Quality Assurance and Quality Control in Environmental Analysis

Environmental
DENR-EMB Research & Lab

Services Division
2018 Intercomparison Exercises for DENR-EMB Laboratory Analysts
Quality Assurance and Quality Control

in Environmental Analysis
Ma. Fatima Anneglo R. Molina
Roger C. Evangelista
Sammy L. Aytona
EMB Region XII Laboratory
23 May 2018
Environmental
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Quality Assurance Quality Control

An overall A series of
management plan to analytical
guarantee the measurements used
integrity of data to assess the
(The “system”) quality of the
analytical data
(The “tools”)
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Quality Assurance Quality Control
a laboratory operations processes needed
program that specifies to demonstrate
the measures required the laboratory’s
to produce defensible competence
data with known
precision and accuracy
SMEWW 23rd edition
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Laboratory Services Sample

Collection
Sample Transport
QA/ QC
Planning &
Policies Mobilization
SOPs
WI
Data Management Sample Reception
& Login
Laboratory Analysis
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Quality Assurance (QA) elements

- quality system
documentation
A structured and
documented management
system describing how and
by whom an organization
assures quality in its work.
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Main objectives of an organization’s
documentation:
a) Communication of Information
- as a tool for information transmission and
communication.
e.g. quality policy, quality manual, SOPs, work
instructions
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documentation:
b) Evidence of conformity
- provision of evidence that what was planned, has
actually been done
objective evidence - “data supporting the

existence or verity of something”
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documentation:
c) Knowledge sharing
- to disseminate and preserve the organization’s
experiences
e.g. methods validation/ verification study ,
method detection limits study
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- staff organization and responsibilities
- sample control and documentation
- test method documentation
- analyst training
- equipment calibration and maintenance
- corrective and preventive action
- internal quality control
- performance audit
- data assessment
- data reduction, validation and reporting
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- Sample tracking procedures (i.e. chain of
custody procedures)
Institute procedures to trace a sample

and its derivatives through all steps: from
collection through analysis, reporting of final
results, and sample disposal.
- SMEWW 23rd
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Chain of Custody (COC)

• written documentation of the security of a sample
from the time it is collected to the time it is
transferred to the representative of the laboratory
that is conducting the analysis
• Allows for routine control of samples and also aides in
litigation issues
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Chain of custody procedures

• COC provided by the laboratory and
taken to the field.
• Sampler fills in the COC form at the
time of sample collection and returns it
to the lab along with the collected
sample
• Specific information in the COC
includes:
• Client and its contact details
- Sampling source, sampling point ID
number (assigned by the sampling
supervisor)
- Date and time of sampling
- Name and signature of the sampling
crew
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Chain of custody procedures, contd

Type of sample
- Analyses requested ,
preservatives, containers
- Submitted by (or
relinquished by) – name/
signature of the person that
relinquishes sample to lab
personnel
- Date/ time sample is
submitted to the laboratory
- Special instructions/
comments - includes any
special notes to the lab,
such as special analysis
required of the sample,
sample pH and
temperature
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• After sampling is completed at a
site, the sampling crew labels the
containers.
• Samples are sealed with chain of
custody seals (optional) and
placed in an ice chest for
transportation to the lab.
• Samples and the accomplished
COC are submitted to the
laboratory.
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• * The laboratory logs the
samples and assigns a
unique reference number to
the sample. Sample is
tracked by means of this
number.
• Lab personnel sign and date
the form. A copy is given to
the sampler.
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Chain of Custody
Traceability
Shows who handle
the sample from
collection,
preservation,
storage, and analysis.
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Sample Reception and Login

A. Chain of custody
verification
B. Physical Inspection of the
condition of the sample
• Holding Time
• Sample volume
• Bottle or container type
• Preservative
• Sample Label https://www.google.com.ph/search?biw=1600&bih=769&tbmknodg3j2QyO1L
M:
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Sample Reception and Login
C. Recording of samples into a master

log and assignation of a unique
laboratory identification codes
D. Perform sample pre-handling
where necessary (compositing/
preservation)
E. Store samples appropriately
http://lab-training.com/2015/02/19
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Holding Time
Holding time - the maximum amount of time that can

pass from collection before a sample is analyzed and
still obtain valid results.
• Samples analyzed beyond the maximum holding time

generate questionable or invalid results.
In addition to meeting the published hold times,

sample collectors must keep in mind courier routes
and scheduling and the hours of operation of the
assigned laboratory
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Holding Time
The holding time depends upon the analyte of interest
and the matrix under consideration. e.g.
• metals (Pb, Cd, Cu) in water - 6 months
• Coliforms, BOD5 - 6 hours
• pH – analyze immediately
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Sample volume
• Sufficient to perform all the required

analyses with an additional amount
collected to provide for any QC needs
such as:
• duplicates
• matrix spikes
• split samples
• confirmations or repeat examinations
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Sample volume
• Determinations for some parameters may be
submitted in the same sample bottle if the bottle
contains sufficient sample for each analysis and require
compatible collection and preservation techniques.
The most common practices include:
• one 500-ml sample bottle – ammonia, nitrate + nitrite, and
phosphate analyses
• One 1000-2000 ml – BOD, COD, TSS
• One 1000 ml – heavy metals (Cd, Cu, Pb, Hg)
• One 1000 ml – oil and grease
• One gallon – OCPs and PCBs
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Sample container
• Selection of a sample container
• Based on the parameter to be measured
• Made of chemically resistant material, and do not
affect the concentrations of the pollutants to be
measured
• Have a closure (i.e., leak proof/resistant, Teflon
lined) that protects the sample from contamination
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Sample container
• Plastic containers • Glass containers
~ inorganic parameters ~ organic parameters
(teflon lined caps,
Or lined with solvent
rinsed aluminum foil
• Sterile container
~microbiological
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Sample Preservation
• The sample must be representative of the

environment. Both physical and chemical
processes may be involved in changing the
composition of a sample after it is collected.
• Proper steps should be taken so that the
pollutants are not lost or physically/ chemically
altered during sample collection, preservation,
and transport.
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Sample Preservation
• Common physical processes which may degrade a sample
are volatilization, diffusion, and adsorption.
• Possible chemical changes include photochemical reaction,
oxidation and microbial degradation.
• Example: Organic materials in water or soil samples, for
instance, can be readily attacked and digested by
bacteria present in the sample.
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Sample Preservation
- prevent or minimize
 biological activity e.g. microbial respiration
 chemical activity e.g. precipitation or pH
change
 physical activity e.g. aeration or high
temperature
within the sample after it has been collected.
Responsibility
sampling personnel, NOT the lab
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Methods of Preservation
Thermal i.e. cooling
 most samples must be thermally preserved at
the time of collection
 low temperature
 reduces microbial growth and metabolism
 Reduces thermal and spontaneous
denaturation
 Reduces adsorption on to the container wall
 bacterial samples – T ≤ 8°C

 other samples – T≤6°C( with no evidence of
freezing)
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 When collecting samples from multiple

sites, ice must be added to the cooler prior
to or immediately after the first samples
are collected
 In order to ensure that samples obtain
appropriate cooling, they should be nearly
covered by, rather than resting on top of
the ice.
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Chemical addition
• chemical additives such as acids or bases
used to control pH, or
• reagent solutions such as sodium thiosulfate
used to reduce the effect of residual
chlorine and other oxidizers.
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Recommended Volume, Container, Preservative and Holding Time

Parameters Minimum Container Type
Sample Volume Preservation Holding
Time
Liquid Solid (g) Liquid Solid Liquid/Solid Liquid/Solid
(ml)
Ammonia as 500 - P, G, FP - ASAP, or add H2SO4 to 7d
NH3-N pH<2, Cool (≤6°C)
Anions (Cl, 400 - P, G, FP - Cool (≤6°C) 28 d

SO4)
BOD5 1000 - P, G, FP - Cool (≤6°C) 6h; 48 h
Boron 200 - P - HNO3 to pH<2 28 d
COD 100 - P, G, FP H2SO4 to pH<2, Cool 7d
(≤6°C)
Chromium, 300 - P(A)/ - Cool (≤6°C) 24 h; 28 d
Hexavalent G(A) [Note: pH 9.3 - 9.7
ammonium sulfate
buffer preservative to
extend holding time to
28 d]
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Sample Preservation Holding
Volume Time
Liquid Solid Liquid Solid Liquid/Solid Liquid/Soli
(ml) (g) d
Color 500 - P, G, FP - Cool (≤6°C) 48 h
Conductivity 500 - P, G - Cool (≤6°C) 28 d
Cyanide 500 - P, G, FP - NaOH to pH >12, Cool 24 h
(≤6°C) in the dark
Nitrate as NO3-N 100 - P, G, FP - ASAP, Cool (≤6°C) 48 h
Oil & Grease 1000 - G(wide- - HCl or H2SO4 to pH<2, 28d
mouth) Cool (≤6°C)
Oxygen, dissolved - - G, BOD - ASAP 0.25 h
Bo.
pH 100 - P, G - ASAP 0.25 h
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Volume Time
(ml) (g) d
Phosphate 200 - G(A) - Cool (≤6°C) 48 hr
Residue (solids) 1000 - P, G - Cool (≤6°C) 7d
Salinity 100 - G - ASAP 0.25 h
Surfactants 1000 - G, - H2SO4 to pH<2, Cool 48 h
rinsed (≤6°C)
with
methan
ol, P FP
Temperature - - P, G, FP - ASAP 0.25 h
Turbidity 100 - P, G, FP - ASAP, Cool (≤6°C) 24 hr
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Volume Time
(ml) (g) d
Bacteriological P(E),
Analysis 100 100 G(E) or P (E), Cool (≤8°C) 6 hr
Coliform *P(E), G(E)
*G(E)
Metals Analysis
Total (As, Ba, Cd, 1000 100 P(A), P(A) Liquid: HNO3 to pH<2, 6 mo
Cu, Fe, Pb, Mn, Ni, G(A) , cool ≤6°C
Se, Zn) FP(A) Solid: cool ≤6°C
Dissolved Copper 500 - P(A), - Filter immediately, add 6 mo
G(A) HNO3 to pH<2
Total Mercury 500 50 P(A), P (A) Liquid: HNO3 to pH<2, 28 d
G(A) cool ≤6°C
Solid: cool ≤6°C
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Volume Time
(ml) (g) d
Organics Analysis Liquid: cool ≤6°C
Semi-volatiles 1000 100 G(S) G(S) Solid: cool ≤6°C 7 d/ 14 d
(OCPs, OPPs, PCBs, amber, amber [Note: for solids
PAHs) PTFE freezing to ≤ - 20°C to
lined or extend holding time to
Al 1 year]
covered
cap
Phenol and 1000 G (S) HCl or H2SO4 to pH<2, 28 d
Phenolic amber Cool (≤6°C)
Substances
Volatile Organic 2 x 40 G, PTFE G, PTFE Liquid: HCl to pH<2, 7d
Compounds (BTEX, lined lined Cool (≤6°C)
TCE) cap cap Solid: cool ≤6°C
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Notes:
- Vials, caps heated at 105˚C for an hour before use; septa > 1hour
- Fill container to completely exclude air.
G = glass; P = plastic (polyethylene or equivalent); G(A) or P(A) =

rinsed w/ 1+1 HNO3; G(B) = glass, borosilicate; G(S) = glass, rinsed w/
organic solvents;
G(E) = glass, sterile; P (E) = plastic, sterile; *P(E) or *G(E) = sterile
plastic or glass and containing pre-sterilized sodium thiosulfate
(Na2S2O3) for samples with residual chlorine; FP = fluoropolymer
(PTFE or Teflon); ASAP = analyze immediately; h = hour; d = days;
mo = month/s
Reference/s: 23rd Edition SMEWW, EPA Victoria Industrial Waste

Resource Guidelines
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Sample Identification
• Sample ID label contents:
• station number or sample ID
• date of collection
• analysis requested
• Collector/ project name
• preservative(s)
• Label info
- unequivocally link the collected
sample to the field sheet and
COC documentation
- written legibly and in indelible
ink
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QA Elements
• Standard operating procedures describing the analytical
methods to be used in the laboratory in sufficient detail
that a competent analyst unfamiliar with a method can
conduct a reliable review and/or obtain acceptable
results.
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QA Elements
• SOPs should include, where applicable, the ff items:
• title of referenced, consensus test method;
• sample matrix or matrices;
• MDL;
• scope and application;
• summary of SOP;
• definitions;
• interferences;
• safety considerations;
• waste management;
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QA Elements
• apparatus, equipment, and supplies;
• reagents and standards;
• sample collection, preservation, shipment, and
storage requirements;
• specific QC practices, frequency, acceptance criteria,
and required cor-rective action if acceptance criteria
are not met;
• calibration and standardization;
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QA Elements
• details on the actual test procedure, including sample preparation;
• calculations;
• qualifications and performance requirements for analysts
(including number and type of analyses); data assessment/data
management;
• references; and any tables, flowcharts, and validation or method
performance data.
SMEWW 23rd ed.

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QA Elements
Preventive-maintenance procedures for instrumentation and
equipment.
- an effective preventive maintenance program will reduce instrument
malfunctions, maintain more consistent calibration, be cost-effective,
and reduce down- time.
- include measurement traceability to the International System of Units
(SI) through a National Metrology Institute, such as the National
Institute of Standards and Technology (NIST).
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Quality Assurance Plan

COMPONENTS
(1) Cover sheet with approval signatures (11)Major equipment, instrumentation, and reference
measurement standards used
(2) Quality Policy Statement
(3) Organizational Structure (12)Standard Operating Procedures for each
analytical method
(4) Staff Responsibilities
(13) Procedures for generating, approving and
(5) Document Control controlling policies and procedures
(6) Analyst Training and Performance Requirements (14) Procurement procedures for reference materials
(7) Tests performed by the laboratory and supplies
(8) Procedures for handling and receiving samples (15)Procedures for procuring subcontractors’ services
(9) Sample control and documentation procedures (16) Internal QC activities
(10) Procedures for achieving traceable measurements (17) Procedures for calibrating, verifying, and
maintaining instrumentation and equipment
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Quality Assurance Plan

COMPONENTS
(18) Data verification practices, including inter- (24) Procedures for archiving records
laboratory comparison and PT programs
(25) Procedures and systems for controlling the testing
(19) Procedures for feedback and corrective actions environment
for testing discrepancies (26) Procedures for dealing with complaints from data
(20) Procedures for permitted exceptions to users
documented policies
(21) Procedures for system and performance audits
and reviews
(22) Procedures for assessing data precision and
accuracy and determining MDLs
(23) Procedures for data reduction, validation and
reporting
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Quality Control
• Minimum required QC for each analysis should be included
in each analytical method or SOP.
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1. Initial Demonstration of Capability

PURPOSES:
1. To demonstrate proficiency of each analyst in performing
the method and obtaining acceptable results for each
analyte;
2. To demonstrate that the laboratory’s modifications to a

method will produce results as precise and accurate as
those produced by the reference method.
FREQUENCY:
At least once before analysing the sample.
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COMPONENTS (MINIMUM):
a. Reagent blank
b. Laboratory-Fortified Blanks (at least 4) at a conc’n between
10x the MDL and the midpoint of the calibration curve (or
other level specified in the method)
INDICATORS:
a. RB should not contain any analyte of interest at a conc’n >
½ the MQL (or other level specified in the method)
b. Precision (%RSD) and accuracy (%Rec) for LFBs are within the
acceptance criteria of the method of choice or generated by
the lab ( if there are no established mandatory criteria);
commonly, 70-130% Rec and 20 %RSD, or PT acceptance
limits from a PT-provider.
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NOTE: LABORATORY-GENERATED ACCURACY LIMITS
a. Analyze at least 20 spike samples.

b. Calculate the upper and control limits from the mean and
std deviation of percent recovery.
UCL = Mean + 3SD
LCL = Mean – 3SD
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2. Operational Range
PURPOSE:
To determine the operational (calibration) range (upper and lower limits).
FREQUENCY:
Before using a new method or instrument.
PROCEDURE:
a. Analyze prepared standard solutions ranging from low to high concentrations.
b. Determine the maximum concentration that can be measured within 10% of its
true value based on the calibration curve: this is the limit of linearity.
NOTE: All samples whose concentrations are above the limit of linearity or the highest
calibration point, whichever is lower, must be diluted.
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3. Method Detection Level

• MDL is the constituent concentration that, when
processed through the entire method, produces a signal
that has 99% probability of being different from the
blank.
• For seven replicates of the sample, the mean must be
3.14s above the blank result (where s is the standard
deviation of the seven replicates).
• The MDL will vary with every matrix, analyte and
method to be used.
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• MDL is the constituent concentration that, when processed through
the entire method, produces a signal that has 99% probability of
being different from the blank.
• For seven replicates of the sample, the mean must be 3.14s above
the blank result (where s is the standard deviation of the seven
replicates).
• The MDL will vary with every matrix, analyte and method to be
used.
• Not applicable to methods that do not produce results with a
continuous distribution (e.g. effluent toxicity, presence/absence
methods, micro methods that involve counting colonies).
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REQUIREMENTS:
• Analyze at least 7 portions of a solution spiked at or near the minimum
calibration concentration and an equal number of blanks over a 3-day
period.
• If one MDL will be used for multiple instruments, MDL determination
must be determined across all of them (however, it is unnecessary to
analyse all samples on all instruments).
• Analyst must prepare and analyze at least two (2) spikes and two
blanks on different calendar dates for each instrument.
• If determining MDL for more than three instruments, one set of spikes
and blanks can be analysed on multiple instruments, so long as at least
7 sets of spikes and blanks total are used.
• Alternatively, determine instrument-specific MDLs.
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REQUIREMENTS:
• Calculate estimated sample standard deviation, ss , of the 7
replicates and multiply by 3.14 to compute the MDLs.
• MDLb is calculated as follows:
• If none of the method blanks give numerical result (positive or negative),
then MDLb is not applicable, and MDL = MDLs.
• If some give numerical results, then MDLb equals the highest method
blank result
• If all the method blanks give numerical results, calculate MDLb as follows:
MDLb = X + 3.14sb.
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REQUIREMENTS:
MDLb = X + 3.14sb.
Where: X = mean of blank results (set negative values to zero)
sb = standard deviation of the blank results
• MDL then is equal to whichever is greater: MDLs or MDLb.

• If using more than 7 replicates, adjust value from 3.14 using the
Student’s t table for n-1 degrees of freedom
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4. Reagent Blank
A reagent blank consists of reagent water and all reagents (including preservatives) that
normally are in contact with sample during the entire analytical procedure.
PURPOSE:
To determine whether, and how much, reagents and preparative analytical steps contributes
to measurement uncertainty.
FREQUENCY:
• one reagent blank with each set of samples or on 5% basis, whichever is more frequent.
• analyse after the daily calibration standard and after highly contaminated samples
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4. Reagent Blank
REQUIREMENTS:
• Evaluate results of reagent blanks for contamination and identify and eliminate the source when
unacceptable contamination is present.
• Typically, sample results are suspect if analyte(s) in the reagent blank are greater than the MQL.
Samples analyzed with a contaminated blank must be re-prepared and re-analyzed. Refer to the
method of choice for specific reagent-blank acceptance criteria.
General guidelines for qualifying sample results with regard to reagent blank quality are as
follows:
• If the reagent blank is less than the MDL and sample results are greater than the MQL, then no
qualification is required.
• If the reagent blank is greater than the MDL but less than the MQL and sample results are greater
than the MQL, then qualify the results to indicate that analyte was detected in the reagent blank.
• If the reagent blank is greater than the MQL, further corrective action and qualification is required.
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5. Laboratory-Fortified Blank/Laboratory Control Standard

A laboratory-fortified blank [laboratory control standard (LCS)] is a reagent water sample
(with associated preservatives) to which a known concentration of the analyte(s) of interest has
been added.
Its concentration should be high enough to be measured precisely but not high enough to be
irrelevant to measured environmental concentrations; preferably, rotate LFB concentration to
cover the different part of the calibration range.
PURPOSE:
To evaluate laboratory performance and analyte recovery in a blank matrix.
FREQUENCY:
At least one (1) with each sample batch, or on a 5% basis, whichever is more frequent.
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NOTES:
• Added concentration of at least 10x the MDL/MRL, ≤ to the midpoint of the calibration
curve, or level specified in the method.
• A low-level LFB with concentrations 2-5 times the MDL can be used to check for false
positives and in verifying the MDL/MRL.
• Depending on the method’s requirements, prepare this from either same source used for
calibration or from an independent source.
ACCEPTABLE PERFORMANCES:
• Low-level LFBs may have variable control limits, depending on the method, but typically
are expected to be between 50 to 150%.
• Other LFB recoveries are to be compared with method-specific limits, control charts or
other approved criteria.
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USES:
• Evaluation of batch performance
• Calculation of recovery limits
• Control Chart generation
UNACCEPTABLE PERFORMANCE:
If LFB results are out of control, take corrective action, including re-preparation and re-analysis of
associated samples if necessary
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6. Laboratory-Fortified Matrix
A laboratory-fortified matrix (LFM) is an additional portion ofma sample to which a known
amount of the analyte(s) of interest is added before sample preparation.
CAUTION: LFM IS NOT APPROPRIATE FOR ALL ANALYTES. Consult specific methods for
guidance when an LFM is relevant.
PURPOSE:
To evaluate analyte recovery in a sample matrix.
FREQUENCY:
At least one (1) with each sample batch, or on a 5% basis, whichever is more frequent;
provided that the LFB is feasible for the matrix and the analyte.
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NOTES:
• Added concentration of at least 10x the MDL/MRL, ≤ to the midpoint of the calibration
curve, or level specified in the method.
• Preferably use the same concentration as that for the LFB to allow for separation of matrix
effects from laboratory performance.
• Prepare the LFM from the same source used for the LFB/LCS.
• Make the addition such that sample background levels do not adversely affect recovery
(preferably adjust LFM concentrations if the known sample is more than five times the
background level).
• Evaluate the results obtained for LFMs for accuracy or percent recovery.
• Refer to the specific method for LFM acceptance criteria until the laboratory develops
statistically valid, laboratory-specific performance criteria.
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If LFM results are out of control, take corrective action to rectify matrix effect, use another
method, use the method of standard addition, or flag the data if reported.
Base sample batch acceptance on results of LFB analyses rather than LFMs alone, because the
LFM sample matrix may interfere with method performance.
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8. Duplicate Sample/ Laboratory-Fortified Matrix Duplicate

• Duplicate samples are analyzed randomly to assess precision on an ongoing basis.
• If an analyte is rarely detected in a matrix type, use an LFM duplicate, if the sample
volume collected permits this additional QC. If not, use a portion of an alternate sample
(a duplicate) for precision assessment.
PURPOSE:
To evaluate measurement precision in analytical batch.
FREQUENCY:
At least one (1) with each sample batch, or on a 5% basis, whichever is more frequent.
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• If LFMD results are out of control, take corrective action to rectify matrix effect, use another
method, use the method of standard addition, or flag the data if reported.
• If duplicate results are out of control, then re-prepare and re-analyze the sample and take
additional corrective action, as needed.
NOTES:
• When the value of one or both duplicate samples is less than or equal to five times the MRL, the
laboratory may use the MRL as the control limit, and the duplicate results are not used.
• Refer to the specific method for LFM acceptance criteria until the laboratory develops
statistically valid, laboratory-specific performance criteria.
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NOTES:
• If the method of choice does not provide limits, calculate preliminary limits from the IDC.
• Base sample batch acceptance on results of LFB analyses rather than LFM duplicates
alone, because the LFM sample matrix may interfere with method performance.
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9. Internal Standard
• An internal standard is a unique analyte included in each standard and added to each
sample or sample extract/digestate just before sample analysis.
• These analytes should mimic the target analytes and should not interfere with the analysis.
USES:
• Organic analyses by GC-MS, HPLC, LC-MS, and other GC methods and IC methods, and
some metals analyses by ICP-MS
PURPOSE:
• To monitor retention time, calculate relative response, or quantify the analytes of interest
in each sample or sample extract/digestate.
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9. Internal Standard
NOTES:
• Choose an internal standard whose retention time or mass spectrum is separate from the
analytes of interest and that elutes in a representative area of the chromatogram.
• When quantifying by the internal standard method, measure all analyte responses
relative to this internal standard, unless interference is suspected.
• If internal standard results are out of control, take corrective action, including re-analysis
if required. Refer to the method of choice for specific internal standards and their
acceptance criteria.
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10. Surrogates, Tracers and Carriers

PURPOSE:
• To evaluate method performance in each sample.
SURROGATE STANDARD – used for used for organic analyses; a unique compound with a
known concentration that is added to each sample before extraction; they mimic the analytes
of interest and are unlikely to be found in the samples being analysed.
TRACERS – used for radiochemistry analyses; these are generally different isotopes of the
analyte or element of interest that are measured based on their characteristic radioactive
emission.
CARRIERS – used for radiochemistry analyses; these are stable isotopes of the element
being analyzed, or analogs thereof that are quantified by chemical or physical means.
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10. Surrogates, Tracers and Carriers

Out-of-control results for recoveries of surrogates and tracers requires appropriate
corrective actions to be conducted, such as re-preparation or re-analysis, if required.
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11. Calibration curves

INSTRUMENT CALIBRATION – performed according to method or instrument manual
instructions.
INITIAL CALIBRATION – perform this using at least three standard concentrations for linear
curves, at least five concentrations for nonlinear curves, or as specified by the method; lowest
concentration should be at the reporting limit and the highest concentration standard defines
the upper end of the calibration curve; shall encompass the expected concentration of
samples and its required dilutions.
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CALIBRATION FUNCTIONS:
• Response Factor – for internal standard calibration
• Calibration Factor – for external standard calibration
• Calibration Curve
Calibration curves can be:

• Linear through the origin
• Linear not through the origin
• Nonlinear through the origin
• Nonlinear not through the origin
Environmental
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RECOMMENDED ACCEPTANCE CRITERIA
IF USING RESPONSE OR CALIBRATION FACTORS:
% RPD FOR EACH ANALYTE < METHOD-SPECIFIED VALUE
IF USING LINEAR REGRESSION:
• Minimum correlation coefficient is defined in the method; if not, use 0.995 is recommended.
• Compare each calibration point to the curve by recalculating the concentration, if concentration of the
standard is not within the method’s specified criteria, determine source and correct before sample
quantitation.
• Alternatively, calibration of a method can be judged by comparing it to a reference method by measuring
its calibration linearity or %RSD among the RFs at each calibration level or concentration.
NOTES:
• Use the initial calibration with any of the of the above functions to quantitate analytes and samples of
interest.
• Initial calibration checks are done through calibration verification
• Initial calibration is to be done on new instrument is set up and CV criteria is not met.
Environmental
Services Division
CALIBRATION VERIFICATION
• CV involves running a calibration standard to confirm instrument performance has not
changed significantly since initial calibration.
• Base this verification on time (e.g. every 12 hrs) or on the number of samples analyzed
(e.g. after every 10 samples).
• Run one standard with a concentration near or at the calibration range.

Environmental
Services Division
UNACCEPTABLE PERFORMANCE
• Evaluate the calibration-verification analysis based either on allowable deviations from
the values obtained in the initial calibration or from specific points on the calibration
curve.
• If the calibration verification is out of control, then take corrective action, including re-
analysis of any affected samples. Refer to the method of choice for the frequency of and
acceptance criteria for calibration verification.
Environmental
Services Division
QUALITY CONTROL CALCULATIONS

A. INITIAL CALIBRATION
RELATIVE RESPONSE FACTOR (RRF)
RESPONSE FACTOR (RF)

Environmental
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A. INITIAL CALIBRATION
CALIBRATION FACTOR (CF) RELATIVE STANDARD DEVIATION (%RSD)

Environmental
Services Division

B. CALIBRATION VERIFICATION
% DIFFERENCE (%D) FOR RFs % DIFFERENCE FOR VALUES

Environmental
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C. LABORATORY-FORTIFIED BLANK/ LABORATORY CONTROL SAMPLE
D. SURROGATES
E. LABORATORY-FORTIFIED MATRIX
Environmental
Services Division
QUALITY CONTROL CHARTS

• Graphical record of quality through display of QC results over time to demonstrate
statistical control of an analytical process and to detect apparent changes in the process
that may erode the control.
• Can either be computer-generated or manually plotted.
Control charts for individuals – term used to refer to QC charts generated based on a single
QC result per batch, which is the basis of accepting or rejecting the results from this batch;
the rational size group is 1.
Environmental
Services Division

TYPES
A. ACCURACY (MEANS) CHART
• For RBs, LCSs, Calibration Check Standards, LFBs, LFMs, and Surrogates
• Constructed from average standard deviation of a specified number of measurements of the
analyte of interest.
Environmental
Services Division

TYPES
A. ACCURACY (MEANS) CHART
• Components:
• UPPER AND LOWER WARNING LEVELS (WLs) - ±2s (s = standard deviation)
• UPPER AND LOWER CONTROL LEVELS (CLs) - ±3s
• Notes
• Calculated limits should not exceed method-specified limits
• Standard deviation is derived from a series of measurements or trials performed before the QC Chart is established.
• Number of points required to generate the chart limits is method-specific.
• Set up an accuracy chart by using either the calculated values for mean and standard deviation or else the percent
recovery. (Percent recovery is necessary if the concentration varies.)
• Each analyte and method shall have its own chart
Environmental
Services Division

TYPES
A. PRECISION (RANGE) CHART
• For replicate or duplicate analyses of the analyte of interest
• Constructed from average standard deviation of a specified number of measurements, either as
%RSD or RPD, for replicate or duplicate analyses of the analyte of interest.
Environmental
Services Division

TYPES
A. PRECISION (RANGE) CHART
• Mean range:
• Control Limit
• Warning Limit
Control charts
If the data follow a normal distribution, 95 % of them

should fall within x ± 2s (between the Upper Warning Limit
and Lower Warning Limit) and 99.7 % should fall within x ±
3s (between the Upper Action Limit and Lower Action
Limit).
Control charts
• Data are plotted in time order, has a central

line for the average, upper line for the upper
control limit, lower line for the lower control
limit
- DAO 63 requires labs to display QC charts in a

conspicuous place.
Chart Analyses
a. One measurement exceeds a CLs.

Corrective action = repeat the analysis immediately. If the
repeat analysis is within the control limit, continue analysis; if it
exceeds the control limit, discontinue analysis and correct the
problem.
Chart Analyses
b. Two out of three successive points exceed a warning
limit
Corrective action = analyze another sample. If the next point is
within the WL, continue analysis; if the next point exceeds the
WL, check the method for bias (systematic error) and correct the
cause prior to additional analysis.
Chart Analyses
c. Trending: Seven consecutive plotted points are

on the same side (above or below) of the mean
Corrective action = discontinue analysis and correct the problem.
Chart Analyses
d. If 4 out of 5 successive points exceed 1s, or are in
decreasing or increasing order
Corrective action = Analyze another sample. If the plotted
point from this sample continues the trend of the previous
plotted 5 points, discontinue analysis and correct the problem,
if not, continue analysis.
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THANK YOU!!!

Quality Assurance and Quality Control in Environmental Analysis

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Quality Assurance and Quality Control in Environmental Analysis

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Environmental

DENR-EMB Research & Lab

2018 Intercomparison Exercises for DENR-EMB Laboratory Analysts

Quality Assurance and Quality Control

Quality Assurance and Quality Control

Quality Assurance Quality Control

Quality Assurance and Quality Control

Laboratory Services Sample

Quality Assurance (QA) elements

Quality Assurance (QA) elements

Quality Assurance (QA) elements

objective evidence - “data supporting the

Quality Assurance (QA) elements

Quality Assurance (QA) elements

Quality Assurance (QA) elements

Institute procedures to trace a sample

Chain of Custody (COC)

Chain of custody procedures

Chain of custody procedures, contd

Chain of custody procedures

Chain of custody procedures

Sample Reception and Login

Sample Reception and Login

C. Recording of samples into a master

Holding time - the maximum amount of time that can

• Samples analyzed beyond the maximum holding time

In addition to meeting the published hold times,

• Sufficient to perform all the required

• The sample must be representative of the

 bacterial samples – T ≤ 8°C

 When collecting samples from multiple

Recommended Volume, Container, Preservative and Holding Time

Anions (Cl, 400 - P, G, FP - Cool (≤6°C) 28 d

Recommended Volume, Container, Preservative and Holding Time

Parameters Minimum Container Type

Recommended Volume, Container, Preservative and Holding Time

Parameters Minimum Container Type

Recommended Volume, Container, Preservative and Holding Time

Recommended Volume, Container, Preservative and Holding Time

Recommended Volume, Container, Preservative and Holding Time

G = glass; P = plastic (polyethylene or equivalent); G(A) or P(A) =

Reference/s: 23rd Edition SMEWW, EPA Victoria Industrial Waste

SMEWW 23rd ed.

Quality Assurance Plan

Quality Assurance Plan

1. Initial Demonstration of Capability

2. To demonstrate that the laboratory’s modifications to a

1. Initial Demonstration of Capability

1. Initial Demonstration of Capability

a. Analyze at least 20 spike samples.

3. Method Detection Level

3. Method Detection Level

3. Method Detection Level

3. Method Detection Level

3. Method Detection Level

• MDL then is equal to whichever is greater: MDLs or MDLb.

5. Laboratory-Fortified Blank/Laboratory Control Standard

5. Laboratory-Fortified Blank/Laboratory Control Standard

5. Laboratory-Fortified Blank/Laboratory Control Standard

8. Duplicate Sample/ Laboratory-Fortified Matrix Duplicate

8. Duplicate Sample/ Laboratory-Fortified Matrix Duplicate

8. Duplicate Sample/ Laboratory-Fortified Matrix Duplicate