwxudwlrq/ qdskwkdohqh frqfhqwudwlrqv dqg glvvroyhg r{|jhq1


619 Vhqvlwlylw| Dqdo|vlv 

61914 Glvvroxwlrq Udwh 

Wkh glvvroxwlrq udwh frh!flhqw +b � 

�� lq htxdwlrq +6145,/ dqg wkh Vkhuzrrg qxpehu 

E7 lq sduwlfxodu/ frqwuro wkh h hfwlyh glvvroxwlrq udwh ri wkh uhvlgxdo glhvho1 Wr 

lqyhvwljdwh wkh lq xhqfh ri wkh glvvroxwlrq udwh lq wkh slorw vfdoh h{shulphqw/ wkh 

prgho zdv uxq xvlqj Vkhuzrrg qxpehuv ri rqh0whqwk dqg 43 wkrvh fdoleudwhg 

+Wdeoh 617,1 Wkh uhvxowv duh frpsduhg wr wkh fdoleudwlrq uxq lq Iljxuh 6154 zklfk 

looxvwudwhv wkdw wkh orzhu glvvroxwlrq udwh vljql fdqwo| uhgxfhv wkh euhdnwkurxjk 

frqfhqwudwlrqv/ hyhq diwhu wkh kxplf dflg fduulhu duulyhv1 Wkh hduo|0wlph +3083 gd|v, 

revhuyhg frqfhqwudwlrq sodwhdxv duh qrz xqghuhvwlpdwhg dqg wkhuh lv vljql fdqwo| 

pruh wdlolqj lq wkh euhdnwkurxjk sur ohv uhvxowlqj lq pxfk orqjhu glvvroxwlrq wlphv1 

Lqfuhdvlqj wkh glvvroxwlrq udwhv e| d idfwru ri 43/ krzhyhu/ kdv yhu| olwwoh lq xhqfh 

rq wkh euhdnwkurxjk frqfhqwudwlrqv zklfk vxjjhvwv wkdw wkh glhvho ixho lv glvvroylqj 

xqghu htxloleulxp ru qhdu0htxloleulxp frqglwlrqv1 Vrph ghjuhh ri qrq0xqltxhqhvv 

pxvw eh dfnqrzohgjhg khuh/ vlqfh d orzhu glvvroxwlrq udwh zrxog kdyh d vlplodu 

h hfw rq wkh euhdnwkurxjk fxuyhv dv d orzhu KD elqglqj frh!flhqw +vhh vhfwlrq 

61917,1 

Revhuylqj wkh lqlwldo frqfhqwudwlrq sodwhdxv iurp 3083 gd|v/ lw vhhpv olnho| 

wkdw wkh qdskwkdohqh frpsrqhqwv duh glvvroylqj dw qhdu0htxloleulxp frqglwlrqv/ dw 

ohdvw ryhu wkh hduo|0wlph shulrg/ dqg shukdsv wkurxjkrxw wkh h{shulphqw1 Wklv zdv 

frq uphg e| uxqqlqj d 4G htxloleulxp pl{lqj fhoo prgho xvlqj lghqwlfdo sdudphwhuv 

iurp wkh slorw vfdoh prgho1 Wzr frqfhswxdo htxloleulxp prghov zhuh whvwhg= d 

vlqjoh vroxelolw| prgho lq zklfk wkh dfwlylw|0fruuhfwhg +qrq0hqkdqfhg, vdwxudwlrqv 

+ � @�, duh frqvwdqw wkurxjkrxw wkh prqlwrulqj shulrg/ dqg d gxdo vroxelolw| prgho 

zkhuh wkh vroxelolwlhv duh lqvwdqwdqhrxvo| lqfuhdvhg dw 84 gd|v wr uhsurgxfh wkh 

hqkdqfhg glvvroxwlrq diwhu dgglwlrq ri kxplf dflg1 Wkh dssurdfk lv vlpsol hg lq 

wkdw lw dffrxqwv iru wkh kxplf dflg rqo| e| lqfuhdvlqj wkh h hfwlyh frpsrqhqw 

vroxelolwlhv1 Qrq0olqhdu h hfwv dqg elrghjudgdwlrq duh qrw frqvlghuhg1 Uhvxowv duh 

djdlq frpsduhg dw prqlwru W6E7/ mxvw grzqjudglhqw iurp wkh vrxufh1 

Wkh gxdo0htxloleulxp prgho +Iljxuh 6155, surylghv d vxusulvlqjo| jrrg pdwfk wr 

wkh revhuyhg gdwd zklfk olh qhdwo| ehwzhhq wkh wdlov ri wkh vlpxodwhg euhdnwkurxjk 

fxuyhv1 Wkh gxdo vroxelolw| prgho glvvroyhv wkh qdskwkdohqhv pruh udslgo| zkloh 

wkh vlqjoh prgho wdnhv voljkwo| orqjhu/ uhodwlyh wr wkh hog gdwd1 Dowkrxjk wkh 

htxloleulxp prgho grhv qrw frqvlghu uhdfwlyh pdvv orvv/ wkh w lv txlwh uhdvrqdeoh 

vlqfh elrghjudgdwlrq ri wkh qdskwkdohqhv lv olnho| txlwh orz qhdu wkh vrxufh zkhuh 

pruh uhdglo| ghjudgdeoh frpsrqhqwv kdyh ghsohwhg wkh r{|jhq1 Wkh vroxwlrq lv yhu|


Conc (g/L) 

Conc (g/L) 

Conc (g/L) 

10 -3 

10 -4 

10 -5 

10 -3 

10 -4 

10 -5 

10 -3 

10 -4 

10 -5 


+ + + + + + + +++ + + ++++ + + ++++++ +++ + + + + 


* * * * * * ** ** * * *** * * * * **** *** * * * * 


10 1 

[Sh]=10x higher 

HA added 

10 2 

Time (days) 

+ * 

[Sh] = 10x lower 

Calibration 

[Sh] = 10x higher 

observed 

10 3 

+ 

* 

[Sh] 

=10x lower 

Iljxuh 6154= Vhqvlwlylw| ri qdskwkdohqh euhdnwkurxjk wr glvvroxwlrq udwh +Vkhuzrrg 

qxpehu,/ dw prqlwru W6E71 

vhqvlwlyh wr wkh dvvxphg hqkdqfhg vroxelolw| zklfk pd| dffrxqw iru wkh dssduhqw 

srru w dw odwhu wlphv1 Dq htxloleulxp dssurdfk pd| wkhuhiruh |lhog d uhdvrqdeoh 

uvw dssur{lpdwlrq ri wkh glvvroxwlrq ehkdylrxu> krzhyhu wkh ixoo uhdfwlyh prgho 

fohduo| uhsurgxfhv d ehwwhu w1


Conc (g/L) 

Conc. (g/L) 

Conc. (g/L) 

10 -3 

10 -4 

10 -5 

10 -3 

10 -4 

10 -5 

10 -3 

10 -4 

10 -5 

10 1 

observed T3B4 

single equilibrium model 

dual equilibrium model 

Methylnaphthalene 

Dimethylnaphthalene 

Trimethylnaphthalene 

10 2 

Time (days) 

Iljxuh 6155= Revhuyhg yv1 vlpxodwhg euhdnwkurxjk fxuyhv ri wkh qdskwkdohqh frp0 

srqhqwv dw W6E7 xvlqj vlqjoh dqg gxdo0vroxelolw| htxloleulxp glvvroxwlrq prghov1 

10 3 

10 4

FKDSWHU 61 HQKDQFHG GLHVHO IXHO GLVVROXWLRQ :3 

61915 Elrghjudgdwlrq Udwh 

Wkh pd{lpxp elrghjudgdwlrq udwh +& � lq htxdwlrq 51; dqg Wdeoh 618, zdv qrw lq0 

ghshqghqwo| nqrzq iru wkh slorw vfdoh h{shulphqw dqg kdg wr eh fdoleudwhg edvhg rq 

wkh revhuyhg euhdnwkurxjk fxuyhv1 Fdoleudwlrq wr wkh elrghjudgdwlrq udwh zdv gl!0 

fxow ehfdxvh r{|jhq olplwdwlrqv pdgh wkh vroxwlrq jhqhudoo| ohvv vhqvlwlyh wr fkdqjhv 

lq wklv rwkhuzlvh fulwlfdo sdudphwhu1 Iruwxqdwho|/ wkh h hfw ri wkh elrghjudgdwlrq 

udwh zdv fohduo| glvwlqjxlvkdeoh iurp wkdw ri wkh glvvroxwlrq udwh1 Lqfuhdvlqj wkh 

elrghjudgdwlrq udwh/ iru h{dpsoh/ uhgxfhv wkh frqfhqwudwlrqv wkurxjkrxw wkh revhu0 

ydwlrq shulrg zkhuhdv ghfuhdvlqj wkh glvvroxwlrq udwh rqo| uhgxfhv wkh hduo|0wlph 

frqfhqwudwlrqv/ dqg fdxvhv vljql fdqw wdlolqj +uhodwlyho| kljkhu frqfhqwudwlrqv, dw 

orqjhu wlphv1 Lq wklv vhfwlrq/ wkh pd{lpxp elrghjudgdwlrq udwh ri wkh qdskwkdohqhv 

lv fkdqjhg zkloh ohdylqj wkh udwhv iru EWH[ dqg wkh uhpdlqlqj frpsrqhqwv xq0 

fkdqjhg1 

Wkh vhqvlwlylw| ri wkh frpsrqhqw frqfhqwudwlrqv wr & � lv surylghg lq Iljxuhv 

6156 dqg 6157 zklfk vkrz wkh euhdnwkurxjk fxuyhv iru wkh phwk|o0qdskwkdohqhv 

dw prqlwruv W6E7 +lpphgldwho| grzqjudglhqw iurp wkh vrxufh, dqg W:F7 +418 

p grzqjudglhqw,/ uhvshfwlyho|1 Lqfuhdvlqj wkh pd{lpxp udwh e| d idfwru ri 43 

uhgxfhv wkh frqfhqwudwlrqv dqg surgxfhv d vrphzkdw srruhu w wr wkh revhuyhg 

gdwd/ sduwlfxoduo| qhdu wkh vrxufh> ixuwkhu iurp wkh vrxufh wkh revhuyhg gdwd ehfrph 

pruh vfdwwhuhg dqg wkh ehvw w ydoxh lv gl!fxow wr ghwhuplqh1 Ghfuhdvlqj wkh udwh 

e| d idfwru ri 43 kdv uhodwlyho| ohvv h hfw zklfk pd| eh gxh wr r{|jhq olplwdwlrqv1 

Wkh uhvxowv dovr vkrz d vrphzkdw juhdwhu vhqvlwlylw| ixuwkhu iurp wkh vrxufh duhd 

vlqfh pruh pdvv fdq elrghjudgh gxulqj wkh orqjhu wudyho wlph1


Conc (g/L) 

Conc (g/L) 

Conc (g/L) 

10 -3 

10 -4 

10 -5 

10 -3 

10 -4 

10 -5 

10 -3 

10 -4 

10 -5 

+ + + + + + + ++++ + ++++ + + ++++++ +++ + + + + 


* * * * * * ** ** * * *** * * * * **** *** * * * * 


10 1 

HA added 

10 2 

Time (days) 

+ * 

kmax = 10x higher 

Kmax calibrated 

kmax = 10x lower 

observed 


k 10x higher 

max kmax 10x lower 

Iljxuh 6156= Euhdnwkurxjk fxuyhv dw W6E7 +lpphgldwho| grzqjudglhqw iurp wkh 

vrxufh, vkrzlqj h hfw ri wkh pd{lpxp elrghjudgdwlrq udwh iru wkh qdskwkdohqhv1 

10 3 

+ 

*


Conc (g/L) 

Conc (g/L) 

Conc (g/L) 

10 -3 

10 -4 

10 -5 

10 -3 

10 -4 

10 -5 



+ 

10 -3 trimethylnaphthalene 

10 -4 

10 -5 

10 1 

+ + + 

* * * 

HA added 

k max 10x higher 

+ 

+ 

++ 

++ + + 

++ + + + 

+ 

+ 

+ 

+++ 

+ 

+ + 

+ * 

* ** 

** * * 

* * **** 

* * 

* 

* * * 

* 

10 2 

Time (days) 

+ 

kmax = 10x higher 

K calibrated 

max 

k =10xlower 

max 

observed 

10 3 

k max 10x lower 

Iljxuh 6157= Euhdnwkurxjk fxuyhv dw W:F7 +418 p grzqjudglhqw, vkrzlqj h hfw ri 

wkh pd{lpxp elrghjudgdwlrq udwh iru wkh qdskwkdohqhv1


61916 Vxevwudwh0Fduulhu Vruswlrq 

Wkh frqfhqwudwlrq ri d uhdfwlyh fduulhu zloo gluhfwo| lq xhqfh wkh udwh ri glvvroxwlrq 

ri d uhvlgxdo QDSO wkurxjk wkh hqkdqfhphqw idfwru +htxdwlrq 6147,1 Dowkrxjk 

kljkhu fduulhu frqfhqwudwlrqv zloo dozd|v lqfuhdvh wkh glvvroxwlrq udwh/ vruswlrq wr 

dtxlihu vrolgv dw orz fduulhu frqfhqwudwlrqv pd|/ lq idfw/ uhgxfh wkh prelolw| ri wkh 

glvvroyhg skdvh rujdqlfv1 Lq wklv vhfwlrq/ wkh vhqvlwlylw| ri wkh glhvho ixho glvvrox0 

wlrq lv whvwhg zlwk uhvshfw wr wkh kxplf dflg fduulhu frqfhqwudwlrq1 Wkh elqglqj 

frh!flhqwv +g�, uhpdlq wkh vdph dv lq wkh fdoleudwlrq vlpxodwlrq1 

Lq wkh slorw vfdoh h{shulphqw/ kxplf dflg zdv dgghg wr wkh wdqn dw dq h hf0 

wlyh frqfhqwudwlrq ri 31;6 j2O/ dqg zdv pdlqwdlqhg dw wkdw ohyho wkurxjkrxw wkh 

80|hdu h{shulphqw1 Lq hog vfdoh dssolfdwlrqv/ krzhyhu/ pdlqwdlqlqj frqvwdqw fdu0 

ulhu frqfhqwudwlrqv pd| eh pruh gl!fxow ehfdxvh ri wudqvlhqw rz hogv ru dtxlihu 

khwhurjhqhlwlhv1 Frqyhuvho|/ rqh pd| dovr eh lqwhuhvwhg lq xvlqj hyhq kljkhu frq0 

fhqwudwlrqv wkdq 31;6 j2O1 

Lq rughu wr h{dplqh wkh lq xhqfh ri fduulhu frqfhqwudwlrqv/ vlpxodwlrqv ri wkh 

slorw vfdoh h{shulphqw zhuh uhshdwhg zlwk kxplf dflg frqfhqwudwlrqv ri 3158 j2O 

dqg 43 j2O/ dqg uhvxowv frpsduhg zlwk wkh h{shulphqwdo dqg fdoleudwhg uhvxowv lq 

Iljxuh 61581 Wkh 3158 j2O frqfhqwudwlrq zdv fkrvhq dv lw olhv dw wkh euhdnsrlqw 

ri wkh Odqjpxlu lvrwkhup +Iljxuh 617,/ dqg Mrkqvrq ) Mrkq +4


Conc (g/L) 

Conc (g/L) 

Conc (g/L) 

10 -3 

10 -4 

10 -5 

10 -3 

10 -4 

10 -5 

10 -3 

10 -4 

10 -5 


[HA]=10.0 

[HA]=0.83 

HA added 

+ * 

+ + + + + + + ++++ + ++++ + + ++++++ +++ + + + + 


* * * * * * ** ** * * *** * * * * **** *** * * * * 


10 1 

10 2 

Time (days) 

10 3 

[HA] = 10.0 g/L 

[HA] = 0.83 g/L 

[HA] = 0.25 g/L 

observed 

+ 

* 

[HA]=0.25 

Iljxuh 6158= Euhdnwkurxjk fxuyhv dw W6E7 vkrzlqj h hfw ri kxplf dflg frqfhqwud0 

wlrq rq hqkdqfhg glvvroxwlrq ri glhvho ixho1


Conc (g/L) 

10 -3 

10 -4 

10 -5 


* * * * * * ** ** * * *** * * * * **** *** * * * * 

10 1 

HA added 

10 2 

Time (days) 

+ * 

10 3 

Km = 5 L/g 

Km = 10 L/g 

Km = 15 L/g 

observed 

Iljxuh 6159= Euhdnwkurxjk ri wulphwk|oqdswkdohqh dw W6E7 vkrzlqj vhqvlwlylw| wr 

wkh elqglqj frh!flhqw Np1 

61917 Elqglqj Frh!flhqw= WPQ 0 KD 

Wkh elqglqj frh!flhqw +g�, ghvfulehv wkh whqghqf| iru wkh rujdqlf frpsrqhqwv wr 

elqg wr wkh preloh kxplf dflg1 Iru wkh edvh fdvh +fdoleudwlrq, vlpxodwlrq/ ydoxhv 

ri g� zhuh rewdlqhg iurp ode0ghulyhg gdwd surylghg e| Ydq Vwhpsyrruw hw do1 

+5333,/ dqg olvwhg khuh lq Wdeoh 6161 Iru wkh wkuhh qdskwkdohqh frpsrqhqwv/ wkh 

prvw vljql fdqw yduldwlrq dqg xqfhuwdlqw| zdv revhuyhg iru wulphwk|oqdskwkdohqh 

ehfdxvhriwkhjuhdwhuqxpehurilvrphuv/rizklfkrqo|rqhzdvwhvwhg+5/6/80WPQ,1 

Vlqfh wulphwk|oqdskwkdohqh lv dovr wkh ohdvw vroxeoh ri wkh wkuhh qdskwkdohqhv/ lwv 

elqglqj frh!flhqw zrxog kdyh wkh juhdwhvw h hfw rq wkh exon glvvroxwlrq udwh1 

Wr ghwhuplqh wkh vhqvlwlylw| ri wkh glhvho glvvroxwlrq surfhvv wr wkh elqglqj 

frh!flhqw ri wulphwk|oqdskwkdohqh/ wkh edvh vlpxodwlrq zdv uhshdwhg iru 5 gl huhqw 

ydoxhv ri g�/ dqg wkh uhvxowv surylghg lq Iljxuh 61591 Wkh udqjh ri g� zdv vhohfwhg 

edvhg rq hvwlpdwhg xqfhuwdlqw| lq wkh revhuyhg gdwd1 Uhgxflqj wkh frh!flhqw iurp 

43 O2j lq wkh edvh vlpxodwlrq wr 8 O2j fohduo| grhv qrw pdwfk wkh revhuyhg gdwd dqg 

vljql fdqwo| lqfuhdvhv wkh wlph iru frpsohwh glvvroxwlrq1 Lqfuhdvlqj wkh frh!flhqw 

iurp 43 O2j wr 48 O2j surylghv d vrphzkdw lpsuryhg pdwfk dw hduo| wlph +840833 

gd|v,/ exw voljkwo| xqghuhvwlpdwhv wkh glvvroxwlrq wlph1 Wkh h hfw ri fkdqjlqj wkh 

elqglqj frh!flhqw ri WPQ kdg d qhjoljleoh h hfw rq wkh ehkdylrxu ri wkh rwkhu wzr 

qdskwkdohqhv1 

*


Conc. (g/L) 

10 -2 

10 -3 

10 -4 

10 -5 

10 1 

Other 

DMNap 

TMNap 

enhanced dissolution 

no enhancement 

10 -1 

10 2 

Time (years) 

10 0 

MNap 

Time (days) 

Iljxuh 615:= Orqj0whup glvvroxwlrq ri wkh glhvho ixho vrxufh= frpsdulvrq ehwzhhq 

wkh fdoleudwhg/ kxplf dflg0hqkdqfhg prgho/ dqg dq htxlydohqw vlpxodwlrq zlwkrxw 

d fduulhu1 Duurzv lqglfdwh vkliw lq frpsrqhqw glvvroxwlrq fxuyhv iurp wkh fduulhu0 

hqkdqfhg vlpxodwlrq wr wkh qr0hqkdqfhphqw vlpxodwlrq1 

61918 Orqj0Whup Glvvroxwlrq 

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hwkdqro soxph1 

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r{|jhq ohyhov dv lq wkh hwkdqro0iuhh fdvh1


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Elev (m) 

Elev (m) 

Elev (m) 

Elev (m) 

Elev (m) 

10 

5 

0 

10 

5 

0 

10 

5 

0 

10 

5 

0 

10 

5 





ethanol, 20 years 


0 

0 100 200 300 400 

Iljxuh 719= Vlpxodwhg ehq}hqh soxphv iurp wkh jdvrkro vrxufh dw 43/ 48 dqg 53 

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frqwrxuv ydu| iurp d edfnjurxqg ri 61; pj2O wr 313 pj2O zlwklq wkh jdvrolqh dqg 

hwkdqro soxphv1


Benzene Mass (kg) 

0.5 

0.4 

0.3 

0.2 

0.1 

biodegraded mass 

aqueous mass 

0 

0 2000 4000 6000 8000 

Time (days) 

gasoline source 

gasohol source 

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shuvlvwhqfh1


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Wkhvh qglqjv frqwudglfw wkh dvvxpswlrqv pdgh e| PfQde hw do1 +4


Vfhqdulr 7= Pxowlsoh Vsloo 

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Elev (m) 

Elev. (m) 

Elev. (m) 

10 

5 

0 

15 years 

10 

5 

0 

20 years 

10 

5 


10 years 


10 years 

15 years 

20 years 

0 

0 50 100 150 200 0 50 100 150 200 



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Travel Distance (m) 

400 

300 

200 

100 

R ben =1.1 

benzene plume from gasohol source 

benzene plume from gasoline source 

R ben =1.5 

0 

0 5 10 15 20 25 

Time (years) 

Iljxuh 71


Elev (m) 

Elev. (m) 

Elev. (m) 

10 

5 

5 

0 

20 years 

10 

5 


10 years 

0 

15 years 15 years 

10 

0 

0 100 200 300 400 



10 years 

20 years 

0 100 200 300 400 


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r{|jhq frqfhqwudwlrq ri 513 pj2O1


Elev (m) 

Elev. (m) 

Elev. (m) 

10 

5 

5 


10 years 

0 

15 years 

10 

0 

20 years 

10 

5 

0 

0 100 200 300 400 



10 years 

15 years 

20 years 

0 100 200 300 400 


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10 5 

10 4 

10 3 

10 2 

10 1 

10 0 

ethanol spilled 

at 5 years 

ethanol 

benzene 

TEX 

0 2500 5000 7500 10000 

Time (days) 

remaining components 

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Elev (m) 

Elev. (m) 

Elev. (m) 

10 

5 

5 

10 years 

0 

15 years 

10 

5 

0 

20 years 

10 

0 

0 100 200 300 400 


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Elev (m) 

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10 

5 

0 

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0 

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5 

0 

10 

5 

1yr. 

1yr. 

20 years 

5yrs. 

5yrs. 

10 yrs. 

0 

0 100 200 300 400 

ethanol, benzene (µg/L) 

20 yrs. 

10 100 1000 10000 

20 yrs. 


ethanol 

methane 

oxygen 

benzene 

methane, oxygen (mg/L) 

0.1 0.5 1 1.5 2 2.5 3 3.5 

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