U'S' EPA REGION SIX

1
U.S. EPA REGION SIX OKLAHOMA ARKANSAS
DEPARTMENTS OF ENVIRONMENTAL QUALITY 24th ANNUAL
PRETREATMENT ASSOCIATION WORKSHOP HOW TO
IMPLEMENT A BULLETPROOF CLEAN MERCURY MONITORING
PROGRAM14 August 2008Oklahoma City, OK
Dr. Paul N. BootheSenior ScientistAlbion
Environmental College Station, TX
2
PRESENTATION OUTLINE

• Clear trend toward increasing use of lower
  Minimum Quantification Limits (MQLs) in support
  of NPDES permitting
• What does this trend mean to you?
• How to set-up an effective implementation program
  incorporating lowered MQLs
• Use low-level mercury as an example
• Focus on method compliant valid data reporting
• Conclusions

3
THE HANLON MEMO

• in the light of existing regulatory
  requirements for NPDES permitting, only the most
  sensitive methods such as Methods 1631E and 245.7
  are appropriate in most instances for use in
  deciding whether to set a permit limitation for
  mercury and for sampling and analysis of mercury
  pursuant to the monitoring requirements within a
  permit.
• 
  James A. Hanlon, Director
• 
  EPA Office of Wastewater Management
• 
  August 23,2007

4
THE HOSCH MEMO

• EPA Region 6 has revised the MQLs
  (Minimum Quantification Levels) which we will be
  accepting for EPA issued permits. Region 6
  expects that you (delegated States) will revise
  your procedures to incorporate these revised
  MQLs into your permitting procedures.
• 
  Claudia V. Hosch, Chief
• 
  EPA Region 6
• 
  NPDES Permits and TMDLs Branch
• 
  February 8, 2008

5
REVISED EPA REGION 6 MQLs
6
WHO IS ALBION ENVIRONMENTAL?

• One of the most experienced low-level mercury
  metals laboratories in the U.S.
• Helped the EPA write the book on clean sampling
  and analysis
• Acknowledged by name as significant contributor
  to EPA 1631E, 1638 (ICP-MS) and other 1600
  series clean methods
• Participated in validation studies for EPA 245.7
  1638
• Re-writing the book on dissolved Hg metals
  filtration
• One of the most inter-calibrated labs
• NELAC PT samples plus USGS, LAMPS, EPA split
  sample studies, etc.
• AE frequently supplies clean Hg metals sampling
  equipment to the U.S. EPA Office of Water in
  support of new national rulemaking initiatives

7
LOWER MQLs- SO WHAT?

• Increased use of clean sampling procedures to
  collect contamination-free samples
• Increased use of clean (low-detection limit)
  analytical methods
• Increased cost
• Cost can be moderate if implement smartly
• Permitees will have to take a more active role in
  data QC and data validation
• Region 6 and States can help by collaborating to
  provide good implementation guidance

8
BULLETPROOF IMPLEMENTATION

• Goal is accurate, method compliant and valid data
  at lower MQLs
• Use low-level Hg as example
• Starts with useful implementation guidance
• Method selection
• Specific method recommendations
• Digestion procedures as an example
• EPA 1631E guidance daunting
• Permittes need guidance they can use

9
CLEAN METALS MERCURY CHEMISTRY

• Comprehensive field and laboratory quality
  assurance (QA) procedures and samples
• Clean sampling and storage procedures
• Clean, sensitive analytical methods
• Focuses on data accuracy

10
OPTIMAL SAMPLING PROCEDURE

• Use in-house personnel who are interested in the
  challenge
• Powder-free gloves (multiple easy change)
• Ground cover
• Clean outer clothes
• CleanBox
• Dont skimp on field blanks or field dups
• Field blanks exactly same as samples
• Dont sample in the rain
• Ground shipping

11
EPA METHOD 1631E

• Low-level mercury
• Purge trap/ Cold vapor atomic fluorescence
• Reporting limit (ML) 0.0005 ppb
• Approved for CWA use November 2002
• Driven by Great Lakes Initiative (WQC 1.3 pptr)
  and National Toxics Rule (WQC 12 pptr)
• Rigorous and difficult clean method to perform
• Ease of contamination at sub-pptr level is great
• Good results achievable using good equipment and
  guidance

12
EPA METHOD 245.7

• New, alternative low-level Hg method
• Cold Vapor Atomic Fluorescence
• Direct method- no gold traps
• MDL 1.8 pptr ML 5 pptr (ng/L)
• Validation study conducted 2001
• Albion Environmental 1 of 7 labs submitting
  validation data plus referee laboratory (Total 8
  labs)
• AMSA petitioned EPA to promulgate 245.7
• Approved for 40 CFR Part 136 use by Method Update
  Rule effective 4-12-2007

13
EPA 1631E vs 245.7
14
EPA 245.7 INFERIOR TO 1631E

• EPA 245.7 more prone to interferences
• Tendency to underestimate true Hg concentration
• Cause is quenching from air, O2, organics not
  removed by Nafion (Perma-Pure) permeation dryer
• Low recovery is matrix dependent and varies on a
  sample by sample basis.
• All standard QC passes. Only see poor recovery
  with MS/MSD
• Have to perform MS/MSD on every sample matrix
• Validation Study
• Several labs for low samples reported ND when
  true value was more than twice the MDL of 1.8
  ng/L
• In many cases, the results reported were even
  less than the spike additions.
• Very poor performance on elevated chloride
  (seawater) and industrial wastewaters
• EPA 245.7 data more variable due to interferences
• Wide spread of data in Validation Study (4 of 7
  labs outliers)
• Enhanced variability related to interferences
  varying from sample to sample

15
EPA 245.7 INFERIOR TO 1631E

• 245.7 not really cheaper than 1631E
• Higher gas usage
• Nafion tubes high maintenance item
• Consensus in scientific community 1631E more
  robust and reliable
• Most research labs and many State labs have
  stopped using EPA 245.7 in favor of automated,
  flow-injection EPA 1631E

16
EPA 1631E GUIDANCE

• Method 1631, Revision E Mercury in Water by
  Oxidation, Purge and Trap, and Cold Vapor Atomic
  Fluorescence Spectrometry. EPA-821-R-02-019. EPA
  Office of Water, Engineering Analysis Division,
  Washington, DC. November 23, 2002.
• Guidance for Implementation and Use of EPA Method
  1631 for the Determination of Low-Level Mercury
  (40 CFR part 136). EPA 821-R-01-023. EPA Office
  of Water, Engineering Analysis Division,
  Washington, DC. March 2001
• www.epa.gov/waterscience/methods

17
DIGESTION OF MERCURY SAMPLES

• Limited use EPA Alternate Test Procedure (ATP)
  N0-0025 12-8-2005
• Preparation of aqueous samples by microwave for
  the analysis of total mercury by ICP-MS.
• Granted to City of Portland, OR

18
MERCURY DIGESTIONS DATA COMPARISONS
19
Heated vs Unheated Mercury Digestions
20
BETWEEN A ROCK A HARD PLACE

• only sample results that are associated with QC
  requirements in Method 1631 may be reported or
  used for permitting or regulatory compliance
  purposes.
• EPA 1631E
  Implementation Guidance page 5-18
• Applies in spades to all clean methods

21
BETWEEN A ROCK A HARD PLACE (Cont)

• EPA 1631E FULL METHOD COMPLIANCE CHALLENGING
• Is a rigorous, onerous and difficult method to
  perform according to EPA guidance
• From our experience full method compliance is
  poor in most commercial labs
• Discharge Monitoring Report (DMR) Catch 22
• Permittee responsible for submitting valid data

22
FOLLOW THE METHOD

• Must tell the permittee how to insure reporting
  of valid data
• What lab data do they need to validate data?
• For EPA 1631E two major QA/QC issues
• Acceptable field blanks
• For every sampling point and report to MDL
• Batch specific AND DISCHARGE (MATRIX) SPECIFIC
  matrix spikes/MS duplicates
• Frequency spiking level

23
FOLLOW THE METHOD (Cont)

• Other QA/QC
• Equipment blanks (bottle and sampler)
• Field QA Field duplicates
• Required Lab QA/QC Method blanks, reagent
  blanks, quality check samples,
• Instrument calibration
• Optional Lab QA/QC Laboratory duplicate, blank
  spikes, certified reference materials

24
CONCLUSIONS

• Clean Hg and metals methods coming into wider use
  in NPDES permitting
• Use EPA 1631E not EPA 245.7
• Report 1631E at MQL of 5 pptr if necessary
• Provide detailed, usable implementation guidance
• Guidance on optimal implementation of clean
  sampling procedures
• Specific recommendations about method
  implementation
• Specific guidance on how to evaluate method
  compliance and valid data

25
QUESTIONS?
Paul N. Boothe, PhD.ALBION ENVIRONMENTAL4505
Boyett StreetBryan, TX 77801-4614(979)
268-2677 pboothe_at_albionenv.com