Stacie Metzler, Quality Assurance Manager
Hampton Roads Sanitation District
William (Bill) Ray, William Ray Consulting, LLC
Quality Assurance Manager, California State
Water Resources Control Board
MODERATOR:
Akin Babatola, Laboratory/Environmental
Compliance Manager
WWTF City of Santa Cruz
Moderator
Married and lives in Santa Cruz
Akin Babatola
Occupation:
•
Laboratory/Environmental Compliance Manager WWTF City of Santa
Cruz. Since 2002.
•
Previously the Research Microbiologist/Process Lab Section Manager at
the City of San Jose Environmental Services Department Laboratory
(1993-2002)
Laboratory/Environmental
Compliance Manager,
WWTF City of Santa Cruz
Author of several articles and presentations in wastewater analyses and
NPDES permit issues.
Led the development of the BOD/TOC conversion equation at the City of Santa
Cruz; the implementation of new bacterial monitoring regimen and the
introduction of monitoring techniques for trace organic compounds in the
effluent at the City of Santa Cruz. All of these are now embedded in the NPDES
permit of the City of Santa Cruz WWTF.
Notable Professional Associations and Memberships:
•
Water Environment Federation, since 1992
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American Society of Microbiologists, since 1996
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American Public Health Laboratories, since 2009
Education:
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MS Molecular Biology, University of Arizona, (1988)
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BS (Hons) Microbiology, University of Ibadan, Nigeria.
Notable Professional Awards:
•
Past Chair of Water Environment Foundation Laboratory Practices
Committee, 2008-2011, and
•
Previous winner of the Crystal Crucible Awards for Environmental
Laboratory Management in 2003.
Stacie Metzler
Quality Assurance Manager
Hampton Roads Sanitation District
Stacie received her Bachelor’s of Science from Ohio University in
1992 and soon after started her career in the environmental
laboratory sector with Hampton Roads Sanitation District as has
worked in their Central Environmental Laboratory in various
positions over the last 19 years, including as Quality Assurance
Manager for the last 12 years. During that time, Stacie has led the
effort to develop and implement a NELAC compliant quality system,
and worked with laboratory staff and Accreditation Body
Representatives to ensure accreditation requirements are met to
maintain a scope of over 500 fields of certification. In addition Stacie
has been involved with many activities external to HRSD including:
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Current Chair of the NELAC Institute Proficiency Testing
Executive Committee
Current member of the NELAC Institute Proficiency Testing
Expert Committee
Current member of the WEF Lab Practices Committee and
Revitalization Workgroup
Current Vice- Chair of the WEF Operations Challenge
Committee
Past Lab event Coordinator for both VWEA and WEF Operations
Challenge
Current Vice- President of VWEA
Past JAM Committee Co-Chair
Past Chair and Member of the VWEA VA AWWA Lab Practices
Committee
Background
• Guidelines Establishing Test Procedures for
the Analysis of Pollutants Under the Clean
Water Act; Analysis and Sampling
Procedures (40 CFR Part 136)
– Notice for Public Comment September 10, 2010
– Published May 18, 2012
– Promulgated June 1, 2012
– Effective June 18, 2012
Background
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New and Revised Wastewater Methods
Examples of Allowed Method Flexibility
New QA/QC Requirements
Clarifications and Corrections to Previously
Approved Methods
• Revisions to Preservation and Holding
Times
Intent of adding the 12 QA/QC
Elements (136.7)
• Codify that a permittee or laboratory is
required to use suitable QA/QC when
conducting Clean Water Act Compliance
Analyses.
• Applies to methods listed in table 136.3 that
DO NOT have QA/QC procedures as part of
the method or compendium from which the
method was taken.
Intent of adding the 12 QA/QC
Elements (136.7)
• Not the intent for approved methods that
include QA/QC to be updated to include
additional requirements.
• If an approved method with QA/QC does not
include all 12 elements it is not required that
the laboratory add the missing elements
– Could result in laboratories establishing
acceptance criteria for QC elements not
appropriate to the analysis
Intent of adding the 12 QA/QC
Elements (136.7)
• All Laboratories should have SOPs
that document procedures based
on approved methods
–QA/QC including acceptance limits
as included in the reference method
or compendium
• Standard Methods
Options for Implementation
• Follow and reference protocols in
“equivalent” EPA method for the parameter
not containing QA/QC
• Reference the QA/QC section of an
approved Part 136 method from a
consensus organization compendium
• Incorporate the applicable part 136.7
QA/QC elements into the laboratory’s SOP
12 QA/ QC Elements
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Demonstration of Capability (DOC)
Method Detection Limit (MDL)
Laboratory Reagent Blank (LRB)
Laboratory Fortified Blank (LFM)
Matrix Spike (MS) and Matrix Spike Duplicate (MSD)
Internal Standards, Surrogates or Tracers
Calibration
Control Charts
Corrective Action
QC Acceptance Criteria
Preparation and Analytical Batches
QC Frequency
Demonstration of Capability
(DOC)
A Procedure to establish the ability of the
analyst to generate results of acceptable
accuracy and precision (TNI 2009)
Method Detection Limit
• The constituent concentration that,
when processed through the entire
method produces a signal that has 99%
probability of being different from the
blank. (SM 22nd Edition: 2011)
• Performed according to 40 CFR Part
136 Appendix B.
Laboratory Reagent Blank
(LRB)
• Also known as Method Blank (MB)
• A sample consisting of reagent(s), without
the target analyte or sample matrix,
introduced into the analytical procedure at
the appropriate point and carried through
all subsequent steps to determine the
contribution of the reagents and of the
involved analytical steps to error in the
observed value. (EPA QA Glossary)
Laboratory Fortified Blank
(LFB)
• Also known as Laboratory Control
Sample (LCS)
• A sample matrix, free from the analyte
of interest, spiked with verified known
amounts of analytes or a material
containing known and verified amounts
of analytes and taken through all
sample preparation and analytical steps
of the procedure. (2009 TNI Standard)
Matrix Spike (MS)/ Matrix Spike Duplicate
(MSD)
• Also know as Laboratory Fortified Matrix (LFM)/
Duplicate LFM (DLFM)
• MS- a sample prepared by adding a known mass
of target analyte to a specified amount of matrix
sample for which an independent estimate of
target analyte concentration is available. Spiked
samples are used, for example, to determine the
effect of the matrix on a method's recovery
efficiency. (EPA)
• MSD- Duplicate MS. Together the MS and MSD
are used to determine precision. (EPA)
Internal Standards, Surrogates
or Tracers
• Internal Standard- a standard added to a test portion of a
sample in a known amount and carried through the entire
determination procedure as a reference for calibration and
controlling the precision and bias of the applied analytical
method. (EPA)
• Surrogate- a pure substance with properties that mimic the
analyte of interest. It is unlikely to be found in environmental
samples and is added to them for quality control purposes.
(EPA)
• Tracer- a known quantity of a radioisotope that is added to a
solution of a chemically equivalent radioisotope of unknown
concentration so that the yield of the chemical separation can
be monitored. (EPA)
Calibration- Initial and Continuing
• Initial Calibration- use at least three concentrations
of standards for linear curves, five for nonlinear
curves. Ensure the calibration range encompasses
the analytical concentration values expected in
samples. (SM 22nd Edition: 2011)
• Continuing Calibration- analysis of one standard at
a concentration near or at the mid-point of the
curve periodically through the run to ensure
instrument performance has not changed
Control Charts
• Control Chart- a graph of some measurement
plotted over time or sequence of sampling,
together with control limit(s) and, usually, a
central line and warning limit(s)
• A useful tool to trend quality control results and
monitor performance of the analytical system
• Each certifying or regulatory body determines
implementation of acceptance limits based on
control charting
Corrective Action
• Corrective Action- the action taken to
eliminate the causes of an existing
nonconformity, defect or other
undesirable situation on order to
prevent recurrence.
QC Acceptance Criteria
• Quality Control- the overall system of technical
activities whose purpose is to measure and
control the quality of a product or service so
that it meets the needs of users. The aim is to
provide quality that is satisfactory, adequate,
dependable, and economical.(EPA)
• Acceptance limits must be documented and
followed as a way to determine the analytical
system is in control
Preparation and Analytical Batches
• Batch- Samples prepared and/or analyzed together with
the same process and personnel, using the same lot(s)
and reagents
• Preparation Batch-one to twenty samples of the same
quality systems matrix, meeting the above criteria with a
maximum time between the start of processing of the first
and last sample to be 24 hours (TNI 2009)
• Analytical Batch- prepared samples which are analyzed
together as a group. An analytical batch can include
prepared samples originating from various quality system
matrices and can exceed 20 samples (TNI 2009)
Quality Control Frequency
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Method dependant
Program dependant
Customer requirements
Define Protocols in SOPs, Quality
Assurance Manual and other supporting
documentation
• Meet state specific requirements
William (Bill) Ray
William Ray Consulting, LLC
Began work at a full-service commercial laboratory located in
Southern California where I did everything from bacterial
testing to ocean monitoring. Left there to go to work for the
State at the Colorado River Regional Water Quality Control
Board in their one-man laboratory. Transferred to the
Sanitation and Radiation Laboratory in Health Services
eventually moving over to laboratory certification. Was in
California ELAP for 5 years before transferring to the State
Board where I was the Quality Assurance Program Manager.
Bill is the Owner/President of William Ray Consulting, LLC. A
recently formed consulting firm specializing in technical and
compliance assistance to the environmental laboratory
community. WRC has developed training tools and self-study
guides to basic statistical elements and working with censored
(non-detect) data sets. WRC’s first publication, now in the
August/September edition of WEF Laboratory Solutions, is
titled “Legally Defensible, how well will your data hold up”.
Education:
•
Bachelor’s in Chemistry from UC Irvine
•
Master’s in Chemistry from Cal Poly Pomona
EPA’s Method update rule
2012
The Final Rule and Strategies to
meet the 12
Topics
• Key elements of the Rule
• Changes between Proposed and Final
Rule
• Challenges in this Rule
• Strategies to help meeting the “12”
Key Elements of the Rule
• Addition new methods
• Changes in citation of methods from
Standard Methods…
• Changes to Table II
• Changes to sections 136.4 thru 136.6
• Addition of 12 Essential Quality Control
Elements
Addition of Luminescence DO
• LDO added to Table IB under both
dissolved oxygen and BOD (NOTE 63)
• Approved method is 10360 v1.2
• Those with ATPs used v1.1
• Only change between versions is the
addition of BOD procedure
Citing Standard Methods
• Change from edition citation to
approved year citation of methods from
Standard Methods
• Best source is Standard Methods online
• Most invested in print editions due to
costs
• 22nd edition best if print desired
Table II (Preservation/Hold times)
• Change to bacterial hold times –
removed separate times for collection to
receipt and receipt to analysis
• Changes notes for cyanide preservation
– reference ASTM 7369-09a
• Affirms filtration of orthophosphate
samples within 15 minutes
Sections 136.4 thru 136.6
• Minor changes to ATP processes found
in 136.4 and 136.5
• Includes modification of preservation
and hold times
• Addition to 136.6 of many “allowed”
modifications
The 12 Quality Assurance
Elements
• Added reference to equivalent EPA
methods and consensus-setting standards
for missing elements
• Added requirement to specifically state
reasons for any element not included in
SOP
• Possible consensus-setting bodies include
Standard Methods, ASTM, NELAC
Changes made in Final Rule
• Removal of methods for PCB and Polybrominated biphenyl (PBDE) congeners
– methods considered not ready
• 600 series methods (Appendix A) and
EPA method 200.7 (Appendix C) not
removed
Some future modifications
• PCB and PBDE congeners when
methods improved
• Non-solvent method for oil and grease
• Fecal coliforms by IDEXX Colilert
Challenges in this Rule
Standard Methods
• Changes in Standard Methods citations
still freezes the reference in time
• Standard Methods’ approval date is for
all methods within a section
• Not clear what constitutes an “editorial”
versus substantive change
Challenges in the Rule – the 12
• Failed to add sample duplication. No
measure of precision possible where there
is no MS or LFB available
• Does not stipulate use of a current version
of a consensus-setting standard
• Does not mandate missing elements come
from other sources – labs may still
establish their own processes/criteria
• Reasons need only be documented –
reasons may vary
Possible sources and
Suggested Strategies
The 12
Elements Usually Covered
• Elements 2 (MDL), 3 (LRB), 4 (LFB), 5
(MS/MSD), 7 (Calibration), 10
(Acceptance Criteria) very likely already
specified in method
• At least for Chemistry.
• Other types such as microbiology and
toxicity testing will require “inventive”
processes
Sources
• Almost no method will include all 12
elements
• Use of Standard Methods including the
10X0 and the X020 sections will prove
most helpful
• The common missing elements will be
Trend Analyses (Element 8) and Root
Cause Analyses (Element 9)
Problematic Elements
• Element 2 in cases where the procedure in
Appendix B does not apply
• Elements 4 and 5 in cases where a
solution of known concentration cannot be
produced
• Element 7 where there is nothing to
calibrate
• Strategies exist to creatively deal with
these but they can also be easily
dismissed
Strategies – Element 2
• Method may state minimum
measureable quantity
• Example – Minimum depletion of
oxygen stated in the BOD method
• Method may state a minimum resolution
• Example – temperature or pH
Strategies – Element 4
• Cannot make a solution of known
concentration
• Microbiology - All positive and negative
culture checks represent tests of an
LFB
• Dissolved oxygen – saturated water is
only assumed to be saturated
Strategies – Element 5
• Not possible if no LFB can be created
• The Element’s purpose is the
establishment of precision assessment
mechanism
• Substitute sample replication
• Question remains why sample
replication not listed as a possible
mechanism for this Element
Strategies – Element 7
• The Element is about calibrating a
quantitation system by the comparison of a
response vs. concentration
• Some tests do not directly calibrate in this
fashion
• Examples are gravimetric and bacterial
tests
• Substitute indirect calibrations or
calibration of critical devices controlling
test
Element 8 Trend analysis
The general direction in which
something tends to move
Purpose
• It is assumed that all individual small
errors in a method are random
• A lack of randomness moves the
system in a noticeable direction
• Trend analyses point out this movement
in time to take action
Control Charts
• Control charts are very common
• However so is control chart abuse
• Control charts great for any quality
control parameter that is based on
statistics
• Other forms of trend analyses
necessary when the parameter is not
based on statistics
130
120
110
Results
100
LCL
UCL
90
80
70
1
4
7 10 13 16 19 22 25 28 31 34 37 40 43 46 49 52 55 58 61 64 67 70 73 76 79 82 85 88 91 94 97 100
Another form of trend analysis
Date
3/12/11
3/13/11
3/14/11
4/10/11
4/11/11
4/12/11
5/14/11
5/15/11
5/16/11
6/9/11
6/10/11
6/11/11
7/13/11
7/14/11
7/15/11
7/16/11
Correction Factor oC
+0.5 (set 6/1/10)
+0.3 (set 6/2/11)
Temperature Reading oC
103.5
103.2
102.9
102.0
103.1
105.4
105.3
104.6
104.2
103.2
104.2
103.8
101.9
101.2
102.1
101.8
Corrected Reading oC
102.6 oC – 105.4 oC
104.0
103.7
103.5
102.6 ADJ up
103.6
105.9 ADJ dn
105.8 ADJ dn
105.1
104.7
103.5
104.5
104.1
102.2 ADJ up
101.5 ADJ up
102.4 ADJ up
102.1 ADJ up
Oven Replaced
Element 9 Root cause
analyses
The real reason for failure
Corrective Action
• Everyone takes corrective action
• What isn’t noticed is how often the
same corrective action is taken
• Root cause analyses asks the question
of why a corrective action was needed
more than once
• Improves the quality system
• Some things will remain a mystery
So when implementing the 12
• Use a check list
• Mark which Elements are already there
• State any inventive processes and why it
meets the Element criteria
• Format reasons why an Element will not
be included
• Rewrite the SOP to include missing
Elements and reasons for not including
Elements
Use all of your resources
Talk to others and trade your
experiences
BILL RAY
WILLIAM RAY CONSULTING, LLC
925-300-3350
[email protected]