3/13/2012

Analysis of Major Ions in Water Sample using Ion Chromatography

By: Tenzin Lhundup

3/13/2012 Introduction: Ion exchange Chromatography or Ion Chromatography (IC) can be describe as method in which ions are separated based on ion exchanged affinity differences of each analyte. Further, the process takes advantage of reaction of ions is solution to its oppositely charged columns. It is is widely used to analyze for major anion, cations and trace elements in aqueous samples such as drinking water, rivers, effluents and rain water. IC can also be used to analysis for ions in chemical products, food, cosmetics, and for trace ions in power industries. It is possible to use other modes of ion quantification via implementing principle of ion pair formation and ion exclusion. In the laboratory exercise, IC machine located at Queen College will be used to prepare standard calibration and use water sample for random sources to analyze for major ion such as Nitrite, Nitrate, Sulfate, Phosphate, Chloride, Fluoride, and Bromide. Difference between ion concentration using peak area and peak height were compared. Apparatus Ion Chromatography DIONEX-500 IC system was used to perform this laboratory analysis. Method Followed the standard protocol set forth by EPA and method 300 for sample preparation. Standard factory calibration kit was use to set the ion standards. Four standard trials were run with different dilution factor of 20x 10x, 4x and 2x. Six samples from random sources such as Sands point, local tap water, Hudson river, fish tanks and a unknown source was used to determine the major ions. Data: Table 1 to Table 7 shows the standard concentration used to obtain the peak area and peak height for each major ions. Two standard calibration curves were constructed for each ion by comparing standard concentration verses the peak height and the standard concentration verses the peak area. Figure 1 to 14 provides the graphical representation of the calibration curve with liner regression line. Ion concentration in each sample source was calculated by using slope of the regression line for each analyte from peak area and peak height value. Concentration of each major ions derived by using the peak area as well as peak height for each sample are presented in table 8. Analysis: With exception of Nitrate and Nitrite, the least square value for Phosphate, Sulfate, Fluoride, Bromide and Chlorides standard verses peak area calibration curve and standard verses peak height calibration curve remain relatively close to desired value of one. This may have been due to error during preparation of calibration standard.

3/13/2012 The ion concentration derived using IC peak area and IC peak height are consistently similar for Fluoride, Chloride, Bromide, Sulfate, and Phosphate. The differences in concerentraion are between 0.5 ppm to 1ppm. However, we observed large difference in ion concentration between Nitrate and Nitrite. Concentration derived from using the IC peak height are exponentially lower than concentration derived from IC peak area. Conclusion: In future, one way to have higher confidence in ion concentration is by adding internal control in each sample. This can be done by adding know amount of any of the major ions to determine the predicted ion concentration in additional to unknown concentration in sample. In additional, further improvement can be made on setting the standards calibration prior to the actual analysis.

Acknowledgment: Queens College EESs graduate student, Kale Clauson and classmate David Jakim was responsible for setting the standards calibration as well as preparing water samples for the anlaysis. David will be using the IC more regularly for this research project. Without their effort, this laboratory report would have been possible.

Table 1: Fluoride Standard value vs IC Peak Area and Peak Height Sample Name: 1.000 2.000 3.000 4.000 Standard mg/l 8 15 30 75 Fluoride Peak Fluoride Peak Area (uS) Height: 116,955.50 235,333.00 594,179.50 1,301,406.00 14,671.60 31,891.40 80,069.91 176,920.41

Figure1: Fluoride Standard Curve (Peak Area and Peak Height)

1,400,000.0
1,200,000.0
y = 17572x + 1846 R = 0.993

Flouride Peak Area

1,000,000.0 800,000.0 600,000.0 400,000.0 200,000.0

0.0

0
Fluoride Peak Area (uS)

10

20

30

40

50

60

70

80

Fluoride standard (mg/l)

Figure 2:Fluoride Standar Curve (Peak Height vs Standard):

200,000 180,000 160,000
Flouride Peak Height y = 2400.x - 641.0 R = 0.993

140,000 120,000 100,000

80,000

60,000 40,000
20,000

0 0
Fluoride Peak Height:

10

20

30

40
Standard (mg/l)

50

60

70

80

Table 2: Chloride Standard value vs IC Peak Area and Peak Height Sample Name: Standard mg/l 1.000 2.000 3.000 4.000 2.5 5.0 12.5 25.0 Chloride Peak Chloride Peak Area: Height: 185,374.00 399,144.00 1,017,192.00 2,332,309.50 20,373.87 44,038.50 116,293.72 272,438.09

Figure 3: Chloride Standard Curve (Peak Area vs Standard)

2,500,000.00 y = 95426x - 90033 R = 0.996 2,000,000.00 Chloride Peak Area

1,500,000.00

1,000,000.00

500,000.00

0.00 0.0
Chloride Peak Area:

5.0

10.0

15.0

20.0

25.0

30.0

Standard (mg/l)

Figure 4:Chloride Standard Curve (Peak Height vs Standard) 300,000.00 250,000.00 Chloride Peak Height 200,000.00 150,000.00 100,000.00 50,000.00 0.00 0.0
Chloride Peak Height:

y = 11226x - 13003 R = 0.995

5.0

10.0

15.0 Standard (mg/l)

20.0

25.0

30.0

Table 3: Nitrite Standard value vs IC Peak Area and Peak Height Sample Name: 1.000 2.000 3.000 4.000 Diluted standard mg/l 1.25 2.50 7.25 12.50 Nitrite Peak Area: 195,310.25 419,971.00 1,067,940.50 2,368,007.19 Nitrite Peak Height: 16,957.33 36,979.32 94,062.94 206,986.45

Figure 5: Nitrite Standard Curve (Peak Area vs Standard):

2,500,000

y = 18884x - 96629 R = 0.979 2,000,000

Nitrite Peak Area

1,500,000

1,000,000

500,000

0
Nitrite Peak Area:

6 8 Standard (mg/l)

10

12

14

Figure 6: Nitrite Standard Curve (Peak Height vs Standard):

250,000 y = 16514x - 8273. R = 0.980 Nitrite Peak Height 200,000

150,000

100,000

50,000

0
Nitrite Peak Height:

10

12

14

Standard (mg/l)

Table 4: Bromide Standard value vs IC Peak Area and Peak Height Sample Name: Standard mg/l 1 2 3 4 5 10 20 50 Bromide Peak Area: 156,632.50 337,505.25 864,005.50 1,938,199.94 Bromide Peak Height: 12,305.75 26,697.02 67,901.12 155,420.29

Figure 7: Bromide Standard Curve (Peak Area vs standard):

2,500,000 2,000,000
Bromide Peak Area

y = 39632x - 18086 R = 0.994

1,500,000
1,000,000

500,000 0
0 10 20 30 40 50 60

Bromide Peak Area:

Standard (mg/l)

Figure 8: Bromide Standard Curve (Peak Height vs Standard):

180,000 160,000 Bromide Peak Height 140,000 120,000 100,000 80,000 60,000 40,000 20,000 0 0
Bromide Peak Height:

y = 3186.x - 2125. R = 0.995

10

20

30

40

50

60

Standard (mg/l)

Table 5: Nitrate Standard value vs Peak Area and Height Sample Name: Standard mg/l 1 2 3 4 1.25 2.50 7.25 12.50 Nitrate Peak Area: 223,729.25 481,867.50 1,224,336.75 2,788,015.96 Nitrate Peak Height: 15,162.70 33,094.12 83,345.48 182,955.32

Figure 9: Nitrate Standard Curve (Peak Area vs Standard)

3,000,000
2,500,000

y = 22266x - 12866 R = 0.976

Nitrate Peak Area

2,000,000 1,500,000 1,000,000 500,000 0 0 2 4 6 8 10 12 14

Nitrate Peak Area:

Standard (mg/l)

Figure 10: Nitrate Standard Curve (Peak Height vs Standard)

200,000 180,000 Nitrate Peak Height
160,000

y = 14573x - 6974. R = 0.980

140,000 120,000
100,000

80,000 60,000 40,000 20,000

0

0.00
Nitrate Peak Height:

2.00

4.00

6.00

8.00

10.00

12.00

14.00

Standard (mg/l)

Table 6: Phosphate Standard value vs IC Peak Area and Peak Height Sample Name: Standard mg/l 1 2 3 4 7.5 15 30 75 Phosphate Peak Area: 146,919.00 328,050.25 815,393.75 1,835,111.25 Phosphate Peak Height: 6,733.03 15,058.54 38,175.61 87,266.73

Figure 11: Phosphate stadard curve (Peak Area vs Standard)

2,000,000 1,800,000 Phosphate Peak Area 1,600,000 1,400,000
1,200,000

y = 24978x - 14793 R = 0.994

1,000,000 800,000 600,000 400,000

200,000

0
0.0
Phosphate Peak Area:

20.0

40.0 Standard (mg/l)

60.0

80.0

Figure 12: Phosphate Standard Curve (Peak Height vs standard)

100,000
90,000

Phosphate Peak Height

80,000 70,000
60,000

y = 1193.x - 1243. R = 0.995

50,000 40,000 30,000 20,000

10,000

0 0
Phosphate Peak Height:

10

20

30

40 Standard (mg/l)

50

60

70

80

Table 7: Sulfate Standard value vs IC Peak Area and Peak Height Sample Name: Standard mg/l 1 2 3 4 7.5 15 30 75 Sulfate Peak Area: 403,005.50 885,766.50 2,267,635.50 5,143,215.50 Sulfate Peak Height: 17,091.13 37,821.65 99,226.73 231,630.68

Figure 13: Sulfate standard curve (Peak Area vs Standard)

6,000,000 5,000,000

y = 70301x - 65942 R = 0.995

Sulfate peak area

4,000,000 3,000,000 2,000,000

1,000,000 0

0
Sulfate Peak Area:

20

40

60

80

Standard (mg/l)

Figure 14: Sulfate Standard Curve (Peak Height vs Stndard)

250,000 y = 3190.x - 5245. R = 0.996 Sulfate Peak Height 200,000

150,000

100,000

50,000

0 0
Sulfate Peak Height:

20

40 Standard (mg/l)

60

80

Table 8: Comparison of Ion Concentration Derived from IC Peak Area and Peak Height Sample Name: 5 Sands Point 6 David's Tap Wat. 7 Erin's Fish Tank 8 Sarah's Tap 9 Hudson River 10 Unknown sample Concentration (mg/l) 0.769 0.233 7.119 6.004 0.898 11.272 Fluoride Peak Area (uS) 13,506.50 4,100.25 125,088.25 105,506.75 15,780.07 198,070.75 Concentration (mg/l) 0.66 0.26 6.75 5.55 0.24 10.83 Fluoride Peak Height: 1,583.76 620.07 16,203.79 13,308.45 568.02 25,989.24

Sample Name: 5 Sands Point 6 David's Tap Wat. 7 Erin's Fish Tank 8 Sarah's Tap 9 Hudson River 10 Unknown sample

Concentration (mg/l) 15.26 41.52 9.83 7.54 2.97 3.50

Chloride Peak Area: 1,456,063.50 3,962,364.50 938,218.50 719,158.25 283,645.75 333,885.00

Concentration (mg/l) 15.03 41.68 9.49 7.22 2.76 3.20

Chloride Peak Height: 168,727.37 467,905.17 106,543.50 81,024.23 31,029.80 35,881.95

Sample Name: 5 Sands Point 6 David's Tap Wat. 7 Erin's Fish Tank 8 Sarah's Tap 9 Hudson River 10 Unknown sample ND = Not Detected Sample Name: 5 Sands Point 6 David's Tap Wat. 7 Erin's Fish Tank 8 Sarah's Tap 9 Hudson River 10 Unknown sample ND = Not Detected Sample Name: 5 Sands Point 6 David's Tap Wat. 7 Erin's Fish Tank 8 Sarah's Tap 9 Hudson River 10 Unknown sample

Concentration (mg/l) ND ND 2.47 ND ND 18.27

Nitrite Peak Area: ND ND 46,626.50 ND ND 344,997.00

Concentration (mg/l) ND ND 0.25 ND ND 1.81

Nitrite Peak Height: ND ND 4,085.82 ND ND 29,875.57

Concentration (mg/l) ND ND ND ND ND 7.23

Bromide Peak Area: ND ND ND ND ND 285,752.20

Concentration (mg/l) ND ND ND ND ND 6.87

Bromide Peak Height: ND ND ND ND ND 21,874.80

Concentration (mg/l) 11.83 42.80 32.12 1.67 0.61 17.95

Nitrate Peak Area: 263,335.50 952,920.75 715,275.50 37,192.00 13,542.25 399,628.53

Concentration (mg/l) 1.16 4.27 3.35 0.17 0.06 1.88

Nitrate Peak Height: 16,873.67 62,237.33 48,880.22 2,505.80 935.87 27,325.66

Table 8: Comparison of Ion Concentration Derived from IC Peak Area and Peak Height Concentration Phosphate Concentration Phosphate Sample Name: (mg/l) Peak Area: (mg/l) Peak Height: 5 Sands Point ND ND ND ND 6 David's Tap Wat. ND ND ND ND 7 Erin's Fish Tank 3.98 99,469.00 3.86 4,605.38 8 Sarah's Tap 1.77 44,236.00 1.68 2,002.12 9 Hudson River ND ND ND ND 10 Unknown sample 10.84 270,881.25 10.44 12,449.38 ND = Not Detected Sample Name: 5 Sands Point 6 David's Tap Wat. 7 Erin's Fish Tank 8 Sarah's Tap 9 Hudson River 10 Unknown sample Concentration (mg/l) 20.33 21.78 6.22 4.61 1.13 10.43 Sulfate Peak Area: 1,429,335.75 1,531,134.50 437,608.50 324,319.00 79,557.50 732,957.75 Concentration (mg/l) 19.39 20.78 5.80 4.28 1.06 9.73 Sulfate Peak Height: 61,866.87 66,284.11 18,500.15 13,667.67 3,392.29 31,042.15