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Initial environmental risk assessment of hazardous and noxious substances (HNS) spill accidents to mitigate its damages
Marine Pollution Bulletin 139 (2019) 205–213
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Marine Pollution Bulletin journal homepage: www.elsevier.com/locate/marpolbul
Baseline
Initial environmental risk assessment of hazardous and noxious substances (HNS) spill accidents to mitigate its damages
T
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Young-Ryun Kima,1, Moonjin Leeb,1, Jung-Yeul Jungb, , Tae-Won Kima, Daejoong Kimc a
Marine Eco-Technology Institute, Busan 48520, Republic of Korea Marine Safety and Environmental Research Division, Korea Research Institute of Ships and Ocean Engineering, KIOST, Daejeon 34103, Republic of Korea c Department of Mechanical Engineering, Sogang University, Seoul 04107, Republic of Korea b
A R T I C LE I N FO
A B S T R A C T
Keywords: Exposure assessment HNS Initial environmental risk assessment Marine ecosystem Spill accident Toxicity assessment
In this study, a system was established to perform an initial environmental risk assessment of hazardous and noxious substances (HNS) spill accidents. Initial environmental risk assessment was performed using exposure and hazard assessments. An integrated hydrodynamic and chemical fate model was used to predict HNS concentrations at harbors, taking into account local environmental conditions. To consider the worst case HNS spill accident, the spill amount of 10,000 tonnages, was used for this study. The results show that highly soluble HNS are fatal to marine organisms during the neap tide. The results were based on a hypothetical worst case HNS spill accident and, not any specific actual HNS spill accident. Nevertheless, the method and system developed in this study, which includes the physical/chemical properties of 158 priority HNS, can be readily used to perform an initial environmental risk assessment for future HNS spill accidents.
Global seaborne trade continues to grow with developments in the world economy and trade. For example, a compound annual growth rate of 3.2% between 2017 and 2022 has been projected by the United Nations Conference on Trade and Development (UNCTAD) (UNCTAD, 2017). The Republic of Korea is the 7th largest ownership country and the Port of Busan is the 6th largest container port (UNCTAD, 2017). Also the shipping quantity of hazardous and noxious substances (HNS) in Korean ports during 2014–2015 was approximately 90 million tons (Jang et al., 2017). HNS spill accidents can cause hazards to the environment, human health, living resources, and amenities. To mitigate the hazards and damages from HNS spill accidents, initial environmental risk assessment is essential; it is an important step towards making a risk characterization and aiding with decision-making about further assessments by analyzing and assessing the exposure and hazard assessments. Environmental risk assessment and monitoring after HNS spill accidents have been recognized as the most effective methods to reduce environmental damages and to help in preparation of the contingency plan (Neuparth et al., 2011; Guillén et al., 2012; Neuparth et al., 2012; Radović et al., 2012; Lee and Jung, 2013; Neuparth et al., 2013; Kirby et al., 2014; Lee and Jung, 2015; Valdor et al., 2015; Cunha et al., 2016; Fernández-Macho, 2016). There are various studies on environmental risk assessment and monitoring after HNS spill accidents (Fuhrer et al.,
2012; Neuparth et al., 2012; Radović et al., 2012; Lee and Jung, 2013; Kirby et al., 2014; Koo et al., 2015; Takeda et al., 2015). However, there are only a few initial environmental risk assessment of HNS spills in Korea, as well as worldwide. In this study, we suggest a method to carry out the initial environmental risk assessment using exposure and hazard assessments. The results show that highly soluble HNS spills are fatal to marine organisms during the neap tide. The initial step in assessing the environmental risk of an HNS spill accident involves using the early stage information to identify known chemicals that require a more detailed risk assessment of their impact on ecosystems and human health. The initial environmental risk assessment is carried out through exposure and hazard assessments, and then the risk priority is determined using the results of both assessments. The exposure assessment is that estimates the exposure resulting from a release or occurrence of a chemical, physical, or biological agent in a medium. And it strives to quantify, using measurement or predictive tools, the magnitude, duration, and extent of exposure (SuterII, 1995). The hazard assessment is a preliminary activity that helps define the assessment problem by determining which environmental components are potentially exposed to toxic concentrations and how those components might be affected by the exposure (SuterII, 1995). In this study, an initial environmental risk assessment of marine ecosystems was performed based on the effects of HNS spills occurring
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Corresponding author. E-mail address: [email protected] (J.-Y. Jung). 1 Equally contributed authors. https://doi.org/10.1016/j.marpolbul.2018.12.044 Received 17 September 2018; Received in revised form 26 November 2018; Accepted 21 December 2018 0025-326X/ © 2018 Elsevier Ltd. All rights reserved.
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of HNS in the environment. A worst case HNS spill accident has not occurred in the waters surrounding the Korean Peninsula (Lee and Jung, 2013; KCG, 2018). However, the possibility of a worst case HNS spill accident may increase due to the increasing volume of maritime HNS traffic. Therefore, it is necessary to estimate the maximum possible HNS spill amount. In Korea, the deadweight tonnage (DWT) of the largest HNS carrier is 60,000, so the maximum spill amount could be assumed of 10,000 tonnages (which was from a correlation 3 × 10−7 × DWT2 + 0.1362 × DWT (R2 = 0.9926) to estimate leakage amounts of loaded HNS for a grounding accident) (IPIECA, 2000; Lee and Jung, 2013). However, the maximum possible spill amount varies by country. In the United States, the maximum possible spill amount is considered to be the total amount of cargo. In the case of Japan, it is 9% of DWT. In Canada, the national control capacity of an HNS spill amount is 10,000 tonnages. There are more than 10 HNS traffic ports in Korea. We observed the HNS species and amount of maritime transportation occurring at each of 13 major ports as shown in Table 1. To carry out the initial environmental risk assessment, three ports (i.e. the ports are Ulsan port, Gwangyang port and Daesan port) were selected based on their total traffic quantity, where the traffic quantity of HNS was > 14 M tonnages at each port. We already developed the HNS priority scoring and ranking system in our previous study (Kim et al., 2016). The risk prioritization is performed using the combined score (i.e., the times of the hazard and the exposure), which can be described as (Kim et al., 2016),
Table 1 Maritime transportation data at major ports in Korea during 2014–2015 (Kim et al., 2016). Port name
No. of HNS
Quantity, tons
Ulsan Gwangyang Daesan Pyeongtaek Incheon Masan Gunsam Busan Yeosu Pohang Mokpo Jeju Total
108 91 32 45 19 3 10 55 34 3 1 2 158
38,273,680 21,868,160 14,940,481 6,695,806 4,035,371 2,143,879 450,933 413,616 369,706 65,604 61,736 34,941 89,353,913
The bold was highlighted to emphasize the target ports and its imformation.
during loading or unloading at ports, which is different from previous risk assessment studies of HNS spill accidents (Lee and Jung, 2013; Takeda et al., 2015; Fernández-Macho, 2016). To estimate the maximum spill amount, a value used in calculations in this study, we used the results of our previous study in which the maximum HNS spill amount is estimated based on the maximum dead-weights of HNS carriers and credible regression value from the International Petroleum Industry Environmental Conservation Association (IPIECA) (IPIECA, 2000; Lee and Jung, 2013). We used a hydrodynamic model, based on the maximum spill amount, to predict the concentration and behavior
Risk = Toxicity × Exposure
Fig. 1. A schematic diagram of the HNS scoring and ranking systems (Kim et al., 2016). 206
(1)
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Fig. 2. The MAMPEC model input and output display.
Fig. 3. Real pictures of the each harbor and harbor type selected in this study.
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Fig. 4. Measuring stations of the water, sediment and tidal current characteristics. Table 2 Characteristics and PEC calculation results (for the spill amount of 10,000 tonnages) of priority HNS at Ulsan port. Priority rank
1 2 3 8 10 13 14 18 31 37 48 53 57 68 76 85 a b
HNS name
Coal tar Phenol Ammonia aqueous (28% or less) Acrylonitrile Sulfur (molten) Acetone Ethyl Alcohol Sulphuric acid Methyl alcohol Ethylene dichloride Acetic acid Phosphoric acid Nitric acid (< 70%) Sodium hydroxide solution Vinyl acetate Methyl methacrylate
CASRN
8007-45-2 108-95-2 7664-41-7 107-13-1 7704-34-9 67-64-1 64-17-5 7664-93-9 67-56-1 107-06-2 64-19-7 7664-38-2 7697-37-2 1310-73-2 108-05-4 80-62-6
MARPOL Pollution category (MEPC, 2006)
X Y Y Y Z Z Z Y Y Y Z Z Y Y Y Y
Physical behaviora
S S DE DE S DE D D DE SD D D D D ED ED
Biodegradationb
NR R R NR Inorg R R Inorg R NR R Inorg Inorg Inorg R R
PEC (ug/L) Neap tide
30 days mean
Spring tide
7.11E + 02 1.58E + 04 1.81E + 04 2.56E + 04 2.98E + 04 1.29E + 05 2.68E + 05 6.03E + 05 5.93E + 05 2.12E + 03 2.83E + 05 6.03E + 05 2.95E + 04 6.03E + 05 1.08E + 04 4.45E + 03
6.74E + 02 1.48E + 04 1.70E + 04 2.42E + 04 2.85E + 04 1.21E + 05 2.52E + 05 5.65E + 05 5.57E + 05 2.01E + 03 2.66E + 05 5.65E + 05 2.80E + 04 5.65E + 05 1.02E + 04 4.19E + 03
6.14E + 02 1.32E + 04 1.52E + 04 2.18E + 04 2.62E + 04 1.09E + 05 2.26E + 05 5.05E + 05 4.99E + 05 1.82E + 03 2.38E + 05 5.05E + 05 2.56E + 04 5.05E + 05 9.27E + 03 3.77E + 03
S: Sinks, SD: Sinks/Dissolves, D: Dissolves, DE: Dissolves/Evaporates, ED: Evaporates/Dissolves (GESAMP, 2014, 2016). R: readily biodegradable, NR: not readily biodegradable, Inorg: Inorganic substance (GESAMP, 2014, 2016).
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Table 3 Characteristics and PEC calculation results (for the spill amount of 10,000 tonnages) of priority HNS at Gwang-yang port. Priority rank
1 2 3 8 10 13 14 18 19 31 37 45 48 53 57 68 76 85 a b
HNS name
CASRN
Coal tar Phenol Ammonia aqueous (28% or less) Acrylonitrile Sulfur (molten) Acetone Ethyl Alcohol Sulphuric acid Creosote (coal tar) Methyl alcohol Ethylene dichloride Hydrochloric acid Acetic acid Phosphoric acid Nitric acid (< 70%) Sodium hydroxide solution Vinyl acetate Methyl methacrylate
8007-45-2 108-95-2 7664-41-7 107-13-1 7704-34-9 67-64-1 64-17-5 7664-93-9 8001-58-9 67-56-1 107-06-2 7647-01-0 64-19-7 7664-38-2 7697-37-2 1310-73-2 108-05-4 80-62-6
MARPOL Pollution category (MEPC, 2006)
X Y Y Y Z Z Z Y X Y Y Z Z Z Y Y Y Y
Physical behaviora
S S DE DE S DE D D S DE SD DE D D D D ED ED
Biodegradationb
NR R R NR Inorg R R Inorg NR R NR Inorg R Inorg Inorg Inorg R R
PEC (ug/L) Neap tide
30 days mean
Spring tide
1.13E + 02 7.70E + 03 8.22E + 03 5.90E + 03 3.76E + 04 4.11E + 05 1.01E + 05 2.96E + 05 – 2.25E + 05 3.54E + 02 2.98E + 02 1.13E + 05 2.96E + 05 4.22E + 03 2.96E + 05 1.83E + 03 1.16E + 03
8.92E + 01 5.60E + 03 6.07E + 03 4.71E + 03 2.87E + 03 3.21E + 04 7.73E + 04 2.16E + 05 1.72E + 05 2.80E + 02 2.08E + 02 8.57E + 04 2.16E + 05 3.29E + 03 2.16E + 05 1.45E + 03 9.21E + 02
9.70E + 01 6.32E + 03 6.81E + 03 5.12E + 03 3.15E + 03 3.52E + 04 8.56E + 04 2.43E + 05 – 1.90E + 05 3.05E + 02 2.42E + 02 9.53E + 04 2.43E + 05 3.59E + 03 2.43E + 05 1.58E + 03 1.00E + 03
Neap tide
30 days mean
Spring tide
1.00E + 02 1.97E + 03 4.52E + 03 1.65E + 04 3.40E + 04 7.51E + 04 2.96E + 02 3.57E + 04 4.28E + 03 7.51E + 04 1.50E + 03 5.81E + 02
6.02E + 01 1.18E + 03 2.72E + 03 9.90E + 03 2.04E + 04 4.50E + 04 1.78E + 02 2.14E + 04 2.57E + 03 4.51E + 04 9.00E + 02 3.49E + 02
4.48E + 01 8.77E + 02 2.02E + 03 7.37E + 03 1.52E + 04 3.35E + 04 1.32E + 02 1.60E + 04 1.91E + 03 3.35E + 04 6.70E + 02 2.60E + 02
S: Sinks, SD: Sinks/Dissolves, D: Dissolves, DE: Dissolves/Evaporates, ED: Evaporates/Dissolves (GESAMP, 2014, 2016). R: readily biodegradable, NR: not readily biodegradable, Inorg: Inorganic substance (GESAMP, 2014, 2016).
Table 4 Characteristics and PEC calculation results (for the spill amount of 10,000 tonnages) of priority HNS at Daesan port. Priority rank
1 2 10 13 14 31 37 48 57 68 76 85 a b
HNS name
Coal tar Phenol Sulfur (molten) Acetone Ethyl Alcohol Methyl alcohol Ethylene dichloride Acetic acid Nitric acid (< 70%) Sodium hydroxide solution Vinyl acetate Methyl methacrylate
CASRN
8007-45-2 108-95-2 7704-34-9 67-64-1 64-17-5 67-56-1 107-06-2 64-19-7 7697-37-2 1310-73-2 108-05-4 80-62-6
Marpol Pollution category (MEPC, 2006)
X Y Z Z Z Y Y Z Y Y Y Y
Physical behaviora
S S S DE D DE SD D D D ED ED
GESAMP* biodegradationb
NR R Inorg R R R NR R Inorg Inorg R R
PEC (ug/L)
S: Sinks, SD: Sinks/Dissolves, D: Dissolves, DE: Dissolves/Evaporates, ED: Evaporates/Dissolves (GESAMP, 2014, 2016). R: readily biodegradable, NR: not readily biodegradable, Inorg: Inorganic substance (GESAMP, 2014, 2016).
the risk characteristic can be calculated through the Hazard Quotient (HQ, =PEC/PNEC). For analyzing the behavior of the spilled HNS, we used the integrated hydrodynamic and chemical fate model MAMPEC. The MAMPEC is a steady-state 2D integrated hydrodynamic and chemical fate model, originally developed for the exposure assessment of antifouling substances (van Hattum et al., 2016); however, it was revised by the IMO and the Joint Group of Experts on the Scientific Aspects of Marine Environmental Protection (GESAMP) in 2011 for the purpose of assessing the chemical effect of ballast water treatment systems (BWTS) on the marine ecosystem. The revised model has been recommended for risk assessment during the basic and final approval of BWTS by the IMO MEPC. The model can predict the concentration distribution of HNS in the four marine environments (i.e., the open harbor, marina, open sea, and commercial harbor) as shown in the top-left portion of Fig. 2. MAMPEC calculates the total water exchange volume (Ve, m3) as the sum of the tidal prism (Vt) and the exchange volumes due to the horizontal eddy in the harbor entrance (Vh), due to density currents (Vd), wind-driven exchange (Vw), non-tidal exchange flow (Vnt) and the extra flush flow from within the harbor (Vef), which is expressed as follows (van Hattum et al., 2016);
where the hazard is expressed as a function of acute toxicity, chronic toxicity, carcinogenic toxicity, and other toxicity, and the exposure is expressed as a function of persistence, bioaccumulation and transportation. The details of the scoring and ranking system were described in our previous study (Kim et al., 2016) and the schematic diagram is shown in Fig. 1. This method is similar to previous studies (Haimes, 2009; Harold et al., 2014). Using the system described above and information about HNS traffic in Korea, we prioritized 158 HNS, which will be used to establish the preparedness and contingency plans for HNS spill accidents in Korea. Eventually, the prioritization will be expanded to 545 species of HNS traffic in Korea. Among the current 158 priority HNS, there are 16, 18, and 12 of zero-tier priority HNS traffic at Ulsan port, Gwangyang port, and Daesan port, respectively. The total species of zero-tier priority HNS is considered to be 18 because almost all HNS traffic overlapped between ports. The initial environmental risk assessment of an HNS spill accident is performed based on the approach and the prioritization described above. First, the predicted environmental concentration (PEC) is calculated using the integrated hydrodynamic and chemical fate model (van Hattum et al., 2016). Second, the predicted no-effect concentration (PNEC), at which HNS will likely have no toxic effect on marine organisms, is evaluated to determine possible HNS toxicity. Then, finally,
Ve = Vt + Vh + Vd + Vw + Vnt + Vef 209
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Fig. 5. Assignment of assessment factors (AF) used for deriving PNEC values (IMO, 2017) and the template for HNS eco-toxicity database.
Table 5 Results of PNEC, hazard quotient and aquatic risk characterization (for the spill amount of 10,000 tonnages) of priority HNS in Ulsan port. Priority rank
1 2 3 8 10 13 14 18 31 37 48 53 57 68 76 85
HNS name
Coal tar Phenol Ammonia aqueous (< 28%) Acrylonitrile Sulfur (molten) Acetone Ethyl alcohol Sulphuric acid Methyl alcohol Ethylene dichloride Acetic acid Phosphoric acid Nitric acid (< 70%) Sodium hydroxide solution Vinyl acetate Methyl methacrylate
PNEC source
Assessment factor
Taxonomic group
Acute or chronic
Endpoint
Fish Fish Crustacea
Chronic Chronic Chronic
LOEL LC50 NOEC
100 10 100
Crustacea Other Fish Other Crustacea Fish Fish Crustacea Fish Fish Crustacea
Chronic Chronic Chronic Chronic Chronic Chronic Chronic Chronic Acute Acute Acute
NOEC LC50 LOEC NOEC NOEC NOEC NOEC NOEC LC50 LC50 EC50
Fish Crustacea
Acute Chronic
LC50 NOEC
PNEC (ug/L)
Hazard Quotient (PEC/PNEC)
Aquatic risk characterization (A/B/C/D/E)
Neap tide
30 days mean
Spring tide
19 7 5.5
3.74E + 01 2.26E + 03 3.29E + 03
3.55E + 01 2.11E + 03 3.09E + 03
3.23E + 01 1.89E + 03 2.76E + 03
C D D
100 100 100 100 100 10 50 100 10,000 1,000 10,000
5 15.4 49.5 1 1.3 10 36.4 320 6 72 4.038
5.12E + 03 1.94E + 03 2.61E + 03 2.68E + 05 4.64E + 05 5.93E + 04 5.82E + 01 8.84E + 02 1.01E + 05 4.10E + 02 1.49E + 05
4.84E + 03 1.85E + 03 2.44E + 03 2.52E + 05 4.35E + 05 5.57E + 04 5.52E + 01 8.31E + 02 9.42E + 04 3.89E + 02 1.40E + 05
4.36E + 03 1.70E + 03 2.20E + 03 2.26E + 05 3.88E + 05 4.99E + 04 5.00E + 01 7.44E + 02 8.42E + 04 3.56E + 02 1.25E + 05
D D D D D D C D D D D
10,000 100
1.4 370
7.71E + 03 1.20E + 01
7.29E + 03 1.13E + 01
6.62E + 03 1.02E + 01
D C
The chemical behavior of spilled HNS can be calculated by considering factors such as the volatilization, photo-degradation, biodegradation, background concentration, and sedimentation, of HNS. The
details can be found in MAMPEC Handbook (van Hattum et al., 2016). In this study, the environmental concentrations were estimated using the MAMPEC model with the maximum exchange volume and the
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Table 6 Results of PNEC, hazard quotient and aquatic risk characterization (for the spill amount of 10,000 tonnages) of priority HNS in Gwang-yang port. Priority rank
1 2 3 8 10 13 14 18 19 31 37 45 48 53 57 68 76 85
HNS name
Coal tar Phenol Ammonia aqueous (28% or less) Acrylonitrile Sulfur (molten) Acetone Ethyl alcohol Sulphuric acid Creosote (coal tar) Methyl alcohol Ethylene dichloride Hydrochloric acid Acetic acid Phosphoric acid Nitric acid (< 70%) Sodium hydroxide solution Vinyl acetate Methyl methacrylate
PNEC source
Assessment factor
Taxonomic group
Acute or chronic
Endpoint
Fish Fish Crustacea
Chronic Chronic Chronic
LOEL LC50 NOEC
100 10 100
Crustacea Other Fish Other Crustacea Crustacea Fish Fish Crustacea Crustacea Fish Fish Crustacea
Chronic Chronic Chronic Chronic Chronic Chronic Chronic Chronic Acute Chronic Acute Acute Acute
NOEC LC50 LOEC NOEC NOEC EC50 NOEC NOEC LC50 NOEC LC50 LC50 EC50
Fish Crustacea
Acute Chronic
LC50 NOEC
PNEC (ug/L)
Hazard Quotient (PEC/PNEC)
Aquatic risk characterization (A/B/C/D/E)
Neap tide
30 days mean
Spring tide
19 7 5.5
5.95E + 00 1.10E + 03 1.49E + 03
5.11E + 00 9.03E + 02 1.24E + 03
4.69E + 00 8.00E + 02 1.10E + 03
B D D
100 100 100 100 100 100 10 50 10,000 100 10,000 1,000 10,000
5 15.4 49.5 1 1.3 0.446 10 36.4 24 320 6 72 4.038
1.18E + 03 2.44E + 03 8.30E + 03 1.01E + 05 2.28E + 05 – 2.25E + 04 9.73E + 00 1.24E + 01 3.53E + 02 4.93E + 04 5.86E + 01 7.33E + 04
1.02E + 03 2.05E + 02 7.11E + 02 8.56E + 04 1.87E + 05 – 1.90E + 04 8.38E + 00 1.01E + 01 2.98E + 02 4.05E + 04 4.99E + 01 6.02E + 04
9.42E + 02 1.86E + 02 6.48E + 02 7.73E + 04 1.66E + 05 – 1.72E + 04 7.69E + 00 8.67E + 00 2.68E + 02 3.60E + 04 4.57E + 01 5.35E + 04
D D D D D E D B C D D C D
10,000 100
1.4 370
1.31E + 03 3.14E + 00
1.13E + 03 2.70E + 00
1.04E + 03 2.49E + 00
D B
Table 7 Results of PNEC, hazard quotient and aquatic risk characterization (for the spill amount of 10,000 tonnages) of priority HNS in Daesan port. Priority rank
1 2 10 13 14 31 37 48 57 68 76 85
HNS name
Coal tar Phenol Sulfur (molten) Acetone Ethyl alcohol Methyl alcohol Ethylene dichloride Acetic acid Nitric acid (< 70%) Sodium hydroxide solution Vinyl acetate Methyl methacrylate
PNEC source
Assessment factor
Taxonomic group
Acute or chronic
Endpoint
Fish Fish Other Fish Other Fish Fish Crustacea Fish Crustacea
Chronic Chronic Chronic Chronic Chronic Chronic Chronic Chronic Acute Acute
LOEL LC50 LC50 LOEC NOEC NOEC NOEC NOEC LC50 EC50
100 10 100 100 100 10 50 100 1,000 10,000
Fish Crustacea
Acute Chronic
LC50 NOEC
10,000 100
PNEC (ug/L)
Hazard quotient (PEC/PNEC)
Aquatic risk characterization (A/B/C/D/E)
Neap tide
30 days mean
Spring tide
19 7 15.4 49.5 1 10 36.4 320 72 4.038
5.26E + 00 2.81E + 02 2.94E + 02 3.33E + 02 3.40E + 04 7.51E + 03 8.13E + 00 1.12E + 02 5.94E + 01 1.86E + 04
3.17E + 00 1.69E + 02 1.77E + 02 2.00E + 02 2.04E + 04 4.50E + 03 4.89E + 00 6.69E + 01 3.57E + 01 1.12E + 04
2.36E + 00 1.25E + 02 1.31E + 02 1.49E + 02 1.52E + 04 3.35E + 03 3.63E + 00 5.00E + 01 2.65E + 01 8.30E + 03
B D D D D D B D C D
1.4 370
1.07E + 03 1.57E + 00
6.43E + 02 9.43E-01
4.79E + 02 7.03E-01
D B
Table 8 Classification of the results on initial marine environmental risk assessment. Classification
Hazard quotient
Explanation
A B
<1 1–10
C D E
10–100 > 100 –
Harmful effects are not likely Harmful effects cannot be ruled out Further testing and assessment requiredImmediate further testing and assessment required Major concern, risk reduction measures should be required Harmful effects cannot be assessed in current situation
tide, and the spring tide from the Korea Hydrographic and Oceanographic Agency (KHOA). Fig. 4 shows the measuring points and the measured tidal current characteristics at the three ports. The water and sediment characteristics data were obtained from the Marine Environmental Information System (MEIS) co-operated by the Ministry of Oceans & Fisheries of Korea and the Korea Environmental Management Corporation (KOEM). The maximum spill amount of HNS is set as 10,000 tonnages as mentioned above and suggested in our previous study (Lee and Jung, 2013). Using the MAMPEC and the information,
spilled HNS for each port (i.e., Ulsan port, Gwangyang port, and Daesan port), according to the HNS spill scenario. In order to calculate the environmental concentrations, the harbor type should be determined in advance of the simulation. Fig. 3 shows actual photos of the three ports and the harbor type, selected by considering its topographic conditions. The Ulsan and the Gwangyang ports are considered commercial harbors, while the Daesan port is considered an open harbor. The hydrodynamic behavior was calculated using the average value of the real sea data such as the tidal current, the period of tide, the neap 211
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acid, methanol, phosphoric acid, and sodium hydroxide solution are likely to have a high concentration at an early stage, which has high toxic effects on marine organisms. As shown in Tables 5–7, the HQs of most substances are high due to the assumption of 10,000 tonnages of HNS spill. In this study, an initial environmental risk assessment was conducted using the worst case HNS spill (i.e., 10,000 tonnages). Therefore, we can readily perform the initial environmental risk assessment for further investigations using real-time monitoring of HNS spill accidents, because we developed the systems for calculating PEC and PNEC with DB of physical/chemical properties of HNS (i.e., 158 priority HNS in Korea). Initial environmental risk assessment for HNS spill accidents were developed in this study. The initial environmental risk assessment is a preliminary analysis tool for further detailed examining of the HNS risk assessment. To apply the developed method, we selected the three major ports (i.e., Ulsan port, Gwangyang port, and Daesan port) of HNS traffic around the Korean Peninsula. The data for analyzing the initial environmental risk assessment were from the credible Korean national providers (i.e., the Ministry of Oceans and Fisheries and the Korea Hydrographic and Oceanographic Agency). To consider the worst possible HNS spill accident, the HNS spill amount is assumed to be 10,000 tonnages which is regarded as the maximum HNS spill amount in Korea. The results of the initial environmental risk assessment show that the highly soluble HNS are more harmful to marine ecosystems during neap tide because the seawater exchange volume is the smallest. It should be noted that this study is based on a worst case HNS spill accident, not a specific actual HNS spill accident. Nevertheless, the systems developed in this study, which could calculate the PEC and PNEC with the physical/chemical properties of 158 priority HNS, can readily perform the initial environmental risk assessment for future HNS spill accidents. Our results also help enlarge the understanding of the environmental risk assessment of an HNS spill accident.
Table 9 Criteria for identification of PBT substances (IMO, 2017). Criterion Persistent Bioaccumulation Toxicity (Environment) Toxicity (Human health, CMR)
PBT Criteria Marine water Marine sediment BCF Log Pow Chronic NOEC Carcinogenic Mutagenic Reproduction
60 days 180 days > 2,000 >3 < 0.01 mg/L Category 1A or 1B Category 1A or 1B Category 1A, 1B or 2
the PECs were calculated. The results show that the PECs are relatively higher in the cases of the highly soluble materials such as the acids, bases, and alcohols. The PEC at Daesan port is relatively lower than those at other ports, which is attributed that the Daesan port is open harbour at which the seawater exchange volume is the greater than those of other ports. Tables 2–4 show the characteristics and PEC calculation results of priority HNS at each port. It should be noted that the X, Y, and Z in Tables 2–4 are; X: Noxious liquid substances (NLS) which, if discharged into the sea, are deemed to present a major hazard to either marine resources or human health and, therefore, justify the prohibition of the discharge into the marine environment; Y: NLS which, if discharged into the sea, are deemed to present a hazard to either marine resources or human health or cause harm to amenities or other legitimate uses of the sea and therefore justify a limitation on the quality and quantity of the discharge into the marine environment; Z: NLS which, if discharged into the sea, are deemed to present a minor hazard to either marine resources or human health and therefore justify less stringent restrictions on the quality and quantity of the discharge into the marine environment (MEPC, 2006). To establish the PNEC DB for this study, we refer to IMO BWM (which was updated, 20 July 2017) (IMO, 2017). According to the IMO BWM, to assess the HNS effects on the marine environment, an appropriate PNEC should be derived. A PNEC could be derived from the level at which, the marine ecosystem is not affected by the toxicity of long-term exposures. The definition of PNEC is the lowest LC50, EC50 or NOEC divided by an AF, where the LC50 is the median lethal concentration, the EC50 is the median effective concentration, the NOEC is the no observed effect concentration, and the AF is the assessment factor. As shown the bottom-left of Fig. 5, the AF values were allocated in five stages, ranging from 10 to 10,000, depending on the number of available toxicological data. In cases where a comprehensive data-set is available, the PNEC could be derived using a mathematical model of the sensitivity distribution among species. The guideline details for the assessment factors has been reported in the IMO BMW (IMO, 2017). In this study, we developed the ‘HNS Eco-Toxicity Database’ system (the details are not discussed here), which includes the physical and chemical properties and the eco-toxicity data as shown in the right side of Fig. 5. As the results, the PNEC of priority HNS at the three ports were calculated using the definition of the PNEC as shown in Tables 5–7. The initial environmental risk assessment results are represented in Table 8, there are five stages reflecting the hazard analysis, the characteristics of the persistence, bioaccumulation, and toxicity (PBT) of the HNS. For the PBT, the criteria for the risk assessments of BWMS have been applied as shown in Table 9 (IMO, 2017). As a result of the initial environmental risk assessment of HNS in the three major ports of Korea, all HNS were classified as needing a detailed evaluation and additional testing with HQ > 1, because the spill amount of HNS is 10,000 tonnages of HNS is assumed to present the worst case and could be used to establish a preparedness and national contingency plan in the Korean Peninsula. Also, the HQ of the neap tide case was applied to classify the risk characterization of HNS, to consider the worst case in which the seawater exchange volume is the smallest. The results show that highly soluble HNS such as ethanol, sulphuric
Acknowledgment This work is carried out as a part of the study on “Development of Management Technology for HNS Accident,” funded by the Ministry of Oceans and Fisheries, South Korea. References Cunha, I., Oliveira, H., Neuparth, T., Torres, T., Santos, M.M., 2016. Fate, behaviour and weathering of priority HNS in the marine environment: an online tool. Mar. Pollut. Bull. 111, 330–338. Fernández-Macho, J., 2016. Risk assessment for marine spills along European coastlines. Mar. Pollut. Bull. 113, 200–210. Fuhrer, M., Péron, O., Höfer, T., Morrissette, M., Le Floch, S., 2012. Offshore experiments on styrene spillage in marine waters for risk assessment. Mar. Pollut. Bull. 64, 1367–1374. GESAMP, 2014. Revised GESAMP Hazard Evaluation Procedure for Chemical Substances Carried by Ships (IMO/FAO/UNESCO-IOC/WMO/IAEA/UN/UNEP/UNIDO/UNDP). Joint Group of Experts on the Scientific Aspects of Marine Environmental Protection (GESAMP No. 64). GESAMP, 2016. GESAMP Composite List 2016 Issued June 2016 as PPR.1/Circ.3. Replaces all Previous Versions. http://www.imo.org/en/OurWork/Environment/ PollutionPrevention/ChemicalPollution/Documents/GESAMP%20CompList %202016.pdf, Accessed date: 12 August 2018. Guillén, D., Ginebreda, A., Farré, M., Darbra, R.M., Petrovic, M., Gros, M., Barceló, D., 2012. Prioritization of chemicals in the aquatic environment based on risk assessment: analytical, modeling and regulatory perspective. Sci. Total Environ. 440, 236–252. Haimes, Y.Y., 2009. On the complex definition of risk: a systems-based approach. Risk Anal. 29, 1647–1654. Harold, P.D., de Souza, A.S., Louchart, P., Russell, D., Brunt, H., 2014. Development of a risk-based prioritisation methodology to inform public health emergency planning and preparedness in case of accidental spill at sea of hazardous and noxious substances (HNS). Environ. Int. 72, 157–163. IMO, 2017. International Convention for the Control and Management of Ships' Ballast Water and Sediments (BWM). http://www.imo.org/en/About/Conventions/ ListOfConventions/Pages/International-Convention-for-the-Control-andManagement-of-Ships'-Ballast-Water-and-Sediments-(BWM).aspx, Accessed date: 12 August 2018.
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Neuparth, T., Moreira, S.M., Santos, M.M., Reis-Henriques, M.A., 2012. Review of oil and HNS accidental spills in Europe: identifying major environmental monitoring gaps and drawing priorities. Mar. Pollut. Bull. 64, 1085–1095. Neuparth, T., Capela, R., Rey-Salgueiro, L., Moreira, S.M., Santos, M.M., Reis-Henriques, M.A., 2013. Simulation of a hazardous and noxious substances (HNS) spill in the marine environment: lethal and sublethal effects of acrylonitrile to the European seabass. Chemosphere 93, 978–985. Radović, J.R., Rial, D., Lyons, B.P., Harman, C., Viñas, L., Beiras, R., Readman, J.W., Thomas, K.V., Bayona, J.M., 2012. Post-incident monitoring to evaluate environmental damage from shipping incidents: chemical and biological assessments. J. Environ. Manag. 109, 136–153. SuterII, G.W., 1995. Introduction to ecological risk assessment for qauatic toxic effects. In: Fundamentals of Aquatic Toxicology Effects, Environmental Fate, and Risk Assessment, 2nd ed. CRC Press, Boca Raton, Florida, pp. 803–816. Takeda, F., Mano, H., Suzuki, Y., Okamoto, S., 2015. Initial environmental risk assessment of Japanese PRTR substances in treated wastewater. J. Water Environ. Technol. 13, 301–312. UNCTAD, 2017. Review of Maritime Transport. United Nations Conference on Trade and Development (UNCTAD). Valdor, P.F., Gómez, A.G., Puente, A., 2015. Environmental risk analysis of oil handling facilities in port areas. Application to Tarragona harbor (NE Spain). Mar. Pollut. Bull. 90, 78–87. van Hattum, B., van Gils, J., Markus, A., Elzinga, H., Jansen, M., Baart, A., 2016. MAMPEC Handbook. Deltares, Delft, The Netherlands.
IPIECA, 2000. A Guide to Contingency Planning for Oil Spills on Water. International Petroleum Industry Environmental Conservation Association. Jang, H.-L., Ha, M.-J., Jang, H.-S., Yun, J.-H., Lee, E.-B., Lee, M., 2017. Design and implementation of an HNS accident tracking system for rapid decision making. J. Kor. Soc. Mar. Environ. Safety 23, 168–176 (in Korean). KCG, 2018. Korea Coast Guard. www.kcg.go.kr, Accessed date: 12 August 2018. Kim, Y.-R., Choi, J.-Y., Son, M.-H., Oh, S., Lee, M., Lee, S., 2016. Prioritizing noxious liquid substances (NLS) for preparedness against potential spill incidents in Korea coastal waters. J. Kor. Soc. Mar. Environ. Safety 22, 846–853 (in Korean). Kirby, M.F., Gioia, R., Law, R.J., 2014. The principles of effective post-spill environmental monitoring in marine environments and their application to preparedness assessment. Mar. Pollut. Bull. 82, 11–18. Koo, J., Jung, J.-Y., Lee, S., Lee, M., Chang, J., 2015. Development of waterborne oil spill sensor based on printed ITO nanocrystals. Mar. Pollut. Bull. 98, 130–136. Lee, M., Jung, J.-Y., 2013. Risk assessment and national measure plan for oil and HNS spill accidents near Korea. Mar. Pollut. Bull. 73, 339–344. Lee, M., Jung, J.-Y., 2015. Pollution risk assessment of oil spill accidents in Garorim Bay of Korea. Mar. Pollut. Bull. 100, 297–303. MEPC, 2006. International Maritime Organization, Marine Environment Protection Committee, 55th Session Agenda Item 23 Annex 28, Consolidated Text of the Draft Amendments to Chapter 17, 18 and 19 of the IBC Code, MEPC55/23/Add.1. pp. 221–304. Neuparth, T., Moreira, S., Santos, M.M., Reis-Henriques, M.A., 2011. Hazardous and noxious substances (HNS) in the marine environment: prioritizing HNS that pose major risk in a European context. Ma. Pollut. Bull. 62, 21–28.
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Baseline
Initial environmental risk assessment of hazardous and noxious substances (HNS) spill accidents to mitigate its damages
T
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Young-Ryun Kima,1, Moonjin Leeb,1, Jung-Yeul Jungb, , Tae-Won Kima, Daejoong Kimc a
Marine Eco-Technology Institute, Busan 48520, Republic of Korea Marine Safety and Environmental Research Division, Korea Research Institute of Ships and Ocean Engineering, KIOST, Daejeon 34103, Republic of Korea c Department of Mechanical Engineering, Sogang University, Seoul 04107, Republic of Korea b
A R T I C LE I N FO
A B S T R A C T
Keywords: Exposure assessment HNS Initial environmental risk assessment Marine ecosystem Spill accident Toxicity assessment
In this study, a system was established to perform an initial environmental risk assessment of hazardous and noxious substances (HNS) spill accidents. Initial environmental risk assessment was performed using exposure and hazard assessments. An integrated hydrodynamic and chemical fate model was used to predict HNS concentrations at harbors, taking into account local environmental conditions. To consider the worst case HNS spill accident, the spill amount of 10,000 tonnages, was used for this study. The results show that highly soluble HNS are fatal to marine organisms during the neap tide. The results were based on a hypothetical worst case HNS spill accident and, not any specific actual HNS spill accident. Nevertheless, the method and system developed in this study, which includes the physical/chemical properties of 158 priority HNS, can be readily used to perform an initial environmental risk assessment for future HNS spill accidents.
Global seaborne trade continues to grow with developments in the world economy and trade. For example, a compound annual growth rate of 3.2% between 2017 and 2022 has been projected by the United Nations Conference on Trade and Development (UNCTAD) (UNCTAD, 2017). The Republic of Korea is the 7th largest ownership country and the Port of Busan is the 6th largest container port (UNCTAD, 2017). Also the shipping quantity of hazardous and noxious substances (HNS) in Korean ports during 2014–2015 was approximately 90 million tons (Jang et al., 2017). HNS spill accidents can cause hazards to the environment, human health, living resources, and amenities. To mitigate the hazards and damages from HNS spill accidents, initial environmental risk assessment is essential; it is an important step towards making a risk characterization and aiding with decision-making about further assessments by analyzing and assessing the exposure and hazard assessments. Environmental risk assessment and monitoring after HNS spill accidents have been recognized as the most effective methods to reduce environmental damages and to help in preparation of the contingency plan (Neuparth et al., 2011; Guillén et al., 2012; Neuparth et al., 2012; Radović et al., 2012; Lee and Jung, 2013; Neuparth et al., 2013; Kirby et al., 2014; Lee and Jung, 2015; Valdor et al., 2015; Cunha et al., 2016; Fernández-Macho, 2016). There are various studies on environmental risk assessment and monitoring after HNS spill accidents (Fuhrer et al.,
2012; Neuparth et al., 2012; Radović et al., 2012; Lee and Jung, 2013; Kirby et al., 2014; Koo et al., 2015; Takeda et al., 2015). However, there are only a few initial environmental risk assessment of HNS spills in Korea, as well as worldwide. In this study, we suggest a method to carry out the initial environmental risk assessment using exposure and hazard assessments. The results show that highly soluble HNS spills are fatal to marine organisms during the neap tide. The initial step in assessing the environmental risk of an HNS spill accident involves using the early stage information to identify known chemicals that require a more detailed risk assessment of their impact on ecosystems and human health. The initial environmental risk assessment is carried out through exposure and hazard assessments, and then the risk priority is determined using the results of both assessments. The exposure assessment is that estimates the exposure resulting from a release or occurrence of a chemical, physical, or biological agent in a medium. And it strives to quantify, using measurement or predictive tools, the magnitude, duration, and extent of exposure (SuterII, 1995). The hazard assessment is a preliminary activity that helps define the assessment problem by determining which environmental components are potentially exposed to toxic concentrations and how those components might be affected by the exposure (SuterII, 1995). In this study, an initial environmental risk assessment of marine ecosystems was performed based on the effects of HNS spills occurring
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Corresponding author. E-mail address: [email protected] (J.-Y. Jung). 1 Equally contributed authors. https://doi.org/10.1016/j.marpolbul.2018.12.044 Received 17 September 2018; Received in revised form 26 November 2018; Accepted 21 December 2018 0025-326X/ © 2018 Elsevier Ltd. All rights reserved.
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of HNS in the environment. A worst case HNS spill accident has not occurred in the waters surrounding the Korean Peninsula (Lee and Jung, 2013; KCG, 2018). However, the possibility of a worst case HNS spill accident may increase due to the increasing volume of maritime HNS traffic. Therefore, it is necessary to estimate the maximum possible HNS spill amount. In Korea, the deadweight tonnage (DWT) of the largest HNS carrier is 60,000, so the maximum spill amount could be assumed of 10,000 tonnages (which was from a correlation 3 × 10−7 × DWT2 + 0.1362 × DWT (R2 = 0.9926) to estimate leakage amounts of loaded HNS for a grounding accident) (IPIECA, 2000; Lee and Jung, 2013). However, the maximum possible spill amount varies by country. In the United States, the maximum possible spill amount is considered to be the total amount of cargo. In the case of Japan, it is 9% of DWT. In Canada, the national control capacity of an HNS spill amount is 10,000 tonnages. There are more than 10 HNS traffic ports in Korea. We observed the HNS species and amount of maritime transportation occurring at each of 13 major ports as shown in Table 1. To carry out the initial environmental risk assessment, three ports (i.e. the ports are Ulsan port, Gwangyang port and Daesan port) were selected based on their total traffic quantity, where the traffic quantity of HNS was > 14 M tonnages at each port. We already developed the HNS priority scoring and ranking system in our previous study (Kim et al., 2016). The risk prioritization is performed using the combined score (i.e., the times of the hazard and the exposure), which can be described as (Kim et al., 2016),
Table 1 Maritime transportation data at major ports in Korea during 2014–2015 (Kim et al., 2016). Port name
No. of HNS
Quantity, tons
Ulsan Gwangyang Daesan Pyeongtaek Incheon Masan Gunsam Busan Yeosu Pohang Mokpo Jeju Total
108 91 32 45 19 3 10 55 34 3 1 2 158
38,273,680 21,868,160 14,940,481 6,695,806 4,035,371 2,143,879 450,933 413,616 369,706 65,604 61,736 34,941 89,353,913
The bold was highlighted to emphasize the target ports and its imformation.
during loading or unloading at ports, which is different from previous risk assessment studies of HNS spill accidents (Lee and Jung, 2013; Takeda et al., 2015; Fernández-Macho, 2016). To estimate the maximum spill amount, a value used in calculations in this study, we used the results of our previous study in which the maximum HNS spill amount is estimated based on the maximum dead-weights of HNS carriers and credible regression value from the International Petroleum Industry Environmental Conservation Association (IPIECA) (IPIECA, 2000; Lee and Jung, 2013). We used a hydrodynamic model, based on the maximum spill amount, to predict the concentration and behavior
Risk = Toxicity × Exposure
Fig. 1. A schematic diagram of the HNS scoring and ranking systems (Kim et al., 2016). 206
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Fig. 2. The MAMPEC model input and output display.
Fig. 3. Real pictures of the each harbor and harbor type selected in this study.
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Fig. 4. Measuring stations of the water, sediment and tidal current characteristics. Table 2 Characteristics and PEC calculation results (for the spill amount of 10,000 tonnages) of priority HNS at Ulsan port. Priority rank
1 2 3 8 10 13 14 18 31 37 48 53 57 68 76 85 a b
HNS name
Coal tar Phenol Ammonia aqueous (28% or less) Acrylonitrile Sulfur (molten) Acetone Ethyl Alcohol Sulphuric acid Methyl alcohol Ethylene dichloride Acetic acid Phosphoric acid Nitric acid (< 70%) Sodium hydroxide solution Vinyl acetate Methyl methacrylate
CASRN
8007-45-2 108-95-2 7664-41-7 107-13-1 7704-34-9 67-64-1 64-17-5 7664-93-9 67-56-1 107-06-2 64-19-7 7664-38-2 7697-37-2 1310-73-2 108-05-4 80-62-6
MARPOL Pollution category (MEPC, 2006)
X Y Y Y Z Z Z Y Y Y Z Z Y Y Y Y
Physical behaviora
S S DE DE S DE D D DE SD D D D D ED ED
Biodegradationb
NR R R NR Inorg R R Inorg R NR R Inorg Inorg Inorg R R
PEC (ug/L) Neap tide
30 days mean
Spring tide
7.11E + 02 1.58E + 04 1.81E + 04 2.56E + 04 2.98E + 04 1.29E + 05 2.68E + 05 6.03E + 05 5.93E + 05 2.12E + 03 2.83E + 05 6.03E + 05 2.95E + 04 6.03E + 05 1.08E + 04 4.45E + 03
6.74E + 02 1.48E + 04 1.70E + 04 2.42E + 04 2.85E + 04 1.21E + 05 2.52E + 05 5.65E + 05 5.57E + 05 2.01E + 03 2.66E + 05 5.65E + 05 2.80E + 04 5.65E + 05 1.02E + 04 4.19E + 03
6.14E + 02 1.32E + 04 1.52E + 04 2.18E + 04 2.62E + 04 1.09E + 05 2.26E + 05 5.05E + 05 4.99E + 05 1.82E + 03 2.38E + 05 5.05E + 05 2.56E + 04 5.05E + 05 9.27E + 03 3.77E + 03
S: Sinks, SD: Sinks/Dissolves, D: Dissolves, DE: Dissolves/Evaporates, ED: Evaporates/Dissolves (GESAMP, 2014, 2016). R: readily biodegradable, NR: not readily biodegradable, Inorg: Inorganic substance (GESAMP, 2014, 2016).
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Table 3 Characteristics and PEC calculation results (for the spill amount of 10,000 tonnages) of priority HNS at Gwang-yang port. Priority rank
1 2 3 8 10 13 14 18 19 31 37 45 48 53 57 68 76 85 a b
HNS name
CASRN
Coal tar Phenol Ammonia aqueous (28% or less) Acrylonitrile Sulfur (molten) Acetone Ethyl Alcohol Sulphuric acid Creosote (coal tar) Methyl alcohol Ethylene dichloride Hydrochloric acid Acetic acid Phosphoric acid Nitric acid (< 70%) Sodium hydroxide solution Vinyl acetate Methyl methacrylate
8007-45-2 108-95-2 7664-41-7 107-13-1 7704-34-9 67-64-1 64-17-5 7664-93-9 8001-58-9 67-56-1 107-06-2 7647-01-0 64-19-7 7664-38-2 7697-37-2 1310-73-2 108-05-4 80-62-6
MARPOL Pollution category (MEPC, 2006)
X Y Y Y Z Z Z Y X Y Y Z Z Z Y Y Y Y
Physical behaviora
S S DE DE S DE D D S DE SD DE D D D D ED ED
Biodegradationb
NR R R NR Inorg R R Inorg NR R NR Inorg R Inorg Inorg Inorg R R
PEC (ug/L) Neap tide
30 days mean
Spring tide
1.13E + 02 7.70E + 03 8.22E + 03 5.90E + 03 3.76E + 04 4.11E + 05 1.01E + 05 2.96E + 05 – 2.25E + 05 3.54E + 02 2.98E + 02 1.13E + 05 2.96E + 05 4.22E + 03 2.96E + 05 1.83E + 03 1.16E + 03
8.92E + 01 5.60E + 03 6.07E + 03 4.71E + 03 2.87E + 03 3.21E + 04 7.73E + 04 2.16E + 05 1.72E + 05 2.80E + 02 2.08E + 02 8.57E + 04 2.16E + 05 3.29E + 03 2.16E + 05 1.45E + 03 9.21E + 02
9.70E + 01 6.32E + 03 6.81E + 03 5.12E + 03 3.15E + 03 3.52E + 04 8.56E + 04 2.43E + 05 – 1.90E + 05 3.05E + 02 2.42E + 02 9.53E + 04 2.43E + 05 3.59E + 03 2.43E + 05 1.58E + 03 1.00E + 03
Neap tide
30 days mean
Spring tide
1.00E + 02 1.97E + 03 4.52E + 03 1.65E + 04 3.40E + 04 7.51E + 04 2.96E + 02 3.57E + 04 4.28E + 03 7.51E + 04 1.50E + 03 5.81E + 02
6.02E + 01 1.18E + 03 2.72E + 03 9.90E + 03 2.04E + 04 4.50E + 04 1.78E + 02 2.14E + 04 2.57E + 03 4.51E + 04 9.00E + 02 3.49E + 02
4.48E + 01 8.77E + 02 2.02E + 03 7.37E + 03 1.52E + 04 3.35E + 04 1.32E + 02 1.60E + 04 1.91E + 03 3.35E + 04 6.70E + 02 2.60E + 02
S: Sinks, SD: Sinks/Dissolves, D: Dissolves, DE: Dissolves/Evaporates, ED: Evaporates/Dissolves (GESAMP, 2014, 2016). R: readily biodegradable, NR: not readily biodegradable, Inorg: Inorganic substance (GESAMP, 2014, 2016).
Table 4 Characteristics and PEC calculation results (for the spill amount of 10,000 tonnages) of priority HNS at Daesan port. Priority rank
1 2 10 13 14 31 37 48 57 68 76 85 a b
HNS name
Coal tar Phenol Sulfur (molten) Acetone Ethyl Alcohol Methyl alcohol Ethylene dichloride Acetic acid Nitric acid (< 70%) Sodium hydroxide solution Vinyl acetate Methyl methacrylate
CASRN
8007-45-2 108-95-2 7704-34-9 67-64-1 64-17-5 67-56-1 107-06-2 64-19-7 7697-37-2 1310-73-2 108-05-4 80-62-6
Marpol Pollution category (MEPC, 2006)
X Y Z Z Z Y Y Z Y Y Y Y
Physical behaviora
S S S DE D DE SD D D D ED ED
GESAMP* biodegradationb
NR R Inorg R R R NR R Inorg Inorg R R
PEC (ug/L)
S: Sinks, SD: Sinks/Dissolves, D: Dissolves, DE: Dissolves/Evaporates, ED: Evaporates/Dissolves (GESAMP, 2014, 2016). R: readily biodegradable, NR: not readily biodegradable, Inorg: Inorganic substance (GESAMP, 2014, 2016).
the risk characteristic can be calculated through the Hazard Quotient (HQ, =PEC/PNEC). For analyzing the behavior of the spilled HNS, we used the integrated hydrodynamic and chemical fate model MAMPEC. The MAMPEC is a steady-state 2D integrated hydrodynamic and chemical fate model, originally developed for the exposure assessment of antifouling substances (van Hattum et al., 2016); however, it was revised by the IMO and the Joint Group of Experts on the Scientific Aspects of Marine Environmental Protection (GESAMP) in 2011 for the purpose of assessing the chemical effect of ballast water treatment systems (BWTS) on the marine ecosystem. The revised model has been recommended for risk assessment during the basic and final approval of BWTS by the IMO MEPC. The model can predict the concentration distribution of HNS in the four marine environments (i.e., the open harbor, marina, open sea, and commercial harbor) as shown in the top-left portion of Fig. 2. MAMPEC calculates the total water exchange volume (Ve, m3) as the sum of the tidal prism (Vt) and the exchange volumes due to the horizontal eddy in the harbor entrance (Vh), due to density currents (Vd), wind-driven exchange (Vw), non-tidal exchange flow (Vnt) and the extra flush flow from within the harbor (Vef), which is expressed as follows (van Hattum et al., 2016);
where the hazard is expressed as a function of acute toxicity, chronic toxicity, carcinogenic toxicity, and other toxicity, and the exposure is expressed as a function of persistence, bioaccumulation and transportation. The details of the scoring and ranking system were described in our previous study (Kim et al., 2016) and the schematic diagram is shown in Fig. 1. This method is similar to previous studies (Haimes, 2009; Harold et al., 2014). Using the system described above and information about HNS traffic in Korea, we prioritized 158 HNS, which will be used to establish the preparedness and contingency plans for HNS spill accidents in Korea. Eventually, the prioritization will be expanded to 545 species of HNS traffic in Korea. Among the current 158 priority HNS, there are 16, 18, and 12 of zero-tier priority HNS traffic at Ulsan port, Gwangyang port, and Daesan port, respectively. The total species of zero-tier priority HNS is considered to be 18 because almost all HNS traffic overlapped between ports. The initial environmental risk assessment of an HNS spill accident is performed based on the approach and the prioritization described above. First, the predicted environmental concentration (PEC) is calculated using the integrated hydrodynamic and chemical fate model (van Hattum et al., 2016). Second, the predicted no-effect concentration (PNEC), at which HNS will likely have no toxic effect on marine organisms, is evaluated to determine possible HNS toxicity. Then, finally,
Ve = Vt + Vh + Vd + Vw + Vnt + Vef 209
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Fig. 5. Assignment of assessment factors (AF) used for deriving PNEC values (IMO, 2017) and the template for HNS eco-toxicity database.
Table 5 Results of PNEC, hazard quotient and aquatic risk characterization (for the spill amount of 10,000 tonnages) of priority HNS in Ulsan port. Priority rank
1 2 3 8 10 13 14 18 31 37 48 53 57 68 76 85
HNS name
Coal tar Phenol Ammonia aqueous (< 28%) Acrylonitrile Sulfur (molten) Acetone Ethyl alcohol Sulphuric acid Methyl alcohol Ethylene dichloride Acetic acid Phosphoric acid Nitric acid (< 70%) Sodium hydroxide solution Vinyl acetate Methyl methacrylate
PNEC source
Assessment factor
Taxonomic group
Acute or chronic
Endpoint
Fish Fish Crustacea
Chronic Chronic Chronic
LOEL LC50 NOEC
100 10 100
Crustacea Other Fish Other Crustacea Fish Fish Crustacea Fish Fish Crustacea
Chronic Chronic Chronic Chronic Chronic Chronic Chronic Chronic Acute Acute Acute
NOEC LC50 LOEC NOEC NOEC NOEC NOEC NOEC LC50 LC50 EC50
Fish Crustacea
Acute Chronic
LC50 NOEC
PNEC (ug/L)
Hazard Quotient (PEC/PNEC)
Aquatic risk characterization (A/B/C/D/E)
Neap tide
30 days mean
Spring tide
19 7 5.5
3.74E + 01 2.26E + 03 3.29E + 03
3.55E + 01 2.11E + 03 3.09E + 03
3.23E + 01 1.89E + 03 2.76E + 03
C D D
100 100 100 100 100 10 50 100 10,000 1,000 10,000
5 15.4 49.5 1 1.3 10 36.4 320 6 72 4.038
5.12E + 03 1.94E + 03 2.61E + 03 2.68E + 05 4.64E + 05 5.93E + 04 5.82E + 01 8.84E + 02 1.01E + 05 4.10E + 02 1.49E + 05
4.84E + 03 1.85E + 03 2.44E + 03 2.52E + 05 4.35E + 05 5.57E + 04 5.52E + 01 8.31E + 02 9.42E + 04 3.89E + 02 1.40E + 05
4.36E + 03 1.70E + 03 2.20E + 03 2.26E + 05 3.88E + 05 4.99E + 04 5.00E + 01 7.44E + 02 8.42E + 04 3.56E + 02 1.25E + 05
D D D D D D C D D D D
10,000 100
1.4 370
7.71E + 03 1.20E + 01
7.29E + 03 1.13E + 01
6.62E + 03 1.02E + 01
D C
The chemical behavior of spilled HNS can be calculated by considering factors such as the volatilization, photo-degradation, biodegradation, background concentration, and sedimentation, of HNS. The
details can be found in MAMPEC Handbook (van Hattum et al., 2016). In this study, the environmental concentrations were estimated using the MAMPEC model with the maximum exchange volume and the
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Table 6 Results of PNEC, hazard quotient and aquatic risk characterization (for the spill amount of 10,000 tonnages) of priority HNS in Gwang-yang port. Priority rank
1 2 3 8 10 13 14 18 19 31 37 45 48 53 57 68 76 85
HNS name
Coal tar Phenol Ammonia aqueous (28% or less) Acrylonitrile Sulfur (molten) Acetone Ethyl alcohol Sulphuric acid Creosote (coal tar) Methyl alcohol Ethylene dichloride Hydrochloric acid Acetic acid Phosphoric acid Nitric acid (< 70%) Sodium hydroxide solution Vinyl acetate Methyl methacrylate
PNEC source
Assessment factor
Taxonomic group
Acute or chronic
Endpoint
Fish Fish Crustacea
Chronic Chronic Chronic
LOEL LC50 NOEC
100 10 100
Crustacea Other Fish Other Crustacea Crustacea Fish Fish Crustacea Crustacea Fish Fish Crustacea
Chronic Chronic Chronic Chronic Chronic Chronic Chronic Chronic Acute Chronic Acute Acute Acute
NOEC LC50 LOEC NOEC NOEC EC50 NOEC NOEC LC50 NOEC LC50 LC50 EC50
Fish Crustacea
Acute Chronic
LC50 NOEC
PNEC (ug/L)
Hazard Quotient (PEC/PNEC)
Aquatic risk characterization (A/B/C/D/E)
Neap tide
30 days mean
Spring tide
19 7 5.5
5.95E + 00 1.10E + 03 1.49E + 03
5.11E + 00 9.03E + 02 1.24E + 03
4.69E + 00 8.00E + 02 1.10E + 03
B D D
100 100 100 100 100 100 10 50 10,000 100 10,000 1,000 10,000
5 15.4 49.5 1 1.3 0.446 10 36.4 24 320 6 72 4.038
1.18E + 03 2.44E + 03 8.30E + 03 1.01E + 05 2.28E + 05 – 2.25E + 04 9.73E + 00 1.24E + 01 3.53E + 02 4.93E + 04 5.86E + 01 7.33E + 04
1.02E + 03 2.05E + 02 7.11E + 02 8.56E + 04 1.87E + 05 – 1.90E + 04 8.38E + 00 1.01E + 01 2.98E + 02 4.05E + 04 4.99E + 01 6.02E + 04
9.42E + 02 1.86E + 02 6.48E + 02 7.73E + 04 1.66E + 05 – 1.72E + 04 7.69E + 00 8.67E + 00 2.68E + 02 3.60E + 04 4.57E + 01 5.35E + 04
D D D D D E D B C D D C D
10,000 100
1.4 370
1.31E + 03 3.14E + 00
1.13E + 03 2.70E + 00
1.04E + 03 2.49E + 00
D B
Table 7 Results of PNEC, hazard quotient and aquatic risk characterization (for the spill amount of 10,000 tonnages) of priority HNS in Daesan port. Priority rank
1 2 10 13 14 31 37 48 57 68 76 85
HNS name
Coal tar Phenol Sulfur (molten) Acetone Ethyl alcohol Methyl alcohol Ethylene dichloride Acetic acid Nitric acid (< 70%) Sodium hydroxide solution Vinyl acetate Methyl methacrylate
PNEC source
Assessment factor
Taxonomic group
Acute or chronic
Endpoint
Fish Fish Other Fish Other Fish Fish Crustacea Fish Crustacea
Chronic Chronic Chronic Chronic Chronic Chronic Chronic Chronic Acute Acute
LOEL LC50 LC50 LOEC NOEC NOEC NOEC NOEC LC50 EC50
100 10 100 100 100 10 50 100 1,000 10,000
Fish Crustacea
Acute Chronic
LC50 NOEC
10,000 100
PNEC (ug/L)
Hazard quotient (PEC/PNEC)
Aquatic risk characterization (A/B/C/D/E)
Neap tide
30 days mean
Spring tide
19 7 15.4 49.5 1 10 36.4 320 72 4.038
5.26E + 00 2.81E + 02 2.94E + 02 3.33E + 02 3.40E + 04 7.51E + 03 8.13E + 00 1.12E + 02 5.94E + 01 1.86E + 04
3.17E + 00 1.69E + 02 1.77E + 02 2.00E + 02 2.04E + 04 4.50E + 03 4.89E + 00 6.69E + 01 3.57E + 01 1.12E + 04
2.36E + 00 1.25E + 02 1.31E + 02 1.49E + 02 1.52E + 04 3.35E + 03 3.63E + 00 5.00E + 01 2.65E + 01 8.30E + 03
B D D D D D B D C D
1.4 370
1.07E + 03 1.57E + 00
6.43E + 02 9.43E-01
4.79E + 02 7.03E-01
D B
Table 8 Classification of the results on initial marine environmental risk assessment. Classification
Hazard quotient
Explanation
A B
<1 1–10
C D E
10–100 > 100 –
Harmful effects are not likely Harmful effects cannot be ruled out Further testing and assessment requiredImmediate further testing and assessment required Major concern, risk reduction measures should be required Harmful effects cannot be assessed in current situation
tide, and the spring tide from the Korea Hydrographic and Oceanographic Agency (KHOA). Fig. 4 shows the measuring points and the measured tidal current characteristics at the three ports. The water and sediment characteristics data were obtained from the Marine Environmental Information System (MEIS) co-operated by the Ministry of Oceans & Fisheries of Korea and the Korea Environmental Management Corporation (KOEM). The maximum spill amount of HNS is set as 10,000 tonnages as mentioned above and suggested in our previous study (Lee and Jung, 2013). Using the MAMPEC and the information,
spilled HNS for each port (i.e., Ulsan port, Gwangyang port, and Daesan port), according to the HNS spill scenario. In order to calculate the environmental concentrations, the harbor type should be determined in advance of the simulation. Fig. 3 shows actual photos of the three ports and the harbor type, selected by considering its topographic conditions. The Ulsan and the Gwangyang ports are considered commercial harbors, while the Daesan port is considered an open harbor. The hydrodynamic behavior was calculated using the average value of the real sea data such as the tidal current, the period of tide, the neap 211
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acid, methanol, phosphoric acid, and sodium hydroxide solution are likely to have a high concentration at an early stage, which has high toxic effects on marine organisms. As shown in Tables 5–7, the HQs of most substances are high due to the assumption of 10,000 tonnages of HNS spill. In this study, an initial environmental risk assessment was conducted using the worst case HNS spill (i.e., 10,000 tonnages). Therefore, we can readily perform the initial environmental risk assessment for further investigations using real-time monitoring of HNS spill accidents, because we developed the systems for calculating PEC and PNEC with DB of physical/chemical properties of HNS (i.e., 158 priority HNS in Korea). Initial environmental risk assessment for HNS spill accidents were developed in this study. The initial environmental risk assessment is a preliminary analysis tool for further detailed examining of the HNS risk assessment. To apply the developed method, we selected the three major ports (i.e., Ulsan port, Gwangyang port, and Daesan port) of HNS traffic around the Korean Peninsula. The data for analyzing the initial environmental risk assessment were from the credible Korean national providers (i.e., the Ministry of Oceans and Fisheries and the Korea Hydrographic and Oceanographic Agency). To consider the worst possible HNS spill accident, the HNS spill amount is assumed to be 10,000 tonnages which is regarded as the maximum HNS spill amount in Korea. The results of the initial environmental risk assessment show that the highly soluble HNS are more harmful to marine ecosystems during neap tide because the seawater exchange volume is the smallest. It should be noted that this study is based on a worst case HNS spill accident, not a specific actual HNS spill accident. Nevertheless, the systems developed in this study, which could calculate the PEC and PNEC with the physical/chemical properties of 158 priority HNS, can readily perform the initial environmental risk assessment for future HNS spill accidents. Our results also help enlarge the understanding of the environmental risk assessment of an HNS spill accident.
Table 9 Criteria for identification of PBT substances (IMO, 2017). Criterion Persistent Bioaccumulation Toxicity (Environment) Toxicity (Human health, CMR)
PBT Criteria Marine water Marine sediment BCF Log Pow Chronic NOEC Carcinogenic Mutagenic Reproduction
60 days 180 days > 2,000 >3 < 0.01 mg/L Category 1A or 1B Category 1A or 1B Category 1A, 1B or 2
the PECs were calculated. The results show that the PECs are relatively higher in the cases of the highly soluble materials such as the acids, bases, and alcohols. The PEC at Daesan port is relatively lower than those at other ports, which is attributed that the Daesan port is open harbour at which the seawater exchange volume is the greater than those of other ports. Tables 2–4 show the characteristics and PEC calculation results of priority HNS at each port. It should be noted that the X, Y, and Z in Tables 2–4 are; X: Noxious liquid substances (NLS) which, if discharged into the sea, are deemed to present a major hazard to either marine resources or human health and, therefore, justify the prohibition of the discharge into the marine environment; Y: NLS which, if discharged into the sea, are deemed to present a hazard to either marine resources or human health or cause harm to amenities or other legitimate uses of the sea and therefore justify a limitation on the quality and quantity of the discharge into the marine environment; Z: NLS which, if discharged into the sea, are deemed to present a minor hazard to either marine resources or human health and therefore justify less stringent restrictions on the quality and quantity of the discharge into the marine environment (MEPC, 2006). To establish the PNEC DB for this study, we refer to IMO BWM (which was updated, 20 July 2017) (IMO, 2017). According to the IMO BWM, to assess the HNS effects on the marine environment, an appropriate PNEC should be derived. A PNEC could be derived from the level at which, the marine ecosystem is not affected by the toxicity of long-term exposures. The definition of PNEC is the lowest LC50, EC50 or NOEC divided by an AF, where the LC50 is the median lethal concentration, the EC50 is the median effective concentration, the NOEC is the no observed effect concentration, and the AF is the assessment factor. As shown the bottom-left of Fig. 5, the AF values were allocated in five stages, ranging from 10 to 10,000, depending on the number of available toxicological data. In cases where a comprehensive data-set is available, the PNEC could be derived using a mathematical model of the sensitivity distribution among species. The guideline details for the assessment factors has been reported in the IMO BMW (IMO, 2017). In this study, we developed the ‘HNS Eco-Toxicity Database’ system (the details are not discussed here), which includes the physical and chemical properties and the eco-toxicity data as shown in the right side of Fig. 5. As the results, the PNEC of priority HNS at the three ports were calculated using the definition of the PNEC as shown in Tables 5–7. The initial environmental risk assessment results are represented in Table 8, there are five stages reflecting the hazard analysis, the characteristics of the persistence, bioaccumulation, and toxicity (PBT) of the HNS. For the PBT, the criteria for the risk assessments of BWMS have been applied as shown in Table 9 (IMO, 2017). As a result of the initial environmental risk assessment of HNS in the three major ports of Korea, all HNS were classified as needing a detailed evaluation and additional testing with HQ > 1, because the spill amount of HNS is 10,000 tonnages of HNS is assumed to present the worst case and could be used to establish a preparedness and national contingency plan in the Korean Peninsula. Also, the HQ of the neap tide case was applied to classify the risk characterization of HNS, to consider the worst case in which the seawater exchange volume is the smallest. The results show that highly soluble HNS such as ethanol, sulphuric
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