Chemosphere 52 (2003) 17811795 www.elsevier.

com/locate/chemosphere

Self-purication ability of a resurgence stream

Roberta Vagnetti a, Paola Miana b, Mario Fabris b, Bruno Pavoni
a

a,*

Dipartimento di Scienze Ambientali, Universit CaFoscari di Venezia, Calle Larga S. Marta, 2137-30123 Venice, Italy a b VESTA S.p.A., Venezia Servizi Territoriali Ambientali, Palazzo Bonfadini, Cannaregio 462-30121 Venezia, Italy Received 5 July 2002; received in revised form 10 April 2003; accepted 16 April 2003

Abstract The self-purication ability of a resurgence stream has been investigated by taking samples along the course of a channeled tract made up of a rst part in beaten soil (3.3 km) and a second in concrete (7.2 km). The study has been conducted by statistically processing pre-existent data, acquired monthly by analyzing waters at the beginning and at the end of the whole canal for 6 years, from 1995 to 2000 (historic data), and by performing specic experiments (recent data) to evaluate dierently the self-purication capacity of the beaten soil section and that in concrete. A signicant abatement of concentrations has been observed from historic data for ammonium, phosphates, turbidity, heavy metals and bacteria. From the recent data, all these parameters seem to decrease in the beaten soil tract. Whereas signicant further decreases in the concrete tract were observed only for ammonium, phosphates and bacteria. For other parameters, e.g. pH, dissolved oxygen, chlorides, uorides, sodium, and sulfates, a signicant increase was observed from the historic data. 2003 Elsevier Ltd. All rights reserved.
Keywords: Self-purication; Resurgence stream; Nutrients; Metals; Turbidity; Bacteria

1. Introduction The water environment reacts to the input of polluting substances by means of a number of mechanisms aiming to restore its original conditions. This process, referred to as self-purication, actually consists of a recycling of materials (Vismara, 1998). More precise denition for self-purication could be: self-purication means the partial or complete restoration, by natural processes, of a stream pristine condition following the introduction (usually through the agency of man) of foreign matter sucient in quality and quantity to cause a measurable change in physical, chemical and/or biological characteristics of the stream (Benoit, 1971). This transformation produces compounds having a less neg-

ative impact than the starting ones. The natural selfpurication process is therefore consisting of various complex phenomena involving numerous physical, chemical and biological factors acting and interacting more or less eectively.

1.1. Physical processes Dilution is an important component of self-purication, for it allows the achievement of suitable concentrations for biological assimilation (Vismara, 1998). Adsorption is the binding of molecules and ions which are present in solution to solid particles. During the adsorption process other ions are displaced from the solid matrix into the solution (Benoit, 1971). Clays and other colloidal particles (e.g. oxideshydroxides of Fe and Mn) can adsorb several organic and/or inorganic solutes. Furthermore the solid phase can be a proper support for bacterial degradation (Vismara, 1998). In

Corresponding author. Tel.: +39-41-234-8522; fax: +39-412348582. E-mail address: brown@unive.it (B. Pavoni).

0045-6535/03/$ - see front matter 2003 Elsevier Ltd. All rights reserved. doi:10.1016/S0045-6535(03)00445-4

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particular, heavy metals are frequently adsorbed onto the surface of suspended particulate matter instead of being dissolved in the liquid phase as free or complexed ions. This process plays a very important role in the cycles of natural materials in the environment. Many species are accumulated in the suspended solids or in sediments, and partitioning between the solid and liquid phase inuences the transport and fate of contaminants in the water bodies (Suzuky, 1997). Sedimentation is one of the most important selfpurication mechanisms, especially in lakes, lagoons and lentic waters. By this means suspended particles are removed along with their adsorbed ions and molecules, thus removing soluble materials from the water column. Pollutants generally remain on the bottom, but can be remobilized during period of increased water ow or turbulence, with the concurrent activities of desorption and ionic exchange, which are mainly favored by anaerobic conditions (Vismara, 1998). Sediment and suspended particles are depositories of large amounts of heavy metals, which can be present as distinct compounds or associated with clays, insoluble humic substances or iron and manganese oxides. Accumulation of heavy metals in bottom sediments is one of the most eective factors in self-purication. However, since this is a reversible process, metal accumulation can be considered a constant potential for secondary pollution, caused by resuspension and release phenomena (Linnik and Zubenko, 2000). Volatilization (transfer of pollutants from water to the gas phase) causes a permanent removal of compounds from the liquid phase. From the vapor pressure of the compounds, its tendency to volatilize can be inferred, however its solubility and other features can also be important (Brusseau and Bohn, 1996).

or carbonates, involve the removal of cations from solution. Processes leading to the formation of aggregates from colloidal suspensions are also very important and result in sediment formation and water clarication (Manahan, 1994). These processes are coagulation and occulation, which are complex phenomena of a physical and chemical nature, and are not yet well understood. 1.3. Biological processes Bacterial degradation is the most important removal process for organic substances and some inorganic substances, especially nitrogen and phosphorus compounds. Bacteria obtain the necessary energy for their survival by redox reactions, which transform organic matter and nutrients. Plants can protect an ecosystem by assimilation and removal of a portion of the macronutrients present in the water body (Chambers and Prepas, 1994; Volterra and Mancini, 1994; Cunningham and Davi, 1996; Borin and Marchetti, 1997). Mostly nitrogen and phosphorus compounds are involved, but many plants can accumulate heavy metals and toxic substances. It is necessary to distinguish between the phytoremediation of inorganic elements and toxic organic compounds (Meagher, 2001): elemental pollutants are essentially immutable by any biological and physical process, whereas organic substances are mineralized into relatively non-toxic constituents. Assimilation is higher in summer, when nutrients are stored in expectation of the winter season (Volterra and Mancini, 1994). Finally it must be considered that the rhizosphere hosts a very abundant population of microorganisms and that vegetation itself can act as a lter for the suspended particulate matter. From a preliminary examination of historic analytical results, a considerable decrease of some substances was observed in water samples taken at the beginning and at the end of a canal. The aim of the present investigation was to establish, by means of a statistical treatment of pre-existent data (historic data) and some ad hoc conrmation experiments (recent data), for which parameters the abatement is signicant and to formulate possible interpretations.

1.2. Chemical processes Acidbase reactions maintain the natural water pH by neutralizing acid and base pollutants. Water buer capacity is strongly related to alkalinity which is the waters content of carbonate and hydroxide species (Vismara, 1998). Within the very high number of redox reactions, very important are the oxidation of organic matter which consumes oxygen and the oxidation of ammonia to nitrate, which is important for nitrogen to be assimilated by plants and therefore removed. It must be considered that many of the most important redox reactions are catalyzed by microorganisms or governed by other biological processes (Manahan, 1994). Precipitation reactions, depending on the solubility product of several compounds, are very important for removing ions from the liquid phase. Many precipitation reactions, such as the formation of salts of phosphates

2. Materials and methods 2.1. Study site The stream investigated in this study is an articial canal (averagely 2 m deep, 5 m large with a ow rate of about 2.2 m3 /s) feeding a municipal purication plant for household (285 000 people served) and industrial use. Main treatments carried out are coagulation, activated carbon adsorption, clarication, ltration and disinfec-

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tion. The canal conveys water from the resurgence river Sile, in Quarto dAltino to Favaro Veneto (Veneto Region, NorthEast of Venice, Italy). Surrounding area is only used for agriculture and along the course of the canal (10.5 km) some water can be derived for irrigation. The rst section of the canal (3.3 km) is in beaten soil and the second section (7.2 km) is in concrete. Various plants species are present, mainly in the beaten soil tract: Apium nodiorum (abundance 01), Callitriche stagnalis (ab. 23), Ceratophillum demersus (ab. 12), Elodea canadensis (ab. 34), Potamogeton natans (ab. 34), Potamogeton pectinatus (ab. 34), Ranunculus uitans (ab. 34), Vallisneria spiralis (ab. 12) (Marconato, 2003). The extended biotic index value for the canal (beginning of the canal) is 8, i.e. the water is slightly polluted (Marconato, 2003). Fish species present are Anguilla anguilla, Cobitis taenia, Esox lucius, Padogobius martensii, Rutilus erythrophthalmus, Scardinius erythrophthalmus (Marconato et al., 2000). 2.2. Statistical analyses The historic data set consisted of pre-existent analytical results of water samples collected at stations located at the beginning and at the end of the canal during 6 years (19952000) with a monthly frequency. These data were processed with the Statistical t Test using paired data (Piccolo, 2000) to discriminate signicant dierences between the pairs of values obtained for any single parameter at the beginning and at the end of the canal in the same sampling session. A 5% signicance level was used. A parametric method was chosen after checking data normality. 2.3. Sampling design To validate the results obtained by means of the statistical data processing, some additional experiments were carried out. Sampling sessions took place on 27th March, 27th June, and 12th September 2001 (recent data). The sampling stations were the following: 1. 2. 3. 4. Quarto dAltino (Head of the canal). End of canal tract # 1 (Beaten soil). Siphon. Favaro Veneto (End of the canal).

samplings it was noticed that the siphon was partly plugged with sediment and that an intense resuspension was evident in the tract downstream. In order to establish the sampling times necessary to collect the same water parcel at the beginning and at the end of its travel along the canal, the water velocity was preliminarily estimated. During each sampling session the ow rate was measured by means of a oat moving at a water depth of about 20 cm below the surface to avoid wind inuence. Water samples (one sample for microbiological analyses, one for chemical analyses) were collected by dipping the containers about 1 m below the surface. Containers for microbiological analyses were previously sterilized, whereas those for chemical analyses were previously cleaned in the laboratory and then simply rinsed with the water to be sampled. Samples were then transferred to the laboratory by means of a portable refrigerated container and kept at 4 C before analyses, which were performed the same or the following day. The parameters selected for the analyses were those showing a signicant abatement. In addition, nitrates and nitrites were also analyzed to estimate the total inorganic nitrogen budget. In this study the organochlorine compounds, such as 1,1,1-trichloroethane and tetrachloroethylene were not included because they were considered to be clearly lost to the atmosphere by evaporation. All microbiological and chemical analyses (historic and recent data) were performed according to the procedures reported in the manuals Standard Methods for the Examination of Water and Wastewater (AWWA, 1998) and Analytical Methods for Waters (CNR, 1994).

2.4. Microbiological analyses Water samples were ltered through a membrane with a pore size of about 0.45 lm, which traps most of the bacteria on its surface. The membrane was then placed in a pad saturated with a medium selected to favor growth and dierentiation of organisms. Media used were M-endo agar for total coliforms, M-FC agar for fecal coliforms, KF-streptococcus agar for fecal streptococci and plate count agar for heterotrophic count at 22 and 36 C. The bacterial number was then reported as colony forming units (CFU) per unit of water volume. Precisions for microbiological analyses, calculated as coecient of variations from six replicates, were: 8% for heterotrophic count at 22 C, 13% for heterotrophic count at 36 C, 21% for total coliforms, 3% for fecal coliforms, 2% for fecal streptococci and 15% for clostridia spores. Increases and decreases (percent), for each parameter, were considered signicant when higher than coecients of variations.

A map of the canal is shown in Fig. 1. Sampling times were established according to the water velocity. Sampling station 2 was selected in order to possibly distinguish the self-purication ability of the canal tract bordered by beaten soil from that framed by concrete. Sampling station 3 was chosen to detect the inuence of a siphon along the course of the canal enabling the crossing of the river Zero. During the

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Fig. 1. Map of the canal (NorthEast of Venice). Station 1 (head of the canal), station 2 (end of beaten soil tract), station 3 (siphon) and station 4 (end of the canal, purication plant).

2.5. Physicalchemical analyses Turbidity was measured by the Nephelometric Method using a HACH 2100 AN instrument, provided with a tungsten source and a photoelectric detector. Ammonium concentration was measured by the phenol-hypochlorite method, using a spectrophotometer UVVIS Lambda 2, Perkin Elmer, operating at 660 nm.

Nitrates concentration was determined spectrophotometrically at 220 nm, after sample acidication to eliminate carbonates. Nitrites concentration was determined through formation of a reddish purple azo dye (measured spectrophotometrically at 540 nm) produced at a pH 2.02.5 by coupling diazotized sulfanilamide with N-(1-naphtyl)ethylenediamine dihydrochloride.

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Phosphates concentration was measured after transformation of polyphosphates into orthophosphates with sulfuric acid and potassium persulphate. Orthophosphates concentration was measured spectrophotometrically at 650 nm, after reaction with ammonium molybdate and potassium antimonyl tartrate in acid medium to form phosphomolybdic acid, and further reduction to the intensely colored molybdenum blue by ascorbic acid. Dissolved organic carbon (DOC) concentration was determined potentiometrically as CO2 using a selective

electrode. Samples were previously ltered, acidied to remove carbonates/bicarbonates and nally oxidized with persulphate and UV irradiation. Heavy metals concentration was determined by an Atomic Absorption Spectrophotometer (3030, Perkin Elmer) after acidication of the non-ltered sample with nitric acid. The following wavelengths were used: Al, 309.3 nm; Fe, 248.3 nm; Mn, 279.5 nm; Pb, 324.7 nm; Zn, 213.19 nm. Precisions for chemical analyses, calculated as coecient of variations from six replicates, were: 2% for turbidity, 2% for ammonium, 3% for

Table 1 Average and percent abatement of the parameters analyzed at the beginning and at the end of the canal from 1995 to 2000 (historic data) Average dierence pH Conductivity Turbidity Alkalinity Ammonium Sodium Potassium Calcium Magnesium Total hardness Dissolved oxygen Fluorides Chlorides Nitrites Nitrates Total phosphates Sulfates D.O.C. Al Cr Fe Pb Mn Ba B Cu Zn Chloroform 1,1,1-Trichloroethane Trichloroethylene Dichlorobromomethane Tetrachloroethylene Dibromochloromethane Bromoform Heterotrophic count at 22 C Heterotrophic count at 36 C Total coliforms Fecal coliforms Fecal streptococci Sulte-reducing clostridia spores 0.12 )2 lS/cm )3.3 NTU 1 mg/dm3 CaCO3 )0.16 mg/dm3 0.70 mg/dm3 0.04 mg/dm3 0.49 mg/dm3 )0.19 mg/dm3 )0.5 mg/dm3 CaCO3 0.3 mg/dm3 0.01 mg/dm3 0.55 mg/dm3 0.05 mg/dm3 0.01 mg/dm3 )0.04 mg/dm3 0.57 mg/dm3 0.1 mg/dm3 )65.9 lg/dm3 )0.4 lg/dm3 )38.2 lg/dm3 )0.2 lg/dm3 )3.9 lg/dm3 )3.0 lg/dm3 0.8 lg/dm3 )1.1 lg/dm3 )3.8 lg/dm3 )0.28 lg/dm3 )0.07 lg/dm3 )0.01 lg/dm3 )0.11 lg/dm3 )0.18 lg/dm3 )0.04 lg/dm3 )0.01 lg/dm3 )8001 UFC/cm3 )6580 UFC/cm3 )19 661 UFC/100 cm3 )4382 UFC/100 cm3 )371 UFC/100 cm3 )3 UFC/100 cm3 % abatement 0.15 )0.4 )61 0.5 )69 10 3 0.7 )0.8 )0.2 3 10 6.6 31 0.07 )25 1.3 8 )58.3 )27 )50.2 )25 )43 )6 2 )46 )35 )82 )35 )11 )92 )30 )80 )4 )71.1 )77.2 )86.8 )90.8 )90.5 )60 n 81 81 80 79 81 65 65 81 81 80 73 79 80 80 80 77 80 73 75 74 74 74 70 22 19 31 28 72 71 72 72 72 72 72 75 76 76 76 75 69 t 6.57 )1.41 )7.26 0.26 )13.25 13.40 1.28 0.52 )1.62 )0.64 1.67 2.16 9.20 6.21 0.40 )6.51 3.72 0.36 )4.41 )1.79 )5.73 )2.33 )4.49 )1.25 0.42 )2.49 )2.35 )1.20 )6.40 )1.78 )1.40 )10.64 )1.26 )0.28 )5.10 )3.32 )10.20 )10.02 )11.11 )3.84 Signicance Signicant Non-sign. Signicant Non-sign. Signicant Signicant Non-sign. Non-sign. Non-sign. Non-sign. Non-sign. Signicant Signicant Signicant Non-sign. Signicant Signicant Non-sign. Signicant Non-sign. Signicant Signicant Signicant Non-sign. Non-sign. Signicant Signicant Non-sign. Signicant Non-sign. Non-sign. Signicant Non-sign. Non-sign. Signicant Signicant Signicant Signicant Signicant Signicant

Negative dierence abatement; positive increase. Results of t-test (5% signicance level): n number of observations, t statistic t value.

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nitrites, 1% for nitrates, 18% for phosphates, 2% for DOC and 2% for heavy metals. Increases and decreases (percent), for each parameter, were considered signicant when higher than coecients of variations.

3. Results Average abatement and the percent abatement for historic data are shown in Table 1. For a clear identication of the most important parameters involved in the self-purication of the canal, these data were represented in a Box Whisker Plot (Fig. 2). By means of the t Test using paired data, the following parameters were found as having a signicant decrease between the beginning and the end the canal (5% signicance level; t values are reported in Table 1): turbidity, ammonia, total phosphates, Al, Fe, Pb, Mn, Cu, Zn, 1,1,1-trichloroethane, tetrachloroethylene, heterotrophic count at 22 and 36 C, total and fecal coliforms, fecal streptococci, sultereducing clostridia spores. For some others (pH, chlorides, uorides, nitrites, sodium, and sulfates) a signicant increase was observed. Also dissolved oxygen showed a signicant increase with a 10% signicance level. Statistical results are evident also in Fig. 3, which shows the trends of pH (Fig. 3(a)), oxygen (Fig. 3(b)), nitrates (Fig. 3(c)), nitrites (Fig. 3(d)) and phosphates (Fig. 3(e)), from historic data (19952000). Dissolved oxygen, nitrites concentration and pH were generally higher at station 4 than at station 1 (particularly in

summer for nitrites). Phosphates were lower at station 4 than at station 1 and nitrates were also lower, but only in summer. However for nitrates and nitrites a seasonal trend was more evident. Analytical results (recent data) are reported in Tables 24, and plotted in Figs. 46. For ammonium, phosphates, turbidity, heavy metals and bacteria a net abatement was observed from station 1 to station 2. Only ammonium, phosphates and bacteria decreased from station 2 to station 4. Whereas for turbidity and heavy metals an increase was observed from station 2 to station 4 and also from station 2 to station 3 on 12th September. Concentration of nitrites grew signicantly from station 1 to station 4. Nitrates and dissolved organic carbon did not show a particular trend. An estimation of the budget for all species of inorganic nitrogen was attempted, in order to establish if these species were simply transforming from one species into another or if a total inorganic nitrogen decrease also occurred. Concentrations of inorganic nitrogen for historic data is reported in Table 5 and for recent data in Table 6.

4. Discussion 4.1. Nitrogen From historic data, a systematic decrease of total inorganic nitrogen during the summer period (especially

Box Whisker Plot of differences 20

10

-10

Means+SD Means-SD Means+SE Means-SE Means HeterCount22C/1000 HeterCount36C/1000 Total Coliform/10000 1,1,1Trichloroet*100 Tetrachloroeth*10 Fluoride*100 Chloride*10 Fecal Cliform/1000 Phosphates*100 Manganese Sodium*10 Copper Iron/10 pH*10 Fecal Strept./100 Clostridia Spores Nitrites*100 Turbidity Potassium*10 Aluminum/10 Ammonium Sulfates Oxygen Zinc

-20

-30

Fig. 2. Box Whisker Plot of dierences for routinely acquired historic data: negative dierence abatement; positive increase. See Table 1 for units.

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Fig. 3. Trends of pH (a), oxygen (b), nitrates (c), nitrites (d) and phosphates (e) from 1995 to 2000 (historic data obtained from monthly analyses) at stations 1 and 4 (see Fig. 1, map of the canal).

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Table 2 Concentrations of selected parameters obtained by analyzing water samples during sampling session I (27th March), at stations 1 (Quarto dAltino), 2 (End soil tract) and 4 (Favaro Veneto) (recent data) St. 1 2 4 Turbidity (NTU) 7.4 2.8 8.0 Aluminum (lg/dm3 ) 1 2 4 162 111 352 Heterotrophic count at 22 C (CFU/cm3 ) 1 2 4 150 000 17 300 50 400 Ammonium (mg/dm3 ) 0.26 0.12 0.07 Iron (lg/dm3 ) 145.0 53.0 147.5 Heterotrophic count at 36 C (CFU/cm3 ) 100 000 11 900 50 000 Nitrites (mg/dm3 ) 0.10 0.20 0.19 Lead (lg/dm3 ) <0.1 <0.1 <0.1 Total coliforms (CFU/100 cm3 ) 33 400 4750 10 000 Nitrates (mg/dm3 ) 15.6 15.5 15.5 Manganese (lg/dm3 ) 10.1 6.0 9.4 Fecal coliforms (CFU/100 cm3 ) 6000 700 360 Total phosphates (mg/dm3 ) 0.27 0.30 0.24 Copper (lg/dm3 ) 2.5 1.8 7.4 Fecal streptococci (CFU/100 cm3 ) 246 71 3 DOC (mg/dm3 ) 2.20 2.32 2.16 Zinc (lg/dm3 ) 14.8 10.2 11.4 Clostridia spores (CFU/100 cm3 ) 42 15 30

R. Vagnetti et al. / Chemosphere 52 (2003) 17811795

Table 3 Concentrations of selected parameters obtained by analyzing water samples during sampling session II (27th June), at stations 1 (Quarto dAltino), 2 (End soil tract) and 4 (Favaro Veneto) (recent data) St. 1 2 4 Turbidity (NTU) 9.4 7.4 14.4 Aluminum (lg/dm3 ) 1 2 4 42.5 48.8 266.0 Heterotrophic count at 22 C (CFU/cm3 ) 1 2 4 80 000 40 000 20 000 Ammonium (mg/dm3 ) 0.19 0.08 0.08 Iron (lg/dm3 ) 87.6 98.1 207.0 Heterotrophic count at 36 C (CFU/cm3 ) 20 000 4000 3000 Nitrites (mg/dm3 ) 0.15 0.19 0.18 Lead (lg/dm3 ) <0.1 <0.1 <0.1 Total coliforms (CFU/100 cm3 ) 97 400 39 000 24 800 Nitrates (mg/dm3 ) 18.99 16.92 17.05 Manganese (lg/dm3 ) 9.9 11.0 11.8 Fecal coliforms (CFU/100 cm3 ) 7560 3960 780 Total phosphates (mg/dm3 ) 0.13 0.11 0.09 Copper (lg/dm3 ) 2.8 2.5 3.1 Fecal streptococci (CFU/100 cm3 ) 400 44 19 DOC (mg/dm3 ) 1.9 1.8 1.7 Zinc (lg/dm3 ) 6.6 4.7 7.6 Clostridia spores (CFU/100 cm3 ) 30 22 20

R. Vagnetti et al. / Chemosphere 52 (2003) 17811795 Table 4 Concentrations of selected parameters obtained by analyzing water samples during sampling session III (12th September), at stations 1 (Quarto dAltino), 2 (End soil tract), 3 (Siphon) and 4 (Favaro Veneto) (recent data)

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in June) was observed. This phenomenon can last until the early autumn depending on the particular year. This is evident from the data reported in Table 5. During the other periods of the year, the inorganic nitrogen budget can be considered closed: in other words the concentration of total inorganic nitrogen remains constant. This trend has been conrmed by the results of the experiments (Table 6). The only total inorganic nitrogen decrease was monitored in the sampling session of 27th June. In the other sampling sessions the concentration at station 1 is not dierent from the concentration at station 4. The summer abatement of nitrogen species was observed by several investigators (Elosegui et al., 1995; Bratli et al., 1999; Jing et al., 2001) and it can be reasonably ascribed to a greater assimilation by living organisms, particularly plants. In fact, in this season the most ecient nutrient and pollutant uptake occurs, because higher air and water temperatures and a more intense light irradiation favor higher plant productivity (Volterra and Mancini, 1994). The vegetale species present in the canal include also some which are used for phytoremediation: e.g. Elodea canadensis, Potemogeton natans, Ceratophyllum demersus (Volterra and Mancini, 1994). In addition, nitrogen can be denitively removed by denitrication, a biological process which is dependent on temperature and favored in the summer (Bratli et al., 1999; De Crespin De Billy et al., 2000; Haag and Kaupenjohann, 2001). It is evident from the recent data (Table 6) that this reduction of nitrogen in summer is mostly due to a reduction of nitrate concentrations. In fact, nitrates accounted for more than 98% of the total nitrogen species. Considering the nitrogen species separately, a signicant ammonium abatement was observed both in the historic data and in the experimental data. Considering these latter, it can also be observed that this decrease is more evident at the end of the beaten soil tract. This phenomenon is considered normal in natural oxygenated waters, and it was observed in all considered selfpurication studies (Elosegui et al., 1995; Lam-Leung et al., 1996; Bratli et al., 1999; Jing et al., 2001). It is caused by several mechanisms, including oxidation (nitrication) and biological assimilation. In parallel to an ammonium drop, a signicant increase of nitrites was observed both in the historic data and in the experiments. In this case, the more important increase of nitrites was monitored between the beginning of the canal and the end of beaten soil tract. It is known that the overall process of nitrogen oxidation from ammonia to nitrate can be considered a two step process, i.e. the oxidation from ammonia to nitrite and from nitrite to nitrate. The concentration of the intermediate species nitrite depends on the relative rates of the two steps. When the step from nitrite to nitrate is somehow slowed down, the nitrite concentration increases. According to Von der Wiesche

1.9 1.8 1.8 1.8

6.7 3.1 4.9 7.9

Clostridia spores (CFU/100 cm3 ) Fecal streptococci (CFU/100 cm3 ) Fecal coliforms (CFU/100 cm3 ) Total coliforms (CFU/100 cm3 ) Heterotrophic count at 36 C (CFU/cm3 ) Heterotrophic count at 22 C (CFU/cm3 )

DOC (mg/dm3 )

Zinc (lg/dm3 )

Total phosphates (mg/dm3 )

0.14 0.13 0.13 0.12

Copper (lg/dm3 )

Nitrates (mg/dm3 )

Manganese (lg/dm3 )

Nitrites (mg/dm3 )

Lead (lg/dm3 )

Ammonium (mg/dm3 )

Iron (lg/dm3 )

Aluminum (lg/dm3 )

Turbidity (NTU)

93 76 155 238

St.

103 100 332 487

6.0 3.3 6.2 9.7

1 2 3 4

1 2 3 4

1 2 3 4

3760 2000 2320 1680

13 200 2440 4680 2100

0.16 0.07 0.07 0.06

82 600 12 000 5900 5100

0.13 0.17 0.18 0.17

<0.1 <0.1 <0.1 <0.1

6000 2440 780 550

17.6 17.5 17.6 17.5

7.7 5.5 7.7 10.5

750 100 300 70

1.0 0.6 0.7 2.9

83 56 26 32

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Sampling session I - Stations 1,2,4 - Nutrients

0.32

0.28

NH 4 (mg/dm3) NO 2 (mg/dm3) NO 3 (mg/dm3)*10 -2 PO4 (mg/dm3) DOC (mg/dm 3)*10 -1

0.24

0.20

0.16

0.12

0.08

(a)
0.04 Station 1 Station 2 Station 4

Sampling session I - Stations 1,2,4 - Turbidity and metals 40 35 30 25 20 15 10 5 0 -5

Turbidity (NTU) Al (mg/dm 3 )*10 -1 Fe (mg/dm 3 )*10 -1 Mn (m g/dm 3 ) Cu (mg/dm 3 ) Zn (mg/dm 3 )

(b)
Station 1 Station 2 Station 4

Sampling session I - Stations 1,2,4 - Bacteria 350

3 -3

300

250

Heter. count 22C (CFU/cm )*10 3 -3 Heter. count 36C (CFU/cm )*10 3 -2 Total coliforms (CFU/100cm )*10 3 -1 Fecal coliforms (CFU/100cm )*10 3 Fecal streptococci (CFU/100cm ) 3 Clostridia spores (CFU/100cm )

200

150

100

50

(c)
0 Station 1 Station 2 Station 4

Fig. 4. Recent data obtained by analyzing water samples during sampling session I (27th March) at stations 1 (Quarto dAltino), 2 (End soil) and 4 (Favaro Veneto): (a) concentrations of ammonium, dissolved organic carbon, nitrates, nitrites and phosphates, (b) turbidity, aluminum, copper, iron, manganese, and zinc, (c) heterotrophic count at 22 and 36 C, total coliforms, fecal coliforms, fecal streptococci, clostridia spores.

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Sampling session II - Station 1,2,4 - Nutrients 0.20

1791

0.18

0.16 NH4 (mg/dm 3 ) 0.14 NO2 (mg/dm3 ) NO3 (mg/dm3 )*10-2 0.12 PO4 (mg/dm3 ) DOC (mg/dm3)*10-1

0.10

0.08

(a)
0.06 Station 1 Station 2 Station 4

Sampling session II-Stations 1-2-4- Turbidity and metals 30

Turbidity (NTU) Al ( g/dm 3 )*10 -1 Fe ( g/dm 3 )*10 -1 Mn ( g/dm 3 ) Cu ( g/dm 3 ) Zn ( g/dm 3 )

24

18

12

(b)
0 Station 1 Station 2 Station 4

Sampling sessionII-Stations1-2-4-Bacteria 110

Heter. count 22C (CFU/cm 3)*10 -3 Heter. count 36C (CFU/cm 3)*10 -3 Total coliforms (CFU/100cm 3)*10 -3 Fecal coliforms (CFU/100cm 3 )*10-2 Fecal streptococci (CFU/100cm 3 )*10 -1 Clostridia spores (CFU/100cm 3 )

90

70

50

30

10

(c)
-10 Station 1 Station 2 Station 4

Fig. 5. Recent data obtained by analyzing water samples during sampling session II (27th June) at stations 1 (Quarto dAltino), 2 (End soil) and 4 (Favaro Veneto). Same parameters as Fig. 4.

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Sampling session III - Stations 1,2,3,4 - Nutrients 0.20

0.18

0.16 0.14

0.12

0.10 NH 4 (mg/dm 3 ) 0.08 NO 2 (mg/dm 3 ) NO 3 (mg/dm 3 )*10 -2 0.06 0.04 Station 1 Station 2 Station 3 Station 4 PO 4 (mg/dm 3) DOC (mg/dm3 )*10 -1

(a)

Sampling session III-Stations 1,2,3,4 - Bacteria

140 Heter. count 22C (CFU/cm3)*10 Heter. count 36C (CFU/cm3)*10-2 3 Total coliforms (CFU/100cm )*10-3 Fecal coliforms (CFU/100cm3)*10-2 -1 Fecal streptococci (CFU/100cm3)*10 Clostridia spores (CFU/100cm3 )
-2

120

100

80

60

40

20

(b)
0 Station 1 Station 2 Station 3 Station 4

Sampling session III - Stations 1,2,3,4 - Turbidity and metals

50

40

Turbidity (NTU) Al (g/dm 3 )*10-1 Fe (g/dm 3)*10-1 Mn (g/dm 3) Cu ( g/dm 3) Zn (g/dm 3)

30

20

10

(c)
0 Station 1 Station 2 Station 3 Station 4

Fig. 6. Recent data obtained by analyzing water samples during sampling session III (12th September) at stations 1 (Quarto dAltino), 2 (End soil), 3 (Additional point) and 4 (Favaro Veneto). Same parameters as Fig. 4.

R. Vagnetti et al. / Chemosphere 52 (2003) 17811795

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Table 5 Total inorganic nitrogen (NNH4 + NNO2 + NNO3 ) at the beginning and at the end of the canal (station 1 and 4) from 1995 to 2000 (historic data) Date Temperature (C) 8.1 10.6 10.3 11.0 14.0 15.0 16.3 18.3 19.8 18.0 16.5 13.6 10.5 10.4 11.2 8.0 10.1 11.9 14.0 17.4 17.4 18.2 18.0 14.5 13.7 13.2 9.9 9.5 9.6 13.7 16.3 14.3 18.5 19.2 18.2 21.3 11.7 Total nitrogen (mg/dm3 ) 1 16/01/95 13/02/95 27/02/95 13/03/95 10/04/95 22/05/95 05/06/95 03/07/95 24/07/95 28/08/95 25/09/95 30/10/95 20/11/95 18/12/95 15/01/96 12/02/96 11/03/96 09/04/96 06/05/96 03/06/96 01/07/96 29/07/96 26/08/96 23/09/96 21/10/96 18/11/96 16/12/96 14/01/97 17/02/97 10/03/97 05/05/97 02/06/97 01/07/97 28/07/97 25/08/97 22/09/97 17/11/97 4.17 3.93 4.09 3.43 4.12 4.06 3.61 4.09 4.01 4.25 4.33 4.50 3.65 3.42 3.73 4.08 3.96 3.50 3.33 3.32 3.30 3.77 3.66 3.68 3.68 3.42 3.51 3.80 3.65 3.59 3.32 3.27 3.11 3.41 3.55 3.48 3.58 4 4.15 3.78 3.92 3.21 3.93 4.13 3.37 3.46 3.68 3.56 4.10 4.46 3.70 3.58 3.83 3.87 3.88 3.01 3.02 2.92 2.98 3.46 3.27 3.41 2.81 3.07 3.32 3.59 3.35 3.38 2.89 2.79 2.92 3.18 3.35 3.09 3.34 Dierence station 4 1 (mg/dm3 ) )0.02 )0.15 )0.16 )0.23 )0.19 0.07 )0.24 )0.63 )0.33 )0.69 )0.23 )0.04 0.05 0.16 0.10 )0.21 )0.08 )0.48 )0.32 )0.40 )0.32 )0.31 )0.39 )0.27 )0.88 )0.36 )0.19 )0.21 )0.31 )0.21 )0.44 )0.48 )0.19 )0.22 )0.20 )0.40 )0.24 Date Temperature (C) 9.3 10.1 10.0 13.2 13.7 16.3 17.4 19.9 19.6 16.9 15.7 14.1 8.7 8.5 10.9 13.9 16.0 19.2 18.0 18.5 19.1 13.0 11.2 9.6 8.7 11.4 14.4 16.5 17.2 18.6 16.6 15.9 13.7 11.9 12.9 12.3 11.9 Total nitrogen (mg/dm3 ) 1 15/12/97 12/01/98 09/02/98 09/03/98 06/04/98 19/05/98 01/06/98 30/06/98 27/07/98 24/08/98 21/09/98 19/10/98 14/12/98 08/02/99 08/03/99 12/04/99 03/05/99 31/05/99 28/06/99 26/07/99 23/08/99 18/10/99 15/11/99 13/12/99 10/01/00 07/02/00 06/03/00 17/04/00 15/05/00 05/06/00 10/07/00 07/08/00 02/10/00 30/10/00 07/11/00 08/11/00 20/11/00 3.57 3.64 3.65 3.75 3.35 3.16 3.24 3.26 3.33 3.58 3.53 3.86 3.62 3.47 3.97 3.50 3.29 3.04 3.25 3.42 3.39 3.73 3.72 3.71 3.58 3.56 3.96 3.26 3.31 3.50 3.71 3.46 3.52 4.20 3.62 4.10 4.25 4 3.41 3.46 3.36 3.50 3.26 2.79 2.95 3.00 3.31 3.36 3.26 3.65 3.39 3.29 3.77 3.37 2.96 2.61 3.00 3.00 3.17 3.13 3.55 3.50 3.21 3.51 3.72 3.14 3.19 3.32 3.40 3.44 3.25 4.11 3.92 3.67 4.23 Dierence station 4 1 (mg/dm3 ) )0.16 )0.18 )0.29 )0.25 )0.09 )0.36 )0.29 )0.26 )0.03 )0.23 )0.27 )0.21 )0.23 )0.18 )0.19 )0.13 )0.33 )0.43 )0.25 )0.41 )0.22 )0.60 )0.17 )0.21 )0.38 )0.05 )0.24 )0.12 )0.12 )0.19 )0.31 )0.02 )0.27 )0.10 0.30 )0.43 )0.02

Table 6 Nitrogen concentration in ammonium, nitrites, nitrates species and total inorganic nitrogen concentration (mg/dm3 ) from recent data St. 1 2 3 4 27th March NNH4 0.20 0.09 0.05 NNO2 0.03 0.06 0.06 NNO3 3.52 3.50 3.50 Tot 3.76 3.66 3.61 27th June NNH4 0.15 0.06 0.06 NNO2 0.05 0.06 0.05 NNO3 4.29 3.82 3.85 Tot 4.48 3.94 3.97 12th September NNH4 0.13 0.05 0.05 0.05 NNO2 0.04 0.05 0.05 0.05 NNO3 3.98 3.95 3.98 3.95 Tot 4.14 4.06 4.08 4.05

and Wetzel (1998), who observed a similar trend, this phenomenon can occur when the temperature exceeds the range 1017 C, in which the balance between the two forms is maintained. At higher temperatures, inhibition of nitrate formation is greater than the in-

hibition of nitrite formation. In the studied canal, temperatures were often above that range in summer (Table 5). Observing the seasonal trend of nitrite concentration, we can notice winter minima and summer maxima (Fig. 3(d)).

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R. Vagnetti et al. / Chemosphere 52 (2003) 17811795

Considering all of the data, no signicant dierence of nitrate concentrations was observed between the beginning and the end of the canal, apart from the summer period when a signicant decrease of concentrations was detected (Fig. 3(c)). 4.2. Phosphates From the statistical processing of historic data (Table 1), it is evident that total phosphate concentrations signicantly decrease along the course of the canal (Fig. 3(e)). This is a typical phenomenon frequently observed in natural purication processes (Benka-Coker and Ojior, 1995; Elosegui et al., 1995; Lam-Leung et al., 1996; Bratli et al., 1999; De Crespin De Billy et al., 2000; Jing et al., 2001). For phosphorus removal the physical chemical processes, e.g. precipitation with calcium, adsorption and sedimentation, are dominant. Phosphates can be eliminated from water also by uptake by primary producers or microbial decomposers (Elosegui et al., 1995; Bratli et al., 1999). The abatement, for recent data, was signicant (percent higher than coecient of variations) only on 27th June: in fact in the summer period biologic assimilation is greater. 4.3. Bacteria The concentration of bacteria in the water sharply dropped from the beginning to the end of the canal as a consequence of sedimentation and natural decay, but an important abatement factor is also the ltration by aquatic plants (mainly by rhizosphere) (Benka-Coker and Ojior, 1995; Elosegui et al., 1995; Borin and Marchetti, 1997). 4.4. Turbidity and heavy metals The observed behavior for turbidity and heavy metal concentrations was dicult to explain. A net abatement was observed from the data collected for six years (19952000). This decrease was attributed to sedimentation or to a combination of adsorption and sedimentation (Linnik and Zubenko, 2000). However data investigated from the second half of 2000 only, showed remarkable increases of these parameters. This phenomenon non-remarkable overall, being limited to the last period, is conrmed by all recent data. From the analytical results of the experiments, it can be seen that a decrease occurs in the beaten soil tract, whereas in the sample corresponding to the siphon located 1 km downstream at the end of this tract (station 3), some resuspensions occur that causes turbidity and heavy metal concentrations to exceed the values at the beginning of the canal. The above observation is further emphasized by a remarkable drop in concentrations observed at the end of the beaten soil tract for other

parameters more sensitive to the self-purication process, namely ammonia, phosphates and all bacteria. For other parameters e.g. pH, chlorides, uorides, sodium, sulfates and dissolved oxygen, a signicant increase from the beginning to the end of the canal was observed from the historic data. Whereas it is easy to explain the increase of pH and dissolved oxygen (Fig. 3(a) and (b)) due to more photosynthesis occurring in the canal, the explanation for increases of chlorides, uorides, sodium and sulfates is unclear. It can be reasonably hypothesized that these parameters, which are typical of marine waters, would increase as a consequence of deposition of marine spray (Wilson, 1975) transported from the Venice Lagoon, which is less than 5 km from the canal. 5. Conclusions Along the course of the canal, a self-purication process was observed to occur which was signicant for ammonium, total phosphates and bacteria. The largest extent of this process took place in the rst tract of the canal (beaten soil) in which a net abatement of turbidity and metals occurred as well. Evidence of an increase of turbidity and metals in the second tract and the remarkable increase of some parameters such as chlorides, uorides, sodium, sulfates in the whole tract are under further investigation. It can be therefore concluded that a more natural condition, such as that in the beaten soil tract, can signicantly favor natural self-purication processes leading to improved water quality. References
AWWA, 1998. Standard Methods for the Examination of Water and Wastewater, 20th ed. APHA, Washington. Benka-Coker, M.O., Ojior, O.O., 1995. Eect of slaughterhouse wastes on the water quality of Ikpoba River, Nigeria. Bioresource Technology 52, 512. Benoit, R.J., 1971. Self-purication in natural waters. In: Ciaccio, L.L. (Ed.), Water and Water Pollution Handbook, vol. 1. Dekker, New York. Borin, M., Marchetti, C., 1997. Sistemi di depurazione delle acque basati sulluso di vegetazione macrota. Ambiente Risorse Salute 55, 713. Bratli, J.L., Skiple, A., Mjelde, M., 1999. Restoration of lake Borrevannetself-purication of nutrients and suspended matter through natural reed-belts. Water Science and Technology 40 (3), 325332. Brusseau, M.L., Bohn, H.L., 1996. Chemical processes aecting contaminant fate and transport in soil and water. In: Pollution Science. Academic Press, San Diego, pp. 6178. Chambers, P.A., Prepas, E.E., 1994. Nutrient dynamics in riverbeds: the impact of sewage euent and aquatic macrophytes. Water Research 28 (2), 453464. C.N.R.Istituto di Ricerca sulle Acque, 1994. Metodi analitici per le acque. Istituto poligraco e Zecca dello Stato, Roma.

R. Vagnetti et al. / Chemosphere 52 (2003) 17811795 Cunningham, S.D., Davi, W.O., 1996. Promises and prospect of phytoremediation. Plant Physiology 110, 715719. De Crespin De Billy, V., Reyes-Marchant, P., Lair, N., Valadas, B., 2000. Impact of agricultural practices on a small headwater stream: terrestrial and aquatic characteristics and self-purifying processes. Hydrobiologia 421, 129 139. Elosegui, A., Arana, X., Basaguren, A., Pozo, J., 1995. Selfpurication processes along a medium-sized stream. Environmental Auditing 19 (6), 931939. Haag, D., Kaupenjohann, M., 2001. Landscape fate of nitrate uxes and emissions in Central Europea critical review of concepts, data, and models for transport and retention. Agriculture, Ecosystems and Environment 86 (1), 121. Jing, S.R., Lin, Y.F., Lee, D.Y., Wang, T.W., 2001. Nutrient removal from polluted river water by using constructed wetlands. Bioresource Technology 76 (2), 131135. Lam-Leung, S.Y., Cheung, M.T., He, Y.Q., Zheng, Q.H., Wen, W.Y., Zhang, Y.Y., 1996. Natural removal of added nutrients, reactive phosphorus, crude oil, and heavy metals from the water phase in a simulated water/sediment system. Environment International 22 (2), 195212. Linnik, P.M., Zubenko, I.B., 2000. Role of bottom sediments in the secondary pollution of aquatic environments by heavy-

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metal compounds. Lakes and Reservoirs: Research and Management 5 (1), 1121. Manahan, S.E., 1994. Environmental Chemistry. Lewis Publishers by CRC Press, Boca Raton, FL. Marconato, E., Aquaprogram S.r.l., 2003. Private communication of unpublished results obtained during the survey: La fauna ittica della provincia di Venezia. Provincia di Venezia. Marconato, E., Maio, G., Salviati, S., 2000. La fauna ittica della provincia di Venezia. Provincia di Venezia, Assessorato alla Caccia, Pesca e Polizia Provinciale. Meagher, R.B., 2001. Phytoremediation of toxic elemental and organic pollutants. Current Opinion in Plant Biology 3 (2), 153162. Piccolo, D., 2000. Statistica. Il Mulino, Bologna. Suzuky, M., 1997. Role of adsorption in water environment processes. Water Science and Technology 35 (79), 111. Vismara, R., 1998. Ecologia Applicata. Hoepli U, Milano. Volterra, L., Mancini, L., 1994. Fitodepurazione e riuso successivo delle macrote. Ambiente Risorse Salute, 3036. Von der Wiesche, M., Wetzel, A., 1998. Temporal and spatial dynamics of nitrite accumulation in the river Lahn. Water Research 32 (5), 16531661. Wilson, T.R.S., 1975. Salinity and the major elements of sea water. In: Riley, J.P., Skirrow, G. (Eds.), Chemical Oceanography, 2nd ed., vol. 1. Academic Press, London.