The 2015 TNI Standard
and Other News of
Interest
TCEQ
May 5, 2015
THE 2009 TNI NELAP
STANDARDS





Developed by consensus
Ensured key elements were retained.
Removed redundant language
Removed non-essential requirements
Considered the following goals:




Easy to use and understand;
Easy to grow and expand;
Easy to revise and implement; and
Applicable to all laboratories.
THE 2009 NELAP
STANDARDS

Four Small Volumes = Four Standards

Volume 1: Requirements for Laboratories


Volume 2: Requirements for Accreditation
Bodies



7 Modules
3 Modules
Volume 3: Requirements for PT Providers
Volume 4: Requirements for a PT Provider
Accreditor
VOLUME 1

Everything a lab needs to know




Proficiency testing (Module 1)
Personnel requirements (Module 2)
Quality systems (Module 2)
Technical requirements (Modules 3-7)
3: Asbestos
 4: Chemistry
 5: Microbiology
 6: Radiochemistry
 7: Toxicity

Volumes 2, 3 and 4


Interesting reading, for maybe QA
Manager
Volume 2: Requirements for ABs


Volume 3: Requirements for PT Providers


Includes how to assess PT sample analysis
Includes scoring of PT results
Volume 4: Requirements for PT Provider
Accreditors
So why do we need a 2015
standard?
Issues with the 2015
Standard

PT reporting not acceptable to some ABs


All of ISO 17025 not included






Other minor PT issues
Reference Materials
Method Validation
DOC language confusing and inconsistent
Chemistry module needs improving
Microbiology and Radiochemistry modules
written by chemists
Other minor issues
Standards Development Process

Committee develops Working Draft Standard (WDS)

Presented to TNI Members and Public for Comment
Comment Period for Working Draft Standard - V1M5 (Microbiology)
The EL-V1M5 (Microbiology) Working Draft Standard (WDS) was presented by
webinar to those stakeholder groups who may subsequently adopt, use, or be
accredited to the standard. Pursuant to SOP 2-100, any stakeholder or
stakeholder group is invited to submit written comments to the Microbiology Expert
Committee Chair Robin Cook (cookr@codb.us) and Program Administrator Ilona
Taunton (ilona.taunton@nelac-institute.org), no later than Friday September 5.

Committee develops Voting Draft Standard (VDS)

Presented to TNI Members for Vote


Positive, Positive with Comment, Negative with Comment, Abstain
Committee must resolve all comments
Persuasive, Non-Persuasive, Hold for Next Revision

Standards Development Process

Committee develops Interim Standard (IS)


Presented to TNI Members and Public for Comment
Response to Comments document also published
Comment Period for Interim Standard - V1M4 (Calibration)
The EL-V1M4 (Calibration) Voting Draft Standard (VDS), dated March 2013, was
approved by the membership. Pursuant to SOP 2-100, changes were made to the
standard as a result of persuasive comments received from voters. On June 18,
2014 it was presented by webinar as an Interim Standard (IS) to those stakeholder
groups who may subsequently adopt, use, or be accredited to the standard. Any
stakeholder or stakeholder group is invited to submit any further comments on the
changes. As a result of this input, the Chemistry Expert Committee may further
modify the IS.

Committee works with stakeholder groups to resolve any
remaining comments and pass a Final Standard
Changes to PT Standards

Reverse some decisions made in the 2009
standard







LOQ reporting
Analysis date
5-7 months
No QC check sample for chemistry
New sections for WET and Protozoa
Many changes affecting PT Providers
Clarification of role of AB in reviewing PT
results
2012 Quality System
Standard





Revised to include all of ISO/IEC 17025
verbatim
Clarified confusing language on method
validation in Modules 3-7
Moved general language on method
selection and validation to Module 2
New definition for LOD to be consistent
with MDL
Other minor clarifications

2015 Quality System Standard
Correct a note about ISO/IEC 17025


Revise temperature calibration (5.5.13.1)




V1M2: Section 5.6.1
Allow single point verification at mandated
condition
Comments due May 20
Publish Response to Comments
Document
Finalize a revised standard
Chemistry: Module 4

Accomplishments




VDS for Calibration passed. Response to
Comments completed. Interim standard published,
Response to Comments for IS completed.
Modified the EPA MDL procedure; published on the
website, presented to EPA
MDL Procedure published in the February 19 MUR
Plans


Finalize Calibration Standard
Start work on detection and quantitation WDS,
incorporating the modified MDL procedure
Revised Calibration Section





Removal of calibration points
Number of standards required
Relative Error / Relative Standard Error
Corrective action for CCV
Many other minor changes
Microbiology: M5

Accomplishments

Published WDS for V1M5




Clarified definition of source water
Revised Method Selection and Validation
Revised chlorine residual check
Plans

Complete standards development cycle for V1M5
Radiochemistry: M6

Accomplishments



Published a Voting Draft Standard for V1M6
Comments due May 15
Summary of Changes


Many new terms
Major rewrite
The 2015 Standard





Changes to PT, Quality Systems, Chemistry,
Microbiology and Radiochemistry
Also changes to Volumes 2, 3, and 4
Expected to be adopted by CSDP in August
2015.
Will need review by LASEC for suitability
Will need adoption by NELAP for implementation
NELAP implementation will be for a specific date,
likely 2017
Implementation of 2015
Standard





2-3 year process
Extensive training will be provided to labs
and lab assessors
New checklists will be developed
Quality Manual template will likely be
revised
Half-day webinar planned for July 15 in
conjunction with TNI’s summer meeting
Exploring the Future of
National Environmental
Laboratory Accreditation
Background
• ELAB letter to FEM, FEM response
• TNI Board assigned action to
Advocacy Committee
• Advocacy committee proposed
outreach to stakeholders
Discussion

Original assumptions
EPA would direct the program
 All states would participate
 May not be valid assumptions today


How do we move forward?
Objective


Get input on the state of national
accreditation from stakeholders to learn
what is and is not working in the current
program
Ask participants to identify barriers to state
and federal participation in the current
program in order to determine how to best
move national accreditation forward
Direction from
Louisville Meeting

Conduct interviews of non-NELAP states

Hold a webinar for other stakeholders

Conduct a face to face workshop session
in DC in August 2014
Issues Identified

Technical Issues





EPA/State Issues





Method vs Quality System Audits
1 vs 2 PT samples
Harmonization with EPA Cert Manual
Simplify TNI Standard and Accreditation Process
Recognition of NELAP accreditation by other states
Encourage more EPA involvement
Consistency among NELAP states
Accreditation of State labs
Communications and Outreach



Help for small labs
Outreach to Non-NELAP states
Technical resources
Technical Issues




Misperception that these two approaches are not already
integrated. TNI should better publicize how the quality
systems approach supports a method based approach.
Open to change PT only if there was a guarantee that
non-participating states would join. Look at all the
compromises that went into the 2 PTs per year decision.
TNI standard is more than DW. Don’t want to force all
labs into DW requirements. If incorporate into the TNI
standard, need to make DW a consensus standard.
Generic application. Guidance to help labs with processmentors, tools. Surveillance assessments. Better use of
tools and technology for ABs to manage programs
EPA/State Issues







Work at the grass roots level with lab associations. Assign
a TNI ambassador to every non-NELAP state.
Re-visit the crosswalk with TNI standard and DW
certification manual.
Develop an bi-annual “State of National Accreditation”
report and offer briefings to EPA
Increase management oversight of assessments
Promote assessor calls and assessor forum to
disseminate information.
Encourage state labs to use non-governmental
accreditation bodies (NGABs).
Promote EPA lab competency policy.
Communication and
Outreach




Explore website changes. Consider a “tool box”
format with flow charts, diagrams, templates,
examples and other graphics to make information
more readily available.
Establish a mentoring group for small labs and
FSMOs.
Consistently have a seminar at NEMC to
introduce new labs to TNI.
Develop a free webinar to introduce TNI and
highlight the benefits of accreditation.
Bob Beimer
Bill Telliard
Bruce Colby
Larry Keith
Somebody from Texas
2015 Methods Update Rule






Proposed on February 19, 2015
Updated EPA Methods 608.3, 624.1, 625.1
New and Updated Standard Methods, ASTM
methods and methods from other sources
Changes to sample preservation and holding
times for microbiology
Many more
Revised MDL Procedure
details in TNI
Other “Technical Corrections”




Methods 1600. 1603. 1680. 1682
WET methods manuals
Footnotes
2,2’-oxybis(1-chloropropane)
webcast
Footnotes
Table 1B
52. Adds 1999 errata sheet to Method 300.1, cover sheet is not
on EPA methods page, but can be found by searching.




Method is shown as 300.1-1
Clarifying analyst role in meeting criteria when modifying
methods
Correctly typo LRB to LFB
Clarifying reporting data qualifiers for failed QC
Table 1A

Added footnote 30 for 9222D: The verification frequency is at
least five typical and five atypical colonies per sampling site on
the day of sample collection and analysis.
Table 1C: Dichlorobenzenes

2007 MUR removed approval of
dichlorobenzenes from Method 625



“significant losses of these volatiles can occur
using the prescribed sample collection
procedures in the LLE methods, resulting in
relatively low recovery of these compounds”
Method 624 approved for all three isomers
2015 proposed rule list 624.1 for two isomers
(1,3 and 1,4) and 625.1 for one (1,2)
Method Modifications: 136.6

Deleted some language that has been added to
Methods 608.3, 624.1 and 625.1, e.g.


alternate extraction, concentration, and cleanup
procedures, changes in column and type of mass
spectrometer
Added new section on Method Modifications

The permittee must notify their permitting authority of the
intent to use a modified method. Such notification should be
of the form “Method xxx has been modified within the
flexibility allowed in 40 CFR 136.6.” The permittee may
indicate the specific paragraph of 136.6 allowing the method
modification. Specific details of the modification need not be
provided, but must be documented in the Standard
Operating Procedure (SOP) and maintained by the
analytical laboratory that performs the analysis.
600 Series Methods

Developed in the 1970s and reflected
the best practice at the time, e.g.






Analytes = priority pollutants
Liquid-liquid extraction
Packed columns
Separate base/neutral and acid fractions
because of special column needed for
phenols
3-point calibration
Methods were inter-laboratory validated
Since 1979

Other EPA Programs used these methods as a basis





Expanded analyte lists
New technology





Contract Laboratory Program SOWs
Drinking Water: 508, 524, 525
SW-846: 8080, 8081, 8082, 8240, 8250, 8260, 8270
Capillary columns
Solid Phase Extraction (SPE)
Selected Ion Monitoring (SIM)
Hydrogen carrier gas
Additional QC
Summary of Changes

Expanded to include additional analytes








Table 1 = “Analytes of Interest”
Table 2 = Expanded Analytes (Table 3 for 625.1)
Added Reporting Limits (Minimum Level or ML)
Much more flexibility in the procedure
More QC and more requirements for reporting
Some inconsistencies
Some interesting new concepts
Some interest new identification techniques
Analytes of Interest



Those required to be determined by a
regulatory/control authority or in a
permit, or by a client.
If a list of analytes is not specified, the
analytes in Table 1 must be determined,
at a minimum, and QC testing must be
performed for these analytes.
MDLs and MLs provided for most
analytes
Expanded Analytes

Very long lists





Very little performance data
Includes some that are likely not measurable



67 pesticides
105 volatiles
315 semivolatiles
Methanol
Phthalic anhydride
Includes analytes of little or no regulatory
concern that may not be measurable
May lead some data users to requests
tests that are not practicable
Minimum Level


EPA Concept that has existed for >20 years
ML = MDL x 3.18


Round to the nearest 1, 2 or 5 x 10n



3.18 =10/3.14 = Curries LQ
So ML Values would be 1, 2, 5, 10, 20, 50, etc
MLs published in the method = MDL x 3
If MDL is wrong, 3 x MDL is also wrong
Inconsistencies


Storage and replacement of standards
Standard traceability




Second Source standard
Closing CCV



608.3 = to a national standard, when available.
624.1/625.1 = to NIST or other national standard
608.3 = Yes
624.1/625.1 = No
Batch definitions


608.3/625.1 = 20 samples
624.1 = 12 hours
Storage of Standards

608.3



Store neat standards
or single analyte
standards in the dark
at -20 to -10 °C.
Store multi-analyte
standards at 4°C or
per manufacturer’s
recommendations.
Place a mark on the
vial at the level of the
solution so that
solvent evaporation
loss can be detected.


624.1
 Store standard solutions at 10 to -20°C, protected from
light, in fluoropolymer-sealed
glass containers with minimal
headspace.
625.1
 Store at <6 °C and protect
from light.
 Check frequently for
degradation or evaporation,
especially just prior to
preparing calibration
standards from them.
Replacement of Standards

608.3
 Stock standard solutions
must be replaced after 12
months or sooner if
comparison with quality
control check standards
indicates a change in
concentration.
 Analyze all standard
solutions within 48 hours of
preparation. Replace
purchased certified stock
standard solutions per the
expiration date. Replace
stock standard solutions
prepared by the laboratory
or mixed with purchased
solutions after one year, or
sooner


624.1
 Replace after one month, or
sooner if the concentration
changes by more than 10
percent.
625.1
 Replace purchased certified
stock standard solutions per
the expiration date. Replace
stock standard solutions after
one year, or sooner if
comparison with QC check
samples indicates a problem.
Second Source Standard


608.3



different
manufacturer or
different certified lot
verify the accuracy
of the initial
calibration
concentrations must
be within 20%
difference of the true
value
624.1






Not listed in Reagents
Not used to check ICAL
= LCS
Criteria = Table 7
May run 2 consecutive
LCS
625.1





Not listed in Reagents
Not used to check ICAL
= CCV
Criteria = Table 6
May run 2 consecutive
Calibration Curves
 608.3
 At least three levels (5
recommended, 6 for quadratic)
 Low point must be below
published ML
 External Standard
o If the RSD is less than 20%,
linearity can be assumed
o If curve, must be inversely
weighted to concentration
o Must have R2 of 0.99 or RSE of
20%
 Internal Standard
o If the RSD is less than 15%,
linearity can be assumed
o If curve, must be inversely
weighted to concentration
o Must have R2 of 0.99 or RSE of
15%
 624.1/625.1

At least five levels (6 for
quadratic)

Average RF may be used if
RSD < 35%
If curve, must be inversely
weighted to concentration
Must have R2 of 0.92 or RSE
of 35%
Low point must be below
published ML
ML can be rounded, but may
not be above published level;
i.e., ML of 4.8 cannot be
rounded to 5




Correlation Coefficients for
Evaluation of Calibration
Anal. Chem. 1981 (C.L. Grant)
 One practice which should be discouraged
is the use of the correlation coefficient as a
means off evaluating goodness of fit of
linear models.
 Thorough statistical analysis of analytical
calibration data should be used to provide
optimal evaluation of results. The correlation
coefficient is not an effective statistic for this
purpose.
Calibration Verification

608.3


Aldrin =75-125
 Dieldrin = 48-125
Table 4 criteria
includes all sample
processing steps
608 was once per day and 15%
624.1

Verified at the
beginning and end of
each 24-hour shift
Criteria published in
Table 4, e.g.




= LCS
Criteria in Table 7, e.g.


Bromoform = 70-130
Bromomethane = 15-185
This is the same as 624

625.1


20% difference changed
to Table 6 (Q?)
Values can be as high as
13-200%
Quality Control

Old Methods

DOC per analyst
Precision and
accuracy
 One time

New Methods







Blank
10% MS
10% QC Check
Statements of
accuracy
DOC per laboratory








Precision, accuracy and MDL
Initial and annually (should)
Blank
5% MS; 5% MSD
LCS per batch
Surrogates
Internal standard areas (50200%)
Statements of accuracy
PT Samples
(recommended)
IDC/DOC

4 replicate QC Check samples



Concentration at or below mid-point
Compare results to QC criteria (Tables 4, 6, or 7)
For analytes with no criteria, use 136.6
Criteria from an “equivalent” method
 Default criteria (e.g., 60-140%)


MDL Study



As described in Appendix B
MDLs must be equal to or lower than those in the
method, OR
1/3 the regulatory level
MS/MSD





Spike at least 5% of samples from each site
Data user to identify samples and analytes
If direction cannot be obtained, the laboratory must spike
at least one sample in duplicate per batch.
Spiked sample results should be reported only to the data
user whose sample was spiked.
If recovery falls outside the designated range, the
result for the analyte in the sample is suspect and
may not be reported or used for permitting or
regulatory compliance.
Statements of Accuracy




Calculate the average recovery and sd
from MS/MSD (for each discharge?)
Calculate interval X ± 2sd
Update on a regular basis
What would this be used for?
This was in the 1984
versions of these methods
QC Limits for MS/MSD




Calculate new limits after 20 MS/MSD
Update every two years
80% of limits better than QC Table
QC Table are the maximum limits
LCS




One LCS per batch of 20 or less
Use criteria in QC Table (Table 4, 6 or 7)
Repeat the test for those analytes that failed to meet the
criteria. If these analytes now pass, system performance is
acceptable and analysis of samples may proceed. If this
occurs, repeat the test using a fresh LCS, or perform and
document system repair.
Update criteria using same procedure as MS/MSD
Blanks


One blank per batch
Re-extract if blank result is:




Greater than MDL, or
Greater than 1/3 compliance limit, or
Greater than 1/10 sample concentration
If re-testing of blanks results in repeated failures,
the laboratory should document the failures and
report the problem and failures with the data.
NELAP: the concentration is at or above the reporting
limit, AND greater than 1/10 of the amount measured
in the sample
Surrogates




Must be spiked in every sample
Laboratory develops limits; 60-140%
can be used as interim limits
Any failure, re-analyze sample if
available
Surrogate recoveries from the blank and LCS may be
used as pass/fail criteria by the laboratory or as
required by a regulatory authority, or may be used to
diagnose problems with the analytical system.
Blank Subtraction




When subtracting two measurements,
the uncertainty in the final measurement is
equal to the sum of the uncertainties in the
original measurements:
(A ± s) - (B ± s) = (A - B) ± (sA + sB)
Dieldrin: MDL = 6; ML = 18; s = 42%
C = (18 -6) ± (7.5+2.5) = 2 - 22
http://physicsed.buffalostate.edu/pubs/MeasurementAnaly
sis/MA1_9ed.pdf
Specific Method Issues
608.3 Second Column
Confirmation


If values from two columns are in
agreement within a factor of 2,
analyte is present
If not within factor of 2
If interferent is detected on second column,
report result and advise data user of
interference
 If no interferent is detected, report ND at the
lower concentration

624.2 Mass Spectrometer


Scan rate changed to 7 scans/second
Mass range = 35-260 with suggestion to go to 25260 for:





Acrolein (m/z 56, 55, 58)
Acrylonitrile (m/z 53, 52, 51)
Choloromethane (m/z 50, 52)
Vinyl chloride (m/z 62, 64)
Interferences below m/z 35




Methanol (m/z 29, 31, 32)
Nitrogen (m/z 28)
Oxygen (m/z 32)
Argon (m/z 40)
624.1 GC resolution



Valley between 1,2-dibromoethane and
chlorobenzene must not exceed 25%
1,2-dibromoethane is not listed as an
analyte
The two compounds have very different
spectra


1,2-dibromoethane 107 (109, 188)
chlorobenzene 112 (77, 114)
GC/MS Identification




Retention time: ±30 seconds changed to 0.06
RRT
Relative intensities changed from ±20% to 50% to
200%
New: “m/z’s present in the acquired mass
spectrum for the sample that are not present in
the reference mass spectrum must be accounted
for by contaminant or background m/z’s.”
Isomers must have peak resolution of 50%
compared to 25% in Method 624/625 (and
methods 524/525)
QC Failures
If continued re-testing results in repeated
failures, the laboratory should document the
failures (e.g., as qualifiers on results) and either
avoid reporting results for analytes that failed or
report the problem and failures with the data.
Failure to report does not relieve a discharger or
permittee of reporting timely results. Results for
regulatory compliance must be accompanied by
QC results that meet all acceptance criteria.
624 allowed QC check to override MS failure; no
criteria for blanks
Reporting





Report quantitative data to ML to 3 significant
figures
Report the lower of two results from 608.3
Report results less than ML as < ML, “or as
required by the regulatory authority or permit”
Allows for blank subtraction if requested or required
Results from tests performed with an analytical
system that is not in control must not be reported or
otherwise used for permitting or regulatory
compliance purposes, but do not relieve a
discharger or permittee of reporting timely results.
Reporting Caveat (1.7.1)
 EPA has promulgated this method at 40 CFR
Part 136 for use in wastewater compliance
monitoring under the National Pollutant
Discharge Elimination System (NPDES). The
data reporting practices described in Section
15.2 are focused on such monitoring needs and
may not be relevant to other uses of the method.
600s: Summary of Technical




Updated technology to current practice
Much more flexibility
Additional analytes
Some inconsistencies between the
methods
Summary: QC and Reporting

New concepts may be troublesome






Daily calibration checks are problematic



Making data user select samples to be spiked
Establishing accuracy/precision per site/discharge
Reporting rules for 608.3
Revised identification criteria for 624.1 and 625.1
Blank subtraction
Not consistent with current industry practice
Will greatly increase error
QC section is problematic




Not consistent with current industry practice
Cannot realistically be done
Will increase laboratory fraud
The caveats help, but not enough
Changes to Appendix B
Revised MDL Procedure
 Developed by TNI’s Chemistry Committee
 Addresses issues with current procedure



Blanks not centered around 0
Short term variance does not equal long term
variance
Lack of guarantee of actual detectability
Summary of Procedure



One procedure, start with 7 spikes and 7
blanks
MDLS = tSs (Std Dev of spikes)
MDLB = X + tSb (Std Dev of blanks)


Use whichever is highest as the MDL
Requires ongoing spikes
Details






Requires spreading the initial 7 replicates
across at least 3 batches
Includes instructions for multiple instruments
with the same assigned MDL
Requires that spike results meet qualitative ID
criteria
Requires ongoing (quarterly) spikes
Recalculate (but do not redo) every year
Includes instructions for determination of a MDL
in a specific matrix
Much more tomorrow:
Richard Burrows
SUMMARY

Not as dramatic as the 2010 rule




Most of this just adds new methods and corrects
problems
New 600 Methods a great improvement from a
technology perspective but will create enormous
hardships if finalized in their current form
MDL is a incredible improvement!
Send in your comments!



Deadline extended to May 20
www.regulations.gov
Docket ID: EPA–HQ–OW–2014–0797
Contact TNI
Jerry Parr, Executive Director
www.nelac-institute.org
 jerry.parr@nelac-institute.org
 817-598-1624
