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EPA Office of Water Method Update Rule
proposed -2015
Virginia Good Laboratory Practices
Conference
July 2015
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William Lipps
Shimadzu Scientific Instruments
Environmental/Mining Business Unit Manager
[email protected]
Andrew Eaton, PhD, BCES
Eurofins Eaton Analytical Inc.
Lab Technical Director
Vice President
[email protected]
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The 2015 proposed MUR revises and adds
Part 136 methods
Clean Water Act Methods
increased flexibility
To improve data quality
keep current with technology advances
Amendments to the MDL procedure
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The proposal consists of minor changes,
edits, and 7 new methods
~100 method revisions from ASTM International
and Standard Methods
6 Alternate Test Procedures (ATPs)
1 USGS Method (based off of an ATP)
Revisions to Methods 608, 624, and 625
Method Detection Limit (MDL) Revision
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How a MUR becomes a Law, and other
important items from schoolhouse rock
EPA seeks new and revised methods
• ASTM
• Standard Methods
• ATP
• EPA
EPA prepares proposal
• Workgroup
• Office of General Counsel
• Senior Management
• Office of Policy
• Administrator
Proposed in Federal Register
• Public comment
EPA prepares a Response
• Workgroup
• Office of General Counsel
• Senior Management
• Office of Policy
• Administrator
Final Rule
published
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Comment period closed May 20, 2015
175 comments, representing
400 pages and numerous
organizations
Inconsistent comments.
Mostly on revisions to the organic methods and
the MDL
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You Can Find All The Comments Yourself
www.regulations.gov
EPA-HQ-OW-2014-0797
Open Docket Folder
Open all
Good luck, go nuts and have fun!
http://www.regulations.gov/
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When Can You Expect a Final MUR?
The 2012 MUR was proposed in 2010
Likely late 2016…. But don’t hold your breath.
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If a comment is made on topics not under
discussion, then:
“this was not an item subject to revision”
Is the likely answer
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The 2015 proposed updates includes no
new EPA methods
Revised or corrected EPA methods
Revised or corrected Standard Methods
Revised or corrected ASTM methods
6 new ATPs
2 new USGS methods
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A Note on Revisions to EPA Methods
A revision does not include a technical change Technical change
requires re-validation
Therefore, these revisions do not completely re-
write methods! Revisions consolidated memos and letters
Method data from initial inter-lab studies (early
1980’s)
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The pathway to new CWA EPA methods
requires validation and inter-lab studies
Methods at Part 136 require multiple laboratory
validation (9 labs and 9 matrices)
Without an ILS EPA can only make minor changes
Or, rely on consensus standard organizations and
ATPs
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ASTM and Standard Methods Changes in
this (2015) MUR
Proposed ASTM and SM Revisions Editorial changes
Minor QC changes
Technical clarifications
Neither ASTM nor Standard Methods submitted any new
methods (for regulated parameters) for this MUR
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EPA Method Activity for the 2015 MUR
3 revised methods
5 corrections
Updated MDL
Read my lips,
No new
Methods
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Methods 608.3, 624.1, and 625.1
Revisions only – limited changes
Updated technology
Capillary columns, updated references
Method Flexibility Allows more changes with internal
documentation (no ATP
required)
Method Harmonization Altered some QA/QC frequencies and
standards to match
OGWDW and SW-846 methods
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EPA revised Method 608 (now 608.3) and
adds a detector
New name – GC/HSD Halogen specific detector in addition to
ECD
New detector data EPA 1656
New analytes – Table 2 Allows GCMS if sensitive enough
Toxaphene and PCB in Table 2
Includes SPE
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EPA Revised Method 608 - Comments
New detector data single lab
Higher detection limits
New analytes Table 2
Single lab only
When do you reject a SPE?
To allow or not to allow qualifiers
Requests to use CLP data
Allow < 1000 ml sample
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EPA revised Method 624
100 new compounds
Bring your own QC limits (BYOQC)
1984 is not that far away
Allows H2 as a carrier gas
Adds flexibility from Part 136.6
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EPA Revised Method 624 Comments
Allow exceedances instead of repeating on QC failure
Remove ML from Table 1 (1984 data)
Update/ add tune criteria for H2 Remove flexibility and leave in
Part 136.6
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EPA revised Method 625
Lots of new compounds in a new Table 3
Bring your own QC limits (BYOQC)
Allows the use of SPE (with 9 matrices)
Adds flexibility from Part 136.6
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EPA Revised Method 625 Comments
Allow exceedances instead of repeat QC
Remove ML from Table 1 (1984 data)
Provide more specific guidance in many sections
Remove flexibility and leave in Part 136.6
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General QC Comments from ELAB on
Revisions to 608, 624, and 625
Methods 608.3, 624.1 and 625.1 have statements related to
the
need to have acceptable quality control (QC) for all tests
before
the data can be “used for permitting or regulatory
compliance
purposes.” To require that all QC results meet acceptance
criteria before use in compliance or for regulatory decisions
is
unreasonable and may not be achievable
Translation = Add qualifiers
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Revision to the Part 136 Appendix B MDL
Originally Submitted by TNI
MDL Calculation of spikes remains unchanged.
Addresses background contamination, and multiple
instrument MDLs
Diverse Comments! A lot of people like it….
Some think it just adds costs
It does need some clarifications to make it usable.
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Notice that the MDL is redefined
Current Definition New Definition
99% Confidence that
signal is greater than
ZERO
99% Confidence that
signal is greater than
BLANK
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How to do the “Burrows” MDL
Do 7 replicates across 3 or more batches Comes from the drinking
water approach
Do 7 blanks
Spike results must meet qualitative ID criteria
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Calculation of the MDL
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
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Hypothetical Calculations of the MDL
Spiked Blank 1 Blank 2
0.020 0 0
0.015 0 0
0.025 0.005 0.005
0.018 0.020 0.005
0.022 0 0
0.016 0 0
0.011 0 0
X 0.018 0.0036 0.0014
Sx 0.00467 0.0075 0.0024
MDL 0.014 0.022 0.009
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One commenter’s evaluation on change in their
MDL
Compound
(mg/L)
Old MDL New MDL
SO4 10 38
P 0.005 0.84
CN 0.005 0.014
TKN 0.5 1.59
B 0.010 0.036
Ag 0.003 0.006
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Typical Comments on the MDL Revisions
Multi analyte/multi calibration methods like 608 could
represent a lot of work for the quarterly verification.
Provide better guidance on multiple instruments and
addition of new instruments.
Quarterly verification will add significant costs. Require less
frequent verification.
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Specific Comments on Revisions to the MDL
Procedure
Laboratories would be required to evaluate the MDL to
account
for background levels of contamination.
If a laboratory uses multiple instruments, then the laboratory
will
have to calculate the MDL for all the instruments.
Laboratories will be required to check their MDL quarterly
ACIL and ELAB supported these changes (original concept came
from ACIL), but did seek a lot of clarification to ensure that
the
method is practical.
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For the new procedure, use ML and blanks
from 7 previous batches to re-evaluate
Perform ML spikes with each batch to verify MDL
Verify quarterly
Recalculate MDL annually using existing data
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USGS methods for nitrate/nitrite
Replaces cadmium with reductase Low level and high level
methods
First well validated Discrete Analyzer methods
Same technique as NECi ATP
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ATP methods included in the 2015 MUR
NECi – Nitrate/Nitrite by Reductase
Timberline – Ammonia by FIA GD-EC
IDEXX – Colilert18
NCASI (paper and pulp specific) – TN and TP
HACH – sTKN
HACH – Nitrate
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NECi Nitrate/Nitrite Method
Reduces nitrate to nitrite using an enzyme
Nitrite measured colorimetrically Extensive Multiple laboratory
study
All used Discrete Analyzers Different manufacturers
Results equivalent to Cd reduction
Green method
Currently approved as an ATP
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Timberline Ammonia method
Flow Injection Gas diffusion with conductivity
detection
Green method
Currently approved as an ATP
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IDEXX Colilert18 Method
Allows incubation at 44.5 ± 0.2 ºC
Currently approved as an ATP
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NCASi TN (TKN) and TP Method
Limited to paper and pulp (do not use)
Alkaline persulfate digestion
PO4 and NO3 measured by CFA
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HACH TN (TKN) Test n Tube Method
Alkaline persulfate digestion
NO3 measured colorimetrically
Requires 2 tests Total N
NO3
TN – NO3 = TKN
Currently approved as an ATP
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HACH NO3 Test n Tube method
NO3 measured colorimetrically (345nm)
Measures NO3+NO2 on preserved samples
Currently approved as an ATP
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Wait till MUR is published!
Most 608, 624, 625 modifications
are already allowed at 136.6
ATP’s get State approval
Start tracking blank data
Run ML standards
Use these ML and Blanks in two
years when MUR passes
Caution – Warning, Warning, Warning
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And now for a summary of who done it
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Method Activity By Organization
0
10
20
30
40
50
60
70
StandardMethods
ASTM ATP EPA USGS
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Most Method Development Activity Is Done
By Volunteers
ATP Manufacturers
Individual industry
Consensus standards Manufacturers
Industry
Commercial Labs
Municipal Labs
Universities
Government
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What methods may end up in the next
MUR?
Total Nitrogen and Phosphorus Alkaline persulfate and IC
Total Nitrogen High temperature combustion with
chemiluminescence detection
PCB’s GCMSMS?
On-line analyzer methods
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Consensus Standards Organizations are
developing methods you must follow
Who are these people?
Who is making these methods you must use?
Shouldn't you be involved?
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Any Questions?
Andy Eaton, PhD, BCES
Technical Director/Vice President
[email protected]
William Lipps
Environmental/Mining Business Unit
Manager
[email protected]
