USC Chemical Engineering Student

Air Pollution Control 2017

D e p a r t m e n t o f Term/Academic Year:
Chemical Engineering Second Semester AY 2017-2018
Talamban, Cebu City, Philippines 6000

Case Study:
“Moss biomonitoring of atmospheric deposition of
minor and trace elements in Macedonia”

CHE EB13
Air Pollution Control

Submitted by:
John Christopher A. Torrefiel

Submitted to:
Engr. Ramir L. Jarabis

Date Submitted:
January 4, 2017
Introduction

Air pollution has been one of the major threats to human health and the environment in the
past century. The degree and extent of environmental changes over the last few decades have given
a new urgency and relevance to the detection and understanding of environmental change due to
human activities and other pollutants. Monitoring toxic air pollutants is needed to understand their
spatial and temporal distribution and ultimately to minimize their harmful effects. In addition to
direct physical and chemical methods of air pollution monitoring, bioindication has also been used
to evaluate air pollution risk (Dmuchowski and Bytnerowicz 2009). Biomonitoring with mosses is
based on the fact that terrestrial carpet-forming species obtain most of their nutrients directly from
wet and dry deposition, so they clearly reflect the atmospheric deposition, making them especially
well-suited to measure heavy metal pollution on a larger time scale (Čeburnis et al. 2002). Mosses
as bioindicitors are popular not only due to their environmental features but also because of their
economic advantages. Biological indicators are applied as the cheapest and simplest indicators for
monitoring the potentially toxic metals’ concentrations in the atmosphere. The technique of moss
analysis provides a surrogate, time-integrated measure of metal deposition from the atmosphere to
terrestrial systems. It is easier and cheaper than a conventional precipitation analysis as it avoids
the need to deploy large numbers of precipitation collectors, with an associated long-term program
of routine sample collection and analysis. Therefore, a much higher sampling density can be
achieved than with conventional precipitation analysis. Biological monitoring of airborne
contaminants has made great progress since the early observations of environmentally induced
stress on plants and its applications have grown to an extent (Kuang et al. 2007).

Air pollutants are deposited on mosses in aqueous solution in gaseous form or attached to
particles. The attachment of particles in mosses is affected e.g., by the size of the particles and the
surface structure of the mosses. Ion exchange is a fast physiological-chemical process that is
affected e.g., by the number and type of free cation exchange sites, the age of the cells and their
reaction to desiccation, growing conditions, temperature, precipitation pH, composition of the
pollutants, and leaching. In the ion exchange process, cations and anions become attached to
functional organic groups in the cell walls among other things through chelation. Mosses cannot
prevent ions penetrating into their tissues because they have high counter-gradient mechanisms by
which they accumulate significant concentrations of metals in their bodies (Shakya, Chettri, &
Sawidis, 2008). In particular, the increase of the lead and zinc content in the eastern parts of
Macedonia should be emphasized, especially due to reactivation of the mines and flotations of Pb
and Zn ore. The first results of the air pollution research for heavy metals pollution have led to
increased interest in the application of biomonitoring with mosses for extensive research in certain
regions in Macedonia (Stafilov, 2014). Such investigations were carried out for Cu in the vicinity
of the “Bučim” copper mine near Radoviš; for Cr and Ni in Kavadarci; for Pb and Zn near mines
and flotations “Toranica” near Kriva Palanka, “Zletovo” near Probištip and “Sasa” near
Makedonska Kamenica and for arsenic, antimony, and thallium in the vicinity of the abandoned
mine “Allchar” south of Kavadarci (Bačeva et al. 2013) as well as in the surroundings of the
thermoelectric coal-fired power plant “REK Bitola” near the town of Bitola.

Key Issues

The main issue discussed in the research article is the increase in the concentrations of
metals deposited in mosses in Macedonia. Different moss surveys were conducted in 2002, 2005,
2010, and 2015. The results showed that there was significant increase in the concentrations of
potentially toxic metals (As, Cd, Co, Cr, Cu, Ni, Pb, and Zn) in the collected moss samples
throughout the Republic of Macedonia. The atmospheric deposition of heavy metals poses serious
risks to the ecological system and human health, therefore, assessing the concentrations of these
metals in the atmosphere is important in developing strategies to remediate or reduce their
concentrations in the atmosphere.

With the rapid industrialization, agricultural modernization and urban expansion in China,
the mining and smelting of metal minerals, thermal power, automobile exhaust and waste
incineration emissions are the major sources of the atmospheric heavy metal pollutants. Recent
research studies demonstrated that atmospheric heavy metal emissions have rapidly increased in a
linear fashion during the past two decades. Heavy metals in the atmosphere eventually return to
land and water surfaces by the processes of dry and wet deposition (in-cloud or below-cloud
scavenging). Public concern due to heavy metal transfer and accumulation in the food chain by
atmospheric deposition into the ecosystem has increased rapidly with the substantial atmospheric
emissions. Cadmium is particularly ecologically hazardous because of its easy uptake by plants,
its tendency to accumulate in crops, and its persistent nature once it is in the environment (Ye,
Huang, Zhong, Wang, & Tu, 2017).

Spatial distribution of heavy metals in Macedonia

A study conducted by Robert, Barandovski, & Ba (2017) aimed to develop a spatial profile
of the concentration of heavy metals in Macedonia using data from moss surveys conducted in
2002, 2005, 2010, and 2015. Presented in Figure 1 is the location of the moss sampling site in
Macedonia.

Figure 1. Moss survey sampling site (Robert et al., 2017)

Figure 2. Spatial distribution of atmospheric metals in Macedonia
Analysis

With the rapid industrialization, agricultural modernization, urban expansion, mining and
smelting of metal minerals, thermal power, automobile exhaust and waste incineration emissions
are the major sources of the atmospheric heavy metal pollutants. Recent research studies
demonstrated that atmospheric heavy metal emissions have rapidly increased during the past two
decades (Ye et al., 2017). Heavy metals in the atmosphere eventually return to land and water
surfaces by the process of dry and wet deposition. In the case of the moss surveys conducted in
the Republic of Macedonia, the increase in the metals concentration in the mossed samples
analyzed was related to the reopening of lead and zinc mining in Eastern Macedonia and due to
large amount of flotation tailings deposited in landfills. Other factors such as the increase in
capacity of the ferronickel smelter in the city of Kavardaci could have contributed to the increase
in the metals concentration of the analyzed moss samples.

Another factor could be the geographic location and topography of the country. The
Republic of Macedonia is a land-locked country in the central part of the Balkan Peninsula
positioned between 40°50′ and 42°20′ North and between 20°27′ and 23°05′ East. The Republic
of Macedonia covers an area of 25,713 km2. It has a total population of 2,022,547 inhabitants
(census of 2002), with an average population density of 78.6 inhabitants/km2. Macedonia is
geographically defined by a central valley formed by the river Vardar and framed by mountain
ranges. The terrain is mostly rugged, located be- tween the Šar Planina and Osogovo mountains,
which frame the valley of the river Vardar. Three large lakes—Lake Ohrid, Lake Prespa, and Lake
Dojran—are situated on the southern borders, bisected by the frontiers with Albania and Greece.
Macedonia is also rich in minerals, with substantial deposits of chromium and other nonferrous
metals such as copper, lead, zinc, manganese, and nickel. The country also has gypsum, marble,
and granite mines. Lignite provides 80% of the electricity in Macedonia. In addition to mines and
quarries, the country has large cement plants and metal complexes created in the last century.
Because of the characteristic natural and geographical features, there are two different climates in
Macedonia—an altered Mediterranean climate and a temperate continental climate with two
distinct seasons: cold, wet winters and dry, hot summers associated with the transitional seasons,
spring and autumn. In mountainous regions, the climate is characterized by short, cool summers,
and significantly cold and moderately wet winters, with precipitation mostly as snow.
Recommendations

The use of biological indicators in monitoring air pollution is an indirect method in assessing the
state of the presence of atmospheric pollutants that can be bioaccumulated by plants and animals.
These types of monitoring techniques are often cheaper than direct air monitoring using expensive
equipment. Despite this advantage, it also has certain disadvantage. The rate at which different
organisms accumulate pollutants in their cells are varying. For the case of the moss survey in
Macedonia, the rate of accumulation of metals in moss could be dependent on the species. This
could affect the accuracy of the results so this factors should also be considered in future
biomonitoring activities. Another recommendation would be to conduct co-sampling with a more
reliable method or machine to determine the validity of the results obtained using biomonitoring
methods. This would ensure that the results from the biomonitoring surveys could be give a rough
assessment on the state of atmospheric pollution in the area.

Conclusion

The survey conducted in 2015 revealed a situation with air pollution with potentially toxic metals
in Macedonia that was similar to that established in 2010. This is because all activities in the field
of mining and metallurgy are in continuous work with the same capacity in 2010–2015. Still the
largest anthropogenic impact of air pollution with heavy metals was found near a smelter for
ferronickel near Kavadarci (Ni and Cr) and lead and zinc mines in the vicinity of Probištip,
Makedonska Kamenica, and Kriva Palanka (Cd, Pb, and Zn).
References:
Robert, Š., Barandovski, L., & Ba, K. (2017). Moss biomonitoring of atmospheric deposition study of
minor and trace elements in Macedonia.
Shakya, K., Chettri, M., & Sawidis, T. (2008). Impact of heavy metals (copper, zinc, and lead) on the
chlorophyll content of some mosses. Arch Environ Contam Toxicol, 54, 412–421.
Stafilov, T. (2014). Environmental pollution with heavy metals in the Republic of Macedonia. Contrib Sect
Nat Math Biotech Sci MASA, 35, 81–119.
Ye, L., Huang, M., Zhong, B., Wang, X., & Tu, Q. (2017). Wet and dry deposition fluxes of heavy metals in
Pearl River Delta Region (China): Characteristics, ecological risk assessment, and source
apportionment. Journal of Environmental Sciences, 1–19.
https://doi.org/10.1016/j.jes.2017.11.019