The August 2007 ISPAC newsletter
This newsletter is for the benefit of ISPAC members. If you have information to share, such as
your newest publications, a source of standards, news of new books, etc., please pass them
along for including in the next issue.
The ISPAC webpages are at http://www.ispac.org/
ISPAC membership inquiries or refer potential members to either:
Treasurer, Jocelyne Hellou
HellouJ@mar.dfo-mpo.gc.ca
Secretary, Dianne Poster
poster@nist.gov
Information on the Journal Polycyclic Aromatic Compounds will be found at:
http://www.tandf.co.uk/journals/titles/10406638.html
For other inquiries, including volunteering to be a reviewer, contact Philippe Garrigues at
p.garrigues@lptc.u-bordeaux1.fr
Dr. Tim Roy sent a link to his latest PAH article:
http://www.ncbi.nlm.nih.gov/sites/entrez?Db=pubmed&Cmd=ShowDetailView&TermToSearch=1
7503280&ordinalpos=1&itool=EntrezSystem2.PEntrez.Pubmed.Pubmed_ResultsPanel.Pubmed_R
VDocSum
Literature search results:
JA Andresen, D Muir, D Ueno, C Darling, N Theobald, K Bester
Emerging pollutants in the north sea in comparison to Lake Ontario, Canada, data
Environmental Toxicology and Chemistry, 2007, Vol 26, Iss 6, pp 1081-1089
In the present study, the concentrations and fate of contaminants such as organophosphate
flame retardants and plasticizers, musk compounds such as galaxolide (HHCB), tonalide (AHTN),
musk ketone and musk xylene, the bactericide triclosan, as well as the metabolites HHCB-lactone
and triclosan-methyl were compared in the aqueous phase of the German Bight (North Sea). The
concentrations of these compounds were around 1 to 10 ng/L in nearshore areas, and the
concentrations were lower in the more pristine areas. The highest concentrations were
determined for tris-(2-chloro-isopropyl) phosphate in the North Sea with concentration exceeding
10 ng/L even for the offshore samples. The samples contained 1 to 20 ng/L chlorinated
organophosphates, approximately 1 ng/L nonchlorinated organophosphates, and 0.3 to 3 ng/L
fragrance compounds. Some samples from Lake Ontario (Canada) were analyzed in comparison.
Per capita emissions were calculated for both regions. These emissions were compared and
turned out to be very similar for the Canadian and German locations. For the North Sea, some
observations concerning stability, dilution, and degradation, as well as sources of the respective
substances, were performed. These data indicate that the chlorinated organophosphates and
some musk fragrances exhibit half lives exceeding the residence times and thus can be
considered to be persistent in this ecosystem. In the German Bight, the river Elbe is the
dominating source for the more hydrophilic compounds, such as chlorinated organophosphate
flame retardants, which are diluted only into the North Sea. However, for the more lipophilic
compounds such as the musk fragrances, different input patterns as well as distribution patterns
are relevant, though the river Elbe is still a major source of pollution to the German Bight of the
North Sea. The data seem to indicate either relevant inputs further west of the sampling area or
mobilization from the sediments.
VH Teixeira, S Casal, MBPP Oliveira
PAHs content in sunflower, soybean and virgin olive oils: Evaluation in commercial samples and
during refining process
Food Chemistry, 2007, Vol 104, Iss 1, pp 106-112
PAHs are environmental carcinogenic compounds that may contaminate vegetable oils and their
levels can be reduced by refining. In order to understand the influence of the refining steps, the
content of 15 PAHs was assessed throughout alkaline refining in soybean, sunflower and olive oil
samples. Eight commercial brands of these oils were also analysed. The analytical method
involved a liquid-liquid extraction, a solid-phase clean up (C-18 and Florisil) followed by RP-HPLC
with fluorimetric detection. The total PAHs content in the studied samples can be considered
generally low. The light PAHs (2-4 rings) were predominant. Virgin olive oils showed the highest
values (max. 26 mu g/kg). An evident decrease of PAHs contents during alkaline refining was
observed (71%, 88% and 85% in sunflower, soybean and olive oils, respectively) being more
pronounced in light PAHs. Neutralization and, particularly, deodorization were the more effective
steps contributing to the PAHs decrease. Bleaching was responsible for a slight increase in the
PAHs content in soybean and olive oils.
D Lapole, G Rychen, N Grova, F Monteau, B LeBizec, C Feidt
Milk and urine excretion of polycyclic aromatic hydrocarbons and their hydroxylated metabolites
after a single oral administration in ruminants
Journal of Dairy Science, 2007, Vol 90, Iss 6, pp 2624-2629
The aim of this study was to establish the transfer of phenanthrene, pyrene, and benzo[a] pyrene
and their major hydroxylated metabolites to milk and to urine after a single oral administration
(100 mg per animal of each compound) in 4 lactating goats. Detection and identification of the
analytes (native compounds, 1-OH pyrene, 3-OH phenanthrene, 3-OH benzo[a]pyrene) were
achieved using gas chromatography-mass spectrometry. Benzo[a] pyrene, phenanthrene, and
pyrene were rapidly detected in the plasma stream, whereas 1-OH pyrene and 3-OH
phenanthrene appeared later in plasma. These data suggest that pyrene and phenanthrene are
progressively metabolized within the organism. Recovery rates of pyrene and phenanthrene in
milk over a 24-h period appeared to be very low (0.014 and 0.006%, respectively), whereas the
transfer rates of their corresponding metabolites were significantly higher: 0.44% for 1-OH pyrene
and 0.073% for 3-OH phenanthrene. Recovery rates in urine were found to be higher (1 to 10
times) than recovery rates in milk. The 1-OH pyrene was found to be the main metabolite in urine
as well as in milk. Thus, as has been established for humans, 1-OH pyrene could be considered
as a marker of ruminant exposure to PAHs. Because 1-OH pyrene and 3-OH phenanthrene were
measured in milk (unlike their corresponding native molecules), metabolites of PAHs should be
taken into consideration when evaluating the safety of milk. Benzo[a] pyrene and 3-OH benzo[a]
pyrene were (less than 0.005%) transferred to milk and urine in very slight amounts. This very
limited transfer rate of both compounds suggests a low risk of exposure by humans to benzo[a]
pyrene or its major metabolite from milk or milk products.
MD Guillen, G Palencia, P Sopelana, ML Ibargoitia
Occurrence of polycyclic aromatic hydrocarbons in artisanal palmero cheese smoked with two
types of vegetable matter
Journal of Dairy Science, 2007, Vol 90, Iss 6, pp 2717-2725
Palmero cheese is a fresh smoked cheese from the Isle of Palma (Canary Islands), manufactured
with goat's milk. To guarantee its safety, the occurrence of PAHs in artisanal Palmero cheese
smoked with 2 types of vegetable matter (almond shells and dry prickly pear) was studied. The
determination of PAH includes extraction and clean-up steps, followed by separation,
identification, and quantification of PAH by gas chromatography-mass spectrometry in selected
ion-monitoring mode. The most abundant PAH are those with 2 and 3 aromatic rings. Although
the highest total PAH concentrations corresponded to the cheeses smoked with almond shells,
the degree of PAH contamination of the cheeses studied was lower than that found in other
cheeses smoked in the traditional way. The nature of the vegetable material used for smoking
seemed to have an influence on the type of PAH formed, especially on alkylderivatives and some
light PAH. However, despite the artisanal, and consequently variable, production process of these
cheeses, many similarities have been found among their PAH profiles. In fact, relatively constant
relationships are observed between the concentrations of certain pairs of PAH. Benzo(a) pyrene
was only present in 2 samples, and in much lower concentrations than the maximum allowed
legal limits. Therefore, according to the results obtained, it appears that it is possible to obtain a
safe product without renouncing the artisanal character or the sensory properties of this type of
cheese.
JP Hutchinson, L Setkova, J Pawliszyn
Automation of solid-phase microextraction on a 96-well plate format
Journal of Chromatography A, 2007, Vol 1149, Iss 2, pp 127-137
Studies have been performed assessing the feasibility and characterizing the automation of solidphase microextraction (SPME) on a multi-well plate format. Four PAHs, naphthalene, fluorene,
anthracene and fluoranthene, were chosen as test analytes to demonstrate the technique due to
their favorable partition coefficients, K-fw between polydimethylsiloxane (PDMS) extraction
phases and water. Four different PDMS configurations were investigated regarding their
suitability. These included (i) a PDMS membrane; (ii) a multi-fiber device containing lengths of
PDMS-coated flexible wire; (iii) a stainless steel pin covered with silicone hollow fiber membrane
and (iv) commercial PDMS-coated flexible metal fiber assemblies. Of these configurations, the
stainless steel pin covered with silicone tubing was chosen as a robust alternative. An array of 96
SPME devices that can be placed simultaneously into a 96-well plate was constructed to
demonstrate the high-throughput potential when performing multiple microextractions in parallel.
Different agitation methods were assessed including magnetic stirring, sonication, and orbital
shaking at different speeds. Orbital shaking whilst holding the SPME device in a stationary
position provided the optimum agitation conditions for liquid SPME. Once the analytes had been
extracted, desorption of the analytes into an appropriate solvent was investigated. Liquidphase
SPME and solvent desorption on the multi-well plate format is shown to be a viable alternative for
automated high-throughput SPME analysis compatible with both gas- and liquid-chromatography
platforms.
B Veyrand, A Brosseaud, L Sarcher, V Varlet, F Monteau, P Marchand, F Andre, B LeBizec
Innovative method for determination of 19 polycyclic aromatic hydrocarbons in food and oil
samples using gas chromatography coupled to tandem mass spectrometry based on an isotope
dilution approach
Journal of Chromatography A, 2007, Vol 1149, Iss 2, pp 333-344
An efficient and selective analytical method for the detennination and the quantification of 19
PAHs in food and oil has been developed. This method includes the monitoring of 15 PAHs
stated as a priority by the EU in their 2005/108 recommendation. The samples were extracted
according to a selective extraction step using pressurized liquid extraction followed by a
purification with polystyrenedivinylbenzene SPE. Identification and quantification were performed
using GC-MS/MS, with an isotope dilution approach using C-13-labelled PAHs. The novel
combination of selective extraction followed by purification provides highly purified analytes
combined to a fast and automated method. The advantages of GC-MS/MS as compared to other
detection methods are tremendous in terms of sensitivity, selectivity and interpretation facilities.
Limits of detection varied between 0.008 and 0.15 mu g kg(-1) limits of quantification between
0.025 and 0.915 mu g kg(-1) for PAHs in food. The calibration curves showed a good linearity for
all PAHs (R-2 > 0.99) and precision and recovery were fit for purpose. Trueness of the method
was carried out using the US National Institute of Standards and Technology SRM 2977
reference material.
R Singh, B Kaur, I Kalina, TA Popov, T Georgieva, S Garte, B Binkova, RJ Sram, E Taioli, PB
Farmer
Effects of environmental air pollution on endogenous oxidative DNA damage in humans
Mutation Research - Fundamental and Molecular Mechanisms of Mutagenesis, 2007, 620, pp 7182
Epidemiological studies conducted in metropolitan areas have demonstrated that exposure to
environmental air pollution is associated with increases in mortality. Carcinogenic polycyclic
aromatic hydrocarbons (c-PAHs) are the major source of genotoxic activities of organic mixtures
associated with respirable particulate matter, which is a constituent of environmental air pollution.
In this study,we wanted to evaluate the relationship between exposure to these genotoxic
compounds present in the air and endogenous oxidative DNA damage in three different human
populations exposed to varying levels of environmental air pollution. As measures of oxidative
DNA damage we have determined 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodG) by liquid
chromatography-tandem mass spectrometry (LC-MS/MS) and cyclic pyrimidopurinone N-1,N-2
malondialdehyde-2'-deoxyguanosine (M(1)dG) by the immunoslot blot assay from lymphocyte
DNA of participating individuals. The level of endogenous oxidative DNA damage was
significantly increased in individuals exposed to environmental air pollution compared to
unexposed individuals from Kosice (8-oxodG adducts) and Sofia (M(1)dG adducts). However,
there was no significant difference in the level of endogenous oxidative DNA and exposure to
environmental air pollution in individuals from Prague (8-oxodG and M(1)dG adducts) and Kosice
(M(1)dG adducts). The average level of M(1)dG adducts was significantly lower in unexposed
and exposed individuals from Kosice compared to those from Prague and Sofia. The average
level of 8-oxodG adducts was significantly higher in unexposed and exposed individuals from
Kosice compared to those from Prague. A significant increasing trend according to the interaction
of c-PAHs exposure and smoking status was observed in levels of 8-oxodG adducts in individuals
from Kosice. However, no other relationship was observed for M(1)dG and 8-oxodG adduct levels
with regard to the smoking status and c-PAH exposure status of the individuals. The conclusion
that can be made from this study is that environmental air pollution may alter the endogenous
oxidative DNA damage levels in humans but the effect appears to be related to the country where
the individuals reside. Genetic polymorphisms of the genes involved in metabolism and
detoxification and also differences in the DNA repair capacity and antioxidant status of the
individuals could be possible explanations for the variation observed in the level of endogenous
oxidative DNA damage for the different populations.
LG Shields, DT Suess, KA Prather
Determination of single particle mass spectral signatures from heavy-duty diesel vehicle
emissions for PM2.5 source apportionment
Atmospheric Environment, 2007, Vol 41, Iss 18, pp 3841-3852
The size and chemical composition of individual diesel exhaust particles were measured in order
to determine unique mass spectral signatures that can be used to identify particle sources in
future ambient studies. The exhaust emissions from seven in-use heavy-duty diesel vehicles
(HDDVs) operating on a chassis dynamometer were passed through a dilution tunnel and
residence chamber and analyzed in real time by aerosol time-of-flight mass spectrometry
(ATOFMS). Seven distinct particle types describe the majority of particles emitted by HDDVs and
were emitted by all seven vehicles. The dominant chemical types originated from unburned
lubricant oil, and the contributions of the various types varied with particle size and driving
conditions. A comparison of light-duty vehicle (LDV) exhaust particles with the HDDV signatures
provide insight into the challenges associated with developing an accurate source apportionment
technique and possible ways of how they may be overcome. (c) 2007 Published by Elsevier Ltd.
T Oliveira, C Pio, C Alves, A Silvestre, M Evtyugina, J Afonso, A Caseiro, M Legrand
Air quality and organic compounds in aerosols from a coastal rural area in the Western Iberian
Peninsula over a year long period: Characterisation, loads and seasonal trends
Atmospheric Environment, 2007, Vol 41, Iss 17, pp 3631-3643
Ambient samples of fine organic aerosol collected from a rural area (Moitinhos) in the vicinity of
the small coastal Portuguese city of Aveiro over a period of more than one year have been
solvent-extracted and quantitatively characterised by gas chromatography-mass spectrometry.
Particles were also analysed with a thermal-optical technique in order to determine their
elemental and organic carbon content. In addition, meteorological sensors and real-time black
carbon, ozone and carbon monoxide monitors were used. Particulate matter values were higher
than background levels in continental Europe. A patent seasonal variation for organic and
elemental carbon concentrations was observed, presumably related to stronger local primary
emissions and to limited vertical dispersion. The higher levels were most likely a result of
residential wood burning, since black carbon and carbon monoxide maximised during late
evening hours in wintertime. Of the bulk of elutable organics, more than a half, on average, was
present as acidic fraction. Alcohols, aliphatic and polyaromatic hydrocarbons represented
together, more than 30% of the elutable mass, also showing a marked seasonal pattern with a
minimum in summer and a maximum in winter. The winter increase was more evident for resinic
acids, phytosterols, n-alkanoic acids and polycyclic aromatic hydrocarbons.
RP Philp
The emergence of stable isotopes in environmental and forensic geochemistry studies: a review
Environmental Chemistry Letters, 2007, Vol 5, Iss 2, pp 57-66
In the past decade, environmental forensics has emerged as a discipline directed toward
determining parties liable for causing spills of contaminants into the environment. Such
investigations, while geared toward determining the guilty parties in order to recover costs of the
cleanup and remediation, require various questions to be addressed. These include
determination of the nature of the product; Where did it come from?; Extent of weathering, if any;
How long has it been there?; and Is it degrading naturally? Traditionally, these studies have been
addressed through utilization of techniques such as gas chromatography (GC) and gas
chromatography-mass spectrometry (GCMS). However, in recent years, stable isotopes, primarily
determined through the use of combined gas chromatography-isotope ratio mass spectrometry
(GCIRMS), have emerged as an equally important tool in environmental forensics. For relatively
low molecular, volatile compounds such as MTBE, BTEX, or chlorinated solvents, the isotopes,
primarily carbon and hydrogen, have been used extensively for evaluating the onset of natural
attenuation. For larger molecules such as PCBs or PAHs, in which the effects of biodegradation
on the isotope composition of these molecules is minimal, the isotopic fingerprints of the
individual compounds can be used for correlation purposes. In this paper, a brief introduction to
isotope geochemistry will be given, followed by a review of applications of stable isotopes to a
variety of environmental problems. While the review may not necessarily be exhaustive, it will
provide a comprehensive overview of areas where isotopes have been used and potential
applications for the future. Most of the review is concerned with carbon and hydrogen isotopes,
although a brief overview of the emerging area of chlorine isotopes will also be discussed.
MD Casal, MA Diez, R Alvarez, C Barriocanal
Suitability of Gray-King pyrolysis to evaluate coking pressure
Journal of Analytical and Applied Pyrolysis, 2007, Vol 79, Iss 1-2, pp 161-168
Two coals of different rank and coking pressure characteristics together with a blend containing
50 wt% of each coal were employed for this study. High-temperature carbonizations in a movable
wall oven of 250 kg capacity were carried out to assess the degree of dangerousness during
coking. At the same time, the gas evolved during the process was condensed. In order to obtain
the different layers that are formed during coking, partially coked charges were recovered from
the oven. The central part of the charge was treated with organic solvents. Moreover, primary tar
generated from the two coals and the blend was obtained by means of a Gray-King apparatus.
The extract of the partially coked coal together with the high-temperature and the primary tars
were studied by means of gas and liquid chromatography. It was found that the composition of
the extract was similar to that of the primary tar, its composition depending on the coking
pressure characteristics of the coals tested. By contrast, the high-temperature tar is similar for the
coals and blend tested in the present work regardless of their rank or coking pressure
characteristics.
CK Huynh, TV Duc, F Deygout, P LeCoutaller, F Surmont
Identification and quantification of pah in bitumen by GC-ion-trap MS and HPLC-fluorescent
detectors
Polycyclic Aromatic Compounds, 2007, Vol 27, Iss 2, pp 107-121
Bitumen is a complex product with a large matrix of heavy aliphatic/naphthenic/aromatic
hydrocarbons as well as a large number of isomeric compounds such as PACs. Some PACs and
derivatives are known to have a mutagenic and carcinogenic activity, and there is no generally
satisfactory clean-up method for separating PACs from this very complex hydrocarbon matrix.
Moreover, from an analytical point of view, the isomeric compounds usually co-elute in the same
gas chromatography (GC) retention range, GC being one of the most widely used techniques in
this area. However, the use of a suitable clean-up procedure for isolating the aromatic fractions,
combined with two selective detection techniques such as mass spectrometry ( GC-Ion Trap MS)
and HPLC-Fluorescent detector ( HPLC-FL), is expected to provide an effective tool for
accurately determining certain PAC species in bitumen. In this paper we compare two
quantitative extractions to analyse the 16 PAHs that occur in bitumen according to the US EPA
reference list. Two clean-up protocols are assessed and compared by using both GC-Ion Trap
MS and HPLC-FL chromatographic/detection techniques. The first extraction method combines
well-established and proven clean-up operations with an automatic fractionation by semipreparative HPLC ( certification test program for PAHs in sewage sludge, in creosotecontaminated soil and in harbour sediment organised by the Community Bureau of Reference,
BCR). The second method uses a multiple step-by-step liquid/liquid and liquid/solid extraction
clean-up procedure. After the bitumen extracts are cleaned up, only the use of both GC-MS &
HPLC-FL can provide reliable results. The more sensitive FL provides enhanced fluorescent
selectivity signals that facilitate identification of PAH compounds. However, for their
quantification, the capillary GC-ion trap mass spectrometric technique is preferred because of the
insufficient resolution of the HPLC column and the possible quenching or co-elution effect of
matrix compounds. Both detection techniques are regarded as complementary.
JC Fetzer
The chemistry and analysis of large PAHs
Polycyclic Aromatic Compounds, 2007, Vol 27, Iss 2, pp 143-162
A large economic problem in petroleum processing, the plugging of catalytic hydrocracking units,
led to a study of the production of large PAHs in this process. Through that work, many other
studies of PAHs happened. These included the analysis of coal tar pitches, hydrothermal-vent
bitumens, carbon black, Diesel particulate, and fullerene soots. Many new PAHs were
synthesized or isolated during the course of these many studies.
JLP Pavon, MD Sanchez, MEF Laespada, CG Pinto, BM Cordero
Determination of naphthalene and total methylnaphthalenes in gasoline using direct injectionmass spectrometry
Talanta, 2007, Vol 72, Iss 1, pp 256-262
A high-speed determination of naphthalene and total methylnaphthalenes using a non-separative
method based on direct injection into the mass spectrometer was performed. The results
obtained for total methylnaphthalenes were very similar to those provided with fast gas
chromatography-mass spectrometry (GC-MS). However, the non-separative method afforded
higher concentrations in the determination of naphthalene than those found when fast GC-MS
was used. We propose a correction that removes this error very satisfactorily and allows the
same results to be obtained with both methodologies. The non-separative method is rapid, simple
and - in view of the results - highly suitable for the determination of naphthalene and total
methylnaphthalenes in gasoline samples.
G Pojana, A Marcomini
Determination of monohydroxylated metabolites of polycyclic aromatic hydrocarbons (OH-PAHs)
from wastewater-treatment plants
International Journal of Environmental Analytical Chemistry, 2007, Vol 87, Iss 9, pp 627-636
A high-performance liquid chromatography separation coupled with mass spectrometry via an
electrospray interface is proposed for the determination of the hydroxylated PAHs in treated and
untreated wastewaters and suspended solids from sewage treatment plants (STPs). The
developed SPE procedure was applied to spiked wastewater samples, with recovery yields (1000
mL; 100 ngL(-1) spiking level) in the 65-87% (RSD: 6-12%) range for the selected OH-PAHs. The
limits of detections ranged between 0.3 and 3.2 ng L-1, depending on the selected compound
and on the investigated matrix. The proposed method was applied to the determination of the
selected analytes in real samples from a sewage-treatment plant (STP). The investigated OHPAHs were detected mainly in the particulate fraction. The exhibited mean concentrations of
positive samples (as the sum of dissolved and particulate matter) in the STP final effluent ranged
from 15 to 68 ng L-1.
M Buratti, L Campo, S Fustinoni, C Valla, I Martinotti, PE Cirla, D Cavallo, V Foa
Application of ultraviolet spectrophotometry to estimate occupational exposure to airborne
polyaromatic compounds in asphalt pavers
Journal of Occupational and Environmental Hygiene, 2007, Vol 4, Iss 6, pp 412-419
An ultraviolet (UV) spectrophotometric procedure was devised for the determination of polycyclic
aromatic compound-oriented organic soluble matter in vapors and particulate collected from
emissions of hot asphalt mix. Ultrasonic extraction was carried out with acetonitrile, followed by
UV measurements at 254 nm. PACs in volatile and particulate fraction were quantified as
phenanthrene or benzo[k]fluoranthene equivalents. A comparison between UV and highpressure liquid chromatography with fluorescence detection showed that PACs were one to three
orders of magnitude higher than the sum of 15 priority PAHs; still, significant correlations were
found between volatile or particulate PACs and, respectively, total volatile or particulate PAHs.
Moreover, in the particulate phase, PACs correlated with total particulate matter quantified by
gravimetry. The proposed procedure was employed in a field study for monitoring personal
exposure to asphalt emissions of workers engaged in road construction. Observed levels of
acetonitrile- soluble PACs in air samples were very low (2- 20 mu g/m(3)); however, asphalt
pavers were exposed to significantly higher concentrations of volatile PACs than construction
workers (geometric mean, 5.9 mu g/m(3) vs. 4.1 mu g/m(3)). This method for estimating the
global content of volatile or particulate PACs in air samples satisfies our requirements of
simplicity and is suitable for conducting an initial screening to assess exposure to airborne
polyaromatic organics in asphalt pavers.
M Buratti, L Campo, S Fustinoni, PE Cirla, I Martinotti, D Cavallo, V Foa
Urinary hydroxylated metabolites of polycyclic aromatic hydrocarbons as biomarkers of exposure
in asphalt workers
Biomarkers, 2007, Vol 12, Iss 3, pp 221-239
Background. Fumes and vapours released during laying of hot asphalt mix have been recognised
as a major source of exposure for asphalt workers. Objectives. We investigated the relationships
between inhalation exposure to asphalt emissions and urinary biomarkers of PAHs in asphalt
workers (AW, n = 75) and in ground construction workers (CW, n = 37). Methods. Total PACs and
15 priority PAHs in inhaled air were measured by personal sampling. Hydroxylated PAH
metabolites (OH-PAHs) (2-naphthol, 2-hydroxyfluorene, 3-hydroxyphenanthrene, 1hydroxypyrene, 6-hydroxychrysene and 3-hydroxybenzo[a] pyrene) were determined in urine spot
samples collected in three different times during the work week. Results. Median vapour-phase
PAC (5.5 mu g m(-3)), PAHs ( <= 50 ng m(-3)) and OH- PAHs (0.08-1.11 mu g1(-1)) were
significantly higher in AW than in CW, except in the cases of air naphthalene and 2-naphthol.
Airborne levels of particle-phase contaminants were similar in the two groups and much lower
than vapour-phase levels; metabolites of particulate PAHs were never found in quantifiable
amounts. An appreciable increase in OH-PAH levels during the work day and work week was
found in AW; median levels for 2- hydroxyfluorene, 3-hydroxyphenanthrene and 1-hydroxypyrene
were, respectively, 0.29, 0.08 and 0.18 at baseline; 0.50, 0.18 and 0.29, pre-shift; 1.11, 0.44 and
0.44 mu g 1(-1), post-shift. Each OH-PAH exhibited a characteristic profile of increase, reflecting
differences in half-lives of the parent compounds. In non-smoking subjects, positive correlations
were found between vapour-phase PAC or PAHs and OH-PAHs both in pre- and post-shift
samples (0.34 <= r <= 69). Smokers exhibited 2-5-fold higher OH- PAHs than non-smokers, at
any time and at both workplaces. Conclusions. Our results suggest that OH-PAHs are useful
biomarkers for monitoring exposure to asphalt emissions. The work-related exposure to PAC and
PAHs was low in all AW, but urinary metabolites reflected exposure satisfactorily.
XQ Tao, GN Lu, Z Dang, XY Yi, C Yang
Isolation of phenanthrene-degrading bacteria and characterization of phenanthrene metabolites
World Journal of Microbiology & Biotechnology, 2007, Vol 23, Iss 5, pp 647-654
Three aerobic bacterial consortia GY2, GS3 and GM2 were enriched from polycyclic aromatic
hydrocarbon-contaminated soils with water-silicone oil biphasic systems. An aerobic bacterial
strain utilizing phenanthrene as the sole carbon and energy source was isolated from bacterial
consortium GY2 and identified as Sphingomonas sp. Strain GY2B. Within 48 h and at 30 degrees
C the strain metabolized 99.1% of phenanthrene (100 mg/l) added to batch culture in mineral
salts medium and the cell number increased by about 40-fold. Three metabolites 1-hydroxy-2naphthoic acid, 1-naphthol and salicylic acid, were identified by gas chromatographic mass
spectrometry and UV-visible spectroscopy analysis. A degradation pathway was proposed based
on the identified metabolites. In addition to phenanthrene, strain GY2B could use other aromatic
compounds such as naphthalene, 2-naphthol, salicylic acid, catechol, phenol, benzene and
toluene as a sole source of carbon and energy.
R Schiewek, M Schellentrager, R Monnikes, M Lorenz, R Giese, KJ Brockmann, S Gab, T
Benter, OJ Schmitz
Ultrasensitive determination of polycyclic aromatic compounds with atmospheric-pressure laser
ionization as an interface for GC/MS
Analytical Chemistry, 2007, Vol 79, Iss 11, pp 4135-4140
Recently we introduced atmospheric pressure laser ionization (APLI) as a complementary
ionization method for coupling LC-MS systems (HPLC and CEC), allowing ionization of nonpolar
aromatic compounds via near-resonant two-photon excitation. In this paper, we demonstrate that
APLI with the same source enclosure as for LC coupling is also suited for hyphenation of GC with
atmospheric-pressure ionization mass spectrometry. This technique permits the qualitative and
quantitative determination of aromatic compounds in an ultralow concentration range, as we show
here with PAHs, alkylated PAHs, and hetero-PAHs as examples. The outstanding sensitivity is
demonstrated for chrysene, with a detection limit of 22 amol. Polar functional groups reduce the
sensitivity, but after methylation or silylation, the analytes can also be determined very sensitively
in complex matrixes, as is shown with 1-hydroxypyrene in urine.
S Kayillo, GR Dennis, RA Shalliker
Retention of polycyclic aromatic hydrocarbons on propyl-phenyl stationary phases in reversedphase high performance liquid chromatography
Journal of Chromatography A, 2007, Vol 1148, Iss 2, pp 168-176
A study on the retention of PAHs on three Propyl-phenyl stationary phases was conducted,
assessing absolute retention, selectivity, retention correlation and thermodynamic behaviour. The
chromatographic retention data revealed that each of the three Propyl-phenyl columns exhibited
differences in absolute retention, however, comparison of the compensation temperatures
derived from enthalpy-entropy compensation plots showed that the underlying processes
responsible for the retention on these columns were the same.
C SanchezBrunete, E Miguel, JL Tadeo
Analysis of 27 polycyclic aromatic hydrocarbons by matrix solid-phase dispersion and isotope
dilution gas chromatography-mass spectrometry in sewage sludge from the Spanish area of
Madrid
Journal of Chromatography A, 2007, Vol 1148, Iss 2, pp 219-227
A method for the determination of 27 PAHs in sludge from wastewater treatment plants (WWTPs)
located in urban, industrial or rural zones is presented. PAHs were extracted by matrix solidphase dispersion (MSPD) assisted by sonication. Purification of extracts was carried out by solidphase extraction with C-18 and PAHs were eluted with acetonitrile. PAHs were determined by
isotope dilution gas chromatography with electron impact mass spectrometric detection in the
selected ion-monitoring mode (GC-MS-SIM), using deuterated PAHs as internal standards. The
limits of detection ranged from 0.03 ng/g for acenaphthylene to 0.45 ng/g for benzo[b]naphtho[2,
1-d]thyophene. After optimization, the method was validated with a certified reference sludge.
The proposed analytical method was applied to determine PAH levels in sewage sludge samples
collected from 19 water treatment plants located in the province of Madrid (Spain). In most of the
examined samples, phenanthrene was the main compound with a mean concentration of 1062
ng/g. PAHs were detected in all of the samples, with total concentrations between 390 and 6390
ng/g dry weight for the 27 PAHs analyzed and from 310 to 5120 ng/g dry weight for the sum of
the 10 PAHs considered in the draft European Union directive.
LT Molina, CE Kolb, B deFoy, BK Lamb, WH Brune, JL Jimenez, R RamosVillegas, J Sarmiento,
VH ParamoFigueroa, B Cardenas, V GutierrezAvedoy, MJ Molina
Air quality in North America's most populous city - overview of the MCMA-2003 campaign
Atmospheric Chemistry and Physics, 2007, Vol 7, Iss 10, pp 2447-2473
Exploratory field measurements in the Mexico City Metropolitan Area ( MCMA) in February 2002
set the stage for a major air quality field measurement campaign in the spring of 2003 ( MCMA2003). Involving over 100 scientists from more than 30 institutions in Mexico, the United States
and Europe, MCMA-2003 revealed important new insights into the meteorology, primary pollutant
emissions, ambient secondary pollutant precursor concentrations, photochemical oxidant
production and secondary aerosol particle formation in North America's most populated and
polluted megacity. A description of meteorological and atmospheric chemistry and aerosol
microphysics measurements performed during MCMA-2003 is presented. More than 40 published
or submitted MCMA-2003 research papers are reviewed and key discoveries pertinent to
understanding and improving air quality in Mexico City and similar megacities in the developing
world are summarized.
BZ Yan, DL Stoner, JR Scott
Direct LD-FTMS detection of mineral-associated PAHs and their influence on the detection of coexisting amino acids
Talanta, 2007, Vol 72, Iss 2, pp 634-641
PAHs and amino acids (AAs) are both ubiquitous throughout the universe and can be co-located
in mineral matrices (e.g., meteorites); therefore, co-detection of PAHs and AAs associated with
terrestrial and extra-terrestrial minerals is of interest. Nine PAH compounds representing four
chemical classes of PAH (unsubstituted, acetyl-, amino-, and nitro-substituted) were applied onto
the surface of quartz, plagioclase, olivine, and ilmenite mineral standards and analyzed using
laser desorption/ionization Fourier transform mass spectrometry (LD-FTMS). Mass-to-charge
peaks derived from PAH compounds were detected from the surfaces of all minerals evaluated.
All PAH compounds were detected in the positive ion mode, whereas only nitro-substituted PAH
compounds were detected in negative ion mode. In this and earlier studies, the ability to directly
detect mineral-associated AAs by LD-FTMS was dependent on the mineral geomatrix. On ironbearing minerals AAs appeared as highly fragmented ions in the spectra or were not detectable;
however, the addition of the PAH chrysene enabled the ionization and detection of AAs threonine
and histidine by LD-FTMS. Thus, for mineral systems such as meteorites, interstellar dust
particles, soils, and sediments, the co-detection of AAs associated with PAHs by LD-FTMS is
feasible.
HW Chen
Polycyclic and nitro-polycyclic aromatic hydrocarbons in air particulates from a semiconductor
manufacturing area of Taiwan
Fresenius Environmental Bulletin, 2007, Vol 16, Iss 5, pp 543-547
During winter and summer 2005, airborne particulates were collected in three administrative
districts of Hsinchu, a semiconductor-manufacturing city in Taiwan. Pollution sources were diesel
and gasoline engine automobiles, as well as factory emissions. Nine PAHs and four nitro-PAHs
(NPAHs) present in the extracts from the particulates were analysed by high performance liquid
chromatography (HPLC) with fluorescence detection. Atmospheric concentrations of PAHs and
NPAHs in Science-based Industrial Park (SIP) were significantly higher than in North and
Hsiangshan districts (p < 0.05). As expected, seasonal variations were observed in the three
administrative districts. Major contributors of atmospheric PAHs in SIP were identified, and the
ratios were close to urban air particulates from factory emissions. Emissions of semiconductor
factories significantly increased atmospheric pollution in Hsinchu area.
MS Neal, JP Zhu, AC Holloway, WG Foster
Follicle growth is inhibited by benzo-[a]-pyrene, at concentrations representative of human
exposure, in an isolated rat follicle culture assay
Human Reproduction, 2007, Vol 22, Iss 4, pp 961-967
The adverse effects of cigarette smoking on human fertility have been well documented.
However, the mechanism(s) underlying the detrimental effects of cigarette smoking are unknown.
Using a novel isolated rat follicle culture assay, we tested the hypothesis that benzo-[a]-pyrene
(B[a]P), a constituent of cigarette smoke, can inhibit follicle growth. METHODS: B[a]P levels were
quantified in the serum and follicular fluid (FF) of women undergoing in vitro fertilization (IVF)
treatment exposed to mainstream smoke (n = 19) and non-smokers (n = 10) by gas
chromatography mass spectrometry. Isolated rat follicles were cultured with increasing
concentrations of B[a]P (1.5300 ng ml(-1)) and follicle diameter was measured daily. RESULTS:
Mean (+/- Standard error of the mean) B[a]P) was quantified in the serum (0.40 +/- 0.13 ng ml(1)) and FF (1.32 +/- 0.68 ng ml(-1)) of women who smoke. IVF stimulation and outcome
measures were similar between female smokers and non-smokers with the exception of
implantation rate and pregnancy rate, which were both significantly lower (P < 0.05) in the MS
group. B[a]P treatment significantly reduced rat follicle diameter and attenuated FSH stimulated
growth in a dose-dependent manner, beginning at 1.5 ng ml(-1). CONCLUSIONS: Our data
suggest that B[a]P, at levels representative of those measured in human FF, may adversely affect
follicle development and be an ovarian toxicant.
D Luo, QW Yu, HR Yin, YQ Feng
Humic acid-bonded silica as a novel sorbent for solid-phase extraction of benzo[a]pyrene in
edible oils
Analytica Chimica Acta, 2007, Vol 588, Iss 2, pp 261-267
A novel solid-phase extraction (SPE) sorbent, humic acid-bonded silica (HAS), was prepared.
Humic acids (HAs) were grafted onto silica matrices via an amide linkage between humyl chloride
and the amido terminus of 3-aminopropyltrimethoxysilane (APTS)-silica gel. The resulting
material was characterized by Fourier transform infrared spectrometer, elemental analysis, and
nitrogen adsorption analysis. This sorbent exhibits an excellent adsorption capacity for some
electron-abundant analytes owing to its peculiar structure. In this paper, we choose
benzo[a]pyrene (BaP) in oil as a probe to validate the adsorption capacity of the material. Thus a
fast, cheap and simple SPE method with humic acid-bonded silica cartridge for edible oil cleanup, followed by high-performance liquid chromatography (HPLC) with fluorescence detection was
established. The effects of experimental variables, such as washing and elution solvents, and the
amount of sorbents have been studied. The recoveries of BaP in edible oils spiked at 0.2-100 mu
g kg(-1) were in the range of 78.8-102.7% with relative standard deviations ranging between 1.3
and 9.3%; the limit of detection was -0.06 mu g kg(-1.) (c) 2007 Elsevier B. V. All rights reserved.
S Lee, HF Chen, JW Peng
Investigation of soot deposition and composition in a radio frequency plasma of benzene
Plasma Chemistry and Plasma Processing, 2007, Vol 27, Iss 3, pp 256-266
A radio frequency (rf) discharge has been utilized to study the decomposition of benzene. SEM
inspection has shown that the size of soot particles ranged from 0.5 to several mu m. The soot
deposited on silicon wafers was analyzed by gas chromatography/mass spectrometry (GC/MS). It
was shown that the main components of the soot are polyphenyls (biphenyl and terphenyls) and
a trace amount of PAHs. Acetylene and hydrogen have been detected by plasma diagnostics
techniques using Fourier transform infrared (FTIR) and optical emission spectroscopic
techniques. However, GC/MS analysis has shown that the relative yields of PAHs are much less
than those of polyphenyls, which indicates that the conventional hydrogen abstraction-acetylene
addition (HACA) model for soot formation is not applicable to the benzene plasma due to the
reason of temperature. The rf power, the carrier gas flow-rate, the relative yields of polyphenyls,
and plasma temperatures were correlated. The reaction pathways of benzene elimination and
soot formation in plasma are discussed. This study has provided a new route to control the
contamination due to PAHs.