Atmospheric fall-out of POPs (PCDD-Fs, PCBs, HCB, PAHs) around the industrial district of Porto Marghera, Italy

1

___________________

* Corresponding author. Tel.: +39-0541-791050; fax +39-0541-791045.

E-mail address: [email protected] (Paolo Rossini).

Atmospheric fall-out of POPs (PCDD-Fs, PCBs, HCB, PAHs) around the industrial

district of Porto Marghera, Italy

Paolo Rossini1,*, Stefano Guerzoni2, Gabriele Matteucci1, Massimo Gattolin3, Giorgio Ferrari4,

Stefano Raccanelli5

1 Istituto di Ricerca Gruppo CSA, via Al Torrente 22, 47900 Rimini, Italy

2 CNR - Istituto di Scienze Marine, Riva VII Martiri 1364/A, 30122 Venezia, Italy

3 Provincia di Venezia, Via della Rinascita 156, 30175 Marghera, Italy

4 Magistrato alle Acque, S. Polo 19, 30125 Venezia, Italy

5 Consorzio INCA, via della Libertà 5/12, 30175 Marghera, Italy

Abstract

In order to estimate the importance of atmospheric fall-out of persistent organic pollutants

(POPs) around the industrial district of Porto Marghera, Italy, atmospheric depositions of

POPs were collected using bulk samplers inside the Lagoon of Venice. 77 atmospheric

deposition samples were collected monthly over a 12-month period (March 2003–March

2004) at seven sites located close to the industrial area of Porto Marghera. Samples were

analysed by HRGC/HRMS for PCDD-Fs, PCBs, HCB and PAHs. Differences in mean daily

fluxes of all organic pollutants between industrial, urban and lagoonal stations were clear,

atmospheric depositions at industrial sites being higher than target values for dioxin

deposition recommended by the EU strategy on dioxins, furans and polychlorobiphenyls. In

order to calculate atmospheric loadings of POPs around the industrial district, we considered

an area defined by a distance of 10 km from the hypothetical centre-point of the main

* Manuscript

P. Rossini et al. / submitted to The Science of the Total Environment 2

sources of atmospheric emissions from Porto Marghera. The calculated loadings, compared

with the previous estimates, show that annual loadings of POPs are 12 g, 510 g, 90 g and 130

kg of PCDD-Fs, PCBs, HCB and PAHs, respectively, corresponding to 350-500 mg TEQ,

thus indicating a slight decrease in PCBs and a great decrease in HCB with respect to 1998-

99. The input coming from the atmosphere is of the same order of magnitude of that due to

the watershed runoff and approximately one-half of the direct industrial discharges.

Keywords: Atmospheric deposition; Dioxins, Furans; Organic micropollutants; Lagoon of

Venice; Guidelines

1. Introduction

The Lagoon of Venice is probably one of the most well-known examples in the world of

an ecosystem that has been historically influenced by human intervention since the XVth

century. Its long history has been characterized by industrial activity (even recent, mainly

after World War II), with oil refining and several chemical production plants around the

Lagoon. Only recently Venice has also been recognised for its environmental problems,

mainly due to POPs accumulating in sediments and seafood (Green et al., 1999; Jimenez

1998; Alcock et al., 2002), which have aroused local concern.

P. Rossini et al. / submitted to The Science of the Total Environment 3

Based on a recent study carried out by the Province of Venice (Provincia di Venezia,

2002), major anthropogenic activities having an important influence on air quality in the

Venice area may be summarised as follows: (i) oil refining; (ii) metallurgy, now mainly

confined to the production of Al; (iii) chloro-soda cycles, discharging dicloroethane (DCE),

vinyl chloride monomer (VCM) and polyvinylchloride (PVC); (iv) power generation (oil and

coal); (v) urban waste incineration, and (vi) traffic emissions. Most of these activities take

place inside the almost 12 km2 wide industrial area of Porto Marghera, which employs more

than 10,000 people and produces the following emissions, expressed in tons unless otherwise

stated, and averaged on annual basis (ARPAV, 2001): CO=2,000; SOx=20,000;

NOx=15,000; VOC=800; VCM=7 (dioxins=440 mg TEQ), inorganic Cl compounds=9,

chlorine=2, NH4=30; total metals= 3 (Pb=0.5, Hg=0.003); PAHs=0.6 kg; PCBs=0.1 kg.

A recent study provided by the Regional Environmental Protection Agency (ARPAV,

2003) reported that emission levels of POPs from the industrial district of Porto Marghera

have been declining by almost a factor of 2-3 within the past 5 years Unfortunately no

studies carried out in the area of Venice are available on the possible correlated decrease in

vegetations, cow’s milk, seafood, as seen by Cole and co-workers (1999) in UK.

Several studies conducted over the past 20-–30 years have focused on the potential human

health and ecological risks associated with the presence of persistent pollutants such as trace

metals (As, Hg), polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls in the

Lagoon of Venice (Fattore et al., 1997; Di Domenico et al., 1997; Marcomini et al., 1997;

Wenning et al., 2000).

P. Rossini et al. / submitted to The Science of the Total Environment 4

Some works have already revealed the evident influence of atmospheric deposition in the

area. For instance, preliminary results from soil and atmospheric deposition studies show

clearcut decreases in some metals in soil with distance, connected with a main source in the

industrial zone (Di Domenico et al., 1998). Similar results come from bulk deposition

sampling, which shows marked trends in atmospheric fluxes of trace metals with distance

from Porto Marghera (Guerzoni et al., 1995; Marcomini et al., 1999; Rossini et al., in press).

Preliminary available data on atmospheric dioxin fall-out were provided with bulk

deposition sampling (Rossini et al., 2001; Guerzoni et al., 2004), and a budget of dioxin

showed that atmospheric deposition accounted for one-quarter of the total load in the Lagoon

of Venice (Marcomini et al., 1999). Data on soils collected around the industrial zone

suggested an airborne PCDD-Fs fall-out effect up to several km downwind (Della Sala et al.,

1999).

This paper shows data of persistent organic pollutants (POPs) in atmospheric fall-out,

coming from one year sampling of monthly bulk depositions in seven stations inside the

Lagoon of Venice during one year (March 2003-March 2004). The purposes of this study

were to estimate trends of total deposition fluxes and atmospheric loadings of POPs around

the industrial district of Porto Marghera and compare them to other inputs resulting from the

same area of the lagoon, as those derived from direct industrial discharges and the runoff of

watershed .

P. Rossini et al. / submitted to The Science of the Total Environment 5

2. Materials and Methods

A total of 77 atmospheric deposition samples was collected monthly (i.e. every 29±7

days) over a 12-months period (March 2003 – March 2004) at seven sites located close to the

Porto Marghera industrial area (Fig. 1). Sites ADM and IBM were located respectively in the

cities of Mestre and Venice, upwind from the atmospheric emissions from the main

industrial district. Sites EZI and DOG were respectively located inside and about 5 km

downwind (SW) of the industrial area of Porto Marghera, in an area facing the lagoon. Sites

L1, L2 and L3 were located in the lagoon, L1 and L3 being far from large industrial and

urban sources, and L2 in the proximity of the industrial area.

Atmospheric depositions were collected by 7 bulk samplers similar to those tested by

Horstmann and McLachlan (1997) in a rural environment. The samplers were polymer

structures, formed by a cylindrical container and a protection ring to avoid damages caused

by birds and animals, clamped to a more than 1.5 m high pole. Organic micropollutants were

collected in a Pyrex bottle with a Pyrex funnel (surface area = 0.043 m2). Both bottle and

funnel have previously been silanized with dimethyldichlorosilane 5 % in toluene, thus

preventing retention of analytes. Operations for cleaning and silanisation were as follows: (i)

washing with basic detergents and rinsing in water; (ii) treatment with solution of

ammonium persulfate, (NH4)S2O8, (350 g/lt of 98 % H2SO4); (iii) rinsing with

demineralised, organic residue-free water; (iv) internal and external treatment with acetone;

(v) silanisation with dimethyldichlorosilane 5 % in toluene; (vi) second rinse with

demineralised organic residue-free water; (vii) internal and external drying with acetone;

(viii) heating at 250 °C for two hours.

P. Rossini et al. / submitted to The Science of the Total Environment 6

Bulk sampling has been extensively used, since these samplers are easier to operate than

wet and dry ones, and can also be located at sites with no electrical power supply.

Horstmann and McLachlan (1997) recently found that parallel bulk sampling reproducibility

was lower than 10% in more than 80% of cases and lower than 20% in 99% of cases, and

also that the diffusive fraction is small compared with total deposition. The limitation of this

sampling method is mainly possible under-estimation of fluxes because of the limited

collection of dry gases which, according to Schroder et al. (1997), are of minor importance

for PCDD/Fs. The advantages rising from this are the integration of samples over one month

and the possibility of large scale application with low-cost equipment.

Horstmann and McLachlan (1997) showed that rinsing the funnel with toluene at the end

of one month sampling was not different from doing it every day for 30 days. On the

contrary, daily operations added some artefacts. They therefore decided to rinse the funnel

monthly, thus keeping artefacts due to particle blow-out to 10 %. We avoided blowing up of

particles by using a longer funnel wall (60 cm instead of 15) and applied this method for

sample recovery: the rinsement of the funnel wall with double-distilled water (DDW) in

order to avoid dissolution of insects, and after the water rinse more intense cleaning of the

funnel wall using glass wool to detach any particles sticking to the wall.

The following organic compounds were analysed in total atmospheric samples:

polychlorobiphenyls (PCBs), hexachlorobenzene (HCB), polychlorinated dibenzo-p-dioxins

and dibenzofurans (PCDD-Fs), polyciclic aromatic hydrocarbons (PAHs).

P. Rossini et al. / submitted to The Science of the Total Environment 7

Total atmospheric samples were first spiked with a series of 15 13

C12-labeled 2,3,7,8

PCDD-Fs, 12 13

C12-labeled PCB, 13

C12-HCB substituted isomers, and 5 deuterated PAH

(Acenaphthene-D10, Chrysene-D12, Naphtalene-D8, Perylene-D12, Phenanthrene-D10) as

internal standards, then extracted in a separatory funnel with dichloromethane. Extracts were

transferred to hexane before clean-up treatment. Sample extracts were first spiked with 37

Cl4-

labeled 2,3,7,8 PCDD and 3 13

C12-labeled PCB, and then cleaned using an automatic system

(Power Prep; Fluid Management System Inc.). Pre-packed disposable columns containing

multilayer silica and sodium sulphate were used for PAH clean-up. After PAH analysis,

extracts were treated with sulphuric acid (98%) and potassium hydroxide (20%) in a 100-mL

separatory funnel and then cleaned using the automatic three-column system with pre-

packed disposable columns containing multilayer silica, alumina and carbon for PCDD-Fs,

PCB and HCB. HRGC/HRMS analyses were conducted using a HP 6890 plus gas

chromatograph coupled to a Micromass Autospec Ultima mass spectrometer, operating in EI

mode at 35 eV and with a resolution of 10.000 (5% valley). A quantitative determination of

PCDD-Fs, PCBs, HCB and PAHs was performed by isotope dilution methods, by the use of

relative response factors previously obtained from standard solution injections (US EPA

Method 1613B/94; US EPA Method 1668A/99).

P. Rossini et al. / submitted to The Science of the Total Environment 8

All solvents (n-hexane, dichloromethane, acetone, toluene, ethylacetate) were Picograde®

reagent grade (Pomochem GmbH, Wesel, Germany). Native and deuterated PAH standards

were purchased from Supelco (Belfonte, PA, USA), native and 13

C12-labeled PCDD/F, PCB,

HCB, Acenaphtylene-D8 and benzo[e]pyrene-D12 standards were purchased from

Cambridge Isotope Laboratories (Woburn, MA, USA). Recoveries always ranged between

50 % and 110 %. Reproducibility was 15 % for lower values, or more. Laboratory blanks,

repeated twice a week, were lower than 9 % with respect to the minimum concentration

found.

3. Results and Discussion

Atmospheric deposition samples were analysed for PCDD-Fs, PCBs, HCB and PAHs.

During data processing, values below the detection limit (DL) were considered equal to

0.5DL.

Atmospheric deposition fluxes

Mean daily bulk fluxes have been calculated from the monthly deposition values

measured. In Figure 1 and Table 1 the mean bulk deposition fluxes of POPs observed during

the study period are reported. Most of the POPs present a high monthly variability, as well as

strong differences among sampling stations. PCDD-Fs fluxes range from 12 to 2767 pg m-2

d-1

, with all maxima in station EZI (annual mean ~ 400 pg m-2

d-1

) followed by the two

nearest station on land (DOG, ADM) with much lower fluxes (~ 90 pg m-2

d-1

). All the

remaining station inside the lagoon (L1, L2, L3, IBM) present values one order of magnitude

lower (~ 50 pg m-2

d-1

).

P. Rossini et al. / submitted to The Science of the Total Environment 9

PCBs variability is very similar, with maxima in EZI (~ 20 ng m-2

d-1

), followed by DOG

and ADM ~ 4 ng m-2

d-1

) and the minima in the four “lagoonal” stations (1-2 ng m-2

d-1

).

The fluxes of PCDD-Fs can also be expressed in toxicity with (WHO-TEQ, Van den Berg

et al., 1988) and without (I-TEQ, NATO/CCMS, 1998) the contribution due to dioxin-like

PCBs. Also in this case, the patterns are consistent with the previous description, as it can be

seen in Figure 1, where the location of stations is indicated, together with the relative

importance of PCDD-Fs and PCBs in the total WHO-TE fluxes of each sample. In this case

the fluxes decrease from EZI (12 pgWHO-TE m-2

d-1

) to DOG (7 pgWHO-TE m-2

d-1

) and

ADM (3.4 pgWHO-TE m-2

d-1

), reaching an average value of ~ 2 pgWHO-TE m-2

d-1

for all

the stations inside the Lagoon of Venice. The contribution of dioxin-like PCBs is always

lower than 20 % with the exception of EZI where PCBs contribute to almost one-half of the

total flux. While some of the monthly maxima found in EZI are similar to dioxin deposition

measured near industrial sites in Belgium, most of the other data fall within the range of

deposition measured in urban and rural areas of that region (Van Lieshout et al., 2001).

HCB fluxes among stations are quite different , with a very high “local” maximum in EZI

station (~4 ng m-2

d-1

), that drops immediately to values one order of magnitude lower in the

rest of the studied area (0.3-0.4 ng m-2

d-1

).

Finally, PAHs fluxes from the atmosphere still show higher values in EZI (> 3000 ng m-2

d-1

) than in all other stations (500-1000 ng m-2

d-1

). There is a slightly different pattern for

what concerns the stations inside the lagoon, where IBM is more similar to the ”industrial”

(DOG) and “urban” station (ADM), being presumably impacted by the traffic of big ships

passing the main entrance channel directed to the city of Venice.

P. Rossini et al. / submitted to The Science of the Total Environment 10

Seasonal variability is evident for PCDD-Fs and PAHs, while the fluxes of HCB and

PCBs seem to be independent from the season. The values found in winter (median October-

March PCDD-Fs: 82 pg m-2

d-1

; PAHs: 1091 ng m-2

d-1

) were higher than the summer ones

(median April–September: PCDD-Fs: 32 pg m-2

d-1

; PAHs: 417 pg m-2

d-1

), in line with

similar seasonal differences reported by Duarte-Davidson et al. (1994) and Halsall et al.

(1997) (Fig. 2).

On the other hand , monthly fluxes of PCBs and HCB do not show any seasonal trends,

with the overall median value maxima in May and August, respectively.

In order to understand the ability of different stations to capture the variability in the

deposition within the study area we have performed a discriminant analyses to check the

“distance” among sites - in other words, to highlight discriminating chemical elements, or

common groups of elements, not discriminants (Swan and Sandilands, 1995). The results

demonstrate that the six stations can be grouped into three main cluster (Fig. 3): (a) the

station inside the industrial zone (EZI), b) the urban station inside the city of Mestre (ADM)

and c) the stations inside and on the lagoon (L1, L2, L3, DOG and IBM). With the second

plot (F1 vs F3) the more distant station inside the lagoon (IBM) is separated from the others

because of some “urban” characteristics due to ship traffic and town activities.

P. Rossini et al. / submitted to The Science of the Total Environment 11

To summarize, from Table 1 and Figure 1 we can see that mean daily fluxes of all organic

pollutants were one-two order of magnitude higher in station EZI than in the others, and at

site DOG high levels of PCBs were also measured. In particular, differences between

“industrial” (EZI, DOG), “urban” (ADM, IBM) and “lagoonal” (L1, L2, L3) sites were clear,

at least for periods when all stations were operating (March 2003-March 2004). For PAHs,

high deposition levels were also observed in correspondence of stations ADM and IBM, and

at site ADM the PCDD-Fs mean daily flux was also remarkable. Some striking observations

are that within few kilometres (2-5) from the principal sources of emissions (located close to

EZI) there is a significant drop in the deposition value, while some spikes of PCBs and

PAHs call for other sources than the industrial ones both in the city of Mestre and inside the

Lagoon of Venice (traffic, urban activity, glass industry, etc.)

PCDDF guide value

Emission into the atmosphere followed by deposition on plants and animal uptake is the

main pathway of human exposure to dioxin. The World Health Organisation states that the

tolerable daily intake (TDI) of dioxins for humans is 1–4 pg TEQ kg-1

d-1

. By means of

selected transfer models, daily intake values have been translated by the Flemish Institute for

Technological Research (VITO) into quality objectives for dioxin deposition. A chain model

was used to establish the relationship between TDI and guide values for deposition (Van

Lieshout et al., 2001). The chain model includes three submodels: an atmospheric model for

the calculation of the wet and dry deposition, a model for the calculation of concentrations in

soil and grass and finally a cow model describing the transfer to milk and meat. Since the

design of the samplers used by the authors is very similar to that used in the present study,

P. Rossini et al. / submitted to The Science of the Total Environment 12

therefore the extrapolation of the target values is appropriate. Taking into account all

pathways of human exposure, the model was applied to derive total human intake by highly

exposed population subgroups near sources (De Fré et al., 2000). The TDI values proposed

by the WHO of 1-4 pg TEQ kg-1

d-1

corresponds to deposition limits of 3.4-14 pg TEQ m-2

d-

1 as a yearly average. A commission on air quality standards in Flanders decided to allow a

2-fold higher value (6.8-27 pg TEQ m-2

d-1

) for the monthly measurements, in order to

account for the shorter measurement period and the observed seasonal fluctuations (Van

Lieshout et al., 2001).

More recently, the European Union strategy on PCDD-Fs and PCBs has aimed at

reducing human intake levels to 14 pg TEQ kg-1

week-1

(European Commission, 2001, EU

strategy on dioxins, furans and polychlorobiphenyls, COM(2001) 593 final), corresponding

to 7 pg TEQ m-2

d-1

. In addition, it is important to keep in mind that Van Birgelen proposed

HCB to be a major contributor to the dioxin-like activity in chemical mixtures (Van

Birgelen, 1998; Van Birgelen, 1999).

As it can be seen in Fig. 1, the TEQ of mean atmospheric deposition flux at station EZI

(12.3 pgWHO-TE m-2

d-1

) is twice higher than guideline, and at site DOG, located about 5

km downwind of the industrial area (7.0 pgWHO-TE m-2

d-1

), is comparable to the limit.

Input budgets

By exploring the relationships between PCDD-Fs levels in surface soil, atmospheric

deposition, and distances from Porto Marghera industrial area, Matteucci et al. (submitted)

highlighted a strong industrial signal with an exponential decay of dioxins and furans with

P. Rossini et al. / submitted to The Science of the Total Environment 13

increasing distances from the industrial district. As authors show, PCDD-Fs industrial signal

attenuation values in surface soil were reached at distances higher than 8 km.

Based on this considerations, in order to calculate atmospheric loadings of POPs around

the industrial district, we considered a distance of 10 km from the hypothetical emission

centre of the main point sources of atmospheric emissions from the Porto Marghera

industrial area, obtaining an area equal to 314 km2 (Fig. 1).

Annual atmospheric loadings have been calculated by means of the equation:

annual loading = ( )=

=•

12

1

i

i

i Af

where, as above, the index i represents the 12 contiguous time intervals (months) into which

the monitoring period was divided, fi is the mean deposition estimated for the whole area

(i.e. the average of deposition fluxes estimated at all sampling sites) for the ith

month, and A

is the surface considered for calculation (314 km2).

Calculated loadings, compared with previous estimates (Rossini et al., 2001), are reported

in Table 2. Monthly total deposition loadings inside the study area vary from 0,3 to 4 g of

PCDD-Fs, 14 to 87 g of PCBs, 3 to 14 g of HCB and 3 to 17 kg of PAHs, corresponding on

average to 10-100 mg TEQ. As it can be seen in Table 2, annual atmospheric loadings of

POPs equal to 12 g, 510 g, 90 g and 130 kg of PCDD-Fs, PCBs, HCB and PAHs,

respectively, corresponding to 350-500 mg TEQ.

Results of atmospheric fall-out to the whole lagoon (surface area 550 km2) (Rossini et al.,

2001) carried out in 1998-99 suggest that atmospheric deposition may account for an

average annual loading of approximately 350-600 mg TEQ or 15 g, 1300 g, 2200 g and 160

Kg of PCDD-Fs, PCBs, HCB and PAHs, respectively. In order to compare the atmospheric

P. Rossini et al. / submitted to The Science of the Total Environment 14

fall-out on the same area (Fig. 1), we recalculated 1998-99 loadings using only data from

IBM and DOG sites, that were also included in the previous study.

Once carried out the recalculation (Table 2), the comparison indicate a slight decrease of

PCBs and a strong decrease of HCB with respect to years 1998-99. This reduction is difficult

to explain, and is possibly related to an “anomaly” of the industrial chlorine plant, already

seen in the strong month-to month variability. Thus, in order to obtain good estimates of

atmospheric deposition of POPs, extended monitoring network must be set up and

continuous sampling must be undertaken.

Lastly, this study indicate that POPs atmospheric depositions to the Porto Marghera and

the Venice Lagoon are significant. In fact, if we consider the direct inputs from industrial

district and the portion of watershed that runs into the designed area (see Table 2), the

relative importance of the three inputs is shown. In particular, from the table it can be seen

that atmospheric deposition is comparable to industrial discharges for all POPs , with the

exception of HCB, due to the very significant decrease of the last period. The watershed

seems to contribute less than other inputs only for PCDD-Fs. For these reasons, the

atmospheric compartment must be constantly monitored by supervisory authority and

considered by Italian law which, until now, has not provided limits for these pollutants,

especially considering the proximity of the Industrial Zone and the city of Mestre to a

sensitive area like the Lagoon of Venice

P. Rossini et al. / submitted to The Science of the Total Environment 15

Acknowledgements

This work was carried out on behalf of the Water Management Authority of Venice, the

Venice District Administration and the Venice Municipality. We acknowledge the Porto

Marghera Industrial Zone Agency for meteorological data.

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Provincia di Venezia. Rapporto sullo stato dell'Ambiente. Provincia di Venezia, Venezia,

2002, 138 pp. (in Italian).

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PAH DDT) in atmospheric deposition: sampling and analytical problems. Organohal

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Atmospheric input of organic pollutants to the Venice lagoon. Ann Chim (Rome) 2001;

91: 491–501.

Rossini P, Guerzoni S, Molinaroli E, Rampazzo G, De Lazzari A, Zancanaro A.

Atmospheric bulk deposition to the lagoon of Venice: Part I, fluxes of metals, nutrients

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US EPA Method 1613B/94: Tetra-through octa-chlorinated dioxins and furans by isotope

dilution HRGC/HRMS.

P. Rossini et al. / submitted to The Science of the Total Environment 18

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P. Rossini et al. / submitted to The Science of the Total Environment

Figure captions

Figure 1

Mean bulk deposition fluxes of POPs observed during the study period. Units = pg m-2

d-1

.

Dashed line represents the integrated guideline values for dioxin depositions, recently

proposed by the European Commission, (European Commission, 2001, EU strategy on

dioxins, furans and polychlorobiphenyls, COM(2001) 593 final) corresponding to 7 pg TEQ

m2 d

-1. The circle represents the area considered for atmospheric load calculations (radius =

10 km).

Figure 2

Median, 25%, 75%, min (non outlier) and max (non outlier) values of the monthly bulk

deposition flux (of all stations) of PCDD-Fs, PAHs, HCB and PCBs during the study period.

Figure 3

Discriminant score scatterplots for the first three discriminant functions.

P. Rossini et al. / submitted to The Science of the Total Environment

Table captions

Table 1

Bulk deposition fluxes of POPs observed during the study period. Values below DL were

considered equal to 0.5DL.

Table 2

Annual atmospheric loadings of POPs around the Porto Marghera industrial area (surface area

314 km2) compared with estimates of atmospheric fall-out to the whole lagoon carried out in

1998-99 and recalculated for homogeneity with present study. Values below DL were considered

equal to 0.5DL. The inputs derived from the direct water discharges of the industrial zone and

the watershed inputs are listed for comparison.

P. Rossini et al. / submitted to The Science of the Total Environment

Figure 1

PCBs

PCDD-Fs

EU guideline

0

2

4

6

8

10

12

14

WHO-TEQ

ADM

0

2

4

6

8

10

12

14

WHO-TEQ

EZI

0

2

4

6

8

10

12

14

WHO-TEQ

DOG

0

2

4

6

8

10

12

14

WHO-TEQ

L1

0

2

4

6

8

10

12

14

WHO-TEQ

IBM

0

2

4

6

8

10

12

14

WHO-TEQ

L2

0

2

4

6

8

10

12

14

WHO-TEQ

L3

#Y

#Y

#Y

#Y

#Y

#Y

#Y

ADM

DOG

EZI

L1

L2

L3

IBM

P. Rossini et al. / submitted to The Science of the Total Environment

Figure 2

PC

DD

/Fs (

pg

m-2

d-1

)

-20

20

60

100

140

180

220

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

PA

Hs (

ng m

-2 d

-1)

-500

500

1500

2500

3500

4500

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

HC

B (

ng m

-2 d

-1)

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

PC

Bs (

ng

m-2

d-1

)

-2

0

2

4

6

8

10

12

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

P. Rossini et al. / submitted to The Science of the Total Environment

Figure 3

Function 1

20100-10

Fu

nctio

n 2

4

2

0

-2

-4

-6

-8

S

Function 1

20100-10

Fu

nctio

n 3

4

2

0

-2

-4

-6

-8

St

L3

L2

L1

IBM

EZI

DOG

ADM

P. Rossini et al. / submitted to The Science of the Total Environment

Table 1

Bulk deposition fluxes of POPs observed during the study period. Values below DL were

considered equal to 0.5DL.

PCDD-Fs PCBs HCB PAHs TEQa

TEQb

rain

pg m-2

d-1

ng m-2

d-1

ng m-2

d-1

ng m-2

d-1

pgWHO-TE m-2

d-1

pgI-TE m-2

d-1

mm

deposition range 67-2767 11-44 1,9-6,7 1032-10575 7-30 2,2-24 3,7-84

mean value 403 21 4,1 3525 12 6 40

median value 121 19 4,1 3381 10 4,3 33

samples 11 11 11 11 11 11 11

deposition range 15-431 0,9-31 0-0,9 184-3984 0,6-48 0,1-47 4,9-177

mean value 92 4,2 0,4 1164 7 6 56

median value 51 1,6 0,4 957 2,9 1,6 55

samples 12 12 12 12 12 12 12

deposition range 46-169 1,5-6,1 0,1-1,2 327-2301 1-5 0,4-3,7 4-100

mean value 92 3,1 0,4 1002 3,4 1,7 47

median value 75 2,8 0,3 624 3,3 1,3 37

samples 11 11 11 11 11 11 11

deposition range 13-200 0,7-2,3 0-0,7 219-3969 0,1-11 0-10 4,9-174

mean value 49 1,3 0,3 1108 2,1 1,7 53

median value 33 1,2 0,2 560 1,6 1,1 42

samples 12 12 12 12 12 12 12

deposition range 16-136 0,5-8 0-1,1 143-1847 0,1-8 0,1-7 0,5-130

mean value 51 1,9 0,4 544 2,7 2,1 39

median value 40 1,0 0,3 385 2,3 1,5 35

samples 11 11 11 12 11 11 12

deposition range 12-157 0,4-6,4 0,1-1,3 73-957 0-9 0-8 0-77

mean value 45 1,2 0,3 464 2,2 1,9 40

median value 28 0,8 0,2 447 1,2 0,8 50

samples 12 12 12 12 12 12 12

deposition range 15-162 0,3-0,9 0-1 263-1458 0-8,1 0,9-8 1,4-112

mean value 55 0,6 0,3 546 2,6 2,9 53

median value 41 0,6 0,2 357 2,0 2,2 60

samples 7 7 7 7 7 6 7

mean deposition range 31-506 2,2-10 0,4-1,3 337-2443 2-12 0,7-9 5-129

mean deposition 116 5 0,9 1234 5 3

a Van Den Berg et al. (1998)b NATO/CCMS (1998)

EZI

DOG

ADM

IBM

whole area

L1

L2

L3

P. Rossini et al. / submitted to The Science of the Total Environment

Table 2

Annual atmospheric loadings of POPs around the Porto Marghera industrial area (surface area 314

km2) compared with estimates of atmospheric fall-out to the whole lagoon carried out in 1998-99 and

recalculated for homogeneity with present study. Values below DL were considered equal to 0.5DL.

The inputs derived from the direct water discharges of the industrial zone and the watershed inputs

are listed for comparison.

PCDD-Fs

g

PCBs

g

HCB

g

PAHs

kg

TEQ a

mgI-TE

This study 12 513 94 126 346

1998-99b 11 522 1125 111 380

Industrial area c 25 400* 1600 68 650

Watershed d 7 449 924 n.a. 60

aNATO/CCMS (1988);

bRossini et al. (2001);

cMagistrato alle Acque (2004);

d Bettiol et al. (in press); * only 170CB+180CB; n.a. = not available.

PCBs

PCDD-Fs

EU guideline

0

2

4

6

8

10

12

14

WHO-TEQ

ADM

0

2

4

6

8

10

12

14

WHO-TEQ

EZI

0

2

4

6

8

10

12

14

WHO-TEQ

DOG

0

2

4

6

8

10

12

14

WHO-TEQ

L1

0

2

4

6

8

10

12

14

WHO-TEQ

IBM

0

2

4

6

8

10

12

14

WHO-TEQ

L2

0

2

4

6

8

10

12

14

WHO-TEQ

L3

#Y

#Y

#Y

#Y

#Y

#Y

#Y

ADM

DOG

EZI

L1

L2

L3

IBM

Figure 1

Figure

PC

DD

-Fs (

pg

m-2

d-1

)

-20

20

60

100

140

180

220

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

PA

Hs (

ng m

-2 d

-1)

-500

500

1500

2500

3500

4500

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

HC

B (

ng m

-2 d

-1)

0,0

0,2

0,4

0,6

0,8

1,0

1,2

1,4

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

PC

Bs (

ng m

-2 d

-1)

-2

0

2

4

6

8

10

12

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

Figure 2

Function 1

20100-10

Fu

nctio

n 2

4

2

0

-2

-4

-6

-8

S

Function 1

20100-10

Fu

nctio

n 3

4

2

0

-2

-4

-6

-8

St

L3

L2

L1

IBM

EZI

DOG

ADM

Figure 3