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

I:\MEPC\59\2-1.doc

INTERNATIONAL MARITIME ORGANIZATION

IMO 

# E

MARINE ENVIRONMENT PROTECTION COMMITTEE 59th session Agenda item 2 MEPC 59/2/1 4 December 2008 Original: ENGLISH

HARMFUL AQUATIC ORGANISM S IN BALLAST WATER

Application for Final Approval of the Special Pipe Hybrid Ballast Water Management System (combined with Ozone treatment)

Submitted by Japan

SUMMARY

Executive summary: This document contains the non-conf idential informatio n related to the application for Final Approval of the Special Pipe Hybr id Ballast Water Management System (combined w ith Ozone treatment) under the ìProcedure for approval of ballast wa ter management systems that make use of Active Substances (G9)î adopted by resolution MEPC.169(57)

Strategic direction: 7.1

High-level action: 7.1.2

Planned output: 7.1.2.4

Action to be taken: Paragraph 6

Related documents: BWM/CONF/36; MEPC 55/2; MEPC 55/2/16; MEPC 57/2/10; MEPC 57/21; BWM.2/Circ.13 and BWM.2/Circ.15

Introduction

1 Regulation D-3.2 of the International Conventio n for the Control and Management of Shipsí Ballast Water and Sediments, 2004 stipulates that ballast water management systems that make use of Active Substances to comply with the Convention shall be approved by the Organization.

2 Japan herewith submits an application for Final Approval according to the ìProcedure for approval of ballast water management systems that make use of Active Substances (G9)î adopted by resolution MEPC.169(57). This Pr ocedure stipulates the required information (MEPC 57/21, annex 1, paragraph 4.2.1) which, accord ing to section 6, should be evaluated by the Organization. In accordance with the Meth odology for information gathering and conduct of work of the GESAMP-BWWG (BWM.2/Circ.13), th e annex to this document contains the non-confidential part of the manufacturerís application dossier including the following:MEPC 59/2/1 - 2 -

I:\MEPC\59\2-1.doc .1 summary of the research conducted for the Special Pipe Hybrid Ballast Water Management System combined with Ozone treatment version according to Procedure (G9);

.2 reference list; and

.3 statement and quality assurance statement.

The complete dossier will be made available to the experts of the GESAMP-BWWG with the understanding of conf idential treatment.

3 ìSpecial Pipe Hybrid Ballast Water Management System combined with Ozone treatment versionî (SP-Hybrid BWMS Ozone version) is the same system as previously called the ìSpecial Pipe Ballast Water Management System (combined with Ozone treatment)î, which was reviewed for Basic Approval based on Procedure (G9) at the second meeting of the GESAMP-Ballast Water Working Group (G ESAMP-BWWG) held in May 2006 and was granted Basic Approval at MEPC 55 in Octobe r 2006. The name was slig htly changed for the purpose of future commercialization.

4 The application for Final Approval is submitted by the manufacturer, Mitsui Engineering & Shipbuilding Co., Ltd., instead of the Japan Association of Mari ne Safety, that applied for Basic Approval, as a coordinator of th e project development at that time.

5 The receiving competent authority in Japan ha s verified the application dossier and has considered it in line with the da ta requirements of Procedure (G9).

Action requested of the Committee

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

***MEPC 59/2/1

I:\MEPC\59\2-1.doc ANNEX

NON-CONFIDENTIAL INFORMATION ON THE SPECIAL PIPE HYBRID BALLAST WATER MANAGEMENT SYSTEM COMBINED WITH OZONE TREATMEN T VERSION (JAPAN)

Contents

1 INTRODUCTION

1.1 Application process with Procedure G9 for ìSpecial Pipe Hybrid Ballast Water Management System combined with Ozone treatment ve rsionî (SP-Hybrid BWMS Ozone version) 1.2 Points made by GESAMP-BWWG at time of G9 Basic Approval 1.3 Constitution of the application for G9 Final Approval 1.4 Conditions of system application 1.5 Conclusion of Final Assessment Report

2 APPLICATION DATA SET

2.1 Identification of the Substa nce or Preparation (G9: 4.1) 2.1.1 Preparations (G9: 4.2.2) 2.1.2 Active Substances 2.1.3 Relevant Chemicals (G9: 2.1.4) 2.1.4 Other Chemicals 2.2 Data on effects on aquatic plants, inverteb rates and fish, and other biota, including sensitive and representativ e organisms (G9: 4.2.1.1) 2.2.1 Acute aquatic toxicity 2.2.2 Chronic aquatic toxicity 2.2.3 Endocrine disruption 2.2.4 Sediment toxicity 2.2.5 Bioavailability/biomagni fication/bioconcentration 2.2.6 Food web/population effects 2.3 Data on mammalian toxicity (G9: 4.2.1.2) 2.4 Data on e nvironmental fate and effect under aerobic and anaerobic conditions (G9: 4.2.1.3) 2.4.1 Modes of degradat ion (biotic; abiotic) 2.4.2 Bioaccumulation, partition coefficient, octanol/water partition coefficient 2.4.3 Persistence and identification of the main metabo lites in the releva nt media (ballast water, sea and fresh water) 2.4.4 Reaction with organic matter 2.4.5 Potential physical effects on wildlife and benthic habitats 2.4.6 Potential residues in seafood 2.4.7 Any known inter active effects 2.5 Physical and chemical properties of the Ac tive Substances and prep arations and treated ballast water, if applicable (G9: 4.2.1.4) 2.6 Analytical methods at environmenta lly relevant concentration (G9: 4.2.1.5)MEPC 59/2/1 ANNEX Page 2

I:\MEPC\59\2-1.doc 3 USE OF THE ACTIVE SUBSTANCE

3.1 Summary of SP-Hybrid BWMS Ozone version 3.1.1 Components and outline 3.1.2 The characteristics 3.1.3 Materials of major components 3.1.4 Results of environmental tests of component units 3.1.5 Approval of on board system by Classification Society 3.2 The manner of application (G9: 4.2.6 and 7) 3.2.1 The maximum dosage concentration of Ozone 3.2.2 Holding time 3.2.3 The maximum allowable discharge con centration of the Relevant Chemicals 3.2.4 Handling, use, storage and transport of the chemicals 3.2.5 Procedures and use of the system 3.2.6 Risk management measures in case of emergency 3.2.7 Other safety measures 3.2.8 Control of discharge water and countermeasures 3.2.9 Waste control and recycle

4 MATERIAL SAFETY DATA SHEETS (G9: 4.2.7)

5 RISK CHARACTERIZATION

5.1 Screening for persistence, bioaccu mulation and toxicity (G9: 5.1) 5.1.1 Persistence (G9: 5.1.1.1) 5.1.2 Bioaccumulation (G9: 5.1.1.2) 5.1.3 Toxicity test (G9: 5.1.2.3) 5.1.4 Do the Ozone and Relevant Chemical s meet all three criteria for PBT?

6 EVALUATION OF THE TREATE D BALLAST WATER (G9: 5.2)

6.1 Tests of the treated ballast water impl emented for the purpose of Final Approval 6.1.1 Outline of tests 6.1.2 Test facilities 6.1.3 Justification of test facilities 6.1.4 Quality control of test 6.2 Full-scale land-based acute toxicity test (G9: 5.2.2) 6.3 Repetition of chronic to xicity test (G9: 5.2.1) 6.4 Degradation test for generated Relevant Chemicals 6.5 Removal test for generated Relevant Chemicals 6.6 Long-term performance test of Discharge Water Treatment Tank 6.7 Determination of holding time 6.8 Risk characterization and analysis 6.8.1 Reaction with organic matter (G9: 4.2.1.3) 6.8.2 Characterization of degrada tion route and rate (G9: 5.3.5)MEPC 59/2/1 ANNEX

Page 3

I:\MEPC\59\2-1.doc 6.9 Prediction of discharge and environmental concentrations 6.9.1 Discharge concentration of Relevant Chemicals 6.9.2 Target port and the designated s ea area for the estimation of PEC 6.9.3 Calculation conditions of PEC 6.9.4 Calculation results 6.10 Assessment of potential for bioaccumulation 6.11 Effects assessment 6.12 Effects on aquatic organisms 6.12.1 Estimated PNEC 6.12.2 PEC/PNEC ratio 6.13 Effects on sediment 6.14 Comparison of effect assessment with discharge toxicity

7 RISK ASSESSMENT

7.1 Risk to safety of ship 7.1.1 Increased corrosion 7.1.2 Fire and explosion 7.1.3 Storage and handling of the substances 7.1.4 Contact with, or inhalation of, process products 7.1.5 Noise 7.2 Risk to human health 7.2.1 Health effects in humans (G9: 5.3.12) 7.2.2 Human Exposure Scenario (HES) (G9: 6.3.3) 7.2.3 Conclusion 7.3 Risk to the aquatic environment

8 CONCLUSION

REFERENCES

STATEMENT and QUALITY ASSURANCE STATEMENTMEPC 59/2/1 ANNEX Page 4

I:\MEPC\59\2-1.doc 1 INTRODUCTION

1.1 Application process with Procedure (G9) for ìSpecial Pipe Hybrid Ballast Water Management System combined with Ozon e treatment versionî (SP-Hybrid BWMS Ozone version)

The ìSpecial Pipe Hybrid Ballast Water Manage ment System combined with Ozone treatment versionî (SP-Hybrid BWMS Ozone version) used to be called the ìSpecial Pipe Ballast Water Management System (combined with Ozone treat ment)î. The ìSpecial Pipe Ballast Water Management System (combined with Ozone tr eatment)î was reviewed for Basic Approval according to the Procedure for approval of ballas t water management systems that make use of Active Substances (G9) at the second mee ting of GESAMP-Ballast Water Working Group (GESAMP-BWWG) held from 22 to 26 May 2006 a nd was granted Basic A pproval at MEPC 55, held from 9 to 13 October 2006.

The SP-Hybrid BWMS Ozone version for which an application is made for Final Approval with Procedure (G9) is identical to the system granted Basic Approval except for the following modifications for practical use:

.1 Name of the system

Another application with procedure (G9) is also considered by developing a BWMS which will combine the main compone nt of Special Pipe with an Active Substance other than Ozone. Therefore, an Active Substance combined with Special Pipe Hybrid Ballast Water Manage ment System was added to its name to clarify the components of th e system. Since the pres ent application for Final Approval with G9 uses Ozone as an Activ e Substance, the name was changed to ìSpecial Pipe Hybrid Ballast Water Management System combined with Ozone treatment versionî with the abbrevia tion of SP-Hybrid BWMS Ozone version.

.2 Operation of Discharge Water Treatment Tank (DWTT)

An application was made for Basic Approval of the system with two alternatives. One was to discharge the ba llast water after longer th an 48 hoursí storage in the ballast tanks following treatment of ballast water with maximum 4 mg/L Ozone at the time of ballasting. The other was to discharge ballast water after the residual Relevant Chemicals in the ballast water were reduced to an allowable level by post-treatment by the DWTT regardless of the time of storage after treatment at the time of ballasting.

Ozone was injected also for th e Final Approval in such mann er as to maintain 4 mg/L maximum Ozone concentration in the collect ed ballast water. However, this time the DWTT was applied to any ballast water discharge so that the safety of ballast water discharge to the environment could be assured. Furthermore, post-treatment by the DWTT without designating tank storage time was implemented in order to be able to discharge at any time.

This application for Final Approval is ba sed on Ozone injection to achieve 4 mg/L Ozone concentration for the intake of ballast water so that safety to the receiving environment of the discharged ballast water is assured. Furthermore, on the assumption that the holding time is zero, the system design was changed to apply post-treatment of the DWTT to every occasion.MEPC 59/2/1 ANNEX

Page 5

I:\MEPC\59\2-1.doc .3 Change of the applicant

The application for Basic Approval was submitted by the Japan Association of Marine Safety who had been acting as a c oordinator of the system development. However, the application for Final A pproval is presented by the manufacturer, Mitsui Engineering & Shipbuilding Co., Ltd.

1.2 Points made by the GESAMP-BWWG at the time of G9 Basic Approval

As stated in document MEPC 55/2/16, anne x 5, GESAMP-BWWG had brought up the following points on the application for Ba sic Approval (MEPC 55/2, as well as the confidential version) and recommended that these should be examined dur ing further development and testing and that the results should be reported at the time of submission of the application for Final Approval.

1.2.1 Recommendations by the GESAMP-BWWG, contained in document MEPC 55/2/16, annex 5, paragraph 10.4

.1 Due consideration should be given to the fact that the risk assessment currently performed has been based upon an incomple te data set and therefore the risk assessment should be considered as indi cative only. A complete data set may result in a different conclusion.

.2 Due consideration should be given to the fact that the information on the substance Bromoform as a possible Relevant Chemical is considered insufficient for a risk assessment on this chemical on all topics, therefore, additional information should be provided on this substance.

.3 The discharge from the ìwaste Ozone de struction unitî should be suitably sited and included in the Ozone monitoring and alarm system.

.4 It should be confirmed that the levels of THM and free Ozone in the ballast tanks remain acceptable. Additional safety precau tions should be put in place until such confirmation is obtained.

.5 It should be confirmed that the noise levels when the system is in operation remain within permitted levels for machinery spaces (MEPC 55/2/16, annex 5, paragraph 10.4.2.5).

.6 It should be confirmed that the initial as sessment that the corrosion effect will be limited is correct and that there is no add itional corrosion effect on ballast piping, ballast tanks or degradation of protective coatings resulting from the use of the system.

.7 The apparent discrepancy between the m easured chronic toxicity of the treated ballast water and the assessment of Brom ate should be investigated further. Awaiting the results of such investigations , the discharge of ballast water treated with Ozone during further development a nd testing should only take place under controlled conditions and in to an environment where a sufficient dilution can be assured for avoiding unreasonable ri sks to the aquatic environment.MEPC 59/2/1 ANNEX Page 6

I:\MEPC\59\2-1.doc 1.2.2 Other recommendations by the GESAMP-BWWG

GESAMP-BWWG made 17 comments in addition to those contained in document MEPC 55/2/16, annex 5, paragraph 10.4, so the total number of their comments and recommendations has reached 24.

1.3 Constitution of the application for G9 Final Approval

This application for Final Approval has been developed in compliance with the latest ìMethodology for information gathering and the conduct of work of the GESAMP-BWWG (updated May 23, 2008)î. The following further test s have been implemented for the application for Final Approval:

.1 acute toxicity tests of treated ballast water from the land-based test facility;

.2 repetition of chronic toxicity test;

.3 degradation test for gene rated Relevant Chemicals;

.4 removal test for generated Relevant Chemicals;

.5 long-term performance test of DWTT;

.6 inspection for hull corrosion in full-scale shipboard system;

.7 analysis for volatile Bromof orm from ballast tank; and

.8 noise measurement test in full-scale shipboard system.

Furthermore, taking in to consideration the co mments made previously by the GESAMP-BWWG on the application for Basic Approval (MEPC 55/2/ 16, annex 5), the requireme nt for Basic Approval as well as all the sections following section 2 ìA pplication data setî, have been reproduced, and ultimately risk assessment (see section 7) has been conducted.

1.4 Conditions of system application

SP-Hybrid BWMS Ozone version should be applied under the following conditions. This application for Final Approval requires review and permission with reference to the use of BWMS under the following conditions:

.1 Ballast water required for treatment

Sea and brackish water containing br omide ion. Fresh water containing no bromide ion is not includ ed in this application.

.2 Times of ballast water treatment

It is treated only once on ballasting.MEPC 59/2/1 ANNEX

Page 7

I:\MEPC\59\2-1.doc .3 Concentration of Active Substance (Ozone) when in use

Ozone as Active Substance is injected on ballasting in such manner to achieve the concentration of 3 mg/L in the ballasting water.

.4 Holding time

Holding time following ballast water treatment is not specified. Ballast water can be discharged immediately after treatment.

.5 Use of DWTT

At the time of ballast water discharge, the Relevant Chemicals should be removed by the DWTT.

.6 The maximum allowable discharge c oncentration of Relevant Chemicals

The concentration of relevant chemicals at the time of discha rge following removal by the DWTT is less than 0.07 mg/L for Bromate ion, less than 0.19 mg/L for Bromoform and less than 0.2 mg/L for TRO (as O 3 ).

1.5 Conclusion of Final Assessment Report

SP-Hybrid BWMS Ozone version uses Ozone, which is a powerful oxidizing agent as the Active Substance. Ozone reacts with ballast water to generate the Relevant Chemicals, Bromate ions, Bromoform and TRO in the ballast water. However, as this BWMS has thorough safety measures for Ozone put in place on board a vessel , safety to the vessel and crew is completely secured. Furthermore, as the concentration of generated Relevant Chemicals can be reduced through the DWTT, the potential impact to public health and environment in the ambient waters of ballast discharge is deemed almost negligible. Therefore, this system is considered to deserve Final Approval under Procedure (G9).

2 APPLICATION DATA SET

2.1 Identification of the Substa nce or Preparation (G9: 4.1)

2.1.1 Preparations (G9: 4.2.2)

SP-Hybrid BWMS Ozone version is a BWMS, which inactivates aquatic organisms in the ballast water by using the inactivation effect of Special Pi pe and Ozone against the organisms. Ozone is generated by use of air as raw material. First ai r is converted to a gas with more than 90% oxygen concentration using an Oxygen Ge nerator then Ozone is produced by a cylindrical water cooled silent discharge type Ozone Generator. The gene rated Ozone is injected into the ballasting line by the Ozone Injector. Various items of equipm ent installed on board a vessel make all these treatment processes available at th e time of intake of ballast water. Therefore, this system does not require any preparation of chemical substa nces and does not need to store Ozone on board.

The Ozone gas mixture, which is injected to ball asting line contains other gaseous components of the air. The concentration of Ozone is in th e range of 6 to 12 v/v%. Table 2.1-1 showed the components of the gas injected to ballasting line of this system, showi ng concentration, CAS No. and classification of Active Substances, etc. As this BWMS generates all the components on board, the UN number and shipping name of each component do not need to be reported.MEPC 59/2/1 ANNEX Page 8

I:\MEPC\59\2-1.doc Ozone is the only Active Substance in the inje cted Ozone gas mixture. As oxygen and other components are either components of the air or present temporarily in small amounts, they are not deemed to be Active Substa nces or Relevant Chemicals.

Table 2.1-1: Component of Ozone gas inje cted to ballasting line of this system

Composition of Ozone gas mixture Component Chemical Name CAS Number Empirical formula Molar Mass Concentration (%) AS, RC or Other *

Ozone 10028-15-6 O 3 48.00 6-12 v/v % AS Oxygen 7782-44-7 O 2 32.00 80-88 v/v % Nitrogen 7727-37-9 N 2 28.01 2-3 v/v % Argon 7440-37-1 Ar 39.95 4-5 v/v % component of the air

* AS: Active Substance, RC: Relevant Chemicals, Other: Any other Chemicals

2.1.2 Active Substances

The Active Substance of SP-Hybrid BWMS Ozone version is Ozone. Information on Ozone follows below:

.1 trade name: Not applied as this is generated on board a vessel;

.2 chemical (IUPAC) name: Ozone;

.3 CAS number: 10028-15-6;

.4 UN number and proper shipping name: Not applied as this is generated on board a vessel;

.5 Molar mass: 48.00;

.6 empirical formula: O 3;

.7 structural formula: ;

.8 classification in accordance with the UN GHS system: Omitted;

.9 purity of the technical mate rial and identification of impurities (chemical name and CAS- number, etc.): Refer Table 2.1-1; and

.10 identity of any stabilizer or neces sary additives: No need to report.

2.1.3 Relevant Chemicals (G9: 2.1.4)

Natural seawater contains many dissolved substan ces. In particular, a maximum concentration of 60 mg/L (8.14 × 10 -4 mol/L) of bromide ion (Br - ) is present and this has the potential to react with Ozone injected into the ballast water as il lustrated in Figure 2.1-1. This reaction varies depending on conditions such as the concentrati on of organic matter in seawater and inorganic substances like ammoniacal nitrogen. The r eaction also varies with temperature and pH.MEPC 59/2/1 ANNEX

Page 9

I:\MEPC\59\2-1.doc When Ozone comes into contact with bromide ions, reactions (1) to (4) shown in Figure 2.1-1 generate the oxidizing agents hypobromous acid ion (BrO - ) and Bromate ions ( BrO 3 - ). In addition, some bromide ions reform. Bromate ions have th e potential to be transformed to bromic acid (HBrO 3 ) which is more oxidiz ing but it is only limited to pH < 0.8, which do es not happen normally. A calculation of the equilibrium ratio of hypobromous acid ( HBrO ) and hypobromous acid ion under the normal circumstance of pH 6 - 8, wh ich was performed by using the dissociation coefficient of pKa = 8.73, has shown that the hypobromous acid io n is stable above Ph = 10 but this is very rare in natural seawater. Eventua lly hypobromous acid dominates. When hypobromous acid is oxidized by Ozone, it is changed to bromous acid ions ( BrO 2 - ) and oxygen. Further bromous acid ions are transformed to bromide ions by Ozone oxidization.

Hypobromous acid reacts with natural organic matter (NOM) to generate bromine organic compounds such as trihalomethanes (THM). In the presence of ammoniacal nitrogen hypobromous acid reacts with ammonia instantaneous ly and reverts to bromide. A comparison of reaction velocity between ammoniacal nitrog en and organic matter reveals that ammoniacal nitrogen reacts faster than the reaction formul a (6) (see Figure 2.1-1), with the result that Bromoform is generated by reaction with orga nic matter after this reaction is finished.

When Ozone self-degrades in water, free radicals are generated. As the free radicals disappear in a short period, Ozone is considered to disa ppear completely before it is discharged.

On the assumption of these reacti ons between seawater and Ozone and also based on the results of experimental concentration measurements of chemi cal substances occurring after treatment of the intake ballast water by Ozone in jection (to achieve the maximum 4 mg/L Ozone concentration in the ballast water) but before the post-treatment of the discharged water, the following substances were determined as Relevant Chemicals of the SP-Hybrid BWMS Ozone version:

.1 Bromate ions as an ultimate product ge nerated by reaction be tween seawater and Ozone;

.2 Bromoform potentially generated by react ion between seawater and Ozone; and

.3 TRO showing mass of all oxidants gene rated by reaction between seawater and Ozone including undetectable intermediate products.

Table 2.1-2 showed information on the Relevant Chemicals of the SP-Hybrid BWMS Ozone version in addition to information on Ozone as the Active Substance. Comprehensive testing showed the following maximum concentrations of Relevant Chemicals in the ballast water discharge: Bromate ions: 0.07 mg/L, Brom oform: 0.018 mg/L and TRO 1.18 mg/L (as O 3 ).

The maximum generated concentration of Br omoform was found to be relatively low at 0.19 mg/L, which potentially resulted from the relatively low Ozone concentration of 4 mg/L in the ballast water and also from the rapid removal of the non-reacted Ozone in the Gas/Liquid Separation Tank immedi ately after Ozone injection.

Since 0.21 to 1.21 mg/L TRO (as O 3 ) was detected in the test water (natural water) prior to treatment by this BWMS, the whole TRO contained in ballast water discharge is not necessarily generated by ballast water treatment (Ozone treatm ent) of this BWMS. This result indicates that the substances constituting TRO involve unidentif ied oxidizing materials in addition to the toxic Bromate ion and the extremely short-lived hy pobromous acid, which are generated by ballast water treatment of the BWMS. The TRO concentra tion in the test water prior to treatment by BWMS (natural water) can be deducted from th e TRO value in the ballast water discharge inMEPC 59/2/1 ANNEX Page 10

I:\MEPC\59\2-1.doc order to derive the actual TRO value generated and ultimately discharged by this BWMS. Its maximum concentration is 0.69 mg/L in the repe tition of the chronic toxi city test as detailed in section 6.3 of this document.

The Final Approval application of this BWMS is based on the risk assessment with the maximum discharge concentration of 0.69 mg/L TRO (as O 3 ). However, the maximum allowable discharge concentration of 0.2 mg/L was applied to this BWMS for the Final Approval application for the following reasons:

.1 Application of 0.2 mg/L TRO (as O 3 ), which is lower than the discharge concentration of the risk assessment, thoroughly el iminates the environmental impact.

.2 Various tests were conduct ed to collect a total of 64 measurements of TRO (O 3 ) in the ballast water discharge follow ing injection of 4 mg/L Ozon e and almost simultaneous removal of Relevant Chemical s in the DWTT. 45% of the measurements were less than the detectable lim it of 0.15 mg/L, 6% were between 0.14 and 0.2 mg/L and 45% were between 0.2 and 0.3 mg/L. Data showing a TRO (O 3 ) of less than 0.3 mg/L constitute 97 % and data s howing more than 0.3 mg/L including the maximum value of 0.69 mg/L constitute only 3% (2 data points). As the data represent TRO concentrations corresponding to an Ozone concentration of as much as 1 mg/L higher than the 3 mg/L to be actually used for this BWMS and as it was discharged without a detention time, the concentration is presumed to be substantially higher than that which w ill occur during actual operation of this BWMS. It is considered that the TRO (as O 3 ) in the ballast water discharge will be less than 0.2 mg/L in most cases when operating this BWMS.

.3 From the standpoint of environmenta l consideration and actual operational circumstances of this BWMS, the maximu m allowable discharge concentration is defined as 0.2 mg/L.

The toxicity of TRO (as O 3 ) generated and discharged by this BWMS is summarized as follows:

.1 The TRO (as O 3 ) concentration generated by this BWMS and discharged following post-treatment of the DWTT in the repetition of the chronic toxicity test as detailed in section 6.2 of this document was 0.69 mg/L at the maximum and less than 0.3 mg/L in most of the cases. No toxicity was observed in the chronic toxicity test for three kinds of marine organisms when they were exposed to the ballast water with these TRO concentr ations. When 0.69 mg/L was observed, it resulted from an extremely high TRO (as O 3 ) concentration of 0.6 mg/L in the test intake water (natural seawater) supplied to this BWMS.

.2 The maximum TRO (as O 3 ) concentration in the full-scale land-based acute toxicity test was 0.21 mg/L. No acute t oxicity was observed, as in the chronic toxicity test.

.3 The results of these toxicity tests are cons idered to reflect the degree of toxicity of oxidant generated by the reacti on of Ozone with seawater.

.4 The TRO (as O 3 ) concentration in the ballast wa ter discharge depends on removal performance of post-treatment in the DWTT. The sustainability of the removal performance of this BWMS was confirmed in the test for sustainable performance to remove Relevant Chemicals as de scribed in 6.6 of this document.MEPC 59/2/1 ANNEX Page 11

I:\MEPC\59\2-1.doc The results of various te sts showed the TRO (as O 3 ) generated by this BWMS for risk assessment as well as the TRO (as O 3 ) actually measured before subtracting the TRO (as O 3 ) contained in the natural seawater used for the test. As prev iously stated, the observed maximum discharge concentration was 0.69 mg/L, which was higher th an 0.15 mg/L, which was presented at the time of the Basic Approval. This resulted from the ma ny subsequent tests and so the concentration for risk assessment should be revised accordingl y. The method used to monitor TRO (as O 3 ) and to operate the DWTT was detailed in section 3 ìUse of the Active Substanceî of this document.

Reactions and Rate Constants for Molecular Ozone Mechanism

No. Reaction k or p K a(20 °C ) Reference No. (Refer to APPENDIX1-1) (1) O 3 + Br - → O 2 + OBr
- 50 M
- 1 s - 1 1 (2) O 3 + OBr
- → 2O 2 +Br - 300 M
- 1 s - 1 2 (3) O 3 + OBr
- → Br O 2 - + O 2 100 M
- 1 s - 1 3 (3a) O 3 + HOBr → Br O 2 - + O 2 +H + ≦ 0.013 M
- 1 s - 1 4 (4) Br O 2 - + O 3 → BrO 3 - +O 2 10 5 M - 1 s - 1 4 (5) HOBr ⇄ H + + OBr
- 50M
- 1 s - 1 5

5×10 10 M - 1 s - 1 6 (6) HOBr + NH 3 → NH 2 Br + H 2 O 8×10 7 M - 1 s - 1 7 (7) O 3 + NH 2 Br → Y 40 M
- 1 s - 1 7 (8) Y+ 2O 3 → 2H + + NO 3 - +Br - +3O 2 k8 ≫ k7 7

Figure 2.1-1: Reactions of bromide ions with Ozone in water O 3 NH 3 CHB r 3 NH 2 Br

BrO 2 - B rO 3 -

CO 3 - ・ , Br 2 - ・ OBr

- HOB r NOT

Br

-

O 3

Br ・ O 3 O 3

BrO ・ O 3

Y*

NO 3 - H +

H 2 O O 3 O 3 O 3 CO 3 - ・ BrO 2 Br 2 O 4

OH

- OH

-

Br -

Br

2 - ・

Br 3 - ・ OBr

-

* Y are unknown products that react in later r eactions ( 1 )

( 2 ) ( 3 )
( 4 ) ( 5 ) ( 5 ) ( 6 )

( 7 )

( 8 ) ( 8 ) ( 3a )

O 3 O 2 - ・ O 3 NH 3 CHB r 3 NH 2 Br

BrO 2 - B rO 3 -

CO 3 - ・ , Br 2 - ・ OBr

- HOB r NOT

Br

-

O 3

Br ・ O 3 O 3

BrO ・ O 3

Y*

NO 3 - H +

H 2 O O 3 O 3 O 3 CO 3 - ・ BrO 2 Br 2 O 4

OH

- OH

-

Br -

Br

2 - ・

Br 3 - ・ OBr

-

* Y are unknown products that react in later r eactions ( 1 )

( 2 ) ( 3 )
( 4 ) ( 5 ) ( 5 ) ( 6 )

( 7 )

( 8 ) ( 8 ) ( 3a )

O 3 O 2 - ・MEPC 59/2/1 ANNEX Page 12

I:\MEPC\59\2-1.doc 2.1.4 Other Chemicals

Ballast water treatment by this BWMS theo retically generates hypobromous acid, hypobromous acid ions and bromous acid ions. However, due to the reaction rate formula (3) to (5) described in Figure 2.2-1, these react to fo rm Bromoform or Bromate ions w ithin a few seconds and so they are unlikely to exist long in the ballast water discharge. D. Fisher and others also state these substances exist for an extr emely short period (Fisher.D et al ., 1999). Furthermore, it is practically impossible to detect their concentrati on in the ballast water after treatment. Also, free radicals such as the hydroxyl-radical (OH

- ) are produced in the process of Ozoneís decomposition in water. Hydroxyl-radicals have an extremely strong oxidizing property. They react 10 6 times faster than Ozone and do not exist in the ballast water except for a very short period immediately after treatment.

Some tests have shown generation of dibromochlor omethane, which is a kind of trihalomethane. However, its generated concentr ation is only 0.0049 mg/L at maximum which is about 1/20 of the 0.1 mg/L, WHO Drinking Water Standard (W HO, 1996) Most of this small amount of dibromochloromethane was removed in the DWTT and its maximum concentr ation in the ballast water discharge was found to be 0.0002 mg/L, but th e concentration was too low to be detected in most of the tests.

From the above standpoint, hypobromous acid, hypobromous acid ion, free-radicals and dibromochloromethane, which are generated by ba llast water treatment of this BWMS, are not left in the ballast water discharge. Furtherm ore, as they have no pot ential to affect the environment in the local sea area, they are not considered to be Relevant Chemicals.

Table 2.1-2: Information about Relevant Ch emicals of SP-Hybrid BWMS Ozone version

Chemical Name Empirical Formula Molar

mass Structural formula CAS Number The classification in accordance with the UN GHS system Concentration in discharge ballast water, after treatment of the DWTT (Bio)degradation rate

or half-life AS, RC or Other

Ozone O 3 48.00 10028-15-6 (1956) APPENDIX 7-2 N/A 5.8 Sec AS

Bromate ion BrO 3 - 127.9 15541-45-4 N/A <0.01 - 0.07 mg/L Over 40 days RC

Bromoform CHBr 3 252.7 75-25-2 APPENDIX 7-2 0.0001 - 0.018 mg/L 32-185 days RC

TRO (as O 3 ) N/A N/A N/A N/A N/A 0.21 - 1.18 mg/L (<0.15 - 0.69 mg/L) 0.75-4.5 days RC

* N/A; Not Available

2.2 Data on effects on aquatic plants, invert ebrates and fish, and other biota, including sensitive and representative organisms (G9: 4.2.1.1)

With reference to effects by Ozone as the Acti ve Substance, Bromate ion and Bromoform as Relevant Chemicals, and TRO on aquatic plants , aquatic invertebrates (crustacean, mollusc) and fish, information was collated from ECOTOX (U .S.EPA 2007a). Regarding TRO, there are published data on specific oxidants, but relevant data were not found since the TRO is not a specific chemical. However, some data from th e tests on treated ballast water are available.MEPC 59/2/1 ANNEX Page 13

I:\MEPC\59\2-1.doc 2.2.1 Acute aquatic toxicit y

2.2.1.1 Active Substance

Table 2.2-1 showed acute toxicity data ( LC 50 ) on Ozone. As Ozone degr ades within a short period, it does not exist in the di scharge ballast water and it does not affect aquatic organisms in the ambient seawater after discharge.

2.2.1.2 Relevant Chemicals

Table 2.2-2 showed acute toxicity data ( LC 50 and EC 50 ) on Bromate ions. The lowest value among the data was 30 mg/L at 96 hour EC 50 for molluscs of the type Crassostrea giga

.
Table 2.2-3 showed acute toxicity data ( LC 50 and EC 50 ) on Bromoform. The lowest value of LC 50 was 7.1 mg/L for fish of the type Cyprinodon variegates.

Data on TRO were not available as it shows the total mass of oxidant s and is not a sp ecific chemical.

Table 2.2-1: Acute Aquatic Toxicity Data on Ozone

Species LC 50 (mg/L/duration) Reference/Comments/ Justification for missing data

Morone saxatilis , SW 0.08 (96-h LC 50 ) ECOTOX database (U.S. EPA, 2007a)

Morone Americana , SW 0.2 (96-h LC 50 ) ECOTOX database (U.S. EPA, 2007a)
Oncorhynchus mykiss , FW 0.0093 (96-h LC 50 ) ECOTOX database (U.S. EPA, 2007a) Fish

Ictalurus punctatus , FW 0.03 (96-h LC 50 ) ECOTOX database (U.S. EPA, 2007a)

Crustacea N/A N/A ECOTOX database (U.S. EPA, 2007a). Other literature was not available for data.

Molluscs Dreissena polymorpha, FW 0.53 (5.8-h LC 50 ) Harrington et al. (1997)

Algae N/A N/A ECOTOX database (U.S. EPA, 2007a). Other literature was not available for data.

N/A; Not Available

Table 2.2-2: Acute Aquatic T oxicity Data for Bromate ion

Species LC 50 and EC 50 (mg/L/duration) Reference/Comments/ Justification for missing data

Fish Oncorhynchus keta , SW 512 (96-h LC 50 ) ECOTOX database (U.S. EPA, 2007a)

Crustacea Neomysis awatschensis , SW 176 (24-h LC 50 ) ECOTOX database (U.S. EPA, 2007a)
Crassostrea gigas ,SW 30 (96-h EC 50 ) ECOTOX database (U.S. EPA, 2007a) Molluscs Crassostrea gigas ,SW 170 (24-h EC 50 ) ECOTOX database (U.S. EPA, 2007a)

Algae N/A N/A ECOTOX database (U.S. EPA, 2007a). Other literature was not available for data.

N/A; Not AvailableMEPC 59/2/1 ANNEX Page 14

I:\MEPC\59\2-1.doc Table 2.2-3: Acute Aquatic Toxicity Data for Bromoform

Species LC 50 (mg/L/duration)

or EC 50 (mg/L/duration) Reference/Comments/ Justification for missing data

Cyprinodon variegates

, SW 7.1 (96-h LC 50 ) ECOTOX database (U.S. EPA, 2007a) Brevoortia tyrannus , SW 12 (96-h LC 50 ) ECOTOX database (U.S. EPA, 2007a) Fish
Lepomis macrochirus

, FW 29 (96-h LC 50 ) ECOTOX database (U.S. EPA, 2007a) Americamysis bahia

, SW 24.4 (96-h LC 50 ) ECOTOX database (U.S. EPA, 2007a)
Penaeus aztecus , SW 26 (96-h LC 50 ) ECOTOX database (U.S. EPA, 2007a) Daphnia Magana , FW 46 (48-h LC 50 ) ECOTOX database (U.S. EPA, 2007a) Crustacea

Daphnia pulex , FW 44 (96-h LC 50 ) ECOTOX database (U.S. EPA, 2007a) Skeletonema costatum

, SW 12.3 (96-h EC 50 ) ECOTOX database (U.S. EPA, 2007a) Pseudokircheneriella subcapitata , FW 42 (72-h EC 50 ) ECOTOX database (U.S. EPA, 2007a) Algae

Pseudokircheneriella subcapitata , FW 40.1 (96-h EC 50 ) ECOTOX database (U.S. EPA, 2007a)

2.2.1.3 Treated ballast water (G9: 5.2.3)

An acute toxicity test for ballast water tr eated by the SP-Hybrid BWMS Ozone version was applied to the following test water under the G8 intake test water conditions for seawater and brackish water by using the full-s cale system adopted for Guidelines (G8) land-based test. Ozone was injected into the flow to achieve an Ozone concentration at 4 mg/L in the intake ballast water (200 m3/h) at intake time.

Test water: Discharged ballast water after Rele vant Chemicals were removed through the DWTT immediately following treatment by Ozone injection (Holding time: 0 h)

Table 2.2-4 showed the maximum concentrations of the Relevant Chemicals at exposure time and the results of acute toxicity tests to determine LC 50 and ECr 50 using diluted samples of the discharged ballast water. Almost all of th e undiluted samples (i.e.100%) did not meet the toxicity criteria for LC 50 or ECr 50 , so the entry in the table indicates that the result is >100%. The test with brackish water reporte d 0.4 mg/L as the lowest c oncentration of dissolved oxygen, which resulted from a decrease of dissolved oxygen in line with the decomposition of highly concentrated organic matter in the test water du ring the experiment. M easures to restore the dissolved oxygen by aeration were not taken in th e acute toxicity test in order to preclude underestimation due to vaporization of Bromoform, etc. Such a low concentration of dissolved oxygen may possibly have affected the result of test and 71% (96h-LC 50 ) represented by the

crustacean Hyale barbicornis presumably resulted from th is decrease of dissolved oxygen.

If this effect was taken into consideration, no acute toxicity ex isted in the test water and the discharged ballast water. The maximum concentr ation of detectable Relevant Chemicals in the test water using both sea and brack ish water is Bromate ions: 0.07 mg/L,MEPC 59/2/1 ANNEX Page 15

I:\MEPC\59\2-1.doc Bromoform: 0.015 mg/L, TRO (as O 3 ): 1.18 mg/L, TRO (as O 3 ) generated by ballast water treatment of this BWMS is le ss than 0.15 mg/L. The concentr ations of Bromate ions and Bromoform are substantially lower than the acut e toxicity values stated in the ECOTOX data base. Also 1.18 mg/L TRO and 0.15 mg/L TRO in terms of TRO generated by ballast water treatment of this BWMS resulted in showing no acute toxicity.

Table 2.2-4: Maximum concentration of discharged ballast water to meet LC 50 and ECr 50 criteria in the full-scale land-based toxicity test

2.2.2 Chronic aquatic toxicity

2.2.2.1 Active Substance

Table 2.2-5 showed chronic toxicity data (NOEC) for Ozone. Accord ing to chronic toxicity data for fish of the type Oncorhynchus mykiss the 90 day NOEC is 0.002 mg/L. As described in the acute aquatic toxicity section of this dossier, Oz one dissolves in a short period. Therefore, it does not reside in the ballast water discharge and has no effect on aquatic organisms in the ambient seawater after discharge.

Table 2.2-5: Chronic Aquatic Toxicity Data for Ozone

Species NOEC (mg/L/duration) Reference/Comments/Justification for missing data

Fish Oncorhynchus mykiss 0.002 ( 90 day NOEC ) Wedemeyer et al ., 1979

Crustacea N/A N/A ECOTOX database (U.S. EPA, 2007a). Data were not available in other literature.
Algae N/A N/A ECOTOX database (U.S. EPA, 2007a). Data were not available in other literature

N/A; Not Available

2.2.2.2 Relevant Chemicals

Table 2.2-6 showed chronic toxicity data (NOE C) for Bromate ions. According to chronic toxicity data for algae of the type Skeletonema costatum , the 7 day NOEC was >0.125 mg/L.

Test water Max. concentration of Relevant Chemicals (mg/L) Fish: Oryzias javanicus Crustacea: Hyale barbicornis (96h-LC 50 ) Algae: Skeletonema

costatum (72h-ECr 50 ) Bromate ion 0.07 Bromoform: 0.0023 TRO (as O 3 ) 0.85 Seawater Generated TRO by Ozone Treatment (mg/L as O 3 ) <0.15 >100% >100% >100%

Bromate ion 0.04 Bromoform: 0.015 TRO (as O 3 ) <1.18 Brackish

water Generated TRO by Ozone Treatment (mg/L as O 3 ) <0.15 >100% 71% >100%MEPC 59/2/1 ANNEX Page 16

I:\MEPC\59\2-1.doc Table 2.2-7 showed chronic toxicity data ( NOEC or MATC) for Bromoform. The minimum concentration is 4.8 mg/L of 28 day MATC (M aximum Acceptable Toxican t Concentration) for fish of the type Cyprinodon variegates

.
As TRO represent the total mass of oxidants and is not a specific chemical, data were not available.

Table 2.2-6: Chronic Aquatic Toxicity Data for Bromate ions

Species NOEC (mg/L/duration) Reference/Comments/Justification for missing data

Fish N/A N/A ECOTOX database U.S. EPA, 2007a). Data were not available in other literature.

Crustacea N/A N/A ECOTOX database (U.S. EPA, 2007a). Data were not available in other literature.
Algae Skeletonema

costatum , SW >0.125 (7 days NOEC) Erickson and Freeman, 1978

N/A; Not Available

Table 2.2-7: Chronic Aquatic toxicity Data for Bromoform

Species MATC (mg/L/duration) or NOEC (mg/L/duration) Reference/Comments/ Justification for missing data

Fish Cyprinodon variegates MATC; 4.8(28 days) Ward et al ., 1981

Crustacea N/A N/A ECOTOX database (U.S. EPA, 2007a). Data were not available in other literature.
Algae Pseudokircheneriella subcapitata , FW NOEC;10 (96 hours) ECOTOX database (U.S. EPA, 2007a)

N/A; Not Available

2.2.2.3 Treated ballast water (G9: 5.2.3)

A chronic toxicity test for the ballast wate r treated by SP-Hybrid BWMS Ozone version was conducted for Basic Approval. The NOEC in terms of TRO (as O 3 ) generated by ballast water treatment of this BWMS was determined to be equal to or greater than 0.16 mg/L. With reference to this NOEC, it was reported that the TRO concentration in the ballast water discharge after removal of Relevant Chemicals by DWTT is consistently under 0.15 mg/L.

However, GESAMP-BWWG recommended clarification of the relative toxicity of the discharge and Relevant Chemicals such as Bromate io ns and Bromoform (MEPC 55/2/16, annex 5). To address this recommendation, a second chr onic toxicity test was conducted including measurement of Relevant Chemicals in the test water.

This repetition of the chronic t oxicity test was conducted for the following test water and for the purpose of determining the NOEC in the ballast wa ter discharge. A prerequisite condition for test water flown to BWMS applied Guidelines (G 8) land-based test requir ement using seawater. From the various test results it was confirmed th at seawater contains a higher concentration of bromide ions than brackish water and consequently a higher concentration of Relevant Chemicals is generated by reaction with Ozone . This was the reason to use s eawater. Ozone is injected in such manner to achieve an Ozone concentration of 4 mg/L in the intake ballast water (20 m3/h).MEPC 59/2/1 ANNEX Page 17

I:\MEPC\59\2-1.doc Test water:

.1 Control water (i.e. the original wate r, which was also used for dilution).

.2 Discharge ballast water after rem oval of Relevant Chemicals by DWTT immediately following treatme nt (Ozone injection) w ithout holding time ñ Two samples were made: (a) undiluted discharg e ballast water 100%, and (b) discharge ballast water diluted to 10% using original water.

.3 Original water treated by Ozone inj ection without holding time and without removal of Relevant Chemicals by DWTT ñ Four samples were made: (a) undiluted discharge ballast water (100%) and discharge ballast water diluted to (b) 10%, (c) 3.125% and (d) 1% using original water.

The maximum concentration of detectable Relevant Chemicals in the NOEC test water indicated by this test was Bromate ions: 0.03 mg/L, Bromofor m: 0.0093 mg/L, TRO (as O 3 ): 0.96 mg/L, the TRO (as O 3 ) generated by ballast water treatment of this BWMS is 0.69 mg/L. Above all, the concentrations of Bromate ions and Bromoform were well below the previous NOEC and MATC and results in supporting both data. In terms of TRO (as O 3 ) generated by ballast water treatment of this BWMS, the no effect maximum concentr ation in the test water was 0.69 mg/L. This supports the value of NOEC, which was found to be equal to or greater than 0.16 mg/L in the chronic toxicity test con ducted for Basic Approval.

Table 2.2-8: NOEC in repetition of chroni c toxicity test and maximum concentration of Relevant Chemicals at time of exposure

Test water Max. concentration of Relevant Chemicals in No Observed Effect Test Water Case (mg/L) Fish: Oryzias javanicus

(28 dayNOEC) Crustacea: Hyale barbicornis

(21 dayNOEC) Algae: Skeletonema

costatum (78 h-NOEC)

Bromate ion 0.03 Bromoform: 0.0093 TRO (as O 3 ) 0.96 Seawater Generated TRO by Ozone Treatment (mg/L as O 3 ) 0.69 Before PT;10% After PT;100% Before PT;10% After PT;100% Before PT;10% After PT;100%

2.2.3 Endocrine disruption

Information about endocrine disr uption by Ozone and the Relevant Chemicals was not available presumably because from the standpoint of their st ructure it is unlikely to occur. Japan Ministry of Environment reports that these chemicals are not included in the list of chemicals expected to cause endocrine disruption (MOEís Perspective on Endocrine Disrupting Effects of Substances). As TRO represent the total mass of oxidants and is not a specific chemical, such data were not available.

2.2.4 Sediment toxicity

As Ozone is an inorganic compound and its half lif e is as short as 5.3 to 5.8 seconds in seawater and several minutes or several tens of minutes in fresh wa ter, it is unlikely to adhere to sediment or to accumulate in the sediment. Therefore sedi ment toxicity does not need to be considered.MEPC 59/2/1 ANNEX Page 18

I:\MEPC\59\2-1.doc Information about the toxicity eff ect of Bromate ions on benthic organisms was not available. As Bromate ions are water soluble and dissolve in wate r as ions, sediment toxi city is not applicable.

Information about toxicity effects of Bromof orm on benthic organisms was not available. As logPow of Bromoform is 2.4 smaller than L ogPow 3, which is applie d as an indication of adherence or accumulation, Bromoform is consid ered unlikely to cause sediment toxicity.

As the TRO represent the total mass of oxidants a nd is not a specific chemical, data were not available. The half life of TRO generated by the SP-Hybrid BWMS Ozone version is as short as 0.75 to 4.5 days and the TRO ar e considered unlikely to adhere to or accumulate in the sediment.

2.2.5 Bioavailability/biomagnification/bioconcentration

Table 2.2-9 showed bioavailability, biomagnifi cation and bioconcentration for Ozone as the Active Substance and Bromate ions, Bromof orm and TRO as Relevant Chemicals.

Information about bioavail ability/biomagnification/bio concentration of Ozone wa s not available. As Ozone is an inorgani c compound and its half life is as short as 5.3 to 5.8 seconds in water and several minutes to several tens of minutes in fresh wate r, bioavailability/biomagn ification/bioc oncentration are unlikely to occur.

As logPow of Bromate ion is as sma ll as -7.18 (SRC, 2007), biomagnification and bioconcentration are unlikely to occur.

According to the test for carp, which is a fresh water fish, exposed to 0.1 mg/L and 0.01 mg/L of Bromoform for 6 weeks, BCF showed 7.1 to 21 and 7.7 to 19, respectively, (NITE, 2007). Therefore, biomagnification and bioconcentration is unlikely to occur. Since Bromoform shows a small value of logPow equal to 2.4, this corresponds well to the above BCF.

As the TRO represent the total mass of oxidants and are not a specific chemical, data were not available. Since the half life of TRO generate d by SP-Hybrid BWMS Ozone version is as short as 0.75 to 4.5 days, biomagnification and bioconcentration is unlikely to occur.

Table 2.2-9: Bioavailability/biomagnif ication/bioconcentration of Ozone and Relevant Chemicals

Chemical

name logPow/BCF information Cause for

concern (Yes/No) Reference/Comments/ Justification for missing data

logPow N/A Ozone BCF N/A No Due to Ozone being an inorganic compound and having a short half life in the environment, there is no need for it to be considered logPow -7.18 Bromate ion BCF N/A No SRC, 2007
logPow 2.4

Bromoform BCF 0.1 mg/L: 7.1-21 0.01 mg/L: 7.7-19 No NITE, 2007

logPow N/A TRO BCF N/A No Due to the short half life of the TRO, there is no need for it to be considered.

N/A; Not AvailableMEPC 59/2/1 ANNEX Page 19

I:\MEPC\59\2-1.doc 2.2.6 Food web/population effects

As the half life of Ozone is as short as 5.3 to 5.8 seconds in seawater and several minutes to several tens of minutes in fresh water, it has little potential for bioaccumulation in organisms constituting the food web (algae, invertebrate and fish). Ther efore, the poten tial impact on the food web and population is considered to be minimal.

As the logPow of Bromate ions is extremely small (-7.18), its bioaccumulation potential in any organism constituting the food web (algae, invertebra te and fish), and its potential impact on the food web and population is considered to be minimal.

As the BCF of Bromoform is below 21, its bi oaccumulation in any organism constituting food web (algae, invertebrate and fish) is low and potential impact on the food web and population is considered to be minimal.

As the half life of TRO generated by SP-H ybrid BWMS Ozone version is as short as 0.75 to 4.5 days, biomagnification and bioconcentra tion are considered to be nil. The potential impact on the food web and population is considered to be minimal.

2.3 Data on mammalian toxicity (G9: 4.2.1.2)

Literature relating to mammalian toxicity for Ozone as Active Substance and Bromate ions, Bromoform and TRO as Relevant Chemicals of SP-Hybrid BWMS Ozone version were scrutinized. The information is summarized as follows:

.1 Active Substance

As Ozone causes strong toxicity through inhala tion exposure, stringent measures to protect human being from inhalation exposure of Oz one are required. Furt hermore, Ozone has the potential to cause mutagenic ity in humans. However, as no Ozone exists in the ballast tank and ballast water discharge of this system , the potential is considered to be nil.

.2 Bromate ion

Numerous studies indicate that potassium Bromate has the po tential for mutagenicity and carcinogenicity in humans. Based on the possi bility that Bromate ions may act as a mutative carcinogen, the United States curr ently regulates the maximum contaminant level of Bromate ion in the drinking water to 0.010 mg/L ( 10 μg/L ) with a target of zero (U.S. EPA, 2007). Therefore, exposure to Brom ate ion should be completely prevented. Considering the potential residue in the ba llast tank, shipboard personnel should be protected with protective clot hing at the time of entry to the tank. Though 0.70 mg/L of Bromate ions may exist in the discharge ballas t water in the worst scenario, the dilution after discharge causes little impact to the residents in the neighborhood.

.3 Bromoform

In an acute toxicity test where Bromofor m was given to laborat ory animals by oral administration, the LD 50 of mice was 707-1,550 mg/kg and th at of rats was 933-2,440 mg/kg. Inhibition of the central nervous system and effects on livers and kidne ys were observed. Inhibition of the central ner vous system and hepatopathy of humans caused by accidental ingestion was also reported. Its irritant propert y on eyes was low since it disappeared relatively quickly. Its irritant property on human skin and eyes was also reported.MEPC 59/2/1 ANNEX Page 20

I:\MEPC\59\2-1.doc The target organs of Bromoform in a repeated dose toxicity test were found to be the liver and kidney. In case target is given to imp act on liver (cavitation of liver cell) at one month oral dose (composite gavage) test using Wistar rats, LOAEL is 680 ppm (56.4 mg/kg/day). In a reproduction toxicity test, there was no impact up to a dose of 200 mg/kg/day.

Development toxicity tests also indicate th at doses up to 200 mg/kg/day have no fetotoxic effect and do not increase external malforma tion or disorders of the bone structure or internal organs.

In genetic toxicity tests in vitro using CHL cells and CHO cells, there was a contradictory result between a DNA damage test and a chro mosomal aberration test. Also, there were positive results in a DNA damage test using micro-organisms, a mutagenicity study, a chromosomal aberration test using Aspergillus nidulans and a mutagenicity study using mouse lymphoma cells. Furthermore, in vivo , an SCE test using mice and a micronucleus assay showed positive. From these results, it seems that Bromoform has genetic toxicity.

Though incidence of malignancy for mice did not increase in the oral administration tests, rats dosed with a large amount (200 mg/kg/day) showed substantial di fference in the rate of occurrence of tumors of the large inte stine. IARC concluded that there were inadequate human data and limited animal da ta and assigned Bromoform to weight of evidence category 3, which is not classifi able as to carcinogenicity in humans.

Considering the information on the mammalian toxicity of Bromoform, there does not appear to be a big risk considering that th e generated amount of Bromoform concentration generated by this system is very low, bei ng a maximum of 0.19 mg/L. However, since it potentially remains in the ballast tank, as in the case of Bromate ions, shipboard personnel should wear protective clothing when ente ring the tank. Tho ugh 0.018 mg/L Bromoform potentially remains in the ballast discharge in the worst scenario, it would have little impact on the residents in the neighbor hood because of dilution after discharge.

.4 Total Residual Oxidants (TRO)

As TRO represent the total mass of oxidants and are not a specific chemical, data were not available in the literature. However, as it has a potential to remain in the ballast tank, for reasons of personal safety shipboard pers onnel should wear prot ective clothing when entering the tank. Though 0.69 mg/L of TRO ge nerated by this BWMS potentially exists in the ballast water discharge in the worst scenario, it is considered to cause little impact on the population in the neighborhood due to dilution after discharge.

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

2.4.1 Modes of degradation (biotic; abiotic)

As Ozone is an unstable substance, it decomp oses into oxygen and water under aerobic and anaerobic conditions in addition to biodegradation. As Ozone degradation proceeds under anaerobic conditions, the generated oxygen may incr ease the concentration of dissolved oxygen. Hydrolysis does not occur.MEPC 59/2/1 ANNEX Page 21

I:\MEPC\59\2-1.doc Bromate ions are converted into bromide ions by microbe degradation under anaerobic conditions in the presence of methane bacteria, denitrification bacteria and sulfate reducers. Physicochemically, it reacts in the pr esence of ferrous ions (Siddiqui et al. , 1995 ) or activated
carbon ( Siddiqui et al ., 1996). It is also transformed to bromide ions in the presence of high energy electronic irradiation (Siddiqui et al. , 1996). Reaction by hydrol ysis does not occur.

In an aerobic biodegradation test based on the Japanese Domestic La w ìLaw Concerning the Examination and Regulation of Manufacture, etc ., of Chemical Substancesî, improved culture flasks for volatile substances were used with a concentration of the test substance of 100 mg/L, a concentration of activated sludge of 30 mg/L and a test period of 4 weeks. The degradation rate of Bromoform measured by biochemical oxygen consumption (BOD) measurement was 0%. Bromoform is therefore considered to be a persistent substance.

Furthermore, the degradation rate was also 0% according to gas chromatograph (GC) measurements (MITI, Japanese Government, 1986). On the other hand, one of the reports shows that biodegradation was confirmed in a case where the test substance was of lo w concentration and was naturalized for a prolonged period. In a test wh ere yeast extract was added to a broth for seven days at a test temperature of 25oC with test subs tance concentrations of 5 mg/L and 10 mg/L, the degradation rates measured by the Total Organic Carbon (TOC) concentration were 11% and 4%. Furthermore, in a test involvi ng repeated cultivations every 7 days, with a test substance concentration of 5 mg/L, the degr adation rate increased with progress of subcultures as follows: primary culture: 22%; s econdary culture: 40%; third culture: 48% (Tabak et al. , 1981). These results suggest that that biodegradation of Brom oform is strongly affect ed by its concentration and by the naturalization of micro-organisms, si nce the degree of aerobic biodegradation is high if its concentration is low and the start of the degradation curve is relatively late.

A report shows that low concentr ations of Bromoform (less th an 100 μg/L) were biodegraded under anaerobic conditions. More than 99% of Br omoform in an average initial concentration of 34 μg/L was decomposed in a column filled with carriers to which a methane producer had been attached in an environment with acet ate (retention time 2 days at 22 to 23oC) (Bouwer and McCarthy, 1983a). It is also reported that in a test where nitrite and nitrate were reduced to nitrogen and nitrogen monoxide by nitr ate respiration of denitrifying bacteria under anaerobic conditions (denitrifying condition), an initia l Bromoform concentration of 66 μg/L decreased to 59, 37, 35 and 2 μg/L after 2, 3, 4 and 6 week s, respectively, (Bouwer and McCarty, 1983b).

In conclusion, it is considered that Bromoform does not tend to be biodegraded under aerobic conditions. However, it is considered that Bromoform is biodegraded under conditions of low concentration, naturalization for a prolonged period, and others. It is also considered that Bromoform is biodegraded under anaerobic conditions if its concentration is low. Since no chemical bond of Bromoform is easily hydrolyzed, Bromoform itself is not hydrolyzed in water environment.

As TRO are not a specific chemical and represents the total mass of oxidant s, its degradation is difficult to determine. However, oxidants gene rated by reaction between seawater and Ozone are ultimately transformed to Bromate ions and Bromoform, which are treated as Relevant Chemicals of this system. The half life of TRO generated by the SP-Hybrid BWMS Ozone version was determined to be 0.75 to 4.5 days as a result of degradation tests.MEPC 59/2/1 ANNEX Page 22

I:\MEPC\59\2-1.doc 2.4.2 Bioaccumulation, partition coeffici ent, octanol/water partition coefficient

Table 2.2-9 summarized bioavailability/bioma gnification/bioconcentrationon for Ozone and Relevant Chemicals. Information about bioaccumulation of Ozone was not available. However, Ozone is an inorgani c substance and though its half lif e period depends on conditions of the environment, it is as s hort as 5.3 to 5.8 seconds in seawater and seve ral minutes to several tens of minutes in fresh water. Therefore, bioaccumulation is not applicable to Ozone.

As the logPow of Bromate ion is as low as -7.18 , Bromate ions are assumed not to bioaccumulate. According to the test for carp the maximu m BCF for Bromoform is 21 (NITE, 2007) and no bioaccumulation occurrence for Bromoform was de termined. The small value of 2.4 for the logPow of Bromoform corres ponds well to this result.

As TRO are not a specific chemical and represen ts the total mass of oxi dants, data were not available in the literature. However, the half life of TRO generated by SP-Hybrid BWMS Ozone version was determined to be 0.75 to 4.5 days thr ough the degradation test. This degradation rate prevents bioaccumulation.

2.4.3 Persistence and identification of the main metabolites in the relevant media (ballast water, sea and fresh water)

Table 2.4-1 identified the main metabolites for th e Active Substance and Relevant Chemicals and showed their persistence. Information was gather ed from the test with the same components and structure as SP-Hybrid BWMS Ozone version as a pplied to Guidelines (G8) land-based test but using the scaled down BWMS with 20 m3/h treatme nt rated capacity. Ballast water treated by this system is usually discharged through the DWTT. However, since the intention of this test was to examine ìpersistence (degradation) of chemi cals in the treated ballast waterî, the test was done by storing the treated ballast water in dar kness at a temperature of 25oC for 40 days and without passing it through the DWTT.

As the half life of Ozone is as short as 5.3 to 5.8 seconds in seawater and several minutes to several tens of minutes in fresh water, the Ozone decomposed within a short period and there was no Ozone in the ballast water discharge. Fu rthermore, this system adopts a Gas/Liquid Separation Tank to separate Ozone wh ich is not dissolved in ballast wa ter so that it does not exist or is not left in the ballast tank.

Relevant Chemicals are generated in the case wher e bromide ions exist in seawater or intake ballast water but not in fresh water where bromide ion does not exist.

As the half life of Bromate ions is lo nger than 40 days, it has high persistency.

As the half life of Bromoform is 32 to 185 days, it has high persistency.

As the half life of TRO is 1.3 to 4.5 days, it has low persistency. The half life in brackish water is even lower at 0.75 days.MEPC 59/2/1 ANNEX Page 23

I:\MEPC\59\2-1.doc Table 2.4-1: Persistence and Identification of Main Metabolites of Active Substance and Relevant Chemicals

Chemical

name Metabolites Method Results(halflife) Reference/Comments/ Justification for missing data

N/A N/A N/A Due to high degradation rate, Ozone does not exist in discharge ballast water. Ozone

N/A N/A N/A Due to high degradation rate, Ozone does not exist in discharge ballast water.

N/A 3 kinds of seawater (salinity: 29.7-32, pH:8.2-8.3, DO:10.6-12.6 mg/L, NTU: 1.1-1.9 ) treated by BWMS and stored at 25oC under darkness for 40 days >40 day Test result in Confidential version, Appendix 2

Bromate ions

N/A Brackish water (salinity:20.6, pH:7.8, DO:12.1 mg/L, NTU: 5.5 ) treated by BWMS and stored at 25oC under darkness for 40 days >40 day Test result in Confidential version, Appendix 2

N/A 3 kinds of seawater (salinity:29.7-32, pH:8.2-8.3, DO:10.6-12.6 mg/L, NTU: 1.1-1.9 ) treated by BWMS and stored at 25oC under darkness for 40 days 32.0- 185 day Test result in Confidential version, Appendix 2

Bromoform

N/A Brackish water (salinity:20.6, pH:7.8, DO:12.1 mg/L, NTU: 5.5 ) treated by BWMS and stored at 25oC under darkness for 40 days 34.7 day Test result in Confidential version, Appendix 2

N/A 3 kinds of seawater (salinity:29.7-32, pH:8.2-8.3, DO:10.6-12.6 mg/L, NTU: 1.1-1.9 ) treated by BWMS and stored at 25oC under darkness for 40 days 1.3-4.5 day Test result in Confidential version, Appendix 2

TRO

N/A Brackish water (salinity:20.6, pH:7.8, DO:12.1 mg/L, NTU: 5.5 ) treated by BWMS and stored at 25oC under darkness for 40 days 0.75 day Test result in Confidential version, Appendix 2

* N/A; Not Available

2.4.4 Reaction with organic matter

Table 2.4-2 showed the results of analysis fo r halogenated hydrocarbons in the test water produced for the additional chronic toxicity test. The concern is that halogenated hydrocarbons may be produced during the reaction with organic ma tter. However, according to the test result, the generation of halogenated hydrocarbon using the SP-Hybrid BWMS Ozone version was not confirmed.

Ozone reacts with organic matter before reacti ng with inorganic bromide ions and Ozone is consumed in the process. Consequently the am ount of Relevant Chemi cals generated by reaction between Ozone and bromide ions is reduced.MEPC 59/2/1 ANNEX Page 24

I:\MEPC\59\2-1.doc Bromate ions are oxidants and they ultimately reve rt to bromide ions thr ough reaction with organic matter (WHO, 1996) and by biodegra dation (Hijnen et al. , 1995). With regard to the relationship between the concentration of orga nic matter and the generated quantity of Bromate ions, the test result described in sectio n 2.4.3 of this document showed that in seawater where TOC concentration of the source water was f ound to be relative ly low (1.6 to 2. 0 mg/L), the genera tion concentration was 0.031 to 0.081 mg/L. However in brackish water wher e the TOC concentration was relatively high (2.1 mg/L), the generate d concentration was 0.027 mg/L.

Bromoform is a THM and hypobromous acid, which is precursor and inte rmediate product of THMs, is generated by reaction with organic ma tter. Bromoform does not react with organic matter due to its stable structure. With regard to the relationship between the concentration of organic matter and the amount of Bromoform gene ration, the test result described in section 2.4.3 of this document showed that the amount of Br omoform generated in brackish water (including water with a high TOC concentr ation) is low (0.033 mg/L) compar ed with seawater, where the concentration of Bromoform generated was 0.074 to 0.13 mg/L (the TOC concentration was relatively low in the intake water).

As the TRO represent the total mass of oxidants, it is not possible to identify how much of this reacts with organic matter. Generally oxidants su ch as Bromate ions, hypobromous acid ions and bromous acid ions increase the degradation rate of the TRO by reaction with organic matter. With regard to the relationshi p between the concentration of organic matter and the amount of generated Bromoform, the test result described in section 2.4.3 of this document showed that in seawater, where the TOC concentration of inta ke water was relatively low, the generated concentration was 0.62 to 1.4 mg/L but in bracki sh water, where the TOC concentration was relatively high (2.1 mg/L) the generated concentr ation was 0.48 mg/L lower than in seawater.

2.4.5 Potential physical effects on wildlife and benthic habitats

Regarding the potential physical effects on wildlif e and benthic habitats, the following is a summary based on various tests on the physical a nd chemical properties of the Active Substances and of preparations of treated ballast wate r (if applicable under G9: 4.2.1.4) described in section 2.5 of this dossier.

As Ozone disappears with self-degradation a nd by transformation to Relevant Chemicals immediately after injection into water, it has less potential to be discharged overboard. Therefore, there is little potential for physical effects on wildlife and benthic habitats.

Bromates have high solubility (70 g/L-20 oC ) and normally dissolve in water as ions. Even though ballast water after treatment may contain Bromat e ions, the maximum disc harge concentration is as low as 0.07 mg/L. If discharg ed, they revert to bromide ions by reaction with organic matter. Therefore, there is little potential for physi cal effects on wildlife and benthic habitats.

Due to its high volatility Bromoform dissipates in air and may have an impact on wildlife. Its emission concentration, however, is low because of low generated concentration and potential physical effects are considered to be marginal. Since the density of Bromoform dissolved in water is greater than water itself, Bromoform may have potential physical effects on wildlife and benthic habitats by sinking to the bottom. However, the maxi mum discharge concentration of Bromoform is as low as 0.19 mg/L so its discharge is considered to cause no potential physical impact, taking into consideration its diluti on in the environment and its half life.MEPC 59/2/1 ANNEX Page 25

I:\MEPC\59\2-1.doc 2.4.6 Potential residues in seafood

Since the half life of Ozone is as short as 5.3 to 5.8 seconds in seawater and several minutes to several tens of minutes in fres h water, it is considered to have no potential for accumulation in wildlife and benthic habitats. Th erefore, potential residues in seaf ood are considered to be nil.

Bromate ion can be cons idered to have no pote ntial physical effects on wildlife and benthic habitats.

Bromoform can be also considered to have no potential physical effects on wildlife and benthic habitats.

TRO can be considered to have no potential phys ical effects on wildlife and benthic habitats. Therefore, these can be considered that there are no potential residues in seafood.

2.4.7 Any known interactive effects

Table 2.4-3 showed any known interactive eff ects of the Active Substance and Relevant Chemicals.

When Ozone is decomposed in water, oxygen is generated, which results in an increase of concentration of dissolved oxygen in seawater.

Bromate ions are rarely reduced in the water envir onment. However, they revert to bromide ions in the presence of ferrous ions or activated carbon.

Bromoform is a relatively stable substance and is rarely deco mposed under aerobic conditions but reverts to methane bacteria under anaer obic conditions or is biodegraded during denitrogenation.

TRO are the mass of oxidants generated by reaction of Ozone with bromide ions in water and is ultimately transformed to Bromoform and bromide ions.

Table 2.4-2: Chemical concentrations in untre ated intake water and treated ballast water discharge in the repetition of the ch ronic toxicity test Seawater case

Items Untreated influent water Treated BWT water Treated discharge water Water Temperature ( °C ) Salinity (PSU) pH Dissolved oxygen (mg/L) POC (mg/L) DOC (mg/L) TSS (mg/L) 18.1 - 21.1 3.0 - 4.0 7.4 - 8.1 0.3 - 12.8 <0.1 - 1.0

1.0 - 1.1

7 - 9 17.7 - 21.7 31.0 - 33.5

7.3 - 8.1 11.3 - 19.9

-

-

- 17.9 - 21.7 31.0 - 33.5

7.5 - 8.2 13.3 - 19.9

-

-

- Bromate ion (mg/L) THMís Bromoform (mg/L) Chloroform (mg/L) Bromodichlotomethane (mg/L) Dibromochloromethane (mg/L) TRO (mg/L as O 3 ) Generated TRO by Ozone Treatment (mg/L as O 3 ) <0.01 <0.0001 <0.0001 <0.0001 <0.0001 0.23 - 0.90

- 0.022 - 0.10 0.076 - 0.17

<0.0001 <0.0001 <0.0001 - 0.0042 0.90 - 1.25 0.55 - 1.00 0.017 - 0.030 0.0001 - 0.0068 <0.0001 <0.0001 <0.0001 0.42 - 0.96 <0.15 - 0.69MEPC 59/2/1 ANNEX Page 26

I:\MEPC\59\2-1.doc Items Untreated influent water Treated BWT water Treated discharge water AOX (mg/L) Chlorophenols ( μ g/L) 2,3,4,5-Tetrachlorophenol Phenol Pentachlorophenol 4-Chlorophenol 3-Chlorophenol 3,5-Dichlorophenol 3,4-Dichlorophenol 3,4,5-Trichlorophenol 2-Chlorophenol 2,6-Dichlorophenol 2,4-u.2.5-Dichlorophenol 2,4,6-Trichlorophenol 2,4,5-Trichlorophenol 2,3-Dichlorophenol 2,3,6-Trichlorophenol 2,3,5-Trichlorophenol 2,3,5,6-Trichlorophenol 2,3,4-Trichlorophenol 2,3,4,6-Trichlorophenol 0.012 - 0.16

<0.1 0.4 - 0.5

<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 -

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

- 0.020 - 0.37

<0.1 0.3 - 0.7

<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

Table 2.4-3: Any known intera ctive effects of Active Subs tance and Relevant Chemicals

Substance Interaction with other chemicals, BWMS or receiving environment Discussion of potential effects Reference/ Comments

Ozone Relevant substances are generated by reaction of Ozone with seawater. Ozone does not exist in ballast water at discharge. Oxygen is generated by Ozone degradation. 2.1 in this document

Bromate ions (Potassium Bromate) They revert to bromide ions in presence of organic matter including ferrous ions and activated carbon. They revert to bromide ions by reaction with ferrous ions and activated carbon. Siddiqui (1995) Siddiqui (1996)

Bromoform It is a relatively stable substance and does not react with other chemicals. Anaerobic situation is assumed to occur in treated ballast water during treatment. Biodegradation is not likely either before discharge. Interactive effects in the environment of ballast discharge assume degradation by photolysis and bio-degradation under anaerobic conditions It is rare to be decomposed under aerobic condition and is biodegraded under anaerobic condition. Bouwer and McCarty, 1983a Bouwer and McCarty, 1983b

TRO It represents the total mass of oxidants generated by reaction of Ozone with bromide ions and is ultimately transformed to Bromoform and bromide ions. N/A Section 2.1 of this document

N/A; Not Available

2.5 Physical and chemical properties of th e Active Substances and preparations and treated ballast water, if applicable (G9: 4.2.1.4)

Tables 2.5-1 to 2.5-3 showed phys ical and chemical properties of the Active Substance and Relevant Chemicals. As TRO represents the tota l mass of oxidants and is not a specific chemical, data were not available.MEPC 59/2/1 ANNEX Page 27

I:\MEPC\59\2-1.doc Table 2.5-1: Physical and chemical pr operties of the Active Substance (Ozone)

Property Value Reference/Comments/ Justification for missing data

CAS number 10028-15-6 Ullmannís Encyclopedia of Industrial Chemistry Sixth Edition, 2001 Molecule weight 48.0 ISCS 1993
Liquid density 1358 g/L ( at -112 °C) Ullmannís Encyclopedia of Industrial Chemistry Sixth Edition, 2001
Evaporation heat 15.2kJ/moL Ullmannís Encyclopedia of Industrial Chemistry Sixth Edition, 2001 Melting point -193 °C ISCS 1993 Boiling point -112 °C ISCS 1993

Flammability Non-combustible but promotes burning of other substances. No inflammability to liquid. ISCS 1993

Density (20 °C ) 2.144g/L(N.T.P) (at 0 °C ,101kPa) Ullmannís Encyclopedia of Industrial Chemistry Sixth Edition, 2001 Vapour pressure (20 °C ) >1 atm ISCS 1993 Vapour density (air=1) 1.6 (air=1) ISCS 1993 Water solubility 0.1g/100mL ( at 0 °C) ISCS 1993 pH in solution N/A Exits as a gas Dissociation constant N/A Not applicable since Ozone is a gas.

Oxidation reduction potential 2.07V Ullmannís Encyclopedia of Industrial Chemistry Sixth Edition Section 2.Physical Properties P.39-P.40, June 2001

Corrosivity to Material Yes Ozone reacts with inorganic compounds including metals and organic compounds. See section 2.1, APPENDIX 1-1 (confidential dossier).

Reactivity to container material Yes Ozone reacts with inorganic compounds including metals and organic compounds. See section 2.1, APPENDIX 1-1.

Auto ignition temperature ( °C ) Non-combustible but promotes burning of other substances. Various reactions may cause a fire or explosion. Ozone reacts with inorganic compounds including metals and organic compounds. See section 2.1, APPENDIX 1-1.

Explosive Properties May cause a fire or explosion when heated or coming in contact with a combustible material (alkene, ether). ISCS 1993

Oxidizing properties Yes ISCS 1993

Surface tension 3.84×10 -2 N/mm (at -183 °C ) Refer to section 2.1 and APPENDIX 1-1
Viscosity 1.57×10 -3 Pa. s (at -183 °C ) Ullmannís Encyclopedia of Industrial Chemistry Sixth Edition, 2001 Thermal stability and breakdown product Oxygen Ullmannís Encyclopedia of Industrial Chemistry Sixth Edition, 2001 Other physical and chemical properties N/A Refer to section 2.1 and APPENDIX 1-1

* N/A; Not AvailableMEPC 59/2/1 ANNEX Page 28

I:\MEPC\59\2-1.doc Table 2.5-2: Physical and chemical properties of Relevant Chemicals: Bromate ions (Potassium Bromate)

Property Value Reference/Comments/ Justification for missing data CAS number 7758-01-2 WHO, 2005 Molecule weight 167.01 WHO, 2005 Liquid density N/A Not liquid but solid
Evaporation heat Not considered to be a fire hazard MSDS (APPENDIX 7-1-2)

Melting point 350 °C WHO, 2005 Boiling point 370 °C( decomposes ) WHO, 2005 Flammability Yes ICSC, 2003
Density (20 °C ) 3.27g/m 3 WHO, 2005 Vapour pressure (20 °C ) N/A MSDS (APPENDIX 7-1-2) Vapour density(air=1) N/A MSDS (APPENDIX 7-1-2)

Water solubility 70g/L(20 °C ) 133g/L(40 °C ) 498g/L(100 °C ) HydroChem Industrial Services, Inc.

pH in solution Not Found MSDS (APPENDIX 7-1-2) Dissociation constant Not Found WHO, 2005 Oxidation reduction potential 1.05V NTP 2008a Corrosivity to Material Yes NTP 2008a Reactivity to container material Yes MEPC 55/2 Auto ignition temperature ( °C ) No MEPC 55/2

Explosive Properties Risk of fire and explosion on contact with combustible, organic or other easily oxidizable materials. MEPC 55/2

Oxidizing properties Oxidizer HydroChem Industrial Services, Inc.

Surface tension Not Found Material Safety Data Sheet of Potassium Bromate Viscosity No ICSC, 2003 Thermal stability and breakdown product No HydroChem Industrial Services, Inc.

Other physical and chemical properties contact with combustible materials may cause fire. Incompatible with combustible material, organics, reducing agents, aluminium, finely powdered metals. The substance decomposes on heating or on burning producing toxic and corrosive fumes including bromine, and oxygen, which increases fire hazard. The substance is a strong oxidant and reacts violently with combustible and reducing materials, metal powder, fats, carbon, sulphur, phosphorus, ammonium salts, a nd metal sulphides causing fire and explosion hazard http://physchem.ox.ac. uk/MSDS/PO/potassiu m_Bromate.html http://www.itcilo.it/en glish/actrav/telearn/os h/ic/7758012.htm

* Values assuming the water viscosity coefficient at 0oC to be 100 (density, 14.02-34.64wt%).

* N/A; Not AvailableMEPC 59/2/1 ANNEX Page 29

I:\MEPC\59\2-1.doc Table 2.5-3: Physical and chemical pr operties of Relevant Ch emicals: Bromoform

Physical property Value Reference/Comments/ Justification for missing data CAS number 75-25-2 U.S. EPA 2005 Molecule weight 252.77 U.S. EPA 2005 Liquid density 2.899 g/mL(20 °C) U.S. EPA 2005 Evaporation heat 46.05 kJ/mol ATSDR 2005 Melting point 8 °C U.S. EPA 2005 Boiling point 149-150 °C U.S. EPA 2005 Flammability No ATSDR 2005 Density (20 °C ) 2.899 g/mL ATSDR 2005 Vapour pressure (20 °C ) 667 Pa NTP 2008b Vapour density (air=1) 8.7 NTP 2008b Water solubility 3190 mg/L(30 °C ) U.S. EPA 2005 pH in solution N/A Not hydrolyzed Dissociation constant N/A No dissociable group Oxidation-reduction potential N/A No ionization Corrosivity to Material Yes ATSDR 2005

Reactivity to container material Yes ATSDR 2005

Auto-ignition temperature ( °C ) - N/A
Explosive Properties Not considered to be an explosion hazard MSDS (APPENDIX 7-1-2)

Oxidizing properties N/A MSDS (APPENDIX 7-1-2) Surface tension 41.50mN/m(20 °C) NTP 2008b Viscosity 1.8 cP NTP 2008b
Thermal stability and breakdown product May form toxic fumes of bromides when heated to degradation MSDS (APPENDIX 7-1-2)

Other physical and chemical properties Volatilize ATSDR 2005

* N/A; Not Available

2.6 Analytical methods at environmentally relevant concentrations (G9: 4.2.1.5)

Table 2.6-1 showed measurement methods for Ozone as Active Substance and analytical methods for Relevant Chemicals.

Table 2.6-1: Analytical methods of Ac tive Substance and Relevant Chemicals at environmentally relevant concentrations

Substance Method Applicability Sensitivity Reference/ Comments/Justification for missing data

Ozone ・ UV method

・ KI method (as oxidant) for gas

for liquid 0.01 mg/L±1%FS ( UV method ) 0.15 mg/L

( KI method ) IOA Standardization Committee

Bromate ion IC + PC method for liquid 0.005 mg/L ISO 15061:2001

Bromoform PT-GC/MS method or HS-GC/MS method for liquid 0.0002 mg/L or 0.0001 mg/L drinking water test method in Japan *

TRO KI method for liquid 0.15 mg/L KI methodMEPC 59/2/1 ANNEX Page 30

I:\MEPC\59\2-1.doc 3 USE OF THE ACTIVE SUBSTANCE

3.1 Summary of SP-Hybrid BWMS Ozone version

SP-Hybrid BWMS Ozone version has been designe d taking the compactness, integration, safety and reliability of the system fully into c onsideration. Well established shipbuilding and evironmental technologies have been utilized for th is system and it is desi gned to be retrofitted easily on ballast piping of eith er new or existing vessels.

3.1.1 Components and outline

Figure 3.1-1 showed the configuration of SP- Hybrid BWMS Ozone version. Table 3.1-1 summarizes the arrangement of the main components.

Figure 3.1-1: Configuration of SP-Hybrid BWMS Ozone version S.C. Gas/Liquid Separation Control Panel

Pre

- Filter Gas/Liquid Separation Tank To ballast tank O.B.

Waste Ozone Destruction Unit

Special Pipe

( Slit plate ) Ballast Water Treatment Control Panel

Ballast Pump Ballast Control Panel

Ozone Generator Oxygen Generator Discharge Water Treatment Tank From ballast tank Inactivation Unit

Gas/Liquid Separation Unit Flow Meter Ozone Generator Module

Ozone Injector Flow of Ozone

Electric Control Wire

Ballast Line

TRO Sensor Post

- Treatment Unit Flow of Ozone (low concentration)

Flow of Oxygen

S.C. Gas/Liquid Separation Control Panel

Pre

- Filter Gas/Liquid Separation Tank To ballast tank O.B.

Waste Ozone Destruction Unit

Special Pipe

( Slit plate ) Ballast Water Treatment Control Panel

Ballast Pump Ballast Control Panel

Ozone Generator Oxygen Generator Discharge Water Treatment Tank From ballast tank Inactivation Unit

Gas/Liquid Separation Unit Flow Meter Ozone Generator Module

Ozone Injector Flow of Ozone

Electric Control Wire

Ballast Line

TRO Sensor Post

- Treatment Unit Flow of Ozone (low concentration)

Flow of OxygenMEPC 59/2/1 ANNEX Page 31

I:\MEPC\59\2-1.doc Table 3.1-1: Roles of major componen ts of SP-Hybrid BWMS Ozone version

Major components Outline

Ballast Water Treatment Control Panel Integrally controls the system. Allows start or stop of the system, displays alerts, and various operations. Operati on data for more than 2 years can be recorded.

Pre-Filter Positioned on the downstream side of th e ballast water intake port to remove relatively large size suspended substan ces in the ballast water to prevent clogging of the Special Pipe.

Flow Meter Measures the ballast water flow rate and outputs its data to Ozone Generator. The Ozone Generator calculates the Oz one production based on this data. (Accuracy of Flow Meter is ± 3% of measurement range).

Ozone Injector Positioned on the downstream side of Pr e-Filter and upstream side of Ballast Pump. Injects Ozone into incoming ballast water.

Ballast Pump High-pressure pump positioned on the downstream side of Ozone Injector and upstream side of the Special Pipe to cause enough shearing force and cavitation at the slit plates of the Special Pipe.
Special Pipe (Slit plate ) Consists of 2 pairs of slit plates positioned on the downstream side of Ballast Pump. Inactivates aquatic organisms by shearing force and cavitation caused by slit plate. Also functions to dissolve the Ozone effectively.
Ozone Generator Module Ozone Generator Oxygen Generator Generates oxygen with Oxygen Generator using compressed air and generates Ozone using such oxygen. Supplies Ozone to Ozone Injector.

Gas/Liquid Separation
Tank Positioned on the downstream side of Special Pipe to allow the injected Ozone to react with water and at the same time it separates gas from water.

Waste Ozone Destruction
Tank Positioned on the downstream side of the Gas/Liquid Separation Tank to convert the Ozone into oxygen using a catalyst and activated carbon when the gas from Gas/Liquid Separation Tank is discharged to the atmosphere. Discharge Water Treatment Tank (DWTT) Positioned immediately before the ball ast water outlet to remove Relevant Chemicals from the ballast water when discharged. Uses coconut husk charcoal as activated carbon.

TRO Sensor Installed immediately after DWTT. Measures TRO in the ballast water after passing through the DWTT and monitors TRO removal performance of DWTT. This sensor measures the TRO generated by the reaction of Ozone and seawater (Determination limit: 0.05 mg/L).

3.1.2 The characteristics

The features of the SP-Hybrid BWMS Ozone version are as follows:

.1 This system efficiently utilizes mechan ical shearing of the water and chemical effects of Ozone and Relevant Chemical s, which are generated by reaction of Ozone with bromide ions in seawater, in or der to inactivate organisms in the water.

.2 Since Ozone as the Active Substance is produced by the Ozon e Generator Module installed on board, it is not necessary to lo ad and store Active Substances or other chemical substances on board.

.3 The inactivation treatment of ballast water is only required at th e time of intake of ballast water.MEPC 59/2/1 ANNEX Page 32

I:\MEPC\59\2-1.doc .4 Most of the Relevant Chemicals genera ted by Ozone injection in seawater are degraded in the ballast water tanks. Ho wever, in the case of a short holding time Relevant Chemicals remain. In order to el iminate the residue of Relevant Chemicals, the DWTT is put in place. The discharge of ballast water is designed to go through the DWTT at any time. A TRO sensor is also installed right after the DWTT to survey its performance. This sensor m easures the TRO generated by the reaction of Ozone with seawater. If the meas ured TRO concentration exceeds 0.15 mg/L, an alarm is raised. Should the TRO c oncentration exceed the maximum allowable discharge concentrati on of 0.2 mg/L, the discharge is automatically stopped. This measure ensures the environmental safety of the ballast water. Installation of the DWTT and surveillance of the removal pe rformance by the TRO Sensor prevents migration of aquatic organisms th rough the ballast water and ensures environmental safety, which is the mo st important feature of this BWMS.

.5 Each major component and its valves are automatically operated or remotely controlled (remote operation) from the Balla st Water Treatment C ontrol Panel. The operating condition can be monitored on the di splay screen of this control panel. No manual operation of equipment or valves by the officers or crew is required except for maintenance or emergency operation, in the case of a serious failure.

.6 All possible safety measures have been made for Ozone leakage and waste Ozone

treatment.

.7 All possible measures have been taken agai nst corrosion for areas affected by Ozone.

3.1.3 Materials of major components

Ozone, which is an Active Substance, and all ot her Relevant Chemicals used with the SP-Hybrid BWMS Ozone version have corrosive effects. Therefore, corrosi on-proof materials should be used where corrosive effects are expected. However, fr om the results of variou s tests (land-based and on board tests), it can be judged th at there are no corrosive effect s due to Relevant Chemicals. So that, in this system, either stainless steel is adopted or a corrosion-proof coating is applied only against the corrosive effects of Ozone. Stainless steel is used for the Ozone Generator, Ozone Injector, and the Waste Ozone Destruction Unit. The piping from the Ozone Generator to Ozone Injector, the piping from the Oz one Injector to the Gas/Liquid Se paration Tank and the piping from the outlet of Gas/Liquid Separation Tank to the gas exhaust port are al so made of stainless steel. Consideration shall be given to prevent galvan ic corrosion between different kinds of metal.

3.1.4 Results of environmental tests of component units

Environmental tests for the electr ical and electronic equipment of a BWMS have to be carried out according to the Guidelines for approval of ba llast water management systems (G8) in order to secure its safety and reliability required for ma rine use. Therefore, environmental tests were conducted for the following components. The safety and reliability of ot her electronic equipment are secured by adopting type approved products of classification societies.

.1 Ballast Water Treatment Control Panel.

.2 Control Panel for Ozone Generator /Oxygen Generator.

.3 Ozone Generator Tube.MEPC 59/2/1 ANNEX Page 33

I:\MEPC\59\2-1.doc .4 Power Supply Unit for Ozone Generator.

.5 Ozone Leak Monitor.

.6 Flow Meter.

3.1.5 Approval of onboard system by Classification Society

The SP-Hybrid BWMS Ozone version was insta lled on a 4,600 TEU contai ner ship to conduct onboard tests. At the time of system insta llation, application drawings were submitted for approval to the American Bureau of Shipping (ABS), which registers this ship, and were approved. In the course of this application, th e comments of the ABS were incorporated and the system safety was improved.

3.2 The manner of application (G9: 4.2.6 and 7)

3.2.1 The maximum dosage concentration of Ozone

Ozone is injected to achieve 3 mg/L in the intake ballast water. As the amount of Ozone injection is automatically controlled , the Ozone concentrati on is maintained at 3 mg/L in the intake ballast water regardless of the flow rate. The Ozone concentration applied to the ballast water flow rate for Procedure (G9) application was 4 mg/L. The reason for this was to evaluate the effects on ships, human beings and the environment in a more seve re manner than by using 3 mg/L. This ensures a margin of safety when the syst em is actually in use. Various tests required for Procedure (G9) application were also conducted with 4 mg/L Ozone concentration in the ballast water.

3.2.2 Holding time

The holding time in the ballast tanks after the treatment with the SP-Hybrid BWMS Ozone version is not specified. The performance of the DWTT to remove Relevant Chemicals ensures that the concentration of Relevant Chemicals in the discharged ballast water does not exceed the maximum allowable discharge concentration of th e Relevant Chemicals even if the discharge occurs immediately after th e inactivation treatment.

3.2.3 The maximum allowable discharge concentration of the Relevant Chemicals

In accordance with the results of various tests, the maximum discha rge concentration of the Relevant Chemicals is 0.07 mg/L for Br omate ion, 0.018 mg/L for Brom oform and 0.69 mg/L for TRO (O 3 ) generated by Ozone treatment of this BWMS. Si nce many subsequent tests have resulted in higher TRO concentration th an the 0.15 mg/L (as O 3 ) presented at the time of the Basic Approval, the maximum discharge TRO concentration for this system should be revised to 0.69 mg/L. Also, Bromoform was defined as 0.19 mg/L taking into consideration the remova l performance of the DWTT (refer to section 3.2.5.2 of this document). Furthermore, the maximum discharge concentration of TRO (as O 3 ) to be applied (i.e. the maximum al lowable discharge concentration for actual operation of th e BWMS) was defined as 0.2 mg/L TRO (as O 3 ) generated by Ozone treatment of this BWMS as an independent index in order to provide bette r protection of the environment.

3.2.4 Handling, use, storage and transport of the chemicals

As Ozone, the Active Substance, is produced by the Ozone Generator Module installed on board a vessel, there is no need to transport, load and store either the Active Substance or other chemicals on board.MEPC 59/2/1 ANNEX Page 34

I:\MEPC\59\2-1.doc 3.2.5 Procedures and use of the system

3.2.5.1 Ballasting operation

Operation at intake is automated by the Ballast Water Treatment Control Pa nel and Ozone is also produced automatically to achieve 3 mg/L in th e loading ballast water, by measuring the flow rate with the Flow Meter. Even when the ballas t water flow rate varies excessively, the system has the required Ozone injection capacity, which is based on the predicted maximum water flow rate. When a serious failure occurs in one of the major components such as the Ozone Generator or the Ballast Pump or if an a bnormal value for pressure or water flow rate is shown, the system is automatically stopped and an alarm is activated.

Operation at discharge is automatically executed by the Ballast Water Treatment Control Panel. When an instruction to discharge ballast water is given, the valves are automatically opened and the ballast water discharge line flowing through the DWTT is established. Arbitrary action by the officers and crew cannot interfere with this line. The performance of the DWTT is secured by using an automatic valve to discharge the effluent. Clogging of the DWTT is prevented by reversing the direction of water flow. The TRO Sensor is installed right after the DWTT to survey TRO concentration constantly. If th e measured TRO concentration exceeds 0.15 mg/L, an alarm is raised to check the amount of ac tivated carbon in the DWTT. Should the TRO concentration exceed the maximum allowable disc harge concentration of 0.2 mg/L, the discharge is automatically stopped. The TRO concentration is automatically recorded by the Ballast Water Treatment Control Panel.

3.2.5.2 Maintenance and inspection

Maintenance and inspection invol ves the exchange of activated carbon used in the DWTT. Activated carbon is excha nged at the time of periodi cal surveys of the ship.

In the case of a medium size bulk carrier (Ha ndy Max BC) engaged in a tramp service, which seems to have the longest annual deballasting ti me among typical vessels, the annual discharge time amounts to 690 hours on the assumption that ba llast water is discharg ed for 15 hours with a frequency of discharge of once every 8 days. Ba sed on 3 years as the l ongest interval between periodical surveys, the total discharge time during that period is 2,070 hours.

The results of performance tests on the removal of Relevant Chemic als, which involved 230 hours of continuous operation of the DWTT showed that the concentration of Bromate ions in the discharged ballast water was stable throughout the test. This result was obtai ned in spite of the low removal performance for Bromate and high re moval performance for TRO. Ther efore, the removal efficiency for these two substances is confirmed to stay co nstant for the period betw een periodical surveys.

The Bromoform removal ratio, however, decreased fr om 99% at the beginning of the test to 85% after 230 hours of operati on. This reduction of rem oval ratio presumably re sults from a decrease of adsorption capacity of the activ ated carbon. However, even if the removal ratio decreases in the case that no Bromoform removed, the PEC/PNEC ra tio in the maximum discharge concentration of 0.19 mg/L is well below 1 and it was confir med that there is no environmental effect.

3.2.6 Risk management measures in case of emergency

If there is a fire or other emergency, the whol e system of SP-Hybrid BWMS Ozone version may be shut down by an emergency stop button located in the engine room or the area of Ozone Generator Module. When a fire alarm activated, the Ozone Genera tor Module automatically stops.MEPC 59/2/1 ANNEX Page 35

I:\MEPC\59\2-1.doc 3.2.7 Other safety measures

If Ozone is detected by one of the Ozone Leak M onitors located at several points, an audible and visible alarm is raised and the Ozone Generator Module automatically stops. Other measures are also put in place such as inst allation of the Ozone Generator Module in an enclosure with sufficient ventilation, a notice on the bulletin board and provision of protective clothing and protective masks.

3.2.8 Control of discharge water and countermeasures

The SP-Hybrid BWMS Ozone version is designed to discharge ballast water after all the residual Relevant Chemicals are removed by the DWTT. The removal performance of the DWTT is ensured by exchanging the activated carbon at the time of periodical surveys. If the measured TRO concentration exceeds 0.15 mg/L according to the sensor installed ne xt to the DWTT, an alarm is raised to check the amount of activated carbon in the DWTT. Should the TRO concentration exceed 0.2 mg/L, the discharge is automatically brought to a standstill. These measures ensure that the maximum allo wable discharge concentration of TRO.

3.2.9 Waste control and recycle

With the SP-Hybrid BWMS Ozone version, wastes are generated by pre-filter backwash. Since the backwash water is returned to the same wate r, there is no problem. Another waste is the removed activated carbon used in the Discharge Water Treatmen t Tank. The removed activated carbon is to be properly treated (recycled) according to the ìBasel Convention on the Control of Transboundary Movements of Hazardous Wastes and their Disposalî.

4 MATERIAL SAFETY DAT A SHEETS (G9: 4.2.7)

The MSDS for Ozone, which is the Active Subs tance of SP-Hybrid BWMS Ozone version, and for Relevant Chemicals are submitted.

5 RISK CHARACTERIZATION

5.1 Screening for persistence, bioaccu mulation and toxicity (G9: 5.1)

5.1.1 Persistence (G9: 5.1.1.1)

There is no persistence because th e half life of Ozone as the Activ e Substance, and of the TRO as Relevant Chemicals are extremely short in wate r. However as the half life of Bromate ions and Bromoform as Relevant Chemicals is not le ss than 40 days and 32 to 185 days, respectively, they have persistence.

5.1.2 Bioaccumulation (G9: 5.1.1.2)

As Ozone, the Active Substance, is an inorgani c compound and its half life in water environment is short, there is no bioaccumulation. As descri bed in section 2.2.5 of this document, Bromoform, Bromate ion and TRO as Relevant Chemicals do not bioaccumulate.MEPC 59/2/1 ANNEX Page 36

I:\MEPC\59\2-1.doc 5.1.3 Toxicity test (G9: 5.1.2.3)

Toxicity is determined by having a chronic t oxicity value of less th an 0.01 mg/L NOEC. As Ozone has an chronic toxicity NOEC of 0.002 mg /L, it is considered to be toxic. As the chronic toxicity NOEC for Bromate ions and chronic toxicity NOEC (MATC) for Bromoform are 0.125 mg/L and 4.8 mg/L, respectively, both these Relevant Chemicals are considered to be non-toxic. As the chronic toxicity test of TRO using treated ballast water showed 0.96 mg/L TRO (as O 3 ) and the test result using sample water containing 0.69 mg/L TRO (as O 3 ) generated by Ozone treatment of this BWMS showed no eff ect, it is also considered to be non-toxic.

5.1.4 Do the Ozone and Relevant Chemical s meet all three criteria for PBT?

In view of the above results, the following Ta ble 5.1-1 summarized PBT of the Active Substance and Relevant Chemicals of the SP-Hybrid BWMS Ozone version. The Active Substance and Relevant Chemicals of this system ar e not considered to be PBT substances.

Table 5.1-1: PBT of Active Substance and Relevant Chemicals

Persistent (y/n) Bioaccumulation (y/n) Toxic (y/n) Reference/ Comments/ Justification for

missing data

PBT criteria Half-life:> 60 days in seawater, or> 40 days in freshwater or > 180 days in seawater sediments, or> 120 days in freshwater sediments Experimentally determined BCF > 2000, or if no experimentally BCF has been determined, Log Pow>3 Toxicity Chronic NOEC < 0.01 mg/L

Ozone N N Y Sections 2.2.2, 2.2.5, 2.4 of this document

Bromate ion Y N N Sections 2.2.2, 2.2.5, 2.4 of this document

Bromoform Y N N Sections 2.2.2, 2.2.5, 2.4 of this document

TRO N N N Sections 2.2.2, 2.2.5, 2.4 of this document

6 EVALUATION OF THE TREATED BALLAST WATER (G9: 5.2)

6.1 Tests of the treated ballast water implem ented for the purpose of Final Approval

6.1.1 Outline of tests

.1 Acute toxicity test using full-scale land- based test facility described in 6.1.2.1 of this document:

Acute toxicity test for treated ballast water (ballast water discharge) using full-scale (200 m3/h treatment capacity) system for Guidelines (G8) land-based test of SP-Hybrid BWMS Ozone version.MEPC 59/2/1 ANNEX Page 37

I:\MEPC\59\2-1.doc .2 Repetition of chronic toxicity test usi ng small-scale test facility described in paragraph 6.1.2.2 of this document:

Chronic toxicity test including measuremen t and evaluation of Relevant Chemicals such as Bromoform reco mmended by GESAMP-BWWG (MEPC 55/2/16, annex 5).

.3 Degradation test for generated Relevant Chemicals using small- scale test facility described in paragraph 6.1.2.2 of this document:

Identification of Relevant Chemicals generated when Ozone is injected to seawater by SP-Hybrid BWMS Ozone version, pred iction of the amounts and degradation test on assumption that they are held in the ballast tank.

.4 Removal test for generated Relevant Ch emicals using small-scale test facility described in paragraph 6.1.2.2 of this document:

Test to confirm removal performance of DWTT for Relevant Chemicals generated by SP-Hybrid BWMS zone version.

.5 Long-term performance test of DWTT by us ing small-scale test facility described in paragraph 6.1.2.2 of this document:

Test to confirm removal performance for Relevant Chemicals in case of operating DWTT for 24 days totalling 230 hours.

6.1.2 Test facilities

Various tests were conducted by using two kinds of test facility according to the purpose of tests.

6.1.2.1 Full-scale land-based test facility

This is a test facility with treatment capacity 200 m3/h arranged for Guid elines (G8) land-based test of SP-Hybrid BWMS Ozone version.

6.1.2.2 Small-scale test facility

This facility has 20 m3/h treatm ent water flow rate and has fundamentally the same structure and components as the full-scale land-b ased test facility. Since the difference from the full-scale land-based test facility is the water treatment rate only, the reaction with seawater, the kind and concentration of Relevant Chemicals gene rated, and the kind and concentration of Relevant Chemicals in the ballast water discharge can be considered to be the same as in the full-scale land-based test facility.

6.1.3 Justification of test facilities

SP-Hybrid BWMS Ozone version is designed to render organi sms harmless by oxidation by the injection of Ozone into the ballast water and by disinfection by Relevant Chemicals generated by the reaction of Ozone with the ballast water. Therefore, in the case of variations in time from Ozone injection to the evaluation for wate r quality and disinfection effect (reaction time), differences may arise in the disinfection effect or in the amount of Relevant Chemicals generated. In order not to create contradiction between the small-scale test facility and the full-scale land-based test facility, the same reaction time a nd treatment time have been applied to each test.MEPC 59/2/1 ANNEX Page 38

I:\MEPC\59\2-1.doc Table 6.1-1: Scale of test facilities and reaction time

TRC Ozone injection method Reaction time (From Ozone Injector to the exit of Gas/Liquid Separation Tank) Full-scale land-based test facility 200 m 3 /h Aeration tube About 61 seconds

Small-scale test facility 20 m 3 /h Aeration tube About 59 seconds

6.1.4 Quality control of test

Full-scale land-based acute toxicity test, the repet ition of chronic toxicity test and the degradation test for Relevant Chemicals were conducted under the surveillance of ìIDEA Consultants, Inc.î in accordance with OECDís GLP standard ìOEC D Principles of Good Laboratory Practiceî (1997). Their affidavit for confidence assurance is attached. The analysis of Relevant Chemicals for other tests was conducted by IDEA Consultants, Inc.

6.2 Full-scale land-based acute toxicity test (G9: 5.2.2)

The full-scale land-based acute toxicity test wa s applied to the treated ballast water discharge prepared in the same manner as the full-scale land-based test for SP-Hybrid BWMS Ozone version in accordance with Guid elines (G8). The acute toxicity test using test organisms was conducted in order to calculate th e 50% lethal c oncentration (LC 50 or 50% effect concentration
rate ECr 50 ) and No Observed Acute Effect Concentration ( NOAEC ) for test organisms. The test facility used for this test was the full-scale land-based test facility with 200 m3/h flow rate arranged for the G8 land-based test.

The test organisms are all marine species consisting of Oryzias javanicus (fish), Hyale barbicornis (crustacea) and Skeletonema costatum (algae).

Ozone was injected to achieve 4 mg/L concentr ation in the intake ballast water (200m3/h).

The test water exposed to each test organism was the ballast water which was treated by Ozone injection and then immediately discha rged without retention via the DWTT.

After sampling, the test wa ter was immediately tr ansported in darkness to th e IDEA Consultants, Inc. Exposure started within 8 hours from sampling.

The test intake water to the system conformed to the conditions of sea a nd brackish test water specified in Guidelines (G8) land-based test. Though Guidelines (G8) require 5 mg/L for DOC for the test using brackish water, the concentration was 2.4 mg/L, which is just under half this value. However, since the sum of TOC and POC was 12.6 mg/L, which is higher than the 10 mg/L the total value of POC and DOC sp ecified in Guidelines (G8), this DOC value should be of no concern for the purpose of implem enting the test in an environment with highly concentrated organic matter.

After the sampled test water was transported to the toxicity laboratory, it was diluted by various different amounts before exposure to the test organisms. There was no other treatment or filtration of the sampled water. The discharge water was diluted to achieve the following concentrations: 100%, 50%, 25%, 12.5% and 6.3% (v/v). Natural seawater was used for dilution.MEPC 59/2/1 ANNEX Page 39

I:\MEPC\59\2-1.doc The same untreated test intake wa ter was also exposed to each test organism as a reference. The result of this reference test wa s not applied to calculation of LC 50 , ECr 50 or NOAEC.

The acute toxicity test for each test organism was conducted in accordance with the following guidelines:

.1 Fish; Oryzias javanicus

OECD Chemical Test Guideline No.203 ìF ish, Acute Toxicity Testî (1992) and U.S. EPA Guideline ìMethods for Measuri ng the Acute Toxicity of Effluents and Receiving Waters to Freshwater and Ma rine Organisms, Fifth Editionî (2002).

.2 Crustacea; Hyale barbicornis

U.S. EPA Guideline ìGammarid Acute Toxicity Testî (1996) ìMethods for Measuring the Acute Toxicity of Effluent s and Receiving Waters to Freshwater and Marine Organisms, Fifth Editionî (2002).

.3 Algae; Skeletonema costatum

ISO 10253 ìWater quality -Marine alg ae growth inhibition test with Skeletonema

costatum and Phaeodactylum tricornutum, Second editionî (2006) and U.S. EPA Guideline ìMethods for Measuring the Acut e Toxicity of Effluents and Receiving Waters to Freshwater and Marine Organisms, Fifth Editionî (2002).

Table 6.2-1 showed the results of the acute toxicity test water and the con centrations of Relevant Chemicals in the exposed water. No acute toxicity effect was observed in the test using seawater. An acute toxicity effect for brackish water was observed in the tests with Hyale barbicornis

, crustacea, at 96 h LC 50 : 71% and 96 h NOAEC: 50%, with Skeletonema costatum , algae, at 72 h NOAEC: 50%. However, it is not appropriate to judge from this test result only that treated ballast water discharged from SP- Hybrid BWMS Ozone version posse sses acute toxicity. Taking into consideration that the result was a ffected by oxygen consumption by decomposition of organic matter in the brackish water test, it was considered that the treated ballast water discharged from the SP-Hybrid BWMS Ozone version had no acute toxicity effect.

Table 6.2-1: Result of acute toxicity test using full-scale land-b ased test facility

Concentration of Relevant Chemicals in test solutions (mg/L)

Test water Test organisms Endpoint Results Bromate ion Bromoform TRO (as O 3 ) Generated TRO by

Ozone Treatment (mg/L as O 3 ) 96h - LC 50 >100% Fish: Oryzias javanicus 96h NOAEC 100%

96h -LC 50 >100% Crustacea: Hyale barbicornis 96h-NOAEC 100%

72h -ECr 50 >100% Seawater

Algae: Skeletonema

costatum 72h -NOAEC 100% 0.07 0.0023 0.54 - 0.85 <0.15MEPC 59/2/1 ANNEX Page 40

I:\MEPC\59\2-1.doc Concentration of Relevant Chemicals in test solutions (mg/L)

Test water Test organisms Endpoint Results Bromate ion Bromoform TRO (as O 3 ) Generated TRO by

Ozone Treatment (mg/L as O 3 ) 96h-LC 50 >100% Fish: Oryzias javanicus 96h-NOAEC 100%

96h -LC 50 71% Crustacea: Hyale barbicornis 96h-NOAEC 50%

72h -ECr 50 >100% Brackish
water Algae: Skeletonema

costatum 72hNOAEC 25% 0.04 0.015 0.93 - 1.18 <0.15

6.3 Repetition of chronic toxicity test (G9: 5.2.1)

Chronic toxicity tests for the treated ballast water discharged from SP-Hybrid BWMS Ozone version were originally conducted at the time of application for G9 Basic Approval both for the case of discharge after 48-hour retention at tank without using DWTT and for the case of discharge through the DWTT without retenti on at tank (refer to document MEPC 55/2).

It was reported that the TRO concentration in the ballast water discharge after removal of Relevant Chemicals by the DWTT was always under 0.15 mg/L, despite the conclusion of NOEC >0.16 mg/L(O 3 ) for TRO. With regard to this report, the GESAMP-BWWG pointed out the need to clarify the toxicity relationship be tween the discharge and the Relevant Chemicals such as Bromate ion and Bromoform (MEPC 55/2/16, annex 5). Taking into account this comment, a second chronic toxicity test includi ng measurements of Relevant Chemicals in the test water was conducted.

The test facility with 20 m3/h treatment rated capacity had th e same structure and components, and possibly the same concentrati ons of Relevant Chemicals in th e ballast water discharge as the test facility used for the full-scale land-based test.

The test organisms were all marine species consisting of Oryzias javanicus (fish), Hyale barbicornis (crustacea) and Skeltonema costarum (algae), which were the identical species to those in the full-scale land-based acute toxicity test.

Ozone was injected to achieve 4 mg/L in the intake ballast water (20 m3/h).

The following test water samples we re exposed to test organisms:

.1 control (original water before dilution);

.2 test water without removal of Rele vant Chemicals by the DWTT immediately after treatment by Ozone injection (zero holding time) ñ Four samples were made (a) undiluted sample (100%), dilu ted samples of (b) 10%, (c) 3.125% and (d) 1% concentration (v/v); andMEPC 59/2/1 ANNEX Page 41

I:\MEPC\59\2-1.doc .3 ballast water discharge with Rele vant Chemicals removed in the DWTT immediately Ozone injection (zero holding time) ñ Two samples were made (a) no dilution (treated discharge water 100%) and (b) 10% concentration (v/v).

The test water was transported to the IDEA Consultants, Inc., toxi city test labora tory under cool and dark conditions immediately after sampling. Exposure started within 24 hours after sampling. Test water flowing in the system met the seawater test conditions specified according to Guidelines (G8). As stated in section 6.2 of this document, in the case of Guidelines (G8) land-based test using brackish water, the d ecrease of DOC by the decomposition of highly concentrated organic matter may have influenced the result of the toxicity test. This is the reason why seawater was used for the test. A higher concentration of Relevant Chemicals is generated in the test water used for exposure if the concentration of the organic matter is lower.

After sampling, the test water was transported to the toxicity la boratory and samples of various dilutions were prepared prior to exposure to test organisms. Transported test water was used for adjusting test water at each expos ure area without treatment by f iltration. Dilution was applied to natural seawater filtered through 3 μm diameter filter. Natural seawater used for dilution was exposed to each test organism for control.

Chronic toxicity tests for each test organism we re conducted with test methods specified in the following guidelines:

.1 Fish; Oryzias javanicus

OECD Guideline for the testing of chemi cals No.215: Fish, Juvenile Growth Test (2000); U.S. EPA: Short-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Ma rine and Estuarine Organisms, Third Edition (2002).

.2 Crustacea; Hyale barbicornis

Method with reference to Anasco et al . (2005)

U.S. EPA: Short-term Methods for Estima ting the Chronic Toxicity of Effluents and Receiving Waters to Marine and Estu arine Organisms, Third Edition (2002).

.3 Algae; Skeletonema costatum

ISO 10253: Water quality ñ Mari ne algae growth inhibitio n test with Skeletonema costatum and Phaeodactylum tricornutum, Second edition (2006).

Table 6.3-1 showed the no observed effect concentrat ion of treated ballast water in the additional chronic toxicity test and the maximum concentr ation of Relevant Chem icals at exposure time.

The maximum concentration of detectable Rele vant Chemicals in the test water which was considered to be the no observed effect concentr ation in this test was: Bromate ions: 0.03 mg/L, Bromoform: 0.0093 mg/L, TRO: 0.96 mg/L, and TRO (as O 3 ) generated by ballast water treatment of this BWMS: 0.69 mg/L. The concen trations of Bromate ions and Bromoform fell far short of the aforementioned existing NOEC a nd MATC and resulted in supporting both data.MEPC 59/2/1 ANNEX Page 42

I:\MEPC\59\2-1.doc Table 6.3-1: NOEC at chronic toxici ty test and maximum concentration at time of exposure

Test water Max. concentration of Relevant Chemicals in No Observes Effect Test Water Case (mg/L) Fish: Oryzias javanicus

(28 day NOEC) Crustacea: Hyale barbicornis

(21 day NOEC) Algae: Skeletonema

costatum (78 h NOEC)

Bromate ion 0.03 Bromoform: 0.0093 TRO (as O 3 ) 0.96 Seawater Generated TRO by Ozone Treatment (mg/L as O 3 ) 0.69 Before PT:10% After PT:100% Before PT:10% After PT:100% Before PT:10% After PT:100%

* PT; Post Treatment

6.4 Degradation test for ge nerated Relevant Chemicals

A degradation test was conducted by identifying Relevant Chemicals generated at the time of Ozone injection into seawater and brackish wa ter by the SP-Hybrid BW MS Ozone version and by assuming the amount generated and retained in the ballast tank. The sma ll-scale test facility (20 m3/h) was used, however, the DWTT was not used in the degradation tests. The test water consisted of four samples using three kinds of seawater and one of brackish water.

The test showed that three substances, Br omate ions, Bromoform and TRO, which were identified as Relevant Chemicals, were generated when Ozone was injected into the ballast water in such a manner to achieve 4 mg/L Ozone. It was also found that the half life of Bromate ions was longer than 40 days and that the half liv es of Bromoform and TRO were 32 to 185 days and 0.75 to 4.5 days, respectively.

6.5 Removal test for generated Relevant Chemicals

The intention of this test was to confirm the removal performance of Relevant Chemicals by the DWTT, which is the most importa nt equipment of SP-Hy brid BWMS Ozone vers ion for the removal of Relevant Chemicals from the ballast water disc harge. Ozone was injected in such manner as to achieve 4 mg/L Ozone in the intake ballast wate r. The small-scale test facility was used. The water quality of the original test water used fo r the land-based test usi ng the small-scale test facility was identical to the water quality for inta ke water specified for the land-based test in the Guidelines (G8).

Table 6.5-1 showed the Bromate ion concentration at each sampling point. Bromate ions in the source water (A) was less than the determination limit (< 0.01 mg/L). Th ough 0.053 to 0.061 mg/L Bromate ion was generated by the Ozone treatmen t, it did not show much change during the elapsed time. Since the Bromate ion concentrat ion remained in the ra nge of 0.050 to 0.058 mg/L even after treatment by the DWTT, so it had little effect on removal.

Table 6.5-2 showed the Bromoform concentrati on at each sampling point. The Bromoform concentration in the source wa ter (A) was less than the de termination limit (<0.0002 mg/L). Bromoform increased to 0.13 to 0.14 mg/L obviously by generation and its concentration during the retention period after treatment also increa sed to 0.18 to 0.19 mg/L. Bromoform post-treated by the DWTT decreased remarkably to near the determination limit (0.0003 to 0.0009 mg/L). Therefore, it was proved that the performance of the DWTT in the removal of Bromoform was close to 100%.MEPC 59/2/1 ANNEX Page 43

I:\MEPC\59\2-1.doc Table 6.5-3 showed the TRO concentration at e ach sampling point. TRO was detected in the sample of test source water (A), which indicates that there exists oxidant detectable as TRO in the background when natural seawater is measured with the KI method. It was found that after this test source water had been treated with Ozone by this BWMS, the TRO increased. After passing through the DWTT, the TRO was reduced to the level of test source water (natural seawater). Therefore, the DWTT is considered to have a thorough removal effect on TRO.

Table 6.5-1: Bromate ion concentrations in the test water collected from (A) raw water, (B) Gas/Liquid Separati on Tank, and (C) downstream of DWTT

- : No measurement

Table 6.5-2: Bromoform concentrations in the test water collected from (A) source water, (B) Gas/Liquid Separation Tank, and (C) downstream of discharge water treatment unit

The day after treatment Ozonation at: (Water used for treatment) Run Sampling point Day-1 Day-2 Day-3

A <0.0002 - - B 0.14 0.19 0.18 #1 C 0.0006 0.0003 0.0003 A <0.0002 - - B 0.13 0.13 0.18 4.0 mg/L (Seawater) #2 C 0.0009 0.0004 0.0003

- : No measurement

Table 6.5-3(1): TRO(as O 3 ) concentrations in the test water collected from (A) original water, (B) Gas/Liquid Separation Tank, and (C) downstream of DWTT

The day after treatment Ozonation at: (Water used for treatment) Run Sampling point Day-1 Day-2 Day-3

A 0.29 0.40 0.38 B 1.25 1.09 0.88 #1 C 0.37 0.50 0.46 A 0.32 0.36 0.32 B 1.36 1.16 0.92 4.0 mg/L (Seawater) #2 C 0.38 0.46 0.43MEPC 59/2/1 ANNEX Page 44

I:\MEPC\59\2-1.doc Table 6.5-3(2): Generated TRO( as O 3 ) concentrations by Ozone Treatment in the test water collected from (A) original water, (B) Gas/Liquid Separation Tank, and (C) downstream of DWTT

The day after treatment Ozonation at: (Water used for treatment) Run Sampling point Day-1 Day-2 Day-3

A <0.15 - - B 0.96 0.69 0.50 #1 C <0.15 <0.15 <0.15 A <0.15 - - B 1.04 0.80 0.60 4.0 mg/L (Seawater) #2 C <0.15 <0.15 <0.15

- : No measurement

6.6 Long-term performance test of Discharge Water Treatment Tank

This test was conducted in order to obtain data to cons ider the sustainable time of the removal performance of Relevant Chemicals by DWTT, na mely time to exchange the activated carbon installed in the tank. The small-scale test facili ty was used. Test source water was collected from seawater in the bay in front of the test facility. The operation wa s continuous for about 10 hours a day for 24 days and totalled 230 hours. Th e sampling points were at 3 locations, namely the original intake water, before DWTT and after discharge treatment tank (ballast water discharge). Ozone was injected on ballasting in such manner to achieve an Ozone concentration of 4 mg/L. When the DWTT runs in actual opera tion, the flow direction changes at the time of ballast water discharge but in this test run th e flow was in the same direction for 230 hours.

Table 6.6-1 showed measurement results for Relevant Chemicals. Though the removal performance for Bromate ions was low, the gene rated concentration as well as the discharge concentration remained stable all through the test. The removal effect of the DWTT was maintained even after 230 hours of operation.

Therefore, the performance of DWTT for these two Relevant Chemicals does not appear to decrease even after a long and continuous oper ation. However the removal performance for Bromoform decreased as time passed since the 99% removal at the start of the test was reduced to 85% after 230 hours. In case of ballast water discharge, the Bromoform concentration after the DWTT started with 0.002 mg/L and ended up at about 10 times this figure, namely 0.018 mg/L, after 230 hours. It is considered that a reducti on in the adsorption capacity of the activated carbon caused the decrease of in the removal performance.MEPC 59/2/1 ANNEX Page 45

I:\MEPC\59\2-1.doc Table 6.6-1: Observation result of Relevant Chemicals by long operation of a replicate process of DWTT

6.7 Determination of holding time

The holding time following ballast water treatment is not specified. The ballast water can be discharged immediately after treatment.

6.8 Risk characterization and analysis

6.8.1 Reaction with organic matter (G9: 4.2.1.3)

With regard to the formation of halogenated hydrocarbons, which may occur in the reaction with organic matter, untreated intake water, which was prepared for the repetiti on of chroni c toxicity test described in section 6.5 of this document, a nd ballast water discharge water were analysed. As described in section 2.4.4 of this document, this resulted in the finding that no halogenated hydrocarbons existed in the ballast water discharge. With regard to trihalomethanes generated by the reaction of Ozone with organic matter in seawater, the generation of Bromoform as a Relevant Chemical and small amounts of dibromochliromethane may occur.

Bromoform generated in comparatively large amounts is treated as a Relevant Chemical and various risk assessments were conducted on this compound. The maximum generated dibromochloromethane was 0.0049 mg/L, which is about 1/20 of 0.1 mg/L, which is the WHO Dri nking Water Standard (WHO, 1996). Most of this small amount of dibromochloromethane was removed in the DWTT and its maximum concentration in the ballast wate r discharge was 0.0002 mg/L , but the concentration was too small to be detected in most of the tests.Th erefore, it is considered to cause no risk to the environment. As TRO mainly consist of oxidants, it is decomposed by react ion with organic matter.

6.8.2 Characterization of degradat ion route and rate (G9: 5.3.5)

Details about the decomposition of Active Substa nces and Relevant Chemicals under abiotic and biotic environment are described in section 2.4.1 of this document. Ozone as the Active Substance is completely decomposed or eliminated by Gas/Liquid Separation Tank in the SP-Hybrid BWMS Ozone version. Cumulative treatment time(h) 0 20 40 90 158 230 Original Water (Un t reated intake water) <0.01 <0.01 <0.01 <0.01 <0.01 <0.01

before DWTT 0.02 0.02 0.02 <0.01 0.02 0.01 Bromate ion (mg/L) after DWTT 0.02 0.02 0.02 <0.01 0.02 0.01 Original Water (Untreated intake water) <0.0001 0.0001 0.0001 <0.0001 0.0002 <0.0001

before DWTT 0.1700 0.1600 0.1400 0.0890 0.1300 0.1200 Bromoform (mg/L)
after DWTT 0.0020 0.0035 0.0054 0.0067 0.0110 0.0180 Original Water (Untreated intake water) 0.21 0.30 0.25 0.22 0.33 0.33

before DWTT 2.53 2.28 2.05 1.12 2.03 1.91 Generated TRO by Ozone Treatment 2.33 1.98 1.80 0.90 1.70 1.58

after DWTT 0.42 0.35 0.46 0.29 0.47 0.40 TRO (mg/L as O 3 )

Generated TRO by Ozone Treatmen t <0.15 <0.15 0.21 <0.15 <0.15 <0.15MEPC 59/2/1 ANNEX Page 46

I:\MEPC\59\2-1.doc The half life of Bromate ions as a Relevant Chemical is l onger than 40 da ys and little decomposition occurs even in the DWTT. T hough the half life of Bromoform is as long as 32 to 185 days, most of the Bromoform is d ecomposed by the DWTT. The half life of TRO are 0.75 to 4.5 days and the DWTT eliminates most of it.

6.9 Prediction of discharge and environmental concentrations

The predicted environmental concentration (P EC) of Bromate ions, Bromoform and TRO of Relevant Chemicals contained in the ballast water discharged from SP-Hybrid BWMS Ozone version was predicted by using the MAMPEC m odel ver. 2.0 as applied to the Port of Tokyo as described below.

6.9.1 Discharge concentration of Relevant Chemicals

The following summarizes the maximum discha rge concentration of Bromate ion, Bromoform and TRO as Relevant Chemicals discharged fr om SP-Hybrid BWMS Ozone version determined by various tests:

With reference to TRO (O 3 ), 0.2 mg/L was independently de fined as the maximum allowable discharge concentration for actua l operation to provide better protection of the environment:

.1 Bromate ion: 0.07 mg/L .2 Bromoform:0.19 mg/L .3 TRO: 0.69 mg/L.

As TRO (as O 3 ) are more properly evaluated by using TR O generated by this BWMS rather than direct values analysed by the KI method, the va lue based on the subtraction of the concentration in the ballast water (untreated intake water) from the concentration in the ballast water discharged from DWTT was used for the following reasons:

.1 TRO which was analysed by the KI met hod specified in section 2.6 of this document is usually detected in natural seawater with subs tantial oxidants. For example, the full-scale land-based acute toxicity test described in section 6.2 of this document detected 0.44 to 0.73 mg/L TRO in natural se awater prior to treatment (prior to Ozone in jection). Many tests conducte d in the past resulted in affirming the findings of TRO in natural seawater as well.

.2 TRO concentration in natural seawater can be considered to cause no impact to aquatic organisms.

.3 PEC and PNEC were predicted by usi ng 0.44 to 0.73 mg/L TRO concentration in natural seawater. As the concentration detected as TRO in natural seawater resulted from dissipation and decompositi on, PEC remained the same. PNEC was predicted by using the toxicity of Bromate ion constituting a part of TRO. PNEC of Bromate ion is assumed to be 30 μg /L for PNEC long and 300 μg/L for PNEC short as described in 6.11.1 of this document.

.4 PEC/PNEC long and PEC/PNEC short are assumed to be 730/30=25.5 and 730/300=2.55. PEC/PNEC of natural seawater far exceeds 1.0, which may lead to the conclusion that TRO in natural seawater causes a substantial environmental impact.MEPC 59/2/1 ANNEX Page 47

I:\MEPC\59\2-1.doc .5 Environmental evaluation for ballast wa ter discharge should be performed on the substances generated by ballast water treatment and ultimately discharged.

.6 It is appropriate to evaluate the e nvironmental effect of TRO generated and discharged by SP-Hybrid BWMS Ozone version on the assumption that the environmental concentration is 0 μg/L excluding TRO in natural seawater.

6.9.2 Target port and the designated se a area for the estimation of PEC

The Port of Tokyo was selected as a target since accurate calculation parameters such as geomorphology, tide, water quality and benthics n ecessary for prediction are available and it has been visited by most ships in Japan. If the mooring areas for ships engaged on international voyages which are covered by the International Convention for the Control and Management of Shipsí Ballast Water and Sediments, 2004 were se lected as the designate d sea area, the results would be underestimated for the following reasons . Therefore, the sea area was limited to the area around a container pier of the Port of Tokyo.

.1 About 80% of ships engaged on internatio nal voyages calling in the Port of Tokyo are container ships (out of a total of 4,726 ships engaged on international voyages calling in the Port of Tokyo, 3,952 ships are container ships).

.2 Container piers for international trade st and close together in certain areas. (equivalent to about 25% of total sea area around be rthing space for ships engaged on international voyages).

.3 About 85% of annual ballast water discha rge at the Port of Tokyo is discharged from container ships.

6.9.2.1 Scale of harbour facilities in designated sea area

The container piers for internatio nal trade at the Port of Tokyo c onsists of three container piers and a berth allowing berthing of 15 ships with a total area of 1,504,718 m 2

.
6.9.2.2 Tidal current in designated sea area

The tide in the designated area flows to north-north west (or to the south-southeast on the opposite tide) in parallel with the fairwa y route with approximate speed of 0.4 to 0.9 knots (0.2 to 0.5 m/s).

6.9.2.3 Amount of ballast water discharge in the designated sea area

The intake and discharge of ballast water in the designate d area amounts totally to 1,378,117 m 3 annually. 1,888 m 3 /day ballast water is estimated to be discharged.

6.9.2.4 Number of ships calling po rts in the designated sea area

The number of visiting ships amounts to 3,952 annually.

6.9.2.5 Ship mooring frequency in designated sea area

Most of the container ships are in regular liner service and the time of entrance into port for each route has been usually evenly-assigned. As they are moored to each berth everyday (open 24 hours) at the Port of Tokyo, it leads to the calculated result: 3,952 ships (calling annually)/365 days/15 berths = 0.72 ships/day/berth.MEPC 59/2/1 ANNEX Page 48

I:\MEPC\59\2-1.doc 6.9.3 Calculation conditions of PEC

6.9.3.1 Dimensions and properties of the environment

The area for the predictive calculation was limite d to the sea area around the berthing space of the container pier for internati onal trade specified in the aforem entioned section 6.9.2. The area is 3.5 km long x 1.4 km wide. Table 6.9-1 summari zes the environmental conditions such as tide and water quality which were used for the calculation.

Table 6.9-1: Calculation and environm ental conditions at the designated sea area of the Port of Tokyo

Environmental conditions Layout Tidal period 12 hour Length x1 x2 350 m 3,500 m Silt concentration 35 mg/L Width y1 y2 1,400 m 140 m POC concentration DOC concentration 1 mgOC/L 2 mg/L Depth 10 m Chlorophyll 3 mg/L Salinity 34 s.e. Mouth width 3,500 m

Temperature 15 °C
Latitude 35 degree NH Flow velocity(F) 0.35 m/s

pH 8 Depth mixed sediment layer 2.3 m Sediment density 2,800 kg/m 3 Fraction organic Carbon in sediment 0.032

Net sedimentation Velocity 1.2 m/d Exchange volume 1.08E+7 m 3 /tide 22.04% tide

6.9.3.2 Background concentration of the Relevant Chemicals

As Bromate ions and Bromoform do not norma lly exist in the natural environment unless artificially introduced, their background con centration was considered to be 0 μg/L.

The backgound concentration of TRO were also cons iderd to be 0 μg/L for the reasons given in section 6.9.1 of this document.

6.9.3.3 Condition of the discharge ballast water

6.9.3.3.1 Concentration of Relevant Chemicals

The following maximum discharge concentrations are shown in section 6.9.1 of this document:

.1 Bromate ion: 0.07 mg/L (132 g/d) .2 Bromoform: 0.19 mg/L (359 g/d) .3 TRO( as O 3 ): 0.69 mg/L (1,303 g/d).

6.9.3.3.2 Physical input values of Relevant Chemicals

Physical input values of Relevant Chemical s required for prediction calculations using the MAMPEC model was set up in accordance with info rmation in chapter 2 of this document. As TRO represent the total mass of oxid ants and accurate physical data are not available, Bromate ion data were substituted, except for the degradation ra te (expressed in terms of half life), which was obtained from the test.MEPC 59/2/1 ANNEX Page 49

I:\MEPC\59\2-1.doc 6.9.4 Calculation results

Table 6.9-2 showed computation results of MAMP EC for the Relevant Chemicals discharged from SP-Hybrid BWMS Ozone version based on the application to the Port of Tokyo.

This computation indicated the following pred icted environmental co ncentration (PEC):

.1 PEC of Bromate ion :0.00517 μ g/L
.2 PEC of Bromoform :0.0113 μ g/L .3 PEC of TRO( as O3) :0.0432 μ g/L

Table 6.9-2: Result of prediction using MAMPEC model ver. 2.0 for the Port of Tokyo

6.10 Assessment of potential for bioaccumulation

Referring to section 2.4.2 in this document, the LogPow of Releva nt Chemicals discharged from SP-Hybrid BWMS Ozone version is -7.18 for Br omate ions and 2.4 for Bromoform. Though the TRO represent the total mass of oxidants and th e octanol/water partition coefficient is not available, it is considered to run under logPow 3 which indicated to cause bioaccumulation due to its short half life. Therefore, bioaccumu lation is not caused by the Relevant Chemicals discharged from the SP-Hybrid BWMS Ozone version.

6.11 Effects assessment

The maximum concentration of Relevant Chem icals discharged from the SP-Hybrid BWMS Ozone version is 0.07 mg/L for Bromate ions , 0.19 mg/L for Bromoform, 1.18 mg/L for TRO and no more than 0.69 mg/L for TRO (O 3 ) generated by the Ozone treatment of this BWMS.

With reference to TRO (O 3 ), 0.2 mg/L was independently de fined as the maximum allowable discharge concentration for actua l operation to provide better protection of the environment.

The acute toxicity value of Relevant Chemicals as described in section 2.2.1 of this document far exceeds these discharge concentrations. As show n in section 2.2.2 of this document, the chronic toxicity value NOEC also far exceeds those disc harge concentrations. According to the acute toxicity test (section 6.2 of this document) a nd the chronic toxicity te st (section 6.3 of this document) for ballast water discharged from this system, the results of bot h cases showed there is no potential for toxicity effect in the ballast wate r discharge. As summarized in section 6.9, bioaccumulation of the Relevant Chemicals is unlikely to occur and any effect of toxicity resulting from accumulation through the food web is also unlikely to take place.

From the above standpoint, the Relevant Chem icals discharged from the SP-Hybrid BWMS Ozone version are considered not to cause impact on the environment either in short term or in the long term. PEC of Relevant Chemicals (μ g/ L ) Bromate ion Bromoform TRO(as O 3 ) Maximum concentration 0.00875 0.0195 0.0740 95% concentration 0.00806 0.0179 0.0682 Average concentration 0.00517 0.0113 0.0432 Median concentration 0.00517 0.0112 0.0427 Minimum concentration 0.00112 0.0025 0.0093MEPC 59/2/1 ANNEX Page 50

I:\MEPC\59\2-1.doc 6.12 Effects on aquatic organisms

6.12.1 Estimated PNEC

The PNEC of Relevant Chemi cals discharged from the SP-H ybrid BWMS Ozone version is determined as follows:

.1 Bromate ion: LC 50 or EC 50 for three marine species are required and its minimum concentration for 96 h EC 50 is 30 mg/L. If the assessm ent factor is set at 1,000 for long and 100 for short, PNEC long is 30 μg/L and PNEC short is 300 μg/L.

.2 LC 50 or EC 50 for total five marine species and four freshwater species are required and its minimum concentration is 7.1 mg/L for 96h LC 50 . If the assessment factor is set at 1,000 for long and 100 for short, PNEC long is 7.1 μg/L and PNEC short is 71 μg/L.

.3 TRO: As TRO represent the total mass of oxi dants, toxicity data are not available. Therefore, the PNEC was calculated by using the result of the acute toxicity test and the chronic toxicity tests for 3 marine species in sections 6.2 and 6.3 of this document. An acute toxicity effect was not observed in the acute toxicity test with a maximum concentration of 0.85 mg/L a nd at the maximum TRO concentration generated by this BWMS (less than 0.15 mg/L). Therefore, if the assessment factor is set at 10, PNEC short is >16 μg/L (as O 3 ). In the chronic toxicity test the NOEC was evaluated as 100% (no dilution) of the c oncentration for ballast water discharge. The maximum TRO concentration generate d by this BWMS was 0.69 mg/L for this case. If the assessm ent factor is set at 100, PNEC long is 6.9 μg/L(as O 3 ).

6.12.2 PEC/PNEC ratio

Based on the PEC calculated in section 6.9 of this document and the PNEC assumed in section 6.12.1, PEC/PNEC was computed a nd its result is shown in Table 6.12-1.

PEC/PNEC of Relevant Chemicals discharged from SP-Hybrid BWMS Ozone version falls far below 1.0.

Table 6.12-1: PEC, PNEC and ratio of PEC/PNEC

PNEC( μ g/L) PEC/PNEC Relevant Chemicals PEC( μ g/L) long short long short Bromate ion 0.00517 30 300 0.000172 0.0000172

Bromoform 0.0113 7.1 71 0.00159 0.000159 TRO ( as O 3 ) 0.0432 6.9 >16 0.00626 0.00270

6.13 Effects on sediment

As described in this document, section 2.2.4, any Relevant Chemical discharged from SP-Hybrid BWMS Ozone version is unlikely to cause adhesi on or accumulation in the sediment. Therefore, it can be considered that th ere is no effect on sediment.MEPC 59/2/1 ANNEX Page 51

I:\MEPC\59\2-1.doc 6.14 Comparison of effect assessm ent with discharge toxicity

Evaluation of the treated ballast wa ter summarized section 6 of this document is identical to the finding that neither acute toxicity nor chronic t oxicity has been observed in the various tests on ballast water discharged from this system.

7 RISK ASSESSMENT

7.1 Risk to safety of ship

7.1.1 Increased corrosion

One of main concerns about safety to ships with this system is the possible corrosive effect of Ozone on the hull and the equipment. As Ozone is a strong oxidizing agent, corrosion-resistant materials should be selected.

The area requiring corrosion protection is iden tified by electro-chemical measurements and corrosion tests (refer to document MEPC 55/2) and measures to use corrosion resistant materials such as stainless steel have been put in place. Th is section reports the resu lts of an investigation of corrosion effects at the identifie d areas, in which corrosion resistant material is used, as well as in other representative areas.

7.1.1.1 Confirmation of corrosion condition on board

This system with 300 m3/h trea tment capacity has been already installed on board a container vessel in order to gather various data and is actually in operation. A corrosion assessment was conducted after 8 monthsí operation.

7.1.1.1.1 Ballast tank

A visual survey of corrosion befo re operation and again after 8 m onthsí operation of this system was conducted in the ballast tank where particular corrosion prevention meas ures were not put in place. The result showed no diff erence in corrosion between before operation and after 8 monthsí operation of this system, which confir med that there was no corrosion effect.

7.1.1.1.2 Ozone Injector

Corrosion-resistant stainless steel was used for the Ozone Injector where Ozone is injected into the ballasting line. No corrosion effect was obser ved as a result of visual inspection including the connecting pipes.

7.1.1.1.3 Special Pipe

The Special Pipe, which is a core item of equipment of this system designed to inactivate aquatic organisms, comes into contact with highly concen trated Ozone. This ite m was also made from corrosion resistant stainless steel. Visual insp ection after 8 months of operation showed no corrosion effect on the Special Pi pe or on the connecting pipes.MEPC 59/2/1 ANNEX Page 52

I:\MEPC\59\2-1.doc 7.1.1.1.4 Casing and impeller of Ballast Pump

The Ballast Pump located in the middle of Ozone Injector and Special Pipe also comes in contact with highly concentrated Ozone. Bronze and stainless steel were used for the casing of the Ballast Pump and impeller. No corrosi on effect was observed in a visual inspection after 8 monthsí operation.

7.1.1.1.5 Conclusion of the result of corrosion condition inspected on board

As described above, the SP-Hybrid BWMS Ozone ve rsion was visually insp ected 8 months after the beginning of the operation. The absence of corrosion was confirmed both in the ballast tank, where the corrosion-control measures were judged not to be necessary at th e application of Basic Approval, and in the equipment, where the corrosi on-control measures were required due to contact with a high concentration of Oz one. Therefore, the materials described in paragraph 3.1.3 are considered to be unaffected by Ozone corrosion.

7.1.2 Fire and explosion

Generally speaking, the major risk s with ships are fire and flood. Regarding fire, safety is enhanced by implementing the following measures:

.1 In case of fire occurring in the engine room or in another room where the Ozone Generator is installed, the Ozone Generato r can be stopped from outside the room; and

.2 In case of a fire alarm, the electric po wer supply to Ozone Generator will be shut down immediately to halt pr oduction of Ozone which woul d otherwise help the fire.

7.1.3 Storage and handling of the substances

The SP-Hybrid BWMS Ozone version uses Ozone as the Active Substance, which is generated by the Ozone Generator Module installed on board. There is no need to store and handle the Active Substance on board, which reduces the risk.

7.1.4 Contact with, or inhalation of, process products

Ozone as Active Substance and the Relevant Chemicals may cause the following potential risk to shipboard personnel when this system operates:

.1 hazard to respiratory organ by inhalation of Ozone; and

.2 hazard to eye and dermis by contact with Ozone and Relevant Chemicals.

This system applies the following measures to mi nimize all potential risks. As mentioned by the GESAMP-BWWG at the time of the Basic Approval (MEPC 55/2/16, annex 5), Bromoform (one of the Relevant Chemicals) is volatil e and may cause exposure effects on shipboard personnel. The air in ballast tank was sampled immediately follo wing operation of this system, and the Bromoform concentration in the sampling air was analysed. The measured concentration was less than the lower limit of 0.019 μg/m3, wh ich shows that the Bromoform concentration would have no effect on shipboard personnel.MEPC 59/2/1 ANNEX Page 53

I:\MEPC\59\2-1.doc 7.1.4.1 Countermeasures for Ozone leakage

This system is equipped with Ozone Leak Monito rs located at the Ozone Generator, near the Ozone Injector and near the Waste Ozone Destruc tion unit so that Ozone leakage can be always under surveillance. If leakage be detected, a visible and audi ble alarm is raised, the Ozone Generator is stopped and the evacu ation of shipboard personnel is urged. Portable Ozone Leak Monitors are installed on board so that the Oz one concentration can be measured by shipboard personnel at appropriate locations and inhalation of air containi ng Ozone can be prevented. Goggles and protective masks are also provided on board. Caution plates are located near the Ozone Leak Monitors to draw attention to the hazard.

As Ozone is a strong oxidizing substance, appropri ate materials are used where Ozone is present so that the integrity of the system is maintained and Ozone leakage is prevented.

7.1.4.2 Safety measures of compon ents constituting the system

This system sufficiently ensures safety to shipbo ard personnel with robust quality control of each component constituting the system including use of corrosion resistant materials, ventilation by mechanical exhaust fans, surveillance based on the working environmental standards for Ozone, automatic stoppage on failure, visible and audible alarms, preparation of caution plates, etc.

7.1.5 Noise

The noise of this system was measured when th e installed on board syst em was operating. The result was below 110 dB(A) which is the noise limit for ìMachinery spaces (not continuously manned)î thereby ensuring safety to shipboard personnel.

7.2 Risk to human health

7.2.1 Health effects in humans (G9: 5.3.12)

The health effect scenario in humans (exc ept for shipboard personne l) is estimated by consideration of the seafood web and the ecosystem . As the ballast water discharge from this system is unlikely to cause any impact on the envi ronment, however, this route has a little risk. As described in section 7.1.4, Bromoform is poten tially dissipated from the ballast tank. When the Bromoform was measured, it was under the detectable limit 0.019 μg /m3 and was not at a level to affect human health. Therefore, vol atile Bromoform has no ri sk to human health.

Though residual Bromate ion and TRO in the ballast water are unlikely to affect human health during inspection of the ballast tank, protective equipment is worn during inspection to avoid any risk.

Health effects in humans were summarized as fo llows, making reference to the method specified in the Methodology (MEPC 57/2/10, annex 4, appendix 2).

7.2.2 Human Exposure Scenario (HES) (G9: 6.3.3)

A third party organization conducted an assessme nt of the exposure to humans of the Active Substance and Relevant Chemicals of this system . A summary of results is described below.MEPC 59/2/1 ANNEX Page 54

I:\MEPC\59\2-1.doc 7.2.2.1 Ozone

As the half life of Ozone in water is short, the potential exposure to shipboard personnel is considered to be very low level and temporary. The effects on respiratory organs by inhalation exposure and mutation are the co ncerns. However, implementa tion of safety measures as described in section 7.1 of this document decrease the risk to shipboard personnel. As there is little potential for exposure to the general public, the risk is low.

7.2.2.2 Bromate ion

The maximum Bromate ion concentration in the ba llast water collected from the experiment was 0.07 mg/L after treatment by this system. As it exists as ions in water, the exposure to humans through the air is unlikely to occur. Due to the low bioconcentration factor the risk of exposure to shipboard personnel and to the general public thr ough consumption of seafood is extremely low. Since from the stan dpoint of toxicity it is regard ed as carcinogenic, the exposure to humans especially chronic exposure should be avoided by all means. Therefore, protective equipment should be worn during inspection of the ballast tank.

7.2.2.3 Bromoform

7.2.2.3.1 Risk of exposure to shipboard perso nnel by volatility from ballast water

Exposure of shipboard personnel to Bromoform is expected to be caused by the volatilization from the ballast water.

The maximum concentration of Bromoform in the balla st water is 0.19 mg/L, and about 3.25% of it is expected to transfer into the atmosphere a ccording to the environmen tal distribution prediction based on Mackey Level III, which takes into account the half-life of Bromoform in water (t 1/2 = 185 days as the maximum) (see Table 7.2-1). For a typical ship, th e volume of the ballast water taken on board is normally ca 15,000 m 3 and the gas volume in the headspace of the ballast water tank is ca 5,000 m 3 . According to the expected dist ribution patterns based on Mackey Level III, 3.25% of Bromoform di stributes into the atmosphere, and the Bromoform concentration in air in the ballast tank can be calculated as 0.0185 mg/L = 0.0185 g/m 3 using the equation below:

0.19 mg/L × 0.0325 × (15,000 m 3 /5,000 m 3 ) = 0.0185 mg/L = 0.0185 g/m 3

Assuming, as the worst case, that the Bromoform dissipate s into the atmosphere (inboard) and stays in the ship without being diluted, it is possible that the shipboard personnel could be exposed to Bromoform vapour of about 0.0185 g/m 3 . When a member of shipboard personnel works in the ballast tank on maintenance and other activities, th e work normally takes 5 hours and is performed once a month. Assuming that the weight of the worker is 60 kg a nd the volume of breath is 10 m 3 for an activity lasting 5 hours, e xposure of Bromoform to shipboa rd personnel is estimated to be 3.088 mg/kg for one activity of this kind. The acu te toxicity value of Bromoform obtained from the study using rats is 1,147 mg/kg (LD 50 ). Using the acute toxicity value of 1,147 mg/kg and the estimated exposure, the Margin of Safety (MOS) can be calculated as more than 370. Based on the obtained MOS of more than 370, the ri sk of acute exposure for shipboard personnel in the ballast tank is very low.

On the other hand, the chronic hazard of Brom oform (NOAEL: No Observed Adverse Effect Level) is reported as 25 mg/kg/ day based on the 13-week study of ra ts. As for the chronic risk assessment for shipboard personnel who work in the ballast water tank, the daily exposure value is calculated as 0.103 mg/kg/da y since the activity is normally performed once a monthMEPC 59/2/1 ANNEX Page 55

I:\MEPC\59\2-1.doc (3.088 mg/kg/30day = 0.103 mg/kg/day). Compari ng the hazard data from animal studies (NOAEL = 25 mg/kg/day) and estimated exposure le vel to the shipboard pe rsonnel in the ballast water tank (0.103 mg/kg/day), the MOS is more than 240 and so there is no concern on the health risk of the shipboard personnel in the ballast water tank.

The living space in the ship is ca 1,600 m 3 . Assuming that the living space is directly connected to the headspace of the ballast tank, the concentr ation of Bromoform in the living space would be diluted to 75% of the concentration in th e ballast tank (5,000/(5,000 + 1,600) = ca 0.75; 0.0185 × 0.75 = 0.0139 g/m 3 ). In the living space, a continuous ventilation system is installed and the lowest ventilation rate is 78 m 3 /min when a cooling unit is worki ng. Therefore, air in the living space is replaced with fresh air every 20 minutes and the Bromoform concentration should be diluted 72 times a day from the original concen tration. Assuming that th e exposure to shipboard personnel is 24 hours a day, the daily breathing volume is 20m 3 /day, the weight of personnel is 60 kg, the daily exposure volume is calculate d as 0.064 mg/kg/day using the equation below:

0.0139 g/m 3 × 1/72 × 20 m 3 × 1/60kg = 0.064 mg/kg/day

Comparing the estimated exposure value of 0.064 mg/kg/day and hazard data of 25 mg/kg/day (NOAEL from 13 weeksí study of ra ts), the MOS is more than 390, so no health risk for the shipboard personnel is expected.

Table 7.2-1: Estimated environmental distribution of Bromoform according to Mackey Level III

Mass Amount (%) Half-life (hr) Emissions (kg/hr)
Air 3.25 17 0
Water 96.6 4,440 (185 days) 1000
Soil 0.0147 170 0 Sediment 0.115 170 0

7.2.2.3.2 Atmospheric risk from Bromoform vap or from the treated ballast water

Bromoform may vaporize into the atmosphere during th e ballast water treatment and discharge. It is reported that the half-life of Bromoform vaporized into the atmosphere is 66 hours (IARC, 1991). It is also reported that the concentration of Bromoform in the atmosphere (background level) of marine areas is between 6.2 and 4.8 μg/m 3 (IARC, 1991). The predicted environmental concentration (PEC) during the ballast water di scharge was determined to be 0.0113 μg/L by the MAMPEC model calculation. Assuming that no dilution occurs in the atmosphere and 3.25% of the Bromoform vaporizes into the atmosphere based on the Mackey Level III calculation, the concentration in the atmosphere is determined to be 0.367 μg/m 3 . This concentration is much lower than the background level, and there should be no health ri sk caused by volatilization into the atmosphere. Furthermore, it is normally expected that vaporized Bromoform should be diluted into the atmosphere as much as hundred s to thousands of times , and the concentration should be much lower than the estimated value, ther efore, no risk to the gene ral public is expected.

7.2.2.3.3 Risk of Bromoform exposure to public health via sea food

The maximum generated concentration of Bromof orm is 0.19 mg/L and th at concentration is assumed to be the maximum discharging concen tration in the seawater. Using the maximum concentration of 0.19 mg/L, the predicted environm ental concentration (PEC ) is determined toMEPC 59/2/1 ANNEX Page 56

I:\MEPC\59\2-1.doc be 0.0113 μg/L by the MAMPEC model calculation. As a worst ca se scenario, the intake amount of Bromoform to the general pub lic can be estimated using the calculated PEC and the following parameters:

- Bromoform concentration at the time of ballast water discharge: 0.19 mg/L;

- Predicted environmental concentr ation of Bromoform: 0.0113 μg/L;

- Bioconcentration factor: 14.06;

- Human ingestion dose of marine products per day: 188 g * ;

- Average weight of adults: 60 kg; and

- Human ingestion dose per day: 0.0113 μg/L×14.06×0.188 ̃60=0.000498 μg/kg/day.

As to the hazard level of Bromoform on humans, the NOAEL value was determined to be 25 mg/kg/day by a test of 13 weeks using rats . Comparing the estimated daily intake amount of 0.000498 μg/kg/day and the NOAEL of 25 mg/kg/day, MOS is more than ca 50 million and therefore there is no health risk due to the Bromoform generated by the system.

________________
* A ccording to the statistics of FAO (1999), annual consumption of fish and shellfish in Japan is the largest among the 10 world major countries, which is 68.5 kg. This figure corresponds to 188 g/day.

7.2.2.3.4 Effect of Bromoform cont ained in ballast water discharge to sea bathers

According to the MAMPEC model calculation, the predicted environmenta l concentration (PEC) at the time of ballast water discharge is 0.0113 μg /L. As to the hazard level of Bromoform on humans, the value NOAEL was determined to be 25 mg/kg/day by a test of 13 weeks using rats. Comparing these values, the hazard level is equi valent to a person swallowing ca 2 million litres a day of seawater. Therefore this valu e causes no concern for health effects.

Taking into account the above very low risk level, no effect on the health of children and elderly people is expected either.

7.2.2.4 Total Residual Oxidants(TRO)

As Total Residual Oxidants (TRO) presumably have no volatility, its exposure to shipboard personnel is restricted to such temporary works as inspection in the ballast tank. The Predicted Environmental Concentration (PEC) is 0.0432 μg/L, which is not harm ful to a sea batherís health.

7.2.3 Conclusion

The results of the investigation into the toxicity and exposure to Ozone as the Active Substance and to the Relevant Chemicals shows that the risk to human health is low for all substances and that no effect on human health is expected.

7.3 Risk to the aquatic environment

As summarized in this document section 6, the ba llast water discharged from this system has no potential effect on the environment.MEPC 59/2/1 ANNEX Page 57

I:\MEPC\59\2-1.doc 8 CONCLUSION

SP-Hybrid BWMS Ozone version uses th e powerful oxidizing agent, Ozone, as the Active Substance, which generates Relevant Chemicals by reaction with the intake ballast water. There are some residual Bromate ions, Bromoform and TRO (Total Residual Oxidants) in the discharged ballast water. However, th e safety of the ship and shipboard personnel is sufficiently secured by placing safe ty measures for Ozone on board.

Also, since all the ballast wate r is discharged through the DWTT , the concentrations of the residual chemicals are considered to cause no risk to the general public or to the receiving marine environment.

Therefore, this system is considered to deserve Final Approval under Procedure (G9).

REFERENCES

ATSDR 2005; U.S. DEPARTMENT OF HEALTH AND HUMAN SERVICES, Public Health Service Agency for Toxic Substances and Di sease Registry; TOXICO LOGICAL PROFILE FOR BROMOFORM AND DIBROMOCHLOROMETHANE, p139, August 2005.

Bouwer E.J. and McCarty P.L. ( 1983a). Transfomations of 1- and 2-carbon halogenated aliphatic organic compounds under methanogenic conditio ns. Appl. Environ. Microbiol. 45, 1286-1294.

Bouwer E.J. and McCarty P.L. (1983b). Tran sfomations of halogenated organic compounds under denitrification conditions. Ap pl. Environ. Microbiol. 45, 1295-1299.

ECOTOX DATA BASE (U.S. EPA, 2007a).

Erikson, S.J. and Freeman, A.E. (1978). Toxicity screening of fifteen chlorinated and brominated compounds, using four species of marine phytopla nkton. In, Water Chlorination: Environmental Impact and Health Effects, Vol. 2 (Ed. R. L. Jolley) pp 307-311. Ann Arbor Science.

Fisher D.J., Burton D.T., Yonkos L.T., Turley S.D. and Ziegler G.P., (1999). The relative acute toxicity of continuous and intermittent exposures of chlorine and bromine to aquatic organisms in the presence and absence of a mmonia. WATER RESEARCH, 33, 760-768.

Harrington, D.K., Van Benschoten, J.E., Jense n, J.N., Lewis, D.P., Neuhauser, E.F. (1997), Combined use of heat and oxidants for cont rolling adult zebra mussels Water Research 31(11):2783-2791.

Hayashi, M., Kishi, M., Sofuni, T. and Ishidate, M. , Jr. (1988) Micronucleus tests in mice on 39 food additives and eight miscellaneous chemicals. Fd. Chem. Toxicol., 26, 487-500.

Hijnen W,R Voogt, HR Veenendaal, H van der Jagt and D van der Kooij (1994), Bromate Reduction by Denitrifying Bacteria; Appl. E nviron. Microbiol, Jan 1995, Vol 61, No. 239-244.

ICSC 1993; International Chemical Safety Cards (ICSC). (1993) Ozone Retrieved on April 1993 http://www.ilo.org/public/english/protection/safework /cis/products/icsc/dta sht/_icsc00/icsc0068.pdf.

ICSC 2003; International Chemical Safety Cards (IC SC). (2003) Potassium Bromate. Retrieved on November 2003, http://www.inchem.org/ documents/icsc/icsc/eics1115.htm.MEPC 59/2/1 ANNEX Page 58

I:\MEPC\59\2-1.doc NITE 2007 ; National Institute of Technology a nd Evaluation, Biodegradation and Bioconcentration of Existing Chemical Substances under the Chemical Substances Control Law http://www.safe.nite.go.jp/data/ hazkizon/pk_e_kizon_disp.html?k_no=0657.

NTP 2008a; CAS Registry Number: 7758-01 Potassium Bromate.

NTP 2008 b; CAS Registry Number: 75-25-2 Bromoform.

Siddiqui, M.S., Amy, G.L. and Rice, R.G., 1995. Br omate ion formation: A critical review. Journal of American Water Works Association 87, pp. 58ñ70.

Siddqui M S., Thai W., Amy G., Mysore C., 1996. Bromate ion removal by activated carbon Water Research Volume 30, Issue 7, July 1996, Pages 1651-1660.

SRC 2007; Bromate ion.

Tabak H.H., Quaze S.A., Mashni C.I. and Barth E.F. (1981). Biodegradability studies with organic priority pollutant compounds. J. Water Pollut. Control Fed. 53, 1503-1518.

Ullmannís Encyclopaedia of Industrial Chemistry Six Edition, Section 2. Physical Properties, Ozone, June, 2001.

U.S. EPA, Environmental Protection Agen cy (2007) Drinking water contaminants. Retrieved on May 10th, 2007.(http://epa.gov/ safewater/contaminants/index.html#dbps).

U.S. EPA (2005); Environmental Protect ion Agency, DRINKING WATER CRITERIA DOCUMENT FOR BROMINATED TRIHALOMETHANES.

Ward, G.S., Parrish, P.R. and Rigby, R.A. (1981) Ea rly life stage toxicity tests with a saltwater fish: Effects of eight chemicals on survival, grow th, and development of Sheepshead minnows. J. Toxicol. Environ. Health, 8, 225-240.

Wedemeyer, G.A., N.C. Nelson, a nd W.T. Yasutake. 1979. Physio logical and Biochemical Aspects of Ozone Toxicity to Rainbow Trout (Salmo gairdneri). J. Fish. Res.Board Can. 36(6):605-614.

WHO (1996) Guidelines for drinking- wate r quality, Second Edition Volume 2, pp 851. http://www.who.int/water_sanit ation_health/dwq /en/2edvol2p1.pdf.

WHO (2005) Bromate in Drinking-w ater Background document for de velopment of WHO Guidelines for Drinking-water, Quality, Geneva,World Hea lth Organization (WHO/SDE/ WSH/05.08/78) (2005) (http://www.who.int/water_s anitation_health/dwq/che micals/bromate030406.pdf).MEPC 59/2/1 ANNEX Page 59

I:\MEPC\59\2-1.doc STATEMENT and QUALITY ASSURANCE STATEMENT

Example: Acute toxicity test for the treated wate r discharge (seawater, treat ed before discharge, retention time 0 Day) with Special Pipe Ballast Water Treatment System (combined with Ozone Treatment Version) using salt water fish Java medeka, Oryzias javanicus

.MEPC 59/2/1 ANNEX Page 60

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