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Measurements of persistent organic pollutants in Estonian ambient air (1990-2013)/Pusivad orgaanilised saasteained Eesti valisohus.

1. INTRODUCTION

Persistent organic pollutants (POPs) harm human health and the environment. The atmosphere is an important contributor of persistent organic pollutants to the land and marine ecosystems (UNEP, 2002a, 2002b). POPs are included in the UNECE Convention on Long-range Transboundary Air Pollution Protocol on Persistent Organic Pollutants (http://www.unece.org/env/lrtap/pops_h1.html). The Executive Body adopted the Protocol on Persistent Organic Pollutants on 24 June 1998 in Aarhus (Denmark).

Passive air samplers (PAS) can be used for the evaluation of point sources at the scale of some square kilometres or even less--from the local plants to diffusive emissions from transportation or household incinerators as well as for evaluating diffusive emissions from secondary sources. Although not sensitive to short-time accidental releases PAS are suitable for measurements of long-term average concentrations at various levels. These samplers are sensitive enough to mirror even small-scale differences, which makes them capable of monitoring spatial, seasonal, and temporal variations (Agrell et al., 2001; Jaward et al., 2003, 2004a, 2004b; Klanova et al., 2006; Gioia et al., 2007; Halse et al., 2011).

Different PAS were employed between 1990 and 2013 from time to time in six Estonian air monitoring stations (Lahemaa, Kunda, Kohtla-Jarve, Tallinn, Muuga, and Vilsandi). Considering results of these POPs measurements in ambient air, the Estonian Lahemaa air monitoring station was selected as a background station for monitoring POPs in European air. Although concentrations of different POPs in Estonian ambient air were very low, they allowed tracking transboundary air pollution carried to Estonia from outside the country (Roots, 1992; Agrell et al., 2001). As the availability of data on the environmental levels of POPs in the ambient air is generally limited in Estonia (Nordic, 1999; Agrell et al., 2001; Schleicher et al., 2004a, 2004b, 2005; Roots and Sweetman, 2007; Roots et al., 2008, 2010, 2011) as well as in the whole of Central and Eastern Europe (CEE) (Nordic, 1999; Agrell et al., 2001; Lassen et al., 2003; Klanova et al., 2006, 2009; Skarek et al., 2007; Miluskaite et al., 2008; Bartos et al., 2009; Dvorska et al., 2009; Pribylova et al., 2012), the aim of this article is to provide information on ambient air pollution with persistent organic pollutants and changes in their emission levels in Estonia from 1990 to 2013. Another aim is to analyse the potential of the Lahemaa station as a background station for monitoring POPs in the European area.

2. MATERIAL AND METHODS

2.1. Sampling sites

Five sampling sites were situated in northern Estonia along the shoreline of the Gulf of Finland and one ambient air monitoring station on Vilsandi Island in western Estonia. Vilsandi is small: 6 km long and barely 3 km wide. A background EMEP (Co-operative programme for monitoring and evaluation of the long-range transmissions of air pollutants in Europe) site Lahemaa has been included in most European projects as a potential candidate for a background monitoring station in Europe (Table 1).

2.2. Sampling

The passive air samplers (PAS) consisting of polyurethane foam disks (diameter 15 cm, thickness 1.5 cm, density 0.030 g [cm.sup.-3]; type N 3038; Gumotex Breclav, Czech Republic) housed in protective chambers (Fig. 1) were employed in this study. A theory of passive air sampling using similar devices was described elsewhere (Shoeib and Harner, 2002; Harner et al., 2004). The sampling chambers were prewashed and solvent-rinsed with acetone prior to installation. All PolyUrethane Filter (PUF) disks were prewashed, cleaned (8 h extraction in acetone and 8 h in dichloromethane), wrapped in two layers of aluminium foil (before and after the sampling), placed in zip-lock polyethylene bags, and kept in the freezer prior to their deployment. The PUF disks were exposed for 4 weeks and the field blanks were obtained by installing and removing the PUF disks at all sampling sites. The average sampling rate of such device was estimated to be 3.5-7 [m.sup.3] per day (Kohoutek et al., 2006; Klanova et al., 2009; Pribylova, et al., 2012) based on the co-employment of the active and passive samplers (giving 100-200 [m.sup.3] of air in 4 weeks of deployment). The exposed PUF disks were wrapped in two layers of aluminium foil, labelled, placed in ziplock polyethylene bags and transported in a cooler at 5 [degrees]C to the laboratory where they were kept in a freezer at -18[degrees]C until analysis.

2.3. Sample analysis

The surrogate recovery standards (PCB 30 and PCB 185 for analysis of polychlorinated biphenyls (PCB) and organochlorine pesticides (OCP); dS-naphthalene, d10-phenanthrene, d12-perylene for analysis of polyaromatic hydrocarbons (PAHs)) were spiked on each sample prior to extraction. One laboratory blank and one reference material were analysed with each set of ten samples. All samples were extracted with dichloromethane in a Buchi System B-811 automatic extractor. After extraction, the sample volume was reduced under a gentle stream of nitrogen at ambient temperature. Fractionation was achieved on a silica gel column; a sulphuric acid modified silica gel column was used for PCB and OCP samples. As the internal standards for PCB and OCP and PAH analyses PCB 121 and terphenyl were used, respectively. Samples were analysed using a GC-MS instrument (GC 7890/MS-MS Triple Quadrupole 7000B; Agilent) with a J&W Scientific fused silica column DB-5MS (5% Ph) in electron impact ionization mode for 16 US EPA PAHs as described earlier (Klanova et al., 2009) and SGE Analytical Science fused silica column HT-8 (8% Ph) in electron impact ionization and MS/MS mode for PCBs: PCB 28, PCB 52, PCB 101, PCB 118, PCB 153, PCB 138, PCB 180 and OCPs: hexachlorocyclohexanes (HCH) ([alpha]-HCH, [beta]-HCH, [gamma]-HCH, [delta]-HCH); 1,1'-(2,2,2trichloroethylidene)-bis[4-chlorobenzene] (DDT); 1,1'(2,2-dichloroethenylidene)-bis[4-chlorobenzene] (DDE); 1,1'-(2,2-dichloroethylidene)-bis[4-chlorobenzene] (DDD); hexachlorobenzene (HCB); and pentachlorobenzene (PeCB).

2.4. Quality assurance and quality control

Recoveries were determined for all samples by spiking with the surrogate standards prior to extraction. Recoveries were for all samples 76-100% and for PCBs/OCPs and for PAHs 71-98%. Recovery factors were not applied to any data. Recovery of native analytes measured for the reference material varied from 88% to 103% for PCBs, from 75% to 98% for OCPs, and from 72% to 102% for PAHs. The laboratory blanks were under the detection limits for all compounds. The field blanks consisted of the pre-extracted PUF disks and were taken at each sampling site. They were extracted and analysed in the same way as the samples, and the levels in field blanks never exceeded 3% of the quantities detected in the samples for PCBs, 1% for OCPs, and 3% for PAHs, indicating a minimal contamination during the transport, storage, and analysis.

More detailed specification of sampling and sample analysis methods, limits of quantifications (for PCBs and OCPs 0.1 ng/PUF per disk), quality assurance/ quality control methods, and the use of field blanks are presented in (Jaward et al., 2004a, 2004b; Schleicher et al., 2004a, 2004b, 2005; Gioia et al., 2007; Roots and Sweetman, 2007; Miluskaite et al., 2008; Klanova et al., 2009; Roots et al., 2010; Halse et al., 2011; Pribylova et al., 2012). The analytical procedures were monitored using NS/EN ISO/IEC 17025 accredited routines (Klanova et al., 2009; Halse et al., 2011).

3. RESULTS AND DISCUSSION

The relationship between the amount of POPs captured on a PUF filter and their concentrations in the sampled air has not been mathematically fully established yet. Thus only empirically estimated information (for example based on parallel active and passive measurements) is available to interpret the results (Jaward et al., 2004a, 2004b; Kohoutek et al., 2006). Results depend on whether they were obtained by passive or active measurements. Passive air sampling is a cheap screening method for comparison of contamination on various sites or for verification of information obtained by active samplers. Different PAS were employed between 1990 and 2013 from time to time in six Estonian air monitoring stations: Lahemaa, Kunda, Kohtla-Jarve, Tallinn, Muuga, and Vilsandi. Distribution of ground-boundary wind directions at regional level at Lahemaa corresponds to that measured at the Vaike-Maarja meteorological station, at Kunda to the Kunda station, at Kohtla-Jarve to the Johvi station, and at Tallinn and Muuga to the Tallinn-Harku station (Roots et al., 2010).

3.1. Comparison of the previously reported results

The first field study was organized in October 1990 by Lund University in order to determine POPs in the air and precipitation from six Baltic Sea countries (Estonia, Finland, Latvia, Lithuania, Poland, and Sweden). All together 16 air monitoring stations participated. Among them were two Estonian air monitoring stations--Lahemaa and Vilsandi (Figs 2-4). The median concentrations in the air samples for all stations were 57 pg/[m.sup.3] for PCBs, 1.6 pg/[m.sup.3] for DDTs, and 25 pg/[m.sup.3] for HCHs. The station in Latvia (Salaspils) showed the highest values of PCBs and DDTs in the air, with a median concentration of 454 pg/[m.sup.3] of PCBs and 12 pg/[m.sup.3] of DDTs. The median concentrations of HCHs were the highest in two Polish stations (Swibno 103 pg/[m.sup.3] and Dziwnow 72 pg/[m.sup.3]). At these stations DDT concentra tions were high too, 6 and 9 pg/[m.sup.3], respectively (Appendix 1, Tables 1A-3A). According to the data by Agrell et al. (2001), the rivers and the atmosphere contributed about equally to the PCB load, while for POPs atmospheric deposition to the Baltic Sea was about five to seven times more important.

The second field study was organized in 1993-1994. The analyses on PCB, made by Lund University, on the samples taken near the Gulf of Riga in the five Baltic air research stations in Estonia and Latvia showed that the air and rain water samples taken in Estonian stations (Vilsandi near Saaremaa 0.05 ng/[m.sup.3] and Tahkuse in western Estonia 0.15 ng/[m.sup.3]) were relatively cleaner compared with the samples taken in Latvia (Salaspils 0.62 ng/[m.sup.3], Salacgriva 0.22 ng/[m.sup.3], and Slitere 0.10 ng/[m.sup.3]). The movement of some POPs, for example PCB, from southern sources outside Estonia was highly significant. Estonian sampling sites were relatively clean, but allow tracking transboundary air pollution carried to Estonia by southern and south-western winds (Roots, 1992; Nordic, 1999).

Scientists of Lancaster University Environmental Chemistry and Ecotoxicology Group completed a large European-scale air sampling campaign in 2002 within the project 'POPs Fate Modelling'. Seventy-one samplers were successfully deployed across 22 countries. Among the stations were two Estonian stations: Lahemaa, a background EMEP station, and Kohtla-Jarve, an industrial (oil shale chemistry) region station. In Estonia the so-called 'new pollutants', which were in Estonian air for the first time analysed, attracted attention. These were polychlorinated naphtalenes (PCNs) and polybrominated diphenyl ethers (PBDEs). The PAS were changed after a six-week period (15 June-30 July 2002), and analysed by the methods presented by Jaward et al. (2003, 2004a, 2004b). For Estonia positive information was that the concentrations of PCN-12 isomers in the samples from the two Estonian air monitoring stations were under detection limit (Foday et al., 2004) and that PBDE values in Estonian air were generally low (Gioia et al., 2007; Roots and Sweetman, 2007).

In 2004 PAS were deployed at 23 background locations along a broadly west-east transect in eight northern European countries (Ireland, the United Kingdom, Denmark, Norway, Sweden, Finland, Estonia, and Russia) and analysed for PCBs, PBDEs, PAHs, HCBs, and DDTs (Gioia et al., 2007) (Fig. 5). Among them was the Estonian Lahemaa station, a background EMEP station (sampling period 10.08.-28.10.2004) (Table 2). The cleanest air samples were collected from Norway and Estonia. By the data in (Gioia et al., 2007), advection from southern and western Europe appeared to contribute to ambient POPs levels for countries in the central and north-eastern part of the transect (among these Estonia).

In the coordinated campaign in various European countries (34 countries and 86 sites) during late summer 2006 samplers were exposed for about 3 months (Halse et al., 2011). Among the sites was the Estonian Lahemaa station (sampling period 06.07.-10.10.2006) (Table 3). As at the beginning of August 2006 the wind was flowing from the north-east at a relatively high speed (4-7 m/s), it brought in air from the north-western part of Russia (Leningrad Oblast and Karelia) suffering several big forest fires at the time (Roots et al., 2008, 2010). Therefore for example naphthalene concentrations in the Lahemaa and Kunda stations increased 9 and 6 times and for benzo(a)pyrene 6.5 and 2.5 times, respectively (Klanova et al., 2006).

3.2. Emissions of persistent organic pollutants

At present, the Estonian Environmental Agency uses the CollectER tool for the calculation of emissions from diffuse sources. Data on point sources (emissions and burnt fuel) are transferred from OSIS (Valisohu saasteallikate infosusteem--Estonian ambient air polluters infosystem) to CollectER (EEA, 2013). The national emission inventory data that are stored in the CollectER annual inventory databases are used for reporting (Kohv et al., 2012, 2013). In 2010 the emissions of pollutants had increased due to increasing biomass consumption in the energy and residential sectors (Fig. 6) (Kohv et al., 2012). These estimates are subject to large uncertainty as emission factors (EFs) used in this inventory were derived from only one general study and need not be representative for Estonia; moreover, the used EFs do not depend on the type of combustion appliance. For example, HCB EFs are two times higher in the cooking stove compared to the other combustion facilities, and PCDD/Fs EFs in the fireplace are ca 46 times higher compared to the masonry heater and the cooking stove. These three facilities are typically used in Estonian households (Mots et al., 2013).

At the beginning of the 2000s the project 'Dioxin in Candidate Countries' was carried out on behalf and with financial support of the European Commission, DG Environment (Quass et al., 2004). The very low dioxin emissions from two Estonian power plants, oil plant, and cement factory are due to the very efficient combustion in the furnaces thanks to very high temperatures, turbulence, and long retention times (Quass et al., 2004; Roots, 2004; Schleicher et al., 2004a, 2004b, 2005; Roots and Sweetman, 2007).

As measurements of real dioxin emissions in Estonia were highly needed, in March 2003 PCDD/Fs emissions were measured from two power plants (Estonian and Baltic Power Plants) and the shale oil producing plant located near the town of Narva in NE Estonia. The Danish environmental assistance to Eastern Europe (DANCEE) sponsored the project, and dk-TEKNIK ENERGY & ENVIRONMENT (now FORCE Technology) was responsible for measurements, which were conducted in cooperation with the Estonian Environmental Research Centre in Tallinn (Schleicher et al., 2004b, 2005).

The two power plants produce more than 90% of the electricity consumed in Estonia by combusting more than 10 million tonnes of oil shale per year, which is around 85% of the total consumption of oil shale in the country. These power plants are the world's largest thermal power stations burning low-grade oil shale. All the measured concentrations of dioxins emitted from the Estonian and Baltic Power Plants are very low. The total annual dioxin emission from the two oil shale fired power plants (Fig. 7) into the air is estimated at 160 to 300 mg International Toxicity Equivalents (I-TEQ) (Schleicher et al., 2004b, 2005), which is more than ten times lower than previous estimations (Lassen et al., 2003).

All the measured concentrations of dioxin emissions from the shale oil plant were very low, and much lower than the EU emission limit value for municipal solid waste incineration (MSWI): 0.1 ng I-TEQ/[m.sup.3] (n,d). The total emission of dioxins is estimated at 0.2 mg ITEQ/year into air and 700 mg/year with ash (Schleicher et al., 2004a). The naphthalene and PAH concentrations were much lower than the Danish emission limit values (Guidances for Air Emission Regulation, 2002).

3.3. Comparison of results from Lahemaa and some Central and Eastern European stations during 2006-2012 (2013)

Estonia, Northeast Europe, is located in a transitional zone between a maritime climate in the west and a continental climate in the east. Changes in the percentages of eight main surface wind directions at 14 meteorological stations in Estonia were studied during 1966-2008. At the Lahemaa station the percentages of western (W) and south-western (SW) winds have clear positive trends (increase 5-8%) (Fig. 8) while southeastern (SE), eastern (E), and north-eastern (NE) winds showed negative tendencies in winter. It appeared that there had been much less changes for certain directions (N, S) and months (April, July, October, November, December) and much more changes for other directions (W, SE) and months (January, February, March, May, June) (Jaagus and Kull, 2011).

Advection from the south and west of Europe appeared to contribute to ambient POPs levels for countries in the central and north-eastern part of the transect (Gioia et al., 2007). Major emissions of [alpha]-HCH in Poland, [gamma]-HCH in France, PCBs in Germany, Poland, and the Czech Republic, and DDT in the Czech Republic and Germany measured in 1997-1999 had significantly decreased by 2004-2006 (Dvorska et al., 2009). It was estimated that air from the south, southeast, and south-west accounted for approximately 80% of the wet deposition and 50% of the gaseous deposition of dioxins (PCDD/F) to the Baltic Sea (Sellstrom et al., 2009).

The model monitoring network in the Czech Republic has been functioning since 2005, and passive air sampling surveys of Central and Eastern Europe (CEE) were initiated in 2006 (Klanova et al., 2006; Kohoutek et al., 2006). Samples were exposed in eight CEE countries (Bosnia and Herzegovina, Czech Republic, Estonia, Latvia, Lithuania, Romania, Serbia, and Slovakia) (Fig. 9) over 4-weeks periods. The Estonian data are presented in (Klanova et al., 2006; Roots et al., 2008, 2010). During all four sampling periods of the study the wind speeds followed the main course of long-term seasonal wind speed at ground level (Kull and Laas, 2003) and at 850- or 500-hPa level (Keevallik and Soomere, 2008). The concentrations of PCB and its congeners, HCB, PeCB, HCH, and DDT were very low in Estonian ambient air (Klanova et al., 2006; Roots et al., 2008, 2010) and soil (Klanova et al., 2006; Sajwan et al., 2008; Kumar et al., 2009; Roots et al., 2011).

Compared to 2006-2007, the concentrations of HCHs, PCBs, and DDTs in the ambient air at Lahemaa had significantly decreased by 2009-2012 (Fig. 10 and Appendix 1, Tables 4A-6A). Two easily volatile PCB compounds (PCB 28 and 52) accounted for about 50% of the sum of the concentrations of 7 PCBs (PCB 28, 52, 101, 118, 138, 153, and 180) in the ambient air at Lahemaa. Long-range pollution transport is supposed to be a major pollution source. In an earlier study (Roots et al., 2010) we found that the relatively consistent ratio of HCB and PeCB fluctuated between 2.5 and 5.6 in 2006, but in 2009-2012 it increased to 11.9 (July-September 2011). This indicates that the HCB and PeCB do not stem from incineration processes but are mainly evaporates of industrial HCB with a minor impact of PeCB. The evaporate theory is consistent with the finding of higher HCB and PeCB values in the warm months (July, August, September) of our studies. In July and August 2010 very high concentrations of particulate matter (PM) PM 10 and PM2.5 were analysed in the Lahemaa ambient air, respectively 13.20 and 7.60 [micro]g/[m.sup.3] in July and 11.03 and 6.94 [micro]g/[m.sup.3] in August (Kabral et al., 2012). To detect the PBDEs source the correlation between PCBs and PBDEs in Estonian soil was analysed. If there was a significant correlation, then the source of PBDEs would be the same as for the accumulation of PCBs in soil. However, the results showed a very weak correlation ([r.sup.2] = 0.165), and therefore the PBDE source in North Estonia is entirely different than that of PCBs (Kumar et al., 2009).

The import of OCPs was prohibited in Estonia at the end of 1967, and none of these pesticides have ever been produced in Estonia (Muur, 1996). All the old OCP stocks in Estonia have been destroyed (Roots et al., 2010). Based on the data on PCBs, OCPs, and PBDEs in a limited number of soil samples from Estonia, the contamination level with these POPs seems to be relatively low (Sajwan et al., 2008; Kumar et al., 2009; Roots et al., 2011).

4. CONCLUSIONS

The level of contamination with persistent organic pollutants seems to be relatively low in Estonia as the limited number of ambient air and soil samples suggest. The concentrations of HCHs, PCBs, and DDTs measured in the ambient air at Lahemaa in 2006-2007 had significantly decreased by 2009-2012. The very low POPs emissions from the Estonian two power plants, the shale oil plant, and the cement plant are due to the very efficient combustion in the furnaces achieved by very high temperatures, turbulence, and long retention times. The concentrations of PCB and its congeners, HCB, PeCB, HCH, DDT, PBDE, and PCN in the Estonian ambient air were very low, but they allow tracking transboundary air pollution carried into the country.

To assess long-term trends in the atmospheric levels of POPs, required for the effectiveness evaluation of the Stockholm Convention, selected background sites in the CEE region continue to be monitoring within the framework of the MONET passive sampling network. The Lahemaa background station seems to be an appropriate candidate for continuous background monitoring of POPs in Europe.

In order to improve the quality of the environment in Europe, the technologies used in power engineering and industry need to be optimized.

doi: 10.3176/proc.2015.2.07

ACKNOWLEDGEMENTS

This work was carried out with the support of the Estonian State Monitoring Programme (ESMP); core facilities of the Research Centre for Toxic Compounds in the Environment (RECETOX)--National Infrastructure for Research of Toxic Compounds in the Environment, project No. LM2011028, funded by the Ministry of Education, Youth and Sports of the Czech Republic under the activity 'Projects of major infrastructures for research, development and innovations'; and large European-scale air sampling campaigns. The United States Department of Energy (DOE) and the United States Environmental Protection Agency (Contract No. DE-FG09-96SR18558) supported analyses of the Estonian soil samples.

APPENDIX 1

SUPPORTING MATERIAL

Table 1A. Summary PCB concentrations in the air and
precipitation and calculated depositions
(Agrell et al., 2001)

Latitude          Station           Air, pg/
                                   [m.sup.3]

54[degrees]00'    Dziwnow          55 (n = 5)
54[degrees]15'    Swibno           69 (n = 6)
55[degrees]25'    Ventes R.        61 (n = 10)
56[degrees]14'    Oland            76 (n = 21)
56[degrees]17'    Breanas          79 (n = 21)
56[degrees]50'    Salaspils        454 (n = 20)
58[degrees]20'    Vilsandi         79 (n = 9)
58[degrees]21'    Gotska s.        60 (n = 24)
59[degrees]17'    Stockholms s.    80 (n = 21)
59[degrees]30'    Lahemaa          49 (n = 16)
63[degrees]02'    Vasa             32 (n = 27)
63[degrees]03'    Docksta          50 (n = 24)
63[degrees]32'    Norrbyn          48 (n = 24)
63[degrees]36'    Holmogadd        57 (n = 23)
64[degrees]31'    Bjuroklubb       38 (n = 24)
65[degrees]44'    Kalix            47 (n = 24)
                  All stations     57 (n = 299)

Latitude          Precipitation,    Deposition,
                       ng/L        ng/[m.sup.2] x d

54[degrees]00'     1.4 (n = 2)      2.3 (n = 2)
54[degrees]15'     4.4 (n = 4)      5.0 (n = 4)
55[degrees]25'     2.0 (n = 15)     3.7 (n = 15)
56[degrees]14'     8.3 (n = 15)     3.5 (n = 15)
56[degrees]17'     2.8 (n = 12)     2.8 (n = 12)
56[degrees]50'     10.7 (n = 15)    17.9 (n = 15)
58[degrees]20'     1.5 (n = 9)      2.2 (n = 9)
58[degrees]21'     2.0 (n = 15)     3.0 (n = 15)
59[degrees]17'     1.3 (n = 10)     2.4 (n = 10)
59[degrees]30'     0.8 (n = 12)     1.8 (n = 12)
63[degrees]02'     0.9 (n = 12)     1.2 (n = 12)
63[degrees]03'     1.8 (n = 15)     2.6 (n = 15)
63[degrees]32'     1.8 (n = 17)     3.2 (n = 14)
63[degrees]36'     4.9 (n = 12)     5.7 (n = 12)
64[degrees]31'     2.9 (n = 13)     2.2 (n = 13)
65[degrees]44'     2.4 (n = 14)     1.5 (n = 14)
                   2.3 (n = 192)    2.7 (n = 192)

Table 2A. Summary DDT concentrations in the air and
precipitation and calculated depositions
(Agrell et al., 2001)

Latitude          Station             Air,
                                  pg/[m.sup.2]

54[degrees]00'    Dziwnow         9.0 (n = 5)
54[degrees]15'    Swibno          6.3 (n = 6)
55[degrees]25'    Ventes R.       2.3 (n = 10)
56[degrees]14'    Oland           5.1 (n = 21)
56[degrees]17'    Breanas         3.3 (n = 20)
56[degrees]50'    Salaspils       12.4 (n = 20)
58[degrees]20'    Vilsandi        6.9 (n = 8)
58[degrees]21'    Gotska s.       2.0 (n = 24)
59[degrees]17'    Stockholms s.   2.0 (n = 21)
59[degrees]30'    Lahemaa         2.0 (n = 16)
63[degrees]02'    Vasa            0.8 (n = 26)
63[degrees]03'    Docksta         1.2 (n = 24)
63[degrees]32'    Norrbyn         0.9 (n = 24)
63[degrees]36'    Holmogadd       1.2 (n = 22)
64[degrees]31'    Bjuroklubb      0.7 (n = 22)
65[degrees]44'    Kalix           0.9 (n = 24)
                  All stations    1.6 (n = 281)

Latitude          Precipitation,    Deposition,
                       ng/L        ng/[m.sup.2] x d

54[degrees]00'    0.21 (n = 2)     0.30 (n = 2)
54[degrees]15'    1.24 (n = 3)     1.0 (n = 3)
55[degrees]25'    0.18 (n = 15)    0.38 (n = 15)
56[degrees]14'    0.71 (n = 13)    0.38 (n = 13)
56[degrees]17'    0.17 (n = 12)    0.19 (n = 12)
56[degrees]50'    0.40 (n = 15)    0.64 (n = 15)
58[degrees]20'    0.28 (n = 5)     0.23 (n = 5)
58[degrees]21'    0.15 (n = 15)    0.19 (n = 15)
59[degrees]17'    0.09 (n = 10)    0.12 (n = 10)
59[degrees]30'    0.06 (n = 12)    0.1 (n = 12)
63[degrees]02'    0.03 (n = 12)    0.05 (n = 12)
63[degrees]03'    0.08 (n = 15)    0.08 (n = 15)
63[degrees]32'    0.07 (n = 16)    0.09 (n = 16)
63[degrees]36'    0.18 (n = 8)     0.16 (n = 8)
64[degrees]31'    0.04 (n = 11)    0.05 (n = 11)
65[degrees]44'    0.07 (n = 14)    0.05 (n = 14)
                  0.13 (n = 178)   0.15 (n = 178)

Table 3A. Summary HCH concentrations in the air and
precipitation and calculated depositions
(Agrell et al., 2001)

Latitude        Station             Air,
                                [pg/m.sup.3]

54[degrees]00'  Dziwnow         72 (n = 5)
54[degrees]15'  Swibno          103 (n = 6)
55[degrees]25'  Ventes R.       26 (n = 10)
56[degrees]14'  Oland           20 (n = 21)
56[degrees]17'  Breanas         45 (n = 21)
56[degrees]50'  Salaspils       39 (n = 20)
58[degrees]20'  Vilsandi        33 (n = 28)
58[degrees]21'  Gotska s.       45 (n = 24)
59[degrees]17'  Stockholms s.   24 (n = 21)
59[degrees]30'  Lahemaa         26 (n = 16)
63[degrees]02'  Vasa            30 (n = 16)
63[degrees]03'  Docksta         18 (n = 24)
63[degrees]32'  Norrbyn         7 (n = 24)
63[degrees]36'  Holmogadd       20 (n = 23)
64[degrees]31'  Bjuroklubb      28 (n = 15)
65[degrees]44'  Kalix           4 (n = 21)
                All stations    25 (n = 275)

Latitude        Precipitation,    Deposition,
                     ng/L        ng/[m.sup.2] x d

54[degrees]00'  0.63 (n = 2)     1.4 (n = 2)
54[degrees]15'  8.65 (n = 3)     5.7 (n = 3)
55[degrees]25'  1.63 (n = 15)    3.2 (n = 15)
56[degrees]14'  2.5 (n = 13)     0.98 (n = 13)
56[degrees]17'  1.8 (n = 12)     1.9 (n = 12)
56[degrees]50'  1.3 (n = 15)     2.5 (n = 15)
58[degrees]20'  2.1 (n = 5)      3.7 (n = 5)
58[degrees]21'  1.4 (n = 15)     2.2 (n = 15)
59[degrees]17'  1.0 (n = 10)     1.3 (n = 10)
59[degrees]30'  0.31 (n = 12)    0.53 (n = 12)
63[degrees]02'  0.38 (n = 12)    1.3 (n = 12)
63[degrees]03'  0.92 (n = 15)    1.7 (n = 15)
63[degrees]32'  0.16 (n = 17)    0.61 (n = 17)
63[degrees]36'  1.3 (n = 8)      0.82 (n = 8)
64[degrees]31'  0.46 (n = 10)    0.22 (n = 10)
65[degrees]44'  0.33 (n = 14)    0.16 (n = 14)
                1.0 (n = 178)    1.3 (n = 178)

Table 4A. Concentrations of POPs (ng/PAS) in the air at five
Estonian air monitoring stations from March to August 2006
(Klanova et al., 2006) with starting and ending dates
of exposure

Start         21.03.06   19.04.06   17.05.06   12.07.06

End           19.04.06   17.05.06   12.07.06   08.08.06

Sampling      29         28         56         27
days

POP           Tln_01-1   Tln_01-2   Tln_01-3   Tln_01-4

PCB28         11.4       36.3       17.3       48.1
PCB52         4.2        11.3       6.3        13.1
PCB101        1          3.2        2.3        3
PCB118        1.2        3.2        2.5        3.2
PCB153        0.5        1.6        0.7        1.4
PCB138        0.4        1.2        0.6        0.9
PCB180        <LOQ       0.6        0.2        0.3
[alpha]-HCH   6.2        19.9       5.2        2.3
[beta]-HCH    6.8        8          2.7        2.5
[gamma]-HCH   6.4        6.7        4          4.2
o.p'-DDE      0.3        <LOQ       0.2
p.p"-DDE      1.7        1.8        1.3        1.7
o.p'-DDD      0.3        0.3        0.3
p.p'-DDD      0.6        0.8        0.5        0.3
o.p'-DDT      0.2        <LOQ       0.1
p.p'-DDT      0.5        0.8        0.2        0.6
PeCB          3.2        3.2        0.8        1.6
HCB           8          8.3        2.9        5.5

Start         21.03.06     19.04.06     17.05.06     12.07.06

End           19.04.06     17.05.06     12.07.06     08.08.06

Sampling      29           28           56           27
days

POP           Muuga_02-1   Muuga_02-2   Muuga_02-3   Muuga_02-4

PCB28         1.2          5.4          1.9          2.4
PCB52         0.7          3.1          1.4          2.7
PCB101        0.3          1            0.9          0.8
PCB118        0.3          1.6          0.8          0.8
PCB153        0.3          0.6          0.4          0.6
PCB138        <LOQ         0.4          0.2          0.2
PCB180        <LOQ         0.2          <LOQ         0.5
[alpha]-HCH   0.9          13.6         0.5          56.6
[beta]-HCH    4            5.5          1.5          3.1
[gamma]-HCH   2.4          5.5          2.6          3.8
o.p'-DDE      <LOQ         <LOQ         <LOQ         <LOQ
p.p"-DDE      0.9          1.5          0.7          0.9
o.p'-DDD      <LOQ         <LOQ         0.1          <LOQ
p.p'-DDD      <LOQ         0.5          0.3          0.5
o.p'-DDT      <LOQ         <LOQ         <LOQ         <LOQ
p.p'-DDT      0.2          0.6          0.4          0.4
PeCB          2.3          2.5          0.7          1.2
HCB           <LOQ         7.3          2.9          <LOQ

Start         21.03.06   19.04.06   17.05.06   12.07.06

End           19.04.06   17.05.06   12.07.06   08.08.06

Sampling      29         28         56         27
days

POP           Lahemaa_   Lahemaa_   Lahemaa_   Lahemaa_
              03-1       03-2       03-3       03-4

PCB28         0.8        1.2        0.7        1.9
PCB52         0.8        1.1        0.4        0.6
PCB101        0.2        0.7        0.3        0.3
PCB118        <LOQ       1          0.2        <LOQ
PCB153        0.2        0.4        0.2        0.5
PCB138        <LOQ       0.3        0.1        <LOQ
PCB180        <LOQ       <LOQ       <LOQ       <LOQ
[alpha]-HCH   0.6        6.6        1.2        1.6
[beta]-HCH    3          2          1.5        1
[gamma]-HCH   2.6        1.8        1.5        1.6
o.p'-DDE      <LOQ       <LOQ       <LOQ       <LOQ
p.p"-DDE      0.9        0.5        0.5        0.6
o.p'-DDD      <LOQ       <LOQ       <LOQ       <LOQ
p.p'-DDD      0.4        0.2        < LOQ      0.2
o.p'-DDT      <LOQ       <LOQ       <LOQ       <LOQ
p.p'-DDT      <LOQ       <LOQ       <LOQ       <LOQ
PeCB          2.2        1.6        0.6        1
HCB           6.6        5.3        2.5        4.6

Start         21.03.06     19.04.06     17.05.06     12.07.06

End           19.04.06     17.05.06     12.07.06     08.08.06

Sampling      29           28           56           27
days

POP           Kunda_04-1   Kunda_04-2   Kunda_04-3   Kunda_04-4

PCB28         3            1.2          0.6          1.4
PCB52         0.7          1.2          0.4          1
PCB101        0.2          0.3          0.2          <LOQ
PCB118        0.4          0.6          0.1          0.5
PCB153        0.2          0.5          0.1          0.4
PCB138        0.2          0.2          < LOQ        <LOQ
PCB180        0.2          <LOQ         <LOQ         0.3
[alpha]-HCH   7.6          11.6         0.5          2.4
[beta]-HCH    3.3          2.7          0.3          0.9
[gamma]-HCH   2.5          2.4          0.7          1.5
o.p'-DDE      <LOQ         <LOQ         <LOQ         <LOQ
p.p"-DDE      0.9          0.6          0.4          0.7
o.p'-DDD      <LOQ         <LOQ         <LOQ         <LOQ
p.p'-DDD      0.3          <LOQ         0.2
o.p'-DDT      <LOQ         <LOQ         <LOQ         <LOQ
p.p'-DDT      0.6          <LOQ         0.2          <LOQ
PeCB          2.3          1.7          0.6          1.3
HCB           5.9          5.6          2.2          4.6

Start         21.03.06   19.04.06   17.05.06   12.07.06

End           19.04.06   17.05.06   12.07.06   08.08.06

Sampling      29         28         56         27
days

POP           Kohtla-    Kohtla-    Kohtla-    Kohtla-
              J_05-1     J_05-2     J_05-3     J_05-4

PCB28         2.5        3.5        2.5        4.2
PCB52         2.1        5.8        2          1.8
PCB101        0.9        5.7        1.3        1.1
PCB118        1.3        8.7        1.2        1.2
PCB153        0.6        2.1        0.6        0.9
PCB138        0.4        1.6        0.4        0.3
PCB180        <LOQ       0.3        <LOQ       <LOQ
[alpha]-HCH   13.6       4.3        0.4        2
[beta]-HCH    8.2        4.2        1.7        3.6
[gamma]-HCH   4.6        2.7        2.5        3.9
o.p'-DDE      0.2        0.2        0.1        <LOQ
p.p"-DDE      1.6        1.2        1.1        1
o.p'-DDD      0.4        0.2        0.1        <LOQ
p.p'-DDD      0.6        0.3        0.3        <LOQ
o.p'-DDT      <LOQ       <LOQ       0.1        <LOQ
p.p'-DDT      0.9        0.4        0.2        0.4
PeCB          2.8        2.2        0.5        2
HCB           8.7        6.7        2.8        <LOQ

Table 5A. Concentrations of POPs (ng/[m.sup.3])
in the air at the Lahemaa air monitoring station with
starting and ending dates of exposure in 2006-2012
(RECETOX, GENASIS database system, www.genasis.cz)

POP                21.03.2006    19.04.2006    17.05.2006

PCBs (indicator)
PCB28              0.007         0.011         0.003
PCB52              0.007         0.010         0.002
PCB101             0.002         0.006         0.001
PCB118             <LOQ          0.009         0.001
PCB138             <LOQ          0.003         0.001
PCB153             0.002         0.003         0.001
PCB180             <LOQ          <LOQ          <LOQ

OCPs (basic)
A HCH              0.005         0.065         0.007
B_HCH              0.026         0.018         0.007
G_HCH              0.023         0.017         0.008
D HCH              <LOQ          <LOQ          <LOQ
HCB                0.063         0.055         0.017
PP_DDD             0.003         0.002         <LOQ
PP_DDE             0.008         0.004         0.002
PP_DDT             <LOQ          <LOQ          <LOQ
OP_DDT             <LOQ          <LOQ          <LOQ

POP                12.07.2006    25.04.2007    15.05.2007

PCBs (indicator)
PCB28              0.019         0.007         0.011
PCB52              0.006         0.005         0.009
PCB101             0.003         <LOQ          0.002
PCB118             <LOQ          <LOQ          0.003
PCB138             <LOQ          <LOQ          0.002
PCB153             0.004         <LOQ          0.003
PCB180             <LOQ          <LOQ          <LOQ

OCPs (basic)
A HCH              0.018         0.077         0.033
B_HCH              0.010         0.016         0.014
G_HCH              0.016         0.004         0.018
D HCH              <LOQ          <LOQ          0.008
HCB                0.054         <LOQ          0.051
PP_DDD             0.002         <LOQ          0.002
PP_DDE             0.005         0.005         0.006
PP_DDT             <LOQ          0.003         <LOQ
OP_DDT             <LOQ          <LOQ          <LOQ

POP                19.06.2007    17.07.2007    2.08.2007

PCBs (indicator)
PCB28              0.013         0.012         0.010
PCB52              0.010         0.016         0.007
PCB101             0.002         <LOQ          0.002
PCB118             0.002         0.004         0.002
PCB138             <LOQ          0.003         <LOQ
PCB153             0.005         0.008         0.004
PCB180             <LOQ          <LOQ          <LOQ

OCPs (basic)
A HCH              0.074         0.030         0.041
B_HCH              0.015         0.029         0.004
G_HCH              0.031         0.032         0.025
D HCH              <LOQ          <LOQ          <LOQ
HCB                0.076         0.101         0.065
PP_DDD             <LOQ          <LOQ          <LOQ
PP_DDE             0.009         0.012         0.009
PP_DDT             0.003         0.004         <LOQ
OP_DDT             <LOQ          <LOQ          <LOQ

POP                6.10.2009     3.11.2009     2.12.2009

PCBs (indicator)
PCB28              0.014         0.012         0.008
PCB52              0.005         0.016         0.005
PCB101             0.001         0.001         0.000
PCB118             <LOQ          0.002         0.001
PCB138             <LOQ          0.001         <LOQ
PCB153             0.002         0.001         0.002
PCB180             <LOQ          <LOQ          <LOQ

OCPs (basic)
A_HCH              0.002         0.005         0.001
B_HCH              <LOQ          <LOQ          <LOQ
G_HCH              0.016         0.013         <LOQ
D_HCH              <LOQ          <LOQ          <LOQ
HCB                0.056         0.053         0.030
PP_DDD             0.001         0.001         0.000
PP_DDE             0.007         0.006         0.004
PP_DDT             0.003         0.002         0.001
OP_DDT             <LOQ          <LOQ          <LOQ

POP                29.12.2009    27.01.2010    25.02.2010

PCBs (indicator)
PCB28              0.009         0.011         0.009
PCB52              0.009         0.008         0.008
PCB101             0.000         0.002         <LOQ
PCB118             <LOQ          0.001         0.001
PCB138             0.001         0.001         <LOQ
PCB153             0.001         0.004         0.002
PCB180             <LOQ          <LOQ          <LOQ

OCPs (basic)
A_HCH              0.007         0.002         0.002
B_HCH              <LOQ          0.003         0.009
G_HCH              0.006         0.023         0.010
D_HCH              <LOQ          <LOQ          <LOQ
HCB                0.038         0.050         0.049
PP_DDD             <LOQ          <LOQ          <LOQ
PP_DDE             0.002         0.004         0.004
PP_DDT             <LOQ          0.002         <LOQ
OP_DDT             <LOQ          <LOQ          <LOQ

POP                23.03.2010    20.04.2010    19.05.2010

PCBs (indicator)
PCB28              0.009         0.009         0.004
PCB52              0.004         0.005         0.003
PCB101             <LOQ          0.005         0.002
PCB118             0.002         0.002         0.001
PCB138             0.002         <LOQ          0.001
PCB153             0.002         0.002         0.002
PCB180             <LOQ          <LOQ          <LOQ

OCPs (basic)
A_HCH              0.015         0.023         0.013
B_HCH              <LOQ          0.005         <LOQ
G_HCH              0.011         0.015         0.007
D_HCH              <LOQ          <LOQ          <LOQ
HCB                0.084         0.077         0.040
PP_DDD             <LOQ          <LOQ          0.001
PP_DDE             0.004         0.005         0.002
PP_DDT             <LOQ          <LOQ          <LOQ
OP_DDT             <LOQ          <LOQ          0.001

POP                14.07.2010    10.08.2010    9.09.2010

PCBs (indicator)
PCB28              0.006         0.004         0.004
PCB52              0.006         0.005         0.004
PCB101             0.008         0.005         < LOQ
PCB118             0.002         0.002         <LOQ
PCB138             0.002         0.002         <LOQ
PCB153             0.002         0.002         0.002
PCB180             <LOQ          <LOQ          <LOQ

OCPs (basic)
A_HCH              0.024         0.019         0.021
B_HCH              <LOQ          <LOQ          <LOQ
G_HCH              0.014         0.009         0.012
D_HCH              <LOQ          <LOQ          <LOQ
HCB                0.063         0.073         0.094
PP_DDD             0.002         <LOQ          <LOQ
PP_DDE             0.007         0.005         0.008
PP_DDT             <LOQ          <LOQ          <LOQ
OP_DDT             <LOQ          <LOQ          <LOQ

POP                5.10.2010     3.11.2010     1.12.20

PCBs (indicator)
PCB28              0.004         0.007         0.007
PCB52              0.004         0.005         0.005
PCB101             0.002         0.002         0.002
PCB118             <LOQ          <LOQ          <LOQ
PCB138             <LOQ          <LOQ          <LOQ
PCB153             <LOQ          <LOQ          <LOQ
PCB180             <LOQ          <LOQ          <LOQ

OCPs (basic)
A HCH              0.013         0.015         0.013
B HCH              <LOQ          <LOQ          <LOQ
G HCH              0.011         0.009         0.005
D HCH              <LOQ          <LOQ          <LOQ
HCB                0.103         0.132         0.144
PP_DDD             <LOQ          <LOQ          <LOQ
PP DDE             0.003         0.005         0.005
PP DDT             <LOQ          <LOQ          <LOQ
OP_DDT             <LOQ          <LOQ          <LOQ

POP                30.12.2010    25.01.2011    28.06.2011

PCBs (indicator)
PCB28              0.006         0.002         0.006
PCB52              0.004         0.002         0.005
PCB101             <LOQ          <LOQ          0.003
PCB118             <LOQ          <LOQ          0.001
PCB138             0.004         0.002         <LOQ
PCB153             <LOQ          0.002         0.001
PCB180             <LOQ          <LOQ          <LOQ

OCPs (basic)
A HCH              0.012         0.011         0.024
B HCH              <LOQ          <LOQ          <LOQ
G HCH              0.010         <LOQ          0.011
D HCH              <LOQ          <LOQ          0.003
HCB                0.096         0.087         0.071
PP_DDD             <LOQ          <LOQ          <LOQ
PP DDE             0.004         0.002         0.005
PP DDT             <LOQ          <LOQ          0.001
OP_DDT             <LOQ          <LOQ          0.002

POP                20.09.2011    14.12.2011    7.03.2012

PCBs (indicator)
PCB28              0.003         0.003         0.004
PCB52              0.003         0.002         0.003
PCB101             0.001         <LOQ          0.001
PCB118             <LOQ          <LOQ          <LOQ
PCB138             <LOQ          <LOQ          <LOQ
PCB153             <LOQ          <LOQ          <LOQ
PCB180             <LOQ          <LOQ          <LOQ

OCPs (basic)
A HCH              0.016         0.009         0.010
B HCH              <LOQ          <LOQ          <LOQ
G HCH              0.008         0.003         0.006
D HCH              <LOQ          0.003         <LOQ
HCB                0.091         0.097         0.065
PP_DDD             <LOQ          <LOQ          <LOQ
PP DDE             0.006         0.003         0.003
PP DDT             <LOQ          <LOQ          <LOQ
OP_DDT             <LOQ          <LOQ          <LOQ

POP                31.05.2012    22.08.2012    14.11.2012

PCBs (indicator)
PCB28              0.004         0.003         0.004
PCB52              0.003         0.002         0.003
PCB101             <LOQ          <LOQ          <LOQ
PCB118             <LOQ          <LOQ          <LOQ
PCB138             <LOQ          <LOQ          <LOQ
PCB153             <LOQ          <LOQ          <LOQ
PCB180             <LOQ          <LOQ          <LOQ

OCPs (basic)
A HCH              0.010         0.011         0.008
B HCH              <LOQ          <LOQ          <LOQ
G HCH              0.006         0.005         0.004
D HCH              <LOQ          <LOQ          <LOQ
HCB                0.048         0.065         0.073
PP_DDD             <LOQ          <LOQ          <LOQ
PP DDE             0.003         0.006         0.005
PP DDT             <LOQ          <LOQ          <LOQ
OP_DDT             <LOQ          <LOQ          <LOQ

Table 6A. Concentrations of POPs (ng/sample) in the air at the
Lahemaa air monitoring station with starting and ending dates
of exposure in 2006-2013 (RECETOX, GENASIS database
system, www.genasis.cz)

POP       21.03.2006    19.04.2006    17.05.2006    12.07.2006

          19.04.2006    17.05.2006    12.07.2006    8.08.2006

A_HCH     0.58          6.62          1.22          1.637
B_HCH     3.04          2.04          1.46          1.034
D HCH     <0.1          <0.1          <0.1          <0.1
G_HCH     2.6           1.82          1.5           1.551
OP_DDD    <0.1          <0.1          <0.1          <0.1
OP_DDE    <0.1          <0.1          <0.1          <0.1
OP_DDT    <0.1          <0.1          <0.1          <0.1
PP_DDD    0.4           0.22          <0.1          0.237
PP DDE    0.9           0.5           0.49          0.56
PP_DDT    <0.1          <0.1          <0.1          <0.1
PECB      2.18          1.64          0.64          1.034
HCB       6.58          5.34          2.5           4.631

PCB28     0.82          1.16          0.66          1.938
PCB52     0.82          1.14          0.42          0.646
PCB101    0.22          0.68          0.29          0.28
PCB118    <0.1          0.96          0.21          <0.1
PCB138    <0.1          0.3           0.12          <0.1
PCB153    0.2           0.36          0.2           0.452
PCB180    <0.1          <0.1          <0.1          <0.1

POP       25.04.2007    15.05.2007    19.06.2007    17.07.2007

          15.05.2007    19.06.2007    17.07.2007    2.08.2007

A_HCH     5.74          3.92          7.04          1.76
B_HCH     1.3           1.94          1.7           1.84
D HCH     <0.1          1.1           <0.1          <0.1
G_HCH     0.34          2.22          3.12          1.92
OP_DDD    <0.1          <0.1          <0.1          <0.1
OP_DDE    <0.1          <0.1          <0.1          <0.1
OP_DDT    <0.1          <0.1          <0.1          <0.1
PP_DDD    <0.1          0.32          <0.1          <0.1
PP DDE    0.4           0.88          0.98          0.76
PP_DDT    0.2           <0.1          0.3           0.24
PECB      1             1.04          1.12          1.12
HCB       <0.1          5.6           6.72          5.64

PCB28     0.56          1.4           1.36          0.72
PCB52     0.38          1.16          1.02          1.02
PCB101    <0.1          0.28          0.22          <0.1
PCB118    <0.1          0.36          0.26          0.26
PCB138    <0.1          0.3           <0.1          0.22
PCB153    <0.1          0.46          0.52          0.54
PCB180    <0.1          <0.1          <0.1          <0.1

POP       2.08.2007     6.10.2009     3.11.2009     2.12.2009

          11.09.2007    3.11.2009     2.12.2009     29.12.2009

A_HCH     5.34          0.18          0.56          0.07
B_HCH     0.64          <0.02         < 0.02        <0.02
D HCH     <0.1          <0.02         < 0.02        <0.02
G_HCH     3.5           1.66          1.42          <0.02
OP_DDD    <0.1          <0.02         < 0.02        <0.02
OP_DDE    <0.1          0.12          0.12          <0.02
OP_DDT    <0.1          <0.02         < 0.02        <0.02
PP_DDD    <0.1          0.12          0.12          0.04
PP DDE    1.38          0.82          0.7           0.39
PP_DDT    <0.1          0.32          0.22          0.06
PECB      1.06          1.32          1.52          0.68
HCB       7.76          5.5           5.54          2.96

PCB28     1.46          1.46          1.32          0.87
PCB52     1             0.58          1.82          0.54
PCB101    0.28          0.1           0.12          0.02
PCB118    0.28          <0.02         0.28          0.06
PCB138    <0.1          <0.02         0.14          <0.02
PCB153    0.66          0.26          0.16          0.22
PCB180    <0.1          <0.02         <0.02         <0.02

POP       29.12.2009    27.01.2010    25.02.2010    23.03.2010

          27.01.2010    25.02.2010    23.03.2010    20.04.2010

A_HCH     0.8           0.2           0.2           1.6
B_HCH     <0.02         0.32          0.92          <0.02
D HCH     <0.02         <0.02         <0.02         <0.02
G_HCH     0.7           2.6           1             1.2
OP_DDD    <0.02         <0.02         <0.02         <0.02
OP_DDE    <0.02         0.18          0.04          0.2
OP_DDT    <0.02         <0.02         <0.02         <0.02
PP_DDD    <0.02         <0.02         <0.02         <0.02
PP DDE    0.26          0.48          0.46          0.4
PP_DDT    <0.02         0.18          <0.02         <0.02
PECB      1.88          0.38          1.72          2.6
HCB       4.14          5.36          4.68          8.4

PCB28     1             1.26          0.96          1
PCB52     1.04          0.94          0.82          0.4
PCB101    0.04          0.2           <0.02         <0.02
PCB118    <0.02         0.14          0.08          0.2
PCB138    0.14          0.08          <0.02         0.2
PCB153    0.16          0.42          0.2           0.2
PCB180    <0.02         <0.02         <0.02         <0.02

POP       20.04.2010    19.05.2010    14.07.2010    10.08.2010

          19.05.2010    14.07.2010    10.08.2010    9.09.2010

A_HCH     2.4           2.2           2.2           2
B_HCH     0.6           <0.02         <0.02         <0.02
D HCH     <0.02         <0.02         <0.02         <0.02
G_HCH     1.6           1.2           1.4           1
OP_DDD    <0.02         <0.02         <0.02         <0.02
OP_DDE    <0.02         <0.02         <0.02         <0.02
OP_DDT    <0.02         0.2           <0.02         <0.02
PP_DDD    <0.02         0.2           0.2           <0.02
PP DDE    0.6           0.4           0.8           0.6
PP_DDT    <0.02         <0.02         <0.02         <0.02
PECB      1.6           0.8           1             1
HCB       7.6           6             5.4           7

PCB28     1             0.8           0.6           0.4
PCB52     0.6           0.6           0.6           0.6
PCB101    0.6           0.4           0.8           0.6
PCB118    0.2           0.2           0.2           0.2
PCB138    <0.02         0.2           0.2           0.2
PCB153    0.2           0.4           0.2           0.2
PCB180    <0.02         <0.02         <0.02         <0.02

POP       9.09.2010     5.10.2010     3.11.2010     1.12.2010

          5.10.2010     3.11.2010     1.12.2010     30.12.2010

A_HCH     2             1.4           1.6           1.4
B_HCH     <0.02         <0.02         <0.02         <0.02
D HCH     <0.02         <0.02         <0.02         <0.02
G_HCH     1.2           1.2           1             0.6
OP_DDD    <0.02         <0.02         <0.02         <0.02
OP_DDE    <0.02         <0.02         <0.02         <0.02
OP_DDT    <0.02         <0.02         <0.02         <0.02
PP_DDD    <0.02         <0.02         <0.02         <0.02
PP DDE    0.8           0.4           0.6           0.6
PP_DDT    <0.02         <0.02         <0.02         <0.02
PECB      1.8           2             3.4           5.2
HCB       8.4           10.4          13.4          15.4

PCB28     0.4           0.4           0.8           0.8
PCB28     0.4           0.4           0.6           0.6
PCB101    <0.02         0.2           0.2           0.2
PCB118    <0.02         <0.02         <0.02         <0.02
PCB138    <0.02         <0.02         <0.02         <0.02
PCB153    0.2           <0.02         <0.02         <0.02
PCB180    <0.02         <0.02         <0.02         <0.02

POP       30.12.2010    25.01.2011    28.06.2011    20.09.2011

          25.01.2011    23.02.2011    20.09.2011    14.12.2011

A_HCH     1.2           1.2           5.233         4.494
B_HCH     <0.02         <0.02         <0.66         <0.66
D HCH     <0.02         <0.02         1.047         <0.72
G_HCH     1             <0.02         2.666         2.277
OP_DDD    <0.02         <0.02         <0.33         <0.33
OP_DDE    <0.02         <0.02         <0.2          <0.2
OP_DDT    <0.02         <0.02         0.554         <0.36
PP_DDD    <0.02         <0.02         <0.36         <0.36
PP DDE    0.4           0.2           1.506         1.909
PP_DDT    <0.02         <0.02         0.468         <0.39
PECB      2.8           3.6           1.118         3.629
HCB       9.4           9.4           13.07         22.17

PCB28     0.6           0.2           1.691         1.042
PCB52     0.4           0.2           1.393         0.87
PCB101    <0.02         <0.02         0.832         0.469
PCB118    <0.02         <0.02         0.445         <0.24
PCB138    0.4           0.2           <0.34         <0.34
PCB153    <0.02         0.2           0.409         <0.27
PCB180    <0.02         <0.02         <0.32         <0.32

POP       14.12.2011    7.03.2012     31.05.2012

          7.03.2012     31.05.2012    22.08.2012

A_HCH     2.591         2.636         2.092
B_HCH     <0.66         <0.66         <0.73
D HCH     0.85          <0.72         1E-06
G_HCH     1.065         1.654         1.456
OP_DDD    <0.33         <0.33         <0.53
OP_DDE    <0.2          <0.2          <0.31
OP_DDT    <0.36         <0.36         <0.72
PP_DDD    <0.36         <0.36         <0.54
PP DDE    1.09          1.115         0.867
PP_DDT    <0.39         <0.39         1E-06
PECB      5.621         1.687         0.609
HCB       26.52         15.37         8.558

PCB28     0.916         1.324         1.078
PCB52     0.69          0.984         0.841
PCB101    <0.32         0.496         <0.57
PCB118    <0.24         <0.24         <0.44
PCB138    <0.34         <0.34         <0.5
PCB153    <0.27         <0.27         <0.44
PCB180    <0.32         <0.32         <0.39

POP       22.08.2012    14.11.2012

          14.11.2012    5.02.2013

A_HCH     2.758         2.448
B_HCH     <0.73         <0.73
D HCH     1E-06         1E-06
G_HCH     1.401         1.117
OP_DDD    <0.53         <0.53
OP_DDE    <0.31         <0.31
OP_DDT    <0.72         <0.72
PP_DDD    <0.54         <0.54
PP DDE    2.067         1.802
PP_DDT    1E-06         1E-06
PECB      1.779         4.631
HCB       14.15         19.23

PCB28     0.97          1.282
PCB52     0.75          0.936
PCB101    <0.57         <0.57
PCB118    <0.44         <0.44
PCB138    <0.5          <0.5
PCB153    <0.44         <0.44
PCB180    <0.39         <0.39


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Ott Roots (a) *, Tiit Lukki (b), Petra Pribylova (c), Jana Boruvkova (c), Petr Kukucka (c), Ondrej Audy (c), Jiri Kalina (c), Jana Klanova (c), Ivan Holoubek (c), Andrew Sweetman (d), and Ole Schleicher (e)

(a) Estonian Environmental Research Institute, Estonian Environmental Research Centre, Marja 4D, 10617 Tallinn, Estonia

(b) Tallinn University, Narva mnt 25, 10120 Tallinn, Estonia

(c) Research Centre for Toxic Compounds in the Environment (RECETOX), Masaryk University, 753/5 Kamenice Str., 625 00 Brno, Czech Republic

(d) Lancaster Environment Centre, Lancaster University, LA1 4YQ Lancaster, United Kingdom

(e) FORCE Technology, Park Alle 345, 2605 Brnndby, Denmark

* Corresponding author, ott.roots@klab.ee

Received 15 December 2014, revised 23 February 2015, accepted 25 February 2015, available online 22 May 2015

Table 1. Characteristics of monitoring sites in Estonia
(Roots and Sweetman, 2007; Roots et al., 2010)

Site           Location             Target

Lahemaa        59[degrees]29'40"N   A European Monitoring and
               25[degrees]55'50"E   Evaluation Programme (EMEP)
                                    background station.
                                    Long-range impacts

Tallinn        59[degrees]27'22"N   Capital city of Estonia.
               24[degrees]41'23"E   Urban impacts

Muuga          59[degrees]29'40"N   Muuga suburban site.
               24[degrees]55'51"E   Industrial impacts

Kunda          59[degrees]29'40"N   Suburban area of an industrial
               26[degrees]35'30"E   town. Industrial impacts

Kohtla-Jarve   59[degrees]24'35"N   Suburban area of an industrial
               27[degrees]16'43"E   town. Industrial impacts

Vilsandi       58[degrees]22'34"N   Background station. Long-range
               21[degrees]50'42"E   impacts

Site           Site specifics

Lahemaa        Lahemaa National Park. 80 km east of
               Tallinn.
               Long-range pollution transport is
               supposed to be major pollution source

Tallinn        Near a car park

Muuga          17 km east of Tallinn, near the main
               cargo harbour of the port of Tallinn.
               Nearly 75% of cargo loaded consisted
               of crude oil and oil products
               in mid-2010s

Kunda          120 km east of Tallinn. Major pollution
               sources are cement and pulp industries
               and transportation

Kohtla-Jarve   160 km east of Tallinn. Major pollution
               sources are oil shale processing,
               chemical industry, and power engineering

Vilsandi       Vilsandi National Park for protecting
               the nature and cultural heritage of the
               coastal landscapes on western Estonian
               islands. Park includes ca 100 islands,
               surface area 180 [km.sup.2]. Vilsandi
               itself is 6 km long and 3 km wide

Table 2. Concentrations of POPs (pg/[m.sup.3]) in ambient air
at the Lahemaa station and concentration ranges for all other
sites (A. Sweetman, personal information)

Site      PCB *    PBDE    pp DDT   HCB

Lahemaa   63.65    1.66    11.57    104.52
Other     34.95-   1.66-   3.55-    79.44-
sites     508.37   20.00   122.6    260.99

* - sum of 7 compounds.

Table 3. Concentrations of POPs (pg/[m.sup.3]) and PAHs (ng/[m.sup.3])
in the air of the Lahemaa station and concentration
ranges of all 86 sites (Halse et al., 2011)

                [SIGMA]7 PCB *   [SIGMA]3 HCH *   [SIGMA]4 DDT *

Lahemaa **          20.77            43.51            12.83
All 86 sites     2.17-121.40      8.63-310.76      1.06-323.63

                [SIGMA]8 PAH *        HCB           [SIGMA]4 *
                                                    chlordanes

Lahemaa **           3.73            46.43             2.20
All 86 sites      0.19-34.93      22.78-115.49      0.16-19.38

* - sum of 7, 3, 4, 8, and 4 compounds, respectively.

** In August-September 2006 the great forest fires near
the Estonian and Finnish boarders with Russia (Leningrad
Oblast and Karelia) caused elevated concentrations of fine
particles and some POPs in the Lahemaa station air.
Wind direction was from Russia towards Estonia and Finland.
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Title Annotation:ENVIRONMENTAL SCIENCE
Author:Roots, Ott; Lukki, Tiit; Pribylova, Petra; Boruvkova, Jana; Kukucka, Petr; Audy, Ondrej; Kalina, Jir
Publication:Proceedings of the Estonian Academy of Sciences
Article Type:Report
Geographic Code:4EXES
Date:Jun 1, 2015
Words:10702
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