**5. Case studies**

It is well known that a large scale of chemical pollutants as well their incaution management and damaging land uses make in menace the quality of our surrounding environment at world wide scale. Usually the environmental contaminants (having as main source anthropogenic activities) have great effects on the entire environmental system as draw down loss of habitats, diminish of biodiversity or adverse effects on humans that are exposed to these contaminant through food web chain, health care and/or recreational/working activities.

Fig. 3. Map of the studied regions during period of 2008 - 2010.

The damage of environment quality and living things health status has as result the increasing of necessity to monitor these environmental contaminants. More than that becomes a necessity to monitor their qualitative and quantitative presence even in organisms of living subjects whether it is humans or animals in order to could get regulatory, remedial and treatment decisions.

These studies were conducted in north western part of Transylvania including rural, urban and industrial zones – see map presented in figure 3. In figure 3 zone 1 represent a part of Salaj district which include both rural as well urban sites, zone 2 represent the north part of Cluj district and the western part of Bistrita-Nasaud district, this region including industrial, rural and urban sites while zone 3 represent the south part of Cluj district including urban as well rural areas. In idea to get a clear and realistic image regarding environmental contaminants presence and the degree of exposure of living beings to those contaminants environmental (soil, water) and biota samples (vegetables, biological samples from animal and human origins) were collected monthly in period of 2008-2010.

It is well known that a large scale of chemical pollutants as well their incaution management and damaging land uses make in menace the quality of our surrounding environment at world wide scale. Usually the environmental contaminants (having as main source anthropogenic activities) have great effects on the entire environmental system as draw down loss of habitats, diminish of biodiversity or adverse effects on humans that are exposed to these contaminant through food web chain, health care and/or

**5. Case studies** 

recreational/working activities.

Fig. 3. Map of the studied regions during period of 2008 - 2010.

and human origins) were collected monthly in period of 2008-2010.

regulatory, remedial and treatment decisions.

The damage of environment quality and living things health status has as result the increasing of necessity to monitor these environmental contaminants. More than that becomes a necessity to monitor their qualitative and quantitative presence even in organisms of living subjects whether it is humans or animals in order to could get

These studies were conducted in north western part of Transylvania including rural, urban and industrial zones – see map presented in figure 3. In figure 3 zone 1 represent a part of Salaj district which include both rural as well urban sites, zone 2 represent the north part of Cluj district and the western part of Bistrita-Nasaud district, this region including industrial, rural and urban sites while zone 3 represent the south part of Cluj district including urban as well rural areas. In idea to get a clear and realistic image regarding environmental contaminants presence and the degree of exposure of living beings to those contaminants environmental (soil, water) and biota samples (vegetables, biological samples from animal

#### **5.1 Living things exposure to organochlorine compounds – Case study of paper mills**

During previous studies it was observed an increased presence of organochlorine compounds in regions near Dej city (zone 2 from figure 3). Main organochlorine compounds that were detected were chlorophenols (dichlorophenol, trichlorophenol and pentachlorophenol) and chlorinated solvents (trichloroethylene, tetrachloroethylene and carbon tetrachloride).

Presence of these compounds in environmental samples as soil and water were between range of 0.3 – 32 μgkg-1 and 0.5 – 25.1 μgL-1, respectively, usually with higher levels in case of soil samples.

Major amounts being detected in case of dichlorophenol and trichloroethylene compounds, usually with higher amounts in case of soil samples – see table 2 and figure 4.a. and 4.b.


Table 2. Chlorophenols average amounts in soil and water samples.

Increased presence of these compounds was attributed to the presence of paper mills that discharge its waste water in Somes River (one of the main river that cross northern part of Transylvania which is used as water source both for drinking water purposes and for irrigation networks of agricultural lands). This was demonstrated by the results of environmental monitoring before and after the closing of factory in 2009, when the factory was closed for a period of two months for rehabilitation – see figure 4a and 4b, when it was observed a decreasing tendency of organochlorine compounds presence in environmental samples (as soil and surface water) from the moment when the factory was closed.

In order to evaluate these pollutants impact on living beings it was observed that are quite strong correlation between the amount of these chlorinated compounds in surrounding environment and the amount of organochlorine compounds detected in animals and humans hair samples collected from subjects that live in the corresponding environment – see figure 5. But such dependence was obtained just in this special case, for other regions such correlation (in case or organochlorine compounds) wasn't applicable.

Consulting the obtained results it was observed that the amount of these compounds were lower in case of poultries feathers and higher in the case of cow hair. Also in case of human hair subjects their levels were higher even 30 – 50 percent than in other living beings. This could be explained by the cumulative effects of these pollutants, therefore once with age increases are possible to increase also the levels of environmental contaminants from animals and humans body.

Non-Invasive Matrices Use in Pollution Evaluation

surrounding environment.

the fat from the organisms.

**hydrocarbon compounds** 

were detected usually.

Environmental contaminant

Monoaromatic hydrocarbon

samples.

Polycyclic aromatic hydrocarbon

at Nanoscale Levels: A Way Forward in Ecotoxicological Studies 181

Fig. 5. Organochlorine amount dependence from humans and animal body by the

As regards the amounts detected in human breast milk samples, the amount of chlorinated compounds were higher than in case of hair samples of the same subjects with almost 10 – 15 %. This fact could be attributed to the increased lipid content of breast milk, much more than exist in hair samples, therefore chlorophenol compounds being more easily bounded to

**5.2 Inhabitants and home grown animals' exposure to mono- and polycyclic aromatic** 

As regards monoaromatic hydrocarbon compounds the most detected compounds in the most increased amounts were benzene and toluene, if we take in consideration the fact that their uses was restricted in the last decades. Average values of mono- and polycyclic aromatic hydrocarbons detected in soil and water samples collected from this studied regions are presented in table 3. Higher amounts in case of anthracene and benzo[a]pyrene

Table 3. Mono- and polycyclic aromatic hydrocarbons average amounts in soil and water

Average value during time period 2009 2010

Soil 0.3 – 19.2 µgkg-1 0.2 – 22.3 µgkg-1 Water 0.4 – 16.7 µgL-1 0.8 – 15.9 µgL-1

Soil 0.2 – 22.9 µgkg-1 0.4 – 16.9 µgkg-1 Water 0.4 – 15.2 µgkg-1 0.5 – 13.8 µgkg-1

Environmental compartment

Fig. 4a. Organochlorine compounds amount in surface water while paper mills operating on and off.

Fig. 4b. Organochlorine compounds amount in soil samples while paper mills operating on and off.

Fig. 4a. Organochlorine compounds amount in surface water while paper mills operating on

Fig. 4b. Organochlorine compounds amount in soil samples while paper mills operating on

and off.

and off.

Fig. 5. Organochlorine amount dependence from humans and animal body by the surrounding environment.

As regards the amounts detected in human breast milk samples, the amount of chlorinated compounds were higher than in case of hair samples of the same subjects with almost 10 – 15 %. This fact could be attributed to the increased lipid content of breast milk, much more than exist in hair samples, therefore chlorophenol compounds being more easily bounded to the fat from the organisms.

#### **5.2 Inhabitants and home grown animals' exposure to mono- and polycyclic aromatic hydrocarbon compounds**

As regards monoaromatic hydrocarbon compounds the most detected compounds in the most increased amounts were benzene and toluene, if we take in consideration the fact that their uses was restricted in the last decades. Average values of mono- and polycyclic aromatic hydrocarbons detected in soil and water samples collected from this studied regions are presented in table 3. Higher amounts in case of anthracene and benzo[a]pyrene were detected usually.


Table 3. Mono- and polycyclic aromatic hydrocarbons average amounts in soil and water samples.

Non-Invasive Matrices Use in Pollution Evaluation

blood samples in case of the same person.

mainly through the consumed contaminated food.

pollutants in their tissues at significant concentrations.

**7. Conclusions** 

been showed to be suitable.

compounds.

**8. References** 

**biological samples collected non-invasively** 

at Nanoscale Levels: A Way Forward in Ecotoxicological Studies 183

Main disadvantages of these techniques are the difficulty in making difference between external and internal contamination – as regards hair samples. Also in case of hair samples the results vary intensively once with color, age and gender without existing a good correlation between the same parameters. The lack of a standardized procedure of analysis make more difficult to establish the reliability of results in order to estimate the method uncertainty and making real laboratory intercomparisons. Also a large number of studies showed that there are no correlation between the contaminant level from hair samples and

As regards the study performed by us using of such sampling matrixes made possible to evaluate the impact of certain environmental contaminants on humans and animals (grown for consumption purposes) which are living in such contaminated areas. Also through the significant number of subjects that were monitored we was able to conclude that the environmental contaminants are uptake by humans mainly through food web chains (as a result of consumption of contaminated vegetables and animals). This is the same in case of home grown animals which are similarly exposed to these environmental contaminants

Major environmental pollutants that were detected in different environmental compartments of the studied regions were monoaryomatic hydrocarbons and chlorinated solvents, which were also the most prevalent as presence as well as amount. Methylmercury presence in environment is considered as a special case – environmental contamination in this case coming from the old banned chemical factory on which sites no remediation was applied. In almost all environmental contaminants cases, their presences are attributed to the industrial activities through these regions. All these contaminants leave an impact on the living things that live in the surrounded environment. Vegetables growing on a soil contaminated by former industrial activities may contain chlorinated or hydrocarbon

Uses of noninvasive matrices in both animals as well humans' biomonitoring purposes have

These compounds were detected in all humans and animals' hair samples. Compounds with higher molecular weight masses were easily accumulated by human bodies than the easier

Bhandari, A.; Surampalli, Y.P.; Adams, D.G.; Champagne, P.; Ong, S.K.; Tyagi, R.D.; Zhang,

T.Ch. (2009). *Contaminants of emerging environmental concern*. pp. 1-6, American Society of Civil Engineers (ASCE) ISBN 978-0-7844-1014-1, Reston, Virginia USA. Hansen, A. (1993). *The mass media and environmental issues – Studies in communication and society*. pp. 12-28, ISBN 978-0718520533 Leichesters University Press, UK.

**6. Advantages and limitation in eco-toxicological profiling based on** 

In order to compare the results obtained after human hair analysis and the amount of these compounds detected in vegetables samples it was observed a quite good correlation as regards the humans' uptake values to hydrocarbons and the amounts of these compounds which are present in vegetables samples – see figure 6.

Fig. 6. Mono- and polycyclic aromatic hydrocarbons amount from human hair samples dependence by the amount of these compounds in the consumed foodstuffs.

Comparing the uptake levels of mono- and polycyclic aromatic hydrocarbons it was observed that polycyclic aromatic hydrocarbons are better retained in living organisms than monoaromatic hydrocarbons.

#### **5.3 Organometallic compounds fingerprint on biological samples**

Methylmercury was the most prevalent organometallic compound that was detected in environmental samples. This was a special case which is attributed to banned and improper managed old chemical factory. The amount of this compound founded in soil and water samples are listed through table 4.


Table 4. Methylmercury range values in soil and water samples in the last two years. Methylmercury amounts in vegetables samples grown in this region was between 0.5 – 12.1 µgkg-1 while in human and animal hair samples it's amount was between 0.2 – 19.1 and 0.5 – 10.3 ngkg-1, respectively. Once again higher values being detected in case of human subjects.
