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Standards and Plausibility Check

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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?

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]

Multiple determinations How many?

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.

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

3 Plausibility checks

7

Measuring of standard solutions Why?

(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.

Measuring of standard solutions How?

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

208 mg/L

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 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

Selecting the right standards

One-parameter-standard solutions, 1000 mg/L

Multiple-parameter-standard solutions, ready-to-use

One-parameter-standard solutions, ready-to-use

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

The error of the standard solution consists of all single errors of the determination

of concentration and of all devices used.

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

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.

Spectroquant CombiCheck

Control chart

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

CertiPUR Standard solutions

One-parameter-standard solution

This value refers to the determination method!

Self-determination of the control limits

Standard solutions (CRM) for photometric application

One-parameter-standard solutions, ready-to-use

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.

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

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.

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.

Plausibility check by dilution How?

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

Step 3: Calculation of the recovery rate:

Plausibility check by standard addition How?

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.

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

27 WFA Professional Quality Assurance | 2012

Plausibility check by standard addition

Example

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

28 WFA Professional Quality Assurance | 2012

Plausibility check by standard addition

Example

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.

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

Plausibility check by standard addition

Device-supported menu navigation at Spectroquant

Pharo Spectralphotometer

All Spectroquant Pharo spectrophotometers support this function. (AQA3)

AQA3/MatrixCheck Test

Select AQA menu via Setup

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

Plausibility check by standard addition

Spectroquant CombiCheck

for one-time standard addition

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.

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.

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.

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

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.

Comprehensive IQ, OQ and PQ documents

from Merck Millipore

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.

38

Agenda

1 Multiple determinations

3 Plausibility checks

39

Round robin tests

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

40

Round robin tests

For self-monitoring

For determination of the measurement uncertainty

For validation of measuring procedures

norm DIN EN ISO/IEC 17025 or national approval procedures ensuring the

quality of their results and proving their expertise

Planned Round robin solutions from Merck Millipore

Round robin solution Round robin solution

Waste water inlet Waste water outlet

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