Sources, nature, and fate of heavy metal-bearing particles in the sewer system

A preliminary insight into metal cycling within the urban sewer was obtained by determining both the heavy metal concentrations (Cu, Zn, Pb, Cd, Ni, Cr) in sewage and sediments, and the nature of metal-bearing particles using TEM–EDX, SEM–EDX and XRD. Particles collected from tap water, sump-pit deposits, and washbasin siphons, were also examined to trace back the origin of some mineral species. The results show that the total levels in Cu, Pb, Zn, Ni, and Cr in sewage are similar to that reported in the literature, thus suggesting that a time-averaged heavy metal fingerprint of domestic sewage can be defined for most developed cities at the urban catchment scale. Household activities represent the main source of Zn and Pb, the water supply system is a significant source of Cu, and in our case, groundwater infiltration in the sewer system provides a supplementary source of Ni and Cd. Concentrations in heavy metals were much higher in sewer sediments than in sewage suspended solids, the enrichment being due to the preferential settling of metal-bearing particles of high density and/or the precipitation of neoformed mineral phases. TEM and SEM–EDX analyses indicated that suspended solids, biofilms, and sewer sediments contained similar heavy metal-bearing particles including alloys and metal fragments, oxidized metals and sulfides. Copper fragments, metal carbonates (Cu, Zn, Pb), and oxidized soldering materials are released from the erosion of domestic plumbing, whereas the precipitation of sulfides and the sulfurization of metal phases occur primarily within the household connections to the sewer trunk. Close examination of sulfide phases also revealed in most cases a complex growth history recorded in the texture of particles, which likely reflects changes in physicochemical conditions associated with successive resuspension and settling of particles within the sewer system.     

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.     

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.     

Chemical coagulation of combined sewer overflow: heavy metal removal and treatment optimization

The coagulation of combined sewer overflow (CSO) was investigated by jar-testing with two commercial coagulants, a ferric chloride solution (CLARFER) and a polyaluminium chloride (WAC HB). CSO samples were collected as a function of time during various wet-weather events from the inlet of Boudonville retention basin, Nancy, France. Jar-tests showed that an efficient turbidity removal can be achieved with both coagulants, though lower optimum dosages and higher re-stabilization concentrations were obtained with the aluminum-based coagulant. Optimum turbidity removal also yielded effective heavy metal elimination. However, the evolution with coagulant dosage of Cu, Zn, Pb, Cr, soluble and suspended solids contents followed various patterns. The removal behaviors can be explained by a selective aggregation of heavy metal carriers present in CSO and a specific interaction between hydrolyzed coagulant species and soluble metals. Stoichiometric relationships were established between optimal coagulant concentration, range of optimal dosing, and CSO conductivity, thus providing useful guidelines to adjust the coagulant demand during the course of CSO events.     

Consideration of metals levels in identifying CSO abatement options

Levels of total metals (Pb, Cu, Zn, Cr, Ni) from samples in Buffalo, NY, were generally higher in combined sewage than sanitary flow. Sewer separation should therefore be considered carefully when choosing combined sewer overflow (CSO) abatement options. The first flush phenomenon was typically observed for sampled CSO events and first flush control may be effective in reducing receiving water impacts. Event mean concentration is often used for runoff quality evaluation, without consideration of concentration variability. The Weibull and lognormal distributions best fit the event mean concentration data and could be used to assess contaminant loading variability.     

Metal partitioning in a sulfidic canal sediment: metal solubility as a function of pH combined with EDTA extraction in anoxic conditions

The chemical forms of low concentrations of metals (Zn, Pb, Cu, Cd, Co and Mn) and main components (Fe and Ca) were determined under the original reducing conditions of a sulfide-rich sediment from the Gent-Terneuzen Canal (Belgium). Therefore, dissolution experiments as a function of pH were made in a salt solution mimicking the canal water. The centrifugates remaining after the dissolution vs. pH experiments were subsequently further extracted with 0.1 M EDTA/0.5 M NaAc (pH 4.65) to determine eventually readsorbed and/or reprecipitated metal ions. The experimental dissolution vs. pH edge of calcium, iron, manganese and cobalt had a lower slope than theoretically expected on the basis of the solubility of, respectively, calcium carbonate, iron sulfide/iron carbonate, manganese sulfide/manganese carbonate and cobalt sulfide and was explained by the combination of (a) the solubilities of the various minerals and (b) metal readsorption onto clay minerals and organic matter. Higher metal recoveries were measured in the 0.1 M EDTA/0.5 M NaAc mixture and proved that in addition coprecipitate formation with iron sulfide/iron carbonate minerals may occur. The solubility of zinc, lead, cadmium and copper was very low in the mimicking salt solution even at very low pH values (up to pH 1) in agreement with the theoretical solubility of their discrete metal sulfides. However, by using an additional 0.1 M EDTA/0.5 M NaAc extraction on the centrifugates remaining after the dissolution vs. pH experiments, it was qualitatively shown that zinc and lead were partly associated with iron sulfide/iron carbonate phases in the real sediment (in addition to their presence in discrete metal sulfides). Cadmium was present solely in discrete cadmium sulfide phases. It was not possible to verify whether copper was present in discrete copper sulfide phases and/or in mixed coprecipitates with iron sulfide/iron carbonate minerals.     

Comparison of sediments and organisms in identifying sources of biologically available trace metal contamination

Sediments and an indicator organism (Macoma balthica, a deposit-feeding bivalve) were used to assess the relative importance of secondary sewage, urban runoff, a landfill containing metal-enriched ash wastes and a yacht harbor in contributing to Ag, Cu and Zn enrichment in South San Francisco Bay. Spatial gradients in sediments and organisms showed Cu and Ag enrichment originated from sewage discharge, whereas Zn enrichment originated from both sewage and urban runoff. Elevated concentrations of Cu in the sediments of the yacht harbor resulted from a high abundance of fine particles. The biological availability of Cu, Ag and Zn did not coincide with metal enrichment in sediments. The availability of Cu and Ag was greatest nearest the sewage outfall and greater in winter and spring than in summer. The availability of Zn in urban runoff appeared to be lower than the availability of Zn associated with sewage.     

The significance of entry routes as point and non-point sources of pesticides in small streams

In an agricultural catchment area in Germany we analyzed water samples from five entry routes for 2 insecticides. 5 fungicides and 13 herbicides. The sewage plant outlet and the emergency overflow of a sewage sewer contained only herbicides. In each farmyard runoff we found on average 24 g pesticides during application period, presumably caused by cleaning the spraying equipment. In comparison, the field runoff and the rainwater sewer contained less load, but also insecticides, fungicides and herbicides. The sewage plant caused 65.9% of the total herbicide load, the sewage sewer 19.8% and the farmyard runoff 12.8%. The farmyards also caused 83.7% of total insecticide and 83.8% of fungicide load. The total load of all entry routes is correlated with the amount of pesticides applied in the catchment area and the Ko/w value for each pesticide (mult. regress. r2: 0.82; p<0.0001; n = 14). In stream A the sewage plant caused a slight but continuous contamination by herbicides with 82% of the total load found during low-water phases. In comparison, stream B had only farmyard runoff and non-point sources, which caused high peaks of herbicide and a contamination by insecticides. Consequently, high-water phases generated 70% of the total pesticide load.     

Heavy metals in the lagos lagoon sediments

Concentrations of cadmium, cobalt, copper, chromium, iron, manganese, nickel, lead and zinc were determined in surface sediments of the Lagos Lagoon, Nigeria. The results revealed largely anthropogenic heavy metal enrichment and implicated urban and industrial wastes and runoff water transporting metals from land‐derived wastes, as the sources of the enrichment. Higher levels (F < 0.05) of cadmium, iron, manganese, nickel and zinc occurred in sediment samples collected near industrialized‐urban areas than in those from unindustrialized‐rural areas only in the wet season. While iron constituted about 1% of dry sediment by weight, the other metals were present in trace amounts.     

Hydrogeochemische Reaktionen im Sicker- und Grundwasserbereich von Braunkohlentagebaukippen

The changes in the chemical composition of water and solid phases in pyrite oxidation zones and in lignite mining dump aquifers are described and modelled. At pH-values below pH 4, sulfate and ferrous iron as pyrite oxidation products, are mobile. They are observed in a stoichiometric ratio of 1 to 2 in the aqueous phase. If pyrite oxidation takes place with no pH-buffering with the solid phases, pH-values below 1 are possible. This leads to more intensive silicate weathering which increases the pH-value of the solution to pH 2–3. However, equilibrium with silicates is not reached. At pH-values above pH 4, the iron concentration of water under oxidized conditions is limited by the precipitation of ferric hydroxide. This has an impact on sulfide oxidation itself, because ferric iron is involved in the oxidation reactions of pyrite. Products of sulfide oxidation stored in acidic material in overburden are leached by seepage water and ground water filling the dumps. Reaction with carbonate phases in non-acidic material mainly takes place during ground water recharge. The geogenic calcite minerals of the non-acidic sediments are dissolved. Gypsum and iron-rich carbonates precipitate as secondary minerals in the dump aquifer. The pH-value increases and the concentration of iron and trace metals (Co, Ni, Zn) in the ground water are controlled by equilibrium with iron-rich carbonates at pH-values above pH 5.     

国内外对合流制管道溢流污染的控制与管理

随着城市化进程的加快,城市雨水问题以及合流制排水管道的溢流污染问题变得日益严重.合流制管道的溢流污染已成为部分城市改善水体水质的主要制约因素之一.若未经有效处理的溢流污水直接排入水体中,不仅会严重地破坏水环境功能,还将危及人类健康.介绍了国内外部分城市控制合流制管道溢流污染的概况,分析了我国目前控制合流制管道溢流污染存在的问题和不足,讨论国外经验对我国的启示并提出一些建议,为我国对合流制管道的溢流污染控制提供借鉴.     

Sulfide-iron interactions in domestic wastewater from a gravity sewer

Interactions between iron and sulfide in domestic wastewater from a gravity sewer were investigated with particular emphasis on redox cycling of iron and iron sulfide formation. The concentration ranges of iron and total sulfide in the experiments were 0.4-5.4mgFeL(-1) and 0-5.1mgSL(-1), respectively. During anaerobic conditions, iron reduction kinetics were investigated and reduction rates amounted on average to 1.32mgFeL(-1)d(-1). Despite the very low solubility of iron sulfide, the reduced iron reacted only partly with sulfide to produce iron sulfide, even when dissolved sulfide was in excess. When a ferric chloride solution was added to sulfide containing anaerobic wastewater, the ferric iron was quickly reduced to ferrous forms by oxidation of dissolved sulfide and the ferrous iron precipitated almost completely as iron sulfide. During aerobic conditions, iron sulfide was oxidized with a half-life period of 11.7h. The oxidation rate of iron sulfide was significantly lower than that reported for the oxidation of dissolved sulfide.     

Chemical partitioning and remobilization of heavy metals from sewage sludge dumped in Dublin Bay

During the disposal of sewage sludge to the marine environment, chemical changes may alter the mobility of trace elements, thus affecting their potential toxicity and availability to marine organisms. Primary sludge from the Ringsend treatment plant in Dublin receives both domestic waste and trade wastes which contain heavy metals, and approx. 250,000 tons per annum is periodically dumped in Dublin Bay. The purpose of this study was to determine changes which may occur in the chemical partitioning of heavy metals in the sludge during disposal. Samples of sludge were collected from the treatment plant in July 1987. Sequential chemical extraction of heavy metals (Cu, Pb, Cd, Zn, Fe, Mn) was carried out in a nitrogen-filled glove box using 1 M ammonium acetate, 1 M sodium acetate, 0.1 M hydroxylamine HCl (pH 2), 0.2 M ammonium oxalate (pH 3), 30% hydrogen peroxide and concentrated HNO₃. Seawater-extractable metal was determined by mixing subsamples of sludge with filtered seawater from Dublin Bay for 2 h. Chemical partitioning of heavy metals among solid phases in the sludge residue was redetermined by sequential chemical extraction. Both sludge and dumpsite sediments were analysed for total heavy metal content and organic content. The sludge was found to be only slightly anaerobic with a water content of 88% and significant concentrations of some metals, notably copper and zinc. Most of the non-residual copper, lead and cadmium was found in the organic/sulphidic fraction of the sludge (hydrogen peroxide extract), while the dominant phase for zinc was the moderately reducible fraction (ammonium oxalate extract) and only iron and manganese had substantial proportions of metal in more labile phases. Agitation with seawater mobilized cadmium and manganese to a significant extent (56 and 43%, respectively) but negligible amounts of copper or lead (0 and 2%, respectively). However, significant changes in solid-phase partitioning of lead and zinc occurred resulting in mobilization from stronglybound to more labile fractions. No deleterious effects were found at the dumpsite but localized effects are possibly due to the increased mobility of zinc, lead and particularly cadmium.     

Contribution of combined sewer overflows to trace contaminant loads in urban streams

The present study examines the contribution of combined sewer overflows (CSO) to loads and concentrations of trace contaminants in receiving surface water. A simple method to assess the ratio of CSO to wastewater treatment plant (WWTP) effluents was applied to the urban River Spree in Berlin, Germany. The assessment indicated that annual loads are dominated by CSO for substances with removal in WWTP above ∼95%. Moreover, it showed that substances with high removal in WWTP can lead to concentration peaks in the river during CSO events. The calculated results could be verified based on eight years of monitoring data from the River Spree, collected between 2000 and 2007. Substances that are well removed in WWTP such as NTA (nitrilotriacetic acid) were found to occur in significantly increased concentration during CSO, while the concentration of substances that are poorly removable in WWTP such as EDTA (ethylenediaminetetraacetic acid) decreased in CSO-influenced samples due to dilution effects. The overall results indicate the potential importance of the CSO pathway of well-removable sewage-based trace contaminants to rivers. In particular, high concentrations during CSO events may be relevant for aquatic organisms. Given the results, it is suggested to include well-removable, sewage-based trace contaminants, a substance group often neglected in the past, in future studies on urban rivers in case of combined sewer systems. The presented methodology is suggested for a first assessment, since it is based solely on urban drainage data, which is available in most cities.     

Metal speciation in sulphidic sediments: a new method based on oxidation kinetics modelling in the presence of EDTA

The solid phase partitioning of metals (Zn, Cu and Pb) was determined in four anoxic, metal polluted sediments by investigating at pH 8 the 1 day oxidation kinetics of the metal sulphide phases present in the sediments in a background solution containing excess EDTA. A mathematical model consisting of a combination of two pseudo-first order reactions was used to fit the metal release data as a function of oxidation time. The model permitted to fractionate the trace metals in a 'quickly-oxidizable' and a 'slowly-oxidizable' fraction, which could be assigned to two different trace metal pools, respectively (1) FeS minerals (e.g. amorphous FeS, mackinawite) and (2) discrete trace metal sulphide phases. The sum of the fractions associated with these sulphide pools was taken as an approximation for the sulphide-associated fraction of the trace metals and coincided (for the case of Zn and Pb) with the sulphide-associated fraction derived from the analysis of acid volatile sulphide (AVS) and simultaneously extracted metals (SEM). Oxidation kinetics modelling allowed also determining the sulphide-associated fraction of a broad range of trace metals (as demonstrated for Cu) more accurately than the AVS/SEM method, which suffers from non-efficient extraction of a number of trace metal sulphides. A correction was made for the determination of the sulphide-associated fraction by subtracting the trace metal fraction dissolved after 1 day under anoxic conditions in the background EDTA solution. The combination of (1) one day oxidation kinetics modelling and (2) correction for the 1 day anoxic EDTA-soluble fraction is a suitable method to determine accurately the true sulphide speciation of trace metals in anoxic sediments.     

Phosphate dynamics in an urban sewer: A case study of Nancy, France

The nature of phosphate phases present in suspended matter, biofilm, and sediment of Greater Nancy sewer system was investigated over a period of two years. The phosphate speciation was determined by two approaches: a direct identification of phosphorus mineral phases was conducted by Transmission Electron Microscopy (TEM) coupled with energy-dispersive X-ray spectroscopy (EDXS), whereas a chemical extraction of samples provided an estimate of phosphorus pools defined by the fractionation scheme. Quantitative analysis of 1340 individual particles by TEM-EDXS allowed to draw a picture of phosphate species distributions along the sewer system and over time. Amorphous Ca-phosphates (brushite, whitlockite, octacalcium phosphate, Mg-brushite, hydroxyapatite and carbapatite) were ubiquitous although brushite dominated upstream, and octacalcium phosphate and apatite prevailed downstream and in sediments. Al-Ca-phosphate minerals such as foggite, bearthite, gatumbaite, and crandallite appeared downstream and in biofilms. Ca-phosphate phase assemblages in the different locations of the sewer system were dependent on phase transformations from brushite to hydroxyapatite that were shown to be kinetically driven. The restriction of Al-Ca-phosphates to downstream of the sewer system was most probably related to the lower pHs measured at these sites. The pH dependency was confirmed by stability calculations. Chemical extractions were not reliable. TEM examination of extraction residues revealed the presence of neoformed Al-Ca-phosphate species that invalidated the fractionation scheme. Nonetheless, it confirmed that phosphate phases may undergo significant geochemical changes over a short time scale.     

Mobilization of heavy metals from Le An River sediment

The release of sediment-bound heavy metals can have a significant influence on river water quality. Generally speaking, variations of pH and oxygen are among the most important chemical factors that affect the mobility of sediment-bound metals. Recent research has indicated that sulfide, measured as acid-volatile sulfide (AVS), is an important partitioning component of heavy metals. We determined the metal release potential of sediments from the Le An River which receives drainage from a major copper mining operation. We found that the in-situ Cu, Pb, Zn, Cd and As concentrations of the Le An River sediments below the mine are much higher than are the global background values, but that Ni was not elevated. There is potential for mobilization of bound metals to the overlying water, the order of metal release ratio in terms of pH dependencies is Zn > Cu > Cd approximately Pb. Sulfide is not a major binding component for metals in Le An River sediment. It is more likely that the iron and manganese oxides are the most important metal binding components in the sediments of the Le An River.     

Diagenesis of magnetic minerals in the intertidal sediments of the Yangtze Estuary, China, and its environmental significance

In this study, diagenesis of iron oxides in intertidal sediments of the Yangtze Estuary, China, has been investigated by combined environmental magnetic and geochemical methods. The results indicated that the magnetic properties of the sediments were dominated by ferrimagnetic magnetite. The content of Fe, DCB- and AOD-extractable iron oxides correlated positively with the concentration of fine grained magnetite near the superparamagnetic/stable single domain (SP/SSD, approximately 0.03 microm) boundary, and with anti-ferromagnetic minerals (hematite/goethite). The magnetic parameters for core SDK indicated a substantial decrease in magnetite concentration from a depth of approximately 20 cm toward the surface, together with a shift in the grain-size distribution of magnetic minerals toward the coarse end, suggesting selective dissolution of fine grained magnetite under reducing conditions. The reduction of iron oxides inferred from magnetic measurements was supported by the similar decrease in the concentration of Fe and Mn and a lower ratio of Mn/Fe. Magnetic measurements on another core from elsewhere also indicated substantial reductive dissolution of iron oxides. In conjunction with the results of heavy metal analysis, it was suggested that the dissolution of iron oxides had a direct effect on the cycling of heavy metals. Therefore, magnetic measurements may provide useful information as to early diagenesis within intertidal sediments, which greatly influences the behavior of heavy metals in coastal environments.     

Iron salts dosage for sulfide control in sewers induces chemical phosphorus removal during wastewater treatment

Chemical phosphorus (P) removal during aerobic wastewater treatment induced by iron salt addition in sewer systems for sulfide control is investigated. Aerobic batch tests with activated sludge fed with wastewater containing iron sulfide precipitates showed that iron sulfide was rapidly reoxidised in aerobic conditions, resulting in phosphate precipitation. The amount of P removed was proportional to the amount of iron salts added, and for the sludge used, ratios of 0.44 and 0.37 mgP/mgFe were obtained for ferric and ferrous dosages, respectively. The hydraulic retention time (HRT) of iron sulfide in sewers was found to have a crucial impact on the settling of iron sulfide precipitates during primary settling, with a shorter HRT resulting in a higher concentration of iron sulfide in the primary effluent and thus enabling higher P removal. A mathematical model was developed to describe iron sulfide oxidation in aerated activated sludge and the subsequent iron phosphate precipitation. The model was used to optimise FeCl₃ dosing in a real wastewater collection and treatment system. Simulation studies revealed that, by moving FeCl₃ dosing from the WWTP, which is the current practice, to a sewer location upstream of the plant, both sulfide control and phosphate removal could be achieved with the current ferric salt consumption. This work highlights the importance of integrated management of sewer networks and wastewater treatment plants.     

基于管道沉积物控制的CSOs污染负荷削减分析

管道沉积物是合流制排水系统溢流(CSOs)污染的重要来源,因此控制沉积物对于削减CSOs污染具有重要意义。在合流制排水系统截流泵站的上游管道中安装穿孔管,给穿孔管提供高压水产生7.5 m/s以上的射流以冲洗管道,同时在截流泵站内设置旋流分离系统来去除冲洗水中的沉积物。对于水层较浅、管径为DN400、管长为40 m、沉积层厚度为3 cm的管道,可使管道流中的SS从冲洗前的75～170 mg/L增加到2 500～3 000 mg/L,且在2～3 min内冲洗干净。旋流分离器对冲洗水中SS的去除率达到55.6%。两周一次的管道例行清洗维护,可使CSOs中污染物降低25%左右,减轻了受纳水体的污染负荷。