A survey of heavy metals in municipal wastewater in combined sewer systems during wet and dry weather periods

During wet weather, combined sewer system overflows affect the quality of water in watercourses. For planning overflows, the lowest possible load of priority substances according to Directive 2008/105/EC is crucial and the knowledge of variability in concentrations of elements in the sewer system is necessary. The behaviour of heavy metals in a sewer system was observed in the course of dry weather flow (DWF) and wet weather flow (WWF). We found, from the comparison of concentration medians for the WWF and DWF that during wet weather periods, an increase in the concentrations of As, Cr, Cd, Pb, Mn and Fe occurs in the sewer system and the effect of nonpoint sources manifests itself. Zn, Cu and Ni concentrations decreased during wet weather periods, and Hg concentrations did not significantly change. During the WWF period, a considerable nonhomogeneity of the sewage system was demonstrated.     

Contribution of different sources to the pollution of wet weather flows in combined sewers

Experiments performed on "Marais" catchment, in central Paris, aimed to follow up the quality of wet weather flows from the entry to the exit of a combined sewer network. SS, VSS, COD, BOD5, Cd, Cu, Pb, Zn concentrations were measured for an important number of rain events in roof, yard, street runoff, as well as in dry and wet weather flows at the catchment outlet. Mass entry-exit totals, at the scale of the catchment, were calculated over 31 rain events in order to evaluate the contribution of different types of runoff, of sanitary sewage and of sewer sediments to the total wet weather pollutant loads at the catchment outlet. The erosion of in-sewer pollutant stocks was found to be the main source of particles and of organic matter in wet weather flows, whereas heavy metal loads mainly originated from roof runoff, due to the corrosion of metallic roofs. Particles eroded inside the sewer during rain events were found to be quite different from the particles constituting the main part of sewer sediments: they are organic and biodegradable, with rather important settling velocities and seem to accumulate during dry weather periods. A change of the chemical form of heavy metals was noticed during the transport in the sewer and it is suspected that a fraction of the dissolved metals from the runoff is adsorbed on sewer sediments.     

The physical factors affecting heavy metals accumulated in the sediment deposited on road surfaces in dry weather: a review

The main objective of this review is to identify and analyse physical factors (PF) involved in the heavy metal accumulation phenomenon in the road-deposited sediment (RDS) in dry weather. Electronic databases were used to establish an order of prevalence by establishing quartiles (Q-citation frequency) for the PF identified. The results show that the eleven PF can most likely be classified into three categories: climatic-anthropogenic-morphometric. The studies most frequently referenced land use (Q1), rainfall (Q2), particle size (Q2) and vehicles (Q3) as key PF. There is a similar behaviour between the concentrations of Zn-Pb-Cu associated with the RDS in dry weather and the dissolved fraction washed from the surface in road runoff. The size fraction <250 μm is representative of RDS to characterize the metals. The review expands knowledge about the influences of the PF in the processes of deposition-suspension-interception-removal of the metals load in road environments.     

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 BOD₅), 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.     

Regression models for estimating storm runoff load and its application to Lake Kasumigaura

Regression models are proposed for accurate estimation of storm runoff load. Regression equations are obtained for the relationship between final cumulative load and flow during direct runoff by each storm event. The models are applied to estimate annual nutrients load by all influent rivers into the Lake Kasumigaura for a model year of average annual rainfall. The load in dry weather is calculated from observed data of all influent rivers. Total annual load for a year is the sum of loads in dry weather days and loads in wet weather days. The ratios of the load in a wet weather day to total annual loads are 29 percent for T‐N, 51 percent for T‐P, 53 percent for T‐COD, 22 percent for D‐N, 22 percent for D‐P and 30 percent for D‐COD.     

PCB dry and wet weather concentration and load comparisons in Houston-area urban channels

All 209 PCB congeners are quantified in water in both dry and wet weather urban flows in Houston, Texas, USA. Total water PCBs ranged from 0.82 to 9.4 ng/L in wet weather and 0.46 to 9.0 ng/L in dry. Wet weather loads were 8.2 times higher (by median) than dry weather with some increases of over 100-fold. The majority of the PCB load was in the dissolved fraction in dry weather while it was in the suspended fraction in wet weather. Dissolved PCB loads were correlated with rain intensity and highly developed land area, and a multiple linear regression (MLR) equation was developed to quantify these correlations. PCA generated five PCB components with nearly all positive loadings. They were interpreted as DOC-associated A1248, wet weather primarily suspended fraction A1254/A1260 likely from building sealants, truly dissolved-associated wastewater dechlorination, watershed-sourced PCB 11, and monochlorinated PCBs (likely connected to a different state or source of dechlorination). The PCB 11 component was statistically higher in wet versus dry weather when no other component showed such clear distinctions. Hierarchical cluster analysis (HCA) did not always group dry and wet weather samples from the same location together illustrating the different congener composition that often exists between dry and wet conditions. Four wet weather samples from high percentage developed land (> 90%) watersheds had nearly the same fingerprint suggesting a generic “urban” signature in runoff, which in this case was caused by residual A1254/A1260 PCB stocks and currently produced PCB 11 in consumer goods.     

Spatial variability of the characteristics of combined wet weather pollutant loads in Paris

An on-site observatory of urban pollutant loads in combined sewers has been created in Paris in order to investigate wet weather pollutant loads at different spatial scales. This observatory is composed of six urban catchments, covering areas from 41 to 2581ha. For a wide range of parameters including suspended solids (SS), volatile suspended solids (VSS), chemical oxygen demand (COD), biochemical oxygen demand (BOD5), total organic carbon (TOC), total Kjeldahl nitrogen (TKN), metals (Cd, Cu, Pb, Zn), aliphatic hydrocarbons and polycyclic aromatic hydrocarbons (AHs and PAHs), this article serves to evaluate the potential scale effect on wet weather flow (WWF) quality. Although the extensive data set compiled herein has emphasized the high variability in WWF quality from one rain event to the next, no scale effect could be observed for a given rain event on pollutant concentrations, distributions between dissolved and particulate phases, pollutant contents and loads. Such results are of prime importance since they suggest (i) no spatial scale influence on WWF quality for the considered catchments and (ii) similar dominant sources and transfer processes at the various spatial scales.     

Stormwater quality associated with a silt trap (empty and full) discharging into an urban watercourse in Scotland

The aim was to assess the influence of a full silt trap at the end of a stormwater drainage pipe on the water quality of stormwater discharged into a semi‐natural urban watercourse. For approximately eleven weeks, the water qualities of the preliminarily treated stormwater and of the receiving watercourse (Braid Burn) were studied. The mean outflow concentrations of suspended solids were 2.0 mg/l and 34.1 mg/l during dry and wet weather conditions, respectively. Suspended solids concentrations of up to 141.6 mg/l were recorded during storm events. Suspended solids values for treated stormwater were often too high compared to international secondary wastewater treatment standards of around 30 mg/l. Pollutants including heavy metals (e.g., zinc, copper and nickel) accumulated in the silt trap. However, high outflow velocities during heavy rainfall events did not result in clearly defined sediment layers due to sediment re‐suspension. Metals did not accumulate in the receiving watercourse.     

Eutrophication problems in Emilia Romagna,Italy: Monitoring the nutrient load discharged to the littoral zone of the Adriatic Sea

The deteriorating eutrophic state of the northern Adriatic Sea led to the commissioning of a study between 1977 and 1979 to identify the sources and forms of the nutrients phosphorus and nitrogen discharged from the basin of the river Savio. The study investigated the reduction in the phosphorus load in sewage per head of population caused by a reduction in the phosphorus content of detergents used in the basin and by the use of septic tanks. The flow and nutrient loads carried by the river were monitored during dry and wet weather to establish annual nutrient loads carried to the sea. An extensive sampling programme was carried out to quantify the principal sources of nutrients of which the most important were pig farming, Man and chemical fertilisers. An attempt was made to balance the nutrient loads discharged from the basin.     

Wastewater quality and pollutant loads in combined sewers during dry weather periods

An observatory of urban pollutants was created in Paris in order to assess, at the urban catchment scale, the quality of sanitary sewage and pollutant loads during dry weather periods in the Paris combined sewer. Investigations were carried out for six urban catchments (varying from 42 to 2580 ha) focusing on a wide range of parameters, including: suspended solids (SS), chemical and biochemical oxygen demand (COD and BOD₅), total organic carbon (TOC), total Kjeldahl nitrogen (TKN), heavy metals (Cd, Cu, Pb, Zn), and aliphatic and polycyclic aromatic hydrocarbons (AHs and PAHs). Despite the marginal intra-site variability of some pollutants, which serves to reflect the impact of point sources, this work attests to the spatial homogeneity, at the physical scales considered, of wastewater quality and pollutant loads within the Paris combined sewer network. These results imply that similar production and transfer processes are occurring within sewers during dry weather periods and strongly suggest that data obtained on one specific catchment could be extrapolated to smaller or larger catchments that display quite similar land use and sewer characteristics.     

Modelling operational costs of a large water resource recovery facility receiving stormwater contributions

The main objective of this paper is to develop a methodology for modelling dry and wet weather operational costs applied to the Alcântara Water Resource Recovery Facility (WRRF), which is the largest Portuguese WRRF. Following data collection and intensive data treatment and validation, dry weather patterns of WRRF performance were combined with specific operational costs and described by a conceptual model. The impact of infiltration flows on operational costs was identified. The model simulations show a significant variation of distribution costs during wet weather periods compared with dry weather periods. The methodology can be used for predicting dry and wet weather operational costs and for defining dry weather tariffs and wet weather tariffs. Moreover, the analysis of the dry and wet weather period can also be used for infiltration quantification.     

Occurrence and load of selected herbicides and metabolites in the lower Mississippi River

Analyses of water samples collected from the Mississippi River at Baton Rouge, Louisiana, during 1991-1997 indicate that hundreds of metric tons of herbicides and herbicide metabolites are being discharged annually to the Gulf of Mexico. Atrazine, metolachlor, and the ethane-sulfonic acid metabolite of alachlor (alachlor ESA) were the most frequently detected herbicides and, in general, were present in the largest concentrations. Almost 80% of the annual herbicide load to the Gulf of Mexico occurred during the growing season from May to August. The concentrations and loads of alachlor in the Mississippi River decreased dramatically after 1993 in response to decreased use in the basin. In contrast, the concentrations and loads of acetochlor increased after 1994, reflecting its role as a replacement for alachlor. The peak annual herbicide load occurred in 1993, when approximately 640 metric tons (t) of atrazine, 320 t of cyanazine, 215 t of metolachlor, 53 t of simazine, and 50 t of alachlor were discharged to the Gulf of Mexico. The annual loads of atrazine and cyanazine were generally 1-2% of the amount annually applied in the Mississippi River drainage basin; the annual loads of acetochlor, alachlor, and metolachlor were generally less than 1%. Despite a reduction in atrazine use, historical data do not indicate a long-term downward trend in the atrazine load to the Gulf of Mexico. Although a relation (r2 = 0.62) exists between the atrazine load and stream discharge during May to August, variations in herbicide use and rainfall patterns within subbasins can have a large effect on herbicide loads in the Mississippi River Basin and probably explain a large part of the annual variation in atrazine load to the Gulf of Mexico.     

Water quality and uses of the Bangpakong River (eastern Thailand)

The Bangpakong River is the most important watershed in the Eastern part of Thailand. Water quality parameters were sampled from June 1998 through May 1999 at 11 sites along a 227 km gradient, covering the wet season (June-November) and the dry season (December-May). Surface water was collected at three different stations per site (close to the banks and in the middle of the river), and analyzed for temperature, dissolved oxygen, turbidity, suspended solids, pH. ammonia, fecal coliforms, biochemical oxygen demand and chemical oxygen demand as well as conductivity, phosphate, and heavy metals. The Scottish water quality index (WQI) was adaptated to the tropical environment. The averaged WQI was low (41%) and quality declined significantly during the dry season (ANOVA, p<0.001). Although the quality rose somewhat at middle sites, only 27% of the WQI values during wet season and 2.5% during dry season were higher than 50%, denoting poor environmental quality. Within each season, the main sources of variability were the differences between sites along the gradient (48% during the wet season, 63% during the dry season), whereas monthly variability represented less than 20% of the variability. The seasonal results show that the river is suitable only for tolerant fish and wildlife species and is of doubtful use for potable water supply during the dry season. As quality improves during the wet period, water can be used for the production of potable water, but only with advanced treatment, and for indirect and noncontact recreational activities. In the middle stretches of the river, higher water quality permits multiple uses at moderate cost.     

Contribution of trace metals from atmospheric deposition to stormwater runoff in a small impervious urban catchment

The contribution of atmospheric deposition to emissions of trace metals in stormwater runoff was investigated by quantifying wet and dry deposition fluxes and stormwater discharges within a small, highly impervious urban catchment in Los Angeles. At the beginning of the dry season in spring 2003, dry deposition measurements of chromium, copper, lead, nickel, and zinc were made monthly for 1 year. Stormwater runoff and wet deposition samples also were collected, and loading estimates of total annual deposition (wet+dry) were compared with annual stormwater loads. Wet deposition contributed 1-10% of the total deposition inside the catchment, indicating the dominance of dry deposition in semi-arid regions such as Los Angeles. Based on the ratio of total deposition to stormwater, atmospheric deposition potentially accounted for as much as 57-100% of the total trace metal loads in stormwater within the study area. Despite potential bias attributable to processes that were not quantified in this study (e.g., resuspension out of the catchment or sequestration within the catchment), these results demonstrate atmospheric deposition represents an important source of trace metals in stormwater to waterbodies near urban centers.     

Production and transport of urban wet weather pollution in combined sewer systems: the “Marais” experimental urban catchment in Paris

An experimental catchment area was set up in the centre of Paris (France) so as to follow up the quality of wet weather flows from the entry to the exit of a combined sewer network. The distinctive characteristic of this site is its location in a town centre and the extent of the equipment used to monitor the water pollution over the whole length of its course through the catchment area. The results obtained show a change in quality between the runoff entering the sewer network and the combined storm water flow at the sewer's outlet, which cannot be explained only by the mixture with domestic wastewater. In particular, an increase was observed in the concentrations of suspended solids (SS), VSS, COD, BOD and Cu, in the proportion of pollutants linked to particles and in the characteristics of the particles. A calculation of the total masses going in and out of the sewer network during a rainfall event shows that the erosion of in-sewer pollution stocks is the main source of particles and of organic matter in wet weather flows, whereas heavy metals loads originated from roof runoff, due to the corrosion of metallic roofs. Particles eroded from the sewer sediments during rain events were found to be quite different from the particles of type A deposits and organic biofilms. Nevertheless, they have mean organic and metallic loads that are of the same order of magnitude as the particles of the organic layer at water sediment interface. A change in the chemical form of heavy metals was noticed during the transport in the sewer and it is suspected that a fraction of the dissolved metals from the runoff is adsorbed on sewer sediments.     

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.     

Source characterisation and loads of metals and pesticides in urban wet weather discharges

Contaminants in urban wet weather discharges originate from a number of sources such as materials from wet and dry atmospheric deposition, wastewaters, urban surface erosion, traffic-related activities, in-sewer deposits, etc. In the current study, four contributions (rainwater, dry atmospheric deposition, dry weather discharge and catchment surface + possible erosion of in-sewer deposits) to the total concentrations of priority substances have been assessed at the outlet of two urban catchments (one residential catchment with a combined system and one industrial area with a separate stormwater system) for 12 storm events (six for each catchment). Mass balances were calculated for seven metals and four pesticides, as well as for total suspended solids and chemical oxygen demand. The respective contributions of dry and wet atmospheric deposition, wastewater and catchment surface differ for each pollutant type, corresponding to different land use, activities, environments and sewer systems. For most of the pollutants, the catchment surface appears to be the main contribution, with significant storm event variability, excepted for atrazine in one catchment.     

Combined use of the EPA-QUAL2E simulation model and factor analysis to assess the source apportionment of point and non point loads of nutrients to surface waters

Diffuse pollution is generally indirectly estimated by area and specific emission factors as function of land use. However in many cases these estimates were proven to be remarkably inaccurate. Aim of this study was to combine a water quality simulation model, (USEPA-QUAL2E) and Factor Analysis to increase the understanding of the water pollutants source apportionment. The study concerned two different watersheds, an upland area characterised by a very scarce agricultural use, and another area covering both the upland and the lowland physiographic regions. Particularly the lowland region is included in one of the most productive agricultural areas in Italy. By comparing instream measurements with QUAL2E simulations during dry and wet weather conditions, a good fit (errors +/-20%) was found for the dry weather scenario, whereas very poor was the model performance on the wet weather scenario. This was in the same way expected since the rainfall-driven pollutants scenario deviates significantly from QUAL2E general assumptions of constant emissions in steady state streamflow conditions. However the poor fit was also due to the scarcer reliability of the adopted non point emission estimates. Despite of approximations the model wet weather simulations enabled to estimate the non point contribution to the instream load at the rainfall event scale resolution. Such diffuse sources contribution was found around 80% in the area of extensive agricultural land use, and around 40% in the upland region. Factor Analysis applied to the instream measurements data shed light on the exchange from the groundwater to the surface water system that occurred in the upland region. The hypothesis of a groundwater contribution to the instream total load of nitrates was also supported by QUAL2E simulations that, when considering only the point loads, systematically underestimate the dry weather nitrate concentrations. The same pattern was not observed for the lowland region.     

Cadmium transport in the Lot-Garonne River system (France) - temporal variability and a model for flux estimation

Fluvial cadmium (Cd) inputs into the Gironde estuary via the Lot-Garonne River system were evaluated using nine years of daily measurements of water discharge and total suspended sediment content (TSS) combined with monthly analyses of dissolved and particulate Cd concentrations. This study demonstrates that dissolved and particulate Cd concentrations in the Lot River have strongly decreased in the early 1990s. However, dissolved and particulate Cd concentrations in the Lot River are still higher than those in the Garonne River. In 1992-1998 mean annual Cd concentrations are more or less constant and thus, annual Cd fluxes mainly depend on hydrology. Daily total Cd fluxes range from 0.26 to 966 kg day(-1) in the Lot River and from 0.31 to 1360 kg day(-1) in the Garonne River, downstream their confluence. During dry years, Cd fluxes at La Réole are dominated by inputs from the upstream Garonne River, whereas during wet years they are controlled by inputs from the polluted Lot River watershed. The relation between particulate and dissolved Cd fluxes depends on TSS concentrations, which appear to be mainly controlled by the succession of floods and low waters reflecting short-term basin-scale climate variability. Cadmium concentrations, fluxes and the ratio between the particulate and dissolved Cd fluxes depends on the absolute value and instantaneous evolution (strong relative increase or decrease) of discharge. An empiric model permits deducing intervals of daily dissolved Cd fluxes from discharge, hydrological key situation and related intervals of 'typical' dissolved Cd concentrations. In 1992-1998 the Lot-Garonne River system shows close relations between annual dissolved and particulate Cd fluxes. These relations allow deducing annual particulate Cd fluxes using annual dissolved Cd fluxes obtained from the model. The validation a posteriori shows that our empiric model accurately reproduces the annual Cd fluxes estimated from the field data with uncertainty lower than 25% for dissolved fluxes and lower than 30% for the particulate fluxes. Consequently, the empiric model permits estimating annual dissolved and particulate Cd fluxes in the Lot-Garonne River system, from daily discharge data, without Cd analysis. Cadmium fluxes obtained from the model may be used as approximate values for gross fluvial Cd inputs into the Gironde estuary.     

Estuarine capacity in removal of trace metals from contaminated river water, Southern Caspian Sea

In the present investigation, the flocculation of dissolved Cd, Cu, Ni, Pb, Mn and Zn with initial concentrations of 1, 2.5 and 5 mg/L in Tadjan River water during mixing with the Caspian Sea water has been studied in order to determine estuarine capacity to remove dissolved metals in the accidental contamination of the river. The flocculation process was investigated on a series of mixtures with salinities ranging from 0.1 to 11 p.p.t. The flocculation rates were indicative of the nonconservative behaviour of Cd, Cu, Ni, Pb, Mn and Zn during estuarine mixing. The order of the final flocculation rate of dissolved metals at 1, 2.5 and 5 mg/L of initial metal concentrations in the river water is as follows:Cu (99%)>Cd (95%)>Zn (88%)>Mn (85%)>Pb (83%)>Ni (73%), Cu(95.6%)>Pb(92.4%)>Cd (90%)>Zn(88.4%)>Mn (81.6%)>Ni(78.8%) and Cd (100%)>Cu(88%)>Ni (85.2%)>Pb (84%)>Zn (83.2%)>Mn (81.2%), respectively. The results also revealed that removal of dissolved metals is not influenced by pH changes and precipitation processes. The flocculation rates revealed that the overall dissolved metal pollution loads may be reduced to about 70% up to about more than 90% during estuarine mixing of Tadjan River with the Caspian Sea water.