The June 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
An interesting abstract of an paper on the use of a PAH for its electro-optical behavior:
http://www.nature.com/news/2007/070423/full/070423-11.html
Literature Review
KJ Brassington, RL Hough, GI Paton, KT Semple, GC Risdon, J Crossley, I Hay, K Askari, SJT
Pollard
Weathered hydrocarbon wastes: A risk management primer
Critical Reviews in Environmental Science and Technology, 2007, Vol 37, Iss 3, pp 199-232
We provide a primer and critical review of the characterization, risk assessment, and
bioremediation of weathered hydrocarbons. Historically the remediation of soil contaminated with
petroleum hydrocarbons has been expressed in terms of reductions in total petroleum
hydrocarbon (TPH) load rather than reductions in risk. There are several techniques by which
petroleum hydrocarbons in soils can be characterized. Method development is often driven by the
objectives of published risk assessment frameworks. Some frameworks stipulate analysis of a
wide range of petroleum hydrocarbons; for example, the United Kingdom (UK) approach
suggests compounds from EC5 to EC70 be examined. Methods for the extraction of petroleum
hydrocarbons from soil samples have been reviewed extensively in the open literature. Although
various extraction and analytical methods are available for petroleum hydrocarbons, their results
suffer from inter-method variation, with gas chromatography methods being used widely.
Currently, the implications for risk assessment are uncertain. Bioremediation works well for
remediating soils contaminated with petroleum hydrocarbons. As a result, the optimization of
environmental conditions is imperative. For petroleum hydrocarbons in soil, international
regulatory guidance on the management of risks from contaminated sites is now emerging. There
is also growing support for the move toward compound-specific risk-based approaches for the
assessment of hydrocarbon-contaminated land.
T Hattori, N Tang, K Tamura, A Hokoda, X Yang, K Igarashi, M Ohno, Y Okada, T Kameda, A
Toriba, K Hayakawa
Particulate polycyclic aromatic hydrocarbons and their nitrated derivatives in three cities in
Liaoning Province, China
Environmental Forensics, 2007, Vol 8, Iss 1-2, pp 165-172
Airborne particulates were collected in nine size fractions by using Andersen low-volume air
samplers in the cities of Shenyang, Fushun, and Tieling, Liaoning Province, in northeast China,
during the period from July 2001 through December 2003. Nine polycyclic aromatic hydrocarbons
(PAHs) and seven nitropolycyclic aromatic hydrocarbons (NPAHs) in the airborne particulates
were determined. The mean concentrations of the sums of the nine PAHs and seven NPAHs
were highest in Fushun, which is an industrial city, and lowest in Shenyang, which is a
commercial city, although the consumption of petroleum and coal were largest in Shenyang. The
nine fractions were grouped into three groups: >7 mu m, 2.1-7 mu m and <2.1 mu m. In each city,
more than 50% of the total PAHs and total NPAHs were found in the fine particulate fraction (<2.1
mu m). In each city, all PAHs and all NPAHs were clearly higher in winter than in summer. The
concentration ratio of 1-nitropyrene to pyrene, which is a suitable indicator to identify diesel
engine and coal combustion as proposed by our previous study, showed that the major
contributors of PAHs and NPAHs in the airborne particulates were coal-combustion systems both
in summer and winter in Fushun and Tieling. In Shenyang, atmospheric PAHs and NPAHs also
seemed to be affected by coal combustion systems in winter, whereas gasoline engine vehicles
seemed to be a major contributor in summer by the larger concentration ratio of 1-nitropyrene to
pyrene. Cluster analysis and other diagnostic ratios such as benz[a]anthracene to chrysene,
benzo[ghi]perylene to benzo[a]pyrene supported these results.
DL Poster, JR Kucklick, MM Schantz, BJ Porter, LC Sander, SA Wise
New developments in Standard Reference Materials (SRMs) for environmental forensics
Environmental Forensics, 2007, Vol 8, Iss 1-2, pp 181-191
For nearly three decades the National Institute of Standards and Technology (Gaithersburg, MD)
has been involved in the development of Standard Reference Materials (SRMs) for the
determination of organic contaminants in environmental matrices. Classes of organic
contaminants characterized in these materials include polycyclic aromatic hydrocarbons (PAHs),
polychlorinated biphenyls (PCBs), chlorinated pesticides, and most recently, brominated flame
retardants (polybrominated diphenyl ethers [PBDEs]). Environmental matrices include fossil fuels,
air and diesel particulate matter, house dust, coal tar, sediment, mussel and fish tissue, fish oil,
and whale blubber. Recent SRM developments and activities have led to a number of
environmental SRMs that are useful for assuring quality of analytical measurements in
environmental forensics where source profiling of organic contaminants is often conducted in a
range of environmental or biological matrices. Particle-related SRM developments include the
issue of a new house dust material (SRM 2585 Organic Contaminants in House Dust), and the
recertification of two SRMs: a diesel particulate matter material (SRM 1650b Diesel Particulate
Matter) for certified and reference values for 97 PAHs and nitro-PAHs and a river sediment (SRM
1939b PCBs in River Sediment A) for a greater number of PCB congener concentrations relative
to its former certification in 1998 as well as for total PCBs. A coal tar SRM (SRM 1597a Complex
Mixture of PAHs from Coal Tar) has also been reissued with an expanded range of values for
PAHs (including methyl- and dimethyl-substituted PAHs, PAH isomers of molecular mass 302,
and polycyclic aromatic sulfur heterocycles [PASH]). The latest biological SRM developments
include the issue of a new fish tissue SRM (SRM 1947 Lake Michigan Fish Tissue) and the
recertification of a cod liver oil (SRM 1588b Organics in Cod Liver Oil) and a human serum (SRM
1589b PCBs, Pesticides, PBDEs, and Dioxins/Furans in Human Serum). SRM 1588b has values
assigned for 124 constituents, and SRM 1589b has values assigned for 88 constituents. An
overview of these recent SRM activities is provided in this paper, and selected organic
contaminant values in newly developed particulate-related and biological SRMs are presented.
The usefulness of these materials for assuring quality in environmental forensic measurements is
also discussed.
JW McClaine, MJ Wornat
Reaction mechanisms governing the formation of polycyclic aromatic hydrocarbons in the
supercritical pyrolysis of toluene: C28H14 isomers
Journal of Physical Chemistry C, 2007, Vol 111, Iss 1, pp 86-95
Reaction pathways for the formation of C28H14 polycyclic aromatic hydrocarbons (PAH) sof
which there are eight benzenoid isomers during the supercritical pyrolysis of toluene are
described in detail. These reaction mechanisms involve the addition of benzyl, methyl, and/or
phenyl radicals to smaller PAH products in three specific reactions: (A) addition of methyl and
benzyl, usually to a position adjacent to a bay region; (B) addition of phenyl to a bay region; and
(C) addition of two methyls to a bay region. Using these three types of reactions, we are able to
explain why the five identified C28H14 PAH-benzo[a] coronene, phenanthro[ 5,4,3,2efghi]perylene, benzo[cd]naphtho[3,2,1,8-pqra]perylene, benzo[ghi]naphtho[8,1,2-bcd] perylene,
and benzo[pqr]naphtho[8,1,2-bcd] perylene-are present in our product mixture and why
bisanthene, a C28H14 isomer that we know is not present from UV spectral data, is not formed.
We then determine reaction pathways for the remaining two C28H14 benzenoid isomers,
naphthaceno[3,4,5,6,7-defghij] naphthacene and tribenzo[cd,ghi,lm]-perylene, to deduce that the
sixth C28H14 PAH detected in our product mixture by HPLC/MS is most likely tribenzo[cd,ghi,lm]
perylene.
G Scherer, J Engl, M Urban, G Gilch, D Janket, K Riedel
Relationship between machine-derived smoke yields and biomarkers in cigarette smokers in
Germany
Regulatory Toxicology and Pharmacology, 2007, Vol 47, Iss 2, pp 171-183
In order to determine whether smokers of cigarettes in the contemporary yield ranges of the
German market (0.1-1.0 mg nicotine, 1-10mg tar) differ in their actual exposure to various smoke
constituents, we performed a field study with 274 smokers and 100 non-smokers. The following
biomarkers were determined: In 24-h urine: Nicotine equivalents (molar sum of nicotine, cotinine,
trans-3'hydroxycotinine and their respective glueuronides), 4-(methylnitrosamino)-1-(3-pyridyl)-1butanol (NNAL, metabolite of the tobaccospecific nitrosamine 4-(methylnitrosamino)-1-(3-pyridyl)1-butanone, NNK), 3-hydroxypropyltnercapturic acid (metabolite of acrolein), trans,trans-muconic
acid, S-phenylmercapturic acid (metabolites of benzene), 1-hydroxypyrene (metabolite of
pyrene); in saliva: Cotinine and trans-3'-hydroxycotinine; in exhaled air: Carbon monoxide; in
blood: Methyl-, hydroxyethyl-, cyanoethyl- (biomarker of acrylonitrile) and carbamoylethylvaline
(biomarker of acrylamide) hemoglobin adducts. All biomarkers were found to be significantly
higher in smokers compared to non-smokers and showed strong correlations with the daily
cigarette consumption. Biomarker levels and per cigarette increases in smokers were at most
weakly related to the machine-derived smoke yields. It is concluded that machine-derived yields
of cigarettes from the contemporary German cigarette market have little or no impact on the
actual smoking-related exposure determined by suitable biomarkers.
AM Peck, JR Kucklick, MM Schantz
Synthetic musk fragrances in environmental standard reference materials
Analytical and Bioanalytical Chemistry, 2007, Vol 387, Iss 7, pp 2381-2388
Synthetic musk fragrances have been measured in water, air, sediments, sewage sludge, and
biota worldwide. As the study of the environmental fate and impacts of these compounds
progresses, the need for Standard Reference Materials (SRMs) for these compounds to facilitate
analytical method improvement and interlaboratory comparisons becomes increasingly important.
The National Institute of Standards and Technology (NIST) issues environmental matrix SRMs
with certified concentrations for a variety of persistent organic pollutants including polycyclic
aromatic hydrocarbons (PAHs), chlorinated pesticides, and polychlorinated biphenyl congeners
(PCBs). Until now synthetic musk fragrance concentrations have not been reported in NIST
SRMs. The objective of this study was to provide reference values for several commonly detected
synthetic musk fragrances in several NIST natural matrix SRMs. In this study five polycyclic musk
fragrances [HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2benzopyran), AHTN (7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene), ADBI (4acetyl-1,1-dimethyl-6-tert-butylindane), AHMI (6-acetyl-1,1,2,3,3,5-hexamethylindane), and ATII
(5-acetyl-1,1,2,6-tetramethyl-3-isopropylindane] and two nitro musk fragrances [musk xylene (1-
tert-butyl-3,5-dimethyl-2,4,6-trinitrobenzene) and musk ketone (4-tert-butyl-3,5-dinitro-2,6dimethylacetophenone)] were measured in selected environmental SRMs. Gas chromatographyelectron impact mass spectrometry (GC/EI-MS) was used for all analyses. HHCB was the most
frequently detected synthetic musk fragrance and was detected in SRM 2585 Organic
Contaminants in House Dust, SRM 2781 Domestic Sludge, SRM 1974b Organics in Mussel
Tissue (Mytilus edulis), and SRM 1947 Lake Michigan Fish Tissue. It was not detected in SRM
1946 Lake Superior Fish Tissue or SRM 1945 Organics in Whale Blubber. Concentrations of
HHCB in these SRMs ranged from 1.12 ng/g in SRM 1947 to 92,901 ng/g in SRM 2781. All of the
polycyclic musk fragrances were detected in SRM 2781 and all of the target compounds were
detected in SRM 2585.
ZR Ma, MD Halling, MS Solum, JK Harper, AM Orendt, JC Facelli, RJ Pugmire, DM Grant, AW
Amick, LT Scott
Ring current effects in crystals. Evidence from C-13 chemical shift tensors for intermolecular
shielding in 4,7-di-t-butylacenaphthene versus 4,7-di-t-butylacenaphthylene
Full source
Journal of Physical Chemistry A, 2007, Vol 111, Iss 10, pp 2020-2027
C-13 chemical shift tensor data from 2D FIREMAT spectra are reported for 4,7-di-tbutylacenaphthene and 4,7-di-t-butylacenaphthylene. In addition, calculations of the chemical
shielding tensors were completed at the B3LYP/6-311G** level of theory. While the experimental
tensor data on 4,7-di-t-butylacenaphthylene are in agreement with theory and with previous data
on polycyclic aromatic hydrocarbons, the experimental and theoretical data on 4,7-di-tbutylacenaphthene lack agreement. Instead, larger than usual differences are observed between
the experimental chemical shift components and the chemical shielding tensor components
calculated on a single molecule of 4,7-di-t-butylacenaphthene, with a root mean square (rms)
error of +/- 7.0 ppm. The greatest deviation is concentrated in the component perpendicular to the
aromatic plane, with the largest value being a 23 ppm difference between experiment and theory
for the (CH2)-C-13 carbon delta(11) component. These differences are attributed to an
intermolecular chemical shift that arises from the graphitelike, stacked arrangement of molecules
found in the crystal structure of 4,7-di-t-butylacenaphthene. This conclusion is supported by a
calculation on a trimer of molecules, which improves the agreement between experiment and
theory for this component by 14 ppm and reduces the overall rms error between experiment and
theory to 4.0 ppm. This intermolecular effect may be modeled with the use of nuclei independent
chemical shieldings (NICS) calculations and is also observed in the isotropic H-1 chemical shift of
the CH2 protons as a 4.2 ppm difference between the solution value and the solid-state chemical
shift measured via a C-13-H-1 heteronuclear correlation experiment.
U Kammann
PAH metabolites in bile fluids of dab (Limanda limanda) and flounder (Platichthys flesus): Spatial
distribution and seasonal changes
Environmental Science and Pollution Research, 2007, Vol 14, Iss 2, pp 102-108
Background, Aims and Scope. Polycyclic aromatic hydrocarbons (PAH) are important
environmental contaminants which may lead to increased levels of neoplastic aberrations or
tumours in fish liver. Therefore, monitoring of PAH and their effects are part of several
international environmental programmes. The aim of the present field study was to investigate the
concentrations of the PAH metabolites in fish bile, to elucidate spatial, seasonal and species
differences as well as to discuss different strategies of normalisation with regard to environmental
monitoring. Material Methods. PAH metabolites were determined in the bile fluid of dab (Limanda
limanda) and flounder (Platichthys flesus) caught in the North Sea and Baltic Sea between 1997
and 2004. After enzymatic deconjugation, two metabolites were determined by means of HPLC.
The limit of detection and the limit of quantification were calculated. The accuracy of the method
was tested with a standard reference material. Results were referred to bile volume as well as to
biliverdin. Results. The main metabolite, 1-hydroxypyrene, was determined in concentrations from
< 0.7 to 838 ng/ml in bile of dab (Limanda limanda) and flounder (Platichthys flesus) caught
between 1997 and 2004. The values for 1-hydroxyphenanthrene in fish bile were considerably
lower (< 0.4-87 ng/ml). Significant differences in the 1-hydroxypyrene levels were found between
summer and winter surveys as well as between the sampling sites in the data set from 2004 (383
dabs and 62 flounders): Highest levels of PAH contamination were found in dab from the German
Bight and in flounder from the Baltic Sea. Discussion. Spatial differences in 1-hydroxypyrene
concentrations between North Sea and Baltic Sea were discussed, as well as differences in
relation to season, sex and species. Three parameters of normalisation (biliary protein, biliverdin
and bile pigments) were discussed. Biliverdin was identified as a suitable parameter for the
normalisation of PAH metabolites in field samples. Conclusions. Spatial differences in 1hydroxypyrene concentrations of dab demonstrate the usefulness of PAH metabolites in fish bile
as a monitoring parameter in marine regions. Significant differences in 1-hydroxypyrene
concentrations were found between summer and winter sampling campaigns. This may be linked
to an annual cycle of 1-hydroxyprene in dab. It is also possible that bile synthesis/release in dab
differs between the seasons. There is no indication for a time trend from 1997 to 2004.
Recommendations and Perspectives. It is recommended to relate PAH metabolites in fish bile to
biliverdin concentrations. Although the concentrations are low in offshore regions and bile
volumes are small, the method presented here allows one to measure PAH metabolites on an
individual level which is a crucial prerequisite for meaningful monitoring studies.
M Reinik, T Tamme, M Roasto, K Juhkam, T Tenno, A Kiis
Polycyclic aromatic hydrocarbons (PAHs) in meat products and estimated PAH intake by children
and the general population in Estonia
Food Additives and Contaminants, 2007, Vol 24, Iss 4, pp 429-437
The concentrations of benzo[a] pyrene and 11 other PAHs were analysed from 322 commercial,
cured meat products and 14 home-grilled meat samples as part of the Estonian food safety
monitoring programme during 2001-2005. The maximum acceptable concentration of 5 mu g kg(1) for benzo[a]pyrene was exceeded in 3.4% of samples. The highest PAH concentrations were
detected in home-grilled pork samples. Using of disposable grilling unit resulted in 1.6 times
higher PAH concentrations compared to the traditional wood-burning grill. The average intake of
benzo[a]pyrene and sum of 12 PAHs from meat products was estimated for children (age 1-16
years) on the basis of an individual food consumption questionnaire and, for the general
population, based on national food consumption data. The highest total PAH concentrations
detected were 16 mu g kg(-1) in smoked meat and ham, 19 mu g kg(-1) in smoked sausage and
6.5 mu g kg(-1) in smoked chicken samples. Since smoking and grilling are prevalent meatcooking methods in Estonia, the impact of meat products is assessed to be significant in overall
PAH intake.
S Kayillo, GR Dennis, RA Shalliker
An assessment of the retention behaviour of polycyclic aromatic hydrocarbons on reversed phase
stationary phases - Thermodynamic behaviour on C18 and phenyl-type surfaces
Journal of Chromatography A, 2007, Vol 1145, Iss 1-2, pp 133-140
The thermodynamic retention behaviour of a linear series of PAHs was investigated on C18 and
selected phenyl-type reversed-phase stationary phases, namely C18, C18 Aqua, Propyl-phenyl
and Synergi polar-RP stationary phases, using methanol mobile phases. The Propyl-phenyl
stationary phase, despite having the lowest surface coverage, was found to exhibit significantly
larger enthalpic interactions to the other Phenyl-type phase (Synergi polar-RP) even though this
had a much higher surface coverage. This indicated that stronger interactions between the PAHs
and the stationary phase ligands were occurring on the Propyl-phenyl phase. Evaluation of the
elution band profile of the FAHs in the aqueous methanol mobile phase revealed fairly
symmetrical bands for the C18, C18 Aqua and Synergi polar-RP, but severe peak tailing on the
Propyl-phenyl phase. A change in mobile phase from methanol to acetonitrile improved the peak
shape of the PAHs on the Propyl-phenyl phase, leading to the assumption that unfavourable pi-pi
interactions were occurring between the electron-rich PAHs and the electron-rich phenyl rings of
the Propyl-phenyl phase.
W Buchberger, P Zaborsky
Sorptive extraction techniques for trace analysis of organic pollutants in the aquatic environment
Acta Chimica Slovenica, 2007, Vol 54, Iss 1, pp 1-13
Environmental water analysis requires the determination of organic contaminants down to the low
ng L-1 range which makes efficient sample preconcentration and sample clean-up mandatory
prior to high-performance separation techniques combined with selective detection. Solid-phase
extraction has become one of the most important sample pre-treatment procedures in
environmental analytical chemistry, based on either single equilibration or multiple equilibration of
analytes between the aqueous sample and the sorbent. Procedures based on a single
partitioning step between sample and sorbent phase (such as solid-phase microextraction, stir
bar sorptive extraction and related variants) are generally called sorptive extraction techniques.
The increasing popularity of these techniques is due to reduced time-consumption and increased
cost-effectiveness. In this review paper, the current state of sorptive extraction with respect to
organic trace analysis in water samples is discussed regarding both the theoretical aspects as
well as the applications for organic xenobiotics in the aquatic environment. The ongoing
acceptance of sorptive extraction techniques into official methods clearly indicates that they offer
satisfactory reliability and robustness for routine monitoring purposes.
Y Ooki, M Kumemura, M Itoh, T Korenaga
Inhibitory analysis of the effect of polycyclic aromatic hydrocarbons on the activity of chitinase by
means of liquid chromatography-mass spectrometry of chitin oligosaccharides
Analytical and Bioanalytical Chemistry, 2007, Vol 387, Iss 8, pp 2641-2644
The analytical method of determining enzyme activity by liquid chromatography-mass
spectrometry (LC/MS) was developed and applied for investigation of the effect of PAHs on the
enzyme activity of chitinase. The measurement of chitinase activity by LC/MS is useful in order to
use the nonderivatized substrate, which can show in vivo chitinase activity. Substrate
consumption and product formation were monitored in order to determine chitinase activity. It was
shown that, for the first time, in vitro addition of PAHs inhibited the activity of chitinase in a
noncompetitive manner. The IC50 value of benzo[a]pyrene was 1.4 mu M, and PAHs containing
four or more aromatic rings showed the same or higher inhibitory effect, whereas PAHs with a
lower number of aromatic rings showed lower inhibition of the chitinase activity than
benzo[a]pyrene.
J Happold, HH Grotheer, M Aigner
Distinction of gaseous soot precursor molecules and soot precursor particles through
photoionization mass spectrometry
Rapid Communications in Mass Spectrometry, 2007, Vol 21, Iss 7, pp 1247-1254
Samples were drawn from sooting premixed low-pressure ethylene oxygen flames and
investigated through photoionization mass spectrometry using either KrF or ArF lasers as the
radiation source. With the former, mass spectra were obtained as described in the literature and
characterized through a series of signal groups, one for each C-number and extending to about
m/z 1000, assigned as a PAH series. When the ArF laser was used the same series was
observed with a somewhat higher sensitivity. In addition, a new series was observed overlaid on
the PAH series and starting at about m/z 680. The new series exhibited abundant ions and it
completely dominated the spectrum beyond m/z 1000. This series was identified as being the
spectrum of soot precursor particles. Through measurement of the ionization order it was
concluded that at least two photons are needed for ionization of PAHs whereas the particles need
only one photon. Consequently, they can be measured with high sensitivity when an ArF laser is
used as the radiation source. Furthermore, the discrimination of soot precursor molecules and
soot precursor particles becomes possible through photoionization and this enables an improved
understanding of the mass spectra. This should allow a particle growth mechanism to be deduced
in the near future.
JAE Cavanagh, L Brown, K Trought, S Kingham, MJ Epton
Elevated concentrations of 1-hydroxypyrene in schoolchildren during winter in Christchurch, New
Zealand
Science of the Total Environment, 2007, Vol 374, Iss 1, pp 51-59
Particulate air pollution is significantly elevated during the winter in Christchurch, New Zealand,
largely attributable to use of wood bumers for domestic home heating, topography, and
meteorological conditions. Polycyclic aromatic hydrocarbons (PAHs) are a key component of
airborne particulate matter (PM) and urinary 1-hydroxypyrene (1-OHP) has previously been used
to assess exposure of people to PAHs. We examined urinary 1-OHP in Christchurch male nonsmoking schoolchildren (12-18 yr) on two occasions after high pollution events (48 and 72 mu g
PM10/m(3) 24-h average) and two occasions during periods of low pollution (19 and 12 mu g
PM10/m(3)). Concentrations of urinary I-OHP were significantly elevated in the students during
high pollution events (median (mean +/- SD) 0.043 (0.051 +/- 0.032) and 0.042 (0.060 +/- 0.092)
mu mol OHP/mol creatinine respectively) compared with low pollution periods (median (mean +/SD) 0.019 (0.026 +/- 0.032) and 0.025 (0.028 +/- 0.018) mu mol/mol creatinine respectively). The
observed 1-OHP concentrations are at the lower end of those determined in children and nonoccupationally exposed adults in international studies and suggest a generally low exposure to
PAHs. The increased urinary I-OHP concentrations following nights of elevated particulate
concentrations in ambient air suggest increased exposure to ambient air pollution during winter
time, and could potentially be used as a biomarker of exposure in this population.
MF GomezRico, R Font, I Aracil, A Fullana
Analysis of organic pollutants in sewage sludges from the Valencian community (Spain)
Archives of Environmental Contamination and Toxicology, 2007, Vol 52, Iss 3, pp 306-316
Seventeen sewage sludges were studied to analyse, with the minimum number of steps, the
organic pollutants that the European Union proposes to be controlled for land application. The
compounds determined were a selection of PAHs; a selection of polychlorinated biphenyls
(PCBs); di(2-ethylhexyl)phthalate (DEHP); nonylphenolic compounds, including nonylphenol (NP)
and nonylphenol ethoxylates with 1 and 2 ethoxy groups (NP1EO + NP2EO); extractable organic
halides (EOX); and linear alkylbenzene sulphonates (LAS) with an alkylic chain of 10 to 13
carbon atoms. The results were compared with the proposed regulatory limit values, and it was
observed that NP + NP1EO + NP2EO and LAS exceeded the maximums in most samples, and
DEHP exceeded some of them, whereas PAHs, PCBs, and EOX almost always went beyond the
limits. The values obtained are similar to those from other countries, and it can be said that it is
difficult to comply with the limits for NP + NP1EO + NP2EO and LAS in many of them, although
this latter parameter was not considered in the study carried out by Leschber (2004) concerning
the toxicity of sewage sludge. Statistical multivariant analysis was used to look for some
relationship between the results of pollutants and the characteristics of the samples, and it was
found that the ratio of NP1EO + NP2EO to NP was related to sludge treatment at the sewage
plant. At the same time, it was seen that the higher values of organic pollutants belonged to
digested sludges.
SA Barker
Matrix solid phase dispersion (MSPD)
Journal of Biochemical and Biophysical Methods, 2007, Vol 70, Iss 2, pp 151-162
A review of the many uses of matrix solid phase dispersion (MSPD) in the extraction and analysis
of a variety of compounds from a range of samples is provided. Matrix solid phase dispersion
(MSPD) has found particular application as a somewhat generic analytical process for the
preparation, extraction and fractionation of solid, semi-solid and/or highly viscous biological
samples. Its simplicity and flexibility contribute to it being chosen over more classical methods for
these purposes. MSPD is based on several simple principles of chemistry and physics, involving
forces applied to the sample by mechanical blending to produce complete sample disruption and
the interactions of the sample matrix with a solid support bonded-phase (SPE) or the surface
chemistry of other solid support materials. These principles are discussed as are the factors to be
considered in conducting a MSPD extraction.
S Bogialli, A DiCorcia
Matrix solid-phase dispersion as a valuable tool for extracting contaminants from foodstuffs
Journal of Biochemical and Biophysical Methods, 2007, Vol 70, Iss 2, pp 163-179
This review updates our knowledge on matrix solid-phase dispersion (MSPD), a sample
treatment procedure that is increasingly used for extracting/purifying contaminants from a variety
of solid, semi-solid, viscous, and liquid foodstuffs. MSPD is primarily used because of its
flexibility, selectivity, and the possibility of performing extraction and cleanup in one step, this
resulting in drastically shortening of the analysis time and low consumption of toxic and expensive
solvents. Technical developments and parameters influencing the extraction yield and selectivity
are examined and discussed. Experimental results for the analysis of pesticides, veterinary drugs,
persistent en v iron mental chemicals, naturally occurring toxicants, and surfactants in food are
reviewed.
DA Lambropoulou, TA Albanis
Liquid-phase micro-extraction techniques in pesticide residue analysis
Journal of Biochemical and Biophysical Methods, 2007, Vol 70, Iss 2, pp 195-228
Modem trends in analytical chemistry are towards the simplification and miniaturization of sample
preparation, as well as the minimization of organic solvent used. In view of this aspect, several
novel micro-extraction techniques are being developed in order to reduce the analysis step,
increase the sample throughput and to improve the quality and the sensitivity of analytical
methods. One of the emerging techniques in this area is liquid-phase micro-extraction (LPME). It
is a miniaturized implementation of conventional liquid/liquid extraction (LLE) in which only
microliters of solvents are used instead of several hundred milliliters in LLE. It is quick,
inexpensive and can be automated. In the last few years, LPME has been combined with liquid
chromatography (LC) and capillary electrophoresis (CE), besides the generally used coupling to
gas chromatography (GC), and has been applied to various matrices, including biological,
environmental, and food samples. This work is aimed at providing an overview of the major
developments of LPME, coupled with chromatography and CE, as reported in the literature. The
paper will focus on the application of the technique to different matrices and the aim is to reveal
the panorama of opportunities and to try to indicate the potential of LPME in pesticide analysis. A
critical review of the first applications to pesticide analyses is presented in the main part of the
manuscript. The optimization of LPME as well as advantages and disadvantages are discussed.
It is concluded that, because of its high preconcentration factor, LPME can be introduced with
benefit into water analysis for several pesticide groups. In particular, the application of LPME to
non-polar pesticides in environmental analysis appears to be promising. However, similar to other
micro-extraction techniques, such as solid phase micro-ex traction (SPME), serious limitations
still remain when analyzing semi-solid and solid environmental, food or biological matrices and/or
highly polar compounds. Thus, other pre-concentration techniques may be a good alternative if
an analytical problem cannot be sufficiently dealt with LPME. (c) 2006 Elsevier B.V. All rights
reserved.
W Wardencki, J Curylo, J Namiesnik
Trends in solventless sample preparation techniques for environmental analysis
Journal of Biochemical and Biophysical Methods, 2007, Vol 70, Iss 2, pp 275-288
The paper presents recent trends in solventless sample preparation techniques for environmental
analysis. First, a general classification of solventless methods is given. Next, three of them,
treated as preferable techniques, i.e. SPME, SDME and HS, are presented in detail, with respect
to their usability and effectiveness for environmental samples. Examples of all discussed
techniques are given in the tables.
L Zanieri, P Galvan, L Checchini, A Cincinelli, L Lepri, GP Donzelli, M DelBubba
Polycyclic aromatic hydrocarbons (PAHs) in human milk from Italian women: Influence of
cigarette smoking and residential area
Chemosphere, 2007, Vol 67, Iss 7, pp 1265-1274
The presence of PAH in breast milk collected from 32 smoking and non-smoking lactating
women, residing in urban and rural areas of Tuscany (Italy) was investigated. The results
indicated a significant contribution of tobacco smoke to the PAH contamination of milk: the
condensate contained in the cigarettes smoked daily by each subject was strongly related with
the polynuclear hydrocarbon content (R-2 = 0.92, P < 0.005). An experiment carried out under
controlled exposure conditions to cigarette smoke allowed to demonstrate that individual
metabolic activity and smoking habits affect the PAH concentration in milk samples. Mothers
living in rural environments showed significantly lower PAH concentrations than those observed
in urban subjects. The risk evaluation due to PAH ingestion via breast milk was assessed on the
basis of the acceptable daily intake of Benzo(a)pyrene in drinking water, evidencing that a hazard
cannot be excluded for heavy smokers residing in urban areas.
SY Zang, PJ Li, WX Li, D Zhang, A Hamilton
Degradation mechanisms of benzo[a]pyrene and its accumulated metabolites by biodegradation
combined with chemical oxidation
Chemosphere, 2007, Vol 67, Iss 7, pp 1368-1374
A high degradation extent of benzo[a]pyrene (BaP) should not be considered as the sole
desirable criterion for the bioremediation of BaP-contaminated soils because some of its
accumulated metabolites still have severe health risks to human. Two main metabolites of BaP,
benzo[a]pyrene-1,6-quinone (BP1,6-quinone) and 3-hydroxybenzo[a]pyrene (3-OHBP) were
identified by high performance liquid chromatography (HPLC) with standards. This study was the
first time that degradation of both BaP and the two metabolites was carried out by chemical
oxidation and biodegradation. Three main phases during the whole degradation process were
proposed. Hydrogen peroxide-zinc (H2O2-Zn), the fungus - Aspergillus niger and the bacteria Zoogloea sp. Played an important role in the different phases. The degradation parameters of the
system were also optimized, and the results showed that the effect of degradation was the best
when fungus-bacteria combined with H2O2-Zn, the concentration range of BaP in the cultures
was 30-120 mg/l, the initial pH of the cultures was 6.0. However, as co-metabolites,
phenanthrene significant inhibited the degradation of BaP. This combined degradation system
compared with the conventional method of degradation by domestic fungus only, enhanced the
degradation extent of BaP by more than 20% on the 12 d. The highest accumulation of BP1,6quinone and 3-OHBP were reduced by nearly 10% in the degradation experiments, which further
proved that the combined degradation system was more effective as far as joint toxicity of BaP
and its metabolites are concerned.
DG Petersen, I Dahllof
Combined effects of pyrene and UV-light on algae and bacteria in an arctic sediment
Ecotoxicology, 2007, Vol 16, Iss 4, pp 371-377
The phototoxicity potential of pyrene on natural algae and bacteria in an arctic sediment was
evaluated and compared to that of pyrene treatment alone based on some functional and
structural endpoints. Microcosms with arctic sediment from a shallow-water marine bay were
incubated with pyrene under three different light regimes, natural sunlight with UV-light
(Light(UV)), natural sunlight without UV-light (Light) and dark. Presence of pyrene directly
affected the algal community measured as decreased C-14-incorporation and decreased
ammonium, nitrate and silicate uptake. These direct toxic effects from pyrene on the algae
eventually led to indirect effects on the bacterial community observed as increased oxygen
consumption. Besides the direct toxicity of pyrene to the benthic microbial community, indications
of phototoxicity were found on the bacterial community detected as decreased oxygen
consumption and increased bacterial diversity under Light(UV) compared to Light. No indication
of phototoxicity of pyrene was found on the algae, which might be due to the high direct toxicity of
pyrene. Our results indicate that shallow arctic marine areas might be affected by phototoxicity if
concentrations of oil components in the sediments increase.
A Kronimus, J Schwarzbauer
Non-target screening of extractable and non-extractable organic xenobiotics in riverine sediments
of Ems and Mulde Rivers, Germany
Environmental Pollution, 2007, Vol 147, Iss 1, pp 176-186
ubaquatic, sediment samples derived form Elbe and Mulde Rivers, Germany, were analyzed for
extractable and non-extractable anthropogenic organic compounds by a non-target screening
approach. Applied methodologies were gas chromatography-mass spectrometry, dispersion
extraction and degradation procedures, particularly alkaline and acidic hydrolysis, boron
tribromide treatment, ruthenium tetroxide oxidation as well as pyrolysis and TMAH
(tetramethylammonium hydroxide)-thermochemolysis. Numerous compounds were identified,
including halogenated benzenes, anisoles, styrenes, alkanes, diphenylmethane derivates,
anilines, phenols and diphenyl ethers. The results were interpreted with respect to compound
specific modes of incorporation as well as to potential sources (e.g. Municipal, agricultural,
industrial). Extractable and non-extractable fractions differed significantly with respect to their
qualitative and quantitative composition. For example, quantities in the extractable and nonextractable fractions of chlorinated benzenes differed up to factor 50. Among other significant
results, the investigation revealed hints for a dependence of the mode of incorporation of
chlorinated benzenes on their substitution pattern. (c) 2006 Elsevier Ltd. All rights reserved.
SP Wu, S Tao, ZH Zhang, T Lan, Q Zuo
Characterization of TSP-bound n-alkanes and polycyclic aromatic hydrocarbons at rural and
urban sites of Tianjin, China
Environmental Pollution, 2007, Vol 147, Iss 1, pp 203-210
Total suspended particle (TSP) was collected and analyzed at rural and urban sites in Tianjin,
China during the domestic heating season (from 15 November to 15 March) of 2003/4 for nalkanes and 16 polycyclic aromatic hydrocarbons (PAHs). The normalized distribution of nalkanes with the peak at C-22, C-23, C-24 or C-25 suggested that fossil fuel utilization was the
major source of particulate n-alkanes at both sites. PAHs normalized distribution for each sample
was similar and the higher molecular weight PAH dominated the profile (around 90%) indicating a
stronger combustion source at both sites. Precipitation and wind were the most important
meteorological factors influencing TSP and PAHs atmospheric concentrations. In the urban area
the emission height had significant influence on PAHs levels at different heights under the relative
stable atmospheric conditions. Coal combustion was the major source for TSP-bound PAHs at
both sites based on some diagnostic ratios.
SA Tfouni, MCF Toledo
Determination of polycyclic aromatic hydrocarbons in cane sugar
Food Control, 2007, Vol 18, Iss 8, pp 948-952
Different brands and types of commercial cane sugar available oil the Brazilian market were
analysed Cor five polycyclic aromatic hydrocarbons (PAHs) by HPLC-FL. PAHs were detected in
57% of the amples at levels ranging from not detected to 1.35 mu g/kg. The most commonly
found PAH was benz(a)anthracene, found in 51%, of the analysed samples, while
dibenz(a,h)anthracene was not detected. The results indicate that the practice of burning sugar
cane bet-ore harvest may be responsible I-or the presence of PAHs in commercial cane sugar
and suggests that the levels of PAH residues in the final product depend oil the amount of burnt
sugar cane being processed and on the steps involved in the sugar refining process.
XP Li, VL McGuffin
Thermodynamics and kinetics of chiral separations with beta-cyclodextrin stationary phase: II.
Effect of temperature and pressure
Journal of Liquid Chromatography & Related Technologies, 2007, Vol 30, Iss 5-8, pp 965-985
In this study, a series of coumarin-based compounds is separated using a beta-cyclodextrin
stationary phase with a polar-organic mobile phase. Temperature and pressure are varied in
order to observe the effects and determine important thermodynamic and kinetic parameters.
Increasing the temperature decreases the retention and chiral selectivity, but increases the mass
transfer rates for all chiral compounds. Increasing the pressure decreases the retention, but does
not significantly affect the chiral selectivity. Van't Hoff plots of the natural logarithm of retention
factor versus inverse temperature are linear with positive slopes, indicating an enthalpically
favorable transfer from mobile to stationary phase. The second eluted enantiomer has a more
negative change in molar enthalpy than the first, suggesting an enthalpically more favorable
transfer. For all compounds, both the differential change in molar enthalpy and the differential
change in molar entropy between the two enantiomers are negative. From these values, the
compensation temperature is determined and is above ambient temperature, indicating an
enthalpy-driven separation. Although all the compounds have similar structures, different
compensation temperatures are determined and enthalpy-entropy compensation is not observed.
This suggests that the retention mechanism is distinctly different. The change in molar volume is
positive, indicating that the compounds occupy more space in the stationary phase than in the
mobile phase and that inclusion in the cyclodextrin cavity does not occur to a significant extent.
With regard to the kinetic behavior, the rate constants generally increase with increasing retention
factor for the cournarin-based solutes. However, the second eluted enantiomer has a surprisingly
faster rate constant than the first enantiomer. The activation energy is positive, and the second
eluted enantiomer always has larger activation energy than the first enantiomer. These
thermodynamic and kinetic measurements provide a detailed and comprehensive view of the
chiral retention mechanism.
LC Short, SS Cai, JA Syage
APPI-MS: Effects of mobile phases and VUV lamps on the detection of PAH compounds
Journal of the American Society for Mass Spectrometry, 2007, Vol 18, Iss 4, pp 589-599
The technique of atmospheric pressure photoionization (APPI) has several advantages over
electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI), including
efficient ionization of nonpolar or low charge affinity compounds, reduced susceptibility to ion
suppression, high sensitivity, and large linear dynamic range. These benefits are greatest at low
flow rates (i.e.,< 100 mu L/min), while at a higher flow, photon absorption and ion-molecule
reactions become significant. Under certain circumstances, APPI signal and S/N have been
observed to excel at higher flow, which may be due to a nonphotoionzation mechanism. To better
understand APPI at higher flow rates, we have selected three lamps (Xe, Kr, and Ar) and four
mobile phases typical for reverse-phase, high-pressure liquid chromatography: acetonitrile,
methanol, (1:1) acetonitrile:water and (1:1) methanol:water. As test compounds, three
polyaromatic hydrocarbons are studied: benzo[a]pyrene, indeno[1,2,3-c, d]pyrene and
benz[a]anthracene. We find that solvent photoabsorption cross-section is not the only parameter
in explaining relative signal intensity, but that solvent photo-ion chemistry can also play a
significant role. Three conclusions from this investigation are: (1) methanol photoionization leads
to protonated methanol clusters that can result in chemical ionization of analyte molecule; (2) use
of the Ar lamp often results in greater signal and S/N; (3) acetonitrile photoionization is less
efficient and resulting clusters are too strongly bound to chemically ionize the analyte efficiently,
so that analyte ion formation is dominated by direct photoionization.
A ValeroNavarro, JF FernandezSanchez, AL MedinaCastillo, F FernandezIbanez, A
SeguraCarretero, JM Ibanez, A FernandezGutierrez
A rapid, sensitive screening test for polycyclic aromatic hydrocarbons applied to Antarctic water
Chemosphere, 2007, Vol 67, Iss 5, pp 903-910
We describe a rapid, sensitive, fluorescence screening test for polycyclic aromatic hydrocarbons
in water samples that avoids more costly time-consuming methods. The screening test works by
detecting benzo[a]pyrene. It runs without the need for any pre-concentration step, thus rendering
it suitable for routine use in water-quality-control laboratories. The test recognizes contaminated
samples rapidly (150s) and inexpensively with a cut-off level of 10 ng l(-1), which is the value that
the European Union and World Health Organization (WHO) have laid down in its assessment of
the quality of water for human consumption. This was first ascertained by analysing tap and
waste-water samples before studying environmental water samples from the Antarctic region.
The reliability of the screening test was 2% false positives and 4% false negatives in 200 samples
of tap and waste-water. The applicability was confirmed by the fact that the predictions of the
screening test coincided exactly with results obtained with gas chromatography-mass
spectrometry assays. We also discuss the polluted Antarctic samples and the possible sources of
the contamination involved.
YM Rhee, TJ Lee, MS Gudipati, LJ Allamandola, M HeadGordon
Charged polycyclic aromatic hydrocarbon clusters and the galactic extended red emission
Proceedings of the National Academy of Sciences of the United States of America, 2007, Vol
104, Iss 13, pp 5274-5278
The species responsible for the broad extended red emission (ERE), discovered in 1975 and now
known to be widespread throughout the Galaxy, still is unidentified. Spanning the range from
approximate to 540 to 900 nm, the ERE is a photoluminescent process associated with a wide
variety of different interstellar environments. Over the years, a number of plausible candidates
have been suggested, but subsequent observations ruled them out. The objects that present the
ERE also emit the infrared features attributed to free polycyclic aromatic hydrocarbon (PAH)
molecules, suggesting that closely related materials are plausible ERE carriers. Here, we show
that the peculiar spectra and unique properties of closed-shell cationic PAH dimers satisfy the
existing observational constraints and suggest that emission from mixtures of charged PAH
clusters accounts for much of the ERE. This work provides a view into the structures, stabilities,
abundances, and ionization balance of PAH-related species in the emission zones, which, in turn,
reflects physical conditions in the emission zones and sheds fundamental light on the nanoscale
processes involved in carbon-particle nucleation and growth and carbonaceous dust evolution in
the interstellar medium.
G Smith, UD Wermuth, PC Healy, JM White
3,5-dinitrosalicylic acid in molecular assembly. III. Proton-transfer compounds of 3,5dinitrosalicylic acid with polycyclic aromatic and heteroaromatic amines, and overall series
structural systematics
Australian Journal of Chemistry, 2007, Vol 60, Iss 4, pp 264-277
The crystal structures of the 1: 1 proton-transfer compounds of 3,5-dinitrosalicylic acid (dnsa) with
a series of common polycyclic aromatic and heteroaromatic amines (quinoline, 1-naphthylamine,
1,2,3,4-tetrahydroquinoline, quinaldic acid, benzimidazole, 1,10-phenanthroline, and 2,2'bipyridine) have been determined and the hydrogen-bonding associations in each analyzed. The
compounds are [(C9H8N)(+)(dnsa)(-)] 1, [(C10H10N)(+)(dnsa)(-)] 2, [(C9H12N)(+)(dnsa)(-)] 3,
[(C10H8NO2)(+)(dnsa)(-)] 4, [(C7H7N2)(+)(dnsa)(-)] 5, [(C12H9N2)(+)(dnsa)(-)] 6, and
[(C10H9N2)(+)(dnsa)(-)] 7. In all compounds, protonation of either the substituent amino group or
the hetero-N of the Lewis base occurs, with subsequent hydrogen bonding via this and other
hydrogen donors variously to the carboxylate, phenate, and nitro oxygen acceptors of the dnsa
anions. The result is the formation of primary N+-H center dot center dot center dot O
associations which with secondary peripheral interactions, which within this set of compounds
includes an increased incidence of aromatic C-H center dot center dot center dot O associations,
give framework polymer structures. In three of the compounds [ 1, 4, and 6], cation - anion p - p
interactions are also found. The completion of this series of compounds has now allowed the
categorization of the molecular assembly modes in the proton-transfer compounds of 3,5dinitrosalicylic acid.
HS Dorea, JRL Bispo, KAS Aragao, BB Cunha, S Navickiene, JPH Alves, LPC Romao, CAB
Garcia
Analysis of BTEX, PAHs and metals in the oilfield produced water in the State of Sergipe, Brazil
Microchemical Journal, 2007, Vol 85, Iss 2, pp 234-238
During oil and gas exploitation, large amounts of produced water are generated. This water has
to be analyzed with relation to the chemical composition to deduce the environmental impact of
its discharge after a treatment process. Therefore, a study was carried out to evaluate
preliminarily the BTEX (benzene, toluene, ethylbenzene and xylenes), PAHs and metals contents
in produced water samples taken from effluents of the Bonsucesso treatment plant located in the
city of Carmopolis, the most important oil and gas producer in the State of Sergipe, Northeast of
Brazil. Three methods were optimized to determine the target compounds. Polycyclic aromatic
hydrocarbons were determined by gas chromatography with mass spectrometric detection
(GC/MS), volatile aromatic hydrocarbons (BTEX) by gas chromatography with photoionization
detector (GC/PID) and metals were analyzed by flame atomic absorption spectrometry (FAAS).
The results showed that concentrations of the target compounds in these samples ranged from
96.7 to 1397 mu g L-1 for BTEX, from 0.9 to 10.3 mu g L-1 for PAHs and from 0.003 to 4540 mg
L-1 for metals.