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Li cm n

Trong thi gian va qua, ngoi s n lc ca bn thn, ti nhn


c s gip nhit tnh ca cc thy c gio, cn b, gia nh cng bn b
hon thnh kho lun ca mnh. Nhn dp ny, cho php ti by t lng
bit n su sc n tt c nhng s gip qu bu .

Li u tin ti xin trn trng cm n cc thy c ging dy v hng


dn thc tp khoa Ti nguyn v Mi trng, trng i hc Nng nghip
H Ni to iu kin thun li nht cho ti trong thi gian hc tp v rn
luyn ti trng. Ti xin by t lng bit n su sc ti ThS. inh Tin
Dng Vin Mi trng Nng nghip v ThS. Nguyn Th Thu H trng
i hc Nng nghip H Ni, nhng ngi trc tip hng dn v gip
ti trong sut qu trnh thc tp hon thnh kho lun ny.

Ti xin chn thnh cm n d n Nghin cu nh hng ca ho


cht nng nghip n hin tng tm cht hng lot ng bng Sng Cu
Long cung cp k thut, phng tin v kinh ph thc hin nghin cu
ny. Ti xin cm n cc cn b lm vic ti Trung tm Phn tch v Chuyn
giao Cng ngh Mi trng Vin Mi trng nng nghip to iu kin
v trc tip gip ti trong b tr th nghim v phn tch mu.

Cui cng ti mun dnh li cm n chn thnh nht ti gia nh


vbn b, nhng ngi ng vin, gip ti trong sut thi gian hc tp,
rn luyn ti trng i hc Nng nghip H Ni.

H Ni, ngy 10 thng 05 nm


2013
Ngi thc hin

Nguyn Th Cng

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MC LC

2
DANH MC VIT TT
AOT Cng ngh oxy ha tin tin
BVTV Bo v thc vt
CPSH Ch phm sinh hc

DCVA 3 - (2,2 - dichlorovinyl) - 2,2 - dimethyl cyclopropanecarboxylic


acid

DDT Dichlorodiphenyltrichloroethane
BSCL ng bng sng Cu Long
GAC Granular Activated Carbon (than hot tnh dng ht)
GC/MS Gas ChromatographyMass Spectrometry (sc k kh khi ph)
HCBVTV Ho cht bo v thc vt

IUPAC International Union of Pure and Applied Chemistry

(Linhip Ha hc Thun ty v ng dng Quc t)

NN Nng nghip

NTTS Nui trng thy sn

PAC Powdered Activated Carbon (than hot tnh dng bt)

PBA 3 - phenoxybenzoic acid

PTNT Pht trin Nng thn

TCE Tricloetylen

VLHP Vt liu hp ph

VSV Vi sinh vt

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DANH MC CC HNH

Phn 1. T VN
1.1. Tnh cp thit ca ti

Vic s dng ha cht v thuc bo v thc vt (BVTV) c tc dng


tch cc trong nui trng thy sn (NTTS) nhng d tha ha cht v thuc
BVTV li lm suy gim mi trng. Cht lng ngun nc phc v cho
NTTS cng ang c coi l mi nguy e da n an ton v bn vng ca
ngnh NTTS ca nc ta.Phan Thanh Cng (2011) cho bit theo bo co
ca Cc Th y (2011), tnh hnh dch bnh trn tm ti cc tnh ven bin ng
bng sng Cu Long (BSCL) din bin rt phc tp, c bit l hin tng

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tm nui cht hng lot, trn din rng. Tm cht ch yu cc vng nui
tm thm canh, c tnh din tch thit hi t 80 - 90%. Thng k tnh hnh
nui tm ti 12 tnh trng im cho thy din tch th ging l 622.750 ha
trong din tch th tm s l 609.994 ha (chim 97,95%); din tch th tm
chn trng l 12.775 ha (chim 2,05%).

Nguyn nhn chnh gy ra cht tm hng lot trong thi gian qua mt
phn do virus, vi khun, vt ch mang mm bnh ly lan cng ng, cn
nguyn nhn chnh na l do thuc dit gip xc. Rt nhiu bo co khoa hc,
kin ca cc nh qun l, nng dn cho rng chnh t thuc BVTV hoc ha
cht c ngun gc t thuc BVTV m ngi nng dn lm dng dng dit
tp cho ao nui ca mnh lm cho tm ng c. Trong cc thuc BVTV th
Cypermethrin c s dng rt ph bin.

Mc d nhim ha cht c coi l mt trong s cc tc nhn gy


cht tm quan trng nhng cho n nay trong nc vn cha c cng trnh
nghin cu chuyn su no v lnh vc ny. Trong khi , cc cng ngh x
l d lng ha cht trong ao nui ni ring v trong nng nghip ni chung
hin cn rt hn ch k c trn th gii ln trong nc. Than hot tnh c s
dng kh ph bin trong cng ngh hp ph cht nhim hu c c nng
thp, thm vo trong nc v trn Th gii hin nay c nhiu nghin
cu lm c s ng dng cng ngh hp ph s dng than hot tnh vo x
l d lng thuc BVTV. Mc d vic s dng than hot tnh kh ph bin
trong x l nc ngt, trong nc mn v nc l hin c rt t nghin cu.

T nhng l do trn chng ti tin hnh thc hin ti: nh gi


kh nng hp ph Cypermethrin ca than hot tnh (GAC) trong nc
lqua xut thit k m hnh ct hp ph Cypermethrin bng than hot
tnh (GAC) x l Cypermethrin trong nc l.

1.2. Mc ch nghin cu

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- Xc nh cc yu t nh hng n kh nng hp ph Cypermethrin
ca than hot tnh dng ht (GAC) trong mi trng nc l.
- nh gi kh nng hp ph Cypermethrin ca than hot tnh GAC
lm c s xy dng phng n hp ph x l Cypermethrin.
1.3. Yu cu nghin cu

- Xy dng c c s d liu v kh nng hp ph Cypermethrin ca


than hot tnh.

- S liu trung thc, r rng

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Phn 2. TNG QUAN CC VN NGHIN CU
2.1. Hin trng tn d ca Cypermethrin trong nui tm nc l
Ho cht c s dng vi nhiu mc ch khc nhau: cng nghip,
nng nghip, sinh hot ca con ngi... Trn th gii hin nay c trn
4.000.000 loi ha cht khc nhau, trung bnh hng nm c khong 30.000
cht mi c pht minh v a vo s dng. Trong s cc ha cht trn c
khong 60.000 n 70.000 loi c dng thng xuyn v rng ri. Mt s
lng ng k trong s c s dng trong NTTS, l mi nguy him e
da n mi trng v sc khe con ngi.

Theo tp on nghin cu kinh doanh quc t Freedonia, doanh s ca


mt hng ha cht nng nghip th gii nm 2009 l 45 t USD v d kin s
tng ln mc 52 t USD vo nm 2014. Trong , Trung Quc lun l nc
ng u c hai v tr, nh sn xut v ngi tiu th. Vin Cy trng thuc
Vin Hn lm khoa hc Trung Quc cho bit nhu cu s dng cc loi thuc
tr su ca nc ny tng t 700.000 tn nm 1990 ln 1,7 triu tn nm
2008 (tng ng 30 kg/ha). Nu thng k trung bnh lng thuc tr su s
dng theo din tnh th con s ny ca Trung Quc cao hn t 3 n 5 ln so
vi cc quc gia khc, lng tiu th chim 35% th phn th gii, tng
ng c hai nc M v n cng li.

Nghin cu ca Lyle-Fritch v cng s (2006),cho thy vic s dng


ha cht v ch phm sinh hc c s dng trong cc trang tri nui tm
cc nc nh Philipine, Mexico, Thi lan, n . Khong 40 loi ha cht v
ch phm sinh hc c s dng ci to, x l ao nui tm ti nhng vng
nui cng nghip v bn thm canh Thi Lan thp nin 90 n nm2000
s lng hot cht tng ln ti70. Mexico, nm 2001 c ti 179 ha cht
s dng trong ao nui tm.

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Theo nghin cu ca Kanchanakarn (1986), Thi Lan, Dipterex c
khuyn co s dng rng ri lng 0,25 0,3 ppm dit cc loi gip xc,
sinh vt v k sinh trng n bo trong ao nui c. S dng Dipterex cao hn
2 - 3 ln. Khi phn tch chi ph/li ch ca cc trang tri khc nhau min
ng Thai Lan Tonguthai, Kamonporn (2000) cho thy nng dn chi
khong 10 baht cho s dng ha cht cho mi 1 kg tm thng phm. Nm
1995, khi sn lng tm t 250.000 tn, c tnh t nht 2.500 triu Baht
(100 triu USD) phi chi cho ring cc ha. Nhng ha cht ny Thai Lan
nhp khu ch yu t M, Canada, Anh, Australia v Nht Bn.

Bn cnh thuc BVTV c s dng trc tip dit gip xc trong


ao, 1 lng thuc cng xm hp vo ao qua ngun nc b nhim thuc
BVTV do r r, thm thu trong qu trnh s dng trn cc cy trng NN.

2.1.1. c im v tnh cht ca Cypermethrin

Theo Trng Quc Ph (2012), Cypermethrin l mt loi thuc tr su


tng hp thuc pyrethoid (thuc bo v thc vt tho mc chit sut t cc
loi thuc nhm hoa cc), chng c tng hp thnh cng vo nm 1974 v
c tung ra th trng ln u tin vo nm 1977do cc nh sn xut Zeneca
Inc., FMC Corp., v American Cyanamid co., vi cc tn thng mi nh
Demon, Cybush, Ammo, Cynoff Cypermethrin l mt hp cht hu c c
tn ha hc l Cyano (3 -
phenoxyphenyl)methyl 3 - (2,2 -
dichloroethenyl) - 2,2 - dimethylcyclo
propanecarboxylate. Cng thc phn t
ca Cypermethrin l C22H19Cl2 NO3.
Cypermethrin l cht bn rn (st), khng mi, c mu vng nu v t
tan trong nc (khong 0,005 - 0,01 mg/l) nhng tan tt trong dung mi hu
c nh aceton (620g/L), xylen (351 g/L) v cyclohexanone (515 g/L).
Khi b thy phn, thi gian bn hy (DT 50) ca cypermethrin ph thuc

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vo dng ng phn v pH ca mi trng. iu kin nhit 25 0C, thi
gian bn hy ca dng ng phn trans l 923 ngy, 136 ngy, 5 ngy v 23
pht tng ng vi iu kin pH l 3, 7, 8 v 11. Dng ng phn cis bn hn
nn c thi gian bn hy l 1302 ngy, 221 ngy, 21 ngy v 38 pht, tng
ng vi iu kin pH l 3, 7, 8 v 11.Thi gian bn hy ca cypermethrin do
quang phn tng i nhanh hn so vi thy phn. Trong nc (nhit 20 0C
v pH = 4) thi gian bn hy l 12,4 - 14,8 ngy, trong khng kh thi gian
bn hy l 3,47 gi v trong t thi gian bn hy l 34,2 - 38,2 ngy.
2.1.2. Ngun gc ca Cypermethrin trong ao nui tm

Ngun ch ng: Theo kt qu nghin cu ca Vin nghin cu nui


trng thy sn I (2004), t nht c 1893 ch c 1500 sn phm c cp php,
trong c 476 sn phm c cha cht khng sinh c s dng trong NTTS.
Trong c 373 loi dit tr dch hi, 14 loi x l t v nc, 6 cht gy mu
nc, 86 cht kh trng v dit tp, 138 khng sinh, 47 loi ch phm sinh hc
(CPSH), 13 loi vitamin, 57 loi thc n b sung, 10 loi hormone, 5 loi khng
xc nh. Nui tm dng 186 loi (c 32 loi khng sinh); sn xut tm ging 98
loi (39 khng sinh); nui c bin 29 loi (14 loi khng sinh); nui c lng nc
ngt 74 loi (41 loi khng sinh); nui c ao nc ngt 67 loi (31 khng sinh);
sn xut c ging nc ngt 85 loi (37 khng sinh). Trong s , theo Mai Vn
Ti v ctv (2004) vn cn 5 loi b B thy sn (nay l b Nng nghip v
Pht trin nng thn) cm kinh doanh, sn xut v s dng.

Nh vy c th nhn thy cc ha cht chnh c trong ao nui tm xut


pht t hot ng kh trng v dit tp, ha cht s dng trong cc sn phm
ch phm sinh hc v thc n b sung, hoocmon. C 194 loi thuc, ha cht
v CPSH c s dng trong nui tm vi 32 loi thuc khng sinh c
29% h s dng; 98 loi trong sn xut tm ging vi 39 loi thuc khng
sinh. Khng sinh c dng ch yu l nhm Oxytetracyclin (Oxytetracyclin,
Tetracyclin, Doxycyclin), c bit l cc c s sn xut ging tm

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(67%).Ngoi ra ngi dn cn ch ng s dng cc ha cht kh trng v
dit tp. Mt s cht nh: Formalin, ng sulfat, thuc tm, Dipterex, l xoan,
v cc cht kch thch tm lt xc nh Saponin, Saprotex, B Ht Tr.

Hnh 2.1: T trng cc sn phm ho cht s dng trong NTTS

(Ngun: Mai Vn Ti v cng tc vin,2004)

Theo iu tra ca Nguyn Vn Ho, L Hng Phc v Cao Thnh


Trung (2011), th100% cc h s dng cc loi vi lng, men tiu ha tng h
min dch, ci thin hp thu dng cht v gip tng trng tt trong c th
tm nh Oceanic, Azomite, Sorbitol, Kenton, Enrolive, Betaglucan,Olimos
v khng sinh nh Flofenicol (0,5 - 1 g/kg thc n), Oxytetraciline (10 - 20
g/kg thc n) nhm phng nga v dit khun gy bnh trn tm khi c dch
bnh. Theo Hunh Th T (2006),trong nui tm s ti Sc Trng v Bc Liu
s dng 74 loi thuc v ha cht trong c 20 loi thuc v ha cht dng
dit tp v ty trng; 19 loi khng sinh; 10 loi ha cht dng x l t v
nc; 10 loi men vi sinh v mt s loi thuc v ha cht khc nh phn bn,
sn phm dng tng cng h min dch b sung vo thc n cho tm.Theo
Nguyn Th Phng Nga (2004) th Sc Trng, Bc Liu v C Mau c n 116

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sn phm thuc v ha cht c s dng trong nui trng thy sn thuc cc
nhm vi cc mc ch khc nhau. Trong ha cht l 40 loi, ch phm sinh
hc 35 loi, nhm khng sinh 15 loi, nhm khong thin nhin 4 loi, nhm
vitamin, khong , lipid c 22 loi. Ha cht vi hot cht nh saponin,
trichlorofol, dichlorofol organophosphate, pyrethorid c s dng ph bin
nht. Tng t, khng sinh c ngi nui s dng trong qu trnh nui
thng dng khng sinh n l ch yu l nhm fluoroquinolones. Trong
42,9% s h iu tra s dng enrofloxacin v 25% s h s dng norfloxacin.
Ngoi ra, sulfamethoxazol, cortrimoxazol, aminosid, colistin v trimethoprim
cng c s dng nhiu nhng chim t l thp.

Qunh Hng (2012) cho rng trn th trng hin c khong 20 sn


phm c cha Cypermethrin vi cc tn gi khc nhau nh Sherpa, Ambush
C, Cymbush, Peran, Cyperan, Barricade, Ripcord, Ammo, Cypermethrine,
Cyperator, Hilcyperi, Neramethrin...Cht c chaCypermethrin lu nay ch
c dng lm thuc BVTV nhng c trng hp ngi dn dng nhng sn
phm c Cypermethrin vo nui trng thy sn dit gip xc ti cc ao
nui thy sn, nht l trong qu trnh ci to ao nui tm. y l cht rt c,
ch cn nng 0,05 ppm cng lm tm cht 50%.

Bn nn y ao:cng l ngun nhim quan trngi vi cc vng


nui thm canh, khi s lng ng cc cht nhim trong mt thi gian di m
kh nng ci to cng khng th lm sch ng nn y ao. Nguyn Vn
Ho, L Hng Phc v Cao Thnh Trung (2011), nghin cu cc m
hnh Trang ti ti M Thanh, Sc Trng cho thy trong16mu t bn y ao
trn16aonuitrongttccctrangtrithc50% (8/16 ao) cha hm lng
Cypermethrin dao ng t 31.5 - 603.5 ppb. Kt qu phn tch ny cho thy
d hm lng thuc dit gip xc (Cypermethrin) trong ao nui rt ln.
nhng ao c hm lng thuc dit gip xc c nng tn lu cao, th tm

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cht rt nhanh v thi gian sng ca tm ngn. Nh vy c th nhn thy qu
trnh thm canh lu nm dn n s lu tr ca Cypermethrin t cht dip
gip xc, hoocmon m qu trnh ci to ao cng khng th ty ht.

2.1.3. S tn ti v tch ly sinh hc Cypermethrin trong c th tm

Theo DeeAn Jones, th kh nng ha tan ca Cypermethrin trong nc


rt l thp, 4 ppb 200C. Cypermethrin rt k nc v s nhanh chng
chuyn t dung dch nc thnh cc ht l lng. Nh vy, mt lng
tng i nh cc cht l lng c th loi b mt s lng ng k ca
cypermethrin t pha nc. t v trm tch ca cc h cha l mi trng
chnh cho Cypermethrin.

Nghin cu ca DeeAn Jones cng tin rng Cypermethrin thy phn


trong nc chm pH 7 v nhanh hn pH 9. Di nhit mi trng bnh
thng v pH n nh, Cypermethrin thy phn vi chu k bn r > 50
ngy. N cng n nh quang phn vi chu k bn r > 100 ngy. Trong dung
dch v trng trong iu kin c nh sng mt tri, cypermethrin bin i
chm, <10% b mt trong 32 ngy.Trong bng ti, cypermethrin tng i n
nh vi 88,7 v 95,6% phc hi sau 10 ngy tng ng trong nc sng v
nc ct. Theo Kidd v James (1991), trong nc sng Cypermethrin bin i
nhanh vi chu k bn r khong 5 ngynhanh hn so vi trong nc ct ba
n bn ln. iu ny cho thy s quang phn gin tip lin quan n cht
trong t nhin m kt qu tng cng thoi quang hc. Khi thoi quang hc
ca cypermethrin xy ra, sn phm ln sinh ra l DCVA, PBA v mt lng
nh 3 phenoxybenzaldehyde.

Theo Agnihorti et al.(1986), vic loi b cypermethrin c c trong


dung dch nc l nhanh chng, vi khong 95% b mt trong vng 24 gi
sau khi s dng nc v trm tch cha trong hm m. H s phn vng ca
cypermethrin l rt cao (Kow = 3.98x106), do n lin kt mnh m vo

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cht hu c. Bi sc ht mnh m i vi t, cypermethrin c th c di
chuyn ti cc vng nc ln cn trong trm tch do ma v ti tiu. Tuy
nhin, mt khi phn t thuc tr su c hp th trong t, gim bt nguy c
c tnh vi ng vt thy sn. Nghin cu ca Crossland (1982) ch ra
rng trong cc th nghim ao, c vn cn tn ti trong nc ao c cha nng
gy cht cacypermethrin (5ppb) v ha cht c hp ph vo cht rn
l lng.

Nhm thuc tr su pyrethroid (hin c trn 30 hot cht) tc ng n


sinh vt bng con ng tip xc v v c. Pyrethroid tc ng trc tip n
h thn kinh ca cn trng v ng vt mu nng; gy ri lon s dn truyn
xung ng ca knh natri dc si trc ca t bo thn kinh cn trng. cn
trng, pyrethroid ch tc ng n cc trung tm h hp; cn ng vt mu
nng, pyrethroid tc ng n cc trung tm h hp tu sng v h thn
kinh kim sot chc nng ca tim. Triu chng ng c ca pyrethroidtrong
cn trng v ng vt mu nng rt ging nhau: trc tin l kch ng, rng
mnh, ri lon tip sau l bi lit v cht. i din nhm ny gm
cypermethrin, permethrin, fenvalarate, deltamethrin...

Khi tm tip xc vi ha cht s lm tng s cng thng, do lm


gim tng trng ca tm, tng kh nng mn cm vi VSV. Theo Bainy
(2000), cc cht kh trng, khng sinh, thuc tr su, phn bn v ph gia
thc n ... c s dng trong nui tm, tt c u c mt nguy c tim n
gy ra tc dng c hi i vi tm nui.

Kh nng tc ng ca Cypermethrin n tm nghin cu c tnh ca


Cypermethrin i vi ng vt thn mm v c nui nc ngt c
nghin cu t rt sm. Cc ng vt thn mm c nng gy cht 50%
trong 24 gi (24h LC50) t 0,5 n 2 ppb Cypermethrin.

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Cc tc gi ngi M Pahl & Opitz (1999), cng nghin cu tc ng
ca Cypermethrin i vi tm hm nui, kt qu cho thy LC 50 trong 1 - 48
gi dao ng t 0,058 n 1,69 ppb ty thuc vo nhit v giai on pht
trin ca tm hm. Cc nghin cu v c tnh ca Cypermethrin trn tm
hm nhm cnh bo tc hi ca vic s dng thuc Excis (1%w/c
Cypermethrin) dit rn bin (Lepeophtheirus salmonis v Caligus
elongatus) gy bnh trn c hi nui. Trong khi liu gy cht ng k tm
hm u trng trong 1 gi thp hn 100 ln so vi liu cht khuyn co. c
cp tnh ca Cypermethrin (gi tr LC50) i vi gip xc v cn trng thng
nng nh hn 0,01 mg/l, i vi c nh hn 1 mg/l.

Bng 2.1. Gi tr LC50 ca Cypermethrrin i vi mt s loi thy sinh

Loi thy sinh vt LC50 96 gi (mg/l)


C hi (Oncorhynchus mykiss) 0,39
C tu (Cyprinodon variegatus) 0,95
C chp (Cyprinus carpio) 0,05
C tr phi (Clarias gariepinus) 63,0
Tm nc ngt (Palaemonetes argentinus) 0,002
Tm nc l (Mysidopsis bahia) 0,005
Tm hm (Homarus americanus) 0,04
Gip xc bi nghing (Gammarus pulex) 0,0036
Gip xc ru ngnh (Daphnia magna) 0,001
u trng chun chun (Cloeon dipterum) 0,004
Ngun: PGS.TS. Trng Quc Ph ,2011

Theo bo co ca Vin Nghin cu NTTS II, Cc Th y, V NTTS


phn tch nguyn nhn bng pht ly lan dch bnh tm nui, hin tng
tmcht ti cc tnh BSCL nm 2011 c th l do nh hng cc cht dit
gip xc c ngun gc thuc BVTV tng gp 3 ln. Phn ln ngi nui s
dng thuc dit tp c thnh phn Cypermethrin, thm ch, rt nhiu h s
dng trc tip thuc BVTV nh Padan, Decid, Thiodan.... Cc loi ny c tc

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dng dit tp rt mnh (do rt c), gi li r hn so vi thuc kh trng ao
nui trong thy sn nn nhiu nng dn s dng. Chng tn lu di trong t,
nc, gy ng c mn tnh cho tm, lm cho gan ty b yu, sc khng
km nn d pht sinh dch bnh. Khi gp thi tit bin ng mnh, tm c th
cht hng lot. Cc chuyn gia ca Trng i hc Arizona cng nhn nh
rng, hi chng hoi t gan ty gy cht hng lot trn tm thi gian qua c
th do b nhim c t cc c t trong mi trng, trong c sn phm dit
tp c cha Cypermethin.

Nguyn Vn Ho, L Hng Phc v Cao Thnh Trung (2011)


nghin cu v thuc dit gip xc tn d trong ao nui cho thy, trong 16 mu
t trn 16 ao nui trong tt c cc trang tri th c 50% (8/16 ao) c hm
lng Cypermethrin dao ng t 31,5 - 603,5 ppb. Kt qu ny cho thy d
lng thuc dit gip xc (Cypermethrin) trong ao nui rt ln. nhng ao
c hm lng thuc dit gip xc c nng tn lu cao,th tm cht rt
nhanh v thi gian sng ca tm ngn. Nhiu nghin cu cho thy vi mt
hm lng nh thuc tr su nh DDT, Methyl parathion, vi nng 0,6 - 6
ppb, 2 - 7 ppb c th gy cht cho loi gip xc n 50%. Theo th nghim
ca Flegel v ctv (1992), vi nng 0,1 g trong nc c th gy cht tm
(1 - 3g) n 10% trong 10 ngy th nghim iu ny cho thy vi mt nng
cc nh 0,1 g/l gy cht tm.

Kt qu phn tch 8 mu nc v 13 mu bn lng ly t 2 tnh c thit


hi tm cht nghim trng nht nm 2011 l Sc Trng v Bc Liu ca Cc
BVTV v Vin Mi trng nng nghip cho thy, 100% cc mu nc ny
u b nhim d lng thuc BVTV Cypermethrin vt mc cho php t 3
n hn gp 6 ln. Theo kt qu nghin cu gn y ca Vin nghin cu
Nui trng thy sn II t l tm cht do Cypermethrin gy ra cc nng
0,05 ppb l 100% trong vng 10 ngy th nghim, cc nng thp hn, t l

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cht t 30 76% trong 35 ngy th nghim. Trong tm mu i chng
khng c du hiu hoi t gan ty. Tm cht bt u c du hiu hoi t gan
ty vo ngy th 7, th 16 v th 12 khi nui cc nng : 0,01; 0,001 v
0,0001 ppb. Kt qu quan trc cht lng mi trng nc v bn y ca
Cc BVTV trong nm 2011 cho thy d lng ca Cypermethrin trongc 8
mu nc cp vo ao nui u bin ng t 0,016 n 0,032 phn t, c 3/13
mu bn y cha d lng hot cht ny mc 0,0050,18 ppb.

2.2. Cc phng php x l tn d thuc bo v thc vt trong nc hin


nay

Theo Cng ty C phn u t cng ng Mi trng Vit Nam, hin


nay trn th gii c nhiu bin php khc nhau c nghin cu v s
dng x l nhim cc ho cht hu c c hi kh phn hy trong c
ha cht BVTV, cc phng php v cng ngh nh sau:

2.2.1.Bin php phn hu nh vi sng Plasma

Bin php ny c tin hnh trong thit b cu to c bit. Cht hu


c c dn qua ng phn ng y l Detector Plasma sinh ra sng pht x
electron cc ngn (vi sng). Sng pht x electron tc dng vo cc phn t
hu c to ra nhm gc t do v sau dn ti cc phn ng to SO 2, CO2,
HPO32 - , Cl2, Br2 V d: Malathion b ph hu nh sau:

Plasma + C10H19OPS + 15O2 SO2 + 10CO2 + 7H2O + HPO3 + NO2

u im ca bin php ny l hiu sut x l cao, thit b gn nh. Kt


qu thc nghim theo bin php trn mt s loi HCBVTV ph hu n
99% (vi tc t 1,8 n 3 kg/h).Kh thi khi x l an ton cho mi trng.
Tuy nhin, nhc im ca bin php ny l ch s dng hiu qu trong pha
lng v pha kh, chi ph cho x l cao, phi u t ln.

2.2.2. Bin php oxy ho bng ozon/tia cc tm

16
Ozon ho kt hp vi chiu tia cc tm l bin php phn hu cc cht
thi hu c trong dung dch hoc trong dung mi. K thut ny thng c
p dng x l nhim thuc tr su M. Phn ng phn hu ho hc:

Thuc tr su, dit c + O3 CO2 + H2O + cc nguyn t khc

u im ca bin php ny l s dng thit b gn nh, chi ph vn hnh


thp, cht thi ra mi trng sau khi x l l loi t c, thi gian phn hu rt
ngn. Nhc im ca bin php l ch s dng c hiu qu cao trong cc pha
lng, pha kh. Chi ph ban u cho x l l rt ln.

2.2.3. Bin php phn hu sinh hc

Trong nhng nm gn y xu hng s dng vi sinh vt phn hu


lng tn d ha cht BVTV mt cch an ton c ch trng nghin cu.
Phn hu sinh hc tn d ho cht BVTV trong t, nc, rau qu l mt
trong nhng phng php loi b ngun gy nhim mi trng, bo v sc
kho cng ng v nn kinh t. Bin php phn hu ha cht BVTV bng tc
nhn sinh hc da trn c s s dng nhm vi sinh vt c sn mi trng t,
cc sinh vt c kh nng ph hu s phc tp trong cu trc ho hc v hot
tnh sinh hc ca ha cht (BVTV). Tp on vi sinh vt t c th phn hu
ha cht BVTV v dng thuc nh l ngun cung cp cht dinh dng v
nng lng chng xy dng c th.

Mt s loi thuc thng ch b mt s loi vi sinh vt phn hu nhng


c mt s loi vi sinh vt c th phn hu c nhiu ha cht BVTV trong
cng mt nhm hoc khc nhm. V d, thuc tr c 2,4-D b 7 loi vi khun,
2 loi x khun phn hu. Ngc li, mt s loi VSV cng c th phn hu
c cc thuc trong cng mt nhm hoc thuc cc nhm rt xa nhau. V d,
nm Trichoderma viridi c kh nng phn hu nhiu loi thuc tr su clo,
ln hu c, cacbamat, thuc tr c. Cc nghin cu cho thy trong t tn ti
rt nhiu nhm vi sinh vt c kh nng phn hu cc hp cht photpho hu

17
c, v d nh nhm Bacillus mycoides, B.subtilis, Proteus vulgaris Nhiu
vi sinh vt c kh nng phn hu 2,4-D nh Achromobacter, Alcaligenes,
Corynebacterrium, Flavobaterium, Pseudomonas Yadav J. S v cng s
pht hin nm Phanerochaete chrysosporium c kh nng phn hu 2,4-D v
rt nhiu hp cht hu c quan trng c cu trc khc nh Clorinated phenol,
PCBs, Dioxin, Monoaromatic v Polyaromatic hydrocacbon, Nitromatic.Nm
1974, Type and Finn cho thy kh nng thch nghi v s dng thuc BVTV
nh ngun dinh dng cacbon ca mt s chng Pseudomonas sp. Nm
1977, Doughton v Hsieh khi nghin cu s phn hu parathion nh mt
ngun dinh dng th qu trnh phn hu din ra nhanh hn. Theo Brown
(1978) th mt loi thuc BVTV c th b mt hay mt s loi VSV phn hu.

Theo Fild v Hemphill (1968); Brown (1978), nhng thuc d tan trong
nc, t b t hp ph thng b vi khun phn hu, cn nhng thuc kh tan
trong nc, d b t hp ph li b nm phn hu l ch yu.Qu trnh phn
hy ha cht BVTV ca sinh vt t xy ra trong mi trng c hiu xut
chuyn ho thp. tng tc phn hu HCBVTV v ph hp vi yu cu
x l, ngi ta ti u ho cc iu kin sinh trng v pht trin ca vi sinh
vt. Mt s tr ngi c th s dng vi sinh vt trong x l sinh hc l nhng
iu kin mi trng ti ni cn x l, nh s c mt ca cc kim loi nng
c, nng cc cht nhim hu c cao c th lm cho vi sinh vt t nhin
khng pht trin c v lm cht vi sinh vt a vo, gim ng k ngha
ng ngha thc t ca x l sinh hc. Ngoi ra, vi nhng k thut sinh hc
phn t hin ai c th to ra nhng chng vi khun c kh nng phn hu
ng thi nhiu ho cht c hi m khng yu cu iu kin nui cy phc
tp v khng gy hi cho ng thc vt cng nh con ngi. Phng php ny
s c ng dng rng ri trong tng lai v ngha thc t ca n khi x l
cc cht thi c hi ngy cng c mi ngi chp nhn.

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2.2.4. Cng ngh oxy ha tin tin (AOT)

L qu trnh to ra tc nhn xy ho OH, thng qua s dng tc nhn


ho hc H2O2 (vi cc cht xc tc thch hp nh mui ca Cu, Mn), Ozone,
2+
Fenton (H2O2/ Fe ), Bichromat, Permanganat. Phn ng xy ra nhiu giai
on vi cc sn phm trung gian. Cn nghin cu xc nh iu kin ti u
trong tng trng hp c th nc ta phn ng xy ra c hiu sut cao
nht. Tc nhn quang ho (Photochemical) l qu trnh xy ho quang ho m
cht hu c c hi b phn hu di tc dng ca tia UV (bc sng 280 -
410 nm) v cht xc tc nh TiO 2 (H TiO2/UV), vi s c mt ca xy trong
khng kh. Tuy y l phng php c chi ph thp song ch c th ng dng
khi hm lng cht c thp v thi gian x l ko di. Phi hp tc nhn
xy ho v quang ho (Ozone+ UV, Fenton + UV,...) c th tng hiu qu
phn hu cht c hu c. Tuy nhin, hiu qu phn hu cng ph thuc vo
nhiu yu t nh: dy ca lp cn x l, iu kin thi tit, s phn hu
quang ho ca chnh H2O2.

Phng php Ozone + UV ch c th p dng c cho pha lng v


pha kh. Tm li, cc phng php AOT c th thc hin vi ngun nhim
c hm lng cht c thp tuy nhin phi tm ra iu kin ti u cho qu
trnh phn hu trong cc trng hp c th.

2.2.5. Bin php xy ha kh ho hc

C hai loi phn ng oxy ha kh l oxy ha trong mi trng axt v


oxy ha trong mi trng kim.Mc ch ca qu trnh oxy kh l dng cc
cht c tnh xy ho ph v mt s lin kt nht nh, chuyn ho cht c
c tnh cao thnh cht c tnh c tnh thp hn hoc khng c. u im l s
dng thit b n gin, d ch to, vt t ho cht d kim, c sn trn th
trng trong nc. Nhc im l phi c quy trnh ph hp i vi tng loi
thuc BVTV v phi c s kim sot cht ch hiu qu ca qu trnh x l.

19
2.2.6. Cng ngh s dng tc nhn xy ho mnh
2+
y l cng ngh da trn tc nhn xy ho mnh ca Fe + H2O2.
2+
Tc nhn Fenton (Fe + H2O2) l mt trong cc h xy ha mnh nht c
nghin cu mt cch h thng nht v c ng dng x l rt c hiu qu
trn nhiu loi hp cht hu c khc nhau, mang li hiu qu to ln v kinh t
x hi v mi trng. Quy trnh cng ngh khng qu phc tp, phn ng xy
ra nhit v p sut thng, khng gy chy n, khng c hi vi mi
trng, an ton khi x l, gi thnh x l c th chp nhn.

Flaherty et al. (1992) p dng qu trnh Fenton x l nc thi


cha thuc nhu m hot tnh Reactive Blue 15. Nc thi c pH 12, kim
CaCO3 21.000 gl/l, COD 2.100 mg/l v tng nng ng 14 mg/l. Nng
Fe2+ gi 2.10 - 2 M, pH chnh xung 3,5. Trong th dng lin tc, phn ng
xy ra trong thit b phn ng dung tch 1 lt, c khuy tr n trong 2 gi.
Kt qu, gim c 70% COD. Sau khi lng 24 gi, nng ng trong
nc lng trong ch cn 1 mg/l, tng ng vi mc x l 93%.Vella et
al. (1993) tin hnh nghin cu phn hy Tricloetylen (TCE) trong nc
vi nng pha ch 10mg/l bng qu trnh Fenton. Phn ng thc hi n
gia 3,9 v 4,2 vi t l mol Fe2+: H2O2 bng 0,2 v s dng liu lng H 2O2
l 53 v 75 mg/l. Kt qu cho thy khi th nghi m vi H2O2 53 mg/l ho c cao
hn, trn 80% TCE b phn hy sau 2 pht. Hunter (1996) nghin cu x
l 1,2,3 - Triclopropan vi nng ban u l 150 mg/l v cho thy iu
ki n xy ra tt nht khi pH t 2,0 n 3,3. Khi tng nng Fe2+ c kh nng
lm tng tc phn hy 1,2,3 - Triclopropan.

2.2.7. Bin php hp ph

Bin php hp ph c th s dng i vi nhiu i tng cht nhim


khc nhau: khng kh, dung dch. Trong x l thuc BVTV, phng php hp
ph c u im: gi thnh x l thp, hiu qu x l cao i vi nhiu cht

20
nhim tng t c chng minh. Tuy nhin, bn cnh phng php
ny cng c mt s nhc im nh sau: kh b tr h thng x l quy m
ln, cha c nhiu nghin cu trong nc l, tn ti vn hp ph cnh
tranh khi trong nc c nhiu tc nhn nhim khc nhau. c tnh v kh
nng ng dng ca phng php c ch ra phn 2.3.

2.3. Phng php hp ph trong x l tn d thuc bo v thc vt


2.3.1. Nguyn l ca hin tng hp ph

Theo L Vn Ct, (2002);TrnVnNhn,HTh Nga (2005);Trn Vn


Nhn, Nguyn Thc Su, Nguyn Vn Tu, (1998) th Hp ph l s tch
ly cht trn b mt phn cch cc pha (kh - rn,lng - rn, kh - lng, lng -
lng). Cht c b mt, trn xy ra s hp ph c gil cht hp ph; cn
cht c tch lu trn b mt cht hp ph gi l cht b hp ph. Bn cht
ca hin tng hp ph l s tng tc gia cc phn t cht hp ph v cht
b hp ph. Tu theo bn cht ca lc tng tc m ngi ta phn bit hai loi
hp ph l hp ph vt l v ho hc:

Hp ph vt l: Cc tc gi L Vn Ct, (2002);TrnVnNhn,HTh
Nga (2005);Trn Vn Nhn, Nguyn Thc Su, Nguyn Vn Tu, (1998)
cng ch ra rng phn t cht b hp ph lin kt vi nhng tiu phn
(nguyn t,phn t, cc ion...) b mt phn chia pha bi lc lin kt Van
Der Walls yu. l tng hp ca nhiu loi lc ht khc nhau: tnh in, tn
x, cm ng v lc nh hng. Lc lin kt ny yu nn d b ph v.Trong
hp ph vt l, cc phn t ca cht b hp ph v cht hp ph khng to
thnh hp cht ho hc (khng hnh thnh cc lin kt ho hc) m cht b
hp ph ch b ngng t trn b mt phn chia pha v b gi li trn b mt
cht hp ph. hp ph vt l, nhit hp ph khng ln.

Hp ph ho hc: Theo L Vn Ct, (2002);TrnVnNhn,HTh Nga


(2005);Trn Vn Nhn, Nguyn Thc Su, Nguyn Vn Tu, (1998) th hp

21
ph ha hc xy ra khi cc phn t cht hp ph to hp cht ho hc vi cc
phn t cht b hp ph. Lc hp ph ho hc khi l lc lin kt ho hc
thng thng (lin kt ion, lin kt cng ho tr, lin kt phi tr...). Lc lin
kt ny mnh nn kh b ph v. Nhit hp ph ho hc ln, c th t ti gi
tr 800kJ/mol.

Hp ph trong mi trng nc: Trong nc, tng tc gia mt


cht hp ph v cht b hp ph phc tp hn rt nhiu v trong h c t nht
ba thnh phn gy tng tc: nc,cht hp ph v cht b hp ph. Do s c
mt ca dung mi nn trong h s xy ra qu trnh hp ph cnh tranh gia
cht b hp ph v dung mi trn b mt cht hp ph. Tnh chn lc ca cp
tng tc ph thuc vo tan ca cht b hp ph trong nc, tnh a nc
hoc k nc ca cht hp ph, mc k nc ca cc cht b hp ph trong
mi trng nc. So vi hp ph trong pha kh, s hp ph trong mi trng
nc thng c tc chm hn nhiu do khuch tn phn t cht tan chm.

Cng theo L Vn Ct, (2002);TrnVnNhn,HTh Nga (2005);Trn


Vn Nhn, Nguyn Thc Su, Nguyn Vn Tu, (1998) th s hp ph trong
mi trng nc chu nh hng nhiu bi pH ca mi trng. S thay i
pH khng ch dn n s thay i v bn cht cht b hp ph (cc cht c
tnh axit yu, baz yu hay trung tnh phn li khc nhau cc gi tr pH khc
nhau) m cn lm nh hng n cc nhm chc trn b mt cht hp
ph.Trong mi trng nc, cc cht hu c c tan khc nhau. Kh nng
hp ph trn VLHP i vi cc cht hu c c tan cao s yu hn vi cc
cht hu c c tan thp hn. Phn ln cc cht hu c tn ti trong nc
dng phn t trung ho, t b phn cc. Do qu trnh hp ph trn VLHP
i vi cht hu c ch yu theo c ch hp ph vt l.ng Trn Phng,
Trn Hiu Nhu (2005) cho rng kh nng hp ph cc cht hu c trn

22
VLHP ph thuc vo: pH ca dung dch, lng cht hp ph, nng cht b
hp ph.

ng hc hp ph: Trong mi trng nc, qu trnh hp ph xy ra


ch yu trn b mt ca cht hp ph, v vy qu trnh ng hc hp ph xy
ra theo mt lot cc giai on k tip nhau.Trong , giai on no c tc
chm nht s quyt nh hay khng ch ch yu ton b qu trnh hp ph.

Cc cht b hp ph chuyn ng n b mt cht hp ph - Giai on


khuch tn trong dung dch.
Phn t cht b hp ph chuyn ng n b mt ngoi ca cht hp
ph cha cc h mao qun - Giai on khuch tn mng.
Cht b hp ph khuch tn vo bn trong h mao qun ca cht hp
ph - Giai on khuch tn vo trong mao qun.
Cc phn t cht b hp ph c gn vo b mt cht hp ph - Giai
on hp ph thc s.

Qu trnh hp ph l mt qu trnh thun nghch. Cc phn t cht b


hp ph khi hp ph trn b mt cht hp ph vn c th di chuyn ngc
li pha mang. Theo thi gian, lng cht b hp ph tch t trn b mt cht
rn cng nhiu th tc di chuyn ngc li pha mang cng ln. n mt
thi im no , tc hp ph bng tc gii hp th qu trnh hp ph
t cn bng. Mt h hp ph khi t n trng thi cn bng, lng cht b
hp ph l mt hm ca nhit , p sut hoc nng ca cht b hp ph:
q = f (T, P hoc C)
nhit khng i (T=const), ng biu din s ph thuc ca q
voP hoc C (q= fT (P hoc C)) c gi l ng ng nhit hp ph.
ng ng nhit hp ph c th xy dng trn c s l thuyt, kinh nghim
hoc bn kinh nghim, hin nay c mt s phng trnh ph bin sau:
Trong cc phng trnh trn, l th tch cht b hp ph, m l th tch
hp ph cc i, p l p sut cht b hp ph pha kh, p o l p sut hi bo
ho ca cht b hp ph trng thi lng tinh khit cng nhit . Cc k

23
hiu a, b, k, n l cc hng s. nh gi kh nng hp ph ca mt h hp
ph, c bit l hp ph trong mi trng nc, ngi ta thng p dng
phng trnh ng nhit Freundlich (vi gi thit nhit hp ph vi phn khng
thay i khi che ph (dung lng hp ph) thay i v khong nng
cht b hp ph nh) hoc Langmuir (vi gi thit b mt cht hp ph ng
nht v nng lng), do cc phng trnh ny c ngha vt l cao v lin
quan trc tip n cc thng s cu trc xp ca cht hp ph.
Bng 2.2. Mt s ng ng nhit hp ph thng dng

ng ng nhit Bn cht s
Phng trnh
hp ph hp ph
V b. p Vt l v ha
=
Langmuir Vm 1+b . p
hc
v =k . p Vt l v ha
Henry
hc
1
Vt l v ha
Freundlich v =k . p n ,(n>1)
hc
Shygin - Frumkin - V 1
= lnCo . p
Vm a Ha hc
Temkin
Brunauer - Emmett - p 1 C1 p
= + .
v ( po p) Vm .C Vm . C po Vt l, nhiu lp
Teller (BET)
Ngun: ng Trn Phng, Trn Hiu Nhu, 2005

Phng trnh hp ph ng nhit Freundlich c th biu din di dng:


1
q=K f C n (1)

Trong : q: Dung lng hp ph (mg/g)

Kf: hng s hp ph Freundlich,

1/n: l tr s c trng cho tng tc hp ph ca h

Logarit hai v ca phng trnh (1) ta c phng trnh (2):

24
log q = logKf + 1/n logC (2)

H s Kf lin quan n dung lng nn hp ph ca cht hp ph i


vi cht b hp ph. 1/n l hm cng hp ph. T phng trnh ng
nhit ta thy c, i vi mt gi tr ca K f v C, gi tr 1/n cng nh th kh
nng hp ph cng ln. Khi 1/n rt nh th hp ph c xu hng c lp i
vi C. V i vi mt gi tr cho trc C v 1/n, gi tr K f cng ln th kh
nng hp ph cng ln.

2.3.2. c im v kh nng hp ph ca than hot tnh

Than hot tnh: Theo Bansal R.C. , Goyal M.(2005), c rt nhiu nh


ngha v than hot tnh, tuy nhin c th ni chung rng, than hot tnh l mt
dng ca cacbon c x l mang li mt cu trc rt xp, do c
din tch b mt rt ln.Than hot tnh dng than g hot ha c s
dng t nhiu th k trc. Ngi Ai cp s dng than g t khong 1500
trc cng nguyn lm cht hp ph cho mc ch cha bnh. Ngi Hindu
c n lm sch nc ung ca h bng cch lc qua than g. Vic sn
xut than hot tnh trong cng nghip bt u t khong nm 1900 v c s
dng lm vt liu tinh ch ng. Than hot tnh ny c sn xut bng cch
than ha hn hp cc nguyn liu c ngun gc t thc vt trong s c mt
ca hi nc hoc CO2.

Tt c cc nguyn liu cha cacbon u c th chuyn thnh than hot


tnh, sn phm thu c s c s khc nhau ph thuc vo bn cht ca
nguyn liu c s dng, bn cht ca tc nhn hot ha v iu kin hot
ha. Trong qu trnh hot ha hu ht cc nguyn t khc trong nguyn liu
to thnh sn phm kh v bay hi, cc nguyn t cacbon s nhm li vi
nhau thnh cc lp thm lin kt vi nhau mt cch ngu nhin. S sp xp
ca cc lp thm ny khng tun theo qui lut do li cc ch trng gia
cc lp to ra kh nng hp ph cao cho than hot tnh.

25
Than hot tnh c s dng rng ri cho nhiu mc ch nh loi b
mu, mi, v khng mong mun v cc tp cht hu c, v c trong nc thi
cng nghip v sinh hot, thu hi dung mi, lm sch khng kh, trong kim
sot nhim khng kh t kh thi cng nghip v kh thi ng c, trong lm
sch nhiu ha cht, dc phm, sn phm thc phm v nhiu ng dng
trong pha kh. Chng c s dng ngy cng nhiu trong lnh vc luyn kim
thu hi vng, bc, v cc kim loi khc, lm cht mang xc tc. Chng
cng c bit n trong nhiu ng dng trong y hc, c s dng loi
b cc c t v vi khun ca mt s bnh nht nh.

Cu trc b mt xp ca than hot tnh: Nghin cu caBansal


R.C. , Goyal M.(2005) cng ch ra rng than hot tnh vi s sp xp ngu
nhin ca cc vi tinh th v vi lin kt ngang bn gia chng, lm cho than
hot tnh c mt cu trc l xp kh pht trin. Chng c t trng tng i
thp (nh hn 2g/cm3) v mc graphit ha thp. Cu trc b mt ny c
to ra trong qu trnh than ha v pht trin hn trong qu trnh hot ha, khi
lm sch nha ng v cc cht cha cacbon khc trong khong trng gia
cc tinh th. Qu trnh hot ha lm tng th tch v lm rng ng knh l.
S hot ha cng loi b cacbon khng phi trong cu trc, lm l ra cc tinh
th di s hot ng ca cc tc nhn hot ha v cho php pht trin cu
trc vi l xp. Trong pha sau cng ca phn ng, s m rng ca cc l tn
ti v s to thnh cc l ln bng s t chy cc vch ngn gia cc l cnh
nhau c din ra. iu ny lm cho cc l trng c chc nng vn chuyn v
cc l ln tng ln, dn n lm gim th tch vi l.

Theo Dubinin v Zaveria (1947), than hot tnh vi l xp c to ra


khi mc t chy nh hn 50% v than hot tnh l macro khi mc t
chy l ln hn 75%. Khi mc t chy trong khong 50 75% sn phm
c hn hp cu trc l xp cha tt c cc loi l.Ni chung than hot tnh c

26
b mt ring pht trin v thng c c trng bng cu trc nhiu ng
mao dn phn tn, to nn t cc l vi kch thc v hnh dng khc nhau.
Than hot tnh c l xp t 1 nm n vi nghn nm. Dubinin xut mt cch
phn loi l xp c IUPAC chp nhn. S phn loi ny da trn chiu
rng ca chng, th hin khong cch gia cc thnh ca mt l xp hnh
rnh hoc bn knh ca l dng ng bao gm 3 nhm:

L nh (Micropores) c kch thc c phn t, bn knh hiu dng nh


hn 2nm. S hp ph trong cc l ny xy ra theo c ch lp y th tch l,
v khng xy ra s ngng t mao qun. Nng lng hp ph trong cc l ny
ln hn rt nhiu so vi l trung hay b mt khng xp v s nhn i ca lc
hp ph t cc vch i din nhau ca vi l. Ni chung chng c th tch l t
0.15 0.7cm3/g. Din tch b mt ring ca l nh chim 95% tng din tch
b mt ca than hot tnh. Cu trc vi l c th chia nh thnh 2 cu trc vi l
bao gm cc vi l c trng vibn knh hiu dng nh hn 0.6 0.7 nm v
siu vi l vi bn knh hiu dng t 0.7 n 1.6nm.

L trung (Mesopore) hay cn gi l l vn chuyn c bn knh hiu


dng t 2 n 50 nm, th tch ca chng thng t 0.1 n 0.2cm 3/g. Din
tch b mt ca l ny chim khng qu 5% tng din tch b mt ca than.
Tuy nhin, bng phng php c bit ngi ta c th to ra than hot tnh c
l trung ln hn, th tch ca l trung t c t 0.2 0.65cm 3/g v din tch
b mt ca chng t 200m2/g. Cc l ny c trng bng s ngng t mao
qun ca cht hp ph vi s to thnh mt khum ca cht lng b hp ph.

L ln (Macropore) khng c nhiu ngha trong qu trnh hp ph


ca than hot tnh bi v chng c din tch b mt rt nh v khng vt qu
0.5m2/g. Chng c bn knh hiu dng ln hn 50nm v thng trong khong
500 - 2000nm vi th tch l t 0.2 0.4cm 3/g. Chng hot ng nh mt

27
knh cho cht b hp ph vo trong l nh v l trung. Cc l ln khng c
lp y bng s ngng t mao qun.

Mi nhm ny th hin mt vai tr nht nh trong qu trnh hp ph.


L nh chim 1 din tch b mt v th tch ln do ng gp ln vo kh
nng hp ph ca than hot tnh, min l kch thc phn t ca cht b hp
ph khng qu ln i vo l nh. L nh c lp y p sut hi tng
i thp trc khi bt u ngng t mao qun. Mt khc, l trung c lp
y p sut hi tng i cao vi s xy ra ngng t mao qun. L ln c
th cho phn t cht b hp ph di chuyn nhanh ti l nh hn.

Cu trc ha hc ca b mt: Nghin cu ca Bansal R.C. , Goyal


M.(2005)cng ch ra rng cu trc tinh th ca than c tc ng ng k n
hot tnh ha hc. Tuy nhin, hot tnh ha hc ca cc tm mt tinh th c
s t hn nhiu so vi tm cnh hay cc v tr khuyt. Do , cacbon c
graphit ha cao vi b mt ng nht cha ch yu mt c s t hot ng
hn cacbon v nh hnh. Grisdale v Hennig thy rng tc oxy ha ca
nguyn t cacbon tm nm cnh ln hn 17 n 20 ln b mt c s.

Bn cnh cu trc tinh th v cu trc l xp, than hot tnh cng c


cu trc ha hc. Kh nng hp ph ca than hot tnh c quyt nh bi
cu trc vt l v l xp ca chng nhng cng b nh hng mnh bi cu
trc ha hc. Thnh phn quyt nh ca lc hp ph ln b mt than l thnh
phn khng tp trung ca lc Van der Walls. Trong trng hp than hot tnh,
s phc tp ca cc cu trc vi tinh th, do s c mt ca cc lp graphit chy
khng hon ton trong cu trc, gy ra bin i v s sp xp cc electron
trong khung cacbon v kt qu l to ra cc electron c thn v ha tr khng
bo ha iu ny nh hng n c im hp ph ca than hot tnh c bit
l i vi cc hp cht phn cc v c th phn cc. Than hot tnh hu ht
c lin kt vi mt lng c th xc nh oxy v hydro. Cc nguyn t

28
khc loi ny c to ra t nguyn liu ban u v tr thnh mt phn cu
trc ha hc l kt qu ca qu trnh than ha khng hon ho hoc tr thnh
lin kt ha hc vi b mt trong qu trnh hot ha hoc trong cc qu trnh
x l sau . Cng c trng hp than hp ph cc loi phn t xc nh
nh amin, nitrobenzen, phenol v cc loi cation khc.

Nghin cu nhiu x tia X cho thy rng cc nguyn t khc loi hoc
cc loi phn t c lin kt vi cnh hoc gc ca cc lp thm hoc vi
cc nguyn t cacbon cc v tr khuyt lm tng cc hp cht cacbon oxy,
cacbon hydro, cacbon nitr, cacbon lu hunh, cacbon halogen trn b
mt, chng c bit n nh l cc nhm b mt hoc cc phc b mt. Cc
nguyn t khc loi ny c th sp nhp trong lp cacbon to ra h thng cc
vng khc loi lm bin i c tnh b mt v c im ca than hot tnh.

c. Hin trng ng dng than hot tnh trong hp ph x l thuc BVTV

Quy trnh x l nc bng hp ph ch yu c s dng kim sot


v v mi cng nh loi b cc hp cht hu c tng hp, kim loi c hi, v
clo. Hp ph l mt qu trnh lin kt ha l o ngc ca cc cht trn cht
hp ph. C ch kim sot hp ph ph thuc vo cc qu trnh vt l nh thu
ht tnh in (tng tc lng cc - lng cc, tng tc phn tn (lc van
der Waalsv lin kt hydro). M hnh cn bng phi tuyn tnh nh cc m
hnh Langmuir v Freundlich c s dng d on kh nng hp th
cc cht nhim hu c. Hp cht vi h s Freundlich cao c kh nng hp
ph bng than hot tnh. Mt cch tip cn khc d on kh nng hp ph
l hc thuyt Polanyi.

Than hot tnh dng ht (GAC) v than hot tnh dng bt (PAC) l cc
cht hp ph ph bin. Theo James M. Montgomery Consulting Engineers
(1985), than hot tnh bao gm cc m rng ca lp than ch, dn n t l
khi lng din tch b mt rt cao cho sorption. S khc bit chnh gia

29
GAC v PAC l kch thc ht, PAC c cc ht nh hn so vi GAC. Cc
cht hp ph t ph bin khc c s dng nhnhm silica gel, nhm silicat
tng hp, nha cy, cc cht nha cao phn t, v cc loi nha carbonized.
GAC c s dng nh mt vt liu hp ph lc v v kim sot mi hi, v
dng trong b lc loi b hu c tng hp. Ngc li, PAC c thm vo
trong cc h thng x l thng thng trc hoc trong qu trnh ng t/keo
t v qu trnh lng.

Dung lng hp ph ca than hot tnh loi b thuc tr su b nh


hng bi nng , nhit , pH, cnh tranh t cc cht gy nhim khc
hoc cc vt cht hu c t nhin, hu c np trc, thi gian, iu kin x
l, v tnh cht vt l/ha hc ca cc cht gy nhim. Hiu qu ct GAC
ph thuc vo tc dng nc v thi gian lu trong khi hiu qu PAC ph
thuc vo khi lng carbon. Ni chung, than hot tnh c bm dnh i
vi cc cht gy nhim k nc ( ha tan thp), mc d cc thng s khc
nh mt v trng lng phn t c th l quan trng.

Bng 2.3. Loi b thuc tr su bng tnh hp ph ca than hot tnh


dng ht nh

Co
Thuc tr su GAC Hiu qu x l (%)
(g/L)
4.83
Atrazine CalgonFiltrasorb300 47
(SW)
1.62
Cyanazine CalgonFiltrasorb300 67
(SW)
0.89
Metribuzin CalgonFiltrasorb300 57
(SW)
0.39
Simazine CalgonFiltrasorb300 62
(SW)
3.70
Alachlor CalgonFiltrasorb300 72
(SW)

30
5.60
Metolachlor CalgonFiltrasorb300 56
(SW)
0.20
Pendimethalin CalgonFiltrasorb300 >99
(SW)
(Ngun: Miltner et al, 1989. & Milner et al, 1987)

Theo Speth v Miltner (1990); Speth v Adams (1993) th hng ng


nhit c bo co c th d on gi tr d on liu than hot tnh
bm mt loi thuc tr su c bit.Nhn chung cc hp cht vi mt h s
Freundlich trn than hot tnh ln hn 200 ug/g (L/ug) 1/n c th hiu chnh
loi b bi cht hp ph carbon.

Hiu sut ca GAC trong vic loi b thuc tr su t nc th


c chng minh bi cc nghin cu ca Miltner et al. (1989), ng s
dng thuc bo v thc vt thuc triazine, acetanilide, v cc lp
dinitroaniline. So vi nng ban u ca thuc tr su, vic loi b hai
thuc tr su acetanilide (72 - 98%) cao hn so vi thuc tr su triazine (47 -
62%). Hiu qu x l cao nht (> 99%) Filtrasorb 400 i vi Pendimethalin.

31
Phn 3. NI DUNG V PHNG PHP NGHIN CU
3.1. i tng v phm vi nghin cu
- Vt liu hp ph: Than hot tnh dng ht hnh trht mu en, kh,
ri, c gc cnh 3 - 3,36 mm, chiu di ca vin than2 - 4 mm.
c tnh ca than:

T trng: 520 - 550 kg/m3.


Ch s hp ph iod: 650 - 850 mg/g
hp ph CCl4: 40 - 60%
hp ph Benzene: 23 - 33%
hp phMethylene: 130 - 170
ml/g
Ch s cng: 95%
tro: 2 - 5%
m: 6%
pH: 78 Hnh 3.1: Than hot tnh GAC
- Cht b hp ph: hot cht Cypermethrin pha t dung dch chun
trong nc l.
- Phm vi khng gian: Nghin cu quy m phng th nghim ti
Trung tm phn tch v chuyn giao cng ngh mi trng Vin Mi trng
Nng Nghip.
- Phm vi thi gian: t thng 2 n thng 4 nm 2013.
3.2. Ni dung nghin cu
- Xc nh nh hng ca pH, thi gian, hm lng than v nng
Cypermethrin ban u n kh nng hp ph ca than hot tnh(GAC) i vi
Cypermethrin
- nh gi hiu qu hp ph ca than hot tnh (GAC) i vi
Cypermethrin trong iu kin phng th nghim

32
3.3. Phng php nghin cu
3.3.1. Phng php b tr th nghim.
Trc khi tin hnh kim tra kh nng hp ph ti a ca than i vi
Cypermethrin chng ti i xc nh cc yu t nh hng ti hiu qu hp
ph ca than trc. Cc th nghim ny c tin hnh trc nhm tm ra
iu kin l tng nht cho than trong kim tra kh nng hp ph ti a ca
khong.C nhiu yu t nh hng ti kh nng hp ph Cypermethrin ca
khong nh: thi gian tip xc, pH dung dch, hm lng than, nng dung
dch, nhit , din tch b mt...Tuy nhin trong bo co ny ti ch cp
ti 4 yu t nh hng ti kh nng hp ph Cypermethrin ca than l: pH
mi trng, thi gian tip xc, hm lng khong, nng dung dch.
Th nghim a. nh hng ca pH
Ngng th nghim ca pH ly cc gi tr 7; 8; 9 ng vi gi tr pH t
nhin ca mt s mu nc ao nui trng thu sn ven bin ng bng sng
Cu Long (pH ca nc l).
Bc 1: Tin hnh ly nhim ncbng dung dch Cypermethrin
nng 10 ppm. Hiu chnh pH cc gi tr 7; 8; 9 bng dung dch axit
CH3COOH 0,01N v dung dch kim NaOH 0,01N.
Bc 2: Cn 1g than hot tnh cho vo ng ly tm c th tch 50 ml.
Ly chnh xc 20 ml nc gy nhim nhn to Cypermethrin vo ng li
tm. Nhit c gi n nh nhit phng 25oC.
Bc 3: a cc ng ny ln my lc, lc ti tc 150 vng/pht
trong 90pht, sau em ly tm vi tc 5000 vng/pht trong 5 pht, gn
phn nc trong em xc nh nng Cypermethrin sau hp ph.
Mi gi tr pH c lp li 3 ln, o c c tin hnh lp li 3 ln
mi nghim thc th nghim. Nh vy s ln lp n = 9.

33
Th nghim b. nh hng ca thi gian tip xc
Bc 1: Tin hnh ly nhim nc l bng dung dch Cypermethrin
nng 10 ppm. Gi tr pH ca dung dch th nghim ng vi kt qu ca th
nghim 1.a
Bc 2: Cn 1 g than hot tnh GAC cho vo ng ly tm c th tch 50
ml, s dng c mu trng. Ly chnh xc 20 ml nc gy nhim nhn to
Cypermethrin vo ng li tm cha than hot tnh nhit phng 25oC.
Bc 3: a cc ng ny ln my lc, lc ti tc 150 vng/pht vi
cc khong thi gian khc nhau 15, 30, 60 90 v 120 pht, sau em ly tm
vi tc 5000 vng/pht trong 5 pht, gn phn nc trong em xc nh
nng Cypermethrin cn li ca dung dch sau hp ph.
Mi nghim thc theo thi gian c lp li 3 ln, o c c tin
hnh lp li 3 ln mi nghim thc th nghim. Nh vy s ln lp n = 9.
Th nghim c. nh hng ca hm lng than hot tnh
K tha kt qu th nghim 1.a v 1.b v pH v thi gian.
Bc 1: Tin hnh ly nhim nc l bng dung dch Cypermethrin
nng 10 ppm. Gi tr pH ng vi kt qu ca th nghim 1.a
Bc 2: Cn 0,1 g; 0,2g; 0,5g v 1g than hot tnh GAC cho vo cc
ng ly tm c th tch 50 ml, s dng c mu trng. Ly chnh xc 20 ml nc
gy nhim nhn to Cypermethrin vo ng li tm cha than hot tnh
nhit phng 25oC.
Bc 3: a cc ng ny ln my lc, lc ti tc 150 vng/pht
trong khong thi gian ng vi kt qu ca th nghim 1.b, sau em ly tm
vi tc 5000 vng/pht trong 5 pht, gn phn nc trong em xc nh
nng Cypermethrin cn li ca dung dch sau hp ph.
Mi nghim thc v hm lng than lp li 3 ln, o c c tin
hnh lp li 3 ln mi nghim thc th nghim. Nh vy s ln lp n = 9.
Th nghim d. nh hng ca nng Cypermethrin
K tha kt qu th nghim 1.a; 1.b v 1.c v pH; thi gian v hm
lng than hot tnh s dng.
Bc 1: Tin hnh ly nhim nc l bng dung dch Cypermethrin

34
cc nng khc nhau: 0,5 ppm; 1 ppm; 2 ppm; 5 ppm; 10 ppm.
Bc 2: Cn khi lng than hot tnh ng vi kt qu th nghim 1.c
cho vo ng ly tm c th tch 50 ml, s dng c mu trng. Ly chnh xc 20
ml nc gy nhim nhn to Cypermethrin vo ng li tm cha than hot
tnh nhit phng 250C.
Bc 3: a cc ng ny ln my lc, lc ti tc 150 vng/pht
trong thi gian ng vi kt qu th nghim 1.b, sau em ly tm vi tc
5000 vng/pht trong 5 pht, gn phn nc trong em xc nh nng
Cypermethrin cn lica dung dch sau hp ph.
Mi nghim thc v hm lng than lp li 3 ln, o c c tin
hnh lp li 3 ln mi nghim thc th nghim. Nh vy s ln lp n = 9.
3.3.2. Phng php phn tch trong phng th nghim
+ Nhit c o c bng nhit k thu ngn

+ Xc nh nng ca Cypermethrin trong nc ca mu phn ng


bng phng php sc k kh phi kh GC/MS: Dng ng ong 100ml ong
chnh xc 200ml mu cho vo bnh chit, thm 25ml dichlormethan,10ml
dung dch NaCl bo ha, lc mnh trong khong 5 pht, cho tch lp. Tch
lp di xung qua phu lc cha 20g Na 2SO4 vo bnh cu 250ml (A). Lp
trn thm 25ml dichlormethan, lc mnh trong 5 pht, tch lp.Tch lp
di qua phu lc cha 20g Na2SO4 vo bnh cu 250ml (A). C kh dung
dch trong bnh cu A vi my ct quay chn khng. Ha tan phn cn vi
2ml dung mi, a hn hp dung mi thu c qua ct SPE lm sch, ra
gii bng dung mi n - hexan : dichlormethan. Phn dung mi thu xung bnh
cu 100ml, lm kh bnh cu bng my ct quay chn khng. Ha tan phn
cn vi 2ml dung mi dng lm mu th phn tch trn thit b sc k.

+ pH c o bng my pH Mettler Toledo.


3.3.3. Phng php nh gi kh nng hp ph ca than hot tnh i
vi Cypermethrin.
+ nh gi dung lng hp ph

35
Dung lng hp ph ca than c xc nh theo cng thc:
C 0C cb
q= .V (mg/g) (3.1)
m

Trong :

C0 - l nng ban u cht b hp ph (mg/l)

Ccb - l nng ca cht b hp ph cn li trong pha lng (mg/l)

V- l th tch dung dch s dng ban u (l)

m- l khi lng than hot tnh (g).


+ nh gi hiu qu hp ph
Hiu qu hp ph c tnh theo cng thc sau:
(C 0C cb )
H= .100 (3.2)
C0

Trong :

C0 - l nng ban u cht b hp ph (mg/l)

Ccb - l nng ca cht b hp ph cn li trong pha lng (mg/l)

+ nh gi ti trng hp ph:

nh gi kh nng hp ph ca h hp ph nu trn s dng phng


trnh ng nhit hp ph Freundlich (chi tit c trnh by trong tng quan).

3.3.4. Phng php x l s liu


S liu th nghim c x l bng phng php thng k c bn v
phn mm Excel.

36
Phn 4. KT QU NGHIN CU

4.1. Cc yu t nh hng n kh nng hp ph Cypermethrin ca than


hot tnh

C ch hp ph ca than hot tnh i vi cht hu c ni chung v


cht hu c kh phn hu sinh hc ni ring a phn thng qua c hai c ch
hp ph vt l v hp ph ho hc. Trong , do khi lng phn t cht b
hp ph ln nn a s cc trng hp hp ph vt l chim u th. V vy,
cc yu t quan trng quyt nh hiu qu ca qu trnh hp ph thng qua
quyt nh kh nng hp ph ca than hot tnh i vi cypermethrin l: nhit
, pH ca mi trng, hm lng than s dng, nng cypermethrin v
thi gian din ra phn ng. Trong , do nhit c khng ch 25 oC
(qu trnh ng nhit) nn chng ta xem xt nh hng ca cc yu t cn li
ln kh nng hp ph ca than hot tnh i vi cypermethrin.

4.1.1. nh hng ca pH

Trong mi trng, gi tr pH th hin tnh axt hay kim v ng thi


th hin cc mui tan mang tnh axit hoc baz, gim trong iu kin axt v
tng trong iu kin kim. Trong t, s chua ho l do tn ti cc thnh phn
cahydroxit ca Fe v Al cng nh s hnh thnh cc axt hu c t qa trnh
khong ho cc vt cht hu c, s ra tri ca chng vo nc lm thay i
pH ca nc. pH trong nc trung tnh lun nm trong khong 6,5 v 7,5, cc
gi tr thp hn l do s tn ti ca CO 2 t do trong nc do khuch tn, h
hp, phn hy cht hu c...

pH ca dung dch l mt yu t quan trng trong bin php hp ph.


Cc bin th ca pH khng ch thay i b mt carbon m n cng c th
nh hng n trng thi ca ion trong dung dch. pH khng ch nh hng
trc tip n c ch hp ph ho hc ca than hot tnh i vi cc ion kim

37
loi thng qua nh hng ca n ti cn bng ho tan kt ta m cn nh
hng n qu trnh hp ph vt l thng qua cn bng in gia cc nhm
chc ca cht b hp ph dng hu c.

nh gi s nh hng ca pH ti kh nng hp ph Cypermethrin


ca than hot tnh chng ti tin hnh th nghim nh sau: Cn 1g VLHP cho
ln lt vo cc ng ly tm c dung tch 50ml nh s th t v thm vo
20 ml dung dch c nng Cypermethrin 10 ppm cc gi tr pH khc nhau
7; 8; 9. Tin hnh lc vi tc 150 vng/pht nhit phng (25 0C) trong
khong thi gian 90 pht. Ly tm ly dung dch em i xc nh nng
Cypermethrin con li bng phng php GC/MS.

Kt qu nng ca Cypermethrin sau phn ng (C cb) c trnh by


trong bng 4.1

Bng 4.1: Nng ca Cypermethrin sau th nghim xc nh nh hng


ca pH ti kh nng hp ph

Nng Cypermethrin sau th nghim


pH dung Ln lp
(ppm)
dch li
Mu 1 Mu 2 Mu 3
I 0,261 0,213 0,288
pH = 7 II 0,202 0,255 0,245
III 0,285 0,213 0,298
I 0,350 0,350 0,351
pH = 8 II 0,349 0,350 0,350
III 0,348 0,351 0,351
I 0,500 0,505 0,500
pH = 9 II 0,485 0,495 0,502
III 0,510 0,513 0,495
Ngun: Kt qu th nghim, 2013

38
Kt qu phn tch ca cc mu lp khng c s khc bit ng k cho
thy phng php s dng trong th nghim c tin cy tng i cao ng
thi cho thy phng php hp ph t ra kh n nh i vi qu trnh hp
ph Cypermethrin iu kin nghin cu. Theo kt qu ca nghin cu ny,
kt qu khc bit ng k v nng Cypermethrin u ra ch yu do pH ca
mu gy ra. Trong , pH 7, nng Cypermethrin sau x l dao ng
trong khong 0,202 n 0,298 ppm. Nng Cypermethrin sau x l ca mu
c pH 8 dao ng trong khong 0,348 n 0,351 ppm. Ti dung dch ho cht
c pH 9,nng Cypermethrin sau x l dao ng trong khong 0,485 n
0,505 ppm.

Chi tit v nh hng ca s thay i pH mi trng nc ti kh nng


hp ph ca than i vi Cypermethrin c trnh by trong bng 4.2.

Bng 4.2: nh hng ca pH n s hp ph Cypermethrin

Khi
Nng Nng Dung lng Hiu qu
pH th lng
ban u sau x l hp ph x l
nghim than
m (g) C0 (ppm) Ccb (ppm) q (mg/g) H (%)
7 1 10 0,251 0,195 97,49
8 1 10 0,350 0,193 96,50
9 1 10 0,501 0,190 94,99
Trong : Nng sau x l c xc nh bng gi tr trung bnh (n = 9)

Ngun: Kt qu th nghim, 2013

Dung lng hp ph ca than i vi Cypermethrin gim dn t 0,195


- 0,190 mg/g khi tng pH t 7 - 9. Tng ng vi hiu qu x l gim dn t
97,49% xung cn 94,99%. iu ny c th gii thch nh sau: dung dch
c pH thp (tnh axit) b mt carbon ch yu mang in tch dng, trong khi
dung dch c pH cao th trn b mt carbon s xut hin cc in tch m do

39
s bin i ca cc nhm chc (Cacbonyl, Cyanua...). Do vy m b mt than
mang in tch dng hn in tch m th kh nng hp ph s cao hn v
ngc li. Nh vy, nh hng ca pH ti qu trnh hp ph Cypermethrin
ca than ch yu lin quan ti cc ng phn nhm chc ca Cypermethrin.

Tuy nhin, khi xem xt xu hng ca cc mu lp khc nhau trong


cng mt gi tr pH ca mi trng, s thay i ny l khng ng k v hiu
qu x l nu trn l kh cao i vi cc nghin cu th nghim x l ho
cht bo v thc vt bng than hot tnh (tham kho v so snh vi kt qu
ca bng 2.3). Mc d c th nhn nh rng gi tr pH mc trung tnh s
cho hiu qu x l tt hn so vi gi tr pH kim nhng trong gii hn gi tr
pH ca mi trng nc nui tm trong t nhin, th hiu qu ca x l hu
nh khng b nh hng bi iu kin pH ca mi trng nc.

0.2 100

0.19 98

0.19 96
Dung lng hp ph (mg/g) Hiu qu x l (%)
0.19 94
q (mg/g) H (%)

0.19 92

0.19 90
pH 7
pH th nghim

Hnh 4.1. nh hng ca pH n s hp ph Cypermthrin

Do , cc mu th nghim cho cc th nghim tip theo s c la


chn nh gi pH c gi tr bng 7 do ti y hiu qu x l t c l cao

40
nht. M rng ra trong iu kin x l ca Cypermethrin bng than hot tnh,
khng nht thit phi h pH ca mi trng trc khi i qua h thng x l
hp ph. Bn cnh , cn lu l khng x l hp ph sau khi x l ao nui
bng vi (vi nc hoc vi bt) do iu ny dn ti vic gia tng gi tr pH
ca ao v gim hiu qu x l ca than hot tnh dng ht.

4.1.2. nh hng ca thi gian tip xc

Theo thuyt hp ph ng nhit, cc phn t cht b hp ph trn b


mt cht hp ph khi hp ph trn b mt cht hp ph vn c th di
chuyn ngc li. Lin quan n yu t thi gian tip xc gia cht hp ph
v cht b hp ph, thi gian ngn th cha cc trung tm hot ng trn
b mt cht hp ph c lp y bi Cypermethrin. Ngc li khi thi gian
di th lng cht b hp ph tch t trn b mt cht hp ph cng nhiu, tc
di chuyn ngc li vo nc cng ln, nn hiu qu hp ph gn nh
khng tng v dn t v trng thi cn bng.

nh gi s nh hng ca thi gian tip xc ti kh nng hp ph


Cypermethrin ca than hot tnh chng ti tin hnh th nghim nh sau: Cn
1g VLHP cho ln lt vo cc ng ly tm c dung tch 50ml nh s th t
v thm vo 20 ml dung dch c nng Cypermethrin 10 ppm. Tin hnh lc
vi tc 150 vng/pht nhit phng (250C) trong cc khong thi gian
khc nhau 15 pht; 30 pht; 60 pht; 90 pht; 120 pht. Sau cc khong thi
gian khc nhau, cc mu tng ng c ly ra xc nh gi tr nng
ca Cypermethrin sau khi hp ph.

Th nghim c tin hnh pH = 7

Kt qu nng sau x l ca Cypermethrin (C cb) c trnh by trong


bng 4.3:

41
Trong , mi thi gian s lng mu c lp li 03 ln v mi mu
c o c ngu nhin 03 ln. Kt qu th nghim cho thy: Mu tin hnh
lc trong thi gian 15 pht, nng Cypermethrin sau x l dao ng trong
khong 2,104 n 2,2 ppm. Nng Cypermethrin sau x l ca mu tin
hnh lc trong 30 pht dao ng trong khong 1,312 n 1,390 ppm.Mu c
thi gian lc 60 pht, nng Cypermethrin sau x l dao ng trong khong
0,685n 0,950 ppm. Trong khi , cc mu tin hnh phn ng trong 90 v
120 pht th nng cn li Cypermethrin trong dung dch tng ng nhau
v dao ng trong khong 0,348 n 0,351 ppm.

Bng 4.3: Nng ca Cypermethrin sau th nghim xc nh nh hng


ca thi gian tip xc ti kh nng hp ph

Nng Cypermethrin sau th nghim


Thi gian Ln lp
(ppm)
(pht) li
Mu 1 Mu 2 Mu 3
I 2,193 2,192 2,104
15 II 2,191 2,200 2,120
III 2,195 2,196 2,200
I 1,312 1,332 1,332
30 II 1,361 1,390 1,355
III 1,332 1,350 1,350
I 0,910 0,950 0,820
60 II 0,917 0,880 0,768
III 0,900 0,724 0,685
I 0,350 0,350 0,351
90 II 0,349 0,350 0,350
III 0,348 0,351 0,351
I 0,350 0,350 0,351
120 II 0,349 0,350 0,350
III 0,348 0,351 0,351
Ngun: Kt qu th nghim, 2013

42
Tng t nh i vi kt qu th nghim nh hng ca pH, kt qu
phn tch ca cc mu lp li khng c s khc bit ng k. iu ny mt
ln na cho thy phng php s dng trong th nghim c tin cy tng
i cao ng thi cho thy phng php hp ph kh n nh i vi qu
trnh hp ph Cypermethrin iu kin nghin cu (pH = 7, nhit 25 oC v
kch thc ca mt bnh th nghim l 20 ml).

Bng 4.4: nh hng ca thi gian n s hp ph Cypermethrin

Dung
Khi lng Nng Nng Hiu qu
Thi lng hp
than ban u sau x l x l
gian(pht) ph
m (g) C0 (ppm) Ccb (ppm) q (mg/g) H (%)
15 1 10 2,177 0,156 78,23
30 1 10 1,346 0,173 86,54
60 1 10 0,839 0,183 91,61
90 1 10 0,350 0,193 96,50
120 1 10 0,350 0,193 96,50
Trong : Nng sau x l c xc nh bng gi tr trung bnh (n = 9)

Ngun: Kt qu th nghim, 2013

Kt qu nghin cu nh hng ca thi gian tip xc ti hiu qu hp


ph ca than hot tnh c trnh by bng 4.4 v hnh 4.2. Kt qu cho
thy qu trnh hp ph Cypermethrin ca than GAC din ra tng i chm
nhng hiu qu x l kh cao, sau 120 pht lc vi dung dch dung lng hp
ph t 0,193 mg/g. Qu trnh hp ph din ra nhanh trong khong thi gian
t 15 - 30 pht u (dung lng hp ph t 0,156 mg/g; 0,173 mg/g tng
ng vi 15 pht, 30 pht tip xc) v sau c xu th gim dn t (dung
lng hp ph t 0,183 mg/g; 0,193 mg/g; 0,193 mg/g tng ng vi 60
pht; 90 pht; 120 pht tip xc). Trong khong thi gian t 60 90 pht tip

43
xc th dung lng hp ph tng chm t 0,183 mg/g 0,193 mg/g. Trong ,
ng ch l khong thi gian t 90 120 pht tip xc th dung lng hp
ph khng i v bng 0,193 mg/g.

Nh vy trong iu kin tin hnh th nghim trn ta thy rng sau 90


pht tip xc th trng qu trnh hp ph t cn bng.

Tng t nh xu th v dung lng hp ph ca than hot tnh i vi


hot cht th nghim, hiu qu x l tng dn t 78,23% 15 pht phn ng
ln mc 91,61% 60 pht v n nh mc 96,5% sau khi qua pht th 90.
iu ny c gii thch bng kh nng din tch b mt tip xc gia than v
Cypermethrin c bo ho thi gian tip xc 90 pht. Do , nhiu kh
nng gi tr 0,193 mg/g gn vi dung lng hp ph ti a ca vt liu i vi
hot cht th nghim (hnh 4.2).

0.2 0.20
0.17
0.19 0.16

0.18 0.12
0.10
Dung lng hp ph (mg/g)0.17 0.08Vn tc hp ph (ug/s)
q (mg/g) 0.05 v (g/s)
0.04
0.16 0.030.04

0.15 0.00

Thi gian (pht)

Hnh 4.2: nh hng ca thi gian n s hp ph Cypermethrin

Nu xem xt vn tc phn ng trung bnh trn tng khong thi gian


tip xc, vn tc phn ng nhanh nht t c nghim thc th nghim 15

44
v 30 pht tip xc ng vi vn tc phn ng tng ng 0,17 v 0,10 g/s.
Trong khi , t pht th 30 n pht th 60, vn tc chm li ch t 0,05
0,03 g/s v n nh gi tr ny trong khong thi gian t 60 120 pht.
iu ny cho thy, tc phn ng tng nhanh trong khong thi gian 30
pht, sau 30 pht, vn tc phn ng chm li mc d qu trnh hp ph vn
tip tc xy ra v t hiu qu cao hn sau 90 pht. iu ny cng c
khng nh bi Ken - Lin Chang & cs nm 2011.

V mt l thuyt, mun gia tng hiu qu x l th phi tng thi gian


tip xc gia vt liu hp ph v cht b hp ph. Tuy nhin, vic gia tng
thi gian ng ngha vi: lu lng x l nh, kch thc ca h thng x l
ln v ng thi chi ph cho qu trnh x l cng tng ln. Vn ny rt
quan trng trong mt h thng x l thc tin v gia tng thi gian phn ng
s ko theo nhng yu cu v c s vt cht, din tch, h tng, chi ph x l
v cng phc tp.

Do vy, tnh ton chi ph (tiu tn v thi gian) v li ch (gia tng hiu
qu) thu c t vic x l cypermethrin bng than hot tnh, nhn thy thi
gian ti u cho mt h thng x l c kh nng p dng trong thc tin l 15 -
30 pht (Ti , tc phn ng l nhanh nht trong khi hiu qu x l vn
t trn 75%). thi gian tip xc 30 pht, gi tr dung lng hp ph t
c 0,173 mg/g v hiu qu hp ph t 86,54%.

Tuy nhin trong khun kh th nghim ny, chng ti chn khong thi
gian 90 pht xc nh nh hng ca cc yu t liu lng than v nng
Cypermethrin. Sau khong thi gian ny hiu qu x l l cao nht v hp
ph c th t trng thi cn bng. Do , thi gian tip xc 90 pht c
chn nh gi c ch ca qu trnh hp ph.

45
4.1.3. nh hng ca hm lng than

Trong nghin cu ny cc hm lng than c s dng vi mc


ch xc nh khi lng than ti u trong qu trnh hp ph Cypermethrin.
V mt l thuyt, khi tng lng than hot tnh trong x l, hiu qu x l
tng. Tuy nhin, vic tng lng than ng ngha vi vic tng chi ph x l.
Do , xc nh ra mt hm lng than ti u tho mn c yu cu v mt
hiu qu v yu cu v mt kinh t l rt quan trng trong qu trnh ng dng
h thng x l Cypermethrin vo thc tin.

K tha cc th nghim nh gi hiu kh nng x l ca than hot


tnh i vi cc hot cht BVTV ca cc tc gi trc y, nh gi s nh
hng ca khi lng than ti kh nng hp ph Cypermethrin ca than hot
tnh chng ti tin hnh cn ln lt 0,1g; 0,2 g; 0,5 g; 1 g than cho vo 20 ml
dung dch c nng Cypermethrin 10 ppm. Tin hnh lc trong khong thi
gian 90 pht. Nh vy, hm lng than b sung vo mu nc cn x l cha
Cypermethrin tng ng vi cc gi tr 5; 10; 25; 50 g/l.

Th nghim c tin hnh pH = 7


Thi gian phn ng din ra: 90 pht

Mu c hm lng than 5 g/l, nng Cypermethrin sau x l dao


ng trong khong 1,44 n 1,655 ppm. Nng Cypermethrin cn li sau x
l mu c hm lng than 10 g/ldao ng t 1,267 n 1,38 ppm. Cn
mu ch 25g/l than nng Cypermethrin cn li sau khi x l dao ng
trong khong 0,662 n 0,764 ppm. Cui cng, mu c hm lng than ln
nht 50g/l th nng Cypermethrin cn li sau khi x l dao ng trong
khong 0,361 n 0,368 ppm.

46
Bng 4.5:. Nng ca Cypermethrin sau th nghim xc nh nh
hng ca hm lng than ti kh nng hp ph

Nng Cypermethrin sau th nghim


Hm lng Ln lp
(ppm)
than (g/l) li
Mu 1 Mu 2 Mu 3
I 1,543 1,54 1,554
5 II 1,542 1,537 1,553
III 1,440 1,535 1,655
I 1,270 1,375 1,350
10 II 1,268 1,377 1,347
III 1,267 1,380 1,345
I 0,662 0,666 0,662
25 II 0,665 0,664 0,663
III 0,663 0,664 0,764
I 0,367 0,366 0,362
50 II 0,365 0,367 0,361
III 0,368 0,365 0,363
Ngun: Kt qu th nghim, 2013

Kt qu chi tit v mc nh hng gia hm lng than s dng


trong hp ph vi hiu qu x l Cypermethrin ca th nghim c m t chi
tit trong bng 4.6.

Theo kt qu th nghim ny, ta nhn thy nng cn li trong dung


dch sau khi hp ph tng i thp. Vi cc mu c khi lng than khc
nhau ln lt l 0,1g; 0,2g; 0,5g; 1g u t kt qu cao v cao nht mu c
khi lng 1g. Vi mu cha 5 g/l than hot tnh, nng cn li trong dung
dch thu c l 0,36 ppm. Qua ta cng thy c l khi tng dn khi
lng than th hiu qu x l cng cao. iu ny ph hp vi cc ti liu
trch dn. Vic tng liu lng than s lm tng s lng cc v tr hp ph.

47
Do khi tng liu lng than th hiu qu hp ph tng (nng
Cypermethrin cn li trong dung dch gim) th dung lng hp ph s gim.

Bng 4.6: nh hng ca hm lng than n s hp ph Cypermethrin

Hm lng Nng Nng sau Dung lng Hiu qu


than ban u x l hp ph x l
m (g/l) C0 (ppm) Ccb (ppm) q (mg/g) H (%)
5 10 1,543 1,691 84,57
10 10 1,331 0,867 86,69
25 10 0,675 0,373 93,25
50 10 0,365 0,193 96,35
Trong : Nng sau x l c xc nh bng gi tr trung bnh (n = 9)

Ngun: Kt qu th nghim, 2013

Hiu qu x l t c thp nht l 84,75% v cao nht l 96,35%;


hiu qu x l tng dn khi tng hm lng than cho thy hiu qu kh cao.
Tuy nhin mc chnh lch gia cc nghim thc th nghim khng ln cho
thy hiu qu x l chu nh hng khng ng k bi hm lng than b
sung c tin hnh trong th nghim ny. iu ny c th c gii thch
l do phn ln cc nghim thc th nghim c tin hnh u c b
sung mt lng than kh cao so vi nhu cu x l nng c chn.

Xem xt xu hng thay i kh nng hp ph v hiu qu x l ca th


nghim, nhn thy hiu qu x l tng nhanh v gn nh tng tuyn tnh khi
hm lng than thay i t 5 n 25 g/l trong khi n nh khong 25
50 g/l. Tng t nh vy, dung lng hp ph ca than hot tnh gim dn khi
b sung thm than hot tnh vo mi trng x l nhng n nh mc 0,2
0,4 mg/g khi hm lng than trong khong 25 50 g/l.

48
2.0 100

1.6 96

1.2 92

Dung lng hp ph (mg/g) Hiu qu x l (%)


0.8 88
q (mg/g) H (%)
0.4 84

0.0 80

Hm lng than (g/l)

Hnh 4.3. nh hng ca hm lng than n s hp ph Cypermethrin

Nh vy, tng hm lng than l lm tng hiu qu nhng ng thi


lm gim kh nng hp ph ti a ca vt liu. Do , im ct nhau gia hai
ng biu din mi quan h gia hm lng than vi dung lng hp ph v
hiu qu x l chnh l gi tr ph hp cho qu trnh x l cypermethrin trong
thc t. Hm lng than ph hp x l cypermethrin l 12 13 g/l ng vi
hiu qu x l t khong 88% v dung lng hp ph t khong 0,8 mg/g
(theo hnh 4.3). Tuy nhin, do hm lng than b sung cng ln, hiu qu x
l cng cao nn trong th nghim ny, la chn lm lng than b sung l 50
g/l nh gi nh hng ca nng cypermethrin n kh nng hp ph
tng ng khi lng b sung l 1g.

4.1.4. nh hng ca nng Cypermethrin

Nng u vo ca cypermethrin quyt nh c tnh ca qu trnh


hp ph tng t nh i vi qu trnh lng: hp ph ring r hoc hp ph
cnh tranh. V nguyn tc, nu hm lng than khng thay i, hiu qu s

49
tng dn khi nng ca cht b hp ph trong mi trng thp. y cng l
nguyn nhn v sao phng n hp ph hay c t cui cng ca mt h
thng x l (x l hp ph nng cao) nhm loi b cc cht ho hc kh x l
bng phng php khc.

nh gi s nh hng ca nng Cypermethrin ti kh nng hp


ph Cypermethrin ca than hot tnh chng ti tin hnh th nghim nh sau:
Cn 1g VLHP cho ln lt vo ng ly tm cha 20 ml dung dch c nng
Cypermethrin khc nhau 1 ppm; 2 ppm; 5 ppm; 10 ppm. Tin hnh lc vi tc
150 vng/pht nhit phng (250C) trong thi gian 90 pht. Ly tm ly
dung dch em i xc nh nng Cypermethrin con li bng GC/MS.

Bng 4.7: Nng ca Cypermethrin sau th nghim xc nh nh hng


ca nng Cypermethrin ti kh nng hp ph

Nng Cypermethrin sau th nghim


Nng Ln lp
(ppm)
(ppm) li
Mu 1 Mu 2 Mu 3
I 0,014 0,014 0,015
1 II 0,014 0,014 0,015
III 0,014 0,014 0,014
I 0,047 0,047 0,047
2 II 0,047 0,047 0,047
III 0,047 0,047 0,047
I 0,148 0,149 0,147
5 II 0,148 0,150 0,147
III 0,149 0,167 0,147
I 0,360 0,370 0,361
10 II 0,361 0,370 0,360
III 0,362 0,371 0,362
Ngun: Kt qu th nghim, 2013

K tha cc kt qu trc, th nghim c din ra iu kin:

50
pH mi trng = 7;
Thi gian phn ng: 90 pht;
Hm lng than: 50 g/l

nng 1 ppm, th nng Cypermethrin cn li sau khi x l dao


ng trong khong 0,014n 0,015 ppm. Cn mu c nng ban u l 2
ppm, sau khi x l nng Cypermethrin cn li dao ng trong khong
0,047ppm. Mu c nng ban u l 5 ppm, th nng Cypermethrin cn
li sau khi x l nm trong khong 0,147 n 0,167 ppm. Cui cng, mu
c nng u vo ln nht 10 ppm th nng Cypermethrin cn li sau khi
x l dao ng trong khong 0,360 n 0,371 ppm.

Kt qu ca th nghim cui cng ny cng ging nh kt qu ca cc


th nghim trc n, c bit l iu kin nng u vo t 10 ppm. iu
ny cho thy mc n nh cao ca phng php th nghim v phng
php nh gi cht lng kt qu th nghim.

Bng 4.8: nh hng ca nng u vo n s hp ph Cypermethrin

Nng ban Nng sau x Dung lng hp Hiu qu x


u l ph l
C0 (ppm) Ccb (ppm) q (mg/g) H (%)
1 0,014 0,020 98,60
2 0,047 0,039 97,65
5 0,150 0,097 97,00
10 0,366 0,193 96,34
Trong : Nng sau x l c xc nh bng gi tr trung bnh (n = 9)

Ngun: Kt qu th nghim, 2013

Qua bng 4.8 v hnh 4.4 ta nhn thy rng khi tng nng dung dch
Cypermethrin t 1 ppm - 10 ppm th dung lng hp ph ca than i vi

51
Cypermethrin cng tng. Dung lng hp ph ca than i vi Cypermethrin
thp nht mu 1 ppm (0,020 mg/g) v cao nht mu c nng l0 ppm
(0,193 mg/g). Ngc li vi xu hng , hiu qu hp ph ca than i vi
Cypermethrin dao ng trong khong 96,34 n 98,60% tng ng vi cc
nng l 10 ppm - 1ppm. Hiu qu x l thp nht nng 10 ppm
(96,34%) tng ng vi dung lng hp ph ca than t c l 0,193 mg/g.
Hiu qu x l t hiu qu cao nht nng 1 ppm (98,60%) tng ng
vi dung lng hp ph ca than ch t c l 0,020 mg/g.

Xu th bin i nng ny cho thy c tnh hp ph ca vt liu i


vi cypermethrin. Tng t nh i vi hm lng vt liu hp ph s dng,
vic gia tng nng ca cht b hp ph u vo dn n gim hiu qu x
l v tng dung lng hp ph.

0.20

0.15

0.10
Dung lng hp ph (mg/g)
0.05

0.00
1 2 5 10
Nng Cypermthrin (ppm)

Hnh 4.4. nh hng ca nng u vo n s hp ph Cypermethrin

Do , im x l ti u l im gp nhau gia hai xu hng thay i


ny. Trong nghin cu ny, ti nng Cypermethrin u vo khong 5 ppm
th qu trnh x l vi nhng iu kin th nghim l ti u. Ti nng 5
ppm, dung tch hp ph t c 0,097 mg/g v hiu qu t c 97%. Tuy
nhin, kt qu ny ch c ngha iu kin th nghim (pH = 7; nhit

52
25oC, hm lng than 50 g/l, nng cht b hp ph dao ng trong khong
1 10 ppm). Mun ng dng vo thc t quy lut quan h gia nng v
hiu qu x l, cn phi s dng cc phng trnh ton l thuyt nh gi.

4.2. Kh nng hp ph ca than hot tnh i vi Cypermethrin

T c im qu trnh hp ph: hp ph vt l hoc ho hc gia than


hot tnh v Cypermethrin, phng trnh ng nhit Freundlich l ph hp vi
iu kin ca nghin cu ny. Do , phng trnh ny c s dng m
t mi quan h gia nng v kh nng hp ph ca than hot tnh c
biu din bng dung lng hp ph.

T kt qu 4.1.4, xy dng ng ng nhit hp ph ca than hot


tnh i vi Cypermethrin. Da vo ng hp ph ng nhit
Freundlichdng tuyn tnh biu din s ph thuc ca x/m vo C 0 s xc nh
c dung lng hp ph q v hng s n, K.Theo l thuyt kh nng hp ph
ca than tnh theo phng trnh Freundlich l:
1
q=K f C n (4.1)

Trong : q: Dung lng hp ph (mg/g)

Kf v 1/n: hng s hp ph Freundlich,

Logarit hai v ca phng trnh (3.1) ta c phng trnh (3.2):

Log q = logKf + 1/n logC (4.2)

Do nng cng tng th kh nng hp ph cng gim nn mi quan h


ca phng trnh Freundlich l mi quan h nghch. Phng trnh tng quan
tuyn tnh c biu din l y = ax + b.

53
-2

-1.6 f(x) = 0.99x - 1.7


R = 1
-1.2
log (q)
-0.8

-0.4
0 0.2 0.4 0.6 0.8 1
0
Log (Co)

Hnh 4.5: ng ng nhit hp ph Freundlichchuyn dng tuyn tnh


ca than hot tnh GAC i vi Cypermetrin

Nh vy, cn c vo phng trnh tng quan tuyn tnh (4.2) c th


hin trong hnh 4.5 ta c cc hng s ca phng trnh Freundlich nh sau:

a= 0,985; b= -1,7018vR= 1

1/n= 0,985 n= 1,0152 (1)

log10Kf = -1,7018 Kf = 0,0199 (2)

Thay (1), (2) vo phng trnh (4.1) ta c phng trnh biu din
mi quan h gia dung lng hp ph ca than hot tnh i vi nng ca
Cypermethrin l:

q=0,0199C00,985 (mg/g) (4.3)

T kt qu phng trnh tng quan 4.3 thu c c th xy dng


ng hp ph ng nhit Freundlich vi cc khong nng khc nhau.
Trong trng hp nghin cu ny, xy dng ng Freundlich vi nng t
0 n 10 ppm cho bi hnh 4.6.

54
2
1.6
1.2
Dung lng hp ph (mg/g) 0.8

0.4
0
0 2 4 6 8 10
Nng Cypermethrin (mg/l)

Hnh 4.6: ng ng nhit hp ph Freundlich thu c trong khong


nng nghin cu
T kt qu nghin cu tng quan, hin nay vn tm cht hng lot
ng bng sng Cu Long c th do nng qu cao ca Cypermethrin trong
nc nui tm gy ra. V d, theo kt qu phn tch mi trng bn y ao
nui cho thy nng Cypermethrin vt qu t 3 n 6 ln so vi tiu chun
cho php (0,1 mg/kg) ng vi mc 300 600 ppb trong khi gi tr LC 50 ca
tm l 0,005 (ppm) ng vi 5 ppb (tham kho kt qu nghin cu ca Trng
Quc Ph, 2011). Nng ca Cypermethrin trong nc thp hn trong bn,
nhng cng mc cao: 30 100 ppb.
Nu cn c vo nng ny, nhu cu x l Cypermethrin phi t c
hiu qu t 83 95% th mi m bo gi tr ca Cypermethrin trong mi
trng khng gy cht hng lot. Vic thiu s liu v gi tr ngng an ton
sinh hc ca Cypermethrin i vi tm nui hin nay cng gy kh khn cho
vic xc nh tiu ch x l. Trong khi , hiu qu x l phi t c cao
hn 83% cng rt ph hp vi nhng kt qu th nghim ca nghin cu ny
(v d: pH 9; thi gian phn ng 30 pht; hm lng than 0,1 g/l v khng
cn xem xt ngng nng trc khi x l).
Theo kt qu ca bng 4.8, dung lng hp ph than hot tnh cn phi

55
t c x l t hiu qu trn 95% i vi tt c cc nng ca
Cypermethrin trong t nhin thp hn hng nghn ln so vi kt qu th
nghim t c (0,567 1,857g/g so vi 0,020 0,193 mg/g (kt qu cc
th nghim). Do , vic p dng kt qu nghin cu vo thc tin x l
Cypermethrin trong nc l hon ton c cn c.
V d, tnh ton trong trng hp nc nui tm cn x l c nng
Cypermethrin l 30 ppb ta c dung lng hp ph phi t c l 0,567 g/g
than hot tnh. h thng x l t hiu qu cao nht, cc thng s vn hnh
phi c khng ch mc ti u ca cc th nghim phn 4.1 bao gm:

Nhit x l dao ng xung quanh 25oC


pH mi trng nc = 7
Thi gian phn ng 30 pht
Khng c yu t hp ph cnh tranh v cc yu t khc gy cn tr qu
trnh x l v hiu qu x l.
Khi , hiu qu ti a t c ca x l 86,54% (bao gm nh hng
ca pH v ca thi gian tip xc kt qu th nghim phn 4.1 v 4.2) tng
ng h s b ca phn ng l 0,8654. Lng Cypermethrin trong mt mt
khi nc cn x l l: 30 * 0,8654 = 25,96 (mg). Trong kh , dung lng
hp ph ca than hot tnh l 0,567 g/g tng ng lng than cn s dng l
52,91g. Nh vy lng than cn s dng cho 1 m3 nc ao nui trng thu
sn l 52,91 g hiu qu x l t 86,54% v cht lng nc sau khi x l
l 4,04 ppb thp hn so vi gi tr LC50 ca Cypermethrin i vi tm nui.
Tng t nh vy cc nng khc ca Cypermethrin, khi lng
vt liu hp ph cn thit dao ng trong khong 53 54 g s dng cho 1 m 3
nc cn x l. Tuy nhin cn phi lu rng khi nng tng th hiu qu
x l gim xung k c trong trng hp nng x l ch vo khong thp
hn 100 ppb.

Bng 4.9: D kin dung lng hp ph ca than hot tnh i vi

56
Cypermethrin v hm lng than cn s dng x l nc thi

Nng ban u Dung lng hp ph Hm lng vt liu hp ph


C0 (ppb) q (g/g) m (g/m3)
30 0,567 52,91
40 0,753 53,12
50 0,938 53,30
60 1,123 53,43
70 1,307 53,56
80 1,491 53,66
90 1,674 53,76
100 1,857 53,85
Trong : q c xc nh bng cng thc 4.3

Gi thit phi x l mt ao c dung tch nh: vo khong 500 m 3 nc,


phi bm nc trong vng 4 gi nc y ao hoc phi thot nc trong
vng 4 gi ao cn nc. Phng n x l la chn l hp ph ct s dng
than hot tnh dng ht (GAC) th phng n x l nh sau:
Nng Cypermethrin trong ao: 30 100 ppb
Nhit phn ng dao ng xung quanh 25oC
pH mi trng nc = 7
Thi gian lu nc trong ct lc c khng ch khong 30 pht
Ct lc hp ph s dng khi lng than hot tnh:

Thp nht (52,91)* (500/ (4/0,5)) = 3.307 g = 3,3 kg

Cao nht (53,85)* (500/ (4/0,5)) = 3.366 g = 3,4 kg

Khng c yu t hp ph cnh tranh


Khng c cc yu t gy cn tr qu trnh x l v hiu qu x l

Theo kt qu ca phn 4.1, nu qu trnh x l l ti u, d bo hiu


qu x l s t c khong 86,54% i vi tt c cc nng (do nh

57
hng ca pH x l v thi gian tip xc gia hot cht cn x l v than
hot tnh dng ht (GAC) s dng). Vi hiu qu x l tng i thp ny,
nng 0 37 ppb, x l hp ph 01 ln s cho hiu qu ph hp vi yu cu
u ra. Trong khi cc nng > 37 ppb s cho cht lng nc u ra
khng m bo thp hn 5 ppb. Trong trng hp ny nc sau khi x l cn
c x l cp hai bng cng mt phng php hoc bng mt phng n
cng ngh khc.

Bng 4.10: D kin hiu qu thc t x l nc l cha Cypermethrin


nhng nng khc nhau

Nng ban u Nng sau x l ln 1 Nng sau x l ln 2


C0 (ppb) C1 (ppb) C2 (ppb)
30 4,04 0,54
40 5,38 0,72
50 6,73 0,91
60 8,08 1,09
70 9,42 1,27
80 10,77 1,45
90 12,11 1,63
100 13,46 1,81
Trong : hiu qu x l l 86,54% cho 1 ln

Ngoi ra, do hin nay cha c nghin cu chnh thc nh gi ngng


an ton sinh hc ca Cypermethrin trong ao nui i vi tm nc l, v vy
vic x l t gi tr LC50 ch c th hn ch c hin tng tm cht hng
lot m khng th khng ch c cht lng mi trng ao nui tt cho sinh
trng v pht trin ca tm. Do , vic x l t nht hai ln vi hiu qu t
khong trn 80% trong mt ln x l l iu cn thit. D kin hiu qu x l

58
nhiu ln bng phng php: s dng 02 ct hp ph trong v d ny c
trnh by trong bng 4.10.

Cc kt qu trn y phn no s b nh gi c kh nng p dng


ca phng php hp ph trong x l tn d Cypermethrin trong ao nui tm
nc l s dng vt liu hp ph l than hot tnh. Tuy nhin, p dng
phng n ny vo thc t x l mi trng cn c nhiu nghin cu su hn
thit lp cc thng s vn hnh ph hp.

59
Phn 5: KT LUN V KIN NGH
5.1 Kt lun
Cc yu t quan trng nh hng n hiu qu ca x l bng phng
php hp ph i vi Cypermethrin l pH, thi gian, hm lng than v nng
hot cht u vo. T kt qu nghin cu cho thy mc nh hng ca
cc thng s khng ging nhau:
pH gy nh hng khng ng k n hiu qu x l khong gi tr
t trung tnh n hi kim (7 9) vi hiu qu thp nht pH 9 (94.99%) v
cao nht pH 7 (97,49%) tuy nhin khc bit ny khng ng k. Thi
khong 15 30 pht sau khi cho than hot tnh hp ph Cypermethrin c hiu
qu x l khong 86,54% nhng tc phn ng l nhanh nht. Hm lng
khong thch hp trong x l nc l 12 13 g/l nc. Nng u vo tng
lm tng dung lng hp ph ca than (t 0,020 n 0,193 mg/g) trong khi
lm gim hiu qu hp ph (t 98,6 xung 96,34%). Do , cht lng mi
trng t nhin c nng Cypermethrin thp (vi chc ppb) khi x l s cho
hiu qu rt cao.
Cn c vo ng biu din nng ban u v kh nng hp ph ca
vt liu nhn thy ng ng nhit hp ph tun theo phng trnh
Freundlich. Phng trnh ng nhit hp ph m t c trong iu kin phn
ng l:
0,985
q=0,0199C0 (mg/g)
Phng trnh ng nhit Freundlich xc nh c l c s khoa hc
quan trng xut xy dng h thng x l nc nui tm ph hp vi
iu kin thc t v nng Cypermethrin trong ao nui.

60
5.2 ngh

Xc nh c s l thuyt v cc yu t nh hng thc t ca mt cng


ngh x l l mt hng nghin cu phc tp i hi rt nhiu thc nghim
khc nhau. Vi mc ch cao hn l xut xy dng c mt h thng x
l c hiu qu d lng ca Cypermethrin trong nc nui tm bng than
hot tnh dng ht cn c cc nghin cu i su hn na vo c ch v cc
thng s vn hnh ca cng ngh v bin php x l. Tuy nhin, nghin cu
hin ti c thc hin vi quy m th nghim jar test, s lng cc yu t
nh hng t v s lng im o c cha nhiu nn cha th m t chnh
xc v chi tit c bn cht ca qu trnh hp ph, iu ny nm ngoi mong
mun ca tc gi khi thc hin nghin cu ny. V vy trong tng lai, nu c
c s gip ti mong mun c thm c hi tip tc hng nghin cu
ca mnh v a ra nhng kt qu mang tnh chnh xc cao hn:
Kim tra nh hng ca nhit ti qu trnh hp ph Cypermethrin
ca than hot tnh dng ht (GAC) tm ra khong nhit thch hp
nht cho qu trnh hp ph ca than s dng trong nghin cu.
Th nghim vi b hp ph kim tra kh nng loi b Cypermethrin ti
a ca b nhm tm ra gii hn x l ca b, tc l tm ra dung tch ln
nht m b hp ph c th x l t tiu chun. Tin hnh th nghim
vi khi lng than, thi gian lu v vn tc dng ra.
Tng bc a b hp ph vo thc nghim cc vng nui tm nhm
x l nc trc khi cp cho ao nui v xy dng phng n ti ch
than c hiu qu v x l bn trong b sau khi x l.

61
TI LIU THAM KHO
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65
Ph lc: Mt s hnh nh trong qu trnh thc hin ti

Hnh 1: Tin hnh lc mu Hnh 2: Tin hnh ly tm mu

Hnh 3: Ly tm mu Hnh 4: Tin hnh ly tm mu


(5000 vng/pht trong 5 pht)

Hnh 5: Tin hnh hiu chnh pH Hnh 6: Ha cht dng chit mu

66
Hnh 7: Tin hnh chit mu Hnh 8: Tin hnh c mu

Hnh 9: Tin hnh lu mu chy Hnh 10: H thng GC/MS


GC/MS

67