Determination of Lead in Dust Wipes using Field Analytical Technology

11

Determination of Lead in Determination of Lead in Dust Wipes using Field Dust Wipes using Field Analytical TechnologyAnalytical Technology

Presented byPresented by

U.S. Environmental Protection Agency’s (EPA) Office of Superfund U.S. Environmental Protection Agency’s (EPA) Office of Superfund Remediation and Technology Innovation (OSRTI) and Remediation and Technology Innovation (OSRTI) and

Office of Research and Development (ORD) Office of Research and Development (ORD)

and the Department of Energy’s (DOE) and the Department of Energy’s (DOE) Oak Ridge National Laboratory (ORNL)Oak Ridge National Laboratory (ORNL)

22

Background Background Environmental Technology Environmental Technology

Verification ProgramVerification Program

Early 1990s - Need for environmental technology Early 1990s - Need for environmental technology verification identifiedverification identified Slow rate of innovation; poor U.S. marketsSlow rate of innovation; poor U.S. markets Lack of credibility of new technologiesLack of credibility of new technologies Inertia of system, risk aversion of purchasers and Inertia of system, risk aversion of purchasers and

permitterspermitters Burgeoning international marketBurgeoning international market

EPA initiates ETV in October, 1995 EPA initiates ETV in October, 1995

33

ETV ObjectivesETV Objectives Provide credible Provide credible performance dataperformance data for for

commercial environmental technologiescommercial environmental technologiesto aid to aid vendorsvendors in selling innovative technologies, in selling innovative technologies, purchaserspurchasers in making decisions to purchase in making decisions to purchase

innovative technologies, andinnovative technologies, and regulatorsregulators in making permitting decisions in making permitting decisions

regarding environmental technologies.regarding environmental technologies.

44

ETV SuccessesETV Successes 240 Verifications, 78 protocols240 Verifications, 78 protocols to date Vendor demand continues – over 100 technologies in

testing/evaluation, over 100 applications pending Increasing funding from vendors and others 805 Stakeholders in 21 groups Commendations from EPA science and policy

advisory boards Supports regulatory and voluntary Agency, other

Federal and state programs Growing international interest New role in homeland security verifications

55

ETVETV VerifiesVerifies onlyonly

Definition:Definition: Verify Verify is to determine performance is to determine performance under test plan defined conditions under test plan defined conditions NoNo winners or losers winners or losers NoNo approvals approvals NoNo certification certification NoNo pass or fail pass or fail NoNo guarantees guarantees

Responsibility rests with the technology user to Responsibility rests with the technology user to correctly choose and apply technologiescorrectly choose and apply technologies

66

Stakeholder RolesStakeholder Roles

Help set verification prioritiesHelp set verification priorities Review protocols and operating Review protocols and operating

proceduresprocedures Review other important documentsReview other important documents Assist in designing and conducting Assist in designing and conducting

outreach activitiesoutreach activities Serve as information conduits to Serve as information conduits to

their constituenciestheir constituencies

77

ETV CentersETV CentersETV ETV Air Pollution ControlAir Pollution Control Technology Center Technology Center

Research Triangle InstituteResearch Triangle InstituteETV ETV Drinking WaterDrinking Water Systems Center Systems Center

NSF InternationalNSF International ETV ETV Greenhouse GasGreenhouse Gas Technology Center Technology Center

Southern Research InstituteSouthern Research InstituteETV ETV Advanced MonitoringAdvanced Monitoring Systems Center Systems Center

BattelleBattelleETV ETV Water Quality ProtectionWater Quality Protection Center Center

NSF InternationalNSF InternationalETV- ETV- Building DecontaminationBuilding Decontamination Center Center

BattelleBattelleETV ETV P2 Coatings and Coating EquipmentP2 Coatings and Coating Equipment PilotPilot

Concurrent Technologies CorporationConcurrent Technologies Corporation

88

46 Verifications in 200346 Verifications in 2003AMS:AMS: 5 Arsenic Detection; 5 Mercury CEMs; 1 Onboard 5 Arsenic Detection; 5 Mercury CEMs; 1 Onboard Mobile Mobile Emission Emission Monitor; 1 Portable Multi-Gas Emission Monitor; 1 Portable Multi-Gas Emission Monitor; Monitor; 2 Multi-Parameter Water 2 Multi-Parameter Water Probes; 6 Cyanide Detection KitsProbes; 6 Cyanide Detection KitsSCMT:SCMT: 1 Lead in Dust; 2 Groundwater Sampling Devices 1 Lead in Dust; 2 Groundwater Sampling Devices APCT:APCT: 3 Mobile Source Devices3 Mobile Source DevicesGHG:GHG: 1 Fuel Cell; 2 Micro-turbine CHP; 1 Vehicle Axle 1 Fuel Cell; 2 Micro-turbine CHP; 1 Vehicle Axle Lubricant; 1 Natural Gas Dehydration Lubricant; 1 Natural Gas Dehydration DWS:DWS: 2 Filtration Technologies2 Filtration TechnologiesWQP:WQP: 5 Residential Nutrient Reduction Systems; 1 Animal Waste 5 Residential Nutrient Reduction Systems; 1 Animal Waste Treatment (Solids Separator); 3 UV DisinfectionTreatment (Solids Separator); 3 UV DisinfectionCCEP:CCEP: 1 Liquid Paint; 1 UV Curable Coating; 1 High Transfer 1 Liquid Paint; 1 UV Curable Coating; 1 High Transfer Efficiency Paint Efficiency Paint Spray GunSpray GunP2-MF:P2-MF: 1 Sludge Reduction 1 Sludge Reduction

99

Projections for 2004Projections for 2004

Over 80 verificationsOver 80 verifications half in base ETV half in base ETV half in homeland security technologieshalf in homeland security technologies

1010

ETV is partnering with ..ETV is partnering with .. US National Oceanic and Atmospheric AdministrationUS National Oceanic and Atmospheric Administration

Multi-parameter water probesMulti-parameter water probes US Coast GuardUS Coast Guard

Ballast water treatmentBallast water treatment US Dept of Energy, State of MassachusettsUS Dept of Energy, State of Massachusetts

Continuous emission mercury monitorsContinuous emission mercury monitors US Dept of DefenseUS Dept of Defense

Monitors for explosives; PCBs in soils; dust suppressantsMonitors for explosives; PCBs in soils; dust suppressants States of Alaska, PennsylvaniaStates of Alaska, Pennsylvania

Drinking water arsenic treatment Drinking water arsenic treatment States/counties in Georgia, Kentucky, MichiganStates/counties in Georgia, Kentucky, Michigan

Storm water treatmentStorm water treatment States of New York, ColoradoStates of New York, Colorado

Waste to energyWaste to energy USDA USDA

Ambient ammonia monitorsAmbient ammonia monitors

1111

www.epa.gov/etvwww.epa.gov/etv

Note: There were 76,588 total hits and 7,075 international hits in September 2003.

International HitsTotal Hits

(1999) (2000) (2001)

Hit

s/Q

uar

ter

(2002) (2003)(1998)

0

40,000

80,000

120,000

160,000

200,000

1st 3rd 1st 3rd 1st 3rd 1st 3rd 1st 3rd 1st 3rd

1212

Getting to ETV OutcomesGetting to ETV OutcomesMeasuring outputs to outcomesMeasuring outputs to outcomes

Number of protocols and verificationsNumber of protocols and verifications Value placed on ETV by vendors in Value placed on ETV by vendors in

selling and innovating technologyselling and innovating technology Value to potential purchasers; Value to potential purchasers;

influence of ETV on purchase influence of ETV on purchase decisionsdecisions

Use of better technologies; reduced Use of better technologies; reduced emissions because of ETVemissions because of ETV

Reduced exposure; reduced risk Reduced exposure; reduced risk because of ETVbecause of ETV

Improved health/environmental quality Improved health/environmental quality because of ETVbecause of ETV

Outputs

Outcomes

1313

Technology developers analyze Technology developers analyze randomized samples under field randomized samples under field

conditions.conditions.

Samples are collected, homogenized, labeled, and assembled for distribution.

Product is report and verification statement.

Experimental Plan

Statisticians

Chemists

Project Officers

Stakeholders

Overview of Environmental Technology Verification Overview of Environmental Technology Verification ProcessProcess

Developers

1414

Lead in Dust:Lead in Dust:Rationale for Performance VerificationRationale for Performance Verification

““Childhood lead poisoning remains a major Childhood lead poisoning remains a major preventable environmental health problem in the preventable environmental health problem in the United States.”United States.”

- Centers for Disease Control and Prevention- Centers for Disease Control and Prevention

““Children are most frequently lead poisoned by Children are most frequently lead poisoned by household lead paint dust.”household lead paint dust.”

- - Massachusetts Dept of Public HealthMassachusetts Dept of Public Health

1515

Selection of the Most Appropriate Selection of the Most Appropriate Material to TestMaterial to Test

Technical panel prioritized current industry Technical panel prioritized current industry needs for evaluation of field technologies needs for evaluation of field technologies

for detection of lead as:for detection of lead as:

DUSTDUST PAINTPAINT SOILSOIL

Greatest need

1616

Fundamental Issue:Fundamental Issue:Can Field Analytical Technology be Used to Can Field Analytical Technology be Used to

Facilitate Home Reuse Following Facilitate Home Reuse Following Remediation?Remediation?

1717

Why “dust wipes” versus “bulk Why “dust wipes” versus “bulk dust”?dust”?

Wipe sampling estimates Wipe sampling estimates surface lead loadingsurface lead loading g of lead per unit areag of lead per unit area

Risk-based dust-lead loading Risk-based dust-lead loading standards established based on standards established based on dust wipe samplingdust wipe sampling

Testing under the NLLAP is Testing under the NLLAP is restricted to dust wipes.restricted to dust wipes.

Readily available ELPAT Readily available ELPAT samples with certified samples with certified concentrationsconcentrations ““Real-world” samples of Real-world” samples of

known contentknown content

1818

What were the regulatory drivers What were the regulatory drivers for this dust wipe testing?for this dust wipe testing?

ETV tests provide information on potential ETV tests provide information on potential applicability of field technologies for clearance applicability of field technologies for clearance testing.testing.

Relevancy to clearance levelsRelevancy to clearance levels††

40 40 g/ftg/ft22 floors floors 250 250 g/ftg/ft22 window sills window sills 400 400 g/ftg/ft22 window troughs window troughs

ApplicationsApplications Clearance testingClearance testing Risk assessmentRisk assessment

† Identification of dangerous levels of lead, Final Rule, 1/5/01, 40 CFR 745.65

1919

How did we arrive at this How did we arrive at this experimental design?experimental design?

Technical Panel

EPA HUDAIHA

Massachusetts

NISTNIOSH

RTI

VENDORS

ORNL

2020

How did we arrive at How did we arrive at 160 samples?160 samples?

Looked at all of the archived ELPAT Looked at all of the archived ELPAT samples; selections based on samples; selections based on concentration and number of concentration and number of samples availablesamples available

Requested newly-prepared samples Requested newly-prepared samples to focus on particular clearances to focus on particular clearances levels (40, 250, 400 levels (40, 250, 400 g)g)

Implemented statistically-balanced Implemented statistically-balanced design of four replicatesdesign of four replicates

2121

Determining the Number of Blank Determining the Number of Blank Samples to Evaluate False Positive Samples to Evaluate False Positive

Error RateError Rate

Number of Blank Samples

0 4 8 12 16 20 24 28 32 36 40

Up

pe

r 9

5%

Co

nfi

de

nc

e I

nte

rva

l

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Positive Error = 0 Positive Error = 1Positive Error = 2

Confidence in the estimate of the

false positive error rate increases as

more blank samples are evaluated.

2222

050

100150200250300350400450500

0 5 10 15 20 25

Sample Number

Tes

t Lev

el (u

g pe

r w

ipe)

Attention to Clearance LevelsAttention to Clearance Levels

Clearance levels

Four replicate samples analyzed for each test level.

2323

Testing Venues Focused on Where Testing Venues Focused on Where the Interest Liesthe Interest Lies

2424

Two Very Different Analytical Two Very Different Analytical Techniques VerifiedTechniques Verified

Portable X-ray fluorescencePortable X-ray fluorescence Portable anodic stripping voltammetryPortable anodic stripping voltammetry

2525

Vendors That Participated in the Vendors That Participated in the Lead in Dust ETV TestsLead in Dust ETV Tests

Niton Corporation (3 XRF systems)Niton Corporation (3 XRF systems) Monitoring Technologies International (ASV)Monitoring Technologies International (ASV) Palintest (ASV)Palintest (ASV) Key Master Technologies/EDAX (XRF) Key Master Technologies/EDAX (XRF)

2626

Anodic Stripping Voltammetry for Anodic Stripping Voltammetry for Determination of LeadDetermination of Lead

Anodic stripping voltammograms for the Anodic stripping voltammograms for the sample and two standard additions of 50 sample and two standard additions of 50 ppb Pb(II). Deposition potential = -600 ppb Pb(II). Deposition potential = -600

mV; deposition time = 1 min.; quiet time = mV; deposition time = 1 min.; quiet time = 10 sec. S.W. frequency = 15 Hz; step 10 sec. S.W. frequency = 15 Hz; step

potential = 4 mV; potential = 4 mV;

S.W. amplitude = 25 mVS.W. amplitude = 25 mV

Pb(II) is reduced to Pb(0) by holding potential at cathodic value for brief period; Pb quantified with anodic potential sweep, measuring current for oxidizing Pb(0) to Pb(II) and stripping it from solid electrode.

Electrochemical cell uses a working (W), reference (R), and auxillary (A) electrodes in cylindrical tube with teflon cap.

2727

Anodic Stripping VoltammetryAnodic Stripping Voltammetry

AdvantagesAdvantages Low capital costLow capital cost Disposable materialDisposable material Very high sample throughputVery high sample throughput

DisadvantagesDisadvantages Generates small amounts of chemical wasteGenerates small amounts of chemical waste

2828

X-Ray FluorescenceX-Ray FluorescenceExposing metallic materials to high energy x-rays stimulates ejection of electronsthe energies of which provide information concerning the identity of the metal in

question.

2929

X-Ray FluorescenceX-Ray Fluorescence

AdvantagesAdvantages Non-destructive analysisNon-destructive analysis Produces no chemical wasteProduces no chemical waste Good sample throughputGood sample throughput

DisadvantagesDisadvantages High capital costHigh capital cost May need radiation source licenseMay need radiation source license

3030

NITON XL300NITON XL300

0

5

10

15

20

25

ELP AT Samples UC Samples

NITON 300

Ref Lab

Precision

75

80

85

90

95

100

105

110

115

120

125


NITON 300

Ref Lab

Accuracy

Less is better

Ideal

3131


Clearance Clearance LevelLevel

µg/wipeµg/wipe

UC UC Samples,Samples,

µg/wipeµg/wipe

ELPAT ELPAT Samples,Samples,

µg/wipeµg/wipe

4040 3939 4242

250250 224224 213213

400400 346346 303303

Reported Concentrations at Clearance Levels

True Pb Concentration (ug/wipe)

30 35 40 45 50P

r(R

epor

t < 4

0 gi

ven

True

Pb)

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

DataChemNiton XL-300

Probabilities of False Negatives

3232


Comparability: R = 0.999 (ELPAT samples); R = 0.999 (UC samples)

False positive results (relative to clearance levels): 0% (0 of 12 ELPAT Samples); 0% (0 of 30 UC samples)

False negative results (relative to clearance levels): 54% (15 of 38 ELPAT); 70% (21 of 30 UC samples) [25% and 77% for Reference Laboratory]

Reporting limit: 15 µg/wipe

Throughput (1 analysts): 40 samples/12 hr day

Statistically significant negative bias (“penalty” for high precision) but within acceptable bias range.

3333


75

80

85

90

95

100

105

110

115

120

125


NITON XL700

Ref Lab

0

5

10

15

20

25


NITON XL 700

Ref Lab

Accuracy

Precision

Less is better

Ideal

3434



µg/wipeµg/wipe


µg/wipeµg/wipe


µg/wipeµg/wipe

4040 4242 4949

250250 276276 272272

400400 431431 372372True Pb Concentration (ug/wipe)

30 35 40 45 50

Pr(

Rep

ort

< 4

0 g

iven

Tru

e P

b)

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

DataChem

Niton XL-700



3535




False negative results (relative to clearance levels): 7% ( 2 of 28 ELPAT); 8% (2 of 26 UC samples) [25% and 77% for Reference Laboratory]


Throughput (1 analyst): 30 - 60 samples/12 hr day

Statistically significant positive bias (“penalty” for high precision) but within acceptable bias range.

3636

NITON XLt 700NITON XLt 700

75

80

85

90

95

100

105

110

115

120

125


NITON XL700

Ref Lab

0

5

10

15

20

25


NITON XL 700

Ref Lab

AccuracyPrecision

Less is betterIdeal

3737






Throughput (2 analysts): 45 - 50 samples/10 hr day

Statistically significant negative bias (“penalty” for high precision) but within acceptable bias range.

3838


10 15 20 25 30 35 40 45 50 55P

r(R

epo

rt <

40

giv

en T

rue

Pb

)0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

NITON XLt 700

DataChem



µg/wipeµg/wipe


µg/wipeµg/wipe


µg/wipeµg/wipe

4040 4242 4242

250250 232232 234234

400400 371371 361361



3939

Keymaster Pb-Test XRFKeymaster Pb-Test XRF

75

95

115

135

155

175

195

ELP ATSamples

UC Samples

Keymaster P bTest

Ref Lab

Keymaster >200ug/wipe

0

5

10

15

20

25


Keymaster P bTest

Ref Lab

Accuracy Precision

Less is betterIdeal

4040


35 40 45 50P

r(R

epo

rt <

40

giv

en T

rue

Pb

)0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

DataChem

Pb-Test

Keymaster Pb Test XRFKeymaster Pb Test XRF


µg/wipeµg/wipe


µg/wipeµg/wipe


µg/wipeµg/wipe

4040 118118 9999

250250 275275 254254

400400 365365 248248



Due to the positive biasat low lead levels, there was nochance of a false negative Response at the 40 µg/wipe level

4141

Keymaster Pb Test XRFKeymaster Pb Test XRF

Comparability: R = 0.967 (for samples ≤ 200 µg/wipe); R = 0.989 (for samples > 200 µg/wipe);



Reporting limit: None provided

Throughput (2 analysts and 2 instruments): 80 samples/10 hr day

Statistically significant positive bias for samples ≤ 200 µg/wipe; unbiased for samples above 200 µg/wipe; acceptable precision.

4242

MTI PDV 5000MTI PDV 5000

75

80

85

90

95

100

105

110

115

120

125


P DV 5000

Ref Lab

0

5

10

15

20

25


P DV 5000

Ref Lab

AccuracyPrecision

Less is betterIdeal

4343


25 50 75 100 125 150 175 200P

r(R

epo

rt <

40

giv

en T

rue

Pb

)

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

DataChem

MTI PDV 5000



µg/wipeµg/wipe


µg/wipeµg/wipe


µg/wipeµg/wipe

4040 2929 4444

250250 240240 213213

400400 375375 258258



4444


Comparability: R = 0.999 (for UC samples ); R = 0.988 (for ELPAT samples);



Reporting limit: < 20 µg/wipe

Throughput (2 analysts and 1 instrument): 80 samples/10 hr day

Statistically significant negative bias; less precise than typically acceptable levels; strong linear relationship between PDV 5000 response and that of comparable lab method.

4545

PalintestPalintestScanning Analyzer Scanning Analyzer SA-5000 SA-5000

75

80

85

90

95

100

105

110


SA-5000

Ref Lab

0

1

2

3

4

5

6

7

8

9

10


SA-5000

Ref Lab

AccuracyPrecision

Less is better

Ideal

4646


35 40 45 50 55 60P

r( R

epo

rt <

40

giv

en T

rue

Pb

)0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

DataChemPalintest

PalintestPalintestScanning Analyzer SA-5000 Scanning Analyzer SA-5000


µg/wipeµg/wipe


µg/wipeµg/wipe


µg/wipeµg/wipe

4040 3535 3636

250250 189189 221221

400400 308308 372372



4747

PalintestPalintestScanning Analyzer SA-5000 Scanning Analyzer SA-5000

Comparability: R = 1.00 (for UC samples ); R = 0.995 (for ELPAT samples);



Reporting limit: < 25 µg/wipe

Throughput (1 analyst and 1 instrument): 80 samples/10 hr day

Statistically significant negative bias; very precise; strong linear relationship between SA-5000 response and that of comparable lab method; no false positives, high number of false negatives.

4848

ETV Program does NOT make ETV Program does NOT make Head to Head comparisons of Head to Head comparisons of

technologies, because there are technologies, because there are needs for a variety of tools in the needs for a variety of tools in the environmental technology toolboxenvironmental technology toolbox

4949

Asking: “What is the Best Asking: “What is the Best Technology?” is Like Asking “What Technology?” is Like Asking “What is the Best Vehicle to Purchase?”is the Best Vehicle to Purchase?”

It depends on what you need!It depends on what you need!

Sports car vs. MiniVan

PS: Your mileage may vary

5050

Upcoming Technology Verifications Upcoming Technology Verifications by the Advance Monitoring Systems by the Advance Monitoring Systems

CenterCenter

More rounds of arsenic test kits for waterMore rounds of arsenic test kits for water Multi-parameter water monitorsMulti-parameter water monitors Ambient ammonia monitors for animal feed Ambient ammonia monitors for animal feed

operationsoperations Ammonia continuous emission monitorsAmmonia continuous emission monitors Immunoassay kits for anthrax, botulinum toxin, Immunoassay kits for anthrax, botulinum toxin,

& ricin& ricin PCR kits for anthrax, plague, Tularemia, PCR kits for anthrax, plague, Tularemia,

BrucellosisBrucellosis

5151

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Determination of Lead in Dust Wipes using Field Analytical Technology