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MA
ST
ER
THESIS
Master's Programme in Applied Environmental Science, 60 credits
Environmental presence of heavy metalcontamination of industrial tributary in a ruralriver catchment.
-A case study on Trönningeån stream in SouthernSweden.
Irshad Mohamed
Degree Project in Environmental Science, 15 credits
Halmstad 2017-06-01
1
Abstract
Heavy metal pollutants are a worldwide concern. It causes negative effects on aquatic
organisms and human health. Heavy metals concentration and transport of copper, zinc and
cadmium were investigated in high and low flow conditions in Trönningeån River, southern
Sweden. A total of 33 surface water samples collected from the river and Kistingebäcken
tributary were analyzed. Concentration (high to low) of heavy metals in the Trönningeån river
and its tributary were- copper(Cu) > zinc (Zn) > cadmium (Cd). The concentration of Copper
was found to be high in low flow condition whereas in the case of zinc, high concentrations
were found in both the flows (high and low). Study further showed that, the tributary has high
pH and conductivity. And finally, the study concluded that there is high concentration and
transport of heavy metals in the above-mentioned industrial tributary.
Keywords: Heavy metal pollution, Heavy metal transport, Trönningeån river, industrial
tributary.
2
Contents
1. Introduction………………………………………….....4
2. Background…………………………………………….4
3. Objective…………………………………………...…..5
4. Materials and methods……………………………..…..6
5. Results………………………...………………………..8
6. Discussion……………………………………………..11
7. Conclusion…………………………………………......13
8. Recommendations. …………...……………………….13
9. References……...……………………………………...14
I. Appendix…………………………………………17
3
1. Introduction
This study aims to assess heavy metal pollution in the stream Trönningeån in southern Sweden.
The study could be a possible addition to the LIFE GOOD-STREAM project which is
currently, focusing on the complete catchment area of the rural stream Trönningeån, southern
part of Sweden (fig1) and installation of wetlands. According to the VISS database (Vatten
Information Systemet Sverige); a database for classification of all Swedish waters according
to the European Water Framework Directive), the rural stream has a moderate to poor water
quality (Vattenmyndigheterna.se, 2017). The LIFE GOOD-STREAM project is mainly
concentrated on retention of nutrients using wetlands. Assessment of heavy metals is expected
to be an added benefit to the already undergoing LIFE GOOD-STREAM project.
2. Background
According to World Health Organization, zinc, copper and cadmium are among 10 toxic heavy
metals with major issue (World Health Organization, 2017). Heavy metal pollution in river and
streams is primarily caused due to industrialization (Nguyen et, al., 2016; Staley et al., 2015).
Industries such as - textiles industries, diaries, recycle facilities, fertilizer industries, tin and
drug industries located besides, the river catchment are the primary causes for heavy metal
pollution (Patil and Kaushik, 2016). River sediments become the storage of heavy metals,
which in turn becomes the potential secondary source of metal pollution to the connected
aquatic systems (Wang, 2017). As the nature of heavy metals are non-degradable and toxic,
heavy metal pollution in rivers has been the subject of several studies and hence has drawn
global attention towards it (Shafie et al, 2014).
Heavy metals are deposited in the river sediments during the process of adsorption,
precipitation and hydrolyzation (Loska and Wiechuła, 2003). Also, it has been observed that
the mechanical disturbance of the sediments increases the risk of contamination when they are
re-suspended (Ishaku et al., 2016). Toxicity of zinc, copper and cadmium (Molahoseini, 2014;
Khan et al., 2013) in the aquatic environment increases the risk of entering in to the living
systems directly or indirectly, causing serious health issues (Guan et al., 2014; Chen et al.,
2016). Long term zinc, copper and cadmium exposure leads to health problems such as
physiological problems in blood production and liver malfunction.
Also, zinc and cadmium intake through food and water could cause metal poisoning for which
appropriate medical care must be taken to avoid further damage (Baby et al., 2011). A previous
study has identified traces of heavy metal (Zn and Cu) samples in teeth dentine of humans, that
4
could have toxic effect. The study concluded that the teeth dentine tests can act as a possible
biomarker for environmental pollution (Asaduzzaman et al., 2017).
A study observed that aquatic systems are prone to heavy metal pollution especially in fishes
like Tilapia nilotica. Fish liver contained traces of Zn and Cu (Rashed, 2001). As per this study,
heavy metal concentration in different parts of the fish varied with the growth of the fish and
that the heavy metal concentration in the edible parts of the fish were under permissible safety
level. Similar case was found in another study where the subject was the muscle of a
commercial shrimp (Metapenaeus affinis) found in the muscle, liver and gills of two fish
species (Thryssa vitrirostris and Johnius belangerii) taken from Arvand river in the northeast
Persian Gulf (Monikh et al., 2015).
An initial monitoring performed within the LIFE-GOODSTREAM project indicated that the
water quality in two tributaries to the stream Trönningeån was strongly influenced by industrial
activities (Martens, 2016). This included indications of heavy metal pollution (unpublished
data) suggesting that the LIFE-GOODSTREAM project should not only focus on nutrients or
pollution from agriculture, but also the project should focus on heavy metal pollution, towards
achieving good water quality status of the whole catchment. The municipality has also showed
uncertainty regarding the possibility of heavy metal pollution, because of industries and landfill
near the river tributary Kistingebäcken.
3. Objective
This study aims investigate possible industrial pollution of the tributary Kistingebäcken in the
catchment of the rural stream Trönningeån. It is done by sampling at strategical points and
analyzing water samples, to detect heavy metals such as zinc, copper and cadmium among the
group of heavy metals, in addition to pH and conductivity of water.
Some of the important research questions for the study are:
1. Can concentrations of heavy metals be found in water samples of Kistingebäcken
tributary?
2. Can we detect that industrial activities and landfill situated at the Kistingebäcken is
responsible for the heavy metal pollution in Kistingebäcken tributary by collecting
water sample only?
3. Is Kistingebäcken tributary responsible for the heavy metal pollution in Trönningeån
main stream?
5
4. Materials and methods
The Trönningeån catchment area (Figure 1) is about 32 km² with the stream of length of 12
km. Forest constitute 42% of the surrounding area with close to 50% agricultural land.
Remaining 8% of the land (Länsstyrelsen Hallands Län, 2015) situated in the village Trönninge
with a population of 1555 (Countrybox, 2016). One of the area of Natura 2000 is situated at
the point where the stream leaves Trönninge village. Natura 2000 is a renowned natural reserve
in the territory of European Union. It comprises of Special Areas of Conservation (SACs)
and Special Protection Areas. The network includes both terrestrial and marine sites (Marine
Protected Areas).
This study is focussed on Kistingebäcken tributary (figure 1) which has a length of about 2.9
km with a catchment area of 7 km2. A few industries including recycling industries and a
landfill is situated at the area as shown in appendix (3).
Figure 1:Trönningeån catchment area.
6
Fig 1 shows a Trönningeån catchment area map, from which water samples were collected on
7 locations- 1 is situated close to the landfill. 2 is at Kistingebäcken tributary. 3 represents the
point at which ‘1’ and ‘2’ meet. 4 is a point nearby the industry in the Kistingebäcken tributary.
5 is end of Kistingebäcken tributary. 6 is a point in Trönningeån main stream. 7 is the point
nearby the intersection of Kistingebäcken tributary and Trönningeån main stream.
Water samples were collected on two different conditions- high flow and low flow. Low flow
condition simply means that the water sample was collected before rain on 30th march, 4th April
and 16th April of year 2017 respectively. And high flow condition means sample was collected
after rain on 11th and 13th of April 2017.
A 100-ml clean glass bottle with 1 ml of nitric acid (HNO3) was used to collect 50 ml water
samples using a measurement jar in all the sample locations.
Conductivity and pH of the water samples were measured using a multi meter (HANNA
HI991301). The measurement of pH and conductivity were directly done below the water
surface.
Flow rate was measured using flow rate meter. Procedure followed was to check the number
of rotations per minute. The cross-sectional area of the water sample locations was assessed
using the measured length and breadth. The flowrate was estimated from the measured area
and rotation from the water velocity calibration chart.
For the analysis of the heavy metals, an atomic absorption spectrophotometer was used in the
laboratory at Halmstad University.Sample bottles are arranged based on the sampled location.
Water samples are filtered by the addition of 1 ml of HNO3. Further filtration was done only
for water sample collected from location 2 using filter paper. Initial set up of atomic absorption
spectrophotometer is done. Further calibrations are made in the instrument based on the
required heavy metal analysis in the water samples as given below (Appendix: 4)
The guidance values referred were obtained from the published book- Bedomningsgrunder for
miljokvalitet belonging to ‘Swedish Environmental Protection Agency’. These guidance values
were used as a threshold value to compare with the analysed sample values
(Bedomningsgrunder for miljokvalitet, 1999).
Heavy metal transport refers to the product of concentration of metal found at a location and
the rate of water flow. Water samples at location 5,6 and 7 were collected on different days
characterized by high and low flow.
Since the concentration of cadmium is very low, it was difficult to detect its presence with the
instrument used for the study. Hence for accurate detection, advance instruments will be
needed.
7
5.Results
pH .value
Figure 2: Graph of ph value- for both high and low flow condition (16th April and 11th April)
The pH values for the sampled location for high and low flow respectively were measured. A
graph plotted with the values for high flow and low flow for different dates shows that pH
value at sample locations 1 and 2 is always higher irrespective of high or low flow. The Ph
values in the Trönningeån main stream is showing lower compared to Ph values at
Kistingebäcken tributary.
Conductivity
.
Figure 3 :Graph of conductivity- for both high and low flow condition (16th April and 11th April)
7.85 7.8 7.83 7.47 7.49 7.456.49
7.85
7.78 7.547.46
7.43 7.41 7.58
0
2
4
6
8
10
0 1 2 3 4 5 6 7 8
pH
Sampled Points
pH Level
Low flow-16/Apr High flow-11/Apr
1.121.01
0.250.38 0.4
0.17 0.2
1.38
0.84
0.250.31 0.31
0.17 0.210
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
0 1 2 3 4 5 6 7 8
Co
nd
uct
ivit
y
Sampled locations
Conductivity (S/m)
Low flow-16/Apr High flow-11/Apr
8
The conductivity for the sampled location for high and low flow respectively were measured.
A graph plotted with the values for high and low flow for different dates show that conductivity
value at sample locations 1 and 2 is always higher irrespective of the flow conditions. The
results of conductivity measured is like that of Ph. The conductivity values in the Trönningeån
main stream is showing less value compared to Ph values at Kistingebäcken tributary.
Copper concentration
Figure 4: Graph of copper concentration for both high and low flow condition (16 April and 11th April)
When guidance value and obtained values were compared, on a low flow day, it was found
that there is high risk of biological effect even with short term exposure in all the locations.
Similarly, on a high flow day, locations 1,2 and 4 showed the same result as mentioned
before. Location 3 showed increased risk for biological effects. For location 5,6,7 obtained
sample values had negative readings, so zero value was considered in all the cases.
The analyzed values indicated that the concentration of copper was bit higher in low flow
condition compared to high flow condition. Appendix (1) depicts that the sample values or
the concentration of copper metal is higher in the tributary than the main stream. And some
analyzed values are comparatively higher than guidance value as shown in the table above.
0.1455
0.18250.1641 0.1651 0.1651 0.1589 0.1592
0.0790.096
0.012
0.056
0 0 0
0
0.05
0.1
0.15
0.2
0 1 2 3 4 5 6 7 8
Co
pp
er c
on
cen
trat
ion
Sampled locations
Copper Analysis
Low flow-16/Apr High flow-11/Apr
9
Zinc concentration
Figure 5: Graph of zinc concentration for both high and low flow condition (30 March and 11th April)
When guidance value and obtained values were compared, on a low flow day, it was found
that there is high risk of biological effect even with short term exposure in the locations 2 and
3. Locations 1,4,5 showed increased risk for biological effects. And location 6,7 indicated
that biological effects can occur.
Similarly, on a high flow day, locations 1and 4 showed increased risk for biological effects.
Location 2,3,4 showed high risk of biological effect even with short term exposure. Location
6,7 showed biological effects can occur.
The analyzed values indicated that the concentration of zinc was bit higher in both the
conditions. Appendix (2) depicts that the sample values or the concentration of zinc metal is
higher in the tributary than the main stream. And some analyzed values are comparatively
higher than guidance value as shown in the table above.
0.2748
0.8853
0.5805
0.1864 0.1772
0.0339 0.0303
0.1624
0.4026 0.37450.3268
0.0839
0.01220.02640
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 1 2 3 4 5 6 7 8
Zin
c C
on
cen
trat
ion
Sampled locations
Zinc Analysis
Low flow-30/Mar High flow-11/Apr
10
Heavy metal transport
Table 1 : Heavy metal transport of copper and zinc for both high and low flow condition (kg/day) in sampled
locations.
Two days were chosen taking into consideration the two different levels- Low flow level and
high flow level respectively. During these two days, water samples were analyzed which
were collected from three different locations (Kistingebäcken, Trönningeån and near the
intersection point of the former). Samples were collected from both low and high flow levels
respectively. High heavy metal flow was found in Kistingebäcken.
6. Discussion
When high pH and conductivity are found in industrial stream, it signifies pollution (Patil and
Kaushik, 2016). Former pH and conductivity values, were found at locations 1 and 2, since
they are near to landfill area (A et al., 2017). This shows that the initial research questions
proposed are satisfied with the results obtained.
Heavy metal concentration
If the concentration of copper found in water sample is high, then it causes heavy metal
pollution (Asaduzzaman et al., 2017). Appendix (1) shows the analyzed readings of the copper
concentration in the water samples at the given locations. figure 7 and 8 shows the graph of
heavy metal concentration at locations for both high and low flow conditions respectively.
Referring Appendix (1), copper co8ncentration was found to be higher with respect to the
guidance values given. In fact, copper concentration was found above the range of Class
Sam. NoCopper
(Kg/day)
Zinc
(Kg/day)
4.156116 2.097654
9.720104 2.799004
2.000609 0.954426
2.958486 0.954426
6.432307 1.177805
9.903514 1.8413577
High
Low
High
Low
High
Low
High/Low flow
5
6
11
5(Bedomningsgrunder for miljokvalitet, 1999) which corresponds to high risk of biological
effects. Concentration was found to be clearly higher at locations 1,2 and 3 (i.e., the place close
to the landfill) compared to others.
However, concentration is comparatively lower at location 5 i.e., at the Trönningeån
mainstream. negative readings were obtained for locations 5,6 and 7 during high flow conditions. Hence, it was marked zero. This could be owed to the fact that as it’s been a high
flow condition, metal concentrations could have diluted and hence was not detected in the
instrument. Also, the instrument used in the study cannot determine low concentrations. From
the analyzed results, it can be concluded that Kistingebäcken tributary where industries and
landfills are situated contributes to the high concentration levels of copper in to the main
stream.
If the concentration of zinc found in water sample is high, then it causes heavy metal pollution
(Sun et al., 2017). Appendix (2) shows the analyzed readings of the zinc concentration in the
water samples at the given locations. figure 9 and 10 shows heavy metal concentration at
respective locations for both high and low flow conditions. With reference to Appendix (2),
zinc concentration is found to be higher with respect to the guidance values given. Once again,
zinc concentration is found above the range of Class 5, which corresponds to high risk of
biological effects (Bedomningsgrunder for miljokvalitet, 1999) even with short term exposure
at all locations. But, it is significantly higher at location 2 compared to others. However,
concentration is comparatively lower at location 5 i.e., at the Trönningeån mainstream.
If the concentration of cadmium found in water sample is high, then it causes heavy metal
pollution (Kilunga et al., 2017). The range of cadmium concentration given as the guidance
values is very low to be detected, by the instrument used for the study (Table 2). Hence,
cadmium presence could not be detected effectively.
It has been observed that the occurrence of several toxic heavy metals closely to heavy metal
pollution (Tripathee et al., 2016) Further study can be done on heavy metal concentrations of
other metals like lead(Pb), chromium (Cr), Arsenic(As) and nickel (Ni) in the tributary.
Heavy metal transport
Metal deposits in the rural stream contribute more heavy metal transport to the main stream
(Myangan et al., 2017). Results obtained in the table (1) shows that in high flow, heavy copper
mass transport is observed in Kistingebäcken tributary. It is obtained that mass transport of the
order of 4 kg/ day and 9 kg/ day in high flow and low flow respectively is present in
Kistingebäcken tributary based on the calculations. The copper concentration is only of the
order of 2.9 kg/ day in Trönningeån main stream. It is evident that Kistingebäcken stream is
responsible for heavy metal pollution in Trönningeån river. From the analyzed results, it can
be concluded that Kistingebäcken tributary where industries and landfills are situated
contributes to the high concentration levels of copper in to the main stream.
Results obtained in the table (9) shows that in high flow, heavy zinc concentration is observed
in Kistingebäcken tributary. Based on the calculations done, the weights are of the order - 2.1
kg/ day and 2.7 kg/ day in high and low flow conditions respectively in Kistingebäcken
tributary. The copper mass transport is only of the order of 0.9 kg/ day in Trönningeån main
stream. It is evident that Kistingebäcken stream is responsible for heavy metal pollution in
Trönningeån river.
12
There is no cadmium presence observed in the locations. One of the limitation found in this
case was, the concentration of cadmium is very low. It was difficult to detect its presence with
the instrument used for the study. Hence for accurate detection, advance instruments will be
needed.
7. Conclusion
Metal concentration and transport present at the Kistingebäcken tributary is the main
contributor of heavy metal pollution to the main stream. These results are significantly
alarming, concerning the amount of transport of heavy metal into the main stream.
Study gave the analysis of metal deposition with respect to concentration which concluded that
the presence of copper is higher than zinc. Cadmium metal mass transport was not traced. High
Ph and conductivity value were found at the Kistingebäcken tributary compared to Trönninge
main stream. Further study can be done on heavy metal concentrations of other metals like
lead(Pb), chromium (Cr), Arsenic(As) and nickel (Ni) in the tributary.
Finally, study concluded that there is a very high concentration of heavy metal pollution at
locations 1,2,3 and 4.
8. Recommendations
Heavy metal mass transportation is analyzed to be high and are even above the range of Class
5 based on the guidance values referred. Steps must be taken to ensure that either wetlands or
aeration is created before the water flows into the sea to avoid further damage to aquatic
organisms. It is suspected that improper recycling waste deposit at the industrial facility leads
to, the heavy metal pollution with storm water (Appendix 5). Strict action must be taken by the
concerned Municipality. Further studies are required to detect the presence of cadmium. It is
also recommended to analyze the presence of other heavy metals like Lead, Chromium, Nickel
and Arsenic.
13
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16
I. Appendix
Appendix 1: Copper concentration in water samples.
Appendix 2 : Zinc concentration in water samples.
30-Mar 04-Apr 16-Apr 11-Apr 13-Apr
1 0.093 0.1455 0.079
2 0.063 0.1825 0.096
3 0.01 0.1735 0.1641 0.1671 0.012
4 0 0.1846 0.1651 0.2175 0.056
5 0 0.1678 0.1651 0.1608 0
6 0 0.1622 0.1589 0.1572 0
7 0 0.1651 0.1592 0.1551 0
Sam. No
Date (2017)
Low flow High flow
Sample Analysis
Calibration :(0.5 , 1.0 , 2.0) HNO3(mg/L)
Instrument : Atomic Absorption Spectometer
Type of Heavy Metal: Copper
Slit : 0.5
30-Mar 04-Apr 16-Apr 11-Apr 13-Apr
1 0.2748 0.3623 0.1624
2 0.8853 0.4358 0.4026
3 0.5805 0.2438 0.1796 0.1696 0.3745
4 0.1864 0.1798 0.1122 0.2039 0.3268
5 0.1772 0.164 0.1562 0.1686 0.0839
6 0.0339 0.0289 0.0144 0.0361 0.0122
7 0.0303 0.0336 0.0296 0.0284 0.0264
High flow
Sample Analysis
Instrument : Atomic Absorption Spectometer
Type of Heavy Metal: Zinc
Slit : 1.0
Calibration :(0.1 , 0.5 , 1.0) HNO3(mg/L)
Sam. No
Date (2017)
Low flow
17
Appendix 3: Sampled locations
18
19
20
21
Appendix 4 : Heavy metals analysis
Copper analysis
Slit of the instrument is adjusted to 0.5 and the knob is adjusted to copper tube position
manually. Further, light position is adjusted using position detector card. Air is let out and spark
plug is switched on to ignite the fire. Reading is displayed in the connected computer system.
The reference reading values are obtained using calibration with HNO3 (mg/L) in 0.5,1.0 and
2.0 respectively. The instrument is ready for proper operation once a smooth calibration curve
is obtained. Reading of the diagnosed water is taken (Diagnosed reading (DR)). Collected water
sample reading is taken. Final value is obtained by subtracting diagnosed reading from sample
reading.
Zinc analysis
Slit of the instrument is adjusted to 1 and the knob is adjusted to zinc tube position manually.
Further, light position is adjusted using position detector card. Air is let out and spark plug is
switched on to ignite the fire. Reading is displayed in the connected computer system. The
reference reading values are obtained using calibration with HNO3 (mg/L) in 0.1,0.5 and 1.0
respectively. The instrument is ready for proper operation once a smooth calibration curve is
obtained. Reading of the diagnosed water is taken (Diagnosed reading (DR)). Collected water
sample reading is taken. Final value is obtained by subtracting diagnosed reading from sample
reading.
Cadmium analysis
Slit of the instrument is adjusted to 0.5 and the knob is adjusted to cadmium tube position
manually. Further, light position is adjusted using position detector card. Air is let out and spark
plug is switched on to ignite the fire. Reading is displayed in the connected computer system.
The reference reading values are obtained using calibration with HNO3 (mg/L) in 0.5,1.0 and
2.0 respectively. The instrument is ready for proper operation once a smooth calibration curve
is obtained. Reading of the diagnosed water is taken (Diagnosed reading (DR)). Collected water
sample reading is taken. Final value is obtained by subtracting diagnosed reading from sample
reading.
Appendix 5 : Heavy metal pollution with storm water.
