Quality Control

for Sampling and

Chemical Analysis
By:
Dr. Prakash S. Kelkar
What is QA/QC?
• Quality Assurance (QA)
– Are we doing the right things?
– Management

• Quality Control (QC)

– Are we doing things right?
– Technical
Quality Control

Are we doing things right?

A technical concept:
– Did we do the test?
– Did the results pass or fail the criteria?
– If the results failed did we perform a corrective
action?
Purpose of QA/QC
• Determine precision and accuracy,

• Demonstrate absence of interferences,

• Demonstrate absence of contamination

(from sampling equipment, glassware, and
reagents)
Quality Assurance

Are we doing the right things?

A management concept:
• Planning
• Assessment
• Continued improvement
What Qualities do We Want to
Control?

• Accuracy - closeness to the “true” value

• Precision - repeatability
Accuracy
• Composed of precision and bias

• Measure of the overall agreement

of a measurement to a known value
– when random errors are tightly controlled, bias dominates the
overall accuracy
– when random errors predominate, variance (imprecision)
dominates the overall accuracy

• Use bias and precision as separate measures rather

than accuracy
Precision
• Precision is the measure of agreement among
repeated measurements under identical
conditions

• A precision QC is a quantitative indicator of the

random errors or fluctuations in the
measurement process
– e.g., standard deviation or variance
Sensitivity
• Usually regarded as detection limit

• Capability of a method or instrument to discriminate

between measurement responses
– but this term is often used without defining what is intended (minimum
detection or quantitation)

• A sensitivity QC describes the capability of measuring a

constituent at low levels
– a Practical Quantitation Level describes the ability to quantify a
constituent with known certainty
• e.g., a PQL of 0.05 mg/L for mercury represents the level where a precision
of +/- 15% can be obtained
Bias
• Bias is systematic or persistent distortion of a
measurement process that causes error in one
direction

• A bias can result from:

– biased sampling design
– calibration errors
– response factor shifts
– unaccounted-for interferences
– chronic sample contamination
Influence of Bias and Imprecision on
Overall Accuracy
Imprecise and Imprecise and Precise and Precise and
biased unbiased biased unbiased
Data Verification
• The procedures needed to ensure that a set of
data is a faithful reflection of all the processes
and procedures used to generate the data

– verification entails the examination of objective

evidence that the specified method, procedures, and
contractual requirements were fulfilled
Data Validation
• Analyte and sample matrix-specific process to determine
the analytical quality of a data set

– inspection of data handling practices for deviations from

consistency,
– review of quality control (QC) information for deviations,
– assessment of deviations,
– assignment of data qualification codes

• Validation can entail the examination of the data with

respect to the QA Project Plan
Accuracy
Closeness to the “true” value
Types of QC to assess accuracy:
– Matrix Spike
– Laboratory Control Sample
– Laboratory Fortified Blank
– Standard Reference Material
Bias
Error in a specific direction
Blanks are used as an indication of bias
• Field Blank
– analyte contamination - positive bias
• Method Blank
– analyte contamination - positive bias
• Calibration Blank
– analyte contamination - negative bias
– Matrix mismatch – positive or negative bias
• Calibration Check Blank or Instrument Blank
– Instrumental drift over time - positive or negative bias
Data Integrity
• Lack of integrity affects all aspects of data
interpretation, especially data used for decision
making

• Lack of integrity includes:

– manipulation of QC measurements
– dry-labbing (complete falsification of data)
– manipulation of results during analysis
– failure to conduct required analytical steps
– post-analysis alteration of results
Precision
Precision = repeatability
Types of QCs to assess precision:
– Duplicate Field Sample
– Duplicate Lab Sample
– Duplicate Matrix Spike
– Duplicate Laboratory Control Sample
– Duplicate Laboratory Fortified Blank
QC – Tools for the Analyst
1. Use Quality Control samples to identify
accuracy and precision problems,

1. AND to isolate the problems,

1. AND to address the problems

Field Blank
Field blanks should be of the same quality as laboratory
blanks. Also called Trip Blank or Preservation Blank.

Confirms that the source of contamination was not from

laboratory contamination.

Equipment Blanks - some field blanks are actual washings

of field equipment, and should be so designated. These
blanks may well show some elements above detection.
Calibration Blank

• Used to set the zero end of the calibration curve.

• If contaminated, can skew the whole curve - biasing the

sample results low, especially at low concentrations.
Method Blank
• Analyte-free matrix taken through the same laboratory
preparation and analysis process as the samples.

• Lab needs to set criteria of acceptance range

• Typically, if contamination is found in the method blank

but at less than 1/10 of the sample concentration, the
method blank contamination is disregarded for that
sample.
Calibration Check Blank
An instrument blank (the same blank that used for
calibration) must be run:
– Immediately after calibration
– Minimum frequency – after every 10 samples
– At the end of the analysis run
Calibration is the set of operations
which establish, under specified
conditions, the relationships between
values indicated by a measuring
instrument or measuring system , or
values represented by a material
measure or reference material, and
the corresponding values of a quantity
realized by a reference standard.
Calibration can be carried out for
three possible purposes viz.

I) Determining whether or not

a particular instrument or standard is
within some established tolerance in
respect of its deviation from a
reference standard.
ii) Reporting of deviation in
measurements from nominal values.

iii) Repairing /adjusting the instrument or

standard to bring it back within the
established tolerance.
Calibration System

In a calibration system, the following items
shall be defined.

1. Classification of calibration

2. Standard and levels of standard. 
3. Interval of calibration and limit of 
correction

4. Procedures of calibration

5. Action after calibration

6. Conditions to use measuring 
instrument 

7. Procedures of measurement
 Why  Measurements?
Measurements are basic tools in S & T. Said a German philosopher:
If I can define it, I can measure it.
If  I can measure it, I can analyze it.
If  I can analyze it, I can control it.
If I can control it, I can improve it.

Measurements are needed to
Choose ,develop, and validate models used to predict, control or 
Improve various phenomena. Measurements provide the very basis
Of all control actions.
 What are Measurements?
Measurement :
A Process that follows a defined sequence of 
steps/activities involves physical, material and technological  
resources;and results in a numerical value/a set of numerical 
values that is assigned to an item in respect of a defined property/ 
parameter/ characteristic.

Measurement : The output of a (measurement)                     
process.                                    
‐ a numerical value
 Errors in  Measurements:

Errors in the observed results of a           
measurements (process) give rise to uncertainty 
about the true value of the measured as is 
obtained (estimated) from those results. Both 
systematic and random errors affecting the 
observed results (measurements) contribute to 
this uncertainty.
Random errors presumably arise from unpredictable and spatial
Variations of influence quantities ,for example.

• the way connections are made or the measurement method
employed
• uncontrolled environmental conditions or their influences

• inherent instability of the measuring equipment

• personal judgment of the observer or operator, etc.

These cannot be eliminated totally but can be reduced by exercising 
appropriate controls.
Various other kinds of errors, recognized as systematic, are
also observed.

Some common type of these errors are

• those reported in the calibration certificate of the reference
standards/instruments used.

• those due to different influence conditions at the time of 
measurement compared with those prevalent at the time of 
calibration of the standard(quite common in length and d. c.
measurements) etc.

It should be pointed out that errors which can be recognized
as systematic and can be isolated in one case may simply 
pass off as random in another case. 
 Quality in Measurements
Quality of measurements is comprehended in terms of
accuracy and Precision, based on systematic/random errors
respectively that get reflected in repeat measurements. A more recent 
development takes care of both random and systematic errors and results 
in a measure of Uncertainty about the true value.

Accuracy is the critical parameter, and is not the same as
precision. Accuracy is closeness to the true value (of the
measured), while precision implies consistency among repeat 
measurements(not always available).
 NABL Requirements :Technical Criteria

‰ Standard required : ISO/IEC  17025 : 2005
‰ What are Technical requirements ?    Need to be satisfied in order to establish technical
competence of a Laboratory to carry out the Testing
and Calibration activities of the Organization

™ Note : Whatever we speak these three  days, the single most important purpose is to find
the true value of the parameter we want to measure(measured) as close as possible.

™ In ISO/IEC 17025, the Technical requirements are elaborated in Section 5.0.
™ The requirements are:
5.1       General
5.2       Personnel
5.3       Accommodation and Environmental conditions
5.4       Test and Calibration Methods and Method Validation
5.5       Equipment
5.6       Measurement Traceability
5.7       Sampling
5.8       Handling of Test and Calibration items
5.9       Assuring the Quality of Test and Calibration Results
5.10     Reporting of Results

You can very well imagine that all these factors can affect the correctness
and reliability of the test results performed by a laboratory.
 Personnel
z This is the human factor and is an  important  one ,    since
error(random) will be  introduced due to personnel who are       involved in 
carrying out the tests, evaluate and sign  test           reports.
z Basic concepts of this requirement is to ensure               competence 
of the person/persons in  a particular testing or       calibration activity. This 
involves both operation of the                equipment correctly and carrying out 
test according to the          laid down validated test methods.

How can we do that?

z We can ensure educational part by specifying qualification       and  
experience during recruitment of Scientist/Technical           Officer/  Technical 
Assistant at a certain level. 
z CSIR has a definite Recruitment policy to take care of this    criteria.
 Accommodation and Environment

z All aspects discussed here are basically for leading to create a conducive      atmosphere for 
conducting the tests accurately and reliably.

Policy should be framed so that:
z All technical requirements of space, temperature, power, atmosphere          should be met 

in the testing area.
z The laboratory should provide facilities for the effective monitoring,              control and 

recording of environmental conditions as appropriate
z Adequate measures are to be taken to ensure good house keeping in the     laboratory.

z Testing areas should be separated  from neighboring areas and access         should be 

limited.

Procedures: how to implement these policies
z Procedures can be laid down according to the convenience and practice       followed by 
the laboratory.
z Some improvements in practices should be done taking advantage of the     NABL 

requirements
™ What is validation?
Validation is the confirmation by examination and the provision of objective 
evidence that the particular requirements for 
a specific intended use are fulfilled.

™ What to validate?
z Standard methods, national or international, do not need         validation.
z Not‐standard methods, laboratory developed methods, standard      methods used 

outside their intended scope , amplifications and        modifications of standard  
methods need validation
z Should be extensive to check that it meets the need of the given      

application/field  of application
z Should record the results obtained, procedure used for validation     and a 

statement indicating suitability
z Validation may include sampling, handling and transportation
™ How  to validate? 
By following one or a combination of the following methods:
ƒ Calibration using reference standards or reference materials
ƒ Comparison of results achieved with other methods
ƒ By participating in Interlaboratory comparisons
ƒ Systematic assessment of the factors influencing the result
ƒ Assessment of the uncertainty of the results based on scientific understanding of the 
theoretical principles of the method and practical experience

™ Uncertainty of measurement
A Testing laboratory or a Calibration laboratory has to apply a procedure to estimate 
the uncertainty of measurement for each test.
Reference Standards and Reference Materials(RM)

ƒ RM is a generic term
ƒ Definition: Material, sufficiently homogeneous and stable with respect to one or more
specified properties, which has been established to be fit for its intended use in a
measurement process
ƒ properties can be quantitative, e.g. identity of substances or species.
ƒ Uses may include the calibration of measurement system, assessment of a measurement
procedure, assigning values to other materials , and quality control.
ƒ A single RM cannot be used for both calibration and validation of results in the same
measurement procedure.

Certified Reference Material(CRM) –Reference material characterized by a

metro logically valid procedure for one or more specified properties, accompanied by a
certificate that provides the value of the specified property, its associated uncertainty, and a
statement of metrological traceability.

N.B.Intermediate checks, transport and storage of the RM should also be taken care of
™ Reporting of results
ƒ ISO 17025 gives a specific format for Test Report(clause 5.10.2 of IS/ISO/IEC 17025)
ƒ In addition, the followings should be mentioned
- deviations from, additions to or exclusions from the test method and information on specific
test condition such as environmental conditions.
- a statement of compliance/non-compliance with requirement or specification
- a statement on the estimated uncertainty of measurement, if applicable
- opinions and interpretations, if needed
- details on sampling

™ Opinions and Interpretations

ƒ This standard offers the scope of giving opinions and interpretations based on test results

™ Amendments of test report/calibration certificate

ƒ Further document should be issued which should include the following:
“Supplement to test report/Calibration Certificate, serial no. or any other identification no”
 LATEST TERMINOLOGIES
AND TRENDS IN CALIBRATION

™ Nominal Value:- A target value intended as the

general value to be measured

™ True Value:- A value measured without any

errors.

™ OFFSET:- The difference between the Nominal value and

the true value which can be corrected for
“It is what we want to measure”.

™ ERROR:- The difference between the true value and

measured value.
 LATEST TERMINOLOGIES
AND TRENDS IN CALIBRATION
. . . . contd

™ UNCERTAINITY:-

An estimate of the range of

values which contains the true
values of a measured quantity. It is usually reported
of probability that the true value lies within a
stated range of values.

Errors also can never be known exactly only

estimated.
Error is not the same as uncertainty

™ It is an additional factor applied

to the measured value to allow for the
Presence of measurement error.
Measurement = Measured value +/- M. Uncertainty
Basic requirements of a Calibration Lab

™ Instruments(Standards)

™ Personnel

™ Documentation
 ADVANTAGES OF CALIBRATION

1. Insures that all tools & test standards

properly agree

2. Verifies compatibility of parts, systems &

assemblies

3. Obtain peak performance of all systems

in use

4. Insures that everyone in the company

stays working to the same standard
 contd . . .

5. Ensures performance after

recalibration

6. Avoids damage during performance

checking because of improperly
calibrated or functioning instruments
 STANDARDS

Standards means physical realization of various units of

measurements
Standards in terms of hierarchy
¾ International Standards
¾ Primary National Standards
¾ secondary Standards
¾ Working Standards or Industrial Standards

International Standards are constructed as per specification of an

International agreement. They represent the units of
measurements of various physical quantities of the highest
possible accuracy.

Primary National Standards represent the fundamental and derived

quantities and are calibrated by absolute measurements. These
are maintained normally by the National Laboratories, e.g.,
Standard for Temperature using “Freezing Point of Pure Metal”
secondary Standards includes devices which carries down the
SI units from the primary local standards. It is normally used to
either calibrate or enhance the performance of calibrator.

Some more types of standards which are also used are

Consensus Standards which can be an artifact or a process that

is mutually acceptable to supplier/customer, having no national
standard. Example: Particle contamination

Indirectly Derived standards which are inferred by measuring

other quantities. example: Direct Current even as one of the SI
units, not directly traceable to national standards. Current is
standardized through measurement of voltage developed
according to Ohms Laws.
ERRORS IN MEASUREMENT

Types of error
Gross error

Random error

Systematic error
 ERRORS IN MEASUREMENT
Contd. . .

Gross errors
Are strictly under the control of individual
(independent of instrumentation)
Examples-
Misreading of instrument
Making incorrect adjustments
Improper application of instruments
Recording interpolated data
Can be avoided by-
Care and attention
Close supervision
More systematic training
ERRORS IN MEASUREMENT
contd…

Random errors
A scatter about an average when a multiple no. of
measurements are taken
As a result of:
Variations in measuring system
Changes in quality being measured
Detectable when:
Repeated measurements are taken with a seemingly
constant set-up and consistent technique
Internal Standard
Some tests (e.g., ICP-MS) make routine use of internal
standards.

For each specific analysis, the limits on the recovery of the

internal standards are determined by the lab.
Matrix Spike and Duplicate Spike
Spike – add a known amount of analyte to a separate aliquot of sample from
the same sample container and take it through the entire prep and analysis
procedure.

Analyze a matrix spike/duplicate pair for every 10 samples, with a minimum of

one for each batch from a survey.

Two matrix spikes are evaluated separately as matrix spikes, and the pair is
evaluated as above for a sample/duplicate pair.

The matrix spike/duplicate pair should be evaluated together for evidence of

sample homogeneity problems.

Matrix spike duplicates may be used in place of sample duplicates.

Analytical Spike
Some tests (e.g., GFAA) make routine use of analytical
spikes.

The limits on the recovery of the analytical spikes is

determined by the lab.

Indicates bias of results.

Laboratory Control Sample (LCS)
• An LCS is a sample of known concentration for the
analyte of interest.

• Made from a standard from a source independent of the

calibration standard source (referred to as “second
source”)

• Prepared and analyzed with the samples.

• Limits on recovery are determined by the lab.

• The LCS may be the only independent check of the

standards used to prepare the calibration curve.
Instrument Performance Check
Some methods (ICP, ICP-MS) have instrument
performance checks periodically performed to confirm
the instrument is operating properly before analysis.

– Spectral Position Optimization

– Interference Check Samples:
– ICP-MS Tuning:
– Short-Term Stability Check
Which QC to use?
Your QC Tools:
1. Field Blank
2. Field Dup
3. Lab Blank
4. Lab Dup
5. LCS
6. Matrix Spike
7. Matrix Spike Dup
8. Spike Blank
9. Calibration Check Blank (initial and continuing)
10. Calibration Check Standard (initial and continuing)
11. Special QC
QC for Titration
• Field Blank
• Field Dup
• Lab Blank
• Lab Dup
• LCS
• Matrix Spike
• Matrix Spike Dup
• Spike Blank
QC for a simple analysis
e.g. Colour
1. Field Blank
2. Field Dup
3. Lab Blank
4. Lab Dup
QC for Instrumental Analysis
• Field Blank
• Field Dup
• Lab Blank
• Lab Dup
• LCS
• Matrix Spike
• Matrix Spike Dup
• Spike Blank
• Calibration Check Blank (initial and continuing)
• Calibration Check Standard (initial and continuing)
QC for ICP
• Field Blank
• Field Dup
• Lab Blank
• Lab Dup
• LCS
• Matrix Spike
• Matrix Spike Dup
• Spike Blank
• Calibration Check Blank (initial and continuing)
• Calibration Check Standard (initial and continuing)
• Inter-Element Correction Factor Check
• Reporting Limit Check
• Spectral Optimization Check
USEPA Websites for QA/QC
• Agency-wide Quality System Documents (EPA Order; QMPs: QA/R-2;
QAPPs: QA/R-5, QA/G-5, QA/G-5G, QA/G-5S, QA/G-5M)
• http://www.epa.gov/quality/qa_docs.html

• Training courses on QA/QC activities

• http://www.epa.gov/quality/trcourse.html

• Quality Management Tools – QAPP (FAQs, checklist, and all QA/R & G
documents)
• http://www.epa.gov/quality/qapps.html

• Doing Business with EPA: Quality Specifications for non-EPA

Organizations
• http://www.epa.gov/quality/exmural.html
Thanking you