The 2012 updates to CFR 40 Part 136
Clean Water Act methods and how they
affect you
William Lipps
Market 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
Implementation?
Depends on permits
Rule effective 30 days after FR publication
Conflicts with Permits
Always follow permit!
Some specify Part 136
Some specify method
“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
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
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
• New Methods
Table
1b
•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
Oil and Grease – Parameter 41
Not Included
ASTM D7575
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
136.6
ATP
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
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
What are some hot issues in near future?
Oil&Grease
Total Nitrogen
Low level Total Phosphorus
Updated 624 and 625
More frequent updates
Continual Improvement – one
scoop at a time
William Lipps
William.lipps@xyleminc.com
www.oianalytical.com