The February 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
Literature Review
D. Kim, J. L. Petersen, and K. K. Wang
Synthesis of Bowl-Shaped Polycyclic Aromatic Hydrocarbons via Palladium Catalyzed Intramolecular Arylation
Reactions
Organic Commun., 8, 2313-2316
AL Pikkarainen
Ethoxyresorufin-O-deethylase (EROD) activity and bile metabolites as contamination indicators in Baltic
Determination by HPLC
Chemosphere, 2006, 65, 1888-1897
Exposure of Baltic Sea perch (Perca fluviatilis) to organic contaminants was investigated by means of liver
enzyme activity, measured as ethoxyresorufin-O-deethylase (EROD) activity, and PAH metabolites excreted to
bile. Female perch used in the study were caught in coastal waters of the western Gulf of Finland. Reaction
conditions were optimised for determination of EROD activity in liver. A high-performance liquid chromatography
(HPLC) method with fluorescence detection was developed to separate the interfering fluorescent signal from the
signal due to EROD activity. EROD activity in perch varied within a concentration range of 0.30-14 pmol min(-1)
mg(-1) protein. Recent PAH exposure was indicated in enhanced levels of the bile metabolite 1-hydroxypyrene,
which varied between 213 and 1149 mu g kg(-1). No correlation was indicated between hepatic EROD activity
and concentration of 1-hydroxypyrene.
JL Bonin, MJ Simpson
Variation in phenanthrene sorption coefficients with soil organic matter fractionation: The result of structure or
conformation?
Environmental Science & Technology, 2007, 41, 153-159
Sorption of phenanthrene to varying soil types was investigated to better understand sorption processes. Humic
acid and humin fractions were isolated from each soil sample, and sorption coefficients were measured by batch
equilibration. Samples were characterized by carbon analysis and C-13 cross polarization magic angle spinning
(CP/MAS) nuclear magnetic resonance (NMR) spectroscopy. Measured organic carbon-normalized sorption
coefficients (K-oc) of the fractions were greater in all cases when compared to the soils. The humin fractions
exhibited greater K-oc values than did source samples, suggesting that fractionation may reorganize organic
matter in humin resulting in an increased availability of and/or more favorable sorption domains. Mass balance
calculations revealed that the sum of sorption to the fractions is greater than sorption to the whole sample. The
greatest difference between sorption values was found to occur with the mineral soils, suggesting that clay
minerals influence the physical conformation of soil organic matter (SOM) and availability of sorption domains.
The mass balance, sorption data, and a lack of consistent trends between observed K-oc values and solid-state
C-13 NMR data suggest that the physical conformation of SOM and chemical characteristics both play important
roles in sorption processes.
JKC Nieman, RC Holz, RC Sims
C-13 NMR analysis of biologically produced pyrene residues by Mycobacterium sp KMS in the presence of humic
acid
Environmental Science & Technology, 2007, 41, 242-249
Cultures of the pyrene degrading Mycobacterium sp. KMS were incubated with [4-C-13]pyrene or [4,5,9,10-C-
14]pyrene with and without a soil humic acid standard to characterize the chemical nature of the produced
residues and evaluate the potential for bonding reactions with humic acid. Cultures were subjected to a ''humic
acid/humin'' separation at acidic pH, a duplicate separation followed by solvent extraction of the humic acid/humin
fraction, and a high pH separation. C-13 NMR analysis was conducted on the resulting solid extracts. Results
indicated that the activity associated with solid extracts did not depend on pH and that approximately 10% of the
added activity was not removed from the solid humic acid/humin fraction by solvent extraction. C-13 NMR
analysis supported the conclusion that the majority of pyrene metabolites were incorporated into cellular material.
Some evidence was found for metabolite reaction with the added humic material, but this did not appear to be a
primary fate mechanism.
CC Abnet, RB Fagundes, PT Strickland, F Kamangar, MJ Roth, PR Taylor, SM Dawsey
The influence of genetic polymorphisms in Ahr, CYP1A1, CYP1A2, CYP1B1, GST M1, GST T1 and UGT1A1 on
urine 1-hydroxypyrene glucuronide concentrations in healthy subjects from Rio Grande do Sul, Brazil
Carcinogenesis, 2007, 28, 112-117
Polymorphisms in genes encoding polycyclic aromatic hydrocarbon (PAH) metabolizing enzymes may alter
metabolism of these carcinogens and contribute to inter-individual difference in urine concentrations. We
investigated the influence of genetic polymorphism on PAH metabolism in urine from 199 healthy subjects from
Southern Brazil. We measured urine 1-hydroxypyrene glucuronide (1-OHPG) concentrations using immunoaffinity
chromatography and synchronous fluorescence spectroscopy and genotyped subjects using standard methods.
Genetic variants in CYP1B1 (rs1056827, rs1800440, rs10012) were strongly associated with urine 1-OHPG with
P-values < 0.010. Variants in aryl hydrocarbon receptor (Ahr) (rs4986826), CYP1A1 (rs1799814) and CYP1A2
(rs2069514) were also, although less strongly, associated with changes in urine 1-OHPG concentrations. These
variants had P-values of 0.074, 0.040 and 0.025, respectively. The median urine 1-OHPG concentrations
(pmol/ml) in the homozygous wild-type and homozygous variants for CYP1B1 (rs10012) and the Ahr, CYP1A1
and CYP1A2 variants listed above were 2.16 and 0.10, 2.16 and 0.41, 2.03 and 0.46, 2.19 and 2.79, respectively.
We found no effect of deletions in GST M1 or GST T1, or different alleles of UGT1A1*28. Adjusting for age, sex,
place of residence, tobacco smoke exposure, mate drinking, cachaca and barbeque preparation had only a minor
impact on the associations. A model containing just exposure variables had an r(2) of 0.21; a model with single
genotypes for Ahr, CYP1A1, CYP1A2 and CYP1B1 had an r(2) of 0.10; and a model combining both exposure
and genotype information had a total r(2) of 0.33. Our results suggest that CYP1B1 genotypes are strongly
associated with urine 1-OHPG concentrations in this population.
H Moriwaki
Liquid chromatography mass spectrometry for the analysis of environmental mutagens
Current Analytical Chemistry, 2007, 3, 69-79
One of the most important ecological problems is mutagenic pollution in the environment, and the determination
of mutagenic compounds in environmental samples is of special interest. In the current article, a review of the
liquid chromatography-mass spectrometry (LC/MS) based methods published so far for the determination of
mutagens in the environment is presented. Mutagens included in this review are polycyclic aromatic compounds,
heterocyclic aromatic amine compounds, azo dyes, aldehydes and pesticides. Advanced aspects of current
analysis of mutation research using LC/MS, including analysis of urinary metabolites of mutagens and DNA
modification, are also discussed.
FJ Wrona, TD Prowse, JD Reist, JE Hobbie, LMJ Levesque, RW Macdonald, WF Vincent
Effects of ultraviolet radiation and contaminant-related stressors on Arctic freshwater ecosystems
Ambio, 2006, 35, 388-401
Climate change is likely to act as a multiple stressor, leading to cumulative and/or synergistic impacts on aquatic
systems. Projected increases in temperature and corresponding alterations in precipitation regimes will enhance
contaminant influxes to aquatic systems, and independently increase the susceptibility of aquatic organisms to
contaminant exposure and effects. The consequences for the biota will in most cases be additive (cumulative)
and multiplicative (synergistic). The overall result will be higher contaminant loads and biomagnification in aquatic
ecosystems. Changes in stratospheric ozone and corresponding ultraviolet radiation regimes are also expected to
produce cumulative and/or synergistic effects on aquatic ecosystem structure and function. Reduced ice cover is
likely to have a much greater effect on underwater UV radiation exposure than the projected levels of
stratospheric ozone depletion. A major increase in UV radiation levels will cause enhanced damage to organisms
(biomolecular, cellular, and physiological damage, and alterations in species composition). Allocations of energy
and resources by aquatic biota to UV radiation protection will increase, probably decreasing trophic-level
productivity. Elemental fluxes will increase via photochemical pathways.
JS Seo, YS Keum, YT Hu, SE Lee, QX Li
Degradation of phenanthrene by Burkholderia sp C3: initial 1,2- and 3,4-dioxygenation and meta- and ortho-
cleavage of naphthalene-1,2-diol
Biodegradation, 2007, 18, 123-131
Burkholderia sp. C3 was isolated from a polycyclic aromatic hydrocarbon (PAH)-contaminated site in Hilo, Hawaii,
USA, and studied for its degradation of phenanthrene as a sole carbon source. The initial 3,4-C dioxygenation
was faster than 1,2-C dioxygenation in the first 3-day culture. However, 1-hydroxy-2-naphthoic acid derived from
3,4-C dioxygenation degraded much slower than 2-hydroxy-1-naphthoic acid derived from 1,2-C dioxygenation.
Slow degradation of 1-hydroxy-2-naphthoic acid relative to 2-hydroxy-1-naphthoic acid may trigger 1,2-C
dioxygenation faster after 3 days of culture. High concentrations of 5,6- and 7,8-benzocoumarins indicated that
meta-cleavage was the major degradation mechanism of phenanthrene-1,2- and -3,4-diols. Separate cultures
with 2-hydroxy-1-naphthoic acid and 1-hydroxy-2-naphthoic acid showed that the degradation rate of the former to
naphthalene-1,2-diol was much faster than that of the latter. The two upper metabolic pathways of phenanthrene
are converged into naphthalene-1,2-diol that is further metabolized to 2-carboxycinnamic acid and 2-
hydroxybenzalpyruvic acid by ortho- and meta-cleavages, respectively. Transformation of naphthalene-1,2-diol to
2-carboxycinnamic acid by this strain represents the first observation of ortho-cleavage of two rings-PAH-diols by
a Gram-negative species.
M Bergknut, K Frech, PL Andersson, P Haglund, M Tysklind
Characterization and classification of complex PAH samples using GC-qMS and GC-TOFMS
Chemosphere, 2006, 65, 2208-2215
Author keywords soil; anti-skid sand; urban dust; traffic; creosote; peak deconvolution; PCA
The aim of this study was to compare the polycyclic aromatic hydrocarbon (PAH) contents in a number of
complex samples, including soil samples from industrial sites, anti-skid sand, urban dust and ash samples from
municipal solid waste incinerators. The samples were characterized by routine analysis of PAHs (gas
chromatography-quadrupole mass spectrometry) and gas chromatography-time of flight mass spectrometry (GC-
TOFMS). Classification of the samples by principal component analysis (PCA) according to their composition of
PAHs revealed that samples associated with traffic and the municipal incinerator formed homogeneous clusters,
while the PAH-contaminated soils clustered in separate groups. Using spectral data to resolve co-eluting
chromatographic peaks, 962 peaks could be identified in the GC-TOFMS analysis of a pooled sample and 123-
527 peaks in the individual samples. Many of the studied extracts included a unique set of chemicals, indicating
that they had a much more diverse contamination profile than their PAH contents suggested. Compared to routine
analysis, GC-TOFMS provided more detailed information about each sample and in this study a large number of
alkylated PAHs were found to be associated with the corresponding unsubstituted PAHs. The possibility to filter
peaks according to different criteria (e.g. To include only peaks that were detected in the analysis of another
sample) was explored and used to identify unique as well as common compounds within samples. This procedure
could prove to be valuable for obtaining relevant chemical data for use in conjunction with results from various
biological test systems.
TG Luan, KSH Yu, Y Zhong, HW Zhou, CY Lan, NFY Tam
Study of metabolites from the degradation of polycyclic aromatic hydrocarbons (PAHs) by bacterial consortium
enriched from mangrove sediments
Chemosphere, 2006, 65, 2289-2296
The PAH metabolites produced during degradation of fluorene, phenanthrene and pyrene by a bacterial
consortium enriched from mangrove sediments were analyzed using the on-fiber silylation solid-phase
microextraction (SPME) combining with gas chromatography-mass spectrometry (GC-MS) method. Seventeen
metabolites at trace levels were identified in different PAH degradation cultures based on the full scan mass
spectra. In fluorene degradation cultures, 1-, 2-, 3- and 9-hydroxyfluorene, fluorenone, and phthalic acid were
detected. In phenanthrene and pyrene degradation cultures, various common metabolites such as phenanthrene
and pyrene dihydrodiols, mono-hydroxy phenanthrene, dihydroxy pyrene, lactone and 4-hydroxyphenanthrene,
methyl ester, and phthalic acid were found. The detection of various common and novel metabolites
demonstrates that SPME combining with GC-MS is a quick and convenient method for identification as well as
monitoring the real time changes of metabolite concentrations throughout the degradation processes. The
knowledge of PAH metabolic pathways and kinetics within indigenous bacterial consortium enriched from
mangrove sediments contributes to enhance the bioremediation efficiency of PAH in real environment.
.
P Konieczka, TPI Linsinger, J Namiesnik
Determination of PON in environmental matrices - proficiency tests for Polish laboratories
Accreditation and Quality Assurance, 2006, 11, 584-589
Thirty Polish laboratories participated in proficiency tests (PT) for determination of persistent organic pollutants -
POPs (PCBs polychlorinated biphenyls, PAHs polyaromatic hydrocarbons and pesticides) in solid environmental
matrices (sediments, soil). Participants used their in-house method. The aim of the exercises was to obtain
information about the ''state of the art'' of POPs analysis in environmental samples. The CV (coefficient of
variation) of analytical results submitted varied from 45 to 65%, with an outlier rate 2 to 7%. The averages of
results for all analytes were in good agreement with reference values. Statistical treatment of results was made.
Comparison of the each result with the certified values characterizing the material has been done. Additionally, z-
scores were calculated taking into account the uncertainty of a certified value and the acceptable deviation from
the certified value in the range of -20% to +10% (in accordance with recommendations in the newest directives of
European Union (EU) [1]); For rejecting outliers Hampel test has been applied.
K Cizek, J Barek, J Zima
Polarographic and voltammetric determination of trace amounts of 3-nitrofluoranthene
Collection of Czechoslovak Chemical Communications, 71, 1571-1587
The polarographic behavior of 3-nitrofluoranthene was investigated by DC tast polarography ( DCTP) and
differential pulse polarography ( DPP), both at a dropping mercury electrode, differential pulse voltammetry (DPV)
and adsorptive stripping voltammetry (AdSV), both at a hanging mercury drop electrode. Optimum conditions
have been found for its determination by the given methods in the concentration ranges of 1 x 10(-6) - 1 x 10(-4)
mol l(-1) (DCTP), 1 x 10(-7) - 1 x 10(-4) mol l(-1) (DPP), 1 x 10(-8) - 1 x 10(-6) mol l(-1) (DPV) and 1 x 10(-9) - 1 x
10(-7) mol l(-1) (AdSV), respectively. Practical applicability of these techniques was demonstrated on the
determination of 3-nitrofluoranthene in drinking and river water after its preliminary separation and
preconcentration using liquid - liquid and solid phase extraction with the limits of determination 4 x 10(-10) mol l(-
1) ( drinking water) and 2 x 10(-9) mol l(-1) ( river water).