Kevin Ashley, Ph.D. - American Industrial Hygiene Association · Analytical Methods for Beryllium Kevin Ashley, Ph.D. U.S. Department of Health and Human Services Centers for Disease

Analytical Methods for BerylliumAnalytical Methods for Beryllium

Kevin Ashley, Ph.D.Kevin Ashley, Ph.D.

U.S. Department of Health and Human ServicesU.S. Department of Health and Human ServicesCenters for Disease Control and PreventionCenters for Disease Control and Prevention

National Institute for Occupational Safety and HealthNational Institute for Occupational Safety and HealthCincinnati, OhioCincinnati, Ohio

DISCLAIMERS:DISCLAIMERS:

Mention of company names or products does not Mention of company names or products does not constitute endorsement by the Centers for Disease constitute endorsement by the Centers for Disease

Control and Prevention.Control and Prevention.

The findings and conclusions in this report are The findings and conclusions in this report are those of the authors and do not necessarily those of the authors and do not necessarily

represent the views of the National Institute for represent the views of the National Institute for Occupational Safety and Health.Occupational Safety and Health.

IntroductionIntroductionBackground:Background:-- Applicable limit valuesApplicable limit values-- Current state of the art / trace analysisCurrent state of the art / trace analysis-- Validated methods ensure defensibility of dataValidated methods ensure defensibility of data

Sample Preparation & Analysis:Sample Preparation & Analysis:-- Governmental & Consensus standard methodsGovernmental & Consensus standard methods-- Available reference materialsAvailable reference materials-- Standards & methods development activitiesStandards & methods development activities

Summary:Summary:-- What is available now? Data gaps?What is available now? Data gaps?-- What methods & standards are still needed?What methods & standards are still needed?

Beryllium limit valuesBeryllium limit values

DOE (10 CFR 850):DOE (10 CFR 850):0.2 0.2 µµg/mg/m33 Air contaminationAir contamination0.2 0.2 µµg/100 cmg/100 cm22 Surface contamination for equipment Surface contamination for equipment releaserelease3 3 µµg/100 cmg/100 cm22 Surface contamination for housekeepingSurface contamination for housekeeping

OSHA Permissible Exposure Limit (PEL):OSHA Permissible Exposure Limit (PEL):2 2 µµg/mg/m3 3 Air contaminationAir contamination

NIOSH Recommended Exposure Limit (REL):NIOSH Recommended Exposure Limit (REL):0.5 0.5 µµg/mg/m3 3 Air contaminationAir contamination

ACGIH Threshold Limit ValueACGIH Threshold Limit Value®® (TLV(TLV®®) NIC:) NIC:0.05 0.05 µµg/mg/m33 Air contamination (8Air contamination (8--hr TWA)hr TWA)0.2 0.2 µµg/mg/m33 Air contamination (STEL)Air contamination (STEL)

Media for beryllium analysis:Media for beryllium analysis:

Air samples (membrane filters)Air samples (membrane filters)Surface samples (e.g., wipes; vacuum): Surface samples (e.g., wipes; vacuum):

Hard / SmoothHard / SmoothSoft / RoughSoft / Rough

Dermal samples (e.g., wipes; patch)Dermal samples (e.g., wipes; patch)Bulks (e.g., soils; thick dust deposits)Bulks (e.g., soils; thick dust deposits)

Salient standardized methods for beryllium Salient standardized methods for beryllium sampling in workplace airsampling in workplace air

Membrane or Membrane or FibrousFibrous

““TotalTotal””, , InhalableInhalable or or RespirableRespirable

ASTM IntASTM Int’’l: l: D7035; D7202D7035; D7202

Membrane or Membrane or FibrousFibrous

InhalableInhalable or or RespirableRespirable

ISO 15202ISO 15202--11

Quartz filterQuartz filterInhalableInhalableFrance (INRS)France (INRS)

MembraneMembraneInhalableInhalableUK (HSE); UK (HSE); Germany (BGIA) Germany (BGIA)

MembraneMembrane““TotalTotal””USA (NIOSH & USA (NIOSH & OSHA)OSHA)

Filter Filter type(stype(s))Aerosol Aerosol fraction(sfraction(s))Method(sMethod(s) )

Standardized surface sampling methodsStandardized surface sampling methods

CarpetsCarpetsVacuum samplerVacuum samplerASTM D5438ASTM D5438

Rough, porous or Rough, porous or fragile surfacesfragile surfaces

MicroMicro--vacuumvacuumASTM D7144ASTM D7144

Special substratesSpecial substratesDry wipe (Be only)Dry wipe (Be only)ASTM D7296ASTM D7296

Dermal samplesDermal samplesPatch or RinsePatch or RinseNIOSH & OSHA NIOSH & OSHA

Smooth surfacesSmooth surfacesAdhesive tapeAdhesive tapeASTM E1216ASTM E1216

Smooth surfacesSmooth surfacesWet wipeWet wipeASTM D6966ASTM D6966

Smooth; DermalSmooth; DermalWet wipeWet wipeNIOSH (several)NIOSH (several)

Smooth / Hard; Smooth / Hard; DermalDermal

Wet or dry filter or Wet or dry filter or wipewipe

OSHA (several)OSHA (several)

Surface(sSurface(s))Media / deviceMedia / deviceMethod(sMethod(s))

Standardized sample preparation methods for beryllium

∆∆, , ≈≈ or )))or )))Various optionsVarious optionsAir filterAir filterISO 15202ISO 15202--22

∆∆ or or ≈≈Various optionsVarious optionsAir filterAir filterASTM D7035ASTM D7035

∆∆ or or ≈≈HNOHNO33 / HF/ HFAir filterAir filterINRS 003 INRS 003 (France)(France)

∆∆HNOHNO33 / H/ H22SOSO44Air filterAir filterHSE 29/2 (UK)HSE 29/2 (UK)

∆∆HClHCl / HNO/ HNO33Air filter, Wipe or Air filter, Wipe or BulkBulk

OSHA IDOSHA ID--206206

∆∆HNOHNO3 3 / H/ H22SOSO4 4 //HClHCl

Air filter, Wipe or Air filter, Wipe or BulkBulk

OSHA IDOSHA ID--125G125G

∆∆ or or ≈≈HNOHNO33 / HClO/ HClO44Air filter / WipeAir filter / WipeNIOSH 7300 / NIOSH 7300 / 73027302

∆∆HNOHNO33 / H/ H22SOSO44Air filterAir filterNIOSH 7102NIOSH 7102

∆∆, , ≈≈, ))), )))AcidsAcidsMatrixMatrixMethodMethod

Beryllium spectrometric analysis

Atomic spectrometry by:

- GFAAS (single element)

- ICP-AES (multielement)

- ICP-MS (ultratrace analysis)

Standardized methods for beryllium Standardized methods for beryllium by spectrometric analysisby spectrometric analysis

------ICPICP--AESAESISO 15202ISO 15202--330.0090.009ICPICP--AESAESASTM D7035ASTM D70350.001; 0.00050.001; 0.0005ICPICP--MSMSEPA 200.8; 6020EPA 200.8; 60200.008; 0.0050.008; 0.005ICPICP--AESAESEPA 200.7; 6010BEPA 200.7; 6010B0.0050.005GFAASGFAASEPA 7091EPA 7091

0.013; 0.00720.013; 0.0072ICPICP--AESAESOSHA IDOSHA ID--125G; ID125G; ID--206206

0.0050.005ICPICP--AESAESNIOSH 7300NIOSH 73000.0050.005GFAASGFAASNIOSH 7102NIOSH 7102MDL (MDL (µµg Be)g Be)TechniqueTechniqueMethod(sMethod(s))

Voluntary consensus standard ICPVoluntary consensus standard ICP--MS MS method for elements in workplace air:method for elements in workplace air:

Under parallel development within ASTM Under parallel development within ASTM International and ISOInternational and ISO

InterlaboratoryInterlaboratory study to evaluate ~20 elements study to evaluate ~20 elements (beryllium is one)(beryllium is one)

Sample preparation procedures to include:Sample preparation procedures to include:-- Hot plate digestionHot plate digestion-- Microwave digestionMicrowave digestion-- HotHot--block extractionblock extraction-- [Ultrasonic extraction an option][Ultrasonic extraction an option]

Alternative dissolution solution Alternative dissolution solution for berylliumfor beryllium

Dilute aqueous ammonium Dilute aqueous ammonium bifluoridebifluoride, , (NH(NH44)HF)HF22::

Less hazardous than concentrated acids (e.g., Less hazardous than concentrated acids (e.g., HH22SOSO44, HF), HF)Effective for dissolving Be metal and Effective for dissolving Be metal and BeOBeODoes not dissolve matrix (filter or wipe)Does not dissolve matrix (filter or wipe)Heat (~85 Heat (~85 ooCC) assists in dissolution of ) assists in dissolution of refractory refractory ““highhigh--firedfired”” BeOBeO

Beryllium fluorescence method: Beryllium fluorescence method: fluorophorefluorophore for trace detectionfor trace detection

Beryllium binds Beryllium binds phenolatephenolate groups groups stronglystronglyA six member A six member chelatechelatering provides ideal ring provides ideal BeBe--O / BeO / Be--N N stereochemistrystereochemistry

N OH

SO3H

Hydroxybenzoquinolinesulfonic acid (HBQS)

Beryllium fluorescence with HBQSBeryllium fluorescence with HBQS

Detection is Detection is quantitative above quantitative above 0.036 ppb (<0.001 0.036 ppb (<0.001 µµg Be/sample)g Be/sample)

Linear response, Linear response, wide dynamic rangewide dynamic range

Verified lack of Verified lack of interference from interference from other metalsother metals

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

0.45

0.5

300 400 500 600 700 800Wavelength (nm)

Rel

ativ

e In

tens

ity

0 ppb Be 0.5 ppb Be

1 ppb Be 4 ppb Be

10 ppb Be 30 ppb Be

N

O

HO3S

Be+

N

OH

HO3S

Beryllium fluorescence method (1)Beryllium fluorescence method (1)

Collect sample on media:Surface wipeAir filter

Dissolve beryllium:Dilute ammonium bifluorideHeating block for BeO samplesRecovery >90% in ~30 min.

Beryllium fluorescence method (2)Beryllium fluorescence method (2)

FilterCommercial filter syringe

MixMix fluorescent dye and sample

(1:19 routine; 1:4 trace)

MeasurePlace cuvette in instrumentMeasure [Be] to trace levels

Key advantages:Key advantages:BerylliumBeryllium--byby--fluorescence methodfluorescence method

Field or laboratory deployable Field or laboratory deployable Detection limit <0.0003 Detection limit <0.0003 µµg Be/sample (0.011 ppb)g Be/sample (0.011 ppb)Good recoveries from Be & Good recoveries from Be & BeOBeO with (NHwith (NH44)HF)HF22

Rapid turnaround (test results within one hour)Rapid turnaround (test results within one hour)High throughput (can process ~30 samples/90 minutes)High throughput (can process ~30 samples/90 minutes)BerylliumBeryllium--specific (other metals do not interfere)specific (other metals do not interfere)Low capital cost (< $10,000)Low capital cost (< $10,000)Quantification from Quantification from <0.002 <0.002 µµg g to >4 to >4 µµgg using portable using portable fluorometerfluorometer (5(5xx / 20/ 20xx dilution)dilution)

→→LOD for Be comparable to ICPLOD for Be comparable to ICP--MSMS

Beryllium fluorescence method Beryllium fluorescence method acceptance:acceptance:

ASTM International:ASTM International:ASTM D7202, ASTM D7202, ““Standard Test Method for Standard Test Method for Determination of Beryllium in the Workplace Using Determination of Beryllium in the Workplace Using FieldField--Based Extraction and Fluorescence DetectionBased Extraction and Fluorescence Detection””((www.astm.orgwww.astm.org))

CDC/NIOSH:CDC/NIOSH:NIOSH Manual of Analytical Methods NIOSH Manual of Analytical Methods ((www.cdc.gov/niosh/nmamwww.cdc.gov/niosh/nmam))Methods 7704 (air) & 9110 (wipes)Methods 7704 (air) & 9110 (wipes)

Beryllium NIST Beryllium NIST SRMsSRMs

5 mg/L (Be 10/9 = 5 mg/L (Be 10/9 = 3 3 ×× 1010--1111))

Be 10/9 MS Be 10/9 MS standard solutionstandard solution

43254325

10 mg/L10 mg/LSingle element Single element standard solutionstandard solution

3105a3105a

1.6 1.6 µµg/gg/gNY/NJ waterway NY/NJ waterway sedimentsediment

19441944

1.0 1.0 µµg/gg/gBituminous coalBituminous coal1632c1632c

1.75%1.75%BeBe--Cu alloy (block)Cu alloy (block)C1122C1122

0.360%; 1.82%; 0.360%; 1.82%; 1.86%1.86%

BeBe--Cu alloy (chips)Cu alloy (chips)458; 459; 460458; 459; 460

Certified [Be]Certified [Be]MaterialMaterialSRM No.SRM No.

Desired beryllium Desired beryllium CRMsCRMsCompound:

Beryllium Oxide (esp. high-fired)

- NIST/DOE/NIOSH BeO SRM project

Media:

Air filters (aerosols)

Spiked wipes

BeO-spiked filter CRMs are commercially available.

SEM of SEM of BeOBeO on MCE filter*on MCE filter*

*BeO-spiked filters courtesy of High-Purity Standards;SEM by J. Fernback, CDC/NIOSH

SummarySummaryAnalytical methods for Beryllium:- Use of more sensitive methods than ICP-AES and GFAAS (i.e.: ICP-MS, fluorescence) may be required in near future

- Data gaps remain for Be recoveries from sampling media & sample prep protocols

- Reference materials lacking, but efforts to fill this need are underway

IHs & labs should harmonize sampling & analysis procedures!

AcknowledgmentsAcknowledgments

AnoopAnoop AgrawalAgrawal, , BerylliantBerylliant, Inc., Inc.Mike Mike BrissonBrisson, Washington Savannah River Co., Washington Savannah River Co.Alan Howe, Health & Safety Laboratory (UK)Alan Howe, Health & Safety Laboratory (UK)Mark Mark McCleskeyMcCleskey, Los Alamos National Laboratory, Los Alamos National LaboratoryKennKenn White, AIHA FellowWhite, AIHA Fellow

Beryllium Health & Safety Committee, Sampling & Beryllium Health & Safety Committee, Sampling & Analytical SubcommitteeAnalytical Subcommittee

ASTM International Subcommittee D22.04 on Workplace ASTM International Subcommittee D22.04 on Workplace Air QualityAir Quality

ISO Workplace Air Quality subcommittee, Inorganic ISO Workplace Air Quality subcommittee, Inorganic working group (ISO TC 146/SC 2/WG 2)working group (ISO TC 146/SC 2/WG 2)