Airborne chloronaphthalenes in Scots pine needles of Poland

Chemosphere 75 (2009) 1196–1205

Contents lists available at ScienceDirect

Chemosphere journal homepage: www.elsevier.com/locate/chemosphere

Airborne chloronaphthalenes in Scots pine needles of Poland Anna Orlikowska a,*, Nobuyasu Hanari b, Barbara Wyrzykowska a,1, Ilona Bochentin a, Yuichi Horii b, Nobuyoshi Yamashita b, Jerzy Falandysz a a b

´ sk, 18 Sobieskiego Str., PL 80-952 Gdan ´ sk, Poland Department of Environmental Chemistry, Ecotoxicology and Food Toxicology, University of Gdan National Institute of Advanced Industrial Science and Technology, Environmental Measurement Group, Onogawa 16-1, Tsukuba, Ibaraki 305-8569, Japan

a r t i c l e

i n f o

Article history: Received 13 December 2008 Received in revised form 31 January 2009 Accepted 6 February 2009 Available online 12 March 2009 Keywords: Air pollution Plants Environment Organochlorine contaminants POPs

a b s t r a c t The amounts, profiles and origin of CNs (from triCNs to octaCN) sequestered in Scots pine needles collected from 25 spatially distant sites in Poland have been studied based on congener-specific data obtained after a several clean-up and fractionation steps and final HRGC/HRMS separation and determination. The absolute concentrations of CNs varied largely from site to site, i.e., by 15-fold. The sum of trito octaCN concentration at fifteen of the least contaminated sites ranged from 70 to 280 pg g 1 ww, and at further eight sites were from 340 to 540 pg g 1 ww, while at two the most contaminated were 1000 and 1100 pg g 1 ww. There were some substantial similarities but also variations in triCN to octaCN homologue group profiles depending on the site. Among triCNs the isomers such as 1,2,4-/1,3,7-/1,4,6triCNs (nos. 14/21/24) dominate in Scots pine needles. For majority of the sites examined 1,2,4-/1,3,7-/ 1,4,6-triCNs are also the major contributors to the bulk of CNs determined. Among tetraCNs isomer 1,2,5,8-tetraCN (no. 38) was dominant contributor at eighteen sites, while 1,2,4,6-/1,2,4,7-/1,2,5,7-tetraCN (nos. 33/34/37) at seven other sites. In the case of pentaCNs isomer 1,2,4,5,8-pentaCN (no. 59), was dominant contributor alone. Octachloronaphthalene frequently contributed substantially to the bulk of CNs. The Cluster Analysis and Principal Component Analysis did indicate that the compositional profiles of CNs found in Scots pine needles resemble somehow these found in the bottom ashes after coke and coal burning as well as of Halowax 1000 and 1099 formulations. Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction Tropospheric diffusion is important pathway for world-scale distribution and partitioning of semi-volatile and persistent environmental pollutants possessing similar physical and chemical features, including organochlorine pesticides as well as many halogenated aromatic compounds, originating from industrial and combustion-related sources (Di´Guardo et al., 2003; Lee et al., 2005). Chloronaphthalenes (CNs; polychlorinated naphthalenes, PCNs) are a group containing 75 individual compounds (congeners) differing depending on a number of chlorines attached (from mono- to octachloronaphthalene) and position of chlorine substitution at the naphthalene nuclei. These industrial compounds are well-known as hazardous chemicals because of many earlier appliances and also as persistent environmental pollutants (Falandysz, 1998; Howe et al., 2001; Falandysz, 2003). Chloronaphthalenes * Corresponding author. Present address: Department of Marine Chemistry, Leibniz Institute for Baltic Sea Research Warnemünde (IOW), Seestrabe 15, 18119 Rostock, Germany. Tel.: +49 381 5197 315; fax: +49 381 5197 302. E-mail address: [email protected] (A. Orlikowska). 1 US Environmental Protection Agency, Office of Research and Development, National Risk Management Research Laboratory, 109 Alexander Drive, Research Triangle Park, NC 27711, USA. 0045-6535/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.chemosphere.2009.02.024

were found in many environmental compartments, e.g., in the air (Harner and Bidleman, 1997; Helm and Bidleman, 2003; Mari et al., 2008), soil (Wyrzykowska et al., 2007), biota and sediments (Falandysz et al., 1996, 1997; Falandysz and Rappe, 1997; Horii et al., 2004; Helm et al., 2008). Since development of more advanced analytical methods in the mid 1990s an interest and number of studies on CNs has grown largely (Horii et al., 2004; Falandysz et al., 2006a,b; Noma et al., 2006; Jansson et al., 2008). However in reports on CNs frequently no information is given for mono-, di-, tri-, and heptaCNs or octaCN. Sometimes only a few of 75 congeners have been determined, and what, depending on environmental material, prevents comprehensive data comparison and assessment. An environmental occurrence of CNs is due to their manufacture and use, and much less to their presence as by-side impurity in technical chlorobiphenyls (CBs; polychlorinated biphenyls, PCB) formulations. Chloronaphthalenes in environmentally relevant amount could be formed and released due to processes of fossil fuels and wood combustion, and of waste incineration (Helm and Bidleman, 2003; Lee et al., 2005; Noma et al., 2006; Jansson et al., 2008). Separate incidents of illegal sale and use of CN stockpiles took place also (Yamashita et al., 2003; Falandysz et al., 2008).

A. Orlikowska et al. / Chemosphere 75 (2009) 1196–1205

As unexpectedly found nowadays, some unrecognized earlier problems with CNs could persist locally for century and more. Recently information has been published on the ‘‘LeBlanc” soda factory contaminated site with CNs and dioxins, which could persist in the local environment from 160 years until today (Bogdal et al., 2008). Another fact is a release of CNs from the multiple sources into ambient air and further their atmospheric diffusion worldwide (Lee et al., 2007). Both manufacture and unintentional production of CNs in thermal and chlorination processes yielded the formation and release of probably all 75 CN congeners to the environment (Falandysz, 2003). Certain CN congeners are considered relevant due to dioxin-like potency at low doses, although animal-based or in vitro toxicity data for numerous congeners are scare or absent (Blankenship et al., 2000; Villeneuve et al., 2000; Puzyn et al., 2007). Chloronaphthalenes caused toxicological problems pointing from early years of their manufacture. Crookes and Howe (1993) have summarized published data on toxicity of technical CN mixtures to man and animals due to occupational, accidental and experimental exposure. A few further insights on impact on human and laboratory animals were given by Popp et al. (1997) and Kilanowicz et al. (2004). However, usefulness of the ‘‘total CN” toxicity data must be limited due to many CN constituents, batch-tobatch compositional variability and occurrence of toxic by-side impurities in CNs mixtures (Falandysz et al., 2006a,b). The plant biomass and especially of coniferous needles is considered useful and effective as well as cheap matrix for passivesampling to study atmospheric diffusion of semi-volatile and low-volatile lipophilic compounds, which partition between surrounding ambient air and a surface wax layer (Di´Guardo et al., 2003; Kylin et al., 2003; Hanari et al., 2004a,b; Loganathan et al., 2008). The aim of this study is to investigate amounts, profiles and origin of CNs (from triCNs to octaCN) sequestered in Scots pine needles in Poland, and to provide the data set useful for further local and regional identification of sources and budget-inventories of dioxin-like compounds. Some data regarding dioxin-like compounds and POPs in these Scots pine needles have been communicated previously (Wyrzykowska et al., 2006, 2007; Bochentin et al., 2007).

1197

2. Materials and methods 2.1. Samples and analyses Scots pine (Pinus sylvestris L.) needles were collected at 25 sites across Poland in late October 2002 (Fig. 1). A detailed data about the sampling sites and chemical and statistical analyses are given in Supplementary materials. The quantitative standards of CN congeners and equivalent amounts (1:1:1:1) of the technical CN formulations (Halowax 1000, 1001, 1014 and 1051) were used, while internal standards were 13C-labeled. All solvents and reagents used were of pesticide grade or analytical grade. The Scots pine needle samples were Soxhlet-extracted. The concentrated extracts were cleaned-up and fractionated using a multi-layer silica gel column chromatography, followed by activated basic alumina column chromatography, Hypercarb-HPLC and PYE-HPLC. Finally, they were analyzed for CNs using high-resolution gas chromatography and high-resolution mass spectrometry (HRGC–HRMS). The detection limits of chloronaphthalene congeners are given in Table 1. The recovery rates for 13C-labeled internal standards varied from 92.8% to 116.0% (100.8 ± 7.9%) for PCBs and 71.0–119.3% (106.9 ± 13.3%) for PCDD/Fs. All details of the analytical procedure used are presented and illustrated in details in articles previously published (Hanari et al., 2004a,b). An analysis of chloronaphthalenes profile’s similarity between 25 sites examined was done using principal component analysis (PCA). 3. Results and discussion P 3.1. Absolute CNs ( triCNs to octaCN) concentrations in pine needles Scots pine needles at all sites surveyed contained quantifiable amount of CNs (Table 1). The site-to-site total concentrations of CNs varied largely, i.e., by 15-fold. The sum of tri- to octaCN concentration at fifteen of the least contaminated sites ranged from 70 to 280 pg g 1 ww, and at further ten sites were 340 pg g 1 ww and more. At eight of these more contaminated sites CNs content

Fig. 1. Location of the sampling sites (1a–14c) of Scots pine needles in Poland.

1198

A. Orlikowska et al. / Chemosphere 75 (2009) 1196–1205

Table 1 Chloronaphthalenes content of Scotch pine needles across Poland (pg/g ww). CN no.

Sampling site 1c

1d

2a

2b

3a

56.4

57.0

64.7

59.5

58.5

Trichloronaphthalenes 13 1.3 14/21/24 58 15 9.0 16 2.8 17 3.8 18 2.1 19 3.3 20 0.63 22/23 20 25 3.9 26 <0.10

0.42 27 4.1 0.83 0.92 0.59 2.1 0.11 7.2 1.6 <0.10

1.1 44 6.2 0.84 2.5 0.84 4.0 0.55 9.7 2.3 0.21

1.9 77 13 2.7 4.3 1.1 6.0 0.69 15 3.6 0.17

<0.10 19 3.2 0.50 0.67 0.68 1.4 <0.10 6.1 1.1 <0.10

Tetrachloronaphthalenes 27/39 2.2 28/36 4.1 29/39 2.2 30 2.7 31 <0.06 33/34/37 18 35 14 38 38 40 2.1 41 2.6 42 <0.06 43/45 15 44 <0.06 46 16 47 10 48 <0.06

1.2 1.5 0.63 0.97 <0.06 9.7 4.1 11 0.11 0.68 0.84 4.6 <0.06 5.4 3.9 <0.06

2.4 3.3 1.7 2.2 <0.06 13 10 23 0.39 2.2 1.7 12 <0.06 12 1.5 <0.06

2.0 3.8 2.3 3.3 <0.06 17 8.8 24 1.1 1.7 2.3 13 <0.06 13 1.9 <0.06

Pentachloronaphthalenes 49 1.0 50 2.7 51 1.5 52/60 5.0 53 19 54 0.82 55 <0.06 56 <0.06 57 13 58 0.45 59 29 61 12 62 17

0.22 1.2 0.67 2.8 2.3 0.11 <0.06 0.06 3.1 0.15 7.7 2.4 3.3

0.56 2.1 1.1 3.9 4.5 0.88 <0.06 0.47 5.5 0.17 14 3.8 5.0

Hexachloronaphthalenes 63 1.2 64 1.1 65 7.2 66/67 3.1 68 6.2 69 6.5 70 <0.10 71 10 72 5.5

0.74 <0.10 0.83 0.74 0.40 1.6 <0.10 1.6 <0.10

Heptachloronaphthalenes 73 14 74 25

3.9 7.3

Water (%)

Octachloronaphthalene 75 140 PCNs 542

34 170

4a

4b

5a

5b

6a

6b

57.9

59.9

57.3

56.5

58.8

57.6

0.70 31 3.8 0.85 1.5 0.76 2.4 0.33 11 1.7 <0.10

1.2 66 9.5 2.3 4.0 1.5 6.0 1.2 15 5.5 <0.10

1.7 67 8.8 2.9 4.0 1.9 5.6 0.79 20 4.5 0.24

0.83 92 17 3.2 1.5 0.72 7.5 0.20 13 2.5 <0.10

2.4 93 15 3.2 4.4 2.8 8.7 0.61 32 6.6 <0.10

2.5 100 15 5.5 7.6 4.5 6.0 1.5 47 10 <0.10

1.2 45 7.1 1.5 1.3 0.97 4.2 <0.10 10 2.3 <0.10

<0.06 0.85 0.96 0.53 <0.06 2.3 2.0 9.7 <0.06 1.0 <0.06 3.0 <0.06 7.0 1.5 <0.06

1.2 2.4 1.5 1.6 <0.06 8.1 6.7 17 0.32 1.1 0.49 8.4 <0.06 9.5 4.1 <0.06

2.7 4.9 2.2 1.3 <0.06 10 11 27 0.66 2.8 <0.06 13 <0.06 14 5.4 <0.06

3.5 5.5 3.0 2.0 <0.06 16 14 37 0.90 3.8 2.3 16 <0.06 18 6.6 <0.06

0.91 3.5 0.80 1.9 <0.06 18 6.5 12 0.36 0.70 2.7 12 <0.06 5.5 6.0 <0.06

1.8 4.9 3.3 2.3 <0.06 12 12 34 0.42 1.9 0.87 13 <0.06 18 6.0 <0.06

5.9 7.0 2.6 5.7 <0.06 16 26 67 1.2 4.8 0.48 30 <0.06 37 7.5 <0.06

5.5 2.5 0.76 1.5 <0.06 18 7.9 21 0.55 1.9 0.46 10 <0.06 11 7.0 <0.06

0.55 2.1 1.4 4.8 4.5 0.79 <0.06 0.09 4.5 0.55 10 4.8 3.8

<0.06 0.51 <0.06 0.54 <0.06 <0.06 <0.06 <0.06 0.49 <0.06 3.5 <0.06 0.45

<0.06 2.0 0.30 3.7 3.1 2.4 <0.06 <0.06 5.7 <0.06 16 3.5 2.7

<0.06 <0.06 <0.06 6.1 8.0 6.8 <0.06 <0.06 9.2 <0.06 20 5.8 9.5

0.70 2.6 2.0 3.7 4.5 1.7 <0.06 0.87 5.7 <0.06 13 2.4 4.7

<0.06 <0.06 <0.06 <0.06 0.85 <0.06 <0.06 <0.06 <0.06 <0.06 5.4 <0.06 0.78

0.35 2.0 1.3 5.7 5.0 0.56 <0.06 0.43 5.7 0.35 11 2.8 6.5

2.1 9.3 <0.06 5.5 34 <0.06 <0.06 <0.06 27 0.98 64 22 34

<0.06 1.6 0.92 3.3 7.4 0.95 <0.06 <0.06 4.5 0.54 15 6.4 8.5

3.1 <0.10 2.2 3.0 1.2 3.0 0.51 3.8 0.67

1.4 0.44 1.4 3.1 1.5 1.9 <0.10 2.5 0.73

<0.10 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10

1.7 0.89 0.80 2.3 5.0 3.6 <0.10 9.2 2.2

3.8 <0.10 3.0 3.4 <0.10 <0.10 <0.10 5.1 <0.10

1.5 0.38 1.1 3.1 1.5 2.2 0.76 2.2 0.32

0.42 <0.10 <0.10 0.90 0.87 <0.10 <0.10 <0.10 <0.10

1.1 <0.10 1.8 1.1 <0.10 1.6 <0.10 1.6 0.47

4.0 <0.10 16 <0.10 <0.10 15 <0.10 12 8.1

1.8 <0.10 3.0 1.7 2.6 2.9 <0.10 4.8 2.2

11 15

6.0 13

<0.29 0.86

3.8 10

13 22

8.3 8.9

0.87 1.7

2.4 4.6

27 64

7.5 10

130 370

96 390

3b –

3.3 71

81 280

140 460

59 300

12 230

28 340

290 1100

87 340

CN no.

Sampling site 6c

7a

7b

7c

8a

9b

9c

Water (%)

56.7

55.0

60.2

54.4

57.9

53.0

57.1

60.1

58.9

58.9

49.5

58.7

59.3

1.4 38 5.2 1.5

0.77 30 4.1 1.2

1.5 64 9.1 2.7

2.8 99 14 4.0

1.7 170 27 3.1

1.5 60 8.5 2.3

0.84 46 7.7 1.5

1.5 150 22 5.0

2.3 300 49 7.3

2.3 92 12 3.4

0.76 22 3.2 0.89

1.7 50 7.1 2.9

Trichloronaphthalenes 13 1.3 14/21/24 92 15 15 16 3.2

10b

11a

12a

13a

14b

14c

1199

A. Orlikowska et al. / Chemosphere 75 (2009) 1196–1205 Table 1 (continued) CN no.

Sampling site 6c

17 18 19 20 22/23 25 26

2.7 1.0 8.6 0.85 23 4.3 <0.10

7a

7b

7c

8a

9b

9c

10b

11a

12a

13a

14b

14c

2.3 1.3 4.3 0.63 11 3.1 0.21

1.5 0.26 2.1 <0.10 7.6 1.9 <0.10

2.6 1.3 5.5 1.1 15 4.0 <0.10

5.3 2.0 8.4 1.2 25 6.6 0.38

3.8 1.7 19 0.65 26 5.0 <0.10

2.7 1.1 5.6 0.73 15 3.3 <0.10

1.6 4.0 4.0 0.23 16 2.3 <0.10

4.0 2.0 13 <0.10 36 4.7 <0.10

4.9 2.9 34 0.66 57 7.9 0.32

5.2 2.4 8.0 0.44 35 7.6 0.29

1.4 0.62 2.2 0.46 6.2 2.0 <0.10

3.2 1.3 5.0 1.1 16 4.6 <0.10

Tetrachloronaphthalenes 27/39 2.0 28/36 3.5 29/39 1.1 30 1.6 31 <0.06 33/34/37 19 35 6.3 38 14 40 <0.06 41 0.58 42 1.9 43/45 9.1 44 <0.06 46 6.6 47 9.3 48 <0.06

0.92 2.6 2.6 1.7 0.12 7.0 7.3 27 <0.06 2.1 0.66 9.7 <0.06 14 3.5 0.10

0.92 1.5 0.78 0.50 <0.06 5.9 2.1 5.6 0.07 0.52 0.64 3.6 <0.06 3.0 3.0 0.12

1.5 4.1 3.0 2.3 0.19 8.3 8.3 23 0.53 1.5 0.64 11 <0.06 12 3.7 <0.06

4.7 7.0 3.6 2.7 <0.06 22 17 47 0.90 5.1 2.9 18 0.37 22 11 <0.06

2.1 4.5 1.4 2.2 <0.06 42 8.8 21 0.61 1.3 5.0 27 <0.06 10 13 <0.06

2.3 3.0 0.99 1.5 <0.06 13 6.0 19 0.71 1.3 1.6 10 <0.06 9.4 4.8 <0.06

2.4 4.1 1.3 2.0 <0.06 21 8.9 16 0.89 0.85 1.9 13 <0.06 9.1 9.2 <0.06

5.3 6.7 1.5 4.4 <0.06 83 18 37 <0.06 1.4 11 29 <0.06 19 26 <0.06

9.6 11 2.4 6.0 <0.06 75 28 57 1.0 2.9 13 47 <0.06 32 25 <0.06

5.3 7.3 4.5 3.3 0.49 22 18 44 0.87 3.7 2.9 20 0.46 23 9.9 <0.06

1.3 2.4 2.1 1.1 <0.06 5.3 4.5 14 0.67 1.8 0.68 6.9 <0.06 7.5 2.6 <0.06

2.1 3.3 1.4 1.6 <0.06 7.1 6.1 17 7.6 1.4 1.0 9.0 <0.06 8.3 4.4 <0.06

Pentachloronaphthalenes 49 <0.06 50 0.53 51 0.39 52/60 1.0 53 0.80 54 0.27 55 <0.06 56 <0.06 57 0.71 58 <0.06 59 2.4 61 0.43 62 0.73

0.62 2.0 0.66 4.2 4.4 0.28 <0.06 0.27 4.6 0.06 10 3.0 4.6

<0.06 <0.06 <0.06 0.32 0.32 <0.06 <0.06 <0.06 0.59 <0.06 2.3 <0.06 0.36

0.57 2.7 1.3 5.7 6.0 0.48 <0.06 0.75 5.2 0.59 14 3.8 6.4

0.93 3.5 2.5 6.7 7.3 1.9 <0.06 0.78 7.7 0.46 17 6.3 7.9

<0.06 2.1 0.89 27 3.3 1.7 <0.06 <0.06 5.2 2.6 13 24 3.4

<0.06 1.1 <0.06 11 10 3.4 <0.06 <0.06 10 1.1 30 13 9.4

<0.06 0.59 0.54 1.4 1.2 0.40 <0.06 <0.06 1.2 <0.06 3.9 0.68 0.84

<0.06 2.6 1.5 6.0 2.7 <0.06 <0.06 <0.06 5.6 <0.06 11 3.3 4.9

0.27 2.9 0.63 6.8 2.4 0.39 <0.06 0.06 3.9 0.57 9.9 5.0 2.1

0.58 2.6 1.8 6.2 6.2 1.6 <0.06 0.62 5.1 0.25 13 3.0 3.0

<0.06 2.1 1.2 3.5 3.5 2.7 <0.06 0.53 4.7 <0.06 7.8 3.4 4.0

<0.06 1.8 0.93 4.9 4.5 1.7 <0.06 <0.06 3.4 0.45 8.8 4.9 4.7

Hexachloronaphthalenes 63 <0.10 64 <0.10 65 <0.10 66/67 <0.10 68 <0.10 69 <0.10 70 <0.10 71 <0.10 72 <0.10

0.98 <0.10 0.86 0.78 0.71 1.5 <0.10 1.6 <0.10

<0.10 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10

<0.10 <0.10 0.76 1.7 0.51 2.0 <0.10 1.3 0.49

1.4 0.84 1.6 4.2 1.8 2.8 0.73 3.8 0.42

1.4 2.4 0.94 5.3 5.7 3.2 0.38 30 5.5

6.1 1.5 3.8 4.6 5.6 6.8 <0.10 17 4.9

0.65 <0.10 <0.10 1.8 0.64 <0.10 <0.10 <0.10 <0.10

1.5 <0.10 1.5 2.6 1.5 1.5 <0.10 1.1 <0.10

1.2 0.60 0.47 2.7 1.2 2.0 <0.10 3.0 0.43

2.1 0.79 1.4 4.2 1.2 2.9 0.29 3.7 0.55

<0.10 <0.10 <0.10 3.1 9.2 1.9 <0.10 9.8 6.1

1.6 <0.10 2.5 1.4 4.8 2.4 <0.10 11 11

Heptachloronaphthalenes 73 0.91 74 1.3

3.5 4.9

0.96 0.90

4.0 4.9

10 19

14 84

17 18

5.4 12

6.1 13

140 580

400 1000

110 460

Octachloronaphthalene 75 7.2 PCNs 240

24 220

6.4 90

23 270

ranged from 340 to 540 pg g 1 ww (the sites: 1c, 2a, 2b, 4a, 5a, 6b, 8a and 9c), and at two others (6a and 9b) were 1000 and 1100 pg g 1 ww. One of these two most contaminated sites is localized in central-western (6a) and another (9b) in eastern regions of Poland (Fig. 1). The sites showing smallest CNs concentrations in Scots pine needles are localized in central to north-eastern (3a, 3b, 6c, 7a, 7b and 7c), western (1d, 5a and 5b), and south-eastern (14b and 14c) regions of the country (Fig. 1). Surprisingly, a few of these less contaminated sites are localized at the south of Poland (10b, 11a, 12a and 13a). The southern part of Poland is known for greater concentration of heavy and chemical industries, when compared to other regions. Nevertheless, the sampling sites of

1.9 0.84 8.8 200

73 110

89 130

7.4 15 100 150

11 7.5 60 230

3.8 8.0 27 280

Scots Pine needles surveyed in this study even at more industrialized and urbanized regions of Poland were relatively far away from the large cities. Hence, they reflect semi-volatile contaminant’s concentrations of areas with influence from somewhat distant industrial/urban sources. These findings seem to confirm observation by Loganathan et al. (2008) that pine needles are effective passive-sampling matrix to identify degree of local CNs pollution. The characteristics of CNs diffusion in ambient air over Poland as reflected by Scots pine needles data in this study differs somehow from that observed for CDD/Fs (Bochentin et al., 2007). There are only a few data available on amount of CNs sequestered in pine needles worldwide, and no environmentally relevant data on these compounds in other kinds of green plant biomass.

1200

A. Orlikowska et al. / Chemosphere 75 (2009) 1196–1205

Pine needles collected at five residential and three industrial sites in western Kentucky contained CNs at 100 (92–110) and 100 (76– 100) pg g 1 dry weight, respectively, and in a superfund site at Brunswick, Georgia (USA), was 19 000 (610-38 000) pg CNs g 1 dw (Loganathan et al., 2008). In another study, the pine needles collected at nine sites around the Tokyo Bay in Japan in 1999 contained from 490 to 2100 pg CNs g 1 ww, while for a single and slightly remote site near the Pacific Ocean was 250 pg CNs g 1 ww (Hanari et al., 2004a,b). At a wider scale, the global atmospheric survey of CNs conducted in 2005–2006 did indicate the greater contamination of some urban areas in northern hemisphere, when compared to all the rural/agricultural or background sites; geometric means were 14 and 1.9 pg CNs m 3, respectively (Lee et al., 2007). There is much more data on concentrations and percentage profiles of higher molecular weight CNs in ambient air, i.e., for triCNs to octaCN than for mono- and diCNs, even though lighter congeners can possibly be largest sole contributors among atmospheric CNs. For example in air over the city of Barcelona in Spain the concentrations of mono- and diCNs accounted enormously, i.e., from 140 to 270 and from 99 to 220 pg m 3, respectively, to the total CNs concentrations ranging from 290 to 620 pg m 3 (Mari et al., 2008). 3.2. CN homologue groups composition of pine needles P The CN homologue groups’ compositional profile (%; triCNs to octaCN) determined in Scots pine needles at selected sites across Poland is given in Fig. 2. Certainly, there are some substantial similarities but also variations in these CN homologue group’s profiles depending on the site. A striking feature is that at certain locations three CN congeners having the greatest molecular weight, i.e., two heptaCNs (nos. 73 and 74) and octaCN (no. 75) are relatively large P contributors in bulk of triCNs to octaCN in pine needles. As stated earlier, the Scots Pine needles are sensitive passive indicator of airborne CNs, and this profile noted reflects local sources of heptaCNs and OCN at these sites. On the other side the triCNs, which are the most volatile group among CNs determined in this study, are, when compared to the load due to heptaCNs and octaCN, larger contributors to total chloronaphthalene concentrations at certain other locations (Fig. 2). It is worth noting, that monoCNs (two theoretically possible isomers) and diCNs (ten theoretically possible isomers) have not been analyzed in Scots pine needles in this study. This is important notice, because monoCNs are relatively more volatile when compared

to tri-, tetraCNs and more chlorinated congeners (melting point for monoCNs is from 17 °C to 2.3 °C, for diCNs is from 34 °C to 141 °C, for triCNs is from 74 °C to 145 °C, and for tetraCNs is from 98 °C to 205 °C) (Howe et al., 2001). Unquestionably, mono- and diCNs, due to physical-chemical features mentioned above, are volatile and therefore more air soluble and of more diffusive nature than any other CN homologue group (Puzyn et al., 2008) and could contribute largely to CNs in ambient air worldwide. Possible sources of CNs in pine needles in this study could be related to all potential types of CNs emission to the atmosphere. These could be due to residual uses and evaporative loses from technical PCN and technical PCB formulations contained in manufactured materials and products, depositions and leakage from the waste dumping sites, degassing from soil but also due to unintentional production of CNs in thermal (combustion, incineration, smelting) reactions (Falandysz, 1998, 2003). That aspect is examined in more detail further, as related to congener-specific data and chemometric approach. There are some reports on source-related emissions and occurrence of monoCNs to octaCN in ambient air. As mentioned, it is well-known fact that mono- and diCNs highly dominate in total CNs of atmospheric air over the cities, as was observed in Barcelona (Mari et al., 2008). Similarly, tri-, di- and monoCNs, decidedly dominated in ambient air at a hot spot site in the USA (Erickson et al., 1978). In other study, monoCNs to octaCN occurred in fly ash and contribution from octaCN to total CNs was 0.1%. An experimental annealing of the fly ash at 300 °C for 0.5–4 h leaded to production in excess (regarding to their original content in fly ash) of tetra-, di-, tri-, penta-, hexa- and monoCNs. At the same time contribution from 1,2,3,4,5,6,7-heptaCN remained unchanged, and 1,2,3,4,5,6,8-heptaCN and octaCN diminished (<0.1 ng g 1) after annealing (Schneider et al., 1998). Mono- and diCNs could stay mainly in atmospheric gas-phase. Harner and Bidleman (1997) could support these from observation in urban air of the Chicago metropolis. These researchers found that octaCN and to slightly less degree hepta- and hexaCNs were compounds mostly particle bounded (60–90%). In a most comprehensive study of CNs diffusion in ambient air worldwide – as related to the Global Atmospheric Passive Sampling (GAPS) program, triCNs and tetraCNs, depending on the location, were major individual contributors to CNs determined (Lee et al., 2007). Taking into account relative contribution of a particular CN homologue groups the dominating compounds in Scots pine needles are tri- and tetraCNs, and if add also pentaCNs these three homologue groups altogether contributed from 47% to 96% to CNs determined (Fig. 2). OctaCN alone is substantial contributor (3–38%) at five sites but is minor at seven other sites (Table 1). Due to largely varying CN homologue groups profiles across the country it is difficult to assess at this stage if only gas-phase airborne sources could play a role. Another possibility could be that incorporated but hardly washable ultra fine particles, which are usually highly enriched in octaCN but also in hepta- and hexaCNs, had contributed to the bulk of CNs detected. 3.3. Congener-specific CN composition of pine needles

Fig. 2. CN homologue group (triCNs- to octaCN) composition (%) of Scots pine needles from 25 sites (1c–14c) across Poland.

Chloronaphthalene congener compositional profiles for Scots pine needles are given in Table 1, and in Supplementary materials. Among triCNs, the isomers 1,2,4-/1,3,7-/1,4,6-triCNs (nos. 14/21/ 24) dominate in Scots pine needles. For majority of the sites examined 1,2,4-/1,3,7-/1,4,6-triCNs are also the major contributors to the bulk of CNs determined. Among tetraCNs isomer 1,2,5,8-tetraCN (no. 38) was dominant contributor at eighteen sites, while 1,2,4,6-/1,2,4,7-/1,2,5,7-tetraCN (nos. 33/34/37) at seven sites (5a, 6c, 7b, 9b, 10b, 11a and 12a). In the case of pentaCNs one isomer, namely 1,2,4,5,8-pentaCN (no. 59), was dominant contributor

A. Orlikowska et al. / Chemosphere 75 (2009) 1196–1205

alone. Octachloronaphthalene, as mentioned before, frequently contributed substantially to the bulk of CNs (Table 1). The principal component analysis (PCA) provided statistically supported insight into CNs compositional variations between the sites, as well as to possible origins of these contaminants in Scots pine needles (Figs. 3 and 4 and Supplementary materials). The PCA model, which relates to total CN concentration, based on six most significant principal components explain 94% of the total variance in data set (Fig. 3). First two factors accounted for 47% and 20% of variance and their loading are presented at Fig. 3a. An outlier is the Konstantynowo site (6a) and the sites, which represent mostly large forested, rural and agricultural regions, cluster at the opposite site of the map (Fig. 3a). The greatest positive loadings to Factor 2 are from a low molecular weight CNs, while greatest negative loadings are from a higher chlorinated CNs (Fig. 3a). The lower molecular weight CNs could be found at greatest concentration in pine needles at the sites Je˛drzejów (12a) and Opole (11a), which both are localized at more heavily industrialized region in southern part of the country. (Fig. 3a, Table 1).

1201

These contributions could be attributed both to land based evaporative and in some portion to combustion-related CNs emissions but this is hard to assess in detail. An attempt to define an existence and impact of potential sources of CNs emission in Poland when based on Scots pine needles data is discussed in more detail later. The third largest loading that explains 12% of variation in data set is due to contribution of 1,2,3,5,7-/1,2,4,6,7-pentaCNs (nos. 52/60), 1,2,4,5,7-pentaCN (no. 58), 1,2,3,4,5,7-/1,2,3,5,6,8-hexaCNs (nos. 64/68), 1,2,4,6,8-pentaCN (no. 61), 1,2,3,4,6,7-/1,2,3,5,6,7hexaCNs (nos. 66/67), 1,2,4,5,6,8-/1,2,4,5,7,8-hexaCNs (nos. 71/ 72), 1,2,3,4,5,6,8-heptaCN (no. 74) and octaCN (no. 75) (Fig. 3b). A load from CNs belonging to third factor vary greatly for that of location such as Sobibór (9b) and to some extend also of Biłgoraj (9c) (Fig. 3b). Factor 4 represents mainly 1,2,3,5,6-pentaCN (no. 51), 1,2,3,7,8pentaCN (no. 56) and 1,2,3,4,6,7-/1,2,3,5,6,7-hexaCNs (nos. 66/67), and it explains 7% of the variance in the dataset (Fig. 3b). Once more, the Konstantynowo site (6a) is evidently unlike the others.

Fig. 3. Plots of loadings based on the concentration of CN congeners in Scots pine needles and score plots of the sampling sites in space of first and second (a), third and fourth (b) and fifth and sixth (c) factors.

1202

A. Orlikowska et al. / Chemosphere 75 (2009) 1196–1205

On the other hand could be noted clustering of the sites situated close to urbanized and industrial areas of the towns of Kutno (8a), Olkusz (13a) and Włocławek (4b) (Fig. 3b).

The greatest negative loading of the fifth factor that explains almost 4% of the variance is from 1,2,3,6,7-pentaCN (no. 54) (Fig. 3c). 1,2,3,6,7-PentaCN is absent or highly minor constituent

Fig. 4. Plot of loadings based on CN congeners relative content (%) composition and score plot of the sampling sites, technical CN and CB formulations and bottom ashes in the space of the first and second (a), third and fourth (b), fifth and sixth (c), and seventh and eighth (d) factors.

A. Orlikowska et al. / Chemosphere 75 (2009) 1196–1205

of technical CN and CB formulations (Yamashita et al., 2000; Noma et al., 2004; Taniyasu et al., 2005; Falandysz et al., 2006a,b; Falandysz, 2007). 1,2,3,6,7-PentaCN to some degree could be preferentially formed during thermal reactions thus it is relevant CN found in combustion-related waste products. Relative contribution of 1,2,3,6,7-pentaCN in Scots pine needles fluctuates spatially and _ ˛ dowo site (4a) and folthe greatest enrichment is found at Zołe lowed by Biłgoraj (9c), Je˛drzejów (12a) and Olecko (3b) sites (Fig. 3c). None of CN congeners determined could be attributed explicitly to Factor 6. The Konstantynowo (no. 6a) and Sobibór (no. 9b) sites because of relatively elevated concentration of CNs differ significantly from other locations (Fig. 3). It could suggest the existence of the local and more potent emission sources there, when compared to other sites surveyed. Chloronaphthalenes were manufactured worldwide till the 1970s (Falandysz, 1998), however little is known about possible use and disposal of technical CN formulations and the materials containing these compounds in Poland, particularly at special locations like e.g., industrial storage sites or the military bases. The case of the ‘‘LeBlanc” soda factory site mentioned in introductory section, and an over 160 years persistence of CNs in the ground there (Bogdal et al., 2008), implies on possibly complicated history of more or less contaminated with CN sites elsewhere. 3.4. Relationships between CNs of pine needles and possible CNs emission sources Chloronaphthalenes can enter the environment by different ways. Emissions from multiple point sources of various natures and re-emissions from environmental compartments result in global diffusion of CNs. Atmospheric gas phase and aerosol partitioning of relatively persistent and semi-volatile compounds is controlled by ambient temperature, substance vapor pressure, and the nature, size and concentration of particles (Pankow and Bidleman, 1991). Chloronaphthalenes are chemically stable compounds. Nevertheless, similarly as many other more or less gas-phase free or particle bound atmospheric pollutants these compounds under favorable condition could in part undergo degradation (photolysis) processes (Puzyn et al., 2008). These could take place both by absorbing UV energy directly, impacts due to ionized molecules that are quite highly abundant in the lower troposphere, and by possible reactions with atmospheric free radicals and electron-induced molecules. Nevertheless, real and simultaneous impacts – in term of significance of all these atmospheric (photolytic) destruction forces, and depending on geographic zone and season of the year are an open question. Despite these possible natural processes influencing CNs atmospheric chemistry, and consequently their compositional profiles sequestered by plant biomass, it seems possible to some extent to examine origin of CNs sequestered in Scots pines. As already mentioned the chemometric’s tools used helped also to elucidate and identify possible emission sources of CNs determined in pine needles across Poland (Fig. 4, Supplementary materials). This additional PCA approach based on CNs compositional profiles (%) determined in Scots pine needles and on already known data of CNs compositional profiles of technical CN and CB formulations as well as of the bottom ashes obtained after coal, coke or wood burning (Yamashita et al., 2000; Noma et al., 2004; Wyrzykowska et al., submitted for publication). The evaporative loses of CNs into atmosphere, because of the past appliances of technical CN and CB formulations as well as of unfavorable disposal of materials and products containing these compounds, still are consider as important source of CNs found in the natural environment. Furthermore, the thermal reactions are recognized as another source of air pollution with CNs. Helm and Bidleman (2003) assessed that

1203

54% of CNs in ambient air in industrial part of Toronto is from combustion-related sources. The incineration until now is not a popular way of municipal solid waste disposal in Poland, while landfill disposal is very common. It has to be mentioned that combustion of hard coal and its derivatives in large and small power plants takes place across entire country. Moreover, household combustion of fossil fuels and wood, occasionally with addition of burnable domestic waste is common practice especially at small towns and rural regions. The PCA model with eight the most significant factors explains more than 85% of the total variance in the data set. TriCNs, except 1,2,3-triCN (no. 13), followed by tetraCNs introduced the positive loadings to the first factor, while negative loadings were from higher chlorinated congeners, mainly hexaCNs (Fig. 4). In the case of second principal component (Factor 2) the largest negative loadings are from most of pentaCNs, and the major positive loadings are both from heptaCNs and octaCN. Factors 1 and 2 account, respectively, for 35% and 22% of the total variance observed (Fig. 4a). The low molecular weight CNs make up the largest percentage at less urbanized, agricultural or vastly forested regions (the sites nos. 6c, 5a, 5b, 7b, 3a and 10b). But they contributed also at the sites being under impact of industrial and urbanized areas, as seen for Opole (11a), Je˛drzejów (12a) and Olkusz (13a) (Fig. 4a). Tri- and tertaCNs constitute a large percentage in homologue profile of bottom ashes (Wyrzykowska et al., submitted for publication). As mentioned tri- and tetraCNs are the most volatile between CNs determined and their preferable occurrence in pine needles at certain sites could be related to intensity of combustion processes there. Loganathan et al. (2008) observed that apart from nearly six fold to three hundred eighty times greater concentration of CNs in pine needles at superfund site, when compared to residential sites. Also a higher percent composition of CNs having 5–8 chlorines occurred in these highly contaminated needles, what could be due to evaporative loss of CNs from dumped products containing Halowax 1013 and Aroclor 1254 and 1260. The profiles of CN congeners in Scots pine needles at the Sobibór site (no. 9b) as well as at the Biłgoraj (9c), De˛bica (14b), Konstantynowo (6a), De˛bno (1c) and Olecko (3b) sites seem to resemble to some extent the profiles determined in certain technical CB formulations (Fig. 4a). The third largest load that explains 7% of variance in data set is due to contribution of 1,3,5,7-tetraCN (no. 42), 1,4,6,7-tetraCN (no. 47) and 1,2,4,6-/1,2,4,7-/1,2,5,7-tetraCNs (nos. 33/34/37) (Fig. 4b). Significant influence of compounds related to this factor can be seen in pine needles from the south western part of Poland (Opole (11a) and Oława (10b)), while an opposite case is at the rural and forested site of Kudypy (no. 3a) in north-eastern part of Poland (Fig. 4b). CNs related to this principal component in the case of the Opole (11a) and Oława (10b) sites show some compositional similarity to CN impurities found in technical CB formulations of Sovol, Aroclor 1254 and Phenoclor DP5 (Fig. 4b). Sovol as a transformer oil constituent was imported to Poland from the Soviet Union (Falandysz and Szymczyk, 2001). The greatest negative loading of the fourth factor, which explains 6% of the variance, is from octaCN (no. 75) (Fig. 4b). This isomer is relatively abundant compound among CNs sequestered in Scots pine needles at majority of the sites examined (Table 1). OctaCN is primary (80–90%) constituent of Halowax 1051, and at around 1% occurs in Halowax 1014 (Falandysz et al., 2006a,b). This compound is also by-side CN in technical CB formulations such as Chlorofen, the Aroclors (1260, 1262, 1016 and 1232), Phenoclor DP3 and DP6, Kanechlor 300 and 600, Clophen T64 and Halowax 1051, 1013 and 1099 (Yamashita et al., 2000; Taniyasu et al., 2005; Falandysz, 2007). As pointed out earlier octaCN at high rate is adsorbed on the atmospheric particles and thus abundance of

1204

A. Orlikowska et al. / Chemosphere 75 (2009) 1196–1205

Fig. 5. The relative content of combustion-related CNs (nos. 13, 26, 29, 44 and 54) in Scots pine needles and in several CNs sources (*Hanari et al., 2004b; Bidleman, 2003; ***Wyrzykowska et al., 2009; ****Yamashita et al., 2000; ****Noma et al., 2004).

this compound in Scots pine needles at certain sites implies on greater concentrations of atmospheric dust in these regions. The fifth principal component explains slightly less than 5% of the total variance in data set. 1,2,3-TriCN (no. 13) brings the highest positive loading to this factor, however CNs such as 1,2,7,8-tetraCN (no. 41), 1,2,3,6,7-pentaCN (no. 54), 1,2,3,7,8-pentaCN (no. 56), and 1,2,3,4,6,7-/1,2,3,5,6,7-hexaCNs (nos. 66/67), which are preferentially formed in combustion processes (Schneider et al., 1998; Imagawa and Lee, 2001) are important contributors to negative loadings (Fig. 4c). None of CN congeners could be specifically attributed to Factor 6 (Fig. 4c). It seems that CNs compositional profiles of pine needles at the _ ˛ dowo (no. 4a) are influenced to sites of De˛bica (no. 14b) and Zołe some degree by these combustion related CNs (Fig. 4c). It can also be observed that CNs composition from rural region of Kudyby (3a) mostly resembles profile of wood burning. Moreover, cluster analysis showed that the composition of CNs in Scots pine needles at this site differs by some means from the majority of samples. Therefore it can be presumed that wood burning could contribute significantly to levels of CNs at this location. From the other hand coal burning could contribute to some extend to CNs bulk in many other sites, although technical chlorobiphenyl formulations could be also consider as important source. The greatest loading of the seventh factor is highly dominated by 1,2,3,6,7-pentaCN (no. 54) with almost 4% of variance’s explanation (Fig. 4d). As explained earlier, 1,2,3,6,7-pentaCN is absent or is a trace constituent in technical CN or CB formulations, but is more combustion processes related compound and is relevant in fly ash (Imagawa and Lee, 2001; Helm and Bidleman, 2003). Because of that, 1,2,3,6,7-pentaCN is one of a few CN congeners suitable as markers of combustion-related sources. The Scots pine needles at _ ˛ dowo (4a), De˛bica (14b) and Olecko (3b), the sites such as Zołe and less for Biłgoraj (9c) and Brzozów (14c) did indicate an elevated concentration of 1,2,3,6,7-pentaCN (Fig. 4d), and so influence of combustion-related sources in these regions. 1,2,3,4,5,6-hexaCN (no. 63) carries the major negative loading into the eighth factor, which explains almost 3% of the variance (Fig. 4d). The compositional inputs of CN congeners belonging to this factor is similar at many sites examined (Fig. 4d). In addition, a similar influence of congeners related to this PC could be observed for majority of technical CB formulations. Not only 1,2,3,6,7-pentaCN (no. 54) but also 1,2,3-triCN (no. 13), 2,3,6-triCN (no. 26), 1,2,3,6-tetraCN (no. 29) and 1,3,6,7-tetraCN (no. 44) are minor CN constituents in evaporative sources containing the technical chloronaphthalene (Halowax series) or chlorobiphenyl (various brands) formulations but they are generated during thermal reactions (Yamashita et al., 2000; Imagawa and Lee, 2001; Helm and Bidleman, 2003; Noma et al., 2004; Falandysz et al., 2006a,b). Consequently, these CNs are considered as the suitable markers to identify thermal sources of CNs. _ ˛ dowo (4a), Kutno (8a) and The Scots pine needles at the Zołe Olkusz (13a) sites certainly were enriched with these combustion-related CNs and showed elevated total CNs concentrations.

**

Helm and

The average amount of these combustion-related congeners in bulk of CNs in Scots pine needles from Poland was around 1.3% (0.5–2.4%), while in pine needles from Japan (Hanari et al., 2004b) was around 9% (5.8–12.5%) (Fig. 5). This probably could be explained by large differences in a magnitude of combustion-related activities between these both countries, including automobile traffic. In Japan at some period was localized almost 2/3 of large solid waste incinerators of the world (Hiraoka and Okajima, 1994). At Fig. 5 apart from a relative content of combustion-related ‘‘the marker” CNs in pine needles of Poland and Japan is given also information on contribution of these compounds in bulk of CNs determined in technical CN/CB formulations and in some combustion-related waste products. Lee et al. (2005) observed that during coal and wood burning mainly 1,4,6-triCN (no. 24) is formed and it constituted 18% and 27% of total CNs found, respectively. In study by Lee et al. (2005) 1,2,4-triCN (no. 14) and 1,3,7-triCN (no. 21) have not been determined. In our study 1,2,4-/1,3,7-/1,4,6-triCNs (nos. 14/21/24) coeluted and were recorded as a single peak at the chromatogram. The relative contribution of 1,2,4-/1,3,7-/1,4,6-triCNs to total CNs in Scots pine needles of Poland was from 9.5% to 40%, while in pine needles of Japan was less than 9% (Hanari et al., 2004b). In addition, in technical CN/CB formulations these congeners are minor constituents among CNs and the greatest concentration did not excide 8.2% (Noma et al., 2004; Yamashita et al., 2000). These foundlings together with awareness of a very limited scale of the municipal and hazardous waste incineration but extensive use of fossil fuels and wood burning at the regions of Scots pine needles sampling imply on coal/wood combustion as an important source of CNs into the ambient air in Poland. 4. Conclusions The compositional profiles of CNs found in Scots pine needles imply on existence of multiple sources of these contaminants in air over Poland. At the sites with relatively elevated levels of CNs certainly local and specific sources occur. It seems that the sources of evaporative nature, which could be related to soil CN reservoirs and dumped or still used materials and products containing technical CN and CB formulations, contributed the most in these regions. Nevertheless, history of the past uses of CNs and subsequent environment contamination could be somewhat complicated. In the further step any ‘‘hot spot” displayed by analyzing pine needles could be additionally examined in more detail using other site-related biological and abiotic materials as well as relevant written documents about history of the site if available. Furthermore, in addition to CN and CB formulations, there are other probable sources which could contribute to the bulk of chloronaphthalenes in Poland. The thermal sources could be mostly associated to hard coal, lignite and wood combustion but also to open combustion of burnable household wastes and high temperature processes at industrial sites (ore roasting, metal refining, metal reclamation etc.), and possibly also to automobile engine exhaust.

A. Orlikowska et al. / Chemosphere 75 (2009) 1196–1205

A widespread occurrence of CNs in Scots pine needles implies to some degree on contamination with these compounds of vegetable food as well as of pasture and other animal feeds of plant origin. Acknowledgements The authors are grateful to Dyrekcja Generalna Lasów Pan´stwowych, Warsaw, Poland and to Dyrekcje Regionalne Lasów Pan´stwowych for kind cooperation. This study has been supported by the Ministry of Science and Higher Education under Grant No. DS8250-4-0092-9. Appendix A. Supplementary material Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.chemosphere.2009.02.024. References Blankenship, A., Kannan, K., Villalobos, S., Villeneuve, D., Falandysz, J., Imagawa, T., Jakobsson, E., Giesy, J., 2000. Relative potencies of Halowax mixtures and individual polychlorinated naphthalenes (PCNs) to induce Ah receptormediated responses in the rat hepatoma H4IIE-Luc cell bioassay. Environ. Sci. Technol. 34, 3153–3158. Bochentin, I., Hanari, N., Orlikowska, A., Wyrzykowska, B., Rostkowski, P., Horii, Y., Yamashita, N., Falandysz, J., 2007. PCDD/Fs in pine needles of Poland. J. Environ. Sci. Health 42, 1969–1978. Bogdal, C., Weber, R., Schmid, P., Zennegg, M., 2008. Formation of polychlorinated naphthalenes in a former LeBlanc soda factory. Organohalogen Compd. 70, 805– 808. Crookes, M.J, Howe, P.D., 1993. Environmental hazard assessment: Halogenated naphthalenes. Report TSD/13. Department of the Environment, London, UK. Di´Guardo, A., Zaccara, S., Cerabolini, B., Acciarri, M., Tetzaghi, G., Calamari, D., 2003. Conifer needles as passive biomonitors of the spatial and temporal distribution of DDT from a point source. Chemosphere 52, 789–797. Erickson, M.D., Michael, L.C., Zweidinger, R.A., Pellizarri, E.D., 1978. Sampling and analysis of polychlorinated naphthalenes in the environment. J. Assoc. Off. Anal. Chem. 61, 1135–1346. Falandysz, J., 1998. Polychlorinated naphthalenes: an environmental update. Environ. Pollut. 10, 77–90. Falandysz, J., 2003. Chloronaphthalenes as food-chain contaminants: a review. Food Addit. Contam. 21, 995–1014. Falandysz, J., 2007. Dioxin-like compounds load of the bulk of Chlorofen – a technical chlorobiphenyl formulation from Poland. J. Environ. Sci. Health 42, 1959–1968. Falandysz, J., Strandberg, L., Bergqvist, P.-A., Kulp, S.E., Strandberg, B., Rappe, C., 1996. Polychlorinated naphthalenes in sediment and biota from the Gdan´sk Basin, Baltic Sea. Environ. Sci. Technol. 30, 3266–3274. Falandysz, J., Strandberg, L., Bergqvist, P.-A., Strandberg, B., Rappe, C., 1997. Spatial distribution and bioaccumulation of polychlorinated naphthalenes (PCNs) in mussel and fishes from the Gulf of Gdan´sk, Baltic Sea. Sci. Total Environ. 203, 93–104. Falandysz, J., Rappe, C., 1997. Specific pattern of tetrachloronaphthalenes in black cormorant. Chemosphere 35, 1737–1746. Falandysz, J., Szymczyk, K., 2001. Data on the manufacture, use, inventory and disposal of polychlorinated biphenyls (PCBs) in Poland. Pol. J. Environ. Stud. 10, 189–193. Falandysz, J., Nose, K., Ishikawa, Y., Łukaszewicz, E., Yamashita, N., Noma, Y., 2006a. Chloronaphthalene composition of several batches of Halowax 1051. J. Environ. Sci. Health 41, 291–301. Falandysz, J., Nose, K., Ishikawa, Y., Łukaszewicz, E., Yamashita, N., Noma, Y., 2006b. HRGC/HRMS analysis of chloronaphthalenes in several batches of Halowax 1000, 1001, 1013, 1014 and 1099. J. Environ. Sci. Health 41, 2237–2255. Falandysz, J., Chudzyn´ski, K., Takekuma, M., Yamamoto, T., Noma, Y., Hanari, N., Yamashita, N., 2008. Multivariate analysis of identity of imported technical PCN formulation. J. Environ. Sci. Health 43, 1381–1390. Hanari, N., Horii, Y., Okazawa, T., Falandysz, J., Bochentin, I., Orlikowska, A., Puzyn, T., Wyrzykowska, B., Yamashita, N., 2004a. Dioxin-like compounds in pine needles around Tokyo Bay, Japan in 1999. J. Environ. Monitor. 6, 305–312. Hanari, N., Horii, Y., Taniyasu, S., Falandysz, J., Bochentin, I., Orlikowska, A., Puzyn, T., Yamashita, N., 2004b. Isomer specific analysis of polychlorinated naphthalenes in pine trees (Pinus thumbergi Parl) and (Pinus densiflora Sieb. et Zucc) needles around Tokyo Bay, Japan. Pol. J. Environ. Stud. 13, 139–151. Harner, T., Bidleman, T.F., 1997. Polychlorinated naphthalenes in urban air. Atmos. Environ. 31, 4009–4016. Helm, P.A., Bidleman, T.F., 2003. Current combustion-related sources contribute to polychlorinated naphthalene and coplanar polychlorinated biphenyl levels and profiles in air in Toronto. Canada Environ. Sci. Technol. 37, 1075–1082. Helm, P.A., Gewurtzs, S.B., Whittle, D.M., Marvin, C.H., Fisk, A.T., Tomy, G.T., 2008. Occurrence and biomagnifications of polychlorinated naphthalenes and non-

1205

and mono-ortho PCBs in Lake Ontario sediments and biota. Environ. Sci. Technol. 42, 1024–1031. Hiraoka, M., Okajima, S., 1994. Source control technologies in MSW incineration plants. Organohalogen Compd. 19, 275–291. Horii, Y., Falandysz, J., Hanari, N., Rostkowski, P., Puzyn, T., Okada, M., Amano, K., Naya, T., Taniyasu, S., Yamashita, N., 2004. Concentrations and fluxes of chloronaphthalenes in sediments from the lake Kitaura in Japan in recent 15 centuries. J. Environ. Sci. Health Pt A. 39, 587–609. Howe, P.D., Melber, C., Kielhorn, C., Mangelsdorf, I., 2001. Chlorinated Naphthalenes. WHO, Geneva. Imagawa, T., Lee, W.C., 2001. Correlation of polychlorinated naphthalenes with polychlorinated dibenzofurans formed from waste incineration. Chemosphere 44, 1511–1520. Jansson, S., Fick, J., Marklund, S., 2008. Formation and chlorination of polychlorinated naphthalenes (PCNs) in the post-combustion zone during MSW combustion. Chemosphere 72, 1138–1144. Kilanowicz, A., Galoch, A., Sapota, A., 2004. Tissue distribution and elimination of selected chlorinated naphthalenes. Int. J. Occup. Med. Environ. Health 17, 355– 360. Kylin, H., Hellström, A., Nordstrand, E., Zaid, A., 2003. Organochlorine pollutants in Scots pine needles – biological and site related variation within a forest stand. Chemosphere 51, 669–675. Lee, R.G.M., Coleman, J.L., Jones, K.C., Lohmann, R., 2005. Emission factors and importance of PCDD/Fs, PCBs, PCNs, PAHs and PM10 from the domestic burning of coal and wood in the UK. Environ. Sci. Technol. 39, 1436–1447. Lee, S.C., Harner, T., Pozo, K., Shoeib, M., Wania, F., Muir, D.C.G., Barrie, L.A., Jones, K.C., 2007. Polychlorinated naphthalenes in the global atmospheric passive sampling (GAPS) study. Environ. Sci. Technol. 41, 2680–2687. Loganathan, B.G., Kumar, K.S., Seaford, K.D., Sajwan, K.S., Hanari, N., Yamashita, N., 2008. Distribution of persistent organohalogen compounds in pine needles from selected locations in Kentucky and Georgia USA. Arch. Environ. Con. Tox. 54, 422–439. Mari, M., Schuhmacher, M., Feliubadaló, J., Domingo, J.L., 2008. Air concentrations of PCDD/Fs, PCBs and PCNs using active and passive air samplers. Chemosphere 70, 1637–1643. Noma, Y., Yamamoto, T., Sakai, S.I., 2004. Congener-specific composition of polychlorinated naphthalenes, coplanar PCBs, dibenzo-p-dioxins, and dibenzofurans in the halowax series. Environ. Sci. Technol. 38, 1675– 1680. Noma, Y., Yamamoto, T., Giraud, R., Sakai, S.I., 2006. Behavior of PCNs, PCDDs, PCDFs, and dioxin-like PCBs in the thermal destruction of wastes containing PCNs. Chemosphere 62, 1183–1195. Pankow, J.F., Bidleman, T.F., 1991. Effects of temperature, TSP and percent nonexchangeable material in determining the gas-particle partitioning of organic compounds. Atmos. Environ. 25, 2241–2249. Popp, W., Norpoth, K., Vahrenholz, C., Hamm, S., Balfanz, E., Theeisen, J., 1997. Polychlorinated naphthalenes exposures and liver functions changes. Am. J. Ind. Med. 32, 413–416. Puzyn, T., Falandysz, J., Jones, P.D., Giesy, J.P., 2007. Quantitative structure–activity relationships to predict of relative in vitro potencies (REPs) for chloronaphthalenes. J. Environ. Sci. Health 42, 573–590. Puzyn, T., Mostra˛g, A., Suzuki, N., Falandysz, J., 2008. QSPR-based estimation of the atmospheric persistence for chloronaphthalene congeners. Atmos. Environ. 42, 6627–6636. Schneider, M., Stieglitz, L., Will, R., Zwick, G., 1998. Formation of polychlorinated naphthalenes on fly ash. Chemosphere 37, 2055–2070. Taniyasu, S., Falandysz, J., S´wie˛tojan´ska, A., Flisak, M., Horii, Y., Hanari, N., Yamashita, N., 2005. Clophen A 60 content of CBs, CNs, CDFs and CDDs after 2D-HPLC plus HRGC/LRMS and HRGC/HRMS separation and quantification. J. Environ. Sci. Health 40, 43–61. Villeneuve, D.L., Kannan, K., Khim, J.S., Falandysz, J., Nikiforov, V.A., Blankenship, A.L., Giesy, J.P., 2000. Relative potencies of individual polychlorinated naphthalenes to induce dioxin-like response in fish and mammalian in vitro bioassays. Arch. Environ. Con. Tox. 39, 273–281. Wyrzykowska, B., Bochentin, I., Hanari, N., Orlikowska, A., Falandysz, J., Horii, Y., Yamashita, N., 2006. Source determination of highly chlorinated biphenyl isomers in pine needles – comparison to several technical PCB formulations. Environ. Pollut. 143, 46–59. Wyrzykowska, B., Hanari, N., Orlikowska, A., Bochentin, I., Rostkowski, P., Falandysz, J., Taniyasu, S., Horii, Y., Jiang, Q., Yamashita, N., 2007. Polychlorinated biphenyls and -naphthalenes in pine needles and soil from Poland – concentrations and patterns in the view of the long-term environmental monitoring. Chemosphere 67, 1877–1886. Wyrzykowska, B., Hanari, N., Orlikowska, A., Yamashita, N., Falandysz, J., submitted for publication. Dioxin-like compounds compositional profiles of furnace bottom ashes from household combustion in Poland and their possible association with contamination status of agricultural soil and pine needles. Chemosphere. Yamashita, N., Kannan, K., Imagawa, T., Miyazaki, A., Giesy, J.P., 2000. Concentrations and profiles of polychlorinated naphthalene congeners in eighteen technical polychlorinated biphenyl preparations. Environ. Sci. Technol. 34, 4236–4241. Yamashita, N., Taniyasu, S., Hanari, N., Horii, Y., Falandysz, J., 2003. Polychlorinated naphthalene contamination of some recently manufactured industrial products and commercial goods in Japan. J. Environ. Sci. Health 38, 1745– 1759.