Tracking polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in sediments and soils from the southwest of Buenos Aires Province, Argentina (South eastern part of the GRULAC region)

STOTEN-21074; No of Pages 7 Science of the Total Environment xxx (2016) xxx–xxx

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Short Communication

Tracking polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in sediments and soils from the southwest of Buenos Aires Province, Argentina (South eastern part of the GRULAC region) Norma Tombesi a,⁎, Karla Pozo b,c,d, Mónica Álvarez a, Petra Přibylová b, Petr Kukučka b, Ondřej Audy b, Jana Klánová b a

Universidad Nacional del Sur, Departamento de Química, Av. Alem 1253, 8000, Bahía Blanca, Argentina Masaryk University, Faculty of Science, Research Center for Toxic Compounds in the Environment (RECETOX), Kamenice 753/5, 625 00 Brno, Czech Republic c Universidad Católica de la Santísima Concepción, Facultad de Ciencias, Alonso de Ribera 2850, 407 01 29 Concepción, Chile d Department of Physical, Earth and Environmental Sciences, University of Siena, Via Mattioli 4, 53100 Siena, Italy b

H I G H L I G H T S

G R A P H I C A L

A B S T R A C T

• PCBs and PBDEs were investigated in soils and sediments of Argentina. • The highest PCB and PBDE levels were found close to the port and industrial area. • PBDE-209 was dominant (84 ± 13%) at all sampling sites. • Heavier PCBs (PCB-153 and -180) were predominant in sites near the industrial area.

a r t i c l e

i n f o

Article history: Received 27 May 2016 Received in revised form 30 September 2016 Accepted 1 October 2016 Available online xxxx Editor: D. Barcelo Keywords: PCBs PBDEs Sediments Soils

a b s t r a c t PCBs and PBDEs (7 and 10 congeners, respectively) were analyzed in four coastal surface sediments collected from the northern shore of Bahía Blanca estuary and in nine soils from different locations of Bahía Blanca city and the surrounding region (Southwest of Buenos Aires Province, Argentina). Sediment samples showed PCBs(Σ7) concentrations ranged from 0.61 to 17.6 ng g−1 (dry weight = dw) and PBDEs(Σ10) from 0.16 to 2.02 ng g−1 dw, whereas in soil samples ranged from 0.04 to 1.67 ng g−1 dw for PCBs(Σ7) and 0.04 to 10.7 ng g−1 dw for PBDEs(Σ10). The highest concentrations of both chemicals were detected in the urban and industrial/ port areas showing a dominance of the higher chlorinated PCB congeners: in sediments for PCB-180 (56 ± 33%) and PCB-153 (11 ± 6%); and in soils for PCB-138 (23 ± 3%), PCB-153 (22 ± 2%) and PCB-180 (18 ± 7%). In contrast, lower chlorinated PCB congeners were predominant at more distant sites; in sediments for congeners PCB-28 (33 ± 4%) and PCB-52 (14.5 ± 0.2%); and in soils PCB-28 (56 ± 14%) and PCB-52 (33 ± 19%). PBDE-209 (high brominated PBDE) showed the highest relative abundance in both sample types i.e., sediment (94 ± 7%) and soil (80 ± 12%). These findings can be considered lower or similar when compared with other sites of the world, and are likely associated with anthropogenic activities in their surrounding area, which has experienced

⁎ Corresponding author. E-mail address: [email protected] (N. Tombesi).

http://dx.doi.org/10.1016/j.scitotenv.2016.10.013 0048-9697/© 2016 Elsevier B.V. All rights reserved.

Please cite this article as: Tombesi, N., et al., Tracking polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in sediments and soils from the southwest of ..., Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.10.013

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Argentina GRULAC

a fast industrial growth in the last decade. This is the first investigation of PBDEs levels in the whole study area and of PCBs in soils from the Bahía Blanca city and surrounding region. This article provides new and useful information on POP levels in the South eastern part of the GRULAC region. © 2016 Elsevier B.V. All rights reserved.

1. Introduction Bahia Blanca city is one of the most important urban and industrial emplacements located on the coast in the Southwest of the Buenos Aires province, Argentina. The name of Bahía Blanca is due to the color of the salt covering the soils surrounding its shores, which is typical for this zone, and the coastal system is now considered an estuary (Perillo et al., 2004). Estuarine systems are of great importance since these are biologically productive areas and frequently receive considerable pollutant inputs from land based sources via river runoff and sewage outfalls (González-Macías et al., 2007). The Bahia Blanca Estuary constitutes an ecosystem unique in the world by its physical, geographic and biological characteristics (Zilio et al., 2013), with a total surface area of 2300 km2 (about 410 km2 of islands and 1150 km2 of intertidal sector) (Arias et al., 2010). This estuary presents intensive anthropogenic activity, due to the emplacement of Bahía Blanca and Punta Alta cities, (more than 350,000 inhabitants) located on the north shoreline, which is characterized by industrial activities such as oil, fertilizer, chemical and plastic factories, various commercial harbors, and an army ship-repair yard. Its port complex is one of the most important in the country due to its diversity, its strategic location, and facilities to receive large ships thanks to its deep waters. In addition, the estuary sustains local fisheries i.e., a 12-m over-all length ships, fishing fleet with a total catch of 600 t/yr (Arias et al., 2009). Bahía Blanca city is situated in a transition area between the wet and the dry Pampa region, where only few urban clusters are located on the surroundings. The climate and geographic characteristics make the region favorable for livestock and farming of mainly wheat and barley to the north, and irrigation-assisted production (e.g. garlic and onion among others) to the south (Tombesi et al., 2014). Polychlorinated biphenyls (PCBs) and polybrominated biphenyl ethers (PBDEs) are manufactured chemicals mainly produced for industrial and commercial purposes (Wang et al., 2012). PCBs and PBDEs are groups of compounds considered as persistent organic pollutants (POPs), with certain structural similarities that share physicochemical properties (Cappelletti, 2014). They are persistent, toxic, bioaccumulative, and widely distributed in the environment, with different histories of use (Johannessen et al., 2008). Whereas the PCBs were widely used in industry as heat exchange fluids, in electric transformers and capacitors, and as additives in paints, carbonless copy paper, and plastics, the PBDEs are used as additive flame retardants by their ability to inhibit or suppress combustion in organic materials. In turn, while the PCBs were part of the initial 12 POPs listed by the Stockholm Convention (SC) in 2004, the PBDEs (penta and octabromodiphenyl ethers formulations) were added later in 2009 (UNEP, 2016). Argentina - a member of the Group of the Latin American and Caribbean Countries (GRULAC) - ratified the Stockholm Convention and became a Party in 2005 (SAyDS, 2005). Due to the fact that Bahia Blanca estuary sustains an important marine biological productivity, several studies were conducted to assess levels of pollution on the coastal system. In the last 30 years only a few studies (less than ten) have informed POP levels in different environmental matrices for the Bahia Blanca estuary and particularly most of these reports have been focused on organochlorine pesticides (Sericano and Pucci, 1984; Zubillaga et al., 1987; Lanfranchi et al., 2006; Arias et al., 2010). On the other hand, very little is known about the potential contribution of trace organic contaminant levels from the urban and industrial settlements on its surrounding region in the Southwestern area of Buenos Aires province. Up to this moment, there

is only one report on PCBs levels in sediments of the Bahía Blanca estuary (Arias et al., 2013), and no information is available for flame retardant levels like PBDEs in this area of Argentina. Therefore the aim of this work is to identify and quantify the POPs levels in surface sediments from the northern shoreline of the Bahía Blanca estuary and in soil samples of the Bahía Blanca city and surrounding region in the southwest of the Buenos Aires province, Argentina. In addition, we will assess PCB and PBDE composition patterns (i.e., relative concentrations and homologues congeners) in order to provide an insight on their occurrence in the study region. This investigation will provide new and useful information on POPs levels spatial distribution in the Southeastern part of the GRULAC region to address national, regional and global data needs under the Stockholm convention, as well as the establishment of future environmental surveillance programs. 2. Materials and methods 2.1. Sample collection Sediment and soil samples were collected along a zigzag track (Tack and Verloo, 2001) in the same sampling point of the superficial layer (1– 5 cm), in order to obtain representative composite samples. At each sampling site (n = 8) samples were taken and mixed in glass recipients to be homogenized. In this way, composite samples for each sampling point were obtained. Samples (700–1000 g) were kept at 4 °C until the corresponding analyses were carried out. Then they were air-dried and isolated at ambient laboratory temperatures for at least 72 h. Fig. 1 and Table 1 show the location and description of the sampling sites. Additional satellite Landsat images are provided in the Supplementary material (Figs. S1 to S7). Surface oxic sediments (which have a light brown, flaky appearance, and no sulfide smell) were sampled in March 2011 at four stations of the intertidal zone at the northern shore of Bahía Blanca estuary (southwestern of Buenos Aires Province, Argentina) identified as S1, S2, S3 and S4. Sediments were sieved (250 mesh) and the lower particle size fraction (b63 μm) was retained and analyzed. Soil samples were taken in October–November 2014 at nine stations on the surrounding area, about 100 km, around Bahía Blanca city, identified as B1 and B2 (Bahía Blanca city), and R1 to R7 (surrounding region). 2.2. Chemical analysis Sediment and soil samples (5.00 g) were analyzed for seven PCB congeners (PCB-28, -52, -101, -118, -153, -138, -180) and for ten PBDE congeners (BDE-28, -47, -66, -99, -100, -85, -154, -153, -183, -209). All chemicals used were of analytical and chromatographic grade with high purity. Organic solvents were supplied by J.T. Baker (Poland), PCBs standards by LGC Standards (© LGC Limited, UK), and PBDEs standards by Wellington Laboratories Inc. (Canada). Samples were homogenized with anhydrous sodium sulfate and were spiked with surrogate recovery standards: PCB-30 and PCB-185 for PCBs and OCP analysis (50 μL of concentration 0.2 μg mL-1), 13C PBDE-28, -47, -66, -100, -99, -85, -154, -153, -183 (50 μL of concentration 20 pg mL− 1) for PBDE-28 to -183, and, 13C PBDE-209 (100 pg μL−1) for PBDE-209 analysis. Samples were extracted with 150 mL of dichloromethane in a Büchi System B-811 automatic extractor. One laboratory blank and one reference material were analyzed with each set of ten samples.

Please cite this article as: Tombesi, N., et al., Tracking polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in sediments and soils from the southwest of ..., Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.10.013

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Fig. 1. Site location for soils (orange dots) and sediments (red dots) samples from the southwest of Buenos Aires Province (a) and Bahía Blanca city and estuary (b). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

After extraction, the volumes of the resulting extract were reduced to 2 mL under a gentle stream of nitrogen. The organic extracts were cleaned-up on a glass column filled with sulfuric acid, modified silica gel, and were eluted with 40 mL hexane:CH2Cl2 (1:1) mixture. The eluates were reduced in TurboVap II, transferred into a GC auto sampler conical mini-vial and spiked with recovery standards PCB-121 (50 μL of concentration 0.2 μL mL−1) and 13C PBDE-77 and -138 (10 μL of concentration 20 pg μL− 1) used as internal standards for PCB/OCP and PBDEs, respectively. The extracts were reduced to the final volume (100 μL) under a gentle stream of nitrogen, and stored in amber vials at −20 °C until the final chromatographic analysis. PCBs analysis was performed using a GC–MS/MS instrument. 7890A GC (Agilent, CA, USA) equipped with a 60 m, 0.25 mm, 0.25 μm HT8 column (SGE, Louisiana, USA) coupled to 7000B MS (Agilent, CA, USA) operated in electron impact ionisation and MS/MS mode was used. Table S1 in Supplementary material includes mother and daughter ions, and collision energies (eV) for PCBs quantitation. Injection was pulsed splitless 3 μL at 280 °C, He as a carrier gas at 1.5 mL min−1. The GC temperature ramp was 80 °C (1 min hold), then 40 °C min−1 to 200 °C, and

finally 5 °C min−1 to 305 °C (Cincinelli, et al., 2016, in press). PCBs were quantified with 8 point calibration with concentrations from 1 ng mL−1 to 4000 ng mL−1 and linearity was maintained in the whole range. Instrumental limits of detection and the limits of quantification were calculated from the lowest calibration point as an amount producing signal to noise 3 (LOD) and 10 (LOQ). Table S2 shows values calculated for the corresponding LOD and LOQ. HRGC/HRMS was used for analysis of PBDEs: 7890A GC (Agilent, USA) equipped with a 15 m × 0.25 mm × 0.10 μm DB5 column (Agilent J&W, USA) coupled to an AutoSpec Premier MS (Waters, Micromass, UK). The MS systems were operated in EI+ mode at the resolution of N10,000, and for PBDE-209, the MS resolution was set to N5000. Injection was splitless 2 μL to 280 °C, with He as carrier gas at 1 mL min−1. The GC temperature program was 80 °C (1 min hold), then 20 °C min− 1 to 250 °C, followed by 1.5 °C min−1 to 260 °C (2 min hold), and 25 °C min−1 at 320 °C (4.5 min hold) (Lohmann et al., 2013; Pozo et al., 2015). PBDEs were quantified using five point calibration curve for PBDEs 28–183 (from 1 to 500 ng mL−1) and six point calibration curve for PBDE 209 (from 1 to 1000 ng mL−1). The limits of quantitation

Table 1 Geographic coordinates and description of the sampling sites. Site sample Sediments Cuatreros Harbor Maldonado PBB Galván Harbor Soils Bahía Blanca city Bahía Blanca city Médanos Hilario Ascasubi La Chiquita Cabildo Dorrego Pehuen-Co Napostá

Code

Latitude/longitude

Area description/use

S1 S2 S3 S4

38° 44′ 31″/62° 23′ 11″ 38° 45′ 44″/62° 19′ 25″ 38° 45′ 43″/62° 18′ 15″ 38° 46′ 40″/62° 18′ 18″

Intertidal zone/recreational fishing Intertidal zone/recreational (Park) Intertidal zone/petrochemical industry effluent discharge point Intertidal zone/close to logistic facilities for bulk liquid fuels transportation

B1 B2 R1 R2 R3 R4 R5 R6 R7

38° 42′ 03″/62° 16′ 03″ 38° 45′ 32″/62° 17′ 09″ 38° 49′ 22″/62° 41′ 34″ 39° 23′ 27″/62° 37′ 39″ 39° 35′ 16″/62° 06′ 04″ 38° 34′ 19″/61° 53′ 39″ 38° 44´ 21″/61° 15′ 38″ 39° 00′ 11″/61° 33′ 51″ 38° 26′ 32″/62° 17′ 15″

Urban Industrial/urban Urban Rural, agricultural-livestock area close to urban cluster (b2 km) Small seaside resort (recently become a fishing beach) Agricultural-livestock Rural, agricultural-livestock area close to small aerodrome and urban cluster (b2 km) Urban seaside resort Agricultural-livestock

Please cite this article as: Tombesi, N., et al., Tracking polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in sediments and soils from the southwest of ..., Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.10.013

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Table 2 PCB concentrations (ng g−1 dw) found in superficial sediments and soils from the study area.

Sites Sediments S1 S2 S3 S4 Soils B1 B2 R1 R2 R3 R4 R5 R6 R7

PCB-28

PCB-52

PCB-101

PCB-118

PCB-138

PCB-153

PCB-180

3-Cl

4-Cl

5-Cl

5-Cl

6-Cl

7-Cl

7-Cl

0.18 0.38 0.13 0.44

0.09 0.15 0.11 0.23

0.08 0.13 0.13 0.19

0.07 0.14 0.17 0.17

0.07 0.10 0.25 0.22

0.08 0.10 0.22 0.78

0.04 0.03 0.30 15.60

0.61 1.03 1.31 17.6

0.06 0.07 0.08 0.07 0.03 0.03 0.02 0.03 0.02

0.06 0.17 0.06 0.06 0.003 0.03 0.01 0.02 0.02

0.11 0.29 0.04 0.03 b0.008 0.01 b0.008 0.01 b0.008

0.17 0.23 0.03 0.02 b0.008 b0.008 b0.008 0.01 b0.008

0.34 0.34 0.11 0.02 b0.01 b0.01 0.03 0.07 b0.01

0.30 0.35 0.11 0.03 b0.01 b0.01 0.02 0.07 b0.01

0.12 0.21 0.11 0.01 b0.01 b0.01 0.02 0.09 b0.01

1.17 1.67 0.53 0.25 0.04 0.07 0.09 0.31 0.04

(LOQ) for the PBDEs were calculated from individual chromatograms of individual samples (Table S3) using TargetLynx software (Waters, MIcromass, UK), with concentrations corresponding to 9:1 signal:noise ratio. Table S4 in Supplementary material shows detailed information for PBDEs quantitation (ions, isotopic ratio and retention time). PCBs recoveries were determined for all samples by spiking with the surrogate standards prior to extraction and were 76–100%. Recovery factors were not applied to any of the data. Recovery of native analytes measured in reference material varied from 88 to 103% for PCBs. Isotopic dilution method was used for PBDEs data quantification that means all data were recovery corrected using Mass Lynx software (Waters, UK). The recoveries were in the range 50–125% for BDEs 28–183, and 30–130% for BDE 209. The instrumental linear response range is 5 orders of magnitude for PCBs and PBDEs. Finally the laboratory blanks were below the detection limits for all compounds. 3. Results and discussion 3.1. PCBs PCB concentrations found in soils and superficial sediments from this study are reported in Table 2 an expressed in ng g−1 dry weight (dw). The seven PCB congeners studied (PCB-28, -52, -101, -118, -138, -153, and -180) are considered as indicators due to their relatively high concentrations in technical mixtures and their wide chlorination range (3–7 chlorine atoms per molecule) (Webster et al., 2013). Hereafter the bibliography for this discussion only will include reported values considering the sum of these 7 congeners (Supplementary material, Tables S5 and S6 for sediment and soil information, respectively). 3.1.1. PCBs in sediments Results showed that all congeners of PCB analyzed were detected in the sediment samples PCB(Σ7) concentrations ranged from 0.6 to 18 ng g− 1 dw. This result falls between the range found by Arias et al. (2013) within a wider area of Bahía Blanca estuary (0.20–160 ng g−1 dw); however, concentrations detected in this study were predominantly low. Additionally, these authors considered that PCBs sediment levels in their study correspond to moderately polluted environment compared to other sites of the world (Arias et al., 2013). Colombo et al. (2005) found similar levels of PCBs for Río de la Plata estuary varying from 0.02 to 41.0 ng g−1 dw in the neighbourhood of Buenos Aires city where the main anthropogenic discharges, to the coastal environment, are located. In fact, these findings are two orders of magnitude lower than PCB levels reported by Frignani et al. (2001) in superficial sediments of Venice canals (a zone strongly influenced by industrial sewage) (up to 1794 ng g−1 dw).

ΣPCBs

In this study, PCBs levels showed a clear increasing concentration gradient, from site S1 (0.6 ng g− 1 dw) to S4 (17.6 ng g− 1 dw), with highest PCB levels detected near to a highly industrialized area in Galván Harbor and coinciding with the proximity to urban and industrial areas. These results are similar to other areas of the world associated with industrial and harbor activities. For instance, similar PCB levels were reported by Tolosa et al. (2010) (2.11 to 11.8 ng g−1 dw) in the Cienfuegos bay (Cuba), Vane et al. (2008) (0.1 and 17.7 ng g−1 dw) in New Jersey (USA), Castells et al. (2008) from 1.29 to 30.18 ng g−1 dw in the coastal area of Barcelona (Spain), Salvadó et al. (2013), between 1.3 and 38 ng g−1 dw in the gulf of Lion (France), Nouira et al. (2013) (1.1 to 9.3 ng g−1 dw) for Monastir bay (Tunisia), Lyons et al. (2015) in Kuwait bay and Arabian gulf (Kuwait State) (0.35 and 41.91 ng g−1 dw) and Zhou et al. (2001) from 0.03 to 21.75 ng g−1 dw in the Daya bay (China). The PCB congener composition (%) in sediment showed different PCB patterns (Fig. 2a). In particular, the sites closest to the industrial area (S3 and S4) showed a predominance of heavier PCB congeners i.e., PCB-138 (19%), PCB-153 (17%) and PCB-180 (23%) at site S3 and PCB-180 (89%) at site S4 (coinciding with the highest absolute concentration). These results are likely influenced by the direct emission of local sources (marine traffic, industrial sewage) which played an important role in the accumulation of highly chlorinated PCB congeners (Hong et al., 2005). In contrast, at the sites S1 and S2 there was observed a prevalence of lighter PCB congeners, PCB-28 and PCB-52 in S1 (29% and 14.7%) and S2 (37% and 15%) (sites distant from urban and industrial area), it was suggested substantial atmospheric contribution driven by air-transport of the lighter PCBs congeners (Arias et al., 2013). These findings are consistent with PCB patterns observed by Tombesi et al. (2014) in air at urban sites in the Bahia Blanca city where there was a prevalence of lighter PCB homolog composition represented by 3-Cl (38 ± 7%) and 4-Cl (27 ± 12%). 3.1.2. PCBs in soils PCBs(Σ7) concentrations in soils from Bahía Blanca city and surrounding region were between 0.04 and 1.67 ng g− 1 dw (Table 2). The highest PCB concentrations were detected at urban sites with values from 0.31 (R6) to 1.67 ng g−1 dw (B2, site located in the industrial area of the Bahía Blanca city). Higher PCB concentrations associated with urban or/and industrial sites were also observed in other areas of the world, but with values higher than those found in this study. In this regard, Zhang et al. (2007) reported PCB concentrations up 9.87 ng g−1 dw for soils in urban areas of Hong Kong, China; Wong et al. (2009) up 51 ng g−1 dw in suburban (past industrial sites) from the Greater Toronto Area, Canada; and Motelay-Massey et al. (2004) up 150 ng g−1 dw in industrial sites from the Seine river basin, France (Supplementary material, Table S6).

Please cite this article as: Tombesi, N., et al., Tracking polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in sediments and soils from the southwest of ..., Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.10.013

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a)

5

b)

100%

100%

80%

80%

PCB-153

60%

60%

PCB-138

40%

40%

PCB-118

20%

20%

0%

0%

S1

S2

S3

S4

PCB-180

PCB-101 PCB-52 B1

B2

R1

R2

R3

R4

R5

R6

R7

PCB-28

Fig. 2. PCB congener compositions (%) found in superficial sediments (a) and soils (b) from the study area.

Lower PCB concentrations in soils were observed at rural and agricultural-livestock sites and ranged from 0.04 (R3 and R7) to 0.07 ng g−1 dw (R4). These results were similar to those observed by Zhang et al. (2007) at a natural conservation area in Hong Kong, China (0.04– 0.07 ng g− 1 dw). Finally, in the present study intermediate values were found in rural sites next (b2 km) to urban clusters with concentrations from 0.09 (R5) to 0.25 ng g−1 dw (R2). The PCB congener composition (%) in soil samples (Fig. 2b) also showed different PCB pattern distribution. Urban and/or industrial sites (B1, B2, R1 and R6) showed more contribution of heavier PCB congeners: PCB-138 (23 ± 3%), PCB-152 (22 ± 2%) and PCB-180 (18 ± 7%). In contrast, at rural (R3), and agricultural-livestock (R4 and R7) sites a prevalence of lighter PCB congeners was observed: PCB-28 (56 ± 14%) and PCB-52 (33 ± 19%). Similar trends of spatial distribution of PCBs concentration and congener composition (%) in soil samples was also observed by Motelay-Massei et al. (2004). 3.2. PBDEs Results for PBDE concentrations (ng g−1 dw) found in the superficial sediments and soils from this study are reported in Table 3. 3.2.1. PBDEs in sediments PBDEs(Σ10) concentrations in sediments ranged from 0.16 to 2.02 ng g−1 dw (Table 3). The highest PBDEs concentration was found at site S3 ~2.0 ng g−1 dw next to the effluent discharge point of the Petrochemical Industry Hub. This is consistent with the observation by Moon et al. (2007) and Pan et al. (2011) who identified the petrochemical industry as a possible contaminant source of PBDE contamination. PBDE-209 (high brominated PBDE) was the only congener quantified in all the samples and being the predominant one with concentrations from

0.13 to 2 ng g−1 dw and accounted for 81–100% of total PBDEs composition (Fig. 3a). Similar PBDE-209 congener prevalence in marine sediment was also observed by different authors, and with concentrations varying substantially worldwide. However, the maximum PBDE-209 concentration found in sediments of Bahía Blanca estuary is lower than the highest values observed in other marine sediments of the world, e.g. in the Laizhou Bay area in North China by Pan et al., 2011 (12.0 ng g−1 dw), Concepción Bay in central Chile by Pozo et al., 2015 (21 ng g−1 dw), Yangtze River Delta in China by Chen et al., 2006 (94.6 ng g−1 dw), Belgian North Sea by Voorspoels et al., 2004 (1200 ng g− 1 dw), Scheldt estuary (The Netherlands) by Verslycke et al., 2005 (1650 ng g−1 dw) and at industrialized bays of Korea by Moon et al. 2007 (2248 ng g−1 dw). 3.2.2. PBDEs in soils PBDE concentrations in soils ranged from 0.04 to 10.7 ng g− 1 dw (Table 3). The highest PBDE concentration was found at site B2 (10.7 ng g−1 dw) located in the industrial area of Bahía Blanca city, followed by urban sites B1 (0.49 ng g−1 dw) and R6 (0.20 ng g−1 dw). PBDE-47 and PBDE-209 were the most frequently quantified congeners in the soil samples with concentrations from 0.005 to 0.061 ng g−1 dw and 0.027 to 10.50 ng g−1 dw, respectively. The PBDE-209 values found in urban sites in this study were similar to those reported by Jiang et al. (2010) for urban sites in China (0.48 ± 0.65 ng g−1 dw) and lower than the ones found by Wu et al. (2015) in a residential and commercial area of Shanghai (5.65–116 ng g−1 dw). PBDE-209 levels in soils from different industrial areas of the world were found in varying concentrations, and similar to or higher than the PBDE-209 found in this study (10.7 ng g−1 dw). In this regard, Wu et al. (2015) reported values from 4.74 to 141 ng g−1 dw in Shanghai, and Cetin (2014) informed an average of 22 ± 37 ng g−1 dw, Odabasi et al. (2010) of 36 ± 63 ng g−1 dw, and

Table 3 PBDE concentrations (ng g−1 dw) found in superficial sediments and soils from the study area.

Sites

PBDE-28

PBDE-47

PBDE-66

PBDE-85

PBDE-99

PBDE-100

PBDE-153

PBDE-154

PBD-183

PBDE-209

3-Br

4-Br

4-Br

5-Br

5-Br

5-Br

6-Br

6-Br

7-Br

10-Br

b0.008 0.013 0.005 0.009

b0.02 b0.005 b0.006 b0.002

b0.02 b0.004 b0.02 b0.01

b0.01 0.01 b0.01 b0.007

b0.006 0.002 b0.01 b0.005

b0.009 b0.004 b0.07 b0.009

b0.03 b0.002 b0.03 b0.005

b0.02 b0.004 b0.004 b0.006

0.46 0.13 1.95 0.33

0.46 0.16 2.02 0.34

0.042 0.061 0.005 0.005 0.014 0.021 0.011 0.016 0.007

b0.003 b0.009 b0.002 b0.0006 b0.0007 b0.001 0.0005 0.0007 0.0008

b0.004 b0.005 b0.004 b0.003 b0.0003 b0.0003 b0.0004 b0.001 b0.0003

0.073 0.111 0.006 b0.002 0.004 0.004 0.003 0.008 0.002

0.009 b0.02 b0.002 b0.001 0.001 0.001 0.0008 0.002 0.0007

0.008 b0.02 b0.004 b0.003 0.0005 b0.0006 b0.0007 0.001 b0.0006

0.006 b0.01 b0.002 b0.002 b0.0003 b0.0004 b0.0005 0.001 b0.0004

b0.004 0.019 b0.004 b0.002 0.0005 0.0007 0.0006 0.004 0.0004

0.349 10.50 0.073 0.035 0.072 0.027 0.047 0.170 0.029

0.49 10.7 0.08 0.04 0.09 0.05 0.06 0.20 0.04

Sediments S1 b0.005 S2 0.004 S3 0.067 S4 0.004 Soils B1 b0.001 B2 b0.005 R1 b0.002 R2 b0.0008 R3 0.0009 R4 0.001 R5 0.0009 R6 0.001 R7 0.0006

ΣPBDEs

ΣPBDE = PBDE-28 + PBDE-47 + PBDE-66 + PBDE-85 + PBDE-99 + PBDE-100 + PBDE-153 + PBDE-154 + PBDE-183 + PBDE-209.

Please cite this article as: Tombesi, N., et al., Tracking polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in sediments and soils from the southwest of ..., Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.10.013

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N. Tombesi et al. / Science of the Total Environment xxx (2016) xxx–xxx

a)

b)

100%

100%

80%

80%

60%

60%

40%

40%

20%

20% 0%

0%

S1

S2

S3

S4

B1

B2

R1

R2

R3

R4

R5

R6

R7

Fig. 3. Percent of PBDE-209 (blue) contribution from the total PBDEs composition in superficial sediment (a) and soil (b) samples from study area. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

Cetin and Odabasi (2007) of 40 ± 38 ng g−1 dw, all of them from different areas in Turkey. Fig. 3b showed that PBDE-209 was the predominant congener in soils and accounted for 80 ± 12 percentage of total PBDEs composition. A similar trend was observed for soils from different studies across the globe e.g. Jiang et al. (2010) in urban areas of China, Syed et al. (2013) in agricultural, urban, and industrial locations from Punjab Province, Pakistan, Cetin (2014) in heavily industrialized area in Kocaeli, Turkey, Gevao et al. (2011) in rural and urban sites from Kuwait, and Leung et al. (2007) in Guiyu, Guangdong Province, China. These results are consistent with the fact that PBDE-209 is the most commercial product of PBDEs added into plastic products used in high-tech and other electrical appliances (Zou et al., 2007). 4. Conclusions The results of PCBs and PBDEs concentrations detected in coastal sediments and soils from the Bahía Blanca region were consistent with the anthropogenic activities of the surrounding area. These levels varied from low to moderately polluted environments. These results are an important contribution to the data regarding levels of POPs in this region of the southwest of the province of Buenos Aires and its coastal environment. Particulary this is the first study that reports levels of PBDEs in all the study area, and of PCBs in soils from the Bahía Blanca city and region. Further investigation is still needed to extend the area of study in order the better identify sources of PBDEs and PCBs in this region and to assess the potential influence on the marine food web of the Bahía Blanca area. This study provides useful and new information on POPs levels in the South eastern part of the GRULAC region. Acknowledgments This investigation was supported by Universidad Nacional del Sur, PGI MAyDS (24/MA20) project (Principal investigator, PI: N. Tombesi), by the National Sustainability Programme of the Czech Ministry of Education, Youth and Sports (LO1214) and the RECETOX research infrastructure (LM2015051). Furthermore, the authors would like to thank Fondecyt 1161673 project (PI: K. Pozo). Appendix A. Supplementary data Supplementary data to this article can be found online at http://dx. doi.org/10.1016/j.scitotenv.2016.10.013. References Arias, A.H., Spetter, C.V., Freije, R.H., Marcovecchio, J.E., 2009. Polycyclic aromatic hydrocarbons in water, mussels (Brachidontes sp., Tagelus sp.) and fish (Odontesthes sp.) from Bahía Blanca Estuary, Argentina. Estuar. Coast. Shelf Sci. 85 (1), 67–81. Arias, A.H., Vazquez-Botello, A., Tombesi, N., Ponce-Vélez, G., Freije, H., Marcovecchio, J., 2010. Presence, distribution, and origins of polycyclic aromatic hydrocarbons (PAHs) in sediments from Bahía Blanca estuary, Argentina. Environ. Monit. Assess. 160 (1–4), 301–314.

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Please cite this article as: Tombesi, N., et al., Tracking polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in sediments and soils from the southwest of ..., Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.10.013