Abstract
During 2014 (May-September), the genus Laccobius spp. (Coleoptera:
Hydrophilidae), water and sediment samples from the same location were
collected and heavy element content of these samples were evaluated at
six sampling sites of Erzurum (Turkey).Heavy element concentrations were
measured by Energy Dispersive X-Ray Fluorescence (EDXRF) spectroscopy.
Fourteen elements were detected at measurable levels in all the samples.
Laccobius spp. was evaluated for the first time as a biomonitor of heavy metal
pollution. The results indicated that Laccobius spp. were contaminated by water
and sediment from their habitat, and accumulated higher concentration of
elements than water and sediment, revealed their role as bioindicators of heavy
element pollution. Heavy element concentration levels of the water samples
were compared with national water quality guidelines. Some heavy elements’
concentration was found at high level than the acceptable limits. The mean
concentration of studied elements in the study region increased in the following
order: in sediment samples was Zn Keywords: Biomonitor; EDXRF; Heavy element; Laccobius spp; Turkey Heavy element pollution is a byproduct of industrialization,
urbanization and intensive usage of different chemicals in human
routine activity results in damage to the food chain [1,2]. Therefore,
an early detection of heavy element concentrations in ecosystem is
vital for nature conservation. Heavy element residues at the poles was
widespread during recent years [3]. The use of biota for monitoring quality of environment originated
mainly in Europe early in this century and it has been widely used
[4,5]. Bioaccumulation of elements from air, soil, water and sediment
is currently evaluated with reference to some biological communities
such as plankton [6], periphyton [7], fish [8], lichens, mosses [9],
algae [10], plant [11], insects [12,13]. To assess and monitor the
environment, bioindicators are more useful, because chemical and
physical measurements provide information only on conditions
when the samples were taken, whereas biologic surveillance reflects
long time period conditions [14]. Bioaccumulation process defined
as when chemical pollutant enters into the body of an organism, it
accumulates in the organism’s tissues due to non-degradable feature of
chemicals [15]. Many researchers reported that benthic invertebrates
are most useful in monitoring aquatic ecosystems [4,12,13]. Aquatic
insects have been widely used as biomonitor systems, because they can
accumulate these contaminants in measurable amounts. Even though
for a long time passed over, they can reflect element concentrations
[15]. Hydrophilidae also called water scavenger beetles are large family
and distributed worldwide. These species can live in a wide variety of
habitats and are commonly found in temporary or permanent puddles,
ditches, margin of shallow lakes and ponds. Many aquatic species of
Hydrophilidae, both adults and larvae are abundant in some certain
habitats. The larvae are predatory or carnivorous and not scavenging,
generally feeding on dipteran larvae, small crustaceans and other
hydrophilid larvae. Whereas, adults are scavengers and vegetarians,
usually inhabit in richly vegetated water bodies, and generally feed on
dead or decaying plants also living plants, especially on algae. They
are important in aquatic food chain, since fish, aquatic and birds
depend on these insects [16,17]. In this study heavy element content
of water, sediment, Laccobius spp. and distribution of Laccobius
Erichson 1837 (Coleoptera: Hydrophilidae) was studied. Laccobius
Erichson 1837 is one of the most diverse genus of Hydrophilidae
and 257 species are known worldwide [18]. Laccobius spp. were
evaluated previously by [19] and last status (abundance or absence)
of this genus were evaluated with this study. This genus has greater
swimming ability and occurs in swiftly flowing streams. They can
be easily distinguished from remaining hydrophilid genera by the
combination of abdomen with 6 ventrites, curved posterior tibiae,
and short maxillary palpi [20]. These insects are actively moving on
the water surface and are tolerant to pollution [21]. Many researchers
have reported that, sediment serves as an archive to environmental
pollution, because they are open access to the disposal of industrial,
agricultural and domestic wastewater [22,23]. Sediment function
as a reservoir for industrial contaminants and its quality is a good indicator of environmental pollution. For this purpose sediment,
water samples and insects were collected from selected localities of
Erzurum. Because of the Aras, Çoruh and Euphrates basins originate
in Erzurum province, monitoring these aquatic environments
based on abiotic and biotic samples is important for conservation
of Erzurum’s wetlands. The study was aimed to assess the effect of
pollution on water, sediment of fresh water bodies and to prove
Laccobius spp. as a potential bioindicator of heavy element pollution. Erzurum is a city in eastern Anatolia of Turkey and very rich in
terms of water resources. In this study, six different sampling sites
were selected. Information about these stations was given below
(Figure 1). Station 1: This station is located between 39°55’19 North 40°40’01
East coordinates and west of the cement plant. Altitude is 1636m.
Sampling was done on the edge of Karasu River. Contamination
sources are Erzurum-Trabzon highway traffic pollution and cement
plantash emissions. Station 2: It is located between 39°55’39 North 40°40’41 East
coordinates east of the cement plant. Altitude is1669m. Source of
pollution is less intense traffic and ash emissions from cement plant.
Aquatic habitat was small brook. Station 3: This station is located Askale-Trabzon road, between
39°55’41North 40°38’44 East coordinates. Altitude is 1636m. Stream
source of pollution is traffic. Station 4: This station is located Erzurum-Ilica road, between
39°59’11 North 41°09’21 East coordinates. Altitude is 1753m. Stream
source of pollution is effluents from sugar factory and traffic. Station 5: This station is located between 40°05’34 North 41°22’37
East coordinates, 28 km away to Erzurum center. Altitude is 1819m.
Due to extensive farming and livestock management the effluent to
water bodies is livestock, agricultural and domestic wastes. Station 6: This station is located Erzurum–Çat road, between
39°48’49 North 41°09’45 East coordinates. Teke Stream altitude is
1981m. There is no traffic and also settlements around it. Therefore it
is intended as clean sampling point. Sample collections were done from six different locations in
Erzurum, between May–September 2014. As described in [24] insects
were collected via1 mm mesh aperture sieve and mouth aspirator then
stored in 70% alcohol and station information labeled in the field. In
the laboratory, before identification, insects humidified 1–2 hours in
petri dishthen grass and sand on the insects were cleaned via paint
brush. Male genitalia were dissected under stereo microscope for
identification. Identification was made by first author and certificated
by second author with the aid of Hansen [20]. Five species belonging
to genus Laccobius Erichson 1837 (Hydrophilidae: Coleoptera)
were determined. The following species were recorded: Laccobius
(Dimorpho laccobius) syriacus Guillebeau 1896, Laccobius (D.)
simulatrix D’orchymont 1932, Laccobius (D.) bipunctatus (Fabricius
1775), Laccobius (D.) sculptus D’orchymont 1935, and Laccobius (D.)
sulcatulus Reitter 1909.Insect samples were collected only in summer
months due to marginal ice condition of other months. Benthic zone
sediment was taken via plastic shovel, put into a glass bottle in 30 cm
depth. Water glass bottles washed 4–5 times with the study area water
then filled with water. Then, the samples were kept in the refrigerator
until analysis. The data were subjected to the Mean ± SD variances using SPSS
statistical package programs version 10.0 to perform the analysis.
Elemental analyses were made by using EDXRF. Insect and sediment
samples were dried in an oven at 80°C during 36 hour. Dried insects
were pulverized in mortar and cellulose was added. Cellulose helps
to form a shape. Proportion of cellulose changes according to the
insect size. Insect size and proportion of cellulose do not affect the
measurement of EDXRF. Pulverized insect poured into a DIE set,
which has 13 mm diameter, then put in a press machine and then
applied five tons pressure. For emit photons, an Al sample holder with
Mylar films on both sides were used for water and sediment samples.
Samples were irradiated by 59.5 keV photons, emitted by 1 Ci241Am
radioactive source. X–ray spectra were collected with HPGe detector
which use Genie–2000 software (Canberra) program. HPGe detector
resolution is ~180 eV. The irradiation time was 14.400 s for water
and sediment, 43.200 s for insect samples. Source/Sample distance
was 35.5 mm.To eliminate elements on air, all measurements were
carried out under vacuum. The spectral data were stored on disks,
and the concentration of elements in each samples were determined
by Win AXIL software (Canberra) and WinFund software package
(Canberra), which use the Fundamental Parameters Method (FPM)
for quantitative analysis. Possible error sources for some uncertainties
due to EDXRF (maximum ~5%) are listed in (Table 1). Nature of Uncertainty Uncertainty (%) Counting Statistics ~1.00 Systematic errors ~2.00 Peak evaluation procedure ~3.00 Fundamental parameter methods ~3.00 Results only five species belonging to genus Laccobius were determined. In
total, 236 specimens from six stations in Erzurum were collected and
analyzed for contaminants. The concentrations of these elements
were found to vary in all samples. The results showed that element
concentration in the Laccobius spp. showed differences in accordance
to the sediment and water contamination of the each station.
Concentrations of Ti, Ni and Pb were measured in all stations’
water, sediment and insects samples. The most abundant specie was
Laccobius simulatrix, followed by Laccobius syriacus 48.3% and 26.6%
respectively. On the other hand Laccobius sculptushadless population
(0.84%). Ti, Cr, Fe, Br and Pb were measured in all insects. Heavy
element concentration in water samples indicated that in water of
stations 3 had the highest level of Ti, and in water of Station 6 had
the highest level of Pb, Sr. In all other studied water samples had Cr,
Mn, Fe, Ni, Cu concentration. The rest of the heavy elements in water
samples, that is V, Co, Zn, As, Se and Br had lowest concentration.
Except insects, Station 3 sediment heavy element contents indicated
that V had the highest concentration among the fourteen elements;
in Station 1 and 2 sediments, Cr had the highest level; in Stations 2,
3 and 5 sediments, Mn had the highest level; in Station 2, 3, 4 and 5 sediments, Fe had the highest level; in sediment of Station 6 Sr level was
the highest. Co measured only in Station 2sediment.Zn and Br had the
nearly same level in all sediments. The rest of the heavy elements had
the lowest level. According to the results in insects, L. bipunctatus is
the best accumulator for some certain elements, L. sulcatulus followed
it.Cr, Ni, Cu, Zn, As, Br and Pb were measured in L. bipunctatus in
highest level. Also L. sulcatulus is the best accumulator in regard
to Mn, Fe, Co and Se. The highest level of V and Sr were measured
inL. simulatrix and L. syriacus. The highest level of Ti was measured
inL. syriacus. Ti, Cr, Mn, Fe, As, Br and Pb were only measured in
L. sculptus, but the levels of these elements were not considerable.
As it seen in Table 2, Ti, Cr, Fe, Ni, Cu, Zn, Se, Br, Sr and Pb were
the most abundant elements in the Laccobius spp. In the station 1,
L. syriacus and L. simulatrix have high contamination of titanium,
vanadium, chromium, and the same happens in water. In the station
2 was the most diverse, have the five insect species collected, among
the stations; L. syriacus, L. simulatrix and L. sulcatulus have less metal
contamination of titanium, vanadium, strontium, although except Sr
the water were high; others like L. simulatrix and L. sulcatus have high
contamination of iron and manganese, the same happens in sediment. stations 3 and 6 have the same insect species (L.bipunctatus), and
both have high contamination of lead, the same happens in water and
sediment; station 4 L. syriacus have high contamination of titanium
and vanadium, the same happens with water, and L. sulcatulus have
high contamination ofiron, the same happens in the sediment;
station 5 L. bipunctatus has high contamination of titanium, the
same happens in water; L. syriacus has high contamination of iron
and manganese, and the same happens in sediment and water.The
element concentration showed a general trend of Se Station Samples Heavy Element (Mean ± SD) Ti V Cr Mn Fe Co Ni Cu Zn As Se Br Sr Pb 1 Water 436 ±6.55 82.6 ±4.50 22 ±2.64 6.20 ±0.26 2.96 ±0.15 1 ±1 0.3 ±0.2 0.36±0.15 0 ±0 0.2 ±0.1 0 ±0 0.34±0.14 0 ±0 1.76 ±0.2 Sediment 1.76 ±0.25 0.32 ±0.11 849±6.02 0 ±0 0.13 ±0.06 0 ±0 20 ±2 9.2±0.25 4.90 ±0.65 9.56 ±0.4 10 ±0.51 5.03 ±0.45 9.6 ±0.36 10.8 ±1.04 Laccobius syriacus 130.4±0.52 22.7 ±0.25 19.7 ±0.3 6.6 ±0.45 2.7 ±0.25 1.26 ±0.2 0.57 ±0.09 0.3 ±0.04 0.16 ±0.05 0 ±0 0.4 ±0.01 0.18 ±0.07 317.3 ±3.05 612.6 ±2.94 Laccobius simulatrix 125 ±2.5 22.7 ±0.65 25 ±0.26 8.9 ±0.36 3.8 ±0.2 5.03 ±0.3 0.69 ±0.18 0.33 ±0.1 0.19 ±0.09 0 ±0 0.34 0.2 0.25 0.13 415.6 3.51 0.16 0.05 2 Water 322 20 63.82.75 14.62.51 4.90.65 2.230.25 0.030.02 0.50.1 0.130.05 0.20.1 0.230.15 00 0.250.13 00 1.960.2 Sediment 1.260.25 00 663.613.4 231.312.5 2444.58 8.860.41 153 7.530.45 3.730.37 7.360.77 8.260.30 3.630.55 9.50.5 2.530.5 Laccobius bipunctatus 98.41.27 00 4.260.25 1.30.26 0.730.2 00 0.10 00 00 00 00 0.10.001 0.0030.002 1.430.2 Laccobius sculptus 17.50.5 00 0.50.2 0.160.05 0.10 00 00 00 00 0.020.009 00 0.010.004 00 0.260.1 Laccobius sulcatulus 5.490.19 00 0.140.08 807.63.51 717.62.51 1221 511.6 26.40.5 38.60.45 22.80.75 27.60.35 161.61.52 3.960.45 369.61.5 Laccobius syriacus 0.110.01 00 50.50.81 00 42.31.52 00 10.1 0.510.08 0.430.11 0.430.30 0.40.2 1.20.25 0.110.02 9.60.5 Laccobius simulatrix 2.70.25 00 0.120.02 3722 728.64.16 00 273 12.20.25 17.50.45 11.60.52 12.10.41 23.41.5 1.80.15 1922 3 Water 796.85 140.58 10.20.25 10.10.76 4.80.4 1.80.28 0.70.26 0.260.15 0.20.1 0.230.15 00 0.230.05 00 3.230.2 Sediment 0.290.11 745.382.3 00 4219 32527.8 00 5.531.56 00 0.930.2 2.030.15 2.030.5 1.030.25 1.930.47 0.50.3 Laccobius bipunctatus 2.080.08 00 917.62.51 00 3098.5 00 19.230.25 9.50.51 13.162.84 8.730.25 10.30.26 77.62.51 0.630.15 195.64.9 4 Water 402.33.21 80.60.57 17.51.32 5.80.28 2.20.26 0.60.26 0.430.11 0.130.05 00 0.120.03 00 0.120.03 00 1.930.1 Sediment 0.30.05 00 00 00 6572.57 00 4.930.6 2.20.26 10.05 1.960.2 2.20.26 1.20.26 1.60.52 0.560.2 Laccobius sulcatulus 4.930.40 0.710.21 0.130.05 00 909.33.05 00 37.81.89 201 10.50.5 16.51.5 20.60.79 31.31.5 2.40.35 192.62.5 Laccobius syriacus 9544.58 178.63.05 37.161.75 00 26.61.52 00 0.630.15 0.40.1 0.250.09 0.330.20 0.30.1 1.030.15 0.020.02 6.260.2 5 Water 573.63.51 00 25.60.76 6.962 3.90.26 1.230.25 0.660.2 0.20.1 00 0.20.1 00 0.270.06 0.230.05 2.90.36 Sediment 0.430.2 0.10.1 00 69.61.5 9496.55 00 5.731.1 00 1.430.2 3.260.25 3.560.51 2.960.55 5.330.15 1.030.05 Laccobius simulatrix 0.170.06 429.81.75 91.31.89 26.91.78 15.80.26 00 1.930.3 0.70.2 0.730.37 0.60.1 0.930.11 5.130.61 0.10 80.2 Laccobius bipunctatus 6006.5 112.32.08 222 00 10.50.6 00 0.360.15 0.160.05 0.210.12 0.20 0.130.05 0.360.19 0.020.01 4.030.15 Laccobius syriacus 1.990.55 00 888.35.68 2855.56 315.64.04 423.60 16.31.89 10.21.66 6.930.4 8.230.25 9.360.85 211.04 1.060.4 114.62.5 6 Water 953 15.52.5 22.65.85 8.631.06 3.80.26 00 0.710.22 0.430.11 0.220.04 00 0.360.05 00 3103 6565.29 Sediment 67.32.51 11.160.76 13.31.99 5.410.36 00 00 12.031.37 0.270.06 0.520.14 00 00 00 213.33.05 511.53.77 Laccobius bipunctatus 24.92.73 00 2.380.34 0.670.16 0.930.11 0.180.10 88910.1 3344 181.65.13 6955 00 2003.51 263.6 915.15.83 In Station 6 where the human activity is limited, Pb, As, Cu, Cr,
Co, Ni, Mn and Se residues determinates the extent of the element
spread in Erzurum. When the results were compared to Turkish
Water Pollution and Control Regulation [25], these results signify
that the water bodies are highly polluted (IV). But the waters are high
quality water (I) in regard to Zn and weakly polluted water (II) in
regard to Fe. As it seen in (Table 3) there are four quality classes:
high quality water (I), weakly polluted water (II), polluted water
(III) and highly polluted water (IV) [25]. According to (Table 3), all
stations’ waters have highly polluted (IV) with regard to Pb, As, Cr;
highly polluted water quality (IV) and polluted water quality (III) in
regard to Cu, Co; highly polluted water quality (IV) in regard to Ni
but except to this 4th Station which has pollution free (I) in regard
to Zn and Ba but except to this 6th Station which has high polluted
water quality (IV). Se concentration measured only 6th station and
has highly polluted water quality (IV). 1th and 2nd stations have III
and IV water quality level in regard to Pb, As, Cr, Cu, Co, Ni and Mn,
this can due to cement factory and also highway traffic. 3th Station
has IV water quality level in regard to Pb, As, Cu, Cr, Co, Ni and Mn,
Askale-Trabzon highway may lead to this. 4th Station has IV water
quality level in regard to Pb and Cr this can be due to sugar factory
wastes and also traffic due to Erzurum-Ilica road. 5th Station has IV
water quality level in regard to Pb, As, Cu, Cr, Co, Ni and Mn, this can
be due to traffic and domestic pollution. 6th station, where there is no
industry around it and human activity is limited, has IV water quality
level in regard to Pb, Cu, Cr, Co, Ni, Mn, Se and Ba. Ba measured only
the water of 6th stations and its water quality level is IV. In all samples,
Ce, Mo, Sn, In, Ba, Nb, Pm and Pd elements and their concentrations (ppm) were measured but their concentrations were below EDXRF
detection limit. Heavy Elements 1. Station 2. Station 3. Station 4. Station 5. Station 6. Station TWPCR (μg/L) I II III IV Pb 1.76 0.2 1.960.2 3.230.2 1.930.1 2.90.36 6565.29 10 20 50 >50 As 0.2 0.1 0.230.15 0.230.15 0.120.03 0.20.1 00 20 50 100 >100 Cu 0.36 0.15 0.130.05 0.260.15 0.130.05 0.20.1 0.430.11 20 50 200 >200 Cr 22 2.64 14.62.51 10.20.25 17.51.32 25.60.76 22.65.85 20 50 200 >200 Co 1 1 0.030.02 1.80.28 0.60.26 1.230.25 00 10 20 200 >200 Ni 0.3 0.2 0.50.1 0.70.26 0.430.11 0.660.2 0.710.22 20 50 200 >200 Zn 0 0 0.20.1 0.20.1 00 00 0.220.04 200 500 2000 >2000 Fe 2.96 0.15 2.230.25 4.80.4 2.20.26 3.90.26 3.80.26 300 1000 5000 >5000 Mn 6.200.26 4.90.65 10.10.76 5.830.28 6.962 8.631.06 100 500 3000 >3000 Se 0 0 0 0 0 0 0 0 0 0 0.360.05 10 10 20 >20 Ba 0.0071 0.0053 0.0114 0.000182 0.0093 3.3 1000 2000 2000 >2000 In this study, concentration of heavy element in the water, the
sediment and aquatic insect due to anthropogenic activity were
measured. Also, potential use of some Laccobius spp. as biomonitor for
heavy element pollution was evaluated. Laccobius spp. was evaluated
for the first time as a biomonitor of heavy metal pollution. The study
shows that the heavy element concentrations in sediments varied
significantly. The sediments of station 1, 2 and 3 are enriched with
these elements and byproduct of human activities (industrial, traffic
and agricultural). Besides to sediment quality, water quality played a
key role in space richness of Laccobius spp. because the contaminant
residues in biologic materials reflect quality of environment
[26]. Laccobius is a suitable species as bioindicator. Because it is;
cosmopolitan; easily identifiable; represented in high abundance
and wide spread in all over the monitoring area; have numerical
abundance. Our study is in agreement with the earlier reports [12,13]
and Laccobius spp. embodies all these criteria. Also as it is seen (Table
2) that aquatic beetles accumulate some elements in higher levels
than their environments, hence these beetles can be useful tool for
environmental monitoring studies. Most literature supports the fact
that some aquatic insects are quite sensitive whereas others tolerant
to pollution. Resulted degradation of aquatic environment and
element concentrations in aquatic environments lead to a reduction
of these insects’ richness and abundance. [27] reported that industrial
and mining activities alter water beetle populations, [28] noted that
the insects impacted by sugar cane cultivation, [29] in their studies
showed that pollutants in the environment, resulted in obvious
changes in biochemical processes and cytogenetic parameters and
this will affect growth competence of insects, thus decrease in both
richness and diversity of insects. Decreasing species level in Laccobius
spp. as compared to [19] can be explained the current pollution
statius of Erzurum province. Thus, our results are in accordance with
the same studies. When all of the findings are summarized, results confirm that Laccobius spp. accumulate more elements than their environments
and can play important role to transport the elements from the
sediments up into food web. These insects take up elements in excess
of their need or they do not need such as Pb, As and accumulate
these elements at higher concentration than their surrounding
environments. As a food source of fishes, birds these insects represent
a dangerous link for the transference of elements to upper trophic
levels and finally to human. Analysis of the heavy element status of
the sediment and water complemented the study. The accumulations
of elements in the sediments reduce environmental quality and
leads to bioaccumulation of elements by aquatic organisms. Despite
being widely disturbed in Turkey, there is no Laccobius spp. based
study to assess ecological quality. [19] recorded 11 spp. of Laccobius
from Erzurum region. In this study were collected only 5 species.
This decrease can be due to wide spread pollution in Erzurum. This
pollution may cause in a near future severe damage to Erzurum
wetlands and also other aquatic communities. Many of the measured
heavy elements may have detrimental effects to the environment
include human health. Thus, understanding the status and level of
heavy element pollution is the basic idea for remediating the pollution
from the environment. If pollution prevention does not occur,
environmental pollution damage, decreasing of tourism activities,
public health risk will rise in the future. This work was supported by Atatürk University Scientific
Research Project (SRP) under grant (162/2012), and is a part of first
author’s Ph. D. Thesis. The authors express their sincere gratitude to
Dr. Bugrahan EMSEN in department of Biology at the University of
Karamanoglu Mehmet Bey, for statistical analysis of samples.
Introduction
Materials and Methods
Results
Discussions
Conclusion
Acknowledgments
References