1、Ambient air Report on nitro- and oxy-PAHs Origin, toxicity, concentrations and measurement methods PD CEN/TR 16998:2016 BSI Standards Publication WB11885_BSI_StandardCovs_2013_AW.indd 1 15/05/2013 15:06National foreword This Published Document is the UK implementation of CEN/TR 16998:2016. The UK pa
2、rticipation in its preparation was entrusted by Technical Committee EH/2, Air quality, to Subcommittee EH/2/3, Ambient atmospheres. A list of organizations represented on this committee can be obtained on request to its secretary. This publication does not purport to include all the necessary provis
3、ions of a contract. Users are responsible for its correct application. The British Standards Institution 2016. Published by BSI Standards Limited 2016 ISBN 978 0 580 91098 2 ICS 13.040.20 Compliance with a British Standard cannot confer immunity from legal obligations. This Published Document was pu
4、blished under the authority of the Standards Policy and Strategy Committee on 31 December 2016. Amendments/corrigenda issued since publication Date Text affected PUBLISHED DOCUMENT PD CEN/TR 16998:2016 TECHNICAL REPORT RAPPORT TECHNIQUE TECHNISCHER BERICHT CEN/TR 16998 November 2016 ICS 13.040.20 En
5、glish Version Ambient air - Report on nitro- and oxy-PAHs - Origin, toxicity, concentrations and measurement methods Air ambiant - Rapport sur les nitro- et oxy-HAP - Origine, toxicit, concentrations et mthodes de mesure Auenluft - Bericht ber Nitro- und Oxy-PAHs - Herkunft, Toxizitt, Konzentratione
6、n und 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 Republ
7、ic 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 COMIT EUROPEN DE NORMALI
8、SATION EUROPISCHES KOMITEE FR 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 worldwide for CEN national Members. Ref. No. CEN/TR 16998:2016 E PD CEN/TR 16998:2016CEN/TR 16998:2016 (E) 2 Contents Page
9、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 Analytic
10、al 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
11、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
12、 in this Technical Report 36 Bibliography . 43 PD CEN/TR 16998:2016CEN/TR 16998:2016 (E) 3 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 o
13、f 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. PD CEN/TR 16998:2016CEN/TR 16998:2016 (E) 4 Introduction Nitro-PAHs and oxy-PAHs are found in ambient air samples and there are strong
14、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, Kautzma
15、n 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 Rep
16、ort presents the state of the art of the oxy- and nitro-PAHS topics. PD CEN/TR 16998:2016CEN/TR 16998:2016 (E) 5 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
17、 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 compo
18、unds 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
19、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 Mas
20、s 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
21、 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 3, N 2O 5, O 3, OH and peroxide radicals (Arey et al., 1986; Atkinson et al.,
22、1990; Keyte et al., 2013; Pitts et al., 1985; Pitts Jr et al., 1978) in the presence of nitrogen oxides. PD CEN/TR 16998:2016CEN/TR 16998:2016 (E) 6 3.1.1.2 Direct emissions Nitro-PAHs from direct emissions are formed by high temperature electrophilic nitration of PAHs with NO 2 during combustion pr
23、ocesses (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
24、 wood burning but in relative low amounts due to low emissions of NO 2 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 referen
25、ces 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
26、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; Hayaka
27、wa 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 Mller, 1988; Environmental Health Criteria (EHC) 229, 2003; Finlayson-Pitts and Pit
28、ts 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 3 radicals at night in the presence of NO x producing nitro-PAHs, with subsequent partitioning to or depositing on
29、 the 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 studie
30、s 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; Pschl et al., 2001). These reactions may dramatically differ from the homogene
31、ous 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
32、3, O 3 or NO 2 (Cazaunau et al., 2010; Esteve et al., 2003; Kwamena et al., 2007; Miet et 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 Abb
33、att, 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-derivativ
34、es of fluoranthene and heterogeneous formation of isomeric nitro-benzoapyrenes are shown in Figure 1 and 2, respectively. PD CEN/TR 16998:2016CEN/TR 16998:2016 (E) 7 Figure 1 Oxidation mechanisms of fluoranthene by OH during the day (Arey, 1998) and by NO 3 during the night (Atkinson and Arey, 1997)
35、 Figure 2 Mechanism proposed for the nitration of benzoapyrene (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
36、 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). P
37、D CEN/TR 16998:2016CEN/TR 16998:2016 (E) 8 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 concen
38、trations are in the range of 0,1 to 1000 pgm 3in both, gaseous and particulate phases (e.g. Albinet et al., 2007; Albinet et al., 2008a; Bamford and Baker, 2003; Ciccioli et al., 1995; Ciccioli et al., 1996; Feilberg et al., 2001; Feilberg and Nielsen, 2001; Hayakawa et al., 1995a; Hayakawa et al.,
39、2002; Maria del Rosario Sienra, 2006; Valle-Hernandez et al., 2010; Wang et al., 2011). Nitronaphthalene isomers in gas phase and 2-nitrofluoranthene and 9-nitroanthracene in particulate phase are generally the most abundant nitro-PAHs and account for about 15 % to 50 % of the total nitro-PAHs conce
40、ntrations. PD CEN/TR 16998:2016CEN/TR 16998:2016 (E) 9 Table 1 summarizes the reported concentration ranges of the most important nitro-PAHs. Table 1 List of concentration ranges of important nitro-PAHs in ambient air Substance Concentration range ng/m 3Traffic Urban Rural/remote 1-Nitronaphthalene
41、0,07 0,2 (n, o) 0,2 (h, n) 0,01 0,2 (h, n) 2-Nitronaphthalene 0,03 0,06 (n, o) 0,12 (h, n) 0,01 0,1 (h, n) 2-Nitrofluorene 0,001 0,021 (l, n) 0,05 0,4 (d, g, h, n) 0,001 0,005 (h, n) 9-Nitroanthracene 0,002 0,01 (n, o) 0,03 0,2 (a, c, d, g, h, j, l, n) 0,002 0,03 (g, h, n) 3-Nitrophenanthrene 0,007
42、0,1 (n, o) 0,001 0,02 (l, o) 0,0007 0,001 (o) 9-Nitrophenanthrene 0,005 0,05 (l, n) 0,01 0,3 (h, i, n) 0,0002 0,03 (h, n) 2-Nitrofluoranthene 0,03 0,2 (l, o) 0,03 2 (a, e, f, g, j, l, m, n) 0,02 0,03 (e, k, n) 3-Nitrofluoranthene 0,018 (i) 0,003 0,1 (d, j, l) 0,01 (e) 1-Nitropyrene 0,02 0,2 (l, o) 0
43、,01 2 (a, b, e, f, g, h, j, l, n) 0,0006 0,01 (e, h, n, o) 2-Nitropyrene 0,007 0,2 (n, o) 0,01 0,04 (a, h, j, n) 0,001 0,08 (e, h, k, n) 4-Nitropyrene 0,02 0,03 (o) 0,001 (h, n) 0,0006 (h, n) 1,3-Dinitropyrene 0,0009 0,02 (n, o) 0,01 0,03 (d, h, n) 0,004 (n) 1,6-Dinitropyrene up to 0,0002 (o) 0,01 (
44、d, h, n) 0,0001 0,004 (n) 7-Nitrobenzoaanthracene 0,005 0,01 (n, o) 0,004 0,3 (a, h, l, m) 0,002 (h, n) 6-Nitrochrysene 0,003 0,004 (n, o) up to 1,5 (b, h, j, l, n) 0,0003 0,002 (e, h, n) 6-Nitrobenzoapyrene 0,007 0,01 (l, n) 0,001 0,01 (h, n) 0,0002 0,005 (n, o) 3-Nitrobenzanthrone 0,001 0,01 (l) a
45、) Atkinson et al. (1988) Glendora (USA) b) Matsushita and Ida (1986) Tokio (Japan) c) Hunt and Meisel (1995) Fresno (USA) d) Tokiwa et al. (1990a) Sapporo (Japan) e) Vasconcellos et al. (1998) Alta Floresta (Brazil) f) Wilson et al. (1995) Houston (USA) g) Berlincioni et al. (1995) Florence (Italy)
46、h) Albinet et al. (2007) Marseille (France) i) Mcke et al. (2009) Munich (Germany) j) Di Filippo et al. (2010) Rome (Italy) k) Tsapakis et al. (2007) Finokalia (Greece) l) Valle-Hernandez et al. (2010) Mexico City (Mexico) m) Wang et al. (2011) Bejing (China) n) Albinet et al. (2008a, 2008b) Chamoni
47、x, Maurienne (France) o) Ringuet et al. (2012) Paris (France) PD CEN/TR 16998:2016CEN/TR 16998:2016 (E) 10 Nitro-PAHs gas/particle partitioning is poorly documented (Albinet et al., 2007; Albinet et al., 2008a; Araki et al., 2009; Atkinson and Arey, 1994; Bamford and Baker, 2003; Dimashki et al., 20
48、00; Huang et al., 2014; Reisen and Arey, 2005; Wilson et al., 1995). 2-Rings nitro-PAHs (nitronaphthalenes) are mainly associated to the gaseous phase. Nitro-PAHs with 4 or more rings are mainly bound to particles. 3-ring nitro-PAHs are partitioned in both gaseous and particulate phase. Due to their
49、 relative low vapour pressures (90 %) to the fine particle fraction (D p 1 m) and about 20 % are associated to the ultrafine particle fraction (D p 0,1 m). These results are important information regarding the risk assessment because nitro-PAHs can thus penetrate deeply into the lung. Nitro-PAHs react with hydroxide and nitrate radicals, with ozone and they are decomposed by photolysis. As a result the atmospheric half life time of nitro-PAHs ranges from less t
