Comparison of mussels and semi-permeable membrane devices as intertidal monitors of polycyclic aromatic hydrocarbons at oil spill sites

Side-by-side comparisons of polycyclic aromatic hydrocarbon (PAH) concentrations in resident blue mussels (Mytilus trossulus) and in semi-permeable membrane devices (SPMDs) were made at four sites in Prince William Sound, Alaska. SPMDs were deployed for approximately 30 days on the surface of the beach sediment at three tidal elevations on each shore and in 0.5 m deep open pits in the middle intertidal zone. Total PAH (TPAH) concentrations in mussels and in SPMDs were correlated, but the PAH compositions were different. The lower molecular weight PAH were relatively more abundant in the SPMDs than in the mussels at oiled and HA sites. TPAH concentrations in SPMDs deployed in pits and mussels collected adjacent to those pits at oiled sites were higher than in SPMDs and mussels from non-pitted SPMD locations approximately 3-15 m from the pits. Pitting released buried oil making its PAH bioavailable. SPMDs deployed in the supratidal zone (+4.0 m tidal elevation) were exposed to atmospheric contaminants for a large fraction of the deployment time and accumulated primarily pyrogenic (combustion-sourced) PAH from the atmosphere. The SPMD strips supplied by the manufacturer contained significant amounts (approximately 125 ng/strip) of primarily alkylated 2-3 ring PAH. These blank levels make SPMDs unsuitable for shoreline assessments when environmental PAH concentrations are low. Consequently, where available, mussels are recommended for use in assessments of the bioavailability of buried oil residues sequestered in intertidal sediments following an oil spill. Mussels are the preferred monitoring tool when the assessments involve food-chain effects. At locations where the absence of mussels necessitates the use of SPMDs or other passive sampling devices, their limitations need to be carefully considered in the interpretation of results.     

Concentrations of PAHs (polycyclic aromatic hydrocarbons) in various marine organisms in relation to those in sediments and to trophic level

Sediments and marine organisms such as mussels (Mytilus galloprovincialis), fish (Mullus barbatus, Serranus scriba), crabs (Polybius henslowi) and shrimp-like crustaceans (mysids, euphausiids) were sampled on European coasts, France, Spain) and analysed for their PAH content by gas chromatography/mass spectrometry (GC-MS). The PAH concentrations determined in the organisms were significantly negatively correlated with logK_ow values, but to different extents according to the species. This was explained by the greater exposure of the organisms to the lower molecular weight compounds with differences resulting from different feeding habits, habitat, and biotransformation capacities of the organisms in relation to trophic levels. The influence of these observations on the use of different sentinel species in biomonitoring programmes is discussed.     

Polycyclic aromatic hydrocarbons loads into the Mediterranean Sea: estimate of Sarno River inputs

The polycyclic aromatic hydrocarbons (PAHs) pollution in the Sarno River and its environmental impact on the Gulf of Naples (Tyrrhenian Sea, Central Mediterranean Sea) were estimated. The 16 PAHs identified by the USEPA as priority pollutants and perylene were determined in the water dissolved phase (DP), suspended particulate matter (SPM) and sediments. Total PAHs concentrations ranged from 23.1 to 2670.4 ng L(-1) in water (sum of DP and SPM) and from 5.3 to 678.6 ng g(-1) in sediment samples. Source analysis revealed that PAHs mainly came from combustion process. Contaminant discharges of PAHs into the sea were calculated in about 8530 gd(-1) showing that this river should account as one of the main contribution sources of PAHs to the Tyrrhenian Sea.     

Levels of chlorinated hydrocarbons in marine animals from the central Mediterranean

Concentrations of chlorinated hydrocarbons (DDT and metabolites, PCBs, aldrin, dieldrin, HCB and BHCs) have been determined in the tissues of five species of marine animals sampled in selected areas of the central Mediterranean.     

Polycyclic aromatic hydrocarbons in commercial fish and lobsters from the coastal waters of Madagascar following an oil spill in August 2009

Concentrations of polycyclic aromatic hydrocarbons were determined in species of commercial fish and lobsters following an oil-spill just off the protected Madagascan coastline. Samples were collected along the coastline within and outside the affected area. Summed PAH concentrations ranged from 1.9 μg kg⁻¹ to 63 μg kg⁻¹ wet weight, but with no higher molecular weight PAHs (>202 Da) being detected. All concentrations of benzo[a]pyrene, benz[a]anthracene and dibenz[a,h]anthracene were <0.1 μg kg⁻¹ wet weight, well within the EU and UK set limits for the protection of human health. Additionally, samples were calculated as the benzo[a]pyrene toxic equivalency quotient (TEQ) and found to be well below the level of concern in relation to health of human consumers. Evaluation of the biota PAH data indicated the origin of PAH was predominantly petrogenic with >80% arising from oil sources. Profile studies indicate a low-level multisource petrogenic contamination probably representing a pre-spill background for the area.     

Fate of polycyclic aromatic hydrocarbon (PAH) contamination in a mangrove swamp in Hong Kong following an oil spill

The fate of polycyclic aromatic hydrocarbon (PAH) contamination in a mangrove swamp (Yi O) in Hong Kong after an oil spill accident was investigated. The concentrations and profiles of PAHs in surface sediments collected from five quadrats (each of 10 m×10 m) covering different degrees of oil contamination and the most contaminated mangrove leaves were examined in December 2000 (30 days after the accident) and March 2001 (126 days later). The concentrations of total PAHs in surface sediments ranged from 138 to 2135 ng g⁻¹, and PAHs concentrations decreased with time. In the most contaminated sediments, total PAHs dropped from 2135 (30 days) to 1196 ng g⁻¹ (120 days), and the decrease was smaller in less contaminated sediments. The percentage reduction in sediment PAHs over three months (44%) was less significant than that in contaminated leaves (85%), indicating PAH in or on leaves disappeared more rapidly. The PAH profiles were very similar in sediments collected from quadrats Q1 and Q2 with benzo[a]anthracene and pyrene being the most abundant PAH compounds, but were different in the other three quadrats. The proportion of the light molecular weight PAHs to total PAHs increased after three months, especially phenanthrene. Results suggest that physical and photo-chemical weathering (tidal washing and photo-oxidation) of crude oil in surface sediments and on plant leaves were important processes in the first few months after the oil spill. The PAH contamination in Yi O swamp came from both petrogenic and pyrolytic sources. The petrogenic characteristic in the most contaminated sediment was confirmed with high values of phenanthrene to anthracene ratio (>10) and low values of fluoranthene to pyrene ratio (0.3–0.4).     

Distribution and mass inventory of polycyclic aromatic hydrocarbons in the sediments of the south Bohai Sea, China

Recent occurrence, distribution and mass inventories of 16 priority polycyclic aromatic hydrocarbons (PAHs) proposed by USEPA in the south Bohai Sea (BS) were studied based on the analytical data of 71 surface sediment samples. The concentrations of 16 PAHs varied from 37 to 537 ng g⁻¹ (dry weight). A clear difference was observed between the coastal Bohai Bay (CBB) and its adjacent BS (ABS) in the distribution and compositions of PAHs. The petrogenic source of phenanthrene in CBB was attributable to the industrial wastewater, fugitive fuel leakages from ships and offshore oil production. Four to six ring PAHs were predominantly from the coal and wood combustions in the whole area. The estimated PAH input to the south BS (43,000 km², 56% of BS in area) was 36.6 ton yr⁻¹, indicating that the study area was one of the important reservoirs of PAHs in world.     

Scientific management of Mediterranean coastal zone: a hybrid ocean forecasting system for oil spill and search and rescue operations

The oil spill from Prestige tanker showed the importance of scientifically based protocols to minimize the impacts on the environment. In this work, we describe a new forecasting system to predict oil spill trajectories and their potential impacts on the coastal zone. The system is formed of three main interconnected modules that address different capabilities: (1) an operational circulation sub-system that includes nested models at different scales, data collection with near-real time assimilation, new tools for initialization or assimilation based on genetic algorithms and feature-oriented strategic sampling; (2) an oil spill coastal sub-system that allows simulation of the trajectories and fate of spilled oil together with evaluation of coastal zone vulnerability using environmental sensitivity indexes; (3) a risk management sub-system for decision support based on GIS technology. The system is applied to the Mediterranean Sea where surface currents are highly variable in space and time, and interactions between local, sub-basin and basin scale increase the non-linear interactions effects which need to be adequately resolved at each one of the intervening scales. Besides the Mediterranean Sea is a complex reduced scale ocean representing a real scientific and technological challenge for operational oceanography and particularly for oil spill response and search and rescue operations.     

Distributions of polycyclic aromatic hydrocarbons in the Daliao River Estuary of Liaodong Bay, Bohai Sea (China)

The distributions of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in the aqueous phase, suspended particulate matter (SPM), sediment, and pore water of the Daliao River Estuary in Liaodong Bay, Bohai Sea (China). Total PAH concentrations ranged from 139.16 to 1717.87 ng L⁻¹ in surface water, from 226.57 to 1404.85 ng L⁻¹ dry weight in SPM, from 276.26 to 1606.89 ng g⁻¹ dry weight in sediments, and from 10.20 to 47.27 μg L⁻¹ in pore water. PAH concentrations were at relatively moderate levels in water, SPM, sediment and pore water in comparison with those reported for other estuary and marine systems around the world. Sedimentary PAH concentrations decreased offshore owing to active deposition of laterally-transported river-borne particles. PCA analysis of the possible PAH source suggested petrogenic and pyrolytic PAH inputs in the studied region.     

Shallow sublittoral meiofauna communities and sediment polycyclic aromatic hydrocarbons (PAHs) content on the Galician coast (NW Spain), six months after the Prestige oil spill

The aim of this work was to detect the impact of Prestige oil spill on meiobenthic community structure at higher levels of taxonomic aggregation. In addition, the relationship between sediment individual polycyclic aromatic hydrocarbon (PAH) concentration and meiofauna community structure was investigated. Six months after the Prestige oil spill, meiobenthos community and sediment PAHs content from seven shallow subtidal localities along the Galician coast were studied. Two sites presented differences in community structure, characterized by high densities of nematodes, gastrotrichs and turbellarians, and low densities of copepods. Chrysene and triphenylene were only found at these two disturbed sites and could be responsible for differences of meiobenthos community structure. However, differences in community structure of sites could be linked with sedimentary parameters, and discrimination between the effect of PAHs and sedimentary parameters was impossible due to the lack of baseline studies on meiobenthos and PAHs contents in this area.     

Spatial and temporal distribution of dissolved/dispersed aromatic hydrocarbons in seawater in the area affected by the Prestige oil spill

Seawater samples collected at three depths from 68 stations along the Northern Spanish coast were analysed for dissolved/dispersed petroleum aromatic hydrocarbons by UV-fluorescence and for 25 individual compounds by GC-MS. Sampling was performed in December 2002, just after the Prestige oil spill, and in February-March and September 2003. Higher concentrations of total aromatic hydrocarbons were found at all depths in the samples collected during December 2002 off the Galicia coast, with levels ranging between 0.19 and 28.8 microg/L eq. oil (0.1-4.8 microg/L chrysene eq.). These values decreased in the following cruises, till <0.05-2.86 microg/L oil eq. (av. 0.23 microg/L chrysene eq.) in September 2003, possibly representing the background levels for the region. However, in the Cantabrian coast they were still high at the surface in the March cruise, probably by the late arrival of the fuel-oil to this area. Some coastal hot spots were also identified, with values up to 29.2 microg/L fuel-oil eq., close to river mouths and urban areas. The individual PAH distributions in the December 2002 sampling off-Galicia were dominated by alkyl-naphthalene derivatives, consistently with the pattern distribution shown by the fuel-oil water accommodated fraction. The higher concentrations were found in the subsurface samples along the Costa da Morte, the area most heavily affected by the spill (av. 0.46 microg/L Sigma16 PAHs). The rest of the samples collected in other areas exhibited lower concentrations and a more even distribution of 2-4 ring PAHs, that ranged from 0.09 to 0.37 microg/L (av. 0.15 microg/L Sigma16 PAHs), with decreasing trends offshore and downward the water column. In September 2003, the values were rather uniform, averaging 0.09 microg/L (Sigma16 PAHs).     

Sedimentary record of polycyclic aromatic hydrocarbons in a sediment core from the Pearl River Estuary, South China

Owing to the hydrodynamic and sedimentation conditions, the western shoal of the Pearl River Estuary (PRE) is known to be an important sink of terrestrial substances including particle-associated pollutants from the Pearl River Delta (PRD) region. In this study, we report the sedimentary record of polycyclic aromatic hydrocarbons (PAHs) during the 20(th) century in a sediment core from the western shoal of the PRE. The summation PAH concentration ranged from 59 ng g(-1) to 330 ng g(-1) in the core with two distinct peaks. An initial increase of summation PAH concentration was found around the 1860s. The amounts of PAHs remained relatively constant for roughly 100 years, followed by the first peak in the 1950s. Then, there was a decrease in PAH concentration and flux in the 1960s and 1970s. A sharp increase of PAH concentration was observed in the early 1980s with a maximum concentration in the 1990s. The PAH diagnostic ratios indicated that the PAHs in the sediment core were mainly of pyrolytic origin, and that atmospheric deposition and land runoff may serve as the important pathways for PAHs input to the sediment. The Gross Domestic Product (GDP) was used as an index of socioeconomic development in the PRD region, which was correlated positively with the changes of PAH concentration and flux in the sediment core. The rapid increase in vehicle numbers and energy consumption in the region in the last two decades may have contributed to the rapid PAH increase since the early 1980s. The results clearly elucidated the impact of regional economic development on the estuarine environment.     

Induction of DNA strand breaks in the mussel (Mytilus trossulus) and clam (Protothaca staminea) following chronic field exposure to polycyclic aromatic hydrocarbons from the Exxon Valdez spill

In 2002, 13 years after the Exxon Valdez spill, mussels and clams were examined for lingering oil exposure and damage. Known oil patches were sampled at four locations, and compared to nearby reference areas (same bay), and were also compared to "hot reference" sites to verify the methods used (Cordova harbor and fresh diesel spill at Port Chalmers). Passive samplers deployed for a month at the sites, along with tissue samples, confirmed that the oiled sites were oiled (fingerprinting back to Exxon Valdez oil) and that reference sites were clean. The highest PAH loads were detected in sub-surface interstitial waters at oiled sites. Exposure at the surface was generally low level, and probably intermittent. DNA damage was assessed in blood cells using sensitive comet analyses. DNA strand breakage was detected in both mussels and clams, with the highest level of damage detected at "hot reference" sites of Cordova harbor and Port Chalmers. Bioavailability and DNA damage at the oiled sties was low, indicating there has been substantial progress in recovery from the spill 13 years before, yet low level bioavailability and damage were still detectable.     

Phase distribution of hydrocarbons in the water column after a pelagic deep ocean oil spill

Spills from wrecks are a potential major source of pollution in the deep ocean. However, not much is known about the fate of a spill at several kilometers depth, beyond the oceans continental shelves. Here, we report the phase distribution of hydrocarbons released from the wrecks of the Prestige tanker, several years after it sank in November 2002 to depths between 3500 and 3800 m. The released oil reached the surface waters above the wrecks without any signs of weathering and leaving an homogenous signature throughout the water column. At depths of several kilometers below the sea surface, the occurrence and spread of the deep sea oil spill could be evaluated better by quantifying and characterizing the dissolved hydrocarbon signature, rather than just the investigation of hydrocarbons in the suspended particulate matter.     

Composition, distribution and sources of polycyclic aromatic hydrocarbons in sediments of the Gulf of Trieste, Northern Adriatic Sea

The composition, distribution and the sources of polycyclic aromatic hydrocarbons (PAHs) in the surficial sediments of the Gulf of Trieste were investigated. To document the spatial PAH input, surficial sediment samples from 17 locations throughout the Gulf were analysed. The total PAH load determined in the surficial sediment samples are between 30 and 600 ng g-1, and were the highest in the immediate vicinity of the Port of Trieste. The PAH contents decline rapidly with increasing distance from the shore. The ratios of methylphenanthrenes/phenanthrene and methylpyrene/pyrene are sensitive indicators of the origin of PAH pollution in the Gulf which is mostly pyrolitic. The phenanthrene/anthracene ratio was used to determine the approximate location and distance from the source of PAH pollution, while 1-methy 1-7-isopropylphenanthrene (retene) was used as indicator for forest fires. A sediment depth profile indicates a major increase in the PAH concentrations after the First World War.