Fate of emerging and priority micropollutants during the sewage sludge treatment: Case study of Paris conurbation. Part 1: Contamination of the different types of sewage sludge.

This article provides data on the contamination of different kinds of sludge (raw, centrifuged, digested, thermally dried sludge and sludge cake) from Paris conurbation by 71 various pollutants including pharmaceutical products (PHPs), hormones, perfluorinated acids (PFAs), linear alkylbenzene sulfonate (LAS), alkylphenols (APs), phthalates (PAEs), polycyclic aromatic hydrocarbons (PAHs) and polychlorobiphenyls (PCBs). Very high contents of LAS (0.1-10g/kg dry matter - DM) compared to other compounds were found in all types of sludge followed by DEHP (10-100mg/kg DM) and fluoroquinolones (1-100mg/kg DM). APs were measured at intermediary contents in Parisian sludge, lying in the 2-20mg/kg DM range. Finally, hormones, PAHs, PCBs, PAEs, PFAs and the remaining PHPs were all found at contents lower than 1mg/kg DM. For most compounds (PHPs, PFOS, DEHP, PAHs), no significant differences in the micropollutant contents were found for similar types of sludge from different WWTP in Paris, highlighting the homogeneity of sludge contamination in downstream Paris catchment. The variability of concentration is rather high (coefficient of variation >100%) for several PHPs, PFAs or PCBs while it is moderate (<100%) or low (<50%) for fluoroquinolones, hormones, PAHs, APs or LAS. In addition, digestion seems to have a buffer effect as variabilities are lower in digested sludge for PHPs, PFAs, APs and PCBs. During sludge treatment (centrifugation, digestion, thermal drying, sludge conditioning+press filtration), the hormones, LAS, APs, PAHs, DEHP and PCBs concentrations increased, while those of PHPs and PFAs decreased. In the case of digestion, the increase of content can be explained by no pollutant removal or a lower removal than DM removal (concentration phenomenon) whereas the decrease underlines that the compound is more removed than the DM. In any case, these concentration variations presuppose the mechanisms of dissipation that could be attributed to volatilization, biotic or abiotic transformation (complete or with metabolites production), bound residues formation. In addition, data on sludge liquors - centrifuged (CW) and condensed (TDW) waters - from respectively centrifugation and thermal drying were collected. Several hormones, PHPs, PFAs, LAS, PAEs, APs, PCBs and PAHs were quantified in CW and TDW, displaying a transfer through the water removal. The concentrations observed are rather comparable to those found in wastewater.

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.

Influence of effluent organic matter on copper speciation and bioavailability in rivers under strong urban pressure.

This study focuses on spatiotemporal variations in the type of dissolved organic matter (DOM) and copper binding ability both upstream and downstream of Paris. It also compares the relative influence of both natural DOM upstream of Paris and effluent dissolved organic matter (EfDOM) output from a wastewater treatment plant (WWTP) on trace metal speciation and bioavailability in aquatic systems. In addition to the typical high- and low-affinity binding sites, a third family of very high-affinity binding sites has been highlighted for EfDOM. In receiving waters downstream of Paris during low-flow periods, the percentage of high- and very high-affinity sites originating from EfDOM reaches nearly 60 %. According to the speciation computation, the free copper concentration upstream of Paris exceeds the downstream Paris concentration by a factor of 2 to 4. As regards copper bioavailability, the highest EC50tot values were observed for EfDOM and downstream DOM, with a very low aromaticity and low UV absorbance. This finding suggests that specific ultraviolet absorbance (SUVA) is unlikely to be useful in assessing metal speciation and toxicity in aquatic systems subject to strong urban pressures. These results also highlight that the copper speciation computation for surface water exposed to considerable human pressures should include not only the humic and/or fulvic part of dissolved organic carbon but more hydrophilic fractions as well, originating for example from EfDOM.

Benzalkonium runoff from roofs treated with biocide products - In situ pilot-scale study.

Roof maintenance practices often involve the application of biocide products to fight against moss, lichens and algae. The main component of these products is benzalkonium chloride, a mixture of alkyl benzyl dimethyl ammonium chlorides with mainly C12 and C14 alkyl chain lengths, which is toxic for the aquatic environment. This paper describes, on the basis of an in-situ pilot scale study, the evolution of roof runoff contamination over a one year period following the biocide treatment of roof frames. Results show a major contamination of roof runoff immediately after treatment (from 5 to 30 mg/L), followed by an exponential decrease. 175-375 mm of cumulated rainfall is needed before the runoff concentrations become less than EC50 values for fish (280 µg/l). The residual concentration in the runoff water remains above 4 µg/L even after 640 mm of rainfall. The level of benzalkonium ions leaching depends on the roofing material, with lower concentrations and total mass leached from ceramic tiles than from concrete tiles, and on the state of the tile (new or worn out). Mass balance calculations indicate that a large part of the mass of benzalkonium compounds applied to the tiles is lost, probably due to biodegradation processes.

Study of a large scale powdered activated carbon pilot: Removals of a wide range of emerging and priority micropollutants from wastewater treatment plant effluents.

The efficacy of a fluidized powdered activated carbon (PAC) pilot (CarboPlus(®)) was studied in both nominal (total nitrification + post denitrification) and degraded (partial nitrification + no denitrification) configuration of the Seine Centre WWTP (Colombes, France). In addition to conventional wastewater parameters 54 pharmaceuticals and hormones (PhPHs) and 59 other emerging pollutants were monitored in influents and effluents of the pilot. Thus, the impacts of the WWTP configuration, the process operation and the physico-chemical properties of the studied compounds were assessed in this article. Among the 26 PhPHs quantified in nominal WWTP configuration influents, 8 have high dissolved concentrations (>100 ng/L), 11 have an intermediary concentration (10-100 ng/L) and 7 are quantified below 10 ng/L. Sulfamethoxazole is predominant (about 30% of the sum of the PhPHs). Overall, 6 PhPHs are poorly to moderately removed (<60%), such as ibuprofen, paracetamol or estrone, while 9 are very well removed (>80%), i.e. beta blockers, carbamazepine or trimethoprim, and 11 are well eliminated (60-80%), i.e. diclofenac, naproxen or sulfamethoxazole. In degraded WWTP configuration, higher levels of organic matter and higher concentrations of most pollutants are observed. Consequently, most PhPHs are substantially less removed in percentages but the removed flux is higher. Thus, the PAC dose required to achieve a given removal percentage is higher in degraded WWTP configuration. For the other micropollutants (34 quantified), artificial sweeteners and phthalates are found at particularly high concentrations in degraded WWTP configuration influents, up to µg/L range. Only pesticides, bisphenol A and parabens are largely eliminated (50-95%), while perfluorinated acids, PAHs, triclosan and sweeteners are not or weakly removed (<50%). The remaining compounds exhibit a very variable fate from campaign to campaign. The fresh PAC dose was identified as the most influencing operation parameter and is strongly correlated to performances. Charge and hydrophobicity of compounds have been recognized as crucial for the micropollutant adsorption on PAC, as well as the molecular weight. Finally, a PAC dose of 10 mg/L allows an average removal of 72-80% of the sum of the PhPHs in nominal WWTP configuration. The comparaison of the results with those from the scarce other studies tends to indicate that an extrapolation of them to different PAC processes and to other WWTPs could be possible and relevant, taking into account the differences of water quality from WWTP to WWTP.

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.).

Dynamics of pollutant discharge in combined sewer systems during rain events: chance or determinism?

A large database of continuous flow and turbidity measurements cumulating data on hundreds of rain events and dry weather days from two sites in Paris (called Quais and Clichy) and one in Lyon (called Ecully) is presented. This database is used to characterize and compare the behaviour of the three sites at the inter-events scale. The analysis is probed through three various variables: total volumes and total suspended solids (TSS) masses and concentrations during both wet and dry weather periods in addition to the contributions of diverse-origin sources to event flow volume and TSS load values. The results obtained confirm the previous findings regarding the spatial consistency of TSS fluxes and concentrations between both sites in Paris having similar land uses. Moreover, masses and concentrations are proven to be correlated between Parisian sites in a way that implies the possibility of some deterministic processes being reproducible from one catchment to another for a particular rain event. The results also demonstrate the importance of the contribution of wastewater and sewer deposits to the total events' loads and show that such contributions are not specific to Paris sewer networks.

Assessment of the contribution of sewer deposits to suspended solids loads in combined sewer systems during rain events.

Within the French observatories network SOERE "URBIS," databases of continuous turbidity measurements accumulating hundreds of events and many dry weather days are available for two sites with different features (Clichy in Paris and Ecully in Lyon). These measurements, converted into total suspended solids (TSS) concentration using TSS-turbidity relationships and combined with a model of runoff event mean concentration, enable the assessment of the contribution of sewer deposits to wet weather TSS loads observed at the outlet of the two watersheds. Results show that the contribution of sewer deposits to wet weather suspended solid's discharges is important but variable (between 20 and 80 % of the mass at the outlet depending on the event), including a site allegedly free of (coarse) sewer deposits. The uncertainties associated to these results are assessed too.

Micropollutants in urban stormwater: occurrence, concentrations, and atmospheric contributions for a wide range of contaminants in three French catchments.

This study aimed at: (a) providing information on the occurrence and concentration ranges in urban stormwater for a wide array of pollutants (n = 77); (b) assessing whether despite the differences between various catchments (land use, climatic conditions, etc.), the trends in terms of contamination level are similar; and (c) analyzing the contribution of total atmospheric fallout (TAF) with respect to sources endogenous to this contamination. The studied contaminants include conventional stormwater contaminants (polycyclic aromatic hydrocarbons (PAHs), Zn, Cu, Pb, etc.), in addition to poorly or undocumented pollutants such as nonylphenol and octylphenol ethoxylates (NPnEO and OPnEO), bisphenol A (BPA), polybrominated diphenyl ethers (PBDEs), a wide variety of pesticides, and various metals of relevance (As, Ti, Sr, V). Sampling and analysis were performed using homogeneous methods on three urban catchments with different land use patterns located in three distinct French towns. For many of these pollutants, the results do not allow highlighting a significant difference in stormwater quality at the scale of the three urban catchments considered. Significant differences were, however, observed for several metals (As, Cr, Cu, Ni, Sr and Zn), PAHs, and PBDEs, though this assessment would need to be confirmed by further experiments. The pollutant distributions between dissolved and particulate phases were found to be similar across the three experimental sites, thus suggesting no site dependence. Lastly, the contributions of TAF to stormwater contamination for micropollutants were quite low. This finding held true not only for PAHs, as previously demonstrated in the literature, but also for a broader range of molecules such as BPA, NPnEO, OPnEO, and PBDEs, whose high local production is correlated with the leaching of urban surfaces, buildings, and vehicles.

Biofiltration vs conventional activated sludge plants: what about priority and emerging pollutants removal?

This paper compares the removal performances of two complete wastewater treatment plants (WWTPs) for all priority substances listed in the Water Framework Directive and additional compounds of interest including flame retardants, surfactants, pesticides, and personal care products (PCPs) (n = 104). First, primary treatments such as physicochemical lamellar settling (PCLS) and primary settling (PS) are compared. Similarly, biofiltration (BF) and conventional activated sludge (CAS) are then examined. Finally, the removal efficiency per unit of nitrogen removed of both WWTPs for micropollutants is discussed, as nitrogenous pollution treatment results in a special design of processes and operational conditions. For primary treatments, hydrophobic pollutants (log K ow > 4) are well removed (>70 %) for both systems despite high variations of removal. PCLS allows an obvious gain of about 20 % regarding pollutant removals, as a result of better suspended solids elimination and possible coagulant impact on soluble compounds. For biological treatments, variations of removal are much weaker, and the majority of pollutants are comparably removed within both systems. Hydrophobic and volatile compounds are well (>60 %) or very well removed (>80 %) by sorption and volatilization. Some readily biodegradable molecules are better removed by CAS, indicating a better biodegradation. A better sorption of pollutants on activated sludge could be also expected considering the differences of characteristics between a biofilm and flocs. Finally, comparison of global processes efficiency using removals of micropollutants load normalized to nitrogen shows that PCLS + BF is as efficient as PS + CAS despite a higher compactness and a shorter hydraulic retention time (HRT). Only some groups of pollutants seem better removed by PS + CAS like alkylphenols, flame retardants, or di-2-ethylhexyl phthalate (DEHP), thanks to better biodegradation and sorption resulting from HRT and biomass characteristics. For both processes, and out of the 68 molecules found in raw water, only half of them are still detected in the water discharged, most of the time close to their detection limit. However, some of them are detected at higher concentrations (>1 µg/L and/or lower than environmental quality standards), which is problematic as they represent a threat for aquatic environment.

Removal of alkylphenols and polybromodiphenylethers by a biofiltration treatment plant during dry and wet-weather periods.

This paper investigates the occurrence of alkylphenols (APs) and polybromodiphenylethers (PBDEs) in raw wastewater during dry and wet-weather periods, and their removal by physico-chemical lamellar settling and biofiltration techniques. Due to in-sewer deposit erosion and, to a lesser extent, to external inputs, raw effluents exhibit from 1.5 to 5 times higher AP and PBDE concentrations during wet periods compared with dry ones. The lamellar settler obtains high removal of APs and PBDEs under both dry and wet-weather flows (>53% for Σ(6)AP and >89% for Σ(4)PBDE), confirming the insensitivity of this technique to varying influent conditions. Indeed, despite the higher pollutant concentrations observed in raw effluents under wet-weather flows, adjusting the addition of coagulant-flocculent allows for efficient removal. By combining physical and biological processes, the biofiltration unit treats nutrient pollution, as well as Σ(6)AP and Σ(4)PBDE contamination (58 ± 5% and 75 ± 6% respectively). Although the operating conditions of the biofiltration unit are modified during wet periods, the performance in nutrient pollution, APs and light PBDE congeners remains high. Nevertheless, lower efficiency has been noted in nitrogen pollution, i.e. no denitrification occurs, and BDE-209 (not removed during wet-weather periods). In conclusion, this study demonstrates that the combination of both techniques treats AP and PBDE pollution efficiently during dry periods, but that they are also suitable for stormwater treatment.

Towards the determination of an optimal scale for stormwater quality management: micropollutants in a small residential catchment.

Stormwater and atmospheric deposits were collected on a small residential urban catchment (0.8 ha) near Paris in order to determine the levels of certain micropollutants (using a preliminary scan of 69 contaminants, followed by a more detailed quantification of PAHs, PCBs, alkylphenols and metals). Atmospheric inputs accounted for only 10%-38% of the stormwater contamination (except for PCBs), thus indicating substantial release within the catchment. On this small upstream catchment however, stormwater contamination is significantly lower than that observed downstream in storm sewers on larger adjacent urban catchments with similar land uses. These results likely stem from cross-contamination activity during transfers inside the sewer system and underscore the advantages of runoff management strategies at the source for controlling stormwater pollutant loads. Moreover, it has been shown that both contamination levels and contaminant speciation evolve with the scale of the catchment, in correlation with a large fraction of dissolved contaminants in upstream runoff, which differs from what has been traditionally assumed for stormwater. Consequently, the choice of treatment device/protocol must be adapted to the management scale as well as to the targeted type of contaminant.

Influence of the land use pattern on the concentrations and fluxes of priority pollutants in urban stormwater.

This paper presents the results of the concentrations (µg/L) and fluxes (g/ha) of priority substances in stormwater from three watersheds with different land use patterns (namely, residential, urban dense, high urban density). Samples were collected at the outlet of these watersheds. Thirteen chemical groups were investigated corresponding to 88 individual substances before treatment. Results showed that stormwater discharges contained 55 substances, among them some metals, organotins, PAHs, PCBs, alkylphenols, pesticides, phthalates, cholorophenols and volatile organic compounds. Therefore, stormwater was highly contaminated. However, this contamination was often comparable from site to site, since no significant difference of the pollutant load was observed between the land use patterns.

Efficiency of a turbidity-based, real-time control strategy applied to a retention tank: a simulation study.

This paper compares several real-time control (RTC) strategies for a generic configuration consisting of a storage tank with two overflow facilities. Two of the strategies only make use of flow rate data, while the third also introduces turbidity data in order to exercise dynamic control between two overflow locations. The efficiency of each strategy is compared over a wide range of system setups, described by two parameters. This assessment is performed by simulating the application of control strategies to actual measurements time series recorded on two sites. Adding turbidity measurements into an RTC strategy leads to a significant reduction in the annual overflow pollutant load. The pollutant spills spared by such a control strategy strongly depend on the site and on the flow rate based strategy considered as a reference. With the datasets used in this study, values ranging from 5 to 50% were obtained.

Relationship between turbidity and total suspended solids concentration within a combined sewer system.

This article confirms the existence of a strong linear relationship between turbidity and total suspended solids (TSS) concentration. However, the slope of this relation varies between dry and wet weather conditions, as well as between sites. The effect of this variability on estimating the instantaneous wet weather TSS concentration is assessed on the basis of the size of the calibration dataset used to establish the turbidity - TSS relationship. Results obtained indicate limited variability both between sites and during dry weather, along with a significant inter-event variability. Moreover, turbidity allows an evaluation of TSS concentrations with an acceptable level of accuracy for a reasonable rainfall event sampling campaign effort.

Zn and Pb emissions from roofing materials--modelling and mass balance attempt at the scale of a small urban catchment.

Many studies have shown that roofing materials are an important source of metals in urban runoff. Today, in the context of the European Water Directive (2000/60 CE), the quantification of these emissions is necessary, and thus the development of assessment tools is needed. This study focuses on a small urban catchment (drained by a separative sewer system). Atmospheric fallout, road runoff, roof runoff and total runoff at the outlet of the catchment were sampled. The aim is (1) to verify the contribution of roofing materials to metallic flows of Zn and Pb at the catchment scale and (2) to try to model emissions using some models previously developed at the test-bed scale. These models have to be tested at different spatial scales. Results obtained confirm the strong contribution of roofing materials to Zn and Pb flows at the catchment scale. For Zn, models tested were successfully transposed and validated at the roof and the catchment scales, permitting a good quantification of Zn emissions. For Pb, the use of the models highlights some difficulties, especially concerning the identification and the quantification of lead surface areas implemented.

Research of trace metals as markers of entry pathways in combined sewers.

Combined sewers receive high toxic trace metal loads emitted by various sources, such as traffic, industry, urban heating and building materials. During heavy rain events, Combined Sewer Overflows (CSO) can occur and, if so, are discharged directly into the aquatic system and therefore could have an acute impact on receiving waters. In this study, the concentrations of 18 metals have been measured in 89 samples drawn from the three pollutant Entry Pathways in Combined Sewers (EPCS): i) roof runoff, ii) street runoff, and iii) industrial and domestic effluents and also drawn from sewer deposits (SD). The aim of this research is to identify metallic markers for each EPCS; the data matrix was submitted to principal component analysis in order to determine metallic markers for the three EPCS and SD. This study highlights the fact that metallic content variability across samples from different EPCS and SD exceeds the spatio-temporal variability of samples from the same EPCS. In the catchment studied here, the most valuable EPCS and SD markers are lead, sodium, boron, antimony and zinc; these markers could be used in future studies to identify the contributions of each EPCS to CSO metallic loads.

Alkylphenols in atmospheric depositions and urban runoff.

A sampling campaign was conducted in order to determine alkylphenol (AP) concentrations in stormwater as well as potential AP sources in suburban environments. An analytical procedure was developed to quantify APs in bulk atmospheric deposition, building runoff, road runoff and stormwater. Both nonylphenols and octylphenols could be quantified in each sample. Median stormwater concentrations amounted to: 470 ng/l for nonylphenols, and 36 ng/l for octylphenols. These concentrations are 3 times higher than those found in atmospheric deposition, thus proving that local human activity constitutes a significant source of contamination. The contributions of the various sources to stormwater have been assessed from mass balances at the catchment scale. 70% of AP mass in stormwater originates from building and road emissions. Annual AP fluxes have been extrapolated from the total AP mass measured over our sampling periods for atmospheric depositions (44 to 84 µgNP/m(2)/yr) and stormwater (100 to 190 µgNP/m(2)/yr). Moreover, since APs were mainly found in the dissolved fraction, runoff treatment devices based on settling are unlikely to be very efficient.

Contributions of wastewater, runoff and sewer deposit erosion to wet weather pollutant loads in combined sewer systems.

An observatory of urban pollutants was created in Paris for the purpose of assessing the dynamics of wastewater and wet weather flow (WW and WWF) pollutant loads within combined sewers. This observatory is composed of six urban catchments, covering land areas ranging in size from 42 ha to 2581 ha. For a wide array of parameters including total suspended solids (TSS), chemical and biochemical oxygen demand (COD and BOD(5)), total organic carbon (TOC), total Kjeldahl nitrogen (TKN), heavy metals (Cu and Zn) and polycyclic aromatic hydrocarbons (PAHs), this article is intended to evaluate the contributions of wastewater, runoff and in-sewer processes to WWF pollutant loads through the use of an entry-exit mass balance approach. To achieve this objective, a total of 16 rain events were sampled on these sites between May 2003 and February 2006. This study has confirmed that at the considered catchment scale (i.e. from 42 ha to 2581 ha) the production and transfer processes associated with WWF pollutant loads do not vary with basin scale. Entry-exit chemical mass balances over all catchments and for a large number of rain events indicate that wastewater constitutes the main source of organic and nitrogenous pollution, while runoff is the predominant source of Zn. For Cu, PAHs and TSS, the calculation underscores the major role played by in-sewer processes, specifically by sediment erosion, as a source of WWF pollution. A significant loss of dissolved metals was also observed during their transfer within the sewer network, likely as a consequence of the adsorption of dissolved metals on TSS and/or on sewer deposits. Moreover, the nature of eroded particles was examined and compared to the various sewer deposits. This comparison has highlighted that such particles exhibit similar organic and PAH contents to those measured in the organic layer, thus suggesting that the deposit eroded during a wet weather period is organic and of a nature comparable to the organic layer. Despite the extent of initial field investigations, no organic deposit was observed to be present on sewer lines within the catchments, which implies that this organic deposit is probably present in another form or to be found elsewhere in the main trunks.

Annual metallic flows in roof runoff from different materials: test-bed scale in Paris conurbation.

A substantial database of annual metal runoff loads, obtained from a 14-month field exposure campaign on 12 different metal roofing materials at two sites within Paris conurbation, is presented herein. Thirteen metallic species have been considered. A comparison among the various roofing materials yields a ranking of their runoff pollution potential, which highlights that aluminum, coated products, and stainless steel display the lower emission levels, before zinc and copper materials. Lead materials appear to release more metallic species, and tend to do so in quite large quantities. Whatever the material family considered, older materials apparently release more metallic species with higher levels of emission. In considering zinc emissions from zinc-based materials, it is clear that surface coatings significantly reduce zinc emissions (40% less for the Zn3(PO4)2 surface-treated Anthra zinc, compared to natural zinc; and 99% less for prepainted galvanized steel compared to standard galvanized steel). In the case of Anthra zinc however, surface treatment induces the release of Ni into the runoff, and Ni constitutes a priority pollutant in the European Water Framework Directive (2000/60 CE). A high level of consistency with literature data has been found for Zn runoff when considering runoff rates reported at the same inclination.