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EPA Office of Water Method Update Rule

proposed -2015

Virginia Good Laboratory Practices

Conference

July 2015

William Lipps

Shimadzu Scientific Instruments

Environmental/Mining Business Unit Manager

wclipps@shimadzu.com

Andrew Eaton, PhD, BCES

Eurofins Eaton Analytical Inc.

Lab Technical Director

Vice President

andyeaton@eurofinsus.com

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

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

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

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

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!

When Can You Expect a Final MUR?

The 2012 MUR was proposed in 2010

Likely late 2016…. But don’t hold your breath.

If a comment is made on topics not under

discussion, then:

“this was not an item subject to revision”

Is the likely answer

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

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)

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

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

EPA Method Activity for the 2015 MUR

3 revised methods

5 corrections

Updated MDL

Read my lips,

No new

Methods

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

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

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

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

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

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

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

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

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.

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

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

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

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

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

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.

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.

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

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

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

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

Timberline Ammonia method

Flow Injection Gas diffusion with conductivity

detection

Green method

Currently approved as an ATP

IDEXX Colilert18 Method

Allows incubation at 44.5 ± 0.2 ºC

Currently approved as an ATP

NCASi TN (TKN) and TP Method

Limited to paper and pulp (do not use)

Alkaline persulfate digestion

PO4 and NO3 measured by CFA

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

HACH NO3 Test n Tube method

NO3 measured colorimetrically (345nm)

Measures NO3+NO2 on preserved samples

Currently approved as an ATP

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

And now for a summary of who done it

Method Activity By Organization

0

10

20

30

40

50

60

70

StandardMethods

ASTM ATP EPA USGS

Most Method Development Activity Is Done

By Volunteers

ATP Manufacturers

Individual industry

Consensus standards Manufacturers

Industry

Commercial Labs

Municipal Labs

Universities

Government

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

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?

Any Questions?

Andy Eaton, PhD, BCES

Technical Director/Vice President

andyeaton@eurofinsus.com

William Lipps

Environmental/Mining Business Unit

Manager

wclipps@shimadzu.com