A NEW VOLTAMMETRIC METHOD FOR THE SIMULTANEOUS MONITORING OF HEAVY METALS IN SEA WATER, SEDIMENTS, ALGAE AND CLAMS:

APPLICATION TO THE GORO BAY ECOSYSTEM

CLINIO LOCATELLI and GIANCARLO TORSI
Department of Chemistry G. Ciamician, University of Bologna, Bologna, Italy ( author for correspondence, e-mail: clinio@ciam.unibo.it)

(Received 5 December 2000; accepted 2 May 2001)

Abstract. Arsenic(III), selenium(IV), copper(II), lead(II), cadmium(II), zinc(II) have been determined in sea water, sediments, algae and clams by differential pulse cathodic (DPCSV) and anodic (DPASV) stripping voltammetry. The voltammetric measurements are carried out using a conventional three-electrode cell and the ammonia-ammonium chloride buffer pH 9.2 as supporting electrolyte. The analytical procedure has been veried by the analysis of the standard reference materials (Estuarine Sediment BCR- CRM 277, Ulva Lactuca BCR-CRM 279 and Mussel Tissue BCR-CRM 278). The precision and the accuracy are less than 5%. This procedure is utilized for the monitoring of heavy metals in the Po river mouth area (Italy). Keywords: algae, clams, marine environmental matrices, sea Water, sediments, stripping voltammetry

1. Introduction Toxic and persistent substances are increasing in the environment continuously due to anthropic activities. They tend to concentrate in all the aquatic matrices in the environment (Chapman et al., 1982), i.e. in the aquatic food chain, and for this reason, in particular the rapid heavy metal diffusion as an environmental contaminant has called attention to their determination at trace and ultratrace level (Sarzanini and Mentasti, 1991; Clement et al., 1995) and especially to their speciation (Waller and Pickering, 1990; Florence, 1992; Das et al., 1995). Several sample treatment procedures (Van Loon, 1985; Stoeppler, 1997), and different analytical techniques have been reported for this purpose (Sarzanini and Mentasti, 1991). However, spectroscopic (Slavin, 1984; Welz, 1985) and voltammetric (Bond, 1980; Wang, 1985) techniques have been routenly employed. The voltammetric methods are a valid and effectual option in the multicomponent analysis of metals, as they are highly sensitive (Bond, 1980; Wang, 1985; Bobrowski and Bond, 1993) and selective (Bobrowski and Bond, 1993; Bond et al., 1976; Locatelli et al., 1987). The sensitivity and selectivity can be further improved by the use of new types of electrodes (Christensen et al., 1982; Wang et al., 1984). In the eld of multicomponent determinations multiple-element schemes, coupEnvironmental Monitoring and Assessment 75: 281292, 2002. 2002 Kluwer Academic Publishers. Printed in the Netherlands.

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ling anodic stripping and cathodic stripping voltammetry, have been reported by Adeloju et al. (Adeloju et al., 1983), while Gil and Ostapczuk (Gil and Ostapczuk, 1994) have developed an interesting potentiometric stripping analysis approach. The present work examines the possibility of simultaneously determining As(III), Se(IV) and Cu(II), Pb(II), Cd(II) and Zn(II) in environmental matrices like sea water, sediments, algae and clams (Po river mouth area, Italy), by differential pulse cathodic (DPCSV) and anodic (DPASV) stripping voltammetry, using a conventional three electrode cell and ammonia-ammonium chloride buffer solution (pH 9.2) as supporting electrolyte. Moreover, few data relevant to metal concentrations in the Goro Bay ecosystem are available (Fagioli et al., 1994; Locatelli et al., 1996; Bondavalli et al., 1996). Therefore, the present paper can be considered as the most complete and exhaustive rst reference on the analytical quantication of toxic metals in this area.

2. Experimental 2.1. A PPARATUS AMEL (Milan, Italy) Model 433 Multipolarograph, with stationary mercury electrode, Ag/AgCl, KCl satd. electrode and platinum wire was used. The voltammetric cell was kept at 20.0 0.5 C. All the solutions were deaerated with pure nitrogen for 15 min prior to the measurements, and a nitrogen blanket was maintained above the solution during the analysis. The reaction mixture was deaerated for 2 min after each standard addition. 2.2. R EAGENTS AND REFERENCE SOLUTIONS All solutions were prepared with deionized water (Millipore, Milli Q), and all reagents were suprapure grade. Ammonia-ammonium chloride buffer solution pH 9.2 was prepared by mixing an appropriate amount of 1 mol L1 hydrochloric acid (50 mL) and 1 mol L1 ammonia solution (85.5 mL). Aqueous stock solutions of As(III), Se(IV), Cu(II), Pb(II), Cd(II) and Zn(II) were prepared by dilution of the respective standard 1000 mg L1 solutions (Merck, Germany). The Teon voltammetric cell was rinsed every day with suprapure concentrated nitric acid. The following standard reference materials were used: Estuarine Sediment BCRCRM 277, Ulva Lactuca BCR-CRM 279 and Mussel Tissue BCR-CRM 278.

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Figure 1. Sampling sites in the Goro Bay.

2.3. S AMPLING Sea water, sediments, algae and clams were sampled in the Goro Bay (Province of Ferrara, Italy), a very important area devoted to the shing and breeding of mussels and clams for food, but with considerable pollution problems for its location in proximity of the mouth of the Po river, the carrier towards the sea of a large amount of industrial and domestic waste water. The samples were collected (February and August 2000) in six different positions (Figure 1), during winter and summer. a) Sea Water. Sea water samples were collected using suction pump, made of non-polluting material (stainless steel and pyrex), immediately ltered on the spot on 0.45 m membranes, transferred to polyethylene bottles (previously washed with a solution of 10% suprapure HNO3 for 48 h, and, successively, many times with deionized water), stored at 4 C and analysed within 72 hr (see section Sample Preparation). b) Sediments. Sampling was performed by means of a plastic device: single columns (section: 63.6 cm2 , height: 10 cm) were drawn out and put in previously treated polyethylene bottles. The sample was completely dried at room temperature, passed through a 10 mesh inox sieve to eliminate coarse material, powdered by means of a corundum ball mill, passed through a 150 mesh inox sieve, nally dried at 50 C for 48 hr prior to sample preparation.

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c) Algae. About 78 Kg, wet weight, of algae, species Ulva Rigida were collected with a small net, washed thoroughly on the spot with deionized water, transferred into polyethylene bags, transported to the laboratory in a portable refrigerator, dried for 48 hr at 4045 C, ground and homogenised. Then aliquots were exactly weighed, digested (see section Sample Preparation) and analysed. d) Clams. About 10 kg of clams, species Tapes Philippinarum, were collected, the edible parts carefully sampled with a plastic appliance, immediately liophilized for 30 hr, successively homogenised in an agate mortar, digested (see section Sample Preparation) and analysed. 2.4. S AMPLE PREPARATION a) Sea Water. Sea water samples were buffered at pH 9.2 and then analysed. b) Sediments. Approximately 0.50.8 g of sediment was accurately weighed in a Pyrex digestion tube and dissolved in hydrochloric acid (7 mL of 37%) and nitric acid (5 mL of 69%). The tube was inserted into a cold home-made block digester, gradually raising the temperature up to 130 C and keeping this temperature for all the time of mineralization (2h). After cooling, the digest was ltered through Whatman N. 541 lter paper, evaporated almost to dryness and the soluble salts dissolved in 100 mL buffer solution (pH 9.2). c) Algae and Clams. Approximately 0.50.8 g of sample, accurately weighed in a Pyrex digestion tube, was dissolved in hydrochloric acid (5 mL of 37%) and nitric acid (5 mL of 69%). The tube was inserted in the cold home-made block digester, the temperature of which was gradually raised through a heating plate up to 130150 C and maintained until the red nitrous fumes stopped. After cooling 4 mL of 96% sulphuric acid were added to it, the temperature was raised again up to 130150 C, and it was kept for 2 hr. After cooling the digest was ltered through Whatman N. 541 lter paper, slowly boiled, evaporated almost to dryness and, after cooling, the soluble salts were dissolved in 100 mL of buffer solution (pH 9.2).

3. Results and Discussion 3.1. AQUEOUS REFERENCE SOLUTIONS At rst, the analytical procedure was set up and standardised using the aqueous reference solutions and the standard reference materials. The experimental conditions of the voltammetric analytical procedure and the experimental peak potentials are reported in Table I. Aqueous reference solution was used to determine the analytical calibration functions for all the elements by differential pulse cathodic and anodic stripping

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TABLE I Experimental conditions for the simultaneous determination of As(III)-Se(IV) and Cu(II)-Pb(II)-Cd(II)-Zn(II) by differential pulse cathodic (DPCSV) and anodic stripping voltammetry (DPASV)a . Supporting electrolyte: ammonia-ammonium chloride buffer (pH 9.2) As(III)-Se(IV) (DPCSV) Ed Ef td tr dE/dt E r 1.050 1.700 230 10 10 50 0.065 0.250 600 Cu(II)-Pb(II)-Cd(II)-Zn(II) (DPASV) 1.300 0.200 180 10 10 50 0.065 0.250 600

a E : deposition potential (V/Ag, AgCl, KCl sat.); E : d f nal potential (V/Ag, AgCl, KCl sat.); td : deposition time (s); tr : delay time before the potential sweep (s); dE/dt: potential scan rate (mV/s); E: amplitude of pulse superposed (mV); : pulse duration (s); : pulse repetition (s); r: stirring rate (r.p.m.). Experimental peak potentials (V/Ag, AgCl, KCl sat.): 1.308 0.010[As(III)], 1.423 0.010 [Se(IV)], 0.458 0.005 [Cu(II)], 0.603 0.010 [Pb(II)], 0.769 0.010 [Cd(II)], 1.027 0.005 [Zn(II)].

voltammetry. In all cases, the correlation coefcients are good (r > 0.9990), the precision of the method is found to be satisfactory, i.e. lower than 5% (Miller and Miller, 1984). 3.2. S TANDARD REFERENCE MATERIALS ( QUALITY CONTROL PROCEDURE ) The method developed in aqueous reference solutions was applied to standard reference materials (Estuarine Sediment BCR-CRM 277, Ulva Lactuca BCR-CRM 279 and Mussel Tissue BCR-CRM 278), in order to conrm and verify the applicability of the analytical procedure. Using the experimental conditions of Table I, accuracy, expressed as relative error e, and the precision, expressed as relative standard deviation sr , are satisfactory, i.e. less than 6% (Table II). For water samples, accuracy was determined by percentage recovery test, and it was found to be 95106% for all the metals,

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TABLE II Accuracy and precision of the analytical procedure, calculated on ve independent measurements (concentration: g g1 , dry weight).a As Se Cu Pb Cd Zn

Reference material

Estuarine Sediment BCR-CRM 277

C. LOCATELLI AND G. TORSI

Ulva Lactuca BCR-CRM 279

Mussel Tissue BCR-CRM 278

Certied Determined e, % sr , % LOD Certied Determined e, % sr , % LOD Certied Determined e, % sr , % LOD

47.3 1.6 49.6 2.4 + 4.7 3.2 0.06 3.09 0.20 2.98 0.15 3.6 2.8 0.05 5.9 0.2 5.7 0.3 3.4 2.9 0.06

2.04 0.18 2.11 0.09 + 3.4 2.8 0.05 0.593 0.032 0.569 0.028 4.0 3.5 0.05 1.66 0.04 1.72 0.08 + 3.6 4.1 0.05

101.7 1.6 97.0 5.0 4.6 3.7 0.04 13.14 0.37 13.72 0.53 +4.4 4.2 0.04 9.60 0.16 9.96 0.49 +3.8 3.5 0.05

146 3 150 8 +2.7 3.1 0.03 13.48 0.36 12.89 0.45 4.4 3.7 0.04 1.91 0.04 1.83 0.10 4.2 3.9 0.04

11.9 0.4 11.3 0.8 5.0 4.6 0.01 0.274 0.022 0.264 0.11 3.6 3.6 0.01 0.34 0.02 0.32 0.03 5.9 3.8 0.02

547 12 558 23 +2.0 3.5 0.6 51.3 1.2 53.2 2.0 +3.7 4.1 0.7 76 2 79 4 +3.9 3.6 0.6

a e: relative error; s : relative standard deviation; the limit of detection (LOD) is expressed according to IUPAC (IUPAC, 1978) (K = 3) and corresponds r

to a probability of 99% (Miller and Miller, 1984). In the case of sea water, the limits of detection (LOD), expressed in g L1 are: 0.3 (As), 0.4 (Se), 0.3 (Cu), 0.2 (Pb), 0.1 (Cd), 0.5 (Zn).

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TABLE III Metal concentration in sea water (g L1 ) and in sediments, algae and clams (g g1 , dry weight) sampled in the Goro Bay (Winter Sampling).a Sampling site A Sea water Sediments Algae Clams B Sea water Sediments Algae Clams C Sea water Sediments Algae Clams D Sea water Sediments Algae Clams E Sea water Sediments Algae Clams F Sea water Sediments Algae Clams As(III) 2.1 0.1 49.2 2.3 1.0 0.1 5.2 0.3 61.8 3.9 1.4 0.2 < LOD 23.0 1.7 0.12 0.01 1.1 0.1 48.7 2.3 0.71 0.03 4.3 0.3 69.3 2.8 1.3 0.1 0.53 0.01 3.2 0.1 0.23 0.01 Se(IV) 0.77 0.04 1.5 0.1 1.1 0.1 0.96 0.05 1.7 0.1 0.91 0.03 < LOD 0.93 0.04 0.34 0.02 0.52 0.02 1.2 0.1 0.55 0.01 0.78 0.04 1.8 0.1 1.0 0.1 < LOD 0.67 0.03 0.15 0.01 Cu(II) Pb(II) Cd(II) 1.8 0.2 0.49 0.02 2.3 0.1 3.8 0.2 0.23 0.01 3.2 0.2 1.7 0.1 0.17 0.01 1.6 0.1 1.5 0.1 0.14 0.01 2.4 0.1 4.9 0.3 0.69 0.02 3.1 0.1 1.3 0.1 0.14 0.02 1.7 0.1 Zn(II) 25.6 1.2 210.0 7.7 106.8 4.9 46.3 2.1 270.5 6.9 119.1 4.3 15.8 0.6 77.0 2.9 73.4 1.8 13.4 0.5 130.7 6.9 96.9 4.0 39.0 1.9 276.1 11.3 123.0 4.7 14.9 0.7 83.4 4.3 69.6 1.9

38.5 1.4 11.2 0.4 70.2 3.5 29.6 1.2 8.0 0.3 12.1 0.6 91.3 2.9 32.5 1.6 71.3 3.1 50.4 1.8 16.2 0.6 19.2 1.3 21.2 0.9 6.4 0.4 32.6 1.3 14.3 0.7 5.4 0.3 6.9 0.2 23.9 1.1 7.6 0.4 35.6 1.8 27.2 1.2 6.3 0.3 11.0 0.4 105.4 5.1 29.6 1.3 80.3 2.9 49.0 1.9 9.6 0.5 25.3 1.1 23.0 1.6 6.9 0.3 34.6 1.4 20.0 1.2 5.2 0.3 8.3 0.4

a The concentrations are the mean value of ve independent measurements.

In all cases the relative standard deviation was lower than 5%. In the winter season algae were not present in the ecosystem considered.

and the precision, expressed as relative standard deviation sr on ve independent determinations was found to be less than 5%. The limit of detection for each element is also recorded in Table II. It is expressed according to IUPAC (IUPAC, 1978) (K = 3), correspond to a probability of 99% (Miller and Miller, 1984) and was calculated by the analytical calibration function of each element in the different matrices.

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TABLE IV Metal concentration in sea water (g L1 ) and in sediments, algae and clams (g g1 , dry weight) sampled in the Goro Bay (Summer Sampling).a Sampling site A Sea water Sediments Algae Clams B Sea water Sediments Algae Clams C Sea water Sediments Algae Clams D Sea water Sediments Algae Clams E Sea water Sediments Algae Clams F Sea water Sediments Algae Clams As(III) 2.7 0.1 53.3 2.3 0.71 0.03 1.5 0.1 5.2 0.2 59.3 2.1 0.96 0.02 1.6 0.1 < LOD 21.6 1.1 0.31 0.01 0.25 0.01 0.91 0.02 49.2 2.0 0.67 0.03 0.82 0.02 5.1 0.2 61.8 2.1 0.78 0.03 1.2 0.1 0.61 0.01 89.8 2.3 0.32 0.01 0.21 0.01 Se(IV) Cu(II) Pb(II) Cd(II) Zn(II) 59.6 1.5 223.1 7.7 128.4 3.5 97.3 2.6 30.4 1.9 296.8 7.3 157.6 4.2 128.1 2.1 26.3 0.7 87.4 3.0 118.2 3.5 81.2 2.8 19.7 0.5 149.0 7.3 135.1 5.8 118.6 3.9 49.8 1.5 315.0 12.9 136.3 5.1 149.6 4.3 16.3 0.3 96.0 2.4 120.1 3.8 85.4 1.5

0.63 0.02 43.2 2.2 12.3 0.7 2.1 0.1 1.7 0.1 77.4 2.9 31.2 1.0 0.68 0.03 0.81 0.02 31.2 1.6 8.3 0.2 0.35 0.02 1.2 0.1 9.6 0.5 15.8 1.2 3.1 0.2 0.96 0.03 109.4 4.0 37.2 0.8 4.3 0.1 1.8 0.1 81.5 2.3 69.2 2.0 0.21 0.01 0.61 0.02 36.3 0.8 10.2 0.1 0.49 0.01 0.95 0.01 17.3 1.0 23.0 1.3 3.0 0.1 < LOD 25.6 1.4 10.8 0.2 1.9 0.1 0.88 0.07 37.2 1.2 18.4 0.5 0.08 0.01 0.22 0.01 28.6 1.3 6.9 0.1 0.25 0.01 0.46 0.02 7.8 0.3 15.9 0.3 1.4 0.1 0.59 0.02 29.0 1.2 10.5 0.3 1.4 0.1 1.3 0.1 43.8 1.5 35.6 1.2 0.15 0.01 0.42 0.01 25.1 0.8 8.3 0.4 0.18 0.01 0.63 0.03 7.2 0.2 20.2 1.1 2.3 0.1 1.2 0.1 106.0 4.2 35.9 1.0 5.3 0.1 1.6 0.1 88.7 2.6 56.7 1.5 0.77 0.02 0.82 0.03 36.8 1.3 11.6 0.4 0.37 0.01 1.1 0.1 10.4 0.5 45.6 1.7 3.7 0.1 < LOD 31.2 1.3 12.4 0.4 1.5 0.1 0.68 0.02 43.4 1.8 37.6 1.6 0.23 0.01 0.30 0.01 27.3 1.2 6.2 0.2 0.22 0.01 0.28 0.01 6.1 0.2 10.8 0.4 1.9 0.1

a The concentrations are the mean value of ve independent measurements.

In all cases the relative standard deviation was lower than 5%.

3.3. A PPLICATION TO THE GORO BAY ZONE , P O R IVER D ELTA (I TALY ) The analytical procedure, so set up on the standard reference materials, was used for real samples: the sea water, sediments, algae and clams sampled inside the Po river delta in the Goro Bay zone. The results, listed in Tables III and IV, lead to consider some environmental aspects about the spatial (at the same time, but in different sampling sites) and temporal (in the same site, but in different sampling times) variability of the heavy metal concentrations in the different matrices. The metal concentrations are higher

TABLE V Metal contamination in sea water sampled in the Goro Bay ecosystem. Comparable investigations

Sampling site

Winter sampling

Cu(II) Summer sampling Winter sampling

Pb(II) Summer sampling

Cd(II) Winter Summer sampling sampling

Winter sampling

Zn(II) Summer sampling

38.5 1.4 3.2 0.2 91.3 2.9 10.5 0.6 21.2 0.9 1.5 0.1 23.9 1.1 1.5 0.1 105.4 5.1 10.5 0.4 23.0 1.6

43.2 2.2 4.9 0.1 109.4 4.0 11.7 0.5 25.6 1.4 1.5 0.1 29.0 1.2 1.7 0.1 106.0 4.2 11.6 0.5 31.2 1.3

11.2 0.4 2.1 0.1 32.5 1.6 2.8 0.1 6.4 0.4 2.3 0.1 7.6 0.4 2.1 0.1 29.6 1.3 2.2 0.1 6.9 0.3

12.3 0.7 4.3 0.2 37.2 0.8 5.1 0.2 10.8 0.2 3.2 0.1 10.5 0.3 2.4 0.2 35.9 1.0 3.6 0.2 12.4 0.4

1.8 0.2 0.4 0.1 3.8 0.2 0.7 0.1 1.7 0.1 0.4 0.1 1.5 0.1 0.3 0.1 4.9 0.3 0.4 0.1 1.3 0.1

2.1 0.1 1.3 0.1 4.3 0.1 0.9 0.1 1.9 0.1 0.6 0.1 1.4 0.1 0.5 0.1 5.3 0.1 0.9 0.1 1.5 0.1

25.6 1.2 1.7 0.1 46.3 2.1 2.9 0.2 15.8 0.6 3.0 0.2 13.4 0.5 2.7 0.2 39.0 1.9 3.8 0.3 14.9 0.7

59.6 1.5 8.1 0.2 30.4 1.9 3.5 0.2 26.3 0.7 6.9 0.3 19.7 0.5 2.7 0.1 49.8 1.5 4.7 0.2 16.3 0.3

SIMULTANEOUS MONITORING OF HEAVY METALS: A NEW VOLTAMMETRIC METHOD

Present work, see Tables III and IV. Fagioli et al., 1994.

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TABLE VI Metal contamination in sediments sampled in the Goro Bay ecosystem. Comparable investigations

Sampling site

Winter sampling

Cu(II) Summer sampling Winter sampling Winter sampling Winter sampling

Pb(II) Summer sampling

Cd(II) Summer sampling

Zn(II) Summer sampling

C. LOCATELLI AND G. TORSI

70.2 3.5 71.3 3.1 48.2 1.9 32.6 1.3 27.4 1.8 35.6 1.8 22.1 0.9 80.3 2.9 34.6 1.4

77.4 2.9 81.5 2.3 63.5 3.0 37.2 1.2 29.8 1.4 43.8 1.5 24.7 1.2 88.7 2.6 43.4 1.8

29.6 1.2 50.4 1.8 19.9 0.8 14.3 0.7 7.8 0.3 27.2 1.2 25.4 1.0 49.0 1.9 20.0 1.2

31.2 1.0 69.2 2.0 28.6 1.2 18.4 0.5 9.6 0.2 35.6 1.2 25.5 0.8 56.7 1.5 37.6 1.6

0.49 0.02 0.23 0.01 0.14 0.01 0.17 0.01 0.12 0.01 0.14 0.01 0.11 0.01 0.69 0.02 0.14 0.02

0.68 0.03 0.21 0.01 0.19 0.01 0.08 0.01 0.06 0.01 0.15 0.01 0.12 0.01 0.77 0.02 0.23 0.01

210.0 7.7 270.5 6.9 205.0 7.7 77.0 2.9 64.6 3.1 130.7 6.9 115.8 4.3 276.1 11.3 83.4 4.3

223.1 7.7 296.8 7.3 227.3 8.2 87.4 3.0 71.2 3.9 149.0 7.3 117.7 3.8 315.0 12.9 96.0 2.4

Present work, see Tables III and IV. Fagioli et al., 1994.

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in sites B and E than other four sites during summer. Hence it seems that the greater anthropic activities and the weak currents concentrate the pollution load in central and eastern part of the Goro Bay (Figure 1). However, these values, if compared with those found in the sediments sampled in different ecosystems (Merian, 1991), for selenium and arsenic are of the same order of magnitude and in the substantial agreement. In case of copper, lead, cadmium and zinc, pollution seems general, uniform and in same cases very high. With a view to establishing the levels of anthropogenic contamination inside the Goro Bay ecosystem, a comparison (Tables V and VI) relevant only to some sampling site, only to Cu, Pb, Cd, Zn and only to sea water and sediments may be carried out. As regards As and Se concentrations, comparable data are not available in literature, but it can be reasonable to think that anthropogenic contamination is absent. The data reported in Tables V and VI show that for Cu, Pb, Cd and Zn a general anthropogenic contamination is happened, since the values relevant to the last samplings (February and August, 2000) show, in all cases, metal concentrations higher than that found in 1992 samplings. In particular, in sea water all metals present increases: Cu and Zn for all the sampling sites show high concentration increases, some times also of one order of magnitude; Pb and Cd concentrations increase in all sampling sites, but especially in the sites B and E. As regards the sediments, a very substantial increase in the metal concentrations is present in the sampling sites where the comparison is possible. Moreover, the data relevant to 1992 samplings conrm that summer samplings show to have, in all cases and generally for all the metals, concentrations higher than winter samplings. At last it is important to highlight that the greater advantage in using the voltammetric techniques is that a single instrumental measurement, allows the simultaneous determination of several elements (ICP spectrometry shows to have the same advantage, but the instrumentation is much more expensive). Moreover the voltammetric techniques are sensitive, selective and very suitable for monitoring heavy metals in complex environmental samples like sea water, sediments, algae and clams.

References
Adeloju, S. B., Bond, A. M., Briggs, M. H. and Hughes, H. C.: 1983, Stripping voltammetric determination of selenium in biological materials by direct calibration, Anal. Chem. 55, 20762082. Bobrowski, A. and Bond, A. M.: 1993, A comparison of qualitative and quantitative methods used to dene the resolution of two overlapping reversible processes in second and fundamental harmonic alternating current voltammetry, Croatica Chemica Acta 66, 499508. Bond, A. M., OHalloran, R. J., Ruzic, I. and Smith, D. E.: 1976, Fundamental and second harmonic alternating current cyclic voltammetric theory and experimental results for simple electrode reactions involving solution-soluble redox couples, Anal. Chem. 48, 872883. Bond, A. M.: 1980, Modern Polarographic Methods in Analytical Chemistry, Marcel Dekker Publ., New York.

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