Dr. Paul N. Boothe Senior Scientist Albion Environmental College Station, TX

A L B I O N E N V I R O N M E N T A LA 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 ASSOCIATION WORKSHOP ANNUAL PRETREATMENT ASSOCIATION WORKSHOP

HOW TO IMPLEMENT A HOW TO IMPLEMENT A BULLETPROOF CLEAN MERCURY BULLETPROOF CLEAN MERCURY

MONITORING PROGRAMMONITORING PROGRAM

14 August 200814 August 2008Oklahoma City, OKOklahoma City, OK

Dr. Paul N. BootheDr. Paul N. BootheSenior ScientistSenior Scientist

Albion EnvironmentalAlbion EnvironmentalCollege Station, TXCollege Station, TX


PRESENTATION OUTLINEPRESENTATION OUTLINE• Clear trend toward increasing use of

lower Minimum Quantification Limits (MQL’s) in support of NPDES permitting

• What does this trend mean to you?• How to set-up an effective

implementation program incorporating lowered MQL’s– Use low-level mercury as an example– Focus on method compliant valid data

reporting

• Conclusions

• Clear trend toward increasing use of lower Minimum Quantification Limits (MQL’s) in support of NPDES permitting

• What does this trend mean to you?• How to set-up an effective

implementation program incorporating lowered MQL’s– Use low-level mercury as an example– Focus on method compliant valid data

reporting

• Conclusions


“THE HANLON MEMO”“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

“… 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


“THE HOSCH MEMO”“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

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


REVISED EPA REGION 6 MQL’sREVISED EPA REGION 6 MQL’s

ELEMENT

EXISTING MQL (ppb)

REVISED MQL (ppb)

ANALYTICAL METHOD

Ag 2 0.50 EPA 200.8

Al 100 2.5 EPA 200.8

As 10 0.50 EPA 200.8

Be 5 0.50 EPA 200.8

Cu 10 0.50 EPA 200.8

Hg 0.2 0.005 / 0.0005 EPA 245.7 / 1631E

Ni 40 0.50 EPA 200.8

Pb 5 0.50 EPA 200.8

Se 5 5 EPA 200.8

Tl 10 0.50 EPA 200.8


WHO IS ALBION ENVIRONMENTAL?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

• 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


LOWER MQL’s- SO WHAT?LOWER MQL’s- 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

• 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


BULLETPROOF IMPLEMENTATIONBULLETPROOF IMPLEMENTATION

• Goal is accurate, method compliant and valid data at lower MQL’s– 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

• Goal is accurate, method compliant and valid data at lower MQL’s– 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


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


OPTIMAL SAMPLING PROCEDUREOPTIMAL SAMPLING PROCEDURE• Use in-house personnel who are interested in

the challenge• Powder-free gloves (multiple easy change)• Ground cover• 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

• Use in-house personnel who are interested in the challenge

• Powder-free gloves (multiple easy change)• Ground cover• 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


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


EPA METHOD 245.7EPA 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

• “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


EPA 1631E vs 245.7EPA 1631E vs 245.7Method 1631 Method 245.7

Status Approved 40 CFR part 136

11-32-2002

Approved 40 CFR part 136

MUR 4-12-2007

Digestion BrCl / SnCl2 /NH2OH•HCl

KBr /KBrO3 /SnCl2 /

NH2OH•HCl

Separation Vapor Separation

Gold Trap

Vapor Separation

Dryer 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


EPA 245.7 INFERIOR TO 1631EEPA 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

• 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


EPA 245.7 INFERIOR TO 1631EEPA 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

• 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


EPA 1631E GUIDANCEEPA 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

• 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


DIGESTION OF MERCURY SAMPLESDIGESTION 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

• 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


MERCURY DIGESTIONS DATA COMPARISONS

MERCURY DIGESTIONS DATA COMPARISONS

Sample matrix SIC Code

Mercury: Avg Ratio

Unheated 1631E/ Microwave ICP-MS

Industrial Effluent 2077, 2611, 2621, 4953,

7389, 7699, 8062, 87330.52

WWTP Influent 4952 0.55

WWTP Effluent 4952 0.54

Surface water NA 0.57


Heated vs Unheated Mercury Digestions

Heated vs Unheated Mercury Digestions

0

50

100

150

200

250

Ind. Eff. WWTP Inf. WWTP Eff. Surf. Water

1631E

MicrowaveICP-MS

0

50

100

150

200

250

Ind. Eff. WWTP Inf. WWTP Eff. Surf. Water

1631E

MicrowaveICP-MS


BETWEEN A ROCK & A HARD PLACE

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

“…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


BETWEEN A ROCK & A HARD PLACE (Con’t)

BETWEEN A ROCK & A HARD PLACE (Con’t)

• 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

• 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


FOLLOW THE METHODFOLLOW 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

• 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


FOLLOW THE METHOD (Con’t)

• 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


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


QUESTIONS?QUESTIONS?

Paul N. Boothe, PhD.ALBION ENVIRONMENTAL

4505 Boyett StreetBryan, TX 77801-4614

(979) 268-2677 [email protected]

Dr. Paul N. Boothe Senior Scientist Albion Environmental College Station, TX

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