Time-varying microplastic contributions of a large urban and industrial area to river sediments.

The quantification of microplastic (MP) pollution in rivers is often constrained by a lack of historical data on a multi-decadal scale, which hinders the evaluation of public policies. In this study, MP contents and trends were analyzed in dated sediment cores sampled upstream and downstream of a large metropolis, in environmental deposits that exhibited consistent sedimentation patterns from the 1980s to 2021. After a thorough sedimentological analysis, MPs were quantified in samples by micro Fourier Transform InfraRed spectroscopy (µFTIR imaging) and a density separation and organic matter digestion procedure. Microplastics recorded in the upstream core are relatively ubiquitous all along the dated sequence. The results also confirmed a sever increase of microplastics levels in the downstream core, by one order of magnitude, and an increase of polymer types. Polypropylene, polyethylene, and polystyrene represent ubiquitous contamination and were predominant at the two stations, whereas polyvinyl chloride and polytetrafluoroethylene were suspected to be abundant at the downstream station, but were not detected at the upstream station. Their presence could be linked to local contamination from specific industrial sources that manufactured and utilized these polymers. Surprisingly, in the downstream station sediment has recorded a relative improvement in polymers associated with industrial sources since the 2000s and, to a lesser extent, for ubiquitous ones since the 2010s. This trend of mitigation diverges from that of global assessments, that assume uncontrolled MP pollution, and suggest that European Union wastewater policy and regulation on industrial discharges have positively influenced water quality, and certainly also on MPs. However, the accumulation of microplastics remains high in recent deposits and raises the emerging concern of the long-term management of these reservoirs.

Organophosphate ester additives and microplastics in benthic compartments from the Loire estuary (French Atlantic coast).

We report the first empirical confirmation of the co-occurrence of organophosphate esters (OPEs) additives and microplastics (MPs) in benthic compartments from the Loire estuary. Higher median concentrations of MPs (3387 items/kg dw), ∑13tri-OPEs (12.0 ng/g dw) and ∑4di-OPEs (0.7 ng/g dw) were measured in intertidal sediments with predominance of fine particles, and under higher anthropogenic pressures, with a general lack of seasonality. Contrarily, Scrobicularia plana showed up to 4-fold higher ∑tri-OPE concentrations in summer (reaching 37.0 ng/g dw), and similar spatial distribution. Polyethylene predominated in both compartments. Tris(2-ethylhexyl) phosphate (TEHP), its degradation metabolite (BEHP) and tris-(2-chloro, 1-methylethyl) phosphate (TCIPP) were the most abundant OPEs in sediments, while TCIPP predominated in S. plana. The biota-sediment accumulation factors suggest bioaccumulation potential for chlorinated-OPEs, with higher exposure in summer. No significant correlations were generally found between OPEs and MPs in sediments suggesting a limited role of MPs as in-situ source of OPEs.

Microplastic trapping in dam reservoirs driven by complex hydrosedimentary processes (Villerest Reservoir, Loire River, France).

Dam reservoirs can strongly influence the spatial distribution of sediment pollution by microplastics (MP). The Villerest reservoir (Loire River, 36 km long) is a good candidate to study the relationship between MP pollution and hydrosedimentary processes. Sediments were collected from the dam-controlled river section and from 3 km downstream. Geomorphological and sedimentological analyses were performed and microplastics were analysed using µFTIR imaging (polymer identification for particle sizes ≥ 25 µm). This paper highlights strong MP levels (on an order of 104 items/kg dw) over the section characterized by fine-grained sediments (FGS). In coarse-grained sediments (CGS), at the upstream part of the reservoir and downstream of the dam, levels are one order of magnitude lower. FGS are indicator of long-time settling processes. Such conditions lead to foster the MP trapping as low-density suspended materials in the water column. CGS deposits originate from the river bed load. These sediments are transported in high-velocity and high-turbulent flow conditions. Moreover, post-depositional reworking of the finest fraction can occur according to hydrofluctuations. Here are adverse conditions for the MP trapping. The polymer diversity is also higher in FGS than in CGS. However, the range of plastic particle sizes is similar in FGS and CGS and is not related to the sediment grain-size distribution. Moreover, in both FGS and CGS, the polymer abundance is not correlated with the grain-size distribution or with the organic matter content. In the reservoir context, a change in the polymer partition appears over the FGS section in the downstream direction, depending on the polymer density. From a fundamental point of view, this work contributes to improving our understanding of the key role played by hydrosedimentary processes in MP repartition. These findings also have operational scopes, providing significant elements to advocate for a better consideration of MP pollution during sediment management operations.

Macroplastic transfer dynamics in the Loire estuary: Similarities and specificities with macrotidal estuaries.

The quantification of macroplastic fluxes transferred by rivers toward the pelagic environment requires a better understanding of macrodebris transfer processes in estuarine environments. Following the strategy adopted in the Seine estuary, this study aims to characterize macroplastic trajectories in the Loire estuary. Between January 2020 and July 2021, 35 trajectories were monitored using plastic bottles equipped with GPS-trackers. With total travelled distances between 100 m and 103.6 km, trajectories show great spatiotemporal variability. The various forcing factors (macroplastic buoyancy, estuaries tidal and hydrometeorological conditions, geomorphology and vegetation) lead to chaotic trajectories, preventing accurate predictions in macroplastic transfer and storage/remobilization dynamics. In the Loire estuary like in the Seine one, no tracked bottle reached the Atlantic Ocean. It confirms that macrotidal estuaries under temperate climates constitute accumulation zones and slow pathways for macroplastics, but raises question on the real fluxes transferred from continental areas to oceans.

Amount, composition and sources of macrolitter from a highly frequented roadway.

Many researches mention the need to identify the land-based sources of riverine macrolitter but few field data on litter amount, composition and sources are available in the scientific literature. Describing macrolitter hotspot dynamics would actually allow a better estimation of fluxes in the receiving environments and a better identification of the more appropriate mitigation strategies. This study provides new insights in roadway macrolitter production rates, typologies and input sources (i.e. deliberate or accidental). The macrolitter from an 800 m portion of a highly frequented roadway (around 90,000 vehicles per day) was collected during almost one year. Typologies were defined using the OSPAR/TGML classification. Results show high annual loads of macrolitter (42.8 kg/yr/ha), suggesting significant contributions of the road runoff to the litter fluxes in urban stormwater. Over the course of a year, 88.5 kg of debris were collected, including 53.2 kg (60%) of plastic debris. In total, 36,439 items were characterized, of which 84% were plastics. The macrodebris collected present a low diversity of components with Top 10 items accounting for 92% by count and a majority of small and lightweight items like plastic fragments (31%) or cigarette butts (18%). Input sources were estimated for 43% of the mass collected in which 37.2% were deliberately littered and 62.8% were accidental leaks, illustrating a major contribution of uncovered trucks and unsecured loads. The accumulation rates show a linear correlation with the road traffic. Such data are of prime interest since they enable to determine the potential contribution of road traffic to plastic fluxes to the environment.

Riverine litter in a small urban river in Marseille, France: Plastic load and management challenges.

Small urban rivers are thought to be major sources of riverine litter, especially macroplastics, into the ocean. In well-developed countries, waste management infrastructures and recovery systems are sometimes implemented to prevent their emission into the sea meeting environmental and economic goals. The Huveaune River in Marseille, South of France, is a typical case study showing a non-negligible and uncontrolled leakage of riverine litter remains, despite all recovery systems implemented. Giant bar screens are settled over the river to collect riverine litter from the whole water column before water is released into the Sea. In this paper, screened material was characterized during a dry, wet and heavy rainfall period and annual macroplastic mass flows were estimated. The plastic fraction represented 83% by count of the 3147 items sorted and counted. Mass flow of plastic debris ranged between 1.1 and 5.8 mt/yr (equivalent to 2.1-11.4 g/cap/yr), in which 0.4-2.1 mt/yr (equivalent to 0.8-4.1 g/cap/yr) are bypassed to the sea during heavy rainfall periods. Giant bar screens across the Huveaune River prevent 65% of the mass flow to reach the sea annually, but 35% remain uncontrolled. When compared to the Seine River and other European Rivers, macroplastic leakage into the ocean per capita may range between 1 and 10 g/cap/yr. This suggests that end-of-pipe solutions are not enough and further supports urgent regulations of the plastic production on local to global scales to tackle the plastic pollution at its source.

Transfer dynamics of macroplastics in estuaries - New insights from the Seine estuary: Part 3. What fate for macroplastics?

Macroplastic emissions from the Seine estuary to the English Channel were estimated using institutional cleaning of riverbanks, combined with a tagged litter experiment. Cleaning were performed between March 2018 and April 2019 by the non-profit company Naturaul'un over 19 sites covering 20 km of riverbanks. A total of 365 tagged litter (90% macroplastics) was released in the estuary in March (n = 200), at the end of the winter/spring flood 2018, in July (n = 58), August (n = 56) and September 2018 (n = 51) during low river flow periods. Over the total tagged litter, 102 (28%) were recovered by Naturaul'un. Relative to the total amount of macroplastics (>5 cm) collected and the estimated amount of smaller/hidden macroplastics (>5 mm) not collected, the maximum macroplastic emission to the English Channel was estimated to be ~100-200 metric tons per year.

Fate of emerging and priority micropollutants during the sewage sludge treatment - Part 2: Mass balances of organic contaminants on sludge treatments are challenging.

This paper analyzes the fate of 71 priority and emerging organic contaminants all along the treatment trains of sewage sludge treatment facilities in Paris including dewatering by centrifugation, thermal drying and anaerobic digestion. It aimed at proposing and applying a mass balances calculation methodology to each process and pollutant. This data validation strategy demonstrated the complexity to perform representative inlet/outlet sampling and analysis campaigns at industrial scales regarding organic compounds and to propose options to overcome this issue. Centrifugation and drying processes only implied physical mechanisms as phase separation and water elimination. Hence, correct mass balance were expected observed for organic contaminants if sampling and analysis campaigns were representative. This was the case for hydrophobic and neutral compounds. For the other more hydrophilic and charged compounds, the mass balances were scarcely correct. Thus, the conventional sampling and analytical practices used with sludge should be questioned and adapted to better take into account the high heterogeneity of sludge and the evolution of matrix effect within sludge treatment processes on micropollutant determination. For the biological anaerobic digestion process where degradations can occur and removals can be observed, the mass balances were deeply interpreted for 60 contaminants. This process contributed to the elimination above 70% of 21 detected compounds including 16 pharmaceuticals, 2 phthalates, 2 hormones and 1 perfluorinated compound. Removals of domperidone, propranolol, escitalopram, lidocaine, verapamil and cefoperazone under this condition were reported for the first time.

Transfer dynamics of macroplastics in estuaries - New insights from the Seine estuary: Part 2. Short-term dynamics based on GPS-trackers.

The dynamics of plastic debris were assessed in the Seine River, especially in the estuary, using plastic bottles equipped with GPS-trackers. In one year, 50 trajectories were recorded, covering a wide range of hydrometeorological conditions. Results show a succession of stranding/remobilization episodes in combination with alternating upstream and downstream transport in the estuary. In the end, 100% of the tracked bottles stranded somewhere, for hours or weeks, from one to several times at different sites. The overall picture shows that different physical phenomena interact with various time scales ranging from hours/days (high/low tides) to weeks/months (spring/neap tides and highest tides) and years (seasonal river flow). Thus, the fate of plastic debris is highly unpredictable, but the consequence of those interactions is that the transfer of debris is chaotic and not straightforward, and its residence time is much longer than the transit time of water.

Transfer dynamic of macroplastics in estuaries - New insights from the Seine estuary: Part 1. Long term dynamic based on date-prints on stranded debris.

Rivers are a major pathway for plastics between lands and the ocean. At the land-ocean interface, estuaries make the transfer dynamic of plastics complex and nonlinear. That is why very little is known about this dynamic. In this respect, a specific marker (i.e. Microlax packaging) showing date-prints was systematically investigated in different riverbanks of the Seine estuary to identify the share of "old" and "recent" litter transiting through the estuary toward the ocean. Up to 70% of Microlax were "old" plastic items probably related to the meandering dynamic of the river over large time and space scales, and hydrodynamic conditions (tides) at smaller scales. This contributes together to increase the residence time of plastics into the estuary up to decades with almost endless transport, deposit and remobilization cycles. Consequently, the Seine estuary may function as a "microplastic factory" resulting from the fragmentation of macroplastics into microplastics well before they reach the ocean.

Non-target strategies by HRMS to evaluate fluidized micro-grain activated carbon as a tertiary treatment of wastewater.

Among the release solutions for reducing the discharge of organic and persistent contaminants in the aquatic environment, the use of a tertiary treatment in addition to existing conventional wastewater treatment processes is considered. The use of micro-grain activated carbon in a fluidized bed is a promising technique investigated in this study. The effluents from a large-scale pilot system were analyzed by liquid chromatography coupled with high-resolution mass spectrometry (QToF). Several strategies were deployed, namely molecular fingerprint comparison, suspected and non-target analyses, identification of refractory compounds to treatment, and finally, quantification of identified compounds. The evaluation of the molecular fingerprints provided evidence of the overall effect of the tertiary treatment on the treated wastewater quality. The suspected approach highlighted the presence of 83 pharmaceuticals and pesticides as well as transformation products in the effluents. The non-target approaches also highlighted compounds refractory to tertiary treatment, such as illicit drugs or some pharmaceuticals. The identification and quantification of identified compounds underscored the suitability of micro-grain activated carbon in eliminating many classes of pharmaceuticals with various physicochemical properties, such as anti-hypertensive, analgesic, anti-viral, antidepressant and even various pesticides.

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.

Temporal trends of persistent organic pollutants in dated sediment cores: Chemical fingerprinting of the anthropogenic impacts in the Seine River basin, Paris.

Persistent organic pollutants (POPs) were extensively produced and used throughout the last century. In the early 1980s, a rising concern on the environmental impact of these chemicals has led to the establishment of regulations and changes of use including bans. Long term monitoring of the environmental impacts of these emissions and regulations is a challenge because regular monitoring was not mandatory at the beginning of the first emissions. Moreover, the analytical methods have been strongly improved over the decades. To overcome the lack of monitoring and accurate data, sediment cores are powerful tools to construct contamination records. In this study, a high resolution record was constructed for four POPs families (13 polycyclic aromatic hydrocarbons (PAHs), 15 polychlorinated biphenyls (PCBs), 3 alkylphenols (APs) and 8 polybromodiphenyl ethers (PBDEs)) to establish their historical trends in a long-term urbanized and industrialized environment: the Seine River basin, France. These specific families were selected because they had different sources, uses and histories. The results showed concentrations up to 90 mg/kg for ∑PAHs, 2.3mg/kg for ∑PCB, 1.2mg/kg for ∑APs and 0.06 mg/kg for ∑PBDE. The vertical distribution profiles were different from one family to another and presented a good correlation with uses (e.g. transition from coal to natural gas for PAHs), and regulation implementation (e.g., AP ban after "OSPAR Convention" in 1992). The study of compounds distribution provided original information on sources, e.g. temporal variations in PAH uses. This study demonstrates the usefulness and accuracy of sedimentary archives in floodplain to assess the fate of POPs through time in continental hydrosystems. These first results give a comprehensive overview of the contamination in the Seine River basin downstream of Paris Megacity. They were in good agreement with previous studies dedicated to European areas and highlighted specificities of this basin that were not reported before.

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.

Phthalates and alkylphenols in industrial and domestic effluents: case of Paris conurbation (France).

Phthalates and alkylphenols are toxics classified as endocrine disrupting compounds (EDCs). They are of particular concern due to their ubiquity and generally higher levels found in the environment comparatively to other EDCs. Industrial and domestic discharges might affect the quality of receiving waters by discharging organic matter and contaminants through treated waters and combined sewer overflows. Historically, industrial discharges are often considered as the principal vector of pollution in urban areas. If this observation was true in the past for some contaminants, no current data are today available to compare the quality of industrial and domestic discharges as regards EDCs. In this context, a total of 45 domestic samples as well as 101 industrial samples were collected from different sites, including 14 residential and 33 industrial facilities. This study focuses more specifically on 4 phthalates and 2 alkylphenols, among the most commonly studied congeners. A particular attention was also given to routine wastewater quality parameters. For most substances, wastewaters from the different sites were heavily contaminated; they display concentrations up to 1200 µg/l for di-(2-ethylhexyl) phthalate and between 10 and 100 µg/l for diethyl phthalate and nonylphenol. Overall, for the majority of compounds, the industrial contribution to the flux of contaminant reaching the wastewater treatment plants ranges between 1 and 3%. The data generated during this work constitutes one of the first studies conducted in Europe on industrial fluxes for a variety of sectors of activity. The study of the wastewater contribution was used to better predict the industrial and domestic contributions at the scale of a huge conurbation heavily urbanized but with a weak industrial cover, illustrated by Paris. Our results indicate that specific investigations on domestic discharges are necessary in order to reduce the release of phthalates and alkylphenols in the sewer systems for such conurbations.

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.).

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.