Large-scale risk assessment of polycyclic aromatic hydrocarbons in shoreline sediments from Saudi Arabia: Environmental legacy after twelve years of the Gulf war oil spill

A large-scale assessment of polycyclic aromatic hydrocarbons (PAHs) from the 1991 Gulf War oil spill was performed for 2002-2003 sediment samples (n = 1679) collected from habitats along the shoreline of Saudi Arabia. Benthic sediment toxicity was characterized using the Equilibrium Partitioning Sediment Benchmark Toxic Unit approach for 43 PAHs (ESBTU_FCV,43). Samples were assigned to risk categories according to ESBTU_FCV,43 values: no-risk (≤1), low (>1-≤2), low-medium (>2-≤3), medium (>3-≤5) and high-risk (>5). Sixty seven percent of samples had ESBTU_FCV,43 > 1 indicating potential adverse ecological effects. Sediments from the 0-30 cm layer from tidal flats, and the >30-<60 cm layer from heavily oiled halophytes and mangroves had high frequency of high-risk samples. No-risk samples were characterized by chrysene enrichment and depletion of lighter molecular weight PAHs, while high-risk samples showed little oil weathering and PAH patterns similar to 1993 samples. North of Safaniya sediments were not likely to pose adverse ecological effects contrary to sediments south of Tanaqib. Landscape and geomorphology has played a role on the distribution and persistence in sediments of oil from the Gulf War.     

Cation exchange in a glacial till drumlin at a road salt storage facility

At a former wood preservation plant severely contaminated with coal tar oil, in situ bulk attenuation and biodegradation rate constants for several monoaromatic (BTEX) and polyaromatic hydrocarbons (PAH) were determined using (1) classical first order decay models, (2) Michaelis–Menten degradation kinetics (MM), and (3) stable carbon isotopes, for o-xylene and naphthalene. The first order bulk attenuation rate constant for o-xylene was calculated to be 0.0025 d^− 1 and a novel stable isotope-based first order model, which also accounted for the respective redox conditions, resulted in a slightly smaller biodegradation rate constant of 0.0019 d^− 1. Based on MM-kinetics, the o-xylene concentration decreased with a maximum rate of k_max = 0.1 µg/L/d. The bulk attenuation rate constant of naphthalene retrieved from the classical first order decay model was 0.0038 d^− 1. The stable isotope-based biodegradation rate constant of 0.0027 d^− 1 was smaller in the reduced zone, while residual naphthalene in the oxic part of the plume further downgradient was degraded at a higher rate of 0.0038 d^− 1. With MM-kinetics a maximum degradation rate of k_max = 12 µg/L/d was determined. Although best fits were obtained by MM-kinetics, we consider the carbon stable isotope-based approach more appropriate as it is specific for biodegradation (not overall attenuation) and at the same time accounts for the dominant electron-accepting process. For o-xylene a field based isotope enrichment factor ε_field of − 1.4 could be determined using the Rayleigh model, which closely matched values from laboratory studies of o-xylene degradation under sulfate-reducing conditions.     

Oil Identification Based on a Goodness-of-Fit Metric Applied to Hydrocarbon Analysis Results

Assessment of environmental damage following accidental oil spills requires reliable oil identification methods. Results from hydrocarbon analyses of environmental samples are often difficult to interpret, because of the changes in oil composition (or weathering) that follows release into the environment, and because of confounding by hydrocarbons from other sources. To a first-order approximation, weathering proceeds according to simple first-order loss-rate (FOLR) kinetics for polycyclic aromatic hydrocarbons (PAH) based on molecular size. This relationship between relative weathering rate and molecular size can be exploited to infer the initial PAH composition of spilled oils, and this information can be combined with results for weathering-invariant analytes to substantially increase the precision and accuracy of hydrocarbon source recognition methods. The approach presented here evaluates a goodness-of-fit metric between the measured hydrocarbon composition of an environmental sample and a suspected source, after correcting for PAR weathering losses based on FOLR kinetics. Variability from analytical and sampling error may thus be accounted for, and source identifications can be expressed as objective probability statements. This approach is illustrated by application to four independent case studies.     

Polycyclic aromatic hydrocarbons in cigarette sidestream smoke particulates from a Taiwanese brand and their carcinogenic relevance

Polycyclic aromatic hydrocarbons (PAHs) adsorbed on cigarette sidestream smoke particulates (CSSPs) have been regarded as important contributors to lung carcinogenesis in never smokers. However, limited information is available on PAH levels in cigarette sidestream smoke. Here we determine the concentrations of 22 PAHs, including 16 US EPA priority PAHs, in CSSPs generated from a high market-share domestic brand in Taiwan. Five of the 22 PAHs are undetectable. The remaining 17 PAHs constitute about 0.022% of the total mass of CSSPs. Near one fifth of the PAH mass come from IARC group 1 and group 2 carcinogens. Carcinogenic potency is equivalent to 144 ng benzo[a]pyrene per cigarette converted according to potency equivalency factors (PEFs). The CSSP condensate could activate AhR activity and induce AhR target gene expression. High concentrations of CSSPs also exhibited AhR-independent cytotoxicity. However, mixing the 17 PAHs as the composition in the CSSP condensate could not reconstitute either capacity. Since AhR activation and cytotoxicity are important mechanisms underlying carcinogenic potency, the results suggest that other component compounds play a more active role in carcinogenesis. The approach of individual PAH profiling plus PEF conversion commonly used in risk assessment is likely to underestimate the risk caused by environmental cigarette smoke exposure.     

Assessment of sediment contamination in Casco Bay, Maine, USA

The current status of contaminant concentrations in Casco Bay, decadal trends of these contaminants and changes in their geographical distribution are assessed using sediment samples collected approximately 10 years apart. In general, regulated contaminants appeared to be decreasing in concentration. Total PAH and dioxins/furans concentrations did not significantly change over this period. Total organochlorine pesticides, 4,4-DDE, 4,4-DDD, total DDT, PCB, tributyltin and total butyltin decreased in concentration. Trace element concentrations in sediments decreased at the majority of the sampling sites for chromium, nickel, and selenium while arsenic, cadmium, copper, lead, mercury, silver, and zinc remained relatively constant. None of the contaminants measured has increased by more than a factor of 2. Selected sites located in the Inner Bay, where concentrations are higher and new inputs were more likely, showed increased concentrations of contaminants. Most contaminants were not found at concentrations expected to adversely affect sediment biota based on ERL/ERM guidelines.     

Phytotoxicities of fluoranthene and phenanthrene deposited on needle surfaces of the evergreen conifer, Japanese red pine (Pinus densiflora Sieb. et Zucc.)

Polycyclic aromatic hydrocarbons (PAHs) have been widely studied with respect to their carcinogenic and mutagenic effects on animals and human cells. Phenanthrene (PHE) and fluoranthene (FLU) effects on the needle photosynthetic traits of 2-year-old Japanese red pine (Pinus densiflora Sieb. et. Zucc.) seedlings were investigated. Three months after fumigation of foliage with solutions containing these PAHs (10 microM each), FLU had negative effects on net photosynthesis at near-saturating irradiance, stomatal conductance, initial chlorophyll fluorescence, and the contents of total chlorophyll, magnesium, and ribulose 1,5-bisphosphate carboxylase (rubisco) of current-year needles. PHE had similar negative effects to FLU but in lesser magnitude. The effects of the PAHs were mitigated by the addition of an OH-radical scavenger (mannitol) into the PAH solutions. PAHs deposited on the surface of pine needles may induce the generation of reactive oxygen species in the photosynthetic apparatus, a manner closely resembling the action of the herbicide paraquat.     

The use of physiological characteristics for comparison of organic compounds phytotoxicity

The influence of intact (FLT) and photomodified (phFLT) fluoranthene (0.05, 0.5 and 5 μmol l⁻¹) and herbicide Basagran (5, 20, 35 and 50 nmol l⁻¹) on the germination, growth of seedlings and photosynthetic processes in pea plants (Pisum sativum L., cv. Garde) was investigated. The germination was significantly inhibited already by the lowest concentration (0.05 μmol l⁻¹) of FLT and phFLT, while Basagran caused inhibition only in higher concentrations (35 and 50 nmol l⁻¹). The growth of roots was significantly inhibited by higher concentration 5 μmol l⁻¹ of both FLT and phFLT and the shoot of seedlings was significantly influenced only by photomodified form. The length of root and shoot was inhibited already by concentration 5 nmol l⁻¹ of Basagran. Organic compounds applied on chloroplasts suspension influenced primary photochemical processes of photosynthesis. In chlorophyll fluorescence parameters, the significant increase of F₀ values and the decrease of F_V/F_M and Φ_II values by application of FLT (0.5 and 5 μmol l⁻¹) and phFLT (0.05, 0.5 and 5 μmol l⁻¹) was recorded. The maximum capacity of PSII (F_V/F_M) was influenced by the highest (50 nmol l⁻¹) and the effective quantum yield of PSII (Φ_II) already by the lowest (5 nmol l⁻¹) concentration of Basagran. Hill reaction activity decreased and was significantly inhibited by higher concentration (0.5 and 5 μmol l⁻¹) of FLT and phFLT and already by the lowest concentration (5 nmol l⁻¹) of Basagran.     

Toxicity of carbaryl,diquat dibromide,and fluoranthene,individually and in mixture,to larval grass shrimp,Palaemonetes pugio

This study examined the toxicity of two pesticides (carbaryl and diquat dibromide) and one polycyclic aromatic hydrocarbon (fluoranthene), both singly and in mixture, to grass shrimp larvae (Palaemonetes pugio). These three chemicals are all present in coastal environments and can easily enter estuarine ecosystems. Fluoranthene was the most toxic chemical with a 96-h LC₅₀ value of 32.45 μ g/L, followed by carbaryl (43.02 μ g/L) and diquat dibromide (1624 μ g/L). In the chemical mixture tests, the binary carbaryl/diquat dibromide mixture and the ternary carbaryl/diquat dibromide/fluoranthene mixture had additive results.     

Biological effect monitoring in dab (<Emphasis Type="Italic">Limanda limanda</Emphasis>) using gene transcript of CYP1A1 or EROD—a comparison

BACKGROUND, AIM, AND SCOPE: Gene expression analyses with real-time (RT)-polymerase chain reaction (PCR) gains importance in marine monitoring. This new technique has to be compared to the classical approaches like the well known biomarker ethoxyresorufin-O-deethylase (EROD) to test their suitability for monitoring programmes. The goal of the present study is to compare EROD activity and CYP1A1 mRNA expression in the important monitoring fish species dab (Limanda limanda) and to answer the question of whether these parameters reflect the polycyclic aromatic hydrocarbon (PAH) contamination of the fish. Further on, glyceraldehyd-3-phosphate dehydrogenase (GAPDH) was investigated as a potential housekeeping gene. MATERIALS AND METHODS: Female dab were caught in the summer of 2004 in the North Sea and in the Baltic. EROD activity was determined in liver samples by a kinetic fluorimetric assay according to a standard protocol. The gene expression of CYP1A (cytochrome P450 1A) and GAPDH were determined by means of RT-PCR. Results were compared to gonado somatic index and to the concentration of PAH metabolite 1OHPyr (1-hydroxypyrene) analysed in the bile fluids of the fish, respectively. RESULTS: Dab from all stations showed a considerable individual variation in the levels of both CYP1A mRNA and EROD. Highest mean values for CYP1A mRNA and EROD were detected in the northern part of the sampling area. In contrast, the PAH metabolite 1OHPyr was found at the highest concentration in fish caught near the German coast. CYP1A mRNA and EROD showed only a minor but significant correlation (r = 0.32, p < 0.05, n = 123). 1OHPyr in bile correlated significantly (p < 0.05) with the amount of GAPDH mRNA content in the liver. DISCUSSION: The significant but low correlation of CYP1A mRNA and EROD activity on an individual basis illustrates that these two parameters are apparently not closely linked. However, maximum EROD values correspond with maximum CYP1A mRNA concentrations when station means are regarded. Because EROD and CYP1A mRNA in dab follow different physiological principles, their application will lead to related but not identical monitoring results. This should be taken into account when future marine monitoring programmes are designed. The results also indicate that PAH are not the crucial factor for CYP1A and EROD levels in dab from the off-shore areas in the North Sea. This is remarkable because the PAH metabolism is known to be CYP1A-dependent and the widely used biomarker EROD has been recommended for monitoring PAH-related effects in fish from the North Sea. Due to a correlation between GAPDH and 1OHPyr, GAPDH was not suitable as housekeeping gene for dab. CONCLUSIONS: Neither the results from EROD nor from CYP1A1 mRNA measurements in dab reflected their exposure to PAH as measured by the PAH metabolite 1OHPyr. Thus, the question arises of whether EROD or CYP1A mRNA is a suitable biomarker at all to indicate PAH exposure in dab from the open North Sea. RECOMMENDATIONS AND PERSPECTIVES: For future biological effect monitoring, it is advisable to measure more and predominately independent parameters by RT-PCR and to incorporate more components of the detoxification system.     

PAHs Contamination in Bank Sediment of the Yamuna River, Delhi, India

This study was performed to elucidate the distribution, concentration trend and possible sources of PAHs in bank sediment of river Yamuna in Delhi, India. The levels of 16 priority polycyclic aromatic hydrocarbons (PAHs) were analyzed during pre-monsoon, monsoon and post-monsoon seasons in the sediment fraction < 53 μm. Reference standards and internal standards were used for identification and quantification of PAHs by HPLC. The sum of 16 PAH compounds ranged from 4.50 to 23.53 μg/g with a mean concentration of 10.15 ± 4.32 μg/g (dry wt.). Among 5 sites studied, the site, Income Tax Office (ITO) was found to be the hotspot attaining highest concentration. Predominance of 2–4 ring PAHs suggests a relatively recent local sources of PAHs in the study area. Moreover, molecular indices based source apportionment also illustrates pyrogenic source fingerprint of PAHs. No significant temporal trend was observed.