CEN/TR 16998:2016
(Main)Ambient air - Report on nitro- and oxy-PAHs - Origin, toxicity, concentrations and measurement methods
Ambient air - Report on nitro- and oxy-PAHs - Origin, toxicity, concentrations and measurement methods
This Technical Report is focused on the presence of nitro- and oxy-PAH compounds in ambient air. It describes how nitro- and oxy-PAH are formed, what typical concentrations are found, what is known about their toxicity, and what sampling and measurement techniques are available. The conclusions of this report are that nitro- and oxy-PAH concentrations are present in the atmosphere in level that are of concern regarding their high toxicity. Information on the presence of these compounds in ambient air is at least as relevant as information about PAH. Validated techniques for the measurement of nitro- and oxy-PAH are available.
Außenluft - Bericht über Nitro- und Oxy-PAHs - Herkunft, Toxizität, Konzentrationen und Messverfahren
Air ambiant - Rapport sur les nitro- et oxy-HAP - Origine, toxicité, concentrations et méthodes de mesure
Zunanji zrak - Poročilo za nitro- in oksi-PAH - Izvor, strupenost, koncentracije in merilne metode
To tehnično poročilo se osredotoča na prisotnost nitro- in oksi-PAH spojin v zunanjem zraku. Opisuje, kako nastanejo nitro- and oksi-PAH spojine, kakšne so tipične koncentracije, kaj je znano o njihovi toksičnosti in katere tehnike vzorčenja in meritev so na voljo. Ugotovitve tega poročila kažejo, da je raven koncentracije nitro- in oksi-PAH spojin v ozračju zaskrbljujoča z vidika njihove močne toksičnosti. Informacije o prisotnosti teh spojin v zunanjem zraku so najmanj tako pomembne kot informacije o PAH-u. Potrjene merilne metode za merjenje nitro- in oksi-PAH spojin so na voljo.
General Information
Standards Content (Sample)
SLOVENSKI STANDARD
01-julij-2017
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Ambient air - Report on nitro- and oxy-PAH - Origin, toxicity concentrations and
measurement methods
Außenluft - Nitro- und Oxy-PAHs - Herkunft, Toxizität, Konzentrationen und
Messverfahren
Air ambiant - Rapport concernant les HAP nitrés et les HAP oxygénés - Origine, toxicité,
concentrations et méthodes de mesure
Ta slovenski standard je istoveten z: CEN/TR 16998:2016
ICS:
13.040.20 Kakovost okoljskega zraka Ambient atmospheres
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
CEN/TR 16998
TECHNICAL REPORT
RAPPORT TECHNIQUE
November 2016
TECHNISCHER BERICHT
ICS 13.040.20
English Version
Ambient air - Report on nitro- and oxy-PAHs - Origin,
toxicity, concentrations and measurement methods
Air ambiant - Rapport sur les nitro- et oxy-HAP - Außenluft - Bericht über Nitro- und Oxy-PAHs -
Origine, toxicité, concentrations et méthodes de Herkunft, Toxizität, Konzentrationen und
mesure Messverfahren
This Technical Report was approved by CEN on 21 October 2016. It has been drawn up by the Technical Committee CEN/TC 264.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and
United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2016 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TR 16998:2016 E
worldwide for CEN national Members.
Contents Page
European foreword . 3
Introduction . 4
1 Scope . 5
2 Symbols and abbreviations . 5
3 Literature overview . 5
4 Conclusions . 20
5 Recommendations . 20
Annex A (informative) Sampling and analysis by GC-MS of some nitro- and oxy-PAHs
associated to ambient particulate matter . 22
A.1 Sampling . 22
A.2 Analytical materials . 22
A.2.1 Glassware and sample handling . 22
A.2.2 Reagents and Solvents . 22
A.2.3 Extraction apparatus and materials . 23
A.2.4 Evaporation apparatus and materials . 24
A.2.5 Clean-up Material . 24
A.2.6 Weighting Apparatus . 24
A.2.7 Analytical system . 24
A.3 Extraction . 24
A.4 Clean-up . 24
A.5 Analysis . 25
A.6 Results . 25
A.7 Quality assurance . 30
Annex B (informative) Carcinogenicity and references to nitro- and oxy-PAHs . 31
Annex C (informative) Mutagenicity of nitro-PAHs . 34
Annex D (informative) Diesel exhaust data . 35
Annex E (informative) Structures of nitro- and oxy-PAHs referred in this Technical Report . 36
Bibliography . 43
European foreword
This document (CEN/TR 16998:2016) has been prepared by Technical Committee CEN/TC 264 “Air
quality”, the secretariat of which is held by DIN.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent
rights.
Introduction
Nitro-PAHs and oxy-PAHs are found in ambient air samples and there are strong indications that they
are as harmful as PAHS. Several compounds are classified as probably carcinogenic for humans (see
Table in Annex A) and nitro-PAHs are reported to be strongly mutagenic. Photooxidation of volatile
PAHs gives rise to the formation of secondary aerosols (Chan et al. 2009, Kautzman et al. 2010, Shakya
and Griffin, 2010).
1-Nitropyrene and 2-nitrofluorene are discussed as marker compounds for diesel exhaust and other
combustion processes. 2-Nitropyrene and 2-nitrofluoranthene are good marker substances for the
formation of nitro-PAHs by secondary reactions.
This Technical Report presents the state of the art of the oxy- and nitro-PAHS topics.
1 Scope
This Technical Report is focused on the presence of nitro- and oxy-PAHs in ambient air. It describes
how nitro- and oxy-PAH are formed, what typical concentrations are found, what is known about their
toxicity, and what sampling and measurement techniques are available.
The conclusions of this report are that nitro- and oxy-PAHs concentrations are present in the
atmosphere in levels that are of concern regarding their high toxicity. Information on the presence of
these compounds in ambient air is as relevant as information about PAHs. Validated techniques for the
measurement of nitro- and oxy-PAHs are available.
2 Symbols and abbreviations
DNA Deoxyribonucleic acid
EI Electron ionization
CD Chemiluminescence detection
FD Fluorescence detection
GC-MS Gas chromatography – mass spectrometry
GC-NICI-MS Gas chromatography – negative ion chemical ionization – mass spectrometry
HPLC High performance liquid chromatography
HPLC-FD HPLC – fluorescence detection
HPLC-CD HPLC – chemiluminescence detection
IARC International Agency for Research on Cancer
LC Liquid chromatography
MS Mass spectrometry
NICI Negative ion chemical ionization
Nitro-PAHs Nitrated polycyclic aromatic hydrocarbons
Oxy-PAHs Oxygenated polycyclic aromatic hydrocarbons
PAHs Polycyclic aromatic hydrocarbons
SPE Solid phase extraction
ToF-MS Time of flight mass spectrometry
3 Literature overview
3.1 Nitro-PAHs
3.1.1 Sources
3.1.1.1 General
Nitro-PAHs in the atmosphere originate mainly from combustion sources and are produced from both
gas and heterogeneous phase reactions of the parent PAHs with atmospheric oxidants such as NO ,
N O , O , OH and peroxide radicals (Arey et al., 1986; Atkinson et al., 1990; Keyte et al., 2013; Pitts et al.,
2 5 3
1985; Pitts Jr et al., 1978) in the presence of nitrogen oxides.
3.1.1.2 Direct emissions
Nitro-PAHs from direct emissions are formed by high temperature electrophilic nitration of PAHs with
NO during combustion processes (Nielsen, 1984). Nitro-PAHs have been observed in vehicle exhaust
(particularly diesel), industrial emissions, waste incinerator emissions (DeMarini et al., 1996) and
emissions from domestic residential heating/cooking (Kinouchi et al., 1988; Van Houdt, 1990). Nitro-
PAHs are also emitted by wood burning but in relative low amounts due to low emissions of NO during
this type of combustion process (Alfheim and Ramdahl, 1984, Orasche et al., 2012; Orasche et al., 2013;
Shen et al., 2011; Shen et al., 2012a; Shen et al., 2012b), (Environmental Health Criteria (EHC) 229,
2003 and references therein).
Recently, nitro-PAHs have also been quantified in exhausts of modern biodiesel engines (Karavalakis et
al., 2010a; Karavalakis et al., 2010b; Karavalakis et al., 2011). Additionally, several studies have shown
the formation nitro-PAHs in situ on catalytic diesel particulate filters as they act as chemical reactors for
the nitration of PAHs (Carrara et al., 2010; Carrara and Niessner, 2011; Heeb et al., 2008). In this case,
nitro-PAHs would be considered as primarily emitted. Gasoline emissions have also been reported but
at lower concentration levels (Alsberg et al., 1985; Hayakawa et al., 1994; IARC, 1989; Sera et al., 1994).
Overall, 1-nitropyrene, 2-nitrofluorene and 2-nitrofluoranthene are the most abundant nitro-PAHs in
diesel and gasoline exhaust (gas and particulate phases) (Beije and Möller, 1988; Environmental Health
Criteria (EHC) 229, 2003; Finlayson-Pitts and Pitts Jr, 2000; Paputa-Peck et al., 1983; Schuetzle and
Perez, 1983).
3.1.1.3 Atmospheric formation
Gas-phase reactions of parent PAHs are initiated by OH radicals during the day and by NO radicals at
night in the presence of NO producing nitro-PAHs, with subsequent partitioning to or depositing on the
x
particulate matter. (Arey et al., 1986; Atkinson et al., 1989a; Atkinson et al., 1989b; Atkinson et al.,
1990; Atkinson and Arey, 1994; Environmental Health Criteria (EHC) 229, 2003; Helmig and Harger,
1994; Keyte et al., 2013; Sasaki et al., 1997; Vione et al., 2006).
Recently, research studies reported that heterogeneous reactions may be the dominant process for loss
of atmospheric PAHs and a significant source for nitro-PAHs in the atmosphere (Keyte et al., 2013;
Kwamena et al., 2007; Perraudin et al., 2007; Pöschl et al., 2001). These reactions may dramatically
differ from the homogeneous reactions in their rates, mechanisms, and products. Numerous studies
showed results obtained with model particles (soot, sea salt, organic aerosol, silica, graphite or azelaic
acid particles) coated artificially with single or a mixture of PAHs and their reaction with various
oxidants as OH, NO , O or NO (Cazaunau et al., 2010; Esteve et al., 2003; Kwamena et al., 2007; Miet et
3 3 2
al., 2009; Perraudin et al., 2005; Zhang et al., 2011).
Few studies reported results obtained with natural soot particles laboratory generated (liquid
carburant burners) (Bedjanian et al., 2010; Kwamena and Abbatt, 2008), with natural ambient air
particles (Ringuet et al., 2012b; Zimmermann et al., 2013) or with diesel engine exhaust particles
(Esteve et al., 2006; Kamens et al., 1990; Nguyen et al., 2009; Rattanavaraha et al., 2011).
Mechanistic reaction schemes for gas phase formation of nitro-derivatives of fluoranthene and
heterogeneous formation of isomeric nitro-benzo[a]pyrenes are shown in Figure 1 and 2, respectively.
Figure 1 — Oxidation mechanisms of fluoranthene by OH during the day (Arey, 1998) and by NO
during the night (Atkinson and Arey, 1997)
Figure 2 — Mechanism proposed for the nitration of benzo[a]pyrene (Cazaunau et al., 2010)
22-Nitrofluoranthene and 2-nitropyrene are the most abundant substances formed by gas phase
reaction of PAHs with oxidants and oxides of nitrogen. A high 2-nitrofluoranthene/1-nitropyrene ratio
is a good indicator for the secondary formation of nitro-PAHs (Albinet et al., 2007b; Albinet et al., 2008;
Arey et al., 1989; Atkinson and Arey, 1994; Bamford and Baker, 2003; Reisen and Arey, 2005; Mariano
et al., 2000; Ringuet et al., 2012a; Ringuet et al., 2012c; Zielinska et al., 1989; Zimmermann et al., 2012).
3.1.2 Concentrations, gas/particle partitioning and size distribution
Overall, in continental areas (urban, sub-urban and rural areas), nitro-PAHs atmospheric
concentrations are one or two orders lower than PAHs atmospheric concentrations. Nitro-PAHs
–3
concentra
...
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