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 μg l^?1, while metals tend to display concentrations above 10 μg l^?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 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.     

Contribution of treated wastewater to the microbiological quality of Seine River in Paris

Urban part of Seine River serving as drinking water supply in Paris can be heavily contaminated by Cryptosporidium spp. and Giardia duodenalis. In the absence of agricultural practice in this highly urbanized area, we investigated herein the contribution of treated wastewater to the microbiological quality of this river focusing on these two parasites. Other microorganisms such as faecal bacterial indicators, enteroviruses and oocysts of Toxoplasma gondii were assessed concurrently. Raw wastewaters were heavily contaminated by Cryptosporidium and Giardia (oo)cysts, whereas concentrations of both protozoa in treated wastewater were lower. Treated wastewater, flowed into Seine River, had a parasite concentration closed to the one found along the river, in particular at the entry of a drinking water plant (DWP). Even if faecal bacteria were reliable indicators of a reduction in parasite concentrations during the wastewater treatment, they were not correlated to protozoal contamination of wastewater and river water. Oocysts of T. gondii were not found in both raw and treated wastewater, or in Seine River. Parasitic contamination was shown to be constant in the Seine River up to 40 km upstream Paris. Altogether, these results strongly suggest that treated wastewater does not contribute to the main parasitic contamination of the Seine River usually observed in this urbanized area.     

Priority pollutants in urban stormwater: Part 1 – Case of separate storm sewers

Organic and mineral pollutants have become part of today's urban environment. During a rain event, stormwater quality as well as the corresponding contaminant loads is affected by both atmospheric deposition and the various types of impervious surfaces (roads, rooftops, parking lots etc.) on which runoff occurs. This study provides results on stormwater pollution in Paris and its suburbs from three separate storm sewers (n = 20 samples). These results show that the stormwater had been contaminated by 55 chemical substances out of the 88 investigated. A particular attention was given to stormwater particle contamination. Concentrations are provided for: metals, PAHs, PCBs, organotins, alkylphenols, phthalates, pesticides, and VOCs. Our findings are among the first available in the literature since the relevant analyses were all conducted on both the particulate (P) and dissolved (D) phases. For most substances, particles from the three storm sewers were more heavily contaminated than dredged sediments and settleable particles from the Seine River. As a consequence of this finding, the release of untreated stormwater discharges may impact the receiving waters and contribute to sediment contamination.     

The spatial and temporal trends of Cd, Cu, Hg, Pb and Zn in Seine River floodplain deposits (1994-2000)

Fresh floodplain deposits (FD), from 11 key stations, covering the Seine mainstem and its major tributaries (Yonne, Marne and Oise Rivers), were sampled from 1994 to 2000. Background levels for Cd, Cu, Hg, Pb, and Zn were established using prehistoric FD and actual bed sediments collected in small forested sub-basins in the most upstream part of the basin. Throughout the Seine River Basin, FD contain elevated concentrations of Cd, Cu, Hg, Pb and Zn compared to local background values (by factors>twofold). In the Seine River Basin, trace element concentrations display substantial downstream increases as a result of increasing population densities, particularly from Greater Paris (10 million inhabitants), and reach their maxima at the river mouth (Poses). These elevated levels make the Seine one of the most heavily impacted rivers in the world. On the other hand, floodplain-associated trace element levels have declined over the past 7 years. This mirrors results from contemporaneous suspended sediment surveys at the river mouth for the 1984-1999 period. Most of these temporal declines appear to reflect reductions in industrial and domestic solid wastes discharged from the main Parisian sewage plant (Seine Aval).     

Fecal bacteria in the rivers of the Seine drainage network (France): sources, fate and modelling

The Seine river watershed (France) is a deeply anthropogenically impacted area, due to the high population density, intense industrial activities and intensive agriculture. The water quality and ecological functioning of the different rivers of the Seine drainage network have been extensively studied during the last fifteen years within the framework of a large French multidisciplinary scientific program (PIREN Seine program). This paper presents a synthesis of the main data gained in the scope of this program concerning the microbiological water contamination of the rivers of the Seine drainage network. The more common indicator of fecal contamination (fecal coliforms) was mainly used; some complementary works used E. coli and intestinal enterococci as alternative fecal indicators. Point sources (outfall of wastewater treatment plants) and non point sources (surface runoff and soil leaching) of fecal pollution to the rivers of the watershed were quantified. Results showed that, at the scale of a large urbanised watershed as the Seine basin, the input of fecal micro-organisms by non-point sources is much lower than the inputs by point sources. However, the local impact of diffuse non-human sources (especially surface runoff of pastured fields) can be of major importance on the microbiological quality of small headwater rivers. Fecal contamination of the main rivers of the Seine watershed (Seine, Marne, Oise rivers) was studied showing high level of microbiological pollution when compared to European guidelines for bathing waters. The strong negative impact of treated wastewater effluents outfall on the microbiological quality of receiving rivers was observed in different areas of the watershed. Once released in rivers, culturable fecal bacteria disappeared relatively rapidly due to mortality (protozoan grazing, lysis) or loss of culturability induced by stress conditions (sunlight effect, nutrient concentration, temperature). Mortality rates of E. coli were studied in different types of rivers within the watershed showing, in summer conditions, no major difference in the mortality rates in small and large rivers. As a result of these studies, a module describing the dynamics of fecal bacteria has been developed and embedded within a hydro-ecological model describing the functioning of the rivers of the whole watershed (the SENEQUE model). Once validated, such a model can be used for testing predictive scenarios and thus can be a very useful tool for the management of microbiological water quality at the scale of the whole basin.     

Hydrological and chemical factors controlling the concentrations of Fe, Cu, Zn and As in a river system contaminated by acid mine drainage

The seasonal variations in the trace element concentrations and flow rates in the Carnon River system, south west England have been investigated on a monthly basis for a period of 1 yr. Approximately 85% of Fe, Zn and As, and 45% of Cu originate from mine waters. A strong seasonal dependence of the flux of trace elements in the natural and mine waters is observed. There appears to be a direct correlation between trace element concentrations and the proportion of infiltrated surface drainage in mine waters. Rises in these concentrations in the Carnon River due to increased fluxes from mine waters in winter months are offset by higher flow rates in surface discharge.Iron is transported predominantly in the particulate phase in Carnon River waters and virtually all dissolved Fe (< 0.45 μm) precipitates in estuarine waters. Dissolved concentrations of Cu, Zn and As appear to be regulated by sorptive processes particularly with Fe oxyhydroxides in both fresh and saline waters.     

Microbial partitioning to settleable particles in stormwater

The degree to which microbes in the water column associate with settleable particles has important implications for microbial transport in receiving waters, as well as for microbial removal via sedimentation (i.e. detention basins). The partitioning behavior of several bacterial, protozoan and viral indicator organisms is explored in three urban streams under both storm and dry weather conditions. The fraction of organisms associated with settleable particles in stormwater is estimated through use of a centrifugation technique which is calibrated using suspensions of standard particles (e.g., glass, latex). The fraction of organisms associated with settleable particles varies by type of microbe, and the partitioning behavior of each organism generally changes between dry weather and storm conditions. Bacterial indicator organisms (fecal coliforms, Escherichia coli, enterococci) exhibited relatively consistent behavior, with an average of 20-35% of organisms associated with these particles in background samples and 30-55% in storm samples. Clostridium perfringens spores exhibited the highest average level of particle association, with storm values varying from 50% to 70%. Results related to total coliphage partitioning were more variable, with 20-60% associated with particles during storms. These estimates should be valuable in surface water quality modeling efforts, many of which currently assume that all microbes exist as free (unattached) organisms.     

Partition of pollution between dissolved and particulate phases: what about emerging substances in urban stormwater catchments?

This paper presents results about the occurrence, the concentrations of urban priority substances on both the dissolved and the particulate phases in stormwater. Samples were collected at the outlet of a dense urban catchment in Paris suburb (2.30 km²). 13 chemical groups were investigated including 88 individual substances. Results showed that stormwater discharges contained 45 substances among them some metals, organotins, PAHs, PCBs, alkylphenols, pesticides, phthalates, cholorophenols and one volatile organic compound, i.e. methylene chloride. With respect to the European Water Framework Directive, these substances included 47% of the priority hazardous substances (n = 8), 38% of the priority substances (n = 10). The remaining substances (n = 27) belong to a list of others specific urban substances not included in the Water Framework Directive but monitored during this work. Finally, stormwater quality was evaluated by comparing the substance concentrations to environmental quality standards (EQS) and the particulate content to Canadian sediment quality guidelines. This showed that stormwater was highly contaminated and should be treated before being discharged to receiving waters in order to avoid any adverse impact on the river quality.     

Short-term variability of dissolved trace element concentrations in the Marne and Seine rivers near Paris

The concentrations of dissolved trace elements (Li, B, Mn, Cu, As, Rb, Sr, Mo, Cd, Ba, Pb) in the Marne and Seine rivers in the Paris urban area were monitored over a 2-year period. The resulting data indicated moderate contamination of waters by the most toxic elements (Cu, As, Cd and Pb). The River Marne upstream and the River Seine downstream of the city of Paris displayed similar concentrations. However higher fluxes of trace elements were observed in the Seine than in the Marne due to their different discharges. Li, B, Rb, Sr and Ba concentrations were correlated with river discharge and concentrations were higher during high river flow. This was interpreted as a dilution by discharge from a major natural or anthropogenic source. Mn, Cu, Mo, Cd and Pb concentrations were not correlated with discharge. Dissolved Mn, Cu and Cd increased rapidly in summer, whereas the concentration of Mo decreased. These variations were attributed to redox processes. During summer when the dissolved oxygen concentrations decrease, Mn, Cu, Cd and Pb are released into solution whereas Mo is immobilised. Like metals, variations in arsenic contents were not linked with discharge. Its similarity with phosphate distribution suggests similar controls involving phytoplankton uptake and release from sediments through organic matter mineralization.     

Nitrous oxide sources and sinks in coastal aquifers and coupled estuarine receiving waters

Sources and sinks of the atmospherically reactive gas nitrous oxide (N(2)O) were determined in the heavily nutrient loaded Childs River in Cape Cod, MA. Surface waters were supersaturated and bottom waters were depleted with N(2)O throughout the system. In apparent septic effluent plumes, N(2)O concentrations reached 3 orders of magnitude above atmospheric equilibrium. Because nitrate and N(2)O concentrations correlated in groundwater entering the estuary, septic tank effluent appeared responsible for the supersaturated concentrations of N(2)O in surface waters. A hyperbolic function fit nitrate and N(2)O concentrations in the water column of the estuary with a maximum supersaturation of approximately 60 nM. From surface water supersaturation we predicted a release of 480 nmol N(2)O m(-2) h(-1) to the atmosphere in the summer. Property plots of salinity vs. bottom-water N(2)O suggested a benthic sink of N(2)O. Consistent with this trend, sediments consumed rather than released N(2)O in most flux measurements. Nutrient loading did not directly alter benthic N(2)O flux, potentially because stratification limited exposure of sediments to nitrate-rich surface waters, but macroalgal cover increased benthic N(2)O consumption. Sediment N(2)O consumption averaged 111 nmol N(2)O m(-2) h(-1) and correlated with oxygen uptake. Losses from the system to the atmosphere and sediments exceeded inputs of N(2)O contaminated groundwater, which suggests missing N(2)O sources.     

Intra-storm variability in microbial partitioning and microbial loading rates

Association with particles in the water column can have a significant impact on microbial fate and transport. This study analyzed multiple stormwater samples taken throughout the duration of three separate storms (at two different sites) to evaluate the fraction of microbes partitioning to denser "settleable" particles and to examine how partitioning behavior varied over the course of a storm. Intra-storm sampling also allowed for estimates of microbial loading rates (both total and particle-associated) and cumulative storm-induced microbial load. Five different indicator organisms were examined, with the fraction of microbes associated with settleable particles assessed via a calibrated centrifugation method. Partitioning behavior varied across microorganism type, with an average of 40% of fecal coliforms, Escherichia coli, and enterococci associating with settleable particles, compared to approximately 65% of Clostridium perfringens spores and only 13% of total coliphage. Partitioning remained fairly constant for each type of organism throughout storm events. Nonetheless, higher concentrations of both settleable particles and microbes entering the water column soon after the onset of a storm led to higher loading rates of settleable microbes in the storm's earliest stages, a trend that could have important implications for the design of stormwater management structures (e.g., detention basins). Estimates of cumulative storm-induced microbial loading suggested that one day's worth of storm loading can be the equivalent of months, or even years, of dry-weather loading.     

Pharmaceuticals and personal care products (PPCPs) in surface and treated waters of Louisiana,USA and Ontario,Canada

A newly developed analytical method was used to measure concentrations of nine pharmaceuticals and personal care products (PPCPs) in samples from two surface water bodies, a sewage treatment plant effluent and various stages of a drinking water treatment plant in Louisiana, USA, and from one surface water body, a drinking water treatment plant and a pilot plant in Ontario, Canada. The analytical method provides for simultaneous extraction and quantification of the following broad range of PPCPs and endocrine-disrupting chemicals: naproxen; ibuprofen; estrone; 17beta-estradiol; bisphenol A; clorophene; triclosan; fluoxetine; and clofibric acid. Naproxen was detected in Louisiana sewage treatment plant effluent at 81-106 ng/l and Louisiana and Ontario surface waters at 22-107 ng/l. Triclosan was detected in Louisiana sewage treatment plant effluent at 10-21 ng/l. Of the three surface waters sampled, clofibric acid was detected in Detroit River water at 103 ng/l, but not in Mississippi River or Lake Pontchartrain waters. None of the other target analytes were detected above their method detection limits. Based on results at various stages of treatment, conventional drinking-water treatment processes (coagulation, flocculation and sedimentation) plus continuous addition of powdered activated carbon at a dosage of 2 mg/l did not remove naproxen from Mississippi River waters. However, chlorination, ozonation and dual media filtration processes reduced the concentration of naproxen below detection in Mississippi River and Detroit River waters and reduced clofibric acid in Detroit River waters. Results of this study demonstrate that existing water treatment technologies can effectively remove certain PPCPs. In addition, our study demonstrates the importance of obtaining data on removal mechanisms and byproducts associated with PPCPs and other endocrine-disrupting chemicals in drinking water and sewage treatment processes.     

Quality of dredged material in the river Seine basin (France). II. Micropollutants

Dredging rivers is needed to ensure safe navigable waters, rivers and waterways. To anticipate the management of dredged materials in the case of the river Seine basin, the quality of the sediments in the river is checked every 3 years before dredging operations. The river Seine Basin is heavily submitted to pollution pressure from nearby industrial activities and urban expansion of Paris and its region. Here, the micropollutant content of the sediment sampled in 1996, 1999 and 2000 before dredging is discussed compared to regulatory standards. The results indicate that most of the sediment samples from the river Seine basin are lightly to moderately contaminated with organic and inorganic micropollutants (heavy metals, PAH, PCB), which makes the management after dredging easier. This pollution is strongly correlated with the organic matter content and to the fine fraction (<50 microm) of the sediment. These results can lead to other management options than the ones already used in the river Seine basin: (1) dumping of lightly to moderately polluted sediments in quarries; and (2) physical treatment (sieving, hydrocycloning) of contaminated sediments issued from 'hot spots'.     

Use of microbial and toxicant screening tests for priority site selection of degraded areas in water bodies

In this study, a new approach has been taken to evaluate Saint John River water and sediment conditions. A battery of biochemical, microbiological and bioassay tests were used to identify degraded or degrading sediments and waters. Data were obtained from waters and sediments at 38 sites within the Saint John River Basin. The data suggested that the following four sites had the highest priority concern: Little River No. 34, Grand Bay, Saint John River near Boars Head No. 33, Madawaska River below mill No. 7 and St Francois-de-Madawaska, mill stream No. 2. The data also indicated that microbial population, biochemical or bioassay tests performed independently do not provide realistic evaluations of priority concern areas and that the “battery of tests” approach is necessary to provide additional information.     

Perfluorinated compounds in surface waters and WWTPs in Shenyang, China: mass flows and source analysis

Concentrations of 10 perfluorinated chemicals (PFCs) were investigated in the Hun River (HR), four canals, ten lakes, and influents and effluents from four main municipal wastewater treatment plants (WWTPs) in Shenyang, China. Mass flows of four main PFCs were calculated to elucidate the contribution from different sections of the HR. Overall, perfluorooctanoic acid (PFOA) and perfluorohexanoic acid (PFHxA) were the major PFCs in the HR, with ranges of 2.68-9.13 ng/L, and 2.12-11.3 ng/L, respectively, while perfluorooctane sulfonate (PFOS) was detected at lower levels, ranging from 0.40 to 3.32 ng/L. The PFC concentrations in the HR increased after the river passes through two cities (Shenyang and Fushun), indicating cities are an important contributor for PFCs. Mass flow analysis in the HR revealed that PFC mass flows from Fushun are 1.65-5.50 kg/year for C6-C8 perfluorinated acids (PFCAs) and 1.29 kg/year for PFOS, while Shenyang contributed 2.83-5.18 kg C6-C8 PFCAs/year, and 3.65 kg PFOS/year. The concentrations of PFCs in four urban canals were higher than those in the HR, with the maximum total PFCs of 240 ng/L. PFOA and PFOS showed different trends along these canals, suggesting different sources for the two PFCs. Total PFCs in ten lakes from Shenyang were at low levels, with the greatest concentration (56.2 ng/L) detected in a heavily industrialized area. The PFC levels in WWTP effluents were higher than those in surface waters with concentrations ranging from 18.4 to 41.1 ng/L for PFOA, and 1.69-3.85 ng/L for PFOS. Similar PFC profiles between effluents from WWTPs and urban surface waters were found. These results indicate that WWTPs are an important PFC source in surface water. Finally, we found that the composition profiles of PFCs in surface waters were similar to those in tap water, but not consistent with those in adult blood from Shenyang. The calculation on total daily intake of PFOS by adults from Shenyang showed that the contribution of drinking water to human exposure was minor.     

PM10 composition during an intense Saharan dust transport event over Athens (Greece)

The influence of Saharan dust on the air quality of Southern European big cities became a priority during the last decade. The present study reports results on PM₁₀ monitored at an urban site at 14 m above ground level during an intense Saharan dust transport event. The elemental composition was determined by Energy Dispersive X-ray Fluorescence Spectrometry (EDXRF) for 12 elements: Si, Al, Fe, K, Ca, Mg, Ti, S, Ni, Cu, Zn and Mn. PM₁₀ concentrations exceeded the EU limit (50 μg/m³) several times during the sampling period. Simultaneous maxima have been observed for the elements of crustal origin. The concentrations of all the elements presented a common maximum, corresponding to the date where the atmosphere was heavily charged with particulate matter permanently for an interval of about 10 h. Sulfur and heavy metal concentrations were also associated to local emissions. Mineral dust represented the largest fraction of PM₁₀ reaching 79%. Seven days back trajectories have shown that the air masses arriving over Athens, originated from Western Sahara. Scanning Electron Microscopy coupled with Energy Dispersive X-ray analysis (SEM-EDX) revealed that particle agglomerates were abundant, most of them having sizes < 2 μm. Aluminosilicates were predominant in dust particles also rich in calcium which was distributed between calcite, dolomite, gypsum and Ca-Si particles. These results were consistent with the origin of the dust particles and the elemental composition results. Sulfur and heavy metals were associated to very fine particles < 1 μm.     

PCB pollution behaviour in the River Seine

The contamination of the River Seine (France) and its main tributaries (Yonne, Marne, Oise) have been studied, under different hydrological conditions, at the end of spring before the low watermark and at the beginning of autumn after the first swelling of flow.The sector under study consists of the Seine basin, centered on the Paris area; the variability of PCB concentration in water, apart from flow dependence, shows that important lateral discharges are involved. The pollution level is particularly noticeable at Paris and downstream from Paris and the median concentration in sediments reaches 3800 ng l⁻¹ (ppb). Data on particulate organic carbon and various grain size fractions show the PCB to be preferentially adsorbed on organic-rich sedimentary particles.Partition coefficients between particulate matter and liquid phase have been computed and show that the liquid phase has the main role in micropollutant transport.     

Mass balance for polycyclic aromatic hydrocarbons in the urban watershed of Le Havre (France): transport and fate of PAHs from the atmosphere to the outlet

Polycyclic aromatic hydrocarbon (PAH) concentrations have been monitored simultaneously in ambient air, bulk atmospheric deposition and runoff waters during one year in a small urban watershed of the Seine river basin (France). PAH fluxes from the atmosphere to the outlet of the urban watershed have been calculated to establish a mass balance for PAHs. PAH flux in runoff waters was 5.2 kg km(-2) yr(-1) while PAH atmospheric deposition was 0.21 kg km(-2) yr(-1). The comparison between atmospheric input and output by runoff has shown the importance of street deposits that appeared to be the most important source of PAHs for surface waters in urban areas. PAH profiles in the various compartments showed the fate of PAHs in the air-water system: proportion of carcinogenic PAHs was more important in runoff waters (35%) than in bulk atmospheric deposition (22%) and air (6%).     

Quality of dredged material in the River Seine basin (France). I. Physico-chemical properties

In rivers, sediments are frequently accumulating persistent chemicals, especially for those that are more contaminated as a consequence of pressure related to environmental pollution and human activity. The Seine river basin (France) is heavily polluted from nearby industrial activities, and the urban expansion of Paris and its suburbs within the Ile de France region and the sediments present in the Seine river basin are contaminated. To ensure safe, navigable waters, rivers and waterways must be dredged. In this paper, the quality of the sediment dredged in 1996, 1999 and 2000 is discussed. Physico-chemical characteristics of the sediment itself and of the pore-water are presented. Seine basin sediments show very diverse compositions depending on the sampling site. Nevertheless, a geographic distribution study illustrated that the Paris impact is far from being the only explanation to this diversity, the quality of this sediment is also of great concern. The sediment once dredged is transported via barges to a wet disposal site, where the dredged material is mixed with Seine water in order to be pumped into the receiving site. This sort of dumping might be responsible for the potential release of contaminants to the overlying water from the significantly contaminated sediments.