LUN VN THC S KHOA HC HA HC

Chuyn ngnh: Ha hc phn tch 60.44.29

NGHIN CU, XC NH HM LNG CC

KIM LOI KM, CAIMI, CH, NG TRONG NC
V TRM TCH SNG CU BN (QUNG NINH)
THEO MT S THNG TRONG NM 2010

Ngi hng dn khoa hc: TS: L C LIM

PGS.TS: TRN TH HNG VN
Ngi thc hin:
KHNG V HI

H Ni, thng 10 nm 2010

L do chn ti:
Nghin

cu, xc nh hm lng cc kim loi km,

caimi, ch, ng trong nc v trm tch sng Cu Bn
(Qung Ninh) theo mt s thng trong nm 2010

Nhim v c bn:
1

Nhim
Nhim
v

11

Tip cn, v s dng thnh tho

1 cc ph POL150 v thit b km theo.
my

Nghin cu, xy dng quy trnh

phn tch nh lng s dng phng
php von-ampe ha tan anot xung vi
phn bng phng php thm chun
nhm 1xc nh hm lng cc kim loi
km,caimi, ch , ng trong nc v
trm tch sng Cu Bn (Qung Ninh)
theo mt s thng trong nm 2010.
Kt lun, xut phng n trin
khai ng dng ti trong nh gi v kim
sot mi trng trong thc t.

NI DUNG
I

TNG QUAN

II

THC NGHIM V PHNG PHP

III

KT QU V THO LUN

III
IV

KT LUN

TNG QUAN

I.1.Tng quan vm mi trng m than o Nai v m than Cc Su

I.1.1.Tng quan vm mi trng m than o Nai
I.1.2.Tng quan vm mi trng m than Cc Su
I.1.3. c im kh hu khu vc m than o Nai - Cc Su
I.1.4. iu kin thy vn ca khu vc
I.1.5. c im nc thi m
I.2. Gii thiu v cc nguyn t km, caimi, ch, ng
I.3. Gii thiu v phng php cc ph v von-ampe ha tan
I.3.1. C s l thuyt ca phng php cc ph
I.3.2. C s l thuyt ca phng php von-ampe ha tan
I.3.3. in cc dng trong phn tch von - ampe ha tan
I.3.4. Cc k thut ghi ng von ampe
I.3.5. u im, cc hng ng dng v hng pht trin ca phng php
I.3.6. Mt s phng php phn tch lng vt kim loi nng
I.4. Gii thiu cc cng trnh s dng pp cc ph v von-ampe ha tan
xc nh hm lng cc kim loi nng

II 1THC NGHIM V PHNG PHP

II.1.Thit b, dng c v ha cht

II.2. Phng php nghin cu
Kho st xy dng quy trnh phn tch theo
phng php von-ampe ha tan anot xung vi phn (DPASV)

III

KT QU V THO LUN

III.1. Kho st cc iu kin ti u

III.2. ng chun nh lng cc ion Zn2+, Cd2+, Pb2+, Cu2+
III.3. Kho st lp li, LOD, LOQ

III.4. Phng php (k thut) thm chun

III.5. Xc nh hm lng cc ion trong mu nc v mu trm tch

III

1 KT QU V THO LUN

III.1. KHO ST CC IU KIN TI U

Mi trng
phn tch

Thng s
k thut o

nh hng ca nh hng qua

mt s cation
li gia cc ion

nh hng ca
ion Ga3+

1
Bng
3.1. Cc thng s k thut ghi o

III.1.1.1.
Kho st chn nn in li ti u
1
(KCl, NaCl, NaAc+HAc, NH4Ac + HAc)

Hnh 3.1. Ph kho st nn KCl

III.1.1.1.
Kho st chn nn in li ti u
1
(KCl, NaCl, NaAc+HAc, NH4Ac + HAc)

Hnh 3.2. Ph kho st nn NaCl

III.1.1.1.
Kho st chn nn in li ti u
1
(KCl, NaCl, NaAc+HAc, NH4Ac + HAc)

Hnh 3.3. Ph kho st nn (NaAc + HAc)

III.1.1.1.
Kho st chn nn in li ti u
1
(KCl, NaCl, NaAc+HAc, NH4Ac + HAc)

Hnh 3.4. Ph kho st nn (NH4Ac + HAc)

Nn ti u: (NH4Ac + HAc)

III.1.2.
Kho st chn pH ti u
1

(Ghi o dng Ip vi gia tr pH = 2,5; 3,0; 3,5; 3,8; 4,2; 5,0; 5,5)

4,2
Hnh 3.5.Ph
Hnh
3.6.IpS
ca
ph
bn
thuc
nguyn
Ip vo
t pH
cc pH khc nhau

pH ti u: 4,2

III.1.1.3.
Kho st chn nng nn ti u
1
(o Ip cc gi tr Cnn = 0,004 M 0,04 M )

300
Zn2+

250

Ip (nA)

200

Cd2+

150
Pb2+

100
50

Cu2+

0
0

0.01

0.02 0,024 0.03

0.04

0.05

C (mol/l)

Hnh 3.8. S ph thuc Ip vo nng nn in li

Nng nn in li ti u : 0,024 M

III.1. KHO ST CC IU KIN TI U

III.1.2.Kho st cc thng s k thut o ti u:
1

Bng3.13. Cc thng s k thut o ti u

in cc lm vic
HMDE

Ch o

S git

Thi gian sc kh

Tc khuy

p sut

Thi gian cn bng

15s

Thi gian in phn lm giu

180s

Bin xung

50mV

10

Thi gian xung

40ms

11

Bc bin

2mV

12

Bc thi gian

0,4s

13

Khong qut th
-1150mV 135mV
Mn
hnh
my
Tc
qut
thhin th chn thng s 5mV/s

14

DPP
01 git

180s
300rpm
1bar

III.1.1KHO ST CC IU KIN TI U
III.1.3. Kho st nh hng ca mt s cation
III.1.3.1 Kho st nh hng ca Fe3+
350
Zn2+

300

Ip (nA)

250
Cd2+

200
150

Pb2+

100
50

Cu2+

0
0

20

40

60

80

100

120

140

160

C (Fe3+)/C(M2+)

Hnh
Hnh3.24.
3.25.Ph
S ph
kho
thucst
Ip nh
vo hng
t l CFeca
/CM2+
Fe3+

III.1. 1KHO ST CC IU KIN TI U

III.1.4. Kho st nh hng qua li gia cc ion
2+
2+
III.1.4.1.
Kho
st
nh
hng
ca
Zn
/C/C
= 1 150
ln)
M2+
III.1.4.3.
Cu
l C
CZn2+
150
ln
III.1.4.2.
Kho
st
nh
hng
ca
Cd
l
C
ln
) )
Cu2+ /C
M2+==11 80
Cd2+
III.1.4.3.
Pb2+ (((( tttt l
l
C
Pb2+ /CM2+
M2+= 1 150 ln)

2+ ti
Cu2+
Hnh 3.36.
3.30. Ph kho st nh hng ca nng ion Pb
3.32.
3.34.
Zn
Cd
ti cc
cc ion
ion cn
cn li
li

III.1.1KHO ST CC IU KIN TI U
III.1.5. Kho st nh hng ca cation ph tr Ga3+

Nhn xt :
Vi nhng iu kin ti u kho st trn nh
nn in li, pH, nng nn, thi gian ui oxi, cc iu
kin k thut ghi, o dng von-ampe ho tan v s nh
hng ca cc ion cn tr cng nh s nh hng qua li
gia cc ion phn tch, c th thy rng hon ton c th
nh lng ng thi Zn2+, Cd2+, Pb2+ v Cu2+ cc iu
kin ti u kho st trn.

Hnh 3.38. S ph thuc Ip ca bn nguyn t vo CGa3+ trong mu o

III.2. NG
CHUN XC NH HM LNG CC ION
1

2+, Cdca
2+, Pb
2+, Cu2+)
3.40. Ph kho
st xy
dng
ng
chun
4 ion
Hnh 3.(41,42,43,44).
ng
chun
cc
ion Zn

III.1.1KHO ST LP LI, LOD, LOQ

Bng 3.27. Kt qu o kho st lp li
Ip (nA)
Ln o

2+
2+
Pb2+
-9 (M)
GiiZnhn
pht hin :CdLOD
Zn2+ = 4,0.10

1
2

3
4
5
6

288,0

120,0

44,0

-8 (M)
Gii 287,0
hn nh lng:119,5LOQ Zn2+ = 1,3.10
43,0
43,5
-9 (M)
Gii289,0
hn pht hin :122,0
LOD Cd2+ = 5,0.10
287,0

122,3

42,6

-8 (M)
Gii286,0
hn nh lng:
121,5
LOQ Cd2+ = 1,69.10
43,2

208,8
206,5
208,3

7
8

119,8LOQ Pb2+ = 1,49.10-8(M)

41,9
Gii285,0
hn nh lng:

207,0

10
Gi tr TB
S
lch gt TB

121,0

Gii 286,7
hn pht hin 121,7
: LOD

42,0

207,5

206,9

286,6

123,0

208,0

Gii287,5
hn pht hin 121,4
: LOD Pb2+ = 42,3
4,48.10-9(M)

285,0

Cu2+

Cu2+

42,0

= 3,26.10-9
(M)
42,8

42,73
Gii286,78
hn nh lng121,18
: LOQ Cu2+ = 1,08.10-8
(M)
0,445

Nhn xt
0,140 :

207,2

208,2
207,8
207,62

0,252

0,284

0,255

0,0798

0,09

0,0808

q%

0,706

0,793

0,468

0,088

tbng

2,26

2,26

2,26

2,26

ttnh

Phng php von-ampe ho tan xung vi phn vi in

cc git
treo c kh nng
thi nhiu nguyn
1,540
1,777 xc nh ng
0,501
0,341 t v

Kt lun cPhng
nhy
trnh
rt ng
cao (n.10-9M).
chun ph hp v m bo tnh thng k, s sai
Hnh
3.45.
Ph

o
kho st lp li (o lp 1 ln)
khc ch l ngu nhin.

1 THUT THM CHUN XC NH HM LNG CC ION

III.4.
III.5. K
XC NH HM LNG ION TRONG MU THT
III.5.1. Kho
III.5.2.
Ly mu
st v
phng
bo qun
php
mu
x l mu
nh
gicc
hiu
thu hi
theo
t
PhaBng3.29.
dung dch hn
hp
ionsut
thm
chun
vipp
cc
nng ln lt nh
sau : CNguyn
C (Cd2+)
0,1(mg/l)
(Zn2+) = 15,0(mg/l)
Lng cht;
Lng cht c tm
Sai s=tng
Hiu; sut
C (Pb2+)
C (Cu2+)i%
= 20,0(mg/l).
t = 10,0(mg/l)
chun ;
thy (trung bnh) mg
thu hi
thm
vodung dch mu vo bnh nh mc 25ml.
%
Ly chnh xc
1ml
Thm
Zn vo 100l
300dung dch Ga3+(100mg/l).
285,00
5,00
95,0
Thm
dung dch m.14,13
Cd vo 6ml 15
5,78
94,22
Thm nc ct 2 ln n ht bu trn ca bnh nh mc ri o pH.
Pb
15
14,27
4,89
95,11
Dng HAc c chnh pH n gi tr 4,2.
3,56
96,44
nhCumc dung15dch n vch 14,46
nh mc.
a dung dch va pha vo bnh in phn.
Tin hnh ghi o dng von-ampe ly Ip(1).
Bng3.31. nh gi hiu sut thu hi theo pp kh
Thm vo bnh in phn 100l dung dch thm chun pha trn.
Tin hnh o,
ghicht
dng von-ampe
Ip(2). Sai s tong Hiu sut
Lng
Lng cht ly
chun
Thm
vo bnh
200l
dung dch thm

Nguyn
chunin
thm phnc
tm thy(mg)
i chun
%
thupha
hi trn.
vo(mg)
%
Tinthnh o,
ghi dng von-ampe ly Ip(3).
Thm
in phn 300l
dung dch thm
chun 95,00
pha trn.
Zn vo bnh300
285,00
5,00
TinCdhnh o, ghi
15 dng von-ampe
14,27 ly Ip(4).
4,89
96,11
Pp v Tin
c ha
t
Pp
v
c
ha
kh
hnh tnh 15
ton nng , x
l thng k, xy
dng ng
thm chun, tnh
Pb
14,20
5,33
94,67
ton hm lng bng phn mm Microsoft Excel v km tra ,tnh ton hm lng
Cu
15
14,30
4,67
bng chng
trnh pascal
c lp
trnh trn c s
p dng 95,33
ton thng k v phn
mm Turbo pascal 7.0
Hnh 3.46. Quy trnh nh lng

III.5.4.1 PHN TCH MU V KT QU PHN TCH

Ktsnh
qukt
xc
lng
caimi,
trong
Bng 3.41. So
qunh
phnhm
tch bng
pp km,
DP-ASV
vi pp ch,
AASng
(mu TT
thng 9)

2+
2+
2+
nc
v(mg/l)
trm tch theoZncc
thng bng
thmCuchun
vi
Ion/Nc
Cd2+ phng
Pbphp
phn
mm pascal x l3,189
s liu ta thu
c kt 1,467
qu :
Pp: DP-ASV
0,0885
1,285

Pp AAS

Bng A.

3,442

0,0940

1,512

1,393

Bng B.

lch
7,35% 2+
5,85%
2+
7,75%
2+
Ion/
nc
Zn2,97%
Cd2+
Pb
Cu2+
Ion/trm
Zn2+ Cd2+
Pb2+
Cu
(mg/l)
Bng
DP-ASV vi pp AAS (mu TT thng 9)
tch 3.42. So snh kt qu phn tch bng pp
(mg/kg)
Thng
3,76Pb2+ 0,156 1,377
Ion/TT (mg/kg)
Zn2+
Cd2+ 3
Cu2+ 1,740
0,14

Thng 3
35,1 0,880 28,91 14,66
Pp: DP-ASV
35,71
0,9541
22,1420,003 0,068
12,73 0,087

0,90

0,033 38,25
0,75 0,9957
Pp AAS 1,2
23,2130,135 1,670
13,62 1,432
Thng 5
3,67

0,06

Thng 5
42,7 0,922 22,11 13,12
lch
6,64%
4,17%
4,61%
6,53%
0,169
0,005
0,076

0,72

0,7kt qu
0,029
1,01
Nhn xt:Vi
tin hnh ghi o
thu cThng
ta thy,
cnh phng
AAS vi
7 bn2,22
0,065 php
1,217
1,19

pht
hin
v
tnh
chn
lc
cao,
tin
hnh
mt
cch
nhanh
chng,
thun
tin
cho
vic
Thng 7
31,0 0,769 19,03 10,69
0,09

0,06
phn tch nh
tng nguyn
lnghng lot,
1,13c bit
trong vic xc nh hm lng
0,001
0,065 t
km, caimi,
ch, ng
1,0
0,026th vic xc nh
0,78hm lng cc ion kim loi nng trn bng
phng php von-ampe h tan anot khng ch l
phng
cht ch
v l 1,467
thuyt , 1,28
Thng
9 php
3,189
0,088
Thng
9
35,7
0,954
22,14
12,73
thit b n gin, gn nh,hiu qu v kinh t m cn l mt phng
php
c

nh lng

0,80

tnh u vit cao trong phn tch xc nh hm lng nh, vt,

siu vt0,002
cho kt 0,066
qu c
0,152
0,067
1,1
0,027
0,76
lch khng ng k so vi kt qu phn tch bng phng php AAS.

NI DUNG

III

KT QU V THO LUN

III.5. Phn tch v kt qu phn tch

III.5.4.4. S bin thin v mi tng quan hm lng cc ion trong nc v trm tch

NI DUNG

III

KT QU V THO LUN

III.5. Phn tch v kt qu phn tch

III.5.4.5. So snh hm lng cc kim loi trong N v TT vi QC Vit Nam
Bng 3.44.
3.43. So snh hm lng kim loi nng trong trm
nctch
vi QCVN
vi QCVN
Nhn
xt:
2+
Ion/nc tch
Ion/trm
(mg/l)
Zn
Zn2+2+
Cd2+
Pb2+
Cu2+
Theo di s liu kt qu kho st, ta thy Nc
QCVN-2008-Ncmt
1,0
0,005
0,02
0,2
QCVN-2008
- t NN (A2)
200
2
70
50
sng
Cu Bn(B1)
lun trong
QCVN-2008-Ncmt
1,5 tnh trng
0,01 nhim
0,05 nng
0,5 cc
QCVN 2008 - t CN
300
10
300
100
kim
loi km, caimi, ch
QCVN-2009-NcthiCN(A)
3,0 v ng.
0,005V trm
0,1 tch sng
2,0
Thng
3
35,10
0,880
28,91
14,66
QCVN2009-Ncthi
CN(B)
3,0
0,01
0,5
2,0
nu so snh vi quy chun
v t
cng nghip,
1,26
0,033
0,90
t
0,75
Thng 3
3,76
0,156
1,377
1,740
nng
nghip
th
vn
cha
b

nhim,
tuy
vy
vn
nh
Thng 5
42,77
0,14
0,922
0,003
22,11
0,068
13,12
0,087
0,72
0,029
0,72
1,01
hng
Thng 5 ln ti cht lng
3,67 nc sng
0,1357 v hm
1,67 lng
1,432
31,00
0,169
0,769
0,005
19,03
0,06
10,69
0,076
Thng
7
kim
loi
trong
trm
tch
v
trong
nc
c

tng
Thng 7
2,22
1,01
0,0651
0,026
1,217
1,13
1,19
0,78
0,09
0,001
0,065
0,06
quan tuyn tnh nht nh.
Thng 9
Thng 9

35,70
3,189
1,10
0,152

0,954
0,0885
0,027
0,002

22,14
1,467
0,80
0,066

12,73
1,28
0,76
0,067

IV

Tip cn, v s
dng thnh tho
my cc ph
POL150 v thit b
km theo, t p
dng thnh cng
vic nh lng
ng thi 4 ion kim
loi trn b mt
in cc git thy
ngn treo, xy dng
quy trnh xc nh
ng thi nhiu
nguyn t trong
nc v trm tch
bng phng php
DP-ASV vi vic x
l s liu thng k
tnh ton
nhanh,chnh xc

KT LUN

nghin cu
tm dung dch nn
thch hp, thi
gian in phn lm
giu, th in
phn, tc qut
th, ln git
thy ngn (theo p
sut), thi gian
ui oxi, xc nh
thnh cng ng
thi hm lng vt
cc ion kim loi
Zn2+, Cd2+, Pb2+,
Cu2+ trong nn
(NH4Ac +HAc)
0,024M trn in
cc git thy ngn
treo (HMDE).

Tnh khoa hc,

tin cy ca
phng php v
quy trnh phn tch

c xc nhn
thng qua vic
nh gi chnh
xc v cc kt qu
phn tch mu
chun ca hng
Merck, thng qua
tnh ton hiu sut
thu hi ta thy sai
s 5,33%, lp
tt, xc nh c
gii hn pht hin
v gii hn nh
lng ca cc ion.

tin hnh theo

di, phn tch nc
v trm tch sng Cu
Bn xc nh ng
thi hm lng cc
kim loi km, caimi,
ch, ng theo mt s
thng trong nm
2010.
Kt qu thu c
cho thy nc sng
lun lun trong
tnh trng nhim
gp nhiu ln QCVN2008 v nc mt loi
A2, v QCVN-2008 v
nc thi cng
nghip

Cm ph: 25-03-2010 -/-/- H Ni 26-10-2010

Em xin chn thnh cm

n cc thy c!

III.1. Kho st cc iu kin ti u

III.1.2.Kho st cc thng s k thut o ti u:
III.1.2.1. Kho st bc
III.1.2.8.
III.1.2.2.
III.1.2.3.
III.1.2.4.
III.1.2.5.
III.1.2.6.
III.1.2.7.
thisut
tc
p
bin

gian

thi
bin
khuy:
t
xung:
in
xung:
cn
gian:
:
vo
bng:
phn
bulm
thygiu:
ngn:
Bng3.13. Cc thng s k thut o ti u

1
Bcthi
350
350
gian2500
(s)
3450

300
300
4400

in
cc lm
vic
Thi
gian

HMDE

Ip (nA)

Ch
o
qut

DPP

Sth(s)
git
Thi gian sc kh

01 git

Zn2+

Cd2+

Pb2+

180s

Tc khuy

6300

p sut

1bar

7200
250

Thi gian cn bng

15s

(nA)
Ip
Ip(nA)
(nA)
Ip

5350
250
250

200

0,1
8200
150

150
9150
100
100
10
0,2
100
11 50
50
12
0,400
13 0
14

1,0
15

64in phn271,0
Thi gian
lm giu

98,4

33,2

257

Khong qut th

180s

Cd2+
Cd2+

182,0

50mV

285,0

105,0

35,5

Bc bin
Bc thi gian

Cu2+

300rpm

Bin xung
Thi gian
128xung

Zn2+
Zn2+
Zn2+

40ms

209,0

2mV

327,0

126,0

00
50100 100 200 150 300200 400
250
0 Tc qut
5 th 10
15
20
25
t( s)..
( rpm)
643
..V khuy
pH dung
dch
t( s)

43,8

0,4s

239,0

-1150mV 135mV

300
500
30

5mV/s
35

350
600

..

4,2

..

Pb2+
Pb2+
Cu2+
Cu2+