Polycyclic Aromatic Hydrocarbons In Fish Research Articles

Evaluation of the impact of anthropogenic activities on arsenic, cadmium, chromium, mercury, lead, and polycyclic aromatic hydrocarbon levels in seafood from the Gulf of Naples, Italy

ABSTRACTThe principal aim of this study was to monitor the occurrence of some metals and polycyclic aromatic hydrocarbons (PAHs) in fish and mussels from the Gulf of Naples. A comparison with previous researches of the same area was carried out, and the intakes of these compounds through the diet and their effect on the tolerable intake values (when available) were assessed. Cadmium (Cd), chromium (Cr), and lead (Pb) were detected by flameless atomic absorption spectroscopy (Cd, Cr, and Pb); arsenic (As) and mercury (Hg) were detected by applying the hydride method. PAHs were detected by high-performance liquid chromatography. Widespread contamination was found. Among the metals, Hg showed the highest maximum levels of 284.94 ng/g wet weight (ww) in fish and 480.00 ng/g ww in mussels. Chrysene, phenanthrene, fluoranthene, anthracene, and benzo[k]fluoranthene were the most common PAHs in fish, whereas benzo[a]anthracene, pyrene, phenanthrene, acenaphthylene, and acenaphthene were the most frequently occurring compounds in mussels. The concentrations of As, Cr, Hg, Pb, and PAHs in fish were found to decrease over a period of 30 years, whereas the Cd levels remained constant. The Hg, Pb, and PAH levels in mussels increased over the period 2010 to 2016. Finally, the average consumption of mussels led to the highest effect on the Tolerable Daily Intake of Hg, which was exceeded by 19%.

Species-specific metabolism of naphthalene and phenanthrene in 3 species of marine teleosts exposed to Deepwater Horizon crude oil.

The 2 most abundant polycyclic aromatic hydrocarbons (PAHs) measured in Deepwater Horizon crude oil, naphthalene and phenanthrene, and their associated homologs have both been shown to be acutely toxic in fish. Although fish have a relatively high metabolic capacity for PAHs, hydroxylated PAH (OH-PAH) derivatives formed during the initial metabolic response can negatively impact the health of fish. Species-specific metabolism of naphthalene and phenanthrene was evaluated in 3 marine teleosts, red drum (Scianops ocellatus), Florida pompano (Trachinotus carolinus), and southern flounder (Paralichthys lethostigma). Fish were exposed to Deepwater Horizon crude oil by intraperitoneal injections at time 0 and 48 h, with bile sampling events at 24 and 72 h post injection. The data suggested metabolic induction in Florida pompano and red drum, whereas southern flounder may have demonstrated metabolic fatigue. By 24 h post injection, overall profiles of red drum and southern flounder were dominated by hydroxylated phenanthrene metabolites; conversely, the Florida pompano profiles were dominated by monohydroxylated naphthalenes. In addition, Florida pompano had faster overall relative biotransformation rates, suggesting their potential decreased susceptibility to adverse effects. Red drum and southern flounder had much lower relative biotransformation rates, indicating their probable susceptibility to adverse outcomes after naphthalene and phenanthrene exposures. To our knowledge, the present study is the first to investigate monohydroxylated PAHs in fish exposed to Deepwater Horizon oil. Environ Toxicol Chem 2017;36:3168-3176. © 2017 © 2017 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.

Products of biotransformation of polycyclic aromatic hydrocarbons in fishes of the Athabasca/Slave river system, Canada.

Concentrations of products of biotransformation of polycyclic aromatic hydrocarbons (PBPAH) were measured in bile of five fishes of nutritional, cultural and ecological relevance from the Athabasca/Slave river system. Samples were collected in Alberta and the Northwest Territories, Canada, during three seasons. As a measure of concentrations of PBPAHs to which fishes are exposed and to gain information on the nature and extent of potential exposures of people or piscivorous wildlife, concentrations of biotransformation products of two- and three-ringed, four-ringed and five-ringed PAHs were measured using synchronous fluorescence spectroscopy. Spatial and seasonal differences were observed with greater concentrations of PBPAHs in samples of bile of fish collected from Fort McKay as well as greater concentrations of PBPAHs in bile of fish collected during summer compared to those collected in other seasons. Overall, PBPAHs were greater in fishes of lower trophic levels and fishes more closely associated with sediments. In particular, goldeye (Hiodon alosoides), consistently contained greater concentrations of all the PBPAHs studied.

The influence of seasonality, fish size and reproductive status on EROD activity in Plagioscion squamosissimus: Implications for biomonitoring of tropical/subtropical reservoirs

Ethoxyresorufin-O-deethylase (EROD) activity is considered an important biomarker for aquatic environmental contamination. Although EROD activity has been widely used as a biomarker of exposure to polycyclic aromatic hydrocarbons in fish, this activity can be influenced in the field by spatial-, seasonal- or individual-related factors. We therefore performed a comparative study of hepatic EROD activity levels in the croaker Plagioscion squamosissimus to determine whether variations existed in enzyme activity levels, especially in relationship to reproductive status, fish size, age, and seasonality. For this purpose, we collected fish from three reservoirs with different pollution levels during the early-rainy (November 2012), rainy (March 2013), and dry (July–August 2013) seasons from the Tietê River, Brazil. We tested whether size, age and sex affected EROD activity among the localities and seasons. We found a marked effect of pollution during the dry season on variation among the localities in EROD activity in P. squamosissimus. An analysis of covariance indicated that sex had a significant negative effect on the seasonal variability of the EROD activity levels at the most polluted locality (near São Paulo). A possible explanation for the statistical association between EROD activity and sex is that the reproductive status of the females influenced the EROD activity levels. A possible explanation for the statistical association between EROD activity and sex is that the reproductive status of the females influenced the EROD activity levels, also largely reported in the literature. Our results suggest that reproductive status can be a significant confounding factor for determining EROD activity in female P. squamosissimus in freshwater ecosystems when compared to males. Moreover, our results suggest that the presence of phenanthrene during the dry season at Barra Bonita reservoir might explain the highest EROD activity responses in this period of study.

How does predation affect the bioaccumulation of hydrophobic organic compounds in aquatic organisms?

It is well-known that the body burden of hydrophobic organic compounds (HOCs) increases with the trophic level of aquatic organisms. However, the mechanism of HOC biomagnification is not fully understood. To fill this gap, this study investigated the effect of predation on the bioaccumulation of polycyclic aromatic hydrocarbons (PAHs), one type of HOC, in low-to-high aquatic trophic levels under constant freely dissolved PAH concentrations (1, 5, or 10 μg L(-1)) maintained by passive dosing systems. The tested PAHs included phenanthrene, anthracene, fluoranthene, and pyrene. The test organisms included zebrafish, which prey on Daphnia magna, and cichlids, which prey on zebrafish. The results revealed that for both zebrafish and cichlids, predation elevated the uptake and elimination rates of PAHs. The increase of uptake rate constant ranged from 20.8% to 39.4% in zebrafish with the amount of predation of 5 daphnids per fish per day, and the PAH uptake rate constant increased with the amount of predation. However, predation did not change the final bioaccumulation equilibrium; the equilibrium concentrations of PAHs in fish only depended on the freely dissolved concentration in water. Furthermore, the lipid-normalized water-based bioaccumulation factor of each PAH was constant for fish at different trophic levels. These findings infer that the final bioaccumulation equilibrium of PAHs is related to a partition between water and lipids in aquatic organisms, and predation between trophic levels does not change bioaccumulation equilibrium but bioaccumulation kinetics at stable freely dissolved PAH concentrations. This study suggests that if HOCs have not reached bioaccumulation equilibrium, biomagnification occurs due to enhanced uptake rates caused by predation in addition to higher lipid contents in higher trophic organisms. Otherwise, it is only due to the higher lipid contents in higher trophic organisms.

Distribution and accumulation of polycyclic aromatic hydrocarbons (PAHs) in the food web of Nansi Lake, China.

The concentrations of polycyclic aromatic hydrocarbons (PAHs) were analyzed in water, sediment, and biota (aquatic plant, shrimp, and fish) of Nansi Lake by gas chromatography-mass spectrometry (GC-MS). The concentrations of total PAHs were 27.54-55.04 ng L(-1) in water, 80.31-639.23 ng g(-1) dry weight (dw) in sediments, 20.92-192.78 ng g(-1) dw in aquatic plants, and 67.3-533.9 ng g(-1) dw in fish and shrimp muscles. The ratios of phenanthrene to anthracene (Ph/An), fluoranthene to pyrene (Flu/Pyr), and low molecular weight to high molecular weight (LMW/HMW) in sediment indicated that the sources of the PAHs were a mixture of pyrolytic and petrogenic contamination at most sampling sites in Nansi Lake. The composition profile of PAHs in plants was similar to that in water and animals with 2-3 ring PAHs being dominant. The 4-6 ring PAHs were the dominant PAH compounds in sediment. There is a positive correlation between sediment and aquatic plants, but their PAH composition profiles were different, implying that aquatic plant absorption of PAHs from sediment is selective and the accumulation of PAHs in aquatic plants is different. The concentration of PAHs in fish showed a positive correlation with plants, reflecting that the PAHs in fish are mainly absorbed from aquatic plants rather than directly from the water. Bioaccumulation of LMW PAHs in aquatic biota was higher than HMW PAHs. The biota-sediment accumulation factor (BSAF) values of total PAHs in the plants Potamogeton lucens Linn and Ceratophyllum demersum Linn were higher than that in most animals. The BSAF values of total PAHs in animals were in the following order: Cyprinus carpio>Macrobrachium nipponense>Carassius auratus>Channa argus. There was no significant relationship between PAH bioaccumulation and trophic levels in Nansi Lake. Risk assessment of PAHs in water, sediment, and animals indicated that the water environment of Nansi Lake is safe at present. It is worthwhile to note that benzo [a] anthracene (BaA), benzo [a] pyrene (BaP), indeno [1,2,3-cd] pyrene (InP), dibenz [a, h] anthracene (DBA), and benzo [ghi] perylene (BghiP) were detected in sediment, plants, and animals at all sampling sites, and they have potential carcinogenicity to the organisms of Nansi Lake.

Multi-pathway assessment of human health risk posed by polycyclic aromatic hydrocarbons.

To assess aggregate exposure to polycyclic aromatic hydrocarbons (PAHs) via several environmental media and pathways, a probabilistic framework for multi-pathway health risk assessment that integrates PAHs potency equivalence factors, risk estimation modeling, and Monte Carlo simulation was applied to a case study in Nanjing, which is an important industrial city in China. Incremental lifetime risk of additional cancers posed by exposure to 16 USEPA priority PAHs in air, water, soil, and fish was assessed. Risks to three age groups, infants, children, and adults, through various exposure pathways, including oral ingestion, dermal absorption, and inhalation, were estimated. Results of the analysis of risk indicated that B[a]P, B[b]F, and BA were the predominant PAHs pollutants in Nanjing. Risk of additional cancer for local adults was on average 2.62×10(-5). The risks were primarily due to ingestion of fish and inhalation, which contributed 99% of the total risks. By contrast, risk to infants was essentially negligible. Results of a sensitivity analysis indicated that the input variables of concentration of PAHs in fish (C f), the body weight (BW), and the ingestion rate of fish (IRf) were the major influences on estimates of risks.

QuEChERS Method Followed by Solid Phase Extraction Method for Gas Chromatographic-Mass Spectrometric Determination of Polycyclic Aromatic Hydrocarbons in Fish.

A gas chromatography equipped with mass spectrometer (GCMS) method was developed and validated for determination of 16 polycyclic aromatic hydrocarbons (PAHs) in fish using modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method for extraction and solid phase extraction for sample cleanup to remove most of the coextract combined with GCMS for determination of low concentration of selected group of PAHs in homogenized fish samples. PAHs were separated on a GCMS with HP-5ms Ultra Inert GC Column (30 m, 0.25 mm, and 0.25 µm). Mean recovery ranged from 56 to 115%. The extraction efficiency was consistent over the entire range where indeno(1,2,3-cd)pyrene and benzo(g,h,i)perylene showed recovery (65, 69%), respectively, at 2 µg/kg. No significant dispersion of results was observed for the other remaining PAHs and recovery did not differ substantially, and at the lowest and the highest concentrations mean recovery and RSD% showed that most of PAHs were between 70% and 120% with RSD less than 10%. The measurement uncertainty is expressed as expanded uncertainty and in terms of relative standard deviation (at 95% confidence level) is ±12%. This method is suitable for laboratories engaged daily in routine analysis of a large number of samples.

Polycyclic aromatic hydrocarbons in fish from St Helena, South Atlantic, in relation to an historic wreck

Concentrations of polycyclic aromatic hydrocarbons were determined in edible tissues of fish species consumed by the islanders of St Helena to assess any risk to human health posed by oil leaking from an historic wreck. Samples were collected from the vicinity of the wreck site and at two reference locations at which fishing activity occurs. Summed PAH concentrations ranged from 2.2 to 20μgkg−1 wet weight, and no PAHs with more than 4 fused rings were detected. All concentrations of the four PAH used as a basis for assessment in relation to health risks to human consumers of foods within the EU (benz[a]anthracene, benzo[a]pyrene, benzo[b]fluoranthene and chrysene) were<0.1μgkg−1 wet weight and raised no concerns. Additionally, concentrations were calculated as the benzo[a]pyrene toxic equivalency quotient and found to be well below the level of concern (0 to 0.05μgkg−1 wet weight benzo[a]pyrene equivalents).

An Evaluation of Polycyclic Aromatic Hydrocarbons in &lt;i&gt;Hemichromis fasciatus&lt;/i&gt; (Peters, 1857) from an Urban Reservoir in Southern Nigeria

The concentrations of Polycyclic Aromatic Hydrocarbons (PAHs) were analysed in Hemichromis fasciatus netted from the Ikpoba reservoir in Benin City, Nigeria, using Gas chromatographic technique, in order to evaluate the potential ecological risk of these organic pollutants on the investigated ecosystem. The mean concentrations in μg/kg of 2-methynaphthalene,1-methynapthalene, acenaphthylene, acenaphthene, flourene, phenanthrene, anthracene, flouranthene, pyrene, benzo(a)anthracene, benzo(k)flouranthene, benzo(b)flouranthene, indeno(123-cd)pyrene and benzo(ghi)perylene in the fish species were 0.0034, 0.0025, 0.0047, 0.0007, 0.0093, 0.0023, 0.0178, 0.0147, 0.0039, 0.0185, 0.0014, 0.0152, 0.0012 and 0.0027respectively. There were significant differences (P < 0.05) in the mean concentrations of PAHs in fish between stations with the exception of phenanthrene and indeno (123 cd) pyrene. The peak concentrations of the PAHs in H. fasciatus were generally observed in the month of August with the exception of benzo(ghi)perylene, whose peak concentration was observed in October. The Hazard Quotient values for PAHs ranged from 0.0014 for acenaphthene to 0.037 for benzo(a)anthracene while the estimated daily intake of PAHs ranged from 0.000028 mg/person/day for acenapthene to 0.00074 mg/person/day for benzo(a)anthracene. The Toxic Equivalency Quotient (TEQ) values ranged from 0.000014 for benzo(k)flouranthene to 0.00185 for benzo(a)anthracene. The mean concentrations of PAHs detected in H. fasciatu s in this study, did not exceed the World Health Organisation (WHO) recommended background concentration of 0.5μg/kg for benzo(a)pyrene in food samples. This finding indicates that the consumption of this fish species by man, does not present an immediate health risk and it is therefore safe to eat as it is relatively free from hazardous levels of PAHs. However, the TEQ values recorded in this study revealed that benzo(a)anthracene poses the greatest potential risk in the reservoir and should thus be closely monitored by relevant authorities in order to avert unwholesome ecological impacts. Keywords : Polycyclic Aromatic Hydrocarbons, Potential Ecological Risk, Ikpoba reservoir, Nigeria.

In-situ partitioning and bioconcentration of polycyclic aromatic hydrocarbons among water, suspended particulate matter, and fish in the Dongjiang and Pearl Rivers and the Pearl River Estuary, China

The partitioning and bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) in water, suspended particulate matter (SPM), and fish samples from the Dongjiang River (DR), Pearl River (PR), and the Pearl River Estuary (PRE) were examined. Although PAHs are much lower in PRE than in DR or PR, PAHs in some fish species are significantly higher in PRE than in DR or PR. Aqueous or particulate PAHs respectively show significant correlations with dissolved organic carbon, particulate organic matter, and chlorophyll a, suggesting that biological pumping effect regulates their distribution. The in situ partitioning coefficients (logKoc) for PAHs are one order magnitude higher than the empirical logKoc–logKow correlation. The bioconcentration factor (BCF) is slightly higher for the marine fish than for the freshwater fish. The above phenomena indicate that BCF may vary due to the diversity of fish species, feeding habits, and metabolism of PAHs in fish.

EROD activity and antioxidant defenses of sea bass (Dicentrarchus labrax) after an in vivo chronic hydrocarbon pollution followed by a post-exposure period

Chronic concentrations of polycyclic aromatic hydrocarbons (PAHs) have been commonly detected in international estuaries ecosystems. Reliable indicators still need to be found in order to properly assess the impact of PAHs in fish. After an in vivo chronic exposure to hydrocarbons, the enzymatic activity of 7-ethoxyresorufin O-deethylase (EROD) and the antioxidant defense system were assessed in sea bass, Dicentrarchus labrax. A total of 45 fish were exposed to the water-soluble fraction of Arabian crude oil, similar to a complex pollution by hydrocarbons chronically observed in situ, while 45 other control fish sustained the same experimental conditions in clean seawater. Fish samples were made after a 21-day exposure period and after a 15-day recovery period in clean fresh water. Throughout the experiment, liver EROD activity was significantly higher in contaminated fish than in control fish. In addition, nonenzymatic (total glutathione) and enzymatic (GPx, SOD, and CAT) antioxidant defense parameters measured in liver were not significantly different in fish. Furthermore, in gills, glutathione content had significantly increased while SOD activity had significantly decreased in contaminated fish compared to controls. On the other hand, CAT and GPx activities were not affected. Chronic exposure to PAHs disturbing the first step (SOD) and inhibiting the second step (GPx and CAT) could induce oxidative stress in tissues by the formation of oxygen radicals. After the postexposure period, there was no significant difference between control and contaminated fish in any of the antioxidant defense parameters measured in gills, attesting to the reversibility of the effects.

Gas chromatography–triple quadrupole tandem mass spectrometry: a powerful tool for the (ultra)trace analysis of multiclass environmental contaminants in fish and fish feed

A new method for rapid determination of 73 target organic environmental contaminants including 18 polychlorinated biphenyls, 16 organochlorinated pesticides, 14 brominated flame retardants and 25 polycyclic aromatic hydrocarbons in fish and fish feed using gas chromatography coupled with triple quadrupole tandem mass spectrometry (GC-MS/MS) was developed and validated. GC-MS/MS in electron ionization mode was shown to be a powerful tool for the (ultra)trace analysis of multiclass environmental contaminants in complex matrices, providing measurements with high selectivity and sensitivity. Another positive aspect characterizing the newly developed method is a substantial simplification of the sample preparation, which was achieved by an ethyl acetate QuEChERS (quick, easy, cheap, effective, rugged and safe) based extraction followed by silica minicolumn clean-up. With use of this sample preparation approach the sample laboratory throughput was increased not only because six samples may be prepared in approximately 1 h, but also because all the above-mentioned groups of contaminants can be determined in a single GC-MS/MS run. Under the optimized conditions, the recoveries of all target analytes in both matrices were within the range from 70 to 120% and the repeatabilities were 20% or less. The method quantification limits were in the range from 0.005 to 1 μg kg(-1) and from 0.05 to 10 μg kg(-1) for fish muscle tissue and fish feed, respectively. The developed method was successfully applied to the determination of halogenated persistent organic pollutants and polycyclic aromatic hydrocarbons in fish and fish feed samples.

Implementation of comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry for the simultaneous determination of halogenated contaminants and polycyclic aromatic hydrocarbons in fish

In the presented study, comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC × GC-TOFMS) was shown to be a powerful tool for the simultaneous determination of various groups of contaminants including 18 polychlorinated biphenyls (PCBs), seven polybrominated diphenyl ethers (PBDEs), and 16 polycyclic aromatic hydrocarbons (PAHs). Since different groups of analytes (traditionally analyzed separately) were included into one instrumental method, significant time savings were achieved. Following the development of an integrated sample preparation procedure for an effective and rapid isolation of several groups of contaminants from fish tissue, the GC × GC-TOFMS instrumental method was optimized to obtain the best chromatographic resolution and low quantification limits (LOQs) of all target analytes in a complex mixture. Using large-volume programmable temperature vaporization, the following LOQs were achieved-PCBs, 0.01-0.25 μg/kg; PBDEs, 0.025-5 μg/kg; PAHs 0.025-0.5 μg/kg. Furthermore, several capillary column combinations (BPX5, BPX50, and Rxi-17Sil-ms in the first dimension and BPX5, BPX50, Rt-LC35, and HT8 in the second dimension) were tested during the experiments, and the optimal separation of all target analytes even of critical groups of PAHs (group (a): benz[a]anthracene, cyclopenta[cd]pyrene and chrysene; group (b): benzo[b]fluoranthene, benzo[j]fluoranthene and benzo[k]fluoranthene; group (c): dibenz[ah]anthracene, indeno[1,2,3-cd]pyrene and benzo[ghi]perylene) was observed on BPX5 × BPX50 column setup. Moreover, since the determination of target analytes was performed using TOFMS detector, further identification of other non-target compounds in real life samples was also feasible.

Analysis of polycyclic aromatic hydrocarbons in fish: Optimisation and validation of microwave-assisted extraction

Abstract An accurate and sensitive method for determination of 18 polycyclic aromatic hydrocarbons (PAHs) (16 PAHs considered by USEPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) in fish samples was validated. Analysis was performed by microwave-assisted extraction and liquid chromatography with photodiode array and fluorescence detection. Response surface methodology was used to find the optimal extraction parameters. Validation of the overall methodology was performed by spiking assays at four levels and using SRM 2977. Quantification limits ranging from 0.15–27.16 ng/g wet weight were obtained. The established method was applied in edible tissues of three commonly consumed and commercially valuable fish species (sardine, chub mackerel and horse mackerel) originated from Atlantic Ocean. Variable levels of naphthalene (1.03–2.95 ng/g wet weight), fluorene (0.34–1.09 ng/g wet weight) and phenanthrene (0.34–3.54 ng/g wet weight) were detected in the analysed samples. None of the samples contained detectable amounts of benzo[a]pyrene, the marker used for evaluating the occurrence and carcinogenic effects of PAHs in food.

Simplified and rapid determination of polychlorinated biphenyls, polybrominated diphenyl ethers, and polycyclic aromatic hydrocarbons in fish and shrimps integrated into a single method

In this study, a new rapid and flexible method for the simultaneous determination of 18 key representatives of polychlorinated biphenyls (PCBs), 7 polybrominated diphenyl ethers (PBDEs), and 32 polycyclic aromatic hydrocarbons (PAHs) in fish and shrimps by gas chromatography coupled to mass spectrometry (GC–MS) was developed and validated. A substantial simplification of sample processing prior to quantification step was achieved: after addition of water to homogenized sample, transfer of hydrophobic analytes into ethyl acetate was supported by added inorganic salts. Bulk fat, contained in crude organic extract obtained by partition, was subsequently removed on a silica minicolumn. This approach enabled to process six samples in less than 1 h; moreover, the volume of an extraction solvent and consumption of other chemicals can be significantly reduced compared to, e.g., traditional Soxhlet extraction followed by gel permeation chromatography. The recoveries of target analytes were in the range of 73–120% even at the lowest spiking level (1 μg kg −1), repeatabilities (relative standard deviations, RSDs) ranged from 1 to 20%. Under optimized GC–MS conditions (time-of-flight mass analyzer, TOF), the limits of quantification (LOQs) were as follows: PCBs 0.1–0.5 μg kg −1, PBDEs 0.5 μg kg −1, and PAHs 0.05–0.25 μg kg −1. Ambient mass spectrometry employing a direct analysis in real time (DART) ion source was shown as an effective tool for fat control in extract, which is needed during the method development and examination of unknown samples prior to the analysis. Further extension of a method scope by other similar analytes is easily possible.

Polycyclic aromatic hydrocarbons in fish and crayfish from the Calumet region of southwestern Lake Michigan

We identified and quantified polyaromatic hydrocarbons (PAHs) in six aquatic taxa from the Calumet region of southwestern Lake Michigan in order to examine their differential exposure to and health risks from PAH. There was a high degree of variation in PAH concentrations across and within sites. Mean concentrations of total PAH were high in alewife (1,064 ng/g) and minnows (345 ng/g) collected from the Indiana Ship Canal, when compared to other taxa and locations. Concentrations of PAH in sunfish were relatively low (10 to 79 ng/g), even where environmental concentrations were elevated. In sunfish, regardless of location, concentrations of CHR, FLA, FLU, PHE and PYR were high whereas DBA, IPE, BAP, BBF, BGP and BKF concentrations were low. PAH concentrations in crayfish exceeded those of other taxa at three of four locations where they co-occurred. PAH profiles were similar in crayfish, sunfish and minnows from locations where sediment concentrations were low. Profiles for crayfish and minnows from a location where sediment concentrations were elevated displayed lower concentrations of ACY, and higher concentrations of BAA, BBF, and BKF, than those from the other three locations. In contrast, the profiles in sunfish from those three locations were similar. The PHE/ANT and FLA/PYR ratios for crayfish, minnows and sunfish suggested that the primary sources at most locations were pyrogenic, although some sites had strong petrogenic influences. Toxic equivalency factors in biota generally reflected the magnitude of sediment contamination. In three of four locations where they co-occurred, TEQs were higher in crayfish than in sunfish and minnows. Sunfish had higher TEQs than minnows at most, though not all, locations; TEQs were notably higher in minnows as compared to sunfish from the Little Calumet River. The selection of aquatic species as sentinels of PAH exposure and risks needs to consider differences in ecologies of taxa as well as the relative magnitude of sediment contamination.

POLYCYCLIC AROMATIC HYDROCARBONS (PAHS) IN SEAFOOD CAUGHT OFF IN NAPOLI GULF (ITALY)

Benzo(a)pyrene and other 12 polycyclic aromatic hydrocarbons (PAHs) were determined by high performance liquid chromatography (HPLC) with fluorescence detection in different seafoods (Merluccius merluccius, Arnoglossus laterna, Scomber japonicus, Eledone moschata and Penaeus kerathurus) collected along the coast of Napoli gulf (Italy). The results showed that Bap levels exceeded the limit fixed by EU Regulation 1881/2006 in several species and the concentrations of PAHs were higher in winter than in summer season. The presence of carcinogenic PAH in fish is dangerous to human health and should be seriously considered.

Analysis of polycyclic aromatic hydrocarbons in fish: evaluation of a quick, easy, cheap, effective, rugged, and safe extraction method

QuEChERS method was evaluated for extraction of 16 PAHs from fish samples. For a selective measurement of the compounds, extracts were analysed by LC with fluorescence detection. The overall analytical procedure was validated by systematic recovery experiments at three levels and by using the standard reference material SRM 2977 (mussel tissue). The targeted contaminants, except naphthalene and acenaphthene, were successfully extracted from SRM 2977 with recoveries ranging from 63.5-110.0% with variation coefficients not exceeding 8%. The optimum QuEChERS conditions were the following: 5 g of homogenised fish sample, 10 mL of ACN, agitation performed by vortex during 3 min. Quantification limits ranging from 0.12-1.90 ng/g wet weight (0.30-4.70 microg/L) were obtained. The optimized methodology was applied to assess the safety concerning PAHs contents of horse mackerel (Trachurus trachurus), chub mackerel (Scomber japonicus), sardine (Sardina pilchardus) and farmed seabass (Dicentrarchus labrax). Although benzo(a)pyrene, the marker used for evaluating the carcinogenic risk of PAHs in food, was not detected in the analysed samples (89 individuals corresponding to 27 homogenized samples), the overall mean concentration ranged from 2.52 +/- 1.20 ng/g in horse mackerel to 14.6 +/- 2.8 ng/g in farmed seabass. Significant differences were found between the mean PAHs concentrations of the four groups.

Polycyclic Aromatic Hydrocarbons in Fishes and Sediments from the Guanabara Bay, Brazil

Polycyclic aromatic hydrocarbons (PAHs) were identified and quantified in sediment and fish samples. The samples were analyzed by gas chromatography/mass spectrometry to gather information about the degree of contamination. PAH total concentration ranged from 79 to 487 μ g/kg dry weight in surficial sediment samples and from 4 to 53 μ g/kg in fish samples. Most sediment samples were classified as fairly contaminated (at 250–500 μ g/kg of total PAH). The lowest and highest Σ PAH concentrations in fish (4 to 53 μ g/kg) were found for Mugil lisa and Micropogonias furniere, respectively. The PAHs in sediment and fish samples are derived primarily from mixed sources.