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Marine Pollution Bulletin 46 (2003) 1015–1023

Persistence of petroleum hydrocarbon contamination in sedimentsof the canals in Venice, Italy: 1995 and 1998

Dana L. Wetzel 1, Edward S. Van Vleet *

University of South Florida, College of Marine Science, 140 7th Avenue South, St. Petersburg, FL 33701, USA

Abstract

Total hydrocarbon and selected polycyclic aromatic hydrocarbon (PAH) levels were examined in sediments collected from

known problematic areas in the canals of Venice, Italy, in 1995 and 1998. Hydrocarbon concentrations were greatest in the interior

canals, moderate in the partially enclosed locations and lowest in the open-water sites. Total hydrocarbon and PAH concentrations

declined from 1995 to 1998. Ancillary data suggest that this decline may have been in response to the elimination of many industrial

activities in the lagoon and to initiating an aggressive canal dredging program. The distributions of individual components were

generally similar both years regardless of the total PAH concentration or the location of sample collected. PAH alkyl homolog

distributions suggest that atmospheric deposition of petrochemical combustion products is the main source of PAHs to Venice�ssediments. In some cases however, the presence of low levels of the two-ring naphthalene homologous series indicate additional low-

level inputs of fresh oil.

� 2003 Elsevier Ltd. All rights reserved.

Keywords: Petroleum hydrocarbons; Pollution; Sediments; Venice; Italy

1. Introduction

The city of Venice, Italy, lies in the Lagoon of Venice

and is connected to the Northern Adriatic Sea through

the port entrances of Lido, Malamocco and Chioggia

(Fig. 1). Over its history, the structure and configuration

of Venice has been altered through human and natural

influences, resulting in a network of numerous canals,which are firmly integrated within the constructs of the

city. More recently, the city and lagoon have undergone

dramatic changes tied to the advent of industrialization

and the associated pollution growth.

The first major industrial zone affecting the lagoon

was established in the 1920s on the mainland at Porto

Marghera, which is located at the end of the 3.5 km

bridge that brought the railroad to the Island of Venicein 1866 (Fig. 1). Concurrently, boats in Venice�s canalsbecame predominately motor driven, further enhancing

contamination coming from the industrialized zone. By

*Corresponding author. Tel.: +1-727-553-1165; fax: +1-727-553-

1189.

E-mail address: [email protected] (E.S. Van Vleet).1 Mote Marine Laboratory, 1600 Thompson Parkway, Sarasota,

FL 34236, USA.

0025-326X/$ - see front matter � 2003 Elsevier Ltd. All rights reserved.

doi:10.1016/S0025-326X(03)00124-3

the 1960s, a second industrial zone had been created to

the southwest of the first over what had previously been

tidal lands, compounding the effects of human activity

with the addition of more industrial chemicals, petro-

leum and industrial/municipal wastes to the burden of

the lagoon (Lane, 1973).

Today, the Lagoon serves as the drainage basin for

approximately 200,000 km2 and has a population baseof about 1.4 million persons (Van Vleet et al., 1988).

Moreover, the Lagoon of Venice serves as a major oil

transport harbor in Italy. Losses of petroleum from

tankers, commercial and pleasure craft, along with in-

dustrial effluents, agricultural runoff and aerial deposi-

tion, contribute to the much-deteriorated condition of

the marine ecosystem of Venice. About 1200 ships enter

the lagoon annually, of which roughly 60 are large oiltankers transporting crude oil to the area. Within the

last decade, more than 12 million tons of crude oil and

other chemical products have been transported through

the lagoon each year. Since Venice is a major oil port for

Italy, inevitable contamination from the accumulation

of polycyclic aromatic hydrocarbons (PAHs) is a sig-

nificant concern.

The disappearance of animal and plant species is aclear indication of the problems associated with water

Fig. 2. Station locations for 1995 and 1998 studies.

Fig. 1. Location of Venice, Italy in the Venice Lagoon.

1016 D.L. Wetzel, E.S. Van Vleet / Marine Pollution Bulletin 46 (2003) 1015–1023

quality in Venice. Since the 1930s, the diversity of spe-

cies, such as birds, has decreased by 20%, the number of

plant species has declined by 50%, and coverage bymarine eelgrass is down by as much as 80% of its orig-

inal distribution (Salve, 1999). Adequate tidal flushing

of the canals is required to mitigate increased anthro-

pogenic contamination and prevent build-up of con-

taminants in sediments and organisms. In the past,

maintenance of these canals has been inadequate, lead-

ing to high levels of pollutant accumulation. Dredging

of the canals has been attempted as a means of reme-diating the build-up of pollutants. While this strategy

may provide a temporary solution, the long-term success

of dredging is not clear.

Sedimentation is particularly problematic for Venice

due to the strong association of pollutants with fine-

grained sediments, leading to a significant accumulation

of toxic contaminants. Fine-grained sediments provide a

‘‘sink’’ for many contaminants and therefore informa-tion on the long-term accumulation of pollutants. The

more soluble pollutants can be removed by currents or

tidal flow while the insoluble constituents may become

associated with particulate material and ingested by

organisms or deposited in the sediments where they

accumulate. Until the 1980s, virtually no legal regula-

tion of the Porto Marghera industrial area was in place,

and discharges into the lagoon went largely unchecked(Salve, 1999). The potential effects of these pollutants

still remain, since the material was dispersed and de-

posited throughout the lagoon.

The current study examined sediments collected from

known problematic areas in the canals of Venice to as-sess the temporal trends in distributions and concen-

trations of petroleum hydrocarbons in 1995 and 1998.

The sediments were analyzed for total petroleum hy-

drocarbons (TPHs) and selected PAH levels. Diagnostic

techniques such as the distribution of n-alkanes and

PAH homologs were used to help identify potential

sources of hydrocarbons in these environmental sam-

ples. Although some previous studies have investigatedthe distribution of petroleum hydrocarbons in sediments

from the canals of Venice, none have focused on tem-

poral variations of these contaminants for the purposes

of examining the area�s long-term health (Fossato and

Dolci, 1976; Van Vleet et al., 1988).

2. Methods

Sediment samples were collected from eight locations

representing three environmentally different areas within

the canals and lagoon of Venice in 1995 and five loca-

tions in 1998 (Fig. 2). These areas included the interior

canals of Venice, which have limited flushing capacities

and a predominance of fine-grained sediments (stations

23, 24 and 26), the partially enclosed canals with sometidal flushing (stations 2, 8 and 15) and the open-water

locations which had the greatest amount of regular tidal

influences (stations 10 and 11). Surface sediments (ap-

proximately top 5 cm) were collected with a sediment

grab sampler and stored in sterilized glass jars. Addi-

tionally, in the 1995 study, gravity cores from stations 23

and 24 were also collected and sub-samples were taken

from each core at the top (�0–15 cm) and at mid-core(�32–45 cm). Sediments were transported back to the

D.L. Wetzel, E.S. Van Vleet / Marine Pollution Bulletin 46 (2003) 1015–1023 1017

laboratory on ice where they were immediately frozen

until extraction. Sediment sub-samples were taken to

determine moisture content. Approximately 20 g (wet

weight) of each sediment sample were extracted by re-fluxing for 2 h with a fivefold volume excess of 2:1(v/v)

dichlormethane:methanol. Internal standards (5a-androstane and o-terphenyl) were added to each sample

prior to extraction for quantitative hydrocarbon analy-

sis. Following extraction, the organic phase was parti-

tioned with deionized water and separated, and the

extracts were dried over anhydrous sodium sulfate. The

extracts were separated into F1 (aliphatics/saturates)and F2 (aromatics/unsaturates) by silica gel-alumina

column chromatography (Van Vleet et al., 1988). Each

fraction was evaporated to near dryness and redissolved

in hexane for analysis by gas chromatography (GC) and

combined gas chromatography–mass spectrometry

(GCMS). All hydrocarbon fractions were analyzed by

high-resolution GC using a Hewlett-Packard 5890 GC

equipped with a 30 m DB-5 fused silica column andflame ionization detector with hydrogen as the carrier

gas. Oven temperature was held at 50 �C for 2 min and

then programmed from 50 to 280 �C at 6 �C/min and

held at 280 �C for 15 min. Individual compounds were

corrected for detector response factors and integrated

using a Hewlett-Packard data processor. Selected F2

fractions were further analyzed by GCMS for qualita-

tive and quantitative identification of individual PAHsusing a Hewlett-Packard 5971 Mass Selective Detector

under conditions similar to those employed by GC using

helium as the carrier gas. The mass spectrometer was

scanned from mass 40–500 in 0.5 s at an ionization

potential of 70 eV. All mass spectral data were com-

pared to spectra produced by authentic standards and to

Fig. 3. 1995 and 1998 total sediment hydrocarbon concentrations (a

previously published library spectra. The minimum de-

tectable amounts were calculated at 100 ng/g of the ex-

tracted environmental samples.

3. Results

3.1. 1995 sediment samples

Sediments collected from eight locations in the three

different environments, open-water (stations 10 and 11),

partially-enclosed (stations 2, 8 and 15) and interiorcanals (stations 23, 24 and 26), exhibited somewhat

different petroleum hydrocarbon characteristics. Con-

centrations of hydrocarbons were greatest in the interior

canal stations, moderate in the partially enclosed loca-

tions and lowest in the open-water sites with averages

from these three areas of 908, 332 and 145 lg/g dry wt.

respectively (Fig. 3). The mid-core samples from interior

canal stations 23 and 24 had two to three times theamount of total hydrocarbons found in the corre-

sponding surface sediments from these stations. The

unresolved complex mixture (UCM), indicative of

weathering, was significant in samples collected from the

interior canal locations, moderate in the partially en-

closed sites and minimal in the open-water stations (Fig.

4). While biogenic hydrocarbon contributions were

found superimposed onto the UCMs in all the sedimentsamples, the hydrocarbon profiles from the partially

enclosed and interior canal sediments were characteristic

of petroleum contamination with an odd to even pre-

ference of close to unity in each case.

Selected sediments samples were further analyzed

by GCMS for 37 individual PAHs including parent

ll sediments collected from 0 to 5 cm unless otherwise noted).

Fig. 4. 1995 sediment chromatograms: (A) open-water station, (B)

partially enclosed station, (C) interior canal station.

1018 D.L. Wetzel, E.S. Van Vleet / Marine Pollution Bulletin 46 (2003) 1015–1023

compounds and their associated alkyl substituted ho-mologs to determine the amount, distribution and per-

cent composition of the targeted PAHs for diagnostic

source information. The total concentrations of these

selected PAHs ranged from 54 to 160 lg/g dry wt. in the

surface sediments (Table 1). The concentrations of total

PAHs were not significantly different in the surface

sediments of the interior canal stations 23 and 24 and at

the mid-core depth for these samples. While the totalPAH concentrations for the stations varied by location,

the distributions of individual components and percent

compositions were similar regardless of the total PAH

concentration or the location of sample collected (Fig. 5;

distributions are also similar for stations not shown in

figure). The major contributions of PAHs in each of

these sediment samples came from the fluoranthene/

pyrenes (�43%), the phenanthrene/anthracenes (�25%)and the benzo(a)anthracene/chrysene series (�16%;

Table 1).

3.2. 1998 sediment samples

During 1998, sediments were collected from five lo-

cations (Fig. 2) common to the 1995 study representing

the same three types of environments, open-water lo-cation (station 10), partially enclosed site (station 15)

and interior canals (stations 23, 24 and 26) and analyzed

for petroleum hydrocarbons in the same manner as

the 1995 study. The TPH concentrations were lowest in

the open-water station (57 lg/g dry wt.), moderate in the

partially enclosed station (96 lg/g dry wt.) and highest inthe three interior canal stations (average �213 lg/g dry

wt.; Fig. 3). As in 1995, the sediment samples from the

three types of environments had differing intensities of

UCMs. None were evident in the open-water station,

but were significant in the partially enclosed station and

increased in predominance in the interior canal samples,

with UCMs falling in the same general hydrocarbon

range superimposed with biogenic hydrocarbon signa-tures (Fig. 6). Each of these sediment samples were

further analyzed by GCMS for identification and

quantitation of the same 37 selected PAHs as in the 1995

study. Concentrations of the targeted PAHs were fairly

low (7–12 lg/g dry wt.) and consistent in each of the

sediment samples with the exception of the interior canal

station 23, which had a PAH concentration of 81 lg/gdry wt. (Table 2). The dominant PAH contributions seenin each of the sediment samples were from the fluo-

ranthene/pyrenes (�48%), the phenanthrene/anthra-

cenes (�20%) and the benzo(a)anthracene/chryseneseries (�17%). Although the total PAH concentration

was much higher at station 23, the distribution of PAH

homologs was consistent from station to station (Fig. 7).

4. Discussion

Surface sediment samples taken from each of the

three location categories (open-water, partially enclosed

and interior) in both 1995 and 1998 all showed distinct

similarities in hydrocarbon characteristics; however, not

only was there a significant decrease in total hydrocar-

bon concentrations from 1995 to 1998, there was also asubstantial decrease in PAH concentration in all but the

interior canal station 23 which remained the same (Fig.

3; Tables 1 and 2). The range of resolved n-alkanes in

surface sediments was analogous for each of the location

types in each of the two studies with the exception of the

1995 surface sediments from interior canal station 26.

The n-alkane distribution for this station was more

similar to those found in the 1995 mid-core sedimentsamples from the other interior canals than to other

surface sediments collected during that year. Dredging

of surface sediments at this station by the Venice Water

Authority had been completed shortly before our sam-

pling of the surface sediments in 1995. According to the

official plan for dredging, the canal on which station 26

was located was dry excavated (asciutto) from an orig-

inal water depth of 1.38 m to a final depth of 1.90 m fora total of 0.52 m of sediments removed (Commune Di

Venezia, 1984). As a result, the newly exposed surface

sediments (i.e., those collected for our study) were ac-

tually sediments that were roughly at the same original

Table 1

1995 sediments selected PAH composition lg/g dry wt

Station number 2 10 15 23 Top 23 Mid 24 Top 24 Mid 26

Naphthalene <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.2

C1N <0.1 <0.1 <0.1 <0.1 0.3 <0.1 <0.1 0.5

C2N 0.4 <0.1 0.4 <0.1 0.4 <0.1 0.3 1.8

C3N 0.5 0.2 0.9 0.4 0.3 0.1 0.7 1.8

C4N 0.3 0.1 0.6 <0.1 <0.1 <0.1 0.4 1.0

Fluorene 1.5 0.9 2.1 1.8 1.0 0.4 0.3 3.8

C1F 0.7 0.4 1.4 0.6 <0.1 0.2 0.2 1.0

C2F 0.4 0.2 0.9 0.2 <0.1 <0.1 0.2 0.6

C3F 0.4 <0.1 1.0 <0.1 <0.1 <0.1 <0.1 <0.1

C4F <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

Dibenzothiophene 1.3 0.7 1.8 0.9 0.6 0.4 0.3 1.8

C1DBT 0.4 0.3 1.0 <0.1 0.3 0.2 0.4 0.6

C2DBT 0.4 0.3 0.7 <0.1 1.0 0.2 1.4 1.7

C3DBT 0.3 <0.1 <0.1 <0.1 <0.1 <0.1 2.2 <0.1

C4DBT <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

Anthracene 13.8 9.5 21.0 14.7 9.7 7.0 2.0 22.4

Phenanthrene 2.8 2.0 6.6 3.6 2.5 2.2 0.5 4.7

C1A+P 3.9 2.9 8.1 3.6 2.5 2.4 0.8 5.4

C2A+P 1.7 1.3 4.0 1.8 1.6 1.0 1.0 3.6

C3A+P 0.8 0.5 1.5 <0.1 1.7 0.3 0.8 <0.1

C4A+P 1.5 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

Fluoranthene 13.8 11.5 29.2 21.8 21.8 12.1 5.0 39.8

Pyrene 14.0 8.6 27.1 17.3 18.8 8.4 4.3 29.8

C1Fl +Py 6.0 2.7 8.4 4.2 5.0 2.6 1.7 8.5

C2Fl +Py 2.1 1.2 3.3 0.7 1.3 0.9 1.0 2.1

C3Fl +Py 0.4 0.5 1.4 <0.1 <0.1 <0.1 <0.1 0.9

C4Fl +Py <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

Benzo(a)anthracene 6.6 3.4 3.4 4.5 5.9 3.9 0.8 7.7

Chrysene 6.2 3.0 9.4 4.2 5.3 3.6 1.7 7.5

C1Ba+C 2.8 1.5 4.6 1.0 1.8 1.7 1.0 2.7

C2Ba+C 1.0 0.4 1.6 <0.1 0.4 0.4 0.6 0.6

C3Ba+C 0.4 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

C4Ba+C 0.2 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

Benzo(a)pyrene 2.3 1.0 3.9 1.0 1.7 1.4 0.8 2.0

Benzo(e)pyrene 1.8 0.7 2.9 1.2 1.4 1.2 0.8 1.8

Benzo(k)fluoroanthene 5.9 2.4 8.6 2.5 4.5 3.7 1.4 5.8

Dibenzanthracene 0.2 <0.1 0.3 <0.1 <0.1 0.1 <0.1 0.1

Total in lg/g dry wt. 94.8 56.2 156.1 86.0 89.8 54.4 30.6 160.2

% of total F2 HC 53% 56% 68% 60% 26% 39% 11% 48%

D.L. Wetzel, E.S. Van Vleet / Marine Pollution Bulletin 46 (2003) 1015–1023 1019

depth as the 1995 mid-core (�32–46 cm) sediment

samples from stations 23 and 24. In this context, station

26 was not an anomaly and compared well with the two

mid-core samples for both the total hydrocarbon con-

centration and PAH distribution. Mid-core hydrocar-

bon concentrations from the 1995 collections at stations

23 and 24 were considerably higher than the corre-

sponding surface sediments (Fig. 3), however the PAHconcentrations were similar within each core (mid-core

and surface sediments; Table 1), suggesting that much of

the hydrocarbon concentration was attributable to bio-

genic material. The 1995 total PAH concentrations

varied among the stations, ranging from a high of 160

lg/g dry sediment in the surface sediments at station 26

to a low of 31 lg/g dry wt. in the mid-core sediments of

station 24 (Table 1). Again, because station 26 had beendredged prior to this sampling event, the newly exposed

surface sediments did not reflect the 1995 PAH inputs

but instead represented concentrations deposited under

previous environmental conditions. Station 24 was also

included in the overall dredging plan and was dredged in

1997 when 0.81 m of sediments were removed. Decreases

in 1998 total hydrocarbon concentrations and total

targeted PAH concentrations at this station suggest an

improved environmental condition from the previous

1995 study. The total concentration of PAHs in station23 surface sediments remained relatively constant from

the 1995 to 1998 study. This may be explained because

station 23, an internal canal station, was not included in

the dredging plan and is not subject to intensive circu-

lation and tidal flushing.

Surface sediments from each of the stations within

the three location categories during the two sampling

years shared characteristics of n-alkane maxima, percentF1 of total hydrocarbons, percent resolved F1 fractions,

range of the UCMs and, with the exception of station

0

5

10

15

20

25

Nap

htha

lene C1N

C2N

C3N

C4N

Fluo

rene C1F

C2F

C3F

C4F

Dib

enzo

thio

phen

e

C1D

BT

C2D

BT

C3D

BT

C4D

BT

Phen

anth

rene

Anth

race

ne

C1P

C2P

C3P

C4P

Fluo

rant

hene

Pyre

ne

C1P

Y

C2P

Y

C3P

Y

C4P

Y

Benz

o(A)

Anth

race

ne

Chr

ysen

e

C1C

H

C2C

H

C3C

H

C4C

H

Benz

o(A)

Pyre

ne

Benz

o(E)

Pyre

ne

Benz

o(K)

Flu

roan

then

e

Dib

enza

nthr

acen

e

ug/g

dry

wei

ght

Station 10-Open WaterStation 2-Partially EnclosedStation 23 (surface)-InteriorStation 23 (Mid Depth)-Interior

Fig. 5. 1995 sediment PAH concentrations and distributions.

1020 D.L. Wetzel, E.S. Van Vleet / Marine Pollution Bulletin 46 (2003) 1015–1023

26, similar total hydrocarbon concentrations. These

three location categories also shared almost identical

PAH characteristics, not only within the categories, butalso among the whole sample set (Figs. 5 and 7). Each

sample contained significant contributions of the

major PAHs and their homologs, with the dominant

PAHs (anthracene, phenanthrene, fluoranthene, pyrene,

benzo(a)anthracene and chrysene) consistent for every

sample.

Aromatic hydrocarbons from petrochemical com-

bustion sources can be characterized by a lesser degreeof alkylation than aromatics originating from direct

petroleum inputs. This lower degree of alkylation results

from the cleaving of the substituted side chains during

high temperature combustion (Youngblood and Blu-

mer, 1975; Laflamme and Hites, 1978; NRC, 1985).

These homolog distributions can be used to discriminate

petrogenic sources of PAHs from combustion sources.

As was observed in the sediment samples from these twostudies (Figs. 5 and 7), the parent compounds were more

abundant than their homologs. The fluoranthene/pyrene

series were the most abundant PAHs followed by the

anthracene/phenanthrene and benzanthracene/chrysene

series, indicating that combustion-related hydrocarbons

were the key source of PAHs to Venice�s sediments

(NRC, 1985). With the extensive boat traffic on these

canals and the proximity of the industrial plants atnearby Porto Marghera, it is probable that these are the

sources of many of the petroleum hydrocarbons (par-

ticularly the petroleum combustion products) found in

the canal sediments. In some cases however, there were

also low levels of the two-ring naphthalene homologous

series. This is particularly indicative of fresh oil inputs.

Because naphthalene is both highly volatile and soluble

in water (rapidly weathering), the presence of thesePAHs suggests very recent contributions of petroleum to

the environment (Wetzel, 1995). These naphthalene

contributions, while relatively small in comparison to

the other PAHs, suggest that not all the hydrocarbons

are derived from combustion sources since naphthalenes

do not generally survive the combustion process. In-

deed, since motorized boats are the only means of me-

chanical transportation in Venice, accidental spillage,bilge water discharge and oily ballast water containing

petrogenic hydrocarbons are by-products of a commu-

nity whose very culture depends on utilizing the water-

ways for travel. While the hydrocarbon loads found in

sediments in the canals of Venice contain significant

biogenic contributions characterized by odd-numbered

n-alkanes such as nC15, nC17 and nC19, they are gener-

ally superimposed on a characteristic petroleum signa-ture.

Although there was little difference in qualitative

petroleum hydrocarbon characteristics between 1995

and 1998 samples, the total hydrocarbon concentrations

for surface samples collected in 1995 ranged from a low

of 108 lg/g in the open-water sites to a high of 1090 lg/gdry sediment in the interior canals but dropped con-

siderably in 1998 to 57 lg/g in the open-water locationand 294 lg/g dry sediment in the interior station (Fig. 3).

What is important to note here is that not only the total

hydrocarbon concentration decreased from 1995 to

1998, but the percent targeted PAHs of the total hy-

drocarbon load also decreased in each station (Tables 1

Table 2

1998 sediments total PAH concentration and % F2

Station number 10 15 23 24 26

Total in lg/g dry wt. 8.8 10.5 81.0 11.2 7.3

% of total F2 HC 43% 33% 65% 31% 13%

Fig. 6. 1998 sediment chromatograms: (A) open-water station, (B)

partially enclosed station, (C) interior canal station.

D.L. Wetzel, E.S. Van Vleet / Marine Pollution Bulletin 46 (2003) 1015–1023 1021

and 2) except at one of the interior sites (station 23)

which coincidentally was the only interior station not to

have been dredged before the 1998 study, thus suggest-ing that petroleum input sources may have been the

same, but the amount of input appears to have de-

creased. Mid-core hydrocarbon concentrations from the

1995 collections at stations 23 and 24 had considerably

higher total hydrocarbon concentrations than the cor-

responding surface sediments, but the corresponding

PAH content was approximately equal to that found in

the surface sediments indicating that much of the total

hydrocarbon content at mid-core was attributed to large

contributions of biogenic material which, again de-

creased substantially by 1998.

This significant decrease in both total hydrocarbonand petroleum hydrocarbon contamination may be at-

tributable to the aggressive pollution remediation efforts

undertaken by the Venetian government in response to

legislative laws enacted in 1984. One of the many pol-

lution intervention methods established by the Venice

Water Authority includes dredging of most of the canals

within Venice and the industrial areas of Porto Marg-

hera. Two of the interior canal stations (station 24 and26) common to both the 1995 and 1998 studies were

included in the dredging program schedule during these

studies. Data from these studies indicate a reduction in

biogenic inputs to the sediment. This can be attributed

to government efforts to lower nutrient inputs into the

lagoon by creating buffer areas of trees, shrubs and

eelgrass (termed ‘‘estuary phytopurfication systems’’) to

capture agricultural nutrients and associated pollutants.Comparisons to previous sediment petroleum con-

tamination studies can be made with the results from the

current study to assess the degree of contamination that

exists in this sensitive environment. Since Venice does

not currently utilize any extensive wastewater treatment

processes, comparisons to sewage outfalls in other areas

of the world can be drawn to get an idea of how the

direct inputs from Venice compare to a range of envi-ronmental conditions. Although Venice is not a site of

direct sewage outfall or acute petroleum spills, it is an

area of chronic non-point source sewage and pollution

inputs, unique in its environmental characteristics and

condition making it difficult to find suitable compari-

sons.

Sediment hydrocarbon loads found in sewage outfall

areas of Chesapeake Bay (Brown and Wade, 1984) andthe Providence River (Van Vleet and Quinn, 1978)

ranged from 2.4 to 153 lg/g dry wt. and 570 and 5410

lg/g dry sediment respectively. These values, represent-

ing significant anthropogenic inputs, are perhaps indi-

cative of the high-end of systems that experience sewage

and municipal discharges. For low-end natural hydro-

carbon concentrations, examination of non-anthropo-

genically impacted areas can be made. Saliot et al.(1988) investigated ambient levels of hydrocarbon con-

centrations in uncontaminated marine sediments from

the deep-sea region of the Cariaco Trench, and the

Northeastern Atlantic of the Mauritanian and Senega-

lian coasts. In this study, concentrations found in the

sediments ranged from no detectable hydrocarbons to

20.8 lg/g dry sediment. In an earlier study, Van Vleet

and Quinn (1979) found similar levels in uncontami-nated sediments from the Equatorial South Atlantic.

This information helps establish the natural background

(low-end) of hydrocarbon concentrations found in

marine sediments while the sewage discharge studies

0

2

4

6

8

10

12

14

16

18

20

Nap

thal

ene

C2N

C4N

Flu

oren

e

C2F

C4

F

Dib

enzo

thio

phen

e

C2D

BT

C4D

BT

Phe

nant

hren

e

C1P

C3P

Pyr

ene

C2P

Y

C4P

Y

Ben

zo(A

)Ant

hrac

ene

C1C

H

C3C

H

ug/g

dry

wei

ght

Station 10Station 15Station 23Station 24Station 26

Fig. 7. 1998 sediment PAH concentrations and distributions.

1022 D.L. Wetzel, E.S. Van Vleet / Marine Pollution Bulletin 46 (2003) 1015–1023

represent a chronic high-level hydrocarbon contamina-tion condition. The total hydrocarbon concentrations

found in the sediments of the Venice Lagoon in 1995

and 1998 are high compared to the discharge study in

Chesapeake Bay but similar to those found near the

Providence River outfall. This places the Lagoon of

Venice in the same category with highly impacted sew-

age discharge areas.

To further evaluate the significance of the hydrocar-bon levels found in Venice sediments, it is also worth-

while to consider the levels of hydrocarbons found in

marine sediments following an acute oil spill in the

marine environment. For example, in three separate

spills of either crude or refined oil, average sediment

hydrocarbon levels were reported for a 38.3 million liter

spill of medium crude oil in Galeta, Panama (Burns

et al., 1994), the Exxon Valdez tanker loss of 41 millionliters of crude oil (Bragg et al., 1994) and a smaller spill

of 1.2 million liters of Bunker C (no. 6) fuel oil in Tampa

Bay, Florida (Wetzel, 1995). The sediment hydrocarbon

loads ranged from 104 to 105 lg/g dry sediment for the

Panama spill, 103 to 104 lg/g dry sediment in the Exxon

Valdez incident and 101 to 102 lg/g dry sediment in the

Tampa Bay spill. Total hydrocarbon concentrations for

the sediments in the Lagoon of Venice ranged from 102–103 lg/g dry sediment during the current studies. While

the contamination from hydrocarbons in the sediments

in Venice are not as high as in many acute oil spill areas,

the levels found in this study suggest that sediments in

the canals of Venice, Italy are substantially impacted by

anthropogenic petroleum hydrocarbon inputs.

5. Conclusions

The Lagoon of Venice, ancient in origin, complex in

design and fragile in its current ecological condition has

undergone significant deterioration attributable to long-

term anthropogenic impact. Temporal variation studies

and subsequent trend analyses of contaminated envi-

ronments offer a better understanding of the pollution

status of a complex ecosystem, particularly in areaswhich are attempting systematic remediation of im-

pacted areas.

Three different types of environments were identified

in the Lagoon of Venice: open-water sites, partially en-

closed canals and interior canals. These three environ-

ments were classified by different amounts of flushing

and tidal influences which affect the concentration of

contaminants deposited in the sediments. Petroleumcontamination in the lagoon has been problematic for

several decades due to the industrialization of Porto

Marghera and to the increase in motor-boat traffic in the

canals. Diagnostic chemical techniques for assessing

petroleum components suggest that the existing con-

tamination can primarily be attributed to atmospheric

deposition of petroleum combustion products, with

smaller amounts from fresh oil inputs probably due toboat traffic. Both the TPH and the total PAH concen-

trations appeared to decline from the 1995 to 1998 in

each of the three environments. This decline in petro-

leum contamination may very well be in response to the

elimination of many industrial activities in the lagoon

and to the aggressive canal dredging program initiated

D.L. Wetzel, E.S. Van Vleet / Marine Pollution Bulletin 46 (2003) 1015–1023 1023

by the Venice government. Continued progress on the

restoration of the lagoon environment enhanced by

public and scientific awareness and assessment may

prove to successfully arrest the rapid deterioration of thelagoon and help restore it to a stable and productive

environment.

Acknowledgements

Funding for this work was provided by Italy�sConsiglio Nazionale delle Ricerche Short-term ForeignExchange Fellowship Program and by the Gladys

Krieble Delmas Foundation. We are greatly indebted to

the administration and scientists at the Istituto di Bio-

logia del Mare for their hospitality and assistance. We

especially appreciate the scientific collaboration and

viticultural interactions with Dr. Valentino Fossato,

Dr. Giancarlo Campesan, Dr. Danieli Cassin and Mr.

Francisco Dolci.

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