1、Ambient air Report on nitro- and oxy-PAHs Origin, toxicity, concentrations and measurement methodsPD CEN/TR 16998:2016BSI Standards PublicationWB11885_BSI_StandardCovs_2013_AW.indd 1 15/05/2013 15:06National forewordThis Published Document is the UK implementation of CEN/TR 16998:2016. The UK partic
2、ipation in its preparation was entrusted by TechnicalCommittee EH/2, Air quality, to Subcommittee EH/2/3, Ambient atmospheres.A list of organizations represented on this committee can be obtained onrequest to its secretary.This publication does not purport to include all the necessary provisions ofa
3、 contract. Users are responsible for its correct application. The British Standards Institution 2016.Published by BSI Standards Limited 2016ISBN 978 0 580 91098 2ICS 13.040.20Compliance with a British Standard cannot confer immunity fromlegal obligations.This Published Document was published under t
4、he authority of theStandards Policy and Strategy Committee on 31 December 2016.Amendments/corrigenda issued since publicationDate Text affectedPUBLISHED DOCUMENTPD CEN/TR 16998:2016TECHNICAL REPORT RAPPORT TECHNIQUE TECHNISCHER BERICHT CEN/TR 16998 November 2016 ICS 13.040.20 English Version Ambient
5、 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, Konzentrationen und Messverfahren T
6、his 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, Fran
7、ce, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey andUnited Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOM
8、ITEE 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 EPD CEN/TR 16998:2016CEN/TR 16998:2016 (E) 2 Contents Page European foreword . 3 I
9、ntroduction 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 G
10、lassware 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 Res
11、ults 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 Repo
12、rt 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 of the elements of this
13、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 indications that they a
14、re 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 a
15、nd 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
16、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 is known about their t
17、oxicity, 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
18、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-NI
19、CI-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 Neg
20、ative 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
21、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 NO3, N2O5, O3, OH and peroxide radicals (Arey et al., 1986; Atkinson et al., 1990; Keyte et al., 2013; P
22、itts 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 NO2during combustion processes (Nielsen, 1984). Nitr
23、o-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
24、low amounts due to low emissions of NO2during 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-PA
25、Hs 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 fo
26、r 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; Ser
27、a 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 Pitts Jr, 2000; Paputa-Peck et al.,
28、 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 NO3radicals at night in the presence of NOxproducing nitro-PAHs, with subsequent partitioning to or depositing on the particulate matter. (Arey et al
29、., 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 reacti
30、ons 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 homogeneous reactions in their rates, mechan
31、isms, 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, NO3, O3or NO2(Cazaunau et al., 2010; Es
32、teve 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 Abbatt, 2008), with natural ambient air part
33、icles (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 form
34、ation 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 NO3during the night (Atkinson and Arey, 1997) Figure 2 Mechanism proposed for the nitrat
35、ion 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 for the secondary formation of nitro-PAHs
36、(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). PD CEN/TR 16998:2016CEN/TR 16998:2016 (E) 8
37、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 concentrations are in the range of 0,1 to 1000 pg
38、m3in 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., 2002; Maria del Rosario Sienra, 2006; Valle-
39、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 concentrations. PD CEN/TR 16998:2016CEN/TR 16998:
40、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/m3Traffic Urban Rural/remote 1-Nitronaphthalene 0,07 0,2 (n, o) 0,2 (h, n) 0,01 0,2 (h, n) 2-
41、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 0,1 (n, o) 0,001 0,02 (l, o) 0,0007 0,001 (o)
42、 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) 0,01 2 (a, b, e, f, g, h, j, l, n) 0,0006 0,01
43、 (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 (d, h, n) 0,0001 0,004 (n) 7-Nitrobenzoaanthra
44、cene 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) Atkinson et al. (1988) Glendora (USA) b) Ma
45、tsushita 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) h) Albinet et al. (2007) Marseille (France) i
46、) 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) Chamonix, Maurienne (France) o) Ringuet et al. (2012
47、) 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., 2000; Huang et al., 2014; Reisen and Arey, 2005
48、; 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 relative low vapour pressures (90 %) to the
49、fine particle fraction (Dp90 %) to the fine particle fraction (Dp50 m3. NOTE For sampling of volatile compounds a sampling system according to ISO 12884 can be used. A.2 Analytical materials A.2.1 Glassware and sample handling Laboratory vessel (beakers, funnels, etc.) Micro-pipettes Micro-syringe (or equivalent) Glassware should be rinsed with acetone and cleaned using a surfactant before rinsing using deionised or ultrapure water. All the non-volume
