12
! ! / !"#$%&' Johnson Mathew* US EPA Region 6 Houston Laboratory 10625 Fallstone Road Houston, TX 77099 Jay Gandhi Metrohm-Peak, Inc. 12521 Gulf Freeway Houston, TX 77034 Joe Hedrick Agilent Technologies, Inc. 2850 Centerville Rd. Wilmington, DE 19808 !"#$%&'/ ! (IC/MS) ppb !"#$%& IC/MS !" EPA 314 ! ! IC !"#$!" 1 ppbIC/MS !"#$%&'()314!"#$%&'() !" !"#$%& 0.5 1 ppb !"#$% 90%-105%!" (DML) 100 ppt !"#$%&'()*+,-./012304 !"#$ (CA) !"#$%&'( !" !"#$%&'( !"#$% ! ! !"#$%&'()*+ !"#$%&'()*+,-./0 IC !"#$"%&'()'*+,-./01 EPA 314 !"#$% 1-5 ppb !"!"#$%&'(!"#$ !"#$%& !"#$%&'() !"#$%& !"#$%&'(&)*+ EPA!"#$%&'()1-2 ppb!"# !"#$%&' (DL) !"#$% !"#$%&' !"#$%&'()*+,-./&'(0(50- 100 ppt)!"#$%&'() (ESI) !" !"#$%& !"#$%&' !"#!"#$%&'()*+,-

 · 2 4 6 8 10 12 14 16 min 8000 10000 12000 14000 16000 18000 MSD1 TIC, MS File (ICDATA~1\ICBLK1D\IC000045.D) API-ES, Neg, SIM, Frag: 140, "neg sim" MSD1 TIC, …

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Page 1:  · 2 4 6 8 10 12 14 16 min 8000 10000 12000 14000 16000 18000 MSD1 TIC, MS File (ICDATA~1\ICBLK1D\IC000045.D) API-ES, Neg, SIM, Frag: 140, "neg sim" MSD1 TIC, …

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Johnson Mathew*

US EPA Region 6

Houston Laboratory

10625 Fallstone Road

Houston, TX 77099

Jay Gandhi

Metrohm-Peak, Inc.

12521 Gulf Freeway

Houston, TX 77034

Joe Hedrick

Agilent Technologies, Inc.

2850 Centerville Rd.

Wilmington, DE 19808

��

�� !"#$%&'/�� ! (IC/MS) �� ppb��

�� !"#$%&IC/MS�� !"EPA��314�� !

���� ! IC�� !"#$�� !" 1� ppb�IC/MS

�� !"#$%&'()��314�� !"#$%&'()

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EPA�� !"#$%&'()1-2 ppb�� !"#

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Page 2:  · 2 4 6 8 10 12 14 16 min 8000 10000 12000 14000 16000 18000 MSD1 TIC, MS File (ICDATA~1\ICBLK1D\IC000045.D) API-ES, Neg, SIM, Frag: 140, "neg sim" MSD1 TIC, …

2

�� !"#$ !%&'�� !"#$m/z (99�

101) �� !"#$%&'()�� !"#$%&

�� !�� !"#$%&'()*+�� ��

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���� !"#$%API�� !"#$%�&'(

�� !"�� !"#$%&�� !"#$%&'

IC�� !1100 MSD�� !"#$%&integral�

�� �� !"#$ESI���� !"#$% &

�� !"#$%&'()*+�,-./0123

�� !"#$%&�� !"#$%&'(MS��

�� !"#�� !"#$%&'()�� !"#

���� !"#$%NaOH �� !"#$%&'

�� !"#$

�� !"#$%&'() (Metrohm-Peak ��) �

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�4-mm�� !"#$2-mm�� !�� !"#

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�� !"#�� !"#$%&'()*+

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� 1. �� !

Metrohm �� IC�� !" 100 L

�� MetroSep ASUPP-5 (4 mm x 100 mm)

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�� 0.8 mL/min

Agilent 1100 MSD�� ! �� !" �� !"#

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�� !"#$%& 9 L/min @ 320�

�� !" 20 psig

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Dwell �� m/z 99 1 s

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Metrohm�� !"#$%��Metrohm 788�� !"#� ICNet2.3�� 830�� 833�� !"#819�� IC�� !820 IC��� !818 IC�� !"#

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Page 3:  · 2 4 6 8 10 12 14 16 min 8000 10000 12000 14000 16000 18000 MSD1 TIC, MS File (ICDATA~1\ICBLK1D\IC000045.D) API-ES, Neg, SIM, Frag: 140, "neg sim" MSD1 TIC, …

3

m/z 99

m/z 101

min2 4 6 8 10 12 14 16

2000

3000

4000

5000

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MSD1 99, EIC=98.7:99.7 (ICDATA~1\ICBLK1D\IC000017.D) API-ES, Neg, SIM, Frag: 140, "neg sim"

MSD1 101, EIC=100.7:101.7 (ICDATA~1\ICBLK1D\IC000017.D) API-ES, Neg, SIM, Frag: 140, "neg sim"

�� !"#$%&�'()*+�� !"#$%

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Page 4:  · 2 4 6 8 10 12 14 16 min 8000 10000 12000 14000 16000 18000 MSD1 TIC, MS File (ICDATA~1\ICBLK1D\IC000045.D) API-ES, Neg, SIM, Frag: 140, "neg sim" MSD1 TIC, …

min2 4 6 8 10 12 14 160

2000

4000

6000

8000

10000

12000

MSD1 99, EIC=98.7:99.7 (ICDATA~1\ICBLK1D\IC000048.D) API-ES, Neg, SIM, Frag: 140, "neg sim"

MSD1 101, EIC=100.7:101.7 (ICDATA~1\ICBLK1D\IC000048.D) API-ES, Neg, SIM, Frag: 140, "neg sim"

m/z 99

m/z 101

�� !"#$%&'�� !"#$%&'()*

�� !�2�� 1000-ppm�� !�� !��

�� ! 1-ppb�� !"m/z 99� 101�� !�

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�� !"�� !"#$%&'()9�� !"#

�� !"#$%&'()*+,-./01��

�� !" 13�� !"#$%&'()*+

� 2. �� Cl _, CO3

-2, SO4-2 � 1000 ppm� 1-ppb�� ! (m/z 99 and 101) �� !"#$%

4

Page 5:  · 2 4 6 8 10 12 14 16 min 8000 10000 12000 14000 16000 18000 MSD1 TIC, MS File (ICDATA~1\ICBLK1D\IC000045.D) API-ES, Neg, SIM, Frag: 140, "neg sim" MSD1 TIC, …

Amount (ng/mL)

0 1

Area

0

50000

100000

150000

200000

Perchlorate 99, MSD1 101

Correlation: 0.99874

Rel. Res% (4): _3.377

Area = 44472.7433*Amt -1931.1962

2 3 54

Amount (ng/mL)

0 1

Area

0

100000

200000

300000

400000

500000

600000

700000Perchlorate 101, MSD1 99

Correlation: 0.99942

Rel. Res % (3): 1.9387e-2

Area = 143840.996* Amt -2810.7345

2 3 4 5

5

� 3 � 4�� 0.1 � 5 ppb�� m/z 99 � 101 �

�� !"�� !"#$%&'()*+,-

� 3. �� ! (m/z 99)�

� 4. �� ! (m/z 101)�

�� !"# 0.1 ppb �5 ppb (ClO4

_)

�� !"# 0.1 ppb �5 ppb (ClO4

_)

Page 6:  · 2 4 6 8 10 12 14 16 min 8000 10000 12000 14000 16000 18000 MSD1 TIC, MS File (ICDATA~1\ICBLK1D\IC000045.D) API-ES, Neg, SIM, Frag: 140, "neg sim" MSD1 TIC, …

min2 4 6 8 10 12 14 16

8000

10000

12000

14000

16000

18000

MSD1 TIC, MS File (ICDATA~1\ICBLK1D\IC000045.D) API-ES, Neg, SIM, Frag: 140, "neg sim"

MSD1 TIC, MS File (ICDATA~1\ICBLK1D\IC000046.D) API-ES, Neg, SIM, Frag: 140, "neg sim"

MSD1 TIC, MS File (ICDATA~1\ICBLK1D\IC000047.D) API-ES, Neg, SIM, Frag: 140, "neg sim"

MSD1 TIC, MS File (ICDATA~1\ICBLK1D\IC000048.D) API-ES, Neg, SIM, Frag: 140, "neg sim"

No interferents200 ppm Cl

_, CO3

_2, SO4

_2

500 ppm Cl_, CO3

_2, SO4

_2

1000 ppm Cl_, CO3

_2, SO4

_2

� 5�� ! 1-ppb�� !"#$%&'"m/z 99

�� !"#$�� !"#$%&'()*+,-

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6

Page 7:  · 2 4 6 8 10 12 14 16 min 8000 10000 12000 14000 16000 18000 MSD1 TIC, MS File (ICDATA~1\ICBLK1D\IC000045.D) API-ES, Neg, SIM, Frag: 140, "neg sim" MSD1 TIC, …

7

� 3�� !"#$%&' 0.49� 0.78 ppb�� !

�� !"#$%�� !"#$%&'()*+,

�� !"#$%&�� !"#$%&'()*+,

� 3. � 0.48 � 0.78 ppb�� !"#$%&'(

Nominal �� ! �� !�� ID �� ! ppb �� % ppb �� %ppb ppb m/z 99 m/z 99 m/z 101 m/z 101

0.5 0.480 0.487 101.46 0.519 108.130.5 0.480 0.477 99.38 0.471 98.130.5 0.480 0.460 95.83 0.490 102.080.5 0.480 0.477 99.38 0.492 102.500.5 0.480 0.520 108.33 0.505 105.210.5 0.480 0.494 102.92 0.509 106.04

�� 0.480 0.486 101.22% 0.498 103.68%

�� ! 0.020 0.042 0.017 0.035

RSD (%) 4.18 4.18 3.41 3.41

Nominal �� ! �� !�� ID �� ! ppb �� % ppb �� %ppb ppb m/z 99 m/z 99 m/z 101 m/z 101

1.0 0.780 0.756 96.92 0.768 98.461.0 0.780 0.810 103.85 0.830 106.411.0 0.780 0.776 99.49 0.772 98.971.0 0.780 0.799 102.44 0.754 96.671.0 0.780 0.788 101.03 0.768 98.461.0 0.780 0.792 101.54 0.807 103.46

�� 0.780 0.787 100.88% 0.783 100.41%

�� ! 0.019 0.024 0.029 0.037

RSD (%) 2.40 2.40 3.70 3.70

0.78 ppb�� !

0.48 ppb�� !

Page 8:  · 2 4 6 8 10 12 14 16 min 8000 10000 12000 14000 16000 18000 MSD1 TIC, MS File (ICDATA~1\ICBLK1D\IC000045.D) API-ES, Neg, SIM, Frag: 140, "neg sim" MSD1 TIC, …

� 4�� !"#$%&'()*+� 1-ppb��

EPA��314�� !"#$%&'()*+,-.�

9�� !"#�� !"#$%&'(�� !"#$

�� !" ppb�� !"#$%&'(�� !"

�� !"#$%&'()*+, 95%��� !"

�� !"#$%&'()*+,-./0123/

�� !

�� !

�� ! �� !�� ! ppb �� % ppb �� %

�� ppb m/z 99 m/z 99 m/z 101 m/z 101200 ppm each of Cl

_, CO3

-2 and SO4-2 0.780 0.799 102.44 0.784 100.51

500 ppm each of Cl_, CO3

-2 and SO4-2 1.000 0.804 80.40 0.808 80.80

1000 ppm each of Cl_, CO3

-2 and SO4-2 1.000 0.930 93.00 0.940 94.00

200 ppm each of Cl_, CO3

-2 and SO4-2 0.780 0.700 89.74 0.770 98.72

500 ppm each of Cl_, CO3

-2 and SO4-2 1.000 0.870 87.00 0.860 86.00

1000 ppm each of Cl_, CO3

-2 and SO4-2 1.000 0.973 97.30 0.986 98.60

200 ppm each of Cl_, CO3

-2 and SO4-2 0.780 0.810 103.85 0.796 102.05

500 ppm each of Cl_, CO3

-2 and SO4-2 1.000 0.851 85.10 0.846 84.60

1000 ppm each of Cl_, CO3

-2 and SO4-2 1.000 0.990 99.00 0.977 97.70

�� 0.000 0.000 0.000

CC 1.0 ppb (No interferents) 0.780 0.747 95.77 0.742 95.13

200 ppm each of Cl_, CO3

-2 and SO4-2 0.780 0.799 102.44 0.777 99.62

500 ppm each of Cl_, CO3

-2 and SO4-2 1.000 0.920 92.00 0.921 92.10

1000 ppm each of Cl_, CO3

-2 and SO4-2 1.000 1.000 100.00 1.040 104.00

200 ppm each of Cl_, CO3

-2 and SO4-2 0.780 0.860 110.26 0.830 106.41

500 ppm each of Cl_, CO3

-2 and SO4-2 1.000 0.930 93.00 0.913 91.30

1000 ppm each of Cl_, CO3

-2 and SO4-2 1.000 1.090 109.00 1.050 105.00

200 ppm each of Cl_, CO3

-2 and SO4-2 0.780 0.800 102.56 0.850 108.97

500 ppm each of Cl_, CO3

-2 and SO4-2 1.000 0.890 89.00 0.904 90.40

1000 ppm each of Cl_, CO3

-2 and SO4-2 1.000 1.040 104.00 1.070 107.00

�� (%) 96.67 97.10

�� ! 0.082 0.080

RSD (%) 8.48 8.22

� 4. �� !"#$%&'()*+,-

8

Page 9:  · 2 4 6 8 10 12 14 16 min 8000 10000 12000 14000 16000 18000 MSD1 TIC, MS File (ICDATA~1\ICBLK1D\IC000045.D) API-ES, Neg, SIM, Frag: 140, "neg sim" MSD1 TIC, …

9

�5�� !"#$%&'()*+,-./0��

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�� ! �� !�� �� ! ppb �� % ppb �� %ID ppb m/z 99 m/z 99 m/z 101 m/z 101�� ��

�� 1 0.50 0.44 88.00 0.51 102.0 �� !"# 0.5 ppb

�� 2 1.00 0.91 91.00 1.01 100.7 �� !"# 1.0 ppb

�� 3 1.00 0.95 95.16 1.00 99.7 �� !"# 1.0 ppb

�� 4 0.42 0.41 97.33 0.43 102.1 �� w/0.42 ppb

�� 5 ? 0.00 0.00 �� !�� !"#�� !"#$%

�� 6 0.35 0.30 86.93 0.33 95.0 �� w/0.35 ppb

�� 6A 1.35 1.18 87.41 1.36 100.6 Sx-6 + 1 ppb

�� 7 0.00 0.00 100.00 0.00 100.0 �� w/�� !"

�� 8 0.00 0.00 0 0.00 �� !"

�� 9 7.92 7.35 92.86 7.41 93.6 �� !"#$%

Page 10:  · 2 4 6 8 10 12 14 16 min 8000 10000 12000 14000 16000 18000 MSD1 TIC, MS File (ICDATA~1\ICBLK1D\IC000045.D) API-ES, Neg, SIM, Frag: 140, "neg sim" MSD1 TIC, …

10

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35000 MSD1 TIC, MS File (ICDATA~1\ICBLK1E\IC000037.D) API-ES, Neg, SIM, Frag: 140, "neg sim"

MSD1 TIC, MS File (ICDATA~1\ICBLK1E\IC000039.D) API-ES, Neg, SIM, Frag: 140, "neg sim"

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Page 11:  · 2 4 6 8 10 12 14 16 min 8000 10000 12000 14000 16000 18000 MSD1 TIC, MS File (ICDATA~1\ICBLK1D\IC000045.D) API-ES, Neg, SIM, Frag: 140, "neg sim" MSD1 TIC, …

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MSD1 TIC, MS File (ICDATA~1\ICBLK1E\IC000052.D) API-ES, Neg, SIM, Frag: 140, "neg sim"

MSD1 TIC, MS File (ICDATA~1\ICBLK1E\IC000053.D) API-ES, Neg, SIM, Frag: 140, "neg sim"

�7�� !"#$%&'()*+�� !"#$%

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Page 12:  · 2 4 6 8 10 12 14 16 min 8000 10000 12000 14000 16000 18000 MSD1 TIC, MS File (ICDATA~1\ICBLK1D\IC000045.D) API-ES, Neg, SIM, Frag: 140, "neg sim" MSD1 TIC, …

www.agilent.com/chem

�� !"#$%&'()*+,-.�� !"�� !"#$%&'()*+,-./

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2004 � 5 � 28 �

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1. EPA METHOD 314.0, "Determination of Per-chlorate in Drinking Water Using Ion Chro-matography", Revision 1.0. November 1999,US EPA, Office of Ground Water and Drink-ing Water, publication 815-B-99-003http://www.epa.gov/ogwdw/methods/met314.pdf

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