Marine Pollution Bulletin, Vol. 36. No. 9, pp.
729 738, 1998
Pergamon
PII: S0025-326X(98)00053-8
Effect of Urbanization on Metal
Deposition in the Bay of T6616nlahti,
Southern Finland
JUHANI VIRKANEN
Laboratory of Physical Geography, Department of Geography, p.o. Box 9, (Siltavuorenpenger 20 A),
University of Helsinki, 00014 Helsinki, Finland
A sediment core from the Bay of T6616nlahti in the
centre of Helsinki, Finland was analysed by a selective
extraction method in order to examine the geochemical
impacts of urbanization. Concentrations of Al, Ca, Cu,
Fe, Mn and Zn i n the extracts and total P and S were
measured at intervals of 1 cm to a depth of 100 cm.
The data were subjected to principal components
analysis. Sedimentation rate was determined using
137Cs- and 14C-measurements and SCP-analysis and it
varied from 0.4 to 0.6mm.yr-1. Most of the
background metal deposition in the basin is acid
soluble. The intense eutrophication began around 1900
and is reflected in the sedimen~ by a rise in the
concentrations of S, P, organically bound Cu, Fe, Mn,
Zn and hydroxide Zn, Total Al, Ca and M n decrease
towards the surface, probably because of dilution by
organic inputs or by biogenic silica. The total Cu and
Zn were high in the surface with a large proportion of
labile forms. © 1998 Elsevier Science Ltd. All rights
reserved
Keywords: geochemistry; solid-solution extraction;
estuarine sediments; eutrophication.
The natural and man-made environments are in the
process of profound alterations due to land-use
changes, to use and production of materials, to loading
by contaminants, and to other human activities.
Urbanization stress in the form of building, industry,
energy generation, traffic and waste, for example, all
impose a chemical load on the bottom sediments of
water bodies (Owens and CornweiL1, 1995; Finney and
Huh, 1989; Schmidt and Reimers, 1991; Szefer et al.,
1995; Blomqvist et al., 1992). The effects may be distri-
buted over long periods especially in slowly reacting
compartments, such as sediments.
Total element analyses can be used to identify
temporal and quantitative variations in loading
(Schmidt and Reimers, 1991; Norton et al., 1992;
Virkanen et al., 1997), although this technique lends
itself poorly to examination of the factors which
regulate deposition and solubility. These factors are
© 1998 EIscvier Science Ltd. All rights reserved
Printed in Great Britain
0025-326X/98 $19.00+0.00
those that determine the potential ecological hazard
attached to a particular element in an aquatic
ecosystem. A more appropriate method for the latter
purpose is selective extraction, a technique which
determines different modes of occurrence of particular
elements in the sediment (Tessier et al., 1979, 1985,
1989). Knowledge of binding is an effective tool for the
planning of lake or river restoration measures or the
treatment of waste water.
This paper is concerned with the effects of urbaniza-
tion on the binding of elements to the bottom sediment
of a marine bay. Variations in A1, Ca, Cu, Fe, Mn and
Zn concentrations in the sediment and their distribu-
tion among compounds of chemically different types
are determined (F6rstner, 1987), these metals having
been selected as representatives of the groups
considered relevant to the classification of lake
sediments (H~kanson and Jansson, 1983): major
elements (AI), carbonate elements (Ca), mobile
elements (Fe, Mn), and trace elements (Cu, Zn). The
aim is to evaluate the mobility of metals bound in
different ways to the sediment of T6616nlahti Bay in
the centre of Helsinki, Finland. The site is well suited
for such a purpose. An earlier analysis of total metal
concentrations in the sediment of the bay (Tikkanen et
al., 1996) enabled the element parameters to be
divided roughly into those correlating closely with loss
on ignition and those correlating closely with minero-
genic matter. The history of eutrophication in the bay
has also been examined by means of diatom analyses
(Tikkanen et al., 1996; Korhola and Blom, 1996).
The Bay of T6616nlahti
Located in the centre of Helsinki, Finland (Fig. 1),
the Bay of T6616nlahti is some 650m long and
200-300m wide, with a surface area of 20 ha. The
maximum depth is 2 m, and its shore slopes are gener-
ally gentle except for steep cliffs in the eastern part.
The bay is connected to the brackish Baltic Sea by an
opening 6 m wide and 1 m deep crossed by a bridge
and a series of narrow channels extending from this
729

opening (Tikkanen et al., 1996). The average salinity of
the water during the 1990s has been 4.6%o (Kansanen
et al., 1995).
The population of Helsinki increased substantially
during the present century up to the 1970s, after which
it began to decline, only to be followed by an increase
in the 1990s. The areas to the south of the bay had
already been built up by 1940, whereas building has
continued to the north up to the present day. There
was a sugar refinery functioning on the northern Shore
of the bay from 1823 to 1965 (Tikkanen et al., 1996).
The growth in population served to increase the
waste water entering the bay. The sugar refinery also
discharged untreated effluent directly into the bay. The
first sewage pipe, conducting waste water into the
southern part of the bay, was completed in 1878, and
the first waste water purification plant was established
in the area in 1910, remaining in use until 1935. By
1960 all direct emissions into the bay had ceased, waste
enters the bay only through occasional overflows, in the
form of soluble air-borne deposition or by leaching
from the sediment itself, or from animal excrement
(Tikkanen et al., 1996).
T661Onlahti is classified as eutrophicated, its water
quality varying from satisfactory to poor according to
local standards (Pesonen et al., 1978; Varmo, 1991;
X Sample site • • . • = Watershed = Main road
B Built-up area i~!~ii~
i~ijJi~iHField or meadow iii:iiiiiiiiForest, waste land :::::::
Fig. l The Bay Of T6616 in the center of the capital Helsinki
(redrawn from Tikkanen et al., 1996).
730
Marine Pollution Bulletin
Rinne and Varmo, 1990). The mean total phosphorus
is 90 mg'm -3 in the surface water and 98 mg.m -3 in
the bottom layers. Major seasonal variations in total
nitrogen concentration varied between 600 and
1200 mg.m -3 in 1994. The density of faecal bacteria in
July-September is > 100 pcs.100 m1-1. The principal
source of these bacteria is the extensive population of
waterfowl (Kansanen et al., 1995).
Sampling and Analytical Methods
A sediment core 450 cm in length was taken from
the centre of the bay in winter 1995 by means of a
large Russian corer (diameter 100ram, length
500ram). The core was wrapped immediately in
polyethylene film on location, cut into 1-cm slices on
plastic sheeting in the laboratory, dried in Minigrip©
bags at 80°C (Tanner and Leong, 1995), and homoge-
nized in an Ika A10 © mill with a W-Co blade. The bags
containing the dried, homogenized samples were kept
at a temperature of 4°C.
Total acid soluble Cu and Zn analyses were done at
intervals of 10 cm for the whole 4.5 m core in order to
determine the most polluted layer of the sediment
core. 0.2-0:5 g of dry material was weighed into a
Tecator tube with a mixture of a HNO3-HC104-
HzSO4 mixture (10:2:1). The samples were subjected to
wet digestion in increasing temperature until the first
white SO3 vapour was observed. Digestion was then
continued for 15 rain, a few millilitres of water was
added and the mixture was boiled for a few minutes.
The mixture was finally filtered through S&S 58950
filter paper and diluted to a volume of 25 ml (Allen,
1989).
Total Cu starts to increase from a depth of 80 cm
and total Zn from a depth of 60 cm, indicating that the
most contaminated section of the sediment occurs at
the upper part of the sediment profile. The extraction
study was applied at intervals of 1 cm for the topmost
100 cm of the sediment.
A maximum of 1.0 g of sample was weighed and
divided equally between two polypropylene test-tubes
for isolation of the following fractions from the
sediment material:
(I) Exchangeable cations: 8 ml of MgCI2 (1 M, pH
7.0) was added to the sample and the mixture shaken
at room temperature for 1 h.
(II) Carbonates: 8 ml of NaOCOOH (1 M, pH 5.0,
adjusted with acetic acid) was added to the residue
from stage I and the mixture shaken for 6 h.
(III) Fractions bound to Fe-Mn oxides: 20 ml of
NH2"OH'HC1 (in 25% CH3COOH (0.04M)) was
added to the residue from stage II and the mixture
-----, Railway heated at 96_+3°C for 6 h using a Grant QBT2 block
ii!iii Park thermostat, with occasional stirring.
(IV) Fractions bound to organic material: 3 mt of
0.02 M HNO3 and 5 ml H202 (30%, pH 2.0, adjusted
Volume 36/Number9/September 1998
with HNO3) was added to the residue from stage III
and the mixture was heated at 85+2°C for 2 h with
occasional stirring. 3 ml of H202 was then added (30%,
pH 2, adjusted with HNO3) and the mixture heated
again for 3 h with occasional stirring. 5 ml of NH4OAc
(3.2 M 20% (v/v) in HNO3) was added after cooling
and the mixture was diluted to 20 ml and shaken at
room temperature for 30 min.
After stages I-IV, the sample was centrifuged for
30 min using a 4000 RPM Sorvall TC 5 centrifuge, the
supernatant pipetted off and the precipitate washed
with Type I Reagent Grade Water (ASTM-Dl193,
Barnstead Nanopure II). Two parallel filtrates were
combined and diluted to a volume of 25ml in a
volumetric flask. The residue was used for the next
extraction step.
(V) Acid soluble (residual fraction): the residue
from stage IV was transferred to a Tecator tube and
subjected to wet digestion prescripted earlier. The
HF-HC104 treatment prescribed at this point in the
original instructions had to be omitted because of the
lack of platinum and teflon crucibles. Thus, the yields
from the acid soluble fraction were smaller than they
should have been, which must be taken into considera-
tion when interpreting the results. HC1-HNO3-
HCIO4-digestion (Vuorinen et al., 1986) and
HC1-HNO3-digestion (Young et al., 1992) have been
used for total metal analyses in extraction studies. All
the equipment was washed in 1 M HNO3 and rinsed in
Reagent Grade Water.
A1, Ca, Cu, Fe, Mn and Zn concentrations in the
dilutions were measured on a Varian SpectrAA 10+ ©
atomic absorption spectrophotometer. Cu, Fe, Mn and
Zn were determined using an air-C2H2 flame, and A1
and Ca using an N20-C2H2 flame. The standards were
prepared from 1000 mg.m1-1 stock: solutions immedia-
tely before the measurements and corresponding
quantities of the extraction solutions were added to
these. The matrix problems produced memory effects
when analysing the stage III solutions, but these effects
were eliminated by additional dilutions (1:4) and
repeated calibrations performed at short intervals.
The total phosphorus concentration of the separate
parallel samples after wet digestion in the
HNO3-HC104-H2SO4 mixture (10:2:1) was deter-
mined by the ammonium molybdate method with
ascorbic acid reduction (Enell and Larsson, 1986). The
total sulphur concentration was determined by SO42-
turbidimetrically from samples dried with HNO3 (p.a.
67%) and Mg(NO3)2 and dry-ashed at 550°C for 12 h
(Allen, 1989; Grimshaw et al., 19891). All concentrations
were transformed into concentrations in dry matter.
Total metal concentration was determined by counting
up the concentrations of all the extract steps.
A principal components analysis (PCA) executed
with the STATGRAPHICS V5.0 statistics program was
used to illustrate variations within the data and correla-
tions among the variables. All the parameters were
log-transformed prior to the analysis. T-test was used
in order to examine the possible differences between
total metal concentrations from the extraction study
and total metal concentrations from the parallel
separate sediment column made earlier. Analysis was
done using the STATISTICA V5.0 computer program.
The rate of sedimentation was determined using
137Cs- and 14C-measurements and spheroidal carbona-
ceous particle (SCP) analysis. 137Cs-measurements
were done in the laboratory of the Environmental
Center of Helsinki. ~4C-measurements were carried out
in the dating laboratory of the University of Helsinki.
SCP analysis was done according to Rose (1990). Its
application to chronology is based on comparison
between the total areal fossil fuel combustion history
and the SCP concentration in the sediment (Renberg
and Wiik, 1985).
Extraction methods and their selectiveness and
accuracy have been examined previously (Luoma, 1986;
Kheboian and Bauer, 1987; Shannon and White, 1991;
Young et al., 1992). Problems include the danger of the
redeposition of material already extracted (Kheboian
and Bauer, 1987). In addition, the extraction system
may be non-selective, i.e. not all the elements are
released in the same manner at the various stages. In
sequential extraction, stage IV of the extraction
releases compounds bound as sulphides as well as
those bound to the organic fraction (Luoma, 1986).
In a simultaneous extraction system in which the
sample is divided into parallel parts which are
processed separately (Young et al., 1992), three groups
of compounds are determined: (1) easily reducible (Mn
oxides), (2) easily reducible and reducible (Mn-Fe
oxides), and (3) organically bound. The advantage of
simultaneous extraction over the sequential extraction
method of Tessier et al. (1979) is the shorter processing
time and the lesser exposure of the samples to possible
impurities in the extraction chemicals. The yields
obtained from simultaneous extraction differ from
those achieved by the sequential method. The distribu-
tion of Cu into fractions were identical in the two
methods, but Fe and Mn yields were smaller in sequen-
tial extraction and the Cu yield in simultaneous extrac-
tion. These differences were attributed to technical
deficiencies in the sequential extraction technique
(Young et al., 1992).
Results
Sediment description and dating
The following horizons were encountered in the
sediment column, 4.5 m long
Depth (cm) Sediment type
0-25 Almost homogeneous grey-green clay
731
 Marine Pollution Bulletin

gyttja (Seppfi, 1997). These trees were planted in the

25 -50 Dark clay gyttja with light streaks adjacent parks in the 1920s and 1930s.
50-66 Dark clay gyttja with fading streaks
66-77 Homogeneous, dark grey clay gyttja
S and P concentration
77-95 Clay gyttja with black sulphide streaks
The phosphorus concentration increases gradually
95-200 Black sulphitic clay gyttja
from the lower layers upwards (Fig. 3), reaching a peak
200-252 Black sulphitic clay gyttja with light streaks
at around 55 cm and declines above this to the surface
252-300 Gray homogenic clay gyttja
where it is the same as in the lower part of the
300-325 Gray clay gyttja with weak streaks sequence. The sulphur concentration also increases
325 -350 Gray clay gyttja with black sulphide streaks towards the surface layers (Fig. 3), reaching a peak at
350-390 Increasingly lightening clay gyttja 40-50 cm, corresponding to the depths where the most
390-450 Homogenic light gray clay gyttja pronounced reducing conditions are observed. Above
40 cm, it declines but remains higher than in the
Loss on ignition (550°C, 2 h), which approximates bottom of the sediment core. The P and S concentra-
the concentration of organic material in the sediment, tions indicate that evidence of the most intense period
remains constant at 8-11% up to a depth of 80 cm of eutrophication occurs at depths of 30-60 cm, repre-
(Fig. 2), above which it increases slowly to 56 cm and senting the period from the turn of the century to the
1950s. Eutrophication can also be detected from
then begins to vary considerably, with maximum values
changes in the diatom communities, which contain
as high as 20%. It remains in the range 13-14% from
species indicative of a high nutrient concentration from
23 cm upwards.
between 60 and 30cm (Korhola and Blom, 1996).
The activity curves for 137Cs and concentration of
According to Kansanen et al. (1995) some 2.3% of the
SCP are shown in Fig. 2. There is a clear maximum in
total P in the surface sediment (0-30 cm) and 3.1% of
SCP concentration at 24 cm, which goes together with
the total P in the deeper sediment (100-150 and
the increase in the consumption of fossil fuels in
250-300 cm) is easily soluble.
Finland from 1960s onwards. The 137Cs peak at 26 is
obviously caused by a nuclear test in the early 1960s.
Another peak at 8 - 9 c m can be associated with Extra ctions
Chernobyl (1986). A total radiocarbon age of 1780_+ 80 Acid soluble fraction accounts for over 80% of the
(Hel-3673) was obtained for 145-155 cm. Together, total A1 in the lower part of the sequence (Fig. 4).
these methods yielded an average sedimentation rate Organically bound A1 increases slightly at the most
of ca. 0.6cm'yr -1 for the topmost 55cm and ca. intense eutrophication stage. Exchangeable A1
0.4 cm.yr-1 for the rest of the core (Tikkanen et al., increases at the surface. Exchangeable carbonates and
1996). This is further supported by the pollen stratig- hydroxides account for a negligible proportion of total
raphy, for example, the frequencies of unique pollen of deposition. The total A1 concentration decreases
park trees start to increase in the core at ca. 1932 slightly from the bottom to the surface.
Exchangeable and acid soluble Ca make up a large
proportion of the total Ca (Fig. 4). The total Ca
increases from the bottom to a depth of 55 cm, where
l~Cs Bq.g °1 Loss-on-ignition Carbonaceous particles g'lx104 the maximum concentration of t h e total Ca occurs.
0 0,2 0,4 8 10 12 14 16 18 20%0 40 80 120 160
t i i i
During eutrophication, organic Ca increases tempo-
rarily. Carbonate and Fe-Mn bound Ca stay almost
constant. Towards the surface, the total Ca decreases
2O with several sharp and temporary drops.
Most of the background Cu is acid soluble (Fig. 5),
30
but the amount of organic Cu increases gradually from
o, 40' a depth of 80 cm, reaching a peak during the most
1930
pronounced eutrophication. The amount of Cu in
~. 50,
1900
exchangeable carbonate and hydroxide and acid soluble
Cz
60 form also increases. The proportion of loosely bound
forms of Cu is markedly higher in the surface layers
70' than in the background sequence. Total Cu concentra-
80. tion is also very high in the surface sediment.
The acid soluble forms are dominant in the deposi-
90. tion of Fe, reaching almost 80% at their maximum
100
(Fig. 5). The proportion of organic Fe increases in the
Fig. 2 LOI, ~37Cs activity and concentration of SCP (redrawn from contaminated layers and decreases above this,
Tikkanen et al., 1996). returning almost to the background level in the surface

732
Volume 36/Number 9/September 1998

P (pg/g) S (pg/g)

500 1000 1500 2000 2500 3000 0 10000 20000 30000 40000
I i r ~ I i I,I i I i I

1o

20
<..
30

40 ._¢
/

/
50

60 J

70 i

80

90

lOO
(cm)
Fig. 3 Total P and S concentrations (gg.g- i in dry weight).

layers. Loosely b o u n d forms of Fe are lowest during Like Fe, Mn is mostly acid soluble (Fig. 6). The
the most intense pollution. T h e proportion of a m o u n t of organic Mn increases at the eutrophication
exchangeable and carbonate b o u n d Fe of the total Fe stage, but falls again in the surface layers. Unlike Fe,
is negligible. however, Mn also occurs in the form of exchangeable

Al(pg/g) Ca (pg/g)

10000 20000 30000 2000 4000 6000

i ~ I i f i I r t

,(
\
/

i ~"/
.... 7 " " ~

5oi-¢ )

60 - ~ t',,.
)

70-
I I

80- 7 '~
90-
|
100' - ~ - - - ~ - -
(cnl) .......... Exchangeable- Carbonate . . . . . . . . Fo-Mn-oxide bound . . . . Organie bouud Acid soluble
Fig. 4 Distribution of total A1 and Ca in sediment core solubilised in
the sequential extraction (~tg.g- J in dry weight).

733
 Marine Pollution Bulletin

'@'
Cu (pg/g) Fe (IJg/g)
100 200 300 20000 40000 60000
i [ i I r I I
, L e.~l I
"I I 1 * "x

10- N

'%
20
J

30

40
-.-~---~..~.~ f I ~
- - - " _- ---_--5__

5o

~ ¢
60 /
( ;

, /
tt

90-
v, --e
100 -
(cm) .......... Exchangeable - - Carbonate . . . . . . . . Fe-Mn -oxide hound . . . . Organic bound Acid soluble

Fig. 5 Distribution of total Cu and Fe in sediment core solubilised in

the sequential extraction (rtg'g- J in dry weight).

cations, the amount of which declines temporarily Zn occurs in the background sediment, mainly in
during the most intense eutrophication. The proportion acid soluble form (Fig. 6). Its amount remains
of carbonates and hydroxides is small. Between 20 and relatively stable throughout the sequence, but the
0 cm of the total Mn clearly decreases. proportions of more loosely bound forms, particularly

Mn (og/g) Zn (pg/g)
0 100 200 300 400 500 0 500 1000 1500 2000 2500 3000

10-

20 -- ~" r~
<.

30- ~
/

40 - ~ ; " ~

'. 21,
60
I
_ ." %
70
t
80

90

100
(era) . . . . . . . . . . Exchangeable- Carbonate . . . . . . . . Fe-Mn -oxide bound . . . . Organic bound Acid soluble

Fig. 6 Distribution of total Mn and Zn in sediment core solubilised

in the sequential extraction (pg-g- 1 in dry weight).

734
Volume 36/Number9/September 1998

exchangeable cations and hydroxide Zn, increase diagram was acid soluble with very little ecological
towards the surface also causing an increase in the availability. Corresponding situations have been
total Zn. The amount of hydroxide Zn momentarily observed in undisturbed offshore sediments (Zhang,
reaches approximately 20% of the total during eutro- 1995; Windom et al., 1989; Giordano et al., 1992).
phication. Exchangeable cations increase consistently The geochemical fluctuations in deposition in the
throughout the sequence, however, constituting as most polluted part of the sediment can best be ascer-
much as 60% of the total Zn at the surface. The total tained and summarized by means of a principal compo-
Zn concentration is very high in the surface sediment. nent analysis (PCA); the first two principal components
The total yields obtained in the analyses were accounted for 65.4% of the variance. The correlations
compared with those of a series of analyses performed between the variables, directions and intensities of the
from a separate parallel sediment column (Tikkanen et variation (arrow length) and locations of the sampling
al., 1996; Virkanen, unpublished data). The totals of depths are indicated in the PCA diagram in Fig. 7. The
Cu and Zn achieved by the extraction method came variables form an almost regular, circular radial pattern
very close to those obtained by wet digestion with which is surrounded by a U-shaped distribution of
HNO3. The t-test showed no s~:atistically significant sample depths. Variables that are closely situated are
difference (p<0.01), however, the results for A1, Fe, positively correlated. Variables that are at an angle of
Ca and Mn when using wet digestion with 180° to each other are negatively correlated. In the
HNO3-HC104-H2SO4 (Tikkanen et al., 1996) were PCA diagram a number of correlated variables can be
smaller than those determined with the extraction seen. These clusters are typical for samples of the same
method or with HNO3 wet digestion. Statistically these depth. It is doubtful that all these correlations are
differences were significant (p <0.05). Generally, total meaningful.
concentration variations were the same in all analyses. The deepest cluster of samples is composed of acid
soluble MnV, CaV and A1V at approximately 80 cm,
occupying a position at an angle of almost 180° to the
Discussion loss on ignition (LOI). This cluster can be dated to a
It can be deduced from the concentration curves period before 1900. Ca represents the highest degree
that most of the deposition in the lower part of the of solubility in granite weathering, Mn an intermediate

h.. i

':'"" ""%. i
,'~ / "".-~ Mnlll
3.4
................................................... ;....../...-,~:.,,~.~.-;; ......................,...x..... ,:. ............................................................. 8~.~. ....................

i,:,/ .... ":/

ir .: c.,%1
"",I~..,
c,,,,i :i M~v '~.~,.;,,
CaV/,,~
'
/~,,
E
0
.." l.~.....~.
I ` ",, i&fv ,(~,-:" ,.
e= ! : " AIIII, },'- '~'i~ : ./" lOOcm
0
O= 0.8 ...................................... ;':'"~""~. .................... =:~;~'~ ................... '........................... ~,>-:'"'"i......... ~ ................. #',-,~.-1............
E
0
0
/ / ',
"0 ,"_.,..--'~ "~ , - - ~ e V .~ - . . ~ J - ~ l ~ k ~ : ~Fe III
t- ,',,.,,~ i .... ~" ,,': Mn JY " ~ . ~ . ~ / M . ' ~ I ' ~ F e ~/
O
0
0
,
O9
-1,8 ................................................... ~ ................................ ~,U" ~'"'i" ....I...I ...... .&=z.2.2~dm......-.)~ ..................................................

i ) / "..A,,i
-4.4
................................................... i ............. i cu, ~"~ !
",,'L,i
"!2~- ~o~m

71 cm

-7
-10 -6 -2
First component
Fig. 7 PCA-biplot for the first two principal components.

735

level and A1, Fe and Cu the least soluble components
of all (Harriss and Adams, 1966). The detrital concen-
trations of A1 and Mn observed in the T6616nlahti
sediments are in line this scheme. Another cluster
composing of hydroxide Fe and Mn may be observed
slightly closer to the surface.
A cluster comprising organic, carbonate and
hydroxide Ca together with total P is located in the
middle of the sediment sequence, representing a
period around the turn of the century. An increase in
the nutrient concentration at the beginning of the
eutrophication gave rise to an expansion in diatom
populations indicative of eutrophic conditions (Korhola
and Blom, 1996). According to De Kanel and Morse
(1978), calcite and aragonite co-precipitate efficiently
with orthophosphates in sea water. It is likely that
advancing eutrophication led to changes in the water in
T6616nlahti which have favoured the deposition of
Ca-P rich compounds. Towards the surface, the total
Ca decreases, perhaps because of dilution by organic
matter or biogenic silica (Blomqvist et al., 1992; Owens
and Cornwell, 1995). Because the net change of LOI is
about 5% between 100 and 0cm, excluding the
55-20 cm level, the dilution of total Ca is perhaps
exceeded by biogenic silica. This sedimentation of
biogenic silica could also explain the temporary drops
of total Ca between 60 and 0 cm. Total A1 and Mn
have perhaps been influenced by the same dilution.
The next more or less tight cluster dominated by A1
IV, Cu II-V, Zn I-IV, Fe IV, LOI, Mn IV and total S
are located at a depth of 40-30cm, representing
sediments deposited from 1930 to 1950. Borg and
Jonsson (1996) have noticed elevated concentrations of
Cd, Zn, Pb and Cu in reduced sediments compared to
oxidized sediments in the Baltic Sea. According to
Charlesworth and Foster (1993), Zn occurs mainly in
Fe/Mn hydroxides and organic material and in the
form of carbonates and exchangeable cations in lake
sediments polluted by urbanization. A similar trend is
evident in the deposition of Cd, Cu, Ni and Pb, and
only minimal amounts of metals were found to be
deposited in detrital material.
Laboratory tests have demonstrated that as much as
99.99% of Cu becomes absorbed in organic material
(Benetetti et al., 1996), while Cu(II) and Zn(II) react
with functional groups in dissolved humic acids, the
former with a markedly higher reaction sensitivity than
the latter (Balestrieri and Murray, 1984; Ashley, 1996).
Fe, Cu, Mn and Zn belong to a group of 'borderline
elements' which form oxides, sulphides and nitrates in
aquatic ecosystems, A1 is oxygen-seeking (Phillips,
1995). LOI seems to control the elevated concentra-
tions of total Zn, Cu II-V, Fe V, Mn IV and A1 IV in
this cluster. Elements are in organic compounds or
attached in labile forms to suspended particles. The
presence of total S in this group suggests that sulphides
may also serve as a sink for Fe, Cu and Zn. On the
other hand, the correlation of total S and LOI
736
Marine Pollution Bulletin
indicates that S is in organic form and that the major
source for S is seawater sulphate (Finney and Huh,
1989).
The cluster is located at the surface (0-20 cm) and
in the middle of the U-pattern formed by samples. It
contains the loosely bound materials A1 I-II, Ca I, Cu
I, Mn I-II and Fe I, III, V which may be considered as
an indication of a eutrophication-induced rise in
solubility and an accumulation of dissolved material in
loosely bound forms (Giordano et al., 1992; Vuorinen
et al., 1986). This increased solubility may be attribut-
able to Fe, Mn and sulphate reduction reactions, for
example, in which a large amount of decomposable
organic material is also consumed (Salomons et al.,
1987), the material bound to these fractions being
released for re-circulation. According to Schoer and
Eggersgluess (1982), an enrichment of > 60-70% of
heavy metals is in the labile fraction for suspended
matter and bottom sediments in the estuaries of
Weser, Elbe and Ems. These changes in solubility are
closely related to anthropogenic pollution.
The appearance of Ca I, Fe II-III, Fe V and Mn I
occurs in the open part of the U pattern formed by the
sampling depths. The values attached to these variables
are highest in the upper and lower parts of the
sequence and lowest in the middle part. These concen-
tration changes may indicate the gradual return of the
ecosystem to the state prevailing before the disturb-
ance and they were simply diluted by large organic
inputs or by biogenic silica deposited as a result of
eutrophication, as Blomqvist et al. (1992) observed.
Exchangeable Ca is a result of dissolved Ca in
seawater. The presence of labile Fe and Mn in this
cluster may suggest that they occur in their reduced
forms Fe z+ and Mn 2+ in the pore water, the most
labile forms constituting a markedly larger proportion
of total Mn than of total Fe. According to Balzer
(1978), anoxic Baltic Sea sediments and bottom waters
contain high concentrations of dissolved Mn 2+. This
may be a reflection of the weak level of oxygenation in
the water and sediment of the bay even in a natural
state.
Conclusions
The fractionating extraction performed on the
sediment samples from the Bay of T6616nlahti
indicates that eutrophication has given rise to both
temporary and permanent changes in the sediment
geochemistry during the course of time. The former
can be taken to comprise an increase in the binding of
organic matter at the most intense eutrophication
stage, most notably as regards Cu, Fe, Mn and Zn. A
distinct fall occurs in the organic binding of these
elements after the stage of maximum pollution. The
hydroxide peak for Zn at the beginning of the most
Volume 36/Number 9/September 1998
intense eutrophication should also be regarded as a
temporary phenomenon.
The progression of deposition from a situation in
which acid soluble forms are dominant to one that
favours labile forms should be regarded as a more
permanent phenomenon. This is clearly evident from
the distribution of the Cu and Zn concentrations.
Loosely bound metals are ecologically available. The
occurrence of Ca, Fe and Mn in loosely bound forms
can be regarded as a natural feature caused by salinity
and a weak oxygen state which was disturbed by the
dilution effect of organic or biogenic silica inputs. The
decrease of total Ca, AI and Mn may also reflect a
gradual change in the quality' of sedimentation.
Although the present paper and earlier investigations
have pointed to a gradual return of the ecosystem to
the state that prevailed prior te eutrophication, the
poor condition of the Bay of T6616nlahti can be
regarded as a fairly permanent state unless sufficient
restoration measures can be taken to rectify it.
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