Chemical and genotoxic characterization of bioaccessible fractions as a comprehensive in vitro tool in assessing the health risk due to dust-bound contaminant ingestion.

In the last two decades, awareness grew on the matter of the impact of environment on human health. Contaminants sorbed onto soil and settled dust can be ingested and thus represent a hazard, particularly to young children, who play on the ground and bring their hands and objects to their mouth. Metal(loid)s and polycyclic aromatic hydrocarbons (PAHs) are of concern as they are both carcinogenic to humans and ubiquitous in outdoor environments. The present study aims to assess the total and bioaccessible fractions of PAHs and metal(loid)s present in settled dust of four preschools located in industrial, urban, and suburban areas. On the one hand, children's incremental life cancer risks (ILCR) were calculated according to ingestion pathway. On the other hand, the genotoxicities of the bioaccessible dust-bonded contaminants were determined on gastric cells. PAH concentrations ranged from 50.9 to 2267.3 ng/g, and the bioaccessible fraction represented 10.7% of the total in average. Metal(loid) concentration ranged from 12,430 to 38,941 µg/g, and the mean bioaccessibility was of 40.1%. Cancer risk ranged from 2.8.105 to 8.6.105, indicating that there is a potential cancer risk for children linked to the ingestion of settled dust. The inorganic bioaccessible fraction induced little DNA (< 20%TailDNA) and chromosomal damages (30% increase in micronuclei), whereas the organic bioaccessible fraction induced higher DNA (17-63%TailDNA) and chromosomal damages (88% increase in micronuclei). Such experimental approach needs to be deepen, as a tool complementary to cancer risk calculation, since the latter only lays on a set of targeted contaminants with known toxicity values.

Ongoing Laboratory Performance Study on Chemical Analysis of Hydrophobic and Hydrophilic Compounds in Three Aquatic Passive Samplers.

The quality of chemical analysis is an important aspect of passive sampling-based environmental assessments. The present study reports on a proficiency testing program for the chemical analysis of hydrophobic organic compounds in silicone and low-density polyethylene (LDPE) passive samplers and hydrophilic compounds in polar organic chemical integrative samplers. The median between-laboratory coefficients of variation (CVs) of hydrophobic compound concentrations in the polymer phase were 33% (silicone) and 38% (LDPE), similar to the CVs obtained in four earlier rounds of this program. The median CV over all rounds was 32%. Much higher variabilities were observed for hydrophilic compound concentrations in the sorbent: 50% for the untransformed data and a factor of 1.6 after log transformation. Limiting the data to the best performing laboratories did not result in less variability. Data quality for hydrophilic compounds was only weakly related to the use of structurally identical internal standards and was unrelated to the choice of extraction solvent and extraction time. Standard deviations of the aqueous concentration estimates for hydrophobic compound sampling by the best performing laboratories were 0.21 log units for silicone and 0.27 log units for LDPE (factors of 1.6 to 1.9). The implications are that proficiency testing programs may give more realistic estimates of uncertainties in chemical analysis than within-laboratory quality control programs and that these high uncertainties should be taken into account in environmental assessments.

A Novel Multi-ion Evaluation Scheme to Determine Stable Chlorine Isotope Ratios (37Cl/35Cl) of Chlordecone by LC-QTOF.

Organochlorinated pesticides are highly persistent organic pollutants having important adverse effects in the environment. To study their fate, compound-specific isotope analysis (CSIA) may be used to investigate their degradation pathways and mechanisms but is currently limited to 13C isotope ratios. The assessment of 37Cl isotope ratios from mass spectra is complicated by the large number of isotopologues of polychlorinated compounds. For method development, chlordecone (C10Cl10O2H2; hydrate form), an organochlorine insecticide that led to severe contamination of soils and aquatic ecosystems of the French West Indies, was taken as a model analyte. Chlorine isotope analysis of chlordecone hydrate was evaluated using high-resolution liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS), enabling smooth ionization to detect the molecular ion. First, a new evaluation scheme is presented to correct for multiple isotope presence in polychlorinated compounds. The scheme is based on probability calculations of the most frequent isotopologues, distributions by binomial probability functions, and corrections for the presence of nonchlorine heavy isotopes. Second, mobile-phase modifiers, ionization energy (sampling cone tension) and scan time were optimized for accurate chlorine isotope ratios. Chlordecone standard samples were measured up to 10-fold and bracketed with a second chlordecone external standard. δ37Cl values were obtained after conversion to the SMOC scale by a two-point calibration. The robustness of the analysis method and evaluation scheme were tested and gave satisfactory results with standard errors (σm) of ±0.34‰ for precision and ±0.89‰ for long-term accuracy of chlorine isotope ratios of chlordecone hydrate. This work opens perspectives for applications of the C-Cl CSIA approach to investigate the fate of highly toxic and low reactive polychlorinated compounds in the environment.

Toward an interdisciplinary approach to assess the adverse health effects of dust-containing polycyclic aromatic hydrocarbons (PAHs) and metal(loid)s on preschool children.

Settled dust can function as a pollutant sink for compounds, such as polycyclic aromatic hydrocarbons (PAHs) and metal(loid)s (MMs), which may lead to health issues. Thus, dust represents a hazard specifically for young children, because of their vulnerability and hand-to-mouth behavior favoring dust ingestion. The aim of the present study was to explore the influence of the season and the microenvironment on the concentrations of 15 PAHs and 17 MMs in indoor and outdoor settled dust in three preschools (suburban, urban, and industrial). Second, the potential sources and health risks among children associated with dust PAHs and MMs were assessed. Third, domestic factors (risk perception, knowledge and parental style) were described to explore protective parental behaviors toward dust hazards. The suburban preschool had the lowest concentrations of dust PAHs and MMs, while the industrial and urban preschools had higher but similar concentrations. Seasonal tendencies were not clearly observed. Indoor dusts reflected the outdoor environment, even if specific indoor sources were noted. Source analysis indicated mainly vehicular emissions, material release, and pyrogenic or industrial sources. The non-cancer health risks were non-existent, but potential cancer health risks (between 1.10-6 and 1.10-4) occurred at all sampling locations. Notably, the highest cancer risk was observed in a playground area (>1.10-4) and material release should be further addressed. Whereas we assessed higher risk indoors, parents perceived a higher risk in the open-air environment and at the preschool than at home. They also perceived a lower risk for their own children, revealing an optimism bias, which reduces parental anxiety.

In Vitro Genotoxicity Evaluation of PAHs in Mixtures Using Experimental Design.

Settled dusts are sinks for environmental pollutants, including Polycyclic Aromatic Hydrocarbons (PAHs) that are ubiquitous, persistent, and carcinogenic. To assess their toxicity in mixtures, Toxic Equivalent Factors (TEFs) are routinely used and based on the hypothesis of additive effects, although PAH interactions may occur and remain an open issue. This study investigated genotoxic binary interaction effects for six PAHs in mixtures using two in vitro assays and estimated Genotoxic Equivalent Factors (GEFs) to roughly predict the genotoxicity of PAH in mixtures. The Design of the Experiment approach was used with the micronucleus assay for cytostasis and micronuclei frequency and the alkaline comet assay for DNA damage. GEFs were determined for each PAH independently and in a mixture. For the cytostasis endpoint, no PAHs interaction was noted. BbF and BaP had a synergistic effect on DNA damage. All the PAH interacted between them regarding chromosomal damage. Although the calculated GEFs were similar to the TEFs, the latter may underestimate the genotoxic potential of a PAH mixture. GEFs calculated for PAH alone were lower than GEFs for PAHs in mixtures; thus, mixtures induce greater DNA/chromosomal damage than expected. This research helps to advance the challenging issue of contaminant mixtures' effects on human health.

Passive sampling of chlorinated paraffins by silicone: Focus on diffusion and silicone-water partition coefficients.

Short-chain chlorinated paraffins (SCCPs) are under regulation through the European Water Framework Directive and were recently classified as POPs. Consecutively, the increasing use of middle-chain chlorinated paraffins (MCCPs) becomes of growing concern. Knowledge on the occurrence of chlorinated paraffins (CPs) is still scarce particularly in water phase. To achieve sufficient method sensitivity, the passive sampling approach, acting as a relevant alternative to usual grab sampling, has been considered only very recently for the monitoring of CPs in water. The present work aimed at determining the diffusion coefficients in silicone (Ds) and the silicone-water partition coefficients (Ksw) of various CP groups, having different chlorine contents and carbon chain lengths, in four commercial CP mixtures. Log Ds (-10.78 to -10.21) was found to vary little and to be high for the groups of CPs studied. Thus, their uptake in silicone is controlled by the water boundary layer, which allows to consider the release of performance and reference compounds for in-field estimation of the sampling rate. Moreover, CPs partitioned strongly towards silicone rubbers. Both the chlorination degree and the carbon chain length of CPs cause large uncertainties in the partitioning between silicone and water (log Ksw between 4.85 and 6.30), indicating that instead of an average value, differentiated Ksw should be used to estimate aqueous CPs more accurately. Even so, the probable influence of chlorine atoms position on polarity and partitioning may be an argument for favoring sampling in the kinetic stage.

First study of passive sampling to monitor short-chain chlorinated paraffins in water: Comparing capabilities of Chemcatcher® and silicone rubber samplers.

Short-chain chlorinated paraffins (SCCPs) are high-volume chemicals raising concerns because of their classification as priority hazardous substances by the European Water Framework Directive (WFD) and their recent inclusion in the persistent organic pollutants' (POPs) list by the Stockholm convention. As this group cover up to 5000 isomers, their measurement is still challenging. Hence the SCCPs occurrence in the environment is poorly documented in comparison with other POPs, especially in matrices where they are present at ultratrace levels such as waters. In the two-past decades, passive sampling has been increasingly used as it overcomes some major drawbacks associated to the conventional grab sampling. This study constitutes the first work aiming to examine the passive sampling's applicability for the monitoring of such complex analytes' mixtures in waters. Optimization and calibration of two proven passive samplers, namely silicone rubbers and Chemcatcher®, were performed through batch and laboratory pilot experiments. Despite the thousands of molecules present in the SCCPs mixture, the resulting global kinetic uptakes fitted well with the theorical model, for both samplers. Sampling rates of 8.0 L d-1 for silicone rubbers and 0.53 L d-1 for Chemcatcher® were found, and logKsw determined for silicone rubbers equaled 4.24 to 4.95. These values are in complete agreement with published data for other HOCs. A field trial carried out in marine coastal environments provided further evidence to demonstrate the applicability of the passive samplers to measure CPs amounts in water bodies. All these results unveil that passive sampling using silicone rubbers or Chemcatcher® can be a relevant approach to track traces of such complex mixtures in water.

Persistent organic pollutants in sediments of the Wouri Estuary Mangrove, Cameroon: Levels, patterns and ecotoxicological significance.

The anthropogenic impact in the Wouri Estuary Mangrove located in the rapidly developing urban area of Douala, Cameroon, Africa, was studied. A set of 45 Persistent Organic Pollutant were analysed in surficial mangrove sediments at 21 stations. Chlorinated Pesticides (CLPs), Polychlorinated Biphenyls (PCBs) and Polycyclic Aromatic Hydrocarbons (PAHs) have concentrations ranging from 2.2 - 27.4, and 83 - 544 ng/g, respectively. The most abundant CLPs were endosulfan, alachlor, heptachlor, lindane (γ-HCH) and DDT, which metabolites pattern revealed recent use. Selected PAHs diagnostic ratios show pyrolytic input predominantly. The sum of 7 carcinogenic PAHs (ΣC-PAHs) represented 30 to 50% of Total PAHs (TPAHs). According to effect-based sediment quality guidelines, the studied POPs levels imply low to moderate predictive biological toxicity. This study contributes to depict how far water resources are shifting within what is now termed the Anthropocene due to increasing local pressures in developing countries or African countries.

Kinetic study of glyphosate degradation in wet air oxidation conditions.

Glyphosate is one of the most widely used herbicides in the world against perennial and annual weeds. It has been reported to be a micro pollutant, and its degradation in different wastewater treatment processes must be studied. For that purpose, the kinetics of wet air oxidation of glyphosate was studied in an autoclave reactor at a temperature range of 423-523 K and under a total pressure of 15 MPa. Oxidation reactions obeyed the first-order kinetics with respect to glyphosate concentration. The activation energy for glyphosate oxidation was found to be equal to 68.4 kJ mol-1. Furthermore, the possible reaction intermediates and main end products of glyphosate degradation in the wet air oxidation process were identified and quantified using UV-spectrophotometry and liquid chromatography coupled to high resolution mass spectrometry. A degradation pathway for glyphosate oxidation was proposed.

Advances and limits of two model species for ecotoxicological assessment of carbamazepine, two by-products and their mixture at environmental level in freshwater.

In order to evaluate the environmental impacts associated with the presence of low-level of pharmaceuticals in waters, chronic ecotoxicity of carbamazepine (CBZ), oxcarbazepine (OxCBZ) and acridine 9-carboxylic acid (9-CAA) and their mixture was investigated using two species from different trophic levels. Innovative approaches were developed by monitoring: (i) phytometabolites in the duckweed Lemna minor L. and, (ii) alterations at the population, cellular and molecular levels on the cnidarian Hydra circumcincta Schulze 1914, to assess the effects of 14-day chronic exposure. On H. circumcincta, the approach was conducted at 19.5 °C, the optimal growth temperature, and at 23 °C, to simulate global warming impact. In L. minor, results showed alterations of the nitrogen balance and the chlorophyll indices for OxCBZ and 9-CAA separately at environmental concentrations and for the mixture of the three studied products. However, phenolic compound index deeply varied depending on pharmaceuticals and time of exposure with no specific trend. In H. circumcincta, effects on morphology, reproduction and lipid peroxidation were observed at low level of CBZ. OxCBZ impacted the total antioxidant capacity of H. circumcincta, whereas exposure to 9-CAA affected all parameters, except the reproduction rate. Finally, 14-day exposure to the mixture of the three products also slowed the reproduction rate and altered the morphology of this cnidarian. Higher damages were detected when experiments were conducted at a temperature 3.5 °C above the optimum for Hydra growth, suggesting the relevance of taking into account possible ecotoxicological consequences of global warming. Our results confirmed the necessity of selecting sensitive organisms at different trophic levels to better assess ecotoxicity of pharmaceuticals and their mixture, especially at environmental levels and facing global changes.

Occurrence and ecotoxicological assessment of pharmaceuticals: Is there a risk for the Mediterranean aquatic environment?

Due to their pseudo-persistence and their biological activity, pharmaceuticals are emerging contaminants of major concern for the environment. The aim of this review is to provide an updated inventory of the contamination of aquatic environments by 43 drugs representing different classes of pharmaceuticals, such as antibiotics, anti-inflammatory drugs, anti-depressants, sex hormones, lipid regulators and beta-blockers. The data collected is focused on contamination levels reported in marine coastal waters and in waste and river waters flowing into the Mediterranean Sea. The most widely produced/prescribed classes of medicines are compared with the substances most widely searched for in the environment. Ranges of pollution levels according to the type of water body are also presented, to examine the fate in sewage treatment plants and the persistence in the environment of the targeted molecules. Levels of pharmaceuticals ranged from 100 to 10,000 or even 100,000 ng·L-1 in sewage waters, dropping to 1 to 10,000 ng·L-1 in rivers and to not detected to 3000 ng·L-1 in sea water. However, this paper evidences a lack of data for seawater and also for several countries along the southern coast of the Mediterranean Sea. In order to assess the risk for aquatic ecosystems associated with pharmaceuticals, experimental ecotoxicological values obtained using normalized acute and/or chronic bioassays carried out with different trophic levels were collected for each drug. Targeted biological species and associated bioassays are classified on the basis of their sensitivity to each class of compounds. Occurrence and ecotoxicology are then linked by using the Hazard Quotient (HQ) to assess the environmental risk caused by pharmaceuticals in the Mediterranean Basin. Correlations between HQ and frequency of detection of pharmaceuticals highlighted thirteen compounds that are cause for concern in Mediterranean fresh and sea waters, such as 17α-ethinylestradiol, metoprolol, 8 antibiotics and 3 analgesics/anti-inflammatories.

Distribution and risk assessment of hydrocarbons (aliphatic and PAHs), polychlorinated biphenyls (PCBs), and pesticides in surface sediments from an agricultural river (Durance) and an industrialized urban lagoon (Berre lagoon), France.

The distributions of organic pollutants (like hydrocarbons, polychlorinated biphenyls (PCBs), and pesticides) and the risks on the ecosystem were studied in the Durance River and the Berre lagoon (France). High levels of aliphatic hydrocarbons were observed in all stations (1399 to 11,202 µg kg(-1) dw). The n-alkanes were mainly from terrigenous origin confirmed by the values of different ratios calculated (carbon preference index (CPI), natural n-alkanes ratio (NAR), terrigenous/aquatic ratio (TAR), and ratio of low molecular weight to high molecular weight (LMW/HMW)). Total polycyclic aromatic hydrocarbon (PAH) concentrations in the surface sediments of the Durance River and Berre lagoon are 57-1528 and 512-863 µg kg(-1) dw, respectively. Several ratios between parent polycyclic aromatic hydrocarbons showed that the sources of hydrocarbons in the sediments were generally more pyrolytic than petrogenic. The sum of seven PCB contents ranged from 0.03 to 13.13 µg kg(-1) dw. Higher levels of PCBs were detected in sediments from the northern parts of the Berre lagoon (stations B1 and B3). Total pesticides contents ranged from 0.02 to 7.15 µg kg(-1) dw. Among these compounds, ∑DDE and ∑DDT contents ranged, respectively, from 0.35 to 1.65 and from 0.37 to 1.52 µg kg(-1) dw. However, PAH and PCB levels are not high enough to be a threat to aquatic organisms and human beings. Total PAH levels were below the effects range low (ERL) of 3500 µg kg(-1) dw. For PCBs, only two stations (B1 and B3) are higher than the effect range median (ERM) of 180 µg kg(-1) dw. For endrin (pesticide), the concentrations are between the ERL (0.02 µg kg(-1) dw) and the ERM (45 µg kg(-1) dw).

Impact of organic pollutants on metal and As uptake by helophyte species and consequences for constructed wetlands design and management.

Various industrial processes and anthropogenic activities in urban areas induce a release of metals, metalloids and organic pollutants. Phytoremediation of co-contaminated waters in constructed wetlands is a promising solution for reducing the impact on natural environments. In order to improve the design and management of constructed wetlands, more knowledge is needed concerning the effect of organic pollutants on plant metal and metalloid uptake. In this study, the effects of a mixture of organic pollutants commonly found in industrial effluents (hydrocarbons, polycyclic aromatic hydrocarbons, anionic detergent) on the uptake of ten metals and metalloids (MM), i.e. Al, As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn, by five helophytes having a wide European distribution were studied. Main effects of plant species and pollutant conditions on metal uptake and interactions between factors were determined by a statistical treatment of a microcosm experiment. Overall, the order of element uptake in plants was Fe > Al > Mn > Cr, Ni, Zn, > Cu > As, Cd, Pb, which was consistent with relative concentrations in the rhizosphere environment of microcosms. Larger amounts of metals were retained in belowground biomass of plants than in aboveground parts. Statistical analysis showed that organic pollutants enhanced the accumulation of Mn in whole plants and the retention of Fe in belowground parts, while they reduced the accumulation of Cd, Ni, and Zn in whole plants and the retention of Cu in belowground parts. For the other MM (Al, As, Cr, Pb), effects were variable, depending on the plant species. Among the five plants tested, Carex cuprina generally removed the highest quantities of MM, which was the result of both a high metal accumulation capacity and high biomass production. Nevertheless, no significant proportion of the MM total loading could be removed in plants' aboveground parts.

Selection of wild macrophytes for use in constructed wetlands for phytoremediation of contaminant mixtures.

Constructed wetlands (CWs) offer an alternative to traditional industrial wastewater treatment systems that has been proved to be efficient, cost-effective and environmentally friendly. Most of the time, CWs are planted with proliferative species such as Phragmites australis or with plants originating from nurseries, both representing a risk for the natural biodiversity conservation of aquatic ecosystems located downstream of the CWs. For the removal of metals and organic pollutant mixtures present in industrial effluents, it is necessary to select tolerant plant species that are able to produce a high aboveground biomass and to develop a healthy belowground system. Wild plant species growing in aquatic bodies at industrial outfalls could constitute suitable tolerant species to use in CWs for industrial effluent treatment. To test this hypothesis, we assessed, under laboratory conditions (using an experimental design), the tolerance to mixtures of metals (Al, As, Cd, Cu, Cr, Fe, Mn, Ni, Pb, Sn, Zn) or/and organic pollutants (THC, PHE, PYR, LAS) of five European sub-cosmopolitan native macrophytes (Alisma lanceolatum, Carex cuprina, Epilobium hirsutum, Iris pseudacorus and Juncus inflexus) that had been collected in a polluted Mediterranean wetland, after a field study (crossing ecological relevés and analyses of contaminant concentrations in water and sediments). Our results demonstrated that research on phytoremediation of industrial effluents should focus much more on the use of native macrophytes growing at short distances from industrial discharges (such as C. cuprina in this study), and that root/shoot ratio, aerial height and proportion of green leaves are good and cost-effective indicators of plant tolerance to metals and organic pollutant mixtures in laboratory studies.

Molecular insights of oxidation process of iron nanoparticles: spectroscopic, magnetic, and microscopic evidence.

Oxidation behavior of nano-Fe(0) particles in an anoxic environment was determined using different state-of-the-art analytical approaches, including high resolution transmission electron microscopy (HR-TEM) combined with energy filtered transmission electron microscopy (EFTEM), X-ray absorption spectroscopy (XAS), and magnetic measurements. Oxidation in controlled experiments was compared in standard double distilled (DD) water, DD water spiked with trichloroethene (TCE), and TCE contaminated site water. Using HR-TEM and EFTEM, we observed a surface oxide layer (∼3 nm) formed immediately after the particles were exposed to water. XAS analysis followed the dynamic change in total metallic iron concentration and iron oxide concentration for the experimental duration of 35 days. The metallic iron concentration in nano-Fe(0) particles exposed to water, was ∼40% after 35 days; in contrast, the samples containing TCE were reduced to ∼15% and even to nil in the case of TCE contaminated site water, suggesting that the contaminants enhance the oxidation of nano-Fe(0). Frequency dependence measurements confirmed the formation of superparamagnetic particles in the system. Overall, our results suggest that nano-Fe(0) oxidized via the Fe(0) - Fe(OH)2 - Fe3O4 - (γ-Fe2O3) route and the formation of superparamagnetic maghemite nanoparticles due to disruption of the surface oxide layer.

Assessment of potential positive effects of nZVI surface modification and concentration levels on TCE dechlorination in the presence of competing strong oxidants, using an experimental design.

Nanoscale zero-valent iron (nZVI) particles are efficient for the remediation of aquifers polluted by trichloroethylene (TCE). But for on-site applications, their reactivity can be affected by the presence of common inorganic co-pollutants, which are equally reduced by nZVI particles. The aim of this study was to assess the potential positive effects of nZVI surface modification and concentration level on TCE removal in the concomitant presence of two strong oxidants, i.e., Cr(VI) and NO3(-). A design of experiments, testing four factors (i.e. nZVI concentration, nZVI surface modification, Cr(VI) concentration and NO3(-) concentration), was used to select the best trials for the identification of the main effects of the factors and of the factors interactions. The effects of these factors were studied by measuring the following responses: TCE removal rates at different times, degradation kinetic rates, and the transformation products formed. As expected, TCE degradation was delayed or inhibited in most of the experiments, due to the presence of inorganics. The negative effects of co-pollutants can be palliated by combining surface modification with a slight increase in nZVI concentration. Encouragingly, complete TCE removal was achieved for some given experimental conditions. Noteworthily, nZVI surface modification was found to promote the efficient degradation of TCE. When degradation occurred, TCE was mainly transformed into innocuous non-chlorinated transformation products, while hazardous chlorinated transformation products accounted for a small percentage of the mass-balance.

Aliphatic hydrocarbons, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorine, and organophosphorous pesticides in surface sediments from the Arc river and the Berre lagoon, France.

INTRODUCTION: The Arc River and Berre lagoon are one of important river basin hydrosystem in the South of France that receives industrial and municipal wastewaters from the adjacent area. MATERIALS AND METHODS: Due to its social and economic impact as well as ecological function of basin, an assessment of environmental risk due to mobilization of contaminants is necessary. Thus, the study aims to determine the spatial distribution of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine and organophosphorous pesticides in surface sediments and their potential origins by using gas chromatography coupled to mass spectrometry. RESULTS AND DISCUSSION: Total alkanes concentrations ranged from 563 to 5,068 µg kg(-1) sediment dry weight (dw), the sum of 17 PAHs ranged from 153 to 1,311 µg kg(-1) dw, the sum of seven PCBs concentrations ranged from 0.3 to 466.8 µg kg(-1) dw, and the total pesticides concentrations ranged from 0.02 to 7.15 µg kg(-1) dw. Ratios of specific n-alcanes (carbon preference index, natural n-alkanes ratio, and terrigenous/aquatic ratio) and ratios of selected PAH (anthracene (Ant)/(Ant + Phe), fluoranthene (Fl)/(Fl + pyrène (Pyr)), BaA/(BaA + chrysene (Chry)), indeno[1,2,3,c,d]pyrene (IPyr)/(IPyr + BghiP)) were calculated to evaluate the possible sources of hydrocarbons. CONCLUSIONS: The evaluations suggest the sources of hydrocarbons in the sediments were generally biogenic and markedly more pyrolytic rather than petrogenic. In the perspectives of environmental risk assessment, all contaminants levels were also compared with sediments quality guidelines (SQG) resulting that the contamination levels in all stations were most of the time lower than their respective SQG. While, for PCBs concentrations, three stations (A8, B1, and B2) were higher than their effect range median values which may indicate high potential toxicity of the sediment with probable adverse effects to the living biota.

Distribution of organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs) in marine sediments directly exposed to wastewater from Cortiou, Marseille.

INTRODUCTION: The future 'Calanque National Park' coastlines of the Bouches-du-Rhône and Var departments in France, constitute one of the ten biodiversity hot spots identified in the Mediterranean basin that receives industrial and urban wastewaters discharged from Marseille and its suburbs. MATERIALS AND METHODS: Organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs) were measured in sediments collected from 12 sampling sites (C1-C12) of sewage discharge to the sea from the wastewater treatment plant of Cortiou-Marseille. This study aims to determine the extent of these compounds in the sediments and to establish the possible sources of these contaminants. RESULTS AND DISCUSSION: Total pesticides in the sediments ranged from 1.2 to 190.6 ng g(-1) dry weight of sediment. The highest value was found at station C1, with a decreasing trend in total OC concentrations seaward. Among these compounds, the concentrations of the sum of dichlorodiphenyltrichloroethane (ΣDDT) were the highest, ranging from 0.7 to 114.3 ng g(-1). PCB concentrations, expressed as equivalent to Arochlor 1260, varied from 9.1 to 226.9 ng g(-1). Individually, the dominant coplanar PCB congeners CB-153, CB-138 and CB-101. Generally, PCB concentrations at stations C2, C3, C5 and C7 were higher than those at stations C10, C11 and C12. Through some pollution indices, we showed the long-term contamination input of these OCs (DDT, endosulfan, HCH and heptachlor cases) rather than a recent release resulting from degradation and long-term weathering (dieldrin, aldrin and methoxychlor cases). Occurrence of PCBs might be due to their resistance to degradation processes or/and chronic inputs. CONCLUSIONS: By comparison with available sediment quality guideline (SQG) values, the environmental significance and toxicological implications of PCBs and OCs (i) reveal the probable adverse effects for the sediments from C1, C5, C6, C9 and (ii) confirm the adverse effect for marine biota and more particularly for benthic communities at C2-C4, C7 and C8.

Comparison of two extraction procedures for the assessment of sediment genotoxicity: implication of polar organic compounds.

Four sediment samples (Vaïne Airport VA, Vaïne Center VC, Vaïne North VN and Reference North RN) were collected in the Berre lagoon (France). Sediments were analyzed for polycyclic aromatic hydrocarbons (PAHs) by use of pressurized fluid extraction with a mixture of hexane/dichloromethane followed by HPLC with fluorescence detection analysis. Organic pollutants were also extracted with two solvents for subsequent evaluation of their genotoxicity: a hexane/dichloromethane mixture intended to select non-polar compounds such as PAHs, and 2-propanol intended to select polar contaminants. Sediment extracts were assessed by the Salmonella/microsome mutagenicity test with Salmonella typhimurium TA98+S9 mix and YG1041±S9 mix. Extracts were also assessed for their DNA-damaging activity and their clastogenic/aneugenic properties by the comet assay and the micronucleus test with Chinese Hamster ovary (CHO) cells. The PAH concentrations were 611ngg(-1)dw, 1341ngg(-1) dw, 613ngg(-1)dw and 482ngg(-1)dw for VA, VC, VN and RN, respectively. Two genotoxic profiles were observed, depending on the extraction procedure. All the non-polar extracts were mutagenic for TA98+S9 mix, and VA, VC, VN sediment samples exerted a significant DNA-damaging and clastogenic activity in the presence of S9 mix. All the polar extracts appeared mutagenic for TA98+S9 mix and YG104±S9 mix, and VA, VC, VN were genotoxic and clastogenic both with and without S9 mix. These results indicate that the genotoxic and mutagenic activities mainly originated from PAHs in the non-polar extracts, while these activities came from other genotoxic contaminants, such as aromatic amines and nitroarenes, in the polar extracts. This study focused on the important role of uncharacterized polar contaminants such as nitro-PAHs or aromatic amines in the global mutagenicity of sediments. The necessity to use appropriate extraction solvents to accurately evaluate the genotoxic hazard of aquatic sediments is also highlighted.

Thermodynamic and kinetic study of phenol degradation by a non-catalytic wet air oxidation process.

This work is dedicated to an accurate evaluation of thermodynamic and kinetics aspects of phenol degradation using wet air oxidation process. Phenol is a well known polluting molecule and therefore it is important having data of its behaviour during this process. A view cell is used for the experimental study, with an internal volume of 150 mL, able to reach pressures up to 30 MPa and temperatures up to 350°C. Concerning the thermodynamic phase equilibria, experimental and modelling results are obtained for different binary systems (water/nitrogen, water/air) and ternary system (water/nitrogen/phenol). The best model is the Predictive Soave Redlich Kwong one. This information is necessary to predict the composition of the gas phase during the process. It is also important for an implementation in a process simulation. The second part is dedicated to kinetics evaluation of the degradation of phenol. Different compounds have been detected using GC coupled with a MS. A kinetic scheme is deduced, taking into account the evolution of phenol, hydroquinones, catechol, resorcinol and acetic acid. The kinetic parameters are calculated for this scheme. These data are important to evaluate the evolution of the concentration of the different polluting molecules during the process. A simplified kinetic scheme, which can be easily implemented in a process simulation, is also determined for the direct degradation of phenol into H(2)O and CO(2). The Arrhenius law data obtained for the phenol disappearance are the following: k=1.8×10(6)±3.9×10(5)M(-1)s(-1) (pre-exponential factor) and E(a)=77±8 kJ mol(-1) (activation energy).