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Standards and Plausibility Check

Adam Aradea
Application Specialist for WFA & LW
MerckMillipore Division, PT Merck Tbk
Agenda

1 Multiple determinations

2 Measuring of standard solutions

3 Plausibility checks

4 Round robin tests

2
Multiple determinations Why?

Multiple determination allow the user to detect random errors


e. g. variations of pipetting.
These errors belong to analytic practice and become noticeable in the form of
unavoidable variation in the measured values.

"Repeated analysis of identical portions of the same, homogeneous sample does not, in
general, lead to a series of identical results. Rather, the results are scattered about
some central value. The scatter is attributed to random error, so called because the
sign and magnitude of the error of any result vary at random and cannot be
predicted exactly. Precision is said to improve as the scatter becomes smaller, i.e. as
random errors decreases, and imprecision is therefore a synonym for random error."
[ISO/TS 13530]

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Multiple determinations How many?

Usually it is sufficient to carry out a double determination of the sample to be


analysed.
A triple determination additionally increases the analytic reliability of the
measuring results and should be carried out for greater variations in the
measured values.
Multiple determination should always refer to the complete method of analysis.
If, for example, decomposition is integrated into the process of analysis, it should certainly
be carried out several times, e.g. total nitrogen determination.

From the single results a mean value must be calculated, which represents the
measuring result. Here, all single results must be included in the mean.

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Multiple determinations
How do I judge my result?
The biggest difference is decisive for the interpretation of the multiple determination.
If the maximum mean variation lies within the quality target, everything is ok. If the
difference is greater, the entire multiple determination should be repeated.
A mean variation of 10 15% is recommended.

Date Name Sample Measured Measured Measured Mean Maximum mean variation Interpretation:
designation value 1 value 2 value 3 Difference Difference x 100% Quality target
Mean achieved?
mg/L mg/L [%]
05 January 04 Bast Discharge NK 37 39 38 38 2 5,3 yes
12 January 04 Bast Discharge NK 42 40 41 2 4,9 yes
12 January 04 Klumm Inflow 370 350 380 360 30 8,2 yes
19 January 04 Bast Discharge NK 61 45 47 51 16 31,4 no
19 January 04 Bast Discharge NK 43 44 46 44 3 6,8 yes
26 January 04 Bast Discharge NK 41 48 45 7 15,7 no

5 WFA Professional Quality Assurance | 2012 Source: Norm DWA A 704 / State 2007
Multiple determinations
How do I deal with deviations?
Reasons for large deviations can often be found in the sample preparation.
e.g. inappropriate homogenisation

If the single results lie outside the quality target even after repeating the
measurement, a further investigation is necessary:
Analyse a standard solution if possible, in double determination in order to
check the analytic system.
For further support the manufacturer of the operating method must be
contacted.

6 WFA Professional Quality Assurance | 2012 Quelle: Norm DWA A 704 / Stand 2007
Agenda

1 Multiple determinations

2 Measuring of standard solutions

3 Plausibility checks

4 Round robin tests

7
Measuring of standard solutions Why?

Each measurement method has a characteristic level of uncertainty


(scattering) depending on the concentration.
This results in a permissible range of values which is restricted by the
control limits.
It can be determined by experiments, but is also given by the manufacturer.
Each parameter and each measuring range should be checked with a
convenient standard solution.

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Measuring of standard solutions How?

Define the control limits:


Preferably, the nominal value of the standard lies in the middle measuring
range of the method and should be typical of the concentration values to be
expected.
For ready-to-use standards, the manufacturer provides a range within which
the measured values should lie = confidence interval of the manufacturer
The permissible value range for self-prepared standards can be determined
by experiments.
The standard deviation is calculated from around 20 independent measurements of the standard.
Nominal value 3-times Standard deviations
Often, in practice, also the simple rule is sufficient: Nominal value 10 %.
Recommendation
Self-determination of the control limits for the lower measuring range.
The simplified alternative can be applied for the middle and the upper measuring
range.
9 WFA Professional Quality Assurance | 2012 Source: Norm DWA A 704 / State 2007
Measuring of standard solutions
Documentation
The following must be listed:
the analysed parameter,
the wastewater plant,
the operation method,
the measuring range,
the standard that is used,
the nominal value,
the control limits and
the type of the photometer used.

10 WFA Professional Quality Assurance | 2012 Source: Norm DWA A 704 / State 2007
Measuring of standard solutions
Documentation
Wastewater plant: Treatment plant Hoppenstdt Parameter: COD
Operating method: XYZ 123 Measuring range: 50 300 mg/l
Standard: ST 200 Photometer/type no. ABC 567

Upper control limit


208 mg/L

Nominal value 200 mg/L

Lower Control limit


192 mg/L

Measuring value
200 205 204 196 204 205 208 186 200 202 204 199 199 202 186 187 201
mg/L
Date D/M/Y D/M/Y D/M/Y D/M/Y D/M/Y D/M/Y D/M/YD/M/Y D/M/Y D/M/Y D/M/Y D/M/YD/M/Y D/M/YD/M/Y D/M/Y D/M/Y

Batch number of the test 12 12 12 12 12 12 12 12 12 12 12 12 66 66 66 66 66

Batch number standard 287 287 287 287 287 287 287 287 287 287 287 287 287 287 287 377 377

Tester Ba Ba Ba Ba Kl Ba Ba Ba Ba Ba Ba Kl Kl Kl Kl Kl Kl

11 WFA Professional Quality Assurance | 2012 Source: Norm DWA A 704 / State 2007
Measuring of standard solutions
Interval frequency
General rule:
The more frequently you check, the more you can trust your
measuring results!

Recommendation
1 x per test series
~ each 20th sample
When the user changes
When the testkit batch changes
When measuring results are not plausible

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Selecting the right standards

Self-prepared standard solutions


One-parameter-standard solutions, 1000 mg/L
Multiple-parameter-standard solutions, ready-to-use
One-parameter-standard solutions, ready-to-use

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Self-prepared standard solutions

Due to the limited storage life of several parameters (e.g. chlorine), ready-to-use
standard solutions are not available for these parameters.
e.g. Weighing and Dissolving of solids, if necessary dilution to target value
each with determination of concentration via reference method, e.g. titration

How huge is the error of this standard solution?


The error of the standard solution consists of all single errors of the determination
of concentration and of all devices used.

Experimental or simplified determination of the control limits

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Spectroquant CombiCheck
Ready-to-use multi-parameter-standard solutions

R-1 = Multiple parameter standard solution, available for every photometric method
R-2 = Spiking solution only for Spectroquant test kits

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Spectroquant CombiCheck

The error caused by the photometric measuring system (test kits, photometer, analytical
procedure) and by the principal of operation can be determined using the standard solution.
This solution will be used instead of the sample.

Depending on the parameters and the accuracy of the method, the working tolerance
is an estimation including an acceptable error and is calculated as a range of 10-15 %
of the target value.
So, also less-skilled staff obtain acceptable results.

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Spectroquant CombiCheck
Control chart

COD 1.14540 10 - 150


Pharo 100, serial no. 0845026

92
x
x x
80 x x x x x
x x
x x
x x x
68 x x x x
x

82 83 81 79 82 77 77 81 80 86 85 74 91 73 70 71 70 66 73 70
Feb. 2005, 01 04 05 06 07 08 11 12 13 14 15 18 19 20 21 22 25 26 27 28.
.De .De .De .De .De .De .De .De .De .De .De .XY .XY .XY .XY .XY .XY XY .XY XY

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CertiPUR Standard solutions
One-parameter-standard solution

Accuracy of the method: 2 mg/L


This value refers to the determination method!

1000 mg/L Standard solution Dilute to target value


Self-determination of the control limits

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Standard solutions (CRM) for photometric application
One-parameter-standard solutions, ready-to-use

Standard solutions for all analyses


Standard methods and test kits
Specific concentration and expanded
measurement uncertainty additionally to
the named concentration
All errors of the concentration
determination are included in the
expanded measurement uncertainty.

No more dilution required!

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Measuring of standard solutions
How to deal with deviations?

If the measured values always lie within the control limits, there is no need for
action.
If this is not the case, a repeated measurement (completely new preparation)
must be carried out.
If the measured value then is within the control limits, the first measured value
was an error measurement.
If, however, the too high or too low measured value is confirmed, the entire
measuring system must be checked, possibly with the help of the
manufacturer (standard solution, batch of the reagent, (piston stroke) pipette,
photometer, if necessary the thermoblock, etc.).
Faulty components must be replaced.

20 WFA Professional Quality assurance | 2012 Source: Norm DWA A 704 / State 2007
Agenda

1 Multiple determinations

2 Measuring of standard solutions

3 Plausibility checks

4 Round robin tests

21
Plausibility checks Why?

Generally, a sample contains not only the parameter of interest study but also
foreign substances. Under certain circumstances, the interferences can be
present in such a level, that they influence the recovery rate of the parameter.
e.g. wastewater samples: a big variation of the composition (matrix) of the samples
should be considered which can strongly influence the result of the analysis.

Influences that depend on the matrix must be determined seperately for each
sample.
For this purpose, a plausibility check by dilution or standard addition is
necessary.

22 WFA Professional Quality Assurance | 2012 Source: Norm DWA-A 704 / State 2007
Plausibility check by dilution How?

The dilution of the sample with distilled water must be carried out in such a way
that the measured value still lies within the measurement range of the
method after the dilution is completed.

Remark:
The used distilled water must be free of contaminations such as ammonium
and/or amines, COD or TOC (e.g. caused by ion exchanger).
If necessary, the water has first to be checked for the absence of impurities.
The usual measurement of conductivity is not a guarantee for the absence of
organic pollutants, since here only ions are measured.

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Plausibility check by dilution How?

A corresponding dilution e.g. 1:2 or 1:3 must be carried out, so the value of
the original sample and the measured value of the dilution both lie within
the measurement range of the method.
At least three dilution steps should be carried out.

If this is impossible, because the value of the diluted sample would reach or
exceed the limit of the measuring range, the method of standard addition must
be applied.

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Plausibility check by dilution How?

Step 1: Measurement of the undiluted sample (Measuring value A in mg/L)


Step 2: Measurement of the diluted sample (Measuring value B in mg/L)
Step 3: Calculation of the recovery rate:

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Plausibility check by standard addition How?

Standard addition method


In this method, sample volumes - gradually decreasing by the same amount -
are mixed with correspondingly increasing volumes of a pure standard
solution of the analyte (addition solution).
1. At least, four mixtures should be prepared.
2. The expected measuring values of the spiked solutions must lie within and
indeed as centered as possible the measuring range of the corresponding
test kit.
3. To receive a big difference between the sample and the spiked solution, the
addition solution should be relatively highly concentrated, Additionally, it is
necessary, that only small amounts of the addition solution are added, so that
there are only marginal changes in the matrix of the sample.

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Plausibility check by standard addition
How?
Step 1: Measurement of the undiluted sample (Measuring value A in mg/L)
Step 2: Measurement of the diluted sample (Measuring value B in mg/L)
Step 3: Calculation of the recovery rate:

v = Volume
c = Concentration
1 = Sample
2 = Standard solution
3 = Mixture
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Plausibility check by standard addition
Example

Measuring range of the test kit: 10 150 mg/L


Concentration of the addition solution: 1000 mg/L (i.e. 1 mg/mL)

How do you judge this sample matrix?


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Plausibility check by standard addition
Example

Evaluation of the results


A matrix effect is present when the recovery rate lies considerably below 80 % or
considerably above 120 %.
When only very small quantities of addition solution are added (see line 2 of the
table), the range of variation of the measurement values may result in these limits
being undermet or exceeded!
The decisive factor here is always the assessment of the measurement series
as a whole. In the example above, therefore, a matrix effect can be excluded.

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Plausibility check by standard addition
Selecting the right standards
Self-prepared standard solutions
One-parameter-standard solutions, 1000 mg/L
Multiple-parameter-standard solutions, ready-to-use
One-parameter-standard solutions, ready-to-use

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Plausibility check by standard addition
Device-supported menu navigation at Spectroquant
Pharo Spectralphotometer
All Spectroquant Pharo spectrophotometers support this function. (AQA3)

Measure the sample Choose AQA Choose


AQA3/MatrixCheck Test
Select AQA menu via Setup

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Plausibility check by standard addition
Instrument-supported navigation with Spectroquant
Pharo Spectrophotometer

CombiCheck
User-defined:
Self-prepared standard solution
One-parameter standard solutions, 1000 mg/L
One-parameter standard solutions, ready-to-use

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Plausibility check by standard addition
Spectroquant CombiCheck

- Ready-to-use addition solution


for one-time standard addition

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Plausibility check by standard addition
Spectroquant CombiCheck

After selecting the CombiCheck, both, the volume of the sample und the volume of the
addition solution are shown automatically and the new target value is calculated.
Only one single measurement is necessary.

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Plausibility check by standard addition
User-defined standard solutions

Method:
Measure the sample in the photometer
Preparation of sample mixture + standard solution in separate vessels
Select MatrixCheck function in the menu
StandardID = user-defined
Input of mixture volumes

The left cuvette contains only the sample (after color reaction), the other ones include
the sample and the self-prepared addition solution in a preliminarily defined mixing
ratio.

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Plausibility check by standard addition
User-defined standard solutions

After the data of the mixture ratio have been entered, the photometer calculates each
single target value.
Then, every round cuvette is measured separately.
The measuring value is shown on the display and the photometer calculates the
recovery rate automatically.

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Plausibility check by standard addition
How to deal with deviations?
Check the pipettes
Check the handling
Repeat the measurement
Repeat the testing with a different dilution ratio

If a matrix effect is existent, the concerning sample cannot be analyzed


wisely without appropriate sample preparation.
If there is an individual case, where a matrix problem cannot be solved by
the method used, another adequate method in doubt the reference
procedure must be chosen.

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Comprehensive IQ, OQ and PQ documents
from Merck Millipore

Installation Qualification (IQ) is done one-time


while installing the instrument.
Operational Qualification (OQ) and Performance
Qualification (PQ) are frequently required.
During the Operational Qualification (OQ) the
correct function of the instrument is checked.
Performance Qualification (PQ) consists of
two parts: Total System Monitoring and the
Matrix Check.

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Agenda

1 Multiple determinations

2 Measuring of standard solutions

3 Plausibility checks

4 Round robin tests

39
Round robin tests

Method of external quality assurance for measurement processes and


laboratories as a confidence building measure
Identical samples are analyzed either by the same or by different methods
Comparison of the results provides information about the measuring
accuracy and measuring quality of the institutes involved

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Round robin tests

For self-monitoring
For determination of the measurement uncertainty
For validation of measuring procedures

Accredited laboratories must regularly attend Interlaboratory tests according to


norm DIN EN ISO/IEC 17025 or national approval procedures ensuring the
quality of their results and proving their expertise

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Planned Round robin solutions from Merck Millipore

Parameter Spectroquant Spectroquant


Round robin solution Round robin solution
Waste water inlet Waste water outlet

COD 550 - 800 mg/l COD 25,0 - 35,0 mg/l COD

TOC 200 - 300 mg/l TOC 10,0 - 15,0 mg/l TOC

Nitrate 15,0 - 25,0 mg/l NO3-N 2,00 - 4,00 mg/l NO3-N

Ammonium 8,0 -16,0 mg/l NH4-N 1,0 - 2,0 mg/l NH4-N

Total Nitrogen 25 - 45 mg/l N 4,0 - 7,0 mg/l N

Phosphate 5,0 - 10,0 mg/l PO4-P 0,50 - 1,00 mg/l PO4-P

Total Phosphorus 10,0 - 20,0 mg/l P 1,00 - 2,00 mg/l P

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Thank You

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