Air Pollution in Study (2013)

Air Pollution Study in Croatia Using Moss Biomonitoringand ICPAES and AAS Analytical Techniques

Zdravko Spiric Ivana Vuckovic Trajce Stafilov

Vladimir Kusan Marina Frontasyeva

Received: 8 December 2012 / Accepted: 11 February 2013 / Published online: 7 March 2013

Springer Science+Business Media New York 2013

Abstract Moss biomonitoring technique was applied in a

heavy-metal pollution study of Croatia in 2006 when this

country participated in the European moss survey for the

first time. This survey was repeated in 2010, and the results

are presented in this study. For this purpose, 121 moss

samples were collected during summer and autumn 2010.

The content of 21 elements was determined by inductively

coupled plasmaatomic emission spectrometry and atomic

absorption spectrometry. Principal component analyses

was applied to show the association between the elements.

Six factors (F1F6) were determined, of which two are

anthropogenic (F3 and F6), two are mixed geogenic

anthropogenic (F1 and F5), and two are geogenic factors

(F2 and F4). Geographical distribution maps of the ele-

ments over the sampled territory were constructed using

geographic information systems technology. Comparison

of the median values of some of the anthropogenic ele-

mentssuch as arsenic, cadmium, chromium, copper,

mercury, nickel, lead, vanadium, and zincwith those

from the 2006 study shows that anthropogenic pollution

has changed insignificantly during the last 5 years. The

data obtained in the investigation in Norway are taken for

comparison with pristine area, which indicates that Croatia

is somewhat polluted but still, shows a more favourable

picture when compared with two neighbouring countries.

Environmental pollution is one of the largest problems the

world faces today. It is an issue that troubles our economy,

our health, and our daily lives. The contamination of the

environment is also being linked to some of the diseases

that are currently present. The major sources of air pollu-

tion are power and heat generation, burning of solid wastes,

industrial processes, and transportation. The best way to

determine the extent of contamination in living organisms

is by measurement of the levels of contaminants in the

organisms themselves, for which plants have proven to be

the most suitable. The use of mosses as biomonitors is a

convenient way of determining levels of atmospheric

deposition (Puckett 1988). Many studies have showed that

terrestrial mosses have good bioaccumulating ability, par-

ticularly for heavy metals, where metal concentrations

reflect deposition without the complication of additional

uptake by way of a root system (Bargagli et al. 1995;

Mulgrew and Williams 2000; Gjengedal and Steinnes

1990). The moss biomonitoring technique, first introduced

in Scandinavia, has proven to be feasible for studying the

atmospheric deposition of heavy metals as well as other

trace elements (Ruhling and Tyler 1971; Gjengedal and

Steinnes 1990; Ruhling 2002). A few studies have shown

that the content of metals in moss is correlated with

atmospheric deposition during the moss growth period

(Berg and Steinnes 1997; Thoni et al. 2011).

Many national and international organizations have

performed a number of monitoring and modelling studies

to determine the levels of heavy metals and toxic metals in

the air, soil, and water to take further precautions. The first

Z. Spiric (&) V. KusanInstitute for Applied Ecology, OIKON Ltd., Trg senjskih

uskoka 1-2, 10020 Zagreb, Croatia

e-mail: [email protected]

I. Vuckovic T. StafilovInstitute of Chemistry, Faculty of Natural Sciences and

Mathematics, Ss. Cyril and Methodius University,

POB 162, 1000 Skopje, Macedonia

M. Frontasyeva

Frank Laboratory of Neutron Physics, Joint Institute for Nuclear

Research, Str. Joliot-Curie6, 141980 Dubna, Moscow Region,

Russian Federation

123

Arch Environ Contam Toxicol (2013) 65:3346

DOI 10.1007/s00244-013-9884-6

local study of mercury (Hg) and some other elements from

the petroleum industry in Croatia was undertaken in

19962004 using lichens (Horvat et al. 2000). In

20052006, Croatia participated for the first time in a moss

survey in the framework of the International Cooperative

Programme on effects of air pollution on natural vegetation

and crops with heavy metals in Europe (UNECE ICP

Vegetation) (Spiric et al. 2012). The method of moss

monitoring has become well established and is used on a

national basis to evaluate the level of heavy-metal pollution

in European countries every 5 years. The first survey

started in 1990.

In this study, a portion of the results obtained for the

2010 moss survey will be presented. The recommended

species of mosses for metal-deposition monitoring (Hyp-

num cupressiforme, Pleurozium schreberi, Brachythecium

rutabulum, and Homalothecium sericeum) (Ruhling et al.

1987; Ruhling 1994; Buse et al. 2003) were collected from

121 sampling sites evenly distributed throughout the ter-

ritory of Croatia. The purposes of this study were as fol-

lows: (1) to present the results from the 2010 moss survey

in Croatia based on moss biomonitoring technique, (2) to

compare these with the results obtained in the 2005 survey

in Croatia to evaluate temporal deposition trends, (3) to

compare the results obtained with similar 2005 surveys

performed in some neighboring countries, and (4) to

compare the result with those obtained in the latest survey

(2010) in Norway, which were used for comparison with a

pristine area.

Study Area

The Republic of Croatia covers an area of 87.677,

56.610 km2 of which is land mass. Croatia is a Mediter-

ranean and southeastern European country geographically

located between 13.5s and 19.5s eastern longitudes and

42.5s and 46.5s northern latitudes. It is located between

BosniaHerzegovina and Serbia in the east, Slovenia in

the west, Hungary in the north, and Montenegro and

the Adriatic Sea in the south. Croatian territory is divided

into three large natural and geographic entities: Half of

the territory (54.5 %) is located in the Pannonian and

Fig. 1 Geographical position ofCroatia

34 Arch Environ Contam Toxicol (2013) 65:3346

123

peri-Pannonian region, one-third (31.6 %) belongs to the

Adriatic part, and the rest is hilly and mountainous area

(14 %). Most of Croatia has a moderately warm and

rainy continental climate as defined by Koppen climate

classification (Halamic and Miko 2009). The climate is

strongly conditioned by relief, ranging from continental

temperate in the north to the Mediterranean climate along the

coastline and in the adjacent hinterland. Temperatures

increase from west to east, whereas precipitation varies

reversely. Mountain ranges are characterized by high amounts

of precipitation (B2000 mm/years), whereas areas in their

shadow or in the mainland (Pannonian region) receive little

precipitation (\800 mm/years) (Halamic et al. 2012).Two geologically specific and different areas can be

distinguished within the area of the Republic of Croatia: (1)

the area of north Croatia, or the Pannonian part, composed

predominantly of clastic sedimentary rocks and metamor-

phic and magmatic rocks; and (2) the mountainous and

coastal part, which is made up of predominantly of car-

bonate rocks (Halamic and Miko 2009).

Croatia has a large reserve of freshwater and is one of the

richest areas in Europe in terms of biodiversity. Industries are

mostly located near the larger cities (Zagreb, Sisak, Kutina,

Osjek, Split, Sibenik, etc.). The main industries are heavy

industry, light industry, metallurgy, chemical, steel, and tex-

tile industry. There are also thermoelectric power plants and

oil deposits. All of these previously mentioned industries are

reasons for anthropogenic air pollution with heavy metals. As

a consequence of the overall economic recession since 1990,

air emissions of the main pollutants from stationary and

mobile sources in Croatia have decreased and have a low

influence to the environment. Croatia has a relatively clean

environment compared with European Union industrial

countries (Fig. 1)

Materials and Methods

Sampling

Moss samples of the four most dominant moss species

H. cupressiforme, P. schreberi, B. rutabulum, and H. seri-

ceumwere collected during the summer and autumn in

Fig. 2 Locations of mosssampling points in 2010

Arch Environ Contam Toxicol (2013) 65:3346 35

123

2010 at 121 sampling sites evenly distributed over the

territory of Croatia. The map of sampling points is shown

in Fig. 2. The sampling was performed in accordance with

the strategy of the European Moss Survey Programme and

the monitoring manual of the ICP Vegetation Coordination

Centre (Ruhling and Steinnes 1998; Harmens 2009).

Sampling sites were located at least 300 m from main

roads, 100 m from local roads, and 200 m from villages.

Each sampling point was situated at least 3 m away from

the nearest tree canopy. Samples in forests were collected

primarily in small gaps, without influence from canopy drip

from trees, preferably on the ground. Each sample was

composed of 510 subsamples collected within an area of

50 9 50 m2 to make the moss samples representative. A

separate set of polyethylene gloves was used for collection

of each sample. Collected material was stored in paper

bags.

Sample Preparation

Moss samples were air-dried and cleaned of soil particles

and other contaminants. Only the 34 cm of green and

greenbrown shoots from the top of the moss, which rep-

resents the last 3 years of growth, were separated,

homogenized, and used for analyses (Harmens 2009). All

of the reagents used for this study were of analytical grade:

nitric acid; trace pure (Merck, Germany); hydrogen per-

oxide, p.a. (Merck, Germany); and bidistilled water.

Approximately 0.5 g of moss material was placed in a

Teflon vessel and treated with 7 ml of concentrated nitric

acid (HNO3) and 2 ml of hydrogen peroxide (H2O2)

overnight. The moss material was put in microwave

digestion system (Mars; CEM, USA) for full digestion.

Digestion was performed in two steps: (1) ramp: temper-

ature 180 C, time 10 min, power 400 W, and pressure20 bar; (2) hold: temperature 180 C, hold time 20 min,power 400 W, and pressure 20 bar. Digests were filtrated

and quantitatively transferred to 25-ml calibrated flasks

with the addition of bidistilled water to a whole volume of

25 ml.

Instrumentation

Inductively coupled plasmaatomic emission spectrometry

(ICP-AES; 715ES; Varian, USA) was used for analyzing the

content of 19 elements (silver [Ag], aluminum [Al], barium

[Ba], calcium [Ca], cadmium [Cd], chromium [Cr], copper

[Cu], iron [Fe], lithium [Li,] potassium [K], manganese

Table 1 Descriptive statistic for all chemical elements analysed in 121 moss samples (mg kg-1)

Xa Xg Median Minimum Maximum P10 P90 rx

Ag 0.035 0.027 0.032 0.001 0.155 0.010 0.061 0.024

Al 1061 802 878 112 4493 320 1995 808

As 0.39 0.30 0.36 0.05 1.00 0.09 0.70 0.24

Ba 24.53 20.80 20.64 4.49 94.30 10.40 39.95 15.87

Ca 7399 6786 6632 2649 20795 4136 11984 3241

Cd 0.43 0.37 0.38 0.10 1.42 0.19 0.74 0.24

Cr 2.25 1.86 1.94 0.41 8.55 0.90 3.91 1.48

Cu 9.23 8.75 8.53 4.72 22.69 5.96 13.13 3.29

Fe 881 689 789 85.00 4028 305 1658 638

Hg 0.043 0.039 0.043 0.010 0.145 0.023 0.063 0.018

K 4366 4008 3891 1552 9279 2411 6883 1859

Li 0.74 0.57 0.55 0.11 4.27 0.24 1.42 0.60

Mg 3099 3023 3059 1619 4740 2254 4051 683

Mn 161 106 99.10 16.10 928 31.60 324 165

Na 131 125 120 65.00 304 89.00 181 43.96

Ni 3.70 3.15 3.16 1.04 14.66 1.61 6.39 2.35

P 1237 1121 1134 419 3117 631 1954 570

Pb 3.79 3.27 3.21 1.11 36.64 1.87 5.48 3.42

Sr 17.09 15.59 16.00 4.74 54.03 9.02 25.54 7.56

V 3.50 2.42 2.55 0.23 37.26 0.86 6.17 4.05

Zn 27.13 25.18 24.80 11.64 77.13 16.31 41.61 11.86

Xa aritmetical mean; Xg geometrical mean; P10 10th percentile; P90 90th percentile; rx SD


123

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123

[Mn], magnesium [Mg], sodium [Na], nickel [Ni], phos-

phorus [P], lead [Pb], strontium [Sr], vanadium [V], and zinc

[Zn]) in moss samples. Ultrasonic nebulizer CETAC (ICP/

U-5000AT?; Varian, USA) was used for better sensitivity

and signal stability. The calibration solutions were prepared

from a 1000 mg L-1 stock solution (ICP-multielement

standard solution IV; Merck, Germany).

The determination of As and Hg using ICP-AES is

difficult at low concentration levels. Therefore, these ele-

ments were determined by AAS. As was determined by

Zeeman electrothermal AAS (SpectrAA 640 Z; Varian,

USA), whereas Hg was determined by cold vapour AAS

(SpectrAA 55B; Varian, USA) using a continuous flow

vapour generation accessory (VGA-76; Varian, USA). The

optimal instrumental parameters for these techniques are

given in previously published articles (Balabanova et al.

2010; Serafimovski et al. 2008).

Statistical Analysis and Mapping

Data matrix for statistical analysis was prepared using all

field observations, analytical data, and measurements. Data

processing was performed using software Statistica (Stat-

Soft version 6). Descriptive statistic for all (n = 21)

chemical elements (Ag, Al, As, Ba, Ca, Cd, Cr, Cu, Fe, Hg,

K, Li, Mg, Mn, Na, Ni, P, Pb, Sr, V, and Zn) from 121

locations were calculated (Tables 1 and 2). Parameters of

descriptive statistics used were as follows: arithmetical

mean, geometrical mean, median, minimum, maximum,

10th percentile, 90th percentile, and SD.

Relationships between heavy-metal contents in mosses

and some environmental, geologic, and anthropogenic fac-

tors have been established by multivariate coordination

methods (Figueira et al. 2002). Principal component analysis

and cluster analysis are frequently used chemometric

methods for the assessment of relationships among heavy

metals in mosses and the identification of their pollution

sources (Gramatica et al. 2006; Pesch and Schroeder 2006).

To discover the associations of chemical elements and to

decrease the number of variables for the obtained data

principal component analysis and factor analysis (PCFA),

R-mod was used (Johnson and Wichern 2002). All sites and

all 21 chemical elements were included in the PCFA. No

standardisation of variables was performed because the

variable standardisation did not give any improvement dur-

ing the analysis preparation and testing phase. For orthogo-

nal rotation, varimax method was used. Other parameters of

analysis were performed according to Stevens (2002): The

number of calculated factors was set to 6 and the minimum

eigenvalue to 1. The threshold of statistical significance was

set to 0.65. With such a high threshold, we decreased the

number of significant loadings in particular factors. It is

clearly visible in factor 2, where Zn has a loading of 0.645,

and in factor 4, where Sr has a loading of 0.646 (Table 3).

For the spatial distribution of factor scores, universal

krigging, i.e., the linear variogram interpolation method,

was used (Barandovski et al. 2012). The parameters of

interpolation were as follows: the number of closest points

was 8, the maximum distance was 200 km, and the basic

grid cell size was 500 m 9 500 m. Spatial representation

for interpolated factors were made by using percentile class

limits of 10 (010, 1020, 2030 90100).

Results and Discussion

Results of the descriptive statistics made for all 21 chem-

ical elements are listed in Table 1. Values of medians and

ranges obtained for the elements in the present study are

compared with the values of the same parameters obtained

in the 2005 study in Croatia and two neighbouring

Table 3 Factor analysis of the data obtained in moss samples fromCroatia

Rotated matrix component

Factor

1

Factor

2

Factor

3

Factor

4

Factor

5

Factor

6

Ag 0.12 0.12 0.72 0.10 0.29 0.09

Al 0.97 0.04 0.01 0.10 0.13 0.02

As

(ETAAS)

0.39 0.26 0.07 0.28 0.36 0.26

Ba 0.09 0.30 0.82 0.11 0.08 0.03

Ca 0.31 0.01 0.31 0.66 0.32 0.04

Cd 0.81 0.24 0.02 0.07 0.14 0.32

Cr 0.93 0.04 0.02 0.07 0.26 0.08

Cu 0.30 0.43 0.04 0.01 0.47 0.50

Fe 0.97 0.02 0.02 0.06 0.12 0.05

Hg (AAS) 0.21 0.03 0.12 0.17 0.31 0.58

K 0.15 0.90 0.03 0.11 0.06 0.05

Li 0.97 0.03 0.02 0.03 0.00 0.00

Mg 0.27 0.75 0.12 0.03 0.01 0.05

Mn 0.06 0.04 0.91 0.03 0.03 0.08

Na 0.03 0.29 0.22 0.65 0.23 0.10

Ni 0.42 0.05 0.13 0.05 0.74 0.12

P 0.04 0.83 0.27 0.15 0.12 0.00

Pb 0.13 0.08 0.11 0.01 0.19 0.81

Sr 0.19 0.36 0.07 0.65 0.12 0.05

V 0.39 0.06 0.10 0.10 0.72 0.09

Zn 0.16 0.64 0.10 0.01 0.36 0.40

%

Explained

25.0 14.9 11.0 7.1 9.9 7.8

Prp total 0.25 0.15 0.11 0.07 0.09 0.07

Bolded values for separate element shows that the element belongs to

the corresponding factor group

ETAAS Electrothermal atomic absorption spectrometry; Prp. total

Total proportion


123

countries, Serbia and Slovenia. The data obtained from the

latest research in Norway in 2010 were used for compari-

son with a pristine area. These comparisons are listed in

Table 2. The Norwegian values were obtained by ICP

mass spectrometry method and are based on nitric acid

solutions (the same as in the present study), possibly

leaving out fractions of the elements contained in silicate

minerals (soil particles).

From data listed in Table 2, it can be seen that the

median values and ranges of all elements obtained in this

study are similar to the median values and ranges obtained

in the 2005 study (Spiric et al. 2012). Only a few elements

have slightly greater values for medians. The median value

for Cd is 1.4 times, for Cu 1.13 greater, for Mg 1.44, for Ni

1.17 times, and for Pb 1.3 times greater. For some typical

anthropogenic elements, such as Cr, Hg, V and Zn, lower

median values are recorded. For these elements in 2005,

median values of 2.8 mg, 0.064 mg, 3.1 mg, and

29 mg kg-1, respectively, are measured, whereas in the

present study, for the same elements, median values of

1.94, 0.043, 2.55, and 24.8 mg kg-1, respectively, are

measured. According to this comparison and the decrease

of median values for some important anthropogenic ele-

ments, it is obvious that the state of anthropogenic pollu-

tion in Croatia in the last 5 years has not changed

significantly even as the anthropogenic influence is

decreasing.

From the comparison of median values for those ele-

ments for which there is data from Serbian moss samples

(Harmens et al. 2008), it can be seen that the median values

for all heavy metals in Croatian moss samples are lower,

except for Cd (0.38 mg kg-1), which has a slightly higher

value. Comparing Croatian with Slovenian moss analyses

(Harmens et al. 2008), it can be concluded that these two

countries have similar median values for all elements. Only

Cd, Cu, and Ni have (insignificantly so) 1.15, 1.04, and

Fig. 3 Geographicaldistribution of factor 1 scores

(Al, Cd, Cr, Fe, and Li)


123

1.15 times greater median values in Croatian moss sam-

ples. It should be pointed out that the Croatian data refers

to sampling in 2010, whereas the data from the other two

Balkan countries are from the 2005 to 2006 moss survey,

and the situation in those countries may have changed in

the meantime.

The data for Norwegian moss samples refers to the

mosses taken from the latest study in 2010 (Steinnes et al.

2011). Norway, as pristine area, has lower median values

for typical air pollution elements (As, Cd, Cr, Cu, Ni, Pb,

and V), whereas Croatia has lower median values only for

Ba (20.64 mg kg-1), Hg (0.043 mg kg-1), and Zn

(24.8 mg kg-1).

Association of Chemical Elements

A multivariate statistical approach was adopted to assist the

interpretation of metal concentration data in moss samples

and to visualize the sites with greater metal content. Factor

analysis is a multivariate statistical technique commonly

used in atmospheric deposition and other environmental

studies to deduce source from data set (Garson 2000). With

PCFA, the characteristics of the 21 individual elements

were decreased to 6 synthetic variables (F1 to F6), which

account for 75.7 % of the total variability of treated ele-

ments (Table 3). The first three factors are reliable (they

have more than three significant loadings) and explain

50.9 % of total variability. The other three factors are less

reliable. Factors 4 and 5 have two significant loadings, and

factor 6 only has one significant loading. Together, they

explain 24.8 % of the total variability.

Factor 1

Factor 1 has high factor loadings for Al, Cd, Cr, Fe,

and Li and represents mixed (geogenicanthropogenic)


(K, Mg, and P)


123

association of elements. It is the strongest factor repre-

senting 25 % of the total variability. The geographical

distribution of factor 1 is shown in Fig. 3. The regional

distribution of Al, Fe, and Li are typical for the group of

crustal elements predominantly supplied to the moss by

windblown soil dust; thus, the content is not solely due to

atmospheric deposition. Al compounds are insoluble, and

most of the Al found in biological systems comes from dust

contamination (Pais and Jones 1997). In contrast, high

values for Cd and Cr, especially around industrial areas

near Zagreb (sampling site no. 93B, Sisak [no. 104], Kutina

[no. 51], Osjek [no. 40], and Sibenik [no. 81A]), indicate

that the contents of these elements are the result of

anthropogenic sources. According to the Geochemical

Atlas of Croatia (Halamic and Miko 2009), soils of coastal

Croatia have greater contents of these two elements, and it

can be concluded that greater values for their content in

moss samples collected from Coastal region have a natural

origin. The reasons for higher Cd and Cr values near

Zagreb, Sisak, Kutina, and Osijek are probably due to

chemical and heavy-metal industries and near Sisak and

Sibenik are due to metallurgy.

Factor 2

Factor 2 (K, Mg, and P) is the second factor accounting for

14.9 % of total variability (Fig. 4). These elements are

typical for crustal material,and are significantly influenced

by soil particles attached to the moss samples. K, Mg, and

P are lithophile elements, and their increased contents are

typical for the northern part of the country in the regions of

central Croatia, Posavina, Podravina, and part of moun-

tainous Croatia. Igneous and metamorphic rocks rich in K

minerals are represented in the central (Slavonic moun-

tains) and western parts (Moslavacka, Medvednica, and

Ivanscica Mountains) of northern Croatia, which lead to

K-enrichment in the soil and moss samples (Halamic et al.

2012). In these regions, Mg content is a direct consequence


(Ag, Ba, and Mn)


123

of the geological substrate (bedrock) because these areas

are built of Mesozoic dolomite (Halamic and Miko 2009).

In the Podravina region, high contents of K and Mg in moss

samples are a result of natural occurrence. Flood plain

sediments of the Drava River are composed of particles

originating from weathering of igneous and metamorphic

rocks in the Alps (Slovenia, Austria), which abound in K

minerals and from which K is deposited on moss samples.

The high content of ferromagnesian minerals in the

deposits of the Sava and Danube flood plains can explain

the high Mg contents in moss (Halamic and Miko 2009;

Halamic et al. 2012). In coastal Croatia, K content is

generally associated with siliciclastic lithology, namely,

turbidite deposits and micaceous sandstones (Halamic et al.

2012). Greater contents of P are registered in areas with

intensive agricultural production (central Croatia, Posavi-

na, Podravina, and coastal Croatia). P is introduced into

soils and mosses due to intensive agricultural production

and the use of P-based artificial fertilizer. P also can be

found in soils and moss samples as a result of geogenic

origin in heavy mineral fraction apatite (Halamic and Miko

2009).

Factor 3

Factor 3 has high loadings for Ag, Ba, and Mn. The dis-

tribution map is shown in Fig. 5. From the map of distri-

bution, it can be noted that the highest distribution of those

elements is focused in major industrial centres. According

to this, it can be concluded that this is an anthropogenic

factor. The highest values of Ag, Ba, and Mn are recorded

in the moss samples collected near Zagreb at sampling site

no. 94 and in Sisak at sampling sites no. 104 and 105. Ag

has the highest value in the sample collected at sampling

site no. 104 (0.115 mg kg-1). Ba has highest content in


(Ca and Na)


123

the sample at sampling site no. 94 (928 mg kg-1), whereas

Mn has the highest content in the sample collected at

sampling site no. 105 (94.3 mg kg-1). These three ele-

ments probably occur in greater contents in moss samples

as a result of industrial activities, processing of ores, steel

refining, cement manufacture, and similar activities near

Zagreb, Sisak, Kutina, and some other industrially devel-

oped cities.

Factor 4

Factor 4 is a geogenic factor that is present with Ca and Na

(Fig. 6).Ca and Na are the main elements in the Earths

crust. Their contents in moss samples are mainly from

geogenic origin. Those elements are found in igneous rocks

(ultrabasites, basalts, and granites). They are also

commonly found in the form of carbonates. High contents

of Ca are registered in mosses collected in central Croatia

where carbonate rocks as bedrock are dominant. Here, high

contents of Na are found as a result of igneous and clastic

rocks that contain Na-rich minerals. Increased Ca contents

are found in samples collected near the Valley of Sava

River where flood sediments predominantly consist of

carbonate pebbles and fine-grained deposits, which are also

deposited on moss samples. The highest contents of Na are

found in the Podravina region where sediments are enri-

ched with minerals having high Na concentrations. The

coastal region contains the highest content of Ca, which is

associated with undeveloped soils on flysch bedrock

(Halamic and Miko 2009). High content of Na in moss

samples collected from the coastal region is probably a

result of the sea influence.


(Ni and V)


123

Factor 5

Factor 5 shows high loadings for Ni and V (Fig. 7). It is

generally an anthropogenic factor but can also be of geo-

genic origin. High contents of these elements in the

northern parts of Croatia are of anthropogenic origin. Ni

and V may be associated with burning of heavy fuel oil for

heating and electricity production or with metal industry.

The two metals show sufficient covariation to support the

conclusion that combustion of heavy fuel oil is a significant

factor. Highest contents of Ni (14.66 mg kg-1) and V

(37.26 mg kg-1) are found in the moss sample collected

near Rijeka at sampling site no. 108 where a thermoelectric

plant is located, which is an anthropogenic source of these

elements. In the vicinity of developed industrialized cities,

such as Zagreb and Sisak, greater contents of these ele-

ments are also found. According to the Geochemical Atlas

of Croatia, it can be noted that high contents of Ni and V in

the regions of coastal and mountainous Croatia are found

as a result of geogenic influence. These elements are

associated with a complex of Palaeozoic siliciclastic rocks

(Halamic and Miko 2009).

Factor 6

Factor 6 is dominated by Pb and is an anthropogenic

factor (Fig. 8). Pb is a nonessential element, and it is

harmful. It is introduced into the environment by leaded

gasoline, mining and smelting activities, coal, and waste.

The highest content of Pb (36.64 mg kg-1) in moss is

found at sampling site no. 98, near Zagreb, as a result of

anthropogenic influence of the developed industries in this

region. In the Drava River valley, high contents of this

element are also found as a consequence of Pb ore deposits

situated more upstream (Austria, Slovenia) where intense

mining activity has existed for the last two centuries


(Pb)


123

(Bleiberg, Mezica) (Sajn et al. 2011). High contents of Pb

are also found in moss samples collected from areas with

developed industry (Sisak, Kutina, Rijeka, Split) as a

result of anthropogenic activities.

Conclusion

In this study, moss biomonitoring technique was applied

for investigation of air pollution in Croatia. The content of

21 elements was determined in 121 moss samples. Statis-

tical analyses were performed on the obtained results. With

PCFA, the characteristics of 21 individual elements were

decreased to 6 synthetic variables (F1 to F6), of which 2

are anthropogenic (F3 and F6 [Ag, Ba, Mn, and Pb]), 2 are

mixed geogenic-anthropogenic (F1 and F5 [Al, Cd, Cr, Fe,

Li, Ni, and V[), and 2 are geogenic (F2 and F4 [K, Mg, P,

Ca, and Na]). By comparing the results of this study with

those obtained in 2005, it can be concluded that the air

pollution, along with some of the anthropogenic elements,

in Croatia has not significantly changed. Compared with

neighboring countries, Croatia is less polluted than Serbia

and has similar values of the content of typical anthropo-

genic elements as those obtained in the investigation in

Slovenia. By comparing with the data obtained in the latest

study in Norway as the least anthropogenically polluted

area of Europe, it may be noted that Croatia is negligible

polluted. The main anthropogenic factors are highly

developed light and heavy industry, transportation, steel

industry, textile industry, thermoelectric plant, and oil

deposits, which activities are performed near large indus-

trialized cities, such as Zagreb, Sisak, Kutina, Split, Rijeka,

and Sibenik. Moss samples collected near these regions

showed the highest content of heavy metals typical for air

pollution of anthropogenic derivation.

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c.244_2013_Article_9884.pdfAir Pollution Study in Croatia Using Moss Biomonitoring and ICP--AES and AAS Analytical TechniquesAbstractStudy AreaMaterials and MethodsSamplingSample PreparationInstrumentationStatistical Analysis and Mapping

Results and DiscussionAssociation of Chemical ElementsFactor 1Factor 2Factor 3Factor 4Factor 5Factor 6

ConclusionReferences

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