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1. 1 / 9
Suggested QC Practices for
On-Line Analysis
William Lipps
Analytical & Measuring Instrument Division
Shimadzu Scientific Instruments, Columbia, MD.

2. 2 / 92 / 9
Why Do We Need
Continuous Monitoring?
Laboratory sampling
is only a “snapshot”
of the sample on a
good day.

3. 3 / 93 / 9
Sampling At “The Pipe” Does Not Sample
Storm or Irrigation Water

4. 4 / 94 / 9
Sources of Pollution May be
Outside “The Pipe”

5. 5 / 95 / 9
Rarely Do We Sample When Rivers
Are Flooding
Just one more bottle

6. 6 / 96 / 9
But There Are No USEPA Approved
Methods For On-Line Analysis!
EPA approved methods include:
• Sampling
• Preservation
• Calibration verification
• Duplicates
• Spikes
• LCS

7. 7 / 97 / 9
Can Get Around
Sampling and Preservation…
Collection
Manual
Sample
Preserve
Store
Analysis
Physical
Treatment
Chemical
Treatment
Measurement
Reporting
Report
Generation
Review/React
…since analysis is immediate.

8. 8 / 98 / 9
No Lab Report is Created,
No Batch QC
Analysis
Physical
Treatment
Chemical
Treatment
Measurement
Reporting
Report
Generation
Review/React

9. 9 / 99 / 9
A Significant Portion of “Normal” is
Eliminated
Analysis
Physical
Treatment
Chemical
Treatment
Measurement
Reporting
Review/React

10. 10 / 910 / 9
But a Method Includes “Batch” QC
Steps That Must Be Done
Including:
l Calibration and calibration verification
l Blanks
l Duplicates
l Matrix spikes
l Analysis of control samples

11. 11 / 911 / 9
Calibration of On-Line Analyzers
Can Be Automated
l Methods should ensure that analyzers automatically recalibrate.
l Should use multiple points if necessary
l Or, operators should periodically recalibrate.

12. 12 / 912 / 9
Calibration Verification Should Be
Automated
l Methods should ensure that analyzers automatically verify the
calibration in a fixed interval.
l Failed CCV should repeat calibration or flag

13. 13 / 913 / 9
Analyzer Should Run “Blanks” If
Target Analyte Varies
Process control blanks
Ambient water blanks

14. 14 / 914 / 9
The Concept of “Duplicates” Does Not Apply…
• The on-line method should require a way to
collect repeatability data
• Stick the sampling straw in a beaker
…however, precision should be evaluated

15. 15 / 915 / 9
The Concept of “Spikes” Does Not Apply…
• The on-line method should require a way to
determine recovery in the matrix
• Recovery determined on commissioning
…however, recovery should be evaluated

16. 16 / 916 / 9
The Concept of “LCS” Does Not Apply…
• The on-line method should periodically evaluate
an LCS
• LCS defined as comparison to approved method
…however, precision and recovery should be
evaluated

17. 17 / 917 / 9
Example of TN (On-Line)
Compared to TKN (Approved)
0
10
20
30
40
50
11/19/04 11/29/04 12/9/04 12/19/04 12/29/04 1/8/05
AverageTotalNitrogen
(mg/L/day)
Date
TKN vs TN TKN
TN

18. 18 / 918 / 9
Example of TKP (Approved)
Compared to TP (Online)
TPK vs TP
0
1
2
3
4
5
6
7
11/19/04 11/29/04 12/9/04 12/19/04 12/29/04 1/8/05
Date
AverageTotal
Phosphorus(mg/L/day)
TP Manual
TP

19. 19 / 919 / 9
On-Line Monitoring Allows You To
See “Upsets”
0
1
2
3
4
5
6
7
10/4/2004 10/24/2004 11/13/2004 12/3/2004 12/23/2004
RelativeTP(mg/L)
Date
Biweekly Monitor
Hourly Monitor
0
1
2
3
4
5
6
8:32 19:32 6:32 19:32 6:32 18:32 16:32 14:32
Time (Hrs)
RelativeTP(mg/L)
Laboratory
On-line

20. 20 / 920 / 9
Any New “Method” For Continuous
On-Line Monitoring Should:
l Obtain equivalent results to approved laboratory methods
l Be “rugged”
l Use few reagents
l Have a sufficient range
l Sample/”handle” a complex matrix
l Calibrate with multiple points
l Require periodic check samples compared to lab

21. 21 / 921 / 9
On-Line Analyzer Must Be Rugged
Enough For Field / Plant Use

22. 22 / 922 / 9
The On-Line Analyzer Should Be Capable of
Sampling Multiple Streams
Multi-Stream Sample Switching Unit

23. 23 / 923 / 9
The On-Line Analyzer Should Be Capable of
Handling TSS, If Needed
Multiple Stream TSS Unit

24. 24 / 924 / 9
Benefits of On-Line Monitoring
Achieve Maximum Efficiency
• Faster response
• Better treatment
• Cost reduction
Reduce
• Labor
• Time
• Money
Flexibility of Sampling
• Hourly
• Daily
• Weekly
• Monthly
Automatic
• Sampling
• Pretreatment
• Digestion
• Analysis
• Report

25. 25 / 925 / 9
On-Line Analyzer Methods Are Needed If
Data Is Reported For Compliance
l Some QC in existing methods does not apply.
l New methods can be written that still provide sufficient QC.
l On-line results should be compared to lab results.

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