A L B I O N E N V I R O N M E N T A L U.S. EPA REGION SIX & OKLAHOMA & ARKANSAS DEPARTMENTS OF ENVIRONMENTAL QUALITY 24 th ANNUAL PRETREATMENT ASSOCIATION WORKSHOP HOW TO IMPLEMENT A BULLETPROOF CLEAN MERCURY MONITORING PROGRAM 14 August 2008 Oklahoma City, OK 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 L PRESENTATION 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

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 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 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 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 REVISED EPA REGION 6 MQL’s ELEMENT EXISTING MQL (ppb) REVISED MQL (ppb) ANALYTICAL METHOD Ag20.50EPA Al1002.5EPA As100.50EPA Be50.50EPA Cu100.50EPA Hg / EPA / 1631E Ni400.50EPA Pb50.50EPA Se55EPA Tl100.50EPA 200.8

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 & 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 & 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

A L B I O N E N V I R O N M E N T A L 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

A L B I O N E N V I R O N M E N T A L BULLETPROOF 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

A L B I O N E N V I R O N M E N T A L 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 Comprehensive field and laboratory quality assurance (QA) procedures and samples –Clean sampling and storage procedures –Clean, sensitive analytical methods Focuses on data accuracy

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 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

A L B I O N E N V I R O N M E N T A L EPA METHOD 1631E Low-level mercury –Purge & trap/ Cold vapor atomic fluorescence –Reporting limit (ML) 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 Low-level mercury –Purge & trap/ Cold vapor atomic fluorescence –Reporting limit (ML) 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

A L B I O N E N V I R O N M E N T A L EPA METHOD “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 Approved for 40 CFR Part 136 use by Method Update Rule effective “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 Approved for 40 CFR Part 136 use by Method Update Rule effective

A L B I O N E N V I R O N M E N T A L EPA 1631E vs Method 1631Method Status Approved 40 CFR part Approved 40 CFR part 136 MUR Digestion BrCl / SnCl2 / NH2OHHCl KBr /KBrO3 /SnCl2 / NH2OHHCl Separation Vapor Separation Gold Trap Vapor Separation Dryer Tube (Nafion) Detection CVAFS MDL / ML 0.2 / 0.5 ng/L1.8 / 5.0 ng/L Range 0.5 – 100 ng/L5 – 100 ng/L

A L B I O N E N V I R O N M E N T A L EPA INFERIOR TO 1631E EPA 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 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 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 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

A L B I O N E N V I R O N M E N T A L EPA INFERIOR TO 1631E 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 in favor of automated, flow-injection EPA 1631E 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 in favor of automated, flow-injection EPA 1631E

A L B I O N E N V I R O N M E N T A L EPA 1631E GUIDANCE Method 1631, Revision E: Mercury in Water by Oxidation, Purge and Trap, and Cold Vapor Atomic Fluorescence Spectrometry. EPA-821-R EPA Office of Water, Engineering Analysis Division, Washington, DC. November 23, Guidance for Implementation and Use of EPA Method 1631 for the Determination of Low-Level Mercury (40 CFR part 136). EPA 821-R EPA Office of Water, Engineering Analysis Division, Washington, DC. March Method 1631, Revision E: Mercury in Water by Oxidation, Purge and Trap, and Cold Vapor Atomic Fluorescence Spectrometry. EPA-821-R EPA Office of Water, Engineering Analysis Division, Washington, DC. November 23, Guidance for Implementation and Use of EPA Method 1631 for the Determination of Low-Level Mercury (40 CFR part 136). EPA 821-R EPA Office of Water, Engineering Analysis Division, Washington, DC. March

A L B I O N E N V I R O N M E N T A L DIGESTION OF MERCURY SAMPLES Limited use EPA Alternate Test Procedure (ATP) N –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) N –Preparation of aqueous samples by microwave for the analysis of total mercury by ICP-MS. –Granted to City of Portland, OR

A L B I O N E N V I R O N M E N T A L MERCURY DIGESTIONS DATA COMPARISONS Sample matrixSIC Code Mercury: Avg Ratio Unheated 1631E/ Microwave ICP-MS Industrial Effluent 2077, 2611, 2621, 4953, 7389, 7699, 8062, WWTP Influent WWTP Effluent Surface water NA 0.57

A L B I O N E N V I R O N M E N T A L Heated vs Unheated Mercury Digestions

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 “…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

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 (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

A L B I O N E N V I R O N M E N T A L 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 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

A L B I O N E N V I R O N M E N T A L 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 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

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 into wider use in NPDES permitting Use EPA 1631E not EPA –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 Clean Hg and metals methods coming into wider use in NPDES permitting Use EPA 1631E not EPA –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

A L B I O N E N V I R O N M E N T A L QUESTIONS? Paul N. Boothe, PhD. ALBION ENVIRONMENTAL 4505 Boyett Street Bryan, TX (979)