Update on USEPA Methods,
Regulations, Accreditation and Related
Activities
Midwest Environmental Laboratory
Stakeholders Summit
December 3, 2011
Jerry L. Parr
Catalyst Information Resources
A SLOW YEAR (Except for TNI)
 No New SW-846 Methods
 Method Update Rule Not Finalized
 No progress on Detection and Quantitation
 UCMR 3
 No other significant new regulations
 Many minor actions by EPA and States
 The NELAC Institute actions
 Will be presented on Friday
Excluding Air methods
For the period December 7, 2010 through December 2, 2011.
SW-846
 No new methods
 Look for revised Method 8000 in 2012
Methods Update Rule
 Proposed September 23, 2010
 New methods
 Updated versions of approved methods
 Revised method modification and analytical
requirements
 Clarifications and corrections
 Changes to sample collection, preservation, and
holding time requirements
 Minimum QC requirements
Expected to be final in January 2012
Regulations Affected
 Part 423: Steam Electric
Power NPDES
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Revise definitions related to
residual chlorine
 Part 430: Pulp and Paper
NPDES
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Remove Methods 1650 and
1653
 Part 435: Oil and Gas NPDES
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Method revisions and
corrections
 Part 136: Wastewater
Methods
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Many, many, many
changes
 Part 260: RCRA Methods
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Update 1664A to 1664B
Changes to Part 136
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New EPA Methods
Updated EPA Methods
New and Updated Standard Methods
New and Updated ASTM Methods
> 250 New Analytes
New table for microbiology in ambient water
Table II: Preservation & Holding Time
Sections 136.4 and 136.5 on ATP
Section 136.6, Method Modifications
New Section 136.7 on minimum QC
Remove Appendices A (600 methods) and C (200.7)
Revise Appendix D (metals P/A data)
New EPA Methods
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200.5
525.2
608.1
608.2
614
614.1
617
619
622
622.1
632
1614A
1668C
1627
Trace Elements by Axially Viewed ICP-AES
Organics by GC/MS (Table 1G only)
Organochloride Pesticides. (Table 1G only)
Organochlorine Pesticides. (Table 1G only)
Organophosphorus Pesticides. (Table 1G only)
Organophosphorus Pesticides (Table 1G only)
Organohalide Pesticides and PCBs. (Table 1G only)
Triazine Pesticides. (Table 1G only)
Organophosphorus Pesticides (Table 1G only)
Thiophosphate Pesticides. (Table 1G only)
Carbamate and Urea Pesticides (Table 1G only)
Brominated Diphenyl Ethers by HRGC/HRMS.
Chlorinated Biphenyl Congeners by HRGC/HRMS.
Prediction of Mine Drainage Quality.
Revised/Updated EPA Methods
 1664B
 624
 1622
 1623
 1103.1
 1106.1
 1600
 1603
 1680
 1650
 1653
Oil and Grease (HEM and SGT-HEM)
Add acrolein and acrylonitrile as approved analytes
Cryptosporidium
Giardia
E. coli
Enterococci
Enterococci
E. coli
Fecal Coliform
New Analyte
121. Adsorbable Organic Halides
122. Chlorinated Phenolics
New Analyte
A Closer Look: Methods 1622 and 1623
 Update to 2005 version
 flexibility to choose among several types of filters,
quality controls, and stains,
 clarification on measuring sample temperatures,
quality control sample requirements and use of
quality control sample results,
 minimizing carry-over debris,
 analyst verification procedures, and
 sample condition criteria upon receipt.
 Change preservation to 1-10 degrees C
Methods 1103.1, 1106.1, 1600, 1603, and 1680
 Minor technical corrections, e.g.
 tryptone broth should be tryptone water
 positive control organism for the cytochrome oxidase
reagent has been changed to P. aeruginosa from E.
faecalis,
 negative control organism for Simmons citrate agar
has been changed to S. flexneri from E. coli
Standard Methods
 Generally, only most recent version will now be approved
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17th, 18th, 19th, etc. no longer approved
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Method approval is shown by the year, not the edition
 New Methods
 Updated Methods
 New method and a new analyte: 17A. Chlorine - Free available
New and Updated Standard Methods
 5520 B-2001 and 5520 F-2001
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Oil and Grease.
SM 5520 G-2001 not approved because it allows use of a co-solvent, such as acetone.
4500-NH3 G-1997
Ammonia (as N) and TKN
4500-B B-2000
Boron.
4140-1997
Inorganic Ions
3114 C-2009
Arsenic and Selenium.
3111 E-1999
Aluminum and Beryllium.
5220 B-1997
Chemical Oxygen Demand.
4500 NORG D-1997
Kjeldahl Nitrogen - Total.
4500 P G and 4500 P H-1999
Phosphorus.
4500 P E and 4500 P F-1999
Phosphorus.
4500 O B, D, E and F-2001
Oxygen.
4500 O D-2001
Oxygen.
4500 O E-2001
Oxygen.
3500 K C-1997
Potassium.
2540 E-1997
Residues – Volatile.
4500 SiO2 and 4500 SiO2 F- 1997 Silica.
4500 SO4 C, D, E, F and G-1997 Sulfate.
4500 S2- B-2000 and C-2000,
Sulfide.
New and Updated ASTM Methods
 D2036, D6888, D7284, and D7511
 D888
 D7573
Total Cyanide
Dissolved Oxygen
Total Carbon and Organic Carbon.
ASTM New Analytes and Methods
 D4282 and D7237
 D7065, D7574, & D7485
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24A. Free Cyanide
114. Nonylphenol
115. Bisphenol A
116. p-tert-Octylphenol
117. Monoethoxylate
118. Nonylphenol Diethoxylate
More New Methods
 SM 3125-2009
 ASTM 1976-2007
ICP/MS for 24 metals
ICP/AES for 25 metals
Not discussed in preamble
ICP/AES and ICP/MS for Additional Metals
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Gold by ICP/MS (4 methods)
Iridium by ICP/MS (SM 3125)
Magnesium by ICP/MS (4 methods)
Mercury by ICP/AES and ICP/MS (4 methods)
Palladium by ICP/MS (SM 3125)
Phosphorous by ICP/AES (3 methods)
Platinum by ICP/MS (SM 3125)
Potassium by ICP/MS (4 methods)
Not discussed in
Rhodium by ICP/MS (SM 3125)
preamble
Rhodium by ICP/MS (SM 3125)
Silica by ICP/MS (4 methods)
Sodium by ICP/MS (4 methods)
Tin by ICP/MS (4 methods)
Titanium by ICP/MS (4 methods)
ASTM - Oil and Grease Methods
 D7066 and D7575 not included
 Do not use n-hexane
 Other significant changes from 1664
 TPH is not an analyte in Part 136
New Alternate Test Procedures
 Hach Method 10360 Luminescence Measurement
of Dissolved Oxygen (LDO®),
 In-Situ Incorporated’s
Method 1002-8 Dissolved Oxygen (DO),
 Method 1003-8 BOD, and
 Method 1004-8 CBOD,
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 Mitchell Methods M5271 and M5331 for turbidity;
 Thermo Scientific’s Method AQ4500 for turbidity;
 Systea Scientific, LLC’s Systea Easy (1-Reagent)
Nitrate.
Clarifications and Corrections
 Grab samples must be filtered within 15 minutes
for o-PO4 Preamble only
 Fecal coliform, total coliform, and fecal
streptococcus methods added to Table 1H
 Other minor corrections
Holding Times and Sample Preservation
 Information in this table takes precedence over
instructions provided in specific methods or elsewhere
unless a party documents the acceptability of an
alternative to the Table II instructions. The nature,
timing and extent of the required documentation (i.e.
how to apply and review as well as the amount of
supporting data) are left to the discretion of the
permitting authority (State Agency or EPA Region) or
other authority and may rely on instructions, such as
those provided for method modifications at 136.6.
 Examples provided:
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24-hour BOD
Cyanide
Holding Times and Sample Preservation
 E. Coli and Enterococcus
 Change from 2 hours to 8 hours
 Cyanide
 Footnotes 5 and 6 extensively rewritten (shortened) to
reference ASTM Methods and allow analyst flexibility
 WET
 Samples cannot be frozen
 Do not need to be 0-6 C if analyzed on day of collection
 Hold time only refers to first use
Alternate Test Procedures
 136.4: Nationwide
 Application to National
Coordinator
 Provide a detailed
description of the
proposed procedure.
 Provide comparability
data
 Procedure may be used
for limited use prior to
regulation
 136.5: Limited
 Application to Regional
Coordinator
 Provide justification
 Provide a detailed
description of the
proposed procedure.
 Demonstrate
applicability to specific
effluents
Method Modifications: 136.6
 Extensively rewritten with more examples
 Acceptable reasons for an analyst to modify a method
include:
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analytical practices that lower detection limits,
improve precision,
reduce interferences,
lower laboratory costs, and
promote environmental stewardship by reducing generation of
laboratory wastes.
 Acceptable modifications may use existing or emerging
analytical technologies that achieve these ends provided
that they do not depart substantially from the
underlying chemical principles employed in methods
Examples of Allowed Modifications
 Changes between manual method, flow analyzer and discrete
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instrumentation.
Changes between automated and manual sample preparation.
Use of interference reduction for ICP-MS.
Using a different acid to adjust pH in colorimetric methods.
Changes in calibration model.
Use of Relative Standard Error (RSE).
Use of prepackaged reagents.
Use of Selected Ion Monitoring (SIM).
Changes in purge-and-trap sample volumes or operating
conditions.
Combine base/neutral and acid fractions for Method 625.
New 136.7: Required Quality Control
 Mandatory for all methods
 12 Essential QC Checks
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(1) Demonstration of Capability (DOC);
(2) Method Detection Limit (MDL);
(3) Laboratory reagent blank (LRB), also referred to as
method blank;
(4) Laboratory fortified blank (LFB), also referred to as a
spiked blank, or laboratory control sample (LCS);
(5) Matrix spike, matrix spike duplicate, or laboratory
fortified blank duplicate (LFBD) for suspected difficult
matrices;
(6) Internal standards, surrogate standards (for organic
analysis) or tracers (for radiochemistry);
12 QC Checks (the last 6)
 (7) Calibration (initial and continuing), initial and
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continuing performance (ICP) solution also referred to as
initial calibration verification (ICV) and continuing
calibration verification (CCV);
(8) Control charts (or other trend analyses of quality control
results);
(9) Corrective action (root cause analyses);
(10) QC acceptance criteria;
(11) Definitions of a batch (preparation and analytical); and
(12) Specify a minimum frequency for conducting these QC
checks.
Changes to Appendix D
 Precision and Accuracy Data for EPA AA
Methods
 Almost all methods were deleted in 2007 MUR
 Proposed rule would remove all Appendix D
data except for:
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279.2, Thallium
289.2, Zinc
Changes to Part 423
 NPDES Regulations for power plants
 Revise definitions for residual and free chlorine
 Total residual chlorine (or total residual oxidants for
intake water with bromides) means the value obtained
using any of the chlorine-total residual methods in
Table IB.
 Free available chlorine means the value obtained using
any of the chlorine-free available methods in Table IB.
Changes to Part 430
 NPDES Regulations for pulp and paper plants
 Remove Methods 1650 and 1653 for adsorbable
organic halides (AOX) and chlorinated
phenolics
 Add adsorbable organic halides (AOX) and
chlorinated phenolics as analytes 121 and 122 in
Table 1C
Analyte 122: Chlorinated Phenolics
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Trichlorosyringol
3,4,5-Trichlorocatechol
3,4,6-Trichlorocatechol
3,4,5-Trichloroguaiacol
3,4,6-Trichloroguaiacol
4,5,6-Trichloroguaiacol
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
Tetrachlorocatechol
Tetrachloroguaiacol
2,3,4,6-Tetrachlorophenol
Pentachlorophenol
Changes to Part 435
 NPDES Regulations for offshore oil and gas wells
 Remove methods and create Analytic Methods for the
Oil and Gas Extraction Point Source Category
 Incorporate additional QA procedures in the marine
anaerobic biodegradation analytic method
 Correct some erroneous references and omissions in the
method for identification of crude oil contamination
 Add a schematic flow diagram for qualitative
identification of crude oil
Methods for Offshore Oil and Gas
 1617 Static Sheen Test
 1619 Drilling Fluids Toxicity Test
 1646 Procedure for Mixing Base Fluids With
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Sediments.
1647 Degradation of Non Aqueous Base Fluids in a
Marine Closed Bottle Biodegradation Test System:
1655 Crude Oil Contamination in Non-Aqueous
Drilling Fluids by GC/MS.
1670 Detection of Oil Contamination in NonAqueous Drilling Fluids (NAF).
1674 Non- Aqueous Drilling Fluid (NAF) Base Fluid
from Drill Cuttings
UCMR 3
 Unregulated Contaminant Monitoring Proposed Rule
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March 3, 2011; 76 FR 11713
 30 contaminants for monitoring over a 5-year period
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28 chemicals
2 viruses
 Monitoring provided by EPA contract labs and large
municipals
 All labs will require EPA approval
 Monitoring scheduled to begin in 2013
UCMR 3 CHEMICALS
 9 Volatile Organic
Compounds using Method
524.3
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1,2,3-trichloropropane
1,3-butadiene
chloromethane
1,1-dichloroethane
n-propylbenzene
bromomethane
sec-butylbenzene
chlorodifluoromethane
bromochloromethane
 Synthetic Organic
Compound using Method
522
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1,4-dioxane
 7 Hormones using EPA
Method 539
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17-[beta]-estradiol
17-[alpha]-ethynylestradiol
(ethinyl estradiol)
estriol (16-[alpha]-hydroxy-17[beta]-estradiol)
equilin
estrone
testosterone
4-androstene-3,17-dione
UCMR 3 CHEMICALS
 6 Perfluorinated
Chemicals using
Method 537
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perfluorooctane sulfonate
perfluorooctanoic acid
perfluorononanoic acid
perfluorohexane sulfonic
acid
perfluoroheptanoic acid
perfluorobutane sulfonic
acid
 4 Metals using EPA
Method 200.8
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cobalt
molybdenum
strontium
vanadium
 Oxyhalide Anion
using Method
300.1
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chlorate
UCMR 3 VIRUSES
 Enterovirus
 Norovirus
 Would be monitored by a tissue culture or qPCR
assay
OTHER MINOR EPA ACTIONS
 New CLP Guidance for Field Samplers
http://www.epa.gov/superfund/programs/clp/dow
nload/sampler/CLPSamp-01-2011.pdf
 Saccharin removed from Appendix VIII
(12/17/10; 75 FR 78918)
 Guidance for Enhanced Monitoring of
Hexavalent Chromium in Drinking Water
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Where the systems should collect samples
How often they should be collected
Guidance on analytical methods
http://water.epa.gov/drink/info/chromium/guidance.cfm
OTHER MINOR EPA ACTIONS (Cont)
 EPA Publishes Water Laboratory Alliance Response Plan
 Procedures for coordinated laboratory response to water contamination
incidents that may require additional analytical support and a broader
response than a typical laboratory can provide.
 http://water.epa.gov/infrastructure/watersecurity/secres/upload/WLARe
sponsPlan_November2010.pdf
 EPA Publishes Policy on Competency of Laboratories and Other
Similar Organizations
 Requires organizations that provide data to EPA under contract submit
documentation of their competency, which may include accreditation:

Organizations performing environmental analysis for the Agency shall
demonstrate their qualifications in the fields of analyses to be conducted, prior to
performing such analyses. Where accreditation or certification is available for
those fields of analysis, organizations may submit documentation of existing
accreditations or certifications. Accreditation/ certification granted by an
organization that accredits environmental data operations to an international
consensus standard, or a state accreditation or certification program acceptable
to EPA, or that the contracted laboratory is participating in the EPA Contract
Laboratory Program.
 http://www.epa.gov/osa/fem/pdfs/fem-lab-competency-policy.pdf
OTHER MINOR EPA ACTIONS (Cont)
 Training Courses on Analysis of Radionuclides in Water
 The training provides an understanding of how and why to analyze water
samples for the presence of radionuclides according to the methods specified
in the EPA 900 series procedures and EPA's Manual for the Certification of
Laboratories Analyzing Drinking Water. The training also provides insight
on how to plan, implement, and document appropriate quality control and
quality assurance procedures for the analysis of radionuclides in water.
http://www.epa.gov/safewater/radionuclides/training/index.html
 LCMRL Calculator Published
 The Lowest Concentration Minimum Reporting Level (LCMRL) is defined as
the lowest spiking concentration at which recovery of between 50 and 150%
is expected 99% of the time by a single analyst. The LCMRL is estimated
using statistical procedures which estimates a probability distribution for
spike recovery as a function of spiking concentration. This requires
regression modeling that estimates expected value and expected variance for
repeated measurements as functions of spiking concentration.
http://water.epa.gov/scitech/drinkingwater/labcert/analyticalmethods_ogw
dw.cfm#four
OTHER MINOR EPA ACTIONS (Cont)
 Clarification on Sample Preservation for
Total Phenolics
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CuSO4 not needed
OK to use H2SO4
Etc.
Memo available from Catalyst upon request
STATE ACTIONS: PA
 Pennsylvania Develops Guidance for
Homeowners for Basic Oil & Gas Parameters
 The PA DEP has developed a list of parameters that are
recommended for homeowners who wish to have their
private well tested before drilling operations for oil and gas
production.
 http://files.dep.state.pa.us/RegionalResources/Labs/LabsPortalFil
es/2010-10_OG_Pre-Drill_Guidance.pdf
 Pennsylvania Publishes Guidance on
Compositing Samples for Volatile Organics
 http://files.dep.state.pa.us/RegionalResources/Labs/LabsPortalFil
es/2011-0323_SDWA_Composite_Analysis_FAQ.pdf
STATE ACTIONS: MN
 Free Webinar on Testing for Hexavalent
Chromium
 http://slhstream.ad.slh.wisc.edu/Mediasite4/Viewer/Viewers/Viewer
AudioOnly.aspx?mode=Default&peid=c6234999-2f57-4f45-8bfb9f7f0033aa80&pid=2a300f37-2483-44cf-9ccfb5c68083ba57&playerType=WM7#
 TBA Added to List of Volatiles in Wisconsin
 http://www.dnr.state.wi.us/org/es/science/lc/OUTREACH/3Guid/-
VOC_List_WI.pdf
OTHER INTERESTING NEWS
 Analyzing Data with Multiple Detection Limits

This paper proposes rank-based procedures for analyzing non-normally
distributed data collected at different sites over a period of time in the presence of
multiple detection limits. http://pubs.acs.org/doi/abs/10.1021/es101304h
 Emerging Chemicals of Concern in the Great Lakes
 Synthetic musk fragrances ;
 Pharmaceuticals, including the antiepileptic drug, carbamazepine;
 Pesticides atrazine, metolachlor, and mecoprop;
 Brominated and chlorinated flame retardants and chlorinated
paraffins;
 Perfluorinated surfactants;
 Alkylphenols including nonylphenol and octylphenol;
 Plasticizers, especially bisphenol A; and
 Polycyclic aromatic hydrocarbons.
http://www.ijc.org/php/publications/pdf/ID696.pdf
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Jerry L. Parr
Catalyst Information Resources
The Information Resource for Environmental Professionals
817-598-1155
jparr@catalystinforesources.com
www.CatalystInfoResources.com