News On Air - Sigma

Environmental
Welcome to News on Air
2014 Volume 3
This edition will cover the recent developments
in sampling of isocyanates with the ASSET™
EZ4-NCO Dry Sampler.
This new and easy to use sampling device for the determination of
Isocyanate monomers and oligomers in air offers
detection limits and high capacity, with sampling times from 5
• Low
minutes up to 8 hours for true TWA determinations
derivatisation using Dibutylamine (DBA) - no refrigeration or
• Stable
infield extraction is needed
derivatisation of particles, preventing underestimation of
• Complete
isocyanate exposure
with ISO17734-1 “Determination of organonitrogen
• Compliance
compounds in air using liquid chromatography and mass
The sampler is supported by a set of calibration standards including a
deuterated internal standard mix for LC-MS/MS.
Isocyanates are used in the production of polyurethane (PUR) materials,
one of the most widely used plastics in the world. Workers who are
exposed to these compounds either in a production or by treating/
handling PUR coated materials (e.g. welding or spray coating) are at risk
for respiratory disorders, asthma and other health conditions. Particulate
isocyanates often show incomplete reactions with the used reagent
using common sampler types, which can results in underestimation of
exposure. Additionally filter samples often show very limited capacity
allowing only fro short sampling times.
The ASSET EZ4-NCO sampling device is a unique dry sampler
based on derivatization of isocyanate groups with di-n-butylamine.
The sampler consists of a denuder and a filter, both impregnated
with DBA. The sampler extract is analyzed using LC-MS or LC-MSMS offering the ultimate sensitivity and low detection limits not
achievable with other methods.
spectrometry —Part 1: Isocyanates using dibutylamine derivatives”
Introducing the Comprehensive
Air Monitoring Capabilities of the
NCO Dry Sampler-ASSET EZ4
For more information and to watch a video on the
sampler's functionality and use, visit
sigma-aldrich.com/asset
News On Air | Volume 3
Sampling of Isocyanates
Field Sampling Recommendations
Flow Rate: 200 mL/min (suggested)
Range (100 to 250 mL/min)
Low back-pressure (suitable for most air sampling pumps):
9 inches of water @ 200 mL/min
Sampling Time: 15 minutes is typical,
(range can be 5 minutes to 8 hours)
Analysis of the sampler
Extraction of Sampler.
The denuder & filter section of the sampler are extracted with
solvent For a step by step procedure on the extraction of the ASSET
sampler, including an equipment and reagents list, please visit
wwwsigmaaldrich.com/asset
LC-MS/MS Analytical Conditions for Isocyanate Analysis
Using ASSET Sampler
Escort® Elf Air Sampling Pump
sigma-aldrich.com/analytical
PAS-500 Micro Air Sampler with Low Flow Orifice
While a range of air monitoring applications use GC for analysis, the
analysis of the ASSET sampler uses a liquid.
3
ASSET™ EZ4-NCO Standards
This set of analytical standards supports the LC/MS Analysis of the Isocyanates collected with the ASSET sampler:
40141-U DBA Isocyanate Mix (acetonitrile:methanol, 99:1, varied conc) 6 x 1 mL
Isocyanic acid-di-n-butylamine (ICA-DBA)
1 μg/mL
Ethyl isocyanate-di-n-butylamine (EIC-DBA)
1 μg/mL
Hexamethylene diisocyanate-2(di-n-butylamine) (HDI-2(DBA)
1 μg/mL
Isophorone isocyanate-2(di-n-butyl amine) isomer 1 (IPDI-2(DBA)
1 μg/mL
Isophorone isocyanate-2(di-n-butyl amine) isomer 2 (IPDI2-2(DBA)
0.4 μg/mL
4,4’-Methylenediphenyl diisocyanate-2(di-n-butylamine) (4,4’-MDI-2(DBA)
1 μg/mL
Methyl isocyanate-di-n-butylamine (MIC-DBA)
1 μg/mL
Phenyl isocyanate-di-n-butylamine (PhI-DBA)
1 μg/mL
Propyl isocyanate-di-n-butylamine (PIC-DBA)
1 μg/mL
2,4-Toluene diisocyanate-di-n-butylamine (2,4-TDI-2(DBA)
1 μg/mL
2,6-Toluene diisocyanate-2(di-n-butylamine) (2,6-TDI-2(DBA)
1 1 μg/mL d9-DBA
40142-U Isocyanate Internal Standard Mix 6 x 1 mL
Isocyanic acid-di-n-butylamine-d9 (ICA-DBA- d9)
1 μg/mL
Ethyl isocyanate-di-n-butylamine-d9 (EIC-DBA-d9)
1 μg/mL
Hexamethylene diisocyanate-2(di-n-butylamine-d9) (HDI-2(DBA-d9)
1 μg/mL
Isophorone diisocyanate-2(di-n-butylamine-d9) isomer 1 (IPDI-2(DBA-d9)
1 μg/mL
Isophorone diisocyanate-2(di-n-butylamine-d9) isomer 2 (IPDI2-2(DBA-d9)
0.28 μg/mL
4,4-Methylenediphenyl diisocyanate-2(di-n-butylaine-d9) (4,4’-MDI-2(DBA-d9)
1 μg/mL
Methyl isocyanate-di-n-butylamine-d9 (MIC-DBA-d9)
1 μg/mL
Phenyl isocyanate-di-n-butylamine-d9 (PhI-DBA-d9)
1 μg/mL
Propyl isocyanate-di-n-butylamine-d9 (PIC-DBA-d9)
1 μg/mL
2,4-Toluene diisocyanate-2(di-n-butylamine-d9) (2,4-TDI-2(DBA-d9)
1 μg/mL
2,6-Toluene diisocyanate-2(di-n-butylamine-d9) (2,6-TDI-2(DBA-d9)
1 μg/mL
40143-U DBA Isocyanate Standard Kit 2 x 1 mL
Includes 1 mL of DBA Isocyanate Mix and 1 mL of d9-DBA Internal Standard Mix
Analytical Service
An range of international contract laboratories offer an analytical service
for the ASSET-EZ4 NCO sampler. Please visit our website sigma-aldrich.
com/asset to find more details.
We recently launched Certified Reference Material (CRM) Standards for analysis of new
monomers HMDI and TMX diisocyanates and HDI adducts are also available . IPDI adducts
and pMDI are coming soon. For more information on availability, please contact Kristen
Schultz at [email protected].
World Regulatory Update
Piperazine compounds are commonly used in isocyanate sampling
devices as derivatives to convert the reactive isocyanates into stable
compounds that can be analyzed by HPLC. In the United Kingdom,
early in 2013, piperazine compounds were declared controlled
substances as a result of these compounds being used for the
More information is available at
www.sigmaaldrich.com/asset
manufacturing of illegal designer drug formulations. Therefore the
1,2-pyridyl piperazine (PP) wet sampler for OSHA methods 42 & 47
cannot be used as well as the impinger solution containing
1-(9-anthracenylmethyl) piperazine (MAP) for NIOSH 5525 and the UK
MDHS 25/3 methods. In addition, the ISO-CHEK® back-filter
containing 1-(2-methoxyphenyl) piperazine (MOPIP) can also not be
used for sampling and analysis of isocyanates
Since ASSET EZ4-NCO Dry Sampler does not contain any piperazine
compounds, it does not face regulatory or compliance issues in the UK.
OSHA National Emphasis Program (NEP) on Isocyanates
In June 2013, OSHA announced a new National Emphasis Program
(NEP) for occupational exposure to isocyanates that will focus on
workplaces in the general, construction and maritime industries in
which isocyanate compounds are used. Over a 3-year period, OSHA
will focus outreach efforts and inspections on isocyanate hazards in
an effort to reduce occupational illnesses, injuries and deaths, and to
News On Air | Volume 3
raise awareness of the health effects associated with exposure to
isocyanates, which can cause occupational asthma, irritation of
the skin, eyes, nose, and throat and cancer. Workers in jobs such as
painting, blowing foam insulation, and the manufacture and thermal
degradation of polyurethane products may be exposed to these
hazardous chemicals.
Within this program, OSHA issued an official statement that it is now
their recommendation that all isocyanates regardless of physical state
(vapor or aerosol) shall be field desorbed. The rationale behind this
decision is confirmed by the article from Karoly, American Industrial
Hygiene Journal 59:645-647, 1998, which showed under reporting of
MDI when samples were not field desorbed. There is a consensus in
the industry that the majority of the isocyanate sampling, especially
when aerosols reach a certain size (> 2 µm) the sample collected will
underestimate the airborne concentration.
Basically, OSHA is now recognizing that using a wet sampler
underestimates isocyanate exposures because it does not discern
collection of vapors from aerosols. This means that field desorption
will be required for wet samplers such as 1,2-PP coated filters and the
ISO-Chek back-filter. As a result, other sampling techniques must be
used to avoid this inconvenience, complexity and reliability issues
associated with field desorption. Therefore impinger methods or the
Supelco ASSET EZ4-NCO dry sampler must be used.
If you want to be in compliance with the OSHA NEP you will either
need to sample with glass impingers, derivatize your wet samplers in
the field, or collect your samples on the easy to use ASSET sampler.
Publications:
ISO 17734-1:2006, Determination of Organonitrogen Compounds in
Air Using Liquid Chromatography and Mass Spectrometry
Part 1: Isocyanates Using Dibutylamine Derivatives.
Part 2: Amines and Aminoisocyanates Using Dibutylamine and Ethyl
Chloroformate Derivatives.
Authors: Gunnar Skarping, Marianne Dalene and Daniel Karlsson
Isocyanates, Amines and Alkanolamines: Sampling, Chromatography
and Detection
Author: Riddar, Jakob B,
Affiliation: Department of Analytical Chemistry, Faculty of Science,
Stockholm University, P.O. Box 460, S-28124 Hassleholm, Sweden
Journal: Doctoral thesis, comprehensive summary (Other academic), 2013
Dry Sampling of Gas-Phase Isocyanates and Isocyanate Aerosols from
Thermal Degradation of Polyurethane
Authors: Daniel Gylestam, Jakob B Riddar, Marianne Dalene and
Gunnar Skarping
Affiliation: Department of Analytical Chemistry, Work Environment
Chemistry, Stockholm University, P.O. Box 460, S-28124 Hassleholm, Sweden
Journal: Annals of Occupational Hygiene, 2013, Aug 9
Solvent-Free Sampling with Di-n-Butylamine for Monitoring of
Isocyanates in Air
Authors: Asa Marand, Daniel Karlsson, Marianne Dalene and Gunnar
Skarping
Affiliation: Department of Analytical Chemistry, Work Environment
Chemistry, Stockholm University, P.O. Box 460, S-28124 Hassleholm, Sweden
Journal: Journal of Environmental Monitoring, 2005, 7, 335-343
Determination of Airborne Isocyanates as Di-n-Butylamine Derivatives
Using Liquid Chromatography and Tandem Mass Spectrometry
Authors: Daniel Karlsson Jakob Dahlin, Asa Marand, Gunnar Skarping,
Marianne Dalene
Affiliation: Department of Analytical Chemistry, Work Environment
Chemistry, Stockholm University, P.O. Box 460, S-28124 Hassleholm, Sweden
Journal: Analytica Chimica Acta, 2005, 534, 263-269
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