For reasons of economy, this document is pr inted in a limited number. Delegates are kindly asked to bring their copies to mee tings and not to request additional copies.

I:\MEPC\60\2-8.doc

INTERNATIONAL MARITIME ORGANIZATION

IMO 

# E

MARINE ENVIRONMENT PROTECTION COMMITTEE 60th session Agenda item 2 MEPC 60/2/8 26 August 2009 Original: ENGLISH

HARMFUL AQUATIC ORGANI SMS IN BALLAST WATER

Application for Basic Approval of the OceanGuard TM Ballast Water ManagementSystem

Submitted by Norway

SUMMARY
Executive summary: This document contains non-confidential information for Basic Approval of the OceanGuard TM Ballast Water Management System under the “Procedure for approval of ballast water management systems that make use of Activ e Substances (G9)” adopted by resolution MEPC.169(57). The doc umentation complies with the requirements related to asse ssments for Basic Approval.
Strategic direction: 7.1
High-level action: 7.1.2
Planned output: 7.1.2.4

Action to be taken: Paragraph 5

Related documents: BWM/CONF/36, MEPC 57/21 and BWM.2/Circ.18

Introduction

1 The Ballast Water Management Conventi on (BWM Convention), in regulation D-3.2, provides that ballast water management systems wh ich make use of Active Substances to comply with the Convention shall be approved by the Organization.

2 The “Procedure for approval of ballast water management systems that make use of Active Substances (G9)” identifie s the information that should be included in a proposal for approval (MEPC 57/21, annex 4, paragraph 4.2.1) and provisions for risk characterization and analysis (MEPC 57/21, annex 4, paragraph 5.3). Section 6 of Procedure (G9) presents the evaluation criteria the Organizati on should apply in the evaluation of the information provided in the application.

3 The competent authority in Norway has veri fied the application dossier and the test protocols applied for all tests undertaken and belie ves it to satisfy the data requirements of Procedure (G9) adopted by resolution MEPC.169(57).MEPC 60/2/8 - 2 -

I:\MEPC\60\2-8.doc 4 Norway therefore submits th e non-confidential part of th e manufacturer’s application dossier, in the annex of this document, to the Organization for evaluation according to Procedur (G9). The complete dossier wi ll be made available to the experts of the GESAMP-BWWG with th e understanding of conf idential treatment.

Action requested of the Committee

5 The Committee is invited to consider the pr oposal for approval and decide as appropriate.

***MEPC 60/2/8

I:\MEPC\60\2-8.doc ANNEX

NON-CONFIDENTIAL INFORM ATION OF THE OCEANGUARD TM
BALLAST WATER MANAGEMENT SYSTEM

Contents

1 ABBREVIATION

2 SUMMARY

3 SYSTEM DESCRIPTION

3.1 Introduction of OceanGuardTM BWMS 3.1.1 Automatic back flushing filter 3.1.2 EUT unit 3.1.3 Control unit 3.1.4 Sensors 3.2 Chemical reactions in the EUT unit 3.2.1 Reactions in fresh water 3.2.2 Reactions in seawater 3.2.3 Secondary with the possibil ity of bromide ion in water 3.2.4 Secondary reactions with the possibility of organics in water 3.3 Treatment process 3.4 Test results of biological efficacy

4 IDENTIFICATION OF THE SUBS TANCES OR PREPARATIONS

4.1 Preparations 4.2 Active Substances 4.2.2 Hydroxyl free radical 4.2.3 Hydrogen peroxide 4.2.4 Hypochlorite and hypochlorous acid 4.3 Relevant Chemicals 4.4 Others

5 DATA OF ACTIVE SUBSTANCES GENERATED IN BALLAST WATER

5.1 Hydroxyl free radical 5.2 Hydrogen peroxide 5.2.1 Physical and chemical pr operties of hydrogen peroxide 5.2.2 Effects on aquatic organisms 5.2.3 Toxic effects on mammals 5.2.4 Environmental fate and effect under aerobic and anaerobic conditions 5.2.5 Risk characterization 5.3 Hypochlorous acid 5.3.1 Physical and chemical properties of hypochlorous acidMEPC 60/2/8 ANNEX Page 2

I:\MEPC\60\2-8.doc 5.4 Sodium hypochlorite 5.4.1 Physical and chemical prope rties of sodium hypochlorite 5.4.2 Effects on aquatic organisms 5.4.3 Toxic effect on mammals 5.4.4 Environmental fate and effect under aerobic and anaerobic conditions 5.4.5 Testing methods 5.4.6 Risk characterization 5.4.7 PNEC/PEC evaluation

6 DATA OF THE RELEVANT CHEMICALS IN BALLAST WATER

6.1 Dibromochloromethane 6.1.1 Physical and chemical propert ies of dibromochloromethane 6.1.2 Effects on aquatic organisms 6.1.3 Toxic effect on mammals 6.1.4 Environmental fate and effect under aerobic and anaerobic conditions 6.1.5 Testing method 6.1.6 Risk characterization 6.1.7 PNEC/PEC evaluation (MAM-PEC) 6.2 Tribromomethane 6.2.1 Physical and chemical properties of tribromomethane 6.2.2 Effects on aquatic organisms 6.2.3 Toxic effect on mammals 6.2.4 Environmental fate and effect under aerobic and anaerobic conditions 6.2.5 Testing methods 6.2.6 Risk characterization 6.2.7 PEC/PNEC evaluation 6.3 Dibromoacetic acid 6.3.1 Physical and chemical properties of di bromoacetic acid (DBAA) 6.3.2 Effects on aquatic organisms 6.3.3 Toxic effect on mammals 6.3.4 Environmental fate and effect under aerobic and anaerobic conditions 6.3.5 Testing methods 6.3.6 Risk characterization 6.3.7 PNEC/PEC evaluation 6.4 2,4,6-tribromophenol 6.4.1 Physical and chemical pr operties of 2,4,6-tribromophenol 6.4.2 Effects on aquatic organisms 6.4.3 Toxic effect on mammals 6.4.4 Environmental fate and effect under aerobic and anaerobic conditions 6.4.5 Testing methods 6.4.6 Risk characterization 6.4.7 PNEC/PEC evaluationMEPC 60/2/8 ANNEX

Page 3

I:\MEPC\60\2-8.doc 6.5 Bromate ion 6.5.1 Physical and chemical properties of potassium bromate 6.5.2 Effects on aquatic organisms 6.5.3 Toxic effect on mammals 6.5.4 Environmental fate and effect under aerobic and anaerobic conditions 6.5.5 Testing methods 6.5.6 Risk characterization 6.5.7 PNEC/PEC evaluation 6.6 Carbon monoxide 6.6.1 Physical and chemical pr operties of carbon monoxide 6.6.2 Effects on aquatic organisms 6.6.3 Toxic effect on mammals 6.6.4 Environmental fate and effect under aerobic and anaerobic conditions 6.6.5 Analytical method 6.6.6 Risk characterization 6.7 Methane 6.7.1 Physical and chemical properties of methane 6.7.2 Effects on aquatic organisms 6.7.3 Toxic effect on mammals 6.7.4 Environmental fate and effect under aerobic and anaerobic conditions 6.7.5 Analytical method 6.7.6 Risk characterization

7 TOXICITY ASSESSMENT OF THE TREATED BALLAST WATER

7.1 Contents of Oxidants 7.2 Determination of holding time 7.3 Ecotoxicity

8 RISK ASSESSMENT

8.1 Risks to the safety of the ship 8.1.1 Corrosion 8.1.2 Fire and exposure 8.1.3 Storage, loading/unloading and noise 8.2 Risks to human health 8.2.1 Human exposure scenario (HES) 8.2.2 Risk control measures 8.3 Effects on the aquatic environment

REFERENCESMEPC 60/2/8 ANNEX Page 4

I:\MEPC\60\2-8.doc 1 ABBREVIATION
μg/L Microgram per litre ATSDR Agency for Toxic Substances and Diseases Registry BCAA Bromochloroacetic Acid CAS Chemical Abstracts Service DBAA Dibromoacetic Acid DBPs Disinfection By-products
EC 50 Half Effective Concentration EPI Suite Environmental Estimation Program Interface Suite ESIS European chemical Substances Information System FC Free Chlorine EUT Electrocatalysis enhanced by Ultrasonic Technology HAAs Haloaceticacids IARC International Agency for Research on Cancer ICSC International Chemical Safety Card IMO International Maritime Organization ISO International Standa rdization Organization IUPAC International Union of Pure and Applied Chemistry Koc Sediments-water partition coefficient
LC 50 Half Lethal Concentration
LD 50 Half Lethal Dose LOAEL Lowest Observed Adverse Effect Level Log Pow Logarithm of octanol/w ater partition coefficients

m 3 /d Cubic meter per day MBAA Monobromoacetic Acid MEPC Maritime Environm ent Protection Committee mg/kg/d Milligram medicines pe r kilogram weight per day mg/L Milligram per litre Ml Millilitre MOS Margin of Safety MOS(ref) Margin of Safety (reference) MSDS Material Safety Data Sheet NOAEL No Observed Adverse Effect Level NOEC No Observed Effect Concentration NTP National Toxicology Program PEC Predicted Effect Concentration PNEC Predicted No Effect Concentration Ppm Part per million (volume or mass ratio) THM Trihalomethanes TC Total Chlorine US EPA U.S. Environmental Protection Agency WHO World Health OrganizationMEPC 60/2/8 ANNEX

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I:\MEPC\60\2-8.doc 2 SUMMARY

OceanGuard TM Ballast Water Management System (BWMS) is the technology of Qingdao Headway Technology Co., Ltd., which ha s been under development for five years. The technology uses advanced Electrocatalysis enhanced by Ultrasonic Treatment (EUT) to achieve the ballast water treatment. The balla st water goes through a 50 μm filter and the EUT unit during ballasting. At de-ballasting, the 50μm filter is bypassed and the water goes through the ultrasonic treatment and is discharg ed without applying the electrocatalysis.

Small-scale testing of the ballast water treatmen t technology has been carried out by NIVA at their test facilities in Norway in January 2009. NIVA has established a centre for land-based, full-scale testing of ballast water management systems in accordance with IMO Guidelines and has operated laboratories which are accredited according to the international standards, i.e. “NS-EN ISO/IEC 17025”. The whole tes ting was under the supervision of DNV.

The small-scale tests performed at NIVA have b een carried out using th e medium salinity water (between 3 and 32 PSU, approximately. 22 PSU ) and high salinity water (>32 PSU) according to Guidelines (G8). For both water quali ties, 1, 2 and 4 mg/L were set as the initial Total Residual Oxidants (TRO) level in the EUT. The test results show that the ballast water can reach the D-2 standard after treatmen t. Active Substances and other chemicals have been identified, and the concentrations of the Relevant Chemicals are found to be in direct proportion to the TRO concentration generated duri ng ballasting. Considering the decay rate of TRO, the concentration of Releva nt Chemicals generated, and the toxicity testing results, initial TRO concentrations of 1 mg/L and 2 mg/L have been found to be sufficient for treatment of seawater (33 PSU) and brackish water (22 PSU) resp ectively. In this a pplication, all testing results arrive from the small-scale tests performe d at NIVA. Additional test results are indicated in the attached NIVA report.

In the testing cycle with seawater (33 PSU) tr eated with the initial TRO level of 1 mg/L, after 1 day storage, the TRO level was below 0.2 mg/L . On day 5, i.e. after 5 days storage, only very few chemical substances in low concentrati on were detected, and no explosive or toxic gas was detected. According to the related OECD or ISO standard (NIVA report), undiluted treated water has some toxicity to aquatic organisms, however, after low dilution, it will be suitable to discharge into the environment nearby.

In the test with brackish water (22 PSU) with th e initial TRO level of 2 mg /L, after 1 day storage, the TRO level was below 0.2 mg/L, however, carbon monoxide and methane in low concentration was detected during ballasting. On day 5, only a few chemical substances in low concentration were detected, a nd no carbon monoxide, or methane, or other explosive or toxic gas was detected. According to related toxicity testing results, even undiluted treated water did not show significant effect to aquatic organisms.MEPC 60/2/8 ANNEX Page 6

I:\MEPC\60\2-8.doc The biological efficacy is achieved mainly thr ough Active Substances generated in the water, which we call TRO. The ultrasonic part acts as a supplementary of the electrocatalysis part, to enhance the biological efficacy. In seawater and brackish water, which contain chloride ion, TRO are mainly in the form of sodium hypochlorite. In fresh water, since the c oncentration of chloride ion is low, TRO in the water are mainly in th e mode of oxidants with high oxidizing ability, composing of the elements hydrogen and oxygen, a nd some sodium hypochlorite. Theoretically, the degradation rate of TRO in fresh water is much faster th an that in seawater, and the concentration of chemical substa nces generated is even lower, so there is basically no harmful effect to the environment. Toxicity of the treat ed waters with low salinity should be smaller than that of water with high salinity. Toxicity of wa ter of different salinities treated with the same initial TRO level, should be in direct proportion to the salinity.

The mechanical filter to be used has a filter me sh of 50 μm. The filter can remove particles and viable organisms ≥ 50 μm in minimum diameter. After a cert ain time of storage, since there will be re-growth of bacteria and other organisms in order to make sure water being discharged can still reach requirements of regul ation D-2, a second treatment by the EUT unit will be conducted during de-ballasting before discha rge over a long period of travel. Only the ultrasonic part works during this process.

In this application for Basic Approval, only smal l-scale testing has been carried out. During application for Final Approval, equipment tested will be completely the same as the final product, including treatment unit, automatic control unit, etc., as required by IMO. The treatment unit adopted the design of modular structure, with 250t/h flow for each module, which makes the system suitable to be installed on ships with different ballast water capacities.

The ballast water treatment is performed in a totally sealed system and all Active Substances are generated in the EUT unit. This makes it unnece ssary to buy or store any additional chemicals on board and eliminates the hazards related to storage and handing of extra chemicals.

Results from toxicity testing of the treated ballas t water are in line with what was expected from the PEC/PNEC assessment of Active Substances. Available data therefor e do not indicate that there are Active Substances produced by the Ocean Guard TM which are not already accounted for in the present assessment.

Active Substances were also assessed for their Persistence, Bioaccumulation and Toxicity (PBT) potential. Although sodium hypochlorite shows signi ficant chronic toxicity and tribromomethane is fairly persistent in the environment, no Active Substance fulfilled more than one of the PBT criteria, and none therefore are e ligible for a PBT classification.MEPC 60/2/8 ANNEX

Page 7

I:\MEPC\60\2-8.doc 3 SYSTEM DESCRIPTION

3.1 Introduction of OceanGuardTM BWMS

Sea Door P Symbols

Valve

Filter

Ballast Pump P Control Water Tank

Electromagnetic Flow sensor EM EUT Power Electrically Operated Valve

PSU Outlet

Sewage Outlet

EM Treated Water Tank

PSU Salinity Sensor EUT Unit Sample 1

Sample 2 Sample 3 Sample 4

Figure 3.1 : Treatment Process with OceanG uardTM Ballast Water Management System

Figure 3.2 : Model of OceanGuardTM Ballast Water Management SystemMEPC 60/2/8 ANNEX Page 8

I:\MEPC\60\2-8.doc Figure 3.1 shows an OceanGuardTM BWMS with one single treatment unit of 250 t/h. Ballast water is pumped in from the sea chest, throug h the filter and into the EUT unit. After the ultrasonic treatment and electrocatal ysis in the EUT unit, which kills the aquatic organisms, the water flows through the ballast wate r pipes into the ballast water ta nks. During de-b allasting, the ballast water bypassed the filter and pumped into the EUT unit where only the ultrasonic unit is used before discharge. Figure 3.2 shows the model of the OceanGuardTM Ballast Water Management System.

The key components of OceanGuardTM Ballast Wate r Management System are described in the following paragraphs.

3.1.1 Automatic back flushing filter

In order to prevent partic les and viable organisms ≥ 50 μm in diameter from getting into the system, an automatic back-flushing filter with th e filtration degree of 50μm is set before the treatment unit. This filter will start backwashing automatically when the pressure loss exceeds the set point without any artificial operations. The filter is working during ballasting, while during de-ballas ting, it is bypassed.

Figure 3.3 : Automatic back flushing filter

3.1.2 EUT unit

This part is the core component of the system. It is composed of two parts: the electrocatalysis part and the ultrasonic part. In the electrocat alysis part, semiconductor catalyzing materials of high performance are adopted, which generate the Active Substances. The electrocatalysis part can realize high current efficienc y, with long lifespan of more th an two years, suppose working hours is 24-hour per day. It can re move the vast majority of the remaining biological bacteria. The ultrasonic part adopts the technology now commonly used in sterilization technology. It can generate oscillating force within very short period of time, crush cells, so the bactericidal effect can be realized. As a supplementary part of the electrocatalysis unit, this can further improve the sterilization effects.MEPC 60/2/8 ANNEX

Page 9

I:\MEPC\60\2-8.doc Figure 3.4 : EUT unit

3.1.3 Control unit

The control unit for the entire syst em is in charge of various type s of sensors, handling of alarm signals, as well as startup and s hutdown of the system. It contai ns all the necessary controlling procedures and displays the ope rating conditions of every components of the system. If the treatment system fails, it will make an audio an d light alarm and automatically switch to a safe mode. Data of operating conditions of the system can be recorded, memorized, displayed and printed. The operators can take control and make adjustment through this control unit.

3.1.4 Sensors

Parameters like salinity, flow rate, TRO and EUT power consumption can be measured by the sensors. The control unit can respond on the sy stem condition and initiate adjustments accurately in time to get an ideal treatment effect. Salinity, flow rate and TRO are very important parameters in the process. The most suitable in itial operational mode of the EUT unit can be set by the control unit through the internal memory procedures. With the TRO sensors, power supply parameters can be adjusted by the control un it, so that suitable init ial TRO level can be set to ensure the biological treatment efficacy and al so to limit the toxicity. Figure 3.5 shows the principle of the control system.

Data from TRO sensors will be transmitted to the control unit. If the data is higher than the required value set, parameters of EUT power s upply will be adjusted to lower the initial TRO level, and vice versa. Therefore, the initial concentration of TRO will remain in a range of constant concentration.MEPC 60/2/8 ANNEX Page 10

I:\MEPC\60\2-8.doc Figure 3.5 : Principle of the control system

The laboratory testing system mainly includes th e automatic back-flushing filter and EUT unit.

3.2 Chemical reactions in the EUT unit

The EUT unit can remove and kill the organisms by combing the technologies of electrocatalysis and ultrasonic sound. The chemical reactions take place in the electrocatalysis part of the EUT unit. The electrocatalysis unit kills the organisms mainly by us ing the online-generated hydroxyl free radical, which has extremely strong oxidizab ility to oxidize the cel l wall and cause the damage and death of the organisms. Meanwhile, on the surface of the semiconductor catalyst, it can make a direct oxidation of the organisms.

Some semiconductor catalyst material may cause cavitation effect in the electric field. The cavitation has very high abil ity to capture electrons, so that the redox reactions on the surface of the materials and in the solution were triggered. In the redox reactions of the solution, H 2 O become ·OH by losing electrons, which is of high oxidation abil ity. This free radical will either take decomposition reaction or go on reacti ng with the other ions and molecules in the water and then generate other kinds of oxidizi ng substances like hydroge n peroxide. Because of their strong oxidizability, these substances will continue taking reactions with organisms and other substances in the water and change into other products. All of th ese oxidizing substances have the effective components of oxidizing the or ganisms. In this ap plication, the oxidizing substances are narrated as TRO.MEPC 60/2/8 ANNEX Page 11

I:\MEPC\60\2-8.doc 3.2.1 Reactions in fresh water

At the Anode 

### e Cat OH Cat OH +

− ⋅ − (a)



### e H Cat O Cat OH + +

− === − ⋅ + (b) O H Cat O Cat OH 2 2 +

− === − ⋅ (c)
Cat O Cat O 2 2 + === − ⋅ (d)
2·OH-Cat===H 2 O 2 +Cat (e) 2H 2 O 2 ====2H 2 O+O 2 (f)

At the Cathode (g) H 2e 2H 2 === + + (g)

As the oxidation potential of hydroxyl is much higher than that of chlorine, the generated hydroxyl will oxidize chloride immediately in to chlorine, hypochlor ite or hypochlorous, depending on different pH values of the water. See figure 4.1.

3.2.2 Reactions in seawater

At the Anode e Cat OH Cat OH +

− ⋅ − (a)

e H Cat O Cat OH + +

− === − ⋅ + (b) O H Cat O Cat OH 2 2 +

− === − ⋅ (c)
Cat O Cat O 2 2 + === − ⋅ (d)
2·OH-Cat===H 2 O 2 +Cat (e) 2H 2 O 2 ====2H 2 O+O 2 (f)

e Cat Cl Cat Cl +

− ⋅ − (g)

2 Cl Cat Cl 2 = == − ⋅ (h)

Reactions in the water +

− + + === + 2H Cl ClO O H Cl
- 2 2 (i)

At the Cathode (g) H 2e 2H 2 === + + (j)

3.2.3 Secondary reactions with the possibility of bromide ion in water

If there is a fraction of bromide in the seaw ater, the bromide ion can be oxidized into hypobromous acid or hypobromite by hypochlorite or hypochlorous. These substances will take reactions with the organics in the water and produce DBPs.

− + === + Cl HOBr HOCl Br - (k)

+

− + === H OBr HOBr (l)MEPC 60/2/8 ANNEX Page 12

I:\MEPC\60\2-8.doc 3.2.4 Secondary reactions with the possibility of organics in water

The formation and main components of DBPs are under the influence of many factors, such as the water quality, including TOC, bromide ion c oncentration, pH value and temperature. DBPs can also be affected by the treatment conditions li ke dose, and the removal extent of the organics before treatment, etc. All the chemical substanc es that maybe generated during the process have been tested (NIVA report). See test results in figures 4.1 and 4.2.

Reactions: HOBr+Organics===CHBr 3

3.3 Treatment process

Figure 3.6 : Experiment layout

Simulative ballast tanks for treated and control ballast water were set up according to the IMO requirements. Tanks for treated water and control water are sealed. Tests w ith seawater (33 PSU) and brackish water (22 PSU) were car ried out in different time pe riod, with the same procedure and a flow rate of 2 m 3 /h.

Ballasting of treated water and control water was on the same day. Test water was pumped in, through the filter and the EUT unit, into the 1 m 3 treated water tank. On day 5, pump was adopted to mix the water in the tank. Treated water was discharged without sec ond treatment of the EUT unit. Samples were collected from the pipe.

For control water, test water was pumped in, and directly came into the 1 m 3 control water tank. On day 5, pump was adopted to mix the water in the tank. Control water was discharged through the pump directly and samples were collected then. All tanks were closed with a lid and covered to protect from light (refer to section 2.4.1, NIVA report).MEPC 60/2/8 ANNEX Page 13

I:\MEPC\60\2-8.doc 3.4 Test results of biological efficacy

Environmental settings and conditions of samplin g are set according to the IMO requirements in the four tests with different water qualities and salinities. Guidelines (G8) requirements for test water have been fulfilled in all the tests. Du ring the whole process, the system shows good stability and effectiveness, with the flow rate of 2 t/h. See testing result s in Table 3.1(refer to pages 30 to 33, NIVA report).

Table 3.1 : Test results of biological efficacy

Control water Treated water Detection Item Salinit y (PSU) TRO (mg/L) Day 0 Day 5 Day 0 Day 5 Requirement 10 3 /ml >100/m l <10/ml 33 1 9248 7779 0.7 0.3 0-50μm Organisms 22 2 3008 2852 0 0 Requirement 10 4 (cfu/m l 33 1 7.9x10 4 9.2x10 4 1.3x10 3 4.5x10 3 Heterotroph 22 2 1.3 x 10 5 1.5 x 10 2.8 x 1 0 3.0 ± 0.3 x 10 5 Requirement E.coli <250 cfu/100ml 33 1 1.6x10 0 0 0 0 0 Coliform group 22 2 1 0 0 0 0

Requirement V. cholerae <1cfu/100ml 33 1 1.7x10 3 1.9x10 3 1.3x10 1 1.8x10 0 < 1 Vibrio group 22 2 2.2 x 10 3 3.2 x 1 0 1.3 x 1 0 1.6 x 1 0 < 1 Requirement I nt.En t .<100 cfu/100ml 33 1 0 0 0 0 0 Enterococci 22 2 0 0 0 0 0

4 IDENTIFICATION OF THE SU BSTANCES OR PREPARATIONS

4.1 Preparations

In the OceanGuardTM System, the only component th at generates chemical substances is the EUT unit, in which a certain concentration of fr ee radical group like hydroxyl free radical will be generated on the activator’s surface. Chloride an d other ions or organics will be oxidized by this free radical, then hypochlor ous or other kinds of substances w ill be generated. During the whole process, no chemicals are needed, so there is no need to buy, store, or tr ansfer chemicals on board.

4.2 Active Substances

4.2.1 Total Residual Oxidants (TRO)

There are some chemical reactions in the EU T unit (refer to section 3.2), and some Active Substances are generated, which we call TRO. TR O do not refer to one specific substance; it is the generic term for a class of substances with oxidizability. Many substances can not be measured because of their instability, so TRO in this application refer to all the oxidants which have the ability of disinfection. DPD met hod is used during the tests to measure the concentration of Total Chlorine (TC) and Free Ch lorine (FC), with the un it of mg/L chlorine. Substances with oxidizability react with the DPD preparation, and stable compound with red colour will be generated.
Active Substances generated in the EUT unit include hydroxide radical, hypochlorous acid, hypochlorite and hydrogen peroxide.MEPC 60/2/8 ANNEX Page 14

I:\MEPC\60\2-8.doc 4.2.2 Hydroxyl free radical

Active Substances generated directly on board are hydroxyl free radicals, or there might be hydrogen peroxide, oxygen free radical in low concentration, whic h can be indicated from the chemical reactions. The substances have very high oxidation potential with the extremely short generation and existence time of nanosecond. Since the existence time is so short, it is almost impossible to carry out the concentration measurement.
George V. et al. have listed the varied reaction kinetic s parameters in every kind of solution. They had worked over the rate constant of so me kinds of unstable substances in different solutions. Many documents show that the oxid izability of hydroxyl free radical second only to fluorine, so hydroxyl free radical can take variou s reactions with almost all biomacromolecules, organics and inorganics. Hydroxyl free radical can have direct or indirect redox reactions with most of the micro-organisms and or ganics in water. The reactions hydroxyl free ra dical takes are the free radical reaction, which is very fast, and wh ile reacting with organics the rate constant is always above 10 9 L/ (mol ·s), which reaches or goes beyond the limiting value of diffusion rate [ 10 10 L/ (mol ·s) ]. Thus, it is difficult to measur e its accurate concentr ation by instruments for the very short existence time of hydroxyl free radical.

4.2.3 Hydrogen peroxide

Hydrogen peroxide is a kind of common used disi nfectant, which has very strong oxidability and short lifespan. Theoretically, hydrogen peroxide can react with hydroxid e radicals in the EUT unit. However, no evidence was detected in the pilo t testing. Description about this substance is in section 5 of this application.

4.2.4 Hypochlorite and hypochlorous acid

According to the formula (g)-(h) of reactions in seawater, the mixture cons ists of one or several substances of chlorine, hypochlorous acid and hypochlorite generated from reactions between hydroxyl free radical and sodium chloride. The percentage concen tration of chlorine, hypochlorous acid and hypochlorite in the mi xture will vary with different pH values (see figure 4.1). When pH<5, there will be chlorine and hypochlor ous acid. When the pH value is between 5 and 10, there will be hypochlorite and hypochlor ous acid. When pH>10, there will be hypochlorite. Since the pH value of ballast water is between 7 a nd 8, they will be mainly in the form of hypochlorite and hypochlorous aci d, and there is no outlier chlorine detected from the testing results. Hypochlorous aci d and hypochlorite are both listed he re as the Active Substances.MEPC 60/2/8 ANNEX Page 15

I:\MEPC\60\2-8.doc 4.3 Relevant Chemicals
DBPs are generated by the reactions of Active Subs tances, organics and bromide ion in the water, including THMs, HAAs and so on. These substances are paid close attention to in recen t years as they may cause carcinogenicity and organism accumu lations. Also this kind of substances may be a threat to human health with their steady chemical property and long half-life, as they may accumulate in the organisms, so the generating quantity must be reduced. During the tests, substance tested includes AOX, EOX, bromat e ion, THMs, phenol and other halogenation organics. As it is shown in Table 4.1, trib romomethane is the main THMs in the tested halogenation organics listed. In the tests selected, i.e. seawater (33 PSU), treated with 1 mg/L initial TRO, and brackish water (22 PSU), treated with 2 mg/L initial TRO, the maximum levels detected are as follows: DBCM 1.7 μg/l, tr ibromomethane150 μg/l, DBAA 5.9 μg/l, 2.4.6- tribromophenol 0.1 μg/l and bromate ion 3.5 μg/l (r efer to section 3.5, NIVA report). Therefore, the five substances above-men tioned are identified as Relevant Chemicals (Table 4.2).

Table 4.1 : DBPs concentration in seawater ( 33 PSU) and brackish water (22 PSU) tests (samples are collected after 5-day storage).

Component Unit Seawater (33 PSU) Day 5 Brackish water (22 PSU)

Day 5 Chloroform μg/l <0.50 <0.50 Bromodichloromethane μg/l <0.50 <0.50 Dibromochloromethane μg/l 1.7 5 Tribromomethane μg/l 44 150 Monochloroacetic acid μg/l <0.50 <0.50 Dichloroacetic acid μg/l <0.30 <0.30 Acetocaustin μg/l <0.20 <0.20 Bromoacrtic μg/l <0.20 <0.20 Dibromoacetic acid μg/l 0.66 5.9 Bromochloroacetic acid μg/l <0.10 <0.10 Bromodichloroacetic acid μg/l <0.10 <0.10 Chlorodibromoacetic acid μg/l <0.10 <0.10 Tribromoacetic acid μg/l <0.10 <0.10 2,4-Bromophenesic acid μg/l <0.10 <0.10 2,6-Bromophenesic acid μg/l <0.10 <0.10 2,4,6-Bromophenisic acid μg/l <0.10 0.1 1,2- Nephis μg/l <1.0 <1.0 1,2,3- Trichloropropane μg/l <1.0 <1.0 2- Chlorotoluene μg/l <0.50 <0.50 4- Chlorotoluene μg/l <0.50 <0.50 1,2-dibromo-3- Chloropropane μg/l <1.0 <1.0 1,2,3- Tribromo-benzene μg/l Note note 1,3,5- Tribromophenol μg/l <1.0 <1.0 AOX mg/L 0.02 0.1 EOX mg/L <0.010 0.012 Bromate ion μ gl 1.0 3.5MEPC 60/2/8 ANNEX Page 16

I:\MEPC\60\2-8.doc

Table 4.2 : Detected Relevant Chemicals in trea ted ballast water (the highest concentration in the tested waters of different quality)

Name Concentration (μg/L) Dibromochloromethane 1.7 Tribromomethane 150 Dibromoacetic Acid 5.9

Tribromophenol 0.1

Bromate Ion 3.5

4.4 Others

According to the reaction formulas in section 3. 2, a certain amount of hydrogen and chlorine will be generated at the cathode of the EUT unit, and most hydrogen will escape on the surface because of its low water solubility. Hydrogen will violently react with oxygen and cause explosion once the explosion limit of 4% is re ached. So, concentra tions of hydrogen and oxygen are also measured besides chlorine. While the syst em is operating, chlorine may be generated in the high TRO concentration condition. Chlorine is a toxic gas with high hazard to human body. Carbon monoxide, methane and hydr ogen sulfide are the products from the incomplete oxidation of TRO and the organics in a hi gh concentration of the organics in the water. Also, carbon monoxide is toxic gas. The United States O ccupational Safety and Health Administration (OSHA) had specified the concentration threshol d for long-term contact in workshop as 50 ppm. Methane is a flammable gas and it will cause e xplosion once the concentration reaches 5%-15% in air. Hydrogen sulfide is also flamma ble, and makes adverse effects on human body (human LC 50 is 500 ppm). So these kinds of gases are harmful to human and ship.

Table 4.3 : Concentration of gas detect ed (Refer to section 2.3, NIVA report)

Unit Salinity (PSU) TRO (mg/L) Day 0 Day 5
33 1 0 0 Hydrogen % LEL
22 2 0 0
33 1 0 0 Chorine ppm
22 2 0 0
33 1 20.9 20.9 Oxygen %
22 2 20.9 20.9
33 1 0 0 Carbon
monoxide ppm 22 2 25 0
33 1 0 0 Hydrogen
sulfide ppm 22 2 0 0
33 1 0 0 Methane % LEL
22 2 2.5 0MEPC 60/2/8 ANNEX Page 17

I:\MEPC\60\2-8.doc Listed above are the results from the selected testing cy cles. In test with seawater of 33 PSU, treated by 1 mg/L initial TRO, concentration of oxygen is in normal, no other testing gases are detected. In test with brackish water of 33 PSU, treated by 2 mg/L initial TRO, 25 ppm carbon monoxide and 2.5% methane are detected (R efer to section 2.3, NIVA report). The above-mentioned 25 ppm carbon monoxide, 2.5% methane is analysed in the HES assessment.

5 DATA OF ACTIVE SUBSTANCES GENERATED IN BALLAST WATER

5.1 Hydroxyl free radical

Due to the momentary life of hydr oxyl free radical, it will react wi th the organics and inorganics completely by the moment it is generated, and these reactions will produce a series of other oxidative substances in the form of TRO. Since the lifespan of hydroxyl free radicals is very short, it can only exist in the EUT un it. For this free radical itself, it is hard to take concentration measurement, and it will not cause any effects for relative staff or the environment. Meanwhile, existing research about hydroxyl free radical is very few, so we can not provide more data in detail. Only the following data can be provided.

CAS No. 3352-57-6 Name Hydroxyl radical Formula · OH Molecular weight (g/mol) 17.01 Structural formula HO Redox potential 2.8 V

5.2 Hydrogen peroxide

5.2.1 Physical and chemical prop erties of hydrogen peroxide

Property Value References
CAS No. 7722-84-1
Molecular formula H 2 O 2 Molecular Weight (g/mol) 34.02
Structural formula HO-OH Melting point ( ° C) -0.43 OSHA, H 2 O 2 Boiling point ( ° C) 152 OSHA, H 2 O 2 Flammability Not combustile Density (20 ° C, water=1) 1.39 ATSDR, H 2 O 2 Vapour pressure (30 ° C, mmHg) 5 OSHA, H 2 O 2

Vapour density (air=1) 1.2 ATSDR, H 2 O 2 Solubility in water (0 ° C) Soluble OSHA, H 2 O 2 PH in solution Weak acid; PH values change according
to concentration HSDB, H 2 O 2

Dissociation constant (pKa,
25 ° C) 11.75 HSDB. H 2 O 2MEPC 60/2/8 ANNEX Page 18

I:\MEPC\60\2-8.doc

Oxidation/ reduction potential 1.8 MEPC 55/2/4, anne x page 6
Corrosion to material or equipment It can react with some materials.

Reactivity to container
material Contact with metals could result in explosions. OSHA, H 2 O 2

Auto-ignition temperature N/A Explosivity Contract with combustile materials may cause ignition or combustion. Mixed with some special organic materials can cause explosions. OSHA, H 2 O 2

Oxidizability Powerful oxidizer Surface tension (20 ° C) 80.4 dynes/cm HSDB, H 2 O 2 Viscosity 1.245 centipoises(liquid) HSDB, H 2 O 2 Thermal stability and decomposition product Exposure to heat can create potential fire or explosion hazard OSHA, H 2 O 2

Octanol- water partition coefficients (log Pow) -1.57 EPI Suite v3.2

Sediment- water partition coefficients (Koc) 14.3 EPI Suite v3.2

Henry constant (Pa.m 3 /mole,
20 ° C) 7.5E-4 EU risk assessment

EPI Suite is downloaded from the EPA website. In situation where documents are incomplete, this software is used to make an analysis of the Relevant Chemicals. The Estimation Programs Interface (EPI) SuiteTM is a Windows®-based suite of physical/chemical property and environmental fate estimation program developed by the EPA’s Office of Pollution Prevention Toxics and Syracu se Research Corporat ion (SRC). EPI SuiteTM uses a single input to run the followi ng estimation programs: KOWWINTM, AOPWINTM, HENRYWINTM, MPBPWINTM, BIOWINTM, BioHCwin, KOCWINTM, WSKOWWINTM, WATERNTTM, BCFBAFTM, HYDROWINTM, KOAWIN and AEROWINTM, and the fate models WVOLWINTM, STPWINTM and LEV3EPITM. ECOSARTM, which estimates ecotoxicity, is also included in EPI SuiteTM.EPI SuiteTM is a screening- level tool and should not be used if acceptable measured values are available.MEPC 60/2/8 ANNEX Page 19

I:\MEPC\60\2-8.doc 5.2.2 Effects on aquatic organisms

5.2.2.1 Acute aquatic toxicity

Species Effect Value(mg/L) References Bluegill (fresh) 96hLC 50 26.7 ECOTOX database Cutthroat trout (fresh) 30minLC 50 514 ECOTOX database Rainbow trout (fresh) 96hLC 50 22 ECOTOX database Dusky spinefoot (sea) 24hLC 50 224 ECOTOX database Jack Mackerel (sea) 24LC 50 89 ECOTOX database Fish

Chameleon goby (sea) 24LC 50 155 ECOTOX database Water flea (fresh) 24hEC 50 2.3 ECOTOX database Crustacea Water flea (fresh) 48hEC 50 24 ECOTOX database Blue green algae (fresh) 90minEC 50 3.4 ECOTOX database Algae Blue green algae (fresh) 22hminEC 50 0.9 ECOTOX database

5.2.2.2 Chronic aquatic toxicity

Species Effect Value(mg/L) Reference

Mollusca Zebra mussels (fresh) 56dNOEC 2 EU risk assessment

5.2.2.3 Information on endocrine discrupiton

There is no relevant data available.

5.2.2.4 Sediment toxicity

Koc of hydrogen peroxide is 14.3 L/kg (EPI SuitTM, v3.20), which is lower than the limit value Koc of 500 L/kg . Thus, the substance is not likely to accumulate in sedi ments and testing with sediment dwelling species is not relevant for the assessment.

5.2.2.5 Bioconcentration/biomagnification

Log Pow of hydrogen peroxide is -1.57 (EPI Su itTM, v3.20), which is lower than the limited Log Pow of 3, indicating a very low potentia l for bioconcentration/biomagnification.

5.2.2.6 Food web/population effects

Log Pow of hydrogen peroxide is -1.57 (EPI Suit TM, v3.20), which is lower than Log Pow 3 that is limit value. So the possibility of hydrogen peroxide’s impact to food web and population effect should be insignificant.MEPC 60/2/8 ANNEX Page 20

I:\MEPC\60\2-8.doc 5.2.3 Toxic effects on mammals

5.2.3.1 Acute toxic effect on mammals

Species Effect Value(g/kg) Reference Male and female rats Oral LD 50 0.8-5 EU risk assessment Rabbits Dermal LD 50 9.2 EU risk assessment Mice and rats Inhalation LD 50 2 g/m 3 EU risk assessment

Part of the data in this article can not be writte n more clearly, because it is not described in detail in the reference. Descriptions are made in as much detail as possible based on the references.

5.2.3.2 Effects on skin and eye

Species Method Results Reference Skin Rabbits 3%-8%, single Mild reactions EU risk assessment Rabbits 22 ppm, daily for 3 months No eye injury HSDB,H 2 O 2 Eye

Rabbits 0.5% solution, singl e Disturbance of epithelium and returned to normal within 24 h. HSDB,H 2 O 2

5.2.3.3 Repeated-dose toxicity

Exposure Route Exposure Duration Exposure Dose Species Results Reference

Oral 90 days 100- 3,000
ppm solution Mice Body weights reduced; food and water consumption. NOAEL=100 ppm EU risk
assessment

Dermal 4 months, 5 h/day, 5 days/week 0.1-10.1 mg/m 3 Rats Threshold concentration was 1 mg/m 3 , no-effect concentration was 0.1 mg/m 3 EU risk
assessment

Inhalation 6 months, 6 h/day, 5 days/week 10 mg/m 3 Dogs Skin irritation, sneezing. Skin thickened, hair bleached. HSDB,H 2 O 2

5.2.3.4 Development and reproductive toxicity

Pregnant rats were fed contai ning 10% hydrogen peroxide. Mate rnal and fetal weights were reduced but no significant malfor mation was reported (HSDB, H 2 O 2 ).MEPC 60/2/8 ANNEX Page 21

I:\MEPC\60\2-8.doc 5.2.3.5 Carcinogencity/mutagenicity/reproductive toxicity

There is limited evidence in e xperimental animals for the carc inogenicity of hydrogen peroxide. Overall evaluation: Hydrogen peroxi de is not classifiable as to its carcinogenicity to humans (Group 3) (HSDB, H 2 O 2 ).
Hydrogen peroxide was proven to be mutagenic to Salmonella typhimurium TA92 and TA102 and was positive in a forward mutation test in Salmonella typhimurium SV50 (HSDB, H 2 O 2 ).

5.2.3.6 Toxicokinetics

When hydrogen peroxide comes in contact with catalase, an enzyme found in blood and most tissues, it is rapidly decomposed into oxygen and water (HSDB, H 2 O 2 ).

5.2.3.7 Human toxicity

Workers exposed to vapours from 90% H 2 O 2 have noted irritation primar ily, but splash of such high concentration is generally feared as pote ntial cause of sever corn eal damage. A 33-year old woman unintentionally ingested a 1 pint bottle of 35% hydrogen peroxide. She vomited, collapsed, and experienced a brief tonic-clonic se izure within minutes. The patient was markedly cyanotic and had copious white foam emanating from her mouth. After therapy, she was transferred to a rehabilitation facility (HSDB, H 2 O 2 ).

5.2.4 Environmental fate and effect under aerobic and anaerobic conditions

5.2.4.1 Modes of degradation

Environment Degradation
outcome Period Results Reference

Abiotic, seawater, sunlight Oxygen and
water Half-life(90% purity) was 8.3 days EPA review of hydrogen peroxide

Aerobic, water, non-sterile conditions oxygen and
water Half-life was 1.1- 5.3 h EPA review of hydrogen peroxide Aerobic, water, sterile conditions oxygen and
water Half-life was 80 h EPA review of hydrogen peroxide

Anaerobic, soil Half-life was 4h EPA review of hydrogen peroxide

5.2.4.2 Reactions with the organics

Hydrogen peroxide may react as an oxidant, as a reductant or form addition compounds. It reacts easily with various functional gr oups. Most aromatic and aliphatic amines as well as most aldehydes do react with hydrogen pe roxide (EU risk assessment).

5.2.4.3 Potential physical effects on wildlife and benthic habitats
No information is observed that hydrogen peroxide makes effects on wildlif e or benthic habitats. Considering the extremely low (-1.57) and Koc (14.3) value, this effect can be ignored.MEPC 60/2/8 ANNEX Page 22

I:\MEPC\60\2-8.doc 5.2.4.4 Potential residues in seafood
Residues of hydrogen peroxide is almost impossi ble to be found in seafood, because it has no bioaccumulation and biomagnification toxicity.

5.2.5 Risk characterization

Criteria PBT Criteria Reach the Criteria or not Persistence Half life In seawater > 60 days, or in fresh water > 40 days, or in seawater se diment >180 days, or in fresh water sediment >120 days. No (refer to section 5.2.4.1)

Enrichment BCF > 2,000 or LogP ≥ 3 No (refer to section 5.2.1) Toxicity Chronic NOEC<0.01 mg/L No (refer to section 5.2.3.3)

5.3 Hypochlorous acid
Hypochlorous acid has even strong er oxidability than that of hypoc hlorite, and it has extremely short lifespan. It reacts with other substances immedi ately after being generated in the EUT unit. Since the properties of hypochlorous acid and hypoc hlorite are similar to each other, here only physical and chemical properties are listed below. For other data, please re fer to section 5.4 on sodium hypochlorite in this application.

Physical and chemical propert ies of hypochlorous acid

Property Value References CAS No. 7790-92-3 Molecular formula HOCl Molecular Weight (g/mol) 52.46 Structural formula Melting point ( ° C) N/A Boiling point ( ° C) N/A Flammability Non-flammability Density (25 ° C) N/A Vapour pressure (20 ° C, Pa) N/A Vapour density (20 ° C, air=1) N/A Solubility in water (0 ° C) Soluble PH in solution N/A Dissociation constant (pKa, 25 ° C) 7.5 EHC, 216 Oxidation/ reduction potential 1.49 EHC, 216 Corrosion to material or equipment Corrosive to active metal material Reactivity to container material React with many material because of its oxidizability Auto-ignition temperature N/A Explosivity N/A Oxidizability Strong oxidizability Surface tension N/A Viscosity (20 ° C) N/A Thermal stability and decomposition product Generate chloric acid and chlorineMEPC 60/2/8 ANNEX Page 23

I:\MEPC\60\2-8.doc

Octanol- water partition coefficients (log Pow) -0.87 EPI Suite v3.2 Sediment- water partition coefficients (Koc) 14.3 EPI Suite v3.2 Henry constant (Pa.m 3 /mole) 1.277E-14 EPI Suite v3.2

5.4 Sodium hypochlorite
5.4.1 Physical and chemical prop erties of sodium hypochlorite

Property Value References CAS No. 7681-52-9 Molecular formula ClO·Na Molecular Weight (g/mol) 74.4 Structural formula Na + ClO - Melting point ( ° C) -20

─ -30 ESIS, 2007 Boiling point ( ° C) 96-120 ESIS, 2007 Flammability Non-flammability ESIS, 2007 Density (25 ° C) 1.23 g/cm 3 ESIS, 2007 Vapour pressure (20 ° C, Pa) 17.4-20 hPa ESIS, 2007 Vapour density (20 ° C, air =1) N/A Solubility in water (0 ° C) Soluble (29.3 g/100g water) ESIS, 2007 PH in solution N/A Dissociation constant (pKa, 25 ° C) 7.5 EHC, 216 Oxidation/ reduction potential 1.7 MEPC 56/2/3, annex, page 8 Corrosion to material or equipment Corrosive to active metal material Reactivity to container material Can react with many material because of its oxidizability Auto-ignition temperature N/A Explosivity Anhydrous sodium hypochlorite is explosive ESIS, 2007

Oxidizability Strong oxidizability, used and stored in water usually ESIS, 2007

Surface tension N/A Viscosity (20 ° C) 2.6mPa.s MEPC 57/2/7, annex, page 17 Thermal stability and decomposition product Generate sodium chlorate and sodium chloride ESIS, 2007

Octanol- water partition coefficients (log Pow) -3.42 EPI Suite v3.2

Sediment- water partition coefficients (Koc) 14.3 EPI Suite v3.2

Henry constant (Pa.m 3 /mole) 0.39 ESIS, 2007MEPC 60/2/8 ANNEX Page 24

I:\MEPC\60\2-8.doc 5.4.2 Effects on aquatic organisms

5.4.2.1 Acute aquatic toxicity

Species Effect Value (μg/L) References
Clupea harengus (sea) 24hLC 50 360 Dempsey, C.H., 1986 Bluegill (fresh) 96hLC 50 2130 Wilde, E.W., et al. , 1983 Silverside (sea) 96hLC 50 143 Fisher, D.J., et al. , 1999 Golden shiner (fresh) 96hLC 50 304 Fisher, D.J., et al. , 1999 Menidia beryllina (sea) 96hLC 50 128 Fisher, D.J., et al. , 1994 Rainbow trout (fresh) 96hLC 50 59 Fisher, D.J., et al. , 1999 Pimephales promelas (fresh) 96hLC 50 180 Wilde, E.W., et al. , 1983 Fish

Pimephales promelas (fresh) 96hLC 50 580 Wilde, E.W., et al. , 1983 Mysid (Sea) 96hLC 50 62 Fisher, D.J., et al. , 1999 Dapnia magna (fresh) 96hLC 50 32 Fisher, D.J., et al. , 1999 Amphipod (fresh) 96hLC 50 78 Fisher, D.J., et al. , 1999 Ceriodaphnia dubia (fresh) 24hLC 50 80 Taylor, P.A., 1993 Crustacea

Mysidopsis bahia (sea) 96hLC 50 73 Fisher, D.J., et al., 1994

5.4.2.2 Chronic aquatic toxicity

Species Effect Value (μg/L) Reference

Fish Menidia peninsulae (sea) 28dNOEC 40 Goodman et al. , 1983 Dreissena polymorpha (fresh) 11d LC50 1,000 Martin et al. 1993 Dreissena polymorpha (fresh) 20d NOEC 500 Martin et al. 1993

Mollusca In a field study on chlorinated condenser co oling effluents using mollusk bivalves (Liden et al. , 1980), the survival of oysters ( Crassostrea virginica ) and clams ( Rangia cuneata ) maintained at three TRO concentrations for 15 days was not affected at concentration as high as 62 μ g/l, while oyster mean shell deposition was significantly reduced in the treated an imals. At the lowest test concentration (14 μ g/l) a 14% reduction in shell deposition was observed, so that following TGD the NOEC can be estimated as LOEC/2, i.e. 7 μ g/l (ESIS,2007) Algae Natural algae (fresh) 24dNOEC 79 Pratt et al. , 1988
Community Protozoa and algae NOEC 3 ESIS, 2007

5.4.2.3 Information on endocrine disruption

There are no data indicating that sodium hypochlor ite has effects on the endocrine of the aquatic organisms.MEPC 60/2/8 ANNEX Page 25

I:\MEPC\60\2-8.doc 5.4.2.4 Sediments toxicity

Koc of sodium hypochlorite is 14.3 L/kg (EPI SuitTM , v3.20), which is lower than the limit value Koc of 500 L/kg. Thus, the substa nce is not likely to accumulate in sediments and testing with sediment dwelling species is not relevant for the assessment.

5.4.2.5 Bioconcentration/biomagnification

Log Pow of sodium hypochlorite is -3.42 (EPI SuitTM, v3.20), which is lower than the limited Log Pow of 3, indicating a very low potenti al for Bioconcentration/biomagnification.

5.4.2.6 Food web/population effects

Log Pow of sodium hypochlorite is -3.42 (EPI SuitTM, v3.20), which is lower than Log Pow 3 that is limit value. So the possibility of sodi um hypochlorite’s impact to food web and population effect should be insignificant.

5.4.3 Toxic effect on mammals

5.4.3.1 Acute toxic effect on mammals

Species Effect Value(g/kg) Reference Wistar rats Oral LD 50 8.8 ESIS, 2007 Albino mouse Oral LD 50 8.91 ESIS, 2007 Rabbits Dermal LD 0 10 ESIS, 2007 Mouse Inhalation LD 50 10.5 ESIS, 2007

5.4.3.2 Effects on skin and eye

Species Method Results Reference Skin Rabbits, guinea pigs and human 0.5 ml 12.7% sodium hypochlorite, 4 hrs Moderate irritant Nixon, G.A, 1975

Eye Rabbits 0.1ml 12.7% sodium hypochlorite, 24 hrs Severe irritation. ESIS, 2007MEPC 60/2/8 ANNEX Page 26

I:\MEPC\60\2-8.doc 5.4.3.3 Repeated-dose toxicity

Exposure Route Exposure Duration Exposure Dose Species Results Reference

Oral 90 days 0-250 mg/L Male and femaleSpragueDawley rats No integrative or regular data were observed. Daniel et al.

, 1990

Oral 90 days 0-200 mg/L B6C3F1 Rats Water consumption obviously decreased. Weights of all the mice were decreased. NOAEL=10mg/kg/d Daniel et al.

, 1991

Oral 12 and 17 weeks 0.75-1.5 mg/kg/d Rats and mice Pathological changes in the immune system were detected. NTP, 1992

5.4.3.4 Development and reproductive toxicity

Exposure Route Exposure Duration Exposure Dose Species Results Reference

Oral 66-76 days 1.0-5.0
mg Cl 2 /kg/d Male and female mice No Reproductive Toxicity was found. NOAEL= 5 mg/kg/d Carlton et al.

, 1986

5.4.3.5 Carcinogenicity/mutagen icity/reproductive toxicity

Exposure Route Exposure Duration Exposure Dose Species Results Reference

Oral 103 weeks 500 or 1,000 mg/L B6CF1 mice No tumours were observed Sodium hypochlorite HSDB Oral 104 weeks 0-2,000 mg/L Male and female Fischer 344 rats No tumours were observed Sodium hypochlorite HSDB

Oral 2 years 0-275
ppm Rats and mice Leukaemia cases in the female mice can not indicate that this substance is carcinogenic. NTP, 1992

Oral 104 weeks 500 ppm or 1,000
ppm female and male mice There was no obvious tumour found Kurokawa, 1986MEPC 60/2/8 ANNEX Page 27

I:\MEPC\60\2-8.doc 5.4.3.6 Toxicokinetics

The apparent radiochlorine absorption was appr oximately 65%. Urine was the primary route of elimination where 65%-100% of the radio labelled material was the parent chlorate. Chloride was the only radiochlorine labelled me tabolite detected (MEPC 58/2/2).

5.4.3.7 Human toxicity

It is reported that the fatal dose of active chlo rine is 200 ml with the concentration of 3%-6% (F. Racioppi, et al. , 1994). However, there is a record showing that someone had drunk 1L of the 5.25% concentration of NaOCl disinfectant and did not die. Anothe r record shows that someone had drunk 0.5 L of this disinfectant with the concentration of 10% and also survived (Ward and Routlcdge, 1988). Furthermore, it was mentioned in Racioppi’s reports that 250 ml-500 ml of the 12.5% concentration of NaClO solution will be sufficient to cause death if ingested (Racioppi et al. , 1994). And a report from Froner in 1987 shows that a 27-year old youngster had drunk 60 ml hypoc hlorite solution with the inje cted concentration of 5.25% became lethargic, however, after he was revived la ter, he became safe and sound again as usual.

At present, the repeated dose of dermal toxicity test for the human body is mainly focused on the partial skin exposure. None of the 60 allergic de rmatitis patients felt irritation after being coated with 1% concentration of NaClO (Habets et al. , 1986).

5.4.4 Environmental fate and effect under aerobic and anaerobic conditions

5.4.4.1 Modes of degradation

Environment Degradation
outcome Period Results Reference

Light, rising temperature chlorate, chloridion, chlorition <1,500 mins and 7hrs The degradation rate is faster in solutions with higher concentration. M.W. Lister, 1956; Church, 1994 Light, rising temperature oxygen and chloridion <1,500 mins and 7hrs The most active catalysts are nickel, cobalt and
copper. M.W. Lister, 1956; Church, 1994 Dark, immobile The degradation is in accordance with the initial reaction kinetics formula, i.e. half-life is less than 15 minutes. Johnson, 1978

5.4.4.2 Reactions with the organics

Due to its high oxidizability, the active chlorine can react with many organics. For example, the aquatic natural organics and brom ide ion in the water, generati ng a series of DBPs including THMs, HAAs and phenolic compounds. The kind and concentration of substance generated depends on the kind of organics and concentration of active chlorine.MEPC 60/2/8 ANNEX Page 28

I:\MEPC\60\2-8.doc 5.4.4.3 Potential physical effects on wildlife and benthic habitats

No information is observed that sodium hypochlor ite hass effects on wildlife or benthic habitats. Considering the extremely low (-3.14) and Koc (14.3) value, this effect can be ignored.

5.4.4.4 Potential residues in seafood

Residues of sodium hypochlorite are almost impo ssible to be found in seafood, because it has no bioaccumulation and biomagnification toxicity.

5.4.5 Testing methods

Testing method Colorimetric DPD-method Applicability Salt water Sensitivity 0.02 mg/L Cl 2 Reference American Public Health Association, 1989

5.4.6 Risk characterization

The PBT criteria identification of sodium hypochlorite are as follows:

Criteria PBT Criteria R each the Criteria or
not Persistence Half life In seawater>60 days, or in fresh water>40 days, or in seawater sediment >180 days, or in fresh water sediment>120 days. No (refer to section 5.4.4.1)

Enrichment BCF>2,000 or LogP ≥ 3 No (refer to section 5.4.1) Toxicity Chronic NOEC<0.01 mg/L Yes (refer to section 5.4.3.3)

5.4.7 PNEC/PEC evaluation

5.4.7.1 PEC evaluation (MAM-PEC)

MAM-PEC is a user-friendly model of statistics and analysis, whic h can take different standard aquatic scenarios by using different parameters. It is suggested to calculate PEC using this model by IMO. The latest version, vers ion 2.0 of MAM-PEC is applied in the study. For more detailed information, please refer to the Assessment on Human Exposure Scenario of Ballast Water Treated by OceanGuard T M Ballast Water Management System.

The ballast water discharging capacity of OE CD-EU commercial harbour has an exchange volume of 51,117,000 m 3 (refer to ESD). The daily volume of discharged. treated ballast water is simulated as 300,000 m 3 /d, according to the description of Port of Rotterdam in document MEPC 57/2/7. Concentration of sodium hypochlorite in the discharged ballast waterMEPC 60/2/8 ANNEX Page 29

I:\MEPC\60\2-8.doc is 0.05 mg/L. After all the physical and chemi cal properties being input ted, the conclusions derived from the software are as follows:

The result shows the calculated concentration in th e Harbour and the Surroundings. The above figure shows the definition of Harbour and Surroundings.

Average concentration of the Harbour: 1.51x10 -2 μg/L Maximum concentration of the Harbour: 3.27x10 -2 μg/L Average concentration of the Surroundings: 7.72x10 -4 μg/L Maximum concentration of the Surroundings: 4.00x10 -3 μg/L

5.4.7.2 PNEC evaluation

According to the aquatic organism acute toxicity data and aquatic organism chronic toxicity data, PNEC is calculated with the lowest value of th e data against different species. The impact factors are made and corrected according to th e Methodology for information gathering and the conduct of work of the GESAMP-BWWG. According to the shortest period LC 50 of species from two different trophic leve ls, and lowest chronic NOEC of species from several different trophic levels, the impact fact or is decided to be 50.

Species Effect Value (μg/L) Minimum Impact factor PNEC Menidia beryllina (fish/sea) 96hLC 50 128 Mysid (crustacea/sea) 96hLC 50 62 Menidia peninsulae (fish/sea) NOEC (28d) 40

Dreissena polymorpha (molluscafresh) NOEC (20d) 500

Crassostrea virginica (sea) NOEC (134 ) 7 Natural algae (algae/fresh) NOEC (24d) 79 Community changes NOEC (7d) 3 3 (μg/L) 50 0.06 ug/L

PEC/PNEC=0.0151/0.06 =0.252<1
Therefore, this PEC value should be of no harmfu l effects on the environm ent when discharging.MEPC 60/2/8 ANNEX Page 30

I:\MEPC\60\2-8.doc 6 DATA OF THE RELEVANT CHEMICALS IN BALLAST WATER

6.1 Dibromochloromethane

6.1.1 Physical and chemical propert ies of dibromochloromethane

Property Value Reference

CAS No. 124-48-1 Molecular formula CHBr 2 Cl Molecular Weight (g/mol) 208.08 Structural formula

Melting point ( ° C) -20 ATSDR, 2005 Boiling point ( ° C) 120 ATSDR, 2005 Flammability Non-Flammable ATSDR, 2005 Density (20 ° C g/cm 3 ) 2.451 ATSDR, 2005 Vapour pressure (20 ° C, mmHg) 76 ATSDR, 2005 Vapour density (air=1) N/A water solubility (20 ° C, g/L) 2.7 ATSDR, 2005 pH in solution N/A Dissociation constant (pKa) N/A Oxidation/ reduction potential N/A Corrosivity to material or equipment NO

Reactivity to container material N/A Auto-ignition temperature N/A Explosivity N/A Oxidizability N/A Surface tension N/A Viscosity N/A Thermal stability and decomposition product Toxic hydrogen bromide gas Octanol- water partition coefficients (log Pow) 2.16 ATSDR, 2005

Sediment- water partition coefficients (Koc) 57 ATSDR, 2005

Henry constant (Pa.m 3 /mole) 81.0 EPI Suite v3.2MEPC 60/2/8 ANNEX Page 31

I:\MEPC\60\2-8.doc 6.1.2 Effects on aquatic organisms

6.1.2.1 Acute aquatic toxicity

Species Effect Value (mg/L) Reference
Oryzias latipes (fresh) 96hLC 50 79 MEPC 56/2, annex, page 9 Fish Cyprinus carpio (fresh) 45minL C 50 52 Mattice, J.S, 1981

Crustacea Daphnia magna (fresh) 48hEC 50 27 MEPC 56/2, annex, page 9, Tertrahymena pyriformis (fresh) 24hLC 50 65 MEPC 57/2/1, annex, page 17 Algae Selenastrum capricornutum (fresh) 72hEC 50 6.1 MEPC 56/2, annex, page 9

6.1.2.2 Chronic aquatic toxicity

Species Effect Value (mg/L) Reference Cyprinus carpio (fresh) 3-5dLC 50 33.5 Mattice, J.S, 1981

Fish Oryzias latipes (fresh) 21dNOE C 3.2 MEPC 58/2, annex, page 9

6.1.2.3 Endocrine toxicity

There is no information found that dibromochlorom ethane has effects on th e endocrine of aquatic species.

6.1.2.4 Sediment toxicity

Dibromochloromethane is very stable in the water. The Koc value is 57 L/kg (ATSDR, 2005), which is lower than the limit value of 500 L/kg. Thus, the substance is not likely to accumulate in sediments and testing with sediment dwelling species is no t relevant for the assessment.

6.1.2.5 Bioconcentration/biomagnification

Log Pow of sodium dibromochlorom ethane is 2.16 (EPI SuitTM, v3.20), which is lower than the limit of Log Pow 3, indicating a low potenti al for bioconcentration/biomagnification.

6.1.2.6 Food web/population effects

Log Pow of sodium dibromochloromethane is 2. 16 (EPI SuitTM, v3.20), which is lower than the limited Log Pow of 3, so the possibility of food web/population effects is predicted to be insignificant.MEPC 60/2/8 ANNEX Page 32

I:\MEPC\60\2-8.doc 6.1.3 Toxic effect on mammals

6.1.3.1 Acute toxic effect on mammals

Species Effect Value (mg/L) Reference Male rat Oral LD 50 800 Bowman et al., 1978 Female rat Oral LD 50 1200 Bowman et al ., 1978 Male mouse Oral LD 50 916 Chu et al .,1980 Female

mouse Oral LD 50 969 Chu et al., 1980

Male mouse Oral LD 50 2600 Hewitt WR et al .,1983

6.1.3.2 Effects on skin and eye

Dibromochloromethane is classified as a skin and eye irritant (MSDS). Whereas, in the NTP report, there are no histopathologi cal alterations detected after the 2-year toxicity test on the skins and eyes of rats and mice (ATSDR, 2005).

6.1.3.3 Repeated-dose toxicity

Exposure Route Exposure Duration Exposure Dose Species Results Reference

Oral 90 days 0-200 mg/kg/d SpragueDawley
rats The weight of the testing animals decreased, while weight of brain, thymus, liver and kidney increased. LOAEL = 50 mg/kg/d Daniel FB et al.

, 1990

Oral 14 days and 90 days 200-300 times toxic to human beings Rats No abnormality was found Balster et al.

, 1982 Oral 30 days 100 mg/kg/d and 400 mg/kg/d Rats Did not impact the passive avoidance of the rats whereas obvious toxicity was detected with the dose of 400 mg/kg/d. Balster et al.

, 1982

Oral 14 days 125 mg/kg/day Rats Immunity of the rats was decreased Munson et al.

, 1982

6.1.3.4 Growth and reproductive toxicity

Exposure Route Oral Exposure Duration 6-15 days Exposure dose 50-2,000 mg/kg/d Species Sprague-Dawley rats Results For the group exposed to high dose, the matrix weight decreased and toxicity to embryo was caused. Reference Ruddick et al. ,1983MEPC 60/2/8 ANNEX Page 33

I:\MEPC\60\2-8.doc 6.1.3.5 Carcinogenicity/mutagen icity/reproductive toxicity

Rapson and Simmon claimed the carcinogenicity of this substance in 1980 and 1978 respectively. No other available information about the toxi city of dibromochloromethane was found.

6.1.3.6 Toxicokinetics

Dibromochloromethane is lipophilic, and it does not appear to accumulate in adipose tissue. It can be absorbed quickly. Two route-i ndependent pathways ar e thought to metabolize it: oxidation by cytochrome P-450 mixed function oxidase system and conjugation via glutathione S-transferase. It is primarily ex creted via exhalation as the parent compound or carbon dioxide (ATSDR, 2005).

6.1.3.7 Human toxicity

There is little informatio n about toxicity of dibr omochloromethane to human. It is claimed by IARC (ATSDR 2005) that dibromochloromethane ’s carcinogenicity to human body is not classified (Group 3) on the basi s of laboratory data at present. Whereas, EPA classified it as Group C for it is a potential human carcinogen.

6.1.4 Environmental fate and effect under aerobic and anaerobic conditions

6.1.4.1 Modes of degradation (biotic and abiotic)

Environment Degradation period Results Reference

Aerobic, biotic 7 days 10%-25% being degraded Tabak et al. , 1981

Underground water, anaerobic, biotic Half life <50 days Bouwer et al. , 1981

Packed tower, anaerobic, biotic 2 days Removal ratio >99% Bouwer and McCarty, 1984

6.1.4.2 Reactions with organic matters

The chemical property of dibromochloromethane is very stable, and there is no data indicating its capability of reacting with other organic matters.

6.1.4.3 Potential physical effects on wildlife and benthic habitats

No data is found to show that dibromochlorometha ne has effects on wildlife or benthic habitats. Considering its low octanol/water partition coefficient (Log Pow value of 2.16) and low sediment/water partition coefficients Ko c value (57), the effects are slight.MEPC 60/2/8 ANNEX Page 34

I:\MEPC\60\2-8.doc 6.1.4.4 Potential residues in seafood

Gotoh, M. et al. had verified in the 1992 report that th ere were no dibromochloromethane found in oysters, clams and sediments of Ariho River a nd Yoshinaga River. There are no studies about the sorption in soil or substances like soil. However, in 2004, Keefe et al. reported that in the everglade of nearby sewage outfall in P hoenix and Arizona, the removal rate of dibromochloromethane was up to 86.5% thought to be mainly from volatilization.

6.1.5 Testing method

Testing method Gas-chromatographic methods Applicability Salt water Sensitivity 0.5 μg/l Reference ISO 10301-F4: 1997

6.1.6 Risk characterization

Criteria PBT Criteria Reach the Criteria or
not Persistence Half life In seawater >60 days, or in fresh water >40 days, or in seawater sediment>180 days, or in fresh water sediment>120 days. No (refer to section 6.1.4.1)

Enrichment BCF>2,000 or LogP
r ≥ 3 No (refer to section 6.1.1) Toxicity Chronic NOEC>0.01 mg/L No (refer to section 6.1.3.3)

6.1.7 PNEC/PEC evaluation (MAM-PEC)

6.1.7.1 PNEC evaluation
Data on the Ecotoxicity of dibr omochloromethane is very limite d. According to the shortest period L(E)C 50 of species from three different trophi c levels, and lowest chronic NOEC of species from one trophic levels, the im pact factor is decided to be 1000.

Species Effect Value (mg/L) Minimu

m Impact factor PNEC
Cyprinus carpio (fish/fresh) 45min LC 50 52 Daphnia magna (crustacea/fresh) 48h EC 50 27

Selenastrum capricornutum (algae/fresh) 72h EC 50 6.1

Oryzias latipes (fish/fresh) 21d NOEC 3.2 3.2 mg/L 1000 3.2μg/LMEPC 60/2/8 ANNEX Page 35

I:\MEPC\60\2-8.doc 6.1.7.2 PEC evaluation

In the discharged ballast water scenario, th e maximum value of undiluted concentration is 1.7 μg/L, which is already lower than PNEC valu e, so it is implied that there will be no effects on the aquatic environment even if it is undiluted (100%) before discharge.

6.2 Tribromomethane

6.2.1 Physical and chemical pr operties of tr ibromomethane

Property Value Reference CAS No. 75-25-2 Molecular formula CHBr 3 Molecular Weight (g/mol) 252.73

Structural formula

Melting point ( ° C) 8.0 ATSDR,2005 Boiling point ( ° C) 149.1 ATSDR,2005 Flammability Non-flammable ATSDR,2005 Density (20 ° C g/cm 3 ) 2.899 ATSDR,2005 Vapour pressure (20 ° C, mmHg) 5mmHg ATSDR,2005 Vapour density (air=1) 8.7 ATSDR,2005 Water solubility (20 ° C, g/L) 3.1g/L ATSDR,2005 PH in solution N/A Dissociation constant (pKa) N/A

Oxidation/ reduction potential 2.06V MEPC 56/2/3, annex, page 8

Corrosivity to material or equipment Reacting with substances of strong corrosivity and metal, e.g., Sodium hypochlorite, sodium, potassium, calcium, aluminium powder and zinc. IARC, 52

Reactivity to container material Reacting with some plastic, rubber and coatings ATSDR,2005

Auto-ignition temperature N/A Explosivity No MSDS Oxidizability N/A Surface tension 41.53dynes/cm ATSDR,2005 Viscosity N/A Thermal stability and decomposition product Generating toxicbromine hydride gas by pyrolysis MSDS

Octanol- water partition coefficients (log Pow) 2.4 ATSDR,2005

Sediment- water partition coefficients (Koc) 62-126 ATSDR,2005

Henry constant (Pa.m 3 /mole) 54.54 Bromoform HSDBMEPC 60/2/8 ANNEX Page 36

I:\MEPC\60\2-8.doc 6.2.2 Effects on aquatic organisms

6.2.2.1 Acute toxicity on aquatic organisms

Species Effect Value (mg/L) Reference Cyprinodon variegatus (sea) 96hLC 50 18 Heitmuller et al., 1981 Lepomis macrochirus (fresh) 24hLC 50 33 Buccafusco et al., 1981
Lepomis macrochirus (fresh) 96hLC 50 29 Buccafusco et al., 1981 Fish

Cyprinodon variegatus (sea) 96hLC 50 7.1 G.S. Ward et al., 1981 Daphnia magna (fresh) 24hLC 50 56 LeBlanc G.A. 1980 Crusta

cea Daphnia magna (fresh) 48hLC 50 46 LeBlanc G.A. 1980 Selenastrum capricornutum (fresh) 96EC 50 28.1 MEPC 56/2/3, annex, page 18 Algae Skeletonema costatum (sea) 96EC 50 12.3 MEPC 56/2, page 8

6.2.2.2 Chronic toxicity on aquatic organisms

Species Effect Value(mg/L) Reference
Cyprinodon variegatus (sea) 28dNOEC 4.8 MEPC 57/2/7, annex, page 19 Fish Cyprinodon variegatus (sea) 4dNOEC 2.9 Heitmuller et al. , 1981 Algae Selenastrum capricornutum (fresh) 4d NOEC 10 MEPC 57/2/8, annex, page 10

6.2.2.3 Information on producti on of endocrine disruption

No evidence shows the effect of tribromothem ane on the endocrine disruption of aquatic organisms.

6.2.2.4 Sediment toxicity

Tribromothemane is relatively stable in water an d its degradation rate is very low without the existence of bacteria. The Koc value is 62-12 6 L/kg, which is lower than the maximum limit of 500 L/kg, indicating that there is very low possi bility for tribromomethane to be adsorbed in the sediment and that it has strong mobility. Thus, the substance is not likely to accumulate in sediments and testing with sediment dwelling species is not relevant for the assessment.

6.2.2.5 Bioconcentration/biomagnification

Log Pow value of tribromomethane is 2.4 (EPI SuitTM, v3.20), which is lower than the limit of 3, indicates a low potential for bioc oncentration/biomagnification.MEPC 60/2/8 ANNEX Page 37

I:\MEPC\60\2-8.doc 6.2.2.6 Food web/population effects
Log Pow value of tribromomethane is 2.16 (EPI SuitTM, v3.20), which is lower than the limit of 3, indicates the possibility of food web/population effects woul d be predicted to be low.

6.2.3 Toxic effect on mammals

6.2.3.1 Acute toxic effect on mammals

Species Effect Value (mg/L) Reference ICR Swiss male rats Oral LD 50 1.4 (g/kg) Bowman et al. , 1978 ICR Swiss female rats Oral LD 50 1.550 (g/kg) Bowman et al .,1978 Sprague-Dawley male
rats Oral LD 50 1.39 (g/kg) Chu et al. , 1980 Sprague-Dawley female
rats Oral LD 50 1.15 (g/kg) Chu et al. , 1980

Dogs Inhalation LC 50 7 (mg/L/4h) MEPC 57/2/6, annex page 44

6.2.3.2 Effects on skin and eye

In NTP report, after being expe rienced for two years, no tissue changes were observed in the skins and eyes of the rats and mice tested (ATSDR , 2005). This substance is classified as a skin and eye irritant and sensitizer. It will cause burning and tear for individuals exposed to vapour or dust. Repeated contacts with this substanc e could cause dermatitis in the long term (bromoform, HSDB).

6.2.3.3 Repeated-dose toxicity

Exposure Route Exposure Duration Exposure dose Species Results Reference

Oral 14 days 50-250 mg/L CD-1 female and male
rats In the group taking tribromothemane of 250 mg/L, there was decrease in the body weight. The weight of liver increased, however no change in spleen was detected. Munson et al.

, 1982

Oral 14 days 400 mg/kg and 800 mg/kg Rats and mice Weight of the mice taking the 400 mg/kg dose decreased by 14%. Rats in the 800 mg/kg dose group died. NTP, 1989

Oral 13 weeks 12-200 mg/kg and 200 mg/kg Mice No death observed in the 12-200mg/kg. No differences detected in average weight. NOAEL=25 mg/kg NOAEL=50 mg/kg NTP, 1989

Oral 2 years 100, 200 mg/kg The rats and mice No notable difference was observed in the livability or weight. The female rats died after 77 weeks. NTP, 1989

mouth 14 days 145 mg/kg/d Rats Ashen central lobule was observed Condie et al.

, 1983MEPC 60/2/8 ANNEX Page 38

I:\MEPC\60\2-8.doc 6.2.3.4 Development and reproductive toxicity

Exposure Duration 6-15 days

Exposure dose 0, 50, 100 or 200 mg CHBr 3 /kg/d Species Rats Results No maternal toxicity observed; no alteration of litter size or fetal weight and incidence of resorptions , but a dose-related increase in the incidence of skeletal variations. Reference IARC, 52

6.2.3.5 Carcinogenicity/mutagen icity/reproductive toxicity

In the carcinogenicity study of Fujie, K. in 1993, salmonella was used, the in vitro sister chromatid exchange without the S9 activation condition was observed. Also, it was found that this was relative to the dose of tribromomethane.

In the same way, Simmon et al. had concluded the carcinogenicit y of tribromomethane by using salmonella in 1978. In the documents of Rapson ( 1980), total contrary c onclusions were made. Tribromomethane did not show carcinogenicity in Ames test (Rapson W.H., 1980). In the NTP report in 1989, it is claimed that tribromomethane did not cause tumour to the rat but intestinal cancer caused by tribromomethane was observed in mice.

In the relevant reports, some are positive while some are negative, so the tribromomethane carcinogenicity is difficult to determine.

6.2.3.6 Toxicokinetic

Tribromomethane is moderately lipophilic. It does not appear to accumulate in adipose tissue. It can be absorbed quickly. Two route-i ndependent pathways ar e thought to metabolize it: oxidation by cytochrome P-450 mixed function oxidase system and conjugation via glutathione S-transferase. It is primarily ex creted via exhalation as the parent compound or carbon dioxide (ATSDR, 2005).

6.2.3.7 Human toxicity

Tribromomethane was used as painkiller for chil dren in the early 20th century. The normal dose is 180 mg for 3-6 times per day. Few reports had been observed for death by overdose. The lethal dose for children is 300 mg/k g claimed by US EPA (WHO EHC 216).

IARC (IARC 52) assessed the car cinogenicity of tribromomethan e and the conclusion was that there was no sufficient data of hum an test. Therefore, this substa nce is classified as Group 3. However, it was classified as Group B2 (possibility of hu man carcinogenicity) by US EPA (IRIS).MEPC 60/2/8 ANNEX Page 39

I:\MEPC\60\2-8.doc 6.2.4 Environmental fate and effect under aerobic and anaerobic conditions

6.2.4.1 Modes of degradation

Environment Degradation period Results Reference

Aerobic, biotic 7 days 10%-25% being degraded Tabak et al. , 1981

Packed tower, anaerobic, biotic 2 days Removal ratio >99% Bouwer and McCarty, 1984

6.2.4.2 Reaction with organic matters

Tribromomethane is relatively stable, due to its p hysical and chemical properties. It is not active in reacting with organic matters.

6.2.4.3 Potential physical effects on wildlife and benthic habitats

No data were observed about the effects on wildlif e or benthic habitats, and considering its low log Pow value (2.4) and Koc value (62-126) , the effects are relatively small.

6.2.4.4 Potential residues in seafood

Gotoh, M. et al. verified in the report in 1992 that tribromomethan e was not observed in the oysters, clams and sediments in Ariho River and Yoshinaga River. Due to its low log Pow and Koc value, the bioaccumulation possibility of trib romomethane was determined to be very low.

6.2.5 Testing methods

Method Gas-chromatographic methods Applicability Salt water Sensitivity 0.5 μg/l Reference ISO 10301-F4: 1997

6.2.6 Risk characterization

Criteria PBT Criteria Reach the Criteria or
not Persistence Half life : In seawater>60 days, or in fresh water>40 days, or in seawater sediment>180 days, or in fresh water sediment>120 days. No (refer to section 6.2.4.1)

Enrichment BCF>2,000 or LogP ≥ 3 No (refer to section 6.2.1) Toxicity Chronic NOEC<0.01 mg/L No (refer to section 6.2.3.3)MEPC 60/2/8 ANNEX Page 40

I:\MEPC\60\2-8.doc 6.2.7 PEC/PNEC evaluation

6.2.7.1 PEC evaluation (MAM-PEC)

The ballast water discharging capacity of OE CD-EU commercial harbour has an exchange volume of 51,117,000m 3 (refer to ESD). The daily volume of discharged treated ballast water is simulated as 300,000m 3 /, which is according to the description of Port of Rotterdam in document MEPC 57/2/7. Concentration of trib romomethane in the discharged ballast water is 150 μg/L. After all the physic al and chemical properties be ing inputted, the conclusions derived from the MAM-PEC software are as follows:

Average concentration of the Harbor: 9.62x10 -1 μg/L Maximum concentration of the Harbor: 2.62x10 0 μg/L Average concentration of the Surroundings: 2.80x10 -2 μg/L Maximum concentration of the Surroundings: 1.58x10 -1 μg/L

6.2.7.2 PNEC evaluation

According to the shortest period LC 50 of species from three different trophic levels, and lowest chronic NOEC of species from tw o different trophic levels, the im pact factor is decided to be 500.

Species Effect Value (mg/L) Minimum Impact factor PNEC

Cyprinodon variegatus (fish/sea) 96hLC 50 7.1 Daphnia magna (crustacea/fresh) 48hLC 50 46 Skeletonema costatum (algae/sea) 96EC 50 12.3 Cyprinodont variegatus (fish/sea) 4dNOEC 2.9 2.9 (mg/L) 500 5.8μg/L

Selenastrum capricornutum (algae/fresh) 4d NOEC 10

PEC/PNEC=0.962/5.8=0.166 <1.

Therefore, this PEC value indicates no harmfu l effects to the environment upon discharge.MEPC 60/2/8 ANNEX Page 41

I:\MEPC\60\2-8.doc 6.3 Dibromoacetic acid

6.3.1 Physical and chemical propertie s of dibromoacetic acid (DBAA)

Property Value Reference CAS No. 631-64-1 Molecular formula C 2 H 2 Br 2 O 2 Molecular Weight (g/mol) 217.84 Structural formula

Melting point ( ° C) 49 WHO,2004 Boiling point ( ° C) 242.94 MEPC 58/2, annex, page 45 Flammability 94 MEPC 58/2 annex, page 45 Density (20 ° C, g/cm 3 ) N/A Vapour pressure(25 ° C, Pa) 1.84 MEPC 58/2 annex, page 45 Vapour density (air =1) N/A Water solubility (25 ° C, g/L) Diffluent MEPC 58/2 annex, page 45 PH in solution N/A Dissociation constant (pKa) 1.5 Schultz et al. , 1998 Oxidation/ reduction potential N/A Corrosivity to material or equipment N/A

Reactivity to container material Store in a tight closed container. Store in a cool place. Use spark-proof tools and explosion-proof equipment. MSDS

Auto-ignition temperature N/A Explosivity Explosive Oxidizability Oxidizer MSDS Surface tension N/A Viscosity N/A Thermal stability and decomposition product N/A

Octanol- water partition coefficients (log Pow) 1.22 WHO,2004

Sediment- water partition coefficients (Koc) 1.89 EPI Suite v3.2

Henry constant (Pa.m 3 /mole) 7.3x10 -4 EPI Suite v3.2 O O H

B r
B rMEPC 60/2/8 ANNEX Page 42

I:\MEPC\60\2-8.doc 6.3.2 Effects on aquatic organisms

6.3.2.1 Acute toxicity on aquatic organisms

Species Effect Value (mg/L) Reference

Fish Pimephales promelas (fresh) 96h LC 50 69 MEPC 58/2 annex, page 8 Algae Pseudokirchneriella subcapitata (fresh) 72hEC

50 5.95 ESIS, 2007

6.3.2.2 Chronic toxicity on aquatic organisms

No reports indicating that di bromoacetic acid might have a ny chronic toxicity on aquatic organisms were found.

6.3.2.3 Information on endocrine disruption

No reports indicating that dibromoacetic acid might have any endocrine effects on aquatic organisms were found.

6.3.2.4 Sediment toxicity

Dibromoacetic acid’s Koc value is 1.9 L/kg, which is far lower than the maximum limit Koc of 500 L/kg. So the possibility of being absorbed in the soil is predicted to be very low. Thus, the substance is not likely to accumulate in sedi ments and testing with sediment dwelling species is not relevant for the assessment.

6.3.2.5 Bioconcentration/biomagnification

The Log Pow value of dibromoacetic acid is 1. 22 (EPI SuitTM, v3.20), which is lower than the limit value of 3, indicates a low potentia l for bioconcentration/biomagnification.

6.3.2.6 Food web/population effects

The Log Pow value of dibromoacetic acid is 1. 22 (EPI SuitTM, v3.20), which is lower than the limit value of 3. Therefore, the possibility of Food web/population e ffects is predicted to be very low.

6.3.3 Toxic effect on mammals

6.3.3.1 Acute Toxic effect on mammals

Species Effect Value (mg/L) Reference

Sprague-Dawley Male rats Oral LD 50 1.737 Linder et al .,1994MEPC 60/2/8 ANNEX Page 43

I:\MEPC\60\2-8.doc 6.3.3.2 Effects on skin and eye

No data was available for the effects on skin and eye.

6.3.3.3 Repeated-dose toxicity

Exposure Route Exposure Duration Exposure Dose Species Results Reference

Oral 3 weeks 0-500 mg/kg/d Male B6C3F1
rats Hepatic weight gained WHO, 2004 Oral 2 weeks, 3 months, 2 years 0-270 mg/kg Female and male mice. Hepatic weight gained. NTP, 2007

6.3.3.4 Development and reproductive toxicity

Exposure Route Exposure Duration Exposure dose Species Results Reference

Oral 8 days before the gestation period 0-250 mg/kg/d Female mice No effects on the number of implantation sites, pregnancy norm or weight of young mice were observed Cummings et al. , 1998

Oral 31 days 0-250 mg/kg/d Male mice Changes in the sperm form and mobility were observed. Linder et al. , 1995 Oral 14 days 1250 mg DBAA/kg/d Male mice Blood testosterone was decreased, after 14 days returned to be normal. Linder et al.

, 1994a Oral 14 days 0-279 mg DBAA/kg/d Male mice In the highest dose group, decrease in epididymal sperm amount and sperm form alteration was observed Linder et al.

, 1994b

6.3.3.5 Carcinogenicity/mutagen icity/reproductive toxicity

Exposure Duration 2-year

Species Female and male mice and rats Results Increased incidence rate of malignant mesothelioma and monocytic leukaemia observed. Liver cell tumour (LCT) and hepatoblastoma observed. Reference NTP, 2007

6.3.3.6 Toxicokinetic

Following gavage exposure in rats, the concentr ation of DBAA in blood peaked within 1h after dosing, suggesting rapid intestinal absorption. It appears to be rapidly excreted. The urine and faeces were minimal contributors to overall bl ood clearance, suggesting biotransformation was responsible for the rapid disa ppearance of DBAA from blood.MEPC 60/2/8 ANNEX Page 44

I:\MEPC\60\2-8.doc 6.3.3.7 Human toxicity

Despite there being many animal toxicity laboratory reports, there are few reports on toxicity to human, so the toxic effect on mamm alian can be used as reference.

6.3.4 Environmental fate and effect under aerobic and anaerobic conditions

6.3.4.1 Modes of degradation (biotic and abiotic)

Holmes et al. tested the degradation rates of DBAA in vivo and vitro . It was reported that the half-life is 1.5 hours (MEPC 57/2/ 7). It is estimated that ha lf-life in the air is 16 days (MEPC 57/2/1).

Mode Half-life Reference Biotic 1.5 hrs MEPC 57/2/7, annex, page 24 Abiotic 16 days MEPC 58/2, annex, page 13

6.3.4.2 Reaction with organic matters

No data was available to show its reaction with other organic matters.

6.3.4.3 Potential physical effects on wildlife and benthic habitats

No data was available to show its effects on wildlife and benthic habitats. Considering its relatively low Log Pow value (1.22) and Koc va lue (1.89), the effects are predicted to be insignificant.

6.3.4.4 Potential residues in seafood

Considering its relatively low Log Pow value (1. 22) and Koc value (1.89), the possibility of potential residues in seafood wa s predicted to be low.

6.3.5 Testing methods

Method Gas-chromatographic methods Applicability Salt water Sensitivity 0.1-0.5 μg/l Reference ISO 23631-2006MEPC 60/2/8 ANNEX Page 45

I:\MEPC\60\2-8.doc 6.3.6 Risk characterization

Criteria PBT Criteria Reach the Criteria or not Persistence Half life In seawater>60 days, or in fresh water>40 days, or in seawater sediment>180 da ys, or in fresh water sediment>120 days. No (refer to section 6.3.4.1)

Enrichment BCF>2,000 or LogP ≥ 3 No (refer to section 6.3.1) Toxicity Chronic NOEC>0.01 mg/L No (refer to section 6.3.3.3)

6.3.7 PNEC/PEC evaluation

6.3.7.1 PNEC evaluation

Documentation of dibromoacetic acid is very li mited, so we choose the PNEC value from other applications as reference. The PNEC value of 6.9 μg/l in document MEPC 56/2/2 is chosen as reference in this application (MEPC 56/2/2, annex, page 40).

6.3.7.2 PEC evaluation

In the discharged ballast water scenario, the maximum value of undiluted concentration is 5.9 μg/L which is already lower than PNEC value 6.9μg/L, so it is implied that for this concentration of dibromoacetic ac id, there will be no effects on the aquatic environment even if it is undiluted (100%) before being discharged.

6.4 2,4,6-tribromophenol

6.4.1 Physical and chemical properties of 2,4,6-tribromophenol

Property Value Reference CAS No. 118-79-6 Molecular formula C 6 H 3 Br 3 O Molecular Weight (g/mol) 330.80 Structural formula

O H B r

B r B r

Log Kow (estimated): 4.18Phenol, 2,4,6-tribromoEPI Suite v3.2

Melting point ( ° C) 89-96 WHO, 2005b Boiling point ( ° C) 244-290 WHO, 2005b Flammability Non-flammable Density (20 ° C, g/cm 3 ) 2.55 MEPC 57/2/6,
annex, page 26 Vapour pressure (25 ° C, Pa) 4.2x10 -2 WHO, 2005b Vapour density (air =1) N/A Water solubility (25 ° C, g/L) 0.059 WHO, 2005b PH in solution N/A Dissociation constant (pKa) 6.08 WHO, 2005b Oxidation/ reduction potential N/AMEPC 60/2/8 ANNEX Page 46

I:\MEPC\60\2-8.doc Corrosivity to material or equipment —— Reactivity to container material Incompatible materials and strong oxidants MSDS

Auto-ignition temperature Non–ignition MSDS Explosivity N/A Oxidizability N/A Surface tension N/A Viscosity N/A Octanol- water partition coefficients (log Pow) 4.18 EPI Suite v3.2

Sediment- water partition coefficients (Koc) 1.19x10 3 EPI Suite v3.2

Henry constant (Pa.m 3 /mole) 4.82x10 -3 EPI Suite v3.2

6.4.2 Effects on aquatic organisms

6.4.2.1 Acute toxicity on aquatic organisms

Species Effect Value (mg/L) Reference Rainbow trout (fresh) 96hLC 50 0.2 WHO, 2005b Lepomis macrochirus (fresh) 96hLC 50 0.3 WHO, 2005b Oryzias latipes (fresh) 96hLC 50 1.5 WHO, 2005b Pimephales promelas (fresh) 96hLC 50 6.3 WHO, 2005b Cyprinus carpio (fresh) 96hLC 50 1.1 WHO, 2005b Fish

Pimephales promelas (fresh) 8dLC 50 4.5 Phipps G.L.,1981 Daphnia magna (fresh) 48hLC 50 5.5 WHO, 2005b Crustacea Daphnia magna (fresh) 48hEC 50 2.2 WHO, 2005b Selenastrum capricornutum (fresh) 72hEC 50 0.8 WHO, 2005b Algae Selenastrum capricornutum (fresh) 72hNOEC 0.2 WHO, 2005b

Protozoa Tetrahymena pyriformis (fresh) 60hEC 50 3 WHO, 2005b

6.4.2.2 Chronic toxicity on aquatic organisms

Species Effect Value (mg/L) Reference Crustacea Daphnia magna (fresh) 21dNOEC 0.2 WHO, 2005b Algae Thalassiosia pseudonana (sea) 7dLC 50 160 MEPC 57/2/6, annex, page 38

6.4.2.3 Information on endocrine disruption

No reports were found, indicating that 2,4, 6-tribromophenol (2,4,6-TBP) might have any endocrine effects on aquatic organisms.MEPC 60/2/8 ANNEX Page 47

I:\MEPC\60\2-8.doc 6.4.2.4 Sediment toxicity

The Koc value of 2,4,6-TBP is 1.19x10 3 L/kg, which is higher than the limit value of 500L/kg. If it is released in the water, there will be 93% in water and 7% in soil; if released in the soil, there will be 99% absorbed in soil (OECD SIDS ), so it has very strong absorption tendency, which makes it easy to be absorbed in soil and sediments.

6.4.2.5 Bioconcentration/biomagnification

The Log Pow value of 2,4,6-tribromophenol is 4.18, wh ich is higher than the li mit value of 3, and the substance thus has a potential for bioaccumulation. However, a 28-day exposure test with the fresh water fish Lepomis macrochirus (http://www.epa.gov/hpv/pubs/sum maries/tribomop/c14177rs.pdf) showed a BCF value of only 20. Based on this, 2, 4,6-tribromophenol is not likely to accumulate in organisms or the food chain.

6.4.2.6 Food web/population effects

The Log Pow value of 2,4,6-TBP is 4.18. Availa ble data from fish bioaccumulation studies, and also from toxicokinetic studies in rats, indicate that food web effect is not an issue for this substance.



### 6.4 .3 Toxic effect on mammals

6.4.3.1 Acute toxic effect on mammals

Species Effect Value(mg/kg) Reference Mice Inhalation LC 50 >50 (mg/L) WHO, 2005b Mice Oral LD 50 1486 WHO, 2005b Male mice Oral LD 50 1995 WHO, 2005b Female mice Oral LD 50 1819 WHO, 2005b Mice Dermal LD 50 >2,000 WHO, 2005b Rabbits Dermal LD 50 >2,000 WHO, 2005b

6.4.3.2 Effects on skin and eye

Species Method Results Reference Skin Rabbits and mice 4 h No irritants WHO, 2005b Eye Rabbits 100 mg in

one injection Diffuse corneal opacity was observed and irritating response with moderate conjunctiva burn. WHO, 2005bMEPC 60/2/8 ANNEX Page 48

I:\MEPC\60\2-8.doc 6.4.3.3 Repeated-dose toxicity

Exposure Route Oral Exposure dose 100, 300 and 1,000 mg 2,4,6-TBP/kg Species Female and male mice Result The weight decreased seriously. We ight of hepatic and renal gained. Decrease in bilirubin and ka lium in blood was observed. NOAEL 100 mg/kg Reference WHO, 2005b

6.4.3.4 Development and reproductive Toxicity

Exposure Route Exposure Duration Exposure dose Species Result Reference

Oral 6 to 15 days 300 and 1,000 mg/kg/d Female and male mice In the 1,000 mg/kg/d dose group, survival ratio and weight of the newborn decreased. In the 300 mg/kg/d dose group, no effect observed. NOAEL for adults, 1,000 mg/kg/d; NOAEL for juvenile. 300 mg/kg/d WHO, 2005b

Oral 6 to 15 days 10- 3,000 mg/kg Pregnant

mouse In 1,000 mg/kg and lower dose group, decrease in embryo livability detected. In 3,000 mg/kg dose group, deaths observed. No abnormal observed in 300 mg/kg dose group. NOAEL, 1,000 mg/kg; NOAEL for the pregnant, 300 mg/kg WHO, 2005b

6.4.3.5 Carcinogenicity/mutagen icity/reproductive toxicity

No data was available for the carcinogenicity/mu tagenicity/reproductive toxicity of 2,4,6-TBP.

6.4.3.6 Toxicokinetic

From the test of rats, the following results were obtained: 2,4,6-TBP was rapidly absorbed, with the concentration in blood peaking after 1hour. The bulk of radioactivit y (50%-91%) was rapidly excreted via urine, with 4%-14% eliminat ed in the faeces within 48 hours. The blood concentration fell down w ithin 24 hours (WHO, 2005b).

6.4.3.7 Toxicity on human

No data was available for the human toxicity. This substance is rapidly absorbed from the gastro-intestinal tract and is rapidly ex creted via urine and faeces in mammal.MEPC 60/2/8 ANNEX Page 49

I:\MEPC\60\2-8.doc 6.4.4 Environmental fate and effect under aerobic and anaerobic conditions

6.4.4.1 Modes of degradation

Environment Degradation products Period Results Reference

Air, light Hydroxyl free radicals Half life 34 days WHO, 2005b

Air, ultraviolet light Hydroxyl free radicals Half life 4.6 hrs WHO, 2005b

Active sludge, aerobic, bacteria 28 days 49% being decreased WHO, 2005b

River water 3 days 82% being decreased WHO, 2005b Seawater 3 days 9% being decreased WHO, 2005b River mouth sediment, anaerobic, bacteria Phenol <19 days 100% being decreased Boyle et al.

, 1999 anaerobic, bacteria Phenol Half life 4 days WHO, 2005b

6.4.4.2 Reaction with organic matters

No data is available for reaction with organic matte rs: 2,4,6-TBP is very stable in water, so the possibility of reacting with other matters in natural water is predicted to be very low.

6.4.4.3 Potential effects on wildlife and benthic habitats

No data is available for its effects on wildlife and benthic habitats.

6.4.4.4 Potential residues in seafood

Exposure of bluegills to 2,4,6-TBP for 28 days, plateau levels were reached by 3-7 days of exposure. The half-life for re sidues was less than 24 hours fo llowing termination of exposure (WHO, 2005b).

6.4.5 Testing methods

Method Gas-chromatographic methods Applicability Salt water Sensitivity 0.1μg/l Reference DIN-EN 12673: 1999MEPC 60/2/8 ANNEX Page 50

I:\MEPC\60\2-8.doc 6.4.6 Risk characterization

Criteria PBT Criteria Reach the Criteria or not Persistence Half life In seawater>60 days, or in fresh water>40 days, or in seawater sediment>180 days, or in fresh water sediment>120 days. No (refer to section 6.4.4.1)

Enrichment BCF> 2,000 or LogP ≥ 3 No (refer to section 6.4.2.5) Toxicity Chronic NOEC<0.01 mg/L No (refer to section 6.4.3.3)

6.4.7 PNEC/PEC evaluation

6.4.7.1 PNEC evaluation

According to the shortest period L(E)C 50 of species from two different trophic levels, and lowest chronic NOEC of species from tw o different trophic levels, the im pact factor is decided to be 500.

Species Effect Value (mg/L) Minimum Impact factor PNEC

Rainbow trout (fish/fresh) 96hLC 50 0.2 Daphnia magna (crustacea/fresh) 48hEC 50 2.2 Selenastrum capricornutum (algae/fresh) 72hNOEC 0.2

Daphnia magna (crustacea/fresh) 21dNOEC 0.2 0.2 (mg/L) 500 0.4 μg/L

6.4.7.2 PEC evaluation

In the discharged ballast water scenario, the maximum value of undiluted concentration is 0.1 μg/L, which is already lower than PNEC value 0.4μg/L, so it implies that for this concentration of 2,4,6- TBP, th ere will be no effects on the aquati c environment even if it is undiluted (100%) before being discharged.

6.5 Bromate ion

6.5.1 Physical and chemical prop erties of potassium bromate

Property Value Reference CAS No. 7758-01-2 Molecular formula KBrO 3 Molecular Weight (g/mol) 167 Structural formula

Melting point ( ° C) 350 WHO, 2005 Boiling point ( ° C) 370 WHO, 2005 Flammability Non-Flammable ICSC:1115 Density (20 ° C g/cm 3 ) 3.27 WHO, 2005MEPC 60/2/8 ANNEX Page 51

I:\MEPC\60\2-8.doc

Vapour pressure (20 ° C, Pa) N/A Vapour density (air =1) 5.8 MEPC 56/2/3, annex, page 8 Water solubility (40 ° C, g/L) 133 WHO, 2005 PH in solution N/A Dissociation constant (pKa) 0.7(HBrO 3 ) EHC,216 Oxidation/reduction potential N/A Corrosivity to material or equipment Corrosive MEPC 56/2/3, annex, page 8 Reactivity to container material No touching with flammable and reductive substances ICSC:1115

Auto-ignition temperature N/A Explosivity Explosion may be caused by heating. Sensitive with mechanical impact. MSDS

Oxidizability Strong oxidizer ICSC:1115 Surface tension N/A Viscosity 66.6-67.6 MEPC 56/2/3, annex, page 8 Thermal stability and decomposition product N/A

Octanol- water partition coefficients (log Pow) -7.18 EPI Suite v3.2

Sediment- water partition coefficients (Koc) 35 EPI Suite v3.2

Henry constant (Pa.m 3 /mole) 0.85 MAM-PEC V2.0

6.5.2 Effects on aquatic organisms

6.5.2.1 Acute toxicity on aquatic organisms

Species Effect Value (mg/L) Reference
Oncorhynchus keta (fresh) 96hLC 50 512 MEPC 56/2/3, annex, page 16 Saltwater fish (sea) 96hLC 50 427-512 Thomas H., 1997 Fish
Saltwater fish lavae (sea) 96hLC 50 31 Thomas H., 1997 Daphnia magna (fresh) 48 hLC 50 179 Thomas H., 1997 Polycelis nigra (fresh) 48hLC 50 2258 Thomas H., 1997 Crustacea Mysid shrimp (sea) 24hLC 50 176 Thomas H., 1997MEPC 60/2/8 ANNEX Page 52

I:\MEPC\60\2-8.doc 6.5.2.2 Chronic toxicity on aquatic organisms

Species Effect Value (mg/L) Reference Fish N/A Crustacea N/A Algae Unknown (sea) EC50 >13.6 Tomas H.,1997

6.5.2.3 Information on endocrine disruption

No reports indicating that bromate ion might ha ve any endocrine effect s on aquatic organisms were found.

6.5.2.4 Sediment toxicity

Bromate ion is inorganic ion with the Log Pow of -7.18, which is lower than the limit value of 3, and the Koc is 35 l/kg, which is also lower than th e limit value of 500 l/kg. It is indicated that the possibility for potassium bromate being absorbed in the soil is very low and it has strong mobility. Thus, the substance is not likely to accumulate in sediments and testing with sediment dwelling species is not relevant for the assessment.

6.5.2.5 Bioavailability/biocon centration/biomagnification

The Log Pow value of potassium bromate is -7. 18 (EPI SuitTM, v3.20), which is lower than the limit value of 3. Therefore, the potential for bioconcentration/biomagnification is insignificant.

6.5.2.6 Food web/population effects

The Log Pow value of potassium bromate is -7. 18 (EPI SuitTM, v3.20), which is lower than the limit value of 3. Therefore, the possibility of effects on food web/population effects is predicted to be low.

6.5.3 Toxic effect on mammals

6.5.3.1 Acute toxic effect on mammals

Species Effect Value (mg/L) Reference

F344 male mouse Oral LD 50 400 Kurokawa et al. , 1990 F344 female mouse Oral LD 50 495 Kurokawa et al. , 1990 B6C3F1 male rat Oral LD 50 280 Kurokawa et al. , 1990 B6C3F1 female rat Oral LD 50 355 Kurokawa et al. , 1990 Syrian golden male hamster Oral LD 50 388 Kurokawa et al. , 1990 Syrian golden female hamster Oral LD 50 460 Kurokawa et al. , 1990MEPC 60/2/8 ANNEX Page 53

I:\MEPC\60\2-8.doc 6.5.3.2 Effects on skin and eye

Main symptom Result Reference Skin Redness, stinging and pain to the skin. The skin will be slightly burned after a long time. Irritant MSDS

Eye Redness, pain and damage Irritant to
eyes MSDS

6.5.3.3 Repeated-dose toxicity

Exposure Route Exposure Duration Exposure dose Species Results Reference

Oral 15 weeks 30 mg/kg/d Mice NOAEL=30 mg/kg/d MEPC 56/2/3 Oral 2 weeks 0-540 mg/kg/d Male SPF
rats Decrease in weight was observed in the high dose group. Weight of kidney, lung and liver increased. NOAEL=107 g/kg/d WHO, 2005

Oral 13 weeks 150-10,000
ppm Female and male F344 mice All animals taking the dose of >1250ppm died. Animals taking the dose of <600ppm all survived, and weight suppression was observed. Kurokawa et al. , 1986

Oral 78 weeks 0-91.6 mg kg/d Female B6C3F1
rats No side-effects. Kurokawa et al. , 1986

Oral 4 and 8 and 12 weeks 75 ppm Mice, dogs and monkeys No side-effects WHO, 2005a

Oral 15 months 30 mg/kg/d Male Wistar mice Development suppressions were observed. Sponge kidney, nitrogen increased and abnormal structure of renal tubes were caused. LOAEL=30mg/kg/d WHO, 2005a

Oral 100 weeks 0-28.7 mg/kg/d Female and male F344 mice Death and weight gain were observed in male mice of highest dose group. NOAEL=1.1 mg/kg/d WHO, 2005a

Oral 100 weeks 0, 6.9, 32.5 and 59.6 mg/kg/d B6C3F1
rats No changes were observed. NOAEL=59.6 mg BrO 3 — /kg/d WHO, 2005aMEPC 60/2/8 ANNEX Page 54

I:\MEPC\60\2-8.doc 6.5.3.4 Development and reproductive toxicity

Exposure Route Exposure Duration Exposure dose Species Results Reference

Oral 0-250 ppm Female andmale SpragueDawley rats Only a little sperm number decrease of epididymides were observed. NOAEL=80
ppm NTP, 1996, abstract for RDGT9400

Oral 10 months 14 ppm and 100 ppm Female and male mice No changes were observed. Kurokawa, 1990

6.5.3.5 Carcinogenicity/mutagen icity/reproductive toxicity

Exposure Route Exposure Duration Exposure dose Species Results Reference

Oral 110 weeks 500 and 250 ppm Female and male mice Not only cause renal carcinoma to the mice but also peritoneal mesothelioma to the male mice Kurokawa, 1986

Fills the stomach 78-104 weeks 500- 1,000
ppm Female and male F344 mice For the 1,000 ppm dose group, lung cancer, liver cancer and lymphoma were observed. For the 600 mg/kg group, one renal carcinoma case was observed. Kurokawa, 1990

Oral 24 hrs 167-501 mg/kg Mice Dramatically increase of intraosseous chromosome aberration rate was observed and the value decreased in 24 hours. Fujie, 1988

6.5.3.6 Toxicokinetic

There were some tests reports about the kinetics and metabolism in animals and humans, though different results were concluded. Following oral administration, bromate is absorbed from the gastrointestinal tract in both humans and animals. Bromate is excreted mainly in the urine, partly as bromate and partly as bromide (WHO, 2005a).

6.5.3.7 Toxicity on human

Potassium bromate can cause naupathia, vomiting, bellyache, diarrhea, anuria and centrum neurothlipsis, hemolytic anemia, hydropneumonia of varied degrees, et c. Most of these symptoms were reversible. Af ter taking the dose of 240-500 mg/kg/ d, renal failure and deafness may be caused, some of which ma y be irriversible (WHO, 2005).

According to the massive outcomes in animal test s, potassium bromate is classified as Group 2B by IARC (IARC Supplement 7) (possibility of carcinogenicity to human).MEPC 60/2/8 ANNEX Page 55

I:\MEPC\60\2-8.doc 6.5.4 Environmental fate and effect under aerobic and anaerobic conditions

6.5.4.1 Modes of degradation

Environment Route Degradation
outcome Results Reference

Water React with substances with reducibility, including metal and organics. bromide ion Half-life 12 hours MEPC 56/2/3, annex, page 20

6.5.4.2 Reaction with organic matters

As described in WHO (2005) doc uments, bromate is not a volatile substance, and it can be absorbed in the soil and sediments only in slight amount. It can react with many organic matters and produce bromate ion.

6.5.4.3 Potential physical effects on wildlife and benthic habitats

No data is available for the potential physi cal effects on wildlife and benthic habitats. Considering its relatively low Log Pow of -7.18, and Koc of 35 L/kg, the effects are predicted to be insignificant.

6.5.4.4 Potential residues in seafood

Because of its low Log Pow of -7.18 and Koc of 35 L/kg, the possibility of bioaccumulation is insignificant, and it is assumed to be no residues in seafood.

6.5.5 Testing methods

Method IC-ICP-MS technique Applicability Salt water Sensitivity 1μg/l

6.5.6 Risk characterization

Criteria PBT Criteria Reach the Criteria or not Persistence Half life In seawater > 60 days, or in fresh water> 40 days, or in seawater sediment>180 days, or in fresh water sediment>120 days. No (refer to section 6.5.4.1)

Enrichment BCF>2,000 or LogP ≥ 3 No (refer to section 6.5.1) Toxicity Chronic NOEC<0.01 mg/L No (refer to section 6.5.3.3)MEPC 60/2/8 ANNEX Page 56

I:\MEPC\60\2-8.doc 6.5.7 PNEC/PEC evaluation

6.5.7.1 PNEC evaluation

Toxicity data of bromate is limited. According to the shortest period LC 50 of species from two different trophic levels, and lo west chronic NOEC of species fr om two different trophic levels, the impact factor is decided to be 5000.

Species Effect Value (mg/L) Minimum Impact factor PNEC

Saltwater fish lavae (fish/seawater) 96hLC 50 31 31 (mg/L) 5000 6.2 μg/l

Mysid shrimp (crustacea/seawater) 24hLC 50 176

6.5.7.2 PEC evaluation

In the simulated discharged ballast water (refer to section 3.5, NIVA re port), the maximum value of undiluted concentration is 3.5μg/L which is al ready lower than PNEC value 6.2 μg/L, so it implies that for the ballast water with this concen tration of bromate ion, there will be no effects on the aquatic environment ev en if it is undiluted (100%) before being discharged.

6.6 Carbon monoxide

6.6.1 Physical and chemical prop erties of carbon monoxide

Property Value Reference CAS No. 630-08-0 Molecular formula CO Molecular weight (g/mol) 28.01 Structural formula C-O Melting point ( ° C) -205 Carbon monoxide HSDB Boiling point ( ° C) -191.5 Carbon monoxide HSDB Flammability Flammable; react with oxygen Density (0 ° C, g/l) 1.25 Carbon monoxide HSDB Vapour pressure (20 ° C, Pa) > 1 atm Carbon monoxide HSDB Vapour density (air =1) 0.968 Carbon monoxide HSDB Solubility in water (20 ° C, g/l) Slight, 2.3ml/100cc Carbon monoxide HSDB PH in solution N/A Dissociation constant (pKa) N/A Oxidation/reduction potential N/A Corrosivity to material or equipment No

Reactivity to container material No reaction in normal condition MSDSMEPC 60/2/8 ANNEX Page 57

I:\MEPC\60\2-8.doc

Auto-ignition Temperature ( ° C) 639 ° C MSDS

Explosivity It may explode when heated Carbon monoxide OSHA

Oxidizability Yes Surface tension 9.8 mN/m Carbon monoxide HSDB Viscosity 16.62 uN s/sq m Carbon monoxide HSDB Thermal stability and decomposition product decompose into carbon and carbon dioxide at 400- 700 ° C Carbon monoxide HSDB

Octanol-water partition coefficients (Log Pow) Sediment-water partition

coefficients (Koc) Henry constant (Pa.m 3 /mole)

6.6.2 Effects on aquatic organisms

6.6.2.1 Acute aquatic toxicity

There are no data indicating that carb on monoxide has acute aquatic toxicity.

6.6.2.2 Chronic aquatic toxicity

There are no data indicating that carb on monoxide has chronic aquatic toxicity.

6.6.2.3 Information on endocrine disruption

There are no relevant data available.

6.6.2.4 Sediments toxicity

There are no relevant data available.

6.6.2.5 Bioconcentration/biomagnification

There are no relevant data available.

6.6.2.6 Food web/population effects

When carbon monoxide is inhaled, the body will pos sibly die because of absence of oxygen. It does not have a potential for bioconcentration/bi omagnification, so the possibility of food web/population effects is negligible.MEPC 60/2/8 ANNEX Page 58

I:\MEPC\60\2-8.doc 6.6.3 Toxic effect on mammals

6.6.3.1 Acute toxic effect on mammals

Species Effect Value(ppm) Reference Rats Inhalation LC 50 1807 Carbon monoxide OSHA

6.6.3.2 Effects on skin and eye

Inhalation is the main exposure route. It causes no skin toxicity and no effect on skin or eyes either.

6.6.3.3 Repeated-dose toxicity

Exposure
route Duration Dose Species Method Results Reference

Inhalation 6 weeks 57 and 110 mg/m 3 Dogs Intermittently

or continuously Abnormal electrocardiograms EHC 213

Inhalation 14 months 570 mg/m 3 (500 ppm) Monkeys Continuously No effects on the electrocardiogram EHC 213

Inhalation 38-47 days 570 mg/m 3 (500 ppm) Rats Continuously Heart weight to body weight ratios increased EHC 213

6.6.3.4 Development and reproductive toxicity

Exposure
route Duration Dose Species Method Results Reference

Inhalation Last 18 days of gestation 230 mg/m 3 Rats Continuously Decrease in litter size and birth weights EHC 213

Inhalation Continuously through gestation 210 mg/m 3 Rabbits Continuously Increase in fetal mortality; malformations EHC 213

6.6.3.5 Carcinogenicity/mutagen icity/reproductive toxicity

No relevant data are available.

6.6.3.6 Toxicokinetic

It can combine with haemoglobin to pr oduce carboxyhaemoglobin, decreasing the oxygen-carrying capacity of blood and interferi ng with oxygen release at the tissue level. Hypoxia of sensitive tissues can affect the function of many organs, including the lungs (EHC 213).MEPC 60/2/8 ANNEX Page 59

I:\MEPC\60\2-8.doc 6.6.3.7 Human toxicity

Inhalation of carbon monoxide causes tissue hypoxia by preven ting the blood from carrying sufficient oxygen. It combines reversibly with hemoglobin to from carboxyhemoglobin. Acute exposure may cause headache, flushing, naus ea, vertigo, weakness, irritability and unconsciousness. Chronic exposure can cause persis tent sighs and symptoms, such as anorexia, headache, lassitude and ataxia.
Healthy young men exposed to carbon monoxide at a concentration of 44 ppm for a prolonged period suffered no adverse health effects. Men e xposed to 50 ppm for seve ral days without relief complained of headaches, but exposure to 40 ppm for 60 days was without effect. Workers in the Holland Tunnel working 8-hour wing shifts of 2 hour s in and 2 hours out at an average carbon monoxide exposure concentration of 70 ppm had av erage carboxyhemoglobin le vels of 5 percent, and none had levels above 10 percent (carbon monoxide OSHA).

6.6.4 Environmental fate and effect under aerobic and anaerobic conditions

6.6.4.1 Modes of degradation

Carbon monoxide exists in na ture. It is a product of th e incomplete combustion of carbon-containing fuels. It has small solubility in water. But it can react with other chemicals by photolysis. The average atmospheric lifetime of carbon monoxide can be calculated to be about 2 months, with a range between 1 and 4 mont hs, which can vary enor mously with latitude and season (EHC 213).

6.6.4.2 Reactions with the organic matters
There is no data indicating its capability of reacting with other organic matters.

6.6.4.3 Potential physical effects on wildlife and benthic habitats

No relevant data are available.

6.6.4.4 Potential residues in seafood

Since carbon monoxide has no effect on bioc oncentration, it is impossible to have residu e in seafood.

6.6.5 Analytical method
The gas concentration of carbon monoxide was measured by handheld gas sensors.

6.6.6 Risk characterization

Criteria PBT Criteria R each the Criteria or
not Persistence Half-life: >60 days in marine water, or >40 days in fresh water, or >180 days in marine sediments, or >120 days in fresh water sediments No (low solubility in water)

Enrichment BCF >2,000 or LogP ≥ 3 No (refer to section 6.6.2.5) Toxicity Chronic NOEC<0.01 mg/L No (refer to section 6.6.3.3)MEPC 60/2/8 ANNEX Page 60

I:\MEPC\60\2-8.doc 6.7 Methane

6.7.1 Physical and chemical properties of methane

Property value reference CAS No. 74-82-8 Molecular formula CH 4 Molecular weight(g/mol) 16.05 Structural formula

Melting point ( ° C) -183 Methane OSHA Boiling point ( ° C) -161.5 MSDS Flammability yes Density (0 ° C, g/l) 0.55 MSDS Vapour pressure (mmHg, 37.8C) 258574 Methane OSHA Vapour density (air =1) N/A Solubility in water (20 ° C, g/l) negligible MSDS PH in solution N/A Dissociation constant (pKa) N/A Oxidation/reduction potential N/A Corrosivity to material or equipment No

Reactivity to container materi al No touch with oxidizer Auto-ignition Temperature ( ° C) 580 MSDS Explosivity Reaction with oxygen may cause explode Oxidizability No Surface tension N/A Viscosity N/A Thermal stability and decomposition product decompose into carbon and hydrogen under high temperature (>1,000 ° C) without oxygen Octanol-water partition coefficients (Log Pow) Sediment-water partition coefficients (Koc) Henry constant (Pa.m 3 /mole)

6.7.2 Effects on aquatic organisms

6.7.2.1 Acute aquatic toxicity

There are no data indicating that methane has acute aquatic toxicity.MEPC 60/2/8 ANNEX Page 61

I:\MEPC\60\2-8.doc 6.7.2.2 Chronic aquatic toxicity

There are no data indicating that me thane has chronic aquatic toxicity.

6.7.2.3 Information on endocrine disruption

No relevant data are available.

6.7.2.4 Sediment toxicity

No relevant data are available.

6.7.2.5 Bioconcentration/biomagnification

Methane is a simple asphyxiant. It can cause asphyxia in high con centration. It has a very low potential for bioconcentr ation/biomagnification.

6.7.2.6 Food web/population effects

Due to a low potential for bioconcentration/bi omagnification, the possibility of food web/population effects is negligible.

6.7.3 Toxic effect on mammals

6.7.3.1 Acute toxic effect on mammals

No report in detail is relevant with acute toxic effect on mammalian. The main exposure route is inhalation. The body will possibly be unconscious or die because of the absence of oxygen in high concentration.

6.7.3.2 Effects on skin and eye

It is not stimulated in ACGIH (7th, 2001), it was carried ou t outside the category for both skin and eye (MSDS).

6.7.3.3 Repeated-dose toxicity

No relevant data are available.

6.7.3.4 Development and reproductive toxicity

Oxygen deficiency during pregnancy has produc ed developmental abnormalities in humans and experimental animals (MSDS).

6.7.3.5 Carcinogenicity/mutagenic ity/reproductive toxicity

No relevant data are available.MEPC 60/2/8 ANNEX Page 62

I:\MEPC\60\2-8.doc 6.7.3.6 Human toxicity

Methane is a simple asphyxiant. Effects of oxygen deficiency re sulting from simple asphyxiants may include rapid breathing, diminished mental aler tness, impaired muscular coordination, faulty judgement, depression of all sensations, emo tional instability, and fatigue. As asphyxiation progresses, nausea, vomiting, pr ostration, and loss of consciousness may result, eventually leading to convulsions, co ma and death (MSDS).

6.7.4 Environmental fate and effect under aerobic and anaerobic conditions

6.7.4.1 Modes of degradation

No relevant data is available.

6.7.4.2 Reactions with the organic matters

There is no data indicating its capability of re acting with other organic matters in nature.

6.7.4.3 Potential physical effects on wildlife and benthic habitats

No relevant data is available.

6.7.4.4 Potential residues in seafood

Methane is unlikely to be pres ent as a residue in seafood.

6.7.5 Analytical method

The gas concentration of methane wa s measured by handheld gas sensors.

6.7.6 Risk characterization

Criteria PBT Criteria Reach the Criteria or not Persistence Half-life: >60 days in marine water, or >40 days in fresh water, or >180 days in marine sediments, or >120 days in fresh water sediments No (negligible solubility in water)

Enrichment BCF>2,000 or LogP ≥ 3 No (refer to section 6.7.2.5) Toxicity Chronic NOEC<0.01 mg/L No (MSDS)MEPC 60/2/8 ANNEX Page 63

I:\MEPC\60\2-8.doc 7 TOXICITY ASSESSMENT OF THE TREATED BALLAST WATER

Toxicity tests for the treated ballast water of OceanGuardTM Ballast Water Management System was carried out at NIVA, includi ng Active Substances and Relevant Chemicals in the discharged water, and the toxicity of the discharged water.

The 1 mg/L concentration was chosen for full toxi city testing of seawater . Water treated with initial TRO concentrations of 2 mg /L and 4 mg/L, was only tested w ith respect to algae toxicity.

The 4 mg/L concentration was chosen for full t oxicity testing of brackish water, based on the rapid decay of TRO in brackish water and low c oncentrations of TRO measured on day 5. The test concentrations of 1 mg/L and 2 mg/L in brack ish water were only tested with respect to algae toxicity. The two initial TRO concentrations are selected on the basis of the biological efficacy outcome and the TRO degradation condition. Ho wever, since the initial TRO of 2 mg/L in brackish water testing has reached the optimum of the balance be tween biological efficacy and toxicity, 2 mg/L and 1 mg/L will be chosen for the following tests with brackish water (22 PSU) and seawater respectively.

Since the ecotoxicological responses to emission scenario are caused mostly by TRO, so the TRO concentration has been measured timely in fixed point during the test.

7.1 Contents of oxidants

Figure 7.1 : Column diagram of varied initial TRO degrading with time in seawater (33 PSU) (refer to section 3.4, NIVA report)

Note the part in blue colour show s the results of the selected tes ting cycle. In this cycle, TRO concentration of treated seawater is be low 0.2 mg/L after one day storage.MEPC 60/2/8 ANNEX Page 64

I:\MEPC\60\2-8.doc Figure 7.2 : Column diagram of varied initial TRO degrading with time in brackish water (22 PSU) ( refer to section 3.4, NIVA report)

Note the part in yellow colour shows the results of the selected testing cycle. In this cycle, TRO concentration of treated brackish water is below 0.2 mg/L after one day storage.

During the tests, the TRO concentration was meas ured every day at the same time for 5 days. The degradation progress of TRO in different test waters can be seen in figures 7.1 and 7.2. Initial TRO levels were set at 1, 2 and 4 mg/L for the two differe nt waters. The red dashed line in the figure indicates that th e TRO concentration of 0.2 mg/L after 5 days as suggested by the GESAMP-BWWG (Ref. 0.1-0.2 mg/L, Report of th e seventh meeting of the GESAMP Ballast Water Working Group, MEPC 58/2/8).

According to figures 7.1 and 7.2, TRO concentr ation of seawater (33 PSU) and brackish water (22 PSU) treated by 1 mg/L and 2 mg/L initial TR O, is all below 0.2 mg/L. Presuming this system is installed on vessels with short voyage period, the TRO of treated ballast water before discharge can meet the requirement, without the need of adopting the TRO neutralization equipment.

7.2 Determination of holding time

After the treatment of the EUT unit, there is 1-2 mg/L Cl 2 TRO existing in the treated water for some time, and there is a certain degradation m ode for the TRO. In order to determine the degradation of TRO, samples were taken everyday (refer to figure 7.1). TRO concentrations of seawater (33 PSU) and brackish water (22 PSU) tr eated by 1 mg/L and 2 mg/L initial TRO, respectively, are below 0.2 mg/L on Day 1, (i .e. with the TC of 0. 14 mg/L and 0.09 mg/L respectively), and the FC of 0.08 mg/L and 0.04 mg/L, respectively. On day 3, the TRO concentration is stable, with the TC of 0.07 mg/L and 0.04 mg/L, resp ectively, and the FC of 0.04 mg/L and <0.02 mg/L, respectively (ref er to section 3.4, NIVA report). So the determination of holding time is 3 days.MEPC 60/2/8 ANNEX Page 65

I:\MEPC\60\2-8.doc The fast degradation rate of TRO is in the first 3 days. The degradation ratio is more than 95% in the first 3 days. From day 3 to day 5, the degr adation slows down. There is no significant difference between the TRO concen tration of day 3 and day 5.

Toxicity tests have been carried out for the trea ted water, sampled on day 5. According to the results, there is residual ecotoxi city of 33 PSU seawater treated with the 1 mg/L initial TRO, however, after dilution to some extent, it is sa fe to discharge to the environment around. No ecotoxicity will be caused by th e 22 PSU brackish water treated by the 2 mg/L initial TRO (refer to section 3.7, NIVA report). So , the suggested holding time is 3 days.

7.3 Ecotoxicity

Toxicity tests were carried out on the algae, inve rtebrate and fish. The 1 mg/L concentration was chosen for full toxicity testing of seawater. Th e test concentrations of 2 mg/L and 4 mg/L TRO were only tested with respect to marine algal growth inhibition. The 4 mg/L concentration was chosen for full toxicity testing of brackish water. The test con centrations of 1 mg/L and 2 mg/L in brackish water were only tested with respect to algae toxicity. See outcomes in the figures below (refer to figure 1, NIVA report).

1 10 100 1000

0 20 40 60 80

hours106cells/l

Cont rol

32

56

100

Figure 7.3 : Algae growth curve for 100, 56 and 32% of 33 PSU seawater treated by 1 mg/L initial TRO, sampled on day 5

In the treated seawater (33 PSU) with the ini tial TRO concentration of 1 mg/L, after being diluted in varied multiples of 32%, 56% and 100% (undiluted), respectively, no absolute effects on the growth of algae were observed. For the 32% concentration, the normal growth of algae was not affected, while for the 56% and 100% con centrations, algae was not killed, however, the growth was inhibited by different degrees. So th e simulated ballast water can cause no effects on the most sensitive algae by being diluted 3-4 times.MEPC 60/2/8 ANNEX Page 66

I:\MEPC\60\2-8.doc Table 7.1 : Ecotoxicity tests performed on t reated seawater (33 PSU), sampled on day 5

Results are presented as percenta ge (%) of treated ballast water. Dilution water is non-treated ballast water (refer to Table 18, NIVA report).

Test Species Test Result Marine algae growth inhibition 1 mg/L Skeletonema costatum EC 10 = 92% EC 50 = >100%

Marine algae growth inhibition 2 mg/L Skeletonema costatum EC 50 = 33% EC 10 = 30%

Marine algae growth inhibition 4 mg/L Skeletonema costatum EC 50 = 18% EC 10 = 11%

Acute invertebrate 1 mg/L Acartia tonsa LC 50 = >100% NOEC = 56% Acute fish test 1 mg/L Scopthalmus maximus LC 50 = >100% NOEC = ≥ 100%

Table 7.1 shows the toxic ity data of different initial TRO concentrations. In the water treated by the initial TRO of 1 mg/L, EC 50 and LC 50 levels are not reached ev en for the undiluted water, indicating that water can be discha rged directly with no significan t toxicity to the environment. It is observed that toxicity of water, treate d by the initial TRO of 2 mg/L and 4 mg/L, is obviously greater than that of 1 mg/L and the line ar relation with the TRO initial concentration is shown (refer to Table 8, NIVA report).

1 10 100 1000 10000

0 20 40 60 80

Hours106cells/l Control

32

56

100 Concentration %

Figure 7.4 : Algae growth curves for 100, 56 a nd 32% of 4 ppm TRO in 22 PSU brackish water treated by 2 mg/L initial TRO, sampled on day 5MEPC 60/2/8 ANNEX Page 67

I:\MEPC\60\2-8.doc In the treated salt water (22 PSU) with the initial TRO of 2 mg/L, after being diluted in varied multiples of 32%, 56% and 100% (undiluted), respect ively, no absolute effects on the growth of algae were observed. For the 32% and 56% con centrations, the normal growth of algae was not affected, while for the 100% concentration, light inhibition on the algae growth is observed. Thus, 2 mg/L is selected as the initial TRO le vel, and the effects on organisms will not be significant after few multiple dilution of the emission.

Table 7.2 : Ecotoxicity test performed on treated brackish water (22 PSU).

Results are presented as percenta ge (%) of treated ballast water. Dilution water is non-treated ballast water (refer to Table 19, NIVA report).

Test Species Test Result Marine algae growth inhibition 1 mg/L Skeletonema costatum EC 50 = >100% EC 10 = ≥ 100% Marine algae growth inhibition 2 mg/L Skeletonema costatum EC 50 = >100% EC 10 = ≥ 100% Marine algae growth inhibition 4 mg/L Skeletonema costatum EC 50 = >100% EC 10 = 82% Acute invertebrate 4 mg/L Acartia tonsa LC 50 = >100% NOEC = ≥ 100% Acute fish test 4 mg/L Scopthalmus maximus LC 50 = >100% NOEC = ≥ 100%

The toxicity of treated brackish water is to some extent in line with the concentration of initial TRO. No ecotoxicity will be caused by the 22 PSU brackish water treated by the 2 mg/L initial TRO, even without dilution (refer to section 3.7, NIVA report).

Two test waters with different qualities were adopted in the pilot tests carried in NIVA, according to the related Guidelines of IMO. Thr ee different TRO levels were set in the tests, i.e. 1, 2 and 4 mg/L. After 5 days storage, toxicity tests of treated water were carried out for fish, invertebrate, and algae. Results show that the t oxicity of treated seawater and brackish water is different. However, toxicity shows positive correl ation with the TRO concentration, i.e. toxicity increases with the increase of TRO concentration, which indicates that toxicity is mainly caused by TRO.

8 RISK ASSESSMENT

8.1 Risks to the safety of the ship

8.1.1 Corrosion

All the units of this system, including the pipeli nes are made of anti-corrosion materials or in anti-corrosion coatings, a nd also ballast tanks have anti-corrosi on coatings on themselves. In this system, organisms are killed by a certain concentr ation of oxidants. In the seawater itself, Cl

– poses corrosion to the ship. There is the possi bility of enhancing the corrosion to ballast tank by the oxidants from this system. However, th e degradation rate is very fast when the concentration of the oxidants is low, so the possibi lity of corrosion is predic ted to be very low. Corrosion tests for this system w ill be carried out and data will be submitted in the application for Final Approval.MEPC 60/2/8 ANNEX Page 68

I:\MEPC\60\2-8.doc 8.1.2 Fire and exposure

In tests with 33 PSU seawater treated by 1 mg/L initial TRO and 22 PSU brackish water treated by 2 mg/L initial TRO, no hydrogen, chlorine , hydrogen sulfide, or surplus oxygen were detected.

In the tests, on day 0, just after the tr eatment, 25 ppm carbon monoxide and 2.5% LEL (lower explosive limit) methane were detected. However, on day 5, these gases were not detected.

Methane is flammable. When the concentration comes to 5%-15% in the air, it will cause fire. However, 2.5% LEL is far lower, so the po ssibility to cause fire is insignificant (refer to section 3.2, NIVA report)

Carbon monoxide is toxic. The concentratio n threshold for workshop long-term exposure is 50 ppm. So exposure to 25 ppm carbon monoxi de in short time will not pose toxicity to human.

8.1.3 Storage, loading/unloading and noise

The chemical substances are generated online in this system so there is no n eed to store, load or unload any chemical substances.

When operating, there will be some noise from the fans of the system, and the effect on the surroundings and staff is insignificant.

8.2 Risks to human health

8.2.1 Human exposure scenario (HES)

The document of assessment to human health risk will be submitted as an annex. There are Active Substances and Relative Chemicals generated by the system. When certain concentrations are reached, the substances will be harmful to human health.

Since there is no data available on the toxicity to human, data on the experimental animals and the maximum allowable concentration to the environment determined by some relevant organizations are adopted as reference. The MOS values calculated fro m the measure-reaction relations, are all lower than the reference valu e MOSref, so the substances generated by the system can be acceptable to human body. Two groups, including the crew (occupational exposure) and people in public are tested and predicted in the human exposure scenario, on the different exposur e approaches and exposure time.

8.2.2 Risk control measures

The possibility of leaking or breakdown of the system in normal working condition is insignificant, as the components used in the syst em are of good quality and stable performance. Once any error occurs, the system will be stoppe d working automatically instantly, and there will be light and sound alarms at the same time. Wh en carrying out repairs, the staff should follow the existing safety protection measures on board.MEPC 60/2/8 ANNEX Page 69

I:\MEPC\60\2-8.doc 8.3 Effects on the aquatic environment

According to the analysis of test results above, after 5 days’ storage, in 33 PSU seawater treated by 1 mg/L initial TRO, and 22 PSU brackish water treated by 2 mg/L initial TRO, there are only a few Relevant Chemicals with very lo w concentrations, and the concentration of Active Substances detected is very low. Ac tive Substances and Rele vant Chemicals and the concentration are as follows (refer to s ections 3.2, 3.4 and 3.5, NIVA report):

Table 8.1 : Concentration of chemical substances, PEC and PNEC value (The highest concentration in the te sted waters of different quality)

Name Concentration PEC PNEC TRO (sodium hypochlorite) 0.05 mg/L 0.0151μg/l 0.06μg/l

Dibromochloromethane 1.7μg/l 3.2μg/l Tribromomethane 150μg/l 0.962μg/l 5.8μg/l Dibromoacetic acid 5.9μg/l 6.9μg/l 2,4,6-tribromophenol 0.1μg/l 0.4μg/l Bromate ion 3.5μg/l 15.5μg/l

Concentrations of dibromochloromethane, di bromoacetic acid, 2,4,6-tribromophenol and bromate ion, even in undiluted treated water, ar e lower than the PNEC value, so they will not have any effects on the aquatic environment when being discharged. Concentrations of tribromomethane and TRO in undiluted treated wate r exceed the relevant PN EC value, so treated water needs to be diluted in order to make sure it will not cause any effects to aquatics. By adopting the MAM-PEC model scenario, the PEC/PNEC value of tribromomethane and active chlorine calculated is lower than 1. Therefore, it is presumed that the possi bility of toxicity from the treated ballast water to the environment is insignificant after dilution by port seawater.

Results from toxicity testing of the treated ballas t water is in line with what was expected from the PEC/PNEC assessment of Active Substances. Available data therefor e do not indicate that there are Active Substances produced by the Ocean Guard TM , which are not already accounted for in the present assessment.

Active Substances were also assessed for their Persistence-Bioaccumulation-Toxicity (PBT) potential. Although sodium hypochlorite shows signi ficant chronic toxicity, no Active Substance fulfilled more than one of the PBT criteria , and therefore none are eligible for a PBT classification.MEPC 60/2/8 ANNEX Page 70

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.MEPC 60/2/8 ANNEX Page 75

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