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MARINE ENVIRONMENT PROTECTION

COMMITTEE

61st session Agenda item 2 MEPC 61/2

9 March 2010 Original: ENGLISH

HARMFUL AQUATIC ORGANISMS IN BALLAST WATER

Application for Basic Approval of Techwin Eco Co., Ltd. (TWECO) Ballast Water Management System (PurimarTM)

Submitted by the Republic of Korea

SUMMARY

Executive summary: This document contains the non-confidential information related to the application for Basic Approval of Techwin Eco Co., Ltd. (TWECO) Ballast Water Managem ent System (PurimarTM), in accordance with the "Procedure for approval of ballast water management systems that make use of Active Substances (G9)" 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; MEPC 59/2/13 and

BWM.2/Circ.24

Introduction

1 Ballast water management systems, which make use of Active Substances 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 "Procedure for approval of ballast wa ter management systems that make use of Active Substances (G9)", adopted by resoluti on MEPC.169(57), defines the principal aspects to be documented by data or testing (MEPC 57/21, annex 1, paragraph 4.2.1) and some basic principles for risk evaluation (MEPC 57/21, annex 1, paragraph 5.3). According to section 6 of Procedure (G9), the Organization should evaluate the information provided in the application.

3 According to BWM.2/Circ.24, proposals for 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.MEPC 61/2 Page 2

I:\MEPC\61\2.doc In the meantime, a document on the proposal for approval containing all the non-confidential data related to the respective ballast water management systems that make use of

Active Substances needs to be submitted to MEPC 61.

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

5 The Republic of Korea therefore submits the non-confidential part of the applicant's 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 confidential treatment.

Action requested of the Committee

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

***MEPC 61/2 Annex, page 1

I:\MEPC\61\2.doc ANNEX

NON-CONFIDENTIAL INFORMATION ON TECHWIN ECO CO., LTD. (TWECO) BALLAST WATER MANAGEMENT SYSTEM (PurimarTM)

Contents

LIST OF ABBREVIATIONS

1 INTRODUCTION

1.1 History of TWECO’s ballast water management system development

1.2 Terms and definitions 1.3 Facility description of Purimar TM system

1.3.1 Filter

1.3.2 Electrolizer

1.3.3 Neutralization unit 1.3.4 Monitoring and control system

2 GENERAL

2.1 Legal provision 2.2 Principles of acceptability 2.3 Submission of an application for Basic Approval 2.4 Confidentiality and data protection

2.5 Test methods 2.5.1 Sampling 2.5.2 Efficacy testing 2.5.3 Chemical analysis 2.5.4 Whole Effluent Toxicity (WET) testing 2.6 Alternatives to testing

2.7 Procedures and timelines

3 DATASETS REQUIRED IN THE APPLICATION

3.1 Identification of Preparation, Active Substances and Relevant Chemicals 3.1.1 Preparation

3.1.2 Active Substance

3.1.3 Relevant Chemicals 3.1.4 Other Chemical (sodium thiosulfate) 3.2 Results of efficacy testing 3.2.1 Preliminary experiments for the system application 3.2.2 Land-based test run for the system confirmation 3.3 Results of chemical analysis (Relevant Chemicals) 3.4 Data on effects on aquatic plants, invertebrates and fish, and other Biota, including sensitive and representative organisms 3.4.1 Whole Effluent Toxicity (WET) test for the evaluation of acute and chronic aquatic toxicity 3.4.2 Acute and chronic aquatic toxicity of Active Substance, Other Chemical and

Relevant Chemicals 3.4.3 Endocrine disruption 3.4.5 Bioavailability/biomagnification/bioconcentration 3.4.6 Food web/population effectsMEPC 61/2 Annex, page 2

I:\MEPC\61\2.doc 3.5 Data on mammalian toxicity

3.6 Data on environmental fate and effect under aerobic and anaerobic condition 3.6.1 Modes of degradation (Biotic; Abiotic) 3.6.2 Bioaccumulation, partition coefficient, octanol/water partition coefficient

3.6.3 Persistence and identification of the main metabolites in the relevant media 3.6.4 Reaction with organic matter 3.6.5 Potential physical effects on wildlife and benthic habitats

3.6.6 Potential residues in seafood 3.6.7 Any known interactive effects 3.7 Physical and chemical properties 3.8 Analytical methods at environmentally relevant concentrations

4 USE OF THE ACTIVE SUBSTANCE OR THE RELEVANT CHEMICAL

5 MATERIAL SAFETY DATA SHEETS

5.1 Hazard classification of Active Substance

5.2 Hazard classification of Relevant Chemicals

5.2.1 DBPs 5.2.2 Hydrogen gas

5.3 Hazard classification of Other Chemical

6 RISK CHARACTERIZATION

6.1 Screening for Persistence, Bioaccumulation and Toxicity

6.2 Evaluation of the treated ballast water 6.3 Risk characterization and analysis 6.3.1 Reaction with organic matter 6.3.2 Characterization of degradation route and rate 6.3.3 Prediction of discharge and environmental concentrations 6.3.4 Assessment of potential for bioaccumulation

6.3.5 Effects assessment 6.3.6 Effects on aquatic organisms

6.3.7 Effects on sediment 6.3.8 Comparison of effect assessment with discharge toxicity

7 RISK ASSESSMENT

7.1 Risk to safety of ship

7.1.1 Corrosion 7.1.2 Fire and explosion (formation of gases) 7.1.3 Storage and handling of the substances

7.2 Risks to human health

7.2.1 Risk characterization 7.3 Risks to the aquatic environment

8 ASSESSMENT REPORT

8.1 Overview of data and endpoint 8.2 Quality of the test reports

9 REFERENCES

10 APPENDICESMEPC 61/2 Annex, page 3

I:\MEPC\61\2.doc LIST OF ABBREVIATIONS

For the purpose of this report, any abbreviations used are the same as specified in Procedure (G9)

, as follows:

Abbreviation Description Abbreviation Description

% Percent mN/m millinewton per metre

°C Celsius degree mPa millipascal

AS Active Substance MS Matrix Spikes

ASTM American Society for Testing and

Materials MSD Matrix Spikes Duplicates

ATS Agency for Technology and

Standards MSDS Material Safety Data Sheets

BCF Bioconcentration factor mV Millivolts

BPA Busan Port Authority N.D Not detected

Br 2 Bromine N/A Not available, Not applicable

BWMS Ballast Water Management System Na 2 S 2 O 3 Sodium thiosulfate

CAS Chemical Abstract Service NaOCl Sodium hypochlorite

CASRN Chemical Abstracts Service Registry Number NELAP National Environmental Laboratory Accreditation Program

CFU Colony Forming Unit NFRDI National Fisheries Research & Development Institute

Cl - Chloride ion NIOZ Netherlands Institute for Sea

Research

Cl 2 Chlorine NOAEL No Observed Adverse Effect Level

CO 2 Carbon dioxide NOEC No Observed Effect Concentration

Conc. Concentration NOEL No Observed Effect Level (used interchangeably with NOAEL)

COPC Chemical(s) of Potential Concern NPOC Non-purgeable organic carbon

CSA Catalytic Stable Anode O&M Operational/Maintenance

DAPI 6-diamidino-2-phenylindole OBr - Hypobromite ion

DAU Dong-A University OCl - Hypochlorite ion

DBPs Disinfection By-products OECD Organization for Economic Co-operation and Development

DC Direct Current OIT Operator Interface Terminal

DGPS Differential Global Positioning System OPPTS Office of Prevention, Pesticides,

and Toxic Substances

DO Dissolved Oxygen ORP Oxidation Reduction Potential

DOC Dissolved Organic Carbon OSHA Occupational Safety and Health

Administration

DPD N,N-diethyl-p-phenylenediamine Pa Pascal

dph days post-hatch PBT Persistence, Bioaccumulation, and Toxicity

DQOs Data Quality Objectives PBT profiler Persistent, Bioaccumulative, and

Toxic ProfilerMEPC 61/2 Annex, page 4

I:\MEPC\61\2.doc

Abbreviation Description Abbreviation Description

dynes/

cm dynes per centimetre PE Polyethylene

EC 50 Effective concentration of

substance that causes 50% of maximum response PEC Predicted Environmental

Concentrations

ECR Engine Control Room PEL Permissible Exposure Limit

EDCs Endocrine Disrupting Chemicals PFD Process Flow Diagram

EM Excellent Materials pKa Dissociation Constant

EPI Environmental Sustainability Index PLC Programmable Logic Controller

FRP Fibre reinforced plastic PM Phase Rotation Monitor

g/day gram per day PNEC Predicted No-Effect

Concentrations

G/T Gross Tonnage POC Particulate Organic Carbon

GESAMP

-BWWG Joint Group of Experts on the Scientific Aspects of Marine

Environmental Protection–Ballast Water Working Group PPE Personal Protective Equipment

H + Hydrogen ion ppm Parts per million

H 2 Hydrogen gas PQL Practical Quantification Limit

HAAs Haloacetic acids PSU Practical Salinity Units

HAMP Harmful Aquatic Microorganisms and Pathogens QAPP Quality Assurance Project Plan

HANs Haloacetonitriles QMP Quality Management Plan

HOBr Hypobromous acid R&D Research and development

HOCl Hypochlorous acid RC Relevant Chemicals

hPa hecto-Pascal RDL Required Detection Limits

HPhs Halophenols RfD Reference Dose

HSDB Hazardous Substances Data Bank RPD Relative Percent Difference

IARC International Agency for Research

on Cancer RPhrases Risk Phrases

IC Inorganic carbon SB Sterile bottles

ICSC International Chemical Safety

Cards SCGE Single Cell Gel Electrophoresis

IMO International Maritime Organization SCR Silicon Controlled Rectifier

IPCS International Programme on Chemical Safety SCWO Supercritical water oxidation

ISO International Organization for

Standardization SGPT Serum Glutamate-Pyruvate

Transaminase

IUCLID International Uniform Chemical

Information Database SIDS Screening Information Dataset

kg/m 3 kilogram per cubic metre SOPs Standard Operating Procedures

KHNP Korea Hybrid & Nuclear Power Co.

Ltd. SPhrases Safety Phrases

Koc Organic Carbon Partition

Coefficient SP-IDC Shipping & Port-Internet Data

CentreMEPC 61/2 Annex, page 5

I:\MEPC\61\2.doc

Abbreviation Description Abbreviation Description

KOLAS Korea laboratory accreditation

scheme SST Stainless Steel

Kow Octanol/Water Partition Coefficient SVOCs Semi-Volatile Organic Compounds

L/kg Litre per kilogram TCA Trichloroacetic acid

L/min Litre per minute THMs Trihalomethanes

LC 50 Lethal Concentration 50 TOC Total Organic Carbon

LD 50 Lethal Dose for 50% of test population TOXNET Toxicology Data Network

LEL Lower Explosive Limit TRO Total residual oxidants

M Meter TSS Total Suspended Solids

mA Milliampere TWECO Techwin Eco

MAMPEC Marine Antifoulant Model to

Predict Environmental

Concentrations UCL Upper Confidence Level

MBDC Marine Bio-industry development

centre UI User Interface

MDL Minimal Detection Limit US EPA United States Environmental Protection Agency

MEPC Marine Environment Protection

Committee Vdc Volts of continuing current

mg/kg

bw milligram per kilogram body weight W/H Wheel House

mg/kg-d milligram per kilogram per day WET Whole effluent Toxicity

mg/L milligram per litre WHO World Health Organization

MLTM Ministry of Land, Transport and

Maritime Affairs wt % Weight per cent

Mm 2 /s square millimetre per second μg/L microgram per litre

mmHg millimetre of mercury μg/ml microgram per millilitre

mN/m millinewton per metre μM micro-molarity

mPa millipascal μS/cm microsiemens per centimeter

1 INTRODUCTION

1.1 Ballast water management system ("Purimar TM ")

The Purimar TM Ballast Water Management System (or simply Purimar TM System) developed by Techwin Eco (TWECO) is a system utilizing proven technology to filter out, oxidize and disinfect all harmful aquatic organisms and pathogens present in the ballast water with Sodium Hypochlorite.

The system testing of the Purimar TM System was carried out through the two-step process. The preliminary operating experiments for the syst em application were performed by using the pilot-scale test set-up with a flow rate of 5 m 3 /hr and the supplementary laboratory-scale. After accomplishing the preliminary operating experiments, the land-based test runs were executed by using the full-scale Purimar TM system with a capacity of 250 m 3 /hr installed onMEPC 61/2 Annex, page 6

I:\MEPC\61\2.doc the TWECO test barge at two different sites with more than 10 PSU difference in salinity – seawater test in Busan Port (>32 PSU) and brackish water test in Nakdong River or similar estuary (3~32 PSU). At each operating event of the land-based test run, water quality parameters of influent water were measured immediately on site and at the laboratory. Only those events fulfilled the requirements of Guidelines (G8). Water quality was taken into further consideration for the test cycles of the land-based test run.

1.2 Terms and definitions

For the purpose of this report, terms and definitions are the same as specified in Procedure (G9)

, and are therefore not repeated here, except for the following which are specific to this report:

- "Pre-treated Water" is seawater treated by only a filtration system, which is a pre-treatment part of the PurimarTM System.

- "Treated Water" is seawater treated by the PurimarTM System.

- "Ballast Water Discharge" is the treated ballast water that has passed through the neutralization unit during deballasting. The neutralization is a process for further decrease of the total residual oxidants (TRO) concentration if required before discharge at deballasting.

- "Active Substance" refers to the total residual oxidants (TRO) generated in treated ballast water from the electrolysis-based chlorination process of the

Purimar TM System, which is completely responsible for inactivating all harmful aquatic organisms and pathogens (HAMP) present in the ballast water. Active

Substances are discussed in detail in section 3.1.2.

- "Preparation" has the same meaning as "Active Substance" for the Purimar TM
System as it does not intenti onally add any preparation besides chlorination.This preparation is discussed in detail in section 3.1.1.

- "Relevant Chemicals" refer to the chlorination by-products formed by the reaction of chlorine with natural organic matter. Relevant Chemicals are

discussed in section 3.1.3.

The above interpretations of the definitions contained in Procedure (G9) mean that in the

case of the Purimar TM System, these terms all refer to the treated ballast water that is discharged following the sequence of:

.1 ballasting;

.2 treatment,

.3. voyage; and

.4 deballasting.

As have been applied for other electrolysis- based ballast water management systems that have been granted Final Approval by MEPC, it is therefore the treated ballast water that is considered in this application and thus tested for efficacy, toxicity and content of chemicals.MEPC 61/2 Annex, page 7

I:\MEPC\61\2.doc 1.3 Facility description of Purimar TM system

1.3.1 Filter

The filter unit can remove particles and organisms having a size of more than 50μm from the ballast water, and includes an automatic back-flushing system. In the automatic back-flushing system, the self-cleaning system operates to remove foreign materials attached to the surface of the filter and always maintains uniform treatment efficiency when there is a stoppage phenomenon in the filter due to change in pressure.

1.3.2 Electrolyzer

The electrolysis unit has an objective of producing and injecting sodium hypochlorite (NaOCl), through electrolysis of ballast water at the time of ballasting. In the ballasting mode, a part of seawater divided from the ballast main piping line is electrolyzed and then injected to the main piping line again. The PurimarTM System uses the divided seawater in an amount less than 1% of the total flow-rate of seawater that flows into the main ballast pipeline. The electrolyzer uses the CSA electrode that applies the unique technology of TWECO and is designed to be able to control the fouling.

Hydrogen gas is a by-product generated during the production of sodium hypochlorite. The mixed solution of the hypochlorite and the hydrogen gas flows into the hydrogen-hypo separation unit immediately after they are produced from the electrolyzer. More than 95% of the hydrogen having a low specific gravity is separated from the hydrogen-hypo solution and is transmitted by the action of cyclone to the de-gas tank by piping through a small titanium orifice at the upper part of the cyclone, and th e remaining sodium hypochlorite solution is injected into the ballast water main pipeline through the injector.

1.3.3 Neutralization unit

The neutralization unit is installed in the PurimarTM System to achieve the objective of reducing the residual TRO included in the ballast water to a level that is not harmful to humans and natural environment and then discharging it at the time of deballasting. The injection point of the neutralizing agent is disposed on the inlet or outlet of the ballast pump for the even mixing of the neutralizing agent and the ballast water. The ballast water whose neutralization is completed maintains the TRO value of less than 0.1 ppm.

1.3.4 Monitoring and control system

The Purimar TM System is designed to enable monitoring and control from any places in the ship, from a W/H (Wheel House) to an ECR (Engine Control Room) because the network function is possible. The PurimarTM System is also designed to monitor and control the filter unit, electrolysis unit (electrolyzer and rectifier), TRO sensor and neutralization unit for the optimal full-scale test. The main functions thereof are detailed in the complete confidential

dossier.

2 GENERAL

2.1 Legal provision

The legal provision for this application is regula tion D-3.2 of the International Convention for the Control and Management of Ships’ Ballast Water and Sediments, which stipulates that ballast water management systems that make use of Active Substances shall be approved by the Organization.MEPC 61/2 Annex, page 8

I:\MEPC\61\2.doc During its fifty-third session, the Marine Environment Protection Committee (MEPC) adopted the Procedure for approval of ballast water management systems that make use of Active Substances (G9) through resolution MEPC.126(53).

This application and the comprehensive testing program that has been conducted by TWECO to support it are in full compliance with Procedure (G9).

2.2 Principles of acceptability

In accordance with Procedure (G9) and as presented in this report, TWECO has sought to meet the principles of acceptability by underta king comprehensive toxicity testing of ballast water treated by the Purimar TM System in system testing, in order to determine if the system can be used and under which conditions the potential for harming the receiving environment or human health is acceptably low.

2.3 Submission of an application for Basic Approval

This application is for Basic Approval. The information in this dossier includes:

- results of the comprehensive toxicity testing and chemical analysis, as required in Procedure (G9);

- results of the efficacy testing, as required in Guidelines (G8);

- Quality Assurance Project Plan (QAPP); and

- technical specifications of the optimized Purimar TM System.

2.4 Confidentiality and data protection

TWECO accepts that all items listed in section 2.4 of the GESAMP-BWWG Methodology shall not be regarded as confidential once the system and Active Substance are approved.

2.5 Test methods

The undertaking of comprehensive testing for efficacy and toxicity of the Purimar TM System comprises four major tasks:

.1 sampling (Laboratory, Pilot-scale, and Land-based testing);

.2 determination of water quality parameters and efficacy testing of the samples (Guidelines (G8) testing);

.3 chemical analysis of the samples (Procedure (G9) testing); and

.4 whole Effluent Toxicity (WET) testing of the samples (Procedure (G9) testing).

The quality assurance arrangements for the tasks are the subject of a QAPP developed by TWECO and Dong-A University (appendix 3). All staf f involved in the efficacy and toxicity of

the Purimar TM System received training in the QAPP and its application to the procedures for each test. All test methods were carried out in compliance with the requirements of Guidelines (G8) and Procedures (G9).MEPC 61/2 Annex, page 9

I:\MEPC\61\2.doc 2.5.1 Sampling

In the preliminary experiments for the system application, water samples were collected during the operation of the pilot-scale test set-up using seawater in Ulsan as source water. For the preparation of brackish water samples, source water was diluted with tap water and passed through the test set-up. In addition, water samples for supplemental laboratory-scale experiments were obtained by adding a sodium hypochlorite solution, generated from the electrolysis of 3% NaCl solution, to the filtered commercial sea or brackish water. Every test run was performed on two water samples; sequentially, a control (untreated) experiment bypassing the filter and disinfection processes were conducted first.

In the land-based test runs for the system confirmation, water samples were collected during the operation of the full-scale Purimar TM System fitted on the TWECO test barge, at the Busan Port. At each operating event, water quality parameters of influent water were measured immediately on site and at the laboratory of MBDC. Only the event fulfilled Guidelines (G8) requirements as the water quality has been taken into further consideration for the test cycle of the land-based test run.

If required in ballast water discharge at deballasting, sodium thiosulfate was added to the treated water samples to immediately decrease the total residual oxidants (TRO) concentration as a neutralization process.

An overview of the testing scheme is presented in Table 2.1 and Figure 2.1. (See the complete confidential dossier.)

Collection of field samples was undertaken by a joint team of marine biologists and environmental engineers from TWECO, NLP and DAU, using standard water sample collection methods and in accordance with Guidelines (G8). Standard operating procedures (SOPs) were employed to provide consist ency and reproducibility of the sampling methods used by field personnel, as outlined in t he Quality Assurance Project Plan (QAPP).

Water samples were taken from both the control (untreated) and treatment tanks at two or three times of intervals following treatment – at the ballasting (immediately after treatment, Day O), at the two days storage (Day 2) or the discharge (deballasting with neutralization process, Day 2n), and at the five days after treatment with or without neutralization (Day 5 or Day 5n). An overview of the sampling points is presented in Figure 2.2.MEPC 61/2 Annex, page 10

I:\MEPC\61\2.doc Figure 2.2: Sampling points at the pilot-scale test set-up (A) and the

full-scale Purimar TM System (B)

Water samples were taken directly into a clean bucket after washing with sample water, pre-filtered with 45 μ m net to remove large particles and poured into sterile plastic bags to prevent possible contamination. The analytical laboratory provided pre-labelled sample containers which included the required preservative for each parameter.

The collected samples were cooled immediately in an ice-box, packed and transported to the laboratory test facilities by the field staff from NLP; to MBDC by car within one (1) hour of being collected and to SGS by KTX train, and parcel delivery service within five (5) hours. All the field and laboratory test facilities prepared written standard operating procedures (SOPs) for sample custody, and examples of the sample chain-of-custody form were contained in the QAPP. When the samples arrived at the laboratory test facilities, the sample custodian received the samples, signed the form, opened the sample coolers, carefully checked the contents for evidence of leakage and to verify that samples were kept on ice, and then verified that all information on the sample container label were correct and consistent with the information on the chain-of-custody form.MEPC 61/2 Annex, page 11

I:\MEPC\61\2.doc Full details of the collection of samples, including their handling and transmission under chain of custody for each testing, were contained in the QAPP.

2.5.2 Efficacy testing

Assurance of fulfillment of water quality test criteria and bio-efficacy testing was conducted by MBDC, based on the quality system of ISO/IEC 17025, in accordance with Guidelines (G8). Full details were contained in the QAPP.

2.5.3 Chemical analysis

At each sampling event Active Substance (TRO) was measured immediately on site, and the samples were then sent to MBDC for further analysis of TRO and SGS for analysis of Relevant Chemicals (disinfection by-products; DBPs).

Active Substance

Active Substance, in this dossier, is defined as the total of all oxidants present in treated

water of the Purimar TM System, which are discussed in detail in section 3.1.2.

TRO level was measured in situ (on the field and test barge) using two different analytical procedures, which are as follows:

- automatic sampling and testing using TRO concentration analyser (CLX Online Residual Chlorine Monitor, HF Scientific), installed separately in ballast line and deballast stream; and

- manual testing of water samples using portable Spectrophotometer (Chlorine Pocket Photometer, HF Scientific).

During further analysis of TRO at MBDC, TRO measurements were performed internally by the researchers using a Hach DR2800 colorimeter and Hach method 8167.

All these methods are based on a standard DPD (N,N-diethyl-p-phenylenediamine) colorimetric method (equivalent to US EPA METHOD 330.5). The TRO oxidizes triiodide ion (I 3 - ) to iodine (I 2 ). The iodine and free chlorine react with DPD to form a red solution. The colour intensity is proportional to the TRO concentration, which is displayed as the equivalent of mg/L as Cl 2.

Relevant Chemicals

"Relevant Chemicals", in this dossier, is defined to refer to the chlorinated/brominated by-products formed by the reaction with nat ural organic matter. These Relevant Chemicals

are discussed in detail in section 3.1.3.

The following items were measured to analyse Re levant Chemicals or a number of DBPs from reactions between chlorine and naturally-occurring compounds in the treated water, in accordance with Procedure (G9):

- Bromate (BrO 3 - );

- Trihalomethanes (THMs) including Trichloromethane (Chloroform), Tribromomethane (Bromoform), Chlorodibromomethane and Dichlorobromomethane;MEPC 61/2 Annex, page 12

I:\MEPC\61\2.doc - Haloacetic acids (HAAs) including Monochloroacetic acid, Dichloroacetic acid, Trichloroacetic acid, Monobromoacetic acid , Dibromoacetic acid, Tribromoacetic acid, Bromochloroacetic acid, Bromodichlo roacetic acid and Dibromochloroacetic acid;

- Haloacetonitriles (HANs) including Dichloroacetonitrile and Dibromoacetonitrile;

and

- Halophenols (HPhs) including Pentachlorophenol.

The analytical laboratory services for the measurement of DBPs using the discharge water samples from the Purimar TM System were carried out by the qualified and accredited laboratories under internationally-recognized guidelines (OECD or equivalent) and quality system of ISO/IEC 17025. Full details were given in the QAPP.

2.5.4 Whole Effluent Toxicity (WET) testing

WET testing was carried out by a joint organization of MBDC and Dong-A University Quality Assurance (QA) team, under internationally-recognized guidelines (OECD or equivalent) and internationally recognized quality assurance sy stem (GLP). This study aims to assess the residual toxicity of whole-effluent ballast water after treatment by the Purimar TM System, in accordance with Procedure (G9). The objectives are to analyse the impact of treated ballast

water on seawater and of brackish water ecos ystems to evaluate pos sible risks to humans and other recipients, posed by current and future exposure to ballast water treated by

the Purimar TM System, and to determine what additional measures might be needed to reduce any risks.

Immediately after verification of field water samples, the water samples were passed through the filtering system (pore size 0.45 μ m) by using peristaltic pump. After measurements of pH, temperature, salinity, and dissolved oxygen (DO), test substances prepared from the treated water samples were subjected to the concentration-response tests, which consisted of control dilution water (0%) and a minimum of three concentrations commonly selected to approximate a geometric series, i.e. 100%, 75%, 50%, 25% and 12.5%. With respect to the formulation of the dosing preparation, commercial natural seawater was used as a diluent. As the test substances prepared from the untreated ballast water samples were likely to be non-toxic, the single concentration (undiluted, 100% solution) was subjected to the limit test.

All WET tests were initiated simultaneously within 6 hours of sampling. For some tests which are necessary for the renewal of test substances, samples were kept in a secure storage (locked refrigerators) where they were maintained at 4 degrees Celcius.

In accordance with the Procedures (G9), a number of different tests were required, as listed

below:

- Growth Inhibition Test with Microalgae;

- Survival Test with Rotifer;

- Survival Test with Larval Fish;

- Reproduction Test with Rotifer; and

- Growth Test with Larval Fish.MEPC 61/2 Annex, page 13

I:\MEPC\61\2.doc Each test was the subject of a specific Study Plan, as contained in appendix 3 of the QAPP. All the test methods were carried out in compliance with the requirements of Procedure (G9) and all staff involved in the WET testing received training in the QAPP and its application to the Study Plan for each test.

2.6 Alternatives to testing

As outlined in section 1.1 of this annex, consistent with the approach that has been applied for other electrolysis-based ballast water management systems that have been granted Final Approval by the MEPC, it is the treated ballast water that is considered in this application and thus tested for efficacy, content of chemicals and toxicity. Accordingly, each testing was

undertaken with the Purimar TM effluent, using test methods that comply with Guidelines (G8) and Procedure (G9).

However, the GESAMP-BWWG's review of the other BWMS submissions, requested that data be provided on chemicals of Active Subs tance and Relevant Chemicals. TWECO has not undertaken direct toxicity testing of those chemicals. Rather, the data has been collected from existing literature, and these are presented and interpreted in sections 3.4 and 3.5 of

this annex.

2.7 Procedures and timelines

The submission of this application is in accordance with the procedures and timelines of Procedure (G9).

3 Datasets required in the application

All results presented in this section are taken from the raw data sheets contained in appendices 1, 4, and 5.

3.1 Identification of Preparation, Active Substances and Relevant Chemicals

3.1.1 Preparation

"Preparation" means any commercial formulation containing one or more Active Substances including any additives.

As outlined above, the Purimar TM System does not involve the formulation of any Preparation for carriage on board the ship for use in the BWMS. Rather, the Active Substance chlorine is generated on board as required.

Strictly speaking then, TRO is the Active Substances of relevance to the Purimar TM System. The by-products of chlorination are collectively referred to as Disinfection By-Products (DBPs), and may be considered as Relevant Chemicals.

However, as stated above, for the purposes of this application and the whole effluent testing that has been conducted to support it, "Preparation", "Active Substance" and "Relevant Chemicals", as well as "Ballast Water Discharge", all have the same meaning. This "whole effluent" approach has been adopted for other oxidant-based ballast water management systems that have been granted Final Approval by MEPC.

Nevertheless, relevant data as required by Procedure (G9) are provided below for Active

Substance and Relevant Chemicals.MEPC 61/2 Annex, page 14

I:\MEPC\61\2.doc 3.1.2 Active Substance

The general definition of "Active Substance" is a substance or organism, including a virus or a fungus that has a general or specific action on or against harmful aquatic organisms and pathogens.

The key method of the Purimar TM system for inactivating harmful aquatic organisms and pathogens is the use of direct chlorination with electrolysis of seawater. Seawater is passed through electrolytic cells (electrolyzers) which are comprised of a cathode and a CSA ®
anode. The primary cell reactions occurring in the electrochemical generation process in

seawater are as follows:

At the anode: Cl
- + Cl
- → Cl 2 + 2e - (1)

2H 2 O → 4H + + O 2 + 4e - (2)

Br - + Br - → Br 2 + 2e - (3)

At the cathode: 2H 2 O + 2e
- → H 2 + 2OH
In the seawater: Cl 2 + 2OH
- + 2Na + → NaOCl + H 2 O + NaCl

At the CSA ® anode, reaction (1) occurs mainly in seawater. However, in fresh water having a very low chloride concentration, reaction (2) may occur such that the efficiency of reaction (1) may decrease.

Moreover, the use of reaction (2) as a controllable biocide is not suitable because a clear mechanism for the electrochemical intermediate product (OH*) is not established.

Also, seawater contains 50~70 ppm of brom ide ion which forms bromine as shown in reaction (3) in a manner similar to chloride ion.

As can be seen in Figure 3.1, sodium hypochlorite (NaOCl) produced in the electrolyzer is present as chlorine (Cl 2 ), hypochlorite ion (OCl
- ) and hypochlorous acid (HOCl) depending on the pH of seawater.

Cl 2 + H 2 O ↔ HOCl + H + + Cl
-
HOCl ↔ OCl
- + H +

At the pH of seawater (typically ranges from 7.5-8.4), the solution generated by the

Purimar TM System will consist of a near equal mixt ure of hypochlorous acid and hypochlorite

ion.

Also, bromine is present as bromine (Br 2 ), hypobromous acid (HOBr) and hypobromite ion (OBr
- ) depending on the pH of seawater in a manner similar to chlorine, in which hypobromous acid (HOBr) may be produced from t he reaction of hypochlorous acid (HOCl) with bromide ion (Br-).

Br 2 + H 2 O ↔ HOBr + H + + Br -
HOBr ↔ OBr
- + H +

HOCl + Br
- → HOBr + Cl
At the pH of seawater, the solution generated by the Purimar TM System will also consist of a mixture of hypobromous acid and hypobromite ion, with a slightly greater proportion of the mixture existing as hypobromous acid.MEPC 61/2 Annex, page 15

I:\MEPC\61\2.doc Thus, at the outlet of the electrochemical generator, the seawater contains a mixture of chemicals produced at both the anode and cathode. The electrochemical process results in the formation of the actual disinfecting agents – hypochlorous acid in equilibrium with hypochlorite ion and hyprobromous acid in equ ilibrium with hypobromite ion – and hydrogen gas produced as a by-product. During the electr ochemical process a small amount of caustic (OH
- ) is also produced, which is effectively neutralized within the cell and causes no apparent increase in the pH of treated ballast water.

Further, chlorine and bromine can undergo reactions with ammonia naturally present in seawater, and may result in the formation of low concentrations of chloramines and bromines. Chloramine and bromine are import ant to discuss in disinfection chemistry because these are also considered disinfectants. However, they are less effective disinfectants (i.e. weak oxidants) and the amount of disinfection attributed to chloramine and

bromine is not considered relevant. The amount of chloramine and/or bromine potentially formed is related to the amount of ammonia present, amount of oxidant present, reaction time, and pH of the water treated. The amount of chloramine and bromine formed during use

of the Purimar TM System is expected to be insignificant because of the neutral pH at which treatment is occurring and the long reaction time required for their formation.

The common factor in all of these chemical spec ies is that they are considered oxidants, and due to the difficulty in measuring each chemical species individually in a complex water sample, the term Total Residual Oxidants (TRO) is used to include all of these oxidants when present in a sample and is referred as "Active Substance".

Therefore, in this dossier, TRO is used to describe the total of all oxidants present in water treated by the Purimar TM System. The chemical methods used for analysing TRO often state that the measurement is calculated as mg Cl 2 /L. However, these methods include all of the oxidants present in a water sample as mentioned above, not just Cl 2 . All concentrations of TRO are given as equivalent chlorine in this application dossier for reasons of better comparability.

During the preliminary and land-based test runs of the Purimar TM System, pre-filtration of the ballast water incorporated as part of the test set-up removed bigger zooplankton and showed excellent results in eliminating viable organisms present in the water before treatment at a TRO concentration of 3 mg/L TRO. The existing results of efficacy testing are presented in

section 3.2.

Actually, in the Purimar TM System, the Active Substance is generated at a concentration of less than 1,000 mg/L prior to injection into the ballast pipelines. As the biocide solution enters the ballast system, it is diluted to no more t han 10 mg/L TRO. Because the Active Substance is generated in situ , it is not stored on board the vessel except in the ballast tanks at expectable maximum concentrations <10 mg/L TRO.

3.1.3 Relevant Chemicals

According to Procedure (G9), "Relevant Ch emicals" mean transformation or reaction products that are produced during the treatment process or in the receiving environment and may be of concern to the aquatic environment and human health when discharged.

Trihalomethanes (THMs), Haloacetonitriles (HANs), Halophenols (HPhs) and Haloacetic acids (HAAs)

Disinfection of water with chlorine-based disinfectants can result in the formation of various by-products. Chlorine is very reactive towards natural organic matter, leading to the formationMEPC 61/2 Annex, page 16

I:\MEPC\61\2.doc of several by-products. While trihalomethanes (THMs) are the major compounds formed, other by-products are of concern due to their possible toxicity towards aquatic organisms: haloacetonitriles (HANs), halophenols (HPh s) and haloacetic acids (HAAs).

The type and relative amounts of the chlorination by-products vary with the organic content of the water and also with the inorganic species present. Hence, the chlorination of waters containing ammonia, bromide and organic matter, leads to competitive reactions with chlorine. Chlorine preferentially reacts with ammonia until monochloramine formation is complete. However, at high bromine concentrations and low ammonia levels, bromine may be formed before the break-point; this is often the case in marine waters. Thus, the bromine and chlorine species are therefore in competition to react with the organic matter, either as oxidizing or as substituting agents. As a consequence, brominated compounds may be

formed.

Bromate

Formation of bromate (BrO 3 - ) may occur during the electrochemical treatment process. The following equation (1) shows the reaction occurring at the electrode:

Br - + 3H 2 O → BrO 3 - + 6e - (1)

The amount of bromate formed will vary based on t he amount of bromide ion present in the incoming seawater and the overall production rate of the treatment system.

Early work by Kretzschmar and by Bray enables us to postulate the following alternative

reactions:

6Br - → 3Br 2 + 6e - (2)

2Br 2 + 2OH
- → 2HBrO + 2Br
- (3)

Br 2 + 2OH
- → BrO
- + H 2 O + Br - (4)

2HBrO + BrO
- → BrO 3 - +2HBr (5)

Which is a sequence similar to that postulated for chlorate formation although reaction (5) has a rate constant some two orders of magnitude greater than that of the analogous reaction with chlorine-containing species, and reactions (3) and (4) do not proceed as rapidly.

Other potential mechanisms for bromate ion formation include the secondary reaction of HOCl with bromide ion to form hypobromite ion, which can further react to form bromate ion:

HOCl + Br
- → HOBr + Cl
- (6)

As mentioned previously, these reactions are dependent on the concentration of available bromide ion and pH. At the concentrations of oxidant produced in the electrolytic cell, the formation of bromate ion through these secondary pathways is expected to be minimal.

Hydrogen gas

Hydrogen (H 2 ) is formed as a by-product of seawater electrolysis, as can be seen in reaction occurring at the cathode. Due to the explosive properties of hydrogen gas, allowing it to

accumulate in the ballast tanks would create an unsafe situation.

In the Purimar TM System, the hydrogen produced during the electrochlorination process is separated immediately upon exit from the elec trolytic cell using a cyclone separation deviceMEPC 61/2 Annex, page 17

I:\MEPC\61\2.doc and is not allowed to enter the ballast water piping. As the formed hydrogen is not present in treated ballast water, it is not evaluated in regards to aquatic toxicity.

The separated hydrogen gas is diluted to less than 1% hydrogen by air blowers and vented to the air outside the ship. The lower explosive limit (LEL) for hydrogen is 4% and the operating limitations of the system provide a four-fold safety factor. Therefore, hydrogen gas

in the air is not considered relevant for the assessment of human health risks.

Therefore, the system testing of the Purimar TM System evaluated treated water samples collected at different time intervals for Relevant Chemicals. The following items were

measured:

- Bromate (BrO 3 - );

- Trihalomethanes (THMs) including Trichloromethane (Chloroform), Tribromomethane (Bromoform), Chlorodibromomethane and Dichlorobromomethane;

- Haloacetic acids (HAAs) including Monochloroacetic acid, Dichloroacetic acid, Trichloroacetic acid, Monobromoacetic acid , Dibromoacetic acid, Tribromoacetic acid, Bromochloroacetic acid, Bromodichlo roacetic acid and Dibromochloroacetic acid;

- Haloacetonitriles (HANs) including Dich loroacetonitrile and Dibromoacetonitrile;

and

- Halophenols (HPhs) including Pentachlorophenol.

Tables 3.9, 3.10, 3.11, 3.12, and 3.13 (see the complete confidential dossier) present data from samples collected immediately after treatm ent (Day 0), two days after treatment (Day 2) and five days after treatment (Day 5). The samples collected on Day 2n and Day 5n were analysed after neutralization with sodium thiosulfate.

Bromate and HPhs were not detected. Two THMs (tribromomethane and chlorodibromomethane), nine HAAs (monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, dibromoacetic acid, tribromoacetic acid, bromochloroacetic acid, bromodichloroacetic acid, and dibromochloroacetic acid), and two HANs (dichloroacetonitrile, dibromoacetonitril e) were detected, at a maximum total THM concentration of 0.394 mg/L (test cycle P-4(1) on Day 5, Table 3.11), HAA concentration of 0.109 mg/L (test cycle P-3 on Day 5, Table 3.10), and HAN of 0.0517 mg/L (test cycle P-4(1) on Day 2 following neutralization, Table 3.11), respectively.

3.1.4 Other Chemical (sodium thiosulfate)

The Purimar TM System chlorinates ballast water during uptake – at the start of the voyage,

and the ballast water oxidant demand dramatica lly reduces the resultant residual oxidant level. It is therefore unlikely that there will be any residual oxidants remaining in the ship's ballast after a typical voyage of several days to weeks.

Nevertheless, the Purimar TM System applies a neutralization process upon discharge of the treated ballast water to ensure environmental acceptability. Neutralizing agents chemically reduce any free chlorine and/or hypochlorous acid to chloride ion and any free bromine and/or hypobromous acid to bromide ion. Because neuralizing agent is not an Active Substance or a Relevant Chemical, it is considered to fall under the Other Chemical category.MEPC 61/2 Annex, page 18

I:\MEPC\61\2.doc Sodium thiosulfate is used in the Purimar TM System to neutralize residual oxidants that may be present in treated ballast water discharge. Sodium thiosulfate has been used in the pulp and paper industry and is currently tried to be used as a neutralizing agent.

Compared to the single reaction of other neutralizing agents (sodium sulfite, bisulfate or metabisulfite), sodium thiosulfate has multiple reactions with chlorine or bromine species. It is also an effective means of removal for any co mbined chlorine or bromine species such as

chloramines or bromine:

Sodium sulfite: Na 2 SO 3 + HOCl → Na 2 SO 4 + HCl

Sodium bisulfite: NaHSO 3 + HOCl → NaHSO 4 + HCl

Sodium metabisulfite: Na 2 S 2 O 5 + 2HOCl + H 2 O → 2NaHSO 4 + 2HCl

Sodium thiosulfate: Na 2 S 2 O 3 + 4Cl 2 + 5H 2 O → 2NaCl + 2H 2 SO 4 + 6HCl

Na 2 S 2 O 3 + 4OCl + H 2 O → 2NaCl + 2SO 4 + 2HCl

Na 2 S 2 O 3 + 4HOCl + H 2 O → 2NaHSO 4 + 4HCl

2Na 2 S 2 O 3 + HOCl → Na 2 S 4 O 6 + NaCl + NaOH

Na 2 S 2 O 3 + 4NH 2 Cl + 5H 2 O → 2NaHSO 4 + 4NH4Cl

At the pH of seawater, theoretical dosing rate of sodium thiosulfate to remove one part of chlorine (present at mg/L concentrations) will be 1.7 - 1.8 parts by weight.

TWECO has conducted the lab-scaled test to evaluate the actual dosing rate of sodium

thiosulfate to neutralize residual TRO in the Purimar TM System. Although the level of TRO was decreased in proportion to the amount of sodium thiosulfate, theoretical dosing rate of 1.8 parts was not sufficient to neutralize TRO below 0.1 mg/L TRO. Rather, depending on water condition and initial TRO level, the required dosing rates to ensure residual TRO level below 0.1 mg/L TRO were ranged from 2.57 parts. Based on these results, 3 parts of sodium thiosulfate against residual TRO is applied as set point for the neutralizing agent of

the Purimar TM System.

During the preliminary and land-based test runs of the Purimar TM System, measurement of TRO concentrations in the discharged ballast water after addition of 3 parts of sodium thiosulfate has been conducted for different water types at various Active Substance treatment and at different holding times. TRO was detected below 0.1 mg/L even at the worst expectable condition of immediately after treatm ent of 3 mg/L TRO Active Substance, in which 9 mg/L sodium thiosulfate was added. Actually, in the Purimar TM System, a 32% aqueous solution of sodium thiosulfate is loaded aboard from a filling station, stored in holding tanks and injected into the ballast line during deballasting operations to neutralize any residual TRO. The injected amount of sodium thiosulfate is monitored and controlled to apply a small excess (<9 mg/L [3 parts against TRO of 3 mg/L TRO]) to ensure that residual TRO level is maintained below 0.1 mg/L TRO in the discharged ballast water.

The added sodium thiosulfate is approved to chem ically reduce any residual oxidants and is expected to be in the form of sulfate ion (SO 4 2- ). Seawater typically contains approximately 3 g/L (or 3,000 mg/L) of sulfate ion. Thus, the concentration of sodium thiosulfate that might be added to the discharged ballast water is negligible, and the generated sulfate ion concentration in the seawater will also be negligible. The reaction might produce some acid, which in the highly buffered ballast water will not lower the apparent pH of the treated water. Exact value experiment ing from land-based test and onboard test will be

calculated.MEPC 61/2 Annex, page 19

I:\MEPC\61\2.doc 3.2 Results of efficacy testing

3.2.1 Preliminary experiments for the system application

The preliminary operating experiments for the syst em application were performed by using the TWECO pilot-scale test set-up with the flow rate of 5m 3 /hr and the TWECO supplementary laboratory-scale apparatus at NLP R&D Centre in Ulsan and MBDC in Busan, respectively.

3.2.1.1 Laboratory-scale efficacy testing

The laboratory-scale efficacy testing was conducted at MBDC. Varying hypochlorite concentrations were applied and TRO levels were measured at different time intervals after treatment. Tables 3.2 and 3.3 (see the complete confidential dossier) below presents the results of commercial seawater sample containing 1.5 mg/L total organic carbon (TOC). Whereas a TRO concentration of 7 mg/L was needed to inactivate zooplankton ( Artemia salina) at Day 2 after treatment, 3 mg/L TRO was sufficient to inactivate phytoplankton ( Tetraselmis suecica ) immediately after treatment.

When using chlorine-based water disinfection, it is important to discuss the concept of oxidant decay and demand.

Studies on the decay of TRO produced by the TWECO laboratory-scale electrolytic apparatus have been performed, and Figure 3.4 (see the complete confidential dossier) provides example of the decay of TRO observ ed over time for varying concentrations of hypochlorite treatment. Regardless of the in itial oxidant dose, the residual oxidant concentration decay over time.

Oxidant demand is defined simply as the diff erence between the amount of oxidant added to the water and the amount of oxidant remaining at the end of a specified contact period. When an oxidant is added to natural waters, it will react (oxidize) with organisms and other components (e.g., natural minerals, organic matter) normally present in natural waters. These components, often measured as TOC, determine the oxidant demand of the water. As such, for effective treatment, an oxidant needs to be applied at a concentration that

exceeds the demand of the water source and also maintain a residual concentration within the ballast tanks. This allows for sufficient concentration and contact time to ensure complete

and effective inactivation of HAMP.

Studies on the demand/decay of TRO produced by the TWECO laboratory-scale electrolytic apparatus have been performed, and Figure 3.5 (see the complete confidential dossier) provide examples of the TRO demand/decay results of commercial seawater samples added with various amounts of glucose. The initial TRO concentration decays quickly immediately after treatment, which is proportional to the amount of added glucose, and then more slowly after the demand of the water was met. Regardless of water type, decay of TRO follows a predictable and consistent pattern.

Empirical studies over a wide range of water qualities and TOC levels have shown that an applied concentration of <10 mg/L of TRO results in effective ballast water treatment. This relationship is consistent with the results shown in Figure 3.5. Initial TRO concentration of 10 mg/L sustained a sufficient TRO level (>6 mg/L at 3 hours after treatment and >1 mg/L at 1 day after treatment) to disinfect the seawater sample containing TOC level up to 20 mg/L.MEPC 61/2 Annex, page 20

I:\MEPC\61\2.doc 3.2.1.2 Pilot-scale efficacy testing

The pilot-scale efficacy testing was conducted at NLP R&D Centre in Ulsan. TOC level of the source seawater in Ulsan was 1.08 mg/L - 2.77 mg/L. The test set-up is not simply a system for laboratory testing, but rather closely resembles a ship's ballast water system regarding filtering and neutralizing units. Pre-filtration of the ballast water incorporated as part of the test set-up removed bigger zooplankton and show ed excellent results in eliminating viable organisms present in the water before treatment at a TRO concentration of 2 mg/L – 3.5 mg/L. Results of biological efficacy testing are summarized in Tables 3.4 and 3.5 (see the complete confidential dossier).

Studies on the decay of TRO also have been performed during the preliminary operating experiments for the system application using the TWECO pilot-scale test set-up as shown in Figure 3.6. Although all TRO levels in the ballast tanks declined over time especially within 24 hours, the pattern of decay is variable depending on water condition. From time to time, changes of the water quality parameters, such as biological production rates, TOC, pH, and temperatures, may affect both the dissolution and decay rates of an oxidant.

During the pilot-scale efficacy testing of brackish water sample, tap water was added to the source seawater to adjust salinity. All the water quality parameters of the test water will be evaluated during the land-based test runs, and only those events fulfilled Guidelines (G8) requirements for the water quality will be taken into further considerations for the test cycles. In the case of brackish water treatments, am endments will be made to increase the organic and suspended solids loads.

Figure 3.6: TRO decay of TWECO pilot-scale test cycles (P1 – P4)

3.2.2 Land-based test run for the system confirmation

The efficacy testing of full Purimar TM system installed on the TWECO test barge was conducted at Busan Port (>32 PSU). The test protocol evaluated biological treatment performance based on IMO Guidelines (G8), and operational/maintenance tests and challenge water tests were accomplished for operation and maintenance, reliability, cost factors, environmental acceptability, and safety.MEPC 61/2 Annex, page 21

I:\MEPC\61\2.doc 3.2.2.1 Fulfilment of the chemical water quality criteria

All relevant environmental water parameters are summarized in Table 3.6.

Table 3.6: Chemical water quality parameter of the land-based test runs for the Purimar TM
System (F-1) (see the complete confidential dossier)

The test run fulfilled Guidelines (G8) requirem ents for the chemical water quality criteria for land-based test, and thus, have been taken into further considerations for other testing.

3.2.2.2 Fulfillment of the biological water quality criteria

Results of measurement of TRO concentra tion and biological efficacy testing are summarized in Tables 3.7 and 3.8, respectively.

Table 3.7: TRO concentration of the land-based test runs for the Purimar TM System (F-1) (see the complete confidential dossier)

Table 3.8: Biological water quality parameter of the land-based test runs for the Purimar TM
System (F-1) (see the complete confidential dossier)

The number of living organisms in the untreated and Purimar TM System-treated water samples met the D-2 regulation. TRO concentration of 3 mg/L treating ballast seawater containing 6.95 mg/L TOC effectively inactivated zooplankton, phytoplankton and bacteria. This result indicates that it is sufficient to disinfect HAMP in ballast water with only

the Purimar TM system operating in situ during ballast water uptake. Thus no other treatment mechanism is required to boost the efficacy of the Purimar TM system.

Water qualities where ballast water uptake may occur can impact the oxidant demand as it can vary by location and season. This in turn can affect the concentration of biocide solution needed to adequately inactivate HAMP. Therefore, the effective concentration generated by

the Purimar TM System to meet the oxidant demand of the incoming ballast water while also maintaining a residual concentration is adjusted based on the water quality.

In this sense, the Purimar TM System is designed to control the amount of Active Substances produced to effectively treat HAMP, yet avoid over-production of the biocide to control the level of potential DBPs. This is accomplished using TRO sensor (CLX), which allows for a

direct on-site measurement of TRO level. As TRO sensor (CLX) needs a time gap of 7.5 min for an initial reading of TRO level, ORP sensor (Jumo) is additionally adopted for an in-line rapid determination of the amount of oxidation reduction potential (ORP) of the water. The amounts of TRO and ORP are measured in mg Cl 2 /L and millivolts (mV), respectively. When biocide solution is added to water, the TRO and ORP readings increase with an increase in the concentration of biocide solution. Similarly, when a neutralizing agent such as sodium thiosulfate is added to the water, the TRO and ORP readings will drop to a low level. In this way, TRO and ORP measurements provide a practical and efficient method of controlling biocide concentration and ensure optimized water disinfection. More discussions on how the

Purimar TM System incorporates TRO and ORP technology is presented in appendix 7.

In 2010, further land-based efficacy testing of the Purimar TM System will be conducted according to IMO Guidelines (G8) at two different sites with significant difference in water qualities – seawater test in Busan Port (>32 PSU) and brackish water test in Nakdong River or similar estuary (3~32 PSU). Shipboard testing of a commercial Purimar TM System will also

be executed in 2010.MEPC 61/2 Annex, page 22

I:\MEPC\61\2.doc 3.3 Results of chemical analysis (Relevant Chemicals)

During the system testing using the TWECO pilot-scale test set-up and the full-scale

Purimar TM system, measurements of the concentra tions of Relevant Chemicals were performed by SGS. A water sample was taken from each sampling point, poured into pre-labelled sample containers, which included the required preservative for each parameter, and transported to the laboratory of SGS.

The results are summarized in Tables 3.9, 3.10, 3.11, 3.12, and 3.13 (detailed in the complete confidential dossier), and the individual test reports including raw data sheets are contained in appendix 5. Data were obtained from the water samples collected immediately after treatment (Day 0), two days after treatm ent (Day 2) and five days after treatment (Day 5). The samples collected on Day 2n and Day 5n were analysed after neutralization

with sodium thiosulfate.

The results, as presented in the above-mentioned tables, indicate that bromate was always below the MDL in all samples. Considering the relatively high MDL of SGS, the same water samples were requested to Korea Testing and Research Institute (KTR) for the measurement of bromate. Even the finding of MDL of KTR was as low as 0.1 μ g/L, bromate was not detected in all water samples (appendix 5).

From the other tested compounds, two THMs (tribromomethane and chloro-dibromomethane), all nine HAAs (monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, dibromoacetic acid, tribromoacetic acid, bromochloroacetic acid, bromodichloroacetic acid and dibromochloroacetic acid), and two HANs (dichloroacetonitrile and dibromoacetonitrile) were detected.

The maximum concentrations of total THM, HAA, and HAN, which have been detected in treated ballast water during the development of Purimar TM System, were 0.394 mg/L (test cycle P-4(1) on Day 5, Table 3.11), 0.109 mg/L (test cycle P-3 on Day 5, Table 3.10), and 0.0517 mg/L (test cycle P-4(1) on Day 2 following neutralization, Table 3.11), respectively. The detected highest concentration of each Relevant Chemical is summarized in Table 3.14 (see the complete confidential dossier).

The data show high levels of brominated by-products, particularly tribromomethane, in treated water. In oxidation reactions with hypobr omous acid, the bromide ion is formed; so, in excess of chlorine, this ion is rapidly rec onverted to hypobromous acid. Thus, while chlorine is consumed, the bromine concentration remains constant upon oxidation reactions. Consequently, the loss of bromine may be mainly attributed to substitution reactions as long as chlorine is present in the water. For that reason, the production of brominated by-products upon chlorination is greatly enhanced with increased bromide concentrations in the water samples; on the contrary, increasing the free available chlorine results in a reduction in bromine incorporation.

For the brackish water test run, there is an additional factor likely contributing to the levels of brominated organic by-products observed. To r each the desired brackish water salinity, natural seawater was diluted with tap water from a municipal water source (such as test cycle P-3). This water had been previously chlorinated using chlorine gas. The researchers aerated the water to remove pre-existing chlorine; however, at the pH level of the test water most of the residual chlorine presented in the tap water would exist as HOCl/OCl
- and some

HOBr/OBr
- if the chlorine had a small bromine impurity. Therefore, use of local chlorinated tap water may potentially affect the level of hypochlorite ion in treated water and may also be

a source of bromine.MEPC 61/2 Annex, page 23

I:\MEPC\61\2.doc Further analysis of DBPs will be conducted during land-based test runs for the land-based testing of the Purimar TM System in 2010. In the case of the brackish and fresh water test runs, amendments will be made to increase the organic matter and suspended solids loads. Their addition to test waters appears to have unintentionally changed the production of DBPs. Therefore, due to the addition of amendments, the potential presence of bromine present in the chlorine source prior to treatment, along with the presence of pre-existing disinfection by-products, it can be reasonably deduced that these factors influence the levels of brominated by-products in the fresh water and brackish water studies.

3.4 Data on effects on aquatic plants, invertebrates and fish, and other Biota, including sensitive and representative organisms

WET testing of water treated with the Purimar TM System has been conducted by MBDC. All WET data disclosed were obtained at the preliminary and land-based test runs that meet ballast water performance standards concerning biological efficiency. For every Active Substance and Relevant Chemical, data are presented and discussed either on the basis of toxicological tests (whole effluent water) or existing toxicological knowledge for separate

Active Substances and Relevant Chemicals.

3.4.1 Whole Effluent Toxicity (WET) test for the evaluation of acute and chronic aquatic toxicity

All WET tests followed short-term methods deemed qualitatively equivalent to OECD and ASTM for estimating acute and chronic aquatic toxicity. Samples were collected from challenge tests in which organism and organic-enriched ballast water was treated with hypochlorite to a TRO concentration to disinfect sufficiently. These tests were done in conjunction with evaluation of efficacy and DBPs.

MBDC evaluated treated water collected at differing time intervals after treatment and after neutralization with sodium thiosulfate using algae, invertebrates, and fish in saltwater. Water samples were collected immediately after treatm ent with hypochlorite (Day 0), two days after hypochlorite treatment, and five days after hypochlorite treatment. These samples were collected and tested prior to the neutralization step (i.e. pre-neutralization). For toxicity testing post-neutralization, samples were collected from challenge tests in which hypochlorite treated water was held for two days or five days and then neutralized with an excess

concentration of sodium thiosulfate.

Immediately after verification of field water samples, the water samples were passed through the filtering system (pore size 0.45 μ m) and measured the TRO, pH, temperature, salinity, and dissolved oxygen (DO). Test substances prepared from the treated water samples were subjected to the concentration-response tests – control dilution water (0%) and a minimum of three concentrations commonly selected to approximate a geometric series, i.e. 100%, 75%, 50%, 25% and 12.5%. With respect to the formulation of the dosing preparation, commercial natural seawater was used as a diluent. As the test substances prepared from the untreated ballast water samples are likely to be non-toxic, the single concentration (undiluted, 100% solution) was subjected to the limit test.

All WET tests were initiated simultaneously within 6 hours of sampling. For chronic toxicity test with larval fish, single treated water samples stored in locked refrigerator (stored sample) or daily treated water samples (fresh sample) were used for the renewal of test substances.MEPC 61/2 Annex, page 24

I:\MEPC\61\2.doc 3.4.1.1 Water quality parameters in WET test substances

All the water quality parameters satisfied the criteria for the validity of WET test. The results are summarized in Table 3.15. (See the complete confidential dossier.)

3.4.1.2 TRO in WET test substances

As soon as the test substances for WET tests were prepared and diluted, the concentration of Active Substance was measured shortly prior to the beginning of the WET test. Results are summarized in Table 3.16 (see the complete confidential dossier). The TRO level after filtration was dramatically reduced comparing to that on delivery (at laboratory TRO concentration in Tables 3.4 and 3.7). This result suggests that chlorination-produced oxidants may dissipate very quickly from sa mples that are exposed to sunlight and atmosphere and bubbled with ambient air. Therefore, investigators should consider the implications of the loss of oxidants during sampling process and test substance preparation for WET testing in estimating overall or residual toxicity of Active Substance in chlorinated seawater. In this sense, TWECO has opted to include a TRO neutralizer as standard in the PurimarTM System design to address any possibility of residual TRO of concern in the treated ballast water discharge.

Results of WET tests

The WET test results are presented in the following sections, and the individual test reports including raw data sheets are contained in appendix 4.

Growth inhibition test with marine algae

Ninety-six hour growth inhibition test with marine algae, Phaeodactylum tricornutum and

Dunaliella tertiolecta was performed on the Purimar TM System. Table 3.17 summarizes the results. (See the complete confidential dossier.)

Acute toxicity (survival) test with invertebrates

Twenty-four hour survival test with marine invertebrates, Brachionus plicatilis was performed

on the Purimar TM System. Table 3.18 summarizes the results. (See the complete confidential dossier.)

Acute toxicity (survival) test with larval fish

Sheepshead minnow, Cyprinodon variegatus , larvae (preferably less than 24 hours old) exposed in a static non-renewal system for 96 hrs was performed on the Purimar TM System. Table 3.19 summarizes the results (see the complete confidential dossier).

Chronic toxicity (reproduction or population growth) test with invertebrates

Four-day reproduction (population growth) test with marine rotifer, Brachionus plicatilis was performed on the Purimar TM System. Table 3.20 summarizes the results. (See the complete confidential dossier.)

Chronic toxicity (growth) test with larval fish

Sheepshead minnow, Cyprinodon variegatus , larvae (preferably less than 24 hours old) exposed in a static renewal system for 7 days was performed on the Purimar TM System. Table 3.21 summarizes the results. (See the complete confidential dossier.)MEPC 61/2 Annex, page 25

I:\MEPC\61\2.doc As would be expected, the untreated samples (C0, C2, and C5) exhibited no minimal toxicity in any of the tests. The median lethal concentrations (LC 50 ) were greater than 100% solution, meaning that the untreated seawater showed no toxicity.

For the treated samples, in summary, all test substances prepared from water samples immediately after treatment (T0) and most test substances prepared from water samples two days after treatment (T2) showed residual toxicity. Although the results of WET tests indicate that the latent toxicity is not expected in the discharged ballast water after five days storage (T5), data of TRO concentrations at field from the same test run cycles of

the Purimar TM System (see Table 3.4 and 3.7) suggest that some chlorination-produced oxidants responsible for marine organism mortality may persist at toxic concentrations in the ballast waters two to five days follow ing treatment depending on storage conditions and exposure to sunlight.

Risk-based decisions need to be made to set maximum acceptable discharge concentrations and conditions (potentially taking into account discharge rates and dilution or degradation following discharge into receiving waters). As has been applied for other electrolysis-based Ballast Water Management Systems that has been granted IMO Approval by MEPC, it is therefore, the TRO of 0.1 mg/L that is considered in this application. Chemical treatments, such as with sodium thiosulfate, may provide a fast and effective means of reducing residual TRO concentrations without the risk of endangering organisms in the vicinity of the vessel undergoing chlorination.

Actually, no residual toxicity was observed for all test species in the sodium thiosulfate-treated (post-neutralized) water samples of Day 2 (T2n) and Day 5 (T5n) regardless of pre-neutralized TRO concentrations. Furthermore, MBDC additionally performed repeated-dosing chronic toxicity test with larval fish using post-neutralized water samples for the daily renewal of test substances. Water samples were prepared by diluting the biocide solution generated from the TWECO laboratory-scale electrolytic apparatus with commercial seawater to a 1 mg/L of TRO, and then neutralizing with a 2.36 mg/L of sodium thiosulfate. Seven repeated dosing of freshly prepared water samples showed no toxicity (see Table 3.21), which suggests that sodium thiosulate up to 16.52 mg/L would not be expected to exhibit an adverse e ffect against aquatic organisms.

In conclusion, evaluating toxicity to aquatic organisms at various holding times after treatment (without neutralization) demonstrates that the residual chlorine remains effective after treatment. Additionally, performing toxicity testing with post-neutralization verifies that the sodium thiosulfate treatment is effectively removing residual oxidants, making treated water discharge environmentally safe and that the neutralizing agent is not itself toxic.

3.4.2 Acute and chronic aquatic toxicity of active substance, other chemical and

relevant chemicals

A literature search was conducted to locate existing aquatic toxicity data for the substances

associated with the Purimar TM System. The data summarized in Tables 3.22 and 3.23. (See the complete confidential dossier.)

3.4.3 Endocrine disruption

Endocrine disrupting chemicals (EDCs) is a compound, either natural or synthetic, which environmental or inappropriate development ex posures alters the hormonal and homeostatic systems that enable the organism to communi cate with and respond to its environment.MEPC 61/2 Annex, page 26

I:\MEPC\61\2.doc There are no indications, e.g., from the structure of the substance or results of other available studies that any of Active Subst ance (TRO; HOCl/HOBr) or Relevant Chemicals causes endocrine disruption. Active Subst ances and Relevant Chemicals that were mentioned above were not found in any literature.

3.4.4 Sediment toxicity

The sediment toxicity of a chemical is a function of the ability of the chemical to be adsorbed to sediment as well as its persistence and toxicity. The organic carbon partition coefficient (Koc) is the chemical adsorption coefficient normalized to the organic carbon content of soil or sediment. This parameter can provide insight as to whether a material will cling to soils or sediments in water and whether they will desorb or be tightly bound. The octanol/water partition coefficient (Kow) is defined as the ratio of a chemical’s concentration in the octanol phase to its concentration in the aqueous phase of a two-phase octanol/water system. Measured values of Log Kow for organic chemicals range from -4.53 to 2.4. Generally, chemicals with low Log Kow values can be considered relatively hydrophilic (i.e. tendency for high water solubility, low potential for sedim ent adsorption), while chemicals with high Log Kow values are considered hydrophobic (i.e. low water solubility, high potential for sediment adsorption).

Active Substances and Relevant Chemicals have been assessed for persistence in natural waters and concerning accumulation potential in sediments. The literature reported and/or estimated log Kows and Kocs are shown for the Active Substances and Relevant Chemicals in Table 3.24 (see the complete confidential dossier).

The TRO Active Substances are all inorganic substances and therefore have a very low calculated Koc. None of the organic Relevant Chemicals appear to have the potential to be absorbed to sediments to a significant extent based on their low Kocs (<500 L/kg) and other information in the literature (HSDB/TOXNET). With the exception of the THMs, all of the Active Substances and Relevant Chemicals have very low log Kow’s, which indicates the compounds are hydrophilic. The THMs, as woul d be expected, are moderately hydrophobic. However, none of the log Kow values located in the literature and/or estimated is ≥ 3.

Thus, the low Kocs and log Kow values for all of the Active Substances and Relevant

Chemicals indicate that the chemicals would not readily partition and accumulate to sediment and therefore, be of concern to benthic organisms residing in the sediment. (See the complete confidential dossier.)

3.4.5 Bioavailability/biomagnification/bioconcentration

The bioconcentration factor (BCF) is the concentration of a particular chemical in/on fish or specified tissues thereof divided by the concentration of the chemical in the surrounding medium at steady state. The bioconcentration factors (BCFs) are used to relate pollutant residues in aquatic organisms to the pollut ant concentration in ambient waters (reported as L/kg). This physical property is used as the indicator of a chemical potential to bioaccumulate and especially characterizes the accumulation of pollutants through chemical partitioning from the aqueous phase into an organic phase, such as fish or other aquatic organism tissues. The BCF is the best measure of bioavailability, biomagnification, and bioconcentration. Generally, a high potential BCF is greater than 1000, a moderate potential BCF is less than a 1000 but greater than 250, and a low potential BCF is less than 250. When the BCF of specific chemical is more than 1000, the chemical is considered bioaccumulative. The BCFs summarized in Table 3.24 are all much lower indicating a lowMEPC 61/2 Annex, page 27

I:\MEPC\61\2.doc potential for significant bioconcentration/bioaccumulation in aquatic organisms (HSDB/TOXNET). Little biomagnification should occur in the food web since the chemicals are not readily bioconcentrated or bioaccumulated.

3.4.6 Food web/population effects

In case of that properties of the substances have the tendency of bioaccumulation and/or persistence in the environment, food web and population effects will occur.

Little biomagnification and persistence in aquatic and mammalian food webs is anticipated

from the Active Substances or Relevant Chem icals. This conclusion is based on the results from aquatic toxicity testing, low PEC values, mammalian toxicity evaluation and low Kocs

and BCFs of the Active Substances and Relevant Chemicals.

3.5 Data on mammalian toxicity

Mammalian toxicity studies have not been perfo rmed separately for Active Substances or Relevant Chemicals formed during or after application of the Purimar TM System. Testing with vertebrate animals should be avoided if other types of information are available that allow an

assessment of hazards and risks to humans.

Tables 3.25 to 3.30 (see the complete confidential dossier) show data on mammalian toxicity for different endpoints and effects. The data in tables are referred from the government reports such as WHO, IPCS and USEPA and so on. Some data was also referred from Material Safety Data Sheets (MSDS).

Potential for human exposure to the substances associated with the Purimar TM System is discussed in detail in appendix 8.

3.6 Data on environmental fate and effect under aerobic and anaerobic condition

3.6.1 Modes of degradation (Biotic; Abiotic)

The Active Substances (hypochlorous acid and hypobromous acid) decay in seconds to hour as shown in key data summary (appendix 1); This shows how to produce an oxidizing environment and Active Substances action mechanism. DBPs are generated with the presence of organic matter by the action mechanism of the Active Substances. The generated DBPs are described in section 3.1.3 and the degradation data of biotic and abiotic of DBPs are shown in key data summary (appendix 1). The degradation of biotic for all of these simple halogenated organic compounds is on the order of days to weeks. The degradation of abiotic of these compounds is longer than biotic.

3.6.2 Bioaccumulation, partition coefficient, octanol/water partition coefficient

The bioconcentration factor (BCF) is the concentration of a particular chemical in/on fish or specified tissues thereof divided by the concentration of the chemical in the surrounding medium at steady state. The bioconcentration factor (BCF) is used to relate pollutant residues in aquatic organisms to the pollut ant concentration in ambient waters (reported as L/kg). This physical property characterizes the accumulation of pollutants through chemical partitioning from the aqueous phase into an organic phase, such as the gill of a fish. Generally, a high potential BCF is greater than 1000, a moderate potential BCF is less than a 1000 but greater than 250, and a low potential BCF is less than 250. The literature reported and/or estimated BCFs are shown for the Active Substances and Relevant Chemicals in Table 3.24 (see the complete confidential dossier).MEPC 61/2 Annex, page 28

I:\MEPC\61\2.doc The organic carbon partition coefficient (Koc) is the ratio of the mass of chemical that is adsorbed in the soil per unit mass of organic carbon in the soil or sediment per equilibrium chemical concentration in solution. Koc values are useful in predicting the mobility of organic contaminants in soil or sediment; high Koc values correlate to less mobile organic chemicals while lower Koc values correlate to more mobile organic chemicals. The octanol/water partition coefficient (Kow) is defined as the ratio of a chemical’s concentration in the octanol phase to its concentration in the aqueous phase of a two-phase octanol/water system. Measured values of log Kow for organic chemicals range from -4.53 to 2.4. Generally, chemicals with low Log Kow values can be considered relatively hydrophilic (i.e. tendency for high water solubility, low potential for sediment adsorption), while chemicals with high Log Kow values are considered hydrophobic (i.e. low water solubility, high potential for sediment adsorption). The literature reported and/or estimated Log Kows are shown for

the Active Substances and Relevant Chemicals in Table 3.24.

Based on the BCFs data shown in Table 3.24 for both Active Substances and Relevant Chemicals all of these substances have less than 250 of BCFs, indicating that there is no bioaccumulation in aquatic organisms or present a significant food chain risk. With the exception of the THMs, all of the Active Substances and Relevant Chemicals have very low log Kow’s, which indicates the compounds are hydrophilic. The THMs, as would be expected, are moderately hydrophobic. However, none of the log Kow values located in the

literature and/or estimated is ≥ 3. The log Kow and BCF are related to each other with the BCF being the more relevant parameter to determine the likelihood of impacts of a chemical to aquatic organisms. The Kocs for all chemicals in Table 3.24 show that all of chemicals are expected to have high mobility and if released water, all of chemicals are not expected to absorb to suspended solids and sediment in water.

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

Higher tier simulation tests not required; this section is not applicable.

3.6.4 Reaction with organic matter

The formation of DBPs in electrolysis system which generates chlorine is well known. Bromated and four major classes of DBPs such as THMs, HAAs, HANs, and HPhs have

been measured in treated ballast water with the Purimar TM System.

DBP formation is a result of disinfectant reactions with natural organic matter, often measured as TOC, which serves as the organic pr ecursor, and/or bromide ion, which serves as the inorganic precursor. Reactions between disinfectant halogens (e.g., chlorine and bromine) and DBP precursors include substitution reactions and carbon bond oxidation reactions. Water quality (e.g., pH, temperature, bromide level, TOC) and treatment conditions (e.g., hypochlorite dose, contact time, removal of organic matter prior to treatment) influences the formation of DBPs.

Analysis for DBP concentrations has been conducted during system testing of the Purimar TM
System. Different water types (brackish and seawater) were treated and then evaluated for DBPs. The data are presented in section 3.3 "Result of chemical analysis (Relevant Chemicals)". Additional analysis of DBP concentrations in treated ballast water will be performed during land-based testing for Final Approval and the results will be reported in the Final Approval dossier.MEPC 61/2 Annex, page 29

I:\MEPC\61\2.doc 3.6.5 Potential physical effects on wildlife and benthic habitats

As shown in Tables 3.31 and 3.32, the chemical and physical properties of the Active Substances and Relevant Chemicals generated from the PurimarTM System do not have physical effects on wildlife and benthic habitats.

3.6.6 Potential residues in seafood

Chemicals detected in treated ballast water that is discharged may affect seafood consumers only if they tend to bioaccumulate (within a trophic level, an increase in concentration of a substance in tissues due to uptake from food and sediments) or biomagnify (an increase in the concentration of a substance in the food web) in seafood.

The bioaccumulation criteria per the Methodology for information gathering and the conduct of work of the GESAMP-BWWG (MEPC 58/2/7, annex 4) include an octanol-water partition coefficient (Log Kow) of ≥ 3 or a bioconcentration factor (BCF) >2000. The chemicals identified in this risk assessment all have Log Kows less than 3 and BCFs less than 2000, and are therefore not expected to persist in the food web.

3.6.7 Any known interactive effects

No other interactive effects are known.

3.7 Physical and chemical properties

The physical and chemical properties for the Active Substances, Relevant Chemicals and Other Chemical are briefly shown in Table 3.31 (see the detailed data in the confidential dossier and appendix 1 "Key data").

3.8 Analytical methods at environmentally-relevant concentrations

Please refer to section 2.5 "Test methods". Full details are contained in appendix 3 "QAPP" (see the complete confidential dossier).

4 USE OF THE ACTIVE SUBSTANCE OR THE RELEVANT CHEMICAL

The Purimar TM System is designed to require minimal input from the ship's crew, with the system starting and stopping the necessary tr eatment steps based on electronic signals. This minimizes added duties to ship’s crew and ensures proper ballast water treatment. Please refer to section 4 "General description of the Purimar TM System" (see the complete confidential dossier), section 3.1 "Identification of Preparation, Active Substance and Relevant Chemical", and section 3.2 "Results of efficacy testing". Full details of operation

for Purimar TM System are contained in appendix 7 "Purimar TM BWMS Manual" (see the complete confidential dossier).

5 MATERIAL SAFETY DATA SHEETS

In this section, the hazard classifications are presented for reflecting report hazards only, but actual potential hazards related to the Purimar TM System are not considered. The Purimar TM
System will mitigate the potential hazards with the proper safety mechanisms and practices. Hazard classification of Active Substance, Other Chemical and Relevant Chemicals described below is based on MSDS of commercially available products that contain referenced chemicals at significantly greater concentrations that were produced by the PurimarTM System or could be found in the treated ballast water.MEPC 61/2 Annex, page 30

I:\MEPC\61\2.doc Material Data Safety Sheet (MSDS) and/or In ternational Chemical Safety Card (ICSC) information is provided in appendix 6 (see the complete confidential dossier).

5.1 Hazard classification of Active Substance

Hypochlorous acid to be known as bleach will be generated at a concentration of 1,000 mg/L before injected into the ballast water. But after injected, the concentration will be approximately 10 mg/L in the ballast water.

MSDS is not available for the chemical composition to be generated inside the PurimarTM System. ICSC #0482 (<10% solution) has been used for hazard classification instead of

MSDS:

- R-Phrases: R31, R36/38 / S-Phrases: S1/2, S28, S45, S50, S61

Normally, sodium hypochlorite is generated and used during the PurimarTM System is only running and after stopping the system; it is not stored on board. The only storage of sodium hypochlorite on board the vessel is in the ballast tanks at a concentration of < 10 mg/L.

5.2 Hazard classification of Relevant Chemicals

5.2.1 DBPs

THMs, HAAs, HANs, HPhs and bromate disinfection by-products (DBPs) may be generated at varying low-level concentrations in ballast water during the Purimar TM treatment process.

Concentrated solutions of these substances will never be transported or utilized on board ship and exposed to human. As such, typical MSDSs for these low-level substances (parts per billion range) do not accurately represent the potential hazards that may be presented by these chemicals in treated ballast water. Determining the hazards for these substances at part per billion levels is not feasible when the MSDSs reflect hazards for much higher concentrations. As such, the R-phrases and S-phrases are not detailed for these disinfection by-products; however, the MSDSs are included in appendix 6 (see the complete confidential dossier).

5.2.2 Hydrogen gas

During electrochemical process, the Purimar TM System generates hydrogen gas as a by-product. As discussed in section 3.1.3, hydrogen is separated immediately upon exit from the electrolytic cell using a cyclone separation device and is not allowed to enter the ballast water piping. Hydrogen gas transmitted to the de-gas tank is diluted with the air supplied by air blower. The concentration of diluted hydrogen gas is less than 1% (well below the 4% Lower Explosive Limit) before reaching the air. Furthermore, non-compressed hydrogen is not considered a hazardous material; however, hazard classifications according to

ICSC #0001 are as follows:

- R-Phrases: R12 / S-Phrases: S2, S9, S16, S33 / F+ symbol

5.3 Hazard classification of Other Chemical

Sodium thiosulfate 32% solution is added to hypochlorite treated ballast water as it is being discharged from the ship. This is the only substance stored on board. The quantity stored will vary depending on the amount of ballast water treated and will be specific to eachMEPC 61/2 Annex, page 31

I:\MEPC\61\2.doc installation. Sodium thiosulfate is stored in vented SST(stainless steel) or PE(polyethylene) or FRP(fibre reinforced plastic) tanks. Hazards according to the MSDS are as follows:

- R-Phrases: R20, R22, R36, R37, R38 / S-Phrases: S26, S36

6 RISK CHARACTERIZATION

6.1 Screening for Persistence, Bioaccumulation and Toxicity

Persistence

According to the data from mode of degradation (biotic/abiotic) and an evaluation of the environmental persistence data for Active S ubstances, Relevant Chemicals, and Other Chemical, there was no significant residual which met the criteria of PBT (Persistence Half-life > 60 days in marine water, or > 40 days in fresh water, or > 180 days in marine sediment, or > 120 days in fresh water sediment).

Bioaccumulation

Using the PBT criteria of either BCF > 2000 or Log Kow ≥ 3, the data for Active substances, Relevant Chemicals, and Other Chemical show that the substances have low potential for

bioaccumulation.

Toxicity tests

According to the data on effects on aquatic plants, invertebrates and fish, and other biota, including sensitive and representative organisms, there was no significant residual, which met the criteria of PBT (Chronic NOEC < 0.01 mg/L). As the chronic aquatic toxicity data was not located for all substances, the lowest acute toxicity data points available were

considered.

6.2 Evaluation of the treated ballast water

The Purimar TM System uses chlorination in the ballast water treatment process. Because of

the concern that toxic materials could be introduced into ballast waters as a result of chlorination, numerous studies have been conducted on the Purimar TM System to evaluate many aspects of treated water. In addition to the aquatic toxicity data, data on TRO, water quality parameters and DBPs have been measured and recorded.

It is conclusive to say that the latent toxicity is not expected in the final discharged ballast

water of Purimar TM System in more than two days of storage. Please refer to section 3 of Part B "Datasets required in the applic ation (the confidential dossier)".

Determination of holding time

The PurimarTM System has the neutralization unit using sodium thiosulfate and this unit will be operated to neutralize all residual oxidants at discharge. And also the concentration to be used will be properly controlled through using CLX and ORP sensor. So there is no specified holding time for the treated water to discharge safely to the environment.

For the treated water before discharging and the treated water to be mixed neutralizing agent, sodium thiosulfate, at discharging, aquatic toxicity testing is performed. In the result, there is no adverse effect. And also the result of the repeated dosing toxicity testing using excessive treatment of neutralizing agent shows that there is no adverse effect.MEPC 61/2 Annex, page 32

I:\MEPC\61\2.doc Therefore, the holding time that treated ballast water needs to be retained is determined by the amount of contact time required to properly disinfect and inactivate HAPM. Efficacy testing determined that, at low TOC concentrations, a TRO concentration of 7 mg/L was needed to inactivate zooplankton ( Artemia salina ) at Day 2 after treatment, and 3 mg/L TRO was sufficient to inactivate phytoplankton ( Tetraselmis suecica ) immediately after treatment. Actually the pilot and full-scale efficacy testing showed that pre-filtration of the ballast water incorporated as part of the Purimar TM System removed bigger zooplankton, and TRO concentration of 3 mg/L was sufficient to inactivate HAMP present in the water before treatment. Furthermore, at high TOC concentrations, initial TRO concentration of 10 mg/L sustained a sufficient TRO level (>6 mg/L at 3 hours after treatment and >1 mg/L at 1day after treatment) to disinfect the seawater sample containing TOC level up to 20 mg/L. Empirical studies over a wide range of water qualities and TOC levels have shown that an applied concentration of <10 mg/L of TRO results in effective ballast water treatment.

Consequently, the PurimarTM System treats ballast water and even though the treated water is discharged after short time storage, the numbe r of live organisms is very limited. And also there is no aquatic toxicity due to using the neutralization unit.

6.3 Risk characterization and analysis

6.3.1 Reaction with organic matter

As discussed in section 5.3.1, DBPs are generated in disinfection system using chlorine and DBPs concentration normally depends on the Active Substance dose and the parameter of the treated water such as temperature, pH, TOC. Specially, TOC among the parameter of the water affects the concentration of DBPs. So, DBPs will be generated small quantity in low TOC level. The PurimarTM System has the filter unit and this unit will pre-treat the ballast water. Therefore, the filter unit will reduce an amount of TOC and also reduce the amount of the generated DBPs during disinfection.

In section 3.3, the levels of DBPs of the treated ballast water are shown at various doses of Active Substance in different water types and water quality condition.

The concentrations of DBPs in treated water discharge will be monitored further during land-based testing. Results of this testing will be reported in the future dossier for Final Approval.

6.3.2 Characterization of degradation route and rate

For all substances related to the use of the Purimar TM System, both the biotic and abiotic degradation data are shown in key data summary (appendix 1). For DBPs, biotic degradation for all of these simple halogenated organic compounds is on the order of days to weeks. Abiotic degradation of these compounds is longer. In the case of sodium thiosulfate, no specific degradation information was located in the existing literatures. However, for these inorganic substances, the BCF, Koc, and Log Kow values indicate low potential for bioaccumulation, low adsorption to sediment, and high water solubility.

6.3.3 Prediction of discharge and environmental concentrations

Due to the oxidant neutralization step during ballast water discharge, the TRO in treated water discharge of the Purimar TM System will be below 0.1 mg/L which is risk-based maximum acceptable discharge concentration. Sodium thiosulfate added to ballast water discharge is reduced to sulfate ion in the marine environment, and sulfate ion is ubiquitous and does not pose unacceptable environmental risks. And it is important to note that acuteMEPC 61/2 Annex, page 33

I:\MEPC\61\2.doc and chronic toxicity testing of the neutralized whole effluent from the Purimar TM System was not toxic to aquatic organisms, regardless of the Relevant Chemical discharge concentrations which were detected during the system testing. Therefore Prediction of discharge and Environmental Concentrations (PEC) may not be relevant.

Nonetheless, TWECO derived meaningful PEC values for Active Substances, Other Chemicals, and detected stable Relevant Chem icals, reflecting actual environmental

concentrations when treated ballast water was released in a harbour where dilution and mixing would occur. A suitable environmental emission scenario was developed by using

the MAMPEC model.

Busan port was chosen because of the detailed statistics available via:

- Shipping & Port-Internet Data Centre (SP-IDC) http://www.spidc.go.kr/jsp/index.jsp ;

- Busan Port Authority (BPA) http://www.busanpa.com ;

- National Fisheries Research & Development Institute (NFRDI) http://www.nfrdi.re.kr ; and

- Marine Charts.

Environment definition for MAMPEC Model

As the Busan port is directly connected with an open sea, Default Marina type was used as prototype for the MAMPEC model. The land area included in the simulation was excluded from total volume. Environment definition using these data is summarized in Table 6.1 (see the complete confidential dossier).

Compound definition for MAMPEC Model

Parameters for compound definition derived from dataset of Active Substance, Other Chemical, and Relevant Chemicals are summarized in Table 6.2. (See the complete confidential dossier).

Emission definition for MAMPEC Model

The estimated amount of discharged ballast water and the resulting emission definition are provided in Tables 6.3 and 6.4, respectively (s ee the complete confidential dossier). Given that the discharged ballast water is generally applied to 30% of G/T (Case 1) and throughout (Case 2), the average total release of ballast water is 280,794 m 3 /day and 93,399 m 3 /day, respectively. This is believed to be a conservative estimate as it is unlikely that all ships will

have ballast water that is treated with the Purimar TM System, and not all the ships will discharge ballast water. Rather the opposite is the case as ships unloading cargo will take on ballast water to compensate for the cargo taken on board.

Results of MAMPEC Model

PECs of Active Substance, Other Chemical , and Relevant Chemicals calculated from

MAMPEC are summarized in Tables 6.5 and 6.6 (see the complete confidential dossier).MEPC 61/2 Annex, page 34

I:\MEPC\61\2.doc 6.3.4 Assessment of potential for bioaccumulation

Seafood such as shellfish and fish can be harvested from areas where treated ballast water is discharged. According to the data from bioaccumulation, partition coefficient, and octanol/water partition coefficient, there was no significant residuals which met the criteria of PBT (Bioaccumulation BCF > 2,000 or LogPoctanol/water [log Kow] ≥ 3).

As the BCF and log Kow values of the Active Substance, Other Chemical, and Relevant Chemicals in the discharged effluent of the Purimar TM System are very low, secondary poisoning through the food chain is unlikely to occur, and these compounds will not be found in seafood. As a result, the potential for bioaccumulation is not considered necessary to be assessed in marine or freshwater organisms, and there is no health risk connected to consumption of seafood taken from areas where ballast water is discharged.

In addition, an assessment of effects to sediment species is not considered necessary to be conducted since all the chemicals of concern to partition into the sediment is low (e.g., Koc < 500 L/kg).

6.3.5 Effects assessment

Chlorination-related toxicity tests have been conducted for several marine taxa, including primary producers (microalgae), consumers (z ooplankton or amphipod) and predators (fish). Unfortunately, the wide range of exposure conditions and test endpoints used among all of the marine toxicity tests makes it difficult to quantify a general effect concentration for chlorination. Furthermore, analytical measurements taken in most tests were not specific to chlorination. As described in section 3.1, the most Active Substance toxic against marine organisms exposed to chlorination is oxidants. Chlorination-related toxicity is thus most correctly expressed as a function of chlorination-produced oxidants, rather than chlorination

per se

.

The study to determine the ability of chlorinati on to reduce the numbers of a spectrum of marine organisms and to estimate the minimum chlorination concentrations as measured by TRO revealed that chlorination was effective in removing bacteria, phytoplankton, and mesozooplankton with initial TRO concentrations of 3 mg/L. Persistence of TRO resulted in an extended period of toxicity and cumulative mortality.

As shown in section 3.2, the initial field TRO level of ballast water treated with Purimar TM
System was satisfied with this condition.

Various reports confirm that TRO can induce rapid mortality to marine organisms, but comparisons of specific effect concentrations are complicated by the variety of exposure times and oxidant measurement methods used in each study. A recent study was reported

that LC 50 values of the most sensitive organism tested, juvenile topsmelt was 0.38 mg/L TRO, and juvenile sheepshead minnows were nearly as sensitive (0.35 mg/L TRO). The study sought to evaluate the effects of exposing Rotifer, Brachionus plicatilis to residual

oxidants in seawater indicated that survival of the rotifers was affected significantly only when TRO values were higher than 0.22 mg/L, which would be considered the no observable effect concentration (NOEC). In our all WET tests, similar results were observed.

As shown in section 3.2, the TRO level measured at field showed an initial increase and subsequent decrease in concentration presumably due to back reactions as the reaction time

increased. Chlorine and bromine residual woul d likely be maintained or degrade slowly in chlorinated ballast waters for a limited time period and would continue to have a biocidal effect if chlorinated waters remain in dark ballast tanks. However, the results of WET test ofMEPC 61/2 Annex, page 35

I:\MEPC\61\2.doc neutralized ballast water discharge against aquatic organisms, being primary producers, consumers and predators showed that even the full strength effluent of the Purimar TM System did not have any deleterious effects on any of the test species (NOEC values of ≥ 100% discharged ballast water containing TRO concentration lower than 0.1 mg/L).

Therefore, it is conclusively to say that although chlorination is identified as having the most potential for risk to aquatic organisms, WET testing results of discharged ballast water suggest that potential risk is absent.

6.3.6 Effects on aquatic organisms

Although no significant chemicals identified as potential ecotoxic substances were found in

the treated ballast water of Purimar TM System, appropriate Predicted No-Effect Concentrations (PNEC) is derived for Active Substance, Other Chemical and Relevant Chemicals that may be of concern for the aquatic environment.

PNEC values are estimated from short-term and/or long-term aquatic toxicity data for relevant aquatic species by dividing the lowest available effect concentration with an appropriate assessment factor as shown in Table 6.7. (See the complete confidential dossier.) Although a thorough literature review of available data was performed and summarized in Tables 3.23 and 3.24, some dataset was limited and did not meet validity criteria. Other dossiers submitted for Procedure (G9) approval also used incomplete datasets for fish, crustaceans, and algae for the derivation of the individual PNEC value. When a complete and valid dataset was not obtained from the literature review, the lowest effect concentration reported was utilized for PNEC derivation.

The resulting PEC/PNEC ratios of Active Substance, Other Chemical, and Relevant Chemicals are indicated in Tables 6.8 and 6.9. (Full data detailed in the complete confidential dossier.)

Table 6.8: PEC/PNEC ratios of case 1

Emission

Conc. Emission PEC Assessment

factor Endpoint PNEC PEC /

PNEC Chemical name

(mg/L) (g/day) (μg/L) ( - ) (mg/L) (μg/L) ( - )

TRO (without neutralization) 3.00000 842,382.00 8.04E+00 100 0.1 1 8.04E+0

0 TRO (with neutralization 0.1ppm) 0.10000 28,079.40 2.68E -01 100 0.1 1 2.68E-01

Chlorodibromomethane 0.01640 4, 605.02 3.91E-02 1000 34 34 1.15E-03

Tribromomethane 0.38100 106,982. 51 9.41E-01 1000 1 1 9.41E-01
Monochloroacetic acid 0.02160 6,065. 15 6.21E-02 1000 0.07 0.07 8.87E-01
Monobromoacetic acid 0.00540 1,516. 29 1.48E-02 1000 0.2 0.2 7.40E-02

Dichloroacetic acid 0.01620 4, 548.86 4.66E-02 1000 23 23 2.03E-03

Trichloroacetic acid 0.03890 10,922.89 1.17E-0 1 1000 1.2 1.2 9.75E-02

Bromochloroacetic acid 0.00594 1, 667.92 1.71E-02 1000 0.07 0.07 2.44E-01

Dibromoacetic acid 0.04300 12, 074.14 1.24E-01 1000 69 69 1.80E-03

Bromodichloroacetic acid 0.00277 777.80 7.96E-03 1000 23 23 3.46E-04

Dibromochloroacetic acid 0.00368 1,033.32 1.06E-02 1000 23 23 4.61E-04

Tribromoacetic acid 0.01040 2,920. 26 2.99E-02 1000 5.61 5.61 5.33E-03

Dichloroacetonitrile 0. 00056 157.24 1.67E-03 1000 0.55 0.55 3.04E-03

Dibromoacetonitrile 0.05170 14,51 7.05 1.55E-01 1000 0.55 0.55 2.82E-01

Sodium thiosulfate 9.00000 2,527, 146.0 2.79E+01 1000 805 805 3.47E-02

NOTE: The estimated ratios between predict ed concentrations of the Active Substa nce, Other Chemical, or Relevant Chemicals and the respective PNEC values are all below 1. Th is, together with the results of WET tests, indicates that no further assessment of direct toxic effects to the aquatic environment is necessary.MEPC 61/2 Annex, page 36

I:\MEPC\61\2.doc 6.3.7 Effects on sediment

As shown in section 3.4, there are no effects on sediment for the chemical and properties of the substances of PurimarTM System.

6.3.8 Comparison of effect assessment with discharge toxicity

A major concern following treatment of ballast water with any biocide is the discharge of potentially toxic chemicals to the environm ent. Acceptable ballast treatment for the prevention of non-indigenous species must be able to remove viable organisms from the ballast water and upon discharge be non-toxic to the receiving waters.

For the Purimar TM System, chlorination-induced oxidant is most likely to exist for any extended period of time, in concentrations potentially harmful to marine organisms. Various disinfection by-products were identified as possible constituents of toxicological importance

in the Purimar TM System treated ballast water, however, they did not reach toxic levels in the residual ballast water. Thus, chlorination-induced residual oxidant, as measured by TRO, is thought to be the only effective by-product that persists long enough to have been measured in the toxicity tests. However, a potential problem and alternatively an attractive feature of

chlorination treatment of ballast water is that the concentration of TRO in seawater declines over time. It should be noted that the chemistry and toxicity of chlorination of seawater is strongly affected by the chemistry of the water (e.g., TOC, temperature, pH, salinity and sediment loading), and the chlorine and bromine re sidues are extremely labile in sunlight and would not persist long in the environment, thus oxidant concentrations diminish quickly in chlorinated seawater exposed to the atmosphere.

The results of the WET tests indicated that test substances prepared from water samples taken immediately after treatment of the Purimar TM System (T0), showed residual toxicity. At that time point, the practical result indicates that the laboratory TRO level immediately on delivering was much lower than the corresponding field level at 5 hours after completion of chlorination. Furthermore, the laboratory TRO level after filtration was dramatically reduced. These results suggest that chlorination-induced oxidants may dissipate very quickly from samples that are exposed to sunlight and atmosphere and bubbled with ambient air. Our experiments may have underestimated the efficacy of chlorination resulting from the laboratory TRO level and possible residual toxi city of chlorination-induced residual oxidant over time. Therefore, the Purimar TM System was equipped with neutralizing unit, and the final discharged ballast water was dechlorinated with sodium thiosulfate to maintain the TRO concentration below 0.1 mg/L. All toxicity tests using neutralized water samples regardless of residual TRO concentration showed no residual toxicity.

Therefore, it is conclusively to say that the Purimar TM System is an excellent ballast water management system which prevents non-indigenous species from the influent ballast water and maintains non-toxic to the receiving waters upon discharge.

7 RISK ASSESSMENT

7.1 Risk to safety of ship

A risk analysis will be conducted by the Korean R egistry of Shipping to demonstrate that the

Purimar TM System is acceptable for installati on on TWECO test barge. A qualitative comparative analysis will be conducted for the chemical dosing and ballast water sampling systems involved in the installation.MEPC 61/2 Annex, page 37

I:\MEPC\61\2.doc Further, the Purimar TM System will be certified for shipboard installation by the Korean Registry of Shipping, in compliance with international design and construction standards for ship safety.

7.1.1 Corrosion

Corrosion in metal and steel is the important concern to the ship industry. This is why a majority of the surfaces internal to the ship and in contact with seawater such as piping and tanks are coated with protective paints and coatings. Tests of how well these paints and coatings protect metal and steel surfaces are completed by various organizations and coating vendors.

Now we will conduct corrosion testing with Korea Testing & Research Institute (KTR) applying IMO standard during land-based testing and the results will be reported in the Final Approval dossier.

Referring to the report of the eighth meeting of the GESAMP-Ballast Water Working Group document and in progressing an experiment, corrosion test should include uncoated substrates and marine epoxy coated steel. Coatings should be in accordance with the IMO Performance standard for protective co atings for dedicated seawater ballast tanks in all types of ships and double-side skin space of bulk carriers (MEPC 59/2/16, GESAMP-BWWG 8/6, paragraph 5.1.1.1; MSC.215(82)).

7.1.2 Fire and explosion (formation of gases)

Potential fire and explosion risks associated with the Purimar TM System are related to the hydrogen gas generated during the electrochemical process, the sodium thiosulfate (neutralizing agent) stored on board or electrical components of the system.

The PurimarTM System will generate hydrogen gas as a by-product during producing sodium hypochlorite. Hydrogen gas can be explosive at concentrations >4% volume in air.

The Purimar TM System has several safety mechanisms that are engineered into the system to ensure that hydrogen gas is effectively removed from the ship. These include a patented cyclone separator device that removes the hydrogen gas from the biocide solution and air blowers to reduce the concentration of hydrogen gas to <1% (well below the 4% Lower Explosive Limit) within a vent line to the air outside the ship. Additionally, a hydrogen gas detector is located in the space(s) where hydrogen gas may enter should a Purimar TM
System failure occur. The monitor and control will manage all of these safety features and will result in an alarm condition should the system require maintenance.

Hydrogen and chlorine gas will be measured during land-based test run, and the results will be submitted in the final report.

Sodium thiosulfate is a non-flammable, stable liquid. Excessive heating and/or contact with acids can liberate sulfur dioxide fumes, but does not create a fire hazard.

The PurimarTM System is already adopting the proven electrical components by Classification Society such as KR, ABS, DNV, LR, and GL. So, these components already met the existing safety guideline of Classification Societies. A part of electrical component which is not certified will be also tested and certified by Classification Society.

Considering the above safety measures, the fire and explosion risk in the PurimarTM System on board is very low.MEPC 61/2 Annex, page 38

I:\MEPC\61\2.doc 7.1.3 Storage and handling of the substances

As shown in section 3.1.4, the only chemical needs storage in the Purimar TM System is Sodium thiosulfate as neutralizing agent. Sodium thiosulfate is non-flammable and there is no possibility of fire risk on board as above- mentioned. The storage tank will be designed according to the guideline of Classification Society and the Purimar TM System including installation of storage tank will be certified by Classification Society. Consequently, the potential risks to the ship due to chemical storage are very low.

7.2 Risks to human health

The health risks to all recipients from the Purimar TM System under normal operating conditions are very small and well within a cceptable levels. Even an TWECO technician, exposed to concentrated sodium thiosulfate dur ing a spill during chemical resupply, and who is not wearing PPE (Personal Protective Equipment) – an unlikely scenario – would have low health risk. Cancer risk and non-cancer hazards for the general public/beachgoers are well below levels of concern; actual risks to these recipients are expected to be even lower, as they are unlikely to be repeatedly exposed to treated ballast water as assumed in this risk evaluation. Since the risk assessment only evaluated direct exposure via ingestion and dermal contact with chemicals or ballast water, as these were considered the most relevant pathways, further semi-qualitative evaluation of the inhalation pathway was performed for the

volatile THMs. This assessment demonstrated that conservative concentrations of airborne THMs generated by a release of ballast water were well below occupational exposure limits. Full details are contained in appendix 8 "Human Exposure Assessment".

7.2.1 Risk Characterization

Risk characterization is a summary for t he risk assessment components and serves to outline the key findings and inform the risk manager in public health decisions. It is an analysis and integration of the conclusions from the hazard assessment, the exposure assessment, and the health effect assessment.

7.2.1.1 Risk characterization during normal operation

Risk characterization for the operator during ballasting

Under normal operation, the system is to be considered as a closed circuit. There is no exposure to the in situ production of biocide solution, treated ballast water itself, or stored sodium thiosulfate in storage tanks. It is conclusive to say that there is no health risk for the operator during normal operation.

Risk characterization for the crew, dock workers, and general public during ballasting

The low concentrations of COPCs in ballast water compared to WHO guidelines for drinking

water and U.S. OSHA PELs indicate that the health risk related to inhalation of tank air for persons on deck is very low. It is worth noting that exposure to tank air is less frequent and of lower intensity than exposure to drinking water vapours, which should imply that the risk characterization is conservative. Therefore, it is conclusive to say that there is no need for risk mitigation measures.MEPC 61/2 Annex, page 39

I:\MEPC\61\2.doc If the wind directs the released tank air to the nearby port/coast, third party in the port/coast can be exposed to the tank air. Because the THMs in vent air would quickly dissipate into the atmosphere, it is anticipated that air exposures will decrease as distance to the ballast water increases; therefore, potential air exposures for dock workers and the general public in the third party would be even less than those for the ship’s crew.

Risk characterization for the operator and crew during deballasting

There is no exposure to the operator or crew during discharge of ballast water as the ballast water is discharged under sea level.

Risk characterization for the general public during deballasting

The chemicals identified in this risk assessment all have Log Kows less than 3 and BCFs less than 2000. Hence, these compounds will not be found in seafood. As a result, there is no health risk connected to consumption of seafood taken from areas where ballast water is discharged.

Most chemical compounds in treated ballast water are much lower in concentrations than the WHO guidelines for drinking water quality to assess the health risks in connection with swimming at beaches near areas where treated ballast water has been discharged from the ship. Although bromoform is found to be higher than the guideline, its concentration will be dramatically reduced in the swimming point as the plume of ballast water will be diluted in seawater when discharged to sea. As it is highly unlikely that the general public would recreate very close to docked ships, the health risk in connection with swimming in the vicinity of ships discharging ballast water is assessed as very low.

7.2.1.2 Risk characterization during maintenance of the ballast water tanks

Although the volatile THMs produced as disinfectant by-products could be inhaled near ballast water or vent air outlets, existing procedures for work in a tank means that any volatile gas in the tank due to ballast water treatment will not pose any additional health risk to personnel entering the tank. Furthermore, the potential exposures and risks associated with vent air during ballasting and de-ballasting are discussed in the above section, and it is concluded that, there is no need for additional risk mitigation measures.

7.2.1.3 Risk characterization during system maintenance and accidental situations

The operator of the Purimar TM System could have direct contact with COPCs within the system during maintenance activities and to sodium thiosulfate during chemical resupply activities. And the ship's crew including the operator could have oral and dermal exposure to

the treated ballast water in tanks.

Although the COPCs generated in situ at aqueous concentrations are at concentrations too low to cause serious eye and skin irritation, direct contact to whatever volume that is spilled may cause minor irritation to the eyes, sensitive skin and throat. Conventional personal protective equipment (PPE; i.e. gloves, and goggles) is considered adequate in order to minimize the potential for these acute health effects. Only trained personnel should be handling the concentrated solution. In case of ventilation breakdown or leakage, there is a risk of vapour or fumes to be released. These fumes may cause dizziness and nausea, and inhalation should be avoided. Respiratory protecti on should be available. As the acute health effects of COPCs are easily preventable, the risk to acute human health is considered to be

low.MEPC 61/2 Annex, page 40

I:\MEPC\61\2.doc The more critical endpoint for potential exposure to ballast water COPCs at low concentrations are chronic health issues. Thus, health effect assessment of COPCs exposures against ship's crew including the operator of the Purimar TM System are evaluated quantitatively in the appendix 8. The US EPA states that action is generally not warranted at a site when the cumulative non-carcinogenic hazard index is less than 1.0, and uses a potential excess individual lifetime cancer risk of 1 x 10 -6 (1 in 1,000,000) as a point of departure for risk management actions. As shown in Tables 7 and 8, the total non-carcinogenic hazard indexes of the operator and ship's crew are 0.237 and 0.0000977, respectively, which are well below the level of concern. And as shown in Tables 9 and 10, the total estimated cancer risk of the operator and ship's crew are 3.9 x 10 -9
(3.9 in 1,000,000,000) and 3.35 x 10 -9 (3.35 in 1,000,000,000), respectively, which are far below the US EPA point of departure.

It is believed that the potential risks presented in appendix 8 would be considered the worst-case estimates. The actual health risks to the populations of the exposures to

chemicals associated with the Purimar TM System are to be even lower, as they are unlikely to be repeatedly exposed to COPCs as assumed in this risk evaluation. In addition, the use of conventional personal protective equipment and safe chemical handling procedures will further reduce any potential exposures and associated effects.

7.3 Risks to the aquatic environment

The data for the substances associated with use of the Purimar TM System indicate that there is a low potential for bioaccumulation, sediment adsorption, and persistence in the aquatic environment. No effects or risks in the form of secondary (food chain) poisoning or to sediment species are anticipated. As such, toxicity presents the only likely potential risk for aquatic organisms.

Whole effluent toxicity testing (acute and sub-lethal endpoints) of neutralized ballast water discharge indicates no apparent toxicity for all species and endpoints tested (L(E)C 50 and/or

NOEC values of ≥ 100% ballast water sample).

To ensure that no risks can be expected from the neutralizing agent, further chronic toxicity testing was conducted with repeated dosing of ballast water neutralized with a large excess of sodium thiosulfate. Water samples were prepared by diluting the biocide solution generated from the TWECO laboratory-scale electrolytic apparatus with commercial seawater to a 1 mg/L of TRO, and then neutralizing with a 2.36 mg/L of sodium thiosulfate. Seven repeated dosing of freshly prepared water samples including a total of 16.52 mg/L sodium thiosulfate, which is much larger than would normally be applied, showed no toxicity (see Table 3.21).

Therefore, the toxicity testing of the treated ballast discharge indicates that unacceptable risks to the aquatic environment are not expected from use of the Purimar TM System.

8 ASSESSMENT REPORT

8.1 Overview of data and endpoint

The constituents associated with the Purimar TM System were evaluated for a variety of endpoints, including toxicity, bioaccumulation, and persistence in the environment. The physical and chemical properties were evaluated to assess proper chemical handling and/or storage in a shipboard setting, and risks such as fire/explosion. Treated ballast water discharge and the risks of the COPCs to human health were also evaluated.MEPC 61/2 Annex, page 41

I:\MEPC\61\2.doc As the Active Substance is generated on board as required and neutralized prior to discharge, it is the treated ballast water and DBPs potentially present that are the most important to consider for this evaluation.

Whole effluent discharge toxicity testing has been conducted for different water types at various Active Substance treatment and TOC levels, and at different holding times. As expected, toxicity was observed for all species in the samples collected immediately after hypochlorite treatment (Day 0). Some toxicity was observed in the Day 2 and Day 5 pre-neutralization samples. However, in all species tested, no toxicity was observed in the Day 2 and Day 5 post-neutralization samples concomitantly with non-detectable TRO.

During the preliminary and land-based test runs of the Purimar TM System meeting ballast water performance standard concerning biological efficiency, the amount of Active

Substance and Relevant Chemicals were measur ed. The evaluation of the toxicological, chemical, and physical properties of all chemic als obtained from eminent literatures and databases suggest that bioaccumulation, sediment adsorption, or persistence is not expected to occur. Further, none of the chemicals met all three PBT substance criteria.

The DBP concentrations from the studies noted a bove consider analysis of the whole effluent only and do not reflect actual environmental concentrations when treated ballast water is released in a harbour where dilution and mixing will occur. The PEC in the port of Busan was predicted by using the modelling of MAMPEC and the PNEC was determined from the selected aquatic toxicity data and assessment factors. The PEC/PNEC ratio of all chemicals

in ballast water treated with the Purimar TM System, were below 1 even at the worst case

emission scenario.

Potential human exposures and health effects were evaluated qualitatively and quantitatively, when possible. Overall, the risk assessment determined risks to all recipients from

the Purimar TM System under normal operating conditions are very small and well within acceptable levels.

8.2 Quality of the test reports

Both the efficacy and toxicity (including chemical analysis) testing complied with Guidelines (G8) and Procedure (G9) requirements regarding quality control, including the implementation of a comprehensive QAPP.

The quality assurance (QA) team of Dong A University (DAU) GLP Centre provided support and guidance in developing QAPP, and also provided technical review comments on the test reports, to assist in assessing their quality. DAU GLP centre is certified to Principles of Good Laboratory Practice by the Korea Food and Drug Administration, National Institute of Environmental Research, and Rural Development Administration.

Quality of the test reports is further assured by the fact that Busan Techno-Park Marine Bio-industry Development Centre (MBDC), which undertook the efficacy and toxicity testing, maintains QA certification of the Korean Laboratory Accreditation Scheme (KOLAS) for ISO/IEC 17025; and SGS testing Korea, which under took chemical analysis, also maintains QA certification of KOLAS for ISO/IEC 17025 and National Environmental Laboratory Accreditation Program (NELAP), which is the program that implements the National Environmental Laboratory Conference standards, States and Federal agencies serve as Accreditation Authorities with coordination currently facilitated by US EPA to assure uniformity.MEPC 61/2 Annex, page 42

I:\MEPC\61\2.doc For the study of risk assessment, a variety of reputable sources were consulted to gather test data and conduct the assessments required. These sources include, but are not limited to WHO, IPCS, OECD and US EPA. Information was also gathered from published independent research, which in most cases is peer-reviewed by others with similar levels of expertise. In some cases the test method used was not specified; however if the dataset was limited, this data was included to provide at l east some information. Due to the primary sources relied upon during the evaluation; the leve l of uncertainty with this assessment is

low.

9 REFERENCES

See the complete confidential dossier.

10 APPENDICES

Appendix 1: Key Data Summary Appendix 2: Certificates of TWECO and Test Facilities Appendix 3: Quality Assurance Project Plan (QAPP) Appendix 4: Test Report on Toxicity and Efficacy by MBDC Appendix 5: Test Report on Chemical Analysis by SGS Appendix 6: Material Safety Data Sheets Appendix 7: Purimar TM BWMS Manual Appendix 8: Human Exposure Assessment

(See the complete confidential dossier.)

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