ESN Presentation

29
Transition of ESN Nitrogen Release Analysis to Rudolph Refractometer Comparison of Controlled Release Profile of ESN Products using Antek 9000 Nitrogen Analyzer with auto sampler and Rudolph Refractometer J57 with auto sampler.

Transcript of ESN Presentation

Page 1: ESN Presentation

Transition of ESN Nitrogen Release Analysis to Rudolph

RefractometerComparison of Controlled Release Profile of

ESN Products using Antek 9000 Nitrogen Analyzer with auto sampler and Rudolph

Refractometer J57 with auto sampler.

Page 2: ESN Presentation

Study Outline• On May 28, 2013 the CNO Laboratory undertook a study to validate the transition

of the analysis of Control Release Profile (CRP) of ESN products (ESN, ESN Blue & Poly-R) from the Antek Nitrogen Analyzers to the Rudolph Refractometer J57.

• Four sets of samples were chosen for analysis: a recent ESN Daily Composite (May 24), an ESN Blue Daily Composite (December 2012), a Poly-R composite (March 2013) & the CNO Lab’s ESN Check (November 2007 production).

• Ten vials of each material were prepared, incubated at 23oC & tested weekly until 80% release of nitrogen was achieved.

• No data was discarded though Day 56 results for ESN Blue & Poly-R by Rudolph were not obtained due to staff shortages.

• Standard deviations between the replicates in each set were calculated & F test applied to determine method equivalency. values obtained from

• Note: The specification data was obtained from AAT Specialist; specifications are the same for all ESN products.

Page 3: ESN Presentation

Data Collected: ESN Composite

DayAntek (ave)

Antek Std Dev

Antek Range

Rudolph (ave)

Rudolph Std Dev

Rudolph Range Delta N2 % Delta F Value Upper Spec Lower Spec

1 2.58 1.17 3.69 3.16 0.80 2.36 0.58 18.35 2.12 20 0

7 12.72 1.94 6.20 11.25 2.10 6.79 1.47 13.07 1.18 20 0

14 23.02 2.74 9.62 19.01 2.66 9.08 4.01 21.09 1.06 20 0

21 30.26 2.78 8.69 24.24 2.52 8.65 6.02 24.83 1.21 20 0

28 36.66 2.86 8.14 33.22 2.40 7.22 3.44 10.36 1.41 20 0

35 42.50 2.70 10.17 38.18 2.97 8.29 4.32 11.31 1.21 40 0

42 48.49 2.55 8.81 47.01 2.44 7.79 1.48 3.15 1.09 60 0

49 55.56 2.86 10.16 53.65 2.39 7.79 1.91 3.56 1.43 80 11.4

56 61.32 2.91 9.97 59.83 2.43 7.15 1.49 2.49 1.43 22.8

63 64.61 2.59 8.30 65.04 2.44 7.50 0.43 0.66 1.13 34.2

70 74.66 3.39 11.87 70.11 2.15 6.65 4.55 6.49 2.48 45.6

77 71.70 3.00 9.37 73.58 1.87 6.22 1.88 2.56 2.56 57

84 72.88 2.42 8.53 76.61 1.81 5.72 3.73 4.87 1.79 68.4

91 77.89 2.37 8.92 77.67 1.51 5.00 0.22 0.28 2.48 80

98 86.12 2.46 8.81 78.82 1.31 4.64 7.30 9.26 3.54

105 81.18 1.29 4.36

Ave 2.58 8.75 Ave 2.07 6.57 2.86 8.82 1.74

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ESN Composite Controlled Release Profile

0 14 28 42 56 70 84 980

2

4

6

8

10

12

AntekRudolph Upper SpecLower Spec

Days

% N

itrog

en

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Std Dev of Data Replicates ESN Composite

0 14 28 42 56 70 84 980.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

Antek Std DevRudolph Std Dev

Days

Page 6: ESN Presentation

Range of Data Replicates ESN Composite

0 14 28 42 56 70 84 980.0

2.0

4.0

6.0

8.0

10.0

12.0

14.0

Antek RangeRudolph Range

Days

Page 7: ESN Presentation

F Value of ESN Composite by Rudolph vs. Antek

0 14 28 42 56 70 84 980.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

F Value of ESN Composite by Rudolph vs. Antek

F Value

Days

Page 8: ESN Presentation

Observations:

• The Controlled Release Profile (CRP) of the ESN Composite as determined by Rudolph RI exhibits a more predictable & reliable increase above 60% as compared to the CRP determined by Antek.

• While the CRP’s of the ESN Composite do not exhibit the desired S-curves (as per AAT specifications) by either method, the results of analysis by Rudolph RI are statistically similar to those determined by Antek analysis.

• Comparison of the standard deviation & range of the replicates in each set shows that the Rudolph method produces less variable data particularly at the higher end of nitrogen release.

• The F Values for Rudolph analysis as compared to Antek analysis all fall below the acceptable equivalence limit of 2.98 with the exception of the last value which reflects an increase in the standard deviation of Antek results as compared to lower SD of Rudolph results.

• The average F Value is 1.74 which is well below the acceptable equivalence limit of 3.18 (at 9 degrees of freedom & 95% confidence level).

Page 9: ESN Presentation

Data Collected: ESN Check

DayAntek

(ave)Antek

Std DevAntek Range

Rudolph (ave)

Rudolph Std Dev

Rudolph Range Delta N2 % Delta F Value Upper Spec Lower Spec

1 1.4 0.58 1.98 1.95 0.88 3.14 0.55 28.21 2.34 20 0

7 5.21 0.78 2.52 5.24 1.14 3.93 0.03 0.57 2.14 20 0

14 9.15 1.19 4.60 8.91 1.48 4.93 0.24 2.69 1.55 20 0

21 12.29 1.38 5.26 11.59 1.42 4.79 0.70 6.04 0.94 20 0

28 19.29 1.39 4.71 18.17 1.47 5.15 1.12 6.16 1.12 20 0

35 28.08 1.85 6.22 26.27 1.19 3.86 1.81 6.89 2.39 40 0

42 41.52 2.35 7.09 38.65 1.65 5.86 2.87 7.43 2.03 60 0

49 54.52 2.61 8.16 50.47 1.69 5.86 4.05 8.02 2.40 80 11.4

56 63.39 1.75 5.50 64.48 1.44 4.57 1.09 1.69 1.49 22.8

63 66.2 1.72 5.75 67.56 1.16 4.43 1.36 2.01 2.20 34.2

70 75.03 1.88 5.35 72.18 1.12 3.93 2.85 3.95 2.83 45.6

77 72.81 0.96 2.99 74.94 0.98 3.07 2.13 2.84 1.04 57

84 73.64 1.18 3.74 77.31 0.94 3.14 3.67 4.75 1.56 68.4

91 77.38 1.35 4.77 77.13 0.91 2.72 0.25 0.32 2.18 80

98 80.49 0.96 2.95 78.75 0.84 2.43 1.74 2.21 1.32

105 81.04 0.81 2.57

Ave 1.46 4.77 Ave 1.20 4.02 1.63 5.59 1.84

Page 10: ESN Presentation

ESN Check Controlled Release Profile

0 14 28 42 56 70 84 980

10

20

30

40

50

60

70

80

90

AntekRudolph Upper SpecLower Spec

Days

% N

itrog

en

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Std Dev of Data Replicates ESN Check

0 14 28 42 56 70 84 980.0

0.5

1.0

1.5

2.0

2.5

3.0

Antek Std DevRudolph Std Dev

Days

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Range of Data Replicates ESN Check

0 14 28 42 56 70 84 980.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

Antek RangeRudolph Range

Days

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F Value of ESN Check by Rudolph vs. Antek

0 14 28 42 56 70 84 980.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

F Value of ESN Check by Rudolph vs. Antek

F Value

Days

Page 14: ESN Presentation

Observations:

• The Controlled Release of the ESN Check as determined by Rudolph RI exhibits a more predictable & reliable increase above 60% as compared to the CRP determined by Antek.

• The CRP’s of the ESN Check both exhibit the desired S-curves as per the specifications & the results of analysis by Rudolph RI are statistically similar to those determined by Antek analysis.

• Comparison of the standard deviation & range of the replicates in each set shows that the Rudolph method produces less variable data overall. The graphs however show similar trends in data variation during the same testing periods.

• The F Values for Rudolph analysis as compared to Antek analysis all fall below the acceptable equivalence limit of 3.18 & the average F Value is 1.84 which is well below the acceptable equivalence limit of 3.18 (at 9 degrees of freedom & 95% confidence level).

Page 15: ESN Presentation

Data Collected: ESN Blue

DayAntek (ave)

Antek Std Dev

Antek Range

Rudolph (ave)

Rudolph Std Dev

Rudolph Range Delta N2 % Delta F Value Upper Spec Lower Spec

1 0.82 0.81 2.73 1.41 0.64 1.86 0.59 41.84 1.59 20 07 3.56 1.46 4.04 3.93 1.38 4.43 0.37 9.41 1.12 20 0

14 8.34 2.29 7.05 8.25 2.20 6.50 0.09 1.09 1.08 20 021 14.47 2.99 9.99 13.86 2.31 6.65 0.61 4.40 1.67 20 028 22.89 2.67 8.37 20.94 2.69 8.50 1.95 9.31 1.01 20 035 29.69 2.50 8.85 29.58 2.85 9.72 0.11 0.37 1.29 40 042 38.67 2.63 9.81 38.24 3.36 11.00 0.43 1.12 1.64 60 049 44.78 1.92 6.28 47.53 3.25 10.50 2.75 5.79 2.86 80 11.456 55.09 1.73 5.97 22.863 62.08 2.56 8.78 59.99 2.31 7.36 2.09 3.48 1.23 34.270 65.27 1.37 4.25 65.62 1.96 6.43 0.35 0.53 2.07 45.677 68.08 1.13 4.09 70.49 1.58 5.50 2.41 3.42 1.94 5784 70.75 1.56 5.87 73.43 1.41 4.72 2.68 3.65 1.23 68.491 72.45 1.22 3.60 73.86 1.21 4.29 1.41 1.91 1.01 8098 74.32 0.55 2.04 75.48 1.28 4.07 1.16 1.54 5.41

105 77.67 3.78 13.82 78.07 1.03 3.64 1.52 1.95 1.78 112 78.07 0.45 1.46 78.66 1.07 3.43 0.59 0.75 5.54 119 79.63 0.50 1.43 79.52 1.03 3.14 0.11 0.14 4.29 126 82.32 2.06 7.00 80.36 0.87 2.64 1.96 2.44 5.58

Ave 1.80 6.08 Ave 1.80 5.80 1.18 5.18 2.27

Page 16: ESN Presentation

ESN Blue Controlled Release Profile

0 14 28 42 56 70 84 98 112 1260

10

20

30

40

50

60

70

80

90

AntekRudolph Upper SpecLower Spec

Days

% N

itrog

en

Page 17: ESN Presentation

Std Dev of Data Replicates ESN Blue

0 14 28 42 56 70 84 98 112 1260.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

Rudolph Std DevAntek Std Dev

Days

Page 18: ESN Presentation

Range of Data Replicates ESN Blue

0 14 28 42 56 70 84 98 112 1260.0

2.0

4.0

6.0

8.0

10.0

12.0

14.0

16.0

Rudolph RangeAntek Range

Days

Page 19: ESN Presentation

F Value of ESN Blue by Rudolph vs. Antek

0 14 28 42 56 70 84 98 112 1260.0

1.0

2.0

3.0

4.0

5.0

6.0

F Value

Days

Page 20: ESN Presentation

Observations

• The Controlled Release Profile (CRP) of the ESN Blue as determined by Rudolph RI exhibits a very similar curve to the CRP determined by Antek.

• The CRP’s of the ESN Blue were quite smooth & both exhibit the desired S-curves as per AAT specifications.

• The F Values for Rudolph analysis as compared to Antek analysis all fall below the acceptable equivalence limit of 3.18 for the first 91 days.

• The Controlled Release Profile of ESN Blue was found to be extended well beyond the expected 91 days (to 126 days) but this has been observed with the ESN Blue product in general.

• Although the CRP’s of the average results for both methods produced similar, smooth curves comparison of the standard deviation & range of the replicates in each set shows that the Antek method produces highly variable results. The overall average SD for both methods were exactly the same & the overall average ranges between the methods were similar (6.08 for Antek as compared to 5.80 for Rudolph).

• Most of the F Values ESN Blue beyond 91 days are above the acceptable equivalence limit of 3.18 due to high variation within sets of nitrogen release data.

• The average F Value for Rudolph analysis as compared to Antek analysis is 2.27 which is well below the acceptable equivalence limit of 3.18 (at 9 degrees of freedom & 95% confidence level).

Page 21: ESN Presentation

Data Collected: Poly-R

DayAntek (ave)

Antek Std Dev

Antek Range

Rudolph (ave)

Rudolph Std Dev

Rudolph Range Delta N2 % Delta F Value Upper SpecLower Spec

1 2.87 1.17 3.12 3.73 0.90 3.14 0.86 23.06 1.72 20 07 12.23 1.32 4.14 11.30 1.42 3.57 0.93 8.23 1.15 20 0

14 21.53 1.80 5.86 19.89 1.85 4.36 1.64 8.25 1.07 20 021 28.34 2.13 6.76 28.37 2.00 6.22 0.03 0.11 1.14 20 0

28 37.71 2.41 7.96 36.81 2.33 8.36 0.90 2.44 0.83 20 0

35 45.54 2.24 7.39 46.63 2.46 8.79 1.09 2.34 1.21 40 042 55.54 2.04 7.11 55.90 2.39 8.15 0.36 0.64 1.37 60 0

49 62.27 1.83 6.35 64.55 2.32 7.57 2.28 3.53 1.61 80 11.456 73.15 1.99 6.48 4.10 5.94 22.8

63 75.04 2.67 7.73 73.55 1.65 5.22 1.49 2.03 2.62 34.270 77.83 1.08 4.12 77.71 1.52 4.29 0.12 0.15 1.97 45.6

77 79.5 1.85 6.16 80.83 1.22 3.86 1.33 1.65 2.31 57

84 82.73 0.89 2.90 83.02 1.02 3.14 0.29 0.35 1.32 68.4

91 80

Ave 1.80 5.85 Ave 1.68 5.20 1.19 4.52 1.66

Page 22: ESN Presentation

Poly-R Controlled Release Profile

0 14 28 42 56 70 840

10

20

30

40

50

60

70

80

90

AntekRudolph Upper SpecLower Spec

Days

% N

itrog

en

Page 23: ESN Presentation

Std Dev of Data Replicates Poly-R

0 14 28 42 56 70 840.0

0.5

1.0

1.5

2.0

2.5

3.0

Antek Std DevRudolph Std Dev

Days

Page 24: ESN Presentation

Range of Data Replicates Poly-R

0 14 28 42 56 70 840.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

10.0

Antek RangeRudolph Range

Days

Page 25: ESN Presentation

F Value of Poly -R by Rudolph vs. Antek

0 14 28 42 56 70 840.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

F Value

Days

Page 26: ESN Presentation

Observations:

• The Controlled Release Profile of the Poly-R as determined by Rudolph RI exhibits a very similar curve to the CRP determined by Antek; both methods showed over 80% nitrogen release at 84 days.

• While the CRP’s of Poly-R do not exhibit the desired S-curves (as per AAT specifications) by either method, the results of analysis by Rudolph RI are statistically similar to those determined by Antek analysis.

• The F Values for Rudolph analysis as compared to Antek analysis all fall below the acceptable equivalence limit & the average F Value is 1.66 which is well below 3.18, the acceptable equivalence limit (at 9 degrees of freedom & 95% confidence level).

Page 27: ESN Presentation

Summary

• As can be seen in the preceding graphs the majority of the F Values obtained from comparison of nitrogen release analysis by Rudolph refractometer & Antek nitrogen analyzer fall below the acceptable equivalence limit of 3.18 for the ESN Composite, the Poly-R Composite & the CNO ESN Check sample.

• The ESN Blue Composite Controlled Release Profile exhibits F Values well below 3.18 up to 91 days; however, it is recognized by AAT that the ESN Blue product has proved to exhibit slower nitrogen release than specified.

Page 28: ESN Presentation

Conclusions:

• Since the overall aver F value for all products tested in this study (1.88) is well below the acceptable equivalence limit of 3.18, the new method (RI by Rudolph refractometer) can be considered to be equivalent to the existing approved method (Antek nitrogen analyzer) for analysis of all ESN products.

Page 29: ESN Presentation

Next Steps

• The CNO lab will switch testing of all ESN products to the Rudoph refractometer commencing post-2013 TA.

• The November 2007 produced urea designated as the CNO ESN Check will continue to be used as the check sample for the new method.