Further strengthening the capacities for effective implementation of the
acquis in the field of air quality
This project is funded by the European Union
Ministry of Environment and Physical Planning Finnish Meteorological Institute
Report on the Heavy Metal and PAH campaign 2015‐2016
Twinning project ‐ Further strengthening the capacities for effective
implementation of the acquis in the field of air quality
Table of Contents
Summary of the campaigns ..................................................................................................................................3
1. Introduction ..................................................................................................................................................7
2. Sampling sites ...............................................................................................................................................8
3. Sampling and analysis methods ................................................................................................................ 10
3.1 instrumental methods ............................................................................................................................. 10
3.2 Source apportionment ............................................................................................................................ 12
4. Results and conclusion .............................................................................................................................. 12
4.1 Karpos ................................................................................................................................................ 14
4.1.2 Karpos source apportionment ....................................................................................................... 21
4.2 Tetovo ...................................................................................................................................................... 23
5. Emission sources ....................................................................................................................................... 27
6. Comparison to other HM and PAH studies performed in Macedonia ...................................................... 29
7. Comparison to European levels. ................................................................................................................ 31
8. References ................................................................................................................................................. 33
Annex 1. ............................................................................................................................................................. 34
Annex 2. ............................................................................................................................................................. 47
Summary of the campaigns
A campaign to measure heavy metals (HM) and polycyclic aromatic hydrocarbons (PAH) in particulate matter
(PM10) in air was organized in Karpos, Skopje, between August 2015 and March 2016. Additionally, the monitor
data (SO2, NO, NO2, CO, O3, PM10, PM2.5) routinely collected at the station was utilized in this report. Main ions
(Ca, Cl, K, Mg, oxalate, Na, NH4, NO3, SO4), monosaccharide anhydrides (levoglucosan, mannosan, and
galactosan) and black carbon in PM10 were also measured for the campaign.
In the EU air quality legislation (AQ Directives 2004/107/EC and 2008/50/EC) and national legislation, there are
limit and target values with upper and lower assessment thresholds for certain elements and compounds in air.
Here, the annual limit value of lead and annual target values of arsenic, cadmium, nickel and benzo(a)pyrene
were compared with the campaign results (Figure 1). For benzo(a)pyrene, the annual target value was clearly
exceeded during the campaign and most likely the annual target value is exceeded at Karpos station. For the
heavy metals, the target values were not exceeded when compared to campaign averages (Table 1). Moreover,
the lower assessment thresholds, according to this campaign, were not exceeded in Karpos.
Levoglucosan level at Karpos were among the highest measured in Europe (average 852 ng/m3, Fig.24), but
similar levels have been measured also in some other campaigns in Europe, for example in Dettenhausen
(Germany) and Lycksele (Sweden).
Figure 1. Arsenic (As), cadmium (Cd), nickel (Ni), lead (Pb) and benzo(a)pyrene (b(a)p) in PM10 aerosol in Karpos during
August 2015 – March 2016. The annual target values are the red lines while the upper assessment thresholds (UAT) and
lower assessment thresholds (LAT) are the dashed lines: UAT is the upper line and LAT is the line underneath.
0
5
10
15
1/8/15 1/12/15 1/4/16
As
0
2
4
6
1/8/15 1/12/15 1/4/16
Cd
0
5
10
15
20
25
1/8/15 1/12/15 1/4/16
Ni
0
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400
600
1/8/15 1/12/15 1/4/16
Pb
0
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20
1/8/15 1/11/15 1/2/16
b(a)p
Table 1. The limit and target values with upper and lower assessment thresholds as stated in the AQ Directives for heavy
metals and benzo[a]pyrene in PM10 aerosol. In the last column, the average concentration of the pollutant during the
measurement campaign is given.
Pollutant Limit value (ng/m3)
Target value (ng/m3)
Upper assessment threshold (ng/m3)
Lower assessment threshold (ng/m3)
Average conc. (ng/m3)
Lead 500 ‐ 350 250 11.5
Arsenic ‐ 6 3.6 2.4 1.8
Cadmium ‐ 5 3 2 0.4
Nickel ‐ 20 14 10 6.0
Benzo[a]pyrene ‐ 1 0.6 0.4 5.2
Source apportionment using positive matrix factorization (PMF) method was made for Karpos data. 8‐factors
solution was selected to further analysis. (Figures 2 and 11).
These eight sources were: soil (F1), traffic (F2), sea salt (F3), biomass burning (F4), sulphate aerosol (F5),
industry (F6), nitrate aerosol (F7) and long‐range transported pollution (LRT) (F8).
According to this solution, majority of PM10 pollution came from five sources, which were soil (19%), traffic
(19%), biomass burning (32%), sulfate aerosol (7%) and industry (18%). Other three sources (nitrate aerosol,
LRT and sea salt) had only minor contribution to modeled PM10 mass at Karpos site (Figure 2).
Figure 2. PM10 pollution sources at Karpos station.
Additionally, a heavy metal campaign in Tetovo was organized. The data from Tetovo HM campaign indicates
the As, Ni and Cd concentrations in PM10 aerosol in Tetovo are below EU target values and within EU AQ limits
(Figure 3). However, the comparison to target values is only indicative as the measurements should have been
continued for a full year with even distribution over the year to fulfill the data quality objectives from the
legislation. The available data is limited to four months. In addition, the Jugohrom Ferroalloys DOO Jegunovce
smelter, a point source with highest emissions in the country and located some 15 km from Tetovo, was under
maintenance during January and February. Thus, the results do not reflect the typical situation. The two month
average of arsenic during October‐December (when Jugohrom Ferroalloys DOO Jegunovce was normally
operating) exceeds the lower assessment threshold (Table 2).
Figure 3. Arsenic (As), cadmium (Cd), nickel (Ni) and lead (Pb) in PM10 aerosol in Tetovo during October 2015 – February
2016.
Table 2. The limit and target values with upper and lower assessment thresholds as stated in the AQ Directives for heavy
metals and benzo[a]pyrene in PM10 aerosol. In the last column, the average concentration of the pollutant during the
measurement campaign in Tetovo is given. Additionally, the average concentration in Oct‐Dec is given in parenthesis.
Pollutant Limit value (ng/m3)
Target value (ng/m3)
Upper assessment threshold (ng/m3)
Lower assessment threshold (ng/m3)
Average conc. (ng/m3)
Lead 500 ‐ 350 250 21 (28)
Arsenic ‐ 6 3.6 2.4 1.8 (2.7)
Cadmium ‐ 5 3 2 1.0 (1.4)
Nickel ‐ 20 14 10 4.6 (6.3)
There were some concerns with the representativeness of data with both campaigns. Both campaigns were
performed for under a year so they do not represent the annual situation but do give indication of the
concentration levels. In Karpos campaign, the quality of data regarding heavy metal results analysed at the
second analysis laboratory was unsatisfactory for reasons stated later in this report. In Tetovo campaign, the
0
2
4
6
8
30/10/15 30/12/15 29/2/16
As
0
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30/10/15 30/12/15 29/2/16
Cd
0
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10
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20
25
30/10/15 30/12/15 29/2/16
Ni
0
200
400
600
30/10/15 30/01/16
Pb
influence of Jugohrom Ferroalloys DOO Jegunovce to local air quality is clearly seen but since the smelter was
under maintenance during half of the campaign period, the results obtained do not present the typical air
quality situation in Tetovo.
The uncertainty of the heavy metal campaign results in Skopje influenced the PMF modelling significantly
especially for the definition of the impact of those sectors with largest contribution to the heavy metal
concentrations. This for example resulted that the contribution of industry and soil to the overall
concentrations was not possible to be separated and was estimated as one sector. To improve the source
apportionment, availability of a longer period of monitoring data for heavy metals and PAHs and good quality
analyses of the samples is essential.
1. Introduction
A measurement campaign to study the heavy metal (HM), levoglucosan and polycyclic aromatic hydrocarbons
(PAH) concentrations in air was organized in Skopje in order to find out if the local air quality meets the
requirements of the Fourth Daughter Directive* and the CAFÉ Directive** regarding these pollutants. Of the
metal components mentioned in the Directive, mercury was not analysed since only monitoring requirements
are specified for this pollutant (and thus no limit nor target value is established).
The samples were collected at one station in Skopje and one station in Tetovo for 8 and 4 months, respectively,
in 2015‐2016. Here we present the time series of these pollutants with special note on the limit and target
values specified in the EU and national legislation. Additionally, source apportionment analysis was conducted
to study the sources of the pollutants. For the source apportionment study, filters for main ion, black carbon
and levoglucosan analysis were collected at Karpos for 6 months. Moreover, monitor data on gases (SO2, NO2,
O3, CO, benzene) and particles (PM2.5 and PM10) sampled in Skopje and Tetovo were utilized in the data
analysis.
*Directive 2004/107/EC of the European Parliament and of the Council relating to arsenic, cadmium, mercury,
nickel and polycyclic aromatic hydrocarbons in ambient air
**Directive 2008/50/EC of the European Parliament and of the Council of 21 May 2008 on ambient air quality
and cleaner air for Europe
2. Sampling sites
The sampling for heavy metals, levoglucosan and PAH’s was performed in the City of Skopje at the Karpos
station during 5.8.2015‐21.3.2016 (Figure 4). Altogether 60 PAH and ion samples, 43 levoglucosan samples and
80 heavy metal samples were collected, once in every third day. The station is categorized as an urban
background station located in a schoolyard in the middle of an urban residential area. A heavy fuel oil‐fired
district heat production plant ‘West’ is located 700 m northwest of the station. Additionally, the monitor data
and main ion data used for the source apportionment study were collected at this station.
Figure 4. MCZ filter samplers at Karpos site in August 2015
Moreover, atmospheric heavy metal samples (PM10) were collected in Tetovo, an urban traffic station (Figure
5). The sampling was performed in 30.10.2015‐27.2.2016. The station is located some 15 km from a smelter
Jugohrom Ferroalloys DOO Jegunovce, a point source with highest emissions in the country (Figure 5). In this
report, the data from Tetovo is presented as a time series and compared to the EU and national legislation limit
and target values. Source apportionment analysis was not performed for Tetovo due to insufficient data.
More details on the measurement sites can be found in the air quality portal
(http://airquality.moepp.gov.mk/?lang=en) and in Anttila et al., 2015.
Figure 5. The map of air quality stations Karpos in Skopje and Tetovo (blue stars). The point source with highest emissions
in the country, the Jugohrom Ferroalloys DOO Jegunovce, is marked with a red star.
10 km
3. Sampling and analysis methods
3.1 instrumental methods
The samples for HM, PAH and main ions were collected every three days according to the European Standard
EN 12341 Ambient air, Standard gravimetric measurement method for the determination of the PM10 or PM2.5
mass concentration of suspended particulate matter. The gaseous pollutants were measured according to
European Standards EN 14211 (NO2), EN 14212 (SO2), EN 14625 (O3) and EN 14626:2012 (CO), while
particulate masses were measured according to the Technical Specification (CEN) CEN/TS 16450:2013 (PM2.5
and PM10) prepared by European Committee on Standardization.
24h filter samples were collected on Teflon filters, every third day. The sample duration for HM and PAH filters
was changed to 12 h in Tetovo in the middle of the campaign due to the overload and blocking of the filters.
For main ions, the flowrate was reduced to 1 m3/h in the middle of the campaign, in order to keep the sampling
duration in 24h. For gases and particulate matter data, hourly averages from the monitor data were averaged
into daily values according to the filter sampling. Particulate matter was monitored in two size fractions as
stated in the EU legislation: fine particles (PM2.5) and coarse particles (PM10).
There were some sampling problems during the campaign with occasional power cuts, minor pump problems
with the filter sampling and filter overload and blocking, which resulted to some small gaps in the data.
The HM filter pretreatment and analysis was performed partly at the Finnish Environmental Institute FEI
(Karpos samples from August to September and all the Tetovo samples) and partly at the Institute for Labour
Protection (Istitut za zashtita na radu, Serbia), which was a subcontractory laboratory of Technolab (Karpos samples from October 2015 to March 2016). Both laboratories are accredited according to EN/ISO IEC 17025.
At FEI and the Serbian laboratory, the samples were digested and analysed according to EN 14902:2005. The
FEI method is based on microwave assisted acid digestion of the filter samples followed by analysis with
inductively coupled mass spectrometry (ICP‐MS) while the Serbian laboratory reports to use same
pretreatment method and GF‐AAS for analysis. Both methods are the reference methods stated in the
Commission Directive (EU) 2015/1480 amending several annexes to Directives 2004/107/EC and 2008/50/EC.
The quality of the data from Technolab was not satisfactory as stated in the results later in this report.
The PAH samples were extracted and analysed at the Finnish Meteorological Institute (FMI) in the accredited
air quality laboratory according to standards EN 15549 and ISO 12884:2000. The method is based on
dichloromethane extraction followed by analysis with gas chromatography mass spectrometer (GC‐MS). The
standard EN 15549 is the reference method stated in the Commission Directive (EU) 2015/1480 amending
several annexes to Directives 2004/107/EC and 2008/50/EC.se of ISO standard 12284 for the other polycyclic
aromatic hydrocarbons in the absence of a CEN method.
The ion filters were analysed for ammonium (NH4), black carbon (BC), calcium (Ca), chloride (Cl), magnesium
(Mg), nitrate (NO3), oxalate (Ox), potassium (K), sodium (Na) and sulfate (SO4) at the Finnish Meteorological
Institute in the laboratory of Atmospheric Aerosols group in co‐operation with National Institute for Health and
Welfare. For ion analysis, a European standard is under preparation and will be published in 2016‐2017. The
filters were extracted with ultrapure Milli‐Q (MQ) water and analysed with IC.
The levoglucosan filters were analyzed using high performance anion exchange chromatography‐mass
spectrometry method (HPAEC‐MS). Levoglucosan, mannosan and galactosan are burning products of cellulose
and hemicellulose, which, along with lignin, ash components and some other extractives, are the main
components of plant biomass. Because these monosaccharide anhydrides have low vapour pressures, they
exist in the particulate phase in the atmostphere. Levoglucosan is produced in large amounts in biomass
burning processes, and due to it’s stability in atmosphere, it is a good qualitative marker for biomass burning.
(Saarnio et al, 2010).
Levoglucosan data was used as a supportive data for PMF and it confirmed our previous identification of
biomass burning source.
The gases and particulate masses were measured by the Ministry of Environment and Physical Planning
(MEPP), Skopje. These components are part of the continuing air quality measurements conducted by the
laboratory of MEPP. A summary of all the measurements is given in Table 3.
Table 3. Sampling and analysis methods applied during the campaign. For HM, PAH, levoglucosan and ions, laboratory
analyses are needed while gases, PM2.5 and PM10 are measured with monitors (and thus the sampling column includes all
the needed information).
Sampling Sample pretreatment Sample analysis Analysis laboratory
Heavy metals in PM10
Filter sampling according to EN 12341 (instrument: MCZ LVS 16, Derenda
Acid digestion according to EN 14902 (instrument: Milestone Ultrawave 240º)
ICP‐MS analysis according to EN 14902 (instrument: Thermo iCAP Q)
FEI, T003, Accredited Laboratory Centre (Finland)
Acid digestion according to EN 14902 (instrument: unknown)
GF‐AAS analysis according to EN 14902 (instrument: Varian 240 FS)
Subcontractor of Technolab (Serbia)
PAH in PM10 Filter sampling according to EN 12341 (instrument: MCZ LVS 16, Derenda
Soxtherm extraction in DCM
GC/MS analysis,
EN 15549, ISO 12884:2000, Agilent 6890N GC, 5973 MS,
FMI, T097, Accredited Air Quality Laboratory (Finland)
Ions in PM10 Filter sampling according to EN 12341 (instrument: MCZ LVS 16/PM10 – L)
Extraction with ultrapure water (MQ)
IC analysis (instrument: Dionex 1CS‐2000 Ion Chromatography System)
FMI, Atmospheric Aerosols laboratory, in co‐operation with National Institute for Health and Welfare (Finland)
Levoglucosan (Ma:s)
Filter sampling according to EN 12341 (instrument: MCZ LVS 16/PM10 – L)
Extraction with ultrapure water (MQ)
High performance anion exchange chromatography/MS Dionex ICS‐3000
FMI, Atmospheric Aerosols laboratory
Sulphur dioxide
EN 14212 (instrument: ML2050 CASELLA MONITOR)
‐ ‐ MEPP (Skopje)
Nitrogen oxide
EN 14211 (instrument: ML2041 CASELLA MONITOR)
‐ ‐ MEPP (Skopje)
Nitrogen dioxide
EN 14211 (instrument: ML2041 CASELLA MONITOR)
‐ ‐ MEPP (Skopje)
Carbon monoxide
EN 14626 (instrument: ML2030 CASELLA MONITOR)
‐ ‐ MEPP (Skopje)
Ozone EN 14625 (instrument: ‐ ‐ MEPP (Skopje)
ML2010 CASELLA MONITOR)
PM10 CEN/TS 16450 (instrument: PM10 5030 SHARP Monitor ‐ Thermo Scientific Model)
‐ ‐ MEPP (Skopje)
PM2.5 CEN/TS 16450 (instrument: PM2.5 5030 SHARP Monitor ‐ Thermo Scientific Model)
‐ ‐ MEPP (Skopje)
3.2 Source apportionment
The positive matrix factorization (PMF) method was used for source apportionment of the chemical species in the daily samples. PMF is a factor analysis tool that decomposes the sample data matrix (which is a combination of pollutant time series measured at the site) into two matrices: factor contributions and factor profiles, according to their correlations; what species come together in the time series. These factors can be used for determining air pollution sources, such as biomass burning or industrial sources, according to the knowledge of the local sources and their emissions.
It should be acknowledged that for PMF, as with all modeling, the quality of the modeled PMF solution highly depends on the amount of input data and data quality, as well as user knowledge of the data and of the potential pollution sources that might have an effect on the air quality on the receptor site.
Conditional probability function, CPF, was used to combine Karpos wind data into PMF factor results. In CPF calculation, area around Karpos station was divided into four sectors: northern, eastern, southern and western sectors (315‐45, 45‐135, 135‐225 and 225‐315 degrees, respectively). An average wind vector was calculated for each sample (“sampling day”, which is 24h sample, typically from 11am). CPF calculates the ratio of days that it took for the averaged wind vector to hit into each sector that peaked in the each factor time series, to total amount of days that came into same sector. Sampling days that peaked in the factor (over 0.8th percentile of the contribution values) and which did not overlap to each other, were taken into account in the calculation.
CPF gives approximate direction for pollutant sources. It should be mentioned that during the measuring period, wind speeds were altogether quite low at the Karpos station, probably because of the tranquil location of the station in the park. This caused some mixing in the CPF analysis.
Challenges to achieve accurate results with PMF in this project were
‐ Limited gas and PM data; there was some missing gas and PM data and gaps in the time series;
however, this wasn’t a significant issue and it was taken into account in the model
‐ More challenging was the changes of sampling in the middle of the campaign; this caused severe
quality problems in the second part of the Karpos data on heavy metals starting already from October
until to the end of campaign.
‐ As a result, two third of Karpos HM data was of low quality:
o HM concentration level changed as the analysis laboratory changed with many metals,
suspicious results of Al and Zn, high amount of results with <LOD results).
o This, along with insufficient background information of Technolab analysis methods including
LODs and uncertainties (we had to make rough assumptions regarding to the Technolab data),
caused incoherence and mixing to the model results and made the interpretation of the results
quite a challenging task.
‐ Low wind speeds at the Karpos station
‐ Low amount of levoglucosan data; there were difficulties with sampling of levoglucosan filters.
However, overall quality of the levoglucosan data was good and it was used as a supportive data for
biomass factor identification.
‐ The absence of local heavy metal emission data (to be able to distinguish the industrial factor from soil
factor)
‐ The pollutants have many emission sources, which logically divided into different factors and also
caused mixing for the factors.
4. Results and conclusion
4.1 Karpos
4.1.1 Pollutant levels at Karpos
Data from Karpos HM and PAH campaign is presented in Figures 6‐9 for components covered by the legislation
and in Annex 1 for the other HMs and PAHs, main ions, monosaccharide anhydrides (MA; levoglucosan,
mannosan, galactosan) and monitor data. HM levels in the Karpos area, according to this campaign data, are
below the limit and target values (Table 4) of EU legislation (AQ Directives 2004/107/EC and 2008/50/EC).
Average benzo(a)pyrene concentration exceeded EU target value (1 ng/m3) and this half year campaign
indicates that benzo(a)pyrene in PM10 aerosol (annual average concentration) might be in exceedance in
Karpos area according to the EU fourth daughter AQ directive (2004/107/EC). In Table 5, the average
concentration for the metal and PAH not mentioned in the AQ Directive but measured during the campaign are
also given. Levoglucosan level at Karpos were among the highest measured in Europe (average 852 ng/m3,
table 9), but not unique, similar levels have been measured in some European sites (figure 20, table 2 in Annex
1). From the figure 14 it is seen that monthly averages of levoglucosan, b(a)p and PM10 follow nicely each
other. This means that biomass burning has effect on PM10 concentrations at Karpos, which also supports the
conclusion from the modeled result.
Table 4. The limit and target values with upper and lower assessment thresholds as stated in the AQ Directives for heavy
metals and benzo[a]pyrene in PM10 aerosol. In the last column, the average concentration of the pollutant during the
measurement campaign is given.
Pollutant Limit value (ng/m3)
Target value (ng/m3)
Upper assessment threshold (ng/m3)
Lower assessment threshold (ng/m3)
Average conc. (ng/m3)
Lead 500 ‐ 350 250 11.5
Arsenic ‐ 6 3.6 2.4 1.8
Cadmium ‐ 5 3 2 0.4
Nickel ‐ 20 14 10 6.0
Benzo[a]pyrene ‐ 1 0.6 0.4 5.2
0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
16.0
8/1/2015 10/1/2015 12/1/2015 2/1/2016 4/2/2016
UATLAT
Annual target
Arsenic in PM10 (ng/m3) in Karpos
0.0
1.0
2.0
3.0
4.0
5.0
6.0
8/1/2015 10/1/2015 12/1/2015 2/1/2016 4/2/2016
UAT
LAT
Annual target
Cadmium in PM10 (ng/m3) in Karpos
Figures 6‐9. Arsenic, cadmium, nickel and lead in PM10 aerosol in Karpos during August 2015 – March 2016. The annual
target values with upper assessment thresholds (UAT) and lower assessment thresholds (LAT) are also presented in the
figure. The solid blue line represents the results of the filters analysed by FEI and the dashed blue line the filters analysed
by Technolab.
0.0
5.0
10.0
15.0
20.0
25.0
8/1/2015 10/1/2015 12/1/2015 2/1/2016 4/2/2016
UAT
LAT
Annual target
Nickel in PM10 (ng/m3) in Karpos
0.0
100.0
200.0
300.0
400.0
500.0
600.0
8/1/2015 10/1/2015 12/1/2015 2/1/2016 4/2/2016
UAT
LAT
Annual target
Lead in PM10 (ng/m3) in Karpos
Figure 10. Benzo[a]pyrene in PM10 aerosol in Karpos during August 2015 – February 2016. The annual target value 1
ng/m3 is also presented in the figure. The upper assessment thresholds (UAT, 6ng/m3) and lower assessment thresholds
(LAT, 3 ng/m3) are the dashed lines: UAT is the upper line and LAT is the line underneath.
0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
16.0
18.0
20.0
01/08/2015 01/10/2015 01/12/2015 01/02/2016
Annual target
Benzo[a]pyrene in PM10 (ng/m3) in Karpos
Figures 11 and 12, Levoglucosan and MA (blue solid line) vs. modelled biomass burning factor time series
(yellow dotted line) in PM10 aerosol in Karpos during the campaign from August 2015 to February 2016.
0.0
1000.0
2000.0
3000.0
4000.0
5000.0
6000.0
7000.0
8000.0
‐1
0
1
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23.10.2015
07.11.2015
22.11.2016
07.12.2015
22.12.2016
31.12.2015
15.01.2016
30.01.2016
08.02.2016
23.02.2016
09.03.2016
levoglucosan
ng/m
3
biomass factor
levoglucosan (ng/m3) and biomass burning factor in Karpos
Biomass Burning Levoglucosan
0
1000
2000
3000
4000
5000
6000
7000
8000
‐1
0
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23.10.2015
07.11.2015
22.11.2016
07.12.2015
22.12.2016
31.12.2015
15.01.2016
30.01.2016
08.02.2016
23.02.2016
09.03.2016
MA sum, ng/m3
biomass factor
Sum of MA(ng/m3) and biomass burning factor in Karpos
Biomass Burning Levoglucosan
Figures 13a and 13b. Scatterplots and linear fit of MA sum and levoglucosan vs. modelled biomass burning
factor time series in PM10 aerosol in Karpos .
Figure 14. Monthly average levels for benzo(a)pyrene (ng/m3), PM10 (g/m3) and levoglucosan (ng/m3) at Karpos station,
from aug 2015 to feb 2016. Note logarithmic scale.
For PAH’s the analysis for the filter samples was performed in the laboratory of FMI. However, for the heavy
metal filters collected at Karpos, the laboratory was changed during the Karpos campaign. Unfortunately, this
change is visible in the results. The results of the first laboratory are well above the provided detection limits,
y = 868.59x ‐ 74.954R² = 0.6199
0
1000
2000
3000
4000
5000
6000
7000
0 5 10
levoglucosan, ng/m
3biomass factor
Levoglucosan
Levoglucosan
Linear(Levoglucosan)
0.10
1.00
10.00
100.00
1000.00
10000.00
aug sep oct nov dec jan feb
Monthly averages for b(a)p, PM10 and levoglucosan
b(a)pAVE Levoglucosan_AVE PM10AVE
y = 1000.5x ‐ 45.084R² = 0.654
0
1000
2000
3000
4000
5000
6000
7000
0 5 10
MA sum , ng/m
3
biomass factor
MA sum
MA sum
Linear (MAsum)
the measurement uncertainties are reasonable, the laboratory has a long experience in analyzing such filters
and the method is accredited. Additionally, it is typical for certain elements (such as soil derived elements Al,
Co, Cr, Mn, Fe) to show similar concentration patterns, and this was evident in the data of the first laboratory.
The results of the second laboratory did not show this similar pattern, moreover, the detection limits and
measurement uncertainties were not provided by the laboratory regardless of several requests. The second
laboratory is accredited but it remained unsolved if the analysis method is accredited or not. Thus, good quality
data for HM is only available during the two first months of the study.
The filters were additionally analysed for other heavy metals and PAHs not mentioned in the AQ Directive and
average results are shown in Tables 5 and 6.
Table 5. The average values (ng/m3) of other heavy metals during the campaign.
Al Co Cr Cu Fe Mn Ni V Zn
Average 916 0.12 1.90 10.8 708 13.7 6.03 2.93 392
Table 6. The average values (ng/m3) of other PAHs during the campaign.
phenantrene anthracene fluoranthene pyrene benz(a)anthracene
Average 3.42 0.53 8.40 8.05 4.73
chrycene/triphenylene
benzo(b+j+k)fluoranthene
benzo(ghi)perylene
indeno(1,2,3‐cd)pyrene
dibenz(a,h+a,c)anthracene
Average 6.62 9.24 4.03 3.60 0.49
During the campaign, the average concentration of measured gases were below annual limit values (Table 7).
However, the annual and daily limit values for PM10 and PM2.5 mass were well exceeded. Main ions and black
carbon (BC) in PM10 were collected by filters during the campaign but no limit or target values are set for these
components. Black carbon mass was roughly estimated from reflectance measurements using MAC coefficient
7.5. This should be verified with other methods before using these BC results as the absolute level. Here we
were mainly interested of the concentration differences in BC data, for modeling purposes, but not of the real
BC value. In the EU legislation, main ions in PM10 are to be measured at one background station per 100 000
km2 regardless of the concentration levels. The average values of main ions and BC are shown in Table 8. The
time series of these components is shown in Annex 1.
Table 7. The average values (µg/m3) of gases and particulate matter masses during the campaign.
CO O3 PM2.5 PM10 SO2 NO NO2 Benzene
Average 605 33.1 79.9 85.3 1.66 13.1 24.0 0.41
Table 8. The average values (µg/m3) of main ions and black carbon (BC) during the campaign.
Cl NO3 SO4 Ox Na+ NH4+ K+ Mg2+ Ca2+ BC Mass
Average 0.47 4.77 4.12 0.23 0.14 1.64 1.11 0.07 1.66 222*
* estimated value from reflectance measurements
Table 9. The average values (ng/m3) of the sum of saccharide anhydrides (MA), levoglucosan, mannosan and
galactosan measurements during the campaign.
levoglucosan mannosan galactosan Sum of MA
Average 852 120 76 1023
4.1.2 Karpos source apportionment
For PMF analysis, eight‐factors (sources) solution was selected to further analysis. (Figure 11). These eight sources were: soil (F1), traffic (F2), sea salt (F3), biomass burning (F4) sulphate aerosol (F5), industry (F6), nitrate aerosol (F7) and long‐range transported pollution (LRT) (F8).
Factor one (F1) includes typical soil components: aluminium, iron, manganese, cobalt, as well as chromium (soil and industrial sources) and arsenic, zinc, lead and vanadium which come typically from industrial sources. This source was named as soil, but it may also contain some industrial pollution, maybe contaminated soil. According to the CPF picture, the soil source was all around the station, which is realistic. 19% of PM10 pollution came from soil source.
Factor 2 includes majority of benzene, as well as nitrogen monoxide and nitrogen dioxide. Other components include chromium, iron, nickel (oil), vanadium (oil) and carbon monoxide (burning), as well as calcium and minor amount of PAHs. F2 was named as traffic. Source sectors for this factor also points to all four sectors around the station, but with major impact from east (Skopje traffic). Traffic contributes to 20% of PM10 mass.
Factor 3 contains most of sodium, as well as half of magnesium and one third of chlorine. This is a clear sea salt source and originated mainly from west, but with only very minor fraction (0.3%) of the total PM10 mass.
Factor 4 contains most of the PAHs, as well as carbon monoxide and black carbon, potassium and nickel. This is biomass burning source. This factor contributes to one third (32%) of the total PM10 pollution mass and came from around the Karpos site, which also refers to residential heating. When we compared this factor to levoglucosan and MA time series, it can be seen that model result follows levoglucosan and MA time series data nicely (figures 11 and 12) and they also correlate fairly well (r2 = 0,62 and 0,65 in figures 13a and 13b). This, in addition to K+ and b(a)p in factor 4, further confirmed our interpretation of this factor as the biomass burning factor.
Factor 5 contains ammonium sulphate with minor amounts of nitrogen dioxide, benzene, aluminium, arsenic, and cobalt. This is called sulphate source, and contains ammonium sulphate, which is a secondary pollutant from the reaction of sulphur dioxide with ammonia in contaminated air. This secondary source contributed to 7% of PM10 mass. The major source direction for F5 was west, which can include sulphur‐rich source further away in the western side of Karpos site.
Factor 6 includes most of cadmium and lead, and has also major contribution from carbon monoxide and NO. It also contains some heavier PAH‐compounds. This is industry source and contributes to 18% of the total PM10 pollution, with potential sources in northern sector, and also partly in eastern sector from Karpos.
Factor 7 includes secondary ammonium nitrate and ammonium sulphate, as well as some chlorine and other ions. This was named as nitrate source with only 2% contribution of total PM10 mass and with source areas around the station, except from western sector.
Factor 8 contains major part (91%) of ozone, with small amount of sulphur dioxide, nitrogen dioxide, benzene and aluminium. This factor represents long‐range transported pollution (LRT) source, where ozone has
developed by the photochemical reactions in the polluted air. The contribution was higher during summertime and the source direction was around the station, but mainly south. This factor accounted only very minor amount (2%) of the PM mass.
Figure 15. PMF factors, factor time series and CPF pictures for Karpos data.
Figure 16. Pie charts for PM2.5, PM10, benzo(a)pyrene and cadmium from Karpos PMF.
4.2 Tetovo
The results from Tetovo heavy metal campaign are presented in Figures 17‐20 and in Annex 2. The data from
Tetovo HM campaign indicates the As, Ni and Cd concentrations in PM10 aerosol in Tetovo are below EU target
values and within EU AQ limits. However, the comparison to target values is only indicative as the
measurements should have been continued for a full year with even distribution over the year to fulfill the data
quality objectives from the legislation. The available data is limited to four months.
At Tetovo, only heavy metals in PM10 were sampled for the campaign. Additionally, gases and PM are routinely
sampled at the station.
In Figures 17‐20, it is evident that the concentration levels dropped after the New Year. In November to
December, the concentration levels of especially arsenic and cadmium (but also nickel and lead) are higher
than the concentration levels during January to February. During the same time, the Jugohrom Ferroalloys DOO
Jegunovce smelter was under maintenance. It is evident that this maintenance period was reflected in the air
concentrations. The average concentration of metals in PM10 during January‐February was approximately half
of that in November‐December (the decrease was 49–70 % depending on the component). Similarly, the
decrease of PM10 and SO2 concentrations were 36 % and 50 %, respectively, between these two time periods.
In Tables 8‐10, the campaign average concentrations for heavy metals and monitor data are given. The two
month average of arsenic during October‐December (when Jugohrom Ferroalloys DOO Jegunovce was normally
operating) exceeds the lower assessment threshold as seen in Table 8, concentration in parenthesis.
PMF analysis was made also for Tetovo. However, because of the low amount of samples, 39 altogether, and
lack of biomass burning marker compounds (K+, b(a)p, levoglucosan) in Tetovo data, PMF analysis for Tetovo
data was unsuccessful.
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
10/30/2015 12/30/2015 2/29/2016
UAT
LAT
Annual target
Arsenic in PM10 (ng/m3) in Tetovo
0.0
1.0
2.0
3.0
4.0
5.0
6.0
10/30/2015 12/30/2015 2/29/2016
UAT
LAT
Annual target
Cadmium in PM10 (ng/m3) in Tetovo
Figures 17‐20. Arsenic, cadmium, nickel and lead in PM10 aerosol in Tetovo during November 2015 – February 2016. The
annual target values with upper assessment thresholds (UAT) and lower assessment thresholds (LAT) are also presented in
the figure.
0.0
5.0
10.0
15.0
20.0
25.0
10/30/2015 12/30/2015 2/29/2016
UAT
LAT
Annual target
Nickel in PM10 (ng/m3) in Tetovo
0.0
100.0
200.0
300.0
400.0
500.0
600.0
10/30/2015 12/30/2015 2/29/2016
UAT
LAT
Annual target
Lead in PM10 (ng/m3) in Tetovo
Table 10. The limit and target values with upper and lower assessment thresholds as stated in the AQ Directives for heavy
metals and benzo[a]pyrene in PM10 aerosol. In the last column, the average concentration of the pollutant during the
measurement campaign in Tetovo is given. Additionally, the average concentration in Oct‐Dec is given in parenthesis.
Pollutant Limit value (ng/m3)
Target value (ng/m3)
Upper assessment threshold (ng/m3)
Lower assessment threshold (ng/m3)
Average conc. (ng/m3)
Lead 500 ‐ 350 250 21 (28)
Arsenic ‐ 6 3.6 2.4 1.8 (2.7)
Cadmium ‐ 5 3 2 1.0 (1.4)
Nickel ‐ 20 14 10 4.6 (6.3)
Table 11. The average values (ng/m3) of other heavy metals during the campaign.
Al Co Cr Cu Fe Mn V Zn
Average 1130 0.64 6.55 23.5 1550 43.2 6.25 80.3
Table 12. The average values (µg/m3) of gases and particulate matter masses during the campaign.
SO2 NO2 CO O3 PM10
Average 5.03 40.5 2290 21.1 210
5. Emission sources
The map of the air quality stations is shown in Fig. 5.The prevalent wind directions are from N/NE and W/SW as
seen in windroses for Karpos (Figure 21). In Skopje, major industrial activities include manufacturing of steel
products and cement and concrete production approximately 5 km to the west and south of the city centre
(Figure 22), respectively, and oil refining approximately 20 km southeast of the city centre (Anttila et al., 2015).
In early 2015, the steel factory introduced new filtering methods and thus lower emissions are expected than
during the previous years. During the study period, the heat production plants in the city used natural gas while
the occasional use of heavy oil is unclear.
The largest point source for particulate emissions is believed to be the Jugohrom Ferroalloys DOO Jegunovce
situated in a small municipality of Jegunovce. It is situated some 15 km from the Tetovo air quality monitoring
station and some 30 km from Skopje. The factory was not working in Jan‐Feb 2016 while it was fully working in
2015.
Figure 21. Wind roses for Karpos in 2014 and 2015.
Figure 22. Map of Skopje with the local air quality stations marked with blue four‐pointed stars and the local emission
sources marked with five‐pointed stars.
The annual emissions of particulate matter, SO2 and NO2 in 2014 in Skopje area are given in Table 13 for the
relevant industries. Additionally, the annual emission of Jugohrom Ferroalloys DOO Jegunovce in 2013 and
2014 are given.
Table 13. Annual emissions of PM, SO2, NOx and CO of relevant sources in Skopje and of Jugohrom Ferroalloys DOO
Jegunovce in 2014 (for Jugohrom Ferroalloys DOO Jegunovce, also 2013 values are given).
Source PM (t) SO2 (t) NOx (t) CO (t)
ELEM Energy production NA 7.4 35 ‐
ISTOK Energy production 1.8 0.0 42 ‐
ZAPAD Energy production 4.2 0.0 30 ‐
Oktomvri Energy production 0.8 0.0 4.7 ‐
Arcelormittal steel indusrtry 5.5 0.9 0.8 ‐
Makstil steel industry 3.8 2.1 119 ‐
USJE cement production 11 47 1113 ‐ Jugohrom Ferroalloys DOO (2014) 9760 773 559 675 Jugohrom Ferroalloys DOO 2013 15574 1899 1260 1311
6. Comparison to other HM and PAH studies performed in the country
The heavy metal concentrations in air have been previously measured in a few campaigns while for PAH, this
measurement campaign was the first in Skopje.
The previous campaign time coverages have been from five days in one month to 80 x 12h samples during 11
months (Table 14). The analysis methods have been ICP‐MS and XRF, thus, the measurement methods have
not been in all cases according to the reference methods in AQ legislation.
In the last two campaigns performed in 2014‐2015, there were exceedances for arsenic, cadmium and nickel
while for lead, no exceedance of limit value has been ever reported. During this campaign, it has been evident
that the limit value of lead is not close to be exceeded and the results from previous campaigns support this
conclusion. In Skopje, high cadmium concentrations in PM10 have earlier been measured in both campaigns in
2014‐2015 in contrast with the results from this study. Nickel has been found to exceed the target value only in
Kavadarci where ferronickel industry is located. For arsenic, the target value exceedances have been reported
in Skopje and Jegunovce, the latter being the municipality where the Jugohrom Ferroalloys DOO Jegunovce
smelter is located. In this study, arsenic in Tetovo during the full operation of Jugohrom Ferroalloys DOO
Jegunovce was over the lower assessment threshold. In Karpos, the arsenic data does not give much
information due to very limited data set of high quality.
Table 14. Summary about the previous heavy metal campaigns (in PM2.5 or PM10) performed in Skopje and other sites in
the country.
Measured components of AQ Directives
Exceedances of the annual limit and target values (y/n) Analysis method Measurement sites Measurement period Ref.
As, Cd, Ni, Pb
Yes, for As, Cd and Ni (but not at all stations).
Modification of EN 14902 and EN ISO 17294‐2
Six stations around Macedonia (incl. 2 in Skopje)
Jul‐Aug, Oct 2014 (25 daily samples)
1
As, Cd, Ni, Pb Yes, for As and Cd. XRF Karpos, Skopje
Jun 2014 – Jan 2015 (9‐46 daily samples)
2
Ni, Pb No. EDXRF Skopje Dec 2006 – Oct 2007 (80 x 12h samples)
3
Table 15. Average concentrations of heavy metals in particulate matter measured in previous campaigns in Skopje and
elsewhere in the country. The exceedances of annual limit and target values are shown in red.
Measured components of AQ Directives Average Measurement sites Measurement period Reference
As Cd Ni Pb
4.6 57.1 8.8 288
Skopje (Usje, Cement)
Jul, Oct 2014 (10 daily samples)
1
As Cd Ni Pb
4.2 198 7.3 484
Skopje (Gaza Baba, metallurgy)
Oct 2014 (5 daily samples)
1
As Cd Ni Pb
18.8 15.8 6.0 58.9
Jegunovce (Jugohrom Ferroalloys DOO Jegunovce, smelter)
Jul, Oct 2014 (10 daily samples)
1
As Cd Ni Pb
1.7 2.3 75.3 16.3
Feni (ferronickel)
Jul, Oct 2014 (10 daily samples)
1
As Cd Ni Pb
2.0 5.0 6.0 75.0
Veles (No current industry, closed smelters)
Aug, Oct 2014 (5 daily samples)
1
As Cd Ni Pb
1.7 <3.6 9.0 <LOD
Bitola (REK Bitola, Thermo‐electric plant that uses coil)
Jul, Oct 2014 (5 daily samples)
1
As Cd Ni Pb
7.6 15.4 2.6 44.3
Skopje (Karpos)
Jun 2014 – Jan 2015 (9‐46 daily samples)
2
As Cd Ni Pb
N.A. N.A. 8.9 57
Skopje (42°00’N, 21°26’E)
Dec 2006 – Oct 2007 (80 x 12h samples)
3
7. Comparison to European concentration levels
According to the Air Quality in Europe 2015 –report, exceedances of As was measured at approximately 12
stations in Europe (of several hundreds stations) in 2013. Cd and lead exceeded at less than 10 stations. Ni
exceeded at two stations. Instead, about the half of the stations in Europe that had continuous benzo(a)pyrene
measurements in measured concentrations above the target value 1 ng/m3 in 2013, in 13 of EU‐28 countries.
Benzo(a)pyrene is a common problem in Europe (Figure 23).
Figure 23. Comparison of benzo(a)pyrene concentrations in Europe, 2013 from Air Quality in Europe 2015 report. (Karpos
8/2015‐1/2016 measured 5.2 ng/m3)
Average levoglucosan level at Karpos during the campaign was relatively high, 852 ng/m3, which is among the
highest value measured in Europe. However, cities such as Dettenhausen ,Germany (winter average 806
ng/m3), Graz, Austria (winter average 860 ng/m3) or Lycksele, Sweden (Jan‐Mar 2002 average 900 ng/m3) have
had similar levels of levoglucosan during winter season (Figure 24 and table A2 in Annex 1).
Fig. 24. Comparison of selected levoglucosan studies in Europe
0100200300400500600700800900
1000
Barcelona (Spain) 2009
‐ Feb‐M
ar
Borgerhout (Belgium)
Feb. 2010 ‐ Feb
. 2011
Vindinge (Den
mark)
2005 ‐ Feb
‐Apr
Salzburg (Austria) 2004
‐ Jan‐Feb
, Dec
Florence (Italy) 2009‐
2010 (w
inter)
Gen
t (Belgium) Nov
2000‐ Mar 2001
Dettenhausen
(Germ
any) Nov 2005 ‐
Mar 2006
Skopje, M
acedonia Aug
2015 ‐ Feb
2016
Lycksele (Sw
eden) 2002
–Jan‐M
ar
ng/m
3
Levoglucosan in Europe
8. References
Pia Anttila, Aneta Stefanovska , Aleksandra Nestorovska‐Krsteska, Ljupco Grozdanovski, Igor Atanasov, Nikola
Golubov, Pece Ristevski, Martina Toceva, Sari Lappi, Jari Walden (2015). Characterisation of extreme air
pollution episodes in an urban valley in the Balkan Peninsula, Air Quality, Atmosphere and Health, DOI
10.1007/s11869‐015‐0326‐7
Kovacevik, B., Wagner, A., Boman, J., Laursen, J. and Pettersson, J. B. C. (2011), Elemental composition of fine particulate matter (PM2.5) in Skopje, FYR of Macedonia. X‐Ray Spectrom., 40: 280–288. doi: 10.1002/xrs.133 Karri Saarnio, Kimmo Teinilä, Minna Aurela, Hilkka Timonen, Risto Hillamo (2010), High‐performance anion‐exchange chromatography–mass spectrometry method for determination of levoglucosan, mannosan, and galactosan in atmospheric�fine particulate matter, Anal Bioanal Chem (2010) 398:2253–2264 DOI 10.1007/s00216-010-4151-4 AIRUSE, LIFE11 ENV/ES/584, Action B4, Biomass burning in Southern Europe References in the Tables 14‐15:
1) Test Report No. 1411/0950. Chemical analysis of filters for PM10. Unweltbudesamt Gmbh, Austria. 2014.
2) IAEA project RER 1013, presentation by Marta Almeida, Instituto Superior Técnico, Universidade de Lisboa, Portugal given in Final Assessment Meeting Supporting Air Quality Management (Phase II) at International Atomic Energy Agency, Vienna, Austria, January, 25‐29, and the related data sheets provided by the Ministry of Environmental and Physical Planning.
3) Kovacevik, B., Wagner, A., Boman, J., Laursen, J. and Pettersson, J. B. C. (2011), Elemental composition of fine particulate matter (PM2.5) in Skopje, FYR of Macedonia. X‐Ray Spectrom., 40: 280–288. doi: 10.1002/xrs.133
4) Air quality in Europe, 2015 report. European Environment Agency 2015, doi:10.2800/62459
Annex 1.
Time series of heavy metals, PAHs, ions and black carbon in PM10, gases and particulate masses measured at
Karpos is given below.
Figure A1. Time series of As, Cd and Zn in PM10 measured at Karpos. These components are likely to have industrial
sources. Notice the use of primary (As, Cd) and secondary (Zn) axis for concentrations.
Figure A2. Time series of Ni and V in PM10 measured at Karpos. These components are likely to have heavy oil as their
source.
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
0
2
4
6
8
10
12
14
16
8/1/2015 10/1/2015 12/1/2015 2/1/2016 4/2/2016
Cd_S
Cd_T
As_S
As_T
Zn_S
Zn_T
As, Cd, Zn in PM10 (ng/m3) in Karpos
0
5
10
15
20
25
30
8/1/2015 10/1/2015 12/1/2015 2/1/2016 4/2/2016
Ni_S
Ni_T
V_S
V_T
Ni, V in PM10 (ng/m3)
Figure A3. Time series of Cr and Cu in PM10 measured at Karpos. These components are likely to have industrial sources
while Cr may also originate from soil.
Figure A4. Time series of Al, Co, Cr, Fe and Mn in PM10 measured at Karpos. These components are likely to
originate from the soil but may have other sources as well. Notice the use of primary (Co, Cr, Mn) and
secondary (Al, Fe) axis for concentrations.
0
10
20
30
40
50
60
70
8/1/2015 10/1/2015 12/1/2015 2/1/2016 4/2/2016
Cu_S
Cu_T
Cr_S
Cr_T
Cu, Cr in PM10 (ng/m3) in Karpos
0
2000
4000
6000
8000
10000
12000
0
10
20
30
40
50
60
8/1/2015 10/1/2015 12/1/2015 2/1/2016 4/2/2016
Co_S
Co_T
Cr_S
Cr_T
Mn_S
Mn_T
Al_S
Al_T
Fe_S
Fe_T
Al, Co, Cr, Fe, Mn in PM10 (ng/m3)
Figure A5. Monthly time series of PAHs in ng/m3 (in PM10) measured at Karpos.
0
20
40
60
80
100
120
140
160
Aug‐15 Sep‐15 Oct‐15 Nov‐15 Dec‐15 Jan‐16
dibenz(a,h+a,c)anthracene
indeno(1,2,3‐cd)pyrene
benzo(ghi)perylene
benzo(a)pyrene
benzo(k+b+)fluoranthene
chrycene/trifenyleeni?
benz(a)anthracene
pyrene
fluoranthene
anthracene
phenantrene
Figure A6. Time series of particulate masses (PM2.5 and PM10) measured at Karpos. The annual mean limit values are
exceeded. Surprisingly, the PM10 at Karpos is about the same as PM2.5.
Figure A7. Time series of O3, NO and NO2 measured at Karpos. The annual mean limit value for NO2 and the daily 8h max
for O3 are given. As typically, O3 has summer highs while NO and NO2 have winter highs.
0
50
100
150
200
250
300
350
8/1/2015 10/1/2015 12/1/2015 2/1/2016
PM2.5
PM10
PM2.5 annual limit
PM10 annual limit
PM10 daily limit
0
20
40
60
80
100
120
140
8/1/2015 10/1/2015 12/1/2015 2/1/2016
O3
NO
NO2
O3 daily max (8h)
NO2 annual limit
Figure A8. Time series of CO and benzene measured at Karpos. The annual mean limit value for benzene and the daily 8h
limit value for CO are given.
Figure A9. Time series of SO2 measured at Karpos. The annual mean limit value of SO2 is given.
0
1
2
3
4
5
6
7
8
9
10
8/1/2015 10/1/2015 12/1/2015 2/1/2016
CO
Benzene
Benzene annual limit
CO 8h limit
0
5
10
15
20
25
8/1/2015 10/1/2015 12/1/2015 2/1/2016
SO2
SO2 annual limit
Figure A10‐A12. Time series of main ions (in PM10) measured at Karpos. (1) Components associated with long range
transport, (2) components associated with sea salt and (3) other compounds and the biomass marker potassium (K). In Fig.
A11, the primary axis is for Na and Mg while the secondary axis is for Cl. In Fig. A12, the primary axis is for Ca, K and Ox
while the secondary axis is for BC.
0
5
10
15
20
25
30
8/1/2015 10/1/2015 12/1/2015 2/1/2016
NO3
SO4
NH4+
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
8/1/2015 10/1/2015 12/1/2015 2/1/2016
Na+
Mg2+
Cl
0
200
400
600
800
1000
1200
0
1
2
3
4
5
6
7
8
8/1/2015 10/1/2015 12/1/2015 2/1/2016
Ox
K+
Ca2+
BC Mass
Figure A13. PMF factors from Karpos data
020406080
100
Soil
Soil
020406080
100
Traffic
Traffic
020406080
100
Sea Salt
Sea Salt
020406080
100
Biomass Burning
Biomass Burning
020406080
100
CO…
PM 2.5,…
SO2…
NO2…
Al
Cd Cr
Fe Ni V
phen
antr…
fluoranth…
benz(a)an…
ben
zo(k+…
ben
zo(ghi…
diben
z(a,…
NO3
Ox
NH4+
Mg2+
BC M
ass…
Secondary Sulfate Aerosol
Secondary Sulfate Aerosol
020406080
100
Industry
Industry
020406080
100
CO…
PM 2.5,…
SO2…
NO2…
Al
Cd Cr
Fe Ni V
phenantr…
fluoranth…
ben
z(a)an…
ben
zo(k+…
ben
zo(ghi…
diben
z(a,…
NO3
Ox
NH4+
Mg2+
BC M
ass…
Nitrate Rich Aerosol
Nitrate Rich Aerosol
020406080
100
LRT
LRT
Figure A14. Factor contributions and CPF for Karpos data
Figure A15. Karpos PMF: Percentages of sources for selected pollutants
Table A1. Factor profile data from Karpos PMF
Factor Profiles (% of species sum) from Base Run #11 (Convergent Run)
Soil Traffic Sea Salt Biomass BurnSulfate Aeros Industry Nitrate AerosoLRTCO (mg/m3)A 5.8 17.7 0.0 36.9 5.4 29.5 3.2 1.3O3 (µg/m3)AV 5.4 0.0 2.9 0.0 0.0 0.0 0.4 91.3PM 2.5 20.1 15.9 0.0 35.7 6.8 18.2 2.2 1.2PM10 19.2 19.4 0.3 32.1 7.0 18.0 2.4 1.7SO2 (µg/m3)A 8.6 11.6 0.0 26.3 7.1 9.9 0.0 36.5NO (mg/m3) 0.0 55.0 0.0 0.0 0.0 41.0 0.9 3.0NO2 (µg/m3)A 9.9 41.6 10.4 4.3 16.6 4.2 0.0 13.1Benzene (µg/ 9.9 55.7 2.9 0.0 18.8 0.0 2.8 10.0Al 37.8 6.1 0.0 3.3 14.5 0.9 0.9 36.5As 57.1 0.0 0.1 7.9 18.6 3.0 0.4 12.9Cd 20.0 0.0 2.4 0.0 12.6 63.3 0.0 1.7Co 75.3 7.9 0.0 6.4 4.3 0.0 0.0 6.1Cr 51.7 22.0 6.4 6.0 3.8 8.8 0.7 0.7Cu 16.6 15.6 19.3 14.1 2.8 25.2 0.0 6.5Fe 32.3 40.0 4.3 3.5 1.9 15.5 0.0 2.4Mn 54.9 8.8 1.5 8.7 0.0 23.6 2.6 0.0Ni 17.8 27.8 3.0 29.5 1.1 18.1 1.5 1.1Pb 31.1 0.0 5.3 8.7 4.2 46.4 4.4 0.0V 39.1 22.4 4.4 16.0 5.3 11.2 0.0 1.6Zn 87.8 0.0 4.2 0.0 4.4 0.0 0.2 3.5phenantrene 0.2 0.0 2.1 81.5 4.5 0.0 5.1 6.6anthracene 0.0 0.0 1.7 81.8 2.0 0.0 7.2 7.3fluoranthene 0.0 2.8 1.5 79.8 4.6 3.6 4.6 3.1pyrene 0.0 3.6 1.5 78.0 4.5 4.9 4.5 3.0benz(a)anthra 0.0 8.2 2.8 69.6 0.3 13.1 2.6 3.4chrycene/triph 0.8 8.0 2.5 69.1 1.2 12.5 2.8 3.0benzo(b+k+j)f 1.2 12.1 2.0 58.2 1.8 19.0 2.8 2.9benzo(a)pyren 0.5 16.8 0.9 52.9 1.3 22.8 2.5 2.4benzo(ghi)per 1.7 14.7 2.3 52.1 3.0 20.8 3.6 1.8indeno(1,2,3-c 1.4 14.7 1.7 53.9 1.5 21.3 3.2 2.2dibenz(a,h+a, 2.2 16.9 2.4 50.8 0.6 22.9 3.0 1.3Cl 0.0 0.0 29.5 12.0 0.0 17.5 38.8 2.3NO3 2.8 17.1 4.3 15.8 7.2 1.9 50.9 0.0SO4 5.9 7.0 1.4 0.0 45.5 0.0 35.7 4.5Ox 22.8 13.3 11.7 12.3 10.0 0.0 28.5 1.4Na+ 7.9 1.0 76.1 2.4 6.8 0.0 5.8 0.0NH4+ 0.0 0.0 0.0 7.4 35.3 0.0 56.2 1.1K+ 6.1 10.2 0.0 28.2 4.3 12.0 37.4 1.8Mg2+ 10.8 18.6 46.8 0.0 7.7 4.3 7.0 4.8Ca2+ 15.8 46.0 0.0 0.0 5.5 8.2 10.3 14.2BC Mass [ug/ 3.6 9.4 20.0 28.0 15.4 0.0 18.8 4.9
study time Average value Min-max matrix
Urban Bakersfield (California)
Dec 1995 ‐ Jan 1996
2390 PM2.5 Nolte et al. (2001)
Fresno (California) Dec 1995 ‐ Jan 1996
2980
Gent, Belgium 1998 ‐ Jan 12‐Mar 11
477 121‐1133 PM10 Zdráhal et al. (2002)
1998 ‐ Jun 10‐Aug 21
19.4 4.1‐34.6
Oslo (Norway) 2001 ‐ Nov 4‐Dec 14
166 nd ‐ 475 PM10 Yttri et al. (2005)
Elverum (Norway) 2002 ‐ Jan 30‐Mar 15
407 134‐971
Missoula (Montana) 2003 ‐ Aug 10‐23
900‐6000 PM2.5 Ward et al. (2006)
Graz (Austria) 2004 ‐ Jan‐Feb, Dec
860 PM10 Caseiro et al. (2009)
2004 ‐ Jun‐Aug 100 Salzburg (Austria) 2004 ‐ Jan‐Feb,
Dec 330
2004 ‐ Jun‐Aug 50 Libby (Montana) Nov 2004 ‐ Feb
2005 3040 PM2.5 Bergauff et al. (2008)
Dettenahusen (Germany) Nov 2005 ‐ Mar 2006
806 35‐3223 PM10 Bari et al. (2010)
Brno (Czech Republic) 2009 (winter) 326 PM2.5 Křůmal et al. (2010)
2009 (summer) 47.1 Slapanile (Czech Republic) 2009 (winter) 572 2009 (summer) 55.6
Geeveston (Tasmania) Mar 2009 ‐ Nov 2010
2430 720‐6020 PM2.5 and PM10 Reisen et al. (2013)
Urban‐Background Vienna (Austria)
2004 ‐ Jan‐Feb, Dec
190‐220 PM10 Caseiro et al. (2009)
2004 ‐ Jun‐Aug 20‐30 Graz (Austria) 2004 ‐ Jan‐Feb,
Dec 450
2004 ‐ Jun‐Aug 80 Salzburg (Austria) 2004 ‐ Jan‐Feb,
Dec 250
2004 ‐ Jun‐Aug 30 Cantù (Italy) 2005 ‐ Feb 21‐
27 963 PM10 Piazzalunga et al. (2010)
Milan (Italy) 2005 ‐ Feb 21‐27
385
Mantova (Italy) 2005 ‐ Feb 21‐27
569
Florence (Italy) 2009‐2010 (winter)
371 PM2.5 Giannoni et al. (2012)
2009 (summer) 13 Borgerhout (Belgium) Feb. 2010 ‐ Feb.
2011 81 11.9‐300 PM10 Maenhaut et al. (2012)
Gent (Belgium) 69 14.8‐330 Gent (Belgium) Nov 2000‐ Mar
2001 420 PM10 Pashynska et al. (2002)
Lens (France) 2011‐2012 10 310 PM10 Waked et al. (2014)
Barcelona (Spain) 2009 ‐ Feb‐Mar 60 PM2.5 Reche et al. (2012)
Šlapanice (Czech Republic) 2009 ‐ Feb 420 PM1 Křůmal et al. (2010)
570 PM2.5 Brno (Czech Republic) 2009 ‐ Feb 220 PM1 320 PM2.5 Zurich (Switzerland) 2003 ‐ Feb 620±160 PM10 Szidat et al. (2006)
Zurich (Switzerland) 2006 ‐ Jan 310±160 PM1 Sandradewi et al. (2008)
Suburban background Mechelen (Belgium) Feb. 2010 ‐ Feb. 2011 95 13.8‐330 PM10
Maenhaut et al. (2012)
Lycksele (Sweden) 2002 – Jan‐Mar 900 PM10 Hedberg et al. (2006)
Vindinge (Denmark) 2005 ‐ Feb‐Abr 170±90 PM2.5 Glasius et al. (2008)
Dettenhausen (Germany) Nov 2005 ‐ Mar 2006 806 35‐3223 PM10 Bari et al. (2006)
Skopje (Macedonia) Aug 2015 ‐ Feb 2016 852 0.2‐5800 PM10 this study
Table A2. Previous levoglucosan studies in Europe (from AIRUSE, LIFE11 ENV/ES/584, Action B4, Biomass
burning in Southern Europe)
Annex 2.
Time series of pollutants measured in Tetovo.
Figure B1. Time series of As, Cd and Zn in PM10 measured at Tetovo. Notice the use of primary (As, Cd) and
secondary (Zn) axis for concentrations.
Figures B2. Time series of Ni and V in PM10 measured at Tetovo.
Figures B3. Time series of Cu and Cr in PM10 measured at Tetovo. Notice the use of primary (Cr) and secondary
(Cu) axis for concentrations.
0
50
100
150
200
250
300
0
1
2
3
4
5
6
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As
Cd
Zn
As, Cd, Zn in PM10 (ng/m3) in Tetovo
0
5
10
15
20
25
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Ni
V
Ni, V in PM10 (ng/m3) in Tetovo
0
5
10
15
20
25
0
20
40
60
80
100
Cu
Cr
Cu and Cr in PM10 (ng/m3) in Tetovo
Figures B4. Time series of Al, Co, Cr, Fe and Mn in PM10 measured at Tetovo. Notice the use of primary (Co, Cr)
and secondary axis (Al, Fe, Mn) for concentrations.
Figure B5. Time series of PM10 mass measured at Tetovo. The annual mean limit value is well exceeded.
0
1000
2000
3000
4000
5000
0
5
10
15
20
25
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Cr
Al
Co
Fe
Mn
Al, Co, Cr, Fe, Mn in PM10 (ng/m3) in Tetovo
0
200
400
600
800
1000
1200
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PM10
annual limit
daily limit
Figure B6. Time series of O3 measured at Tetovo. The annual mean limit value is not exceeded.
Figure B7. Time series of NO2 measured at Tetovo. The annual mean limit value is exceeded.
0
20
40
60
80
100
120
140
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O3
daily max 8h
0
50
100
150
200
250
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NO2
annual limit
Figure B7. Time series of CO measured at Tetovo. The annual mean limit value is not exceeded.
Figure B7. Time series of SO2 measured at Tetovo. The annual mean limit value is not exceeded.
0
5
10
15
20
25
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CO
annual limit
0
20
40
60
80
100
120
11/1/2015 1/1/2016 3/2/2016
SO2
annual limit
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