The 2012 updates to CFR 40 Part 136 Clean Water Act methods and how they

affect you

William LippsMarket Specialist –Water Analysis Products

http://water.epa.gov/scitech/methods/cwa/update_index.cfm

Signed into law April 17, 2012

Examples of potentially regulated entities

• States, territories, and Indian tribes

• Industry

• Municipalities

Depends on permits

Rule effective 30 days after FR publication

Implementation?

Always follow permit!

Some specify Part 136

Some specify method

Conflicts with Permits

“Or Equivalent” in permit?

Any Part 136 method

Notify permitting authority

“Or Equivalent” not in permit?

Ask permitting authority

What happens if a method is delisted?

Use method in your permit until a new permit is issued

40 CFR Part 136

Changes to Part 136

• New Methods• New Parameters

• More than 250• Mostly pesticides

• Updated Methods• Microbiology • Metals• Method Modification (clarification)• Quality Control procedures

Bacteria and Microbiology

• Revised and Updated

• E. Coli• Enterococci• Fecal• Cryptosporidium• Giardia

Minor Changes and Flexibility

• Cryptosporidium (1622) and Giardia (1623)

• Different filters and stains• QC clarifications• Temperatures

• Bacteria

• Minor technical corrections

Oshiro.robin@epa.gov

Method 624 VOCs

Pesticides and PCB’s

• Organochlorine• Organophosphate• Herbicides• Triazines• Thiophosphates• Carbamates

Pesticides and PCB’s

• New methods means new parameters (lots)

• Mostly GC with ECD or FPD/NPD

• Some NPD only• Method 525.2 = SPE GC/MS• Method 632 carbamates = HPLC

Pesticides and PCB’s

• Flexibility • Different columns• Different detectors

• Cannot modify extraction

Gomez-Taylor.Maria@epa.gov

Metals

• ASTM D1976 - 2007 - ICP-AES

• SM 3125-2009 - ICP/MS

New ICP Methods

• Method 200.5 Axial

• Method 200.7 allows Axial

• Collision cells allowed

for 136.3

Table 1b

• New Methods

• New Analytes

• Updated methods

• New ATPs

• Fewer Columns

• Indentations

• Headers

Standard Methods?

Only one version

By year, not edition

New Standard Methods and new Parameter

17a Free Chlorine

Ammonia Nitrogen – Parameter 4

Manual Distillation6

Footnote 6

Manual distillation not required if:• comparable data on file• 9 different matrices• Matrix spikes• Matrix spike duplicates• With and without distillation• Comparable = RPD < 20% on all

Diffusion

Total Cyanide – Parameter 23

• 2 new ASTM Standards• D 7511 – UV gas diffusion amperometry• D 7284 – Distillation gas diffusion amperometry

• 1 Updated ASTM Standard• D 2036

• Gas diffusion amperometry• Ion Chromatography

Available Cyanide – Parameter 24

• 2 updated ASTM Standards• D 6888 – LE gas diffusion amperometry• D 2036 – recommends D 6888

• Updated OIA-1677

Free Cyanide – new Parameter 24a

• 2 ASTM Standards• D 7237 – automated gas diffusion amperometry • D 4282 – passive diffusion colorimetry

• OIA-1677

Fluoride – Parameter 25

Manual Distillation6

TKN – Parameter 31

• Methods/techniques that need distillation• Titration • Nessler• ISE• Manual phenate*• Automated phenate*

* Or salicylate

Diffusion

TKN – Parameter 31

• Methods / Techniques with no manual distillation• Automated distillation• Automated diffusion• Direct colorimetry

Nitrate + Nitrite – Parameter 39

Reduction Colorimetric • Proprietary• Discrete Analyzer• Not an enzyme

Not IncludedASTM D7575

Oil and Grease – Parameter 41

TOC – Parameter 42

• New ASTM Standard – D 7573

DO – Parameter 46

• Updated ASTM Standard – D 888

• Optical Sensors• Allowed for BOD

Multiple ATPs for BOD approved in footnotes

Orthophosphate – Parameter 44

Thank goodness for ASTM D7365

Part 136.6 Flexibility

Method

Modifications Equivalency

ATP

136.6

Restrictions to part 136.6

Cannot be Method Defined Analyte• Temperature• Oil & Grease• Total Phenols• TSS, SS, TDS• BOD, COD

Restrictions to part 136.6

ATP ≠ modifications to existing methods

No ATP letter

Chemistry = “essentially” the same

Determinative step = “essentially” the same

Equivalent Results = meet or exceed

You must document allowed changes with data

• Demonstration of Capability

• Spikes and duplicates

• Method detection limits

• Blanks

• LCS

Document the reason for the modification, and how it was modified

• Overcome an interference

• Less hazardous

• Green Chemistry

• Suitable calibration range

• Better precision and accuracy

Examples of allowed modifications

• Gas diffusion

• Different wavelengths

• Interchange of oxidants

• Discrete, manual, or continuous flow

• Automated or manual sample prep

• Collision cells

• Buffer reagents and complex reagents

Calibration Model that fits data

Chromatography

• Nitrogen purge• Traps• Desorb time• Heated Sparge

Part 136.7 Quality Control

12 Quality Control Checks

• DOC

• MDL

• Method Blanks

• LCS

• MS/MSD

• Internal Standards, Surrogates, or tracers

12 Quality Control Checks (continued)

• CCV / ICV

• Control Charts

• Corrective Action

• QC Acceptance Criteria

• Definition of the Batch

• Specified minimum frequency of QC checks

Walker.lemuel@epa.gov

Oil&GreaseTotal Nitrogen

Low level Total PhosphorusUpdated 624 and 625More frequent updates

What are some hot issues in near future?

Continual Improvement – one scoop at a time

William Lipps

William.lipps@xyleminc.com

www.oianalytical.com