[RADIOCARBON, VOL. 34, No. 3, 1992, P.

585-592]

ANTHROPOGENIC INFLUENCE ON THE 14C ACTIVITY AND OTHER

CONSTITUENTS OF RECENT LAKE SEDIMENTS: A CASE STUDY'

SRDOONADA HORVATINOICMARIJANAHEL2 WALTER GIGER3

CHRISTIAN SCHAFFNER3 INES KRAJCAR BRONICZ DONAT PETRICIOLI2
JOIE PEZDIO 4, ELENA MAR and ANDELKA PLENKO VIC-MORAJ s

ABSTRACT. Anthropogenic activities that introduce an excess of nutrients and other pollutants into rivers and lakes are
causing significant changes in their aquatic environment. Excessive nutrients greatly accelerate eutrophication, and lake marl
formed during eutrophication differs from that formed in oligotrophic water.
We analyzed recent sediment cores from Prone and Kozjak lakes located in Plitvice National Park, central Croatia.
Analyses consisted of 14C activity of calcareous lake marl, the ratio of stable isotopes (b13C, 5180), organic compounds in
the sediment and the distribution of diatoms. Previous 14C activity measurements helped to determine the sedimentation rate
and thus the time period of increased input of nutrients into lakes. We determined the increased 14C activity in lake sedi-
ments caused by nuclear bomb effect in recent depth profiles. We attributed the sudden increase in diatom species, Cyclo-
tella operculata unipuctata andAchnanthes clevei rostrata, in the uppermost 5-cm layer, to eutrophication of the lake water.
We performed a molecular characterization of hydrocarbons isolated from the sediments, and applied computer-assisted
high-resolution gas chromatography/mass spectrometry to estimate contributions of biogenic, fossil and pyrolytic hydro-
carbons.

INTRODUCTION

The anthropogenic impact on lacustrine environments over the past 50-100 years is recorded in
lake sediments in the form of significant changes in chemical and isotopic constituents (Schell &
Barnes 1986; Giger, Schaffner & Wakeham 1980). In less affected environments, such as Plitvice
National Park, located in a sparsely populated karst area of northwestern Dinarides, the
concentration of major ionic species in freshwater, dissolved inorganic carbon (DIC) and
sedimentation rates have not changed recently (Srdoc et a1.1985). Consequently, recent calcareous
deposits in lake marl contain up to 95% of CaCO3, undifferentiated from older sediments (Srdoc
et al. 1986). However, trace elements, isotopes, organic compounds and diatom frustules reflect
changes in the environment, mostly as a consequence of human activity.

We have investigated changes in the uppermost, X30-cm-thick layers of lake marl from karst lakes,
Prosce and Kozjak, fed by springwater and interconnected by numerous cascades and falls formed
by travertine barriers (Fig. 1). One of us (D.P.) retrieved several cores from each lake using a hand
corer. Upper Lake Prosce has been exposed mostly to changes in global conditions, such as
increased 14C activity of atmospheric CO2 due to thermonuclear bomb tests, whereas lower Lake
Kozjak has, in addition, suffered increased local anthropogenic pollution. Lake Kozjak is situated
in the middle of a busy tourist traffic center. The number of annual National Park visitors was
recently estimated at one million.
Besides recent tourism, local farming and a primitive logging industry were recorded since 1800.
Often interrupted by fire and two World Wars, logging and sawmills never developed into a mod-

1Work supported in part by NSF Grants JF-800 and JF-839

ZRudjer Bokovic Institute, 41001 Zagreb, Croatia
3Swiss Federal Institute for Water Resources and Water Pollution Control, 8600 Dubendorf, Switzerland
4Joief Stefan Institute, 61000 Ljubljana, Slovenia
SFaculty of Natural Sciences, Department of Botany, University of Zagreb, Zagreb, Croatia

585
586 Dusan Srdoc et al.

PLIT VICE NATIONAL PARK

Korana river catchment area

Spring Bijela Spring Crna Fig, 1. Map of the central part of Plitvice National Park

RiJ'eka 'Rijeka
em, fossil-fuel-powered industry, and were phased out entirely by the early 1960s. However, thick
deposits of partly degraded sawdust still cover the bottom of parts of Lake Kozjak.

EXPERIMENTAL

Ca. 50 g of sediment was dissolved in dilute HCI. The evolved CO2 was flushed with nitrogen and
trapped at liquid nitrogen temperature. Subsequent procedures including conversion of CO2 to CH4
and gas purification, as well as the counting procedure, are described elsewhere (Srdoc, Breyer &
Sliepcevic 1971).
We took samples for 14C measurements from several X30-cm-long cores from Lakes Kozjak and
Prosce. The sediments were cored in 1989 and 1990 at several points and at different depths
(21.5 m and 38 m in Lake Kozjak, and 20 m and 32 m in Lake Prosce). We used 5-cm-thick
sections for 14C activity measurements, except for the uppermost core section from Lake Kozjak,
which was cut into 2-cm-thick slices for more precise determination of 14C spatial distribution.
Milligram-sized samples of calcareous sediment were treated with diluted HCl to dissolve CaCO3.
Diatom frustules were subsequently cleaned with HNO3 in oxidizing medium to remove organic
detritus. Detailed microscopic analysis was carried out on a compound microscope at 600-1000 x
magnifications (dry and oil immersion) using transmitted light and phase contrast illuminations.
Aliphatic and aromatic hydrocarbons have been extensively analyzed in various types of aquatic
sediments (Blumer & Sass 1972; Youngblood & Blumer 1975; Laflamme & Hites 1978; Giger,
Schaffner & Wakeham 1980; Wakeham, Schaffner & Giger 1980a, b). Giger and Schaffner (1978)
described in detail the analytical methodology used in this study. Briefly, air-dried samples (3.5-
 Anthropogenic Impact on 14C
in Recent Lake Sediments 587

9 g) were Soxhlet-extracted with methylene chloride, fractionated into an aliphatic and aromatic
fraction, and analyzed by high-resolution gas chromatography and gas chromatography/mass
spectrometry.

RESULTS AND DISCUSSION

Isotope Measurements
14C
activity and stable isotope content (13C and 180) of segments of long sediment cores retrieved
in 1983 from both lakes (Srdoc et al. 1986), represent the reference points for comparison with
recent changes in the uppermost sedimentary layer. It was assumed that the calcite sedimentation
rate in both lakes has not changed recently, in spite of anthropogenic influence described in this
paper. Recent morphologic measurements by Wong (1992) substantiate this assumption. Thus, on
the basis of 14C measurements of a 12-m-long sediment profile from Lake Prosce, we concluded
that the sedimentation rate has been constant at 1.6 mm yr'1 over the past 8 ka. Lake Kozj ak has
had a more turbulent history, as demonstrated by stratigraphy, seismic, '4C and diatom profiles of
a 12-m-long core. However, the upper 2 m of sediment show a uniform stratigraphy and a constant
diatom frequency, except in the uppermost 6 cm, which is affected by human influence. The sedi-
mentation rate was determined by 14C measurements at 0.8 mm yr'1 covering the past 2 ka (Srdoc
et al. 1986). We have applied these sedimentation rates to estimate the age of short sediment cores.
The 14C activity of the calcareous part of the lake sediment, expressed in percent modern carbon
(pMC) vs. sediment depth, shows an interesting and peculiar shape, when compared to atmospheric
C02 activity after the bomb-test period. Essentially, the 14C activity of the lake marl increased due
to the thermonuclear bomb tests in 1963. However, the peak 14C activity in the lake sediment was
less pronounced than the atmospheric 14C peak (Fig. 2). While atmospheric 14C activity doubled
during the peak period in the northern hemisphere (Levin, Mi nnich & Weiss 1980), the highest
14C
activity of Lake Kozjak sediment reached X91 pMC, that is only .20% above the pre-bomb-
test level (76 pMC, Krajcar Bronic et al. 1992). The explanation for such a damped response to
the stepwise increase of atmospheric 14C activity lies in the fact that most biogenic carbon in DIC
is derived from biodegradation of topsoil detritus of terrestrial plants. This process is relatively
slow in temperate zones (Scharpenseel & Becker-Heidmann 1989), averaging the 14C activity in
soil CO2 over several decades. In addition, the bomb-produced 14C activity penetrated deeply into
sediment, reaching 8-10 cm below the injection level (Fig. 2). Assuming a constant sedimentation
rate of 0.8 mm yr in Lake Kozjak, this corresponds to 100-125 years, thus contaminating the
1

entire uppermost layer deposited in this century. The process of sediment redeposition, caused very
likely by bioturbation, also contributes to blurring the 14C activity peak in sediments.

Although increased 14C activity in lake sediments reflects a global change in the 14C activity of
atmospheric carbon, the two lakes differ in their responses to global 14C increase. Lake Kozjak is
fed by water from Lake Prosce (Fig. 1), cascading over dozens of cataracts and falls, which brings
about an additional exchange with atmospheric C02, resulting in increased DIC 14C activity of
pMC. This process is very fast, as opposed to the previously described biodegradation of organic
detritus. We observed a pronounced 14C peak in Lake Kozjak sediment after measuring 2-cm-thick
sections, as opposed to 5-cm-thick core sections from Lake Prone.
As expected, the carbon stable isotope content (&3C) and that of oxygen (8160) in recent calcareous
lake marl, consisting of calcite microcrystals, did not change with respect to older sediment. The
S13C
and 5180 values remained constant for the past 8 ka, indicating steady climatic and
hydrological conditions during the Holocene (Srdoc et al. 1986). In contrast to the inorganic sedi-
ment, the recent organic sediments, consisting mainly of degraded detritus of terrestrial and aquatic
588 Dugan Srdoc et al.

A. LAKE PROSCE

0
+
2
+ ft
4
ft
6

12

H
24

26
28

30
t
t
65 67 69 71 73 75 77 79 -30 -25 -20 -15 -10 -5 0 10 20 30 40 0.5 1 1.5 2 2.5
'4C, 613C, x.ve
S modern PDB C17/C18 N2 of diatoms:l0-e
per 100mp

6. LAKE KOZJAK

a 1

2 t f!
+ ft
t 8
4
t f4
6
f ft
J.
t + ft

r
a
C) 14
+ + ft
16
C 1
+
1 + ft

+ ft
24
+ p
26

28
+ ft
30
70 75 80 85 90-35 -30 -25 -20 -15 -10 -5 0 2 4 6 8 0 1 2 3 4 5
11C 613C,
S modern ..vs PDB C17/C18 N2 of diatoms x10'6
per t00mg

Fig. 2. Results of analyses of sediment cores from Lakes Prone and Kozjak;14C activity: - and o = 2 cores, from A, Lake
Prone; B, Lake Kozjak; S13C: : = organic residue; ; = calcareous sediment; hydrocarbons: + = concentration ratio of n-
heptadecane to n-octadecane; diatoms: * = number of diatom frustules/100 mg of dry sediment. See text for sediment profile
age.

plants, showed a change toward more negative b13C values during the past 25-30 years, represented
by the uppermost 3-4 cm of the sediment (Fig. 2). Along with noticeable eutrophication of the lake
water, we observed more intensive growth of aquatic plants. Stands of Miriophyllum verticillatum
cover parts of the bottom of both lakes, where only clean lake marl existed 20-30 years ago. In
 Anthropogenic Impact on 14C
in Recent Lake Sediments 589

turn, expanded aquatic vegetation led to more detritus from aquatic plants in the uppermost 3-4 cm
of sediment. Most of the aquatic plants growing in the lakes have very pronounced negative S13C
values, down to -40%o vs. PDB (Marcenko et al. 1989). This shift in S13C values for organic
residue, from an average of -30.5%o to -33.5%o in the top layer, results from anthropogenically
induced eutrophication in both lakes. The b180 value is not affected by human activity and remains
constant throughout the sediment core.
Diatom Analysis
We recorded a substantial increase in diatom frustules in the upper 5 cm, and especially in the
uppermost 2 cm of the sediment collected in 1989 in Lake Kozjak (Fig. 2), which is due to the
sudden growth of diatoms, Cyclotella operculata, var. unipunctata associated with planktonic
Stephanodiscus minutulus and Achnanthes clevei var. rostrata. Cyclotella operculata var. uni-
punctata is a tiny diatom that occurs facultatively in plankton, but may also be found in periphyton.
Achnanthes clevei var. rostrata is a frequent member of diatom assemblages of alpine and Baltic
lakes. In 1983 we found this species throughout the 12-m sediment core, but always below 1% of
the total diatom population. We repeated the diatom analysis in sediments in 1990, using several
short cores. We observed a decline in Achnanthes diatoms, which meant that their mass develop-
ment may have been a temporary and/or local event. However, the samples collected in 1990 were
dominated by another periphytic and facultative planktonic form, Fragilaria construens. Typical
plankters, however, such as Cyclotella plitvicensis, C. comta, Fragilaria crotonensis and Asteri-
onella formosa, decreased in frequency. Concurrent analyses of plankton indicate that the
phytoplankton populations have also changed from dominance by diatoms to Chrysophytes and
Chlorophytes, which, by itself, is a sign of accelerated eutrophication, probably due to an influx
of waste waters. Cyclotella operculata and its var. unipunctata are gradually becoming dominant
in Lake Prone as well. However, the total number of diatoms g 1
of lake sediment in this lake did
not change recently, as opposed to their substantial increase in Lake Kozjak (Fig. 2). Planktonic
diatoms still dominate in this lake, although the cyanophyte, Chroococcus turgidus f quaternaria,
not present before, appears as an ominous sign of eutrophication.

Cyclotella operculata var. unipunctata remains dominant in both lakes. Once frequent planktonic
forms, such as Cyclotella plitvicensis, C. ocellata, Fragilaria crotonensis and Asterionella formosa,
which are still abundant in Lake Prosce, are depleted in Lake Kozjak. On the basis of diatom
species and frequency analysis, Lake Prosce is less affected anthropogenically than Lake Kozjak.
The occurrence of planktonic chrysophytes (Dinobryon divergens), chlorophytes (Sphaerocystis
planktonicus and Crucigenia irregularis) and cyanophytes (Microcystis) in Lake Kozjak indicates
a higher trophic level, compared to previous measurements in 1983.

Results of combined analyses of plankton and sediment raise concern about anthropogenic effects
on the trophic level of these lakes.

Hydrocarbons in Sediments
Molecular characterization of sedimentary hydrocarbons is widely accepted as a valuable method
of studying sources and transformations of organic matter in the aquatic environment. Such an
approach proves to be particularly useful in investigations of aquatic sediments that contain historic
record of the environmentally relevant events, such as climate, primary productivity, erosion and
human activity.
We investigated recent sediments from Plitvice Lakes for their hydrocarbon composition in order
to decouple various sources of organic matter, as well as to estimate the variability of particular
590 Dugan Srdoc et al.

inputs throughout the recent history of the lakes. Among the different classes of hydrocarbons, the
highest concentrations were determined for n-alkanes, whereas the concentrations of polycyclic
aromatic hydrocarbons (PAH) were much lower. Carbon preference indices (CPI) for all of the
investigated samples varied in relatively narrow ranges of 5.97-9.49 and 6.92-8.40 for Lakes
Kozjak and Prone, respectively. Such high values of CPI clearly indicate that the major portion
of the determined hydrocarbons was of terrestrial origin (Giger, Schaffner & Wakeham 1980).
Figure 3 shows the sediment depth profiles for two dominant types of n-alkanes, n-heptadecane
(n-C17) and n-nonacosane (n-C29). It is known that n-heptadecane represents a very good indicator
of autochthonous planktonic input, particularly by diatoms (Giger, Schaffner & Wakeham 1980).
Consequently, the increasing levels of this compound in the youngest sediments were attributed to
an enhanced primary productivity of the lakes, i.e., to eutrophication.

Depth (cm)
0 S

A. Prosce
5

10 m

15

20

25 n-C17
n-C29

30
0 1 2 3 4 5 6
Concentration (Thousands np/p )

Depth (cm)
0

10

15

20

Fig. 3. Depth profiles of n-heptadecane (n-C17) and

25
n-nonacasane (n-C29) in sediment cores from A,
Lake Prone and B, Lake Kozjak. See text for
1 2 3 explanation of depth profiles.
Concentration (Thousands ng/y)

A much clearer picture of the eutrophication trends can be obtained when concentration of
heptadecane is normalized against the concentration of octadecane, a compound with a very similar
chemical structure but of rather different origin (Giger, Schaffner & Wakeham 1980). The depth
profile of n-C17/n-C18 concentration ratio (Fig. 2) shows that the increase in eutrophication coincides
with logging and sawmill activity around 1850, and that it significantly accelerated towards the
youngest sediments in both lakes. In terms of absolute concentrations of n-heptadecane, the
concentrations of that compound in the Plitvice Lakes are significantly lower than those found in
highly eutrophic Greifensee (Giger, Schaffner & Wakeham 1980).
 Anthropogenic Impact on 14C
in Recent Lake Sediments 591

The concentrations of n-nonacosane are significantly higher than n-heptadecane in Lakes Prone
and Kozjak. This suggests that the dominant input of organic matter into the lakes derives from
terrestrial plants (Giger, Schaffer & Wakeham 1980). A large part of that input can be considered
of purely natural origin, since the lakes are surrounded by large forest areas. However, a portion
of the input from this particular source is influenced by human activity, such as timber cutting and
sawing, which could increase the input of higher plant debris, particularly sawdust, into the lakes.
We obtained very informative data about human activity around the Plitvice Lakes by analyzing
PAH, which are predominantly of anthropogenic origin (Wakeham, Schaffner & Giger 1980a).
Figure 4 shows the concentration profiles for three selected PAHs representing compounds with
4-6 rings. Apparently, the concentration profiles of individual PAH are very similar, suggesting
that they might have had a common origin. As expected, the lowest anthropogenic PAH
concentrations were determined in the deepest sections of the sediment cores. The maximum of
the PAH contamination, found in sediment depths of 10-15 cm in Lake Prosce and 5-10 cm in
Lake Kozjak, coincides with intensive timber cutting and sawmill activities around 1850. Recently,
most of the industrial activity around the Plitvice Lakes ceased, and traffic was diverted farther
from the lakes. Thus, the concentrations of the anthropogenic PAH sharply decreased to values
similar to those found in sediment sections as old as 200-300 years.

Depth (cm)
0

10

15

20

25

30
D 50 100 150 200 250
Concentration (np/p)

Depth (cm)
0
B. Koz jak
5

10

15

20 Fig, 4, Depth profiles of anthropogenic polycyclic

-e- Fl aromatic hydrocarbons (PAH) in sediment cares
m * BaP from A, Lake Proee and B, Lake Kozjak; F1= fluo-
-8 IndP ranthene; BaP = benzo(a) pyrene; IndP = indeno
30 `
(1,2,3-cd) pyrene, See text for explanation of depth
0 50 100 150 200
Concentration (np/p) profiles.

CONCLUSIONS

Anthropogenic influence on ground and surface waters can be traced in recent lacustrine sediments.
In many cases, the history of environmental pollution and future trends can be derived from sedi-
592 Dugan Srdoc et al.

ment analyses. Both global and local impacts are recorded in lake sediments, very often featuring
site-specific characteristics. In the Plitvice Lakes, contamination of lake sediment by bomb-
14C
produced 14C has been pervasive, even though minor differences in activity of lake marl from
two lakes are evident. We noticed a damped response to atmospheric 14C contamination and,
14C
presently, a downward trend in the 14C activity of the lake marl. The peak activity of the lake
sediment reached 91 pMC, which is only 20% above the pre-bomb-test activity of the sediment.
Aliphatic and polycyclic aromatic hydrocarbons generated by natural processes or human activity
usually spread over the entire drainage area. The hydrocarbon indicators in sediments also follow
human activity in the region, peaking during the most intensive logging and sawmill activity.
Whereas the concentration of n-alkanes (C17 and C29) continues its upward trend in Lake Kozjak
due to degradation of thick deposits of sawdust, it is interesting and encouraging to note that a
recent tourist boom did not bring an increase to PAH concentration from fossil-fuel combustion.
Under the environment-oriented National Park policy, traffic is diverted from the vicinity of the
lakes. Unfortunately, local pollution of Lake Kozjak by waste waters persist, as is evident from
diatom analysis.

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