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\2-6.doc

INTERNATIONAL MARITIME ORGANIZATION

IMO 

# E

MARINE ENVIRONMENT PROTECTION COMMITTEE 60th session Agenda item 2 MEPC 60/2/6 24 August 2009 Original: ENGLISH

HARMFUL AQUATIC ORGANI SMS IN BALLAST WATER

Application for Basic Approval of Hy undai Heavy Industries Co., Ltd. (HHI) Ballast Water Management System (HiBallast)

Submitted by the Republic of Korea

SUMMARY
Executive summary: This document contains the non-c onfidential information related to the application for Basic Approval of the Hyundai Heavy Industries Co., Ltd. (HHI) Ballast Water Manage ment System (HiBallast), in accordance with the ìProcedure for approval of ballast water management systems that make use of Active Substances (G9)î adopted by resolution MEPC.169(57)
Strategic direction: 7.1
High-level action: 7.1.2
Planned output: 7.1.2.4

Action to be taken: Paragraph 6

Related documents: BWM/CONF/36; MEPC 53/24; MEPC 58/23; BWM.2/Circ.18 and MEPC 59/2/13

Introduction

1 Ballast water management systems, which make use of Active Substanc es or Preparations containing one or more Active Substances, shall be approved by the Organization under regulation D-3.2 of the BWM Convention.

2 The ìProcedure for approval of ballast wa ter management systems that make use of Active Substances (G9)î, adopted by resolu tion MEPC.169(57), defines the principal aspects to be documented by data or testing (MEP C 57/21, annex 1, paragraph 4.2.1) and some basic principles for risk evaluation (MEPC 57/21, anne x 1, paragraph 5.3). Ac cording to section 6 of Procedure (G9), the Organiza tion should evaluate the informa tion provided in the application.MEPC 60/2/6 - 2 -

I:\MEPC\60\2-6.doc 3 According to BWM.2/Circ.18, proposals fo r approval of ballast water management systems that make use of Active Substances are to be submitted to the Marine Environment Division of the Organization to be reviewed by the GESAMP -Ballast Water Working Group. In the meantime, a document on the proposal for approval contai ning all the non-confidential data related to the respective ballast water management systems that make use of Active Substance needs to be submitted to MEPC 60.

4 The competent authority in the Republic of Korea has verified the application dossier prepared by Hyundai Heavy Industries Co., Ltd. (HHI) and believes it to satisfy the data requirements of Procedure (G9).

5 The Republic of Korea therefore submits th e non-confidential part of the applicantís dossier in the annex of this document to the Organization for evaluation according to Procedure (G9). The complete dossier will be made available to the experts of the GESAMP-Ballast Water Working Group with the understanding of confid ential treatment.

Action requested of the Committee

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

***MEPC 60/2/6

I:\MEPC\60\2-6.doc ANNEX

NON-CONFIDENTIAL INFORMATION ON THE HYUNDAI HEAVY INDUSTRIES CO., LTD. (HHI) BALLAST WATER M ANAGEMENT SYSTEM (HiBallast)

Contents

1 INTRODUCTION

1.1 Terms and definitions 1.2 Abbreviations used in the text

2 DESCRIPTION OF SYSTEM

2.1 Working principles 2.2 Description of the ìHiBallastî system and equipment 2.3 Small-scale and laboratory test

2.3.1 Laboratory test 2.3.2 Small-scale test

2.4 Test Methods

3 PRINCIPLES OF SYSTEM

3.1 Disinfection principl es by chlorination 3.2 Principles of electro-chlorination 3.3 Principles of de-chlorination 3.4 Chlorination by-product

4 IDENTIFICATION OF THE SUBSTANCE (G9: 4.1)

5 DATA-SET FOR ACTIVE SUBSTANCES AND PREPARATIONS

5.1 Data on effect on aquatic plants, invertebrates and fish (G9: 4.2.1.1) 5.2 Data on mammalian toxicity (G9: 4.2.1.2) 5.3 Data on environmental fate and effect under aerobic and anaerobic conditions (G9: 4.2.1.3) 5.4 Physical and chemical properties for the Active Substances and Preparation and treated ballast water, if applicable (G9: 4.2.1.4) 5.5 Analytical methods at environmentally relevant concentrations (G9: 4.2.1.5)

6 USE OF ACTIVE SUBSTANCE

7 HAZARD CLASSIFICATION OF THE DBP S AND THEIR MATERIAL SAFETY DATA SHEETS (G9: 4.2.7)MEPC 60/2/6 ANNEX Page 2

I:\MEPC\60\2-6.doc 8 RISK CHARACTERIZATION

8.1 Screening for persistence, bioaccumulation and toxicity 8.2 Toxicity testing of treated ballast water 8.3 Risk characterization and analysis 8.4 Risk to the aquatic environmental

9 RISK ASSESSMENT

9.1 Risk to safety of ship 9.2 Risk to human health 9.3 Risk to the aquatic environment

10 ASSESSMENT REPORT

10.1 Summary of HAZID report 10.2 Summary of Risk assessment on aquatic environment

REFERENCES

APPENDICES

A ppendix 1 Quality Assurance Project Plan (QAPP) For ìHiBallastî System and Laboratory-scale (2 m 3 /hr) Test Report

A ppendix 2 Quality Assurance Proj ect Plan (QAPP) For ìHiBallastî System and Test Report of chemical analysis

A ppendix 3 Aquatic Toxicity Test Report with Discharged Water from Laboratory-scale (2 m 3 /hr) ìHiBallastî

A ppendix 4 Key Data-Set

A ppendix 5 Hazid Study on ìHiBallastî

A ppendix 6 System Description of HHI Ballast Water Management System ìHiBallastî

A ppendix 7 Environmental Risk Assessment Report

A ppendix 8 MSDSMEPC 60/2/6 ANNEX

Page 3

I:\MEPC\60\2-6.doc This report is structured in accordance with the headlines in the ìProcedure for approval of ballast water management systems that make use of Active Substances (G9)î.

1 INTRODUCTION

Hyundai Heavy Industries Co., Ltd. (HHI) has devel oped a ballast water management system for ships, named ìHiBallastî, which will protect the marine environment from the transfer of alien harmful species via ballast water. The Interna tional Convention for the Control and Management of Shipsí Ballast Water and Sediments (BWM Convention) was adopt ed at a diplomatic conference of the Internationa l Maritime Organization (IMO) in February 2004. Following its ratification, a ballast water treatment system has to be used on board all ships.

HHI is the worldís largest shipbuilding compa ny and leads the global shipbuilding industry. There are several requirements and requests fro m organizations, admini strations, shipowners, crews and shipyards on ballast water management system to comply with IMO regulations.

It is clear to consider those requirements and requests in deve lopment stage of ballast water management system. Above all, considerations such as installation spa ce and economy as well as performance and safety are the most importa nt things to facilitate application of the BWM Convention. Therefore, the system was devised to minimize installation space and operation cost as well as to satisf y performance and safety concerns.

HHI believes that we could submit test data which will be in full compliance with regulation D-2 of the BWM Convention, satisfying the standards and procedures of ìGuidelines for approval of ballast water management systems (G8)î, and complying with the ìProcedure for approval of ballast water management systems that make use of Active Substances (G 9)î, after successful land-based and shipboard test.

In addition, HHI recognizes that in case of usi ng filter unit the required disinfectant quantity can be significantly decreased, ther efore environmental risk due to disinfection by-products also could be mitigated. However, installation of fi lter unit has a weak point due to the limited space, increase of ballast pump head, or prolonged ballas ting and de-ballasting ope ration time and so on. These shortcomings are more seve re in the case of retrofit.

Thus, the experiment for Basic Approval was perf ormed without using filter unit, which has the most severe environmental risk due to disinfec tion by-products. HHI belie ves that if we could find appropriate dosage of di sinfectant which does not have harmful impact on marine environment without using filter unit, it is possible to devel op simple, easy to install and economical ballast water treatment process.

However, from the result of experiment, we c ould find some disinfection by-products that have an environmental impact, therefore, the system needs mitigation measures to prevent overdose of disinfectant through more exact cont rol of disinfectant, to minimi ze environmental risk. Needless to say, the ultimate objective of development is to protec t the marine environment.MEPC 60/2/6 ANNEX Page 4

I:\MEPC\60\2-6.doc 1.1 Terms and definitions

1.2 Abbreviations used in the text

ABBREVIATIONS

< less than ≤ less than or equal to > greater than ≥ greater than or equal to μg Microgram

b.p. boiling point Bw body weight BWMS ballast water management system

C Coulomb °C degree of Celsius (Centigrade) CAS Chemical Abstract Service cc cubic centimetre

D day(s) DOC Dissolved Organic Carbon DT50 Disappearance Time, 50%

EC50 Effect Concentration, 50% (m edian effective concentration)

FRO(C) Total Residual Oxidant (Chlorine) as chlorine

g gram GHS Globally Harmonized System

h hour

IARC International Agency for Research on Cancer IC50 inhibition concentration, 50% ISO International Organiza tion for Standardization IUPAC International Union of Pure and Applied Chemistry

K degree of Kelvin kg kilogram K oc organic carbon-water partition coefficient

L litre LC50 lethal concentration, 50% LD50 lethal dose, 50% LOAEL lowest observed adverse effect level LDLO lowest lethal dose LOEL(C) lowest observed eff ect level (Concentration) Log P ow logarithm of the octanol/w ater partition coefficientMEPC 60/2/6 ANNEX

Page 5

I:\MEPC\60\2-6.doc MEPC Marine Environment Protection Committee m.p. melting point mg milligram ml millilitre

ng nanogram NOAEL No observed a dverse effect level NOEL(C) No observed eff ect level (Concentration)

OECD Organization for Economic Co-operation and Development Organization the Internati onal Maritime Organization

PEC Predicted Environmental Concentration PNEC Predicted No Effect Concentration POC Particulate Organic Carbon P ow Octanol/water partition coefficient pH -Log [H + ] PSU Practical Salinity Unit

TLV Threshold limit value TRO(C) Total Residual Oxidant (Chlorine) as chlorine TSS Total Suspended Solid

US EPA United States Envi ronmental Protection Agency

WHO World Health Organization wt Weight

2 Description of system

2.1 Working Principles

The HHI Ballast Water Management System ìHiBallastî produces Sodium Hypochlorite (NaOCl) to disinfect harmful marine organisms. ìHiBallastî uses in-situ seawater electrolysis to produce high concentration (more than 1,000 mg/L as Cl 2 ) of disinfectant (NaOCl) from brackish water or seawater. To produce disinfectant, part of ballast water is fed to electrolyzer and the disinfectant generated in electrolyzer is directly injected into the ballast pipe during shipís ballasting operation. The disinfec tion of marine organisms and bi o-fouling control using on-site generated chlorine compounds have been widely us ed in power and desali nation plant, swimming pool, Marine Growth Prevention Sy stem (MGPS) of ship, etc.

During voyage, hypochlorite and its derivatives will disinfect a ll marine organisms and final concentration of marine organisms in discharged water will meet IMO D-2 st andard. Th e remaining hypochlorite concentration will be significantly lower than initial dose, however, to protect the marine environment, the reducing agent will be inj ected into the de-ballasting pipe to remove any remaining oxidant which might have harmful effect when discharged without neutralization. The ìHiBallastî can be installed in sk id-mounted unit or container-enclose d unit in any place in the ship. The installation of filter will be optional. The f ilter can remove large size of marine organisms and sediments and can reduce the necessary am ount of hypochlorite to disinfect all marine organisms, which was proven in laboratory scale e xperiments. Final confi guration of ìHiBallastî will be decided with evaluation of life cycle cost of ìHiBallastî during land-based pilot-scale test.MEPC 60/2/6 ANNEX Page 6

I:\MEPC\60\2-6.doc 2.2 Description of the ìHiBallastî system and equipment

The ìHiBallastî System is a promising system to protect the marine environment from the risk of Aquatic Invasive Species (AIS) a nd its units can be divided into three main functions: filtration (optional); in situ seawater electrolysis to produce and inject high concentrate of hypochlorite into main ballast pipe; and neutralization during de-ballasting operation. The ìHiBallastî system is illustrated schematica lly in figure 2.1. The detailed desc ription of ìHiBallastî system is prepared in appendix 6.

The system consists of five units as follows:

.1 Electrolysis Unit; .2 Neutralization Unit; .3 Filter Unit (optional); .4 System Control Unit; and .5 Sampling Unit.

In the case of using filter unit, the first trea tment phase is filtration with fully automatic back-flushing filter. The principal function of f ilter unit is removal of suspended objects such as large organisms, mud, silt particles and organic and inorganic particulates that could be included in sediment. The additional purpose of filter unit is to ensure water quality for treatment efficiency of electrolysis unit. The system uses filter unit only in uptake (ballasting) operation and returns back-flushed water to its point of origin. Therefore, no new waste is produced from filter.

The second phase is treatment wi th electrolysis unit. The key role of electrolysis unit is generating Active Substances, whic h is a kind of disinfectant, us ing electro-chemical reaction and injecting concentrate of disinf ectant, Active Substances, into the mainstream of ballast water. The operation of this unit is only in ballasting ope ration. In addition, to ensure safety operation of electrolysis unit, specially devi sed gas venting system was adopted.

The purpose of neutralization unit is to detoxify possible residuals, which could be residual chlorine or bromine derivatives measured as Tota l Residual Oxidant (TRO) in ballast water. In de-ballasting operation, remaining disinfectant which might be harmful to marine environment will be reduced by neutralizing agent, such as thiosulfate and sulfite.

In the case of not using filter unit, the first treat ment is done by electrolysi s unit during ballasting. In this case, more concentration of disinfectan t is required to inactiv ate intake of marine organism. The more residuals remain in discharg ed water, the more neutralizing agent will be consumed during the de-ballasting operation.

The results of laboratory- scale experiments indicate that: without f ilter unit, 10-15 ppm of TRO, chlorine dose was necessary; and with filter unit, about 5 ppm of TRO, chlorine was necessary to comply with regulation D-2. In addition, an equi valent of about 1.3-1.7 times of thiosulfate was needed for neutralization of residual TRO.MEPC 60/2/6 ANNEX

Page 7

I:\MEPC\60\2-6.doc BALLAST
WATER
TANKS FILTRATION

(Option) ELECTROLYSIS Ballasting

Sea

Sea NEUTRALIZATION S-1 S-2 S-3

S-4 S-5 De-Ballasting

Figure 2.1 : Schematic Process Diagram of th e ìHiBallastî Water Management System

.1 Electrolysis unit

The principal function of el ectrolysis unit is production of high concentration of disinfectant, hypochlorite generated from in situ electro-chemical reaction. Electrochemical production of chlorine is well establishe d technology and has wide applications, such as Marine Growth Preven tion System (MGPS) of ship and off-shore plant, land-based on-shore chemical , power and desalination plant.

As shown in figure 2.2, in the case of using filt er unit, part of seawater will be fed to electrolysis unit after filter unit as in case 2. In the case of not using filter unit, part of seawater will be also fed to electrolysis unit ju st after ballast pump as in case 1. In this case, to ensure water quality for electrolysis, st rainer will be installed before electrolyzer.

Electro-chemically-produced disinfectant is inj ected to the mainstream of ballast pipe only during ballasting operation. After inj ection, disinfectant will be diluted with seawater in pipe and will flow to ballast tank. During the voyage period, residual of disinfectant will kill marine or ganisms and suppress re-growth of organisms. As a side reaction of electro-chemical pr oduction of chlorine, hydrogen is generated on cathode of cell. Because the gas is highly explosive, it should be properly vented from the system as soon as possible whenever it is produced. Th erefore, specially devised vent system was adopted. The vent system uses water eductor and discharges gas over board with water. After discharge, some part of hydrogen gas wi ll dissolve in seawater and other parts will be out of water and diluted with air. The vent system does not need vent line up to upper deck when the system is installed in engine-room. The ìHiB allastî system will selectively adopt eductor vent system and air blowing vent system according to the installation location and customerís requirement.MEPC 60/2/6 ANNEX Page 8

I:\MEPC\60\2-6.doc The dosage of disinfectant will be controlled by feedback of TRC (total residual chlorine) or FRC (free residual chlorine) measuremen t and supplementary pH and ORP of diluted seawater. Cascade control of disinfectant concentration will be carried out by using control of rectifier curren t and estimated or measured disinfectant concentration.

.2 Neutralization unit

The objective function of neutra lization unit is to detoxify possible residual chlorine or other chemical oxidants cont ained in ballast water during de-ballasting operation. For effective neutralization reac tion, effective mixing and react ion time are important. Therefore, to make effective mixing between neutralizing agent and ballast water, the agent is fed to the suction part of ballast water pump. Then, the agent will be mixed passing through pump. The residua l concentration is measured or estimated and the value is fed back to the neutralizing agent flow controller. For more accurate and robust control, cascade control of discharged residua l chlorine regulates residual concentration to maintain discharged TRO (or FRO) under certain concentration (e.g., 0.2 mg/L as Cl 2 ). In addition, to correct and monitor possi ble measurement error, simultaneous and supplementary oxidation and reduction pot ential (ORP) and pH measurement are recommended. The detailed description of neut ralization unit is prepared in appendix 6.

Low Sea Chest (S) Water Ballast Pump ELECTROLYSIS UNIT (U1)

High Sea Chest (P)

FILTER UNIT BY-PASS

BALLAST WATER ELECTROLYZER FEED

HIGH CONCENTRATE of DISINFECTANT

BACK-FLUSHED WATER VENT GAS

Filter Unit

(U3)

Overboard Discharge DEBALLAST

WATER

Neutralization Unit (U2) NEUTRALIZING

AGENT Ballast Tanks BALLAST WATER DEBALLAST WATER SYSTEM BOUNDARY

CASE 1

CASE 2 SEA

SEA Figure 2.2: Block diagram of BWMS

.3 Filter unit (optional)

This filter unit is composed of a 50 μm filter elements with automatic back flushing. The filter removes large particles and organisms from the seawater. This filtration reduces the sediment load of the ballast water and, hen ce, reduces sediment build-up in the ballastMEPC 60/2/6 ANNEX

Page 9

I:\MEPC\60\2-6.doc water tanks. According to HHIís laboratory experiments, the filter can reduce the required amount of disinfectant to meet IMO D-2 standard. HHI would like to recommend the installation of filter for new ship and will evaluate the cost of filter installation for retrofit. Also, the exact functi on and cost benefit of filter will be evaluated in the pilot scale and shi pboard test in the future.

.4 System control unit

The system control unit of BWMS, independent of the ship ís Integrated Automation System (IAS) or operator console, controls electrolysi s, neutralization and fi lter units and system valves and monitors the status of system . The unit has commercial programmable logic controller (PLC) and operator can manipulate system via operator interface installed in shipís office or cargo control room (CCR). The operator interface will have a design to facilitate treatment operation by crew. For system operation, the crew should be educated with a minimum required curr iculum for operation and ma intenance. The unit will provide connection of hard wiring or da ta communication through Ethernet to communicate data between IAS or cons ole and other system as an option.

.5 Sampling unit

The sampling unit facilitates sampling of treated water equipped with flow measuring and sample preparation devices. In addition, resi dual water after sample preparation will be returned to ballast pipe to minimi ze load of bilge tank or bilge well.

2.3 Small-scale and laboratory test

2.3.1 Laboratory test

2.3.2 Small-scale test

Small-scale test objective is to verify laboratory test result using marine organisms with the same concentration of IMO influent water. The test wa s performed with seawater and brackish water. Through the test, the system performance and requir ed neutralizing agent quantity were carefully verified. Chemical analysis with control and tr eated water was performed to estimate the basis for environmental risk assessment. As a result, the system performance was enough to meet regulation D-2.

In addition, acute toxicity tests for marine organisms were conduc ted with discharged water of small-scale test. The test in adva nce of land-based test showed that some levels of toxicity were found for algae. Based on acute toxicity test and environmenta l risk assessment, appropriate measures to minimize environmental impact will be proposed after land-based test.

.1 Test facility

The small-scale test system, 1.98 m 3 /hr of treatment capacity, was installed at Jin-Hae Bay (Masan Bay), the Republic of Kore a, as shown in figure 2.7. The small-scale test facility was operated for the toxicity test, treatment performance test and sampling of chemical analysis in water.MEPC 60/2/6 ANNEX Page 10

I:\MEPC\60\2-6.doc Figure 2.7: Small Scale Test Facility of ìHiBallastî

The flow diagram of the test facility is s hown in figure 2.8. It has three tanks and three pumps. All materials for the test facility such as pipes, valves, pumps and tanks are appropriate for electrolysis unit.

.2 Operation of test facility:

- Flow rate 1.98 ± 0.1 m 3 /h - Treated volume about 3.8 m 3 - Salinity 34 PSU (Seawater), 21 PSU (Brackish water)

.3 Sampling and measurements

Sampling locations (points) are indicated by S1-S6 in figure 2.8. All grab samples for chemical analysis and performance analysis were collected in triplicates at beginning, middle, and end of ballasting and de-ballas ting mode, as necessary. S1, S2 and S5 represent the sampling from each tank, T1 (F eed Water Tank), T2 (Control Water Tank) and T3 (Treated Water Tank) , respectively. Sampling point S3 was used for sampling electrolyzer performance analysis. Procedur es for sampling and tran sfer were described in detail in appendix 1.MEPC 60/2/6 ANNEX Page 11

I:\MEPC\60\2-6.doc SEA Feed Water Tank (T1) ELECTROLYSIS UNIT

Control Water Tank (T2) Treated Water Tank (T3) Sampling Tank for Toxicity Test

S1

S2 S3 Neutralizing Agent (Sodium Thiosulfate )

S5 S4

Sampling Tank for Toxicity Test S6

Figure 2.8: Test water flow diagram; Po sitions of sampling are as follows:

S1: Feed water (IMO soup); S2: Control water; S3: Electrolyzer discharge water (concentrate of disinfectant); and S4: Treated water

Table 2.2: Grab sample informat ion from ìHiBallastî system

Sampling Location Sample for Control
water Treated
water On-site
measurements Off-site
measurement Remark

Toxicity S2 S5 - Toxicity
Day 0 before

ballasting S1 S1 Day 0 during

ballasting S2 S3, S4, S5

Day 1 S2 S5
Day 5 before de-ballasting S5 Chemical Analysis

Day 5 after neutralization S2 S5 - DO

- ORP

- pH

- Salinity

- TRO

- Turbidity

- Temperature - DOC, TOC, POC*

- Chemicals

IMO soup S1 S1 Day 0 during

ballasting S2 S4
Day 5 before de-ballasting S5 Performance

Analysis
Day 5 after neutralization (de-ballasting) S2 S5, S6 - DO

- ORP

- pH

- Salinity

- Turbidity

- Temperature - Organisms: ≥ 50 μ m, ≥ 10 - 50 μ m

- Bacteria

- TSS

Note: POC is estimated value from difference between TOC and DOC.MEPC 60/2/6 ANNEX Page 12

I:\MEPC\60\2-6.doc .4 Result of performance te st and chemical analysis

The following table summarizes the result of performance test. As shown in Table 2.4, system performance met regulation D-2. It is remarkable that only about 5 ppm of TRO after 5 days was enough for both salinity cases without using a filter unit. The result was matched well with laboratory experimental result. However, it was found that the discharge water has a toxic effect for algae, although the discharged water was neutralized with agent. The required neutralizing agent quan tities before discharge were about 1.3 and 1.7 times of equivalent of sodi um thiosulfate for seawater and brackish water, respectively. It was presumed that the required concentration of disinfectant depends on the concentration of suspended soli ds and organic compounds in seawater as well as organism concentration. We will ac cumulate all data at different operation conditions during land-based test and sea trial. For more deta iled result of performance and chemical analysis, please re fer to appendix 1 and appendix 2.
As shown in figure 2.9, TRO concentrations were changed according to time. Through the experiment, the required initial TRO concentration to inactivate organisms was estimated in the range of 10 ñ 15 mg/L as Cl 2
. Table 2.4: Data summary of small-scale test

Content Feed Water (Day 0) Control (Day 5) Treated Water before and after Neutralization (Day 5) Remark

Salinity of test water (PSU) 34 21 34 21 34 21

TRO (mg/L as Cl 2 ) 0 0 0 0 5.14/ 0 5.76/ 0 before/after

FRO (mg/L as Cl 2 ) 0 0 0 0 4.25/ 0 3.59/ 0 before/after
DOC (mg/L) 4.74 11.9 POC (mg/L) 9.56 33.5 TSS (mg/L) 43.5 83.3 Organism (10 μ m < size ≤ 50 μ m) (/ml) 726 6,675 1,255 30,252 0 0 Acceptable

Organism (size > 50 μ m) (/m 3 ) 128,100 354,750 3,150 31,500 0 0 Acceptable Heterotrophic Bacteria (cfu/100 ml) 15,909 158,182 1,900 Acceptable

Escherichia coli (cfu/100 ml) 19 TNTC 0 21 0 0 Acceptable

Intestinal Enterococci (cfu/100 ml) 11 208 7 6 0 0 Acceptable

Vibrio cholerae (cfu/100 ml) 0 0 0 0 0 0 Acceptable

Note: TNTC means ìtoo numerous to countî.MEPC 60/2/6 ANNEX Page 13

I:\MEPC\60\2-6.doc .5 Toxicity test
The following tables summarize the result of acute toxicity test for discharged water from small-scale test facility. As a result, algal toxicity was found in both of seawater and brackish water. Therefore, it was conclude d that suitable means, such as preventing over-dose, to minimize environmental impact due to toxicity of discharge water is required. For more detailed test result, please refer to appendix 3 or section 8.2.4.

2.4 Test methods

The detailed sampling and analysis methods were described in a ppendix 1 and appendix 2.

3 PRINCIPLES OF THE SYSTEM

3.1 Disinfection princi ples by chlorination

There are some other disinfectants used today ap art from chlorine, which is one of the most popular disinfectants. Besides disinfection, chlorine in aqueous solutions is widely used for a number of purposes such as disinfection, foulin g control, taste and odour control, bleaching, and as a powerful oxidizing agent in various manufacturing processes. Therefore, the chemical information of chlorine and its derivatives, whic h include equilibrium and toxicity, is relatively well known. In addition, recent concerns of chlorine disi nfection are organic by-product formation and its toxic and hazardous effect and control.

.1 Chlorine chemistry
Chlorine is a strong oxidizing agent and has a germicidal effect to modify the chemical character of water. For example, it is used to control bacteria, algae, and macroscopic bio-fouling organisms in cooling water circuits. It is also us ed to destruct sulfur dioxide and ammonia, the reduction of iron and manga nese by converting insoluble form, and the reduction of color. In contact with water, chlorine gas diss olves and hydrolyzes to form hypochlorous acid (HOCl), as s hown in following reaction:

Cl 2 (gas) ! Cl 2 (aqueous)

Cl 2 (aqueous) + H 2 O ! HOCl + H + + Cl The hypochlorous acid undergoes further ioni zation to form hypochlorite ions (OCl - ):

HOCl ! H + + OCl The equilibrium concentrations of HOCl and OCl - depend on the pH of the water. Increasing the pH of water shifts the above e quilibrium relationships to the right, causing the formation of higher concentration of OCl - . The relative amount of hypochlorous acid or hypochlorite present depends on pH and to a slight extent on temperature. The following figure 3.1 illustrates e quilibrium between HOCl and OCl - as a function of pH. Since many chemical and electrochemical methods used to determine chlorine concentration could not dist inguish between them, it is common to express the two together as free available or re sidual chlorine (FAC or FRC):
FR(A)C = OCl - + HOClMEPC 60/2/6 ANNEX Page 14

I:\MEPC\60\2-6.doc Figure 3.1: Equilibrium changes of free chlorine with pH [Haas]

.2 Chlorine as a disinfectant

It was believed that the superior biocidal effectiveness of hypochlorous acid comes from the relative ease with which it can penetrate cell walls due to its similar structure of water. The penetration is comparable to that of wa ter and can be attributed to both its low molecular weight and to its electrical neutra lity. On the contrary, hypochlorite ion has a relatively poor germicidal effectiveness, becau se of its inability to diffuse through the cell wall of organisms. It is believed that th is obstacle comes from negative charge of hypochlorite ion. In addition to pH, temperatur e could affect biocidal efficiency due to temperature, which can change the equilibrium state, diffusion and metabolic rate of organism.

Although exact germicidal and biocidal mechanis m of chlorine residual is not clear yet, it is believed that chlorine reacts irreversibly with enzymatic system of organism, thereby killing or inactivating the organism. In additio n, it is generally agreed that the relative efficiency of disinfecting compounds is a functi on of the diffusion rate of the active agent through the cell wall and intern al attack after pe netration. Theref ore, disinfection efficiency is affected by the following factors:

- kind of disinfectant and its property; - concentration of disinfectant; - water quality including pH; - contact time with disinfectant; and - temperature.MEPC 60/2/6 ANNEX Page 15

I:\MEPC\60\2-6.doc .3 Chlorine demand

Reaction with ammonia: In the presence of certain dissolved constituents in water, the disinfectant may react and tran sform to less biocidal chemical forms, in other words, lower energy level compound in thermodynamics aspect. In the case of chlorine, these principal reactions are with ammonia and am ino nitrogen compounds. In the presence of ammonium ions, free chlorine can form chlora mines, mono-, di-, and tri- chloramine, as follows:

formation of mono-chloramine: NH 4 + + HOCl = NH 2 Cl + H 2 O + H + formation of di-chloramine: NH 2 Cl + HOCl = NHCl 2 + H 2 O formation of tri-chloramine: NHCl 2 + HOCl = NCl 3 + H 2 O

Reaction with organic matter: Organic amines react with fr ee chlorine to form organic monochloramines. Although the rate constant is generally less than that of inorganic chloramines, the pattern of reaction is similar to inorganic chloramines. In addition to organic chloramines, free chlorine reacts with organic constituents to produce chlorinated organic by-products. Phenols, amines, aldehyde s, ketones, and pyrrole groups are readily susceptible to chlorination. The disinfection by-product (DBPs) will be described in subsequent section.

Reaction with other inorganic compounds: The rate constants of reaction between free chlorine residual and inorganic compounds likel y to be present in water are summarized in the following Table 3.2. From the table, the reaction rates of hypobromite, hypoiodite, and sulfate are the most predominant ones, wh en other conditions are assumed the same.

Table 3.2 : Summary of kinetics of HOCl and OCl- reduction by miscellaneous reducing agents [Haas]MEPC 60/2/6 ANNEX Page 16

I:\MEPC\60\2-6.doc Reaction with bromides: The bromide concentration in the seawater is 50-70 mg/L, which will be in excess of any chlorine appl ied for chlorination purposes [White]. When the chlorine solution is mixed with seawater, the chlorine reacts readily with bromide ions to form hypobromous acid as follows:

HOCl + Br - ! HOBr + Cl Subsequently, hypobromous acid will dissociate as same pattern of hypochlorous acid, which depends on pH, temperature and ionic st rength. On the contrary free chlorine, chloramines which termed as combined ch lorine, cannot oxidize bromide. Besides hypobromous acid and hypobromite, it was report ed that bromate which was known as human carcinogen, and chlorate could be formed by chlorination as follows [Xin, et al. ]:

3.2 Principles of Electro-chlorination

Electrolytic reactions

The following Table 3.3 summarizes probable electro lytic reactions during seawater and brackish water electrolysis. When electri c power supplied, electrons move from the anode to the cathode. The electron transfer results in electrical potential between el ectrodes. The possible chemical reactions as follows:

Oxidations on anode surface

Reductions on cathode surface

Among those reactions, the most probable reactions with seawater and brackish water are chlorine and hydrogen production at anode and cat hode, respectively. Besi des, water hardness, such as calcium and magnesium ions, can result in insoluble scale depo sitions on the cathode surface, as follows:

HCO 3 - + OH - = CO 3 2- + H 2 O

Ca 2+ + CO 3 2- = CaCO 3 (S)
Mg 2+ + CO 3 2- = MgCO 3 (S)

The scale deposition has been an obstacle of electrochemical hypochlorite generation with seawater. Conventionally, to clean the deposit on electrode needs acid cleaning. However, the acid cleaning could be additional shortcoming in shipboard application. Therefore, the development focuses on long-term operation without acid cleaning.MEPC 60/2/6 ANNEX Page 17

I:\MEPC\60\2-6.doc Table 3.3: Electrolytic reactions in electrolysis [Singer, Dean]

Reaction Standard Reduction Potential E o red , Volts Remark

Anodic Reaction

Chlorine Cl 2 (aq) + 2e - = 2Cl - 1.396
Hypochlorite 1.64
Hypochlorous acid 1.48
Hypobromous acid 1.33

Ozone 2.08
Hydrogen peroxide 1.78
Hydroxyl radical 2.85
Oxygen 1.23

Cathodic Reaction
Hydrogen 2H + + 2e - = H 2 0.00

Active Substances of seawater electrolysis unit

It was concluded that the follo wing compounds could be formed during seawater or brackish water electrolysis after lite rature review: Chlorine; H ypochlorous acid; Hypochlorite; Hypobromous acid; Hypobromite; and Chloramines. Therefore, these compounds were defined as Active Substances and some compounds were grouped as a Free Residual Oxidants (FRO) and other compound as a combined residual oxidants. The sum of compounds was termed as Total Residual Oxidants (TRO).

3.3 Principles of de-chlorination

Dechlorination with sodium thiosulfate

As a neutralizing agent, the solu tion of sodium thiosulfate can be used to convert any remaining residual oxidants into stable reduced form such as chloride and bromide. Sodium thiosulfate functions as a neutralizing agent when mixed with residual oxidant s, such as chlorine, in the ballast water and it reacts with chlorine according to the following equation:

Na 2 S 2 O 3 + 4Cl 2 + 5H 2 O ! 2NaHSO 4 + 8HCl

Sodium thiosulfate has been used in the pulp and paper industry and is currently trie d to be used as a neutralizing agent. It has advantage ove r using sodium bisulfite because, theoretically, sodium thiosulfate can reduce f our moles of chlorine while sodium bisulfite only can reduce one mole of chlorine.MEPC 60/2/6 ANNEX Page 18

I:\MEPC\60\2-6.doc Dechlorination with sodium bisulfite

Sodium bisulfite is a powder or granular material and could be used as a neutralizing agent of chlorinated water. The reaction is as follows:

NaHSO 3 + Cl 2 + H 2 O ! NaHSO 4 + HCl

Theoretically, one mole of bisulfite could reduce one mole of chlorine.

3.4 Chlorination by-product

Disinfection by-products (DBPs) are chemical co mpounds produced as an unintended result of water disinfection and oxidation. The compounds of greatest c oncern contain chlorine and bromine atoms. It was reported that more than 700 species of DBPs have been confirmed, among which THMs and HAAs were the most commonly detected groups [Chen].

It was reported that by-products are produced by chlorination as following table [Hrudey]. The more detailed toxicological effects of by-produc ts will be discussed in subsequent sections.

Table 3.5: Classes of established chlorination DBPs [Hrudey]

Group Compounds Remark THMs (THM4) Chloroform Bromodichloromethane Dibromochloromethane Bromoform HAAs (HAA9) Monochloroacetic acid Dichloroacetic acid Trichloroacetic acid Bromochloroacetic acid Bromodichloroacetic acid Dibromochloroacetic acid Monobromoacetic acid Dibromoacetic acid Tribromoacetic acid HANs Trichloroacetonitrile Dichloroacetonitrile Bromochloroacetonitrile Dibromoacetonitrile Halogketones (HKs) 1,1-Dichloroacetone 1,1,1-Trichloroacetone Miscellaneous chlorinated organics Chloral hydrate Chloropicrin Cyanogen halides Cyanogen chloride Cyanogen bromide Oxyhalides Chlorite Chlorate BromateMEPC 60/2/6 ANNEX Page 19

I:\MEPC\60\2-6.doc Group Compounds Remark Aldehydes (including odorous aldehydes*) Formaldehyde Acetaldehyde Glyoxal Methyl glyoxal Isobutyraldehyde* Isovaleraldehyde* 2-Methyl butyraldehyde* Phenylacetaldehyde* Aldoketoacids Pyruvic acid Ketomalonic acid Carboxylic acids Formate Acetate Oxalate Maleic acids 2-tert-Butylmaleic acid Chlorophenols (CPs), (odorous) Chlorophenol Dichlorophenols Trichlorophenols Chloroanisoles (odorous) Trichloroanisoles

Trihalomethanes

Trihalomethanes are formed as a by-product when ch lorine or bromine is us ed to disinfect water for drinking water (commonly known as disinfection by-products). They result from the reaction of chlorine and/or bromine with organic matters in the water being treated. The THMs produced may have adverse health effects at high con centrations, and many governments set limits on the amount permissible in drinking water.

Haloacetic acids

Haloacetic acids (HAAs) are a common undesirable by-product of drinking water chlorination. Following the period of intense research on trih alomethanes and other volatile DBPs in the late 1970s, researchers focused on detection, treatme nt and health effects of polar halogenated DBPs in chlorinated drinking water [Agus]. Results of this research indicated that chlorinated and brominated acetic acids occur in chlorinated water at concentr ations similar to or slightly lower than those of the trihalomethanes.

Halophenols

The chlorination of phenols (CPs) in natural wa ters results in the production of chlorine-, bromine and iodine-substituted phenols. The concentrations of halophenols in chlorinated water normally are in the order of magnitude lower th an standards for protec tion of public health.

Haloacetonitriles

Haloacetonitriles (HANs) are small, nitrogenous haloorganics that are most stable in the dihalogenated form dichloroacetonitrile (DCAN), dibromoacetonitrile (DBAN), and bromochloroacetonitrile (BCAN) [Agus]. Although HANs are usually formed at about in the order of magnitude of lower concentrations than the trihalomethanes and haloacetic acids during chlorination, they are relatively toxic and are beli eved to contribute significantly to the overallMEPC 60/2/6 ANNEX Page 20

I:\MEPC\60\2-6.doc health risks associated with consumption of chlorinated water [Agus]. Therefore, numerous studies have been conducted on the toxicology, formation, and trea tment of haloacetonitriles in drinking water.

Hydrogen

Toxic compounds, explosive gas and hydrogen will be evolved during electrolysis of water. The evolution rate is exactly proportiona l to supplied current into electro lytic cell. In case of bipolar cell unlike mono-polar configuratio n, the evolution rate of hydrogen gas is affected by number of cells in series. Practically, th e electric current efficiency of the hydrogen evolution reaction is below unity; however, the venting system will be designed considerin g current efficiency is unity.

4 IDENTIFICATION OF TH E SUBSTANCE (G9: 4.1)

ìHiBallastî ballast water management system us es brackish or seawater to produce disinfectant in situ using the principles of electro-chemical reacti on and then injects them into the mainstream of ballast water as required quantities to achieve a certain disinfection performance. At the outlet of the electrolyzer, concentrate wi ll contain several pr oducts of electrochemi cal reactions taking place at the anode and cathode surfaces of the el ectrolyzer. These are hypochlorous acid (HOCl) in equilibrium with hypochlorite ion (OCl - ), hypobromous acid (HOBr) in equilibrium with hypobromous ion (OBr - ), certain short-life oxygenated chemical compounds and oxygen gas (O 2 ) generated at the anode and hydrogen gas (H 2 ) generated at the cathode.

The following Table 4.1 summarizes Active Subs tances, Relevant Chemicals and other chemicals in this system. Measured concentrations stated in the table were experimental data of small-scale test on day 5 after neut ralization. Concentrations are in unit of μg/L, except for gas, which is in % volume.

Table 4.1: Active Substances and by-products of ìHiBallastî

Component Chemical Name CAS Number Unit MDL (Minimum Detection

Level) Conc. at 33/20

(PSU) AS, RC, BP

or Other 6
Initial TRO (measured as chlorine) 1 N.A. mg/L 0.22 10.8 * /15.5 * 8.86/12.6 AS Discharged TRO (measured as chlorine) 1 N.A. mg/L 0.22 ND/ND AS
FRO (measured as chlorine) 2 N.A. mg/L 0.05 ND/ND AS Chlorine 7782-50-5 AS Bromine 7726-95-6 AS Sodium hypochlorite 7681-52-9 AS Sodium hypobromite 13824-96-9 AS Hypochlorous acid 7790-92-3 Hypobromous acid N.A. CRO (measured as chlorine) 3 N.A. AS Chloramines 4 N.A. AS Bromamines 5 N.A. AS Sodium bromate 7789-38-0 μg/L 0.10 26.6/32.1 RCMEPC 60/2/6 ANNEX Page 21

I:\MEPC\60\2-6.doc Component Chemical Name CAS Number Unit MDL (Minimum Detection

Level) Conc. at 33/20

(PSU) AS, RC, BP

or Other 6 Halogenated Aliphatic and Aromatic Compounds including THMs N.A. RC
1,1,1-Trichloroethane 71-55-6 μg/L 0.01 ND/ND RC 1,1,2-Trichloroethane 79-00-5 μg/L 0.01 ND/ND RC 1,1-Dichloroethane 75-34-3 μg/L 0.01 ND/ND RC 1,1,2,2-Tetrachloroethane 79-34-5 μg/L 0.01 ND/ND RC 1,1,1,2-Tetrachloroethane 630-20-6 μg/L 0.01 ND/ND RC 1,2,3-Trichlorobenzene 87-61-6 μg/L 0.01 ND/ND RC 1,2,3-Trichloropropane 96-18-4 μg/L 0.01 ND/ND RC 1,2,4-Tribrombenzene 615-54-3 μg/L 0.01 ND/ND RC 1,2,4-Trichlorobenzene 120-82-1 μg/L 0.01 ND/ND RC 1,2-Dibromo-3-chloropropane 96-12-8 μg/L 0.01 ND/ND RC 1,2-Dichloropropane 107-06-2 μg/L 0.01 ND/ND RC 1,3,5-Tribrombenzene 626-39-1 μg/L 0.01 ND/ND RC 2-Chlorotoluene 95-49-8 μg/L 0.01 ND/ND RC 4-Chlorotoluene 106-43-4 μg/L 0.01 ND/ND RC Bromobenzene 108-86-1 μg/L 0.01 ND/ND RC Bromochloromethane 74-97-5 μg/L 0.01 ND/0.25 RC Chlorobenzene 108-90-7 μg/L 0.01 ND/ND RC cis-1,2-dichloroethene 156-59-2 μg/L 0.01 ND/ND RC Dibromochloromethane 124-48-1 μg/L 0.01 0.75/6.96 RC Dibromomethane 74-95-3 μg/L 0.01 3.37/0.73 RC Dichlorobromomethane 75-27-4 μg/L 0.01 0.15/0.51 RC Dichloromethane 75-09-2 μg/L 0.01 0.16/1.57 RC Tetrachloroethene 127-18-4 μg/L 0.02 ND/ND RC Tetrachloromethane 56-23-5 μg/L 0.01 ND/ND RC trans-1,2-dichloroethene 156-60-5 μg/L 0.02 0.01/ND RC Trichlorimethane 67-66-3 μg/L 0.02 0.20/0.10 RC Tribromomethane 75-25-2 μg/L 0.01 0.25/111 RC Halogenated Aceto-nitriles N.A. Trichloroacetonitrile 545-06-2 μg/L 0.01 0.02/ND RC Dichloroacetonitrile 3018-12-0 μg/L 0.02 0.04/0.14 RC Bromochloroacetonitrile 83463-62-1 μg/L 0.01 ND/ND RC Dibromoacetonitrile 3252-43-5 μg/L 0.01 0.01/0.32 RC Chloral hydrate 302-17-0 μg/L 0.02 0.02/0.01 RC Chloropicrin 76-06-2 μg/L 0.01 0.45/1.54 RC Halogenated Acetic Acids N.A. 2-monochloroacetic acid 79-11-8 μg/L 0.04 ND/ND RC 2,2-dichloroacetic acid 79-43-6 μg/L 0.01 ND/ND RC 2,2,2-trichloroacetic acid 76-03-09 μg/L 0.01 ND/ND RC 2-monobromoacetic acid 79-08-3 μg/L 0.01 5.66/6.35 RC 2,2-dibromoacetic acid 631-64-1 μg/L 0.01 55.1/32.0 RCMEPC 60/2/6 ANNEX Page 22

I:\MEPC\60\2-6.doc Component Chemical Name CAS Number Unit MDL (Minimum Detection

Level) Conc. at 33/20

(PSU) AS, RC, BP

or Other 6 2,2,2-tribromoacetic acid 75-96-7 μg/L 0.01 14.9/13.8 RC 2,2-bromochloroacetic acid 5589-96-8 μg/L 0.01 ND/ND RC 2,2,2-bromodichloroacetic acid 71133-14-7 μg/L 0.01 ND/ND RC Dalapon acid N.A. μg/L 0.05 ND/ND RC Halogenated Phenols N.A. Chlorinated Phenols N.A. RC 2-Chlorphenol 95-57-8 μg/L 0.4 ND/ND RC 3-Chlorphenol 108-43-0 μg/L 0.5 ND/ND RC 4-Chlorphenol 106-48-9 μg/L 0.5 ND/ND RC 2,3-Dichlorphenol 576-24-9 μg/L 0.4 ND/ND RC 2,4-Dichlorphenol 120-83-2 μg/L 0.8 ND/ND RC 2,5-Dichlorphenol 583-78-8 μg/L 0.9 ND/ND RC 2,6-Dichlorphenol 87-65-0 μg/L 0.8 ND/ND RC 3,4-Dichlorphenol 95-77-2 μg/L 0.9 ND/ND RC 3,5-Dichlorphenol 591-35-5 μg/L 0.6 ND/ND RC 2,3,4-Trichlorphenol 15950-66-0 μg/L 1.0 ND/ND RC 2,3,5-Trichlorphenol 933-78-8 μg/L 0.8 ND/ND RC 2,3,6-Trichlorphenol 933-75-5 μg/L 0.4 ND/ND RC 2,4,5-Trichlorphenol 95-95-4 μg/L 0.8 ND/ND RC 2,4,6-Trichlorphenol 88-06-2 μg/L 0.4 ND/ND RC 3,4,5-Trichlorphenol 609-19-8 μg/L 1.0 ND/ND RC 2,3,4,5-Tetrachlorphenol 4901-51-3 μg/L 0.3 ND/ND RC 2,3,4,6-Tetrachlorphenol 58-90-2 μg/L 0.3 ND/ND RC 2,3,5,6-Tetrachlorphenol 935-95-5 μg/L 0.4 ND/ND RC Pentachlorophenol 87-86-5 μg/L 0.4 ND/ND RC Bromonated Phenols N.A. ND/ND RC 2,4-Dibromophenol 615-58-7 μg/L 0.5 ND/ND RC 2,6-Dibromophenol 608-33-3 μg/L 0.4 ND/ND RC 2,4,6-Tribromophenol 118-79-6 μg/L 0.5 ND/ND RC Neutralizing Agent N.A. OC Sodium thiosulfate 7772-98-7 OC Gas Hydrogen Gas (% vol) 1333-74-0 % 0.1 87.9/93.5 BP Ozone Gas 10028-15-6 μL/L 0.2 Negligible BP Oxygen Gas 7782-44-7 % 0.1 NA BP Chlorine Gas 7782-50-5 μL/L 0.5 Negligible BP

Note: 1: Total Residual Oxidants 2: Free Residual Oxidants 3: Combined Residual Oxidants 4: A mixture of mono- and di- chloramines, and nitrogen trichloride 5: A mixture of mono- and di- bromamine, and nitrogen tribromide 6: AS (Active Substances), RC (Rel evant Chemicals), BP (By-Products)

ND: Not detected; NA: Not analysed; * Estimated concentration of disinfectant as injected TROMEPC 60/2/6 ANNEX Page 23

I:\MEPC\60\2-6.doc 5 DATA-SET FOR ACTIVE SUBSTANCES AND PREPARATIONS (G9: 4.2)

5.1 Data-sets on effects on aquatic plan ts, invertebrates and fish (G9: 4.2.1.1)

Aquatic toxicity data for the Active Substances and Relevant Chemicals were collected to investigate the effects on the aquatic organisms that are the algae, crustacean and fish. The most of aquatic toxicity data refe r to the literature and toxicology database provided by several research institutes, such as the Toxicology Data Network (ToxNet), Hazardous Substances Data Bank (HSDB), and Eco-toxicity (EPA ), etc. In this dossier, the lowest toxicity values found in the literature and toxicology database for algae, crustacean and fish are de picted. The detailed aquatic toxicity data for the Active Substances and Relevant Chemicals are given in appendix 4.

5.1.1 Acute aquatic toxicity

Acute toxicity data for the Active Substances and Relevant Chemicals were available in freshwater and seawater, and were summarized in Table 5.1. Thes e toxicity data were taken in accordance with the test durations with the 72 hour s, 48 hours and 96 hours for algae, crustacean and fish, respectively. So me toxicity data which did not meet the previous test durations were selected for the reasonable condition.

Table 5.1: Acute aquatic toxicity

Substances F C A * Species End point L(E)C50 (mg/L) NOEC (mg/L) Reference/
comments

Active Substances

Sodium hypochlorite F Oncorhynchus kisutch LC50/96hrs/ Marine 0.026- 0.038 - IUCLID dataset, 2000

C Daphnia magna EC50/96hrs 2.1 - IUCLID dataset, 2000

A Thalassiosira guilardii EC50/24hrs 0.075 - IUCLID dataset, 2000

Monochloramine F Oncorhynchus clarki LC50/96hrs 0.074- 0.094 - PAN Pesticide DB

C Ceriodaphnia dubia LC50/24hrs 0.016-0.02 - PAN Pesticide DB

A NA NA - - -

Relevant Chemicals

Sodium bromate F Bass prolarvae LC50/96hrs 30.8 - HSDB,2009

C Crassostrea gigas(Molluscs) EC50/24hrs/SW 170 - ECOTOX DB

A Skeletonema costatum -/7days/SW 0.125- >16 - ECOTOX DB

1,1,2-trichloroethane F Pleuronectes platessa LC50/96hrs/ Marine 55 - IUCLID dataset, 2000

C Eliminius modestus LC50/48hrs 7.5 - IUCLID dataset, 2000

A Phaeodactylum tricornutum EC50/96hrs 60 - IUCLID dataset, 2000 1,1,2,2- Tetrachloroethane F Lepomis macrochirus LC50/96hrs/SW 13 - ECOTOX DB

C Americamysis bahia LC50/96hrs/SW 9.02 - ECOTOX DB

A Skeletonema costatum EC50/96hrs/FW 6.44 - ECOTOX DBMEPC 60/2/6 ANNEX Page 24

I:\MEPC\60\2-6.doc Substances F C A * Species End point L(E)C50 (mg/L) NOEC (mg/L) Reference/
comments

1,2,3-Trichlorobenzene F Oryzias latipes LC50/96hrs NOEC/14days 3.2 0.32 NITE web site

C Daphnia Magna EC50/48hrs NOEC/21days 0.46 0.17 NITE web site

A Selenastrum capricornutum EC50/72hrs/ NOEC/72hrs 1.6 0.23 NITE web site

1,2,3-trichloropropane F Lepomis macrochirus LC50/96hrs/FW NOEC/96hrs 75 10 IUCLID dataset, 2000

C Daphnia magna LC50/48hrs NOEC/48hrs 20 5.6 IUCLID dataset, 2000

A Phaeodactylum tricornutum EC50/7days 34 - IUCLID dataset, 2000
1,2,4-Trichlorobenzene F Jordanella floridae LC50/96hrs/FW 1.217 - IUCLID dataset, 2000

C Daphnia Magna EC50/48hrs NOEC/0.1days 1.4 0.79 NITE web site

A Selenastrum capricornutum EC50/72hrs 5.7 - NITE web site

2-Chlorotoluene F Salmo gairdneri LC50/96hrs/FW 2.3 - IUCLID dataset, 2000

C Daphnia Magna EC50/48hrs NOEC/21days 0.7 0.31 NITE web site

A Selenastrum capricornutum EC50/72hrs NOEC/72hrs 7.8 2.6 NITE web site

4-Chlorotoluene F Oryzias latipes LC50/96hrs 6.1 - NITE web site

C Daphnia Magna EC50/48hrs NOEC/21days 2.0 0.32 NITE web site

A Selenastrum capricornutum EC50/72hrs 6.1 - NITE web site

Bromobenzene F Pimephales promelas LC50/96hrs/FW 5.6 - ECOTOX DB

C Daphnia magna EC50/24hrs 1.6 - ECOTOX DB

A NA NA - - -

Bromochloromethane F Cyprinus carpio LC50/3-5day/FW 61-95 - ECOTOX DB

C NA NA - - -

A NA NA - - -

Chlorobenzene F Lepomis macrochirus LC50/96hrs/FW 4.5 - IUCLID dataset, 2000

C Daphnia magna EC50/48hrs NOEC/48hrs 19.9 6.25 IUCLID dataset, 2000

A Selenastrum capricornutum LC50/96hrs 12.5 - IUCLID dataset, 2000
Cis-1,2-dichloroethene F Oryzias latipes LC50/67/96hrs/ 67 - NITE web site

C Daphnia Magna EC50/40/48hrs/ 40 - NITE web site

A Daphnia Magna EC50/21days NOEC/21days 17 4.5 NITE web site

Dibromochloromethane F Oryzias latipes LC50/96hrs NOEC/21days 79 3.2 NITE website

C Daphnia Magna EC50/48hrs 27 - NITE web site

A Selenastrum capricornutum EC50/72hrs NOEC/72hrs 9.6 4.5 NITE websiteMEPC 60/2/6 ANNEX Page 25

I:\MEPC\60\2-6.doc Substances F C A * Species End point L(E)C50 (mg/L) NOEC (mg/L) Reference/
comments

Dibromomethane F NA NA - - -

C NA NA - - -

A NA NA - - -

Dichloro-bromometane F Oryzias latipes LC50/96hrs NOEC/21days 28 0.78 NITE web site

C Daphnia Magna EC50/48hrs NOEC/21days 29 0.79 NITE web site

A Selenastrum capricornutum EC50/72hrs 12 NITE web site

Dichloromethane F Pimephales promelas LC50/96 hr/Fresh 177 IUCLID, 2000

C Palaemonetes pugio LC50/48hrs 108.5 IUCLID, 2000

A Skeletonema costatum EC50/-hrs >660 IUCLID, 2000

Tetrachloroethene F Oncorhynchus mykiss LC50/96hr/FW 4.99 IUCLID, 2000

C Daphnia magna EC50/48hrs 7.49 IUCLID, 2000

A Selenastrum capricornutum EC50/72hrs NOEC/72hrs 27 9.1 NITE web site

Tetrachloromethane F Oryzias latipes LC50/96hrs 7.6 NITE web site

C Daphnia Magna EC50/48hrs NOEC/21days 8.1 0.49 NITE web site

A Selenastrum capricornutum EC50/72hrs NOEC/72hrs 0.46 0.12 NITE web site
trans-1,2- dichloroethene (dichloroethene) F NA NA - - -

C Daphnia magna LC50/24hrs/FW <110 ECOTOX DB

A NA NA - - -

Trichloromethane

(Chloroform) F Oncorhynchus mykiss LC50/96hrs 18 IUCLID, 2000

C Daphnia magna EC50/48hrs 29 IUCLID, 2000

A Chlamydomonas reinhardii EC50/72hrs 13.3 IUCLID, 2000

Tribromomethane F Brevoortia tyrannus LC50/96hrs 9-15 ECOTOX DB

C Penaeus aztecus LC50/96hrs 20-33 ECOTOX DB

A Skeletonema costatum LC50/96hrs 12.3 ECOTOX DB

Trichloroacetonitrile F Oryzias latipes LC50/96hrs 0.072 NITE web site

C Daphnia Magna EC50/48hrs 0.044 NITE web site

A NA NA - - -

Dichloroacetonitrile F NA NA - - -

C NA NA - - -

A NA NA - - -MEPC 60/2/6 ANNEX Page 26

I:\MEPC\60\2-6.doc Substances F C A * Species End point L(E)C50 (mg/L) NOEC (mg/L) Reference/
comments

Bromochloroacetonitrile F NA NA - - -

C NA NA - - -

A NA NA - - -

Dibromoacetonitrile F Pimephales promelas LC50/96hrs 0.55 ECOTOX DB

C NA NA - - -

A NA NA - - -

Chloral hydrate F Leuciscus idus melanotus LC50/48hrs/FW 1720 ECOTOX DB

C Daphnia magna EC50/48hrs/FW 500 ECOTOX DB

A Scenedesmus quadricauda LOEC/-/FW 2.8 ECOTOX DB
Chloropicrin F Oncorhynchus mykiss LC50/96hrs/FW 0.014- 0.019 ECOTOX DB

C Daphnia pulex EC50/ 48hrs/FW 0.047- 0.086 ECOTOX DB

A NA NA - - -

2-monochloroacetic acid F Oryzias latipes LC50/96hrs 72 NITE web site

C Brachionus calciflorus LC50/48hrs NOEC/- 68.9 40 EURA RPT.

A Selenastrum capricornutum EC50/72hrs NOEC/72hrs 0.16 0.033 NITE web site

2,2-dichloroacetic acid F NA NA - - -

C Nitocra spinipes LC50/96hrs 21-25 ECOTOX DB

A NA NA - - -
2,2,2-trichloroacetic acid F Salmo gairdneri LC50/96hrs 1050 IUCLID, 2000

C Daphnia magna EC50/48hrs 2000 IUCLID, 2000

A Chlorococcales EC10/24hr 1000 IUCLID, 2000 2-monobromoacetic acid F NA NA - - -

C Daphnia magna EC50/24hrs 65 ECOTOX DB

A Scenedesmus subspicatus EC50/72hrs 0.2-1.4 ECOTOX DB

2,2-dibromoacetic acid F Pimephales promelas LC50/96hrs 69 ECOTOX DB

C NA NA - - -

A NA NA - - -
2,2,2-tribromoacetic acid F NA NA - - -

C NA NA - - -

A NA NA - - -MEPC 60/2/6 ANNEX Page 27

I:\MEPC\60\2-6.doc Substances F C A * Species End point L(E)C50 (mg/L) NOEC (mg/L) Reference/
comments

2,2-bromochloroacetic acid F NA NA - - -

C NA NA - - -

A NA NA - - -
2,2,2- bromodichloroacetic acid F NA NA - - -

C NA NA - - -

A NA NA - - -

Sodium thiosulfate F Notropis atherinoides LC50/5days/FW 2 IUCLID, 2000

C NA NA - - -

A Anlistrodesmus falcatus LC50/1hr 64 IUCLID, 2000

* Note: F is Fish; C is Crustacean; and A is Algae.

5.1.2 Chronic aquatic toxicity

Chronic toxicity data for the Active Substanc es and Relevant Chemicals are summarized in Table 5.2. Chronic toxicity data provided in th e literature and toxicol ogy database were very much restricted. However, the data were summarized in this dossier.

Table 5.2: Chronic aquatic toxicity

Substances F C A Species End point L(E)C50 (mg/L) NOEC (mg/L) Reference/
comments

Active Substances

Sodium hypochlorite F Oncorhynchus gorbuscha NOEC/23days - 0.042 PAN Pesticide DB

C Dreissena polymorpha LC50/295hrs 1.0 - IUCLID dataset, 2000

A NA NA - - -

Relevant Chemicals

1,1,2-trichloroethane F Pleuronectes platessa LC50/56day NOEC/56days 5.5 3 IUCLID dataset, 2000

C Daphnia magna EC50/21days NOEC/21days 32 18 IUCLID dataset, 2000

A NA NA - - -
1,1,2,2- Tetrachloroethane F Jordanella floridae LOEC/10day - 7.23 ECOTOX DB

C Daphnia magna LC50/28day 14 - HSDB,2005

A NA NA - - -MEPC 60/2/6 ANNEX Page 28

I:\MEPC\60\2-6.doc Substances F C A Species End point L(E)C50 (mg/L) NOEC (mg/L) Reference/
comments

1,2,4-Trichlorobenzene F Pimephales promelas NOEC/32day/ FW - 0.5 IUCLID dataset, 2000

C Daphnia magna EC50/28day 0.36-0.6 - IUCLID dataset, 2000

A Green Algae EC50/96hr NOEC/96hr 24 5.6 PAN Pesticide DB

2-Chlorotoluene F Pimeohales promelas NOEC/30 day NA 2.9 Ichem,2001

C Daphnia magna NOEC/21day - 0.14 Ichem dataset,2001

A Scenedesmus subspicatus LC50/72h >60 - Ichem dataset, 2001

Chlorobenzene F Oryzias latipes NOEC - 0.25 NITE web site

C Daphnia magna EC50/14days 2.5 - IUCLID dataset, 2000

A NA NA - - -

Dichloromethane F Oryzias latipes LC50/21day NOEC 106 75 IUCLID dataset, 2000

C NA NA - - -

A NA NA - - -

Tetrachloroethene F Oryzias latipes NOEC - 1.0 NITE web site

C Daphnia magna EC/28day 0.51 - IUCLID data -set,2000

A NA NA - - -

Trichloromethane

(Chloroform) F Oncorhynchus mykiss LC50/648hrs/ FW 2.03 - IUCLID dataset, 2000

C Daphnia magna EC50/16day NOEC/16day 60 15 IUCLID dataset, 2000

A NA NA - - -

Trichloroacetonitrile F Cyprinodon variegatus LC50/<20 days 7.1 - HSDB2009

C NA NA - - -

A NA NA - - -

2-monochloroacetic acid F Brachydanio rerio NOEC/28days - 12.5 EURA RPT.

C Daphnia magna NOEC/21day 32 - EURA RPT.

A NA NA - - -
2,2,2-trichloroacetic acid F Pimephales promelas LC50/96hrs 2000 - OECD-SIDS

C NA NA - - -

A Chlorella pyrenoidosa NOEC/14days - 0.01 OECD-SIDS

Sodium thiosulfate F Oncorhynchus mykiss LC50/18month/F W 600 - IUCLID dataset, 2000

C NA NA - - -

A NA NA - - -MEPC 60/2/6 ANNEX Page 29

I:\MEPC\60\2-6.doc 5.1.3 Endocrine disruption

No reports on the endocrine disruption potential of Active Substances and Relevant Chemicals were found in the literature. Commonl y, it was known that the chemicals such as Dichloro diphenyl trichloroethane (DDT), Polychlorinated biph enyls (PCBís), Bisphenol A, Polybrominated diphenylethers (PBDEís), and a variety of Phthalates, etc., are classified as the endocrine disruptor. However, no potential endocrine disrupting chemicals had been de tected in the treated water.

5.1.4 Sediment toxicity

No report on the sediment toxicity, which is cla ssified to the algae, crustacean and fish, for Active Substances and Relevant Chemicals were found in the literature. The sorption behaviour of substances in the sediment (soils or sludg e) can be described through parameters of the adsorption coefficient (K oc ), which is defined as th e ratio between the concen tration of the substance in the soil/sludge and the con centration of the subs tance in the aqueous phase at adsorption equilibrium. Therefore, the K oc value is a useful indicator of the binding capacity of a chemical on organic matter of the sediment and allows compar isons to be made betwee n different chemicals.

Most of K oc values for Active Substances and Relevant Ch emicals are less than 500 l/kg. Therefore, these compounds are unlikely to have the sediment toxicity. The K oc of 1,2,3-Trichlorobenzene and 1,2,4-Trichlorobenzene is estimated at 1,38 3 l/kg and 1,356 l/kg, respectively. Because the octanol/water partition coefficients (K ow ) are also more than 3, these chemicals may have effect on the sediment toxicity. K oc values for the Active Substances a nd Relevant Chemicals are summarized in Table 5.3. In Relevant Chemicals, 1,2,4- Trichlorobenzene and 1,2,3-Trichlorobenzene have K oc values larger than 500 l/kg, but these compounds were not de tected in discharged water on day 5 in small-scale test.

5.1.5 Bioavailability/ biomagnifi cation/ bioconcentration

The bioaccumulative potential of an organic ch emical substance builds up in tissues of living organisms as a result of direct exposure to polluted water, air or soil, or through consumption of contaminated food. The log K ow value can be used as a sc reening tool to indicate a bioaccumulation potential, but only direct meas urement of the BAF or BCF gives a reliable indication of a substanceís ability to bioaccumulate.

Most of K ow values for Active Substances and Relevant Chemicals are less than three except some chemicals. But, the BCF of these chemical s are less than the EU criteria to determine the PBT screening. Therefore, it is expected th at the potential for the bioavailability, biomagnification and bioconcentration is unlik ely to affect on the aquatic organisms.

5.1.6 Food web/population effects

Based on the K oc and BCF, it is anticipated that the po tential for bioaccumulation in the food chain could be negligible because these factors do not exceed the BCF criteria.

5.2 Data on mammalian toxicity (G9: 4.2.1.2)

Mammalian toxicity data for the Active Substances and Relevant Chemicals is mainly summarized in the database of toxicity revi ew papers, such as Toxicology Data Network (ToxNet), which is a database including Hazard ous Substances Data Bank and Integrated Risk Information System), International Uniform Chem ical Information Database (IUCLID), EU RiskMEPC 60/2/6 ANNEX Page 30

I:\MEPC\60\2-6.doc Assessment Report, and WHO guidelines for drinking water qualities, etc. The studies, discussed in these toxicology summarizes, represent valid and reproducible data. The detailed mammalian toxicity data for the Active Substances and Relevant Chem icals are given in appendix 4.

5.2.1 Acute toxicity

The following table (see confidential dossier) on acute mammalian toxicity lists the 50% kill lethal dose (LD50) of the tested animals for the various chemicals.

5.2.2 Effects on skin and eye

Table 5.6 (see confidential dossier) lists skin and eye effects for the various chemicals. Some of the chemical data could not be f ound for sensitization effects. As shown in Table 5.6, all of the chemicals have potentials to cause irritation to the skin and eyes at sufficient concentrations, especially halo-acetic acids (HAAs) have highly corrosive effect to skin and eyes. They are much higher than concentrations tested in treated ballast water typically.

5.2.3 Repeated-dose toxicity

Data on the sub-chronic toxicity studies, typicall y over a period of 90 days, are listed at Table 5.7 (see confidential dossier). This table notes th e NOAELs (No Observed Adverse Effects Levels) when available.

5.2.4 Chronic toxicity

Table 5.8 (see confidential dossier) lists the result s of chronic mammalian toxicity studies that are conducted in rodents over a period of 12 mont hs. This table notes the NOAELs or Lowest Observed Adverse Effects Levels (LOAEL), when av ailable. Some of the chemicals reported an increase in tumours (see details in section 5.2.6). Effect concentrations are higher than treated ballast water concentrations typically.

5.2.5 Developmental and reproductive toxicity

Table 5.9 (see confidential dossier) lists the developmental and reproductive toxicity studies. The table lists NOAELs or LOAELs when they are available. Even if relatively high doses are used, there are no effects on fertil ity for many of chemicals.

5.2.6 Carcinogenicity

Carcinogenicity studies may be combined with the chronic toxicity st udies over a period of 12 months. Table 5.10 (see confidential dossi er) showed the detail ed carcinogenicity characteristics of chemicals.

5.2.7 Mutagenicity/genotoxicity

Table 5.11 (see confidential dossier ) lists the results of mutagenicity and genotoxicity except for halo-acetic acids (HAAs). For the different chemi cals and tests, various results were observed. According to IPCS, HAAs generall y have some mutagenic potential in case of high concentration from in vitro and in vivo studies.MEPC 60/2/6 ANNEX Page 31

I:\MEPC\60\2-6.doc 5.2.8 Toxicokinetics

Table 5.12 (see confidential dossie r) summarizes the available data on toxicokinetics from WHO drinking water guidelines. Most of chemicals are ra pidly absorbed from gastrointestinal tract and excreted in the urine over th e course of several hours.

5.3 Data on environmental fate and effect under aerobic and anaerobic conditions (G9: 4.2.1.3)

5.3.1 Modes of degradation (biotic; abiotic)

TRO, sodium hypochlorite and sodium hypobromite ar e rapidly degraded in nature and they are not considered to be bio-accumulated on aquatic organisms. Table 5.13 showed biodegradation of Relevant Chemicals. The info rmation used in the table is ma inly from National Institute of Technology and Evaluation database.

Table 5.13: Biodegradation for Relevant Chemicals

Chemical Biodegradation Results Reference
Sodium bromate N.A. Sodium thiosulphate N.A.
1,1,2-Trichloroethane 28 days, MITI-I(OECD TG 301C) Non-biodegradability GC 5% NITE Database
1,1,2,2- Tetrachloroethane 28 days, MITI-I(OECD TG 301C) Non-biodegradability TOC 0%, GC 10% NITE Database

1,2,3-Trichlorobenzene 2 weeks, MITI-I(OECD TG 30 1C) Non-biodegradability BOD 0%, GC 0% NITE Database

1,2,3-Trichloropropane 4 weeks, MITI-I(OECD TG 30 1C) Non-biodegradability BOD 0%, GC 8% NITE Database
1,2,4-Trichlorobenzene Activated sludge, Ae robic=56% after 5 days IUCLID, 2000 2-Chlorotoluene Activated sludge 10 mg/l, Aerobic=0% after 28 days IUCLID, 2000 4-Chlorotoluene MITI-I(OECD TG 301C) Non-biodegradability NITE Database Bromobenzene MITI-II(OECD TG 302C) Non-biodegradability NITE Database Bromochloromethane MITI-I(OECD TG 301 C) Non-biodegradability NITE database Chlorobenzene MITI-II(OECD TG 302C) Non-biodegradability NITE database cis-1,2-dichloroethene MITI-II(OECD TG 302C) Non-biodegradability NITE database

Dibromochloromethane Aerobic, a static flask screening procedure and incubation 28 days, 25-39% loss. HSDB,2006

Dibromomethane No significant biotic or ab iotic degradative processes have been reported in natural waters or soil. HSDB,2002

Dichlorobromomethane Aerobic, a static flask screening procedure and incubation 28 days, 51-59% loss. HSDB,2009

Dichloromethane MITI-I(OECD TG 301C) Non-biodegradability BOD 13% GC 1% NITE database

Tetrachloroethene MITI-I(OECD TG 301C) Non-biodegradability BOD 11% GC 0% NITE database

Tetrachloromethane 2 weeks (MITI-I(OECD TG 301C ) Non-biodegradability BOD 0% TOC 0% NITE databaseMEPC 60/2/6 ANNEX Page 32

I:\MEPC\60\2-6.doc Chemical Biodegradation Results Reference trans-1,2- dichloroethene Closed Bottle Test (OECD TG 301D ) Non-biodegradability BOD 0% NITE database

Trichloromethane MITI-I(OECD TG 301C) Non-biodegradability BOD 0% GC 4.6% 2 weeks NITE database

Tribromomethane MITI-I(OECD TG 301C) Non-biodegradability GC 0% 4 weeks NITE database

Trichloroacetonitrile It is a by-product of water chlorination and hydrolyzes quickly, therefore biodegradation is not expected to be an important fate in the environment. HSDB, 2009

Trichloroacetonitrile It is a by-product of water chlorination and hydrolyzes quickly, therefore biodegradation is not expected to be an important fate in the environment. HSDB, 2009

Bromochloroacetonitrile It is a by-product of water chlorination and hydrolyzes quickly, therefore biodegradation is not expected to be an important fate in the environment. HSDB, 2009

Dibromoaceto-nitrile It is a by-product of water chlorination and hydrolyzes quickly, therefore biodegradation is not expected to be an important fate in the environment. HSDB, 2009

Chloral hydrate Biodegradation data for chloral hydrate were not available HSDB, 2009

Chloropicrin MITI-I(OECD TG 301C) Non- biodegradability GC 4% BOD 0% TOC 0%, 4 weeks Anaerobic, activated sludge inoculums at 20 °C : Aerobic biodegradation rate: 1.5/da y Half-life: 0.46 days NITE database HSDB, 2009

2-monochloroacetic acid MITI-I(OECD TG 301C) R eady biodegradability GC 100% BOD 65% TOC 99.8% 3 weeks NITE Database

2,2-dichloroacetic acid MITI-I(OECD TG 301C) R eady biodegradability HPLC 100% BOD 97% TOC 94% 2 weeks NITE Database
2,2,2-trichloroacetic acid MITI-I(OECD TG 301C) 4 week s, Non-biodegradability BOD 7%, TOC 42% NITE Database

2-monobromoacetic acid MITI-I(OECD TG 301C) 3 weeks, Ready biodegradability BOD 65%, GC 100%, TOC 99.8% NITE Database

5.3.2 Bioaccumulation, partition coefficient, octanol/water partition coefficient

The bioaccumulation factors (BCF s ) and octanol-water pa rtition coefficient (K ows ) for the Active Substances and Relevant Chemicals are listed in Table 5.4 of the section 5.1.5. The adsorption coefficients (K ocs ) for the Active Substances and Releva nt Chemicals are given in section 5.1.4.

5.3.3 Persistence and identification of the main metabolites in the relevant media

Because of low Log P ow and no bioavailability, there was no report on persistence and identification of main metabolites in Active Substa nce. For Relevant Chemicals, the Level III Fugacity models of the EPI suit v.4.0 uses thr ee environmental compartm ents (water, soil, and sediment) to determine the persistence of a chemical in the environment. It has estimated that any chemical is expected to be found predomin antly in any compartment and its persistence estimate is based on its transformation in this me dium (half-life). The pe rsistence of the above by-products is given in sections 5.1, 8.1 and 8.2.MEPC 60/2/6 ANNEX Page 33

I:\MEPC\60\2-6.doc 5.3.4 Reaction with organic matter

When natural organic matter is treated with hypochlorite species (HOCl, OCl), high molecular weight chlorinated compounds form in the first st ep that is followed by the cleavage of benzene rings into trihalomethanes and haloacetic acids. For most of Relevant Chemicals, there is no accumulation through aquatic organisms. And ther e is no information which is available on reaction with organic matter by Relevant Chemicals.

5.3.5 Potential physical effects on wildlife and benthic habitats

No data were available for potential physical eff ects on wildlife and benthi c habitats. Most of Active Substances and Releva nt Chemicals have low K ow and BCF values. Therefore, effects on wildlife and benthic habitats by treated ballast water w ould be expectedly low.

5.3.6 Potential residues in seafood

For Active Substances and Relevant Chemicals, ther e is no potential concentr ation of food chain. Due to low K ow

and BCF values, it is unlik ely that these will be accumul ated through the food chain.

5.3.7 Any known interactive effects

There is no study of interactive effects on Ac tive Substances and Relevant Chemicals.

5.4 Physical and chemical properties for th e Active Substances and Relevant Chemicals (G9: 4.2.1.4)

The physical and chemical properties for the Ac tive Substances and Relevant Chemicals are briefly described in Table 5.14 and detaile d in appendix 4 ì C he m icals data-setî.

Table 5.14: Physical and chemical pr operties for the Active Substances and Relevant Chemicals

Chemical MP BP FA DE VP VD WS DC CM AT Sodium hypochlorite 18 96 Non 1210 1740 ï 293000 ï Y Non

Monochloramine ï ï ï ï ï ï ï ï ï ï
Sodium bromate 381 1390 381 3339 5.6E-16 ï 364000 ï ï ï 1,1,2-trichloroethane -35 113 Non 1.44 225 4.21 4400 ï Y 460 1,1,2,2-Tetrachloroethane -43. 8 146.5 Non 1595 615.95 5.79 2900 ï Y Non

1,2,3-Trichlorobenzene 53.5 218.5 112.7 1453.3 28 6.26 18 ï ï ï 1,2,3-trichloropropane -14. 7 156.85 180 1388.9 492 5.1 1750 ï ï 304 1,2,4-Trichlorobenzene 17 213.5 105 1459 21.5 6.26 19 ï ï 571
2-Chlorotoluene -35.59 158.97 49 1082.6 350 ï 374 ï ï ï
4-Chlorotoluene 7.5 162.4 49 1069.7 374 4.37 106 ï ï 595
Bromobenzene -30.6 156.2 51 1495.2 557.3 5.41 410 ï ï 565
Bromochloromethane -87.9 68 Non 1934.4 18932 ï 16700 ï Y Non
Chlorobenzene -45.2 131.7 29.2 1105.8 1200 3.88 502 ï Y 638 Cis-1,2-dichloroethene -80 60.1 2.2 1283.7 23998 3.54 6410 ï ï 460
Dibromochloromethane -20 121.3 Non 2451 10133 ï 2700 ï ï Non
Dibromomethane -52.5 97 N on 2496.9 5866.2 6.05 11900 ï Y Non
Dichlorobromometane -57 90 Non 1980 666.1 ï 3968 ï ï Non

Dichloromethane -95 39.75 Non 1326 7653 2.93 13700 ï ï 605MEPC 60/2/6 ANNEX Page 34

I:\MEPC\60\2-6.doc Chemical MP BP FA DE VP VD WS DC CM AT

Tetrachloroethene -22.3 121.3 Non 1620 1900 5.7 160 ï Y Non
Tetrachloromethane -23 76.8 Non 1594 11940 5.32 793 ï ï ï

Dichloroethene -49.8 48.7 2.2 1257 44129 3.67 6300 ï ï 460
Trichloromethane -63.4 61.17 Non 1476 20829 4.12 8000 ï Y Non
Tribromomethane 8.69 149.1 Non 2879 718.9 8.7 3100 ï Y ï
Trichloroacetonitrile -42 85.7 195 1440 9879 ï 715 ï ï ï
Dichloroacetonitrile ï 112 ï 1369 376 ï 33500 ï Y ï
Bromochloroacetonitrile ï 138 ï 1680 121.7 ï 18700 ï ï ï

Dibromoacetonitrile ï 68 ï 2296 40.13 ï 9600 ï ï ï

Chloral hydrate 57 96 ï 1908 1999 5.1 793000 ï ï ï

Chloropicrin -64 112 Non 1645 3200 5.7 1620 ï Y ï
2-monochloroacetic acid 63 189.3 126 1370 8.7 3.26 860000 2.85 Y 500 2,2-dichloroacetic acid 9.7 194 ï 1563 23.9 4.45 1.0E+6 1.26 ï ï 2,2,2-trichloroacetic acid 57.5 195.5 Non 1613 8 ï 54000 0.51 ï ï
2-monobromoacetic acid 49 208 113 1934 15.9 ï 1.8E+6 2.89 ï ï 2,2-dibromoacetic acid 48 232 113 ï 3.07 ï 2.1E+6 1.48 ï ï 2,2,2-tribromoacetic acid 129 245 ï ï 0.037 ï 200000 0.72 ï ï 2,2-bromochloroacetic acid ï 215 110 1985 18.7 ï 250000 1.40 ï ï 2,2,2-bromodichloroacet ic acid ï ï ï ï 4.8 ï 4900 0.72 ï ï
Sodium thiosulfate 48.3 100 Non 1667 ï ï 209000 ï ï ï

Note: MP : Melting Point, °C BP : Boiling Point, °C FA : Flammability(Flash point for liquids, °C ) DE : Density, kg/m 3 VP : Vapour Pressure, Pa VD : Vapour Density, Pa WS : Water solubility, mg/l DC : Dissociation Constant, pKa CM : Corrosivity to the Materials or equipment of normal ship Construction, Yes/No Details in appendix 4 AT : Autoignition Temperature Non : Non-Flammable ï : No available data
5.5 Analytical methods at environmenta lly relevant concentrations (G9: 4.2.1.5)

Procedures for sampling, transferring and analysis methods are described in detail in appendix 2 (QAPP by KTR).

6 USE OF ACTIVE SU BSTANCE (G9: 4.2.6)

The system is designed to treat ballast water only during ballasting ope ration and to minimize probable harmful effect by Active Substances, so th at discharged water will be neutralized during discharge operation.

Required dosage of the system

The required quantity, dosage, to treat intake wate r is affected by water quality including natural organic/inorganic material which could reduce applied oxi dants, concentration of organisms, pH, temperature, and so on. The chlorine demand has a key role to determine required dosage of system. The results of lab-scale and small-scale experi ments are: without filter unit, 10-15 ppm of TRO, chlorine dose was necessary; and with f ilter unit, about 5 ppm of TRO, chlorine was enough to comply with regulation D-2 . In addition, about 1.3-1.7 times of equivalent of thiosulfate was enough for neutrali zation of residual TRO. Furt hermore, the over-dosage could lead to environmental problem due to chlorina tion by-products which coul d not be detoxified by neutralization before discharge. Therefore, the system will measure concentration of residual oxidant, pH and temperature simu ltaneously to avoid over-dose.MEPC 60/2/6 ANNEX Page 35

I:\MEPC\60\2-6.doc Retention time

The required retention time is cl osely related to dosage. More dose of Active Substances to ballast water could shorten the required retentio n time. The design basis of system is 5-daysí retention time, but if needed, th e design basis could be changed acc ording to shipís voyage cycle. On the other hand, short retent ion time will affect residual concentration of disinfection by-products and the residual Active Substance concen tration. In case of discharge before 5-day retention time, the more neutralizing agent will be required to re duce residual oxidants.

Power requirement

The power requirement is 4-5.5 kWh/kg of chlorine equivalent, according to operating condition. More detailed specification of system will be available at further development stage.

System limitation

For system operation, operating conditions should be in the following range:

Applicable range of salinity: > 15 PSU Applicable range of water temperature: 15 - 33 o C Applicable range of atmos pheric temperature: 0 - 55 o C Applicable range of pH: 6 - 8.3

System configuration

The ìHiBallastî Ballast water management syst em consists of two main treatment units, electrolysis and neutralization unit, and one optional treatment unit, i.e. the filter unit. In addition, the system includes system contro l and sampling units. The following Table 6.1 summarizes the equipment units in the system.

Table 6.1: System units

Unit Function Remark Electrolysis Unit Side-stream Electrolysis

Neutralization Unit De-chlorin ation during De-ballasting Filter Unit Filtration during Ballasting Optional System Control Unit BWMS Control and Monitoring Sampling Unit Treated Water Sampling

Details of the major components and materials used

The Following Tables 6.2 to 6.6 (see confidentia l dossier) summarize major components of system. For more detailed information of sy stem and units (refer to appendix 6 ìSystem description and attached process flow diagramî).

Materials for system will fully comply with class rule. Especially, electrolyzer and piping for concentrate will be fabricated with FRP (e.g., GRP) when the system is installed in engine-room. In other case, such as installed in upper dec k, CPVC or PVC materials could be applicable.MEPC 60/2/6 ANNEX Page 36

I:\MEPC\60\2-6.doc System control and safety functions

The following Tables 6.7 to 6.10 (see confidential dossier) summarize system control functions and safety functions related to unit and system s hutdown. For more detailed information, refer to appendix 6 ìsystem descriptionî.

Operation and maintenance philosophy

The design objective of the system is to minimi ze operation and maintenance cost by providing fully integrated operatorís interf ace and rugged made element. However, the system is in the developing stage, more detailed operation and ma intenance strategies will be set up at further development stage through HAZOP and RAM studi es. For more detailed information, please refer to appendix 6 ìSystem descriptionî.

Recommended methods and precautions concern ing handling, use, storage and transport

The hazard of storage, use of ch emicals, and accidental release measures will be discussed in section 9.2 ìRisk to human health partî.

7 HAZARD CLASSIFICATION OF THE DBPS AND THEIR MATERIAL SAFETY DATA SHEETS

Of the chlorination disinfection by-products, which are known as more than 600 potential chemical species [Hrudey], 41 kinds of impo rtant groups expected to be produced during ìHiBallastî operation were extrac ted from the MSDS information for risk assessment on Active Substances (hereafter referred as AS) and Relevant Chemical (hereafter referred as RC) including IMO considerations. From hazard identification, typical hazardous chemicals reflecting potential hazards are drawn as shown in Table 7.1. MSDS for all rela ted chemicals are included in appendix 8, for more information.

Table 7.1: Summary of hazard identi fication on the Active Substances and Relevant Chemicals

Chemical class Chemical compound CAS No. AS, RC DSCL (EEC) Hazard Classification Hypochlorous acid (as 5wt.% sodium hypochlorite) 7681-52-9 AS R8, R31, R36/38, S28, S36/37/39, S45 Hypobromous acid (bromine water as potassium bromide) 7758-02-3 AS R36/37/38-36, S26-45-61-7, S9-39-36 Chloramine 10599-90-3 AS R1, R20/22 TRO

Bromamine 14519-10-9 AS N/A

Ozone 10028-15-6 AS R5, R6, R23, R36/37/38 FRO Chlorine 7782-50-5 AS R23, R36/37/38, R50, S7, S9, S44/45, S61 By-product Hydrogen 1333-74-0 AS R12, S9, S16, S33 Neutralizing agent Sodium thiosulfate 7772-98-7 - R36/37/38, S24/25-23-36-26MEPC 60/2/6 ANNEX Page 37

I:\MEPC\60\2-6.doc Chemical class Chemical compound CAS No. AS, RC DSCL (EEC) Hazard Classification Trichloromethane (Chloroform) 67-66-3 RC R20/22, R38, R40, S36/37

Bromodichloromethane 75-27-4 RC R22-37/38-40-41-39/23/24/25- 23/24/25-11 S26-36/39-45-36/37-16- 36/37/39

Dibromochloromethane 124-48-1 RC R22-39/23/24/25-23/24/25, S45-36/37/39-26-36/37 Trihalo methanes (THM)

Tribromomethane (Bromoform) 75-25-2 RC R22, R36/38, R40

Monochloroacetic acid 79-11-8 RC R23/25, R35

Dichloroacetic acid 79-43-6 RC R21, R35

Trichloroacetic acid 76-03-9 RC R35, R50/53, S26, S36/37/39, S45, S60, S61

Monobromoacetic acid 79-08-3 RC R23/24/25, R35, R50, S26, S36/37/39, S45, S61

Dibromoacetic acid 631-64-1 RC R20/21/22-34-40-36/37/38

Tribromoacetic acid 75-96-7 RC R35-40-36/37/38,S26-36, S37/39-45-24/25-36-16

Bromochloroacetic acid 5589-96-8 RC R34-40-36/37/38, S26-27-36, S37/39-45-36-16

Bromodichloroacetic acid 71133-14-7 RC R36/37/38-40-34-20/21/22, S16-26-36-45-36/37/39-27 Haloacetic acids (HAAs)

Dibromochloroacetic acid 5278-95-5 RC R36/37/38-40-34, S16-26-36-45-36/37/39-27

Dichloroacetonitrile 3018-12-0 RC R20/21/22

Trichloroacetonitrile 545-06-2 RC R20/21/22, R36

Dibromoacetonitrile 3252-43-5 RC R20/21/22-36-22, S36/37-26 Haloaceto nitriles (HANs)

Bromochloroacetonitrile 83463-62-1 RC R22-36, S26

Sodium bromate 7789-38-0 RC R8-22-36/37/38-9-36/37 S17-26-36-37/39

1,1,2-Trichloroethane 79-00-5 RC R/20/21/22-40-66-39, R23/24/25-23/24/25-11, S9-36/37-46-45-16

1,1,2,2-Tetrachloroethane 79-34-5 RC R26/27-51/53-59-39, R23/24/25-23/24/25-11, S38-45-61-36/37 Other Chemicals

1,2,3-Trichlorobenzene 87-61-6 RC R22-36/37/38-39/23/24, R25-23/24/25-52/53, S36/37-26-45-61-36MEPC 60/2/6 ANNEX Page 38

I:\MEPC\60\2-6.doc Chemical class Chemical compound CAS No. AS, RC DSCL (EEC) Hazard Classification

1,2,3-Trichloropropane 96-18-4 RC R45-60-20/21/22-29, R23/24/25-23/24/25-11-38 S53-45-36/37-36
1,2,4-Trichlorobenzene 87-61-6 RC R22-36/37/38-39/23/24/25-52- 53, S36/37-26-45-61-36

2-Chlorotoluene 95-49-8 RC R25-51/53-39/23/24, R25-23/24/25-11, S24/25-61-45-36/37-16-7

4-Chlorotoluene 106-43-4 RC R20-51/53-39/23/24/25-23, R25-11-10, S24/25-61-45-36/37-16-7

Bromobenzene 108-86-1 RC R10-38-51/53-39/23/24, R25-23/25, S61-45-36/37

Bromochloromethane 74-97-5 RC R37/38-41-59-36/37/38-20- 39/23/24/25-23, S26-39-59-37/39-45-36/37

Chlorobenzene 108-90-7 RC R10-20-51/53-40-39/23/24/25- 23/24/25-11, S24/25-61-36/37-45

cis-1,2-dichloroethylene 156-59-2 RC R11-20-52/53-39/23/24/25- 23/24/25, S7-16-29-61-45- 36/37

Dibromomethane 74-95-3 RC R20-52/53-39/23/24, R25-23/25-11, S24-61-45-36/37-16-7

Dichloromethane 75-09-2 RC R40-39/23/24/25-23/24/25-11, S23-24/25-36/37-45-16-7

Tetrachloroethylene 127-18-4 RC R40-51/53-23/25-11- 39/23/2425-23/25, S23-36/37-61-45-24-16-7

Tetrachloromethane 56-23-5 RC R23/24/25-40-48/23-52/53-59- 39/23/24/25-11, S23-36/37-45-59-61
trans-1,2-dichloroethene 156-60-5 RC R11-20-52/53-39/23/24/25- 23/25, S7-16-29-61-45-36/37

Chloral hydrate 302-17-0 RC R25-36/38-39/23/24/25-23/25- 11-36/37/38, S26-45-25-23- 36/37-16-27
Chloropicrin 76-06-2 RC R22-26-36/37/38, S36/37-38-45

Note: DSCL: Dangerous Substances Classification Labeling, EEC: European Economic CommunityMEPC 60/2/6 ANNEX Page 39

I:\MEPC\60\2-6.doc 8 RISK CHARACTERIZATION

The study was performed for substances which we re detected in discha rged water on day 5 of 33 PSU experiment. Further study will consider chemicals which were detected in the middle of 5 daysí storage in land-based test. The appli cant recognizes that the intermediate chemical is important from a viewpoint of environmental ri sk assessment because intermediate chemical might be harmful in case of emergency discha rge of ballast water or short voyage period.

8.1 Screening for persistence, bioaccumulation and toxicity

8.1.1 PBT criteria

Persistent, bioaccumulative, and toxic (PBT) subs tances are compounds that possess all three of the following characteristics, making them particularly problematic pollutants.

Persistent

Some substances are very persistent in the enviro nment, with lifetimes in the order of decades to centuries. The molecular structures of these co mpounds allow them to resist the natural fate processes in the atmosphere, waters, and biota th at break down other pollutants. A persistent substance resists physical, biolog ical and chemical degradation. A measure of a substanceís persistence can be determined fr om laboratory tests and from meas urements in the environment. It is difficult to extrapolate laboratory degradation tests to the real world due to their complex nature. In addition, most current standard tests are relatively short and have to be extrapolated to give an indication of persisten ce over longer periods. Tests often rely on indirect measures of degradation, such as oxygen consumption, rather than the direct measurement of a substanceís disappearance. Ideally, realistic laboratory te sts to determine persis tence should give an indication of the time it takes to reduce a subs tanceís concentration in the environment through any degradation process, called the disappearance time (DT). The time it takes to reach 50% of the original concentration is referr ed to as the DT50 or half-life.

Bioaccumulative

Substances that concentrate in fatty tissue tend to build up to much hi gher concentrations in humans and other organisms. They are also more likely to transfer and accumulate up the food chain.

A bioaccumulative substance builds up in tissues of living organisms as a result of direct exposure to polluted water, air or soil, or thr ough consumption of contaminated food. A measure of the ability to bioaccumulate is expressed as a ratio of the substanceís concentration in the organism and the medium to which it is expose d, termed the bioaccumulation factor (BAF). If consumption of contaminated fo od is not relevant, the ratio is called the bioconcentration factor (BCF). A correlation is found between BCFs and the relative solubility of the substance in octanol (representing fat) compar ed to water, known as the log Kow value. For a number of chemicals a good correlation has been established, but there are limitations. Additionally, such a relationship ignores the metabolic degradation of substances w ithin a living organism. As a result, the log Kow value can be used as a screen ing tool to indicate a bioaccumulation potential, but only direct measurement of the BAF or BCF gives a reliable indication of a substanceís ability to bioaccumulate.MEPC 60/2/6 ANNEX Page 40

I:\MEPC\60\2-6.doc Toxic

Laboratory, field, and epidemiologic research i ndicates that some subs tances cause or are suspected to cause adverse effects to humans a nd wildlife in ways that range from minor skin irritations to cancer. A toxic substance has the poten tial to generate adve rse human health or environmental effects at specific e xposures. The intrinsic toxicity of a substance can be identified by standard laboratory tests. For the environment, these properties include short-term (acute) or long-term (chronic) effects. For human healt h, the properties include toxicity through breathing or swallowing the substance, and effects such as cancer, reproductive and neurological effects.

Table 8.1: Overview of PBT criteria

Source P (Persistence) B (Bioaccumulation) Toxicity

OSPAR PBT Criteria Not readily biodegradable Half-life in Water > 50 days log K ow ≥ 4 or BCF ≥ 500 Acute aquatic toxicity L(E)C50 ≤ 1 mg/l or long-term NOEC ≤ 0.1 mg/l or mammalian toxicity: CMR or chronic toxicity

EU PBT Criteria 1) Half-life > 60 days in marine
water or > 40 days in freshwater or >180 days in marine sediment or > 120 days in freshwater sediment BCF > 2000 or log P ow ≥ 3 Chronic NOEC < 0.01 mg/l or CMR cat 1&2 or endocrine disrupting effects

Canada Toxic Substances Management Half-life in Air >2 days Water >2 months Sediment >6 months Soil >1 year BAF or BCF > 5000 or log K ow >5 Inherently toxic

Note: 1) EU PBT criteria were used for this documentation because of marine water data on persistence is included and bioaccumulation value ( BCF) is nearly medium value in this table. However, this data is recommende d by document MEPC 53/24/Add.1, annex 4.

8.1.2 PBT data for the Active Substance and Relevant Chemicals

All Active Substances are not considered to be P (Persistence), B (Bioaccumulative) and T (Toxic), because all Active Substances will be neutralized by Sodium thiosulfate when in de-ballasting mode. Theref ore, all Active Substances are excluded from the PBT.MEPC 60/2/6 ANNEX Page 41

I:\MEPC\60\2-6.doc Table 8.2: PBT data for the Relevant Chemicals as EU PBT criteria

Chemical P *1) (Yes/No) (Half-life, days) B *2) (Yes/No) (BCF: l/kg wet-wt) T *3) (Yes/No) (NOEC)
1,2,3-Trichloropropane No 38 days in water No BCF: 5.3-13.0 NA

Dibromochloromethane No 38 days in water No BCF: 12.78 NA

Dibromomethane No 15 days in water No BCF: 3.23 NA

Dichlorobromomethane No 38 days in water No BCF: 10.01 NA

Dichloromethane No 38 days in water No BCF: 2.0-5.4 No Fish:75mg/l
trans-1,2-dichloroethene No 38 days in water No BCF: 12.92 NA

Trichloromethane No 38 days in water No BCF: 1.4-4.7 No Crustracean:15mg/l

Tribromomethane No 38 days in water No BCF: 7.1-21.2 NA

Trichloroacetonitrile Yes 60 days in water No BCF: 12.66 NA

Dichloroacetonitrile No 38 days in water No BCF: 3.0 NA

Dibromoacetonitrile No 38 days in water No BCF: 1.09 NA

Chloral hydrate No 38 days in water No BCF: 1.63 NA

Chloropicrin Yes 60 days in water No BCF: 11.95 NA

2-monochloroacetic acid No 15 days in water No BCF: 1.04 No Fish:12.5mg/l
2,2-dichloroacetic acid No 15 days in water No BCF: 1.68 NA

2,2,2-trichloroacetic acid No 38 days in water No BCF: 0.4-1.0 No Algal: 0.01

2-monobromoacetic acid No 8.7 days in water No BCF: 1.1 NA

2,2-dibromoacetic acid No 15 days in water No BCF: 1.29 NA

2,2,2-tribromoacetic acid No 15 days in water No BCF: 5.19 NA

2,2-bromochloroacetic acid No 15 days in water No BCF: 1.24 NA

Note: *1) Cited from http://www.pbtprofiler.net *2) Refer to Table 5.4 *3) Refer to Table 5.2 NA: No Available DataMEPC 60/2/6 ANNEX Page 42

I:\MEPC\60\2-6.doc 8.2 Toxicity testing of treated ballast water

The acute aquatic toxicity test on the 33 and 20 PSU seawater treated by ìHiB allastî through final neutralization process was conducted. The pr eparations on the acute aquatic toxicity study are summarized as follows. The detailed conten t on acute aquatic toxicity test is reported in appendix 3 ìAquatic toxicity test report with discharged wate r from laboratory scale (2 m 3 /hr) HiBallastî.

Algae

For the study the effects of the seawater treated by ìHiBallastî on the diatom, Skeletonema
costatum , during 72 hours, EC50 value based on the cell densities at the end of the experiment was calculated for both 33 and 20 PSU of treated seawater.

Crustacean

For the study the effects of the s eawater treated by ìHiBallastî on copepod, Tigriopus japonicus
, during 48 hours, EC50 and LC50 values based on mob ilization and survival da ta at the end of the experiment were calculated for both 33 and 20 PSU of treated seawater.

Fish

For the study, effects of the s eawater treated by ìHiBallastî on olive flounder, Paralichthys olivaceus , during 96 hours, LC50 value based on survival data at the end of the experiment was calculated for both 33 and 20 PSU of treated seawater.

8.2.1 Phytoplankton- Skeletonema costatum

8.2.2 Invertebrate- Tigriopus japonicus

8.2.3 Fish- Paralichthys olivaceus

8.2.4 Conclusions of acute aquatic toxicity test

The result of acute aquatic toxicity study is summarized in Tables 8.3 and 8.4.

Table 8.3: Acute aquatic toxicity of 33 PS U ballast water treated by ìHiBallastî

LC50 and/or EC50 Species End point Conc.(%) Reference/Comments

Algae Skeletonema costatum EC50 72 h 69.30 OECD 201

Crustacean Tigriopus japonicus EC50 48 h LC50 48 h > 100 > 100 OECD 202

Fish Paralichthys olivaceus LC50 96 h > 100 OECD 203MEPC 60/2/6 ANNEX Page 43

I:\MEPC\60\2-6.doc Table 8.4: Acute aquatic toxicity of 20 PS U ballast water treated by ìHiBallastî

LC50 and/or EC 50 Species End point Conc.(%) Reference/Comments

Algae Skeletonema costatum EC50 72 h 63.01 OECD 201

Crustacean Tigriopus japonicus EC50 48 h LC50 48 h > 100 >

100 OECD 202

Fish Paralichthys olivaceus LC50 96 h > 100 OECD 203

As the result of the short-term toxicity study in Tables 8.3 and 8.4, the ìHiBallastî has an acute toxic effect on onl y the growth of diatom, Skeletonema costatum . The others have no effect on the same treated seawater. EC50 value of algae during 72 hours is 69.30% and 63.01% in both 33 and 20 PSU treated ball ast water, respectively.

8.3 Risk characterization and analysis

8.3.1 Reaction with organic matter (G9: 4.2.1.3)

It was known that as an Active S ubstance, chlorine and its derivatives, could result in by-products via reaction with organic matters which can be found in nature. The probable disinfection by-products by chlorination were addresse d in section 3.4. Among those by-products, halogenated trihalomethanes (THMs) and halo acetic acids (HAAs) are two major classes of disinfection by-products (DBPs) co mmonly found in waters disinfect ed with chlorine. There are some studies on relations between by-products and disinfection method a nd correlations between precursors of disinfection by-products and disi nfection conditions [Sadiq, Singer, Gopal].

It was agreed that the type and relative amounts of the chlorination by-p roducts vary with the organic content of the water and also with the inor ganic species present. Hence, the chlorination of water containing ammonia, bromide and organi c matters, leads to competitive reactions with chlorine. The following diagram shows reaction route of by-products:

Figure 8.1: Scheme of the main reactions o ccurring chlorination of waters [Allonier]MEPC 60/2/6 ANNEX Page 44

I:\MEPC\60\2-6.doc In correlations of by-product formation, DOC or TO C, pH, bromide and dose of disinfectant have major functions for formation concentration.

8.3.2 Characterization of degrad ation rout and rate (G9:5.3.5)

Degradation of TRO generally has two routes which are chlorine demand and decay rate. Because ìHiBallastî system is considered using ne utralization system before discharge, it is not noted in this section.

Biodegradation of Relevant Ch emicals is summarized in Ta ble 5.13 of the section 5.3.1. The detailed degradation data used in MAMPEC mo delling for environmental risk assessment were summarized in the following Table 8.6.

Table 8.6: Degradation of Relevant Chemicals for abiotic hydrolysis

Chemical Degradation Route Degradation rate Reference

1,2,3-trichloropropane Abiotic hydrolysis Half-Life 44.0 yrs at 25 °C , pH 9 IUCLID, 2000

Dibromochloromethane Abiotic hydrolysis Half-Life 66.954 yrs at 25 °C

, pH 8 EPI suite 4.0

Dichlorobromometane Abiotic hydrolysis Half-Life 18.57 yrs at 25 °C

, pH 8 EPI suite 4.0

Trichloromethane Abiotic hydrolysis Half-Life 340.8 yrs at 25 °C

, pH 8 EPI suite 4.0

Tribromomethane Abiotic hydrolysis Half-Life 601.994 yrs at 25 °C

, pH 8 EPI suite 4.0

Dichloroacetonitrile Abiotic hydrolysis 10days pH 7, 69% loss HSDB Dibromoacetonitrile Abiotic hydrolysis 10days pH 8, 81% loss HSDB

8.3.3 Prediction of discharge and enviro nmental concentrations (G9: 5.3.8)

The prediction of discharge and environmental concen trations is based on the direct analysis of the Active Substances and Relevant Chemicals of generated from laboratory test of ìHiBallastî and using the modelling of MAMPEC (Marine An ti-foulant Model to Predict Environmental Concentration) VER. 2.0. MAMPEC program was developed by the Antifouling Working Group of the European Paint Makers Association to calculate environmental concentrations of anti-fouling biocides released from ship coatin gs in the marine environment. To know the detailed contents, please refer to the appe ndix 7 ìEnvironmental Risk Assessment Reportî.

8.3.3.1 Analysis of discharged chem icals in de-ballasting water

From chemical analysis results of ìHiBallastî laboratory test on the 33 PSU seawater (please refer to appendix 2), the discharged chemicals are presented in Table 8.7.MEPC 60/2/6 ANNEX Page 45

I:\MEPC\60\2-6.doc Because of the neutralization process using sodium thiosulfate before de-ballasting, Total Residual Oxidant (TRO) and Free Residual Oxidant (FRO) sp ecies containing Active Substances were not detected. Of the analysis items recommended by IMO, monochloramine and sodium thiosufate are not analysed unfortunately. If neutralization agen t would be utilized suffic iently, monochloramine is also expected to be neutralized completel y. Accordingly, monochloramine are also excluded from prediction of discharge and environmental concentrations. Sodium thiosulfate will be followed up in the further study.

As a result of chemical analysis, bromate ion (BrO 3 - ) remained in the de-ballast water. In this study, it is assumed that bromate ion was identifie d with sodium bromate. The concentration of several chemicals which are not det ected in the chemical analysis but included in th e key data-set of IMO consideration is below the Detecti on Limit (DL) value for analysed value.

Table 8.7: Concentrations of potential Relevant Chemicals on control and treated seawater samples under 33 PSU salinity condition

Chemical compounds Unit DL IMO requirement Raw seawater Day 1 Day 5

Active Substance TRO mg/L 0.22 Sodium hypochlorite 0 5.32 0 FRO mg/L 0.05 - 0 4.25 0 Monochloramine μg/L NA O NA NA NA
Relevant Chemical 1,2,3-Trichloropropane μg/L 0.01 O ND ND ND Dibromochloromethane μg/L 0.01 O 0.06 1.93 0.73 Dibromomethane μg/L 0.01 - ND 1.56 3.37 Dichlorobromomethane μg/L 0.01 O 0.09 0.32 0.15 Dichloromethane μg/L 0.01 - 1.29 0.81 0.16 trans-1,2-dichloroethene μg/L 0.02 - ND 0.01 0.01 Trichlorimethane μg/L 0.01 O 0.27 0.34 0.20 Tribromomethane μg/L 0.01 O 0.06 8.80 0.25 Trichloroacetonitrile μg/L 0.01 - ND ND 0.02 Dichloroacetonitrile μg/L 0.02 - 0.03 0.07 0.04 Dibromoacetonitrile μg/L 0.01 O 0.01 0.02 0.01 Chloral hydrate μg/L 0.02 - ND ND 0.02 2-monochloroacetic acid μg/L 0.04 O ND ND ND

2,2-dichloroacetic acid μg/L 0.01 O ND ND ND 2,2,2-trichloroacetic acid μg/L 0.01 O ND ND ND 2-monobromoacetic acid μg/L 0.01 O ND 2.33 5.66

2,2-dibromoacetic acid μg/L 0.01 O ND 12.5 55.1 2,2,2-tribromoacetic acid μg/L 0.01 O ND ND 14.9 2,2-bromochloroacetic acid μg/L 0.01 O ND ND ND Bromate ion(BrO 3 - ) μg/L 0.10 Sodium bromate ND 25.8 26.6 Sodium thiosufate μg/L NA O NA NA NAMEPC 60/2/6 ANNEX Page 46

I:\MEPC\60\2-6.doc 8.3.3.2 Predicted environmental concentrations modelling

In order to calculate the PEC using MAMPEC program, the data of three types should be required as follows:

- dimensions and properties of the harbour environment;

- physico-chemical properties of emission compound; and

- emission scenario in the marine environment.

.1 Dimensions and properties of the harbour environment

The conditions of harbour environment applie d the default data of commercial harbour, which is similar to the Rotterdam port incl uded in MAMPEC. The input data were as follows:

- Tidal period: 12.41 hrs

- Silt concentration: 35 mg/l

- POC: 1 mg OC/l

- DOC: 2 mg/l

- Chlorophyll: 3 μg/l

- Salinity: 30 s.e.

- Temperature: 15°C

- Latitude: 50° N

- pH: 7.5

- Depth of mixed sediment layer: 0.2 m

- Sediment density: 1,000 kg/m 3

- Fraction organic carbon in sediment: 0.03

- Sedimentation velocity: 1 m/d

- Exchange volume 2.59E+08 m3 /tide

Figure 8.2: Dimensions of harbour model

- Length, x1: 2,000 m

- Length, x2: 10,000 m

- Width, y1: 2,000 m

- Width, y2: 500 m

- Depth: 20 m

- Mouth width, x3: 5,000 m

- Flow velocity: 1.5 m/sMEPC 60/2/6 ANNEX Page 47

I:\MEPC\60\2-6.doc .2 Physico-chemical properti es of emission compound

In order to predict the environmental con centration of the rel eased compound in the harbour water and marine environment, physico-chemical properties of emission compound are necessary. Physico-chemical prope rties were referred from key data-set of each chemical compounds which was analysed fr om de-ballasting water. For detailed data as input in the MAMPEC, please refer to the appendix 7.

.3 Emission scenario in the marine environment

The emission load into the marine environm ent was calculated from the concentration of each chemical on the de-ballasting water and emission scenario such as the size and number of ships, capacity of de-ballasting, and leaching rate.

The discharged ballast water volume was calculate d using the statistical data of Rotterdam port for arrivals of seagoing vessels and total th rough. The discharged ballast water volume is different under the ship type and cargo loading volume.

Internationally, oil tankers occupi ed 37% of the ballast water tran sported annually, while dry bulk cargo carriers (coal, iron ore, grains and ot her bulk commodities) occupied 39%. The remaining 24% includes general cargo, container ve ssels, ro-ro ships, chem ical tankers and LNG tankers. The contribution of the latter group ma y be lower since general cargo and container vessels rarely operate return voyages in ballast condition and mainly used for the purpose of ballasting to adjust trim and heel [Oyvind Endresen et al. ]. The discharged ballast water volume is based on these assumptions that about 35% as Dead Weight Ton (DWT), which is the capacity of a ship that can load till the maximum allowa ble immersion. In here, the outgoing loads are considered on the basis of DWTs.

Consequently, it was assumed that there were 91 bulk carriers, all ship s are installed with ìHiBallastî system, anchored in the Rotterdam por t on an average day, and discharged ballast water volume is 103,844 m 3 /day. Detailed statistical data of Rotterdam port is represented in Tables 8.8, 8.9 and 8.10.

Table 8.8: Arrival of sea-going vessels by ty pe of ship [Port of Rotterdam Authority]

2007 2008 Type of ship Number GT(m 3 ) Number GT(m 3 ) Remarks

Bulk carriers 9,103 201,373,000 9,430 209,407,000 Bulk carriers, Ore carrier, Ore-bulk-oil carriers, Tankers

General cargo 24,606 440,978,000 23,179 449,467,000 Container-bulk carriers, General cargo ship, Roll-on/off passenger ship, Full container ship

Other vessels 1,163 4,867,000 1,203 4,453,000 Passenger ship, off-shore ship, Fishing boat, Non classified vessels Total 34,872 647,218,000 33,812 663,327,000

(Source: Port of Rotterdam Authority, http://www.portofrotterdam.com/ )MEPC 60/2/6 ANNEX Page 48

I:\MEPC\60\2-6.doc Table 8.9: Throughput of Rotterdam po rt [Port of Rotterdam Authority]

Item 2007 2008
Incoming (m 3 /year) 330,608,000 312,987,000
Outgoing (m 3 /year) 108,478,000 108,111,000

Total throughput (m 3 /year) 409,086,000 421,098,000

(Source: Port of Rotterdam Authority, http://www.portofrotterdam.com/ )

Table 8.10: Summary of de-ballasting water volume

Port Average Outgoing (m 3 /year) Discharging rate (%) De-ballasting water volume (m 3 /day)

Rotterdam 108,295,000 35 103,844

For the convenience of calculation, it was assumed th at equal size of the ships is anchoring at the port. The ship information for MAMPEC modell ing to calculate the emission load was assumed as follows:

Table 8.11: Information for calculation of the emission load using MAMPEC

Item Value Remarks

Ship type Bulk carriers Assumed value

Surface area (m 2 ) 15,640 Default value (in MAMPEC, OECD-EU commercial harbour)

Ship length class (m) 250 - 300 Default value (in MAMPEC)

Number of ship (ship/day) Average 91 Assumed value (in Port of Rotterdam Authority)

Capacity of de-ballasting 103,844m 3 /day Assumed value (in Port of Rotterdam Authority) Background concentration in the harbour (mg/L) 0 Assumed value

The leaching rate of each chemical was calculated as shown in the following Table 8.12. As stated above, leaching rate of several chem icals, which are not detected in the chemical analysis but included in the key data-set of IMO consideration, are below Detection Limit (DL) value for calculated value.MEPC 60/2/6 ANNEX Page 49

I:\MEPC\60\2-6.doc Table 8.12: Leaching rates of each chemical

Chemical compounds Day1 (mg/m 2 /day) Day5 (mg/m 2 /day) 1,2,3-Trichloropropane 0.066 0.066 Dibromochloromethane 12.815 4.847 Dibromomethane 10.358 22.376 Dichlorobromomethane 2.125 0.996 Dichloromethane 5.378 1.062 trans-1,2-dichloroethene 0.066 0.066 Trichlorimethane 2.257 1.328 Tribromomethane 58.429 1.660 Trichloroacetonitrile 0.066 0.133 Dichloroacetonitrile 0.465 0.266 Dibromoacetonitrile 0.133 0.066 Chloral hydrate 0.133 0.133 2-monochloroacetic ac id 0.266 0.266 2,2-dichloroacetic acid 0.066 0.066 2,2,2-trichloroacetic acid 0.066 0.066 2-monobromoacetic ac id 15.470 37.580 2,2-dibromoacetic acid 82.996 365.844 2,2,2-tribromoacetic acid 0.066 98.931 2,2-bromochloroacetic acid 0.066 0.066 Bromate ion (Sodium bromate) 171.303 176.614

8.3.3.3 The calculation results of modelling

Based on the calculation conditions of secti on 8.3.3.2, the PECs of Relevant Chemicals were estimated using the MAMPEC modelling. The PE C results which are described in Tables 8.13 and 8.14 are the total concentra tion on the harbour and surroundi ng, respectively. For detailed results of MAMPEC modelling, please refer to appendix 7.

Table 8.13: Total concentration of the PEC on the harbour

Chemical Duration Max. conc. (μg/L) 95% conc. (μg/L) Ave. conc. (μg/L) Median

conc. (μg/L) Min. conc. (μg/L)
Day1 2.20E-03 2.17E-03 7.68E-04 1.47E-04 2.54E-05 1,2,3-Trichloropropane Day5 2.20E-03 2.17E-03 7.68E-04 1.47E-04 2.54E-05 Day1 3.98E-01 3.91E-01 1.40E-01 2.82E-02 4.90E-03 Dibromochloromethane Day5 1.50E-01 1.48E-01 5.29E-02 1.07E-02 1.85E-03 Day1 3.00E-01 2.95E-01 1.07E-01 2.27E-02 3.95E-03 Dibromomethane Day5 6.48E-01 6.37E-01 2.30E-01 4.91E-02 8.53E-03 Day1 5.39E-02 5.28E-02 1.95E-02 4.63E-03 8.05E-04 Dichlorobromomethane Day5 2.53E-02 2.48E-02 9.14E-03 2.17E-03 3.77E-04 Day1 1.03E-01 1.00E-01 3.89E-02 1.12E-02 2.01E-03 Dichloromethane Day5 2.04E-02 1.98E-02 7.69E-03 2.21E-03 3.96E-04MEPC 60/2/6 ANNEX Page 50

I:\MEPC\60\2-6.doc Chemical Duration Max. conc. (μg/L) 95% conc. (μg/L) Ave. conc. (μg/L) Median

conc. (μg/L) Min. conc. (μg/L)
Day1 1.29E-03 1.26E-03 4.86E-04 1.38E-04 2.48E-05 trans-1,2-dichloroethene Day5 1.29E-03 1.26E-03 4.86E-04 1.38E-04 2.48E-05 Day1 3.14E-02 3.03E-02 1.26E-02 4.53E-03 8.23E-04 Trichlorimethane Day5 1.85E-02 1.78E-02 7.39E-03 2.66E-03 4.84E-04 Day1 2.05E+00 2.02E+00 7.10E-01 1.30E-01 2.24E-02 Tribromomethane Day5 5.82E-02 5.74E-02 2.02E-02 3.70E-03 6.37E-04 Day1 5.73E-03 5.70E-03 1.83E-03 1.83E-04 2.60E-05 Trichloroacetonitrile Day5 1.15E-02 1.14E-02 3.65E-03 3.66E-04 5.21E-05 Day1 1.96E-02 1.94E-02 6.65E-03 1.11E-03 1.79E-04 Dichloroacetonitrile Day5 1.12E-02 1.11E-02 3.80E-03 6.37E-04 1.03E-04 Day1 5.72E-03 5.66E-03 1.94E-03 3.20E-04 5.13E-05 Dibromoacetonitrile Day5 2.86E-03 2.83E-03 9.68E-04 1.60E-04 2.57E-05 Day1 1.16E-02 1.16E-02 3.70E-03 3.67E-04 5.21E-05 Chloral hydrate Day5 1.16E-02 1.16E-02 3.70E-03 3.67E-04 5.21E-05 Day1 2.33E-02 2.31E-02 7.40E-03 7.33E-04 1.04E-04 2-monochloroacetic acid Day5 2.33E-02 2.31E-02 7.40E-03 7.33E-04 1.04E-04 Day1 5.82E-03 5.78E-03 1.85E-03 1.83E-04 2.60E-05 2,2-dichloroacetic acid Day5 5.82E-03 5.78E-03 1.85E-03 1.83E-04 2.60E-05 Day1 5.81E-03 5.78E-03 1.85E-03 1.83E-04 2.60E-05 2,2,2-trichloroacetic acid Day5 5.81E-03 5.78E-03 1.85E-03 1.83E-04 2.60E-05 Day1 1.36E+00 1.35E+00 4.31E-01 4.27E-02 6.03E-03 2-monobromoacetic acid Day5 3.29E+00 3.27E+00 1.05E+00 1.04E-01 1.47E-02 Day1 7.27E+00 7.23E+00 2.31E+00 2.29E-01 3.25E-02 2,2-dibromoacetic acid Day5 3.21E+01 3.19E+01 1.02E+01 1.01E+00 1.43E-01 Day1 5.82E-03 5.78E-03 1.85E-03 1.83E-04 2.60E-05 2,2,2-tribromoacetic acid Day5 8.67E+00 8.62E+00 2.76E+00 2.73E-01 3.88E-02 Day1 5.82E-03 5.78E-03 1.85E-03 1.83E-04 2.60E-05 2,2-bromochloroacetic acid Day5 5.82E-03 5.78E-03 1.85E-03 1.83E-04 2.60E-05 Day1 1.50E+01 1.49E+01 4.77E+00 4.73E-01 6.72E-02 Bromate ion (Sodium bromate) Day5 1.55E+01 1.54E+01 4.92E+00 4.88E-01 6.93E-02

Table 8.14: Total concentration of the PEC on the surrounding

Chemical Duration Max. conc. (μg/L) 95% conc. (μg/L) Ave. conc. (μg/L) Median

conc. (μg/L) Min. conc. (μg/L)
Day1 1.00E-04 9.21E-05 4.35E-05 4.94E-05 5.81E-11 1,2,3-Trichloropropane Day5 1.00E-04 9.21E-05 4.35E-05 4.94E-05 5.81E-11 Day1 1.90E-02 1.75E-02 8.28E-03 9.41E-03 1.12E-08 Dibromochloromethane Day5 7.19E-03 6.61E-03 3.13E-03 3.56E-03 4.23E-09 Day1 1.51E-02 1.39E-02 6.60E-03 7.50E-03 9.01E-09 Dibromomethane Day5 3.30E-02 3.00E-02 1.43E-02 1.62E-02 1.95E-08 Day1 3.00E-03 2.75E-03 1.32E-03 1.50E-03 1.84E-09 Dichlorobro m omethane Day5 1.40E-03 1.29E-03 6.18E-04 7.02E-04 8.61E-10MEPC 60/2/6 ANNEX Page 51

I:\MEPC\60\2-6.doc Chemical Duration Max. conc. (μg/L) 95% conc. (μg/L) Ave. conc. (μg/L) Median

conc. (μg/L) Min. conc. (μg/L)
Day1 7.06E-03 6.50E-03 3.17E-03 3.59E-03 4.57E-09 Dichloromethane Day5 1.39E-03 1.28E-03 6.25E-04 7.09E-04 9.03E-10 Day1 8.74E-05 8.05E-05 3.92E-05 4.45E-05 5.56E-11 trans-1,2-dichloroethene Day5 8.74E-05 8.05E-05 3.92E-05 4.45E-05 5.56E-11 Day1 2.74E-03 2.52E-03 1.25E-03 1.42E-03 1.87E-09 Trichlorimethane Day5 1.61E-03 1.49E-03 7.35E-04 8.32E-04 1.10E-09 Day1 8.97E-02 8.23E-02 3.87E-02 4.40E-02 5.12E-08 Tribromomethane Day5 2.55E-03 2.34E-03 1.10E-03 1.25E-03 1.46E-09 Day1 1.39E-04 1.27E-04 5.54E-05 5.59E-05 5.96E-11 Trichloroaceto

nitrile Day5 2.79E-04 2.54E-04 1.11E-04 1.12E-04 1.19E-10 Day1 7.53E-04 6.91E-04 3.20E-04 3.64E-04 4.10E-10 Dichloroace t onitrile Day5 4.30E-04 3.95E-04 1.83E-04 2.08E-04 2.34E-10 Day1 2.17E-04 1.99E-04 9.20E-05 1.05E-04 1.17E-10 Dibro m oacetonitrile Day5 1.08E-04 9.93E-05 4.60E-05 5.23E-05 5.86E-11 Day1 2.80E-04 2.56E-04 1.11E-04 1.12E-04 1.19E-10 Chloral hydrate Day5 2.80E-04 2.56E-04 1.11E-04 1.12E-04 1.19E-10 Day1 5.61E-04 5.12E-04 2.23E-04 2.24E-04 2.38E-10 2- m onochloroacetic acid Day5 5.61E-04 5.12E-04 2.23E-04 2.24E-04 2.38E-10 Day1 1.40E-04 1.28E-04 5.56E-05 5.59E-05 5.96E-11 2,2-dichloroacetic acid Day5 1.40E-04 1.28E-04 5.56E-05 5.59E-05 5.96E-11 Day1 1.40E-04 1.28E-04 5.56E-05 5.59E-05 5.96E-11 2,2,2-trichloroacetic acid Day5 1.40E-04 1.28E-04 5.56E-05 5.59E-05 5.96E-11 Day1 3.27E-02 2.98E-02 1.30E-02 1.30E-02 1.39E-08 2- m onobromoacetic acid Day5 7.94E-02 7.24E-02 3.15E-02 3.16E-02 3.37E-08 Day1 1.75E-01 1.60E-01 6.95E-02 6.98E-02 7.45E-08 2,2-dibromoacetic acid Day5 7.73E-01 7.05E-01 3.07E-01 3.08E-01 3.28E-07 Day1 1.40E-04 1.28E-04 5.56E-05 5.59E-05 5.96E-11 2,2,2-tribromoacetic acid Day5 2.09E-01 1.91E-01 8.29E-02 8.33E-02 8.88E-08 Day1 1.40E-04 1.28E-04 5.56E-05 5.59E-05 5.96E-11 2,2-bro m ochloroacetic acid Day5 1.40E-04 1.28E-04 5.56E-05 5.59E-05 5.96E-11 Day1 3.26E-01 3.30E-01 1.44E-01 1.44E-01 1.54E-07 Bromate ion (Sodium bromate) Day5 3.73E-01 3.40E-01 1.48E-01 1.49E-01 1.58E-07

8.3.4 Assessment of potential fo r bioaccumulation (G9: 5.3.7)

The potential for bioaccumulation of chemical s ubstances can be evaluated by the index such as the K ow or BCF. As stated in section 8.1.2, it is expect ed that the potential for bioaccumulation is unlikely to affect on the aquatic organisms because the values of all K ow and BCF are less than 3 and 500 L/kg wt-wt, respectively.

8.3.5 Effect assessment

The acute and chronic aquatic toxicity on the Rele vant Chemicals is summarized in Table 8.15. It is difficult to find the literature review ab out chronic aquatic toxicity due to insufficient experiment data.MEPC 60/2/6 ANNEX Page 52

I:\MEPC\60\2-6.doc The acute aquatic toxicity values on the Tric hloroacetonitrile, 2-monochloroacetic acid, and 2-monobromoacetic acid are the lowest on the Crustacea species ( Daphnia magna ) or Algae species ( Scenedesmus subspicaus ). More detailed data was prepared in appendix 7.

8.3.6 Effects on aquatic organisms

As shown in the key data-set (please refer to appendix 4), the literature review for the aquatic toxicity is carried out to determ ine the PNEC of aquatic organisms, such as algae, crustacean, and fish, with Relevant Chemicals. The short-term toxicity value of L( E)C50 was selected in accordance with the test durations with 72 hours, 48 hours, and 96 hours for algae, crustacean, and fish, respectively. If any substance does not meet the time criterion, the toxicity value makes use of a reference. It is difficu lt to find the literature review about chronic a quatic toxici ty due to insufficient experiment data.

On the basis of the literature review on aquatic toxicity data, the PNEC was determined to be used as a parameter of the environmental risk as sessment. In general, the determination process on the multitude of end points is proposed to calcu late the geometric mean if more than one L(E)C50 value is available for the same species and end-points. In here, the smallest L(E)C50 value is taken in the literature review data on the aquatic t oxicity meets the time criterion at 72 hours, 48 hours, and 96 hours for algae, crust acean, and fish, respectively. If NOEC value on the chronic toxicity test exists, th is value is select ed preferentially.

Finally, the PNEC is determined from the selected aquatic toxicity data and assessment factors. Assessment factors were selected based on the guidance of the GESAMP-Ballast Water Working Group (MEPC 58/2/7, annex 4) as well as the Technical Guidance Document (TGD) on Risk Assessment in support of the EU Commission Joint Research Centre (2003). However, aquatic toxicity data are selected from reasonable wo rst-case assumptions of this study. Assessment factors to determine the PNEC are presented in Table 8.16.

Table 8.16: Assessment factors for determination of PNEC

Assessment Factor Data-set PNEC long PNEC short Freshwater assessment Lowest short-term L(E)C50 from fresh water species representing thr ee trophic levels 1000 10-100

Lowest chronic NOEC from thre e freshwater or saltwater species representing three trophic levels 10

Saltwater assessment Lowest short-term L(E)C50 from marine species representing three trophic levels 1000 10-100

Lowest chronic NOEC from thre e freshwater or saltwater species representing three trophic levels 100
Lowest chronic NOEC from three saltwater species representing thr ee trophic level 100

Lowest chronic NOEC from thre e freshwater or saltwater species representing three trophic levels + at least two chronic NOECs from additional ma rine taxonomic groups 10MEPC 60/2/6 ANNEX Page 53

I:\MEPC\60\2-6.doc The PNEC values for the each Relevant Chemical are summarized in the following Table 8.17. Because the aquatic toxicity data of dibromom ethane, dichloroacetonitrile, 2,2,2-tribromoacetic acid, and 2,2-bromochloroacetic acid could not be found, PNEC of these chemical was not determined.

Table 8.17: Summary of determined PNEC value

Chemical compounds Available data Assessment Factor End point (mg/L) PNEC (mg/L)
1,2,3-Trichloropropane Daphnia magna (Crustacea/acute/LC50/48hrs) 1000 20 0.002

Dibromochloromethane Selenastrum capricornutum (Algae/acute/EC50/72hrs) 1000 9.6 0.0096

Dibromomethane NA - NA -

Dichlorobromomethane Selenastrum capricornutum (Algae/acute /EC50/72hrs) 1000 12 0.012

Dichloromethane Oryzias latipes (Fish/chronic/NOEC) 1000 75 0.75

trans-1,2-dichloroethene Daphnia magna (Crustacea/acute/LC50/24hrs) 1000 110 0.11

Trichlorimethane Ceriodaphnia dubia (Crustacea /chronic/NOEC) 1000 3.4 0.0034

Tribromomethane Brevoortia tyrannus (Fish/acute/LC50/96hrs) 1000 9 0.009

Trichloroacetonitrile Daphnia magna (Crustacea/acute/EC50/48hrs) 1000 0.044 0.000044

Dichloroacetonitrile NA - NA -

Dibromoacetonitrile Pimephales promelas (Fish/acute/LC50/96hrs) 1000 0.55 0.00055

Chloral hydrate Daphnia magna (Crustacea/acute/EC50/48hrs) 1000 500 0.5

2-monochloroacetic acid Brachydanio rerio (Fish/ chronic/NOEC) 1000 25 0.025

2,2-dichloroacetic acid Nitocra spinipes (Crustacea/acute/LC50/96hrs) 1000 21 0.021

2,2,2-trichloroacetic acid Salmo gairdneri (Fish/acute/LC50/96hrs) 1000 1050 1.05

2-monobromoacetic acid Daphnia magna (Crustacea/Chronic/NOEC) 1000 16 0.016

2,2-dibromoacetic acid Pimephales promelas (Fish/acute/LC50/96hrs) 1000 69 0.069
2,2,2-tribromoacetic acid NA - NA - 2,2-bromochloroacetic acid NA - NA -

Sodium bromate Bass prolarvae (Fish/acute/LC50/96hrs) 1000 30.8 0.0308MEPC 60/2/6 ANNEX Page 54

I:\MEPC\60\2-6.doc 8.3.7 Effects on sediment

As shown in section 5, no report on the sediment toxicity, which is classified to the algae, crustacean, and fish were found. However, all K oc values for chemicals are less than 30 L/kg wt-wt. Therefore, it is expected that all chemicals di scharged by the ìHiBallastî system are unlikely to have effect on the sediment.

8.4 Risk to the aquatic environmental

The PEC/PNEC ratio is adjusted to make final de cision of marine envir onmental risk. If the PEC/PNEC ratio is less than 1 on each compartment, it can conclude that evaluated chemical has no effect on the aquatic environment. If the PEC/PNEC ratio is greater than or equal to 1, there is a need for risk reduction measures. The calculated result of PEC/PNEC ratio is given in Table 8.18.

Table 8.18: The calculated result of PEC/PNEC ratio

PEC/PNEC ratio Chemical Duration Max. Ave. Day1 1.10E-04 3.84E-05 1,2,3-Trichloropropane Day5 1.10E-04 3.84E-05 Day1 4.15E-02 1.46E-02 Dibromochloromethane Day5 1.56E-02 5.51E-03 Day1 - - Dibromomethane Day5 - - Day1 4.49E-03 1.63E-03 Dichlorobromomethane Day5 2.11E-03 7.62E-04 Day1 1.37E-03 5.19E-04 Dichloromethane Day5 2.72E-04 1.03E-04 Day1 1.17E-05 4.42E-06 trans-1,2-dichloroethene Day5 1.17E-05 4.42E-06 Day1 9.24E-03 3.71E-03 Trichloromethane Day5 5.44E-03 2.17E-03 Day1 2.28E-01 7.89E-02 Tribromomethane Day5 6.47E-03 2.24E-03 Day1 1.30E-01 4.16E-02 Trichloroacetonitrile Day5 2.61E-01 8.30E-02 Day1 - - Dichloroacetonitrile Day5 - - Day1 1.04E-02 3.53E-03 Dibromoacetonitrile Day5 5.20E-03 1.76E-03 Day1 2.32E-05 7.40E-06 Chloral hydrate Day5 2.32E-05 7.40E-06 Day1 9.32E-04 2.96E-04 2-monochloroacetic acid Day5 9.32E-04 2.96E-04 Day1 2.77E-04 8.81E-05 2,2-dichloroacetic acid Day5 2.77E-04 8.81E-05 Day1 5.53E-06 1.76E-06 2,2,2-trichloroacetic acid Day5 5.53E-06 1.76E-06MEPC 60/2/6 ANNEX Page 55

I:\MEPC\60\2-6.doc PEC/PNEC ratio Chemical Duration Max. Ave. Day1 8.50E-02 2.69E-02 2-monobromoacetic acid Day5 2.06E-01 6.56E-02 Day1 1.05E-01 3.35E-02 2,2-dibromoacetic acid Day5 4.65E-01 1.48E-01 Day1 - - 2,2,2-tribromoacetic acid Day5 - - Day1 - - 2,2-bromochloroacetic acid Day5 - - Day1 4.87E-01 1.55E-01 Sodium bromate Day5 5.03E-01 1.60E-01

The PEC/PNEC ratios of all chemicals on Day 1 and Day 5 are less than 1 with the maximum and average PEC/PNEC ratios. It means that wh en analysed all chemicals have no effect on the aquatic environment. But, due to insufficient toxicity data, a part of chemicals omitted from PEC/PNEC ratio calculati on should be identified in the further study.

9 RISK ASSESSMENT

A HAZID study was conducted to identify potenti al hazardous events and how to manage hazards to ship and crew during the design and ope rational phase of the ìHiBallastî system. All issues on the hazardous event we re included in the Risk Regi ster with recommendations on corrective or preventive actions. A detailed report of HAZID is described in appendix 5 ìHazard Identification Reportî.

9.1 Risk to safety of ship

ìHiBallastî will be installed on the particular side stream of main ballast water inlet line. A part of ballast water, which is pumped by main ballast pumps, will be introduced to the side stream of ìHiBallastî for the seawater elec trolysis. In ìHiBallastî, the high concentration of disinfectant will be generated and injected into the main ba llast line. In the catastrophic failure of the ìHiBallastî system, emergency shut-down valv e should be automatically operated and ìHiBallastî system would be isolated completely.

Because ìHiBallastî generates the high concentrati on of oxidative disinfectant, the electrolyzer and piping could be exposed to the corrosive environmen t. The chloro- or bromo- compounds such as sodium hypochlorite, dibromomethane , trichloromethane, etc., were investigated as the corrosive chemicals in the key data-set. In this Basic Appr oval dossier, neither short nor long-term corrosion test was conducted. The corrosion has potential ri sks on the leakage of ha rmful disinfectant having an effect on the ship and crew. A comprehensive long-term corrosion test will be performed at the ìHiBallastî system during land-based test according to IMO Performance Standard for Protective Coating (PSPC) guideline. The corrosivity test of treated seawat er will be performed using the Simulated Wave Ballast Tank (SWBT) by Coating Performance Test Laboratory in Protective Coatings and Corrosion Research Depa rtment, Hyundai Industrial Research Institute (HIRI) located on Hyundai Heavy Industries Co. LTD. in Ulsan, th e Republic of Korea. The Institute has personnel with a so lid experience in protective co ating and corrosion research, and all tests were performed according to IMO MSC 82/WP.3. Researchers involved in this project are accredited by NACE Certifie d Coating Inspector Level 2.MEPC 60/2/6 ANNEX Page 56

I:\MEPC\60\2-6.doc Hydrogen gas (H 2 ), oxygen gas (O 2 ), and the small amounts of chlorine (Cl 2 ) gas can be produced during the electrolysis. It is known th at hydrogen gas has a flammable range between 4% and 75% in air. ìHiBallastî could be expected to produce hydrogen gas outside of explosion limit concentration. However, a ga s separator and hydrogen gas detector should be installed to obtain complete sa fety. The result of HAZID st udy was prepared in appendix 5.

9.2 Risk to human health

9.2.1 Identification of hazardous chemicals

As stated in section 9.1 ìRisk to safety of ship î, ìHiBallastî generates the corrosive chemicals. These chemicals have a potential hazard on the corrosion in the electrolyzer, piping and their connectors, and pumps. If elect rolyzer or connection piping is damaged in the middle of long-term operation, there is a possibility of leakage of hi gh concentration of disinfectant including Active Substances and Relevant Chemicals. So, strict emergency manual shall be prepared to prevent human exposure. For example, to prevent direct contact or scattering, it is recommended that Acrylic resin-based foam tape should be wound around the possible parts of leakage occurrence. However, the selection of anti-corrosive material for these equipment and piping is more important.

For the emergency situation such as leakage of high concentration of disinfectant, the Human Exposure Scenarios (hereafter re ferred as HES) should be esta blished through other safety analysis independently. In addition, the crew should complete the suitable credit hour for training such as countermeasure on the leakage case, and usage of safety equipment. Also, the MSDS should be supplied to manage the safe hand ling and storage of the harmful chemical.

Hazardous chemicals having a possibility of leakag e from the ìHiBallastî could be classified under the gaseous phase such as hydrogen, chlori ne, and liquid phase such as hypochlorite and dissolved sodium thiosulfate.

Free chlorine gas is corrosive a nd irritating to the ey es of human. It hydr olyzes very rapidly yielding hydrochloric ac id. Skin burns and mucosal irrita tion are like that from exposure to volatile inorganic acids. Chlorine burns exhibi t severe pain, redness, possible swelling and early necrosis. Symptoms include lacrimation, cough , laboured breathing, and excessive salivary and sputum formation. Excessive ir ritation of the lungs causes acute pneumonitis and pulmonary edema, which could be fatal. Residual pulmona ry malfunction may also occur. Chemical pneumonitis and pulmonary edema may result from exposure to the lower respiratory tract and deep lung. When liquid chlorine is exposed to the atmosphere, it vaporizes rapidly to chlorine gas and the resulting physiological effects will be those described above. Chlorine gas has an odour detectable at a concentration as low as 3.55 pp m. Irritation of the throat occurs at 15 ppm. A concentration of 50 ppm is considered danger ous for even short exposures [Cheremisinoff].

Hydrogen is a non-toxic and asphyxiant gas. Hi gh concentrations may exclude an adequate supply of oxygen to the lungs. Effects of oxygen deficiency resulting fr om simple asphyxiants may include: rapid breathing, diminished mental alertness, impaired muscular coordination, faulty judgment, depression of all sensations, em otional instability, and fatigue. As asphyxiation progresses, nausea, vomiting, pros tration, and loss of consciousness may result, eventually leading to convulsions, coma, and death. Natural or artificial ventilation must be provided.

Electrolyte contains large number of chemical sp ecies. Of the chemical species, we can assume that chlorine compounds are pred ominant species. Detailed description on chlorine is contained in previous paragraphs. Also, related emergency measur es should be complied with that of chlorine.MEPC 60/2/6 ANNEX Page 57

I:\MEPC\60\2-6.doc Sodium sulfate is hazardous in ca se of ingestion or inhalation. Al so, sodium sulfate is slightly hazardous (irritant) in case of skin contact or eye contact. When heated to decomposition temperature, it emits toxic fumes of sulfur oxides, hydrogen sulfide, and sodium oxide.

9.2.2 Establishment of human exposure scenario and measures

As shown in figure 9.1, the risk assessment pro cess can be represented as a continuum from source through exposure and dose to effects. Of the series of elements for human health risk assessment, possibilities of human exposure du ring daily operation of ìHiBallastî system are classified with three phases such as gaseous, liqui d, and solid, respectively. The first case is gas leakage originating from emergency condition su ch as welding defect, corrosion, vibration and mechanical damage etc., listed at the HAZID step. The second case is liquid leakage from concentrate of disinfectant and ne utralizing agent (namel y, sodium thiosulfate) due to fastening failure of flanges or overhauling for maintenance. The last case is contact with scattered powder during handling of sodium thiosulfate powder. HES and measures for ìHiBallastî are summarized through preliminary test as shown in Table 9.1, even if the following cases occur scarcely only during emergency situation. If there are some incomplete parts in HES, remainders will be dealt with, with consideration for further studies during land-based pilot verification test.

9.2.2.1 Leakage of hazardous gas

It is deduced that hazardous gas can evolve d from damaged area due to welding defect, corrosion, fatigue fracture originating from vibr ation stress, and evaporation of spilled hazardous liquid as stated in HAZID study. For crew pr otection, avoid contact with eyes, skin, and clothing. Gaseous chlorine hydrolyzes in the pr esence of moisture, forming hydrochloric acid, which irritates the eyes and skin. Wash thoroughly after handling chlorine. Shower using plenty of soap and water. Before wo rking, crew should be equipped w ith goggles, rubber shoes, glove, hard hat, and a National Institute for Occ upational Safety and He alth (NIOSH)-approved respirator with an acid gas cartridge where airborne concentrations are expected to exceed exposure limits or when symptoms have been obser ved that are indicative of over-exposure. It is essential that each individual who may be exposed to chlorine at all times should use a respirator approved for chlorine use. Fo r re-entry into an emergency area, self-contained breathing equipment provided must be used. Also, provide adequate ventilation to reduce the accumulation of liquid or gaseous chlorine in low areas. In some cases, natura l ventilation may be adequate; in others, artificial ventil ation, such as forced air through a syst em of ducts, must be provided. Readily accessible eye wash fountains and del uge showers must be provided in strategic locations wherever electrolyzed solution is use d. Emergency kits are commercially available from an approved supplier.

To prevent evolution of chlorine gas from the system, NDT (Non-Destructive Test) for ballast water treatment system should be carried out to ensure that chlorine gas can not penetrate through joining parts such as welding or adhesion. Because ìHiBallastî is a closed-system, all of chlorine will be discharged with treated ballast wate r if there is no leakage. To detect leakage of chlorine, chlorine gas detect or should be installed.

To prevent evolution of hydrogen gas from the system, strict prevention measures shall be establish in the same manner such as NDT and ventilation as free chlorine gas. Because ìHiBallastî is a closed-system, all of hydrogen w ill be discharged with treated ballast water if there is no leakage. To detect leakage of hydrogen during normal operating phase, hydrogen gas detector should be installed.MEPC 60/2/6 ANNEX Page 58

I:\MEPC\60\2-6.doc Figure 9.1: Scientific elem ents of human health ri sk assessment [WHO, 2005]

Table 9.1: Human exposure scenario and measures for ìHiBallastî

Phase Gas Liquid Solid

Hazardous Chemicals - H 2 - Cl 2 - Concentrate of disinfectant - Sodium thiosulfate

solution - Sodium thiosulfate

Event - Damage of elctrolyzer or gas separator due to corrosion - Fatigue fracture due to vibration - Evaporation of spilled hazardous liquid - Penetration due to

welding defect - Spill of concentrate of disinfectant or sodium thiosulfate due to corrosion under emergency or routine maintenance - Spill of concentrate of

disinfectant or sodium thiosulfate due to fatigue fracture under emergency or

routine maintenance - Scattering of powder during handling for dissolution from storage tank to neutralizing agent tank

Source

Area - Electrolyzer - Gas separator - Pump - Flange - Piping - Packaging bag

Exposure

Route - Skin - Eye - Respiratory organs - Skin - Eye - Respiratory organs - Oral cavity (if any) - Skin - Eye - Respiratory organs - Oral cavity (if any)MEPC 60/2/6 ANNEX Page 59

I:\MEPC\60\2-6.doc Phase Gas Liquid Solid Measures - Use goggles, rubber shoes, glove, hard hat, protective clothing, and a NIOSH approved respirator - Installation of gas

detector - Natural or artificial

ventilation - Providing readily

accessible eye wash fountains and deluge showers - 100% NDT for joining

line - Installation of rubber

mount for support of pipes, pumps, and electrolyzer - Use goggles, rubber shoes, glove, hard hat, protectiveclothing, and a NIOSHapproved respirator - Providing of self-contained

breathing equipment - Providing readily accessible

eye wash fountains and deluge showers - Addition of alkaline material

for neutralization and flushing with fresh water - Installation of rubber mount

for control of support of pipes, pumps, and electrolyzer - Carrying out Hydrotest - Winding of protective tape

(e.g., Acrylic foam tape) for joining parts - Use goggles, rubber shoes, glove, hard hat, protective clothing, and a NIOSH approved respirator

9.2.2.2 Leakage of concentrate of disi nfectant and neutralizing agent

Spill of concentrate of disinfectan t and neutralizing agent could ma inly originate from connecting parts such as welding joint or flange due to corrosion and fatigue fract ure by vibration stress under emergency or routine maintenance. Spill ed concentrate of disinfectant and sodium thiosulfate can be in contact with crew and related equipment of engine-room and can erode human skin or metallic material. Before worki ng, crew should be equipped with goggles, rubber shoes, glove, hard hat, and a NIOSH-approved respirator with an acid gas cartridge where airborne concentrations are expe cted to exceed exposure limits or when symptoms have been observed that are indicative of overexposure. And readily accessible eye wash fountains and deluge showers must be provided in strategic lo cations wherever concentrate of disinfectant and sodium thiosulfate are used.

The chlorine vapour pressure over a concentr ate of disinfectant depends on solution pH, decreasing as pH increases (because of the increa sed formation of non-volatile hypochlorite acid). Therefore, the addition of an alkaline material such as lime or sodium bicarbonate will reduce the volatility of chlorine from accide ntal spills or leaks and thus mi nimize danger to exposed crew. After the completion of concentr ate of disinfectant neutralizati on, exposed equipment should be flushed with fresh water to prevent corrosion. Small amounts of dilute sodium thiosulfate solution can be flushed down a sink with a large quantity of water, unless local rules prohibit this. Larger amounts of solution should be stored for later disposal. To prevent leakage of liquid, hydro test should be thoroughly carried out according to designated test procedure.

9.2.2.3 Contact with sodium thiosulfate powder

The crew can be exposed to sodium thiosulf ate powder during handli ng for dissolution from storage tank to neutralizing agent tank. If so dium thiosulfate powder is scattered in small quantities, use appropriat e tools to put the spilled solid in a convenient wa ste disposal containerMEPC 60/2/6 ANNEX Page 60

I:\MEPC\60\2-6.doc and finish cleaning by spreading water on the c ontaminated surface and dispose of according to local and regional authority requirements. If sodium thiosu lfate powder is dispersed in large quantities, use a shovel to put the material into a convenient waste disposal container and finish cleaning by spreading water on the contamin ated surface and allow evacuating through the sanitary system.

Before handling sodium thiosulfate powder, th e crew should be equipped with goggles, rubber gloves, rubber shoes, glove, hard hat, and a NIOSH approved respir ator. If crewís eyes have been in contact with this powder, check and remove any contact lenses (Do not use an eye ointment). If it is exposed to crewís skin, after contact with sk in, wash immediately with plenty of water. Gently and thoroughly wash the contaminated skin with running water and nonabrasive soap. Be particularly careful to clean folds, crevices, creases and groin. Cover the irritated skin with an em ollient. If irritation persists, seek medical attention. Wash contaminated clothing before reusing. In case of serious skin contact, wash with a disinfectant soap and cover the contaminated skin with an anti-bacterial cream and seek medi cal attention. If crew ingests sodium sulfate, do not induce vomiting. Loosen ti ght clothing such as the collar, tie, belt or waistband. If the victim is not breathing, perf orm mouth-to-mouth resusc itation. Seek immediate medical attention. If crew swallowed sodium thio sulfate solution, give seve ral glasses of milk or water. Vomiting may occur spon taneously, but it is not necessa ry to induce. Never give anything by mouth to an unconscious person. An e xplosion may occur if tr iturated with nitrates, chlorates, or permanganates. Sodium sulfate is hygroscopic material. S o, keep container tightly closed and in a cool, well-ventilated area.

9.3 Risk to the aquatic environment

The acute aquatic toxicity test performed under 33 PSU of seawater treated from laboratory scale ìHiBallastî system, which is an adopted neutra lization process as a fi nal step, was conducted with the aquatic organisms such as the algae ( Skeletonema costatum ), crustacean ( Tigriopus japonicas ), fish ( Paralichthys olivaceus ) in accordance with OECD methods. Algae were only influenced by the seawater treated from ìHiBalla stî system. The others were not affected by the same seawater. The EC50 value of algae for 72 hours is 69.3%.

Environmental risk analysis was conducted to ev aluate potential risk of the Active Substances and Relevant Chemicals generate d from ìHiBallastî. Based on the PEC/PNEC ratio, the aquatic environmental risk was assessed. The PEC was pr edicted from the results of chemical analysis and MAMPEC modelling. PNEC was determined from the literature re views of acute and chronic toxicity test for the ch emicals. For MAMPEC modelli ng, it was assumed that there were 91 bulk carriers, all ships are installed with ìHiBallastî, anchored in the Rotterdam port on an average day, and quantity of discharged ballast water was 103,844m 3 /day.

The PEC/PNEC ratio of all chemicals contained in discharged seawater was less than 1 with the maximum and average PEC. It means that when analysed all chemicals have no effects on the aquatic environment.

Due to the insufficient toxicity data, a part of chemicals omitted from PEC/PNEC ratio calculation should be identified in the further study. Also, the chr onic toxicity test and the risk characterization for the seawater treated from ìHiBallastî system are required to estimate the potential risk for aquatic ecosystem.MEPC 60/2/6 ANNEX Page 61

I:\MEPC\60\2-6.doc 10 ASSESSMENT REPORT

10.1 Overview of data and endpoint

In regard to the Active Substances and Relevant Chemicals by the ìHiBalla stî system, all of the toxicity data for the aquatic organisms and mammalians were investigated from eminent literatures and toxicology database provided in the several research institutes, such as Toxicology Data Network (ToxNet), Hazardous Substances Da ta Bank (HSDB), Eco-toxicity (US-EPA), and European Chemical Bureau (ECB), etc. However, the reliability of endpoi nts and toxicity data presented in Key data-set could not be valid ated by the OECD methods or EPA methods.

The chemical analyses on the Active Substances and Relevant Chemicals of ìHiBallastî system were conducted by Korea Testing and Research Institute (KTR) under the supervision of the Korea Marine Equipment Research Institute (K OMERI) holding the Qualit y Assurance (QA) and the Quality Assurance Project Plane (QAPP) certified by Korea Laboratory Accreditation Scheme (KOLAS). All chemical analyses were carried out according to the OECD methods or EPA methods. Also, the lab-scal e test of ìHiBallastî system is adequate for IMO document MEPC 58/23, annex 4, Part 2, paragrap h 2.3.20 (as well as IMO BWM/CONF/36, BWM Convention, and regulation D-2).

The acute toxicity test on the discharged wa ter treated by ìHiBallast î system was conducted by Marine Eco-Technology Institute (MEI) in the Repub lic of Korea. The acute toxicity test was carried out according to OECD met hods (OECD 201, 202, 203) on the Algae ( Skeletonema
costatum ), Crustacean ( Tigriopus japonicus ), and Fish ( Paralichthys olivaceus ), respectively. Although MEI Institute is not accredited sp ecifically for toxicological testing (e.g., Good Laboratory Practice (GLP)), the Inst itute has an ecotoxicological laboratory, personnel with a solid experience in toxicological research, and all te sts were performed according to GLP.

10.2 Summary of risk assessment on the ship, crew and environmental

The study of the en vironmental risk assessment was pe rformed for substances which were detected in water on day 5 of 33 PSU discharg ed by the lab-scale ìHiBallastî system and referred to the GESAMP-Ballast Water Wo rking Group (MEPC 59 /2/13, annex 1). The Predicted Environmental Concentration (P EC) was predicted using the modelling of MAMPEC (Marine Anti-foulant Model to Predic t Environmental Concentration) VER. 2.0 developed by the Antifouling Working Group of th e European Paint Makers Association. The Predicted Non-effect Concentration (PNEC) is determined from the selected aquatic toxicity data and assessment factors. A ssessment factors were selected based on the guidance of the GESAMP-Ballast Water Working Group (MEPC 58/2/7, annex 4).

For the potential risk identification on the ship and crew, a HAZID study was conducted. A HAZID study identified potential hazardous events and how to manage hazards to ship and crew during the design and operational phase of the ìHiBallastî system. All issues on the hazardous event were included in the Risk Regi ster with recommendations on corrective or preventive actions. According to the human health assessment [WHO, 2005], the Human Exposure Scenario was establishe d on the ìHiBallastî system.MEPC 60/2/6 ANNEX Page 62

I:\MEPC\60\2-6.doc REFERENCES

Agus E., Voutchkovb N. and Sedlaka D. L., Disinf ection by-products and th eir potential impact on the quality of water produced by desalination systems: A lit erature review, Desalination 237: 214ñ237, 2009.

Allonier A.S., Khalanski M., Camel V. and Bermond A., Characterization of Chlorination By-products in Cooling Effluents of Coastal Nu clear Power Stations. Marine Pollution Bulletin Vol. 38, No. 12, 1232-1241, 1999.

ATSDR Toxicological Profile Information Sheet , Agency for Toxic Substances and Disease Registry, 4770 Buford Hwy NE, Atlanta, GA 30341, http://www.atsdr.cdc.gov/MHMI/mmg.htm

Casson L.W. and Bess, Jr. J.W., Conversion to On-Site Sodium Hypochlorite Generation, Water and Wastewater Applicati ons, Lewis Publishers, 2003.

CCRIS, Chemical Carcinogenesis Research Inform ation System. National Library of Medicine, http://toxnet.nlm.nih.gov/cgi -bin/sis/htmlgen?CCRIS

Chen C., Zhanga X.J., Zhua L.X., Liua J., He b W. J. and Hanb H.D., Disinfection by-products and their precursors in a water treatment plant in North China: Seasonal changes, and fraction analysis. Science of the total environment 397:140-147, 2008.

Cheremisinoff N.P., Cheremisinoff P.N. and Trattner R.B., Chemical and Non-chemical Disinfection, Ann Arbor Science, 1981.

Dean J.A., Langeís Handbook of Chemistry, Fi fteenth Edition, McGraw-Hill, Inc., 1999.

ECOTOX Database, United State Environmental Protection Agency Mid-Continent Ecology Division. http://www.epa.gov/med/Prods_Pubs/ecotox.htm

Endresen O., Behrens H.L., Brynestad S., Ande rson A.B. and Skjong R., Viewpoint: Callenages in global ballast water management. Ma rine Pollution Bulletin 48: 615-623, 2004.

EPI suite V4.0. http://www.epa.gov/oppt/exposure/pubs/episuitedl.htm

EU Risk Assessment Report for monochloroacetic acid, European Commission Joint Research Centre, 2005.

EU Risk Assessment Report for sodium hypochl orite, European Commission Joint Research Centre, 2007.

Gopal K., Tripathy S.S., Bersillon J.L. and Du bey S.P., Review: Chlorination byproducts, their toxicodynamics and removal from drinking water. Journal of H azardous Materials 140: 1ñ6, 2007.

Haas C.N., Chapter 14, Disinfection of th e Water Quality and Treatment, A handbook of Community Water Supplies, American Water Works Association (AWWA), 1999.

Hrudey S.E., Review: Chlorination disinfection by-products, public h ealth risk tradeoffs and me, Water Research 43: 2057-2092, 2009.MEPC 60/2/6 ANNEX Page 63

I:\MEPC\60\2-6.doc HSDB, Hazardous Substanc es Data Bank, National Library of Medicine. http://toxnet.nlm.nih.gov/cgi -bin/sis/htmlgen?HSDB

IMO (International Maritime Organization), 2008b. Harmful Aquatic Organisms in Ballast Water. MEPC 58/2/7, GESAMP-BWWG 6/ 9, annex 4. IMO, London, United Kingdom.

IRIS, Integrated Risk Information System database, United State Environmental Protection Agency. http://www.epa.gov/iris/

IUCLID, International Uniform Chemical Information Database, European Chemicals Bureau (ECB). http://ecb.jrc.it/esis

NITE (National Institute of Technology and Evaluation) Database , Biodegradation and Bioconcentration of the Existing Chemical Substa nces under the Chemical Substances Control Law, 2-49-10 Nishihara, Shibuya-ku, Tokyo, 151-0066 Japan. http://www.safe.nite.go.jp/data/h azkizon/pk_e_kizon_input_second.home_object

NTP, National Toxicology Program, National Inst itute of Environmental Health Sciences. http://ntp.niehs.nih.gov:8080/query.html?qt=&col=005main

OECD SIDS, Screening Information Data-Set (S IDS) for calcium hypoc hlorite, Processed by UNEP Chemicals, Copyright International Programme on Chemical Safety (IPCS). http://www.inchem.org/documents/sids/sids/7778543.pdf

OECD SIDS, Screening Information Data-Set (S IDS) for trichloroacetic acid, Processed by UNEP Chemicals, Copyright International Programme on Chemical Safety (IPCS). http://www.inchem.org/documents/sids/sids/76039.pdf

PAN Pesticide Database, Citation: Kegley, S.E., Hill, B.R., Orme S. and Choi A.H., Pesticide Action Network, North America, San Francisco, CA, 2009. http://www.pesticideinfo.or g/Search_Chemicals.jsp

Port of Rotterdam Authority, Arrivals of sea-going vessels by type of ship.

Port of Rotterdam Authority, Throughput port of Rotterdam.

Sadiq R. and Rodriguez M.J., Di sinfection by-products (DBPs) in drinking water and predictive models for their occurrence: a review. Sc ience of the Total Environment 321: 21ñ46, 2004.

Singer P.C. and Reckhow D.A., Chapter 12, Chem ical Oxidation of the Water Quality and Treatment, A handbook of Community Water Supplies, Am erican Water Works Association (AWWA), 1999.

White G.C., Handbook of Chlorination and Alternative Disinfectants, 3 rd Edition, Van Nostrand Reinhold, New York, 1992.

WHO, Brominated Acetic Acids in Dri nking-water, WHO/SDE/WSH/03.04/79, Background document for development of WHO Guide lines for Drinking-water Quality, 2004.

WHO, Monochloroacetic Acid in Drinki ng-water, WHO/SDE/WSH/03.04/85, Background document for development of WHO Guide lines for Drinking-water Quality, 2004.MEPC 60/2/6 ANNEX Page 64

I:\MEPC\60\2-6.doc WHO, Monochloramine in Drinking-wat er, WHO/SDE/WSH/03.04/83, Background document for development of WHO Guidelin es for Drinking-water Quality, 2004.

WHO, Trichloroacetic Acid in Dri nking-water, WHO/SDE/WSH/03.04/120, Background document for development of WHO Guide lines for Drinking-water Quality, 2004.

WHO, Bromate in Drinking-water, WH O/SDE/WSH/05.08/78, Background document for development of WHO Guidelines for Drinking-water Quality, 2005.

WHO, Dichloroacetic Acid in Dri nking-water, WHO/SDE/WSH/05.08/121, Background document for development of WHO Guide lines for Drinking-water Quality, 2005.

WHO Geneva, Principles of Characterizi ng and Applying Human Exposures Models, Harmonization Project Document No. 3, 2005.

Xin H., Naiyun GAO and Yang D., Bromate io n formation in dark chlorination and ultraviolet/chlorination processes for bromide- containing water, Journal of Environmental Sciences 20: 246ñ251, 2008.

* * *MEPC 60/2/6 ANNEX Page 65

I:\MEPC\60\2-6.doc APPENDIX 1



### QAPP FOR ìHiBallastî SYSTEM

Project ID: 09 Elechemtech-BWMS

System Developer: Hyundai Heavy Industry Co., Ltd 1, Jeongha-dong Dong-gu, Ulsan, Republic of Korea Tel. 82-52-202-2114 Fax. 82-52-202-3470 www.hhi.co.kr

System Developer Elchemtech Co., Ltd. 429-1 Gasan-dong Geumchun-gu, Seoul Tel. 82-2-6277-4100~6 Fax. 82-2-6277-4107 www.elchemtech.com
Primary System Tester (Type Approval Test Organization) Korea Marine Equipment Research Institute 1125-22 Dongsam-dong, Youngdo-gu, Busan, Republic of Korea Tel. 82-51-400-5000 Fax. 82-51-400-5091 www.komeri.re.kr

February 2009 

### Quality Assurance Project Plan (QAPP) for testing of Elchemtech-BWM System for Type Approval by the Ministry of Land, Transport and Maritime Affairs (MLTM), Republic of Korea in accordance with the Guidelines for Approval of Ballast Water Management Systems (G8)MEPC 60/2/6 ANNEX Page 66

I:\MEPC\60\2-6.doc Contents

Content ....................................................................................................................... ...............2 Introduction and background ................................................................................................... .5 Quality Management Plan (QMP) ............................................................................................6 1. HHI

............................................................................................................................... .... 2. Korea Marine Equipment Research Institute .................................................................7 Quality Assurance Project Plan (QAPP) ...................................................................................8 Quality Statement ............................................................................................................. 8 Approval Sheet ................................................................................................................ .9 Distribution List ............................................................................................................. 10

1. PROJECT MANAGEMENT .......................................................................................12

1.1 Project Description ÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖÖ.....12 1.1.1 Address of QAPP ........................................................................................12 1.2 Project Organization and Responsibilities ............................................................12 1.3 Project and Task Description .................................................................................15 1.3.1 Test Site .......................................................................................................15 1.3.2 The ECT-BWM System ..............................................................................15 1.3.3 Test Schedule ..............................................................................................17 1.3.4 Task .............................................................................................................17 1.4 Quality Assurance Objectives ...............................................................................18 1.5 Training and Certification .....................................................................................20 1.5.1 Collection and Handling of Samples ..........................................................20 1.5.2 Laboratory Testing and Analysis .................................................................20 1.6 Document and Records .........................................................................................21 1.6.1 QAPP ..........................................................................................................21 1.6.2 Field Sample Records ..................................................................................24 1.6.3 Chain of Custody Records ..........................................................................24 1.6.4 Laboratory Raw Data Records.....................................................................24

2. MEASUREMENT AND DATA ACQUISITION ........................................................25

2.1 Sampling Process Design ....................................................................................25 2.2 Sampling Methods ...............................................................................................26 2.2.1 Sample Collection, Preparation, Decontamination Procedure ....................26 2.2.2 Sampling Equipment, Preservation, and Holding Times ............................26 2.2.3 Sampling/Measurement System Failu re Response and Corrective Action Process .................................................................................................................26 2.3 Sample Handling and Custody ............................................................................26 2.4 Preparation of Samples and Analytical Methods .................................................27 2.4.1 Analysis of Organisms in Water Samples ( ≥ 10 ñ 50 μm and ≥ 50 μm) .....27 2.4.2 Samples for Chemical Analyses (KTR) ......................................................28 2.4.3 Samples for Bacteriological Analysis .........................................................28 2.5 Quality Control Procedures .................................................................................29 2.6 Data Acquisition ..................................................................................................29MEPC 60/2/6 ANNEX Page 67

I:\MEPC\60\2-6.doc 2.7 Data Management ................................................................................................30 2.7.1 Data Recording ...........................................................................................30 2.7.2 Data Validation ............................................................................................30 2.7.3 Data Transformation ...................................................................................30 2.7.4 Data Transmittal ..........................................................................................30 2.7.5 Data Reduction ............................................................................................30 2.7.6 Data Analysis ..............................................................................................31 2.7.7 Data Tracking ..............................................................................................31 2.7.8 Data Storage and Retrieval .........................................................................31 2.7.9 Data Release ................................................................................................31

3. ASSESSEMENT AND OVERSIGHT .........................................................................32

3.1 Assessment and Response Actions ......................................................................32 3.2 Reports to Management .......................................................................................33

4. DATA VALIDATION AND USABILITY ...................................................................33

4.1 Data Review, Validation, and Verification ...........................................................33 4.1.1 Sampling Design .........................................................................................33 4.1.2 Calibration ...................................................................................................33 4.1.3 Data Reduction and Processing ..................................................................33 4.2 Validation and Verification Methods ...................................................................34

5. REFERENCES ............................................................................................................35

6. APPENDICES .............................................................................................................35

Appendix 1 ñ Certification of Accreditation (HHI) ...................................................36 Appendix 2 ñ Certification of Accreditation (KOMERI)...........................................41 Appendix 3 ñ Certificate for ëIdentif ication of Marine Microalgaeí from IOC-UNESCO ............................................................................43 Appendix 4 ñ Electrical Storage Format of QAPP for Elechemtech-BWMS project..........................................................45 Appendix 5 ñ Chain of Custody Record.....................................................................46 Appendix 6 ñ Standard Operat ion Procedures (SOPs) ..............................................99 Appendix 7 ñ Quality Control methods for DOC and TOC analysis .......................126 Appendix 8 ñ Reference ma terials and papers .........................................................128MEPC 60/2/6 ANNEX Page 68

I:\MEPC\60\2-6.doc Sampling and test methods

1 Sampling

Each sample was collected from the sampling ports S1 to S6 during operation of lab-scale ìHiBallastî system. Procedures for sampling and transferring are desc ribed in details in appendix 1 (QAPP, Section 2 ìMeasurement and data acquisitionî). Figure A1 and Table A1 show sampling points and detailed inform ation for sampling points respectively.

From now on, day 0 means the point of ballas ting, day 1 means 1 day after ballasting. Day 5 refers to the point of de -ballasting after 5 days.

Figure A1 Sampling pointsMEPC 60/2/6 ANNEX Page 69

I:\MEPC\60\2-6.doc Table A1: Sampling and Analysis summary

Sampling Analytical Parameter
Point Time Lapse Activity Time Control Treated Water Onsite Analysis Lab Analysis Laboratory for analytical work

Before Ballasting B S1 Salinity, DO, pH, Turbidity Water density, TSS, DOC, POC KTR

DO, pH,

TRO DOC,POC, Byproducts KTR Day

0 During Ballasting

(10 hrs) B, M S2 S3, S4, S5 Microorganism KOMERI Byproducts KTR Day

1 Holding M S2 S5 Microorganism KOMERI Day

2 Holding M Microorganism KOMERI
Day

3 Holding M Microorganism KOMERI
Day

4 Holding M Microorganism KOMERI

Before treating ballast water M S2 S5 TRO KTR

During treating ballast water M S6 TRO KTR

Microorganism KOMERI TRO Byproducts KTR Day

5

After treating ballast water E S6 Toxicity MEI * B : Beginning of the test; M : Middle of the test; E : End of the test

2 Evaluation of system Performance

Test standard used in this test is adequate to the IMO MEPC 58/23, Annex 4, Part 2, 2. 3. 20 (and IMO BWM/CONF/36, BWM Convention, regula tion D-2) and details as below:

ï pH: Standard Method 4500 H+B (APHA, 2005) Measurement with Electrode multiprobe (Hydrolab, USA) ï Water temperature: Standard Method 2550 (APHA, 2005) Measurement with Electrode multiprobe (Hydrolab, USA) ï DO: Standard Method 4500-O G (APHA, 2005) Measurement with Electrode multiprobe (Hydrolab, USA) ï Turbidity: Standard Method 2130 B (APHA, 2005) Measurement with Electrode multiprobe (Hydrolab, USA) ï Salinity: Standard Method 2520 B (APHA, 2005) Measurement with Electrode multiprobe (Hydrolab, USA)MEPC 60/2/6 ANNEX Page 70

I:\MEPC\60\2-6.doc ï DOC and POC: Standard Method 5310 B (APHA, 2005) ï TSS: Standard Method 2540 D (APHA, 2005) ï Viable organism ( ≥ 10~50 μ m): Fluorescein dying with 5-CFDA AM (Anja et al. , 2005) Standard Method 10200 C (APHA, 2005), Culture methods (Manual and Guide, UNESCO, 2005) ï Viable organism ( ≥ 50 μ m): Staining method (Tang et al. , 2006), Standard Method 10200 C (APHA, 2005) ï Heterotrophic bacteria: Standard Method 9215 C and/or US EPA 1604 (2002) ï Total Coliform and E. coli: Standard Method 9215 C and/or US EPA 1604 (2002) ï Enterococci: Standard Method 921 5 C and/or US EPA 1600 (2002) ï Toxicogenic Vibrio cholerae: Standa rd Method 9260 H (APHA, 2005) and/or API 20E kit (BioMerieux, Inc.)

Two tests were performed in accordance with the requirements of the Guidelines for approval of ballast management system (MEPC 58/23, a nnex 4) and regulation D-2 of the BWM Convention). Test results show that this ballas t water treatment system meets the ballast water performance standard D-2 of the BWM Convention. The test results are briefly described as Table A2 and described in deta ils at appendix 1 (Test Report).

Table A2: Test results of ballast water management system

Salinity Test duration (Ballasting to de-ballasting) Results (Reg. D-2) Valid condition (Regulation D-2.1) (IMO resolution MEPC.174(58) Annex 4, Part 2-2.3.36)

33 PSU 25 Feb. 2009 ñ 02 Mar. 2009 PASS PASS

20 PSU 04 Mar. 2009 ñ 09 Mar. 2009 PASS PASS

* * *MEPC 60/2/6 ANNEX Page 71

I:\MEPC\60\2-6.doc APPENDIX 2



### TEST REPORT OF CHEMICAL ANALYSIS

Quality Assurance Project Plan (QAPP)



### Elchemtech-BWM System

Korea Testing & Research Institute

prepared by: Jae-Hong Kim Korea Testing & Research Institute 411 Daun-dong, Jung-gu, Ulsan, Republic of Korea www.ktr.or.kr

reviewed by: Sung-Uk Lee Korea Testing & Research Institute 411 Daun-dong, Jung-gu, Ulsan, Republic of Korea www.ktr.or.kr

Ph.D. Sang-bong Moon Elchemtech 429-1 Gasan-dong, Cumcheun-Gu, Seoul, Republic of Korea Tel. 82-2-6277-4100/Fax. 82-2-6277-4107

co-work to Young-Soo Kim Korean Marine Equipment Research Institute 1125-22 Dongsam-dong, Youngdo-gu, Busan, Republic of Korea eng.komeri.re.kr

February 2009MEPC 60/2/6 ANNEX Page 72

I:\MEPC\60\2-6.doc Chemical analysis

Procedures for sampling, transferring and analysis methods are described in details on appendix 2 (QAPP by KTR).

1 AOX

Filtering of the sample through a filter with an effective pore size of 0.45 μ m. Acidification of the filtrate with nitric acid and elution of the inorganic halides with ethyl acetate. Filter sample containing particles through a filtration apparatus with a pore width of 0.45 μ m. Elution of the test sample 100 mL with ethyl acetate 10 mL.

2 Bromate

Bromate is measured using Ion-Chromatgraphy with the Addition of a Postcolum Reagent. The method uses an IonPac AS9-HC column and followed by postcolumn addition of o-ianisidine(ODA) to visible absorb ance detection of the bromate ion.

3 VOCs/THM

This is a general purpose method for the iden tification and simultaneous measurement of purgeable volatile organic compounds in surface water, ground water, a nd drinking water in any stage of treatment. The method is applicable to a wide range of organic compounds, including the four trihalomethane disinfection by-products that have sufficiently high volatility and low water solubility to be removed from water samples with purge and trap procedures.

4 Halogenated Phenols

Samples are extracted using an appropriate sa mple preparation method-EPA 3510C. Prior to analysis, the extracts are cleaned up, as necessa ry, and the solvent exchanged to 2-propanol. The target Halogenated Phenols also may be deriva tized with pentafluorob enzyl bromide (PFBBr) and analysed by gas chromatography (GC/ECD).

5 TRO

TRO was analysed by US EPA 330. 5(1978). Chlorine (hypochlorite ion, hypochlorous acid) and chloramines stoichiometrically liberate iodine from potassium iodide at pH 4 or less. The iodine is titrated with a standard reducing agent such as sodium thiosulfate using a starch indicator. The results are calculated as mg/L Cl even though the actual measurem ent is of total oxidizing power because chlorine is the dominant oxidizing agent present.

In addition, Phenylenediammonium/potassi um iodide (DPD/K I) indicator and a Pocket Colorimeter (LaMotte). This procedure was equiva lent to US EPA Method 330.5 for wastewater and 94 Standard Meth od 4500-Cl G for drinking water. TRO concentration (mg/L) measurements were calculated and expressed as equivalent concentrations of bromine (Br 2 , 1 mol Cl 2 = 0.44 mol 96 Br 2 ).MEPC 60/2/6 ANNEX Page 73

I:\MEPC\60\2-6.doc 6 By-product of Disinfection (HANs)

Methyl tertiary-butyl ether( MTBE, Merck), sodium chloride(Merck), ammonium chloride (Merck), chloral hydrate(Accu), dibromoacet onitrile(Accu), trichl orocatonitrile(Accu), dichloroacetinitrile(Accu), bromoc hloroacetonitrile(Accu), chloropicrin(Accu). Stock solutions of chlorine by product are prepared in acetone and Internal standard (1,2-dibromo-3- chloropropane) are prepared in MTBE.

7 By-product of Disinfection (HAAs)

A 200-mL volume of sample is adjusted to pH < 0.5 and extracted with 4-mL of methyltert -butylether (MTBE). The haloacetic acids that have b een partitioned into the organic phase are then converted to their methyl esters by the addition of acidic methanol followed by slight heating. The acidic extract is neutralized by a back ex traction with a saturated solution of sodium bicarbonate and the target analytes are iden tified and measured by capillary column gas chromatography using an mass spectrometer (G C/MSD). Analytes are quantitated using procedural standard calibration.

8 Other compounds

- O 3 , ClO 2 : Model Q45H/64, ATi Analyt ical technology, Inc/UAS - S -2 : US Standard method 4500- S-2 -B - H 2 : Agilent GC/TCD - Cl 2 , O 3 gas : Detector tube, GASTEC/Japan - TOC : TOC-VCPH, Shimadzu/Japan

* * *MEPC 60/2/6 ANNEX Page 74

I:\MEPC\60\2-6.doc APPENDIX 3

TEST REPORTS OF AQUATIC TOXICITY

Acute aquatic toxicity

Most sensitive organism for ballast water treated by ìHiBallastî system was algae, Skeletonema
costatum that gave the EC 50 value of 69.30% and 63.01% for the 33 PSU and 20 PSU from aquatic toxicity test result, respectively. Fo r the other test organism s, no significant acute toxicity was observed.

Algae: For the study to assess the eff ects of the seawater treated by ìHiBallastî system on the diatom, Skeletonema costatum , during 72 hours, NOEC and LOEC va lues from Hypothesis Test and EC 50 values based on the cell densities at the end of the experiment were calculated for both 33 PSU and 20 PSU treated ballast water.

Crustacean: For the study to assess the effects of th e seawater treated by ìHiBallastî system on copepod, Tigriopus japonicus, during 48 hours, EC 50 and LC 50 values based on mobilization and survival data at the end of the experiment we re calculated for both 33 PSU and 20 PSU ballast
water.

Fish: For the study to assess the effects of the seawater tr eated by ìHiBallastî system on olive flounder, Paralichthys olivaceus , during 96 hours, LC 50 values based on survival data at the end of the experiment were calculated fo r both 33 PSU and 20 PSU ballast water.MEPC 60/2/6 ANNEX Page 75

I:\MEPC\60\2-6.doc APPENDIX 4

KEY DATA-SET

Key data-sets for the Active Substances and Relevant Chemicals were summarized according to the form of the GESAMP-Ballast Water Working Group [MEPC 59/2/13, annex 2].

* * *MEPC 60/2/6 ANNEX Page 76

I:\MEPC\60\2-6.doc APPENDIX 5

HAZID STUDY

This report is the hazard identification (HAZID) study of ìHiBallastî syst em to be installed on board ship. The objective of this study is to identify and summarize all known hazardous events during the normal operation and maintenance phas es. The HAZID workshop to be composed of experts, who have a lot of experiences of mech anical and process design , manufacture, and ship trial test etc., in HHI, was carried. Th e scopes of HAZID study are as follows:

• Electrolyzer (including power generator and cooler)

• Gas separator

• Injection pump

• Neutralization unit

In the HAZID study, the total 27 hazards we re identified for the normal operation and maintenance phases of ìHiBallastî. The cr itical 23 hazards were compiled in the Hazard Register, and recommended the corr ective or preventive action plans.

The key summaries of HAZID workshop are as follows:

Hazard No. Hazard System (or Sub-system) Mode

1 Electrode clogging due to foreign material Electrolyzer Operation 2 Current breaking Electrolyzer Operation 3 High temperature inside the el ectrolyzer Electrolyzer Operation 4 Electrolyzer leakage Electrolyzer Maintenance 5 Leakage of seawater Electrolyzer Maintenance 6 Too much vibration Electrolyzer Operation 7 Electric shock Electrolyzer Operation 8 Seawater leakage from cooli ng medium. Electrolyzer Operation 9 Electrolyte leakage from the el ectrolyzer Electrolyzer Operation 10 Corrosion of Inlet pipe Electrolyzer Operation
11 Flow control valve Failure Gas separator Operation 12 Vent line leakage (Internal) Gas separator Operation 13 Pump cavitation Gas separator Operation 14 Vent failure Gas separator Operation 15 Gas leakage Gas separator Operation 16 Injection pump: Failure to start Injection pump Operation

17 Back-flow from main ballast water line (Electrolyte injection pump) Neutralization unit OperationMEPC 60/2/6 ANNEX Page 77

I:\MEPC\60\2-6.doc

Hazard No. Hazard System (or Sub-system) Mode

18 Leakage of neutralizat ion solution Neutralization unit Maintenance

19 Neutralization injection pump failure: Failure to start Neutralization unit Operation

20 Flow control valve failure: Failure to Open Neutralization unit Operation

21 Back-flow from main ballast water line(Neutralization line) Neutralization unit Operation
22 TRO meter Failure Neutralization unit Operation 23 No injection of neutralization agent Neutralization unit Operation

* * *MEPC 60/2/6 ANNEX Page 78

I:\MEPC\60\2-6.doc APPENDIX 6

SYSTEM DESCRIPTION OF ìHiBALLASTî SYSTEM

1. Introduction 2. System Overview 2.1 Process summary 2.2 System boundary 2.3 Electric power distributi on for treatment system 2.4 System control 2.5 Safety functions of system
2.6 Utilities 3. Equipment Unit 3.1 System Control Unit
3.2 Filter Unit 3.3 Electrolysis Unit
3.4 Neutralization Unit 4. System Operation
4.1 General 4.2 Modes of operation 4.3 Start-up and Shutdown of System 4.4 Control functions in normal operation 5. Appendix

* * *MEPC 60/2/6 ANNEX Page 79

I:\MEPC\60\2-6.doc APPENDIX 7

ENVIRONMENTAL RISK ASSESSMENT REPORT

Environmental risk analysis was conducted to ev aluate potential risk of the Active Substances and Relevant Chemicals generate d from ìHiBallastî system. Based on the PEC/PNEC ratio, the aquatic environmental risk was assessed. The PE C was predicted from the results of chemical analysis and MAMPEC Marine Anti-foulant Model to Predict Environmental Concentration) modelling. PNEC was determined fr om the literature reviews of acu te and chronic toxicity test for the chemicals. The proce dure of environmental risk anal ysis applied in this study is represented in following Figure A.

Figure A.: Procedure of en vironmental risk analysis

The PEC/PNEC ratios of all chemicals on the Da y 1 and Day 5 were less than 1 with the maximum and average PEC. It means that when analysed all chemicals have no effects on the aquatic environment.

* * *MEPC 60/2/6 ANNEX Page 80

I:\MEPC\60\2-6.doc APPENDIX 8

MATERIAL SAFETY DAT A SHEETS (MSDS)

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