Priority Polyaromatic Hydrocarbons Research Articles

Dietary exposure to polyaromatic hydrocarbons of the Hong Kong population

Polyaromatic hydrocarbons (PAHs) are ubiquitous in the environment and food. The Joint FAO/WHO Expert Committee on Food Additives concluded 13 individual PAHs are carcinogenic and genotoxic in vitro and in vivo. Food is recognized as the main source of exposure to PAHs for adult non-smokers, which contributed to more than 90% of total exposure. In this study, 300 food samples were collected in Hong Kong, analysed the levels of 16 European Union priority PAHs, the dietary exposure to these PAHs by the local adult population from these food items, and the associated health risk. The most predominant detectable PAH was chrysene (CHR) (14.4%), followed by benzo[c]fluorene (11.2%), benzo[a]anthracene (BaA) (10.6%) and benzo[b]fluoranthene (BbFA) (7.8%). The dietary exposures for average consumers of benzo[a]pyrene (BaP) and PAH4 (sum of BaP, CHR, BaA and BbFA) were 0.13–0.90 and 1.4–4.2 ng/kg bw/day respectively for lower and upper bound approaches. Cereal and its products contributed more than 50% to BaP and PAH4 for average consumers in a lower-bound approach. The margin of exposure (MOE) approach was used to assess the health risks of consumers. The calculated MOE values for both BaP and PAH4 of the average and high consumers (90th percentile) were >50,000, indicating a low concern for the health of the Hong Kong population.

Optimization of excitation and emission wavelengths for the UHPLC fluorescence detector for priority polycyclic aromatic hydrocarbons (PAHs)

AbstractPolycyclic aromatic hydrocarbons (PAHs) are persistent organic pollutants (POPs) that are widely distributed in the environment and cause significant environmental damage. Furthermore, they endanger human health by polluting food from the natural environment and food processing. Therefore, it is necessary to accurately detect PAHs in various sample matrices, which requires precise, practical, and rapid detection methods. The purpose of this research is to develop a high sensitivity analysis method by analyzing the optimum excitation and emission wavelengths of EPA's 15 priority polyaromatic hydrocarbons in the UHPLC fluorescence detector (Acenaphthene, Anthracene, Benzo[a]anthracene, Benzo[b]fluoranthene, Benzo[k]fluoranthene, Benzo[ghi]perylene, Benzo[a]pyrene, Chrysene, Dibenzo[a,h]anthracene, Fluoranthene, Fluorene, Indeno[1,2,3-cd]pyrene, Naphthalene, Phenanthrene, and Pyrene). An average of 17–25 analyses were performed for each polyaromatic hydrocarbon, and optimized excitation and emission wavelengths were obtained. LOD levels between 2 and 90 ppt were obtained with the method created in this direction. It is worth mentioning that the limits achieved for some PAH parameters are lower than those reported in the literature after pre-concentration steps.

Impacts of PAH accumulation on reproductive hormones, indices of oxidative stress and BPDE-albumin adduct in women with recurrent pregnancy loss

Chronic exposure to Poly aromatic hydrocarbons (PAHs) may be associated with adverse pregnancy outcomes. Disruption of hormonal and redox balance by toxic PAH metabolites may interfere with successful pregnancy leading to miscarriage. The association of exposure to PAH contaminated mussel via the dietary route with perturbations in reproductive hormones, biomarkers of oxidative stress, and PAH metabolites were assessed in women with recurrent pregnancy loss (RPL). Furthermore, an analysis of the concentration of PAHs in environmentally relevant bivalve animals was performed to preliminary get insights into the levels of these pollutants in the environment. Seventy-six women (20–35 years) were categorized into 18 fertile women without RPL (control), and Groups I, II, and III comprising 24, 18, and 16 women with RPL (2, 3, and > 3 abortions respectively) were studied. Whole blood samples were collected for the estimation of malondialdehyde (MDA), catalase, reduced glutathione (GSH), glutathione-S-transferase (GST), progesterone (P4), follicle-stimulating hormone (FSH), benzo[a]pyren-7,8-dihydrodiol-9,10-epoxide-albumin adduct (BPDE-albumin) and urine for α-naphthol and β-naphthol. Two species of mussel Donax trunculus and Andar aduloii samples were collected for the estimation of 16 priority PAHs. The concentration of PAHs exceeding the maximum limits was observed in the two species of mussels studied. Higher levels of BPDE-albumin, MDA, GST, α and β-naphthol and lower GSH, catalase, FSH, and P4 were observed in women with RPL (Groups I-III) compared to controls (p = < 0.001). Negative associations were observed between BPDE-albumin and catalase (r = − 0.276, p = 0.036), and GSH (r = − 0.331, p = − 0.011) only in women with RPL. Collectively, our findings indicate a possible association of chronic PAH accumulation with recurrent pregnancy loss in women.Graphical abstractHigh PAH exposure in pregnant women is associated with 10-epoxide-albumin adduct formation and highMDA levels in their sera. On the other hand, PAH exposure in those women led to a decrease in theirGSH, catalase, P4, and FSH sera levels. These findings indicate that PAH exposure can exert differentphysiological effects in pregnant women leading to a high level of abortion in those women.

Coupling chemical transport modeling and diagnostic ratio analysis for predicting PAH fingerprint in coal tar and creosote contaminated soils

ABSTRACT This article illustrates the use of a fate and transport model and a diagnostic ratio analysis to determine chemical signatures of polyaromatic hydrocarbons (PAHs) in coal tar and creosote residues in soil. The fate and transport model, based on diffusion, convection – advection of PAHs, helps determine their weathering rates in two soil types and provides an insight on the air – soil exchange of PAHs. Time-averaged volatilisation flux, estimated from the model, was used to determine the residual composition of the 16 priority PAH (non-alkylated PAHs) in coal tar and creosote contaminated soils. Expectedly, lower molecular weight (MW) PAHs volatilised faster than higher MW PAHs. In the absence of water movement towards the surface, vapour diffusion is the primary mechanism of transport, and the flux was observed to be high ranging from 8.52–2167.3 x 10−7 kg m−2 day−1. Higher flux was observed for clayey soils. At high values of organic carbon (foc), the flux was observed to be lower due to the binding of PAHs to the soil. The mass flux was higher with water movement (0.6–1036.5 x 10−3 kg m−2 day−1) indicating that diffusion along with wicking were the key mechanisms for PAH losses from soil residues. The modelled volatilisation flux for the PAHs was observed to be within the range of the flux values (for soils and sediment) reported in literature. Double diagnostic ratio analysis was used to compare chemical signatures of the modelled residues to PAH data in actual PAH contaminated soils. The diagnostic PAH ratios of the modelled weathered coal and creosote residues and the actual soil samples correlated well, especially for 5- and 6-ringed PAHs. A good correlation between the modelled and actual diagnostic ratios suggested that the mathematical model can be used to supplement physical sampling and analysis, thereby providing one additional line of evidence for source apportionment.

Polycyclic aromatic hydrocarbons in citrus fruit irrigated with fresh water under arid conditions: Concentrations, sources, and risk assessment

• PAHs in citrus fruits grown in North of Deir-Alla, Jordan valley were investigated. • Grapefruits showed the highest ∑PAHs concentration (34.857 µg kg −1 ) • The ILCR in the study region indicated a potential cancer risks to population. • PAHs emission sources are biomass burning, vehicular emissions and petrogenic origin. • BCF for ∑16 PAHs was observed in the order of grapefruit > lemon > mandarin > orange. In Jordan, as well as in all the world countries, consumption of citrus fruits is an essential part of the daily diet, so it is important to assess the potential risk of the persistent organic pollutants such as polyaromatic hydrocarbons (PAHs) in these fruits to the human health and identify their sources in order to eliminate or reduce them. This study reports 16 priority PAHs content in four types of peeled citrus fruits grown in Jordan valley. PAHs were detected in all the studied samples in variable quantities depending on the type of citrus fruits. The results showed that the highest PAH level corresponded to acenaphthene (35.018 µg/kg) in grapefruit. Among the carcinogenic PAHs, benzo[a]anthracene (BaA) and benzo(a)pyrene (BaP) were the most representative and found in all the analyzed fruit, soil, and water samples, whereas anthracene (ANT) was not detected at all. The mean ∑16 PAHs for the different fruits were found to be 62.593 µg kg −1 in grapefruit, 24.840 µg kg −1 in lemon, 22.901 µg kg −1 in mandarin, and 5.082 µg kg −1 in orange. The dominance of naphthalene (NAP) and acenaphthene (ACE) in soil under hot climatic conditions indicates the recent and continuous input of these types in the investigated area. The bioconcentration factor (BCF) for ∑16 PAHs was observed in the order of grapefruit > lemon > mandarin > orange. Based on the results of the principal component analysis (PCA), the primary sources of PAHs in agricultural soils mainly originated from biomass burning and vehicular emissions. The incremental lifetime cancer risk (ILCR) indicated that consumption of these four citrus fruits may expose human health to potential cancer risk. The findings of this study call the policymakers and public administrations to the formulation of stringent policies and actions to control biomass burning and vehicular emissions.

Sources and Toxicity Effects of Polyaromatic Hydrocarbons (PAH) in Water Resources and Sediments

PAH’lar, iki veya daha fazla aromatik halkayı bünyesinde bulunduran, yarı uçucu organik bileşiklerdir. Su ortamlarında PAH konsantrasyonları ve etkileri son yıllarda üzerinde önemle durulan konuların başında gelmektedir. Sedimentler, su ortamındaki en önemli PAH rezervuarlarındandır. Bu nedenle sedimentler, sucul ekosistemlerinin su kalitesinin kirliliklerinin değerlendirmesinde sıklıkla kullanılmaktadır. PAH’lar organik bileşiklerin tam yanmamasından dolayı oluşmakta ve çeşitli kaynaklardan alıcı ortamlara ulaşabilmektedirler. PAH’lar çevre ve insan sağlığı açısından zararlı etkilere sahiptir ve endüstriyel gelişme ile doğal ortamlardaki PAH konsantrasyonlarında önemli artışlar olmuştur. Sanayi-yoğun havzalarda kentleşme ve endüstrileşmeden dolayı PAH miktarlarının yüksek olması beklenmektedir. Amerikan Çevre Koruma Ajansı (USEPA) tarafından belirlenen 16 öncelikli PAH türünün su kaynaklarında ve sedimentlerde izlenmesi, PAH’ların su ve sedimentlerdeki konsantrasyonlarının belirlenmesi ve PAH-toksisite ilişkisini ortaya konması açısından oldukça önemlidir. Bu çalışmada literatürdeki çalışmalar derlenerek dünyada bu konuda yapılmış çalışmaların sonuçları ortaya koymaktadır.

Assessment of the risk of urban exposure to polyaromatic hydrocarbons in cities of Transylvania, Romania

The goal of this study is to estimate the urban environmental risk of exposure to polyaromatic hydrocarbons (PAHs) in the atmosphere of six cities of Transylvania region using moss as biomonitor and GC-MS analysis. The carcinogenic potential of the measured atmospheric PAHs was estimated by the benzo[a]pyrene toxicity equivalent (BaPeq) and the toxic equivalence factor (TEF), respectively. The PAHs concentration found in the analysed dried moss ranged from 45.27 ng g-1 in Târgu Mureș (S5) to 393.98 ng g-1 in Cluj-Napoca (S6) with a median of 217.18 ng g-1. Regarding the toxicity results of Σ16BaPeq, these had the minimum value of 5.69 ng g-1 in Bistrița (S4), while the maximum value of 48.65 ng g-1 was reached in Cluj-Napoca (S6). The median of the investigated urban areas was 19.75 ng g-1 being comparable to other studies conducted worldwide. The contribution of the dibenz[a]anthracene (DahA) and benzo[a]pyrene (BaP) to the results of BaP equivalency is significant, the median exceeding 56.33%. Thus, for a better understanding of the possible effects of PAHs on human health, simply measuring the concentration of the 16 priority PAHs would not be sufficient.

Integral assessment of food products contamination with priority polyaromatic hydrocarbons

Polyaromatic hydrocarbons (PAH) occur in the environment as complex mixtures and each congener has different carcinogenic and mutagenic activity. Our research goal was to accomplish an integral assessment of food products contamination with priority PAH basing on their determination with high precision procedures. We validated a procedure for determining the said substances and hygienically assessed contamination of certain food products with benzpyrene, as well as with different carcinogenic and mutagenic PAH equivalents taking into account samples with low contamination. Quantitative determination limit for benz(a)anthracene and benzpyrene was fixed at 0.01 μg/kg; benz(b)fluoranthene and chrysene, 0.1 μg/kg. Detection limit for benz(a)anthracene and benzpyrene amounted to 0.003 μg/kg in our research; for benz(b)fluoranthene and chrysene, 0.03 μg/kg. A procedure for integral assessment of contamination with the examined compounds allowed us to calculate benz(a)anthracene, benzpyrene, benz(b)fluoranthene, and chrysene contents in certain food products taking into account mixture of the examined substances, their individual contributions into aggregated contamination, and their different toxic and mutagenic activity. Median food products contamination with benzpyrene amounted to 0.0065–0.42 μg/kg; PAH taking into account carcinogenic equivalents, 0.03–0.55 μg/kg; PAH based on mutagenic equivalents, 0.04–0.81 μg/kg. Maximum concentrations of benzpyrene and PAH based on carcinogenic and mutagenic equivalents are due to a combination of subsequent technological processes that make for occurrence of the examined substances and also due to physical and chemical properties of the examined food products.

Интегральная оценка уровня контаминации пищевой продукции приоритетными полиароматическими углеводородами

Polyaromatic hydrocarbons (PAH) occur in the environment as complex mixtures and each congener has different carcinogenic and mutagenic activity. Our research goal was to accomplish an integral assessment of food products contamination with priority PAH basing on their determination with high precision procedures. We validated a procedure for determining the said substances and hygienically assessed contamination of certain food products with benzpyrene, as well as with different carcinogenic and mutagenic PAH equivalents taking into account samples with low contamination. Quantitative determination limit for benz(a)anthracene and benzpyrene was fixed at 0.01 μg/kg; benz(b)fluoranthene and chrysene, 0.1 μg/kg. Detection limit for benz(a)anthracene and benzpyrene amounted to 0.003 μg/kg in our research; for benz(b)fluoranthene and chrysene, 0.03 μg/kg. A procedure for integral assessment of contamination with the examined compounds allowed us to calculate benz(a)anthracene, benzpyrene, benz(b)fluoranthene, and chrysene contents in certain food products taking into account mixture of the examined substances, their individual contributions into aggregated contamination, and their different toxic and mutagenic activity. Median food products contamination with benzpyrene amounted to 0.0065–0.42 μg/kg; PAH taking into account carcinogenic equivalents, 0.03–0.55 μg/kg; PAH based on mutagenic equivalents, 0.04–0.81 μg/kg. Maximum concentrations of benzpyrene and PAH based on carcinogenic and mutagenic equivalents are due to a combination of subsequent technological processes that make for occurrence of the examined substances and also due to physical and chemical properties of the examined food products.

Distribution of Policyclic aromatic hydrocarbons in a snow cover in the territory of Ivanovo city, Russia.

The paper presents the results of a study of the content of 12 polyaromatic hydrocarbons (PAHs) in the snow cover of the city of Ivanovo (Russian Federation). It is shown that their average content exceeds the background level by 6.6 times, which made it possible to identify for which compounds the admission channels are associated with transboundary transport (naphthalene, pyrene, benz [b]fluorantin, benzo [a]pyrene and dibenz [a,h]anthracene), and for which with local emission sources (anthracene, phenanthrene, fluoranthene, chrysene, benz [k]fluorantin, and benzo [g,h,i]perylene). According to the known indicator ratios of the concentrations of PAHs, the main sources of release (pyrogenic and mixed) PAHs into the environment were estimated. The combination of experimental data in combination with factor analysis allowed identifying priority PAHs (naphthalene, fluoren, fluoranthene, benzo [a]pyrene and benzo [g,h,i]perylene), which should be included in the environmental monitoring programs of the region. Environmental risk assessments are given, which showed that the level of pollutant does not always adequately reflect the environmental impact for the territories. Thus, the contribution to the total PAH concentration of benz [b]fluorantin is only 9%, and to the amount of environmental risk - 51%. This must be taken into account in order to prioritize the control of individual components of PAHs in environmental objects.

Spatio\u2013Temporal Distribution of Polycyclic Aromatic Hydrocarbons in Urban Soils in Cape Town, South Africa

The spatial and seasonal distribution of eight US Environmental Protection Agency priority poly aromatic hydrocarbons (PAHs); namely benzo(b)fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)pyrene, benzo(k)fluoranthene, chrysene, benzo(a)anthracene, dibenz(a,h)anthracene and fluoranthene were investigated in 35 soil samples. Gas chromatography with flame ionization detection was used for the quantification of the PAHs in the residential, roadside and industrial soil samples collected in proximity to an industrial area, including a petrochemical plant, in Cape Town. The sum of the concentrations of the detected PAHs (ΣPAHs) in winter ranged between nd (not detected) and 13.88 mg/kg, with a mean concentration of 4.08 mg/kg and a standard deviation of distribution of 2.64 mg/kg, while in summer, ΣPAHs ranged between nd and 10.43 mg/kg, with a mean concentration of 0.50 mg/kg and standard deviation of distribution 1.83 mg/kg. The presence and concentration level of the PAHs detected in the soil samples vary significantly under climatic change (p < 0.05). The maximum concentrations of individual PAHs in the soil samples were higher in winter compared to the maximum concentrations of the PAHs detected in summer. The diagnostic ratios of selected PAH compounds showed that petrogenic processes were the most likely sources of the PAH compounds in the soil samples. In summer and winter, the total PAH concentration increased in order of residential soil < industrial soil ≤ roadside soil.

Concentrations and Source Identification of Polycyclic Aromatic Hydrocarbons (PAHs) in Mangrove Sediments from North of Persian Gulf

The concentrations of 16 Environmental Protection Agency (EPA) priority polyaromatic hydrocarbons (PAHs) were quantified in surface sediments from Hormozgan Province mangroves, south of Iran in dry and wet seasons. Sampling stations were selected in Laft and Khamir mangroves with international importance. Polyaromatic hydrocarbons varied from 75.24 ± 11.24 to 581.94 ± 637.39 ng/g dry weight basis. Pollution sources and their contribution for polyaromatic hydrocarbons pollution in sediments of Hormozgan mangroves were appointed based on molecular ratios and statistical methods, including principal components analysis (PCA) and multiple linear regression/principal components analysis (PCA/MLR) tests. Both of pyrogenic and petrogenic sources contributed in detected concentrations of PAHs. Contribution percentages of pyrogenic and petrogenic origins were estimated at 73.20 and 26.79%, respectively. Temporal variations showed that sediments contained higher levels of ∑PAHs in wet season than dry time. However, the mean detected ∑PAHs was lower than international quality guidelines; the high concentration of PAHs was found in Laft mangrove, suggesting the presence of PAH polluted localized area.

Distribution of Polycyclic Aromatic Hydrocarbons (PAHs) and Trace Metals in Ejamah-Ebubu Oil Spill Site

The distribution of polyaromatic hydrocarbons (PAHs) at different georeferenced sampling points: Nwata A, Nwata B, Nwata 3’, Ochani and Eyeyaro in one of the most contaminated mangrove swamp in Nigeria, Ejamah-Ebubu oil spill site was studied. The physico-chemical analysis of the sediment samples and trace metals were also conducted. PAHs were analyzed using gas-chroma-tography flame ionization detection while metals with atomic absorption spectrophotometry (AAS). The result showed that the total PAHs (summation of 16 US EPA priority PAHs) were present at all sampling points and the concentration ranged from 0.070 to 5.521 ppm with Nwatu A > Nwatu B > Ochani > Egeyaro > Nwatu 3’. The pH of the site is acidic. The concentration of trace metals for most sampling points is iron > chromium > lead > nickel > vanadium. Our result indicates that the concentration of PAHs is at level higher than the permitted level therefore; it is recommended that Ejamah-Ebubu oil spill site be remediated.

Determination of Priority Poly Aromatic Hydrocarbons Using Solid Phase Extractionand HPLC in Diyala River

Determination of Priority Poly Aromatic Hydrocarbons Using Solid Phase Extractionand HPLC in Diyala River

Bioremediation of a tropical clay soil contaminated with diesel oil

The removal of polyaromatic hydrocarbons (PAH) in tropical clay soil contaminated with diesel oil was evaluated. Three bioremediation treatments were used: landfarming (LF), biostimulation (BS) and biostimulation with bioaugmentation (BSBA). The treatment removal efficiency for the total PAHs differed from the efficiencies for the removal of individual PAH compounds. In the case of total PAHs, the removal values obtained at the end of the 129-day experimental period were 87%, 89% and 87% for LF, BS and BSBA, respectively. Thus, the efficiency was not improved by the addition of nutrients and microorganisms. Typically, two distinct phases were observed. A higher removal rate occurred in the first 17 days (P-I) and a lower rate occurred in the last 112 days (P-II). In phase P-I, the zero-order kinetic parameter (μg PAH g−1 soil d−1) values were similar (about 4.6) for all the three treatments. In P-II, values were also similar but much lower (about 0.14). P-I was characterized by a sharp pH decrease to less than 5.0 for the BS and BSBA treatments, while the pH remained near 6.5 for LF. Concerning the 16 individual priority PAH compounds, the results varied depending on the bioremediation treatment used and on the PAH species of interest. In general, compounds with fewer aromatic rings were better removed by BS or BSBA, while those with 4 or more rings were most effectively removed by LF. The biphasic removal behavior was observed only for some compounds. In the case of naphthalene, pyrene, chrysene, benzo[k]fluoranthene and benzo[a]pyrene, removal occurred mostly in the P-I phase. Therefore, the best degradation process for total or individual PAHs should be selected considering the target compounds and the local conditions, such as native microbiota and soil type.

Branchial structure and hydromineral equilibrium in juvenile turbot (Scophthalmus maximus) exposed to heavy fuel oil

This study is an attempt to go further in the comprehension of the effects of heavy fuel oil in the context of an accidental oil spill at sea. It focuses on the link between morphological and functional impacts of realistic doses of the dissolved fraction of a heavy fuel oil on fish gills. Juvenile turbot, Scophthalmus maximus were exposed to the dissolved fraction of a heavy fuel oil for 5 days and then placed 30 days in clean sea water for recovery. During the contamination period, the concentration of the 16 US EPA priority poly-aromatic hydrocarbons showed small variations around a mean value of 321.0 ± 9.1 ng l⁻¹ (mean ± SEM). The contamination induced a 64% increase in hepatic cytochrome P 450 1A (Western blot analysis). Osmolality, [Na⁺] and [Cl⁻] rapidly and significantly increased (by 14, 23 and 28% respectively) and slowly decreased to normal levels during the recovery period. At the same time, branchial histology showed decreases in the number of mucocytes (by 30%) and of chloride cells (by 95%) in the interlamellar epithelium. Therefore, it is suggested that the osmotic imbalance observed after the 5 days of exposure to the dissolved fraction of the heavy fuel oil is the consequence of the structural alteration of the gills i.e, the strong reduction of ionocyte numbers.

Validation of the analytical procedure for the determination of polyaromatic hydrocarbons in smoke flavourings using high performance liquid chromatography coupled to an ultraviolet, diode array or fluorescence detector

High performance liquid chromatography (HPLC) coupled to an ultraviolet (UV), diode array or fluorescence detector (UV/DAD/FLD) has been used to set up an analytical procedure for the quantification of 16 EU priority polyaromatic hydrocarbons (PAHs) in smoke flavourings. The following parameters have been determined for the 16 EU priority PAHs: limit of detection, limit of quantification, precision (repeatability and intermediate precision), recovery and measurement uncertainty, using the concept of accuracy profiles. They were in close agreement with quality criteria described in the Commission Regulation (EC) no. 627/2006 concerning PAHs in smoke flavourings.

Analysis of the 16 Environmental Protection Agency priority polycyclic aromatic hydrocarbons by high performance liquid chromatography-oxidized diamond film electrodes

The capabilities of using boron-doped diamond (BDD) thin films as electrode materials for analysis of the 16 US Environmental Protection Agency (EPA) priority polyaromatic hydrocarbons (PAHs) after a liquid chromatographic separation were evaluated. The BDD electrode was able to detect all 16 PAHs with high sensitivity due to the low background current and wide potential window. The method provided detection limits ranging from 12–40 nM (3–10 ppb) and repeatable results over consecutive analysis. Calibration curves were linear up to at least 10 μM for all PAHs. The work shows the promising use of diamond as an amperometric detector in high performance liquid chromatography (HPLC), especially for PAHs and other hydrophobic aromatic compounds.

Evaluation of the relationships between biochemical endpoints of PAH exposure and physiological endpoints of reproduction in male California Halibut (Paralichthys californicus) exposed to sediments from a natural oil seep

Coal Oil Point (COP) is a natural oil seep off the coast of Santa Barbara, California. Although most studies examining the fate and effects of petroleum have focused upon urbanized or anthropogenic sources of inputs, few have examined the effects of polyaromatic hydrocarbons (PAHs) derived from natural seeps. In order to evaluate the effects of PAHs derived from COP on marine fish populations, hatchery-reared California Halibut (Platichthys californicus) were exposed for 30 days to seven dilutions of sediments collected from COP. Hepatic cytochrome P450 1A (CYP1A), biliary fluorescent aromatic compounds (FACs), gonadal somatic indices, and plasma steroid concentrations. Sixteen USEPA priority PAHs were targeted for analysis in each sediment dilution. In general, biochemical responses were somewhat recalcitrant to dose-response relationships and were less sensitive than the literature values established for the same indicators following exposure to urbanized PAHs. Trends toward reductions in plasma 17beta-estradiol concentrations were observed, but reductions in gonadal somatic indices were not observed. FAC values for naphthalene, benzo(a)pyrene, phenanthrene-related compounds reached maximums at 33-100% COP sediment. The resulting insensitivity may be unique for exposure to "natural" petroleum due to a higher concentration of lower molecular weight PAHs or uncharacterized inhibitors.

Quantitative immunoassay for determining polyaromatic hydrocarbons in electrical insulating oils

The development and application of a combined sample extraction and immunoassay protocol for the quantification of polyaromatic hydrocarbons (PAHs) in transformer oils is reported. Tests were performed on 12 different used transformer oils from three major manufacturers. The removal of matrix interferents was achieved by loading oil fractions onto silica solid phase extraction cartridges and eluting with non-polar solvent prior to evaporation and reconstitution in a more polar medium. Extracts were immunoassayed using two commercially available PAH test kits either having broad specificity towards priority PAHs or enhanced binding specificity toward more carcinogenic PAHs. The total and carcinogenic PAH test kits yielded PAH levels in the oil extracts 5.86-fold and 126-fold lower than the industry-standard IP346 method. The latter method, widely used by the industry, since it correlates with biological carcinogenicity tests, grossly over-estimates PAH levels in oils since it is a non-specific gravimetric solvent extraction approach. The assay was found to be unaffected by the extract sample matrix and was capable of determining PAHs at the nanogram per millilitre level. The assay protocol was simple, low-cost and rapid (<2 h) and equally amenable to operation at remote sites or high-throughput sample screening. The binding specificity of the total anti-PAH antibody was examined by preparing and loading an anti-PAH immunosorbent with oil, prior to solvent displacement of antibody-bound compounds and by gas chromatography (GC)–mass spectrometry (MS) analysis.