The Science of the Total Environment 246 2000.

121137

Benthic fluxes of cadmium, lead, copper and nitrogen

species in the northern Adriatic Sea in front of the
River Po outflow, Italy
Cristina Zago a,U , Gabriele Capodaglioa,b, Sergio Ceradini c ,
Giovanni Ciceri c , Luisa Abelmoschi d, Francesco Soggiad,
Paolo Cescona,b, Giuseppe Scarponi e
a

Dipartimento Scienze Ambientali, Uni ersita

` Ca` Foscari di Venezia, Dorsoduro 2137, 30123 Venezia, Italy
Centro di Studio sulla Chimica e le Tecnologie per lAmbiente-CNR, Venezia, c r o Uni ersita
` Ca` Foscari di Venezia,
Dorsoduro 2137, 30123 Venezia, Italy
c
ENEL, SRI, Via Reggio Emilia 39, 20090 Segrate, Milano, Italy
d
Dipartimento di Chimica e Chimica Industriale, Sezione Chimica Analitica ed Ambientale, Via Dodecaneso 31, 16146
Geno a, Italy
e
Instituto di Sciente del mere, Uni ersita
` di Ancona, Via Brecce Bianche, 60131 Ancona, Italy
b

Received 1 June 1999; accepted 13 October 1999

Abstract
Trace heavy metal Cd, Pb and Cu. and nitrogen species N-NO3 , N-NO2 and N-NH 4 . fluxes between sediment
and water were examined for approximately 4 days, in a coastal marine station located in the northern Adriatic Sea
in front of the River Po outflow. An in situ benthic chamber, equipped with electronic devices for monitoring and
adjustment of oxygen and pH and with a temperature detector, was used. The benthic chamber experiment enabled
study of the temporal trend of metals and nutrients when oxygen concentration varied in a controlled environment.
Although particular care was devoted to chamber deposition and parameter control, sediment resuspension occurred
at the beginning of the experiment and O 2 fluctuations were observed during the course of the experiment. Pb
concentration was affected by both resuspension and oxic conditions in bottom water, which prevented determination
of any reasonable Pb flux value. Cd and Cu, not influenced by oxygen fluctuations, reached an equilibrium phase in a
short period with initial positive fluxes from sediment of 0.68 S.D.s 0.07. and 6.9 S.D.s 5.6. pmol cmy2 hy1 ,
respectively. With regard to nitrogen species, the highest positive flux was that of N-NH 4 10.5, S.D.s 2.4, nmol
cmy2 hy1 . whose concentration increased in the chamber, while nitrate concentration initial flux of y5.7,
S.D.s 1.5, nmol cmy2 hy1 . immediately decreased after the beginning of the experiment. Nitrite concentration was

Corresponding author. Tel.: q39-0412578504; fax: q39-0412579549.

0048-9697r00r$ - see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 0 4 8 - 9 6 9 7 9 9 . 0 0 4 2 1 - 0

122

C. Zago et al. r The Science of the Total En ironment 246 (2000) 121137

almost constant throughout the experiment and its flux was generally low initial flux 0.1, S.D.s 0.9, nmol cmy2
hy1 .. 2000 Elsevier Science B.V. All rights reserved.
Keywords: Po River outflow; Metals; Nitrogen; Benthic fluxes

1. Introduction
The sedimentwater interface of a marine basin
is the site where gradients in chemical, physical,
and biological properties are the greatest. Fluxes
of constituents through this interface, called benthic fluxes, affect element concentrations in both
pore waters and overlying bottom waters; thus
they are important processes of the whole marine
biogeochemical cycles of many elements Val
Klump and Martens, 1981; Santschi et al., 1990;
Rivera Duarte and Flegal, 1994; Riedel et al.,
1997.. Processes responsible for these benthic
fluxes are usually the upward flow of pore water
caused by hydrostatic pressure, molecular diffusion due to concentration gradients e.g. concentrations in pore waters are generally higher than
in overlying waters., and mixing of sediment and
water at the interface due to bioturbation and
water turbulence Santschi et al., 1990; Petersen
et al., 1997..
In coastal areas, due to settling of particulate
material, elevated amounts of pollutants are frequently accumulated in sediments, which indeed
constitute an enormous potential repository for
continuing inputs, with capability of transferring
accumulated material to the coastal ecosystem
even after anthropogenic inputs have been reduced or eliminated. For many chemical species,
sediments constitute the final repository. However, chemicals may be recycled many times across
the sedimentwater interface before being permanently buried Santschi et al., 1990.. Diagenetic reactions contribute to this cycling, and,
for example, metals temporarily stored in sediments may dissolve in porewaters and diffuse to
overlying waters due to gradient concentrations.
Direct measurements of benthic fluxes can be
obtained by using benthic chambers Ciceri et al.,
1992; Giblin et al., 1997.. Benthic chambers are
based on a simple principle. A known sea water
volume and a known sediment surface are isolated

inside the chamber during the experiment period.

Water samples are periodically collected and
analysed to monitor oxygen conditions inside the
chamber and to follow the temporal trend of
studied elements. Benthic fluxes are finally estimated from concentration changes in time. Differently from the case of large box core sampling,
an in situ chamber allows a benthic environment
to be enclosed without its removal from the original place, and thus permits estimation of benthic
fluxes with minimal perturbations. Diagnostic
parameters such as temperature, oxygen, pH,
Eh. measured in the enclosed water trace important changes inside the chamber. The rise of
anoxic conditions inside the chamber during the
experiment can produce fluxes which are much
higher than the real ones Hammond et al., 1985;
Sundby et al., 1986.. For this reason oxygen and
pH need to be kept almost constant throughout
the experiment. External additions are generally
performed to balance the effect of microbial decomposition of organic matter, which lowers oxygen and pH inside the chamber.
The use of a benthic chamber to determine
fluxes at the sedimentwater interface in an almost anoxic environment is useful to understand
what happens in metal and nutrient cycling when
low oxygen concentrations are present in bottom
waters, a phenomenon that frequently occurs in
coastal and organic rich waters. In the present
study, a highly anthropised coastal marine environment of the northern Adriatic, influenced by
the River Po outflow, was selected for the benthic
fluxes experiment as anoxic conditions commonly
occur in late summer Spagnoli and Bergamini,
1997.. In summer, the circulation of waters in this
area is rather slow in winter a fast-moving cyclonic system prevails., with a horizontal stratification in the water column Barbanti et al., 1995;
Spagnoli and Bergamini, 1997.. To quantify the
benthic fluxes in the anoxic period a benthic

C. Zago et al. r The Science of the Total En ironment 246 (2000) 121137

chamber was located in early October 1996 by

expert scuba divers at a coastal site, at a depth of
20 m. The benthic fluxes of some heavy metals
Cd, Pb, Cu. and of nitrogen species N-NO3 ,
N-NO2 , N-NH 4 . were studied using an in situ
benthic chamber, fitted with an oxygen control
device. Measurements were carried out in the
dissolved fraction of seawater filtrate from a
0.4-m pore size filter.. In the case of Pb, both
dissolved and particulate concentrations were determined due to the low amount of particulate
matter only one metal could be determined..

2. Materials and methods

2.1. Laboratories, general equipment and materials
Clean chemistry laboratories with Class 100
areas for the most critical procedures preparation and cleaning of sampling equipment and
bottles, filtration and treatment of samples, voltammetric analysis . were available both in the
Venice University laboratory and on board.
Laboratories, equipment and procedures have
been described elsewhere Ciceri et al., 1992;
Capodaglio et al., 1994a; Scarponi et al., 1996;
Zago, 1999. and the reader should refer to this
literature for details.

123

and procedures, storage conditions, pretreatment

of samples and final instrumental analysis see
Scarponi et al., 1996..
Particular attention was devoted to cleaning
the FEP Teflon Fluorinated Ethylene Propylene,
Nalgene. bottles, following the procedure described in Scarponi et al. 1996. which provides
for both HNO3 and HCl Merck, Suprapur. acid
treatments. On board, bottles were conditioned
before use, filling them a few times with filtrated
seawater collected on site.
All the materials used for sampling, filtration
and sample treatments followed similar acid
cleaning procedures in order to obtain an elevated cleanness standard. Policarbonate filters
were cleaned with diluted HCl Merck, Suprapur..
Before use, filters was conditioned with filtered
seawater.
2.3. Benthic chamber experiment
The experiment was carried out from 7 to 11
October 1995 at a coastal site in front of the
River Po outflow, 444445.70N, 122716.30E,
Fig. 1.. During chamber positioning, the scuba
divers observed a high presence of particulate
and colloidal material close to the bottom. The

2.2. Contamination control

Heavy metals dissolved in marine waters are
usually present in very low concentrations nM or
lower.. For this reason it is of primary importance
to keep all materials and procedures involved in
collecting, storing, and sample treatments and
analysis under rigorous contamination control in
order to prevent every possible sample contamination Mart, 1979a,b.. In this work, careful attention with respect to any potential contribution
to contamination was given to general laboratory
equipment, chemical reagents, materials used for
sampling bottles, sampling equipment, storage
bottles and their cleaning, on board laboratories
and other facilities in the field, filtration devices

Fig. 1. Map of the northern Adriatic Sea in front of the river

Po outflow showing the site of study. Cruise Prisma I
MURST., research vessel Urania, October 711, 1995, site
18S1..

124

C. Zago et al. r The Science of the Total En ironment 246 (2000) 121137

chamber was carefully deposited on the bottom

using all precautions required to not disturb the
superficial sediment.
An in situ benthic chamber of cylindrical shape
internal diameter 70 cm, height 32 cm. and
volume of approximately 120 l was used Fig. 2..
Probes for temperature, O 2 and pH measurements were mounted inside the chamber. Devices
for O 2 and pH adjustments were also available to
prevent anoxia and increasing acidity. External
additions of O 2 Chromatographic grade. were
performed by the use of a diving bomb lower
non-intervention limit 1.2 mg ly1 .. Added oxygen
volumes were controlled by an electronic monitoring device located on the water surface. At
irregular time steps, decided in the field by the
operator and related to oxygen concentrations
inside the chamber, but constrained by logistic
feasibility, 30 or 60 ml atmospheric pressure.
oxygen aliquots were added. To prevent pH decrease, 1.4-ml aliquots of a 0.1 M NaOH solution
were automatically added when the pH inside the
chamber passed from the original value of 7.9 to
7.8 lower non-intervention limit defined at the
beginning of the experiment.. The NaOH solution used was previously purified in our clean
laboratory using a Chelex-100 resin column.
To exclude any possible effects of metal contamination from gaseous oxygen and NaOH solu-

Fig. 2. Diagram of the in situ benthic chamber used for the

experiment.

Table 1
Oxygen volumes at atmospheric pressure. pumped inside the
benthic chamber to prevent anoxia during the experiment, at
specified times from the beginning of the experiment
Time h.

Volume
ml.

Time
h.

Volume
ml.

6
9
12
15
18
21
22.7
23.3
24.3
25.3
43.6
44.6
45.6

30
30
30
30
30
30
60
60
60
60
60
60
60

46.6
47.6
62.1
65.1
68.1
71.1
74.1
77.2
80.2
83.2
86.2
89.2
92.2

60
60
30
30
30
30
30
30
30
30
30
30
30

tion injected inside the chamber, tests were previously performed in the laboratory. Two 2-l bottles
filled with ultrapure water were insufflated every
2 h with 45 ml of O 2 for 30 and 60 h, respectively,
using the same oxygen bombs as those of the
benthic chamber experiment. The samples were
then analysed for Cd, Pb and Cu content. The
tests did not show any metal contamination in the
insufflated waters. Similarly, direct analysis of the
NaOH solution showed no metal contamination.
In Table 1 oxygen additions performed during the
experiments are reported. The NaOH additions
1.4 ml injected for 2 min every hour. were performed starting from 16.5 h from the beginning of
the experiment.
Approximately twice per day water samples for
determination of metals approx. 700 ml. and
nutrients approx. 300 ml. were collected by a
peristaltic pump connected with the benthic
chamber through a FEP sampling tube internal
diameter 6 mm.. Samples were collected after
pumping approximately 400 ml of water dead
volume of the sampling tube connecting the benthic chamber with the sea surface .. Water volumes
extracted from the chamber were immediately
balanced by drawing water from the outside
chamber environment through a pressure valve
located in the benthic chamber walls. During the
4 days of the experiment, nine samples were

C. Zago et al. r The Science of the Total En ironment 246 (2000) 121137

collected at the following times hours.: 0 immediately after deposition., 7, 12 only for nitrogen compounds., 23, 33.5, 47, 57, 71, 81 and 95.
The low volume of water collected from the
chamber and replenished from the outside environment is considered irrelevant in comparison
with the total benthic chamber volume approx.
0.8% of the total volume was sampled in each
drawing and only approx. 10% in all the experiment..
Filtration of samples was performed at the
moment of sampling, using an FEP Fluoroware.
apparatus especially developed for on-line pressure filtration. The peristaltic pump was used to
apply a depression in the sampling bottle 2 l,
FEP. and the sample was forced to pass through
the filter mounted in an in-line filter holder Fluoroware, Mod. 411. at the top of the bottle.
Polycarbonate 0.4-m filters Nuclepore. were
used.
To preserve sample integrity with regard to the
total metal concentration Capodaglio et al., 1995.
they were stored frozen at a temperature of
y20C without mineral acid treatment.
2.4. Voltammetric determination of Cd, Pb and Cu
in seawater
The instrumentation assembly for voltammetric
determinations of total dissolved Cd, Pb and Cu
used in our laboratory consists of an electrochemical cell especially developed for ultratrace metal determination in seawater EG & G,
Model Rotel 2, Munich, Germany. Mart et al.,
1980. and of a voltammetric device with anodic
stripping capability in the differential pulse mode,
DPASV EG & G, Polarographic Analyzer, Model
384B, Princeton, NJ, USA..
The electrochemical cell Teflon, PTFE. is
equipped with a rotating glassy carbon disk electrode, RGCDE, and an AgrAgCl, KClsat..
reference electrode to which all potentials are
referred. A Pt wire was used as an auxiliary
electrode. The auxiliary electrode is inserted inside small FEP tubes, filled with saturated KCl
solution, and fitted with porous Vycor tips. A
Teflon cap covers the cell and separates it from
the Plexiglas box holding the electrode motor and

125

the cell controller. The cleanness obtained by this

electrochemical cell makes it possible to ensure a
low detection limit of DPASV of approximately
0.2 ng ly1 for Cd and Pb Scarponi et al., 1997.
and 1 ng ly1 for Cu Capodaglio et al., 1994b..
The working electrode was a preformed thin
mercury film electrode TMFE. deposited on the
surface of the RGCDE just before beginning the
measurement. This technique, avoiding any external preconcentration, allows a high sensitivity and
a low contamination risk.
To prepare the RGCDE for film deposition, it
was rotated at 1000 rev. miny1 and the smooth
surface was polished with wetted alumina powder
0.075 m grain size or lower. using a filter paper.
The electrode was then rinsed for 5 min with
1:200 diluted ultrapure HCl and then two or
three times with ultrapure water. The Hg film was
plated by controlled potential electrolysis of
HgII. nitrate solution. The electrolytic solution is
made 2.5= 10y2 M in KCl ultrapure. and 10y4
M HgNO 3 . 2 and purged with N2 for at least 20
min; HgNO 3 . 2 is prepared by oxidising hexadistilled Hg with HNO3 NIST.. Deposition was carried out at y1.0 V for 20 min while the electrode
was rotating at 4000 rev. miny1 . A quiescent
period of 30 s follows and then a differential
pulse potential scan was carried out in the positive direction until a potential of y0.18 V is
reached with a scan rate of 10 mV sy1 , a pulse
height of 50 mV and a pulse frequency of 5 sy1 .
If the voltammogram obtained did not show
any appreciable peak and the base current is
sufficiently low 300500 nA., then it was possible
to carry on the analysis of the samples; otherwise
the Hg film was destroyed and another prepared.
The electrochemical assembly was rinsed by one
aliquot of degassed sample before starting the
measurements.
Total dissolved metal concentration measurements were carried out on UV digested pHf 2.
samples. In fact, due to the large amount of
organic matter expected in bottom water samples
of coastal areas, acid digestion alone was not
sufficient to release the metals completely especially in the case of Cu. due to very strong binding of macromolecular ligands Scarponi et al.,
1996.. For acid digestion, 100 l of 32% HCl

126

C. Zago et al. r The Science of the Total En ironment 246 (2000) 121137

Ultrapure, NIST National Institute of Standards

and Technology, USA. was added to 50 ml of
sample Nurnberg
et al., 1976.. The metal con
centrations introduced into the samples by this
HCl addition certification shows 0.014 ng ly1 of
Cd and 0.006 ng ly1 of Pb. are lower than the
detection limits reported above Scarponi et al.,
1996.. UV irradiation of acidified samples was
performed by high-power Hg lamp 1.2 kW. for 4
h.
Separate determinations of Cd and Pb on one
side, and Cu on the other were then performed
according to the following procedure. Approximately 50 ml of digested sample precise volume
measured at the end of analysis . is transferred
into the electrochemical vessel in the degassing
position of the cell assembly and purged for 20
min with N2 . The vessel was then rapidly transferred in the measurement position of the cell
where the TMFE has already been prepared,
tested and rinsed. The metal deposition was then
carried out by constant potential electrolysis Cd
and Pb determination:y 0.95 V, 20 min; Cu determination:y 0.85 V, 10 min. with electrode rotating at 4000 rev. miny1 . After a quiescent period of 30 s a pulsed potential scan was applied in
the positive direction from the deposition potential to the final potential y0.18 V for Cd and Pb
and y0.15 V for Cu. and the voltammogram
recorded stripping step.. At the end of the scan
the rotation was restarted 4000 rev. miny1 . and
the potential held at y0.18 V for 5 min to clean
the electrode of the residual amalgamated metals.
To test electrode stability and repeatability of the
voltammogram, a second measurement was performed on the sample solution. Three standard
additions are used for quantification, each able
approximately to double the peak obtained by the
sample deposition 20 % 50 l of Cd and Pb standard solutions of 100 g ly1 , 20 l of Cu standard solutions of 600 g ly1 .. After each addition
the voltammetric measurement is repeated. The
volume of the sample is finally measured using a
graduated cylinder and the working electrode is
prepared for a new determination starting from
polishing.
The accuracy of laboratory measurements was
periodically verified generally every 2 weeks. by

determining the metal content of the NASS-4

seawater reference material National Research
Council of Canada, Ottawa, Canada.. The results
were reported on a control chart, and typical
examples have already been reported see e.g.
Scarponi et al., 1996; Zago, 1999.. Measurements
on samples were carried out only in the case of
values included in the certified tolerance interval.
Otherwise, checks of the overall procedure and
standard concentrations were performed to restore accuracy before running new measurements.
As regards repeatability, it is to be noted that
for each sample measurements were repeated
three times see below. and the relative pooled
standard deviations were approximately 5.5%,
8.4% and 4.8% for Cd, Pb and Cu, respectively.
2.5. Other determinations
Nitrate, nitrite and ammonium in filtrated seawater were determined by colorimetric methods
Parson et al., 1984.. The nitrate concentration
was determined by flow injection analysis FIA.,
using a Lachat Quickchem Automatic Flow Injection Ion Analyzer. The method is based on the
reduction of nitrate to nitrite in a cadmium copperised column followed by a spectrophotometric
determination of nitrite after diazotisation reaction with sulphanilamide by N-1-naftil. ethylenediamine 2 HCl. Nitrite was determined using the
second step of the previous procedure. The detection limits are 2 and 0.1 g ly1 for nitrate and
nitrite, respectively. The ammonium determination was also performed by FIA using the colorimetric method based on the Berthelot reaction
Solorzano, 1969.. The detection limit of this
technique is 1 g ly1 .
Temperature, oxygen concentration and pH
were measured in situ during the benthic chamber experiment, using a multiparametric probe
Idronaut, Mod. 316. modified for trace metal
analysis. The probe was also used to control the
devices for oxygen and pH adjustment inside the
benthic chamber.
Due to the low water volume collected for each
sample, the particulate amount in filters allowed
the analysis of only one metal with the technique.

C. Zago et al. r The Science of the Total En ironment 246 (2000) 121137

Lead was selected due to its known affinity with

particulate material Turekian, 1977; Rivera
Duarte and Flegal, 1994..
Lead in particulate matter was determined by
atomic absorption spectrophotometry GFAAS,
SpectrAA 400 Plus, Varian, equipped with
graphite furnace GTA96. after microwave digestion CEM Corporation, MDS-2000, 630 Watt. in
Teflon containers with pressure control Advanced Computed Vessel, ACV.. Filters were
dried and weighted in a laminar flow hood Class
100.. They were brought to constant weight and
microwave acid digested with 3 ml of 8 M nitric
acid Merck, Suprapur.. The following program
was used: 0.5 min at 30% of microwave power, 0.5
min at 40% and 1 min at 50%. The solution was
then adjusted to 5 ml by adding ultrapure water
Millipore, Milli-Q.. Filters were again dried in
laminar flow and brought to constant weight to
determine, by difference, the amount of solubilized particulate material. Lead determination
was performed in the digested solution by the
standard additions method.
2.6. Calculation of benthic fluxes
The benthic flux of a chemical species at the
sedimentwater interface is defined as the mass
of that species flowing per unit of sediment surface and per unit of time. Considering the generic
time interval between observations i and i q 1
carried out during the experiment with i s 1 ,n.,
and defining the time interval as t i s t iq 1 y t i ,
the corresponding mass gradient measured in water as m i s m i q 1 y m i and S the surface of the
sedimentwater interface in the benthic chamber,
the mean benthic flux in the considered time
interval, Fi , can be computed using the equation:
Fi s

mi
S ti

1.

Usually S is given in cm2 , t i in hours and the

units of flux depend on units of m i which, in
turn, are related to the concentration units. Denoting Ci s Ciq 1 y Ci as the concentration gradient in the considered time interval in nmol ly1 ,

127

i.e. pmol cmy3 , for trace metals, and in mol ly1 ,

i.e. nmol cmy3 , for nitrogen species., V as the
volume of the benthic chamber in cm3 . and H
the chamber height in cm., then
m i s Ci V

2.

and
S s VrH

3.

can be substituted in Eq. 1., giving the following

final equation for flux:
Fi s

Ci H
ti

4.

with Fi expressed as pmol cmy2 hy1 , for trace

metals, and as nmol cmy2 hy1 for nitrogen
species, respectively.
Positive fluxes result when concentrations increase with time. In this event material release
from sediment andror from particulate matter to
the water phase is inferred. On the contrary,
negative fluxes result when concentrations in water decrease with time. This last is the case of
transport toward the sediment or the particulate.
It is to be remarked that in some cases, chemical
transformations between different chemical forms
of the same element present in the water phase
can also simulate benthic fluxes. Moreover, concomitant processes occurring in both directions at
the sedimentwater interface can occur. In both
cases apparent fluxes are observed from measurements carried out only in water, representing
the overall result of all possible processes. Due to
the general non-linear temporal profiles except
for N-NH 4 . natural fluxes were calculated from
concentration gradients determined between the
start of the experiment and the subsequent observation wEq. 4. for i s 1x. In the case of N-NH 4
linearity was observed within the first 33.5 h of
the experiment, thus natural flux was computed
as the average of individual values measured up
to this time.

128

C. Zago et al. r The Science of the Total En ironment 246 (2000) 121137

3. Results and discussion

3.1. General characteristics of the enclosure during
the experiment
Temperature, oxygen, pH and particulate matter changes during the experiment are shown in
Fig. 3. Temperature was almost constant throughout the experiment with a very slight decrease in
time. At the beginning, low oxygen concentration,
approximately 1.3 mg ly1 close to anoxia and to
the intervention limit of 1.2 mg ly1 ., was measured inside the chamber. Similar conditions are
frequently found, at the end of the summer period, in the bottom waters of many estuaries and
coastal areas due to seasonal stratification of water masses Officer et al., 1984; Selinger et al.,
1985.. In spite of the oxygen additions performed
inside the chamber when the intervention limit
was reached 6 h from the beginning of the experiment and continuing every 3 h, see Table 1.,
oxygen concentration decreased continuously. After 21 h it decreased Fig. 3. to the lower acceptable level 0.12 mg ly1 . decided as the point of
further intervention to prevent strongly anoxic
conditions occurring inside the chamber. Then,
the oxygen flow pumped into the benthic chamber
was temporarily enhanced both in quantity from
30 to 60 ml. and in frequency pumping every ; 1
h., the first time from 22.7 to 35.3 h, and the
second from 43.6 to 47.6 h Table 1.. The original
programme of O 2 additions 30 ml every 3 h. was
restored after 62.1 h and continued until the end
of the experiment. The fluctuations in oxygen
concentration measured inside the chamber Fig.
3. are consequences of these changes in oxygen
fluxes.
The pH inside the chamber ranged between
7.90 and 7.67 throughout the experiment Fig. 3..
The reduced variation allowed us to consider pH
almost constant.
Although the chamber was carefully deposited
on the bottom, as already described, a small
amount of resuspension occurred. The particulate
material inside the benthic chamber increased
considerably at the beginning of the experiment
suggesting a sediment and consequently pore
water. resuspension due to chamber placement

Fig. 3. Temporal trends of temperature, oxygen, pH and particulate material inside the benthic chamber.

Fig. 3.. The low value of particulate matter measured at time zero refers to the sample collected
from the top of the chamber, before resuspension
affected this part of the enclosure. For this reason it represents the original particulate content
in the site under study. Subsequently after the
first 7 h, the particulate matter inside the chamber strongly decreased due to particulate settling
and the system reached approximately the initial
conditions after approximately 60 h. In the case
of resuspension, the concentrations of elements
with high affinity with particulate, e.g. Fe, Mn and

C. Zago et al. r The Science of the Total En ironment 246 (2000) 121137
Table 2
Cd, Pb and Cu concentrations determined in seawater samples collected during the experiment
Time h.

Metal concentrations nmol ly1 .

Repetitions

Cadmium
0
7
23
33.5
47
57
71
81
95
Lead
0
7
23
33.5
47
57
71
81
95

0.26, 0.17, 0.21

, ,
0.73, 0.69, 0.69
0.70, 0.64, 0.58
0.69, 0.67, 0.66
0.62, 0.64,
0.63, 0.67, 0.72
0.66, 0.60, 0.65
0.18, 0.27, 0.25

0.26, 0.33, 0.34

0.71, 0.72, 0.62
0.09, 0.11, 0.10
0.50, 0.49, 0.49
0.15, 0.14, 0.14
0.19, 0.19,
0.11, 0.12, 0.11
, 0.08, 0.06
0.04, 0.05, 0.06

Table 3
Particulate Pb concentration during the experiment referred
both to particulate mass and to seawater volume
Time h.

Mean

R.S.D. %.

0.21

0.70
0.64
0.67
0.63
0.67
0.64
0.23

21

3.3
9.4
2.3
2.2
6.7
5.0
20

nmol gy1
0
7
23
33.5
47
57
71a
81
95

14
8.1
10
1.2
4.0
0.0
5.1
20
20

nmol ly1
0
7
23
33.5
47
57
71a
81
95

0.31
0.68
0.10
0.49
0.14
0.19
0.11
0.07
0.05

Copper
0
7
23
33.5
47
57
71
81
95

9.1, 9.2, 8.5

10.0, 9.5, 11.7
9.6, 8.8, 9.2
9.0, 9.6, 9.7
9.2, 9.7, 10.4
9.6, 10.0, 10.7
10.5, 10.6, 10.6
10.6, , 9.9
4.0, , 3.9

8.9
10.4
9.2
9.4
9.8
10.1
10.6
10.2
4.0

4.2
11
4.3
4.0
6.2
5.5
0.5
4.8
1.8

Pb, may artificially change in both water and

suspended matter, with consequent modifications
of the original benthic fluxes Turekian, 1977;
Forstner
and Wittman, 1979; Rivera Duarte and

Flegal, 1994..
3.2. Trace metals
The Cd, Pb and Cu concentrations in sea water
samples and the Pb concentration in particulate
matter referred to both weight of particulate,
nmol gy1 , and volume of water, nmol ly1 .,
together with their mean values and analytical

129

Particulate Pb concentration
Repetitions

Mean

R.S.D. %.

47, 47, 49
155, 154, 159
127, 123, 127
77, 74, 71
28, 29, 29
28, 28, 29
111, 110, 110
57, 57, 59
41, 41, 42

48
156
126
74
29
28
110a
58
41

2.4
1.7
1.8
4.1
2.0
2.0
0.5
2.0
1.4

0.25, 0.25, 0.26

4.00, 3.96, 4.09
2.18, 2.12, 2.19
0.99, 0.95, 0.92
0.34, 0.35, 0.34
0.26, 0.26, 0.26
1.15, 1.14, 1.14
0.49, 0.49, 0.50
0.40, 0.40, 0.41

0.25
4.02
2.16
0.95
0.34
0.26
1.14a
0.49
0.40

2.3
1.7
1.8
3.7
1.7
0.0
0.5
1.2
1.4

Contaminated sample.

repeatabilities, are reported in Tables 2 and 3.

The sample collected for particulate Pb at 71 h
proved to be contaminated and the corresponding
outlying value was not considered in further
elaborations. The different behaviours observed
for Pb, on one side, and Cd and Cu, on the other,
suggest to describe metals results in this two
metal grouping.
3.2.1. Lead
Fig. 4 shows the concentration trends of Pb in
the particulate fractions during the experiment.
Data on particulate content are also shown.
The particulate fraction of the total lead concentration in seawater particulate lead in nmol
ly1 . shows a very similar trend to that of the
particulate amount, both with an initial substantial increase, followed by a gradual decrease during the experiment, initially more rapid and then
rather slow. Indeed, a good correlation r s 0.96.
is observed. This result confirms the occurrence
of sediment resuspension at the beginning of the

130

C. Zago et al. r The Science of the Total En ironment 246 (2000) 121137

Fig. 4. Particulate Pb expressed in nmol gy1 dashed line., and nmol ly1 small dotted line. measured inside the benthic chamber
during the experiment. The content of particulate matter is also reported continuous line.. Error bars "1 S.D.

experiment as observed through the Pb behaviour. As regards the lead content in particulate matter expressed in nmol gy1 , it is less affected by resuspension than the previous variable,
and the correlation with the amount of particulate matter is reduced to 0.88. However, an increase of lead content in particulate matter from
the initial value 47 nmol gy1 . to 7 h later 155
nmol gy1 . was observed, and it corresponds to
the maximum particulate content inside the
chamber. Thus, Pb concentration in suspended
matter ranged between the value of the original
particulate matter, in the case of no resuspension
beginning of the experiment., and that of sediment when resuspended matter predominates in
the particulate. By this result, it is reasonable to
conclude that Pb concentrations in superficial
sediments were higher than those of the original
particulate material. After 47 h, Pb concentrations expressed in nmol gy1 in Fig. 4. again
showed values similar to the initial ones, meaning
that resuspended material, presumably composed
by particles with larger mass grains and with a
higher sedimentation rate, had sank into the sediment Forstner
and Wittman, 1979..

The Pb concentration in the dissolved fraction

shows a temporal trend which highlights the influence of both resuspension and oxygen concentration Fig. 5.. Indeed the trend of soluble lead
concentration in time shows a temporary initial

increase observed after 7 h of experiment. followed by a general decrease during the experiment, related to the sediment resuspension, with
superimposed fluctuations corresponding to those
of oxygen content.
The fluctuations of Pb concentration during the
experiment should not be attributed to possible
external contamination caused by oxygen inflow
for two reasons. First of all, as explained in the
experimental part, the oxygen inflated from the
diving bomb was tested for metal contamination
before the experiment and proved uncontaminated. Secondly, the relationship stressed here
regards the O 2 concentration in water and not
the volume of O 2 added, which has a very different pattern see Table 1..
The observed relationship between dissolved
lead and oxygen concentrations r s 0.61, Fig. 5.
suggests that the detected increase of dissolved
lead concentration could be due to oxidation of
organic matter, caused by increased fluxes of oxygen pumped inside the chamber. The oxidation of
organic matter seems to induce Pb release from
superficial sediment but not from particulate material toward the dissolved phase; practically no
Pb decrease, related to the oxygen increase, is
evident in the particulate matter Fig. 4.. Moreover, oxidation of unstable sulphides present in
superficial sediments could cause upward diffusion fluxes from pore waters. Petersen et al. 1997.

C. Zago et al. r The Science of the Total En ironment 246 (2000) 121137

131

dation of unstable sulphides increased Pb concentrations inside the chamber when oxygen additions were increased.

Fig. 5. Cd, Pb and Cu dissolved concentrations measured

inside the benthic chamber during the experiment. For comparison the oxygen trend is also reported. Error bars "1 S.D.

studied the impact of microbial activity on the

release of trace elements by parallel incubation of
sediment suspensions under different conditions.
The authors found that trace elements can be
released during the reoxidation of anoxic sediments and that this release is strongly affected by
microbial processes. At a temperature of 20C,
similar to the temperature measured inside the
benthic chamber, Petersen et al. 1997. found
that the sediment suspension in oxygenated water
caused an immediate reoxidation of sulphides to
sulphates, which increase in solution. Their investigations illustrated that biological activity had a
significant effect on sulphate release. These results should support the hypotheses that the oxi-

3.2.2. Cadmium and copper

The temporal trends of Cd and Cu concentrations proved similar to each other Fig. 5.. The
concentrations of these two metals initially increased, until they reached an equilibrium period
with stable values after 720 h from the beginning of the experiment. After approximately 80 h,
when oxygen concentration inside the chamber
decreased for a relatively long period, Cd and Cu
concentrations decreased consistently, probably
due to precipitation processes toward the sediment phase. Due to the particular temporal trend
of Cd and Cu concentrations, which did not follow the particulate trend see, e.g. the period of
stable concentrations ., it is reasonable to suppose
that these metals were not affected by sediment
resuspension due to benthic chamber placement.
However, the increase of Cd from 0.2 to 0.7 nmol
ly1 was probably due to porewater release from
sediment due to the increased pressure applied
on sediment during chamber positioning. On the
contrary, an increase of Cu did not occur. If
porewater release from sediment occurred, the
increase of Cd and not of Cu suggests an enrichment of Cd and a higher CdrCu ratio in porewater than in overlying waters.
Cd and Cu concentrations were not influenced
by the observed oxygen fluctuations, with the
exclusion of the final part of the experiment,
when strictly anoxic conditions were present inside the benthic chamber for relatively long time
Fig. 5.. In anoxic conditions, sulphates are reduced to sulphides and metals such as Cd and
particularly Cu commonly precipitate as metal
sulphides in superficial sediments Westerlund et
al., 1986; van der Sloot et al., 1990; Brugmann
et

al., 1992..
3.3. Nitrogen species
Table 4 reports the nitrogen species concentration in the collected seawater samples. The outlying value obtained for N-NO3 at 57 h is not
considered further. Note that the temporal trends

C. Zago et al. r The Science of the Total En ironment 246 (2000) 121137

132

Table 4
N-NO3 , N-NO2 and N-NH 4 concentrations determined in
seawater samples collected during the experiment
Time h.

Concentration mol ly1 .

Repetitions

Mean

R.S.D. %.

N-NO3
0
7
12
23
33.5
47
57
71
81
95

3.41, 3.73, 3.31

2.04, 2.15, 2.53
1.84, 1.72, 2.24
2.01, 1.83, 2.10
1.63, 1.32, 1.35
1.98, 2.19, 1.95
3.67, 4.11, 3.79
2.64, 2.29, 2.33
2.01, 2.29, 2.24
2.25, 2.37, 2.23

3.48
2.24
1.93
1.98
1.43
2.04
3.86a
2.42
2.18
2.28

6.3
11.5
14.1
6.9
11.9
6.4
5.9
7.9
6.9
3.3

N-NO2
0
7
12
23
33.5
47
57
71
81
95

1.33, 1.34, 1.57

1.61, 1.34, 1.36
1.45, 1.59, 1.34
0.80, 1.08, 0.91
1.01, 0.93, 1.16
1.34, 1.34, 1.28
1.17, 1.15, 1.05
1.89, 1.64, 1.65
1.73, 1.54, 1.67
1.12, 0.92, 1.04

1.41
1.44
1.46
0.93
1.03
1.32
1.12
1.73
1.65
1.03

9.6
10.5
8.6
15.2
11.3
2.6
5.7
8.2
5.9
9.8

N-NH4
0
7
12
23
33.5
47
57
71
81
95
a

8.3, 7.7, 7.7

9.5, 9.8, 9.5
12.1, 11.4, 11.5
14.9, 15.4, 14.8
19.0, 18.6, 18.4
19.6, 19.3, 19.8
18.3, 19.8, 18.8
21.7, 21.0, 21.1
22.4, 22.7, 22.7
24.3, 23.4, 23.3

7.9
9.6
11.7
15.0
18.7
19.6
19.0
21.3
22.6
23.7

4.4
1.8
3.2
2.1
1.6
1.3
4.0
1.8
0.8
2.3

Contaminated sample.

of these species Fig. 6. do not show any association with the particulate matter Fig. 3. denoting
that resuspension apparently did not influence
nitrogen species concentrations.
During the experiment, the N-NO3 concentration inside the benthic chamber initially decreased and then it settled at an equilibrium
value approximately 40% lower than the initial
value Fig. 6.. A comparison between the nitrate
and oxygen temporal trends shows that O 2 fluc-

Fig. 6. Temporal trends of nitrogen species inside the benthic

chamber. For comparison the oxygen trend is also reported.
Error bars "1 S.D.

tuations did not affect N-NO3 concentration.

Indeed laboratory experiments carried out by
Petersen et al. 1997. showed that, due to the
growing time required by populations of nitrifying
bacteria, nitrate concentration increased in solution only after longer periods approx. 170 h in
their incubation experiment. than that observed
here during oxygen fluctuation. Probably for this
reason, in our experiment nitrate concentration
was not influenced by oxygen fluctuations. The
initial decrease can be interpreted in terms of
both transport toward the sediment andror nitrate reduction anaerobic conditions. to ammonia Santschi et al., 1990; Overnell et al., 1995..
The N-NO2 concentration was almost constant
throughout the experiment, although some small

C. Zago et al. r The Science of the Total En ironment 246 (2000) 121137

133

Table 5
Benthic fluxes obtained by benthic chamber a
Time h.

7
12
23
33.5
47
57
71
81
95
a

Flux pmol cmy2 hy1 .

Flux nmol cmy2 hy1 .

Cd

Cu

N-NO3

N-NO2

N-NH4

q0.68 0.07.
y0.18 0.19.
q0.07 0.15.
q0.13 0.07.
q0.09 0.11.
y0.10 0.18.
y0.94 0.13.

6.9 5.6.

y2.4 2.4.
q0.6 1.7.
q0.9 1.7.
q0.13 2.6.
q1.1 1.3.
y1.0 1.6.
y14.4 1.1.

y5.7 1.5.
y2.0 2.4.
q0.1 0.9.
y1.7 0.7.
q1.4 0.5.

q0.5 0.3.
y0.8 0.8.
q0.2 0.4.

q0.1 0.9.
q0.1 1.2.
y1.5 0.5.
q0.3 0.6.
q0.7 0.3.
y0.6 0.2.
q1.4 0.4.
y0.3 0.5.
y1.4 0.3.

q7.8 1.8.
q13.4 2.7.
q9.6 1.4.
q11.3 1.3.
q2.1 0.9.
y1.9 2.6.
q5.3 1.9.
q4.2 1.3.
q2.5 1.3.

Values are associated with the upper limits of the observation periods. Standard deviations in parentheses.

fluctuations, apparently inversely related to oxygen changes, were observed. However, these
fluctuations are almost within the experimental
errors see error bars in Fig. 6..
The N-NH 4 concentration increased almost
continuously with time, as usually found in anoxic
environments Santschi et al., 1990.. During ammonification, organic macromolecules present in
the superficial sediment andror in waters both
in dissolved and particulate phases. are hydrolysed, and organically bound nitrogen, mostly in
the form of aminoacids, is brought into solution.
By deamination of aminoacids ammonium is released into solution Santschi et al., 1990.. More
than this, in anaerobic environments, nitrate reduction to ammonia frequently occurs Santschi
et al., 1990; Overnell et al., 1995.; this possibly
happened at the beginning of the experiment see
the N-NO3 concentration decrease from the initial sample..
3.4. Benthic fluxes
Benthic fluxes were computed according to Eq.
4., with i s 1, for all the species measured in this
work. Results are reported in Table 5. Fluxes of
Pb were not considered because, as reported
above, this metal showed strong effects from sediment resuspension and oxygen fluctuations.

Fig. 7. Cd and Cu benthic fluxes measured by the benthic

chamber experiment. Flux values are associated with the upper limits of the observation period. Error bars "1 S.D.

3.4.1. Metal species

The temporal trends of Cd and Cu fluxes inside
the chamber are shown in Fig. 7. For both metals
the flux, after an initial positive value release
from sediment or particulate ., reduces rapidly to
almost zero and it remains negligible until 80 h
when a negative flux is measured. This negative
flux is presumably related to the strictly anoxic
conditions observed in this period see Fig. 3. and

134

C. Zago et al. r The Science of the Total En ironment 246 (2000) 121137

versely related to oxygen fluctuations . are only a

little higher than the experimental error see
error bars in Fig. 8..
Ammonium flux presents higher values than
those of nitrate and nitrite. It assumes the highest
positive values within the first ; 30 h of experiment mean s 10.5, S.D.s 2.4 nmol cmy2 hy1 ., it
remains low or negligible. between ; 30 h and
; 60 h, after which it increases to values around
5 nmol cmy2 hy1 until ; 80 h, and finally it
reduces again.
3.5. Comparison with literature data

Fig. 8. Nitrogen species benthic fluxes measured by the benthic chamber experiment. Flux values are associated with the
upper limits of the observation period. Error bars "1 S.D.

the consequent metal sulphide precipitation in

superficial sediments.
3.4.2. Nitrogen species
Fluxes of nitrogen species Table 5. are shown
in Fig. 8. To allow a direct, quantitative comparison between fluxes of the three nitrogen species,
the same scale was used in the graphs.
Nitrate flux proved negative at the beginning of
the experiment the mean value obtained between
0 and 7 h is y5.7 nmol cmy2 hy1 . after which it
reduces to negligible values within approximately
15 h.
Nitrite flux was generally the lowest of the
nitrogen species. It does not show a clear temporal trend and a few changes apparently in-

To summarise, our best estimates of benthic

fluxes are the following in pmol cmy2 hy1 and
nmol cmy2 hy1 for metal and nitrogen species,
respectively.: Cd 0.68, Cu 7.8, N-NO3 y5.7, NNH 4 10.5. No values could be determined for Pb
due to the influence of sediment resuspension,
whereas for N-NO2 results were not significant
with respect to measurement errors. Thus, except
for nitrate, apparent fluxes from sediment to water have been detected.
In Table 6 metal and nitrogen benthic fluxes
measured in different coastal environments are
compared with our results. The table does not
report N-NO2 data because no reference was
found in the literature. Fluxes obtained in the
present study in the northern Adriatic Sea in
front of the River Po outflow were generally of
the same order of magnitude as values found in
the literature, except for nitrate. The negative
nitrate fluxes and positive ammonium fluxes
observed in our experiment indicate that possibly,
at the beginning of the experiment, nitrate reduces to ammonium as usually found in anoxic
environments Santschi et al., 1990; Overnell et
al., 1995.. This usually happens in coastal waters
when, due to summer water stratification, anoxic
conditions frequently occur close to the bottom.
However, N-NO3 reduction accounts for only part
of the apparent N-NH 4 flux from sediment. Indeed, N-NH 4 can be released from the sediment,
in anoxic conditions, without oxidation at the
sedimentwater interface due to reduction of the
oxic barrier Val Klump and Martens, 1981; Balzer
et al., 1987.. As in our results, Bertuzzi et al.

C. Zago et al. r The Science of the Total En ironment 246 (2000) 121137

135

Table 6
Benthic fluxes measured in different coastal environments standard deviations in parentheses .
Flux pmol cmy2 hy1.

Fluxes nmol cmy2 hy1 .

Cd

Cu

N-NO3

N-NH4

Po Estuary, north Adriatic Sea, Italy

Ansedonia Bay, Tirrenian Sea, Italy
Bang Pakong Estuary, Thailand
Gullmarsfjorden, Sweden Fall, winter.
Kalix River Estuary, Sweden
Chesapeake Bay, USA
Boston Harbor, MA, USA
Cape Lookout Bight, NC, USA

0.68 0.07.
1.4
0.01% 0.03
0.046% 0.054

6.9 5.6.
7.1
3.8% 8.6
0.11% 0.49
0.33% 1.02
1.24% 3.21
1.2% 10

y5.7 1.5.

7.8 2.4.

2 % 120

Boston Harbor, MA, USA

Gulf of Trieste, north Adriatic Sea, Italy

0.4% 54
0.7 3.0.

0.4% 50
3.3 2.9.

Site

1997. obtained the greatest negative nitrate flux

in late summer, when they registered oxygen depletion in bottom waters.

4. Conclusions
Although subsurface sediment may be the sink
for trace metals and nitrogen species, the present
observations with benthic chamber showed that at
the beginning of the experiment the surface sediment is a net source to the overlying water for
Cd, Cu and NH 4 . Under almost anoxic conditions
metals such as Cu and Cd in a reducing environment can be mobilised from sediment and diffuse
from pore waters to the water column, andror
they can also be removed from the water column
by sulphide precipitation Westerlund et al., 1986;
van der Sloot et al., 1990; Brugmann
et al., 1992..

The equal occurrence of both these processes is

presumably the reason why, approximately 20 h
into the experiment, after an initial flux from
sediment to water, Cd and Cu reached an equilibrium phase where release and precipitation
processes were balanced. When strictly anoxic
conditions occurred inside the chamber, Cd and
Cu presumably precipitated as sulphides and
fluxes proved to be negative. Cd and Cu are in
fact known for their high affinity with sulphides to
form a mineral phase in anoxic conditions
Forstner
and Wittman, 1979.. As regards Pb,

concentrations were affected both by lead resus-

Reference

Present study
Ciceri et al. 1992.
Cheevaporn et al. 1995.
Westerlund et al. 1986.
Widerlund 1996.
Riedel et al. 1997.
Zago et al. submitted.
Val Klump and Martens
1981.
Giblin et al. 1997.
Bertuzzi et al. 1997.

pension from surface sediments and pore water

due to the chamber positioning and by oxic conditions inside the chamber. In spite of this, the
benthic chamber experiment proved useful to
study the geochemical behaviour of lead when
oxygen concentration changed in an almost anoxic
environment. In this respect Pb showed a completely different geochemical behaviour to that of
Cd and Cu.
As regards nitrogen species, ammonium showed
the highest positive fluxes. Negative values are
observed for nitrate and negligible fluxes with
respect to the measurement error. are estimated
for nitrite. The total apparent nitrogen flux at
the sedimentwater interface sum of the different nitrogen species fluxes. were positive. This
means that during the sampling period sediment
acted as a source of nitrogen to the overlying
water.
The benthic chamber experiment showed that
in the coastal area in front of the River Po at the
end of the summer period the apparent flux of
Cd, Cu and N-NH 4 moves from the sediment
towards the water column positive net flux values
only at the beginning of the experiment., for
N-NO3 it is in the reverse direction, and for
N-NO2 it shows negligible values.

Acknowledgements
This work was supported by the PRISMA1

136

C. Zago et al. r The Science of the Total En ironment 246 (2000) 121137

Project of the MURST. We would like to thank

Dr Clara Turetta for her helpful comments on
the manuscript and for assistance in the laboratory activities. Financial support was provided to
Cristina Zago by the MAS3 CT95 0021 Project of
the European Union.
References
Balzer W, Erlenkeuser H, Hartmann M, Muller
PJ, Pollehne

F. Diagenesis and exchange processes at the benthic

boundary. Seawatersediment interactions in coastal waters, Lecture Notes on Coastal and Estuarine Studies, chap.
4. Berlin: Springler-Verlag, 1987:112158.
Barbanti A, Bergamini MC, Frascari F, Miserocchi S, Ratta
M, Rosso G. Diagenetic processes and nutrient fluxes at
the sedimentwater interface, northern Adriatic Sea, Italy.
Mar Freshwater Res 1995;46:5567.
Bertuzzi A, Faganeli J, Welker C, Brambati A. Benthic fluxes
of dissolved inorganic carbon, nutrients and oxygen in the
Gulf of Trieste northern Adriatic.. Water Air Soil Pollut
1997;99:305314.
Brugmann
L, Bernard PC, van Grieken R. Geochemistry of

suspended matter from the Baltic Sea 2. Results of bulk

trace metals analysis by AAS. Mar Chem 1992;38:303323.
Capodaglio G, Toscano G, Cescon P, Scarponi G, Muntau H.
Collaborative sampling error assessment of trace metal
determination in seawater. Ann Chim 1994a;84:329345.
Capodaglio G, Toscano G, Scarponi G, Cescon P. Copper
complexation in the surface seawater of Terra Nova Bay
Antartica.. Int J Environ Anal Chem 1994b;55:1291128.
Capodaglio G, Scarponi G, Toscano G, Barbante C, Cescon P.
Speciation of trace metals in seawater by anodic stripping
voltammetry: Critical analytical steps. Fresenius J Anal
Chem 1995;351:386392.
Cheevaporn V, Jacinto GS, San Diego-McGlone ML. Heavy
metal fluxes in Bang Pakong River Estuary, Thailand:
sedimentary vs diffusive fluxes. Mar Pollut Bull
1995;31:290294.
Ciceri G, Maran S, Martinotti W, Quierazza G. Geochemical
cycling of heavy metals in a marine coastal area: benthic
flux determination from porewater profiles and in situ
measurements using benthic chamber. Hydrobiologia
1992;235r236:501517.
Forstner
U, Wittman GTW. Metal pollution in the aquatic

environment. Heidelberg: Springler-Verlag, 1979:473.

Giblin AE, Hopkinson CS, Tucker J. Benthic metabolism and
nutrient cycling in Boston Harbor, Massachusetts. Estuaries 1997;202.:346364.
Hammond DE, Fuller C, Harmon D, Hartman B, Korosek M,
Miller LG, Rea R, Warren S, Berelson W, Hager SW.
Benthic fluxes in San Francisco Bay. Hydrobiologia
1985;129:6990.
Mart L. Prevention of contamination and other accuracy risks
in voltammetric trace metal analysis of natural waters. Part

I. Preparatory steps, filtration and storage of water samples. Fresenius Z Anal Chem 1979a;296:350357.
Mart L. Prevention of contamination and other accuracy risks
in voltammetric trace metal analysis of natural waters. Part
II. Collection of surface water samples. Fresenius Z Anal
Chem 1979b;299:791022.
Mart L, Nurnberg
HW, Valenta P. Prevention of contamina
tion and other accuracy risks in voltammetric trace metal
analysis of natural waters. Part III. Voltammetric ultratrace
analysis with a multicell system designed for clean bench
working. Fresenius Z Anal Chem 1980;300:350362.
Nurnberg
HW, Valenta P, Mart L, Raspor B, Sipos L. Appli
cations of polarography and voltammetry to marine and
aquatic chemistry. II. The polarographic approach to the
determination and speciation of toxic trace metals in the
marine environment. Fresenius Z Anal Chem 1976;
282:357368.
Officer CB, Biggs RB, Taft JL, Cronin LE, Tyler MA, Boynton WR. Chesapeake Bay anoxia: origin, development and
significance. Science 1984;223:2227.
Overnell J, Edwards A, Grantham BE, Harvey SM, Jones KJ,
Leftley JW, Smallman DJ. Sedimentwater column coupling and the fate of the spring phytoplankton bloom in
Loch Linhe, a Scottish Fjordic Sea-loch. Sediment processes
and sedimentwater fluxes. Estuar Coast Schelf Sci
1995;40:117.
Parson T, Maita Y, Lolli CM. A manual for chemical and
biological methods for seawater analysis. Oxford: Pergamon Press, 1984.
Petersen W, Willer E, Willamowski C. Remobilization of trace
elements from polluted anoxic sediments after resuspension in oxic water. Water Air Soil Pollut 1997;99:515522.
Riedel GF, Sanders JG, Osman RW. Biogeochemical control
on the flux of trace elements from estuarine sediments:
water column oxygen concentrations and benthic infauna.
Estuar Coast Schelf Sci 1997;44:2338.
Rivera Duarte I, Flegal AR. Benthic lead fluxes in San Francisco Bay, California, USA. Geochim Cosmochim Acta
1994;5815.:33073313.
Santschi P, Hohener
P, Benoit G, Buchholtz-ten Brink M.

Chemical processes at the sedimentwater interface. Mar

Chem 1990;30:269315.
Scarponi G, Capodaglio G, Barbante C, Cescon P. The anodic
stripping voltammetric titration procedure for study of trace
metal complexation in sea water. In: Caroli S, editor.
Element speciation in bioinorganic chemistry, chemical
analysis series, vol. 135, chap. 11, 1996:363418.
Scarponi G, Capodaglio G, Turetta C, Barbante C, Cecchini
M, Cescon P. Evolution of cadmium and lead contents in
Antarctic coastal seawater during the austral summer. Int J
Environ Anal Chem 1997;66:2349.
Selinger HH, Boggs J, Biggley WH. Catastrofic anoxia in the
Chesapeake Bay in 1984. Science 1985;228:7073.
Solorzano L. Determination of ammonia in natural waters by
phenol-hydroclorite method. Limnol Oceanogr 1969;14:
799801.

C. Zago et al. r The Science of the Total En ironment 246 (2000) 121137
Spagnoli F, Bergamini MC. Watersediment exchange of
nutrients during early diagenesis and resuspension of anoxic
sediments from the northern Adriatic Sea shelf. Water Air
Soil Pollut 1997;99:541556.
Sundby B, Anderson LG, Hall PO, Iverfelt MM, van der Loeff
R, Westerlund SF. The effect of oxygen on release and
uptake of cobalt, manganese, iron and phosphate at the
sedimentwater interface. Geochim Cosmochim Acta
1986;50:12811288.
Turekian KK. The state of metals in the ocean. Geochim
Cosmochim Acta 1977;41:11311144.
Val Klump J, Martens CS. Biogeochemical cycling in an
organic rich coastal m arine basin-II. Nutrient
sedimentwater exchange processes. Geochim Cosmochim
Acta 1981;451.:101121.
van der Sloot HA, Hoede D, Hamburg G, Woitties JRW, van

137

der Weijden CH. Trace elements in suspended matter from

the anoxic hypersaline Tyro and Bannock Basins eastern
Mediterranean .. Mar Chem 1990;31:187203.
Westerlund SFG, Anderson LG, Hall POJ, Iverfeldt A, van
der Loeff RMM, Sundy B. Benthic fluxes of cadmium,
copper, nickel, zinc and lead in the coastal environment.
Geochim Cosmochim Acta 1986;50:12891296.
Widerlund A. Early diagenetic remobilization of copper in
near-shore marine sediments: a quantitative pore-water
model. 1996;54:4153.
Zago C, Giblin AE, Bergamasco A. Changes in the metal
content of surficial sediments of Boston Harbor since the
cessation of sludge discharge. Mar Environ Res, submitted.
Zago C. Benthic fluxes and transport processes of trace elements in sea water. Ph.D. thesis. XI Cycle. Ferrara University, 1999.