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Assessment of organotin and tin-free antifouling paints contamination in the Korean coastal area
Marine Pollution Bulletin xxx (2015) xxx–xxx
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Marine Pollution Bulletin journal homepage: www.elsevier.com/locate/marpolbul
Assessment of organotin and tin-free antifouling paints contamination in the Korean coastal area Mi-Ri-Nae Lee a, Un-Jung Kim a,b, In-Seok Lee c, Minkyu Choi c, Jeong-Eun Oh a,⇑ a
Department of Civil and Environmental Engineering, Pusan National University, San 30, Jangjeon-dong, Geumjeong-gu, Busan 609-735, Republic of Korea Center for Environment, Health and Welfare Research, Korea Institute Science and Technology (KIST), 39-1, Hawolgok-dong, Seongbuk-gu, Seoul 136-791, Republic of Korea c Marine Environment Research Team, National Fisheries Research and Development Institute (NFRDI), 408-1, Sirang-ri, Gijang-eup, Gijang-gun, Busan 619-705, Republic of Korea b
a r t i c l e
i n f o
Article history: Received 12 January 2015 Revised 13 July 2015 Accepted 18 July 2015 Available online xxxx Keywords: Antifouling paints Organotin compounds Tin-free compounds Marine sediment
a b s t r a c t Twelve organotins (methyl-, octyl-, butyl-, and phenyl-tin), and eight tin-free antifouling paints and their degradation products were measured in marine sediments from the Korean coastal area, and Busan and Ulsan bays, the largest harbor area in Korea. The total concentration of tin-free antifouling paints was two- to threefold higher than the total concentration of organotins. Principal component analysis was used to identify sites with relatively high levels of contamination in the inner bay area of Busan and Ulsan bays, which were separated from the coastal area. In Busan and Ulsan bays, chlorothalonil and DMSA were more dominant than in the coastal area. However, Sea-Nine 211 and total diurons, including their degradation products, were generally dominant in the Korean coastal area. The concentrations of tin and tin-free compounds were significantly different between the east and west coasts. Ó 2015 Published by Elsevier Ltd.
1. Introduction Tributyltin (TBT) was the most widely used material in the antifouling paints (AFPs) applied to marine vessels over several decades, but since 2003 its use has been restricted by the International Maritime Organization (IMO) due to its negative effect on non-target organisms (i.e., the occurrence of imposex (imposition of male organs on females) Spooner et al., 1991; IMO, 2002). Therefore, approximately 18 tin-free AFPs are currently used as TBT alternatives worldwide (Yonehara, 2000; Thomas et al., 2001), and in Korea 15,000 tons of tin-free AFPs were used in 2007 (The Korea Offshore and Shipbuilding Association (KOSHIPA), 2008). However, it has been suggested that TBT alternatives are also toxic and among the available tin-free AFPs, the application of Irgarol 1051 and diuron to marine vessels has been restricted in some European countries due to their inhibition of photosystem-II and their toxicity to aquatic organisms at low levels (Geigy, 1995; Hall et al., 1999; Gatidou et al., 2007; Sapozhnikova et al., 2013). Chlorothalonil, Sea-Nine 211, and DMSA, a degradation product of dichlofluanid, have also been reported to be more harmful to some microalga, daphnia, and fish cells than Irgarol 1051 and diuron (Fernández-Alba et al., 2002; Okamura et al., 2002). ⇑ Corresponding author. E-mail address: [email protected] (J.-E. Oh).
Many studies have been performed to investigate the fate and effect of TBT and its alternatives in the marine environment (Filipkowska et al., 2014; Sarradin et al., 1995; Harino et al., 2006a,b; Gatidou et al., 2007; Thomas et al.,2002, 2003; Comber et al., 2002). However, most previous studies of TBT alternatives have focused on Irgarol 1051 and diuron in the marine environment (Sapozhnikova et al., 2013; Cresswell et al., 2006; Balakrishnan et al., 2012; Harino et al., 2009). The highest levels of these two chemicals were found in summer due to high levels of yachting activity and inside marinas due to the low water exchange capacity (Lamoree et al., 2002; Biselli et al., 2000; Gatidou et al., 2007; Sapozhnikova et al., 2008; Albanis et al., 2002). In Korea, several studies of OTs and tin-free AFPs have been conducted, with the highest levels of TBT found in the vicinity of a shipyard in a large port (Choi et al., 2013; Kim et al., 2011). It should be noted that Korea’s shipbuilding industry is renowned the first in the global market and recorded 4000 tons for used TBT amounts in the year of 2000 (MOMAF, 2003). After the regulation of TBT in 2000, the amount of tin-free AFPs used increased by about sixfold in 2001 compared to 1998. A recent study of Irgarol 1051 and diuron in Korean seawater indicated a possibility of reduction in root growth rate among macrophyte species (Kim et al., 2014; Lambert et al., 2006) and an approximate fivefold increase of the concentration of tin-free AFPs from 2006 to 2009, while a twofold decrease in the butyltin concentration in coastal
http://dx.doi.org/10.1016/j.marpolbul.2015.07.038 0025-326X/Ó 2015 Published by Elsevier Ltd.
Please cite this article in press as: Lee, M.-R.N., et al. Assessment of organotin and tin-free antifouling paints contamination in the Korean coastal area. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/j.marpolbul.2015.07.038
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Mi-Ri-Nae Lee et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx
areas was observed in the same period (Lee et al., 2011). Contamination by tin-free AFPs in the Korean marine environment is worsening, but only three domestic studies of tin-free AFPs in seawater have been conducted (Lee et al., 2010, 2011; Kim et al., 2014). In addition, there have been no studies of tin-free AFPs in sediment from the Korean coastal area. Considering the likely settling of antifouling paint particles generated during ship maintenance (Thomas et al., 2003) and the potential detrimental influence of various AFPs on marine organisms through desorption from bottom sediment (Harris et al., 1996), the monitoring of AFPs in sediment is essential to assess their effect on the marine environment. Therefore, the aim of this study was to secure baseline data by investigating the concentration and distribution of 12 OTs (mono, di and tri-substituted analogs of methyl-, octyl-, phenyl-, and butyl-tin), 8 tin-free AFPs (Irgarol 1051, Sea-Nine 211, thiram, zineb, ziram, chlorothalonil, dichlofluanid, and diuron), and the degradation products of diuron (DCPMU, DCPU, and CPDU) and dichlofluanid (DMSA) in marine sediment from Korean coastal areas. The concentrations were then compared with those in the industrialized large ports of Ulsan and Busan. This is the first study to report the concentrations and distribution of various OTs and tin-free AFPs simultaneously in Korean marine sediment. 2. Materials and methods 2.1. Materials Pesticide-grade hexane and methanol (J.T. Baker Co., Phillipsburg, NY, USA), and sulfuric and hydrochloric acid (Matsunoen chemicals Ltd., Osaka, Japan) were obtained. Sodium tetraethylboratesolution and diethyldithiocarbamate were purchased (Sigma–Aldrich Co.). Atrazine-d5 (Sigma–Aldrich Co., St Louis, MO, USA) and triphenyltin-d15 chloride (TPT-d15) (Resolution Systems Inc., Buffalo, NY, USA) were used as internal standards. The target analytes, N,N-dimethyl-N0 -phenylsulfamide (DMSA), and 1-(3,4-dichlorophenyl)-3-methylurea (DCPMU) were purchased (Dr. Ehrenstorfer, Augsburg, Germany). Methyltin trichloride (MMT), dimethyltin dichloride (DMT), trimethyltin chloride (TMT), zincbis-dimethyldithiocarbamate (Ziram), and 4,5-dichloro-2-octyl-4-isothiazolone-3-one (Sea-Nine 211), N-dichlorofluoromethylthio-N0 , N0 -dimethyl-N-phenylsulfa mide (dichlofluanid), 2,4,5,6-tetrachloro isophthalonitrile (chlorothalonil), zinc ethylene-1,2-bis-dithiocarbamate (zineb), bis-dime thylthiocarbamoyl-disulfide (thiram), 2-methylthio-4-t-butylami no-6-cychlopropylamino-s-triazine (Irgarol 1051), 1-(3,4-dichloro phenyl)-3,3-dimethylurea (diuron) and the degradation products of diuron, 3-(3-chlorophenyl)-1,1-dimethylurea,1-(3,4-dichloro phenyl)urea (DCPU), and 3-(3-chlorophenyl)-1,1-dimethylurea (CPDU) were purchased (Sigma–Aldrich Co.). Mono butyltin trichloride (MBT), dibutyltin dichloride (DBT), tributyltin chloride (TBT), monophenyltin trichloride (MPT), diphenyltin dichloride (DPT), triphenyltin chloride (TPT), mono-noctyltintrichloride (MOT), di-n-octyltin dichloride (DOT), and tri-n-octyltin chloride (TOT) was purchased (Resolution Systems, Inc.). Phenanthrene-d10 (AccuStandard, Inc., New Haven, CT, USA) was used as recovery standard. 2.2. Sample collection and study area Marine sediment samples were collected using a box-core sampler from Busan Bay, Ulsan Bay, and national persistent organic pollutants (POPs) monitoring site, during June 2010, April 2011,
and February 2010, respectively. The sediment collection method followed Choi et al. (2009a). Korea is located in northern East Asia and is surrounded by coast on three sides, with a number of large and small ports along the coastline. A total of 15 sediment samples were collected from national POPs monitoring sites in the Korean coastal area. Busan and Ulsan bays are both highly industrialized and urbanized, as well as having large harbor and shipyard facilities, and hence were specifically targeted in this study. A total of 13 and 11 sediment samples were collected from Busan and Ulsan bays, respectively. For details of the sampling sites refer to Choi et al. (2009b). 2.3. Pretreatment and instrumental analysis The pretreatment method was modified from previous studies by Gonzalez-Toledo et al., 2002; Vidal et al., 2003; Zachariadis and Rosenberg, 2009; Rodríguez et al., 2011. Marine sediment samples (10 g) were extracted by mechanical shaking (15 °C, 150 rpm, 1 h), following by sonication (15 min) with 60 mL hexane. Atrazine-d5 and TPT-d15 were spiked as internal standards before the extraction. For derivatization, a minimal amount of sodium tetraethylborate solution (0.5%) and diethyldithiocarbamate (DDTC, 0.1 g equivalent) were mixed. The supernatant was transferred to a round bottom flask and 45 mL 1 N Sulfuric acid was added. Acidic sediment extractions were performed by solid-phase extraction (Supelco, Bellefonte, PA, USA) with OASIS HLB (6 cc, 200 mg), (Waters, Milfold, MA, USA). The cartridge was conditioned with 5 mL hexane, 5 mL MeOH, and 5 mL distilled water. After sample loading, the cartridge was dried for 1 h and eluted with 10 mL hexane. The eluent were passed over an Na2SO4 cartridge (Waters) to remove water and concentrated to 100 lL under nitrogen. Phenanthrene-d10 was spiked to a known concentration as a recovery standard prior to analysis by gas chromatography–mass spectrometry (GC–MS) (GC-HP6890: Hewlett–Packard, Palo Alto, CA, USA) (MS-5973: Agilent Technologies, Palo-Alto, CA, USA), with a DB-5MS column ((5% Phenyl)-methylpolysiloxane, 30 m length, 0.25 mm I.D., 0.25 lm thickness; J & W Scientific, Palo-Alto, CA, USA). Instrumental conditions were modified from earlier studies (Vidal et al., 2003; Zachariadis and Rosenberg, 2009). The oven temperature was programmed to 70 °C for 1 min, increased at 15 °C min1 to 120 °C, then increased at 3 °C min1 to 150 °C, then increased at 12 °C min1 to 265 °C, then increased at 10 °C min1 to 310 °C, and held for 5 min. 2.4. QA/QC The experimental method applied in this study was based on a previously reported from the method test study (Gonzalez-Toledo et al., 2002; Vidal et al., 2003; Zachariadis and Rosenberg, 2009; Rodríguez et al., 2011). We performed the method test that 3 of same sediment samples were spiked with known concentrations of target analytes and went through the modified experimental method to confirm the accuracy and precision. The validation of method test was satisfied with below 15% for precision and 85–110% for recovery and the detailed results were shown in supporting information. Procedural blanks were included in each batch of 11–15 samples in order to check for contamination occurring during the process of experiment. The method detection limit (MDL, signal-to-noise ratio = 3) of target analytes were calculated in sample and ranged from 0.02 to 4.08 ng/g-dry weight. Multi-level calibration curves were used to quantify and satisfied R2 values ranging from 0.95 to 0.99. As internal standard, TPT-d15 and atrazine-d5 were used for OTs and tin-free compounds, respectively. Recoveries were 65.3 ± 26.23% for TPT-d15 and 96.7 ± 12.5% for atrazine-d5.
Please cite this article in press as: Lee, M.-R.N., et al. Assessment of organotin and tin-free antifouling paints contamination in the Korean coastal area. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/j.marpolbul.2015.07.038
Mi-Ri-Nae Lee et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx
Statistical analysis were performed by using SPSS Statics 21 (IBM, USA). The concentrations below MDL were replaced with 1/2 MDL to prevent distortion of the null data, and the data were then normalized to the total antifoulant concentration of each sampling site.
3. Results and discussion 3.1. Organotin and tin-free AFPs in sediments from the Korean coastal area 3.1.1. Concentration of organotin and tin-free AFPs The concentrations of 12 OTs and 12 tin-free AFPs in sediment from 15 sampling points along the Korean coastline, and 13 and 11 sampling points from the harbor areas of Busan and Ulsan bays, respectively, are shown in Fig. 1. The figure adapted the concentration of TBT scale was shown in supporting information. In the Korean coastal area, the concentration of OTs ranged from 21 to 332 ng/g-dry weight (mean: 114 ng/g-dry weight) and the concentration of tin-free AFPs ranged from 195 to 738 ng/g-dry weight (mean: 443 ng/g-dry weight). The concentration of OTs and tin-free AFPs on the east and west coast differed, with higher concentrations of OTs and lower concentrations of tin-free AFPs in the east than the west. This is discussed in more detail in Section 3.1.2. In Ulsan Bay, the concentration of OTs ranged from 23 to 1430 ng/g-dry weight (mean: 276 ng/g-dry weight), and the concentration of tin-free AFPs ranged from 132 to 790 ng/g-dry weight (mean: 505 ng/g-dry weight). In Busan Bay, the concentration of OTs ranged from 52 to 1330 ng/g-dry weight (mean: 360 ng/g-dry weight), and the concentration of tin-free AFPs ranged from 371 to 2664 ng/g-dry weight (mean; 898 ng/g-dry weight). In this study, OTs were detected in samples with a frequency of 20–100% and most tin-free AFPs were detected in over 70% of sediment samples collected from all sampling points, but dichlofluanid and ziram were not detected. In contrast, DMSA, a degradation product of dichlofluanid, was detected in all sediment samples, with the exception of one site (N2) in the Korean coastal area. Previous studies have also reported a similar tendency for dichlofluanid concentrations to be below the detection limit, while DMSA is frequently detected in samples from the marine environment (Hamwijk et al., 2005; Schouten et al., 2005). Dichlofluanid has a fast degradation rate, with a 53-h photodegradation half-life in seawater (Sakkas et al., 2001) and an anaerobic half-life of <0.5 day when released from paint particles into marine sediment (Thomas et al., 2003). Therefore, it is possible that dichlofluanid was not detected in the sediment samples due to its rapid degradation. Likewise, ziram is soluble in water with a log Koc ranging from 0.8 to 1.3 and a solubility ranging from 1.6 to 18.3 mg/L, but is not persistent because of its of rapid hydrolysis (degradation half time of 18 days at pH 8) (Woodrow et al., 1995; Ordelman et al., 1993; Tomlin, 1997). The absence of ziram in sediment samples was therefore a consequence of its physical properties. The concentration of AFPs in sediment samples were compared with those reported in other studies (Table 1). Ziram and dichlofluanid were excluded because they were not detected in this study. The concentrations of methyltin, octyltin, zineb, and thiram in sediments were not available for comparison due to the reported levels being below the detection limit in most previous studies (Radke et al., 2013; Kurihara et al., 2007; Rajendran et al., 2001). As shown in Table 1, the concentration of TBT in Korean marine sediment was similar or lower than that in sediments from other countries, and the concentrations of diuron and Sea-Nine 211
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found in this study were usually higher or similar to those reported in other countries. In particular, Irgarol 1051 and chlorothalonil in Busan and Ulsan bays were detected at higher levels than in other countries, but the Irgarol 1051 concentration reported in Greece was more than threefold higher than the concentrations found in this study. The value of the environment risk limit (ERL) in sediment has only been established for two of the compounds studied here (Irgarol 1051 and chlorothalonil), and therefore we compared these ERLs with the results of this study. For Irgarol 1051, 27%, 73% and 100% of the sediment samples from the Korean coastal area, Ulsan and Busan bays exceeded the ERL of 1.4 ng/g (van Wezel and van Vlaardingen, 2004), respectively. For sediment samples collected from Ulsan and Busan bays, 55% and 69%, respectively, exceeded the chlorothalonil ERL of 50.6 ng/g (van Wezel and van Vlaardingen, 2004), while all of the sediment samples from the Korean coastal area were lower than the ERL. In most samples, the concentration of tin-free AFPs in Busan and Ulsan bays was higher than in other countries and was sufficient to pose a risk to the aquatic ecosystem. Therefore, there is a need for continuous monitoring of these materials in Busan and Ulsan bays.
3.1.2. Spatial distribution of organotin and tin-free AFPs The spatial distribution of OTs and tin-free AFPs are shown according to the sampling site, categorized by coastal area and bay, in Fig. 2. As mentioned in Section 3.1.1., the concentration profile of OTs and tin-free AFPs differed between the east and west coasts. The concentrations of OTs on the east coast were fourfold higher than those on the west coast (r = 3.186, p < 0.05). The concentrations of OTs ranged from 57 to 331 ng/g-dry weight (mean: 200 ng/g-dry weight) on the east coast and from 21 to 69 ng/g-dry weight (mean: 48 ng/g-dry weight) on the west coast. In contrast, the concentration of tin-free AFPs on the west coast were about twofold higher than those on the east coast (r = 3.690, p < 0.05). The concentration of tin-free AFP ranged from 370 to 738 ng/g-dry weight (mean: 553 ng/g-dry weight) on the west coast and from 195 to 413 ng/g-dry weight (mean: 318 ng/g-dry weight) on the east coast. In a previous study of the Korean marine environment similar results were observed, with the concentration of butyltin in seawater from the east coast found to be 3.7-fold higher than in samples from the west coast and the concentrations of some tin-free AFPs (chlorothalonil, dichlofluanid, and Irgarol 1051) in seawater from the west coast found to be 3.5-fold higher than in samples from the east coast (Lee et al., 2010). In another study of OTs in Korea a similar trend was identified, with the concentration of TBT and TPT in bivalves collected from the east coast found to be higher than in bivalves from the west coast (Shim et al., 2005). The higher levels of tin-free AFPs in the west can be explained by the geographical characteristics of Korea, with successive mountain ranges in the east and a well-developed plain along the west coast, resulting in the release of pesticides, including those used in tin-free AFPs, from agriculture activities in the west. The increased persistency of OTs in sediment under oxygen-deficient conditions has been reported due to the limit of aerobic degradation by benthic organism (Filipkowska et al., 2014), and the dissolved oxygen levels from the bottom water layer measuring by winkler method averaged 8.99 mg/L on the east coast and 10.93 mg/L on the west coast (NFRDI, 2011). We conducted a correlation analysis between the dissolved oxygen levels and the concentration of total OTs and obtained a significant negative correlation (r = 0.704, P < 0.01); therefore, the lower oxygen levels might explain the higher levels of OTs in the east. However, further studies should be performed to confirm this, particularly to determine desorption and adsorption in association
Please cite this article in press as: Lee, M.-R.N., et al. Assessment of organotin and tin-free antifouling paints contamination in the Korean coastal area. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/j.marpolbul.2015.07.038
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Mi-Ri-Nae Lee et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx
Fig. 1. Concentrations of total OTs and tin-free AFPs in sediments from the Korean coastal area (a), Busan Bay (b), and Ulsan Bay (c).
with physicochemical parameters (Langston and Pope, 1995; Kram et al., 1989) Compared to the coastal areas and Ulsan Bay, the samples taken from Busan Bay had higher levels of OTs and tin-free AFPs. An earlier study of these areas also reported the highest levels of tin-free AFPs (chlorothalonil and dichlofluanid) in seawater samples from Busan Bay (Lee et al., 2010). The largest container port in Korea is located in Busan Bay, handling over ten million twenty-foot equivalent units (TEUs) per year and accounting for 73% of the container cargo supply in Korea (BPA, 2013). Therefore, cargo container shipping activity in Busan Bay influenced the contamination of the local sediment by OTs and tin-free AFPs. The highest concentration of OTs and tin-free AFPs in Busan Bay were found near the shipyard in sampling site B4 (total
tin = 1330 ng/g-dry weight, total tin-free AFPs = 2664 ng/g-dry weight), which seemed to be caused by the direct input of AFPs. 3.2. The time trend of TBT concentrations in sediment from Korea TBT in the marine environment was extensively monitored before its regulation in Korea, whereas past measurements of other OTs are limited. Therefore, we compared the concentrations of TBT in sediments from the Korean coastal area, and Busan and Ulsan bays with previous studies (Fig. 3). When compared with the average TBT concentration reported by Choi et al. (2009a,b, 2010), the 2002 year TBT concentration in the Korean coastal area was found to be quite high (Fig. 3a). However, overall the average TBT concentration in sediment from the Korean coastal area, and Ulsan and
Please cite this article in press as: Lee, M.-R.N., et al. Assessment of organotin and tin-free antifouling paints contamination in the Korean coastal area. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/j.marpolbul.2015.07.038
Mi-Ri-Nae Lee et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx Table 1 Comparision of TBT and tin-free AFPs concentration in marine sediment between Korean coastal area and foreign contries. Compound
Concentration (ng/g)
Country
Reference
Diuron
15–46 6.9–30 15–39 0.06–18
Korea coastal Busan bay Ulsan bay Japan (bay)
<0.3–4.2
USA (marinas)
0.11–3.0 60–66
Vietnam (coastal area) UK (harbor)
This study This study This study Harino et al. (2007) Sapozhnikova et al. (2013) Harino et al. (2006a) Gatidou et al. (2007)
30–281 61–269 ND-263 <0.04–150
Korea coastal Busan bay Ulsan bay Japan (bay)
0.09–1.3
Vietnam (coastal area)
ND-3.4 1.8–73 ND-39 <0.05–21
Korea coastal Busan bay Ulsan bay Japan (bay)
<0.3–8.9
USA (marinas)
3–690
Greece (marinas&port)
1.2–99 22–1065 1.3–422 <0.12–8.9
Korea coastal Busan bay Ulsan bay USA (Salton Sea)
<4.1–47
UK (estuary)
ND-56
Greece (marinas&port)
3.1–27 3.0–40 2.0–41 2.4–28
0.9–11
Korea coastal Busan bay Ulsan bay Taiwan (harbor&river estuary) Japan (bay)
8.3–51
Vietnam (harbor)
Sea-Nine 211
Irgarol 1051
Chlorothalonil
TBT
⁄
ND: not detected
This study This study This study Harino et al. (2007) Harino et al. (2006a) This study This study This study Harino et al. (2007) Sapozhnikova et al. (2013) Albanis et al. (2002) This study This study This study Sapozhnikova et al. (2004) Voulvoulis et al. (2000) Albanis et al. (2002) This study This study This study Shue et al. (2014)
Eguchi et al. (2010) Nhan et al. (2005)
5
Busan bays, clearly showed a decreasing trend, likely because of the prohibition of the use of TBT since 2003. However, TBT persists in the marine environment and was detected in all of the sediment samples in this study. The TBT concentrations in this study were higher than the 1–2 ng/g environmental quality target value and the 0.7 ng/g maximum permissible concentration (MPC), established in Dutch guidelines for TBT in sediments, at all sampling points (Ceulemans et al., 1998; Stronkhorst and van Hattum, 2003). On the other hand, the TBT concentrations in this study were lower than the high trigger value of 70 ng/g established in Australian sediment quality guidelines. Despite this, the TBT concentrations were not negligible and could still have a deleterious influence on marine ecological systems. Assuming a half-life of 2.82 years for TBT in sediments, which was calculated as a median value from the range of 162 days to 5.2 years reported previously (Dowson et al., 1993; Sarradin et al., 1995; Stang and Seligman, 1986), it would take a maximum of 17 years to satisfy the MPC. Therefore, this study recommends consistent TBT monitoring in sediments from the Korean coastal area to 2027, to confirm that the MPC is met. 3.3. Distribution of organotin and tin-free AFPs in sediment The distribution of target AFPs in sediment samples is presented in Fig. 4, with the sampling sites categorized by coastal area and bay. The outliers (B4 and U8) with the highest concentration of OTs and tin-free AFPs at Busan and Ulsan Bay in Fig. 2 were excluded. The distribution of mono, di, and tri analogue of each tin compounds were investigated to estimate any recent emissions into the study area. In case of butyltin and phenyltin compounds, their mono- to tri- analogue distribution was almost similar in sampling area. Otherwise, the patterns of substituted compounds of methyltin and octyl tin were different in each sampling site. The detailed of distribution patterns for OTs were shown in supporting information. As seen in Fig. 4a, the overall contribution of tin-free AFPs exceeded that of OTs, which was related to the prohibition of the use of OTs, whereas tin-free AFPs were not regulated in Korea at the time of the study. In the western coastal area, as mentioned in Section 3.1.2, concentrations of tin-free AFPs were much higher than in the eastern coastal area (Fig. 4a), with the contribution of zineb found to be about 11-fold higher than in other areas. However, the overall composition of each compound within the OT and tin-free AFP
Fig. 2. Box plots showing the total concentration of OTs (left) and tin-free AFPs (right) at specific sites (;: statistically significant difference (p < 0.05)).
Please cite this article in press as: Lee, M.-R.N., et al. Assessment of organotin and tin-free antifouling paints contamination in the Korean coastal area. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/j.marpolbul.2015.07.038
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Fig. 3. The trend in TBT concentrations in sediment from the Korean coastal area (a), Busan Bay (b), and Ulsan Bay (c) (black bar: this study, gray bar: Choi et al., (2009a,b, 2010)).
Fig. 4. Distribution of total AFPs (a), OTs (b), and tin-free AFPs (c) in sediment from the west (W) and east (E) coasts of Korea, Busan Bay (B), and Ulsan Bay (U) (OTs: total distribution from mono to tri, diurons: diuron + degradation products (DCPMU, DCPU, and CPDU)).
groups were similar, as shown in Fig. 4b and c, which indicates a similar composition of each of the four OTs and that the dominant tin-free AFPs were diurons (W: 42%, E: 49%) and Sea-Nine 211 (W: 33%, E: 21%). In particular, diuron have been mainly used as the active agents in AFPs, but there is still the possibility of its application as herbicides in Korea (Moncada, 2004). In Ulsan and Busan bays, the total distribution of AFPs consisted of approximately 25% OTs and 75% tin-free AFPs. The levels of each of the four OTs were similar in Ulsan Bay, whereas octyltin accounted for over 50% of the total in Busan bay (Fig. 4b). Among tin-free AFPs, the average concentration of diurons and Sea-Nine 211 were similar in the coastal areas. In Ulsan and Busan bays, chlorothalonil (U: 13%, B: 17%) and DMSA (U: 12%, B: 16%), which are degradation products of dichlofluanid, were more widely distributed than in the coastal area. Chlorothalonil and dichlofluanid
might be components of the antifoulants used in the large harbor and shipyard areas of the bays monitored in this study. To determine the detailed spatial distribution, we conducted principal component analysis (PCA) using the normalized concentration data for a total of 39 sediment samples (Fig. 5), excluding ziram and dichlofluanid that were not detected in any of sediment samples. Two principal components were extracted as PC 1 (41.6%) and PC 2 (23.1%). As seen in Fig. 5a, we could identify two distinguishable groups of target compounds in the loading plot, and the samples were also divided into two groups with the sampling sites in the score plot (Fig. 5b). We confirmed a different pattern between groups A and B in Fig. 5c. Group A (n = 16) was composed of 63% samples from the bays (nine samples from Busan Bay and six from Ulsan Bay), with a relatively high concentration; i.e., within the upper 15th percentile.
Please cite this article in press as: Lee, M.-R.N., et al. Assessment of organotin and tin-free antifouling paints contamination in the Korean coastal area. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/j.marpolbul.2015.07.038
Mi-Ri-Nae Lee et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx
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Fig. 5. PCA loading plot (a) and score plot (b) of the AFPs distribution according to the sampling sites and the distribution of two groups identified by PCA (c).
The distribution of AFPs in group A was similar to those in the bays, with chlorothalonil, DMSA, and octyltin being the dominant compounds (Fig. 5c). As seen in Fig. 5c, although Irgarol 1051 comprised only a very small proportion (B, U: 1%), group A was clearly affected by Irgarol 1051 (Fig. 5a), because of the higher mean concentration of Irgarol 1051 in Busan and Ulsan bays than in the Korean coastal area. A previous study also reported similar results, with a high concentration of chlorothalonil and dichlofluanid in seawater from Busan bay, and the highest concentration of chlorothalonil recorded in Ulsan bay seawater (Lee et al., 2010). This suggests that large amounts of chlorothalonil and dichlofluanid have been used in Busan and Ulsan bays and subsequently released to the marine environment. Octyltin is generally used as a PVC additive (food packing, PVC tubes, etc.) (Bancon-Montigny et al., 2004) and therefore could be leached from PVC products and released into the marine environment (Hoch, 2001; Chahinian et al., 2013; Shim et al., 1999). Group B (n = 23) comprised all of the coastal samples and 37% of the bay samples. The distribution of group B was similar to that of the coastal area (Fig. 5c), with diurons and Sea-Nine 211 found to be the dominant target compounds. It has been reported that in Korea, diuron and Sea-Nine 211 have been mainly used as the active agents in AFPs (KOSHIPA, 2008). In contrast, the west coast samples were grouped together (Fig. 5b), and were clearly affected by the contribution of zineb (Fig. 5a). As mentioned in Section 3.1.2, the main geographical feature of the west coast is a
plain, which resulted in the presence of higher concentrations of agriculture-related tin-free AFPs compared to the east coast (e. g; diuron and degradation products of diuron, zineb, thiram). The west coast samples had a relatively high zineb composition (Fig. 4a). This suggests that a large amount of zineb has been used as a fungicide in agricultural activity on the west coast. There has been limited monitoring of the marine environment for OTs and tin-free AFPs, and further studies are required to investigate the general distribution of those compounds and to determine their fate in the marine environment.
4. Conclusion To our knowledge, this study is the first to report the concentration and distribution of OTs and tin-free AFPs in marine sediments from Korea and provides baseline data for future studies. In this study, the sediments collected near shipyards in Busan and Ulsan bay were found to be heavily contaminated by tin-free AFPs, such as chlorothalonil and DMSA, and high concentrations of octyltin were also found. The ERL of Irgarol 1051 and chlorothalonil were exceeded in the heavily contaminated sites. In comparison with previous studies, the concentration of TBT was significantly decreased, but TBT was detected in all sediment samples collected from the Korean coastal areas, and Busan and Ulsan bays, despite its use being restricted. The TBT levels in some Korean coastal areas
Please cite this article in press as: Lee, M.-R.N., et al. Assessment of organotin and tin-free antifouling paints contamination in the Korean coastal area. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/j.marpolbul.2015.07.038
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and most sampling locations in Busan and Ulsan bays were higher than environmental quality target values and the maximum permissible concentration stated in Dutch guidelines for TBT. Therefore, continuous monitoring and management of AFPs in the marine environment is required in Korea. Acknowledgements This study was funded by a grant from the National Fisheries Research and Development Institute (NFRDI, RP-2015-ME-003) and the Korean Ministry of Environment (MOE) through ‘‘The Environment Health Action Program’’, Republic of Korea. Appendix A. Supplementary material Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.marpolbul.2015. 07.038. References Albanis, T., Lambropoulou, D., Sakkas, V., Konstantinou, I., 2002. Antifouling paint booster biocide contamination in Greek marine sediments. Chemosphere 48, 475–485. Balakrishnan, S., Takeda, K., Sakugawa, H., 2012. Occurrence of Diuron and Irgarol in seawater, sediments and planktons of Seto Inland Sea, Japan. Geochem. J. 46, 169–177. Bancon-Montigny, C., Lespes, G., Potin-Gautier, M., 2004. Organotin survey in the Adour–Garonne basin. Water Res. 38, 933–946. Biselli, S., Bester, K., Hühnerfuss, H., Fent, K., 2000. Concentrations of the antifouling compound Irgarol 1051 and of organotins in water and sediments of German North and Baltic Sea marinas. Mar. Pollut. Bull. 40, 233–243. Busan Port Authority (BPA), 2013.. Ceulemans, M., Slaets, S., Adams, F., 1998. Speciation of organotin in environmental sediment samples. Talanta 46, 395–405. Chahinian, N., Bancon-Montigny, C., Brunel, V., Aubert, G., Salles, C., Marchand, P., Rodier, C., Seidel, J., Gayrard, E., Hernandez, F., 2013. Temporal and spatial variability of organotins in an intermittent Mediterranean river. J. Environ. Manage. 128, 173–181. Choi, M., Choi, H., Moon, H., Kim, G., 2009a. Spatial and temporal distribution of tributyltin (TBT) in seawater, sediments and bivalves from coastal areas of Korea during 2001–2005. Environ. Monit. Assess. 151, 301–310. Choi, M., Moon, H., Yu, J., Eom, J., Choi, H., 2009b. Butyltin contamination in industrialized bays associated with intensive marine activities in Korea. Arch. Environ. Contam. Toxicol. 57, 77–85. Choi, M., Moon, H., Yu, J., Eom, J., Choi, H., 2010. Temporal trend of butyltins in seawater, sediments, and mussels from Busan Harbor of Korea between 2002 and 2007: tracking the effectiveness of tributylin regulation. Arch. Environ. Contam. Toxicol. 58, 394–402. Choi, M., Moon, H., Yu, J., Cho, H., Choi, H., 2013. Temporal trends (2004–2009) of imposex in rock shells Thais clavigera collected along the Korean coast associated with tributyltin regulation in 2003 and 2008. Arch. Environ. Contam. Toxicol. 64, 448–455. Comber, S., Franklin, G., Gardner, M., Watts, C., Boxall, A., Howcroft, J., 2002. Partitioning of marine antifoulants in the marine environment. Sci. Total Environ. 286, 61–71. Cresswell, T., Richards, J.P., Glegg, G.A., Readman, J.W., 2006. The impact of legislation on the usage and environmental concentrations of Irgarol 1051 in UK coastal waters. Mar. Pollut. Bull. 52, 1169–1175. Dowson, P., Bubb, J., Lester, J., 1993. Depositional profiles and relationships between organotin compounds in freshwater and estuarine sediment cores. Environ. Monit. Assess. 28, 145–160. Eguchi, S., Harino, H., Yamamoto, Y., 2010. Assessment of antifouling biocides contaminations in Maizuru Bay, Japan. Arch. Environ. Contam. Toxicol. 58, 684– 693. Fernández-Alba, A., Hernando, M., Piedra, L., Chisti, Y., 2002. Toxicity evaluation of single and mixed antifouling biocides measured with acute toxicity bioassays. Anal. Chim. Acta 456, 303–312. Filipkowska, A., Kowalewska, G., Pavoni, B., 2014. Organotin compounds in surface sediments of the Southern Baltic coastal zone: a study on the main factors for their accumulation and degradation. Environ. Sci. Pollut. Res. 21, 2077–2087. Gatidou, G., Thomaidis, N.S., Zhou, J.L., 2007. Fate of Irgarol 1051, diuron and their main metabolites in two UK marine systems after restrictions in antifouling paints. Environ. Int. 33, 70–77. Geigy, C., 1995. Irgarol 1051 in antifouling paints. Technical Information Bulletin. Gonzalez-Toledo, E., Ortuno, A., Compano, R., Granados, M., Prat, M.D., 2002. Solidphase extraction-liquid chromatography-fluorimetry for organotin speciation in natural waters. Chromatographia 55, 19–24.
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Determination of butyl-, phenyl-, octyl-and tributylmonomethyltin compounds in a marine environment (Bay of Bengal, India) using gas chromatography-inductively coupled plasma mass spectrometry. J. Environ. Monit. 3, 627–634. Rodríguez, Á.S., Ferrera, Z.S., Rodríguez, J.J.S., 2011. A preliminary assessment of levels of antifouling booster biocides in harbours and marinas of the island of Gran Canaria, using SPE-HPLC. Environ. Chem. Lett. 9, 203–208. Sakkas, V.A., Konstantinou, I.K., Albanis, T.A., 2001. Photodegradation study of the antifouling booster biocide dichlofluanid in aqueous media by gas chromatographic techniques. J. Chromatogr. A 930, 135–144. Sapozhnikova, Y., Bawardi, O., Schlenk, D., 2004. Pesticides and PCBs in sediments and fish from the Salton Sea, California, USA. Chemosphere 55, 797–809.
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Assessment of organotin and tin-free antifouling paints contamination in the Korean coastal area Mi-Ri-Nae Lee a, Un-Jung Kim a,b, In-Seok Lee c, Minkyu Choi c, Jeong-Eun Oh a,⇑ a
Department of Civil and Environmental Engineering, Pusan National University, San 30, Jangjeon-dong, Geumjeong-gu, Busan 609-735, Republic of Korea Center for Environment, Health and Welfare Research, Korea Institute Science and Technology (KIST), 39-1, Hawolgok-dong, Seongbuk-gu, Seoul 136-791, Republic of Korea c Marine Environment Research Team, National Fisheries Research and Development Institute (NFRDI), 408-1, Sirang-ri, Gijang-eup, Gijang-gun, Busan 619-705, Republic of Korea b
a r t i c l e
i n f o
Article history: Received 12 January 2015 Revised 13 July 2015 Accepted 18 July 2015 Available online xxxx Keywords: Antifouling paints Organotin compounds Tin-free compounds Marine sediment
a b s t r a c t Twelve organotins (methyl-, octyl-, butyl-, and phenyl-tin), and eight tin-free antifouling paints and their degradation products were measured in marine sediments from the Korean coastal area, and Busan and Ulsan bays, the largest harbor area in Korea. The total concentration of tin-free antifouling paints was two- to threefold higher than the total concentration of organotins. Principal component analysis was used to identify sites with relatively high levels of contamination in the inner bay area of Busan and Ulsan bays, which were separated from the coastal area. In Busan and Ulsan bays, chlorothalonil and DMSA were more dominant than in the coastal area. However, Sea-Nine 211 and total diurons, including their degradation products, were generally dominant in the Korean coastal area. The concentrations of tin and tin-free compounds were significantly different between the east and west coasts. Ó 2015 Published by Elsevier Ltd.
1. Introduction Tributyltin (TBT) was the most widely used material in the antifouling paints (AFPs) applied to marine vessels over several decades, but since 2003 its use has been restricted by the International Maritime Organization (IMO) due to its negative effect on non-target organisms (i.e., the occurrence of imposex (imposition of male organs on females) Spooner et al., 1991; IMO, 2002). Therefore, approximately 18 tin-free AFPs are currently used as TBT alternatives worldwide (Yonehara, 2000; Thomas et al., 2001), and in Korea 15,000 tons of tin-free AFPs were used in 2007 (The Korea Offshore and Shipbuilding Association (KOSHIPA), 2008). However, it has been suggested that TBT alternatives are also toxic and among the available tin-free AFPs, the application of Irgarol 1051 and diuron to marine vessels has been restricted in some European countries due to their inhibition of photosystem-II and their toxicity to aquatic organisms at low levels (Geigy, 1995; Hall et al., 1999; Gatidou et al., 2007; Sapozhnikova et al., 2013). Chlorothalonil, Sea-Nine 211, and DMSA, a degradation product of dichlofluanid, have also been reported to be more harmful to some microalga, daphnia, and fish cells than Irgarol 1051 and diuron (Fernández-Alba et al., 2002; Okamura et al., 2002). ⇑ Corresponding author. E-mail address: [email protected] (J.-E. Oh).
Many studies have been performed to investigate the fate and effect of TBT and its alternatives in the marine environment (Filipkowska et al., 2014; Sarradin et al., 1995; Harino et al., 2006a,b; Gatidou et al., 2007; Thomas et al.,2002, 2003; Comber et al., 2002). However, most previous studies of TBT alternatives have focused on Irgarol 1051 and diuron in the marine environment (Sapozhnikova et al., 2013; Cresswell et al., 2006; Balakrishnan et al., 2012; Harino et al., 2009). The highest levels of these two chemicals were found in summer due to high levels of yachting activity and inside marinas due to the low water exchange capacity (Lamoree et al., 2002; Biselli et al., 2000; Gatidou et al., 2007; Sapozhnikova et al., 2008; Albanis et al., 2002). In Korea, several studies of OTs and tin-free AFPs have been conducted, with the highest levels of TBT found in the vicinity of a shipyard in a large port (Choi et al., 2013; Kim et al., 2011). It should be noted that Korea’s shipbuilding industry is renowned the first in the global market and recorded 4000 tons for used TBT amounts in the year of 2000 (MOMAF, 2003). After the regulation of TBT in 2000, the amount of tin-free AFPs used increased by about sixfold in 2001 compared to 1998. A recent study of Irgarol 1051 and diuron in Korean seawater indicated a possibility of reduction in root growth rate among macrophyte species (Kim et al., 2014; Lambert et al., 2006) and an approximate fivefold increase of the concentration of tin-free AFPs from 2006 to 2009, while a twofold decrease in the butyltin concentration in coastal
http://dx.doi.org/10.1016/j.marpolbul.2015.07.038 0025-326X/Ó 2015 Published by Elsevier Ltd.
Please cite this article in press as: Lee, M.-R.N., et al. Assessment of organotin and tin-free antifouling paints contamination in the Korean coastal area. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/j.marpolbul.2015.07.038
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areas was observed in the same period (Lee et al., 2011). Contamination by tin-free AFPs in the Korean marine environment is worsening, but only three domestic studies of tin-free AFPs in seawater have been conducted (Lee et al., 2010, 2011; Kim et al., 2014). In addition, there have been no studies of tin-free AFPs in sediment from the Korean coastal area. Considering the likely settling of antifouling paint particles generated during ship maintenance (Thomas et al., 2003) and the potential detrimental influence of various AFPs on marine organisms through desorption from bottom sediment (Harris et al., 1996), the monitoring of AFPs in sediment is essential to assess their effect on the marine environment. Therefore, the aim of this study was to secure baseline data by investigating the concentration and distribution of 12 OTs (mono, di and tri-substituted analogs of methyl-, octyl-, phenyl-, and butyl-tin), 8 tin-free AFPs (Irgarol 1051, Sea-Nine 211, thiram, zineb, ziram, chlorothalonil, dichlofluanid, and diuron), and the degradation products of diuron (DCPMU, DCPU, and CPDU) and dichlofluanid (DMSA) in marine sediment from Korean coastal areas. The concentrations were then compared with those in the industrialized large ports of Ulsan and Busan. This is the first study to report the concentrations and distribution of various OTs and tin-free AFPs simultaneously in Korean marine sediment. 2. Materials and methods 2.1. Materials Pesticide-grade hexane and methanol (J.T. Baker Co., Phillipsburg, NY, USA), and sulfuric and hydrochloric acid (Matsunoen chemicals Ltd., Osaka, Japan) were obtained. Sodium tetraethylboratesolution and diethyldithiocarbamate were purchased (Sigma–Aldrich Co.). Atrazine-d5 (Sigma–Aldrich Co., St Louis, MO, USA) and triphenyltin-d15 chloride (TPT-d15) (Resolution Systems Inc., Buffalo, NY, USA) were used as internal standards. The target analytes, N,N-dimethyl-N0 -phenylsulfamide (DMSA), and 1-(3,4-dichlorophenyl)-3-methylurea (DCPMU) were purchased (Dr. Ehrenstorfer, Augsburg, Germany). Methyltin trichloride (MMT), dimethyltin dichloride (DMT), trimethyltin chloride (TMT), zincbis-dimethyldithiocarbamate (Ziram), and 4,5-dichloro-2-octyl-4-isothiazolone-3-one (Sea-Nine 211), N-dichlorofluoromethylthio-N0 , N0 -dimethyl-N-phenylsulfa mide (dichlofluanid), 2,4,5,6-tetrachloro isophthalonitrile (chlorothalonil), zinc ethylene-1,2-bis-dithiocarbamate (zineb), bis-dime thylthiocarbamoyl-disulfide (thiram), 2-methylthio-4-t-butylami no-6-cychlopropylamino-s-triazine (Irgarol 1051), 1-(3,4-dichloro phenyl)-3,3-dimethylurea (diuron) and the degradation products of diuron, 3-(3-chlorophenyl)-1,1-dimethylurea,1-(3,4-dichloro phenyl)urea (DCPU), and 3-(3-chlorophenyl)-1,1-dimethylurea (CPDU) were purchased (Sigma–Aldrich Co.). Mono butyltin trichloride (MBT), dibutyltin dichloride (DBT), tributyltin chloride (TBT), monophenyltin trichloride (MPT), diphenyltin dichloride (DPT), triphenyltin chloride (TPT), mono-noctyltintrichloride (MOT), di-n-octyltin dichloride (DOT), and tri-n-octyltin chloride (TOT) was purchased (Resolution Systems, Inc.). Phenanthrene-d10 (AccuStandard, Inc., New Haven, CT, USA) was used as recovery standard. 2.2. Sample collection and study area Marine sediment samples were collected using a box-core sampler from Busan Bay, Ulsan Bay, and national persistent organic pollutants (POPs) monitoring site, during June 2010, April 2011,
and February 2010, respectively. The sediment collection method followed Choi et al. (2009a). Korea is located in northern East Asia and is surrounded by coast on three sides, with a number of large and small ports along the coastline. A total of 15 sediment samples were collected from national POPs monitoring sites in the Korean coastal area. Busan and Ulsan bays are both highly industrialized and urbanized, as well as having large harbor and shipyard facilities, and hence were specifically targeted in this study. A total of 13 and 11 sediment samples were collected from Busan and Ulsan bays, respectively. For details of the sampling sites refer to Choi et al. (2009b). 2.3. Pretreatment and instrumental analysis The pretreatment method was modified from previous studies by Gonzalez-Toledo et al., 2002; Vidal et al., 2003; Zachariadis and Rosenberg, 2009; Rodríguez et al., 2011. Marine sediment samples (10 g) were extracted by mechanical shaking (15 °C, 150 rpm, 1 h), following by sonication (15 min) with 60 mL hexane. Atrazine-d5 and TPT-d15 were spiked as internal standards before the extraction. For derivatization, a minimal amount of sodium tetraethylborate solution (0.5%) and diethyldithiocarbamate (DDTC, 0.1 g equivalent) were mixed. The supernatant was transferred to a round bottom flask and 45 mL 1 N Sulfuric acid was added. Acidic sediment extractions were performed by solid-phase extraction (Supelco, Bellefonte, PA, USA) with OASIS HLB (6 cc, 200 mg), (Waters, Milfold, MA, USA). The cartridge was conditioned with 5 mL hexane, 5 mL MeOH, and 5 mL distilled water. After sample loading, the cartridge was dried for 1 h and eluted with 10 mL hexane. The eluent were passed over an Na2SO4 cartridge (Waters) to remove water and concentrated to 100 lL under nitrogen. Phenanthrene-d10 was spiked to a known concentration as a recovery standard prior to analysis by gas chromatography–mass spectrometry (GC–MS) (GC-HP6890: Hewlett–Packard, Palo Alto, CA, USA) (MS-5973: Agilent Technologies, Palo-Alto, CA, USA), with a DB-5MS column ((5% Phenyl)-methylpolysiloxane, 30 m length, 0.25 mm I.D., 0.25 lm thickness; J & W Scientific, Palo-Alto, CA, USA). Instrumental conditions were modified from earlier studies (Vidal et al., 2003; Zachariadis and Rosenberg, 2009). The oven temperature was programmed to 70 °C for 1 min, increased at 15 °C min1 to 120 °C, then increased at 3 °C min1 to 150 °C, then increased at 12 °C min1 to 265 °C, then increased at 10 °C min1 to 310 °C, and held for 5 min. 2.4. QA/QC The experimental method applied in this study was based on a previously reported from the method test study (Gonzalez-Toledo et al., 2002; Vidal et al., 2003; Zachariadis and Rosenberg, 2009; Rodríguez et al., 2011). We performed the method test that 3 of same sediment samples were spiked with known concentrations of target analytes and went through the modified experimental method to confirm the accuracy and precision. The validation of method test was satisfied with below 15% for precision and 85–110% for recovery and the detailed results were shown in supporting information. Procedural blanks were included in each batch of 11–15 samples in order to check for contamination occurring during the process of experiment. The method detection limit (MDL, signal-to-noise ratio = 3) of target analytes were calculated in sample and ranged from 0.02 to 4.08 ng/g-dry weight. Multi-level calibration curves were used to quantify and satisfied R2 values ranging from 0.95 to 0.99. As internal standard, TPT-d15 and atrazine-d5 were used for OTs and tin-free compounds, respectively. Recoveries were 65.3 ± 26.23% for TPT-d15 and 96.7 ± 12.5% for atrazine-d5.
Please cite this article in press as: Lee, M.-R.N., et al. Assessment of organotin and tin-free antifouling paints contamination in the Korean coastal area. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/j.marpolbul.2015.07.038
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Statistical analysis were performed by using SPSS Statics 21 (IBM, USA). The concentrations below MDL were replaced with 1/2 MDL to prevent distortion of the null data, and the data were then normalized to the total antifoulant concentration of each sampling site.
3. Results and discussion 3.1. Organotin and tin-free AFPs in sediments from the Korean coastal area 3.1.1. Concentration of organotin and tin-free AFPs The concentrations of 12 OTs and 12 tin-free AFPs in sediment from 15 sampling points along the Korean coastline, and 13 and 11 sampling points from the harbor areas of Busan and Ulsan bays, respectively, are shown in Fig. 1. The figure adapted the concentration of TBT scale was shown in supporting information. In the Korean coastal area, the concentration of OTs ranged from 21 to 332 ng/g-dry weight (mean: 114 ng/g-dry weight) and the concentration of tin-free AFPs ranged from 195 to 738 ng/g-dry weight (mean: 443 ng/g-dry weight). The concentration of OTs and tin-free AFPs on the east and west coast differed, with higher concentrations of OTs and lower concentrations of tin-free AFPs in the east than the west. This is discussed in more detail in Section 3.1.2. In Ulsan Bay, the concentration of OTs ranged from 23 to 1430 ng/g-dry weight (mean: 276 ng/g-dry weight), and the concentration of tin-free AFPs ranged from 132 to 790 ng/g-dry weight (mean: 505 ng/g-dry weight). In Busan Bay, the concentration of OTs ranged from 52 to 1330 ng/g-dry weight (mean: 360 ng/g-dry weight), and the concentration of tin-free AFPs ranged from 371 to 2664 ng/g-dry weight (mean; 898 ng/g-dry weight). In this study, OTs were detected in samples with a frequency of 20–100% and most tin-free AFPs were detected in over 70% of sediment samples collected from all sampling points, but dichlofluanid and ziram were not detected. In contrast, DMSA, a degradation product of dichlofluanid, was detected in all sediment samples, with the exception of one site (N2) in the Korean coastal area. Previous studies have also reported a similar tendency for dichlofluanid concentrations to be below the detection limit, while DMSA is frequently detected in samples from the marine environment (Hamwijk et al., 2005; Schouten et al., 2005). Dichlofluanid has a fast degradation rate, with a 53-h photodegradation half-life in seawater (Sakkas et al., 2001) and an anaerobic half-life of <0.5 day when released from paint particles into marine sediment (Thomas et al., 2003). Therefore, it is possible that dichlofluanid was not detected in the sediment samples due to its rapid degradation. Likewise, ziram is soluble in water with a log Koc ranging from 0.8 to 1.3 and a solubility ranging from 1.6 to 18.3 mg/L, but is not persistent because of its of rapid hydrolysis (degradation half time of 18 days at pH 8) (Woodrow et al., 1995; Ordelman et al., 1993; Tomlin, 1997). The absence of ziram in sediment samples was therefore a consequence of its physical properties. The concentration of AFPs in sediment samples were compared with those reported in other studies (Table 1). Ziram and dichlofluanid were excluded because they were not detected in this study. The concentrations of methyltin, octyltin, zineb, and thiram in sediments were not available for comparison due to the reported levels being below the detection limit in most previous studies (Radke et al., 2013; Kurihara et al., 2007; Rajendran et al., 2001). As shown in Table 1, the concentration of TBT in Korean marine sediment was similar or lower than that in sediments from other countries, and the concentrations of diuron and Sea-Nine 211
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found in this study were usually higher or similar to those reported in other countries. In particular, Irgarol 1051 and chlorothalonil in Busan and Ulsan bays were detected at higher levels than in other countries, but the Irgarol 1051 concentration reported in Greece was more than threefold higher than the concentrations found in this study. The value of the environment risk limit (ERL) in sediment has only been established for two of the compounds studied here (Irgarol 1051 and chlorothalonil), and therefore we compared these ERLs with the results of this study. For Irgarol 1051, 27%, 73% and 100% of the sediment samples from the Korean coastal area, Ulsan and Busan bays exceeded the ERL of 1.4 ng/g (van Wezel and van Vlaardingen, 2004), respectively. For sediment samples collected from Ulsan and Busan bays, 55% and 69%, respectively, exceeded the chlorothalonil ERL of 50.6 ng/g (van Wezel and van Vlaardingen, 2004), while all of the sediment samples from the Korean coastal area were lower than the ERL. In most samples, the concentration of tin-free AFPs in Busan and Ulsan bays was higher than in other countries and was sufficient to pose a risk to the aquatic ecosystem. Therefore, there is a need for continuous monitoring of these materials in Busan and Ulsan bays.
3.1.2. Spatial distribution of organotin and tin-free AFPs The spatial distribution of OTs and tin-free AFPs are shown according to the sampling site, categorized by coastal area and bay, in Fig. 2. As mentioned in Section 3.1.1., the concentration profile of OTs and tin-free AFPs differed between the east and west coasts. The concentrations of OTs on the east coast were fourfold higher than those on the west coast (r = 3.186, p < 0.05). The concentrations of OTs ranged from 57 to 331 ng/g-dry weight (mean: 200 ng/g-dry weight) on the east coast and from 21 to 69 ng/g-dry weight (mean: 48 ng/g-dry weight) on the west coast. In contrast, the concentration of tin-free AFPs on the west coast were about twofold higher than those on the east coast (r = 3.690, p < 0.05). The concentration of tin-free AFP ranged from 370 to 738 ng/g-dry weight (mean: 553 ng/g-dry weight) on the west coast and from 195 to 413 ng/g-dry weight (mean: 318 ng/g-dry weight) on the east coast. In a previous study of the Korean marine environment similar results were observed, with the concentration of butyltin in seawater from the east coast found to be 3.7-fold higher than in samples from the west coast and the concentrations of some tin-free AFPs (chlorothalonil, dichlofluanid, and Irgarol 1051) in seawater from the west coast found to be 3.5-fold higher than in samples from the east coast (Lee et al., 2010). In another study of OTs in Korea a similar trend was identified, with the concentration of TBT and TPT in bivalves collected from the east coast found to be higher than in bivalves from the west coast (Shim et al., 2005). The higher levels of tin-free AFPs in the west can be explained by the geographical characteristics of Korea, with successive mountain ranges in the east and a well-developed plain along the west coast, resulting in the release of pesticides, including those used in tin-free AFPs, from agriculture activities in the west. The increased persistency of OTs in sediment under oxygen-deficient conditions has been reported due to the limit of aerobic degradation by benthic organism (Filipkowska et al., 2014), and the dissolved oxygen levels from the bottom water layer measuring by winkler method averaged 8.99 mg/L on the east coast and 10.93 mg/L on the west coast (NFRDI, 2011). We conducted a correlation analysis between the dissolved oxygen levels and the concentration of total OTs and obtained a significant negative correlation (r = 0.704, P < 0.01); therefore, the lower oxygen levels might explain the higher levels of OTs in the east. However, further studies should be performed to confirm this, particularly to determine desorption and adsorption in association
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Fig. 1. Concentrations of total OTs and tin-free AFPs in sediments from the Korean coastal area (a), Busan Bay (b), and Ulsan Bay (c).
with physicochemical parameters (Langston and Pope, 1995; Kram et al., 1989) Compared to the coastal areas and Ulsan Bay, the samples taken from Busan Bay had higher levels of OTs and tin-free AFPs. An earlier study of these areas also reported the highest levels of tin-free AFPs (chlorothalonil and dichlofluanid) in seawater samples from Busan Bay (Lee et al., 2010). The largest container port in Korea is located in Busan Bay, handling over ten million twenty-foot equivalent units (TEUs) per year and accounting for 73% of the container cargo supply in Korea (BPA, 2013). Therefore, cargo container shipping activity in Busan Bay influenced the contamination of the local sediment by OTs and tin-free AFPs. The highest concentration of OTs and tin-free AFPs in Busan Bay were found near the shipyard in sampling site B4 (total
tin = 1330 ng/g-dry weight, total tin-free AFPs = 2664 ng/g-dry weight), which seemed to be caused by the direct input of AFPs. 3.2. The time trend of TBT concentrations in sediment from Korea TBT in the marine environment was extensively monitored before its regulation in Korea, whereas past measurements of other OTs are limited. Therefore, we compared the concentrations of TBT in sediments from the Korean coastal area, and Busan and Ulsan bays with previous studies (Fig. 3). When compared with the average TBT concentration reported by Choi et al. (2009a,b, 2010), the 2002 year TBT concentration in the Korean coastal area was found to be quite high (Fig. 3a). However, overall the average TBT concentration in sediment from the Korean coastal area, and Ulsan and
Please cite this article in press as: Lee, M.-R.N., et al. Assessment of organotin and tin-free antifouling paints contamination in the Korean coastal area. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/j.marpolbul.2015.07.038
Mi-Ri-Nae Lee et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx Table 1 Comparision of TBT and tin-free AFPs concentration in marine sediment between Korean coastal area and foreign contries. Compound
Concentration (ng/g)
Country
Reference
Diuron
15–46 6.9–30 15–39 0.06–18
Korea coastal Busan bay Ulsan bay Japan (bay)
<0.3–4.2
USA (marinas)
0.11–3.0 60–66
Vietnam (coastal area) UK (harbor)
This study This study This study Harino et al. (2007) Sapozhnikova et al. (2013) Harino et al. (2006a) Gatidou et al. (2007)
30–281 61–269 ND-263 <0.04–150
Korea coastal Busan bay Ulsan bay Japan (bay)
0.09–1.3
Vietnam (coastal area)
ND-3.4 1.8–73 ND-39 <0.05–21
Korea coastal Busan bay Ulsan bay Japan (bay)
<0.3–8.9
USA (marinas)
3–690
Greece (marinas&port)
1.2–99 22–1065 1.3–422 <0.12–8.9
Korea coastal Busan bay Ulsan bay USA (Salton Sea)
<4.1–47
UK (estuary)
ND-56
Greece (marinas&port)
3.1–27 3.0–40 2.0–41 2.4–28
0.9–11
Korea coastal Busan bay Ulsan bay Taiwan (harbor&river estuary) Japan (bay)
8.3–51
Vietnam (harbor)
Sea-Nine 211
Irgarol 1051
Chlorothalonil
TBT
⁄
ND: not detected
This study This study This study Harino et al. (2007) Harino et al. (2006a) This study This study This study Harino et al. (2007) Sapozhnikova et al. (2013) Albanis et al. (2002) This study This study This study Sapozhnikova et al. (2004) Voulvoulis et al. (2000) Albanis et al. (2002) This study This study This study Shue et al. (2014)
Eguchi et al. (2010) Nhan et al. (2005)
5
Busan bays, clearly showed a decreasing trend, likely because of the prohibition of the use of TBT since 2003. However, TBT persists in the marine environment and was detected in all of the sediment samples in this study. The TBT concentrations in this study were higher than the 1–2 ng/g environmental quality target value and the 0.7 ng/g maximum permissible concentration (MPC), established in Dutch guidelines for TBT in sediments, at all sampling points (Ceulemans et al., 1998; Stronkhorst and van Hattum, 2003). On the other hand, the TBT concentrations in this study were lower than the high trigger value of 70 ng/g established in Australian sediment quality guidelines. Despite this, the TBT concentrations were not negligible and could still have a deleterious influence on marine ecological systems. Assuming a half-life of 2.82 years for TBT in sediments, which was calculated as a median value from the range of 162 days to 5.2 years reported previously (Dowson et al., 1993; Sarradin et al., 1995; Stang and Seligman, 1986), it would take a maximum of 17 years to satisfy the MPC. Therefore, this study recommends consistent TBT monitoring in sediments from the Korean coastal area to 2027, to confirm that the MPC is met. 3.3. Distribution of organotin and tin-free AFPs in sediment The distribution of target AFPs in sediment samples is presented in Fig. 4, with the sampling sites categorized by coastal area and bay. The outliers (B4 and U8) with the highest concentration of OTs and tin-free AFPs at Busan and Ulsan Bay in Fig. 2 were excluded. The distribution of mono, di, and tri analogue of each tin compounds were investigated to estimate any recent emissions into the study area. In case of butyltin and phenyltin compounds, their mono- to tri- analogue distribution was almost similar in sampling area. Otherwise, the patterns of substituted compounds of methyltin and octyl tin were different in each sampling site. The detailed of distribution patterns for OTs were shown in supporting information. As seen in Fig. 4a, the overall contribution of tin-free AFPs exceeded that of OTs, which was related to the prohibition of the use of OTs, whereas tin-free AFPs were not regulated in Korea at the time of the study. In the western coastal area, as mentioned in Section 3.1.2, concentrations of tin-free AFPs were much higher than in the eastern coastal area (Fig. 4a), with the contribution of zineb found to be about 11-fold higher than in other areas. However, the overall composition of each compound within the OT and tin-free AFP
Fig. 2. Box plots showing the total concentration of OTs (left) and tin-free AFPs (right) at specific sites (;: statistically significant difference (p < 0.05)).
Please cite this article in press as: Lee, M.-R.N., et al. Assessment of organotin and tin-free antifouling paints contamination in the Korean coastal area. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/j.marpolbul.2015.07.038
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Fig. 3. The trend in TBT concentrations in sediment from the Korean coastal area (a), Busan Bay (b), and Ulsan Bay (c) (black bar: this study, gray bar: Choi et al., (2009a,b, 2010)).
Fig. 4. Distribution of total AFPs (a), OTs (b), and tin-free AFPs (c) in sediment from the west (W) and east (E) coasts of Korea, Busan Bay (B), and Ulsan Bay (U) (OTs: total distribution from mono to tri, diurons: diuron + degradation products (DCPMU, DCPU, and CPDU)).
groups were similar, as shown in Fig. 4b and c, which indicates a similar composition of each of the four OTs and that the dominant tin-free AFPs were diurons (W: 42%, E: 49%) and Sea-Nine 211 (W: 33%, E: 21%). In particular, diuron have been mainly used as the active agents in AFPs, but there is still the possibility of its application as herbicides in Korea (Moncada, 2004). In Ulsan and Busan bays, the total distribution of AFPs consisted of approximately 25% OTs and 75% tin-free AFPs. The levels of each of the four OTs were similar in Ulsan Bay, whereas octyltin accounted for over 50% of the total in Busan bay (Fig. 4b). Among tin-free AFPs, the average concentration of diurons and Sea-Nine 211 were similar in the coastal areas. In Ulsan and Busan bays, chlorothalonil (U: 13%, B: 17%) and DMSA (U: 12%, B: 16%), which are degradation products of dichlofluanid, were more widely distributed than in the coastal area. Chlorothalonil and dichlofluanid
might be components of the antifoulants used in the large harbor and shipyard areas of the bays monitored in this study. To determine the detailed spatial distribution, we conducted principal component analysis (PCA) using the normalized concentration data for a total of 39 sediment samples (Fig. 5), excluding ziram and dichlofluanid that were not detected in any of sediment samples. Two principal components were extracted as PC 1 (41.6%) and PC 2 (23.1%). As seen in Fig. 5a, we could identify two distinguishable groups of target compounds in the loading plot, and the samples were also divided into two groups with the sampling sites in the score plot (Fig. 5b). We confirmed a different pattern between groups A and B in Fig. 5c. Group A (n = 16) was composed of 63% samples from the bays (nine samples from Busan Bay and six from Ulsan Bay), with a relatively high concentration; i.e., within the upper 15th percentile.
Please cite this article in press as: Lee, M.-R.N., et al. Assessment of organotin and tin-free antifouling paints contamination in the Korean coastal area. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/j.marpolbul.2015.07.038
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Fig. 5. PCA loading plot (a) and score plot (b) of the AFPs distribution according to the sampling sites and the distribution of two groups identified by PCA (c).
The distribution of AFPs in group A was similar to those in the bays, with chlorothalonil, DMSA, and octyltin being the dominant compounds (Fig. 5c). As seen in Fig. 5c, although Irgarol 1051 comprised only a very small proportion (B, U: 1%), group A was clearly affected by Irgarol 1051 (Fig. 5a), because of the higher mean concentration of Irgarol 1051 in Busan and Ulsan bays than in the Korean coastal area. A previous study also reported similar results, with a high concentration of chlorothalonil and dichlofluanid in seawater from Busan bay, and the highest concentration of chlorothalonil recorded in Ulsan bay seawater (Lee et al., 2010). This suggests that large amounts of chlorothalonil and dichlofluanid have been used in Busan and Ulsan bays and subsequently released to the marine environment. Octyltin is generally used as a PVC additive (food packing, PVC tubes, etc.) (Bancon-Montigny et al., 2004) and therefore could be leached from PVC products and released into the marine environment (Hoch, 2001; Chahinian et al., 2013; Shim et al., 1999). Group B (n = 23) comprised all of the coastal samples and 37% of the bay samples. The distribution of group B was similar to that of the coastal area (Fig. 5c), with diurons and Sea-Nine 211 found to be the dominant target compounds. It has been reported that in Korea, diuron and Sea-Nine 211 have been mainly used as the active agents in AFPs (KOSHIPA, 2008). In contrast, the west coast samples were grouped together (Fig. 5b), and were clearly affected by the contribution of zineb (Fig. 5a). As mentioned in Section 3.1.2, the main geographical feature of the west coast is a
plain, which resulted in the presence of higher concentrations of agriculture-related tin-free AFPs compared to the east coast (e. g; diuron and degradation products of diuron, zineb, thiram). The west coast samples had a relatively high zineb composition (Fig. 4a). This suggests that a large amount of zineb has been used as a fungicide in agricultural activity on the west coast. There has been limited monitoring of the marine environment for OTs and tin-free AFPs, and further studies are required to investigate the general distribution of those compounds and to determine their fate in the marine environment.
4. Conclusion To our knowledge, this study is the first to report the concentration and distribution of OTs and tin-free AFPs in marine sediments from Korea and provides baseline data for future studies. In this study, the sediments collected near shipyards in Busan and Ulsan bay were found to be heavily contaminated by tin-free AFPs, such as chlorothalonil and DMSA, and high concentrations of octyltin were also found. The ERL of Irgarol 1051 and chlorothalonil were exceeded in the heavily contaminated sites. In comparison with previous studies, the concentration of TBT was significantly decreased, but TBT was detected in all sediment samples collected from the Korean coastal areas, and Busan and Ulsan bays, despite its use being restricted. The TBT levels in some Korean coastal areas
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and most sampling locations in Busan and Ulsan bays were higher than environmental quality target values and the maximum permissible concentration stated in Dutch guidelines for TBT. Therefore, continuous monitoring and management of AFPs in the marine environment is required in Korea. Acknowledgements This study was funded by a grant from the National Fisheries Research and Development Institute (NFRDI, RP-2015-ME-003) and the Korean Ministry of Environment (MOE) through ‘‘The Environment Health Action Program’’, Republic of Korea. Appendix A. Supplementary material Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.marpolbul.2015. 07.038. References Albanis, T., Lambropoulou, D., Sakkas, V., Konstantinou, I., 2002. Antifouling paint booster biocide contamination in Greek marine sediments. Chemosphere 48, 475–485. Balakrishnan, S., Takeda, K., Sakugawa, H., 2012. Occurrence of Diuron and Irgarol in seawater, sediments and planktons of Seto Inland Sea, Japan. Geochem. J. 46, 169–177. Bancon-Montigny, C., Lespes, G., Potin-Gautier, M., 2004. Organotin survey in the Adour–Garonne basin. Water Res. 38, 933–946. Biselli, S., Bester, K., Hühnerfuss, H., Fent, K., 2000. Concentrations of the antifouling compound Irgarol 1051 and of organotins in water and sediments of German North and Baltic Sea marinas. Mar. Pollut. Bull. 40, 233–243. Busan Port Authority (BPA), 2013.
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Please cite this article in press as: Lee, M.-R.N., et al. Assessment of organotin and tin-free antifouling paints contamination in the Korean coastal area. Mar. Pollut. Bull. (2015), http://dx.doi.org/10.1016/j.marpolbul.2015.07.038