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.

Labile, dissolved and particulate PAHs and trace metals in wastewater: passive sampling, occurrence, partitioning in treatment plants.

The occurrence and the partitioning of polycyclic aromatic hydrocarbons (PAHs) and seven metals (Al, Cd, Cr, Cu, Ni, Pb and Zn) were investigated in activated sludge wastewater treatment plants by means of passive and active sampling. Concentrations total dissolved and particulate contaminants were determined in wastewater at several points across the treatment system by means of grab sampling. Truly dissolved PAHs were sampled by means of semipermeable membrane devices. Labile (inorganic and weakly complexed) dissolved metals were also sampled using the diffusive gradient in thin film technique. This study confirms the robustness and the validity of these two passive sampling techniques in wastewater. All contaminant concentrations decreased in wastewater along the treatment, although dissolved and labile concentrations sometimes increased for substances with less affinity with organic matter. Solid-liquid and dissolved organic matter/water partitioning constants were estimated. The high variability of both partitioning constants for a simple substance and the poor relation between K(D) and K(OW) shows that the binding capacities of particles and organic matter are not uniform within the treatment and that other process than equilibrium sorption affect contaminant repartition and fate in wastewater.

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.

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.

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.

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.