I:\MEPC\61\2-3.doc 

# E

MARINE ENVIRONMENT PROTECTION
COMMITTEE
61st session Agenda item 2 MEPC 61/2/3
17 March 2010 Original: ENGLISH

HARMFUL AQUATIC ORGANISMS IN BALLAST WATER

Application for Basic Approval of the MES Ballast Water Management System (FineBallast MF)

Submitted by Japan



### SUMMARY

Executive summary: This document contains the non-confidential information related to the application for Basic Approval of MES Ballast Water Management System (FineBallast MF), in accordance with the "Procedure for approval of ballast water management systems that make use of Active Substances (G9)" adopted by resolution MEPC.169(57)

Strategic direction: 7.1

High-level action: 7.1.2

Planned output: 7.1.2.4

Action to be taken: Paragraph 6

Related documents: BWM/CONF/36; MEPC 57/21; BWM.2/Circ.13 and BWM.2/Circ.24

Introduction

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

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

3 According to BWM.2/Circ.24, proposals for approval of ballast water management systems that make use of Active Substances are to be submitted to the Marine Environment Division of the Organization to be reviewed by the GESAMP-Ballast Water Working Group. In the meantime, a document on the proposal for approval containing all the non-confidentialMEPC 61/2/3 Page 2

I:\MEPC\61\2-3.doc data related to the respective ballast water management systems that make use of Active
Substances needs to be submitted to MEPC 61.

4 The competent authority in Japan has verified the application dossier, prepared by Mitsui Engineering and Shipbuilding Co. Ltd. (MES), and believes it to satisfy the data requirements of Procedure (G9).

5 Japan therefore submits the non-confidential part of the applicant's dossier in the annex of this document to the Organization for evaluation according to Procedure (G9). The complete dossier will be made available to the experts of the GESAMP-Ballast Water Working Group with the understanding of confidential treatment.

Action requested of the Committee

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

***MEPC 61/2/3 Annex, page 1

I:\MEPC\61\2-3.doc ANNEX

APPLICATION FOR BASIC APPROVAL OF THE FINEBALLAST MF
BALLAST WATER MANAGEMENT SYSTEM

Contents

1 INTRODUCTION

1.1 "FineBallast MF" BWMS working principles 1.2 Description of the "FineBallast MF" BWMS and its components 1.3 Chemical cleaning 1.4 Sampling and measurements 1.5 Quality control and assurance (G9: 4.2.4)

2 DEFINITIONS

2.1 Terms and definitions
2.2 Active Substances
2.3 Relevant Substances

3 DATA ON THE EFFICACY OF ORGANISM REMOVAL FROM NATURAL SEAWATER

3.1 Preparation for the test
3.2 Test methods
3.3 Test results

4 DATA REGARDING EFFECTS ON AQUATIC PLANTS, INVERTEBRATES, FISH AND OTHER BIOTA, INCLUDING SENSITIVE AND SIGNIFICANT ORGANISMS (G9: 4.2.1.1)

4.1 Acute aquatic toxicity 4.2 Chronic aquatic toxicity 4.3 Endocrine disruption 4.4 Sediment toxicity 4.5 Bioavailability/biomagnification/bioconcentration 4.6 Food web/population effects

5 DATA ON MAMMALIAN TOXICITY (G9:4.2.1.2)

5.1 Acute toxicity 5.2 Effects on eyes and skin 5.3 Repeated-dose toxicity 5.4 Chronic toxicity 5.5 Developmental and reproductive toxicity 5.6 Carcinogenicity 5.7 Mutagenicity/genotoxicity
5.8 ToxicokineticsMEPC 61/2/3 Annex, page 2

I:\MEPC\61\2-3.doc 6 DATA ON ENVIRONMENTAL FATE AND EFFECTS UNDER AEROBIC AND ANAEROBIC CONDITIONS (G9: 4.2.1.3)

6.1 Modes of degradation (biotic; abiotic) 6.2 Bioaccumulation, partition coefficient, octanol/water coefficient
6.3 Persistence and identification of the main metabolites in the relevant media (ballast water, marine and fresh waters) 6.4 Reaction with organic matter 6.5 Potential physical effects on wildlife and benthic habitats
6.6 Potential residues in seafood
6.7 Known interactive effects

7 PHYSICAL AND CHEMICAL PROPERTIES OF THE PREPARATIONS, ACTIVE SUBSTANCE, AND TREATED BALLAST WATER, IF APPLICABLE (G9: 4.2.1.4)

7.1 Physical and chemical properties of the Active Substance 7.2 Corrosivity

8 ANALYTICAL METHODS AT ENVIRONMENTALLY RELEVANT CONCENTRATIONS (G9: 4.2.1.5)

9 RISK CHARACTERIZATION

9.1 Screening for persistency, bioaccumulation and toxicity 9.2 Toxicity testing of the treated ballast water 9.3 Risk analysis for aquatic organisms

10 RISK ASSESSMENT

10.1 Risk to ship safety
10.2 Risk to environment

11 REFERENCES

12 APPENDICES

APPENDIX I EXTRACTION OF QAPP

APPENDIX II CHEMICAL ANALYSIS TEST REPORTS

APPENDIX III AQUATIC TOXICITY TEST REPORTS

APPENDIX IV CORROSIVITY TEST REPORTS

APPENDIX V MODEL ESTIMATION OF H 2 O 2 CONCENTRATION IN AIR IN
THE WORKING PLACE

APPENDIX VI REFERENCE ECOTOXICITY DATA ON H 2 O 2 AND CHLOROFORM
FROM LITERATURES

APPENDIX VII RISK ASSESSMENT

APPENDIX VIII EXPERIMENT USING 10% H 2 O 2 AS WEAK SOLUTION FOR THE
BWMS

APPENDIX IX MANGANESE ANALYSIS FOR THE BWMSMEPC 61/2/3 Annex, page 3

I:\MEPC\61\2-3.doc 1 INTRODUCTION

1.1 "FineBallast MF" BWMS working principles

Ballast water is processed in this system at in take (ballasting) by microfiltration. Organisms are completely removed from the ballast water by passing through the membrane in the separation removal procedure, requiring no other form of disinfection. "FineBallast MF" BWMS is therefore a system that does not use Active Substances in ballast water processing. Chemical cleaning by H 2 O 2 which corresponds to an Active Substance is necessary for membrane maintenance however.

1.2 Description of the "FineBallast MF" BWMS and its components

The "FineBallast MF" BWMS is a complete system and its operation can be divided into four components: pre-treatment; microfiltration; H 2 O 2 cleaning of the membrane; and control. The "FineBallast MF" BWMS is illustrated schematically in Figure 1.1.

The system consists of four components as fo llows (the outline of each component is shown in paragraphs 1.2.1 to 1.2.4):

.1 pre-filter;

.2 membrane module;

.3 CIP (cleaning in place) unit; and

.4 control unit.

A, B and C in Figure 1.1 denote the samples tested: "A" is influent water before filtration which meets IMO requirements, "B" is treated water for ballasting or deballasting, and "C" is the detoxified cleaning solution from the CIP unit before ballasting (see section 1.4 for sampling strategy details).

Figure 1.1: Schematic Process Diagram of the "FineBallast MF" BWMS and sampling position (A, B, C)MEPC 61/2/3 Annex, page 4

I:\MEPC\61\2-3.doc 1.2.1 Pre-filter

The Pre-filter is comprised of a 100~200 μm filter with automatic washing. The filter removes larger particles and organisms to prevent blockage of the flow passage. A filter is selected properly below pore diameter to block the memb rane module flow passage. The filter is fully automatic in terms of operation and washing without affecting the filtration process, and washing water is returned to the sea in situ.

1.2.2 Membrane module

Ballast water is processed by passing through the membrane at intake (ballasting). The membrane used with this system possesses an extremely uniform micro pore size, and can satisfy the D-2 standard without using Active Substances. The membrane improves the ballast water processing module, using tw o or more modules. The system operates automatically, and organisms filtered by the membrane are returned to the sea at regular intervals. The membrane module structure is shown in Figure 1.2.

Figure 1.2: Membrane module design

1.2.3 The CIP Unit

The "FineBallast MF" BWMS has a "Cleaning in Place" (CIP) unit using H 2 O 2 to clean out organisms adhering to the membrane after ballasting. The CIP-unit feeds a prescribed
amount of H 2 O 2 to seawater reserved in the membrane unit and starts cleaning. After cleaning, the remaining H 2 O 2 in the seawater is detoxified by a catalyst. The CIP unit is comprised of an H 2 O 2 feed tank, concentration meter, supply pump, filter, and catalyst unit. After ballasting is completed, chemical cleaning is executed automatically during navigation. The schematic process diagram of the CIP Unit is shown in Figure 1.3.MEPC 61/2/3 Annex, page 5

I:\MEPC\61\2-3.doc Figure 1.3: CIP Unit Schematic Process Diagram



### 1 .2.4 Control unit

The control unit controls the power supply, the automatic air valve, and the warning alarm for all equipment in the "FineBallast MF" BWMS.

This application for Basic Approval will focus on H 2 O 2 used in the CIP unit. The membrane module and other components are not considered to be relevant for Active Substance approval.

1.3 Chemical cleaning

After each ballasting operation, the membrane module is cleaned with seawater containing H 2 O 2 . The H 2 O 2 is added into the circulating seawater reserved in the membrane module, at a concentration of 15,000 mg/L or less. Chemical cleaning repeats circulation and holding for each membrane module for the prescribed time. After the prescribed time passes, H 2 O 2 remaining in the seawater is detoxified by a catalyst to less than 1.0 mg/L, and this seawater (detoxified cleaning solution) is s ent to the ballast tank in the next ballasting operation.

The reserved detoxified cleaning solution volume is smaller than the capacity of each ballast tank. For example, in the case of a 56,000 dwt type bulk carrier ship, the detoxified cleaning
solution would be diluted to over 1/70.

Test facility operation

Flow rate 1.2 m 3 /h/module Chemical cleaning time 12 h
Detoxification time 6 h
H 2 O 2 Concentration (maximum) 15,000 mg/L (at cleaning)
H 2 O 2 Concentration (minimum) Less than 1 mg/L (after detoxification)
Dilution water Seawater Catalyst material Manganese dioxide Space velocity below 100 h -1 Method of analysis Titration by 0.001N KMnO 4MEPC 61/2/3 Annex, page 6

I:\MEPC\61\2-3.doc 1.4 Sampling and measurements

Sampling locations (A, B and C) are indicated in Figure 1.1. All samples for chemical and ecotoxicity analysis (see Table 1.1) were collected in triplicate from untreated water (A), treated seawater (B) and detoxified cleaning solution (C). Sample (A) is untreated water for use as a control. Sample (B) is treated water to be used in performance analysis, chemical analysis, toxicity testing and corrosivity testing, respectively. Sample (C) (washout seawater from the CIP unit) is not required by Procedure (G9) either for toxicity tests or chemical analysis. However, (C) is used as a worst-case sample for any residual chemical, toxicity and corrosivity tests, excluding performance analysis.

Seawater was sampled according to guidelines in order to be analysed (see Table 1.1):

- whether water quality in the initial test water (A) meets the chemical and biological water quality criteria defined by the IMO;

- the efficiency of the "FineBallast MF" BWMS in removing/inactivating target organisms during ballasting after five days of storage (B);

- acute and chronic environmental toxicity after 5 days of storage from the time of ballasting (B);

- the corrosivity of treated seawater after 5 days of storage from the time of ballasting (B);

- any by-product formation after "FineBallast MF" BWMS treatment at day 0 after ballasting (B), and at day 5 after ballasting (B), and;

- acute and chronic toxicity of the detoxified cleaning solution (C) to use as a worst-case scenario after 5 days of storage.

Water samples (A, B, C) collected and stored for 5 days after beginning sampling (Day 0) were used for the toxicity tests for all test species (seawater or brackish), but with fish species, additional water samples (A, B, C) were collected at Day 2 and used for water renewal. The test facility made an additional run for Day 2 sampling.

Five-day stored samples at room temperature (20 o C) were used for the chemical analysis and toxicological tests according to the requirements listed in Guidelines (G8) (MEPC 58/23). The storage aims to simulate the condition for deballasted water at a certain period (at least 5 days) after stored in ballast tanks.MEPC 61/2/3 Annex, page 7

I:\MEPC\61\2-3.doc Table 1.1: Sample information for the "FineBallast MF" BWMS

Sample for Sampling
Location On-site

measurements Off-site measurement

Corrosivity A B C - Corrosivity

Toxicity Day 5 after ballasting A B C Brachionus plicatilis (Rotifer)
Skeletonema costatum (Algae) Monocorophium acherusicum (Amphipod) Ruditapes philippinarum (Bivalve) Cyprinodon variegates (Fish)

Chemical Analysis Day 5 after ballasting A B C - DO - pH
- H 2 O 2 - Salinity
- TRO - Temperature
- TSS
- POC
- DOC Free chlorine

Thiosulfate

Bromate

Bromoform

Chloroform

Dibromochloromethane

Dichlorobromomethane

Monobromoacetic acid

Dibromoacetic acid

Tribromoacetic acid

Monochloroacetic acid

Dichloroacetic acid

Trichloroacetic acid

Bromochloroacetic acid

Dibromoacetonitrile
1,2,3- Trichloropropane

Temperature, salinity, pH and dissolved oxygen concentration were measured for the samples used for acute and chronic toxicity tests using seawater and acute toxicity tests using brackish water before and during the tests. The result of on-site measurement is
shown in Table 1.2.

The same samples, collected and stored for 5 days under the same conditions before testing, were used for each chemical and toxicological test protocol for a given test time and

treatment.MEPC 61/2/3 Annex, page 8

I:\MEPC\61\2-3.doc Table 1.2: The result of water quality on samples for all analyses at consecutive times

Purpose of

Analysis Sample
ID Sampling
Date Storage
after

treatment (d) pH Temperature (°C) Salinity (psu) Dissolved Oxygen (mg/L)

A 2009.09.07 5 8.2 24.2 33.4 7.6
B 2009.09.07 5 8.4 24.7 33.7 7.5 Chemical analysis during acute seawater toxicity
test C 2009.09.08 5 7.7 26.1 34.3 7.4

A 2009.09.07 5 8.2 24.2 33.4 7.6
B 2009.09.07 5 8.4 24.7 33.7 7.5 #1
C 2009.09.08 5 7.7 26.1 34.3 7.4
A 2009.09.17 5 8.1 25.7 33.1 7.5
B 2009.09.17 5 8.2 26.2 33.4 7.8 #2

C 2009.09.18 5 7.8 26.9 33.2 7.4
A 2009.09.27 5 7.9 25.5 33.2 7.4
B 2009.09.27 5 8.1 25.4 33.4 7.6 #3
C 2009.09.28 5 7.8 25.7 33.5 6.9
A 2009.10.07 5 8.2 25.4 34.0 7.6
B 2009.10.07 5 8.1 25.3 34.3 7.4 Chemical analysis during Fish

Chronic Toxicity test

#4

C 2009.10.08 5 7.7 25.5 34.5 6.7

A 2009.10.07 5 8.2 25.4 21.0 7.6

B 2009.10.07 5 8.1 25.3 21.2 7.4 Chemical analysis during acute
brackish water

toxicity test C 2009.10.08 5 7.7 25.5 21.1 6.7

1.5 Quality control and assurance (G9: 4.2.4)

Quality Control and Assurance (QA/QC) is of primary importance. The essential goal is to deliver reliable analytic results of defined qua lity. All testing processes in analytical laboratories contain a rigorous quality contro l/quality assurance program consisting of a Quality Management Plan (QMP) and a Quality Assurance Project Plan (QAPP).

All analyses were carried out in accordance with standard methods, and toxicity testing was performed under supervision of the KORDI (Korea Ocean Research & Development Institute), Korea Testing & Research Institute (KTR) and NeoEnBiz. The KORDI laboratory is accredited by KOLAS (The Korea Laboratory Accreditation Scheme) for phytoplankton and micro-organism analyses. The KORDI study dire ctor is accredited by IOC-UNESCO for identification of harmful microalgae (appendix I). The KTR laboratory is accredited by KOLAS for chemical analysis of environmental sample s (appendix II). All the ecotoxicological tasting was carried out by NeoEnBiz Institute according to GLP. The data on quality assurance (QA) are provided for each test report (appendix III). Although the NeoEnBiz Institute is not accredited specifically for toxicological testing and the accreditation is not required for toxicity testing, the NeoEnBiz has specialized ecotox icology laboratories and personnel with solid experience in many toxicological researc hes mostly funded by the Korean government (e.g., Ministry of Land, Transport and Maritime Affairs). It also has conducted toxicity testing for the approval of previous ballast water management systems including GloEn-PatrolTM of Panasia Co. (MEPC 59/2/7).MEPC 61/2/3 Annex, page 9

I:\MEPC\61\2-3.doc 2 DEFINITIONS

2.1 Terms and definitions

2.1.1 "FineBallast MF" BWMS is the commercial name of the ballast water management system developed and used by the Mitsui Engineer ing & Shipbuilding Co., Ltd. The system is comprised of a microfiltration module with a pre-treatment component (pre-filtration for large particles over 100-200 micrometres, CIP, and a control unit (see paragraph 1.2). "FineBallast MF" BWMS treats ballast water at ballasting. During ba llasting, the seawater is treated by filtration only. Particles and marine organisms retained by the membrane filter are discharged back into the sea through washing of the membrane filter. For maintenance of the membrane filter however, the oxidizing agent, H 2 O 2 is used for cleaning.

2.1.2 "Treated Water" refers to water treated by the "FineBallast MF" BWMS.

2.1.3 "Ballast Water Discharge" refers to ballast water discharged overboard after the treatment by the "FineBallast MF" BWMS.

2.1.4 "Active Substance" in the "FineBallast MF" BWMS, is defined as H 2 O 2 (hydrogen peroxide), which is used for the membrane module cleaning, and the small
amount of H 2 O 2 can remain in treated water.

2.1.5 "Preparation" as defined in Procedure (G9) is not used by the "FineBallast MF"
BWMS.

2.1.6 "Relevant Chemicals" – The oxidizing effect of H 2 O 2 can cause oxidation reactions to produce reactive oxygen species such as hy droxyl radicals (OH•). The hydroxyl radical
can react with various chlorinated and brominat ed chemicals in natural seawater to produce a variety of chloro- and bromo-compounds. Here the oxidation by-products of OH• are
defined as Relevant Chemicals.

2.2 Active Substances

H 2 O 2 is clear colourless liquid normally handled in an aqueous solution. H 2 O 2 in itself (at NTP) is stable. Pure aqueous solutions in clean inert containers are relatively stable. Maximum stability is at pH 3.5~4.5. Commercial solutions must be stabilized with additives to prevent possible violent decomposition due to ca talytic impurities or elevated temperatures and pressure.

H 2 O 2 is not flammable. There is a dangerous fire hazard from the chemical reaction of H 2 O 2 with flammable materials, however. H 2 O 2 is a powerful oxidizer, particularly in its concentrated state, and reacts violently with combustible and reducing materials causing a fire and explosion hazard.

H 2 O 2 can behave both as an oxidizing and as a reducing agent.

as an oxidizing agent: H 2 O 2 + 2H + + 2e - ==> 2H 2 O Eo = + 1.763 V at pH 0
HO 2 - + H 2 O + 2e - ==> 3OH - Eo = + 0.878 V at pH 14

as a reducing agent: H 2 O 2 ==> O 2 + 2H + + 2e - Eo = - 0.66 V at pH 0
HO 2 - + OH - ==> O 2 + H 2 O + 2e - Eo = + 0.08 V at pH 14MEPC 61/2/3 Annex, page 10

I:\MEPC\61\2-3.doc H 2 O 2 is widely used as an oxidizing and reducing agent. In these redox reactions H 2 O 2 is normally degraded. In addition-reactions, the H 2 O 2 molecule as a whole is attached to another molecule to form perhydrates (analogous to hydrates e.g., Na 2 CO 3 •1.5H 2 O 2 , (NH 2 ) 2 CO•H 2 O 2 ). In substitution-reactions, the peroxide group is transferred to another molecule and hydrogen atoms are substituted (e.g., peroxo compounds). H 2 O 2 also forms stable salts with certain cations (e.g., K 2 O 2 ).

H 2 O 2 has been used as an algaecide and bactericide, at concentrations in the millimolar range (e.g., 0.2~1.5 mmol/L against filamentous cyanobacteria; Barroin and Feuilade, 1986).
H 2 O 2 is a powerful oxidant capable of damagi ng nucleic acids, proteins and pigments. Although this damage may be incurred by a direct reaction between biomolecules and the
H 2 O 2 , many of these effects are mediated by the Fenton reaction, whereby more reactive oxidants are generated, in particular the hydroxyl radical (OH•):

H 2 O 2 + Fe 2+ ==> OH• + OH - + Fe 3+

The extreme reactivity of the hydroxyl radical (OH• ) is indicated by its short half-life, typically nanoseconds. Hydroxyl radicals (OH•) attack nucleic acids, proteins and membranes and a consequently few parts of the cell are immune to their effects; even catalyses and peroxidases are attacked and degraded by th is highly reactive oxygen species.

2.3 Relevant Chemicals

The reaction of hydroxyl radicals (OH•) with naturally occurring chlorine and bromine ions in seawater during micro filter cleaning using approximately 1.5% of H 2 O 2 solution can possibly produce the various residual oxidative by-products as listed in Table 2.1. As cleaning solution is catalysed by manganese dioxide before tr ansferring into the ballast tank for more than 6 hours, the remaining H 2 O 2 and its oxidative by-products decrease below a certain level (for H 2 O 2 , less than 1 mg/L) in the ballast tank.

The manganese concentration in seawater is reported with 0.4~10μg/L (US EPA, 1984). Dissolved manganese of 0.198 mg/L was detected in the maximum in the detoxified cleaning solution in the bench-scale test. After it moves to the ballast tank, the detoxified cleaning solution is diluted to at least 70 times or more. Therefore, it is expected that dissolved manganese that remains in the detoxified cleaning solution decreases below the environmental influence concentration (see appendix IX).

Concentrations of potential Relevant Chemical s were measured in the detoxified cleaning solution as well as in the treated water after a 5-day storage period. The detoxified cleaning solution is diluted at least 70 times after transferring to the ballast tank. The concentration of remaining Relevant Chemicals in the cleaning solution is therefore expected to be decreased considerably.

A variety of chemicals can be produced by the reaction of oxidizing chemicals such as H 2 O 2 with seawater in the CIP unit. However, only a limited number of chemicals are known to be potentially harmful to human and ecosystem so far. Potential harmful Relevant Chemicals, which can be produced by the reaction of oxidat ive chemicals with seawater, are listed in Table 2.1, following document MEPC 59/2/13. Such chemicals should be checked in treated
ballast water when oxidative chemicals are used in any capacity that contacts seawater.

Chemicals listed in Table 2.1 were analysed in samples of treated water and detoxified cleaning solution as well as untreated water to evaluate the risk posed by the by-products remained in effluents from the tested BWMS. The measurement of the detoxified cleaningMEPC 61/2/3 Annex, page 11

I:\MEPC\61\2-3.doc solution samples was included to assess the environmental safety under the worst-case
condition.

Table 2.1: Overview of Potential Relevant Chemicals in Ballast Water using
Oxidative Chemicals as Active Substances

Ingredient (IUPAC Name) Identification Numbers (CAS) Chemical Formula Molecular Weight (g/mole)

Total Residual Oxidant - - -

Free chlorine - - -

Sodium thiosulfate 7772-98-7 Na 2 S 2 O 3 158.11

Sodium bromate 7789-38-0 NaBrO 3 150.9

Bromoform 75-25-2 CHBr 3 252.73

Chloroform 67-66-3 CHCl 3 119.38

Dibromochloromethane 124-48-1 CHBr 2 Cl 208.28

Dichlorobromomethane 75-27-4 CHBrCl 2 163.83

Monobromoacetic acid 79-08-3 C 2 H 3 BrO 2 138.95

Dibromoacetic acid 631-64-1 C 2 H 2 Br 2 O 2 217.84

Tribromoacetic acid 75-96-7 C 2 H 1 Br 3 O 2 296.74

Monochloroacetic acid 79-11-8 C 2 H 3 ClO 2 94.5

Dichloroacetic acid 79-43-6 C 2 H 2 Cl 2 O 2 128.94

Trichloroacetic acid 76-03-9 C 2 H 1 Cl 3 O 2 163.36

Bromochloroacetic acid 5589-96-8 C 2 H 2 BrClO 2 173.39

Dibromoacetonitrile 3252-43-5 C 2 HBr 2 N 198.84

1,2,3- Trichloropropane 96-18-4 C 3 H 5 Cl 3 147.43

3 DATA ON THE EFFICACY OF ORGANISM REMOVAL FROM NATURAL SEAWATER

The efficacy of ballast water management systems which produce Active Substances was evaluated by Administration in accordance with the Guidelines for approval of ballast water management systems (G8). The Guidelines (G8) include general requirements concerning design and construction, technical procedures for evaluation and the procedure for issuance of the Type Approval Certificate of ballast water management system. The Guidelines (G8) are unique compared to the requirements for type approval of traditional marine equipment as type approval of ballast water managem ent systems requires both land-based and shipboard test.MEPC 61/2/3 Annex, page 12

I:\MEPC\61\2-3.doc 3.1 Preparation for the test

3.1.1 Cleaning tanks and pipes

The water tanks for test were cleaned by fresh seawater pumped from the sea to remove dirt and residues left over in the tanks. And also each tank was pressure-washed down with
fresh water after each test.

3.1.2 Test water

Test water was prepared in a 10 m 3 tank using high salinity seawater at the Jangmok Bay or brackish water, which is made with addition of groundwater to seawater of Jangmok Bay depending on the required salinity (> 32 PSU or 3-32 PSU, respectively, with a minimum difference of 10 PSU). The 10 m 3 of test water was used for both testing and control.

The combination of indigenous organisms and cultured surrogate species (> 50 μ m : Artemia
salina ) 10 μ m - 50 μ m: Amphidinium carterae, Scrippsiella trochoidea and/or Tetraselemis spp. was added to fulfill the biological water quality criteria. One or more cultured species were used at a time depending on the abundance of harvested indigenous organisms and culture conditions. Also, soluble glucose, seaweed powder and prepared mud were added to adjust the initial concentrations of dissolved organic carbon (DOC), particulate organic carbon (POC) and total suspended solids (TSS) to meet chemical water quality criteria.

3.2 Test methods

All nets for the concentration of organisms in the test site should be strictly separated into three sets (each set uses two types of nets; 7 μ m mesh and 45 μ m mesh in diagonal dimension) to avoid cross-contamination.

3.2.1 Temperature and salinity

Temperature and salinity were measured using an YSI 6600 multiparameter water quality
sonde.

3.2.2 pH

The pH meter used was a model 1230, manufactured by Orion Research Inc.

3.2.3 Dissolved oxygen

DO was measured using an YSI 6600 multiparameter water quality sonde.

3.2.4 Determination of dissolved organic carbon (UNESCO, 1994)

"UNESCO, 1994" process was applied for dissolved organic carbon (DOC) analysis.

3.2.5 Determination of dissolved particulate organic carbon (UNESCO, 1994)

"UNESCO, 1994" process was applied for dissolved particle organic carbon (DOC) analysis.

3.2.6 Determination of total suspended solids (APHA, 1995)

"APHA, 1995" process was applied for total suspended solids analysis.MEPC 61/2/3 Annex, page 13

I:\MEPC\61\2-3.doc 3.2.7 Viability test of organisms

Organisms ≥ 10~50 μm

The disinfection efficacy of the "FineBallast MF" BWMS on 10~50 μm sized organisms (mainly phytoplankton) was assessed by th ree kinds of measurements using light microscope, epifluorescence microscope and fluorometer (Turner Designs 10-AU).

Organisms > 50 μm

Survivorship of the organisms larger than 50 μm (mainly zooplankton) was determined based on the appendage's movement under a stereomicroscope (APHA-804C, 1985).

DAPI count for heterotrophic bacteria

For setting up the condition of influent water, 50 mL seawater was fixed with neutralized formalin (final conc. 2%~4%). One millilitre in we ll-fixed seawater is stained with 0.2 mL DAPI (6-diamidino-2-phenylindole) working solution. After 5 minutes, at least 10 fields were counted under UV filter set of fluorescent microscopy at (× 1,000).

Indicator microbes

The microbes analysis applied for this test is as follows:

Escherichia coli ( E. coli )
Vibrio cholerae (serotypes O1 and O139)
Enterococci

Finally, the test mentioned above was additionally conducted with disinfected distilled water in order to confirm whether there was any contamination as a control or not. Water quality of
each test is summarized in Table 3.1.

Table 3.1: A brief summary of water qualities at the test waters for land-based test (The parenthesis is standard deviation)

Test-1 (Seawater) Test-2 (brackish water)

Salinity (PSU) 32.3 ( ± 0.01) 21.4 ( ± 0.01)

DOC (mg/L) 2.8 ( ± 1.6) 5.4 ( ± 0.4)

POC (mg/L) 1.1 ( ± 0.0) 5.9 ( ± 0.6)

TSS (mg/L) 27.3 ( ± 8.4) 63.3 ( ± 1.5)

3.3 Test results

3.3.1 Test-1 (Seawater)

The organism concentrations of test water for the land-based test sampling were set following Guidelines (G8). The water quality of the location is summarized in Table 3.2. The range of the organism concentration for the group bigger than 50 μm in size was from 177,480 to 194,880 inds/m 3 , while that of the group between 10 μm and 50 μm in sizeMEPC 61/2/3 Annex, page 14

I:\MEPC\61\2-3.doc was from 1,845 to 2,150 inds/mL, in test water (Table 3.3). The range of heterotrophic bacterial population density was from 1.9 to 2.8 ×10 6 inds/mL in test water (Table 3.3). However, after "FineBallast MF" BWMS treatment, the number of living organisms for all groups in treated water met the D-2 standard.

Table 3.2: Water quality of Test-1

Date Sample pH Temp. (°C) Salinity (PSU) DO (mg/L) TSS (mg/L) DOC (mg/L) POC (mg/L)

2009.09.16 Test
water 8.0 25.4 32.3 6.5 27.3 2.8 1.1

2009.09.21 Untreated 7.9 20.4 32.2 6.6 21.1 1.8 0.7

2009.09.21 Treated 8.0 20.3 32.1 7.3 13.2 1.6 0.3

Table 3.3: Biological efficacy of "FineBallast MF" BWMS from land-based test (Test-1)

Date Sample Sampling

at 50μm< (inds/m 3 ) 10~50μm (inds/mL) Heterotro.
Bacteria (inds/mL) E. coli (cfu/100mL) Vibrio
cholerae (cfu/100mL) Entero

coccus (cfu/100mL)

20% 180,960 1,898 2.8E+06 9,683 ND 328

50% 177,480 1,845 1.9E+06 6,217 ND 165 2009.
09.16 Test water

80% 194,880 2,150 2.4E+06 3,033 ND 195

20% 4,361 28 - ND ND 10

50% 9,135 25 - ND ND 1 2009.
09.21 Untreated

80% 42,723 1,560 - ND ND 7

20% ND ND - ND ND 8

50% ND ND - ND ND 4 2009.
09.21 Treated

80% ND ND - ND ND 16



### *ND: not detected.

3.3.2 Test-2 (Brackish water)

The organism concentrations of test water for the land-based test sampling were set as the guideline of Guidelines (G8). The water quality of the location is summarized in Table 3.4. The range of the organism concentration for the group bigger than 50μm in size was from 123,200 inds/m 3 to 132,825 inds/m 3 , while that of the group between 10 μm and 50 μm in size was from 1,627 inds/mL to 1,878 inds/mL in test water (Table 3.5). The range of heterotrophic bacterial population density was from 2.3 to 2.9 ×10 6 inds/mL in test water (Table 3.5). However, after "FineBallast MF" BWMS treatment, the number of living organisms for all groups in treated water met the D-2 regulation.MEPC 61/2/3 Annex, page 15

I:\MEPC\61\2-3.doc Table 3.4: Water quality of Test-2

Date Sample pH Temp. (°C) Salinity (PSU) DO (mg/L) TSS (mg/L) DOC (mg/L) POC (mg/L)

2009.10.07 Test
water 7.6 20.9 21.4 6.5 63.3 5.4 5.9

2009.10.12 Untreated 7.5 16.3 21.2 4.8 42.9 2.8 1.3

2009.10.12 Treated 7.8 16.3 20.9 7.0 6.6 1.9 0.8

Table 3.5: Biological efficacy of "FineBallast MF" BWMS from land-based test (Test-2)

Date Sample Sampling

at 50μm< (inds,/m 3 ) 10~50

μm (inds/mL) Heterotro.
Bacteria (inds/mL) E. coli (cfu/100mL) Vibrio
cholerae (cfu/100mL) Entero

coccus (cfu/100mL)

20% 132,825 1,878 2.8E+06 ND ND 18

50% 130,900 1,627 2.3E+06 83 ND 14 2009.
10.07 Test
water

80% 123,200 1,760 2.9E+06 33 ND 43

20% 1,740 15 - 300 ND ND

50% 4,172 26 - 333 ND 40 2009.
10.12 Untreated

80% 4,869 3,430 - 2,567 ND 3,333

20% ND 1 - ND ND ND

50% ND 3 - ND ND ND 2009.
10.12 Treated

80% ND ND - ND ND ND

*ND: not detected.

4 DATA REGARDING EFFECTS ON AQUATIC PLANTS, INVERTEBRATES, FISH AND OTHER BIOTA, INCLUDING SENSITIVE AND SIGNIFICANT ORGANISMS (G9: 4.2.1.1)

This section is intended to evaluate the effects of preparations and their components on organisms and the environment when released with treated ballast water or accidentally during the process.

The effects of the untreated (A) and treated water (B) as well as detoxified cleaning solution (C) on various marine organisms were compared in acute tests using seawater and brackish water and also in chronic tests using seawater. Undiluted cleaning solution (C), which initially contained 1.0%~1.5% of H 2 O 2 and were consequently catalysed by MnO 2 , was included as the worst-case scenario.MEPC 61/2/3 Annex, page 16

I:\MEPC\61\2-3.doc 4.1 Acute aquatic toxicity

No significantly higher acute toxicity was observ ed in the samples of treated ballast water (B) and detoxified cleaning solution (C) compared to the samples of untreated waters (A) using both seawater (34 psu) and brackish water (21 psu). Data were summarized in Tables 4.1 and 4.2, and the raw data was reported in appendix III. For sampling, see section 1.4. The sample C was included to evaluate the remaining toxicity in the cleaning solution after the detoxification process. Since the cleaning solution is the only water which contacts with
H 2 O 2 , and also it is diluted more than 70 times with treated water before deballasting, the results of sample C can be considered as worst-case condition.

Bacteria : In assessing the toxicity of treated ballast water and cleaning solution on the
bacteria Vibrio fischeri, using the "FineBallast MF" BWMS, through the 30 minutes' period,
NOEC and EC 50 values based on luminescence inhibition at the end of the experiment were
100% and >100% for both seawater and brackish water.

Algae : In assessing the toxicity of treated ballast water and cleaning solution using the "FineBallast MF" BWMS on the marine diatom, Skeletonema costatum , through the 72 hours' period, NOEC values based on growth inhibition at the end of the experiment were 50% for untreated and treated seawater samples or 100% for all other samples. EC 50 for all samples
were >100% for both seawater and brackish water.

Rotifer : In studying the toxicity of treated ballast water and cleaning solution using the "FineBallast MF" BWMS on the marine rotifer, Brachionus plicatils , over a 24 hours' period,
NOEC and LC 50 values based on mortality data at the end of the experiment were 100% and >100% only for seawater.

Amphipod : In assessing the toxicity of treated ballast water and cleaning solution using the "FineBallast MF" BWMS on the marine amphipod, Monocorophium acherusicum , over a 96-hour period, NOEC and LC 50 values based on mortality data at the end of the experiment were 100% and >100% for both seawater and brackish water.

Bivalve : In assessing the toxicity of treated ballast water and cleaning solution using the "FineBallast MF" BWMS on the marine bivalve, Ruditapes philippinarum , over a 96-hour period, NOEC and LC 50 values based on mortality data at the end of the experiment were 100% and >100% only for seawater.

Fish : In assessing the toxicity of treated ballast water and cleaning solution using the "FineBallast MF" BWMS on the marine fish, Cyprinodon variegatus , over a 96-hour period,
NOEC and LC 50 values based on mortality data at the end of the experiment were 100%
and >100% for both seawater and brackish water.MEPC 61/2/3 Annex, page 17

I:\MEPC\61\2-3.doc Table 4.1: The result of acute toxicity tests using various marine organisms exposed to untreated (A), treated ballast water (B) and detoxified cleaning solution (C) using seawater (34 psu)

Taxon Species Test
Protocol Endpoint Sampl

e ID * Results (NOEC, %) Results (LC 50 or EC 50 , %)

A 100 >100

B 100 >100 Bacteria Vibrio fischeri ISO
11348-1 Luminescence
inhibition (30 min) C 100 >100

A 50 >100

B 50 >100 Algae Skeletonema
costatum ASTM
E1218-97a Growth
inhibition (72 hrs) C 100 >100

A 100 >100

B 100 >100 Rotifer Brachionus plicatilis ASTM
E1440-91 Mortality (24 hrs) C 100 >100

A 100 >100

B 100 >100 Amphipod Monocorophium
acherusicum EPA 1994 Mortality (96 hrs) C 100 >100

A 100 >100

B 100 >100 Bivalve Ruditapes philippinarum ASTM
E2122-02 Mortality (96 hrs) C 100 >100
A 100 >100
B 100 >100 Fish Cyprinodon variegatus USEPA
821/R02/
014 Mortality (96 hrs) C 100 >100

Table 4.2: The result of acute toxicity tests using various marine organisms exposed to untreated (A), treated ballast water (B) and detoxified cleaning solution (C) using brackish water (21 psu)

Taxon Species Test Protocol Endpoint Sample
ID * Results (NOEC, %) Results (LC 50 or EC 50 , %)

A 100 >100

B 100 >100 Bacteria Vibrio fischeri ISO 11348-1 Luminescence
inhibition (30 min) C 100 >100

A 100 >100

B 100 >100 Algae Skeletonema
costatum ASTM
E1218-97a Growth
inhibition (72 hrs) C 100 >100

A 100 >100

B 100 >100 Amphipod Monocorophium
acherusicum EPA 1994 Mortality (96 hrs)

C 100 >100

A 100 >100
B 100 >100 Fish Cyprinodon variegatus USEPA
821/R02/
014 Mortality (96 hrs) C 100 >100MEPC 61/2/3 Annex, page 18

I:\MEPC\61\2-3.doc 

### 4 .2 Chronic aquatic toxicity

No significantly higher acute toxicity was observ ed in the samples of treated ballast water (B) and detoxified cleaning solution (C) compared to the samples of untreated waters (A) using seawater (34 psu). Data were summarized in Table 4.3 and the raw data reported in appendix III. For sampling, see section 1.4.

Algae : In assessing the chronic toxicity of treated ballast water and cleaning solution using the "FineBallast MF" BWMS on the marine diatom, Skeletonema costatum , over a 96-hour period, NOEC and EC 50 values based on growth inhibition at the end of the experiment were 100% and >100% for seawater, respectively.

Rotifer : In assessing the chronic toxicity of treated ballast water and cleaning solution using the "FineBallast MF" BWMS on the marine rotifer, Brachionus plicatils , during 96 hours,
NOEC and EC 50 values based on the growth of population at the end of the experiment were 100% and >100% for seawater, respectively.

Fish : For the study to assess the chronic toxicity of treated ballast water and cleaning solution using the "FineBallast MF" BWMS on the marine fish, Cyprinodon variegatus

, during 30 days, NOEC and LC 50 values based on mortality data at the end of the experiment were 100% and >100% for seawater, respectively.

Table 4.3: The result of chronic toxicity tests using various marine organisms exposed to untreated (A), treated ballast water (B) and detoxified cleaning solution (C) using seawater (34 psu)

Taxon Species Test
Protocol Endpoint Sample
ID * Results (NOEC, %) Results (LC 50 or EC 50 , %)

A 100 >100

B 100 >100 Algae Skeletonema
costatum ASTM
E1218-97a Growth
inhibition (96 hrs) C 100 >100

A 100 >100

B 100 >100 Rotifer Brachionus plicatilis ASTM
E1440-91 Population growth (96 hrs) C 100 >100

A 100 >100

B 100 >100 Fish Cyprinodon variegatus USEPA
821/R02/014 Mortality (30 days) C 100 >100

4.3 Endocrine disruption

There is no evidence of H 2 O 2 and its oxidative Relevant C hemicals having any significant endocrine disrupting effect on organisms as low as the detected concentration levels in water samples treated by this system (see Tables 6.1, 6.2 and 6.3), nor at higher levels.

4.4 Sediment toxicity

There were only negligible amounts of residual chemicals with no significant toxicity resulting from the treatment as shown in Tables 4.1, 4.2 and 4.3, and appendices II and III. Additionally, H 2 O 2 and most Relevant Chemicals are highly soluble and highly polar substances; no remarkable adsorption for sediment particles is expected. ResidualMEPC 61/2/3 Annex, page 19

I:\MEPC\61\2-3.doc chemicals from the "FineBallast MF" BWMS treatment will not reach benthic environments to cause any adverse effects on benthic organisms due to both the low level of residual chemicals and also the low reactivity of the chemicals to sediment particles.

4.5 Bioavailability/biomagnification/bioconcentration

There were no experimental results for the Active Substance or possible Relevant Chemicals defined here to be bioconcentrated and/or biomagnified in aquatic organisms. Since H 2 O 2 and most oxidative chemicals are well known to quickly degrade chemically and be biologically metabolized, such chemicals are not easily bioconcentrated and/or biomagnified. From the results of the chemical analyses and toxicity tests for the "FineBallast MF" BWMS treated seawater and the worst-case samples compared to those of untreated water, it is not possible that biologically significant amount s of toxic chemicals are bioavailable for bioconcentration in aquatic organisms or further biomagnification through the marine food
chain.

4.6 Food web/population effects

There were no available results for the Active Substance or possible Relevant Chemicals defined here to be transferred through food web, indirectly adversely affecting the upper trophic level of marine biota. Residual chemicals and toxicity were negligible and biomagnification was not feasible for residual chemicals from the treatment.

It is therefore not possible that significant adverse effects occur indirectly in the transfer of chemicals through the marine food web. In addition, we cannot expect that discharged ballast water would adversely affect the higher level of the ecosystem including populations
and communities in either brackish or full seawater environments.

5 DATA ON MAMMALIAN TOXICITY (G9:4.2.1.2)

The "FineBallast MF" BWMS does not adopt or use any Active Substances intended to be directly exposed to mammalian or non-mammalian organisms. The only chemical used in the system is H 2 O 2 (1.5% or less in seawater), which is only used for cleaning filter modules and is subsequently catalysed by manganese dioxide. The final concentrations of H 2 O 2 and total residual oxidants in the detoxified cleaning solution were never greater than 1.0 mg/L (see appendix II) and no aquatic toxicity was observed even from the detoxified cleaning solution, which can be a worst-case sample for the BWMS treated seawater.

The only possible exposure to H 2 O 2 fumes is to the personnel operating the system during necessary procedures, and likewise exposure to liquid H 2 O 2 is possible in cases of carelessness or accident. There is only little pos sibility, however, of anyone being exposed to Relevant Chemical, oxidizing by-products of the reactive of H 2 O 2 with organic matters in
seawater.

5.1 Acute toxicity

5.1.1 General

H 2 O 2 is corrosive to the skin, eyes, and mucous membranes at high concentrations (>10%); and at lower concentrations may cause irritation. Other effects occur from inhalation or ingestion and may include gas embolism, gastric irritation, gastric distension and emesis, accumulation of fluid in the lungs, unconsciousness, and respiratory arrest. Symptoms
become more severe as the concentration of H 2 O 2 increases (SCCP, 2007).MEPC 61/2/3 Annex, page 20

I:\MEPC\61\2-3.doc The systemic effects of H 2 O 2 result from its interaction with catalase in the tissues liberating oxygen and water as it decomposes. One millilitre of 3% H 2 O 2 liberates 10 mL of oxygen. When the amount of oxygen evolved exceeds maximum blood solubility, venous embolism occurs. Intravascular oxygen embolism may also occur. Ingestion of dilute solutions (3%~10%) produces mild gastrointestinal irritation, gastric distension and emesis, and on rare occasions, gastrointestinal erosion or embolism. Ingestion of 10%~20% solution produces similar symptoms, but exposed tissues may also be burned. Ingestion of 20%~40% produces the symptoms described for lower volumes, but may also induce rapid loss of consciousness followed by respiratory arrest.

5.1.2 Oral Exposure

If ingested, solutions of H 2 O 2 up to concentrations of 9% are generally non-toxic; however, even a 3% solution is mildly irritating to mucosal tissue and may cause vomiting and diarrhea. Ingestion of industrial-strength solu tions (approximately 10%) causes systemic toxicity and has been associated with fatalities.

Ingestion of household solutions (3%) usually causes mild mucosal irritation and vomiting. Gastric distension due to liberation of oxygen in the stomach may occur, but hollow-organ rupture is uncommon when dilute solutions are ingested. Ingestion of concentrated solutions (approximately 10%) can cause extreme irritati on, inflammation, and burns of the alimentary tract, and hollow-organ distension and rupture is a significant danger. H 2 O 2 enemas have caused colonic rupture, intestinal gangrene with gas bubbles, and acute ulcerative colitis.

5.1.3 Respiratory exposure

Vapours, mists, or aerosols of H 2 O 2 can cause upper airway irritation, inflammation of the nose, hoarseness, shortness of breath, and a sensation of burning or tightness in the chest. Exposure to high concentrations can result in severe mucosal congestion of the trachea and bronchi and delayed accumulation of fluid in the lungs.

5.2 Effects on eyes and skin

H 2 O 2 is poorly absorbed through intact skin. It is widely used as a disinfectant medicine for injured skin. When used for disinfectant purposes (a t 3% to 5%), it is mildly irritating to the skin and mucous membranes. At a concentration of 10%, which is found in some hair-bleaching solutions, it is strongly irritating and may be corrosive.

Prolonged exposure to concentrated vapour or dilute solutions can cause irritation and temporary bleaching of skin and hair. Contact with concentrated solutions can cause severe
skin burns with blisters.

Exposure to concentrated vapour, mist, or aerosol can cause stinging pain and tearing. Solutions of 5% or greater can cause injury to the eye surface if splashed in the eye (sometimes with delayed effects).

5.3 Repeated-dose toxicity

There is a sufficient database of animal studies available to characterize the repeated dose toxicity of H 2 O 2 via the oral route. Decreased body weight gain was a typical finding in gavages studies on rats employing a dose range of 50 mg/kg~500 mg/kg BW/day. Regarding other parameters examined, a decreased eryt hrocyte count, haematocrit, plasma protein concentration, and plasma catalase were not uncommon observations. When administered in drinking water, 0.5% H 2 O 2 consistently decreased body weight gain (as well as intake ofMEPC 61/2/3 Annex, page 21

I:\MEPC\61\2-3.doc water) in rats and mice, and further studies at lower dose levels showed the same effect even at 1,500 ppm in rats and at 3,000 ppm in mice (SCCP, 2007). The latter, a well-conducted 90-day study with a catalase deficient strain of mice, indicated that the
NOAEL of H 2 O 2 in drinking water was 100 ppm implying a daily dose of 26 mg/kg BW for males and 37 mg/kg BW for females. LOAEL was 300 ppm based on dose related reductions in food and water consumption among females, and on the observation of duodenal mucosal hyperplasia in one male. Hyperplasia was a consistent finding at higher levels of 1,000 ppm and 3,000 ppm both in males and females, and was completely reversible in the recovery period. At the top dose (3,000 ppm) total plasma protein and globulin concentrations were
reduced.

Repeated exposure H 2 O 2 inhalation toxicity is not well elucidated. Some studies showed that local effects in the skin, airways, and lungs might occur at about 10 mg/m 3 . A recent 28-day range finding inhalation toxicity study in rats (SCCP, 2007) showed respiratory tract irritation and concentration-related necrosis and inflammation of the epithelium in the anterior regions of the nasal cavity at 14.6 mg/m 3 and 33 mg/m 3 but not at 2.9 mg/m 3 (the apparent NOAEL).

5.4 Chronic toxicity

Because H 2 O 2 is rapidly decomposed in the body, it is unlikely to cause chronic toxicity. However, repeated exposures to H 2 O 2 vapour may cause chronic irritation of the respiratory tract and partial or complete lung collapse. Repeated contact with vapour or solution may result in the bleaching of skin and hair.

5.5 Developmental and reproductive toxicity

H 2 O 2 is not included in Reproductive and Developmental Toxicants, a 1991 report published by the U.S. General Accounting Office (GAO) that lists 30 chemicals of concern because of widely acknowledged reproductive and developmental consequences. No reports were located on the developmental or reproductive effects of H 2 O 2 in humans.

5.6 Carcinogenicity

The International Agency for Research on Cancer (IARC) has determined that H 2 O 2 is not classifiable as to carcinogenicity in humans (IARC, 1999).

5.7 Mutagenicity/genotoxicity

H 2 O 2 played a role as a mutagen and genotoxicant in a variety of in vitro test systems. However, regarding the in vivo genotoxicity of H 2 O 2 , studies employing modern methodologies resulted in a negative outcome. The available studies are not in support of a significant genotoxicity/mutagenicity for H 2 O 2 under in vivo conditions as H 2 O 2 is degraded so quickly when introduced into a body regardless of exposure route (oral, dermal and respiratory). According to the principles followed in the EU, H 2 O 2 is not classified as a mutagen.

5.8 Toxicokinetics

Biological membranes are highly permeable to H 2 O 2 ; the permeability constants of 0.2 cm/min for peroxisomal membranes and 0.04 cm/min for erythrocyte plasma membranes may be compared with those for water in a variety of membranes, ranging from 0.02 to 0.42 cm/min (Branco et al. 2004). Thus, H 2 O 2 is expected to be readily taken up by cells constituting absorption surfaces, but at the same time, it is effectively metabolized and it is uncertain to what extent the unchanged substance may enter blood circulation.MEPC 61/2/3 Annex, page 22

I:\MEPC\61\2-3.doc Moreover, in the blood, red blood cells have an immense metabolic capacity to degrade H 2 O 2

.

Animal studies show that administration of high concentrations of H 2 O 2 through various routes, resulting in high rates of absorption, leads to oxygen bubble formation in blood vessels. This indirectly indicates that H 2 O 2 has been absorbed systemically but then rapidly degraded by metabolizing enzymes in the circulating blood.

There are two main H 2 O 2 metabolizing enzymes, catalase and glutathione peroxidase, which
control H 2 O 2 concentration at different levels and in different parts of the cell. In the blood, red blood cells efficiently remove intracellular and extracellular H 2 O 2

.

In aerobic cellular metabolism complete reduction of a molecule of oxygen to water requires four electrons, and in a sequential univalent process the superoxide anion radical (O 2 - ), H 2 O 2 and the hydroxyl radical (OH•) intermediates are formed (Fridovich 1978; 1983). In the presence of reduced metal ions (Fe 2+ ; Cu + ) hydroxyl radicals may originate from H 2 O 2 through the Fenton reaction. The chemical reactions involved in the generation of reactive oxygen species are shown below.

Molecular oxygen is reduced to water by four one-electron reduction steps:

O 2 + e → O 2 – • (superoxide anion)
O 2 – • + e + 2H + → H 2 O 2 (hydrogen peroxide)
H 2 O 2 + e + H + → OH• + H 2 O (hydroxyl radical)
OH• + e + H + → H 2 O (water)

H 2 O 2 is a normal metabolite in the aerobic cell, but there is uncertainty about its true levels in biological media due to analytical difficulties. The steady state level appears to depend on the balance between its generation and degradation. H 2 O 2 passes readily across biological membranes (permeability constant corresponds to that of water) and, because it slowly reacts with organic substrates, it can diffuse at considerable distances in the cell. There are
two main H 2 O 2 metabolizing enzymes, catalase and glutathione peroxidase, which control
H 2 O 2 concentration at different levels and in different parts of the cell as well as in the blood. At low physiological levels H 2 O 2 is mainly decomposed by GSH peroxidase whereas the
contribution of catalase increases with an increase in H 2 O 2 concentration. Red blood cells
remove H 2 O 2 efficiently from the blood due to very high catalase activity whereas in the serum, catalase activity is low.

The systemic absorption of H 2 O 2 is limited by its rapid enzymatic degradation in mucous membrane cells lining the gastrointestinal and respiratory tract and to a certain extent also in skin. Tissue damage, for example, on contact with severely irritant concentrations of H 2 O 2 , can lead to absorption into circulation. In the blood, H 2 O 2 is very rapidly degraded yielding Oxygen and Water. The rapid degradation limits systemic availability of H 2 O 2 . It is therefore unlikely that organs beyond the site of first contact will be affected.

6 DATA ON ENVIRONMENTAL FATE AND EFFECTS UNDER AEROBIC AND ANAEROBIC CONDITIONS (G9: 4.2.1.3)

6.1 Modes of degradation (biotic; abiotic)

All chemical compounds formed by treatment using "FineBallast MF" BWMS are expected to follow natural decomposition processes by natural biotic or abiotic pathways.MEPC 61/2/3 Annex, page 23

I:\MEPC\61\2-3.doc H 2 O 2 is a quite reActive Substance in the presence of other substances, elements, radiation, materials or cells. Both biotic and abiotic degradation processes are important routes in the
removal of H 2 O 2 in the environment.

Biological degradation of H 2 O 2 is an enzyme-mediated process. Abiotic degradation of H 2 O 2 is due to reaction with itself (disproportionation), reaction with transition metals, organic compounds capable of reacting with H 2 O 2 , reaction with free radicals, heat or light.

H 2 O 2 is normally a short-lived substance in the environment. Rapid degradation occurs due to many alternative and compet itive degradation pathways. However, like most substances, in special circumstances when degradation processes are inactive, H 2 O 2 can be an extremely persistent substance in the environment.

The reliable degradation rate of chloroform in water under aerobic condition was not available. However, under anaerobic condition, chloroform is known to be readily biodegraded in water and sediment.

6.1.1 Biotic degradation

H 2 O 2 is biologically degradable. Aerobic bacteri a produce catalase enzymes that convert
H 2 O 2 to water and oxygen. Catalase is present in most aerobic bacteria and therefore biological degradation readily starts when H 2 O 2 is in contact with microbial material (no remarkable lag-phase).

Therefore, the half-life is between minutes and hours in municipal wastewater (> 10 6 cells/mL) and only a few seconds in sludge (10 8 -10 10 cells/mL). In natural waters ( ≤ 10 3 cells/mL) the biodegradation half-life is from hours to a few days. Degradation kinetics is generally assumed to be of the first order with respect to H 2 O 2 at low concentrations and not of the first order at higher concentrations (hundreds of micrograms or more in surface water) leading to longer half-lives as initial concentrations increase (Spain et al. , 1989; Moffett and Zafirioiu, 1990; Wong and Zhang, 2008).

The degradation rate of chloroform in surface water is assumed to be 0 day -1 due to the lack of reliable data and that in sediment to be 0.046 day -1 , which means that the half-life in sediments is 15 days (EU, 2007).

6.1.2 Abiotic degradation

H 2 O 2 decomposes into water and oxygen at rates which depend on contact with catalytic materials (metals, activated carbon, enzymes) and other factors (heat, sunlight) (Moffett and Zafiriou, 1990; Goor et al. 2005).

H 2 O 2 ==> H 2 O + 1/2O 2 , H = -98.30 kJ/mol

This reaction is highly exothermic and takes place in the presence of small amounts of catalyst even in aqueous solution. In the absence of catalyst, it occurs only in the gas phase at high temperature (Goor et al. , 2005).

Many materials and substances have a catalytic action on the degradation of H 2 O 2 . Most transition metals and heavy metals can induce H 2 O 2 decomposition. The range of decomposition rates is large because of varying catalytic efficiency. With the exception of fluorine, the halogens also catalyse the decomposition of H 2 O 2 by a cyclic oxidation-reduction mechanism (Wong and Zhang, 2008).MEPC 61/2/3 Annex, page 24

I:\MEPC\61\2-3.doc In spite of the lack of information, chloroform may not be degraded substantially by any abiotic process.

6.2 Bioaccumulation, partition coefficient, octanol/water coefficient

H 2 O 2 is such a reactive and short-lived polar substance that no significant bioaccumulation is expected. There are no experimental results on bioaccumulation and octanol/water coefficient available. The estimated log P OW (octanol/water coefficient) based on structure analyses of about -1.5 indicates negligible potential of bioaccumulation in aquatic organisms. Therefore, the estimated BCF (bioconcentration factor) for fish is ranged 1.4~3.3, which means that the concentration in fish is only 1.4~3.3 times higher than in water (EU, 2003).

Chloroform is not readily bioaccumulated in aquatic environments. There are some experimental data on bioaccumulation of chloroform in fresh water fish. The BCF of chloroform for fish species ranged from 1.4~ 13 during 1 or 42 days of exposure period with flow-through exposure system (EC, 2007).

6.3 Persistence and identification of the main metabolites in the relevant media (ballast water, marine and fresh waters)

H 2 O 2 is a very reActive Substance in the presence of other substances, elements, radiation, materials or cells. Both biotic and abiotic degradation processes are important routes in the
removal of H 2 O 2 from the environment.
Besides H 2 O 2 is not readily volatilized, chloroform can be fast volatilized into the air compartment. So the volatilization will be the mo st important route for its removal from the aquatic environment.

6.4 Reaction with organic matter

To identify products of concern to the environment from the reaction of radicals with organic matter, some chloro- and bromo-compounds were analysed in three types of test water (untreated-, treated- and detoxified cleaning solution) (Tables 6.1, 6.2 and 6.3).

There was no significant detection of any poten tial Relevant Chemical. Only one chemical, thiosulfate, was detected in one sample of treated seawater prepared for the chronic toxicity test by the BWMS (Table 6.3), however, it was not detected in other 3 samples for the chronic test, and also not detected in all samples for the acute seawater and brackish water

tests.

No other chemical was detected in all the treated water samples for both acute and chronic

tests.

Chloroform was detected in one untreated water sample (0.19 ppb) and two cleaning solution samples (0.09 and 0.20 ppb). In other samples, chloroform concentration was all below 0.01 ppb.

Bromform and 1,2,3- Trichloropropane was detected as 0.03 and 0.42 ppb only in one sample of untreated seawater prepared for acute and chronic toxicity test, respectively. They were not detected in other untreated water or all samples of treated and cleaning solution. These two chemicals detected only from untreated water samples were not related to the BWMS treatment. They were probably produced naturally, but removed during the filtering and/or cleaning process of the BWMS.MEPC 61/2/3 Annex, page 25

I:\MEPC\61\2-3.doc As described above, only two Relevant Chemic als were detected in one treated seawater and two cleaning solution samples. Also the detected concentrations were similar to natural levels, so they would not cause any consider able risk to aquatic organisms or human. There are enough evidences that any of relevant harmful by-products will not be produced and remained in water for at least 5 days after the treatment by "FineBallst MF" BWMS from the chemical and toxicological results.

Detailed methods and results are described in appendix II.

Table 6.1: The concentration of H 2 O 2 and potential Relevant Chemicals in untreated (A), treated by "FineBallast MF" BWMS (B) and detoxified cleaning solution samples (C) prepared together with samples for acute toxicity tests using seawater (34 psu)

Chemical Unit Untreated water (A) [Sample ID: A-A] Treated water (B) [Sample ID: A-B] Detoxified Cleaning solution (C) [Sample ID: A-C]

Total Residual Oxidant mg/L <0.1 <0.1 <0.1

Free chlorine mg/L <0.03 <0.03 <0.03 Thiosulfate mg/L <0.02 <0.02 <0.02 Bromate μg/L <0.39 <0.39 <0.39 Bromoform μg/L 0.03 <0.03 <0.03 Chloroform μg/L <0.01 <0.01 0.09 Dibromochloromethane μg/L <0.02 <0.02 <0.02 Dichlorobromomethane μg/L <0.02 <0.02 <0.02 Monobromoacetic acid μg/L <0.103 <0.103 <0.103 Dibromoacetic acid μg /L <0.049 <0.049 <0.049 Tribromoacetic acid μg/L <0.322 <0.322 <0.322 Monochloroacetic acid μg /L <0.160 <0.160 <0.160 Dichloroacetic acid μg /L <0.130 <0.130 <0.130 Trichloroacetic acid μg /L <0.039 <0.039 <0.039 Bromochloroacetic acid μg/L <0.089 <0.089 <0.089 Dibronoacetonitrile μg/L <0.001 <0.001 <0.001 1,2,3- Trichloropropane μ g/L <0.05 <0.05 <0.05MEPC 61/2/3 Annex, page 26

I:\MEPC\61\2-3.doc Table 6.2: The concentration of H 2 O 2 and potential Relevant Chemicals in untreated (A), treated by "FineBallast MF" BWMS (B) and detoxified cleaning solution samples (C) prepared together with samples for acute toxicity tests using brackish water (21 psu)

Chemical Unit Untreated water (A) [Sample ID: E-A] Treated water (B) [Sample ID: E-B] Detoxified Cleaning solution (C) [Sample ID: E-C]
Total Residual Oxidant mg /L <0.1 <0.1 <0.1
Free chlorine mg/L <0.03 <0.03 <0.03 Thiosulfate mg/L <0.2 <0.2 <0.2 Bromate μg/L <0. 39 <0.39 <0.39 Bromoform μg/L <0.03 <0.03 <0.03 Chloroform μg/L <0.01 <0.01 <0.01 Dibromochloromethane μg/L <0.02 <0.02 <0.02 Dichlorobromomethane μg/ L <0.02 <0.02 <0.02

Monobromoacetic acid μg/L <0.103 <0.103 <0.103 Dibromoacetic acid μg/ L <0.049 <0.049 <0.049

Tribromoacetic acid μg/L <0.332 <0.332 <0.332

Monochloroacetic acid μg/L <0.160 <0.160 <0.160 Dichloroacetic acid μg/ L <0.130 <0.130 <0.130

Trichloroacetic acid μg/L <0.039 <0.039 <0.039

Bromochloroacetic acid μg/L <0.089 <0.089 <0.089 Dibronoacetonitrile μg/ L <0.001 <0.001 <0.001
1,2,3- Trichloropropane μg/L <0.05 <0.05 <0.05

Table 6.3: The concentration of H 2 O 2 and potential Relevant Chemicals in untreated (A), treated by "FineBallast MF" BWMS (B) and detoxified cleaning solution samples (C) prepared together with samples for chronic toxicity tests using seawater (34 psu)

Sample

Type Untreated water (A) Treated water (B) Detoxified Cleaning solution (C)

Time #1 #2 #3 #4 #1 #2 #3 #4 #1 #2 #3 #4 Chemical

Sample ID C1-A C2-A C3-A C4-A C1-B C2-B C3-B C4-B C1-C C2-C C3-C C4-C

Total Residual Oxidant mg/L <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

Free chlorine mg/L <0.03 <0.03 <0.03 <0.03 <0.03 <0.03 <0.03 <0.03 <0.03 <0.03 <0.03 <0.03 Thiosulfate mg/L <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 1.8 <0.2 <0.2 <0.2 <0.2 Bromate μg/L <0.39 <0.39 <0.39 <0.39 <0.39 <0.39 <0.39 <0.39 <0.39 <0.39 <0.39 <0.39 Bromoform μg/L <0.03 <0.03 <0.03 <0.03 <0.03 <0.03 <0.03 <0.03 <0.03 <0.03 <0.03 <0.03 Chloroform μg/L <0.01 0.19 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 0.20 <0.01 <0.01 <0.01 Dibromochloromethane μg/L <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 Dichlorobromomethane μg/L <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 Monobromoacetic acid μg/L <0.103 <0.103 <0.103 <0.103 <0.103 <0.103 <0.103 <0.103 <0.103 <0.103 <0.103 <0.103 Dibromoacetic acid μg/L <0.049 <0.049 <0.049 <0.049 <0.049 <0.049 <0.049 <0.049 <0.049 <0.049 <0.049 <0.049 Tribromoacetic acid μg/L <0.332 <0.332 <0.332 <0.332 <0.332 <0.332 <0.332 <0.332 <0.332 <0.332 <0.332 <0.332 Monochloroacetic acid μg/L <0.160 <0.160 <0.160 <0.160 <0.160 <0.160 <0.160 <0.160 <0.160 <0.160 <0.160 <0.160 Dichloroacetic acid μg/L <0.130 <0.130 <0.130 <0.130 0.13 <0.130 <0.130 <0.130 <0.130 <0.130 <0.130 <0.130 Trichloroacetic acid μg/L <0.039 <0.039 <0.039 <0.039 <0.039 <0.039 <0.039 <0.039 <0.039 <0.039 <0.039 <0.039 Bromochloroacetic acid μg/L <0.089 <0.089 <0.089 <0.089 <0.089 <0.089 <0.089 <0.089 <0.089 <0.089 <0.089 <0.089 Dibronoacetonitrile μg/L <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 1,2,3- Trichloropropane μg/L <0.05 <0.05 <0.05 0.42 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05MEPC 61/2/3 Annex, page 27

I:\MEPC\61\2-3.doc 

### 6 .5 Potential physical effects on wildlife and benthic habitats

There is no logical possibility that the treatment could physically affect wildlife or benthic habitats. The treatment does not seem to affect the physical properties of the seawater and surrounding environment during operation. The chemical and toxicity data showed that there was no significant residual toxic effect from treatment of aquatic organisms including two benthic species (bivalves and amphipods), which serve as an important dietary source
for wildlife.

6.6 Potential residue in seafood

H 2 O 2 and its potential Relevant Chemicals are not readily bioaccumulated in aquatic organisms and not biomagnified through the marine food chain. So no potential residue in
seafood from the treatment seems to occur.

6.7 Known interactive effects

There is no evidence of known or expected interactive effects.

7 PHYSICAL AND CHEMICAL PROPERTIES OF THE PREPARATIONS, ACTIVE SUBSTANCE, AND TREATED BALLAST WATER, IF APPLICABLE (G9: 4.2.1.4)

7.1 Physical and chemical properties of the Active Substance

The "Fine Ballast MF" BWMS uses only one Active Substance, H 2 O 2 for clearing its filter
module. Most H 2 O 2 is catalysed before ballasting so only a limited amount of H 2 O 2 Relevant
Chemicals can remain.

H 2 O 2 is clear colourless liquid, normally handled in an aqueous solution. H 2 O 2 is not flammable. There is a dangerous fire hazard from the chemical reaction of H 2 O 2 with flammable materials. However, H 2 O 2 is a powerful oxidizer, particularly in its concentrated state, and reacts violently with combustible and reducing materials causing fires and explosion hazards.

The identification and physico-chemical properties of the Active Substance are summarized below (see Tables 7.1 and 7.2).

CAS-No: 7722-84-1
EINECS-No: 231-765-0 IUPAC name: hydrogen peroxide Synonyms: dihydrogen dioxide, hydrogen dioxide Molecular weight: 34.02 g/mol
Molecular formula: H 2 O 2 Structural formula: H - O - O - HMEPC 61/2/3 Annex, page 28

I:\MEPC\61\2-3.doc Table 7.1: Physical and chemical properties of pure H 2 O 2 (EC, 2003)

Property Value Melting point -0.4 or -0.43°C Boiling point 150-152°C decomposition Density 1.4425 g/cm 3 (25°C) Viscosity 1.249 (20°C) Vapour pressure 3 hPa (25°C) Water solubility miscible in all proportions pK a 11.62 (25°C) Henry's law
constant 7.5·10 -4 Pa m 3 /mol (20°C) measured

The physico-chemical properties may change depending on the purity of the H 2 O 2

.

Table 7.2: Physical and chemical properties of H 2 O 2 -water mixture solution (EC, 2003 )

H 2 O 2 % 35% w/w 50% w/w 70% w/w 90% w/w Melting point -33 °C -52 °C -40 °C -11 °C
Boiling point 108 °C 114 °C 125 °C 141 °C
Density(25 °C ) 1.1282 1.1914 1.2839 1.3867 Vapour pressure (partial) 0.05 kPa (30 °C ) 0.11 kPa (30 °C ) 0.17 kPa (30 °C ) 0.29 kPa (30 °C ) Vapour pressure (total) - 24 hPa (30 °C ) 14.7 hPa (30 °C ) 6.7 hPa (30 °C )

Saturated vapour
concentration at 25 °C (mg/m 3 ) - 787 1,685 3,049

Surface tension at

20 °C (mN/m) 74.6 75.7 77.3 79.2

Viscosity (1·10 -

3 kg/ms) 1.11 1.17 1.24 1.26

The partial vapour pressure of H 2 O 2 -water mixture considerably decreases with the decrease
of H 2 O 2 concentration in solution from 3 hPa (100%) to 0.48 hPa (35%), therefore, the saturated vapour concentration also decreases with the decrease of H 2 O 2 concentration (Tables 7.1 and 7.2).

Partial vapour pressure is very important to estimate the air concentration of chemicals (e.g., H 2 O 2 ), which can be vaporized in water matrix. Figure 7.1 shows that partial pressure
increases with the increase of H 2 O 2 concentration and temperature. There is no data
for 1.5% H 2 O 2 solution (representative concentration in CIP unit during cleaning process) at room temperature (~20 o C), but the partial vapour pressure of the cleaning solution will be certainly lower than 10 Pa, which is that of 5% H 2 O 2 solution at 50 o C (arrow in Figure 7.1).MEPC 61/2/3 Annex, page 29

I:\MEPC\61\2-3.doc

Figure 7.1: Variation of Partial Vapour Pressure (Pa) of H 2 O 2 -water mixture depending
on the concentration of H 2 O 2 and temperature ( o C). (cited from internet site http://www.h2o2.com/intro/properties/physical.html#13)

7.2 Corrosivity

A corrosivity test was performed with treated ballast water from the "FineBallast" system over 30 days. The test results showed no significant changes in the corrosivity of treated ballast water compared to natural seawater (see Table 7.3 and appendix IV).

Table 7.3: The result of the corrosivity test with ballast water treated by the "FineBallast MF" BWMS

Test Item Sample Rating Number (mean ± S.D) Methods

A 10 ± 0
B 10 ± 0 Rating of unscribed areas
C 10 ± 0

A 9 ± 1.7

B 9 ± 1.7 Rating of failure at scribe

C 10 ± 0 ASTM D 1645-08

8 ANALYTICAL METHODS AT ENVIRONMENTALLY RELEVANT CONCENTRATIONS (G9: 4.2.1.5)

All analyses were done according to standard methods with toxicity testing performed under supervision of KORDI. The testing laboratory, KTR is accredited by KOLAS for chemical analysis of environmental samples including DOC and POC analysis (appendix II). Although the NeoEnBiz Co. LTD Institute laboratory is not specifically accredited for toxicological testing, the personnel of this institute have solid experience in toxicological research, and all tests were performed according to good laboratory practice. Data on quality assurance are provided in each test report (appendix III). 

### 5% H 2 

### O 2 

### 100% H 2 

### O 2MEPC 61/2/3 Annex, page 30

I:\MEPC\61\2-3.doc An extraction of the Quality Assurance Project Plan (QAPP) for all testing is attached in appendix I.

The Quality Management Plan (QMP) addresses the quality control management structure and policies of the Test Organization (including subcontractors and outside laboratories).

The QAPP is a project specific technical docum ent reflecting the specifics of the system to be tested, the test facility, and other conditions affecting the actual design and implementation of the required experiments.

All analyses of Active Substance and Relevant Chemicals including by-products were conducted in accordance with standard operation procedures and the KTR quality manual (see Table 8.1). Quality assurance and control was performed based on a separated study plan as outlined in QAPP.

Table 8.1: List of analytical methods for active and Relevant Chemicals

Chemical CAS No. Molecular
Formula Analytical Method

Total Residual Oxidant - - US EPA 303.3; 1978 Free chlorine - - ISO 7393-1; 1985 (E)

Thiosulfate - S 2 O 3 ISO 10636; 1994 (modified)

Bromate 15541-45-4 BrO 3 ISO 15061; 2001

Bromoform 75-25-2 CHBr 3 US EPA 524.2; 1995

Chloroform 67-66-3 CHCl 3 US EPA 524.2; 1995

Dibromochloromethane 124-48-1 CHBr 2 Cl US EPA 524.2; 1995

Dichlorobromomethane 75-27-4 CHBrCl 2 US EPA 524.2; 1995

Monobromoacetic acid 79-08-3 C 2 H 3 BrO 2 US EPA 552.2; 1995

Dibromoacetic acid 631-64-1 C 2 H 2 Br 2 O 2 US EPA 552.2; 1995

Tribromoacetic acid 75-96-7 C 2 H 1 Br 3 O 2 US EPA 552.2; 1995

Monochloroacetic acid 79-11-8 C 2 H 3 ClO 2 US EPA 552.2; 1995
Dichloroacetic acid 79-43-6 C 2 H 2 Cl 2 O 2 US EPA 552.2; 1995

Trichloroacetic acid 76-03-9 C 2 H 1 Cl 3 O 2 US EPA 552.2; 1995

Bromochloroacetic acid 5589-96-8 C 2 H 2 BrClO 2 US EPA 552.2; 1995
Dibronoacetonitrile 3252-43-5 C 2 HBr 2 N US EPA 551.1; 1995 1,2,3- Trichloropropane 96-18-4 C 3 H 5 Cl 3 US EPA 524.2; 1995

9 RISK CHARACTERIZATION

9.1 Screening for persistency, bioaccumulation and toxicity

The assessments on intrinsic properties of the Active Substance (H 2 O 2 ) and detected Relevant Chemicals (chloroform), such as persistency, bioaccumulation and toxicity were
conducted below.

Persistency : The half-life of H 2 O 2 (100%) in seawater samples varied from 50 to 70 hours. The half life of chloroform in seawater was not available, but in fresh water, those varied from 1.5~10 days. The standard criterion of persistency described in Procedure (G9) isMEPC 61/2/3 Annex, page 31

I:\MEPC\61\2-3.doc half-life >60 days. Both chemicals are removed relatively quickly and tend not to be persistent in aquatic environments.

Bioaccumulation : The highest BCF of H 2 O 2 (100%) and chloroform for fish is 3.3 and 13, respectively. The estimated log P OW of H 2 O 2 is -1.5 and that of chloroform is 2.0. The criterion for bioaccumulation is BCF > 2000 or log P OW > 3.0. Both chemicals are not bioaccumulated
or bioconcentrated because both have low P ow and also H 2 O 2 is fastly degraded and chloroform is fastly volatilized into the air from the surface water.

Toxicity : Not many NOEC results of H 2 O 2 on marine organisms are available from the literature, but the lowest NOEC for fresh water organisms was 0.1 mg/L, which is not in the range of the toxicity criterion for NOEC (<0.01 mg/L). The lowest NOEC for chloroform on fresh water organisms was 1.4 mg/L, which is even higher than that of H 2 O 2

.

PBT screening of the Active Substance and Relevant Chemicals detected in the "FineBallast MF" BWMS treated water showed that they are not included among the PBT
chemicals.

The chemical and ecotoxicological results also support that there is no significant remaining toxic effect in treated water and even in worst-case water after 5 days of storage.

9.2 Toxicity testing of the treated ballast water

Acute and chronic ecotoxicity tests with "FineBallast MF" BWMS treated seawater and brackish water covering multiple test species (a bacteria, an algae, several invertebrates, and a fish) indicated no acute or chronic toxicity to any test organisms at any effluent concentrations as compared to control and the untreated water. Even full strength effluent (100%) did not reveal any significant deleterious effects on any of the test species in both acute and chronic tests. Consequently, the effluent is expected to be non-toxic to aquatic organisms as well as to the marine environment in general (appendix III).

The actual NOEC for "FineBallast MF" BWMS treated seawater and brackish water was not measurable; the statistically determined NOEC was 100% (see appendix III).

The cleaning solution is the only water containing Active Substances as high as 1.5% during the cleaning phase before detoxification by cata lyses. To evaluate the worst-case scenario, the detoxified cleaning solution samples (C) were also included in all chemical and toxicity

tests.

Though TRO and free chlorine were detected in the detoxified cleaning solution that adds
H 2 O 2 of 10% concentration that is the concentration 6.7~10 times (1.0~1.5%H 2 O 2 ) when operating usually, each concentration has decreased with the time passage. TRO value became 0.1 mg/L and free chlorine value became 0.05 mg/L two days later. And, other any Relevant Chemicals were not detected. Therefore, the residual chemicals and toxicities were negligible even in the cleaning solution after 5 days of storage (see appendix VIII).

As free radicals due to H 2 O 2 have a relative short lifetime and after 5 days of degradation, no significant toxic effects are expected for aquatic organisms. There should be no need for holding time in order to observe further adverse effects upon discharge.MEPC 61/2/3 Annex, page 32

I:\MEPC\61\2-3.doc 9.3 Risk analysis for aquatic organisms

Test results revealed no measurable levels of potentially toxic substances and no significant acute or chronic effects of the full strength effluent and also diluted samples on aquatic organisms. No apparent environmental risks could therefore be identified.

Acute and chronic toxicity tests on "FineBallast MF" BWMS treated seawater and brackish water showed no effect on any of the test organisms (appendix III).

The H 2 O 2 concentrations were below 0.1 mg/L and chloroform were below 0.2 mg/L in all treated water samples for deballasting into the environment and also in detoxified cleaning solution, which are ~10 and 1000 times lower than the toxic levels among the reported values for marine organisms, respectively (see appendix VI for ecotoxicity data from the literature).

In spite of the lack of reliable toxicity results, toxic concentration level of thiosulfate ranged tens of thousands ppm in water. The detected concentration of thiosulfate ion in a treated water sample (1.8 mg/L) was much below the reported toxic level and may be included in the range of naturally occurring level in seawater (0.12~2.4 mg/L; CigleneEki and C'osoviC, 1997). Thiosulfate can be produced biol ogically by sulfate reducing bacteria in seawater, however, it is not clear why it was detected only in one sample and not in others.

Most of the toxicity data showed that the remaining levels of Active Substance and potential Relevant Chemicals are not considered toxic to most aquatic organisms.

Two benthic species (amphipods and bivalves) exposed to the treated water also showed negligible toxic effects. Due to the rapid degration rate in sediment as well as low P
ow and K d of both H 2 O 2 and chloroform, a risk for aquatic organisms exposed to sediment is considered to be negligible.

Due to the low bioaccumulative potency and low persistency in water of both H 2 O 2 and chloroform, secondary poisioning and biomagnification through food chain could not occur in the aquatic ecosystems.

In conclusion, it should be noted that the analyses performed and presented in this document are preliminary and will be complemented with furt her tests, both with regard to toxicity as well as the chemical properties of the treated water, if necessary. The test results found no measurable levels of potentially toxic substances and no acute and chronic effects of the full strength effluent and also diluted effluents on aquatic organisms. Therefore, no apparent
environmental risk could be identified. Furt hermore, no carcinogenic, mutagenic or endocrine disruptive substances were found in the samples treated by the BWMS.

10 RISK ASSESSMENT

10.1 Risk to ship safety

10.1.1 Corrosion

Influential factors on corrosion in seawater are salt content, solute gases such as oxygen, carbon dioxide, and pH level. Of the several fact ors, the solute oxygen content is of primary importance as a component influencing the corrosion behaviour of most metal in seawater. The water treated by "FineBallast MF" BWMS contained negligible amount of H 2 O 2 due to the high efficient catalysing procedure, therefore, it seems to have any significant reactiveMEPC 61/2/3 Annex, page 33

I:\MEPC\61\2-3.doc oxygen. There was no pH change in the treated ballast water as compared to untreated water (influent).

The results of the 30-day preliminary corrosion test conducted on the "FineBallast MF" BWMS showed no significant difference in inscribed areas and failure at the scribe between untreated (A) and treated seawater (B). The results indicate that there is no detectable difference in oxidizing potency due to reactive oxygen between the untreated water and
treated water.

Only a small difference (~9%) was detected for the cleaning solution (C) compared to untreated (A) and normally treated water (B) probably due to a greater number of oxidants in the worst-case samples (see appendix IV).

The conditions for the corrosion test here were very severe because the test duration was not long enough; test solutions in each treatment were changed every day with 5-day aged water after sampling. In realistic conditions, the surface of the ballast tank will not likely be exposed to changed water every day. In any event, we should not expect additional corrosivity from the "FineBallast MF" BWMS treated seawater for at least a month. Further experiments adopting a longer test period and realistic exposure conditions should be conducted related to corrosivity in future research.

10.1.2 Personnel safety

A risk assessment (RA) study of a "FineBallast MF" BWMS installed on land was conducted. The objective of the study was to identify and summarize all known hazardous events that could occur during normal operation and maintenance phases (see appendix VII for details). An RA workshop was carried out by attendees with a lot of experience in mechanical and process design, fabrication and installation, etc., in MES. The scope of the RA study is as follows: Membrane module, CIP unit and Human safety.

Table 10.1: Potential hazard list for each module to workers operating the BWMS

Hazard

No. Hazard System (or Sub-system) Mode

1 Membrane module falling Human safety maintenance

2 Membrane module comes out due to fouling Membrane module Operation

3 Cleaning solution floods the CIP tank CIP unit Cleaning

4 CIP tank or chemical line leakage CIP unit Cleaning

5 CIP tank solution levels too low CIP unit Cleaning

6 Oxygen released on decomposition which may intensify fires CIP unit Storage

10.1.3 Exposure values

According to ACGIH guidelines, the exposure limit for H 2 O 2 is 1 ppm. For the Basic Approval test under Procedure (G9), it is difficult to simulate the actual environment on ship, thus we check strict conditions about this matter. During CIP unit working, the seawater containing
H 2 O 2 feeds from the "Feed Tank" (see Figure 1.3) and returns to this tank from membraneMEPC 61/2/3 Annex, page 34

I:\MEPC\61\2-3.doc units. The inside air of the "Feed Tank" is checked during seawater circulation where H 2 O 2 mist is expected to exist. From the two anal yses, the values are 2.7 ppm and 3.1 ppm. These values exceed the ACGIH guidelines, however, the tank hatch is closed for normal operations, and has a very low risk of leakage. For the Guideli nes (G8) test, we would simulate the actual environment on ship as closely as we can, and check exposure values again.

10.1.4 Human health risk assessment

Direct contact during this operation is minimized by recommended handling procedures that include appropriate personal protective equipment, gloves, goggles and, if needed, respiratory protection. No additional risk to workers or ship personnel is considered to arise
from the "FineBallast MF" BWMS.

Furthermore, there is no concern for mutagenicity or carcinogenicity, already argued above (sections 5.6 and 5.7).

After all, the product can be handled safely in this method of ballast water management. The 8-hour averaged air concentration of H 2 O 2 in the BWMS work place should be maintained at below 1 ppm under regulation (Table 10.2). The measured H 2 O 2 concentration in the air of feed tank is below 3.1 ppm and therefore the H 2 O 2 concentration in air of the BWMS working place should be much lower.

To estimate the air concentration using evaporation model, we used the exposure model program. The variable volume of the work place (50~1,000 m 3 ) and the ventilation rate (0~3/hr) was used for the estimation (see appendix V for details). The reasonable conservative values of most the physico-chemical parameters were used for the estimation, the air concentration results are all below 1 ppm, however.

Therefore, we concluded that there is only negligible risk even for the workers staying 8 hours everyday in the place for BWMS operation.

Table 10.2: Standards or guidelines on human health from various agencies
for H 2 O 2 in air

Regulatory body* H 2 O 2 Description

OSHA 1 ppm

AGCIH 1 ppm Permissible exposure limit (PEL), averaged over an 8 hours work shift; TWA (time weighed average)

NIOSH 75 ppm Immediately dangerous to life or health (IDLH)

AIHA 50 ppm Emergency response planning guidelines (ERPG-2),
maximum airborne concentration below which it is believed that nearly all individuals could be exposed for up to 1 hour without experiencing or developing
irreversible or other serious health effects or symptoms which could impair an individual's ability to take protective action

*OSHA: Occupational Safety and Health Administration, USA

AGCIH: American Conference of Industrial Hygienists, USA NIOSH: The National Institute for Occupational Safety and Health Administration, USA AIHA: American Industrial Hygiene Association, USAMEPC 61/2/3 Annex, page 35

I:\MEPC\61\2-3.doc 10.2 Risk to environment

The chemical analyses (appendix II) and the toxicity tests (appendix III) have led to the conclusion that there is negligible risk to the aquatic environment. Neither potential hazardous substances nor significant acute and chronic toxicity in the treated water samples as well as cleaning solution were significantly observed for the BWMS evaluated in this report.

Under realistic emission scenarios, discharged water will be diluted at minimum, dozens of times or more, so any residual toxicity woul d seem to be insignificant both during and after deballasting from the ship if realistic conditions are relevant to the test conditions in this report.

To evaluate the possible environmental effect due to the discharge of ballast water treated by the "FineBallast MF" BWMS, the model estimation of probable environmental concentrations (PECs) of the Active Substance (H 2 O 2 ) and Relevant Chemical (chloroform) was conducted using the similar parameters with Tokyo harbour condition. Then, the PECs of both chemicals were compared to the predicted no effect concentrations (PNECs) reported previously.

10.2.1 Prediction of discharge and environmental concentrations (G9: 5.3.8)

10.2.1.1 Introduction

The Marine Anti-foulant model (MAMPEC) was used in this dossier to predict environmental
concentrations of H 2 O 2 considered as most part of TRO in the port water after discharge. MAMPEC was originally programmed to calculate environmental concentrations of anti-fouling biocides released from ship coatings. In a modified way it can be used to
calculate concentrations that are released const antly into the water by other processes like for example ballast water treatment. The applicabilit y of the model to any chemical substance made it a useful tool for environmental impact studies.

10.2.1.2 H 2 O 2

As a worst case scenario, the following calculations are therefore all based on H 2 O 2 . PECs of
H 2 O 2 were calculated based on a degradation factor (half-life) determined during MAMPEC
simulation.

10.2.1.3 Parameterization of the model

To determine the environmental concentration of the released compound in the harbour water and the sediment, several parameters are necessary. These parameters define the harbour and its characteristics, the compound that is being released in the designated sea area. This section provides detailed parameterization of the model.

10.2.1.4 Half-life

For modelling of various environmental scenarios a wide range of the half-life was used, from an hour to days. Within MAMPEC it was not possible to include the decay of the compound of interest during emptying the ballast water tank. In this case, therefore, a worst-case
scenario was assumed that the water released from the ballast tanks has the same concentration at the start and at the end of discharge.MEPC 61/2/3 Annex, page 36

I:\MEPC\61\2-3.doc 10.2.1.5 H 2 O 2 concentrations in the ballast water and amount of ballast water released

The following discharge H 2 O 2 concentration was used in calculations:

- 0.1 mg/L - a concentration observed in detoxified cleaning solution (when 10%
H 2 O 2 was used; see appendix VIII) 2 days or 5 days after treatment.

Further it was assumed that all ships are equipped with the "FineBallast MF" BWMS with the water characterized by the same holding time (H 2 O 2 level).

It was assumed that there were 15 ships could be anchored in the Port of Tokyo and the total area is 1,504,718m 2 . The total amount of ballasting and deballasting water in the designated sea area was set to be 1,378,117m 3 a year (based on 2001 statistical data). Simply assuming the amount of deballasting to be 1/2 the total amount of ballasting and deballasting, 689,059m 3 /year or 1,888m 3 /day or 78.7m 3 /hour of ballast water will be discharged. These numbers for the Port of Tokyo were used in the publicly available dossiers of other ballast water management system developers and it would be reasonable to
maintain the same scenarios in the current calculations.

The following model inputs result from the assumptions above:

Concentration of
chemical

(mg/L) Ballast water released per day (m 3 ) Chemical released per day (g)

0.1 of H 2 O 2 1,888 188.8 0.0002 of chloroform 1,888 0.3776

10.2.1.6 Background concentration

The background concentration of H 2 O 2 was assumed to be 0 to determine exactly the amount introduced by the "FineBallast MF" BWMS.

10.2.1.7 Results of modelling for H 2 O 2

The half-life is a critical variable to estimate the PEC of H 2 O 2 , however, it can be affected by many factors in the natural environments. The PECs of H 2 O 2 were estimated under conditions described above using MAMPEC when the half-life of H 2 O 2 varied from 0.94 to 960 hours, of which range covers the previously reported half-life of H 2 O 2 (~60 hours) in water.

The PEC of H 2 O 2 increased with the increased of half-life. With the longest half-life, the
maximum PEC of H 2 O 2 was estimated as 0.012 μg/L.

Predicted environmental concentrations of H 2 O 2 (PEC H 2 O 2 ) vary significantly depending on
which value of the H 2 O 2 half-life was selected as a model parameter. For a half-life less than an hour and discharge concentration of 0.1 mg/L, a range of PEC values was between 1.0E-07 and 5.5E-04 μg/L. For a half-life greater than 20 days and discharge concentration of 0.1 mg/L, a range of PEC values was between 1.5E-03 and 1.2E-02 μg/L.MEPC 61/2/3 Annex, page 37

I:\MEPC\61\2-3.doc 10.2.1.8 Results of modelling for chloroform

Similar with the PEC estimation for H 2 O 2 described above, the PECs of chloroform were estimated when the half-life of chloroform varied from 100 days to 900 days. The half-life of chloroform in seawater was not reported previously, so we adopted the conservative range for the PEC estimation. Maximum PEC of chloroform was only 0.000018 μg/L even with the
conservative condition.

10.2.2 Effects on aquatic organisms

Predicted No-Effect Concentration (PNEC) for H 2 O 2 is shown in Table 10.3.

Table 10.3: Predicted No-Effect Concentration (PNEC) for H 2 O 2

Chemical PNEC (μg/L) Factor Applied Comment(s)

H 2 O 2 10 N/A EU RAR (2003)

TRO 0.04 N/A Conservative value (PNEC of HClO in EU RAR (2007)) Chloroform 48-146 N/A EU RAR (2007)

10.2.3 Risk to the aquatic environment

The potential risk to the aquatic environment is based on a series of PEC/PNEC ratios for Active Substance, H 2 O 2 (measured as TRO) and a Relevant Chemical, chloroform using
a worst case scenario.

Given below are the PEC/PNEC ratios fo r the average, minimum, and maximum
concentrations of H 2 O 2 in the Port of Tokyo using the dilutions predicted by the MAMPEC
model for various H 2 O 2 decay half-lives. PEC/PNEC ratios were always below 1 when
the H 2 O 2 concentration in the discharged water was 0.1 mg/L (>2 days after treatment).

PEC/PNEC ratios were always below 1 when we used the PNEC value for H 2 O 2 (10 μg/L)
even under the worst-case conditions.

Table 10.4: H 2 O 2 PEC/PNEC ratios for discharged ballast water in the Port of Tokyo as PNEC 0.04 and 10 μg/L

PEC/PNEC as PNEC 0.04 ug/L
H 2 O 2 in Discharge- 0.1 mg L-1 PEC/PNEC as PNEC 10 ug/L
H 2 O 2 in Discharge- 1.3 mg L-1 Half-life, h

average minimum maximum average minimum maximum
0.9375 2.24E-03 2.50E-06 1.38E-02 8.97E-06 1.00E-08 5.50E-05
1.875 4.48E-03 4.13E-05 2.22E-02 1.79E-05 1.65E-07 8.89E-05
3.75 8.90E-03 3.35E-04 3.48E-02 3.56E-05 1.34E-06 1.39E-04
7.5 1.74E-02 1.55E-03 5.28E-02 6.96E-05 6.18E-06 2.11E-04
15 3.25E-02 4.68E-03 7.85E-02 1.30E-04 1.87E-05 3.14E-04
30 5.63E-02 1.03E-02 1.15E-01 2.25E-04 4.10E-05 4.59E-04
60 8.70E-02 1.77E-02 1.61E-01 3.48E-04 7.06E-05 6.44E-04
120 1.19E-01 2.53E-02 2.09E-01 4.75E-04 1.01E-04 8.37E-04
240 1.45E-01 3.10E-02 2.50E-01 5.79E-04 1.24E-04 9.98E-04
480 1.62E-01 3.50E-02 2.78E-01 6.49E-04 1.40E-04 1.11E-03
960 1.73E-01 3.75E-02 2.95E-01 6.91E-04 1.50E-04 1.18E-03MEPC 61/2/3 Annex, page 38

I:\MEPC\61\2-3.doc The PEC/PNEC results for chloroform were also estimated using the same method with
those for H 2 O 2 . Results showed that PEC/PNEC ratios were far below 1 even under worst-case conditions. Therefore, the risks to aquatic organisms due to chloroform in the discharged water will be negligible.

Table 10.5: Chloroform PEC/PNEC ratios for discharged ballast water in the Port of Toyko as PNEC 48 μg/L

PEC/PNEC Chloroform in Discharge- 0.2 μg/L Half-life, days

average minimum maximum
100 2.06E-07 4.38E-08 3.60E-07
450 2.08E-07 4.46E-08 3.67E-07
900 2.08E-07 4.46E-08 3.67E-07

Overall, the chemical analyses (appendix II) and the toxicity tests (appendix III) have led to the conclusion that there is negligible risk to the aquatic environment. Neither potential hazardous substances nor significant acute and chronic toxicity in the worst-case samples and treated water samples were significantly observed for the BWMS evaluated in this report.

Under realistic emission scenarios, discharged water will be diluted at minimum, dozens of times or more, so any residual toxicity woul d seem to be insignificant both during and after deballasting from the ship if realistic conditions are relevant to the test conditions in this report.

11 REFERENCES

American Public Health Association (APHA), 1985. Standard Method for Examination of
Water and Wastewater. American Water Association and Water Environment Federation
16 th Edition Washington D.C., 742-748 pp.

American Public Health Association (APHA), 1995. Standard Method for Examination of
Water and Wastewater. American Water Association and Water Environment Federation
20 th Edition Washington D.C. 1325 pp.

Barroin, G. and Feuillade, M. (1986). Hydrogen Peroxide as a potential algicide for
Oscillatoria rubescens D.C. Water Research , 20, 619-623.

Branco MR, Marinho HS, Cyrne L and Antunes F. (2004) Decrease of H 2 O 2 Plasma Membrane Permeability during Adaptation to H 2 O 2 in Saccharomyces cerevisiae. The Journal of Biological Chemistry , 279: 6501-6506.

Ciglenecki I and Cosovic B (1997). Electrochemical Determination of Thiosulfate in Seawater in the Presence of Elemental Sulfur and Sulfide. Electroanalysis 9, 775-780.

EC (European Commission), Summary Risk Assessment Report. Hydrogen Peroxide. 2003.

EC (European Commision), 2003. European Union Risk Assessment Report Vol. 38 – Hydrogen peroxide.MEPC 61/2/3 Annex, page 39

I:\MEPC\61\2-3.doc EC (European Commision), 2007. European Union Risk Assessment Report (Draft) –
Chloroform.

EC (European Commision), 2007. European Union Risk Assessment Report (Final) –
Chlorine.

Fridovich I (1978). The biology of oxygen radicals. Science 201, 875-880.

Fridovich I (1983). Superoxide radical: an endogenous toxicant . Ann. Rev. Pharmacol.
Toxicol. 23, 239-257.

Garvey, M., B. Moriceau, and U. Passow1, 2007. Applicability of the FDA assay to determine the viability of marine phytoplankton under different environmental conditions. Marine Ecology Progress Series , 352, 17-26.

Goor G et al. (2005). Hydrogen Peroxide In: Ullmann's Encyclopedia of Industrial Chemistry, 5th completely revised edition, Vol. A 13. Elvers B, Hawkins S, Ravenscroft M and Schulz G (eds), VCH, Weinheim, 443-466.

IARC (1999). Monograph on the Evaluation of Carcinogenic Risk Chemicals to Humans. Volume 71. Re-evaluation of some organic chemicals, hydrazine and hydrogen peroxide.

Jochem, F., 1999. Dark survival strategies in marine phytoplankton assessed by cytometric measurement of metabolic activity with fluorescin diacetate. Mar Biol , 135, 721–728.

Moffett J and Zafiriou OC (1990) An investigation of hydrogen peroxide chemistry in surface waters of Vineyard Sound with H 2 18 O 2 and 18 O 2 . Limnology & Oceanography. 35: 1221-1229.

Pouneva, I., 1997. Evaluation of algal culture viability and physiological state by fluorescent microscopic methods. Bulg. J. Plant Physiol ., 23(1-2): 67-76.

SCCP (Scientific Committee on Consumer Products), Opinion on hydrogen peroxide, in its free form or when released, in oral hygiene products and tooth whitening products,
18 December 2007.

Sharp, J.H., 1974. Improved analysis for "particulate" organic carbon and nitrogen from

seawater. Limnol. Oceanogr. 19, 984-989.

Spain JC, Milligan JD, Downey DC and Slaughter JK (1989). Excessive bacterial decomposition of H 2 O 2 during enhanced biodegradation. Groundwater 27, 163-167.

UNESCO, 1994. Protocols for Joint Global Carbon Flux Study (JGOFS) Core Measurement. Manuals and Guides, 29: 101-118 pp.

US EPA (1984) Health assessment document for manganese. Final draft. Cincinnati, OH, US Environmental Protection Agency, Office of Research and Development (EPA-600/8).

* * *MEPC 61/2/3 Annex, page 40

I:\MEPC\61\2-3.doc APPENDIX I

EXTRACTION OF QAPP

Quality Assurance Project Plan (QAPP)

For

FineBallast MF System Testing

For

Type Approval

By

KORDI

Republic of Korea

In accordance with the Guidelines for approval of balla st water management systems (G8)

Project Name: FineBallast MF – Ballast Water Management System

* * *MEPC 61/2/3 Annex, page 41

I:\MEPC\61\2-3.doc APPENDIX II

CHEMICAL ANALYSIS TEST REPORTS

Quality Assurance Project Plan (QAPP)

FineBallast MF Ballast Water Management System Korea Testing & Research Institute

Chemical Analysis Data for Active Substance and Relevant Chemicals

The Active Substance (H 2 O 2 ) was not detected in water either untreated or treated by
FineBallast MF TM at all tested salinities (21 psu or 34 psu). Consistently, TRO chemicals,
which include H 2 O 2 , were not detected in any samples either.

Only three Relevant Chemicals, chloroform, thiosulfate and 1,2,3- Trichloropropane were detected in a limited number of samples.

A potential Relevant Chemical, 1,2,3- Trichloropropane, was detected in only one untreated water sample, and cannot, therefore, be a by-product of BWMS treatment.

Thiosulfate was detected in one treated sample prepared for the chronic fish toxicity test, of which the concentration was 1.8 mg/L.

Chloroform was detected in two detoxified cleaning solution samples (0.09 ug/L and 0.20 ug/L) and one untreated water sample (0.19 ug/L).

The chemical analysis methods conducted for Basic Approval of BWMS was described and
the raw results shown below.

* * *MEPC 61/2/3 Annex, page 42

I:\MEPC\61\2-3.doc APPENDIX III

AQUATIC ORGANISMS TEST REPORTS

Quality Assurance Project Plan (QAPP)

FineBallast MF Ballast Water Management System
NeoEnBiz Co.

Aquatic Organisms Toxicity Test Report

No significant acute or chronic toxicity was observed in treated water compared to untreated water (natural).

* * *MEPC 61/2/3 Annex, page 43

I:\MEPC\61\2-3.doc APPENDIX IV

CORROSIVITY TEST REPORTS

FineBallast MF Ballast Water Management System Korea Testing & Research Institute

Summary of Corrosivity Test Results

Corrosivity tests were conducted to assess the effects of effluent from the "FineBallast MF" system on water ballast tank protective coatings. For the test, an epoxy coating system, which is the most widely used in ship's ballast tank coating, was applied to a Simulated Wave Ballast Tank (SWBT) according to IMO document MSC 82/WP.3.

In conclusion, the test results clearly indicated that treated seawater, the "FineBallast MF" system effluent, had a negligible effect on ship ballast tank coating performance, when compared with natural seawater and c oating performance meets the IMO PSPC requirements regardless of seawater conditions.

* * *MEPC 61/2/3 Annex, page 44

I:\MEPC\61\2-3.doc APPENDIX V

ESTIMATION OF AIR CONCENTRATION OF HYDROGEN PEROXIDE IN THE WORK PLACE (MAXIMUM REASONABLE APPROACH)

To assess the health risks for workers operating the "FineBallast MF" system, air concentrations in the work place were estimated. Reasonable worst-case conditions were assumed for the conservative estimate. The ConsExpo (Ver. 4.1; RIVM) program was used, and as mode of release, the evaporation model was selected. The conditions for estimating air concentration in the work place are shown in Table AV.1 below.

We assumed that workers work 8 hours every day in the work place. The product amount is 5,000 kg (L) and concentration of H 2 O 2 is 1.5%. The volume of the space varies
from 50 m 3 to 1,000 m 3 , which covers the reasonable volume range of the BWMS operating room in ships (the usual volume is 770 m 3 ). The average ventilation rate is not known, so
variable ventilation rates from 0 to 3 hr -1 were used for the calculation. Partial vapour pressure for room temperature (~20 o C) and 1.5% H 2 O 2 in water solution conditions were not known, so that of the more severe conditions (5% of H 2 O 2 in water at 50 o C ) were used.
The mass transfer rate was not known for H 2 O 2 , so one of the default approximating models (Langmuir's method) in the program was selected as it gives a higher value than other
methods.MEPC 61/2/3 Annex, page 45

I:\MEPC\61\2-3.doc Table AV.1: Conditions for estimating maximum air concentration of H 2 O 2 in working place

Parameter Value

Exposure duration 8 hr/day

Product Amount 5,000 kg

Weight Fraction Compound 0.015 (1.5%)

Room Volume (Variable) 50~1,000 m 3

Ventilation Rate (Variable) 0~3 /hr

Release Area 100 cm 2

Temperature 20 o C

Molecular Wt. 34

Partial Vapour Pressure 10 Pascal (5% of H 2 O 2 in water at 50 o C)

(from Fig.7.1)

Mass Transfer Rate 6,720 m/min

(Approximation using Langmuir's method)

Molecular Wt. of Matrix 18

Exposure Frequency Everyday

Log P ow -1.57

Inhalation Rate 34.7 m 3 /day (default)

Body Weight 65 kg (default)

The results were shown below in Table AV.2. Although the estimation was conducted using the very severe conditions or higher parameters (reasonable worst-case conditions), the estimated air concentrations are always below 1 ppm. If we use the more realistic condition (e.g., the realistic partial vapour pressure would be <1 Pa), the estimated concentration will decrease considerably.MEPC 61/2/3 Annex, page 46

I:\MEPC\61\2-3.doc Table AV.2: Estimated H 2 O 2 air concentration in working place (see Table AV.1 for conditions)

(a) Ventilation Rate: 0~3 times/hr with Room Volume: 770 m 3

Ventilation
Rate (1/hr) Air
Concentration (mg/m 3 ) Air
Concentration (ppm)

0 1.09 0.78

0.25 1.04 0.75

0.5 0.99 0.71

1 0.91 0.65

2 0.78 0.56

3 0.69 0.49

(b) Room Volume: 50~1500 m 3 with Ventilation Rate: 1 /hr

Room
Volume Air
Concentration (mg/m 3 ) Air
Concentration (ppm)

50 1.10 0.79

250 1.04 0.75

500 0.97 0.70

770 0.91 0.65

1500 0.86 0.62

* * *MEPC 61/2/3 Annex, page 47

I:\MEPC\61\2-3.doc APPENDIX VI

REFERENCE ECOTOXICITY DATA ON H 2 O 2 AND CHLOROFORM
FROM THE LITERATURE

Here are shown the reference results of ecological toxicity for the Active Substance (H 2 O 2 ) and the only detected Relevant Chemical (chloroform). There are not many reliable sources of toxicity data for marine organisms. We therefore collected the results from research using either marine or fresh water species. The lowest effect concentration of H 2 O 2 for marine species was 850 μg/L and that for fresh water species was 100 μg/L (see Tables AVI.1 and 2). Algae species were relatively sensitive compared to invertebrate and fish species.

Table AVI.1: Acute Toxicity of H 2 O 2 towards aquatic organisms

Taxon Species name Common

name Toxicity endpoint Conc. (μg/L) Reference

Algae Nitzschia
closterium Diatom (marine) EC 50 (48 h) 850 Florence and Stauber, 1986.

Algae Sceietonema
costatum Diatom (marine) EC 50 (72 h) 1,380 Knight et al. 1995 [recited from EC (2003)]

Rotifer Brachionus plicatilis Rotifer (marine) EC 50 (72 h) 2,400 Smit et al. , 2008.

Amphipod Corophium
volutator Scud (marine) EC 50 (10 d) 611,000 Smit et al. , 2008.

Cladocera Daphnia pulex Water flea (fresh water) EC 50 (48 h) 2,400 Shurtleff, 1989 [recited from EC (2003)]

Fish Pimephales promelas Fathead
minnow (fresh water) LC 50 (96 h) 16,400 Shurtleff (1989) [recited from EC (2003)]

Table AVI.2: Chronic Toxicity of H 2 O 2 towards aquatic organisms

Taxon Species name Common

name Toxicity endpoint Conc. (μg/L) Reference

Algae Anabaena flosaquae Cyanobacteria (fresh water) LOEC (32 days) 100 Kavanagh (1992) [recited from EC (2003)]

The lowest effect concentration of chloroform for marine species was 385 μg/L and that for fresh water species was 1463 μg/L (see Tables AVI.3 and 4).MEPC 61/2/3 Annex, page 48

I:\MEPC\61\2-3.doc Table AVI.3: Acute Toxicity of chloroform towards aquatic organisms

Taxon Species name Common

name Toxicity endpoint Conc. (μg/L) Reference

EC 50 477,000 Algae Skeletonema
costatum Diatom

(marine) NOEC 216,000 Cowgill et al. , 1989.

Bivalve (Molluscs) Crassostrea virginica Oyster (marine) LC 50

(48 h) 385 Stewart et al. 1979 [recited from EC (2007)]

Fish Lepomis
macrochirus Fish (marine) LC 50

(96 h) 18,000 Anderson and Lustry, 1980 [recited from EC (2007)]

Rotifer Brachionus calyciflorus Rotifer (fresh water) LC 50 2,000 Snell et al. , 1991.

Table AVI.4: Chronic Toxicity of chloroform towards aquatic organism

Taxon Species name Common

name Toxicity endpoint Conc. (μg/L) Reference

Algae Chlamydomonas
reinhardii Algae (fresh water) EC 10 (72 h) 3,610 Brack and Rottler, 1994 [recited from EC (2007)]

Invertebrates Daphnia magna Water Flea (fresh water) NOEC (21 days) 6,300 Kuhn et al. 1989 [recited from EC (2007)]

Fish Oryzias latipes Fish (fresh water) NOEC (6/9 months) 1,463 Toussaint et al. 2001 [recited from EC (2007)]

* * *MEPC 61/2/3 Annex, page 49

I:\MEPC\61\2-3.doc APPENDIX VII

RISK ASSESSMENT (RA) FOR THE BWMS

The dangerous operation of six items shown in Table 10.1 was forecast, and listed in risk assessment (RA) that described in section 10. Here, a detailed content and the countermeasure of each dangerous operation are described.

* * *MEPC 61/2/3 Annex, page 50

I:\MEPC\61\2-3.doc APPENDIX VIII

EXPERIMENT USING 10% H 2 O 2 AS CLEANING SOLUTION FOR THE BWMS

The normal concentration of H 2 O 2 in cleaning solution during CIP mode is in the range of 1%~1.5%. To simulate more severe conditions, 10% H 2 O 2 seawater was used as cleaning solution and the chemicals remaining in the cleaning solution during the 5-day storage period
were measured.

Five samples were measured for TRO and other chemicals listed in Table. 1 Sample F1-A was the untreated seawater containing 10% H 2 O 2 and sample F1-B was the same seawater
with 10% H 2 O 2 , but used as cleaning solution for the BWMS. Both F1-A and F1-B were stored for 1 day before analysis. Samples F1-C, F2-C and F5-C were the seawater samples which were used as cleaning solution, but catalysed by MnO 2 and stored for 1, 2 and 5 days, respectively.

Only TRO and free chlorine were detected in all samples. TRO concentrations were about 100 mg/L in samples A and B, which were almost 1000 times lower than the initial nominal concentration level (10% or 100,000 mg/L) of H 2 O 2 . The TRO might decrease during 1-d storage due to the fast degradation of H 2 O 2 . TRO concentrations in the catalysed seawater samples were about 100 times lower than the unanalysed samples, which indicate efficient catalysing performance for MnO 2 in the BWMS.

* * *MEPC 61/2/3 Annex, page 51

I:\MEPC\61\2-3.doc APPENDIX IX

MANGANESE ANALYSIS FOR THE BWMS
FINEBALLAST MF BALLAST WATER MANAGEMENT SYSTEM

Summary of Manganese analysis result

To evaluate the environmental impact of Disso lved Manganese that remained in detoxified cleaning water of "FineBallast MF" BWMS, the Manganese analysis was done.

In conclusion, the Dissolved Manganese concentration was detected from the test result in the detoxified cleaning water and (0.097 mg/L~0.198 mg/L) was detected as for about 10 to 20 times in natural seawater. However, the detoxified cleaning water is expected to become Dissolved Manganese concentration equal with natural seawater from the dilution in the ballast tank to at least 70 times or more. Fish growth inhibitions are assumed to be 0.028 mg/L of the Ministry of the Environment's Predicted No Effect Concentration (PNEC) to the aquatic life, and the diluted detoxified cleaning water does not exceed this value ("Volume 6 of the chemical of the environmental risk evaluation", First Volume (2008)).

_____________