Nghiên cứu xác định cyclic volatile methy siloxanes trong vật chất dạng hạt (PM 0.1 và PM 0.5) thu được từ một số địa điểm tại Bắc Ninh, Việt Nam.

VIETNAM NATIONAL UNIVERSITY, HANOI
UNIVERSITY OF SCIENCE
FACULTY OF CHEMISTRY

GRADUATION THESIS

 

STUDY ON DETERMINATION OF CYCLIC VOLATILE METHYLSILOXANES IN PARTICULATE
MATTER (PM 0.1 AND
PM 0.5) COLLECTED FROM SEVERAL LOCATIONS
IN BAC NINH , VIETNAM

Student:
Nguyễn Ngọc Đức
Student code:
18000561
Class:
K63TTH
SUPERVISOR: Assoc. Prof. Dr. TRAN MANH TRI
PhD students: LE MINH THUY


OBJECTIVES
• Optimization of the siloxanes analysis procedure in PM 0.1 and 0.5
samples
• Determination of the concentration of siloxane in samples collected
from Bac Ninh
• From the above results, assess the risk of exposure to people at all
ages.

INTRODUCTION


RESEARCH SUBJECTS
Mass
Compound

Name

Structure

molecular
(g/mol)

Hexamethylcyclotrisiloxane
(D3)

D3

Hexamethylcyclotrisiloxane

C6H8O3Si3

222

D4

Octamethylcyclotetrasilixane

C8H24O4Si4

297

D5

Decamethylcyclopentasililoxane

C10H30O5Si15

371

D6

Dodecamethylcyclohexasiloxane

C12H36O6Si6

445

Octamethylcyclotetrasiloxane
(D4)

Decamethylcyclopentasiloxane
(D5)

Dodecamethylcyclohexasiloxane
(D6)

APPLICATION OF SILOXANE


Toxicity
Cite
Ciapetti G. et al., 1995;
Kossovsky N. et al.,
1995; Bondurant S. et
al., 2000; Reddy M. et
al., 2007; WHO
Technical Report Series
966, 2011.

Kossovsky N. et al.,
1995; Ericsson D.A.
1998; Bondurant S. et
al., 2000; Horii Y. et al.,
2008.

Regulations

Area

Affect

In human body

• Genital tumors,
Distributed in organs in
the body

• Accumulation in
organs (brain, spinal
cord)
• Carcinogenic

Human immune system

• Immune stimulation,
acting as super antigen
• Changes in the
number and distribution
of cells in the immune
system
• Development of
autoimmune diseases:
arthritis,
hypothyroidism,
myalgia
• Formation of
antibodies against
polymers

D4

D5

D6

Cosmetics,
by weight,

(Canada,
EU)

<0.1%

<0.5%

<0.1%

Air in the
workplace
(EU)

<40 µg/m3

<100 µg/m3

<40 µg/m3

Human
exposure
dose (µg/kgbw/day),
(Canada,
EU)

<15

<50

<15

PATICULATE MATTER


EXPERIMENT

Extract

GCMS

Data


GC/MS/MS TSQ 9000 (Thermo)
DB-5MS 30 m x 0.25 mm x0.25 µm

Chrom. Column

(Agilent)

Injection mode

Spitless

Injection volume

1 µL

Carrier flow

1 mL/min (He)

Inlet temperature

280 oC
40 oC (2 min), 20 oC/min to 220 oC (3 min), 5

Gradient temperature

C/min to 250 oC (2 min), 3 oC/min to 280 oC

o

(3 min)
MS transferline
temperature
Ion source
temperature
Quan.

280 oC

230 oC
SIM mode

Temperature(0C)

Parameters

300

250

200

150

100

50

0

0

5

10

15

20

Time (min)

25

30

35

40


CALIBRATION CURVE
D3
Y = 0.847959+0.0200444*X R^2 = 0.9996 W: Equal

D4
Y = 0.204305+0.00612972*X R^2 = 0.9996 W: Equal

5.0
1.4

4.5

1.2

4.0

1.0
Area Ratio

Area Ratio

3.5
3.0
2.5
2.0

1.5

0.8
0.6
0.4

1.0
0.2

0.5

0.0

0.0
0

20

40

60

80

100

120

140

160

180

200

0

220

20

40

60

80

100

D5
Y = 0.0774884+0.00367263*X R^2 = 0.9999 W: Equal

140

160

180

200

220

D6
Y = 0.025699+0.00187437*X R^2 = 0.9998 W: Equal

0.8

0.40

0.7

0.35

0.6

0.30

0.5

0.25

Area Ratio

Area Ratio

120
ppb

ppb

0.4
0.3

0.20
0.15

0.2

0.10

0.1

0.05

0.0
0

20

40

60

80

100

120

140

160

180

200

0.00

220

0

ppb

Cyclicsiloxane

Cal 1
2

Cal 2
10

Cal 3
20

20

40

60

80

100

120
ppb

Cal 4
50

Cal 5
100

Cal 6
200

ng/mL

140

160

180

200

220

PROCEDURE
10ml Ace:Hex(1:1)
Extraction 10 min
Filter paper

Chopped

Spiked 50 µL M4Q 2000 ng/ml
Equalize 10 min

Extract 3 times
Centrifuge at 4500 rpm for
5 min


Rocket concentrator tube

Evaporate the solvent to ~ 3 mL

SPE with Bond elut LRC-18 column
Concentrated by Nitrogen stream to 0.5mL
Activate the column with 4 mL of hexane
Load the extract onto the column, rinse with hex
Elute 10 mL Hex:DCM(1:1)


Name

IDL(pg/m3)

IQL(pg/m3)

MDL(ng/m3)

MQL(ng/m3)

D3

0.02

0.06

0.001

0.003

D4

0.02

0.06

0.001

0.003

D5

0.02

0.06

MDL =IDL/(R%) * Vaverage

0.001

0.003

D6

0.03

0.09

0.001

0.003

Recovery(%)=(Ctt/
Cc)*100

Recovery (%) of blank sample spk 100ppb
D3

D4

D5

D6

1

79.2

77.4

105

103

2

79.6

81.7

107

135

3

86.2

83.9

114

113

4

78.5

87.1

106

116

5

84.6

81.4

96.2

131

6

85.5

84.3

95.7

135

7

86.4

84.1

105

134

About

78.5-86.4

77.4-84.5

95.7 - 114

103-135

Average

82.9

82.8

104

124

SD

3.58

3.05

6.38

13.0


SAMPLING
Sample collection diagram

Samples were taken at several
locations throughout Bac Ninh
Province in northern Vietnam.

Air

PM 10
PM 2.5
PM 0.5
PM 0.1

40L/min in 21 hour

Sampling map


Date

Information

Time

Flow
(L)

L1

25/9/2021

Phu Khe craft village - Tu Son - Bac Ninh

22h

51348

21°8’18” N

105°56’24” E

L2

25/9/2021

Dong Ky craft village - Tu Son - Bac Ninh

21h

50021

21°8’7” N

105°56’38” E

L3

26/9/2021

Dong Ky craft village - Tu Son - Bac Ninh

22h

50823

21°7’59” N

105°56’50” E

L4

26/9/2021

Duong Son craft village-Tam Son-Tu Son-Bac Ninh

21h

49203

21°9’2” N

105°57’30” E

L5

27/9/2021

Hanaka Industrial Park - Tu Son - Bac Ninh

23h

50249

21°7'23" N

105°57'28" E

L6

27/9/2021

Dong Ngan - Tu Son - Bac Ninh

22h

49291

21°6’59” N

105°57’23” E

L7

28/9/2021

Da Hoi craft village – Tu Son – Bac Ninh

23h

49359

21°7'23" N

105°55'6"E

L8

29/9/2021

Tu Son Medical Center – Bac Ninh

24h

50216

21°7’26” N

105°58’15” E

L9

28/9/2021

Trinh Xa craft village - Tu Son - Bac Ninh

23h

49056

21°6'46" N

105°55'55"E

L10

30/9/2021

Nguyen Trai Street - Vo Cuong - Bac Ninh

24h

48712

21°10’1” N

106°3’52” E

L11

1/10/2021

Construction site, Han Thuyen Street - Bac Ninh

24h

49416

21°10’40” N

106°4’29” E

L12

1/10/2021

Ninh Xa - Bac Ninh

24h

48595

21°10’26” N

106°3’41” E

L13

2/10/2021

Khac Niem Industrial Park - Khac Niem - Bac Ninh

23h

48321

21°8’58” N

106°3’50 E

L14

2/10/2021

Kinh Duong Vuong Street - Vu Ninh - Bac Ninh

23h

45961

21°11'24"N

106°4'30" E

L17

4/10/2021

Duong O craft village - Phong Khe - Bac Ninh

22h

44499

21°10’04” N

106°3’32” E

L18

4/10/2021

Le Thai To / Hoang Hoa Tham street - Vo Cuong - Bac Ninh

21h

38855

21°09’52” N

106°2’23” E

L19

5/10/2021

Dao Xa craft village area, Bac Ninh

22h30’

46809

21°10’08” N

106°2’16” E

Coordinates


Mean concentrations of 4 cVMS
D3(ng/m3)

D4(ng/m3)

D5(ng/m3)

D6(ng/m3)

0.20

0.29

0.72

0.98

PM 0.1

PM 0.1
9.13%

PM 0.5

0.19

0.25

0.61

0.95
13.24%

Both

0.39

0.54

1.33

1.93

About

N.d. - 0.70

N.d. – 0.71

N.d. – 2.42

N.d. – 4.14

44.75%

32.88%

C= measured results(ng/mL)*Vrated ( 0.5 mL)/Vsample ( L)
1.2

D3

D4

D5

D6

1

ng/m3

0.8

PM 0.5
0.6
9.50%

12.50%

0.4
47.50%
0.2

0

0.2

0.19
D3

0.29 0.25

0.72 0.61

0.98 0.95

D4

D5

D6

PM 0.1

PM 0.5

30.50%

D3

D4

D5

D6


RISK OF EXPOSURE
•
In there:
DI (daily intakes): average
exposure (ng/kg/hour)
C: Mean concentration of
siloxane found in the
particulate matter sample
(ng/g)
f: average rate of indoor air
intake (m3/day)
M: body mass (kg)

According to Vietnam Encyclopedia of Knowledge(2014):
Average rate of
Body weight(bw)
indoor air intake
Age group
(kg)

(m3/day)
Infant
Preschool children
Children
Adolescent
Adult

8
15
25
48
66

4.5
7
10
13.5
13.5


Risk of exposure
1.2

1.06
1

0.9

Ng/kg/day

0.8

0.77

0.75
0.62

0.6

0.54

0.53

0.3
0.22
0.2

0

0.4

0.37

0.4

Infant

0.25
0.18

0.27

0.22
0.15
0.11

0.12

Preschool children
D3

D4

Children
D5

Adolescent
D6

0.11
0.08
Adult


CONCLUSION
• We validated the analytical method and determined cVMS in PM 0.1 and PM 0.5:
R(%): 83%-124%, SD: 3-13, Linear: 2 - 200ng/mL, MDL: 0.001 ng/m3, MQL:
0.003 ng/m3
• From that method, we apply and analyze 17 samples PM 0.1 and 17 samples PM
0.5 collected from Bac Ninh, Vietnam.

PM 0.1: 37.2 ng/m3
PM 0.5: 34.0 ng/m3
• Human exposure doses to cVMS through inhalation for various age group based
on measured concentration: infant: 2.33 ng/kg/day, preschool children: 1.95
ng/kg/day, children: 1.89 ng/kg/day, adolescent: 1.17 ng/kg/day, adult: 0.86
ng/kg/day