Vincent Rocher

Priority pollutants in wastewater and combined sewer overflow.

Implementation of the European Water Framework Directive and its affiliated directives requires Member States to improve their understanding of priority pollutants (PPs) in urban areas and obviously within wastewater systems. As a direct consequence, this study is intended to furnish data on both PP occurrence and the significance of concentrations in wastewater during dry and wet periods within combined sewers. Various sampling sites within the Paris combined sewer network were selected; for each sample, a total of 66 determinants, including metals, polycyclic aromatic hydrocarbons (PAHs), pesticides, organotins, volatile organic compounds, chlorobenzenes, phthalates and alkylphenols, were analysed. A broad range of PPs was observed in wastewater during dry as well as wet weather periods. Of the 66 elements investigated, 33 and 40 priority substances could be observed in raw sewage and wet weather effluent, respectively. As expected, a majority of metals were present in all samples, reflecting their ubiquitous nature. For both periods, chlorobenzenes and most of the pesticides always remained below the limit of quantification, while the majority of other organic pollutants assessed were identified within the microg l(-1) range. As highlighted by the larger number of substances detected in wet weather samples and the significance of their concentrations, runoff via atmospheric inputs and/or surface leaching was found to induce a wider range of PPs (n=40) and lead to higher concentrations of certain metals, PAHs, pesticides and other individual compounds. The data generated during this survey, which constitutes one of the first studies conducted in Europe to report concentrations for a variety of priority substances in wastewater within combined sewers, may be used in the future to identify PPs of potential significance for dry and wet weather periods and targeted for further investigation.

Impact of an intense combined sewer overflow event on the microbiological water quality of the Seine River.

For a better understanding of the short and mid-term impacts of a combined sewer overflow (CSO) on the microbiological quality of the receiving river, we studied the composition of a CSO discharge and monitored during several hours the changes in the concentration of fecal indicator bacteria (FIB) in the impacted river water mass. The CSO occurred at the Clichy outfall (Paris agglomeration, France) in summer 2008 as a result of the most intense rainfall of the year. In 6h, 578, 705 m(3) of sewage and 124 t of suspended matter (SM) were discharged into the Seine River. The CSO contained 1.5 × 10(6)E. coli and 4.0 × 10(5) intestinal enterococci per 100 mL on average, and 77% of the E. coli were attached to SM. It was estimated that 89% of the CSO discharge was contributed by surface water runoff, and that resuspension of sewer sediment contributed to ∼75% of the SM, 10-70% of the E. coli and 40-80% of the intestinal enterococci. Directly downstream from the CSO outfall, FIB concentrations in the impacted water mass of the Seine River (2.9 × 10(5)E. coli and 7.6 × 10(4) intestinal enterococci per 100 mL) exceeded by two orders of magnitude the usual dry weather concentrations. After 13-14 h of transit, these concentrations had decreased by 66% for E. coli and 79% for intestinal enterococci. This decline was well accounted for by our estimations of dilution, decay resulting from mortality or loss of culturability and sedimentation of the attached fraction of FIB.

Dye removal from aqueous solution by magnetic alginate beads crosslinked with epichlorohydrin.

Innovative magnetic alginate beads are used to remove organic pollutants from aqueous solution under different experimental conditions. These alginate beads (EpiMAB) are prepared by an extrusion technique and crosslinked with epichlorohydrin. They contain both magnetic nanoparticles and activated carbon (AC). With the addition of magnetic properties, the beads can be easily recovered or manipulated with an external magnetic field. Their capacity to adsorb pollutants is linked to encapsulated AC and to active sites coming from both magnetic nanoparticles and alginate. The efficiency of the beads as biosorbent for the removal of dyes is assessed using methyl orange (MO) and methylene blue (MB) as model molecules. The dye uptake is found to vary with the initial concentration and the charge of the adsorbed molecule. The Langmuir equation fits well the adsorption data with maximum adsorption capacities of 0.02 mmol/g for MO and 0.7 mmol/g for MB. Kinetics experiments are performed to evaluate the equilibrium time; the pseudo-second-order kinetic model adequately describes the experimental data. The influence of the pH of the solution on adsorption is also investigated and a comparison with alginate beads crosslinked by calcium ions is made.

Microplastic contamination in an urban area: a case study in Greater Paris

This study investigates the microplastic contamination of both urban compartments (wastewater and total atmospheric fallout) and surface water in a continental environment (Greater Paris, France). These first investigations on urban environment confirm the presence of microplastics in sewage, freshwater and total atmospheric fallout and provide knowledge on the type and size distribution of microplastics in the [100 µm-5 000 µm] range. For the first time, the presence of microplastics, mostly fibers, is highlighted in total atmospheric fallout (29-280 particles/m2/day). High levels of fibers were found in wastewater (260-320 x103 particles/m3). In treated effluent, the contamination significantly decreases to 14-50 x103 particles/m3. In River Seine, two sampling devices are used to collect both large and small microplastic particles: i) a plankton net (80 µm mesh) and ii) a manta trawl (330 µm mesh). Sampling with the plankton net showed a predominance of fibers with concentrations ranging from 3 to 108 particles/m3. A greater diversity of both microplastic shapes and types was encountered during manta trawl sampling but at much lower concentrations (0.28-0.47 particles/m3). This combined approach could be relevant and implemented in future studies to provide an accurate overview of microplastic distribution in freshwater.

Hydrocarbons and Metals in Atmospheric Deposition and Roof Runoff in Central Paris

Hydrocarbons (aliphatic and aromatic) and metals (heavy metals and major elements) were measured in both atmospheric deposition and roof runoff in central Paris (France). Atmospheric deposition (wet and dry) was collected from December 2001 to October 2002 and roof runoff was sampled on three buildings with different covering materials, i.e., slate tiles and zinc sheets. This paper gives an overview of the results on the flux and distribution points of view for both atmospheric deposition and roof runoff. Results show that atmospheric fluxes of hydrocarbons and major elements increase during cold seasons, due to residential heating occurrence, while heavy metals, whose major sources have constant emission fluxes, exhibit steady atmospheric loads throughout the year. Moreover, hydrocarbon fingerprints reveal mainly biogenic and pyrolytic origins for aliphatic and aromatic hydrocarbons, respectively. The results about roof runoff contamination suggest that the scavenging processes for hydrocarbons and metals are dependent on rainfall amount rather than on the rain event characteristics (number, intensity, duration), and dry deposition weakly contributes to the pollutant loads in roof runoff. Results also highlight that both metallic and slate roofs do not act as a source of hydrocarbons and major elements—exclusively originating from atmospheric deposition—while they act as a source of some heavy metals. Zinc-covered roofs largely release Zn and Ti, while slate roofs mainly release Pb, Ti and Cu. Whatever the material used for roof covering, roof runoff presents high Ni and V loads due to the vicinity of the chimney stacks of heating boilers.

Priority pollutants in urban stormwater: Part 2 - Case of combined sewers

This study has evaluated the quality of combined sewer overflows (CSOs) in an urban watershed, such as Paris, by providing accurate data on the occurrence of priority pollutants (PPs) and additional substances, as well as on the significance of their concentrations in comparison with wastewater and stormwater. Of the 88 substances monitored, 49 PPs were detected, with most of these also being frequently encountered in wastewater and stormwater, thus confirming their ubiquity in urban settings. For the majority of organic substances, concentrations range between 0.01 and 1 μgl(-1), while metals tend to display concentrations above 10 μgl(-1). Despite this ubiquity, CSO, wastewater and stormwater feature a number of differences in both their concentration ranges and pollutant patterns. For most hydrophobic organic pollutants and some particulate-bound metals, CSOs exhibit higher concentrations than those found in stormwater and wastewater, due to the contribution of in-sewer deposit erosion. For pesticides and Zn, CSOs have shown concentrations close to those of stormwater, suggesting runoff as the major contributor, while wastewater appears to be the main source of volatile organic compounds. Surprisingly, similar concentration ranges have been found for DEHP and tributyltin compounds in CSOs, wastewater and stormwater. The last section of this article identifies substances for which CSO discharges might constitute a major risk of exceeding Environmental Quality Standards in receiving waters and moreover indicates a significant risk for PAHs, tributyltin compounds and chloroalkanes. The data generated during this survey can subsequently be used to identify PPs of potential significance that merit further investigation.

Priority pollutants in surface waters and settleable particles within a densely urbanised area: Case study of Paris (France)

Implementation of the European Water Framework Directive 2000/60/EC (WFD) requires Member States to expand their collective knowledge of priority pollutants (PPs) within receiving waters. To achieve this objective, information on the occurrence of PPs in surface waters and, more specifically, within densely urbanized areas needs to be collected. This study has therefore been designed to provide information on both PP occurrence and concentration build-up along a heavily urbanized transect of the Seine River in the Paris region (France). A large range of PPs were observed in settleable particles and, to a lesser extent, in the waters surveyed. In surface waters, a total of 18 PPs, including 15 priority hazardous substances, were indeed detected, yet concentrations rarely exceeded the limit of quantification. In fact, only diuron, DEHP, fluoranthene and para-tert-octylphenol are observed on a frequent basis, with concentrations ranging from <0.01 to 1.0 microg l(-1). As regards the Environmental Quality Standards (EQS), 10 substances or groups of substances were found in surface waters to exhibit concentrations above the annual average value, while only the benzo(a)pyrene concentration exceed the maximum allowable level. As for the Canadian Sediment Quality Guidelines, settleable particles collected in the Seine River appear to be heavily contaminated since most samples contain PP levels above the guideline values (18 PPs) and, in many cases, above the probable effect levels (15 PPs), which underscores that the levels of metals, PAHs and PCBs in settleable particles constitute a potential risk to freshwater organisms.

Occurrence of estrogens in sewage sludge and their fate during plant-scale anaerobic digestion.

Estrogens, which contribute greatly to the endocrine-disrupting activity in sewage, are partially sorbed onto particulate matter during sewage treatment. We thus investigated the occurrence of estrogens in different kinds of sludge and throughout a plant-scale anaerobic digestion process. The analytical method was first validated when sorption interaction between spiked estrogens and sludge could occur. Hence, the recovery ratio of estrone (E1), 17beta-estradiol (E2), estriol (E3) and 17alpha-ethinylestradiol (EE2) were determined when added to liquid sludge and mixed under various conditions. We show that minor non-extractable residues were formed (5-10%), suggesting that the sorption interaction established with sludge did not limit estrogen extraction. Estrogen concentrations measured in collected samples varied with sludge type. Secondary sludge showed higher E1 contents than primary sludge: respectively, 43 and 8 ng g(-1) dry weight (dw). Two pathways of E1 production during secondary treatment are proposed to explain such a result. Higher estrogen concentrations were found in secondary sludge from a conventional plant (55 ng g(-1)dw) compared to those from an advanced plant (13 ng g(-1)dw). Based on estimated estrogen concentrations in sewage, we conclude that operating parameters play a role in the sorption of estrogens during secondary treatment. Also, the hydrophobic properties of the estrogens influenced the individual adsorption of each molecule. Thus, E3 showed the highest estimated concentrations in sewage but very low concentrations in sludge. Finally, plant-scale anaerobic digestion showed low efficiency (<40%) for removing estrogens and, regarding the final dewatering process, concentrations increased for E2 and EE2.

Removal of a wide range of emerging pollutants from wastewater treatment plant discharges by micro-grain activated carbon in fluidized bed as tertiary treatment at large pilot scale

Among the solutions to reduce micropollutant discharges into the aquatic environment, activated carbon adsorption is a promising technique and a large scale pilot has been tested at the Seine Centre (240,000 m(3)/d - Paris, France) wastewater treatment plant (WWTP). While most of available works studied fixed bed or contact reactors with a separated separation step, this study assesses a new type of tertiary treatment based on a fluidized bed containing a high mass of activated carbon, continuously renewed. For the first time in the literature, micro-grain activated carbon (μGAC) was studied. The aims were (1) to determine the performances of fluidized bed operating with μCAG on both emerging micropollutants and conventional wastewater quality parameters, and (2) to compare its efficiency and applicability to wastewater to former results obtained with PAC. Thus, conventional wastewater quality parameters (n=11), pharmaceuticals and hormones (PPHs; n=62) and other emerging pollutants (n=57) have been monitored in μGAC configuration during 13 campaigns. A significant correlation has been established between dissolved organic carbon (DOC), PPHs and UV absorbance at 254 nm (UV-254) removals. This confirms that UV-254 could be used as a tertiary treatment performance indicator to monitor the process. This parameter allowed identifying that the removals of UV-254 and DOC reach a plateau from a μGAC retention time (SRT) of 90-100 days. The μGAC configuration substantially improves the overall quality of the WWTP discharges by reducing biological (38-45%) and chemical oxygen demands (21-48%), DOC (13-44%) and UV-254 (22-48%). In addition, total suspended solids (TSS) are retained by the μGAC bed and a biological activity (nitratation) leads to a total elimination of NO2(-). For micropollutants, PPHs have a good affinity for μGAC and high (>60%) or very high (>80%) removals are observed for most of the quantified compounds (n=22/32), i.e. atenolol (92-97%), carbamazepine (80-94%), ciprofloxacin (75-95%), diclofenac (71-97%), oxazepam (74-91%) or sulfamethoxazole (56-83%). In addition, alkylphenols, artificial sweeteners, benzotriazole, bisphenol A, personal care products (triclocarban and parabens) and pesticides have removals lying in the 50 ->90% range. Overall, the fluidized bed of μGAC allows obtaining performances comparable to PAC at the same activated carbon dose. Indeed, the average removal of the 13 PPHs found at a high occurrence (>75%) in WWTP discharges is similar at 20 g/m(3) of μGAC (78-89%) and PAC (85-93%). In addition, this recycled μGAC operation leads to several operational advantages (no FeCl3, reactivable, higher SRT, higher treated flow) and has a stronger impact on the overall wastewater quality compared to PAC.

Priority and emerging pollutants in sewage sludge and fate during sludge treatment.

This paper aims at characterizing the quality of different treated sludges from Paris conurbation in terms of micropollutants and assessing their fate during different sludge treatment processes (STP). To achieve this, a large panel of priority and emerging pollutants (n=117) have been monitored in different STPs from Parisian wastewater treatment plants including anaerobic digestion, thermal drying, centrifugation and a sludge cake production unit. Considering the quality of treated sludges, comparable micropollutant patterns are found for the different sludges investigated (in mg/kg DM - dry matter). 35 compounds were detected in treated sludges. Some compounds (metals, organotins, alkylphenols, DEHP) are found in every kinds of sludge while pesticides or VOCs are never detected. Sludge cake is the most contaminated sludge, resulting from concentration phenomenon during different treatments. As regards treatments, both centrifugation and thermal drying have broadly no important impact on sludge contamination for metals and organic compounds, even if a slight removal seems to be possible with thermal drying for several compounds by abiotic transfers. Three different behaviors can be highlighted in anaerobic digestion: (i) no removal (metals), (ii) removal following dry matter (DM) elimination (organotins and NP) and iii) removal higher than DM (alkylphenols - except NP - BDE 209 and DEHP). Thus, this process allows a clear removal of biodegradable micropollutants which could be potentially significantly improved by increasing DM removal through operational parameters modifications (retention time, temperature, pre-treatment, etc.).