Polar organic chemical integrative samplers as an effective tool for chemical monitoring of surface waters - Results from one-year monitoring in France.

In an effort to support European Union Water Framework Directive goals, we have set up a national demonstrator project to identify the advantages and limitations of passive samplers for regulatory monitoring of polar contaminants in surface waters. Here we carried out successive 14 day-deployments of polar organic chemical integrative samplers (POCIS) for one year at three sites. In parallel, we used the passive sampler deployment/retrieval operations to collect spot water samples for comparative analysis. We observed that frequency of quantification was significantly higher in POCIS than spot samples for 29 contaminants, similar for 15, and lower for one, because POCIS lowered the limits of quantification for most contaminants (median value factor of 11). We built a database of sampling rates (Rs) according to quality indices to convert concentrations in POCIS to concentrations in water (23 contaminants with a high-quality median Rs value, 20 with an approximate Rs and two with no usable Rs). Several phenomena were observed over one-year monitoring period. For example, after a flood episode, dilution phenomenon in rivers is correctly observed by using POCIS sampling whereas significant concentration increased due to soil leaching is observed with both passive and spot sampling. Cases of episodic contamination that were missed by spot sampling were observed with POCIS as it was able to capture contamination of short duration but sufficient intensity. Contamination by pharmaceuticals was found to come from wastewater treatment plant discharges and showed relatively little variation over the course of the year in both POCIS and spot samples. POCIS enables more reliable annual monitoring of pesticide and pharmaceutical contamination than spot sampling. Furthermore, POCIS also improves the environmental quality standards based assessment of chemical status and on annual average concentrations compared to spot sampling. This study demonstrates the value and practicability of POCIS-based chemical monitoring for use in regulatory control networks.

Ozonation of 47 organic micropollutants in secondary treated municipal effluents: Direct and indirect kinetic reaction rates and modelling.

Micropollutants like pharmaceuticals, hormones and pesticides are still found in treated municipal wastewater. An effective way to degrade micropollutants is to use oxidants such as ozone or hydroxyl radicals. We designed an innovative experimental protocol combining batch experiments and a study of a full-scale WWTP to understand and predict the removal via ozonation of typical micropollutants present in secondary treated effluents. First, the direct and indirect ozonation of 47 organic micropollutants was scrutinized, then a model was developed and calibrated to simulate the ozone transfers and the oxidation of the selected micropollutants. The kinetic rate constants between micropollutants and ozone or hydroxyl radicals (OH●) were determined for 47 micropollutants found in secondary treated effluent. We classified the micropollutants into low- (kO3 between 1.50 and 4.47 × 102 L mol-1. s-1), medium- (kO3 between 1.31 × 103 and 4.92 × 103 L mol-1. s-1) and high-oxidizable groups (kO3 between 9.44 × 104 and 8.18 × 106 L mol-1. s-1) according to their reactivity with ozone, and identified the major degradation pathways for all 47 micropollutants. Micropolluants of the low- and medium-oxidizable groups were largely eliminated by the indirect pathway, at 96% and 84% on average, respectively. In contrast, micropollutants of high-oxidizable group were largely eliminated by the direct pathway, at 98% on average. The model successfully simulated the direct and indirect ozonation of the 47 micropollutants in batch experiments and confirmed the predominant pathways for each group. Finally, the model was applied to the full-scale ozonation process operated at an ozone dose ranging from 0.5 to 1.6 gO3. gDOC-1. The model was found to reliably simulate the ozonation-process removal efficiencies for 4 micropollutants (imidacloprid, fenofibric acid, metronidazole and ketoprofen).

To what extent can the biogeochemical cycling of mercury modulate the measurement of dissolved mercury in surface freshwaters by passive sampling?

Mercury (Hg) is a pollutant of global concern owing to its great toxicity even at very low concentrations. Its toxicity depends on its chemical forms evidencing the importance to study its speciation. Dissolved Hg (Hg(d)) and methylmercury (MeHg(d)) monitoring in surface freshwaters represents a great challenge because of their very low concentrations and substantial temporal variability at different timescales. The Hg(d) temporal variability depends on the environmental conditions such as the hydrology, water temperature, redox potential (Eh), and solar photo cycle. Passive samplers represent an alternative to improve the assessment of Hg(d) and MeHg(d) concentrations in surface freshwaters by integrating their temporal variability. An original sampling strategy was designed to assess the relevance of 3-mercaptopropyl DGT (Diffusive Gradient in Thin films) to integrate in situ the temporal variations of labile Hg (Hg(DGT)) and MeHg (MeHg(DGT)) concentrations. This strategy was implemented on two rivers to study the dynamics of Hg(d), Hg(DGT), MeHg(d) and MeHg(DGT) at diurnal and annual timescales. We evidenced that Hg(DGT) and MeHg(DGT) concentrations were generally consistent with discrete sampling measurements of Hg(d) and MeHg(d) in dynamic surface freshwaters. However, Hg(DGT) concentrations were overestimated (2-16 times higher) in case of low flow or low water depth, low suspended particulate matter (SPM) concentrations and elevated daily photoperiod. The most probable hypothesis is that such conditions promoted Hg0 production, and resulted in Hg0 uptake by DGT. Thus, attention should be paid when interpreting Hg(DGT) concentrations in surface freshwaters in environmental conditions that could promote Hg0 production.

Influence of water depth and season on the photodegradation of micropollutants in a free-water surface constructed wetland receiving treated wastewater.

Micropollutants such as pharmaceutical products and pesticides are still present in treated wastewater. Several of these compounds are photoactive, either by direct or indirect photodegradation. An innovative on-site experimental protocol was designed to investigate the contribution of photodegradation processes to eliminate micropolluants in constructed wetland (CW). The solar photodegradation of 23 organic micropollutants was studied using in situ photoreactors at different depths. A CW-photodegradation model was designed and calibrated to further scrutinize the contribution of direct and indirect photodegradation processes in the elimination of micropollutants. The results show that photodegradation is most effective in the first 10 cm of the water column. A classification of micropollutants in 3 groups was developed to characterize their photodegradation. A significant increase of the half-life by direct photodegradation was observed in winter compared to summer due to a lower light intensity in winter. On the opposite, for direct + indirect photodegradation, no significant difference was observed between seasons. The decrease in light intensity in winter was compensated by higher nitrates concentration which promoted the formation of hydroxyl radicals and increased indirect photodegradation. The CW-photodegradation model successfully simulated the measured concentrations for direct and indirect photodegradation for 23 micropolluants. Nonetheless, it overestimated the indirect photodegradation with hydroxyl radicals when using default parameter values derived for surface waters. Hence, the consumption of hydroxyl radicals was increased by a factor of 20 for treated water. This model highlighted the predominance of direct photodegradation in the elimination of all micropollutants, except sotalol for the winter campaign.

Sampling of suspended particulate matter using particle traps in the Rhône River: Relevance and representativeness for the monitoring of contaminants.

Monitoring hydrophobic contaminants in surface freshwaters requires measuring contaminant concentrations in the particulate fraction (sediment or suspended particulate matter, SPM) of the water column. Particle traps (PTs) have been recently developed to sample SPM as cost-efficient, easy to operate and time-integrative tools. But the representativeness of SPM collected with PTs is not fully understood, notably in terms of grain size distribution and particulate organic carbon (POC) content, which could both skew particulate contaminant concentrations. The aim of this study was to evaluate the representativeness of SPM characteristics (i.e. grain size distribution and POC content) and associated contaminants (i.e. polychlorinated biphenyls, PCBs; mercury, Hg) in samples collected in a large river using PTs for differing hydrological conditions. Samples collected using PTs (n = 74) were compared with samples collected during the same time period by continuous flow centrifugation (CFC). The grain size distribution of PT samples shifted with increasing water discharge: the proportion of very fine silts (2-6 µm) decreased while that of coarse silts (27-74 µm) increased. Regardless of water discharge, POC contents were different likely due to integration by PT of high POC-content phytoplankton blooms or low POC-content flood events. Differences in PCBs and Hg concentrations were usually within the range of analytical uncertainties and could not be related to grain size or POC content shifts. Occasional Hg-enriched inputs may have led to higher Hg concentrations in a few PT samples (n = 4) which highlights the time-integrative capacity of the PTs. The differences of annual Hg and PCB fluxes calculated either from PT samples or CFC samples were generally below 20%. Despite some inherent limitations (e.g. grain size distribution bias), our findings suggest that PT sampling is a valuable technique to assess reliable spatial and temporal trends of particulate contaminants such as PCBs and Hg within a river monitoring network.

Metal measurement in aquatic environments by passive sampling methods: Lessons learning from an in situ intercomparison exercise.

Passive sampling devices (PS) are widely used for pollutant monitoring in water, but estimation of measurement uncertainties by PS has seldom been undertaken. The aim of this work was to identify key parameters governing PS measurements of metals and their dispersion. We report the results of an in situ intercomparison exercise on diffusive gradient in thin films (DGT) in surface waters. Interlaboratory uncertainties of time-weighted average (TWA) concentrations were satisfactory (from 28% to 112%) given the number of participating laboratories (10) and ultra-trace metal concentrations involved. Data dispersion of TWA concentrations was mainly explained by uncertainties generated during DGT handling and analytical procedure steps. We highlight that DGT handling is critical for metals such as Cd, Cr and Zn, implying that DGT assembly/dismantling should be performed in very clean conditions. Using a unique dataset, we demonstrated that DGT markedly lowered the LOQ in comparison to spot sampling and stressed the need for accurate data calculation.

Lab-scale experimental strategy for determining micropollutant partition coefficient and biodegradation constants in activated sludge.

The nitrifying/denitrifying activated sludge process removes several micropollutants from wastewater by sorption onto sludge and/or biodegradation. The objective of this paper is to propose and evaluate a lab-scale experimental strategy for the determination of partition coefficient and biodegradation constant for micropollutant with an objective of modelling their removal. Four pharmaceutical compounds (ibuprofen, atenolol, diclofenac and fluoxetine) covering a wide hydrophobicity range (log Kow from 0.16 to 4.51) were chosen. Dissolved and particulate concentrations were monitored for 4 days, inside two reactors working under aerobic and anoxic conditions, and under different substrate feed conditions (biodegradable carbon and nitrogen). We determined the mechanisms responsible for the removal of the target compounds: (i) ibuprofen was biodegraded, mainly under aerobic conditions by cometabolism with biodegradable carbon, whereas anoxic conditions suppressed biodegradation; (ii) atenolol was biodegraded under both aerobic and anoxic conditions (with a higher biodegradation rate under aerobic conditions), and cometabolism with biodegradable carbon was the main mechanism; (iii) diclofenac and fluoxetine were removed by sorption only. Finally, the abilities of our strategy were evaluated by testing the suitability of the parameters for simulating effluent concentrations and removal efficiency at a full-scale plant.

Removal of xenobiotics from effluent discharge by adsorption on zeolite and expanded clay: an alternative to activated carbon?

Xenobiotics such as pesticides and pharmaceuticals are an increasingly large problem in aquatic environments. A fixed-bed adsorption filter, used as tertiary stage of sewage treatment, could be a solution to decrease xenobiotics concentrations in wastewater treatment plants (WWTPs) effluent. The adsorption efficiency of two mineral adsorbent materials (expanded clay (EC) and zeolite (ZE)), both seen as a possible alternative to activated carbon (AC), was evaluated in batch tests. Experiments involving secondary treated domestic wastewater spiked with a cocktail of ten xenobiotics (eight pharmaceuticals and two pesticides) known to be poorly eliminated in conventional biological process were carried out. Removal efficiencies and partitions coefficients were calculated for two levels of initial xenobiotic concentration, i.e, concentrations lower to 10 µg/L and concentrations ranged from 100 to 1,000 µg/L. While AC was the most efficient adsorbent material, both alternative adsorbent materials showed good adsorption efficiencies for all ten xenobiotics (from 50 to 100 % depending on the xenobiotic/adsorbent material pair). For all the targeted xenobiotics, at lower concentrations, EC presented the best adsorption potential with higher partition coefficients, confirming the results in terms of removal efficiencies. Nevertheless, Zeolite presents virtually the same adsorption potential for both high and low xenobiotics concentrations to be treated. According to this first batch investigation, ZE and EC could be used as alternative absorbent materials to AC in WWTP.

Impact of wastewater treatment plants on receiving surface waters and a tentative risk evaluation: the case of estrogens and beta blockers.

Five estrogenic hormones (unconjugated + conjugated fractions) and 10 beta blockers were analyzed in three wastewater treatment plant (WWTP) effluents and receiving river waters in the area of Lyon, France. In the different samples, only two estrogens were quantified: estrone and estriol. Some beta blockers, such as atenolol, acebutolol, and sotalol, were almost always quantified, but others, e.g., betaxolol, nadolol, and oxprenolol were rarely quantified. Concentrations measured in river waters were in the nanogram per liter range for estrogens and between 0.3 and 210 ng/L for beta blockers depending on the substance and the distance from the WWTP outfall. The impact of the WWTP on the receiving rivers was studied and showed a clear increase in concentrations near the WWTP outfall. For estrogens, the persistence in surface waters was not evaluated given the low concentrations levels (around 1 ng/L). For beta blockers, concentrations measured downstream of the WWTP outfall were up to 16 times higher than those measured upstream. Also, the persistence of metoprolol, nadolol, and propranolol was noted even 2 km downstream of the WWTP outfall. The comparison of beta blocker fingerprints in the samples collected in effluent and in the river also showed the impact of WWTP outfall on surface waters. Finally, a tentative environmental risk evaluation was performed on 15 sites by calculating the ratio of receiving water concentrations to predicted non-effect concentrations (PNEC). For estrogens, a total PNEC of 5 ng/L was considered and these substances were not linked to any potential environmental risk (only one site showed an environmental risk ratio above 1). Unfortunately, few PNECs are available and risk evaluation was only possible for 4 of the 10 beta blockers studied: acebutolol, atenolol, metoprolol, and propranolol. Only propranolol presented a ratio near or above 1, showing a possible environmental risk for 4 receiving waters out of 15.

Occurrence of priority and emerging organic compounds in fishes from the Rhone River (France).

The main objective of this study was to collect new data on the occurrence, levels of priority and emerging organic compounds in freshwater fish sampled in the Rhone River. The 34 studied contaminants included alkylphenols, bisphenol A, polybromodiphenylethers (PBDE), perfluorinated compounds, hexabromocyclododecanes (HBCD), hexachlorobenzene and hexachlorobutadiene (HCBD). About 50 fish samples (individual specimens or pooled fish) were collected from three sites located upstream and downstream of the Lyon metropolitan area in the Rhone River (France). Four species were caught at each site, namely: the barbel (Barbus barbus), the common bream (Abramis brama), the white bream (Blicca bjoerkna) and the chub (Squalius cephalus). Some contaminants were quantified in all the 32 fish samples analysed: 4-nonylphenol, α-HBCD, the six PBDE congeners (28, 47, 99, 100, 153, 154), perfluorooctanesulfonate (PFOS) and perfluorodecanoic acid. Twenty three of the 32 samples had a concentration of PFOS above the Environmental Quality Standards (EQS) (up to six times higher than the EQS), and all the 32 samples had concentrations of PBDE above the EQS (up to 4,000 times higher, with the sum of six PBDE varying from 4.5 to 182 ng/g dry weight). Clearly, the interest to consider PFOS and HBCD as new priority substances is confirmed. In contrast, the pertinence of a priority status for HCBD, which was never quantified in our study, might have to be reconsidered in the future.

Determination of the uptake and release rates of multifamilies of endocrine disruptor compounds on the polar C18 Chemcatcher. Three potential performance reference compounds to monitor polar pollutants in surface water by integrative sampling.

The uptake kinetics of 27 emerging pollutants on the polar C18 Chemcatcher have been investigated. This investigation determined the sampling rates of 20 compounds, including 16 endocrine disruptors and 4 pharmaceuticals, which were used as overall pollution indicators. Calibrations were completed in a 50-L flow-through microcosm with continuous renewal of tap water spiked with approximately 3 µg/L of each pollutant and with sampling times at 1, 3, 6 and 12h and 1, 3, 7, 14, 21 and 28 days. Exponential regressions for the accumulation kinetics were plotted to confirm the maximum linear uptake times for each molecule using the half time of equilibrium (t(1/2)) criteria. Of the compounds tested, 17 were accumulated linearly for up to 14 or 21 days with an R(2) above 0.98 for linear correlations. The evaluation of the release kinetics of a C18 Chemcatcher spiked with 20 deuterated compounds identified 3 potential performance reference compounds (PRCs) with exponential desorption rates showing relatively good isotropic exchange.

Occurrence and fate of relevant substances in wastewater treatment plants regarding Water Framework Directive and future legislations.

The next challenge of wastewater treatment is to reliably remove micropollutants at the microgram per litre range. During the present work more than 100 substances were analysed through on-site mass balances over 19 municipal wastewater treatment lines. The most relevant substances according to their occurrence in raw wastewater, in treated wastewater and in sludge were identified, and their fate in wastewater treatment processes was assessed. About half of priority substances of WFD were found at concentrations higher than 0.1 µg/L in wastewater. For 26 substances, potential non-compliance with Environmental Quality Standard of Water Framework Directive has been identified in treated wastewater, depending on river flow. Main concerns are for Cd, DEHP, diuron, alkylphenols, and chloroform. Emerging substances of particular concern are by-products, organic chemicals (e.g. triclosan, benzothiazole) and pharmaceuticals (e.g. ketoprofen, diclofenac, sulfamethoxazole, carbamazepine). About 80% of the load of micropollutants was removed by conventional activated sludge plants, but about two-thirds of removed substances were mainly transferred to sludge.

On-site evaluation of the removal of 100 micro-pollutants through advanced wastewater treatment processes for reuse applications.

The next challenge of wastewater treatment is to reliably remove micro-pollutants at the microgram per litre range in order to meet reuse applications and contribute to reach the good status of the water bodies. A hundred priority and relevant emerging substances were measured to evaluate at full-scale the removal efficiencies of seven advanced treatment lines (one membrane bioreactor process and six tertiary treatment lines) that were designed for reuse applications. To reliably compare the processes, specific procedures for micro-pollutants were applied for sampling, analysis and calculation of removal efficiencies. The membrane bioreactor process allowed to upgrade the removal efficiencies of about 20% of the substances measured, especially those that were partially degraded during conventional processes. Conventional tertiary processes like high rate clarification, sand filtration and polishing pond achieved significant removal for some micro-pollutants, especially for adsorbable substances. Advanced tertiary processes, like ozonation, activated carbon and reverse osmosis were all very efficient to complete the removal of polar pesticides and pharmaceuticals; metals and less polar substances were better retained by reverse osmosis.

Limiting the emissions of micro-pollutants: what efficiency can we expect from wastewater treatment plants?

The next challenge of wastewater treatment is to reliably remove micro-pollutants at the microgram per litre range in order to meet the environmental quality standards set by new regulations like the Water Framework Directive. The present work assessed the efficiency of different types of primary, secondary and tertiary processes for the removal of more than 100 priority substances and other relevant emerging pollutants through on-site mass balances over 19 municipal wastewater treatment lines. Secondary biological processes proved to be in average 30% more efficient than primary settling processes. The activated sludge (AS) process led to a significant reduction of pollution loads (more than 50% removal for 70% of the substances detected). Biofilm processes led to equivalent removal efficiencies compared to AS, except for some pharmaceuticals. The membrane bioreactor (MBR) process allowed to upgrade removal efficiencies of some substances only partially degraded during conventional AS processes. Preliminary tertiary processes like tertiary settling and sand filtration could achieve significant removal for adsorbable substances. Advanced tertiary processes, like ozonation, activated carbon and reverse osmosis were all very efficient (close to 100%) to complete the removal of polar pesticides and pharmaceuticals; less polar substances being better retained by reverse osmosis.

Occurrence and removal of estrogens and beta blockers by various processes in wastewater treatment plants.

This study aims at evaluating occurrence and treatment efficiency of five estrogenic hormones and ten beta blockers in wastewater treatment plants (WWTP). The use of consistent sampling procedures, analytical techniques and data processing enabled to achieve an accurate comparison of the performances of the different treatment processes. First, the occurrence of molecules was evaluated in fourteen rural and urban WWTP located in France. Free and total estrogens were analyzed showing that more than 84% of estrogens in the dissolved phase of influent samples are in the free form. In effluent samples, comparable mean values but higher variation are underlined (RSD from 13 to 54% depending on the estrogen, compared to 11-21% for influents). Most of the target molecules are quantified in 30 influent and 31 effluent samples. Similar occurrence frequencies are obtained for influents from rural (6 WWTP) and urban areas (8 WWTP), except for betaxolol which is only quantified in urban wastewaters. Removal efficiencies of 8 biological treatments were studied: suspended growth biomass (activated sludge) and attached growth systems (biofilter, rotating biological contactor, reed-bed filter, trickling filter). Biological treatments are efficient to remove estrogens from the dissolved phase, with removal rate around 90%. For beta blockers, acebutolol and nadolol are efficiently removed (mean removal rate of 80%), whereas sotalol and propranolol are hardly impacted by biological treatments (removal rate below 20%). Finally, 9 tertiary treatment processes were evaluated. Ozonation, reverse osmosis and activated carbon filtration prove a high removal efficiency for beta blockers (above 80%). On the contrary, high speed chemical settler, sand filtration, silex filtration, microfiltration and UV present generally removal rates below 30% for all beta blockers. The polishing pond studied presents variable removal performances depending on the molecules (up to 75% for propranolol). The role of the hydraulic retention time on the removal efficiencies is confirmed.

Correlations between dioxin-like and indicators PCBs: potential consequences for environmental studies involving fish or sediment.

Among the numerous PCB congeners, most of the dioxin-like PCBs (DL-PCBs) need to be characterized by hyphenated techniques. It has been shown in several instances that these congeners are well related to the total PCB content in fish. We examined datasets collected mainly in France, on freshwater and marine fish and sediments. A statistical model linking DL- and indicator PCBs was developed for a dataset composed of freshwater fishes, and proved to predict well DL-PCBs from indicator PCBs in all other fish sets, including marine ones. Type II error rates remained low in almost all fish sets. A similar correlation was observed in sediments. Non-dioxin-like PCBs elicit various adverse effects and represent 95% of the total PCBs. A European guideline for them is needed; the correlation between DL- and indicator PCBs could help develop this standard in the future.

Fate of pharmaceuticals and personal care products in wastewater treatment plants--conception of a database and first results.

We created a database in order to quantitatively assess the occurrence and removal efficiency of pharmaceuticals and personal care products (PPCPs) in wastewater treatment plants (WWTPs). From 117 scientific publications, we compiled 6641 data covering 184 PPCPs. Data included the concentrations of PPCPs in WWTP influents and effluents, their removal efficiency and their loads to the aquatic environment. The first outputs of our database allowed to identify the most investigated PPCPs in WWTPs and the most persistent ones, and to obtain reliable and quantitative values on their concentrations, frequency of detection and removal efficiency in WWTPs. We were also able to compare various processes and pointed out activated sludge with nitrogen treatment and membrane bioreactor as the most efficient ones.

Removal efficiency of pharmaceuticals and personal care products with varying wastewater treatment processes and operating conditions - conception of a database and first results.

We created a database in order to quantitatively assess the occurrence and removal efficiency of PPCPs in WWTPs. From 113 scientific publications, we compiled 5887 data on the concentrations and loads of PPCPs in WWTP influents and effluents, and on their removal efficiency. The first outputs of our database include: (1) a list of the most frequently studied molecules, their frequency of detection, their mean concentration and removal in liquid influent and effluent; (2) a comparison of the removal efficiency for different WWTP processes; (3) a study of the influence of the operating conditions (sludge and hydraulic retention times).

Molecular evolution of the s locus controlling mating in the brassicaceae.

Flowering plants possess self-incompatibility (SI) mechanisms that promote outbreeding and thereby increase their genetic diversity. In the self-incompatible Brassicaceae, recognition and rejection of self-pollen is based on a receptor-ligand interaction between male and female SI determinants. A transmembrane receptor kinase (S locus Receptor Kinase, SRK) determines the SI specificity in stigmatic cells, whereas a pollen coat-localized ligand (S locus Cysteine-Rich, SCR) determines the SI specificity in pollen. During recent years, major advances have been made in the understanding of the molecular basis of self-pollen recognition by stigmatic cells. In this review, we will focus on evolutionary aspects of the SI system in Brassicaceae. We will describe how the study of the molecular aspect of SI, not only in the historical Brassica model but also in Arabidopsis species, has contributed to highlight certain aspects of evolution of SI in the Brassicaceae.

Optimization, validation and comparison of various extraction techniques for the trace determination of polycyclic aromatic hydrocarbons in sewage sludges by liquid chromatography coupled to diode-array and fluorescence detection.

There is a need for a better characterization of sludges from wastewater treatment plants which are destined to be spread on agricultural lands. Inorganic pollutants are regularly controlled but organic pollutants have received few attention up to now. On this paper, we have been interested on the analysis of the 16 polycyclic aromatic hydrocarbons (PAHs) listed in the US Environmental Protection Agency (US EPA) priority list and more particularly of the six PAHs listed in the European community list (fluoranthene, benzo[b and k]fluoranthene, benzo[a]pyrene, benzo[ghi]perylene, indeno[1,2,3-cd]pyrene). The analysis step consists on liquid chromatography with both fluorescence and UV detections as described in the EPA Method 8310. As for the extraction step, several techniques such as supercritical fluid extraction, pressurized liquid extraction, focused microwave extraction in open vessels, Soxhlet and ultrasonic extractions are compared after optimization of the experimental conditions (solvent nature and quantity, temperature, pressure, duration, ... ) and validation with certified sludges. When optimized, these five extraction techniques are as much efficient with similar relative standard deviation. Whatever the extraction techniques used, the whole analysis protocol permits to quantify PAHs in the range of 0.09 to 0.9 mg/kg of dried sludges.