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

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

INTERNATIONAL MARITIME ORGANIZATION

IMO 

# E

MARINE ENVIRONMENT PROTECTION COMMITTEE 60th session Agenda item 2 MEPC 60/2/2 20 August 2009 Original: ENGLISH

HARMFUL AQUATIC ORGANI SMS IN BALLAST WATER

Application for Final Approval of the JFE Ballast Water Management System (JFE-BWMS) that makes use of ìTG Ballastcleaner Æ and TG Environmentalguard Æ î

Submitted by Japan

SUMMARY
Executive summary: This document contains non-confiden tial information related to the application for Final Approval of the JFE Ballast Water Management System (JFE-BWMS) that makes use of ìTG Ballastcleaner Æ and TG Environmentalguard Æ î in accordance with the ìProcedure for approval of Ballast Water Management Systems that make use of Active Substances (G9)î adopt ed 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 57/21, MEPC 57/2/8, MEPC 58/2/7 and BWM.2/Circ.18

Introduction

1 Regulation D-3 in the Ballast Water Ma nagement Convention (BWM Convention) requires that Ballast Water Management System s, which make use of Active Substances, be approved by IMO based on a proced ure developed by the Organization.

2 MEPC 57 adopted resolution MEPC.169(57) ìProcedure for approval of Ballast Water Management Systems that make use of Active Substa nces (G9)î. Section 8 of Procedure (G9) sets out the methodology to be followed for the approva l of Active Substances and requests IMO to establish a Technical Group (the GESAMP-Ballast Water Working Group) for reviewing the proposals submitted by Administrations and repo rting to the Organization on its findings.MEPC 60/2/2 - 2 -

I:\MEPC\60\2-2.doc 3 Basic Approval of this system has b een granted by MEPC 58 (see document MEPC 58/23, paragraph 2.6.1).

4 According to BWM.2/Circ.18, proposals fo r approval of Ballast Water Management Systems that make use of Active Substances are to be submitted to the Marine Environment Division of the Organization and to be review ed by the GESAMP-Ballast Water Working Group. In the meantime, a document on the proposal fo r approval containing a ll the non-confidential data related to the respective Active S ubstance needs to be submitted to MEPC 60.

5 Japan therefore submits the non- confidential part of the appl icantís dossier in the annex of this document to the Organization for evaluati on according to Procedur e (G9). The complete dossier will be made available to the experts of the GESAMP-B allast Water Working Group with the understanding of conf idential treatment.

Action requested of the Committee

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

***MEPC 60/2/2

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

NON-CONFIDENTIAL INFORMATIO N ON THE JFE BALLAST WATER MANAGEMENT SYSTEM THAT MAKES USE OF ìTG BALLASTCLEANER Æ
AND TG ENVIRONMENTALGUARD Æ î (JAPAN)

1 PREFACE

The application for Basic Approval was made by TG Corporation, which is a member of the Toagosei Group. However, at that time, tasks rela ted to the onboard insta llation and operation of the ballast water management system (BWMS) as a whole were evaluated considering the case of installation of a system manufactured by JFE Engineering Cor poration, and this basic application was approved.

Based on this, in this ap plication for Final Approval, the ba sic system concept is proposed both by JFE Engineering Corporation as the BWMS maker and TG Corporation as the chemical manufacturer, as a compound process for treatm ent employing the chemicals approved in the Basic Approval.

This summary presents an outline of the system , and the newly added content of the methodology (BWM.2/Circ.13, 10 June 2008) ad opted during MEPC 58 focusi ng around the results of the land-based tests.

In the process of BWMS developm ent and the preparation of proposal for approval, in addition to the BWMS maker, JFE Engineering Corporation, and the chemical manufacturer, the Toagosei Group, development was carried out through jo int development, joint testing, and onboard evaluations of the individual elements of the technology with a shipyard in the JFE Group, and others. The land-based tests were contracted out to the Norwegian company Ballast Tech NIVA, which has an extensive record of tests for BWMS.

At the same time, Quality Assurance and Quality Control related to inspections were conducted by establishing a committee including members of all of the companies c oncerned, and clarifying the system of responsibility for approvals and implementation.

2 GENERAL

2.1 Introduction

In the application for Basic Approval, the TRO c oncentration in the ballast water at the maximum chemical injection rate was set at 30 mg/L. However, from the viewpoint of reducing the by-products of this process, it has become clear through experiment al research that the maximum chemical injection rate of 20 mg/L is acceptable as a rate that satisfies the D-2 standard and is also compatible with environmental needs. Therefore, in the land-based tests and evaluation for Final Approval, the maximum concentration was set at 20 mg/L.

However, if it can be confirmed in the future in onboard tests, etc., that the D-2 standard can be satisfied with a lower injection concentration than 20 mg/L, efforts will be made to further reduce the injection concentration, as the effect on aquatic organism can also be reduced.MEPC 60/2/2 ANNEX Page 2

I:\MEPC\60\2-2.doc 2.2 Outline of Ballast Water Treatment System

Considering the D-2 standard and Guidelines (G8) and Procedure (G9), a hybrid treatment system was adopted in the JFE-Ballast Water Management System (JFE-BWMS), comprising a ìprecision filter,î the Active Substances ìTG Ballastcleaner Æ ,î and the ìphysical action of mixing generated by Venturi tubesî inserted in the main pipi ng route downstream from the position where the Active Substances is injected.

Treatment begins during uptake of ballast wate r. Although the concentration is low, during voyages, TG Ballastcleaner Æ is left in the ballast tanks in or der to prevent regrowth and hatching of egg of marine organisms. On the other hand, when ballast water is discharged during loading in a port, the toxicity of the Total Residual Oxidant (TRO) in the treated ballast water is detoxified using TG Environmentalguard Æ , which is a reducing agent. Because cargo handling patterns and sailing time differ greatly, depending on the type of ship, this is done to provide a function which ensures that non-toxic ballast wa ter is always discharged when taking on or discharging ballast water, corresponding to the cargo handling pattern and sailing time.

Figure 1 shows the conceptual flow of the JFE-BW MS. Seawater is taken up from the sea chest by the ballast pump, and then passes through a strainer and precision filter. Plankton and particles of suspended solids (SS) with a minimu m size of 50 μm or larg er are captured by the filter element and rapidly returned to their original habitat or the waters where they were found by way of the backwash discharge pipe, togeth er with the backwash water collected by the backwash function of the precision filter elem ent, which is performed continuously during ballasting. Because TG Ballastcleaner Æ is injected after this filtration process, this backwash water of filter element does not contain TG Ballastcleaner Æ , and thus has no effect on the marine environment.

Because the filtered seawater has a lower conten t of organic matter (including living organisms) and suspended solids than raw seawater, the disi nfection/biocide effect can be realized with a smaller amount of chemical than if TG Ballastcleaner Æ is added directly to the raw seawater. TG Ballastcleaner Æ acts on the living organisms which have passed through the filter element, and also reacts with soluble organic and inor ganic substances. Accordingly, with the JFE-BWMS, it is possible to deactivate the living organisms with a smaller amount of TG Ballastcleaner Æ , and only a smaller amount of TG Ballastcleaner Æ is necessary.

The seawater, including living organi sms into which TG Ballastcleaner Æ is injected, flows into the Venturi tubes. The rapid agitation/mixt ure of the chemicals is performed by vortices generated in the expansion portion at downstr eam of the throat during flowing through the Venturi tubes and thus also has an effect, wh ich enables the Active Substances to deactivate living organisms more effectively.

The treated water after passing th rough this mixing process flows in to the ballast water tank. A certain concentratio n of TG Ballastcleaner Æ remains in the ballast water tank, and has the function of preventing re-growth of orga nisms and hatching of eggs in the tank.MEPC 60/2/2 ANNEX

Page 3

I:\MEPC\60\2-2.doc Figure 1: B asic conce p t of JFE-BWMS

In many cases, although the concentration is generally low, residual Active Substances may remain at the time where the ballast water is discharged. During international voyages, particularly with short sailing times, there is a possibility that a high concentration of a toxic Active Substances may remain, and this can be e xpected to have harmfu l effects on the natural ecosystem in the receiving waters if it is discharg ed from the ship without proper treatment. In order to solve this problem, the TRO is discharged from the ship after being detoxified by neutralization/reduction by TG Environmentalguard Æ , which is a reducing agent. Because the reductant TG Environmentalguard Æ is injected on the upstream side of the ballast pump during discharge of the ballast water, it is complete ly mixed by the high speed rotation of the pump impeller while passing through the pump so th at the reduction react ion with the TRO is completed immediately in the ballast water di scharge pipe line, ensuring that the TRO is completely eliminated before the water is discharged from the ship.

2.2.1 System concept

In the JFE-BWMS, when the ballast tanks are filled with seawater, etc., (thi s operation is referred to as ìballastingî), the amount of TG Ballastcleaner Æ injected into the water is controlled so that the TRO concentration in the ballast water immediately after treatment will conform to the set value using a TRO meter (Total Residual Oxidant Meter) in order to hold the concentration of TG Ballastcleaner Æ after injection to the lowest possible level.MEPC 60/2/2 ANNEX Page 4

I:\MEPC\60\2-2.doc Based on the TG Ballastcleaner Æ injection rate, Free Available Chlorine (FAC) is set with the maximum of 20 mg/L as an upper limit. Control values are se t so that the operation of the system is stopped if FAC exceeds this upper limit value. Furthermore, in ordinary operation, the system is set so that the TRO concentration wi ll reach approximately 10 mg/L one minute after injection of TG Ballastcleaner Æ

. When treated ballast water is discharged (herei nafter referred to as ìdeballastingî), the TRO concentration in the ballast water is measured using the TRO Meter, and an amount of TG Environmentalguard Æ greater than that necessary to completely neutralize/reduce the measured concentration is injected by arrangin g ìmulti-point injection nozzlesî in the ballast water piping on the upstream side of the ballast pump. Complete mixing is achieved using the mixing effect of the turbulent flow generated by the rotating impeller of the pump when the water passes through the ballast pump on the downstream side from these nozzles. Furthermore, in order to confirm that the discharge has been completely neutralized/r educed, monitoring of complete neutralization/reduction is performed using a high resolution TRO Meter, which is capable of measuring reduction condition.

2.2.2 Composition and roles of equipment

JFE-BWMS comprises a power control panel, ba llast pump operation panel, chemical injection pump operation panel, and BWMS control panel. Although these panels are installed at machine side, remote operation panels ar e also provided, enabling remo te operation from the ballast control room and other locations. The opera ting data acquisition f unction and the report preparation function are us ed to store and analyse operating da ta and output ñ the necessary items requested in Guidelines (G8) in the form of reports.

2.2.3 Injection system of chemicals

The injection of TG Ballastcleaner Æ during ballasting and the injection of TG Environmentalguard Æ for neutralization/reduction treatment of TRO at the time of ballast discharge, are controlled so as to achieve the set TRO concentration by changing the rotational speed of the chemical injection pump drive motor with an inverter using the measured value of the TRO concentration. Furthermore, because it is necessary to change the injection flow rate corresponding to the fluctuations in the flow rate in the main balla st line in order to secure a uniform chemical injection concentration, a flow meter is provided for this purpose.

During deballasting, a TRO Meter is used to conf irm that the TRO concentration in the ballast water has been completely neutralized/reduced . A TRO Meter with a measurement range of 0-30 mg/L is used in order to measure the TRO in the ballast tanks. A high resolution TRO Meter with a measurement range of -0.2 to 3 mg/L had been developed and was used to confirm that the value of TRO concentration of the ballast water after neutralization/reduction (secondary treated water) is 0 or less. The concen tration meter has the capa bility to measure to a reducing condition, and outputs minus values at reducing condition.

TG Environmentalguard Æ is injected via the chemical in jection nozzles in the piping on the upstream side of the ballast pump at a flow rate, which secures the necessary concentration for complete neutralization/reduction of the TRO c oncentration measured immediately after the ballast water leaves the ballast tanks, and is mixed as it passes through the pump.MEPC 60/2/2 ANNEX

Page 5

I:\MEPC\60\2-2.doc The neutralization/reduc tion reaction velocity of TG Ballastcleaner Æ

and TG Environmentalguard Æ

is extremely fast. Because these substances are completely mixed by the turbulent flow generated by the pump impeller as they pass through the ball ast pump, the reaction is 100% complete in the ballast water piping. Accordingly, the ballast water does not contain any TRO when discharged, and thus has no adverse effect on the external environment.

2.3 Additional Data Sets request ed at time of Basic Approval

Detailed replies are given in the assessment repo rt on the items which we re pointed out in the GESAMP-BWWG report of its 6th meeting (M EPC 58/2/7, annex 5) as requiring further clarification in the Final Approval process. The requests by GESAMP-BWWG and the replies are shown briefly, as follows:

.1 Considering corrosion, the Group agreed that the applicantís response was insufficient to quantitatively assess the co rrosion impact to relevant metallic and non-metallic materials likely to be used in ballast water tanks, piping and fixtures.

For non-metallic gasket materials, the applicant responded that tests were not started since they have sufficient information for suitable materials but no details or data were provided.

Reply : The data are stated briefly in 7.1.1.5 of this summary, and additional corrosion tests necessary for evaluation were performe d. (The detailed da ta are given in the confidential part of the assessment report.)

.2 The applicant should provide appropriate QAs and QCs and indicate why there are different detection limits for the same substance being analysed.

Reply : In order to ensure Quality Assurance/ Quality Control for chemical experiments and chemical analyses when applying fo r Final Approval, a decision was made to organize a Quality Assurance Committee including members of all related companies, and to carry out all drafting and implementation of plans and reporting and verification of the results in accordance with a Quality Assurance Project Plan (QAPP) audited and ap proved by the Committee.

Regarding detection limits, these were unified simultaneously with the improvement of making lower detection limits. When some substances have different limit values, the reason fo r this is described separately.

.3 Further measurement and analysis of discharge concentration of THMs and HAAs with adequate QA/QC should be taken duri ng the full-scale land- based test before the submission for Final Approval.

Reply : As mentioned in .2 above, for the appl ication for Final A pproval, appropriate Quality Assurance/Quality Control were performed in accordance with the QAPP, and this obligation was also imposed in commissioned tests (e.g., test contracted out to Ballast Tech ñNIVA AS).

Standard Operation Procedures (SOP) whic h are capable of assuring quality were prepared for all tests, and audits as to wh ether the test were carried out as specified in the SOP were carried out in accord ance with the quality assurance system.MEPC 60/2/2 ANNEX Page 6

I:\MEPC\60\2-2.doc .4 The chemical analyses for THMs were not performed under adequate QAPPs and so recommended that all chemical measurement and analyses should be performed under QAPPs.

Reply : As mentioned in .2 and .3 above for the application for Final Approval, measurements and analyses of all chemical substanc es were conducted based on the QAPP.

.5 Final Approval submission should provide full details of the dosing control arrangements so as to ensure certainty of maintaining specified dosage levels of Active Substances.

Reply : During ballasting, injection control of TG BallastcleanerÆ is performed. Regarding TG BallastcleanerÆ injection c ontrol, at a set after the start of operation of the JFE-BWMS, a set amount of TG Ballastcl eanerÆ corresponding to a free available chlorine (FAC) conc entration of 20 mg/L is injected. Thereafter, the TG Ballastclean erÆ supply rate is controll ed so that the value of the residual chlorine concentration in the ballast water will fall within a target range of residual chlorine concentrati ons which has been set in advance.

On the other hand, during deballasting, discharge neutralization control is performed using the chemical TG Environmentalguard Æ

. In discharge neutralization cont rol using TG Environmentalguard Æ at a set time after the start of operation of the JFE-BWMS, a set amount of TG Environmentalguard Æ

, which will neutralize the 20 mg/L FAC concentration of TG Ballastcleaner Æ that was supplied during ballasting, is inject ed. Thereafter, the supply rate of TG Environmentalguard Æ necessary for neutralization is calculated and adjusted based on the residual chlorine concentration value in the ballast water at the outlet of the ballast tank, and the ballast wate r is discharged into the sea after neutralization/re duction treatment.

Those are brief explanation of control sy stem and more details of the control system are explained in 2.2.3 above.

.6 The Group was satisfied that the flow diagram provided was suitable for Basic Approval. It is appreciated that furt her details for evaluation be supplied for review during any Final Approval.

Reply : The piping system diagram, system co mposition diagram, single line diagram (skeleton diagram), control flowchart, and protective interl ock diagram of the JFE-BWMS and the operational procedure of the JFE-BWMS are described in the confidential part of the assessment report.

.7 The applicant indicated to continue ga thering information related to the two chemicals, bromochloroacetic acid and bromodichloroacetic acid and, if no additional data were to be found, they woul d carry out further algal tests as required.

Reply : As data on dibromochloroacetic acid and bromodichloroacetic ac id were required in the the GESAMP-BWWG report (MEPC 58/2/7, annex 5, paragraph 2.10), a toxicity test (Algal Growth Inhibition Test) was pe rformed, and NOEC was obtained. The test results were added to the conf idential part of the assessment report.MEPC 60/2/2 ANNEX

Page 7

I:\MEPC\60\2-2.doc .8 The Group was satisfied that the applicant had given due preliminary consideration to the concerns concerni ng temperature control put forward but requested that these safety mitigation m easures and requirements should be fully detailed in the operating manual pr esented for any Final Approval.

Reply : In order to prevent self-deg radation of TG Ballastcleaner Æ , it is necessary to control the temperature to 20°C or less. In onboard tests, the TG Ballastcleaner Æ tank was covered with thermal insulation, a nd external heat inputs were prevented as much as possible. The very small amount of input heat which was transmitted through the insulation was radiated to the outside by a water cooling method through cooling tubes arranged between the tank wall and the insulation using an independently controlled electric chiller.

Regarding the temperature control procedure with this chiller, temperature control is performed automatically when the power is turned on, the set temperature is inputted, and operation begins. In the temperature control, cooling operation begins when the temperature exceeds the set temperature by 1°C and ends when the temperature of 1°C lower than the set temperature, is reached.

As another possible method, the tank can be installed in an area where it is air-conditioned to 20°C or less.

.9 Whilst recognizing the validity of the pr essure monitoring/control, the Group considered that further veri fication of this should be made during the ship board testing and included in the doc umentation for Final Approval.

Reply : PV(Pressure-vacuum) valves are provided in the chemical storage tanks. When the tank internal pressure exceeds the external atmospheric pressure by 100 mmAq, PV valve opens and reduces the pressure, and when the internal pressure decreases to 100 mmAq less than the external atmospheric pressure, PV valve opens and increases the pressure.

In onboard tests, the internal pressure increased and d ecreased due to the loading and use of the chemicals, respectively. It was confirmed that the PV valves operated normally, and the tank internal pr essure was kept within the set range.

Normal operation of the level gauges and hi gh level alarms was also confirmed in shipboard experiments.

.10 The Group is of the opinion that the acute toxicity tes ting for treated ballast water and the information for acute toxicity testing by simulated ballast water in a laboratory scale and full-scale land-bas ed system are needed for evaluation.

In addition, the Group request ed that quantification anal ysis and degradation rates of sodium sulphite in various conditions should be carried out for the submission for Final Approval.

Reply : These were performed in land-based test s carried out by Ballast Tech-NIVA. The evaluation is described in Chapter 3.MEPC 60/2/2 ANNEX Page 8

I:\MEPC\60\2-2.doc .11 The Group recommended that the followi ng human exposure information related to TG BallastCleaner Æ should be addressed:

.1 in advance identification of all leaki ng points; these are to be considered critical points for the HSE (due to the corrosive properties of the preparation);

Reply : All locations where leaks can be exp ected were designated in advance, and those positions were indicated on the piping system diagram.

.2 foreseen safety measures for spills/l eaks in the wastewater collection tank;

Reply : Because the periphery of the tank is surrounded by a coaming, there will be no effect on the surrounding area in the unlikely event of a leak. It should also be noted that the colle cted wastewater is discharged immediately after confirming with a simp le sensor that it does not contain residual chlorine, and is not stored in the tank.

.3 manual handheld (residual chlorine meter) measurements of residual chlorine concentration in the waste water tank.

Reply : The operation procedure for the port able residual chlorine meter was attached to the appendix of the assessment report.

2.4 Identification of chemicals

The disinfectant/biocidal agent (trade name: TG Ballastcleaner Æ ), which is used in JFE-BWMS is an aqueous solution of s odium hypochlorite (CAS No. 7681-52-9) . The content of Free Available Chlorine (FAC) consists of two classes: TG Ballastcleaner Æ having a FAC concentration of more than 5% to 10%, or TG Ballastcleaner Æ having a FAC concentration of mo re than 10% to 13% or less.

A reducing/neutralizing agen t, TG Environmentalguard Æ , consists of two classes: an aqueous solution with a concentration of 10% to 13%, and a solid form.

2.5 Definition of Active Substances, ot her components and Relevant Chemicals

TG Ballastcleaner Æ comprises sodium hypochlorite as an Active Substances (AS) as its main component, and sodium chloride and sodium h ydroxide as other components (OC), which are contained due to the manufacturing method.

Regarding the second chemi cal TG Environmentalguard Æ , which is used to eliminate the TRO in the ballast water including residual chlorines and others, this chemical co mprises sodium sulfite, which is the other component as its main compon ent, and sodium sulfate as the other component, which is contained as a result of the manufacturing process.

Relevant Chemicals (RC) in this ballast wate r treatment system are the following 23 chemicals which were pointed out in the Basic Approva l process by the GESAMP-BWWG: hypochlorous acid, chloroform, dichlorobromomethane, dibrom ochloromethane, bromoform, hypobromous acid, sodium hypobromite, bromate ion, mo nochloroacetic acid, dichloroace tic acid, trichloroacetic acid, bromochloroacetic acid, bromodichloroacetic ac id, dibromochloroacetic acid, monobromoacetic acid, dibromoacetic acid, tribromoacetic acid, chloroacetonitrile, dichloroacetonitrile, trichloroacetonitrile, dibromoacetonitrile, brom ochloroacetonitrile and monochloramine.MEPC 60/2/2 ANNEX

Page 9

I:\MEPC\60\2-2.doc A list of chemical identification of the above Active Substances, other components and Relevant Chemicals is shown in Table 2.5.1.

Table 2.5.1: List of Chemical Identification

Name of chemical substance IUPAC CAS No. Molecular weight Chemical formula Structural formula
Active Substances

AS Sodium hypochlorite Sodium hypochlorite 7681-52- 9 74.45 NaClO Na-Cl-O Other Components
OC1 Sodium hydroxide Sodium Hydroxide 1310-73- 2 40.00 NaOH NaOH

OC2 Sodium chloride Sodium Chloride 7647-14- 5 58.44 NaCl NaCl

OC3 Sodium sulfite Sodium Sulfite 7757-83- 7 126.06 Na 2 SO 3
NaO NaO

S O

OC4 Sodium sulfate Sodium Sulfate 7757-82- 6 142.04 Na 2 SO 4 S O

O ONa NaO

Relevant Chemicals
RC1 Hypochlorous acid Hypochlorous acid 7790-92- 3 84.64 HClO H-O-Cl

RC2 Chloroform Trichloromethane 67-66-3 119.4 CHCl 3 C H Cl

Cl

Cl

RC3 Dichlorobromo methane Dichlorobromom etahne 75-27-4 163.82 CHBrCl 2 C Cl

Br H Cl

RC4 Dibromochloro methane Dibromochlorom ethane 124-48-1 208.27 CHBr 2 Cl C Cl

Br

Br H

RC5 Bromoform Tribromomethane 75-25-2 252.7 CHBr 3 C Br H

Br Br

RC6 Hydrobromous acid Hypobromous acid 13517- 11-8 96.91 HBrO H-O-Br

RC7 Sodium hypobromite Sodium hypobromite 13824- 96-9 118.89 NaBrO Na-O-Br

RC8 Bromate ions (CAS No., molar mass, etc., are shown at sodium bromate.) Bromate 7789-38- 0 150.9 NaBrO 3 Br O

O NaOMEPC 60/2/2 ANNEX Page 10

I:\MEPC\60\2-2.doc Name of chemical substance IUPAC CAS No. Molecular weight Chemical formula Structural formula

RC9 Monochloro acetic acid Monochloroacetic acid 79-11-8 94.5 CH2ClC OOH C O

Cl C OH H

H

RC10 Dichloro acetic acid Dichloroacetic acid 79-43-6 128.9 CHCl 2 CO OH C O

Cl C OH H Cl

RC11 Trichloroacetic acid Trichloroacetic acid 76-03-9 163.4 CCl 3 COO H C O Cl

Cl Cl C OH

RC12 Bromochloroacetic acid Bromochloroacetic acid 5589-96- 8 173.39 CBrClHC OOH C O

C OH H Cl

Br

RC13 Bromodichloroacetic acid Bromodichloroacetic acid 71133- 14-7 207.84 CBrCl 2 C OOH C O

C OH Cl

Cl

Br

RC14 Dibromochloroacetic acid Dibromochloroacetic acid 5278-95- 5 138.95 Br 2 ClCC OOH C O

C OH Br

Cl

Br

RC15 Monobromoacetic acid Monobromoacetic acid 79-08-3 138.95 BrCH 2 C OOH C O

C OH H

H

Br

RC16 Dibromoacetic acid Dibromoacetic acid 631-64-1 217.84 CHBr 2 C OOH C O

C OH Br

H

Br

RC17 Tribromoacetic acid Tribromoacetic acid 75-96-7 296.74 Br 3 CCO OH C O

C OH Br

Br

Br

RC18 Chloroacetonitrile Chloroacetonitrile 107-14-2 75.47 CH 2 ClCN C C H Cl

N

H

RC19 Dichloroacetonitrile Dichloroacetonitrile 3018-12- 0 109.94 CHCl 2 CN C

Cl C H Cl

N

RC20 Trichloroacetonitrile Trichloroacetonitrile 545-06-2 154.39 CCl 3 CN C

Cl C Cl

N Cl

RC21 Dibromoacetonitrile Dibromoacetonitrile 3252-43- 5 198.84 CHBr 2 C N C C H N

Br BrMEPC 60/2/2 ANNEX Page 11

I:\MEPC\60\2-2.doc Name of chemical substance IUPAC CAS No. Molecular weight Chemical formula Structural formula

RC22 Bromochloroacetonitrile Bromochloroacetonitrile 83463- 62-1 154.39 CHBrClC N C C H Cl

N

Br

RC23 Monochloramine Chloramide 10599- 90-3 51.48 NH 2 Cl N H Cl H

3 TEST RESULTS AND DATA ON TOXICITY

3.1 Results of land-based test and onboard test

Land-based test and onboard test were conducted to collect da ta for evaluating the treatment performance of the system and conducting the ri sk assessment. The following summarizes the ballast water management systems used for th e land-based and onboard tests and describes the results.

3.1.1 Land-based test

The land-based test of the ballas t water management syst em was conducted at Ba llast Tech NIVA AS (called BTN, http://www.ballasttech-niva.no/ ) in Norway. The 10 land-based test cycles including 5 cycles each for brackish water and s eawater were conducted in total at a sodium hypochlorite concentration of 20 mg/L, the maxi mum injection concentration converted to effective chlorine. A test cycle consisting of th e experimental items provided by Guidelines (G8) was conducted for brackish water in the operating condition in which the measurement of TRO meter is 10 mg/L which is normal operation conditi on. Verification test to determine whether the neutralization/reduction of TRO is completed in the ballast pipe during deballasting was performed for all test cycles.

3.1.1.1 Results of the land-based test

Chemical and biotic water quality parameters of the test water specified in Guidelines (G8) satisfied the reference value in all test cycles of land-based test. Treatment performance of organisms such as plankton and bacteria sati sfied the D-2 standard in all test cycles.

The following show the concentration of Relevant Ch emicals, and the results of the toxicity tests to the five marine organisms for the 4-cycle seawater test and the 4-cycle brackish water test in which Relevant Chemicals were analyse d. Only the results of the test on the sec ondary treated ballast water after the neutralization/reduction conducted af ter 5 days (Day 5) are shown in this summary.

3.1.1.1.1 Analysis of Relevant Chemicals

Table 3.1.1 shows the mean, standard deviation, a nd maximum values of relevant chemicals in the 4 test cycles for brackish wa ter and 4 test cycles for seawater , respectively, as a summary of the results of measurements.

The analytical values below th e detection limit are mentioned as ìLT.DL.î in a note underneath the table.MEPC 60/2/2 ANNEX Page 12

I:\MEPC\60\2-2.doc In the table, the shade cells are the substances for which analytical valu es above the detection limit were detected. Those detected in the br ackish water tests were bromodichloromethane, dibromochloro-methane, bromoform (tribromomet hane), bromate ion, bromochloroacetic acid, and dibromoacetic acid. In addition to these, monobromoacetic acid a nd tribromoacetic acid were detected in the seawater tests.

Bromoform, which particularly attrac ted attention, showed a mean of 310 μ g/L (maximum: 330 μ g/L) in the brackish water tests, wh ereas, in the seawat er test, a mean of 123 μ g/L (maximum: 180 μ g/L) was detected. It is consid ered that the difference of water quality in the brackish water and seawater has influence on the test.

Bromate ion showed a mean of 12.0 μ g/L (maximum: 18.0 μ g/L) in the brackish water tests, but a mean of 34.0 μ g/L (maximum: 46.0 μ g/L) was detected in the seawater tests.

Dibromoacetic acid showed a mean of 24.0 μ g/L (maximum: 47.0 μ g/L) in the brackish water tests, but a mean of 5.8 μ g/L (maximum: 8.7 μ g/L) was detected in the seawater tests.

Table 3.1.1: Analytical values of Re levant Chemicals in the land-based test

maximum

value mean value standard deviation maximum value mean value standard deviation μg/l μg/l μg/l μg/l μg/l μg/l μg/l
RC2 Chloroform 0.1 LT.DL.* LT.DL LT.DL. - LT.DL. LT.DL. LT.DL. - RC3 Bromodichloromethane 0.1 0.88 0.81 0.08 3,4,5,6 0.70 0.33 0.25 7,8,9,10 RC4 Dibromochloromethane 0.1 16.00 13.00 2.16 3,4,5,6 6.60 4.50 1.45 7,8,9,10 RC5 Bromoform 0.1 330.00 310.00 21.60 3,4,5,6 180.00 122.50 38.62 7,8,9,10 RC6 Hydrobromous acid - - RC7 Sodium hypobromate - - RC8 Bromate ion 1.0 18.00 12.00 7.62 3,4,6 46.00 34.00 14.45 7,8,9,10 RC9 Monochloroacetic acid 0.5 LT.DL. LT.DL. LT.DL. - LT.DL. LT.DL. LT.DL. - RC10 Dichloroacetic acid 0.3 LT.DL. LT.DL. LT.DL. - LT.DL. LT.DL. LT.DL. - RC11 Trichloroacetic acid 0.2 LT.DL. LT.DL. LT.DL. - LT.DL. LT.DL. LT.DL. - RC12 Bromochloroacetic acid 0.1 0.47 0.39 0.08 3,4,5,6 0.43 0.24 0.17 9,10 RC13 Bromodichloroacetic acid 0.1 LT.DL. LT.DL. LT.DL. - LT.DL. LT.DL. LT.DL. - RC14 Dibromochloroacetic acid 0.1 LT.DL. LT.DL. LT.DL. - LT.DL. LT.DL. LT.DL. - RC15 Bromoacetic acid 0.2 LT.DL. LT.DL. LT.DL. - 5.70 1.58 2.75 7 RC16 Dibromoacetic acid 0.1 47.00 23.98 19.06 3,4,5,6 8.70 5.80 2.97 7,8,9,10 RC17 Tribromoacetic acid 0.1 LT.DL. LT.DL. LT.DL. - 0.10 0.10 0.00 9,10 RC18 Chloroacetonitrile 1.0 LT.DL. LT.DL. LT.DL. - LT.DL. LT.DL. LT.DL. - RC19 Dichloroacetonitrile 1.0 LT.DL. LT.DL. LT.DL. - LT.DL. LT.DL. LT.DL. - RC20 Trichloroacetonitrile 1.0 LT.DL. LT.DL. LT.DL. - LT.DL. LT.DL. LT.DL. - RC21 Dibromoacetonitrile 1.0 LT.DL. LT.DL. LT.DL. - LT.DL. LT.DL. LT.DL. - RC22 Bromochloroacetonitrile 1.0 LT.DL. LT.DL. LT.DL. - LT.DL. LT.DL. LT.DL. - RC23 Monochloroamine - - * : LT.DL.. = less than detection limit Bold character indicate the measured maximum value Detected substances are indicated in the shaded cells Measured as TROHaloacetic acidsHalo-acetonitriles

Measured as TRO Measured as TRORelevant ChemicalsTrihalomethanesBromate Measured as TRODetectionLimit. Brackish Water Seawater
Test Cycle 3,4,5,6 Detected Test Cycle Test Cycle 7,8,9,10 Detected Test CycleClass No. Name of chemical species

3.1.1.1.2 Biological parameters

The results of the toxicity test conducted on the 5 types of marine organisms are shown below. In this table, TGBC and TGEG are ab breviations of TG Ballastcleaner Æ and TG Environmentalguard Æ

, respectively.MEPC 60/2/2 ANNEX Page 13

I:\MEPC\60\2-2.doc A. Results of the growth inhibi tion test on marine algae ( Skeletonema costatum )

Table 3.1.2 shows the values of EC 10 and EC 50 obtained from the growth inhibition test.

These results indicate that the ef fect on growth inhibition was not seen except in the case of 66% of EC 10 on Day 5 during the test cycle 1 and 100% of EC 10 on Day 5 during the test cycle 2.

Table 3.1.2: Results of the growth inhibition test on marine algae ( Skeletonema costatum )

Test cycle Test water Day No. Water condition EC10 (%) EC50 (%)

0 Immediately after TGBC injection 2.0 2.3 1 Seawater 5 After TGEG neutralization 66 >100 0 Immediately after TGBC injection 1.0 1.4 2 Brackish
water 5 After TGEG neutralization 100 >100 0 Immediately after TGBC injection 1.9 1.8 3 Brackish
water 5 After TGEG neutralization >100 >100 0 Immediately after TGBC injection 3.1 3.4 4 Brackish
water 5 After TGEG neutralization >100 >100 0 Immediately after TGBC injection 3.7 4.4 5 Brackish
water 5 After TGEG neutralization >100 >100 0 Immediately after TGBC injection 1.5 1.7 6 Brackish
water 5 After TGEG neutralization >100 >100 0 Immediately after TGBC injection 0.98 0.95 7 Seawater 5 After TGEG neutralization >100 >100 0 Immediately after TGBC injection 0.15 0.27 8 Seawater 5 After TGEG neutralization >100 >100 0 Immediately after TGBC injection >1.8 >1.8 9 Seawater 5 After TGEG neutralization >100 >100 0 Immediately after TGBC injection 0.42 0.70 10 Seawater 5 After TGEG neutralization >100 >100 0 Immediately after TGBC injection 1.9 1.7 11 Brackish
water 5 After TGEG neutralization >100 >100

Note : (ì>100%î means that no effect was seen in th e test using the raw wa ter for the secondary treated ballast water.)

B. Results of the acute toxicity test to marine copepods ( Acartia tonsa )

Results of the acute toxicity test to marine copepods ( Acartia tonsa ) are shown in Table 3.1.3.

Table 3.1.3: Acute toxicity test on Acartia tonsa , a type of marine copepods

Acute toxicity test on invertebrate ( Acartia tonsa )
Test cycle Test water Collection date Test result 48H-NOEC % Comment

8 Seawater 2009.02.25 >100 % The death rate was zero in all test concentrations up to the 100% concentration of the secondary treated
water.MEPC 60/2/2 ANNEX Page 14

I:\MEPC\60\2-2.doc C. Reproduction toxicity (chronic toxicity) to Nitocra spinipes , a type of marine copepods

Reproduction toxicity (c hronic toxicity) to Nitocra spinipes , a type of marine copepods is shown in the Table 3.1.4.

Table 3.1.4: Results of th e chronic toxicity test on Nitocra spinipes , a type of marine copepods

Results of reproducible toxicity test (chronic toxicity test) on Nitocra spinipes , a type of marine copepods Test cycle Test water Collection date Test result 14d-NOEC % Comment

3, 4 Brackish
water 2009.01.19 2009.01.26 >100 % No significant effect was seen on reproducibility.

D. Oyster embryo

Chronic toxicity test was conduc ted on oyster embryo. Table 3.1.5 shows the results. No effect was seen at all concentrations.

Table 3.1.5: Results of the chro nic toxicity test on oyster embryo

E Acute toxicity to juvenile turbot ( Scophthalmus maximus )

Acute toxicity to juvenile turbot ( Scophthalmus maximus ) is shown in Table 3.1.6.

Table 3.1.6: Results of the acute toxicity test on fish

Results of the acute toxicity te st on fish (juvenile turbot)

Test cycle Test water Collection date Test result 96H-NOEC (%) Comment

6 Brackish
water 2009.02.09 >100 % The limit test showed no effect

7 Seawater 2009.02.16 >100 % Th e limit test showed no effect Results of the chronic toxicity test on oyster embryo

Test cycle Test water Collection date Test result 48H-LC 50 (%) Test result 48H-NOEC (%) Comment

3 Brackish
water 2009.01.19 >100 % ≥ 100 % No effect was seen at all concentrations.

7 Seawater 2009.02.16 >100 % ≥ 100 % DittoMEPC 60/2/2 ANNEX Page 15

I:\MEPC\60\2-2.doc F. Chronic toxicity to juvenile turbot ( Scophthalmus maximus )

Chronic toxicity to juvenile turbot ( Scophthalmus maximus ) is shown in Table 3.1.7.

Table 3.1.7: Results of the ch ronic toxicity test on fish

Results of the acute toxicity test on fish (juvenile fish) Test cycle Test water Collection date Test result 28d-NOEC (%) Comment

3-6 Brackish
water 2009.01.19 -2009.02.17 >100 % The limit test showed no effect. Lack of weight increase at controlled section.

7-10 Seawater 2009.02.16 -2009.03.17 >100 % The limit test showed no effect.

G. Chronic toxicity on Brachiomus plicatilis using a reproduction test

Chronic toxicity on Brachiomus plicatilis , a type of marine rotatoria, tested using a reproduction test is shown in Table 3.1.8.

Table 3.1.8: Results of the chronic toxicity test on marine rotatoria

Reproduction test usin g marine rotatoria ( Brachiomus plicatilis )(chronic toxicity)
Test cycle Test water Collection date Test result LC 50 (%) Test result NOEC (%) Comment

5 Brackish
water 2009.01.26 >100 % ≥ 100 % No effect was seen at all concentrations.

10 Seawater 2009.03.09 >100 % ≥ 100 % No effect was seen at all concentrations,

The following conclusion was obtained from the results of these toxicity tests:

In the growth inhibitory experiments using Skeletonema costatum , only two out of 11 cases exhibited minor effects as measured utilizing EC 10 . No effects were observed in other organisms and in other te st conditions. These results demonstrate ballast water after neutralization/reduction tr eatment in the present system has no effect against aquatic organisms.

3.1.1.2 Neutralization verification experiments

In this system, since a larger amount of TG Environmentalguard Æ than what is stoichiometrically needed is injected to neutralize/reduce TRO comp letely, the discharge water contains a slightly excessive amount of sodium sulfite. Because re duction speed with TRO is extremely high, ballast water is completely neutralized an d reduced in the piping if the sti rring after injection is sufficient.

To validate the above, ballast water is sampled from the lower side of piping below the nozzle where TG Environmentalguard Æ is injected to. The fact that TRO is less than 0.02 mg/L was confirmed after TRO analysis using a newly de veloped ìhigh resolution absorption photometryî with a detection limit of 0.0012 mg/L and a lower quantification limit of 0.004 mg/L.MEPC 60/2/2 ANNEX Page 16

I:\MEPC\60\2-2.doc The reduction of dissolved oxygen concentrat ion of ballast water before and after neutralization/reduction tr eatment during deballasting is confir med to be at only about 10%. Therefore, it was concluded that it has no eff ect of reduction of dissolved oxygen against living organisms.

3.1.2 Onboard test (Reference data)

Although the main subject of this ap plication is the risk assessment using the data obtained in the land-based test, a voluntary onboard test was conducted in order to obtain data for the case in which this system is actually operated on a ship.

The ship used in the onboard test was a Box Shape Bulker with a dead weight of 46,882MT. This ballast water treatment system was installed only in the ballast piping system on the left side of the ship when the ship was newly constructed.

As a result of this experiment, it was possible to confirm that this system conforms to the D-2 performance standard contained in the Ballast Water Management Conven tion, including cases in which ballasting and deballastin g operations are performed with actual ballast tanks. The experiment also confirmed that neutralizatio n and reduction treatment during discharge are performed in the same manner as in the land-based test, and furthe rmore, the species of Relevant Chemicals contained in the discharged ballast wa ter after neutralization are the same, and their concentrations are lower than the maximum values in the land-based test.

3.2 Methods of analysing en vironmental concentration

In this system, control of injection rates related to chemicals, measurements of TRO, and analysis to confirm complete neutralization a nd reduction are performed as follows.

3.2.1 Analytical method for TRO

(TRO: hypochlorite, hypochlorous acid, hypobrom ite, hypobromous acid, and monochloramine)

The analytical methods used were the ordinary N, N-Diethyl-P-Ph enylenediamine method (DPD); (lower detection limit: 0.02 mg/L) and, as a high re solution analytical method (lower detection limit: 0.0012mg/L) for detection of TRO in low con centrations after neutra lization treatment, a method in which the optical path length in the DPD method was 5 cm or longer.

These methods were also used in calibration of the TRO meters used in chemical injection control and monitoring of TRO neutralization and reduction.

3.2.2 Analytical method for bromate

The analysis is obtained by a post-column me thod using an ion chromograph. The lower detection limit is on the order of 1 μ g/L.

3.2.3 Analytical method for trihalomethanes, haloacetic acids, and haloacetonitriles

The analysis of trihalomethanes and haloaceton itriles in seawater was performed in accordance with Japanís Tap Water Test Method. Measurements were made using a purge-and-trap gas chromatograph/mass spectrometer (GC/MS). The lower detection limit is on the order of 1 μg/L.MEPC 60/2/2 ANNEX Page 17

I:\MEPC\60\2-2.doc In the analysis of haloacetic acids, tert -butyl methyl ether extraction was performed, and measurements were made with a GC/MS following methylation with diazomethane.

For the haloacetonitriles, tert -butyl methyl ether extraction was performed, and measurements were made with a GC/MS.

3.3 Quality Assurance and Quality Control

For reliable implementati on of Quality Assurance/Quality Contro l (QA/QC) in chemical experiments and chemical analyses for resolving the main chemi cal items related to this application, a Quality Assurance Committee including me mbers of all the companies c oncerned was established, and the system for audits/approvals and respons ibility for implementa tion was clarified.

3.3.1 QA/QC system

All drafting and implementation of plans and re porting and verification of the results were performed in accordance with the Quality Assurance Project Plan (QAPP) audited and approved by the Quality Assurance Committee.

3.3.2 QA/QC

In this application, appropria te QA/QC were performed in accordance with the Quality Assurance Project Plan (QAPP) and the Standard Operation Procedures (SOP), and the same obligation was also imposed in commi ssioned tests (e.g., Ballast Tech-NIVA).

3.4 Data on effects on aquatic plants, inv ertebrates, fish, and other biota, including

s ensitive and representative organisms

In this section, only data of the influence on aquatic organisms are shown. The evaluation of each item is described in Chapter 6.

3.4.1 Acute aquatic toxicity

3.4.1.1 Active Substances

The object of study as an Active Substances is sodium hypochlorite, which is the main component of TG Ballastcleaner Æ

. Because the sodium hypochlorite (NaC lO) contained in TG Ballastcleaner Æ partially forms hypochlorous acid (HClO) in ballast water, the acut e toxicity value for the most sensitive species in free chlorine is for the Water flea ( Ceriodaphnia dubia ), which shows LC 50 24 h with a concentration of 0.005 mg/L 1 . The acute toxicity of many life forms is between 0.01 and 0.1 mg/L.

3.4.1.2 Other components

The other components are sodium hydroxide (NaOH) , sodium chloride (NaCl), sodium sulfite (Na 2 SO 3 ) and sodium sulfate (Na 2 SO 4 ). Sodium chloride is the main component of ballast water (seawater) and as sodium hydroxide exists onl y in a trace amount, sodium hydroxide does not cause changes in the pH of seawater. Therefore, these two substances were excluded from the scope of study in this secti on. Sodium sulfite, which is the main component of TG Environmentalguard Æ , and sodium sulfate were cons idered as object substances.MEPC 60/2/2 ANNEX Page 18

I:\MEPC\60\2-2.doc Sodium sulfite, which is the main component of TG Environmentalguard Æ , reduces and neutralizes TRO in disinfected s eawater, thereby completely eliminating this substance. The unreacted sodium sulfite reacts with the diss olved oxygen in the disinfected ballast water, forming sodium sulfate, and is released into the ballast-water discharge waters.

The acute toxicity for aquatic organisms is described as follows: the most sensitive species of aquatic life for sodium sulfite at 16-32 mg/L (as SO 3 -S) 2 are Green algae ( Chlamydomonas reinhardtii ) EC 50 8.9 h, ( Chlorella vulgaris ) EC 50 6.4 h, and ( Scenedesmus basiliensis ) EC 50 8.2 h. On the other hand, the most sensitive species for sodium sulfate is the aquatic plant Diatom ( Nitzschia linearis ), which showed TLm 120 h = 1,900 mg/L 3

.

3.4.1.3 Relevant Chemicals

Substances in this summary is limited to 8 type s of Relevant Chemicals detected in the landbased test, among which most sensitive species from the acute toxicity test are described. Other Relevant Chemicals are described in the fu ll text or in the appendix 1 (Key Data).

Data on the toxity of RC12-bromochloroacetic aci d is not available and was substituted by the data of dibromochloroacetic acid which has hi gher toxicity based on the chemical structure.

Table 3.4.1: Acute toxicity of most sensitive species fo r Relevant Chemicals by class

Class Species End point Period Concentration (mg/L) Reference

RC3 Dichlorobromomethane

Other life forms (ciliates) ( Tetrahymena pyriformis ) EC 50 Growth rate 24h 240 Y.Yoshioka et al. (1985)
RC4 Dibromochloromethane
Other organisms (ciliates) Ciliate ( Tetrahymena pyriformis ) EC 50 24h (Growth

rate) 65 Y.Yoshioka et al. (1985) RC5 Bromoform (tribromomethane)

Fish (seawater

acclimation) Sheepshead minnow ( Cyprinodon variegatus ) LC 50 96h 7.1 G.S.Ward et al. (1981)

RC8 Sodium bromate Invertebrate (molluscan) Pacific Oyster (Crassostrea gigas) LC 50 96h >30 E.A. Crecelius

RC12 Bromochloroacetic acid - - - - No data RC15 Monobromoacetic acid

Aquatic plants (algae) Green algae ( Scenedesmus

subspicatus ) E μ C 50 Growth rate 72h 1.4 R. Kuhn et al. (1990)

RC16 Dibromoacetic acid

Fish Fathead minnow ( Pimephales promelas ) LC 50 96h 69 M.A. Mayes et al. (1985) RC17 Tribromoacetic acid

Fish Java medaka ( Oryzias javanicus ) LC 50 96h 101 Appendix 13 9MEPC 60/2/2 ANNEX Page 19

I:\MEPC\60\2-2.doc 3.4.2 Chronic aquatic toxicity

The chemical substances examined in section 3.4.1 were also the objects of this section.

3.4.2.1 Active Substances

The object of study as an Active Substances is sodium hypochlorite, which is the main component of TG Ballastcleaner Æ

. Because the sodium hypochlorite contained in TG Ballastcleaner Æ partially forms hypochlorous acid (HClO) in ballast water, the chronic toxicity results for the most sensitive species in free chlorine was Cladoceran ( Daphnia magna ), NOEC 14d = 2-4 μ g/L 10 . Thus, other genera, not limited to the water flea, showed t oxicity values on the order of 10 μ g/L.

3.4.2.2 Other Components

Although a search of the literature was carried out, chronic toxicity values for sodium sulfite and sodium sulfate could not be obtained.

Sodium sulfite, which is the main component of TG Environmentalguard Æ , changes to sodium sulfate, and the second main component of seaw ater, in a short period of time (15 minutes: materials were submitted at time of Basic Approva l). Therefore, it is judged that no chronic toxicity exists.

3.4.2.3 Relevant Chemicals

Eight limited kinds of Relevant Chemicals, whic h were detected in the land-based tests are described in this summary.

It was not possible to find chronic toxi city data for RC3-bromodichloromethane, RC4-dibromochloromethane, RC8-bromate ion, RC12-bromochloroacetic acid, and RC17 tricbromoacetic acid. The evaluations of the chronic toxicities of bromodichloromethane and dibromochloromethane were performed usi ng data for bromoform, based its structural relationship with the aforementioned substances.

The chronic toxicity values for bromate ion, bromochloroacetic acid, and tribromoacetic acid were evaluated considering a safety f actor in the acute toxicity values.

Table 3.4.2: Chronic toxicity of most sensit ive aquatic life in Rele vant Chemicals by class

Class Species End point Period Concentration ( mg/L ) Reference RC5 Bromoform (tribormomethane)

Fish Sheepshead minnow ( Cyprinodon

variegatus ) NOEC 4d 2.9 P.T. Heitmuller et al. (1981) RC15 Monobromoacetic acid

Invertebrate (crustaceans) Water flea (Daphnia magna ) NOEC 21d 3.2 R.Kuhn et al. (1989)MEPC 60/2/2 ANNEX Page 20

I:\MEPC\60\2-2.doc 3.4.3 Endocrine disruption

The applicants confirmed that the Active Subs tances, four other chemical substances, and 23 Relevant Substances re lated to TG Ballastcleaner Æ and TG Environmentalguard Æ are not included in the Candidate list of 553 substances in the EC report, ìTowards the establishment of a priority list of substances for further eval uation of their role in endocrine disruption.î

In submitting this proposal, the applicants also confirmed that there have been no changes in the contents of the above-mentioned report from the time of Basic Approval.

3.4.4 Sediment toxicity

For substances which have the potential property of accumulating or adsorbing in large quantity in sediments, toxicity with respect to or ganisms inhabiting sediments will be evaluated.

As the evaluation standard, Log Kow has been adopted in accordance with the Methodology for information gathering and conduct of work of the GESAMP-BWWG (BMW.2/C irc.13, 10 June, 2008), by referring Hazardous Substances Data Bank (HSDB), a database of the National Library of Medicineís TOXNET system ( http://toxnet.nlm.nih.gov/ )) and Syracuse Research Corporationís database ( http://www.srcinc.com/what-we-do/databaseforms.aspx?id=385 ).

3.4.5 Bioavailability, biomagnifi cation, and bioconcentration

Evaluation criteria are the bi oconcentration factor (BCF) > 2000 obtained in the experiment Methodology (BM W .2 / Circ.13, 10 June 2008).

Therefore, these values are cited from HSDB an d the Syracuse Research Corporation database.

3.4.6 Food web and population effects

Because no data are available, it was evaluated by using the BCF values.

3.5 Data on mammalian toxicity

In this section, only data on mammalian toxicity is described, and evaluation for each item is described in section 7.2.

3.5.1 General

Mammalian and human toxicity by Active S ubstances, other components and Relevant Chemicals in relation to TG Ballastcleaner Æ was assessed.

Subjects evaluated include acute toxicity, effects on skin and eyes, repeated dose toxicity, chronic toxicity, developmental and reproductive toxicity , carcinogenicity, mutagenicity and genotoxicity and toxicokinetics. Only Active Substances a nd bromoform, the most concerned chemical in Relevant Chemicals, are de scribed in this summary.MEPC 60/2/2 ANNEX Page 21

I:\MEPC\60\2-2.doc 3.5.2 Acute toxicity

3.5.2.1 Acute toxicity of Active Substances

Toxicity in oral dosage of chlori ne water (sodium hypochlorite) to rats and toxicity in inhalation of sodium hypochlorite in mice are shown in Table 3.5.2.1.

Table 3.5.2.1: Acute toxicity and LD 50 of Active Substances in mammals

Value Species Reference/Comments/ Justification for missing data AS Sodium hypochlorite Oral LD 50 (mg/L) 1.23-1.46g/kg 12.5% FAC Rat Proposal for the Health Classification and Labelling of the ESR substance Sodium Hypochlorite,ECBI/14/05 Dermal LD 50 (mg/L) No data Inhalation LC 50 (mg/L/4h) >10.5mg/L air rate 10 L/min Rat IUCLID P.61 (95)

3.5.2.2 Acute toxicity of Relevant Chemicals

Toxicity in oral dosage and toxicity in inhala tion of bromoform to rats are shown in Table 3.5.2.2.

Table 3.5.2.2: Acute toxicity and LD 50 of bromoform in mammals

Value Species Reference/Comments/Justification for missing data RC5 Bromoform Oral LD 5 0 (mg/L) 1
, 1 47 m g/kg Rat fe m ale H S D B(2005) Dermal LD 5 0 (mg/L) N o Data Inhalation LC 50 (mg/L/4h) No Data Can be substituted with data for chloroform, which displays high volatility.

3.5.3 Effects on skin and eye

3.5.3.1 Effects of Active Substances on skin and eye

Exposure to sodium hypochlorite in a percent ra nge caused skin and eye irritation, but no effect was observed in the concentration of general use (10-100 ppm as free available chlorine).

3.5.3.1.1 Skin and eye irritation

(Effects will be described depending on a level of free available chlorine.)

A. Case of 10% free available chlorine or higher

A study by Colgate-Palmolive Company (1985) indi cates exposure of 12.7% hypochlorite caused only mild irritation of normal or scratched sk in of rabbits. Duprat (1974) found exposure of 12.5% hypochlorite caused severe skin irritation in rabbits, but concl uded this irritation does not correspond to corrosive effects according to EU criteria. In eye irritation (including corrosive effects), corrosive effects on eye were demonstr ated at the concentra tion of 14.25% (Grant, 1962) and 12.7% (Colgate-Palmolive, 1985).MEPC 60/2/2 ANNEX Page 22

I:\MEPC\60\2-2.doc B. Case of an aqueous solution of 5-10% free available chlorine

Osterberg (1977) reported significan t irritation effects were not observed in skin irritation of animals exposed to about 5% solution as well as Nixon (1975) found very minor irritation to rabbits in toxicity test. However, the expos ure to 5% solution or higher caused human skin irritation (Nixon, 1975).

3.5.3.1.2 Skin sensitization

Skin sensitization was not found in an animal test with an 8% hypochlorite solution according to a standard sensitization procedure. There are a few reports on cases of allergic contact dermatitis caused by skin sensitization to the hypochlorite and conclusive agreement has not been reached yet. No skin sensitization of sodium hypochlorite ha s been proposed based on these collected data.

3.5.3.2 Effects of other components on skin and eye

Irritation of the skin and eyes by s odium hydroxide is extremely strong.

Regarding irritation of the skin and eyes by sodium sulfite, although based on limited study, the results have shown that this substance is not a strong irritant. Descriptions of the skin sensitization of sodium sulfite we re not found in IUCLID or HSDB.

With sodium sulfate, no irritation was observed, ev en when 500 mg was appl ied in a rabbit test. Regarding irritation of the eyes, the description states that this chemical causes very slight irritation in cases where it actually penetrates th e eyes, but the affected part recovers. Although no direct data were available for sensitization by sodium sulfate, as noted in the table, OECD SIDS has rejected the possibility that s odium sulfate causes increased sensitization.

3.5.3.3 Effects of Relevant Chemicals on skin and eye

Table 3.5.3.1: Effects of bromoform on skin and eye

Species Method Results (including scores where available) Reference/Comments/ Justification for missing data RC5 Bromoform
Skin Ra b b it Sing l e dose s o f 2,0 0 0 m g/kg u n der a c u f f on the intact skin of rabbits were survived by two rabbits treated with undiluted bromoform. HSDB(2005)

Eye Rabbit The undiluted liquid was moderately irritating to rabbit eyes. Healing appeared complete in 1 to 2 days. HSDB(2005)

3.5.4 Repeated dose toxicity tests

3.5.4.1 Repeated dose toxici ty of Active Substances

Repeated dose toxicity of the Active Substances in mammals was not available in the data listed in NOAEL.MEPC 60/2/2 ANNEX Page 23

I:\MEPC\60\2-2.doc 3.5.4.2 Repeated dose toxi city of Relevant Chemicals

NOEL data was obtained on RC3-Dichlorobromomethane, RC4-Dibromochloromethane, RC-Bromoform, and RC16-Dibromoacetic acid, and listed in the tables below.

Table 3.5.4.1: Repeated dose of RC3-Dichlorobromomethane

Exposure Route Oral administration Exposure Duration 102 weeks Exposure dose 0, 25, or 50 mg/kg/day Species 50 male B6C3F1 mice
Method Gavage
Results renal cytomegaly in male mice, an effect considered minimal in the absence of data demonstrating renal functional impairment

NOAEL 1.79 mg/kg/day = LOAEL 17.9 mg/kg/day (25 mg/kg/day x 5 days/7 days) x 0.1 NOEL No description
Reference/Comments/ Justification for missing data EPA IRIS (2008)

Table 3.5.4.2: Repeated dose of RC4-Dibromochloromethane

Exposure Route Oral administration Exposure Duration 13 weeks Exposure dose 0, 15, 30, 60, 125, or 250 mg/kg Species Fischer-344 rats and B6C3F1 mice
Method Fischer-344 rats and B6C3F1 mice were administered 0, 15, 30, 60, 125, or 250 mg/kg chlorodibromomethane for 13 weeks by gavage. Results A Fisher Exact test showed that incide nces of these liver lesions at doses of 60 mg/kg/day or above were elevated relative to the vehicle controls, thus 30 mg/kg/day is the NOEL. NOAEL 21

. 4 m g/kg/ d a y NOEL No description
Reference/Comments/ Justification for missing data EPA IRIS (2008)

Table 3.5.4.3: Repeated dose of RC5-Bromoform

Exposure Route Oral Exposure Duration 13w Exposure dose 0, 12, 25, 50, 100, 200 mg/kg/day (5 days/week) Species Rat Method Gavage Bioassy Results Hepatocellular vacuolization was observed in most male rats (10/l0 at 200 mg/kg, 8/10 at 100 mg/kg, 8/10 at 50 mg/kg, 5/10 at 25 mg/kg, 6/10 at 12 mg/kg, and 3/10 vehicle controls). NOAEL 17

. 9 m g/kg/ d a y (con v ert e d f r o m 2 5 m g/k g / da y ) NOEL No description Reference/Comments/ Justification for missing data EPA IRIS (2008)MEPC 60/2/2 ANNEX Page 24

I:\MEPC\60\2-2.doc Table 3.5.4.4: Repeated dose of RC16-Dibromoacetic acid

Exposure Route Oral (Gavage) Exposure Duration 2 to 79days Exposure dose No description Species Rats Method Rats were gavaged daily for 2 to 79 d with a by-product of water disinfection, dibromoacetic acid (DBAA). Results No abnormalities were detected at the dosage of 2 mg/kg. The changes suggest that the testicular effects of DBAA are sequelae to structural and/or functional changes in the Sertoli cell. NOAEL 2 m g/k g /da y NOEL No description Reference/Comments/ Justification for missing data HSDB(2009)

3.5.5 Chronic Toxicity
3.5.5.1 Chronic toxicity of Active Substances

NOAEL data were obtained and listed in the table below.

Table 3.5.5.1: Chronic toxici ty of AS-Sodium hypochlorite

Exposure Route Oral Exposure Duration 2 years Exposure dose 0, 70, 140, 275 mg/L Species F344 rats
Method Drinking water
Results No effects seen at 14 and 66 weeks.
NOAEL 14

. 4 m g/kg/ d a y NOEL No description
Reference/Comments/ Justification for missing data Proposal for the Health Classification and Labelling of the ESR subtance Sodium Hypochlorite,ECBI/14/05

3.5.5.2 Chronic toxicity of Relevant Chemicals

NOAEL data of RC8-bromate ion were obtained and listed in the table below.

Table 3.5.5.2: Chronic t oxicity of RC8-Bromate ion

Exposure Route Oral Exposure Duration 100 weeks Exposure dose 0, 1.1, 6.1, 12.9, and 28.7 mg BrO 3 - /kg-day Species F344 rat male Method Drinking water Results Nonneoplastic kidney lesions were observed in rats. Although the severity of chronic nephropathy was comparable between control and treated rats, there was a signific ant dose-dependent increase in theincidence of urothelial hyperplasia in rats in dose groups of 6.1 mg/kgday and higher. NOAEL 1.1 mg BrO 3 - /kg-day (converted from 1.5 mg KBrO 3 /kg-day) NOEL No description Reference/Comments/ Justification for missing data EPA IRIS (2001)MEPC 60/2/2 ANNEX Page 25

I:\MEPC\60\2-2.doc 3.5.6 Developmental and reproductive toxicity

3.5.6.1 Developmental and reproducti ve toxicity of Active Substances

Data on developmental and reprodu ctive toxicity of sodium hypochl orite is limited, but there is no direct evidence to indicate the adverse effect of sodium hypochlorite on development and reproduction. Similarly, there is no evidence of adverse effect in an epidemiological study on people drinking chlorinated water. These studie s indicate sodium hypoc hlorite should not be classified into the substances adversely affecting reproduction.

3.5.6.2 Developmental and reproducti ve toxicity of Relevant Chemicals

An example for the case of bromoform is shown below.

Table 3.5.6.1: Developmental and repr oductive toxicity of RC5-bromoform

Exposure Route Injection Exposure Duration 10 days Exposure dose 100-200 mg/kg/day Species Guinea pig Method Injection of 100-200 mg/kg/day to Guinea pig for 10 days Results Pathological change in kidney and liver NOAEL No description NOEL No description Reference/Comments/ Justification for missing data HSDB (2005)

3.5.7 Carcinogenicity

3.5.7.1 Carcinogenicity of Active Substances

In a study on carcinogenicity of the drinking wate r in rats and mice, ther e was no evidence to demonstrate the incidence of tumor increase by Activ e Substances. Available data do not indicate that sodium hypochlorite has to be classified as carcinogenic. International Agency for Research on Cancer (IARC) presumes sodium hypochlorite belongs to Group 3 (not classifiable as carcinogenic to human). Sodium hypochlorit e is therefore not tr eated as carcinogenic.

3.5.7.2 Carcinogenicity of Relevant Chemicals

Data on bromoform is listed in below.

Table 3.5.7.1: Carcinogenicity of RC5-Bromoform

Species Method Details Results Reference/Comments/ Justification for

missing data F344/N rats 2 yr gavage studies There was no evidence of carcinogenic activity for male B6C3F1 mice given 50 or 100 mg/kg bromoform or for female B6C3F1 mice given 100 or 200 mg/kg; male mice might have been able to tolerate a higher dose. Survival of female mice was reduced, partly due to a utero-ovarian infection HSDB(2005)MEPC 60/2/2 ANNEX Page 26

I:\MEPC\60\2-2.doc 3.5.8 Mutagenicity and genotoxicity

3.5.8.1 Mutagenicity and genot oxicity of Active Substances

There was some data indicating in vitro mutagenic activity of sodium hypochlorite , but a detailed in vivo study using mice indica tes this substance has no mu tagenic activity (Hayashi et al. , 1988). Other in vivo study also showed no mutagenic effect of this subs tance. These data related to genetic toxicity of sodium hypochlorite did not indicate the final conclusion 15 , but further data would not be required based on no effects on carci nogenicity. Data obtained indicate sodium hypochlorite does not exhibit mutageni city so that this substance is not classified as mutagenic.

3.5.8.2 Mutagenicity and genot oxicity of Relevant Chemicals

A case of bromoform is described in table below.

Table 3.5.8.1: Mutagenicity and genotoxicity of bromoform

Species Method Details Results Reference/ Comments/ Justification for

missing dataAroclorinduced rat liver S9 fraction Based on preliminary bacterial toxicity determinations, bromoform was evaluated for mutagenicity at concentrations of 5, 10, 50, 100, 500, and 1000 ug/plate using the direct plate incorporation method. The mutagenicity of bromoform was also tested for mutagenicity in Salmonella tester strains TA98, TA100 and TA1535, both with and without metabolic activation at dose levels of 0.02, 0.05, 0.1, and 0.2 ml/dessicator. In this study, bromoform caused a reproducible positive response in all three strains. HSDB(2005)

3.5.9 Toxicokinetics

3.5.9.1 Toxicokinetics of Active Substances

No data existed.

3.5.9.2 Toxicoki n etics of Relevant Chemicals

An example of bromoform is described in the table below.

Table 3.5.9.1: Toxicokinetics of RC5-Bromoform

Species Observation/Remarks Reference/ Comments/ Justification for

missing data No description Bromoform metabolized to carbon monoxide by hepatic microsomal mixed function oxidases. HSDB(2005)MEPC 60/2/2 ANNEX Page 27

I:\MEPC\60\2-2.doc 4 USE OF ACTIVE SUBS TANCES AND CHEMICALS

4.1 Method of using chemicals

Usage of TG Ballastcleaner Æ and TG Environmentalguard Æ was described in ìOnboard instruction manual of chemicalsî supplie d separately by the chemical producer.

4.2 Chemical Supply System

The system shall be supplied with the chemicals TG Ballastcleaner Æ and TG Environmentalguard Æ produced and quality-assured by Toagosei Co., Ltd. and the supply network.

4.3 Chemical supply method

The chemicals shall be safely and securely s upplied to chemical storage tanks on the ship equipped with the system by using small containe rs made of proper materials, tank trucks, and small chemical tankers.

5 MATERIAL SAFETY DATA SHEETS (MSDS)

The material safety data sheets (MSDS) for TG Ballastcleaner Æ and TG Environmentalguard Æ have been revised from the Basic Approval vers ion in accordance with GHS classification. Details are shown in appendix of the assessment report.

6 RISK CHARACTERIZATION

6.1 Screening for persistency, bioaccumulation and toxicity

Risk evaluations in connection with persisten ce, bioaccumulation and toxicity were conducted for the chemicals detected in the land-based tests (treated ballast water after neutralization/reducti on). The chemicals detected in thos e land-based tests a nd their measured maximum concentrations are shown below in Table 6.1.1.

Table 6.1.1: Chemicals detected in land-ba sed test and their maximum concentrations

Chemical Measured maximum concentration (mg/L)
RC3 Dichlorobromomethane 0.88×10 -3

RC4 Dibromochlormethane 16×10 -3

RC5 Bromoform 330×10 -3

RC8 Bromate 46×10 -3

RC12 Bromochloroacetic acid 0.47×10 -3

RC15 Monobromoacetic acid 5.7×10 -3

RC16 Dibromoacetic acid 47×10 -3

RC17 Triibromoacetic acid 0.1×10 -3MEPC 60/2/2 ANNEX Page 28

I:\MEPC\60\2-2.doc It should be noted that sodium sulfite, which is the main component of TG Environmentalguard Æ and is classified as an Other Component, rapi dly changes to sodium sulfate by reaction with dissolved oxygen that exists in the surface layer water. Accordingly, for sodium sulfite, it is appropriate to evaluate only acute toxicity for aquatic life.

Regarding sodium sulfate, which forms by decom position of sodium sulfite, the sulfuric acid ion concentration calculated from the composition of general seawater is 2,701mg/kg, whereas the sulfuric acid ion concentration contributed by ballast water treated with sodium sulfite is 24.8 mg/L, and thus is approximately 1/100 of the concentration that naturally exists in seawater. Although there is consid ered to be no risk of effect s on aquatic environments into which treated ballast water is discharged, the acute toxicity of this chemical will be evaluated.

6.1.1 Persistency

Degradation of the object chemical substances occurs by abiotic degradation (hydrolysis) and biotic degradation (aerobic degradation and anaerobic degradation). However, because the amount of micro-organisms necessary to demonstrate the degradation capacity in the judgment criteria (half-life in seawater of 60 days or less) does not exist in ballast water or in waters where ballast water is discharged, biotic degradation virtually cannot be expected. Acco rdingly, because abiotic degradation (hydrolysis) is the main reaction, all of the object chemicals were determined to be persistent (Yes), based on the criterion for pers istency (half-life in seawater exceeds 60 days).

6.1.2 Bioaccumulation

Object chemical substances are determined to be non-bioaccumulative as the log Pow is less than three for all compounds.

6.1.3 Toxicity tests

6.1.3.1 Acute toxicity

Acute toxicity of object chemical substances against aquatic organisms is listed in the aforementioned Table 3.4.1.

Because sodium sulfite, which is an ot her component of TG Environmentalguard Æ , is added in a quantity greater than the equivalent amount nece ssary to reduce all of the residual chlorine, excess sodium sulfite remains in the treated ballas t water and is discharged into the waters during deballasting. The water into which the treated ballast water is discharged is the surface layer water. The remaining sodium sulfite from th e reaction with TRO reacts with the dissolved oxygen that exists in the surface layer of the wate r and is rapidly oxidized to sodium sulfate. Accordingly, based on this property of sodium su lfite, it is appropriate to evaluate only acute toxicity for aquatic life, a nd evaluation based on the PEC/PN EC ratio will be performed.

Sodium sulfite reacts with dissolved oxygen to form sodium sulfate. This reaction was confirmed at the time of Basic Approval, and the fact that it is almost consumed within 15 minutes was shown.

From the above fact, it is considered that all of the sodium sulfite, which is added in an excess quantity forms sodium sulfate within 15 minutes after deballasting in the treated ballast water and seawater. In the above-mentioned land-based tests, it has been confirmed that it does not affect dissolved oxygen.MEPC 60/2/2 ANNEX Page 29

I:\MEPC\60\2-2.doc 6.1.3.2 Chronic toxicity

The chronic toxicity values of the object chemical s for aquatic life obtained from the database, as shown in the previous Table 3.4.2, were RC5-b romoform, 2.9 mg/L and RC15-monobromoacetic acid, 3.2 mg/L. As these values greatly excee ded the T criterion, NOEC<0.01mg/L, in the PBT criteria, chronic toxicity was determ ined to be No (no chronic toxicity).

Chronic toxicity data were not obt ained on RC3-dichlorobromomethane, RC4-dibromochloromethane, RC12-bromochl oroacetic acid, RC16-dibromoacetic acid, RC17-tribromoacetic acid, and RC8-bromate ion. NOE C 0.01 mg/L or more can be expected, as those acute toxicity values listed in Table 3.4.1 are 1.0 mg/L level or more. Therefore, the evaluations were NO (does not display chronic toxicity).

6.1.4 Evaluation by PBT Criteria

The results up to this point fo r the respective substances were arranged according to the PBT criteria as shown in Table 6.1.2.

Table 6.1.2: PBT criteria for 8 chemical substances

Object chemical substances of PBT criteria Persistence P (Yes or No) Bioaccumulation B (Yes or No) Toxicity T (Yes or No)
OC Sodium hypochlorite No No No RC3 Dichlorobromomethane Yes No No RC4 Dibromochloromethane Yes No No RC5 Bromoform Yes No No RC8 Sodium bromate Yes No No RC12 Bromochloroacetic acid Yes No No RC15 Monobromoacetic acid Yes No No RC16 Dibromoacetic acid Yes No No RC17 Triibromoacetic acid Yes No No

Substances which are evaluated ìYesî for all of the items Persistence, Bioaccumulation, and Toxicity in this table are identified as PBT substances.

As shown in the table, all of the chemicals are not PBT substances. However, for chemical substances which are evaluated as displaying pers istence, PEC/PNEC values were calculated in order to evaluate the effects on the aquatic environment, and this evaluation was made.

6.1.5 Evaluation by PEC/PNEC

The PEC/PNEC ratio was evaluated using the acu te toxicity data for the aquatic organisms against the target substance, the maximum concentr ation of the target substance detected in the land-based test, and the MAM-PEC Model to calcul ate the degree of dilution of ballast water in the port. The input data used in MAM-PEC Model assumes higher ballast water amount so as not to underestimate actually discharged ballast water in a year in the Rotterdam port.

The chemical species for which PEC/PNEC calcu lations were made were the 9 species of dichlorobromomethane, dibromochlorometha ne, bromoform, bromochloroacetic acid, monobromoacetic acid, dibromoacetic acid, tribromoacetic acid, bromate ion, and sodium sulfite.MEPC 60/2/2 ANNEX Page 30

I:\MEPC\60\2-2.doc Because the acute toxicity values were used, the factor 1000 was taken from Table 2 in the Methodology (BWM.2/Circ.13, 10 June 2008) and was selected as th e assessment factor for use in the calculations.

An average GRT in the table is recalculated fo r daily basis to generate 1,067 kt/day for the number of arriving ships, which is then multiplied by 0.5 for a ratio of the ballast water discharging ship for evaluation, resulting in a GRT of 533.5 kt/day. Using the above calculation results in 280.1 kt/day for the amount of ballast water per day.

The values of predicted environmental concen tration (PEC) obtained by dividing the maximum measured value obtained in the land-based te st by the dilution factor obtained from the aforementioned MAM-PEC Model, the predicted no-effect concentration (PNEC) obtained by dividing each maximum acute toxicity value by the assessment factor of 1000, and the obtained PEC/PNEC ratio are shown in Table 6.1.3. As the evaluation standard, PEC/PNEC>1 is considered to indicate that the subs tance has an effect on aquatic life.

As a result, all of the substances to be designated as evaluation object were determined as having no effect on aquatic life.

Table 6.1.3: PEC/PNEC values Yes: Effect on aquatic organism, No: No effect on aquatic organism

Test substance Species Dilution factor Maximum measured

value PEC PNEC PEC/ PNEC Evaluation

( )

mg/L (mg/L) ( ) mg/L

RC3

Dichlorobromo-

-methane Other life forms (Ciliates) ( Tetrahymena pyriformis ) 379 0.88×10 -3 0.00232
×10 -3 240×10 -3 9.7
×10 -6 No

RC4

Dibromochloro-

-methane Other life forms (Ciliates) ( Tetrahymena pyriformis ) 465 16×10 -3 0.0344
×10 -3 65×10 -3 5.3
×10 -4 No

RC5

Bromoform Fish (acclimatization to seawater) Sheepshead minnow ( Cyprinodon

variegatus ) 418 330×10 -3 0.789
×10 -3 7.1×10 -3 0.111 No

RC8

Sodium bromate Mollusks Pacific oyster ( Crassostrea gigas ) 184 46×10 -3 0.250
×10 -3 25.4×10 -3 0.0098 No

RC12

Bromochloroacetic

acid Not possible to obtain

data.
Based on structure, substituted with high toxicity

bromodichloroacetic

acid. 182 0.47×10 -3 0.00258
×10 -3 53×10 -3 4.9
×10 -5 NoMEPC 60/2/2 ANNEX Page 31

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

Test substance Species Dilution factor Maximum measured

value PEC PNEC PEC/ PNEC Evaluation

( )

mg/L (mg/L) ( ) mg/L

RC15

Monobromoacetic

acid Aquatic plant (algae) Green algae ( Scenedesmus

subspicatus ) 182 5.7×10 -3 0.0313
x10 -3 1.4
x10 -3 0.022 No

RC16

Dibromoacetic

acid Fish

Fathead minnow ( Pimephales

promelas ) 182 47×10 -3 0.258
×10 -3 69
×10 -3 3.74
×10 -3 No

RC17

Tribromoacetic

acid Fish
Java medaka ( Oryzias javanicus ) 182 0.1×10 -3 0.55x10 -6 101x10 -3 5.4x10 -6 No

OC3

Sodium sulfite Aquatic plant (algae) Green algae ( Chlamydomonas

reinhardtii, Chlorella vigaris,

Scenedemus

basiliensis ) 442656 22 0.0497 ×10 -3 63 ×10 -3

*1 0.00080 (Short term) No

Note: 1: Method of calculating PNEC for sodium sulfite PNEC: The most sensitive species used for sodium hypochlorite is Aquatic plant (algae) ( Chlamydomonas reinhardtii

, Chlorella vilgaris

, Scenedesmus basiliensis ), EC 50 , 6.4 h-8.9 h, 16-32 mg/L (as SO 3 -S). Accordingly, the value is 40 mg/L (=(16 x 80)/32) as SO3, that is, 63 mg/L (=(16 x 126)/32) as sodium sulfite. PNEC is obtained by dividing this value by the above-mentioned assessment factor of 1000, the result being PNEC=63 μ g/L.

6.2 Evaluation of treated ballast water

6.2.1 Results and evaluati on of land-based tests

The land-based tests of this ballast water treatment system were performed at Ballast Tech NIVA AS in Norway. The location of the experiments was an experimental station in Solbergstrand, which is approximately 30 km south of Oslo. Land-based tests comprised a total of 10 cycles were conducted consisti n g of 5 cycles each with b r ackish water and seawate r

. During the period when the land-based tests were performed, this ballast water treatment system operated smoothly. All equipment in the injection of TG Ballastcleaner Æ , the neutralization process using TG Environmentalguard Æ etc., including concentra tion control, operated as expected.

Various types of measurements were performe d. The operation of the treatment system was smooth, and also satisfied the treatment effect as judged by the D-2 standard. Measurements of the environmental risk of Relevant Chemicals were also performed, and vari ous data contributing to the study of risk were collected.MEPC 60/2/2 ANNEX Page 32

I:\MEPC\60\2-2.doc .1 Treatment rate:

- The test water treatment rate was at the set value of 350 m 3 /h and satisfied the test condition.

.2 Water quality items:

- The water quality of the test water was water temperature: 0.15-5.1°C, pH: 7.95-8.6, DO: 8.8-11.8 mg/L, salinity: 20.6-21.5 (PSU, in tests of brackish water) and 32.1-33.6 (PSU, in tests of s eawater). Although the tests were performed under rather low water temperat ure conditions, there were no items that showed abnormal values.

In both the brackish water tests and the s eawater tests, the values of DOC, POC, and TSS all exceeded the levels specifi ed in the Guidelines (G8), and tests succeeded.

.3 Relevant Chemicals:

- Analysis of Relevant Chemicals was pe rformed for the 23 substances designated by the GESAMP-BWWG..

As a result, 8 items shown in Table 6.1.1 were detected, and these were studied respectively as objects of risk assessment.

.4 Analysis of chemical activity:

- For the trihalomethanes, etc., time-dependent change was analysed up to 48 hours immediately after neutralization. As a result, the trihalomethanes showed a tendency to decrease slightly after neutra lization treatment. Bromate ion showed virtually no change. In brackish water, the halogenated acetic acids showed a peak after 2

− 4 hours, and a decreasing tendency thereafter. In seawater, these substances showed a peak after 24 ho urs, followed by a decreasing tendency.

.5 D-2 standard biological items:

- As results of the measurem ents of L and S size aquatic organisms and bacteria, the D-2 standards were fullfiled in all tests.

.6 Toxicity tests:

- The toxicity tests, which were performed included a growth inhibition test for diatoms, acute toxicity test for cr ustaceans, reproduction effect test for crustaceans, acute toxicity test for oys ter embryos, acute toxicity and chronic toxicity tests for juvenile fish, and a reproduction effect test for rotifers.

Summarizing the results as a whole, in these toxicity tests, the deballast water after neutralization treatment can be ev aluated as displaying no toxicity. However, effects of the treated water could be seen in one test item. It was the growth inhibition test of the diatom Skel etonema costatum. In 2 of 11 cases, values of 66% and 100% were measured for EC10. (In all other cases, theyMEPC 60/2/2 ANNEX Page 33

I:\MEPC\60\2-2.doc were >100%.) However, it is difficult to sa y that there was any large effect, as the value when calculated as EC50 was >100%, and the value of 66% also shows no effect when diluted by 2 times. Because no effects were observed with the exceptions of this item, the effect on aquatic life of the deballast water treated with this system is considered to be extremely slight.

.7 Confirmation of neutralization

- With this system, ballast water is discharged after neutralization of the TRO. The TG Environmentalguard Æ used in neutralization is added in an excess quantity. Confirmation of neutralization was perf ormed by a residual chlorine sensor incorporated in the system. However, in the land-based tests, these results were verified by manual analysis. The DPD method was used. In measurements using an absorption spectroscopy (man ufactured by HACH), th e detection limit was 0.02 mg/L, and it was not possible to confirm reductions below this level. Therefore, neutralization was confirmed by also using a high resolution absorption spectroscopy measurement method with detection lim it of 0.0012 mg/L, using an absorption spectroscope with a 5 cm cell le ngth. The complete neutralization was successfully confirmed, and sati sfactory result was obtained.

.8 Reduction of dissolved oxygen concentration in discharged water

- Theoretically, it can be judged that the reduction of dissolved oxygen by TG Environmentalguard Æ (main component: sodium sulf ite), which is added in an excess amount in the neutralization process, is minimal. However, because there were misgivings regarding the ef fect of TG Environmentalguard Æ on the dissolved oxygen in environmental waters, the actual va lues were measured. As a result, the difference in dissolved oxygen before and after neutralization was judged to be very slight.

6.2.2 Evaluation of onboard tests

Voluntary onboard tests were carried out twice. Due to the small amount of the S size (10 μ m to less than 50 μ m) existing in these tests, the tests were not completely consistent with the official test cycle. However, results, which satisfied th e D-2 standard, were obtai ned from measurements of aquatic organism of the L size (50 μ m and larger) and S size. The evaluation of bacteria is omitted because these were qualitative tests.

It was confirmed that neutralization and reducti on treatment during discharge are performed in the same manner as in the land-based test and, fu rthermore, the species of Relevant Chemicals contained in the discharged ballast water after neutralization are the same and their concentrations are lower than the maximum values in the land-based test.

6.2.3 Determination of holding time

Holding time is not necessary before discharge of the treated ballast water because no TRO in the ballast water is discharged outboard in this ba llast water treatment system by being instantly reduced and neutralized by sodium sulf ite immediately prior to discharge.MEPC 60/2/2 ANNEX Page 34

I:\MEPC\60\2-2.doc 6.3 Risk characteriza tion and analysis

6.3.1 Reaction with organic matter

The Relevant Chemicals detected in the land-base d test and their concentrations are shown in Table 6.1.1. The following evaluations were conducted.

6.3.2 Characterization of de gradation routes and rates

Degradation of the object chemical substances occurs by abiotic degradation (hydrolysis) and biotic degradation (aerobic degr adation and anaerobic degradati on). However, because abiotic degradation (hydrolysis) is the main reaction, all of the chem icals, which were subject to evaluation, were determined to be persistent ìYesî.

6.3.3 Prediction of discharge and environmental concentration

The predicted environmental concentration (PEC) at the Port of Rotterdam was calculated using the maximum concentrations detected in the land-based test and a MAM-PEC Model for obtaining the degree of dilution of the ball a st w ater in the h arbo u r

. 6.3.4 Evaluation of pote ntial for bioaccumulation

The substances of concern were evaluated as having no effects, as BCF<2000 or LogKow<3 for all of the substances.

6.3.5 Environmental assessments

Because all of the substances of concern displayed BCF<500 and have low bioaccumulation potential, assessment of secondary poisoning of top predators such as mammals, birds, etc., is not necessary.

All of the substances of concer n also displayed Koc<500 and have low potential to partition into sediments; therefore, assessment of eff ects on sediment species is not necessary.

6.3.6 Effect on aquatic organisms

The evaluation criterion value (P EC/PNEC) based on PEC (Predicted Environmental Concentration), which is obtained by dividing the ma ximum measured values obtained in the land-based test by the dilution factor obtained with th e MAM-PEC model, and thePredicted No-Effect Concentration (PNEC), which is obtained by di viding the respective maximum acu te toxicity values by an assessment factor of 1000, was <1 for all of th e chemical substances which were objects of evaluation. Therefore, all of the chemicals were evaluated as having no effect on aquatic life.

6.3.7 Effect of sediment species

The substances of concern were evaluated as ha ving no effect because LogKow<3 in all cases.

6.3.8 Effect on mammalian species

NOAEL was described, this being necessary in ev aluations by the Margin of Safety (MOS), as described in section 3.5 above. Re garding toxicokinetics, the results of a search of databases were shown in the section 3.5 a bove. However, it was no t possible to obtain data that could be evaluated.MEPC 60/2/2 ANNEX Page 35

I:\MEPC\60\2-2.doc 6.3.9 Comparison of effect Asse ssments and discharge toxicity

A toxicity test of the discharge water during de ballasting in the land-based test was performed using the 5 species shown in 3.1.1. 1, and it was confirmed that the discharge water displays no acute toxicity or chronic toxicity. Because th is does not contradict the results for the acute toxicity and chronic toxicity of the individual substances in section 3.4, a more detailed evaluation of effects is not necessary.

Regarding dissolved oxygen in the land-based test and environmental waters, judging from the measured values obtained in the land-based test, any effects are extremely slight.

7 RISK ASSESSMENT

7.1 Risks to ship safety

7.1.1 Effects on ship hull and safety

Figure 2 summarizes the systems for supplying TG Ballastcleaner Æ and TG Environmentalguard Æ used for ballast water treatment (JFE-BWMS).

Figure 2: Diagram of TG Ballastcleaner Æ and TG Environmentalguard Æ supply systems

7.1.1.1 Effects on hull

The past durability tests on coating have proved that the concentration of a solution injected into ballast tanks has no effect on the hull and pipes as measures such as epoxy lining or coating are taken to protect them from the corrosion caused by treated ballast water. Pumps and valves are operated by the remote auto-controllerMEPC 60/2/2 ANNEX Page 36

I:\MEPC\60\2-2.doc Since TG Environmentalguard Æ is only limited to the reaction of the reduction of TG Ballastcleaner Æ and the consumption of dissolved oxyg en, it has no effect on the hull and ballast water pipes where tr eated ballast water flows.

7.1.1.2 Effects on ballast tanks

The surfaces (for tank inner surfaces) must be coated or lined (for pipes) with chlorine- and salt water-resistant epoxy resins and other materi als to protect ballas t tanks from corrosion.

7.1.1.3 Effects on hull plates

During deballasting, residual chlorine disappears and TG Environmentalguard Æ becomes somewhat excessive. At that time, TG Environmentalguard Æ acts as a reducing agent of residual chlorine in treated ballast water and its reducing power is str onger than those of tran sition metals such as iron and zinc. It has therefore no effect on the ou tside plating of the ship made of steel plates.

7.1.1.4 Measures related to ba llast water management system

Possible leakage places such as the surrounding of ch emical storage tanks were chosen and proper measures such as coaming were taken.

7.1.1.5 Countermeasures for corrosion

Since sodium hypochlorite, which is the main component of TG Ballastcleaner Æ , is a corrosive substance, the risk of corrosion of the parts directly touching treated ballast water such as ballast tanks and pipes is likely to increase compared to the normal case of ballasting with seawater.

Corrosion tests were conducted to quantitatively understand the effects on the following parts of the hull related to the taking and discharging of ballast water:

.1 Coated steel plates:

- used for the inner surfaces of ballast tanks and ballast pipings

.2 Uncoated steel plates:

- Bulk carriers sometimes take seawater into their cargo holds in heavy ballast condition.

.3 Galvanized steel pipe:

- used for parts of ballast pipings

.4 Zinc electrode for elect ric corrosion protection:

- used for electrolyte corrosion protection in ballast tanks

.5 Gasket:

- used for the flanged joints of ballast pipingsMEPC 60/2/2 ANNEX Page 37

I:\MEPC\60\2-2.doc .6 Constituent material for butterfly valve:

- Material constituting the butterfly valve used in the ballast piping

.7 Rubber material for valve sealing:

- used for ballast piping valves

Most of the inner surfaces of ballast tanks and ballast pipes are epoxy resin coated. Existing ships and new ships mostly use tar epoxy paints and modified epoxy paints, respectively. Using these two types of paints with a film thickness of about 250 μm to 300 μm, ìcoating durability testsî and ìsimulated defective coat ing durability testsî were conducted.

Since bulk carriers sometimes take seawater into their cargo holds in heavy ballast condition and their uncoated steel plates have ch ances to touch ballast water, uncoa ted steel plates were tested. We also tested galvanized steel pipes, which are occasionally used for parts of ballast water pipes.

For comparison, natural seawater and the simulate d ballast water made of natural seawater and TG Ballastcleaner Æ with a concentration of 20 mg/L (upper injection limi t concentration) were used.

Assuming an actual uptaking and discha rging pattern of ballast water, we set an effective concentration of initially injected chloride at 20 mg/L, left the specimens in the air for 3 days after soaking them in the solution for 7 days, and again injected TG Ballastcleaner Æ to a concentration of 20 mg/L. Experiments were conducted by repeating th is cycle of 10 days 18 times for 180 days.

As a result, the difference between the seaw ater environment and the natural seawater environment had no significant effect on the potentials.

7.1.2 Chemical supply system

7.1.2.1 Chemical supply equipment

TG Ballastcleaner Æ and TG Environmentalguard Æ are supplied to ballast pipes from their chemical storage tanks by remotely controlling the valves and pumps. Crew has hence no chances of touching the chemicals during normal ballast water treatment operation.

7.1.2.2 Chemical storage requirements

Chemicals are supplied to their storage tanks on th e ship from a tank truck on land or a chemical supply boat anchored close aboard th e ship when the ship is moored.

7.1.2.3 Chemical storage tanks

Materials for the TG Ballastcleaner Æ storage tank shall be steel pl ates coated or lined with polypropylene, polyethylene, or polyvinyl chlori de, or Titanium and Titanium alloy plates.

Materials for the TG Environmentalguard Æ storage tank shall be steel plates coated or lined with polypropylene, polyethylene, or polyvinyl chloride, stainless steel plates.

7.1.2.4 Flash point/ignition temperature of chemicals

Both chemicals have no danger of self-ignition.MEPC 60/2/2 ANNEX Page 38

I:\MEPC\60\2-2.doc 7.1.3 Chemical management methods

7.1.3.1 Management method for TG Ballastcleaner Æ

If TG Ballastcleaner Æ is stored at a high temperature, it s main component sodium hypochlorite partly decomposes into sodium chloride and o xygen. The liquid temperature needs to be kept at 20°C or less to inhibit the decomposition. Measures, such as installing an equipment to directly cool the storage tank or placing the tank in an air-conditioned compartment, shall be taken.

TG Ballastcleaner Æ freezes when cooled at 0°C or less. The frozen chemical causes pipes to clog and the inner pressures to increase, leading to po ssible pipe rupture. The temperature hence shall be kept at 0°C or higher by wrapping insulating material around the pipe.

7.1.3.2 Management method for TG Environmentalguard Æ

When TG Environmentalguard Æ is used in a cold region, the chemical freezes. The liquid temperature hence shall be kept at 0°C or higher, taking measures such as covering the container with insulating materials.

7.1.3.3 Precautions in handling of chemicals

Since TG Ballastcleaner Æ is a strong alkali reactive chemical, it needs to be handled with the greatest care referring to the in struction manual (for example, operation supplying the chemical to the ship).

7.1.4 Health risk to crew and deck personnel

7.1.4.1 Effects on health of crew and deck personnel

Since the ballast water control sy stem installed on the ship is remotely operated, human exposure to chemical substances is hardly probable dur ing ballast water treatment operation on the ship.

7.1.4.2 Crew and deck pers onnel exposure scenarios

No human exposure occurs under normal operation.

7.1.4.3 Response to leaks

When chemical leakage occurs, the main valve of the chemical storage tank concerned shall be immediately closed. When a sma ll quantity of TG Ballastcleaner Æ leaks on the floor in a coaming, the leaked liquid shall be washed out to the wastewater collection tank after diluting it with a large quantity of general service water. In the case of a large quantity of leakage, the leaked liquid shall be washed out to the wastewater collection tank after neutralizing and reducing it with TG Environmentalguard Æ for the reduction of TB Ballastcleaner Æ . The crew engaged in the washing operation shall wear safety glasses and a disaster-prevention mask, protective equipment, and protective gloves.

Although TG Ballastcleaner Æ is a safe chemical, it produces chlorine when contacting acids, and hence chemical products such as acids shall not be stored near the chem ical tank and the supply line. Bulletin boards shall be placed in worki ng spaces to call attention to the safety of this operation.MEPC 60/2/2 ANNEX Page 39

I:\MEPC\60\2-2.doc 7.1.4.4 Response during emerge ncy stops and power outages

The following are emergency shutdown a nd power failure response procedures:

Emergency shutdown:

- When emergency shutdown is needed, injection pumps shall be immediately stopped at the machine side or through remo te control to discontinue the injection of TG Ballastcleaner Æ into ballast water.

Power outage response:

- When power outage occurs, the whol e system of both TG Ballastcleaner Æ and TG Environmentalguard Æ supply lines shall be stoppe d to prevent uncontrollable chemicals from flowing into ballast tanks and discharge area. A safety device such as the one needing resetting shall be installed in the system for the case of restarting the system after power return.

7.1.4.5 Response during supply of chemicals

When supplying TG Ballastcleaner Æ or TG Environmentalguard Æ to their chemical storage tanks on the ship, operation shall be carried out following the instructions in the manual.

7.1.4.6 Response during inspections and maintenance

The daily inspection of chemical tanks shall be carried out to check leakage and damage to equipment, taking account of the safety of crew according to the manual.

The repair of chemical tanks shall be carried out following the instructions in the manual on the washing and ventilation in the tanks, protective cl othing, etc., to prevent crew and personnel from exposure to chemicals.

7.1.5 Crew safety

If the ballast water treatment system is normally operated and adequately maintained, the safety of crews can be provided.

7.2 Risk to human health

This section will study the risk to human health of the chemicals related to the JFE-BWMS, the treated ballast water which is stored in the ballast tanks before neutralization (primary treatment water), and the treated ballast water which is discharged from the ship after neutralization (secondary treatment water).

The study of risk will be carried out in four stages, as follows:

.1 Designation of the chemical subs tances which are objects of study. .2 Designation of the toxicities of the respective chemical substance. .3 Designation of the exposure level (concen tration and duration or frequency) for the respective chemical substances. .4 Quantification of risk using these data.MEPC 60/2/2 ANNEX Page 40

I:\MEPC\60\2-2.doc Predictions of exposure levels were made by calculation of the Margin of Safety (MOS) by the following formula, using the simulation program EUSES 2.1 for Hu man Exposure Scenario (HES).

) / / (

_ ) / / (
d kg mg Level Exposurel d kg mg NOAEL MOS =

Comparing the MOS obtained here and MOSref, this toxicity is allowable in cases greater than this; in other words, it is c onsidered safe. As MOSref, 100 is generally used (this being the product of 10, representing the difference between humans and the species for which toxicity values were obtained, and 10, representi ng individual differences in humans).

7.2.1 Exposure assessment

.1 The chemical substances which are object s of study are the substances contained in the following liquids.

.1 Chemicals (TG Ballastcleaner Æ , TG Environmentalguard Æ )

.2 Treated ballast water which has been treated by the BWMS and is stored in the ballast tanks before neutralization (primary treatment water)

.3 Treated ballast water which has been wi thdrawn from the ballast tanks and is discharged from the ship after neutra lization (secondary treatment water).

.2 Classified in terms of the persons who are objects of study and exposure routes, the following two categories are considered.

.1 Persons on onboard (crew, 8 hours/day x 5 days/week) Exposure routes: Normally, re spiration and dermal contact

.2 General public (persons in port while ship is at anchor, persons in area near shore)

Exposure routes: Oral ingestion, respiration and der m

.3 Condition of B W MS al contact.

A summary of the individual oper ations studied for human risk on these liquids is shown in Table 7.2.1.

Table 7.2.1: Individual oper ations studied for human risk and object liquids

Crew General population (a) Normal operation (ballasting) B -- (a) Normal operation (deballasting) -- C (b) Resupply of chemicals A -- (c) Equipment breakdown A -- (d) Ship accident or other emergency A -- (e) Maintenance of ballast tanks and equipment A and B -- Here, A: Chemicals (TG Ballastcleaner Æ , TG Environmentalguard Æ ) B: Treated ballast water store in ballast tanks before neutralization C: Treated ballast water discharged from ship after neutralizationMEPC 60/2/2 ANNEX Page 41

I:\MEPC\60\2-2.doc 7.2.2 Human health effects

In the land-based tests, 23 species of Relevant Chemicals contained in the treated ballast water were analysed. A total of 9 chem ical substances, including sodium hypochlorite, which is Active Substance, and sodium sulfite, which is other co mponent, in addition to 8 chemical substances detected in therein, were identified as object s of the following study of human health risk.

7.2.3 Human Exposure Scenarios (HES)

The single operation conditions recommended by the GESAMP-BWWG (MEPC 58/2/7, annex 5, paragraph 2.15.1 (A) and studied here were as follows:

.1 Resupply of chemicals .2 Ballasting (taking on ballast water) .3 Deballasting (discharging ballast water) .4 Inspection and maintenance of equipment and chemical tanks .5 Inspection and maintenance of ballast tanks .6 Trouble and emergency states (concretely, this assumes breakdowns of the system and accidents)

7.2.3.1 Exposure scenario during ballast water uptake and ballast tank maintenance

Exposure levels for the Active Substance, sodium hypochlorite and the 8 Relevant Chemicals shown in Table 7.2.2 were estimated using EUSES 2.1, and were then used to determine risk. The oral NOAEL and inhalation NOAEL of the chronic toxicity of these chemical substances is shown in Table 7.2.2.

The equation mentioned in EUSES 2.1 Background Report, Model Calculation, page III, and the conversion default values were used for conve rting the oral NOAEL to inhalation NOAEL. In the general population, IH air (respiration rate) is 20m 3 /day, however, because a value of 10m 3 for one 8-hour day was shown for personnel, this value was followed here.

Table 7.2.2: Concentration contained in treated ballast water in land-based tests ( μ g/L)

No. Chemical substances Oral NOAEL (mg/kg/d) Inhalation NOAEL(mg/m 3 ) Reference

AS Sodium hypochlorite 14.4 50.4 ECBI/14/05
RC3 Dichlorobromomethane 1.79 6.26 EPA IRIS
RC4 Dibromochloromethane 21.4 74.9 EPA IRIS
RC5 Tribromomethane 17.9 62.7 EPA IRIS
RC8 Bromate 1.1* 3.85 EPA IRIS
RC12 Bromochloroacetic acid 2* 7 -
RC15 Monobromoacetic acid 2 7 -
RC16 Dibromoacetic acid 2 7 HSDB
RC17 Tribromoacetic acid 2* 7 -

Note: * Because no NOAEL data were available for br omochloroacetic acid, monobromoacetic acid, and tribromoacetic acid, the NOAEL data for dibromoacetic acid, which is considered to have stronger toxicity, were substitute d for these substances.MEPC 60/2/2 ANNEX Page 42

I:\MEPC\60\2-2.doc The maximum concentration of sodium hypochlorite in the treated ballast water in the ballast tanks (primary treatment water) is 20 mg/L. Ho wever, the crews on onboard are not exposed to the treated ballast water as the ballast water pipi ng and the ballast tanks form a closed loop. In the ballast tanks, ventilation vents are provided in or der to keep the air pressure in the tank head space at the same level as the atmosphere, and th e vent holes are normally on the deck. Because the air in the ballast tanks is discharged from these vents during ballasting, the effect on human health during this operation wa s studied by the following method.

When the ship takes on ballast water, the air in the ballast tank head space is discharged outside of the ship through vents installed on the deck, etc., as the water le vel in the ballast tanks rises. Because exposure on deck is limited to mooring work when berthing and deberthing, the worst case is airborne exposure in the ballast tank head space during internal inspection work in the ballast tanks, which is performed with a fre quency of approximately one time in 6 months. Using the assumed exposure time of 8 hours per month which was calculated based on the hearing results with domestic shipping companie s and the maximum concen tration detected in the land-based tests as input data, the human health risk was studi ed by calculations using EUSES 2.1. The calculated results of th e obtained RCR (Risk Characterization Ratio = MOS/MOSref) are shown in Table 7.2.3. Because the result is larger than 1, it can be judged that there is no health risk to humans, and it is not necessary for the crew to wear personal protective equipment (PPE).

Table 7.2.3: Health risk to cre w of remaining water in ballast tank (prima ry treatment water)

No. Test substance MOS MOSref RCR(MOS/MOSref) AS Sodium hypochlorite 1870 100 18.7 RC3 Dichlorobromomethane 1640 100 16.4 RC4 Dibromochloromethane 2930 100 29.3 RC5 Tribromomethane 174 100 1.74 RC8 Bromate ion 5000 100 50 RC12 Bromochloroacetic acid 3.291x10 6 100 3.29x10 6
RC15 Monobromoacetic acid 9.21x10 7 100 9.21x10 5
RC16 Dibromoacetic acid 1.65x10 7 100 1.65x10 5
RC17 Tribromoacetic acid 1.02x10 10 100 1.02x10 8

7.2.3.2 During ballast water discharge

A EUSES 2.1 simulation was performed to consid er exposure of the general population to bromoform, bromate ion, bromochloroacetic acid, monobromoacetic acid, and dibromoacetic acid.

The calculated results of the obtained Risk Ch aracterization Ratio ( RCR) = MOS/MOSref) are shown in Table 7.2.4. Because the result is larger than 1, it can be judged that there is no health risk to humans, and risk control measures are not necessary.MEPC 60/2/2 ANNEX Page 43

I:\MEPC\60\2-2.doc Table 7.2.4: Health risk to genera l public of discharged ballast water (secondary treatment water)

Risk Characterization Ratio (MOS/MOSref) Local Regional No. Chemical substance Inhalatory Total Exposure Inhalatory Total Exposure RC3 Dichlorobromomethane 9.16 x10 6 5.92 x10 6 9.48 x10 6 6.55x10 6
RC4 Dibromochloromethane 1.27x10 7 3.01 x10 6 1.29 x10 7 3.38x10 6
RC5 Tribromomethane 4.89x10 5 9.85x10 4 4.96x10 5 1.11x10 5
RC8 Bromate ion 1.58x10 10 9.41x10 4 6.24x10 12 1.06x10 5
RC12 Bromochloroacetic acid 1.50x10 9 1.32x10 7 1.58x10 9 1.46x10 7
RC15 Monobromoacetic acid 1.85x10 8 1.87x10 5 2.01x10 8 1.89x10 5
RC16 Dibromoacetic acid 1.20x10 6 1.56x10 5 1.25x10 8 1.79x10 5
RC17 Tribromoacetic acid 5.60x10 12 5.60x10 7 9.66x10 12 6.11x10 7

7.2.3.3 Replenishment of chemicals and insp ections and maintenance of equipment and chemical tanks

It is necessary to conduct advance safety trai ning for crew members using the Userís Manuals and Material Safety Data Sheets pr ovided by the manufacturer of the chemicals. Safety is also secured by crew wearing personal prot ective equipment (PPE) during work.

7.2.3.4 Inspections and maintenance of ballast tanks

In cases where personnel enter balla st tanks, safety management is performed in accordance with a manual. There are no health-related problems for personnel under the condition that work is performed 8 hours/month, and it can be judged that wearing PPE is not necessary. However, in cases where work may exceed this frequency, in a ddition to securing safety by wearing PPE, it is desirable to wear an in -line mask or oxygen tank, particularly in cases where protection against inhalation is necessary. In the MOS cal culation by EUSES 2.1, a condition, in which considerable time has passed sin ce air was taken into the ballast tank, and the air and ballast water have reached a state of equilibrium, was cal culated as the worst case . However, in cases where personnel actually enter ballast tanks to pe rform maintenance, etc., it can be assumed that virtually all of the air in the tank has been replaced with fresh air as a result of complete discharge of the ballast water imme diately before the pers onnel enter the tank. Therefore, in the operational aspect, there are considered to be no safety-related problems even if personnel do not wear PPE.

Normally, when entering a ballast tank for mainte nance or other reasons, safety is further secured by performing gas detection and oxygen starvation measurements in the tank, and personnel enter the tank only after ventilation measures are taken.

7.2.3.5 Malfunctions and accidents

In the event of a chemical leak, clean-up work for TG Ballastcleaner Æ and TG Environmentalguard Æ is performed. In this work, crew must wear the protective glasses or protective masks, rubber gloves, rubber boots, helmets, and othe r PPE and protective clothing specified in those paragraphs.MEPC 60/2/2 ANNEX Page 44

I:\MEPC\60\2-2.doc 7.3 Risk to water environment

The assessment in the previous sections showed that involved substances are not PBT substance, and the PEC/PNEC ratios do not exceed 1. It is, th erefore, judged that further assessment is not
necessary.

8 CONCLUSIONS

Test results and evaluations up to the pr eceding chapters are summarized as follows.

.1 The present system for treating ballast water has been smoothly operated for the land-based test and all equipment have b een operated as planned in the injection of TG Ballastcleaner Æ including controlling the concentration and the neutralization with TG Environmentalguard Æ

.

.1 The amount of test water treated was 350 m 3 /hr as a set value, satisfying the test conditions.

.2 There were no test terms showing abnorma lity in the quality of test water. All of DOC, POC, and TSS values in te sts of brackish water and seawater exceeded the standard specified by Guidelines (G8), thus meeting the test requirements.

.3 Twenty-three substances specified by the GESAMP-BWW G were analysed as Relevant Chemicals. Following analys is of the results, 8 substances in the test required further ev aluation for risk assessment.

.4 Aquatic organisms, both large and small in size, as well as bacteria were tested in biological terms for the D-2 standard of ballast water. All tests results met the specified D-2 standard.

.5 Toxicity tests performed included measuring the growth inhibition of Skeletonema costatum, acute toxicity to marine copepods, effects on the reproduction of marine copepods, chroni c toxicity to oyster embryo, acute toxicity and chronic toxi city to juvenile fish, effects on reproduction of Rotifera (Brachinonus plicatilis), respectively.

After reviewing overall results, these t oxicity tests demons trate neutralized deballasted water is not toxic.

.6 In the present system, the DPD me thod was used to confirm if the neutralization were completed, while the TRO is neutralized to be released into the aquatic environment. Using the absorbance method (by a spectrophotometer from Hach Co.), a detection limit was determined to be 0.02 mg/L. Hence, in conjunc tion, ìhigh resolu tion absorption spectroscopyî with an optical path of 5 cm was used to extend the detection limit to 0.0012 mg/L to confirm full neutralization. The measurement results were satisfactory.MEPC 60/2/2 ANNEX Page 45

I:\MEPC\60\2-2.doc .7 The concentration of dissolved oxyg en in discharged water was actually measured. Results demonstrate the difference of the dissolved oxygen concentration before and after neutra lization was found to be in the level where no problem exists.

.2 Although the main subject of th is application is the risk assessment using the data obtained from the land-based test, a vol untary onboard test was conducted by actually operating the system onboard and performing ballasting and deballasting operations on actual ballast tanks to check the accordance of th e system with the D-2 standard and to find the values of chemical by-products.

Results of the voluntary onboa rd test are as follows:

.1 Results of the neutraliz ation/reduction of TRO:

The time series data on the change in TRO in the monitoring data of TRO during the neutralization/reduction pro cess conducted using the system in the onboard test started to show nega tive values indicating a reduced state immediately after the injection. The confirmed value with the ORP meter, which was installed to check TRO tw ice during deballas ting in the onboard test, represents satisfactory results.

.2 Results of chemical analysis:

The detected values for byproducts we re lower than those for the landbased test, indicating that there is no problem.

.3 Results of biological analysis:

Due to the small amount of the S size (10 μ m to less than 50 μ m) existing in these tests, the tests were not comple tely consistent with the official test cycle. However, results, which satis fied the D-2 standard were obtained from measurements of aquatic organism of the L size (50 μ m and larger) and S size.

.3 Persistency, bioaccumulability, and toxi city were evaluated for the chemical substances detected in the above land-based test (treated ball ast water) to confirm that all of these chemical substances are not the persistent, bioaccumulative, and toxic (PBT) substance.

.4 To evaluate the effects on the aquatic environment, values of PEC/PNEC were further calculated to be 1 or less in all cas es, thus indicating there is no risk to the aquatic environment.

.5 We estimated there are no effects on the bottom sediment because logKow is less than three.

.6 Concerning the effects on mammals, oral NOAEL of mammals were investigated. Data on toxicokinetics are also described.MEPC 60/2/2 ANNEX Page 46

I:\MEPC\60\2-2.doc .7 As effects of chemicals associated w ith the BWMS, treated ballast water before neutralization (primary treated water) and stor ed in a ballast tan k, and treated ballast water after neutralization and discharged overboard (secondary treated water) on human health were evaluated, the obtain ed RCR (MOS/MOSref) was higher than 1 in all cases, thus we estimated there is no risk.

.8 If it can be confirmed in land-based test s carried out in the future that the D-2 standard can be satisfied with a lower injection concentration, it will be possible not only to reduce bromoform, but also to reduce the effects on aquatic organisms due to the Relevant Chemicals as a whole. Therefore, continuing efforts will be made to further reduce th e injection concentration.

REFERENCES

1 P.A. Taylor, ìAn Evaluation of the Toxi city of Various Forms of Chlorine to Ceriodaphnia dubia ,î Environ Toxicol. Chem. 12 , 1993.

2 IUCLID DATASET (2000), Sodium Sulfite.

3 R. Patrich, J. Cairns Jr., a nd A. Scheier, ìThe relative sens itivity of diatoms, snails, and fish to twenty common constitu ents of industrial wastesî, The Progessive Fish-Cultirist, 1968.

4 Y. Yoshioka, Y. Ose and T. Sato, ìTes ting for the Toxicity of Chemicals with Tetrahymena pyriformis .î Sci. Total Environ. 43 , 1985.

5 G.S. Ward, P.R. Parrish and R.A. Rigby, ìEarly life st age toxicity tests wi th a saltwater fish: Effects of eight chemicals on survival, gr owth, and development of sheepshed minnows ( Cyprinodon variegates )î, Journal of Toxicology and Environmental Health, 8, 1981.

6 E.A. Crecelius, ìMeasurements of oxidants in ozonized seawater and some biological reactionî Journal Fish Research Board Canada, 36 , 1979.

7 R. Kuhn and M. Pattard, ìResu lts of the harmful effects of water pollutants to green algae ( Scenedesmus subspicatus ) in the cell multiplication in habitation testî,Wat. Res. 24 , 1990.

8 M.A. Mayes, F.A. Blanchard, D.L. Hopkins an d I.T. Takahashi, ìStatic acute toxicity of dibromonitrilopropionamide and selected degr adation products to the fathead minnow ( Pimephales Promelas Rafinesque )î, Environmental Toxicology and Chemistry, 4 , 1985.

9 Appendix 13: (Chronic toxicity test).

10 J.W. Arthur, et al. , ìComparative Toxicity of Sewage-E ffluent Disinfection to Freshwater Aquatic Lifeî, PB-248 653, U.S. EPA, 1975.

11 Unpublished paper: K. Hayashi, ìBehav ior of Sodium sulfite in Seawaterî.

12 P.T. Heitmuller, T.A. Hollister and P.R. Parrisk, ìAcute toxicity of 54 industrial chemicals to Sheephead Minnows ( Cyprinodon variegates ) Bull. Environm. Contam. Toxicol. 27 , 1981.MEPC 60/2/2 ANNEX Page 47

I:\MEPC\60\2-2.doc 13 R. Kuhn, M. Pattard, K. Peynak and A. Winter , ìResults of the Harm ful effects of water pollutants to Daphnia Magna in the 21 days reduction testî, Wat. Res. 23 , (4), 1989.

14 EUROPEAN COMMISSION DG ENV, ìTowards th e establishment of a priority list of substances for further evaluation of th eir role in endocrine disruptionî, 2000.

15 ìProposal for Health Classification and Labelling of the ESR substance Sodium Hypochloriteî ECBI/14/05.

16 IUCLID DATASET (2000), Sodium Hypochlorite.

17 Hazardous Substances Date Bank (HSDB), a database of the National Library of Medicineís TOXNET system ìTRI BROMOMETHANEî 20050623 on March 3, 2009.

18 IUCLID DATASET (2000), Sodium Sulfite.

19 ìOECD SIDS Initial Assessment Report: S odium sulfateî SIAM 20, 19-22 April 2005.

20 EPA IRIS: Toxicological review of Bromodichloromethane, January 11th, 2008.

21 EPA IRIS: Toxicological review of Dibromochloromethane, January 11th, 2008.

22 EPA IRIS: Toxicological review of Bromoform, January 11th, 2008.

23 Hazardous Substances Date Bank (HSDB), a database of the National Library of Medicineís TOXNET system ìDIBRO MOACETIC ACIDî 20090105 on March 3, 2009.

24 EPA IRIS: Toxicological review of Bromate, March 2001.

25 J Floor Anthoni, ìThe chemi cal composition of seawaterî, http://www.seafriends.org.nz/oceano//seawater.htm

___________