54
ISTISAN 94'5
IST
ISA
N 94'5
ISTISAN 9415 (ISSN 0391.167S)
ISTITUTO SUPERIORE DI SANITA'
Polycyclic aromatic hydrocai.bons: identity, pbysksl snd chemid propertie8,
nmly t id methods
E d d Menichini
iuboraiorio di Igiene Ambieniale
Roma 1994
A b . r i r f m p l u u i i a g & ~ h r n v h m a i l l l f & d l w c h o f p o l ~ c l i e ~ n n l t i c hymoarbons(PAHs). u weU r teiuod hunun ammu l. mwideb Infmnrtioa on PAH chcmicai idmtity b givm md chcmicai proprtica
uc rrportcd f a 33 campoun& melting dbo i l ing poinb. iìuh p i n i ud expbrion limib, density, v i p o u r p s t u e ud vipour dairitv. ~ lubi l i ty in wim. n-Vwlla mrtilioncoefficient andHeny's law mnstuu. Andytical methods for
istituto S u p e n a di Sani* Roma Idrocarburi polkiclkl sromaticl: identitq proprietà Itslche c chhnkhc, metodi ansiiticl EdmrQ Mcnichini Giu 94.48 p R a p i t i ISTISAN 9415 (in inglese)
Sono fornite mnorunrc di bisc p a la pmgrmmazionc di i M i riguardanti il datino e i livelli ambientali &gli i d r o c ~ p o l i c n i c i m m t i c i @A). nonché I'espoluion&1l'uomo essociataa lali livelli. Vengono date informazioni sulYidentitàchMicadegliPAeeriassunte Lepro~etàChimidiedLlIicla~se.P~33sostsnze, sonopoinpOriateleproprietà fisickdi interesse ai h i &h bro valutuione tossimlogicaedeu>tossicobgica: punti di b i o n e edi ebollizione, p n t o di infummabilità e Limiti di cspbswne, &nsi& tensionc di vapore e daisità di vspom. rolubilità in acqua. mefficiente dir@aMone n-ottMololuqua e amiinte di Hauy. Segue una rassegna critica &i metodi analitici per la d*erminuione &gli iPA in divmc muri& in prticoluc. a i a ed acque. ambienti di lavom. suolo. sedimenti, alimenti. rifhti. piante. fluidi e tessuti aologici. Lifuie. vengono riporlate alcune lkte di spe i f r i IPA. ia,cui determinazione v& richiesta o m m u d a i i a livello nuionale o inianazionale.
Puok chiavc Idrochwi poliiiclici ammatici. IPA, Ropnah chimiche. Pmpzietà fisiche.
AflmowbdlanenL mi Qcumat his becn pepared fm Intanitiond Rogramme on Chemieal Safety (UNEP-IU>- WHO) u pPt of i b woik ai "Eminmaitil M I h C r i b for Polycyclic Amm& Hydmcabons".
8 I~iiuto Supriorr di Smiid 199Q
IMROOUCTION
1 . I D E N T I N
2. PHYSICAL AND CHEMICAL PROPERTIES
ANALYTICAL M-
Sam1 i ng
Ambient ai r
Workplace a i r
Ccnnbustion effluents
Water
Col i d sampl es
Preoaration
Anal ysi s
Gas chrcinatography
High-performance liquid chrmatography
Thin-layer chrmatography
Other techniques
Choice of PAHs to be detemined
REFERENCES
Polycyclic aromatic hydrocarbons (PAHs) are widespread
environmental pollutants. They are formed during incomplete combustion
and pyrolysis of organic materials, frm both natura1 and
anthropogenic cources, the l a t t e r being by far the greatest
contributors - (Lee et a l . , 1981, Ch. 2). Hundreds of PAHs may be
forrned. For example, over one hundred PAHs have been ident i f ied i n
atmospheric part iculate matter (Lao et a l . , 1973; Lee et a l . , 1976)
and i n emissions frm coal-fired residential furnaces (Grimer e t al . ,
19851, about two hundred i n tobacco smoke (reviewed by Lee et a l . ,
1981, Ch. 2) .
The experimental carcinogenicity and mutagenicity shown by many
PAHs have resulted i n a strong suspicion that they are also human
carcinogens (IARC, 1983, 1987). I n the l i g h t of such significance for
human health, much interest has been shown i n studying the i r
environmental fate, as well as the i r environmental levels and human
exposures.
With the aim o f contributing t o the development of such studies,
t h i s report presents a c r i t i ca1 review of the important physical and
chemical properties of PAHs, and of analytical methods for PAH
determination i n va r iws matrices.
I n part icular, properties are presented for 33 compounds (31
parent PAHs and two alky l derivatives, Figure 1 and Table 1): these
PAHs have been selected as being those most commonly reported i n
l i te ra ture , with regard t o toxicological and/or exposure data. As to
the analytical methods, PAHs are considered here as a class.
CPP
TRI
ACL
BbFL
CHR
Fig. 1. Structural fonnulac of PAHfi.
PHE
ATR
COR
Fig. l (continucd)
Table 1. PAHs considered i n t h i s r e p o r t
Common namea Abbr.b CAS name Synonymc
Naphthalene N A Naphthalene Acenaphthylene ACL Acenaphthylene Acenaphthene AC Acenaphthylene, 1,2-dihydro- Fluorene FL Anthracene AN Phenanthrene PHE 1-Methylphenanthrene 1-MPH Fluoranthene FA Pyrene PY Benzo(a)f luorene BaFL Benzo(b)fluorene BbFL Benzo(ghi) f luoranthene BghiF Cyclopenta(cd)pyrene CPP Benz(a)anthracene BaA Benzo(c)phenanthrene BcPH Chrysene CHR Triphenylene T R I 5-Methylchrysene 5-MCH Benzo(b)f luoranthene BbFA Benzo( j ) f luoranthene BjFA Benzo(k)f luoranthene BkFA Benzo(a)pyrene BaP Benzo(e)pyrene BeP Perylene PE Anthanthrene ATR Benzo(ghi Ipery lene BghiP Indeno(l,2,3-cdlpyrene I P Dibenz(a,h)anthracene DBahA Coronene COR Dibenzo(a,e)pyrene DBaeP Dibenzo(a, h lpyrene DBahP Dibenzo(a, i )pyrene DBaiP Dibenzo(a, l )pyrene DBalP
9H-Fluorene Anthracene Phenanthrene Phenanthrene, l-methyl- Fluoranthene Pyrene 11H-Benzo[a]fluorene 11H-Benzo[b]fluorene Benzo[ghi l f luoranthene Cyclopenta[cdlpyrene Benz[alanthracene Benzo[c]phenanthrene Chrysene Triphenylene Chrysene, 5-methyl- Benz[elacephenanthrylene Benzo[ j ] f luoranthene Benzo[k]f luoranthene Benzo[alpyrene Benzo[elpyrene Perylene Dibenzo[def,mnolchrysene Benzo[ghi lperylene Indeno[l,2,3-cdlpyrene Dibenz[a,hlanthracene Coronene Naphto[l,2,3,4-deflchrysene Di benzo[b,def lchrysene Benzo[rstlpentaphene Dibenzo[def,plchrysene
1,12-Benzoperylene 2,3-o-phenylenpyrene 1,2:5,6-Dibenzanthracene Hexabenzobenzene 1,2:4,5-Dibenzopyrene 3,4:8,9-Dibenzopyrene 3,4:9,10-Dibenzopyrene 1,2:3,4-Dibenzopyrene
a Ranked according t o increas ing molecular mass (see Table 2) and, f o r isomers, i n a lphabe t i ca l order.
b AS used i n t h i s repor t . Common synonym which appeared i n t h e l i t e r a t u r e .
The name "polycyclic aromatic hydrocarbons" oonnionly refers t o a
large class o f organic ccnipwnds containing two or more fused aromatic
rings, even though, interpreted i n a broad sense, m- fused r ing
systems should also be included. I n particular, the term PAHs refers
t o -)pwnds containing only carbon and hydrogen atoms (i.e.,
unsubsti tuted parent PAHs and their alkyl-substi tuted derivatives),
whereas the more genera1 term "pol ycycl i c aromatic canpounds" (PACs)
alco includes the functional derivatives (e.g., n i t ro- and hydroxy-
PAHs) as well as the heterocyclic analogs, which contain one or more
heteroatms i n the aromatic structure (aza-, oxa- and thia-arenes). A
number o f authors have also referred t o PACs as "polycyclic organic
matter" (M). I n addition, the term "polynuclear" i s frequently used
for "polycycl ic " , e.g., "pol ynuclear a r m t i c (PNA) canpwnds".
I n the past. the t r i v i a l names and dif ferent systems used to
ident i fy r ing fusions by numbers or le t te rs have often led to
confusion, with respect to the noinenclature of PAHs (Loening 8
Merr i t t , 1990). Nowadays, the system codif ied by the International
Union o f Pure and Appl ied Chemistry (IWAC, 1979) and used by the
Chemical Abstracts Service ( W , 1988, 1990) i s generally accepted.
However, a number o f compounds are s t i l l m 1 y known and reported
i n the l i te ra ture with the nonsystematic names. For each compound,
Table 1 l i s t s the umnon name and i t s abbreviation, as used throughout
t h i s report, together with the CAS name and any alternate name which
most umnonly appeared i n the l i terature. Most o f the alternate names
use numbers t o denote the sides where fusion occurs, but th i s type of
nomenclature i s def in i te ly desappearing frm publications. Extensive
l i s t s of synonyms are reported i n IARC (1983) and Loening & b r r i tt
(1990).
Molecular formulae, re lat ive molecular masses, and CAS registry
numbers (RN) are shown i n Table 2.
Table 2. I d e n t i t y
R e l a t i v e Mo lecu la r mo lecu la r
Compound fo rmu la mass CAS RNa
NA C1oHa 128.2 91 -20-3 ACL AC F L AN PHE 1 -MPH FA PY BaFL BbFL BghiF CPP BaA BcPH CHR TR I 5-MCH BbFA B j FA Bk FA BaP BeP PE ATR BghiP I P DBahA COR DBaeP DBahP DBai P DBal P
l Chemical A b s t r a c t s S e r v i c e r e g i s t r y number .
2. M I C M AH) CHBIICAL nIDPBTTIES
Physical and chemical properties relevant to the toxicological
and ecotoxicological evaluation of PAHs are surmarized i n Tables 3-5.
I t should be kept i n mind that values of me parameter which are
reported for various compounds, may derive from different xrurces and
hence frun different measurement - or calculation - methcds. I f th is
i s so, individua1 values cannot be directly compared other than
roughly, unless the origina1 xrurces are consulted for the methcds
used. I n particular, the vapour pressures reported i n the l i terature
for the same PAH vary even up to severa1 orders of magnitude (Mackay
and Shiu, 1981; Lane, 1989). Variations are also noticeable for water
solubi l i t ies, although these are generally within one order of
magnitude (NXX, 1983, pp. 32-33).
Physical and chemical properties are dominated by the conjugated
n-electron systems. They vary quite regularly with the number of rings
and the molecular mass. giving r ise to a more or less wide range of
values for each parameter, within the whole class. Under ambient
temperatures, al1 the PAHs are solids. The general characteristics
camwn to the class are high melting and boil ing points, low vapour
pressures, and very low water solubi l i t ies. PAHs ere soluble i n many
organic solvents (IARC. 1983; US DHHS, 1990; Lide, 1991) and are
highly l ipophil ic.
Vapour pressures generally tend to decrease with increasing
molecular mass, varying more than ten orders of magnitude f r a low- to
high-molecular compounds. This affects the different percentages of
individual PAHs that are adsorbed on particulate matter i n the
atmosphere and that are retained on the particulate matter during
sampling on f i l t e r s (Thrane 6 Mikalsen, 1981). Vapour pressures
increase markedly with ambient temperatures (Murray et al.. 1974),
which then additionally affects the distribution coefficients between
gas and part icle phases (Lane, 1989). As a general trend, water
solubi l i ty decreases with increasing molecular mass.
PAHs ere chemically rather inert ccmpounds. When they react, PAHS
undergo two types of react ions characteristic of arunatic
hydrocarbons: electrophilic substitution and addition. The former i s
NA ACL AC FL AN PHE 1 -MPH FA PY BaFL BbFL BghiF CPP B aA BcPH CHR TR I 5-MCH BbFA BjFA BkFA BaP BeP PE ATR BghiP I P DBahA COR DBaeP DBahP DBai P DBal P
Table 3. Phys i ca l p r o p e r t i e s ( 1 s t p a r t )
M e l t i n g B o i l i n g F lash Exp los ion po i n t i p o i n t p o i n t t l i m i t sv
Compound Colour ( 'C) ( 'C) ( 'C) ( v o l . % )
whi tea 81 217.gb 78.9(OClU 0.9-5.9
whitea whi teb co lour1essc co lou r l essd
p a l e y e l lowa co lou r l essb
y e l lowf
c o l o u r l e s s ~ ye l lowa p a l e ye l low* y e l l ow i shb
ye l low t o c o l o u r l e s s b golden y e l low' p a l e ye l low-greenf y e l lowh c o l o u r l essh y e l lowe p a l e ye l lowa golden y e l lowh green ish-ye l lowh p a l e ye l lowh
( n o t e s on t h e f o l l o w i n g page)
Notes t o Table 3
a Frm: Lewis (1992).
b Frm: Budavari (1989).
C When pure, co lwr less with v io le t fluorescence. Frm: Budavari
(1989).
d Frm: Haviey (1987).
e Frcm Lide (1991).
f Frm: IARC (1983).
g With blue fluorescence. Frm: IARC (1973).
h Frm: IARC (1973).
i Frm: Karcher et al. (1985); Karcher (1988).
j From: Kruber & Marx (1938).
k From: Kruber (1937).
1 F r a : Kruber & Grigolei t (1954).
m Reported in: Grimner (1983).
n Calculated. From: White (1986).
o F r m the review of : Bjorseth (1983); the origina1 references ara
c i ted in: White (1986).
p Frm: Verschueren (1983).
q Frm: HSDB (1993).
r Frm: Von Boente (1955).
s Estimated frm the gas chromatographic retention time. From: Grimner
(1983).
t Open cup (OC) or closed cup (CC) inethod i s indicated.
u 87.8.C by closed cup method. Frm: HSDB (1993).
v Lower-upper, for NA; lower, fo r AN. From: Lewis (1992).
T a b l e 4. P h y s i c a l p r o p e r t i e s (2nd p a r t )
Vapour p r e s s u r e Vapour
Compound (Pa a t 25'C) D e n s i t y ' d e n s i t y.
1 . i5425 j 4.42' NA ACL AC FL AN PHE 1 -MPH FA PY BaFL BbFL Bgh i F CPP BaA BcPH CHR TRI 5-MCH BbFA BjFA BkFA BaP BeP P E ATR Bgh iP I P DBahA COR DBaeP DBahP DBai P DBal P
( n o t e s on t h e f o l l o w i n g page)
Notes t o Table 4
a Fran: Swinefeld e t al. (1983).
b Reported in: Sims & Overcash (1983).
C Calculated by Syracuse Research Center. Frm: HSDB (1993).
d Fran: US EPA (1980).
e Fran the review of: Santodonato et a l . (1981).
f Fran: LB DHHS (1990).
g Temperature not given.
h Calculated. Fran: HSDB (1993).
i Wen tw temperatures are reported as superscripts, the datum
indicates the specif ic gravity (the density o f the substance at the
f i r s t reported temperature re lat ive t o the density of water at the
second reported temperature). When there i s no value, or only one,
for temperature, the datun i s i n grams per m i l l i l i t r e , at the
indicated temperature ( i f any).
j Fran: Lide (1991).
k Fran: Schuyer et a l . (1953).
1 Fran: Bei lstein (1993).
m Fran: Budavari (1989).
n Approximate value. Fran: Klug (1950).
o Fran: Kronberger & Weiss (1944).
p A t ambient temperature. F m : Inokuchi & Nakagaki (1959).
q Fran: White (1948).
r Fran: IARC (1973).
s A i r=l . t Fran: Lewis (1992).
u F m : NIOSH/OSHA (1981).
v Fran: Ehrl ich & Beevers (1956).
Table 5. Phys i ca l p r o p e r t i e s ( 3 r d p a r t )
n-Octanol /water S o l u b i l i t y Henry 's law p a r t i t i o n i n waterm const ant c o e f f i c i e n t a t 25OC a t 25'C
Compound ( l o g K O W ( ~ g / l i t r e ) (kPams/mol )
NA 3.4. 3 .17~104 4 .89~10 -2 u ACL AC FL AN PHE 1 -MPH FA PY BaFL BbFL BghiF CPP BaA BCPH CHR TRI 5-MCH BbFA B j FA BkF A BaP BeP P E ATR BghiP I P DBahA COR DBaeP DBahP DBai P DBal P
(no tes on t h e f o l l o w i n g page)
Notes to Table 5
a F r a : Karickoff e t a l . (1979).
b F r a : HSDB (1993).
C Fran: Brooke et a l . (1986).
d Calculated. Fran: Karcher et a l .
e Calculated. F r a : M i l l e r et a l . ( - f F r a : Bruggeman et a l . (1982).
g Calculated. F r a : Yalkowsky 6 Valvani (1979).
h F r a : Ten Milscher et a l . (1992).
i Calculated as per Leo et a l . (1971). F r a : US EPA (1980).
j Calculated. F r a : Ruepert e t a l . (1985).
k Calculated. F r a : HSDB (1993).
1 F r a : Means et al. (1980).
m F r a : Mackay & Shiu (19771, except where noted.
n F m : May et a l . (1978).
o F r a : Davis et al. (1942).
p Temperature not given. Reported in: Sims & Overcash (1983).
q Temperature not given. Uipublished result. c i ted in: Wise et a l .
(1981).
r From: Schwarz (1977).
s Temperature not given.
t Calculated by Syracuse Research Center. Fran: HSOB (1993).
u From: Mackay e t a l . (1979).
v F r a : Mackay 6 Shiu (1981).
preferred since i t does not destroy the aromatic character o f the
benzene r ing affected; addition i s often followed by elimination
result ing i n a net substitution. Chemical and photochemical reactions
o f PAHs i n the atmosphere have been reviewed (Valerio et al . , 1984;
Lane, 1989). Following photodecomwsition, i n the presence of a i r and
sunlight. a nunber of oxidative products have been identif ied,
par t icular ly quinones and endoperoxides. Various experimental studies
have revealed reactions o f PAHs with nitrogen oxides and n i t r i c acid
t o form the nitro-derivatives of PAHs, as well as with sulphur oxides
and su l fur ic acid ( i n solution) to form su l f i n i c and sulfonic acids.
PAHs may also be attacked by ozone and hydroxyl radicals, which ere
present i n the atmosphere.
The formation o f nitro-PAHs i s part icular ly imwrtant w i n g to
the i r biologica1 impact, and part icular ly to the i r well-documented
mutagenic ac t i v i t y (Howard e t al., 1990).
I n general, the above-mentioned reactions are of interest with
regard t o the environmental fate o f PAHs, but the results of
experimental studies are s t i l l d i f f i c u l t t o interpret because o f the
cunplexity o f interactions occurring i n environmental mixtures and the
d i f f i c u l t y i n eliminating a r t i f ac t s during analytical determinations.
These reactions are also considered responsible for possible PAH
losses during arnbient atrnospheric sarnpling (see 3.1.1).
3. ANALMICAL t€rtms Hwidreds o f publications have described analytical methcds for
PAHs. Tables 6 and 7 synthetically present a l imi ted mmber o f methods
applied t o ' real ' samples of d i f ferent matrices, taken as examples.
The methods and sources were selected, as far as possible, according
t o the following c r i te r ia : accessibi l i ty of the bibliographic swrce,
completeness of the procedure description (or including reference t o
other acscessible sources), prac t icab i l i ty with urmxri equipment for
t h i s type o f analysis (sven i f requiring experienced perconnel),
recency, status o f o f f i c i a l or validated or reconmended methcd.
3.1 m l i n g
3.1.1 Ambient a i r
When selecting the sampling apparatus, m e must consider the
physical state o f PAHs i n the atmosphere. Conipounds with 5 or more
rings are present almost exclusively adsorbed on suspended particulate
matter, whereas lawer-rnolecular mass PAHs are par t ia l l y or t o ta l l y
present i n the vapour phase (Coutant e t al., 1988).
I t i s urmxri that i n invest igat ims for mni tor ing purposes i n
ambient a i r (reviewed by Menichini. 1992a), m l y particle-bound PAHs
are detenined. This i s l i ke l y due t o the increased workload when
vo la t i l e compounds must be trapped (both i n assembl ing the sampl ing
un i t and i n analysing samples), but also t o the lesser toxicological
interest for l igh ter compcunds: emong 'probable' and 'possible'
carcinogenic PAHs (IARC, 1987), only BaA i s found at signif icant
levels i n the vapour phase (Van Vaeck et al., 1984; Coutant et al..
1988).
Sampling i s generally perfornied by col lect ing to ta l suspended
part iculate matter for 24 h on glass f iber (W) f i l t e r s by means o f
high-volwm, samplers. Other f i l t e r media have been used: tef lon
membrane (Benner et al., 1989; Baek e t al., 1992), teflon-coated W,
and quartz f iber.
Al1 these f i l t e r s have b e n evaluated comparatively. with respect
t o the effect o f the f i l t e r materia1 on the PAH decanposition during
sampling (see chapter 2) . Some studies have shorm that higher PAH
recoveries are obtained frm tef lon or teflon-coated f i l t e r s (Lee et
al., 1980; Grosjean, 1983). However, successive investigations d id not
confirm th i s f inding (Lindskog et al., 1987; Ligocki 6 Pankow, 1989;
De Raat et al., 1990), so that the importante of t h i s ef fect i s s t i l l
d i f f i c u l t t o assess, and a conclusion cannot be drawn. More rarely,
cellulose acetate membranes have been used (Baek et al., 1992); when
conipared wi th GF f i l t e r s , they yielded similar col lect ion eff ic iencies
for heavier PAHs, and better eff ic iencies for 3- and 4-ring cunpounds
(Spitzer 6 Dannecker, 1983).
The method most used t o trap vepair-phase PAHs i s adsorption on
plugs of polyurethane foam (WF) located behind the GF f i l t e r (Keller
6 Bidleman, 1984; Chuang et al., 1987; De Raat et al., 1987; Benner et
al., 1989; Hawthorne et al., 1992). The success of WF probably
results from the low pressure drop, low blanks, low cost, and ease of
handling. Among the va r iws other sorbents tested (reviewed by:
Leinster 6 EVMS, 1986; Davis et al., 1987). two polymeric materials
have received part icular attention: the Aniberlite XAD-2 resin, which
i s a va l id al ternat ive t o PUF (Chuang e t al., 19871, and Tenax (Baek
e t al., 1992). Trapped vapwrs include both PAHs i n i t i a l l y present i n
the vapair phase, and those already collected on the f i l t e r and
vo la t i l i zed during sampling (the 'blowing-off' e f fect) (Van Vaeck et
al., 1984; Coutant e t al., 1988). The amounts o f PAHs which are fwnd
i n the vapour phase increase with ambient temperatures (Yamasaki et
al., 1982).
A useful method has been proposed t o contro1 c h i c a l degradation
and vo la t i l i za t ion losses frm f i l t e r s , based on the invar iab i l i t y of
PAH-profiles (i.e., the ra t i o o f al1 PAHs t o one another) during the
col lect ion time (Grimner et al., 1982).
Elutr iators and cascade impactors have been used t o perform a
par t ic le size-selective sampling o f PAHs (measurmts reviewed i n
Menichini, 1992a). Instrments designed as additions t o h i g h - v o l ~
samplers are available, including ' P M i o ' i n le ts (enabling col lect ion
of part iculate matter below a 10 cut size; UC EPA, 1987) (Lioy et
al., 1988; Hawthorne et al., 1992) and cascade impactors (Van Vaeck et
al., 1984; Catoggio et al., 1989).
I n atmospheric PAH determination, the sampling step i s by far the
most important source of var iab i l i ty i n the rewl ts . Generally
speaking, different invest igat imi are poorly cmparable aving to
differences i n factors such as season, meteorologica1 conditions, time
of day, number and characteristics of sampling sites, and sampling
parameters (Menichini, 1992a).
3.1.2 Workplace a i r
Genera1 msiderat ions expressed for ambient a i r are val id also
for the wrking envirannent.
The smowits of volat i le PAHs which are not retained by f i l t e r may
be higher than i n ambient air , because of the elevateci temperatures
often present at the wrkplace. I n a pot-room of a Coderberg aluminim
plant, 42% of BaA was found i n the vapair phase (Andersson et al.,
1983); i n an i ron fwndry, at a s i te where the temperature of PAH
source was abait 800-700eC, 4- to 7-ring PAHs were determined i n the
vapour phase at mcentrat ions corresponding to, on an average, abait
70% of the total (Knecht et al., 1986).
GF- or te f lon- f i l ters are usually used to collect porticle-bcund
PAHs. A miniber of back-up systems ef f ic ient ly trap volat i le PAHs: in
particular, l iqu id impingers. and sol id sorbeots soch 8s Tenax-GC,
Chmsorb, and W 2 (reviewed by: Bjorseth 6 Becher, 1986; Davis et
al.. 1987). The la t ter seems t o be the most practicable.
The NIOCH (1985) recairnends the use of a teflorr-lminated membra-
ne followed by a tube containing tw sections of XAD-2.
The wrker's actual exposure i s best estimated by 'persona1
sampling': portable battery-operated a i r puiiip+ ere used at low flow
rates (ca. 2 litres/min). w i t h the f i l t e r holder placed i n the
'breathing-zone', i.e., clipped to the sh i r t collar of the wrker.
3.1.3 Coinbustion effluents
Tha val id i ty o f the collected sample, i.e., i t s capability to
ref lect the 'true' composition of the emission, i s a crucial factor i n
the determination of PAH emissions.
The problems associated with .collection eff ic iency for vo la t i l e
PAHs are enhanced when sampling for combustion effluents, such as
stack gases and vehicle exhausts, because o f the elevated temperatures
at sampling positions.
A sampling device for stack gases i s constituted by a glass- or
quartz-fiber f i l t e r , followed by a special un i t generally consisting
i n a cooler for col lect ing condensable matter and an adcorbent
cartridge (Colmsjo et al . , 1986; Funcke et al., 1988). Tenax-GC has
been used as an adcorbent (Jones et al., 1976), but XAD-2 seems t o be
more suitable (Warman, 1985) and i s generally preferred.
Two sampling procedures have been described i n detai l by the US
EPA (1986~). I n the f i rs t one ( 'Modified method 5 sampling t ra in ' ),
the t r a i n basically includes a GF or quartz-fiber f i l t e r kept at ca.
120°C, a condenser coi1 conditioning the gas at max. 20°C, and a bed
o f XAD-2 jacketed t o mantain the interna1 gas temperature at ca. 17'C.
The second procedure ('Cairce assessment sampling system') i s often
used i n stationary investigations (Warman, 1985). The apparatus
consists o f a stainless steel probe which enters a themstated oven:
t h i s contains the f i l t e r preceded by three cyclone separators i n
series (the cutoff diameters are 10, 3, and 1 m, respectively); the
vo la t i l e organics are cooled and trapped by XAD-2. The corbent i s
followed by a condensate col lect ion trap and an impinger t ra in.
Sampling o f vehicle exhausts i s made under laboratory conditions,
using chassis or engine dynameter testing. Standard dr iv ing cycles
are ernployed to simulate on-road conditions: usually, the US 'Federa1
Test Procedure' (FTP) (CONCAWE, 1991) and the 'Europa Test' (or ECE-15
Test) (Off J Eur Comm, 1983). The choice o f the cycle does not seem t0
play an important ro le i n levels o f PAH emissions (Stenberg, 1985).
Basically, two techniques have been used for exhaust col lect ion
(sampling and analytical methods reviewed by: Levsen, 1988; IARC,
1989). I n the f i r s t one ('raw gas sampling'), the exhaust pipe i s
d i rec t ly connected t o the sampling apparatus: undiluted emissions are
cooled i n a condenser and then allowed t o pass thraigh a f i l t e r for
part iculate col lect ion (Grimer et al., 1979,1988; VDI , 1989).
Ncwadays, a second technique ( ' d i l u t i on tube sampling') i s often
adopted: hot exhaust i s di luted with f i l t e red cold a i r i n a tunnel,
f ran which samples are collected isokinet ical ly. This technique
simulates the process of d i l u t ion occurring under rea1 road
conditions. Di lut ion apparatus and related sampling systems were
described by the VC EPA (1992).
Particles are almost always collected by f i l t e r s : GF, GF with
tef lon binder, and quartz-fiber f i l t e r s , as well as tef lon nembranes;
the l a t t e r have been reported t o be part icular ly adequate i n terms of
eff ic iency and chemical ìnertness (Lee (r Schuetzle, 1983). GF f i l t e r s
impregnated with l i qu id paraff in are also used (Grimmer et al., 1979;
VDI, 1989). Collection of vepwr-phase PAHs (reviewed by Stenberg.
1985) may be performed by cryo-condensation (Stenberg et al., 1983) or
by an adsorbent trap wi th a polyneric material such as XAD-2 (Lee &
Schuetzle, 1983).
Ar t i fac ts during f i l t e r col lect ion may result f r a chemical
conversion of PAHs, part icular ly i n to nitro-PAHs and oxidation
products (reviewed by: Lee 6 Schuetzle. 1983; Schuetzle. 1983; IARC,
1989); such effects s t i l l need t0 be f u l l y evaluated.
3.1.4 Water
PAH concentrations are generally very small, at 0.1 and 1
ng / l i t r e levels i n uncontminated grauidwater supplies and i n drinking
waters. This implies: (a) ' the possib i l i ty , during col lect ion and
storage of samples. o f se r iws errors ar is ing fran adsorption losses
and contamination; (b) the need. i n some cases. for a preconcentration
step t o enrich the sample. Sempl ing i s recomnended t o be perfoned
on-site, d i rec t ly i n the extraction vessel (Smith et al., 1981).
Variws so l id sorbents have been successfully used for the
preconcentration (reviewed by Smith et al.. 1981 ): Tenax-OC.
pref i l tered i f necessary (Leoni et al., 1975); XAD resins (reviewed by
Griest 6 Caton, 1983); operi-pore PLJF (Basu e t al., 1987); and
prepacked disposable cartridges o f bonded-phase s i l i c a gel (Chladek h
Marm, 1984; Van Noort 6 Wondergem, 1985). Colid sorbents have
l imi tat ions when the sample contains suspended material, since
adsorbed PAHs may be los t by f i l t r a t i o n (Van Wrt h Wcndergem, 1985).
3.1.5 Colid samples
A homogenization o f the materia1 (e.g., m e foodstuffs, so i l ,
sediment, tissues, plants) i s normally required before a sample i s
extracted. Pretreatment o f food products has been reviewed (together
wi th techniques for the i r analysis) by Liem et a l . (1992).
3.2 Preoaration
Most environmental samples contain ma l1 amounts o f PAHs,
requiring sophisticated techniques for detection and quantif ication.
Therefore, i t i s essential t o perform an ef f i c ien t extraction frm the
sample matrix, followed by m e or more pur i f icat ion steps enabling the
sample t o be analysed as much as possible free f rm impuri t i es and
interferences. A vary large number o f extraction and pur i f i ca t ion
techniques, as well as of the i r canbinations ( ' i so la t ion schemes'),
are described i n the l i terature. Also considering one specif ic matrix.
there i s no single scheme camwxily recognized as 'the best', although
va r iws methods have been validated and remended. A c l ass i f i ca t i a i
o f iso lat ion schemes, according t o specif ic groups of matrices. has
been made (Jacob & Grinuner, 1979; Grirnmer, 19831, which basically i s
s t i l l widely used and i s b r i e f l y sununarized here.
The avai lable techniques have 'been reviewed (Lee e t al., 1981 ;
Santodonato et al., 1981; Grinuner, 19831, part icular ly the extraction
methods (Griest 8 Caton, 1983): i n very genera1 terms, depending on
the m a t r i x , PAHs are extracted frm the sample by a Soxhlet apparatus
(e.g., f i l t e r s loaded with part iculate matter or vehicle exheusts.
sediments), or d i rec t ly by l iquid-l iquid par t i t i on (water samples), or
- af ter complete sample dissolution (e.g., fats, vegetable and mineral
o i l s ) or alkaline digestion (e.g., meat products) - by a selective
solvent such as N,N-dimethylformamide or (Natusch 8 Tmkins, 1978)
dimethylsulfoxide. The complete PAH extraction frm samples such as
soot emitted by diesel engines, carbon blacks, and 6ther carbonaceous
materials i s part icular ly d i f f i c u l t .
As an alternat ive t o Coxhlet extraction, par t icular ly frm sol id
smlples and f i l t e r s loaded with part iculate matter, ultrasonic
extraction (review by Griest 8 Caton, 1983) i s becaning more and more
successful for the advantages i n tenns of reduced tima of extraction
(minutes versus hours), with recovery efficiencies and
reproducibilities which may also be superior. There i s not a generally
val id conclusiai regarding which technique i s most favourable since
the results of a comparim depend on mat r ix , solvent and experimental
conditions.
Recently, supercritical f l u id extraction ( S E ) (Langenfeld et
al.. 1993) has gained attention as a rapid alternative to conventional
l iquid extraction fran WF sorbents (Hawthorne et al., 1989a), soi l
(Wenclawiak et al.. 1992). and other e n v i r o m t a l solids wch as
urban dust, f l y ash, and sediment (HrPnthorne 6 Mil ler, 1987). SFE may
also be directly coupled with on-colm GC (see 3.3.1): the extract i s
quantitatively transferred into the GC colum, yielding rapid (less
than 1 h) analysis with maxirnun sensitivity. This technigue has b e n applied to urban dust smples (Hawthorn et al., 1989b).
Purif ication of extracted samples f ra other classes of
interfering substances i s most amnonly accoinplished by adsorption
colunn chrcunatography. The classica1 sorbents. almina and especially
s i l i ca gel, are widely used. In addition, the hydrophobic Sephadex
-20 has been fwnd to be suitable to isolate PAHs frm nonaromatic,
nonpolar compounds (which i s important i f the sample i s analysed by
GC) (Griimier 6 Bonke, 197961, a d - i n part i t ion chromatography, as a
carrier of the stationary phase - to separate PAHs f r m alkyl
derivatives (Griimier 6 Bonke, l979a). Chromatographies on s i l ica gel
and Sephadex are often canbined (Jacob 6 Griiinier, 1979; Grinmer,
1983). Clean-up has been perfornied also by eluting extracted sanrples
thrwgh XAD-2 (so i l sanrples: Spi tzer 6 Kwatsuka. 1986). or XAD-2 and
Sephadex W20 i n series (foods: Vaessen et al., 1988). or F lo r is i l
colunns (food, water and sediment sanples: ref. i n Table 7).
Conventimal chrcunatographic c o l m s may be wbstituted with
prepacked conunercial cartridges, with advantages i n tenns of time and
solvents consuned, and of reproducibility performance. For exarnple,
s i l i ca cartridges have been used i n purif ication of foodstuffs (Dennis
et al., 1983), urine (Becher 6 Bjorseth, 19831, vehicle emissions
(Benner et al., 1989), mineral o i l mist (Menichini et al., 1990), and
atrnospheric samples (Baek et al., 1992); soi 1 samples have been
cleaned up through F l o r i s i l cartridges (Jones et al., 1989).
Alternatively t o chromatography on s i l i c a gel colwns,
preparative thin-layer chromatography i s also used, e.g., with a i r
particulates (see Table 6) and vegetable o i l s (Menichini e t al..
1991 ).
To avoid photodecomposition o f PAHs, sample handling i n the
absence of W l i g h t i s recommended at any stage, and part icular ly
during adsorption on chromatographic media. To avoid s igni f icant
losses o f more vo la t i l e PAHs, samples do not have t o be evaporated t o
dryness. Other generally recommended precautions are: t o contro1
possible sairces of contaminaticm (part icular ly, from solvents), t0
store samples - at a l1 stages - refrigerated and i n the dark, t o keep
the water bath temperature of the rotary evaporator under about
35-4O0C.
3.3 Analvsis
A t present, ident i f i ca t ion and quantif ication of PAHs are
rout inely performed by gas chromatography (a) or high-performance
l i qu id chromatography (HPLC). Each technique presents a nwnber of
advantages over the other one. Both o f them are rather expensive,
par t icular ly HPLC, and requi re qual i f i e d operating perconnel.
Nevertheless, they are deemed necessary t o analyse ' real ' samples for
a large number of PAHs wi th accuracy and precision.
Reference rnaterials o f ce r t i f i ed higher than 99% pur i ty are
available for 22 o f the PAHs ms ide red (BCR, 1992); the remaining
conipowids are m e r c i a l l y available as chemical standards, with
pur i t i es of 99% or higher.
3.3.1 Gas chromatography
Excellent separation capacities (about 3000 and more plates per
meter) are obtained by fused s i l i c a capi l lary columns which are
comercia l ly available. This makes i t possible t o analyse very ccmplex
mixtures containing over one hundred PAHs.
The most widely used stationary phases are the
methylplylsiloxanes: especially SE-54 (5% phenyl, 1% vinyl-
substituted) and SE-52 (5% phenyl-1, but also SE-30 and W-l01
(unsubsti tuted), W-17 (50% phenyl-), Dexsil 300 (carborane-), as well
as the i r equivalent phases. The use o f chemically-bonded phases i s
increasing because o f the advantages i n terms o f r i nsab i l i t y t o
restore c o l m performance and lower bleeding at the high temperatures
o f analysis (about 3W.C) that are required for determining high-
bo i l ing cunpounds.
Spl i t less or on-colum injections are necessary t o gain
sens i t iv i ty i n trace analysis, the l a t t e r being preferred as i t allows
better reproducibil i ty. A flane ionization detector (FID) i s almost
universally employed because o f i t s excellent response l inear i ty ,
sensi t iv i ty m d re l i ab i l i t y . Since the FID signal i s related l inear ly
t o the carbon mass o f the cunpound, PAHs are recorded i n proportion t o
the i r quantit ies and the chrwtogram d i rec t ly represents the quanti-
ta t ive composition of the sample. Because o f the non-selectivity o f
FID, samples for GC need t o be highly pur i f ied frm interferences.
Peak ident i f icat ion. which i s r w t i n e l y performed by means of
retention data, has t o be confirmed by analysing the sample with a
d i f ferent GC column or by an independent technique, such as HPLC. or
by a mass spectrmetric ( N ) detector d i rec t ly ccupled to the gas
chromatograph (GC-FtC) . MS detectors have gained wide acceptance. They are powerful tools
i n ident i fy ing compounds, especially when the comnercially available
l ib rar ies of reference spectra are used to match the spectra obtained
and contro1 the cunpound puri ty. Howaver, icomeric cunpounds often
exhibi t indistinguishable spectra, so that the fina1 assignment must
also re ly upon retention data.
For applications o f GC and N t o PAHs, reference i s made to
published reviews (Lee et al., 1981; Cortland Olufsen 6 Bjorseth,
1983; Bartle, 1985; Hites, 1989)
An on-line coupling of l i qu id chrmatography (LC), capi l lary OC
and quadruple MS has been performed i n determining PAHs i n vegetable
o i l s (Vreuls et al., 1991 ).
3.3.2 High-performance l i qu id chromatography
The packing materia1 considered the most suitable for PAH
separation consists of s i l i c a part ic les chemically bonded t o l inear
C18 hydrocarbon chains. Typically, 25-cm columns packed with 5-W
part ic les are used with the gradient e lut ion technique, and the mobile
phase consists o f mixtures of acetoni t r i le/water or methanol/water
('reversed-phase HPLC'). The separation eff ic iency which can be
achieved with HPLC columns i s quite lower than i n capi l lary GC, which
makes HPLC generally less suitable for samples containing complex PAH
mixtures.
On the other hand, relevant advantages o f HPLC derive frm the
capabi l i t ies o f the detectors. Those most widely used for PAHs are
u l t rav io let (W) and f lwrescence detectors, genera1 l y arranged i n
series, employing f low-ce1 l photcmeters or spectrophotometers. Both of
them, and especially the la t te r , are high specif ic and sensitive (the
detection l im i t s i n flwrescence are at least one order o f inagnitude
lower than i n W). Speci f ic i ty of flwrescence detector allows for the
determination o f individua1 PAHs i n the presence of other non-
f lwresc ing substances. I n addition, since di f ferent PAHs have
di f ferent absorptivit ies or d i f ferent flwrescence spectral
characteristics at given wavelengths, the detectors can be optimised
for maximum response f o r specif ic compounds; i n particular, th i s may
prove advantageous i n the ident i f icat ion of unresolved cunponents.
HPLC i s not suitable for lowermolecular mass mpounds (namely, MA,
AC, and ACL), which have re lat ively high detection l im i t s (US EPA,
1984).
I n addition, owing t o the select iv i ty of packing materials,
va r iws isomers which cannot be separated, or only pa r t i a l l y so, by
usual capi l lary GC columns, are baseline resolved and ident i f ied by
WLC: for example, the pairs CHRTRI, and BbFA-BkFA (Wise et al.,
1980).
The coupling of an MS detector t o HPLC has been developed and
also applied to PAH detection (e.g., Q u i l l i a m 8 Sim, 1988).
Much information on the isomeric structure may be obtained from
spectra acquired during the elut ion of chromatographic peaks. For t h i s
purpose. the W diode-array detector (DADI i s gaining acceptance i n
PAH analysis for m f i r m a t i o n of peaks (Dong 6 Greenberg, 1988;
Kicinski e t al., 1989).
For applications o f HPLC t o PAHs, reference i s rnade t o published
reviews (Lee et al., 1981; Wise 1983,1985).
3.3.3 Thin-layer chrunatography
Nowadays. thin-layer chrunatography (TLC) i s ccimwxily lirnited to
the ident i f icat ion o f individua1 cunpounds (namely, BaP), part icular ly
fo r screening purposes (IUPAC. 1987), or o f selected PAHs such as the
s ix PAHs (Borneff 6 Kunte, 1979) whose determination was reconmeoded
by the W 0 (1971) i n drinking water. Indeed. i t i s an inexpensive and
quick analytical techique, but with lcu separation efficiency. This
last parameter i s irnprwed by two-diinensional processes (e.g., Borneff
6 Kunte, 1979).
u tant i f ica t ion may be performed by spectrophotometric or
spectrofluorimetric methods i n solution a f ter extracting the scrubbed
substance spot (Hauard, 1979; also reported i n W , 1990). or i n s i t u
by SCming spectrofluarimetry (Borneff 6 Kunte. 1979).
As M adsorbent, acetylated cellulose has been m t l y used for
one-step separation o f the PAH fraction, and mixed alminun oxide and
acetylated cellulose for two-dimensional developnent (reviewed by
Daisey, 1983)
3.3.4 Other techiques
A m b e r o f ~ m o n v e n t i o n a l instrunents and techniques, based on
spectroscopic principles, have been - and s t i l l are being - developed
as possible alternatives t o the chmatographic methods for PAHs.
Hauever, m s t o f t h m are quite expensive, require sk i l led persmnel,
and are not yet ms ide red useful for the practicing analyst. For
detai ls on such techniques and their applications to PAHs, reference
i s rnade to published reviews (Wehry, 1983; Vo-Dinh, 1989. various
chapters). Lcu-temperature luninesceoce i n frozen solutions
("Shpol'skii effect") has been applied t o various envirunnental
samples, part iculàr ly t o ident i fy methylated PAH isuners (Garrigues 6
Ewald, 1987; Saber e t al., 1987). Synchronous lminescence and m temperature phosphorimetry have been reported as simple and cost-
ef fect ive screening techniques for PAHs (Vo-Dinh et al., 1984; Abbott
e t al., 1986).
Infrared analysis - and part icular ly F w r i e r transform infrared
(FTIR) spectroscopy coupled t0 GC ( S t w t Mamantov, 1989) -, and
capi l lary supercrit ical f l u i d chromatography (SFC) (Wright & Smith,
1989) have a l so been appl i ed t o PAHs.
3.4 Choice o f PAHs t o be detennined
The choice depends on the purpose o f measurement. For example,
carcinogenic PAHs are o f interest i n hwnan health studies; other, more
abundant compounds may be of interest i n ecotoxicological studies. I n
addition, a multitude o f compounds are advantageous when PAH prof i les
have t o be correlated t o swrces and/or effects.
Table 8 (p. 32) shows come l i s t s o f compounds whose determination
has been required or recommended at national or international levels.
According t o an EEC Directive ( O f f J Eur Comm, 1980), which
followed a WHO (1971) recommendation, the concentrations o f s ix
reference compounds (also known as 'Borneff PAHs') must be measured i n
drinking waters i n order t o check thei r compliance with the cumulative
l i m i t value of 0.2 & l i t r e for the PAH class. The origina1 WHO choice
o f these six PAHs was not based on any toxicological considerations,
but on the fact that analytical investigations were then largely
confined t o these ( re la t ive ly easi ly detected) compounds (M, 1984).
The method required by the US EPA (1984) for the analysis o f
municipal and industria1 wastewater covers the determination of 16
PAHs ( ' p r i o r i t y pollutant PAHs') considered representative of the
class. Even outside the USA, t h i s l i s t of compounds i s often taken as
a reference l i s t fo r the analysis of va r iws environmental matrices.
The European Aluminium Ascociation (W-EHC, 1990) has
recommended a l i s t of 19 PAHs t o be determined i n any kind of samples
related t o operations i n that specif ic industry. The l i s t i s based on
the PAH composition o f emissions from aluminium mel ters, the IARC
c lassi f icat ion o f carcinogenicity, and the exist ing o f f i c i a l l i s t s .
The I ta l ian National Advisory Toxicological C m i t t e e (Menichini,
1992b) has reconmended including the determination of seven PAHs i n
health-related investigations, based on their carcinogenicity
('probably' or 'possibly' carcinogenic to hunans; IARC, 1987) and
their occurrence i n the enviromient.
As a conclusion of an international Workshop on PAHs (SFT-SNT,
1992), i t was recommended to determine 15 carcinogenic PAHs i n
health-related studies and to include another six abundant PAHs for
envirunnent-related studies.
T ib la 6. A n i l y t i c i l i a t h o d r ( i i t r i x : i i r )
L i n i t of I i t r i x S i i p l i n g , e x t r i c t ion C l i in -up Analysis d t t cc t i on ' Rt fer inca
p----- - ;;bient i i r s u p l i n p on GFtPUF, l i q . - l i q . p i r t i t i o n GCIYS Y i i r r i k i et a l .
rt 45 i i l h ; (C-hexrn8:HtO:MISO); 11982) soxhlet i x t r . (C-h tx rne l t h i n CC (SiOt)
t i i r r i o n s [ i u n i c i p i l i ncene r i t o r )
veh ic le axhtur t
r i i p l i n p on G W F , i t 30 i i l h ; soxhlot ex t r . r i t h pa t r . ether (6F) i n d DW IPUF)
s i i p l i n g on GF l p r r t i c l i d < l 5 W), i t 68 P l h ; r o x h l i t ax t r . r i t h C-hexinc t DCM 4 rcctone
s i i p l i n g on Gf, i t 83 $/h; s o n i c i t i o n (C-h tx ine)
r r i p l i n g by p l i s s r o o l 4 condtnrcr t XAD-2; ex t r . i i t h ice tona I g l i s s r o o l t nd XAD-2: by soxh le t )
r i i p l i n p by GF t condanrer; 1 iq.- l iq. p i r t i t i o n i i t h icetone:H10:c-hexrni i n d WF:HiO:c-hixinc
r r i p l i n g i n d i l u t i o n tunnel by t i f lon-coi ted GF 4 c o n d ~ n r w ; r o x h l i t ax t r . o f f i l t e r (DCM) i n d condansitc ( i c i t o n 8 ) ; r i i i i n i n p iqu tour phart ex t r . i i t h DCY
CC i A l i O ì t SiOt i
TLC (SiOt
TLC (Si02 )
1 i q . - l i q . p i r t i t i o n i i t h DYF
l i q . - l i q . p i r t i t i o n (C-hcxina:ntO:WF)
HPLCIUVtFI 0.01-0.4 Grcenberg et il. n g l i 3 (1985)
V r l e r i o at il. (1992)
GC 10 n # / i 3 C o i i s i o et il. (198s)
GC 2.5-20 ng G r i u t r e t il. per 'Europa 11919) t e s t '
I e s t t r h o l i @t il. 11988)
T ib l t 6 (contd.) -
indoor t i r r u ~ l i ~ ~ on 6F I p i r t i c l t d TLC l i c t t r l o x v l i t r d r ~ t c t r o f l u o r . Liov i t il. < 10 ri i t 10 l i t r i r l i i n ; c t l l u lose ì wn icc t ion (C-htr rnt )
t u p l i n f on quart i f i b t r f i l t t r t XAD-4, i t 228 l i t r t r l i i n ; soxhlt t t x t r . r i t h OCY
r u p l i n g on t i f l on - co i t t d f i l t r r t i o n ; th tn CC 6F, at 20 l i t r i r l i i n for 24 [SiOi c i r t r i dg i ) , h; roxhlot txtr. r i t h DCT optional
s u p l l n g on purrtz f i b t r CC (Si& or u i n o - f i l t t r t PUF or XAD-t, rt 20 t i l i ne ) , il nctdtd l i t r t r l i i n for 24 h; r o i h l t t t x t r . r i t h DCT ( f i l t t r rnd XAD-2) or 8tbir:n-hixrnt ( M I )
uorkp l tc i r i i p l i n g en t t f l o n f i l t e r t i i r UQ-2, rt 2 l i t r i i / i i n ;
ronicr t ion or r oxh l i t i x t r . of f i l t t r , t x t r . o f UW i i t h t o l u t n i i f o r CC) or t c i t o n i t r i l @ (far HPLC)
i u p l l n g on f i l t t r (W or CC (XAD-2) qui r tz f i b i r or t t f l o n or r i l v t r i u b r i n i ) i t 2 l i t r o l i i n ; r on i c i t i on or toxhl#t i x t r . i i t h C-htxine or to lu tn t
tobicco r u p i i a q by i c t t o n t tra); Ce (Si01 t StpLadw ~ k t to lv tn t p i r t i t ion r c h w t LI-20); th tn HPLClUV
ircidrlbtrtrln~utri1rlPAHi)
Chuug i t il. (1991)
CC: c o l u n chrmitogrrphy; C-htxrnt: cyc ldaxint ; D#: d ich loro ic thmt; W: N,N-d i r thy l fonu id i ; W: d i i t t h y l - sulfoxidt; FI: fluor6sctnct; IIYR: nuc l t r r i i g n t t i c rtroninci; o tht r r bb r t v i i t i om : IIO ttit. i Ringt r t f i r r t o t h i v i r i o u i PAW.
Tht f o l l m i n q PANI c m b t dot i r i ined: FA, PV, CM, BtP, BbFA, BkFA, W , BHiP, W , e Approprictt solvint h o t o b t d i t i r i i n o d throuth r tcovtry t i i t i on t h t r p t c i f i c i u p l i .
Tcbh l. A n i l y t i c r l icthods ( n r t r i c t i o th r r th rn r i r ) v-- -- P
--p --- L i u i t of
Y i t r i x E x t r i c t ion Clern-up Ani lys is da t i c t iona R t t i r t n c t W- -p---- --
t r p rrt ir pr#concentrr t ion on PUF; 1iq.-liq. p t r t i t i o n 66 or 0.1 n g l l i t r a B t ru L Sixtnc t x t r . ( i ce ton t t C-hextne) r i t h C-htxrnc:HtO:YeOH TLC (Al tOi : (1918)
cnd C-hexrni:HtO:DYSO; c c t t y l . c i l l u l . ) then CC l f l o r i s i l ) r i t h FI d t tactor
CC (SiOt), i f neaded ground r i t c r l i q . - l i q . p t r t i t ion r i t h DCY
i) 6C i ) p g l l i t r i I t v t l US fPA (19868) b) 6CIYS b) 10 p g l l i t r t C ) HPLCIUVtFI C ) 0.01-2 p g l l i t r t
i c s t c rrttr l i q . - l i ( . p i r t i t ion r i t h DW
CC or 0.01-0.2 ~ g l l i t r t US EPA 11984) HPLCIUVtFI l by HPLC)
r t i rrttr l i q . - l i q . p r r t i t i o n r i t h n-hexrnt or CC14
i o i l sonicct ion r i t h DCY CC lA1101); t h i n l i q . - l i q . p i r t i t l o n (n-htxrnt:HiO:DUSO)
1 soxhlot txtr. r i t h DCY
b t d i r t n t r o x h l t t ixtr. r i t h DCY CC (SiOi t Scphidax LH-20)
P u i l l i r i 1 S i i ( toae)
i o n i c r t i o n r i t h tct tont:n-htxtnt
HPLCIUVtf I 1-180 pglko Yrrcus #t 81. (tosa)
i t r t tnd f i r h I ) digest ion ( i l c . KOH), productr ( I ) , t h t n l i q . - l i q . p o t i t i o n v t g c t t b l r (Yt0H:HiO:c-hexrne) o i l r ( I l ) , 11) d i i s o l u t i o n i n C-hexrne ind serrga I l ! ) r t f l u x i n g r i t h ccetons i ludgc (111)
1 iq . - l iq . p i r t i t i o n (C-hextnt:HtO:WF); thcn CC (SiOt t S ~ p h t d t ~ LH-20)
p d rc f l ux ing r i t h t l c , KOH,
t o t r l d i t t ) ox t r . r i t h i rooct rnc I i ~ . - l i q . p r r t i t i o n (iiooctrnt:HiO:DYF); t h t n CC (Si01 c i r t r i d g t )
HPLC/Fl 0.002-0.1 p ~ l k ~ Dinn i r rt a \ . (1983)
r c p o n i f i c i t i o n ( r l c . (OH), t x t r . r i t h C-h ixrn i
HPLCIFI 0.03-2 pglkg De Voi @t 11. ( l W )
r i p o n i f i c c t i o n ( r l c . KOH), i x t r . i i t h i r o o c t i n i
CC ( f l o r i r i l ) ; t h t n 1 ip . - l iq . p i r t i t i o n (isooctrnt:HtO:DYSO)
T i b l i T 1contd.i ---W----
r t t f o o d d i g i i t i o n r i t h i l c . (OH, CC lA110i + S i & t HPLC/FI 0.01-0.6 pp/kg P n r f e t t i t x t r . r i t h TCTFE
s iok id food d i g i r t i o n r i t h r l c . (OH, t x t r . r i t h TCTFE
r t f b x i n g r i t h C-h tx in i or TCTFE, t x t r . r i t h Yt0H:HiO
s o l i d r i s t t soxh l t t i x t r . r i t h OCY or r o n i c i t i o n r i t h DCY:ictton:
i i n e r i l o i l l i q . - l i q . p i r t i t i o n i n d f u t l (C-hex~nt:HiO:MIF)
m t d i c i n i l o i l l i q . - l i q . p i r t i t i o n (C-hixinn:H~O:MIf i
p l i n t i
u r i na
u r ine i n d f i t c e r
t issu:
r k i n e
CC (Al tOI + SiOtl ; l i q . - I i q . p i r t i t i o n (C-htxinr:H~O:WSO)
l i q . - l i q . p r r t i t i o n [C-htxini: i i~O:OYF); t h t n CC IS iOi )
CC (Si01 i , il netdtd
son icr t ion l r c i t o n i t r i l t l , CC (Si011 c x t r . r i t h pentine
i d j u i t t d t o pH3, i x t r . by CC ISiOt c t r t r i d g t l C i i c r r t r i d g i , r t duc t ion o f a i t i b o l i t t t r i t h H1
i d d i t i o n o f HCI, re f l ux ing CC ISiOt + r i t h t o l u t n i , i d d i t i o n of Siphidix LH-201 YtOH t d i t z o i i t h i n i i n t t h c r ( f i t c o i r e s i p o n i f i c i t i d b t fo rc i c i d i f i c i t i o n )
hoaogenizit ion CC I F l o r i i i I l (btztncn-hexcn:)
t o n i c r t l o n o f i x p o r u r i p i d t r i t h DCY, c t n t r i f u g i t i o n
TLCIUVtF 1
TLCIFI' (only BiPI
I) GC b l 6ClYS C) HPLC/UY+FI
6C
HPLCIFI t 6C
6C
HPLC'
BC i n d GCIYSI
GClUS
HPLCIFI
i t il. (1992)
0.03-0.4 pg/kg Jo i tt il. ( 1 9 ~ 4 )
0.5 ng/kg IUPAC 119811
(,C) pglkg l e v t l US EPA I I986b) b) 1-200 mglkg
100 nglkg G r i l a t r L Bohnki 119111
0.2-200 nglkg Gtihchin t t il. (1991)
C o i t t r t t il 119M)
Btchtr I Bjo rs t th 119831
Jtcob et il. 119891
6 ng lc i2 J o g t n o l t n ,t il. 119681
-- TCTFE: 1,1,2-trichlorotrifluoroithinc; o t h i r i b b r t v i r t i o n r : s i i T i b l i 6. 1 Ring: r e f t r r t o t h i v i r i o u r PANI.
Tht I i P cont tn t i s t c t l i i t t d t o bc > o r ( 0.6 ug/kg ( r c r t t n i n g ie thod l . O t t t r i i n i t i o n o f u n i i t i b o l i z i d i n d a t t i b o l i z i d PAHi.
6 D t t i r a i n i t i o n of PV rnd l -hydroxypyrtnt . e M e i r u r t i t n t of r k i n c o n t i i i n i t i o n r i t h t o f t po lypropy l tn i t xpo ru r i p161 i o u n t t d on r i i n i i t a a .
l Table 8. Some e x i s t i n g l i s t s of PAHs t o be determined
WHO/EECa EAAC SFT-SNT" d r i n k i n g US EPAb aluminium C C T N ~ ----------------
Compound water wast ewat e r i ndust r y a i r hea l t h environ.
l
b
d
l
Recommended by WHO (1971 ) and requ i red by an EEC D i r e c t i v e (O f f J Eur C m , 1980). Required by US EPA (1984) f o r the ana lys i s o f munic ipa l and i ndus t r i a1 wastewater. Recommended by the European Aluminium Associat ion (EAA-EHS, 1990) Recommended by the I t a l i a n Nat iona l Advisory Tox ico log ica l Committee (CCTN) i n hea l th - re la ted s tud ies (Menich in i , 1992b). Recommended at the I n t e r n a t i o n a l Workshop on PAHs (SFT-SNT, 1992) hea l th - re la ted s tud ies ( l e f t column) and i n envi ronment-related s tud ies ( r i g h t ) .
Abbott W. Moody RL, Mann M, & Vo-Dinh T (1986) Synchronous luminescence screening for polynuclear aromatic canpounds i n environnental samples collected at a coal gasif ication process development unit . Am Ind Hyg Asscc J, 47(7): 379-385.
Anderson K, Levin J-O, Nilsson C-A (1983) Sampling and analysis o f part iculate and gaseous polycyclic aranatic hydrocarbons fran coal tar sources i n the working environment. Chemosphere, 12(2): 197-207.
AOAC (1990) Pol ycycl i c aromatic hydrocarbons and benzo[alpyrene i n food - Spectrophotanetric method (No. 973.30). In: Helrich K ed. O f f i c i a l methods o f analysis of the Asscciation o f Of f i c ia l Analytical Chemists, 15th ed. Arlington, Virginia, Association o f Of f i c ia l Analytical Chemists, Inc., pp 11784178.
Baek SO, Goldstone ME, Kirk M, Lester JN, & Perry R (1992) Concentrations o f part iculate and gaseats polycyclic aromatic hydrocarbons i n London a i r following a reduction i n the lead content o f petrol i n the United Kingdan. Sci Total Environ, 111: 169-199.
Bart le KD (1985) Recent advances i n the analysis o f polycyclic aranatic arnpounds by gas chromatography. In: Bjorseth A & Ramdahl T eds. Handbook of polycyclic aronuitic hydrocarbons, Vol 2. New York, Marce1 Dekker, Inc, pp 193-236.
Basu DK & & Saxena J (1978) Monitoring o f polycyclic aromatic hydrocarbons i n water 11. Extraction and recovery o f s i x representative arnpounds w i t h polyurethane f m s . Envi ron Sci Technol , 12(7): 791-795.
Basu M<, Saxena J, Stoss W , Santodonato J, Neal W, & Kopfler FC (1987) Comparison of drinking water mutagenicity with leaching o f polycyclic aranatic hydrocarbons fran water d ist r ibut ion pipes. Checnosphere. 16( 10-1 2) : 2595-281 2.
BCR (1992) Reference materials. Bwssels. Cumnission o f the European Conununities, Conununity Bureau of Reference - BCR.
Eecher G & Bjorseth A (1983) Deternination o f exposure t o polycyclic aranatic hydrocarbons by analysis o f hunan urine. Cancer Letters, 17: 301-311.
Beilstein (1993) Data Base. Frankfurt. Bei lstein Ins t i tu te for Organic Chemistry. February 22, 1993.
Benner BA Jr, Gordon GE, €i Wise SA (1989) Mobile satrces o f atmospheric polycyclic a r m t i c hydrocarbons: a roadway tunnel study. Environ Sci Technol, 23: 1269-1278.
Bjorseth A (1983) Appmdix. In: Bjorseth A ed. Handbook of polycyclic a rmat ic hydrocarbons. New York, Marce1 Dekker, Inc., pp 709-718.
Bjorseth A 6 Becher G (1986) PAH i n work atmospheres: occurrence and determination. Boca Raton, Florida, CRC Press, Inc.
Borneff J & Kunte H (1979) Method 1 - Analysis of polycyclic aromatic hydrocarbons i n water using t h i n layer chrmatography and spectrofluorornetry. In: Egan H, Castegnaro M, Bogovski P, Kunte H, & Walker EA eds. Environmental carcinogens - Selected niethods o f analysis, Vol 3 - Analysis o f polycycl i c armat ic hydrocarbons i n environmental samples. Lyon, International Agency for Research on Cancer, pp 129-139 (IARC Publications No 29).
Brooke DN, Dobbs AJ, & Williams N (1986) 0ctanol:water par t i t i on coeff ic ients (P): measurement, estimation, and interpretation, part icular ly for chemicals with P>lOs. Ecotoxicol Environ Safety, 11: 251 -260.
Bruggeman WA, Van der S t m J, 6 Hutzinger O (1982) Reversed-phase thin-layer chromatography o f polynuclear aromatic hydrocarbons and chlorinated biphenyls. Relationship with hydrophobicity as measured by aqueous so lub i l i t y and octanol-water par t i t i on coefficient. J Chrm, 238: 335-346.
Budavari S ed. (1989) The Merck Index: M encyclopedia of chemicals, drugs, and biologicals, l l t h ed. Rahway, New Jersey, Merck and Co., Inc.
CAS (1988) Ring Systems Handbook. Washington, DC, Pnarican Chemica1 Society - Chemical Abstracts Service.
CAS (1990) Chemical abstracts index guide. Colunbus, Ohio, American Chemical Society - Chemical Abstracts Service.
Catoggio JA, Succar SD, & Roca AE (1989) Polynuclear aromatic hydrocarbon content o f part iculate matter suspended i n the atmosphere o f La Plata, Argentina. Sci Total Environ, 79: 43-58
Chladek E 6 Marano RS (1984) Use o f bonded phase s i l i c a sorbents fo r the sampling o f p r i o r i t y pollutants i n wastewaters. J Chromatwr Sci, 22: 313-320.
Chuang JC, Hannan W , & Wilson NK (1987) Fie ld mpar i son o f polyurethane foam and XAD-2 resin fo r a i r sampling for polynuclear armat ic hydrocarbons. Environ Sci Technol. 21: 798-804.
Chuang JC, Mack W, Kuhlman Wt, 6 Wilson NK (1991) Polycyclic armat ic hydrocarbons and the i r derivatives i n indoor and outdoor a i r i n an eight-hcme study. Atmos Environ 258(3): 369-380.
Coates JY, Elzerman AW, & Garrison AW (1986) Extraction and determination of selected polycyclic a rmat i c hydrocarbons i n plant tissues. J Assoc Off Anal Chem, 69(1): 110-114.
Colmsj6 A, ZebOhr W, & ostman CE (1986) Polynuclear aromatic compainds i n f lue gases and ambient a i r i n the v i c i n i t y of a municipal incineration plant. Atmos Environ, 20(11): 2279-2282.
CONCAWE (1991) Motor vehicle emission regulations and fuel specifications - 1991 update. Brussels, CONCAW (The o i l wpan ies ' European organization for envirorwnental and health protection) (Report no. 3/91).
Coutant W, Brown L, Chuang JC, Riggin RM, & Lewis RG (1988) Phase dist r ibut ion and a r t i f ac t formation i n ambient a i r sampling for polynuclear aromatic hydrocarbons. Atmos Envi ron, 22(2): 403-409.
Daisey JM (1983) Analysis of polycyclic aromatic hydrocarbons by thin-layer chromatography. In: Bjorseth A ed. Handbook o f polycyclic aromatic hydrocarbons. New York, M. Dekker, Inc., pp 397-437.
Daisey JM & Gundel LA (1993) Method 20 - Determination o f extractable part iculate organic matter and selected polycyclic aromatic hydrocarbons. In: Seifert B, van de Wiel HJ, Dodet B, & O'Neill I K eds. Environmental carcinogens - Methods of analysis and exposure measurement, Vol 12 - Indoor a i r . Lyon, International Agency for Research on Cancer, pp 314-327. (IARC Sc ient i f i c Publ ications No 109).
Davis W, Krahl ME, & Clowes GHA (1942) Solubi l i t y of carcinogenic and related hydrocarbons i n water. J Am Chem Soc, 64: 108-110.
Davis CC, Fe l l i n P, & O t m R (1987) A review o f sampling methods for polyaromatic hydrocarbons i n a i r. JAPCA, 37(12): 1397-1408.
Dennis MJ, Massey RC, McWeeny, Knowles ME, & W a t m D (1983) Analysis of polycyclic aromatic hydrocarbons i n UK to ta l diets. Fd Chem Toxic, 216) : 569-574
De Raat WK, Xhu l t i ng FL, Burghardt E, & De Mei jere FA (1987) Application o f polyurethane foam for sampling vo la t i l e mutagens frani ambient a i r . Sci Total Environ, 83: 175-189.
De Raat WK, Bakker GL, & De Meijere FA (1990) Compariwxi of f i l t e r materials used for smpl ing of mutagens and pol ycycl i c aromatic hydrocarbons i n ambient a i rborne part ic les. Atms Envi ron, 24A( 11 ): 2875-2887.
Desideri PG, Lepri L, Heimler D, Giannessi S, & Checchini L (1984) Concentration, separation and determination of hydrocarbons i n sea water. J Chrmatogr, 284: 167-178.
De Vos RH, Van Dokkun W, Schouten A, 6 De Jong-Berkhout P (1990) Polycyclic arunatic hydrocarbons i n Dutch to ta l d ie t samples (1984-1986). Fd Chem Toxic, 28(4) 263-268.
DFG (1991 ) Pol ycycl i c armat ic hydrocarbons (PAH) (particle-bound) . In: Kettrup A ed. Analyses of hazardous substances i n a i r , Vol. 1. Weinheim, Germany, VCH Publisher Inc., pp 41-52, Deutsche Forschungsgemeinschaft (DFG) - Commission for the investigation of health hazards o f chemical mpounds i n the work a i r , Working Grwp Analytical Chemistry.
Dong W 6 Greenberg A (1988) Liquid chrunatographic analysis of polynuclear aromatic hydrocarbons with diode array detection. J L iq Chrun, ll(9610): 1887-1905.
W-EHS (1990) Document 'Polycycl i c armat ic hydrocarbons' . 0510, Norway, Aluniniumindustriens M i 1 iosekretariat, EAA-EHS (European Alminiun Association - Envirment, Health and Safety) Working Grwp on PAH (ALUM./TEKN.-HYG.UW. Nr . 80-90).
Ehrl ich W 6 Beevers CA (1956) The crystal strutture of 2:13-benzfluoranthene. Acta Crystal, 9: 602-606.
Funcke W, Konig J, & Balfanz E (1988) Determination o f polycyclic arunatic hydrocarbons i n f lue gases frun coal-fired power plants. In: Cooke M 6 Dennis AJ eds. Polynuclear aromatic hydrocarbons: a decade of progress. Columbus, Ohio, Bat te l le Press, pp 277-284.
Garrigues P 6 Ewald M (1987) High resolution emission spectroscopy (Shpol'skii effect): a new analytical technique for the analysis o f pol ycycl i c aromatic hydrocarbons (PAH) i n the envi r m t a l samples. Chwsphere, 16(2/3) : 485-494.
Geahchan A, Le Gren I, Chambon P, 6 Chambon R (1991 ) Improved method fo r determination of p01 ynuclear armat ic hydrocarbons i n pharmacopoeial paraf f in and mineral o i l s . J Assoc O f f Anal Chein, 74(6): 968-973.
Greenberg A. Darack F, Harkov R, Lioy P. 6 Daisey J (1985) Polycyclic armat ic hydrocarbons i n New Jersey: a comparicon o f winter and sumnier concentrations over a two-year period. Atmos Environ, 19(8): 1325-1 339.
Griest WH 6 Caton JE (1983) Extraction o f polycyclic armat ic hydrocarbons for quantitative analysis. In: Bjorseth A ed. Handbook of polycyclic aromatic hydrocarbons. New York, Marce1 Dekker, Inc, pp 95-1 48.
Grinmner G (1983) Chemistry. In: Grinbner G ed. Environmental carcinogens: polycyclic arunatic hydrocarbons. Bcca Raton, Florida, CRC Press, Inc., pp 27-60.
Grimer G 6 M k e H (1979a) Method 3 - Gas chromatographic p ro f i l e analysis of polycyclic aromatic hydrocarbons i n lubricat ing oi1, cut t ing o i l and fuel. In: Egan H, Castegnaro M, Bogovski P, Kunte H, 6 Walker EA eds. Environmental carcinogens - Selected methods of analysis, Vol 3 - Analysis of polycyclic aromatic hydrocarbons i n environmental sampies. Lyon, International Agency for Research m Cancer, pp 155-162 (IARC Publications No 29).
Grimer G Bonke H (1979b) Method 4 - Gas chromatographic p ro f i l e analysis o f polycyclic aromatic hydrocarhs i n ( I ) high protein foods, (11) fats and vegetable o i l s and (111) plants, so i ls and sewage sludge. In: Egan H, Castegnaro M, Bogovski P, Kunte H, & Walker €A eds. Environmental carcinogens - Selected methods of analysis, Vol 3 - Analysis of polycyclic aromatic hydrocarhs i n environmental samples. Lyon, Internat imal Agency for Research on Cancer, pp 163-173 (IARC Publications No 29).
Grimer G, Hildebrandt A, & Bonke H (1979) Method 2 - Gas chromatographic p ro f i l e analysis o f polycyclic aromatic hydrocarhs i n automobile exhaust gas condensate. In: Egan H, Castegnaro M, Bogovski P, Kunte H, & Walker EA eds. Envi romnental carcinogens - Selected methods o f analysis, Vol 3 - Analysis of polycyclic aromatic hydrocarbons i n env i rmenta l -10s. Lyon, International Agency for Research on Cancer, pp 141-154 (IARC Publications No 29).
Grimer G, Naujiack K-W, 6 Schneider D (1982) Prof i l e analysis of pol ycycl i c aromatic hydrocarbons by glass capi l l a r y gas cromatography i n atmspheric suspended particulate matter i n the nanogram range col lect ing 10 m3 o f a i r . Fresenius Z Anal Chem, 311: 475-484.
Grimner G, Jacob J, Dettbarn G, & Naujack K-W (1985) Determination of polycyclic aromatic hydrocarbons, azaarenes. and thiaarenes emitted f ra coal-fired residential furnaces by gas chranatography/masc spectrometry. Fresenius Z Anal Chem, 322: 595-602.
Grimmer G. Jacob J, Dettbarn G. & Naujack K-W (1988) Effect o f the pH- value o f diesel exhaust on the amaint o f f i l ter-col lected nitro-PAH. In: Cooke M 6 Dennis AJ eds. Polynuclear aromatic hydrocarbons: a decade o f progress. Columbus. Ohio, Bat te l le Press, W 341-351.
Grosjean D (1983) Polycyclic aromatic hydrocarbons i n Los Angeles a i r from samples collected on teflon, glass and quartz f i l t e r s . Atms Envi ron, 17(12): 2565-2573.
Hawley G (1987) Hawley's Condensed Chemical Dictionary, I l t h ed. revised by Sax N1 & Lewis RJ, Sr. New York, Van Nostrand Reinhold COmPanY.
Hawthorne SB 6 M i l l e r DJ (1987) Extraction and recovery of polycyclic aromatic hydrocarbons from env i rmenta l sol ids using supercrit ical f luids. Anal Chem, 59: 1705-1708.
Hawthorne Sf3, Krieger MS & Mi1 l e r DJ (1989a) Supercrit ical carbon dioxide extraction of polychlorinated biphenyls, polycyclic a rmat i c hydrocarbons, heteroatom-containing polycyclic aromatic hydrocarbons, and n-alkanes frm polyurethane foam sorbents. Anal Chem, 81: 736-740.
Hawthorne CB, M i l l e r DJ, & Krieger MS (1989b) Coupled SFE-OC: a rapid and simple technique for extracting, identifying, and quantitating organic analytes from so l id and sorbent resins. J Chrmatogr Sci, 27: 347-354.
Hawthorne CB, M i l l e r DJ, Langenfeld JJ, & Krieger MS (1992) PM-10 high-volume col lect ion and quantitation o f semi- and nonvolatile phenols, methoxylated phenols, alkanes, and polycyclic aromatic hydrocarbons from winter urban a i r and the i r relationship t o wood smoke emissions. Environ Sci Technol, 26(11): 2251-2262.
Hites RA (1989) Mass spectrmetry o f polycyclic aromatic cunpounds. In: Vo-Dinh T ed. Chemical analysis of polycyclic aromatic compounds. New York, John Wiley & Cons, pp 219-261.
Howard J (1979) Method 5 - Analysis o f benzoCalpyrene and other polycyclic armat ic hydrocarbons i n foods. In: Egan H, Castegnaro M, Bogovski P, Kunte H, Walker €4 eds. Environmental carcinogens - Selected methods o f analysis, Vol 3 - Analysis o f polycyclic a rmat i c hydrocarbons i n environmental samples. Lyon, International Agency for Research on Cancer, pp 175-191 (IARC Publications No 29).
Howard PC, Hecht CC, & Beland FA eds. (1990) Ni troarenes - Occurrence, metabolism, and biologica1 impact. New York, Plenum Press.
HCDB (1993) Hazardws Substances Data Bank. Bethesda, MD, National Library o f Medicine, National Toxicology Program. February 22, 1993.
IARC (1973) Certain polycyclic a rmat i c hydrocarbons and heterocyclic compounds. Lyon, International Agency for Research on Cancer (IARC Monographs on the evaluation o f the carcinogenic r i s k o f chemicals t o man, Vol 3).
IARC (1983) Polynuclear armat ic cunpounds, Part 1, Chemical, envi r m e n t a l and experimental data. Lyon, Internat ional Agency for Research on Cancer (IARC Monographs on the evaluation of the carcinogenic r i sk o f chemicals t o humans, Vol 32).
IARC (1987) Overall evaluations o f carcinogenicity: un updating of IARC Monographs Volumes 1 t o 42. Lyon, International Agency for Research on Cancer (IARC Monographs on the evaluation o f carcinogenic r isks to humans, Supplement 7).
IARC (1989) Diesel and gasoline engine exhausts and some nitroarenes. Lyon, International Agency for Research on Cancer (IARC Monographs on the evaluation o f carcinogenic r isks t o humans, Vol 46).
Inokuchi H & Nakagaki M (1959) The densi t y o f the polycycl i c aromatic cmpounds. Bul l Chem Soc Japan, 32( 1 1: 65-67.
IuPAC (1979) Nmenclature o f organic chemistry. Sections A, 0, C, D, E, F and H. Oxford, Pergamon Press, International Unicm of Pure and Applied Chemistry.
IUPAC (1987) International Union o f Pure and Applied Chemistry - Recommended method for a thin-layer-chrmatographic screening rnethod for the determinatim o f benzo(a)pyrene i n smoked food (prepared far publication by Grimmer G & Jacob J). Pure B Appl Chern, 59(12): 1735-1 738.
Jacob J & Grinuner G (19791 Extraction and enrichrnent of polycyclic aromatic hydrocarbons (PAH) frm environmental metter. In: Egan H, Castegnaro M, Bogovski P, Kunte H, 8 Walker EA eds. Environmental carcinogens - Selected methods o f analysis, Vol 3 - Analysis of polycyclic aromatic hydrocarbons i n enviromnental samples. Lyon, International Agency for Research on Cancer, pp 79-89 (IARC Publications No 29).
Jacob J, Brune H, Gettbarn G, Gr immer D, Heinrich U, Mohtashamipur E. Norpoth K, Pott F & Wenzel-Hartung R (1989) Urinary and faecal excretion of pyrene and hydroxypyrene by rats af ter oral , intraperi tmeal, intratracheal or in t rapu lmary application. Cancer Letters, 46: 15-20.
Joe FL Jr, Salemme J, & Fazio T (1984) Liguid chromatographic determination of trace residues of polynuclear aromatic hydrocarbons i n smoked foods. J Assoc Off Anal Chem, 67(6): 1076-1082.
Jones W, Giamnar RD, Strup PE, & Stanford TB (1976) Ef f ic ient col lect ion o f polycyclic organic compounds from cmbustion effluents. Environ Sci Technol, 10(8): 806-810.
Jones KC, Stratford JA, Waterhcuse, & Vogt NB (1989) OrganiC contaminants i n Welsh soils: pclynuclear aromatic hydrocarbons. Environ Sci Technol, 23(5): 540-550.
Jongeneelen FJ, Scheepers PTJ, Groenendi j k A, Van Aerts LAGJM, Anzim RBM, Bos RP, & Veenstra SJ (1988) Airborne cmcentrations, skin contamination, and urinary metabolite excretion of polycyclic aromatic hydrocarbons among paving workers expcsed t o coal tar derived road tars. Am Ind Hyg Assoc J, 49( 12): 600-607.
Karcher W ed. (1988) Spectral at las of polycycl i c aromatic mpounds, Vol. 2. Dordrecht, The Netherlands, Kluwer Acadernic Publishers f0r the Commission o f the European Ccinmunities.
Karcher W, Fordham RJ, Dubois JJ, Glaude FGJM, & Ligthart JAM eds. (1 985) Spectral at las of p01 ycycl i C aromat i c mpainds. Dordrecht,
Holland, D. Reidel FUblishing Coinpany for the Connissim of th. European Connuni t i es . Karcher W, Devillers J, Garrigues ph, 6 jacob J e&. (1991 ) Spectral atlas of p o l ~ c ~ c l i c aroniatic canpowids, vol. 3. Dordrecht, The Netherlands, Kluwer Academic Wblishers for the Conniission of the European CoiAimxii ties.
Karickhoff SW, Bram DS, 6 scott TA (1979) Sorptim of hydrophobic poi lutants on natura1 sediments. Water Resesrch, 13: 241-248.
Keller CD 6 Bidleman TF (1984) Collection of airborne polycyclic armatic hydrocarbons and other organics w i th a glass fiber f i l t e r - p01 yurethane foeni systm. Atmos Envi ron, 18(4) : 837-845.
Kicinski ffi, Adamek S. 6 Kettrup A (1989) Trace mrictutent cind analYSis Of WlyCycl i c armatic hydrocarbons i n envi romiental sainples, using sol id phase extraction i n connection with WfiIS diode-array tluorescence detection. Chromatographia, 28(3/4): 203-208.
Klug A (1950) The crystal and niolecular structure of triphenyl-, C t i H i z . Acta Cryst, 3: 165-175.
Knecht U, Elliehausen H-J, 6 bitwitz H-J (1988) (hseais Md adsorbed PAH i n an im foundry. B r i t J Ind W, 43: 834-838.
Krmberger H 6 Weiss J (1944) Forrnatim and structure of some or9anjc nioieCUìar canpowids. Part 111. The dielectr ic polarisation of some sol id crystall ine niolecular canrpamds. J chm Soc, 148: 484-469.
Kruber O (1937) Uber einige neue B e s t ~ d t e i l e des Steinkohlenteer-hs [m new GC+lStituents of coal tar pitch]. Berichte D e ~ t ~ C h m ChenisCherì Ges, 70(7): 1556-1564 ( i n f&nan).
Kruber O 6 Grigoleit G (1954) iJber neue stoffe des Steinkohlenteep Pechs [New ccinpounds isolated fm -1 tar pitch]. Chm Ber, 87(12): 1895-1905 ( i n Gernwi).
Kruber O 6 Marx A (1938) Bei trage zur Kmntnis des Anthracenols des Steinkohlenteers [The anthracene o i l of -1 tar]. Berichte Deutschen Chemischen Ges, 71 (12): 2478-2484 ( i n Oerinan).
Lmgenfeld JL, Hwthorne SB. M i l l e r DJ, 6 Pawliszyn J (1993) Effects of temperature end pressure m supercritica1 f l u i d extraction e f f icencies O f poi ycycl i c ar-tic hydrocarbons d p01 ychlorinated biphenyls. h a 1 Chm, 65(4) : 338-344.
Lao RC, Thunas RS, Oja H, & Cubois L (1973) Appiication of a gas chrunatograph-niass spectrcnieter-data processar combination t0 the analysis of the polycyclic a m a t i c hydrocarbon mtent of airbome pollutants. Anal Chem, &(e): 908-915.
Lee FS-C 8 Schuetzle D (1983) Sampling, extraction, and analysis of polycyclic aromatic hydrocarbons f m interna1 ccinbustion engines. In: Bjorseth A ed. Handbook of polycyclic armatic hydrocarbs. New York, Marce1 Dekker, Inc, pp 27-94.
Lee --C. Harvey TM, Prater TJ, Paputa MC, 8 Schuetzle D (1980) Chemical analysis of diesel particulate matter and an evaluation of ar t i fact formation. In: Sampling and analysis of toxic organics i n the atmosphere. Philadelphia. Pa., h r i c a n Cociety for Testing and Materials. p(, 92-110 (ASTM STP 721 ).
Lee ML, Novotny M, & Bartle KD (1976) Gas chrmatography/mass spectrmetric and nuclear magnetic remance determination of polynuclear armatic hydrocarbons i n airborne particulates. Anal Chm, 48(11): 1566-1572.
Lee ML, bvotny UV, & Bartle KD (1981) Analytical chemistry of polycyclic armatic compcunds. New York, Academic Press.
Leinster P & Evans MJ (1986) Factors affecting the smlpling of airborne polycyclic armatic hydrocarbons - A review. Ann Occup Hyg, 30(4) 481-495.
Leo A, Hansch C, & Elkins D (1971) Parti t ion coefficients and their uses. Chem Rev, 71(6): 525-616.
Leoni V. Riccetti G. & Grella A (1975) Preliminary results on the use of Tenax for the extraction of pesticides and polycycl i c aronuitic hydrocarbs fran surface and drinking waters for analytical pirposes. J Chmatogr, 106: 119-124.
Levsen K (1988) The analysis of diesel particulate. Fresenius Z Anal Chem, 331: 467-478.
Lewis RJ, Sr (1992) W ' s dangerms properties of industria1 materials, 8th ed. New York, Van Nostrand Reinhold, v01 11.
Liao W, Smith WD, Chiang TC, & Wi l l ims LR (1988) Repid, ~W-COS~ clean-up procedure for detenination of semivolati l e organic canpwnds i n human and bovine adipose tissues. J Asxx: O f f Anal Chm. 71(4): 742-747.
Lide M (1991) CRC Handbook of chemistry and physics, 72nd ed. Boca Raton, CRC Press, Inc.
Liem AKD, Baumann RA, de Jong APJM, van der Velde H;, & van Zoonen P (1992) Analysis o f organic micropol lutants i n the l i p i d fract ion o f foodstuffs. J Chrun 624: 317-339.
Ligocki MP & Pankow JF (1989) Measurements o f the gas/particle distr ibut ions o f atrnospheric organic compounds. Environ Sci Technol, 23( 1 ) : 75-63.
Lindskog A, Brorstrth-LundBn E, Alfheim I. & Hagen I (1987) Chemical transformation o f P U I ai a i r k r n e part ic les by exposure t o NOz during sampling: a comparison between two f i l t e r media. Sci Total Environ, 61 : 51 -57.
1 Lioy PL, Waldman JM, Greenberg A, Harkov R, & Pietarinen C (1988) The to ta l human environmental exposure study (THEES) t o benzo(a)pyrene: comparicon o f the inhalation and food pathways. Arch Environ Health, 43: 304-312.
Loening KL 6 Merr i t t JE (1990) Some aids fo r naming polycyclic a rmat ic hydrocarbons and the i r heterocyclic analogs. In: Loening K, Merr i t t J, Later D, & Wright W. Polynuclear aromatic hydrocarbons - Nomenclature guide. 1st ed. Columbus, Ohio, Bat te l le Press, pp 1-25.
Mackay D & Shiu WY (1977) Aqueous so lub i l i t y o f polynuclear aromatic hydrocarbons. J Chem Eng Data, 22(4): 399-402.
Mackay D 6 Shiu WY (1981 ) A c r i t i c a l r e v i w of Henry's lw constants fo r chemicals and enviromental intarest. J Phys Chem Ref Data, lO(4): 1175-1199.
Mackay D. Shiu WY, & Sutherland RP (1979) ùetermination o f air-water Henry's law constants for hydrophobic pollutants. Environ Sci Technol, 13( 3) : 333-337.
Marcus JM, Swearingen GA, Williams AD, 8 Heizer DD (1988) Polynuclear arunatic hydrocarbon and heavy meta1 concentrations i n sediments a t coastal South Carolina marinas. Arch Environ Contam Toxiwl , 17: 103-113.
May WE, Wasik W , & Freeman D (1978) Determination of the tiqueous so lub i l i t y o f polynuclear armat ic hydrocarbons by a coupled wlunn l i q u i d crunatographic technique. Anal Chem, 50(1): 175-179.
Means JC, Wood SG, Hassett JJ, & Banwart WL (1980) Corption o f polynuclear arunatic hydrocarbons by sediments and soi ls. Environ Sci Technol. 14(12): 1524-1528.
Menichini E (1992a) Urban a i r pol lut ion, by polycyclic a m a t i c hydrocarbons: levels and sources of variabi 1 i ty. Sci Total Envi ron, 116: 109-135.
Menichini E ed. (1992b) Opinion adopted by the Italian National Advisory Toxicological Comnittee on polycyclic armatic hydrocarbons (containing the origina1 Italian text). Roma, Istituto Superiore di SanitA (Serie Relazioni 92/41.
Menichini E, Bonanni L, 6 Merli F (1990) Determination of polycyclic aromatic hydrocarbons in mineral oils and oi1 aerosols in glass manufacturing. Toxicol Envi ron Chem, 28: 37-51.
Menichini E, di Domenico A, Bonanni L, Corradetti E, Mazzanti L, & Zucchetti G (1991) Reliability assessment of a gas chrmatographic method for polycyclic aromatic hydrocarbons in olive oil. J Chrom, 555: 211-220.
Miller M, Wasik SP, Huang GL, Shiu W, & Mackay O (1985) Relationships between octanol-water partition coefficient and aqueous solubility. Environ Sci Technol, 19(6): 522-529.
Murray JJ, Pottie RF, & Pupp C (1974) The vapor pressures and enthalpies of subl imation of f ive pol ycycl ic armatic hydrocarbons. Can J Chem, 52: 557-563.
Natusch DFS 6 Tomkins @A (1978) Isolation of polycyclic organic compounds by solvent extraction with dimethyl sulfoxide. Anal Chem, 50(11): 1429-1434.
NIOCH/OCHA (1981) Occupational health guideline for coal tar pitch volatiles. In: Mackim MI, Stricoff RS, & Partridge LJ Jr eds. Occupational health guidelines for chemical hazards, Cambridge, MA. Natimal Institute for Occupational Health and Safety - Occupational Safety and Health Administration (DHHC (NIOCH) Publ. No. 81-123; US NTIS PB83-154609, Part 1 of 3 ) .
NIOCH (1985) Polynuclear armatic hydrocarbans, Methods Nos. 5506 (HPLC) & 5515 (OC). In: Eller PM ed. NIWManual of analytical methods, 3rd ed., Cuppl. 1985, Cincinnati, Ohio, National Institute for Occupatimal Heal th and Safety (DHHC (NIOSH) Publ . No. 84-100). NACC (1983) Polycyclic aromatic hydrocarbons in the aquatic environment: formation, cources, fate and effects on aquatic biota. National Research Counci l Canada, Associate mi ttee on scienti f ic criteria for environmental quality (M332 No. 18981).
Off J Eur Comm (1980) Caincil Directive of 15 July 1980 relating t0 the quality of water intended for human consumption (80/778/EEC). Official Jcurnal of the European Communities No. L 229, 30.8.1980, pp 11-29.
Off J Eur Comm (1983) Cowicil Directive of 16 June 1983 amending Council Directive 70/220/EEC on the approximation of the laws of the Member States relating to measures to be taken against air pollution by gases from positive-ignition engines of motor vehicles
(83/351/EEC). Official Journal o f the European Conrnunities No. L 197, 20.7.1983.
Perfett i OA, Nynian PJ, Fisher C, Joe FL Jr, 6 Diachenko W (1992) Determination of polynuclear a m a t i c hydrocarbons i n seafcad by l iqu id chromatography with fluorescence detection. J W C Intern, 75(5): 872-877.
Quil l iam M4 6 Sim PG (1988) Determination of polycyclic aromatic compounds by high-performance l iqu id chromatography with simultaneous mass spectrometry and ultraviolet diode array detection. J Chromatogr Sci, 28: 160-167.
Ruepert C, Grinwis A, 6 Oovers H (1985) Prediction of part i t ion coefficients of unsubstituted polycyclic arcinatic hydrocarbons frun Ci 8 chrunatographic and structural properties. Chemocphere, 14(3/4): 279-291.
Saber A, Jarosz J, Martin-Bouyer M, Paturel L, 6 Via1 M (1987) Analysis of polycyclic aranatic hydrocarbons i n lacustral sediments by high resolution Shpol 'sk i i spectrofluorimetry at 10 K. Intern J Environ Anal Chem, 28: 171-184.
Santodonato J, Howard P, 6 Basu D (1981) Health and ecologica1 assessment of polynuclear arunatic hydrocarbons. J Environ Pathol Toxicol, 5(l): 1-364.
Schuetzle D (1983) Sampling of vehicle emissions for chmical ~ a l y s i s and biologica1 testing. Environ Health Perspect, 47: 65-80.
Schuyer J, Blom L, & Van Krevelen OW (1953) The molar refraction of condensed aromatic compounds. Trans Faraday Soc. 49: 1391-1401.
Schwarz FP (1977) Detennination of temperature dependence of solubi l i t ies of polycyclic arunatic hydrocarbons in aqueous solutions by a fluorescence method. J Chem Eng Data, 22(3): 273-277.
SFT-SNT (1992) Reurnmendations fra the Workshop on PAH. In: Proceedings of the Workshop on Polyaromatic Hydrocarbons (PAH), Oslo, 11-13 Noveniber 1991. Oslo, State Pollution COntrOl Authority (Si) and Norwegian Fcad Contro1 Authority (W). pp 4-23 (TA-816/1992).
Sims RC 6 Cvercash (1983) Fate of polynuclear aromatic coiyxxinds (PNAs) i n soi l plant systems. Residue Reviews, 88: 1-88.
Ynith W, Tanaka J, Futorna DJ, Snith TE (1981) Sawling and premcentration methods for the analysis of polycyclic arcmatic hydrocarbons i n water systems. CRC C r i t Rev Anal Chem, lO(1): 375-425.
Sonnefeld WJ, Zoller W, 6 May WE (1983) Dynmic coupled-colum l iqu id chroinatographic detenination of ambient temperature vapor pressures of polynuclear aromatic hydrocarbons. Anal Chem, 55: 275-280.
Sortland Olufsen B 6 Bjorseth A (1983) Analysis o f polycyclic aranatic hydrocarbons by gas chranatography. In: Bjorseth A ed. Handbook of polycyclic aromatic hydrocarbons. New York, Marcel Dekker, Inc, pp 257-300.
Spitzer T & Dannecker W (1983) Membrane f i l t e r s 8s adsorbents for polycyclic aromatic hydrocarbons during high-volume sampling of a i r part iculate matter. Anal Chem, 55: 2226-2228.
Spitzer T & Kwatsuka S (1986) Simple method for determination of polynuclear aromatic hydrocarbons i n so i l by clean-up on XAD.2. J Chromatogr, 358: 434-437
Stenberg UR (1985) PAH emissions fran automobiles. In: Bjorseth A & Ramdahl T eds. Handbook of polycycl i c aromatic hydrocarbons, Vol 2. New York. Marcel Dekker, Inc, pp 87-111.
Stenberg U, Alsberg T, & Westerholm R (1983) Appl icabi l i ty of a cryogradient technique for the enrichment o f PAH frm autunobile exhausts: demst ra t ion o f methodology and evaluation experiments. Environ Health Perspect, 47: 43-51
S t w t P & Meinantw G (1989) Recent advances in infrared analysis of polycyclic aromatic ccinpounds. In: Vo-Dinh T ed. Chemical analysis o f polycyclic aranetic conipwnds. New York, John Wiley L% Sons. pp 41 1-432.
Ten Hulscher ThEM, Van Der Velde LE, & Bruggman WA (1992) Temperature dependence of Henry' s l w s t a n t s fo r selected chlorobenzenes, polychlorinated biphenyls and polycyclic aromatic hydrocarbons. Environ Toxicol Chem, 11: 1595-1603.
Thrane KE 6 Mikalsen A (1981 ) High-volune sampl ing o f airborne polycyclic aromatic hydrocarbons using glass f ib re f i l t e r s and p01 yurethane f w . Atrnos Envi ron. 15(6 1: 909-918.
US W (1990) Toxicological p r o f i l e fo r polycyclic aranetic hydrocarbons. US Oepartment o f Health & Huaan Services, Public Health Service, Agency for Toxic Cubstances and Disease Registry (TP-90-20).
US EPA (1980) Ainbient water qual i ty c r i t e r i a for polymiclear aranatic hydrocarbons. Washington, DC, US Envi romiental Protect ion Agency ( EPA 440/5-80-069 1.
US EPA (1984) Guidelines Establishing Test Procedures for the Analysis of Pollutants Under the Clean Water Act. Method 610-Polynuclear Aromatic Hydrocarbons. In: US Federa1 Register, Vol 49, No 209. October 26, 1984, pp 43344-43352.
US EPA (1986a) ( I ) Method 3510 'Separatory funnel l iquid- l iquid extraction'; (11) Method 3520 'Continuow 1 iquid-liquid extraction' ; (111) Method 3630 'S i l i ca gel cleanup'; ( IV) MetW 8100 'Polynuclear
arunatic hydrocarbons'; (V) Method 8270 'Gas chrunatography/mass spectrometry f O r semivolatile organics: capil lary colunn technique'; (VI) Method 8310 'Polynuclear aromatic hydrocarbons'. In: Test methods for evaluating sol id waste, 3rd ed, Vol 10. Washington, DC, US Envi r m t a l Protection Agency (EPA-W-846).
US EPA (1986b) ( I ) Method 3540 'Coxhlet extraction'; (11) Method 3550 'Sonication extraction'; (111) Method 3630 'Si l ica gel cleanup'; (IV) Method 8100 'Polynuclear aromatic hydrocarbons'; (V) Method 8270 'Gas chromatography/mass spectranetry for semivolati l e organics: capi l lary wlumn technique'; (VI) Method 8310 'Polynuclear arunatic hydrocarbons' . In: Test methods for evaluating sol i d waste, 3rd ed, Vol IB. Washington, DC, US Envirmental Protection Agency (EPA- W-846).
US EPA (1986~) ( I ) Method 0010 'Modified method 5 sampling train'; (11) Method 0020 ' W r c e assessment sampling system (U9CC)'. In: Test methods for evaluating sol i d waste, 3rd ed, Vol 11. Washington, DC, US Environmental Protection Agency (EPA--846).
US EPA (1987) Appendix J-Reference Method for the Determination of Part iai late Matter as PMio i n the Atmosphere. In: US Federa1 Register, Vol 52, No 126, July 1, 1987, pp 24864-24666.
US EPA (1992) Protection of the e n v i r m t , Chapter l - E n v i m t a l Protection Agency, Part 86, Sections 86-109, 86-110. US Code Fed Regul, T i t l e 40, Parts 86 to 99, Revised as of July 1, 1992, pp 377-41 O.
Vaessen W, Jekel AA, & Wilbers AAMM (1988) Dietary intake of polycyclic aromatic hydrocarbons. Tox Environ Chem, 16: 281-294.
Valerio F, Bottino P. Ugolini D, Cimberle F R , Tozzi Cd & Frigerio A (1984) Chemical and photochemical degradation of polycycl i c arunatic hydrocarbons i n the atmosphere. Sci Total Environ, 40: 169-188
Valerio F, Brescianini C, Pala M, Lazzarotto A, Balducci D, IL Fontana V (1992) Wrces and atmospheric concentrations of polycyclic arunatic hydrocarbons and heavy metals i n two I ta l ian tcniuns (Genoa and La Spezia). Sci Total Environ, 114: 45-57. -
Van Noort PCM & Wondergem E (1985) The icolation of some polymtclear aromatic hydrocarbons frun aquews samples by means of reverse6phase concentrator columns. Anal Chim Acta. 172: 335-340.
Van Vaeck L, Van Cauwanberghe K, & Janssens (1984) The gas-particle distr ibution of organic aerosol mst i tuents : measurement of the volat i l isat ion artefact i n hi-v01 cascade impactor sampling. At- Environ, 18(2): 417-430.
VOI (1989) Emission measurement. Measurement of polycyclic aromatic hydrocarbons (PAH). Measurement of PAH i n the exhaust gas frun
gasoline and diesel engines o f passenger cars - gas chrunatographic determination. hisseldorf. Germsny, Verein Deutscher Ingenieure - Kcnmission Reinhaltung der Luft (VDI 3872, Part 1).
Verschueren K (1983) Hmdbook of e n v i r m t a l data on organic chemicals, 2nd ed. New York, Van Nostrand Reinhold Company.
Vo-Dinh T ed. (1989) Chmical analysis of polycyclic armat ic ccmpowids. New York, John Wiley & Sons.
Vo-Dinh T, Bruewer TJ, Colovos GC, Wagner TJ, & Jungers RH (1984) F ie ld evaluation o f a wst-effect ive screening procedure for polynuclear aromatic pollutants i n ambient a i r samples. Envirwr Sci Technol , 18(6): 477-482.
Vogt NB, Brakstad F, Thrane K, Nordenson S, Krane J, Aainot E, Kolset K, Esbensen K, (L Steinnes E (1987) Polycyclic armat ic hydrocarbons i n so i l and a i r : s tat is t ica1 analysis and c lassi f icat ion by the SIMCA method. Environ Sci Technol, 21(1): 35-44.
Von Boente L (1955) Bei trag zur Chemie des Coronens [Role o f coronene i n the products o f high-preswre hydrogenationl Brennstoff-Chemie, 36(13/14): 210-214 ( i n German).
Vreuls JJ, De Jong GJ, & Brinknwi UATh (1991) Cn-line coupling o f l i qu id chrmatography, capi l lary gas chmtography and mass spectrornetry for the determination and ident i f icat ion o f polycyclic armat ic hydrocarbons i n vegetable o i l s . Chrmatographia, 31(3/4): 113-118.
Warman K (1985) PAH emissions frm coal-fired plants. In: Bjorseth A & Ramdahl T eds. Handbook of polycyclic armat ic hydrocarbons, Vol 2. New York, Marcel Dekker, Inc, pp 21-59.
Wehry EL (1983) Optical spectrmetric techniques for determination of polycycl i c armat ic hydrocarbons. In: Bjorseth A ed. Handbook of polycyclic armat ic hydrocarbons. New York, Marcel Dekker, Inc, W 323-396.
Wenclawiak 8, Rathmann, & Teuber A (1992) Supercrit ical-f luid extraction o f so i l samples and determinaticm of polycyclic armat ic hydrocarbons (PAHs) by HPLC. Fresenius J Anal Chem, 344: 497-500.
White CM (1986) Prediction of the boi l ing point, heat of vaporization, and vapor pressure at var ia is temperatures for polycyclic armat ic hydrocarbons. J Chm Eng Data, 31: 198-203.
White JG (1948) The crystal strutture of 1:12-benzperylene: a quantitatve X-ray investigation. J Chem Soc, 1398-1408.
WHO (1971) Internat imal standards for drinking water, 3rd ed. Oeneva, World M a l t h Organization.
WHO (1984) Guidelines for d r i nk inma te r quality, ( I ) Vol. 1 - Recomiendations, pp 66-68, (11) Vol. 2 - Health c r i t e r i a and other supporting information, pp 185-186. Geneva. World Health Organization.
Winberry Wi Jr, Forehand L, Wrphy M, Ceroli A, Phinney 8, 8 EVMS A (1990) Method I?-7 'Determination o f benzo(a)pyrene [B(a)Pl and other polynuclear arunatic hydrocarbons (PAHs) i n indoor a i . In: Cunpendiun, o f methods for the determination o f a i r pollutants i n indoor a i r . Research Triangle Park, W , US Enviroivnental Protection Agency, pp 552-639 (EPA/600/4-%/O1 O; US M I S -90-200288).
Wise SA (1983) High-performance l iquid chrunatography for the determination of polycyclic armat ic hydrocarbons. In: Bjorseth A ed. Handbook of polycyclic aromatic hydrocarbons. New York, Marcel Dekker. Inc. pp 183-256.
Wise SA (1985) Recent progress i n the determination o f PAH by high performance l i qu id chrmatography. In: Bjorseth A & Ramdahl T eds. Handbook of polycyclic armat ic hydrocarbons, Vol 2. New York, Marcel Dekker, Inc, pp 113-191.
Wise SA, Bonnett WJ, & May WE (1980) Nomal- and reverse-phase l i qu id chromatographic separations o f polycyclic armat ic hydrocarbons. In: Bjorseth A & Dennis AJ eds. Polynuclear arunatic hydrocarbons: chemistry and biologica1 effects. Colurnbus, Ohio, Bat te l le Press. pp 791-806.
Wise SA, Bonnett WJ, Guenther FR. & May WE (1981) A relationship between reversed-phase C18 l iqu id cranatographic retention ami the shape of polycyclic aromatic hydrocarbons. J Chromatogr Sci, 19: 457-465.
Wright BW & Smith W) (1989) Capil lary supercrit ical f l u i d chrunatography methods. In: Vo-Dinh T ed. Chemical analysis of polycyclic armat ic compounds. New York, John Wiley (L Sons, pp 111-149.
Yalkavsky Sii & Valvani SC (1979) Solub i l i t ies and part i t ioning 2. Relationships between aqueous solubi l i t ies. par t i t i on coefficients, and nmlecular surface areas o f r i g i d aromatic hydrocarbons. J Chem Eng Data. 24(2): 127-129.
Yamasaki H, Kwata K, & Miyamoto H (1982) Effects of ambient tempera- ture on aspects o f airborne polycyclic aromt ic hydrocarbcns. Environ Sci Technol, 16(4): 189-194.
Direiiore reggente dell'lsrifuto Superiore di Sanità e Responsabile scieniifico: Giuseppe Vicari
Direaore responsabile: V i l m Alberuni
Sramparo dal Servizio per le orrivird editoriali dell'lsriruio Superiore di Sanild, Viale Regim 1:leno. 299 - 00161 ROMA
La riproduzione parziale o rorole dei Rapporti e Congressi ISTISAN deve essere prevenrivamenre oiitorizzota.
Reg. Stampa - Tribunale di Roma n. 131/Nl del Io m r z o 1988
Roma, giugno 1994 in. 2) l' Suppl,
Lo responsabiliid &i dai scientifici e iecnici pubblic011' nei Rapporri e Congr*isi ISTISAN I! &i singoli autori
