11
1 INTRODUCTION
Once introduced into the marine environment
through human activities (i.e. the shipbuilding
industry, the chemical industry, the agriculture),
metals (i.e. Zn, Ni, Cr, Cu, Cd, Pb), as well as
organotin compounds (OTC: tributyltin (TBT),
dibutylitin (DBT), monobutylitin (MBT), triphenyltin
(TPhT),diphenytlin(DPhT),monophenyltin(MPhT))
presenthigherpersistenceinbenthicsedimentsanda
hazardtoliving,ma
rineorganisms(Alzieu,2000).
Because of favourable navigation conditions and
easy access to the sea, most harbours are located
within the coastal zone of the land. The better
developed this section of the coast is, the more
efficient the transportand movement of ships in the
harbour are. The demersal hydrodynamic regime
present in harbours, however, is mostly dictated by
the movement of ships and, consequently, differs
from the natural hydrological and sedimentation
condit
ionsofthesea.Ontheotherhand,mechanical
resuspensionofthesedimentcausedbyshipsmoving
in the harbour may lead to repeat pollut
ion of the
waterbasin(duetothereleaseofchemicalsubstances
from the harbour sediments). Such a phenomenon
mayleadtochangesoccurringnearthebottomofport
channels, above all: changes to chemical and
biological composition of sediments, changes to pH
values and oxidation/reduction conditions,
bioavailability of old and new pollut
ants.
Furthermore,theunnaturalincreaseinthewaterflow
in the port may give rise to the inflow of sea
sediments into port channels and contribute to the
increased rate of sedimentation (e.g. in the Port of
Gdańsk this amounts to approximately 7 cm per
year
‐1
, in the Baltic Sea – between 0.13 and 2.92 mm
per year
–1
(Szwernowski, 1957; Pempkowiak, 1992)).
In the end this provokes the port channels bottom
shoal patching and gives rise to the necessity of
removing the accumulated sediment in order to
ensuresafenavigationthroughouttheharbour.Spoil
Aspects of Pollution in Gdansk and Gdynia Harbours
at the Coastal Zone of the South Baltic Sea
B.Radke&S.Piketh
The Unit of Environmental Sciences and Management, Geography and Environmental Sciences, The North‐West
University,Potchefstroom,SouthAfrica
A.Wasik&J.Namieśnik
DepartmentofAnalyticalChemistry,ChemicalFaculty,GdańskUniversityofTechnology,Gdańsk,Poland
G.Dembska
DepartmentofEnvironmentalProtection,MaritimeInstitute,Gdańsk,Poland
J
.Bolałek
Department of Marine Chemistry and Environmental Protection, Institute of Oceanography, University of Gdańsk,
Gdynia,Poland
ABSTRACT:Organotincompounds(OTC),aswellasmetals,aretoxictomanyorganisms.Evenatvery low
concentrationsOTCandmetalscanhaveseveralnegativeeffects.Thepaperdiscusseskeyissues relatingtothe
locationofharboursinthecoastalzone(includingneartherivermouthsandsemi‐closedaccesstothesea)and
the pollut
ion of harbour sediments with heavy metals (e.g. zinc, copper, nickel and lead) and organotin
derivatives (e.g. butyltin, phenyltin, octyltin, and tricyclohexyltin), using the examples of the Gdańsk and
Gdynia ports. The aut
hors have described key spatial factors of the two ports which largely determine
sedimentation processes. It has been shown that the heavy metals content in the sediments of the Port of
Gdańsk does not exceed the concentration values permitted by Polish law, however, the problem with the
establishmentofstandardconcentrationlevelsfororganotinderiva
tivesremains.
http://www.transnav.eu
the International Journal
on Marine Navigation
and Safety of Sea Transportation
Volume 7
Number 1
March 2013
DOI:10.12716/1001.07.01.01
12
dredged from the harbour may be stored, under
certainconditions,onthelandorinthesea,onareas
speciallyassignedforthispurpose.Becauseofahigh
risk of polluting the sea regions with chemical
substances, however, the port sediment should be
testedinordertoreducetheinflow
ofpollutantsinto
thesea.Resultspresentedinthesepapershaveinpart
already been published by Dembska et al. (2001),
Radkeetal.(2004,2008,2012a,b),Pustelnikovasetal.
(2005, 2008). Tests results for samples of sediments
collectedinyears1998‐2010fromthechannelsofthe
Portof
GdańskandthePortofGdyniaarediscussed
inthesearticles. Areviewoftheresultsofmanyyears
of tests on the content of trace metals and organotin
derivativesatthePortofGdańsk,aswellasorganotin
derivativesatthePortofGdynia,willbepresentedin
thisarticle.
1.1 Samplearea
PortGdańskiS.A.isthelargestmarineportinPoland.
The port consists of two major areas, i.e. the inner
port located on both sides of the Dead Vistula river
(lengthof27km,depthof10‐12m)andtheouterport
(the
NorthernPort) (depth of 10‐15m) lying directly
withinthecoastalzoneoftheGulfofGdańsk(Fig.1).
The mean flow values range from 2 to 5 cm s‐1,
salinity ranges from 6.13 to 2.48 PSU (Majewski,
1990),andtheinflowofsalineseawateroccursin
the
near‐bottom water layer in the river. The Port of
GdyniaisthethirdlargestportinPolandandconsists
oftheWestPort(innerport)andtheEastPort(outer
port). The port is protected year‐round by a 2.5 km
breakwaterandneverfreezesoverduringwinter.The
valueofwatersalinityrangesfrom 7.94 to 8.12PSU,
whilepHrangesfrom7.48to8.35.
Figure1.MapofthePortofGdańskandthePortofGdynia
where: Z– sampling sites at Ziółkowskiego Quay; W–
Wiślane Quay; O‐Oliwskie; WG– Węglowe Quay; S–
SiarkoweQuay;PN–NorthernPort,I,II,III,IV,V,VI,VII,VIII–
individualdocks
1.2 Samplesandmethods
Sediments(25cm)foranalysiswerecollectedin1997‐
2010onboardr/vDrLubecki(thevesseloftheMarine
Institute) and Oceanograf2 (Institute of
Oceanography, University of Gdańsk), respectively.
Sediments were collected using a gravity corer
Niemistö from the following locations: the Port of
Gdańsk
(Oliwskie Quay, Siarkowe Quay, Northern
Port and Wiślane Quay); the Port of Gdynia (quays
III, IV, V, VI, VII and VIII). Two locations were
designated for each of the docks (Fig. 1).
Granulometric(grain size from2.00 to 0.0625 mm in
mesh diameter), as well as chemical analyses
(organotin,
metals and organic matter (LOI)), were
performed for the samples. The methodologies
proposed by Luoma & Bryan (1981) and Loring &
Rantal(1992)wereusedtodeterminethetotalcontent
and the labile form content of metals. Organotin
derivatives were measured using a procedure
developedbyWasiketal.(2007).The
totalcontentof
metalswasmeasuredbymeansofatomicabsorption
spectroscopy (AAS) (using SpectrAA 250 PLUS
spectrometerbyVarian).Inductivelycoupledplasma
atomicemissionspectroscopy(ICP‐OES)wasapplied
in the case of the labile form of metals (OPTIMA
2000DV spectrometer by Perkin‐Elmer). Organotin
compounds assay was performed
using a gas
chromatograph (GC 8000 series by Carlo Erba). The
determined limits ofdetection areshown in Table 1.
Reference materials PACS‐2, BCR‐646 (for organotin
derivatives) and PACS‐2 (for metals) were used for
the method validation (Table 1). The achieved
recoveryamountedtobetween82and96%.
Table1Determined limitsofdetection(MDL)ofmetals(mg
kg
‐1
d.w.)andorganotinderivativesngSng
‐1
d.w.
Assay
method
Metals
Zn Ni Cr Cd Pb
AAS 0.17 0.56 0.53 0.05 0.42
ICP‐OES 0.08 0.05 0.08 0.01 0.08
Or
g
anotinderivatives
MBT DBT TBT MPhT DPhT TPhT
GC‐FPD 4.5 3.8 6.9 7.0 5.6 4.1
*Methodquantificationlimit(MQL)wasdeterminedas
follows:MQL=3xMDL
2 RESULTSANDDISSCUSSION
2.1 Sedimentation
Sedimentation within both harbours may be
conditioned, above all, by the sediments graining
level, the change of migration forms of the
sedimentation material, the effect of near‐bottom
currents generated by ships, as well as periodical
spreadingofsedimentsintotheharbourarea(Bolałek
& Radke, 2010). Based on the results obtained by
(Radke et al., 2008, 2012a,b) it was found that there
was sand (mostly silty sand and sandy silt) in the
entirematerialcollectedfromthePortsofGdyniaand
Gdańsk.Moreover,thelithodynamicanalysisofgrain
sizeperformedforindividual
samplesconfirmedthat
the bottoms of both ports have undergone
transformation by shipping activity (mechanical
mixing) and dredging works. As a result sediment
samples were very poorly sorted. In the case of the
Port of Gdańsk the most important factors affecting
thehydrologicalconditions,aswellassedimentation
in the
bottom were: storm surges, backwater and
waves (from the sea side), river flooding (from
Motława) (Szczecińskie Quay, Figure 1.) (Bolalek &
Radke,2010).Furthermore,thetendencyforclayand
silt (<0.063 mm fraction) sediments to flow into the
13
middle section of the port (5.1‐ 6.6% Wiślane and
Węglowe Quays) was observed, but sediments from
Ziółkowskiego,OliwskiegoQuaysandNorthernPort
havebeenenriched incoarserfractionsanddepleted
of fine ones (Radke et al., 2008) (Fig.1). Sediments
originating from the latter location are subjected to
spring flooding of Motława which stimulates the
washing‐out of fine fract
ions and their transport in
thedirectionoftheWiślaneQuay.Thisphenomenon
is the most likely cause of the low content of fine
fractions by the Szczecińskie Quay and the high
content by the Wiślane Quay (Bolałek et al., 2006;
Radkeetal.,2008;Pustelnikovasetal.,2005,2008).On
the other hand, the area close to the Vist
ula river
mouth(Ziółkowskiego Quay) ischaracterized by the
influence of marine waters. Such location stimulates
the transport of fine ‐grainedfractions from the river
mouthtowa
rdsthegulf.Incomparisontothesamples
from the Port of Gdańsk, samples from the Port of
Gdynia presented higherpercentage offinefractions
(between 36.8 and 76.9%) (Table 2). This reflects the
highly sorptive properties of silt and clay (Langston
andPope,1995;Hoch,2001).Moreover,theobtained
resultsofthermogravimetricanalysis(TGA)(Radkeet
al., 2008) indicat
ed the existence of kaolinite and
biogenic minerals (carbonates) in the samples from
this region. Such sediment compositions give rise to
conditionsthatarefavourabletotheaccumulationof
any chemical substances including metals and
organotincompounds.AlthoughthePortofGdyni
ais
protected year‐round by the outer breakwater (2.5
km), which prevents mixing from currents or high
waves in the port, during sustained strong westerly
windsthewaterlevelcanrisebyupto0.6mandcan
decreaseduringstrongeasterlywindsbyasmuchas
0.6 m. This phenomenon ma
y cause intensive
movementofwater massandsedimentsintotheport
channel and consequently lead to direct and
consistent distribution of sediment materials toward
individual docks. In this particular instance the
largest percentage of fine fraction (43.2‐76.9%) was
found in sedimentsamples fromthe stations located
inthesectionsoftheportfurt
hestfromthesea(docks
VI, VII and VIII). The sediments from the docks
locatedin themiddlesection of the port (IV, V) and
itsimmediatevicinity(III)containedlessclayandsilt
(36.8‐38.5%)andmoresand(61.5‐63.2%)(Radkeetal.,
2010,2012a,b
).Itshouldbementionedthatindividual
docks ofthe Port of Gdynia provide easier access to
the water mass from the sea, in comparison to the
quays from the inner Port of Gdańsk, which are
mostlyaffected by theriver. Taking intoaccountthe
above details it may be assumed tha
t storms and
winds may play the main natural role in the
formationofsedimentation,aswellasthetransportof
watermassinthePortofGdyniachannel.
2.2 Influenceoftheareasubjecttotheseainfluenceand
thearearelatedwiththelandonthedistributionof
chemicalsubstancesinharbours
A significant fact
or conditioning the distribution of
chemical substances in sedimentation in harbour
areas are the increased erosion phenomena related
with ships movement in the harbour and dredging
works. In the discussed ports, however, we can
differentiate between two areas responsible for the
distributionofchemicalsubstancesinsedimentation:
the area subject to the influence of the sea and the
area tha
t is strictly related with the land and the
anthropogenic influence (Table 2). A geochemical
barrier(Pustelnikovasetal.,2005,2008)thatisformed
asaresultoffreshwater(fromtheriver)cominginto
contact with saline water (from the sea), as well as
storm surges and the distance from the sea mouth,
ma
y have a significant influence on this kind of
distribution of chemical substances. A geochemical
barrierisespeciallyemphasizedinthecaseofthePort
of Gdańsk where there is a strong inflow of fresh
water originat
ing from the Motława to the port
channel.Majewski(1972)estimatedthattheinflowof
fresh water to the Vistula River basin (the longest
river in Poland, introducing the largest amount of
water mass to the Gulf of Gdańsk of the Baltic Sea)
mostly originat
es from the Motława River
(approximately 87.0%), while the Dead Vistula river
on its own contributes very little – approximately
0.99%. In the case of the Port of Gdynia the local
inflow of underground fresh water from the
Chylonkariverismuchlesssignificant.Althoughthe
watercourse may locally form a geochemical barrier
(proba
bly within the area of dock VII) it seems that
the zonation in the port is caused by storm surges,
whose inflows may even reach basin V (large
amountsofclams,shells,coarse‐grainedmaterialand
a smaller share of clay fraction and organic matter
were found in the sediment samples in comparison
withba
sinsVI,VIIandVIII).
Table2. Division of the Port of Gdynia and the Port of
Gdańskareasintozonesof theseaandthelandinfluence,
considering the organic matter, as well as the fine and
coarse‐grainedfractionvalues.
Port Port area Coarse
fraction
(>0.063
mm
)
Fine
fraction
(<0.063
mm
)
Organic
matter
(%)
PortofGdańsk
Seainfluence
NorthernPort 96.2% 3.8 1.9
OliwskieQua
y
98.1 1.9 0.9
SiarkoweQua
y
96.1 3.9 1.9
Ziółkowskiego
Qua
96.7 3.3 2.0
Land
influence
Wę
g
loweQua
y
94.9 5.1 4.9
WiślaneQua
y
93.4 6.6 6.8
Szczecińskie
Qua
95.9 4.1 1.8
PortofGd
y
nia
Dock
Sea
influence
III 61.5 38.5 3.1
IV 63.2 36.8 3.9
V 62.5 37.5 0.8
Land
influence
VI 23.1 76.9 7.4
VII 56.8 43.2 5.0
VIII 24.2 75.8 7.6
The regularities presented ab
ove can be easily
observed in relation to all the results (granulometric
analysis, results of metal and organotin derivatives
content)obtainedforsamplescollectedfromthePort
of Gdańsk. A similar analysis of sediments samples
from the Port of Gdynia does not pose many
14
difficulties, as it is based on granulometric analysis,
thermogravimetric analysis and the analysis of
organotinderivatives (Radkeetal.,2008,2010,2012a).
Thelatterbehaveinthemarineenvironmentsimilarly
to metals (in a similar way they are accumulated in
sediments, adsorbed on the surface of clay minerals
and organic
matter, etc.) (Langston & Pope, 1995;
Hoch, 2001). Coarse‐ and medium‐grained fraction
(varioustypesofsandandstone,aswellaspebbles)
prevails in the samples of sediments from zone one
over the fine fraction (sludge, clay). This particular
fraction of fine sediments (<0.063 mm) is the main
element
of the marine environment responsible for
the accumulation of the largest contamination loads
in sediments. A smaller share of organic matter
(mostly organic carbon, humic and fulvic acids)
(Hoch, 2001) that is the second important factor
supporting the share of pollutants in the sediments
canbeobservedinthisarea.Considering
theaspects
describedaboveitisnotdifficulttoconcludethatthis
zone is characterised with lower concentrations of
chemicalsubstances(thePortofGdańsk–metalsand
organotinderivatives,thePortofGdynia–organotin
derivatives), and due to the easy exchange with the
seathereareno
conditionsinthisareathatwouldbe
favourabletotheaccumulationofhighconcentrations
of pollutants. In the case of both ports this concerns
sedimentsoriginatingfromthemiddleandtheouter
sectionoftheport:thePortofGdynia–docksIII,IV,
V; the Port of Gdańsk –
the Northern Port and the
following quays: Ziółkowskiego, Siarkowe and
Oliwskie.Physicalandchemicalconditionsoccurring
withinthe area with the influence of the land differ.
Sediments from this zone are characterised with a
largershareofthefinefractionandtheyareenriched
with organic matter that increases
the sorptive
capacity of the sediments. Therefore, the highest
concentrationsofmetalsandorganotinderivativesin
thecollectedmaterialmaybeexpectedinthisareaof
the harbour. Furthermore, a characteristic feature of
theregion is theprevalence of anthropogenic factors
originatingbothfromthelandandtheport(e.g.high
level of industrialization and operation, municipal
waste, repair and handling works, removal of waste
from ships, release of pollutants from ships hulls,
emission from stokeholds and treatment plants, etc.)
over natural factors (Bolałek & Radke, 2010). The
second zone involves samples of port sediments
collected from stations located in
the port sections
furthest from the sea: docks VI, VII and VIII in the
case of the Port of Gdynia, and quays: Wiślane,
Węglowe and Szczecińskie in the case of the Port of
Gdańsk. A similar dependence was obtained by
Pustelnikovasetal.(2005, 2008) when examining
the
distribution of trace elements in the sediments from
thePortofKlaipėdainLithuania,intheregionofthe
SouthBalticSea.
2.3 Metalsandorganotinderivativesinthesediments
fromthePortofGdyniaandthePortofGdańsk
Figures 2‐5 provide information on the
content of
chemical substances examined in the port samples.
Thehighestlevelsofmetalsandorganotinderivatives
content were discovered in samples collected from
regionswithahighindustrializationlevelandlocated
inthevicinityofashipyard.InthecaseofthePortof
Gdańsk these are quays Wi
ślane, Węglowe and
Szczecińskie. An additional factor that could have
contributed to the increase of the determined
components is the basin dynamics. In thisparticular
case this concerns the Wiślane and the Węglowe
Quays (the Szczecińskie Quay is located in the
immediate vicinity of a
shipyard) located within the
areapronetoaccumulation(Fig.2).
(A) The total forms
0
20
40
60
80
100
120
W O S PN Sz
(mgkg
-1
d.w.)
Ni Pb Cu
Zn Cr Cd
(B) The labile form
0
20
40
60
80
100
120
W O S PN Sz
(mg
-1
kg d.w.)
Ni Pb Cu
Zn Cr Cd
Figure2. Comparison of average concentrations of metals
mg.kg
–1
d.w.,totalmetalscontent(A)andinthelabileform
(B),inafractionbelow2.00mminsedimentsofthePortof
Gdańsk quays where W – Wiślane, O – Oliwskie, S –
Siarkowe,NP–NorthenPort,Sz–Szczecińskie
Figure3. Comparison of average concentrations of
organotinderivatives(ngSn.g
–1
d.w.)inthe totalfractionof
sedimentsbelow2.00mmandin fraction <0.063 mm from
thePortofGdańsk,whereW–WiślaneQuay,O–Oliwskie
Quay, S – Siarkowe Quay, NP –Northern Port, WG –
WęgloweQuay