Quantitative ecological risk assessment of inhabitants exposed to polycyclic aromatic hydrocarbons in terrestrial soils of King George Island, Antarctica

Polar Science xxx (2016) 1e11

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Quantitative ecological risk assessment of inhabitants exposed to polycyclic aromatic hydrocarbons in terrestrial soils of King George Island, Antarctica S. Pongpiachan a, *, M. Hattayanone b, O. Pinyakong c, V. Viyakarn d, S.A. Chavanich d, C. Bo e, C. Khumsup f, I. Kittikoon f, P. Hirunyatrakul f a

School of Social & Environmental Development, National Institute of Development Administration (NIDA), Bangkok, Thailand Faculty of Environmental Management, Prince of Songkla University, Hat-Yai, Songkhla, Thailand Bioremediation Research Unit, Department of Microbiology, Faculty of Science, Chulalongkorn University, Bangkok, Thailand d Reef Biology Research Group, Department of Marine Science, Faculty of Science, Chulalongkorn University, Bangkok, Thailand e Polar Biological Science Division, Polar Research Institute of China, Shanghai, China f Bara Scientific Co., Ltd., Bangkok, Thailand b c

a r t i c l e i n f o

a b s t r a c t

Article history: Received 3 October 2016 Accepted 2 December 2016 Available online xxx

This study aims to conduct a quantitative ecological risk assessment of human exposure to polycyclic aromatic hydrocarbons (PAHs) in terrestrial soils of King George Island, Antarctica. Generally, the average PAH concentrations detected in King George Terrestrial Soils (KGS) were appreciably lower than those of World Marine Sediments (WMS) and World Terrestrial Soils (WTS), highlighting the fact that Antarctica is one of the most pristine continents in the world. The total concentrations of twelve probably carcinogenic PAHs (SPAHs: a sum of Phe, An, Fluo, Pyr, B[a]A, Chry, B[b]F, B[k]F, B[a]P, Ind, D[a,h]A and B[g,h,i] P) were 3.21 ± 1.62 ng g
1, 5749 ± 4576 ng g
1, and 257,496 ± 291,268 ng g
1, for KGS, WMS and WTS, respectively. In spite of the fact that KGS has extremely low SPAHs in comparison with others, the percentage contribution of Phe is exceedingly high with the value of 50%. By assuming that incidental ingestion and dermal contact are two major exposure pathways responsible for the adverse human health effects, the cancer and non-cancer risks from environmental exposure to PAHs were carefully evaluated based on the “Role of the Baseline Risk Assessment in Superfund Remedy Selection Decisions” memorandum provided by US-EPA. The logarithms of cancer risk levels of PAH contents in KGS varied from
11.1 to
7.18 with an average of
7.96 ± 7.73, which is 1790 times and 80,176 times lower than that of WMS and WTS, respectively. All cancer risk levels of PAH concentrations observed in KGS are significantly (p < 0.001) lower than those of WMS and WTS. Despite the Comandante Ferraz Antarctic Station fire occurred in February 25th, 2012, both the cancer and non-cancer risks of environmental exposure to PAHs were found in “acceptable level”. © 2016 Elsevier B.V. and NIPR. All rights reserved.

Keywords: PAHs Cancer risk King George Island Antarctica Terrestrial soils

1. Introductions Polycyclic aromatic hydrocarbons (PAHs), usually acknowledged as a group of persistent organic pollutants (POPs), have been comprehensively investigated in the past decades because these congeners have a profound association with a wide range of adverse health effects and other respiratory diseases (Bhargava et al., 2004; Chalbot et al., 2012; Claxton and Woodall Jr., 2007).

* Corresponding author. E-mail address: [email protected] (S. Pongpiachan).

PAHs are widely detected in various types of environmental compartments including marine organisms (Pongpiachan et al., 2013a,b; Pongpiachan, 2013a,b; Sette et al., 2013; Yoshimine et al., 2012). It is well known that PAHs can be generated from both anthropogenic and natural sources (Lu et al., 2012; Okuda et al., 2002; Slezakova et al., 2011; Yang et al., 2002). According to recent studies, particulate PAHs are harmful to human health due to its responsibilities for cancer, endocrine disruption, and reproductive and developmental effects (Liao et al., 2011; Hoyer, 2001; Matsui, 2008; Wickramasinghe et al., 2012). Although the majority of PAHs generally have a low degree of acute toxicity to humans, numerous investigations have demonstrated non-carcinogenic

http://dx.doi.org/10.1016/j.polar.2016.12.001 1873-9652/© 2016 Elsevier B.V. and NIPR. All rights reserved.

Please cite this article in press as: Pongpiachan, S., et al., Quantitative ecological risk assessment of inhabitants exposed to polycyclic aromatic hydrocarbons in terrestrial soils of King George Island, Antarctica, Polar Science (2016), http://dx.doi.org/10.1016/j.polar.2016.12.001

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effects of PAHs involve primarily the pulmonary, gastrointestinal, renal, and dermatologic systems after chronic exposure (Gupta et al., 1991). It is a strenuous task to evaluate observed health effects in epidemiological studies to certain PAH congener because most exposures are related to PAH mixtures, which include both carcinogenic and non-carcinogenic PAHs. A recent study found that both phenanthrene (non-carcinogenic) and benzo[b]fluoranthene (carcinogenic to experimental animals) induced hepatic histopathological changes that highlight metabolic failure and inflammation, particularly in animals exposed to mixtures (Martins et al., 2015). It is also crucial to underline that two or more PAH congeners within a mixture may compete for receptors or active sites of metabolizing enzymes and chaperones, producing synergistic, antagonistic or additive impacts that may responsible either in cocarcinogenic or chemopreventive effects (Jarvis et al., 2014). As a consequence of distress over its potential hazard to public health, numerous studies were conducted to investigate the impact of meteorological parameters on its temporal variation and spatial distribution (Akyüz and Çabuk, 2009; Amodio et al., 2009). Further attempts on clarification of factors governing diurnal variation of PAHs have also been carried out in different countries (Chetwittayachan et al., 2002; Gu et al., 2010; Ringuet et al., 2012; Zhang et al., 2012). Regardless of numerous studies on variations of PAHs in soils and sediments around the world, the knowledge of the magnitude of their contamination in Antarctic soil, which is still considered as one of the most pristine areas of the world, is strictly limited. During the past decades, there are numerous studies have been attempted to elucidate the degree of contamination as well as its emission source strength of PAHs in Antarctic soils (Aislabie et al., 1999; Curtosi et al., 2007; Prus et al., 2015). In order to obtain some references for global migration of PAHs, snow samples were collected in Fildes Peninsula in the Southwestern end of King George Island in the South Shetland Islands of Antarctica. Principal component analysis revealed that Naphthalene, Fluorene and Phenanthrene were three main factors of PAHs detected in snow samples accounted for 61%, 22%, and 10%, respectively (Na et al., 2011). Similar patterns were also observed in marine sediments sampled from Prydz Bay, East Antarctica with two- and three-ring PAHs as the most abundant compounds detected at the majority of the observatory sites of Prydz Bay (Xue et al., 2016). Further source apportionment analysis in sediment cores of Admiralty Bay, Antarctica were conducted by using PAHs and carbonaceous particles (SCPs) as two markers used for assessing the local input of anthropogenic materials as a consequence of the impact of human activities in both sub-Antarctic region and South America. By interpreting the diagnostic binary ratios of PAHs, fossil fuels/petroleum, biomass burning and sewage contribution were generally considered as three main sources of PAHs in this region. In spite of countless studies focusing on spatial and temporal distributions of PAHs in Antarctic environment, there are no compelling studies and their outcomes demonstrating the magnitude of exposure and ecological risk of PAHs in King George Island. Overall, the objectives of this study are i) to analyse PAH concentrations in terrestrial soils of King George Island, ii) to use a variety of comparable ecological risk assessment models to obtain more advantageous insights of the potential carcinogenic risk in the SubAntarctic Region for the first time. It is crucial to underline that the main purpose of this study is to illustrate the general principle of applying PAHs as chemical indicators for cancer risk assessment in King George Island. Neither source apportionment nor the assessment of temporal variation and spatial distribution of PAHs is the prominent goal of this investigation.

2. Materials and methods 2.1. Collections of terrestrial soils All terrestrial soils (n ¼ 21) were collected from 8th January 2014 to 23rd January 2014 at Southwestern part of King George Island with the depth of 0e10 cm (see Table 1 and Fig. 1A). King George Island is the largest of the South Shetland Islands coordinates at 62 020 S 58 210 W with the area of 1150 km2 (i.e. 440 sq mi). King George Island possesses three main bays, namely Maxwell Bay, Admiralty Bay, and King George Bay. Admiralty Bay has three fjords, and is generally protected as an Antarctic Specially Managed Area under the Protocol on Environmental Protection to the Antarctic Treaty. The majority of samples were collected around the Great Wall Station, which lies on the Fildes Peninsula on King George Island, and is approximately 2.5 km from the Chilean Frei Montalva Station. Terrestrial soil samples were wrapped in clean aluminum foil, placed in a glass bottle, and kept frozen at
20  C in order to avoid sample degradation caused by heat, ozone, NO2, and ultraviolet (UV) during sample transport. They were freeze-dried prior to being grounded and sieved to homogenize the samples, and then kept in the refrigerator at
4  C until analysis. Procedural precautions (e.g. special precautions for trace contaminant soil sampling), sample homogenization, dressing soil surfaces, sampling methodology for low concentrations (<200 ng g
1), and quality control/quality assurance (QA/QC) were clearly explained in soil sampling US-EPA Method 5035 and will not be discussed here (US-EPA, 2002). 2.2. PAHs analysis All organic solvents (i.e. DCM and Hexane) are HPLC grade, purchased from Fisher Scientific. A cocktail of 15 PAHs Norwegian Standard (NS 9815: S-4008-100-T) (phenanthrene (Phe), anthracene (An), fluoranthene (Fluo), pyrene (Pyr), 11h-benzo[a]fluorene (11H-B[a]F), 11h-benzo[b]fluorene (11H-B[b]F), benz[a]anthracene (B[a]A), chrysene (Chry), benzo[b]fluoranthene (B[b]F), benzo[k] fluoranthene (B[k]F), benzo[a]pyrene (B[a]P), benzo[e]pyrene (B[e] P), indeno[1,2,3-cd]pyrene (Ind), dibenz[a,h]anthracene (D[a,h]A), benzo[g,h,i]perylene (B[g,h,i]P); each 100 mg mL
1 in toluene: unit: 1  1 mL) and a mix of recovery Internal Standard PAHs (d12-perylene (d12-Per), d10-fluorene (d10-Fl); each 100 mg mL
1 in xylene: unit: 1  1 mL) were supplied by Chiron AS (Stiklestadveine 1, N7041 Trondheim, Norway). A 30 g free-dried terrestrial soil sample was transferred to pre-cleaned Thimber. The chemical extraction of PAHs was performed by using 250 ml of Soxhlet extractors, spiked with a known quantity of internal standard (d10-Fl: Phe, An, Fluo, Pyr, B[a]A, Chry; d12-Per: B[b]F, B[k]F, B[a]P, Ind, D[a,h]A, B[g,h,i]P) and extracted with DCM containing 1 g of copper powder for 8 h. In order to avoid any method interferences, which may be caused by contaminants in glassware, reagents, solvents, and other experimental devices, the laboratory blanks were routinely analyzed to ensure that all mentioned materials were to be free from interferences under the conditions of the analysis. The fractionation/clean-up technique, blowing down process (e.g. a combination of rotary evaporation with a gentle nitrogen stream) was strictly performed in accordance with the standard protocol applying the difference in solvent polarity (Gogou et al., 1996, 1998). The reduced extract was subsequently diluted in 10 ml of n-hexane before being transferred to the top of a column of disposable silica gel, which was activated at 150  C for 3 h. Two different compound groups (i.e. light molecular weight PAHs and heavy molecular weight PAHs) were classified by eluting 15 ml nhexane and 15 ml toluene-n-hexane (5.6:9.4). The gas chromatography (GC) temperature programming coupled with the

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Table 1 Study area and sampling site description. Sample Name

Date of Collection

Site Name

P1 P2 P3 P4 P5 P6 P7 P8 P9 P10 P11 P12 P13 P14 P15 P16 P17 P18 P19 P20 P21 P22 P23

8-Jan-14 8-Jan-14 8-Jan-14 10-Jan-14 10-Jan-14 10-Jan-14 11-Jan-14 15-Jan-14 15-Jan-14 15-Jan-14 16-Jan-14 16-Jan-14 16-Jan-14 16-Jan-14 16-Jan-14 18-Jan-14 21-Jan-14 22-Jan-14 22-Jan-14 22-Jan-14 22-Jan-14 22-Jan-14 23-Jan-14

Around Great Wall Around Great Wall Around Great Wall Niujiao Niujiao Niujiao Around Great Wall Ardley Island Ardley Island Ardley Island Around Great Wall Around Great Wall Around Great Wall Around Great Wall Around Great Wall Around Great Wall Around Great Wall On the mountain On the mountain On the mountain On the mountain On the mountain Around Great Wall

station station station

station

station station station station station station station

station

optimization of mass spectrometric setting for both qualitative and quantitative identification of PAHs was previously mentioned in Pongpiachan et al. (2009). The QA/QC processes of the analytical method were conducted by employing the standard SRM 1941b. Mean recovery (based on extraction of matrix-matched certified reference materials, (n ¼ 8) was in range of 77e119%. The precision of the procedure, calculated as relative standard deviation on the duplicate samples, was less than 10%. All sample concentrations were calculated using standardized relative response factors run with each batch (Pongpiachan et al., 2009a,b). In addition, all statistical analysis of this study was done by using SPSS (statistical package for the social sciences) version 13.

2.3. Evaluation of terrestrial soil toxicity based on the total toxic B [a]P equivalent (TEQcarc) B[a]P is widely acknowledged as a representative congener of PAHs because of its comparatively high mutagenicity and carcinogenicity. Despite its relatively high diversity of molecular structure, only B[a]A, B[a]P, B[b]F, B[k]F, Chry, D[a,h]A and Ind have been classified as seven potentially carcinogneic PAH compounds (CPAHs) which are probable human carcinogens by US EPA. Since the toxicity of PAHs is extremely structurally dependent, it is therefore crucial to adopt the concept of toxic equivalency factors (TEFsCarc) for the evaluation of total effects caused by all probable human carcinogenic PAHs. In this study, the default values of TEFsCarc for B[a]A, B[a]P, B[b]F, B[k]F, Chry, D[a,h]A and Ind are 0.1, 1, 0.1, 0.01, 0.001, 1 and 0.1, respectively, as defined by the US-EPA. Further attempts to convert the above-mentioned seven PAHs into one toxic concentration for each observatory site were conducted by using the corresponding TEFsCarc. The evaluation of total toxic B[a]P equivalent (TEQCarc) for all seven PAHs was calculated as described below;

TEQ

Carc

¼

X i

Ci 

TEFiCarc

Condition of the Site

Sampling Position

On the moutain-back from the station Close to the oil tanks (red tank) Close to the bay-front of station Close to penquin rockery and seal coastal line-close to #4 Close to penquin rockery (Chintrap) In front of the building Close to penquin rockery Close to penquin rockery Close to penquin rockery Near the road, on the beach On the road, near Chinese charater On the road, near the station building Under moss On the road, near moss On the moutain-back from the station Under moss, near Chinese character Near Great Wall Station Near Great Wall Station Near Great Wall Station Near Great Wall Station Near Great Wall Station Around the construction area

S S S S S S S S S S S S S S S S S S S S S S S

13 13 13 10 10 10 12 12 12 12 12 12 12 12 12 13 13 13 13 13 13 13 13

11 W 58 57 33 10 W 58 57 26 5 W 58 57 33 28 W 58 59 29 29 W 58 59 56 28 W 58 59 4 58 W 58 57 38 38 W 58 55 41 41 W 58 55 57 41 W 58 54 4 51 W 58 57 46 42 W 58 57 45 56 W 58 57 49 41 W 58 57 44 53 W 58 57 47 14 W 58 57 27 40 W 58 57 45 19 W 58 57 19 25 W 58 57 58 27 W 58 58 11 32 W 58 57 42 35 W 58 57 32 5 W 58 57 36

2.4. Assessments of cancer and non-cancer risks Quantitative ecological cancer risk assessments have been internationally conducted on several environmental compartments including terrestrial soils, marine sediments, and fresh water lake deposits (Bejarano and Michel, 2010; Cachada et al., 2012; Li et al., 2012; Mebarka et al., 2012; Mirsadeghi et al., 2011; Zhang et al., 2012). It is crucial to highlight that the concept of both ecological cancer and non-cancer risks was originally based on the following calculations reported by The Agency for Toxic Substances and Disease Registry (ATSDR), which is a federal public health agency of the U.S. Department of Health and Human Services. In this study, the quantitative ecological risk assessment associated with cancer risks was done by assuming that both incidental ingestion and dermal contact of PAHs contaminated terrestrial soils are two major pathways responsible for the adverse health effects (carcinogenic and non-carcinogenic).

CancerRisk ¼ SFðCDIi þ CDId Þ

Eq. (2)

where SF, CDIi and CDId stand for Slope Factor (1.5 mg kg
1 body weight day
1)
1, Chronic Daily Intake due to Ingestion (mg kg
1 body weight day
1) and Chronic Daily Intake for Dermal exposure.(mg kg
1 body weight day
1), respectively (ATSDR, 2005).

CDIi ¼

CS  IR  EF  CF BW  ATc

Eq. (3)

The acronyms of the incidental ingestion equation (Eq. (3)) can be further explained as bellows:CS ¼ Chemical Concentration (ng g
1) CF ¼ Conversion Factor of 10
6 kg mg
1EF ¼ Exposure Frequency ¼ 40 days year
1.ED ¼ Exposure Duration ¼ 10 yearsIR ¼ Ingestion Rate ¼ 50 mg sediment day
1BW ¼ Body Weight ¼ 53 kgATc ¼ Averaging Time for cancer risk ¼ 25,550 days

CDId ¼ Eq. (1)

62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62

CS  SA  AF  EF  ED  DAF  CF BW  ATc

Eq. (4)

Where the acronyms of dermal contact equation (Eq. (4)) can be described as follows:AF ¼ Skin Adherence Factor ¼ 0.3 mg sediment

Please cite this article in press as: Pongpiachan, S., et al., Quantitative ecological risk assessment of inhabitants exposed to polycyclic aromatic hydrocarbons in terrestrial soils of King George Island, Antarctica, Polar Science (2016), http://dx.doi.org/10.1016/j.polar.2016.12.001

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Fig. 1. . A) Sampling locations for the spatial distribution of PAHs in terrestrial soils of King George Island, Antarctica. B) Spatial distribution feature of PAHs in terrestrial soils of King George Island, Antarctica.

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Fig. 1. (continued).

cm
2DAF ¼ Dermal Absorption Factor ¼ 0.03 (unitless)SA ¼ Skin Surface Area (available for contact) ¼ 4700 cm2 The assessment of non-cancer risk can be further performed by using Eq. (5), where the non-cancer risk can be computed by dividing the total ADD by the oral reference dose (RfD) (ATSDR, 2005).

Non Cancer Risk ¼ HI ¼

ADDi þ ADDd RfD

Eq. (5)

where ADDi, ADDd and RfD stand for Average Daily Dose Ingestion (mg kg
1 body weight day
1), Average Daily Dose Dermal (mg kg
1 body weight day
1) and Reference Dose (3.0  10
4 mg kg
1 body weight day
1), respectively. Where ADDi is computed with the following equation:

ADDi ¼

CS  IR  EF  ED  CF BW  ATNC

Eq. (6)

where the acronyms of incidental ingestion equation (Eq. (6)) can be written as bellows:ATNC ¼ Averaging Time for non-cancer effects ¼ 3650 days Dermal contact can be computed by employing Eq. (7) as written follows:

ADDd ¼

CS  SA  AF  EF  ED  DAF  CF BW  ATNC

Eq. (7)

3. Results and discussion 3.1. PAH concentrations in King George terrestrial soils Table 2 itemizes the arithmetic mean content and standard deviation of PAHs in the King George Terrestrial Soils (KGS), World

Marine Sediments (WMS), and World Terrestrial Soils (WTS). The total concentrations of twelve probably carcinogenic PAHs in KGS varied from 0.296 ng g
1 to 10.4 ng g
1 with an arithmetic mean of P 3.25 ± 2.74 ng g
1. It is important to note that the 12PAHs indicates to the total of detected Phe, An, Fluo, Pyr, B[a]A, Chry, B[b]F, B[k]F, B[a]P, Ind, D[a,h]A and B[g,h,i]P. In this study, the measured P 12PAHs were appreciably lower than those of terrestrial soils collected at Victoria & South Australia (291,453 ± 254,589 ng g
1), Northern Guangdong Province of China (1161 ± 1735 ng g
1), Dalian, China (15,930 ± 15,568 ng g
1), Neuves-Maisons, France (1053 ng g
1), and Dhanbad District of Jharkhand, India (3009 ± 2255 ng g
1) (Juhasz et al., 2016; Laurent et al., 2012; Suman et al., 2016; Wang et al., 2009, 2012). Percentage contribution of each PAH congener to SPAHs (i.e. sum of Phe, An, Fluo, Pyr, B [a]A, Chry, B[b]F, B[k]F, B[a]P, Ind, D[a,h]A and B[g,h,i]P) varied from 0.01 to 50%, with an average of 8.33 ± 14.3%, from 3.13 to 13.95% with an average of 8.33 ± 3.56% and from 1.03% to 25.1% with an average of 8.33 ± 7.66% for KGS, WMS and WTS, respectively (see Fig. 2). Further attempts to elucidate the magnitude of PAH contaminations in KGS were conducted by comparing SPAHs obtained from this study with previous reports. SPAHs contents in KGS varied between 0.296 and 10.4 ng g
1 (mean ¼ 3.25 ± 2.74 ng g
1). These values were lower than the 0.01e0.28 ng g
1 (Signy (UK): Cripps, 1992) but comparable to the results found in Ardley Island (7.33e13.64 ng g
1) reported by Dauner et al., 2015. The average content was also ten times lower than the baseline limit calculated for Admiralty Bay (30e70 ng g
1: Martins et al., 2014). Furthermore, these values were in the same range as or within one or two order of magnitude below those detected around other research stations such as Davis (AUS) (77270 ng g
1: Green et al., 1992), Old Palmer (USA) (2959,478 ng g
1: Kennicutt II et al., 1992), McMurdo (USA) (36013,000 ng g
1: Crockett and White, 2003), Comandante Ferraz (BRA) (9.45-270.5 ng g
1: Martins et al., 2010), Carlini (ARG) (361908 ng g
1: Curtosi et al., 2007), and Mendel (CZ) (1.4-205 ng g
1:

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Table 2 Statistical descriptions of PAH concentrations (ng g
1) collected in KGS in comparison with those of WMS and WTS. KGSa

Phe An Fluo Pyr B[a]A Chry B[b]F B[k]F B[a]P Ind D[a,h]A B[g,h,i]P Total PAHs 3-Ring PAHs 4-Ring PAHs 5-Ring PAHs 6-Ring PAHs 3-Ring PAHs/4-Ring PAHs 4-Ring PAHs/5-Ring PAHs 5-Ring PAHs/6-Ring PAHs

WMSb

WTSc

Aver

Stdev

Aver

Stdev

Aver

Stdev

1.60 0.0799 0.492 0.570 0.0767 0.163 0.0559 0.102 0.0482 0.000194 0.00521 0.0179 3.21 1.68 1.30 0.212 0.0181 1.29 6.16 11.7

1.36 0.106 0.578 0.528 0.165 0.239 0.182 0.131 0.0742 0.000891 0.0149 0.0820 1.62

673 180 802 776 483 407 663 391 376 427 225 347 5749 853 2468 1654 774 0.346 1.49 2.14

1621 447 2285 2095 1092 840 1911 623 794 841 832 730 4576

46,612 11,687 64,616 45,580 17,241 16,900 18,219 6064 13,439 7146 2654 7338 257,496 58,299 144,337 40,375 14,485 0.404 3.57 2.79

149,030 33,510 209,527 119,658 24,927 33,377 29,177 9569 19,711 10,036 3827 10,129 291,268

WMS/KGS

WTS/KGS

421 2255 1629 1362 6289 2490 11,852 3820 7799 2,197,366 43,216 19,356

29,134 146,316 131,293 79,990 224,699 103,366 325,802 59,299 278,989 36,742,853 509,039 409,917

a

Note that the average concentrations of PAHs in KGS obtained from this study. Note that WMS is the average of PAHs in sediments collected from Marine Sediments of Bayou St. John, New Orleans, USA (Mielke et al., 2001), Harbor Sediments of San Diego Harbor, California, USA (Deshmukh et al., 2001), Marine Sediments of Northern Irish Sea, Northern Ireland, UK (Guinan et al., 2001), Harbor Sediments of Mystic River, Boston, USA (Wang et al., 2001), Harbor Sediments of Island End River, Boston, USA (Wang et al., 2001), Marine Sediments, Mangrove, Sai Keng, Hong Kong (Tam et al., 2001), Marine Sediments, Mangrove, Tolo, Hong Kong (Tam et al., 2001), Marine Sediments of Mangrove, Ho Chung, Hong Kong (Tam et al., 2001), Marine Sediments, Mangrove, Mai Po, Hong Kong (Tam et al., 2001), River Sediments of Pearl River, Guangzhou Channel, China (Bixian et al., 2001), River Sediments of Pear River, Shiziyang Channel, China (Bixian et al., 2001), River Sediments of Pearl River, Lingding Bay, China (Bixian et al., 2001), Marine Sediments of Northern Adriatic Sea, Italy (Notar et al., 2001), Coastal Sediments of Cotonou (benin), Africa (Soclo et al., 2000), Coastal Sediments of Aquitaine, France (Soclo et al., 2000), Coastal Sediments of Mediterranean, France (Baumard et al., 1998), Coastal Sediments of Mediterranean, Spain (Baumard et al., 1998), Coastal Sediments, Brazil (Medeiros and Bícego, 2004), Coastal Sediments of Guba Pechenga, Russia (Savinov et al., 2003). c Note that WTS is the average of PAHs in terrestrial soils collected in Victoria, Australia (Juhasz et al., 2016), Northern Guangdong Province of China (Wang et al., 2012), Dalian, China (Wang et al., 2009), Beijing, China (Sun et al., 2012; Luo et al., 2013), Helsinki, Finland (Winquist et al., 2014), Neuves-Maisons, France (Laurent et al., 2012), Northern Region of France (Lors et al., 2012; Techer et al., 2012), Dhanbad District of Jharkhand, India (Suman et al., 2016), Ulsan, Korea (Kwon and Choi, 2014), Northern Part of Poland (Melnyk et al., 2015), Dilovasi, Turkey (Cetin, 2016), and Southern Part of Thailand (Pongpiachan et al., 2013b). b


et al., 2008). In addition, spatial distribution feature of Kl
anova PAHs was illustrated in Fig. 1B. In spite of the fact that the average concentrations of PAHs measured in KGS are exceedingly low, the diagnostic binary ratios of 3-Ring PAHs/4-Ring PAHs (i.e. 1.29), 4-Ring PAHs/5-Ring PAHs (i.e. 6.16), and 5-Ring PAHs/6-Ring PAHs (i.e. 11.7) are substantially high in comparison with those of WMS and WTS (see Table 2). These imply that low and middle molecular weight PAHs are two dominant congeners found in King George terrestrial soils. It is also interesting to underline that Phe is the most abundant congener observed in KGS with the percentage contribution of 49.8% followed by Pyr (17.7%), Fluo (15.3%), Chry (5.09%), and B[k]F (3.18%). Fluo shows the highest percentage contribution in WMS and WTS, with the percentage contribution of 14.0% and 25.1%, respectively. The percentage contributions of Phe detected in KGS were 4.3 times and 2.8 times higher than those of WMS and WTS, respectively. Since several previous studies have been highlighted Phe as a major component of diesel exhaust particles (DEP) (Tavares et al., 2004; Tsien et al., 1997), the comparatively high percentage contribution of Phe observed in KGS can be attributed to the volatilization of the Arctic grade diesel fuel possibly as a consequence of the fire at the Brazilian Antarctic Station (The Comandante Ferraz Antarctic Station fire: 62100 S; 58 240 W) located on King George Island in Admiralty Bay on February 25th, 2012 (Colabuono et al., 2015; Guerra et al., 2013). The results obtained from this study appear somewhat consistent with a previous research highlighting that low molecular weight PAHs are the major components detected in Antarctic soils (Colabuono et al., 2015) and snows (Na et al., 2011).

3.2. Assessment of terrestrial soil toxicity based on the total toxic B [a]P equivalent (TEQcarc) As illustrated in Tables 2 and 3, the genotoxic effect caused by Ind is almost negligible due to its extremely low concentration. In this study, the average toxic B[a]P equivalent of Ind is almost 37 million times lower than those of WTS (see Table 3). This can be explained due to several reasons. Depending on the magnitude of heterogeneous reactions with trace gaseous species (e.g. OH radicals, NO3 radicals and O3) coupled with photolysis rates, the atmospheric lifetimes of each particulate PAH congener can largely vary across a broad spectrum. A previous study conducted at Whitbourne, UK had estimated the atmospheric lifetime of Ind with the value of 2.4 days (Pongpiachan, 2006). Similar value of 2.5 days was also reported by estimating atmospheric lifetimes of surface-adsorbed Ind with respect to photolysis under conditions representative of a cloudless sky over the Southern UK in summer (Behymer and Hites, 1988). The comparatively high deposition velocities of Ind observed in deciduous forest (0.60 cm s
1) and coniferous forest (0.038 cm s
1) indicate that the long range atmospheric transportation (LRAT) might be a minor of importance in term of governing Ind content in Antarctic terrestrial soils. It is also worth mentioning that TEQcarc obtained from this study was much lower than those of WMS and WTS for 11,237 times and 300,898 times, respectively. This underlines the importance of Antarctica as the most pristine area on earth and thus it appears reasonable to use KGS as natural background terrestrial soils.

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S. Pongpiachan et al. / Polar Science xxx (2016) 1e11

7

Island (see Fig. 1), which has been identified as an Important Bird Area (IBA) by Birdlife International, it appears reasonable to include these three sampling points into AIS group. It is also well known that sampling points named P4, P5, and P6, which are located at the Northwestern area of Great Wall Station, are the hotspots for Antarctica seal researchers. Therefore, it seems rationale to categorize these three points into AIS group. The rest of sampling points were classified as NIS group. It is also worth mentioning that there is no ideal pristine area without external human influence in Southern part of King George Island. As a consequence, it is almost impossible to find the location representing hypothetical pristine area adjacent to the Great Wall Station. As illustrated in Table 4, the diagnostic binary ratios of NIS/AIS of all individual PAH (except for Ind and B[g,h,i]P) were higher than one indicating that the averages of PAH concentrations measured at NIS were higher than those detected at AIS. These results underline that the major source of PAHs in NIS seems to derive from anthropogenic emissions and that human activities-derived PAHs appear to be a minor of importance in protected areas for Antarctica animals. The average PAH concentrations of both AIS and NIS were subjected to an independent t-test to see if there has been any evidence of a significant change in individual PAH between the two groups. Table 4 shows the only significance enhancement of An (p < 0.01) indicating that 3-ring PAHs is the main carcinogenic compounds derived from human activities in non-animal impacted sites of King George Island. Previous studies highlight the importance of diesel emissions as the main contributors of An in ambient air (Jensen and Hites, 1983; Miguel et al., 1998). Although it is crucial to note that the significance levels could be changed with more samples collected in both groups, the application of diagnostic binary ratios of PAHs can provide some insight into the source identification of PAHs in KGS. 3.4. Application of diagnostic binary ratios of PAH congeners

Fig. 2. Percentage contribution of PAHs collected in KGS, WMS, and WTS.

Over the past few decades, the diagnostic binary ratio method for PAH source identification, includes comparing ratios between pairs of regularly detected PAH congener characteristics of various contributors. The diagnostic binary ratio of certain PAH congener can offer some insight associated with the influence of various

Table 3 Statistical descriptions of B[a]PEquivalent concentrations (ng g
1) and TEQCarc (ng g
1) collected in KGS in comparison with those of WMS and WTS. TEF (US-EPA)

B[a]A Chry B[b]F B[k]F B[a]P Ind D[a,h]A TEQCarc

0.1 0.001 0.1 0.01 1 0.1 1

KGS

WMS

WTS

Aver

Stdev

Aver

Stdev

Aver

Stdev

0.00767 0.000163 0.00559 0.00102 0.0482 0.0000194 0.00521 0.0679

0.0165 0.000239 0.0182 0.00131 0.0742 0.0000891 0.0149 0.125

48.3 0.407 66.3 3.91 376 42.7 225 763

109 0.840 191 6.23 794 84.1 832 2018

1724 16.9 1822 60.6 13,439 715 2654 20,431

2493 33.4 2918 95.7 19,711 1004 3827 30,082

3.3. Assessment of PAHs collected at animal and non-animal sites Further investigations had been conducted for the comparison between the animal impacted sites with other sites in terms of PAH contents as illustrated in Table 4. Sampling sites were classified into two main groups on the basis of relative frequency of appearances of animals namely “Animal Impacted Site (AIS)” and “Non-Animal Impacted Site (NIS)”. Since P8, P9, and P10 were located in Penguin

contributors of PAHs (Bi et al., 2003; Guo et al., 2003). For instance, Fl/(Fl þ Pyr), B[e]P/(B[e]P þ B[a]P), B[b,j,k]F/B[g,h,i]P, Ind/B[g,h,i]P, B [a]P/B[e]P, B[a]A/Chry, B[a]P/B[g,h,i]P and Ind/(Ind þ B[g,h,i]P), can be applied as unique indicators to classify their emission sources (Tsapakis and Stephanou, 2005; Yunker and Macdonald, 2003). As illustrated in Table 5, An/(An þ Phe), Fluo/(Fluo þ Pyr), B[a]A/(B[a] A þ Chry), and Ind/(Ind þ B[g,h,i]P) ratios were employed as diagnostic parameters to identify PAH congeners from lubricating

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Table 4 Statistical descriptions of PAH concentrations (ng g
1) collected at Animal and Non-Animal Sites in King George Island. Conc. (ng g
1)

Phe An Fluo Pyr B[a]A Chry B[bþk]F B[e]P B[a]P Ind D[a,h]A B[g,h,i]P

AIS (n ¼ 6)

NIS (n ¼ 15)

Aver

Stdev

Aver

Stdev

1.46 0.137 0.243 0.403 0.0483 0.0507 0.0509 0.00537 0.0427 ND 0.00218 ND

0.999 0.125 0.215 0.257 0.118 0.0759 0.0514 0.00878 0.0552 ND 0.00379 ND

1.66 0.489 0.522 0.651 0.189 0.184 0.216 0.0514 0.0524 0.00445 0.00567 0.0221

1.51 0.0925 0.651 0.599 0.183 0.268 0.343 0.121 0.0822 0.00105 0.0176 0.0971

NIS/AIS

t-Test (p < 0.01)

1.139 3.580 2.152 1.615 3.916 3.628 4.243 9.572 1.226 NA 2.605 NA

NS S NS NS NS NS NS NS NS NA NS NA

Table 5 Characteristic values of selected diagnostic binary ratios for petroleum and single-source combustion in comparison with those values obtained from this study (Modified from Yunker et al., 2002). Source This study AIS NIS Petroleum Lubricating oil Asphalt Combustion Gasoline Road dust Used engine oil, gasoline passenger car Used engine oil, diesel car, truck and bus

An/(An þ Phe)

Fluo/(Fluo þ Pyr)

B[a]A/(B[a]A þ Chry)

Ind/(Ind þ B[g,h,i]P)

0.086 0.23

0.38 0.45

0.49 0.51

ND 0.17

e e

0.29 e

0.10 0.50

0.12 0.52e0.54

0.11 0.18 0.22 e

0.44 0.42 0.30 0.37

0.33e0.38 0.13 0.50 e

0.09e0.22 0.51 0.18 0.29

oil, asphalt, gasoline combustion, road dust, used engine oil, and diesel exhausts. Four diagnostic binary ratios of PAH congeners of King George Island terrestrial soils were computed and compared with a previous study of PAH fingerprints reported by Yunker and Macdonald (2003). An/(An þ Phe) and B[a]A/(B[a]A þ Chry) ratios were employed as parameters to distinguish petroleum combustions from other agricultural waste and biomass burnings, with comparatively low binary ratios (0.11 and 0.33e0.38, respectively) signifying gasoline combustion, intermediate ratios (0.22 and 0.50) indicating used engine oil (Yunker and Macdonald, 2003). Since the average values of An/(An þ Phe) obtained from NIS was 0.23, it denoted the contamination of used engine oil and gasoline passenger car on non-animal impacted sites. This interpretation is further supported by the results of Ind/(Ind þ B[g,h,i]P) (0.17), Fluo/ (Fluo þ Pyr) (0.45) and B[a]A/(B[a]A þ Chry) (0.51), underlining the impact of petroleum combustions over King George Island terrestrial soil samples.

3.5. Assessment of cancer and non-cancer risks By assuming that incidental ingestion and dermal contact are two major exposure pathways of PAH contaminated soil dust, both cancer and non-cancer risk levels of PAH concentrations can be computed as previously written in Eqs. (2)e(7). Incidental ingestion has the percentage contribution of 54% while the dermal contact is approximately 46%. This implies that incidental ingestion is the main route of PAH bioaccumulations into human body. These findings are also in good agreement with previous studies highlighting that incidental ingestion is the main exposure pathways of toxic chemicals (Du et al., 2013; Zhou et al., 2014). As illustrated in Fig. 3, the logarithms of cancer risk levels of PAH concentrations in

KGS ranged from
11.1 to
7.18 with an average of
7.96 ± 7.73, which is 1790 times and 80,176 times lower than that of WMS and WTS, respectively. All cancer risk levels of PAH concentrations observed in KGS are significantly (p < 0.001) lower than those of WMS and WTS. The Superfund Program adopts a cancer risk level of 10
6 to highlight the point at which risk management actions should be seriously evaluated (US-EPA, 1989, 2001). Based on the analytical results, the average of cancer risk in KGS is 91.4 times lower than the US-EPA baseline, underlining the fact that the magnitude of cancer risk falls in the “acceptable level” range. Based on the “Role of the Baseline Risk Assessment in Superfund Remedy Selection Decisions” memorandum reported by US-EPA (1991), the non-carcinogenic Hazard Index (HI) can be employed as an indicator to evaluate the cumulative non-carcinogenic site risk to an individual based on the rational highest exposure. In the case of HI < 1, it seems pragmatic to interpret that there is no substantial risk of non-carcinogenic impacts. Conversely, if HI > 1, this suggests a higher risk of non-carcinogenic impacts, and thus the probability increasing with the rising value of HI. In the case of HI is less than one, the action generally is not warranted unless there are adverse ecological effects for both current and future land use. As demonstrated in Fig. 4, all the logarithms of HI values observed in KGS samples are less than zero emphasizing that adverse human health impacts triggered by non-carcinogenic compounds are minor of importance in King George Island.

4. Conclusions Despite its comparatively low atmospheric lifetime, Phe is the most abundant congener of PAHs observed in King George terrestrial soils. This indicates local diesel combustions as a consequence

Please cite this article in press as: Pongpiachan, S., et al., Quantitative ecological risk assessment of inhabitants exposed to polycyclic aromatic hydrocarbons in terrestrial soils of King George Island, Antarctica, Polar Science (2016), http://dx.doi.org/10.1016/j.polar.2016.12.001

S. Pongpiachan et al. / Polar Science xxx (2016) 1e11

Fig. 3. Logarithms of CDIi, CDId, and Cancer Risk collected in KGS, WMS, and WTS.

of the Comandante Ferraz Antarctic Station fire occurred in February 25th, 2012. Incidental ingestion is the main exposure pathway of PAH contaminated soil dusts followed by dermal contact. This pattern is similar to previous ecological risk assessment studies conducted outside Antarctica leading concerns of bioaccumulation and biomagnification, in which PAHs occur in their

9

Fig. 4. Logarithms of ADDi, ADDd, and Non-Cancer Risk collected in KGS, WMS, and WTS.

largest ecological concentration in high-level predators at the top of food chain. Both cancer risk and non-carcinogenic HI of KGS falls in acceptable level, highlighting the importance of Antarctica as one of the most pristine environment on earth.

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Acknowledgement The authors acknowledge the Information Technology Foundation under the Initiative of Her Royal Highness Princess Maha Chakri Sirindhorn, Polar Research Project under the Initiatives of Her Royal Highness Princess Maha Chakri Sirindhorn, National Science and Technology Development Agency, Chinese Arctic and Antarctic Administration, and T. C. Pharmaceutical Industries Co., Ltd for supporting this study. The authors would also like to thank all members of CHINARE 30 for their kind assistances. References Aislabie, J., Balks, M., Astori, N., Stevenson, G., Symons, R., 1999. Polycyclic aromatic hydrocarbons in fuel-oil contaminated soils, Antarctica. Chemosphere 39 (13), 2201e2207. Akyüz, M., Çabuk, H., 2009. Meteorological variations of PM2.5/PM10 concentrations and particle-associated polycyclic aromatic hydrocarbons in the atmospheric environment of Zonguldak, Turkey. J. Hazard. Mater 170 (1), 13e21. Amodio, M., Caselli, M., Gennaro, G., Tutino, M., 2009. 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Please cite this article in press as: Pongpiachan, S., et al., Quantitative ecological risk assessment of inhabitants exposed to polycyclic aromatic hydrocarbons in terrestrial soils of King George Island, Antarctica, Polar Science (2016), http://dx.doi.org/10.1016/j.polar.2016.12.001