Professional Documents
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Adam Aradea
Application Specialist for WFA & LW
MerckMillipore Division, PT Merck Tbk
Agenda
1 Multiple determinations
3 Plausibility checks
2
Multiple determinations Why?
"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]
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.
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
3 Plausibility checks
7
Measuring of standard solutions Why?
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
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 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
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
R-1 = Multiple parameter standard solution, available for every photometric method
R-2 = Spiking solution only for Spectroquant test kits
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.
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
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
3 Plausibility checks
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.
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.
v = Volume
c = Concentration
1 = Sample
2 = Standard solution
3 = Mixture
27 WFA Professional Quality Assurance | 2012
Plausibility check by standard addition
Example
CombiCheck
User-defined:
Self-prepared standard solution
One-parameter standard solutions, 1000 mg/L
One-parameter standard solutions, ready-to-use
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.
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.
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.
38
Agenda
1 Multiple determinations
3 Plausibility checks
39
Round robin tests
40
Round robin tests
For self-monitoring
For determination of the measurement uncertainty
For validation of measuring procedures