EPA REGION VI MINIMUM EPA REGION VI MINIMUM QUANTIFICATION LEVELS (MQLs)QUANTIFICATION LEVELS (MQLs)

WHAT THE “L” IS GOING ON?WHAT THE “L” IS GOING ON?

2525thth EPA Annual Pretreatment Workshop EPA Annual Pretreatment WorkshopAddison, TXAddison, TX

8/5/098/5/09

Allen GilliamAllen GilliamADEQ State Pretreatment CoordinatorADEQ State Pretreatment Coordinator

gilliam@adeq.state.ar.usgilliam@adeq.state.ar.us

REGION 6’s FIRST “WARNING”REGION 6’s FIRST “WARNING”4/10/06 EPA Region 6 “Claudia Hosch Memo” 4/10/06 EPA Region 6 “Claudia Hosch Memo”

(“for review and comment”)(“for review and comment”) ““In 1992 Region 6 developed guidance on the use In 1992 Region 6 developed guidance on the use

of MQLs and how they would be used in the of MQLs and how they would be used in the NPDES permit decision making progress”NPDES permit decision making progress”

“…“…labs have made advancements in quantification labs have made advancements in quantification levels thru method enhancements and EPA levels thru method enhancements and EPA approved test methods have become more approved test methods have become more commonly available.”commonly available.”

““In a number of cases, the new MQL values are In a number of cases, the new MQL values are now below WQ criteria which were previously now below WQ criteria which were previously unattainable.”unattainable.”

““Most of our states have incorporated these MQL Most of our states have incorporated these MQL values into their permitting procedures…”values into their permitting procedures…”

Some Proposed Minimum Some Proposed Minimum Quantification Levels (MQLs)Quantification Levels (MQLs)

8/23/07 - “Hanlon Memo” (EPA HQs) 8/23/07 - “Hanlon Memo” (EPA HQs) discussing Mercury compliance with discussing Mercury compliance with Water Quality Standards to RegionsWater Quality Standards to Regions

““This memorandum clarifies and explains This memorandum clarifies and explains that, in light of existing regulatory that, in light of existing regulatory requirements for NPDES permitting, only requirements for NPDES permitting, only the most sensitive methods such as the most sensitive methods such as Methods 1631E and 245.7 are appropriate in Methods 1631E and 245.7 are appropriate in most instances for use in deciding whether most instances for use in deciding whether to set a permit limitation for Hg and for to set a permit limitation for Hg and for sampling and analysis of Hg pursuant to the sampling and analysis of Hg pursuant to the monitoring requirements within a permit.”monitoring requirements within a permit.”

““Hanlon Memo” discussing compliance Hanlon Memo” discussing compliance with WQ Standards (cont.)with WQ Standards (cont.)

““For [delegated] States, EPA Regions…For [delegated] States, EPA Regions…should strongly consider objecting to should strongly consider objecting to permits that are issued based on permits that are issued based on analytical data that is collected and analytical data that is collected and analyzed using an EPA approved method analyzed using an EPA approved method not sufficiently sensitive or that do not not sufficiently sensitive or that do not require use of a sufficiently sensitive require use of a sufficiently sensitive EPA approved method for monitoring…”EPA approved method for monitoring…”

Region 6 / States WQ Managers’Region 6 / States WQ Managers’ “Love-In” meeting excerpts (10/30/07) “Love-In” meeting excerpts (10/30/07)

MDL – Method Detection LevelMDL – Method Detection Level– minimum concentration of a substance that can minimum concentration of a substance that can

be measured and reported with 99% confidence be measured and reported with 99% confidence that the analyte concentration is > 0 and is that the analyte concentration is > 0 and is determined from analysis of a sample in a given determined from analysis of a sample in a given matrix containing the analytematrix containing the analyte

LOD – Limit of DetectionLOD – Limit of Detection– approximately 3 times the standard deviation

obtained from replicate measurements and may be described as that value determined to be statistically significant from the measurement of a reagent blank

Region 6 / States’ WQ Managers’ “Love-Region 6 / States’ WQ Managers’ “Love-In” meeting notes (10/30/07 cont.)In” meeting notes (10/30/07 cont.)

LOQ – Limit of Quantitaion– attempts to define a level of analyte that may be

repeatedly measured

Region 6 has elected to define MQL as the lowest concentration at which a particular substance can be quantitatively measured– LOD = 3 standard deviations– LOQ = 10 standard deviations– LOQ = 10/3 LOD– LOD = MDL ???– MQL = 3.3 MDL

Some Some FinalFinal Region 6 MQLs Region 6 MQLsOctober 30, 2007October 30, 2007

““Existing”Existing” RevisedRevised

ParameterParameter MQL MQL g/l MQL MQL g/l

AluminumAluminum 100100 2.52.5

ArsenicArsenic 10 10 0.50.5

BerylliumBeryllium 5 5 0.50.5

CopperCopper 10 10 0.50.5

LeadLead 5 5 0.50.5 (Method) (Method)

MercuryMercury 0.2 0.2 0.0005 / 0.005 (1631E / 245.7)0.0005 / 0.005 (1631E / 245.7)

NickelNickel 40 40 0.50.5

SeleniumSelenium 5 5 55

SilverSilver 2 2 0.50.5

ThalliumThallium 10 10 0.50.5

CyanideCyanide 20 20 1010

WHAT DO THESE MQLsWHAT DO THESE MQLs MEAN TO YOU? MEAN TO YOU?

Do you know your state’s permitting Do you know your state’s permitting procedures (should be part of your procedures (should be part of your “Continuing Planning Process” document “Continuing Planning Process” document req’d by 40 CFR 130.5)?req’d by 40 CFR 130.5)?

States’ procedures in Region 6 are States’ procedures in Region 6 are somewhat similarsomewhat similar

NPDES renewal? Majors must analyze / NPDES renewal? Majors must analyze / report results from a Priority Pollutant Scan report results from a Priority Pollutant Scan (PPS) – One sampling event / 5 years(PPS) – One sampling event / 5 years

PERMITTING PROCEDURESPERMITTING PROCEDURESOne SampleOne Sample (Hg for example) (Hg for example)

1.1. Calculate “reasonable potential” to exceed Calculate “reasonable potential” to exceed WQ standardWQ standard

Hg Water Quality Standard = 0.012 Hg Water Quality Standard = 0.012 g/l

Priority Pollutant Scan result X 2.13 Priority Pollutant Scan result X 2.13 (EPA’s (EPA’s statistical multiplier from their “Technical Support statistical multiplier from their “Technical Support Document for WQ-based Toxics Control”. Arguable…)Document for WQ-based Toxics Control”. Arguable…)

PPS Hg result = 0.006 PPS Hg result = 0.006 g/l

0.006 ug/l X 2.13 = 0.0128 0.006 ug/l X 2.13 = 0.0128 g/l)

2.2. Reasonable potential? 0.0128 > 0.012 Reasonable potential? 0.0128 > 0.012 g/l??

YES, Hg limit will be incorporated into permit.YES, Hg limit will be incorporated into permit.

ARKANSAS WORST CASE “WQ LEVELS ARKANSAS WORST CASE “WQ LEVELS NOT TO EXCEED” 7Q10 = 0 CFS NOT TO EXCEED” 7Q10 = 0 CFS

(Intermittent Stream)(Intermittent Stream)PollutantPollutant Monthly Avg. Monthly Avg.

((g/l)g/l)MQL MQL

((g/l)g/l)

ArsenicArsenic 335335 0.50.5

BerylliumBeryllium 5.915.91 0.50.5

CopperCopper 8.78.7 0.50.5

LeadLead 2.62.6 0.50.5

MercuryMercury 0.0120.012 0.0050.005

NickelNickel 9090 0.50.5

SeleniumSelenium 5.65.6 55

SilverSilver 0.940.94 0.50.5

CyanideCyanide 6.06.0 1010

EXTRA “SCRUTINY” FOR THE EXTRA “SCRUTINY” FOR THE PRETREATMENT CITIES?PRETREATMENT CITIES?

Region 6 Pretreatment Cities required to do Region 6 Pretreatment Cities required to do quarterly influent / effluent monitoring, quarterly influent / effluent monitoring, maybe more?maybe more?– Hopefully, you’re using the most sensitive Hopefully, you’re using the most sensitive

methods for both (for most valid site specific methods for both (for most valid site specific removal efficiencies)removal efficiencies)

More data points for NPDES permit writer to More data points for NPDES permit writer to use in calculating “reasonable potential”!use in calculating “reasonable potential”!– PLEASEPLEASE use common sense clean sampling use common sense clean sampling

techniquestechniques

METALS, CYANIDE and PHENOLS

MAHC(Total)

((g/l)g/l)

INFLUENT DATES SAMPLED

(g/l)Once/quarter WQ

level/limit(g/l)

EFFLUENT DATES SAMPLED

(g/l)Once/quarter

LAB ANALYSIS

EPA MQL(g/l)

EPAMethod

Used

Detection Level

Achieved (g/l)

Date Date Date Date Date Date Date Date

Cadmium 1.921.92 0.5

Copper 8.78.7 0.5

Lead 2.62.6 0.5

Mercury 0.0120.012

.005

Selenium 5.65.6 5

Silver 0.940.94 0.5

Cyanide 5.85.8 10

Arsenic 335335 0.5

PERMITTING PROCEDURES FOR PERMITTING PROCEDURES FOR LIMITED DATA SETS (<20)LIMITED DATA SETS (<20)

1.1. Permit writer takes data points:Permit writer takes data points:

2.2. Calculates geometric mean (GM)Calculates geometric mean (GM)a. GM = [ (Xa. GM = [ (X11)(X)(X22)(X)(X33)........(X)........(XNN) ]) ]1/N1/N;;

3.3. Multiplies GM X 2.13 to determine Multiplies GM X 2.13 to determine “reasonable potential”;“reasonable potential”;

4.4. If reasonable potential exists If reasonable potential exists Permittee gets permit limitPermittee gets permit limit

METALS, CYANIDE and PHENOLS

MAHC(Total)

(g/l)

INFLUENT DATES SAMPLED

(g/l)Once/quarter WQ

level/limit(g/l)

EFFLUENT DATES SAMPLED

(g/l)Once/quarter

LAB ANALYSIS

EPA MQL(g/l)

EPAMethod

Used

Detection Level

Achieved (g/l)

Date Date Date Date Date Date Date Date

2/082/08 5/085/08 8/088/08 11/0811/08

Cadmium 1.921.92 0.5

Copper 8.78.7 0.5

Lead 2.62.6 0.5

Mercury 0.0120.012 0.028 0.028 0.0070.007 0.0160.016 0.0460.046 .005 16311631EE

0.00050.0005

Selenium 5.65.6 5

Silver 0.940.94 0.5

Cyanide 5.85.8 10

Arsenic 335335 0.5

PERMITTING PROCEDURES FOR PERMITTING PROCEDURES FOR LIMITED DATA SETS (<20) for HgLIMITED DATA SETS (<20) for Hg

1.1. Permit writer takes data points:Permit writer takes data points:

2.2. Calculates geometric mean (GM)Calculates geometric mean (GM)a.a. GM = [ (.026)(.007)(.016)(.046) ]GM = [ (.026)(.007)(.016)(.046) ]1/41/4 = = 0.0180.018 (g/l)

b.b. Don’t even have to calculate “reasonable potential”Don’t even have to calculate “reasonable potential”

3.3. WQ “level not to exceed” = WQ “level not to exceed” = 0.0120.012 (g/l)

4.4. Reasonable potential definitely exists Reasonable potential definitely exists

Permittee gets permit Hg limitPermittee gets permit Hg limit

METALS, CYANIDE and PHENOLS

MAHC(Total)

(g/l)

INFLUENT DATES SAMPLED

(g/l)Once/quarter WQ

level/limit(g/l)

EFFLUENT DATES SAMPLED

(g/l)Once/quarter

LAB ANALYSIS

EPA MQL(g/l)

EPAMethod

Used

Detection Level

Achieved (g/l)

Date Date Date Date Date Date Date Date

2/082/08 5/085/08 8/088/08 11/0811/08

Cadmium 1.921.92 0.5

Copper

8.78.7 <0.5<0.5 <0.5<0.5 1010 1212 0.5 200.8200.8 0.50.5

Lead 2.62.6 0.5

Mercury 0.0120.012 .005

Selenium 5.65.6 5

Silver 0.940.94 0.5

Cyanide 5.85.8 10

Arsenic 335335 0.5

PERMITTING PROCEDURES FOR PERMITTING PROCEDURES FOR LIMITED DATA SETS (<20) for CuLIMITED DATA SETS (<20) for Cu

1.1. Permit writer takes data points Permit writer takes data points (if there’s (if there’s

even one detect, “NDs” are treated as ½ MQL)even one detect, “NDs” are treated as ½ MQL)::

2.2. Calculates geometric mean (GM)Calculates geometric mean (GM)a.a. GM = [ (.25)(.25)(10)(12) ]GM = [ (.25)(.25)(10)(12) ]1/41/4 = 1.65 = 1.65 g/l

3.3. GM X 2.13 to determine “reasonable GM X 2.13 to determine “reasonable potential” = 1.65 X 2.13 = potential” = 1.65 X 2.13 = 3.53.5 g/l

4.4. WQ “level not to exceed” = WQ “level not to exceed” = 8.78.7 g/l

5.5. Reasonable potential does not exist Reasonable potential does not exist Permittee gets no Cu limitPermittee gets no Cu limit

METALS, CYANIDE and PHENOLS

MAHC(Total)

(g/l)

INFLUENT DATES SAMPLED

(ug/l)Once/quarter WQ

level/limit(g/l)

EFFLUENT DATES SAMPLED

(ug/l)Once/quarter

LAB ANALYSIS

EPA MQL(g/l)

EPAMethod

Used

Detection Level

Achieved (g/l)

Date Date Date Date Date Date Date Date

2/082/08 5/085/08 8/088/08 11/0811/08

Cadmium 1.921.92 0.5

Copper

8.78.7 0.5

Lead 2.62.6 0.5

Mercury 0.0120.012 .005

Selenium 5.65.6 5

Silver 0.940.94 0.5

Cyanide

5.85.8 <10<10 77 <10<10 8.058.05 10 330.5330.5 55

Arsenic 335335 0.5

YOUR WORST NIGHTMARE!

PERMITTING PROCEDURES FOR PERMITTING PROCEDURES FOR LIMITED DATA SETS (<20) for CNLIMITED DATA SETS (<20) for CN

1.1. Permit writer takes data points Permit writer takes data points (if there’s (if there’s

even one detect, “NDs” are treated as ½ MQL)even one detect, “NDs” are treated as ½ MQL)::

2.2. Calculates geometric mean (GM)Calculates geometric mean (GM)a.a. GM = [ (5)(7)(5)(8.05) ]GM = [ (5)(7)(5)(8.05) ]1/41/4 = = 6.136.13 g/l

b.b. Don’t even have to calculate “reasonable Don’t even have to calculate “reasonable potential”potential”

3.3. WQ “level not to exceed” = WQ “level not to exceed” = 5.85.8 g/l Reasonable potential exists Reasonable potential exists Permittee gets CN limitPermittee gets CN limit

METALS, CYANIDE and PHENOLS

MAHC(Total)

(g/l)

INFLUENT DATES SAMPLED

(g/l)Once/quarter

WQlevel/limit(g/l)

EFFLUENT DATES SAMPLED

(g/l)Once/quarter

LAB ANALYSIS

EPA MQL(g/l)

EPAMethod

Used

Detection Level

Achieved (g/l)

Date Date Date Date Date Date Date Date

2/082/08 5/085/08 8/088/08 11/0811/08

Cadmium 1.921.92 0.5

Copper

8.78.7 0.5

Lead 2.62.6 0.5

Mercury 0.0120.012 .005

Selenium 5.65.6 <10<10 <10<10 <10<10 <10<10 5 200.8200.8 22

Silver 0.940.94 0.5

Cyanide

5.85.8 10

Arsenic 335335 0.5

NEED LAB EXPLANATION ON THIS ONE!

PERMITTING PROCEDURES FOR PERMITTING PROCEDURES FOR LIMITED DATA SETS (<20) for CNLIMITED DATA SETS (<20) for CN

1.1. Permit writer takes data points Permit writer takes data points (if the (if the

“NDs” “NDs” >> the MQL, values will be entered the MQL, values will be entered atat the MQL) the MQL)::

2.2. Calculates geometric mean (GM)Calculates geometric mean (GM)a.a. GM = [ (10)10)(10)(10) ]GM = [ (10)10)(10)(10) ]1/41/4 = = 1010 g/l

b.b. Don’t even have to calculate “reasonable Don’t even have to calculate “reasonable potential”potential”

3.3. WQ “level not to exceed” = WQ “level not to exceed” = 5.65.6 g/l Reasonable potential exists Reasonable potential exists Permittee gets Se limitPermittee gets Se limit

What the “L” is going on with What the “L” is going on with this logic?this logic?

Do notDo not sample effluent after a rain event or when sample effluent after a rain event or when your plant is suspected of being “upset”your plant is suspected of being “upset”

Require your labs to explain why they could Require your labs to explain why they could not meet the required MQLnot meet the required MQL (“had to dilute (“had to dilute because of matrix condition being turbid or because of matrix condition being turbid or suspected of containing matrix interferences….”)suspected of containing matrix interferences….”)

Note to your permit writer: “results should not be Note to your permit writer: “results should not be used in calculating ‘reasonable potential’ because used in calculating ‘reasonable potential’ because they were not representative”they were not representative”

Contest / ask permit writer about the rationale Contest / ask permit writer about the rationale behind the “reasonable potential” multiplier of behind the “reasonable potential” multiplier of 2.13 (if your state uses it)2.13 (if your state uses it)