A L B I O N E N V I R O N M E N T A L U.S. EPA REGION SIX & U.S. EPA REGION SIX & OKLAHOMA & ARKANSAS DEPARTMENTS OF ENVIRONMENTAL QUALITY OKLAHOMA & ARKANSAS DEPARTMENTS OF ENVIRONMENTAL QUALITY 24 24 th th ANNUAL PRETREATMENT PROGRAM WORKSHOP ANNUAL PRETREATMENT PROGRAM WORKSHOP EVERYTHING YOU WANTED TO KNOW EVERYTHING YOU WANTED TO KNOW ABOUT CLEAN MERCURY AND METALS ABOUT CLEAN MERCURY AND METALS SAMPLING BUT HOPED YOU’D NEVER SAMPLING BUT HOPED YOU’D NEVER HAVE TO ASK HAVE TO ASK Dr. Paul N. Boothe Dr. Paul N. Boothe Senior Scientist Senior Scientist Albion Environmental Albion Environmental College Station, TX College Station, TX 13 AUGUST 2008 13 AUGUST 2008 OKLAHOMA CITY, OK OKLAHOMA CITY, OK
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Dr. Paul N. Boothe Senior Scientist Albion Environmental College Station, TX
U.S. EPA REGION SIX & OKLAHOMA & ARKANSAS DEPARTMENTS OF ENVIRONMENTAL QUALITY 24 th ANNUAL PRETREATMENT PROGRAM WORKSHOP EVERYTHING YOU WANTED TO KNOW ABOUT CLEAN MERCURY AND METALS SAMPLING BUT HOPED YOU’D NEVER HAVE TO ASK. 13 AUGUST 2008 OKLAHOMA CITY, OK. - PowerPoint PPT Presentation
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A L B I O N E N V I R O N M E N T A L
U.S. EPA REGION SIX & U.S. EPA REGION SIX & OKLAHOMA & ARKANSAS DEPARTMENTS OF ENVIRONMENTAL QUALITYOKLAHOMA & ARKANSAS DEPARTMENTS OF ENVIRONMENTAL QUALITY
2424thth ANNUAL PRETREATMENT PROGRAM WORKSHOP ANNUAL PRETREATMENT PROGRAM WORKSHOP
EVERYTHING YOU WANTED TO KNOW EVERYTHING YOU WANTED TO KNOW ABOUT CLEAN MERCURY AND ABOUT CLEAN MERCURY AND
METALS SAMPLING BUT HOPED METALS SAMPLING BUT HOPED YOU’D NEVER HAVE TO ASKYOU’D NEVER HAVE TO ASK
Dr. Paul N. BootheDr. Paul N. BootheSenior ScientistSenior Scientist
• Where do you go from here?– Implementation of a low-level Hg monitoring program
• Conclusions• Q & A
A L B I O N E N V I R O N M E N T A L
What did you need to know about Hg & metals in your wastewaters & receiving waters? - “The Good Ole Days (2003)”
• Very little– Ignorance is bliss?– Non-detects are your friend.
• Still largely conventional sampling and analysis metals data– Relatively high detection limits- mostly ND’s– False positives due to contamination during
sampling and analysis contamination and other anomalies
A L B I O N E N V I R O N M E N T A L
“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
A L B I O N E N V I R O N M E N T A L
“THE HOSCH MEMO” EPA Region 6 has “… revised the MQL’s
(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 MQL’s” into your permitting procedures.
Claudia V. Hosch, Chief EPA Region 6 NPDES Permits and TMDL’s Branch February 8, 2008
A L B I O N E N V I R O N M E N T A L
HOW CAN CLEAN SAMPLING & ANALYSIS HELP YOU?
• Does your WWTP have metals limits?– Would you like to be able to accurately measure metals at the
levels at which you are being regulated? • Would you like to know how close you are to violating your permit
limits?• Would you like to avoid metal limits?• Would you like to know how well your WWTP is
operating in terms of metals removal?– Would you like higher, site specific technically based local
limits?• Would you like to know how much your effluent
discharge is affecting metals levels in the receiving waters (i.e. reasonable potential dterminations)?
A L B I O N E N V I R O N M E N T A L
Pretreatment Local LimitsMetal Conventional EPA
Surrogate Data (mg/L)Clean Metals Site
Specific Data (mg/L)Ratio Clean/Conventional
Cd 0.008 0.052 6.5
Cu 0.061 1.66 27.2
Hg 0.0012 0.0066 5.5
Pb 0.049 0.19 3.9
Zn 0.18 3.58 19.8
A L B I O N E N V I R O N M E N T A L
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
– Wear powder-free gloves– Adapt to or control airborne particulates
• On-site filtration for dissolved measurements
• Low detection limits require low blanks
A L B I O N E N V I R O N M E N T A L
EPA DISSOLVED METALS & HG GUIDANCE• New “15 Minute Rule” for dissolved trace metals
(Footnote 7)– “For dissolved metals, filter grab samples within 15 minutes of collection
and before adding preservatives. For a composite sample collected with an automated sampler … filter the sample within 15 minutes after completion of collection and before adding preservatives ...”
• Exception for dissolved mercury (Footnote 17)– “A sample collected for dissolved trace level mercury (< 100 ng/L) should
be filtered in the laboratory within 24 hours of the time of collection.” – “However, if circumstances preclude overnight shipment, the sample
should be filtered in a designated clean area in the field in accordance with procedures given in Method 1669.”
– “If sample integrity will not be maintained by shipment to and filtration in the laboratory, the sample must be filtered in a designated clean area in the field within the time period necessary to maintain sample integrity.”
• Information in TABLE II takes precedence over information in specific methods or elsewhere.
Source: Method Update Final Rule, Part 136, Table II Required Containers, Preservation Techniques and Holding Times. Federal Register 72(47): 11236-11239. Effective 4-12-2007.
A L B I O N E N V I R O N M E N T A L
Side-by-side East Texas Sites (2-3 April 2008)Diss. Mercury vs Filter Type
• Approved for CWA use November 2002– Driven by Great Lakes Initiative (WQC 1.3 pptr)
and National Toxics Rule (WQC 12 pptr)• Most difficult clean method to perform
– Ease of contamination at sub-pptr level is great– Good results achievable using good equipment
and guidance
A L B I O N E N V I R O N M E N T A L
EPA 1631E vs 245.7Method 1631 Method 245.7
Status Approved 40 CFR part 13611-32-2002
Approved 40 CFR part 136MUR 4-12-2007
Digestion BrCl / SnCl2 /NH2OH•HCl
KBr /KBrO3 /SnCl2 /NH2OH•HCl
Separation Vapor SeparationGold Trap
Vapor SeparationDryer Tube (Nafion)
Detection CVAFS CVAFS
MDL / ML 0.2 / 0.5 ng/L 1.8 / 5.0 ng/L
Range 0.5 – 100 ng/L 5 – 100 ng/L
A L B I O N E N V I R O N M E N T A L
STARTING A CLEAN HG MONITORING PROGRAM
• Decide how much assistance you want or need– Continuum: turnkey to using all in-house
resources– Optimal compromise:
• Specialized clean equipment and analysis laboratory (vendor)
• All sampling done using in-house personnel with level of training needed from specialized lab
A L B I O N E N V I R O N M E N T A L
OPTIMAL SAMPLING PROCEDURE• Use in-house personnel who are interested in
the challenge• Use reliable, blanked bottles & equipment• Powder-free gloves (multiple easy change)• Ground cover & all plastic sampling gear• Clean outer clothes• CleanBox• Don’t skimp on field blanks or field dups
– Field blanks exactly same as samples• Don’t sample in the rain• Ground shipping
A L B I O N E N V I R O N M E N T A L
BETWEEN A ROCK & A HARD PLACE
• 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
A L B I O N E N V I R O N M E N T A L
QUESTIONS TO ASK POTENTIAL 1631E LABORATIES
• “Innocent”, non-leading questions to see what the prospective lab knows:
• # 1: What modifications have they made to promulgated method in their implementation of EPA method 1631E?• # 2: Ask for suggested compliant sampling plan• # 3: Ask for sample data report including narrative• # 4: Ask for recent reports for ALL performance test (PT) sample programs they participate in• # 5: Ask about turnaround time (TAT)• # 6: Ask for raw instrument data run log
A L B I O N E N V I R O N M E N T A L
CONCLUSIONS• Clean Hg and metals methods coming
– Adaptable to virtually any sampling scenario– You can make them work to your advantage
• Use of trained in-house personnel is optimal• Use EPA 1631E not EPA 245.7
– Can report 1631E data at MQL of 5 pptr if needed• Chose your equipment and laboratory vendor
carefully– No field preservation, no icing, no expedited
shipping allows you to use any clean metals or Hg lab you want to