Report Heavy Metal PAH...Moreover, atmospheric heavy metal samples (PM10) were collected in Tetovo,...

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

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6

1/8/15 1/12/15 1/4/16

Cd

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20

25

1/8/15 1/12/15 1/4/16

Ni

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400

600

1/8/15 1/12/15 1/4/16

Pb

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15

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.



measurement campaign in Tetovo is given. Additionally, the average concentration in Oct‐Dec is given in parenthesis.






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

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30/10/15 30/12/15 29/2/16

As

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Cd

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30/10/15 30/12/15 29/2/16

Ni

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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



Nitrogen dioxide



Carbon monoxide



Ozone EN 14625 (instrument: ‐ ‐ MEPP (Skopje)

ML2010 CASELLA MONITOR)

PM10 CEN/TS 16450 (instrument: PM10 5030 SHARP Monitor ‐ Thermo Scientific Model)


PM2.5 CEN/TS 16450 (instrument: PM2.5 5030 SHARP Monitor ‐ Thermo Scientific Model)


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.



measurement campaign is given.






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

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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

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20.0

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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

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200.0

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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

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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.

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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

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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

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levoglucosan, ng/m

3biomass factor

Levoglucosan

Levoglucosan

Linear(Levoglucosan)

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10.00

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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

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2000

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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



measurement campaign in Tetovo is given. Additionally, the average concentration in Oct‐Dec is given in parenthesis.






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)


1

As Cd Ni Pb

1.7 2.3 75.3 16.3

Feni (ferronickel)


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)


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.

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As, Cd, Zn in PM10 (ng/m3) in Tetovo

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Ni, V in PM10 (ng/m3) in Tetovo

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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.

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Al, Co, Cr, Fe, Mn in PM10 (ng/m3) in Tetovo

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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.

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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.

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Report Heavy Metal PAH...Moreover, atmospheric heavy metal samples (PM10) were collected in Tetovo,...

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