IOSH102-A302

Environment measurement and analysis

of organic solvents of workers of
automobile manufacturing and body
repair and spray painting

IOSH102-A302

Environment measurement and analysis

of organic solvents of workers of
automobile manufacturing and body
repair and spray painting

102 4 15 102 12 10

103 03

16
(Volatile organic compound,
VOCs)

(Toluene)(Xylene)(n-Heptane)(Propene)
(Butyl acetate)(Amyl acetate)(Methanol)
21

6.75ppm 1.22ppm
GC/MS
ATD-GC-FID

Abstract
Booming economic development is accompanied by a rapid increase in the numbers of
motor vehicles. The number of traffic accidents is highly correlated with the number of
vehicles on the road, and Taiwan now records nearly 160,000 traffic accidents a year. The
result is growing demand on the sheet-metal spraying industry. Sheet-metal spraying is one
category of the surface-coating industry, and workers in this industry come into contact with
a number of volatile organic compounds (VOCs). Furthermore, specific organic solvents
must be added to paints before they are used, and this causes an additive effect that increases
the hazard to workers.
This study focused on auto repair shops operated directly by auto vendors and by
private parties, automobile factories, and motor-scooter factories, where on-site safety and
health inspections were carried out, and took and analyzed samples of the organic solvents
toluene, xylene, n-heptane, propene, butyl acetate, amyl acetate, and methanol.
Air samples were taken at 21 auto plants, motor-scooter plants, and repair shops using
activated carbon tubes and thermal desorption tubes, and were analyzed separately for
volatile organic compounds using GC/MS and ATD-GC-FID. In addition to providing an
understanding of the exposure of sheet-metal spraying workers to specific organic
compounds, comparison of the differences in and convenience of using activated carbon
tubes and thermal desorption tubes can serve as a reference in carrying out follow-up studies.
Key Words: Volatile Organic Compound, ATD-GC-FID

ii

....................................................................................................................................... i

Abstract .................................................................................................................................... ii
..........................................................................................................................................iii
..................................................................................................................................... iv
..................................................................................................................................... vi
.................................................................................................................... 1
........................................................................................................................ 1
........................................................................................................................ 1
................................................................................................................ 2
.................................................................................................................... 3
.................................................................................... 3
.................................................................................................... 5
................................................................................................................ 8
.............................................................................................................. 10
...................................................................................... 10
...................................................................................... 17
.............................................................................. 23
.............................................................................. 27
.......................................................................................................................... 39
...................................................................................................................... 39
...................................................................................................................... 39
........................................................................................................................................ 40
................................................................................................................................ 41

iii


1 ........................................................................ 4
2 GC/MS ......................................... 12
3 GC/MS .............................................................................................................. 12
4 GC/MS ............................................................................................................. 12
5 ....................................................................................................................... 13
6 ....................................................................................................................... 13
7 ............................................................................................................... 14
8 ............................................................................................................... 14
9 ....................................................................................................................... 15
10 ..................................................................................................................... 15
11 ..................................................................................................................... 16
12 ..................................................................................... 18
13 ..................................................................................................................... 19
14 ..................................................................................................................... 19
15 ..................................................................................................................... 20
16 ................................................................................................................. 20
17 ............................................................................................................. 21
18 ..................................................................................................... 21
19 ............................................................................................................. 22
20 ............................................................................................................. 22
21 1 .............................................................................................. 23
22 2 .............................................................................................. 24
23 ..................................................................................... 25
24 ...................................................................................... 28
25 .................................................................................. 28
26 ...................................................................................... 30
27 ...................................................................................... 30
28 .......................................................................................... 32
29 ...................................................................................... 32
30 .......................................................................................... 35

iv

 31 .......................................................................................... 35
32 ...................................................................................... 36
33 ...................................................................................... 36
34 .......................................................................................... 37
35 ...................................................................................... 38


1 ........................................................................... 4
2 ........................................................................................................... 7
3 ............................................................................ 10
4 (RETENTION TIME) ...................................................................................... 11
5 .................................................................................................... 11
6 ................................................................................................... 17
7 GC ..................................................................................................................... 17
8 ................................................................................... 18
9 (PPM) ............................................................ 27
10 (PPM) .......................................................... 29
11 ............................................................. 31
12 ..................................................................... 33
13 (PPM) ....................................................... 37

vi

16
(Volatile organic compound,
VOCs)

(Toluene)(Xylene)(n-Heptane)(Propene)
(Butyl acetate)(Amyl acetate)(Methanol)
GC/MS
ATD-GC-FID

GC-FIDGC/MS
(Toluene)(Xylene)(n-Heptane)(Propene)(Butyl acetate)
(Amyl acetate)(Methanol)

1. GC-MS
2.
3.
4.

(Bouyer et al., 1993; Fischer et al. 1995;

Franklin et al., 2000; Liden, 1994; Newman, 1995)
Franklin
et al., 2000; Hogberg et al., 1980; Holmes et al., 1993; Kanerva et al., 1995; Lezcano-Meza
et al., 1999; Liden, 1994Cianchetti 122

Cianchetti et al., Liden, 1994; Kanerva et al.,

1995

(Baur, 1996; Bernstein, 1996; Bouyer et al., 1996)

(13.5%)(11.5%)
(Lezcano-Meza et al., 1999)

1
150 33 13
4 8 9 21 25 (Xia et al., 2010)

1
1

TWA 100
PPM

Toluene

C7H8

108-88-3

Xylene

C8H10

106-42-3

TWA 100
PPM

1239

n-Heptane

C7H16

142-82-5

TWA 400
PPM

Propene

Butyl acetate

C3H6

115-07-1

C6H12O2

123-86-4

TWA 700
PPM

CLA1215

Amyl acetate

C7H14O2

123-92-2

TWA 525
PPM

1241

Methanol

CH3OH

67-56-1

TWA 200
PPM

OSHA 91

1235

alkanealkene

(1)

(2)

(3)

IARC****

TLV

STEL

a.gasoline

300ppm

375ppm

++

b. n-Hexane

50 ppm

75 ppm

+++

c. petroleum naphtha 100ppm

125ppm

++

++

+++

+++

Hydrocarbons
Aliphatic hydrocarbons
+

2B

Aromatic Hydrocarbons
a.benzene
b. toluene
c. xylene
d.2,4-2,4-Toluene
diisocyanate,TDI
e.styrene
2

5 ppm

10 ppm

()

()

100ppm

125ppm

()

()

100ppm

125ppm

50ppm

75ppm

50ppm

75ppm

0.005pp
m

+++

b.tetrachloroethylene 50ppm

++

+/-

+/-

2B

+++

++

2A

75ppm

+++

2A

c.methylene chloride
d.carbon tetrachloride
e.chloroform

75ppm

()

()

2ppm

4ppm

()

()

1000ppm

1000ppm

200ppm

250ppm

()

()

+++

10ppm

+/+++

+/-

+++

2B

2B

+++

++

2B

Alcohols
a.ethanol
b.methanol

50ppm

+++

400pm

500ppm

+++

5ppm

10ppm

()

()

10ppm

15ppm

()

()

+++

(
)

++

Glycols
a.ethylene glycol
Ethers
a.(ethyl ether)
b.
ethylene glycol monomethyl
ether

50ppm

2B

Chlorinated Hydrocarbons
a.trichloroethylene

+++

a.carbon disulfide

b.Methyl

Tertiary-Butyl Ether,MTBE
c.dimethyl

10ppm

15ppm

formamide

()

()

d.Ethylene oxide

1ppm

2ppm

+++

+++

++

+++

3 5
10 3

200 cc/min 360

Perkin Elmer ATD-50 50

Tenax-TA -30
40/sec Hewlett Packard 5890
(FID)DB-130 m 0.53 mm (I.D.) 3 mATD
9 cm 0.635 cm 250 mg Tenax-TA (60/80mesh)
Tenax-TA Poly(2,6-diphenylene oxide) 350
5 L10 L 1 mL1.8 mL
(1) 250 mg Tenax-TA

300 16
(2)ATD-400

 13.3 g/6 27.1g

(i)200225250280

(ii)5 10 15

(iii)150180200

(iv)0-20-30

(v)5 10

9.23 g/ 18.7 g/
(CV)

9.20g/mg~38.95g/mg

3
100 ppm
TWA-200 ppm TWA-400 ppm
TWA-700 ppmTWA-525 ppm

(short carbon chain)

TWA
100
PPM

106-42-3

TWA
PPM

100

1239

C7H16

142-82-5

TWA
PPM

400

Propene

Butyl acetate

C3H6

115-07-1

C6H12O2

123-86-4

TWA
PPM

700

CLA1215

Amyl acetate

C7H14O2

123-92-2

TWA
PPM

525

1241

Methanol

CH3OH

67-56-1

TWA
PPM

200

OSHA 91

Toluene

C7H8

108-88-3

Xylene

C8H10

n-Heptane

10

1235

 4 (retention time)

Toluene
Xylene
n-Heptane
Propene
Butyl acetate
Amyl acetate
Methanol

()
3.746
6.366
2.828
16
4.84
7.801
1.2

5

(ng
RT
)

2.835

3.479

4.84

6.366

7.801

16

1.2

10

1061147

2008806

759058

935521

600209

83691

50

4217645

6435310

3235540

3973471

2459872

146722

28135

100

10700402

15938975

8046150

10080459

6407738

234357

502571

34220870

19754789

25273472

15804391

354361

1358186

593104

2592421

200
400

52385946

800

73043311

121864226

1600

131041061

217261091

124002744

11

94347439

56833509

181846214

101996709

1052969

 2 GC/MS

3 GC/MS

4 GC/MS

12

13

14

10

15

 11

16


Perkin Elmer ATD-50 50
Tenax-TA -30
40/sec Hewlett Packard 5890
(FID)DB-130 m 0.53 mm (I.D.) 3 mATD
9 cm 0.635 cm 250 mg Tenax-TA (60/80mesh)Tenax-TA
Poly(2,6-diphenylene oxide) 350
5 L10 L 1 mL1.8 mL
6

6
6
ATD-50

260 oC
280 oC
40 oC
1 min
15 min
8 min

20:1

220 oC
-30
280 oC
50 mL/min
60 mL/min
1 min

9.5 psi

35 oC
150 oC
250 oC

230 oC
250 oC

GC 7
7 GC
Agilent-6890

20 oC/min
50 oC/min

260 Oc
450 mL/min
40 mL/min
2 mL/min

17

8 min
1 min
1 min

1.48
2.421
4.003
5.279
6.479
8.560
9.662

12

18

 13

14

19

 15

16

20

 17

18

21

 19

20

22

12 1 10

21 1

23

22 2

24

23

25

26


9 (ppm)

1
n=5

2
n=5

3
n=5

1.32
<LOD
6.59
5.12
1.05
<LOD
2.11
2.88
0.54 # <LOD#
0.63
0.31
0.12 #
2.13 #
4.09
<LOD
0.72
<LOD
4.34
6.97
0.63
0.31
0.12#
2.13 #
4.09
<LOD
0.72
<LOD
4.34
6.97

1.86
<LOD
2.02
<LOD
3.46
<LOD
0.52
0.38
0.13 # <LOD#
1.91
<LOD
0.07 #
1.24 #
11.33
<LOD
5.71
<LOD
2.96
<LOD
1.91
<LOD
0.07#
1.36#
11.33
<LOD
5.71
<LOD
2.96
<LOD

0.19
<LOD
2.62
1.97
1.81
0.96
0.34
0.31
0.13# <LOD#
1.97
<LOD
0.05# <LOD#
12.09
<LOD
5.81
<LOD
3.12
<LOD
1.97
<LOD
0.05# <LOD#
12.09
<LOD
5.81
<LOD
3.12
<LOD

0.34
<LOD
<LOD <LOD
<LOD <LOD
<LOD <LOD
<LOD# <LOD#
<LOD <LOD
<LOD# <LOD#
<LOD <LOD
<LOD <LOD
<LOD <LOD
<LOD <LOD
<LOD# <LOD#
<LOD <LOD
<LOD <LOD
<LOD <LOD

27

0.08
<LOD
0.09
<LOD
0.67
0.11
<LOD <LOD
<LOD# <LOD#
<LOD <LOD
<LOD# <LOD#
<LOD <LOD
0.10
43.80
<LOD <LOD
<LOD <LOD
<LOD# <LOD#
<LOD <LOD
0.10
43.80
<LOD <LOD

<LOD 123.80
<LOD <LOD
<LOD <LOD
<LOD <LOD
<LOD# <LOD#
0.03
0.24
<LOD# <LOD#
<LOD <LOD
<LOD <LOD
<LOD <LOD
0.03
0.24
<LOD# <LOD#
<LOD <LOD
<LOD <LOD
<LOD <LOD

<LOD <LOD
<LOD <LOD
<LOD <LOD
<LOD <LOD
<LOD# <LOD#
<LOD <LOD
<LOD# <LOD#
<LOD <LOD
<LOD <LOD
<LOD <LOD
<LOD <LOD
<LOD# <LOD#
<LOD <LOD
<LOD <LOD
<LOD <LOD

7.00
6.00
5.00
4.00

3.00

2.00
1.00
0.00

24
12.00
10.00
8.00
6.00

4.00
2.00
0.00

25

28

 10 (ppm)

1
n=5

2
n=5

3
n=5

2.14
2.67
<LOD
2.18
<LOD
<LOD
<LOD
0.79
4.44
<LOD
0.94
0.18
<LOD
<LOD
<LOD#
0.43 #
0.73 #
0.21 #
<LOD# <LOD# <LOD#
<LOD
1.95
<LOD
1.87
<LOD
<LOD
<LOD
<LOD
8.26
1.17
6.14
79.30
<LOD
<LOD
1.01
0.20
8.43
0.19
<LOD
<LOD
<LOD
1.80
12.14
1.36
1.37
<LOD
<LOD
<LOD
6.27
13.82
0.28
2.06
0.03
<LOD
<LOD
1.15
0.59
<LOD
0.30
<LOD
<LOD
<LOD
0.41#
0.40#
0.99 #
0.10#
<LOD# <LOD# <LOD#
0.31
0.54
0.43
<LOD
<LOD
<LOD
<LOD
3.54
8.34
6.94
<LOD
<LOD
<LOD
<LOD
6.11
1.36
1.11
<LOD
<LOD
<LOD
<LOD
6.54
10.79
6.41
<LOD
<LOD
<LOD
<LOD
0.31#
0.52 #
0.67 #
<LOD# <LOD# <LOD# <LOD#

5.58
2.93
0.41 #
1.15
0.68
0.79
8.20
9.88
1.35
0.48 #
0.51
4.31
6.24
7.01
0.33 #

29

<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD# <LOD# <LOD# <LOD# <LOD# <LOD#
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.07
0.64
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD#
0.25 #
0.02 #
0.39#
<LOD# <LOD#
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD# <LOD# <LOD# <LOD# <LOD# <LOD#

10.00
9.00
8.00
7.00
6.00
5.00

4.00
3.00
2.00
1.00
0.00

26

14.00

12.00

10.00

8.00

6.00

4.00

2.00

0.00

3
1

3
3

27

30

 11

1
n=5

2
n=5

3
n=5

4
n=5

5
n=5

2.05 *
1.78*
1.56*
1.47*
0.16*
0.09*
2.04*
1.93*
<LOD* <LOD* <LOD* <LOD* <LOD* <LOD*
2.13
1.86
1.74
1.65
0.08
0.06
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
1.03
0.76
0.55
0.46
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.94
0.67
0.91
0.82
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.64
0.37
0.34
0.25
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
1.21 *
0.94 *
1.05 *
0.96 *
0.21 *
0.14*
1.05 *
0.89 *
<LOD* <LOD* <LOD* <LOD* <LOD* <LOD*
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
3.12
2.85
2.98
2.89
0.17
0.12
0.94
0.76
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.13
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
4.78*
4.51*
0.16*
0.07 *
1.04*
0.94 *
0.51 *
0.33*
<LOD* <LOD* <LOD* <LOD* <LOD* <LOD*
3.56
3.29
0.18
0.09
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
1.33
1.06
0.33
0.24
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.56
0.29
0.43
0.34
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
1.32
1.05
0.21
0.12
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.12
<LOD
0.13
0.04
0.19
0.11
0.10
0.06
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.31*
0.04*
0.21 *
0.12 *
0.11*
0.09*
0.07 *
0.03 *
<LOD* <LOD* <LOD* <LOD* <LOD* <LOD*
0.11
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.14
<LOD
0.80
0.71
<LOD
<LOD
0.70
0.51
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.45
0.18
0.44
0.35
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
3.13*
2.86*
0.62*
0.53 *
<LOD* <LOD* <LOD* <LOD* <LOD* <LOD* <LOD* <LOD* <LOD* <LOD*
3.15
2.88
0.78
0.69
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.38
0.11
0.16
0.07
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD

31

5.00
4.50
4.00
3.50
3.00
2.50

2.00
1.50
1.00
0.50
0.00

28

3.00

2.50

2.00

1.50

1.00

0.50

0.00

3
1

3
2

29

32

3
5

 12

1
n=5

2
n=5

3
n=5

4
n=5

5
n=5

2.35
0.83
0.81
<LOD
0.56
<LOD
<LOD
<LOD
0.19
0.17
<LOD
<LOD
<LOD
<LOD
0.27
<LOD
0.10
<LOD
0.07
<LOD
<LOD
<LOD
<LOD
<LOD
0.21
0.18
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.33
0.28
0.07
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
2.21
2.04
3.49
2.87
1.84
1.79
3.09
2.84
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
2.08
2.00
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.16
0.06
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.35
0.33
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.31
0.30
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
6.34
5.94
1.53
<LOD
1.17
1.02
3.06
2.94
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
5.28
5.11
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.61
0.34
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.33
0.33
2.01
1.34
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.46
0.39
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
1.18
1.11
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
10.73
8.36
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.15
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
1.37
1.01
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
3.34
3.01
0.10
0.37
0.13
0.14
0.16
0.09
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
1.62
1.35
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.12
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.22
0.13
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.41
0.34
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD

33

6
n=5

7
n=5

8
n=5

9
n=5

10
n=5

0.13
0.08
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.31
0.40
0.19
0.07
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
8.94
6.98
1.79
1.49
<LOD
<LOD
2.79
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
1.74
1.46
<LOD
<LOD
<LOD
<LOD
0.31
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
32.79
30.18
64.47
60.24
<LOD
<LOD
26.53
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
75.11
60.34
28.36
26.79
<LOD
<LOD
60.09
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
5.33
3.87
4.01
3.61
<LOD
<LOD
3.22
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.43
0.38
3.16
3.11
4.74
4.61
36.43
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
3.52
3.16
6.34
5.94
6.79
5.67
21.09
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
2.93
2.59
4.64
4.13
4.50
4.12
1.65
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
8.95
7.89
11.94
10.46
4.99
4.52
44.87
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.21
0.17
0.74
0.73
4.61
3.89
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
58.73
55.97
<LOD
<LOD
24.73
10.00
<LOD
<LOD
<LOD
<LOD
2.94
<LOD
<LOD
<LOD
30.95
28.73
<LOD
<LOD
9.46
8.16
<LOD
<LOD
<LOD
<LOD
1.84
<LOD
<LOD
<LOD
48.24
46.31
<LOD
<LOD
6.76
6.54
<LOD
<LOD
<LOD
<LOD
3.75
<LOD
<LOD
<LOD
2.97
1.94
22.79
18.97
1.90
1.88
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
5.53
4.68
<LOD
<LOD
0.89
0.90
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
4.57
4.13
<LOD
<LOD
2.39
1.46
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
3.95
3.55
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.78
0.65
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.62
0.49
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
0.55
0.51
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD

34

12.00

10.00

8.00

6.00

4.00

2.00

0.00

1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5
1

10

30

80.00
70.00
60.00
50.00
40.00

30.00
20.00
10.00
0.00

3
9

31

35

12.00

10.00

8.00

6.00

4.00

2.00

0.00

1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5
1

10

32

70.00
60.00
50.00
40.00

30.00

20.00
10.00
0.00

33

36

 13 (ppm)

2.0
9
3.4
8
1.2
2
6.7
5

1.79

3.46

0.20

3.41

0.22

0.02

<LOD

0.07

5.85

<LOD

8.29

<LOD

<LOD

1.61

4.80

1.60

1.16

0.05

<LOD

<LOD

<LOD

0.06

<LOD

0.03

<LOD

<LOD

1.02

0.54

0.47

0.08

0.06

0.22

0.18

<LOD

<LOD

<LOD

<LOD

<LOD

<LOD

5.95

3.13

2.80

1.51

1.09

4.07

0.12

<LOD

<LOD

0.17

<LOD

<LOD

<LOD

7.00
6.00
5.00
4.00

3.00
2.00
1.00
0.00

34
37

5.00
4.50
4.00
3.50
3.00

2.50

2.00
1.50
1.00
0.50
0.00

35
5 4
1

2.09 ppm
3.48 ppm 1.22 ppm 6.75
ppm 3.46 ppm 4.80
ppm 0.18 ppm 3.13 ppm
1.79 ppm 1.61 ppm
1.02 ppm 5.95 ppm
0.6 ppm 1.60 ppm
0.47 ppm 1.80 ppm

38

0.995

6.75ppm 3.48ppm 2.09ppm

1.22ppm

1.

2.

39


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42