The July 2008 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 new and improved ISPAC webpages are at http://www.ispac.org/
You can now pay your dues through the website!.
International Symposium on Polycyclic Aromatic Compounds, ISPAC
22, Charleston, South Carolina, USA: September 20- 24, 2009
http://www.ispac.org/Announcement%20ISPAC%2022.pdf
ISPAC members get a discount on registration!
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@ism.u-bordeaux1.fr
Literature search:
RT Kay, TL Arnold, WF Cannon, D Graham
Concentrations of polycyclic aromatic hydrocarbons and inorganic constituents in ambient surface soils,
Chicago, Illinois: 2001-2002
Soil & Sediment Contamination, 2008, Vol 17, Iss 3, pp 221-236
Samples of ambient surface soils were collected from 56 locations in Chicago, Illinois, using stratified
random sampling techniques and analyzed for polycyclic aromatic hydrocarbon (PAH) compounds and
inorganic constituents. PAHs appear to be derived primarily from combustion of fossil fuels and may be
affected by proximity to industrial operations, but do not appear to be substantially affected by the organic
carbon content of the soil, proximity to nonindustrial land uses, or proximity to a roadway. Atmospheric
settling of particulate matter appears to be an important mechanism for the placement of PAH compounds
into soils. Concentrations of most inorganic constituents are affected primarily by soil-forming processes.
Concentrations of lead, arsenic, mercury, calcium, magnesium, phosphorus, copper, molybdenum, zinc, and
selenium are elevated in ambient surface soils in Chicago in comparison to the surrounding area, indicating
anthropogenic sources for these elements in Chicago soils. Concentrations of calcium and magnesium in
Chicago soils appear to reflect the influence of the carbonate bedrock parent material on the chemical
composition of the soil, although the effects of concrete and road fill cannot be discounted. Concentrations
of inorganic constituents appear to be largely unaffected by the type of nearby land use.
PC VanMetre, V Mesnage, B Laignel, A Motelay, J Deloffre
Origins of sediment-associated contaminants to the Marais Vernier, the Seine Estuary, France
Water Air and Soil Pollution, 2008, Vol 191, Iss 1-4, pp 331-344
The Marais Vernier is the largest freshwater wetland in the Seine Estuary in northern France. It is in a
heavily urbanized and industrialized region and could be affected by atmospheric deposition and by fluvial
input of contaminants in water diverted from the Seine River. To evaluate contaminant histories in the
wetland and the region, sediment cores were collected from two open-water ponds in the Marais Vernier: the
Grand-Mare, which was connected to the Seine by a canal from 1950 to 1996, and the Petite Mare, which
has a small rural watershed. Diversions from the Seine to the Grand-Mare increased sedimentation rates but
mostly resulted in low contaminant concentrations and loading rates, indicating that the sediment from the
Seine was predominantly brought upstream by tidal currents from the estuary and was not from the
watershed. Atmospheric sources of metals dominate inputs to the Petite Mare; however, runoff of metals
from vehicle-related sources in the watershed might contribute to the upward trends in concentrations of Cr,
Cu, and Zn. Estimates of atmospheric deposition using the Petite Mare core are consistent with measured
deposition in the region and are mixed (similar for Hg and Pb; larger for Cd, Cu, and Zn) compared with
deposition estimated from sediment cores in the northeastern United States. A local source of PAHs in the
watershed of the Petite Mare is indicated by higher concentrations, higher accumulation rates, and a
different, more petrogenic, PAH assemblage than in the Grand-Mare. The study illustrates how diverse
sources and transport pathways can affect wetlands in industrial regions and can be evaluated using
sediment cores from the wetland ponds.
S Paria
Surfactant-enhanced remediation of organic contaminated soil and water
Advances in Colloid and Interface Science, 2008, Vol 138, Iss 1, pp 24-58
Surfactant based remediation technologies for organic contaminated soil and water (groundwater or surface
water) is of increasing importance recently. Surfactants are used to dramatically expedite the process, which
in turn, may reduce the treatment time of a site compared to use of water alone. In fact, among the various
available remediation technologies for organic contaminated sites, surfactant based process is one of the
most innovative technologies. To enhance the application of surfactant based technologies for remediation
of organic contaminated sites, it is very important to have a better understanding of the mechanisms
involved in this process. This paper will provide an overview of the recent developments in the area of
surfactant enhanced soil and groundwater remediation processes, focusing on (i) surfactant adsorption on
soil, (ii) micellar solubilization of organic hydrocarbons, (iii) supersolubilization, (iv) density modified
displacement, (v) degradation of organic hydrocarbon in presence surfactants, (vi) partitioning of surfactants
onto soil and liquid organic phase, (vii) partitioning of contaminants onto soil, and (viii) removal of organics
from soil in presence of surfactants. Surfactant adsorption on soil and/or sediment is an important step in
this process as it results in surfactant loss reduced the availability of the surfactants for solubilization. At the
same time, adsorbed surfactants will retained in the soil matrix, and may create other environmental
problem. The biosurfactants are become promising in this application due to their environmentally friendly
nature, nontoxic, low adsorption on to soil, and good solubilization efficiency. Effects of different parameters
like the effect of electrolyte, pH, soil mineral and organic content, soil composition etc. On surfactant
adsorption are discussed here. Micellar solubilization is also an important step for removal of organic
contaminants from the soil matrix, especially for low aqueous solubility organic contaminants. Influences of
different parameters such as single and mixed surfactant system, hydrophilic and hydrophobic chain length,
HLB value, temperature, electrolyte, surfactant type that are very important in micellar solubilization are
reviewed here. Microemulsion systems show higher capacity of organic hydrocarbons solubilization than the
normal micellar system. In the case of biodegradation of organic hydrocarbons, the rate is very slow due to
low water solubility and dissolution rate but the presence of surfactants may increase the bioavailability of
hydrophobic compounds by solubilization and hence increases the degradation rate. In some cases the
presence of it also reduces the rate. In addition to fundamental studies, some laboratory and field studies on
removal of organics from contaminated soil are also reviewed to show the applicability of this technology.
(C) 2007 Elsevier B.V. All rights reserved.
T Boubellouta, E Dufour
Effects of mild heating and acidification on the molecular structure of milk components as investigated by
synchronous front-face fluorescence spectroscopy coupled with parallel factor analysis
Applied Spectroscopy, 2008, Vol 62, Iss 5, pp 490-496
This paper reports the potential of synchronous front-face fluorescence spectroscopy in the characterization
at the molecular level of milk changes during mild heating from 4 to 50 degrees C and acidification in the pH
range of 6.8 to 5.1. Synchronous fluorescence spectra were collected in the 250-550 nm excitation
wavelength range using offsets of 20, 40, 60, 80, 100, 120, 140, 160, 180, 200, and 240 nm between
excitation and emission monochromators. The potential of parallel factor (PARAFAC) analysis in the
decomposition of the whole synchronous fluorescence data set into the contribution of each of the
fluorescent compounds present in milk has been investigated for heating and acidification data sets. Models
were fitted from 1 to 7 components. Considering the core consistency values, PARAFAC models with three
components have been considered. The first three components explained 94.43% and 94.13% of the total
variance for heating and acidification data sets, respectively. The loading profiles of the first and second
components derived from PARAFAC analysis performed on heating and acidification data sets
corresponded quite well with the characteristics of tryptophan and vitamin A fluorescence spectra,
respectively. The third component corresponded to the riboflavin fluorescence spectrum. Considering the
heating experiment, the profile of the concentration mode for the second component showed large variations
according to the temperature, which were assigned to the melting of triglycerides between 4 and 50 degrees
C. For the acidification experiment, drastic changes in the concentration modes of the three components
were observed for pH below 5.6, in agreement with structural changes in casein micelles.
Y Marcus
On the preferential solvation of drugs and PAHs in binary solvent mixtures
Journal of Molecular Liquids, 2008, Vol 140, Iss 1-3, pp 61-67
The preferential solvation parameters, i.e., the differences between the local and bulk mole fractions of the
solvents in solutions of certain drugs and polycyclic aromatic hydrocarbons (PAHs) are derived from their
solubilities in binary solvent mixtures by means of the inverse Kirkwood-Buff integral (IKBI) and the quasilattice quasi-chemical (QLQC) methods. The solutes include caffeine, niflumic acid, diazepam, benzocaine,
phenacetin, paracetamol, nalidixic acid, anthracene, and tr-stilbene and both aqueous and non-aqueous
mixtures are considered. The findings are rationalized in terms of the interactions between the solute and
solvents and the solvent components among themselves..
S Hyun, MY Ahn, AR Zimmerman, M Kim, JG Kim
Implication of hydraulic properties of bioremediated diesel-contaminated soil
Chemosphere, 2008, Vol 71, Iss 9, pp 1646-1653
The hydraulic properties, such as hydraulic conductivity and water retention, of aged diesel-contaminated
and bioremediated soils were examined and implications of the hydraulic properties for assessing
bioremediation performance of soils were proposed. Bioremediation of diesel-contaminated soil was
performed over 80 d using three treatments; (I) no nutrient added, column-packed soil, (II) nutrient added,
column-packed soil, and (III) nutrient added, loosen soil. Diesel reduction in treatment I soil (control soil) was
negligible while treatment III showed the greatest extent of diesel biodegradation. All treatments showed
greatest rates of diesel biodegradation during the first 20 d, followed by a much retarded biodegradation rate
in the remaining incubation period. Reduction of the degradation rate due to entrained diesel within
inaccessible soil pores was hypothesized and tested by measuring the hydraulic properties of two columnpacked soils (treatments I and II). The hydraulic conductivity of treatment II soil (nutrient added) was
consistently above that of treatment I soil (no nutrient added) at pressure heads between 0 and 15 cm. In
addition, the water retention of treatment II soil was greater at pressure heads <100 cm (equivalent to pore
size of >30 mu m), suggesting that biodegradative removal of hydrocarbons results in enhanced wettability
of larger soil pores. However, water retention was not significantly different for control and biodegraded soils
at pressure heads >100 cm, where smaller size soil pores were responsible for the water retention,
indicating that diesel remained in smaller soil pores (e.g., <30 mu m). Both incubation kinetics and hydraulic
measurements suggest that hydrocarbons located in small pores with limited microbe accessibility may be
recalcitrant to bioremediation.
R Piazza, AC RuizFernandez, M Frignani, R Zangrando, LG Bellucci, I Moret, F PaezOsuna
PCBs and PAHs in surficial sediments from aquatic environments of Mexico City and the coastal states of
Sonora, Sinaloa, Oaxaca and Veracruz (Mexico)
Environmental Geology, 2008, Vol 54, Iss 7, pp 1537-1545
Concentrations of PCBs and PAHs were measured in 13 surficial sediment samples collected at three
lacustrine locations in the surroundings of Mexico City and four coastal areas of the States of Sinaloa,
Sonora, Oaxaca and Veracruz. Total PCB concentrations span the interval 3.18-621 ng g(-1). The highest
values (63.7-621 ng g(-1)) were found in Mexico City, which is a highly anthropogenically impacted area,
whereas low concentrations (3.18-12.9 ng g(-1)) were characteristic of seven places, some of them subject
to intense hydrodynamics. In these latter cases, values increase by 18-73 times if normalised against the
fine fraction (silt plus clay) content in sediment. Two samples from Mexico City exceed the ERM (Effect
Range Median) guidelines and are likely to cause adverse effects. Samples contain only lower chlorinated
PCBs (mainly 2-, 3- and 4-CB), thus suggesting that the most used PCB commercial mixture was Aroclor
1242. The homologue composition of the sample taken close to the nuclear power plant of Laguna Verde is
identical to this commercial mixture. PAHs in the same samples have relatively low concentrations (14.9-287
ng g(-1)), well below ERL (Effect Range Low) guidelines. The composition of PAH mixtures accounts for the
influence of both petrogenic and pyrolitic sources, with these latter prevailing at some places in Mexico City.
GF Slater, BR Cowie, N Harper, IG Droppo
Variation in PAH inputs and microbial community in surface sediments of Hamilton Harbour: Implications to
remediation and monitoring
Environmental Pollution, 2008, Vol 153, Iss 1, pp 60-70
Variations in concentrations of polycyclic aromatic hydrocarbons (PAHs) and microbial community indicators
were investigated in representative highly contaminated and less contaminated surface sediment sites of
Hamilton Harbour. Inputs of PAH to the upper 3 cm of sediments up to four times the average upper
sediment concentrations were observed. Associated PAH fingerprint profiles indicated that the source was
consistent with the PAH source to the industrial region of the harbour. Increased PAH loadings were
associated with decreased bacterial populations as indicated by phospholipid fatty acid (PLFA)
concentrations. However, relatively minor impacts on overall community composition were indicated.
Porewater methane concentrations and isotopic data indicated a difference in the occurrence of methane
oxidation between the two sites. This study confirms temporally limited transport of contaminants from highly
impacted regions as a vector for contaminants within the harbour and the impact on microbial carbon cycling
and bed stability.
I Zorita, M OrtizZarragoitia, I Apraiz, I Cancio, A Orbea, M Soto, I Marigomez, MR Cajaraville
Assessment of biological effects of environmental pollution along the NW Mediterranean Sea using red
mullets as sentinel organisms
Environmental Pollution, 2008, Vol 153, Iss 1, pp 157-168
A biomonitoring program was carried out in spring and autumn in three pollution hot-spots and sensitive
areas of the NW Mediterranean Sea using red mullets (Mullus barbatus) as sentinel organisms and a battery
of biomarkers together with gonad histology. In fish from anthropogenic impacted areas (Fos-sur-mer,
Cortiou, Arenzano, Delta of Ebro) lysosomal membrane destabilization occurred indicating disturbed health.
There were no significant differences in inetallothionein (MT) levels among stations. Peroxisomal acyl-CoA
oxidase (AOX) activity was highest in fish from Cortiou. Both MT levels and AOX activities were significantly
correlated with gamete development. Prevalence of melanomacrophage centers were high in Cortiou in all
samplings and in Fos-sur-mer in September samplings. In conclusion, the application of a battery of
biomarkers in red mullets provided relevant data for the assessment of environmental pollution in the NW
Mediterranean Sea but also showed the difficulties of using native fish as sentinels. For future studies
caging strategies are recommended.
A Abrahamson, I Brandt, B Brunstrom, RC Sundt, EH Jorgensen
Monitoring contaminants from oil production at sea by measuring gill EROD activity in Atlantic cod (Gadus
morhua)
Environmental Pollution, 2008, Vol 153, Iss 1, pp 169-175
An ex vivo gill EROD assay was applied in Atlantic cod (Gadus morhua) as a biomarker for waterborne
CYP1A-inducing compounds derived from oil production at sea. Exposure to nominal concentrations of 1
ppm or 10 ppm North Sea crude oil in a static water system for 24 h caused a concentration-dependent gill
EROD induction. Further, exposure of cod for 14 days to environmentally relevant concentrations of
produced water (PW, diluted 1:200 or 1: 1000) from a platform in the North Sea using a flow-through system
resulted in a concentration-dependent induction of gill EROD. Crude oil (0.2 ppm) from the same oil field
also proved to induce EROD. Finally, gill EROD activity in cod caged for 6 weeks at 500-10000 m from two
platforms Outside Norway was measured. The activities in these fish were very low and did not differ from
those in fish caged at reference sites.
LQ Pan, JJ Miao, J Wang, J Liu
AHH activity, tissue dose and DNA damage in different tissues of the scallop Chlamys farreri exposed to
benzo[a]pyrene
Environmental Pollution, 2008, Vol 153, Iss 1, pp 192-198
A collaborative study was performed on scallops (Chlamys farreri) exposed to 0.5, 3 and 10 mu g/L
benzo[a]pyrene (B[a]P) for 20 days. The levels of aryl hydrocarbon hydroxylase (AHH) activity, B[a]P
accumulation and DNA strand break were assayed in the gill and digestive bland. Results showed that AHH
activity and B[a]P accumulation were significantly related to B[a]P dose. AHH activity was induced and then
became stable gradually. B[a]P accumulation increased first and showed an incoming plateau. DNA strand
break levels in the 0.5 and 3 mu g/L B[a]P groups remained high and significantly different from control
values until day 6, followed by a reduction in the gill and no recovery in the digestive gland. The 10 mu g/L
B[a]P groups remained significantly lower than control until the end. These results suggested that the
application of comprehensive indices may give information on the actual exposure of organisms to
pollutants, and also information on toxic effects.
YC Lin, WJ Lee, HR Chao, SL Wang, TC Tsou, GP ChangChien, PJ Tsai
Approach for energy saving and pollution reducing by fueling diesel engines with emulsified
biosolution/biodiesel/diesel blends
Environmental Science & Technology, 2008, Vol 42, Iss 10, pp 3849-3855
The developments of both biodiesel and emulsified diesel are being driven by the need for reducing
emissions from diesel engines and saving energy. Artificial chemical additives are also being used in diesel
engines for increasing their combustion efficiencies. But the effects associated with the use of emulsified
additive/biodiesel/diesel blends in diesel engines have never been assessed. In this research, the premium
diesel fuel (PDF) was used as the reference fuel. A soy-biodiesel was selected as the test biodiesel. A
biosolution made of 96.5 wt % natural organic enzyme-7F (NOE-7F) and 3.5 wt % water (NOE-7F water)
was used as the fuel additive. By adding additional 1 vol % of surfactant into the fuel blend, a
nanotechnology was used to form emulsified biosolution/soy-biodiesel/PDF blends for fueling the diesel
engine. We found that the emulsified biosolution/soy-biodiesel/PDF blends did not separate after being kept
motionless for 30 days. The above stability suggests that the above combinations are suitable for diesel
engines as alternative fuels. Particularly, we found that the emulsified biosolution/soy-biodiesel/PDF blends
did have the advantage in saving energy and reducing the emissions of both particulate matters (PM) and
polycyclic aromatic hydrocarbons (PAHs) from diesel engines as compared with PDF, soy-biodiesel/PDF
blends, and emulsified soy-biodiesel/PDF blends. The results obtained from this study will provide useful
approaches for reducing the petroleum reliance, pollution, and global warming. However, it should be noted
that NOx emissions were not measured in the present study which warrants the need for future
investigation.
PL Ferguson, GT Chandler, RC Templeton, A Demarco, WA Scrivens, BA Englehart
Influence of sediment-amendment with single-walled carbon nanotubes and diesel soot on bioaccumulation
of hydrophobic organic contaminants by benthic invertebrates
Environmental Science & Technology, 2008, Vol 42, Iss 10, pp 3879-3885
Single-walled carbon nanotubes (SWNT) have extremely high affinity for hydrophobic organic contaminants,
considerably higher than natural or refractory (e.g., soot and detrital) carbon found in sediments. To evaluate
the effect of sediment-associated SWNT on contaminant uptake from sediments by infaunal deposit feeders,
we have conducted a comparative bioaccumulation study using two infaunal estuarine invertebrates. The
deposit-feeding meiobenthic copepod Amphiascus tenuiremis and the deposit/suspension-feeding
polychaete Streblospio benedicti were exposed to hydrophobic organic contaminants (HOCs) including
polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls, and polybrominated diphenyl ethers for
14 days in the presence of sediment amended with (1) SWNTs, (2) NIST diesel soot, or (3) no carbon
amendment. Coaddition of SWNT to sediments significantly reduced bioaccumulation of HOCs in S.
Benedicti, however, soot addition tended to increase the bioaccumulation of these same compounds in the
polychaete worm. Bioaccumulation of HOCs from sediments by copepods (A. Tenuiremis) was less
dependent on black carbon addition to sediment; neither SWNT nor soot significantly impacted
bioaccumulation of PAHs from sediment by this organism. Exposure of both copepods and polychaetes to
radiolabeled (C-14) SWNT in estuarine sediments revealed that these organisms did not assimilate these
materials into their tissues, although S. Benedicti did ingest C-14-SWNT, as fecal rods from this organism
contained identical IT activity as that of the sediment to which the worms were exposed.
E CervantesGonzalez, NG RojasAvelizapa, R CruzCamarillo, J GarciaMena, LI RojasAvelizapa
Oil-removal enhancement in media with keratinous or chitinous wastes by hydrocarbon-degrading bacteria
isolated from oil-polluted soils
Environmental Technology, 2008, Vol 29, Iss 2, pp 171-182
The aim of this work was to isolate oil-degrading bacteria that use chitin or keratin as carbon sources from
oil contaminated soils; and additionally to study if oil removal by these bacteria is enhanced when a
chitinous or a keratinous waste is added to the culture media. To isolate the above-mentioned bacteria, 12
soil samples were collected close to an oil-well. Such soils showed unsuitable nutrients content, but their
counts of heterotrophic bacteria ranged within 10(5) - 10(8) CFU g(-1) soil, of which 0.1-77% corresponded
to oil hydrocarbon-degrading ones. By sampling on plates, 109 oil-degrading bacterial isolates were
obtained. Their keratinase and chitinase activities were then screened by plate assays and
spectrophotometric methods, resulting in 13 isolates that were used to integrate two mixed cultures, one
keratinolytic and the other chitinolytic. These mixed cultures were grown in media with oil, or oil
supplemented with chicken-feathers or shrimp wastes. The oil-hydrocarbon removal was measured by gas
chromatography. Results showed that keratinolytic bacteria were better enzyme producers than the
chitinolytic ones, and that oil removal in the presence of chicken-feathers was 3.8 times greater than with
shrimp wastes, and almost twice, in comparison with oil-only added cultures. Identification of
microorganisms from the mixed cultures by 16S rDNA, indicated the presence of seven different bacterial
genera; Stenotrophomonas, Pseudomonas, Brevibacillus, Bacillus, Micrococcus, Lysobacter and
Nocardiodes. These findings suggest that the isolated microorganisms and the chicken-feather wastes could
be applied to the cleaning of oil-contaminated environments, whether in soil or water.
JL Goldfarb, EM Suuberg
Vapor pressures and thermodynamics of oxygen-containing polycyclic aromatic hydrocarbons measured
using Knudsen effusion
Environmental Toxicology and Chemistry, 2008, Vol 27, Iss 6, pp 1244-1249
PAHs and their oxygenated derivatives (OPAHs) are ubiquitous environmental pollutants resulting from the
incomplete combustion of coal and fossil fuels. Their vapor pressures are key thermodynamic data essential
for modeling fate and transport within the environment. The present study involved nine PAHs containing
oxygen heteroatoms, including aldehyde, carboxyl, and nitro groups, specifically 2-nitrofluorene, 9fluorenecarboxylic acid, 2-fluorenecarboxaldehyde, 2-anthracenecarboxylic acid, 9-anthracenecarboxylic
acid, 9-anthraldehyde, 1-nitropyrene, 1-pyrenecarboxaldehyde, and 1-bromo-2-naphthoic acid. The vapor
pressures of these compounds, with molecular weights ranging from 194 to 251 g/mol, were measured
using the isothermal Knudsen effusion technique in the temperature range of 329 to 421 K. The
corresponding enthalpies of sublimation, calculated via the Clausius-Clapeyron equation, are compared to
parent, nonoxygenated PAH compound data to determine the effect of the addition of these oxygencontaining heteroatoms. As expected, the addition of -CHO, -COOH, and -NO2 groups onto these PAHs
increases the enthalpy of sublimation and decreases the vapor pressure as compared to the parent PAH;
the position of substitution also plays a significant role in determining the vapor pressure of these OPAHs.
YW Yang, XY Dong, MC Jin, QL Ren
Rapid determination of polycyclic aromatic hydrocarbons in natural tocopherols by high-performance liquid
chromatography with fluorescence detection
Food Chemistry, 2008, Vol 110, Iss 1, pp 226-232
A simple and rapid method has been developed and validated for the determination of seventeen PAHs in
natural tocopherol products. Samples were dissolved in n-hexane, cleaned by an alumina column, and
separated and determined by reversed-phase high-performance liquid chromatography (HPLC) with
fluorescence detection. The recoveries were greater than 77.9%, except for the lowest molecular weight
PAHs (Na, 1-Me, 2-Me, AC, F) which were between 15.9% and 75.8%. The limits of quantification were less
than 0.38 ng/g for the heavy PAHs and less than 1.50 ng/g for the light PAHs. Good repeatabilities were
achieved with RSD less than 10.7% for all the objective compounds. This method has been applied to
evaluating PAHs contents in various natural tocopherol products and controlling natural tocopherol product
quality.
D Dimitriadou, A Zotos, D Petridis, AKD Taylor
Improvement in the production of smoked trout fillets (Salmo Gairdnerii) steamed with liquid smoke
Food Science and Technology International, 2008, Vol 14, Iss 1, pp 67-77
A fish smoking process was applied using a combination of liquid smoke and steaming at pressures up to 1
bar above atmospheric pressure. Drying and brining prior to smoking have not shown any significant effect
on the quality of the trout fillets. The nondried and dried for 4 h trout fillets prior to processing were assessed
as slightly more acceptable products, processing yield, sensory analysis, instrumental color, pH, available
lysine, polycyclic aromatic hydrocarbons ( PAHs) and preservation time were estimated. The losses due to
processing of the nondried samples were 23.7%, while 28.8% for those dried for 4 h. The fillets processed at
1.5 and 2 bar steam pressure were assessed as highly acceptable. Lightness ( L*) showed a decreasing
trend due to pressure while redness ( a*), and yellowness ( b*) an increasing one. The destruction of
available lysine was low ( 13.20% +/- 1.01) and it was slightly dependent upon the process. No PAHs were
detected. The preservation time, studied via total viable count, lactic acid bacteria, existence of Listeria
monocytogenes, and sensory analysis, extended to more than 98 days at 4 +/- 1 8 degrees C. The drying
prior to processing seems to affect the preservation time. This processing technique is much simpler, faster,
environmental effective, and leads to high quality smoked products.
G Coral, MNU Coral
Detection of polycyclic aromatic hydrocarbon (PAH) degradation genes in polluted soil by DNA extraction
and colony hybridization
Fresenius Environmental Bulletin, 2008, Vol 17, Iss 4, pp 478-485
The aim of this study is to detect the DNA sequences for the PAH-dioxygenase gene, the key enzyme of the
aerobic catabolic for polycyclic aromatic hydrocarbon degradation, in soil microorganisms by using
extraction of total DNA, PCR amplification PAH-dioxygenase sequences, and detection with colony
hybridization. To determine whether bacteria containing PAH-dioxygenase gene actually exist in
environments contaminated by crude oil or not, the genomic DNA was purified using a genomic DNA
purification kit. Purified genomic DNA was then amplified with a thermal cycler, and the PCR products were
separeted by agarose gel electrophoresis. Pseudomonas sp. Strain ARP 26, which is capable of degrading
phenanthrene, was used as target for colony hybridization. It was confirmed that Pseudomonas sp. Strain
ARP 26 demonstrated DNA sequence homology to the digoxigenin-labeled DNA probes used.
P Soonthornnonda, ER Christensen
Source apportionment of pollutants and flows of combined sewer wastewater
Water Research, 2008, Vol 42, Iss 8-9, pp 1989-1998
To reduce the combined sewer overflows (CSOs) and improve surface water quality in the Greater
Milwaukee area, construction of a 19.5-mile (31.4km) inline storage system (ISS) was completed in 1994 to
capture and convey sanitary sewage and stormwater for treatment. However, one to six overflows per year
still occur. Chemical mass balance (CMB) and positive matrix factorization (PMF) modeling was done in
order to find origins of flows and pollutants in CSOs. Based on overflow events from 2000 to 2006 (CMB)
and 2004 to 2006 (PMF), we found that between 27% and 56% of the total overflow is from sanitary sewage
and most of the remaining from stormwater with possible minor contribution (<= 8%) from groundwater. Most
total suspended solids and metals (Cd, Cr, Cu, Pb, Ni, Hg, and Zn) are from stormwater, while sanitary
sewage carries large contributions (>= 28%) of BOD5, NH3, and total phosphorus. The fraction of NH3 is
especially high, i.e., >= 58%. Implications for a possible future sewer separation in combined sewer areas
into separate sanitary and storm sewers are discussed. (C) 2007 Elsevier Ltd. All rights reserved.
J Tollback, MB Bigata, C Crescenzi, J Strom
Feasibility of analyzing fine particulate matter in air using solid-phase extraction membranes and dynamic
subcritical water extraction
Analytical Chemistry, 2008, Vol 80, Iss 9, pp 3159-3167
We have evaluated the feasibility of using Empore solid-phase extraction (SPE) membranes as an
alternative to conventional techniques for sampling fine airborne particulate matter (PM), including
nanoparticles, utilizing a scanning mobility particle sizer (SMPS) and a condensation particle counter to
evaluate their efficiency for trapping fine particles in the 10-800 nm size range. The results demonstrate that
the membranes can efficiently trap these particles and can then be conveniently packed into an extraction
cell and extracted under matrix solid-phase dispersion (MSPD) conditions. The potential utility of sampling
PM using Empore membranes followed by dynamic subcritical water extraction (DSWE) for fast, efficient,
class-selective extraction of polycyclic aromatic hydrocarbons (PAHs) associated with the particles, prior to
changing the solvent and analysis by GC/MS, was then explored. The performance of the method was
tested using National Institute of Standards and Technology (NIST)-certified ''urban dust'' reference material
(SRM 1649a) and real samples collected at a site in central Rome with heavy road traffic. Ne method
appears to provide comparable extraction efficiency to that of conventional techniques and with using
GC/MS, detection limits ranged in the few picograms per cubic meter level. Sampling PM by Empore
membranes may reduce the risks of losses of semivolatile compounds, while allowing relatively high
sampling flow rates and safe sample storage. Moreover, the combination of MSPD with DSWE permits
specific fractions of the PM components to be eluted, thereby generating clean extracts and reducing both
analysis time and sample manipulation.
Y Kodama, LI Stiknowati, A Ueki, K Ueki, K Watanabe
Thalassospira tepidiphila sp nov., a polycyclic aromatic hydrocarbon-degrading bacterium isolated from
seawater
International Journal of Systematic and Evolutionary Microbiology, 2008, Vol 58, Part 3, pp 711-715
A Gram-negative, mesophilic bacterial strain, designated 1-1B(T), which degrades PAHs, was isolated from
petroleum-contaminated seawater during a bioremediation experiment. A 16S rRNA gene sequence
analysis indicated that the isolate was affiliated with the genus Thalassospira in the Alphaproteobacteria; the
sequence was found to be most similar to those of Thalassospira profundimaris WP0211(T) (99.8%),
Thalassospira xiamenensis M-5(T) (98.2%) and Thalassospira lucentensis DSM 14000(T) (98.1%).
However, the levels of DNA-DNA relatedness between strain 1-1B(T) and these type strains were 50.7 +/17.2, 35.7 +/- 17.8 and 32.0 +/- 21.1%, respectively. In addition, strain 1-1B(T) was found to be distinct from
the other described species of the genus Thalassospira in terms of some taxonomically important traits,
including DNA G+C content, optimum growth temperature, salinity tolerance, utilization of carbon sources
and fatty acid composition. Furthermore, strain 1-1B(T) and T. Profundimaris were also different with regard
to motility and denitrification capacities. On the basis of physiological and DNA-DNA hybridization data,
strain 1-1B(T) represents a novel species within the genus Thalassospira, for which the name Thalassospira
tepidiphila sp. Nov. Is proposed. The type strain is 1-1B(T) (=JCM 14578(T) = DSM 18888(T)).
VI Petrova, GI Batova, AV Kursheva, IV Litvinenko, VM Savinov, TN Savinova
Geochemistry of polycyclic aromatic hydrocarbons in the bottom sediments of the eastern Arctic shelf
Oceanology, 2008, Vol 48, Iss 2, pp 196-203
Sources and pathways of supply of polycyclic aromatic hydrocarbons (PAH) in the surface sediments of the
Laptev and East Siberian seas were identified based on an analysis of the lithological-geochemical
characteristics and distribution of organic matter (OM). The distribution of organic carbon, humic acids,
bitumoids, and hydrocarbons demonstrates the determining role of the riverine runoff in the formation of the
recent sediments. The total average content of PAH in the sediments of this region approximates 37 ng/g,
not exceeding 80 ng/g of dry sediment. The biogenic components of the PAH (alkylphenanthrenes,
alkylchrysenes, perylene) dominate in the estuarine-shelf and coastal-shelf sediments enriched with plant
detritus and significantly decrease in the pelagic zone. The anthropogenic influence is observed in
sediments of the port of Tiksi, where the total content of PAH with dominant pyrogenic components is two
orders of magnitude higher as compared with the background values in the study region.
V Bartkevics, A Kukare, A Morozovs
Polycyclic aromatic hydrocarbons in meat smoked with different types of wood
Food Chemistry, 2008, Vol 110, Iss 3, pp 794-797
The influence of the wood used for the smoking of meat on the formation of PAHs has been studied. Ten
types of wood and charcoal were used for preparation of smoked meat samples. The analytical sample
preparation method implied extraction of PAH with cyclohexane, liquid-liquid extraction with N,Ndimethylformamide/water, back extraction with cyclohexane, followed by clean-up on silica solid phase
extraction (SPE) column and quantification by gas chromatography-mass spectrometry. It was found that the
type of wood has a significant influence on the amount of PAH in smoked meat. The samples smoked with
apple-tree and alder contained the smallest PAH concentrations. The samples smoked with spruce had the
highest concentrations of PAH. The difference in content of benzo[a]pyrene (from 6.04 till 35.07 mu g/kg)
and total PAH (from 47.94 till 470.91 mu g/kg) indicates that choice of wood for smoking is one of the critical
parameter to be controlled in order to diminish the contamination of food products. (C) 2008 Elsevier Ltd. All
rights reserved.
K Vatsavai, HC Goicoechea, AD Campiglia
Direct quantification of monohydroxy-polycyclic aromatic hydrocarbons in synthetic urine samples via solidphase extraction-room-temperature fluorescence excitation-emission matrix spectroscopy
Analytical Biochemistry, 2008, Vol 376, Iss 2, pp 213-220
A screening method for six biomarkers from polycyclic aromatic hydrocarbons (PAH) exposure in urine
samples is presented. Solid-phase extraction is carried out on commercial C18 cartridges via an optimized
procedure that minimizes metabolite loss. PAH metabolites are directly determined in the eluting solvent (3
mL of methanol) without the need of previous solvent evaporation. Spectral overlapping is resolved with the
combination of unfolded partial least squares and residual bilinearization. Excellent analytical figures of merit
were obtained for all the studied metabolites. Analytical recoveries varied between 87.9% (9hydroxyphenanthrene) and 99.4% (3-hydroxybenzo[o]pyrene). For 10 mL of urine sample, the limits of
detection varied between 0.01 ng.mL(-1) (3-hydroxybenzo[o]pyerene and 1-hydroxybenzopyrene) and 0.3
ng.mL(-1) (2-hydroxynaphthalene). Because the chemometric algorithm is capable of handling more than six
metabolites at once, the application of this approach to a larger number of metabolites is feasible.
R Kobayashi, RA Okamoto, RL Maddalena, NY Kado
Polycyclic aromatic hydrocarbons in edible grain: A pilot study of agricultural crops as a human exposure
pathway for environmental contaminants using wheat as a model crop
Environmental Research, 2008, Vol 107, Iss 2, pp 145-151
The concentrations of PAHs were investigated in a pilot study of field wheat grain as a model indicator for
environmental contamination. The edible grain would serve as a portal for human exposure. Wheat grain
was initially studied since it is one of the major food crops consumed internationally by many including
infants and children. Wheat grain samples from five different geographical growing locations in California
that span approximately 450 kin were collected during the same growing season. The same variety of grain
was harvested and analyzed for PAHs that ranged from 2- to 6-rings. PAHs were detected in all grain
samples and were mainly 2- to 4-ring PAHs with naphthalene the most abundant among them. There were
geographical differences in the levels of PAHs in the grain. The sources of the PAHs were not known in this
pilot study, but the principal component analysis indicates that the major source is similar in all locations
except for naphthalene. Grain naphthalene concentrations may reflect local naphthalene emissions. Dieselfueled harvesting operations did not appear to contribute to the observed PAH concentrations in the grain.
An estimate of naphthalene intake from eating grain compared to inhalation intake demonstrated the
potential importance of field contamination of grain as a possible portal of human exposure. The relationship
between PAH concentrations in grain and air should be quantitatively investigated to better quantitate
exposure and to identify effective measures to lower the risk from PAH exposure through eating grain.
K Taguchi, M Shimada, S Fujii, D Sumi, X Pan, S Yamano, T Nishiyama, A Hiratsuka, M Yamamoto, AK
Cho, JR Froines, Y Kumagai
Redox cycling of 9,10-phenanthraquinone to cause oxidative stress is terminated through its
monoglucuronide conjugation in human pulmonary epithelial A549 cells
Free Radical Biology and Medicine, 2008, Vol 44, Iss 8, pp 1645-1655
9, 10-Phenanthraquinone (PQ), a component of airborne particulate matter, causes marked cellular protein
oxidation and cytotoxicity through a two-electron reduction to 9,10-dihydroxyphenanthrene (PQH(2)), which
is associated with the propagation of reactive oxygen species (K. Taguchi et al., Free Radic. Biol. Med.
43:789-799, 2007). In the present study, we explored a biotransformation pathway for the detoxification of
PQ Exposure of human pulmonary epithelial A549 cells to PQ resulted in a time-dependent appearance of
an unknown metabolite in the medium that was identified as the monoglucuronide of PQH2 (PQHG).
Whereas a variety of isozymes of uridine 5'-diphosphate glucuronosyltransferase (UGTs) are responsible for
PQHG formation, UGT1A10 and UGT1A6 were particularly effective catalysts for glucuronide conj Ligation.
In cell-free systems, PQ exhibited a rapid thiol oxidation and subsequent oxygen consumption in the
presence of dithiothreitol, whereas PQHG did not. Unlike the parent compound, PQHG completely lost the
ability to oxidize cellular proteins and cause cell death in A549 cells. In addition, deletion of the transcription
factor Nrf2 decreased PQHG formation and increased PQ-mediated toxicity of mouse primary hepatocytes.
Thus, we conclude that PQHG is a metabolite of PQ, generated through PQH2, that terminates its redox
cycling and transports it to extracellular space.
GN Lu, Z Dang, XQ Tao, C Yang, XY Yi
Estimation of water solubility of polycyclic aromatic hydrocarbons using quantum chemical descriptors and
partial least squares
QSAR & Combinatorial Science, 2008, Vol 27, Iss 5, pp 618-626
Quantitative Structure-Property Relationship (QSPR) modeling is a powerful approach for predicting the
properties of environmental organic pollutants from their structure descriptors. In this study, QSPR models
were established for estimating the water solubility of Polycyclic Aromatic Hydrocarbons (PAHs). Quantum
chemical descriptors computed with density functional theory at the B3LYP/6-31G(d) level and Partial Least
Squares (PLS) analysis with an optimizing procedure were used to generate QSPR models for the logarithm
of the water solubility of PAHs. Two optimized models with high correlation coefficients (R-2=0.966 and
0.970) were obtained for estimating logarithmic mass and molar concentration of water solubility,
respectively. The internal statistics results of a cross-validation test (Q(cum)(2) =0.928 and 0.937,
respectively) showed both the models had high precision and good prediction capability. The logarithmic
water solubility values predicted by the models are close to those observed. The PLS analysis indicated that
PAHs with larger electronic spatial extent and lower total energy values tend to be less soluble.
GE Douberly, AM Ricks, PVR Schleyer, MA Duncan
Infrared spectroscopy of gas phase benzenium ions: Protonated benzene and protonated toluene, from 750
to 3400 cm(-1)
Journal of Physical Chemistry A, 2008, Vol 112, Iss 22, pp 4869-4874
Gas phase C6H7+ and C7H9+ ions are studied with infrared photodissociation spectroscopy (IRPD) and the
method of rare gas tagging. The ions are produced in a pulsed electric discharge supersonic expansion
source from benzene or toluene precursors. We observe exclusively the formation of either the C-2 upsilon
benzenium ion (protonated benzene) or the para isomer of the toluenium ion (protonated toluene). The
infrared spectral signatures associated with each ion are established between 750 and 3400 cm(-1).
Comparing the gas phase spectrum of the benzenium ion to the spectrum obtained in a superacid matrix
[Perkampus, H. H.; Baumgarten, E. Angew. Chem. Int. Ed. 1964, 3, 776], we find that the C-2 upsilon
structure of the gas phase species is minimally affected by the matrix environment. An intense band near
1610 cm(-1) is observed for both ions and is indicative of the allylic pi-electron density associated with the
six membered ring in these systems. This spectral signature, also observed for alkyl substituted benzenium
ions and protonated naphthalene, compares favorably with the interstellar, unidentified infrared emission
band near 6.2 mu m (1613 cm(-1)).
H PalmaFleming, C Cornejo, M Gonzalez, V Perez, M Gonzalez, E Gutierrez, JL Sericano, M Seeger
Polycyclic aromatic hydrocarbons and polychlorinated biphenyls in coastal environments of Valdivia and
Valparaiso, Chile
Journal of the Chilean Chemical Society, 2008, Vol 53, Iss 2, pp 1533-1538
PAHs and PCBs were measured in the mussel Perumytilus purpuratus (Lamarck) collected from three
different sites along the coast of Valdivia and Valparaiso, South-Central and Central Chile, respectively.
Pollution at these sites is considered low with PAHs originating mainly from pyrolytic sources according to
the Phenanthrene/Anthracene and Fluoranthene/Pyrene ratios. Temporal variation of PAHs was observed in
Valdivia, while site variation was observed along the Valparaiso area. Total PAH concentrations in Valdivia
ranged from 29.2 ng/g to 89.5 ng/g in 2001 and from 31.0 ng/g to 48.6 ng/g in 2002 while in Valparaiso
samples the total PAHs ranged from 27.3 ng/g to 253.1 ng/g and from 12.1 ng/g to 26.3 ng/g in 2001 and
2002, respectively. Polychlorinated biphenyls were not found in mussels from Valdivia; however five nonplanar congeners were detected in samples from Valparaiso with total concentrations between 1.0 ng/g and
16.6 ng/g in 2001 and between 3.4 ng/g and 29.0 ng/g in 2002. The pesticide heptachlor epoxide was
detected in all sampling sites of Valdivia during the years 2001-2002 at concentrations ranging between 1
and 3.5 ng/g.
Q Zhang, J Huang, G Yu
Prediction of soot-water partition coefficients for selected persistent organic pollutants from theoretical
molecular descriptors
Progress in Natural Science, 2008, Vol 18, Iss 7, pp 867-872
Quantitative structure-property relationship (QSPR) models were developed for soot-water partition
coefficient (KSC) values of selected persistent organic pollutants (POPs), i.e. 10 polychlorinated dibenzo-pdioxins and dibenzofurans, nine polychlorinated biphenyls, four polycyclic aromatic hydrocarbons and two
polybrominated diphenyl ethers, using partial least squares (PLS) regression. Quantum chemical descriptors
computed by parameterized model revision 3 Hamiltonian method were used as predictor variables. The
cross-validated Q(cum)(2) value for the optimal QSPR model is 0.844, indicating a good predictive capability
for the logK(SC) values of these chemicals. The QSPR results showed that average molecular polarizability
(alpha), standard heat of formation (Delta H-f) and energy of the lowest unoccupied molecular orbital (ELUMO) have dominant effects on KSC of POPs. The results suggested that logK(SC) values of POPs
increase with the increase of alpha. Contrarily, logK(SC) values decrease with the increase of ELUMO and
DHf of POPs.
P Das, E Arunan, PK Das
Infrared spectra of dimethylnaphthalenes in the gas phase
Vibrational Spectroscopy, 2008, Vol 47, Iss 1, pp 1-9
We report the infrared spectra at 0.5 cm(-1) resolution of three dimethylnaphthalenes (DMNs), namely 1,5DMN, 1,6-DMN and 2,6-DMN in the gas phase at an elevated temperature recorded with the help of a
variable path-length cell. DFT calculations have been carried out at B3LYP levels of theory with 6-31G* as
basis set to determine the harmonic frequencies and intensities of the DMNs to assign the experimentally
observed spectra. We have compared the experimentally observed and theoretically calculated spectra of
the dimethylnaphthalenes and assignments have been made. The observed and predicted frequencies and
relative intensities are generally in good agreement. The intense aromatic C-H out-of-plane bending
vibration observed around 800 cm(-1) and three methyl C-H symmetric and asymmetric stretching vibrations
around 2900 cm(-1) have been recognized as unique bands to identify various DMNs in a mixture. The highresolution IR spectroscopy of these three important polycyclic aromatic hydrocarbons which are present in
the atmosphere have been discussed.
VW Lira, L Djinovic
Analysis of polycyclic aromatic hydrocarbons (PAH) in smoked meat products from Serbia
Fleischwirtschaft, 2008, Vol 88, Iss 5, pp 114-120
The contents of the 16 EU priority polycyclic aromatic hydrocarbons (PAHs) in six different cold smoked
meat products from the protected geographic region Zlatibor (Serbia) were determined with a GUMS
method. The PAH contents in beef ham, pork ham, Bacon with and without skin, cajna sausage and
sremska sausage were analysed in dependence of smoking time. The maximum level for benzo[a]pyrene of
5 mu g/kg in smoked meat products was not exceeded in any samples. The contribution of benzo[a]pyrene
to the total content of the 16 EU priority PAHs was 4.6%. By comparison of beef ham and pork ham from
traditional and industrial smoking it was shown that the total contents of PAHs in samples from industrial
smoking were lower.
A Cebron, MP Norini, T Beguiristain, C Leyval
Real-Time PCR quantification of PAH-ring hydroxylating dioxygenase (PAH-RHD alpha) genes from Gram
positive and Gram negative bacteria in soil and sediment samples
Journal of Microbiological Methods, 2008, Vol 73, Iss 2, pp 148-159
Real-Time PCR based assays were developed to quantify Gram positive (GP) and Gram negative (GN)
bacterial populations that are capable of degrading the polycyclic aromatic hydrocarbons (PAH) in soil and
sediment samples with contrasting contamination levels. These specific and sensitive Real-Time PCR
assays were based on the quantification of the copy number of the gene that encodes the alpha subunit of
the PAH-ring hydroxylating dioxygenases (PAH-RHD alpha), involved in the initial step of the aerobic
metabolism of PAH. The PAH-RHD alpha-GP primer set was designed against the different allele types
present in the data base (narAa, phdA/pdoA2, nidA/pdoA1, nidA3/fadA1) common to the Gram positive PAH
degraders such as Rhodococcus, Mycobacterium, Nocardioides and Terrabacter strains. The PAH-RHD
alpha-GN primer set was designed against the genes (nahAc, nahA3, nagAc, ndoB, ndoC2, pahAc, pahA3,
phnAc, phnA1, bphAc, bphA1, dntAc and arhA1) common to the Gram negative PAH degraders such as
Pseudomonas, Ralstonia, Commamonas, Burkholderia, Sphingomonas, Alcaligenes, Polaromonas strains.
The PCR clones for DNA extracted from soil and sediment samples using the designed primers showed
100% relatedness to the PAH-RHD alpha genes targeted. Deduced from highly sensitive Real-Time PCR
quantification, the ratio of PAH-RHD alpha gene relative to the 165 rRNA gene copy number showed that
the PAH-bacterial degraders could represent up to 1% of the total bacterial community in the PAHcontaminated sites. This ratio highlighted a positive correlation between the PAH-bacterial biodegradation
potential and the PAH-contamination level in the environmental samples studied..
N Itoh, M Numata, T Yarita
Alkaline extraction in combination with microwave-assisted extraction followed by solid-phase extraction
treatment for polycyclic aromatic hydrocarbons in a sediment sample
Analytica Chimica Acta, 2008, Vol 615, Iss 1, pp 47-53
Microwave-assisted extraction using 1 M KOH/methanol (alkaline-MAE) in combination with solid-phase
extraction treatment was developed and applied to polycyclic aromatic hydrocarbons (PAHs) in a sediment
sample. Although various conditions were examined (100 or 150 degrees C for 10 or 30 min), comparable
concentrations of PAHs to those obtained by conventional extraction with 1 M KOH/methanol at 70 degrees
C for 4 h were obtained, even at 100 degrees C for 10 min. The concentrations obtained by using MeOH at
150 degrees C for 30 min without KOH were lower (by 1.3-37%) than those obtained by alkaline-MAE at 150
degrees C for 30 min. Since the developed technique can introduce higher concentration of
benzo[ghi]perylene relative to those using pressurized liquid extraction (toluene, 150 degrees C, 15 MPa, 10
min, two cycles), the developed alkaline-MAE is a effective technique.
RS Jose, AG Ruiz, C vonHolst, T Wenzl, E Anklam
Results of a European inter-laboratory comparison study on the determination of EU priority polycyclic
aromatic hydrocarbons (PAHs) in edible vegetable oils
Analytical and Bioanalytical Chemistry, 2008, Vol 391, Iss 4, pp 1397-1408
A collaborative study on the analysis for 15+1 EU priority PAHs in edible oils was organised to investigate
the state-of-the-art of respective analytical methods. Three spiked vegetable oils, one contaminated native
sunflower oil, and one standard solution were investigated in this study. The results of 52 laboratories using
either high-performance liquid chromatography with fluorescence detection or gas chromatography with
mass-selective detectors were evaluated by application of robust statistics. About 95% of the laboratories
were able to quantify benzo[a]pyrene together with five other PAHs included in the commonly known list of
16 US-EPA PAHs. About 80% of the participants also quantified seven additional PAHs in most samples,
two of which were benzo[b]fluoranthene and benzo[k]fluoranthene, which were also known from the EPA
list. Only about 50% of the participants quantified cyclopenta[cd]pyrene, benzo[j]fluoranthene, and
benzo[c]fluorene. The robust relative standard deviations of the submitted results without discrimination
between the methods applied ranged between 100% for 5-methylchrysene in spiked olive oil and 11% for
the same analyte in spiked sunflower oil. The results clearly showed that for these analytes the methods of
analysis are not yet well established in European laboratories, and more collaborative trials are needed to
promote further development and to improve the performances of the respective methods.
N Aguinaga, N Campillo, P Vinas, M HernandezCordoba
Evaluation of solid-phase microextraction conditions for the determination of polycyclic aromatic
hydrocarbons in aquatic species using gas chromatography
Analytical and Bioanalytical Chemistry, 2008, Vol 391, Iss 4, pp 1419-1424
This paper describes a headspace solid-phase microextraction (HS-SPME) procedure coupled to gas
chromatography with mass spectrometric detection (GC-MS) for the determination of eight PAHs in aquatic
species. The influence of various parameters on the PAH extraction efficiency was carefully examined. At 75
degrees C and for an extraction time of 60 min, a polydimethylsiloxane-divinylbenzene (PDMS/DVB) fiber
coating was found to be most suitable. Under the optimized conditions, detection limits ranged from 8 to 450
pg g(-1), depending on the compound and the sample matrix. The repeatability varied between 7 and 15%
(RSD). Accuracy was tested using the NIST SRM 1974b reference material. The method was successfully
applied to different samples, and the studied PAHs were detected in several of the samples.
N Aguinaga, N Campillo, P Vinas, M HernandezCordoba
A headspace solid-phase microextraction procedure coupled with gas chromatography-mass spectrometry
for the analysis of volatile polycyclic aromatic hydrocarbons in milk samples
Analytical and Bioanalytical Chemistry, 2008, Vol 391, Iss 3, pp 753-758
A sensitive and solvent-free method for the determination of ten polycyclic aromatic hydrocarbons, namely,
naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene,
benzo[a] anthracene and chrysene, with up to four aromatic rings, in milk samples using headspace solidphase microextraction and gas chromatography -mass spectrometry detection has been developed. A
polydimethylsiloxane -divinylbenzene fiber was chosen and used at 75 degrees C for 60 min. Detection
limits ranging from 0.2 to 5 ng L-1 were attained at a signal-to-noise ratio of 3, depending on the compound
and the milk sample under analysis. The proposed method was applied to ten different milk samples and the
presence of six of the analytes studied in a skimmed milk with vegetal fiber sample was confirmed. The
reliability of the procedure was verified by analyzing two different certified reference materials and by
recovery studies.
UG Gautam, MP Gautam, T Sawada, M Takafuji, H Ihara
Enhancement of retentivity and selectivity for PAHs in NP-HPLC by high-density immobilization of poly(4vinylpyridine) as an organic phase on silica
Analytical Sciences, 2008, Vol 24, Iss 5, pp 615-621
Poly(4-vinylpyridine)-modified silica with high grafting density have been prepared by a grafting-from (gfrom) approach through radical chain-transfer reactions. The widely used silane coupling agent 3mercaptopropyltrimethoxysilane was used to prepare thiol-terminated silica. Chain-transfer reaction and
polymerization of 4-vinylpyridine was carried out using alpha, alpha'-azobisisobutyronitrile as an initiator.
Thiol-terminated silica and polymer-modified silica were both characterized qualitatively and quantitatively.
The quantification of the organic phase has been done by thermogravimetric analysis and elemental
analysis. Thus, the modified silica was used as a packing material and the retention behavior of PAHs was
studied in normal-phase high-performance liquid chromatography. Results were compared with those of
poly(4-vinylpyridine)-modified silica prepared by a grafting-to (g-to) approach. Commercially available
aminopropyl-bonded silica and bare silica columns were also used as reference columns. The column of
poly(4-vinylpyridine)-grafted silica prepared by the g-from method, having higher grafting density, provided
the better retentivity and selectivity for PAHs compared to the other reference columns.
RL Zhu, LZ Zhu
Thermodynamics of naphthalene sorption to organoclays: Role of surfactant packing density
Journal of Colloid and Interface Science, 2008, Vol 322, Iss 1, pp 27-32
Temperature dependence of naphthalene sorption to four organoclays with different surfactant (CTMA(+))
packing densities was examined. The results showed that both Delta H degrees and Delta S degrees
increase generally with CTMA(+) packing density. For organoclays with a low CTMA(+) packing density, the
sorption process is driven by both the enthalpy term (Delta H degrees) and the entropy term (-T Delta S
degrees), with values ranging from -4.7 to -7.5 kJ mol(-1) and -15.9 to -20.8 kJ mol(-1), respectively. As the
CTMA+ packing density increases, the sorption process is driven by the entropy term (from -29.2 to -65.0 kJ
mol(-1)) while it is opposed by the enthalpy term (from 7.9 to 40.5 kJ mol(-1)). These results indicate that the
enthalpy demand for cavity formation within the surfactant aggregates and the mixing entropy of solute with
surfactant aggregates both increase with the surfactant packing density. This means that the surfactant
aggregates will form various organic phases as their packing density varies. Controlling the surfactant
aggregates within an intermediate packing density range can improve the sorption capacities of the
organoclays.
C Long, AM Li, DB Hu, FQ Liu, QX Zhang
Description of adsorption equilibrium of PAHs on hypercrosslinked polymeric adsorbent using Polanyi
potential theory
Science in China Series B - Chemistry, 2008, Vol 51, Iss 6, pp 586-592
In this research, static adsorption of three polycyclic aromatic hydrocarbons (PAHs), naphthalene,
acenaphthene, and fluorene, from aqueous solutions onto hypercrosslinked polymeric adsorbent within the
temperature range of 288-308 K is investigated. Several isotherm equations are correlated with the
equilibrium data, and the experimental data is found to fit the Polanyi-Dubinin-Manes model best within the
entire range of concentrations, providing evidence that pore-filling is the dominating sorption mechanism for
PAHs. The study shows that the molecular size of adsorbates has distinct influence on adsorption capacity
of hypercrosslinked polymeric adsorbent for the PAHs; the larger the adsorbate molecular size, the lower the
adsorption equilibrium capacity. Based on the Polanyi-Dubinin-Manes model, the molecular size of
adsorbates was introduced to adjust the adsorbate molar volume. Plots of q(v) vs. (sigma epsilon/V-s) are
collapsed to a single correlation curve for different adsorbates on hypercrosslinked polymeric resin.
BL Chen, DD Zhou, LZ Zhu, XY Shen
Sorption characteristics and mechanisms of organic contaminant to carbonaceous biosorbents in aqueous
solution
Science in China Series B - Chemistry, 2008, Vol 51, Iss 5, pp 464-472
A series of carbonaceous biosorbents was prepared by pyrolyzing pine needles, a model biomass, at
various temperatures (100-700 degrees C) under an oxygen-limited condition for 6 h. The elemental
compositions and the specific surface areas (BET-NO Of the biosorbents were analyzed. Sorption properties
of 4-nitrotoluene to the biosorbents and their mechanisms were investigated, and then correlated with the
structures of the blosorbents. The result shows that with the increase of the pyrolytic temperature, the
aromaticity of the carbonaceous biosorbents increases dramatically and the polarity (the (N+O)/C atomic
ratio) decreases sharply. Correspondingly, conformations of the organic matter in the biosorbents transform
gradually from a ''soft-state'' to a ''hard-state'' and the specific surface areas of the resultant biosorbents
extend rapidly. The sorption isotherms fit well with the Freundlich equation. The regression parameters (i.e.,
N and IgK(f)) are linearly related to the aromaticity indices (the H/C atomic ratio). Contributions of adsorption
and partition to total sorption of the carbonaceous biosorbents are quantified. The adsorption of the
carbonaceous biosorbents increases quickly with the increase of the pyrolytic temperature. The saturated
adsorption amounts (Q(max)) increase linearly with the increase of the specific surface areas (SA) of the
biosorbents. For the carbonaceous biosorbents with hard-state carbon, the calculated normalized-Q(max)
values by SA are comparable to the theoretical estimation (2.45 mu mol/m(2)). In comparison, for the
carbonaceous sorbents with soft-state carbon, the calculated normalized-Q(max) values by SA are much
higher than the theoretical estimation. The partition coefficients (K-om) increase with the decrease of the
polarity of the biosorbents, reaching a maximum, and then decrease sharply with further decreasing the
polarity, suggesting that partition mechanism be dominated by the compatibility and accessibility of the
sorbent medium with organic pollutant. These observations will provide a theoretical and practical reference
to design a cost-effective and high-efficient sorbent, and to accurately predict sorption properties and
mechanisms of a given sorbent.