NEW NIOSH SAMPLING AND ANALYTICAL METHODS FOR OCCUPATIONAL EXPOSURE ASSESSMENT
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1 NEW NIOSH SAMPLING AND ANALYTICAL METHODS FOR OCCUPATIONAL EXPOSURE ASSESSMENT Kevin Ashley, Ph.D. US Department of Health and Human Services Centers for Disease Control and Prevention National Institute for Occupational Safety and Health Cincinnati, Ohio Etats-Unis INRS Chemical Risk Conference, Nancy, France, 9 April 2015
2 NIOSH Manual of Analytical Methods (NMAM) History 1 st Edition: nd Edition: P&CAM (Physical & Chemical Analysis Method) S-methods (Standards Completion Program) 3 rd Edition: Format and numbering scheme 4 th Edition: th Edition: since 2007
3 Newer NIOSH methods 1453 Vinyl Acetate (rev) 7704 Beryllium by Field-Portable Fluorometry 8007 Toluenein Blood 8326 S-BenzylmercapturicAcid and S-PhenylmercapturicAcid in urine (metabolites of toluene and benzene) 9106 Methamphetamine and Illicit Drugs on Wipes by Liquid-Liquid Extraction 9109 Methamphetamine and Illicit Drugson Wipes by Solid Phase Extraction 9110 Beryllium on Wipes by Field-Portable Fluorometry 9111 Methamphetamine on Wipes by LC/Mass Spec
4 Newest NIOSH methods [non-bio] ( ) 7906, 7907 & 7908 Inorganic acids 7302 & 7304 Elements (microwave digestion) 7306 Elements (capsule sampler) 5524 Metalworking fluids (rev) 501 & 5100 Gravimetric (capsule sampler)
5 NIOSH aerosol sampling guidance CFCs ) K Ashley & M Harper, J OccupEnviron Hyg10, D29 (2013) Recommendation: Include material adhering to internal cassette surfaces during sampling and analysis of airborne particles 25 mm & 37 mm plastic sampling cassettes
6 Air sampling with capsule inserts Gravimetric PVC: NIOSH 501 & 5100 Metals cellulosic/digestible: NIOSH 7306 (Courtesy of SKC, Inc.) (Courtesy of Zefon International)
7 Gravimetric analysis with PVC internal capsules Analytical figures of merit (AZ Road Dust): LOD mg/sample LOQ 0.25 mg/sample Range: LOQ to >5 mg/sample Weight stable for >28 days A 95 ±16 %
8 Ex. multielement data from interlab study: Aerosol-dosed cellulosic capsules (8 labs) Element /level (µg) Mean±Std. Dev. (µg/m 3 ) RSD (%) Cd (7.5) 5.5 ± Cr (75) 340 ± Co (3.0) 13 ± Cu (150) 110 ± Fe (150) 630 ± Pb(60) 260 ± Mn (3.0) 16 ± Ni (75) 59 ± M Harper & K Ashley, JOEH 10, 297 (2013)
9 Elemental analysis of cellulosic internal capsules (1. dissolution & 2. analysis by ICP-AES) 33 elements, 3 levels (+ blank media), 9-lab round-robin [Considering EN 482 uncertainty criterion] Elements with U< 30%: Al, As, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, La, Li, Mg,Mn, Mo, Ni, P, Pb, Sb, Se, Sr, Te, Ti, Tl, V, Y, Zn, Zr Elements with U> 30%: Ag,In, K,Sn, W
10 New NIOSH methods for inorganic acids (NIOSH-IFA MOU) 7906 PARTICULATE FLUORIDES AND GASEOUS HYDROGEN FLUORIDE 7907 VOLATILE ACIDS: HYDROCHLORIC, NITRIC AND HYDROBROMIC ACIDS 7908 NON-VOLATILE ACIDS: SULFURIC AND PHOSPHORIC ACIDS Based on MAK methods (DFG) Consistent with ISO (3-part std.)
11 Method 7906: Particulate fluorides and HF vapor Sample fluorides in prefilter section Collect HF vapor on impregnated filter Extract in basic buffer Analysis by ion chromatography IMPREGNATED FILTER PREFILTER [Cellulose nitrate filter media]
12 HF and F - measurements from test atmospheres Analyte Conc.(mg/m 3 ) Stddev RSD(%) U(%) (n=6) HF HF HF HF Fluoride Fluoride Fluoride Fluoride
13 Analytical range Fluoride: to >1 mg; 0.04 to >10 mg/m 3 (120-L sample) [NIOSH 7906, cont d] HF recovery at high RH HF: to >1 mg; 0.13 to >10 mg/m 3 (120-L sample)
14 METHOD 7907 FOR VOLATILE ACIDS Quartz fiber filters (prefilter & impregnated) Analytical figures of merit Acid Analytical range U(%) (mg/sample; mg/m 3* ) HCl ; <12 HNO ; <14 HBr ; <12 *[ 240-L air sample]
15 METHOD 7908 FOR NON-VOLATILE ACIDS Quartz fiber or PTFE filter (no prefilter) Analytical figures of merit Acid Analytical range U(%) (mg/sample; mg/m 3* ) H 2 SO ; <23 H 3 PO ; <23 *[420-L air sample]
16 New NIOSH biomonitoring methods Method no. Method name Biological indicator of 8007 Toluene in blood Exposure to toluene 8326 S-Benzylmercapturic Exposure to acid and S- toluene and phenylmercapturic benzene acid in urine Bromoproprionic Exposure to 1- acid in urine bromopropane 8319 Acetone and methyl ethyl ketone in urine Exposure to acetone and methyl ethyl ketone Sample prep. None C18 solidphase extraction Liquid-liquid extraction / derivatization None Analysis technique Headspace/ GC/FID LC/MS/MS GC/MS (SIM) Headspace/ GC/FID
17 Under development (exs.) Draft chapters: Pesticides Direct-reading monitors Biomonitoring guidelines Draft methods: Pesticides (wipe samples) VOCs & semi-volatiles by capillary GC Canister sampling of gases / vapors o-cresol in urine (biomarker) Ketones
18 Acknowledgments Davy Rousset, INRS, Vandoeuvre-lès-Nancy, France Dietmar Breuer, IFA, Sankt Augustin, Germany Sean O Connor, NIOSH, Cincinnati OH, USA Dale Shoemaker, NIOSH, Cincinnati OH, USA Martin Harper, NIOSH, Morgantown WV, USA
19 Contact information Kevin Ashley, Ph.D. US Department of Health and Human Services Centers for Disease Control and Prevention National Institute for Occupational Safety and Health 1090 Tusculum Ave., Mail Stop R-7 Cincinnati, Ohio (USA) Tel.: +1(513) ; 19
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