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

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Why Do We Need Continuous Monitoring?

Laboratory sampling is only a “snapshot” of the sample on a good day.

3  / 93  / 9

Sampling At “The Pipe” Does Not Sample Storm or Irrigation Water

4  / 94  / 9

Sources of Pollution May be Outside “The Pipe”

5  / 95  / 9

Rarely Do We Sample When Rivers Are Flooding

Just one more bottle

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But There Are No USEPA Approved Methods For On-Line Analysis!

EPA approved methods include: •  Sampling

•  Preservation

•  Calibration verification

•  Duplicates

•  Spikes

•  LCS

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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.

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No Lab Report is Created, No Batch QC

Analysis

Physical Treatment

Chemical Treatment

Measurement

Reporting

Report Generation

Review/React

9  / 99  / 9

A Significant Portion of “Normal” is Eliminated

Analysis

Physical Treatment

Chemical Treatment

Measurement

Reporting

Review/React

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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

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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.

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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

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Analyzer Should Run “Blanks” If Target Analyte Varies

Process control blanks

Ambient water blanks

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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

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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

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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

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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

Aver

age

Tota

l Nitr

ogen

(m

g/L/

day)

Date

TKN vs TN TKN

TN

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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

Ave

rage

Tot

al

Phos

phor

us (m

g/L/

day)

TP ManualTP

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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

Relat

ive T

P (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 14:32Time (Hrs)

Rela

tive

TP (m

g/L)

Laboratory

On-line

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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

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On-Line Analyzer Must Be Rugged Enough For Field / Plant Use

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The On-Line Analyzer Should Be Capable of Sampling Multiple Streams

Multi-Stream Sample Switching Unit

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The On-Line Analyzer Should Be Capable of Handling TSS, If Needed

Multiple Stream TSS Unit

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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

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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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Thank you for viewing this presentation. Should you have any questions or require additional information about our research, products or services, please visit our support page: www.ssi.shimadzu.com/support/ or email wclipps@shimadzu.com.

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