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3

Sensitivity

Based on the Japanese Water Quality Standards Ordinance,

the method needs to be able to detect three regulated

haloacetic acids at concentration levels ten times lower than

the regulated amounts. Among the three haloacetic acids,

the compound MCAA has lowest regulated amount at

20 µg/L. The HAA column method was able to confirm all

three haloacetic acids at the 2 µg/L level, which is ten times

lower than 20 µg/L (Figures 3 and 4).

1

0

2

4

6

8

10

12

14

16

18

20

22

24

26

28

30

Time (min)

2

3

a

b

c

d

RT:

5.21 - 9.40

SM:

7G

6 7 8 9

Time (min)

0

20

40

60

80

100

Relative Abundance

RT: 7.30

SN: 23

NL:

2.42E3

TIC F: - c ESI

SRM ms2

93.000

[34.999-35.001]

MS Genesis

25Jun005

RT:

12.63 - 16.82

SM:

7G

14

16

Time (min)

0

20

40

60

80

100

Relative Abundance

RT: 14.83

SN: 133

NL:

1.31E5

TIC F: - c ESI

SRM ms2

127.000

[82.999-83.001]

MS Genesis

25Jun005

RT:

18.23 - 22.41

SM:

7G

20

22

Time (min)

0

20

40

60

80

100

Relative Abundance

RT: 20.36

SN: 496

NL:

1.49E5

TIC F: - c ESI

SRM ms2

161.000

[116.999-

117.001] MS

Genesis

25Jun005

a)

b)

c)

Figure 3. SRM chromatograms for 2 µg/L standard solution: a) MCAA, b) DCAA, c) TCAA

Figure 4. SRM chromatograms for tap water spiked with 2 µg/L standard solution: a) MCAA, b) DCAA, c) TCAA

*A peak from contaminant compound sources was detected before the peak in monochloroacetic acid. The identity of this

contaminant as a chloride ion cluster ion (NaCl

2

- ) was confirmed using a Thermo Scientific accurate-mass MS.

RT:

5.21 - 9.40

SM:

7G

6

7

8

9

Time (min)

0

20

40

60

80

100

Relative Abundance

RT: 7.20

SN: 14

6.07

8.82

NL:

2.69E3

TIC F: - c ESI

SRM ms2

93.000

[34.999-

35.001] MS

25Jun046

RT:

12.63 - 16.82

SM:

7G

14

16

Time (min)

0

20

40

60

80

100

Relative Abundance

RT: 14.76

SN: 482

NL:

2.68E5

TIC F: - c ESI

SRM ms2

127.000

[82.999-83.001]

MS Genesis

25Jun046

RT:

18.23 - 22.41

SM:

7G

20

22

Time (min)

0

20

40

60

80

100

Relative Abundance

RT: 20.19

SN: 807

NL:

2.92E5

TIC F: - c ESI

SRM ms2

161.000

[116.999-

117.001] MS

Genesis

25Jun046

Figure 2. Separation on the Acclaim HAA column. Upper section: Haloacetic acids 1: Monochloroacetic acid

(MCAA), 2: Dichloroacetic acid (DCAA), 3: Trichloroacetic acid (TCAA). Lower section: Matrix components

a: Ascorbic acid, b: Chloride, c: Nitrate, d: Sulfate