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 PROGRAM WORKSHOP EVERYTHING YOU WANTED TO KNOW ABOUT CLEAN MERCURY AND METALS SAMPLING BUT HOPED YOU’D NEVER HAVE TO ASK Dr. Paul N. Boothe Senior Scientist Albion Environmental College Station, TX 13 AUGUST 2008 OKLAHOMA CITY, OK OKLAHOMA CITY, OK

A L B I O N E N V I R O N M E N T A L PRESENTATION OUTLINE What do you need to know about mercury (Hg) & metals in your wastewaters and receiving waters? –How can clean sampling and analysis help you? Clean Hg & metals sampling & analysis techniques –Background Focus on low-level Hg sampling & analysis –Collecting mercury-free samples: Tiered approach DEMONSTRATION Paragould Arkansas –EPA low-level Hg methods: EPA 1631E & EPA Where do you go from here? –Implementation of a low-level Hg monitoring program Conclusions Q & A What do you need to know about mercury (Hg) & metals in your wastewaters and receiving waters? –How can clean sampling and analysis help you? Clean Hg & metals sampling & analysis techniques –Background Focus on low-level Hg sampling & analysis –Collecting mercury-free samples: Tiered approach DEMONSTRATION Paragould Arkansas –EPA low-level Hg methods: EPA 1631E & EPA 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 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 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 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)? 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 Limits

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 WHY CLEAN CHEMISTRY Greater Data Accuracy (no “false positives”) –Conventional data quality a continuing concern Enhanced Data Precision Lower Detection Limits –Minimize Number of “Non-Detects” –Minimize Use of Surrogate Data –Eliminate inaccurate receiving water data Accurate & Site Specific Removal Efficiencies and Background Loads Greater Data Accuracy (no “false positives”) –Conventional data quality a continuing concern Enhanced Data Precision Lower Detection Limits –Minimize Number of “Non-Detects” –Minimize Use of Surrogate Data –Eliminate inaccurate receiving water data Accurate & Site Specific Removal Efficiencies and Background Loads

A L B I O N E N V I R O N M E N T A L CLEAN METALS CHEMISTRY Comprehensive field and laboratory quality assurance (QA)/ quality control (QC) procedures and samples –Clean sampling and storage procedures TIERED APPROACH- TAILOR EFFORT TO DATA QUALITY OBJECTIVES (USABILITY) –Clean, sensitive analytical methods Focuses on data accuracy Comprehensive field and laboratory quality assurance (QA)/ quality control (QC) procedures and samples –Clean sampling and storage procedures TIERED APPROACH- TAILOR EFFORT TO DATA QUALITY OBJECTIVES (USABILITY) –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 COMPREHENSIVE QA Cradle to grave EPA 1600 series methods: – Equipment blanks (sampler and bottle) – Field QA/QC: Blanks and duplicates – Lab QA/QC: Blanks, matrix spike/ matrix spike duplicate, blank spikes, reference materials, duplicates (optional) – Instrument calibration – Failsafe documentation – Stringent acceptance criteria Cradle to grave EPA 1600 series methods: – Equipment blanks (sampler and bottle) – Field QA/QC: Blanks and duplicates – Lab QA/QC: Blanks, matrix spike/ matrix spike duplicate, blank spikes, reference materials, duplicates (optional) – Instrument calibration – Failsafe documentation – Stringent acceptance criteria

A L B I O N E N V I R O N M E N T A L CLEAN SAMPLING METHODS EPA Method 1669 April 1995 –Written for Hg- worst case scenario –Onsite filtered dissolved measurements a driver Carefully cleaned plasticware Clean hands & dirty hands approach –Wear powder-free gloves –Adapt to or control airborne particulates On-site filtration for dissolved measurements Low detection limits require low blanks EPA Method 1669 April 1995 –Written for Hg- worst case scenario –Onsite filtered dissolved measurements a driver Carefully cleaned plasticware Clean hands & dirty hands approach –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): Effective 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): Effective

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

A L B I O N E N V I R O N M E N T A L CLEAN HG SAMPLING DEMO Paragould LW&C, Paragould Arkansas –Ms. Lisa Ellington –Ms. Ashley Barr “Ultra-clean” approach Manual grab sampling procedures –In-lab gravimetric flow-proportioned compositing Paragould LW&C, Paragould Arkansas –Ms. Lisa Ellington –Ms. Ashley Barr “Ultra-clean” approach Manual grab sampling procedures –In-lab gravimetric flow-proportioned compositing

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

CLEAN COMPOSITE SAMPLING

A L B I O N E N V I R O N M E N T A L EPA APPROVED DISSOLVED HG & METALS FIELD SAMPLING KIT

A L B I O N E N V I R O N M E N T A L CLEAN ANALYSIS METHODOLOGY EPA series 1600 methods issued – ICP/MS, STGFAAS, CVAFS (Hg), Hydride AAS (As) Contamination always a concern Sample digestion a problem area Direct analysis (“clean”) vs extraction/preconcentration (“ultraclean”) Select analytical labs carefully EPA series 1600 methods issued – ICP/MS, STGFAAS, CVAFS (Hg), Hydride AAS (As) Contamination always a concern Sample digestion a problem area Direct analysis (“clean”) vs extraction/preconcentration (“ultraclean”) Select analytical labs carefully

A L B I O N E N V I R O N M E N T A L CLEAN ANALYSIS METHODS Clean preservation & digestion (chemical & uv) EPA 1631e and EPA for low-level Hg EPA 1638/ ICP-MS –“Work Horse” method for remaining priority pollutant metals EPA 1632 (mod) hydride generation atomic fluorescence for dissolved As & Se EPA 1640 (mod) preconcentration inductively coupled plasma- mass spectrometry (ICP-MS) –Dissolved Cd, Cu, Ni, Pb, Zn Clean preservation & digestion (chemical & uv) EPA 1631e and EPA for low-level Hg EPA 1638/ ICP-MS –“Work Horse” method for remaining priority pollutant metals EPA 1632 (mod) hydride generation atomic fluorescence for dissolved As & Se EPA 1640 (mod) preconcentration inductively coupled plasma- mass spectrometry (ICP-MS) –Dissolved Cd, Cu, Ni, Pb, Zn

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 (MDL ppb) 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 Low-level mercury –Purge & trap/ Cold vapor atomic fluorescence –Reporting limit (ML) ppb (MDL ppb) 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 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 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 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 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 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 “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 –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 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 –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

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)