Philippe Garrigues

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 logKow 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 in recent sediments and mussels (Mytilus edulis) from the Western Baltic Sea : occurrence, bioavailability and seasonal variations

Abstract Surface sediments and mussels, Mytilus edulis , collected in the Baltic Sea in March 1995, October 1995 and August 1996 have been analysed for polycyclic aromatic hydrocarbon (PAH) content. The analyses have been performed by gas chromatography coupled to mass spectrometry (GC–MS). Total sediment PAH concentrations range from 3 to about 30 000 ng/g while total mussel PAH concentrations range from 90 to about 3900 ng/g. Molecular indices based on isomeric PAH ratios differentiate the pollution sources, pointing out differences between Germany and Poland. Most of the contamination originates from high temperature pyrolytic inputs with some slight overimpositions of petrogenic and diagenetic PAHs. Mussel and sediment total PAH concentrations have been found to be moderately correlated ( r 2 =0.51 for March, 0.58 for August and 0.98 for October). Bioaccumulation factors (BAFs) have been calculated and have shown higher values for the mussels sampled in March. Differences of BAFs have been observed for the different compounds resulting from different uptake pathways and metabolism abilities of Mytilus edulis .

Polycyclic aromatic hydrocarbon (PAH) burden of mussels (Mytilus sp.) in different marine environments in relation with sediment PAH contamination, and bioavailability

Abstract Sediments and mussels (Mytilus edulis, Mytilus galloprovincialis) were sampled in different European coastal environments (Germany, France, Spain) and analysed for their polycyclic aromatic hydrocarbon (PAH) content by Gas Chromatography/Mass Spectrometry (GC-MS). Bioaccumulation factors of individual compounds from the sediment were calculated and discussed according to the compound solubility. The mussels showed different accumulation patterns according to the pollution source they were exposed to (dissolved fraction of PAHs, particulate fraction, petroleum present in the water column). The exposure source also depends on the geographical location of the mussels. In the Mediterranean Sea, the bivalves were mainly exposed to the dissolved fraction of PAHs, while in the Baltic Sea and in the Atlantic Ocean, the PAHs associated to the particles were significant sources.

PAHs in Arcachon Bay, France: Origin and biomonitoring with caged organisms

Abstract The concentration of polycyclic aromatic hydrocarbons (PAHs) has been determined in superficial sediments and caged mussels ( Mytilus galloprovincialis ) of Arcachon Bay, France. The bay sediments are uniformly contaminated at moderate to high levels (900–4100 ng g −1 ), with a lower contamination level at the entrance to the bay (≈ 30 ng g −1 ). This pollution is mainly pyrolytic and related to anthropogenic activity. Caged mussels exposed to sediments with a contamination level of −1 are contaminated at moderate levels (300–500 ng g −1 ), but those exposed to sediment contaminated at a higher level (> 3000 ng g −1 ) have accumulated more PAHs ( > 2000 ng/g). This may result from a different equilibrium between uptake and depuration of the xenobiotics at the sites with greater levels of contamination or from higher levels of bioavailability of the contaminants at these locations. The bioavailability of the contaminants is also discussed in terms of organism exposure and contaminant origin.

Scale of classification based on biochemical markers in mussels: application to pollution monitoring in European coasts.

A battery of biochemical parameters is used to evaluate the response of mussels to a contaminated coastal environment. In the European BIOMAR programme, a multimarker approach was developed, establishing a scale for the classification of the water quality in European coastal sites. AChE activity is highly sensitive to organophosphorus and carbamate insecticides but also to heavy metals. Catalase activity and lipid oxidation (evaluated as MDA) are markers of oxidative stress, GST activity is related to the conjugation of organic compounds and BPH activity is a marker of planar compounds (e.g. PAHs). These parameters were measured either in gills (AChE, GST) or digestive gland (BPH, GST, CAT, MDA). Contamination levels were estimated by measurement of PAHs and heavy metals in animals. For each biomarker, a discriminatory factor was calculated (maximum variation range/confidence interval) and a response index was allocated. For each site, a global response index was calculated as the sum of the response index of each of the five biomarkers. As a result of our calculation method, the quality of the coastal environment at each site can be classified with a five level scale. Mussels were collected during five cruises in 1995-1996 on the Baltic and Mediterranean coasts. The results show that water quality ranged from class 1 (clean areas in some sites of the French Riviera, Spanish Costa Brava and the Baltic coast) to class 5 (high pollution in main harbours, e.g. Kiel and Toulon). Some areas fall into class 4, e.g. Carteau, Cortiou, Barcelona, Warnemunde, Swinemunde, Ebro delta. The global Biomarker Index was positively correlated with the level of PAHs in mussels in Baltic transects. A number of other contaminants or stressors may be present in the marine environment and the Biomarker Index appeared to be relevant to classify coastal environmental pollution.A battery of biochemical parameters is used to evaluate the response of mussels to a contaminated coastal environment. In the European BIOMAR programme, a multimarker approach was developed, establishing a scale for the classification of the water quality in European coastal sites. AChE activity is highly sensitive to organophosphorus and carbamate insecticides but also to heavy metals. Catalase activity and lipid oxidation (evaluated as MDA) are markers of oxidative stress, GST activity is related to the conjugation of organic compounds and BPH activity is a marker of planar compounds (e.g. PAHs). These parameters were measured either in gills (AChE, GST) or digestive gland (BPH, GST, CAT, MDA). Contamination levels were estimated by measurement of PAHs and heavy metals in animals. For each biomarker, a discriminatory factor was calculated (maximum variation range/confidence interval) and a response index was allocated. For each site, a global response index was calculated as the sum of the response inde...

Pyrolytic and Petrogenic Inputs in Recent Sediments: A Definitive Signature Through Phenanthrene and Chrysene Compound Distribution

Abstract Methylphenanthrene and methylchrysene distributions have been determined by Shpolskii Spectroscopy in chromatographic fractions of various environmental samples, including Standard Reference Materials (SRM). This distribution demonstrated to be an indicator of the temperature of the formation of aromatic material in natural matrices. Specific isomer concentration ratios were calculated in each series and were proven to assess pyrolytic or petrogenic contamination in recent sediments.

Degradation of organophosphorus pesticides and their transformation products in estuarine waters.

The degradation of 10 organophosphorus pesticides in natural estuarine waters was studied. Estuarine water samples were spiked with organophosphorus pesticides at 50 μg/L level and were placed into 2-L Pyrex flasks being exposed outdoor to ambient sunlight and temperature. A sample of 10-75 mL of water was collected every week for analysis during a period of 5-6 weeks from January to March. The analytical determinations were performed by solid-phase extraction (SPE) with C 18 Empore disks followed by GC-NPD and GC-MS with El and by on-line SPE using PLRP-s exchangeable cartridges (Prospekt) followed by LC-DAD and LC-thermospray MS in PI mode. Five organophosphorus pesticides were stable for less than 1 week (disulfoton, fenamiphos, fenthion, malathion, and temephos), others had a half-life of ca. 1 week (chlorpyrifos-methyl, methidathion, and diazinon), and the rest showed a half-life of ca. 10 days (isofenphos and pyridafenthion). The half-life of three pesticide transformation products : disulfoton sulfoxide, disulfoton sulfone, and fenthion sulfoxide varied from 7 to 12 days.

One-year monitoring survey of organic compounds (PAHs, PCBs, TBT), heavy metals and biomarkers in blue mussels from the Arcachon Bay, France

Marine mussels Mytilus sp. were transplanted on a monthly basis in cages over one year to oyster farms and harbours in the Arcachon Bay (France) in order to assess the water quality of the bay. Contaminant levels (organotin compounds, trace metals, PCBs and PAHs) were measured in tissues of transplanted mussels and mussels from a reference station, along with physiological parameters of the mussels (condition indexes, lipid content and dry weight). Four biomarkers (AChE: acetylcholinesterase activity, GST: gluthathione S-transferase activity, CAT: catalase activity and TBARS: thiobarbituric acid-reactive substance content) were also monitored. The remote stations monitored (oyster parks) exhibited no accumulation pattern of pollutants. Their respective concentrations therefore constitute a background level of the contamination in the bay ([TBT]= 30 ng Sn g(-1) dw, [SigmaHAPs]= 100 ng g(-1) dw, [SigmaPCBs]= 35 ng g(-1) dw). The elevated chemical contamination of the largest harbour of the bay, the Arcachon harbour, can be interpreted in terms of persistence of organotin compounds ([SigmaOTs]= 1500-2000 ng Sn g(-1) dw) and PAHs ([SigmaHAPs]= 4500-5000 ng g(-1) dw) in sediments and, to a lesser extent, of direct inputs of copper ([Cu]= 20 microg g(-1) dw in harbours versus 7 in oyster parks) and petrogenic PAHs ([methylphenanthrenes]= 1600 ng g(-1) dw in the dockyard versus 170 at the gas stations), related to the use of copper-based antifouling paints and to dockyard activity, respectively. However, the Arcachon Bay presents a low contamination level by PCBs and metals, including harbour stations. Furthermore, higher levels of other PAHs (particularly alkyl PAHs such as methylphenanthrenes/1600 ng g(-1) dw) not included in the 16 PAHs from the EPA priority list (usually studied in biomonitoring programmes/1500 ng g(-1) dw) in the Arcachon harbour underline the need to integrate these compounds in biomonitoring of highly PAH-polluted areas such as harbours in order to avoid misinterpretation of the biological responses observed. Biomarker responses were not able to discriminate the different chemical contamination levels recorded in the Arcachon Bay and rather reflected changes in environmental factors. Furthermore, the strong intraspecies variability of biological responses could be due to genetic differences of mussels from the Arcachon Bay. It is the first time that such an integrated monitoring is performed in the Arcachon Bay, also taking into account seasonal variations of chemical contents and biomarkers levels in mussel tissues.

Ancient polycyclic aromatic hydrocarbons in modern soils: 13C, 14C and biomarker evidence

Abstract Polycyclic aromatic hydrocarbons (PAHs) of soils from two maize growing fields were analyzed for molecular structure by gas chromatography-mass spectrometry, for 13 C/ 12 C ratios by isotope ratio mass spectrometry and for 14 C age by accelerator mass spectrometry. These investigations indicate that the aromatic fractions are dominated by pyrolytic inputs. Calculation of molecular maturity parameters based on hopanes and PAHs gives values typical of high thermal stress such as exhibited by high rank coals and petroleums with equivalent vitrinite reflectances of ∼0.6–1.5%. The interpretations based on molecular compositions are corroborated by isotopic data. Specifically, both the absence of 13 C/ 12 C variations in the aromatic fractions during 23 years of maize cropping, and a 14 C age greater than 9820 years demonstrate that these substances are not derived by the aromatization of modern plant material or soil biomass. Together, these results show that soil PAHs are mainly of pyrolytic origin, e.g. exogenous (airborne) contributions of fossil fuel combustion products and (old) vegetation fires, with a small contribution of uncombusted fossil fuels. This approach using molecular and isotope information represents a promising way to study the fate of ancient, reworked, fossil organic matter in modern media such as soils, sediments, plants, air and food.

Mixed-function oxygenase enzymes as tools for pollution monitoring: field studies on the French coast of the Mediterranean Sea.

1. MFO enzyme activities were measured in microsomes from whole mussels (Mytilus galloprovincialis) comber livers (Serranus cabrilla), or Posidonia oceanica etiolated tissues, and PAH contents were determined in sediments collected in coastal locations of the French Riviera and Corsica during 3 oceanographic cruises in 1987-1988. 2. BaP activities in mussel and EROD activities measured in fish were strongly correlated to the log of PAH content in sediments. The first results for CA4H in Posidonia showed significant differences related to PAH pollution levels. The increase in MFO activities measured in Corsica in summer 1988 indicated a recent petroleum contamination.