Occurrence and health risk estimate of organochlorine pesticides in fruits and vegetables matrices.

Occurrence of 20 organochlorine pesticides (OCPs) in 60 organic and non-organic fruits and vegetables matrices was undertaken using QuEChERS Method EN 15662 for sample preparation analyzed by gas chromatography-mass spectrometry (GC-MS/MS). The procedural method was validated by spiking the OCP standard solutions at three fortified levels at 10, 50, and 100 µg/kg wet weight (ww) to the real matrix of fruit and vegetable with good recovery ranging from 75 to 108% with relative standard deviation (RSD) ≤ 11%, and the limits of detection and quantification (LODs and LOQs) were 0.002-0.02 µg/kg and 0.004-0.1 µg/kg ww, respectively. The assessment of health risks associated with pesticide residues through consumption of vegetables and fruits and the effect of washing and peeling on concentration of various pesticides were also studied. The results showed that the concentration levels of 60% of samples were lower than the LOQs, while the rest was contaminated by OCP residues. Organic fruits and vegetables showed the absence of OCPs, while several of the studied compounds were detected from conventional agriculture. Skin removal (peeling) was the most effective strategy to eliminate or decrease pesticide residues, and should be one of the solutions to reduce the health impact of pesticides in fruits and vegetables. The analysis of health risk assessment was based on the use of the estimated average daily intake (EDI), hazard index (HI), and hazard ratio (HR) for individuals in two weight categories: children (weighing 16.7 kg) and adults (weighing 60 kg). The HI values were less than 1 suggesting that there was no probable non-carcinogenic health effect, except for heptachlor for children (HI of 1.285). However, the values of HR revealed that children were more susceptible to the carcinogenic health effect associated with consuming contaminated vegetables.

Concentrations of bisphenols and phthalate esters in the muscle of Mediterranean striped dolphins (Stenella coeruleoalba).

Bisphenols (BPs) and phthalate esters (PAEs) are important compounds for the plastics industry, also called "everywhere chemicals" due to their ubiquity in daily use products. Both chemical groups are well-known environmental contaminants, whose presence has been reported in all environmental compartments, and whose effects, mainly associated to endocrine disruption, are detrimental to living organisms. Cetaceans, due to their long life-span, low reproduction rate and high position in the trophic web, are especially vulnerable to the effects of contaminants. However, little is known about BP and PAE concentrations in cetacean tissues, their potential relation to individual biological variables, or their trends over time. Here, the concentration of 10 BPs and 13 PAEs was assessed in the muscle of 30 striped dolphins (Stenella coeruleoalba) stranded along the Spanish Catalan coast (NW Mediterranean) between 1990 and 2018. Six BP and 6 PAE compounds were detected, of which only 4,4'-(cyclohexane-1,1-diyl)diphenol (BPZ) was detected in all the samples, at the highest concentration (mean 16.06 µg g-1 lipid weight). Sex or reproductive condition were largely uninfluential on concentrations: only dimethylphthalate (DMP) concentrations were significantly higher in immature individuals than in adults, and the overall PAE concentrations were significantly higher in males than in females. Temporal variations were only detected in bis(4-hydroxyphenyl)ethane (BPE), diethylphthalate (DEP) and dimethylphthalate (DMP), whose concentrations were lower, and 9,9-Bis(4-hydroxyphenyl)fluorene (BPFL), which were higher, respectively, in samples taken between 2014 and 2018, probably reflecting shifts in the production and use of these chemicals. These results provide the first assessment of concentrations of several BP and PAE compounds in the muscle of an odontocete cetacean.

Assessing indicators of arsenic toxicity using variable fluorescence in a commercially valuable microalgae: Physiological and toxicological aspects.

Indicators signaling Arsenic (As) stress through physiology of microalgae using non-destructive methods like variable fluorescence are rare but requisite. This study reports stress markers indicating arsenic (As) toxicity (in two concentrations 11.25 µg/L and 22.5 µg/L compared to a control) exposed to a microalga (Diacronema lutheri), using fast repetition rate fluorometry (FRRf). Growth and physiological parameters such as cell density, chl a and the maximum quantum yield Fv/Fm showed coherence and impeded after the exponential phase (day 9 - day 12) in As treatments compared to the control (p < 0.05). On contrary photo-physiological constants were elevated showing higher optical (aLHII) and functional [Sigma (σPSII)] absorption cross-section for the As treatments (p < 0.05) further implying the lack of biomass production yet an increase in light absorption. In addition, As exposure increased the energy dissipation by heat (NPQ-NSV) showing a strong relationship with the de-epoxidation ratio (DR) involving photoprotective pigments. Total As bioaccumulation by D. lutheri showed a strong affinity with Fe adsorption throughout the algal growth curve. This study suggests some prompt photo-physiological proxies signaling As contamination and endorsing its usefulness in risk assessments, given the high toxicity and ubiquitous presence of As in the ecosystem.

Trace metals exposure in three different coastal compartments show specific morphological and reproductive traits across generations in a sentinel copepod.

The effect of exposure from several compartments of the environment at the level of individuals was rarely investigated. This study reports the effect of contaminants from varied compartments like sediment resuspension, elutriation from resuspended sediment (extract) and seawater spiked trace metal mixtures (TM) on morphological and reproductive traits of the pelagic bioindicator copepod Eurytemora affinis. At the population level of E. affinis, lowest survival was observed in dissolved exposures (TM and extract) in the first generation (G1), showing some adaptation in the second generation (G2). An opposite trend for resuspended sediment showed higher sensitivity in survival at G2. At the individual level, prosome length and volume proved to be sensitive parameters for resuspended sediments, whereas clutch size and egg diameter were more sensitive to TM and extract. Although the generation of decontamination (G3, no exposure), showed a significant recovery at the population level (survival % along with clutch size) of E. affinis exposed to resuspended sediment, morphological characteristics like prosome length and volume showed no such recovery (lower than control, p < 0.05). To the contrary, dissolved exposure showed no significant recovery from G1 to G3 on neither survival %, clutch size, egg diameter, prosome volume, but an increase of prosome length (p < 0.05). Such tradeoffs in combatting the stress from varied sources of toxicity were observed in all exposures, from G1 to G3. The number of lipid droplets inside the body cavity of E. affinis showed a significant positive correlation with trace metal bioaccumulation (p < 0.01) along with a negative correlation (p < 0.05) with survival and clutch size in each treatment. This confirms the inability of copepods to utilize lipids under stressful conditions. Our study tenders certain morphological and reproductive markers that show specificity to different compartments of exposure, promising an advantage in risk assessment and fish feed studies.

Bioaccumulation of trace metal elements and biomarker responses in caged juvenile flounder at a polluted site: Effects of fish density and time exposure.

This study investigates the effect of fish density and exposure duration on trace metal elements (TME) bioaccumulation and several biomarkers response. Juvenile flounders were caged at low, medium and high densities and exposed during 15 or 30 days in the Seine estuary. The concentrations of the TME measured in the muscle of the caged fish were all in agreement with their bioavailability percentage in the sediments. Higher concentrations of TME were found in flounders' muscle exposed for 15 days compared with those caged for 30 days. For the same exposure time, the density of fish had no effect on the accumulation of the TME in the flounders' muscle. Biomarkers responses varied according to density and duration of exposure. Special care should be taken in their interpretation. We underline that for an optimal assessment of TME pollution in the field, 15 days with low densities of fish per cage are sufficient.

Development of a TiO2/Sepiolite Photocatalyst for the Degradation of a Persistent Organic Pollutant in Aqueous Solution.

A clay-based TiO2 nanocomposite material was synthesized by a facile method, to investigate its structure and photocatalytic efficiency. The supported TiO2 nanoparticles were generated using a sol-gel method, and subsequently, mixed with a suspension of sepiolite. The material was recovered in powder form (Mc-80) and then calcined to properly arrange the crystal lattice of the TiO2 particles for use in heterogeneous photocatalysis (Mc-80-500). A powder X-ray diffractogram of Mc-80-500 revealed a dispersion of anatase and rutile phase TiO2 particles on the clay surface, exhibiting a size in the order of 4-8 nm. TEM images of Mc-80-500 confirmed the presence of isolated TiO2 beads on the surface of the fibrous sepiolite. The specific surface area of Mc-80-500 was larger than that of raw sepiolite and that of free TiO2 nanoparticles. Mc-80-500 was found to be more efficient in heterogeneous photocatalysis compared to other TiO2 materials based on sepiolite. Total depollution of a reactive dye (Orange G) was achieved after 1 h irradiation time, which is relatively quick compared to previous reports. The photocatalyst material can be washed with distilled water without chemical additives or calcination, and can be reused several times for photocatalysis, without loss of efficiency.

55 xenobiotic organic compounds in Tripoli landfill-Lebanon leachate and their fluxes to the Abou Ali River and Mediterranean Sea.

Pollution generated from landfill solid wastes constitute one of the major threat to the environment. The landfill leachate contains various toxic pollutants, making it the most dangerous issue of the landfills. Monitoring the xenobiotic organic concentrations in landfill leachate is an important step to evaluate the environmental impacts. This work aims to characterize the seasonal variation of 55 xenobiotic organic compounds including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), phthalic acid esters (PAEs) and bisphenols (BPs) in the leachate from municipal solid waste landfill of Tripoli, Lebanon. And also, the quantity of the pollutant's flux to the Abou Ali River and the Mediterranean Sea nearby has been estimated. The organic pollutants were extracted by using the solid-phase extraction and quantified by using GC-MS/MS. The results showed high level of PAEs, BPs, PCBs, and PAHs in the leachate samples. The fluxes of pollutants to the Abou Ali River and Mediterranean Sea have been detected at 0.23 kg, 0.01 kg, 116.85 kg, 15.93 kg, and 7.58 kg for Σ16PAHs, Σ28PCBs, Σ6PAEs, Σ4BPs, and 4-NP respectively.

Responses of the copepod Eurytemora affinis to trace metal exposure: A candidate for sentinel to marine sediment resuspension effects.

Our study reports the ability of Eurytemora affinis to indicate certain responses in 96 h when exposed to resuspended sediment from a polluted site (PS, Seine estuary, France), less polluted site (LPS, Canche estuary, France) and dissolved trace metals. Mortality from dissolved trace metal was highest (57.5 %) followed by PS (38.59 %) > LPS (24.04 %). The exposure to PS sediment resulted in significantly lower no. of early larval stage (nauplii < 2), sex-ratio (39.24 % of males) and higher ovigerous female (>10). Eurytemora affinis bioaccumulated high concentrations of copper (27.3 mg/kg), nickel (12.8 mg/kg), lead (21.8 mg/kg) and arsenic (13.7 mg/kg) from PS exposure with significantly lower bioaccumulation of metals from LPS. The bioconcentration factor (BCF) was highest from dissolved toxicity (>2000) followed by PS that showed significantly higher BCF for Nickel and Copper, compared to LPS. The responses of E. affinis to different matrices exemplify its role as a sentinel.

Impacts of chemical stress, season, and climate change on the flounder population of the highly anthropised Seine estuary (France).

The main objective of this study was to improve our knowledge on the responses of fish populations to multistress (diffuse pollution and warming waters) in estuaries. Adult flounders were caught in two estuaries in the Eastern English Channel: the heavily polluted Seine estuary vs the moderately contaminated Canche estuary. Fish samplings were conducted in January just before the reproduction period, and in July when gonads were at rest. The overall rise in coastal winter water temperatures detected over the Channel impairs the flounder's phenology of reproduction in the two estuaries, inducing a delay of maturation process and probably also spawning. The higher liver histopathology index in Seine vs Canche could be the consequence of the fish exposition to a complex cocktail of contaminants in a strongly industrialized estuary. Higher levels of neurotoxicity, gill lipid peroxidation, and liver EROD activity were observed in Seine vs Canche. Furthermore, a possible impairment in mitochondrial metabolism was suggested in the Seine flounder population. We confirmed in this study the potential role of two membrane lipids (sphingomyelin and phosphatidylserine) in the resistance towards oxidative stress in Seine and Canche. Finally, we suggest that the Seine flounder population (and possibly the connected Eastern English Channel flounder populations over the French Coast) could be seriously impacted in the future by multistress: higher winter temperatures and chemical contamination.

Intrapopulation and temporal differences of phthalate concentrations in North Atlantic fin whales (Balaenoptera physalus).

The fin whale (Balaenoptera physalus) is a migratory filter-feeding species that is susceptible to ingest plastics while lunge feeding across the oceans. Plastic additives, such as phthalates, are compounds that are added to plastics to give them specific characteristics, such as flexibility. These so-called plasticizers are currently raising major concern because of their potential adverse effects on marine fauna. However, little is known about phthalate concentrations in tissues of baleen whales as well as their potential relation with biological variables (i.e., sex, body length and age) and their trends with time. In this study, we assessed the concentration of 13 phthalates in the muscle of 31 fin whales sampled in the feeding grounds off western Iceland between 1986 and 2015. We detected 5 of the 13 phthalates investigated, with di-n-butylphthalate (DBP), diethylphthalate (DEP) and bis(2-ethylhexyl) phthalate (DEHP) being the most abundant. None of the biological variables examined showed a statistically significant relationship with phthalate concentrations. Also, phthalate concentrations did not significantly vary over the 29-year period studied, a surprising result given the global scenario of increasing plastic pollution in the seas. The lack of time trends in phthalate concentration may be due in part to the fact that phthalates also originate from other sources. Although no adverse effects of phthalates on fin whales have been detected to date, further monitoring of these pollutants is required to identify potential toxic effects in the future.

Multigenerational study of life history traits, bioaccumulation, and molecular responses of Pseudodiaptomus annandalei to cadmium.

Metal pollution provide a substantial challenge for environmental health. This study investigated the multigeneration effects of cadmium on populations of the copepod species Pseudodiaptomus annandalei, exposed to a sublethal concentration, 40 µg/L of cadmium (Cd), over 10 generations. At the end of each generation, copepod individuals were collected to estimate fecundity, bioaccumulation, and real time qPCR quantification of selected differentially expressed genes to evaluate Cd effects and sex-specific responses of copepods across multiple generations. Our results revealed a sex-specific accumulation of Cd integrating 10 successive generations. The concentration of Cd was significantly higher (p < 0.05) in males than in females. We also observed a generational increase in Cd accumulation. Fecundity increased, with the exception of the first generation, possibly as a compensation for a decrease of copepod population size under Cd exposure. Protein expression of copepods exposed to Cd occurred in a sex-specific manner. Hemerythrin was mostly up-regulated in both copepod sexes exposed to Cd with males having the highest expression levels, while heat shock protein 70 was mostly up-regulated in males and down-regulated in female copepods, both exposed to Cd. Although copepods are known to develop adaptive mechanisms to tolerate toxic chemicals, continuous exposure to metals could lead to the bioaccumulation of metals in their offspring through maternal transfer and direct uptake from the medium over several generations. As a consequence, increased metal concentrations in copepods could result in physiological damage, reducing their fitness, and possibly compromise copepod population structures. This study showed that mortality, life history traits and molecular responses of a copepod species provided important toxicological endpoints and bio-markers for environmental risk assessments. Environmental pressure resulting from continuous exposure to persistent pollutants like Cd, could have evolutionary significance. The tendency for copepods to selectively adapt to a toxic environment through modifications, could increase their chance of survival over a long term.

Single toxicity of arsenic and combined trace metal exposure to a microalga of ecological and commercial interest: Diacronema lutheri.

Eco-toxicological assays with species of economic interest such as Diacronema lutheri are essential for industries that produce aquaculture feed, natural food additives and also in drug developing industries. Our study involved the exposure of a single and combined toxicity of arsenic (As V) to D. lutheri for the entire algal growth phase and highlighted that a combined exposure of As V with other essential (Copper, Cu; Nickel, Ni) and non-essential (Cadmium, Cd; Lead, Pb) trace metals reduced significantly the cell number, chlorophyll a content, and also significantly increased the de-epoxidation ratio (DR) as a stress response when compared to the single toxicity of As V. Arsenic, as one of the ubiquitous trace metal and an active industrial effluent is reported to have an increased bio-concentration factor when in mixture with other trace metals in this study. In the combined exposure, the concentration of total As bio-accumulated by D. lutheri was higher than in the single exposure. Hence, polluted areas with the prevalence of multiple contaminants along with the highly toxic trace metals like As can impose a greater risk to the exposed organisms that may get further bio-magnified in the food chain. Our study highlights the consequences and the response of D. lutheri in terms of contamination from single and multiple trace metals in order to obtain a safer biomass production for the growing need of natural derivatives.

Elimination of organochlorine pesticides from water by a new activated carbon prepared from Phoenix dactylifera date stones.

This work focused on the characterization of activated carbon (AC) prepared by pyrolysis-chemical activation with phosphoric acid (60%) from date stones derived from three categories of date palm Phoenix dactylifera (Ajwa, Anbari, Khudri), and on its feasibility of elimination of organochlorine pesticides (OCPs) in water samples. The obtained results showed that the three-produced AC date stone had developed a porous structure, large specific surface area, and acidic property. Due to the high SBET (> 1200 m2/g), Ajwa stones activated coal was considered as the best AC that can be used for the adsorption of environmental contaminants. The effects of several parameters such as the Ajwa AC dose, the time of contact, the initial concentration of pesticides, and the pH were evaluated. The results showed that the adsorption balance of organochlorine pesticides on this AC was reached after a contact time of 60 min at an optimal pHzpc equal to 2. In addition, 0.4 g of AC was the best quantity found to retain the largest quantity of pesticides while considering the economic part.

Simultaneous photocatalytic Cr(VI) reduction and phenol degradation over copper sulphide-reduced graphene oxide nanocomposite under visible light irradiation: Performance and reaction mechanism.

The contamination of water by synthetic organic molecules and trace metals is a growing challenge, in spite of the enormous research efforts being made in the field of water treatment. In this study, reduced graphene oxide-copper sulphide (rGO-CuS) nanocomposites of different rGO/CuS (2/1, 1/1, 1/2) molar ratios were fabricated via a facile one-step hydrothermal method. The nanocomposite materials, named hereafter as 2rGO-CuS, rGO-CuS and rGO-2CuS, were characterized using various analytical techniques, including X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), energy dispersive X-ray (EDX) spectroscopy, X-ray photoelectron spectroscopy (XPS) and UV-visible spectrophotometry. The photocatalytic performance of the nanocomposites was assessed under visible light irradiation (λ > 420 nm) for the simultaneous photocatalytic reduction of Cr(VI) and phenol degradation. It was found that rGO-2CuS achieved a remarkable enhancement of the photocatalytic activity among the prepared nanocomposites for the degradation of phenol and reduction of Cr(VI). Therefore, the simultaneous photocatalytic phenol degradation and Cr(VI) reduction over rGO-2CuS sample was further investigated. The experimental results revealed that rGO-2CuS catalyst maintained good degradation efficacy of mixed pollutants after 6 runs and dissolved oxygen was found to be essential to promote Cr(VI) reduction and phenol degradation. A detailed photocatalytic activity under visible light irradiation mechanism was proposed based on quenching experiments and fluorescence measurements.

Intergenerational effects of resuspended sediment and trace metal mixtures on life cycle traits of a pelagic copepod.

Multiple stressors like metal toxicity, organic compounds and sediment pollution from the Seine estuary are raising concern and novel toxicological approaches are needed to better assess and monitor the risk. In the present study, the copepod Eurytemora affinis from the Seine, was exposed to two different sources of contaminants, which were resuspended polluted sediments and a mixture of trace metals (dissolved phase). The exposure continued for four generations (F0, F1, F2, F3) where F0 is a generation for acclimation to the exposure condition and F3 is a generation for decontamination followed without any exposure, to detect possible maternal carryover effects of pollutants (F0 - F2) and the role of recovery (in F3). Higher accumulation of metals resulted in higher mortalities at both exposure conditions, with particularly F1 being the most sensitive generation showing highest bioaccumulation of metals, highest mortality, and smallest population size. Copper accumulation was highest of all metals in mixture from both the resuspended sediment and the combined trace metal treatment. A significantly lower naupliar production was seen in copepods exposed to resuspended sediment compared to trace metal exposed copepods. However, the decontamination phase (F3) indicated that E. affinis pre-exposed to resuspended sediment had a higher ability to recover the total population size, increase naupliar production, and depurate accumulated Cu. The population exposed to a trace metal mixture showed lower recovery and lower ability to discharge accumulated toxic metals indicating its greater effect on our experimental model when compared to resuspended sediment.

Differential gene expression profile of male and female copepods in response to cadmium exposure.

In this study, the whole transcriptome and sex-specific differential gene expression of the copepod Pseudodiaptomus annandalei exposed to cadmium (Cd) were investigated. P. annandalei were exposed to 40 µg/L Cd from the naupliar stage to male and female adults. High-throughput transcriptome sequencing (RNA-seq) was performed with copepod samples using an Illumina Hiseq™ 2000 platform. TransDecoder analysis found 32,625 putative open reading frame contigs. At p-values of <0.001, a total of 4756 differentially expressed genes (DEGs) (2216 up-regulated and 2540 down-regulated genes) were found in male copepods. Whereas a total of 2879 DEGs (2007 up-regulated and 872 down-regulated genes) were found in female copepods. A few selected cellular stress response genes, involved in xenobiotic metabolism, energy metabolism, growth, and development as a result of Cd exposure in the copepods were discussed. The study showed that most of these processes were changed in a sex-specific manner, accounting for the different sensitivities of male and female copepods. Results suggest and reinforce that sex is an important factor to be considered in ecotoxicogenomics.

Assessment of persistent organic pollutants in surface sediments along Lebanese coastal zone.

The levels of some persistent organic pollutants (POPs) along the Lebanese coastal zone (LCZ) were assessed by collecting15 surface sediments from five hotspot stations. Such stations were influenced by various industrial units, riverine input, and touristic activities. The levels of polycyclic aromatic hydrocarbons (∑16PAHs), their methylated derivatives (∑18Me-PAHs), and polychlorinated biphenyls (∑28PCBs) were in the range of 537-3773 µg∙kg-1 dw, 187-1541 µg∙kg-1 dw, and 143-303 µg∙kg-1 dw respectively. Significant contamination was found at Beirut Port that is surrounded by a densely populated area and is subjected to multidisciplinary activities. Source identification of PAHs was confirmed by using the diagnostic ratio of PAHs with low molecular weight and high molecular weight (LMW/HMW). For PCBs, LCZ is polluted by higher chlorinated congeners with 4 to 9 chlorinated atoms generated from volatilization and combustion processes. Toxicity and biological risks were assessed using toxic equivalent quantity (TEQcarc) and sediment quality guideline quotient (SQGq).

Effects of different routes of exposure to metals on bioaccumulation and population growth of the cyclopoid copepod Paracyclopina nana.

We examined effects of the three metals cadmium (Cd), copper (Cu), and nickel (Ni) on two subpopulations of the cyclopoid copepod Paracyclopina nana. We sought to investigate the effects of metal exposure on population growth and structure of P. nana and to understand the parameters affecting the metal bioaccumulation in copepods. A first experiment tested the hypothesis of competition between these metals in a mixture using a P. nana mass culture in 10 L beakers with the sublethal concentrations (1/3 of LC50) as determined for E. affinis. A second experiment pursued the same with a P. nana population which was adapted to a higher Cu concentration for several generations (226.9 ± 15.9 µg g-1 dw Cu in copepods) and using the proper sublethal concentrations for P. nana. After 96 h of exposure, results from the first experiment showed a decreasing population growth and instead of an increasing metal accumulation in copepods. Cd also appeared to be more accumulated when it was alone, confirming the hypothesis of metal competition in mixture. Results from the second experiment revealed less marked effects. When metal concentrations increased in the treatment it decreased in copepods, indicating depuration activity in the population already adapted to metal exposure. This paper is the first one investigating the parameters affecting the bioaccumulation capacity of P. nana in response to metals. It offers a better understanding of copepod responses to metal contamination in a complex aquatic environment.

Formation and removal of disinfection by-products in a full scale drinking water treatment plant.

In this case study, high sensitivity simple methods for the analysis of trihalomethanes (THM4), iodinated-trihalomethanes (I-THMs), haloacetic acids (HAAs), bromide, iodide and iodate have been developed. A one-step procedure for the analysis of haloacetic acids by head-space GC-MS provides good reproducibility and low limits of quantification (≤50 ng L-1). These methods were applied to characterize the formation of disinfection by-products (DBPs) in a full scale drinking water treatment plant. In this treatment plant, the incorporation of bromine into THMs increases throughout the water treatment line, due to the formation of bromine reactive species favored by the decrease of competition between dissolved organic carbon (DOC) and bromide towards chlorine. A linear correlation has been observed between the bromine incorporation factor and the Br-/DOC mass ratio. The conversion of iodine to iodate by chlorination occurs in this water due to the relatively high bromide concentration. Moreover, a higher formation of iodate compared to iodide levels in the raw water is observed indicating a degradation of organic iodinated compounds. The formation of I-THMs was constant in terms of quantity and speciation between campaigns despite fluctuating concentrations of DOC and total iodine in the raw water. A preferential removal of DBPs formed by the intermediate chlorination in the order I-DBPs > Br-DBPs > Cl-DBPs occurs during the subsequent activated carbon filtration. The removal rates range from 25 to 36% for the regulated THM4, from 82 to 93% for the ∑I-THMs and 95% for haloacetic acids. The assessment of the relative toxicity shows that despite a much lower concentration of HAAs (<10% of the total mass of measured DBPs) compared to THMs, these compounds are responsible for 75% of the relative cytotoxicity of the treated water. Bromoacetic acid on its own accounts for more than 60% of the overall toxicity of the 17 compounds included in this study.

Coupling caging and proteomics on the European flounder (Platichthys flesus) to assess the estuarine water quality at micro scale.

Estuaries are important areas highly vulnerable to anthropogenic pollutions. Therefore, the assessment of estuarine water quality is a major ecological issue. In this study, we sampled juveniles of the European flounder in the "pristine" Canche estuary, and caged them in Canche and in two polluted sites of the Seine estuary, Rouen and Fosse Nord. After one month, the metal and organic pollutants in these sites were assessed, and we evaluated several phenotypic indicators (condition index, RNA/DNA ratios and genotoxicity), and extracted the proteins in fish livers for analysis using a shotgun proteomics approach. The results showed strong modifications in the fish caged in both sites of the Seine estuary, as compared to those caged in Canche. In particular, many proteins involved in phase I and phase II detoxification reactions were accumulated in the liver of fish caged in the site showing the highest pollution, Rouen. In addition, we observed a general disruption of metabolism, in particular an increase in lipid synthesis and carbohydrate degradation in Rouen, and a decrease in the abundance of proteins associated to translational activity in Fosse Nord. At both sites, several stress proteins were decreased. The proteomic impact of the encagement by itself was also evaluated, by comparing the liver proteome of fish caged in Canche to that of fish stayed in natura during the same time. The results showed proteomic signatures of exposure to stressful conditions (particularly heat stress), most probably related to the micro-habitat in which the cages were placed. In conclusion, the caging technique is of great interest for ecotoxicological assessment of estuarine waters, but should consider that the results are representative of the micro-habitat around the cages, which does not necessarily represent the overall heterogeneity of the estuarine environment.