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Antifouling paint booster biocides (Irgarol 1051 and diuron) in marinas and ports of Bushehr, Persian Gulf
MPB-07496; No of Pages 6 Marine Pollution Bulletin xxx (2015) xxx–xxx
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Baseline
Antifouling paint booster biocides (Irgarol 1051 and diuron) in marinas and ports of Bushehr, Persian Gulf Abolfazl Saleh a,⁎, Saeideh Molaei b, Neda Sheijooni Fumani a, Ehsan Abedi a a b
Iranian National Institute for Oceanography and Atmospheric Science, No. 3, Etemadzadeh St., Fatemi Ave., Tehran 1411813389, Iran Faculty of Chemistry, Kharazmi University, 43Mofateh Ave., Tehran 1571914911, Iran
a r t i c l e
i n f o
Article history: Received 1 December 2015 Received in revised form 11 February 2016 Accepted 15 February 2016 Available online xxxx Keywords: Antifouling paint booster biocides Irgarol 1051 Diuron 3,4-dichloroaniline Bushehr Persian Gulf
a b s t r a c t In the present study, antifouling paint booster biocides, Irgarol 1051 and diuron were measured in ports and marinas of Bushehr, Iran. Results showed that in seawater samples taken from ports and marinas, Irgarol was found at the range of less than LOD to 63.4 ng L−1 and diuron was found to be at the range of less than LOD to 29.1 ng L−1 (in Jalali marina). 3,4-dichloroaniline (3,4-DCA), as a degradation product of diuron, was also analyzed and its maximum concentration was 390 ng L−1. Results for analysis of Irgarol 1051 in sediments showed a maximum concentration of 35.4 ng g−1 dry weight in Bandargah marina. A comparison between the results of this study and those of other published works showed that Irgarol and diuron pollutions in ports and marinas of Bushehr located in the Persian Gulf were less than the average of reports from other parts of the world. © 2016 Elsevier Ltd. All rights reserved.
Organic booster biocides are used as additives in copper-based antifouling paints to prevent the settlement and growth of marine organisms on submerged structures (Konstantinou and Albanis, 2004). Biofouling produces some negative environmental and economical consequences, such as increases in fuel consumption and corrosion processes as well as the potential for the introduction of foreign species in new ecosystems (Lewis et al., 2003). Worldwide, around 18 compounds are currently used as antifouling paint booster biocides with differing degrees of regulation. These chemicals are alternatives to organotin-based antifoulants whose use has been completely banned in 2004 due to their high toxicity and their effects on aquatic organisms (Mackie and Lloyd, 2002). Irgarol 1051 (2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine) and diuron (3-(3,4-dichlorophenyl)-1,1-dimethyl urea) have been widely used among others because of their high effectiveness as a growth inhibitor of marine and freshwater algae (Readman, 1999). Diuron has been predominately used for weed control on land as a substituted urea herbicide since the 1950s. It is also widely applied for non-agricultural applications including vegetation control in industrial sites and rights of way along power lines, roads, railways, and buildings (Moncada, 2004). Irgarol and diuron (with aqueous solubility values of 7 and 36.4 mg L−1 and log Kow 3.95 and 2.85, respectively) exert their antifouling action by inhibiting photosynthesis and impairing electron transport within chloroplasts (Dahl and Blanck, 1996; Alyuruk and Cavas, 2013). Both compounds are much more toxic to phytoplankton ⁎ Corresponding author. E-mail address: [email protected] (A. Saleh).
than other aquatic species (Dahl and Blanck, 1996; Malato et al., 2002). Irgarol appears to be especially toxic to the freshwater diatom (5 day EC50 136 ng L−1) and the freshwater macrophytes (14 day EC50 0.017 ng L−1) (Lambert et al., 2006). The environmental risk limits for Irgarol in water (ERLwater) and sediment (ERLsediment) are 24 ng L−1 and 1.4 ng g−1, respectively (Wezel and Vlaardingen, 2004). The Dutch National Institute of Public Health and the Environment suggested a maximum permissible concentration for Irgarol and diuron of 29 and 430 ng L−1, respectively (Lamoree et al., 2002). Due to the Irgarol and diuron harmful effects on the marine ecosystem, some countries, such as the United Kingdom, Denmark and Sweden, have forbidden the use of Irgarol, whereas diuron has been also prohibited in UK and Netherlands (Thomas and Brooks, 2010). In an overview, elimination (volatilization, chemical hydrolysis, biodegradation, photo-degradation) and accumulation rates (sedimentation and uptake by biota) of chemicals are the two phenomena affecting observed levels. Irgarol and diuron are resistant to hydrolysis and they are stable during 17 days of sunlight irradiation (Arai et al., 2009). Moreover, bacterial biodegradation of Irgarol 1051 and diuron are of minor importance (their initial concentration of 0.1 mg L−1 scarcely changed after 60 days) (Arai et al., 2009). 2-methylthio-4-tert-butylamino-6amino-s-triazine (M1) and 3,4-dichloroaniline (3,4-DCA) are the main metabolites of Irgarol and diuron, respectively (Arai et al., 2009). Nevertheless, results of different studies indicate that generally Irgarol (with half-life ranging from 100 to 350 days) and diuron (with half-life ranging from 43 to 2180 days) are fairly stable compounds in seawater (Hall et al., 1999; Thomas et al., 2002; Moncada, 2004). On the other hand,
http://dx.doi.org/10.1016/j.marpolbul.2016.02.037 0025-326X/© 2016 Elsevier Ltd. All rights reserved.
Please cite this article as: Saleh, A., et al., Antifouling paint booster biocides (Irgarol 1051 and diuron) in marinas and ports of Bushehr, Persian Gulf, Marine Pollution Bulletin (2015), http://dx.doi.org/10.1016/j.marpolbul.2016.02.037
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A. Saleh et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx
sorption of these organic pollutants onto settling particulate matters is not only responsible for their concentration reducing in the water column, but also is the principal pathway of their accumulation in sediments. A modular estuarine mesocosm experiment revealed that after 35 days of Irgarol exposure, only 7% of parent compound remained unchanged in the water column and 75% accumulated in the mesocosm sediments (Sapozhnikova et al., 2009). Generally, in sediments, it has been demonstrated that degradation is slow even under aerobic conditions, resulted in booster biocides' elevated persistency in sediments. As a result, the sediments may serve as storage and release sources of pollutants (Thomas et al., 2003; Zhou, 2008). Studies conducted by Tolhurst et al. (2007) and Voulvoulis et al. (2002) showed that disturbance of sediments contaminated with Irgarol can cause desorption of Irgarol with the rate of 1.9–2.4% per 24 h. Environmental monitoring of Irgarol 1051 and diuron has been extensive worldwide, in order to assess the risks to the environment. Since Irgarol and diuron have also agricultural uses, as a result their presence in the aquatic and estuarine environments cannot be attributed solely to the use of antifouling paints. Various studies on detection and distribution of Iragrol and diuron have been conducted in different areas including Northern Europe (Netherlands, Germany, England and Sweden) (Lamoree et al., 2002; Biselli et al., 2000; Thomas et al., 2001; Haglund et al., 2001), Mediterranean Sea (Spain, France and Greece) (Hernando et al., 2001; Tolosa et al., 1996; Sakkas et al., 2002), America (Bermuda and USA) (Konstantinou and Albanis, 2004; Sapozhnikova et al., 2013), and Australia (Konstantinou and Albanis, 2004). Moreover, some studies have been performed in Asia such as South Korea (Kim et al., 2014), Japan (Balakrishnan et al., 2012), Singapore (Basheer et al., 2002) and Malaysia (Rashid Ali et al., 2013) but to date no monitoring survey of these new antifouling biocides has yet been reported in the Persian Gulf (Iran). This study therefore presents the baseline data for occurrence and distribution of Irgarol 1051, diuron and its metabolite (3,4-DCA) in ports and marinas of Bushehr (northwest of the Persian Gulf, Iran). Bushehr peninsula is located in a humid subtropical region. It lies near the head of the Persian Gulf at the northern part of a flat connected with the mainland by tidal marshes (Sheppard et al., 2010). The wide range of seasonal variation of seawater temperature and elevated salinity are important environmental stressors, which could enhance effects of pollution on sensitive marine ecosystems of this area (Schiedek et al., 2007). Bushehr (28.58 N and 50.50 E) is one of the most important ports in the Persian Gulf with a remarkable situation since it is an export market for the agricultural crops of Iranian southern provinces (e.g. Bushehr and Fars provinces) and is one of the largest regional fishing ports of Iran. Water and sediment samples were collected from 16 stations located in the marinas and ports of Bushehr peninsula, northwestern Persian Gulf in October of 2013 at the end of the peak of the shrimp fishing (Table 1). Various sampling sites such as Bushehr port internal canal, marinas and ports for small fishing boats' and dhows' mooring spaces, and shipyards were deliberately chosen as study areas because contamination from antifouling biocides was expected to be high. In locations in which it was possible, samples were collected from the areas dedicated to small boats (b 10 m) and dhows (10–30 m). However, not both vessel classes were present in every location. Three individual water samples were collected at each station. Water samples were taken from approximately 0.5 m below the surface using a Niskin bottle sampler (2 L) and transferred into the pre-cleaned 1 L amber glass bottles. The samples were then kept under 4 °C and brought to laboratory for analysis. Three replicate sediment samples were collected at each site, at 1 m distance from each other and analyzed individually. Surface sediment samples at a water depth between 0.6 and 12.3 m were collected using a VanVeen grab sampler and transferred into the pre-cleaned aluminum containers (500 g) and stored in a freezer at −25 °C until analysis. Measurements of salinity, conductivity, pH and dissolved oxygen (DO) were taken in situ using a Hach HQ40d multimeter with related probs.
Table 1 Sampling location information. Location
Latitude
Longitude
Depth (m)
Jalali marina Jalali marina Open seawater 1 (Persian Gulf) Open seawater 1 (Persian Gulf) Bandargah marina Bandargah marina Open seawater 2 (Persian Gulf) Open seawater 2 (Persian Gulf) Jofre marina Jofre marina Jabri marina Bushehr port internal canal Sadra Ship building factory Sadra Ship building factory Solhabad marina Bushehr port internal canal
28° 55.233′N 28° 55.172′N 28° 52.908′N 28° 52.698′N 28° 49.228′N 28° 49.382′N 28° 56.956′N 28° 56.831′N 28° 58.298′N 28° 58.372′N 28° 58.822′N 28° 59.777′N 28° 58.869′N 28° 58.549′N 28° 58.740′N 28° 58.873′N
50° 48.506′E 50° 48.442′E 50° 49.922′E 50° 49.690′E 50° 54.525′E 50° 54.484′E 50° 48.299′E 50° 47.781′E 50° 49.359′E 50° 49.363′E 50° 50.733′E 50° 49.978′E 50° 51.681′E 50° 51.452′E 50° 50.997′E 50° 50.879′E
3.7 3.1 4.7 6.0 0.6 2.0 5.6 6.2 0.7 1.6 1.6 12.3 4.4 4.7 2.3 5.1
Total organic matter (TOM) was measured for each sediment sample as described elsewhere (Gaspare et al., 2009). For grain size assessments, 10 mL of tetra sodium diphosphate decahydrate (3% w/v) was added into the 1 g of homogenized and freeze-dried sediment. After 20 min of stirring, the mixture was introduced into a laser scattering particle size distribution analyzer (HORIBA, LA-950, Japan & France). Irgarol 1051, diuron and 3,4-dichloroaniline were purchased from Sigma-Aldrich (St. Louis, MO, USA). Analysis of water samples was performed using microfunnelsupported liquid-phase microextraction method (MF-LPME) as previously explained by Saleh et al. (2014). Briefly, a volume of 300 mL of seawater sample was introduced into the glass vessel. A small magnetic rod was inserted into the vessel. The vessel was closed with the stopper through which passed the glass microfunnel. The upper part of the funnel was filled with a 400 μL of toluene by using a syringe. The sample compartment was stirred at 240 rpm with a magnetic stirrer. After the extraction, the extractant was withdrawn by using a syringe and its solvent evaporated under the gentle stream of nitrogen at room temperature. The residual re-dissolved in 50 μL methanol, diluted to 100 μL with deionized water and injected into the HPLC loop followed by analysis. Samples of sediment were freeze-dried by an Operon freeze-dryer (5503-Korean) for 72 h. Analysis of sediments was carried out using ultrasound-assisted extraction (UAE) followed by dispersive liquid– liquid microextraction (DLLME) according to the procedures of Lambropoulou et al. (2003) and Rezaee et al. (2006) with some modifications. Approximately 3 g of freeze-dried, homogenized and ground sediment was leached by ultrasound waves with 4 mL of acetone for 1 h, after which the sample was centrifuged for 10 min at 3000 rpm. The supernatant (approximately 2.5 mL) was transferred into a conical test tube followed by addition of 200 μL of DCM as an extraction solvent. Then, the mixture was rapidly injected into the 10 mL distilled water placed in a conical centrifuge tube to form a cloudy solution (for further cleanup and preconcentration). Using centrifugation at 3000 rpm for 10 min, DCM was settled at the conical bottom of the test tube and 1 μL of which was injected into the gas chromatography-mass spectrometry (GC–MS) for analysis. Chromatographic analysis in seawater samples was carried out on an Agilent 1100 HPLC system (California, USA) equipped with an Agilant G1314A variable wavelength detector (VWD). A C18 column (5 μm, 4.6 mm × 250 mm) from Agilent Eclipse Plus was applied to separate the analytes under isocratic elution condition. A mixture of acetonitrile and water (55:45, v/v) with a flow rate of 1 mL min−1 was used as the mobile phase. The detection was performed at wavelengths of 223 (for Irgarol 1051) and 244 nm (for diuron and 3,4-dichloroaniline). Quantitative analysis of Irgarol in sediment samples was conducted on a gas chromatograph Agilent (Wilmington, DE, USA) 6890 equipped
Please cite this article as: Saleh, A., et al., Antifouling paint booster biocides (Irgarol 1051 and diuron) in marinas and ports of Bushehr, Persian Gulf, Marine Pollution Bulletin (2015), http://dx.doi.org/10.1016/j.marpolbul.2016.02.037
A. Saleh et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx
with split/splitless injector operated at 270 °C in splitless mode and mass detector Agilent 5973. A 30 m HP-5MS fused silica capillary column (0.25 mm I.D., 0.25 μm film thickness) was used for separation. Helium (purity 99.999%) was used as carrier gas at constant flow rate of 1 mL min−1. For quantitative analysis, two selected mass fragments of 182 and 253 m/z were studied in selected ion monitoring (SIM) mode. In order to compensate for matrices effect, analyte-free seawater and sediment were used to obtain calibration curves (extraction calibration using authentic matrix and authentic analyte). Quantification in seawater within the range of 8–5000 ng L−1 for Irgarol 1051 and 3,4DCA, and 48–5000 ng L−1 for diuron was performed using constructed calibration curves with regression coefficients (R2) better than 0.995. The LODs in seawater, calculated at a signal-to-noise (S/N) ratio of 3, were 1.0, 1.4 and 4.8 ng L− 1 and LOQs, calculated at S/N = 10, were 3.2, 4.5 and 15.9 ng L−1 for Irgarol 1051, 3,4-DCA and diuron, respectively. The LOD and LOQ values for Irgarol 1051 in sediment were obtained 2.04 and 6.80 ng g− 1 dry weight, respectively. The relative standard deviations (RSDs) for antifouling biocides in seawater and sediment were below 12 and 9.9%, respectively. Statistical data analysis was performed with SPSS 17.0 for Windows. Shapiro–Wilk W test was used to check for normality. Spearman's rho correlations were used to explore relationships between analyte concentrations and water and sediment quality parameters. Antifouling biocide concentrations in seawater of Bushehr ports and marinas are shown in Table 2. The values of the concentration are reported as mean ± standard deviation of replicate measurements. Irgarol 1051 was detected in 31% of water samples with concentrations ranging from 10.9 ng L−1 to 63.4 ng L−1. The highest Irgarol 1051 concentration was detected in Jalali marina (dhows mooring space, 63.4 ± 16 ng L−1) followed by Jofreh marina (dhows mooring space, 17.2 ± 1.9 ng L−1, small boats mooring space 13.1 ± 2.3 ng L−1), Bandargah marina (dhows mooring space, 11.9 ± 1.5 ng L− 1) and Solhabad marina (dhows mooring space, 10.9 ± 0.4 ng L−1). Diuron was detected at only four stations (i.e. 25% of water samples) in the range of 13.6 ± 1.0 ng L−1 to 29.1 ± 2.5 ng L−1. The rest of stations (12) showed the concentrations below the detection limit of diuron. Jalali marina (dhows mooring space) showed the highest diuron concentration, whereas the second highest diuron concentration corresponded to Solhabad marina (dhows mooring space), with a value of 22.5 ± 0.6 ng L−1. The high presence of both biocides in dhows mooring spaces compared to small boats mooring spaces indicated that these compounds were extensively used in dhows paint formulations. Based on information from indigenous people of Bushehr, small fishing boats are painted once during their lifetime whereas, larger vessels such as dhows are dry ducked and repainted every 3 to 5 years. In addition, larger size and
3
Fig. 1. Average concentrations of Irgarol 1051 in water samples, ng L−1, error bars represent the maximum concentration observed.
contact surface of dhows with seawater could be the reason of the significant differences of levels in dhows and small boats. Moreover, number of factors contribute Irgarol and diuron contaminations in the various sites. Areas including Jalali and Jofreh Marinas with higher density of boats, residence of boats throughout the year, and lower water exchange rates demonstrated higher concentrations of paint booster biocides in contrast to the other areas with less boating activities and higher water exchange rate (Biselli et al., 2000; Konstantinou and Albanis, 2004). The maximum levels of Irgarol found in various Bushehr marinas were significantly lower than the other reported European regions such as Sweden (364 ng L−1), UK (621 ng L− 1), France (491 ng L−1) and Spain (670 ng L−1) and comparable with areas including Denmark (9 ng L− 1), Netherland (39 ng L− 1), and Greece (24 ng L− 1), as indicated in Fig. 1 (Readman, 2006). It should be
Table 2 Concentration of antifouling biocides found in seawater samples taken from Bushehr ports and marinas. Sampling area
St. no.
Station
3,4-DCA (ng L−1) ± SD
Diuron (ng L−1) ± SD
Irgarol 1051 (ng L−1) ± SD
Jalali marina
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
Small boats mooring space Dhows mooring space Nearshore Offshore Small boats mooring space Dhows mooring space Nearshore Offshore Small boats mooring space Dhows mooring space Small boats mooring space Anchorage 2 Ship building and repairing yard Repairing yard Dhows mooring space Middle of the canal
390 ± 10 289 ± 29 18.8 ± 2.2 10.2 ± 3.3 35.2 ± 2.0 74.7 ± 7.0 nd nd 95.2 ± 17 73.9 ± 5.3 23.7 ± 2.7 nd 15.8 ± 4.9 22.7 ± 3.5 47.2 ± 4.6 nd
≈13.6 ± 1.0 29.1 ± 2.5 nda nd nd nd nd nd nd 21.0 ± 1.7 nd nd nd nd 22.5 ± 0.6 nd
nd 63.4 ± 16 nd nd nd 11.9 ± 1.5 nd nd 13.1 ± 2.3 17.2 ± 1.9 nd nd nd nd 10.9 ± 0.4 nd
Open seawater 1 (Persian Gulf) Bandargah marina Open seawater 2 (Persian Gulf) Jofreh marina Jabri marina Bushehr port internal canal Sadra Ship building factory Solhabad marina Bushehr port internal canal a
nd: Not detected
Please cite this article as: Saleh, A., et al., Antifouling paint booster biocides (Irgarol 1051 and diuron) in marinas and ports of Bushehr, Persian Gulf, Marine Pollution Bulletin (2015), http://dx.doi.org/10.1016/j.marpolbul.2016.02.037
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A. Saleh et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx
Table 3 Comparison of antifouling biocide concentrations (ng L−1) found in water in this study with other reported studies. Irgarol 1051 (ng L−1)
Diuron (ng L−1)
Location, year
2–254 1–304 5–1816 2–305 b3.1–136 bLOQ-186 1.3–77 10–257 110–1620 b1.0–2021 0.2–14.1 b1.0–63.4
b2–68 b2–12 Not analyzed b1–78 b7–366 bLOQ-268 13–350 2–18 Not analyzed Not analyzed 13–1360 b4.8–29.1
USA, CA, 2008 Sapozhnikova et al. (2013) USA, CA, 2005 Sapozhnikova et al. (2007) USA, MD, 2004 Hall et al. (2005) UK, 2000 Thomas et al. (2002) UK, 2004 Gatidou et al. (2007) France, 2006 Caquet et al. (2013) Japan, 2003 Harino et al. (2005) Japan, 2007 Eguchi et al. (2010) China, 2004 Lam et al. (2005) Malaysia, 2011 Rashid Ali et al. (2013) South Korea, 2010 Kim et al. (2014) Iran, Bushehr, 2013 (This study)
mentioned that the concentrations of Irgarol up to 2021, 1620, 257, 254 and 186 ng L−1 have been reported in Peninsular Malaysia (Rashid Ali et al., 2013), China (Lam et al., 2005), Japan (Eguchi et al., 2010), USA (Sapozhnikova et al., 2013) and France (Caquet et al., 2013) respectively, which are higher than the levels found in the present study (Table 3). A comparison between the results of diuron and those of other published works showed that diuron pollution in ports and marinas of Bushehr was less than the range of reports from other parts of the world and comparable with areas including USA (b2–12 ng L−1) (Sapozhnikova et al., 2007) and Japan (2–18 ng L− 1) (Eguchi et al., 2010) (Table 3). The study conducted by Hughes and Alexander (1993) revealed that Irgarol 1051 at concentration higher than 136 ng L−1 (EC50) may cause serious damage to some phytoplankton such as Navicula pelliculasa. Dahl and Blanck (1996), working with a periphyton community found that at concentration as low as 63 ng L−1, Irgarol 1051 significantly decreased photosynthetic activity. These values along with ERLwater for Irgarol (24 ng L−1) have been compared with the results of this study (Fig. 1). As no water sample was found to contain Irgarol 1051 above EC50 value, the coastal water in Bushehr (northwest Persian Gulf) may be considered safe for phytoplankton communities. Only one station (Dhows mooring space in Jalali marina) exceeded the values 63 ng L− 1 and ERL of 24 ng L− 1, suggesting some adverse effects on photosynthetic activities of marine organisms and possible environmental risk in this marina. The concentration of diuron in all samples was significantly lower than the proposed EC50 for microalga (450–
2120 ng L−1) (Arai et al., 2009), as a result, it was not sufficient to pose a risk to the aquatic ecosystem in studied areas. In contrast, 3,4-DCA, a degradation product of diuron, was detected in all seawater samples, with the exception of Open seawater and Bushehr port internal canal sites. The concentration of 3,4-DCA ranged from b 1.4 ng L−1 in Open seawater sites to 390 ± 10 ng L−1 in Jalali marina. Jofre marina with the value of 95.2 ± 17 ng L−1 and Bandragah marina with the value of 74.7 ± 7.0 ng L−1 were the next highest polluted sites. The results in Table 2 indicated that the concentrations of 3,4-DCA were higher than the parent compound, diuron. Moreover, no significant relation between the concentration of 3,4-DCA and size of vessels (small boats and dhows) was observed. The higher concentration of 3,4-DCA in comparison with the parent compound could be assigned to the fact that diuron is not the only source of 3,4-DCA in the environment. Degradation of different plant protection agents (such as linuron and propanil) and trichlorocarbanilide (TCC) as an antimicrobial and antifungal compound in personal care products (e.g. soaps, lotions, deodorants etc.) results in releases of 3,4-DCA into the environment (European Commission, 2006). A study showed about 80% of all antimicrobial bar soap sold in the United States contains TCC (Brausch and Rand, 2011). Therefore, discharges of domestic, industrial and vessels untreated wastewater and sewage into the marinas and coastal waters in Bushehr could be the reason that in more than 75% of water samples, 3,4-DCA was detected. The highest concentration of 3,4-DCA in this study (390 ng L−1 in Jalali marina) was lower than the minimum observed effective concentration value (1000 ng L−1) (Giacomazzi and Cochet, 2004) and it can be concluded that the 3,4-DCA concentrations were negligible and could not have a deleterious influence on marine ecological systems in this area. Fig. 2 demonstrates the distribution of antifouling booster biocides in seawater of marinas and ports of Bushehr. Antifouling biocide concentrations detected in this study were tested for significant Spearman's rho correlation (P b 0.05) with water quality parameters such as temperature, salinity, pH, dissolved oxygen and saturated oxygen. No significant correlations were found when Irgarol, diuron and 3,4-DCA concentrations were analyzed with the water quality parameters, which was in accordance with other studies (Sapozhnikova et al., 2007). However, correlations between antifouling biocides were found to be significant. Correlation coefficients (r) for diuron:3,4-DCA, diuron:Irgarol and Irgarol:3,4-DCA were + 0.615, +0.627 and +0.674, respectively. Fig. 3 shows the distribution of Irgarol 1051 in sediments of marinas and ports of Bushehr. Results for analysis of Irgarol 1051 in sediments showed a maximum of 35.4 ng g−1 in Bandargah marina. The
Fig. 2. Distribution of antifouling booster biocides in seawater of marinas and ports of Bushehr.
Please cite this article as: Saleh, A., et al., Antifouling paint booster biocides (Irgarol 1051 and diuron) in marinas and ports of Bushehr, Persian Gulf, Marine Pollution Bulletin (2015), http://dx.doi.org/10.1016/j.marpolbul.2016.02.037
A. Saleh et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx
5
Fig. 3. Distribution of Irgarol 1051 in sediments of marinas and ports of Bushehr.
three highest sediment concentrations of Irgarol were measured in Bandargah marina (dhows mooring space, 35.4 ng g− 1 dry weight), Jalali marina (dhows mooring space, 21.4 ng g− 1 dry weight) and SolhAbad marina (dhows mooring space 2.04–6.80 ng g−1 dry weight). In all other stations, Irgarol concentrations in sediments were lower than LOD. These results suggest that dhows are the main source of Irgarol pollution in sediments of marinas in Bushehr. The maximum values of 3.5, 8.9, 9.8, 23.9, 49.3 ng g−1 dry weight have also been reported for UK (Thomas et al., 2002), USA (Sapozhnikova et al., 2013), Japan (Eguchi et al., 2010), Spain (Sanchez-Rodriguez et al., 2011) and UK (Gatidou et al., 2007) respectively, which are consistent with our data in this study. However, Irgarol has been detected as high as 100, 700 and 1011 ng g−1 dry weight in Japan (Harino et al., 2007), France (Cassi et al., 2008) and UK (Konstantinou and Albanis, 2004), respectively. The maximum concentration of Irgarol detected in sediments was lower than in seawaters taken in our study. This result is supported by research findings suggesting that Irgarol tends to stay in the dissolved aqueous phase rather than partition to or adsorb on sediment (Hall et al., 1999; Comber et al., 2002). It has been indicated that the TOM and grain size of sediments are two significant factors controlling the spatial footprint of pollutants in the aquatic environments (Li et al., 2012). On this basis, TOM and grain size analyses have been performed and no significant Spearman's rho correlation values have been observed between concentrations of Irgarol and values of TOM (r = +0.298) and the fraction of fine particles (clay, r = −0.014 and silt r = −0.44) in sediment samples (P b 0.05). A significant correlation was found between the concentration of Irgarol 1051 in sediment and seawater (r = + 0.535). In this study, sediment samples analyzed in Bandargah, Jalali and Solhabad marinas (i.e. 26% of samples) had Irgarol concentrations exceeding the suggested ERLs for sediments (1.4 ng g−1) (Wezel and Vlaardingen, 2004). These findings appeal a particular attention towards controlling the usage of Irgarol 1051 and other antifouling chemicals for the sustainable conservation of aquatic environment in this area. This work should be considered as a preliminary study of the levels of antifouling booster biocides in waters and sediments of this area and round clock monitoring for preservation of sensitive spots in coastal marine ecosystems of the whole Persian Gulf is needed.
Acknowledgments Authors would like to thank Iranian National Institute for Oceanography and Atmospheric Science (INIOAS) for full funding of this project.
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Please cite this article as: Saleh, A., et al., Antifouling paint booster biocides (Irgarol 1051 and diuron) in marinas and ports of Bushehr, Persian Gulf, Marine Pollution Bulletin (2015), http://dx.doi.org/10.1016/j.marpolbul.2016.02.037
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Baseline
Antifouling paint booster biocides (Irgarol 1051 and diuron) in marinas and ports of Bushehr, Persian Gulf Abolfazl Saleh a,⁎, Saeideh Molaei b, Neda Sheijooni Fumani a, Ehsan Abedi a a b
Iranian National Institute for Oceanography and Atmospheric Science, No. 3, Etemadzadeh St., Fatemi Ave., Tehran 1411813389, Iran Faculty of Chemistry, Kharazmi University, 43Mofateh Ave., Tehran 1571914911, Iran
a r t i c l e
i n f o
Article history: Received 1 December 2015 Received in revised form 11 February 2016 Accepted 15 February 2016 Available online xxxx Keywords: Antifouling paint booster biocides Irgarol 1051 Diuron 3,4-dichloroaniline Bushehr Persian Gulf
a b s t r a c t In the present study, antifouling paint booster biocides, Irgarol 1051 and diuron were measured in ports and marinas of Bushehr, Iran. Results showed that in seawater samples taken from ports and marinas, Irgarol was found at the range of less than LOD to 63.4 ng L−1 and diuron was found to be at the range of less than LOD to 29.1 ng L−1 (in Jalali marina). 3,4-dichloroaniline (3,4-DCA), as a degradation product of diuron, was also analyzed and its maximum concentration was 390 ng L−1. Results for analysis of Irgarol 1051 in sediments showed a maximum concentration of 35.4 ng g−1 dry weight in Bandargah marina. A comparison between the results of this study and those of other published works showed that Irgarol and diuron pollutions in ports and marinas of Bushehr located in the Persian Gulf were less than the average of reports from other parts of the world. © 2016 Elsevier Ltd. All rights reserved.
Organic booster biocides are used as additives in copper-based antifouling paints to prevent the settlement and growth of marine organisms on submerged structures (Konstantinou and Albanis, 2004). Biofouling produces some negative environmental and economical consequences, such as increases in fuel consumption and corrosion processes as well as the potential for the introduction of foreign species in new ecosystems (Lewis et al., 2003). Worldwide, around 18 compounds are currently used as antifouling paint booster biocides with differing degrees of regulation. These chemicals are alternatives to organotin-based antifoulants whose use has been completely banned in 2004 due to their high toxicity and their effects on aquatic organisms (Mackie and Lloyd, 2002). Irgarol 1051 (2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine) and diuron (3-(3,4-dichlorophenyl)-1,1-dimethyl urea) have been widely used among others because of their high effectiveness as a growth inhibitor of marine and freshwater algae (Readman, 1999). Diuron has been predominately used for weed control on land as a substituted urea herbicide since the 1950s. It is also widely applied for non-agricultural applications including vegetation control in industrial sites and rights of way along power lines, roads, railways, and buildings (Moncada, 2004). Irgarol and diuron (with aqueous solubility values of 7 and 36.4 mg L−1 and log Kow 3.95 and 2.85, respectively) exert their antifouling action by inhibiting photosynthesis and impairing electron transport within chloroplasts (Dahl and Blanck, 1996; Alyuruk and Cavas, 2013). Both compounds are much more toxic to phytoplankton ⁎ Corresponding author. E-mail address: [email protected] (A. Saleh).
than other aquatic species (Dahl and Blanck, 1996; Malato et al., 2002). Irgarol appears to be especially toxic to the freshwater diatom (5 day EC50 136 ng L−1) and the freshwater macrophytes (14 day EC50 0.017 ng L−1) (Lambert et al., 2006). The environmental risk limits for Irgarol in water (ERLwater) and sediment (ERLsediment) are 24 ng L−1 and 1.4 ng g−1, respectively (Wezel and Vlaardingen, 2004). The Dutch National Institute of Public Health and the Environment suggested a maximum permissible concentration for Irgarol and diuron of 29 and 430 ng L−1, respectively (Lamoree et al., 2002). Due to the Irgarol and diuron harmful effects on the marine ecosystem, some countries, such as the United Kingdom, Denmark and Sweden, have forbidden the use of Irgarol, whereas diuron has been also prohibited in UK and Netherlands (Thomas and Brooks, 2010). In an overview, elimination (volatilization, chemical hydrolysis, biodegradation, photo-degradation) and accumulation rates (sedimentation and uptake by biota) of chemicals are the two phenomena affecting observed levels. Irgarol and diuron are resistant to hydrolysis and they are stable during 17 days of sunlight irradiation (Arai et al., 2009). Moreover, bacterial biodegradation of Irgarol 1051 and diuron are of minor importance (their initial concentration of 0.1 mg L−1 scarcely changed after 60 days) (Arai et al., 2009). 2-methylthio-4-tert-butylamino-6amino-s-triazine (M1) and 3,4-dichloroaniline (3,4-DCA) are the main metabolites of Irgarol and diuron, respectively (Arai et al., 2009). Nevertheless, results of different studies indicate that generally Irgarol (with half-life ranging from 100 to 350 days) and diuron (with half-life ranging from 43 to 2180 days) are fairly stable compounds in seawater (Hall et al., 1999; Thomas et al., 2002; Moncada, 2004). On the other hand,
http://dx.doi.org/10.1016/j.marpolbul.2016.02.037 0025-326X/© 2016 Elsevier Ltd. All rights reserved.
Please cite this article as: Saleh, A., et al., Antifouling paint booster biocides (Irgarol 1051 and diuron) in marinas and ports of Bushehr, Persian Gulf, Marine Pollution Bulletin (2015), http://dx.doi.org/10.1016/j.marpolbul.2016.02.037
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sorption of these organic pollutants onto settling particulate matters is not only responsible for their concentration reducing in the water column, but also is the principal pathway of their accumulation in sediments. A modular estuarine mesocosm experiment revealed that after 35 days of Irgarol exposure, only 7% of parent compound remained unchanged in the water column and 75% accumulated in the mesocosm sediments (Sapozhnikova et al., 2009). Generally, in sediments, it has been demonstrated that degradation is slow even under aerobic conditions, resulted in booster biocides' elevated persistency in sediments. As a result, the sediments may serve as storage and release sources of pollutants (Thomas et al., 2003; Zhou, 2008). Studies conducted by Tolhurst et al. (2007) and Voulvoulis et al. (2002) showed that disturbance of sediments contaminated with Irgarol can cause desorption of Irgarol with the rate of 1.9–2.4% per 24 h. Environmental monitoring of Irgarol 1051 and diuron has been extensive worldwide, in order to assess the risks to the environment. Since Irgarol and diuron have also agricultural uses, as a result their presence in the aquatic and estuarine environments cannot be attributed solely to the use of antifouling paints. Various studies on detection and distribution of Iragrol and diuron have been conducted in different areas including Northern Europe (Netherlands, Germany, England and Sweden) (Lamoree et al., 2002; Biselli et al., 2000; Thomas et al., 2001; Haglund et al., 2001), Mediterranean Sea (Spain, France and Greece) (Hernando et al., 2001; Tolosa et al., 1996; Sakkas et al., 2002), America (Bermuda and USA) (Konstantinou and Albanis, 2004; Sapozhnikova et al., 2013), and Australia (Konstantinou and Albanis, 2004). Moreover, some studies have been performed in Asia such as South Korea (Kim et al., 2014), Japan (Balakrishnan et al., 2012), Singapore (Basheer et al., 2002) and Malaysia (Rashid Ali et al., 2013) but to date no monitoring survey of these new antifouling biocides has yet been reported in the Persian Gulf (Iran). This study therefore presents the baseline data for occurrence and distribution of Irgarol 1051, diuron and its metabolite (3,4-DCA) in ports and marinas of Bushehr (northwest of the Persian Gulf, Iran). Bushehr peninsula is located in a humid subtropical region. It lies near the head of the Persian Gulf at the northern part of a flat connected with the mainland by tidal marshes (Sheppard et al., 2010). The wide range of seasonal variation of seawater temperature and elevated salinity are important environmental stressors, which could enhance effects of pollution on sensitive marine ecosystems of this area (Schiedek et al., 2007). Bushehr (28.58 N and 50.50 E) is one of the most important ports in the Persian Gulf with a remarkable situation since it is an export market for the agricultural crops of Iranian southern provinces (e.g. Bushehr and Fars provinces) and is one of the largest regional fishing ports of Iran. Water and sediment samples were collected from 16 stations located in the marinas and ports of Bushehr peninsula, northwestern Persian Gulf in October of 2013 at the end of the peak of the shrimp fishing (Table 1). Various sampling sites such as Bushehr port internal canal, marinas and ports for small fishing boats' and dhows' mooring spaces, and shipyards were deliberately chosen as study areas because contamination from antifouling biocides was expected to be high. In locations in which it was possible, samples were collected from the areas dedicated to small boats (b 10 m) and dhows (10–30 m). However, not both vessel classes were present in every location. Three individual water samples were collected at each station. Water samples were taken from approximately 0.5 m below the surface using a Niskin bottle sampler (2 L) and transferred into the pre-cleaned 1 L amber glass bottles. The samples were then kept under 4 °C and brought to laboratory for analysis. Three replicate sediment samples were collected at each site, at 1 m distance from each other and analyzed individually. Surface sediment samples at a water depth between 0.6 and 12.3 m were collected using a VanVeen grab sampler and transferred into the pre-cleaned aluminum containers (500 g) and stored in a freezer at −25 °C until analysis. Measurements of salinity, conductivity, pH and dissolved oxygen (DO) were taken in situ using a Hach HQ40d multimeter with related probs.
Table 1 Sampling location information. Location
Latitude
Longitude
Depth (m)
Jalali marina Jalali marina Open seawater 1 (Persian Gulf) Open seawater 1 (Persian Gulf) Bandargah marina Bandargah marina Open seawater 2 (Persian Gulf) Open seawater 2 (Persian Gulf) Jofre marina Jofre marina Jabri marina Bushehr port internal canal Sadra Ship building factory Sadra Ship building factory Solhabad marina Bushehr port internal canal
28° 55.233′N 28° 55.172′N 28° 52.908′N 28° 52.698′N 28° 49.228′N 28° 49.382′N 28° 56.956′N 28° 56.831′N 28° 58.298′N 28° 58.372′N 28° 58.822′N 28° 59.777′N 28° 58.869′N 28° 58.549′N 28° 58.740′N 28° 58.873′N
50° 48.506′E 50° 48.442′E 50° 49.922′E 50° 49.690′E 50° 54.525′E 50° 54.484′E 50° 48.299′E 50° 47.781′E 50° 49.359′E 50° 49.363′E 50° 50.733′E 50° 49.978′E 50° 51.681′E 50° 51.452′E 50° 50.997′E 50° 50.879′E
3.7 3.1 4.7 6.0 0.6 2.0 5.6 6.2 0.7 1.6 1.6 12.3 4.4 4.7 2.3 5.1
Total organic matter (TOM) was measured for each sediment sample as described elsewhere (Gaspare et al., 2009). For grain size assessments, 10 mL of tetra sodium diphosphate decahydrate (3% w/v) was added into the 1 g of homogenized and freeze-dried sediment. After 20 min of stirring, the mixture was introduced into a laser scattering particle size distribution analyzer (HORIBA, LA-950, Japan & France). Irgarol 1051, diuron and 3,4-dichloroaniline were purchased from Sigma-Aldrich (St. Louis, MO, USA). Analysis of water samples was performed using microfunnelsupported liquid-phase microextraction method (MF-LPME) as previously explained by Saleh et al. (2014). Briefly, a volume of 300 mL of seawater sample was introduced into the glass vessel. A small magnetic rod was inserted into the vessel. The vessel was closed with the stopper through which passed the glass microfunnel. The upper part of the funnel was filled with a 400 μL of toluene by using a syringe. The sample compartment was stirred at 240 rpm with a magnetic stirrer. After the extraction, the extractant was withdrawn by using a syringe and its solvent evaporated under the gentle stream of nitrogen at room temperature. The residual re-dissolved in 50 μL methanol, diluted to 100 μL with deionized water and injected into the HPLC loop followed by analysis. Samples of sediment were freeze-dried by an Operon freeze-dryer (5503-Korean) for 72 h. Analysis of sediments was carried out using ultrasound-assisted extraction (UAE) followed by dispersive liquid– liquid microextraction (DLLME) according to the procedures of Lambropoulou et al. (2003) and Rezaee et al. (2006) with some modifications. Approximately 3 g of freeze-dried, homogenized and ground sediment was leached by ultrasound waves with 4 mL of acetone for 1 h, after which the sample was centrifuged for 10 min at 3000 rpm. The supernatant (approximately 2.5 mL) was transferred into a conical test tube followed by addition of 200 μL of DCM as an extraction solvent. Then, the mixture was rapidly injected into the 10 mL distilled water placed in a conical centrifuge tube to form a cloudy solution (for further cleanup and preconcentration). Using centrifugation at 3000 rpm for 10 min, DCM was settled at the conical bottom of the test tube and 1 μL of which was injected into the gas chromatography-mass spectrometry (GC–MS) for analysis. Chromatographic analysis in seawater samples was carried out on an Agilent 1100 HPLC system (California, USA) equipped with an Agilant G1314A variable wavelength detector (VWD). A C18 column (5 μm, 4.6 mm × 250 mm) from Agilent Eclipse Plus was applied to separate the analytes under isocratic elution condition. A mixture of acetonitrile and water (55:45, v/v) with a flow rate of 1 mL min−1 was used as the mobile phase. The detection was performed at wavelengths of 223 (for Irgarol 1051) and 244 nm (for diuron and 3,4-dichloroaniline). Quantitative analysis of Irgarol in sediment samples was conducted on a gas chromatograph Agilent (Wilmington, DE, USA) 6890 equipped
Please cite this article as: Saleh, A., et al., Antifouling paint booster biocides (Irgarol 1051 and diuron) in marinas and ports of Bushehr, Persian Gulf, Marine Pollution Bulletin (2015), http://dx.doi.org/10.1016/j.marpolbul.2016.02.037
A. Saleh et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx
with split/splitless injector operated at 270 °C in splitless mode and mass detector Agilent 5973. A 30 m HP-5MS fused silica capillary column (0.25 mm I.D., 0.25 μm film thickness) was used for separation. Helium (purity 99.999%) was used as carrier gas at constant flow rate of 1 mL min−1. For quantitative analysis, two selected mass fragments of 182 and 253 m/z were studied in selected ion monitoring (SIM) mode. In order to compensate for matrices effect, analyte-free seawater and sediment were used to obtain calibration curves (extraction calibration using authentic matrix and authentic analyte). Quantification in seawater within the range of 8–5000 ng L−1 for Irgarol 1051 and 3,4DCA, and 48–5000 ng L−1 for diuron was performed using constructed calibration curves with regression coefficients (R2) better than 0.995. The LODs in seawater, calculated at a signal-to-noise (S/N) ratio of 3, were 1.0, 1.4 and 4.8 ng L− 1 and LOQs, calculated at S/N = 10, were 3.2, 4.5 and 15.9 ng L−1 for Irgarol 1051, 3,4-DCA and diuron, respectively. The LOD and LOQ values for Irgarol 1051 in sediment were obtained 2.04 and 6.80 ng g− 1 dry weight, respectively. The relative standard deviations (RSDs) for antifouling biocides in seawater and sediment were below 12 and 9.9%, respectively. Statistical data analysis was performed with SPSS 17.0 for Windows. Shapiro–Wilk W test was used to check for normality. Spearman's rho correlations were used to explore relationships between analyte concentrations and water and sediment quality parameters. Antifouling biocide concentrations in seawater of Bushehr ports and marinas are shown in Table 2. The values of the concentration are reported as mean ± standard deviation of replicate measurements. Irgarol 1051 was detected in 31% of water samples with concentrations ranging from 10.9 ng L−1 to 63.4 ng L−1. The highest Irgarol 1051 concentration was detected in Jalali marina (dhows mooring space, 63.4 ± 16 ng L−1) followed by Jofreh marina (dhows mooring space, 17.2 ± 1.9 ng L−1, small boats mooring space 13.1 ± 2.3 ng L−1), Bandargah marina (dhows mooring space, 11.9 ± 1.5 ng L− 1) and Solhabad marina (dhows mooring space, 10.9 ± 0.4 ng L−1). Diuron was detected at only four stations (i.e. 25% of water samples) in the range of 13.6 ± 1.0 ng L−1 to 29.1 ± 2.5 ng L−1. The rest of stations (12) showed the concentrations below the detection limit of diuron. Jalali marina (dhows mooring space) showed the highest diuron concentration, whereas the second highest diuron concentration corresponded to Solhabad marina (dhows mooring space), with a value of 22.5 ± 0.6 ng L−1. The high presence of both biocides in dhows mooring spaces compared to small boats mooring spaces indicated that these compounds were extensively used in dhows paint formulations. Based on information from indigenous people of Bushehr, small fishing boats are painted once during their lifetime whereas, larger vessels such as dhows are dry ducked and repainted every 3 to 5 years. In addition, larger size and
3
Fig. 1. Average concentrations of Irgarol 1051 in water samples, ng L−1, error bars represent the maximum concentration observed.
contact surface of dhows with seawater could be the reason of the significant differences of levels in dhows and small boats. Moreover, number of factors contribute Irgarol and diuron contaminations in the various sites. Areas including Jalali and Jofreh Marinas with higher density of boats, residence of boats throughout the year, and lower water exchange rates demonstrated higher concentrations of paint booster biocides in contrast to the other areas with less boating activities and higher water exchange rate (Biselli et al., 2000; Konstantinou and Albanis, 2004). The maximum levels of Irgarol found in various Bushehr marinas were significantly lower than the other reported European regions such as Sweden (364 ng L−1), UK (621 ng L− 1), France (491 ng L−1) and Spain (670 ng L−1) and comparable with areas including Denmark (9 ng L− 1), Netherland (39 ng L− 1), and Greece (24 ng L− 1), as indicated in Fig. 1 (Readman, 2006). It should be
Table 2 Concentration of antifouling biocides found in seawater samples taken from Bushehr ports and marinas. Sampling area
St. no.
Station
3,4-DCA (ng L−1) ± SD
Diuron (ng L−1) ± SD
Irgarol 1051 (ng L−1) ± SD
Jalali marina
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
Small boats mooring space Dhows mooring space Nearshore Offshore Small boats mooring space Dhows mooring space Nearshore Offshore Small boats mooring space Dhows mooring space Small boats mooring space Anchorage 2 Ship building and repairing yard Repairing yard Dhows mooring space Middle of the canal
390 ± 10 289 ± 29 18.8 ± 2.2 10.2 ± 3.3 35.2 ± 2.0 74.7 ± 7.0 nd nd 95.2 ± 17 73.9 ± 5.3 23.7 ± 2.7 nd 15.8 ± 4.9 22.7 ± 3.5 47.2 ± 4.6 nd
≈13.6 ± 1.0 29.1 ± 2.5 nda nd nd nd nd nd nd 21.0 ± 1.7 nd nd nd nd 22.5 ± 0.6 nd
nd 63.4 ± 16 nd nd nd 11.9 ± 1.5 nd nd 13.1 ± 2.3 17.2 ± 1.9 nd nd nd nd 10.9 ± 0.4 nd
Open seawater 1 (Persian Gulf) Bandargah marina Open seawater 2 (Persian Gulf) Jofreh marina Jabri marina Bushehr port internal canal Sadra Ship building factory Solhabad marina Bushehr port internal canal a
nd: Not detected
Please cite this article as: Saleh, A., et al., Antifouling paint booster biocides (Irgarol 1051 and diuron) in marinas and ports of Bushehr, Persian Gulf, Marine Pollution Bulletin (2015), http://dx.doi.org/10.1016/j.marpolbul.2016.02.037
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A. Saleh et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx
Table 3 Comparison of antifouling biocide concentrations (ng L−1) found in water in this study with other reported studies. Irgarol 1051 (ng L−1)
Diuron (ng L−1)
Location, year
2–254 1–304 5–1816 2–305 b3.1–136 bLOQ-186 1.3–77 10–257 110–1620 b1.0–2021 0.2–14.1 b1.0–63.4
b2–68 b2–12 Not analyzed b1–78 b7–366 bLOQ-268 13–350 2–18 Not analyzed Not analyzed 13–1360 b4.8–29.1
USA, CA, 2008 Sapozhnikova et al. (2013) USA, CA, 2005 Sapozhnikova et al. (2007) USA, MD, 2004 Hall et al. (2005) UK, 2000 Thomas et al. (2002) UK, 2004 Gatidou et al. (2007) France, 2006 Caquet et al. (2013) Japan, 2003 Harino et al. (2005) Japan, 2007 Eguchi et al. (2010) China, 2004 Lam et al. (2005) Malaysia, 2011 Rashid Ali et al. (2013) South Korea, 2010 Kim et al. (2014) Iran, Bushehr, 2013 (This study)
mentioned that the concentrations of Irgarol up to 2021, 1620, 257, 254 and 186 ng L−1 have been reported in Peninsular Malaysia (Rashid Ali et al., 2013), China (Lam et al., 2005), Japan (Eguchi et al., 2010), USA (Sapozhnikova et al., 2013) and France (Caquet et al., 2013) respectively, which are higher than the levels found in the present study (Table 3). A comparison between the results of diuron and those of other published works showed that diuron pollution in ports and marinas of Bushehr was less than the range of reports from other parts of the world and comparable with areas including USA (b2–12 ng L−1) (Sapozhnikova et al., 2007) and Japan (2–18 ng L− 1) (Eguchi et al., 2010) (Table 3). The study conducted by Hughes and Alexander (1993) revealed that Irgarol 1051 at concentration higher than 136 ng L−1 (EC50) may cause serious damage to some phytoplankton such as Navicula pelliculasa. Dahl and Blanck (1996), working with a periphyton community found that at concentration as low as 63 ng L−1, Irgarol 1051 significantly decreased photosynthetic activity. These values along with ERLwater for Irgarol (24 ng L−1) have been compared with the results of this study (Fig. 1). As no water sample was found to contain Irgarol 1051 above EC50 value, the coastal water in Bushehr (northwest Persian Gulf) may be considered safe for phytoplankton communities. Only one station (Dhows mooring space in Jalali marina) exceeded the values 63 ng L− 1 and ERL of 24 ng L− 1, suggesting some adverse effects on photosynthetic activities of marine organisms and possible environmental risk in this marina. The concentration of diuron in all samples was significantly lower than the proposed EC50 for microalga (450–
2120 ng L−1) (Arai et al., 2009), as a result, it was not sufficient to pose a risk to the aquatic ecosystem in studied areas. In contrast, 3,4-DCA, a degradation product of diuron, was detected in all seawater samples, with the exception of Open seawater and Bushehr port internal canal sites. The concentration of 3,4-DCA ranged from b 1.4 ng L−1 in Open seawater sites to 390 ± 10 ng L−1 in Jalali marina. Jofre marina with the value of 95.2 ± 17 ng L−1 and Bandragah marina with the value of 74.7 ± 7.0 ng L−1 were the next highest polluted sites. The results in Table 2 indicated that the concentrations of 3,4-DCA were higher than the parent compound, diuron. Moreover, no significant relation between the concentration of 3,4-DCA and size of vessels (small boats and dhows) was observed. The higher concentration of 3,4-DCA in comparison with the parent compound could be assigned to the fact that diuron is not the only source of 3,4-DCA in the environment. Degradation of different plant protection agents (such as linuron and propanil) and trichlorocarbanilide (TCC) as an antimicrobial and antifungal compound in personal care products (e.g. soaps, lotions, deodorants etc.) results in releases of 3,4-DCA into the environment (European Commission, 2006). A study showed about 80% of all antimicrobial bar soap sold in the United States contains TCC (Brausch and Rand, 2011). Therefore, discharges of domestic, industrial and vessels untreated wastewater and sewage into the marinas and coastal waters in Bushehr could be the reason that in more than 75% of water samples, 3,4-DCA was detected. The highest concentration of 3,4-DCA in this study (390 ng L−1 in Jalali marina) was lower than the minimum observed effective concentration value (1000 ng L−1) (Giacomazzi and Cochet, 2004) and it can be concluded that the 3,4-DCA concentrations were negligible and could not have a deleterious influence on marine ecological systems in this area. Fig. 2 demonstrates the distribution of antifouling booster biocides in seawater of marinas and ports of Bushehr. Antifouling biocide concentrations detected in this study were tested for significant Spearman's rho correlation (P b 0.05) with water quality parameters such as temperature, salinity, pH, dissolved oxygen and saturated oxygen. No significant correlations were found when Irgarol, diuron and 3,4-DCA concentrations were analyzed with the water quality parameters, which was in accordance with other studies (Sapozhnikova et al., 2007). However, correlations between antifouling biocides were found to be significant. Correlation coefficients (r) for diuron:3,4-DCA, diuron:Irgarol and Irgarol:3,4-DCA were + 0.615, +0.627 and +0.674, respectively. Fig. 3 shows the distribution of Irgarol 1051 in sediments of marinas and ports of Bushehr. Results for analysis of Irgarol 1051 in sediments showed a maximum of 35.4 ng g−1 in Bandargah marina. The
Fig. 2. Distribution of antifouling booster biocides in seawater of marinas and ports of Bushehr.
Please cite this article as: Saleh, A., et al., Antifouling paint booster biocides (Irgarol 1051 and diuron) in marinas and ports of Bushehr, Persian Gulf, Marine Pollution Bulletin (2015), http://dx.doi.org/10.1016/j.marpolbul.2016.02.037
A. Saleh et al. / Marine Pollution Bulletin xxx (2015) xxx–xxx
5
Fig. 3. Distribution of Irgarol 1051 in sediments of marinas and ports of Bushehr.
three highest sediment concentrations of Irgarol were measured in Bandargah marina (dhows mooring space, 35.4 ng g− 1 dry weight), Jalali marina (dhows mooring space, 21.4 ng g− 1 dry weight) and SolhAbad marina (dhows mooring space 2.04–6.80 ng g−1 dry weight). In all other stations, Irgarol concentrations in sediments were lower than LOD. These results suggest that dhows are the main source of Irgarol pollution in sediments of marinas in Bushehr. The maximum values of 3.5, 8.9, 9.8, 23.9, 49.3 ng g−1 dry weight have also been reported for UK (Thomas et al., 2002), USA (Sapozhnikova et al., 2013), Japan (Eguchi et al., 2010), Spain (Sanchez-Rodriguez et al., 2011) and UK (Gatidou et al., 2007) respectively, which are consistent with our data in this study. However, Irgarol has been detected as high as 100, 700 and 1011 ng g−1 dry weight in Japan (Harino et al., 2007), France (Cassi et al., 2008) and UK (Konstantinou and Albanis, 2004), respectively. The maximum concentration of Irgarol detected in sediments was lower than in seawaters taken in our study. This result is supported by research findings suggesting that Irgarol tends to stay in the dissolved aqueous phase rather than partition to or adsorb on sediment (Hall et al., 1999; Comber et al., 2002). It has been indicated that the TOM and grain size of sediments are two significant factors controlling the spatial footprint of pollutants in the aquatic environments (Li et al., 2012). On this basis, TOM and grain size analyses have been performed and no significant Spearman's rho correlation values have been observed between concentrations of Irgarol and values of TOM (r = +0.298) and the fraction of fine particles (clay, r = −0.014 and silt r = −0.44) in sediment samples (P b 0.05). A significant correlation was found between the concentration of Irgarol 1051 in sediment and seawater (r = + 0.535). In this study, sediment samples analyzed in Bandargah, Jalali and Solhabad marinas (i.e. 26% of samples) had Irgarol concentrations exceeding the suggested ERLs for sediments (1.4 ng g−1) (Wezel and Vlaardingen, 2004). These findings appeal a particular attention towards controlling the usage of Irgarol 1051 and other antifouling chemicals for the sustainable conservation of aquatic environment in this area. This work should be considered as a preliminary study of the levels of antifouling booster biocides in waters and sediments of this area and round clock monitoring for preservation of sensitive spots in coastal marine ecosystems of the whole Persian Gulf is needed.
Acknowledgments Authors would like to thank Iranian National Institute for Oceanography and Atmospheric Science (INIOAS) for full funding of this project.
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Please cite this article as: Saleh, A., et al., Antifouling paint booster biocides (Irgarol 1051 and diuron) in marinas and ports of Bushehr, Persian Gulf, Marine Pollution Bulletin (2015), http://dx.doi.org/10.1016/j.marpolbul.2016.02.037